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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).

Selective Catalytic Reduction (SCR) of oxides of nitrogen (NOx) with ammonia gas has established itself as an effective diesel aftertreatment technology to meet stringent emission standards enforced by worldwide regulatory bodies. Typically, in this technology, aqueous urea solution of eutectic composition - known as Diesel Exhaust Fluid (DEF) - is injected into hot exhaust gases leading to a series of thermal, fluid dynamic and reactive processes that eventually produces the ammonia necessary for NOx reduction reactions within monolithic catalytic substrates. Incomplete decomposition of the injected urea can lead to formation of solid deposits that adversely affect system performance by increasing the engine back pressure, reducing de-NOx efficiency, and lowering the overall fuel economy.

Introduction of modern diesel aftertreatment, primarily selective catalytic reduction (SCR) designed to reduced NOx, has increased the presence of urea decomposition byproducts, mainly ammonia, in the aftertreatment system. This increase in ammonia has been shown to lead to particle formation in the aftertreatment system. In this study, a state of the art diesel exhaust fluid (DEF)-SCR system was investigated in order to determine the influence of DEF dosing on solid particle count. Post diesel particulate filter (DPF) particle count (> 23 nm) is shown to increase by over 400% during the World Harmonized Transient Cycle (WHTC) due to DEF dosing. This increase in tailpipe particle count warranted a detailed parametric study of DEF dosing parameters effect on tailpipe particle count. Global ammonia to NOx ratio, DEF droplet residence time, and SCR catalyst inlet temperature were found to be significant factors in post-DPF DEF based particle formation.

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.

Sustained NOx reduction at low temperatures, especially in the 150-200 °C range, shares some similarities with the more commonly discussed cold-start challenge, however, poses a number of additional and distinct technical problems. In this project, we set a bold target of achieving and maintaining 90% NOx conversion at the SCR catalyst inlet temperature of 150 °C. This project is intended to push the boundaries of the existing technologies, while staying within the realm of realistic future practical implementation. In order to meet the resulting challenges at the levels of catalyst fundamentals, system components, and system integration, Cummins has partnered with the DOE, Johnson Matthey, and Pacific Northwest National Lab and initiated the Sustained Low-Temperature NOx Reduction program at the beginning of 2015 and completed in 2017.

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.

Selective catalytic reduction (SCR) is a promising technology for meeting the stringent requirements pertaining to NOx emissions. One of the most important requirements to achieve high DeNOx performance is to have a high uniformity of ammonia to NOx ratio (ANR) at the SCR catalyst inlet. Steady state 3D computational fluid dynamics (CFD) models are frequently used for predicting ANR spatial distribution but are not feasible for running a transient cycle like Federal Test Procedure (FTP). On the other hand, 1D kinetic models run in real time and can predict transient SCR performance but do not typically capture the effect of non-axial non-uniformities. In this work, two 3D to 1D coupling methods have been developed to predict transient SCR system performance, taking the effect of ANR non-uniformity into account. First is a probability density function (PDF) based approach and the second is a geometrical sector based approach.

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.

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 paper covers the design and development of Heavy-Duty (HD) Diesel engines that meet the 2007 HD US EPA emission standards. These standards are the most stringent standards in the world for on-highway HD diesel engines, and have driven the application of new technologies, which includes: particulate aftertreatment, crankcase ventilation systems, and second generation cooled EGR. The paper emphasizes the importance of designing the product to meet the tough expectations of the trucking industry - for lowest total cost of ownership, lowest operating costs, high uptime, ease of maintenance, high performance and durability. A key objective was that these new low emission engines should meet or exceed the performance, reliability and fuel economy standards set by the products they replace. Additionally, these engines were designed to be fully compatible and emissions compliant with bio-diesel B20 blends that meet the ASTM and EMA fuel standards.

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.

Diesel exhaust fluid, DEF, (32.5 wt.% urea aqueous solution) is widely used as the NH3 source for selective catalytic reduction (SCR) of NOx in diesel aftertreatment systems. The transformation of sprayed liquid phase DEF droplets to gas phase NH3 is a complex physical and chemical process. Briefly, it experiences water vaporization, urea thermolysis/decomposition and hydrolysis. Depending on the DEF doser, decomposition reaction tube (DRT) design and operating conditions, incomplete decomposition of injected urea could lead to solid urea deposit formation in the diesel aftertreatment system. The formed deposits could lead to engine back pressure increase and DeNOx performance deterioration etc. The formed urea deposits could be further transformed to chemically more stable substances upon exposure to hot exhaust gas, therefore it is critical to understand this transformation process.

Cu-SSZ-13 selective catalytic reduction (SCR) catalysts are broadly applied in diesel aftertreatment systems for the catalytic conversion of oxides of nitrogen (NO + NO2). Diesel exhaust contains a wide range of water vapor concentrations depending on the operating condition. In this study, we evaluate the impact of water vapor on the relevant SCR catalytic functions including NOx conversion, NO oxidation, NH3 oxidation, and N2O formation under both standard and fast SCR conditions. Reactor-based experiments are conducted in the presence and absence of water vapor. Results indicate that water vapor can have both a positive and negative impact on low temperature NOx conversion for standard SCR reaction. At low inlet NOx concentrations, the presence of water vapor has a negative effect on NOx conversion, whereas, at high inlet NO concentrations, water vapor improves NOx 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.

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.

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.

A simple 1-dimensional filter model, with symmetric and asymmetric channels, has been developed to investigate the fundamental behavior and performance of ceramic partial diesel particulate filters (PFs). The governing equations of mass and momentum are similar to those of a full DPF [7, 15]. A standard DPF with the plugs at its inlet face removed has been referred to as a ‘rear-plugged PF’ while, one with the plugs at the outlet face removed has been referred to as a ‘front-plugged PF’ in the present study. Removal of some of the plugs from a standard ceramic DPF reduces the (i) overall pressure drop (ΔP) across the filter, (ii) filtration efficiency (FE) of the DPF, and (iii) manufacturing cost. Partial filters stand a high chance of being deployed in diesel exhaust after-treatment systems for the emerging markets (Brazil, Russia, India, China) that follow Euro 4 emission regulations.

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.

One field-returned DPF loaded with a high amount of ash is examined using experimental and modeling approaches. The ash-related design factors are collected by coupling the inspection results from terahertz spectroscopy with a calibrated DPF model. The obtained ash packing density, ash layer permeability and ash distribution profile are then used in the simulation to assess the ash impact on DPF backpressure and regeneration behaviors. The following features have been observed during the simulation: 1 The ash packing density, ash layer permeability and ash distribution profile should be collected at the same time to ensure the accurate prediction of ash impact on DPF backpressure. Missing one ash property could mislead the measurement of the other two parameters and thus affects the DPF backpressure estimation. 2 The ash buildup would gradually increase the frequency for the backpressure-based active soot regeneration.

Tailpipe particle number (PN) emission limits for heavy-duty diesel engines have been introduced as part of the off-highway Stage V standards. To meet the required limits a diesel particulate filter (DPF) with high filtration efficiency is required. The DPF relies on formation of a soot cake layer on the channel walls to achieve this high filtration efficiency. Off highway Stage V certification cycles are significantly higher in temperature than their on-highway counterparts, leading to difficulty in creating and maintaining a soot cake in the DPF. Hence for these applications meeting particle number requirements is challenging. To meet the high filtration efficiency requirements the DPF will have to reduce mean pore size, pore standard deviation, and increase wall thickness, in turn increasing backpressure, which results in a fuel consumption penalty. Another option is to evaluate the impact of temperature stable ash accumulation on DPF filtration efficiency.