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Membrane Assisted Liquid-Liquid Extraction of Cerium

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Membrane Assisted Liquid-Liquid Extraction of Cerium MEMBRANE ASSISTED LIQUID-LIQUID EXTRACTION OF CERIUM A thesis submitted for the degree of Doctor of Philosophy to The University of New South Wales School of Chemical Engineering and Industrial Chemistry Faculty of Engineering Sydney, Australia by Karin Helene Soldenhoff B Sc (Hons) University of Witwatersrand M Sc University of Cape Town February 2000 CERTIFICATE OF ORIGINALITY I hereby declare that this submission is my own work and to the best of my knowledge it contains no material previously published or written by another person, nor material which to a substantial extent has been accepted for the award of any other degree or diploma at UNSW or any other educational institution, except where due acknowledgement is made in the thesis. Any contribution made to the research by others, with whom I have worked at UNSW or elsewhere, is explicitly acknowledged in the thesis. I also declare that the intellectual content of this thesis is the product of my own work, except to the extent that assistance from others in the project's design and conception or in style, presentation and linguistic expression is acknowledged. (Signed) .. ABSTRACT Membrane assisted liquid-liquid extraction of cerium was investigated, with emphasis placed on the study of the reaction chemistry and the kinetics of non-dispersive solvent extraction and stripping with microporous membranes. A bulk liquid membrane process was developed for the purification of cerium(IV) from sulfate solutions containing other rare earth elements. The cerium process was studied in both a flat sheet contained liquid membrane configuration and with hollow fibre contactors. Di-2-ethylhexyl phosphoric acid (DEHPA) was identified as a suitable extractant for cerium(IV) from sulfuric acid solution, with due consideration of factors such as extraction ability, resistance to degradation, solvent selectivity and potential for sulfate transfer into a strip solution. A detailed study of the extraction of cerium(IV) with DEHPA defined the extraction reaction chemistry. The Ce/DEHPA/sulfate system was also investigated with a flat sheet bulk liquid membrane configuration, using both sulfuric and hydrochloric acid as receiver solutions. These tests identified that hydrophobic membranes provide better mass transfer for extraction and hydrophilic membranes are better for stripping. The presence of an impurity, mono 2-ethylhexyl phosphoric acid (MEHPA), was found to have a dramatic accelerating effect on the rate of the chemical extraction reaction. This was attributed to its higher interfacial activity and population compared to DEHPA, and the fact that MEHPA was also found to be an active carrier for cerium(IV). The mass transfer rate of membrane assisted extraction and stripping of cerium, using hydrophobic and hydrophilic microporous membranes, respectively, was investigated using a modified Lewis-type cell. It was quantitatively demonstrated that the extraction process was mainly controlled by membrane diffusion and the stripping process was controlled by the chemical reaction rate, with membrane diffusion becoming important at low distribution coefficients. Finally, two hollow fibre contactors were operated continuously for 65 hours, highlighting the positive aspects of this technology. The process proved to be easy to control, with very low entrainment levels measured for solvent in the feed solution. High cerium(IV) extraction and good selectivity over other rare earths was achieved. Note: The main body of the thesis has been changed to correct spelling errors. Where appropriate, footnotes incorporating comments from reviewers have also been included. AKNOWLEDGEMENTS I would like to thank my supervisor Prof. Tony Fane for an introduction into the wonderful world of membranes and his guidance and comments. A special thanks goes to my co-supervisor Dr. Robert Ring for his encouragement throughout the period of this study. The support and help of many colleagues and friends at the Australian Nuclear Science & Technology Organisation is much appreciated. I would like to thank Des Levins for supporting my part-time studies and useful comments on reaction kinetics. Stuart Macnaugton and Jenny Mcculloch for helping with the construction of the hollow fibre rig and the tedious task of fibre potting. Lyle Poppitt and Bruce Breadner for always coming up with a practical solution for equipment fabrication. Thanks to Beate Wildner for the diagrams, collation and printing of the manuscript. A special thanks to Deborah Wilkins and Marleine Shamieh for the many shared cups of coffee and for always being so helpful in the laboratory. I would also like to acknowledge the contribution of Catherine Chan and Kate MacFarlane, who carried out some of the experimental work presented in chapter 5, during their undergraduate summer vacations. Finally a special thanks to my long suffering husband for the many extra hours of child care and the unfailing support. Note: This PhD thesis is submitted with the permission of the Australian Nuclear Science and Technology Organisation. Table of Contents MEMBRANE ASSISTED LIQUID-LIQUID EXTRACTION OF CERIUM 1. INTRODUCTION 1.1 Background 1 1.2 Solvent extraction versus liquid membranes 5 1.3 Scope of work and outline of this thesis 6 1.4 References 7 2. EXPERIMENTAL TECHNIQUES 2.1 Introduction 8 2.2 Chemical Reagents 8 2.3 General analytical procedures 9 2.3.1 Determination of cerium(IV) concentration 9 2.3.2 Determination of metal ions by inductive coupled plasma 11 2.3.3 Determination of aqueous acidity by titration 12 2.3.4 Determination of concentrations of di-2-ethylhexyl phosphoric acid and mono 2-ethylhexyl phosphoric acid 12 2.3.5 Purification of di-2-ethylhexyl phosphoric acid 12 2.4 Experimental procedures for Chapter 3 13 2.4.1 Equilibrium tests 13 2.4.2 Solvent stability tests 13 2.5 Experimental procedures for Chapter 4 14 2.5.1 Membrane characterisation 14 2.5.2 Three compartment flat sheet membrane permeation cell 15 2.5.3 Permeation experiments 15 2.5.4 lnterfacial tension measurements 15 2.6 Experimental procedures for Chapter 5 17 2.6.1 Analytical procedures for the determination of concentrations of iodine, acetone and toluene 17 2.6.2 Two compartment flat sheet membrane permeation cell 19 2.6.3 Permeation experiments 21 2. 7 Experimental procedures for Chapter 6 23 2.7.1 Hollow fibre contactor experimental apparatus 23 2.7.2 Measurement of entrained organic in the raffinate 25 2.8 References 25 Table of Contents 3. SOLVENT SELECTION AND CHEMISTRY 3.1 Introduction 26 3.2 Background 26 3.2.1 Acidic extractants 26 3.2.2 Solvating extractants 28 3.2.3 Basic extractants 29 3.2.4 Solvent extraction processes for cerium(IV) 29 3.2.5 Summary of background literature 30 3.3 Results and discussion 31 3.3.1 Solvent selection 31 3.3.1.1 Effect of aqueous media and acidity 32 3.3.1.2 Solvent selectivity 38 3.3.1.3 Solvent stability 39 3.3.2 Chemistry of extraction of cerium with TOPO and Cyanex 923 40 3.3.3 Chemistry of extraction of cerium with DEHPA 42 3.3.3.1 Acidity range of extraction 43 3.3.3.2 Effect of DEHPA concentration 43 3.3.3.3 Effect of solvent loading 43 3.3.3.4 Extraction reaction in the acidity range 0.5 to 5 M H2S04 46 3.3.3.5 Extraction reaction in the acidity range greater than 5 M H2S04 51 3.4 General discussion 55 3.5 Conclusions 56 3.6 Nomenclature 57 3.7 References 58 4. TRANSPORT OF CERIUM WITH A FLAT SHEET BULK LIQUID MEMBRANE 4.1 Introduction 66 4.2 Background 66 4.2.1 Transport mechanisms in liquid membranes 66 4.2.2 Types of liquid membrane systems 67 4.2.2.1 Emulsion liquid membranes 69 4.2.2.2 Supported liquid membranes 71 4.2.2.3 Bulk liquid membranes 72 4.2.3 The role of interfacial tension 75 4.3 Results and discussion 76 4.3.1 Membrane characterisation and selection 77 4.3.2 Permeation experiments 81 4.3.2.1 Effect of stirrer speed 84 4.3.2.2 Effect of membrane type 86 ii Table of Contents 4.3.2.3 Effect of mono-2ethyl hexyl phosphoric acid 91 4.3.2.4 Effect of receiver solution composition 94 4.3.2.5 Effect of cerium concentration in the feed 95 4.3.3 lnterfacial measurements 95 4.4 General Discussion 107 4.5 Conclusions 108 4.6 Nomenclature 109 4. 7 References 110 5. THE ROLE OF REACTION KINETICS IN MEMBRANE ASSISTED SOLVENT EXTRACTION 5.1 Introduction 116 5.2 Background 116 5.2.1 lnterfacial Zones 117 5.2.2 Extraction Regimes 118 5.2.3 Experimental Techniques 119 5.2.3.1 Stirred vessels with constant interfacial area 119 5.2.3.2 Highly agitated vessels 121 5.2.3.3 Moving drops 121 5.2.3.4 Rotating diffusion cell 122 5.2.3.5 Hollow fiber membrane extractor 122 5.2.4 Kinetic studies with di-2-ethylhexyl phosphoric acid 123 5.3 Results and discussion 129 5.3.1 Choice of experimental technique 129 5.3.2 Hydrodynamic characteristics of membrane permeation cell 129 5.3.3 Calibration of permeation cell with microporous hydrophobic Millipore GVHP membrane 138 5.3.4 Extraction of cerium with a membrane permeation cell 142 5.3.4.1 Determination of chemical extraction rate equation 145 5.3.4.2 Transport mechanism of membrane liquid-liquid extraction process 149 5.3.5 Calibration of permeation cell with microporous hydrophilic Millipore WLP membrane 153 5.3.6 Stripping of cerium with a membrane permeation cell 157 5.3.6.1 Determination of chemical reverse rate equation 158 5.3.6.2 Transport mechanism of membrane liquid-liquid back- extraction process 162 5.4 Conclusions 164 5.5 Nomenclature 166 5.6 Reference List 167 iii Table of Contents 6.
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