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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.

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.

The increasing use of gasoline direct injection (GDI) engines coupled with the implementation of new particulate matter (PM) and particle number (PN) emissions regulations requires new emissions control strategies. Gasoline particulate filters (GPFs) present one approach to reduce particle emissions. Although primarily composed of combustible material which may be removed through oxidation, particle also contains incombustible components or ash. Over the service life of the filter the accumulation of ash causes an increase in exhaust backpressure, and limits the useful life of the GPF. This study utilized an accelerated aging system to generate elevated ash levels by injecting lubricant oil with the gasoline fuel into a burner system. GPFs were aged to a series of levels representing filter life up to 150,000 miles (240,000 km). The impact of ash on the filter pressure drop and on its sensitivity to soot accumulation was investigated at specific ash levels.

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.

U.S. federal vehicle emission standards effective in 2007 require tight control of NOx and hydrocarbon emissions. For light-duty vehicles, the current standard of Tier 2 Bin 5 is about 0.07 g/mi NOx and 0.09 g/mi NMOG (non-methane organic gases) at 120,000 mi. However, the proposed future standard is 0.03 g/mi for NMOG + NOx (~SULEV30) at 150,000 mi. There is a significant improvement needed in catalyst system efficiencies for diesel vehicles to achieve the future standard, mainly during cold start. In this study, a less than 6000 lbs diesel truck equipped with an advanced urea Selective Catalytic Reduction (SCR) system was used to pursue lower tailpipe emissions with an emphasis on vehicle calibration and catalyst package. The calibration was tuned by optimizing exhaust gas recirculation (EGR) fuel injection and cold start strategy to generate desirable engine-out emissions balanced with reasonable temperatures.

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.

An advanced diesel aftertreatment system utilizing Selective Catalytic Reduction (SCR) with urea for lean nitrogen oxides (NOx) control was tested on a 2.7L V6 Land Rover vehicle to demonstrate the capability of achieving Tier 2 Bin 5 and lower emission standards for light-duty trucks. SCR washcoat was applied to a diesel particulate filter (DPF) to perform NOx and particulate reduction simultaneously. Advanced SCR systems employed both traditional SCR catalysts and SCR-coated filters (SCRF) to improve the NOx reduction efficiency. The engine-out NOx level was adjusted by modifying the EGR (Exhaust Gas Recirculation) calibration. Cold start NOx performance was improved by SCR warm-up strategy and urea over injection. This study showed the advanced SCR system could tolerate higher NH₃ storage in the SCR catalyst, resulting in overall higher NOx conversion on the FTP-75 test cycle.

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.

For diesel applications, cold start accounts for a large amount of the total NOx emissions during a typical Federal Test Procedure (FTP) for light-duty vehicles and is a key focus for reducing NOx emissions. A common form of diesel NOx aftertreatment is selective catalytic reduction (SCR) technology. For cold start NOx improvement, the SCR catalyst would be best located as the first catalyst in the aftertreatment system; however, engine-out hydrocarbons and no diesel oxidation catalyst (DOC) upstream to generate an exotherm for desulfation can result in degraded SCR catalyst performance. Recent advances in vanadia-based SCR (V-SCR) catalyst technology have shown better low temperature NOx performance and improved thermal durability. Three V-SCR technologies were tested for their thermal durability and low-temperature NOx performance, and after 600°C aging, one technology showed low-temperature performance on par with state-of-the-art copper-zeolite SCR (Cu-SCR) technology.

Copper/zeolite catalysts are the leading urea SCR catalysts for NOx emission treatment in diesel applications. Sulfur poisoning directly impacts the overall SCR performance and is still a durability issue for Cu/zeolite SCR catalysts. Most studies on sulfur poisoning of Cu/zeolite SCR catalysts have been based on SO2 as the poisoning agent. It is important to investigate the relative poisoning effects of SO3, especially for systems with DOCs in front of Cu/zeolite SCR catalysts. It was observed that SCR activity was significantly reduced for samples poisoned by SO3 vs. those poisoned by SO2. The sulfur was released mainly as SO2 for both samples poisoned by SO2 and SO3. The temperatures and the magnitudes of released SO2 peaks however, were very different between the samples poisoned by SO2 vs. SO3. The results indicate that sulfur poisoning by SO2 and SO3 are not equivalent, with different poisoning mechanisms and impacts.

Base metal/zeolite catalysts, particularly containing copper and iron, are among the leading candidates for treatment of NOx emissions for diesel applications. Even with the use of ultra low sulfur fuel, sulfur poisoning is still a durability issue for base metal/zeolite SCR catalysts. In this study, the impact of sulfur poisoning on SCR activity and the stored sulfur removal effectiveness were investigated on several Cu and Fe/zeolite SCR catalysts after different thermal aging. The impact of sulfur was more significant on the Cu than on Fe/zeolite SCR catalysts for the NOx activity. It was found that the sensitivity of thermal aging status to the sulfur poisoning impact was different. The impact of sulfur on NOx activity changed with thermal aging on some catalysts, while it remained relatively the same for other catalysts. The most thermally durable SCR catalyst was not necessarily the most durable to sulfur poisoning.

Selective catalytic reduction (SCR) is a viable option for control of oxides of nitrogen (NOx) from diesel engines. Currently, copper zeolite (Cu-zeolite) SCR catalysts are favored for configurations where the exhaust gas temperature is below 450°C for the majority of operating conditions, while iron zeolite (Fe-zeolite) SCR catalysts are preferred where NOx conversion is needed at temperatures above 450°C. The selection of Cu-zeolite or Fe-zeolite SCR catalysts is based on the different performance characteristics of these two catalyst types. Cu-zeolite catalysts are generally known for having efficient NOx reduction at low temperatures with little or no NO2, and they tend to selectively oxidize ammonia (NH3) to N2 at temperatures above 400°C, leading to poor NOx conversion at elevated temperatures.

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.

Temperature programmed reduction by CO, H2, and propylene (C3H6), as well as hydrothermal aging in the presence of mixture of NO, HC, CO, H2 and O2 were used to study the deactivation of Cu/zeolite SCR catalysts. The presence of CO had no detrimental effect on catalyst activity. Carbonaceous deposit on the catalyst surface from propylene (C3H6) reduction suppressed the catalyst activity and burn off of carbonaceous deposit recovered activity, the presence of O2 suppressed carbonaceous deposit formation. The presence of H2 under lean conditions had much less effect on catalyst activity than H2 presence under rich conditions. Rich conditions with O2 presence represented the most detrimental effect on catalyst activity.

Selective Catalytic Reduction of NOx is a promising technology to enable diesel engines to meet certification under Tier 2 Bin 5 emissions requirements. SCR catalysts for vehicle use are typically zeolitic materials known to store both hydrocarbons and ammonia. Ammonia storage on the zeolite has a beneficial effect on NOx conversion; hydrocarbons however, compete with ammonia for storage sites and may also block access to the interior of the zeolites where the bulk of the catalytic processes take place. This paper presents the results of laboratory studies utilizing surrogate hydrocarbon species to simulate engine-out exhaust over catalysts formulated to operate in both low (≈175-500°C) and high temperature (≈250-600°C) regimes. The effects of hydrocarbon exposure of these individual species on the SCR reaction are examined and observations are made as to necessary conditions for the recovery of SCR activity.

Selective catalytic reduction (SCR) is a technology capable of meeting Tier 2 Bin 5 emissions levels of oxides of nitrogen (NOX) for diesel engines. Base metal zeolite catalysts show the best combination of thermal durability and NOX conversion activity. It is shown in this work that some base metal zeolite catalysts can store high levels of hydrocarbons (HCs). Also, base metal zeolite catalysts can catalyze oxidation of HCs under certain conditions. Oxidation of stored hydrocarbons can lead to permanent catalyst deactivation due to the exotherm generated in the SCR catalyst (over-temperature condition leading to SCR catalyst damage). This paper discusses a laboratory bench test to characterize hydrocarbon storage and burn-off characteristics of several SCR catalyst formulations, as well as engine dynamometer tests showing hydrocarbon storage and exotherm generation.

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.