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Co2-Selective Membrane for Fuel Cell Applications

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Co2-Selective Membrane for Fuel Cell Applications University of Kentucky UKnowledge University of Kentucky Doctoral Dissertations Graduate School 2006 CO2-SELECTIVE MEMBRANE FOR FUEL CELL APPLICATIONS Louei Abdel Raouf El-Azzami University of Kentucky, [email protected] Right click to open a feedback form in a new tab to let us know how this document benefits ou.y Recommended Citation El-Azzami, Louei Abdel Raouf, "CO2-SELECTIVE MEMBRANE FOR FUEL CELL APPLICATIONS" (2006). University of Kentucky Doctoral Dissertations. 306. https://uknowledge.uky.edu/gradschool_diss/306 This Dissertation is brought to you for free and open access by the Graduate School at UKnowledge. It has been accepted for inclusion in University of Kentucky Doctoral Dissertations by an authorized administrator of UKnowledge. For more information, please contact [email protected]. ABSTRACT OF DISSERTATION Louei Abdel Raouf El-Azzami The Graduate School University of Kentucky 2006 CO2-SELECTIVE MEMBRANE FOR FUEL CELL APPLICATIONS ABSTRACT OF DISSERTATION A dissertation submitted in partial fulfillment of the requirements for the degree of the Doctor of Philosophy in the College of Engineering at the University of Kentucky By Louei Abdel Raouf El-Azzami Lexington, Kentucky Director: Dr. Eric A. Grulke. Professor of Chemical & Materials Engineering Lexington, Kentucky 2006 Copyright © Louei Abdel Raouf El-Azzami ABSTRACT OF DISSERTATION CO2-SELECTIVE MEMBRANE FOR FUEL CELL APPLICATIONS We have developed CO2-selective membranes to purified hydrogen and nitrogen for fuel cell processes. Hydrogen purification impacts other industries such as ammonia production and flue gas purification at reduced costs. Dense chitosan membranes were used for the first time to separate CO2 from a o mixture of 10% CO2, 10% H2, and 80% N2 at temperatures of 20 – 150 C and feed pressures of 1.5 atm – 5 atm. At 1.5 atm and 20 – 150oC, dry chitosan membranes achieved CO2 permeabilities, CO2/N2 and CO2/H2 separation factors of 0.383 – 24.3 barrers, 10.7 – 3.40, and 4.54 – 1.50, respectively. The dry chitosan acted as an ordinary solution-diffusion membrane: permeability increased with temperature but selectivity decreased. The CO2/H2 and CO2/N2 separation factors at all temperatures enhanced CO2 removal, making this membrane a candidate for fuel cell processes. The dual mode transport model fitted the transport data well. To achieve higher CO2 transport properties, chitosan was swollen with water. Water mediated the reaction of chitosan’s amino groups with CO2. Humidifing the feed and sweep gases increased the membrane’s performance. At 1.5 atm and 20 – 110 – o 150 C, CO2 permeabilities, CO2/N2 and CO2/H2 separation factors were 213 – 483 – 399 barrers, 69.4 – 250 – 194, and 18.9 – 43.4 – 29, respectively. The presence of free water and bound water facilitated the transport of CO2. Increasing feed pressure removed the o maxima in permeability and selectivities at 110 C, but led to reduced CO2 permeabilities, CO2/N2 separation factors, and CO2/H2 separation factors to 156 – 286 barrers, 44.2 – 131, and 12.0 – 16.7, respectively. To acquire higher CO2 transport properties, arginine-sodium salts were incorporated in chitosan membranes as additional sites for facilitated transport. The salt’s o percolation threshold was 40 wt %. At 1.5 atm and 20 – 110 – 150 C, CO2 permeabilities, CO2/N2 and CO2/H2 separation factors were 403 – 1498 – 1284 barrers, 122 – 852 – 516, and 31.9 – 144 – 75.5, respectively. Increasing feed pressure to 5 atm resulted in declining CO2 permeabilities, CO2/N2 and CO2/H2 separation factors to 118 – 1078 barrers, 21.6 – 352, and 5.67 – 47.9, respectively. Chitosan was characterized in terms of morphology, solution properties, thermal properties, crystallinity, and degree of deacetylation. KEYWORDS: Chitosan; CO2-Selective Membrane; Facilitated Transport, Incorporation of Arginine; Impact on Fuel Cells Louei Abdel Raouf El-Azzami 7/31/06 CO2-SELECTIVE MEMBRANE FOR FUEL CELL APPLICATIONS By Louei Abdel Raouf El-Azzami Eric A. Grulke Director of Dissertation Barbara Knutson Director of Graduate Studies 7/31/06 RULES FOR THE USE OF DISSERTATIONS Unpublished dissertations submitted for the Doctor’s degree and deposited in the University of Kentucky library are as a rule open for inspection, but are to be used only with due regard to the rights of the authors. Bibliographical references may be noted, but quotations or summaries of parts may be published only with the permission of the author, and with the usual scholarly acknowledgements. Extensive copying or publication of the thesis in whole or in part also requires the consent of the Dean of Graduate School of the University of Kentucky. A library that borrows this thesis for use by its patrons is expected to secure the signature of each user. Name Date DISSERTATION Louei Abdel Raouf El-Azzami The Graduate School University of Kentucky 2006 CO2 - SELECTIVE MEMBRANE FOR FUEL CELL APPLICATIONS DISSERTATION A Dissertation submitted in partial fulfillment of the requirements for the degree of the Doctor of Philosophy in the College of Engineering at the University of Kentucky By Louei Abdel Raouf El-Azzami Lexington, Kentucky Director: Dr. E. A. Grulke, Professor of Chemical and Materials Engineering Lexington, Kentucky 2006 Copyright © Louei Abdel Raouf El-Azzami DEDICATION I dedicate this dissertation to my mother, Naema Al Shihabi, whose memories will always stay in my heart. I hope that she resides in heavens and watching from above with pride of what her son has become. Also, I dedicate this dissertation to my father, Abdel Raouf El-Azzami, whose intelligence and dedication provided me with the opportunity to reach the highest education possible. Last but not least, I dedicate this dissertation to my beloved wife, Heather Harrison, who played a critical factor in my success. ACKNOWLEDGEMENTS I would like to acknowledge my advisor, Dr. Eric A. Grulke, for his support and guidance through good and bad times, and to tell him that our relationship has been unique in every sense. One of the most important people that contributed in a major way in the success of this dissertation is Monica Mehanna that filled my academic years with hope and persistence. What a great person! Appreciation goes to Dr. Barbara Knutson in ensuring that I get the best out of this dissertation. I offer my gratitude to Dr. Dibakar Bhattacharyya for his effort and generosity in sharing his knowledge in the membrane area. Particular gratitude delivered to Dr. Bert Lynn for his help in the chemistry area of this research. Though Dr. Paul Bummer is the outside examiner, he still provided excellent advice that aided me in completing the task in hand, thank you sir. I would also thank the staff members of the Department of Chemical Engineering, and, in particular, Bruce Cole, for their continuous support and help. I give my special thanks to Jerry Vice who was always there when his technical expertise was needed. In addition, I am grateful for the support offered by my friend and colleague, Yit-Hong Tee. i Table of Contents ACKNOWLEDGEMENTS................................................................................................. i List of Tables ...................................................................................................................... v List of Figures.................................................................................................................... vi List of Files ........................................................................................................................ xi Chapter One: Introduction & Research Objectives ............................................................ 1 Chapter Two: Characterization of High Molecular Weight Chitosan Films ...................... 4 Introduction..................................................................................................................... 4 Experimental Methods.................................................................................................... 7 Materials ..................................................................................................................... 7 Synthesis of Chitosan Film ......................................................................................... 7 Thickness of Membrane.............................................................................................. 7 Morphology................................................................................................................. 8 Solubility..................................................................................................................... 8 Density, Swelling Index, and Water Volume Fraction............................................... 8 Moisture Content and Ash Content............................................................................. 9 Bound Water ............................................................................................................... 9 Carbon, Hydrogen, Nitrogen, and Oxygen Content ................................................. 10 Thermal properties and solvents release................................................................... 10 Crystallinity............................................................................................................... 11 Degree of Deacetylation ........................................................................................... 12 Fractional Free Volume ...........................................................................................
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