Proceeding from the aim to reduce global pollution emissions from the continuous burning of hydrocarbons stimulated by increasing energy demand, more efficient and ultra-low emissions’ combustion concepts such as the homogenous charge compression ignition engines (HCCI) have been developed. These new engines rely on the low temperature chemistry (LTC) combustion concept. A detailed investigation of the properties of cool flames, governed by LTC, is essential for the design of these new engines. The primary goal of this work was to build a fundamental counterflow experiment for cool flames studies in a diffusive system, to better understand combustion in LTC engines. The project was intended to provide a basic understanding of the low-temperature reactivity and cool flames properties of butane isomers under atmospheric pressure conditions. This was achieved by establishing self-sustaining cool flames through a novel technique of ozone addition to an oxygen stream in a non-premixed counterflow model. The ignition and extinction limits of butane isomers’ cool flames have been investigated under a variety of strain rates. Results revealed that establishment of cool flames are favored at lower strain rates. Iso-butane was less reactive than n-butane by showing higher ignition and extinction limits. Ozone addition showed a significant influence on cool flame ignition and sustenance; it was found that increasing ozone concentration in the oxidizer stream dramatically increased the reactivity of both fuels. Results showed increased fuel reactivity as the temperature of the fuel stream outlet increased. 4 A numerical analysis was performed to simulate ignition and extinction of the cool flame in diffusive systems. The results revealed that ignition and extinction limits of cool flames are predominantly governed by LTC. The model qualitatively captured experimental trends for both fuels; however, it overpredicted both ignition and extinction limits under all strain rates and ozone concentrations. The discrepancies were within a factor of eight for the ignition limit and a factor of two for the extinction limit. Finally, sensitivity analyses were conducted to understand the reactions responsible for cool flames ignition. It was found that majority of the sensitive reactions are those that occur at low temperatures.

The goal of this project was to understand and model the performance of hybrid inorganic-organic membranes under realistic operating conditions for hydrocarbon gas/vapor separation, using butane isomers as the model vapors and a hybrid membrane of 6FDA-DAM-5A as an advanced separation system. To achieve the set goal, three objectives were laid out. The first objective was to determine the factors affecting separation performance in dense neat polymer. One main concern was plasticization. High temperature annealing has been reported as an effect means of suppressing plasticization. A study on the effect of annealing temperature was performed by analyzing data acquired via sorption and permeation measurements. Based on the findings from this study, a suitable annealing temperature was determined. Another factor studied was the effect of operating temperature. In deciding a suitable operating temperature, factors such as its possible effect on plasticization as well as reducing heating/cooling cost in industrial application were considered. Based on the knowledge that industrial applications of this membrane would involve mixture separation, the second objective was to understand and model the complexity of a mixed gas system. This was investigated via permeation measurements using three feed compositions. An interesting transport behavior was observed in the mixed gas system, which to the best of our knowledge, has not been observed in other mixed gas systems involving smaller penetrants. This mixed gas transport behavior presented a challenge in predictability using well-established transport models. Two hypotheses were made to explain the observed transport behavior, which led to the development of a new model termed the HHF model and the introduction of a fitting parameter termed the CAUFFV fit. Both the HHF model and CAUFFV fit showed better agreement with experimental data than the well-established mixed gas transport model. The final objective was to explore the use of mixed matrix membranes as a means of improving the separation performance of this system. A major challenge with the fabrication of good mixed matrix membranes was the adhesion of the zeolite particle with the polymer. This was addressed via sieve surface modification through a Grignard treatment process. Although a Grignard treatment procedure existed, there was a challenge of reproducibility of the treatment. This challenge was addressed by exploring the relationship between the sieves and the solvent used in the treatment, and taking advantage of this relationship in the Grignard treatment process. This study helped identify a suitable solvent, which allowed for successful and reproducible treatment of commercial LTA sieves; however, treatment of lab-made sieves continues to prove challenging. Based on improved understanding of the Grignard treatment reaction mechanism, modifications were made to the existing Grignard treatment procedure, resulting in the introduction of a "simplified" Grignard treatment procedure. The new procedure requires less control over the reaction process, thus making it more attractive for industrial application. Permeation measurements were made using mixed matrix membranes in both single and mixed gas systems. Selectivity enhancements were observed under both single and mixed gas systems using sieve loadings of 25 and 30wt%. The Maxwell model was used to make predictions of mixed matrix membrane performance. Although the experimental results were not in exact agreement with Maxwell predictions, the observed selectivity enhancement was very encouraging and shows potential for future application. Recommendations were made for future study of this system.