Kinetics of the Selective Oxidation of O-Xylene to Phthalic Anhydride

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Kinetics of the Selective Oxidation of O-Xylene to Phthalic Anhydride Kinetics of the Selective Oxidation of o-Xylene to Phthalic Anhydride Doctoral Thesis (Dissertation) to be awarded the degree of Doctor of Engineering (Dr.-Ing.) submitted by Dipl.-Ing. Robert Marx from Dernbach approved by the Faculty of Mathematics/Computer Science and Mechanical Engineering Clausthal University of Technology Date of oral examination: January 27, 2012 Chairperson of the Board of Examiners: Prof. Dr. rer. nat. Alfred Weber Chief Reviewer: Prof. Dr.-Ing. Thomas Turek Reviewer: PD Dr. rer. nat. Gerhard Mestl Süd-Chemie AG iv Zusammenfassung Die Oxidation von o-Xylol zu Phthalsäureanhydrid auf Vanadiumkatalysatoren wird seit einigen Jahrzehnten industriell in Rohrbündelreaktoren betrieben. Moderne Katalysatorsysteme, die in diesen Reaktoren zur Anwendung kommen, bestehen aus mehreren Katalysatorlagen. Obwohl dieser Prozess sowohl industriell, als auch akademisch stark beforscht wurde, gibt es weiterhin eine Reihe offener Fragen. Dies betrifft insbesondere auch das Reaktionsnetzwerk. Die Bildung von Phthalsäureanhydrid verläuft in einem großen Netzwerk mit einigen Intermediaten. Die Hauptreaktionswege sind weitgehend aufgeklärt. Allerdings fehlen im Reaktionsnetzwerk noch einige Zwischenschritte, insbesondere solche, die zu den Nebenprodukten führen. Da es sich um ein Mehrlagensystem handelt, erfordert die rein empirische Optimierung der Katalysatoren erheblichen experimentellen Aufwand. Die Optimierung auf Basis eines mathematischen Modells der Reaktion bietet hier weitere Möglichkeiten. In der bisherigen Literatur ist die Kinetik dieser Reaktion nur für Laborpräparationen bzw. für vergleichsweise wenig produktive Katalysatoren beschrieben. In dieser Arbeit wird mit Hilfe eines polytrop betriebenen Zapfstellenreaktors im Pilotmaßstab, dessen Reaktionsrohr die Dimensionen eines industriellen Reaktionsrohrs hat, zum einen das Reaktionsnetzwerk weiter aufgeklärt und zum anderen die Kinetiken der verschiedenen Katalysatoren eines industriellen mehrlagen Katalysatorsystems beschrieben. Bei Versuchen mit dem beschriebenen Reaktorsystem wurden einige bisher unbekannte Intermediate gefunden. Durch Dosierungsversuche wurden deren Abreaktions- und Bildungspfade untersucht und es konnten dem bisher bekannten Reaktionsnetzwerk einige fehlende Reaktionsschritte, insbesondere die Bildung von Nebenprodukten wie etwa Maleinsäureanhydrid, Benzoesäure, CO oder CO2 betreffend, hinzugefügt werden. Bei der Entwicklung der Kinetiken der verschiedenen Katalysatorlagen liegt ein besonderes Augenmerk bei der Berücksichtigung des zuvor entwickelten Reaktionsnetzwerks, sowie in der Auswahl des erforderlichen Reaktormodells zur Beschreibung dieser Reaktion. Es wurde gefunden, dass sich in einer der Katalysatorlagen ein Aktivitätsprofil ausbildet. Darüber hinaus kann die kinetische Beschreibung dieser Reaktion durch Berücksichtigung von Stofftransportlimitierungen deutlich verbessert werden. v Summary The oxidation of o-xylene to phthalic anhydride on vanadia catalysts has been an industrial process conducted in multitubular reactor for several decades. Modern catalytic systems applied in this reaction consist of multiple catalytic layers. Although this process was researched both industrially and academically, a number of open tasks persist, particularly also considering the reaction scheme. Phthalic anhydride is produced from o-xylene in a large reaction scheme, involving several intermediate reaction steps. The main intermediates are well described. However, particularly in the formation of by-products several links are missing. In this multilayer system, purely empirical optimization of catalysts involves considerable experimental efforts. Model based optimization offers further perspectives in this point. In literature, the kinetics of this reaction has been described for laboratory preparations or for catalysts with comparatively low productivity for only a small operating range. In this work, on the one hand the reaction scheme of o-xylene oxidation is further investigated. On the other hand, the reaction kinetics of different layers of an industrial multilayer catalytic system is developed. The experimental set-up applied consists of a single tube pilot reactor with industrial tube dimensions with several axial sampling ports conducted in polytropic regime. In experiments with said experimental set-up, several previously unknown intermediates of the reaction were found. The production and decomposition routes of these intermediates were investigated by a series of dosage experiments. Thereby several additional reaction paths could be added to the known reaction scheme, particularly considering the formation of by-products such as maleic anhydride, benzoic acid, CO or CO2. In the development of reaction kinetics, particular focus was put on the proper representation of the developed reaction scheme as well as the choice of the appropriate reactor model to find the best description of the physical system. It was found that an activity profile develops within one of the catalyst layers. In addition, the kinetic description of this reaction could be significantly improved by taking into account also mass transfer limitations within the catalyst pellet. vi Danksagung Bei der Erstellung dieser Arbeit haben viele Menschen ihren Beitrag gehabt, die an dieser Stelle leider nicht alle einzeln erwähnt werden können, bei denen ich mich aber gerne an dieser Stelle bedanken möchte. Ganz pauschal möchte ich meinen Dank auch an die Süd-Chemie AG richten, in deren Laboren der Großteil der Ergebnisse, die zu dieser Arbeit führten, produziert wurde. Insbesondere möchte ich Hr. Prof. Dr.-Ing Thomas Turek danken für die Betreuung der Arbeit an der TU Clausthal, für die durchweg gute Zusammenarbeit im Verlaufe der letzten Jahre und für zahlreiche interessante und zielführende Diskussionen. Darüber hinaus gilt mein Dank Hr. PD Dr. Gerhard Mestl, zum einen natürlich für die Übernahme des Korreferats aber zunächst für die Themenstellung und vor allem für die Begeisterung, mit der er den Verlauf der Arbeit begleitet und bereichert hat. Besonders bedanken möchte ich mich bei Hr. Dr. Hans-Jörg Wölk, für die täglichen Diskussionen und dafür, dass er mir stets den Rücken frei gehalten hat, damit ich mich auf die vorliegende wissenschaftliche Arbeit konzentrieren konnte. Bei Hr. Dr. Andreas Reitzmann bedanke ich mich für das Interesse an meiner Arbeit und damit einhergehend viele Anregungen und Diskussionen, häufig zu fortgeschrittener Stunde. Bei Hr. Bernd Mischke von Chromatographie und Service möchte ich mich für die Durchführung der GC/MS Messungen bedanken. Meinen Bürokollegen, Fr. Nadine Fromm, Hr. Peter Schinke und Hr. Werner Pitschi möchte ich mich für die gute Arbeitsatmosphäre danken und dafür, dass sie stets zur Stelle waren, wenn zwei Hände einmal nicht ausgereicht haben. Schließlich möchte ich auch ein Wort des Dankes an meine Familie richten, die mich bei der Erstellung der vorliegenden Arbeit stets unterstützt hat. Content vii Content 1. Introduction ................................................................................................................... 1 2. Industrial Phthalic Anhydride Production .................................................................. 3 2.1 Production Process ................................................................................................ 3 2.2 Industrial Catalysts ................................................................................................ 4 2.3 Typical Performance of an Industrial Reactor ........................................................ 5 3. Kinetic and Reactor Modeling ...................................................................................... 8 3.1 Reactor Modeling – State of the Art ....................................................................... 8 3.2 Kinetic Modeling .................................................................................................. 13 4. Experimental................................................................................................................ 17 4.1 Reactor ................................................................................................................ 17 4.2 Catalyst ................................................................................................................ 20 5. Reaction Scheme ........................................................................................................ 21 5.1 Literature Overview .............................................................................................. 21 5.2 Selectivity Profiles ................................................................................................ 23 5.3 Identification of Intermediates .............................................................................. 26 5.3.1 Toluene .................................................................................................... 26 5.3.2 Toluquinone ............................................................................................. 27 5.3.3 2,3-Dimethyl-p-benzoquinone .................................................................. 29 5.3.4 Compounds Detected in Traces ............................................................... 30 5.4 Theoretical Aspects ............................................................................................. 30 5.5 Experimental Confirmation .................................................................................. 34 5.5.1 Toluene Dosage ......................................................................................
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