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with algae having tremendous potential as a sustainable and efficient alternative. As such, there is a significant incentive to improve and optimize the processes for algal biofuel production including lipid extraction and conversion. Opportunities in the Algal Biodiesel Production Process. The production of biodiesel from algae is a multi-step process that includes algal growth, harvesting, extraction, and conversion into fuel (Figure 1). In order for algal biofuels to become viable, technologies for each of these steps need to evaluated and optimized for efficiency and sustainability. Life-cycle analysis (LCA) of this process shows that there are significant energy gains to be had over the base case in terms of energy use particularly in the steps of harvesting and extraction/ conversion (Figure 1). Figure 1: Life cycle analysis results of the energy requirements for algal biodiesel production [14]. Current extraction methods, such as the Bligh and Dyer method [11], employ chloroform and/or hexane in a series of extraction and aqueous washing steps. The organic phase is then recovered, and upon evaporation of the chloroform, leaves a residue operationally defined as “lipid”. This extraction process is non-selective as the “lipid” consists of several different components including hydrocarbons, polar lipids, pigments, in addition to the desired triglycerides (TG) [12]. While the Bligh and Dyer method is used for lipid analysis, it is non-selective, time consuming, wasteful, relies on toxic substances, and is not particularly efficient. In the base case scenario for commercial production of biodiesel (Figure 1), hexane extraction is considered the current industry standard due to the common use of hexane for use in other oil extractions [13]. This means of lipid extraction is also quite energy intensive as it requires a dry algae feedstock, and there is embedded energy associated with the production and distillation of hexane [14]. In the production of algal biodiesel, extraction is followed by a step-wise transesterification reaction producing three FAME molecules for every molecule of TG. Diglyceride (DG) and mono-glyceride (MG) are produced as intermediates, with glycerol as a by-product of the overall reaction (Figure 2). The first step of the reaction, TG to DG is generally considered the rate-limiting step in ambient conditions [15], but the reaction kinetics must be explored at supercritical conditions. Since complete transesterification of one TG molecule requires 3 molecules of alcohol, a minimal 3:1 molar ratio of methanol (or ethanol):substrate is required with kinetics being favored at ratios of at least 6:1 or higher [16]. In addition to an alcohol, the transesterification step utilizes an acidic, basic or enzymatic catalyst to carry out the reaction at temperatures below 100 ̊C. Acidic catalysts can be used in feedstocks that may be contaminated with free fatty acids or water, preventing saponification that would occur with basic catalysts. However, basic catalysts have faster reaction kinetics than acidic catalysts [16]. Lipases are also used for transesterification requiring a lower operating temperature, but are expensive compared to the alternatives [16].PDF Image | One-Pot Algal Biodiesel Production in Supercritical CO2
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