A SCR Model based on Reactor and Engine Experimental Studies for a Cu-zeolite Catalyst

A NOx reduction efficiency higher than 95% with NH3 slip less than 30 ppm is desirable for heavy-duty diesel (HDD) engines using selective catalytic reduction (SCR) systems to meet the US EPA 2010 NOx standard and the 2014-2018 fuel consumption regulation. The SCR performance needs to be improved through experimental and modeling studies. In this research, a high fidelity global kinetic 1-dimensional 2-site SCR model with mass transfer, heat transfer and global reaction mechanisms was developed for a Cu-zeolite catalyst. The model simulates the SCR performance for the engine exhaust conditions with NH3 maldistribution and aging effects, and the details are presented. SCR experimental data were collected for the model development, calibration and validation from a reactor at Oak Ridge National Laboratory (ORNL) and an engine experimental setup at Michigan Technological University (MTU) with a Cummins 2010 ISB engine. The model was calibrated separately to the reactor and engine data. The experimental setup, test procedures including a surrogate HD-FTP cycle developed for transient studies and the model calibration process are described. Differences in the model parameters were determined between the calibrations developed from the reactor and the engine data. It was determined that the SCR inlet NH3 maldistribution is one of the reasons causing the differences. The model calibrated to the engine data served as a basis for developing a reduced order SCR estimator model. The effect of the SCR inlet NO2/NOx ratio on the SCR performance was studied through simulations using the surrogate HD-FTP cycle. The cumulative outlet NOx and the overall NOx conversion efficiency of the cycle are highest with a NO2/NOx ratio of 0.5. The outlet NH3 is lowest for the NO2/NOx ratio greater than 0.6. A combined engine experimental and simulation study was performed to quantify the NH3 maldistribution at the SCR inlet and its effects on the SCR performance and kinetics. The uniformity index (UI) of the SCR inlet NH3 and NH3/NOx ratio (ANR) was determined to be below 0.8 for the production system. The UI was improved to 0.9 after installation of a swirl mixer into the SCR inlet cone. A multi-channel model was developed to simulate the maldistribution effects. The results showed that reducing the UI of the inlet ANR from 1.0 to 0.7 caused a 5-10% decrease in NOx reduction efficiency and 10-20 ppm increase in the NH3 slip. The simulations of the steady-state engine data with the multi-channel model showed that the NH3 maldistribution is a factor causing the differences in the calibrations developed from the engine and the reactor data. The Reactor experiments were performed at ORNL using a Spaci-IR technique to study the thermal aging effects. The test results showed that the thermal aging (at 800°C for 16 hours) caused a 30% reduction in the NH3 stored on the catalyst under NH3 saturation conditions and different axial concentration profiles under SCR reaction conditions. The kinetics analysis showed that the thermal aging caused a reduction in total NH3 storage capacity (94.6 compared to 138 gmol/m3), different NH3 adsorption/desorption properties and a decrease in activation energy and the pre-exponential factor for NH3 oxidation, standard and fast SCR reactions. Both reduction in the storage capability and the change in kinetics of the major reactions contributed to the change in the axial storage and concentration profiles observed from the experiments.

Characterizations of partially reduced polyoxometalate catalysts using ammonia adsorption microcalorimetry and methanol oxidation studies / by Suresh Babu Bommineni.

Phosphomolybdic acid (H3PMo12O40) along with niobium,pyridine and niobium exchanged phosphomolybdic acid catalysts were prepared. Ammonia adsorption microcalorimetry and methanol oxidation studies were carried out to investigate the acid sites strength acid/base/redox properties of each catalyst. The addition of niobium, pyridine or both increased the ammonia heat of adsorption and the total uptake. The catalyst with both niobium and pyridine demonstrated the largest number of strong sites. For the parent H3PMo12O40 catalyst, methanol oxidation favors the redox product. Incorporation of niobium results in similar selectivity to redox products but also results in no catalyst deactivation. Incorporation of pyridine instead changes to the selectivity to favor the acidic product. Finally, the inclusion of both niobium and pyridine results in strong selectivity to the acidic product while also showing no catalyst deactivation. Thus the presence of pyridine appears to enhance the acid property of the catalyst while niobium appears to stabilize the active site.

Interrogating the spaces of personal photography : women, identity, and the cultural formation of photographic practice

Personal photographs permeate our lives from the moment we are born as they define who we are within our familial group and local communities. Archived in family albums or framed on living room walls, they continue on after our death as mnemonic artifacts referencing our gendered, raced, and ethnic identities. This dissertation examines salient instances of what women “do” with personal photographs, not only as authors and subjects but also as collectors, archivists, and family and cultural historians. This project seeks to contribute to more productive, complex discourse about how women form relationships and engage with the conventions and practices of personal photography. In the first part of this dissertation I revisit developments in the history of personal photography, including the advertising campaigns of the Kodak and Agfa Girls and the development of albums such as the Stammbuch and its predecessor, the carte-de-visite, that demonstrate how personal photography has functioned as a gendered activity that references family unity, sentimentalism for the past, and self-representation within normative familial and dominant cultural groups, thus suggesting its importance as a cultural practice of identity formation. The second and primary section of the dissertation expands on the critical analyses of Gillian Rose, Patricia Holland, and Nancy Martha West, who propose that personal photography, marketed to and taken on by women, double-exposes their gendered identities. Drawing on work by critics such as Deborah Willis, bell hooks, and Abigail Solomon-Godeau, I examine how the reconfiguration, recontextualization, and relocation of personal photographs in the respective work of Christine Saari, Fern Logan, and Katie Knight interrogates and complicates gendered, raced, and ethnic identities and cultural attitudes about them. In the final section of the dissertation I briefly examine select examples of how emerging digital spaces on the Internet function as a site for personal photography, one that both reinscribes traditional cultural formations while offering new opportunities for women for the display and audiencing of identities outside the family.

DEVELOPMENT OF AN IONIC LIQUID FERROFLUID ELECTROSPRAY SOURCE AND MODE SHAPE STUDIES OF A FERROFLUID IN A NON-UNIFORM MAGNETIC FIELD

An electrospray source has been developed using a novel new fluid that is both magnetic and conductive. Unlike conventional electrospray sources that required microfabricated structures to support the fluid to be electrosprayed, this new electrospray fluid utilizes the Rosensweig instability to create the structures in the magnetic fluid when an external magnetic field was applied. Application of an external electric field caused these magnetic fluid structures to spray. These fluid based structures were found to spray at a lower onset voltage than was predicted for electrospray sources with solid structures of similar geometry. These fluid based structures were also found to be resilient to damage, unlike the solid structures found in traditional electrospray sources. Further, experimental studies of magnetic fluids in non-uniform magnetic fields were conducted. The modes of Rosensweig instabilities have been studied in-depth when created by uniform magnetic fields, but little to no studies have been performed on Rosensweig instabilities formed due to non-uniform magnetic fields. The measured spacing of the cone-like structures of ferrofluid, in a non-uniform magnetic field, were found to agree with a proposed theoretical model.