Thesis Balster
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Membrane module and process development for monopolar and bipolar membrane electrodialysis The research described in this thesis was supported by the Dutch Technology Foundation STW, applied science division of NWO. Membrane module and process development for monopolar and bipolar membrane electrodialysis J. Balster, PhD Thesis, University of Twente, The Netherlands ISBN: 90-365-2452-0 Cover design by J. Balster © J. Balster, Enschede, The Netherlands, 2006. Printed by Wöhrmann Print Service, Zutphen, The Netherlands. MEMBRANE MODULE AND PROCESS DEVELOPMENT FOR MONOPOLAR AND BIPOLAR MEMBRANE ELECTRODIALYSIS DISSERTATION to obtain the degree of doctor at the University of Twente, on the authority of the rector magnificus, prof. dr. W.H.M. Zijm, on account of the decision of the graduation committee to be public defended on Wednesday 13th of December 2006 at 13.15 by Jörg Henning Balster born 28th of July 1975 in Nordhorn, Germany This dissertation has been approved by the promotor Prof. Dr.-Ing M. Wessling and the assistant promotor Dr. D.F. Stamatialis. Preface After more than 5 years in Twente, working on my Master and my PhD thesis in the Membrane Technology Group, it is time to look back and see how the story started. Until the start of the 12th grade in high school (Gymnasium), I always thought that I would study computer science or information technology. When I had to decide which topic I should choose for the main examination course a friend of mine, Jörg Hesselink, persuaded me to take chemistry, so that they had enough people to get the course started. So Jörg, I think I owe you something for that. The next person I would like to acknowledge is Günther Briesemann from the EWABO Chemikalien GmbH. Günther ich danke Dir für deine Ratschläge und für die Möglichkeit, Erfahrung in der chemischen Industrie zu sammeln. Allen Mitarbeitern von EWABO danke ich für die tolle Atmosphäre während meiner Zeit dort. During my studies in Steinfurt I met a lot of new friends with whom I still have contact. Holger, Anja, Ansgar, Uwe, Ralph, 2 mal Melanie, Helga, Sabine, Renny, Matthias...., die Zeit mit Euch war super. Holger, lernen mit Dir war immer sehr erfolgreich, auch wenn wir manchmal etwas von unserem Studium abgeschweift sind. Anja, ohne deine Unterlagen hätten ich mein Studium niemals geschafft ☺. Für mich persönlich war auch der Masterstudiengang eine tolle Zeit. Steffi, Karin, Jürgen, es war toll mit Euch die Schulbank zu drücken. I have to thank especially Prof. Volkmar Jordan, who supervised all my projects from the University of Applied Sciences Münster during my Diplom and my Master studies, and who also helped me to get into contact with Matthias, here in Twente. Volkmar ich danke Ihnen für Ihre Unterstützung und freue mich, dass Sie in meiner Prüfungskommission sind und der Verteidigung beiwohnen. Finally arrived in Twente, I have first of all to thank Matthias for believing in my skills and giving me the opportunity to make my Master thesis and my PhD thesis in his group and also for giving me the possibility to work for the EMI. During my Master thesis I was very impressed by my supervisor Jonathan. Jonathan your enthusiasm in science is affecting the people around you and made that time very special for me. You gave me a lot of inspiration. Some people will now say I really got inspired by you, because my desk looks even more chaotic than the one from you during your time here. My supervisor during my time as PhD was Dimitris. We started both at the same time in our positions, you as Assistant Professor and me as your first PhD. I think we both did our jobs quite well, even when I started to make fun of you when some of my articles or abstracts were corrected for the sixth time and you started to correct your own corrections. In the end of my time I built up traps by giving you abstracts which were already printed to see if you start to correct again, but you recognised it. Dimitris I would like to thank you for all your input, discussions and also your corrections to improve this thesis. In parallel to the scientific part it was always nice to chat with you and I am very grateful that you were one of my wedding witnesses. Especially in the beginning of my period in Twente, but also in between, there was a lot of paper work to be done. Greet, I think without your help nobody in this group would survive. Thank you very much for all your help with these things. If you are working in the lab, a lot of things have to be arranged and prepared. Often people do not notice this help in the background, which is necessary for a working lab. John thank you for all your help. You were always there when I needed something. During my work, I had a lot of help from different people. First of all I have to thank Ineke, who was working 3 years as a technician in my project. Ineke thank you very much for all your effort and the good work you did. Olga who worked as a Postdoc on this project, Hakan, Raghu, Sabeeth and Catarina who worked as students on parts of this thesis, thank you all for your effort. Your measurements gave a big contribution to this thesis, as can be seen in the author list of each chapter. I also would like to thank the users of my project for their scientific input. Especially Hans Lammers from Akzo Nobel and Alber Verver from DMV International. Your ideas and help had a great impact on this work. Two people more contributed to successful experimental work inside the lab. Friedrich, thank you for coming from your work at Audi to Twente to explain the program you developed during your PhD in this group. Most of the experiments carried out for this thesis were not possible without your help. Wilbert, thank you for all your help with Labview and Acrobat. Without you I could not have built and automised the new setup and without your knowledge about Acrobat this thesis never would have been printed. Another special person I would like to acknowledge is Rob. Rob, you joined our group after I started, and the beginning of our relation was under a big shadow ☺. I had to change from the nice office downstairs (which was in Matthias eyes perfect for an Assistant Professor) into the so called chicken box. But you knew how to get light into the darkness immediately, by discussing motor races and soccer while drinking a few beers with me. Even if you were not one of my supervisors you gave a great input into this thesis. You prepared moulds, made Femlab simulations and had always a helping idea or advice. Thank you very much for everything. During the last years I had a lot of room mates. Miriam (who joined me downstairs and also in the chicken box), Benoit, Maik (who was first sharing with me and Miriam the office downstairs and later on in the chicken box next door, so more or less also still my room mate), Joao (who was in the chicken box with Maik, so close enough to say room mate), Dana, Jorrit, Hylke, and Karina, thank you for the nice time. Being for more than 5 years in the Membrane Technology Group means that you meet a lot of people, have a lot of activities and fun together. Thank you all for the nice time being here. Next to my work I was also involved in the organisation of the group trip to Hamburg and of the 7th meeting of the Network Young Membrains in Enschede. I would like to thank everybody who helped me during this tasks, which made it much easier and most of the time also quite nice (Hamburg at least until an angry email appeared ). Miriam and Harmen, I would like to thank you for being my paranimfs during my defence. It is nice to have friends at your side in such a situation. Natürlich möchte ich mich am Ende bei meinen Eltern bedanken, welche mich immer unterstützt haben. Ich danke Euch dass Ihr immer für mich da wart, auch in schwierigen Zeiten. All meinen Freunden möchte ich für Ihre Unterstützung danken. Bastian, besonders Dir möchte ich danken für deine Unterstützung und Hilfe. Du bist immer da wenn ein Freund Hilfe braucht. At the end I would like to say thank you to the two most important persons in my life. Dana and Julian I love you and I will always be there for you. Dana, te iubesc foarte mult. Vreau sa fiu tot timpul împreuna cu tine. Eşti in adâncul inimii mele. Contents Contents Introduction 11 Scope of this thesis 11 General introduction 12 Structure of this thesis 15 References 17 Chapter I: The development of bipolar membrane technology 19 1. Introduction 20 2. Principle of a bipolar membrane 20 3. Principle of bipolar membrane electrodialysis 21 4. Preparation of bipolar membranes 22 5. Characterisation of bipolar membranes 24 6. Limitations of bipolar membrane electrodialysis 27 7. Bipolar membrane electrodialysis processes 28 8. List of symbols 29 9. References 30 Chapter II: Tailoring the intermediate layer of the bipolar membrane 35 1. Introduction 36 2. Experimental 40 2.1 Materials 40 2.2 Bipolar membrane preparation 41 2.3 Characterisation of the ion exchange layers 42 2.4 Characterisation of the bipolar membranes 42 3. Results and discussion 45 3.1 Influence of the amount of ionic groups at the interface layer 45 3.2 Influence of the composition of the anion exchange layer 46 3.3 Fe-based catalytic interface layer 48 3.4 Pyridine based catalytic interface layers 52 3.5 Comparison of prepared bipolar membranes with different catalytic 56 layers 4.