AN ABSTRACT OF THE THESIS OF Wesley C. Miller for the degree of Master of Science in Biological and Ecological Engineering presented on December 22, 2010 Title: Evaluation of Feedstocks for Cellulosic Ethanol and Bioproducts Production in the Northwest Abstract approved: _____________________________ Ganti S. Murthy Cellulosic ethanol production for transportation fuel is one source to help satisfy the increasing worldwide demand for energy and depletion of the fossil fuel supply. Evaluating potential production from plants and waste in Oregon, Washington and Idaho is the purpose of this study. Reed Canary grass, Annual Ryegrass, wheat straw, corn cobs, corn pericarp, gorse and waste newspaper are studied. Except for the newspaper (an analogue of municipal solid waste), these are common agricultural crops or invasive plants which are adapted to this area, and most of the United States. This paper estimates the potential for production of ethanol from these feedstocks through an investigation of available cropland combined with laboratory research into ethanol yield from these materials. Laboratory data for the various feedstocks ranged up to 237kg/Mg (72 gallons/ton) of ethanol produced. Total Northwest cropland is 7,502,272 hectares (18,538,517 acres) with 2,638,955 hectares (6,520,793 acres) of that under irrigation. (2007 Census of Agriculture - County Data, 2008). Common gorse, Ulex europaeus L., was examined for amounts of ether, hexane, ethanol and steam extracts and cellulosic ethanol yield at different times of the year. The highest seasonal amount of each component was approximately double that of the lowest. © Copyright by Wesley C. Miller December 22, 2010 All Rights Reserved Evaluation of Feedstocks for Cellulosic Ethanol and Bioproducts Production in the Northwest by Wesley C. Miller A THESIS submitted to Oregon State University in partial fulfillment of the requirements for the degree of Master of Science Presented December 22, 2010 Commencement June 2011 Master of Science thesis of Wesley C. Miller presented on December 22, 2010. APPROVED: ____________________________ Major Professor representing Biological and Ecological Engineering ____________________________ Head of The Department of Biological and Ecological Engineering ____________________________ Dean of the Graduate School I understand that my thesis will become part of the permanent collection of Oregon State University libraries. My signature below authorizes release of my thesis to any reader upon request. ____________________________ Wesley C. Miller, Author ACKNOWLEDGMENTS I would like to thank Dr. Ganti Murthy for the opportunity to be able to attend graduate school and use his Sustainable Technology Lab facilities for most of my research. His patience, input and direction throughout my Master’s program has been priceless. Many thanks also to the rest of my committee members, Dr. Mike Penner, Dr. Christine Kelly and Dr.Lisbeth Goddik for their advice, lab equipment and valuable assistance. Special thanks to Dr. David Hannaway of Crop and Soil Science, for his thorough and constructive writing input while I was preparing my thesis. Thanks to Dr. John Bolte, Skipper of Biological and Ecological Engineering Department, for his support of my plans and dreams and goals. Thanks to the BEE professors and staff for being very helpful and supportive over the years. Thanks to Ms. Cassie Bouska with OSU Extension and Bandon Dunes Golf Resort for supporting my gorse research. Thanks to Dr. M.E. Tumbleson and Dr. V. Singh, University of Illinois Urbana Champaign for the corn cob and pericarp material. Thanks to Jim Ervin, greenhouse manager, and Russ Karow of Crop and Soil Science Department for use of their Wiley Mill for my sample preparation—I tried to leave it as clean as I found it! Thanks to my fellow Gilmore Hall lab mates, both upstairs and downstairs, for their help and ideas. I couldn’t have done it without you. Special thanks to Kyle Sander, fellow student of biofuels and other interesting areas, for his encouragement and instruction in all things computer, and the many opportunities to take a short break and get outdoors with him for some much needed re-creation. Last but far from least, endless thanks to my wife, Terry, for her patience and work at keeping the home fires burning (biofuel). CONTRIBUTION OF AUTHORS Dr. Ganti Murthy assisted greatly in the organization and direction of my research, and with the thesis editing. TABLE OF CONTENTS Page Chapter 1 General Introduction …………………………………………......1 Chapter 2 – Evaluation of Northwest Cellulosic Feedstocks for Ethanol Production……………………….........................................................4 Introduction…………………………………………………….....….4 Northwest Feedstocks And Potential Supply………………...9 Soil Organic Matter Maintenance............................................11 Feedstocks: Description And Potential Production…….…...13 Pretreatment Methods……………………………………… 18 Analytical Methods………………………………………… 22 Materials and Methods……………………………………………....24 Feedstock Materials…………….…………………………....24 Feedstock Characterization………………………………......25 Pretreatment Methods……………………………………… 25 Simultaneous Saccharification and Fermentation………….. 27 Ethanol Analysis Methods…………………………………...28 Results and Discussion…………………………………………….. 30 Feedstock Characterization…………………………………..30 Ethanol Yield Results and Discussion…………………….…34 Conclusion............................................................................................43 Feedstock And Pretreatment Effects........................................43 Future Fuel Supply Scenarios...................................................43 Chapter 3- Seasonal Evaluation of Gorse for Ethanol and Other Products…………………………………….……...45 Abstract…………………………………………………….………....45 Introduction………………………………………………………......46 Materials and Methods…………………………………………….....48 TABLE OF CONTENTS (Continued) Page Results and Discussion……………………………………………....51 Particle Size Analysis………………………………………..51 Monthly Ethanol Yield Variation……………………....……52 Extraction of Pigments and Oils………………………….….52 Spectrophotometric Analysis………………………………...55 Conclusion…………. …………………………………………….…56 Chapter 4 – General Conclusion……………………………………………..58 Feedstocks and Pretreatments..............................................................58 Gorse and Other Woody Shrub Utilization..........................................58 Future Research....................................................................................59 Bibliography………………………………………………………….............60 Appendix……………………………………………………………......…….68 Fig. A.1 Particle Size Mass Distribution Plot………………………...70 LIST OF FIGURES Figure Page Figure 2.1 Standard and Steam Explosion Tubes…………………………...27 Figure 2.2 Steam Explosion Pretreatment Equipment………………………28 Figure 2.3 Sample Weight on Sieve (g) vs Sieving Time (s)........................30 Figure 2.4 Particle size distribution of feedstocks..........................................32 Figure 2.5 Ethanol Yields Based on Weight Loss (as % of initial wt.) …...35 Figure 2.6 Wheat Straw Ethanol Yield (as % of initial dry weight)...............36 Figure 2.7 Reed Canarygrass Ethanol Yield (as % of initial dry weight).......37 Figure 2.8 Annual Ryegrass Ethanol Yield (as % of initial dry weight)........38 Figure 2.9 Corn Pericarp Ethanol Yield (as % of initial dry weight).............39 Figure 2.10 Corn Cob Ethanol Yield (as % of initial dry weight)..................40 Figure 2.11 Newspaper Ethanol Yield (as % of initial dry weight)................41 Figure 2.12 Ethanol Yield Based on Assay Results (as wt% of initial wt.)...42 Figure 3.1 Steam distillation apparatus……………………………………...50 Figure 3.2 Particle size analysis of Gorse…………………….….....………51 LIST OF TABLES Table Page Table 2.1 Northwest Potential Biomass Yields and Land Areas...................10 Table 2.2 Moisture and Ash Content of Feedstocks……………....………...33 Table 2.3 Lignin content of feedstocks……………………………….……..34 Table 3.1 Gorse ethanol yield by harvest month (% of dry weight)…....…...52 Table 3.2 Seasonal variation in Gorse ether extracts………………………..50 Table 3.3 Direct distillation of gorse………………………………………..54 Table 3.4 Ethanol and Hexane Extraction Yields (%)………………………55 Table 3.5 Gorse component extract absorbance values……………………..56 LIST OF APPENDIX TABLES Table Page Table A.1 Particle Size Distribution (% retained on sieve).............................69 Table A.2 Ethanol yield from weight loss data (% of dry weight).................71 Table A.3 Single factor ANOVA results for weight loss ethanol yields with respect to pretreatments...................................................................................72 Table A.4 Ethanol Assay Data (% of initial dry wt)......................................80 DEDICATION To my grandfathers: Wesley J. Miller, who supplied biomass fuel for Oregon State in the 1930’s, and had a strong dedication to helping others get a good start in life. John A Wells, who fueled my interest in science and research with his own. Evaluation of Feedstocks for Cellulosic Ethanol and Bioproducts Production in the Northwest Chapter 1 General Introduction Increasing cost and rising demand for energy worldwide from population growth and economic development have focused world attention on developing larger and more sustainable supplies of transportation fuel. Cellulosic ethanol has the potential to significantly augment ethanol production for transportation use. This is possible for several reasons. Cellulose is the most abundant structural