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Ultra-Low Temperature Water-Gas Shift Reaction with Supported Ionic Liquid Phase (SILP) Catalysts

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Ultra-Low Temperature Water-Gas Shift Reaction with Supported Ionic Liquid Phase (SILP) Catalysts Ultra-Low Temperature Water-Gas Shift Reaction with Supported Ionic Liquid Phase (SILP) Catalysts Wassergas-Shift-Katalyse mit geträgerten ionischen Flüssigkeiten unter extrem milden Reaktionsbedingungen Der Technischen Fakultät der Friedrich-Alexander-Universität Erlangen-Nürnberg zur Erlangung des Grades Doktor-Ingenieur vorgelegt von Diplom-Ingenieur Sebastian Werner aus Boppard Erlangen 2011 Lehrstuhl für Chemische Reaktionstechnik Vorstand Prof. Dr. P. Wasserscheid Egerlandstr. 3 91058 Erlangen www.crt.cbi.uni-erlangen.de Als Dissertation genehmigt von der Technischen Fakultät der Friedrich-Alexander- Universität Erlangen-Nürnberg. Tag der Einreichung: 10.01.2011 Tag der Promotion: 14.03.2011 Dekan Prof. Dr.-Ing. Reinhard German Berichterstatter: Prof. Dr. Peter Wasserscheid Prof. Dr. Kai-Olaf Hinrichsen Prof. Dr. Jörg Libuda Vorsitzender: Prof. Dr. Martin Hartmann Die vorliegende Arbeit entstand in der Zeit von November 2007 bis November 2010 am Lehrstuhl für Chemische Reaktionstechnik der Friedrich-Alexander- Universität Erlangen-Nürnberg im Rahmen des BMBF-WING Projekts "Sup- ported Ionic Liquid Phase (SILP)-Katalysatoren" (Förderkennzeichen 03X2012H) in Kooperation mit der Süd-Chemie AG (2007-2009). Im Rahmen des Ex- cellenzclusters "Engineering of Advanced Materials (EAM)" der Deutschen Forschungsgemeinschaft (DFG) wurde diese Arbeit weitergeführt (2009-2010). Auf Grund des internationalen Interesses wurde die englische Sprache gewählt. Für meine Eltern. DasProblem erkennenistwichtigeralsdieLösungfinden,denn die genaue Darstellung des Problems führt fast automatisch zur richtigen Lösung. Albert Einstein Danksagung Ich möchte mich an dieser Stelle bei allen am Lehrstuhl für Chemische Reakti- onstechnik bedanken - für kreative Atmosphäre und ein schönes Arbeitsklima! Auch wenn in den meisten Dissertationen eher förmliche Varianten der Dank- sagung zu finden sind, will ich diese Stelle (die ja auch fast die einzige ist, die ich in meiner Muttersprache verfasse), dazu nutzen auch ganz persönlich und offen zu danken. Mein größter Dank geht an Prof. Dr. Peter Wasserscheid für die herausfordern- de Aufgabenstellung und die Betreuung dieser Arbeit. Die unschätzbaren Mög- lichkeiten im Bezug auf Konferenzbesuche und Kontakte - aber auch für das feinfühlige persönliche Coaching/Mentoring, hat mich menschlich wie fachlich sehr viel weiter gebracht! Wenn es wirklich gebrannt hat, warimmer Zeit fürein Gespräch oder eine prompte Antwort - auch das Korrekturlesen dieser Arbeit mal kurz über die Weihnachtsfeiertage ist bestimmt nicht Standard. Danke! Dr. Marco Haumann gilt meine volle Anerkennung - ein Dr.-Ing. ehrenhalber für die vielen Tipps, Ideen und Hilfestellungen auch aus der ingenieurwissen- schaftlichen Ecke, wäre Dir meiner Meinung nach verdient - Danke Marco, das Arbeiten mit Dir als Gruppenleiter war eine wahre Freude. Die Kaffeepausen, lockeren Diskussionsrunden, Konferenzaktionen und auch Koch- und Grill- abende mit Prof. Brinkhoff’s und Dr. Fiege bleiben unvergesslich. Vermissen werde ich selbige sowieso! Viel Erfolg Dir in Korea! Auch Dr. Normen Szesni, Dr. Andreas Geisbauer und Dr. Richard W. Fischer vom Industriepartner Süd-Chemie AG will ich danken. Die wirklich gute Zu- sammenarbeit und die fachlichen Diskussionen haben mir viele neue Einblicke gebracht! Es ist nicht alltäglich, dass man immer ein offenes Ohr bekommt und erst recht nicht, dass sich ein Industriepartner auf so kurzen Zeitskalen auch zu Publikationen durchringt. Ohne diese Kooperation und die externe Reflexi- on der erzielten Ergebnisse wäre vieles nicht so schnell möglich gewesen. Ob bei einem Bier auf der Berghütte im Kaisertal, auf einer Konferenz oder beim Telefonat zwischen Tür und Angel. Sowohl persönlich als auch fachlich war die Zusammenarbeit wirklich super! Dr. Agnes Bittermann und Prof. Dr. Peter Härter vom Lehrstuhl für Anorga- nische Chemie der TU München sei für die Synthese, Charakterisierung und Bereitstellung der Liganden und Komplexe im Rahmen des BMBF Projekts gedankt. Analog auch ein Dank an Dr. Marc Uerdingen von der Merck KGaA für anregende Diskussionen und Bereitstellung der ILs. Auch Frau Dr. Stefa- nie Neuendorf von der Linde AG sei für die Wirschaftlichkeitsabschätzungen und die Messung der Gaslöslichkeiten im Rahmen des Projekts gedankt. Im Rahmen des Excellenzclusters war vor allem die Zusammenarbeit mit der Physikalischen Chemie, im speziellen Prof. Dr. Libuda und Marek Sobota sehr hilfreich. Dr. Wolfgang Hieringer und Hannes Schulz von der Theoretischen Chemie möchte ich für aufschlussreiche Diskussionen rund um die Mechanis- men der WGS danken. Auch Prof. Dr. Zenneck sei für die Tipps in den Untiefen der Ruthenium-Komplexe gedankt. Danke auch den vielen Doktoranden und Diplomarbeitern am CRT - denn das angenehme Arbeitsklima und die produktive Atmosphäre hat mir stets Motivation gegeben! Auch das faire Teamplay in wissenschaftlichen Dingen hat Spass gemacht - auch wenn es zwischen Forschung, Lehre und Raumnot eben ab und an Reibungspunkte gab. Besonders herausheben will ich mei- ne Bürokollegen (Nike, Subi, Karola, Steffi und Rene) sowie PS Schulz, Michi Jakuttis und Grobi, die immer für Diskussionen zu haben waren. Auch das (meist weniger) erfolgreiche Kickern mit diversen Kickerpartnern hat in Moti- vationsminima dann für neue Energie gesorgt :) Als Studien- bzw. Diplomarbeiter waren Matthias „Spüli“ Schirmer, Martin Weschta, Martin „Maddin“ Schneider, Markus Wangler und Willi Peters direkt oder indirekt mit dem Projekt befasst. Zusammen mit den HiWis Simon Wal- ter, Moritz Husmann und vor allem Michael Beck wurden mir erst viele Dinge möglich - und ich habe in der Zusammenarbeit mit Euch auch viel dazu ge- lernt! Danke auch für Eure Geduld und Nachsichtigkeit! Auch die Verdienste meines Vorgängers Tobias will ich für die Vorarbeiten in Sachen WGS nicht verschweigen. Für die kleinen und größeren praktischen Hilfen möchte ich mich bei den Werk- stattmitarbeitern Michael Schmacks, Achim Mannke, Julian Karl und Gerhard Dommer bedanken - ohne Euch wäre das weit schwieriger geworden! Wenn mal wieder was nicht ging und was defekt war, dann habt ihr mit Rat und Tat geholfen, das zeitnah irgendwie wieder in den Griff zu bekommen... Dipl.-Ing. Florian Enzenberger, Bob Mamrak Ph.D. und Dr. Marco Haumann möchte ich besonders für das kritische Korrekturlesen danken. Dem Prüfungskomitee mit Prof. Dr. Hartmann, Prof. Dr. Libuda und Prof. Dr. Hinrichsen danke ich, dass sie sich die Zeit genommen haben, dieses Doku- ment zu lesen und auch das Rigorosum abzunehmen. Der allergrösste und auch tiefste Dank gilt meinen Eltern - Für die moralische Unterstützung, aber vor allem für das Ermöglichen des Studiums! Sicherlich sind kistenweise Lego und die Kosmos Chemiebaukästen auch daran „Schuld“, dass aus mir ein Chemieingenieur wurde. Auch meinem engeren Freundeskreis, also Basti, Alex, Julian, Martin, Uli und den anderen Verrückten, die bei Klettern, Berg- und Skitouren sowie auf Reisen für den nötigen Realitätsabgleich gesorgt haben, bin ich sehr dankbar... Danke auch allen anderen, die direkt oder indirekt zum Gelingen beigetragen haben und deren Namen hier nicht explizit genannt ist! Mir haben die gut 4 Jahre am CRT echt einen Riesenspass gemacht! Publications i Parts of this work have been previously published in the following publications or presented at the conferences listed. Patents Werner, S., Szesni, N., Kaiser, M., Haumann, M., Fischer, R.W., Wasserscheid, P.: Katalysatorzusammensetzung für die Umsetzung von Kohlenmonoxid in Gasströmen. DE102009038690.4 (Priority 24.08.2009), WTO status pending. Peer reviewed articles • Werner, S., Szesni, N., Kaiser, M., Fischer, R.W., Haumann M., Wasser- scheid, P.: Water-Gas-Shift Reaction at ambient pressure and very low tem- peratures using homogenous Ruthenium based Supported Ionic Liquid Phase (SILP) Catalysts. Chem.Cat.Chem. (2010), 2(11), 1399-1402. • Werner, S., Szesni, N., Bittermann, A., Schneider, M.J., Härter, P., Hau- mann, M. Wasserscheid, P.: Very Low Temperature Water-Gas-Shift Reaction - Screening of homogenous Supported Ionic Liquid Phase (SILP) catalysts. Ap- plied Catalysis A (2010), 277, 70-75. • Werner, S., Schneider, M., Szesni, M., Haumann, M., Wasserscheid, P.: Homogeneous Ruthenium-based Water-Gas Shift Catalysts via Supported Ionic Liquid Phase (SILP) Technology at Low Temperature and Ambient Pressure. Physical Chemistry Chemical Physics (2009), 11, 10817-10819. • Werner, S., Weiss, T., Haumann, M., Szesni, N., Wasserscheid, P.: Sup- ported Ionic Liquid Phase (SILP) catalyzed Water-Gas-Shift Reaction. Chemie Ingenieur Technik (2008), 9, 1259 - 1260. Peer reviewed publications on related topics • Kim, T., Celik, F.E., Hanna, D.G., Shylesh, S., Werner, S., Bell, A.T.: Gas-Phase Hydroformylation of Propene over Silica-Supported-PPh3-Modified Rhodium Catalysts. Topics in Catalysis. (In press). ii Publications • Werner, S., Haumann, M., Wasserscheid, P.: Ionic Liquids in Chemical Engineering. Annual Reviews of Chemical and Biomolecular Engineering (2010), 1, 203-230. • Haumann, M., Jakuttis, M., Werner, S., Wasserscheid, P.: Supported Ionic Liquid Phase (SILP) Catalysed Hydroformylation of 1-Butene in a Gradient-free Loop-Reactor. Journal of Catalysis (2009), 263, 321 - 327. Conference contributions • Werner, S., Szesni, M., Haumann, R.W. Fischer, M., Wasserscheid, P.: Supported Ionic Liquid Phase (SILP) Catalysts for the Water-Gas-Shift Reaction at Ambient Pressure and Very Low Temperature. Presentation at AIChE Annual Meeting, Salt Lake City (2010). • Werner, S., Szesni,
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