John Hoard

Reduction of NOx in synthetic diesel exhaust via two-step plasma-catalysis treatment

Abstract Significant reduction of NOx in synthetic light duty diesel exhaust has been achieved over a broad temperature window by combining atmospheric plasma with appropriate catalysts. The technique relies on the addition of hydrocarbon reductant prior to passing the simulated exhaust through a non-thermal plasma and a catalyst bed. The observed chemistry in the plasma includes conversion of NO to NO2 as well as the partial oxidation of the hydrocarbon. The overall NOx reduction has a maximum of less than 80%, with this maximum obtained only at high-energy input into the plasma, high concentration of hydrocarbon reductant and low space velocity. We present data in this paper illustrating that a multiple-step treatment strategy, whereby two or more plasma-catalyst reactors are utilized in series, can increase the maximum NOx conversion obtainable. Alternatively, this technique can reduce the energy and/or hydrocarbon requirements for a fixed conversion efficiency. When propene is used as the reductant, the limiting reagent for the overall process is most likely acetaldehyde. The data suggest that acetaldehyde is formed in concert with NO oxidation to NO2 in the plasma stage. The limited NOx reduction efficiency attained in a single step, even with excess energy, oxygen content and/or hydrocarbon-to-NOx ratio is well explained by this hypothesis, as is the effectiveness of the multiple-step treatment strategy. We present the data here illustrating the advantage of this approach under a wide variety of conditions.

Numerical Modeling and Experimental Investigations of EGR Cooler Fouling in a Diesel Engine

EGR coolers are mainly used on diesel engines to reduce intake charge temperature and thus reduce emissions of NOx and PM. Soot and hydrocarbon deposition in the EGR cooler reduces heat transfer efficiency of the cooler and increases emissions and pressure drop across the cooler. They may also be acidic and corrosive. Fouling has been always treated as an approximate factor in heat exchanger designs and it has not been modeled in detail. The aim of this paper is to look into fouling formation in an EGR cooler of a diesel engine. A 1-D model is developed to predict and calculate EGR cooler fouling amount and distribution across a concentric tube heat exchanger with a constant wall temperature. The model is compared to an experiment that is designed for correlation of the model. Effectiveness, mass deposition, and pressure drop are the parameters that have been compared. The results of the model are in a good agreement with the experimental data.

Controlling cyclic combustion variations in lean-fueled spark-ignition engines

This paper describes the reduction of cyclic combustion variations in spark-ignited engines, especially under idle conditions in which the air-fuel mixture is lean of stoichiometry. Under such conditions, the combination of residual cylinder gas and parametric variations (such as variations in fuel preparation) gives rise to significant combustion instabilities that may lead to customerperceived engine roughness and transient emissions spikes. Such combustion instabilities may preclude operation at air-fuel ratios that would otherwise be advantageous for fuel economy and emissions. This approach exploits the recognition that a component of the observed combustion instability results from a noisedriven, nonlinear deterministic mechanism that can be actively stabilized by small feedback control actions which result in little if any additional use of fuel. Application of this approach on a test vehicle using crankshaft acceleration as a measure of torque and fuel pulse width modification as a control shows as much as 30% reduction in rms variation near the lean limit.

Selective Reduction of NOx in Oxygen Rich Environments with Plasma-Assisted Catalysis: The Role of Plasma and Reactive Intermediates

Catalytic activity of selected materials (BaY and NaY zeolites, and g-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 in 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, 1000ppm of C1 as acetaldehyde, propionaldehyde, and butyraldehyde, and SV=12,000 h?. The hydrocarbon reductants, n-octane and 1-propyl alcohol have also shown high thermal catalytic activity for NOx removal over BaY, NaY and g-alumina. We believe that this activity is due to the fact that in an oxygen rich environment these compounds can be thermally oxidized over the catalysts to form the important aldehyde reaction intermediates.

An Analytical Study of Thermophoretic Particulate Deposition in Turbulent Pipe Flows

The presence of a cold surface in non-isothermal pipe flows conveying submicron particles causes thermophoretic particulate deposition. In this study, an analytical method is developed to estimate thermophoretic particulate deposition efficiency and its effect on overall heat transfer coefficient of pipe flows in transition and turbulent flow regimes. The proposed analytical solution has been validated against experiments conducted at Oak Ridge National Laboratory. Exhaust gas carrying submicron soot particles was passed through pipes with a constant wall temperature and various designed boundary conditions to correlate transition and turbulent flow regimes. Prediction of the reduction in heat transfer coefficient and particulate mass deposited has been compared with experiments. The results of the analytical method are in a reasonably good agreement with experiments.

Diesel exhaust simulator: Design and application to plasma discharge testing

A diesel fuel and air diffusion flame burner system has been designed for laboratory simulation of diesel exhaust gas. The system consists of mass flow controllers and a fuel pump, and employs several unique design and construction features. It produces particulate emissions with size, number distribution, and morphology similar to diesel exhaust. At the same time, it generates NOx emissions and HC similar to diesel. The system has been applied to test plasma discharges. Different design discharge devices have been tested, with results indicating the importance of testing devices with soot and moisture. Both packed bed reactor and flat plate dielectric barrier discharge systems remove some soot from the gas, but the designs tested are susceptible to soot fouling and related electrical failures. The burner is simple and stable, and is suitable for development and aging of plasma and catalysts systems in the laboratory environment.

Cluster formation by barrier discharge in simulated engine exhaust gas at high temperature

Experiments were performed to examine cluster formation when simulated engine exhaust gas passes through an atmospheric pressure plasma discharge cell at 180 °C. The gas composition included N2, NO, CO, CO2, C3H8, C3H6, Ar, H2, H2O, O2 and SO2. Aerosol particles or clusters were measured after the gas was treated with a dielectric barrier discharge, although the quantity of clusters generated was several orders of magnitude smaller than normal engine emissions. The clusters were not formed when water was not present in the mixture. The number and size of clusters increased when hydrocarbons were not present, although the quantity was still very small. Methods to describe cluster formation phenomena are discussed.

Effect of Volatiles on Soot Based Deposit Layers

The implementation of exhaust gas recirculation (EGR) coolers has recently been a widespread methodology for engine in-cylinder NOX reduction. A common problem with the use of EGR coolers is the tendency for a deposit, or fouling layer to form through thermophoresis. These deposit layers consist of soot and volatiles and reduce the effectiveness of heat exchangers at decreasing exhaust gas outlet temperatures, subsequently increasing engine out NOX emission.This paper presents results from a novel visualization rig that allows for the development of a deposit layer while providing optical and infrared access. A 24-hour, 379 micron thick deposit layer was developed and characterized with an optical microscope, an infrared camera, and a thermogravimetric analyzer. The in-situ thermal conductivity of the deposit layer was calculated to be 0.047 W/mK. Volatiles from the layer were then evaporated off and the layer reanalyzed. Results suggest that volatile bake-out can significantly alter the thermo-physical properties of the deposit layer and hypotheses are presented as to how.Copyright

Large Particles in Modern Diesel Engine Exhaust

During research on diesel engine EGR cooler fouling a test stand giving visual access to the building deposit layer has been developed. Initial experiments reveal the presence of large particles in the exhaust. While conventional wisdom is that diesel particulates typically have log-normal size distributions ranging approximately 10–200 nm, the tests reported here observe small numbers of particles with sizes on the order of tens of μm. Such particles are not generally reported in the literature because exhaust particle sizing instruments typically have inertial separators to remove particles larger than ∼1 μm in order to avoid fouling of the nanoparticle measurement system.The test stand provides exhaust or heated air flow over a cooled surface with Reynolds number, pressure, and surface temperature typical of an EGR cooler. A window allows observation using a digital microscope camera. Starting from a clean surface, a rapid build of a deposit layer is observed. A few large particles are observed. These may land on the surface and remain for long times, although occasionally a particle blows away.In order to study these particles further, an exhaust sample was passed over a fiberglass filter, and the resulting filtered particles were analyzed. Samples were taken at the engine EGR passage, and also in the test stand tubing just before the visualization fixture. The resulting images indicate that the particles are not artifacts of the test system, but rather are present in engine exhaust.MATLAB routines were developed to analyze the filter images taken on the microscope camera. Particles were identified, counted, and sized by the software.It is not possible to take isokinetic samples and give quantitative measurement of the number and size distribution of the particles because the particles are large enough that inertial and gravitational effects will cause them to at least partially settle out of the flows. Nonetheless, the presence of particles tens of μm is documented.Such particles are probably the result of in-cylinder and exhaust pipe deposits flaking. While these larger particles would be captured by the diesel particulate filter (DPF), they can affect intake and exhaust valve seating, EGR cooler fouling, EGR valve sealing, and other factors.Copyright

Design of a Flow Reactor for Testing Multi-Brick Catalyst Systems Using Rapid Exhaust Gas Composition Switches

In recent years, diesel exhaust gas aftertreatment has become a core combustion engine research subject because of both increasingly stringent emission regulations and incentives toward more fuel-efficient propulsion systems. Lean NOX traps (LNT) and selective catalytic reduction (SCR) catalysts represent two viable pathways for the challenging part of exhaust gas aftertreatment of lean burn engines: NOX abatement. It has been found that the combination of LNT and SCR catalysts can yield synergistic effects. Switches in the operation mode of the engine, temporarily enriching the mixture, are required to regenerate the LNT catalyst and produce ammonia for the SCR. This paper describes the design of a catalyst flow reactor that allows studying multi-brick catalyst systems using rapid exhaust gas composition switches and its initial validation. The flow reactor was designed primarily to study the potential of combining different aftertreatment components. It can accommodate two sample bricks at a time in two tube furnaces, which allows for independent temperature control. Moreover, the flow reactor allows for very flexible control of the composition and flow rate of the synthetic exhaust, which is blended using mass flow controllers. By using a two-branch design, very fast switches between two exhaust gas streams, as seen during the regeneration process of a LNT catalyst, are possible. The flow reactor utilizes a variety of gas analyzers, including a 5-Hz FTIR spectrometer, an emissions bench for oxygen and THC, a hydrogen mass spectrometer, and gas chromatographs for HC speciation. An in-house control program allows for data recording, flow reactor control, and highly flexible automation. Additionally, the hardware and software incorporate features to ensure safe testing. The design also has provisions for engine exhaust sampling.Copyright