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Four-way, integrated, diesel emission control systems that combine selective catalytic reduction for NOx control with a continuously regenerating trap to remove diesel particulate matter were evaluated under real-world, on-road conditions. Tests were conducted using a semi-tractor with an emissions year 2000, 6-cylinder, 12 L, Volvo engine rated at 287 kW at 1800 rpm and 1964 N-m. The emission control system was certified for retrofit application on-highway trucks, model years 1994 through 2002, with 4-stroke, 186-373 kW (250-500 hp) heavy-duty diesel engines without exhaust gas recirculation. The evaluations were unique because the mobile laboratory platform enabled evaluation under real-world exhaust plume dilution conditions as opposed to laboratory dilution conditions. Real-time plume measurements for NOx, particle number concentration and size distribution were made and emission control performance was evaluated on-road.

Advances in aftertreatment technologies, such as Diesel Particulate Filters (DPF) and Selective Catalytic Reduction (SCR) catalysts, have responded to increasingly stringent PM and NO requirements for diesel engines. Potentially viable SCR materials include copper and iron zeolite, which possess high thermal durabilities and conversion efficiencies. However, concern exists over the metal-catalyzed synthesis of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs), especially since typical SCR operating temperatures overlap with optimal PCDD/F formation from the de novo and precursor mechanisms. Due to the lack of standardized testing methodology for measuring PCDD/F emissions from mobile sources, this study adapted EPA methods 0023A and TO-9A from their original applications of industrial stack and ambient air sampling.

Ammonia oxidation (AMOX) catalysts are critical parts of most diesel aftertreatment systems around the world. These catalysts are positioned downstream of selective catalytic reduction (SCR) catalysts and remove unreacted NH3 that passes through the SCR catalyst. In many configurations, the AMOX catalyst is situated after a diesel oxidation catalyst and catalyzed diesel particulate filter that oxidize CO and hydrocarbons. However, in Euro V and proposed Tier 4 final aftertreatment architectures there is no upstream oxidation catalyst. In this study, the impact of hydrocarbons is evaluated on two different types of AMOX catalysts. One has dual washcoat layers-SCR washcoat on top of PGM washcoat-and the other has only a PGM washcoat layer. Results are presented for NH3 and hydrocarbon oxidation, NOx and N2O selectivity, and hydrocarbon storage. The AMOX findings are rationalized in terms of their impact on the individual oxidation and SCR functions.

Lean-burn natural gas (NG) engines are used world-wide for both stationary power generation and mobile applications ranging from passenger cars to Class 8 line-haul trucks. With the recent introduction of hydraulic fracturing gas extraction technology and increasing availability of natural gas, these engines are receiving more attention. However, the reduction of unburned hydrocarbon emissions from lean-burn NG and dual-fuel (diesel and natural gas) engines is particularly challenging due to the stability of the predominant short-chain alkane species released (e.g., methane, ethane, and propane). Supported Pd-based oxidation catalysts are generally considered the most active materials for the complete oxidation of low molecular weight alkanes at temperatures typical of lean-burn NG exhaust. However, these catalysts rapidly degrade under realistic exhaust conditions with high water vapor concentrations and traces of sulfur.

The oxidation of short-chain alkanes, such as methane, ethane, and propane, from the exhaust of lean-burn natural gas and lean-burn dual-fuel (natural gas and diesel) engines poses a unique challenge to the exhaust aftertreatment community. Emissions of these species are currently regulated by the US Environmental Protection Agency (EPA) as either methane (Greenhouse Gas Emissions Standards) or non-methane hydrocarbon (NMHC). However, the complete catalytic oxidation of short-chain alkanes is challenging due to their thermodynamic stability. The present study focuses on the oxidation of short-chain alkanes by vanadium-based and Cu/zeolite selective catalytic reduction (SCR) catalysts, generally utilized to control NOx emissions from lean-burn engines. Results reveal that these catalysts are active for short-chain alkane oxidation, albeit, at conversions lower than those generally reported in the literature for Pd-based catalysts, typically used for short-chain alkane conversion.

Low-temperature (T ≤ 200°C) NOx conversion is receiving increasing research attention due to continued potential reductions in regulated NOx emissions from diesel engines. At these temperatures, ammonium salts (e.g., ammonium nitrate, ammonium (bi)sulfate, etc.) can form as a result of interactions between NH3 and NOx or SOx, respectively. The formation of these salts can reduce the availability of NH3 for NOx conversion, block active catalyst sites, and result in the formation of N2O, a regulated Greenhouse Gas (GHG). In this study, we investigate the effect of hydrothermal aging on the formation and decomposition of ammonium nitrate on a state-of-the-art Cu/zeolite selective catalytic reduction (SCR) catalyst. Reactor-based constant-temperature ammonium nitrate formation, temperature programmed oxidation (TPO), and NO titration experiments are used to characterize the effect of hydrothermal aging from 600 to 950°C.

Nitrous oxide (N2O), with a global warming potential (GWP) of 297 and an average atmospheric residence time of over 100 years, is an important greenhouse gas (GHG). In recognition of this, N2O emissions from on-highway medium- and heavy-duty diesel engines were recently regulated by the US Environmental Protection Agency (EPA) and National Highway Traffic Safety Administration’s (NHTSA) GHG Emission Standards. Unlike NO and NO2, collectively referred to as NOx, N2O is not a major byproduct of diesel combustion. However, N2O can be formed as a result of unselective catalytic reactions in diesel aftertreatment systems, and the mitigation of this unintended N2O formation is a topic of active research. In this study, a nonroad Tier 4 Final/Stage IV engine was equipped with a vanadium-based selective catalytic reduction (SCR) aftertreatment system. Experiments were conducted over nonroad steady and both cold and hot transient cycles (NRSC and NRTC, respectively).

Studies have shown that there are a significant number of chemical species present in engine exhaust particulate matter emissions. Additionally, the majority of current world-wide regulatory methods for measuring engine particulate emissions are gravimetrically based. As modern engines considerably reduce particulate mass emissions, these methods become less stable and begin to display higher levels of measurement uncertainty. In this study, a characterization of mass emissions from three heavy-duty diesel engines, with a range of particulate emission levels, was made in order to gain a better understanding of the variability and uncertainty associated with common mass measurement methods, as well as how well these methods compare with each other. Two gravimetric mass measurement methods and a reconstructed mass method were analyzed as part of the present study.

A 1.9 liter Volkswagen TDI engine has been modified to accomodate the addition of hydrogen into the intake manifold via timed port fuel injection. Engine out particulate matter and the emissions of oxides of nitrogen were investigated. Two fuels,low sulfur diesel fuel (BP50) and soy methyl ester (SME) biodiesel (B99), were tested with supplemental hydrogen fueling. Three test conditions were selected to represent a range of engine operating modes. The tests were executed at 20, 40, and 60 % rated load with a constant engine speed o 1700 RPM. At each test condition the percentage of power from hydrogen energy was varied from 0 to 40 %. This corresponds to hydrogen flow rates ranging from 7 to 85 liters per minute. Particulate matter (PM) emissions were measured using a scaning mobility particle sizer (SMPS) and a two stage micro dilution system. Oxides of nitrogen were also monitored.

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.

This study analyzed the impact of transient and multi-mode engine conditions on emissions of dioxins and furans from a variety of diesel aftertreatment configurations. Exhaust aftertreatment systems included combinations of diesel oxidation catalyst, diesel particulate filter, and either Cu/zeolite or Fe/zeolite selective catalytic reduction catalyst. EPA method TO-9A was modified for proportional exhaust gas sampling, whereas EPA method 0023A was modified for raw exhaust gas sampling. Dioxin and furan emissions were first measured with modified method TO-9A during Federal Test Procedure transient cycles, but no toxic dioxins or furans were detected. Measurements were then taken with modified method 0023A during Ramped Mode Cycles-Supplemental Emissions Test experiments. Because more rigorous pre-cleaning and sample extraction procedures were used with this method and lower detection limits were achieved by the analytical laboratory, some dioxin and furan congeners were detected.

Titanium dioxide supported vanadium oxide catalysts have been successfully utilized for the selective catalytic reduction (SCR) of nitrogen oxides emitted from both stationary and mobile sources. Because of their cost and performance advantages in certain applications, vanadium-based SCR catalysts are now also being considered for integration into some U.S. Tier IV off-highway aftertreatment systems. However, concern exists that toxic vanadium compounds, such as vanadium pentoxide, could be released from these catalysts as a result of mechanical attrition or high temperature volatility. An experimental study has been conducted to compare various techniques for measuring the release of particle and vapor-phase vanadium from SCR catalysts. Previous research has utilized a powder reactor-based method to measure the vapor-phase release of vanadium, but there are inherent limitations to this technique.

The use of a corona-less electrostatic precipitator as a collection and agglomeration device for diesel soot has been investigated. It collects and grows diesel particles which are emitted in the submicron diameter range and grow into much larger particles. These larger particles may then be collected with a relatively simple inertial device. Previous testing of a full scale precipitator designed for a Caterpillar 3304 engine showed that the reduction in sub-micron sized mass from the engine was roughly 30 to 40%. Greater reductions were desired. A sub-scale electrostatic agglomerator was built to analyze in greater detail the behavior of an existing full scale device. Tests were designed to determine; the charged fraction of the particles from the engine used, the collection efficiency of the electrostatic agglomerator, the effect of geometry on collection efficiency, and the size distribution of the particles reentrained after electrostatic collection.

A study of the sources of variability in particulate measurements using the Heavy-Duty Transient Test (40 CFR Subpart N) has been conducted. It consisted of several phases: a critical examination of the test procedures, visits to representative facilities to compare and contrast facility designs and test procedures, and development of a simplified model of the systems and procedures used for the Heavy-Duty Transient Test. Some of the sources of variability include; thermophoretic deposition of particulate matter onto walls of the sampling system followed by subsequent reentrainment in an unpredictable manner, the influence of dilution and cooling upon the soluble organic fraction, inconsistency among laboratories in the engine and dynamometer control strategies, and errors in measurements of flows into and out of the secondary dilution tunnel.

Soot is the largest component of contaminants found in the diesel engine lubricating oil. The soot enters lubricating oil mainly through thermophoretic deposition on the cylinder wall. Although the mechanism is still not fully understood, it is generally accepted that soot particles promote engine wear, reducing engine component service life, fuel efficiency and performance. This problem will be further exacerbated when more and more diesel engines use EGR to reduce NOx emissions and when lubricating oil consumption is drastically reduced to control particulate emissions. In this study, lubricating oil samples were taken from 7 different operating diesel engines. The size distribution and concentration of the diesel soot particles in the lubricants were investigated by methods of photosedimentation and quantitative spectrophotometry. The size distributions were compared to those of soot particles in the exhaust.

Natural gas-powered engines are widely used due to their low fuel cost and in general their lower emissions than conventional diesel engines. In order to comply with emissions regulations, an aftertreatment system is utilized to treat exhaust from natural gas engines. Stoichiometric burn natural gas engines use three-way catalyst (TWC) technology to simultaneously remove NOx, CO, and hydrocarbon (HC). Removal of methane, one of the major HC emissions from natural gas engines, is difficult due to its high stability, posing a challenge for existing TWC technologies. In this work, degreened (DG), standard bench cycle (SBC)-aged TWC catalysts and a DG Pd-based oxidation catalyst (OC) were evaluated and compared under a variety of lean/rich gas cycling conditions, simulating stoichiometric natural gas engine emissions.

Light absorbing components of aerosols, often called black carbon (BC), are emitted from combustion sources and are believed to play a considerable role in direct atmospheric radiative forcing by a number of climate scientists. In addition, it has been shown that BC is associated with adverse health effects in a number of epidemiological studies. Although the optical properties (both absorbing and scattering) of combustion aerosols are needed in order to accurately assess the impact of emissions on radiative forcing, many models use radiative properties of diesel particulate matter that were determined over two decades ago. In response to concerns of the human health impacts of particulate matter (PM), regulatory bodies around the world have significantly tightened PM emission limits for diesel engines. These requirements have resulted in considerable changes in engine technology requiring updated BC measurements from modern engines equipped with aftertreatment systems.

With the on- and off-road diesel engine emission regulations getting more stringent across the world, diesel aftertreatment systems are expected to deliver outstanding performance and reliability. These objectives should be met by fulfilling tight packaging constraints and incurring only modest material and testing costs. A major strategy for meeting these often conflicting requirements is the effective use of simulation tools such as computational fluid dynamics (CFD) in system design and performance evaluation. Prerequisites for using this CFD analysis-led-design approach, however, are knowledge of the confidence level of the predictions and knowledge of the appropriate transfer functions that establish the relationships between the measured performance parameters and model predictions. The primary aim of the present work is to develop statistically and physically relevant measures that assess the uniformity of flow in aftertreatment systems.

A major problem with many soot emission control devices is the fact that they quickly become loaded with soot which must be removed by a controlled burning (regeneration) process. The need for regeneration greatly complicates such diesel particle emission control devices. In this paper, an electrostatic agglomerator (ESA) which efficiently collects diesel particles but does not require regeneration is described. The ESA is an electrostatic precipitator which is designed to collect and subsequently reentrain diesel soot particles. The collection and reentrainment processes results in growth of particle diameter from roughly 0.2 μm to larger than 1.0 μm. The agglomerated particles are large enough to be collected by a relatively simple inertial device, e.g., a cyclone separator. The collected particle may be either recycled to the engine or disposed of by other means. Electrostatic collection is made easier by the fact that diesel particles are charged by the combustion process itself.

There is a growing body of evidence that in-cylinder surfaces play an important role in determining the nature and quantity of soot emitted by diesel engines. This paper describes recent experimental results which demonstrate the importance of both the deposition of soot on walls during the combustion process and its subsequent reentrainment during exhaust blowdown. Soot deposition was demonstrated both experimentally and theoretically. The principal mechanism of soot deposition during combustion is thermophoresis. Our results suggest that the gross rate of in-cylinder deposition in the indirect injection diesel engine is between 20 and 45 percent of the net soot emission rate. Thus, a significant fraction of the soot emitted may have been stored on combustion chamber surfaces and protected from oxidation. Further evidence of wall deposition and subsequent reentrainment has been obtained by making time-resolved measurements of soot concentrations in the exhaust.