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Solvent Extraction in Hydrometallurgy

Solvent Extraction in Hydrometallurgy

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Published by Yogeshwar Gupta
solvent extraction
solvent extraction

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Published by: Yogeshwar Gupta on May 29, 2013
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11
Solvent Extraction in Hydrometallurgy
MICHAEL COX*
University of Hertfordshire, Hatfield, Hertfordshire,United Kingdom
11.1 INTRODUCTION
The use of solvent extraction as a unit operation in hydrometallurgy nowextends to a wide range of metals from a variety of feed materials includinglow-grade ores, scrap and waste, and dilute aqueous solutions. The tech-nology was pioneered inthe1940s for theextraction ofuranium from its oresand, later, for the treatment of wastes from spent reactor fuel, still animportant use of the technique today (seeChapter 12). The knowledgegained led to processes for the recovery of other high-value metals and theseparation of elements such as the rare earths, zirconium–hafnium, andniobium–tantalum that, before the introduction of this technology, could beseparatedonly by lengthy batch techniques with many recyclesteps to obtainthe desired purity. Gradually, solvent extraction was seen to have applica-tions for the recovery of other less valuable, but important, metals such ascobalt and nickel. At the time, the process was confined to rather smalloperations. It was only after the development of selective chelating acidicreagents in the 1960s that liquid–liquid extraction was seen to be a com-mercially viable addition to the unit operations of hydrometallurgy and wasable to compete with alternative processes like cementation.
{
Liquid–liquid
*Retired.
{
Cementation
is the process of recovery of metals from dilute aqueous solution by reductiveprecipitation using another metal with a more negative electrode potential, e.g., Cu
2+
+Fe
o
?
Cu
o
+Fe
2+
. The product, in this case ‘‘cement’’ copper, is relatively impure because of iron contamination. However, cementation can be used in conjunction with a solvent extractionflow sheet to remove small amounts of a metallic impurity, for example, removal of copper froma nickel solution by cementation with nickel powder. Here the dissolved nickel convenientlyaugments the nickel already in solution.
Copyright © 2004 by Taylor & Francis Group, LLC
 
extraction is now an economic alternative to pyrometallurgy for metalextraction, especially when physical beneficiation of the ore to provide asuitable concentrate for smelting is difficult. The alternative hydrometal-lurgical route(Fig. 11.1) involves leaching of the ore to provide a leachate that, after any necessary solid–liquid separation, can be fed to the extractioncircuit. Control of relative liquid flows allows the concentration of thedesired metal and, thereby, economic processes for the recovery of metalsfrom dilute aqueous wastes such as mine waters and wash solutions from themetal-plating industries.Liquid–liquid extraction of metals has been used for many years as aconcentration technique in analytical chemistry; consequently, it was logicalto use the types of organic compounds employed in these systems for thedevelopment of industrial reagents for the same metals. However, becausethe overall requirements for these two end uses are different, modificationsto the basic structure were necessary to take account of the particularrequirements of hydrometallurgy, summarized by the following criteria:1. The ability to transfer the desired metal selectively across the aqueous– organic interface in both directions2. The ability of the reagent–diluent mixture to function efficiently withthe proposed feed and strip solutions in terms of rates of operation andstability toward degradation3. The ability of the reagent to perform with maximum safety to plant,personnel, and environment at minimum cost4. The ability of the process to interface with other unit operations bothupstream (leaching) and downstream (winning) in the overall extractionflow sheetIt can be seen that these criteria differ from those appropriate toanalytical applications. Thus, in the latter, it is not essential to strip themetal from the organic phase, especially if a colorimetric method is beingused. Also the chemistry of the feed solution is under the control of theanalyst, who can change pH and add buffers and masking agents at will.Finally, because so little reagent is used, toxicity and cost are not primeconsiderations. Thus, although the general class of organic molecule willfind application in both analytical and hydrometallurgical processes, thedetailed structures of the compounds will be different. Examples of suchmodifications can be found in a number of texts [1–3], and factors associatedwith commercial reagent design have been discussed [3–6].
Copyright © 2004 by Taylor & Francis Group, LLC
 
11.2 THEORY OF METAL EXTRACTION
Although a few metal compounds are sufficiently covalent to be extractableinto an inert organic phase (e.g., halides of arsenic, antimony, gallium, andmercury), for a number of reasons, such as their ease of hydrolysis, this typeof compound is unlikely to feature in a commercial extraction process.Normally, metal salts exist in aqueous phases as hydrated species and, assuch, are incompatible with those nonpolar organic diluents normallyused in hydrometallurgy. Therefore, to achieve extraction, species must bemodified to make them more hydrophobic by such procedures as (1) reac-tion of the metal cation with suitable anions to produce a neutral complex,(2) formation of an ion pair, and (3) replacement of hydrated water mole-cules by an organic solvating reagent.Reagents that are capable of such reactions are termed acidic, basic orion pair, or solvating, and their modes of action are typified by the followingequations:M
n
þ
þ
nHA
!
MA
n
þ
nH
þ
(11.1)MX
ð
n
À
p
ÞÀ
p
þð
n
À
p
Þ
R
3
NH
þ
X
À
!
R
3
NH
ð
n
À
p
Þ
MX
p
þð
n
À
p
Þ
X
À
(11.2)
Fig. 11.1
Hydrometallurgical flow sheet using solvent extraction.
Copyright © 2004 by Taylor & Francis Group, LLC

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