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A combination of laboratory reactor measurements and vehicle FTP testing has been combined to demonstrate a method for diagnosing the formation of NO2 from a diesel oxidation catalyst (DOC). Using small cores from a production DOC and simulated diesel exhaust, the laboratory reactor experiments are used to support a model for DOC chemical reaction kinetics. The model we propose shows that the ability to produce NO2 is chemically linked to the ability of the catalyst to oxidize hydrocarbon (HC). For thermally damaged DOCs, loss of the HC oxidation function is simultaneous with loss of the NO2 production function. Since HC oxidation is the source of heat generated in the DOC under regeneration conditions, we conclude that a diagnostic of the DOC exotherm is able to detect the failure of the DOC to produce NO2. Vehicle emissions data from a 6.6 L Duramax HD pick-up with DOC of various levels of thermal degradation is provided to support the diagnostic concept.

Recent work has shown that energy efficiencies as well as yields and selectivities of the NOx reduction reaction can be enhanced by combining a plasma discharge with select catalysts. While analysis of gas phase species with a chemiluminescent NOx meter and mass spectrometer show that significant removal of NOx is achieved, high background concentrations of nitrogen preclude the measurement of nitrogen produced from NOx reduction. Results presented in this paper show that N2 from NOx reduction can be measured if background N2 is replaced with helium. Nitrogen production results are presented for a catalyst system where the catalyst is in the plasma region and where the catalyst is downstream from the plasma. The amount of N2 produced is compared with the amount of NOx removed as measured by the chemiluminescent NOx meter. The measured nitrogen from NOx reduction accounts for at least 40% of the total NOx removed for both reactor configurations.

This paper describes two independent studies on γ-alumina as a plasma-activated catalyst. γ-alumina (2.5 - 4.3 wt%) was coated onto the surface of mesoporous silica to determine the importance of aluminum surface coordination on NOx conversion in conjunction with nonthermal plasma. Results indicate that the presence of 5- and 6- fold aluminum coordination sites in γ-alumina could be a significant factor in the NOx reduction process. A second study examined the effect of changing the reducing agent on NOx conversion. Several hydrocarbons were examined including propene, propane, isooctane, methanol, and acetaldehyde. It is demonstrated that methanol was the most effective reducing agent of those tested for a plasma-facilitated reaction over γ-alumina.

The catalytic activity of selected materials (BaY and NaY zeolites, and γ-alumina) for selective NOx reduction in combination with a non-thermal plasma was investigated. Our studies suggest that aldehydes, formed during the plasma treatment of simulated diesel exhaust, are the important species for the reduction of NOx to N2. Indeed, all materials that are active in plasma-assisted catalysis were found to be very effective for the thermal reduction of NOx in the presence of aldehydes. For example, the thermal catalytic activity of a BaY zeolite with aldehydes gives 80-90% NOx removal at 250°C with 200ppm NOx at the inlet and a VHSV=12,000 h-1. The hydrocarbon reductants, n-octane and 1-propyl alcohol, have also shown high thermal catalytic activity for NOx removal over BaY, NaY and γ-alumina.

In the discharge-catalyst treatment of diesel exhaust the discharge chemistry is known to oxidize NO to NO2 as well as to produce partially oxidized hydrocarbons for the heterogeneous reduction step. We find NO2 to be much more easily reduced to N2 on our catalysts, as long as there is a sufficient supply of reductant present. Unfortunately we typically find that a fraction of the NO2 is only partially reduced back to NO. Since much of the original hydrocarbon survives both the plasma and our catalyst, a subsequent stage of plasma will oxidize NO back to NO2 while at the same time replenishing the supply of partially oxidized hydrocarbon for another stage of heterogeneous catalysis. We present experimental evidence illustrating the advantages of multi-step discharge-catalyst treatment of NOx in simulated diesel exhaust.

We present here a phenomenological analysis of a cascade of two-step discharge-catalyst reactors. That is, each step of the cascade consists of a discharge reactor in series with a catalyst bed. These reactors are intended for use in the reduction of tailpipe emission of NOx from diesel engines. The discharge oxidizes NO to NO2, and partially oxidizes HC. The NO2 then reacts on the catalyst bed with hydrocarbons and partially oxidized HCs and is reduced to N2. The cascade may be essential because the best catalysts for this purpose that we have also convert significant fractions of the NO2 back to NO. As we show, reprocessing the gas may not only be necessary, but may also result in energy savings and increased device reliability.

The NOx reduction performance under lean conditions over γ-alumina was evaluated using a micro-reactor system and a non-thermal plasma-equipped bench test system. Various alumina samples were obtained from alumina manufacturers to assess commercial alumina materials. In addition, γ-alumina samples were synthesized at Caterpillar with a sol-gel technique in order to control alumina properties. The deNOx performances of the alumina samples were compared. The alumina samples were characterized with analytical techniques such as inductively coupled plasma (ICP) emission spectroscopy, temperature programmed desorption (TPD) and surface area measurements (BET) to understand physical and chemical properties. The information derived from these techniques was correlated with the NOx reduction performance to identify key parameters of γ-alumina for optimizing materials for lean-NOx and plasma assisted catalysis.

A slipstream of exhaust from a Caterpillar 3126B engine was diverted into a plasma-catalytic NOx control system in the space velocity range of 7,000 to 100,000 hr-1. The stream was first fed through a non-thermal plasma that was formed in a coaxial cylinder dielectric barrier discharge reactor. Plasma treated gas was then passed over a catalyst bed held at constant temperature in the range of 573 to 773 K. Catalysts examined consisted of γ-alumina, indium-doped γ-alumina, and silver-doped γ-alumina. Road and rated load conditions resulted in engine out NOx levels of 250 - 600 ppm. The effects of hydrocarbon level, catalyst temperature, and space velocity are discussed where propene and in one case ultra-low sulfur diesel fuel (late cycle injection) were the reducing agents used for NOx reduction. Results showed NOx reduction in the range of 25 - 97% depending on engine operating conditions and management of the catalyst and slipstream conditions.

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.

This paper focuses on measuring particle emissions of a representative light-duty diesel vehicle equipped with different engine exhaust aftertreatment in close-coupled position, including one designed to meet the upcoming Euro 6 emission standards. The latter combines a lean NOx trap (LNT) and a diesel particulate filter (DPF) in series to simultaneously reduce NOx and PM. Particle Matter (PM) and particle number emissions are measured throughout testing procedure and instrumentation which are compliant with the UN-ECE Regulation 83 proposals. Specifically measuring devices for particle number emissions, provided by two different suppliers, are alternatively used. No significant differences are observed due to the different system employed. On the other hand particle size distributions are measured by means of a specific experimental set-up including a two stage dilution system and an electrical low pressure impactor (ELPI).

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.

High-speed (12 kHz) imaging of combustion luminosity (enhanced by using a sodium fuel additive) has been analyzed and compared to crank angle resolved heat release rates and mass fraction burn profiles in a spray-guided spark-ignited direct-injection (SG-SIDI) optical single-cylinder engine. The addition of a sodium-containing additive to gasoline greatly increases the combustion luminosity, which allows unintensified high-speed (12 kHz) imaging of early partially premixed flame kernel growth and overall flame propagation with excellent signal-to-noise ratio for hundreds of consecutive engine cycles. Ignition and early flame kernel growth are known to be key to understanding and eliminating poor burn cycles in SG-SIDI engines.

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.

The light-medium load operating range (4-7 bar net IMEP) presents many challenges for advanced low temperature combustion strategies utilizing low cetane fuels (specifically, 87-octane gasoline) in light-duty, high-speed engines. The overly lean overall air-fuel ratio (Φ≺0.4) sometimes requires unrealistically high inlet temperatures and/or high inlet boost conditions to initiate autoignition at engine speeds in excess of 1500 RPM. The objective of this work is to identify and quantify the effects of variation in input parameters on overall engine operation. Input parameters including inlet temperature, inlet pressure, injection timing/duration, injection pressure, and engine speed were varied in a ~0.5L single-cylinder engine based on a production General Motors 1.9L 4-cylinder high-speed diesel engine.

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.

Cooled exhaust gas recirculation (EGR) is widely used in diesel engines to control engine-out NOx (oxides of nitrogen) emissions. A portion of the exhaust gases is re-circulated into the intake manifold of the engine after cooling it through a heat exchanger. EGR cooler heat exchangers, however, tend to lose efficiency and have increased pressure drop as deposit forms on the heat exchanger surface due to transport of soot particles and condensing species to the cooler walls. In this study, condensation of water vapor and hydrocarbons at the exit of the EGR cooler was visualized using a fiberscope coupled to a camera equipped with a complementary metal oxide semiconductor (CMOS) color sensor. A multi-cylinder diesel engine was used to produce a range of engine-out hydrocarbon concentrations. Both surface and bulk gas condensation were observed with the visualization setup over a range of EGR cooler coolant temperatures.

Diesel engine developers are continually striving to reduce harmful NOx emissions through various calibration and hardware strategies. One strategy being implemented in production Diesel engines involves utilizing cooled exhaust gas recirculation (EGR). Although there is a significant NOx reduction potential by utilizing cooled EGR, there are also several issues associated with it, such as EGR cooler fouling and a reduction in cooler effectiveness that can occur over time. The exact cause of these issues and many others related to cooler fouling are not clearly understood. One such unanswered issue or phenomenon that has been observed in both field tested and lab tested EGR coolers is that of a recovery in EGR cooler effectiveness after a shutdown or after cycling between various conditions.

Proposed vehicle emissions regulations for the near future have prompted automotive manufactures and component suppliers to focus heavily on developing more efficient exhaust aftertreatment devices to lower emissions from spark and compression ignition engines. One of the primary pollutants from lean-burn engines, especially from diesels, are oxides of nitrogen (NOx). Current three-way catalytic converters will not have adequate performance to meet future emission reduction requirements. Therefore, there is a need for researchers and engineers to develop efficient exhaust aftertreatment devices that will reduce NOx emissions from lean-burn engines. These devices must have very high conversion of NOx gases, be unaffected by exhaust-gas impurity such as sulfur, and have minimal impact on vehicle operations and fuel economy. An effective technology for NOx control that is currently receiving a lot of attention is a non-thermal plasma system.

With new legislation and federal regulation for vehicle emission levels, automotive and truck manufacturers have been prompted to focus on emission control technologies that limit the level of exhaust pollutants. One of the primary pollutants, especially from diesel engines, is oxides of nitrogen (NOx). One possible solution to this pollution challenge is to design a more efficient internal combustion engine, which would require better engine operating parameter controls. However, there are limitations associated with such tight engine management. This need has led researchers and engineers to focus on the development of exhaust aftertreatment devices that will reduce NOx emissions with current diesel engines. An optimum aftertreatment device must be unaffected by exhaust-gas impurity poisoning such as sulfur products, and must have minimal impact on vehicle operations and fuel economy.

NOx reduction efficiency in simulated lean exhaust conditions has been examined for three proprietary catalyst materials using a non-thermal plasma discharge as a pretreatment stage to the catalyst. Using propene as the reducing agent for selective catalytic reduction, 74% reduction of NOx has been observed in the presence of 20 ppm SO2. For sulfur-free simulated exhaust, 84% NOx reduction has been obtained. Results show that the impact of sulfur on the samples examined can vary widely from virtually no effect (< 5%) to more than 20% loss in activity depending on the catalyst. Any loss due to sulfur poisoning appears to be irreversible according to limited measurements on poisoned catalysts exposed to sulfur-free exhaust streams. Catalysts were tested over a temperature range of 473-773K, with the highest activity observed at 773K. Examination of this large temperature window has shown that the optimum C1:NOx ratio changes with temperature.