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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.

In this study, the formation and decomposition of ammonium nitrate (AN) on a state-of-the-art extruded vanadium-based SCR catalyst (V-SCR) under simulated exhaust conditions has been evaluated. Results show that AN readily forms and accumulates at temperatures below 200°C when exposed to NH3 and NO2. The rate of AN accumulation increases with decreasing temperature. A new low temperature NH3 release peak (not present following NH3 storage conditions with NH3 only) becomes apparent after AN accumulation at 100 and 125°C. This new NH3 release, with a peak release temperature of approximately 180°C, is evaluated in detail to better determine its origin. BET surface area, and thermal gravimetric analysis/differential scanning calorimetry (TGA/DSC), and reactor-based experiments are all used to characterize AN formed on the V-SCR catalyst in comparison to pure AN.

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.

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.

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.

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.

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.

The effects of fuel sulfur content and dilution conditions on diesel engine PM number emissions have been researched extensively through steady state testing. Most results show that the concentration of nuclei-mode particles emitted increases with fuel sulfur content. A few studies further observed that fuel sulfur content has little effect on the emissions of heavily-used engines. It has also been found that primary dilution conditions can have a large impact on the size and number distribution of the nuclei-mode particles. These effects, however, have not yet been fully understood through transient testing, the method used by governments worldwide to certify engines and regulate emissions, and a means of experimentation which generates realistic conditions of on-road vehicles by varying the load and speed of the engine.

A comparative analysis was made on the emissions from a 2004 and a 2007 heavy-duty diesel engine to determine how new engine and emissions technologies have affected the chemical compounds found in the exhaust gases. Representative samples were collected from a source dilution sampling system and analyzed for both criteria and unregulated gaseous and particulate emissions. Results have shown that the 2007 regulations compliant engine and emissions technology not only reduced the specifically regulated exhaust pollutants, but also significantly reduced the majority of unregulated chemical species. It is believed that these reductions were achieved through the use of engine optimization, aftertreatment system integration, and ultra-low sulfur diesel fuel.

While most reductions in diesel particulate matter (PM) have been implemented through internal engine improvements and aftertreatment systems, additional reductions may be found by controlling intake contaminants. Under the ideal conditions of operating with ultra low sulfur diesel fuel and filtered and conditioned intake air, a diesel engine produces a certain amount of PM. The PM emission levels may increase when intake air is polluted during harsh on- or off-road conditions. In this study, contaminants were allowed to enter the intake tract of the engine to determine whether or not increased particle ingestion leads to increased particulate matter expulsion. Diesel and test dust contaminants dispersed in intake air were filtered using both a conventional filtering medium and a nano-medium to determine their effects on diesel engine-out PM emissions. The paper characterizes the two media by microstructure, permeability, porosity, and fractional efficiency.

The characterization of engine particulate matter size distributions has become an important topic in the investigation of particulate matter formation, transport, and emission reduction technology. The majority of current size distribution analyses are conducted during steady state engine conditions. Although steady state analysis is valuable, most engines in mobile applications are operated under transient conditions, creating a demand for the transient state analysis of particulate emission patterns. In order to measure the instantaneous emissions of an engine under transient conditions, instrumentation must respond to the changing engine conditions as quickly as possible. In this study, a fast-scanning nanometer Aerosol Size Analyzer (n-ASA) was used to measure the emitted particles of a heavy duty diesel engine during transient simulations. The results showed patterns of PM emissions at key areas throughout the test.

To meet stringent emission regulations, particulate filters will be required for diesel engines. Effective filters should reduce both the mass and number concentrations of particulate matter. For this reason, the performance of diesel particulate filters (DPFs) should be evaluated by measuring both gravimetric and fractional efficiency. This paper reports on a method developed for measuring particulate emissions on a mass and number basis. A two-stage dilution process was used in which the entire engine exhaust gas is directed into a primary dilution tunnel with a critical flow venturi. This constant volume system maintains proportional sampling throughout temperature excursions. A portion of the diluted exhaust gas is directed to a secondary dilution tunnel, for further dilution and determination of particle size distribution using a scanning mobility particle sizer. The engine was run at ISO 8178 modes.

Regulations on methane emissions from lean-burn natural gas (NG) and lean-burn dual fuel (natural gas and diesel) engines are becoming more stringent due to methane’s strong greenhouse effect. Palladium-based oxidation catalysts are typically used for methane reduction due to their relative high reactivity under lean conditions. However, the catalytic activity of these catalysts is inhibited by the water vapor in exhaust and decreases over time from exposure to trace amounts of sulfur. The reduction of deactivated catalysts in a net rich environment is known to be able to regenerate the catalyst. In this work, a multicycle methane light-off & extinction test protocol was first developed to probe the catalyst reactivity and stability under simulated exhaust conditions. Then, the effect of two different regeneration gas compositions, denoted as regen-A and regen-B, was evaluated on a degreened catalyst and a catalyst previously tested on a natural gas engine.

Natural gas powered vehicles are attractive in certain applications due to their lower emissions in general than conventional diesel engines and the low cost of natural gas. For stoichiometric natural gas engines, the aftertreatment system typically consists only of a three-way catalyst (TWC). However, increasingly stringent NOx and methane regulations challenge current TWC technologies. In this work, a catalyst reactor system with variable lean/rich switching capability was developed for evaluating TWCs for stoichiometric natural gas engines. The effect of varying frequency and duty-cycle during lean/rich gas switching experiments was measured with a hot-wire anemometer (HWA) due to its high sensitivity to gas thermal properties. A theoretical reactor gas dispersion model was then developed and validated with the HWA measurements. The model is capable of predicting the actual lean/rich gas exposure to the TWC under different testing conditions.

Nitrogen dioxide (NO2) is known to pose a risk to human health and contributes to the formation of ground level ozone. In recognition of its human health implications, the American Conference of Governmental Industrial Hygienists (ACGIH) set a Threshold Limit Value (TLV) of 0.2 ppmv NO2 in 2012. For mobile sources, NO2 is regulated as a component of NOx (NO + NO2). In addition, the European Commission has indicated it is considering separate Euro 6 light-duty diesel and Euro VI heavy-duty diesel NO2 emissions limits likely to mitigate the formation of ground level ozone in urban areas. In this study, we conduct component-level reactor-based experiments to understand the effects that various aftertreatment catalyst technologies including diesel oxidation catalyst (DOC), diesel particulate filter (DPF), selective catalytic reduction (SCR) catalyst and ammonia oxidation (AMOX) catalyst have on the formation and mitigation of NO2 emissions.

Titania supported vanadia catalysts have been widely used for the selective catalytic reduction (SCR) of nitrogen oxides (NOx) in diesel exhaust aftertreatment systems. Vanadia SCR (V-SCR) catalysts are preferred for many applications because they have demonstrated advantages of catalytic activity for NOx removal and tolerance to sulfur poisoning. The primary shortcoming of V-SCR catalysts is their thermal durability. Degradation in NOx conversion is also related to aging conditions such as at high temperatures. In this study, the impact that short duration hydrothermal aging has on a state-of-the-art V-SCR catalyst was investigated by aging for 2 hr intervals with progressively increased temperatures from 525 to 700°C. The catalytic performance of this V-SCR catalyst upon aging was evaluated by three different reactions of NH₃ SCR, NH₃ oxidation, and NO oxidation under simulated diesel exhaust conditions from 170 to 500°C.

Achieving high NOx conversion at low-temperature (T ≤ 200 °C) is a topic of active research due to potential reductions in regulated NOx emissions from diesel engines. At these temperatures, ammonium nitrate may form as a result of interactions between NH3 and NO2. Ammonium nitrate formation can reduce the availability of NH3 for NOx conversion and block active catalyst sites. The thermal decomposition of ammonium nitrate may result in the formation of N2O, a regulated Greenhouse Gas (GHG). In this study, we investigate the formation and thermal and chemical decomposition of ammonium nitrate on a state-of-the-art dual-layer ammonia oxidation (AMOX) catalyst. Reactor-based constant-temperature ammonium nitrate formation, temperature programmed desorption (TPD), and NO titration experiments are used to characterize formation and decomposition.