An Experimental Study on the Formation
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Louisiana State University LSU Digital Commons LSU Doctoral Dissertations Graduate School 2008 An Experimental Study on the Formation of Polycyclic Aromatic Hydrocarbons during the Pyrolysis and Oxidation of Catechol[ortho- Dihydroxybenzene]-A Model Compound Representative of Structural Units in Coal, Wood, and Biomass Shiju Thomas Louisiana State University and Agricultural and Mechanical College, [email protected] Follow this and additional works at: https://digitalcommons.lsu.edu/gradschool_dissertations Part of the Chemical Engineering Commons Recommended Citation Thomas, Shiju, "An Experimental Study on the Formation of Polycyclic Aromatic Hydrocarbons during the Pyrolysis and Oxidation of Catechol[ortho-Dihydroxybenzene]-A Model Compound Representative of Structural Units in Coal, Wood, and Biomass" (2008). LSU Doctoral Dissertations. 2543. https://digitalcommons.lsu.edu/gradschool_dissertations/2543 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 Doctoral Dissertations by an authorized graduate school editor of LSU Digital Commons. For more information, please [email protected]. AN EXPERIMENTAL STUDY ON THE FORMATION OF POLYCYCLIC AROMATIC HYDROCARBONS DURING THE PYROLYSIS AND OXIDATION OF CATECHOL [ORTHO-DIHYDROXYBENZENE]⎯A MODEL COMPOUND REPRESENTATIVE OF STRUCTURAL UNITS IN COAL, WOOD, AND BIOMASS 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 Shiju Thomas B.S., University of Calicut, India, 1998 May, 2008 Dedication To my parents… ii Acknowledgements First and foremost, I would like to thank my graduate advisor, Professor Mary J. Wornat. Without her encouragement, guidance, and scientific inputs, this research would not have been possible. I am most indebted to her for the freedom she has given me in my research. I would also like to thank the remaining members of my committee, Professor K.T. Valsaraj, Professor J.J. Spivey, Professor K. E. Thompson, Professor J.E. Henry, and Professor D.A. Spivak for their time and valuable inputs. I would like to thank the following for reference standards and/or UV spectra of PAH: Dr. Arthur Lafleur and Ms. Elaine Plummer, of Massachusetts Institute of Technology; Professor Lawrence Scott and Dr. Atena Necula, of Boston College; Prof. Maximilian Zander, of Rütgerswerke; Dr. John Fetzer, of FETZPAHS; Dr. Albrecht Seidel, of Biochemisches Institut für Umweltcarcinogene; Dr. Dianne Poster, of the National Institute of Standards and Technology; Professor William Alworth, of Tulane University; and Dr. Mark McLaughlin and Mr. Ted Gauthier, of Louisiana State University. I would also like to gratefully acknowledge Philip Morris USA for support of this research. I would like to mention Professor K.V. Narayanan for his guidance and support during my undergraduate years. My supervisors and colleagues at Unilever Research India, especially, Dr. Vijay Naik, Dr. Suresh Nadakatti, and Dr. Hari Koduvely, are gratefully acknowledged for their scientific inputs, support, and encouragement. I would like to extend my appreciation to the Chemical Engineering Department for giving me an opportunity to be a part of the graduate student community at LSU. I would like to thank the Chemical Engineering faculty and support staff for their help and support. I would also iii like to thank the Graduate School at LSU for the Economic Development Assistantship and for the Coates Travel awards. I would like to extend my gratitude to Dr. Elmer B. Ledesma for getting me started on my research and for his continuous support throughout my research. I thank my colleagues Jorge, Jerome, Michelle, Sean, Jennifer, Joy, Xia, Franz, Nimesh, and Davis, for helpful technical contributions as well as for making work in the lab more enjoyable. I would also like to acknowledge my friends and fellow graduate students both in and out of the department, and the big Indian community of Baton Rouge for making life away from home enjoyable. This research would not have been possible without the prayers and support of my family, near and afar⎯my parents who have been a constant source of inspiration; my wife and best friend Shamly, for her patience and moral support throughout the last few hectic years; my brother and sister for their prayers and support. I would also like to acknowledge my friend Anish Andheria, who has been a great influence on my life. iv Table of Contents Dedication………………………………………………………………………………………… ii Acknowledgements……………………………………………………………………………….iii List of Tables...……………………………………………………………………………………ix List of Figures……………………………………………………………………………..............x Abstract..……………………………………………………………………………………….xviii Chapter I. Introduction…………………………………………………………………………. 1 1.1. Background and Motivation ...............................................................................................1 1.2. Structure of the Dissertation ...............................................................................................9 Chapter II. Experimental Equipment and Procedures............................................................13 2.1. Reactor System .................................................................................................................13 2.1.1. Fuel Vaporizer ....................................................................................................13 2.1.2. Reactor ................................................................................................................14 2.1.3. Product Collection ..............................................................................................15 2.2. Sample Collection Procedure ...........................................................................................16 2.2.1. Condensed-Phase Products .................................................................................16 2.2.2. Gas-Phase Products.............................................................................................17 2.3. Analytical Procedures for the Identification and Quantification of Products...................17 2.3.1. C1-C6 Hydrocarbon Products ..............................................................................18 2.3.2. Light (< 3 rings) Aromatic Products...................................................................19 2.3.3. PAH Products......................................................................................................19 Chapter III. PAH Product Identification ..................................................................................23 3.1. Introduction.......................................................................................................................23 3.2. Experimental Equipment and Procedures.........................................................................28 3.2.1. Reactor System ...................................................................................................28 3.2.2. Product Analysis .................................................................................................28 3.3. Results and Discussion .....................................................................................................30 3.3.1. Identification of C24H14 PAH..............................................................................32 3.3.1.1. Perylene Benzologues...................................................................................34 3.3.1.2. Fluoranthene Benzologues............................................................................36 3.3.1.3. Pyrene Benzologues......................................................................................39 3.3.2. Identification of Methylene-Bridged PAH .........................................................43 3.3.2.1. UV Spectral Matches for Methylene-Bridged PAH .....................................45 3.3.2.2. Effects of Methylene-Bridging on the UV Spectra of PAH .........................47 3.3.2.3. Identification of C25H14 PAH: Methylene-Bridged Naphtho[2,1-a]pyrene..54 3.3.2.4. Identification of C25H14 PAH: Methylene-Bridged Naphtho[2,3-a]pyrene..60 3.3.3. Identification of Large PAH ...............................................................................63 3.3.4. Other PAH ..........................................................................................................70 v 3.3.5. Comparison with Coal Products .........................................................................71 3.4. Summary and Conclusions ...............................................................................................72 Chapter IV. Effects of Oxygen Addition: Yields of the C1-C8 Thermal Decomposition Products……… ............................................................................................................................74 4.1. Introduction.......................................................................................................................74 4.2. Experimental Equipment and Procedures.........................................................................77 4.2.1. Reactor System ...................................................................................................77 4.2.2. Product Analysis .................................................................................................78 4.3. Results and Discussions....................................................................................................80