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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.

Dedicated Exhaust Gas Recirculation (D-EGR®) technology provides a novel means for fuel efficiency improvement through efficient, on-board generation of H2 and CO reformate [1, 2]. In the simplest form of the D-EGR configuration, reformate is produced in-cylinder through rich combustion of the gasoline-air charge mixture. It is also possible to produce more H2 by means of a Water Gas Shift (WGS) catalyst, thereby resulting in further combustion improvements and overall fuel consumption reduction. In industrial applications, the WGS reaction has been used successfully for many years. Previous engine applications of this technology, however, have only proven successful to a limited degree. The motivation for this work was to develop and optimize a WGS catalyst which can be employed to a D-EGR configuration of an internal combustion engine. This study consists of two parts.

The Exhaust Composition Transient Operation LaboratoryTM (ECTO-LabTM) is a burner system developed at Southwest Research Institute (SwRI) for simulation of IC engine exhaust. The current system design requires metering and combustion of nitromethane in conjunction with the primary fuel source as the means of NOX generation. While this method affords highly tunable NOX concentrations even over transient cycles, no method is currently in place for dictating the speciation of nitric oxide (NO) and nitrogen dioxide (NO2) that constitute the NOX mixture. NOX generated through combustion of nitromethane is dominated by NO, and generally results in an NO2:NOX ratio of < 5 %. Generation of any appreciable quantities of NO2 is therefore dependent on an oxidation catalyst to oxidize a fraction of the NO to NO2.

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.

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.

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.

The high global warming potential of nitrous oxide (N2O) led to its inclusion in the list of regulated greenhouse gas (GHG) pollutants [1, 2]. The mitigation of N2O on aftertreatment catalysts was shown to be ineffective as its formation and decomposition temperatures do not overlap. Therefore, the root causes for N2O formation were investigated to enable the catalyst architectures and controls development for minimizing its formation. In a typical heavy-duty diesel exhaust aftertreatment system based on selective catalytic reduction of NOx by ammonia derived from urea (SCR), the main contributors to tailpipe N2O are expected to be the undesired reaction between NOx and NH3 over SCR catalyst and NH3 slip in to ammonia slip catalyst (ASC), part of which gets oxidized to N2O.

Gasoline direct injection (GDI) engines have become very attractive in transportation due to several benefits over preceding engine technologies. However, GDI engines are associated with higher levels of particulate matter (PM) emissions, which is a major concern for human health. The aim of this work is to broaden the understanding of the effect of hydrogen combustion and the influence of the three way catalytic converter (TWC) on PM emission characteristics. The presence of hydrogen in GDI engines has been reported to reduce fuel consumption and improve the combustion process, making it possible to induce higher rates of EGR. A prototype exhaust fuel reformer build for on-board vehicle hydrogen-rich gas (reformate) production has been integrated within the engine operation and studied in this work.

Selective Catalytic Reduction is the primary method of NOX emission abatement in lean-burn internal combustion. This process requires the decomposition of a 32.5 wt. % urea-water solution (UWS) to provide ammonia as a reducing agent for NOX, but at temperatures < 250 °C the injection of UWS is limited due to the formation of harmful deposits within an aftertreatment system and decreased ammonia production. Previous work has sufficiently demonstrated that the addition of surfactant and a urea/isocyanic acid (HNCO) decomposition catalyst to UWS can significantly decrease deposit formation within an aftertreatment system. The objective of this work was to further optimize the modified UWS formulation by investigating different types and concentrations of surfactants and titanium-based urea/HNCO catalyst. Because there is a correlation between surface tension and water evaporation, it was theorized that minimizing the surface tension of UWS would result in decreased deposit formation.

SCR-on-filter, or SCRoF, is an emerging technology for different market segments and vehicle applications. The technology enables simultaneous particulate matter trapping and NOX reduction, and provides thermal management and aftertreatment packaging benefits. However, there is little information detailing the lubricant derived exposure effects on functional SCR performance. A study was conducted to evaluate the impact of various oil consumption pathways on a light duty DOC and SCRoF aftertreatment system. This aftertreatment system was aged utilizing an engine test bench modified to enable increased oil consumption rates via three unique oil consumption pathways. The components were characterized for functional SCR performance, ash morphology, and ash deposition characteristics. This included utilizing techniques, such as SEM / EDS, to evaluate the ash structures and quantify the ash elemental composition.

An operational challenge associated with SCR catalysts is the NH3 slip control, particularly for commercial small pore Cu-zeolite formulations as a consequence of their significant ammonia storage capacity. The desorption of NH3 during increasing temperature transients is one example of this challenge. Ammonia slipping from SCR catalyst typically passes through a platinum based ammonia oxidation catalyst (AMOx), leading to the formation of the undesired byproducts NOx and N2O. We have discovered a distinctive characteristic, an overlapping NH3 desorption and oxidation, in a state-of-the-art Cu-zeolite SCR catalyst that can minimize NH3 slip during temperature transients encountered in real-world operation of a vehicle.

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.

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.

Several reactor systems have been used to study the catalytic chemistry of a particular proprietary zeolitic catalyst in conditions that mimic those found in light-duty diesel exhaust after a non-thermal plasma generator. Very similar catalytic results were obtained with NO + plasma or NO2 as the source of NOx using propene (C3H6) as the reductant. The formation of nitrogen, carbon dioxide, and other products were studied from 150°C to 250°C using a He balance gas and NOx in the form of NO2. The results demonstrate that nitrogen is formed by the selective catalytic reduction of NO2 by propene. The highest activity for N2 formation from NO2 was near 50% conversion at 200°C for a space velocity of 12,600 h-1. The NOx conversion by adsorption and by catalytic reduction was quantified. By performing studies with and without the presence of water, a clear separation in behavior between adsorption processes and catalytic reaction was observed.

Ideally, complete thermal decomposition of urea should produce only two products in active Selective Catalytic Reduction (SCR) systems: ammonia and carbon dioxide. In reality, urea thermal decomposition reaction includes the formation of isocyanic acid as an intermediate product. Being highly reactive, isocyanic acid can initiate the formation of larger molecular weight compounds such as cyanuric acid, biuret, melamine, ammeline, ammelide, and dicyandimide [1,2,3,4]. These compounds can be responsible for the formation of deposits on the walls of the decomposition reactor in urea SCR systems. Composition of these deposits varies with temperature exposure, and under certain conditions, can create oligomers such as melam, melem, and melon [5, 6] that are difficult to remove from exhaust systems. Deposits can affect the efficiency of the urea decomposition, and if large enough, can inhibit the exhaust flow.

Ideally, complete decomposition of urea should produce only two products in active Selective Catalytic Reduction (SCR) systems: ammonia and carbon dioxide. In reality, urea decomposition reaction is a two-step process that includes the formation of ammonia and isocyanic acid as intermediate products via thermolysis. Being highly reactive, isocyanic acid can initiate the formation of larger molecular weight compounds such as cyanuric acid (CYN), biuret (BIU), melamine (MEL), ammeline (AML), ammelide (AMD), and dicyandimide (DICY). These compounds can be responsible for the formation of deposits on the walls of the decomposition reactor in urea SCR systems. Composition of these deposits varies with temperature exposure, and under certain conditions can create oligomers that are difficult to remove from exhaust pipes. Deposits can affect efficiency of the urea decomposition, and if large enough, can inhibit the exhaust flow and negatively impact ammonia distribution on the SCR catalyst.

Mitigation of urea deposit formation and improved ammonia production at low exhaust temperatures continues to be one of the most significant challenges for current generation selective catalytic reduction (SCR) aftertreatment systems. Various technologies have been devised to alleviate these issues including: use of alternative reductant sources, and thermal treatment of the urea-water solution (UWS) pre-injection. The objective of this work was to expand the knowledge base of a potential third option, which entails chemical modification of UWS by addition of a titanium-based urea/isocyanic acid (HNCO) decomposition catalysts and/or surfactant to the fluid. Physical solid mixtures of urea with varying concentrations of ammonium titanyl oxalate (ATO), oxalic acid, and titanium dioxide (TiO2) were generated, and the differences in NH3 and CO2 produced upon thermal decomposition were quantified.

The ammonia slip catalyst (ASC), typically composed of Pt oxidation catalyst overlaid with SCR catalyst, is employed for the mitigation of NH3 slip originating from SCR catalysts. Oxidation and SCR functionalities in an ASC can degrade through two key mechanisms i) irreversible degradation due to thermal aging and ii) reversible degradation caused by sulfur-oxides. The impact of thermal aging is well understood and it mainly degrades the SCR function of the ASC and increases the NH3 conversion to undesired products [1]. This paper describes the impact of sulfur-oxides on critical functions of ASC and on NH3 oxidation activity and selectivity towards N2, NOx and N2O. Furthermore impact of desulfation under selected conditions and its extent of ASC performance recovery is explained.

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.

In this contribution, nuanced changes of a commercial Cu-SSZ-13 catalyst with hydrothermal aging, which have not been previously reported, as well as their corresponding impact on SCR functions, are described. In particular, a sample of Cu-SSZ-13 was progressively aged between 550 to 900°C and the changes of performance in NH3 storage, oxidation functionality and NOx conversion of the catalyst were measured after hydrothermal exposure at each temperature. The catalysts thus aged were further characterized by NH3-TPD, XRD and DRIFTS techniques for structural changes. Based on the corresponding performance and structural characteristics, three different regimes of hydrothermal aging were identified, and tentatively as assigned to “mild”, “severe” and “extreme” aging. Progressive hydrothermal aging up to 750°C decreased NOx conversion to a small degree, as well as NH3 storage and oxidation functions.