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Technical Paper

A Case Study of a Cu-SSZ-13 SCR Catalyst Poisoned by Real-World High Sulfur Diesel Fuel

2020-04-14
2020-01-1319
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.
Technical Paper

A Comparison of Black Carbon Measurements to Solid Particle Number Measurements Made over Steady State and Transient Cycles

2015-04-14
2015-01-1074
Diesel engines have been identified as contributing to more than half of the transport sectors black carbon (BC) emissions in the US. This large contribution to atmospheric BC concentrations has raised concern about source specific emission rates, including off-highway engines. The European Union has recently implemented more stringent particulate regulations in the form of particle number via the Particle Measurement Programme (PMP) methodology. The PMP method counts the non-volatile fraction of particulate matter (PM) above 23 nm and below 2.5 μm via a condensation particle counter. This study evaluates a surrogate black carbon method which uses the PMP particle count method with a correlation factor to the BC fraction. The transient capable Magee Scientific Aethalometer (AE-33) 880 nm wavelength channel was used to determine the BC fraction.
Technical Paper

A Study on the Emissions of Chemical Species from Heavy-Duty Diesel Engines and the Effects of Modern Aftertreatment Technology

2009-04-20
2009-01-1084
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.
Journal Article

Comparative Study on Various Methods for Measuring Engine Particulate Matter Emissions

2008-06-23
2008-01-1748
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.
Journal Article

Comparison of Measurement Strategies for Light Absorbing Aerosols from Modern Diesel Engines

2014-04-01
2014-01-1570
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.
Journal Article

Desulfation of Pd-based Oxidation Catalysts for Lean-burn Natural Gas and Dual-fuel Applications

2015-04-14
2015-01-0991
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.
Journal Article

Detailed Effects of a Diesel Particulate Filter on the Reduction of Chemical Species Emissions

2008-04-14
2008-01-0333
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.
Technical Paper

Development and Validation of a Predictive Model for DEF Injection and Urea Decomposition in Mobile SCR DeNOx Systems

2010-04-12
2010-01-0889
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.
Journal Article

Development of Flow Uniformity Indices for Performance Evaluation of Aftertreatment Systems

2011-04-12
2011-01-1239
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.
Technical Paper

Development of a Method to Measure Engine Air Cleaner Fractional Efficiency

1999-03-01
1999-01-0002
The gravimetric method is commonly used in engine air filtration technology for air cleaner, filter element and filter media testing. An “absolute” filter is employed in-line to collect any dust particles passing through the test filter. Air filter efficiency is calculated by comparing the mass of dust collected by the test filter with that fed to the filter. This method measures only the mass of dust penetrating the filter. It does not provide information on contaminant particle size. Moreover, this method, in many cases, has inadequate precision to distinguish between filters. Both the dust mass and its particle size are needed to estimate engine wear. Therefore, the SAE J726 Air Cleaner Committee initiated work on a test method to measure engine air cleaner fractional efficiency. This paper discusses problems associated with development of the fractional efficiency method for engine air cleaners.
Technical Paper

Diesel Particulate Filters: Trends and Implications of Particle Size Distribution Measurement

2003-03-03
2003-01-0046
In order to comply with tightening environmental standards, diesel particulate filters will be used for engine particle emission control. A well-defined testing method is needed to characterize and evaluate the diesel particulate filters. A previously developed testing method yielded unexpected results which were believed to be caused by dilution air contamination and particle formation downstream of the filters. In this study, the testing method has been modified in order to address these issues. Various wall-flow diesel particulate filters of fibrous and porous materials were tested using the modified method in this study. The results were compared with the previous data to evaluate the level of improvement. The results were also analyzed using particle size distributions and filtration mechanisms described by various theories. Particle size distributions demonstrated significant improvement of the modified testing method.
Technical Paper

Effect of Hydrothermal Aging on the Catalytic Performance and Morphology of a Vanadia SCR Catalyst

2013-04-08
2013-01-1079
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.
Technical Paper

Effect of Nano-Filtered Intake Air on Diesel Particulate Matter Emissions

2004-03-08
2004-01-0642
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.
Technical Paper

Experimental and Numerical Investigations of Sprays in Crossflow in Aftertreatment Systems

2021-04-06
2021-01-0596
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.
Technical Paper

Formation and Decomposition of Ammonium Nitrate on an Ammonia Oxidation Catalyst

2018-04-03
2018-01-0342
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.
Journal Article

Impact of Hydrocarbons on the Dual (Oxidation and SCR) Functions of Ammonia Oxidation Catalysts

2014-04-01
2014-01-1536
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.
Journal Article

Impact of Water Vapor on the Performance of a Cu-SSZ-13 Catalyst under Simulated Diesel Exhaust Conditions

2021-04-06
2021-01-0577
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.
Technical Paper

Lab Study of Urea Deposit Formation and Chemical Transformation Process of Diesel Aftertreatment System

2017-03-28
2017-01-0915
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.
Journal Article

Laboratory sulfation of an ammonia slip catalyst with a real-world SO2 concentration

2023-04-11
2023-01-0380
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.
Technical Paper

Measuring the Fractional Efficiency of Diesel Particulate Filters

2002-03-04
2002-01-1007
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.
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