Preface

Solvent extraction (SX) or Liquid-liquid distribution1 techniques have a broad field of

applications: in inorganic and organic chemistry and large-scale industrial separations,

in analytical chemistry, in pharmaceutical and biochemical industries, in waste

treatment. Besides, SX is a good instrument for studying fundamental understanding

of equilibrium and kinetics of complex formation processes. Extraction methods have

now become a routine procedure in separation technologies.

The literature volumes of publications on the subject, and the number of newly

discovered extraction methods, increase every year. Many methods based on chelate

extraction have been considered as routine practice. The hitherto unexplored

potentialities are also very considerable. Extraction is a major tool in the study of the

processes of complex formation and of the state of compounds in solution.

This monograph differs in scope and approach from the recent books by J. Rydberg, M. Cox,

C. Musikas and GR. Choppin (Eds) " Solvent Extraction: Principles and Practice, CRC, New

York, 2004 and GM. Ritcey "Solvent Extraction Principles and Applications to process

Metallurgy", Elsevier, 2006

which give a detailed modern treatment of the extraction processes and is

therefore an excellent reference works.

1
IUPAC designation, but in this book more commonly term Solvent Extraction is used.
The book consists of two parts. The first presents the fundamental 2 principles of

solvent extraction processes and practice during the last decade. The second part

presents the novel principles for Extraction processes and examples of application

these principles in interpretation experimental data at carboxylic acids and metals

solvent extraction. A more detailed treatment has been reserved for the subjects which

have been studied by the author and his colleagues over the last decade. Some

unpublished data have also been included. Special stress has been laid on the general

theory of extraction, on extraction of coordination-unsaturated and charged complexes

and on the methods of determination of the composition of the extracted compounds.

In studying the theoretical aspects of extraction , the chemist often has to deal with a

number of interconnected problems. He has to consider the original form in which the

specie exists in the aqueous solution, all the stages of the interaction with the

extractants and the solvents, the states of the extractant and the complex compound

in aqueous and organic phases.

Topics concerned with extraction, calculation and analytical techniques

were mentioned only at description of novel theory. Specific subjects treated include

the techniques of increasing the selectivity of the extraction, ways of effective

combination of the extraction with subsequent determination methods, characteristic

features of the extraction of this class of compounds, and radiochemical methods.

Table of Contents

Preface
Contents
2 *
In the book we use more often the nomination "classical" taking in mind modern fundumental principles of
extraction..
 1. Introduction

Part I. Conventional (Classical) Principles and Practice of Solvent Extraction.

Chapter 1 Conventional (classical) fundamental principles of solvent extraction

1. Introduction

2 Solvent Extraction by solvation

2.1 Solubility of liquids

2.2. Mixture of solutions

2.2.1. Ideal mixtures
2.2.2. Real mixtures
2.3. Solute – solvent interactions (Extractability)

2.3.1. The Solubility Parameters

2.3.2. Thermodynamic relations

3. Solvent extraction with chemical reactions (by complexation).

3.1. Thermodynamics of extraction systems

3.2. Solute-solvent interactions in aqueous phase

3.2.1. Dissociation

3.3. Solute-solvent interactions in organic phase

4. Driving forces of Solvent extraction

5. Influence of Kinetics factors

5.1 Diffusion transport regime
5.1.1 Mathematical description of the diffusion transport.
5.1.2 Determination of diffusion coefficients
5.1.3 Examples of analysis of diffusional transport.
5.2 Chemical reactions kinetics regime
5.2.1 Complexation-decomplexation
5.2.2. Liquid-liquid interface
5.2.3. Mathematical description of kinetic regime transport
5.2.4 Determination of kinetic parameters.
5.2.4.1. Determination of α (Dimensionless parameter which relates diffusion limited
transport to kinetically limited transport).
5.2.4.2. Determination of Activation Energy.
5.3. Mixed diffusional-kinetic transport regime.
5.3.1. Identification of the rate-controlling transport regimes.
5.3.2. Basic parameters of transport regime
5.3.3. Determination of transport parameters.

6. Selectivity

7. Factors, affecting extraction

7.1 Influence of extractant properties

7.1.1 Mixtures of extractants (Ionic Additives).

7.2 Influence of dissociation constant and partition coefficient of the extractant

7.2.1 Acidity-basicity of the extractant influencing extraction

7.2.2 Influence of dissociation constant and distribution coefficient of the extractant
7.3 Aggregate formation

7.4 Solvent (Diluent) properties influencing extraxtion

7.5 Coupling ions. Anion Type

7.6 Influence of temperature

7.7 Structural considerations Influence of complex structure

7.7.1 Chelate Ring Size

7.7.2 Steric Hindrance effect

7.7.3 Donor Ligand Effects

7.7.4 Inner and Outer Sphere Coordination effect

7.8 Effects of the Aqueous Medium

8. Module design considerations Process (module) design
8.1. Calculation of equilibrium constants

8. 2 Identification of Species

8.2.1 Job’s Method

8.2.2 Ligand number method

8.2.3 Graphic Slope Analysis

8.2.4 Linear plots
8.2.5 Nonlinear Plots
8.2.6 Numerical methods

9. Experimental determination of Distribution ratios

9.1 Stirred Cell Semicontinuous Techniques

10. . Centrifugal Extraction-Separation Systems

11. . Summerizing remurks

12. References

Chapter 2. Principles of Solvent Extraction of Organic and Mineral acids

1. Introduction
2. Extraction of acids by carbon-bonded oxygen-donor extractants and
substituted hydrocarbon solvents
2.1. Thermodynamic (mass action law) extraction equilibria

2.1.1. Dissociation of the acid

2.1.2. Protonation

2.1.3. Dimerization

2.2. Mutual solubilities and Phase Miscibilities

2.3. Parameters of aqueous phase

2.4. Organic phase parameters

2.5. Thermodynamic functions of transfer
 3. Phosphorus-bonded oxygen donor extractants
3.1 Mass action law equilibria
3.2. Extraction characteristics

4. Aliphatic amine extractants

4.1. Mass action law equilibria

4.2. Extraction characteristics

5. Extraction of strong (inorganic) acids

6. Summerizing remarks

7. References

Chapter 3. Chemistry of Metals Solvent Extraction

1. Introduction
2. Metal Extraction by Cation Exchangers (Acidic Extractants)
2.1. Thermodynamic considerations
2.2. Stoichiometry and Structure of Extracted Species
2.3. Properties of Extractants
2.4. Influence of temperature
3. Metal Extraction by Anion Exchangers (Ion pair Formation)
3.1. Equations for Liquid Anion Exchange Extractions

3.2. Properties of Liquid Anion Exchangers

4. Extraction through formation of H-bonding and solvating complexes.

4.1. Extraction of Metal Complexes

4.1.1 Formation of metal – organic complexes of type MLzEb

4.1.2 Extraction of mineral salts

4.1.3 Extraction by MLz(HL)b type complexe (self-adducts)sformation

4.2. Properties of Extractants

5. Extraction through Mixed Complex Formation

5.1. Acid Extractants

5.1.1. Acid Extractants and Neutral Donor Molecules.

5.1.2. Two Acidic Extractants

5.1.3. Acid – Base (Amine) mixed Extractants

5.2. Mixed two amines extractants

5.3. Mixtures of Solvating Ex tractants

6. Extractable Complexation of monovalent metals

7. Extraction with Aqueous Biphasic Systems

8. References

Chapter 4. Engineering development of Solvent Extraction processes.

1. Introduction
2. Extraction stage
2.1. Single stage process
2.2. Stage-wise Cross-Flow systems.
2.3. Countercurrent extraction
2.4. Scrubbing

3. Striping organic solutions

3.1. Regeneration of organic phase

4. Extraction efficiency
4.1. Efficiency in a single stage
4.2. Efficiency in a cascade

5. Equpment design for continuous extraction-stripping processes

5.1. Dispersion and mixing of the phases: types of mixers

5.1.1. Agitated extractors

5.1.2. Pulsing mixers

5.1.3. Centrifugal mixer-settler

 5.2. Separation of the phases
5.3. Differential Extraction

6. Solvent losses
7. Economic considerations
8. Problems with scale up to industrial systems
9. References

Chapter 5. Examples of Application of Solvent Extraction techniques in Chemical,

Radiochemical, Biochemical, Pharmaceutical, Analytical Separations and Wastewater
treatment.

1. Introduction

2. Extraction in Hydrometallurgy (Metals extraction)

2.1. Metal ion-extractant complexes formation

2.2. Types of metal extractants

2.2.1. Chelation Extractants

2.2.2. Organic Acid Extractants
2.2.3. Ligand Substitution Extractants
2.2.4. Neutral or Solvating Extractants
2.2.5. Ion-Pair Extractants

2.3. Modifiers

2.4. Synergistic Mixtures

2.5. Diluents

2.6.Copper extraction

2.6.1. Laboratory scale reaserch

2.6.1.1. Hydroxyoxime copper extractants.

2.6.1.2. Quinoline-based copper extractants

2.6.1.3. β-Diketone copper extractants

2.6.1.4. Solvating, nitrogen-based extractants

 2.6.2. Industrial scale copper extraction

2.7. Cobalt – Nikel Solvent extraction

2.7.1. Laboratory scale Cobalt-Nikel extraction

2.7.1.1. Cobalt-Nikel anion exchange extractants

2.7.1.2. Co-Ni extraction by acidic extractants

2.7.2. Industrial scale solvent extraction of Co-Ni

2.7.2.1. Bulong Process.

2.7.2.2. Cawse Process
2.7.2.3. Murrin-Murrin Process

2.8. Precious group metals (PGM) extraction

2.8.1. Extraction of Gold

2.8.2. Extraction of Silver

2.8.3. Extraction of Palladium and Platinum

2.8.4. Extraction of Indium and Rhodium

2.9. Lanthanide Extraction

2.9.1. Solvating extractants for lanthanides

2.9.2. Amine Extractants

2.9.3. Acidic Extractants

3. Solvent Extraction in Nuclear Chemistry and Technology

3.1. Solvent Extraction in Nuclear fuel processing

3.1.1. Uranium production

3.1.2. Thorium production from its ores
 3.2. Spent Nuclear fuel Recycling (Reprocessing)

3.2.1. Purex Process recycling.

3.2.2. Other reprocessing flow sheets

3.2.3. Reprocessing of Irradiated Thorium Fuels

3.3. Nuclear waste management

3.3.1. TRUEX process

3.3.2. SREX process: Extraction of 90Sr and 134,, 135, 137Cs from acidic Wastes
3.3.3. Phosphine oxide process
3.3.4. Cobalt dicarbollide processes
3.3.5. Universal solvent extraction process
3.3.6. Bifunctional organophosphorus compounds for waste treatment
3.3.7. Monofunctional Organophosphorus Reagents for waste teatment

3.4. Solvent Degradation and Regeneration

3.5. New developments

3.5.1. Partitioning of Wastes
3.5.2. Trivalent Actinide-Lanthanide Group Separations

4. Solvent Extraction in Analytical Chemistry

4.1. Solvent Extraction in samples Preparation and Pretreatment techniques.

4.1.1. Solvent Extraction for Separation Steps
4.1.2. Preconcentration for Trace Element Determination
4.1.2.1. Preconcentration of inorganic compounds
4.1.2.2. Preconcentration and separation of Organic compounds

4.2. Extraction in analytical determination techniques

4.2.1. Methods Based on Spectrophotometric detection

4.2.2. Other detection techniques (Atomic Absorption, Flame Emission

Spectroscopy, X-ray Fluorescence, etc.)

4.3. Basical materials for Solvent Extraction techniques.

4.3.1. Solvent-Impregnated Resin

4.3.2. Solid-Phase Spectrophotometry Applications

4.3.3. Applications for Fiber Optic Chemical Sensors

4.4. Micelles in Analytical Chemistry

4.5. Liquid Membranes in Analytical Chemistry

4.6. Chromatography based Analytical Techniques

4.6.1. Liquid–Liquid Partition Chromatography (LLPC)

4.6.2. Supercritical Fluid Extraction (SFE)

4.6.2.1. Off-line, On-line SFE
4.6.2.2. On-line coupling SFE-GC, SFE-SFC

4.7. Solvent Extraction in Continuous Flow Injection Analysis (FIA)

4.8. Solvent Extraction in Nuclear analytical applications

4.8.1. Preparative techniques for radioactive elements
4.8.2. Radiometric techniques
4.8.2.1. Activation analysis
4.8.2.2. Isotope Dilution Radiometry
4.8.2.3. Liquid Scintillation Counting

5. Application of Solvent Extraction in Biochemical and Pharmaceutical

Separations

5.1 Application Solvent Extraction in Biochemical Separations

5.1.1. Extraction of carboxylic acids
5.1.1.1 Citric acid
5.1.1.2 Acetic acid
5.1.2. Extraction of amino acids
5.2. Separation and purification of drugs
5.3. Life-Science Products
6. Solvent Extraction in Separation of organic compounds
6.1. Petroleum and Petrochemical Processing

6.1.1. The Union Carbide Process

6.1.2. Re-refining Process

6.2. Separation of Isomers

6.2.1. Separation of m-Xylene from o- and p-Xylene

6.2.2. Separation of Alkylnaphthalene Isomers Using Cyclodextrins

6.2.3. Separation of m- and p-cresol isomers

7. Solvent Extraction in Waste treatment

7.1. Solvent Extraction in Metal waste treatment

7.1.1. Treatment of Acidic Metal waste Solutions

7.1.1.1 Extraction of Zinc from Weak Acid Effluents

7.1.1.2. . Extraction of Nickel from Cadmium Electrolytes
7.1.1.3. Extraction of Zinc and Chromium(III)from Electroplating Baths 7.1.1.4.
Extraction of Copper and Zinc from Brass Mill Flue Dust
7.1.1.5. Extraction of Chromium(VI) from Surface Finishing Wastewater
7.1.2. Solvent Extraction from Ammoniacal Feed Solutions
7.1.2.1. Recovery of Nickel and Cadmium from Accumulator Waste
7.2. Recovery of acids from waste by Solvent Extraction
7.2.1. Recovery of Hydrofluoric and Nitric Acids from Stainless Steel Pickling Baths
7.2.2. Purification of Green Phosphoric Acid (H3PO4) to food grade quality
7.2.3. Removal of Arsenic Acid (H3AsO4) from Copper Electrolytes
7.2.4. Cyanide Recovery by Solvent Extraction
7.3. Separation of organic pollutants by Solvent Extract6ion
7.3.1. Phenosolvan Process

8. Nomenclature

9. Acronym list, Symbols, Subscripts

10. References

Part II. Novel Competitive Complexation/Solvation Theory of Solven Extraction. Principles

and Practice

Chapter 6. Backgrounds of the competitive complexation/solvation theory (CCST) of

solvent extraction.
1 Introduction.
2 Complexation through the H-bonding and proton transfer.

3 Distribution isotherm.

4 Modified Competitive Preferential Solvation (COPS) theory.

5 Electronic Acid-Base Theory and Amphoterity.

6 Aggregation.

7 References

Chapter 7. Competitive Complexation/Solvation Theory (CCST) of Solvent

Extraction: General Mechanisms and Kinetics
1 Basic Statements
2 Extraction systems with low solute concentrations in organic phase
3 Systems with medium concentrations of the solute
4 Systems with high solute concentrations.

5 Comparison of Conventional and Presented Theories Description.

6. Summarizing Remarks for the CCST.

7. Nomenclature
8. References

Chapter 8. CCST in Engineering design, procedures and calculations

1 Introduction

2. Engineering considerations in experimental investigation of CCST

3. Experimental Techniques for the Presented Theory.

4. Determination of Extraction constant and its comparison with CCST Affinity

constant ratios.

5. Analytical methods used for the CCST verification.

6. Transferability of the values of affinity constant ratios

7. References
Chapter 9. Solvent Extraction of Acids by Amine based Extractants.

1. Introduction

1.1. Interaction mechanisms

1.2. Acids' extraction modeling by CCST

1.3. Active solvents

1.4. Influence of Temperature

2. Acid-Amine systems in the CCST interpretation.

2.1. The acid-amine (in inert diluent)-water (S-E-W) system

2.2. The system with mixture of two acids; selectivity

2.3. The system with the mixture of two amines.

3. . The systems with active solvent as an additive.

kSE k CSorg C Aorg

 AE 
3.1. Case 1: kSW k AW and C Saq C Aaq

kSE k CSorg C Aorg

 AE 
k
3.2. Case 2: SW k AW but
C Saq C Aaq

3.3. High acid concentrations

kSE k CSorg C Aorg

 AE 
k
3.4. Case 4. SW k AW and
C Saq C Aaq

4. Experimental application of the CCST in carboxylic acids extraction

4.1. Acetic acid extraction

4.2. Lactic acid extraction

4.3. Citric acid extraction

4.4. Active solvent-swing regeneration thechnology.

4.5. Modifying effect of active solvents.

4.6. Temperature-swing regeneration

5. Summerizing Remarks

6. Nomenclature

7. References

Chapter 10. Competitive Complexation/Solvation Theory (CCST) in Metal Solvent

Extraction

1. Introduction

2. CCST basic statements

2.1. Stepwise solvation-complexation interactions

2.2. Competition between basic interactions at extraction

2.3. Acid-base interaction model and Amphoterism

2.4. Aggregation

3. Mathematical supplement for the CCST in metal extraction

3.1. General considerations

3.2. Analysis of the M-E-W system

3.3. Analysis of more complicated Extraction Systems.

3.4. Independence and Transferability of Affinity Constant Values

3.5. Comparison of Conventional and CCST Mathematical Descriptions

4. Experimental verification of the CCST approach

4.1. Experimental techniques used with the CCST

4.2. Titanium(IV) extraction by DEHPA

4.3. Divalent cations extraction

5. Summarizing Remarks for the Presented Theory.

6. Nomenclature

7. References

Chapter 11. Final Remarks on the Competitive Complexation/Solvation Theory of Solvent

Extraction and its Application.

Part III. Modern and Future Trends in Fundamentals and Applications of Solvent Extraction.

Chapter 12. Modern and Future Trends in Fundamentals of Solvent

Extraction
1. Introduction
2. Novel molecular models theoretical approach

3. Low energy reactions measurement

4. Expected advances in Kinetics studies

5. Supramolecular (SUPRAS) theoretical approach

5.1. Supramolecular solvent formation

5.1.1. Principles of self-assembly

5.1.2. The first self-assembly process( Self-assembly of amphiphilic molecules)

5.1.3. Second Self-assemble: from nanometer-sized amphiphilic aggregates to

micrometer-sized. Liquid phases separation

6. References

Chapter 13. Advances in Development of Solvents for Liquid-Liquid Extraction

1. Introduction
1.1. Strategies for Solvent Replacement
2. Organic Solvents
3. Water as a solvent

3.1. Subcritical Hot Water as a Solvent for Extraction

4. Renewable Water-based Solvents

4.1. Aqueous Two-Phase Systems as extractants

4.2. Supercritical Fluid Extraxtants (SFE)

5. Ionic Liquids (IL) as Solvents for Extraction

5.1. Properties of Ils

5.1.1. Toxicology considerations

6. Amphiphilic compounds (Supramolecules) as solvents in solvent extraction

6.1. Surfactants
6.2. . Toxicity of surfactants
7. Recovery of reagents
7.1. On-line decontamination of wastes
8. Future trends in the development of new solvents
9. Concluding remarks
10. References

Chapter 14. Recent Advances in Solvent Extraction Processes and Techniques

1. Introduction

2. Equipment design and scale-up considerations

3. Supercritical Fluid Extraction

3.1. Application of SFE

3.1.1. Separation of Mono- from Triglycerides

3.2. Supercritical Chromatography

3.3. Advantages and Disadvantages of Supercritical Extraction

4. Subcritical hot Water extraction

4.1. Extraction technique

4.2. Extraction from plants using SWE

4.3. Pressurized Liquid Extraction (PLE)

4.4. Superheated Water Chromatography

5. Aqueous Two-Phase Systems

5.1. Application of the process

6. Extraction processes with Ionic liquids

6.1. Ils in separation techniques

6.2. Ionic Liquids in Analytical Separations

7. Liquid Membrane and Nondispersive, membrane-based Solvent Extraction techniques.

8. Supramolecular-based Extraction techniques.

8.1. Nano- and microtechnological extraction

8.2. Surfactant-Based Extraction

8.3. Solvent Extraction with Microemulsions

8.3.1. Metal ion extraction with microemulsion

8.3.2. Extraction of Biological Molecules

8.3.3. Potential Applications of Micellar Extraction

8.3.4. Scale-Up Considerations

8.4. Micellar Liquid Chromatography

9. Solid-liquid extraction systems

9.1. Solid phase Extraction (SPE)

9.2. Solvent impregnated resins

9.3. . Solid-phase microextraction

10. Assisted Solvent Extracion

10.1 . Microwave-assisted extraction.

10.2. Ultrasound-assisted extraction

11. Extraction of gas in analytical applications

12. References
Index