The present invention relates generally to the field of fuel cell systems and more particularly to fuel exhaust separation and recycling schemes for fuel cells.
Fuel cells are electrochemical devices which can convert energy stored in fuels to electrical energy with high efficiencies. In certain fuel cell systems, such as a solid oxide fuel cell (SOFC) system, the anode exhaust stream contains a small amount of fuel. This fuel must be oxidized before discharge into the atmosphere or sequestration into CO2. Typically, this fuel is oxidized with air in a combustion process in an oxidizer such as a burner or a catalyst reactor. However, the amount of fuel in the anode exhaust stream is often low and variable. As such, controlling a burner type oxidizer is difficult. Further, both the burner type and catalyst type oxidizers dilute the discharged stream with nitrogen from air, making sequestration of CO2 also difficult.
One embodiment of the present invention describes a fuel cell system comprising a fuel cell stack comprising a plurality of fuel cells and at least one shorted fuel cell. In the shorted cell, the cell anode is electrically connected to the cell cathode. Further, the at least one shorted fuel cell is positioned within the stack to receive the anode exhaust stream from the plurality cells of the fuel cell stack.
Another embodiment describes a fuel cell system comprising a fuel cell stack and at least one shorted fuel cell or at least one shorted stack located downstream from the fuel cell stack. In the at least one shorted cell, the cell anode is electrically connected to the cell cathode. As in the previous embodiment, the at least one shorted fuel cell is positioned to receive the anode exhaust stream from the fuel cell stack.
Another embodiment describes a method of operating a fuel cell system comprising generating electricity using a fuel cell stack, providing an anode exhaust stream from fuel cells of the fuel cell stack to at least one shorted fuel cell and providing oxygen to the at least one shorted fuel cell. In at least one shorted fuel cell, at least one of H2 and CO from the anode exhaust stream reacts with oxygen to form at least one of H2O and CO2, respectively.
In an embodiment of the invention, fuel cell systems, such as SOFC systems, include additional shorted fuel cells, such as shorted SOFC cells or stacks for oxidizing residual fuel in system exhaust streams such as, but not limited to, fuel cell anode exhaust streams. As used herein. “shorted cell” denotes a fuel cell where the cell anode electrode is electrically connected to the cell cathode electrode. Also as used herein, “shorted stack” denotes a fuel cell stack where all the cells are shorted cells. For example, the shorted cell converts one or both of H2 and CO in the exhaust stream into one or both of H2O and CO2, respectively. Additionally, the exhaust steam can be essentially free of N2 and O2 to facilitate CO2 sequestration. Also, in order to optimize conditions for reacting the residual fuel in the exhaust streams, a shorted fuel cell can be fitted with a shunt (e.g., current sensor) to monitor the fuel cell reactions and determine if any flow rate adjustments are needed.
In
In general, a fuel cell may be shorted in a variety of ways. One non-limiting example includes electrically connecting the anode and cathode electrodes with an external wire or other similar conductor. Another non-limiting example includes forming a channel through the electrolyte which is filled with an electrically conductive material, such as a metal. Another non-limiting example includes a mixed conductor electrolyte which is both ionically and electrically conductive. These are all examples of the shorts 208 shown in
In one embodiment, the fuel cell system comprises a fuel cell stack comprising regular fuel cells (i.e., cells in which the anode is not shorted to the cathode) and at least one shorted fuel cell having the cell anode electrically connected to the cell cathode. The shorted fuel cells may be located at any part of the fuel cell stack. For instance, the shorted fuel cell may be located at the middle or end portions of a fuel cell stack between or after the regular cells. Preferably, the shorted fuel cell receives an exhaust stream, such as but not limited to an anode exhaust stream for the regular cells the stack. In some instances, a fuel cell stack can comprise more than one shorted fuel cell where each shorted fuel cell is located next to and/or distal from another shorted cell in the stack. As a non-limiting example, a SOFC stack may comprise eleven cells where the first ten cells are regular (non-shorted) cells and the last cell located down stream from the other ten cells is shorted.
During operation of the stack in
In another embodiment, a fuel cell system comprises a fuel cell stack (regular fuel cell stack) and at least one shorted fuel cell located downstream from the stack. The shorted fuel cell may be located in a shorted fuel cell stack or stacks, in which every cell's anode is shorted to the cathode. Such shorted stack(s) may be located at any part of the fuel cell system. Particularly, it may be located inside or outside the hot box area in which the regular stacks are located. Preferably, at least one shorted fuel cell stack receives an exhaust stream, such as but not limited to an anode exhaust stream, of a regular fuel cell stack.
Preferably, in a shorted stack, the fuel content is uniformly distributed throughout the cells. This can ensure that the current passes through each cell and the cell does not pump oxygen into the exhaust stream. For example, when a cell in a shorted stack contains an undesirable concentration of fuel, the cell can be driven by other cells into oxygen pumping mode which contaminates the anode exhaust stream with oxygen gas. An effective solution is to employ a mixed conductor electrolyte in the shorted cells. A mixed conductor electrolyte conducts both oxygen ions and electrons (i.e., it is both ionically and electrically conductive).
A non-limiting example of such electrolytes is a mixture of doped ceria and stabilized zirconia where there is limited reaction between the ceria and zirconia phases. Examples of stabilized zirconias include scandia stabilized zirconia (SSZ) (scandia ceria stabilized zirconia (“SCSZ”)), and/or yttria stabilized zirconia (YSZ). Non-limiting examples of doped ceria includes 10 to 40 molar percent trivalent oxides of ceria. The doped ceria is preferably slightly non-stoichiometric with less than two oxygen atoms for each metal atom: Ce1-mDmO2-δ where 0.1≦m≦0.4 and D is selected from one or more of La, Sm, Gd, Pr or Y. However, a doped ceria containing two or more oxygen atoms for each metal atom may also be used. For example, the doped ceria may comprise gadolinia doped ceria (“GDC”). In another non-limiting example, a single phase doped ceria material, such as GDC, is used as a mixed conductor electrolyte which conducts both oxygen ions and electrons.
Preferably, when using shorted stacks, the reaction rates in the anode chamber of the shorted stack is known. The reaction rates can be generally assessed by knowing the air flow rate and measuring the effluent diluted air content. Therefore, one method comprises measuring flow rate of oxygen into the stack of shorted fuel cells, measuring effluent oxygen in said stack of shorted fuel cells and adjusting a flow of oxygen to optimize flow of oxygen. Another method comprises measuring current from a sensor fuel cell in the stack adjusting the air flow to optimize flow of oxygen.
The system 100 contains an exhaust conduit 170 which operatively connects the anode exhaust outlet from the shorted stack 160 to a carbon dioxide storage tank or other vessel 21 for sequestering carbon dioxide and/or water. Preferably, the exhaust conduit 170 is connected to a dryer 20 that separates the carbon dioxide from the water contained in the exhaust stream. The dryer 20 can use any suitable means for separating carbon dioxide from water, such as separation based on differences in melting point, boiling point, vapor pressure, density, polarity, or chemical reactivity. Preferably, the separated carbon dioxide is substantially free of water and has a relatively low dew point. Preferably, the separated carbon dioxide is sequestered in the vessel 21 in order to minimize greenhouse gas pollution by the system 100.
The system 100 further contains a fuel humidifier 119 having a first inlet operatively connected to a hydrocarbon fuel source, such as the hydrocarbon fuel inlet conduit 111, a second inlet operatively connected to the fuel exhaust outlet 103, a first outlet operatively connected to the fuel cell stack fuel inlet 105, and a second outlet operatively connected to the dryer 20. In operation, the fuel humidifier 119 humidifies a hydrocarbon fuel inlet stream from conduit 111 using water vapor contained in a fuel cell stack fuel exhaust stream. The fuel humidifier may comprise a polymeric membrane humidifier, such as a Nafion® membrane humidifier, an enthalpy wheel or a plurality of water adsorbent beds, as described for example in U.S. Pat. No. 6,106,964 and in U.S. application Ser. No. 10/368,425, which published as U.S. Published Application Number 2003/0162067, all of which are incorporated herein by reference in their entirety. For example, one suitable type of humidifier comprises a water vapor and enthalpy transfer Nafion® based, water permeable membrane available from Perma Pure LLC. The humidifier passively transfers water vapor and enthalpy from the fuel exhaust stream into the fuel inlet stream to provide a 2 to 2.5 steam to carbon ratio in the fuel inlet stream. The fuel inlet stream temperature may be raised to about 80 to about 90 degrees Celsius in the humidifier.
The system 100 also contains a recuperative heat exchanger 121 which exchanges heat between the stack 101 fuel exhaust stream and the hydrocarbon fuel inlet stream being provided from the humidifier 119. The heat exchanger helps to raise the temperature of the fuel inlet stream and reduces the temperature of the fuel exhaust stream so that it may be further cooled downstream and such that it does not damage the humidifier.
If the fuel cells are external fuel reformation type cells, then the system 100 contains a fuel reformer 123. The reformer 123 reforms a hydrocarbon fuel containing inlet stream into hydrogen and carbon monoxide containing fuel stream which is then provided into the stack 101. The reformer 123 may be heated radiatively, convectively and/or conductively by the heat generated in the fuel cell stack 101, as described in U.S. patent application Ser. No. 11/002,681, filed Dec. 2, 2004, which published as U.S. Published Application Number 2005/0164051, incorporated herein by reference in its entirety. Alternatively, the external reformer 123 may be omitted if the stack 101 contains cells of the internal reforming type where reformation occurs primarily within the fuel cells of the stack.
Optionally, the system 100 also contains an air preheater heat exchanger 125. This heat exchanger 125 heats the air inlet stream being provided to the fuel cell stack 101 using the heat of the fuel cell stack fuel exhaust. If desired, this heat exchanger 125 may be omitted.
The system 100 also preferably contains an air heat exchanger 127. This heat exchanger 127 further heats the air inlet stream being provided to the fuel cell stack 101 using the heat of the fuel cell stack air (i.e., oxidizer or cathode) exhaust. If the preheater heat exchanger 125 is omitted, then the air inlet stream is provided directly into the heat exchanger 127 by a blower or other air intake device.
The system may optionally comprise a hydrogen separation unit (not shown) such as a Proton Exchange Membrane (PEM) fuel cell stack, to separate any remaining hydrogen in the fuel exhaust stream, as described in U.S. patent application Ser. No. 11/730,255, filed on Mar. 30, 2007 and incorporated herein by reference in its entirety.
The system may also optionally contain a hydrogen cooler heat exchanger (not shown) which cools the separated hydrogen stream, for example provided from a PEM stack, using an air stream, such as an air inlet stream.
The system 100 operates as follows. A fuel inlet stream is provided into the fuel cell stack 101 through fuel inlet conduit 111. The fuel may comprise any suitable fuel, such as a hydrocarbon fuel, including but not limited to methane, natural gas which contains methane with hydrogen and other gases, propane, methanol, ethanol or other biogas, or a mixture of a carbon fuel, such as carbon monoxide, oxygenated carbon containing gas, such as ethanol, methanol, or other carbon containing gas with a hydrogen containing gas, such as water vapor, H2 gas or their mixtures. For example, the mixture may comprise syngas derived from coal or natural gas reformation.
The fuel inlet stream passes through the humidifier 119 where humidity is added to the fuel inlet stream. The humidified fuel inlet stream then passes through the fuel heat exchanger 121 where the humidified fuel inlet stream is heated by the fuel cell stack fuel exhaust stream. The heated and humidified fuel inlet stream is then provided into a reformer 123, which is preferably an external reformer. For example, reformer 123 may comprise a reformer described in U.S. patent application Ser. No. 11/002,681, filed on Dec. 2, 2004, which published as U.S. Published Application Number 2005/0164051, incorporated herein by reference in its entirety. The fuel reformer 123 may be any suitable device which is capable of partially or wholly reforming a hydrocarbon fuel to form a carbon containing and free hydrogen containing fuel. For example, the fuel reformer 123 may be any suitable device which can reform a hydrocarbon gas into a gas mixture of free hydrogen and a carbon containing gas. For example, the fuel reformer 123 may comprise a nickel and rhodium catalyst coated passage where a humidified biogas, such as natural gas, is reformed via a steam-methane reformation reaction to form free hydrogen, carbon monoxide, carbon dioxide, water vapor and optionally a residual amount of unreformed biogas. The free hydrogen and carbon monoxide are then provided into the fuel (i.e., anode) inlet 105 of the fuel cell stack 101. Thus, with respect to the fuel inlet stream, the humidifier 119 is located upstream of the heat exchanger 121 which is located upstream of the reformer 123 which is located upstream of the stack 101.
The air or other oxygen containing gas (i.e., oxidizer) inlet stream is preferably provided into the stack 101 through a heat exchanger 127, where it is heated by the air (i.e., cathode) exhaust stream from the fuel cell stack. If desired, the air inlet stream may also pass through the air preheat heat exchanger 125 to further increase the temperature of the air before providing the air into the stack 101. Preferably, no fuel is combusted with air, and if heat is required during startup, then the requisite heat is provided by the electric heaters which are located adjacent to the stack 101 and/or the reformer 123.
Once the fuel and air are provided into the fuel cell stack 101, the stack 101 operates to generate electricity. The anode exhaust stream of the stack 101 comprises CO, and H2 and optionally CH4, CO2 and H2O. This stream is directed through the fuel heat exchanger 121 into the anode inlet of the shorted stack 160. Air is directed into the cathode inlet of the shorted stack 160 via an air inlet conduit 180 to supply oxygen. Air supply to the shorted stack 160 may be from split from the line providing air to the regular stack 101 or a separate source or it may comprise the stack 101 air exhaust in conduit 25. Furthermore, air exhaust from the shorted stack, may be routed back into the system or directed out of the system via air exhaust conduit 190. The shorted stack 160 converts CO and H2 into CO2 and H2O respectively. The anode exhaust stream from the shorted stack, is essentially free of H2 and CO, and is directed into the air preheater 125 and eventually to the vessel 21 via exhaust conduit 170. Optionally, a water-gas shift reactor can be used, either before of after a shorted stack, to react other possible stream components such as CH4.
The anode exhaust stream from the shorted stack comprising CO2, and H2O is provided to the dryer 20 which separates carbon dioxide from water. Although not shown, the anode exhaust stream from the shorted stack 160 can bypass the air preheater 125 and go directly into fuel humidifier 119, or the dryer 20. The separated carbon dioxide then flows from the dryer 20 through conduit 22 into the vessel 21. In one example, if the fuel cell stack 101 comprises a solid oxide regenerative fuel cell stack, then with the aid of a Sabatier reactor, the sequestered carbon dioxide can be used to generate a hydrocarbon fuel, such as methane, when the stack 101 operates in the electrolysis mode, as described in U.S. Pat. No. 7,045,238, incorporated herein by reference in its entirety. The separated water from dryer 20 is available for humidification of the fuel inlet stream or other industrial uses. For example, conduit 23 may provide the water from the dryer 20 back into the humidifier 119, into a steam generator (not shown) and/or directly into the fuel inlet conduit 111.
In the fuel humidifier 119, a portion of the water vapor in the fuel exhaust stream is transferred to the fuel inlet stream to humidify the fuel inlet stream. The hydrocarbon and hydrogen fuel inlet stream mixture is humidified to 80C to 90C dew point. The remainder of the fuel exhaust stream is then provided into the dryer 20. The dryer 20 then separates the carbon dioxide from the water contained in the exhaust stream. The dry, substantially hydrogen free separated carbon dioxide is then provided to the containment unit 21 for sequestration, and the separated water is available for humidification of the fuel inlet stream or other industrial uses. Thus, the environmentally friendly system preferably contains no burner and the fuel exhaust is not combusted with air. The only exhaust from the system consists of three streams—water, sequestered carbon dioxide and oxygen depleted air cathode exhaust stream through conduit 25.
The fuel cell system described herein may have other embodiments and configurations, as desired. Other components may be added if desired, as described, for example, in U.S. application Ser. No. 10/300,021, filed on Nov. 20, 2002 and published as U.S. Published Application Number 2003/0157386, in U.S. Provisional Application Ser. No. 60/461,190, filed on Apr. 9, 2003, and in U.S. application Ser. No. 10/446,704, filed on May 29, 2003 and published as U.S. Published Application Number 2004/0202914, all of which are incorporated herein by reference in their entirety. Furthermore, it should be understood that any system element or method step described in any embodiment and/or illustrated in any figure herein may also be used in systems and/or methods of other suitable embodiments described above, even if such use is not expressly described.
The foregoing description 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 modifications and variations are possible in light of the above teachings or may be acquired from practice of the invention. The description was chosen in order to explain the principles of the invention and its practical application. It is intended that the scope of the invention be defined by the claims appended hereto, and their equivalents.