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Elements Chemical Rare Earth Groups symbol Yttrium Y Europium Eu Gadolinium Gd Terbium Tb HYDROMETALLURGY OF Dysprosium Dy XENOTIME AND MONAZITE Holmium Ho Erbium Er PROCESSING Thulium Tm Ytterbium Yb Elements Chemical DR MEOR YUSOFF B. MEOR SULAIMAN, symbol Lutetium Lu MATERIALS TECHNOLOGY GROUP Lanthanum La Heavy Rare Cerium Ce Light Rare Earth Group Praseodymium Pr Earth Group Neodymium Nd Samarium Sm
Energy densities of different magnetic materials
RE & Malaysian Car Industry Upward & Downward Trend of Light RE Price
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REE: Demand and Supply
Rare Earth Price (US$/kg) Demand (2016) Supply (2016) Element La 14 35-40,000 tons 75-80,000 tons Ce 15 60-70,000 tons 75-85,000 tons Nd 82 20-30,000 tons 30-35,000 tons Eu 1,800 625-725 tons 450-550 tons Tb 1,400 450-550 tons 300-400 tons Dy 7,500 1500-1800 tons 1300-1600 tons Y 60 12-14 tons 9-11 tons
The Rare Earth Chain Rare earth chain : From Mining to Magnet
Mining Mineral RE recovery process concentrate from mineral Can be generally categorized into the upstream,
midstream and down stream
Upstream includes mining and beneficiation steps Upstream Midstream includes cracking and separation and purification of individual RE element Midstream Downstream includes metal making and production of end-product such as magnet, catalyst, etc RE are turned into Separation and Products metal magnet purification of RE Mixed light and heavy RE
Downstream 10
Rare Earth Magnet: Value-added from Mineral to High Purity Individual Element Tin Mining in Malaysia
Tin mining has been a major activity of Malaysia since 1848
Rare earth products Value-added Up till 1980, Malaysia contributed 30.7 % of the world’s (from mineral) produce of tin Nowadays, Malaysia only produces less than 1.5% of total Monazite 1 world production Mixed light rare earth 5 One of the reason: Total collapse of the world tin industry in carbonate 1985 when the price of tin fell by more than 50% Neodymium (99.9%) 16 With the drop in tin production and the cost of world’s tin, Dysprosium (99.9%) 1500 attention shifted toward processing of amang (a tin by product) for valuable minerals. Amang is a local slang word used by the tin mining community to describe tin tailing consisting of a mixture of tin ore, sand and minerals initially discarded by tin miners
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RE Resource in Malaysia MONAZITE AND XENOTIME DISTRIBUTION
AMANG Mineralogical analysis of an amang sample from Kinta Valley
Minerals Percentage Amang or by- product of tin minerals reprocessing, Ilmenite 59.6 has been found to contain Hydroilmenite 7.9 valuable heavy minerals Quartz 12.2
Topaz 7.7
The minerals which are of Tourmaline 4.6 economic significance in Siderite 2.5 producing thorium are monazite Rutile 2.4 Garnet 1.3 (Ce,La,Nd,Th)PO4 and xenotime (YPO4) Pyrite 0.7 Xenotime 0.5
Zircon 0.4
Monazite 0.2
Cassiterite trace
Production of Monazite and Xenotime in Malaysia Physical Properties of Monazite and Xenotime
Term of Monazite Xenotime reference Pale yellow to brownish Colour Yellow to red brown green
Specific gravity 4.9 – 5.5 4.45 – 4.59
Hardness (Mohs scale) 5 4.5
Crystal structure Monoclinic Tetragonal
Magnetic susceptibility Moderate Moderate
Electrical conductivity Poor Poor
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Beneficiation of Monazite and Xenotime MINERAL ANALYSIS Spiral Shaking table
RE elements RE MINERALS Concentrate/ Concentrate/ middling middling Monazite Xenotime Washing, Dewatering, Cerium 21.20 3.13 drying Tailing Tailing Lanthanum 10.00 1.24 Amang stockpile Discard Discard (mainly quartz) Neodymium 9.02 1.60 (mainly quartz) Dry concentrate Erbium trace 3.93 Magnetic Electrostatic Magnetic Gadolinium trace 1.77 separator separator separator
Xenotime Dysprosium 2.13 4.42 Non-conductor Magnetic Terbium trace 0.40 Monazite • ilmenite • monazite Non-magnetic Yttrium 3.48 43.04 Non-magnetic Conductor • xenotime • tourmaline • garnet • cassiterite Thorium 9.00 1.290 • cassiterite • ilmenite • zircon • zircon • tourmaline • quartz • garnet Uranium 0.35 1.452 • rutile •pyrite
RARE EARTH MINERAL CRACKING PROCESS MALAYSIAN RARE EARTH CORPORATION MONAZITE (MAREC)
CONC.H2SO4 CAUSTIC SODA 180oC 160oC Plant located at same place as ARE in Bukit Merah Industrial Estate, Lahat, TH. RE SO4 & H3PO4 WATER DISSOLUTION Perak. Malaysian company with WATER DISSOLUTION TRISODIUM PHOSPHATE BEH Minerals as major
RE.TH.OXIDE CAKE shareholder SUCCESSIVE PRECIPITATION Starts operation in late 70s Plant has capacity of
RE COMPOUND CONC.HCL LEACHING producing 200 tons of Yttria Stop operation in 1985 to consolidate on ARE TH.PHOSPHATE RE CHLORIDE operation
DIL.ACIDIC SOLUTION OF TH.CONCENTRATE PO4, SO4, RE & TH. 21 29 November 2016 Mining and mineral processing by Meor Yusoff 22
XENOTIM MAREC PROCESS: SULPHURIC ACID ASIAN RARE EARTH (ARE) E CRACKING 24 ROASTIN G 23 Nov 1979 - ARE was set up to recover ACID mixed rare earth DIGESTION compounds from local monazite These mixed RE are THORIUM/URANIUM Solid/Liquid WASTE separation exported mainly to Japan The plant used the YTTRIUM caustic soda route OXALATE where tricalcium phosphate is produced as a by- YTTRIUM product of the process OXIDE
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MONAZITE ASIAN RARE EARTH PROCESS: CAUSTIC SODA Lynas CRACKING
CAUSTIC SODA DIGESTION Lynas Malaysia Sdn. Bhd. (Lynas), a wholly owned subsidiary of Lynas Corporation Limited (Australia) Solid/Liquid TRISODIUM separation PHOSPHATE Lynas Advanced Materials Plant (LAMP) located in an area of 100 ha in the Gebeng Industrial Estate ACID (GIE), Kuantan, Pahang. DIGESTION The plant will process up to 80,000 tonnes per
THORIUM Solid/Liquid annum (tpa) wet weight basis of lanthanide WASTE separation concentrates (basnaesite) imported from Mount LIGHT RE CARBONATE Weld, Australia Multistage solvent extraction HEAVY RE CARBONATE 25
Lynas Products Lynas Plant: Sulphuric acid process
PRODUCT APPLICATION 1 SEG-HRE carbonate phosphors for colour screens and energy efficient lighting (e.g. compact fluorescent lights) 2 LCPN Carbonate downstream processing plants for separation into individual lanthanide products 3 Lanthanum Chloride, Carbonate or Fluid Cracking Catalysis (used in oil Oxide refining) and to the manufacturers of battery alloy for nickel metal hydride (NiMH) rechargeable batteries
4 Lanthanum-Cerium Carbonate glass polishing powder ( plasma TV and LCD TV)
5 Cerium Chloride, Carbonate or automotive catalysts powders for the automotive industry Oxide 6 Didymium Oxide and Neodymium magnetic alloys, metal production. Oxide
Weak Light RE Price & Lynas RADIOACTIVE WASTE ISSUE
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Radioactivity & Safety ARE: Radioactive Waste Processing of radioactive 32 contaminated minerals in 1985: The government decides to particular the thorium waste relocate the radioactive storage issue have contributed to facility from Papan to Kledang public concerned on the Range, 5Km from the ARE plant radioactivity and safety issues The storage facility is known as of radioactive waste Long-Term Storage Facility Protests were held on the (LTSF) issue of thorium produced 1989: Construction of LTSF from Asian Rare Earth plant completed and all thorium waste in Lahat and the recent Lynas were stored there plant in Gebeng
content Brazil India (Dar et al, ARE (Meor (Palabrica et al, 1972) Yusoff, 1992) 1980) Thorium 44.3% 45 – 55% 32.0 – 33.5% Uranium 1.2% 1.5 – 1.8% 1.1 – 1.4% Rare earths 15.2% 10 – 15% 27.0 – 28.0%
Long Term Disposal of ARE Waste Dilution Method by Lynas
The Lynas WLP residue are contains thorium, uranium and their decay products at concentrations of about 1650 ppm thorium and 30 ppm uranium or 6 Bq/kg. Lynas intends to dilute this waste to about the Malaysian permissible level of 1 Bq/Kg and used this diluted material as aggregate for road construction Beneficiation of the residues will be subjected to AELB Act 1984 and EQ Act 1974. If the thorium and uranium levels can be reduced to natural concentration as in Naturally Occurring Radioactive Materials (NORM) the WLP and NUF residues can be feeders to other industries. Failure to do so, permanent safe and secure repository site must be located to cater for WLP, NUF and FGD.
OTHER ISSUES IN RARE EARTH PROCESS
Low recovery of interested elements Used of unfriendly process (eg. concentrated acids) High chemical safety Too many elements of interest to be recovered and separated Unlike monazite, xenotime needs to be processed in harsher conditions
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MONAZITE VS XENOTIME MINERALOGY
THE PROJECT
NEW ALKALINE FUSION PROCESS FOR RECOVERY OF THORIUM, URANIUM, RARE EARTH AND PHOSPHATE FROM XENOTIME AND MONAZITE (SCIENCE FUND 03-03-01-SF0243 )
Residue after Acid digestion Residue after the digestion can be categorized as coarse and fine
Xenotime Monazite
Residue from 100g xenotime Residue from 100g monazite sample; sample; Course = 17g Course = 7g Fine = 3g Fine = 13g
SEM Morphology (Xenotime) SEM-EDS Analysis (Xenotime)
Coarse Fine Coarse Fine
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Coarse vs Fine Residue (Xenotime) Coarse vs Fine Residue (Monazite)
Coarse Fine Coarse Fine
•Coarse – majority of residue •Fine – minor in residue •Mainly made up of silica mineral •xenotime accounted for 30% of the •Relatively no Xenotime detected mineral •>95% recovery for xenotime achieved by the alkaline fusion method
SEM and EDS of phosphate XRD of phosphate
Thorium and Uranium Separation Oxalate & Hydroxide
hydroxide
oxalate
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Oxalate & hydroxide Oxalate: elemental mapping
XRD Oxalate (Monazite)
Thank You
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