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New Routes for Efficient and Sustainable Oxymethylene Ethers Synthesis

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New Routes for Efficient and Sustainable Oxymethylene Ethers Synthesis Fakultät für Maschinenwesen Lehrstuhl für Anlagen- und Prozesstechnik New Routes for Efficient and Sustainable Oxymethylene Ethers Synthesis Mohamed Kamal Ouda Salem Vollständiger Abdruck der von der Fakultät für Maschinenwesen der Technischen Universität München zur Erlangung des akademischen Grades eines Doktor-Ingenieurs genehmigten Dissertation. Vorsitzende(r): Prof. Dr.-Ing. Georg Wachtmeister Prüfer der Dissertation: 1. Prof. Dr.-Ing. Harald Klein 2. Prof. Dr.-Ing. Matthias Kraume Die Dissertation wurde am 03.07.2019 bei der Technischen Universität München eingereicht und durch die Fakultät für Maschinenwesen am 04.12.2019 angenommen. “The first step to knowledge is to know we are ignorant” Socrates 470 to 390 B.C. This cumulative thesis is composed from the following peer reviewed research articles as first author . Paper 1: Ouda, M.; Yarce, G.; White, R. J.; Hadrich, M.; Himmel, D.; Schaadt, A.; Klein, H. et al. (2017): Poly(oxymethylene) dimethyl ether synthesis – a combined chemical equilibrium investigation towards an increasingly efficient and potentially sustainable synthetic route. In: React. Chem. Eng. 2017, 2, S. 50–59. DOI: 10.1039/C6RE00145A. Paper 2: Ouda, M.; Mantei, F. K.; Elmehlawy, M.; White, R. J.; Klein, H.; Fateen, S.-E. K. (2018): Describing oxymethylene ether synthesis based on the application of non-stoichiomsetric Gibbs minimisation. In: React. Chem. Eng. 2018, 3, S. 277- 292. DOI: 10.1039/C8RE00006A. Paper 3: Ouda, M.; Mantei, F. K.; Hesterwerth, K.; Bargiacchi, E; Klein, H.; White, R. J. (2018): A hybrid description and evaluation of Oxymethylene dimethyl ethers synthesis based on endothermic dehydrogenation of methanol. In: React. Chem. Eng. 2018, 3, S. 676-695. DOI: 10.1039/C8RE00100F. Foreword This thesis was written during my time as a scientific assistant at the Fraunhofer institute for solar energy systems ISE and as PhD student at the institute of plant and process technology at the technical University of Munich APT-TUM. A lot of people in both institutes contributed directly and indirectly to this work. I would like to express my appreciation and gratitude for everyone of them. Special thanks to my supervisor Prof. Dr.-Ing. Harald Klein for his trust to supervise this work and his support along this journey which will impact my whole life. His presence and readness to help was something to learn besides the scientific exchange that I enjoyed. Thanks for Prof. Dr.-Ing. Matthias Kraume for taking over the second supervision. Thanks for Dr. Achim Schaadt and Dr. Robin White for their supervision at the Fraunhofer institute for Solar energy systems ISE and for their continouos support and orientation. Many thanks to Dr. Christopher Hebling, the head of Hydrogen- technologies division at Fraunhofer ISE for the trust and support on the personal and professional levels. Many thanks to all the co-authors and my students who did great work and gave me the chance to learn new things and widen my horizons. Special thanks to my colleagues and friends Christoph Hank, Valentine Leible, Lara Theiss, Kläre Chlinsmann, Max Hadrich, Florian Rümmeler, Robert Szolak, Anand Kakadyia, Johannes Full, Florian Nestler, Malte Otromke, Monika Bosilij and Tom Smolinka for their support: Working with you was more than great. My partner and very special supporter Carla: very grateful for your sincere care and support in the good and very hard times. Freiburg, den 01.07.2019 M. Ouda Kurzfassung Die C1-Oxygenate Oxymethylendimethylether (OME) sind ein interessanter Dieselersatz, der bei der Verbrennung in Dieselmotoren auch unter realen Fahrbedingungen eine deutliche Reduzierung der PM-Emissionen ermöglicht. OME werden auch als attraktive "grüne" Lösungsmittel und CO2-Absorber untersucht. Sie werden auf Basis von Methanol (MeOH) hergestellt, so dass ein auf fossilen oder erneuerbaren Energiequellen basierender Rohstoff verwendet werden kann. In dieser Arbeit wird ein einfaches, skalierbares und praktikables OME-Syntheseverfahren (im weiteren Textverlauf bezeichnet als direkte OME-Synthese) eingeführt, welches ausschließlich auf dem Rohstoff MeOH basiert. Die Synthese erfolgt in zwei Schritten, der endothermen katalytischen Dehydrierung von MeOH zu wasserfreiem Formaldehyd (FA) und Wasserstoff (H2). Dieses wasserfreie Produkt wird in einem zweiten Schritt direkt in den -1 OME-Synthesereaktor eingeführt, was zu einer sehr hohen Ausbeute von 14% g g product führt. Die Prozesssimulation wurde in einer hybriden Simulationsplattform implementiert, die die Vorteile der Verwendung von selbst entwickelten Reaktormodellen mit kommerziell verfügbaren Algorithmen kombiniert. Das kombinierte chemische und Phasengleichgewicht der OME-Synthesereaktion wurde durch die Lösung der Gleichgewichtsbeziehungen mit dem Newton-Raphson- Ansatz beschrieben. Versuche im Batch-Autoklaven mit MeOH und para-Formaldehyd (p-FA) wurden mit DW50X2 und Amberlyst 36 Katalysatoren bei unterschiedlichen Temperaturen und Feedverhältnissen durchgeführt. Die Ergebnisse wurden für die Validierung des in Matlab® implementierten OME-Reaktormodells verwendet. Parametrische Studienergebnisse zeigten, dass eine sehr hohe OME3-5 Ausbeute bei einem FA/MeOH-Molverhältnis von 1,8-2, einer Temperatur von 60 °C und dem geringsten Wassergehalt im Feed erreicht werden konnte. Die Ergebnisse zeigten zudem, dass die Temperatur die Gleichgewichtsreaktion nicht wesentlich beeinflusst. Basierend auf den bisherigen Ergebnissen wurde die Prozessleistung des wichtigsten Prozessschrittes, der endothermen MeOH-Dehydrierung zu FA und H2, definiert. Zur Prüfung der Dehydrierungsreaktion wurde eine kontinuierliche Versuchsanlage aufgebaut. Für dieses kinetisch gesteuerte Reaktionssystem wurde ein ringförmiger Gegenstromreaktor entwickelt. Die Tests wurden mit Na2CO3 bei T = 650-700 °C, mit einer MeOH-Feedkonzentration <10 vol.% und GHSV zwischen 7-35×103 h-1 durchgeführt. Die beste Prozessleistung wurde mit 40% MeOH-Umsatz bei >90% FA- Selektivität erzielt. Diese Prozessleistung lag in der Nähe der gewünschten Ergebnisse. Jedoch verringerte sich die Katalysatorselektivität gegenüber FA nach einigen Stunden im Betrieb, während die MeOH-Umsatz zunahm. Die Katalysatorentwicklungen für dieses Reaktionssystem und die Skalierung der innovativen Reaktorkonzepte sollen weiter untersucht werden. Dennoch wurden die Ergebnisse aus den stationären Tests dieser Reaktion zur Ermittlung experimenteller Reaktionsratenkonstanten bei 690 °C verwendet und ein einfaches globales kinetisches Modell dieses Reaktionssystems abgeleitet. Die Ausbeute an OME-Produkten wird durch das chemische Gleichgewicht und die Rückführung von Nicht-Reaktanten begrenzt. Zudem werden andere OME-Fraktionen als die des gewünschten OME-Wunschproduktes für eine zufriedenstellende Prozessausbeute unerlässlich. Die Modellierung dieses komplexen Reaktionsgleichgewichtssystems mit 32 Komponenten, die an 29 gleichzeitigen Reaktionen teilnehmen, unter Berücksichtigung der Rückführung ist herausfordernd. Die OME-Gleichgewichtszusammensetzung unter Berücksichtigung der Rückführung wurde dann durch die Anwendung des nicht-stöchiometrischen Gibbs-Ansatzes zur ungehinderten Minimierung unter Verwendung eines stochastischen globalen Optimierers beschrieben. Dieses Modell wurde mit Hilfe von Trioxan (TRI) und Methylal (OME1) als Feed über den Amberlyst 36 Katalysator validiert. Die Modellergebnisse ermöglichten es das optimale FA/MeOH-Feedmolverhältnis von 1,8 zu definieren, was die gewünschte endgültige OME3-5-Produktverteilung bei einer sehr hohen Ausbeute von 80,3 Gew.% (MeOH zu OME3-5) und einem minimalen Rückführungsverhältnis von -1 ca. 2,8 molrecycle mol feed ergibt. Die Ergebnisse des OME-Reaktionsgleichgewichtsmodells wurden zusammen mit den Ergebnissen des globalen kinetischen Reaktormodells der FA-Synthese sowohl in der Matlab®-Software implementiert als auch in eine CHEMCAD®-Plattform integriert, in der alle Komponenten des Prozessfließbildes enthalten sind. Die Integration erfolgte durch die Einbindung eines benutzerdefinierten Excel®-VBA-Blocks in CHEMCAD®, welcher die beiden Programme miteinander kommunizieren lässt. Ein physikalisches Stoffdatenmodell wurde in CHEMCAD® implementiert und die rigorosen Destillationskolonnen-Algorithmen zur Trennung der OME-Produktmischung verwendet. Die Integration der Prozesswärme erfolgte mit der Software PinCH 2.0. Für die Datenaufbereitung der PinCH-Ergebnisse wurde ein VBA- Code zur Stromdatenextraktion, Prozessstromsegmentierung nach Phasenänderung und Wärmekapazitätsauswertung entwickelt. Schließlich wurde ein einfaches Produktionskostenmodell implementiert und die Prozesskennzahlen definiert. Nach der Integration der Prozesswärme konnte der Dampfverbrauch um 16,1% und der Kühlwasserverbrauch um 30,4% gesenkt werden. Bei einer jährlichen Produktionskapazität von 35 kt OME3-5 beträgt die Gesamtprozessausbeute MeOH bis OME3-5 80,3%, die Prozessenergieeffizienz 71,7%, der spezifische Dampfverbrauch 2,31 MWh pro t OME3-5 und die Produktionskosten 903 US$ pro t OME3-5 (0,16 €ct./kWh). Die MeOH-Kosten sind mit 47% des Produktionskostenanteils der größte Anteil, gefolgt von den Energiekosten mit 22,3% und der Produktionskapazität. Bei einer großen jährlichen Produktionskapazität von 1000 kt und MeOH-Feedkosten von 300 US$ pro t betragen die geschätzten Produktionskosten nach dem in dieser Arbeit beschriebenen Verfahren 599 US$ pro t OME3-5 (0,10 €ct./kWh). Dies stellt die niedrigsten Produktionskosten im Vergleich zum verfügbaren Literaturprozess dar und zeigt das Potenzial des vorgestellten
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