FUNDAMENTALS ANDAPPLICATIONS OF

ANION SEPARATIONS

FUNDAMENTALS AND APPLICATIONS OF

ANION SEPARATIONS

Edited by

Bruce A. Moyer Oak Ridge National Laboratory

Oak Ridge, Tennessee

and

Raj P. Singh Osram Sylvania

Towanda, Pennsylvania

Springer Science+Business Media, LLC

Library of Congress Cataloging-in-Publication Data

Fundamentals and applications of anion separations/[edited by] Bruce A. Moyer and Raj P. Singh.

p. cm. Includes bibliographical references and index.

ISBN 978-1-4613-4742-2 ISBN 978-1-4419-8973-4 (eBook) DOI 10.1007/978-1-4419-8973-4

1. Anion separation-Congresses. 2. Anions-Analysis-Congresses. I. Moyer, Bruce A. II. Singh, Raj Pal. III. American Chemical Society Meeting (2001: Chicago, III.)

QD562.A54F86 2003 541' .3 722-dc22

2003068654

Proceedings of an American Chemical Society (ACS) Symposium, held August 26-31, 2001, in Chicago, IL.

ISBN 978-1-4613-4742-2

©2004 Springer Science+Business Media New York Originally published by Kluwer Academic/Plenum Publishers in 2004 Softcover reprint of the hardcover 1 st edition 2004

AII rights reserved

No part of this book may be reproduced, stored in a retrieval system, or transmitted in any form or by any means, electronic, mechanical, photocopying, microfilming, recording, or otherwise, without written

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Preface

This book documents the proceedings of the symposium "Fundamentals andApplications of Anion Separations" held during American Chemical Society NationalMeeting in Chicago, Illinois, August 25-30 , 200 I. Nearly 40 papers devoted todiscussions on anion separation related to fundamental research and applications werepresented. The symposium, sponsored by Osram Sylvania, BetzDearbom, and theSeparation Science & Technology Subdivision of the Industrial & EngineeringChemistry Division of the American Chemical Society was organized by Bruce A.Moyer, Chemical Sciences Division , Oak Ridge National Laboratory, P.O. Box 2008 ,Building. 4500S , Oak Ridge , TN 37831-6119, and Raj P. Singh , Chemicals andPowders R&D, Osram Sylvania, Chemical and Metallurgical Products Division,Towanda, PA 18848. It drew presenters from Australia, the Czech Republic, France,Germany, Japan , South Africa , Thailand, the United Kingdom, and the United States .

Separations constitute an integral part of chemical industry. Chemical productstypically originate in resources that must be concentrated and purified, chemicallytransformed, and subjected to fmal purification . Effluent streams from the processesmust be treated to recycle reusable components and to remove environmentally harmfulspecies. Some industrial processes are devoted to environmental cleanup after pollutionhas occurred. In addition, many analytical methods require a separation forpreconcentration, or a separation may be an inherent part of the analysis itself. Micro­separations occurring at membranes or interfaces are also related phenomena employed forion sensing. Many species targeted for separation are naturally anionic. Although thestandard separations techniques of extraction, ion exchange, adsorption, precipitation, etc.apply, the chemical approaches required must be tailored specifically to accommodate thenegative charge and electron-rich nature of anionic species. Hence, the topic of anionseparations occupies an important area of interest within the broader scope of separationscience and technology.

The subject of anion recognition and separation has in fact been growing rapidly inrecent years, with exciting discoveries at the fundamental level and economicallysignificant applications at the industrial level. This book, the first of its kind, covers thebreadth of knowledge being pursued at both ends of the basic-applied spectrum of anionseparation research and development. The need for the symposium and correspondingbook was anticipated in that basic discoveries in chemistry often encounter delay inreaching the application stage, basic researchers are often unaware of practical

v

vi PREFACE

applications, and applied chemists are often unaware of basic advances. Thus, reflectingthe objectives of the symposium, the main objectives of the book are (I) to disseminatethe high-impact opportunities for practical applications that can motivate basic research inanion separations , (2) to identify applications for exciting discoveries being made at basicresearch level toward developing innovative products and processes, and (3) to targetfundamental research for understanding and improving selective separation of anions.

Chapters presented in the book focus primarily on chemical approaches formanipulating selectivity in anion separations. In so doing, the chapters deal with thefollowing subtopics: design and synthesis of novel anion receptors, selective separationand recovery of anions by ion exchange, selective separation and recovery of anions byliquid-liquid extraction, anion-selective sorbents and inorganic ion exchangers,environmental remediation and waste treatment, and separation and purification of anionsvia precipitation and crystallization. The subject matter of the various chapters pertainsto applications in nuclear-waste remediation, hydrometallurgy, ion sensing,separation/preparation, and new anion sieves for environmental and other applications.By way of presentation, more fundamental papers are collected at the front of the book,becoming more applied and technique-oriented in later chapters. Approximately a thirdof the chapters deal with the design and use of anion receptors, compounds that display aspecial affinity for anions and function by multi-point interactions. A basicunderstanding of such compounds is only now emerging, and they are graduallybeginning to find their way into applications. Eventually, specific anion receptors havethe potential to enhance standard separation techniques such as liquid-liquid extraction,and several chapters in fact deal with such enhancements. The lead chapter summarizesprogress in the design and synthesis of anion receptors for separations and sensing.Following are two chapters discussing respectively physical and theoretical aspects ofanion binding. Three subsequent chapters describe different families of anion receptorsand their chemical behavior. To begin to shift the focus of the book toward applicationsand methods, specific needs for development of methods for anion separations in theU.S. Department of Energy complex are then described in Chapter 7. Chapters 8-10present specific approaches to anion extraction using receptors to enhance affinity andselectivity. Anion exchange, a work-horse separation technique for half a century, stillrepresents vastly fertile ground for selectivity enhancements, improvements, and novelapplications, as discussed in Chapters 11-13. Materials derived from biological sourcesrepresent an attractive area of development from the "green" perspective. Biosorbents inparticular are the topic of the next three chapters. A subsequent chapter deals with anovel concept in activated-carbon materials, one of the most versatile chemical platformsfor sorbtion of many types of chemical species. Finally, the book is capped off by twochapters on progress in inorganic sorbents and a chapter on a problem in anioncrystallization.

Although a large number of reviews and books are published every year onseparations of cationic species, a book on anion separation containing chapters from theleaders in the field is welcome. This collection of chapters can be used as a guide forgraduate students who desire exposure to recent research results in anion binding andseparation . The book will also be a useful tool to scientists and engineers involved inresearch and development in both academic and industrial settings.

Bruce A. MoyerRaj P. SinghAugust 2003

Acknowledgments

We express our appreciation to the participants in the Chicago symposium. Ourspecial thanks are extended to the tutorial speakers, Spiro Alexandratos and JonathanSessler, and to the many session chairs . We thank the authors for their hard work inpreparing the respective chapters of the book. Financial support for the symposium wasprovided by Osram Sylvania, BetzDearbom, and the Separation Science & TechnologySubdivision of the Industrial & Engineering Chemistry Division of the AmericanChemical Society and is gratefully acknowledged. Thanks are also due to KathyHammerly (Osram Sylvania, Towanda), Deborah A. Smith , Judith H. Moyer, BeckyMaggard, and Deborah L. Goddard (Oak Ridge National Laboratory) for editorial andsecretarial assistance. Bruce A. Moyer was supported by the Division of ChemicalSciences, Geosciences, and Biosciences, Office of Basic Energy Sciences, U.S .Department of Energy , under contract DE-AC05-000R22725 with Oak Ridge NationalLaboratory, managed and operated by UT-Battelle, LLC.

vll

CONTENTS

1. ANIONS IN SUPRAMOLECULAR CHEMISTRYBinding, sensing, and assembly .

Philip A. Gale

I. INTRODUCTION I2. BINDING 13. SENSING 144. ASSEMBLy ............ 215. CONCLUSIONS 276. ACKNOWLEDGMENTS 277. REFERENCES 28

2. MECHANISMS OF ANION RECOGNITIONFrom halides to nucleotides 31

Hans-Jorg Schneider

1. INTRODUCTION 312. ANION COMPLEXATION IN WATER 31

2.1. Ion Pairing 312.2. Salt Effects on Ion Pairing 342.3. Ion Pairing and Additional Lipophilic Effects 352.4. Hydrogen Bond-Based Anion Receptors 382.5. Simple or Highly Preorganized Receptors? 40

3. ACKNOWLEDGMENTS 414. REFERENCES AND NOTES 41

ix

x CONTENTS

3. STRUCTURAL ASPECTS OF HYDROGEN BONDINGWITH NITRATE AND SULFATEDesign criteria for polyalcohol hosts 43

Benjamin P. Hay, David A. Dixon, Gregg 1. Lumett a, Rubiceli a Vargas, andJorge Garza

1. INTRODUCTION 432. METHODOLOGY 443. RESULTS AND DISCUSSION 45

3.1. N03- Complexes 453.2. S042- Complexes 50

4. SUMMARY 555. ACKNOWLEDGMENTS 566. REFERENCES 56

4. SYNTHETIC RECEPTORS FOR ANION RECOGNITION 59

Suzanne L. Tobey and Eric V. Anslyn

1. INTRODUCTION 592. PHOSPHATE RECOGNITION WITH THE INTENT OF RNA

HYDOLYSIS 603. SENSING FOR CARBOXYLATE-CONTAINING NATURAL

PRODUCTS AND PHOSPHATE-CONTAINING COMPOUNDS ....... 614. RECOGNITION OF ACTIVE METHYLENE COMPOUNDS AND

pKA DETERMINATIONS 655. RECOGNITION OF INORGANIC ANIONS 666. SUMMARY 677. ACKNOWLEDGMENTS 678. REFERENCES 67

5. 2,3-DIPYRROLYLQUINOXALINE-BASED ANION SENSORS 71

Jonathan L. Sessler, Bruno Andrioletti, Pavel Anzenbacher, Jr., Chris Black,Leah Eller, Hiroyuki Furuta , Karolina Jurs lkova, Hiromit su Maeda ,Manuel Marquez, Toshihisa Mizuno , and Andrew Try

1. INTRODUCTION 712. SYNTHESIS AND INITIAL STUDIES 723. ' MET AL-CONT AINING SYSTEMS 764. QUINOXALINE SYSTEMS BEARING MULTIPLE PYRROLES 765. MACROCYCLIC SYSTEMS INCORPORATING QUINOXALINES 79

5.1. Quinoxpyrroles.......................................... ..................................... 80

CONTENTS xi

5.2. Quinoxphyrins................................................... ............................. 795.3. Quinoxaline-Br idged Schiff-Base Porphyrinoids........................... 81

6. CONCLUSION 837. ACKNOWLEDGMENT 838, REFERENCES 83

6. METALLA TED CALIXARENES ANDCYCLOTRIVERATRYLENES AS ANION HOSTS 87

K. Travis Holman and Jerry L. Atwood

1. INTRODUCTION 872. rr -METALLATED CALIX[4jARENES 913. A rr-METALLATED CALIX[5jARENE 944. rr-METALLATED CYCLOTRIVERATRYLENES 955. CONCLUSIONS 1036. REFERENCES 103

7. THE PROBLEM WITH ANIONS IN THE DOE COMPLEX 107

Gregg J. Lumetta

1. INTRODUCTION 1072. LITANY OF OFFENDING ANIONS 108

2.1. Tank Wastes 1082.2. The Environment .... 109

3. APPROACHES TO MITIGATING DOE ANION PROBLEMS 1103.1. Removing Problematic Anions from Tank Wastes 1103.2. Removing Problematic Anions from Groundwater 112

4. CONCLUSIONS 1135. ACKNOWLEDGMENTS 1136. REFERENCES 113

8. DlTOPIC SALT-BINDING RECEPTORS FOR POTENTIAL USE INANION SEPARATION PROCESSES 115

Joseph M. Mahoney, John P. Davis, and Bradley D. Smith

1. INTRODUCTION 1152. DITOPIC SALT-BINDING RECEPTORS 1183. LIQUID EXTRACTION OR MEMBRANE TRANSPORT USING

DITOPIC SALT RECEPTORS 1204. SUMMAR Y 1225. ACKNOWLEDGMENTS 1226. REFERENCES 122

xii CONTENTS

9. DUAL·HOST COMBINATIONS: USING TRIPODAL AMIDES TOENHANCE CESIUM NITRATE EXTRACTION BYCROWN ETHERS 125

Konstantinos Kavallieratos, Jeffrey C. Bryan, Richard A. Sachleben,Gary J. Van Berkel, Oscar D. Espetia, Melissa A. Kelly, Andrew Danby,Kristin Bowman-James, and Bruce A. Moyer

1. INTRODUCTION 1252. DESIGN CONSIDERATIONS FOR DUAL-HOST SYSTEMS FOR

CESIUM NITRATE EXTRACTION 1282.1 . Cesium Hosts 1282.2. Nitrate Hosts 129

3. THERMOCHEMICAL MODEL FOR DUAL-HOSTEXTRACTION: BINDING CONSTANTS AND EXTRACTIONENHANCEMENTS 131

4. DUAL-HOST EXTRACTION: AMIDE ANION HOSTS DERIVEDFROM 1,3,5-BENZENETRICARBOXYLIC (TRIMESIC) ACID ........ 135

5. NITRATE BINDING AND DUAL-HOST EXTRACTION USINGAMIDE-TYPE ANION HOSTS DERIVED FROMTRIS-(2-AMINOETHYL) AMINE (TREN) 139

6. 1,3,5-TRIS(AMINOMETHYL) BENZENE DERIVATIVES 1447. CONCLUSIONS 1458. ACKNOWLEDGMENTS 1469. REFERENCES AND NOTES 146

10. BINDING AND EXTRACTION OF PERTECHNETATE ANDPERRHENATE BY AZACAGES 151

Holger Stephan, Karsten Gloe , Werner Kraus, Hartmut Spies, Bernd Johannsen.Kathrin Wichmann, GUnter Reck, Dillip K. Chand, Parimal K. Bharadwa] .Ute MUller, Walter M. MUller, and Fritz Vogtle

1. INTRODUCTION 1512. RESULTS AND DISCUSSION 153

2.1. Liquid-Liquid Extraction Experiments 1532.2. Structural Considerations 158

3. CONCLUSIONS 1644. EXPERIMENTAL SECTION 164

4.1. Synthesis 1644.2. Liquid-Liquid Extraction Procedure 1654.3. X-ray Crystallography............................................................ ....... 165

5. ACKNOWLEDGMENTS 1666. REFERENCES 166

CONTENTS xiii

11. POLYMER·SUPPORTED REAGENTS FOR ANIONICRECOGNITION 169

Spiro D. Alexandrato s

1. INTRODUCTION 1692. SOLUBLE COMPLEXANTS 1703. POLYMER-BOUND COMPLEXANTS 1704. SUMMARY 1765. ACKNOWLEDGMENT 1766. REFERENCES 177

12. FUNDAMENTAL DEVELOPMENTS IN UNDERSTANDING THEINTERACTIONS BETWEEN METAL CYANIDES ANDFUNCTIONAL POLYMERS 179

Grant C. Lukey and Jannie S. J. van Deventer

1. INTRODUCTION 1792. PRINCIPLES OF GOLD RECOVERY USING RESIN

TECHNOLOGY 1812.1. Cyanidat ion 1812.2. The Resin-In-Pulp (RIP) Process 1812.3. Chemistry 182

3. SPECIATION OF METAL CYANIDES IN AQUEOUS MEDIA 1854. CHARACTERIZATION OF SORBED METAL CYANIDES

ON RESINS 1885. THE EFFECT OF SALINITY ON THE CAPACITY

AND SELECTIVITY OF RESINS FOR GOLD CYANIDE 1936. THE ELUTION OF METAL CYANIDES FROM ION-EXCHANGE

RESINS 1977. CONCLUSIONS 2028. REFERENCES 204

13. PREPARATION OF HIGH-PURITY METALS BY ANIONEXCHANGE 207

Minoru Isshiki, Kouji Mimura, and Tamas Kekesi

1. INTRODUCTION 2072. EXPERIMENTAL PROCEDURES 209

2.1. Equilibrium Tests 2092.2. Separation Experiments 211

3. RESULTS AND DISCUSSION 2133.1. Anion Exchange Equilibrium 213

xiv CONTENTS

3.2. Anion Exchange Separation Examples 2154. CONCLUSIONS 2225. REFERENCES 223

14. INFLUENCE OF THE SPECIATION OF METAL IONS ON THEIRSORPTION ON CHITOSAN 225

Eric Guibal, Javier Guzman. Ricardo Navarro. Montserrat Ruiz, and Ana Sastre

1. INTRODUCTION 2252. MATERIAL AND METHODS 227

2.1. Materials 2272.2. Chitosan Modification 2272.3. Methods 2282.4. Distribution of Metal Ion Species .. 228

3. SORPTION OF MOLYBDATE 2293.1. Effect of pH 2293.2. Molybdenum Species 230

4. SORPTION OF VANADATE 2334.1. Sorpt ion Isotherms 2334.2. Vanadium Species 233

5. SORPTION OF PLATINUM GROUP METAL ANIONS 2345.1. Sorption Isotherms in HCI and H2S04 Media 2355.2. Effect of Chitosan Modification 238

6. SORPTION OF COPPER- AND SILVER-CHELATED ANIONS 2427. CONCLUSIONS 2448. ACKNOWLEDGMENTS 2459. REFERENCES 245

15. SELECTIVE UPTAKE AND SEPARATION OF OXOANIONS OFMOLYBDENUM, VANADIUM, TUNGSTEN, AND GERMANIUMBY SYNTHETIC SORBENTS HAVING POLYOL MOIETIESAND POLYSACCHARIDE-BASED BIOSORBENTS 249

Zdenek Matejka, Helena Parschova, Pavia Ruszova, Ludek Jelinek,Pavia Houserova, Eva Mistova, Milan Benes. and Martin Hruby

1. INTRODUCTION 2492. MECHANISM OF SELECTIVE SORPTION OF OXOANIONS 2503. REQUIRED CHARACTERISTICS OF A SOLID SORBENT

CONTAINING DIOL LIGANDS 2514. SORBENTS 252

4.1. Synthetic Sorbents 2524.2. Polysaccharide-Based Biopolymer Sorbents 252

5. EXPERIMENTAL METHODS 2526. UPTAKE OF OXOANIONS BY POLYOL SORBENTS 252

CONTENTS xv

6.1. Uptake on Sorbent with l-deoxy-rnethyl-amino-glucitol MoietyImmobilized in StyreneIDVB Matrix 252

6.2. Uptake on Sorbent with Diethanolamine (DEA) MoietyImmobilized in StyreneIDVB Matrix 254

6.3. Uptake on Crosslinked Chitosan (poly-D-glucosamine) Beads 2566.4. Uptake on Crosslinked Bead Cellulose

(without Functionalization) 2576.5. Uptake on Brown Algea Seaweed (Ascophyllum Nodosum) 258

7. DESORPTION OF OXOANIONS 2608. MUTUAL SEPARATION OF OXOANIONS 2609. REFERENCES 261

16. ADSORPTIVE SEPARATION OF TOXIC ANIONS FROM WATERUSING PHOSPHORYLATED ORANGE JUICE RESIDUE 263

Katsutoshi Inoue, Kedar Nath Ghimire, Rabindra Prasad Dhakal ,Kenjiro Makino, and Tohru Miyajima

I. INTRODUCTION 2632. EXPERIMENTAL 264

2.1. Materials 2642.2. Methods 265

3. RESULTS AND DISCUSSION 2663.1. Batch Experiment 266

4. CONCLUSIONS 2735. ACKNOWLEDGMENT 2756. REFERENCES 275

17. DESIGN AND SYNTHESIS OF POWDERED MAGNETICACTIVATED CARBONS FOR AURODICYANIDE ANIONADSORPTION FROM ALKALINE CYANIDE LEACHINGSOLUTIONS 277

Jan D. Miller, Gustavo A. Munoz, and Saskia Duyvesteyn

I. INTRODUCTION 2772. TECHNOLOGICAL LIMITATIONS 2793. ACTIVATED CARBON 2804. MAGNETIC ACTIVATED CARBON (MAC) 2825. EXPERIMENTAL PROCEDURES 283

5.1. SynthesisofMACs 2835.2. Characterization 284

6. DISCUSSION 2857. CONCLUSIONS 2898. REFERENCES 290

xvi CONTENTS

18. EVALUATIONANDMOLECULAR DESIGN OF INORGANICANION SIEVES 293

Masamichi Tsuji

1. INTRODUCTION 2932. EVALUATION OF ANION UPTAKE 294

2.1. Inorganic Solids and Modes of Anion Uptake 2942.2. Method of Anion Uptake Evaluat ion 295

3. CONTROLLING ANION SELECTIVITY OF INORGANIC SOLIDS . 2993.1. Crystal Structure and Ion Selectivity ............................................ 2993.2. Design of Se032. Sieves 300

4. CONCLUSIONS 3065. LISTOF SYMBOLS AND DEFINITIONS 3076. ACKNOWLEDGMENT 3087. REFERENCES 308

19. SILVER INCORPORATION AT THE INTERLAYER GALLERYREGION OF A LAYERED DOUBLE HYDROXIDEINTERCALATED WITH THIOSULFATE ANION 310

Eiji Kanezaki

1. INTRODUCTION 3102. PROCEDURES 3143. RESULTS ANDDISCUSSION 314

3.1. NMR Analysis 3143.2. Thermal Analysis 3143.3. FTIR Spectroscopy ...................................... ................. ................ 3163.4. Powder X-ray Diffraction (PXRD) 3173.5. Regularity of Interlayer Ag+-Thiosulfate Complex 320

4. APPLICATIONS 3215. CONCLUSIONS 3216. ACKNOWLEDGMENT 3227. REFERENCES 322

20. CARBONATEPRECIPITATION ON SAND(a-QUARTZ) 325

Raj P. Singh

1. INTRODUCTION 3251.1. Industrial Significance of Precip itation 3251.2. Separation of Anions via Precipitation/Crystallization 3251.3. Carbonate Precipitation 326

CONTENTS xvii

2. EXPERIMENTAL PROCEDURES 3262.1. Sample Collectionand Analysis 3262.2. Calculationof Supersaturation of Water Samples with

Respect to Calcite 3272.3. Precipitationof Calcium Carbonatefrom Groundwaters 3272.4. ScanningElectron Microscopic (SEM) and Energy Dispersive

Spectrometric (EDS) Analyses 3282.5. X-ray DiffractionAnalysis 3282.6. X-ray FluorescenceAnalysis 329

3. CHARACTERIZATION OF CARBONATE SCALE 3294. CARBONATE (CALCITE) PRECIPITATION 3295. EPITAXIALGROWTHOF CALCITEON SAND (a-QUARTZ) 3316. APPLICATIONS 3377. INHIBITION OF CALCITEGROWTH ON SAND FILTER 3378. SUMMARY 3379. ACKNOWLEDGMENT 33810. REFERENCES 338

ABOUT THEEDITORS 341INDEX................................................................................................................... 343