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Chapter5 Crystallization and Characterization of a New Propositions accompanying the thesis of F. Elif Genceli Scaling-Up Eutectic Freeze Crystallization 1. In heat flow calculations of crystallization on a cold surface [Pronk, P. et al.; Chemical Engineering Science, 2006, 61, p.4354-4362; Mershmann, A.; Crystallization Technology Handbook, 2001], it is frequently assumed that all heat of crystallization is transferred to the cold side which is not necessarily true (Chapter 7). 2. The Raman spectra presented in the work of Freeman et al. [Freeman J.J.; Wang, A.; Jolliff B.L.; 38th Lunar and Planetary Science Conference, 2007, No. 1338, p.1197] are not those of MgSO4.11H2O (Meridianiite) as they claim, but are spectra of crystal samples which have already been dehydrated into a magnesium sulfate with a lower hydrate content (Chapter 5-6). 3. It is surprising that no care was ever given since 1837 [Fritzsche, C.J.; Poggendorff’s Annalen, 1837, 42, 577-580] to determine the exact phase diagram of MgSO4 aqueous solution nor to determining the crystal structure of the magnesium sulfate phase formed at lower temperatures, despite the fact that the solution has been used in many crystallization applications as the model solution. [e.g.: Hogenboom, D.L.; Kargel, J.S.; Ganasan, J.P.; Lee, L.; Icarus. 1995, 115, 258-277] (Chapter 5). 4. It is easier to make nano-crystals from supercritical CO2 [Jung, J.; Perrut, M.; J. Supercrit. Fluids, 2001, 20, 3, 179-219] than by arrested precipitation from solution. 5. Putting CO2 underground is not a sustainable solution to our energy problem. 6. It is surprising, even paradoxical, that results in highly prestigious journals are not necessarily more reliable than those in second-tier journals. 7. The Turkish saying ‘the mirror of a person is his work, not his word’ is not true when working in a group! ‘Talking skills’ mostly overcome the ‘working skills’. 8. In modern world more intelligent women dedicate themselves to their career rather than to having more children. Due to the changing priorities of women, our society is under the threat of a decrease in the number of intelligent people. 9. Effective valorization and high level scientific research can reinforce each other. 10. The moneys spent on subsidies for “biofuels” would better be spent on purchasing and preserving rain forests. These propositions are considered opposable and defendable as such have been approved by the supervisor, Prof. Dr. G. J. Witkamp. Stellingen behorende bij het proefschrift van F. Elif Genceli Eutectische Vrieskristallisatie Opschalen 1. Bij berekeningen van warmtestromen van kristallisatie op een koud oppervlak [Pronk, P. et al.; Chemical Engineering Science, 2006, 61, p.4354-4362; Mershmann, A.; Crystallization Technology Handbook, 2001], wordt het regelmatig aangenomen dat alle kristallisatiewarmte overgedragen wordt naar de koude zijde wat niet noodzakelijkerwijs waar is (Hoofdstuk 7). 2. De Raman spectra uit het werk van Freeman et al. [Freeman J.J.; Wang, A.; Jolliff B.L.; 38th Lunar and Planetary Science Conference, 2007, No. 1338, p.1197] zijn niet die van MgSO4.11H2O (Meridianiite) zoals zij claimen, maar zijn de spectra van kristalmonsters welke al zijn gedehydrateerd tot een magnesiumsulfaat met een lager watergehalte (Hoofdstuk 5-6). 3. Het is verrassend dat er sinds 1837 geen aandacht is geschonken [Fritzsche, C.J.; Poggendorff’s Annalen, 1837, 42, 577-580] aan het bepalen van het exacte fasediagram van waterige MgSO4 oplossing noch aan het bepalen van de kristalstructuur van de magnesiumsulfaatfase gevormd bij lagere temperaturen, ondanks het feit dat de oplossing in veel kristallisatietoepassingen is gebruikt als modelstof [bijv.: Hogenboom, D.L.; Kargel, J.S.; Ganasan, J.P.; Lee, L.; Icarus. 1995, 115, 258-277] (Hoofdstuk 5). 4. Het is gemakkelijker om nanokristallen te maken vanuit superkritisch CO2 [Jung, J.; Perrut, M.; J. Supercrit. Fluids, 2001, 20, 3, 179-219] dan door middel van arrested precipitatie vanuit oplossing. 5. CO2 onder de grond stoppen is geen duurzame oplossing voor ons energieprobleem. 6. Het is verrassend, zelfs paradoxaal, dat resultaten uit zeer prestigieuze journals niet noodzakelijkerwijs betrouwbaarder zijn dan die uit tweederangs journals. 7. Het Turkse gezegde “de spiegel van een persoon is zijn werk, niet zijn woord” is niet waar wanneer er in een groep gewerkt wordt! ‘spreekvaardigheden’ overtreffen grotendeels de ‘werkvaardigheden’. 8. In de moderne wereld wijden intelligentere vrouwen zichzelf aan hun carrière in plaats van aan het krijgen van kinderen. Door de veranderende prioriteiten van vrouwen, is onze maatschappij onder bedreiging van een afname van het aantal intelligente mensen. 9. Effectieve valorisatie en wetenschappelijk onderzoek op hoog niveau kunnen elkaar versterken. 10. Het geld gespendeerd aan subsidies voor biobrandstoffen zou beter besteed kunnen worden aan het aanschaffen en behouden van tropisch regenwoud. Deze stellingen worden opponeerbaar en verdedigbaar geacht en zijn als zodanig goedgekeurd door de promotor, Prof. Dr. G. J. Witkamp. Scaling-Up Eutectic Freeze Crystallization Fatma Elif GENCELİ Scaling-Up Eutectic Freeze Crystallization Proefschrift ter verkrijging van de graad van doctor aan de Technische Universiteit Delft, op gezag van de Rector Magnificus prof. dr. J.T. Fokkema, voorzitter van het College voor Promoties, in het openbaar te verdedigen op maandag 21 januari 2008 om 12:30 uur door Fatma Elif GENCELİ Master of Science in Chemical Engineering, İstanbul Technical University geboren te Üsküdar/ İstanbul/ Turkije Dit proefschrift is goedgekeurd door de promotor: Prof. dr. G.J. Witkamp Samenstelling promotiecommissie: Rector Magnificus Voorzitter Prof. dr. G.J. Witkamp Technische Universiteit Delft, promotor Prof. dr. S. Kjelstrup Norwegian University of Science and Technology Prof. dr. T. Hondoh Hokkaido University of Japan Prof. dr. ir. A.J. Berkhout Technische Universiteit Delft Prof. dr. W. Buijs Technische Universiteit Delft Ir. H. Vrijenhoef Proton Ventures B.V. Prof. dr. ir. G.M. van Rosmalen reservelid, emeritus Technische Universiteit Delft This research was financially supported by the Ministry of Economic Affairs, the Ministry of Housing, Spatial Planning, and Environment, the Ministry of Education and Science of the Netherlands through the EET program, and Kemira Agro Ventures. The supports from Larox-Pannevis B.V., Nedmag Industries Mining & Manufacturing B.V., TNO, AVR B.V. and DSM Research are acknowledged. Cover design & layout by: Jelan Kuhn & F. Elif Genceli Crystal picture by Prof. dr. G.J. Witkamp ISBN: 978-90-9022729-0 Copyright © 2008 by F.E. Genceli Printed by Sieca Repro, Delft All rights reserved. No part of the material protected by this copyright notice may be reproduced or utilized in any form or by any means, electronic or mechanical, including photocopy, recording or by any information storage and retrieval system, without written permission from the publisher. To my dear mom, dad and sister Her zaman fedakar ve sonsuz sevgi dolu anneme Desteğini ve sevgisini hep kalbimde taşıyacağım babama En güzel yıllarımı beraber geçirdiğim, arkadaşım, dostum, canım ablama Table of Contents Chapter 1. Introduction 1 Chapter 2. Development and Performance of EFC Cooled Disk Column Crystallizer (CDCC) 19 Chapter 3. Inline Determination of Supersaturation and Metastable Zone Width of MgSO4·11H2O with Conductivity and Refractive Index Measurement Techniques 29 Chapter 4. Scaling-up Eutectic Freeze Crystallization 45 Chapter 5. Crystallization and characterization of a new Magnesium Sulfate Hydrate -MgSO4·11H2O- 65 Chapter 6. Meridianiite: Detected In Ice 91 Chapter 7. Coupled heat and mass transfer during crystallization of MgSO4·7H2O on a cooled surface 119 Chapter 8. Cyclic Innovation Model Application: Eutectic Freeze Crystallization 153 Appendix 191 Status of Eutectic Freeze Crystallization 193 English summary 197 Nederlandse samenvatting 203 Özet (Turkish summary) 209 Acknowledgments 215 Curriculum vitae 221 List of publications 222 Chapter1 Introduction Eutectic Freeze Crystallization F. Elif Gencelia a Process Equipment, Process & Energy Department TUDelft, Delft-The Netherlands Contains parts of NPT Processtechnologie, Augustus 2005, No.4, 19-20 Chapter 1 2 Introduction INTRODUCTION The world total energy consumption, global and industrial water usage-withdrawal are increasing very steep (see Figure 1.1) [Energy 2004, United Nations 2007]. It is estimated that without taking precautions and innovative changes, these rises will be even steeper due to multiplication by the increase in the world population [Energy 2004]. Related to this are environmental issues and the water problem. 88.7% of water on the Earth is salty water, and over two thirds of fresh water is frozen in glaciers and polar ice caps, leaving only 0.9% available for human use. Fresh water is a renewable resource, yet the world's supply of clean, fresh water is steadily decreasing. Water demand already exceeds supply in many parts of the world, and as world population continues to rise at an unprecedented rate, many more areas are expected to experience this imbalance in the near future. It is estimated that 15-20 % of world-wide water use is industrial (4% of world-wide water consumption). In general 52% of the world-wide water use is consumed [United Nations 2007, Wikipedia 2007, Coleridge 2006]. The prices of nonrenewable energy sources of petroleum, coal and gas are increasing dramatically. Therefore it is essential to develop true renewable sources such as solar energy, and to use exergy*
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