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Karthikeyan T

Rare Earth Minerals Mining, Mineral Separation, value addition in Kerala

Rare Earth Minerals Mining, Mineral Separation, and its value addition in Kerala an overview
T Karthikeyan
Kerala Minerals and Metals Limited Sankaramangalam, Chavara 691 583, Kerala, India E-mail: mpdnms@kmml.com Abstract. Kerala beaches have one of the richest mineral sand deposits in the world. The main deposits,
referred to as Chavara Beach sand deposits, exist between the tidal channels of Neendakara in the south and Kayamkulam in the north. Mining rights are distributed equally to M/s. Indian Rare Earths Ltd (IREL) and M/s. Kerala Minerals & Metals Ltd (KMML). Heavy minerals like Ilmenite, Rutile, Leucoxene, Zircon, Sillimanite, and Monazite; and traces of Garnet and Kyanite are available in these mineral sand deposits. These minerals are separated by using their own characteristic physical properties. KMML is the only company in the world having integrated facility, i.e., from mining of the mineral sand to its maximum value addition. Titanium bearing minerals (IL, R, and L) end-user industries are Paints, Pigments, Varnish, Rubber, Plastics, Textiles, Ceramics, Paper, Medicine, etc. Zircon and Sillimanite are used mainly in ceramic, refractory, and foundry industries. Monazite is an atomic mineral largely used for obtaining thorium, thorium compounds, rare earth salts, and phosphoric compounds. In KMML, Ilmenite mineral has added value as synthetic Rutile, Titanium tetra chloride, Titanium dioxide pigment, and Titanium sponge (in collaboration with Indian Space Research Organization [ISRO] and Defence Metallurgical Research Laboratory [DMRL]). Kerala has a huge potential for developing value addition manufacturing facilities based on the above two companies. Value addition facilities like Zircon opacifier plants, welding rod manufacturers, ceramic/refractory, foundry industries, etc. may be developed with some marginal investments. Virgin land mineral deposits are available in the northern part of Karunagappally to Alapuzha. The strong support from the state government and local villagers is required for starting mining activities in these areas.

Introduction This presentation will cover an overview of KMML s business including mineral processing issues, value addition, and suggestions for setting up the value addition facilities in the state. Currently most of the end users are located in the northern/western part of the country. Approximately 10% of rare minerals are value added in the state, and balance quantity is value added in other parts of the country. Main resources of placer deposits in India Ilmenite and Rutile along with other heavy minerals are important constituents of beach sand deposits found along the coastal area from Ratnagiri coast (Maharashtra) in the west to Odisha coast in the east. These minerals are concentrated in five well-defined zones: * Over a stretch of 22 km between Neendakara and Kayamkulam, Kollam district, Kerala (known as Chavara deposit after the main mining center). * Over a stretch of 6 km from the mouth of Valliyar river to Colachal, Manavalakurichi, and slightly farther beyond Kanyakumari district, Tamil Nadu (known as MK deposit). * On Chatrapur coast stretching for 18 km between Rushikulya river mouth and Gopalpur lighthouse with an average width of 1.4 km in Ganjam district, Odisha (known as OSCOM deposit after IREL's Orissa Sands Complex). * Brahmagiri deposit stretches for 30 km from Girala nala to Bhabunia villages with an average width of 1.91 km in Puri district, Odisha.

Shaji E & Pradeepkumar AP (Eds) 2014 Mineral Resources of Kerala Trivandrum: Dept of Geology Univ of Kerala ISBN 978-81-923449-0-4 24

Karthikeyan T

Rare Earth Minerals Mining, Mineral Separation, value addition in Kerala

* Bhavanapadu coast between Nilarevu and Sandipeta with 25 km length and 700 m average width in Srikakulam district, Andhra Pradesh. The Atomic Minerals Directorate (AMD) of the Department of Atomic Energy has been carrying out exploration of these mineral deposits. So far, about 3,579 km coastal tract and 128.92 sq km in the inland areas in Tamil Nadu and West Bengal have been investigated for over six decades by AMD. The Ilmenite resource estimation for the areas explored up to 2006 has been almost completed and the resources are up from 461.37 state/deposit Ilmenite reserve million tonnes to 520.38 million tonnes (including leucoxene), inclusive of indicated, inferred, and speculative categories. Resource estimation for the areas explored from 2006 to 2011 is under progress. The most significant deposits which are readily available and attract the attention of the industry for large-scale operations are as follows: Andhra Pradesh 1 . Amalapuram 15.57 2 . Bhavanapadu Hukumpet 10.18 3 . Kakinada (Phase IVII) 29.62 4 . Kalingapatnam 7.63 5 . Narasapur 2.92 6 . Nizampatnam 19.26 7 . Srikurman 14.18 8 . Visakhapatnam 3.60 Kerala 1 . Chavara 13.00 2 . Chavara Eastern Extension 17.00 3 . Chavara (Phase II) 49.00 Maharashtra Ratnagiri 3.04 Odisha 1 . Brahmagiri 61.10 2 . Chatrapur 26.72 Tamil Nadu 1 . Kudiraimozhi 23.00 2 . Navaladi-Periatalai 24.00 3 . Sattankulam 14.48 Source: Department of Atomic Energy, Mumbai. Resources of Ilmenite and Rutile (In million tonnes) State Total in situ # Ilmenite*: Total 520.38 Andhra Pradesh 171.04 Bihar 0.73 Kerala 117.52 Maharashtra 3.74
Shaji E & Pradeepkumar AP (Eds) 2014 Mineral Resources of Kerala Trivandrum: Dept of Geology Univ of Kerala ISBN 978-81-923449-0-4 25

Karthikeyan T

Rare Earth Minerals Mining, Mineral Separation, value addition in Kerala

Odisha 108.23 Tamil Nadu 117.07 West Bengal 2.05 Rutile: Total 29.11 Andhra Pradesh 10.30 Bihar 0.01 Kerala 7.24 Odisha 6.06 Tamil Nadu 5.31 West Bengal 0.19 Source: Department of Atomic Energy, Mumbai. # Inclusive of indicated, inferred, and speculative categories. * Including leucoxene. The Chavara Deposit. The main deposit stretching to a length of 22.54 km north to south, covers an area of 400 Ha, at an average width of 500 m from the high tide line. This area is located in the Geological Survey of India (GSI) toposheet between Latitude 8 45 to 9 18 and longitude 76 15 to 76 48. The deposit has developed in the form of a bar parallel to the Arabian Sea separating Ashtamudi Lake near Kollam, Vatta Kayal lake near Karunagappally, and Kayamkulam lake at Kayamkulam. The Archaein gneisses which occupy a large part of the state are regarded as the ultimate source of heavy minerals. These mineral sand deposits are obtained from disintegration of rocks; erosion and transportation by the action of various rivers flowing westwards; soaring and enrichment of deposition by the action of waves and winds which are responsible for the formation of this deposit. The potential of the deposits was first noticed by Dr. Schomberg, a German mining engineer. But active mining was started for Ilmenite and other minerals only in the 1930s by four companies, viz., Associated Mineral Company, Travancore Mineral Concerns, F.X. Pereria & Sons, and Hopkins & Williams Ltd. Presently in the place of these four companies two government concerns, M/s. Indian Rare Earths Ltd and M/s. Kerala Minerals & Metals Ltd, are functioning. M/s Kerala Minerals & Metals An overview The company operates the following mineral sand value addition units in Chavara: 1. Mineral Separation Unit (MS Unit) 2. Titanium Dioxide Pigment Unit (TP Unit) 3. Titanium Sponge Unit (TSP Unit) Mineral Separation Unit Mining. At present, KMML is mining the mineral sand from Block III only. Beach washings (mineral sand) are collected from Ponmana and Anchumana beach areas and inland deposits from the Kovilthottam and Ponmana area. The heavy mineral content in the beach washings has come down during the last few years. Hence the company decided to mine the land deposits in order to acquire sufficient Ilmenite for the captive plant. Currently beach deposits contain only around 15% heavy minerals (HM). So the company has installed mini spiral concentrator plants for upgrading the HM content up to 50%. Chavara deposit mineral sand has mineral assemblage in the order of decreasing abundance, Ilmenite, Sillimanite, Zircon, Rutile, Leucoxene, and Monazite; and traces of Garnet and Kyanite. Beach wash collection: From the beach, daily accreditation of the mineral sand is scrapped by using Front End Loaders. Depending on the quality of the sand, it is stocked separately. The collected sand is transported by tippers to the mineral separation plant for further processing.
Shaji E & Pradeepkumar AP (Eds) 2014 Mineral Resources of Kerala Trivandrum: Dept of Geology Univ of Kerala ISBN 978-81-923449-0-4 26

Karthikeyan T

Rare Earth Minerals Mining, Mineral Separation, value addition in Kerala

Land deposits which lie above the water table are mined out by using backhoe excavators. Below the water table, deposits are mined out by using high capacity dredgers and Toyo agitator pumps. The collected sand is subsequently transported to the MS plant for further processing. Mineral Separation Plant. In the mineral separation plant, based on physical properties like specific gravity, particle size, conductivity, magnetic susceptibility, and surface attraction, valuable minerals are separated from gangue minerals/impurities. Physical properties of minerals are as follows
Mineral Bulk Density Monazite (Ce, Y, La) PO4 Zircon ZrO2.SiO2 Ilmenite FeO TiO2 Rutile TiO2 Garnet Fe3Al2(SiO4) Sillimanite Al2O3. SiO2 Quartz (SiO2) 1.40 6 to 6.5 2.60 Non-conducting Non-Magnetic 1.79 6 to 6.5 3.24 Non-conducting Non-magnetic 2.17 6.5 to 7.5 4.10 Non-conducting Magnetic 2.48 6 to 6.5 4.25 Conducting Non-magnetic 2.69 5 to 6 4.54 Conducting Magnetic 2.67 6 to 7.0 4.68 Non-conducting Non-magnetic 3.12 Hardness (Mohs) 5 to 5.5 Specific Gravity 5.22 Electrical Conductivity Non-conducting Magnetic Susceptibility Feebly Magnetic

The valuable minerals are separated from the other gangue minerals by processing through spiral gravity concentrators/wet concentration shaking tables (specific gravity separation), sieves (grain size separation), magnetic separator (magnetic susceptibility), high tension roll/electrostatic plate separators (electrical conductivity), froth floatation cell (surface attraction), and using material handling equipment like slurry pumps, conveyors, compressors, elevators, etc. for the purpose. Mineral Separation Process in MS Plant Feed mineral sand is collected and transported from various sites to the mineral separation plant (MSP) stockyard on a daily basis. Initially, the raw sand is washed in the wet mill; thereafter it is sieved through a 4 mm polyurethane sieve. The underflow material is converted into a slurry form by adding sufficient water to the bin in order to process the mineral sand in the spiral concentrators. Five sets/stages of spiral concentrators are available for upgrading the heavy mineral content of the raw sand from 50% (in normal cases) to 90% HM in the concentrate (output of wet mill). Subsequently, this concentrate (contains 90% HM) is fed to a fluidized bed
Shaji E & Pradeepkumar AP (Eds) 2014 Mineral Resources of Kerala Trivandrum: Dept of Geology Univ of Kerala ISBN 978-81-923449-0-4 27

Karthikeyan T

Rare Earth Minerals Mining, Mineral Separation, value addition in Kerala

dryer (FBD) for removing the moisture content to maintain the sand temperature up to 110 C to enable effective separation of conducting and non-conducting minerals. This hot sand from the FBD is fed to the dry plant. In this dry plant, initially the hot sand is passed through High Tension Roll Separators (HTRS) for separating the conducting and non-conducting mineral fractions. Later the conducting fractions (predominantly IL, R, L) are collected in the conveyor for feeding to magnetic separators. In the magnetic separator, the conducting feed sand is separated into magnetic (contains predominantly IL) fraction and non-magnetic (predominantly left out IL, R, Z, S, Q) fraction. The non-magnetic fraction is then fed to the Rutile Recovery Plant (RRP) for separating the left out Ilmenite and Rutile based on the variable physical characteristics of minerals by using the HTs and magnetic separators. The non-conducting fraction from the dry plant and RRP is taken together to the Zircon/Sillimanite recovery circuit in order to recover the Zircon and Sillimanite minerals from the feed sand. This NC fraction mineral sand (predominantly contains Zircon, Sillimanite, Monazite, Quartz, Kyanite, and Garnet) is passed through magnetic separator, spiral concentrators, up-current classifiers, wet table concentrators, HT separators, flotation cells, etc. in order to remove all the conducting and magnetic fractions from the feed sand to obtain the Zircon/Sillimanite products. Application and Uses of Rare Earth Minerals Ilmenite 1. Titanium Dioxide pigment manufacturing 2. Production of synthetic Rutile or Beneficiated Ilmenite 3. Used in the production of Titanium Tetrachloride (TiCL4 ) 4. Production of Titanium metal Rutile 1. Used in welding electrode manufacturing 2. Manufacture of titanium carbide 3. Used in ceramic industries 4. Manufacture of high capacity condensers Zircon 1. Manufacturing of refractory bricks and molds 2. Used in ceramic industries and glass manufacturing 3. Used in the manufacture of Zircon compounds and Zircon metal Sillimanite 1. Used in refractory industry 2. Used in ceramic industry 3. Manufacture of electrical insulators 4. Manufacture of electrical porcelain Monazite The products obtained from Monazite are Thorium, Thorium compounds, rare earth salts, and phosphoric compounds. Manufacturing Process of TP Unit. Production of Titanium Dioxide in KMML is based on chloride technology. The main process facilities in the production of TiO2 are as follows: 1. Ilmenite beneficiation plant (IBP) 2. Chlorination plant 3. Oxidation plant 4. Pigment finishing unit

Shaji E & Pradeepkumar AP (Eds) 2014 Mineral Resources of Kerala Trivandrum: Dept of Geology Univ of Kerala ISBN 978-81-923449-0-4 28

Karthikeyan T

Rare Earth Minerals Mining, Mineral Separation, value addition in Kerala

Ilmenite Beneficiation Plant. Raw Ilmenite containing 5860% Titanium Dioxide is beneficiated to 90% Titanium Dioxide content. The major operation of the Ilmenite beneficiation plant includes reduction/leaching/calcination. The ferric oxide in the raw Ilmenite is subjected to a high temperature of 8500C9000C in a roaster in the presence of Coke (carbon). This is followed by cooling. The reduced and cooled Ilmenite is then conveyed to rotating digesters where it is leached with HCL acid at 1400C under pressure. This is done to remove iron and other metallic impurities as chlorides. The leached Ilmenite is conveyed for chlorination. Chlorination Plant. BI from the Ilmenite beneficiation plant is chlorinated to produce TiCl 4. Chlorine reacts with TiO2 in the presence of Coke at a temperature of 900 0C in a fluidized bed chlorinator to produce TiCl4. TiCl4 is used for making TiO2, Titanium sponge/metal, Titanium salt/Butyl Titanate, and Titanium oxy chloride Oxidation Plant. TiCl4 is vaporized, preheated, and oxidized with oxygen to produce raw TiO 2 pigment at a temperature of approximately 10000C. The oxidation reaction is highly exothermic. The byproduct chlorine is recycled to the chlorination plant. Raw TiO 2 is then slurried and pumped to the pigment finishing unit. Pigment Finishing Unit. The raw pigment slurry is surface treated with varying proportions of silica/alumina/zirconia based on the end-user applications. Application of TiO2: Paints, Plastics, Paper, Printing ink, Rubber, Textiles, and Ceramic industries. TITANIUM SPONGE PLANT PROCESS DESCRIPTION The technology being adopted for production of titanium sponge is a batch process based on the Kroll process. The Titanium sponge plant is designed to produce 500 tpy of commercially pure Titanium sponge from anhydrous Titanium Tetrachloride (tickle). The main steps involved in the process are as follows: i. Purification of pigment grade tickle to metal grade ii. Magnesio-thermic reduction of tickle iii. High temperature vacuum distillation of magnesium and magnesium chloride iv. Handling, grading, and evaluation of Titanium sponge Application of Titanium Sponge: Aerospace, marine, jewels, medical, Titanium metal manufacturing. Conclusion By using the placer deposits in judicious way, a large number of downstream industries may be developed for providing employment to the locals as well as for contributing to the states economic growth. Acknowledgment The author sincerely thanks Shri. P .M.V . Siromony IAS, Managing Director, Shri. Georgekutty Thomas, DGM (MS), Shri. K. Raghavan, AGM (Operations) of M/s. Kerala Minerals & Metals Limited, Chavara, Kollam, Kerala, and Shri. Cheriyan Varghese, Retd. CGM, IREL for extending their necessary support and guidance for this presentation. The suggestions and opinions expressed in this paper are those of the author only and not of his employer.

Shaji E & Pradeepkumar AP (Eds) 2014 Mineral Resources of Kerala Trivandrum: Dept of Geology Univ of Kerala ISBN 978-81-923449-0-4 29