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Biodiesel Production From High Free Fatty Acid Content

Biodiesel Production From High Free Fatty Acid Content

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Published by: edwardjustinian on Jul 16, 2012
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04/22/2014

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 BIODIESEL PRODUCTION FROM HIGH FREE FATTY ACID CONTENTFEEDSTOCKSA DissertationPresented tothe Graduate School of Clemson UniversityIn Partial Fulfillmentof the Requirements for the DegreeDoctor of PhilosophyChemical Engineering byKaewta SuwannakarnMay 2008Accepted by:Dr. James G. Goodwin, Jr., Committee Chair Dr. David A. BruceDr. Christopher L. KitchensDr. Shiou-Jyh Hwu
 
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ABSTRACT
Biomass, such as animal fats and grease, is one of the better sources for transportation fuels, e.g. biodiesel. Use of such biomass in the biodiesel synthesisdecreases the need for fossil energy, provides an outlet for utilizing the abundantresources effectively and economically, results in a cleaner fuel that is biodegradable,renewable, and non-toxic. Free fatty acid (FFA) esterification and triglyceride (TG)transesterification with low molecular weight alcohols are the central reactions for the biodiesel production. The focus of this research is to establish a better fundamentalinsight into heterogeneous catalysis for biodiesel forming reactions, in an attempt todesign the catalyst systems more proficient and durable for applications concerning biodiesel synthesis.Commercial processes normally involve low reaction temperatures (i.e. 60 °C) tomaintain the alcohols in the liquid phase; however, the use of high reaction temperaturesis required to improve the catalytic activity. Using gas-phase esterification of acetic acidwith methanol (as a probe reaction) at the reaction temperatures exceeding the boiling point of water, the intrinsic activities of a variety of solid acid catalysts were investigatedand compared. All catalysts (zeolite (Hβ), sulfated zirconia (SZ), tungstated zirconia(WZ), and Nafion/silica (SAC-13)) exhibited the similar capacity for effectively catalyzeesterification. The nature of the active sites for solid acid catalysts (Brønsted vs. Lewisacid sites) was examined and discovered that Brønsted acid sites were found to be a keyfor the catalysis.
 
iiiKnowledge of the reaction mechanism for heterogeneous esterification at highreaction temperatures was elucidated by using SAC-13 as a catalyst. The resultssuggested that the reaction proceeded via a single site mechanism and followed the samereaction pathway as homogeneous catalysis in which the adsorbed acetic acid appeared toreact with the alcohol from the gas phase. As the reaction temperatures increased, achange in the reaction controlling step for esterification from surface reaction (at lowtemperature) to carboxylic acid adsorption (at high temperature) satisfactorily explainedthe experimental observations. As a result, the reaction orders for the alcohols werechanged toward negative values, suggesting that use of a large excess of alcohol (astypically used at lower temperatures) could result in a significant lower reaction rate.The negative impact of alcohols on the catalyst activity at high reactiontemperatures was further remarked in a parallel study on the solid acid catalyzed liquid- phase transesterification of triglyceride. Operating under N
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atmosphere and temperatureof 120 °C, a solid acid catalyst containing sulfur, i.e. sulfated zirconia, was deactivated by a permanent removal of its active sites in the presence of liquid alcohols. All of theseresults would lead to a better design for the reaction system dealing with the methanolysisof waste greases. Finally, the feasibility of a continuous multiphase reaction system wassuccessfully demonstrated by using a simulative mixture of waste greases (lauric acid intricaprylin). By conducting the reaction at high temperatures (>100 °C) and atmospheric pressure, a residue alcohol and byproduct water were continuously removed, resulting inthe completion in esterification reaction and a better physical-chemical characteristics of ester products.

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