Patent Application
20100190067
This application relates to the field of fuel cells, and more particularly, to dealing with fuel contaminator in the anode reactant of fuel cells.
A low concentration of fuel contaminators such as carbon monoxide (CO) is usually found in the anode reactant of a fuel cell system when hydrocarbon fuel such as natural gas or liquefied petroleum gas (LPG) is chemically processed such as by steam reforming, autothermal reforming or partial oxidation with water-gas shift reaction and CO cleanup processes to provide for the system's hydrogen source. When carbon monoxide enters into the fuel cells, particularly proton exchange membrane fuel cells (PEMFCs), the catalysts are poisoned and the fuel cell performance is therefore degraded. To eliminate CO's negative effect on fuel cell performance, there is provided a common approach of so-called “air-bleeding” in which a certain amount of air, depending on the level of CO concentration in fuel, is externally supplied and mixed to the anode reactant continually (using up about 1% to 10% of anode reactant) prior to enter the fuel cell stack. The oxygen contained in air will then oxidize CO into CO2 under presence of a Pt (or Pt/Ru) catalyst inside the fuel cell, and thus fuel cell performance is expected to be improved.
During the majority of time of the fuel cell operation, however, the fuel processor works well and the CO concentration is considerably low so that no air or only a small amount of air is needed for CO oxidization reaction. In this case, the external air-bleeding system becomes even harder to control and operate.
There is a need to overcome the drawbacks of fuel cell systems due to fuel contaminates.
In accordance with a first broad aspect of the present invention, there is provided a method for managing a fuel cell system having a fuel contaminator present in an anode reactant, the method comprising: monitoring a fuel contaminator concentration in the anode reactant of a fuel cell stack, the fuel cell stack having a plurality of individual fuel cell units each having a membrane electrode assembly (MEA); detecting an increase in the fuel contaminator concentration in the anode reactant; and increasing, when the increase in fuel contaminator concentration is detected, a concentration of a compound that chemically reacts with the fuel contaminator in the anode reactant by a mass transfer through a membrane in the fuel cell system to reduce the fuel contaminator concentration.
In accordance with a second broad aspect of the present invention, there is provided a fuel cell system comprising: a fuel cell stack comprising: a plurality of individual fuel cell units each having a membrane electrode assembly (MEA); a first inlet to deliver an anode reactant to an anode side of each of the individual fuel cell units; a second inlet to deliver a cathode reactant to a cathode side of each of the individual fuel cell units; a diagnosis module for detecting an increase in a fuel contaminator in the anode reactant; and a fuel contaminator control module connected to the diagnosis module and adapted to increase a concentration of a compound that chemically reacts with the fuel contaminator in the anode reactant by a mass transfer through a membrane in the fuel cell system to reduce the fuel contaminator concentration.
The system may also have an anode humidifier sub-system using cathode off gas as a water source. In this case, the fuel contaminate control module may go through the anode humidifier sub-system to increase/decrease pressure of the cathode off gas/anode reactant in order to alter the oxygen transfer from cathode off gas to supplying fuel stream, respectively.
The term “oxygen” is used throughout the description to represent the compound that chemically reacts with the contaminator. It should be understood that the oxygen can be replaced by any compound that chemically reacts with the contaminator or by any fluid comprising the compound. Furthermore, it should be understood that the term “oxygen” is equivalent to the term “dioxygen”.
Furthermore, the term “carbon monoxide” is used throughout the description to represent the fuel cell anode poisoning contaminator. It is understood that the anode poisoning contaminator may also be another chemical compound, such as H2S, ammonia, volatile organic compounds (VOCs), etc.
Further features and advantages of the present invention will become apparent from the following detailed description, taken in combination with the appended drawings, in which:
a is a block diagram of an embodiment of the fuel cell system in accordance with the present invention;
b is a block diagram of an embodiment of the fuel cell system using an anode humidifier sub-system in accordance with the present invention;
It will be noted that throughout the appended drawings, like features are identified by like reference numerals.
where DO
An input anode reactant stream 10 enters the anode side 4 by an anode reactant inlet. This stream comprises molecules of fuel 18 and molecules of carbon monoxide 19. The output anode reactant stream 12 exits the anode side 4 by an anode reactant outlet. A cathode reactant stream 14 enters the cathode side 6 by a cathode reactant inlet. The cathode reactant stream 14 comprises oxygen molecules 20 and potentially other chemical compounds (such as nitrogen when air is used as oxidant). The output cathode reactant stream 16 exits the cathode side 6 by a cathode reactant outlet. In the present example, the anode reactant stream 10 and the cathode reactant stream 14 are co-current flow relative to the MEA 2, but it is understood that they could be counter-current flow or cross-flow. If the partial pressure of oxygen molecules 20 in the cathode side 6 of the MEA is higher than partial pressure of oxygen molecules 20 in the anode side 4 of the MEA, a mass transfer (by any underlying mechanisms including diffusion, convection, etc) of oxygen molecules 20 occurs from the cathode side 6 to the anode side 4, which is illustrated by arrow 24. The gradient of oxygen partial pressure (which is equal to the oxygen molar fraction multiplied by the total pressure of the reactant stream) can be achieved by at least one of increasing the cathode reactant pressure and decreasing the anode reactant pressure.
Various methods known to those skilled in the art are available to alter the anode and/or cathode pressure. For example, precision pressure regulators installed on either or both the anode and cathode outlets can adjust the back pressure to respective values, as desired. Anode and cathode stoichiometry can also be adjusted to provide different preferred pressures on each side (i.e. anode and cathode side).
It should be understood that the present system and method is not limited to proton exchange membrane fuel cells, but rather can be used for any type of fuel cell in which fuel contaminators (such as CO) are present in the anode reactant, thereby poisoning the cell catalysts.
Based on an average anode reactant fuel contaminator concentration during fuel cell operation, nominal membrane thickness is selected for the MEA membrane and/or the anode humidifier membrane. The higher the contaminator concentration in the anode reactant, the thinner the membrane should be for MEA and/or anode humidifier.
Injecting the O2 molecules through the membrane of either the MEA or the anode humidifier results in not requiring additional accessories such as pipes, external sources of O2 and modules to control the amount of O2 molecules injected. This process can also be termed as in-cell or in-site internal air-bleeding. In addition, the utilization of anode side oxygen molecules transferred from the cathode side can be significantly increased compared to normal air bleeding processes, and hence reduce the chemical combustion reactions between fuel and extra oxygen in the anode side.
a is a block diagram showing an embodiment of the fuel cell system of the present invention. In the fuel cell system 200, the fuel cell stack 202 performance is monitored by a diagnosis module 204. If the diagnosis module 204 detects a decrease in the fuel cell stack 202 performance, it may perform a diagnosis to determine the root cause of the cell performance degradation, such as fuel starvation, water flooding or fuel contaminators. In the case that increased contaminator concentration has been detected, the diagnosis module 204 will trigger the fuel contaminator control module 206 to increase the transfer of a contaminator-reacting compound to the anode reactant and thereby decrease the contaminator concentration, as illustrated in
b illustrates an embodiment including an anode humidifier sub-system 208 that uses cathode off gas or a humidifying source external to the stack as a water source, such as the one illustrated in
The diagnosis module may include devices such as a voltage measurement device for a cell or a stack. Other possible devices are measurement devices for stoichiometry, calculation means for theoretical calculations, or storage means for previous experiment results used for comparison.
According to an embodiment of the invention, the diagnosis module that monitors the fuel cell stack performance may include a module that monitors the average cell stack voltage (which is equal to the stack voltage divided by the number of cells) and/or individual cell voltage. All of the individual cells or only a certain number of the individual fuel cells can be monitored at any given time. The monitored fuel cells may be selected randomly or in a specific sequence. When the diagnosis module detects a drop in the average cell stack voltage and/or individual cell voltage, the diagnosis module concludes that CO concentration has increased in the anode reactant and will trigger the fuel contaminator control module to transfer O2 molecules into the anode reactant from cathode side by adjusting anode/cathode and/or anode humidifier pressures to neutralize the CO molecules.
According to an embodiment of the invention, the diagnosis module that monitors the fuel cell stack performance may further include a module that monitors the anode and cathode stoichiometric variations. If the diagnosis module detects a drop in the average cell stack voltage and/or individual cell voltage and further detects no anode and cathode stoichiometric variations, the diagnosis module concludes that the decrease of the stack performance is due to an increase of contaminator concentration in the anode reactant. Then, the diagnosis module triggers the fuel contaminator control module to transfer the compound that chemically reacts with the contaminator into the anode reactant from the cathode side.
According to another embodiment of the invention, the diagnosis module that monitors the fuel cell stack performance comprises a contaminator detector such as a carbon monoxide detector that monitors the carbon monoxide concentration directly in the anode reactant. If the carbon monoxide detector detects an increase in the carbon monoxide concentration, the diagnosis module triggers the fuel contaminator control module to increase the oxygen concentration in the anode reactant. It should be understood that the contaminator detector is adapted to the kind of contaminator present in the anode reactant and the fuel contaminator control module is adapted to inject a compound that chemically reacts with the contaminator.
If an increase of the contaminator concentration is detected, the pressure of at least one of the reactants is adjusted in the MEA and/or the anode humidifier to inject a compound that chemically reacts with the contaminator in the anode reactant.
In an embodiment of the method, monitoring the fuel contaminator concentration comprises monitoring the fuel contaminator concentration in the anode reactant with a fuel contaminator detector.
In an embodiment of the method, monitoring the contaminator concentration and detecting an increase of the contaminator concentration are performed by monitoring the fuel cell stack performance. If the fuel cell stack performance decreases, the fuel cell system concludes that the contaminator concentration in the anode reactant has increased.
Monitoring the fuel cell stack performance may comprise at least one of monitoring the average cell voltage and monitoring the individual cell voltage. An increase of the contaminator concentration in the anode reactant is detected when the average fuel cell voltage and/or the individual fuel cell voltage drop below a threshold. Only a certain number of the individual fuel cells may be monitored at any given time. The monitored fuel cells may be selected randomly or not.
In another embodiment, monitoring the fuel cell stack performance may also comprise monitoring the flow of the anode and/or cathode reactant. If the average fuel cell voltage and/or the individual fuel cell voltage drop below a threshold and the flow of anode and/or cathode reactant remains substantially unvaried, the fuel cell system detects an increase of the contaminator concentration in the anode reactant. Only a certain number of the individual fuel cells can be monitored at any given time. The monitored fuel cells may be selected randomly or not.
In one embodiment of the method, the threshold is set between and 100 mV below the operational voltage, for example, about 10 to 30 mv.
Monitoring the flow of the anode and/or cathode reactant may include monitoring the stoichiometry of the anode and/or cathode reactant. The fuel cell system may have the capability to measure the anode and/or the cathode flow. According to the total stack current and number of stack cells, the stoichiometry can be calculated. An alternative method to monitor the flow consists in monitoring the pressure change of anode/cathode reactant. During normal operation of the fuel cell system, the pressure will be increased if the flow rate increases (assuming all other operational parameters remained unchanged).
If the fuel cell system has detected an increase of the contaminator concentration, the compound that chemically reacts with the contaminator can be injected in the anode reactant stream either in the stack or in the anode humidifier. If the injection takes place in the stack, at least one of increasing the cathode reactant pressure in the stack and decreasing the anode reactant pressure in the stack increases the flux of the compound from the cathode side to the anode side via the MEA membrane. If the injection takes place in the anode humidifier, at least one of increasing the humidifying source pressure and decreasing the anode reactant pressure in the anode humidifier increases the flux of the compound from the humidifying source side to the anode reactant side via the membrane of the anode humidifier. The increased concentration of the compound in the anode reactant then improves fuel cell performance. In an embodiment, the contaminator to be controlled is carbon monoxide and the compound that reacts with the contaminator is oxygen. In this embodiment, the O02 molecules chemically react with the CO molecules to CO2 molecules which have minor effects on fuel cell performance compared to the CO molecules.
In accordance with one embodiment, the amount of compound that reacts with the contaminator transferred into the anode reactant can be adjusted with respect to the importance of the drop of voltage. As the compound is transferred into the anode reactant stream, it suppresses the contaminator present in the anode reactant and the fuel cell stack performance increases. As the fuel cell stack performance gradually increases and the contaminator concentration decreases, the amount of transferred compound is gradually decreased. When the fuel cell stack performance reaches its original level and stabilizes, the transfer of compound is stopped.
It should be noted that a random or low quantity of oxygen may be injected instead of a predetermined quantity. In this case, the injection of oxygen is subsequently increased or decreased as function of the fuel contaminator concentration in the anode reactant.
It should be understood that the contaminator can be other than carbon monoxide and the compound that chemically reacts with the contaminator can be other than oxygen.
The embodiments of the invention described above are intended to be exemplary only. The scope of the invention is therefore intended to be limited solely by the scope of the appended claims.
The present application claims priority of US Provisional Patent Application filed on Aug. 7, 2006 and bearing Ser. No. 60/835,905.
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/CA07/01383 | 8/7/2007 | WO | 00 | 2/9/2009 |
| Number | Date | Country | |
|---|---|---|---|
| 60835905 | Aug 2006 | US |
