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About the Development of a Process for the On-Purpose Production of Propene out of Ethene Via a Sequence of Dimerization, Isomerization and Cross-Metathesis

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About the Development of a Process for the On-Purpose Production of Propene out of Ethene Via a Sequence of Dimerization, Isomerization and Cross-Metathesis About the Development of a Process for the On-Purpose Production of Propene out of Ethene via a Sequence of Dimerization, Isomerization and Cross-Metathesis Über die Entwicklung eines Prozesses für die selektive Umsetzung von Ethen zu Propen über eine Reaktionskaskade bestehend aus einer Dimerisierung, Isomerisierung und Kreuz-Metathese Der Technischen Fakultät der Universität Erlangen-Nürnberg zur Erlangung des Grades DOKTOR-INGENIEUR vorgelegt von Dipl.-Ing. Judith Scholz Erlangen 2013 Als Dissertation genehmigt von der Technischen Fakultät der Universität Erlangen-Nürnberg Tag der Einreichung: 14.09.2012 Tag der Promotion: 12.04.2013 Dekan: Prof. Dr.-Ing. habil. Marion Merklein Berichterstatter: Prof. Dr. rer. nat. Peter Wasserscheid Prof. Dr.-Ing. Andreas Jess Die Ergebnisse der vorliegenden Doktorarbeit entstanden von August 2008 bis Februar 2012 am Lehrstuhl für Chemische Reaktionstechnik der Friedrich-Alexander-Universität Erlangen- Nürnberg. Danksagung Gerne denke ich an die Zeit meiner Promotion zurück. Viele Menschen haben zu dem Gelingen meiner Arbeit beigetragen und diese Episode zu etwas Besonderem gemacht. Daher möchte ich an dieser Stelle die Gelegenheit nutzen, mich für die tollen dreieinhalb Jahre zu bedanken. Dabei geht mein größter Dank an meinen Doktorvater Professor Dr. Peter Wasserscheid. Trotz teilweise herausfordernder Aufgabenstellungen habe ich aufgrund Deiner Motivationskunst nie die Hoffnung und den Spaß an meiner Arbeit verloren. Die Möglichkeiten, die Du im Rahmen einer Promotion bietest, sei es in Form von technischer Ausstattung, Konferenzreisen im In- und Ausland oder auch in Form von Unternehmungen mit dem Lehrstuhl wie Skifahren, Bogenschießen, Rafting und Wandern halte ich für außergewöhnlich. Ich möchte Dir dafür herzlich danken. Herrn Professor Dr. Andreas Jess danke ich für die Übernahme des Zweitgutachtens und für die interessanten Gespräche in Pruggern und auf Konferenzreisen. Darüber hinaus geht mein Dank an die weiteren Mitglieder des Prüfungskollegiums, Herrn Professor Dr. Wilhelm Schwieger und Herrn Professor Dr. Jörg Libuda. Letzteren danke ich zudem für die Übernahme des Mentoring im Rahmen der EAM Graduate School. Für die Finanzierung von industrieller Seite möchte ich mich bei der Süd-Chemie AG bedanken. Zudem danke ich Dr. Normen Szesni und Dr. Roman Bobka für die unkomplizierte Zusammenarbeit, ertragreichen Diskussionen und die Bereitstellung von Trägermaterialien. Der Deutschen Forschungsgemeinschaft (DFG), die in ihrer Exzellenzinitiative den Exzellenzcluster „Engineering of Advanced Materials“ unterstützt, danke ich ebenfalls für die finanzielle Unterstützung und die Möglichkeit im Rahmen eines solchen Clusters forschen zu können. Insbesondere allen Mitgliedern der Research Area D „Catalytic Materials“ bin ich für die gewinnbringende Zusammenarbeit dankbar. Dr. Wolfgang Hieringer danke ich für die Durchführung der DFT-Berechnungen, welche einen großen Teil zur Aufklärung des „Metathese- Mysteriums“ beigetragen haben. Bei Xinjiao Wang bedanke ich mich für die Synthese verschiedenster Nickelkomplexe. Dr. Carsten Schür, Monika Schenk und Kristina Muck danke ich herzlichst für alle organisatorischen Dinge rund ums Thema Cluster und Graduate School. Dr. Marco Haumann danke ich für die stets offene Bürotür, die hilfreichen Tipps rund ums Thema SILP, die interessanten Gespräche zu jeder Gelegenheit und natürlich für das Korrekturlesen meiner Arbeit. Bei Herrn Dr. Nicola Taccardi und Markus Berger möchte ich mich für die Synthese von Katalysatorkomplexen und Ionischen Flüssigkeiten, die Hilfestellung zu NMR-Analysen und die Beratung in chemischen Belangen bedanken. Auch Dr. Andreas Bösmann und Dr. Friderike Agel bin ich für ihre fachliche Unterstützung äußerst dankbar. Dr. Peter Schulz bin ich dankbar für seine Geduld und Beratung rund ums Thema Analytik und für das Korrekturlesen meiner Arbeit. Für die schnelle und kompetente Hilfe bei den Auf-, Um-, und Abbauarbeiten von Anlagen möchte ich mich herzlich bei Michael Schmacks, Achim Mahnke, Julian Karl und Gerhard Dommer bedanken. Kalle, Hendryk und Herrn Fischer danke ich für das Lösen sämtlicher computertechnischer Probleme. Frau Menuet und Frau Singer danke ich für die zuverlässige Unterstützung in allen organisatorischen Belangen. Carolin Meyer danke ich für sämtliche Korrekturlesearbeiten, für das reibungslose Teilen eines Abzuges, für die morgendlichen Kaffeerunden und für alle Erlebnisse die wir mit und ohne Silvaner und unseren Friends hatten. Meinen ehemaligen Arena-Kollegen Caspar, Eva, Joni, Jakitukki, Caro, Matz, Swetlana, Kerstin, Markus und Jens danke ich herzlichst für das super angenehme, lustige und meist konstruktive Arbeitsklima. Insgesamt möchte ich mich bei allen ehemaligen und jetzigen Mitarbeitern des CRT für die tolle Zeit am Lehrstuhl bedanken. Großer Dank geht zudem an Anne, Ferdinand, Clara, Steffi, Denise, Lisa, Simon und Mammut – ohne eure Hilfe im Labor hätte ich weit weniger Ergebnisse erlangt. Zu guter Letzt bedanke ich mich bei allen meinen Freunden und meiner Familie, die mir jederzeit zur Seite standen und ohne die diese Arbeit niemals zustande gekommen wäre. Teile dieser Arbeit wurden bereits in der folgenden Fachzeitschrift veröffentlicht: J. Scholz, S. Loekman, N. Szesni, W. Hieringer, A. Görling, M. Haumann, P. Wasserscheid, Advanced Synthesis and Catalysis 2011, 353, 2701 – 2707. Teile dieser Arbeit wurden bereits als Tagungsbeitrag veröffentlicht: J. Scholz, M. Haumann, P. Wasserscheid: Investigations on the deactivation behavior of Grubbs- type olefin metathesis catalysts. Vortrag, 8th European Congress of Chemical Engineering together with ProcessNet Annual Meeting, Berlin, Deutschland, 2011. J. Scholz, W. Hieringer, M. Haumann, P. Wasserscheid: Investigations on the activity profile of immobilized Grubbs metathesis catalysts in a Supported Ionic Liquid Phase (SILP) system. Poster, 4th Congress on Ionic Liquids, Washington DC, USA, 2011. J. Scholz, W. Hieringer, M. Haumann, P. Wasserscheid: Reversible deactivation of Grubbs metathesis catalysts. Poster, 22nd North American Catalysis Society Meeting, Detroit, USA, 2011. J. Scholz, M. Haumann, P. Wasserscheid: Ethene induced deactivation of Grubbs metathesis catalysts. Poster, 44. Jahrestreffen Deutscher Katalytiker mit Jahrestreffen Reaktionstechnik, Weimar, Deutschland, 2011. J. Scholz, M. Haumann, P. Wasserscheid: Immobilization of Grubbs metathesis catalysts. Poster, 3rd EuCheMS Chemistry Congress, Nürnberg, Deutschland, 2010. J. Scholz, M. Haumann, P. Wasserscheid: Olefin metathesis with supported ruthenium catalysts. Poster, EUCHEM Conference on Molten Salts and Ionic Liquids, Bamberg, Deutschland, 2010. J. Scholz, M. Haumann, P. Wasserscheid: Olefin metathesis with supported ruthenium catalysts. Poster, 43. Jahrestreffen Deutscher Katalytiker, Weimar, Deutschland, 2010. J. Scholz, M. Haumann, P. Wasserscheid: Alken-Metathese mit Hilfe geträgerter Ruthenium- Katalysatoren. Jahrestreffen Reaktionstechnik, Würzburg, Deutschland, 2010. J. Scholz, M. Haumann, P. Wasserscheid: Fast Optimization and Kinetic Measurements of Supported Ionic Liquid Phase (SILP) Catalysts in a Parallel Reactor Set-Up. ISHHC XIV International Symposium on Relations between Homogeneous and Heterogeneous Catalysis, Stockholm, Sweden, 2009. Table of contents 1 Introduction 2 2 General part 6 2.1 Propene 6 2.1.1 Significance 6 2.1.2 On-purpose routes for propene production 7 2.2 Dimerization and oligomerization of ethene 12 2.2.1 Catalytic systems 13 2.2.2 Nickel hydride mechanism 16 2.2.3 Cationic nickel complexes for selective ethene dimerization and butene isomerization 17 2.3 Olefin metathesis 21 2.3.1 Different kinds of metathesis reactions 21 2.3.2 Catalytic systems 23 2.3.3 Metallacyclobutane mechanism 25 2.3.4 Ruthenium based Grubbs-type catalysts 27 2.3.5 Proposed deactivation mechanism of Grubbs-type catalysts 30 2.3.6 Thermodynamic aspects of olefin metathesis 35 2.4 Immobilization of homogeneous catalysts 36 2.4.1 Overview of immobilization concepts 36 2.4.2 Immobilized nickel dimerization and oligomerization catalysts 40 2.4.3 Immobilized ruthenium Grubbs-type metathesis catalysts 44 2.5 Objectives of this work 52 3 Experimental 56 3.1 General working technique 56 3.2 Chemicals 56 3.2.1 Substrates 56 3.2.2 Homogeneous catalysts 57 3.2.3 Ionic liquids 58 3.2.4 Support materials 60 3.3 SILP catalyst preparation 61 3.4 Continuous gas-phase experiments 62 3.4.1 Tenfold screening-rig 62 3.4.2 Continuous test-rig 65 3.5 DFT calculations 70 4 Results and discussion 73 4.1 Conversion of ethene to 2-butene via dimerization and isomerization 73 4.1.1 Reproduction of catalytic performance with literature-known SILP system 73 4.1.2 Optimization of the composition of the SILP system 76 4.1.3 Investigations on the possible reasons for deactivation 87 4.1.4 Approaches for catalyst stabilization 97 4.1.5 Optimized SILP system 113 4.2 Cross-Metathesis 116 4.2.1 Summary of all beneficial trends reported in literature for immobilized ruthenium metathesis catalysts 116 4.2.2 Systematic investigations on the influence of ionic liquid on catalyst stability 118 4.2.3 Influence of ethene on catalyst stability 122 5 Summary / Zusammenfassung 140 5.1 Summary / Abstract 140 5.2 Zusammenfassung / Kurzfassung 145 6 Appendix 153 6.1 Detailed synthesis conditions and NMR-characterization of ionic liquids 153 6.2 Flow sheets of rigs for continuous gas-phase experiments 156 6.3 Further experimental results 158 6.4 Calculations 159 6.5 List of abbreviations and symbols 160 6.6
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