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Exhaust Gas Recirculation, EGR, is one of the most effective means of reducing NOx emissions from diesel engines and is likely to be used in order to meet future emissions standards. Exhaust gases can either be used to replace some of the air that enters the engine or can be added to the intake flow. The former case has been studied in this paper. One advantage of air replacement is that the exhaust mass flow is reduced in addition to the decreased NOx formation. The objective of this study has been to take a closer look at the factors affecting NOx emissions at different EGR rates. This is done by combining heat release analysis, based on measured pressure traces and NO formation in a multi zone combustion model. The model used is an improved version of an earlier presented model [1]. One feature in the new model is the possibility to separate the NO formation during the premixed combustion from NO formed during the diffusive combustion.

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.

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.

Homogeneous Charge Compression Ignition (HCCI) has a great potential for low NOx emissions but problems with emissions of unburned hydrocarbons (HC). One way of reducing the HC is to use direct injection. The purpose of this paper is to present experimental data on the trade off between NOx and HC. Injection timing, injection pressure and nozzle configuration all effect homogeneity of the mixture and thus the NOx and HC emissions. The engine studied is a single cylinder version of a Scania D12 that represents a modern heavy-duty truck size engine. A common rail (CR) system has been used to control injection pressure and timing. The combustion using injectors with different nozzle hole diameters and spray angle, both colliding and non-colliding, has been studied. The NOx emission level changes with start of injection (SOI) and the levels are low for early injection timing, increasing with retarded SOI. Different injectors produce different NOx levels.

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.

Various gold catalysts were prepared using commercial and in-house fabricated advanced catalyst supports that included mesoporous silica, mesoporous alumina, sol-gel alumina, and transition metal oxides. Gold nanoparticles were loaded on the supports by co-precipitation, deposition-precipitation, ion exchange and surface functionalization techniques. The average gold particle size was ∼20nm or less. The oxidation activity of the prepared catalysts was studied using carbon monoxide and light hydrocarbons (ethylene, propylene and propane) in presence of water and CO2 and the results are presented.

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.

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.

A number of oxidation catalysts have been prepared using different types of advanced support materials such as ceria-zirconia, silica-titania, spinels and perovskites. Active metals such as Pd and Au-Pd were loaded by conventional impregnation techniques and/or deposition-precipitation methods. A liquid hydrocarbon delivery system was designed and implemented for the catalyst test benches in order to simulate the diesel engine exhaust environment. The activity of fresh (no degreening) catalysts was evaluated with traditional CO and light hydrocarbons (C2H4, C3H6) as well as with heavy hydrocarbons such as C10 H22.

NOx reduction efficiency under simulated lean burn conditions is examined for a non-thermal plasma in combination with borosilicate glass, alumina, titania, Cu-ZSM-5 and Na-ZSM-5. The non-thermal plasma alone or with a packed bed of borosilicate glass beads converts NO to NO2 and partially oxidizes hydrocarbons. Alumina and Na-ZSM-5 reduce a maximum of 40% and 50% of NOx respectively; however, the energy cost is high for Na- ZSM-5. Cu-ZSM-5 converts less than 20% with a very high energy consumption. The anatase form of titania reduces up to 35% of NOx at a relatively high energy consumption (150J/L) when the catalyst is contained in the plasma region, but does not show any appreciable conversion when placed downstream from the reactor. This phenomenon is explained by photo-activation of anatase in the plasma.

With stringent emission regulations, aftertreatment systems with a Diesel Particulate Filter (DPF) and a Selective Catalytic Reduction (SCR) are required for diesel engines to meet PM and NOx emissions. The adoption of aftertreatment increases the back pressure on a typical diesel engine and makes engine calibration a complicated process, requiring thousands of steady state testing points to optimize engine performance. When configuring an engine to meet Tier IV final emission regulations in the USA or corresponding Stage IV emission regulations in Europe, this high back pressure dramatically impacts transient performance. The peak NOx, smoke and exhaust temperature during a diesel engine transient cycle, such as the Non-Road Transient Cycle (NRTC) defined by the US Environmental Protection Agency (EPA), will in turn affect the performance of the aftertreatment system and the tailpipe emissions level.

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.

Although the urea-SCR technology exhibits high NO reduction efficiency over a wide range of temperatures among the lean NO reduction technologies, further improvement in low-temperature performance is required to meet the future emission standards and to lower the system cost. In order to improve the catalyst technologies and optimize the system performance, it is critical to understand the reaction mechanisms and catalyst behaviors with respect to operating conditions. Urea-SCR catalysts exhibit poor NO reduction performance at low-temperature operating conditions (T ≺ 150°C). We postulate that the poor performance is either due to NH₃ storage inhibition by species like hydrocarbons or due to competitive adsorption between NH₃ and other adsorbates such as H₂O and hydrocarbons in the exhaust stream. In this paper we attempt to develop one-dimensional models to characterize inhibition and competitive adsorption in Fe-zeolite-based urea-SCR catalysts based on bench reactor experiments.

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.

We present data in this paper showing that non-thermal plasma in combination with heterogeneous catalysis is a promising technique for the treatment of NOx in diesel exhaust. Using a commonly available zeolite catalyst, sodium Y, to treat synthetic diesel exhaust we report approximately 50% chemical reduction of NOx over a broad, representative temperature range. We have measured the overall efficiency as a function of the temperature and hydrocarbon concentration. The direct detection of N2 and N2O when the background gas is replaced by helium confirms that true chemical reduction is occurring.

Exhaust Emissions from lean burn natural gas engines may not always be as low as the potential permits, especially engines with open loop lambda control. These engines can produce much higher emissions than a comparable diesel engine without exhaust gas after treatment. Even if the engine has closed loop lambda control, emissions are often unacceptably high for future emission regulations. A three way catalyst is, today, the best way to reduce hazardous emissions. The drawback is that the engine has to operate with a stoichiometric mixture and this leads to; higher heat losses, higher pumping work at low to medium loads, higher thermal stress on the engine and higher knock tendency (requiring lower compression ratio, and thus lower brake efficiency). One way to reduce these drawbacks is to dilute the stoichiometric mixture with EGR. This paper compares lean burn operation with operation at stoichiometric conditions diluted with EGR, and using a three way catalyst.

A two-zone NOx model intended for 1-D engine simulations was developed and used to model NOx emissions from a 2.5 L single-cylinder engine. The intent of the present work is to understand key aspects of a simple NOx model that are needed for predictive accuracy, including NOx formation and destruction phenomena in a DI Diesel combustion system. The presented two-zone model is fundamentally based on the heat release rate and thermodynamic incylinder data, and uses the Extended Zeldovich mechanism to model NO. Results show that the model responded very well to changes in speed, load, injection timing, and EGR level. It matched measured tail pipe NOx levels within 20%, using a single tuning setup. When the model was applied to varied injection rate shapes, it showed correct sensitivity to speed, load, injection timing, and EGR level, but the absolute level was well outside the target accuracy. The same limitation was seen when applying the Plee NOx model.

Power supply systems play a very important role in applications of everyday life. Mainly, for low power generation, there are two ways of producing energy: electrochemical batteries and small engines. In the last few years many improvements have been carried out in order to obtain lighter batteries with longer duration but unfortunately the energy density of 1 MJ/kg seems to be an asymptotic value. If the energy source is an organic fuel with an energy density of around 29 MJ/kg and a minimum overall efficiency of only 3.5%, this device can surpass the batteries. Nowadays the most efficient combustion process is HCCI combustion which is able to combine high energy conversion efficiency and low emission levels with a very low fuel consumption. In this paper, an investigation has been carried out concerning the effects of the compression ratio on the performance and emissions of a mini, Vd = 4.11 [cm3], HCCI engine fueled with diethyl ether.

It is estimated that operating continuously on a B20 fuel containing the current allowable ASTM specification limits for metal impurities in biodiesel could result in a doubling of ash exposure relative to lube-oil-derived ash. The purpose of this study was to determine if a fuel containing metals at the ASTM limits could cause adverse impacts on the performance and durability of diesel emission control systems. An accelerated durability test method was developed to determine the potential impact of these biodiesel impurities. The test program included engine testing with multiple DPF substrate types as well as DOC and SCR catalysts. The results showed no significant degradation in the thermo-mechanical properties of cordierite, aluminum titanate, or silicon carbide DPFs after exposure to 150,000 mile equivalent biodiesel ash and thermal aging. However, exposure of a cordierite DPF to 435,000 mile equivalent aging resulted in a 69% decrease in the thermal shock resistance parameter.

Synergies between various catalytic converters such as SCR and DPF are vital to the success of an integrated aftertreatment system for simultaneous NO and particulate matter control in diesel engines. Several issues such as hydrocarbon poisoning, thermal aging and other coupled aftertreatment dynamics need to be addressed to develop an effective emission control system. This work is significant especially in an integrated DPF-SCR aftertreatment scenario where the SCR catalyst on the filter substrate is exposed to un-burnt diesel hydrocarbons during active regeneration of the particulate filter. This paper reports an experimental and modeling study to understand the effect of hydrocarbons on a Fe-zeolite urea-SCR catalyst. Several bench-reactor tests to understand the inhibition of NO oxidation, to characterize hydrocarbon storage and to investigate the impact of hydrocarbons on SCR reactions were conducted.