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This paper, written in collaboration with Ford, evaluates the effectiveness of higher cell density combined with higher porosity, lower thermal mass substrates for emission control capability on a customized, RDE (Real Driving Emissions)-type of test cycle run on a chassis dynamometer using a gasoline passenger car fitted with a three-way catalyst (TWC) system. Cold-start emissions contribute most of the emissions control challenge, especially in the case of a very rigorous cold-start. The majority of tailpipe emissions occur during the first 30 seconds of the drive cycle. For the early engine startup phase, higher porosity substrates are developed as one part of the solution. In addition, further emission improvement is expected by increasing the specific surface area (GSA) of the substrate. This test was designed specifically to stress the cold start performance of the catalyst by using a short, 5 second idle time preceding an aggressive, high exhaust mass flowrate drive cycle.

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.

To meet future particle mass and particle number standards, gasoline vehicles may require particle control, either by way of an exhaust gas filter and/or engine modifications. Soot levels for gasoline engines are much lower than diesel engines; however, non-combustible material (ash) will be collected that can potentially cause increased backpressure, reduced power, and lower fuel economy. The purpose of this work was to examine the ash loading of gasoline particle filters (GPFs) during rapid aging cycles and at real time low mileages, and compare the filter performances to both fresh and very high mileage filters. Current rapid aging cycles for gasoline exhaust systems are designed to degrade the three-way catalyst washcoat both hydrothermally and chemically to represent full useful life catalysts. The ash generated during rapid aging was low in quantity although similar in quality to real time ash. Filters were also examined after a low mileage break-in of approximately 3000 km.

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 purpose of this work was to examine gasoline particle filters (GPFs) at high mileages. Soot levels for gasoline direct injection (GDI) engines are much lower than diesel engines; however, noncombustible material (ash) can cause increased backpressure, reduced power, and lower fuel economy. In this study, a post mortem was completed of two GPFs, one at 130,000 mi and the other at 150,000 mi, from two production 3.5L turbocharged GDI vehicles. The GPFs were ceramic wall-flow filters containing three-way catalytic washcoat and located downstream of conventional three-way catalysts. The oil consumption was measured to be approaching 23,000 mpqt for one vehicle and 30,000 mpqt for the other. The ash contained Ca, P, Zn, S, Fe, and catalytic washcoat. Approximately 50 wt% of the collected ash was non-lubricant derived. The filter capture efficiency of lubricant-derived ash was about 50% and the non-lubricant metal (mostly Fe) deposition rate was 0.9 to 1.2 g per 10,000 mi.

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 2005 prototype diesel aftertreatment system consisting of diesel oxidation catalysts (DOC), Cu/zeolite Selective Catalytic Reduction (SCR) catalyst, and Catalyzed Diesel Particulate Filter (CDPF) was aged to an equivalent of 120k mi on an engine dynamometer using an aging cycle that incorporated both city and highway driving modes. The program demonstrated durable reduction in particulate matter (PM) and nitrogen oxides (NOx) emissions to federal Tier 2 levels on a 6000 lbs light-duty truck application. Very low sulfur diesel fuel (∼15 ppm) enabled lower PM emissions, reduced the fuel penalty associated with the emission control system, and improved long-term system durability. A total of 643 filter regenerations occurred during the aging that raised the entire catalyst system to high temperatures on a regular basis. After testing the aged system on a 6000 lbs light-duty diesel truck, a post mortem analysis was completed on core samples taken from the DOC, SCR catalyst, and filter.

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.

Urea selective catalytic reduction (SCR) catalysts have the capability to deliver the high NOx conversion efficiencies required for future emission standards. However, the potential for the occasional over-temperature can lead to the irreversible deactivation of the SCR catalyst. On-board diagnostics (OBD) compliance requires monitoring of the SCR function to make sure it is operating properly. Initially, SCR catalyst performance metrics such as NOx conversion, NH3 oxidation, NH3 storage capacity, and BET surface area are within normal limits. However, these features degrade with high temperature aging. In this work, a laboratory flow reactor was utilized to determine the impact on these performance metrics as a function of aging condition. Upon the completion of a full time-at-temperature durability study, four performance criteria were established to help determine a likely SCR failure.

Diesel aftertreatment systems configured with a diesel oxidation catalyst (DOC) upstream of an urea selective catalytic reduction (SCR) catalyst run the risk of precious metal contamination. During active diesel particulate filter (DPF) regeneration events, the DOC bed temperature can reach up to 850°C. Under these conditions, precious metal (especially Pt) can be volatized and then deposited on a downstream SCR catalyst. In this paper, the impact of ultra-low contamination of platinum group metals (PGM) on the SCR catalyst was studied. A method based on precious metal volatilization of a Pt-rich DOC at 850°C and under lean gas conditions was employed to contaminate downstream FeSCR and CuSCR formulations. The contamination resulted in poor NOx conversion (via NOx remake) and excessive N2O formation. The precious metal volatilization method was employed to screen various Pt/Pd based DOCs to avoid contamination of the downstream FeSCR.

Passenger and light duty diesel vehicles will require up to 90% NOx conversion over the Federal Test Procedure (FTP) to meet future Tier 2 Bin 5 standards. This accomplishment is especially challenging for low exhaust temperature applications that mostly operate in the 200 - 350°C temperature regime. Selective catalytic reduction (SCR) catalysts formulated with Cu/zeolites have shown the potential to deliver this level of performance fresh, but their performance can easily deteriorate over time as a result of high temperature thermal deactivation. These high temperature SCR deactivation modes are unavoidable due to the requirements necessary to actively regenerate diesel particulate filters and purge SCRs from sulfur and hydrocarbon contamination. Careful vehicle temperature control of these events is necessary to prevent unintentional thermal damage but not always possible. As a result, there is a need to develop thermally robust SCR catalysts.

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.

This paper presents the development of an analytical model that complements laboratory based experiments to provide a tool for Selective Catalyst Reduction (SCR) applications. The model calibration is based on measured data from NOx reduction performance tests as well as ammonia (NH3) adsorption/desorption tests over select SCR catalyst formulations in a laboratory flow reactor. Only base metal/zeolite SCR samples were evaluated. Limited validations are presented that show the model agrees well with vehicle data from Environmental Protection Agency Federal Test Procedure (EPA FTP) emission assessments. The model includes energy and mass balances, several different NH3 reactions with NOx, NH3 adsorption and desorption algorithms, and NH3 oxidation.

The use of urea-based selective catalytic reduction (SCR) is a promising method for achieving U.S. Tier 2 diesel emission standards for NOx. To meet the Tier 2 standards for Particulate Matter (PM), a catalyzed diesel particulate filter (CDPF) will likely be present and any ammonia (NH3) that is not consumed over an SCR catalyst would pass over the CDPF to make nitrous oxide (N2O) emissions and/or oxides of nitrogen (NOx), or exit the exhaust system as NH3. N2O is undesirable due to its high greenhouse gas potential, while NOx production from the slipped NH3 would reduce overall system NOx conversion efficiency. This paper reviews certain conditions where NH3 slip past an SCR system may be a concern, looks at what would happen to this slipped NH3 over a CDPF, and evaluates the performance of various supplier NH3 slip catalysts under varied space velocities, temperatures and concentrations of NH3 and NOx.

Urea-based Selective Catalytic Reduction (SCR) has the potential to meet U.S. Diesel Tier 2 Bin 5 emission standards for NOx in 2010. The operating and driving conditions of light-duty and heavy-duty vehicles make it necessary to customize catalyst features to the application. This paper reviews the selection of SCR catalyst technology for the U.S. and the appropriate aging and poisoning protocols for current supplier SCR catalysts. Generally, light-duty applications require SCR catalysts to function well at low temperature whereas heavy-duty applications require functionality at high temperature and high space velocity. One main durability requirement of SCR formulations involves withstanding the high temperature process of regenerating particulate filters from accumulated soot. Unrefined engine exhaust temperature control coupled with the inexact temperature measurement may also expose SCR catalysts to additional over-temperature conditions.