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Selective Salt Recovery from Reverse Osmosis Concentrate Using Inter-Stage Ion Exchange Joshua E

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Selective Salt Recovery from Reverse Osmosis Concentrate Using Inter-Stage Ion Exchange Joshua E University of New Mexico UNM Digital Repository Civil Engineering ETDs Engineering ETDs 7-3-2012 Selective salt recovery from reverse osmosis concentrate using inter-stage ion exchange Joshua E. Goldman Follow this and additional works at: https://digitalrepository.unm.edu/ce_etds Recommended Citation Goldman, Joshua E.. "Selective salt recovery from reverse osmosis concentrate using inter-stage ion exchange." (2012). https://digitalrepository.unm.edu/ce_etds/8 This Dissertation is brought to you for free and open access by the Engineering ETDs at UNM Digital Repository. It has been accepted for inclusion in Civil Engineering ETDs by an authorized administrator of UNM Digital Repository. For more information, please contact [email protected]. Joshua E. Goldman Candidate CIVIL ENGINEERING Department This dissertation is approved, and it is acceptable in quality and form for publication: Approved by the Dissertation Committee: Dr. Kerry J. Howe , Chairperson Dr. Bruce M. Thomson Dr. Stephen E. Cabaniss Dr. Jerry Lowry i Selective Salt Recovery from Reverse Osmosis Concentrate Using Inter-stage Ion Exchange BY Joshua E. Goldman B.A., Anthropology, State University of New York at Stony Brook, 2000 M.S, Environmental Science, University of South Florida, 2007 DISSERTATION Submitted in Partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy Engineering The University of New Mexico Albuquerque, New Mexico May, 2012 ii DEDICATION This dissertation is dedicated to the loving memory of my grandmother, Henriette Stein. iii ACKNOWLEDGMENTS This project was funded by the WateReuse Research Foundation. Resins were donated by ResinTech and Purolite. Francis Boodoo of ResinTech provided technical consultation for the pilot design. CDM wrote the Salt Market Analysis and helped with pilot operations. Robert Fowlie of CDM was responsible for the Salt Market Analysis and Doug Brown, Tim Rynders, and Chris Stillwell helped with pilot operations. Angela Montoya of the University of New Mexico, wrote the MATLAB model code, and Lana Mitchell assisted with laboratory analyses. I offer my sincerest gratitude to the following individuals. To my adviser, Dr. Kerry Howe, I thank you so much for mentoring me over the last five years and for the many hours you spent working on this project with me. Your guidance made this project possible. I would also like to thank my committee member, Dr. Bruce Thomson, for always having his office door open for questions and for providing his critical comments. It was only with the encouragement of Dr. Jeff Cunningham, of the University of South Florida, that I gained the confidence to pursue this degree. Thank you, Jeff, for believing in me. I am deeply grateful for the unwavering support of my family. Thank you for being there for me through everything. It is impossible to express the extent of my gratitude. I love you all so much. And finally, to my partner, Gabe Torres, thank you for the patience you have shown over the last two years. Your love sustained me. iv Selective Salt Recovery from Reverse Osmosis Concentrate Using Inter-stage Ion Exchange BY Joshua E. Goldman B.A., Anthropology, State University of New York at Stony Brook, 2000 M.S, Environmental Science, University of South Florida, 2007 Ph.D, Engineering, University of New Mexico, 2012 ABSTRACT A treatment process for reverse osmosis concentrate was developed to recover selected salts and increase fresh water recovery. The process utilizes cation and anion exchange to exchange all ions in the concentrate stream for sodium and chloride. The sodium chloride stream, with reduced scaling potential, can be treated further by a second reverse osmosis stage or another volume reduction technique to recover additional fresh water. The resulting concentrated sodium chloride stream can be used as ion exchange regeneration solution. Regeneration solutions from the cation and anion exchange columns are mixed to precipitate specific salts. In order to demonstrate the concepts behind this process, several phases of research were conducted. First, ion exchange batch isotherms were measured to characterize resin selectivity under ionic strength conditions common to reverse osmosis concentrate. A mathematical model was developed in which these isotherms were used to predict breakthrough curves. Regressions relationships developed from the batch tests were used in conjunction with the model to predict the number of bed volumes to breakthrough of v calcium, magnesium, and sulfate. Model and regression relationships were verified by a series of column experiments. Attempts to separate ions during the regeneration process were not successful. Ion distribution within a loaded column was characterized using a specially designed column from which resin samples could be taken along the longitudinal axis. Third, simulated cation and anion regeneration solutions were combined to precipitate selected salts which were analyzed to determine their constituents. Finally, the process was tested with a continuously operated pilot scale system. Mixing of simulated and pilot generated cation and anion regeneration solutions resulted in precipitation of calcium sulfate when mixed at pH below 4.5 and mixed carbonate salts when pH was not adjusted. The pilot system can produce 12 kg of precipitate per cubic meter of regeneration solution and recover approximately 45% of the calcium and 28% of the sulfate. vi TABLE OF CONTENTS ABSTRACT ....................................................................................................................... V LIST OF FIGURES .......................................................................................................XII LIST OF TABLES ....................................................................................................... XVI LIST OF EQUATIONS ............................................................................................ XVIII CHAPTER 1 .......................................................................................................................1 1.1 INTRODUCTION........................................................................................................1 1.11 Background ............................................................................................................1 1.12 Objectives ..............................................................................................................2 1.13 Proposed Treatment ...............................................................................................3 1.2 LITERATURE REVIEW ...........................................................................................7 1.21 Ion Exchange .........................................................................................................7 1.211 Selectivity ......................................................................................................8 1.212 Selectivity Modeling ....................................................................................11 1.213 Column Processes ........................................................................................13 1.214 Modeling of Column Processes ...................................................................15 1.22 Chemical Precipitation .........................................................................................18 1.221 Precipitation in Combination with RO ........................................................19 vii CHAPTER 2 .....................................................................................................................22 MODELING .....................................................................................................................22 2.1 Chapter Objectives .................................................................................................22 2.2 Chapter Summary ..................................................................................................22 2.3 - Modeling ..............................................................................................................23 CHAPTER 3 .....................................................................................................................32 DEPENDENCE OF RESIN SELECTIVITY ON IONIC STRENGTH AND SOLUTION COMPOSITION ........................................................................................32 3.1 Chapter Objectives .................................................................................................32 3.2 Chapter Summary ..................................................................................................32 3.3 Methods..................................................................................................................32 3.4 Results ....................................................................................................................35 3.41 Cation Exchange Isotherms ...........................................................................35 3.42 Anion Exchange Isotherms ............................................................................45 CHAPTER 4 .....................................................................................................................49 PHASE 2 – COLUMN TESTING FOR SELECTIVITY VERIFICATION AND ION SEPARATION .........................................................................................................49 4.1 Chapter Objectives .................................................................................................49
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