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Alternative Routes to Methyl Mercaptan from C1-Compounds

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Alternative Routes to Methyl Mercaptan from C1-Compounds Fakultät für Chemie, Lehrstuhl für Technische Chemie 2 Alternative routes to methyl mercaptan from C1-compounds Christoph Rudolf Erwin Kaufmann Vollständiger Abdruck der von der Fakultät für Chemie der Technischen Universität München zur Erlangung des akademisches Grades eines Doktors der Naturwissenschaften (Dr. rer. nat.) genehmigten Dissertation. Vorsitzender: Univ.-Prof. Dr. K.-O. Hinrichsen Prüfer der Dissertation: 1. Univ.-Prof. Dr. J. A. Lercher 2. Univ.-Prof. Dr. K. Köhler Die Dissertation wurde am 18.09.2015 bei der Technischen Universität München eingereicht und durch die Fakultät für Chemie am 12.11.2015 angenommen. Fortunato l’uom che prende Ogni cosa pel buon verso E tra i casi e le vicende Da ragion guidar si fà. Quel che suole altrui far piangere Fia per lui cagion di riso E del mondo in mezzo i turbini Bella calma troverà. (Glücklich preis ich, wer erfasset alles von der rechten Seite, der bei Stürmen niemals erblasset, wählt Vernunft als Führerin. Was im Leben andre weinen macht, ist für Ihn ein Grund zum Lachen, drohn Gefahren noch so fürchterlich, wahrt er seinen heitren Sinn.) Lorenzo da Ponte, Cosi fan tutte Acknowledgements First of all I would like to thank Johannes for giving me the opportunity to work on this interesting and challenging topic. Thank you for your trust in me, your guidance, patience and fruitful discussions. Thank you also for the opportunity to visit international conferences (Weimar, Milan). Next I want to thank Oliver. Thank you for your help with the publications and for proofreading this thesis. I am very grateful for your continuous support, be it motivational or sharing your expertise. Building the set up and dealing with operational problems would have been impossible without the help of Xaver, Andreas and Martin. Thank you, I learned a lot! I want to thank Evonik for financial support and highly interesting discussions during project meetings. Special thanks to Jan-Olaf, who was always available to answer urgent questions in a very quick and helpful manner. Heike, Steffi, Helen for helping me get things organized and thereby allowing me to fully concentrate on my scientific work. Those four years at TC 2 would have been less cheerful and for sure less successful without my great colleagues: Hendrik, Jürgen, Matteo, Florian, Andreas S., Andreas J., Roberta, Wolfgang, Phillip, Manuel, Ana, Aonsurang, Prado, Felix, Richard, Manuela, Rino, Krishna, Olga, Christian, Virginia, Elvira, Ben, Florencia, Lay-Hwa, Peter, Praveen, Carsten, Oliver, Stefan, Tobias, Frederik, Xuebing, Yongzhong, Chintan, Dechao. Thank you for the great time we had, at laboratory and office as well as outside university. I also would like to thank my diploma student Max and my internship students Linus, Astrid, Stephan, Bert and Ingrid for their great effort and the contribution to this work. During my time at TC 2 my life changed in a very positive and fundamental way. Not only did I learn and develop a lot, but I also got to know Sandra. Thank you for sharing your time with me ever since, for you love, your support, your encouragement and your help to set things into the right perspective. Last but not least I want to thank my parents for all the financial and non-financial support during my years at school and university. I am well aware that you offered me an ideal start into (working-) life and I am very grateful for that. Mama, vielen Dank für Deine Liebe und Unterstützung. Papa, vielen Dank dafür, dass Du seit meiner frühesten Kindheit mein Interesse an Naturwissenschaften geweckt und gefördert hast. Es tut mir leid, dass diese Arbeit nicht mehr rechtzeitig fertig geworden ist, sodass Du sie hättest lesen können. Diese Arbeit sei Dir gewidmet, ich hoffe, sie hätte Dir gefallen. Table of Contents Chapter 1 ................................................................................................................................................. 1 General Introduction ............................................................................................................................... 1 1.1. Methyl mercaptan .................................................................................................................... 2 1.1.1. Physical and Chemical Properties...................................................................................... 2 1.1.2. Applications of methyl mercaptan .................................................................................... 2 1.1.3. State of the art in the synthesis of methyl mercaptan ..................................................... 4 1.2. Alternative routes towards methyl mercaptan ........................................................................ 5 1.2.1. Synthesis from carbon oxides and H2S .............................................................................. 5 1.2.2. Other routes towards methyl mercaptan ....................................................................... 11 1.2.2.1. Methyl mercaptan from CS2 ..................................................................................... 11 1.2.2.2. Methyl mercaptan from dimethyl sulfide and dimethyl disulfide ........................... 12 1.1.2.3. Diverse ...................................................................................................................... 13 1.3. Catalysts in the synthesis of methyl mercaptan from H2S-containing synthesis gas ............. 13 1.4. Scope of this thesis ................................................................................................................. 20 1.5. References .............................................................................................................................. 22 Chapter 2 ............................................................................................................................................... 25 Effect of H2 in the synthesis of COS using liquid sulfur and CO or CO2 as reactants ............................. 25 2.1. Introduction ............................................................................................................................ 26 2.2. Experimental .......................................................................................................................... 27 2.2.1. Synthesis of catalysts ....................................................................................................... 27 2.2.2. Thermodynamic calculations .......................................................................................... 27 2.2.3. Activity tests .................................................................................................................... 27 2.3. Results .................................................................................................................................... 29 2.3.1. Formation of COS from CO, effect of catalyst ................................................................. 29 2.3.2. Formation of COS from CO, effect of H2 and total pressure ........................................... 30 2.3.3. Formation of COS from CO, effect of residence time and H2/CO ratio ........................... 32 2.3.4. Formation of COS from CO2, H2 and liquid sulfur ............................................................ 33 2.4. Discussion ............................................................................................................................... 34 2.4.1. Description of the reaction media................................................................................... 34 2.4.2. Reaction network ............................................................................................................ 39 2.4.3. Role of pressure and liquid sulfur ................................................................................... 42 2.5. Conclusions ............................................................................................................................. 44 2.6. References .............................................................................................................................. 45 Chapter 3 ............................................................................................................................................... 46 Synthesis of methyl mercaptan from .................................................................................................... 46 carbonyl sulfide over sulfide K2MoO4/SiO2 ........................................................................................... 46 3.1. Introduction ............................................................................................................................ 47 Thermodynamic considerations ................................................................................................ 47 3.2. Experimental .......................................................................................................................... 49 3.2.1. Catalyst preparation and activation ................................................................................ 49 3.2.2. Kinetic measurements ..................................................................................................... 49 3.2.2.1. Activity tests at varying H2/COS and H2S ratios ........................................................ 50 3.2.2.2. Activity tests at varying residence time ................................................................... 51 3.2.2.3. Activity tests in the absence of H2 ...........................................................................
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