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Diss. ETHNo. 17186 Decision-making Framework for Chemical Process Design Including Different Stages of Environmental, Health and Safety (EHS) Assessment A dissertation submitted to ETH Zurich for the Doctor of Sciences degree (Dr. of ETH sc. Zurich) presented by HlROKAZU SUGIYAMA Master of Engineering, The University of Tokyo born 30. 09. 1978 citizen of Japan accepted on the recommendation of Prof. Dr. Konrad Hungerbuhler, examiner Prof. Dr. Masahiko Prof. Dr. Alexander Hirao, co-examiner Wokaun, co-examiner 2007 Acknowledgement This thesis is the result of almost four years of research at the Safety and Environmental
Technology group at ETH Zurich. During this time, many wonderful people provided me with scientific and personal support. appreciation to I would like to express my sincerest Konrad Hungerbuhler for giving me the opportunity to conduct this thesis work at his group. He guided my research with a well- balanced amount of critical and creative, broad and in-depth to comments. My deepest gratitude also belongs my work with Ulrich Fischer who was most dedicated in supervising was so precious ideas, great atmosphere enthusiasm and steadfast our leadership, and besides important for the great in process group.
My special thanks go to Masahiko Hirao who provided the other essential pillar from Japan I was under the international and multicultural collaboration framework. The opportunity given I am to conduct parts of this project to at his group is very much appreciated. a also particularly grateful as Alexander Wokaun for his kind acceptance to be on second reviewer of the thesis well as creative comments this work. The financial support from Nagai Foundation Tokyo greatly is gratefully acknowledged. this work of CIBA Numerous people from industry contributed to by giving Specialty me insights from industrial practice.

I would like to thank Gerhard Giger Chemicals for the Go Inoue big picture of industrial process development, Koichi Nagai, Kunihiko Shigematsu, and Hisanori Watanabe of Sumitomo Chemicals, Hermann Siegelt and Dirk Sarcinelli of Degussa for specific experiences on MMA production processes, and Karl Straessle of Zurich am Financial Services for know-how of industrial hazard assessment. I Iwao Matsumoto of JEEL for his IDEF also very grateful to expertise, and Yoshio Kumagae of PreFEED for his valuable comments on process design heuristics. My research further profited greatly from Volker Hoffmann at ETH Zurich for any academic researchers. Special thanks go to Tetsuo providing at his economy-oriented perspectives, Institute of Fuchino, Atsushi Aoyama and Yuji Naka Tokyo Technology for encouraging the direction of integrated process design, of and all members of Hirao for Laboratory especially working-time Yasunori Kikuchi at the University Tokyo sharing joyful and creative whenever I returned there. During my work I had a constant support from ETH Chemistry Library I would like to express my to access to various kinds of literatures, and representatively appreciation Engelbert Zass for his enthusiastic help. working
I I had a most wonderful time in the creative and am hearty atmosphere of the Safety and Environmental Technology Group. most thankful to Elena Antonijuan, Isaac Kweku Adu, Andrea Bumann and Thomas Albrecht for their excellent performance in master theses and/or post-master database projects. My special a thanks go to Shailesh Shah who set up the EHS ready as perfect information-basis of this work. Many thanks I want to give to Ramon, Laurent, Fabio W, Fabio V, Georg, Valerie, Annette, Maximilian and Stefano who made my starting phase at ETH great and easy, and likewise to Matthias, Heike, Judith, David,
Harald and Roland who shared the office G136 but also the ups and downs of research with me. I am particularly powerful thankful to Prisca for her IT friendly help in all administrative issues and to Erol for his and troubleshooting. My great appreciation belongs experiences and discussions as Andrej M, Levente Andrej S who shared many members of the process group, also to Christian, Martin, Stefanie and Matthew who helped I would like to me through their environmental expertise. and dearly thank all members of our group for all the magnificent days nights including SOLA, bike-tours, ski-weekends, and Toggele. ove, support My deepest appreciation and gratitude is reserved for and their my parents, for all their unwavering faith in me. Zurich, May 2007 Hirokazu Sugiyama Abstract In recent years, chemical a core companies have adopted the concept of sustainable development as business value. The basis of various decision-making in their entire business has been extended to cover aspects, especially non-monetary issues, the in addition to economic performance. sustainability This thesis From the viewpoint of chemical engineering, big challenge is to integrate criteria early a in process design for as design objectives. rocess presents framework of chemical design, which incorporates multi objective consideration economic, and environmental, health and safety (EHS) different aspects in decision-making over design stages. With a focus on the early design according phase, to four stages, Process Chemistry as a I/II and Conceptual Design I/II, modeling are defined the available information basis for process and assessment. For each defined to economy, stage, appropriate modeling methods and evaluation indicators with respect lifethe cycle environmental impacts, EHS hazard and technical aspects are selected. Based at on evaluation esults, multi objective decision-making is performed systematically the each stage. A case study on methyl methacrylate (MMA) production study, which processes is applied throughout routes this thesis. This case uniquely offers 17 potential synthesis and various types of chemicals in the reaction network, is applied for demonstrating the framework. Starting with 17 an possible synthesis routes, optimized inferior routes are eliminated step-by-step and at is the last stage flowsheet of the route with the best multi objective case performance produced. observing Another part of the the evaluation study alidates decisions made within the framework over by profile of six routes when different stages. Most routes are correctly selected at earlier routes. cause design stages are compared are to the detailed assessment results of all six Several factors identified that to available in detail only at later stages, and which significant updates the results. Among these are the magnitude of energy consumption, EHS investment cost, the amount of loss of valuable of materials, and the monetary and a implications newly considered substances. For these parameters there is measures need to have better estimates in the form of proxy lready at earlier stages. Two what-if analyses are presented to examine how the assessment results are change when the different process options or evaluation settings considered. One analysis investigates l impact of specifying process options at the detailed conceptual design stage, i. e. the rigorous flowsheeting stage, economy and and the effect of choosing different setups in evaluation for the criteria of The MMA case life-cycle environmental impacts. options study quantitatively reveals that, among different types of process and evaluation settings, specifying alternatives in reaction chemistry, e. . synthesis path, has the most significant impact. This result confirms the importance layouts of reliable proxy indicators for for different forecasting unknown aspects, e. g. detailed process synthesis paths, in early design stages. the As the second part of the assessment what-if analysis, Several and impact of method selection can on the EHS results is presented. simple methods that The be applied in the early phases are compared qualitatively on quantitatively. assessment results change significantly depending The overall the hazard evaluation method in the applied in each of the EHS aspects. scope, iscrepancy mathematical result stems from the differences in the manner considered mass parameters, formulation, and especially own that process no information is treated. However, each method has its merit of one background and there is unique or method a over the other in any of the EHS aspects. The appropriate simplicity can degree only of detail of method considering early design phases where it be applied is the characteristic that separates the methods. Finally, the developed framework is serves as represented by using a a standardized activity modeling use technique, IDEFO, enables the which of blueprint f the business model. The same of IDEFO The description complex activities in detail and at the time transparently. activity model is defined for the four I to design stages as of the framework, i. e. from Process Chemistry Conceptual Design II, the activities to which appropriate case instructions and are resources are provided by as a project manager. Findings in the from the studies included in this activity model, know-how to be exploited design. traditional economic criteria with In summary, this dissertation demonstrates how to integrate non-conventional environment, health and safety criteria in ecision-making over different the stages of process design. This systematization will support chemical industry to undergo paradigm shift towards sustainability in developing processes. 11 Zusammenfassung Wahrend der letzten als Jahre hat die chemische Die Industrie Basis fur das die Konzept der nachhaltigen Entwicklung Kerngeschaft eingefuhrt. um Entscheidungsfindung besonders im gesamten Geschaftsbetrieb wurde finanzielle verschiedene zu Aspekte erweitert, nicht¬ Gesichtspunkte des wurden zusatzlich den okonomischen Kriterien erfasst. Aus der die grosse von Perspektive Chemieingenieurwesens liegt in Herausforderung ahrend in der die Prozessenticklung Entwicklungsziele. Diese Dissertation welches die der fruhen Integration Nachhaltigkeitskriterien prasentiert ein Rahmenkonzept Zielgrossen fur die aus Entwicklung chemische Prozesse, aus Berucksichtigung mehrere Wirtschaft, sowie den Bereichen Umwelt, Gesundheit und Sicherheit (UGS) wahrend verschiedener Entwicklungsstufen fur eine Entscheidungsfindung beinhaltet. Mit einem Schwerpunkt auf der fruhen I/II Planungsphase den werden die vier Stufen Process Chemistry eine Stufe I/II und Conceptual Design entsprechend und verfugbaren definiert. Informationen als Basis fur die
Prozessmodellierung Bewertung und UGS Fur jede definierte werden entsprechende Modellierungsmethoden okologischen Auf der Bewertungsindikatoren Gefahren und bezuglich Wirtschaftlichkeit, Belastungen, Grundlage in technischen wird Aspekten die ausgewahlt. dieser Stufe Abschatzungsergebnisse multi-kriterielle Entscheidungsfindung jeder systematisch durchgefuhrt. Die Produktion Dissertation von Methylmethacrylat (MMA) Diese wird als Fallstudie wahrend der ganzen 17 verwendet. Fallstudie, welche um potentielle Synthesewege zu und verschiedene Chemikalien aufweist, wird benutzt, werden das Rahmenkonzept demonstrieren. o Ausgehend von 17 Synthesewegen minderwertige Wege systematisch eliminiert, fur den dass in der letzten Stufe ein multi-kriteriellen optimiertes Flussdiagramm Syntheseweg mit der besten Leistung erhalten wird. Ein anderer Teil der Fallstudie validiert wahrend des Entwicklungswerdeganges Evaluationsprofile Synthesewege detaillierten Detail nur von gemachte Entscheidungen durch Beobachtung der sechs Synthesewegen uber verschiedene Stufen. Die meisten der 6 wurden in fruheren Stufen korrekt ausgewahlt, wie der Vergleich mit den im Abschatzungsergebnissen zeigt. verfugbar Mehrere Faktoren wurden identifiziert, die er in spateren Stufen sind und die grosse Veranderungen Ergebnisse verursachen. Solche Faktoren sind das Ausmass des Energieverbrauchs, Investitionskosten, in der Verlust von Wertstoffen, sowie finanzielle Auswirkungen und UGS-Einfluss von neu berucksichtigen eine bessere Substanzen. Diese Parameter sollten deshalb schon in fruheren Stufen fur als Einschatzung Proxyindikatoren verfugbar prasentiert um sein. Zwei wenn what-if Analysen unterschiedliche werden abzuschatzen wie sich die Ergebnisse andern Prozessoptionen oder Bewertungskriterien berucksichtigt werden. Eine d. h. in sowie der beiden der die Analysen rforscht in der detaillierten die konzeptionellen Entwicklungsstufe, von rigorosen Flowsheeting Stufe, Folgen der Wahl von Auswirkungen bestimmten Prozessoptionen verschiedenen Bewertungskriterien bezuglich quantitativ Wirtschaftlichkeit und Umweltbelastung. Typen von Die MMA Fallstudie lasst und den erkennen dass unter verschiedenen Prozessoptionen Synthesechemie fur verlassliche Bewertungskriterien grossen Einfluss in die Spezifizierung Dieses der Alternativen bestarkt die bezuglich Wichtigkeit Aspekte hat. Ergebniss um Indikatoren z. B. fruhen Entwicklungsstufen unbekannte verschiedene abzuschatzen, wie etaillierte Prozess-Auslegung fur Synthesewege. Als zweiter Teil der what-if Analyse prasentiert. wird die Einwirkung einfache der Methoden-Wahl auf die UGS Abschatzungsergebnisse Planungsphase Mehrere Methoden, die in der fruhen benutzt werden andern konnen, werden qualitativ und quantitativ verglichen. Die sich bedeutsam Abschatzungsergebnisse abhangig Die von der verwendeten UGS Bewertungs-Methode bezuglich stammt von aller UGS Aspekte. allgemeine Abweichung von im Resultat Unterschieden des und besonders berucksichtigten Bereiches, von Parametern, mathematischen Formulierungen der Art, wie Informationen ezuglich es Masse behandelt werden. Jede Methode hat Vorteil einer Methode an jedoch ihren eigenen Hintergund und gibt keinen eindeutigen gegenuber den anderen. Die entsprechende Einfachheit oder der Grad Genauigkeit einer Methode in Bezug auf die fruhe „Planungsphase”, ist die einzige charakteristische Grosse mit welcher die Methoden unterschieden werden konnen. Zum Schluss wird das entwickelte Rahmenkonzept mittels einer standartisierten Aktivitats Modellierungs Technik, IDEFO, prasentiert, Die die als ein Entwurf des Busienss Modells dient. die detaillierte Das Nutzung von IDEFO ermoglicht und

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