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Oxidation of Dibenzothiophene to Dibenzothiophene Using Metal

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Oxidation of Dibenzothiophene to Dibenzothiophene Using Metal University of Texas at El Paso DigitalCommons@UTEP Open Access Theses & Dissertations 2010-01-01 Oxidation Of Dibenzothiophene To Dibenzothiophene Using Metal Nanoparticles Supported On Silica Karina Castillo University of Texas at El Paso, [email protected] Follow this and additional works at: https://digitalcommons.utep.edu/open_etd Part of the Geology Commons, Inorganic Chemistry Commons, Oil, Gas, and Energy Commons, and the Organic Chemistry Commons Recommended Citation Castillo, Karina, "Oxidation Of Dibenzothiophene To Dibenzothiophene Using Metal Nanoparticles Supported On Silica" (2010). Open Access Theses & Dissertations. 2656. https://digitalcommons.utep.edu/open_etd/2656 This is brought to you for free and open access by DigitalCommons@UTEP. It has been accepted for inclusion in Open Access Theses & Dissertations by an authorized administrator of DigitalCommons@UTEP. For more information, please contact [email protected]. OXIDATION OF DIBENZOTHIOPHENE TO DIBENZOTHIOPHENE SULFONE USING METAL NANOPARTICLES SUPPORTED ON SILICA KARINA CASTILLO Department of Chemistry APPROVED: Russell R. Chianelli, Ph.D., Chair Keith Pannell, Ph.D. Wen-Yee Lee, Ph.D. Christian Botez, Ph.D. Patricia D. Witherspoon, Ph.D. Dean of the Graduate School Copyright by Karina Castillo 2010 Dedication I want to dedicate my dissertation to my husband Jason Parsons who has always be there to help me, support me and guide me. OXIDATION OF DIBENZOTHIOPHENE TO DIBENZOTHIOPHENE SULFONE USING METAL NANOPARTICLES SUPPORTED ON SILICA by KARINA CASTILLO, MS DISSERTATION Presented to the Faculty of the Graduate School of The University of Texas at El Paso in Partial Fulfillment of the Requirements for the Degree of DOCTOR OF PHILOSOPHY Department of Chemistry THE UNIVERSITY OF TEXAS AT EL PASO May 2010 Acknowledgements I want to thank my advisor Dr. Chianelli for all his support and help him has given me throughout these years. I want to thank my committee members: Dr. Lee, Dr. Botez and Dr. Pannell for their time and help. Especially I want to thank Dr. Lee for her help in my dissertation and Dr. Botez for his help in x- ray diffraction. I also want to acknowledge Dr. Arteaga for all the guidance she provided me when I started my studies in chemistry. Dr. Alvarez she gave me the opportunity to be part of the RISE program and I thank her for that. The RISE program gave the necessary foundations to learn research skills. Additional programs such as MARC and Bridges to the Future provided me also with skills that I used during my master’s and doctorial degrees. I am really thankful to the coordinators of these programs. I also want to thank Dr. Mahmoud for giving me the opportunity to teach at El Paso Community College while pursuing my doctorial degree. This teaching experience helped me academically and financially during my doctorial degree. I want also thank the chemistry secretaries Lucema and Grace for helping me with my paperwork. I want to acknowledge Kristine Gonzalez for proofreading my thesis and distract me by making me adopt cats. I want to acknowledge Renzo Arias and David Chavez for helping with some of the experiments. I also want to thank Brenda Torres for helping me relax by making me go to the yoga and in general for being my friend. I am thankful to Alejandro Fernandez for checking on me throughout these years and making sure I am ok. Lastly I want to thank my mom, sisters, and my little brother for all their emotional support. I want to thank my husband Jason for all the things he has taught me. Without him getting this degree would have been harder and it would have taken a lot longer. Special thanks for financial support to the Welch Foundation, UNEEC Program (NASA) and Stanford Synchrotron Radiation Lab (SSRL) and Department of Energy (DOE). v Abstract Silica and nanoparticles of Pt, Au, and Ag supported on silica were tested for the ability to oxidize dibenzothiophene (DBT) to sulfone. High performance liquid chromatography was used to study the removal of DBT from solution. In addition, X- ray diffraction, infrared spectroscopy and Raman Spectroscopy were used to characterize the product of the oxidation reaction. Further studies involved the use X-ray absorption spectroscopy to characterize the nanoparticle catalysts before and after the oxidation reaction. To better understand the reaction, silica was synthesized at different pHs using three different acids. The acids used to synthesize the silica were HCl, HNO3, and H2SO4. The effect of SiO2 calcination temperature on the reaction was studied by drying silica at different temperatures. In addition, the oxidation reactions were performed at different temperatures and in different solvents. The reaction temperature used to test silica ranged between 115oC and 160oC when using decahydronaphthalene (decalin) as a solvent. Further studies were performed using high boiling point solvents tetrahydronaphthalene (tetralin) and n-dodecane. The percentage removal of DBT was similar when any of the three solvents was used in the reaction. However, when lower boiling point solvents were tested, such as hexane and heptane, no oxidation was observed. Furthermore, oxidation was not observed when the reactions were performed at the boiling point of each tested solvent. Silica synthesized at pH 0 using HCl, removed up to 70% of dibenzothiophene. However, a 90% removal was observed when commercially available silica was tested in this reaction. Studies were performed to determine activation energy of the reactions using silica and then using the metal nanoparticles supported on silica. The activation energy was determined by testing each catalyst at three different temperatures. Each reaction was sampled every 30 minutes for up to 2 h. The Pt/SiO2 catalyst had an activation energy of 20.26 kJ/mol, the Au/SiO2 catalyst an activation energy of 47.04 kJ/mol, and the activation energy of the Ag/SiO2 catalyst was 77.31 kJ/mol. In addition, the vi activation energy of SiO2 catalyst was determined to be 115.56 kJ/mol. The Pt/SiO2 catalyst had the lowest activation energy of all the studied catalysts. Recycling studies showed the Au/SiO2 catalyst maintained the highest catalytic activity when tested four consecutive times in the reaction. Infrared spectroscopy, X-ray diffraction and Raman spectroscopy confirmed that dibenzothiophene was oxidized to dibenzothiophene sulfone in the reaction. Furthermore, extended X-ray absorbed fine structure (EXAFS) showed the metal nanoparticles grew after the reaction. In addition, EXAFS studies also showed the silver catalyst converted to Ag2S after use in the oxidation reaction. vii Table of Contents Acknowledgements…………………… ............. ………………………………………………...V Abstract ........................................................................................................................................ VI Table of Contents…………………… ............ ………………………………………………...VIII List of Tables…………………… ..................... ………………………………………………...XI List of Figures ............................................................................................................................. XII Chapter 1: Background and Significance .......................................................................................1 1.1 Petroleum and its components. .....................................................................................1 1.1.1 Sulfur compounds in petroleum. .................................................................4 1.1.2 Petroleum Separation. .................................................................................5 1.2 Classification parameters of petroleum. .......................................................................7 1.3 Hydrodesulurization Process. .......................................................................................9 Chapter 2: Introduction ..................................................................................................................11 2.1 Oxidative Desulfurization an alternative method for HDS. ........................................11 2.2 Metal nanoparticle support .........................................................................................12 2.3 Reducing agents used to reduce metal nanoparticles ...................................................13 2.4 General methods to synthesize metal nanoparticles ....................................................15 2.5 Synthesis of metal nanoparticles on porous supports ..................................................15 Chapter 3: Material and Methods ..................................................................................................19 3.1 Dibenzothiophene model reaction ...............................................................................19 3.2 Synthesis of the support (SiO2) ...................................................................................20 3.3 Synthesis of metal nanoparticles on silica ...................................................................23 viii 3.4 Bimetallic Metal nanoparticles ....................................................................................23 3.5 Catalyst Recycling .......................................................................................................23 3.6 X-ray diffraction analyses (XRD) ...............................................................................24 3.7 XAS Studies .................................................................................................................24 3.8 XAS Data Analysis ......................................................................................................25
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