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Among various sources for biofuels, microalgae provide at least three-orders-of-magnitude higher production rate of biodiesel at a given land area than conventional crop-based methods. However, microalgal biodiesel still suffers from significantly lower harvesting efficiency, making such a fuel less competitive. To increase the separation efficiency of microalgae from cultivation solution, an orbital microchannel was utilized that enabled the isolation of biofuel-algae particles from the effluent. The results obtained showed that the separation efficiency in the microfluidic centrifugal separator can be as high as 76% within a quick separation time of 30 seconds. Multiple parameters of algae behaviors and separation techniques such as initial concentration, pH and temperature were studied and manipulated to achieve better efficiencies. It was found that changing these factors altered the separation efficiency by increasing or decreasing flocculation, or “clumping” of the microalgae within the microchannels. The results suggested that an acidic condition would enhance the separation efficiency since in a basic environment, large flocs of microalgae would block and hinder the separation process. Furthermore, a hot temperature solution (around 33 °C) yielded to a higher separation efficiency. The important characteristics of the separator geometry and the infusion rate on algae separation were also very effective in the separation process. This study revealed that there is an opportunity to improve the currently low efficiency of algae separation in centrifugal systems using much smaller designs in size, ensuring a much more efficient algae harvesting. / Includes bibliography. / Thesis (MS)--Florida Atlantic University, 2021. / FAU Electronic Theses and Dissertations Collection

Orientador: Mauricio Boscolo / Banca: Devaney Ribeiro do Carmo / Banca: João Cláudio Thoméo / Resumo: Este estudo teve como foco a otimização do processo de produção de biodiesel etílico por transesterificação entre etanol e óleo de soja e catalisado por óxidos mistos derivados de materiais tipo hidrotalcita (Ox-MgAl, Ox-Lu1%, Ox-Yb1%, Ox-Zn10%Fe10% e OxW2,5%). As condições reacionais que afetam o rendimento desta reação foram investigadas. A metodologia de superfície de resposta (MSR) baseada no Planejamento Composto Central de quatro fatores em cinco níveis foi empregada em duas etapas. No primeiro planejamento experimental as variáveis do processo foram temperatura de reação, tempo de reação, razão molar etanol/óleo e massa de catalisador, enquanto que o rendimento do biodiesel foi a variável resposta principal. No segundo planejamento experimental, as variáveis do processo foram o tempo de reação e razão molar etanol/óleo, sendo a massa de catalisador e a temperatura mantidas constantes. Foram obtidos cinco modelos codificados de segunda ordem que descrevem o rendimento do biodiesel em função do tempo e da razão molar etanol/óleo de soja e as condições ótimas de cada catalisador foram encontradas. Os experimentos foram realizados sob estas condições para confirmar a validade do modelo e o maior rendimento de biodiesel etílico obtido utilizando as variáveis otimizadas. O catalisador Ox-Yb1% proporcionou o maior rendimento (83,8%) depois de 15,5 horas com razão molar etanol/óleo de soja igual a 37/1. Os valores experimentais concordaram com os resultados previstos pela MSR... / Abstract: This study focused on the optimization of the biodiesel production process by transesterification between ethanol and soybean oil and catalyzed by mixed oxides derived from hydrotalcite type materials (MgAl, MgAlLu, MgAlYb, MgAlZnFe and MgAlW). The reaction conditions that affect the yield of this reaction were investigated. The response surface methodology (MSR) based on the Central Composite Planning of four factors at five levels was employed in two steps. In the first experimental design the process variables were reaction temperature, reaction time, ethanol / oil molar ratio and catalyst mass, while the biodiesel yield was the main response variable. In the second experimental design, the process variables were the reaction time and the ethanol / oil molar ratio, the catalyst mass and the temperature kept constant. Five second order coded models were obtained that describe the biodiesel yield as a function of time and the ethanol / soybean oil molar ratio and the optimum conditions of each catalyst were found. The experiments were carried out under these conditions to confirm the validity of the model and the highest yield of ethylic biodiesel obtained using the optimized variables. The MgAlYb catalyst gave the highest yield (83.8%) after 15.5 hours with molar ratio ethanol / soybean oil equal to 37/1. The experimental values agreed with the results predicted by the MSR and the optimization models were validated / Mestre

Oleaginous microbes can accumulate over 20% of their cell dry weight as lipids that are stored as intracellular energy reserves. The characterization of other oleaginous bacteria creates opportunities for the development of alternative feedstocks and technologies. Rhodococcus rhodochrous is a gram-positive bacterium known for its biodegradation capabilities, but little is known about its ability to accumulate lipids. As R. rhodochrous is capable of degrading hydrocarbon gasses and other aromatics, this study aims to investigate any associated lipid production during the conversion of waste and nontraditional carbon sources, such as model lignocellulosic inhibitors. Lignocellulosic biomass is the most abundant and renewable organic material in the world and is composed of cellulose, hemicellulose, and lignin, which can be pretreated to release sugars from the complex, and often recalcitrant, lignin polymer for microbial fermentation. R. rhodochrous was cultivated with various carbon sources, including glucose, xylose, acetic acid, furfural, phenol, vanillic acid, hydroxybenzoic acid, and propane. The results suggest that R. rhodochrous can survive in the presence of these compounds, achieving almost 7g/L cell dry weight after 168 hours and still accumulate up to 40-50% of cell dry weight as lipid in glucose supplemented media. Furthermore, the aromatic compounds are undetected after 48 hours indicating that R. rhodochrous was able to tolerate these compounds and accumulate lipids. Fatty acid methyl ester profiles show a prevalence of palmitic and oleic methyl esters. Overall, these studies are contributing to a better understanding and characterization of another oleaginous Rhodococcus species, Rhodococcus rhodochrous.

The potential of enhancing lipid accumulation in municipal sewage activated sludge via fermentation of lignocellulose biomass hydrolyzate was investigated. The overall objective was to increase the levels of feedstock lipids in the activated sludge biomass and increase its biodiesel yield via in situ or ex situ transesterification; and improve its cost competitiveness as an abundant feedstock source for biofuels production. To reduce production costs and maintain environmental sustainability, influent wastewater and waste lignocellulose biomass hydrolyzate were used as cultivation media and substrate, respectively. However, lignocellulose hydrolyzates also contain degradation by-products such as furfural and acetic acid that are known to exert inhibitory effects on microorganisms; hence their effects on the fermentative performance of activated sludge were investigated and fermentation strategies were proposed and evaluated to counteract the microbial toxicity of these compounds. The utilization rate and efficiency of xylose by activated sludge microorganisms for lipid production was also evaluated as pentose sugars such as xylose usually constitute a major percentage of lignocellulose hydrolyzates. Furthermore, variations in the population profile of activated sludge microbiota were determined via 16S rRNA sequence analysis to determine the effect of sugar fermentation at different initial conditions. Results show that activated sludge lipid contents and biodiesel yield could be enhanced by fermentation of sugars at a high initial C:N ratio (70:1). Furfural was found to be highly inhibitory to microbial growth and lipid accumulation while high initial acetic acid concentrations enhanced biomass production but not lipid formation. Xylose was also utilized more efficiently than glucose by the activated sludge microorganisms for biomass and lipid production albeit at relatively slower rates; hence sugar mixtures derived from lignocellulose could be utilized for the process. Semicontinuous and continuous fermentation modes were proposed and evaluated as strategies to reduce inhibitory effect of furfural and acetic acid and improve lipid productivity, but the lack of nutrient supplementation prevented the cultures from sustaining microbial growth and lipid production, leading to cell death and washout. Finally, the reduction in the diversity of the activated sludge microbiota could point to specific microbial strains that are mainly responsible for lipid accumulation.

Current diesel technologies involve a broad spectrum of combustion regimes. Previous diesel combustion models either lack the universality across various combustion regimes or suffer computational cost. This dissertation discusses the development of a phenomenological framework to identify and understand key in-cylinder processes that influence the overall performance of a compression ignition engine. The first part of this research is focused on understanding the ignition delay (ID) of diesel fuel in a pilot-ignited partially premixed, low temperature natural gas (NG) combustion engine. Lean premixed low temperature NG combustion is achieved by using small pilot diesel sprays (2-3% of total fuel energy) injected during early compression stroke (about 60° BTDC). Modeling ignition delay at advanced pilot injection timings (50°-60°BTDC) presents unique challenges. In this study, single component droplet evaporation model in conjunction with the Shell hydrocarbon autoignition (SAI) model is used to obtain ignition delay predictions of pilot diesel over a wide range of injection timings (20°-60° BTDC). Detailed sensitivity analysis of several SAI model parameters revealed that the model parameter Aq, which influences chain initiation reactions, was most important to predict ignition delays at very lean equivalence ratios. Additional studies performed to ascertain critical model parameters revealed that ignition delay was particularly sensitive to intake manifold temperature over the range of injection timings investigated. Finally, the validated SAI model was used to predict ignition delays of pilot diesel fuel at various exhaust gas recirculation (EGR) substitutions, intake manifold temperatures and engine loads (bmep = 6 bar and 3 bar, respectively). The second part of this research involved the development of a phenomenological simulation of diesel/biodiesel combustion, which included sub-models for diesel spray entrainment, evaporation, ignition and premixed and mixing-controlled combustion. In the simulation, the cylinder contents consisted of an unburned zone, packet zones, and a burned zone. The simulation, after appropriate calibration, was capable of predicting cylinder pressure and heat release rates at different engine load conditions over the injection timing range of 0°BTDC to 10°BTDC. The total number of packets, droplet evaporation rates, air entrainment rates; ignition delay and premixed/mixing-controlled reaction rate parameters had a profound influence on combustion predictions.

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It is well known fact that energy is a big issue for this world and substantial amount of research is going on worldwide for alternative fuels that are environmentally friendly, especially because of the fact that crude petroleum reserves are dwindling. Also, research on alternative fuels is essential for increased energy security. Biodiesel is a renewable, biodegradable, and nontoxic fuel. At present, when homogeneous catalysts are used, biodiesel is primarily produced in batch reactors in which the required energy is provided by heating accompanied by mechanical mixing. Alternatively, ultrasonic processing could be an effective way to attain required mixing while providing the necessary activation energy. We found that, using ultrasonication, a biodiesel yield in excess of 99% can be achieved in a short time duration of five minutes or less in comparison to one hour or more using conventional batch reactor systems. Homogeneous acid or base catalysts dissolve fully in the glycerol layer and partially in the fatty acid methyl esters (biodiesel) layer during the triglyceride transesterification process. Heterogeneous (solid) catalysts, on the other hand, can prevent catalyst contamination making product separation much easier. In the present work, one of the objective was to determine the transesterification kinetics of different pure metal oxide catalysts, mixed metal oxide catalysts, layered double hydroxides with their corresponding yield is presented. It was found that heterogeneous catalysts require much higher temperatures (215oC) and pressures to achieve acceptable conversion levels compared to homogeneous catalysts. For some of the mixed metal oxide solid catalysts a conversion level of 99% was observed. The present study also deals with the catalyst characterization on the basis of their acidity/ basicity and site strength, and surface area. Finally the deoxygenation of fatty acid methyl esters was carried out in order to upgrade the biodiesel. As a result, several aliphatic and aromatic hydrocarbons were detected in the mass spectrometric studies. This dissertation consists of five chapters. Chapter I presents a brief introduction to biodiesel production and the objectives of the study. Chapter II contains a review of literature. Chapter III contains the materials and methods used in this study. In this chapter different principles and theories will be mentioned with regard to the use of ultrasonication towards biodiesel production, reaction kinetics of biodiesel production, catalyst characterizations and thermodynamic analysis of deoxygenation of fatty acid methyl esters. Chapter IV presents the results and its discussions. Finally, Chapter V discusses the summary and conclusions of the study.

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