EXPERIMENTAL RESULTS AND COMPUTER SIMULATIONS FOR POST- COMBUSTION CARBON DIOXIDE REMOVAL USING LIMESTONE THESIS Presented in Partial Fulfillment of the Requirements for the Degree Master of Science in the Graduate School of The Ohio State University By William Kane Wang, B.S. ChBE Graduate Program in Chemical and Biomolecular Engineering The Ohio State University 2009 Thesis Committee: Liang-Shih Fan, Advisor Jacques Zakin ABSTRACT Amid growing concerns of global climate change, governmental entities and industry throughout the world are performing research on the capture and sequestration of carbon dioxide (CO2). Coal accounts for nearly half of the United States electricity generation and 40% of the world’s electricity generation. This directly translates into 33% of the United States CO2 emissions and 40% of the world’s CO2 emissions produced from coal- combustion power plants for electricity generation. Not surprisingly, a significant emphasis has been placed on capturing CO2 produced from coal-combustion power plants. To date, though, no large-scale power plant employs the use of carbon capture technologies. Under the leadership of Professor Liang-Shih Fan and his research group at The Ohio State University, a process that employs a solid sorbent to reactively remove CO2 from coal combustion flue gas has been developed. The Carbonation-Calcination Reaction (CCR) Process relies on a carbonation reaction with a metal oxide to remove the CO2 and a subsequent calcination reaction to produce a pure stream of CO2 while regenerating the metal oxide. An additional benefit to the CCR process is the ability of the sorbent to simultaneously remove sulfur dioxide (SO2) present in the flue gas stream. ii Upon successful bench-scale experiments, a 20 pound per hour coal combustion facility was erected to demonstrate the CCR Process. With the ability to capture greater than 90% CO2 and greater than 99% SO2 on a once-through basis with a commercially available calcium-based sorbent, the facility was re-renovated for multicylic investigations. Consistent CO2 removals over multiple cycles were obtained using an intermediate hydration reaction for reactivation of the calcium oxide sorbent. The hydration reaction reverses and eliminates any effect of sintering that occurs during the calcination reaction. Due to its inherently small particle size, along with an increase in surface area and pore volume upon spontaneous dehydration, calcium hydroxide is able to maintain constant CO2 removals. Computer simulations integrating the CCR Process into a power plant shows a high level of compatibility due to its high-temperature operation. Energy penalties between 15% and 20% were obtained, with compression of CO2 while producing a pure, dry stream of CO2 ready for sequestration. iii Dedicated to my family-Mother, Father, and three sisters iv ACKNOWLEDGEMENTS I would like to gratefully acknowledge my advisor, Professor Liang-Shih Fan, for providing the opportunity to obtain my graduate degree and perform research in his group. I have had the ability to learn a considerable amount in several fields that extend beyond research and academics. I would also like to acknowledge Professor Jacques Zakin for agreeing to be on my defense committee. The research performed could not have been achieved without several personnel from industry. I would like to thank Dr. Robert Statnick for providing input, sharing his previous experiences, providing continuous support, even in times of great stress, and his patience. I would also like to thank Dr. Mahesh Iyer for his initial role as mentor, support, and conversations, both during his time at Ohio State and beyond. I would like to thank Bob Brown and the Ohio Coal Development Office for their continued financial support of the research project. The members of the Industrial Review Committee, who have provided important suggestions in areas of experimental design, operational procedures, industrial expectations, safety precautions, and troubleshooting, have my deepest appreciation. They include Jeff Gerken from American Electric Power (AEP), Bartev Sakadjian from Babcock & Wilcox, Lew Benson, Dave McKinney, and James Derby of Carmeuse Lime & Stone, Dan Connell, Steve Winberg, and Dick Winschel of CONSOL v Energy, John Bloemer and Frank Carchedi of Duke Energy, and Mark Golightley of First Energy. I would also like to thank the entire Fan Research Group, which has undergone significant personnel changes during my five years as a graduate student. The members of the Carbonation Calcination Reaction (CCR) group consisting of Danny Wong, Shwetha Ramkumar, Dr. Songgeng Li, Siddharth Gumuluru, and Sun Zhenchao have significantly advanced the progress of the research project. With my initial research focusing on chemical looping combustion, I would like to thank Dr. Luis Vargas, who provided not only invaluable advice but also comic relief, Fanxing Li, Deepak Sridhar, Ray Kim, Andrew Tong, and Fu-Chen Yu. Transitioning into fluidization research, I would like to thank Dr. Bing Du, Dr. Zhe Cui, Dr. Raymond Lau, who taught me how to perform experiments while having fun, Dr. Warsito, Dr. Qussai Marashdeh, Orin Hemminger, Fei Wang, and Zhao Yu. Last but not least, I would like to thank Dr. Alissa Park for her guidance, compassion, and humor. I would also like to extend thanks to all the undergraduate help who didn’t mind the manual labor and not-so-clean conditions. They are Yao Wang, Alex Brown, Zack Patterson, Zack Yoscovits, and Joe Braucher. Without the administrative staff in both the Chemical and Biomolecular Engineering Department and The Ohio State University, the research project would have been far too difficult to handle. I would like to thank Mike Davis, Geoff Hulse, and Dave Jones for maintaining the computer labs and network and David Cade and Carl Scott for maintaining not only Koffolt Laboratory, but also the laboratory at West Campus. Paul Green and Leigh Evrard deserve thanks for their expertise in machining, fabrication, and installation of equipment. Without them, parts of the reactor would still be supported by vi bricks and wood. A special thanks must be given to Susan Tesfai and Lynn Flanagan, the two administrative workhorses of the research project. Their ability to keep the finances of the research project under control, incredible work hours, and ability to successfully obtain authorization for all the “odd” purchases that were made truly made the project run efficiently. The Ohio State Research Foundation also deserves a special thanks for authorizing all purchases in a timely fashion. I would like to thank my entire family-my parents, Kang-bo Wang and Su-Huei Wang, sisters, Jenny, Judy, and Peggy for their unending support and love. I would also like to give a special recognition to my two wonderful cats, Jack Junior (JJ) and Remi, who have provided me with hours of entertainment and joy. I would also like to thank the Capital Area Humane Society, as well as the Columbus Ultimate Disc Community, for providing an enjoyable atmosphere for relaxation. Of special note is Erin Schran for providing Darby, Amy Sminchak for providing Flash, Scott Miller for providing Clevis, Bob for providing Alfa and Bioko, and the entire Ultimate dog community and their owners. I would also like to extend my deepest thanks to Megan Covitz, Bredt Covitz, and their two wonderful cats, Jack and Eva, for providing me with countless meals, their incredible hospitality, and friendship. To Kelly Zilli, her three beautiful greyhounds, Vinnie, Guido, and Verdi, and her two adorable cats, Ezekiel and Elliott, I am forever indebted. The numerous dog walks, runs, randomness, and friendship have truly made my time in graduate school easier and more enjoyable. vii VITA September 18, 1981…………………………………………Born – St. Louis, Missouri June, 2004…………………………………………………...B.S. Chemical and Biomolecular Engineering, University of Illinois at Urbana-Champaign 2004-2009…………………………………………………..Graduate Research Associate The Ohio State University PUBLICATIONS Gupta, Puneet; Wang, William; Fan, Liang-Shih. Synthesis of High-Surface-Area SiC Through a Modified Sol-Gel Route: Control of the Pore Structure. Ind. Eng. Chem. Res. 2004, 43, 4732- 4739. Wang, William; Li, Songgeng; Ramkumar, Shwetha; Wong, Danny; Iyer, Mahesh; Fan, L-S; Statnick, Robert M. Demonstration of Multi-Pollutant Capture Including CO2 and SO2 from Coal Combustion. Proceedings-7th Carbon Capture & Sequestration Conference, 2008. Wang, William; Li, Songgeng; Ramkumar, Shwetha; Wong, Danny; Iyer, Mahesh; Fan, L-S; Statnick, Robert M. Results from 20 pound per hour CO2 Capture Facility. Proceedings- Pittsburgh Coal Conference, 2008. Li, Songgeng; Wang, William; Ramkumar; Shwetha; Wong, Danny; Iyer, Mahesh; Fan, L-S; Statnick, Robert M. Demonstration of Carbon Dioxide Capture from Coal-Fired Flue Gas Using Calcium-based Sorbents. Proceedings-AICHE Annual Meeting, 2008. Wang, William; Ramkumar, Shwetha; Li, Songgeng; Wong, Danny; Iyer, Mahesh; Sakadjian, Bartev; Statnick, Robert; Fan, L.-S. Sub-Pilot Demonstration of the Carbonation-Calcination Reaction (CCR) Process: High-Temperature CO2 and Sulfur Capture from Coal Fired Power Plants. Ind. Eng. Chem. Res. In Press. FIELDS OF STUDY Major Field: Chemical Engineering viii TABLE OF CONTENTS Abstract ............................................................................................................................... ii Dedication .........................................................................................................................