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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).

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.

Diesel oxidation catalyst (DOC) is one of the critical catalyst components in modern diesel aftertreatment systems. It mainly converts unburned hydrocarbon (HC) and CO to CO2 and H2O before they are released to the environment. In addition, it also oxidizes a portion of NO to NO2, which improves the NOx conversion efficiency via fast SCR over the downstream selective catalytic reduction (SCR) catalyst. HC light-off tests, with or without the presence of NOx, has been typically used for DOC evaluation in laboratory. In this work, we aim to understand the influences of DOC light-off experimental conditions, such as initial temperature, initial holding time, HC species, with or without the presence of NOx, on the DOC HC light-off behavior. The results indicate that light-off test with lower initial temperature and longer initial holding time (at its initial temperature) leads to higher DOC light-off temperature.

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.

Cu-SSZ-13 catalysts are widely used for diesel aftertreatment applications for NOx (NO and NO2) abatement via selective catalytic reaction (SCR) due to their high conversion efficiency and excellent hydrothermal stability. Diesel engine exhaust contains small amounts of SOx due to the combustion of sulfur compounds in diesel fuel. The engine out SOx level mainly depends on the sulfur content in the diesel fuel. The presence of SOx from engine exhaust can deteriorate the SCR performance of Cu-SSZ-13 catalysts in real-world applications. This work is focused on the sulfur-induced deactivation process of a Cu-SSZ-13 catalyst under a range of simulated diesel engine operating conditions. Two catalyst deactivation modes, namely chemical poisoning and physical poisoning, are identified, primarily depending on the operating temperature. Chemical poisoning mainly results from the interaction between SOx and Cu species within the zeolite framework.

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.

Biodiesel is a promising alternative to traditional diesel fuel due to its similar combustion properties to diesel and lower carbon emissions on a well-to-wheel basis. However, combusting biodiesel still generates hydrocarbon (HC), CO, NOx and particulate matter (PM) emissions, similar to those from traditional diesel fuel usage. Therefore, aftertreatment systems will be required to reduce these emissions to meet increasingly stringent emission regulations to minimize the impact to the environment. Diesel oxidation catalysts (DOC) are widely used in modern aftertreatment systems to convert unburned HC and CO, to partially convert NO to NO2 to enhance downstream selective catalytic reaction (SCR) catalyst efficiency via fast SCR and to periodically clean-up DPF via controlled soot oxidation. In this work, we focus on the performance difference between biodiesel and diesel over a commercial DOC catalyst to identify the knowledge gap during the transition from diesel fuel to biodiesel.

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.

Worldwide, regulations continue to drive reductions in brake-specific emissions of nitric oxide (NO) and nitrogen dioxide (NO2) from on-highway and nonroad diesel engines. NOx, formed as a byproduct of the combustion of fossil fuels (e.g., natural gas, gasoline, diesel, etc.), can be converted to dinitrogen (N2) through ammonia (NH3) selective catalytic reduction (SCR). In this study, we closely examine the low-temperature storage, isothermal desorption, reactive consumption, and thermal release of NH3 on commercial Cu-SSZ-13 and V2O5-WO3/TiO2 SCR catalysts. Catalyst core-reactor, N2 adsorption (BET) surface area, and in-situ diffuse reflectance Fourier transform infrared spectroscopy (DRIFTS) experiments are utilized to investigate the fundamental chemical processes relevant to low-temperature (T < 250°C) NH3 SCR.

Upcoming, stricter diesel exhaust emissions standards will likely require aftertreatment architectures with multiple diesel exhaust fluid (DEF) introduction locations. Managing NH3 slip with technologies such as an ammonia slip catalyst (ASC) will continue to be critical in these future aftertreatment systems. In this study, we evaluate the impact of SO2 exposure on a state-of-the-art commercially available ASC. SO2 is co-fed at 0.5 or 3 ppmv to either approximate or accelerate a real-world exhaust SO2 impact. ASC performance during sulfur co-feeding is measured under a wide variety of simulated real-world conditions. Results indicate that the loss of NO conversion during SCR is dependent on the cumulative SO2 exposure, regardless of the inlet SO2 concentration. Meanwhile, N2O formation under SCR conditions is nonlinearly affected by SO2 exposure, with formation increasing during 0.5 ppmv SO2 exposure but decreasing in the presence of 3 ppmv SO2.

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.

Selective catalytic reduction (SCR) of oxides of nitrogen (NOx) with gaseous ammonia is the leading technology used to meet on- and off-highway NOx emission standards across the world. In typical SCR systems, a low-pressure injector introduces a solution of urea and water (UWS) into hot exhaust gases leading to atomization and subsequent spray processes that finally lead to production of gaseous ammonia. Through their synergetic effect, the UWS injector and mixing enhancement devices (such as static mixers or baffles) help deliver a uniform mixture of ammonia and NOx to the SCR catalyst with minimal urea-derived solid deposits. To develop an efficient and robust aftertreatment system, it is essential to have experimental and simulation capabilities to assess the behavior of sprays under flow conditions representative of engine exhaust.

U.S. and European nonroad diesel emissions regulations have led to the implementation of various exhaust aftertreatment solutions. One approved configuration, a vanadium-based selective catalytic reduction catalyst followed by an ammonia oxidation catalyst (V-SCR + AMOX), does not require the use of a diesel oxidation catalyst (DOC) or diesel particulate filter (DPF). While certification testing has shown the V-SCR + AMOX system to be capable of meeting the nitrogen oxides, carbon monoxide, and particulate matter requirements, open questions remain regarding the efficacy of this aftertreatment for volatile and nonvolatile organic emissions removal, especially since the removal of this class of compounds is generally attributed to both the DOC and DPF.

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.

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.

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.

Selective catalytic reduction (SCR) of oxides of nitrogen with ammonia gas is a key technology that is being favored to meet stringent NOx emission standards across the world. Typically, in this technology, a liquid mixture of urea and water - known as Diesel Exhaust Fluid (DEF) - is injected into the hot exhaust gases leading to atomization and subsequent spray processes. The water content vaporizes, while the urea content undergoes thermolysis and forms ammonia and isocyanic acid, that can form additional ammonia through hydrolysis. Due to the increasing interest in SCR technology, it is desirable to have capabilities to model these processes with reasonable accuracy to both improve the understanding of processes important to the aftertreatment and to aid in system optimization. In the present study, a multi-dimensional model is developed to simulate DEF spray processes and the conversion of urea to ammonia. The model is then implemented into a commercial CFD code.

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.

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.

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.