Old Dominion University ODU Digital Commons Chemistry & Biochemistry Theses & Dissertations Chemistry & Biochemistry Spring 2016 Low-Temperature Artificial Maturation Studies of Type II and Type III Kerogens: Implications for Biogenic Gas Production Albert Willy Nguena Kamga Old Dominion University, [email protected] Follow this and additional works at: https://digitalcommons.odu.edu/chemistry_etds Part of the Chemical Engineering Commons, Geochemistry Commons, and the Organic Chemistry Commons Recommended Citation Nguena Kamga, Albert W.. "Low-Temperature Artificial Maturation Studies of Type II and Type III Kerogens: Implications for Biogenic Gas Production" (2016). Doctor of Philosophy (PhD), Dissertation, Chemistry & Biochemistry, Old Dominion University, DOI: 10.25777/5sj5-4y45 https://digitalcommons.odu.edu/chemistry_etds/8 This Dissertation is brought to you for free and open access by the Chemistry & Biochemistry at ODU Digital Commons. It has been accepted for inclusion in Chemistry & Biochemistry Theses & Dissertations by an authorized administrator of ODU Digital Commons. For more information, please contact [email protected]. LOW-TEMPERATURE ARTIFICIAL MATURATION STUDIES OF TYPE II AND TYPE III KEROGENS: IMPLICATIONS FOR BIOGENIC GAS PRODUCTION by Albert Willy Nguena Kamga B.S. May 2010, Old Dominion University A Dissertation Submitted to the Faculty of Old Dominion University in Partial Fulfillment of the Requirements for the Degree of DOCTOR OF PHILOSOPHY CHEMISTRY OLD DOMINION UNIVERSITY May 2016 Approved by: Patrick G. Hatcher (Director) Francoise Behar (Co-Director) Francois Baudin (Co-Director) James W. Lee (Member) Sandeep Kumar (Member) John Cooper (Member) ABSTRACT LOW-TEMPERATURE ARTIFICIAL MATURATION STUDIES OF TYPE II AND TYPE III KEROGENS: IMPLICATIONS FOR BIOGENIC GAS FORMATION Albert Willy Nguena Kamga Old Dominion University, 2015 Director: Dr. Patrick G. Hatcher Co-Directors: Dr. Francoise Behar Dr. Francois Baudin Ancient organic matter (OM) in shales and coals, known mainly as Type II and Type III OM are known to produce both biogenic, thermogenic gas and oil. In this dissertation, mild artificial maturation, via closed system pyrolysis, is employed to determine the thermal reactivity of Type II and Type III OM beyond diagenesis. We select three Type II kerogens: i) Type II kerogen isolated from recent cores (3.3 Ma, Ro = 0.28) recovered from an upwelling basin in Namibia, Africa referred to as ODP Sediment, ii) Type II-S isolated from sediments (150 Ma, Ro = 0.38) recovered from an outcrop near the Volga River, Russia referred to as Bazhenov Source Rock (S.R.), iii) Type II kerogen isolated from sediments (185 Ma, Ro = 0.62) recovered from an outcrop in the Paris Basin, France referred to as Toarcian S.R.. Furthermore, we select four Type III kerogens in which three from deep coalbed layers in Shimokita, Japan and the fourth from the Calvert Bluff Formation, Texas, USA. Our results show that the structural identity is significantly altered because a major portion of oxygenated compounds such as Alkyl – O, esters and carboxylic acids is lost based on solid state 13C Nuclear Magnetic Resonance of the solid residues. Gaseous and liquid recoveries quantitatively show that CO2 and asphaltenes are the primary thermal products. For Type II kerogens, CO2 was co-generated with asphaltenes while for Type III kerogen generated less thermal products with CO2 slightly later than asphaltenes. For Type III kerogens, the three coalbeds seem to generate thermal products with respect to their maturity levels. Using optimized activation energies set between 30 and 48 kcal/mole, bulk kinetics studies reveal that the onset of thermal generation of CO2 and asphaltenes from Type II and Type III kerogens initiates at 10oC with maximum product yields reached below 70oC. The molecular characterization of asphaltenes reveals the dominance of long chain fatty acids and diacids with similar bulk kinetic parameters as the global degradation of kerogens. These long chain fatty acids and diacids possess the highest conversion rate into biogenic methane. iv © 2016, by Albert Willy Nguena Kamga, All Rights Reserved. v This dissertation is dedicated to pertinacity, hard work and motivation. vi ACKNOWLEDGMENTS There are more than a few people that I would like to thank for their unmeasurable support and tremendous encouragement throughout my entire college experience at Old Dominion University. First of all, I would like to recognize my advisor Dr. Patrick G. Hatcher for his guidance, motivation, harshness when necessary and fatherly advice throughout my dissertation experience which allowed me to reach my utmost goal so far: to become a Doctoral scholar with my Ph.D. in Chemistry. He transformed my scientific writing to its best shape ever and he also taught me concise critical thinking and how important it is to always think about the next step and next discovery. I would also like to thank Dr. Francoise Behar, my co-advisor, who did so much for me since I met and started working with her in 2011. She has tremendously influenced my Ph.D. research and without her I probably wouldn’t have had research funding especially from a top-tier petroleum company, worldwide. She has taught me the importance of being rigorous, consistent, creative, fully engaged and disciplined in order to conserve my reliability at the top. And for that I am most grateful. I would also like to recognize Dr. Francois Baudin, my co-advisor, who guided me along my last three years of doctoral research and motivated me to go above and beyond which I really appreciate. I also take the opportunity to thank the rest of my doctoral defense committee members, Dr. Lee, Dr. Cooper and Dr. Kumar, for valuable discussions, tremendous insights about my research topic and its application in the real world. It became so easy when working with an amazing Hatcher group. We support each other to the point of critically proof-reading each other’s manuscript. I am so happy to be a part of this vii family and would like to indicate the most influential members during my time at ODU: Dr. Aron Stubbins, Derek Waggoner, Dr. Blaine Hartman, Sarah Gurganus, Dr. Wassim Obeid, Dr. Amanda Willoughby, Dr. Rachel Sleighter, Dr. Andrew Wosniak, Nicole Didonato, Isiah Ruhl, Susan Hatcher, Stephanie McElhenie, Seyyedhadi Khatami and Jared Callan. They all have made my experience at ODU more exciting, more productive and most definitely more positive. I would like to thank my entire family for their infinite support especially the Kamga family, the Wambo family, the Fomenkeu family and the Pô Meche Family especially the Talom family. I also want to thank my friends outside of my doctoral research for being social support, soccer teammates and fishing buddies. I thank in particular David Nminibapiel, Keba Sane, Rodwyn Tucker, Marc St-Cyr, Michael Dondre, Ewa Kenneth, Idriss Njike, Jovanie Tankeu, Manuel Mukuri, Freddy Kameni and the entire “Avengers F.C.” and “Mollywhoppers” squads. I am especially grateful for the reassurance my parents, Rose and Pierre-Joel Kamga, and my siblings, Aurelie, Siegfried and Stephanie Kamga, have provided me throughout all of my academic journey because they are the main reasons that I had the strength to pursue my academic goals. Lastly, I would like to acknowledge Lynzee Horton for her endless support and dealing with my stressful days and happy days. She has been there every day for me since day one and I will always be grateful. viii TABLE OF CONTENTS Page LIST OF TABLES .............................................................................................................x LIST OF FIGURES .........................................................................................................xiii Chapter I. INTRODUCTION ...............................................................................................1 II. QUANTITATIVE ANALYSIS OF LONG CHAIN FATTY ACIDS PRESENT IN A TYPE I KEROGEN USING ESI-FT-ICR-MS: COMPARED WITH BF3/MeOH METHYLATION/GC-FID ..............................................................11 1. INTRODUCTION .........................................................................................11 2. SAMPLE DESCRIPTION .............................................................................15 3. EXPERIMENTAL .........................................................................................15 4. RESULTS AND DISCUSSION ....................................................................20 5. CONCLUSIONS............................................................................................37 III. LOW-TEMPERATURE CRACKING OF TYPE II KEROGEN: KINETIC STUDY OF THE EARLY CO-GENERATION OF ASPHALTENES AND CO2 AS POTENTIAL SUBSTRATES FOR METHANOGENESIS .........................39 1. INTRODUCTION .........................................................................................39 2. METHODS ....................................................................................................42 3. SAMPLE DESCRIPTION .............................................................................47 4. RESULTS ......................................................................................................49 5. DISCUSSION ................................................................................................72 6. CONCLUSIONS............................................................................................90 IV. ASPHALTENES GENERATED FROM LOW-TEMPERATURE CRACKING OF TYPE II KEROGEN: MOLECULAR