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I SYNTHESIS AND TESTING OF A SUPPORTED SHILOV OXIDATION CATALYST II INFLUENCE OF STRUCTURAL FEATURES ON ZEOLITE CHARACTERIZATION BY CONSTRAINT INDEX TESTING Thesis by John Reeves Carpenter III In Partial Fulfillment of the Requirements for the degree of Doctor of Philosophy CALIFORNIA INSTITUTE OF TECHNOLOGY Pasadena California 2010 Defended May 28 2009 ii 2010 John Reeves Carpenter III All Rights Reserved iii ACKNOWLEDGEMENTS Behind any achievement is a group of people whose contributions either directly or indirectly provide the support necessary to reach the goal This work is no different I am indebted to many people for helping me along my path of learning and discovery I will attempt to acknowledge many of those people here but am sure to miss some for which I apologize but assure your interactions were appreciated First I would like to thank Dr Mark Davis for the opportunity to be a member of his research group He has provided support and guidance that has allowed me not only to advance my knowledge scientifically and perform research but also learn on a more general level how to better attack problems and manage work processes In his lab I have had the opportunity to mature and grow as a research engineer Watching the various work in the lab has been exciting and I will continue to look back to see what the future holds for this lab I also would like to thank the other members of my thesis committee Dr Jay Labinger Professor Richard Flagan and Dr Stacey Zones Their time advice and support have been invaluable to me as I have worked to complete my thesis Part one of this thesis received financial support from BP through the Methane Conversion Cooperative The MC2 program provided a unique opportunity to experience a larger effort to research between multiple academic institutions and industry It was a program with a diverse set of views on the issues around methane activation and a interesting set of ideas Dr Labinger Dr John Bercaw and Dr Tom Baker from the program provided helpful guidance and suggestions to this work Part two of the thesis was financially supported by the Chevron Energy Technology Company with collaboration with Dr Zones I would like to express my gratitude to Dr iv Zones for the multitude of assistances he provided from access to his resources to valuable insight into the issues surrounding zeolite structure and activity to his wonderful patience Besides finical support and Dr Zones several other members of the Cheveron Energy Technology Company were helpful in this endeavor Dr Shelia Yeh provided her expertise on the XPS analysis of samples and Dr C Y Chen provided use of his equipment and time on the adsorption measurements Also I thank the other colleagues of Dr Zones though I can not name them all for their assistance in the procurement of several zeolite samples and facilitation of this collaboration During my time as a member of the Davis lab many good people have come and gone from the family Each has played a role in my life for which I thank them Dr Andrea Wight Dr Jonathan Galownia and Dr Victor Diakov were senior members when I arrived and helped my transition into the group Heather Hunt has been a constant office mate who has shared in the attempts to maintain sanity Dr Yuriy Roman Leshkov a recent addition to the lab has proved to be a wonderful assest sharing ideas as our projects have taken similar tracks Raymond Archer deserves lots of gratitude He joined the lab at the same time as I and has been a solid person to lean on for technical advice as a sounding board or even ranting He has done all of this with great openness and expected little back I can continue naming all of the people but then this would never end So to everyone in the Davis lab past and present thank you Finally I must thank my family without whose support this would not have been possible I know the long distance from my parents siblings and extended family has been tough on them as it has been on myself but they have remained supportive throughout recognizing the opportunity presented to me Also my wife Catherine she is my constant v support providing a listening ear when needed providing encouragement when things were not going well providing a distraction away from work when fun was required and tolerating my moments of stressed craziness I only hope I can return the support To everyone I offer my sincere gratitude and best wishes for success vi ABSTRACT This thesis is composed of two separate projects invoking the use of heterogeneous catalyst However that is the point where they diverge Part One details work on the development of a heterogeneous system for the direct oxidation of alkanes Part Two explores the use of competitive catalytic cracking of 3 methylpentane and n hexane as a tool for the characterization of zeolites Part One is about the development of a heterogeneous system for alkane oxidation Three techniques for creating heterogeneous catalyst from homogeneous systems without adding anchoring ligands are investigated supported molten salts supported aqueous phases and ion exchanged zeolites Each of these has been used to create Wacker oxidation catalysts in literature and in this work for comparison purposes From the study of Wacker oxidation the ion exchanged zeolites and supported aqueous phase catalyst were identified as potential methods for developing a Shilov oxidation catalyst The supported molten salt was eliminated because of high levels of chlorinated products and low activity Attempts were made with ion exchanged zeolites to oxidize ethane to ethanol but no products were detected The supported aqueous phase system however provided more promising results Initial work focused on oxidation of ethanesulfonate loaded onto the controlled pore glass support along with the catalyst Similar turnovers were achieved on the supported aqueous system as had been seen in the homogeneous system The reaction parameters of liquid loading oxygen pressure reactant concentration copper II chloride concentration and acid addition were investigated While the supported aqueous system was successful in the vii oxidation of ethanesulfonate attempts to perform ethane oxidation in a flow system were not The loss of chloride ions from the system is believed to lead to the deactivation Part Two investigates anomalous Constraint Index results for small and medium pore zeolites containing cages that are relatively larger than the pore i e cages similar in size to large


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