Angewandte

Reviews Chemie

International Edition: DOI: 10.1002/anie.201605417

Valuable Metals German Edition: DOI: 10.1002/ange.201605417

Valuable Metals—Recovery Processes, Current Trends,

and Recycling Strategies
Peter Frçhlich, Tom Lorenz, Gunther Martin, Beate Brett, and Martin Bertau*

Keywords:
platinum group metals ·
rare earth metals · recycling ·
transition metals ·
valuable metals

Angewandte
Chemie
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This Review provides an overview of valuable metals, the supply of From the Contents
which has been classified as critical for Europe. Starting with
1. Introduction 2545
a description of the current state of the art, novel approaches for their
recovery from primary resources are presented as well as recycling 2. Antimony 2547
processes. The focus lies on developments since 2005. Chemistry
strategies which are used in metal recovery are summarized on the 3. Beryllium 2549
basis of the individual types of deposit and mineral. In addition, the
4. Cobalt 2551
economic importance as well as utilization of the metals is outlined.
5. Gallium 2553

1. Introduction 6. Germanium 2554

It is not only since China announced export limits for their 7. Indium 2556
rare earth metals that we have been dependent on raw
materials. These limitations, however, ceased to be effective 8. Lithium 2557
on 1 May 2015. However, the oil crises of the 1970s and 1980s
have given us an early and strikingly clear picture of these 9. Magnesium 2559
dependences. This was the time when the Chinese leader
Deng Xiao Ping formulated the raw materials doctrine of his 10. Niobium 2562
country for mineral commodities.
In the course of globalization, industrialized countries 11. Platinum Group Metals 2563
compete ever more strongly with the so-called “Emerging
Countries” for raw materials and markets. These countries, 12. Rare Earth Elements 2567
Brazil, Russia, India, Indonesia, China, and South Africa,
often termed the “BRIICS” countries, contribute approx- 13. Tin 2573
imately 25 % (2013) to the global gross domestic product
(GDP). Roughly 40 % of the world population lives in these 13. 4. Recycling Processes 2574
countries, which are driven by the need to secure the
continued existence and livelihoods for no less than 3 billion 14. Summary 2574
people.
This situation results in inherently new challenges emerg-
ing for industrialized nations in terms of securing their supply
of raw materials. Even though economic growth of the
BRIICS countries was weakened in the summer of 2015, and primary product quality exists only to a very limited extent.
even though a gradual relaxation has been observed on the Typically, the vast majority of recycling activities ends up in
raw material markets, the fact must not be ignored that the what is called downcycling. As a consequence, dependences
global population is steadily growing and concomitantly on imports become permanent.
resulting in a steadily growing demand for food and produced However, the situation is much better than is typically
goods. We are experiencing a completely new situation of conceived. For decades, enormous amounts of primary raw
economic uncertainty in Europe, the United States, and materials have been imported. One fraction thereof is
Japan, which is facing the appetite of “Emerging Countries” exported as production goods, that is, refined to a higher
for energy and commodities. The looming economic situation level. This leaves a large fraction that remains in the country
in these countries will cause geopolitical uncertainties, be it and is disposed of at waste-disposal sites. One reason which is
economic recovery or economic decline. In Germany, addi- commonly invoked as justification why these secondary raw
tional risks for industry and consumers are imposed by the so- materials are not exploited is the high diversity of elements,
called energy and raw material shift. Thus, the industrialized paired with a lack of suitable technologies. Of course, there
nations are increasingly caught between political-economical are other issues, legal questions for example, which have to be
challenges on the one hand and technical-scientific ones on solved, but the key problem of technology development is
the other (Figure 1).
In 2014, the European Commission published the most
recent list of critical elements of relevance to the European [*] Dr. P. Frçhlich, T. Lorenz, G. Martin, B. Brett, Prof. Dr. M. Bertau
Institut ffr Technische Chemie
economy.[2] The reason for classifying a commodity as critical
TU Bergakademie Freiberg
are manifold, and they are outlined there in detail. However, Leipziger Strasse 29, 09599 Freiberg (Germany)
industrialized nations which are dependent on the import of E-mail: martin.bertau@chemie.tu-freiberg.de
raw materials are susceptible to geopolitical imponderabili- Homepage: http://tu-freiberg.de/fakultaet2/tech
ties to some degree. These uncertainties can be countered by Supporting information for this article can be found under:
recycling. However, a real recycling in the sense of restoring http://dx.doi.org/10.1002/anie.201605417.

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economical because of the

high dilution of the product.
In addition, alternative
approaches to access raw
materials by recycling or
new process conceptions
must have the ability to be
integrated into existing pro-
cesses to be operated eco-
nomically.
This complex situation
Figure 1. Securing raw materials in response to political-ecomonomical and scientific and technical experiences additional inter-
challenges (modified from Ref. [1]). play from a massive drop in
the prices of raw materials,
which is not equal for all
clearly a starting point for science, and it is chemistry that has commodities, however. Tin and lithium, for example, have
a pivotal role to play. In fact, it is only chemists who are seen considerable price increases in the first half of 2016,
capable of dealing with the high complexity of polymetallic which in the case of lithium is the consequence of the
mixtures in such a way that their extensive substance knowl- politically aspired electromobility.
edge allows the individual components to be channelled to Thus, there is sufficient cause for making an inventory of
industrial utilization and related disciplines. In this way, the the metals classified as critical. The aim is to give a well-
recovery of secondary raw materials will also lead to balanced and differentiated picture of which technical areas
interesting stimuli for the primary raw material sector.[1] of application are affected by which raw material supply, as
In fact, numerous developments have arisen from process well as how these metals are currently recovered from
optimizations, recycling, and substitution, and have culmi- primary and secondary raw materials. These latter will be
nated in holistic approaches. There has been massive progress compared through novel developments, with a focus on the
in the last few years, particularly in the field of recycling, and time after 2005, where a translation in chemical technology
various recovery concepts exist for many critical raw materi- appears feasible or has been realized.
als. Nevertheless, many of these have not progressed from the
laboratory scale, and others have proved to be too expensive.
In addition, in some cases, recycling is far from being

Martin Bertau received his PhD in organic
chemistry at the University of Freiburg/Br. in
1997 with Prof. Horst Prinzbach. He then
headed the biotechnology department of
Rohner AG (Dynamit-Nobel Group) in
Basle, Switzerland. In 2000 he moved to TU
Dresden, where in 2005 he received his
venia legendi in biochemistry and organic
chemistry. Since 2006 he has headed the
Institute of Chemical Technology at Freiberg
University of Mining and Technology. He is
a member of the Saxonian Academy of
Science and in 2012 was awarded the
Resources Efficiency Prize of the German Federal Minister of Economy as
well as in 2014 the wissen.schaft.arbeit Prize.
Gunther Martin graduated in chemistry at
the Technical University of Chemnitz. Since
2012 he has worked as a research assistant
and PhD student at the Institute of Chem-
ical Technology at Freiberg University of
Mining and Technology with Prof. Martin
Bertau. His PhD thesis focuses on extraction
techniques for lithium from primary raw
materials. He is also part of a start-up
company within the frame of the EXIST-
Transfer-of-Research program.

Beate Brett graduated in chemistry with
a thesis on “The self-association of carbohy-
drates in the presence of lipophilic sub-
strates” at Freiberg University of Mining and
Technology. Since 2012 she has worked as
a research assistant at the Institute of
Chemical Technology with a focus on the
recovery of secondary raw materials as well
as on the synthesis of calixarene-based
extracting agents.
Peter Frçhlich received his PhD in 2012 at
Freiberg University of Mining and Technol-
ogy with Prof. Martin Bertau. Since 2012 he
has headed the research group for the
processing of complex raw materials. As
a scholar of the Max-Buchner foundation
(DECHEMA) he is also concerned with the
chemical transport of GeO2 at low temper-
atures. He was awarded the wissen.schaft.ar-
beit Prize in 2014. Since March 2016 he has
coordinated a start-up company within the
frame of the EXIST-Transfer-of-Research pro-
gram.

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2. Antimony

2.1. Economic Significance

Antimony is utilized in metallic and oxidic form as well as

in the form of various antimony compounds. Most metallic
antimony serves as an alloying element (e.g. lead or tin
alloys). It increases the hardness and corrosion resistance of
a material. In the casting industry it prevents precision
castings from shrinking while cooling down.[3]
Oxidic antimony compounds account for a large fraction
of the antimony demand (Figure 2). Firstly, there is antimony
trioxide (Sb2O3), which is mainly used as a flame retardant for
plastics, rubber, textiles, and dyes. Other fields of application
include catalysis, such as polyester production (above all
polyethylene terephthalate (PET)), in the glass and ceramics
industries (sodium antimonate), as well as in future technol-
ogies,[4] such as in microcapacitors or antimony tin oxide
(ATO) for translucent conductive coatings.[3, 5–9]
The antimony market price is largely determined by the
crude metal and antimony trioxide. Production waste has
a lesser effect on the price.[9] In June 2016, the world market
price for traded metallic antimony with 99.65 % purity was
6452.78 USD t@1, what is 53 % less than the price four years
previously (13805.56 USD t@1 in June 2012).[11, 12]

2.2. Raw Materials

Antimony is a rather rare element, which is found in

nature as a sulfidic ore. In some cases it has also been found in
its native form. The most significant primary source for
antimony is the sulfide mineral stibnite (Sb2S3) with an
antimony content of up to 72 wt %. Other industrially utilized
sources are valentinite (Sb2O3), for example, or kermesite
(2 Sb2S3·Sb2O3).
Secondary antimony sources are fly ashes, slags from lead
refineries, or anode sludges from copper refineries, as well as
scraps containing antimony.[5, 6, 13] In the future, industrial by- Figure 2. Global production of antimony and fields of application.[10]
products (e.g. dump material, production waste) from lead,
copper, gold, or antimony production may also become of
increasing interest.[14] Other activities aim at antimony Antimony reserves are estimated to be 1.8 million tonnes.
recovery from catalysts,[10] landfills, or residues from waste As a result of less-expensive substitutes being available,
incineration.[15] antimony output declined from 197 000 t in 2008 to 160 000 t
in 2014. With an annual production of approximately 9 % of
the reserves, static supply is about 11 years. The major
producing country is China, which accounts for 78 % of
Tom Lorenz graduated in chemistry at Frei-
berg University of Mining and Technology in global production (Figure 2). Since China also imports large
2011. Since December 2011 he has worked amounts of antimony, its share of antimony production is as
as a research assistant and PhD student at much as 90 %. Antimony is classified as a strategic metal, the
the Institute of Chemical Technology in export of which is strictly regulated. The Chinese export
Freiberg with Prof. Martin Bertau. Recent quota has remained unchanged at 59 400 t a@1 since
scientific research focuses on developing recy- 2014.[3, 5, 6, 8, 16]
cling processes for rare earth metals from
At present, the annual demand of more than 200 000 t Sb
fluorescent lamp scrap and end-of-life mag-
nets as well as further development of solid- (2015: 241 600 t) cannot be covered by primary production,
state chlorination. In 2014, he was awarded and secondary antimony production (2010: 39.540 t Sb)[17] is
the wissen.shaft.arbeit Prize. not sufficient to close the supply gap. The negative market
balance in combination with ChinaQs monopoly has resulted
in insecurity in terms of antimony supply, which on a short to

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Figure 3. Schematic representation of primary antimony production by pyro- and hydrometallurgical processes with integrated recycling.[3, 13, 18]
medium term can only be counteracted by intensified
exploitation of secondary antimony sources.
2.3. Extraction Technologies
Naturally occurring antimony minerals are often associ-
ated with copper, lead, gold, and silver. Extraction is realized
by both open pit and underground mining. Stibnite (anti-
monite, Sb2S3), which is used as a source of antimony, is
obtained by concentrating the crude ore, followed by pyro- or
hydrometallurgical processing of the mineral (Figure 3).
Stibnite ores with higher levels of additional mineral
components (gangue) are heat-treated prior to further
processing. In this way, the rather low-melting antimony(III)
sulfide, Sb2S3, (m.p.: 547 8C) can drain off on a sloping surface
(segregation).
The choice of the best-suited pyrometallurgical recovery
process depends on the antimony content in the raw material.
Concentrates with lower antimony fractions (5–40 wt %) are
treated by a roast-reduction process, which at 1000 8C produce
volatile Sb2O3 or nonvolatile antimony(III,V) oxide (Sb2O4,
in nature cervantite).[18, 19]
Roast-Reduction Process
Air is blown over the red-hot sulfidic ore. In doing so, the
metal sulfide, here Sb2S3, is converted into the oxidic form,
while the sulfide anion is oxidized to SO2. The metal oxide
formed this way, here Sb2O3, is subsequently reduced to the
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metal. Carbon monoxide (CO), which is provided by the
combustion of coke, acts as a reducing agent. The reactive
roasting process is divided into steps (1) and (2).
Roasting work : 2 Sb2 S3 þ 9 O2 ! 2 Sb2 O3 þ 6 SO2 ð1Þ
Reduction work : Sb2 O3 þ 3 CO ! 2 Sb þ 3 CO2 ð2Þ
According to Equations (3) and (4), Sb2S3 is roasted
completely before it is reduced to the metal. The latter is done
in blast furnaces by smouldering with coke or charcoal in the
presence of alkali carbonate or sulfate as a fluxing agent.
Sb2 S3 þ 5 O2 ! Sb2 O4 þ 3 SO2 ð3Þ
Sb2 O4 þ 4 C ! 2 Sb þ 4 CO ð4Þ
The dedicated generation of Sb2O4 makes deliberate use
of the low volatility of the oxide. It serves to separate more
volatile impurities under the given process conditions, such as
As2O3 (in nature, arsenolite) and PbO (in nature, massico-
tite).[19]
Where the roasting process is conducted under restricted
air flow, heat-volatile antimony(III) oxide (Sb2O3) is formed.
It is discharged together with the exhaust air, from which it is
subsequently recovered by condensation. The high content of
impurities does not allow Sb2O3 to be utilized directly, and
thus it is converted into metallic antimony through carbo-
thermic reduction with coke or coal.[19]
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Roast-Reaction Process
The sulfidic ore is subjected to partial roasting, in the
course of which two thirds of the metal sulfide, here Sb2S3,
turns into the oxide, here Sb2O3, while one third remains
unaltered. In a second step, the reaction material is heated
under exclusion of air, as a result of which the metal sulfide
and oxide are converted into the metal. Instead of atmos-
pheric oxygen, in this case the metal oxide acts as the
oxidizing agent for sulfidic sulfur.[15] The reactive roasting
process is divided into steps (5) and (6).
Roasting work : 2 Sb2 S3 þ 9 O2 ! 2 Sb2 O3 þ 6 SO2
Reaction work : 2 Sb2 O3 þ Sb2 S3 ! 6 Sb þ 3 SO2
The roast-reaction process provides an alternative to
roast-reduction.[18] Here, stibnite is subjected to partial
roasting, during the course of which the roast product Sb2O3
reacts with unconverted Sb2S3 to give antimony metal
[Eq. (7)].
3 Sb2 S3 þ 9 O2 ! 6 Sb þ 9 SO2
The oxygen supply has to be held within narrow limits in
all process variants. Temperature windows also have to be
adhered to, since the vaporization of Sb2S3 at high temper-
atures constitutes a complication.
Concentrates with high antimony content (40–60 wt %)
are smelted at 550–600 8C in a reducing atmosphere, which is
carried out to prevent antimony oxides (Sb2O3 and Sb2O4)
from forming.
The molten intermediate Sb2S3 is refined to give antimony
metal by applying the roast-reduction or the precipitation
process. Metallic antimony obtained this way is sufficiently
pure for subsequent use.[19]
Precipitation Process
Sulfidic ores with 40–60 wt % Sb are smelted with iron at
550–600 8C in crucible or reverberatory furnaces. Iron is
converted into iron sulfide, FeS, and antimony is released
(“cast down”)[14] [Eq. (8)].
Sb2 S3 þ 3 Fe ! 2 Sb þ 3 FeS
Where antimony is recovered from lead ores, these ores
have to be subjected to roast-reduction or roast-reaction to
remove any copper. Further refining produces salt slags,
subsequent roast-reduction of which in turn furnishes metallic
antimony (Figure 3).[20] Crude antimony is often accompanied
by sulfur, arsenic, copper, lead, or iron. These impurities can
easily be removed by smelting the crude metal with soda
(Na2CO3) or sodium nitrate (NaNO3), in the course of which
they are oxidized and driven into the slag.[19] Hydrometallur-
gical processes in combination with electrolysis provide high-
purity antimony, and when combined with a hydrolysis step,
highly pure antimony(III) oxide is obtained.[3, 5, 6, 9, 14]
Independent from the recovery process, further purifica-
tion is achieved by refining electrolysis with Sb anodes, with
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cathodic deposition producing pure antimony metal. To
obtain semiconductor quality, pure antimony metal is con-
verted into SbCl3 and distilled. Antimony is subsequently won
by cathodic reduction and subjected to zone melting. Both
pyro- and hydrometallurgical processes are still a matter of
ongoing research. The optimization of individual process
steps with the aim of reducing toxic waste streams (e.g.
reducing SO2 emissions) with comparably high antimony
contents is currently the focus of research.[3, 21]
2.4. Recycling Processes
ð5Þ
As a consequence of the dissipative distribution of
ð6Þ
antimony, no recycling processes exist on a technical scale
for most fields of application. It is for this reason why the
recycling rate at present is < 5 %.[22] The majority of
secondary antimony originates from the recycling of lead
alloys containing antimony. In this context, the processing of
lead-acid batteries plays an important role. After removal of
the sulfuric acid, the batteries are shredded by mechanical
treatment. A thermal process follows, preferably in shaft or
ð7Þ short rotary furnaces, where antimonial lead and soft lead
alloys are smelted. The antimony content of the melt is rather
low, for which reason it is used directly for the production of
soft lead after impurities have been removed. The major
fraction of impurities is captured in a slag, the further
processing of which leads to new antimony lead. This product
is utilized almost exclusively in the battery sector.[5, 6, 9, 23] In
2014, approximately 3500 t antimony were recycled this way
in the USA.[24] The focus of current developments lies in the
recovery of antimony from printed circuit boards and lamp
phosphors (halophosphates).[25]
3. Beryllium
3.1. Economic Significance
Beryllium is a comparatively rare element. Together with
aluminum and magnesium, it belongs to the light metals. It is
primarily (70–80 %) used for producing beryllium-copper
alloys with 0.5–2.5 wt % beryllium (curing beryllium,
ð8Þ bronzes), for example, for electric equipment. As a conse-
quence of its nuclear physical properties, beryllium is used as
a moderator and reflector material as well in radiography. In
aerospace applications, beryllium is utilized as a metal and in
the form of beryllium base alloys, in particular because of its
high module of elasticity and stiffness with regard to weight,
its high tensile strength, and high degree of resistance to
distortion as well as its low coefficient of thermal expansion.
In addition, it is applied as a pure metal (50 t a@1), of which
roughly 1 t a@1 are used in Germany. With its high melting
point of 1287 8C it belongs to the high melting point metals.
The utilization of beryllium is sometimes regarded as critical,
particularly for toxicological reasons. The technical reference
concentration is 0.002–0.005 mg Be m@3 air. The metal is
classified as indispensable for military technology.[26, 27]
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Apart from its high mechanical stability, ber-

yllium oxide displays excellent heat conductivity
and acts as an electric insulator. Beryllium is
principally traded as metallic beryllium (pure
metal and beryllium copper), beryllium hydroxide,
and beryllium fluoride.[26] The average price of
beryllium metal was approximately 214 USD kg@1
in 2010.[28]

3.2. Raw Materials

Beryllium naturally occurs in several minerals,

but economically recoverable concentrations are
rarely reached. The globally most significant
deposit is Spor Mountain, Utah, USA, with an
average content of 0.71 wt % BeO, where an
epithermal bertrandite (Be4Si2O7(OH)2) deposit
with 40–43 wt % BeO is mined. The proven
reserves there are specified as 15 000 t Be. Beryl
(Be3Al2Si6O18) from pegmatite deposits with a con-
tent of 11–14 wt % BeO is predominantly mined in
Brazil, China, and Russia, as well as to some extent
also in the USA (Figure 4). The value of beryllium
is so high, that even hand sorting can be operated
economically. There are no data for beryllium
reserves, but the global resources are estimated to
80 000 t Be. 65 % of these are located in the USA,
where they are concentrated chiefly in three
deposits: Gold Hill and Spor Mountain in Utah
as well as the Seward Peninsula in Alaska.[27]
In total, roughly 92 % of the global production
of beryllium takes place in the USA, another 7 %
in China. The beryllium recycling quota is com-
parably low and is estimated to be about 10 %.[26]

3.3. Extraction Technologies

The recovery of beryllium from beryllium ores

is tedious and energy-intensive. At present, the
Materion process is chiefly applied, which was
developed in the 1980s and is capable of processing
both bertrandite and beryl for Be(OH)2 and
beryllium metal, respectively. It is essentially
based on the Kjellgren process for beryl and the
Maddox and Foos process for bertrandite.[29, 30]
In the second case, the crude ore is wet milled
to provide a particle size of about 20 mm and
leached with sulfuric acid. After diluting with Figure 4. Global beryllium production and utilization (2015).[27]
water, the solid components are removed by
decanting. The aqueous solution is subjected to solvent further heating to 165 8C in an autoclave eliminates CO2, and
extraction with di-2-ethylhexylphosphoric acid (DEHPA) in yields Be(OH)2 as a precipitate, which is recovered by
kerosene. The re-extraction of beryllium is carried out with filtration (Figure S1 in the Supporting Information).
aqueous ammonium carbonate solution. Coextracted Al and In contrast to bertrandite, beryl (beryl process) is
Fe are precipitated by heating the re-extract to 70 8C, and insoluble in acids. Currently, it is processed according to
separated by filtration. Subsequently, the process solution is a modified Kjellgren sulfate process, which starts with
further heated to 95 8C to precipitate basic beryllium carbon- smelting the ore at 1650 8C followed by quenching with
ate, 2 BeCO3·Be(OH)2. After repulping in deionized water, water to destroy the silicate structure. This pretreated

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material is tempered in a rotary kiln at 900–1000 8C to
increase its reactivity towards sulfuric acid. After cooling, the
beryl frit is wet milled before being leached at 250–300 8C
with sulfuric acid, which converts the beryllium and alumi-
num fraction into water-soluble sulfates. The siliceous residue
is discarded, and the Al,Be-sulfate solution is purified by
solvent extraction.[29, 31]
At this stage, the material flows of both processes can be
combined and further processed to Be(OH)2. There are
several purification steps, which follow, above all, an iron
separation step, before Be(OH)2 is precipitated at pH & 12.
Be(OH)2 is the starting material for beryllium-copper alloys,
beryllium oxide ceramics, and beryllium metal.
The production of metallic beryllium requires BeF2, which
is obtained by the Schwenzfeier process. Be(OH)2 is added to
an ammonium hydrogen fluoride solution to form water-
soluble (NH4)2BeF4 [Eq. (9)], from which impurities are
removed after neutralization and addition of precipitation
reagents, such as CaCO3. The purified fluoroberyllate is
crystallized through concentration in vacuo according to
Equation (10). The solid residue is heated to 900–1000 8C in
an induction furnace to afford pure beryllium fluoride. The
liquid BeF2 is poured into an ingot mold and further
processed to beryllium metal at 900 8C with magnesium in
large graphite crucibles [Eq. (11)].
BeðOHÞ2 þ 2 ðNH4 ÞHF2 ! ðNH4 Þ2 BeF4 þ 2 H2 O ð9Þ
ðNH4 Þ2 BeF4 ! BeF2 þ 2 NH3 þ 2 HF ð10Þ
BeF2 þ Mg ! Be þ MgF2 ð11Þ
The process is highly exothermic and so the crucibles are
incrementally charged with the BeF2 and magnesium. To
ensure good separation of molten beryllium from MgF2,
beryllium fluoride is used in excess, typically, about 75 % of
the BeF2 is reduced.
3.4. Recycling Processes
Beryllium recycling mainly occurs from production waste,
but other sources are WEEE (Waste Electric and Electronic
Equipment) and nuclear reactors.[32–34] In WEEE, beryllium is
normally present as BeO, which reacts with water to form
Be(OH)2. Reaction with CO2 furnishes BeCO3, which after
calcination to the oxide is treated with HCl to provide BeCl2.
The process steps are given in Equations (12)–(15). Alter-
natively, BeCO3 can be introduced into the Materion
process.[32, 34]
2 BeO þ 2 H2 O ! 2 BeðOHÞ2 ð12Þ
BeðOHÞ2 þ CO2 ! H2 O þ BeCO3 ð13Þ
BeCO3 ! BeO þ CO2 ð14Þ
BeO þ 2 HCl ! BeCl2 þ H2 O ð15Þ
Recycling beryllium from nuclear reactors is more labo-
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rious, as tritium and other radionuclide impurities have to be
removed first. Again, the material is converted into BeCl2.[32]
Beryllium can be recovered from BeCl2 by fused-salt
electrolysis. The fused-salt electrolysis that had been applied
at the beginning of the 1940s in Germany with the system
NaCl-BeCl2 was used for a while by Clifton in the USA and
Pechiney in France. Today, this process is no longer carried
out industrially. The alternative system of LiCl-KCl-BeCl2
was used by Materion Beryllium & Composites and Kawecki
Berylco, but this one is also no longer used.[29] Instead, BeCl2
is reduced to beryllium metal in a cathodically connected
nickel crucible with a graphite anode at 900–925 8C. Another
option is thermolysis of gaseous BeCl2 in a SiC bed. For both
approaches, however, no industrial application has yet been
reported.[33]
4. Cobalt
4.1. Economic Significance
Cobalt is rarely applied as a metal. The metallic form is
used mainly as an alloying element, especially for superalloys,
which are characterized by high-temperature stability, good
resistance to wear and corrosion, as well as by its hardness. An
example is the Hanes alloy, with a cobalt content of 25 to
50 wt %, which is employed in gas turbines. The importance of
AlNiCo and SmCo magnets has decreased as they have been
increasing replaced by FeNdB magnets. The total annual
production is currently about 4000 t.
The majority of the produced cobalt is used for the
preparation of cobalt compounds, chiefly cobalt (mixed)
oxides, a large amount of which is consumed in battery
production. China is the main consumer of cobalt worldwide,
with nearly 75 % going into the battery sector.[35] The high
demand for cobalt is one reason for the scepticism towards
the widespread use of lithium ion batteries in electric
mobility. Furthermore, cobalt oxides are employed as cata-
lysts, for example, for the hydro-desulfurization of natural gas
(CoMoX catalysts, Co3O4/MoO3/Al2O3) or hydroformylation
(Co3O4). Cobalt acetate or CoBr2/MnBr2 are utilized as
catalysts in the production of terephthalic acid.[26]
In the forthcoming years demand for refined cobalt is
expected to increase from 50 000 t a@1 (2007) to 110 000 t a@1 in
2030 and 190 000 t a@1 in 2050. The prognoses also show no
shortage in supply until 2050, if the supply situation in Africa
remains unchanged.[36] The market price for cobalt with
> 99.8 % purity was 25 USD kg@1 in June 2016 compared to
30 USD kg@1 in June 2012 (@16 %).[11, 12]
4.2. Raw Materials
In nature, cobalt is a rare element and occurs in a wide-
spread but dispersed form in trace quantities. It is frequently
associated with nickel, copper, silver, iron, and uranium. Like
all Group VIII–X elements, cobalt is a siderophile element. It
occurs in a concentrated form in Ni-laterites as well as in
cobaltite (CoAsS), skutterudite (CoAs3), and linnaeite
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((Co,Ni)3S4). The weathering product of arsenic-containing
cobalt ores, erythrite (Co3(AsO4)2·8 H2O), is less important as
an ore than as an indicator for natural mineral deposits.
Global reserves are 7.1 million t, of which 3.4 million t are
located in the Democratic Republic of the Congo and
1.1 million t in Australia.[35] The global resources are esti-
mated to be 25 million t.[35] In addition, more than 120 mil-
lion t cobalt were detected in the manganese-rich nodules of
the oceanic deep sea and on the ocean floor. The global
production of cobalt is shown in Figure 5.
The most important secondary raw materials for cobalt
are waste rechargeable batteries, the cathode materials of
which contain 5 to 20 wt % cobalt in the form of LiCoO2 and
LiNixMnyCozO2 (x + y + z = 1).[38] In 2014, approximately
15 000 t waste batteries and storage batteries were collected,
Figure 5. Global production and applications of cobalt (2015).[24, 37]
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which represents a quota of 45.3 %.[39] One fifth of the
recycled cobalt comes from hard metals and used catalysts.[26]
4.3. Extraction Technologies
Since in many cases cobalt ores are often associated with
copper and nickel ores, these metals are often processed
together. However, the heterogeneous composition of the
crude ores (oxides, sulfides, arsenides) does not allow
a standard procedure to be applied for the production of
cobalt, instead it will need to be adjusted to the individual
situation.
Sulfidic and arsenic ores are subjected to roasting
processes during the production of cobalt. The procedural
expense is higher for arsenic ores, because of the release of
arsenic vapors, such as As2O3. Recently, this problem has
been solved by pressure leaching, in which parameters are
used to keep the arsenic components in the solid residue.[26]
Two process options are available depending on the compo-
sition of the ore (association with Ni, Cu, Fe, Ag, U):
In pyrometallurgical processes, the iron sulfide present is
partially converted in a melting furnace into iron oxide, which
forms an iron silicate slag with quartz. The so-called cobalt
rough stone produced that way contains in addition to cobalt,
Cu, Ni, Fe, as well as S and As as accompanying elements.
Alkaline roasting with soda and NaNO3 converts sulfides and
arsenides into their sulfates and arsenates, which are removed
by aqueous leaching. The remaining metal oxides are leached
with sulfuric or hydrochloric acid, whereupon Co, Ni, and Fe
dissolve and Cu remains in the rough stone. Depending on the
grade of impurity, it may be necessary to separate accom-
panying elements by solvent extraction or precipitation
before cobalt can be precipitated as cobalt oxide hydrate
(CoOOH) with chlorinated lime and separated by filtration.
Subsequent heating furnishes Co3O4, the starting material for
the carbo- or alumothermic reduction to cobalt metal.
The hydrometallurgical processes encompass leaching of
preprocessed ore concentrates and untreated crude ore
(whole ore leach, WOL). Pretreatment often involves not
only mechanical concentration but a roasting step to convert
sulfides into oxides or to strip arsenic by oxidation.
Leaching with sulfuric or hydrochloric acid provides
highly water-soluble cobalt compounds (CoSO4, CoCl2).
This is also the easiest way. When oxidic roast products are
employed (from sulfidic ores), alkaline leaching with aqueous
ammonia solution is preferentially carried out, which yields
[Co(NH3)6]2+ and avoids the formation of H2S (Caron
process). Products obtained from the oxidizing roasting are
leached with sulfuric acid or simply with water. In the Sherrit–
Gordon process, sulfidic cobalt ores are leached with aqueous
ammonia solution. Arsenic-containing ores are roasted under
oxidizing conditions at 600–700 8C to remove As as As2O3,
followed by leaching with HCl or H2SO4. Subsequent
extraction and precipitation processes, frequently under
pressure (p = 1–40 bar) and increased temperature (T = 40–
250 8C), remove the impurities.[26]
A vapor metallurgical procedure is available as an
alternative to pyrometallurgical or hydrometallurgical treat-
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ment. This approach makes use of the propensity of the computers or smartphones, photodetectors, thin-film solar
elements Fe, Co, and Ni to form gaseous complexes with CO, cells, and optoelectronic devices. A further field of application
which can be separated from each other in accordance to their is the preparation of trimethyl- and triethylgallium.[48] These
boiling points. Ni(CO)4 boils at 43 8C, Fe(CO)5 at 103 8C, organometallic compounds are mainly used to manufacture
while [Co2(CO)8] is not very volatile and melts at 52 8C with epitaxial layers for the production of light-emitting diodes
decomposition. An advantage is the access to metals in highly (LED).[48–50]
pure forms as a result of the easy thermal decarbonylation of The most important gallium producers are China, Ger-
the carbonyl groups. The high process effort because of the many, Kazakhstan, Korea, and Ukraine. Currently, the
high toxicity of CO and in particular of the metal carbonyl primary production capacity of approximately 730 t (2015)
compounds is disadvantageous. For this reason, among others, significantly exceeds the global demand for gallium. Japan is
a large-scale industrial use of the vapor metallurgical route is the most significant producer of secondary gallium.[27] There
not known.[26] has been a massive increase in production capacity, for
More recent approaches are based on the use of hydrogen example, in China, from 140 t in 2010 to 600 t in 2015. As
peroxide. As an example, 90 % of the Co of a Cu-Co ore from
the Congo (Co content 1.5 wt %) can be successfully
extracted at 30 8C within 2 h by adding H2O2 to the leaching
process with sulfuric acid, whereas in the absence of H2O2
only 15 % was obtained.[40] In another case, it was shown with
the example of an Indian laterite that the presence of SO2 has
a beneficial effect on leaching with sulfuric acid. In this way,
the cobalt leaching rate climbed from 85 % to 97 %, while
impurities largely remained in the solid residue.[41]

4.4. Recycling Processes

There is no reliable data available for the total amount of

cobalt recycled, only for partial flows. In 2015, 28 % of the
cobalt contained in steel scrap was recovered. Furthermore,
the rate of recycling of end-of-life (EoL) products at 68 % is
much higher than for most other metals.[42]
Industrially established recycling processes are carried out
pyrometallurgically (e.g. VAL’EAS process from Umicore,
Inmetco process), which also recover metals other than
cobalt, particularly nickel.[43] This process is characterized by
high efficiency and high throughput, whereas the formation of
toxic gases, the high energy requirements, and dust emissions
are problematic. In addition, pyrometallurgical processes are
followed by hydrometallurgical processes for separation and
purification.[44] These disadvantages led to various alternative
approaches being studied that comprise mechanical pretreat-
ment, acid or microbial leaching, and subsequent cobalt
separation.[45] The separation of cobalt from the polymetallic
digestion solution is carried out, in particular, by means of
solvent extraction, for example, with Cyanex 272 or tri-n-
butylphosphate,[46] but also by electrochemical processes[47]
and selective precipitation, for example, as the oxalate
(CoC2O4·2 H2O).[44]

5. Gallium

5.1. Economic Significance

Approximately 75 % of the global production of gallium

(574 t in 2013) is used to produce the semiconductor materials
gallium arsenide (GaAs), gallium phosphide (GaP), and
gallium nitride (GaN; Figure 6). These materials are essential Figure 6. Worldwide gallium production (2013) and applications
for the production of integrated circuits in high-performance (2010).[48, 51]

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a consequence, 99.99 % (4 N) gallium prices have been
plummeting from 341 USD kg@1 (June 2012) to
111 USD kg in June 2016 (@67 %).[11, 12]
@1
5.2. Raw Materials
Gallium is a very common trace element. The content in
the lithosphere is approximately 10 ppm. Gallium does not
form its own minerals under natural conditions, but occurs as
an admixture in aluminum, zinc, or germanium ores. For this
reason, the extraction of gallium-bearing minerals is econom-
ically not viable, and the metal is recovered as a by-product
during the production of aluminum and zinc.[52] The most
important gallium-bearing minerals are gallite, germanite,
sphalerite, chalcopyrite, and especially bauxite.[5] The gallium
content of bauxite is up to 60 ppm, and with huge bauxite
reserves of about 27.5 billion t,[53] it represents the largest
primary gallium deposit (> 1 million t).[49, 54] Important secon-
dary raw materials are fly ashes with a gallium content up to
100 ppm,[55] electronic scrap, as well as gallium-containing
production waste.[55, 56]
5.3. Extraction Technologies
Crude gallium is primarily obtained as a by-product from
the production of aluminum and zinc. Four established
processes are applied for separating and concentrating
gallium in the leach liquor: fractionated precipitation, elec-
trochemical methods, solvent extraction, and ion-exchange
processes (Figure S2 in the Supporting Information).
As a first step in the fractionated precipitation of gallium,
the pH value is adjusted to 10.6 with CO2. This results in
aluminum hydroxide precipitating while gallium remains in
solution. The addition of slaked lime (lime method) or sodium
aluminate solution then allows the gallium to be separated
from the leach liquor. In a next step, the gallate solution
obtained has to be treated to remove heavy metals and is
further processed to crude gallium. However, as a result of the
high consumption of energy and chemicals, laborious multi-
stage precipitation, and considerable amounts of by-products,
fractional precipitation is applied only in low-wage countries,
such as China.[5, 54, 56]
Electrochemical methods such as gallium concentration in
a liquid mercury cathode (amalgam process) as well as
cementation display significant economical deficits, as does
solvent extraction with Kelex100 diluted in kerosene and 1-
decanol. Major drawbacks are the use of mercury (prohibited
in some countries) and the high consumption of mercury and
extraction agent, respectively.[54, 56, 57] This was the impetus to
test new extraction agents, such as di-(2-ethylhexyl)phos-
phoric acid (DEHPA), for which gallium yields of up to
99.9 % have been reported.[58]
The most significant industrial process to date is based on
using ion-exchange resins such as Duolite ES-346 and
DHG586 come. Their advantage lies is their excellent speed
of extraction combined with an excellent selectivity for
gallium over aluminum. However, the instability of the
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amidoxime group is regarded as a major challenge, and
likewise coextraction of vanadium, which has to be separated
prior to gallium extraction.[56] Since solvent extraction and
ion-exchange processes are the most effective ones, the focus
of research lies on improving the extraction kinetics of the
Kelex100 system as well as reducing vanadium coextraction.
In addition, amidoxime groups with higher stability are also
sought.[56]
The production of marketable gallium (4N) is typically
carried out by electrolyzing preprocessed and concentrated
gallium-containing solutions obtained from large-scale oper-
ations.[56]
5.4. Recycling Processes
At present, with a recycling rate of < 1 %, industrial
gallium recycling of EoL products is almost insignificant.[22]
The very low gallium concentrations in EoL products as well
as the high requirements regarding the recycling system and
process technology are responsible for this situation.[59] Thus,
compared to primary recovery there is no process in sight for
recycling gallium from electronic scrap that has the prospect
of being economically viable.[60]
In contrast, the recovery of gallium from the production
waste of GaAs manufacturing bears much more potential,
since the gallium content is considerably higher (up to
48 wt %).[27, 49, 61] The following methods are in use for treating
industrial waste: 1) thermal treatment, 2) oxidation with
oxygen, and 3) nitrification with ammonia and chlorination
with chlorine gas.[49] Membrane-based separation of gallium
from production wastewaters is a potential alternative.[62]
6. Germanium
6.1. Economic Significance
Global demand for germanium is 150 t a@1 and, similar to
platinum group metals, it is required in only small
amounts.[7, 63] It is essential for many technology products
(Figure 7). Almost half of the annual production is accounted
for by optical fibers and infrared optics. Up to 20 % of the Ge
produced is consumed in the production of PET (GeO2
catalyst).[7] Germanium-containing alloys are also used in X-
ray detectors as well as the photovoltaic and semiconductor
sector. Similar to rare earth elements, the European Com-
mission rates Ge among the elements with a high supply risk,
as a result of the complete dependence on imports and the
dominant position of China regarding this element.[2, 64, 65]
ChinaQs share of the global annual production is currently
about 70 %.[7, 63, 66] In addition, recent years have seen several
countries increasing their national reserves. The abandon-
ment of this practice together with the elimination of customs
duties on exports resulted in the commodity prices for 4N
GeO2 dropping by 23 % between June 2012 (1075 USD kg@1)
and June 2016 (833 USD kg@1).[11, 12] Nevertheless, demand for
germanium is currently still falling slightly.
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Figure 7. Global production and applications of germanium (2015).[67]
6.2. Raw Materials
With a natural abundance of 1.5 mg kg@1, Ge is as common
as Zn or Cu, however, it is rarely concentrated in depos-
its.[63, 65, 66, 68] As a consequence of its chemical similarity with
silicon, germanium is incorporated in siliceous soil horizons in
low concentrations. A similar trend is observed for germa-
nium-containing Cu, Zn, Ag, and Pb minerals, for which
either there are no significant deposits (argyrodite) or the
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germanium-content does not justify mining for it alone.[5, 63]
For this reason, germanium production exclusively occurs as
a by-product from smelting processes of sulfidic ores such as
sphalerite or renierite.
Global mineral deposits currently comprise about 9000 t
Ge, of which 40 % are located in China, 30 % in Russia, and
another 20 % in Africa.[69] Other sources of Ge are lignite or
hard coal deposits, in which Ge from plant material has
undergone a natural concentration during the formation
process. High local contents indicate an additional adsorption
of Ge from mountain waters along wall veins of coal seams.
At present, fossil germanium reserves are estimated to be
3900 t.[69] 34 % of the annual global production of 165 t (2015)
originate from fly ashes from coal combustion, while 36 %
comes from mineral deposits and 30 % from recycling
production waste from the manufacture of glass, PET, and
semiconductors.[69]
6.3. Extraction Technologies
Fly ashes, which occur as a by-product from processing
mineral and fossil resources, are an important source of Ge
(Figure S3 in the Supporting Information). As a result of its
excellent adsorption characteristics, Ge accumulates in the
ashes in up to 0.1 wt % in the form of GeS or GeO during ore
roasting or coal combustion.[5, 68, 70] Further processing is
carried out hydrometallurgically, typically starting with acid
leaching followed by precipitation. Germanium is precipi-
tated either as GeS2 by introducing H2S or by organic
complexing agents (e.g. tannins). The precipitate is roasted
once more, thereby producing a GeO2 crude product.
Treating the crude product with concentrated hydrochloric
acid (> 6 m HCl) forms the highly volatile GeCl4
(b.p. 86.5 8C),[71, 72] which is separated by distillation to provide
the required product quality.[73] GeO2 is subsequently pre-
cipitated by hydrolysis. Reducing GeO2 with H2 delivers the
crude metal. Further purification up to semiconductor quality
is realized by zone melting. However, precipitation has the
disadvantage that the separation of germanium is incomplete
and the costs for chemicals are high, since the precipitant gets
lost on roasting. For this reason, solvent extraction has
prevailed on a large scale since the middle of the 20th
Century. Numerous extraction agents are in use for extractive
concentration and purification,[57, 72, 74] for example quinones,
phosphonic acids, and amines.[75] New research projects take
advantage of plants capable of bioaccumulating germanium
from soils, which so far were not suited for Ge recovery
(phytomining). In this approach, germanium is released from
the biomass as a by-product of biogas fermentation. Acid
digestion of the crude product and distillation are carried out
in an analogous manner to the fly ash process. In this way the
PhytoGerm project succeeded in recovering germanium as
GeO2 from reed canary grass.[76] The aim is to recultivate
contaminated soils as well as to contribute to securing the raw
materials for germanium.
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6.4. Recycling Processes

Although secondary sources of raw materials, with a share

of 30 %, contribute significantly to annual world production,
the focus of recycling is almost exclusively on production
waste. Up to 60 % of the Ge can be reused from waste
materials from the manufacturing of photovoltaic modules,
special glasses, or infrared optics.[7] Recycling is carried out by
the same method as for germanium recovery from fly ashes. In
contrast, recycling of EoL products is still in its infancy,
because the separation from multielement mixtures is much
more complex than extraction from primary raw materials. To
date, there is no economic process available for recycling
germanium from EoL products.[77] Another problem is the
low return rates of these products, as a consequence of which
there is no possibility to bring together bulkier waste streams
for effective recycling.

7. Indium

7.1. Economic Significance

Indium is mainly used in the production of indium-tin

oxide (ITO), a mixed oxide composed of 90 wt % In2O3 and
10 wt % SnO2 (Figure 8). The production of 2090 t ITO (2013)
has resulted in roughly 90 % of the indium produced world-
wide having been consumed. The beneficial properties of ITO
are its good electrical conductivity as well as its transparency,
for which reason it is used in thin coatings for the production
of transparent liquid-crystal displays (LCDs).[78, 79] Moreover,
ITO is also a good thermal conductor and has a low melting
point. Further applications are as an alloy compound in
soldering agents or thermally conductive films. Important
indium materials are indium phosphide, which is used in
optoelectronics, and copper indium gallium (di)selenide
(CIGS), for thin film solar cells.[26, 80] According to a UN
study, the indium demand will increase by a factor of three by
not later than 2030.[81]
The indium price dropped during the course of the global
commodity price development. Between June 2012
Figure 8. Worldwide production (2015) and applications (2012) of
(505 USD kg@1 for ingots with 99.97 % purity) and June indium and indium compounds.[82, 83]
2016 it decreased by more than 50 % to 251 USD kg@1.[11, 12] In
addition, 10 % drop in the production volume to 755 t was
observed in 2015.[82] 10 000 ppm, but is commonly within a range of 10 to
20 ppm.[85]
Information on the current indium reserves is not
7.2. Raw Materials available, but in 2008, the worldwide reserves were estimated
to be 10 670 t.[82, 86] Almost 75 % of the indium reserves are
Indium occurs more abundantly in the EarthQs crust assumed to be located in China.[78] The most important
(ca. 0.05 ppm) than silver.[84] Indium-bearing minerals, such as secondary resource of indium is ITO waste, which incurs in
indite (FeIn2S4), cadmoindite (CdIn2S4), roquesite (CuInS2), substantial quantities during the production and disposal of
and dzhalindite (In(OH)3) are rare and insignificant for liquid-crystal displays.[79]
industrial extraction processes. Indium, as a chalcophilic
element, tends to associate with the base metals copper, lead,
zinc, and tin as well as bismuth, cadmium, and silver. 7.3. Extraction Technologies
Therefore, significant amounts of indium can be found in
ores such as sphalerite, chalcopyrite, galenite, cassiterite, and Approximately 95 % of indium production is a by-product
pyrite.[80] The indium content of these ores can be up to of zinc smelting. The majority of the global production (52 %)

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is attributable to China and just 1.5 % to Germany.[82]
Industrial extraction processes commence with an initial
digestion of calcined zinc sulfide with sulfuric acid at
a moderate pH value. In this way, zinc is leached, while the
less-soluble indium oxide remains as a solid residue. The
subsequent addition of more concentrated H2SO4 (25 g L@1)
to provide In2(SO4)3, is followed by the precipitation of
indium hydroxide with NaOH (Figure S4 in the Supporting
Information). Further refining steps comprise re-dissolution
of indium hydroxide, removal of heavy metals as sulfides with
H2S, indium cementation, and a final electrorefining.[5]
Apart from established industrial processes, there are
some approaches that aim to recover indium from primary
indium extraction residues. Pressure leaching of fly ash from
zinc smelting with sulfuric acid, for example, gives a recovery
rate of 90 % when H2O2 or KMnO4 are present.[87]
Roasting sphalerite (zinc blende, black-jack) results in the
formation of iron ferrite, which interferes with zinc recovery
(depending on the iron content). In addition to the classic
procedure—an effective but polluting pyrometallurgical roll-
ing process—hydrometallurgical processes have been devel-
oped.[88] Indium-containing zinc residues are digested in
a reductive leaching process with sphalerite and H2SO4, the
subsequent solvent extraction of which furnishes recovery
rates > 95 %.[89]
In addition to the recovery of indium as a by-product from
zinc smelting, there are also processes for recovering lead,
copper, and tin.[5] For example, lead and indium can be
separated by adding chelators to the hydrometallurgical
leaching process of lead smelter dust. Subsequent acid
digestion provides an indium recovery rate of 88 %.[90]
7.4. Recycling Processes
Recycling of indium can be divided into recovery from
ITO production waste and EoL liquid-crystal displays. During
the manufacture of LCDs, ITO is deposited on glass by
cathodic sputtering of ITO planar targets. However, the yield
is low, with only 15–30 % of the ITO being deposited on the
substrate. The resulting indium-rich waste is directly recycled
with high recovery rates. According to estimates, the secon-
dary production of indium from ITO waste is 1000 t (2012),
which is higher than the primary production in the same
year.[84]
Besides the industrially established processes, studies
were carried out to process ITO production waste by using
H2S to precipitate and thus separate the tin. This approach
afforded tin in quantitative amounts, accompanied by a slight
loss of indium that did not exceed 0.5 %.[91] Solvent extraction
was also found to be suitable for separating indium from tin,
since re-extraction of the organic phase with hydrochloric
acid is selective for indium. However, there is no strategy
published for the required separation of indium from the
organic phase.[92]
The first step of a process for the recovery of indium from
copper indium selenide (CIS) solar cell production is leaching
with acetic acid to separate tin acetate. Subsequently,
a digestion with nitric acid, followed by a cementation with
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Se/Cu is carried our. Indium, which remains in solution, is
precipitated as In(OH)3 in a yield of 98 % and with high purity
(> 99 % at pH 3).[93]
The recycling of EoL LCD screens is considerably more
complex, however. The indium-rich conductive layer is only
about 125–150 nm thick (100–400 ppm In), thus no more than
230 mg In m@2 can be obtained.[79] Studies have shown that an
indium price of about 400 USD kg@1 is required to cover
recycling costs.[80] In addition, more technological effort is
required for treatment of LCD screens compared to ITO
waste, and thus indium recovery from LCD screens is not
implemented on an industrial scale at present.
At present, the recovery of indium from mobile phones
also does not appear to be economically feasible. Although
0.3 kg indium was obtained from one ton of mobile phone
displays after dismantling, leaching with acetone, grinding,
acid digestion, and subsequent ammonia neutralization, this
required 44 m3 of 1 mol L@1 H2SO4 as well as sufficient
ammonia to neutralize it.[94]
A promising laboratory-scale process is the separation of
ITO coatings from LCDs and polarizing filter glass by using
water. ITO separation was 83 % from polarizing filter glasses
compared to 7 % from LCD screens.[95] The meagre separa-
tion rate for LCD screens was increased up to 95 % at 220 8C
by using 0.1 mol L@1 caustic soda. Applying this method to
polarizing filter glass enabled 99 % ITO to be recovered at
160 8C.[96] Advantageously, the ITO layer is not only detached
from the glass surface, it can easily be separated from the
leaching liquor by filtration to enable further processing.
8. Lithium
8.1. Economic Significance
Lithium is a strategic metal which is most commonly
considered as being indispensable for future technologies
such as energy storage, electric mobility, and cordless devices.
However, lithium compounds have a far broader spectrum of
application such as in the glass, enamel and ceramic indus-
tries, lubricating greases, pharmaceutical products, and alu-
minum production (Figure 9).[97]
Since there is no substitute for lithium in its most
important applications, such as ceramics and glass, (recharge-
able) batteries, as well as lubricants, the demand for this metal
is forecasted to grow by approximately 8–11 % a@1.[99] In 2025
there will be a severe supply gap, since lithium demand for
lithium battery production will almost double from its 35 %
share in 2015 to about 70 % in 2025, while lithium demand
from other market segments will not decrease in the foresee-
able future.[98, 100] The most important lithium compound for
the production of tradable products is Li2CO3 at a total
quantity of 46 %. In conjunction with LiOH (19 %), these two
derivatives cover about two thirds of the market.[101] The
demand for Li2CO3 is expected to increase significantly up to
2025 (9–12 % a@1), and for LiOH by up to 14–16 % a@1 since it
is also used for the production of cathode materials in
rechargeable batteries (e.g. LiMn2O4, LiFePO4, LiCoO2).[102]
As a result of the increasing demand for Li2CO3 and LiOH,
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Figure 9. Worldwide lithium production and applications (2015).[98]
the market price is expected to significantly increase in the
future. Some even expect to see a price jump in the current
market price of 6063 USD t@1 (June 2016) to 25 500 USD t@1
not later than 2020.[10, 103] The concerns to some extent became
reality in December 2015 in China, where the spot price was
more than 20 000 USD t@1 tg-Li2CO3 (technical grade,
> 99.0 %).[104] However, the price of tg-Li2CO3 has dropped
by approximately 15 % in the last four years (June 2012,
7187 USD t@1).[11]
8.2. Raw Materials
The estimated reserves (ca. 14 million t Li) and resources
(34 million t Li) show that Li is not a scarce commodity. In
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2014, global production of Li reached roughly 32 000 t. In fact,
the theoretical static supply of Li is about 435 years.[98] Almost
60 % of the Li reserves are found in South America, especially
Chile, Bolivia, and Argentina. Approximately 4.4 million t Li
are located in North America (USA, Canada) and a further
5.4 million t Li in China. The European Li deposits
(ca. 1.1 million t Li), on the other hand, represent only roughly
3.0 % of the worldwide resources.[98]
Li deposits are divided into brine deposits and Li ores. The
most important brine for Li extraction is the Salar de
Atacama in Chile (6.3 million t Li). An even greater brine
deposit is expected at Salar de Uyuni in Bolivia (10.2 million t
Li). The altitude (3650 m), the quite low average Li content of
320 ppm, and less-favorable climatic conditions for concen-
tration, are some of the reasons that have so far prevented the
large-scale production of Li.[105–107]
The most important lithium deposits are igneous rocks
(3.9 million t Li). These pegmatites contain the minerals
spodumene, lepidolite, petalite, and zinnwaldite in particular.
Deposits are found in the USA, China, Zimbabwe, Russia,
Canada, and Europe. The greatest Li ore deposit is the
Greenbushes spodumene mine in Australia with 0.85 million t
Li.[107] Currently, two large spodumene deposits in Whabouchi
(Canada) with about 27 million t raw material (1.53 wt %
Li2O), as well as the Mt. Marion lithium deposit in Australia
(ca. 23 million t raw material, 1.39 wt % Li2O) are devel-
oped.[108] As a consequence of the huge primary reserves and
resources of Li, lithium from secondary sources has had no
significant impact on the total supply so far.[109]
8.3. Extraction Technologies
Currently, lithium is predominantly (ca. 60 %) recovered
from the salt lake brines Salar de Atacama (Chile) and Salar
de Hombre Muerto (Argentina). Lithium production from
brines profits considerably from lower manufacturing costs
combined with less technological effort compared with that
for lithium ores.[110] The standard process steps for a large-
scale production of lithium derivatives from salt lakes, also
called Salar in South America, comprises an initial evapo-
ration of a lithium-containing solution in artificial ponds and
removal of crystallizing salts. Subsequently, impurities and by-
products are precipitated and lithium derivatives are recov-
ered.[111, 112]
A number of different approaches for industrial lithium
extraction has been developed because of the different
compositions of brines and regional conditions of the saline
lithium deposits.[110] For example, because of an unfavorable
Mg/Li ratio of 20.3 at the Salar de Uyuni in Bolivia (c.f. Salar
de Atacama: 6.3), magnesium hydroxide is precipitated by the
addition of lime prior to evaporation.[105] On the other hand,
the climatic conditions do not favor facile evaporation. They
are compensated for by devices to aid evaporation (evapo-
ration cones), which are almost similar to a falling film
evaporator in terms of their mode of function. The brines are
heated by solar power to a temperature that allows for an
evaporative concentration of the Li brines under the given
wind speed.[112, 113]
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The most commonly applied processes for the recovery of
lithium from siliceous lithium ores are pyrometallurgical
roasting with H2SO4 and limestone digestion with CaCO3.[114]
Both methods have significant drawbacks, since 1) the high-
temperature thermal conversion of a- into b-spodumene (T +
800 8C) is associated with considerable energy consump-
tion,[115] 2) roasting with H2SO4 also requires large amounts of
base for precipitation of the hydroxide, as well as the
combined by-product Na2SO4 being of very low value because
of an over-saturated market, 3) the limestone digestion
requires substantial amounts of CaCO3. In fact, the CaCO3
to ore ratio is 3:1 for lepidolite and even 5:1 for zinnwaldite
under optimized conditions.[116]
A number of alternative approaches, particularly for
spodumene, but also for petalite, lepidolite, and zinnwaldite
were more recently developed (summarized in Figure S5 in
the Supporting Information). They comprise a direct chlori-
nation with Cl2 (T = 1000–1100 8C) to yield gaseous lithium
chloride,[117] an autoclaved digestion process for b-spodumene
carbonatization with Na2CO3,[118] and leaching with HF (7 %)
followed by separation of the by-products sodium cryolite
(Na3AlF6) and sodium fluorosilicate (Na2SiF6).[119] However,
these approaches have not yet been scaled up to a commercial
scale.
An alternative approach is a direct carbonation process of
siliceous lithium ores (spodumene, lepidolite, petalite, and
zinnwaldite) with supercritical CO2. The basis is a thermal
treatment for defluorination (lepidolite, zinnwaldite) and
simultaneous decomposition of the lithium-bearing mineral
phases to b-spodumene. Leaching with CO2/water results in
a dilute LiHCO3 solution, which is enriched by means of
electrodialysis. Subsequently, the solution is heated and
Li2CO3 is precipitated under release of CO2. Follow-up
activities aim at optimizing the sintering process under
consideration of the mineral phase formation to increase
the subsequent lithium mobilization.[120]
A promising alternative for processing sulfuric acid
digestion solutions is an electrolysis or electrodialysis process
to obtain LiOH from purified solutions.[121] At present,
Nemaska Lithium Inc. (Quebec, Canada) plans to scale up
the process to a production volume of 28 000 t a@1 LiOH at the
Whabouchi lithium deposit in Canada.[122] However, the main
challenge is the multistep pretreatment of the lithium-
containing solution to separate multivalent cations (e.g.
Fe3+, Al3+) partially down to the ppb range to prevent the
precipitation of hydroxide in the membrane process.
8.4. Recycling Processes
At present, no extensive industrial recycling of Li is
carried out, and even optimistic scenarios forecasted that only
25 % of the supply would be substituted by secondary lithium
in 2050.[109] The greatest potential lies in recycling lithium-ion
batteries. However, the methods currently employed, such as
the pyrolytic VAL’EAS process (Umicore, Brussels) or low-
temperature separation (TOXCO Inc., Anaheim, USA),
mainly aim at recovering other valuable metals, particularly
cobalt and nickel.[123] Processes with the aim of recycling Li
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have mainly only been tested on laboratory and pilot-plant
scales.[110] A battery recycling company which also recovers Li
is Accurec Recycling GmbH (Heissen, Germany), with an
annual recycling quantity of 4000 t a@1 of spent batteries. By
combining pyrolytic and hydrometallurgical process steps,
Li2CO3 is recovered in addition to the high-priced metals.[43]
Another process aproach is the “hybrid lithium recovery”,
developed in Freiberg, Germany. It is currently the only
known process which is capable of processing both primary
(zinnwaldite) and secondary lithium sources (black mass from
spent lithium-ion batteries). Besides Li2CO3, the market-
established by-products CoOOH, a-FeOOH, and
(Na,K)3AlF6 are recovered in this integrated, holistic
approach. However, the processing costs are quite high, so
the approach is economically viable only at the current price
level for Li2CO3.[124]
At present, the most promising Li recycling approach is
a selective, direct carbonation treatment of black mass with
CO2/H2O. After an electrodialytic concentration process,
Li2CO3 is precipitated in battery-grade quality (bg-Li2CO3,
> 99.5 %).[125]
9. Magnesium
9.1. Economic Significance
When considering the economics of the chemical element
magnesium, one has to distinguish between pure, metallic
magnesium and its compounds. Metallic magnesium is rarely
used in technical applications, while magnesium alloys are
increasingly used in electronics and electrical engineering as
well as in mechanical and automotive applications. In
particular, the low density in combination with a high strength
and resistance to corrosion makes magnesium alloys a versa-
tile metallic material for construction. Another advantage is
the practically unlimited availability because the alloys can be
easily recycled. Magnesium metal, especially in combination
with aluminum, is of great economic significance[51] since it
improves the strength, toughness, and corrosion resistance of
the materials. Approximately 45 % of the magnesium metal
produced is used in the production of aluminum alloys, with
a further 35 % being used in other magnesium alloys
(Figure 10).[126] Magnesium is used in the iron and steel
industry to desulfurize pig iron (13 %). Other applications
(7 %) comprise use as a reducing agent in metal production
processes or as a sacrificial anode in electrochemistry or
cathodic corrosion protection.[127–132]
At an estimated 8 million tons (Mg equivalent), magne-
sium compounds have by far the largest market share. The
most important industrial magnesium compound is magne-
sium oxide (magnesia), which is produced as dead burned
magnesia (DBM), fused magnesia (FM), and caustic calcined
magnesia (CCM). DB and F-magnesia are predominantly
used as refractory materials in the iron and steel industry, but
also in the ceramics and building materials industry. The main
application fields for CC-magnesia are for environmental
protection (water treatment, flue gas desulfurization), agri-
culture (feed and fertilisers), and the chemical industry.[134]
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Figure 10. Global production and applications of magnesium
(2015).[127–133]
Furthermore, the average price of metallic magnesium (purity
99.8 %) fell by 38 % (2000 USD kg@1) from June 2012 to June
2016 (3242 USD kg@1).[11, 12]
9.2. Raw Materials
Magnesium is the second most abundant alkaline-earth
metal, the eighth most abundant element in the earthQs crust,
and the third most abundant one in seawater. As a result of its
high reactivity, magnesium only occurs in an ionic form in
nature. Magnesium is primarily extracted from dolomite
(CaCO3·MgCO3), magnesite (MgCO3), and brucite (Mg-
(OH)2). Other primary sources are salts rich in magnesium,
such as carnallite (MgCl2·KCl·6 H2O), bischoffite
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(MgCl2·6 H2O), and kieserite (MgSO4·H2O), as well as salt
lakes, brines, and seawater. By contrast, siliceous magnesium
compounds, such as olivine ((Mg,Fe)2[SiO4]) and forsterite
(Mg2SiO4), are used only rarely as raw materials.[5, 134]
An important secondary source of magnesium is casting
alloys. During their manufacturing process, large quantities of
new scrap are produced as by-products (Figure S6 in the
Supporting Information). The most significant resource for
secondary magnesium is lightweight components of the
automotive industry.[127, 128] In addition, current approaches
deal with the recovery of magnesium from waste streams of
lignite combustion. However, the suitability of magnesium-
rich lignite fly ashes (+ 15 wt % Mg) as a secondary raw
material depends on the mineralogical composition of the ash
(bonding form, accompanying components), which signifi-
cantly influences the extractability of magnesium.[135] The
development of the Latrobe process (Australia), based on the
Hydromet process developed by EcoEngineers Pty Ltd. in
2013, is highly advanced.[136] In this procedure, the S, Fe, and
Si levels in lignite fly ashes are reduced to a level[137] at which
the MgO concentrates can feed into the Pidgeon Pro-
cess.[132, 138]
As a consequence of the high price (see below), magne-
sium is increasingly being replaced by substitutes. For
example, aluminum and zinc are used in forged and cast
products, even though the benefit of the light metal alloy in
terms of the material weight is lost. Calcium carbide (CaC2)
serves as an alternative for desulfurization in the production
of iron and steel. Nevertheless, magnesium is preferred in this
case despite its price, because of the potential formation of
acetylene when CaC2 and water are brought into contact.[139]
As a result of development in its main fields of applica-
tion, the global demand for magnesium metal has more than
doubled since 2000, with an annual growth rate of 6.6 %. The
global production of primary raw materials for 2014 is
estimated to be 970 000 tonnes, with China clearly dominating
the market.[24] Magnesium metal is currently traded at a price
of 2030 USD t@1 (31.03.2016).[140] Primary magnesium has not
been produced in Europe since 2002.[133, 141]
9.3. Extraction Technologies
A distinction is made between the dry and the wet process in
the production of the industrially most important magnesium
compound, magnesium oxide. In the wet process, magnesium
chloride is precipitated as magnesium hydroxide from sea-
water, brines, or even residual liquids of the lime industry by
adding calcined dolomite or lime. As an alternative, lime milk
is added and the precipitate subsequently calcined to MgO
[Eqs. (16) and (17)]. As a result of the high expenditure of
energy, aqueous electrolysis [Eq. (18)] has instead become
common in chemical technology.
MgCl2 þ CaðOHÞ2 ! MgðOHÞ2 # þCaCl2 ð16Þ
MgðOHÞ2 ! MgO þ H2 O ð17Þ
MgCl2 þ 2 H2 O ! MgðOHÞ2 # þH2 þ Cl2 ð18Þ
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Today, magnesium is typically produced by the dry
method, in which magnesite (MgCO3), occasionally brucite
(Mg(OH)2), is calcined to MgO in a high-temperature
furnace. Depending on the temperature, CCM (800 8C),
DBM in one or two phases (1600 and 2200 8C), or FM
(> 2800 8C) is formed.[134]
There are two industrial processes for the production of
magnesium metal, the fused-salt electrolysis of magnesium
chloride and the thermal reduction of magnesium oxide
(Pidgeon process). The Pidgeon process proceeds according
to Equations (19) and (20), and is today the most important
2 ðCa,MgÞCO3 ! CaO ? MgO þ 2 CO2 ð19Þ
2 CaO ? MgO þ ðFe,SiÞ ! 2 Mg " þCa2 SiO4 þ Fe ð20Þ
method. It was developed at the Canadian National Research
Council (NRC). The first plant was operated in 1941 by
Dominion Magnesium in Haley, Ontario, Canada, where
magnesium was produced until 2008. The process is used
chiefly by the market leader China, where significant
quantities of ferrosilicon are available because of the high
steel output. The energy-intensive process is on the one hand
cost-effective and variable regarding the feedstocks, but on
the other hand associated with high CO2 emissions (42 kg per
kg Mg; Figure S7 in the Supporting Information). In compar-
ison, CO2 emission from steel production is 0.5–2.0 kg per
kg@1 steel.[142] In addition, the unwrought magnesium is often
contaminated with Ni, Cu, and Si. The starting point is almost
always dolomite ((Ca,Mg)CO3), which is reduced after
a calcination step to pure magnesium by ferrosilicon at
1160–1200 8C and at reduced pressure (13–67 Pa) in a con-
tainer made of chrome nickel steel.[5, 26, 132, 143–145]
The calcium oxide fraction forms a basic calcium silicate
slag, whereas magnesium is discharged overhead as vapor and
condensed in a water-cooled condenser outside the furnace.
The magnesium is obtained batchwise and can be further
purified by vacuum distillation (see Section 9.4).
The production of magnesium by wet electrolytic methods
is based on magnesium chloride, which is obtained from sea
water by precipitation with lime milk and reaction with
hydrochloric acid. The complete or partial dehydrated salt is
then fed into the electrolysis cells.
Fused-salt electrolysis (Figure S8 in the Supporting Infor-
mation) at T = 700–800 8C and U = 5–7 V is carried out in the
presence of KCl and CaCl2, thus decreasing the melting point.
The rod-shaped anodes are made of graphite and inserted
from above. At the tips they are surrounded by ring-shaped
cathodes made of steel. The cathodically deposited, metallic
magnesium collects on the molten salt, from where it is
skimmed off. The anodically formed chlorine co-product is
used in the I.G. Farben process to produce anhydrous MgCl2
from MgO according to Equation (21).[5, 132, 143, 146]
MgO þ Cl2 þ C ! MgCl2 þ CO ð21Þ
Nevertheless, the Pidgeon process dominates the world
production of magnesium metal. Various process variants
have been developed with the objective to drastically reduce
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energy consumption and to achieve a process intensification
by continuous or semicontinuous process management (Fig-
ure S9 in the Supporting Information).[5, 132, 143–145, 147]
A first approach in this direction was the Magnetherm
process, which was developed in 1963 by Pechiney-Ugine-
Kuhlmann in France. The method belongs to the silicothermic
processes and is carried out in an electric arc furnace, as
typically used for the Wçhler process for the production of
white phosphorus (P4). The reaction mixture of dolomite and
ferrosilicon is mixed with alumina or bauxite to keep the slag
liquid. The magnesium production is carried out at 50 mbar
and 1600–1650 8C. The magnesium vapor is fed into a surface
condenser, where it solidifies to form magnesium metal.
When the condenser is filled, the process is interrupted and
the condenser is replaced by an empty one. The process is
conducted in a batch mode with cycle times of 10–12 h. In
practice, the high vacuum proves to be expensive.
A further development of the Magnetherm method was
developed in South Africa by Mintek in the early 1980s and is
known as the silicothermic Mintek Thermal Magnesium
process (MTMP or Mintek process). Analogous to the
Pidgeon process, it works with calcined dolomite and
ferrosilicon, but is operated in a DC open-arc furnace. It is
essential to work at atmospheric pressure, which requires
a significantly higher process temperature of 1600–1750 8C.
The volatilized magnesium is captured in a surface condenser,
which is operated above the melting point of magnesium
(650 8C), thus keeping the metal in the molten state for
further processing, refining, and finally ingot casting. The
MTMP can be operated continuously or semicontinuously
and was implemented in a pilot plant with a capacity of
100 kg Mg h@1. In contrast to the Pidgeon process, the
required amount of energy is 8.5 MWh per t Mg instead of
35–40 MWh per t Mg. To date, the design of the condenser has
not been finally resolved. In particular, the materials cause
problems, because the storage of the molten magnesium leads
to an entrapment of impurities from the condenser material
into the product.
The Bolzano process, developed in Bolzano (South Tyrol,
Italy), is also based on the Pidgeon process and is operated
today by Brasmag (Brazil). Pulverized calcined dolomite is
pressed with ferrosilicon into ingots, which are electrically
heated by resistance heating. In this way, only the reaction
mixture and not the entire furnace is heated. At 1200 8C, the
temperature is rather low, but the vacuum of 4 mbar is
demanding. The energy consumption is , 7.3 MWh per t Mg
and the magnesium yield was reported to be 71 % compared
to 77 % (Pidgeon). The Bolzano process is intended for
implementation in the Tami-Mosi project in Nevada (USA),
which is currently in the state of planning.[5, 148, 149]
A recent development is the Zuliani process (Canada),
which can be conceived of as a further development of the
Bolzano process. In this procedure, the supplied energy
originates from a combination of electrical hydropower and
natural gas. The magnesium yield is reported to be approx-
imately 90 %, but a large-scale implementation does not
currently exist.[150]
An alternative to the silicothermic methods are alumi-
nothermic processes, the essential advantage of which is the
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lower process temperature of 900 8C. Similar to the silico-
thermic variants, the majority of the total energy demand
results from production of the reducing agent. The Heggie
process as a process variant is carried out at 1500 8C under an
argon atmosphere in a plasma arc furnace. The energy
required is 6 MWh per t Mg.[148]
Carbothermic processes require very high operating
temperatures of approximately 2000 8C. As a consequence
of their high energy demand, they are no longer operated.
A rather recent development is the solid oxide membrane
(SOM) process (Figure S10 in the Supporting Information).
The energy efficiency is at approximately 10 MWh per t Mg
slightly higher that of the Mintek approach. The operating
temperature is 1100–1300 8C, but unlike the carbo- and
metallothermic methods the reduction is realized electrolyti-
cally. The anode and cathode, immersed in a fluoride-based
electrolyte melt (MgF2-CaF2-MgO) with dissolved MgO, are
separated by a membrane of yttria-stabilized zirconia (YSZ).
Application of a voltage results in oxygen anions migrating
through the membrane to the anode under oxidation to give
O2. At the cathode, magnesium vapor is formed, which is
condensed separately, in analogy to the metallothermic
processes. The high selectivity of the membrane towards
oxygen anions prevents halides from passing. This in turn
allows low-melting halogen-based fluxes to be used.[132, 151]
9.4. Recycling Processes
Rising production and increasing use of magnesium alloys
has led to an increasing volume of waste magnesium.
Recycling without a loss of quality is in principle possible,
but extremely demanding because of the susceptibility of
magnesium to oxidation. Therefore, contaminated magne-
sium is, in general, not reused to produce new, purified
magnesium alloys. One exception is the in-plant remelting of
clean production waste. Thus, magnesium recycling is mainly
limited to the recycling of magnesium scrap in the production
of aluminum alloys, as a desulfurization agent in the steel
industry, or in the production of cast iron as an additive to
promote the formation of spheroidal graphite. These are pure
downcycling processes.
The first reason for magnesium recycling is an energy
saving compared to primary production. Magnesium produc-
tion by remelting of low-contaminated magnesium scrap
requires roughly 30 % less energy.[152] By contrast, highly
contaminated magnesium residues are often discarded.[128]
There are many nontrivial challenges in magnesium
recycling, such as its susceptibility to oxidation, the poor
severability of impurities (e.g. Fe, Cu, Ni, Co, Si), and lower
corrosion resistance and strength. Depending on the degree
of contamination, a salt-free (low degree of contamination) or
salt-based (high degree of contamination) remelting is
applied. The salt-free remelting removes undesirable ele-
ments in a two-step process (melting, pouring) under an inert
atmosphere by introducing gases (e.g. SO2/N2). In salt-based
remelting, chlorine-based cleaning salts are used to remove
the impurities. Cover fluxes serve to protect magnesium from
oxidation. Another method for recycling magnesium is
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distillation, where contaminating elements, with the excep-
tion of zinc, can be separated from magnesium as a result of
their different vapor pressures. Magnesium is vaporized
in vacuo (10@3 bar) at approximately 600 8C and subsequently
recondensed. The distillation can be applied to all magne-
sium-containing residues and has the added benefit of
retaining expensive alloying elements (e.g. Y, Ce, Nd).
However, disadvantages are the high technical input and
the energy consumption.[127, 130, 131, 153]
10. Niobium
10.1. Economic Significance
Niobium is mainly used as a material in high-strength low-
alloy (HSLA) and stainless steels (Figure 11). Approximately
94 % of the global niobium demand is required solely for the
production of steel. HSLA steels contain about 0.05 wt % Nb,
and stainless steels 0.04–0.08 wt % Nb. The most important
niobium alloy is ferroniobium (Fe-Nb alloy), which contains
approximately 60 wt % Nb. As well as the alloys, metallic
niobium is also used in the aerospace industry.[16] Further
applications are superconductor wires, in catalysts for the
production of hydrochloric acid and biodiesel synthesis, as
well as niobium(V) oxide (Nb2O5) as an anode material in Nb-
electrolytic capacitors.[154]
In 2014, global Nb production was 55 900 t Nb, with Brazil
(89 %) and Canada (10 %) accounting for almost 99 % of the
global production of niobium.[7] The fact that niobium is listed
as a critical metal can not be explained on the basis of existing
reserves, but is attributed to Brazil having virtually
a monopoly as a supplying country for primary Nb.[2] Current
market prices are not publicly available, since Nb is not traded
freely. The US import price of ferroniobium was listed at
40 000 USD t@1 in 2014.[156] In addition, Nb2O5 (purity 99.5 %)
has lost approximately 56 % of its value within the last four
years. Nb2O5 was listed at 64 USD kg@1 in June 2012 and at
present at 28 USD kg@1 (June 2016).[11, 12]
10.2. Raw Materials
Large reserves in Canada (0.2 million t Nb) and Brazil
(4.1 million t Nb) render niobium a nonscarce commodity.[156]
The most important niobium minerals are columbite,
(Fe,Mn,Mg)Nb2O6, and pyrochlore, Ca2Nb2O7. Columbite is
found in granites and syenites, while pyrochlore occurs in
carbonatites and alkaline rock bodies.[157] The similarities of
the ionic radii of niobium and tantalum results in columbite
forming a mineral series with tantalite, (Fe,Mn)(Ta,Nb)2O6.
The solid solutions of both minerals are known as Coltan
(columbite/tantalite).
As a consequence of the main usage of Nb as an iron-
niobium alloy in stainless steels, steel scrap is a particularly
good secondary resource. Since the Nb concentration in
stainless steels is low and the life cycles long, Nb from
secondary resources has had no significant impact on the total
supply.
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Figure 11. Worldwide niobium production and applications
(2015).[16, 155]
10.3. Extraction Technologies
Niobium and tantalum are extracted from tantalum-
containing niobium ores. Firstly, the ore is digested with
concentrated H2SO4/HF, whereupon the soluble fluoride
compounds H2[NbOF5] and H2[TaF7] are formed. Secondly,
a fractionated precipitation of slightly soluble potassium
heptafluorotantalate K2[TaF7] is conducted by adding potas-
sium fluoride (KF).[5] In recent years, fractionated precipita-
tion has been replaced almost completely by a selective
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solvent re-extraction with methyl isobutyl ketone (MIBK).[158]
Besides MIBK, a variety of other extraction agents, such as
DEHPA, 1-octanol, tributylphosphate (TBP), and cyclohex-
anone, have been investigated for separating the fluo-
ride.[159, 160] In the case of tantalum-poor niobium ores, Nb is
precipitated as K2[NbOF5] by adding KF, or as Nb2O5 with
aqueous ammonia.[161] Three methods are applicable For the
extraction of niobium metal: 1) fused-salt electrolysis of
K2[NbOF5]/NaCl, 2) by reduction with sodium, and 3) by an
aluminothermic process.[159] However, industrially more
important is the production of ferroniobium. It is carried
out by aluminothermic processing of Fe2O3 and Nb2O5 with
aluminum. Subsequently, electron beam melting is carried out
to achieve higher product purities.[162]
The release of HF during the conventional Nb/Ta-
digestion process led to alternative methods being examined.
A promising approach is the chlorination and subsequent
fractional distillation of NbCl5 and TaCl5.[159] Further pro-
cesses are, for example, pressure digestion with sulfuric acid
(10 mol L@1, 98 % Nb yield),[163] as well as roasting at 400 8C in
the presence of KOH and subsequent water leaching (98 %
Nb yield).[164] Despite the higher Nb yield, both methods have
significant drawbacks, which up to now have prevented them
from replacing the H2SO4/HF digestion process. The pressure
digestion with sulfuric acid is hardly justifiable economically
and the roasting process consumes prohibitively high amounts
of KOH.
10.4. Recycling Processes
Niobium is mainly used in steels, where the Nb content is
less than 0.08 wt %. This is the reason why Nb recycling from
EoL steels is economically not viable. However, the recycling
rate of stainless steels is high, and concomitantly also that of
the contained Nb, and there is an overall recovery rate of Nb
of more than 50 %.[165]
Industrially established processes for Nb recovery were
developed for production and target scrap. H. C. Starck
GmbH (Goslar, Germany) runs an integrated thermal and
chemical recycling process, which recovers niobium as a metal
or oxide in high purities.[166] However, detailed information of
the process is not available.
Nb recovery from EoL products was only successfully
achieved in niche applications. For example, approximately
47 % of the contained niobium is recycled in addition to gold,
silver, and copper from computer circuit boards in a labora-
tory-scale sodium cyanide leaching process.[167]
11. Platinum Group Metals
11.1. Economic Significance
Platinum group metals (PGMs) comprise the lighter
metals ruthenium, rhodium, and palladium as well as
osmium, iridium, and platinum, which are termed the heavy
platinoids. Since 2014, the European Union has classified
PGMs as critical commodities, as a result of limited produc-
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tion capacities and various applications, such as automotive

exhaust catalysts, jewelry, and pharmaceuticals (Figure 12).
Although one exhaust catalyst requires no more than 1–3 g of
the PGMs,[168] the overall demand is high because of the sheer
number of automobiles. Furthermore, stricter emission stand-
ards (Euro 6, LEV III, ULEV) further promote an ever-
increasing amount of valuable metals.[169]
At present, there is increasing demand for platinum in the
medical sector, as a result of a growing number of pharma-
ceuticals produced with hydrogenation catalysts, as well as
platinum-based cytostatic drugs for cancer therapy.[170]
Osmium is generally used as a catalyst. The worldwide
production of osmium barely exceeds 120 kg.[171, 172] Figure 13 Figure 13. Application of the six platinum group metals Pt, Pd, Rh, Ru,
depicts applications for all the PGMs as well as the individual Ir, and Os (primary and secondary production, as well as stock
share of production capacities. The trend in the commodity material).[170, 172]
prices of the PGMs varies according to the element. Between

Table 1: Average commodity prices for platinum group metals.[11, 12, 173]
Element Purity Price June 2012 Price June 2016
[USD oz@1] [USD oz@1]
platinum 99.95 % 1447.14 984.32
palladium 99.95 % 612.34 551.32
rhodium 99.95 % 1325.00 659.77
ruthenium n.a.[a] 112.26 42.00[b]
iridium n.a.[a] 1066.23 525.00[b]
osmium n.a.[a] 450.00[c] n.a.[a]
(2010)
[a] n.a.: not available. [b] April 2016. [c] 2010.

2012 and the middle of 2016, the price of Pd dropped by only

10 %, whereas Rh lost approximately half of its value
(Table 1).[11, 12]

11.2. Raw Materials

There are three categories for PGM-containing ores:

Figure 12. Worldwide production of platinum and palladium (2015).[24]
native metals, sulfides, and intermetallic compounds.[174] The
most important deposits are located in the so-called Bushveld
complex (South Africa), which comprises the Merensky Reef,
Upper Group 2 (UG2), and Platreef deposits. Sulfides,
tellurides, and arsenides (Braggite (Pt, Pd, Ni)S, Cooperite
PtS, Mocheite PtTe2 etc.) can be found in the Merensky Reef,
whereas Norilsk in Russia comprises mainly intermetallic
compounds (Atokite, Pd3Sn; Paolovite, Pd2Sn; Rustenbur-
gite, Pt3Sn; Zyvagintsevite, Pd3Pb; Plumbopalladinite,
Pd3Pb2).[174] Apart from South Africa, which produces
almost 95 % of the PGMs,[175] Russia, Zimbabwe, Canada,
and the USA also contribute noticeably to world produc-
tion.[176] The Stillwater complex (Stillwaterite, Pd8As3) in the
USA has the highest content of PGMs (23 g t@1). Finland and
Botswana play a minor role, as PGMs are only produced as
by-products from Ni-containing ores.[35] In Figure S11 (Sup-
porting Information) squares mark deposits with PGM
contents above the average concentration of the EarthQs
crust, although, only a few of them allow PGMs to be
obtained economically under current market conditions.[177]

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In 2015, the four major suppliers of refined PGMs were
South Africa (4465 koz), Russia (715 koz), Zimbabwe
(405 koz), and North America (385 koz).[178] Since PGMs
have extraordinary high chemical resistance, any treatment of
their ores requires laborious, energy-intensive, and thus
expensive processes.[174]
Therefore, secondary raw materials contribute signifi-
cantly to security of supply. Depending on the type of waste,
these secondary sources of PGMs are divided into two groups.
1) Metal materials such as sheets, crucibles, dental alloys, and
castings represent the most valuable waste, whereas 2) non-
metal wastes (e.g. solutions, salts) contain PGMs only in small
amounts together with various extraneous elements. At
present, most of the secondary Pt, Pd, and Rh is recycled
from exhaust catalysts. These catalysts consist of PGMs
applied to a ceramic support made of cordierite,
(Mg,Fe)2Al4Si5O18.[179] PGM recycling in Europe currently
suffers from the large-scale export of used vehicles, which
removes the potential source material.[180]
11.3. Extraction Technologies
Both underground and open-pit mining are used for
extracting PGM-containing ores. The worldQs deepest mine in
South Africa delivers ores from 2.2 km beneath the EarthQs
surface.[177] The mining is work-intensive, classically involving
blasting the ore and transport with a mine railway. Sometimes
both types of mining are combined to exploit different parts
of the deposit at the same time (South Africa; Lac des Iles,
Canada). Only open-pit mining is used in Ethiopia and parts
of South Africa. Depending on each deposit and the ores
found therein, different strategies of processing may become
necessary (Table 2). Methods differ as the ores are crushed,
floated, separated by gravity, or subjected to pyrometallurgic
treatment in varying order to first concentrate the PGMs.[177]
Many facilities work according to the MF2 scheme, which
conducts grinding and floating twice in a row. This method
aims to reduce loses of PGMs because of the varying
compositions of minerals. Afterwards the concentrate is
dried until the moisture decreases below 0.5 wt % and fed
into an electric arc furnace (> 1300 8C) to separate the
valuable metals as matte from the siliceous slag. Limestone
serves as the fluxing agent. Limestone serves as the fluxing
Table 2: platinum group metal content of selected, important deposits.[177]
Deposit Pt con- Pd con-
tent tent
[g t@1] [g t@1]
Merensky 5–7 (Pt&Pd)
PGM domi-
Contact deposits 1–4 (Pt&Pd)
nant
Chromitite 4–8 (Pt&Pd)
Impact associated 1–10 (Pt&Pd)
Ni-Cu domi- Rift/continental 7.31 1.84
nant basalts
Komatiite < 1 (Pt&Pd)
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agent. Ores from the UG2-deposit are never solely smelted
due to the necessity to produce a matte. Therefore, UG2 ores
are always mixed with ores originating from the Merensky
Reef. These mattes are subsequently desulfurized and sepa-
rated from iron impurities. After separating all non-ferrous
heavy metals, all PGMs are recovered by solvent extraction.
The world’s largest platinum producer, Anglo-Platinum,
employs a process by which these mattes are slowly cooled
down. As the temperature decreases large crystals of PGM
containing Cu-Ni alloys are formed, which are subsequently
ground prior to magnetic separation. The resulting residue is
used for further treatment to produce pure PGM metals. In
Norilsk, the ores (manly intermetallic compounds) are
crushed, fed to gravity separation, and floated. The resulting
solid phase is wet-milled and separated by high-pressure
leaching to yield concentrates of Ni, Cu, and Co.[177]
Concentrates from both primary and secondary origins
are separated to give the pure metals.[20] The conventional
process used to separate the individual PGMs in the concen-
trate as well as from accompanying elements commence with
digestion by aqua regia. Typically, Au, Pd, and Pt are in
solution, while Rh, Ru, Ir, Os, and Ag remain in the solid
residue (Figure 14). The solution is treated with Fe2+ (or
worked up by solvent extraction) to yield Au. The addition of
NH4Cl precipitates (NH4)2PtCl6, subsequent calcination of
which provides platinum sponge. Adding NH3 followed by
HCl to the deplatinated solution gives Pd(NH3)2Cl2, calcina-
tion of which furnishes palladium sponge.
The solid residue of heavy PGMs is smelted with PbCO3
and coke, followed by leaching with nitric acid, upon which
Ag and Pb are dissolved. After filtration, the residue is
digested with NaHSO4, which selectively converts Rh into
water-soluble Rh2(SO4)3, before it is precipitated as Rh(OH)3
with NaOH and further processed to rhodium metal. Ru, Ir,
and Os remain in the solid residue. Heating the residue with
sodium hydroperoxide at 500 8C converts Ru and Os into their
water-soluble ruthenates and osmates, thus allowing them to
be separated from insoluble IrO2, which is further processed
to give iridium metal. The separation of Ru/Os is achieved by
chlorination in a Cl2 atmosphere and subsequent distillation.
Gas scrubbing with hydrochloric acid produces water-soluble
OsCl4 and [RuCl6]2@. The addition of nitric acid yields volatile
OsO4. The remaining chlororuthenate is further processed to
Ru metal.[174]
Examples
Merensky Reef, (South Africa); Great Dyke (Zimbabwe); Stillwater (USA); Munni Munni
(Australia)
Bushveld complex (South Africa); Duluth complex (USA); Lac des Iles (Canada);
Portimo (Finland)
Stillwater Complex (USA)
Sudbury (Canada)
Jinchuan (China)
Australia, Russia, Canada
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Figure 14. Recovery and refining of ores containing platinum group metals and secondary raw materials originating from Cu production.[5]

11.4. Recycling Processes a first measure.[181] In addition to WEEE processing, pyrolysis

In the recovery of PGMs from secondary raw materials,
classical pyrometallurgical, hydrometallurgical, and electro-
lytic steps are combined within one process. As a consequence
of the low PGM contents of the source materials and the high
organic impurities, both catalysts and WEEE are calcined as
is being discussed as an alternative to combustion.[182]
In contrast to PGM-containing ores, these wastes are
mixed with a collector metal, such as Cu and smelted in a shaft
furnace to extract the PGMs from the waste material by
forming an alloy with the added metal (Figure 14). The
resulting Cu alloy contains up to 20 wt % PGMs. Slag-forming

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agents are fed into the furnace to remove oxidic impurities.
Afterwards, the Cu-PGM alloy is cast into anodes and
subjected to electrolysis, whereby PGMs accumulate in the
sludge. Alternatively, the alloy can be leached with sulfuric
acid, with the PGMs remaining completely in the solid,
undissolved residue. Afterwards the residue is treated anal-
ogously to primary raw materials, starting with aqua regia
leaching.[183]
Ion exchange and solvent extraction have, in particular,
recently been used for separating PGMs from each other,
since fractional precipitation proved to be laborious and
uneconomical to achieve yields > 95 % (Figure S12 in the
Supporting Information). Only the precipitation of (NH4)2-
[PtCl6] is still used to separate Pt.[184, 185] For example, the use
of Lewatite S100 as an ion-exchange resin easily removes
> 96 % of the Fe and Ni. Excess acid is recovered by
distillation. Solvent extraction processes employ conventional
compounds, such as triisobutylphosphine sulfide (TIBPS) and
di-(2-ethylhexyl)phosphoric acid (DEHPA), which reliably
transfer > 99 % of the Pd into the organic phase. In principle,
the same applies to Pt, when thiosulfate is added for re-
extraction. Finally, Rh is recovered by applying ion-exchange
resins.[185, 186]
Besides conventional methods, Rh may also be recovered
with the help of microorganisms, for example, Shewanella
algae.[187] This bacterium is able to reduce RhIII to metallic Rh
in the presence of lactic acid as an electron donor. Analogous
to Rh, Enterococcus faecalis recovers Pd in the presence of
sodium formate instead of lactic acid.[188] These microbial
recycling approaches yield PGMs in the form of nanoparti-
cles, which have been tested as catalysts for the reduction of
CrVI.[188]
It is even possible to separate Rh and Ir in concentrated
hydrochloric acid by extraction with organic amines (Ali-
quat 336). Re-extraction with thiourea dissolved in water
provides high separating factors of up to 82.5 for Ir.[189]
Another approach deals with removing Ru from acetic
acid solution using E. coli immobilized on filaments made of
polyethylene imine/polysulfone composites. These filaments
showed higher capacities for ion exchange than conventional
resins, and have been applied to recover Ru from waste water
originating from the production of acetic acid.[190]
Osmium-based catalysts (Lemieux–Johnson reaction) can
be recycled by reductive extraction. Subjecting these catalysts
to a 2-propanol/KOH solution reduces OsVIII selectively to
OsO42@, which can be removed thereafter from the organic
phase without any side reactions.[191]
Besides the different ways of extraction already used in
industrial separations (Figure S12 in the Supporting Informa-
tion), ionic liquids, in particular, have recently attracted
increased attention.[192, 193] Ionic liquids allow only one or at
most a few elements to be separated selectively. For example,
1-butyl-3-methylimidazole hexafluorophosphate (([Bmim]-
[PF6]) proved suitable for extracting PtIV and PdII from
a solution of AuIII. Extraction rates for platinum are reported
to reach 80 %.[193] However, the production of ionic liquids is
still too expensive to justify an economic application in
industrial processing.[194]
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12. Rare Earth Elements
12.1. Economic Significance
Between the discovery of the first rare earth metal in
ytterbite in 1887 and the advent of nuclear technology in the
1940s, scandium, yttrium, and the lanthanides were only of
scientific interest.[20] Rare earth metals then gained in
importance since they are produced during the fission of
uranium, and may serve as neutron absorbers (157Gd, 147Sm).
The production of individual rare earth (RE) elements
subsequently led to the development of efficient separation
techniques, for example, ion exchange.[195] Demand as well as
economic significance increased massively as the fields of
application increased. Today, RE metals can be found in
various high-tech products such as permanent magnets,
electric engines, hard drives, wind power plants, and smart-
phones (Figure 15). In addition, RE metals are essential for
industrial products such as alloys, fluorescent lamp materials,
ceramics, and glasses (Table 3).
Figure 15. Application and demand of rare earth elements for 2006,
2012, as well as 2017 (predicted).[196, 197]
As a consequence of the large worldwide deposits of
approximately 130 million t (Figure 16) and comparably low
production rates of 130 000 t a@1 (2015),[24] there is no doubt
that the static supply of RE metals could last for several
centuries.[20] However, both the European Commission[198]
and the Deutsche Rohstoffagentur (DERA)[199] consider RE
metals (particularly the elements Nd, Dy, Tb, and Eu that are
necessary for the production of magnets and lamp materials)
to be most critical commodities with the highest risk of price
fluctuations and delivery shortages. This obvious contra-
diction is caused by the unilateral distribution of exploitable
deposits and production capacities. China dominates the
market, with about 50 % of the worldwide reserves of RE
metals (55 million t) and vast production facilities supplying
85% of the annual world production (105 000 t rare earth
oxides in 2014).[24] Therefore, any shortage of supply is
connected to economic decisions rather than to actual existing
reserves. For example, the announcement by China in 2010 of
an upcoming reduction in RE metal exports down to
35 000 t a@1 caused the commodity prices of rare earth oxides
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Table 3: Commodity prices and applications of all 17 rare earth elements classified according to their use in a) metallurgy, b) magnets, c) catalysts,
d) polishing agents, e) glasses, f) illuminants, and g) ceramics.[5, 11, 12, 20, 63, 174, 196, 201]
Element Application Prices for SE2O3
examples 2012–06 2016–06 a b c d e f g
[USD kg@1] [USD kg@1]
scandium light alloys with Al and Mg 3991.38 1468.39 + @ + @ @ @ @
traces: catalysts, metal vapor lamps (99.5 %) (99.5 %)
yttrium alloys for electrodes, Y2O3 :Eu flourescent material 135.55 3.65 + + @ @ @ + +
traces: FeNdB magnets, YAG laser (99.999 %) (99.999 %)
lanthanum LaCo5 magnets, glasses with high refractive index, polish, FCC catalysts, LAP
25.43 1.90 + + + + + + @
fluorescent material[a] (99 %) (99 %)
cerium Al and Fe alloys, polish for glasses, support of automotive catalysts 25.40 1.53 + @ @ + + + +
(99 % (99 %
CeO2) CeO2)
praseodymium UV-absorbing glasses, Pr-Fe-Co magnets 97.50 51.50 @ + @ @ + @ @
(99 %) (99 %)
neodymium FeNdB magnets, colored glasses (violett) 111.70 40.30 @ + + @ + @ @
(99 %) (99 %)
promethium traces: permanent luminous paint, radionuclide batteries (147Pm) n.a. n.a. @ @ @ @ @ + @
samarium SmCo5/Sm2Co17 magnets, IR-absorbing glasses, catalysts for hydrogenation 65.61 1.93 @ + + @ + @ @
(99 %) (99 %)
europium three-band fluorescent material (ScAp, BAM, Y2O3 :Eu), safety color (50 E bank 2450.00 63.79 @ @ @ @ @ + @
note)[a] (99 %) (99 %)
gadolinium Gd-Fe-Co alloys, MRT contrast agent traces: CRT fluorescent material 92.00 32.00 + @ @ @ @ + @
(Gd,Ce,Tb)MgB5O10[a] (99 %) (99 %)
terbium FeNdB magnets, Tb-Fe-Co-alloys, fluorescent material, safety color (100 E bank 2147.50 428.81 + + @ @ @ @ @
note) (99.9 %) (99.9 %)
dysprosium FeNdB magnets, Tb-Dy alloys, special glasses 1127.50 190.43 + + @ @ + @ @
(99 %) (99 %)
holmium Ho-Fe-Ni-Co alloys for magnetic bubble memory, special glasses; traces: doping n.a. n.a. + @ @ @ + @ @
for YAG laser
erbium IR-absorbing glasses 149.95 26.29 @ @ @ @ + @ @
traces: Er:YAG laser (99 %) (99 %)
thulium traces: activator in fluorescent materials, special glasses n.a. n.a. @ @ @ @ + + @
ytterbium Yb2Co13Fe3Mn magnets, steel alloys n.a. n.a. + + @ @ @ @ @
traces: Yb:YAG laser
lutetium traces: scintillator material, Lu-garnet fluorescent material for LEDs n.a. n.a. @ @ @ @ @ + @
[a] BAM = Eu -doped Ba-Mg aluminate, CRT = cathode ray tube, FCC = fluid catalytic cracking, MRT = magnetic resonance tomography, LAP = Tb3+-
2+

doped La-Ce phosphate, ScAp = Eu2+-doped Sr-Ca-Ba phosphate, n.a. = not available.

(REOs) to increase up to 10 times the level of the year

before.[200]
Secondary raw materials show a very similar situation.
One has to be aware that outside China less than 1 % of the
RE metals are recycled.[22] Fluorescent lamp scrap containing
up to 20 wt % RE elements are forced by German law (KrW/
AbfG) to be disposed of as hazardous waste, since EoL scrap
is typically contaminated with about 0.5 wt % Hg. Before
2011, the recycling of spent NiMH accumulators focused
solely on Ni and Co, while fully ignoring the anode material
containing high levels of RE elements. During pyrometallur-
gical treatment, the RE elements were enriched in the slags
and were disposed of afterwards. The development of
efficient recycling strategies is badly needed to counteract
the current situation.

12.2. Raw Materials

At the moment, five different minerals serve as the raw

material for the primary production of RE elements, namely,
loparite-(Ce) ((Na,Ce,Sr)(Ce,Th)(Ti,Nb)2O6), monazite-(Ce)
Figure 16. Worldwide production of rare earth metals (2015).[24] (Ce(PO4)), bastn-site-(Ce) ((Ce,La)(CO3)F), xenotime-(Yb)

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((Yb,Y,Er)[PO4]), and gadolinite-(Y) (Y2Fe2+Be2Si2O10 ;
Table 4). Since the 1980s, ion-adsorbing clays have been
added to this list.[174] China has access to all RE elements from
various deposits: Light RE elements (Sc, La-Eu) are, for
example, contained in bastn-site deposits in Inner Mongolia.
Deposits containing heavy RE elements (Y, Gd–Lu), such as
various RE-rich clays, are located in Lognan, as well as in
a monazite deposit found in Guandong.[63] Further extensive
deposits are found in Russia (Tomtor in Siberia), Brasil, India,
Australia, Greenland (Kvanefjeld and Kringlerne), and the
USA (Figure S13 in the Supporting Information). Many of
these deposits still remain unexploited because of harsh
climate conditions, low commodity prices, and missing infra-
structure.[202]
Apart from China, countries such as the USA, India,
Russia, Australia, and Thailand contribute to the world
production of rare earth oxides (Figure 16). However, mining
often suffers from Th and U being associated with the RE
minerals. Monazite from Australia typically contains 4–
8 wt % Th and 0.01–0.1 wt % U. The same applies for deposits
in India (8–10 wt % Th), the USA (0.02 wt % Th, 0.002 wt %
U), and Greenland.[174, 202, 203] Both elements require additional
treatment, as they have to be separated from the RE elements
by precipitation and have to be treated as hazardous waste.
Although there are vast fields of application that generate
various secondary raw materials for the recycling of RE
elements, only a few of them are actually fed into recycling
processes for economic reasons. Commodity prices for rare
earth oxides have dropped rapidly since 2011, thus making
many recycling processes uneconomical. For example, recy-
cling spent polish agents containing 90 wt % CeO2 has
become unprofitable, as CeO2 prices decreased from
25.40 USD kg@1 to 1.53 USD kg@1 within four years.[5, 11, 12]
Another issue considers high-tech materials, for example,
YAG lasers, catalysts (Sc), and fluorescent materials, which
contain RE metals only in trace concentrations. It is
conceivable that these RE metals could be recycled as a by-
product, while focusing on valuable metals of higher concen-
tration. At present, recycling only makes use of secondary raw
materials with the highest RE contents available, namely:
1) Nd2Fe14B magnets from wind power plants contain up to
35 wt % RE metals. Rotor segments of only one 3 MW
wind power plant use not less than 500 kg of these
magnets.[204] Nd2Fe14B alloys are also preferred for hard
drives and electric engines, because of their high magnetic
energy densities (BH)max of 450 kJ m@3. Above all, current
challenges consist of collecting distinct magnetic alloys
separately as well as in removing magnets from electronic
waste.[205] Only in 2010 did Hitachi announce the first
process for separating magnets mechanically from old
hard drives.[206]
2) Permanent magnets consisting of Co and Sm are used in
the form of SmCo5 and Sm2Co17 alloys. Compared to
Nd2Fe14B magnets, they suffer from lower magnetic
energy densities (BHmax = 160–260 kJ m@3) and higher
costs of production, but their extraordinarily high Curie
temperatures of 700–850 8C allow for applications above
150 8C.[63, 205] However, at present, less than 2 % of the
spent magnets consist of SmCo alloys, thus leading to
comparable small material flows of 2000–3000 t a@1.[207] It
seems reasonable to collect and recycle both kinds of
alloys together. Besides Sm and Nd, additional RE metals
may be part of magnets. Pr serves as a cheap substitute for
Nd, while Dy and Tb enhance the temperature stability of
Nd2Fe14B alloys. Furthermore, Gd and Ce increase the
temperature stability as well as corrosive resistance of
SmCo magnets.
3) In 2009, when the regulation EG 245 had come into force,
higher standards for light quality became effective, which
the older and rare-earth-free halophosphate fluorescent
materials are unable to meet. Within three years these
halophosphates had to be fully replaced by three-band
fluorescent materials containing RE elements.[208] Subse-
quently, the RE metal content of production wastes has
risen to 22 wt %. Alhough EoL fluorescent lamp scrap
amounts to a much lower content, its levels of RE metals
are also increasing and have reached 7 wt %. EoL wastes
comprise a special challenge for hydrometallurgical recy-
cling, since Hg has to be separated first to avoid any
contamination of process streams. Additionally, the ratio
of three-band to halophosphate fluorescent materials
varies over a wide range. The same applies for the levels
of RE elements. The six RE elements of three-band
fluorescent materials always appear together. Of these,
70–75 % is Y, which occurs jointly with Eu3+ in the form of
the only red-emitting fluorescent substance Y2O3 :Eu3+
(Table 5). The remaining RE elements Gd (2–3 %), Ce
(8–10 %), Eu2+ (4–6 %), and Tb (4–6 %) are essential

Table 4: Rare earth content of selected deposits in % rare earth oxide.[63, 174]
Bastn-site Clays Monazite Loparite Xenotime
REO Bayun Obo, Montain Xunwu, Lognan, Mt. Guandong, Steenkampskraal, Lovozersky, Malaysia
China Pass, USA China China Weld, China South Africa Russia
Australia
La2O3 23.0 33.2 43.3 1.8 25.5 23.0 20.7 28.0 0.5
CeO2 50.0 49.1 2.4 0.4 46.7 42.7 45.8 57.5 5.0
Pr6O11 6.2 4.3 9.0 0.7 5.3 4.1 5.1 3.8 0.7
Nd2O3 18.5 12.0 31.7 3.0 18.6 17.0 17.7 8.8 2.2
Eu2O3 0.2 0.1 0.5 0.1 0.6 0.1 0.1 0.1 0.2
Tb4O7 0.1 < 0.1 < 0.1 1.3 0.1 0.7 0.2 0.1 1.0
Dy2O3 0.1 < 0.1 < 0.1 6.7 0.2 0.8 1.0 0.1 8.7
Y2O3 < 0.1 0.1 8.0 65.0 0.4 2.4 4.2 < 0.1 60.8

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Table 5: Selected three-band fluorescent materials.
Fluorescent material Emission color
Y2O3 :Eu3+ (YOE) red
La(PO4):Ce3+,Tb3+ (LAP) green
(Ce3+, Tb3+)MgAl11O19 (CAT) green
(Gd3+, Ce3+, Tb3+)MgB5O10 (CBT) green
BaMgAl10O17:Eu2+ (BAM) blue
(Ca, Sr, Ba)5(PO4)3Cl:Eu2+ (ScAp) blue
components of green- and blue-emitting fluorescent
materials. La (5–10 %) solely appears in LaPO4 :Ce3+,Tb3+,
which is used as a green-emitting material.[209–211]
4) In NiMH accumulators, La, Ce, and Nd form part of the
anode materials and appear either as type AB5 alloys or
more seldom as type AB2 (A = SE and B = Ni, Co, Al).
Every year 35 000 t of battery scrap is produced within the
EU.[212] The mixture of RE metals (Mischmetal) used for
manufacturing these anodes consists of 50–55 wt % Ce,
18–28 wt % La, and 12–18 wt % Nd.[213] Thus, the levels of
RE elements depend strongly to what extent the accumu-
lators are disassembled. In general, NiMH accumulators
are made up of nine different parts, namely: cathode,
anode, separator, seal, venting mechanism, isolating PVC
disk, electric contacts, protective cover, and metal hous-
ing.[214] The anode easily achieves levels of RE metals
above 30 wt %.[213] If the whole accumulator is ground, this
content decreases to 2.5–10 wt %.[207, 215] The latter is state
of the art, since accumulator recycling focuses on recover-
ing Ni and Co for steel production rather than on RE
metals.[207]
12.3. Extraction Technologies
Processing of RE metals starting from primary raw
materials always follows the same three steps: 1) mining,
2) hydrometallurgical treatment, and 3) separation.[63] Cur-
rently, all ores containing RE elements are mined in opencast
mines (Table 4). At first, the ores undergo several steps of
flotation, magnetic separation, or gravity separation to
remove the gangue.[5, 20] In the case of monazite, the ore is
crushed, wet-milled, and depleted of siliceous impurities
(ca. 2.6 g cm@3) by using jigs, shaking tables, or washing
processes. By this means, minerals of higher density, such as
monazite (4.6–5.4 g cm@3), zircon (ZrO2), rutile (TiO2), ilmen-
ite (FeTiO3), and cassiterite (SnO2) remain as the heavy
part.[20] Further treatment using strong magnetic fields yields
a concentrate of > 95 wt % monazite.[63] The same steps are
applied for hematite-containing bastn-site deposits in Bayun
Obo (China) to concentrate rare earth oxides above 65 wt %,
whereas uranium- and thorium-contaminated bastn-site ores
from Mountain Pass (California, USA) have been subjected
to hot flotation, before the resulting concentrate is treated
with hydrochloric acid to remove any remaining alkaline
earth metals. The objective is a concentrate with approxi-
mately 68–72 wt % rare earth oxides.[20]
Further processing involves several hydrometallurgical
processes and varies depending on the ore, impurities, and RE
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element content (Figure S14 in the Supporting Information).
Sulfuric acid is used preferably to dissolve the REh elements
from monazite ores, in which high levels of siliceous
impurities appear together with comparably low levels of
RE elements. In the case of ores rich in RE elements, the
alkaline process using 12.5 m NaOHaq is applied to yield
Na3PO4 ·12 H2O as a marketable by-product and to uniformly
transfer RE elements to their hydroxides.[20, 174] To separate
them from Th(OH)4 and Fe(OH)3, the precipitate is leached
with hydrochloric or nitric acid at pH 3–4.[5, 20, 63] Since Th
reacts to form radioactive Ra through a decay, Ba2+ and
sulfate ions are added to precipitate any dissolved 228Ra
together with BaSO4. Alternatively, Th may be separated
from RE elements by solvent extraction after dissolving the
hydroxides in dilute nitric acid. For example, Solvay applies
this variant for monazite sands in their facilities in La R-
ochelle.[20]
With the exception of the Molycorp process (Mountain
Pass, California, USA), all the processes suffer, in general,
from their high consumption of chemicals (Figure S14 in the
Supporting Information). This applies, in particular, when
there are multiple changes between strong acid and basic
pH values.
At the end of each winning process, the RE elements are
separated, which can be very laborious because of their
similar physical and chemical behavior. As the atomic
number increases, the 4f orbitals become increasingly occu-
pied, but since the f orbitals are strongly shielded by the
atomic core, any chemical bond is formed with the 5d or
6s orbitals instead. Subsequently, the main oxidation state
(+ 3) is the same for all the RE elements. However, Eu2+ (half
occupied 4f7) and Ce4+ (unoccupied 4f0) provide an oxidation
state different from + 3 in aqueous solution. This property
allows EuSO4 to be precipitated selectively, whereas CeO2
remains untouched by hydrochloric acid, because of its high
acid resistance (Figure S14 in the Supporting Information).
There are three fundamental methods for the separation of all
17 RE elements: 1) fractional precipitation (hydroxides,
double sulfates) as well as crystallization (double nitrates),
2) ion exchange, and 3) solvent extraction.
Fractional precipitation and crystallization are only of
historic interest.[216] Only double sulfates are still used for
separating light rare earth elements from the heavy ones in
one step.[217, 218] Unfortunately, double sulfates are not a mar-
ketable product and require further treatment, which proves
to be disadvantageous compared to simply precipitating with
oxalic acid. The first step involves leaching with NaOHaq to
yield hydroxides followed by either diluting in hydrochloric
acid to yield the corresponding chlorides or drying at > 100 8C
to yield the oxides.
In the 1950s fractional separation of RE elements was
replaced by ion exchange, thereby allowing them to be
produced with the highest purity (> 99.9999 %). However,
laborious recovery of chelating ligands and low concentra-
tions of the RE elements in the resulting eluate (2–10 g L@1
RE element) made this method much more expensive than
solvent extraction.[5] Acidic cation-exchange resins such as
polystyrene-divinylbenzene copolymer or phenol-formalde-
hyde resins are commonly used for the separation.[20, 219] The
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adsorption of RE elements is far from being selective. The narily high levels of RE elements, such as permanent magnets,
separation is conducted by eluting with increasing concen- fluorescent materials, and NiMH accumulators.
trations of hydrochloric acid (often accompanied by NH4Cl)
and by adding different complexing agents, for example, citric 12.4.1. Permanent Magnets
acid, lactic acid, hydroxyethylenediaminetriacetate
(HEEDTA), and ethylenediaminetetraacetic acid (EDTA). In contrast to spent magnets of EoL products, production
Different complex and solution equilibria are able to yield waste can be recycled in many different ways (Table 6).
separated RE elements after 15–34 exchange columns.[20, 219] Approximately 10–30 % of the source alloys leave the
The NH4Cl serves as a regenerating agent for the ion- manufacturing process as a slurry, powder, or chips. Pyrome-
exchange resin. Current research is based on selective ion
exchange using steric distortion of an organic lattice structure
Table 6: Selected recycling processes designed for Fe14Nd2B magnets.
to separate RE elements according to their ionic radius.[220]
Since the 1960s, solvent extraction has primarily been Company Process/source material Yield of Ref.
RE ele-
used for the separation of RE elements. Nowadays, the
ment
organic phase used is kerosene containing 1-decanol to [%]
accelerate phase separation.[218] Chelating ligands, such as
carboxylic acids (EDTA) or phosphoric acids and esters are Shin Etsu[a] blending and melting of produc- n.a. [222]
(Japan) tion waste with FeNdB alloys
commonly used as extracting agents. Typical phosphorus-
(chips) at 1550 8C
based chelating agents are tributyl phosphate (TBP), di-(2- Showa Denko[a] blending and melting of produc- 86.5 [223]
ethylhexyl)phosphoric acid (DEHPA), 2-ethylhexyl hydro- (Japan) tion waste (powder) with new
gen-2-ethylhexylphosphonate (PC-88A), and bis(2,4,4-trime- alloy powder at 1550 8C in an
tylpentyl)dithiophosphinic acid (Cyanex 302). Both the electric arc furnace
extraction and re-extraction are conducted in mixer settler Pure Etch Compa- hydrometallurgic treatment for 95 [224]
ny[a,b] (USA) recovery of RE elements from
systems with a countercurrent flow. They strongly depend on
slurries and chips
the pH values of the aqueous phase (Figure S15 in the Santoku Metal hydrometallurgic treatment for 95 [225]
Supporting Information). Industrya,b) recovery from production waste,
As the pH value is decreased, the light rare earth elements (Japan/USA) precipitation of RE elements
are re-extracted before the heavier elements.[20, 174, 217, 218] using oxalic acid
Product purity is lower than that from ion-exchange process- Panasonic[a] organic solvents remove the n.a. [226]
es, but is somewhat higher than 99.99 %.[219] In contrast to ion (Japan) plastic mantle, blending and
melting of production waste with
exchange, solvent extraction is conducted continuously and
FeNdB alloys at 1550 8C
achieves 10–50 times higher concentrations of the RE ele- Hitachi[a,b] (Japan) mechanic separation of magnets, 95 [206]
ment in the extracts and raffinates.[5] combination of pyrometalluric
With the exception of three RE elements, subsequent and hydrometallurgic recycling
reduction to the metals is conducted by fused-salt electrolysis [a] Sufficient for production waste. [b] Sufficient for EoL waste). n.a.: not
from a chloridic (La-Nd) or fluoridic melt (Gd-Lu).[20] The available.
chlorides serve as the source material for the electrolysis of
light rare earth elements. Moreover, NaCl as well as CaCl2, tallurgical processes are used preferably, thus avoiding the
BaCl2, NaF, and rare earth fluorides are also added. The expensive reduction, but these processes are insufficient when
presence of fluorides lowers the melting temperatures to 700– it comes to recycling EoL materials. Corrosion, adhesives,
900 8C and results in the melts having lower viscosities. plastic sockets, as well as accompanying elements such as Ni,
However, the melting temperatures of the chlorides of the Co, and Zn (corrosion protection) hinder any pyrometallurgic
heavy rare earth elements Gd–Lu are too high. Instead, their recycling and contaminate the recovered RE metals. New
fluorides and oxides are mixed with LiF and BaF2 to yield magnets would subsequently suffer from decreased rema-
a fluoridic melt of comparable temperature. For the elements nence. Wet chemical treatment is more suitable to remove
Sm, Eu, and Yb, for which fused-salt electrolysis is inappro- these impurities.
priate, metallothermic reduction is applied. The oxides or Approaches using mechanical recycling have also been
fluorides are reduced at 1300–1400 8C by adding other RE examined, but have so far failed to meet the requirements for
metals (e.g. La). electric engines. This applies to reusing undamaged magnets
for assembling new engines as well as for blending new
starting alloys with ground EoL magnets during manufactur-
12.4. Recycling Processes ing. Mixing 30 wt % EoL magnet powder with 70 wt % of the
starting alloys resulted in remanence loses of only 3 %, which
As a consequence of the extensive deposits and low was enough to already miss the high standards.[217, 218, 221]
commodity prices, only a few processes are currently capable In the case of wet processing, old magnets are first crushed
of recycling RE elements economically. Furthermore, most of and ground, before mineral acids dissolve the resulting
them focus only on production wastes. Economic concepts for magnet powder completely. In general, hydrochloric
the much more challenging EoL recycling are quite rare and acid,[217, 218, 227] nitric acid,[225] sulfuric acid,[225, 228] or acetic acid
exist exclusively for secondary raw materials with extraordi- are used for leaching.[224] The combination of leaching with

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reactive grinding results in the NaOH added previously
transforming the metals to hydroxides. This compensates for
the lower acidity of the acetic acid used subsequently.
Accompanying elements such as Ni, Co, and Fe can either
be retained by keeping the pH values > 3 or removed from
the leaching solutions by precipitating insoluble sulfides (Ni,
Co) or jarosite and goethite (Fe).[225, 228] Both methods have
their own disadvantages. Selective leaching at pH > 3 will not
entirely leach RE metals without additional pretreatment.
Any Fe retained during the leaching partially shields the RE
metals, which causes lower yields. On the other hand,
precipitating these elements from strongly acidic leaching
solutions also needs an adjustment of the pH value, with
excess acids having to be almost completely neutralized.
Furthermore, impurities also co-precipitate with the RE
metals, which subsequently reduces the yields. For example,
CoS precipitated in the MORE process consisted of about
3 wt % RE elements.[218]
Apart from dissolving magnets, the following treatment
generally uses state of the art process steps already applied for
extraction technologies, such as precipitating rare earth metal
oxalates,[224, 227] fluorides,[224, 228] and double sulfates[217, 218, 228] or
separating rare earth metal ions directly by solvent extrac-
tion.[217, 218] Depending on each element and how it was
precipitated, the reduction to the RE metals may require an
additional halogenation step.
In recent years alternative recycling methods have, there-
fore, gained in importance, for example, solid-state chlorina-
tion with NH4Cl (Figure S16 in the Supporting Information).
This method aims to produce nonvolatile, water-soluble metal
chlorides by thermally decomposing NH4Cl at 338 8C, with the
gaseous HCl released reacting with the secondary raw
material. NH4Cl is a much cheaper source of HCl than
conventional applied mineral acids, as it represents a waste
material itself (e.g. from polysilane production).[229] More-
over, solid NH4Cl contains almost twice as much HCl as
concentrated hydrochloric acid. As the name implies, solid-
state chlorination produces undissolved, dry metal chlorides
instead of strongly acidic solutions. Therefore, dilute acids or
buffer solutions at moderate pH values of 3–4 are sufficient to
dissolve the formed chlorides. The gaseous NH3 also origi-
nating from the decomposition of NH4Cl leaves the reactor
without affecting the chlorination. If transferred to a scrubber,
the NH3 can even yield a marketable by-product, if the
resulting ammonia solution meets the purity requirements. In
addition, thermal decomposition is reversible, which allows
unreacted NH4Cl to be recovered in a subsequent step by
allowing the gaseous phase to cool down. In summary, this
technique is characterized by extraordinary low costs of
chemicals and has been successfully examined for Fe2Nd14B
magnets as well as fluorescent lamp scrap from production
wastes and EoL products.[209–211] In this way, EoL recycling
and pyrometallurgic processes achieved comparative yields of
RE metals of 84–95 %, depending on which method was
used.[209–211, 217, 218, 224]
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12.4.2 Fluorescent Materials
Approximately 250–300 t of mercury-contaminated fluo-
rescent lamp scrap with average levels of RE metals of about
10 wt % are disposed of in Germany every year.[230] Prior to
a wet chemical recovery process, such as used by Solvay Rare
Earth in La Rochelle, Hg has to be fully removed by
distillation at > 357 8C. In addition to EoL lamp scrap, there
are also Hg-free production wastes with rare earth metal
contents up to 22 wt %. Since 2008, both waste materials have
been partially recycled in wet chemical processes for the
recovery of rare earth oxides (Figure S17 in the Supporting
Information). At the moment, Solvay is capable of recycling
about 3000 t of Hg-free energy-saving lamps per year,[230]
whereas FNE Entsorgungsdienste Freiberg treats production
wastes with the SepSELSA process.[231] For recycling of the
more demanding EoL products, a process has been developed
at Freiberg University of Mining and Technology, which
realizes the selective digestion of Y and Eu by solid-state
chlorination, while bypassing any additional step of Hg
removal.[209–211]
Compared to the processes applied by Solvay and Osram,
both the wet chemical recycling practised by FNE as well as
the solid-state chlorination by Freiberg University of Mining
and Technology avoid costly changes in pH values (acid/basic)
and require less production steps. In addition, diffusion
dialysis allows up to 85 % of the excess hydrochloric acid to
be recovered. Furthermore, Eu is separated by cementation
with Zn to reduce Eu, which is precipitated as water-insoluble
EuSO4 on adding sulfate to the solution. This approach results
in the costs for chemicals, processing, as well as disposal being
reduced significantly. The dry chemical digestion through
solid-state chlorination provides further advantages: Hg
removal, selective chlorination of red phosphor Y2O3 :Eu3+,
and production of ammonia as a marketable by-product
proceed simultaneously in one single-process step. In the
following leaching step, up to 99 % of the Y and 96 % of the
Eu can be separated from La, Ce, Tb, and Gd with
selectivities > 99.7 %.[210] However, solid-state chlorination
requires a specially designed rotary kiln with different heating
zones and full control of the gaseous phase. The development
and construction of such a kiln is a matter of current research
activities.
12.4.3. NiMH Accumulators
NiMH accumulators provide high Ni contents of 36–
42 wt % and thus serve as cheap Ni sources for the steel
industry.[207, 232] After mechanical treatment, Ni and Co are
separated from the accumulator scrap as a melt that leaves the
electric arc furnace. The 2.5–10 wt % RE metals remain in the
slag and are lost for recycling. Since La and Ce constitute up
to 80 % of these RE metals, and since low commodity prices
render individual recycling uneconomical, the recycling of RE
metals is based on the slags obtained from Ni recovery.[213]
Purely wet chemical treatment of the accumulators or the
separated anode materials with mineral acid, chiefly
H2SO4[213, 214] or HCl, have not been transferred to a technical
scale so far.[233, 234, 234] The process which has been applied since
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2011 is pyrometallurgical treatment with subsequent slag
processing, as used by Umicore and Solvay Rare Earths.[212]
Umicore recycles Ni and Co from up to 7000 t a@1 accumu-
lator scrap. The slags are handed over to Solvay for further
purification and separation. The individual rare earth oxides
are the final products, but the demanding reduction to the
metals has not yet been realized.[221]
13. Tin
13.1. Economic Significance
In 2012, 337 500 t refined tin were produced world-
wide.[235, 236] The main producers were China (ca. 45 %),
Indonesia (ca. 17 %), Malaysia (11 %), Peru (7 %), and
Thailand (7 %). GermanyQs import volume is about
22 300 t.[235, 236] There is an additional estimated amount of
6000 t secondary tin, which is available for German indus-
try.[235] It is assumed that tin demand will grow by 1 % per
annum on average until 2020.[235] The main field of application
is the electrical and electronic industry as well as the house
installation sector. With a share of 52 %, more than half of the
tin is used for the production of tin solder, an alloy from tin
and lead with low a content of iron, antimony, copper, and
nickel, which melts below 330 8C. As soft solders, they are
used, for example, for the fine-welding of thin sheets as well as
for fixing and connecting components on printed circuit
boards. The current legal situation, according to which lead-
containing soft solders have to be replaced by lead-free
(copper- and silver-containing) alternatives, further increase
the demand for tin. Tin use for the production of tinplate is
also of major significance. About 15 % of the tin is required
for the production of inorganic and organic tin compounds in
the chemical industry. Examples are tin(IV) oxide (SnO2) for
the production of indium tin oxide (ITO) for flat screens, as
well as extremely thin glass coatings on windscreens, electro-
luminescent displays, and less-energy-permeable window
panes (e-glass), tin stannates as flame retardants, and catalysts
for the production of polyurethanes. Thermal stabilizers in
PVC manufacture is another important field of application, as
is the bronze and brass sector with a share of about 5–6 %.
Float glass production, in which a particularly smooth surface
is formed by the surface tensions of tin and liquid glass,
accounts for roughly 2 %. There are many other special
applications for tin with a total share of about 9 %, which
underpins the economic significance of tin. Examples are
substitutes for graphite in anodes for lithium-ion batteries or
for Ni and partially Cr in some special steels, where a further
strongly increasing potential is expected. Tin dioxide is also
used for the production of enamels and white glazes as well as
inorganic pigments.[26, 235]
In 2015 alone, about 14 000 scientific publications for tin
appeared, of which the vast majority dealt with applications of
the metal in the energy sector. This includes the battery sector
(lead-acid or magnesium-ion batteries), fuel cells, solar
energy, power-to-gas (synthetic natural gas, SNG), but also
catalysts for clean fuels.[237] Tin has recently received partic-
ular attention as an electrode material, especially as an anode
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material for sodium-ion batteries.[235, 238] The average market
price for metallic tin (purity 99.85 %) was 16980 USD t@1 in
June 2016.[12]
13.2. Raw Materials
In nature, tin is most abundant as cassiterite (SnO2), which
with a tin content of 78.8 wt % is the most significant primary
raw material for tin mining. A distinction is made between
solid rock and alluvial deposits. Further primary deposits
contain sulfidic minerals, above all stannite (Cu2FeSnS4) as
well as skarn deposits. Global mining production amounted to
294 000 t in 2015, an increase of nearly 3 % compared to
2014.[27] China has been the main producing country with
34 % of the worldwide production, followed by Indonesia
with 17 % (Figure 17). Taking into consideration that a large
part of the tin mining in Myanmar and Indonesia is destined
for export to China, one gets an idea of tin demand there.
Worldwide reserves are estimated at 4.8 million t.[27] The
tin price has increased by approximately 11 % in the last six
months in contrast to the general trend, but it is at about 51 %
of the price level of 32 830 USD t@1 in 2011. The backdrop to
this is adjustments in mining production in Indonesia in
response to price drops resulting from increased production in
Myanmar. Tin belongs to the conflict minerals.
13.3. Extraction Technologies
The choice of the manufacturing process depends on the
type of ore used. Primary ores are often depleted from sulfidic
admixtures by flotation, followed by gravity sorting as a next
step. As additional purification steps, sulfur and arsenic are
removed by roasting and iron minerals by magnetic separa-
tion. Metallic tin is obtained by thermal reduction of
cassiterite with carbon above 1000 8C[239] in shaft or reverber-
atory furnaces. However, additional purification steps are
required to remove iron impurities from crude tin (Figure S18
in the Supporting Information). For these purposes, tin is
smelted in contact with air and separated in liquid form
(segregation process).
Tin ores from alluvial deposits are concentrated by density
separation and subsequent magnetic separation, before
reduction smelting is carried out in a reverberatory furnace
or rotary kiln. Low-grade tin ore concentrates are smelted in
water-jacket or volatilization furnaces, thus avoiding multi-
stage roasting, smelting, and converter refining. Electric
furnaces or rotary converters are suitable for smelting
secondary raw materials. Finally, tin can be refined in dry
form or electrolytically.[26]
The recovery of cassiterite-containing production residues
from mining dumps is an issue in current research. One
approach is to react cassiterite with hydrogen as a reduction
agent, which allows for a fast and nearly quantitative output
of tin.[240] However, pyrometallurgical development to opti-
mize tin recovery is seen only sporadically today. The focus of
these research activities lies in decreasing the temperature
levels as well as exploiting residues with very low tin content
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Figure 17. Global tin production and use (2015).[24, 235]
economically.[241] Additives (e.g. Na2CO3, Na2CO3/NaNO3, or
Na2CO3/NaOH) for the carbothermal reduction are being
investigated with the objective to reduce the working temper-
atures below 900 8C by using fused salts.[242] The cementation
of tin is no longer pursued.[243]
13.4. Recycling Processes
Tin recycling is carried out to its fullest extent. In its main
field of application, the production of tin solder, tin metal
oxide residues (tin solder skimming, solder paste) are almost
completely recycled, thus allowing up to 70 % of the tin alloys
to be recovered. This is supported by the current practice of
substituting lead-based solders and collecting selectively
separated material. Tin plates can be de-tinned electrolyti-
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cally in hot caustic soda, when aluminum-free. However, as
tin coatings become continuously thinner, it becomes increas-
ingly difficult to operate de-tinning plants economically. For
this reason, the de-tinning of tin solder is no longer carried out
in Germany. The Kayser Recycling System (KRS) is a thermal
process which has been developed to process copper-contain-
ing residues (e.g. WEEE scrap) by pyrometallurgical meth-
ods. This process produces a tin-lead slag, which is further
processed to a tin-lead alloy in a directly connected mixed tin
furnace. Tin from bronzes and red brass is completely
recycled. In contrast, recovery from chemicals is possible
only to a partial extent, because of the highly dissipative
distribution of tin as well as consumption during application
(e.g. in PVC coatings). Tin used in the float glass process is
continually reused as long as it does not dope the bottom of
the produced glass. The rate of tin recycling has increased
during the last few years and is estimated to reach far beyond
the 30 % estimated by the International Tin Research
Institute (ITRI).[235]
14. Summary
Securing raw material supplies has always been one of the
key issues for the chemical industry. Industrial organic
chemistry has impressively succeeded in improving resource
efficiency (not least driven by the oil crises of the 1970s and
1980s), but this is not readily transferable to the inorganic
chemical industry. This is due to the rather modest number of
raw materials utilized in the organic chemical industry, above
all oil and gas. This feedstock is diversified to the required
base chemicals in a demand-oriented way. In contrast, the
inorganic chemical industry works with the entire range of
elements, producing goods with even higher complexity. In
the case of metals, one has to consider that metals typically
are utilized, not consumed. This is diametrically opposed to
the situation regarding organic raw materials. The economic
and financial crisis of 2008 and the following years have
demonstrated, though, that there is also a need for action in
the field of inorganic raw materials. In particular, volatility of
the commodity price has chiefly boosted discussions on
valuable metals. A prime example is the rare earth metals.
The term raw material criticality has spread, but requires
differentiated consideration. In some cases, criticality is less
attributable to the raw material situation itself, but to the
dependence on an individual supplying country. The outflow
of production capacity from Europe is at least as much
a reason as the demand situation. In the case of platinum
group metals and indium, criticality is determined by given
reserves and the resulting static supply. The recycling
activities undertaken provide a reliable single measure
thereof. Germanium criticality results from element avail-
ability on the one hand and the dominant position of
a supplier country on the other, and so no final statement
can be made here. Rare earth metals, Sn, Sb, Nb, Ga, and Li
are metals where criticality is given by complete dependence
on supplying countries. This also applies to magnesium.
However, in this case, European production capacity has been
completely removed, which is responsible for the dependence
Angew. Chem. Int. Ed. 2017, 56, 2544 – 2580

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on external suppliers even though domestic raw material is
sufficiently abundant. For beryllium, there is only one single
economically significant producer. In contrast, the criticality
of cobalt is given by the demand situation. Although
approximately 50 % of the reserves are located in the
DR Congo, there is a sufficient number of supplying countries
which could meet the needs. Cobalt demand is chiefly
dominated by China. At present (June 2016) commodity
prices are low, which to some extent is the outcome of the raw
materials and trade policy of the supplying countries and to
some part the result of financial market activities. In
particular, the price peak in 2011 cannot be attributed to
the raw material situation.
It took the Chinese export limitations in June 2010 to
sensitize the public to the dependence on metal commodities.
As can be seen from the technical innovations in the last ten
years outlined in this Review, it was the situation in 2010 that
boosted real technical innovations.
However, it also became clear that chemistry, with its
numerous potentials and abilities to separate complex
polymetallic mixtures with high performance, lags behind its
possibilities. There are various reasons for this: Firstly, metal
recovery from primary resources (mining) is still dominating.
Secondly, although secondary raw materials (recycling) have
gained massive significance over the last five years, it is the
low commodity prices which deter industry from investing in
optimizing metal recovery. Furthermore, traditional metal-
lurgical processes based on well-established routes are often
the only way to remain competitive under the given con-
ditions. Nevertheless, it is starting to emerge that chemistry
will play in increasingly important role. Moreover, there is an
increasingly widespread conviction that it is the substance and
material knowledge of chemists, in particular, which will
markedly contribute to further developing this sector.
Chemistry will be expressly called for as both a scientific
and an industrial discipline, to optimize production processes
with respect to integrated processes. In the future, the
processing of raw materials will aim at not only one target
metal, but all of the raw materials present. This will require
similar chemical compositions of primary and secondary raw
materials to allow for joint processing. Chemistry will have to
consider its future applicability; this is perhaps the greatest
opportunity for this discipline to significantly contribute to
securing our living conditions far beyond 2020.
Acknowledgements
We wish to thank (in alphabetical order) David Anguera
Sempere, Dr. Ines A. Aubel, Andrea C. Guhl, Sebastian
Hippmann, Dr. Carsten P-tzold, Norbert Schreiter, Martin
Seifert, and Radek Vostal for their support during the
preparation of this manuscript.
How to cite: Angew. Chem. Int. Ed. 2017, 56, 2544 – 2580
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Angewandte
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Manuscript received: June 3, 2016
Accepted Article published: August 11, 2016
Final Article published: January 27, 2017
Angew. Chem. Int. Ed. 2017, 56, 2544 – 2580