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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.

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.

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.

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.

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.

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.

A FeCrAlloy mesh-type catalyst has been used to reduce hydrocarbons (HC) and carbon monoxide (CO) emissions from a 4-stroke HCCI engine. Significant for the HCCI engine is a high compression ratio and lean mixtures, which leads to a high efficiency, low combustion temperatures and thereby low NOx emissions, <5 pmm, but also low exhaust temperatures, around 300°C. It becomes critical to: 1. Ensure that the HCCI-combustion generates as low HC emissions as possible, this can be done by very precise control of engine inlet conditions and, if possible, compression ratio. 2. Ensure that the exhaust temperature is high enough, without loosing efficiency or producing NOx; in order to get an oxidizing catalyst to work. 3. Select proper catalyst material for the catalyst so that the exhaust temperature can be as low as possible.

With ever more stringent CO2 emissions mandates, many automobile manufacturers are seeking the fuel economy benefits of diesel and lean-burn gasoline engines. At the same time the emissions standards that diesel and gasoline engines will have to meet in the next decade continue to reduce. Proposed solutions for meeting the stringent emissions standards all appear to have limitations, such as propensities to poisoning from sulfur, narrow operating temperature windows, and requirements for controls that give rapid rich excursions. Non-thermal plasma-catalyst systems have shown good performance in bench testing while being largely unaffected by these same issues. A two-stage system with a unique non-thermal plasma reactor combined with a zeolite-based catalyst has been constructed and shown to work over a wide temperature range.

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.

An ionization sensor has been used to study the combustion process in a six-cylinder lean burn, truck-sized engine fueled with natural gas and optimized for low emissions of nitric oxides. The final goal of the investigations is to study the prospects of using the ionization sensor for finding the optimal operating position with respect to low NOx emission and stable engine operation. The results indicate that unstable combustion can be detected by analyzing the coefficient of variation (CoV) of the detector current amplitude. Close relationships between this measure and the CoV of the indicated mean effective pressure have been found during an air-fuel ratio scan with fixed ignition advance.

NOx reduction under simulated lean burn conditions was studied using a non-thermal plasma in combination with zeolite and alumina catalysts. The influence of temperature and plasma treatment on the catalytic performance was investigated. Zeolite catalyst B showed high activity in the 150-300°C temperature region. Alumina Catalyst D was most active at temperatures higher than 250°C. In addition, the alumina catalyst was effective in oxidation of aldehydes formed during plasma treatment of the reaction mixture. When the reaction was carried out over a catalyst bed consisting of separate layers of the zeolite and alumina catalysts, the catalyst temperature range for significant NOx reduction was expanded to 150-500°C.

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.

A double dielectric barrier discharge reactor driven by an alternating voltage is a relatively simple approach to promote oxidation of NO to NO2 for subsequent reduction in a catalyst bed. The chemical performance of such a non-thermal plasma reactor is determined by its current and electric field behavior in the gap, and by the fraction of the current carried by electrons, because the key reactants which initiate the NO oxidation and accompanying chemical changes are produced there, mostly by electron impact. We have tried to determine by models and experiments the bounds on performance of double dielectric barrier reactors and guidelines for optimization. Models reported here predict chemical results from time-resolved applied voltage and series sense capacitor data.

Experiments on a modern DI Diesel engine were carried out: The engine was fuelled with standard Diesel fuel, RME and a mixture of 85% standard Diesel fuel, 5% RME and 10% higher alcohols under low load conditions (4 bar IMEP). During these experiments, different external EGR levels were applied while the injection timing was chosen in a way to keep the location of 50% heat release constant. Emission analysis results were in accordance with widely known correlations: Increasing EGR rates lowered NOx emissions. This is explained by a decrease of global air-fuel ratio entailing longer ignition delay. Local gas-fuel ratio increases during ignition delay and local combustion temperature is lowered. Exhaust gas analysis indicated further a strong increase of CO, PM and unburned HC emissions at high EGR levels. This resulted in lower combustion efficiency. PM emissions however, decreased above 50% EGR which was also in accordance with previously reported results.