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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.

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.

Global demand for alternative fuels to combat rising energy costs has sparked a renewed interest in catalysts that can effectively remediate NOx emissions resulting from combustion of a range of HC based fuels. Because many of these new engine technologies rely on lean operating environments to produce efficient power, the resulting emissions are also present in a lean atmosphere. While HCs are easily controlled in such environments, achieving high NOx conversion to N2 has continued to elude fully satisfactory solution. Until recently, most approaches have relied on catalysts with precious metals to either store NOx and subsequently release it as N2 under rich conditions, or use NH3 SCR catalysts with urea injection to reduce NOx under lean conditions. However, new improvements in Ag based technologies also look very promising for NOx reduction in lean environments.

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.

Low-cost lean NOx aftertreatment is one of the main challenges facing high-efficiency gasoline and diesel engines operating with lean mixtures. While there are many candidate technologies, they all offer tradeoffs. We have investigated a multi-component Dual SCR aftertreatment system that is capable of obtaining NOx reduction efficiencies of greater than 90% under lean conditions, without the use of precious metals or urea injection into the exhaust. The Dual SCR approach here uses an Ag HC-SCR catalyst followed by an NH3-SCR catalyst. In bench reactor studies from 150 °C to 500 °C, we have found, for modest C/N ratios, that NOx reacts over the first catalyst to predominantly form nitrogen. In addition, it also forms ammonia in sufficient quantities to react on the second NH3-SCR catalyst to improve system performance. The operational window and the formation of NH3 are improved in the presence of small quantities of hydrogen (0.1–1.0%).

The need for improved emissions control in lean exhaust to meet tightening, world-wide NOx emissions standards has led to the development of selective catalytic reduction of NOx with ammonia as a major technology for emissions control. Current systems are being designed to use a solution of urea (32.5 wt %) dissolved in water or Diesel Exhaust Fluid (DEF) as the ammonia source. While DEF or AdBlue® is widely used as a source of ammonia, it has a number of issues at low temperatures, including freezing below −12 °C, solid deposit formation in the exhaust, and difficulties in dosing at exhaust temperatures below 200 °C. Additionally creating a uniform ammonia concentration can be problematic, complicating exhaust packaging and usually requiring a discrete mixer.

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.

The major challenge in diesel NOx aftertreatment systems using NOx adsorbers is their susceptibility to sulfur poisoning. A new computational model has been developed for the thermal management of NOx adsorber desulfation and describes the exothermic reaction mechanisms on the catalyst surface in the diesel NOx trap. Sulfur, which is present in diesel fuel, adsorbs as sulfates and accumulates at the same adsorption sites as NOx, therefore inhibiting the ability of the catalyst to adsorb NOx. Typically, a high surface temperature above 650 °C is required to release sulfur rapidly from the catalyst [1]. Since the peak temperatures of light-duty diesel engine exhaust are usually below 400 °C, additional heat is required to remove the sulfur. This report describes a new mathematical model that employs Navier-Stokes equations coupled with species transportation equations and exothermic chemical reactions.

NOx adsorber catalysts are leading candidates for improving NOx aftertreatment in diesel exhaust. The major challenge in the use of adsorbers that capture NOx in the form of nitrates is their susceptibility to sulfur poisoning. Sulfur, which is present in diesel fuel, adsorbs and accumulates as sulfate (SO4-2) at the same adsorption sites as NOx, and, since it is more stable than nitrates, inhibits the ability of the catalyst to adsorb NOx. It is found that high temperature (> about 650 °C) in the presence of a reducing gas is required to release sulfur rapidly from the catalyst. Since the peak temperatures of diesel engine exhaust are below 400 °C, additional heat is required to remove the sulfur. This work describes a reformate-assisted “sulfur purge” method, which employs heat generated inside the NOx trap catalyst by exothermic chemical reactions between the oxygen in diesel exhaust and injected reformate (H2 + CO).

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.

The reactivity of NOx over two prototype catalysts has been measured in a new bench reactor for characterizing plasma–catalyst systems that allows for in–situ post–analysis of any species which may have adsorbed on the catalyst. In these initial studies without a plasma, NO2 was used to mimic the NOx output of a plasma reactor in a blended feedstream that mimics diesel exhaust. The baseline performance of the catalysts was measured as a function of temperature, hydrocarbon concentration, hydrocarbon type, and water content, usually at a space velocity of 29,000 h–1. Performance was assessed in terms of the percent conversion of the incoming NO2 to desirable non–NOx N–containing species. For the better of the two catalysts the conversion without water present peaked in the 30–40% range between 125°C and 175°C using a propene/propane mixture of hydrocarbons in a 10:1 C1:N ratio. Experiments with NO as the NOx component yielded very poor activities.

An engine-based test has been developed to measure the oxygen storage capacity of a catalyst. The test utilizes the difference in the engine-out and tailpipe A/F ratios following rich-to-lean and lean-to-rich A/F transitions in order to quantify the storage or release of oxygen. The technique also results in the determination of the water-gas shift constant for the tailpipe exhaust. The technique was used to measure the oxygen storage capacity of a fresh catalytic converter at inlet temperatures of 400, 500, and 600°C for catalyst volumes of 1.5L and 2.8L. The procedure was repeated after the converter had been aged at an inlet temperature of 800°C for 20, 40, and 60 hours. The oxygen storage capacities are related to the emissions performance of the converter on A/F ratio sweep tests. For the fresh converter, the calculated oxygen storage capacity increased with temperature.

A study was undertaken to evaluate the feasibility of using the catalyst exotherm to diagnose the emission performance of the catalytic converter. The exotherm was evaluated as a potential diagnostic for large volume underfloor converters as well as for small volume warmup converters. Emphasis was placed on the ability to properly diagnose the emission performance of the converters while the vehicle was driven under a variety of transient driving schedules. For this study, type K thermocouples were used for measuring the temperatures. To minimize the variability of the exotherm data during transient driving, the exotherm needs to be sampled under fairly stable exhaust flow conditions. If a transient maneuver such as an acceleration occurs, a stabilization time is required before the exotherm can be sampled. The steady-state HC conversion of underfloor catalytic converters correlated well with the exotherm measured at the rear of the catalyst over a large range of conversions.

A study was performed to assess the effects of the catalyst volume and the ceria content in the washcoat on the aged emission performance of underfloor catalytic converters containing platinum and rhodium. Catalyst volumes of 1.4 L and 2.8 L were evaluated, while the ceria level was varied from 0 to 60% of the weight of the washcoat. The concentration of noble metals (g/L) was the same for both catalyst volumes, so the larger volume also contained more noble metal. Catalyst performance was evaluated on an air/fuel ratio sweep test, at steady-state conditions on an engine, and on the FTP test. In light of the new catalyst monitoring requirements for OBD II, each catalyst was also evaluated at steady-state conditions using a dual oxygen sensor technique in order to produce an O2 sensor index. The evaluations were performed at several intermediate stages as the catalysts were aged on engines using high temperature durability schedules intended to simulate high mileage conditions.

Ceria has become an increasingly important component in automotive exhaust catalysts over the past decade. Recently, with the proposal that measurements of oxygen storage be used for the on-board evaluation of catalyst performance for both low emission vehicles (LEV) and non-LEV vehicles, understanding the role of ceria and its deterioration with catalyst aging has become even more important. It is well established that ceria in an alumina support promotes oxygen storage/release by automotive catalysts under cycled air/fuel conditions, which in turn promotes the catalyst's conversion performance under those conditions. Another benefit of ceria is its enhancement of the catalytic activity for other reactions, such as the water-gas shift reaction under rich conditions. In addition, ceria may help catalyst durability by promoting precious metal dispersion and playing some role as a stabilizer of the support.