Recovery and Purification

of Rare Earth Metals

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 Rare Earths

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Introduction
RE functional materials and structural materials play an important role in
the development of
• aerospace industry • military equipment
• domestic appliances • new energy saving
• environmental technologies
Furthermore, magnetic energy product of RE permanent magnet
materials is much higher than that of ferrite and Al-Ni-Co permanent
magnet materials.
• NdFeB • SmCo
Therefore, RE permanent magnetic materials have been used in
• air conditioning
• sound box
• permanent magnet motor.
Tb and Dy are the main ingredients of magnetostrictive materials
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Introduction
In the fields of battery, brake, and
RE magnetostrictive materials have refrigeration, RE hydrogen storage
been widely used in alloy shows the advantages of
✻ high-power emitting sonar, ❏ high electric capacity,
❏ good stability,
✻ sensor, and ❏ high hydrogen absorption
✻ communications. efficiency, and
❏ no pollution,

RE improve the fatigue performance The purity of rare earth metals

of bearing steel ➥key factor affecting the
✓modify inclusions performance
➥high oxygen concentration of RE
✓refine grain
could weaken intrinsic coercivity of
✓ strengthen microalloying
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RE permanent magnet
Progress in Preparation of RE Metals
The increasing demand for high-purity rare earth metals
• Stimulated rapid development of preparation technology
The most common methods extract all kinds of RE elements:
• molten salt electrolysis
• metal thermal reduction
Molten Salt Electrolysis:
• Light rare earth metals such as La, Ce, Pr, and Nd
• Economic cost factors as fixed asset investment, raw materials,
and energy consumption are the main considerations.
Metal thermal reduction method
• more suitable for preparing heavy rare earth metals
27/10/24 • such as Gd, Tb, and Y with high melting and boiling point.
Molten Salt Electrolysis
Several kinds of metals are prepared by molten salt electrolysis:
• Cu, Al, and Mg
The preparation of rare earth metals by molten salt electrolysis
• Started from the molten salt system of chloride.
Because of the problems of chloride electrolysis preparation, the
method was banned:
• easy moisture absorption of raw materials
• low yield and serious exhaust pollution
Nowadays, rare earth metals are mainly prepared by:
• fluoride oxide electrolysis in industry.
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Molten Salt Electrolysis
RE2O3 dissolved in fluoride molten salt and dissociated
into rare earth cations and oxygen anions.
• Under DC current, RE cations move toward
cathode
Cathode • reduced to metals by obtaining electrons

• Oxygen anions move to anode ⟹lose electrons

• forms oxygen or interacts with graphite to form
Anode CO2 and CO

• Cathode (reduction) reaction: RE3+ + 3e- = RE

• Anode (oxidation) reaction: 2O2 - 4e- = O2(g)
Reaction • Redox reaction: RE O + C = 2RE + CO + CO
2 3 2
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Molten Salt Electrolysis q Baotou Research
Institute of Rare Earths
successfully developed a
3 kA fluorosalt system
electrolytic bath in
1984.
q After more than 30 years
of development, the scale
of electrolytic bath has
gradually expanded
from 3 to 10 kA, and the
maximum electrolytic
bath could reach 60 kA.
q most of the rare earth
enterprises are still using
6~10 kA electrolytic
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bath.
Molten Salt Electrolysis
Metallic impurities: Interstitial impurities
⟹Al ⟹C
⟹Si ⟹O
⟹Ti
⟹W ⟹N
⟹Mo
⟹Fe
Impurities

Al and Si impurities Al and Si were reduced

mainly are derived from 0.03% to below 0.01%
⟹furnace materials and ⟹ altering the variety of
furnace materials and
⟹raw materials
⟹ purity of raw material
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Molten Salt Electrolysis
Metallic impurities: Interstitial impurities
⟹Al ⟹C
⟹Si ⟹O
⟹Ti
⟹W ⟹N
⟹Mo
⟹Fe
Impurities

W, Ti, and Mo could be

W, Ti, and Mo impurities reduced to below 0.05%
are mainly derived from: ⟹ adjusting the crucible
⟹metal crucible and materials
⟹stirring device ⟹ stirring device
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Molten Salt Electrolysis
Metallic impurities: Interstitial impurities
⟹Al ⟹C
⟹Si ⟹O
⟹Ti
⟹W ⟹N
⟹Mo
⟹Fe
Impurities
C impurity from
⟹graphite anode C in RE metals < 0.03% and
Fe < 0.3%
⟹graphite crucible,
⟹ By adjusting electrolytic
Fe impurity comes from bath structure
⟹anode clamp ⟹ electrolytic temperature
⟹auxiliary tools ⟹ other technical parameters
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Molten Salt Electrolysis

qoxygen concentration of commercial electrolysis RE

metal was as high as 0.1%.
27/10/24 qby regulating technical parameters O impurity↓↓
Metal Thermal Reduction
Sm, Eu, Yb, and Tm have moderate m.p.
Refers to Reduction of RE and relatively vapor pressure↑
compounds into metals at high La or Ce with vapor pressure↓
temperatures by active metal ⟹ can be used as reductants,
reducing agents, such as Ca, La,
⟹ the reduction equation is as follows:
and Ce.
2La + RE2O3 = 2RE↑ + La2O3

Y, Gd, Tb, Dy, Ho, Er, Lu are Impurities:

prepared by Ca thermal reduction:
⟹Metallic impurities such as Ca,
⟹the reduction equation is as Ni, Mo, Ti, W and
follows:
⟹Interstitial impurities C, O, and
3Ca + 2ReF3 = 3CaF2 + 2RE N might exist in rare earth metals
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Metal Thermal Reduction
Schematic diagram of
metal thermal reduction

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Metal Thermal Reduction
Impurities of rare earth Ni impurity from Ni boat. Ni
concentration could be
metals are mainly derived reduced from 0.01% to
from raw materials. 0.003% by
⟹Ni ⟹ reducing the temperature of
⟹Si the fluorination process or
⟹Fe ⟹ applying a protective layer
⟹Mo on the nickel boat.
⟹Ti
Impurities

Total concentration of
Impurities such as Si, impurities in RE metals
Fe, Al, Mo, Ti were could be reduced from
mostly from 0.12% to < 0.01% by
⟹rare earth oxide and ⟹ improving the purity of
raw materials as well as
⟹reagent materials
⟹ using analytical reagent
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Metal Thermal Reduction
Oxygen impurity was Oxygen concentration
mainly derived from could be reduced from
⟹raw materials, 0.1% to < 0.07%
⟹reducing agents, and ⟹by improving the
⟹oxidation of rare earth purity of raw materials.
metals
Impurities

W concentration of RE
metals reduced to <
Impurities of W and Nb 0.008%
⟹were mainly from ⟹by improving vacuum
metal crucible material. remelting or
⟹vacuum distillation
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Metal Thermal Reduction
Up to now, single furnace output of metal thermal reduction
has gradually developed from 100g to 100 kg.

Its advantages are low investment and compact process

There are also some issues such as

• harsh requirements on equipment

• discontinuous production process
• higher impurity concentration than molten salt electrolysis
RE metals
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Metal Thermal Reduction
The researches mainly focused on two aspects:
• Purity and • yield
Purity is mainly concerned with:
• reducing metallic impurities such as Fe, Mg, and Si
• The concentration of impurities can be reduced to a certain extent by
adjusting the material and technical parameters of the equipment.
• Removal of interstitial impurities such as O and N needs further work.
Yield is mainly concerned with
• Low energy consumption
• High recovery rate
• The gas tightness of equipment and automation degree in preparation
process should be more concerned in future.
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Progress in Purification
of Rare Earth Metals
Whether molten salt electrolysis or metal thermal
reduction, the purity of rare earth metals is in a range of
95.5~99.5%

This cannot meet the requirements of high performance

materials.

At present, the purification methods mainly include:

• vacuum distillation
• arc melting
• zone melting
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• solid state electromigration
Vacuum Distillation
In the process of metal thermal reduction:
• excessive reducing agent is added for complete reaction.
Therefore, rare earth metals prepared by this method:
• have high impurity concentration and should be purified
before application.
Vacuum distillation was widely used in industry:
• to remove reductant metals in order to obtain high purity
rare earth metals.
Vacuum distillation means:
• RE metals are separated from impurities under high T and
high vacuum.
Vacuum distillation requires:
• matrix metal should have high saturated vapor pressure and
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vapor pressure difference from the impurity element.
Vacuum Distillation

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Vacuum Distillation
Can remove most metallic and interstitial impurities.

Metallic impurities with high vapor pressure as Ca, Mg, and Al remove.
in Tb impurities such as Ca, Mg, Al, Si, Zn, Cr, and Mn reduced from 0.065%
to < 0.001%.
Metallic impurities Ta, W, Mo, Nb, and Ti and interstitial impurities C, O,
and N that exist in the form of compounds ↓bottom of W crucible-
Because the vapor pressure of the impurities < RE metals.

W concentration of Gd could be reduced from 0.018% to 0.005%

Interstitial
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impurity of Sm <0.0045%, and that of Yb < 0.0051%.
Vacuum Distillation
The removal effect of metallic Vacuum distillation has the
impurities advantages of
➦relatively high production
➦ with small vapor pressure efficiency and yield, but
difference from matrix metal ➦impurities segregation is
was not obvious, such as Fe prevalent in prepared rare
and Cu. earth metals.

Rare earth metal purification by

vacuum distillation is
➦still in the stage of small
batch trial production, and
➦the single furnace output Is
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only 1-5 kg.
Arc Melting
Common method
to purify metals
and alloys
electric arc between
electrode and
molten material
Arc
Melting
impurities with high
saturated vapor
working gas is pressure removed by
mainly Ar, H2, N2, using plasma arc
He and the
mixture
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Arc Melting
Using the mixture of Ar and H2 as the working gas could significantly
improve the purification effect of rare earth metals.

This melting method is called hydrogen plasma arc melting.

When the temperature reaches 5000 K, the dissociation of H2 is > 95%.

The activated hydrogen atoms could combine with oxygen and nitrogen.
The reactions that occur in this system are as follows:
• H2 = H + H
• O (in metal) + 2H = H2O
• N (in metal) + 3H = NH3
This method has been successfully applied to the purification of rare earth
metals
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Arc Melting

Schematic diagram of hydrogen plasma arc melting.

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 Metallic impurities with
high saturated vapor Total concentration of
pressure such as metallic impurities of Tb
⇒Ca decreased
⇒Mg and ⇒from 0.438% to
Arc Melting

⇒Al 0.0580%.
could be removed
by arc-melting.
Impurities

Melting Tb and
⇒H plasma has high LaNi5 alloy in H plasma,
chemical reactivity. ⇒C concentration of Tb
⇒reacts with C, O, N, and from 0.03% to 0.0017%
other impurities to form ⇒C concentration of
gaseous compounds LaNi5 alloy from 0.018%
⇒impurities clearance. to 0.0014%.
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Arc Melting
The concentration of O and N of Tb decreased from 0.05% to
0.0015%.

Hydrogen plasma arc melting have a good removal effect on

metallic impurities and interstitial impurities.

The removal degree of interstitial impurities is obviously better

than other methods.
H plasma arc melting technology for RE metals is still in the
laboratory research stage because high temperature and high
vacuum is required, and its single furnace output is only 10~200 g.
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Zone Melting
⟹process of The metal bar slowly
redistributing Multiple directional
melt
impurities movements
⟹making use of ⟹by moving
⟹to accumulate
their different induction coil from
impurities at both ends
solubility in solid one end of metal bar
of the metal bar.
and liquid phases. to other.

Equilibrium distribution K defined as: K = CS/CL ⟹K < 1 move toward

coefficient refers to
⟹ CS and CL are end of the metal bar
⟹the ratio of solute denoted as impurity ⟹K > 1 move toward
concentration in the solid concentration in solid beginning end of
and liquid phases at and liquid phase. metal bar
equilibrium
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Zone Melting

Schematic diagram of plasma arc zone melting.

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Zone Melting
Zone melting has been widely used
• to purify semiconductor materials such as Si, Sb, Te, and metal
materials such as Zn and Cu.
Metallic impurities with high saturated vapor pressure
• such as Ca, Mg, Zn, Mn could be reduced to less than 0.0001%.
Fe, Cu, Al, Si could be enriched
• at the end as the melted zone moves.
Interstitial impurities such as O and N were enriched
• at the beginning.
Impurities such as C and S showed different migration patterns in
different rare earth metals.
• After zone melting, impurities such as C and S of La were enriched
at the beginning, while C and S of Ce were enriched at the end.
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Zone Melting
Zone melting had obvious migration effect on some metallic
impurities and interstitial impurities.
Different migration rules of impurities are different in RE metals,
and the purification mechanism needs to be further studied.
In order to achieve excellent purification effect, nearly 20 times
of repeated melting of rare earth metals are needed.
Moreover, the purification efficiency of zone melting is low, and
the single furnace output of rare earth metals is only about 30 g.
Therefore, zone melting is only used as the final method to
purify small batches of high purity rare earth metals.
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Solid State Electromigration
Solid state electromigration means that under high vacuum
conditions, the metal bar is placed between two electrodes
and applied with direct current for a long time.
The joule heat make the temperature of the test bar reach
0.8~0.9 times of the metal melting point and keep the test
bar from melting.

Under the action of direct current, atoms are not neutral.

In general, one atom can acquire more or less positive charge

than the other, resulting in different ionization behaviours.
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Solid State
Electromigration

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Solid State Electromigration
Moreover, atoms can be affected by electrostatic force, electron
collision friction and cavity friction, and defined as:
• FS = eEZ0
• Fe = -eEnele𝝈e
• Fh = eEnhlh𝝈h
• F = FS + Fe + Fh = eEZ0 -eEnele𝝈e + eEnhlh𝝈h = eEZ*
• where e is elementary charge in units of C;
• E is electric field intensity in units of V m-1;
• Z0 is the ion valence;
• n is unit volume electron;
• l is the electron mean free path;
• 𝝈 is the electron scattering cross section;
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• Z* is effective valence.
Solid State Electromigration

Atoms with more positive charge migrate to the

cathode extreme, and atoms with more negative
charge migrate to the anode extreme.

In the purification process, the migration rate of

impurity atoms is higher than that of matrix atoms, so
the impurities can be redistributed in matrix metal.

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Solid State Electromigration
Metals exhibit different crystal structures at different T.
• Interstitial impurities show different migration patterns in
different crystal structures.
• For example, when Pr is in double hexagonal closest packed
structure (named as DHCP), H, N, and O atoms
⟹enter the intercellular space except C.
• However, when Pr is transformed into BCC structure,
⟹all atoms cannot enter the intercellular space except H.
Researchers attempt to remove interstitial impurities by solid
state electromigration at transition temperature with a high
migration rate of interstitial impurities.
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Solid State Electromigration
After 216 h of high ⇒Total concentration of Fe
vacuum and high and Ni decreased from
temperature 0.05% to 0.002%.
electromigration, ⇒The concentration of
⇒the concentration of interstitial impurities was
impurities such as Al and from 0.0239% to 0.0049%
Si of Pr decreased from ⇒the O concentration
0.04% to 0.02% reduced to 0.0022%.

Solid state electromigration

had significant removal
effect on most metallic and
interstitial impurities
⇒but not obvious removal
effect on carbon and
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nitrogen impurities.
Solid State Electromigration
Solid state electromigration was
essentially
⟹a process of impurities
redistribution
⟹it did not really remove
impurities, which will seriously
affect the subsequent use of RE.

It is difficult to achieve large-

Solid state electromigration
scale industrial production
process required
⟹this method is mainly used as
⟹high vacuum degree and
the final purification method
energy consumption of
⟹to produce small amount of
equipment.
ultra-high purity metals.
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Challenges
It is not possible to remove all impurities of RE simultaneously by any
of the above methods.
Therefore, after comprehensive consideration of
• the impurity types
• purity requirements and
• removal effect of impurities,
• => several purification methods combined to remove impurities.
For example, vacuum distillation combined with arc melting can
improve the density and purity of rare earth metals.
Ultralow oxygen concentration of rare earth metals can be prepared by
the combination of arc melting and solid state electromigration.
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Challenges
In the past 60 years of development, remarkable achievements have
been achieved forming a relatively well-developed RE industrial system.

But at the same time, it should also be noted that there are issues in
many areas that need to be solved.
(1) Molten salt electrolysis and metal thermal reduction possess high
efficiency and yield, but low purity of rare earth metals and high
energy consumption are generally non-negligible.
(2) The preparation process of rare earth metals is mainly a manual
operation with low automation degree and severe environmental
pollution issue.
(3) Deep purification ability of rare earth metals is insufficient, and the
industrialization is limited to the use of vacuum distillation, which is
difficult to meet the needs of high technology development.
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 Purification of Phosphorus

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Introduction
Solid phosphorus (melting point of 44.2o C) is extremely
flammable when exposed to air.
The lack of a conventional solvent for phosphorus makes the
purification process difficult.
The conventional methods are all in high energy consumption
and may cause environmental pollution.
The purification processes:
• Vacuum distillation
• Liquid–liquid extraction
• Fractional distillation
• Mixing and extraction
• Phase separation
• Oxidation
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• Zone Melting
Vacuum distillation Arsenic iodide has a
Excessive iodine much higher boiling
(around 10,000 times point than
Iodine would then
in excess) is added to phosphorus and,
react with arsenic to
the white phosphorus thus, arsenic can be
form arsenic iodide.
by the stoichiometric separated from
amount. phosphorus by
vacuum distillation.
Most of the arsenic The disadvantage is
can be separated from that this process
This method is,
phosphorus through would produce
therefore, very
the vacuum large amounts of
dangerous to
distillation by the iodine, which is
operate.
difference in boiling both corrosive and
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point. poisonous.
Liquid–liquid extraction
When the mixture is
Most of the arsenic inside heated to melting point, or
Crude yellow
the phosphorus would when more phosphorus is
phosphorus is
react to form arsenic acid melted, liquid phosphorus
first mixed with
but only part of the and nitric acid are
the oxidant,
phosphorus would react separated into two layers
nitric acid.
to form phosphoric acid. by the difference of
specific gravity.
Most of the arsenic acid is
However, this method is not
dissolved into nitric acid due to
widely used because it uses nitric
different selectivity and thus
acid as a solvent, which is a strong
separation of the arsenic can be
acid and highly corrosive and
done by extracting the liquid
highly oxidant.
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Fractional distillation
The materials with a large boiling
Impure phosphorus is
point difference to achieve
continually passed through a
phosphorus vaporization will be
heat exchanger and heated to
separated in a disengaging zone,
vaporize a portion of the
while arsenic will be separated in
phosphorus at a temperature
a fractionating zone due to the
not above 200oC.
vapor–liquid equilibrium.
Distillation is both capital and
labor intensive, and also leaves a
distillation residue product that is
much higher in arsenic and other
heavy metals due to the
concentration caused by the
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Mixing and extraction
The purification of Separating the The spent active
yellow phosphorus purified carbon is mixed
can be done in this phosphorus from with sufficient
process by mixing the spent active liquid phosphorus
liquid yellow carbon containing to form slurry,
phosphorus with adhering which is pumped to
active carbon. phosphorus. a disposal zone.

For example, the

active carbon spent
The disposal of the
gives rise to a
spent active carbon
useless and
can cause several
insignificant
problems.
consumption of
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phosphorus.
Phase separation
The mixture of aqueous
Impure white P mixed with
impurities is first separated
aqueous suspension of a
into a settled phase
purifying amount of active
consisting essentially of a
charcoal can be used to
spent active charcoal and
separate P separation funnel
phosphorus-containing phase
due to different phases.
and an aqueous phase.

Then the phosphorus- However, the production of

containing phase and thus, the active charcoal causes
the purified liquid white much pollution as the acid is
phosphorus can be separated involved and heavy metal is
from another separation. produced.
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Oxidation
The purification of
The crude yellow P is
crude yellow P can be Then, the reactant is
first pre-treated by
treated by oxidizing oxidized with mixed
alkali leaching with
those with mixed acid acid of sulfuric acid
ammonium
of sulfuric acid and and nitric acid.
carbonate.
nitric acid.

The strong acid, H2SO4

The purified The loss of P in
and HNO3, highly
phosphorus can be reaction forming
corrosive, strongly
found after washing phosphorus acid
oxidizing agent is
with hot water. would also occur.
used as oxidant.
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Zone Melting
As seen above, all the methods summarized have significant
disadvantages, such as
• high energy consumption,
• hazardous operation-conditions (toxic solvent and vapor), and
• low yield.
The zone melting process for phosphorus purification is clean,
chemical free, fast, and energy efficient.

It is absolutely a zero pollution process.

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Zone Melting
The main apparatus consists of a The heater heats a narrow band of
heater that can move slowly along the sample to the m. p. first and a
the solid sample bar to be purified. melting zone is formed.

As the heater travels along the

Only the specific area heated by the
sample, the melting zone moves
heater can be melted.
correspondingly.

During the solidification process,

After the heater passes, the melting
impurities are segregated into the
zone cools and solidifies.
liquid-phase region.

It can reduce arsenic concentration

in solid phosphorus from 100 ppm to
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10 ppm in a specific condition.
Zone Melting

Purification of Phosphorus by zone melting

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Electrocatalytic oxidation
Electrocatalytic oxidation is one of the common electrochemical
advanced methods.

Electrocatalytic oxidation is able to work in a mild and

controllable condition by adjusting the size of electrode potential
or current intensity.
Electrocatalytic oxidation does not produce any by-product and it
removes impurities rapidly but the non-selectivity is the
weakness.

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Electrocatalytic oxidation
Different types of electrochemical oxidizing agents are produced for
electrocatalytic oxidation reactions when different kind of
electrolytes are chosen.

For example, ·OH, H2O2, O3, ClO−, Br2 and I2 are able to decompose
the macromolecular organic matters to the simple compounds
completely, like H2O and CO2, without any generation of secondary
pollution.

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Electrocatalytic oxidation
The mechanisms of
electrocatalytic oxidation are
divided into direct reaction
mechanism and indirect reaction
mechanism.

For the indirect reaction

For the direct reaction
mechanism, when active oxidation
mechanism, organic and
site is not on the electrode, the
inorganic substances are oxidized
organic and inorganic matters are
on various metal electrodes
oxidized by other oxidants produced
which are regarded as oxidants at
in the electrolyte solution such as
a higher oxidation potential.
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bromine ions and iodine ions.
Electrocatalytic oxidation

Conventional phosphorus purification is an energy

consuming and environmentally polluting process.

Electrocatalytic oxidation can be an efficient and zero

pollution alternative for producing high purity phosphorus,
the zone melting technique.

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