Latest Scenario in Rare Earth and Atomic Minerals in India...1 Latest Scenario in Rare Earth and...
Transcript of Latest Scenario in Rare Earth and Atomic Minerals in India...1 Latest Scenario in Rare Earth and...
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Latest Scenario in Rare Earth
and Atomic Minerals in India
Dr. R. N. PatraChairman & Managing Director
Indian Rare Earths LimitedMumbai
022 24225778+91 [email protected]
Website: www.irel.gov.in
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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
Major Minerals of RE of Commercial importance
MineralsChemical formula
Countries of origin Remark
Carbonate
Bastnaesite (Ce,La) FCO3USA, China &
Australia
Processing relatively simpler thanMonazite. It has larger content ofEuropium compared to Monazite. InChina it is associated with iron oremining.
Phosphate
Monazite (Ce,La,Th & U) PO4
Australia, India, Malaysia, Brazil,
Thailand & Korea
RE content more or less uniform around60% and minerals available in placerbeach sand resources. The ore containsTh & Uranium which are radioactive
Xenotime YPO4Malaysia, India,
ChinaYttrium major constituent. In Malaysiaproduction is associated with Tin mining
Apatite (CaRE)5[(PSi)O4]3(O,F) CIS, South Africa Occurs in Copper, Tin, Phosphate mining
Ion exchange clay
Weathered apatite & xenotime ore
concentrated in the soil in ionic form
China
Unique deposits found only in southernChina. Though lowest in rare earthcontents easiest to concentrate from theore. Rich source of Y, Eu, Tb & Dy
Minerals Chemical formula
Main Countries of
origin Remark
Oxides
Loparite(Ce,La,Ca,Na)
(TiNb)2 O6CIS Contents above 40% Titania
Euxenite(Y,Ce, Ca,U,Th) (Nb,Ta,Ti)2O6
USASource of Scandium &Yttrium. Recovered as byproduct from Bastnaesite
Sillicate
Gadolinite Be2FeY2Si2O10 USASource of Yttrium.Recovered as by productfrom Bastnaesite
In addition rare earths are also produced as a by product of uranium recovery from its ores in Canada.
Major Minerals of RE of Commercial importance
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
USA
ChinaRussia
Malaysia
South Africa
Canada
Australia
Vietnam
Greenland
India
Brazil
Malawi
Major Mines in operation
APATITENangang, Guangdong, China;Nolans Bore, Australia;Hoidas Lake, Canada.
BASTNAESITEBaiyun Obo & Sichuan, China;Mt Pass, USA;Dong Pao, Vietnam;Dubbo Trachyte, Australia.
EUDIALYTEZeus, Canada;Steenstrupine, Greenland.
FERGUSONITENechalacho, Canada.
XENOTIMEPtinga, Brazil;Lahat Perak, Malaysia;Guandong, China
LOPARITELovozersky, Russia
MONAZITEIndia;Guangdong, China; Mount Weld, Australia;Kangankunde, MalawiZandkopsdrift, SASteenkampskaal, SA.
RE - World Production & Reserves
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S.no Company Country Proposed REO Capacity
1 Lynas Corp Malaysia 22,0002 Molycorp Minerals USA 20,0003 Indian Rare Earths Limited India 5,0004 Great Western Minerals South Africa 2,5005 Alkane Resources Australia 2,6006 Vietnamese Gov/Toyata Tsusho/Sojitz Vietnam 3000 – 5,000
7 Arafura Resources Australia 20,0008 Avalon Rare Metals Canada 5,0009 Kazatomprom/Sumitomo Kazakhstan 15,000
10 Stans Energy Kyrgyzstan 2,00011 Minerals and Energy Greenland 43,70012 Rare Element Resources USA -
13 Resources Canada -14 Quest Rare Metals Canada -15 Ucore Uranium USA -16 US Rare Earths USA -17 Matamec Explorations Canada18 Etruscan Resources Namibia -19 Montero Mining Tanzania -20 Tasman Metals Sweden & Finland21 Neo Material Technologies/ Mitsubishi Brazil -
Total 1,38,800 – 1,42,800
Select RE projects outside China
Indian Context &
Role ofIndian Rare Earths Limited
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 composition
Monazite is rich in LRE and lacks HRE
Indian source of RE
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• 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%.
Properties of Monazite
Gazette notification S.O. 61 (E) dated 20.01.2006 under the Atomic Energy Act, 1962 stipulatesthe 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
Prescribed Substances
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(50-60% TiO2)
Oxide of titanium & iron. Sp. Gr.:4.2-4.6
Magnetic & Conducting
Leucoxene (75-82% TiO2)
Medium Magnetic & Conducting
Rutile(> 92% TiO2)
Non Magnetic & Conducting
Zircon(64-66% ZrO2)
Zirconium SillicateSp. Gr.:4.7
Non Magnetic & Non Conducting
Monazite(58% RE2O3, 9% ThO2 & 27% P2O5)
Phosphate of Rare earths & Thorium
Sp. Gr.:5.2
Low Magnetic & Non Conducting
Sillimanite (56-58% Al2O3)
Aluminium SilicateSp. Gr.:3.2
Non Magnetic & Non Conducting
Garnet (43% FeO, 21% Al2O3, 36% SiO2)
Iron Aluminium SilicateSp. Gr.:4.1
Medium Magnetic & Non Conducting
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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
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Mineral Occurrence
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Three Stage Indian Nuclear Power Programme
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• Indian monazite discovered in 1908
• White titanium pigment production in 1909
• Zircon as substitute of SnO2 post 1st 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
Beach sand minerals processing
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HEAD OFFICE, Mumbai
RARE EARTHS DIV, Kerala
MINERAL DIVISION, Kerala
IRERC, Kerala
MINERAL DIVISION, Tamil Nadu
OSCOM, Odisha
IREL Units
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DREDGING IN PROGRESS
SIMULTANEOUS BACKFILLING ACTIVITY
Sustainable Environment Friendly Dredge Mining
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Mined out area before Plantation
Mined out area after PlantationLand preparation for plantation
Sustainable Environment Friendly Dredge Mining
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Beach Washing /Dredging
Mineral Separation Plant
Heavies Upgrading Plant
Ilmenite, Rutile Garnet, Monazite, Zircon, Sillimanite
Ilmenite Rutile
Garnet Monazite, Zircon, Sillimanite
Monazite Zircon, Sillimanite
Tailing
Froth FlotationSillimanite
Zircon
High Tension Separator Conducting
Low Intensity Magnetic Separator Magnetic Separator Magnetic
Non-magnetic
Magnetic
Magnetic Non-magnetic
Dry/Wet Gravity separator
Mineral Separation Process
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Monazite Processing
Entire phosphate values are recovered in caustic soda process
Monazite Processing
MONAZITE
CONC.H2SO4180oC
CAUSTIC SODA160oC
WATER DISSOLUTION
TRISODIUM PHOSPHATE
RE.TH.OXIDE CAKE
CONC.HCL LEACHING
RE CHLORIDE
TH.CONCENTRATE
TH. RE SO4 & H3PO4
WATER DISSOLUTION
SUCCESSIVE PRECIPITATION
RE COMPOUND
TH.PHOSPHATE
DIL.ACIDIC SOLUTION OFPO4, SO4, RE & TH.
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Steam
T.S.P.
slurry
4
T.S.P. &
NaOH soln.
Drying
1. Alkali digestor
2. Leaching tanks
3. Drum filter
4. Crystalliser
5. Barometric condenser
6. Centrifuge
7. Dryer
8. T.S.P. storage
Cake for
RE recovery
Rare earths & thorium
hydroxide slurry
Mother liquor
for NaOH
recoveryTSP
Ground monazite Caustic lye
Water
1
2
Filtrate for
recycle
3
6
8
7
Water
5
4
Monazite Processing
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.
Thorium& rare earths
hydroxide cake
Hydrochloric
acid
Na2S
Na2SO4
BaCl2
Thorium
hydroxide
cake
Pb-Ba-cake
for disposal
RECl3 soln.
Slurry
pH-3
70oC
For R.E. fractionation
by solvent extraction,
R.E.F. production,R.EO.
Production& Hydrated
cerium oxide production.
Slurry
1
2
3
4
5
6
7
1. Leaching tank
2. Filter
3. Deactivation tank
4. Drum filter
5. Evaporator
6. Flaker
7. Jumbo bag
ReCl3 Flake
Production of RE Chloride & Thorium Hydroxide
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Monazite processing by sulphuric acid
HEAVY RARE EARTH ELIMINATION
Composite RE chloride
(La, Ce, Pr, Nd, Sm, Gd, Y chl.)
HIGH PURITY La, Ce, Nd & Pr SEPARATION
HEAVIES
LEAN RECl
Sm-Gd purification
Yttriumpurification
Ce Chloride Nd ChlorideSm-Gd
chlorideY chloride
Pr ChlorideLa chloride
Y oxide(99.99%)
High Pure RE Production
Sm oxide(99.99%)
Gd oxide(99.99%)
La oxide(99.99%)
Ppt. , Filt. & Calc
Ce Carbonate (99.99%)
Pr oxide(99%)
Nd oxide(99%)
Ppt. , Filt. & Calc
Ppt. , Filt. & Calc
Ppt. , Filt. & Calc
Ppt. , Filt. & Calc
Ppt. , Filt. & Calc
Ppt. , Filt. & Calc
Ppt. , Filt. & Calc Dy oxide (99.99%)
Ppt. , Filt. & Calc
Ppt. , Filt. & Calc
Tb oxide (99.99%)
Eu oxide (99.99%)
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Sulphuric acid Route Caustic soda Route
Grinding of monazite not required Monazite has to be ground to finer than300 mesh
Uranium is recovered from single stream Uranium has to be separated from 3-4streams.
Uranium recovery is 95% Uranium recovery is 75% only
Energy consumption is less sincemonazite grinding is not required
Energy consumption is higher thansulphuric acid route
Processing cost is lower than causticsoda route since the main reagent usedviz sulphuric is cheaper
Processing cost is higher since the mainreagent used is caustic soda
Quantity Volume of radioactive wastegenerated is less
Quantity and volume of radioactivewaste generated is more than bysulphuric acid route
Helium recovery is expected to be better Part of the helium is lost during grindingof monazite.
Salient features of caustic & sulphuric acid process
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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 decahydrate 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% pureneodymium 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 arcapplications
Monazite processing at Aluva
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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 3stage nuclear energy programme of the country.
Every 3 to 5 years a new use for rare earth material is being discovered and thepattern of their usage is significantly changed in every decade
Very close association of industry with research and development activities areessential for developing effective future marketing strategies for these products.
Strategic Importance of RE in India
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Most of the rare earth products finding high tech use are related to strategic areasviz. Defence, fibre optic communications, space and nuclear energy, etc.
The country should be self sufficient in using assimilating and developing the hightechnology rare earth applications.
Dependence on a single country as a supply source for these rare earths materialsmay not be desirable.
Pricing of rare earth products from the view point of developing its market isdependent on its substitutability in various applications and sensitiveness to priceof ultimate product/service.
Strategic Importance of RE in India
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Zirconium sponge is used for manufacture of nuclear gradezirconium alloy which is used for making nuclear fuelbundles.
Production of zirconium sponge involves consumption ofchlorine and magnesium metals which happen to also be vitalprocess inputs for producing titanium sponge. Production oftitanium sponge can be tied up with the production of bothnuclear grade zirconium sponge as well as zirconium spongefor other non-nuclear applications with a view to achievingenhanced production economy by way of establishing highervolume of production of these materials and by exploitingsynergies of use of major common input chemicals such aschlorine, petroleum coke and magnesium metal in theseprocesses.
Strategic Importance of Zircon & Titanium
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• 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
SX-its history & role in industry
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• 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
SX- the agents
Ester of phosphoric acid- tributyl phosphate
Alcohol- butanol, isodecanol
Dialkyl phosphoric acid – 2 diethyl hexyl phosphoric acid
Tertiary alkyl primary amene- Primene JMT
Common use solvents:
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• 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.
SX-Issues & Challenges
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Economic & Population Growth (growing need for energy)
Depleting resources-Energy-Rare Earths/ Metals
Technology Requirement- Storage of thorium as thorium phosphate
- Process for continuous titanium metal production
SUSTAINABLEDEVELOPMENT
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Indian Rare Earths Limited (IREL) under the Department of Atomic Energy isinvolved in processing of monazite for production of various RE compounds since1952.
The RE available in monazite comprises basically of the lighter fractions. Technologyfor producing rare earths from monazite and that for producing separated high purerare earths of 4N purity is available with IREL.
IREL is interested in sourcing heavier fractions of RE and is willing to associate withforeign companies in the above quest.
IREL is on the lookout for technologies to manufacture RE metals & RE permanentmagnets such as samarium cobalt and neodymium iron boron magnet oncommercial scale.
Expected Cooperation
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THANK YOU