Louisiana State University LSU Digital Commons LSU Historical Dissertations and Theses Graduate School 1982 The Reaction Between Calcium Oxide and Nitrogen Dioxide in the Presence of Oxygen: a Variable Solid Property Grain Model. Kenneth Charles Reibert Louisiana State University and Agricultural & Mechanical College Follow this and additional works at: https://digitalcommons.lsu.edu/gradschool_disstheses Recommended Citation Reibert, Kenneth Charles, "The Reaction Between Calcium Oxide and Nitrogen Dioxide in the Presence of Oxygen: a Variable Solid Property Grain Model." (1982). LSU Historical Dissertations and Theses. 3738. https://digitalcommons.lsu.edu/gradschool_disstheses/3738 This Dissertation is brought to you for free and open access by the Graduate School at LSU Digital Commons. It has been accepted for inclusion in LSU Historical Dissertations and Theses by an authorized administrator of LSU Digital Commons. For more information, please contact [email protected]. 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In alt cases we have filmed the best available copy. University' M icrofilm s International 300 N Z EEB RD , ANN ARBOR, Ml 48106 8216867 Retbert, Kenneth Charles T H E REACTION BETWEEN CALCIUM OXIDE AND NITROGEN DIOXIDE IN THE PRESENCE OF OXYGEN: A VARIABLE SOLID PROPERTY GRAIN MODEL The LouisianaState University and Agricultural and MechanicalCoL PH.D. 1982 University Microfilms International 300 N. Zeeb Rend. Ann Arbor, Ml 48106 PLEASE NOTE: In all cases this material has been filmed In the best possible way from the available copy. Problems encountered with this document have been identified here with a check mark V 1. Glossy photographs or pages_____ 2. Colored illustrations, paper or print_____ 3. Photographs with dark background ^ 4. Illustrations are poor copy _____ 5. Pages with black marks, not original copy _____ 6. Print shows through as there is text on both sides of page _____ 7. Indistinct, broken or small print on several pages »— 8. 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Other__________________________________________________________________ University Microfilms International THE REACTION BETWEEN CALCIUM OXIDE AND NITROGEN DIOXIDE IN THE PRESENCE OF OXYGEN: A VARIABLE SOLID PROPERTY GRAIN MODEL 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 Kenneth Charles Reibert B.S., Louisiana State University, 1974 M.S., Louisiana State University, 1976 May, 1982 Dedicated to my father Kenneth Howard Reibert whose total commitment to my education enabled me to complete this work. ii ACKNOWLEDGMENTS Upon completion of this study, I welcome the opportunity to acknowledge with sincere appreciation the people who have made my stay in graduate school an enriching and enjoyable experience. I consider myself extremely fortunate to have had Dr. Douglas P. Harrison as my major professor. His encourage­ ment, technical guidance, suggestions, and helpful criticisms throughout this study are greatefully acknowl­ edged . No one has given more of herself to me than has my dear wife, Pamela. She deserves special recognition as she prepared the figures for this dissertation and typed the rough draft. More importantly, her patience and love have provided me with a limitless supply of moral support. Thanks are also due to Drs. E. McLaughlin, C.D. Callihan, J.B. Cordiner, and D.M. Wetzel of the Chemical Engineering Department, and to Dr. F.A. Iddings of the Nuclear Science Department for serving as members of the examining committee. Their helpful suggestions and guidance are appreciated. A word of appreciation to the many people who have aided me professionally and/or personally is a must. Special gratitude is extended to Miss Hazal LaCoste, Dr. David Caillet, Mr. Larry Veilleux, and Mr. H.L. Sparrow. Mr. Patil of the Chemistry Department provided the I. R. iii analysis. A hearty thank you is due Mr. Warren Abbott who answered many questions concerning the IBM operating system. I wish to thank the Chemical Engineering Department of LSU for their financial support during my graduate study. Also, the financial assistance of the Charles E. Coates Memorial Fund and the Plaquemines Parish Scholarship Committee is appreciated greatly. Thanks are due Jan Easley for her skillful typing of the final manuscript. Finally, I am deeply indebted to my parents for it was they who instilled in me the importance of an education from an early age. My sincerest appreciation is extended to them both for providing me with encouragement and numerous forms of assistance throughout my life to further my education. iv TABLE OF CONTENTS CHAPTER PAGE I. INTRODUCTION...................................1 The NOx Air Pollution Problem...........1 Current stationary Source Control Techniques.......................... 4 Reactions of NOx with CaO.................11 Objectives of Research ................. 16 Literature Cited ........................ 18 II. THERMODYNAMIC STUDY ........................... 21 Free Energy Minimization ............... 23 Procedure for Thermodynamic Study. 26 Gaseous Species Considered.......... 27 Condensed Species Considered. 28 Results of Thermodynamic Study ......... 29 Alkali Metal Oxides ............... 31 Alkaline Metal Oxides ............. 36 Summary of Results of the Thermodyanmic study .................47 Literature Cited ........................ 51 III. APPLICABLE NON-CATALYTIC GAS-SOLID REACTION MODELS...........................................55 Non-Catalytic Gas-Solid Reactions. 55 Conventional Models....................... 57 Unreacted Core Model.................60 Grain Model ......................... 64 Effect of Solid Properties ............. 70 Variable Solid Property Models ......... 73 v CHAPTER PAGE Model of Howard, Williams, and Ghazal........................73 Model of Gidaspow - Pore Closure M o d e l ........................ 76 Model of Hartman and Coughlin. 83 Model of Georgakis, Chang, and S z e k e l y ......................86 Model of Ramachandran and Smith - Single-Pore Model ........... 89 Reaction/Sintering Model of Ramachandran and Smith. 98 Model of Ranade and Harrison . 103 Literature Cited ............................ 112 IV. EXPERIMENTAL APPARATUS AND PROCEDURE .... 116 Thermodynamic Equilibrium of Reactant Gas Mixture........................116 Major Experimental Apparatus - The TGA. 119 M a t e r i a l s .............................. 124 P r o c e d u r e .............................. 127 Auxiliary Equipment ................... 131 Experimental Difficulties.............. 133 Literature Cited........................137 V. EXPERIMENTAL RESULTS ........................ 138 Experimental Results for CaO Pellets. 141 Reaction Reproducibility ......... 146 Effect of Temperature............. 149 Effect of Reactant Gas Concentration ............... 160 Effect of Oxygen Concentration . 164 Effect of Total Gas Flowrate . 168 vi CHAPTER PAGE Effect, of Pellet Properties. 168 Reaction Parameter Analysis. 175 Post Reaction Analyses ........... 188 CaO Powder D a t a ...................... 192 Literature Cited...................... 203 VI. COMPARISON OF EXPERIMENTAL DATA WITH A VARIABLE PROPERTY