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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.

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.

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.

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.

To meet increasingly stringent diesel engine emission regulations, diesel engines are required to use ultra-low sulfur diesel (ULSD) and are equipped with advanced aftertreatment systems. Cu-SSZ-13 zeolite catalysts are widely used as selective catalytic reduction (SCR) catalysts due to their high NOx reduction and excellent hydrothermal stability. However, active Cu sites of Cu-SSZ-13 catalysts can be poisoned by exposure to engine exhaust sulfur species. This poison effect can be mitigated with the use of ULSD and high temperature exposure from engine operation. On the other hand, ULSD is still not universally available where regulations require it, and vehicles may inadvertently operate with high sulfur diesel fuel (HSD) in some locations. The high concentration of exhaust sulfur species resulting from HSD combustion may rapidly poison the Cu-SSZ-13 SCR catalyst. In this study, the catalytic performance of a sulfur poisoned Cu-SSZ-13 SCR catalyst is analyzed.

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.

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.

An advanced exhaust aftertreatment system (ATS) for Tier 4 compliant locomotive applications was successfully designed and developed for use on Cummins QSK95 engines. The engine and ATS were introduced in late 2016. This system provided nitrogen oxides (NOx) reduction capability in excess of 95%. Vanadia-based selective catalytic reduction (V-SCR) extruded catalyst technology was chosen over other readily available component technologies such as diesel oxidation catalyst (DOC) or a combination of DOC and SCR systems to address the stringent Tier 4 standards. In addition to NOx reduction, substantial oxidation of gaseous hydrocarbons (HCs) from unburnt fuel and lubricating oil soluble organic fraction (SOF) was also achieved. This dual functionality (oxidation and reduction capability) was one of the key factors in adopting this technology as the prime path and rendering it suitable for the harsh locomotive application environment.

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.

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.

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).

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.

Advanced emission control systems for diesel engines usually include a combination of Diesel Oxidation Catalyst (DOC), Diesel Particulate Filter (DPF), Selective Catalytic Reduction (SCR), and Ammonia Slip Catalyst (ASC). The performance of these catalysts individually, and of the aftertreatment system overall, is negatively affected by the presence of oxides of sulfur, originating from fuel and lubricant. In this paper, we illustrated some key aspects of sulfur interactions with the most commonly used types of catalysts in advanced aftertreatment systems. In particular, DOC can oxidize SO2 to SO3, collectively referred to as SOx, and store these sulfur containing species. The key functions of a DOC, such as the ability to oxidize NO and HC, are degraded upon SOx poisoning. The impact of sulfur poisoning on the catalytic functions of a DPF is qualitatively similar to DOC.

SCR on Filter (SCRoF) is an efficient and compact NOX and PM reduction technology already used in series production for light-duty applications. The technology is now finding its way into the medium duty and heavy duty market. One of the key challenges for successful application is the robustness to real world variations. The solution to this challenge can be found by using model-based control algorithms, utilizing state estimation by physics-based catalyst models. This paper focuses on the development, validation and real time implementation of a physics-based control oriented SCRoF model. An overview of the developed model will be presented, together with a brief description of the model parameter identification and validation process using engine test bench measurement data. The model parameters are identified following a streamlined approach, focusing on decoupling the effects of deNOx and soot phenomena.

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.

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.

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.

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.

More stringent emission requirements for nonroad diesel engines both in the U.S. and Europe have spurred the development of engines and exhaust aftertreatment technologies. In this study, one such system consisting of a diesel oxidation catalyst, zeolite-based selective catalytic reduction catalyst, and an ammonia oxidation catalyst was evaluated using both nonroad transient and steady-state cycles in order to understand the emission characteristics of this configuration. Criteria pollutants were analyzed and particular attention was given to organic compound and NO2 emissions since both of these could be significantly affected by the absence of a diesel particulate filter that typically helps reduce semi-volatile and particle-phase organics and consumes NO2 via passive soot oxidation. Results are then presented on a detailed speciation of organic emissions including alkanes, cycloalkanes, aromatics, polycyclic aromatic hydrocarbons and their derivatives, and hopanes and steranes.