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Development of a Sustainable Technology Platform for the Homogeneous Friedel-Crafts Alkylation Using Acidic Ionic Liquid Catalyst

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Development of a Sustainable Technology Platform for the Homogeneous Friedel-Crafts Alkylation Using Acidic Ionic Liquid Catalyst Development of a Sustainable Technology Platform for the Homogeneous Friedel-Crafts Alkylation using Acidic Ionic Liquid Catalyst Über die Entwicklung einer nachhaltigen Friedel-Crafts Alkylierung mittels saurer ionischer Flüssigkeiten Der Technischen Fakultät der Friedrich Alexander Universität Erlangen-Nürnberg zur Erlangung des Grades DOKTOR-INGENIEUR vorgelegt von Master of Science (M.Sc.) Joni aus Erlangen Erlangen 2009 Als Dissertation genehmigt von der Technischen Fakultät Der Friedrich Alexander Universität Erlangen-Nürnberg Tag der Einreichung : 14. 04. 2009 Tag der Promotion : 29. 07. 2009 Dekan : Prof. Dr. Johannes Huber Berichterstatter : Prof. Dr. Peter Wasserscheid Prof. Dr. Andreas Jess Teile dieser Arbeit wurden bereits in den folgenden Fachzeitschriften oder als Tagungsbeitrag veröffentlicht: Fachzeitschriften: • J. Joni, M. Haumann, P. Wasserscheid, “Continuous gas phase isopropylation of toluene and cumene using highly acidic Supported Ionic Liquid Phase (SILP) catalysts”, Applied Catalysis A: General, 2009, submitted. • J. Joni, M. Haumann, P. Wasserscheid, “Development of a Supported Ionic Liquid Phase (SILP) Catalyst for Slurry-Phase Friedel-Crafts Alkylations of Cumene”, Advanced Synthesis and Catalysis, 2009, 351(3), 423. • J. Joni, D. Schmitt, P. S. Schulz, T. J. Lotz, P. Wasserscheid, “COSMO-RS aided kinetic studies of alkylation reaction in liquid-liquid biphasic reaction using acidic ionic liquid catalyst”, Chemie Ingenieur Technik, 2008, 80(9), 1253. • J. Joni, D. Schmitt, P. S. Schulz, T. J. Lotz, P. Wasserscheid, “Detailed kinetic study of cumene isopropylation in a liquid-liquid biphasic system using acidic chloroaluminate ionic liquids”, Journal of Catalysis, 2008, 258 (2) , 401. Tagungsbeiträge: • J. Joni, P. Wasserscheid, “Kinetic studies of alkylation reaction in liquid-liquid biphasic reaction using acidic ionic liquid catalyst”, Abstracts of Papers, 236th ACS National Meeting, 2008, Philadelphia, PA, United States. • J. Joni, V. Ladnak, P. Wasserscheid, “Acidic Molten Salts Vs. Acidic Room Temperature Ionic Liquid: A Comparative Study in Cumene Isopropylation“, DGMK/SCI Conference 2007, 2007, Hamburg-Germany. • V. Ladnak, J. Joni, P. Wasserscheid,” Concept Development from Ionic Liquid Solvent Evaluation to Miniplant Design for Homogeneous Friedel-Crafts Alkylation Reaction”, DGMK/SCI Conference 2007, 2007, Hamburg-Germany. • A. Riisager, R. Fehrmann, M. Haumann, M. Jakuttis, J. Joni, P. Wasserscheid,“ Supported Ionic Liquid Phase (SILP) Systems – Novel Fixed Bed Reactor Concepts for Homogeneous Catalysis”, DGMK/SCI Conference 2007, 2007, Hamburg-Germany. • Joni, V. Ladnak, P. Wasserscheid, “Acidic Molten Salts Vs. Acidic Room Temperature Ionic Liquid: A Comparative Study in Cumene Isopropylation“, 40th Deutsche Katalytiker Treffen, 2007, Weimar-Germany. PREFACE / VORWORT ACKNOWLEDGEMENT / VORWORT The following work was carried out in the Lehrstuhl für Chemische Reaktionstechnik of the Friedrich Alexander Universität Erlangen-Nürnberg from July 2006 until March 2009. Above all I would like to thank Prof. Dr. Peter Wasserscheid for giving me the chance to carry out this work in his research group. I thank him for being such an excellent and reliable adviser. His understanding and patient guidance really helped me throughout this project. For his endless support and confidence in me, I am forever grateful. I would like to thank Prof. Dr. Andreas Jess and Prof. Dr. Hans-Peter Steinrück for their willingness to review this work and for the many fruitful scientific comments on this work. In this opportunity I would like to express my highest appreciation to the following persons who have helped me to be able to finish this work. To all my bachelor and master students: Christine Funk, Daniel Schmitt, Melina Machado, Rushikesh Apte who have shown great interest and engagement in this project. This work would be only half as fun and half as successful without you. Thank you! To Michael Schmacks, Achim Mannke, Hans Peter Bäumler and Marco Haumann who have helped me through and through every detail in constructing the continuous alkylation plant. To Peter Schulz for his countless support in the analytics and for making all purchasing administration easier than it looks. To Michelle Menuét and the secretariat staff, I am greatly in debt for their patience and supports in all academic, but mostly non-academic, administrations. I also would like to thank my dear colleagues, Viktor Ladnak, Mitja Medved, Simone Himmler, Esther Kuhlmann, Sven Kuhlmann, Katharina Obert, Tobias Weiss, Michael Jakuttis, Caspar Paetz, Karola Höfener, Karola Schneiders, Natalie Paape, Berthold Melcher, Daniel Assenbaum, Judith Scholz, Alexandra Inayat, Amer Inayat, Soebiakto Loekman and all the coworkers that I cannot mention in this occasion. Thank you for the comfortable and constructive working atmosphere. Last but not least, I would like to show my gratitude to the SI-group Switzerland for the financial support throughout the work. i For my wife Aine TABLE OF CONTENT / INHALTSVERZEICHNIS TABLE OF CONTENT / INHALTSVERZEICHNIS ACKNOWLEDGEMENT / VORWORT ....................................................................................................... i TABLE OF CONTENT / INHALTSVERZEICHNIS ........................................................................................... ii FIGURE INDEX / ABBILDUNGSVERZEICHNIS ............................................................................................ v TABLE INDEX / TABELLEVERZEICHNIS ....................................................................................................ix 1. INTRODUCTION AND WORK SCOPE/ EINLEITUNG UND AUFGABENSTELLUNG ............................................. 1 2. THEORETICAL OVERVIEW / ALLGEMEINER TEIL................................................................................... 7 2.1. General considerations .................................................................................................... 7 2.2. Commercial aspects of Friedel-Crafts alkylation ............................................................. 8 2.3. Mechanistic and kinetic aspects of Friedel-Crafts alkylation reactions ........................ 15 2.3.1. Arenium ion (AE + DE) mechanism .......................................................................... 15 2.3.2. Substitution electrophilic unimolecular (SE1) mechanism ...................................... 17 2.3.3. Orientation and activity enhancement of substituted aromatics .......................... 17 2.3.4. Kinetic aspects of the Friedel-Crafts alkylation ...................................................... 21 2.4. Ionic liquids overview .................................................................................................... 23 2.4.1. Ionic liquids synthesis ............................................................................................. 24 2.4.2. Properties of ionic liquids ....................................................................................... 29 2.4.3 Friedel-Crafts alkylation in Ionic liquids ................................................................... 30 2.4.4. Friedel-Crafts alkylation on SILP catalysts .............................................................. 32 3. EXPERIMENTAL SET-UP AND METHODS/ EXPERIMENTAUFBAU ........................................................... 35 3.1. General remarks ............................................................................................................ 35 3.2. Chemicals ....................................................................................................................... 36 3.2.1. Reactants, products and solvents ........................................................................... 36 3.2.2. Ionic liquid and acid catalyst preparations ............................................................. 36 3.3. Experiment set-up: batch operation ............................................................................. 39 3.4. Experiment set-up: semi-batch operation .................................................................... 40 3.5. Experiment set-up: continuous operation .................................................................... 45 3.6. Analytical procedures .................................................................................................... 51 3.7. Automation and simulation tools .................................................................................. 56 4. RESULTS AND DISCUSSIONS / ERGEBNISSE UND DISKUSSIONEN ............................................................ 59 ii TABLE OF CONTENT / INHALTSVERZEICHNIS 4.1. Characterization of acidic ionic liquids and molten inorganic salts in biphasic reaction systems ................................................................................................................................. 59 4.1.1.Alternative acid catalyst for Friedel-Crafts alkylation reaction ............................... 59 4.1.2. Total reaction pressure effect ................................................................................. 62 4.1.3. Temperature effect ................................................................................................. 64 4.1.4. Solvent effect and COSMO-RS for solvent pre-screening procedure ..................... 67 4.2. Mechanistic understanding of Friedel-Crafts alkylation reaction in the presence of different acidic types ...........................................................................................................
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