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A combination of laboratory reactor measurements and vehicle FTP testing has been combined to demonstrate a method for diagnosing the formation of NO2 from a diesel oxidation catalyst (DOC). Using small cores from a production DOC and simulated diesel exhaust, the laboratory reactor experiments are used to support a model for DOC chemical reaction kinetics. The model we propose shows that the ability to produce NO2 is chemically linked to the ability of the catalyst to oxidize hydrocarbon (HC). For thermally damaged DOCs, loss of the HC oxidation function is simultaneous with loss of the NO2 production function. Since HC oxidation is the source of heat generated in the DOC under regeneration conditions, we conclude that a diagnostic of the DOC exotherm is able to detect the failure of the DOC to produce NO2. Vehicle emissions data from a 6.6 L Duramax HD pick-up with DOC of various levels of thermal degradation is provided to support the diagnostic concept.

Engine and flow reactor experiments were conducted to determine the impact of biodiesel relative to ultra-low-sulfur diesel (ULSD) on inhibition of the selective catalytic reduction (SCR) reaction over an Fe-zeolite catalyst. Fe-zeolite SCR catalysts have the ability to adsorb and store unburned hydrocarbons (HC) at temperatures below 300°C. These stored HCs inhibit or block NOx-ammonia reaction sites at low temperatures. Although biodiesel is not a hydrocarbon, similar effects are anticipated for unburned biodiesel and its organic combustion products. Flow reactor experiments indicate that in the absence of exposure to HC or B100, NOx conversion begins at between 100° and 200°C. When exposure to unburned fuel occurs at higher temperatures (250°-400°C), the catalyst is able to adsorb a greater mass of biodiesel than of ULSD. Experiments show that when the catalyst is masked with ULSD, NOx conversion is inhibited until it is heated to 400°C.

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.

Effects of fuel cell material properties on water management were numerically investigated using Volume of Fluid (VOF) method in the FLUENT. The results show that the channel surface wettability is an important design variable for both serpentine and interdigitated flow channel configurations. In a serpentine air flow channel, hydrophilic surfaces could benefit the reactant transport to reaction sites by facilitating water transport along channel edges or on channel surfaces; however, the hydrophilic surfaces would also introduce significantly pressure drop as a penalty. For interdigitated air flow channel design, it is observable that liquid water exists only in the outlet channel; it is also observable that water distribution inside GDL is uneven due to the pressure distribution caused by interdigitated structure. An in-situ water measurement method, neutron imaging technique, was used to investigate the water behavior in a PEM fuel cell.

Gasoline turbocharged direct injection (GTDI) engines, such as EcoBoost™ from Ford, are becoming established as a high value technology solution to improve passenger car and light truck fuel economy. Due to their high specific performance and excellent low-speed torque, improved fuel economy can be realized due to downsizing and downspeeding without sacrificing performance and driveability while meeting the most stringent future emissions standards with an inexpensive three-way catalyst. A logical and synergistic extension of the EcoBoost™ strategy is the use of E85 (approximately 85% ethanol and 15% gasoline) for knock mitigation. Direct injection of E85 is very effective in suppressing knock due to ethanol's high heat of vaporization - which increases the charge cooling benefit of direct injection - and inherently high octane rating. As a result, higher boost levels can be achieved while maintaining optimal combustion phasing giving high thermal efficiency.

This study extends research previously reported from our laboratory [SAE 2009-01-0285] on diesel NOx control utilizing a new generation of Lean NOx Trap (LNT) plus in-situ Selective Catalytic Reduction (SCR) catalyst systems. Key findings from this work include 1) evidence for a “non-ammonia” reduction pathway over the SCR catalyst (in addition to the conventional ammonia pathway), 2) high NOx conversions utilizing LNT formulations with substantially lower platinum group metal (PGM) loadings than utilized in earlier systems, 3) ability of the downstream SCR catalyst to maintain high overall system NOx efficiency with aged LNTs, and 4) effectiveness of both Cu- and Fe-zeolite SCR formulations to enhance overall system NOx efficiency. FTP NOx conversion efficiencies in excess of 95% were obtained on two light-duty vehicle platforms with lab-aged catalyst systems, thus showing potential of the LNT+SCR approach for achieving the lowest U.S. emissions standards

Aftertreatment system design involves multiple tradeoffs between engine performance, fuel economy, regulatory emission levels, packaging, and cost. Selection of the best design solution (or “architecture”) is often based on an assumption that inherent catalyst activity is unaffected by location within the system. However, this study acknowledges that catalyst activity can be significantly impacted by location in the system as a result of varying thermal exposure, and this in turn can impact the selection of an optimum system architecture. Vehicle experiments with catalysts aged over a range of mild to moderate to severe thermal conditions that accurately reflect select locations on a vehicle were conducted on a chassis dynamometer. The vehicle test data indicated CO and NOx could be minimized with a catalyst placed in an intermediate location.

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.

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.

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.

In this paper, a model-based linear estimator and a non-linear control law for an Fe-zeolite urea-selective catalytic reduction (SCR) catalyst for heavy duty diesel engine applications is presented. The novel aspect of this work is that the relevant species, NO, NO2 and NH3 are estimated and controlled independently. The ability to target NH3 slip is important not only to minimize urea consumption, but also to reduce this unregulated emission. Being able to discriminate between NO and NO2 is important for two reasons. First, recent Fe-zeolite catalyst studies suggest that NOx reduction is highly favored by the NO 2 based reactions. Second, NO2 is more toxic than NO to both the environment and human health. The estimator and control law are based on a 4-state model of the urea-SCR plant. A linearized version of the model is used for state estimation while the full nonlinear model is used for control design.

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.

This paper discusses the poisoning of a selective catalytic reduction (SCR) catalyst by trace levels of platinum originating from an upstream diesel oxidation catalyst (DOC). A diesel aftertreatment system consisting of a DOC, urea based SCR Catalyst and a DPF was aged and evaluated on a 6.4 liter diesel engine dynamometer. The SCR catalyst system consisted of an Fe-zeolite catalyst followed by a Cu-zeolite catalyst. After approximately 400 hours of engine operation at varied exhaust flow rates and temperatures, deactivation of the SCR catalyst was observed. A subsequent detailed investigation revealed that the Cu catalyst was not deactivated and the front half of the Fe-based catalyst showed severe deactivation. The deactivated portion of the catalyst showed high activity of NH3 conversion to NOx and N2O formation. The cause of the deactivation was identified to be the presence of trace Pt contamination.

Compact heat exchangers are commonly used in diesel engines to reduce the temperature of recirculated exhaust gases, resulting in decreased NOx emissions. These exhaust gas recirculation (EGR) coolers experience fouling through deposition of particulate matter (PM) and hydrocarbons (HCs) that reduces the effectiveness of the cooler. Surrogate tubes have been used to investigate the impacts of gas flow rate and coolant temperature on the deposition of PM and HCs. The results indicate that mass deposition is lowest at high flow rates and high coolant temperatures. An oxidation catalyst was investigated and proved to effectively reduce deposition of HCs, but did not reduce overall mass deposition to near-zero levels. Speciation of the deposit HCs showed that a range of HCs from C15 - C25 were deposited and retained in the surrogate tubes.

The buildup of deposits in EGR coolers causes significant degradation in heat transfer performance, often on the order of 20-30%. Deposits also increase pressure drop across coolers and thus may degrade engine efficiency under some operating conditions. It is unlikely that EGR cooler deposits can be prevented from forming when soot and HC are present. The presence of cooled surfaces will cause thermophoretic soot deposition and condensation of HC and acids. While this can be affected by engine calibration, it probably cannot be eliminated as long as cooled EGR is required for emission control. It is generally felt that “dry fluffy” soot is less likely to cause major fouling than “heavy wet” soot. An oxidation catalyst in the EGR line can remove HC and has been shown to reduce fouling in some applications. The combination of an oxidation catalyst and a wall-flow filter largely eliminates fouling. Various EGR cooler designs affect details of deposit formation.

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.

Diesel NOx emissions control utilizing combined Lean NOx Trap (LNT) and so-called passive or in-situ Selective Catalytic Reduction (SCR) catalyst technologies (i.e. with reductant species generated by the LNT) has been the subject of several previous papers from our laboratory [ 1 - 2 ]. The present study focuses on hydrocarbon (HC) emissions control via the same LNT+SCR catalyst technology under FTP driving conditions. HC emissions control can be as challenging as NOx control under both current and future federal and California/Green State emission standards. However, as with NOx control, the combined LNT+SCR approach offers advantages for HC emission control over LNT-only aftertreatment. The incremental conversion obtained with the SCR catalyst is shown, both on the basis of vehicle and laboratory tests, to result primarily from HC adsorbed on the SCR catalyst during rich LNT purges that reacts during subsequent lean engine operation.

Internal combustion (IC) engines fueled by hydrogen are among the most efficient means of converting chemical energy to mechanical work. The exhaust has near-zero carbon-based emissions, and the engines can be operated in a manner in which pollutants are minimal. In addition, in automotive applications, hydrogen engines have the potential for efficiencies higher than fuel cells.[1] In addition, hydrogen engines are likely to have a small increase in engine costs compared to conventionally fueled engines. However, there are challenges to using hydrogen in IC engines. In particular, efficient combustion of hydrogen in engines produces nitrogen oxides (NOx) that generally cannot be treated with conventional three-way catalysts. This work presents the results of experiments which consider changes in direct injection hydrogen engine design to improve engine performance, consisting primarily of engine efficiency and NOx emissions.

During the course of emissions and fuel economy (FE) testing, vehicles that are calibrated to meet Tier 3 emissions requirements currently must demonstrate compliance on Tier 3 E10 fuel while maintaining emissions capability with Tier 2 E0 fuel used for FE label determination. Tier 3 emissions regulations prescribe lower sulfur E10 gasoline blends for the U.S. market. Tier 3 emissions test fuels specified by EPA are required to contain 9.54 volume % ethanol and 8-11 ppm sulfur content. EPA Tier 2 E0 test fuel has no ethanol and has nominal 30 ppm sulfur content. Under Tier 3 rules, Tier 2 E0 test fuel is still used to determine FE. Tier 3 calibrations can have difficulty meeting low Tier 3 emissions targets while testing with Tier 2 E0 fuel. Research has revealed that the primary cause of the high emissions is deactivation of the aftertreatment system due to sulfur accumulation on the catalysts.