Mississippi State University
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Dissertation - Open Access
Biodiesel is one of the most widely used biofuels in the world, due in part to its simplicity of production, compatibility with existing engines, and reduction of green house gas emissions. However, technical difficulties with biodiesel include: (1) the need of highly refined oil for ASTM compliance, (2) incompatibility with the petroleum-diesel pipeline distribution system, and (3) a relatively small inventory of expensive feedstocks. Issues (1) and (2) could be overcome by the production of biofuels using chemical processes associated with petroleum refining. Catalytic lipid cracking could result in green diesel, a fuel chemically similar to conventional diesel but derived from a clean renewable feedstock. The impact of phosphorus poisoning on catalytic cracking of lipids has been studied in this work using both homogeneous and heterogeneous catalysts. Catalytic cracking of model lipids was shown to occur in a homogeneous liquid phase with triflic acid, a superacid 100 times more acidic than sulfuric acid. Products obtained from the reaction were heavily oxygenated and generally unsuitable for fuel use, suggesting the need for heterogeneous catalytic cracking. Reaction kinetics show a high linear dependence on Brönsted system acidity, with an overall reaction order of 3. The affect of phosphorus on heterogeneous acid cracking was then studied. Since lipid feedstocks contain small amounts of phospholipids knowledge of the interactions between phospholipids and zeolites is crucial to a system-wide understanding of the lipid cracking process. Phosphorus-containing compounds were used to poison ZSM-5 (a solid zeolite catalyst) in order to simulate the cracking of phospholipids. Model compounds were then cracked over the poisoned zeolite, with differences in product distribution and kinetics based on phosphorus loading recorded. It was shown that phosphorous has a dramatic effect on both conversion and product distribution of cracking reactions. It is believed that phosphorous binds irreversibly to heterogeneous active sites, causing the majority of deactivation. To address the issue of limited feedstock availability, research was also undertaken to find new lipids sources for biofuel use. It was determined that lipids extracted from microorganisms grown in a municipal wastewater treatment system could be suitable. However, any phosphorous must be removed before catalytic cracking of the extracted lipids.
Dufreche, Stephen Thomas, "Effect of phosphorous poisoning on catalytic cracking of lipids for green diesel production" (2008). Theses and Dissertations. 1677.