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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.

Stoichiometric natural gas engines with three-way catalysts emit less NOx and CH4 due to their higher efficiency compared to lean-burn natural gas engines. Although hydrothermal aging of three-way catalysts has been extensively studied, a deeper understanding beyond hydrothermal aging is needed to explain real-world performance, especially for natural gas engines with near-zero NOx emissions. In this investigation, field-aged three-way catalysts were characterized to identify the contribution of chemical aging to their overall performance. It was found that the sulfur species on the field-aged TWCs were entirely distributed along the catalyst length, showing a decreasing trend, whereas phosphorous contamination was mainly observed at the inlet section of the three-way catalysts, and the phosphorous concentration declined sharply along the axial length.

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.

Detailed characterization of particle emissions from three different engine technologies were performed, two of which were advanced technology engines. One of the engines was a nonroad Tier 4 Final emission regulation compliant 6.8L John Deere PSS 6068 diesel engine operated with its production calibration strategy. The other two engine platforms were advanced engine technologies whose controllers were developed by Southwest Research Institute (SwRI). These included a dual fuel Navistar MaxxForce 13L natural gas-diesel engine and a Cummins ISX 15L diesel engine. The dual fuel engine was operated in two distinct modes, conventional dual fuel (CDF) mode and low temperature reactivity controlled compression ignition (RCCI) mode. The Cummins ISX engine was operated using a “hot” or low EGR combustion strategy. For each engine technology, the test campaign involved steady-state test modes ranging from low speed low load to high speed high load conditions.

With the advancement of engine technologies and combustion strategies, aftertreatment architectures are expected to evolve as they continue to be the primary emissions mitigation hardware. Some of the engine approaches offer unique challenges and benefits that are not well understood beyond criteria pollutant emissions. As such, there continues to be a need to quantify engine emissions characteristics in pursuit of catalyst technology development and the use of advanced simulation tools. The following study discusses results from an extensive engine emissions assessment for current state-of-the-art technology and novel combustion regimes. The engines tested include a Tier 4 final compliant 6.8 L John Deere PSS 6068 diesel engine, a modified 15 L diesel engine, and a dual fuel 13 L natural gas-diesel engine. The dual fuel engine could operate in conventional positive ignition mode (CDF) or low temperature reactivity-controlled compression ignition mode (RCCI).

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.

Formation of urea-derived deposits in selective catalytic reduction (SCR) aftertreatment systems continues to be problematic at temperatures at and below 215 °C. Several consequences of deposit formation include: NOx and NH3 slip, exhaust flow maldistribution, increased engine backpressure, and corrosion of aftertreatment components. Numerous methods have been developed to reduce deposit formation, but to date, there has been no solution for continuous low-temperature dosing of Urea-Water Solution (UWS). This manuscript presents a novel methodology for reducing low-temperature deposit formation in SCR aftertreatment systems. The methodology described herein involves incorporation and dissolution of an HNCO hydrolysis catalyst directly into the UWS. HNCO is a transient species formed by the thermolysis of urea upon injection of UWS into the aftertreatment system.

Increased in-cylinder hydrogen levels have been shown to improve burn durations, combustion stability, HC emissions and knock resistance which can directly translate into enhanced engine efficiency. External fuel reformation can also be used to increase the hydrogen yield. During the High-Efficiency, Dilute Gasoline Engine (HEDGE) consortium at Southwest Research Institute (SwRI), the potential of increased hydrogen production in a dedicated-exhaust gas recirculation (D-EGR) engine was evaluated exploiting the water gas shift (WGS) and steam reformation (SR) reactions. It was found that neither approach could produce sustained hydrogen enrichment in a real exhaust environment, even while utilizing a lean-rich switching regeneration strategy. Platinum group metal (PGM) and Ni WGS catalysts were tested with a focus on hydrogen production and catalyst durability.

Three-way catalysts have been used in a variety of stoichiometric natural gas engines for emission control. During real-world operation, these catalysts have experienced a large number of temporary and permanent deactivations including thermal aging and chemical contamination. Thermal aging is typically induced either by high engine-out exhaust temperatures or the reaction exotherm generated on the catalysts. Chemical contamination originates from various inorganic species such as Phosphorous (P) and Sulfur (S) that contain in engine fluids, which can poison and/or mask the catalyst active components. Such deactivations are quite difficult to simulate under laboratory conditions, due to the fact that multiple deactivation modes may occur at the same time in the real-world operations. In this work, a set of field-aged TWCs has been analyzed through detailed laboratory research in order to identify and quantify the real-world aging mechanisms.

Plug flow reactors, simulating engine exhaust gas, are widely used in emissions control research to gain insight into the reaction mechanisms and engineering aspects that controls activity, selectivity, and durability of catalyst components. The choice of relevant hydrocarbon (HC) species is one of the most challenging factor in such laboratory studies, given the variety of compositions that can be encountered in different application scenarios. Furthermore, this challenge is amplified by the experimental difficulties related to introducing heavier and multi-component HCs and analyzing the reaction products.

The aging impact on oxygen storage capacity (OSC) and catalyst performance was investigated on one degreened and one aged (hydrothermally aged at 955 °C for 50 h) commercial three-way catalyst (TWC) by experiments and modeling. The difference of OSC between the degreened and aged TWCs was dependent on catalyst temperature. The largest difference was found at 600 °C, at which the amount of OSC decreased by 45.5%. Catalyst performance was evaluated through lightoff tests at two simulated engine exhaust conditions (lean and rich) on a micro-reactor. The aging impact on the catalyst performance was different under lean and rich environments and investigated separately. At the lean condition, oxidation of CO and C3H6 was significantly suppressed while oxidation of C3H8 was relatively less degraded. At the rich condition, the inhibition effect was more pronounced on the aged TWC and inhibiting hydrocarbon species from C3H6 partial oxidation can survive at temperatures up to 450 °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.

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.

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.

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.

The 2010 emissions standards for heavy-duty engines have established a limit of oxides of nitrogen (NOX) emissions of 0.20 g/bhp-hr. However, the California Air Resource Board (ARB) projects that even when the entire on-road fleet of heavy-duty vehicles operating in California is compliant with 2010 emission standards, the National Ambient Air Quality Standards (NAAQS) requirement for ambient particulate matter (PM) and Ozone will not be achieved without further reduction in NOX emissions. The California Air Resources Board (CARB) funded a research program to explore the feasibility of achieving 0.02 g/bhp-hr NOX emissions.

Advanced emission control systems for diesel engines usually include a combination of Diesel Oxidation Catalyst (DOC), Diesel Particulate Filter (DPF), Selective Catalytic Reduction (SCR), and Ammonia Slip Catalyst (ASC). The performance of these catalysts individually, and of the aftertreatment system overall, is negatively affected by the presence of oxides of sulfur, originating from fuel and lubricant. In this paper, we illustrated some key aspects of sulfur interactions with the most commonly used types of catalysts in advanced aftertreatment systems. In particular, DOC can oxidize SO2 to SO3, collectively referred to as SOx, and store these sulfur containing species. The key functions of a DOC, such as the ability to oxidize NO and HC, are degraded upon SOx poisoning. The impact of sulfur poisoning on the catalytic functions of a DPF is qualitatively similar to DOC.

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 study, the criteria pollutant emissions from a light duty vehicle equipped with Dedicated EGR® technology were compared with emissions from an identical production GDI vehicle without externally cooled EGR. In addition to the comparison of criteria pollutant mass emissions, an analysis of the gaseous and particulate chemistry was conducted to understand how the change in combustion system affects the optimal aftertreatment control system. Hydrocarbon emissions from the vehicle were analyzed usin g a variety of methods to quantify over 200 compounds ranging in HC chain length from C1 to C12. The particulate emissions were also characterized to quantify particulate mass and number. Gaseous and particulate emissions were sampled and analyzed from both vehicles operating on the FTP-75, HWFET, US06, and WLTP drive cycles at the engine outlet location.