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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.

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.

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.

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 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.

This study analyzed the impact of transient and multi-mode engine conditions on emissions of dioxins and furans from a variety of diesel aftertreatment configurations. Exhaust aftertreatment systems included combinations of diesel oxidation catalyst, diesel particulate filter, and either Cu/zeolite or Fe/zeolite selective catalytic reduction catalyst. EPA method TO-9A was modified for proportional exhaust gas sampling, whereas EPA method 0023A was modified for raw exhaust gas sampling. Dioxin and furan emissions were first measured with modified method TO-9A during Federal Test Procedure transient cycles, but no toxic dioxins or furans were detected. Measurements were then taken with modified method 0023A during Ramped Mode Cycles-Supplemental Emissions Test experiments. Because more rigorous pre-cleaning and sample extraction procedures were used with this method and lower detection limits were achieved by the analytical laboratory, some dioxin and furan congeners were detected.

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.

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.

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.

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.

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.

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.

The performance of diesel particulate filters (DPF) has historically been evaluated by gravimetric efficiency, which measures the mass of particulate matter (PM) trapped in the filters. This method does not measure the filtration efficiency at different PM size ranges and, therefore, cannot provide information on fractional performance of DPFs. This fact becomes significant because the adverse effects of diesel PM emissions on human health and the environment are size dependent. A previous study investigated the fractional performance of DPFs under steady state conditions using a scanning mobility particle sizer (SMPS). In the real world, however, nearly all engines operate under transient conditions. DPFs also have to perform under such conditions, so any measurement of performance must be able to react to quickly changing DPF conditions.

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.

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.

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.

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.

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.