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Fathi Habashi
Department of Mining, Metallurgical, and Materials Engineering
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
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
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
RAW MATERIAL
Monazite and xenotime: phosphates Bastnasite: fluorocarbonate Phosphate rock
Relative abundance
Rare earths 10-4 % Similar to arsenic, antimony, molybdenum, tungsten, beryllium, tantalum, and germanium
Monazite
Color
Specific gravity Hardness, Mohs Crystal structure Yellow to red brown 4.95.5 5 Monoclinic
Xinotime
Pale yellow to brownish green
Separation of monazite and other minerals from black sand by physical methods
Beach sand
Light
Conductor
Nonconductor Nonmagnetic Zircon Magnetic separation Magnetic Monazite Magnetic separation Magnetic Ilmenite Nonmagnetic Rutile
= Lanthanide
93
8.4
98.9
Heavy
91.6
1.37
Filtration
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.
Ion
exchange
Solvent
extraction
Thank s
Fathi Habashi