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An aftertreatment system involving a LNT followed by a SCR catalyst is proposed for treating the NOx emissions from a diesel engine. NH3 (or urea) is injected between the LNT and the SCR. The SCR is used exclusively below 400°C due to its high NOx activity at low temperatures and due to its ability to store and release NH3 below 400°C, which helps to minimize NH3 and NOx slip. Above 400°C, where the NH3 storage capacity of the SCR falls to low levels, the LNT is used to store the NOx. A potassium-based LNT is utilized due to its high temperature NOx storage capability. Periodically, hydrocarbons are oxidized on the LNT under net lean conditions to promote the thermal release of the NOx. NH3 is injected simultaneously to reduce the released NOx over the SCR. The majority of the hydrocarbons are oxidized on the front portion of the LNT, resulting in the rapid release of stored NOx from that portion of the LNT.

Lean NOx Traps are used to treat the NOx emissions from lean-burn engines by storing the NOx under lean conditions and reducing the NOx during periodic rich excursions. However, sulfur poisons the adsorption sites of the traps. The sulfur can be removed from the NOx trap by operating rich at high temperatures for several minutes. This results in the release of some SO2 but also large quantities of H2S, which is a source of customer dissatisfaction that must be reduced or eliminated. This paper describes the use of a nickel-containing catalyst and air/fuel control to maximize the release of SO2 and minimize the emissions of H2S during the desulfation of a lean NOx trap. We present laboratory and vehicle data with a nickel-containing catalyst located downstream of a lean NOx trap during desulfations of the trap. The nickel effectively reduced the emissions of H2S during the desulfation while improving the robustness to fluctuations in the air/fuel control.

A laboratory study was performed to assess the effectiveness of LNT+SCR systems for NOx control in lean exhaust. The effects of the catalyst system length and the spatial configuration of the LNT & SCR catalysts were evaluated for their effects on the NOx conversion, NH₃ yield, N₂O yield, and HC conversion. It was found that multi-zone catalyst architectures with four or eight alternating LNT and SCR catalyst zones had equivalent gross NOx conversion, lower NH₃ and N₂O yield, and significantly higher net conversion of NOx to N₂ than an all-LNT design or a standard LNT+SCR configuration, where all of the SCR volume is placed downstream of the LNT. The lower NH₃ emissions of the two multi-zone designs relative to the standard LNT+SCR design were attributed to the improved balance of NOx and NH₃ in the SCR zones.

Desulfation characteristics of several model and fully-formulated monolithic lean NOx trap materials were studied in a laboratory flow reactor employing a chemical ionization mass spectrometer. For all samples, desulfation at elevated temperatures under reducing conditions resulted in appearance of sulfur dioxide (SO2) followed by carbonyl sulfide (COS) and hydrogen sulfide (H2S). The data appear consistent with a desulfation mechanism involving elimination of SO2 from stored sulfates under reducing conditions, followed by reaction of the SO2 with CO and H2 to produce COS and H2S, respectively. Based on these observations, several cyclic and multistage desulfation strategies were devised which greatly decreased H2S emissions while achieving relatively rapid and complete sulfur removal.

The effects of PGM zoning and washcoat staging have been investigated as a means to lower the cost and simultaneously improve the performance of a lean NOx trap system. It is shown that reverse PGM zoning can be used to reduce the cost of the LNT while essentially maintaining the NOx performance of a similarly-sized trap with a uniformly high PGM loading. In addition, the effective temperature window of the trap can be expanded by staging different NOx trap formulations that are optimized for different temperature ranges. Alternatively, LNT washcoat staging can be used to improve the hydrocarbon conversion of the trap while maintaining good NOx performance. Laboratory data and vehicle data are presented for several NOx trap system combinations that demonstrate the improved performance that can be obtained from a combination of reverse PGM zoning and washcoat staging.

This paper summarizes results from a large study on the release of NOx from a lean NOx trap during rich purges. Under certain purge conditions, some NOx trap formulations have the propensity to release some of the NOx stored during previous lean operation without reducing it. This purge NOx release was examined for different NOx trap formulations. The purge NOx release was evaluated for one of the formulations as a function of several variables, including the aging condition of the trap, the trap temperature, the trap volume, the purge A/F ratio, the purge flow rate, and the amount of NOx stored. The effect of hot lean pretreatments on the purge NOx release was studied. In addition, the effect of the rhodium level on the purge NOx release was examined. Mechanisms for the NOx release are proposed that are consistent with the observed data. The results indicate that the purge NOx release is very low for thermally aged traps and is primarily a concern for fresh or stabilized traps.

A laboratory study was performed to assess the potential capability of passive TWC+SCR systems to satisfy the Tier 2, Bin 2 emission standards for lean-burn gasoline applications. In this system, the TWC generates the NH3 for the SCR catalyst from the feedgas NOx during rich operation. Therefore, this approach benefits from high feedgas NOx during rich operation to generate high levels of NH3 quickly and low feedgas NOx during lean operation for a low rate of NH3 consumption. It was assumed that the exhaust system needed to include a close-coupled (CC) TWC, an underbody (U/B) TWC, and an U/B SCR converter to satisfy the emission standards during the FTP and US06 tests while allowing lean operation for improved fuel economy during select driving conditions. Target levels for HC, CO, and NOx during lean/rich cycling were established. With a 30 s lean/10 s rich cycle and 200 ppm NO lean, 1500 ppm NO rich and the equivalent of 3.3 L of SCR volume were required to satisfy the NOx target.

Lean NOx Traps (LNTs) are one type of lean NOx reduction technology typically used in smaller diesel passenger cars where urea-based Selective Catalytic Reduction (SCR) systems may be difficult to package . However, the performance of lean NOx traps (LNT) at temperatures above 400 C needs to be improved. The use of Rapidly Pulsed Reductants (RPR) is a process in which hydrocarbons are injected in rapid pulses ahead of a LNT in order to expand its operating window to higher temperatures and space velocities. This approach has also been called Di-Air (diesel NOx aftertreatment by adsorbed intermediate reductants) by Toyota. There is a vast parameter space which could be explored to maximize RPR performance and reduce the fuel penalty associated with injecting hydrocarbons. In this study, the mixing uniformity of the injected pulses, the type of reductant, and the concentration of pulsed reductant in the main flow were investigated.

The mechanism for the purging of a lean NOx trap has been investigated. For realistic purge times (e.g., 2 to 5 seconds), the stored NOx species do not decompose simply from equilibrium considerations (i.e., from the drop in O2 and NO concentrations during the rich purge). Instead, the decomposition of stored NOx is promoted by the reductants in the exhaust by a process referred to as reductive elimination. H2 is far more effective than CO or C3H6 for promoting this reductive elimination, particularly at low temperatures (e.g., 250°C). As long as H2 is available in the feedgas, H2O does not participate in the reductive elimination. However, if CO is the only reductant, H2O is needed to convert some of the CO to H2 through the water-gas-shift reaction. H2O is also important for the efficient storage of NOx during lean operation, possibly by enhancing the spillover of NO2 from a precious metal site to a NOx storage site.

A laboratory study was performed to optimize a zoned configuration of an iron (Fe) SCR catalyst and a copper (Cu) SCR catalyst in order to provide high NOx conversion at lean A/F ratios over a broad range of temperature for diesel and lean-burn gasoline applications. With an optimized space velocity of 8,300 hr-1, a 67% (by volume) Fe section followed by a 33% Cu section provided at least 80% NOx conversion from approximately 230°C to 640°C when evaluated with 500 ppm NO and NH3. To improve the lean lightoff performance of the SCR catalyst system during a cold start, a Cu SCR catalyst that was 1/4 as long as the rear Cu SCR catalyst was placed in front of the Fe SCR catalyst. When evaluated with an excess of NH3 (NH3/NO ratio of 2.2), the Cu+Fe+Cu SCR system had significantly improved lightoff performance relative to the Fe+Cu SCR system, although the front Cu SCR catalyst did decrease the NOx conversion at temperatures above 475°C by oxidizing some of the NH3 to N2 or NO.

A laboratory study was performed to assess the potential of using selective catalytic reduction (SCR) with NH3 to treat the NOx emissions from lean-burn gasoline engines. A primary concern was the potential for hot rich exhaust conditions on the vehicle, as such conditions could degrade the zeolite-based SCR catalysts being developed for automotive applications. Samples of an iron/zeolite formulation were aged for 34 hours behind samples of a three-way catalyst (TWC) on a pulse-flame combustion reactor using different A/F ratio schedules that exposed the catalysts to either continuously lean operation, mostly stoichiometric operation, or mostly rich operation. For each A/F ratio schedule, separate SCR samples were aged with inlet temperatures of 750°C, 800°C, or 850°C. The aged SCR samples were evaluated for NOx conversion at 25K hr-1 during lean temperature ramps with 500 ppm NO and NH3.

Selective catalytic reduction (SCR) with NH3 provides an attractive alternative to lean NOx traps for controlling the NOx emissions from lean-burn gasoline engines. This paper summarizes a laboratory study to assess the effects of temperature, space velocity, and the concentrations of NO, NH3, and O2 on the NOx conversion of an iron/zeolite SCR catalyst. A fresh sample was evaluated on slow temperature ramps with 5% O2 and 250, 500, or 1000 ppm of NO and NH3. The NOx conversion at low temperatures decreased with increasing NO and NH3 concentrations due to kinetic limitations. Conversely, the conversion at high temperatures increased with increasing NO and NH3 concentrations because the portion of NH3 oxidized by O2 decreased with increasing NO concentration.

Lean NOx traps (LNT) are currently the technology of choice for treating the NOx emissions from lean burn gasoline engines. With the help of the newly established low sulfur fuel to be introduced in the European and the U.S. markets, the widespread application of LNT technology becomes more promising. However, we found that the sulfur tolerance of aged LNTs is much lower than that of the fresh LNTs. Moreover, the aged LNTs are more difficult to be desulfated relative to the fresh ones. The robustness of the LNT still needs to be improved. This work is focused on understanding the fundamental processes of sulfur poisoning and desulfation as the trap ages. Three LNT samples were selected from different suppliers. These samples were subject to different aging conditions. Flow reactor and pulse flame combustor tests were conducted on the samples to evaluate their performances with regard to sulfur poisoning and desulfation.

A laboratory study was performed to assess the potential capability of TWC+LNT/SCR systems to satisfy the Tier 2, Bin 2 emission standards for lean-burn gasoline applications. It was assumed that the exhaust system would need a close-coupled (CC) TWC, an underbody (U/B) TWC, and a third U/B LNT/SCR converter to satisfy the emission standards on the FTP and US06 tests while allowing lean operation for improved fuel economy during select driving conditions. Target levels for HC, CO, and NOx during lean/rich cycling were established. Sizing studies were performed to determine the minimum LNT/SCR volume needed to satisfy the NOx target. The ability of the TWC to oxidize the HC during rich operation through steam reforming was crucial for satisfying the HC target.

This paper summarizes results from a large study on the desulfation characteristics of lean NOx traps. Degreened and thermally aged NOx trap formulations were poisoned with SO2 multiple times in a flow reactor. The effect of desulfation time and temperature on the recovery of NOx trapping efficiency was evaluated after the poisonings. The relative effectiveness of the reducing agents (CO and H2) used during the desulfation was evaluated for one of the formulations. The results indicate that the high temperatures required for desulfation (e.g., 700°C and above) result in thermal degradation of NOx traps that had been degreened at a lower temperature (e.g., 600°C), and therefore desulfation studies should be performed with traps that have already been exposed to the desulfation temperatures or higher prior to the poisoning.

In anticipation that future gasoline engines will have improved fuel efficiency and therefore lower exhaust temperatures during low load operation, a project was initiated in 2014 to develop three-way catalysts (TWC) with improved activity at lower temperatures while maintaining the durability of current TWCs. This project is a collaboration between Ford Motor Company, Oak Ridge National Laboratory, and the University of Michigan and is funded by the U.S. Department of Energy. The ultimate goal is to show progress towards the USDRIVE goal of 90% conversion of hydrocarbons (HC), carbon monoxide (CO), and nitrogen oxides (NOx) at 150°C after high mileage aging. A reactor was set up at Ford to follow the catalyst testing protocols established by the USDRIVE ACEC tech team for evaluating catalysts for stoichiometric gasoline direct-injection (S-GDI) engines; this protocol specifies a stoichiometric blend of CO/H2, NO, C3H6, C2H4, C3H8, O2, H2O, and CO2 for the evaluations.

It is anticipated that future gasoline engines will have improved mechanical efficiency and consequently lower exhaust temperatures at low load conditions, although the exhaust temperatures at high load conditions are expected to remain the same or even increase due to the increasing use of downsized turbocharged engines. In 2014, a collaborative project was initiated at Ford Motor Company, Oak Ridge National Lab, and the University of Michigan to develop three-way catalysts with improved performance at low temperatures while maintaining the durability of current TWCs. This project is funded by the U.S. Department of Energy and is intended to show progress toward the USDRIVE target of 90% conversion of hydrocarbons (HC), carbon monoxide (CO), and nitrogen oxides (NOx) at 150 °C after high mileage aging. The testing protocols specified by the USDRIVE ACEC team for stoichiometric S-GDI engines were utilized during the evaluation of experimental catalysts at all three facilities.

A study was performed on a lean NOx trap in which the loading of a ceria-containing mixed oxide in the washcoat was varied. After a mild stabilization of the traps, the time required to purge the NOx trap generally increased with increasing amount of mixed oxide. The purge NOx release also increased with increasing mixed oxide level but was greatly diminished after thermal aging. The sulfur tolerance of the NOx trap improved as the mixed oxide content was increased from 0% to 37%. The sample with 0% mixed oxide was more difficult to desulfate than the other samples due to poor water-gas-shift capability. After thermal aging, the NOx reduction efficiency on a 60 second lean/5 second rich cycle was highest for the samples with 0% to 37% mixed oxide at evaluation temperatures of 400°C to 500°C.

This paper summarizes results from a study on the effects of aging temperature and A/F ratio on the NOx storage capacity of a lean NOx trap. When aged at stoichiometry at 700°C, the NOx storage capacity of the NOx trap dropped considerably during the first 200 hours of aging and then at a much slower rate beyond 200 hours. The NOx storage capacity dropped more rapidly as the aging temperature increased, with the drop in capacity particularly evident between 900°C and 1000°C. The drop in NOx capacity was significantly larger for samples aged with part-time lean operation and/or part-time rich operation than for samples aged continuously at stoichiometry. The detrimental effects of lean and rich operation increased as the temperature increased. A Pt/Al2O3 model catalyst was exposed to reducing conditions at temperatures ranging from 670°C to 1041°C and then to oxidizing conditions over the same temperature range, and in-situ XRD was used to investigate Pt particle coarsening.

A laboratory aging study was performed on samples of a lean NOx trap with platinum group metal (PGM) loadings of 0.53, 1.06, 2.12, and 3.18 g/liter. The LNT samples were aged at inlet temperatures of 650°C, 750°C, 800°C, and 850°C behind samples of a three-way catalyst that were aged on a pulse-flame combustion reactor with a Ford-proprietary durability schedule representing 80,000 km of customer use. For all aging temperatures, higher PGM loadings were beneficial for low temperature NOx performance, attributable to an increase in the oxidation of NO to NO2. Conversely, lower PGM loadings were beneficial for high temperature NOx performance after aging at 650°C and 750°C, as higher loadings promoted the decomposition of the nitrates during lean operation and thereby decreased the NOx storage capability at high temperatures. Also, higher PGM loadings increased the OSC of the trap and thereby increased the purge requirements.