The University of Toledo The University of Toledo Digital Repository Theses and Dissertations 2010 Evaluation of Lake Erie algae as bio-fuel feedstock Vasudev Gottumukala The University of Toledo Follow this and additional works at: http://utdr.edu/theses-dissertations Recommended Citation Gottumukala, Vasudev, "Evaluation of Lake Erie algae as bio-fuel feedstock" (2010). Theses and Dissertations. This Thesis is brought to you for free and open access by The University of Toledo Digital Repository. It has been accepted for inclusion in Theses and Dissertations by an authorized administrator of The University of Toledo Digital Repository.
For more information, please contact arjun. A Thesis entitled Evaluation of Lake Erie Algae as Bio-fuel Feedstock by Vasudev Gottumukala Submitted to the Graduate Faculty as partial fulfillment of the requirements for The Master of Science in Chemical Engineering _____________________________ Advisor: Constance A. Schall ______________________________ Committee Member: Thomas Bridgeman ______________________________ Committee Member: Sridhar Viamajala ______________________________ Dean: Dr. Patricia Komuniecki College of Graduate Studies The University of Toledo May 2010 An Abstract of Evaluation of Lake Erie Algae as Bio-fuel Feedstock by Vasudev Gottumukala Submitted to the Graduate Faculty in partial fulfillment of the requirements for the Master of Science in Chemical Engineering The University of Toledo May 2010 Currently, transportation fuels are produced from continuously depleting fossil fuel sources.
This calls for additional renewable sources that could be used for the production of high quality transportation fuel. Bio-diesel is one such alternative. Soybean, a food crop, has been used in the past as a source of lipids for the production of bio-diesel. Algae are an alternative non-food source of lipids for bio-diesel and/or carbohydrates for bio-ethanol.
We have surveyed algae and phytoplankton in the western Lake Erie basin to identify the predominant algae species. The lipid, carbohydrate and the protein content of lake species were determined. Sampling at selected lake sites was performed at regular intervals of time in an attempt to correlate lake conditions (i. temperature, phosphorus and nitrogen) with the selection and composition of species.
Based on the results of these analyses, native species were identified as candidates for bio-diesel or bio-ethanol production. iii Few preliminary experiments were performed to process soybean oil using a batch reactor to convert the triacylglycerides to free fatty acids which would then be converted to fatty acid methyl esters (bio-diesel) through transesterification. The optimized processing conditions can then be utilized to process algae. iv This work is dedicated to my parents, sister & brother-in-law and to my best friends for their tremendous support and encouragement throughout.
Acknowledgements I wish to express my sincere gratitude to my advisor Dr. I would also like to thank Dr. Thomas Bridgeman, Dr. Sasidhar Varanasi and Dr.
Sridhar Viamajala for their guidance and support during my research. I would like to thank Dr. Cyndee Gruden, Dr. Thomas Kina and Dr.
Pannee Burckel for their help with analytical equipments and useful suggestions. I would like to thank Dr. Glenn Lipscomb for giving me admission in University of Toledo. I am grateful to the Department of Chemical and Environmental Engineering for financial assistantship throughout my course of study.
I would also like to thank the Center for Innovative Food technology for funding my project. I would really like to thank my labmates and friends Indira Priya Samayam, Noureen Faizee, Thehazhnan Ponnaiyan, Christopher Barr, Amber Bosley, Brett Digman, Richard Hausman, Justin Chaffin, Olga Mileyeva-Biebesheimer, Ananth Dadi, Kripa Rao and Micheal Mayer for their help, support and encouragement. Last but not the least I would like to thank my colleagues at my company, Midwest Bio Renewables, for believing in me and giving me complete freedom and flexibility in my job timings in order to complete my thesis. vi Table of Contents Abstract.
vi Table of Contents .vii List of Tables. xi List of Figures. 1 Chapter 1 - Characterization of Algae .2 Dry weight analysis .5 Structural carbohydrate & lignin analysis. 26 viii Chapter 2 - Characterization of Aulacoseira granulata .2 Results and Discussion .1 Dry weight analysis .3 Starch, structural carbohydrate and lignin analysis.
40 Chapter 3 - Characterization of Cladophora glomerata .2 Results and Discussion .1 Dry weight analysis .3 Starch, structural carbohydrate and lignin analysis. 51 Chapter 4 - Characterization of Lyngbya wollei.2 Results and Discussion .1 Dry weight analysis .3 Starch, structural carbohydrate and lignin analysis. 60 Chapter 5 – Effect of nutrient availability on growth of Aulacoseira granulata .2 Nutrient availability related to Aulacoseira granulata’s growth. 74 Chapter 6 – Soybean oil processing .3 Hydrolysis of soybean oil .4 Results and Discussion.
89 Chapter 7 – Conclusions and future work. 100 x List of Tables 1-1 Acetanilide (standard) - expected vs. 21 2-1 Average dry weight analysis data - Aulacoseira granulata centrifuged paste. 31 2-2 Gravimetric quantification of lipid – Aulacoseira granulata.
32 2-3 Percent lipid and FAMES extracted from Aulacoseira granulata, calculated on a dry weight basis. 35 2-4 Aulacoseira granulata – Free fatty acid distribution. 35 2-5 GC-MS data – Aulacoseira granulata summer-2008 sample. 36 2-6 GC-MS data – Aulacoseira granulata summer-2009 sample.
37 2-7 C H N weight percent data – Aulacoseira granulata. 39 3-1 Average dry weight analysis data - Cladophora glomerata centrifuged paste. 43 3-2 Gravimetric quantification of lipid – Cladophora glomerata. 44 3-3 Percent lipid and FAMES extracted from Cladophora glomerata, calculated on a dry weight basis.
45 3-4 GC-MS data – Cladophora glomerata December-2008 sample. 46 3-5 Cladophora glomerata – Free Fatty Acid Distribution. 46 3-6 HPLC data from the total carbohydrate analysis – Cladophora glomerata. 47 3-7 HPLC data from the starch analysis – Cladophora glomerata.
48 xi 3-8 C H N weight percent data – Cladophora glomerata. 50 4-1 Average dry weight analysis data for Lyngbya wollei centrifuged paste. 55 4-2 Gravimetric quantification of lipid – Lyngbya wollei. 56 4-3 Percent lipid and FAMES extracted from Lyngbya wollei, calculated on a dry weight basis.
57 4-4 HPLC data from the total carbohydrate analysis – Lyngbya wollei. 58 4-5 HPLC data from the starch analysis – Lyngbya wollei. 59 4-6 C H N weight percent data – Lyngbya wollei. 60 5-1 Set of nutrient ratios (millimolar basis) calculated from the nutrient sources measured at the sampling location of Aulacoseira granulata in the year 2008 on 07/07/2008.
69 5-2 Set of nutrient ratios (millimolar basis) calculated from the nutrient sources measured at the sampling location of Aulacoseira granulata in the year 2009 on 06/26/2009. 69 6-1 Theoretical yields obtained in soybean oil hydrolysis. 89 6-2 FFA distribution at varying reaction times and catalyst loadings. 91 xii List of Figures I-1 Top ten fossil fuel producing and consuming countries in 2008.
1 I-2 Overall energy consumption in the U.S during the years 2003-2007. 2 I-3 Closed carbon cycle – Algae. 6 I-5 Algae life cycle. 7 1-1 Sample calibration curve of a mixed standards analyzed by GC with flame ionization detection (FID).
16 1-2 Sample chromatogram of a mixed standard run through GC. 17 2-1 Microscopic image of Aulacoseira granulata. 30 2-2 Sample chromatogram showing external standards run through GC. 33 2-3 Sample chromatogram showing Aulacoseira granulata (summer-2008) sample run.
34 3-1 Microscopic image of Cladophora glomerata. 42 3-2 Chromatogram – Cladophora glomerata December-2008 sample run. 45 4-1 Microscopic image of Lyngbya wollei. 54 4-2 Chromatogram – Lyngbya wollei July-2009 sample run.
57 xiii 5-1 HPLC Comparison between the TN: TP molar ratio for the data obtained in the year 2008 and 2009. 71 5-2 Comparison between the TSi: TP molar ratio for the data obtained in the year 2008 and 2009. 72 5-3 Comparison between the TSi: TN molar ratio for the data obtained in the year 2008 and 2009. 76 6-2 Reactor assembly along with the controlling unit.
84 6-3 Separation between the fatty acid layer and the aqueous glycerin layer. 85 6-4 Darkening of FFA layer with increasing reaction time (30, 45, 60 min). 87 6-5 Chromatogram showing FFA sample run through GC. 88 6-6 Chromatogram showing overlay of three sample (varying reaction times) runs through GC.
90 xiv Introduction One of the major problems that the world is facing is the dependence on fossil fuels for our day to day energy requirements. Studies have shown that almost 85% of the total energy being utilized is provided by the fossil fuels (Liu L. The increasing use of fossil fuel directly relates to global warming issues due to increased green house gas emissions (Schneider U. Due to high dependence and usage of this fuel, a decline in its availability is being observed (Liu L.
Fossil fuels include petroleum, coal and natural gas. Each of these feed stocks has importance in various energy applications. An important use of fossil fuels is in transportation in the form of liquid fuels. Top ten fossil fuel producing and consuming countries in 2008.
1 The fossil fuel production and consumption based on the data provided by the U. Energy Information Administration (Administration 2008) for the year 2008 is shown in the Fig. While being one of the top fossil fuel producing countries, the U.S is also the highest fuel consuming nation. The consumption rate is close to more than double its fuel production rate.
Because of this, the U.S has to depend on production in other countries and imports most fuel. There are alternative sources which can be investigated for fuel production that could, if not eliminate, reduce the dependence on other nations for fuel requirements. Recent research has focused on development of renewable fuel sources such as corn stover, soy beans, switch grass and algae for producing fuels that could be used directly or blended with the existing fuels. This could not only help in reducing the current fuel pricing but may also utilize agricultural waste and low quality lands in a productive way.
Overall energy consumption in the U.S during the years 2003-2007. 2 An energy survey by the Energy Information Administration (EIA, official energy statistics from the U. government) for the years 2003-2007 (Administration 2007), summarizes the energy use in U. It is clear from Figure I-2 that a major part of U.S energy requirements comes from fossil fuels.
Due to continuously depleting fossil fuel, the focus is now on using renewable sources for producing fuels for our energy requirements. The statistics shown in Figure I-2 clearly indicate that a major portion of renewable energy is obtained from biomass. As mentioned earlier, there are a number of biomass sources available. Biomass with high lignocellulosic content, like corn stover, is being considered for producing bio- ethanol (Sun Y.
Currently, US bio-ethanol is produced primarily from corn grain with the corn stover available as an agricultural residue. Soy bean oil has been used extensively in U.S, because of its high lipid content (also known as triacylglycerols, TAGs), as a feedstock for biodiesel (soy diesel) production (Van Gerpen J. Biodiesel draws attention because of its ease of production and simple blending with diesel fuel. It can also be utilized directly in its pure form (Van Gerpen J.
Other sources of vegetable oils have been evaluated using the fuel extraction process developed for soy bean oil (Van Gerpen J. With limited fossil fuel sources, the need for developing a process of producing alternative fuel using renewable feedstock has increased manifold. An energy crisis was observed during the early 1970’s. This encouraged the U.
Department of Energy (U.E) to look for an alternative energy source.E’s Office of Fuel Development then funded a nationwide research program, named The Aquatic Species 3 Program, which focused on the development of renewable transportation fuels from the high lipid containing algae species (Sheehan J. This 18 year long program eventually ended (in 1996) because the cost of producing biodiesel from algae was higher than fuel prices at that time(Sheehan J.