No description available.

No description available.

No description available.

To date, an estimated 70% of energy consumed comes from fossil fuels, such as coal, oil and natural gas. The major source of sulfur dioxide (SO2) emissions comes from combustion of these fossil fuels. Sulfur dioxide is a significant pollutant, because it and its higher oxidation product (SO3) react with moisture in the atmosphere to produce sulfuric acid. This results in acid rain, which comes back to earth and affects people, animals, and vegetation. Therefore, the governments of Canada, US and European countries are issuing stricter and stricter regulation to control SO2 emissions. In conventional SO2 removal processes, lime or limestone scrubbers are used, but they require large amounts of water and enough landfill sites to deal with the solid wastes. Previous attempts were made in our laboratory to recover SO2 adsorbed on activated carbon to produce sulfuric acid using non-aqueous solvents. Unfortunately, in this adsorption/distillation process, the SO2 recovery was low, as was the quality of sulfuric acid, that could not be marketable. The topic of this thesis was then conceived as an attempt to first recover SO2 via SO3 formation using supercritical carbon dioxide instead of water or non-aqueous flushing agents (desorption step) and then to use the recovered SO3 to produce linear alkylbenzene sulfonates (LAS), the main component of detergent. In the adsorption and oxidation experiments of this project, charcoal activated carbon (AC) was used to adsorb SO2 and to catalyze SO2 oxidation. The process started with a simulated flue gas, 3500 ppm SO2, 5% O2, balanced with N2. When the simulated flue gas passed through the activated carbon bed reactor, more than 95% of SO2 was oxidized to SO3. In the desorption process, SO3 contacted with the AC bed was removed using supercritical carbon dioxide (SCCO2) and 95% sulfur removal was achieved at appropriate operating conditions, for example, for a carbon bed preheated at 250??C for 6 h, and flushed by recycled SCCO2. The LAS production experiments consisted in reacting liquid linear alkylbenzene (LAB) with the recovered SO3 in an absorption column. Ceramic filters and glass beads were used in the absorption columns to break up the gas bubbles and increase the contact time between the gas and the liquid absorbent. When staged pressure columns were used and when LAB was heated to 40??C, nearly 95% of SO3 reacted with LAB to produce LAS.

The technology of supercritical fluid extraction (SFE) offers the opportunity to efficiently extract both relatively non-polar analytes as well as ionic materials (such as metal ions) that can be mobilized with the addition of complexing reagents. The nebulizer of a conventional flame atomic absorption spectrometer (FAAS) was modified to extend the range of metals amenable to on-line detection. The flow injection thermospray-FAAS (FI-TE-FAAS) interface provided efficient detection for a variety of less volatile elements (Co, Cr(III), Cr(VI), Fe, Ni, Mn and Al) present as ions in aqueous media or as complexes in the supercritical fluid (SC-CO2) carrier phase. The range of possible metal analytes that can be monitored has been increased over the nine elements (Ag, As, Cd, Cu, Hg, Mn, Pb, Se and Zn) that could be detected with an all-silica interface. The acetylacetonate complexes offered considerable potential for metal detection in an SC-CO2 carrier phase. Limits of detection (LODs) were used to compare the instrument responses to different metals. (Abstract shortened by UMI.)

Catalytic supercritical water gasification (SCWG) is a promising technology for hydrogen and methane production from wet organic feedstocks at relatively low temperatures (e.g. <500 oC). However, in order to make this process technically and economically viable, solid catalyst with enhanced activity and improved hydrogen selectivity should be developed. In this study, different aspects of catalytic SCWG have been investigated. The performance of several supported-nickel catalysts were examined to identify catalysts that lead to high carbon conversion and high hydrogen yields under near-critical conditions (i.e. near 374 oC). Moreover, for the first time, the effects of several parameters which dominated the activity of the supported nickel catalysts have been systematically investigated. Among the several different catalyst supports evaluated at 5% nickel loading, α-Al2O3, carbon nanotube (CNT), and MgO supports resulted in highest carbon conversions, while SiO2, Y2O3, hydrotalcite, yttria-stabilized zirconia (YSZ), and TiO2 showed modest activities. Comparing the XRD patterns for the support materials before and after the exposure to supercritical water, α-Al2O3, YSZ, and TiO2 were found to be hydrothermally stable among the metal oxide supports. Using the same amount of nickel on α-Al2O3, the methane yield decreased by increasing the nickel to support ratio whereas the carbon conversion was only slightly affected. At a given nickel to support ratio, a threefold increase in methane yield was observed by increasing the temperature from 350 to 410 oC. The catalytic activity also increased by the addition small quantity of potassium. The activity of Ni/γ-Al2O3 catalyst varied based on the affinity of the catalyst to form nickel aluminate spinel. This is also the first report on the role of oxidative pretreatment of the carbon nanotubes by nitric acid on the performance of these catalysts for the supercritical water gasification process. Using different lignocellulosic feeds, it was found that the gasification of glucose, fructose, cellulose, xylan and pulp resulted in comparable gas yields (± 10%) after 60 min, whereas alkali lignin was substantially harder to gasify. Interestingly, gasification yield of bark, which had a high lignin content, was comparable to those of cellulose. In summary, the Ni/α-Al2O3 catalyst had a higher hydrogen selectivity and comparable catalytic activity to the best commercially available catalysts for SCWG of carbohydrates.

Supercritical fluid technology is a well documented and emergent technology used in many industries today for the formation of micro- and nano- particles. The use of supercritical fluids allows synthesis of various types of particles since their properties can be varied with temperature or pressure, which sequentially can control the physical and chemical properties of the particles produced. Several different processes designed to generate powders and composites using supercritical fluids have been proposed in the past 20 years which can be used to synthesize materials with high performance specifications and unique functionality. In this research work, an extrusion micronization process using supercritical fluid has been proposed. This powder production technique could be a promising alternative to conventional techniques in terms of improvement in product quality as it provides a better control over particle size, morphology and particle size distribution, without degradation or contamination of the product. In addition, as extrusion is globally used for polymer production and processing, particle production by extrusion will allow production and processing in a single process step, eliminating the need for secondary particle production methods. The micronization process designed and described in this thesis involves a twin screw extruder equipped with a converging die and a high resistance spraying nozzle for particle production. A special CO2 injection device and polymer collection chamber was designed for CO2 supply and powder collection. To ensure complete dissolution of CO2 into the polymer matrix, stable injection of CO2, pressure generation and constant spray of micronized polymer particles, a special screw configuration was carefully designed for the extrusion process. The feasibility and the performance of this process have been demonstrated by experimental studies performed with low molecular weight polyethylene wax. Carbon dioxide at supercritical conditions was used as a solvent for processing the polymer. The generated polyethylene particles from the polyethylene wax/carbon dioxide solution system were analyzed and studied using an optical microscope, scanning electron microscope, capillary rheometer and differential scanning calorimeter. A detailed study on the effects of the processing parameters, such as temperature, pressure, flow rate and supercritical fluid on properties of polyethylene particle produced was carried out. The particle size data collected using an optical microscope indicate a significant impact of temperature and CO2 content on particle size. The obtained size data were utilized to generate particle size distribution plots and studied to analyze the effect of the processing variables. It was found that particle size distribution is affected by processing temperature and CO2 content. Studies of the SEM images reveal that the morphology of particles can be controlled by varying processing variables like temperature, polymer feed rate and CO2 content. The particles generated during this study indicate that particle production in an extrusion process using supercritical carbon dioxide is achievable and appears to be a promising alternative to conventional polymer particle production methods such as grinding, milling and other supercritical fluid-based precipitation methods. To validate and generalize the applicability of this process, micronization of other polymeric material should be performed. Commercialization of this technology will further require predictability and consistency of the characteristics of the product, for which a detailed understanding of the influence of all relevant process variables is necessary. In addition, development of theoretical models will further assist in the scale-up and commercialization of this supercritical fluid assisted micronization technology in the near future.

Thesis (PhD) -- University of South Australia, 1994

Thesis (Ph.D.)--University of Tulsa, 1991. / Bibliography: leaves 239-249.

Thesis (doctoral)--University of Helsinki, 2008. / Includes bibliographical references. Also available on the World Wide Web.