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Diesel particulate filters are designed to reduce the mass emissions of diesel particulate matter and have been proven to be effective in this respect. Not much is known, however, about their effects on other unregulated chemical species. This study utilized source dilution sampling techniques to evaluate the effects of a catalyzed diesel particulate filter on a wide spectrum of chemical emissions from a heavy-duty diesel engine. The species analyzed included both criteria and unregulated compounds such as particulate matter (PM), carbon monoxide (CO), hydrocarbons (HC), inorganic ions, trace metallic compounds, elemental and organic carbon (EC and OC), polycyclic aromatic hydrocarbons (PAHs), and other organic compounds. Results showed a significant reduction for the emissions of PM mass, CO, HC, metals, EC, OC, and PAHs.

The effect of the ring pack storage mechanism on the hydrocarbon (HC) emissions from an air-cooled utility engine has been studied using a simplified ring pack model. Tests were performed for a range of engine load, two engine speeds, varied air-fuel ratio and with a fixed ignition timing using a homogeneous, pre-vaporized fuel mixture system. The integrated mass of HC leaving the crevices from the end of combustion (the crank angle that the cumulative burn fraction reached 90%) to exhaust valve closing was taken to represent the potential contribution of the ring pack to the overall HC emissions; post-oxidation in the cylinder will consume some of this mass. Time-resolved exhaust HC concentration measurements were also performed, and the instantaneous exhaust HC mass flow rate was determined using the measured exhaust and cylinder pressure.

The performance of a commercial Cu-zeolite SCR catalyst after differing degrees of hydrothermal aging (aged for 72 hours at 500, 700 and 800°C with 10% moisture balanced with air) was studied by spatially resolving different key reactions using gas-phase FTIR measurements. Gases were sampled along a channel at different positions and analyzed using FTIR, which overcomes the interference of water and nitrogen on ammonia concentration detection encountered in standard mass spectrometer-based spatial resolution measurements. The NO:NO₂ concentration ratio was changed so that the standard (NO:NO₂ = 1:0), fast (NO:NO₂ = 1:1) and NO₂ (NO:NO₂ = 0:1) SCR reactions could be investigated as a function of the catalyst's hydrothermal aging extent. In addition, the effects of hydrothermal aging on the activity of NH₃ and NO oxidation were also investigated. Hydrothermal aging had little effect on NO oxidation activity.

On-vehicle proof-of-concept testing was conducted to evaluate the ability of the dual oxygen sensor catalyst evaluation method to identify serious losses in catalyst efficiency under actual vehicle operating conditions. The dual oxygen sensor method, which utilizes a comparison between an upstream oxygen sensor and an oxygen sensor placed downstream of the catalyst, was initially studied by the Environmental Protection Agency (EPA) under steady-state operating conditions on an engine dynamometer and reported in Clemmens, et al. (1).* At the time that study was released, questions were raised as to whether the technological concepts developed on a test fixture could be transferred to a vehicle operating under normal transient conditions.

Unique silver/alumina (Ag-Al₂O₃) catalysts developed using high-throughput discovery techniques in collaboration with BASF Corporation were investigated at General Motors Corporation under simulated lean-burn engine exhaust feed conditions for the selective catalytic reduction of NOx using hydrocarbons (HC-SCR). Hydrocarbon mixtures were used as the reductant to model the multi-component nature of diesel fuel and gasoline. Previous work has shown promising HC-SCR results in both laboratory reactor and engine dynamometer testing. This report investigates several aspects of HC-SCR catalyst durability, including thermal durability, sulfur tolerance, and hydrocarbon deactivation.

Although turbocharging can extend the high load limit of low temperature combustion (LTC) strategies such as reactivity controlled compression ignition (RCCI), the low exhaust enthalpy prevalent in these strategies necessitates the use of high exhaust pressures for improving turbocharger efficiency, causing high pumping losses and poor fuel economy. To mitigate these pumping losses, the divided exhaust period (DEP) concept is proposed. In this concept, the exhaust gas is directed to two separate manifolds: the blowdown manifold which is connected to the turbocharger and the scavenging manifold that bypasses the turbocharger. By separately actuating the exhaust valves using variable valve actuation, the exhaust flow is split between two manifolds, thereby reducing the overall engine backpressure and lowering pumping losses. In this paper, results from zero-dimensional and one-dimensional simulations of a multicylinder RCCI light-duty engine equipped with DEP are presented.

The United States Environmental Protection Agency (U.S. EPA) National Enforcement Investigations Center (NEIC) has developed a test method for the analysis of washcoat material in small engine catalytic converters. Each small engine catalytic converter contains a metallic monolith. Each metallic monolith is removed from its outer casing, manually disassembled, and then separated into washcoat and substrate. The washcoat material is analyzed for platinum group metals (PGMs) using X-ray fluorescence (XRF) spectrometry. Results from the XRF analysis are used to calculate PGM ratios in the washcoat. During monolith disassembly, care is taken to minimize loss of washcoat or substrate, but some material is inevitably lost. The recovered washcoat mass does not necessarily equal the quantity of washcoat that was present in the intact catalytic converter.

A unique catalyst developed using high-throughput discovery techniques in collaboration with BASF Corporation and Accelrys, Inc. was investigated at General Motors under simulated diesel engine exhaust feed conditions for the selective catalytic reduction of NOx. A hydrocarbon mixture was used as the reductant to model the multi-component nature of diesel fuel and the catalyst was evaluated over a wide range of temperatures (150 - 550°C) relevant to light-duty diesel exhaust. This report investigates the effects of NOx (as NO or NO2), hydrocarbon concentration level (HC:NOx ratio), oxygen concentration, NO concentration, catalyst space velocity, catalyst temperature, and the co-presence of hydrogen on steady-state NOx reduction activity. Using these results, a control strategy was developed to maximize NOx conversion over the wide-ranging exhaust conditions likely to be encountered in light-duty diesel applications.

An experimental study was performed to investigate diesel particulate filter (DPF) performance during filtration with the use of real-time measurement equipment. Three operating conditions of a single-cylinder 2.3-liter D.I. heavy-duty diesel engine were selected to generate distinct types of diesel particulate matter (PM) in terms of chemical composition, concentration, and size distribution. Four substrates, with a range of geometric and physical parameters, were studied to observe the effect on filtration characteristics. Real-time filtration performance indicators such as pressure drop and filtration efficiency were investigated using real-time PM size distribution and a mass analyzer. Types of filtration efficiency included: mass-based, number-based, and fractional (based on particle diameter). In addition, time integrated measurements were taken with a Rupprecht & Patashnick Tapered Element Oscillating Microbalance (TEOM), Teflon and quartz filters.

Three distinct types of diesel particulate matter (PM) are generated in selected engine operating conditions of a single-cylinder heavy-duty diesel engine. The three types of PM are trapped using typical Cordierite diesel particulate filters (DPF) with different washcoat formulations and a commercial Silicon-Carbide DPF. Two systems, an external electric furnace and an in-situ burner, were used for regeneration. Furnace regeneration experiments allow the collected PM to be classified into two categories depending on oxidation mechanism: PM that is affected by the catalyst and PM that is oxidized by a purely thermal mechanism. The two PM categories prove to contribute differently to pressure drop and transient filtration efficiency during in-situ regeneration.

In 2005, the United States Environmental Protection Agency (EPA) and Southwest Research Institute (SwRI) embarked on a mission to help the city of Beijing, China, clean its air. Working with the Beijing Environmental Protection Bureau (BEPB), the effort was a pilot diesel retrofit demonstration program involving three basic retrofit technologies to reduce particulate matter (PM). The three basic technologies were the diesel oxidation catalyst (DOC), the flowthrough diesel particulate filter (FT-DPF), and the wallflow diesel particulate filter (WF-DPF). The specific retrofit systems selected for the project were verified through the California Air Resources Board (CARB) or the EPA verification protocol [1]. These technologies are generally verified for PM reductions of 20-40 percent for DOCs, 40-50 percent for the FT-DPF, and 85 percent or more for the high efficiency WF-DPF.

The two most common NOx reducing technologies, in an oxygen abundant exhaust stream, are urea selective catalytic reduction urea-SCR and lean NOx trap (LNT) catalysts. Each technology has advantages and disadvantages. Another selective catalytic reduction (SCR) catalyst that uses hydrocarbons (HC-SCR), specifically diesel fuel, as the reductant to reduce NOx emissions was investigated. This catalyst is a result of a high throughput discovery project and conducted in cooperation with BASF, Accelrys and funded by the Department of Energy (DOE.) Several full size 5.0L monolith catalysts were made and evaluated using a V6 turbo charged diesel engine connected to a dynamometer running light-duty transient test cycles. The NOx efficiency on the HWYFET and US06 tests were measured to be 92% and 76% respectively. The FTP was 60% on a weighted basis.

Homogeneous Charge Compression Ignition (HCCI) combustion is known for its significant fuel economy benefit with near-zero NOx and particulate emissions. Stable HCCI combustion relies on a well-controlled temperature and composition of the cylinder charge at the intake valve closing that in turn requires a precise coordination of all engine inputs. In this paper, the HCCI combustion is realized by retaining hot residual from the previous combustion event using the recompression valve strategy. The recompression valve strategy closes the exhaust valves before the top dead center and opens the intake valves at an angle symmetric to the exhaust valve closing. Depending on the engine load, different valve open/close timings with respect to the crank position are used to trap different amounts of residual gases. It is critical to coordinate the change in the valve open/close timings with the change in the injected fuel quantity during load transients in order to maintain stable combustion.

At the current state of diesel engine technology, all diesel engines require some sort of NOx control device to comply with Tier II Bin 5 light-duty or 2010 heavy-duty NOx emission standards. Selective Catalytic Reduction of NOx with hydrocarbons (HC-SCR) to reduce NOx from diesel exhaust emissions is an attractive technology for lean NOx control, especially when diesel fuel is used as the reductant. However, it has been reported that when diesel fuel is used as the reductant catalyst deactivation occurred. Even though this kind of deactivation is reversible at high enough temperatures, it is a deficiency that needs to be overcome for the successful implementation of the technology. We studied the HC-SCR catalyst deactivation using diesel fuel as the reductant. The variables investigated included catalyst temperature, HC:NOx ratio, NOx concentration, and space velocity. The results showed that one single parameter can be used to measure the catalyst deactivation: the HC-SCR activity.

To comply with Tier II Bin 5 light-duty or 2010 heavy-duty NOx emission standards, all diesel engines require some sort of NOx control device. Selective Catalytic Reduction of NOx with hydrocarbons (HC-SCR) to reduce NOx from diesel exhaust emissions is an attractive technology for lean NOx control, especially when diesel fuel is used as the reductant. However, it has been reported that when diesel fuel is used as the reductant catalyst deactivation occurred (1). In a companion paper, we demonstrated that the HC-deactivation is caused by the mismatch of the adsorption and desorption processes of either the reactants or the products of a normal SCR reaction (2). In this paper, we probe the nature of the catalyst deactivation with various reductants. Both hydrocarbons and oxygenates were used as the reductants. The deactivation or the mismatch in adsorption and desorption rates is molecular size or chain length dependent.

A unique silver/alumina selective catalytic reduction (SCR) catalyst which used hydrocarbons (HC-SCR) to reduce NOx emissions was investigated. Diesel fuel or ethanol were used as the reductants to evaluate catalyst performance. Several full size 5.0L monolith 2.0 and 3.0 wt.% Ag2O-Al2O3 catalysts were created. Testing was conducted using a 6.6L Duramax turbocharged heavy duty diesel engine. Dynamometer testing on the heavy duty FTP and SET 13 transient test cycles was conducted. The NOx conversion efficiency was evaluated as a function of catalyst volume, inlet cone angle, hydrocarbon to NOx ratio (HC:NOx), and space velocity. Oxygen effects on the NOx reaction and the HC slip past the HC-SCR catalyst were also determined. An FTIR was used to evaluate unregulated emissions. Testing on the heavy duty FTP and SET 13 test cycles, with diesel fuel as the reductant, resulted in a 60% and 65% NOx conversion reduction respectively.

One way to achieve low temperature regeneration on diesel particulate traps is to employ NO2 as the oxidant. However, the engine may not produce sufficient NOx to achieve the required particulate regeneration. An RRT (rolling regeneration trap) was proposed as a way to enhance the effective concentration in diesel engine exhaust. The RRT uses catalyzed ceramic foam, which allows repeated use of existing NOx in the exhaust stream. The ceramic foam is a filter itself: thus, it can reduce the particulate loading on the wall-flow filter, which is more prone to plugging by the particulate deposits. Furthermore, the presence of particulate matter in the catalyzed section circumvents the high temperature limit imposed by thermodynamic equilibrium of a simple NO+NO2 +O2 system. However, experimental results revealed that the regeneration efficiency on the wall-flow section was very low and NO2 slip is an issue.

The steady-state reduction of NOx at temperatures between 150-300°C has been investigated under simulated lean-burn conditions using a two-stage transient flow reactor system consisting of non-thermal plasma in combination with a sodium Y zeolite catalyst. Reactivity comparisons were made with and without plasma operation in order to identify the plasma-generated hydrocarbon species necessary for the selective catalytic reduction (SCR) of NOx. With propene as the hydrocarbon in the feed, NO is completely oxidized to NO2 in the plasma and the formation of oxidized carbon-containing species include formaldehyde, acetaldehyde, carbon monoxide, carbon dioxide, and methanol. Fourier transform infrared (FTIR) measurements indicate a close carbon balance between plasma inlet and outlet gas feed concentrations, signifying the major species have been identified.

The use of a partial flow sampling system (PFSS) to measure nonroad steady-state diesel engine particulate matter (PM) emissions is a technique for certification approved by a number of regulatory agencies around the world including the US EPA. Recently, there have been proposals to change future nonroad tests to include testing over a nonroad transient cycle. PFSS units that can quantify PM over the transient cycle have also been discussed. The full flow constant volume sampling (CVS) technique has been the standard method for collecting PM under transient engine operation. It is expensive and requires large facilities as compared to a typical PFSS. Despite the need for a cheaper alternative to the CVS, there has been a concern regarding how well the PM measured using a PFSS compared to that measured by the CVS. In this study, three PFSS units, including AVL SPC, Horiba MDLT, and Sierra BG-2 were investigated in parallel with a full flow CVS.

A single cylinder, Cummins NH, direct-injection, diesel engine has been operated in order to evaluate the effects of aromatic content and aromatic structure on diesel engine particulates. Results from three fuels are shown. The first fuel, a low sulfur Chevron diesel fuel was used as a base fuel for comparison. The other fuels consisted of the base fuel and 10% by volume of 1-2-3-4 tetrahydronaphthalene (tetralin) a single-ring aromatic and naphthalene, a double-ring aromatic. The fuels were chosen to vary aromatic content and structure while minimizing differences in boiling points and cetane number. Measurements included exhaust particulates using a mini-dilution tunnel, exhaust emissions including THC, CO2, NO/NOx, O2, injection timing, two-color radiation, soluble organic fraction, and cylinder pressure. Particulate measurements were found to be sensitive to temperature and flow conditions in the mini-dilution tunnel and exhaust system.