The objective of this work was to study the effect of supercritical water on coke formed on ZSM-5 during its use as a dodecane cracking catalyst. ZSM-5 coking was quantified at different reaction times, finding that the presence of supercritical water reduced coke formation by an order of magnitude or more. Coked samples were analyzed using several methods, including temperature programmed oxidation (TPO), attenuated total reflectance infrared (ATR-IR) spectroscopy, carbon-13 nuclear magnetic resonance (13C NMR), diffuse reflectance ultraviolet-visible spectroscopy (DR-UV-vis) and UV-Raman. Coked produced in the absence of SCW was formed by polycyclic aromatic hydrocarbons (PAHs) with more than 4 aromatic rings containing alkyl side chains. Coke produced in the presence of SCW was formed by aromatics with 1 to 3 aromatic rings. The characteristics of coke formed in the absence of water on ZSM-5 that had been pretreated in SCW were intermediate to those of coke formed on fresh ZSM-5 in the presence and absence of water, suggesting that the presence of water influences coke properties. It was also verified that SCW can decrease coke formation due to its effect on Bronsted acidity of the catalyst and ability to promote coke gasification. The effect of coke deposits produced in the presence and absence of SCW on the rate of ethanol dehydration, a model reaction studied under diffusion-controlled conditions, indicated that SCD/SWC coke deactivated less the catalyst than SCD coke.

The extended DLVO theory was used to develop a flotation model by considering both hydrodynamic and surface forces involved in the process. A stream function was used to estimate the kinetic energies for thinning the water films between bubbles and particles, which were compared with the energy barriers, created by surface forces, to determine the probability of adhesion. A general expression for the probability of detachment was derived from similar mechanism for chemical reaction, and the kinetic energy for detachment was estimated with French and Wilson's model. The hydrophobic force parameter (K132) calculated from the rate constants of single bubble flotation tests showed that, K132 for bubble-particle interaction were close to the geometric means of K131 for particle-particle interactions and K232 for bubble-bubble interaction, indicating that the combining rules developed for dispersion forces may be useful for hydrophobic forces. The model was used to predict flotation results as functions of several important parameters such as contact angle, double-layer potentials, particle size, bubble size, etc. The predictions were consistent with experience, and could be explained in view of the various subprocesses considered in the model development. Furthermore, the model suggested optimum conditions for achieving the maximum separation efficiency. The extended DLVO theory was also used to determine the hydrophobic force between two oil/solution interfaces from the equilibrium film thicknesses of dodecylammonium chloride (RNH3Cl) solutions obtained using Thin Film Balance (TFB) technique. The results showed that, the oil droplets were inherently hydrophobic, and the hydrophobic force played an important role in the stability of emulsions. This force decreased with increasing surfactant concentration, and also changed with pH and the addition of electrolyte. The interfacial area occupied by molecules indicated that, the dodecane molecules might present between two surfactant ions at interface, thus the hydrophobicity of oil/solution interface was less sensitive to the addition of the surfactant than that of air/solution interface. Thermodynamic analysis suggested that, there might exist a relationship between the interfacial hydrophobicity and the interfacial tension. / Ph. D.

Fuel cell is one of the most promising clean energy and alternative energy technologies due to its advantages of low emissions and high efficiency. One application of the fuel cell technology is onboard auxiliary power units (APUs) for power generation in aircrafts, ships, and automobiles. In order to supply hydrogen or syngas for the fuel cell APUs, onboard fuel processing technology was proposed to convert hydrocarbon fuels into syngas through reforming reactions. Two major tasks need to be completed in onboard fuel processing technology. Firstly sulfur compounds have to be removed from hydrocarbon fuels because sulfur can cause reforming catalyst deactivation and fuel cell electrodes poisoning problems. Secondly hydrogen and carbon monoxide shall be produced by reforming of hydrocarbon fuels at a high energy conversion efficiency. This dissertation focused on onboard fuel processing of Jet-A fuel to produce hydrogen and syngas for solid oxide fuel cell (SOFC) APUs. Jet-A fuel was studied because it is the logistic fuel commonly used for civilian airplanes and military heavy duty trucks. Ultra-deep adsorptive desulfurization of Jet-A fuel from over 1,000 ppmw to below 50 ppmw, and autothermal reforming of n-dodecane as a Jet-A fuel surrogate as well as the real desulfurized Jet-A fuel to produce syngas have been systematically investigated in the present study. For the adsorptive desulfurization of Jet-A fuel, a novel NiO-CeO₂/A1₂O₃-SiO₂ adsorbent was proposed and prepared in-house for experimental tests. The sulfur adsorption kinetic characteristic and isotherm at equilibrium were studied in batch tests, and the dynamic desulfurization performance of the adsorbent was investigated in fixed bed tests. Fixed bed tests operation conditions including liquid hourly space velocity (LHSV), adsorbent particle size, and fixed bed dimensions were optimized to achieve the highest adsorbent sulfur adsorption capacity. For the reforming of Jet-A fuel, autothermal reforming (ATR) method was employed and a bimetallic NiO-Rh catalyst was synthesized for the ATR reactions. A lab-scale 2.5 kWt autothermal reforming system including the reformer and balance-of-plant was designed, fabricated, integrated and tested. The reforming system performances at various operation conditions were compared. Reformer operation temperature, steam to carbon ratio and oxygen to carbon ratio, as well as pre-heating temperatures for fuel, air and steam were optimized based on system energy conversion efficiency, H₂ selectivity and COₓ selectivity.

This thesis has studied the low-temperature atmospheric pressure plasma as a potential technological application for the degradation of waste oils. The study has been approached initially by investigating the degradation of oil in gas phase only, in order to understand the gas chemistry and elucidate the plasma-chemical degradation mechanism. Gaseous odourless kerosene and dodecane have been used as simulants to waste oil and their plasma-chemical degradation has been studied using a BaTiO3 packed bed plasma reactor and a gliding arc discharge reactor. Kerosene showed similar degradation behaviour to dodecane and the latter one was chosen as a surrogate to allow quantitative analysis. The dodecane plasma degradation efficiency and the distribution of end-gaseous products have been studied under these two reactors in different gas compositions. Optical emission spectroscopy was used to identify intermediate excited species and calculate the rotational and vibrational temperature profiles. Differences in the dodecane degradation gas chemistry between the packed bed and the gliding arc plasma are discussed and postulated mechanisms are presented for each condition. Gliding arc discharge demonstrates higher degradation efficiency and it will be used mainly for the plasma-liquid treatment. The plasma-liquid dodecane treatment is firstly studied using argon dielectric barrier discharge. The effect of different reactor configuration, humidity and temperature to the discharge characteristics and degradation efficiency will be discussed. The study of the liquid dodecane degradation is extended by using the gliding arc discharge. Using N2 and Ar in both dry and humid conditions for the batch treatment of dodecane, the degradation efficiency, gas chemistry and liquid chemistry are discussed and correlated to the gas chemistry observed during the plasma treatment of gaseous dodecane under the same conditions, in order to gain an overall understanding of the plasma-liquid clean-up process. Finally, the gliding arc plasma treatment of liquid dodecane is studied using the recycling method and shows a significant improvement to the degradation efficiency.

Previous studies have successfully used near and supercritical water (SCW) for cracking and desulfurization of heavy crude oil and bio-oil, suppressing coke formation as a low-value by-product. Some of these studies benefited from using zeolite catalysts to increase the activity and selectivity toward targeted products; however, in depth studies are required to identify the role of water on zeolite catalysis under supercritical condition. Using three common zeolites, ZSM-5, HY, and β for supercritical water cracking of dodecane at 400°C, 24±2 MPa (in a 100 ml batch reactor), we showed that ZSM-5 is the only catalyst that partially retains its crystalline structure and activity under hydrothermal conditions. Further characterization of the ZSM-5 (used under 50/50 wt% SCW/dodecane feed) revealed 95% decrease in Brønsted acid site (BAS) density and 80% decrease in microporous area after 2 h reaction time. However, compared to the runs where SCW was absent, the apparent dodecane cracking rate constant in SCW decreased only by a factor of 2.6. Examining catalytic activity of ZSM-5 degradation products and re-using ZSM-5 showed that the unexpected activity cannot be ascribed to ZSM-5 degradation products. Using a group-type model, we showed that SCW accelerated gas and suppressed coke formations. Additionally a coke gasification pathway was suggested to account for formation of CO and CO2 in the presence of SCW. Additional experiments with two different ZSM-5 particle sizes suggested that dodecane cracking reaction is diffusion-limited in the absence of SCW and reaction-limited in its presence. Zero length chromatography of calcined and hydrothermally treated ZSM-5 showed 10 times greater apparent diffusivity for un-treated catalyst. This, according to Weisz-Prater analysis, suggested a 250 times greater dodecane surface concentration in the absence of SCW. We successfully optimized the water content of feed (5-15 wt%) to decrease the destructive effects of SCW on the structure, increase the selectivity toward BTEX products and eliminate coke formation.

Previous studies have successfully used near and supercritical water (SCW) for cracking and desulfurization of heavy crude oil and bio-oil, suppressing coke formation as a low-value by-product. Some of these studies benefited from using zeolite catalysts to increase the activity and selectivity toward targeted products; however, in depth studies are required to identify the role of water on zeolite catalysis under supercritical condition. Using three common zeolites, ZSM-5, HY, and β for supercritical water cracking of dodecane at 400°C, 24±2 MPa (in a 100 ml batch reactor), we showed that ZSM-5 is the only catalyst that partially retains its crystalline structure and activity under hydrothermal conditions. Further characterization of the ZSM-5 (used under 50/50 wt% SCW/dodecane feed) revealed 95% decrease in Brønsted acid site (BAS) density and 80% decrease in microporous area after 2 h reaction time. However, compared to the runs where SCW was absent, the apparent dodecane cracking rate constant in SCW decreased only by a factor of 2.6. Examining catalytic activity of ZSM-5 degradation products and re-using ZSM-5 showed that the unexpected activity cannot be ascribed to ZSM-5 degradation products. Using a group-type model, we showed that SCW accelerated gas and suppressed coke formations. Additionally a coke gasification pathway was suggested to account for formation of CO and CO2 in the presence of SCW. Additional experiments with two different ZSM-5 particle sizes suggested that dodecane cracking reaction is diffusion-limited in the absence of SCW and reaction-limited in its presence. Zero length chromatography of calcined and hydrothermally treated ZSM-5 showed 10 times greater apparent diffusivity for un-treated catalyst. This, according to Weisz-Prater analysis, suggested a 250 times greater dodecane surface concentration in the absence of SCW. We successfully optimized the water content of feed (5-15 wt%) to decrease the destructive effects of SCW on the structure, increase the selectivity toward BTEX products and eliminate coke formation.

No description available.

No description available.

No description available.