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Recovery of Minor Metals from Secondary Sources Using Solvent Extraction

Conference Paper · September 2014

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ISEC2014 – International Solvent Extraction Conference September 7-11, 2014

Recovery of Minor Metals from Secondary Sources Using Solvent

Extraction

Erkki Paatero* 1, Sami Virolainen2

Summary
A review is presented for the known and potential applications of solvent extraction to recover minor
metals from secondary sources. The utilizing SX is also discussed in relation to other viable options.
The examples in the presentation are based on the authors’ own experiences.
Zn ores contain typically In, Ga and Ge, which often end up to residues or landfills, but these elements
can be recovered by SX the process stream as by-producs. In Cu industry Au, Ag and PGM:s are the
main valuable by-products but the minor metals Mo, Re, Se, Te and W are also worth recovering. The
recovery of Mo from a Cu SX stream as well as the recovery of Mo and Re from a shaft furnace
residue are discussed. An example from steel industry is the recovery of Mo/Cr mixture by SX from
leachates of steelmaking dust.
The most valuable consumer wastes are the Waste Electrical and Electronic Equipment (WEEE). The
recovery methods are not the bottleneck, but gathering enough material to a place where it can be
economically processed and preferably integrated to a larger metallurgical plant (as shown in the
recent UNEP Metal Recycling: Opportunities, Limits, Infrastructure report).

Introduction
As a hydrometallurgical separation method solvent extraction is an option to be used
to recover minor metals from secondary sources. In this presentation the scope is
broad and such raw materials can be by-products from metallurgical processes,
metallurgical wastes or post consumer wastes and products (End of Life, EoL
products). These and other examples have been reported in the Doctoral Thesis by
Virolainen (2013).
In nature the minor metals are mostly associated with host base metals which the
minor metals follow in the metallurgical processing. This has been visualized by
Reuter et al. with the “Metal Wheel” seen in several presentations and reports e.g. in
the EU report on critical raw materials from 2010. The same authors have also
introduced a ”Metal Wheel for EoL” (Fig. 1) which was discussed in detail in the
recent UNIP report (2013). In the EoL Metal Wheel the first annulus from the core
represents society’s essential carrier metals. They are the extractive metallurgy’s
backbone in primary and recycling metallurgy. For instance recycled steel returns
also the alloy metals back to the industry together with the carrier metal iron. The
metals in the second annulus in the Metal Wheel include metals that dissolve mainly
in a carrier metal and can often be fractioned by pyrometallurgy. The metals in the
following (white) annulus end upp in a pyroprocess to dust, slime, speiss and slag

1* Outotec Oyj, Espoo, Finland

2 Lappeenranta University of Technology, Lappeenranta, Finland
ISEC2014 – International Solvent Extraction Conference September 7-11, 2014

from which the valuable metals can be recovered by e.g. hydrometallurgy. The
metals in the outmost annulus are usually lost from the system.

Figure 1. “The Metal Wheel” around the essential carrier metals in End of Life products. (Reproduced
with the permission of M.A.Reuter)

Role of aqueous solution chemistry for separation

The following cases are examples of actual separations that utilize the possibilities
that aqueous solution chemistry offers to make a separation possible. These and
other examples have been reported in a Doctoral Thesis by S. Virolainen (2013).
Knowledge of the speciation at different Eh and pH gives in general a basis for the
development of a hydrometallurgical separation but unfortunately the presence of
other ions, such as Fe2+/Fe3+, complicates the systems. The figures in this
presentation are calculated with MEDUSA software using its databank, except the
Eh-pH diagram for Mo, which is based on other literature data.
Molybdenum from Copper SX
Mo (VI) exists in some copper ores. It is in certain degree soluble in the leach acid
and consequently enters the SX, values between 30 and 120 ppm have been
ISEC2014 – International Solvent Extraction Conference September 7-11, 2014

reported by Cruz and Reghezza, 2007. The hydroxyoxime type extractants

commonly used for copper SX are known to coextract also Mo either as H 2MoO4
(molybdenic acid) and the MoO22+ (molybdenyl) that are present in sulfuric acid (Fig.
2). The extracted Mo can be selectively scrubbed Mo from the loaded organic phase
using an aqueous solution with a high enough pH to have Mo in an oxoanionic form.
The key is to take into account the slow reaction kinetics in the transformations
between the different Mo species at the neutral pH region where Mo is as polymeric
anions. In addition there may appear Mo heteropolymers with e.g. Cu and Fe.
Outotec has developed (Laitala et al., 2009) a special wash tank which acts both as a
loaded organic tank and a scrubber to remove molybdenum from organic phase prior
to Cu stripping. Mo is recovered as Ca-molybdate.
Molybdenum and Rhenium from Copper shaft residue
Outotec (at that time Outokumpu) developed in the late 70’s for its Kokkola works in
Finland a hydrometallurgical process to recover Mo and Re from an imported copper
shaft residue which contained 1.5% Mo in addition to Cu, Co and Ni. According to the
method, the residue is first leached with weak sulfuric acid followed by Fe, Cu, Co, Ni
removal. After that the solid residue is leached with alkaline and from the leach liquor
Mo is extracted with a cation exchanger (D2EHPA) at low pH. Re is then extracted
with an anion exchanger. As seen in Fig. 2 the speciation pattern of Re is very
simple. The perrhenate anion (ReO4-) dominates over a wide pH range. However,
many of the impurities (As, W, P) exist also as anions and again the Mo
heteropolymers require very good control of pH in different stages. In the process Mo
is recovered as Ca-molybdate and Re as ammonium perrhenate. The reader is
advised to see the paper by Y. Bal et al. (2004) that describes the extremely complex
chemistry of Mo in a SX process.
In the above example Re is recovered as a by product from a hydroprocess by SX.
Ion exchange is an alternative and today it is in use e.g. in Poland, Kazakhstan and
USA. The global mine production of Re was in 2012 about 52 ton/a (USGS, 2003).

Mo7O246- HMo7O245- H2Mo7O244-

2.0 1.0
ReO4-
1.5
MoO 4
2-
H2MoO4 MoO22+
1.0

0.5
Fraction, -
Eh, V

0.0 MoO2(s) 0.5

-0.5

-1.0
Mo(s)
-1.5

-2.0 0.0
-7 -6 -5 -4 -3 -2 -1 0 1 -7 -6 -5 -4 -3 -2 -1 0 1
+ +
log [H ] log [H ]

Figure 2. Eh-pH -diagram of Mo(VI) and speciation of 1 mM Re(VII) in 0.5 M sulfate solution.
Ic = 1.0 M, T = 25 °C.
ISEC2014 – International Solvent Extraction Conference September 7-11, 2014

The recycling degree of Ge is obviously quite high due to its value and the fact that it
has only a few main uses. Most of Re is found in superalloys (e.g. in jet engines) and
reforming catalysts which can be collected separately for recycling.
Molybdenum from steelmaking dusts
Argon oxygen decarburization (AOD) dusts are by-products in steelmaking industry
and may contain significant amounts of Mo. Due to the alkaline nature of the raw
material it can be leached with water. Since Mo occurs mostly as oxoanions from
alkaline side until approximately pH 2 (Fig. 2) and thus amine extractants with anion
exchange properties are suitable for selective recovery of Mo from the water
leachate. Most of the other leached metals, like Ca and K, occur as cationic species
and thus they are not extracted. The only exception is Cr(VI), which occurs as CrO 42-
anion in alkaline side (Fig. 3) and is thus co-extracted. Despite that, the combination
of water leaching and solvent extraction with anion exchanger is seen as a simple
and potential route to recover Mo from the AOD dusts (Virolainen et al., 2013).

Cr3+ Cr3(OH)45+ Cr2O3(s) CrO42- Ca(OH)2(s)

1.0 1.0
Ca2+

0.8 0.8
Fraction, -

0.6 0.6

0.4 0.4

0.2 0.2
Cr2(OH)24+ CaOH+
0.0 0.0
0 2 4 6 8 10 12 14 0 2 4 6 8 10 12 14
pH pH

Figure 3. Speciation of Cr and Ca in water leachate. [Me] tot = 100 mM, Ic = 1.0 M, Eh = 0.5 V,
T = 25 °C.

Indium from WEEE waste

In LCD screens Indium Tin Oxide (ITO) is as an electrode material. ITO consists of
90% In2O3 and 10% SnO2. In recycling the LCDs are dismantled and the ITO
containing glass panels are ground. According one method (Virolainen et al., 2011)
this glass powder is leached with 1 M sulfuric acid from which both In and Sn are
extracted with D2EHPA as extractant. The In/Sn separation is obtained by stripping
with an 1.5 M HCl solution where In appears predominantly as a chlorocomplex (Fig.
4). The indium capacity of D2EHPA is high enough to enable sufficient enrichment
although the amount of indium in LCD screens is very low.
ISEC2014 – International Solvent Extraction Conference September 7-11, 2014

1.0 Chloride 1.0 Sulfate

In3+

0.8 0.8
InCl3
In3(OH)45+
Fraction, -

0.6 0.6

0.4 InCl2+ 0.4

In(OH)3(s)

0.2 0.2
InClOH+ InCl2+

0.0 0.0
-7 -6 -5 -4 -3 -2 -1 0 1 -7 -6 -5 -4 -3 -2 -1 0 1
+ +
log [H ] log [H ]

Figure 4. Speciation of In(III) in 1.0 M chloride and 0.5 M sulfate solutions [In] tot = 1 mM, Ic = 1.0 M,
T = 25 °C.

Indium, gallium and germanium as by products

Zn ores contain typically In, Ga and Ge which are today recovered by SX directly
from the Zn process but often end up to residues or landfills. If the amount of in such
such old landfills is high enough the metals could be recovered by combining
pyrometallurgical (e.g. the TSL technology, see Creedy et al., 2013) and
hydrometallurgical treatment. If In, Ga and Ge are in a sulfuric acid solution In and
Ga can be extracted by cation exchange SX using e.g. D2EHPA as extractant. Ge
has quite different speciation (Fig. 5) than In and Ga. At low pH germanic acid
Ge(OH)2 can be extracted with -hydroxyoxime extractant, which can act through a
solvating mechanism. However, adsorption using a resin with N-methylglucamine
functional groups is a good alternative for the selective removal of Ge from acidic
zinc sulfate solution although the possible presence of iron limits its usability
(Virolainen et al., 2013).

GeO(OH) -
3
1.0
Ge(OH)4

0.8 GeO (OH) 2-

2 2

0.6
Fraction

0.4

0.2

0.0
0 2 4 6 8 10 12 14
pH

Figure 5. Speciation of Ge(IV) in sulfate solutions. [Ge] tot = 1 mM, Ic = 2.0 M, Eh = 0.5 V, [SO42-
]tot = 0.5 M, T = 25 °C.
 ISEC2014 – International Solvent Extraction Conference September 7-11, 2014

Conclusions
Many of the minor metals are both high-value and high-tech metals, which also are
classified as critical metals. The most optimal way for their recycling is to physically
sort them without mixing them with other metals as in the cases of In and Ge. In
recycling the recovery methods are not the bottleneck, but gathering enough material
to a place, where it can be economically processed is the difficult leg. The processing
should preferably take place integrated to a larger metallurgical plant, where the
metals in question already appear as by-products. Solvent extraction is a feasible
method to separate and concentrate the minor metals and it could follow the
fractionation the materials in a furnace to dusts, speiss and slag (e.g. Outotec’s Kaldo
or TSL technologies)

References
1. Virolainen,S., Hydrometallurgical recovery of valuable metals from secondary raw materials,
Thesis, Acta Universitatis Lappeenrantaensis 554, Lappeenranta 2013.

2. UNEP Expert report (lead author M.A.Reuter), Metal Recycling, Opportunities, Limits,
Infrastructure, UNEP publications, 2013.

3. Bal.Y., Bal,K-E., Cote,G. and Lallam,A., Characterization of the solid third phase that precipitate
from the organic solutions of Aliquat 336 after extraction of molybdenum(VI) and vanadium(V),
Hydrometallurgy 75(2004) 123-134.

4. USGS, Mineral Commodity Summaries, US Geological Survey, 2013.

5. Virolainen,S., Salmimies,R., Hasan,M., Häkkinen,A. and Sainio,T. Recovery of valuable metals

from argon oxygen decarburization (AOD) dusts by leaching, filtration and solvent extraction,
Hydrometallurgy 140 (2013) 181–189

6. Cruz,A. and Reghezza,A., Molybdenium: New by product at hydrometallurgical operations in

Codelco North?, HydroCopper 2007, Viña del Mar, Chile May 16-18, 2007.

7. Laitala,H., Paatero,E., Nyman,B. and Ekman,E. Apparatus and methos for removing impurities in
connection with liquid-liquid extraction of copper, PCT Pat. WO2010109078 (priority 27.3.2009)

8. Virolainen,S., Ibana,D. and Paatero,E., Recovery of indium from indium tin oxide by solvent
extraction, Hydrometallurgy 107(2011) 56-61.

9. Creedy,S., Glinin,A., Matusewicz,S., Hughes,S and Reuter,M.A., Outotec Ausmelt technology for
treating zinc, ERZMETALL 66(2013) 230-235.

10. Virolainen,S., Heinonen,J. and Paatero,E., Selective recovery of germanium with N-methyl-
glucamine functional resin from sulfate solutions, Separation and Purification Technology
104(2013) 193-199.

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