solvent extraction and liquid membranes

Fundamentals and Applicationsin New Materials SOLVENT EXTRACTION and LIQUID MEMBRANES... CRC Press is an imprint of theTaylor & Francis Group, an informa business Boca Raton London New Y

Fundamentals and Applications

in New Materials

SOLVENT EXTRACTION

and LIQUID MEMBRANES

CRC Press is an imprint of the

Taylor & Francis Group, an informa business

Boca Raton London New York

Fundamentals and Applications

in New Materials

SOLVENT EXTRACTION

and LIQUID MEMBRANES

Edited by Manuel Aguilar José Luis Cortina

6000 Broken Sound Parkway NW, Suite 300

Boca Raton, FL 33487‑2742

© 2008 by Taylor & Francis Group, LLC

CRC Press is an imprint of Taylor & Francis Group, an Informa business

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Library of Congress Cataloging‑in‑Publication Data

Solvent extraction and liquid membranes: fundamentals and applications in new materials / editors, Manuel Aguilar, Jose Luis Cortina.

p cm.

Includes bibliographical references and index.

ISBN 978‑0‑8247‑4015‑3 (hardback : alk paper)

1 Solvent extraction 2 Liquid membranes I Aguilar, Manuel II Cortina, Jose Luis III Title.

We dedicate this book to our esteemed colleague Abraham Warshawsky who passed away during the preparation of his chapter.

Foreword ix

Preface xi

Acknowledgments xiii

About.the.Editors xv

Contributors xvii

Chapter 1 Liquid–Liquid.Extraction.and.Liquid.Membranes.in.the.Perspective.of.the Twenty-First.Century 1

Michael Cox Chapter 2 Fundamentals.in.Solvent.Extraction.Processes:.Thermodynamic,.Kinetic, and.Interfacial.Aspects 21

Hitoshi Watarai Chapter 3 Computation.of.Extraction.Equilibria 59

Josef Havel Chapter 4 Hollow.Fiber.Membrane-Based.Separation.Technology:.Performance.and Design.Perspectives 91

Anil Kumar Pabby and Ana María Sastre Chapter 5 Solvent.Extraction.in.the.Hydrometallurgical.Processing.and.Purification.of Metals:.Process.Design.and.Selected.Applications 141

Kathryn C Sole Chapter 6 Modeling.and.Optimization.in.Solvent.Extraction.and.Liquid.Membrane Processes 201

Inmaculada Ortiz Uribe and J Angel Irabien Gulias Chapter 7 New.Materials.in.Solvent.Extraction 225

Lawrence L Tavlarides, Jun S Lee, and Sergio Gomez-Salazar

The International Solvent Extraction Conferences (ISECs) have been held every

3 years since 1971 in various countries around the world The 1999 conference

Following the activities of the first School in Solvent Extraction in Barcelona in

1986, and coincident with the 1999 International Solvent Extraction Conference

researchers.and.developers.in.the.chemical.industry,.the.mining.and.mineral.pro-cessing industry, and the waste treatment industry The book is also intended for

chemical, metallurgical, mineral processing, and waste treatment engineers who

already.use.this.technique.but.have.a.desire.to.understand.better.or.to.solve.existing

process.problems Furthermore,.the.book.should.be.useful.for.researchers.in.solvent

extraction.who.wish.to.learn.about.its.applications.in.areas.other.than.their.own

Anil Kumar Pabby

Bhabha.Atomic.Research.CentreNuclear.Recycle.Group

Tarapur,.Maharashtra,.India

Yuri Pogorelov

Pridneprovsky.Scientific.CenterUkrainian.Academy.of.SciencesDniepropetrovsk,.Ukraine

Department.of.Chemical.EngineeringUniversitat.Politécnica.de.CatalunyaBarcelona,.Spain

Yuri Shestak

Pridneprovsky.Scientific.CenterUkrainian.Academy.of.SciencesDniepropetrovsk,.Ukraine

Inmaculada Ortiz Uribe

Osaka,.Japan

and Liquid Membranes

in the Perspective of the Twenty-First Century

Michael Cox

Contents

1.1 Liquid–Liquid Extraction 2

1.1.1 Extractants 2

1.1.2 Synergistic Extraction 4

1.1.3 Applications 5

1.1.3.1 Nonferrous Metals 5

1.1.3.2 Precious Metals 10

1.1.3.3 Nuclear Reprocessing 10

1.1.4 Operating Problems 10

1.1.4.1 Extractant Losses 10

1.1.4.2 Solubility Problems—Third-Phase Formation 11

1.1.4.3 Crud 11

1.1.5 Solvent Extraction for Environmental Applications 11

1.1.6 Trends and Future in Solvent Extraction 12

1.2 Liquid Membranes 14

1.2.1 Introduction 14

1.2.2 Surfactant Liquid Membranes 15

1.2.3 Supported Liquid Membranes 16

1.2.4 Applications 16

1.2.4.1 Recovery of Metals 16

Bibliography 17

Books 17

Book Series 18

Conference Proceedings 18

. Liquid–Liquid extraCtion

Liquid–liquid extraction is now very well established, featuring extensively as a

selective separation process Liquid membranes are a more recent development,

Acidic extractants include simple reagents such as carboxylic acids and organo-phosphorus acids, as well as chelating acids The latter are often derived from

analytical reagents, such as β-diketones, 8-hydroxyquinoline, and

on the organophosphorus compounds: alkylphosphates, (RO)3PO;

alkylphospho-nates, (RO)2RPO; alkylphosphinates, (RO)R2PO; and alkylphosphine oxides, R3PO

used in precious metal extraction, and a trialkylphosphine sulfide, R3PS (Cyanex

471X, Cytec Inc., New Jersey), is available commercially Such sulfur donating

extractants will need to be considered when extracting and separating soft

tabLe .

Liquid–Liquid extraction reagents

acids

alkylphosphoric acids

Mono-Di-alkylphosphoric acids and sulfur analogs

Mobil Chemical Co (MEHPA/

DEHPA mixture) Avecia formerly Zeneca Specialties (Acorga SBX50) Daihachi Chem Ind Co Ltd (DP-8R, DP-10R, TR-33, MSP-8)

Bayer AG (BaySolvex D2EHPA, D2EHTPA VP Al 4058)

Albright and Wilson Americas (DEHPA)

Hoechst (PA216, Hoe F 3787)

Fe removal Sb,Bi removal from copper electrolytes Uranium extraction Rare earth extraction Cobalt/nickel separation Zinc extraction, etc.

Alkyl phosphonic

acids

2-ethylhexylphos- phonic acid 2- ethylhexyl ester, and sulfur analog

Daihachi Chem Ind Co Ltd (PC 88A)

Albright and Wilson Americas (Ionquest 801)

Bayer AG (BaySolvex VP-AC

4050 MOOP)

Cobalt/nickel separation Rare earth separation

Alkyl phosphinic

acids

di-alkyl phosphinic acids and sulfur analogs

Daihachi Chem Ind Co Ltd (PIA-8)

Cytec Inc (Cyanex 272, 302, 301)

Cobalt/nickel separation Zinc and iron extraction Aryl sulfonic acids Dinonylnaphthalene

sulfonic acid

King Industries Inc (Synex 1051)

Magnesium extraction

Chelating acid extractants

Hydroxyoxime

derivatives

α -alkarylhydrox- imes (LIX63)

β -alkylarylhy- droxyoximess (LIX860) (M5640)

Cognis Inc formerly Henkel Corp (various e.g., LIX860) Avecia formerly Zeneca Specialties (various e.g., M5640)

Inspec (MOC reagents)

Copper extraction Nickel extraction

8-hydroxyoxine

derivatives

Kelex 100, 120 LIX26

Witco Corp Cognis Inc formerly Henkel Corp

Gallium extraction Proposed for copper extraction

β -diketone

derivatives

LIX 54 Hostarex DK16

Cognis Inc formerly Henkel Corp

Hoechst

Copper extraction from ammoniacal media

tabLe . (Continued)

Liquid–Liquid extraction reagents

phoramide

derivatives

DS 5968, DS 6001 (Withdrawn)

Avecia formerly Zeneca Specialties

Zinc extraction Cobalt/nickel/

manganese separation

Corp

Nuclear fuel reprocessing, iron extraction

Sb, Bi extraction from copper refinery liquors

Adogen 283

Rohm and Haaas Witco Corp

Uranium extraction Proposed for vanadium, tungsten extraction Tertiary amines Alamines (e.g.,

Alamine 336) Adogens

Cognis Inc formerly Henkel Corp

Witco Corp

Uranium extraction Cobalt from chloride media

Tungsten, vanadium extraction, etc.

Quarernary amines Aliquat 336

Adogen 464

Cognis Inc formerly Henkel Corp

Witco Corp

Vanadium extraction Possible chromium, tungsten, uranium, etc.

substituted amide

Iridium separation from rhodium

Corp

Gold extraction from cyanide media

solvating extractants and Chelating nonionic extractants

Carbon–oxygen

donor reagents

Alcohols, (decanol) Ketones (MIBK) Esters

Ethers, etc.

Various chemical companies Niobium/tantalum

separation Zirconium/hafnium separation

Another important application of liquid–liquid extraction for the recovery of

Liquid–Liquid extraction reagents

Albright and Wilson Americas Daihachi Chem Ind Co Ltd Cytec Inc

Bayer AG Hoechst (TBP, DBBP, TOPO) (Cyanex 921 923, 471X) (Hoechst PX324, 320) BaySolvex VP-AC 4046 (DBBP), VP-AC 4014 (DPPP), VP-Al 4059, (DEDP)

U3O8 processing Iron extraction Zirconium/hafnium separation Niobium/tantalum separation Rare earth separation Gold extraction

Sulfur–oxygen

donors

Sulfoxides sulfides Daihachi Chem Ind Co Ltd

(SFI-6) Hoechst (Hoe F 3440) Others

Palladium extraction

in PGM refining

Nitrogen donors Bi-imidazoles and

bi-benzimidazoles Pyridine dicarboxylic ester

Avecia formerly Zeneca Specialties (ZNX 50) Avecia formerly Zeneca Specialties (CLX 50)

Zinc extraction and separation form iron in chloride media Copper extraction form chloride media

Note: This is a historic survey and it is likely that not all of the reagents are currently available or have

been superceded and companies may not still be operating in this field.

and look for new ways of using the existing compounds Thus, combination of

reagents—although currently not favored by the industry—might provide some

Degradation of extractants is important because it affects not only the physical operation but also the chemistry This was recognized a long time ago with the hydrolysis of TBP to give phosphoric acid esters

radation will probably be system specific so it needs to be studied for every system

However, it seems to have been largely ignored recently Note that deg-ing operation

Chemical regeneration of extractants to offset degradation losses dur- 2.Chemical regeneration of extractants to offset degradation losses dur- Diluents

Role poorly understood and choice is often a matter of what is the least expensive available

ents, and modifiers

Basic work is required to study interactions among extractants, dilu-These reagents can also degrade, and often this information is readily available in the organic chemical literature For example, the oxidation

3 Systems

tant as extraction

For real processes stripping the loaded organic phase is just as impor-Most laboratory studies are carried out with dilute solutions, which do not equate to real life in which ionic strength of the leach liquors can be quite high This can affect a number of processing parameters

4 Environment

ates a bad image for liquid–liquid extraction

Potential for release of organic compounds into the environment cre-Removal of trace organic compounds from aqueous raffinates

cycle analysis basis compared with competing technologies

Assess the environmental impact of liquid–liquid extraction on a life-Alternative systems, supercritical fluids, membranes, and so forth where environmental impact could be less

Degradation products affect operating parameters and hence work on systems over a time period long enough to show these problems

Better control of mixing to generate optimum shear

Mixing time based on kinetics to minimize disengagement problems, crud formation, and so forth

Work on real solutions with equipment made of the same material as the eventual plant

large ions such as chromate but not the small monovalent species Ultrafiltration

membranes can retain metal ions when combined with large complexing agents

In spite of these disadvantages emulsion liquid membranes have been widely

organic phase also increases, which slows down the rate of membrane diffusion

J Stary, The Solvent Extraction of Metal Chelates, Pergamon Press, New York (1964).

Y Marcus and S Kertes, Ion Exchange and Solvent Extraction of Metal

C Hanson (Ed.), Recent Advances in Liquid–Liquid Extractions, Pergamon Press, New

York (1971).

V S Schmidt, Amine Extraction, Israeli Programme for Scientific Translations (1973).

T Sekine and Y Hasegawa, Solvent Extraction Chemistry, Marcel Dekker, New York (1977).

T C Lo, M H I Baird, and C Hanson, Handbook of Solvent Extraction, Wiley-Interscience,

New York (1983).

G Ritcey and A W Ashbrook, Solvent Extraction: Part I and II, Elsevier, Amsterdam (1984).

W W Schultz and J D Navratil (Eds.), Science and Technology of Tributylphosphate, 2

K Schügerl, Solvent Extraction in Biotechnology, Springer, Berlin (1994).

R A Bartsch and J Douglas Way (Eds.), Chemical Separations with Liquid Membranes,

American Chemical Society, Washington, D.C (1996).

R Hatti-Kaul (Ed.), Aqueous Two-Phase Systems: Methods and Protocols (Methods in

Bio-technology Series Volume 11), Humana Press, New Jersey (2000).

J Rydberg, M Cox, C Musikas, and G Choppin, Solvent Extraction Principles and Practice

Selected Papers of ISEC ’83, Denver, American Institute of Chemical Engineers

Sympo-sium Series No 238, Vol 80, American Institute of Chemical Engineering, New York

(1984).

Preprints of ISEC ‘86, Munich, DECHEMA, Frankfurt-am Main, 3 vols (1986).

Proceedings of ISEC ‘88, Moscow, Vernadsky Institute of Geochemistry and Analytical

Value Adding through Solvent Extraction, Proceedings ISEC ’96, Melbourne, (D C

Shallcross, R Paimin, and L M Prvcic, eds.), University of Melbourne, 3 vols

found in conferences on hydrometallurgy and specialized conferences concerned

with the recovery of metals from primary and secondary sources Extraction of

organic compounds are also featured in conferences on biotechnology and pharma-ceutical products

Extraction Processes

Thermodynamic, Kinetic, and Interfacial Aspects Hitoshi Watarai

Contents

2.1 Introduction—What Is the Driving Force of Solvent Extraction? 22

2.1.1 Nernst Distribution Isotherm 222.1.2 Classical Extraction Mechanism of Metal Chelate 222.1.3 Modern Extraction Mechanism of Metal Chelate 242.2 Thermodynamics of Solvent Extraction Equilibria 24

2.2.1 Structure-Free Energy Relationship 242.2.2 Theoretical Prediction of Distribution Constant 242.2.2.1 Application of Regular Solution Theory—Solvent

Effect on the Extraction Equilibria 252.2.2.2 Application of Scaled Particle Theory (SPT)—Concept

of Cavity Formation Energy 262.3 Adsorption at Liquid–Liquid Interface 31

2.3.1 Structure of Liquid–Liquid Interface 312.3.2 How to Measure the Interfacial Adsorption 322.3.2.1 Interfacial Tension Measurements 322.3.2.2 High-Speed Stirring Spectrometry 332.3.2.3 Reflection Spectrometry 352.4 Factors Determining the Interfacial Adsorption 36

2.4.1 Capacity of Liquid–Liquid Interface 362.4.2 Correlation between Adsorption Constant and Distribution

Constant 382.4.3 Prediction of Adsorptivity by Computational Simulations 392.5 Solvent Extraction Kinetics and Interfacial Phenomena 40

2.5.1 Modern Techniques for the Measurement of Solvent Extraction Kinetics 422.5.1.1 High-Speed Stirring (HSS) Method 422.5.1.2 Centrifugal Liquid Membrane Method 422.5.1.3 Two-Phase Stopped Flow Method 42