Patent Grant
11309563
This present disclosure relates to multi-stack high efficiency fuel cell system capable of allowing the export of hydrogen and syngas from the anode exhaust of the fuel cell system. The systems of the present disclosure may be used with any types of fuel cells, and particularly with molten carbonate fuel cells and solid oxide fuel cells.
A fuel cell is a device which directly converts chemical energy stored in hydrocarbon fuel into electrical energy by means of an electrical reaction. Generally, a fuel cell comprises an anode and a cathode separated by an electrolyte matrix, which conducts electrically charged ions. In order to produce a useful power level, a number of individual fuel cells are stacked in series with an electrically conductive separator plate between each cell.
In building fuel cell systems, individual fuel cells are stacked together to form a fuel cell stack. The number of fuel cells determines the power rating of the fuel cell stack. To provide systems with higher power ratings, a number of fuel cell stacks are utilized and the outputs of the fuel cell stacks are combined to provide the desired power output. In certain fuel cell systems, the fuel cell stacks may be organized in one or more fuel cell stack modules, each of which includes one or more fuel cell stacks housed in an enclosure or a containment structure.
A multi-stack fuel cell system may include a fuel cell stack module with multiple fuel cell stacks housed within a common enclosure. In a system of this design developed for high temperature fuel cell stacks and, in particular, for molten carbonate fuel cell (MCFC) stacks, a box-like containment structure is employed as the enclosure and the fuel cell stacks may be arranged along the length of the containment structure. Each fuel cell stack within the fuel cell module may have inlet manifolds for receiving fuel and oxidant gases needed to operate the fuel cell stack and outlet manifolds for conveying spent fuel and oxidant gases as anode and cathode exhausts from the fuel cell stack. The containment structure of the fuel cell module includes fuel and oxidant gas inlet ports that communicate through ducts with the respective fuel and oxidant gas inlet manifolds of the fuel cell stacks, and fuel and oxidant gas outlet ports that communicate through ducts with the oxidant and fuel gas outlet manifolds.
In internally reforming fuel cells, a reforming catalyst is placed within the fuel cell stack to allow direct use of hydrocarbon fuels such as pipe line natural gas, liquefied natural gas (LNG), liquefied petroleum gas (LPG), bio-gas, methane containing coal gas, etc., without the need for expensive and complex external reforming equipment. In an internal reformer, water and heat produced by the fuel cell are used by the reforming reaction, and hydrogen produced by the reforming reaction is used in the fuel cell. The heat produced by the fuel cell reaction supplies heat for the endothermic reforming reaction. Thus, internal reforming is used to cool the fuel cell stack.
Two different types of internally reforming fuel cell designs have been developed and used. The first type of an internally reforming fuel cell is a Direct Internally Reforming (DIR) fuel cell module, in which direct internal reforming is accomplished by placing the reforming catalyst within an active anode compartment of the fuel cell. A second type of internally reforming fuel cell utilizes Indirect Internal Reforming (IIR), which is accomplished by placing the reforming catalyst in an isolated chamber within the fuel cell stack and routing the reformed gas from this chamber into the anode compartment of the fuel cell. An internally reforming MCFC system, also called Direct Fuel Cell (DFC), which incorporates both DIR and IIR, has evolved as the choice for environmentally friendly power generation and is the leading commercial option for green power. Carbonate power plants have lower emissions of greenhouse gases and particulate matter than conventional combustion-based power plants. Carbonate power plants emit little NOx gas, SOx gas, or particulate matter. Carbonate power plants have been designated “ultra-clean” by the California Air Resources Board (CARB).
In one embodiment, a fuel cell system comprises at least one topping fuel cell module comprising a topping anode portion configured to output a topping anode exhaust, and a topping cathode portion configured to output a topping cathode exhaust; at least one bottoming fuel cell module comprising a bottoming anode portion configured to output a bottoming anode exhaust, and a bottoming cathode portion configured to output a bottoming cathode exhaust; and an electrochemical hydrogen separation unit configured to receive at least a portion of the topping anode exhaust, to output a hydrogen-rich stream, and to output a CO2-rich stream. The bottoming anode portion is configured to receive the CO2-rich stream from the electrochemical hydrogen separation unit.
In one aspect of this embodiment, the system further comprises a water recovery unit configured to receive the topping anode exhaust, to separate water contained in the topping anode exhaust, to output a water stream, and to output water-depleted topping anode exhaust. The at least a portion of the topping anode exhaust received by the electrochemical hydrogen separation unit is the water-depleted topping anode exhaust from the water recovery unit.
In one aspect of this embodiment, the system further comprises a controller configured to control an amount of the topping anode exhaust that is diverted to the electrochemical hydrogen separation unit.
In one aspect of this embodiment, the electrochemical hydrogen separation unit is configured to receive an entirety of the topping anode exhaust from the at least one topping fuel cell module.
In one aspect of this embodiment, the system further comprises a heat recovery unit configured to: receive the topping cathode exhaust and an incoming water stream, heat the incoming water stream using heat in the topping cathode exhaust, and output a hot water stream.
In one aspect of this embodiment, the system further comprises an Organic Rankine Cycle system configured to receive the topping cathode exhaust, and to generate power using heat in the topping cathode exhaust.
In one aspect of this embodiment, a total number of topping fuel cell stacks in the system is greater than a total number of bottoming fuel cell stacks in the system.
In another embodiment, a method comprises operating a fuel cell system that comprises: at least one topping fuel cell module comprising a topping anode portion configured to output a topping anode exhaust, and a topping cathode portion configured to output a topping cathode exhaust, at least one bottoming fuel cell module comprising a bottoming anode portion configured to output a bottoming anode exhaust, and a bottoming cathode portion configured to output a bottoming cathode exhaust, and an electrochemical hydrogen separation unit. The step of operating the fuel cell system comprises: at the electrochemical hydrogen separation unit, receiving at least a portion of the topping anode exhaust from the at least one topping fuel cell module, outputting a hydrogen-rich stream, and outputting a CO2-rich stream; and at the bottoming anode portion of, receiving the CO2-rich stream from the electrochemical hydrogen separation unit.
In another embodiment, a fuel cell system comprises at least one topping fuel cell module comprising a topping anode portion configured to output a topping anode exhaust, and a topping cathode portion configured to output a topping cathode exhaust; at least one bottoming fuel cell module comprising a bottoming anode portion configured to receive the topping anode exhaust and to output a bottoming anode exhaust, and a bottoming cathode portion configured to output a bottoming cathode exhaust; and a CO2 separation assembly configured to receive the bottoming anode exhaust, to output a hydrogen-rich stream, and to output a CO2-rich stream.
In one aspect of this embodiment, the system further comprises a condenser configured to receive the bottoming anode exhaust, to separate water contained in the bottoming anode exhaust, to output a water stream, and to output water-depleted bottoming anode exhaust. The bottoming anode exhaust received by the CO2 separation assembly is the water-depleted bottoming anode exhaust from the condenser.
In one aspect of this embodiment, the system further comprises a flue gas input configured to receive flue gas from a flue gas generating system and to output the flue gas to the topping cathode portion and the bottoming cathode portion; and a controller configured to control an amount of the flue gas output to the topping cathode portion and the bottoming cathode portion.
In one aspect of this embodiment, the topping anode portion is configured to receive the hydrogen-rich stream from the CO2 separation assembly.
In one aspect of this embodiment, the system further comprises a bleed valve configured to allow a portion of the hydrogen-rich stream from the CO2 separation assembly to be bled off; and a controller configured to control the bleed valve.
In one aspect of this embodiment, the system further comprises a heat recovery unit configured to: receive the topping cathode exhaust, the bottoming cathode exhaust, and an incoming water stream, heat the incoming water stream using heat in the topping cathode exhaust and the bottoming cathode exhaust, and output a hot water stream.
In one aspect of this embodiment, the system further comprises an Organic Rankine Cycle system configured to receive the topping cathode exhaust and the bottoming cathode exhaust, and to generate power using heat in the topping cathode exhaust and the bottoming cathode exhaust.
In one aspect of this embodiment, a total number of topping fuel cell stacks in the system is greater than a total number of bottoming fuel cell stacks in the system.
In another embodiment, a method comprises operating a fuel cell system that comprises: at least one topping fuel cell module comprising a topping anode portion configured to output a topping anode exhaust, and a topping cathode portion configured to output a topping cathode exhaust, at least one bottoming fuel cell module comprising a bottoming anode portion configured to receive the topping anode exhaust and to output a bottoming anode exhaust, and a bottoming cathode portion configured to output a bottoming cathode exhaust, and a CO2 separation assembly. The step of operating the fuel cell system comprises, at the CO2 separation assembly, receiving the bottoming anode exhaust from the at least one bottoming fuel cell module, outputting a hydrogen-rich stream, and outputting a CO2-rich stream.
The present disclosure provides a cost-effective, high efficiency fuel cell system, in which exportation of hydrogen and syngas from the exhaust of the anode of a topping module or modules in a high-efficiency fuel cell system is achieved.
More specifically, the present disclosure relates to a high efficiency fuel cell system that is capable of exporting valuable hydrogen and/or syngas from the system for use in other processes and energy production, thus allowing the system to increase its overall power generation. The high efficiency fuel cell system includes topping fuel cell modules and bottoming fuel cell modules arranged in series, where the topping fuel cell modules are present in the system in a greater number than bottoming fuel cell modules such that more fuel is utilized in the topping fuel cell modules than the bottoming fuel cell modules. This allows for a high electrical efficiency to be achieved with the fuel cell system.
During operation, the bottoming fuel cell module receives anode exhaust output from the topping fuel cell modules. The anode exhaust contains unutilized fuel that was inputted into the topping fuel cell modules for electrical production. In order to capture the value of this unutilized fuel, before being introduced into the bottoming fuel cell module, some or all of the anode exhaust is diverted to a water recovery unit and CO2 separation system. The water recovery unit and CO2 separation system condenses out water contained in the anode exhaust and separates out some or all of the carbon dioxide present in the anode exhaust. This results in an output stream being rich in hydrogen and/or syngas, which can be exported from the system for other uses, such as chemical, metallurgical processes, and/or as fuel for fuel cells to generate additional power. The separated carbon dioxide may then be recycled back into the system and introduced into the bottoming fuel cell module for its production needs.
A controller may be provided to control the amount of anode exhaust that is diverted to the water recovery unit and the CO2 separation system. In some embodiments, the full amount of the anode exhaust is diverted to the water recovery unit and the CO2 separation system. This helps in the reduction of energy requirements of the system by allowing the use of a low temperature anode booster blower that conveys the anode exhaust to the bottoming fuel cell modules.
In other embodiments, a hydrogen and/or syngas stream may be exported by diverting the anode exhaust from the bottoming modules after water recovery and CO2 separation instead of recycling the anode exhaust back into the system.
In addition, in some embodiments, a heat recovery unit may be provided. The heat recovery unit may receive cathode exhaust output from the topping and bottoming fuel cell modules. The heat that is present in the cathode exhaust output may be utilized to generate hot water to meet industrial or residential needs. In other embodiments, the cathode exhaust output may be conveyed to an Organic Rankine Cycle (ORC) system, where the heat present in the cathode exhaust output may be used to generate additional power. By utilizing the heat present in the cathode exhaust output, the fuel cell system may achieve a greater thermal efficiency.
The fuel cell system 200 of
In some embodiments, the first topping fuel cell stack 202A may be an internally reforming fuel cell stack and may include direct internal reforming, indirect internal reforming, or a combination of both direct and indirect internal reforming. In the embodiment shown in
As shown in
The first topping stack 202A may include one or more internal reforming units 248. Hydrogen, carbon dioxide, and carbon monoxide are produced from fuel passing through the one or more internal reforming units 248. Reformed or partially reformed fuel is then supplied to the first topping anode portion 206 of the stack via the fuel turn manifold 206A. In the first topping anode portion 206 of the stack, hydrogen electrochemically reacts to produce water, carbon monoxide either reacts electrochemically to form carbon dioxide or chemically with water to produce hydrogen and carbon dioxide. Direct internal reforming (DIR) may also be provided in each cell of the first topping stack 202A by placing reforming catalyst in one or more anode compartments of the first topping anode portion 206, and in particular, by placing the reforming catalyst in corrugations of an anode current collector of the one or more anode compartments of each cell in the stack.
As discussed above, the first topping fuel cell module 202 may include multiple first topping fuel cell stacks. The number of fuel cell stacks in each fuel cell module may be determined based on the desired power output. The number of fuel cells in each fuel cell stack may be determined by the required output, size and weight of the stacks and ease of transportation. The stacks may be provided vertically, horizontally, or a combination of both.
As shown in
The second topping fuel cell stack 212A includes a second topping cathode portion 214 and a second topping anode portion 216. Each cell of a stack is separated by an electrolyte matrix having molten carbonate electrolyte (not shown). Fuel entering the second topping anode portion 216 is reformed internally to produce partially or fully reformed fuel including hydrogen and carbon monoxide, which then undergoes an electrochemical reaction with oxidant gas passing through the second topping cathode portion 214. In the second topping anode portion 216 of the stack, hydrogen electrochemically reacts to produce water, and carbon monoxide either reacts electrochemically to form carbon dioxide or chemically with water to produce hydrogen and carbon dioxide. The second topping fuel cell stack 212A may include indirect internal reforming, direct internal reforming, or a combination of both direct and indirect internal reforming. In some embodiments, the second topping fuel cell stack 212A may include one or more reforming units 250 configured to receive a portion of the fuel feed and convey reformed or partially reformed fuel, including hydrogen and carbon monoxide, to a fuel turn manifold 216A, which then directs the fuel to the second topping anode portion 216 of the stack where the fuel undergoes the electrochemical reaction with the oxidant gas. As further shown in
As shown in
The second topping fuel cell stack 212A may include one or more internal reforming units 250. Hydrogen, carbon dioxide and carbon monoxide are produced from fuel passing through the one or more internal reforming units 250. Reformed or partially reformed fuel is then supplied to the second topping anode portion 216 of the stack via the turn manifold 216A. Direct internal reforming (DIR) may also be provided in the second topping stack 212A by placing reforming catalyst in the one or more anode compartments of the second topping anode portion 216, and in particular, by placing the reforming catalyst in corrugations of an anode current collector of the one or more anode compartments in each cell of the second topping stack 212A.
Similarly, as described above with respect to the first topping fuel cell module 202, the second topping fuel cell module 212 may include multiple second topping fuel cell stacks having similar construction. The number of fuel cell stacks per module may be determined based on the desired power output. The number of fuel cells in each fuel cell stack may be determined by the required output, size and weight of the stacks and ease of transportation.
As shown in
The bottoming fuel cell stack 222A may be an internally reforming fuel cell stack and may include direct internal reforming, indirect internal reforming, or a combination of both direct and indirect internal reforming. The bottoming fuel cell stack 222A may include a direct internal reforming catalyst placed in the one or more anode compartments of the bottoming anode portion 226, and in particular, in corrugations of an anode current collector of the one or more anode compartments in each cell of the bottoming fuel cell stack 222A. Although in the embodiment shown in
As shown in
The bottoming cathode portion 224 outputs cathode exhaust rich in CO2 into a cathode outlet manifold 228. As shown in
In one embodiment, a portion of the heated oxidant gas supplied by the oxidizer assembly 231, 233 before it is mixed with a second portion of preheated fresh air, is diverted to the cathode exhaust ducting 263 in the bottoming module. This is done to control the concentration of CO2 in the heated oxidant gas that is supplied to the bottoming cathode portion 224. If the cathode inlet to the bottoming fuel cell module becomes too rich in CO2, the CO2 concentration in the cathode inlet gas supplied to the bottoming fuel cell modules may be modulated to minimize Ni dissolution by increasing the second portion of the preheated fresh air. The temperature of the cathode inlet to the bottoming fuel cell module is controlled by modulating the temperature of the preheated fresh air.
The concentration of CO2 and temperature of the inlet oxidant gas conveyed to the first and second topping fuel cell modules 202, 212 and the bottoming module 222 may be adjusted and modulated. Control of these adjustments may be performed by a programmable controller 252 or similar device. For example, the cathode exhaust of the bottoming fuel cell module 222 may be diluted with fresh air in order to control the temperature and concentration of CO2 in the inlet oxidant gas conveyed to the first and second topping fuel cell modules. If the cathode exhaust from the bottoming fuel cell module becomes too rich in CO2, the CO2 concentration in the cathode inlet gas supplied to the first and second topping fuel cell modules may be modulated to minimize Ni dissolution by diluting the bottoming fuel cell module's cathode exhaust with fresh air and/or controlling the amount of fresh air supplied to the oxidizer assembly 231, 233 and the amount of oxidant gas produced by the oxidizer 233 supplied to the bottoming fuel cell module.
In some embodiments, a cathode booster blower 242 may be placed in the cathode exhaust ducting 263 that conveys cathode exhaust from the bottoming module 222 to raise the pressure of the first and second topping cathode portions 204 and 214 in order to maintain required differential pressure between the anode and cathode portions in the first and second topping modules 202 and 212, respectively.
Similarly as described above with respect to the first topping fuel cell module 202, the bottoming fuel cell module 222 may include multiple bottoming fuel cell stacks, each having a cathode portion and an anode portion. The number of fuel cell stacks per module is determined based on the number needed to provide the desired power output and the efficiency. The fuel cell stacks 222a in the bottoming fuel cell module 222 may include high temperature molten carbonate fuel cells.
As shown in
Furthermore, the total number of fuel cell stacks of the first and second topping fuel cell modules 202 and 212 are configured in a two-to-one ratio with the number of fuel cell stacks of the bottoming fuel cell module 222. In other embodiments, the number of topping modules and bottoming modules will vary, and the total number of topping fuel cell stacks and bottoming fuel cell stacks may also vary. For increased efficiency, the number of topping modules may be greater than the number of bottoming modules, and/or the total number of topping fuel cell stacks may be greater than the total number of bottoming fuel cell stacks. The topping modules or stacks have higher current density (because of better fuel quality) and fuel utilization than the bottoming modules or stacks.
During operation, the first and second topping fuel cell modules 202, 212 each receive a portion of the fuel feed, such as methane, natural gas, or other suitable fuel, from a fuel supply. Prior to being conveyed to the topping fuel cell modules 202, 212, the fuel feed may be preheated and/or processed. For example, a humidifier may be used to humidify the fuel feed and a preconverter 234 may be used to partially reform some of the fuel feed externally of the topping fuel cell modules. Moreover, the fuel feed may be deoxidized in a deoxidizer, desulfurized in a desulfurizer (not shown) and/or undergo other processing as may be required to meet fuel cell specifications for purity. Preheated and/or processed fuel feed is then divided between the first and second topping fuel cell modules 202, 212, with the first topping fuel cell module 202 receiving a first portion of the fuel feed and the second topping fuel cell module 212 receiving a second portion of the fuel feed, and the first and second portions of the fuel feed may be controlled to be about the same or to be different in amount. The controller 252 may be used to control the respective amounts of the first and second fuel feeds supplied to the first and second topping fuel cell modules 202, 212. The fuel feed portions received in each of the first and second topping fuel cell modules 202, 212 are then pre-heated using cathode exhaust heat output from the respective topping fuel cell module in first and second heat exchangers 236, 238, respectively. In some embodiments the heat exchangers 236 and 238 can be combined into one heat exchanger. In each of the first and second fuel cell modules 202, 212, the pre-heated fuel feed portion is then conveyed to the topping anode portion 206, 216 of the one or more fuel cell stacks of the respective topping module and may be reformed in an indirect internal reformer 248, 250 before being conveyed to the respective topping anode portion 206, 216.
The first and second topping fuel cell modules 202, 212 consume a portion of the fuel contained in the respective fuel feed portions conveyed to the topping fuel cell module, so that the anode exhaust output from the first and second topping modules 202, 212 contains the remaining fuel portion therein. In the embodiment shown in
As further shown in
The hydrogen-depleted, CO2-rich stream 273 produced by the EHS unit 271 is conveyed back to the anode booster blower 232. The stream 273 is rich in carbon dioxide, which is fed to the anode portion 226 of the bottoming fuel cell module 222. In some embodiments, when supplemental fuel is supplied to the anode portion 226 of the bottoming fuel cell module 222, a first portion of the hydrogen-depleted stream 273 may be returned to the anode booster blower 232, while a second portion of the hydrogen-depleted stream 273 may be exported from the system 200 for other uses.
The controller 252 may control the system 200 such that hydrogen or syngas is produced as the hydrogen-rich stream 272 based on the flow provided to the topping modules. In addition, the controller 252 may increase the fuel flow to the humidifier and pre-converter 234 if it is determined that there is an increased need for hydrogen or syngas. The controller 252 may also regulate how much anode exhaust output is diverted to the water recovery unit 269 as received anode exhaust 267. In some embodiments, the controller 252 is configured to allow the entire flow of the anode exhaust output to be diverted to the water recovery unit 269 to remove water before the hydrogen-depleted stream 273 is conveyed back to the anode booster blower 232. In such embodiments, this would allow the anode booster blower 232 to operate as a low-temperature blower rather than a high-temperature blower.
As shown in
Anode inlet gas comprising anode exhaust from the topping fuel cell modules and optionally supplemental fresh fuel is received in the bottoming fuel cell module 222 and is conveyed to the bottoming anode portion 226 of the fuel cell stack or stacks in the bottoming fuel cell module. As discussed above, the anode inlet gas may be reformed through direct internal reforming in the bottoming anode portion, and anode exhaust produced by the bottoming anode portion is output from the bottoming fuel cell stack or stacks via the anode outlet manifold 230. Anode exhaust output from the bottoming fuel cell module 222 is conveyed to the anode oxidizer assembly that includes a mixer/eductor 231 and the oxidizer 233. The mixer/eductor 231 also receives a first portion of pre-heated air input into the system and mixes the anode exhaust with the pre-heated air, and the oxidizer 233 oxidizes the anode exhaust with the pre-heated air to output a high temperature oxidant gas suitable for use in a fuel cell cathode. As shown in
In one embodiment, a portion of the heated oxidant gas supplied by the oxidizer assembly 231, 233 before it is mixed with a second portion of preheated fresh air, is diverted to the cathode exhaust ducting 263 in the bottoming module via ducting 265. This is done to control the concentration of CO2 in the heated oxidant gas that is supplied to the bottoming cathode portion 224. If the cathode inlet to the bottoming fuel cell module becomes too rich in CO2, the CO2 concentration in the cathode inlet gas supplied to the bottoming fuel cell modules may be modulated to minimize Ni dissolution by increasing the second portion of the preheated fresh air. The temperature of the cathode inlet to the bottoming fuel cell module is controlled by modulating the temperature of the preheated fresh air.
Cathode exhaust ducting 263, in the bottoming module also includes a heat exchanger 264 to cool down the cathode exhaust from the bottoming module before it is conveyed to the first and second topping cathode portions 204 and 214. This is done to control the cathode inlet temperature of the first and second topping cathode portions 204 and 214.
As can be seen in
As shown in
Before oxidant gas output from the oxidizer 233 mixes with the second portion of the preheated fresh air, the cathode exhaust portion from the bottoming module is cooled in a heat exchanger 264, using the second portion of preheated fresh air. This is done to control the cathode inlet temperature of the cathode inlet portion 204 and 214 of the first and second topping modules, respectively.
In such embodiments, all or a portion of the cathode exhaust output from the bottoming module 222 would be conveyed through the heat exchanger 264 and some of the heat in the cathode exhaust would be used to pre-heat the second portion of preheated fresh air being conveyed along with the output of the anode exhaust oxidizer 233 to the inlet of cathode portion 224 of the bottoming module 222. The amount of air supplied to the heat exchanger 264 is adjustable by the controller 252 so as to control the cathode inlet temperature of the first and second topping modules. The amount of cathode exhaust conveyed to the heat exchanger 264 may also be controlled by the controller 252 or similar device by controlling a valve 264a so as to control the cathode inlet temperature of the oxidant gas entering the topping modules. The heat exchanger may be located in the bottoming module 222.
Cathode exhaust output from the bottoming cathode portion 224 is then conveyed to the first and second topping modules 202, 212 for use as oxidant gas in the first and second topping cathode portions 204, 214. The system 200 may also include a cathode exhaust booster 242 provided on the cathode side downstream from the bottoming module 222 and upstream from the topping modules 202, 212 for increasing the pressure of the cathode exhaust output from the bottoming module 222 before being conveyed to the topping modules. In this way, the pressure differential between the anode side and the cathode side in the topping modules may be adjusted and controlled so as to maintain a low differential pressure between the cathode and the anode sides. The controller 252 or similar control device may be used for controlling the operation of the cathode exhaust booster so as to control the differential pressure between the anode and cathode sides.
The cathode exhaust output from the bottoming cathode portion 224 may be divided about equally between the first and second topping cathode portions 204, 214. However, in some embodiments, the amount of cathode exhaust from the bottoming cathode portion 224 received by each of the first and second topping cathode portions 204, 214 may be varied and controlled based on the desired operation and fuel utilization in the topping first and second topping modules 202, 212.
As shown in
After undergoing an electrochemical reaction in the topping fuel cells, spent oxidant is output from the first and second topping cathode portions 204, 214 as cathode exhaust. As discussed above, waste heat from cathode exhaust output from the first topping cathode portion 204 is used for pre-heating a portion of the fuel feed in the heat exchanger 236, and waste heat from the cathode exhaust output from the second topping cathode portion 214 is used to pre-heat the other portion of the fuel feed in the heat exchanger 238. After being output from the first and second topping modules 202, 212, cathode exhaust streams may be combined and conveyed to the fuel humidifier (not shown), which also receives fuel feed and water and where waste heat from the cathode exhaust is used to form steam and to humidify the fuel feed with the steam. The cathode exhaust may also be conveyed to the heat exchanger 246 so that waste heat remaining in the cathode exhaust is used for pre-heating incoming air.
In the embodiment shown in
As a further modification of the system shown in
Like the system 200 shown in
During operation, flue gas generated and outputted from a flue gas generating system is supplied to the system 100 via a flue gas input 168. The amount of flue gas supplied to the system 100 via the flue gas input 168 is controllable via the controller 152. The flue gas is heated using waste heat from cathode exhaust output from the topping and bottoming fuel cell modules in the flue gas heater 166. The heated flue gas is then provided to the topping and bottoming fuel cell modules 102, 112, 122 either in parallel or in series for use as cathode oxidant gas. As described herein below, during operation of the system 100, carbon dioxide in the flue gas used as cathode oxidant gas is extracted in the topping and bottoming fuel cell modules and output with anode exhaust from the bottoming fuel cell module so that the carbon dioxide can be separated out from the system.
Also during operation of the system of
The first and second topping fuel cell modules 102, 112 consume a portion of the fuel contained in the respective fuel feed portions conveyed to the topping fuel cell module, so that the anode exhaust conveyed from the first and second topping modules 102, 112 contains the remaining fuel portion therein. The first and second fuel cell modules 102, 112 consume about two-thirds of the fuel in the fuel feed, and convey anode exhaust containing the remaining portion of fuel, which is about one third of the initial fuel in the fuel feed. During the electrochemical reaction in the first and second fuel cell modules 102, 112, CO2 present in the cathode oxidant stream (flue gas) being conveyed through the respective topping cathode portions 104, 114 is extracted and conveyed across the electrolyte matrix to the respective topping anode portions. As a result, anode exhaust output from the anode topping portions includes not only the remaining unutilized fuel but also CO2 extracted from the cathode oxidant stream of the topping cathode portions 104, 114.
In
As shown in
Anode inlet gas comprising anode exhaust from the topping fuel cell modules and optionally supplemental fresh fuel is received in the bottoming fuel cell module 122 and is conveyed to the bottoming anode portion 126 of the fuel cell stack(s) in the bottoming fuel cell module via the fuel turn manifold 126A. As discussed above, the anode inlet gas may be reformed through direct internal reforming in the bottoming anode portion. During the electrochemical reaction in the bottoming fuel cell module, fuel in the anode inlet gas reacts with cathode oxidant gas (portion of flue gas) conveyed through the bottoming cathode portion, and CO2 present in the cathode oxidant gas is extracted and conveyed through the electrolyte matrix to the bottoming anode portion. As a result, anode exhaust produced by and output from the bottoming anode portion will include CO2 that was already present in the anode inlet gas as well as CO2 extracted from the cathode oxidant gas. That is, the anode exhaust output from the bottoming anode portion 126 will include the CO2 initially present in the fuel feed, the CO2 extracted from the cathode oxidant gas conveyed through the topping cathode portions 104, 114 and present in the anode inlet gas input into the bottoming anode portion 126, and the CO2 extracted from the cathode oxidant gas conveyed through the bottoming cathode portion 124. The anode exhaust from the bottoming anode portion 126 further includes water and unutilized fuel.
Anode exhaust produced by the bottoming anode portion is conveyed via the anode outlet manifold 130 from the bottoming fuel cell stack(s) and is output from the bottoming fuel cell module 122 to the separation assembly 177. In the separation assembly 177 of
The anode exhaust output from the bottoming anode portion may contain about 53% carbon dioxide, 42% water vapor, and a mixture of about 5% of hydrogen and carbon monoxide, e.g., syngas. As shown in
The condenser 178 cools and condenses the anode exhaust from the bottoming fuel cell module 122 to separate water from the anode exhaust. The condenser 178 outputs dry anode exhaust (water separated anode exhaust) to the CO2 separation assembly 180. For example, the dry anode exhaust will contain about 90% carbon dioxide and 9% hydrogen, as well as additional inert gases. The CO2 separation assembly 180 removes carbon dioxide from the dry anode exhaust so that the resulting dry separated anode exhaust has a substantially reduced amount of carbon dioxide and has a composition similar to that of the fuel input to the first and second topping anode portions 106, 116 after reforming. The CO2 separation assembly 180 removes the carbon dioxide from the dry anode exhaust using one or more separation processes such as compression and cooling to cryogenic carbon dioxide, solvent washing, or a membrane process. The dry separated anode exhaust is conveyed from the CO2 separation assembly 180 to an anode pressure booster 182, which increases the pressure of the separated exhaust stream before the separated exhaust stream is exported from the system 100 as a hydrogen-rich stream 190. The hydrogen-rich stream 190 may be in the form of hydrogen or syngas that is suitable for export as a feed supply for chemical and/or metallurgical processes that require hydrogen (e.g., Fischer-Tropsch reactions, hydrogenation, iron and steel industry processes that require reducing gas, copper, and nickel production). Alternatively, the hydrogen-rich stream 190 may be used as fuel for another fuel cell system for supplemental power generation for the system 100. The fuel cells may be low temperature fuel cells (e.g., proton exchange membrane (PEM) fuel cells, phosphoric acid fuel cells) and/or high temperature fuel cells (e.g., MCFC, solid oxide fuel cells). In addition, by exporting the separated exhaust stream as the hydrogen-rich stream 190, a need for placing a bleed valve between the CO2 separation assembly 180 and the anode pressure booster 182 is no longer necessary as there is no risk that inert gases, such as nitrogen, remaining in the hydrogen-rich stream 190 will accumulate in the system 100 due to the recycling of the separated exhaust stream back into the topping fuel cell modules 102, 112.
As further shown in
The controller 152 may control the system 100 such that hydrogen or syngas is produced as the hydrogen-rich stream 190 based on the flow provided to the topping modules. In addition, the controller 152 may increase the fuel flow to the humidifier and pre-converter 134 if it is determined that there is an increased need for hydrogen or syngas. The controller 152 may also be configured to regulate the amount of exhaust 188 diverted to the HRU or ORC unit in order to control the temperature of the hot water or the power generated by the ORC unit.
As utilized herein, the terms “approximately,” “about,” “substantially”, and similar terms are intended to have a broad meaning in harmony with the common and accepted usage by those of ordinary skill in the art to which the subject matter of this disclosure pertains. It should be understood by those of skill in the art who review this disclosure that these terms are intended to allow a description of certain features described and claimed without restricting the scope of these features to the precise numerical ranges provided. Accordingly, these terms should be interpreted as indicating that insubstantial or inconsequential modifications or alterations of the subject matter described and claimed are considered to be within the scope of the invention as recited in the appended claims.
The terms “coupled,” “connected,” and the like as used herein mean the joining of two members directly or indirectly to one another. Such joining may be stationary (e.g., permanent) or moveable (e.g., removable or releasable). Such joining may be achieved with the two members or the two members and any additional intermediate members being integrally formed as a single unitary body with one another or with the two members or the two members and any additional intermediate members being attached to one another.
References herein to the positions of elements (e.g., “top,” “bottom,” “above,” “below,” etc.) are merely used to describe the orientation of various elements in the Figures. It should be noted that the orientation of various elements may differ according to other exemplary embodiments, and that such variations are intended to be encompassed by the present disclosure.
It is important to note that the construction and arrangement of the various exemplary embodiments are illustrative only. Although only a few embodiments have been described in detail in this disclosure, those skilled in the art who review this disclosure will readily appreciate that many modifications are possible (e.g., variations in sizes, dimensions, structures, shapes and proportions of the various elements, values of parameters, mounting arrangements, use of materials, colors, orientations, etc.) without materially departing from the novel teachings and advantages of the subject matter described herein. For example, elements shown as integrally formed may be constructed of multiple parts or elements, the position of elements may be reversed or otherwise varied, and the nature or number of discrete elements or positions may be altered or varied. The order or sequence of any process or method steps may be varied or re-sequenced according to alternative embodiments. Other substitutions, modifications, changes and omissions may also be made in the design, operating conditions and arrangement of the various exemplary embodiments without departing from the scope of the present invention. For example, the heat recovery heat exchangers may be further optimized.
The present application is a U.S. national stage entry of PCT/US2017/028658, filed on Apr. 20, 2017, which claims priority to U.S. Provisional Appl. No. 62/325,780, filed on Apr. 21, 2016, and U.S. Provisional Appl. No. 62/336,094, filed on May 13, 2016, all of which are hereby incorporated by reference in their entireties.
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/US2017/028658 | 4/20/2017 | WO | 00 |
| Publishing Document | Publishing Date | Country | Kind |
|---|---|---|---|
| WO2017/184877 | 10/26/2017 | WO | A |
| Number | Name | Date | Kind |
|---|---|---|---|
| 4620914 | Abens et al. | Nov 1986 | A |
| 5198311 | Nakazawa et al. | Mar 1993 | A |
| 5221586 | Morimoto | Jun 1993 | A |
| 5306577 | Sprouse | Apr 1994 | A |
| 5376470 | Sprouse | Dec 1994 | A |
| 5413878 | Williams et al. | May 1995 | A |
| 5506066 | Sprouse | Apr 1996 | A |
| 5518828 | Senetar | May 1996 | A |
| 5541014 | Micheli et al. | Jul 1996 | A |
| 5658448 | Lasich | Aug 1997 | A |
| 6211643 | Kagatani | Apr 2001 | B1 |
| 6280865 | Eisman et al. | Aug 2001 | B1 |
| 6365290 | Ghezel-Ayagh et al. | Apr 2002 | B1 |
| 6475655 | Nakanishi et al. | Nov 2002 | B1 |
| 6495025 | Velev | Dec 2002 | B2 |
| 6516905 | Baumert et al. | Feb 2003 | B1 |
| 6569298 | Merida-Donis | May 2003 | B2 |
| 7150927 | Hickey et al. | Dec 2006 | B2 |
| 7201979 | McElroy et al. | Apr 2007 | B2 |
| 7364810 | Sridhar et al. | Apr 2008 | B2 |
| 7422810 | Venkataraman et al. | Sep 2008 | B2 |
| 7431746 | Ma et al. | Oct 2008 | B2 |
| 7482078 | Sridhar | Jan 2009 | B2 |
| 7575822 | Mitlitsky et al. | Aug 2009 | B2 |
| 7704618 | Venkataraman et al. | Apr 2010 | B2 |
| 7781112 | Sridhar et al. | Aug 2010 | B2 |
| 7833668 | Ballantine et al. | Nov 2010 | B2 |
| 7846599 | Ballantine et al. | Dec 2010 | B2 |
| 7878280 | Sridhar et al. | Feb 2011 | B2 |
| 7887971 | Hickey et al. | Feb 2011 | B2 |
| 7901814 | Venkataraman et al. | Mar 2011 | B2 |
| 8053136 | Hickey et al. | Nov 2011 | B2 |
| 8062799 | Jahnke | Nov 2011 | B2 |
| 8071241 | Sridhar et al. | Dec 2011 | B2 |
| 8071246 | Mitlitsky et al. | Dec 2011 | B2 |
| 8080344 | Skok et al. | Dec 2011 | B2 |
| 8236458 | Jahnke et al. | Aug 2012 | B2 |
| 8277992 | Mitlitsky et al. | Oct 2012 | B2 |
| 8288888 | Hinatsu et al. | Oct 2012 | B2 |
| 8367256 | Jahnke et al. | Feb 2013 | B2 |
| 8435689 | Venkataraman | May 2013 | B2 |
| 8663859 | Mitlitsky et al. | Mar 2014 | B2 |
| 8852820 | Perry et al. | Oct 2014 | B2 |
| 9133553 | Wilson et al. | Sep 2015 | B2 |
| 9187833 | Wilson et al. | Nov 2015 | B2 |
| 9190693 | Sridhar et al. | Nov 2015 | B2 |
| 9249518 | Hinatsu et al. | Feb 2016 | B2 |
| 9303325 | Hinatsu et al. | Apr 2016 | B2 |
| 9413017 | Bandhauer et al. | Aug 2016 | B2 |
| 9478819 | Lambrech et al. | Oct 2016 | B2 |
| 9502728 | Farooque | Nov 2016 | B1 |
| 9722273 | Perry et al. | Aug 2017 | B2 |
| 9911989 | Mcelroy et al. | Mar 2018 | B2 |
| 9947955 | Sridhar et al. | Apr 2018 | B2 |
| 10096840 | Venkataraman et al. | Oct 2018 | B1 |
| 10581090 | Ballantine et al. | Mar 2020 | B2 |
| 10631442 | Lecourtier | Apr 2020 | B2 |
| 20010036566 | Dekker et al. | Nov 2001 | A1 |
| 20020153263 | Velev | Oct 2002 | A1 |
| 20030207161 | Rusta-Sallehy et al. | Nov 2003 | A1 |
| 20040023097 | Bette et al. | Feb 2004 | A1 |
| 20040131902 | Frank et al. | Jul 2004 | A1 |
| 20040142215 | Barbir et al. | Jul 2004 | A1 |
| 20040205032 | Routtenberg et al. | Oct 2004 | A1 |
| 20040229092 | Take | Nov 2004 | A1 |
| 20050164069 | Margiott et al. | Jul 2005 | A1 |
| 20050227137 | Suga | Oct 2005 | A1 |
| 20060228593 | Grieve et al. | Oct 2006 | A1 |
| 20080236647 | Gibson et al. | Oct 2008 | A1 |
| 20080248349 | McElroy et al. | Oct 2008 | A1 |
| 20090246564 | Mogi et al. | Oct 2009 | A1 |
| 20100114395 | Hinatsu et al. | May 2010 | A1 |
| 20100216039 | Jahnke et al. | Aug 2010 | A1 |
| 20100266923 | Mcelroy et al. | Oct 2010 | A1 |
| 20110189567 | Venkataraman et al. | Aug 2011 | A1 |
| 20120034538 | Jahnke et al. | Feb 2012 | A1 |
| 20130130139 | Kah et al. | May 2013 | A1 |
| 20140311917 | Tamhankar | Oct 2014 | A1 |
| 20140349144 | Kim et al. | Nov 2014 | A1 |
| 20140352309 | Kim et al. | Dec 2014 | A1 |
| 20150134277 | Van Doorn | May 2015 | A1 |
| 20150285141 | Manabe et al. | Oct 2015 | A1 |
| 20160181647 | Lambrech et al. | Jun 2016 | A1 |
| 20200161671 | Ballantine et al. | May 2020 | A1 |
| Number | Date | Country |
|---|---|---|
| 101529632 | Sep 2009 | CN |
| 1 577 972 | Sep 2005 | EP |
| 1 620 906 | Feb 2006 | EP |
| 1 665 441 | Jun 2006 | EP |
| 1 750 321 | Feb 2007 | EP |
| 2 790 256 | Oct 2014 | EP |
| 61-085773 | May 1986 | JP |
| 05-129033 | May 1993 | JP |
| 10-199548 | Jul 1998 | JP |
| 2007-505467 | Mar 2007 | JP |
| 2007-115696 | May 2007 | JP |
| 2008-522942 | Jul 2008 | JP |
| 2009-537954 | Oct 2009 | JP |
| 1020090104548 | Oct 2009 | KR |
| 20110064723 | Jun 2011 | KR |
| 20150020463 | Feb 2015 | KR |
| WO-2004013924 | Feb 2004 | WO |
| WO-2012176176 | Dec 2012 | WO |
| WO-2014140962 | Sep 2014 | WO |
| WO-2017184877 | Oct 2017 | WO |
| Entry |
|---|
| 2nd International Workshop, Durability and Degradation Issues in PEM Electrolysis Cells and its Components, “Lifetime Prediction of PEM Water Electrolysis Stacks Coupled with RES”, Freiburg, Germany, Feb. 2016. |
| Communication pursuant to Rule 164(1) EPC in EP 15871189 dated Jul. 6, 2018 (13 pages). |
| D. Mears, M. Mann, J. Ivy, M. Rutkowski, “Overview of Central H2A Results,” 2004 US Hydrogen Conference Proceedings, Apr. 26-29, 2004. |
| Extended European Search Report in EP 15871187.9 dated Oct. 17, 2018 (12 pages). |
| Final Office Action on U.S. Appl. No. 15/449,583 dated Jun. 25, 2019. |
| International Preliminary Reporton Patentability in PCT/US2017/028658 dated Nov. 1, 2018 (11 pages). |
| International Search Report and Written Opinion in PCT/US2015/066735 dated Feb. 12, 2016 (9 pages). |
| International Search Report and Written Opinion in PCT/US2017/028658 dated Sep. 5, 2017 (14 pages). |
| International Search Report and Written Opinion in PCT/US2018/020577 dated Jun. 11, 2018 (15 pages). |
| International Search Report and Written Opinion in PCT/US2018/021357, dated May 30, 2018 (16 pages). |
| K. Harrison, 228th Electrochemical Society Meeting, “Large Active Area Electrolyzer Stack Test Bed—Design, Data and Development”, Phoenix, Arizona, Oct. 2015. |
| L. Kazmerski, “PV Electrolysis,” ASES Renewable Hydrogen Forum Proceedings, Oct. 1, 2003. |
| M. Peters, Presentation at the ACT Expo, “Renewable Hydrogen Production for Use in Hydrogen Fuel Cell Vehicles,” Dallas, Texas, May 5, 2015. |
| M. Peters, Renewable Electrolysis Integrated System Development & Testing; Jun. 8, 2016 Project ID: PD031. |
| Pre-Interview First Office Action dated Feb. 12, 2019 in U.S. Appl. No. 15/449,583 (3 pages). |
| Pre-Interview First Office Action dated Feb. 14, 2019 in U.S. Appl. No. 15/445,875 (3 pages). |
| Preliminary Rejection in KR2017-7018944 dated Mar. 28, 2019, with English translation (26 pages). |
| R. McConnell, Generating Hydrogen througn Water Electrolysis Using Concentrator Photovoltaics, Conference Paper NREL/CP-520-37093 Jan. 2005. |
| S. Licht, “Solar Water Splitting to Generate Hydrogen Fuel: Photothermal Electrochemical Analysis,” J. Phys. Chem. B 2003, 107, 4253-4260. |
| U.S. Office Action on U.S. Appl. No. 14/578,077 dated Jul. 10, 2015 (17 pages). |
| U.S. Office Action on U.S. Appl. No. 14/578,077 dated Oct. 20, 2015 (18 pages). |
| W. Summers, “Hydrogen Production Using Nuclear Energy,” 15th Annual U.S. Hydrogen Conference Proceedings. Apr. 29, 2004. |
| First Office Action in CN2015800695728 dated Aug. 28, 2019, with English translation (23 pages). |
| International Search Report and Written Opinion in PCT/US2018/021357, dated Sep. 10, 2019 (9 pages). |
| Number | Date | Country | |
|---|---|---|---|
| 20190140298 A1 | May 2019 | US |
| Number | Date | Country | |
|---|---|---|---|
| 62336094 | May 2016 | US | |
| 62325780 | Apr 2016 | US |
