INTEGRATING BIOPROCESSES INTO INDUSTRIAL COMPLEXES FOR SUSTAINABLE DEVELOPMENT A Dissertation Submitted to the Graduate Faculty of the Louisiana State University and Agricultural and Mechanical College in partial fulfillment of the requirements for the degree of Doctor of Philosophy in The Department of Chemical Engineering by Debalina Sengupta B.S., Jadavpur University (India), 2003 December, 2010 DEDICATION This work is dedicated to Objectivism ii ACKNOWLEDGEMENTS I would like to express my deepest gratitude to Dr. Ralph Pike for introducing me to "Sustainability", guiding me at every step and helping me in developing the intricate details of the concepts that formed this work. He is an excellent research supervisor, the best teacher, and above all, a compassionate and caring human being. From him, I have learnt that there is no short-cut path to achieving an “objective function”. I would like to thank my committee members, Dr. Carl F. Knopf, Dr. Jose Romagnoli, Dr. K.T. Valsaraj and Dr. Jonathan Dowling for helping us in evaluating the work with their valuable inputs. Tom Hertwig was an excellent person to work with as an industrial advisor. I remember the August afternoon in Louisiana's "Lower Mississippi River Corridor" when Tom showed me around the "Base Case of Plants". It was indeed a thrilling experience to put on the hard hat and boots and move around the Mosaic facility for acids and fertilizers production complex. I would like to thank all the members of the Total Cost Assessment Users' Group at the AIChE, and especially Lise Laurin for helping me understand the Total Cost Assessment Methodology. It is a great experience working with the group and we hope to continue contributing towards a sustainable future. While I was working towards a sustainable industrial chemical production complex, the Cain Department of Chemical Engineering helped me to sustain financially. I consider myself privileged to have taken a course with Dr. Kerry Dooley at the department. If I become a teacher in the future, I would like to inherit his enthusiasm in teaching and his vision in evaluating a student. My parents, Indranil and Ajanta Sengupta, have given me the “degrees of freedom” throughout my life. Their blessings and wishes and love for me have been the driving force for achieving my dreams. The physical distance with them has never been a “constraint” in “optimizing” my personal life with my educational pursuits. My in-laws, Ranjit and Kajal Mukherjee, have been supportive, and I thank Mouri, my sister-in-law, for taking care of all the details back home, so that we could pursue our dreams. I remember the day when I first met Rajib Mukherjee, my husband. He said that he wanted to dedicate his life in the pursuit of knowledge, and he wanted me to be a part of that journey. So, off we were to a foreign land, and as luck would have it, we were able to complete our studies at Louisiana State University. Thank you for showing me the way. Nothing seems complete without friends. I would like to thank the Das family for giving us a home away from home and never let us miss family life. The Sarkar family has never given us a chance to miss the festivals celebrated back home. The friends at the department and others have given us the comfort and understanding, which has made the LSU and Baton Rouge experience the most cherished memories in our life. iii TABLE OF CONTENTS DEDICATION ...............................................................................................................................ii ACKNOWLEDGEMENTS ...............................................................................................................iii LIST OF TABLES .............................................................................................................................vii LIST OF FIGURES ...........................................................................................................................xvii ABSTRACT ...............................................................................................................................xxvi CHAPTER 1 INTRODUCTION AND BACKGROUND ..........................................................1 1.1 Introduction ..................................................................................................................................1 1.2 A Research Vision .......................................................................................................................1 1.3 New Frontiers ...............................................................................................................................2 1.4 The Chemical Industry in the Lower Mississippi River Corridor ...............................................3 1.5 Criteria for the Optimal Configuration of Plants .........................................................................5 1.6 Optimization of Chemical Complex ............................................................................................7 1.7 Contributions of This Research ...................................................................................................8 1.8 Organization of Chapters .............................................................................................................9 1.9 Summary ......................................................................................................................................14 CHAPTER 2 LITERATURE REVIEW - BIOMASS AS FEEDSTOCK ...................................15 2.1 Introduction ..................................................................................................................................15 2.2 Biomass Formation ......................................................................................................................18 2.3 Biomass Classification and Composition ....................................................................................20 2.4 Biomass Conversion Technologies ..............................................................................................25 2.5 Biomass Feedstock Availability ..................................................................................................37 2.6 Summary ......................................................................................................................................53 CHAPTER 3 LITERATURE REVIEW – CHEMICALS FROM BIOMASS ............................55 3.1 Introduction ..................................................................................................................................55 3.2 Chemicals from Non-Renewable Resources ...............................................................................56 3.3 Chemicals from Biomass as Feedstock ........................................................................................57 3.4 Biomass Conversion Products (Chemicals) .................................................................................59 3.5 Biopolymers and Biomaterials .....................................................................................................87 3.6 Natural Oil Based Polymers and Chemicals ................................................................................89 3.7 Summary ......................................................................................................................................91 CHAPTER 4 SIMULATION FOR BIOPROCESSES ................................................................93 4.1 Introduction ..................................................................................................................................93 4.2 Ethanol Production from Corn Stover Fermentation ...................................................................96 4.3 Ethylene Production from Dehydration of Ethanol .....................................................................108 4.4 Fatty Acid Methyl Ester and Glycerol from Transesterification of Soybean Oil ........................112 4.5 Propylene Glycol Production from Hydrogenolysis of Glycerol ................................................124 iv 4.6 Acetic Acid Production from Corn Stover Anaerobic Digestion ................................................129 4.7 Ethanol Production from Corn Dry Grind Fermentation .............................................................141 4.8 Summary ......................................................................................................................................143 CHAPTER 5 BIOPROCESSES PLANT MODEL FORMULATION .......................................145 5.1 Introduction ..................................................................................................................................145 5.2 Ethanol Production from Corn Stover Fermentation ...................................................................147 5.3 Ethanol Production from Corn Dry Grind Fermentation .............................................................167 5.4 Ethylene Production from Dehydration of Ethanol .....................................................................179 5.5 Acetic Acid Production from Corn Stover Anaerobic Digestion ................................................182 5.6 Fatty Acid Methyl Ester and Glycerol from Transesterification of Natural Oil ..........................195 5.7 Propylene Glycol Production from Hydrogenolysis of Glycerol ................................................202 5.8 Algae Oil Production ...................................................................................................................207