During the past 10 years, there have been incremental advances in the application of solvent extraction to process hydrometallurgy. The most cited areas in the literature include chemistry, chemical engineering, pilot plants, and plant operation. Within these areas, there were considerable interest in synergism, diluents, degradation, contactors, surfactants, hydrometallurgical applications, environmental and secondary applications, and health and safety. The summary to the present is followed by a prediction for the future in the above areas of interest. These include the use of speciation; improved understanding of the role of surfactants on the system; optimization through modelling, pilot plants, and contactor selection; improvements in plant operation; further new applications; and plant safety. The review has indicated that considerable knowledge is now available to optimize and improve on process design and plant applications.

The largest solvent-extraction plant in the world at the time, the Nchanga Copper Operation, was in Zambia. The first commercial process using solvent extraction for the refining of the platinum-group metals was in South Africa. More recently, the Southern African region has seen the implementation of solvent extraction for other base metals, precious metals, and specialty metals. These include the world firsts of primary production of zinc at Skorpion Zinc in Namibia and the large-scale refining of gold by Harmony Gold in South Africa. Several other flowsheets that use solvent-extraction technology are currently under commissioning, development, or feasibility study for implementation in this part of the world, including those for the recovery of copper, cobalt, nickel, tantalum, and niobium.

The development of pressure and bioleaching processes for high grade copper ores and concentrates will result in copper solvent extraction plants treating solutions with high copper and acid concentrations at temperatures up to 45癈 and these copper solvent extraction plants will run with reagent concentrations up to 40 vol.%. There is also a trend to use copper stripping solutions with less acid than typically used in recent years. Cognis has developed a model that accurately predicts the copper strip point for virtually any copper solvent extraction reagent or combination of reagents under a wide variety of conditions. The equilibrium strip points for several well known commercial copper solvent extraction reagents are given as a function of reagent concentration, the copper and acid concentration of the strip aqueous, and the temperature. It is shown that the equilibrium strip point is not a straight line function of reagent concentration and that the equilibrium strip point increases with an increase in temperature. Copper extraction also increases as the temperature increases.

Solvent extraction is now finding applications in a broader range of fields than the past. Many of these applications require process equipment with shorter contact times, and in some cases to the point where the traditional equilibrium stage approach is not a good model for predicting performance. In addition, feed streams are becoming lower in concentration of the solute. This means greater feed to solvent flow ratios are being used and so loss of organics as entrainment in the feed is more of a concern both economically and environmentally. These trends mean that a greater emphasis is being placed on the kinetics of extraction and stripping in models to predict performance and on formation and coalescence of drops to control entrainment. This paper reviews recent advances in the tools for investigating kinetics and coalescence in solvent extraction processes and some of the insights that are being uncovered in these fundamental processes in solvent extraction technology.

In most organics extraction processes, the commonly used solvents employ solely physical interactions. Therefore, for the recovery and purification of products from complex mixtures, the selectivity and/or capacity of classical solvents towards the desired solutes is usually insufficient, enforcing the need for complex and thus expensive separation schemes. Significant simplification and cost-reduction can be achieved when affinity solvents would be available that are able to recognize the solutes of interest by their molecular structure. The main development challenges to establish such affinity solvents are: Selection and incorporation of molecular recognition and complexation capabilities; Evaluation of extraction capabilities; Efficient recovery and recycling of the affinity solvents; Implementation in industrial extraction equipment. This paper presents how these development challenges are addressed at the University of Twente, going all the way from affinity solvent design and synthesis, via high throughput screening and characterization up to pilot plant evaluation. Essential in the successful development of affinity solvents are structural cooperations with molecular chemists and custom synthesis companies for their design and synthesis. The various aspects are illustrated by several examples where newly developed environmentally benign affinity solvents appeared able to create major breakthroughs. The applications addressed involve oxygenates, sugars, and pharmaceutical ingredients, such as optical isomers and biomolecules.

A comprehensive review of recent advances in study on thermodynamic models for real electrolyte solutions is presented. The differences between primitive and non-primitive electrolyte models are demonstrated. Some new thermodynamic models for electrolyte solutions based on the mean spherical approximation and perturbation theory are introduced. An extended scaled-particle theory and modified Clegg-Pitzer equation are presented for physical and chemical absorption processes with mixed solvents, respectively. A pseudo one-component two-Yukawa equation of state is used for the aqueous two-phase extraction process in charged colloidal systems.

Ionic liquids are a distinct sub-set of liquids, comprising only of cations and anions, often with negligible vapor pressure. As a result of the low or non-volatility of these fluids, ionic liquids are often considered in liquid/liquid separation schemes where the goal is to replace volatile organic solvents. Unfortunately, it is often not yet recognized that the ionic nature of these solvents can result in a variety of extraction mechanisms, including solvent ion-pair extraction, ion exchange, and simultaneous combinations of these. This paper discusses current ionic liquid-based separations research where the effects of the nature of the solvent ions, ligands, and metal ion species were studied in order to be able to understand the nature of the challenges in utilizing ionic liquids for practical applications.

Reverse micelles create unique environment in organic media. They are capable of solubilizing hydrophilic biomolecules (e.g., proteins, peptides, amino acids, and DNAs) in their aqueous interior. This feature brings about the practical use of biomaterials in organic media because reverse micelles solubilize them with the intrinsic activity. In this paper, we focus on recent two topics concerning protein extraction and chiral separation of biomolecules using liquid membranes. In the first topic, we present recent attempts to extract proteins from an aqueous solution into isooctane using reverse micelles, and some important operational parameters to achieve an efficient protein transfer are discussed. Furthermore, novel function of reverse micelles as a protein activation medium is introduced. In the reverse micellar phase, denatured proteins were completely reactivated in the reverse micellar solution. The reverse micellar technique is found to be a useful tool not only for protein separation but also for protein refolding. Furthermore, we found that a cyclic ligand carixarene has an extraction ability to set up optimum conditions for protein transfer. In the second topic, we have found that a supported liquid membrane (SLM) encapsulating enzymes shows high enantioselectivity (enantioselective excess value is over 96%) in the transport of racemic pharmaceutical compound ibuprofen. A different experiment also suggests that the α-chymotrypsin-catalyzed reactions droved the enantioselective transport of L-phenylalanine based on the enantioselectivity of the enzyme. The SLM encapsulating the surfactant-enzyme complex enabled the highly enantioselective separation of racemic mixtures. It can be envisioned that arrangement of appropriate enzymes in the SLM system will allow enantioselective separation of various useful organic compounds.

In this paper we report results from on-going theoretical and experimental studies carried out jointly at Imperial College London and University College London. Laser-induced fluorescence (LIF) is used to investigate liquid-liquid phase inversion experimentally and to observe in detail phenomena that accompany the inversion process, such as secondary dispersions and drop coalescence and breakup. Theoretically, a two-region model together with a criterion based on a dynamic balance between drop coalescence and breakup is employed to predict phase inversion. The concept of a radial distribution function for hard spheres was also utilized in order to better model the interaction of drops at high dispersed phase holdup. The modeling work is capable of predicting the existence of ambivalent ranges which are in good agreement with experimental observations.

The objective of the integrated approach is to minimize the cost and duration of the development of the final flow sheet by optimal allocation of the resources to various steps of the development. In the integrated approach, the development of a solvent extraction (SX) flow sheet is done in the following order: 1) Definition of the process: composition of the feed, specification of the product, minimum yield, etc.; 2) Selection of the solvent(s) and studying its chemical and physical properties; 3) Design of the optimal flow sheet using a computer simulation; and 4) Combination of process definition and the results of both the simulation and the laboratory experiments for every battery yields the right type of equipment. Experimental proof of the recommended flow sheet, in the adequate equipment, follows—first in a bench-scale, and then in a full scale pilot or demonstration plant. Following of these simple rules ensures a successful development of the process.

The technique state to design counter-current extraction columns is based on the performance of pilot plant experiments. The modelling is then either with the equilibrium or dispersion model, whereas in the latter the dispersion coefficient accounts for all hydrodynamic non-idealities. A new approach uses single droplet experiments to obtain the basic laws and functions governing droplet breakage, coalescence, relative velocity, and axial dispersion when using droplet populance balance models (DPBM). The hydrodynamics simulation results show that the mean Sauter diameter, hold-up, and concentration profiles could be well predicted, which promotes the use of DPBM models for further applications in industrial scale.

This paper presents the process flow sheet of the main nuclear industrial units in Brazil and discusses some solvent extraction technical support required for these plants. The Center for the Development of Nuclear Technology—CDTN has been investigating alternative ways to supply the nuclear industry in order to improve the industrial processes. Some case study examples are presented, Emulsion from Uranium Solvent Extraction Plant and Itataia Uranium Developments. In Caitité industrial plant the water recirculation has caused continuous changes in the composition of pregnant liquor mainly in the sulfate and chloride concentrations. After some water recirculation cycles, a decrease in the uranium extraction efficiency was noted which was followed by the formation of stable emulsion at the uranium extraction stage. Itataia Uranium Developments were performed in a pilot plant for Itataia ore. This ore has the uranium mineral associated to the phosphate. The process consists of four main steps: 1) phosphate concentration, 2) chemical digestion of the concentrate to produce phosphoric acid with dissolved uranium, 3) uranium recovery, and 4) phosphoric acid purification by solvent extraction.

The aqueous solutions are evaluated as sustainable reactive extraction solvents for the recovery of monohydroxyl alcohols (benzyl alcohol, 1-hexanol, cyclohexanol) present in few-percent concentrations in apolar hydrocarbons (toluene, n-hexane, and cyclohexane) by considering two approaches. An aqueous solution containing a reactive extractant, like borate salts, borate complexes, a monosalt of dicarboxylic acid, hydroxypropyl-cyclodextrins, and silver nitrate, shows limited potential to be used. Another approach, in which the alcohol is chemically modified prior to the extraction into an easy-extractable form, in this case a monoester/carboxylic acid, shows much more potential. An environmentally benign aqueous solution of sodium hydrogen carbonate can provide a distribution ratio of benzyl alcohol up to 200, leaving the solubility of the organic solvent in the aqueous solution unchanged relative to pure water and therefore increasing the selectivity with two orders of magnitude. The modification of aromatic, cyclo-aliphatic, and linear aliphatic alcohols can be performed efficiently in the apolar organic solvent without need for a catalyst. The recovery of the modified alcohol can be performed by back-extraction in combination with a spontaneous hydrolysis.

Two new spectroscopic methods to detect the optical activity of liquid-liquid interfaces have been developed. The first one is the centrifugal liquid membrane (CLM) method combined with a conventional circular dichroism (CD) spectropolarimetry and the second one is a more interfacial specific second harmonic generation CD (SHG-CD) spectrometry. In the CLM-CD method, a cylindrical glass cell containing small amounts of organic and aqueous phases was rotated at about 7000 r/min in a sample chamber of a CD spectropolarimeter to generate an interface with a high specific interfacial area between the two-phase liquid membranes. The CD spectra of the J-aggregate of protonated 5,10,15, 20-tetraphenylporphyrin formed at the toluene-sulfuric acid interface have been measured. As for the SHG-CD, a circularly polarized wavelength-variable fs-laser system was constructed to measure the interfacial SHG spectra of a flat liquid-liquid interface. The ion-associated aggregation of a water-soluble anionic porphyrin promoted with a cationic amphiphile at the heptane-water interface was observed by this technique and the observed SHG-CD spectra proved the generation of a characteristic optical activity accompanied by the formation of the interfacial aggregate of inherently achiral porphyrin molecules. These methods will pioneer a new field of interfacial chiral chemistry in the studies of solvent extraction mechanisms.

A series of organo-ceramic adsorbents have been synthesized by a sol-gel processing technique for metal ion extraction. These adsorbents generally have significantly high metal uptake capacities, good physical-chemical stabilities, and well-designed pore geometries compared to other pre-existing metal-chelating ceramic-based adsorbents. This work describes the synthesis and evaluation of pyrazole and calix[4]arene crown adsorbents for selective separation of platinum, palladium, and gold and cesium ions, respectively, from solutions. These materials exhibit mesoporous properties with high surface areas and pore volumes. The sol-gel synthesis starting with precursor silanes and titania results in gel particles of desired pore characteristics and high capacity and stability. Characterization studies, such as adsorption isotherms, breakthrough curves for fixed bed operation, and material stability, show promising results for applications to metal sepation.

During the last decade, China rare earth (RE) industry has made significant progress and become one of the most important producers in the world. In this paper, the recent developments in both fundamental research and industrial application are briefly reviewed: (1) the development and application of Theory of Countercurrent Extraction, (2) the novel solvent extraction process and its application in industry for separating heavy rare earth elements (Tm, Yb, Lu), yttrium (Y), and scandium (Sc), (3) the on-line analysis and automatic control of countercurrent extraction, (4) the eco-friendly process for RE/Th separation of bastnasite in Sichuan Province and electrochemical process for Eu/RE separation, and (5) the optimized flowcharts for typical rare earth minerals in China.

A novel three-liquid-phase extraction system (TES) composed of butyl acetate, block copolymer polyethylene oxide-polypropylene oxide-polyethylene oxide and ammonium sulphate aqueous solution [(NH4)2SO4] as top, middle, and bottom phase, respectively, has been developed. The copolymer recycling and partitioning behavior of penicillin V has been studied in this system. Results show that the copolymer could be purified and recycled and penicillin V of the filtrated ferment broth could be partitioned unevenly among the phases and purified in the top phase of this TES. About 90 wt.% of penicillin V could be distributed into the top phase around pH 2.5 and only less than 0.1 wt.% left in the bottom phase.

The effect of copper concentration on the performance of the catalytic reaction between silicon and methyl chloride was investigated using online gas chromatogram. The catalyst concentration greatly influences various aspects of the direct organosilane synthesis process, including the reaction rate, the selectivity, and the silicon conversion. The reaction activity and the silicon conversion increase as the catalyst concentration increases. However, the reaction selectivity decreases for the catalyst concentrations more than 9 wt.%. The cross-sections of deactivated contact mass particles were observed by optical microscopy and analyzed by scanning electron microscope combined with energy dispersive X-ray detector (SEM-EDX). The observations showed that a textured substance formed on the original flat surface of the silicon particles after deactivation with copper only in a shallow surface layer of the contact mass. This indicates that the copper diffusion is the rate limiting step which causes the reaction deactivation.