Latest Scenario in Rare Earth and Atomic Minerals in India
Dr. R. N. Patra Chairman & Managing Director Indian Rare Earths Limited Mumbai 022 24225778 +91 9869272093 [email protected] Website: www.irel.gov.in
1 Presentation Summary
Introduction to Rare Earth (RE)
RE-Global scenario
Indian Context & Role of Indian Rare Earths Limited
Monazite Processing & Rare Earth Production
Strategic significance from the view point of its usage and nation’s growth
2 Major Minerals of RE of Commercial importance
Chemical Countries of Minerals formula origin Remark Carbonate Processing relatively simpler than Monazite. It has larger content of USA, China & (Ce,La) FCO Europium compared to Monazite. In Bastnaesite 3 Australia China it is associated with iron ore mining. Phosphate
RE content more or less uniform around Australia, India, 60% and minerals available in placer (Ce,La,Th & U) PO Malaysia, Brazil, Monazite 4 beach sand resources. The ore contains Thailand & Korea Th & Uranium which are radioactive
Malaysia, India, Yttrium major constituent. In Malaysia YPO Xenotime 4 China production is associated with Tin mining
Apatite (CaRE)5[(PSi)O4]3(O,F) CIS, South Africa Occurs in Copper, Tin, Phosphate mining Ion Weathered apatite & Unique deposits found only in southern xenotime ore China. Though lowest in rare earth China exchange concentrated in the soil contents easiest to concentrate from the clay in ionic form ore. Rich source of Y, Eu, Tb & Dy Major Minerals of RE of Commercial importance
Main Countries of Minerals Chemical formula origin Remark Oxides (Ce,La,Ca,Na) Loparite CIS Contents above 40% Titania (TiNb)2 O6 Source of Scandium & (Y,Ce, Ca,U,Th) Euxenite USA Yttrium. Recovered as by (Nb,Ta,Ti) O 2 6 product from Bastnaesite Sillicate Source of Yttrium. Gadolinite Be2FeY2Si2O10 USA Recovered as by product from Bastnaesite In addition rare earths are also produced as a by product of uranium recovery from its ores in Canada. RE contents of major source minerals (%) Light rare earths minerals Heavy rare earths minerals Rare Earths Monazite Bastnasite Xenotime Ion exchange clay* as oxide (Ce,La,Th & U) PO4 (Ce,La) FCO3 YPO4 India Australia, USA China, USA Malaysia China China China Lanthanum 22 17.4 - 27.6 23.0 - 35.0 0.5 - 1.4 1.8 - 43.4 Cerium 46 42.7 - 51.1 49.0 - 51.7 1.75 - 5.0 0.37 - 7.2 Praseodymium 5.5 4.1 - 5.4 3.7 - 6.2 0.47 - 0.7 0.02 - 7.4 Neodymium 20 14.6 - 18.7 9.5 - 18.5 1.59 - 3.5 3.0 - 31.6 Samarium 2.5 1.0 - 4.9 0.45 - 1.25 1.1 - 2.2 2.3 - 6.3 Europium 0.015 0.04 - 0.8 0.05 - 0.25 0.01 - 0.2 0.12 - 0.83 Gadolinium 1.2 0.5 - 6.6 0.16 - 0.7 3.4 - 5.0 3.0 - 6.8 Terbium 0.06 Trace - 0.7 0.01 - 0.1 0.9 - 1.2 trace - 1.29 Dysprosium 0.18 0.2 - 0.9 0.03 - 0.13 8.3 - 9.1 trace - 7.5 Holmium 0.02 Trace - 0.12 Trace - 0.05 1.98 - 2.6 trace - 1.64 Erbium 0.01 Trace - 0.3 Trace - 0.07 5.4 - 7.0 trace - 4.85 Thulium Nil Trace - 0.03 Trace - 0.0009 0.9 - 1.3 trace - 0.7 Ytterbium Nil 0.11 - 2.4 Trace - 0.0006 5.9 - 6.8 0.26 - 3.3 Lutetium Nil trace - 0.14 Trace - 0.0001 0.4 - 1.8 0.1 - 0.47 Yttrium 0.45 0.19 - 3.2 0.09 - 0.76 59.3 - 80.0 8.0 - 65.0 RE-Major end uses Rare Earth Occurrences RE Mines in Operation
Greenland Russia China
Canada
USA
Vietnam
India Malaysia
Brazil Australia
South Africa Malawi Major Mines in operation
BASTNAESITE APATITE Baiyun Obo & Sichuan, China; Nangang, Guangdong, China; Mt Pass, USA; Nolans Bore, Australia; Dong Pao, Vietnam; Hoidas Lake, Canada. Dubbo Trachyte, Australia.
MONAZITE EUDIALYTE India; Zeus, Canada; Guangdong, China; Steenstrupine, Greenland. Mount Weld, Australia; Kangankunde, Malawi Zandkopsdrift, SA Steenkampskaal, SA. LOPARITE Lovozersky, Russia XENOTIME Ptinga, Brazil; Lahat Perak, Malaysia; FERGUSONITE Guandong, China Nechalacho, Canada. RE - World Production & Reserves Select RE projects outside China
S.no Company Country Proposed REO Capacity 1 Lynas Corp Malaysia 22,000 2 Molycorp Minerals USA 20,000 3 Indian Rare Earths Limited India 5,000 4 Great Western Minerals South Africa 2,500 5 Alkane Resources Australia 2,600 6 Vietnamese Gov/Toyata Tsusho/Sojitz Vietnam 3000 – 5,000 7 Arafura Resources Australia 20,000 8 Avalon Rare Metals Canada 5,000 9 Kazatomprom/Sumitomo Kazakhstan 15,000 10 Stans Energy Kyrgyzstan 2,000 11 Minerals and Energy Greenland 43,700 12 Rare Element Resources USA - 13 Resources Canada - 14 Quest Rare Metals Canada - 15 Ucore Uranium USA - 16 US Rare Earths USA - 17 Matamec Explorations Canada 18 Etruscan Resources Namibia - 19 Montero Mining Tanzania - 20 Tasman Metals Sweden & Finland 21 Neo Material Technologies/ Mitsubishi Brazil - Total 1,38,800 – 1,42,800
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Indian Context & Role of Indian Rare Earths Limited Indian source of RE
Monazite composition
Composition %
REEs as Re2O3 59.37
P2O5 27.03
ThO2 8.88
U3O8 0.35 CaO 1.24
SiO2 1.0 MgO 0.63
Fe2O3 0.32
Al2O3 0.12 PbO 0.18
TiO2 0.36
ZrO2 0.49
Monazite is rich in LRE and lacks HRE Properties of Monazite
• Color: Honey Yellow to Golden Yellow. Also Pale Yellow.
• Sp. Gravity: 4.6 - 5.47. Theoretically, higher Th content results in higher Sp. Gr.
• Shape: Subhedral to rounded grains
• Hardness: 5 to 5.5 on the Moh’s scale
• Crystal: Monoclinic, brittle with conchoidal or uneven fractures
• Magnetism: High magnetic susceptibility derived from para magnetism of R.E.
• R.E. & Th.: Typically 60% predominantly light R.E. ThO2 varies 4.0 -8.5%.
15 Prescribed Substances
Gazette notification S.O. 61 (E) dated 20.01.2006 under the Atomic Energy Act, 1962 stipulates the prescribed substances, which are as follows:
Source Material – Uranium containing the mixture of isotopes and Uranium depleted in the isotope 235, – Thorium – Any other material containing one or more of the foregoing
Special Fissionable Material – Plutonium 239 – Uranium 233 & Uranium enriched in the isotopes 235 or 233 – Neptunium – Any material containing one or more of the foregoing. Other Material (Non-nuclear materials for reactors, nuclear related dual – use materials, etc) – Deuterium, Heavy water – Nuclear grade graphite/ carbon – Zirconium, Berillium, Lithium, Hafnium, Niobium & Tantalum – Titanium Alloys – Tritium and its compounds – Radium 226, Boron, Helium-3 – Alpha emitting radionuclides Associated Minerals
(i) Apatite, Beryl, Cassiterite, Columbite, Emerald, Felspar, Lepidolite, Mica, Pitchblende, Quartz, samarskite. Scheelite, Topaz, Tantalite, Tourmaline.
(ii) Iron, Manganese, Titanium, Vanadium and Nickel minerals.
(iii) Lead, Zinc, Copper, Cadmium, Arsenic, Antimony, Bismuth, Cobalt, Nickel, Molybdenum and Uranium minerals, and Gold and Silver, Arsenopyrite, Chalcopyrite Pyrite, Pyrrhotite and Pentlandite.
(iv) Chromium, Osmiridium, Platinum and Nickel minerals.
(v) Kyanite, Sillimanite, Corundum, Dumortierite and Topaz
(vi) Gold, Silver, Tellurium, Selenium and Pyrite..
(vii) Barytes, Fluorite, Chalcocite, Selenium and minerals of Zinc, Lead and Silver.
(viii) Tin and Tungsten minerals.
(ix) Limestone, Dolomite and Magnesite.
(x) Ilmenite, Monazite, Zircon, Rutile, [Leucoxene], Garnet and Sillimanite. (Beach Sand Minerals)
(xi) Sulphides of copper and iron.
(xii) Coal, Fireclay and Shale.
(xiii) Magnetite and Apatite.
(xiv) Magnesite and Chromite.
(xv) Talc, Soapstone and Steatite and Dolomite.
(xvi)Celesite, Phosphatic Nodules, Clay and Gypsum. Beach Sand Minerals
MINERAL COMPOSITION PROPERTIES
Ilmenite Magnetic & Conducting (50-60% TiO2) Leucoxene Oxide of titanium & iron. Medium Magnetic & (75-82% TiO2) Sp. Gr.:4.2-4.6 Conducting Rutile Non Magnetic & (> 92% TiO2) Conducting Zircon Zirconium Sillicate Non Magnetic & Non (64-66% ZrO2) Sp. Gr.:4.7 Conducting Phosphate of Rare earths & Monazite Low Magnetic & Non Thorium (58% RE O 9% ThO & 27% P O ) Conducting 2 3, 2 2 5 Sp. Gr.:5.2
Sillimanite Aluminium Silicate Non Magnetic & Non (56-58% Al2O3) Sp. Gr.:3.2 Conducting
Garnet Iron Aluminium Silicate Medium Magnetic & Non (43% FeO, 21% Al2O3, 36% SiO2) Sp. Gr.:4.1 Conducting Indian Reserves of Beach Sand Minerals (Million Tons)
MINERALS RESERVES Ilmenite 593 Sillimanite 226 Garnet 168 Zircon 34 Rutile 31 Monazite 12 Total 1065
Source : Atomic Minerals Directorate for Exploration & Research, Hyderabad Oct 2012
19 Mineral Occurrence
20 Three Stage Indian Nuclear Power Programme
21 Beach sand minerals processing
• Indian monazite discovered in 1908
• White titanium pigment production in 1909
st • Zircon as substitute of SnO2 post 1 world war • Atomic Energy Commission formed in 1948
• Export of monazite banned due to its thorium content
• Indian Rare Earths Limited (IREL) registered in 1950
• Monazite processing plant at IREL commissioned in 1952 in Aluva
22 IREL Units
HEAD OFFICE, Mumbai
RARE EARTHS DIV, Kerala
MINERAL DIVISION, Kerala
IRERC, Kerala
MINERAL DIVISION, Tamil Nadu
OSCOM, Odisha
23 Sustainable Environment Friendly Dredge Mining
DREDGING IN PROGRESS
SIMULTANEOUS BACKFILLING ACTIVITY
24 Sustainable Environment Friendly Dredge Mining
Mined out area before Plantation
Mined out area after Plantation Land preparation for plantation
25 Mineral Separation Process
Beach Washing /Dredging
Heavies Upgrading Plant
Mineral Separation Plant High Tension Separator Conducting
Ilmenite, Rutile Garnet, Monazite, Zircon, Sillimanite Magnetic Low Intensity Magnetic Separator Magnetic Separator Magnetic Non- Garnet Monazite, Zircon, Sillimanite Ilmenite magnetic Rutile
Magnetic Non-magnetic Monazite Zircon, Sillimanite Dry/Wet Gravity separator
Zircon Tailing
Sillimanite Froth Flotation
26 Monazite Processing
Monazite Processing
MONAZITE
CONC.H2SO4 CAUSTIC SODA 180oC 160oC
TH. RE SO4 & H3PO4 WATER DISSOLUTION
WATER DISSOLUTION TRISODIUM PHOSPHATE
SUCCESSIVE RE.TH.OXIDE CAKE PRECIPITATION CONC.HCL LEACHING RE COMPOUND
RE CHLORIDE TH.PHOSPHATE
TH.CONCENTRATE DIL.ACIDIC SOLUTION OF PO4, SO4, RE & TH.
Entire phosphate values are recovered in caustic soda process
27 Monazite Processing
Water Caustic lye Ground monazite 5
4 1. Alkali digestor 4 2. Leaching tanks 1 3. Drum filter Steam 4. Crystalliser 5. Barometric condenser 6. Centrifuge T.S.P. 7. Dryer Water slurry 3 8. T.S.P. storage
2 6
Filtrate for Drying recycle 7 Cake for T.S.P. & RE recovery NaOH soln. 8
Mother liquor Rare earths & thorium for NaOH hydroxide slurry recovery TSP
28 Production of RE Chloride & Thorium Hydroxide
.
RECl3 soln. 2 Pb-Ba-cake 4 for disposal Thorium& rare earths hydroxide cake Na2S Na SO Hydrochloric 2 4 5 acid BaCl2 Thorium For R.E. fractionation 6 pH-3 hydroxide
o 3 by solvent extraction, 70 C 1 cake R.E.F. production,R.EO. Production& Hydrated cerium oxide production.
7 1. Leaching tank Slurry Slurry 2. Filter 3. Deactivation tank ReCl3 Flake 4. Drum filter 5. Evaporator 6. Flaker 7. Jumbo bag
29 Monazite processing by sulphuric acid
30 High Pure RE Production
Composite RE chloride (La, Ce, Pr, Nd, Sm, Gd, Y chl.)
HEAVIES LEAN RECl HEAVY RARE EARTH HIGH PURITY La, Ce, Nd & Pr ELIMINATION SEPARATION
Ce Chloride Nd Chloride Y chloride Sm-Gd chloride La chloride Pr Chloride Yttrium Sm-Gd purification purification Ppt. , Filt. & Ppt. , Filt. & Ppt. , Filt. & Ppt. , Filt. & Calc Calc Calc Calc
Ppt. , Filt. & Ppt. , Filt. & Ppt. , Filt. & Calc Calc Calc La oxide Ce Pr oxide Nd oxide (99.99%) Carbonate (99%) (99%) Y oxide Sm oxide Gd oxide (99.99%) (99.99%) (99.99%) (99.99%) Ppt. , Filt. & Calc Dy oxide (99.99%) Ppt. , Filt. & Calc Tb oxide (99.99%) Ppt. , Filt. & Calc Eu oxide (99.99%) Salient features of caustic & sulphuric acid process
Sulphuric acid Route Caustic soda Route Grinding of monazite not required Monazite has to be ground to finer than 300 mesh Uranium is recovered from single stream Uranium has to be separated from 3-4 streams. Uranium recovery is 95% Uranium recovery is 75% only Energy consumption is less since Energy consumption is higher than monazite grinding is not required sulphuric acid route Processing cost is lower than caustic Processing cost is higher since the main soda route since the main reagent used reagent used is caustic soda viz sulphuric is cheaper Quantity Volume of radioactive waste Quantity and volume of radioactive generated is less waste generated is more than by sulphuric acid route Helium recovery is expected to be better Part of the helium is lost during grinding of monazite.
32 Monazite processing at Aluva
Patented Process by Societe Products Chemiques Des Terres Rares, France
Caustic soda fusion to break Phosphate bond of Monazite at 150o C
The phosphate content of the ore is recovered as Tri-Sodium Phosphate do deca hydrate crystals.
Rare Earths are leached from the fused mass by Hydrochloric acid dissolution.
Solvent extraction and ion exchange to separate Rare Earths in their purer forms. A large scale facility was established to produce 100 tons per annum of 99% pure neodymium oxide by using a mono acidic phosphonic ester as a solvent.
Product mix comprises of chloride, flouride, hydroxide and carbonate of RE
Mixed RE products are exported to Japan and USA for catalytic and carbon arc applications
33 Strategic Importance of RE in India
Indian RE reserves are richer in lighter fractions and are deficient in heavier ones.
Indian reserves of Titanium and Zirconium are complimentary to use of RE
Applications of Rare Earths are significant in view of their usage in conventional & non-conventional sources of energy utilisation in particular with reference to the 3 stage nuclear energy programme of the country.
Every 3 to 5 years a new use for rare earth material is being discovered and the pattern of their usage is significantly changed in every decade
Very close association of industry with research and development activities are essential for developing effective future marketing strategies for these products.
34 Strategic Importance of RE in India
Most of the rare earth products finding high tech use are related to strategic areas viz. Defence, fibre optic communications, space and nuclear energy, etc.
The country should be self sufficient in using assimilating and developing the high technology rare earth applications.
Dependence on a single country as a supply source for these rare earths materials may not be desirable.
Pricing of rare earth products from the view point of developing its market is dependent on its substitutability in various applications and sensitiveness to price of ultimate product/service.
35 Strategic Importance of Zircon & Titanium
Zirconium sponge is used for manufacture of nuclear grade zirconium alloy which is used for making nuclear fuel bundles.
Production of zirconium sponge involves consumption of chlorine and magnesium metals which happen to also be vital process inputs for producing titanium sponge. Production of titanium sponge can be tied up with the production of both nuclear grade zirconium sponge as well as zirconium sponge for other non-nuclear applications with a view to achieving enhanced production economy by way of establishing higher volume of production of these materials and by exploiting synergies of use of major common input chemicals such as chlorine, petroleum coke and magnesium metal in these processes.
36 SX-its history & role in industry
• SX developed in mid 20th century with nuclear energy
• Simplified processing by reduction of process steps
• Higher productivity and plant through put
• Increased purity and recovery
• Use of simple process equipment and conventional design.
• Negligible solvent consumption and improved economy
• Use of common organic chemicals/re-agent as solvent
37 SX- the agents
• Solvents- acidic, acidic esters & chelating agent, basic, alcohol, ketones, alkyl/aryl sulphoxide • Diluents- aliphatic, aromatic • Modifiers/synergistic agents – aliphatic/aromatic alcohol, acidic ester • Organic compound of common use can be utilised
Common use solvents:
Ester of phosphoric acid- tributyl phosphate
Alcohol- butanol, isodecanol
Dialkyl phosphoric acid – 2 diethyl hexyl phosphoric acid
Tertiary alkyl primary amene- Primene JMT
38 SX-Issues & Challenges
• Solvents are inflammable and bio-toxic
• Limited ion/solute carrying capacity of solvent
• De-gradation of solvents and its cost
• Extractor having low solvent hold up and high efficiency
• Difficulties in obtaining proprietary solvents in India
• Feed pretreatment to remove suspended solids, harmful ions
• Stringent process control – O/A ratio, acidity, solute conc.
39 Economic & Population Growth (growing need for energy)
SUSTAINABLE DEVELOPMENT
Depleting resources Technology Requirement -Energy - Storage of thorium as thorium phosphate -Rare Earths/ Metals - Process for continuous titanium metal production
40 Expected Cooperation
Indian Rare Earths Limited (IREL) under the Department of Atomic Energy is involved in processing of monazite for production of various RE compounds since 1952.
The RE available in monazite comprises basically of the lighter fractions. Technology for producing rare earths from monazite and that for producing separated high pure rare earths of 4N purity is available with IREL.
IREL is interested in sourcing heavier fractions of RE and is willing to associate with foreign companies in the above quest.
IREL is on the lookout for technologies to manufacture RE metals & RE permanent magnets such as samarium cobalt and neodymium iron boron magnet on commercial scale.
41 THANK YOU
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