5. Regeneration. Sulfur inhibition of automobile catalysts can be temporary and recovery to original performance has been achieved by return to low sulfur fuel under the appropriate operating condition. However, emissions data from tests on low-emitting vehicles indicated full recovery was not occurring. Ford reported test results on low sulfur fuel (60 ppm S base fuel), followed by exposure to high sulfur fuel (930 ppm S), and then again a return to low sulfur fuel (8). The tests were performed on a vehicle meeting the California ULEV standards. In this work, Ford showed that exposure to high sulfur fuel increased HC emissions from 0.04 g/mile to about 0.12 g/mile. A return to low sulfur fuel resulted in improved performance but only to about 0.07 g/mile, but a subsequent rich calibration hot cycle was required to return performance to the original performance level. Experiments conducted by Thoss et. al. did not show significant regeneration upon evaluation with low sulfur gasoline (87 ppm sulfur) or with treatments at 700°C under slightly lean conditions (7). A companion paper showed almost complete recovery of an improved Pd-only three-way catalyst when fuel was switched from 1000 ppm to 100 ppm sulfur (19). Benson noted that sulfur inhibition was reversible at high exhaust gas temperatures with low sulfur fuel for U.S. Tier 1 technology vehicles, but that sulfur effects are more critical with lower emission vehicles and may not be reversible (10).
In two studies on the effect of gasoline fuel sulfur on LEV and ULEV-type vehicles by AAMA/AIAM (11) and CRC (12), the issue of sulfur removal was addressed. Both studies used a sulfur purge cycle to remove previous accumulated sulfur from catalysts. The cycle employed a series of five vehicle wide-open-throttle (WOT) acceleration/cruise/deceleration excursions and a steady state drive to increase the catalyst temperature and provide a rich air-to-fuel operating condition to facilitate the release of the sulfur compounds that accumulate on the catalyst. This cycle was repeated to give a minimum of ten acceleration/cruise/deceleration excursions. In this LEV/ULEV test program, some manufacturers increased the stringency of the sulfur purge cycles to ensure adequate sulfur removal. To ensure adequate catalyst temperature (650°C or higher), the catalyst inlet temperature was monitored with a thermocouple. From these studies it appears that special cycle conditions have to exist in order to regenerate catalyst performance via sulfur purging.
Operating the catalyst at a sufficiently high temperature under net reducing conditions can effectively release the sulfur oxides from the catalyst components. However, it cannot completely eliminate the effects of sulfur poisoning. A study of Tier 2 vehicles in the in-use fleet recently completed by EPA shows that emission levels immediately following high speed/load operation is still a function of fuel sulfur levels, suggesting that lower fuel sulfur levels will bring emission benefits unachievable by a catalyst regeneration procedure alone (18). Additionally, regular operation at these temperatures and at rich air-to-fuel ratios is not desirable, due to several reasons. The temperatures necessary to release sulfur oxides are high enough to lead to thermal degradation of the catalyst over time via thermal sintering of active materials. Sintering reduces the surface area available to participate in reactions. It is also not always possible to maintain these catalyst temperatures (because of cold weather, idle conditions, light load operation) and the rich air-to-fuel ratios necessary can result in increased PM, NMOG and CO emissions.
In addition, higher engine efficiencies drive lower exhaust temperature, making sulfur poisoning more problematic. Similarly, hybrid electric vehicle’s start/stop driving mode limits exhaust temperatures, leading to enhanced sulfur poisoning of the catalyst.
5. Regeneration. Sulfur inhibition of automobile catalysts can be temporary and recovery to original performance has been achieved by return to low sulfur fuel under the appropriate operating condition. However, emissions data from tests on low-emitting vehicles indicated full recovery was not occurring. Ford reported test results on low sulfur fuel (60 ppm S base fuel), followed by exposure to high sulfur fuel (930 ppm S), and then again a return to low sulfur fuel (8). The tests were performed on a vehicle meeting the California ULEV standards. In this work, Ford showed that exposure to high sulfur fuel increased HC emissions from 0.04 g/mile to about 0.12 g/mile. A return to low sulfur fuel resulted in improved performance but only to about 0.07 g/mile, but a subsequent rich calibration hot cycle was required to return performance to the original performance level. Experiments conducted by Thoss et. al. did not show significant regeneration upon evaluation with low sulfur gasoline (87 ppm sulfur) or with treatments at 700°C under slightly lean conditions (7). A companion paper showed almost complete recovery of an improved Pd-only three-way catalyst when fuel was switched from 1000 ppm to 100 ppm sulfur (19). Benson noted that sulfur inhibition was reversible at high exhaust gas temperatures with low sulfur fuel for U.S. Tier 1 technology vehicles, but that sulfur effects are more critical with lower emission vehicles and may not be reversible (10).
In two studies on the effect of gasoline fuel sulfur on LEV and ULEV-type vehicles by AAMA/AIAM (11) and CRC (12), the issue of sulfur removal was addressed. Both studies used a sulfur purge cycle to remove previous accumulated sulfur from catalysts. The cycle employed a series of five vehicle wide-open-throttle (WOT) acceleration/cruise/deceleration excursions and a steady state drive to increase the catalyst temperature and provide a rich air-to-fuel operating condition to facilitate the release of the sulfur compounds that accumulate on the catalyst. This cycle was repeated to give a minimum of ten acceleration/cruise/deceleration excursions. In this LEV/ULEV test program, some manufacturers increased the stringency of the sulfur purge cycles to ensure adequate sulfur removal. To ensure adequate catalyst temperature (650°C or higher), the catalyst inlet temperature was monitored with a thermocouple. From these studies it appears that special cycle conditions have to exist in order to regenerate catalyst performance via sulfur purging.
Operating the catalyst at a sufficiently high temperature under net reducing conditions can effectively release the sulfur oxides from the catalyst components. However, it cannot completely eliminate the effects of sulfur poisoning. A study of Tier 2 vehicles in the in-use fleet recently completed by EPA shows that emission levels immediately following high speed/load operation is still a function of fuel sulfur levels, suggesting that lower fuel sulfur levels will bring emission benefits unachievable by a catalyst regeneration procedure alone (18). Additionally, regular operation at these temperatures and at rich air-to-fuel ratios is not desirable, due to several reasons. The temperatures necessary to release sulfur oxides are high enough to lead to thermal degradation of the catalyst over time via thermal sintering of active materials. Sintering reduces the surface area available to participate in reactions. It is also not always possible to maintain these catalyst temperatures (because of cold weather, idle conditions, light load operation) and the rich air-to-fuel ratios necessary can result in increased PM, NMOG and CO emissions.
In addition, higher engine efficiencies drive lower exhaust temperature, making sulfur poisoning more problematic. Similarly, hybrid electric vehicle’s start/stop driving mode limits exhaust temperatures, leading to enhanced sulfur poisoning of the catalyst.
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