Study of Decarbonization Reaction of Sodium Carbonate by Sodium Borates

Western Michigan University ScholarWorks at WMU Dissertations Graduate College 4-2006 Study of Decarbonization Reaction of Sodium Carbonate by Sodium Borates Zaki Yusuf Western Michigan University Follow this and additional works at: https://scholarworks.wmich.edu/dissertations Part of the Engineering Commons Recommended Citation Yusuf, Zaki, "Study of Decarbonization Reaction of Sodium Carbonate by Sodium Borates" (2006). Dissertations. 1007. https://scholarworks.wmich.edu/dissertations/1007 This Dissertation-Open Access is brought to you for free and open access by the Graduate College at ScholarWorks at WMU. It has been accepted for inclusion in Dissertations by an authorized administrator of ScholarWorks at WMU. For more information, please contact [email protected]. STUDY OF DECARBONIZATION REACTION OF SODIUM CARBONATE BY SODIUM BORATES by Zaki Yusuf A Dissertation Submitted to the Faculty of The Graduate College in partial fulfillment of the requirements for the Degree of Doctor of Philosophy Department of Paper Engineering, Chemical Engineering and Imaging Science Advisor: Dr. John H. Cameron Western Michigan University Kalamazoo, Michigan April 2006 Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. STUDY OF DECARBONIZATION REACTION OF SODIUM CARBONATE BY SODIUM BORATES Zaki Yusuf, Ph.D. Western Michigan University, 2006 Today, the chemical process industries are facing many challenges in the wake of skyrocketing energy price. Paper industry as a whole is also not only looking into improving the process efficiency of its chemical recovery process but also is exploring to meet these challenges with gasification based energy/chemical recovery process. Borate based autocausticizing technology appears promising, provided it could be effectively integrated into both types of chemical recovery processes based on the principles of chemistry and chemical engineering. My research was focused on the decarbonization reactions of sodium carbonate by sodium metaborate (NaB 0 2 ) and sodium diborate (Na 4 B2 0 5 ) and drew a parallel between organo-borate complexes and sodium metaborate occurring in the recovery boilers. The primary objectives of this study is to provide information on the stoichiometry and the effect of the rate controlling parameters on the decarbonization reaction between sodium borates and sodium carbonate both above and below the melting points of the reactants. Another objective of the study was to verily the melting/freezing Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. point of trisodium borate (Na 3 BC>3 ), which is the reaction product of the decarbonization reactions. The final objective of the study was to critically examine the stoichiometry of the causticization reaction of Na 3 BC>3 in the aqueous phase since its reaction behavior would provide clue for its viability in various pulping processes. Efforts were also undertaken to obtain the phenomenological rate parameters from the reaction data. The heat of reaction of metaborate-based decarbonization was also estimated at various temperatures. A major finding of the study is that reaction occurs below the melting points of the reactants. However, the reactions are rapid above the pooled meting point of the system. The decarbonization reactions are reversible in nature and carbon dioxide removal is necessary for a high-degree of conversion. Trisodium borate shows incongruent melting/freezing point characteristics. The causticization reaction of Na 3 BC>3 is reversible in nature. Finally, it is recommended that a superheated steam line (with substantial degree of superheat) should be integrated inside the molten bed to periodically sweep out the CO 2 released from the decarbonization reaction to attain quick, efficient and complete conversion of the decarbonization reactions inside the smelt bed or gasification bed. Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. UMI Number: 3209228 Copyright 2006 by Yusuf, Zaki All rights reserved. INFORMATION TO USERS The quality of this reproduction is dependent upon the quality of the copy submitted. Broken or indistinct print, colored or poor quality illustrations and photographs, print bleed-through, substandard margins, and improper alignment can adversely affect reproduction. In the unlikely event that the author did not send a complete manuscript and there are missing pages, these will be noted. Also, if unauthorized copyright material had to be removed, a note will indicate the deletion. ® UMI UMI Microform 3209228 Copyright 2006 by ProQuest Information and Learning Company. All rights reserved. This microform edition is protected against unauthorized copying under Title 17, United States Code. ProQuest Information and Learning Company 300 North Zeeb Road P.O. Box 1346 Ann Arbor, Ml 48106-1346 Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. © 2006 Zaki Yusuf Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. ACKNOWLEDGMENTS I would like to commence by acknowledging Dr. Cameron’s early publication on borate based chemical recovery which inspired me to pursue this experimental research and led to the culmination of the work contained in this dissertation. I would also like to express my sincere gratitude for Dr. John Cameron for his extreme patience and thoughtful guidance throughout the course of this work. My appreciation will continue to grow for him because this work has opened up new vistas for my upcoming research endeavors. Secondly, I would like to thank everybody beginning with my committee members Dr. Peter Parker and Dr. John B. Miller for their support and help during this work with their thoughts, wisdom and valuable time. Dr. Miller was incredibly generous to provide me with packages like Cerisus 2 and CAChe and helped me with DFT calculation. I would also like to thank the department chair, Dr. Said Abu Bakr for his continuous support during the dissertation writing process. I would also like to express my deep appreciation for Dr. Paul D. Fleming, III for inspiring me to undertake molecular modeling (ab intio and semi-empirical) based thermodynamic property estimation. I would like to thank him for initiating interesting discussions on chemical reaction rate theories from molecular level which helped me understand chemical dynamics more intuitively. ii Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. Acknowledgments — Continued I would also like to thank Ms. Barbara Vilenski (Administrative Assistant) for her patience, untiring and silent support and help on various aspects of my dissertation writing process. I also extend my deepest appreciation for Mr. Matthew Stoops for his help on fixing the furnace and my experimental setup. Mr. Richard Reames, the director of Paper Pilot Plant was always extremely gracious to me to use his instruments and supplies. My deepest appreciation also goes to Glen Hall from the engineering department for fabricating the cap of my reactor without which the experimentation would have been impossible. Mr. Abu Sayeed Mia, my old friend from Microsoft Corporation, was the invisible pillar of strength for me and provided me with softwares and all kinds of logistical support from the very beginning of the work. He always emerged from nowhere and was instrumental in sharing even the most difficult of personal problems and vanished immediately without waiting for appreciation. I would also like to thank Dr. Muhammad Razi for providing me with an excellent book on statistics to deal with the nonlinear regression analysis. My deepest appreciation goes to Mr. Tamim Quader, Manager, ASMO Manufacturing, my childhood friend for encouraging me to pursue graduate program at W.M.U. Messer’s Mohammad Shahjahan (Bulldog) and Hussam Alkhasawneh was sent as a blessing for me. 111 Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. Acknowledgments — Continued I would like to express my deepest gratitude for my parents, in-laws and my uncle Mr Ziauddin Yusuf, P.E. for their constant and silent encouragement. I would also like to pay tribute to my deceased uncle, Mr. Nizamuddin Yusuf for his impact in converting my dreams into reality. The main thrust for the work came mainly came from my only son Sulayman and his mother- Yasmin, the love and poem of my life. Zaki Yusuf IV Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. TABLE OF CONTENTS ACKNOWLDGEMENTS.............................................................................................. ii LIST OF TABLES.......................................................................................................... viii LIST OF FIGURES......................................................................................................... ix CHAPTER I. INTRODUCTION............................................................................................. 1 II. LITERATURE REVIEW................................................................................. 20 Boron-Oxygen Chemistry ....................................................................... 20 Structure and Properties of Various Borate Salts ...................... 23 Structure and Properties of Various Borate Ions ......................

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