Extractive Metallurgy of the Rare Earths

Fathi Habashi
Department of Mining, Metallurgical, and Materials Engineering

Laval University, Quebec City Fathi.Habashi@arul.ulaval.ca

Rare Earths in the Periodic Table

La Ce Pr Nd Pm Sm Eu G d Tb D y Ho Er Tm Yb Lu
57 58 59 60 61 62 63 64 65 66 67 68 69 70 71

PERIODIC TABLE METALS

TYPICAL METALS
3 4

Monatomic
METALLOIDS

NONMETALS Covalent
5 6 7 8 1 2

TRANSITION METALS
Horizontal Similarity
22 23 24 25 26 27 28 29

H
9

He
10

Li
11 19

Be
12 13

B Al
21

C
15

N
16

O
17

F Cl
35

Ne
18

Na Mg
20

LESS TYPICAL
METALS 30 31 32

Si
33 50 51

P
34 52

S
53

Ar
36

K
37

Ca Sc
38 39 40

Ti
41

V
42 73 74

Cr Mn Fe Co
43 44 45 46 75 76 77 78

Ni

Cu Zn Ga Ge As Se
47

Br
54

Kr Xe
86

Rb
55 56 87 88

Sr
57 89

Y
*La
72

Zr Hf

Nb Mo Tc Ru Rh Pd
79

Ag

48

49

Cd
80

In
81

Sn Sb
82 83 84

Te
85

I At

Cs Ba Fr

Ta

Re Os

Ir

Pt

Au

Hg

Tl

Pb

Bi

Po

Rn

Ra **Ac
58 59

Vertical Similarity

Vertical & Horizontal Similarity

60

61

62

63

64

65

66

*Lanthanides

Ce
90 91

Pr Pa

Nd Pm Sm Eu Gd Tb
92 93

Dy

67

68

69

70

71

Ho
99

Er Tm Yb Lu
100 101 102 103

**Actinides

Th

Np

94

95

96

97

98

Pu Am Cm Bk

Cf

Es Fm Md No Lw

INNER TRANSITION METALS

RAW MATERIAL
Monazite and xenotime: phosphates Bastnasite: fluorocarbonate Phosphate rock

Other complex minerals

Euxenite (Y,Ce)(Nb,Ta,Ti)2O6 Samarskite (Y,Ce)4(Nb,Ta,Ti)2O6 Fergusonite (Y)(Nb,Ti,Ta)O4 Betafite (U,Ca,Y,Ce2(Nb,Ta,Ti)2O6(OH) Pyrochlor (Na,Ca,Ce)2(NbTa,Ti)2(O,OH,F)7 Loparite (Na,Ca, Ce)2(Nb,Ta,Ti)2O6

Rare earths in China

[1] Associated with iron ore in Baotou, Inner Mongolia Autonomous Region, northern China [2] Associated with clay in Guandzhou, Guandong Province in southern China

Home of rare earths welcomes you

Relative abundance
Rare earths 10-4 % Similar to arsenic, antimony, molybdenum, tungsten, beryllium, tantalum, and germanium

Monazite and Xenotime

The minerals monazite and xenotime are lanthanide phosphate containing some thorium and small amounts of uranium. They differ slightly in crystal structure and the individual lanthanides occur in different proportions. Monazite is widely distributed in the Earths crust and occurs in small proportions in granites. When such rocks are weathered, grains of monazite are carried by waters, then deposited at the mouths of rivers, together with the heavier constituents of the parent rock, to form black sands. Monazite occur mainly in Brazil, India, Australia, and USA, xinotime occurs mainly in South East Asia associated with alluvial tin deposits.

Physical properties of lanthanide minerals

Monazite
Color
Specific gravity Hardness, Mohs Crystal structure Yellow to red brown 4.95.5 5 Monoclinic

Xinotime
Pale yellow to brownish green

4.54.6 4.5 Tetragonal

Separation of monazite and other minerals from black sand by physical methods
Beach sand

Gravity concentration Heavy Magnetic separation

Light

Silica Magnetic Magnetite

Nonmagnetic Electrostatic separation

Conductor

Nonconductor Nonmagnetic Zircon Magnetic separation Magnetic Monazite Magnetic separation Magnetic Ilmenite Nonmagnetic Rutile

Chemical analysis of the concentrates

Monazite concentrat e, % P2O5 Ln2O3[1] ThO2 U 3 O8 SiO2 CaO Fe2O3 Al2O3 ZrO2 SnO2
[

Xenotime concentrate, % 5263 1 3 0.53.5 2 3 0 9

2429 5565 510 0.20.4 13 0.20.8 12 0.10.8 0.7

1]Ln

= Lanthanide

Composition of lanthanides in monazite, xenotime, and bastnasite

Lanthanide oxide Light La2O3 CeO2 Pr6O11 Nd2O3 Sm2O3 Eu2O3 Gd2O3 Tb4O7 Dy2O3 Ho2O3 Er2O3 Tm2O3 Yb2O3 Lu2O3 Y2O3 Monazite % 23.0 46.5 5.1 18.4 2.3 0.07 1.7 0.16 0.52 0.09 0.13 0.013 0.061 0.006 2 Xenotime % 0.5 5.0 0.7 2.2 1.9 0.2 4.0 1.0 8.7 2.1 5.4 0.9 6.2 0.4 60.8 Bastnasite % 32.0 49.0 4.4 13.5 0.5 0.1 0.3 0.01 0.03 0.01 0.01 0.2 0.01 0.1 0.1

93

8.4

98.9

Heavy

91.6

1.37

RECOVERY: Monazite, xenotime

Monazite concentrate Monazite concentrate

NaOH H2SO4 Digestion H2O

Dissolution Filtration

Leaching Residue : hydroxides of U, Th, R.E. Na3PO4 10H2O

Filtration

Residue SiO2 TiO2 ZrSiO4

Crystallization

Solution

Acid method: 2LnPO4 + 3H2SO4 Ln2(SO4)3 + 2H3PO4 Alkali method: LnPO4 + 3NaOH Ln(OH)3 + Na3PO4 Hydroxides of uranium, thorium, and lanthanides, containing small amounts of phosphate; it is dissolved in acid for further separation.

Bastnasite
Bastnasite is a fluorocarbonate: Ln2(CO3)3, LnF3 or LnFCO3.

Bastnasite
In the Molycorp process, the mineral is concentrated to 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 earth elements to go into solution, leaving behind 6580% CeO2

Bastnasite
The scheme of separation of the lanthanides from leach solution of bastnasite concentrates by extraction with D2EHPA. Cerium is already separated in the leaching step since it is transformed into soluble cerium(IV) compound and is recovered from the residue. Each extraction step includes numerous stages of contact with the extractant and the stripping agent under certain conditions of organic/aqueous ratio, and extractant and stripping agent concentrations. The plant is computerized and is fully automated.

MolyCorp process

Phosphate rock
Phosphate rock occurs either as a sedimentary deposit, e.g., in Florida and North Africa, or as igneous rock, e.g., in Kola peninsula, Russia. Only igneous phosphates contain rare earths Igneous phosphates supply about 15% of the phosphate rock for the industry.

Production
Tonnage wise, phosphate rock is the most important source of rare earths as compared with the other material. About 18 million tons of igneous rock are treated annually while only 30 000 tons of monazite and xenotime.

 During the manufacture of phosphoric acid about 70% of the rare earths is lost in the gypsum. However, if acidulation is conducted by nitric acid all will go into solution and can be recovered by organic solvents. In Finland, the lanthanides were recovered commercially by Kemira Oy from phosphate rock during 19651972 using organic solvents. It is believed that a similar operation is in existence in Russia.

Nitric acid leaching

Norsk Hydro BASF Etc. ================================ Can be conducted in heaps ================================

New separation technology

No more fractional crystallization

Ion

exchange

Solvent

extraction

Rare earths and nuclear reactors

Rare earths are fission products [atomic weight 140] They absorb neutrons and must be removed Ce 144 product of atomic bombs [t 285 days]

New uses of rare earths

TV screens Special magnets Special alloys Catalysts Electronics Glass and ceramics

Thank s
Fathi Habashi