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Investigation of the Potential for Algaenan to Produce Hydrocarbon Based Fuels from Algae by Hydrous Pyrolysis

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Investigation of the Potential for Algaenan to Produce Hydrocarbon Based Fuels from Algae by Hydrous Pyrolysis Old Dominion University ODU Digital Commons Chemistry & Biochemistry Theses & Dissertations Chemistry & Biochemistry Spring 2015 Investigation of the Potential for Algaenan to Produce Hydrocarbon Based Fuels From Algae by Hydrous Pyrolysis Wassim Adel Obeid Old Dominion University Follow this and additional works at: https://digitalcommons.odu.edu/chemistry_etds Part of the Bioresource and Agricultural Engineering Commons, Chemistry Commons, and the Geochemistry Commons Recommended Citation Obeid, Wassim A.. "Investigation of the Potential for Algaenan to Produce Hydrocarbon Based Fuels From Algae by Hydrous Pyrolysis" (2015). Doctor of Philosophy (PhD), Dissertation, Chemistry & Biochemistry, Old Dominion University, DOI: 10.25777/v08w-g828 https://digitalcommons.odu.edu/chemistry_etds/37 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]. INVESTIGATION OF THE POTENTIAL FOR ALGAENAN TO PRODUCE HYDROCARBON BASED FUELS FROM ALGAE BY HYDROUS PYROLYSIS by Wassim Adel Obeid B.S. Chemistry, June 2008, American University of Beirut, Lebanon 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 2015 Approvgd By: Patrick G. Hatcher (Director) Sandeep Kumar (Member) Thomas Isenhour (Member) James Lee (Member) ABSTRACT INVESTIGATION OF THE POTENTIAL FOR ALGAENAN TO PRODUCE HYDROCARBON BASED FUELS FROM ALGAE BY HYDROUS PYROLYSIS Wassim Adel Obeid Old Dominion University, 2015 Director: Dr. Patrick G. Hatcher The use of algae as a feedstock for hydrous pyrolysis has a high potential for producing biofuels. The non-food nature of algae in addition to the various advantages associated with the hydrous pyrolysis process makes this combination for the production of biofuels of high interest. However, current results from algae processing have alluded to some challenges: byproducts arising from the thermal transformation of carbohydrates and proteins, which become incorporated in the oil fraction, result in high oxygen and nitrogen contents of the oil. Accordingly, this produces an oil of low quality for refineries. This dissertation investigates use of a pretreatment approach where only the energy-rich component of algae, called algaenan, is used as feedstock for hydrous pyrolysis, thus removing the carbohydrate and proteinaceous - components prior to hydrous pyrolysis. This leads to the production of a higher quality oil with less oxygen and nitrogen content. Algaenan from Scenedesmus spp. was isolated using the three most common chemical isolation protocols followed in the literature to investigate their effects on the algaenan structure. A new isolation protocol was proposed based on selecting the most effective chemical treatments, from each of the three procedures, which had the least effect on the algaenan structure. Algaenan isolated by an abbreviated isolation approach was then subjected to hydrous pyrolysis to investigate its potential to produce a hydrocarbon-rich oil. Detailed analysis of the oil by advanced analytical techniques, including two dimensional gas chromatography coupled to time-of-flight mass spectrometry and electrospray ionization coupled to Fourier transform ion cyclotron mass spectrometry, revealed it to have hydrocarbon-rich and heteroatom-poor qualities similar to many Type I kerogen derived crude oils. Results also showed that hydrous pyrolysis treatment can be used to effectively concentrate algaenan from algal cells by finding the optimum temperature and time parameters. A protocol is presented which outlines a stepwise process to reach the optimum algaenan isolation parameters. Such a need can be envisioned if one is to eventually commercialize the process. From the results, a new two-step strategy is proposed to 1) isolate algaenan, by low temperature hydrous pyrolysis followed by 2) produce high quality oils from the isolated algaenan by high temperature hydrous pyrolysis. This strategy aimed to minimize the incorporation of heteroatoms into the oils by using hydrous pyrolysis to remove the carbohydrates and proteins prior to producing oils from algaenan. Detailed analysis of the produced oil with this approach shows that it is hydrocarbon-rich, heteroatom-poor and similar to that produced from the hydrous pyrolysis of the chemically isolated algaenan. V To my parents whose endless love and support made this a reality and to the soul o f my grandfather, a man like no other. ACKNOWLEDGMENTS A large number of people are to thank because they each affected my time at ODU differently. Mostly I would like to thank my thesis advisor Dr. Patrick Hatcher for accepting me into his group, for the countless hours of guidance and for always believing in me. Thank you for everything. Second, I would like to thank Dr. Elodie Salmon who was always there to provide help and feedback when most needed. I would also like to thank all the members of the hatcher group, for their valuable input and for their friendship. I would like to specifically mention Rajaa Mesfioui, who urged me to join the Hatcher group; Amanda Willoughby, for being the best cubicle neighbor; Derek Waggoner, who is the instrument guru in the lab and who is kinder than many give him credit for; and Blaine Hartman, for her help in the lab and for always telling you what’s on her mind, a quality much needed and only few have. The list would not be complete without mentioning Chelsea When, for her help in performing the experiments mentioned in brown coal chapter; Jason Collins, for all the times we spent at the library and at the gym and for whom the phrase “mind over matter” is forever engraved in my mind; Nardos Sori, who is my oldest friend at ODU; Hussam AbuAssi, who took me in his home in open arms when I first came to Norfolk; Hany SalahEldeen, my roommate and “partner in crime”; Dr. Joe El-khoury and Fadi Jradi, my friends from Lebanon and my academic companions since the days of undergrad. Last but not least, my undergraduate research advisor Dr. Najat Saliba, who was a mentor to me and whose guidance and inspiration is the reason I am here now. NOMENCLATURE HP Hydrous pyrolysis HTL Hydrothermal liquefaction HTG Hydrothermal gasification TAGs Triacylglycerides . FFA Free fatty acids DAGs Diacylglycerides MAGs Monoacylglycerides AA Amino acid AAs Amino acids kj AA formation rate constant k2 AA decomposition rate constant Bb Botryococcus braunii FTIR Fourier Transform Infrared spectrometry EA Elemental Analysis NMR Nuclear magnetic resonance 13C Carbon-13 ssNMR Solid state nuclear magnetic resonance spectrometry Py-GC/MS Flash pyrolysis coupled to gas chromatography mass spectrometry TFA Trifluoroacetic acid CPMAS Cross polarization magic angle spinning CDS Chemical Data Systems GC-MS Gas chromatography mass spectrometry GC-FID Gas chromatography flame ionization detection GCxGC-TOFMS Two-dimensional gas chromatography coupled to time-of-flight mass spectrometry ESI-FTICR-MS Electrospray ionization coupled to Fourier transform ion cyclotron mass spectrometry T Temperature P Pressure KJ Volume of waster at the experimental temperature Mw Mass of water added at room temperature vR Volume of the reaction vessel Pw Density of water at the experimental temperature p i Density of the water vapor (steam) at the experimental temperature NaOH Sodium hydroxide KOH Potassium hydroxide c o 2 Carbon dioxide HMF Hydromethylfurfural Sp. Species (singular) Spp. Species (plural) DCM Dichloromethane DPMAS Direct polarization magic-angle-spinning CDS Chemical Data Systems NSO Nitrogenated, sulfurated, and oxygenated TOF Time-of-flight THF Tetrahydrofuran A I mod Modified aromaticity index DBE Double bond equivalence C.I. Algaenan Chemically isolated algaenan HHV High heating value m/z Mass-to-charge ratio S/N Signal-to-noise ratio X TABLE OF CONTENTS Page LIST OF TABLES......................................................................................................xii LIST OF FIGURES.................................................................................................. xiv Chapter I. INTRODUCTION..........................................................................................1 1. WHY ALGAL BIOFUELS.....................................................1 2. DISSERTATION OBJECTIVES.......................................... 4 3. BACKGROUND INFORMATION......................................6 II. THE EFFECT OF DIFFERENT ISOLATION PROCEDURES ON ALGAENAN MOLECULAR STRUCTURE IN SCENEDESMUS GREEN ALGAE......................................................... 31 1. INTRODUCTION.................................................................. 31 2. MATERIALS AND METHODS........................................33 3. RESULTS AND DISCUSSION.......................................... 38 4. CONCLUSIONS.....................................................................57 III. CONVERSION OF BROWN COAL TO HYDROCARBON BASED OIL BY HYDROUS PYROLYSIS AT SUBCRITICAL CONDITIONS............................................................................................... 61 1. INTRODUCTION.................................................................. 61 2. MATERIALS AND METHODS........................................64 3. RESULTS AND DISCUSSION.........................................
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