OXIDATION OF DRY HYDROCARBONS AT HIGH-POWER DENSITY ANODES

This work builds upon discoveries by the University of Pennsylvania and others pertaining to the oxidation of dry hydrocarbon fuels in high temperature solid oxide fuel cells. The work reported here was restricted primarily to dry methane and confirms that YSZ-based cells, having ceria in the anode as a catalyst and copper in the anode as a current collector, can operate on dry methane for extended periods. Thirty-three lab-scale cells of various designs were fabricated and operated under a variety of conditions. The longest-lived cell gave stable performance on dry methane at 800 C for over 305 hours. Only slight carbon deposition was noted at the completion of the test. A corresponding nickel/YSZ-based anode would have lasted for less than an hour under these test conditions (which included open circuit potential measurements) before carbon fouling essentially destroyed the cell. The best performing cell achieved 112 mW/cm{sub 2} on dry methane at 800 C. Several problems were encountered with carbon fouling and declining open circuit voltages in many of the test cells after switching from operation on hydrogen to dry methane. Although not rigorously confirmed by experimentation, the results suggested that air infiltration through less than perfect perimeter seals or pinholes in the electrolytes, or both gave rise to conditions that caused the carbon fouling and OCV decline. Small amounts of air reacting with methane in a partial oxidation reaction could produce carbon monoxide that, in turn, would deposit the carbon. If this mechanism is confirmed, it implies that near perfect hardware is required for extended operation. Some evidence was also found for the formation of electrical shorts, probably from carbon deposits bridging the electrolyte. Work with odorized methane and with methane containing 100-ppm hydrogen sulfide confirmed that copper is stable at 800 C in dry hydrocarbon fuels in the presence of sulfur. In a number of cases, but not exclusively, the performance life on dry methane with sulfur compounds was much longer than with dry methane alone. The effect of sulfur compounds in these cases appeared to correlate with inhibition of carbon deposition. Mixed results were obtained for the effect of the sulfur compounds on power density. Progress also was made in understanding the mechanisms involved in direct utilization of dry natural gas. Evidence was developed for three possible mechanisms for dry methane utilization in addition to the usually cited mechanism--direct oxidation of methane by oxygen anions. Further work is required at a fundamental level before the knowledge gained here can be translated into higher levels of performance