Extraction of rare earth

elements from mine tailings

Sebastiaan Peelman
Delft University of Technology
Department of Material Science and Engineering
Metals Production, Refining and recycling
s.peelman@tudelft.nl

February 14-18, Downtown Nashville,

Tennessee, Music City Center

Contents
Introduction
Characterization of the mine tailings
Leaching

Residue analysis
Proposed process route
Conclusions

February 14-18, Downtown Nashville,

Tennessee, Music City Center

Introduction
Critical raw materials defined by the EU

http://ec.europa.eu/growth/sectors/raw-materials/specific-interest/critical/index_en.htm

February 14-18, Downtown Nashville,

Tennessee, Music City Center

LKAB mine tailings

Exploration of the
tailings have
revealed:
1200-1500 ppm REE
4-8% P (apatite)

50-100M tons of
tailings currently in
the dam
largest REE
deposit in Europe
February 14-18, Downtown Nashville,
Tennessee, Music City Center

Apatite flotation
The tailings were first treated by Plsson et al. at
LTU Sweden
The REE and P content of the tailings were
upgraded using flotation
Particle sizes after upgrading range from 10100m

February 14-18, Downtown Nashville,

Tennessee, Music City Center

Characterization of the upgraded

tailings
Main minerals:
(Fluor)Apatite
Calcite
Dolomite

Trace minerals:
Silica
Magnetite
REE phosphate
Likely monazite

February 14-18, Downtown Nashville,

Tennessee, Music City Center

Traditional rare earth extraction

Primary REE ores are usually treated via either:
Alkaline pressure leaching
Sulfuric acid roasting

Both processes are not economical to apply to

this low grade REE source
Does nor account for the P content

Methods for P recovery were researched for REE

recovery

February 14-18, Downtown Nashville,

Tennessee, Music City Center

Leaching
H3PO4 is the main P product produced from
apatite
Traditionally H2SO4 leaching is used:
( ) + + +

CaSO4 is detrimental to REE recovery

HCl and HNO3 as alternative:
( ) + + +
( ) + ( ) + +

February 14-18, Downtown Nashville,

Tennessee, Music City Center

HCl leaching: tailings behavior

Ca minerals highly
reactive non
excess acid
required
REE mineral
resistant to
dissolution
large excess of
acid required

February 14-18, Downtown Nashville,

Tennessee, Music City Center

HCl leaching: REE behavior

Heavy REE react
differently from
light REE
REE are chemically
very similar
Indicates the
presence of 2 REE
minerals

February 14-18, Downtown Nashville,

Tennessee, Music City Center

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Identifying the second REE

mineral
A REE mineral other than monazite appears
present
REE can incorporated within the apatite lattice
through substitution
REE should co-dissolve with the apatite
Dissolving apatite also produces H3PO4
H3PO4 dissociates into H2PO4-, HPO42- and PO43depending on the pH

February 14-18, Downtown Nashville,

Tennessee, Music City Center

11

Identifying the second REE

mineral
Phosphate anions can react with dissolved REE
to form insoluble precipitates
+ + =

A pH low enough (0-1) will inhibit the formation

of these anions

Only at high acid concentration (excess) can any

dissolved REE remain in solution
Apatite is likely the second REE mineral and a
source of heavy REE

February 14-18, Downtown Nashville,

Tennessee, Music City Center

12

HNO3 leaching
HNO3 leaching was compared to HCl leaching
Results HNO3 are very similar to HCl
increased acid concentration has little effect

Monazite is not dissolving in HCl or HNO3

Supports that apatite is the second REE mineral

February 14-18, Downtown Nashville,

Tennessee, Music City Center

13

Residue analysis: SEM/EDS

REE particles maintain the same approximate

size before and after leaching and show no sign
of partial dissolution

February 14-18, Downtown Nashville,

Tennessee, Music City Center

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Residue analysis: XRD

Remaining
minerals:

Quartz
Hematite
Magnesio silicates
monazite

February 14-18, Downtown Nashville,

Tennessee, Music City Center

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Ca(NO3)2 precipitation
Ca recovery possible
by cooling solution
Low L/S (2-3) leads to
more effective
recovery
50-75% of Ca was
removed
No REE losses
observed in the
precipitates

February 14-18, Downtown Nashville,

Tennessee, Music City Center

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Proposed process flowsheet

February 14-18, Downtown Nashville,

Tennessee, Music City Center

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Conclusions
Total REE recovery not achievable under present
conditions
Two REE minerals are present in the upgraded
tailings: apatite and monazite

Apatite is rich in heavy REE and monazite is rich

in light REE
Apatite readily dissolves in acidic solutions, but a
low end pH is required for the dissolved REE to
remain in the solution
Monazite does not dissolve, even in heated and
concentrated HNO3
February 14-18, Downtown Nashville,
Tennessee, Music City Center

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Conclusions
Phosphorous is recovered as H3PO4 together with
the heavy REE
Calcium can be partially removed and valorized
as Ca(NO3)2 ,when HNO3 is used as leachant, by
chilling the solution
The leach residue can be treated as a low grade
monazite concentrate and be processed by
alkaline treatment or roasting treatment as a
source of light REE

February 14-18, Downtown Nashville,

Tennessee, Music City Center

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Thank you for your attention

February 14-18, Downtown Nashville,

Tennessee, Music City Center

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