Russell G. Tonkyn

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.

Quantitative reflectance spectra of solid powders as a function of particle size

We have recently developed vetted methods for obtaining quantitative infrared directional-hemispherical reflectance spectra using a commercial integrating sphere. In this paper, the effects of particle size on the spectral properties are analyzed for several samples such as ammonium sulfate, calcium carbonate, and sodium sulfate as well as one organic compound, lactose. We prepared multiple size fractions for each sample and confirmed the mean sizes using optical microscopy. Most species displayed a wide range of spectral behavior depending on the mean particle size. General trends of reflectance versus particle size are observed such as increased albedo for smaller particles: for most wavelengths, the reflectivity drops with increased size, sometimes displaying a factor of 4 or more drop in reflectivity along with a loss of spectral contrast. In the longwave infrared, several species with symmetric anions or cations exhibited reststrahlen features whose amplitude was nearly invariant with particle size, at least for intermediate and large size sample fractions: that is, ≳150  μm. Trends of other types of bands (Christiansen minima, transparency features) are also investigated as well as quantitative analysis of the observed relationship between reflectance versus particle diameter.

Kinetic and internal energy distributions of molecular hydrogen produced from amorphous ice by impact of 100 eV electrons

Abstract We have measured the quantum-resolved translational and internal (vibrational and rotational) energy distributions of the D 2 desorbates produced during electron (100 eV) irradiation of D 2 O amorphous ice using resonance-enhanced multiphoton ionization (REMPI) spectroscopy. The D 2 desorbates have very little translational energy (∼ 20–50 meV) but are vibrationally ( ν = 0–4) and rotationally ( J = 0–12) excited. The rotational state distribution of the D 2 does not change as the ice temperature increases from 88 to 145 K. However, we find that the D 2 yield increases monotonically in this temperature range, with the yield at 145 K approximately double than that at 88 K. Although the mobilities of defects, charge carriers, and radicals are known to be temperature dependent, these results suggest that the final states leading to D 2 production are independent of temperature. We suggest that the dominant mechanisms for production of D 2 at 100 eV incident electron energy are dissociative recombination of holes (D 2 O + or D 3 O + ) with quasi-free or trapped electrons and dissociation of excitons at the vacuum-surface interface. These dissociation events can produce D 2 directly via molecular elimination or indirectly via reactive scattering of the energetic D atom fragments.

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.

Lean NOx Reduction in Two Stages: Non-thermal Plasma Followed by Heterogeneous 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.

Demonstrated Wavelength Portability of Raman Reference Data for Explosives and Chemical Detection

As Raman spectroscopy continues to evolve, questions arise as to the portability of Raman data: dispersive versus Fourier transform, wavelength calibration, intensity calibration, and in particular the frequency of the excitation laser. While concerns about fluorescence arise in the visible or ultraviolet, most modern (portable) systems use near-infrared excitation lasers, and many of these are relatively close in wavelength. We have investigated the possibility of porting reference data sets from one NIR wavelength system to another: We have constructed a reference library consisting of 145 spectra, including 20 explosives, as well as sundry other compounds and materials using a 1064 nm spectrometer. These data were used as a reference library to evaluate the same 145 compounds whose experimental spectra were recorded using a second 785 nm spectrometer. In 128 cases of 145 (or 88.3% including 20/20 for the explosives), the compounds were correctly identified with a mean “hit score” of 954 of 1000. Adding in criteria for when to declare a correct match versus when to declare uncertainty, the approach was able to correctly categorize 134 out of 145 spectra, giving a 92.4% accuracy. For the few that were incorrectly identified, either the matched spectra were spectroscopically similar to the target or the 785 nm signal was degraded due to fluorescence. The results indicate that imported data recorded at a different NIR wavelength can be successfully used as reference libraries, but key issues must be addressed: the reference data must be of equal or higher resolution than the resolution of the current sensor, the systems require rigorous wavelength calibration, and wavelength-dependent intensity response should be accounted for in the different systems.

Modeling Species Inhibition of NO Oxidation in Urea-SCR Catalysts for Diesel Engine NOx Control

Urea-selective catalytic reduction (SCR) catalysts are regarded as the leading NOx aftertreatment technology to meet the 2010 NOx emission standards for on-highway vehicles running on heavy-duty diesel engines. However, issues such as low NOx conversion at low temperature conditions still exist due to various factors, including incomplete urea thermolysis, inhibition of SCR reactions by hydrocarbons and H2 O. We have observed a noticeable reduction in the standard SCR reaction efficiency at low temperature with increasing water content. We observed a similar effect when hydrocarbons are present in the stream. This effect is absent under fast SCR conditions where NO ∼ NO2 in the feed gas. As a first step in understanding the effects of such inhibition on SCR reaction steps, kinetic models that predict the inhibition behavior of H2 O and hydrocarbons on NO oxidation are presented in the paper. A one-dimensional SCR model was developed based on conservation of species equations and was coded as a C-language S-function and implemented in Matlab/Simulink environment. NO oxidation and NO2 dissociation kinetics were defined as a function of the respective adsorbate’s storage in the SCR catalyst. The corresponding kinetic models were then validated on temperature ramp tests that showed good match with the test data.Copyright

Effect of Simulated Diesel Exhaust Gas Composition and Temperature on NOx Reduction Behavior of Alumina and Zeolite Catalysts in Combination With Non-Thermal Plasma

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 degree Celcius temperature region. Alumina Catalyst D was most active at temperatures higher than 250 degrees Celcius. 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 catalyst, the catalyst temperature range for significant NOx reduction was expanded to 150-500 degrees Celcius.

Quantitative Total and Diffuse Reflectance Laboratory Measurements for Remote, Standoff, and Point Sensing

Methods for making total and diffuse directional/hemispherical reflectance measurements in the shortwave to longwave infrared using an integrating sphere are described. The sphere is a commercial, off-the-shelf optical device with its sample port at the bottom, which is essential for examining powdered samples without using a cover glass. The reflectance spectra of recently-developed National Institute of Standards and Technology (NIST, USA) infrared reflectance standards have been measured using the sphere. Reflectance spectra of other materials such as Spectralon and Infragold were also measured. The relative systematic error for the total reflectance measurements is estimated to be on the order of 3%, and random measurement error for multiple samples of each material is on the order of 0.5%.

Non-Thermal Plasma System Development for CIDI Exhaust Aftertreatment

There is a need for an efficient, durable technology to reduce NOx emissions from oxidative exhaust streams such as those produced by compression-ignition, direct injection (CIDI) diesel or lean-burn gasoline engines. A partnership formed between the DOE Office of Advanced Automotive Technology, Pacific Northwest National Laboratory, Oak Ridge National Laboratory and the USCAR Low Emission Technologies Research and Development Partnership is evaluating the effectiveness of a non-thermal plasma in conjunction with catalytic materials to mediate NOx and particulate emissions from diesel fueled light duty (CIDI) engines. Preliminary studies showed that plasma-catalyst systems could reduce up to 70% of NOx emissions at an equivalent cost of 3.5% of the input fuel in simulated diesel exhaust. These studies also showed that the type and concentration of hydrocarbon play a key role in both the plasma gas phase chemistry and the catalyst surface chemistry. More recently, plasma/catalyst systems have been evaluated for NOx reduction and particulate removal on a CIDI engine. Performance results for select plasma-catalyst systems for both simulated and actual CIDI exhaust will be presented. The effect of NOx and hydrocarbon concentration on plasma-catalyst performance will also be shown. SAE Paper SAE-2000-01-1601 {copyright} 2000 SAE International. This paper is published on this website with permission from SAE International. As a user of this website, you are permitted to view this paper on-line, download this pdf file and print one copy of this paper at no cost for your use only. The downloaded pdf file and printout of this SAE paper may not be copied, distributed or forwarded to others or for the use of others.