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The low-temperature performance characteristics of a commercial lean NOX trap catalyst were evaluated using infra-red thermography (IRT) before and after a high-temperature aging step. Reaction tests included propylene oxidation, oxygen storage capacity measurements, and simulated cycling conditions for NOX reduction, using H₂ as the reductant during the regeneration step of the cycle. Testing with and without NO in the lean phase showed thermal differences between the reductant used in reducing the stored oxygen and that for nitrate decomposition and reduction. IRT clearly demonstrated where NOX trapping and regeneration were occurring spatially as a function of regeneration conditions, with variables including hydrogen content of the regeneration phase and lean- and rich-phase cycle times.

Cu- and Fe-zeolite SCR catalysts emerged in recent years as the primary candidates for meeting the increasingly stringent lean exhaust emission regulations, due to their outstanding activity and durability characteristics. It is commonly known that Cu-zeolite catalysts possess superior activity to Fe-zeolites, in particular at low temperatures and sub-optimal NO₂/NOx ratios. In this work, we elucidate some underlying mechanistic differences between these two classes of catalysts, first based on their NO oxidation abilities, and then based on the relative properties of the two types of exchanged metal sites. Finally, by using the ammonia coverage-dependent NOx performance, we illustrate that state-of-the-art Fe-zeolites can perform better under certain transient conditions than in steady-state.

Exposure of hydrocarbons (HCs) and particulate matter (PM) under certain real-world operating conditions leads to carbonaceous deposit formation on V-SCR catalysts and causes reversible degradation of its NOx conversion. In addition, uncontrolled oxidation of such carbonaceous deposits can also cause the exotherm that can irreversibly degrade V-SCR catalyst performance. Therefore carbonaceous deposit mitigation strategies, based on their characterization, are needed to minimize their impact on performance. The nature and the amount of the deposits, formed upon exposure to real-world conditions, were primarily carried out by the controlled oxidation of the deposits to classify these carbonaceous deposits into three major classes of species: i) HCs, ii) coke, and iii) soot. The reversible NOx conversion degradation can be largely correlated to coke, a major constituent of the deposit, and to soot which causes face-plugging that leads to decreased catalyst accessibility.

Typical Lean NOx Trap (LNT) catalyst composition includes precious metal components (Pt, Pd, and/or Rh), responsible for NO oxidation during lean operation and NOx reduction during rich operation. It was found that redox history of commercial LNT catalyst plays a significant role on deciding its NOx conversion under Lean/Rich cyclic condition. Further test had shown that fully formulated LNT catalyst being pre-reduced had shown much better NO reduction activity during the temperature-programmed reduction (TPRx) of NO than the same LNT catalyst being oxidized. The following study with Rh-only and Pt-only catalyst had demonstrated that Rh plays a key role on the large variation of the NO reduction function due to oxidation state change over LNT catalyst.

Future light duty vehicles in the United States are required to be certified on the FTP-75 cycle to meet Tier 3 or LEV III emission standards [1, 2]. The cold phase of this cycle is heavily weighted and mitigation of emissions during this phase is crucial to meet the low tail pipe emission targets [3, 4]. In this work, a novel aftertreatment architecture and controls to improve Nitrogen Oxides (NOx) and Hydrocarbon (HC) or Non Methane Organic gases (NMOG) conversion efficiencies at low temperatures is proposed. This includes a passive NOx & HC adsorber, termed the diesel Cold Start Concept (dCSC™) catalyst, followed by a Selective Catalytic Reduction catalyst on Filter (SCRF®) and an under-floor Selective Catalytic Reduction catalyst (SCR). The system utilizes a gaseous ammonia delivery system capable of dosing at two locations to maximize NOx conversion and minimize parasitic ammonia oxidation and ammonia slip.

Copper- and Iron- based metal-zeolite SCR catalysts are widely used in US and European diesel aftertreatment systems to achieve drastic reduction in NOx emission. These catalysts are highly selective to N2 under wide range of operating conditions. Nevertheless, the type of transition metal has a significant impact on the key performance and durability parameters such as NOx conversion, selectivity towards N2O, hydrothermal stability, and sensitivity to fuel sulfur content. In this study, we explained the differences in the performance characteristics of these catalysts based on their relative acidic-basic nature of transition metal present in these catalysts using practically relevant gas species present in diesel exhaust such as NO2, SOx, and NH3. These experiments show that Fe-zeolite has relatively acidic nature as compared to Cu-zeolite that causes NH3 inhibition and hence explains low NOx conversion on Fe-zeolite at low temperature under standard SCR conditions.

In this paper, a model-based linear estimator and a non-linear control law for an Fe-zeolite urea-selective catalytic reduction (SCR) catalyst for heavy duty diesel engine applications is presented. The novel aspect of this work is that the relevant species, NO, NO2 and NH3 are estimated and controlled independently. The ability to target NH3 slip is important not only to minimize urea consumption, but also to reduce this unregulated emission. Being able to discriminate between NO and NO2 is important for two reasons. First, recent Fe-zeolite catalyst studies suggest that NOx reduction is highly favored by the NO 2 based reactions. Second, NO2 is more toxic than NO to both the environment and human health. The estimator and control law are based on a 4-state model of the urea-SCR plant. A linearized version of the model is used for state estimation while the full nonlinear model is used for control design.

Real-world operation of diesel oxidation catalysts (DOCs), used in a variety of aftertreatment systems, subjects these catalysts to a large number of permanent and temporary deactivation mechanisms. These include thermal damage, induced by generating exotherm on the catalyst; exposure to various inorganic species contained in engine fluids; and the effects of soot and hydrocarbons, which can mask the catalyst in certain operating modes. While some of these deactivation mechanisms can be accurately simulated in the lab, others are specific to particular engine operation regimes. In this work, a set of DOCs, removed from prolonged service in the field, has been subjected to a detailed laboratory study. Samples obtained from various locations in these catalysts were used to characterize the extent and distribution of deactivation.

The high global warming potential of nitrous oxide (N₂O) led to its recent inclusion in the list of regulated pollutants under the emerging greenhouse gas regulations. While N₂O can be present in small quantities among the combustion products, it can also be generated as a minor byproduct in various types of aftertreatment systems. In this work, a systematic review of sources of N₂O is presented, along with the potential mechanisms of formation in a typical selective-catalytic-reduction-based diesel exhaust aftertreatment system. It is demonstrated that diesel oxidation catalysts (DOC), selective catalytic reduction (SCR) catalyst, and ammonia slip catalyst (ASC) can all potentially contribute to N₂O formation, depending on the catalyst material and exhaust gas conditions, as well as aftertreatment operation strategies. Furthermore, catalysts used in SCR aftertreatment system are also shown to decompose and/or reduce N₂O to N₂ under select conditions.

Mitigation of ammonia slip from SCR system is critical to meeting the evolving NH₃ emission standards, while achieving maximum NOx conversion efficiency. Ammonia slip catalysts (ASC) are expected to balance high activity, required to oxidize ammonia across a broad range of operating conditions, with high selectivity of converting NH₃ to N₂, thus avoiding such undesirable byproducts as NOx or N₂O. In this work, new insights into the behavior of an advanced ammonia slip catalyst have been developed by using accelerated progressive catalyst aging as a tool for catalyst property interrogation. The overall behavior was deconstructed to several underlying functions, and referenced to an active but non-selective NH₃ oxidation function of a diesel oxidation catalyst (DOC) and to the highly selective but minimally active NH₃ oxidation function of an SCR catalyst.

Cu/CHA catalysts have been widely used in the industry, due to their desirable performance characteristics including the unmatched hydrothermal stability. While broadly recognized for their outstanding activity at or above 200°C, these catalysts may not show desired levels of NOx conversion at lower temperatures. To achieve high NOx conversions it is desirable to have NO2/NOx close to 0.5 for fast SCR. However even under such optimal gas feed conditions, sustained use of Cu/CHA below 200°C leads to ammonium nitrate formation and accumulation, resulting in the inhibition of NOx conversion. In this contribution, the formation and decomposition of NH4NO3 on a commercial Cu/CHA catalyst have been investigated systematically. First, the impact of NH4NO3 self-inhibition on SCR activity as a function of temperature and NO2/NOx ratios was investigated through reactor testing.

An experimental and modeling study was conducted to study the passive regeneration of a catalyzed particulate filter (CPF) by the oxidation of particulate matter (PM) via thermal and Nitrogen dioxide/temperature-assisted means. Emissions data in the exhaust of a John Deere 6.8 liter, turbocharged and after-cooled engine with a low-pressure loop EGR and a diesel oxidation catalyst (DOC) - catalyzed particulate filter (CPF) in the exhaust system was measured and used for this study. A series of experiments was conducted to evaluate the performance of the DOC, CPF and DOC+CPF configurations at various engine speeds and loads.

Steady-state particulate loading experiments were conducted on an advanced production catalyzed particulate filter (CPF), both with and without a diesel oxidation catalyst (DOC). A heavy-duty diesel engine was used for this study with the experiments conducted at 20, 40, 60 and 75 % of full load (1120 Nm) at rated speed (2100 rpm). The data obtained from these experiments were used and are necessary for calibrating the MTU 1-D 2-Layer CPF model. These experimental and modeling results were compared to previous research conducted at MTU that used the same engine but an earlier development version of the combination of DOC and CPF. The motivation for the comparison of the two systems was to determine whether the reformulated production catalysts performed as good or better than the early development catalysts. The results were compared to understand the filtration and oxidation differences between the two DOC+CPF and the CPF-only aftertreatment systems.

Model-based control strategies are important for meeting the dual objective of maximizing NOx reduction and minimizing NH3 slip in urea-SCR catalysts. To be implementable on the vehicle, the models should capture the essential behavior of the system, while not being computationally intensive. This paper discusses the adequacy of two different reduced order SCR catalyst models and compares their performance with a higher order model. The higher order model assumes that the catalyst has both diffusion and reaction kinetics, whereas the reduced order models contain only reaction kinetics. After describing each model, its parameter identification and model validation based on experiments on a Navistar I6 7.6L engine are presented. The adequacy of reduced order models is demonstrated by comparing the NO, NO2 and NH3 concentrations predicted by the models to their concentrations from the test data.

The performance characteristics of a commercial lean-NOX trap catalyst were evaluated between 200 and 500°C, using H2, CO, and a mixture of both H2 and CO as reductants before and after different high-temperature aging steps, from 600 to 750°C. Tests included NOX reduction efficiency during cycling, NOX storage capacity (NSC), oxygen storage capacity (OSC), and water-gas-shift (WGS) and NO oxidation reaction extents. The WGS reaction extent at 200 and 300°C was negatively affected by thermal degradation, but at 400 and 500°C no significant change was observed. Changes in the extent of NO oxidation did not show a consistent trend as a function of thermal degradation. The total NSC was tested at 200, 350 and 500°C. Little change was observed at 500°C with thermal degradation but a steady decrease was observed at 350°C as the thermal degradation temperature was increased.

A one-dimensional model simulating the oxidation of CO, HC, and NO was developed to predict the gaseous emissions downstream of a diesel oxidation catalyst (DOC). The model is based on the conservation of mass, species, and energy inside the DOC and draws on past research literature. Steady-state experiments covering a wide range of operating conditions (exhaust temperatures, flow rates and gaseous emissions) were performed, and the data were used to calibrate and validate the model. NO conversion efficiencies of 50% or higher were obtained at temperatures between 300°C and 350°C. CO conversion efficiencies of 85% or higher and HC conversion efficiencies of 75% or higher were found at every steady state condition above 200°C. The model agrees well with the experimental results at temperatures from 200°C to 500°C, and volumetric flow rates from 8 to 42 actual m3/min.

Sulfur poisoning from engine fuel and lube is one of the most recognizable degradation mechanisms of a NOx adsorber catalyst system for diesel emission reduction. Even with the availability of 15 ppm sulfur diesel fuel, NOx adsorber will be deactivated without an effective sulfur management. Two general pathways are currently being explored for sulfur management: (1) the use of a disposable SOx trap that can be replaced or rejuvenated offline periodically, and (2) the use of diesel fuel injection in the exhaust and high temperature de-sulfation approach to remove the sulfur poisons to recover the NOx trapping efficiency. The major concern of the de-sulfation process is the many prolonged high temperature rich cycles that catalyst will encounter during its useful life. It is shown that NOx adsorber catalyst suffers some loss of its trapping capacity upon high temperature lean-rich exposure.

Measuring axial exhaust species concentration distributions within a wall-flow aftertreatment device provides unique and significant insights regarding the performance of complex devices like the SCR-on-filter. In this particular study, a less complex aftertreatment configuration which includes a DOC followed by two uncoated partial flow filters (PFF) was used to demonstrate the potential and challenges. The PFF design in this study was a particulate filter with alternating open and plugged channels. A SpaciMS [1] instrument was used to measure the axial NO2 profiles within adjacent open and plugged channels of each filter element during an extended passive regeneration event using a full-scale engine and catalyst system. By estimating the mass flow through the open and plugged channels, the axial soot load profile history could be assessed.

Oxygen storage capacity (OSC) is one of the most critical characteristics of a three-way catalyst (TWC) and is closely related to the catalyst aging and performance. In this study, a dynamic OSC model involving two oxygen storage sites with distinct kinetics was developed. The dual-site OSC model was validated on a bench reactor and a natural gas engine. The model was capable of predicting temperature dependence on OSC with H2, CO and CH4 as reductants. Also, the effects of oxygen concentration and space velocity on the amount of OSC were captured by the model. The validated OSC model was applied to simulate lean breakthrough phenomena with varied space velocities and oxygen concentrations. It is found that OSC during lean breakthrough is not a constant for a particular TWC catalyst and is dependent on space velocity and oxygen concentration. Specifically, breakthrough time exhibits a non-linear, inverse correlation to oxygen flux.

Commercial Cu-Zeolite SCR catalyst can store and subsequently release significant amount of H2O. The process is accompanied by large heat effects. It is critical to model this phenomenon to design aftertreatment systems and to provide robust tuning strategies to meet cold start emissions and low temperature operation. The complex reaction mechanism of water adsorption and desorption over a Cu-exchanged SAPO-34 catalyst at low temperature was studied through steady state and transient experiments. Steady state isotherms were generated using a gravimetric method and then utilized to predict water storage interactions with respect to feed concentration and catalyst temperature. Transient temperature programmed desorption (TPD) experiments provided the kinetic information required to develop a global kinetic model from the experimental data. The model captures fundamental characteristics of water adsorption and desorption accompanied by the heat effects.