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Synthesis of Oxymethylene Ethers Synthesis of Oxymethylene Ethers Dissertation Zur Erlangung des akademischen Grades Doktor der Naturwissenschaften (Dr. rer. nat.) vorgelegt an der Fakultät für Chemie und Biochemie der Ruhr-Universität Bochum von Anna Grünert Bochum Oktober 2019 Die vorliegende Arbeit wurde in der Zeit von Februar 2016 bis Oktober 2019 in der Abteilung für Heterogene Katalyse am Max-Planck-Institut für Kohlenforschung in Mülheim an der Ruhr unter der Leitung von Prof. Dr. Ferdi Schüth angefertigt. Referent: Prof. Dr. Ferdi Schüth Korreferent: Prof. Dr. Martin Muhler I I Acknowledgements Firstly, I would like to thank my team of supervisors, Prof. Dr. Ferdi Schüth and Dr. Wolfgang Schmidt, and my co-examiner Prof. Dr. Martin Muhler. Ferdi, I would like to thank you for your trust that is the basis of the exceptional freedom of work, which you grant not only to me, but to all of your PhD students. You gave me the resources, time and liberty to develop my PhD project in my own way, to make mistakes, to solve challenging problems and to grow as a person. I am grateful for your appreciation of a cooperative and welcoming atmosphere in the group, which is most apparent in your yearly invitation to the group trip to Oberwesel. Wolfgang, I owe my thanks to you for your advice on many topics including material synthesis, catalyst characterisation and manuscript writing. I very much appreciate your welcoming and relaxed attitude. I am also thankful that to you both that you enjoy sharing your knowledge and experience with me and my colleagues in catalysis seminars and other technical seminars and in the focused project meetings. Prof. Muhler, thank you for taking interest in my work and for agreeing to be the co-examiner. The practical realisation of this work would not have been possible without the help of the staff of service departments, the technical staff of Schüth group and fellow PhD students. This is why I feel fortunate to have worked in close cooperation with the team of the Feinmechanics workshop including Wolfgang Kersten, Dirk Ullner, Knut Gräfenstein, Jürgen Majer, Sebastian Plankert and Ralf Thomas. Big thanks to all of you for your technical support and your exceptional willingness to help students in building and maintaining catalytic test equipment. Dirk, thank you so much for your fast and competent support when my set-up gave me troubles. It was also a pleasure to learn about set-up design, properties of steels and other materials and to get an introduction to the tools used in the workshop. Knut and Dirk, I will truly miss your ability to cheer me up with your special humour. I always felt welcomed at the Feinmechanics workshop. I would also like to acknowledge the contributions of locksmith and glassblower workshops to my project. In the pressure lab, where my catalytic test set-up was located, Nils Theyssen, Niklas Fuhrmann and Lars Winkel made sure that everyday operation of set-ups and lab II infrastructure ran smoothly. I owe my thanks to you and to my box neighbours Rene Albert, Dr. Robert Urbanczyk, Kateryna Peinecke and Özgül Sener for regularly helping me out with technical advice and spare parts. In the main lab, the technical staff André Pommerin, Laila Sahraoui and Flo Baum and their team of apprentices made sure that the lab was always safe and functional. Thank you for being approachable and helpful and for knowing where to find all kinds of things. I also owe many thanks to the staff of NMR, electron microscopy, HPLC, GC and IT departments including Dr. Bodo Zibrowius, Silvia Palm, Georg Breitenbruch, Frank Kohler, Philipp Schulze, Marjan Tomas and Marcus Hermes. I learned a lot from my colleagues Dr. Nicolas Duyckaerts, Dr. Ioan-Teodor Trotus, Dr. Daniel Wendt, Dr. Cristina Ochoa-Hernández, Dr. Pit Losch and Hrishikesh Joshi. Nico, Teo and Daniel, thank you for your patience in sharing your knowledge about Swagelok, flow set-ups and reactors. I am grateful for your input regarding the design and assembly of my test set-up at the beginning of my PhD project. Cristina, Pit and Hrishi, I appreciated your interest in my project and our fruitful discussions about chemistry. Of course, there is more to a PhD than working in the lab. I feel thankful for having gotten to know so many inspiring, kind and open fellow researchers. You have made me feel deeply connected to this group and have made my PhD time very enjoyable. I would like to express my gratitude towards my colleagues Özgül Agbaba Sener, Rene Albert, Dr. Ghith Al-Shaal, Dr. Amol Amrute, Alex Bähr, Adrian Barranco, Tugce Beyazay, Marius Bilke, Alex Bodach, Joel Britschgi, Eko Budiyanto, Dr. Matthew Clough, Dr. Yitao Dai, Dr. Isabel de Freitas, Jacopo de Bellis, Dr. Michael Dierks, Dr. Georgios “Jorro” Dodekatos, Dr. Rene Eckert, Dr. Michael Felderhoff, Jessica González, Alexander Hopf, Dr. Daniel Jalalpoor, Kai Jeske, Hrishikesh Joshi, Dr. Marco Kennema, Dr. Jonglack Kim, Klara Kley, Dr. Pit Losch, Dr. Gun-Hee Moon, Dr. Valentina Nese, Edward Nürenberg, Dr. Cristina Ochoa-Hernández, Ezgi Onur Sahin, Dr. Seyma Ortatatli, Dr. Jochen Ortmeyer, Kateryna Peinecke, Dr. Hilke Petersen, Dr. Christian Pichler, Dr. Gonzalo Prieto, Steffen Reichle, Dr. Bidyut Sarma, Dr. Hannah Schreyer, Dr. Stefan Schünemann, Niklas Stegmann, Dr. Harun Tüysüz, Dr. Robert Urbanczyk, Dr. Olena Vozniuk, Dr. Claudia Weidenthaler, Frederik Winkelmann, Mingquan Yu and all other colleagues that I may have forgotten to mention. III Thank you for spending time with me in the lab, at Mensa, in the social room, at lunch group, at group and cake seminars and other social events. Also, I am glad that some of you never forgot how to celebrate and dance. Edward, Niklas, Alex, Özgül and Cristina, it was great to share an office with you. I have appreciated the focused working atmosphere on the one hand and your openness to share matters of every-day life on the other hand. Thank you for your moral support and your valuable advice. Annette Krappweis und Kirsten Kalischer, your assistance in organisational issues was of great help. For financial support of my PhD, I would like to acknowledge the Max Planck Society and Fonds der chemischen Industrie. My participation in the JungChemikerForum Mülheim during my time at the Max-Planck- Institut für Kohlenforschung was also a great experience. It made me feel more connected to colleagues from the other research groups of this institute Minh Dao, Lorenz Löffler, Jonas Börgel, Jens Rickmeier, Suzanne Willems, Fabio Caló, Christine Schulz, Tobias Biberger, Julius Hillenbrand, Van Anh Tran, Marc Heinrich, Sebastian Beeg, Simon Musch, Christina Erken and those that I unfortunately forgot to mention, I would like to thank you for great team work and for your trust when I was your speaker. Last, but not least, I would like to express my gratitude towards my parents Wolfgang and Tanja Grünert and my partner Arne Schüttler. They have supported me during my bachelor’s and master’s degree and during my PhD project. Dad, thank you for passing on your appreciation for sciences, literature and music and especially for sharing your passion for chemistry. Mum, thank you for your unconditional moral support in all situations and for teaching me openness and curiousness. Arne, thank you for sharing your daily life with me, including its challenges and joyful moments. I am deeply grateful for your continuous trust and encouragement over the years. IV V II Table of contents I Acknowledgements ............................................................................................................. I II Table of contents ................................................................................................................ V III Abbreviations ................................................................................................................. VIII 1 Thesis abstract ..................................................................................................................... 1 2 Introduction ......................................................................................................................... 2 2.1 Synthetic fuels ........................................................................................................... 2 2.1.1 Chemical CO2 recycling .................................................................................... 2 2.1.2 Drop-in fuels ...................................................................................................... 3 2.1.3 Reduction of diesel emissions ............................................................................ 4 2.2 Oxymethylene ethers ................................................................................................. 5 2.2.1 Physicochemical and fuel related properties of OME ....................................... 5 2.2.2 Development and future challenges of OME research ...................................... 7 2.2.3 Synthesis ............................................................................................................ 8 2.3 Solid acid catalysis .................................................................................................. 12 2.3.1 Zeolites ............................................................................................................. 13 2.3.2 Supported liquid phase catalysts ...................................................................... 16 2.3.3 Characterisation methods ................................................................................. 18 2.4 Methanol dehydrogenation .....................................................................................
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