US20060216562A1 - Integrated fuel cell system - Google Patents
Integrated fuel cell system Download PDFInfo
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- US20060216562A1 US20060216562A1 US11/347,829 US34782906A US2006216562A1 US 20060216562 A1 US20060216562 A1 US 20060216562A1 US 34782906 A US34782906 A US 34782906A US 2006216562 A1 US2006216562 A1 US 2006216562A1
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- fuel cell
- stream
- water
- fuel
- cell system
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- 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
- H01M8/0625—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 in a modular combined reactor/fuel cell structure
- H01M8/0631—Reactor construction specially adapted for combination reactor/fuel cell
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Definitions
- This invention relates generally to the design and operation of a system for producing electrical power. More specifically, the invention relates to a system for producing electrical power with a fuel cell, especially a proton-exchange-membrane fuel cell (PEMFC).
- a fuel cell especially a proton-exchange-membrane fuel cell (PEMFC).
- PEMFC proton-exchange-membrane fuel cell
- Purified hydrogen is an important fuel source for many energy conversion devices.
- fuel cells use purified hydrogen and an oxidant to produce an electrical potential.
- a process known as steam reforming produces by chemical reaction hydrogen and certain byproducts or impurities.
- a subsequent purification process removes the undesirable impurities to provide hydrogen sufficiently purified for application to a fuel cell.
- a steam reforming process one reacts steam and a carbon-containing compound over a catalyst.
- suitable carbon-containing compounds include, but are not limited to, alcohols (such as methanol or ethanol) and hydrocarbons (such as methane or gasoline or propane).
- Steam reforming requires an elevated operating temperature, e.g., between 250 degrees centigrade and 1300 degrees centigrade, and produces primarily hydrogen and carbon dioxide.
- Some trace quantities of unreacted reactants and trace quantities of byproducts such as carbon monoxide also result from steam reforming.
- a steam reforming unit, or fuel processor is started from a cold, inactive state, it must be preheated to at least a minimum operating temperature before the above reforming reaction will take place.
- the invented system includes a fuel-cell system comprising a fuel cell that produces electrical power from air (oxygen) and hydrogen, and a fuel processor that produces hydrogen from a variety of feedstocks.
- a fuel processor is a steam reformer which produces purified hydrogen from a carbon-containing feedstock and water.
- various mechanisms for implementing the cold start-up of the fuel processor are disclosed, as well as mechanisms for optimizing and/or harvesting the heat and water requirements of the system and/or maintaining the purity of the process water used in the system.
- FIG. 1 is a process flow diagram of a fuel-cell system in which propane or natural gas is used as the fuel to heat the fuel processor during a cold start-up.
- FIG. 2 is a process flow diagram of a fuel-cell system in which a liquid fuel is used to heat the fuel processor during a cold start-up.
- FIG. 3 is an embodiment of the invention in which stored hydrogen is used to heat the fuel processor during a cold start-up.
- FIG. 4 is a process flow diagram of a fuel-cell system in which hydrogen purged from the anode chamber of the fuel cell is combusted to provide additional water for recovery and use.
- FIG. 5 is a process flow diagram of a fuel cell system in which hydrogen purged from the anode chamber of the fuel cell is combusted to provide additional heat and water for recovery and use.
- FIG. 6 is an embodiment of the invention in which high-grade heat is recovered from the fuel processor.
- FIG. 7 shows another embodiment of the invention comprising a dual pump head in which a single motor is used to simultaneously drive two pump heads that deliver both the feedstock and water to the fuel processor.
- FIG. 8 shows yet another embodiment of the invention adapted to preheat either the feedstock or feed water prior to delivery to the fuel processor by heat exchange with hot hydrogen exiting the fuel processor.
- FIG. 9 shows yet another embodiment of the invention comprising one or more ion-exchange beds to maintain low electrical conductivity of the process water.
- FIG. 10 shows a process flow diagram for a fuel cell system in which ion exchange and activated carbon beds are used to purify feed water prior to injection into the fuel processor.
- the invention consists of a fuel-cell system comprising a fuel cell 10 that produces electrical power from air (oxygen) and hydrogen, and a fuel processor 12 that produces hydrogen from a variety of feedstocks.
- a fuel cell is a net producer of water
- said fuel processor 12 is a net consumer of water.
- Fuel cell 10 is preferably a proton exchange membrane fuel cell (PEMFC) and may utilize internal humidification of air and/or hydrogen, including so called self-humidification, or external humidification of air and/or hydrogen.
- Fuel cell 10 produces byproduct water and byproduct heat in addition to electrical power.
- PEMFC proton exchange membrane fuel cell
- feedstocks are suitable for producing hydrogen using fuel processor 12 including, but not limited to, carbon-containing compounds such as hydrocarbons, alcohols, and ethers. Ammonia is also a suitable feedstock.
- Fuel processor 12 preferably produces hydrogen by reacting the carbon-containing feedstock with water by a process commonly known as steam reforming. In this case fuel processor 12 consumes water in addition to consuming feedstock. It is within the scope of the present invention that other chemical methods for making hydrogen from a feedstock, such as partial oxidation and autothermal reforming, may also be used rather than steam reforming.
- FIG. 1 is a process flow diagram for one embodiment of a fuel cell system of this invention.
- the fuel cell 10 receives hydrogen produced by the fuel processor 12 .
- the fuel processor produces hydrogen by reacting, at high temperature, a feedstock from storage reservoir 14 and water from storage reservoir 16 .
- Pump 20 moves feedstock from reservoir 14 and delivers said feedstock to the fuel processor 12 .
- pump 21 moves water from reservoir 16 and delivers said water as stream 22 to the fuel processor 12 .
- Pumps 20 and 21 deliver the feedstock and water to the fuel processor at a pressure ranging from ambient pressure to approximately 300 psig.
- Hydrogen produced by the fuel processor is initially hot because the fuel processor must operate at elevated temperatures of 250° C. to 1300° C.
- the product hydrogen stream 23 from the fuel processor is cooled using heat exchanger 24 and fan 26 to blow cool ambient air over the hot heat exchanger surfaces. Once cooled to a temperature near to or lower than the operating temperature of the fuel cell, which typically is between approximately 0° C. and approximately 80° C., product hydrogen is passed into the anode chamber 28 of the fuel cell stack.
- Air stream 29 is delivered to the cathode chamber 30 of said fuel cell stack 10 by a blower 32 .
- a compressor could also be used in place of blower 32 .
- An example of suitable blowers are centrifugal blowers because of their low noise during operation and low power requirements. However, centrifugal blowers are generally limited to relatively low delivery pressure, typically ⁇ 2 psig.
- a linear compressor may be used. Linear compressors are based on an electromechanical (solenoid) drive that is characterized by relatively low power consumption and low noise.
- An example of a suitable linear compressor is Model Series 5200 sold by Thomas Compressors & Vacuum Pumps (Sheboygan, Wis.).
- a coolant circulating loop is used to maintain the temperature of the fuel cell stack within acceptable limits, such as those described above.
- the coolant serves the purpose of cooling both the cathode and anode chambers of the fuel cell stack.
- coolant circulating pump 34 circulates hot coolant from the fuel cell stack into heat exchanger 36 .
- Fan 38 blows cool air over the hot surfaces of heat exchanger 36 , thereby reducing the temperature of the coolant.
- the coolant may be de-ionized water, distilled water, or other non-conducting and non-corrosive liquids including ethylene glycol and propylene glycol.
- a pressure regulator 40 ensures that the pressure of the hydrogen supplied to the anode chamber 28 of said fuel cell 10 remains at an acceptable value. For most PEM fuel cells, this range of pressures is between ambient pressure to 4 atmospheres, with a pressure range between ambient pressure and approximately 1.5 atmospheres being preferred. Within the anode chamber of the fuel cell hydrogen is consumed and, at the same time, diluted with water vapor. Thus, a periodic purge of hydrogen-rich gas from the anode chamber is required. Purge valve 42 serves this purpose. The purge hydrogen represents a small amount of the total hydrogen supplied to the fuel cell, typically only about 1% to 10% of the total. The purge hydrogen stream 44 may be vented directly to the surroundings, as shown in FIG.
- hydrogen stream 23 may be flowed continuously in excess through anode chamber 28 , eliminating the need for said purge valve 42 . Since some liquid water may be entrained in said purge hydrogen stream 44 , an optional water knock-out may be placed in purge stream 44 for the purpose of separating and collecting said entrained liquid water.
- Excess air is continuously flowed through the cathode chamber 30 .
- the air flow rate is 200% to 300% of the stoichiometric requirement of oxygen to support the magnitude of electrical current produced by the fuel cell, although flow rates outside of this range may be used as well.
- Oxygen-depleted air is discharged from said cathode chamber 30 as stream 52 .
- Stream 52 contains substantial water, as both liquid and vapor, available for recovery.
- Stream 52 is typically saturated with water vapor, and as an example, approximately one third or more of the total water may be freely condensed to liquid water.
- stream 52 is first passed through a knock-out 54 that separates liquid water from the oxygen-depleted air and water vapor.
- Liquid water stream 56 flows out of said knock-out 54 and the liquid water is collected within water reservoir 16 .
- the gas-phase stream 58 exiting knock-out 54 comprises the oxygen-depleted air and water vapor.
- Stream 58 is directed into fuel processor 12 for the purpose of supporting combustion within said fuel processor to generate the required heat for satisfactory operation of the fuel processor (if the fuel processor is based on steam reforming), or to supply oxidant (oxygen) for partial-oxidation of the feedstock (if the fuel processor is based on partial oxidation or autothermal reforming). Since stream 58 is to be used for combustion, there is no primary reason to cool stream 58 or stream 52 , other than to assist with separation of liquid water within said knock-out 54 .
- fuel processor 12 is preferably a steam reformer with internal hydrogen purification.
- suitable steam reforming units are disclosed in pending U.S. patent applications Ser. Nos. 08/741,057 and 08/951,091, which are both entitled “Steam Reformer With Internal Hydrogen Purification” and the disclosures of which are hereby incorporated by reference.
- the operating temperature for steam-reforming is generally between approximately 250° C. and approximately 1300° C., and for most common alcohols and hydrocarbons (except methane) is in the range of approximately 250° C. and approximately 800° C.
- a suitable fuel such as propane or natural gas is fed from a supply source 60 to the fuel processor.
- the fuel is combusted within the fuel processor 12 until the fuel processor is hot enough to begin steam reforming the feedstock.
- a throttle valve 62 regulates the flow of propane or natural gas fuel to the fuel processor during this cold start-up.
- Combustion exhaust stream 64 exits the fuel processor as a hot gas stream laden with water vapor.
- the water vapor in said combustion exhaust stream 64 has essentially two sources: as a byproduct of burning the fuel, and as a component of air stream 58 . It is desirable to recover the water from combustion exhaust stream 64 and to recover heat from said exhaust stream 64 .
- Condenser 66 serves this purpose. Hot, moist exhaust stream 64 passes into said condenser 66 and is chilled using a cold fluid stream 68 . Streams with temperatures near or less than 20° C. have proven effective. Liquid water condenses and flows out of condenser 66 as liquid stream 69 , and is collected in water reservoir 16 .
- Cold fluid stream 68 is warmed by the process of passing hot exhaust stream 64 through said condenser 66 .
- cold outside air may serve as stream 68 and be heated for the purpose of space heating in a residential, commercial, or industrial application.
- cold water may serve as stream 68 and be heated for use as domestic or process hot water, or said hot water may be used for space heating or other heating applications.
- a cold fluid other than air or water including, but not limited to ethylene glycol and propylene glycol, serves as stream 68 .
- fuel processor 12 Once fuel processor 12 has reached a suitable temperature for steam reforming the feedstock, feed water and feedstock are pumped into said fuel processor. For methanol, this temperature should be at least 250° C., with temperatures of at least 450° C. and preferably at least 600° C. being used for most hydrocarbon feedstocks.
- the steam reforming reaction produces a hydrogen-rich reformate gas mixture that is preferably purified within the fuel processor, such as disclosed in our above-identified pending applications, which are incorporated by reference.
- the pure product hydrogen stream 23 is passed to the fuel cell as previously described.
- the hydrogen-depleted stream 75 that is rejected by the hydrogen purifier is passed through throttle valve 78 to be used as fuel for combustion to heat said fuel processor 12 . At this time during the operation of fuel processor 12 there is no longer a need to supply propane or natural gas fuel that was used for the cold start-up, and that fuel supply is shut off.
- FIG. 2 is another embodiment of the present invention in which the fuel processor 12 is heated during a cold start-up by combustion of a liquid fuel, rather than propane or natural gas.
- the liquid fuel may be diesel, gasoline, kerosene, ethanol, methanol, jet fuel, or other combustible liquids.
- liquid fuel is removed from storage supply 100 using pump 102 .
- the discharged liquid fuel from pump 102 is admitted through a suitable nozzle or jet into the combustion region in fuel processor 12 where the fuel is mixed with air and burned to heat said fuel processor.
- the liquid fuel may be vaporized or atomized prior to injection into fuel processor 12 to facilitate combustion.
- FIG. 3 Yet another embodiment of the present invention related to cold start-up of fuel processor 12 is shown in FIG. 3 .
- cold start-up is accomplished by combustion of hydrogen fuel within fuel processor 12 .
- Hydrogen fuel is stored by within hydrogen storage vessel 150 by any known method.
- An example of a particularly well-suited method for storing hydrogen fuel is as a metal hydride.
- Said metal hydride then comprises a metal hydride storage bed serving as storage vessel 150 .
- the equilibrium pressure of hydrogen gas over a given metal hydride is a function of the chemical composition of the metal hydride and the temperature of the system.
- the equilibrium pressure of hydrogen over the metal hydride is between 0 psig (ambient pressure) and 10 psig at a temperature of about 15° C. to 22° C.
- Increasing the temperature of the metal hydride system increases the equilibrium pressure of hydrogen over the metal hydride.
- storage reservoir 150 contains a suitable quantity of a metal hydride, and is called a metal hydride bed.
- fuel hydrogen stream 152 is withdrawn from hydride storage bed 150 and, after passing through isolation valve 154 , is admitted into fuel processor 12 where said hydrogen fuel is combusted to heat the fuel processor.
- the pressure of gaseous hydrogen in said storage bed will begin to decrease and the bed will begin to cool in temperature (phenomena well known to those skilled in the art of hydrogen storage in metal hydride beds).
- warm combustion exhaust stream 64 is flowed through metal hydride storage bed 150 to heat said metal hydride bed. Then, the now cool exhaust exits the warmed metal hydride bed 150 as cool exhaust stream 158 . This allows the pressure of gaseous hydrogen to remain sufficiently high to discharge most of, to nearly all of, the hydrogen from said storage bed 150 .
- isolation valve 154 is closed and hydride storage bed 150 is recharged with hydrogen so that it will be ready for the next cold start-up.
- Recharging of storage bed 150 is accomplished by taking a hydrogen slip stream 160 from purified product hydrogen stream 23 after said product hydrogen stream has been cooled by passing through heat exchanger 24 .
- An optional isolation valve 162 is placed in hydrogen slip stream 160 to facilitate maintenance.
- An advantage of this embodiment of the invention is that the fuel required for cold start-up of fuel processor 12 is clean burning hydrogen, acquired from a previous period of operating the system. Thus, it is not necessary to periodically resupply an auxiliary fuel such as propane or diesel for start-up purposes, nor is it necessary to have a large external storage reservoir for said auxiliary fuels.
- FIG. 4 presents yet another embodiment of the present invention in which purge hydrogen stream 44 is passed into combustor 200 for the purpose of generating additional water to be recovered ultimately by knock-out 54 and condenser 66 .
- Combustor 200 may be catalytic or non-catalytic. Air to support combustion of purge hydrogen stream 44 is supplied by the cathode exhaust stream 52 which is depleted, but not devoid, of oxygen as described previously.
- the single outlet from combustor 200 is exhaust stream 202 that is enriched in water (vapor and liquid) as a result of burning purge hydrogen stream 44 .
- FIG. 5 shows combustor 200 coupled to heat exchanger 250 for the purpose of recovering and using heat generated by combustion of purge hydrogen stream 44 within said combustor 200 .
- Heat exchanger 250 may be simply heat-conductive fins on the exterior of combustor 200 , or a heat exchange fluid may be passed between combustor 200 and heat exchanger 250 . Said heat exchange fluid may be circulated based on natural convection currents, or it may be forcibly circulated by a circulation pump. To utilize the recovered heat a suitable cold fluid stream is passed over hot heat exchanger 250 .
- One such suitable cold fluid stream is air, in which case fan 252 blows a cold air stream over heat exchanger 250 resulting in an increase in the temperature of said air stream.
- suitable cold fluids include, but are not limited to, water, ethylene glycol, propylene glycol, and both the feedstock and feed water to be fed to fuel processor 12 .
- FIG. 6 shows this embodiment of the invention.
- Heat exchanger 300 extracts heat from the high-temperature combustion regions of fuel processor 12 .
- Pump 302 may be used to circulate a heat transfer fluid between fuel processor 12 and heat exchanger 300 , as shown in FIG. 6 , or circulation of said heat transfer fluid may be based on naturally occurring convection currents.
- heat exchanger 300 may comprise a series of heat-conductive fins placed on the hot regions of the fuel processor.
- a suitable cold fluid is passed over the hot heat exchanger 300 .
- Such a suitable cold fluid may be an air stream supplied by fan 305 . In this case said air stream is heated by passing over hot heat exchanger 300 .
- Other suitable cold fluid streams include, but are not limited to, water, ethylene glycol, and propylene glycol.
- Dual-head pump 350 supplies both feedstock from reservoir 14 and feed water from reservoir 16 to fuel processor 12 .
- Dual-head pump 350 comprises two pump heads driven by a single drive motor such that both pump heads are driven at the same speed over the entire operating speed range of the pump motor.
- the pumping rate of each feedstock and feed water is determined by the displacement of each respective cavity in dual-head pump 350 .
- the dual-head pump may be a gear pump with a ratio of displacement volume of the two pump heads being 3:1.
- the flow rate of feed water would be three times greater than the flow rate of feedstock into the fuel processor.
- This ratio would be essentially constant over the entire range of delivery rates achievable with the dual-head pump since this ratio is fixed by the displacement volumes of each of the two pump heads and both pump heads are driven at the same speed by the same drive motor.
- Suitable types of dual-head pumps include, but are not limited to, gear pumps, piston pumps, diaphragm pumps, and peristaltic pumps.
- Yet another embodiment of this invention utilizes the hot product hydrogen stream 23 as it exits fuel processor 12 to pre-heat feed water stream 22 prior to introduction of said feed water into the fuel processor.
- feed water stream 22 enters a counter-current heat exchanger 400 .
- Hot product hydrogen stream 23 also flows into counter-current heat exchanger 400 .
- the feed water stream and the hydrogen stream are isolated from each other, but are in thermal contact such that the hot hydrogen stream is cooled during passage through heat exchanger 400 and the feed water stream is warmed during its passage through heat exchanger 400 .
- product hydrogen stream 23 is cooled to a temperature at or near the operating temperature of the fuel cell (typically between approximately 40° C. and approximately 60° C.).
- Maintaining acceptable water purity in the cooling loop for fuel cell 28 is an important aspect of the successful operation of a PEMFC system. Often, to achieve this objective, fuel cell manufacturers specify stainless steel for all wetted surfaces of the PEMFC cooling loop. This leads to considerable expense, especially since stainless steel radiators (heat exchangers) are expensive and, by virtue of the relatively poor thermal conductivity of stainless steel, large in size.
- FIG. 9 shows an embodiment of this invention that overcomes the need to use stainless steel components throughout the cool loop of the fuel cell, thereby improving the performance of said cooling loop and decreasing its cost.
- This objective is achieved by placing an ion exchange bed 450 in the cooling loop so that cooling water passes through the ion exchange bed during operation of the system. Either all of the cooling water or a portion of the cooling water is passed through the ion exchange bed. Since the objective is to maintain low ionic (both cationic and anionic) concentrations in the cooling water, ion exchange bed 450 should comprise both cation-exchange resins and anion-exchange resins.
- a slip stream of cooling water is passed through ion exchange bed 450 , the flow rate of said slip stream is sized to maintain sufficiently low ionic concentration in the cooling water. Because the cooling water typically passes over electrically charged surfaces within the PEMFC, it is important that the cooling water have a high electrical resistance, but it is not essential that the cooling water be of ultra-high purity with respect to ionic and non-ionic content.
- FIG. 10 shows activated carbon bed 500 and ion exchange bed 502 placed in feed water stream 22 for the purpose of purifying said feed water of ionic and organic contaminants.
- the now purified feed water stream 510 is then admitted into fuel processor 12 .
- Activated carbon bed 500 removes organic impurities from feed water stream 22 .
- Such organic impurities may originate from a variety of sources including, but not limited to, combustion byproducts that are exhausted from fuel processor 12 and carried in exhaust stream 64 to condenser 66 , and from there into condensed liquid water stream 69 .
- Ion exchange bed 502 comprises both cation-exchange resins and anion-exchange resins, thereby removing both cations and anions from feed water stream 22 .
- Ionic contamination of feed water stream 22 may originate from a variety of sources including, but not limited to, corrosion of metallic wetted surfaces in the combustion exhaust line carrying exhaust stream 64 , condenser 66 , the line carrying condensed liquid water stream 69 to water reservoir 16 , and water reservoir 16 .
- the incorporation of ion exchange bed 502 allows the use of materials that are not especially corrosion resistant, but exhibit good thermal conductivity and relatively low cost, for the aforementioned wetted parts of the system, thereby improving the performance of condenser 66 and reducing the cost of the system.
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Abstract
The invented system includes a fuel-cell system comprising a fuel cell that produces electrical power from air (oxygen) and hydrogen, and a fuel processor that produces hydrogen from a variety of feedstocks. One such fuel processor is a steam reformer which produces purified hydrogen from a carbon-containing feedstock and water. In the invented system, various mechanisms for implementing the cold start-up of the fuel processor are disclosed, as well as mechanisms for optimizing and/or harvesting the heat and water requirements of the system and/or maintaining the purity of the process water used in the system.
Description
- This application is a continuation patent application claiming priority to similarly entitled U.S. patent application Ser. No. 11/084,382, which was filed on Mar. 18, 2005, and issued on Feb. 7, 2006 as U.S. Pat. No. 6,994,927, and which is a continuation of U.S. patent application Ser. No. 10/127,030, now U.S. Pat. No. 6,869,707, which was filed on Apr. 19, 2002, and which is a continuation of U.S. patent application Ser. No. 09/190,917, now U.S. Pat. No. 6,376,113, which was filed on Nov. 12, 1998. The complete disclosures of the above-identified patent applications are hereby incorporated by reference for all purposes.
- This invention relates generally to the design and operation of a system for producing electrical power. More specifically, the invention relates to a system for producing electrical power with a fuel cell, especially a proton-exchange-membrane fuel cell (PEMFC).
- Purified hydrogen is an important fuel source for many energy conversion devices. For example, fuel cells use purified hydrogen and an oxidant to produce an electrical potential. A process known as steam reforming produces by chemical reaction hydrogen and certain byproducts or impurities. A subsequent purification process removes the undesirable impurities to provide hydrogen sufficiently purified for application to a fuel cell.
- In a steam reforming process, one reacts steam and a carbon-containing compound over a catalyst. Examples of suitable carbon-containing compounds include, but are not limited to, alcohols (such as methanol or ethanol) and hydrocarbons (such as methane or gasoline or propane). Steam reforming requires an elevated operating temperature, e.g., between 250 degrees centigrade and 1300 degrees centigrade, and produces primarily hydrogen and carbon dioxide. Some trace quantities of unreacted reactants and trace quantities of byproducts such as carbon monoxide also result from steam reforming. When a steam reforming unit, or fuel processor, is started from a cold, inactive state, it must be preheated to at least a minimum operating temperature before the above reforming reaction will take place. A need exists for efficient and alternative methods for this preheating of a steam reforming unit. Efficient operation of the fuel processor also requires careful indexing and control of the ratios of water and carbon-containing feedstock. It is also necessary to maintain and control the purity of the water feeds used with the steam reforming unit and fuel cell.
- The invented system includes a fuel-cell system comprising a fuel cell that produces electrical power from air (oxygen) and hydrogen, and a fuel processor that produces hydrogen from a variety of feedstocks. One such fuel processor is a steam reformer which produces purified hydrogen from a carbon-containing feedstock and water. In the invented system, various mechanisms for implementing the cold start-up of the fuel processor are disclosed, as well as mechanisms for optimizing and/or harvesting the heat and water requirements of the system and/or maintaining the purity of the process water used in the system.
- Many other features of the present invention will become manifest to those versed in the art upon making reference to the detailed description which follows and the accompanying sheets of drawings in which preferred embodiments incorporating the principles of this invention are disclosed as illustrative examples only.
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FIG. 1 is a process flow diagram of a fuel-cell system in which propane or natural gas is used as the fuel to heat the fuel processor during a cold start-up. -
FIG. 2 is a process flow diagram of a fuel-cell system in which a liquid fuel is used to heat the fuel processor during a cold start-up. -
FIG. 3 is an embodiment of the invention in which stored hydrogen is used to heat the fuel processor during a cold start-up. -
FIG. 4 is a process flow diagram of a fuel-cell system in which hydrogen purged from the anode chamber of the fuel cell is combusted to provide additional water for recovery and use. -
FIG. 5 is a process flow diagram of a fuel cell system in which hydrogen purged from the anode chamber of the fuel cell is combusted to provide additional heat and water for recovery and use. -
FIG. 6 is an embodiment of the invention in which high-grade heat is recovered from the fuel processor. -
FIG. 7 shows another embodiment of the invention comprising a dual pump head in which a single motor is used to simultaneously drive two pump heads that deliver both the feedstock and water to the fuel processor. -
FIG. 8 shows yet another embodiment of the invention adapted to preheat either the feedstock or feed water prior to delivery to the fuel processor by heat exchange with hot hydrogen exiting the fuel processor. -
FIG. 9 shows yet another embodiment of the invention comprising one or more ion-exchange beds to maintain low electrical conductivity of the process water. -
FIG. 10 shows a process flow diagram for a fuel cell system in which ion exchange and activated carbon beds are used to purify feed water prior to injection into the fuel processor. - As shown in
FIG. 1 , the invention consists of a fuel-cell system comprising afuel cell 10 that produces electrical power from air (oxygen) and hydrogen, and afuel processor 12 that produces hydrogen from a variety of feedstocks. Generally, said fuel cell is a net producer of water, and saidfuel processor 12 is a net consumer of water.Fuel cell 10 is preferably a proton exchange membrane fuel cell (PEMFC) and may utilize internal humidification of air and/or hydrogen, including so called self-humidification, or external humidification of air and/or hydrogen.Fuel cell 10 produces byproduct water and byproduct heat in addition to electrical power. - Many feedstocks are suitable for producing hydrogen using
fuel processor 12 including, but not limited to, carbon-containing compounds such as hydrocarbons, alcohols, and ethers. Ammonia is also a suitable feedstock.Fuel processor 12 preferably produces hydrogen by reacting the carbon-containing feedstock with water by a process commonly known as steam reforming. In thiscase fuel processor 12 consumes water in addition to consuming feedstock. It is within the scope of the present invention that other chemical methods for making hydrogen from a feedstock, such as partial oxidation and autothermal reforming, may also be used rather than steam reforming. -
FIG. 1 is a process flow diagram for one embodiment of a fuel cell system of this invention. Thefuel cell 10 receives hydrogen produced by thefuel processor 12. The fuel processor produces hydrogen by reacting, at high temperature, a feedstock fromstorage reservoir 14 and water fromstorage reservoir 16.Pump 20 moves feedstock fromreservoir 14 and delivers said feedstock to thefuel processor 12. Likewise,pump 21 moves water fromreservoir 16 and delivers said water asstream 22 to thefuel processor 12.Pumps - Hydrogen produced by the fuel processor is initially hot because the fuel processor must operate at elevated temperatures of 250° C. to 1300° C. The
product hydrogen stream 23 from the fuel processor is cooled usingheat exchanger 24 andfan 26 to blow cool ambient air over the hot heat exchanger surfaces. Once cooled to a temperature near to or lower than the operating temperature of the fuel cell, which typically is between approximately 0° C. and approximately 80° C., product hydrogen is passed into theanode chamber 28 of the fuel cell stack. -
Air stream 29 is delivered to thecathode chamber 30 of saidfuel cell stack 10 by ablower 32. Alternatively, a compressor could also be used in place ofblower 32. An example of suitable blowers are centrifugal blowers because of their low noise during operation and low power requirements. However, centrifugal blowers are generally limited to relatively low delivery pressure, typically <2 psig. For higher delivery pressures, a linear compressor may be used. Linear compressors are based on an electromechanical (solenoid) drive that is characterized by relatively low power consumption and low noise. An example of a suitable linear compressor is Model Series 5200 sold by Thomas Compressors & Vacuum Pumps (Sheboygan, Wis.). - A coolant circulating loop is used to maintain the temperature of the fuel cell stack within acceptable limits, such as those described above. The coolant serves the purpose of cooling both the cathode and anode chambers of the fuel cell stack. To this end,
coolant circulating pump 34 circulates hot coolant from the fuel cell stack intoheat exchanger 36.Fan 38 blows cool air over the hot surfaces ofheat exchanger 36, thereby reducing the temperature of the coolant. The coolant may be de-ionized water, distilled water, or other non-conducting and non-corrosive liquids including ethylene glycol and propylene glycol. - A
pressure regulator 40 ensures that the pressure of the hydrogen supplied to theanode chamber 28 of saidfuel cell 10 remains at an acceptable value. For most PEM fuel cells, this range of pressures is between ambient pressure to 4 atmospheres, with a pressure range between ambient pressure and approximately 1.5 atmospheres being preferred. Within the anode chamber of the fuel cell hydrogen is consumed and, at the same time, diluted with water vapor. Thus, a periodic purge of hydrogen-rich gas from the anode chamber is required.Purge valve 42 serves this purpose. The purge hydrogen represents a small amount of the total hydrogen supplied to the fuel cell, typically only about 1% to 10% of the total. Thepurge hydrogen stream 44 may be vented directly to the surroundings, as shown inFIG. 1 , or it may be used for the purpose of producing heat, or for other purposes. In some embodiments of thisinvention hydrogen stream 23 may be flowed continuously in excess throughanode chamber 28, eliminating the need for saidpurge valve 42. Since some liquid water may be entrained in saidpurge hydrogen stream 44, an optional water knock-out may be placed inpurge stream 44 for the purpose of separating and collecting said entrained liquid water. - Excess air is continuously flowed through the
cathode chamber 30. Typically the air flow rate is 200% to 300% of the stoichiometric requirement of oxygen to support the magnitude of electrical current produced by the fuel cell, although flow rates outside of this range may be used as well. Oxygen-depleted air is discharged from saidcathode chamber 30 asstream 52.Stream 52 contains substantial water, as both liquid and vapor, available for recovery.Stream 52 is typically saturated with water vapor, and as an example, approximately one third or more of the total water may be freely condensed to liquid water. In one embodiment of this invention,stream 52 is first passed through a knock-out 54 that separates liquid water from the oxygen-depleted air and water vapor.Liquid water stream 56 flows out of said knock-out 54 and the liquid water is collected withinwater reservoir 16. The gas-phase stream 58 exiting knock-out 54 comprises the oxygen-depleted air and water vapor. -
Stream 58 is directed intofuel processor 12 for the purpose of supporting combustion within said fuel processor to generate the required heat for satisfactory operation of the fuel processor (if the fuel processor is based on steam reforming), or to supply oxidant (oxygen) for partial-oxidation of the feedstock (if the fuel processor is based on partial oxidation or autothermal reforming). Sincestream 58 is to be used for combustion, there is no primary reason to coolstream 58 orstream 52, other than to assist with separation of liquid water within said knock-out 54. - Still referring to
FIG. 1 ,fuel processor 12 is preferably a steam reformer with internal hydrogen purification. Examples of suitable steam reforming units are disclosed in pending U.S. patent applications Ser. Nos. 08/741,057 and 08/951,091, which are both entitled “Steam Reformer With Internal Hydrogen Purification” and the disclosures of which are hereby incorporated by reference. As described previously, the process of steam reforming involves the chemical reaction of a feedstock with water at elevated temperature, and is generally known to those skilled in the art. The operating temperature for steam-reforming is generally between approximately 250° C. and approximately 1300° C., and for most common alcohols and hydrocarbons (except methane) is in the range of approximately 250° C. and approximately 800° C. To initially heatfuel processor 12 during a cold start-up, a suitable fuel such as propane or natural gas is fed from asupply source 60 to the fuel processor. The fuel is combusted within thefuel processor 12 until the fuel processor is hot enough to begin steam reforming the feedstock. Athrottle valve 62 regulates the flow of propane or natural gas fuel to the fuel processor during this cold start-up. -
Combustion exhaust stream 64 exits the fuel processor as a hot gas stream laden with water vapor. The water vapor in saidcombustion exhaust stream 64 has essentially two sources: as a byproduct of burning the fuel, and as a component ofair stream 58. It is desirable to recover the water fromcombustion exhaust stream 64 and to recover heat from saidexhaust stream 64.Condenser 66 serves this purpose. Hot,moist exhaust stream 64 passes into saidcondenser 66 and is chilled using a coldfluid stream 68. Streams with temperatures near or less than 20° C. have proven effective. Liquid water condenses and flows out ofcondenser 66 asliquid stream 69, and is collected inwater reservoir 16. - Cold
fluid stream 68 is warmed by the process of passinghot exhaust stream 64 through saidcondenser 66. For example, cold outside air may serve asstream 68 and be heated for the purpose of space heating in a residential, commercial, or industrial application. Alternatively, cold water may serve asstream 68 and be heated for use as domestic or process hot water, or said hot water may be used for space heating or other heating applications. Yet another embodiment is that a cold fluid other than air or water including, but not limited to ethylene glycol and propylene glycol, serves asstream 68. - Once
fuel processor 12 has reached a suitable temperature for steam reforming the feedstock, feed water and feedstock are pumped into said fuel processor. For methanol, this temperature should be at least 250° C., with temperatures of at least 450° C. and preferably at least 600° C. being used for most hydrocarbon feedstocks. The steam reforming reaction produces a hydrogen-rich reformate gas mixture that is preferably purified within the fuel processor, such as disclosed in our above-identified pending applications, which are incorporated by reference. The pureproduct hydrogen stream 23 is passed to the fuel cell as previously described. The hydrogen-depletedstream 75 that is rejected by the hydrogen purifier is passed throughthrottle valve 78 to be used as fuel for combustion to heat saidfuel processor 12. At this time during the operation offuel processor 12 there is no longer a need to supply propane or natural gas fuel that was used for the cold start-up, and that fuel supply is shut off. -
FIG. 2 is another embodiment of the present invention in which thefuel processor 12 is heated during a cold start-up by combustion of a liquid fuel, rather than propane or natural gas. The liquid fuel may be diesel, gasoline, kerosene, ethanol, methanol, jet fuel, or other combustible liquids. During a cold start-up, liquid fuel is removed fromstorage supply 100 usingpump 102. The discharged liquid fuel frompump 102 is admitted through a suitable nozzle or jet into the combustion region infuel processor 12 where the fuel is mixed with air and burned to heat said fuel processor. The liquid fuel may be vaporized or atomized prior to injection intofuel processor 12 to facilitate combustion. - Yet another embodiment of the present invention related to cold start-up of
fuel processor 12 is shown inFIG. 3 . In this case cold start-up is accomplished by combustion of hydrogen fuel withinfuel processor 12. Hydrogen fuel is stored by withinhydrogen storage vessel 150 by any known method. An example of a particularly well-suited method for storing hydrogen fuel is as a metal hydride. Said metal hydride then comprises a metal hydride storage bed serving asstorage vessel 150. - Metal hydrides exist in equilibrium with gaseous hydrogen (see F. A. Lewis, “The Palladium Hydrogen System” Academic Press, 1967; and “Hydrogen in Metals I: Basic Properties” edited by G. Alefeld and J Völkl, Springer-Verlag, 1978, the disclosures of which are hereby incorporated by reference). The equilibrium pressure of hydrogen gas over a given metal hydride is a function of the chemical composition of the metal hydride and the temperature of the system. Thus, it is possible to select a metal hydride chemical composition such that the equilibrium pressure of hydrogen over the metal hydride is between 0 psig (ambient pressure) and 10 psig at a temperature of about 15° C. to 22° C. Increasing the temperature of the metal hydride system increases the equilibrium pressure of hydrogen over the metal hydride.
- Returning to
FIG. 3 and for purposes of illustration, it is assumed thatstorage reservoir 150 contains a suitable quantity of a metal hydride, and is called a metal hydride bed. During a cold start-up,fuel hydrogen stream 152 is withdrawn fromhydride storage bed 150 and, after passing throughisolation valve 154, is admitted intofuel processor 12 where said hydrogen fuel is combusted to heat the fuel processor. As fuel hydrogen is withdrawn fromstorage bed 150, the pressure of gaseous hydrogen in said storage bed will begin to decrease and the bed will begin to cool in temperature (phenomena well known to those skilled in the art of hydrogen storage in metal hydride beds). To counteract these trends, warmcombustion exhaust stream 64 is flowed through metalhydride storage bed 150 to heat said metal hydride bed. Then, the now cool exhaust exits the warmedmetal hydride bed 150 ascool exhaust stream 158. This allows the pressure of gaseous hydrogen to remain sufficiently high to discharge most of, to nearly all of, the hydrogen from saidstorage bed 150. - Alternative embodiments of this invention would use other sources to heat
metal hydride bed 150 including electrical resistance heaters and combustion of hydrogen or other fuel to directly heatstorage bed 150. - After completing cold start-up of
fuel processor 12 and hydrogen is being produced by the fuel processor,isolation valve 154 is closed andhydride storage bed 150 is recharged with hydrogen so that it will be ready for the next cold start-up. Recharging ofstorage bed 150 is accomplished by taking ahydrogen slip stream 160 from purifiedproduct hydrogen stream 23 after said product hydrogen stream has been cooled by passing throughheat exchanger 24. During this hydrogen recharging operation, byproduct heat should be removed fromhydride storage bed 150, such as through any known mechanism. Anoptional isolation valve 162 is placed inhydrogen slip stream 160 to facilitate maintenance. - An advantage of this embodiment of the invention is that the fuel required for cold start-up of
fuel processor 12 is clean burning hydrogen, acquired from a previous period of operating the system. Thus, it is not necessary to periodically resupply an auxiliary fuel such as propane or diesel for start-up purposes, nor is it necessary to have a large external storage reservoir for said auxiliary fuels. -
FIG. 4 presents yet another embodiment of the present invention in whichpurge hydrogen stream 44 is passed intocombustor 200 for the purpose of generating additional water to be recovered ultimately by knock-out 54 andcondenser 66.Combustor 200 may be catalytic or non-catalytic. Air to support combustion ofpurge hydrogen stream 44 is supplied by thecathode exhaust stream 52 which is depleted, but not devoid, of oxygen as described previously. The single outlet fromcombustor 200 isexhaust stream 202 that is enriched in water (vapor and liquid) as a result of burningpurge hydrogen stream 44. - In yet another embodiment of the present invention, heat is recovered in addition to water recovery from combustion of
purge hydrogen 44.FIG. 5 shows combustor 200 coupled toheat exchanger 250 for the purpose of recovering and using heat generated by combustion ofpurge hydrogen stream 44 within saidcombustor 200.Heat exchanger 250 may be simply heat-conductive fins on the exterior ofcombustor 200, or a heat exchange fluid may be passed betweencombustor 200 andheat exchanger 250. Said heat exchange fluid may be circulated based on natural convection currents, or it may be forcibly circulated by a circulation pump. To utilize the recovered heat a suitable cold fluid stream is passed overhot heat exchanger 250. One such suitable cold fluid stream is air, in whichcase fan 252 blows a cold air stream overheat exchanger 250 resulting in an increase in the temperature of said air stream. Other suitable cold fluids include, but are not limited to, water, ethylene glycol, propylene glycol, and both the feedstock and feed water to be fed tofuel processor 12. - Useful heat can also be recovered from
fuel processor 12.FIG. 6 shows this embodiment of the invention.Heat exchanger 300 extracts heat from the high-temperature combustion regions offuel processor 12. Pump 302 may be used to circulate a heat transfer fluid betweenfuel processor 12 andheat exchanger 300, as shown inFIG. 6 , or circulation of said heat transfer fluid may be based on naturally occurring convection currents. Alternatively,heat exchanger 300 may comprise a series of heat-conductive fins placed on the hot regions of the fuel processor. For purposes of heat recovery and use, a suitable cold fluid is passed over thehot heat exchanger 300. Such a suitable cold fluid may be an air stream supplied byfan 305. In this case said air stream is heated by passing overhot heat exchanger 300. Other suitable cold fluid streams include, but are not limited to, water, ethylene glycol, and propylene glycol. - Another useful embodiment of the present invention is shown in
FIG. 7 . Dual-head pump 350 supplies both feedstock fromreservoir 14 and feed water fromreservoir 16 tofuel processor 12. Dual-head pump 350 comprises two pump heads driven by a single drive motor such that both pump heads are driven at the same speed over the entire operating speed range of the pump motor. The pumping rate of each feedstock and feed water is determined by the displacement of each respective cavity in dual-head pump 350. For example, to preserve a fixed ratio of feed water to feedstock, as is desirable for steam reforming, the dual-head pump may be a gear pump with a ratio of displacement volume of the two pump heads being 3:1. Thus, if the larger displacement pump head supplied feed water to the fuel processor, and the smaller displacement pump head supplied feedstock (e.g., a liquid hydrocarbon), then the flow rate of feed water would be three times greater than the flow rate of feedstock into the fuel processor. This ratio would be essentially constant over the entire range of delivery rates achievable with the dual-head pump since this ratio is fixed by the displacement volumes of each of the two pump heads and both pump heads are driven at the same speed by the same drive motor. Suitable types of dual-head pumps include, but are not limited to, gear pumps, piston pumps, diaphragm pumps, and peristaltic pumps. - Yet another embodiment of this invention utilizes the hot
product hydrogen stream 23 as it exitsfuel processor 12 to pre-heatfeed water stream 22 prior to introduction of said feed water into the fuel processor. As shown inFIG. 8 , feedwater stream 22 enters acounter-current heat exchanger 400. Hotproduct hydrogen stream 23 also flows intocounter-current heat exchanger 400. The feed water stream and the hydrogen stream are isolated from each other, but are in thermal contact such that the hot hydrogen stream is cooled during passage throughheat exchanger 400 and the feed water stream is warmed during its passage throughheat exchanger 400. When the invented system ofFIG. 8 is used, it is preferable thatproduct hydrogen stream 23 is cooled to a temperature at or near the operating temperature of the fuel cell (typically between approximately 40° C. and approximately 60° C.). - Maintaining acceptable water purity in the cooling loop for
fuel cell 28 is an important aspect of the successful operation of a PEMFC system. Often, to achieve this objective, fuel cell manufacturers specify stainless steel for all wetted surfaces of the PEMFC cooling loop. This leads to considerable expense, especially since stainless steel radiators (heat exchangers) are expensive and, by virtue of the relatively poor thermal conductivity of stainless steel, large in size. -
FIG. 9 shows an embodiment of this invention that overcomes the need to use stainless steel components throughout the cool loop of the fuel cell, thereby improving the performance of said cooling loop and decreasing its cost. This objective is achieved by placing anion exchange bed 450 in the cooling loop so that cooling water passes through the ion exchange bed during operation of the system. Either all of the cooling water or a portion of the cooling water is passed through the ion exchange bed. Since the objective is to maintain low ionic (both cationic and anionic) concentrations in the cooling water,ion exchange bed 450 should comprise both cation-exchange resins and anion-exchange resins. - If a slip stream of cooling water is passed through
ion exchange bed 450, the flow rate of said slip stream is sized to maintain sufficiently low ionic concentration in the cooling water. Because the cooling water typically passes over electrically charged surfaces within the PEMFC, it is important that the cooling water have a high electrical resistance, but it is not essential that the cooling water be of ultra-high purity with respect to ionic and non-ionic content. - It is also important to maintain acceptable levels of purity in the feed water that is to be used within
fuel processor 12 so that the steam-reforming catalysts within said fuel processor are not poisoned and rendered non-effective.FIG. 10 shows activatedcarbon bed 500 andion exchange bed 502 placed infeed water stream 22 for the purpose of purifying said feed water of ionic and organic contaminants. The now purifiedfeed water stream 510 is then admitted intofuel processor 12.Activated carbon bed 500 removes organic impurities fromfeed water stream 22. Such organic impurities may originate from a variety of sources including, but not limited to, combustion byproducts that are exhausted fromfuel processor 12 and carried inexhaust stream 64 tocondenser 66, and from there into condensedliquid water stream 69.Ion exchange bed 502 comprises both cation-exchange resins and anion-exchange resins, thereby removing both cations and anions fromfeed water stream 22. Ionic contamination offeed water stream 22 may originate from a variety of sources including, but not limited to, corrosion of metallic wetted surfaces in the combustion exhaust line carryingexhaust stream 64,condenser 66, the line carrying condensedliquid water stream 69 towater reservoir 16, andwater reservoir 16. The incorporation ofion exchange bed 502 allows the use of materials that are not especially corrosion resistant, but exhibit good thermal conductivity and relatively low cost, for the aforementioned wetted parts of the system, thereby improving the performance ofcondenser 66 and reducing the cost of the system. - The foregoing description of the preferred embodiments of the invention has been presented for purposes of illustration and description. It is not intended to be exhaustive or to limit the invention to the precise form disclosed, and many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and its practical application to thereby enable others skilled in the art to best utilize the invention in various embodiments and with various modifications as are suited to the particular use contemplated. It is intended that the scope of the invention be defined by the claims appended hereto.
Claims (20)
1. A fuel cell system, comprising:
a fuel cell stack adapted to receive hydrogen gas and an oxidant and to produce an electric current therefrom, wherein the fuel cell stack includes an anode chamber to which the hydrogen gas is delivered and a cathode chamber to which the oxidant is delivered, and further wherein the fuel cell stack is adapted to produce a water stream that is removed from the fuel cell stack; and
a cooling assembly that is adapted to receive and cool the water stream, wherein the cooling assembly includes an ion-exchange bed through which at least a portion of the water stream is passed to remove ions from the water stream.
2. The fuel cell system of claim 1 , wherein only a portion of the water stream is passed through the ion-exchange bed.
3. The fuel cell system of claim 1 , wherein all of the water stream is passed through the ion-exchange bed.
4. The fuel cell system of claim 1 , wherein the ion-exchange bed includes an anion-exchange resin.
5. The fuel cell system of claim 1 , wherein the ion-exchange bed includes a cation-exchange resin.
6. The fuel cell system of claim 5 , wherein the ion-exchange bed includes both anion- and cation-exchange resins.
7. The fuel cell system of claim 1 , further comprising a water storage reservoir adapted to receive the water stream.
8. The fuel cell system of claim 1 , further comprising means for providing hydrogen gas for the fuel cell stack.
9. The fuel cell system of claim 1 , further comprising means for producing hydrogen gas for the fuel cell stack.
10. The fuel cell system of claim 9 , further comprising means for recovering water from the hydrogen gas.
11. A method for operating a fuel cell system, the method comprising:
producing hydrogen gas;
combusting a fuel stream to produce a heated combustion exhaust stream;
heating at least a portion of a fuel processor and a heat exchange assembly with the heated combustion exhaust stream;
producing hydrogen gas in the fuel processor via a steam reforming reaction;
delivering at least a portion of the hydrogen gas to a fuel cell stack;
heating a fluid with the heat exchange assembly to produce a heated fluid stream; and
delivering at least a portion of the heated fluid stream to at least one of a residential, commercial, or industrial application.
12. The method of claim 11 , wherein the fluid is air, and the heated fluid stream is delivered to provide space heating to the application.
13. The method of claim 11 , wherein the fluid is water, and the heated fluid stream is delivered to provide space heating to the at least one application.
14. The method of claim 11 , wherein the fluid is water, wherein the application is a residential application, and further wherein the heated fluid stream is delivered to provide domestic hot water to the residential application.
15. The method of claim 11 , wherein the fluid is water, wherein the application is a commercial application, and further wherein the heated fluid stream is delivered to provide process hot water to the commercial application.
16. The method of claim 11 , wherein the fluid is water, wherein the application is an industrial application, and further wherein the heated fluid stream is delivered to provide process hot water to the industrial application.
17. The method of claim 11 , wherein the fluid is at least one of ethylene glycol and propylene glycol, and the heated fluid stream is delivered to provide space heating to the at least one application.
18. The method of claim 11 , wherein the fuel includes hydrogen gas produced by the fuel processor.
19. The method of claim 11 , wherein the fuel includes an exhaust stream from the fuel cell stack.
20. The method of claim 11 , wherein the fuel cell stack is adapted to produce a water stream that is removed from the fuel cell stack, and further wherein the method includes removing impurities from the water stream.
Priority Applications (1)
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US11/347,829 US20060216562A1 (en) | 1998-11-12 | 2006-02-03 | Integrated fuel cell system |
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US11/084,382 US6994927B2 (en) | 1998-11-12 | 2005-03-18 | Integrated fuel cell system |
US11/347,829 US20060216562A1 (en) | 1998-11-12 | 2006-02-03 | Integrated fuel cell system |
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US11/084,382 Expired - Lifetime US6994927B2 (en) | 1998-11-12 | 2005-03-18 | Integrated fuel cell system |
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US11/084,382 Expired - Lifetime US6994927B2 (en) | 1998-11-12 | 2005-03-18 | Integrated fuel cell system |
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Also Published As
Publication number | Publication date |
---|---|
US6869707B2 (en) | 2005-03-22 |
DK1138096T3 (en) | 2010-11-08 |
US6994927B2 (en) | 2006-02-07 |
US20020119353A1 (en) | 2002-08-29 |
DE69942839D1 (en) | 2010-11-18 |
US6376113B1 (en) | 2002-04-23 |
ATE483667T1 (en) | 2010-10-15 |
US20050181248A1 (en) | 2005-08-18 |
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