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RARE EARTH

Rare earth is a group of metallic elements, including No.21 scandium,No.39 yttrium, and from No.57 lanthanum to No.71 Lutetium in periodic table. The discovery of the total rare earth elements took 135 year as much. On account of their similarities, it is not 40's of the century, until that the pure rare earth individuals were not prepared in commercial scale except a small quantity obtained in laboratory. At that time, the pure rare earth individuals were expensive, as such strictly limited their application.

In 1947, Some American scientists developed an effective separation process called ion exchange, then the process was used to separate adjacent rare earth element and successful. F.H.spedding improved the process, by thus this method, high purity rare earth individual compounds in kg scale were prepared.

In 1958, solvent-solvent extraction commenced coming to be used to group separation in a large scale production line. In 1964 pure Europium, Yttrium, Lanthanum oxide were produced by this process, which effectively inspired rare earth industry. Up to 1980'America mining amount was over 25300 tons(REO).

Owing to the abounding of rare earth mineral resources, and the making use of the new extraction: 2-ethylhexyl phosphate mono-(2-ethylhexyl) ester (Developed by Daihachi chemical industrial Co.,ltd) China exceed America in separation capacity for the first time in 1986. China possesses 70% rare earth mineral resources of the globe. The most famous mine in the world is Baiyunebo in Boutou Inner Mongolia which main ingredient is light rare earth. In south China the most important mine is called ion absorption type, which major constitution is heavy rare earth.

China's mining quantum of rare earth in 1995 accounted for 70% of total production in the world. Now, China has become the biggest supplier of rare earth over the world. Nowadays, rare earth in indispensable. The teems below will show you main uses of rare earth. We believe that the rare earth family will play an important role in human life in the coming century definitely.  

WORLD RESERVES OF RARE EARTH MINERALS AND THEIR DISTRIBUTION 


There is large amount of  reserves of rare earth minerals in the world. The largest proved reserves are located in China. Other important reserves of rare earths are located in Australia, Russian Federation, United States, Brazil, Canada and India. In Vietnam. In addition, some deposits of rare earths was found in South Africa, Malaysia, Indonesia, Sri Lanka, Mongolia, North Korea, Afghanistan, Saudi Arabia, Turkey, Norway, Greece and Nigeria, Kenya, Tanzania, Burundi, Madagascar, Mozambique and Egypt.

Deposits with reserves of more than Mt are as follows:
Baiyun Obe iron-niobium-rare earth deposit in Inner Mongolia in China;
Bastnaesite deposit in Sichuan in China;
Ion adsorption clays in Southern provinces in China;
Mount Weld monazite deposits associated with carbonate intrusions in Australia;
Heavy beach san placer deposits in Australia;
Bastnaesite deposit at Mountain Pass in USA;
Alaxia; Zaislagushi rare earth deposit associated with wethering carbonate in Brazil;
Tuomutur rare earth deposit associated with wethering carbonate in Russia;
Shibin rare earth deposit associated with phosphate and nepheline;
Maosai rare earth deposit in Vietnam.
Some of deposits mentioned above contain more than 10 Mt REO and one or two contain more than 100Mt REO.

According to relevant statistical datum, the proportion of Chinese rare earths reserves in world rare earths reserves as a whole decreased to about 69% in 1980s and 45% in 1990s from 74% in 1970s as results of discovering of large and super-large rare earth deposits in Australia, Russia, Canada, Brazil and Vietnam, but China is still the largest country reserves of rare earths in the world, moreover,it has large undefined reserves of rare earths. It is believed that this situation could be maintained for a long time. World reserves of rare earths is shown in table 1.

Table 1 World reserves of rare earths(Mt,REO)*

Country

Reserve

Reserve Base

Year 1989

Year 1993

Year 1989

Year 1993

China

36.00(80.0)

43.00(43)

36.00(75.0)

48.00(43.6)

Russian Federation

0.45(1.0)

19.00(19)

0.48(1.0)

21.00(19.1)

USA

5.50(12.3)

13.00(13)

6.50(13.5)

14.00(12.7)

Australia

0.48(1.5)

5.20(5.2)

0.75(1.6)

5.80(5.3)

India

1.80(4.0)

1.10(1.1)

1.90(4.0)

1.30(1.2)

Canada

0.164(0.36)

0.94(0.94)

0.20(0.4)

1.00(0.9)

South Africa

0.39(0.39)

0.40(0.36)

Brazil

0.02(0.04)

0.28(0.28)

0.073(0.15)

0.31(0.28)

Malaysia

0.03(0.07)

0.03(0.03)

0.035(0.06)

0.035(0.03)

Srilanka

0.012(0.01)

0.013(0.01)

Others

0.174(0.39)

21.00(21)

1.70(3.5)

21.00(19.1)

Total

45.00

100.00

48.00

110.00

*Note:(1)Source: Rare Earth-Mineral Commodity Summaries, U.S.Geological Survey; (2)Figure in the brackets is percentage of world rare earth reserves;

Proved rare earth reserves in China is 43 Mt of REO,contributing a 43% of world rare earth reserves according to the publishing datum from abroad ( It was reported by the committee of Geology Mining-Ore Dressing of Chinese society of Rare Earths that proved rare reserves in China was 52 Mt of REO,contributing more than half of the world rare earth reserves).Rare Earth resources of China are note for their large preserves, varieties of minerals, well partition, higher grade and wide distribution. They lay a foundation for Chinese rare earth industry.

In January 1993 the US Geological Survey estimated Russian Federation's reserves of rare earths as 19 Mt(REO), representing around 19% of the world's total reserves. Rare earth resources in Russian Federation are concentrated in titanoniobates ( such as loparite),phosphorites( such as apatite) and fluorocarbonates (such as yttrosynchisite ). Commercial quantities of rare earth products have been recovered in Russian Federation mainly from apatite.

Rare earth reserves in USA total 13Mt, representing around 13% of the world's total reserves. The important resources are bastnaesite and monazite. The largest single deposit of rare earths is the bastnaesite deposit at Mountain Pass, San Bernnadino County in California. Rare earth reserve totals 4.3Mt,grading 5% กซ10% REO. Monazite deposits are located in beach placers in Florida, in north western fluvial placers and in Atlantic continental shelf sediments. Rare earth reserve at Poken Mountain is 6.8Mt,grading 0.264% REO,and 33.3% of it is yttrium oxide.The ore dressing and extraction test have been carried out.

Australia has the largest monazite reserves.Several rare earth deposits were discovered in recent years.the proved rare earth reserve in Mt.Weld is 1.7Mt.Rare earth reserves in Australia total 5.2Mt,increasing ten times from 1980s.

India's total rare earth reserves total 1.1Mt,representing around 1% of the world's total reserves. The main resource is monazite,accuring in beach placers and continental placers. India's Atomic Minerals Division and Department of Atomic Energy estimated that India's total monazite reserves total 4.56Mt.

Canada recovers rare earths mainly from uranium mining residues. The large unexplored deposit is located in Orka, Quebec. The Strange Lake deposit, located in Labuladuo, contains yttrium and heavy rare earths. The prepared work for exploitation is being done.

South Africa is in a leading position in monazite production in Africa. The apatite deposit, located in Steenkampskraal, Cape, contains monazite and is a only single-vein monazite deposit in the world. The heavy beach sand placer, located in East Coast,also contains rare earths. Fabuluo Fluorite deposit contains monazite and bastnaesite. It is expected to be exploited in future.

Brazil is the oldest country in view of its rare earth production. It was well known for its export of monazite to Germany early in 1884. Placer deposits of beach sands, which contain monazite, extend along the East Coast. The deposits are exploited by Nuclemon. Other deposits were discovered in recent years with grade 4% REO.

 

THE MAIN APPLICATION OF RARE EARTH

1.Metallurgy: de-oxygen de-sulfur, and other injurious ingredients to act reducing agent.

2.Flint, ignition device

3.catalyst for problem crack

4.Automobile exhaust gas crack 

5.Glass ceramic clearing, de-coloring agent, anti-ultraviolet glaze

6.Permnent magnets SmCo,NdFeB

7.Super-conductor

8.Functional ceramic, yttria+zirconia

9.Phosphor for color TV, ceria+zirconia

10.Hydrogen storage, secondary battery

11.Polishing powder

12.Laser material, optical fiber optical lens

13.Magnentic forced extant-contract material

14.Substitution of poisonous Cd pigments

 

GENERAL  DESCRIPTION 

Rare Earth Oxides

RE oxide are most stable from various RE compounds, the fundamental raw material of other compounds and are basic products of raw material in RE industry. RE oxides are generally prepared by ignition of corresponding hydroxide, oxalate, carbonate salt, nitrate salt, soleplate salt in the air. RE oxide are insoluble in water and basic solution, soluble in strong mineral acids, and apt to absorb cabin dioxide from air to form carbonate salt. All RE oxide are powder and their melt points are above 2300℃.

Rare earth hydroxides

RE Hydroxides are generally prepared by mixing corresponding soluble salt with ammonium hydroxide or sodium hydroxide they are soluble in acids, insoluble in water, and generally powder.

Rare earth Chlorides

There are two kinds of RE chlorides, anhydrous and hydrous chlorides. The former is prepared by heating, dewater in vacuum of it's hydrous. The Later is prepared by condensing of its corresponding RE chloride solution. All RE chlorides are hydroscopic and substantially soluble in water.

Rare earth Sulphates 

RE sulphates are generally prepared by adding sulphuric acid to their corresponding oxides, hydroxides, carbonates, and the solid state of the salt can be prepared by condensation of the solution. All RE sulphates are soluble in water, but their solubilities are lower and down with the temperature up.

Rare earth Carbonate

The solid RE carbonate can be prepared by adding more the solution of soluble RE salt. RE carbonates are little soluble in water, soluble in acids to yield corresponding salt and give off CO2 RE carbonates decompose to be oxides over 905℃.

Rear earth Nitrate 

Hydrous RE nitrates can be prepared by condensing the solution of their salt which are obtained by mixing the nitric acid and RE oxide, hydroxide, carbonate. RE nitrates are most soluble in water of various salt and soluble in some organic agents-alcohol acetone etc. When the salts are heated, give off 02,NO,N02,the final products are oxides.

Rear earth Fluorides 

RE fluorides are prepared by adding HF solution RE salt solution are insoluble in water, soluble in thick acid, and the major raw material for electrolysis of RE metal.

Rear Earth Metals 

RE metals appear as of typical metallicity. Their melt points and densities increase with the atomic number except Europium and ytterbium, yet the hardness increases with the atomic number in spite of being soft. Although their tensile stresses are low, RE metals show fairly high stretchy .The activities of the Metals increase in sequence in Sc,Y,La, however decrease from La to Lu sequentially. The metals are liable to oxidize in the air, inert in cool water, but active to hot water and realease hydrogen and violently react with acids, but rather inactive to bases. The metals are combustible. As such should be kept carefully. Normally, RE metals are manufactured by electrolysis or pyroreduction. RE metals are rather effective reductants in metallurgical, the metals have been used to prepare high performance magnetics, fuel batteries, secondary cells, and functional non-ferrous materials. 

 

RARE EARTH OXIDES FORMULA WEIGHT

Atomic

Symbol

Atomic

Number

Atomic

Weight

Rare earth

Oxide

F.Wt Half F.Wt
La 57 138.905 La2O3 305.8 162.9
Ce 58 140.12 CeO2 172.1 172.1
Pr 59 140.908 Pr6O11 1021.4 170.2
Nd 60 144.2 Nd2O3 336.4 168.2
Sm 62 150.4 Sm2O3 348.8 174.4
Eu 63 151.96 Eu2O3 351.9 176.0
Gd 64 157.2 Gd2O3 362.4 181.2
Tb 65 158.925 Tb4O7 747.7 186.9
Dy 66 162.5 Dy2O3 373.0 186.5
Ho 67 164.93 Ho2O3 377.9 188.9
Er 68 167.2 Er2O3 382.4 191.2
Tm 69 168.93 Tm2O3 385.87 192.93
Yb 70 173 Yb2O3 394.0 197.0
Lu 71 174.96 Lu2O3 397.9 199.0
Sc 21 44.9559 Sc2O3 137.91 69.0
Y 39 88.9059 Y2O3 225.8 112.9

RARE EARTH STANDARD ELECTRODE POTENTIAL

Acidic solution V Alkaline solution V
La3++3e=La -2.522 La(OH)3+3e=La+3OH- -2.9
Ce3++3e=Ce   La(OH)3+3e=La+3OH-  
Ce4++e=Ce3+   La(OH)3+3e=La+3OH-  
Pr3++3e=Pr   La(OH)3+3e=La+3OH-  
Nd3++3e=Nd   La(OH)3+3e=La+3OH-  
Sm3++3e=Sm   La(OH)3+3e=La+3OH-  
Sm3++e=Sm2+   La(OH)3+3e=La+3OH-  
Eu3++3e=Eu   La(OH)3+3e=La+3OH-  
Gd3++3e=Gd   La(OH)3+3e=La+3OH-  
Tb3++3e=Tb   La(OH)3+3e=La+3OH-  
Dy3++3e=Dy   La(OH)3+3e=La+3OH-  
Er3++3e=Ho   La(OH)3+3e=La+3OH-  
Ho3++3e=Er   La(OH)3+3e=La+3OH-  
Tm3++3e=Tm   La(OH)3+3e=La+3OH-  
Yb3++3e=Yb   La(OH)3+3e=La+3OH-  
La3++3e=La   La(OH)3+3e=La+3OH-  
La3++3e=La   La(OH)3+3e=La+3OH-  
La3++3e=La   La(OH)3+3e=La+3OH-  
La3++3e=La   La(OH)3+3e=La+3OH-  

 

PHYSICAL PROPERTIES OF RARE EARTH METALS

Atomic Numbe

Atomic Symbol

Atomic Weight

Ionic Radius(A)

Density
(g/cm3)

Melting Point (oC)

Boiling Point(oC)

Oxide's Melting Point(oC)

Specific Resistance

Magnetic Moment

Thermal Neutron Capture Cross Section

57
58
59
60
61
62
63
64
65
66
67
68
69
70
71
21
39

La
Ce
Pr
Nd
Pm
Sm
Eu
Gd
Tb
Dy
Ho
Er
Tm
Yb
Lu
Sc
Y

138.92
140.13
140.92
144.27
147.00
150.35
152.00
157.26
158.93
162.51
164.94
167.27
168.94
173.04
174.99
44.97
88.92

1.22
1.18
1.16
1.15
1.14
1.13
1.13
1.11
1.09
1.07
1.05
1.04
1.04
1.00
0.99
0.83
1.06

6.19
6.768
6.769
7.007
-
7.504
5.166
7.868
8.253
8.565
8.799
9.058
9.318
6.959
9.849
2.995
4.472

920+/-5
80
4+/-5
935
+/-5
1024
+/-5
-
1052
+/-5
826
+/-10
1350
+/-20
1336
1485
+/-20
1490
1500
~1550
1500
~1600
824+/-5
1650~1750
1550~1600
1552

4230
2930
3020
3180
-
1630
1490
2730
2530
2330
2330
2630
2130
1530
1930
2750
3030

2315
1950
2500
2270
-
2350
2050
2350
2387
2340
2360
2355
2400
2346
2400
-
2680

56.8
75.3
68.0
64.3
-
88.0
81.3
140.5
-
56.0
87.0
107.0
79.0
27.0
79.0
-
-

0.00
2.56
3.62
3.68
2.83
1.55
~
1.65
3.40
~3.50
7.94
9.7
10.6
10.6
9.6
7.6
4.5
0.00
-
-

8.9
0.7
11.2
46
-
5500
4600
46000
44
1100
64
166
118
36
108
13
1.27


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