Extractive metallurgy of rare earths

F. Habashi*
A short account is given on the extraction of rare earths from monazite sand, bastnasite ore, and
phosphate rock of igneous origin. This includes mineral beneficiation, leaching methods,
fractional crystallisation [of historical interest], ion exchange, solvent extraction, precipitation from
solution, and reduction to metals.

On donne un bref compte-rendu de l’extraction des terres rares à partir de sable monazité, de
minerai de bastnaésite et de roche phosphatée d’origine ignée. Ceci inclut l’enrichissement du
minéral, les méthodes de lixiviation, la cristallisation fractionnelle (d’intérêt historique), l’échange
d’ion, l’extraction par solvant, la précipitation à partir de solution et la réduction en métaux.
Keywords: Carl Auer, Monazite, Bastnasite, Phosphate rock, Beneficiation, Leaching, Fractional crystallisation, Ion exchange, Solvent extraction,
Precipitation from solution, Reduction

This paper is part of a special issue on Advances in Rare Earths: From Mine to Materials

Historical introduction for gas mantle declined later when the Edison lamp was
invented at the beginning of the twentieth century.
Although most of the rare earth metals were discovered The second industrial application of rare earths came
in Sweden, the industrialisation started in the Austrian when Carl Auer recalled the preparation of metallic cerium
Empire. This was due to the fact that the Swedish by his colleagues at Bunsen’s laboratory and the sparking
chemist Jons Fridrik Bahr (1815–1875) from Uppsala of the metal when scratched or drawn over a rough surface.
went to Heidelberg in Germany in 1855 to analyse some He conceived that this sparking action may be utilised for
rare earth minerals by the spectroscope discovered ignition purposes. However, cerium would be a too costly
recently by chemistry professor Robert Bunsen (1811– material. He, therefore, prepared a cerium–iron alloy and
1899) and his colleague physicist Gustav Kirchhoff found out that when the alloy contained 30%Fe it gave the
(1824–1887). Few years later Carl Auer (1858–1929) best sparking effect suitable for ignition of gases. The ‘Auer
from Vienna went also to Heidelberg to study under lighter’ soon became as famous as his incandescent mantle
Bunsen. He was assigned the task to separate the rare when it was produced on large scale in 1903. Production
earths from these minerals. On his return home, Carl reached 1 000 000 kg annually in 1930; it served to prepare
Auer took with him the remaining minerals to continue 500 million flints which replaced six billion boxes of
his studies at the University of Vienna.1,2 matches. This work was conducted at his new factory at
While in Heidelberg, Carl Auer had noted the re- Treibach in Carinthia which he took possession in 1900
markable light-emitting powers of the rare earth oxides and which is today a successful metallurgical plant known
when they were inserted into the flame of a Bunsen as Treibacher Chemische Werke in Austria.
burner. In Vienna he put this observation into practice
by inventing the gas mantle, a stocking made of cotton
thread and soaked in a solution of the earth metal salts.
Rare earths elements
After the organic matter was burned off, a skeleton of Originally, the term rare earths was only used for the
the metal oxide was left. This emitted light when heated oxides, R2O3, which are similar to one other in their
in a laboratory Bunsen burner. In 1887, he started a chemical and physical properties and are therefore
factory at Atzgersdorf, a suburb of Vienna, to separate difficult to separate. Within the rare earth group, the
the rare earths salts necessary for preparing the soaking elements scandium, yttrium, and lanthanum differ in their
solution for manufacturing the gas mantles for lighting atomic structure from the elements cerium to lutetium.
the streets in Vienna. He also sold the solutions to The term lanthanides was abbreviated Ln by Chemical
customers in Germany, England, and USA. The marked Abstracts. Scandium occupies a special position with
respect to this classification and its other properties, and
therefore does not belong to either of these groups. The
rare earth elements always occur in nature in association
Department of Mining, Metallurgical, and Materials Engineering, Laval with each other. The isolation of groups of rare earth
University, Quebec City, G1V 0A6, Canada elements or of individual elements requires costly separa-
*Corresponding author, email [email protected] tion and fractionation processes owing to the great

ß 2013 Canadian Institute of Mining, Metallurgy and Petroleum

Published by Maney on behalf of the Institute
Received 28 November 2012; accepted 23 April 2013
224 DOI 10.1179/1879139513Y.0000000081 Canadian Metallurgical Quarterly 2013 VOL 52 NO 3
 Habashi Extractive metallurgy of rare earths

1 Separation of monazite and other valuable minerals from monazite sand by physical methods

similarity of the chemical and physical properties of their containing some thorium and small amounts of ura-
compounds, which explains why the history of their nium. It is widely distributed in the Earth’s crust. It
discovery has extended over such a long period. occurs in small proportions in granites. When such rocks
The word ‘rare’, when used to describe this group of are weathered, grains of monazite are carried by waters,
elements, originates from the fact it was thought that then deposited at the mouths of rivers, together with the
these elements could only be isolated from very rare heavier constituents of the parent rock, to form black
minerals. Considering their abundance in the Earth’s sands known as monazite sand. The monazite in these
crust, the term rare is now inappropriate. These elements sands is usually present in rounded grains, showing that
are lithophilic and are therefore concentrated in oxidic the grains have previously been rolled to and fro in
compounds such as carbonates, silicates, titano-tantalo- streams of water. Monazite sands occur mainly in Brazil,
niobates, and phosphates. India, Australia, and USA. Xenotime is also a lantha-
The abundance of the rare earth elements taken nide phosphate but the individual lanthanides occur in a
together is quite considerable. Cerium, the most common different proportion from that in monazite. It occurs
rare earth, is more abundant than cobalt. Yttrium is more mainly in South East Asia associated with alluvial tin
abundant than lead, whereas Lu and Tm are as abundant deposits.
as Sb, Hg, Bi, and Ag. For all practical purposes Monazite sand and xenotime can be easily concen-
promethium does not occur in nature. It forms only in trated from the sands by physical methods. For
nuclear reactors. example, a monazite sand containing 1% monazite can
be concentrated by gravity, magnetic, and electrostatic
Raw material methods to a concentrate containing 85% monazite
The major raw material for rare earths is monazite sand, (Fig. 1). Some physical properties of monazite and
xenotime, bastnasite, and phosphate rock. xenotime concentrates are given in Table 1. A chemical
analysis of the concentrates is given in Table 2. The
Monazite and xenotime composition of the lanthanide fraction in monazite, in
Monazite derives its name from Creek meaninc to be xenotime, and bastnasite is given in Table 3. Scandium,
alone. The mineral monazite is a lanthanide phosphate although in the same group with yttrium, lanthanum,

Table 1 Physical properties of lanthanide phosphate minerals

Monazite Xenotime

Colour Yellow to red brown Pale yellow to brownish green

Specific gravity 4.9–5.5 4.45–4.59
Hardness (Mohs) 5 4.5
Crystal structure Monoclinic Tetragonal

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Habashi Extractive metallurgy of rare earths

Table 2 Chemical analysis of lanthanide phosphate Ce)2(Nb,Ta,Ti)2O6 in the Kola Peninsula and also in
concentrates most uranium minerals as trace substituents.
Monazite Xenotime Scandium occurs in trace amounts in most rare earth
concentrate/% concentrate/% minerals. In many minerals, scandium is present in a
dispersed state. Wolframite and cassiterite can contain
P2O5 24–29 … up to 1% scandium, so that scandium is a byproduct of
Ln2O3* 55–65 52–63 the production of tungsten and tin. Uranium minerals
ThO2 5–10 1–3 contain much smaller amounts of scandium, but, since
U3O8 0.2–0.4 0.5–3.5
SiO2 1–3 … uranium is produced in relatively large quantities,
CaO 0.2–0.8 … scandium is produced in appreciable quantities also.
Fe2O3 1–2 …
Al2O3 0.1–0.8 … Phosphate rock
ZrO2 0.7 2–3 Tonnage wise, phosphate rock is the most important as
SnO2 … 0–9 compared with the other material; about 120 millions
*Ln, lanthanide. tons of rock are treated annually while only 30 000 tons
of monazite and xenotime. However, no production of
and the lanthanides, is not present in any of these rare earths from this source is actually conducted.
minerals. Apatite is the principal constituent of phosphate rock.
Monazite and xenotime are the main source of The mineral received its name from the Greek word
thorium and the lanthanides; uranium is recovered as meaning I deceive when it was realised that it was
frequently confused with other mineral species, includ-
a byproduct.
ing beryl and tourmaline, prior to the latter part of the
Bastnasite eighteenth century. Phosphate rock is the main raw
material for the production of phosphatic fertilisers.
The most important mined rare earth deposit is at the
Phosphate rock is composed mainly of:
Mountain Pass Mine in California, where up to 40 000 t/a
(i) Fluorapatite, Ca10(PO4)6F2
bastnæsite ore concentrate (70% REO) is produced by ore
(ii) Hydroxyapatite, Ca10(PO4)6(OH)2
beneficiation. Other important bastnæsite deposits are in (iii) Carbonato-apatite, Ca10(PO4)6CO3
Burundi, Madagascar, and in Bayan Obo, near the town Depending on the proportion of each component, the rock
of Baotou in Inner Mongolia in China. The bastnasite, may be frankolite, kunskite, or colophanite (Table 4).
with monazite, is associated with magnetite–hematite– Low-grade phosphate rock, may contain appreciable
fluorspar. Bastnasite is a fluorocarbonate, Ln2(CO3)3, amounts of aluminium phosphate wavellite, AlPO4, and/
LnF3, or LnFCO3. or calcium–aluminium phosphate, crandallite.
Phosphate rock occurs either as a sedimentary
Other complex minerals deposit, e.g. in Florida and North Africa, or as igneous
Minerals of this type are oxidic ores containing titanium, rock, e.g., in Kola peninsula, Russia. Sedimentary
niobium, tantalum, uranium, and thorium; for example: phosphates supply about 85% of the phosphate rock
(i) Euxenite (Y,Ce)(Nb,Ta,Ti)2O6 for the industry. Typical analyses of phosphate rocks are
(ii) Samarskite (Y,Ce)4(Nb,Ta,Ti)2O6 given in Table 5. Phosphate rock is used for the
(iii) Fergusonite (Y)(Nb,Ti,Ta)O4 manufacture of fertilisers and elemental phosphorus.
(iv) Betafite (U,Ca,Y,Ce2(Nb,Ta,Ti)2O6(OH) Pure phosphoric acid for other uses than fertilisers is
Useful concentrations (up to 5%) of rare earth ele- prepared from the latter product although attempts are
ments occur in apatite and up to 10% in pyrochlor being made to prepare a moderate grade phosphoric
(Na,Ca,Ce)2(NbTa,Ti)2(O,OH,F)7, and loparite (Na,Ca, acid by leaching the rock.

Table 3 Typical composition of lanthanides in monazite, xenotime, and bastnasite

Lanthanide oxide Monazite/% Xenotime/% Bastnasite/%

Light La2O3 23.0 0.5 32.0

CeO2 46.5 5.0 49.0
93 8.4 98.9
Pr6O11 5.1 0.7 4.4
Nd2O3 18.4 2.2 13.5
Heavy Sm2O3 2.3 1.9 0.5
Eu2O3 0.07 0.2 0.1
Gd2O3 1.7 4.0 0.3
Tb4O7 0.16 1.0 91.6 0.01
7 1.37
Dy2O3 0.52 8.7 0.03
Ho2O3 0.09 2.1 0.01
Er2O3 0.13 5.4 0.01
Tm2O3 0.013 0.9 0.2
Yb2O3 0.061 6.2 0.01
Lu2O3 0.006 0.4 0.1
Y2O3 2 60.8 0.1

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2 Leaching methods for monazite sand

Recovery methods3,4 lanthanides. The residue contains most of the radio-

active decay products of uranium and thorium.
Monazite/xenotime
Sodium hydroxide method
There are two methods used for treating these concen-
trates: the sulfuric acid and the sodium hydroxide The sodium hydroxide process differs from the acid
methods (Fig. 2). The decision between one and the process in that water soluble phosphates are formed
other is an economic one; for example in Brazil, the while the lanthanides, thorium, and uranium form
NaOH process is used because of a shortage in sulfuric insoluble hydroxides
acid. However, the general tendency today is to use the
NaOH process because it is possible to recover sodium LnPO4 z3NaOH?Ln(OH)3 zNa3 PO4
phosphate as a byproduct.
Th3 (PO4 )4 z12NaOH?3Th(OH)4 z4Na3 PO4
Sulphuric acid method
This method involves two steps:5
UO2 HPO4 z2NaOH?UO2 (OH)2 zNa2 HPO4
Digestion
The concentrate is digested in a closed reactor or baked Optimum conditions of digestion are 40–50%NaOH,
in a rotary kiln with 93%H2SO4 at about 200uC for 2– 160uC, NaOH to concentrate 2 : 1, time of reaction
4 h at an acid to concentrate ratio of 2 : 1. An acid-to- about 3 h. Sodium hydroxide should be free from
concentrate ratio lower than this, results in incomplete carbonate otherwise uranium will be lost in solution,
reaction while higher ratio interferes with subsequent since it forms soluble carbonates. The product is a thick
operations. Also, with temperatures lower than the paste; it is slurried in water then filtered, washed, and
above, the reaction will be too slow, and if higher than dried. The cake obtained is composed of hydroxides of
300uC, insoluble thorium pyrophosphate is liable to be uranium, thorium, and lanthanides, containing small
formed. The reaction is exothermic and can be repre- amounts of phosphate; it is dissolved in acid for further
sented by the equation separation. The leach solution contains the unreacted
NaOH as well as the phosphorus originally present in
2LnPO4 z3H2 SO4 ?Ln2 (SO4 )3 z2H3 PO4
the concentrate. When allowed to cool to about 60uC,
Thorium and uranium are also transformed into sul- trisodium phosphate hydrate hydrate (Na3PO4.10H2O)
phates. Due to the high temperature used the product is a crystallises out. After separation, the solution typically
thick paste of anhydrous sulphates. analyse 47?4%NaOH, 0?5%Na3PO4, 1?5%Na2SiO3, and
can be recycled.
Dissolution of reaction mass
The resulting mass is allowed to cool, diluted with water Thorium problem
to allow the insoluble material to settle, and then The association of thorium with rare earths creates a
filtered. Typical analysis of the filtrate is shown in health hazard problem because of its radioactivity.
Table 6. The clear leach solution is then subjected to Thorium disintegrates to radium 224 which in term
further treatment to separate thorium, uranium, and the disintegrates to radon 220 [thoron] which is a gas that

Table 4 Main types of phosphate rock

Type Composition

Frankolite Isomorphous mixture of fluoroapatite and carbonate apatite in the ratio 3 : 1

Kunskite Isomorphous mixture of fluoroapatite and carbonate apatite in the ratio 2 : 1
Colophanite An ultra microcrystalline variety of frankolite

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3 Separation of lanthanides from bastnasite by extraction with D2EHPA (Molycop process)

decays to polonium 216 which is a solid. Hence, the amount of acid used, normal superphosphate or
possibility of respiration of the gas and the deposition of phosphoric acid is produced:
the radioactive decay product in the lungs.6 Methods
must be devised to avoid this problem.
N When a small amount of acid is used the product is
known as normal superphosphate

Bastnasite Ca10 (PO4 )6 F2 z2H2 SO4 z2H2 O?

In the Molycorp process, the mineral is concentrated to ½3Ca(H2 PO4 ) :2H2 Oz7CaSO4 :2H2 Oz2HF
2
60% by flotation and then calcined, converting the
cerium to the tetravalent state. It is then treated with
hydrochloric acid, which causes only the trivalent rare N When a large amount of sulphuric acid is used,
phosphoric acid is produced. The reaction is largely
earth elements to go into solution, leaving behind 65–
complete in few minutes. Three processes are used
80%CeO2 (Fig. 3). The individual earths are then
(Table 7).
separated by solvent extraction (see later).
N Hemihydrate process. Conducted above 80uC and
Phosphate rock produces 30% acid
Phosphate rock is insoluble in water, but when treated Ca10 (PO4 )6 F2 z10H2 SO4 z5H2 O?
with acids water soluble monocalcium phosphate, citrate
soluble dicalcium phosphate, and phosphoric acid can 6H3 PO4 z10CaSO4 :1=2H2 Oz2HF
be obtained. The first two can be used directly as a
fertiliser, while the latter is neutralised with ammonia to
produce an ammonium phosphate fertiliser. The acids
N Dihydrate process. Conducted below 80uC and
produces 60% acid
used for treating the rock are the following.
Ca10 (PO4 )6 F2 z10H2 SO4 z20H2 O?
Sulphuric acid
6H3 PO4 z10CaSO4 :2H2 Oz2HF
Leaching with sulphuric acid is the most common
method for treating phosphate rock. Depending on the More time is needed, about 8 h, to allow for the
proper formation of crystals that can be removed
Table 5 Analysis of typical phosphate rock easily by filtration.
% % Table 6 Typical analysis of monazite leach solution,
pH50?05
P2O5 29–38 Cl 0.01–0.7
CaO 48–52 CO2 2–6 g L21 g L21
MgO 0.2–0.8 SO3 1–3
Fe2O3 0.2–1 SiO2 0.2–5 Th 5.3 Nd2O3 7.0
Al2O3 0.1–1 Organic carbon 0–0.4 U 0.2 Sm2O3 1.3
Na2O 1–2 Uranium 0.01–0.02 Ce2O3 16.0 SO422 128.0
K2O 0.1–0.4 Ln2O3 0.1–1 La2O3 8.5 PO432 26.0
F 3.3–4.3 Pr2O3 1.7 … …

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 Habashi Extractive metallurgy of rare earths

Table 7 Production of phosphoric acid by H2SO4 route

Hemihydrate–
Hemihydrate process Dihydrate process dihydrate process

Crystal form CaSO4.KH2O CaSO4.2H2O Initially CaSO4.KH2O,

then CaSO4.2H2O
Crystal size/mm 15–30 (without modifier) 40–60
40–60 (with modifier)
P2O5 losses in crystal/% 3–6 Lower
Temperature/uC .80 ,80 . 80
Phosphoric acid concentration 45–54 28–30
%P2O5–%H3PO4
Washing system Vacuum belt filter (Lurgi) Counter-current in
thickeners (Dorr)
Phosphoric acid yield/% 91 93 99
Energy requirement Low High
Because less water to Because more water
be evaporated later to be evaporated later

N Hemihydrate–dihydrate process. Conducted above

Ca10 (PO4 )6 F2 z14HCl?3Ca(H2 PO4 )2 z7CaCl2 z2HF
80uC to produce the hemihydrate crystals, then slurry
is agitated for few hours to allow the crystallization of or phosphoric acid
the dihydrate.
There are two types of wet process phosphoric acid: the Ca10 (PO4 )6 F2 z20HCl?6H3 PO4 z10CaCl2 z2HF
‘black acid’ and the ‘green acid’. The black acid is the Calcium chloride is then removed as CaCO3 by
one usually produced and its black coloUr is due to precipitation with (NH4)2CO3
the organic matter originally present in the rock. If the
organic matter is above certain limits it is usually CaCl2 z(NH4 )2 CO3 ?CaCO3 z2NH4 Cl
eliminated by calcining in an oxidizing atmosphere. The
acid derived from such treated rock is the green acid Nitric acid
because it has a green tint. Both acids are a commercial
Nitric acid is also used to produce a fertiliser known as
product, and is shipped to fertiliser producers. It is
nitrophosphate
usually neutralized by ammonia to form ammonium
phosphates: Ca10 (PO4 )6 F2 z14HNO3 ?
N Monoammonium phosphate (46% P2O5, 11% N) ½3Ca(H2 PO4 )2 z7Ca(NO3 )2 z2HF
pH 4
H3 PO4 zNH4 OH ? NH4 :H2 PO4 zH2 O or phosphoric acid
Ca10 (PO4 )6 F2 z20HNO3 ?
N Diammonium phosphate (46%P2O5, 18%N) 6H3 PO4 z10Ca(NO3 )2 z2HF
pH 6
H3 PO4 z2NH4 OH ? (NH4 )2 :HPO4 z2H2 O Calcium nitrate is separated by cooling to –10uC then
centrifuging the crystals of Ca(NO3)2.4H2O. It is usually
Or, reacted with a fresh batch of phosphate rock in a transformed to ammonium nitrate by reaction with
rotary kiln to produce triple superphosphate (40– ammonium carbonate.
48%P2O5)
Present tendency
Ca10 (PO4 )6 F2 z14H3 PO4 zH2 O? The first fertiliser produced in industry was normal
10Ca(H2 PO4 ) :H2 Oz2HF
2 superphosphate. Because of its low concentration in
P2O5, its production has declined gradually in the past
This in turn is usually treated by ammonia to form
years and its place was taken over by triple superpho-
ammoniated triple superphosphates
sphate, and more recently by mono- and diammonium
phosphates. Over 70% of the phosphate rock is used in
Ca(H2 PO4 )2 :H2 OzNH3 ? making phosphoric acid by the wet process. Phosphoric
CaHPO4 zH4 :H2 PO4 zH2 O acid produced by leaching phosphate rock is impure and
cannot be used for manufacturing phosphates needed
Ca(H2 PO4 )2 :H2 Oz2NH3 ? for the food or detergent industries unless it under-
goes extensive purification, e.g. extraction by organic
CaHPO4 z(NH4 )2 HPO4 zH2 O
solvents.
Phosphate rock of sedimentary origin contains about
Hydrochloric acid 0?5% lanthanide oxides while igneous phosphate, e.g. in
Hydrochloric acid is used sometimes to leach phosphate Kola Peninsula, contains about 1% lanthanide oxides.
rock to produce either monocalcium phosphate fertiliser During the manufacture of phosphoric acid about 70%

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Habashi Extractive metallurgy of rare earths

is lost in the gypsum. However, if acidulation is In the separation of the lanthanides, the concentrate is
conducted by nitric acid all will go into solution and dissolved in hydrochloric acid and diluted with water to
can be recovered by organic solvents. In Finland, the make up the feed solution for the cation exchange
lanthanides were recovered commercially by Kemira Oy columns 1?5 m long j 15 cm diameter in the ammonium
from phosphate rock during 1965–1972 using organic form. The solution of the chlorides is loaded on four
solvents. It is believed that a similar operation is in columns which are connected together in series. The
existence in Russia. sorbed band is first washed with distilled water then
eluted with 0?1% citrate solution at pH 8 at a flow rate
Recovery from leach solution of 0?1–1?2 L min21 into a series of six similar columns.
Under these conditions, the front of the adsorbed band
Separation of thorium and the lanthanides from sulfuric
advances at the rate of about one resin bed per day.
acid leach solution of monazite and xenotime concen-
The light lanthanides are sorbed on the first two
trates is based on oxalate precipitation
columns, and the heavy lanthanides are concentrated on
Th4z z2(C2 O4 )2{ ?Th(C2 O4 ) the last two columns, while the bulk of yttrium and a
considerable portion of terbium and dysprosium are
Ln3z z3(C2 O4 )2{ ?Ln2 (C2 O4 )3 concentrated on the two middle columns. Each set of two
columns is further fractioned by elution through a series of
Uranium is not precipitated. The oxalate filter cake is eight smaller columns (1?5 m long j 10 cm diameter) at a
then digested with NaOH solution to convert the much smaller flowrate of 0?5 L min21. Each of these small
oxalates into hydroxides and recover sodium oxalate columns is loaded with a pure metal then separately eluted
for recycle in a container. The pure lanthanide is recovered from the
solution by precipitation with oxalic acid. Individual
Th(C2 O4 )2 z4OH{ ?Th(OH)4 z2(C2 O4 )2{
lanthanides up to 99?99% purity from monazite are
produced on a commercial scale based on elution with
Ln2 (C2 O4 )3 z6OH{ ?2Ln(OH)3 z3(C2 O4 )2{ EDTA (Fig. 4).
The hydroxides are then calcined, and the resulting
oxides dissolved in nitric acid for later separation of
Solvent extraction
thorium by solvent extraction. The solvent used for the separation of the lanthanides
from leach solution of bastnasite concentrates is di
Ion exchange (2-ethylhexyl) phosphoric acid known as D2EHPA
When the acid leach solution containing the lanthanides
is allowed to flow through a cation exchange resin bed in
where R is
hydrogen or ammonium form, they will be sorbed by the
resin. However, the resin has no selectivity for one of the
lanthanides as compared with the other, and therefore
practically no separation can be achieved. In order to Cerium is already separated in the leaching step since it
separate the different metals, use is made of their is transformed into soluble cerium(IV) compound and is
different affinities toward complexing agents in solution. recovered from the residue. Each extraction step
When a buffered solution of some negative ion species, includes numerous stages of contact with the extractant
which forms a stable complex with the lanthanides, is and the stripping agent under certain conditions of
passed through the column, a competition for the organic/aqueous ratio, and extractant and stripping
lanthanide ions between the aqueous phase and resin agent concentrations. The plant is computerized and is
phase will be set up. When equilibrium conditions are fully automated (Fig. 5).
maintained, an individual lanthanide ion continuously
exchanges between the complexing ion and the resin.
The positive ion in the complexing solution replaces the
lanthanide ions at the rear edge of the band, so that the
lanthanide band is driven down the resin bed. Because
the stability constants of the lanthanide complexes differ
appreciably from one lanthanide to another, the most
stable complex moves faster down the column.
Different complexing agents were used as eluents for
example, 5% citric acid adjusted at pH 3 by ammonium
hydroxide, 0?1% citric acid adjusted at pH 5–8 by
ammonium hydroxide, 1M lactate at pH 3, and 0?26M
ethylene diamine tetraacetic acid (EDTA) at pH 3?6.
Uniform rate of elution has been obtained by con-
tinuously varying the pH of the eluent. The eluent at
pH 3?19 was neutralized at a predetermined rate with
1 M lactic acid buffered with ammonia to pH 7 to give a 4 Ion exchange columns for separation of lanthanides at
rate of change of pH of z0?1 unit/hour. Michigan Chemical Corporation, St. Louis, Michigan5

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 Habashi Extractive metallurgy of rare earths

5 Inside of Molycorp’s rare earths extraction plant at

Mountain Pass, California5

Cerium salts are produced by liquid–liquid extraction

from rare earth cerium containing solutions. Cerium can
be extracted out of cerium nitrate–nitric acid solutions in
a few steps in the form of a cerium(IV) nitrate complex a graphite anodes; b molybdenum cathode; c graphite
in tributyl phosphate and therefore separated from the crucible; d liquid electrolyte; e molybdenum crucible; f
accompanying trivalent rare earth elements, which form tapping pipe; g molten mischmetal4
less stable nitrate complexes. Purities of 99?99% and 6 Electrolysis cell for production of mischmetal from oxides
better can be achieved.
reduced electrolytically to the rare earth metals. The
Fractional crystallisation electrolysis cell (Fig. 6) consists of a graphite crucible
This is one of the oldest methods for the separation of with graphite anode and molybdenum cathode, working
rare earths and is now obsolete. It depends on small under an inert gas atmosphere to prevent oxidation of the
differences which are magnified by repeated operations. construction materials. The electrolyte is initially melted
It has been replaced by ion exchange and solvent by resistance heating. Electrolyte and electrodeposited
extraction which are faster and less tedious. rare earth metals are kept liquid by the joule heat. A cell
produces ca. 500 kg of metal per day. If bastnasite is a
Metal production raw material, it must be specially purified prior to
electrolysis.
Mischmetal
Mischmetal (from German: Mischmetall – ‘mixed metals’) Individual rare earth metals
is an alloy of rare earth elements in various naturally- The rare earth metals are produced, both on the labora-
occurring proportions. Monazite-derived Mischmetal tory and industrial scale, by molten salt electrolysis and
typically is about 48% cerium, 25% lanthanum, 17% metallothermic reduction.
neodymium, and 5% praseodymium, with the balance
being the other lanthanides. Bastnasite derived Mischmetall Fused salt electrolysis
is higher in lanthanum and lower in neodymium. La, Ce, Pr, Nd can be produced by molten salt electrolysis
Mischmetal is the lowest priced rare earth metal of a mixture of anhydrous rare earth chlorides and
because no expensive chemical separation is needed to fluorides with alkali and alkaline earth chlorides and
produce it. It is produced predominantly by fused salt fluorides. This process is made possible by the lower
electrolysis of rare earth chlorides. Mischmetal was first melting points of the cerium earth metals, whereas the
produced industrially in 1908 by Auer von Welsbach, yttrium earth metals have higher melting points and
who succeeded in finding an outlet for surplus rare earth therefore do not melt during the electrolysis process. A
in the production of lighter flints. At that time, monazite lower melting point can be achieved by using a cathode
was used exclusively as the source of thorium needed for (e.g. Cd, Zn) that forms a low melting alloy with the rare
the manufacture of incandescent mantles. earth metal. This alloy can also have a lower density than
the fused salt (e.g. Mg), so that it rises to the surface and
Oxide process can be removed from the fused salt. The alloying element
A process developed by the US Bureau of Mines and can then be removed by distillation. By using molten Cd
further improved by Santoku Metal Industries in Japan, or Zn as cathode, Sm, Eu, and Yb can also be produced.
produces mischmetal from rare earth oxides. The process The reactivity of the rare earth metals causes
is similar to Hall–Héroult process for aluminum electro- problems in the choice of construction materials of the
lysis. It avoids emission of chlorine and the consequent electrolysis furnace. High purity metals can be produced
expensive purification of off-gas. Rare earth oxides are by using molybdenum, tungsten, or tantalum as the
dissolved in an electrolyte consisting of alkali fluorides crucible and cathode materials. For industrial manu-
(to improve conductivity), alkaline earth fluorides (to facture, iron crucibles with ceramic or graphite linings
reduce melting point), and rare earth fluorides (to are used. If halogens are liberated during the electrolysis,
improve the solubility of rare earth oxides) and are carbon is used as the anode material.

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Habashi Extractive metallurgy of rare earths

a furnace; b heating element; c stainless steel container;

d water cooling; e vacuum; f baffle; g RE metal; h
molybdenum condenser; i heat shield; j molybdenum
crucible; k pelletised reactants4
8 Reduction–distillation apparatus for production of samar-
a sight glass; b vacuum connection and helium inlet; c ium, europium, and ytterbium
charging tunnel; d charging shut-off mechanism; e steel
reaction chamber; f titanium reaction crucible; g graphite
insulation; h titanium or steel supporting crucible; i water
1000–1300uC. The rare earth oxides and the reducing
cooling4
7 Reduction apparatus for production of yttrium
metal are used in the form of pellets, prepared from
chippings or thin disks. Sm, Eu, and Yb are volatile at
the reaction temperature under vacuum (,10–4 bar),
and can be distilled from the reaction space during the
Metallothermic reduction
reaction and condensed on coolers. Thus, these metals
Metallothermic reduction of the rare earth oxides and can be separated from rare earth metals that are not
anhydrous rare earth chlorides and fluorides can be used volatile under these conditions and obtained in a pure
to produce high purity rare earth metals, especially Gd state. Hence, the starting materials can consist of rare
to Lu, including Y. Alloys can also be produced by this earth oxides in which Sm, Eu, and Yb have merely been
process. Alkali metals, alkaline earth metals, and concentrated. The principle of the reduction distillation
aluminium are suitable reducing agents, as are alloys apparatus is illustrated in Fig. 8. Further purification
of these elements with each other. Lithium, which forms can be carried out by a second distillation.
low melting LiF, is of special importance, as is calcium.
The use of Mg or Zn has the additional advantage of Purification
producing a low melting alloy with the rare earth metal. Production of the pure rare earth metals necessitates the
The alloying elements can be removed by distillation, removal of products of the reaction of the metals with
yielding the pure rare earth metal. the atmosphere, crucible materials, and co-reactants.
For the production of La, Ce, Pr, and Nd, the Suitable methods include melting under a protective gas
metallothermic reduction of the anhydrous rare earth or in a vacuum. The high boiling rare earth metals can
chlorides is preferred. The reaction is carried out in also be purified by distillation. Alloying elements and
crucibles lined with MgO at temperatures up to 1100uC. impurities such as Mg, Cd, Zn, and Ca are distilled off
At higher temperatures, reaction takes place between the under vacuum. The remaining rare earth metal is then in
rare earth metal and the MgO, and the rare earth the form of a sponge, which can be consolidated by
chlorides vaporize. The process is not suitable for the fusion in an electric arc furnace. Zone melting, melt
production of Sm, Eu and Yb, which are merely reduced extraction, and melt filtration, e.g., through tungsten
to the divalent state. powder, degassing in a high vacuum, etc., are other
Gd to Lu and Sc, which have higher melting points, recommended purification methods.
are obtained by reduction of the fluorides with Ca at
1500–1600uC. The reduction is carried out in tantalum
crucibles under a protective gas or in vacuum. The USES
reaction temperature can be reduced by adding a The most important uses of mischmetal or cerium are
booster such as iodine, which gives a slag with good metallurgical. The metallurgical importance of rare
flow properties that separates cleanly from the metal. earth metals is based on reactions to form solids with
Praseodymium is produced by reduction of the fluoride oxygen, hydrogen, nitrogen, sulfur, arsenic, bismuth,
with lithium. The Carlson–Schmidt apparatus is shown and antimony, reducing the effects of these elements on
in Fig. 7. This was used between 1957 and 1959 to the properties of the metals. Mischmetal is added as
produce high-purity yttrium metal in 50 kg batches. lumps, rods, or wire. The principal uses for cerium
Sm, Eu, and Yb can be produced by reduction of the compounds are as polishing agents and as a component
oxides with La or the cheaper cerium mischmetal at in glass. The rare earth metals and their compounds are

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 Habashi Extractive metallurgy of rare earths

used in numerous areas of industry for a wide range of 2012, Montreal, Canadian Institute of Mining, Metallurgy, and
purposes. The most important of these include metal- Petroleum.
3. C. K. Gupta and N. Krishnamurthy: ‘Extractive metallurgy of rare
lurgy, catalysts in the chemical industry, coloring of earths’; 2005, CRC Press.
glass and ceramics, the production of magnets, and 4. I. McGill: ‘Rare earth metals’, in ‘Handbook of extractive
phosphors.4 metallurgy’, (ed. F. Habashi), 1695–1741; 1997, Weinheim,
WILEY-VCH.
References 5. F. Habashi: ‘A textbook of hydrometallurgy’, 2nd edn; 1993,
Québec City, Métallurgie Extractive Québec. Distributed by Laval
1. F. Habashi: ‘Researches on rare earths. History and technology’, University Bookstore. www.zone.ul.ca
Métallurgie Extractive Québec, Québec City, Canada 2008. 6. F. Habashi: ‘Pollution problems in the mineral and metallurgi-
Distributed by Laval University Bookstore, www.zone.coop cal industries’; 1996, Québec City, Métallurgie Extractive
2. F. Habashi: ‘Carl auer and the beginning of the rare earths Québec. Distributed by Laval University Bookstore, www.zone.
industry’, in ‘Rare earths 2012’, (ed. J. R. Goode et al.), 3–13; coop

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