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Mechanisms of NH₃ generation using LNT-like catalysts have been studied in a bench reactor over a wide range of temperatures, flow rates, reformer catalyst types and synthetic exhaust-gas compositions. The experiments showed that the on board production of sufficient quantities of ammonia on board for SCR operation appeared feasible, and the results identified the range of conditions for the efficient generation of ammonia. In addition, the effects of reformer catalysts using the water-gas-shift reaction as an in-situ source of the required hydrogen for the reactions are also illustrated. Computations of the NH₃ and NOx kinetics have also been carried out and are presented. Design and impregnation of the SCR catalyst in proximity to the ammonia source is the next logical step. A heated synthetic-exhaust gas flow bench was used for the experiments under carefully controlled simulated exhaust compositions.

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).

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 nitrogen oxides (NOx) is used in diesel-fueled mobile applications where urea is an added reducing agent. We show that the Ultera® dual-stage catalyst, with intercooling aftertreatment system, intrinsically performs the function of the SCR method in nominally stoichiometric gasoline vehicle engines without the need for an added reductant. We present that NOx is reduced during the low-temperature operation of the dual-stage system, benefiting from the typically periodic transient operation (acceleration and decelerations) with the associated swing in the air/fuel ratio (AFR) inherent in mobile applications, as commonly expected and observed in real driving. The primary objective of the dual-stage aftertreatment system is to remove non-methane organic gases (NMOG) and carbon monoxide (CO) slip from the vehicle’s three-way catalyst (TWC) by oxidizing these constituents in the second stage catalyst.

This paper reviews the relevant literature on the effects of sulfated ash, phosphorus, and sulfur on DPF, LNT, and SCR catalysts. Exhaust backpressure increase due to DPF ash accumulation, as well as the rate at which ash is consumed from the sump, were the most studied lubricant-derived DPF effects. Based on several studies, a doubling of backpressure can be estimated to occur within 270,000 to 490,000 km when using a 1.0% sulfated ash oil. Postmortem DPF analysis and exhaust gas measurements revealed that approximately 35% to 65% less ash was lost from the sump than was expected based on bulk oil consumption estimates. Despite significant effects from lubricant sulfur and phosphorus, loss of LNT NOX reduction efficiency is dominated by fuel sulfur effects. Phosphorus has been determined to have a mild poisoning effect on SCR catalysts. The extent of the effect that lubricant phosphorus and sulfur have on DOCs remains unclear, however, it appears to be minor.

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.

As vehicle fuel economy requirements continue to increase it is becoming more challenging and expensive to simultaneously improve fuel consumption and meet emissions regulations. The Passive Ammonia SCR System (PASS) is a novel aftertreatment concept which has the potential to address NOx emissions with application to both lean SI and stoichiometric SI engines. PASS relies on an underfloor (U/F) SCR for storage of ammonia which is generated by the close-coupled (CC) TWCs. For lean SI engines, it is required to operate with occasional rich pulses in order to generate the ammonia, while for stoichiometric application ammonia is passively generated through the toggling of air/fuel ratio. PASS serves as an efficient and cost-effective enhancement to standard aftertreatment systems. For this study, the PASS concept was demonstrated first using lab reactor results which highlight the oxygen tolerance and temperature requirements of the SCR.

Lean-burn SIDI engine technology offers improved fuel economy; however, the reduction of NOx during lean-operation continues to be a major technical hurdle in the implementation of energy efficient technology. There are several aftertreatment technologies, including the lean NOx trap and active urea SCR, which have been widely considered, but they all suffer from high material cost and require customer intervention to fill the urea solution. Recently reported passive NH₃-SCR system - a simple, low-cost, and urea-free system - has the potential to enable the implementation of lean-burn gasoline engines. Key components in the passive NH₃-SCR aftertreatment system include a close-coupled TWC and underfloor SCR technology. NH₃ is formed on the TWC with short pulses of rich engine operation and the NH₃ is then stored on the underfloor SCR catalysts.

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.

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.

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.

With a tighter regulatory environment, reduction of hydrocarbon (HC) and NOx emissions during cold-start has emerged as a major challenge for diesel engines. In the complex diesel aftertreatment system, more than 90% of engine-out NOx is removed in the underfloor SCR. However, the combination of low temperature exhaust and heat sink over DOC delays the SCR light-off during the cold start. In fact, the first 350 seconds during the cold light-duty FTP75 cycle contribute more than 50% of the total NOx tailpipe emission due to the low SCR temperature. For a fast SCR light-off, electrically heated catalyst (EHC) technology has been suggested to be an effective solution as a rapid warm-up strategy. In this work, the EHC, placed in front of DOC, utilizes both electrical power and hydrocarbon fuel. The smart energy management during the cold-start was crucial to optimize the EHC integrated aftertreatment system.

Diesel engines have the potential to significantly increase vehicle fuel economy and decrease CO₂ emissions; however, efficient removal of NOx and particulate matter from the engine exhaust is required to meet stringent emission standards. A conventional diesel aftertreatment system consists of a Diesel Oxidation Catalyst (DOC), a urea-based Selective Catalyst Reduction (SCR) catalyst and a diesel particulate filter (DPF), and is widely used to meet the most recent NOx (nitrogen oxides comprising NO and NO₂) and particulate matter (PM) emission standards for medium- and heavy-duty sport utility and truck vehicles. The increasingly stringent emission targets have recently pushed this system layout towards an increase in size of the components and consequently higher system cost. An emerging technology developed recently involves placing the SCR catalyst onto the conventional wall-flow filter.

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.

The urea injection is a key function in Urea-SCR NOx reduction system. As the tailpipe NOx emission standard becomes increasingly stringent, it is critical to diagnose the injection faults in order to guarantee the SCR DeNox functionality and performance. Particularly, a blocked injector may cause under-dosing of urea thus reduced DeNox functionality. Monitoring urea injection rate is one of the efficient methods for injection fault diagnosis. However, direct measurement of the urea mass flow is not feasible due to its high cost. This paper presents methods that are promising for detecting and isolating faults in urea injection by processing certain actuator signal and existing sensory measurements, e.g., the injector Pulse Amplitude Modulated (PAM) command and the pressure of the urea delivery line. No additional dedicated sensor is required. Three methods are discussed to detect urea injection system faults.

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.

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.