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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.

Model low temperature NOx adsorbers (LTNA) consisting of Pd on a ceria/zirconia washcoat on monoliths were evaluated for low temperature NOx storage under lean conditions to assess their potential for adsorbing the cold-start NOx emissions on a diesel engine during the period before the urea/SCR system becomes operational. A reactor-based transient test was performed with and without C2H4, CO/H2, and H2O to assess the effects of these species on the NOx storage performance. In the absence of C2H4 or CO/H2, H2O severely suppressed the NOx storage of these model LTNAs at temperatures below 100°C, presumably by blocking the storage sites. When C2H4 was included in the feedgas, H2O still suppressed the NOx storage below 100°C. However, the C2H4 significantly increased the NOx storage efficiency above 100°C, attributable to the formation of alkyl nitrites or alkyl nitrates on the catalyst.

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.

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.

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.

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.

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.

A laboratory study was performed to assess the effects of sulfur poisoning and desulfation temperature on the NO conversion of a LNT+(Cu/SCR) in-situ system. Four LNT+(Cu/SCR) systems were aged for 4.5 hours without sulfur at 600, 700, 750, and 800°C using A/F ratio modulations to represent 23K miles of desulfations at different temperatures. NO conversion tests were performed on the LNT alone and on the LNT+SCR system using a 60 s lean/5 s rich cycle. The catalysts were then sulfur-poisoned at 400°C and desulfated four times and re-evaluated on the 60/5 tests. This test sequence was repeated 3 more times to represent 100K miles of desulfations. After simulating 23K miles of desulfations, the Cu-based SCR catalysts improved the NO conversion of the LNT at low temperatures (e.g., 300°C), although the benefit decreased as the desulfation temperature increased from 600°C to 800°C.

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 effects of SO2 poisoning on the NOx conversion of iron (Fe) and copper (Cu) SCR catalysts. Thermally aged samples of the catalysts were poisoned with SO2 under lean conditions. At various times during the poisonings, the samples were evaluated for NOx conversion with NO and NH3 using lean temperature ramps. The low temperature NOx conversions of both catalysts decreased by 10 to 20% after 1 to 4 hours of poisoning but were stable with continued exposure to the SO2. The poisoned Cu SCR catalyst could be desulfated repeatedly with 5 minutes of lean operation at 600°C. Initially, the poisoned Fe SCR catalyst required 5 minutes of lean operation at 750°C to recover its maximum NOx conversion.

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.

A laboratory study was performed to assess the contributions of platinum and rhodium to the emissions performance of a lean NOx trap. Samples of a barium-only formulation were obtained with either 0.84 g/L of platinum, 0.51 g/L of rhodium, or 1.0 g/L of platinum and rhodium in ratios of 1/0/1 or 5/0/1. 60 s lean/5 s rich tests were performed on fresh samples and samples that were aged on high temperature durability cycles. The results indicate that platinum is necessary for the NOx storage performance of the trap at low temperatures (e.g., 250°C), whereas rhodium is needed for the NOx reduction capability and consequently the purgability of the trap at low temperatures. As a result, the bimetallic Pt/Rh samples provided the best overall NOx conversion at low temperatures fresh and after aging.

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.

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.

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.

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.

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.

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.

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.