Continuous Eutectic Freeze Crystallisation
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CONTINUOUS EUTECTIC FREEZE CRYSTALLISATION Report to the Water Research Commission by Jemitias Chivavava, Benita Aspeling, Debbie Jooste, Edward Peters, Dereck Ndoro, Hilton Heydenrych, Marcos Rodriguez Pascual and Alison Lewis Crystallisation and Precipitation Research Unit Department of Chemical Engineering University of Cape Town WRC Report No. 2229/1/18 ISBN 978-1-4312-0996-5 July 2018 Obtainable from Water Research Commission Private Bag X03 Gezina, 0031 [email protected] or download from www.wrc.org.za DISCLAIMER This report has been reviewed by the Water Research Commission (WRC) and approved for publication. Approval does not signify that the contents necessarily reflect the views and policies of the WRC nor does mention of trade names or commercial products constitute endorsement or recommendation for use. Printed in the Republic of South Africa © Water Research Commission ii Executive summary Eutectic Freeze Crystallisation (EFC) has shown great potential to treat industrial brines with the benefits of recovering potentially valuable salts and very pure water. So far, many studies that have been concerned with the development of EFC have all been carried out (1) in batch mode and (2) have not considered the effect of minor components that may affect the process efficiency and product quality. Brines generated in industrial operations often contain antiscalants that are dosed in cooling water and reverse osmosis feed streams to prevent scaling of heat exchangers and membrane fouling. These antiscalants may affect the EFC process, especially the formation of salts. The first aim of this work was to understand the effects of antiscalants on thermodynamics and crystallisation kinetics in EFC. A continuous EFC process is appropriate for the treatment of large volumes of brines since it allows better control of product quality, reduces waste and has less labour costs. The second aim of this work was to develop a continuous EFC process. To this end, a laboratory size continuous EFC plant was designed and commissioned. It is essential that continuous solid-solid-liquid separation is achieved in order to allow a smooth continuous EFC operation. This requires large ice and salt crystals which easily separate mechanically and since product properties depend on the operating conditions, it is important to understand the effect of residence time and degree of undercooling on product characteristics. Further to this, large production rates are required at industrial process scale. This is sometimes limited by scale formation and a study focused on understanding dynamics around ice scale formation was conducted. The third aim was therefore to investigate the interaction between operating conditions and product quality, as well as operational constraints of a continuous EFC process. Since industrial brines contain more than one component, there is an opportunity to recover ice and more than one salt product. Although the treatment of such brines was proven using batch EFC, the use of continuous EFC would be beneficial for the treatment of large volumes of brines. Therefore, the fourth aim of this research was to investigate the treatment of real multicomponent brines using continuous EFC. Phosphonate-based antiscalants were found to have a marginal effect on the thermodynamics of a Na2SO4-H2O system but showed significant effects on the crystallisation kinetics of both ice and salts. This was mainly attributed to the alteration of the surface free energy and surface coverage. The continuous 2 ℓ EFC plant was successfully commissioned and the crystalliser cooling capacity was found adequate for feed flow rates of 44 to 100 mℓ/min. Gravitational separation was achieved in the separation zones of the crystalliser. Increasing residence time at a constant operating temperature was found to enhance the mean crystal size of ice while increasing the degree of undercooling, at a constant residence time, increased the mean crystal size more significantly. The increase in size was attributed to more time for growth and faster growth rate, respectively. As expected, higher scraper speeds were found to delay the formation iii of an ice scale layer and the presence of impurities increased the induction time for scale formation. Ice and Na2SO4.10H2O were produced from continuous EFC of ternary Na2SO4-MgSO4-H2O synthetic solutions using a non-scraped agitated crystalliser. It was found that increasing the concentration of MgSO4 in the ternary Na2SO4-MgSO4-H2O depressed the eutectic temperatures for Na2SO4.10H2O and ice crystallisation. A real brine was also treated using a continuous EFC process that employed a jacketed column crystalliser. Ice and Na2SO4.10H2O were produced from this hypersaline brine but the production rates of both products varied widely at constant operating conditions. This was attributed to the coupled or interdependent crystallisation dynamics of the products in eutectic systems and short residence times in the column crystalliser, which limited time for salt crystallisation in some runs. The ice product had a high Na impurity content but this reduced significantly after washing. Only traces of impurities were detected in the Na2SO4.10H2O product but these could not be washed effectively. This report provides a literature review and synthesis, experimental methodology and results for each of the four aims of this project. iv Acknowledgements The project team wish to express their gratitude to - the staff of the Crystallisation and Precipitation Research Unit and the Mechanical Workshop, in the Chemical Engineering Department at the University of Cape Town for their contribution to the research reported here; the Water Research Commission (WRC) and University of Cape Town for the funding support; the members of the Reference Group for their contributions to and guidance of the project, namely: Dr JE Burgess, Water Research Commission Mr A Wurster, Independent member Ms R Muhlbauer, Anglo American Mr JS Beukes, Coaltech Prof LF Petrik, University of the Western Cape Mr IW van der Merwe, Proxa Mr P Gunther, Prentec Mr A Viljoen, Prentec Mr D Howard, Worley Parsons Dr G Madzivire, University of the Western Cape Mr HM du Plessis, Independent member Dr L Baratta, Sasol Mr G Gericke, Eskom Mr T Harck, Solution H v Table of Contents Executive summary .................................................................................................................. iii Acknowledgements .................................................................................................................... v Table of Contents ...................................................................................................................... vi Table of Figures ........................................................................................................................ xi List of Tables .......................................................................................................................... xiv Nomenclature ........................................................................................................................... xv Glossary .................................................................................................................................. xvi 1 Introduction ........................................................................................................................ 1 1.1 Problem statement ........................................................................................................ 2 1.1.1 Effect of antiscalants on the EFC process.............................................................. 2 1.1.2 Continuous EFC ..................................................................................................... 2 1.1.3 Operational considerations and limitations in continuous EFC ............................. 2 1.1.4 Multi-component EFC ........................................................................................... 3 1.2 Research aims ............................................................................................................... 3 1.2.1 Research objectives ................................................................................................ 4 1.3 Scope of research .......................................................................................................... 4 2 Theory of crystallisation ..................................................................................................... 5 2.1 Crystallisation ............................................................................................................... 5 2.2 Crystallisation kinetics ................................................................................................. 5 2.2.1 Nucleation .............................................................................................................. 5 2.2.2 Crystal growth ........................................................................................................ 6 2.3 Population balance ........................................................................................................ 7 2.4 Product quality .............................................................................................................. 7 2.4.1 Morphology (Habit) ............................................................................................... 7 2.4.2 Crystal size distribution ......................................................................................... 8