Narayanan P et al.

Rare earthsresources, processing, and uses

Rare earthsresources, processing, and uses

P Narayanan, M Venkata Reddy and S Surya Kumar
Indian Rare Earths Ltd., Rare Earths division Udyogamandal, Kerala 683501, India E-mail: marketing-red@irel.gov.in Abstract. Rare earth elements (REEs) known as lanthanides contain a group of 17 elements including
scandium and yttrium. These are moderately abundant elements in the earths crust that occur in a large number of minerals. Rare earth minerals are found in hard rock and placer deposits located throughout the world, with unusually large deposits occurring in a few countries. Even though there are a large number of rare earth minerals, much of the actual rare earth supply comes from only a handful of sources. Nearly 200 minerals containing >0.01% rare earths occur in nature. As a rule, any rare earth mineral usually contains all the rare earth elements, some of them enriched and certain others in very low concentrations. Although the minerals are numerous, about 95% of all rare earth resources occur as bastnasite, monazite, and xenotime. Among these, bastnasite is predominant, followed by monazite, and then xenotime.

Introduction

The minerals of rare earths, generally in hard rock deposits or in placer sands, occur in a variety of geologic environments. The hard rock deposits are of primary origin and the placer deposits secondary. Bastnasite is found only in hard rock deposits, whereas monazite and xenotime occur in both hard rock and placer deposits and they are fairly well distributed throughout the world. World reserves of rare earths have been estimated at 93.4 million metric tons of which 93% occur in hard rock (primary) deposits and 7% occur in placer (secondary) deposits. These resources occur 20% in monazite and 80% in bastnasite. Geographically, 52% of the worlds REE resources are located in China, 22% in Namibia, 15% in United States, 5% in Australia, 3% in India, and the remainder in several other countries. Monazite was the principal rare earth source from the beginning of the rare earth industry 100 years ago until 1965. Thereafter, production of bastnasite exceeded monazite production.

Indian scenario

India is blessed with rich deposits of REE minerals, mainly monazite, concentrated in southern, south western and eastern coastal regions. In the southern coast of Kerala, it was accidentally discovered in 1908 by a German chemist Herr Schomberg who identified the presence of monazite sand from the coir products imported from Kerala. Other important REE minerals like bastnasite and xenotime are also present but in very insignificant concentrations. The Atomic Minerals Division has established the presence of xenotime concentrate in riverine heavy mineral placer deposits of Jharkhand and Chhattisgarh. The rare earth placer deposits in India are found in the southwestern coast of the peninsula at Manavalakuruchi in Tamilnadu, Chavara in Kerala, and on the eastern coast of Gopalpur in Orissa. The Chavara beach deposits extend over a stretch of 22 km from Kayamkulam in the north to Neeendakara in the south. The Manavalakuruchi beach deposits extend up to about 2 km in length from the mouth of the river Valliar touching Kadiapatanam village to the village Chinnavallai. Extensive dune sand deposits occur along the south Odisha coast over a stretch of about 150 km. Of the several deposits located, the one close to Chatrapur is an extensive single deposit with the highest grade heavy minerals. It runs over a coastal length of nearly 18 km, covering a total area of over 26 square km between Gopalpur in the south and Rushkiya river in the north. Rare earth reserves in India are shown in Fig. 1.

Shaji E & Pradeepkumar AP (Eds) 2014 Mineral Resources of Kerala Trivandrum: Dept of Geology Univ of Kerala ISBN 978-81-923449-0-4 30

Narayanan P et al.

Rare earthsresources, processing, and uses

Processing methods

The mined rare earth ore is put through physical and chemical processing, which converts it to a compound which is either an end product by itself or an intermediate for the production of the metal or alloy or a compound subsequently. Much of the actual extraction of rare earths is principally from the minerals monazite and bastnasite. All the rare earths generally occur together in the minerals due to their chemical similarity, and this makes the separation of rare earths from one another a daunting task.
Monazite Resources in India (Million Tonnes)

1.22

3.72 1.9 AP TN Odisha Kerala W.Bengal

2.41 2.46

Fig 1. Rare earth reserves in India

Physical beneficiation. In placer deposits, monazite occurs as a minor constituent along with sillimanite, garnet, magnetite, while the major minerals are ilmenite, rutile, zircon, and quartz. The minerals can be separated from one another by a sequence of processes that exploit small differences in the specific gravity or the slight differences in magnetic stability. Among the beach sand minerals, specific gravity of monazite is the highest (4.65.7 g/cc). Ilmenite, garnet, xenotime, and monazite occur in decreasing order of magnetisability. In electrostatic separation, ilmenite and rutile behave as conducting minerals and others non-conducting. Xenotime is more strongly magnetic than monazite. The bastnasite rock is crushed and is ground in a ball mill where the particle size is reduced to 100% so that it passes through a 150-mesh. The ground ore is beneficiated by a process known as hot froth flotation. Chemical treatment. The recovery of mixed rare earths and removal of thorium from monazite are accomplished by a variety of methods. The sulphuric acid attack route is practised for unground monazite, whereas ground monazite is required for the sodium hydroxide treatment. In India, at the Indian Rare Earths Ltd. plant at Alwaye in Kerala, chemical breakdown of monazite is done by an alkali attack. In the present process for monazite treatment using caustic soda, the phosphate content of the monazite ore is recovered as a marketable by-product, trisodium phosphate, and this has been a major attraction for the commercial use of this process. Finely ground monazite is attacked with a 50%60% sodium hydroxide solution at 140 0C
Shaji E & Pradeepkumar AP (Eds) 2014 Mineral Resources of Kerala Trivandrum: Dept of Geology Univ of Kerala ISBN 978-81-923449-0-4 31

Narayanan P et al.

Rare earthsresources, processing, and uses

1500C, and the mixed rare earth thorium hydroxide cake obtained is processed for rare earths, thorium and uranium recovery by a variety of methods.

Separation techniques

Small differences in basicity form the basis of separation procedures by fractional crystallization, fractional precipitation, ion exchange, and solvent extraction. These arise from decrease in ionic radius from lanthanum to lutetium and influence solubility of the salts, hydrolysis of ions, and formation of complex species. Ion Exchange. An ion exchange resin or ion exchanger can be considered as an ionic salt in which an ion is attached to an insoluble organic matrix. In an anion exchange resin or anion exchanger, the charge on the ion is negative. The charge on the ion is positive in a cation exchanger. When the ion exchange resin comes into contact with a salt solution, the mobile ion in the resin matrix may be displaced. Generally (i) an ion of higher charge displaces an ion of lower charge, (ii) between similarly charged ions, that with a larger radius displaces the one with the smaller radius, and (iii) the displacement occurs according to the law of mass action. The selectivity in an ion exchange separation is quantified by the distribution coefficient and separation factor among rare earths.

Fig 2. Uses of rare earths

Solvent extraction. The separation of rare earths by solvent extraction depends upon the preferential distribution of individual rare earths between two immiscible liquid phases that are in contact with each other. One of the liquid phases is an aqueous solution containing rare earths and the other non-aqueous phase is the organic phase. One of the many advantages in using solvent extraction as the process for rare earth separation is that the rare earth loading in the solvent can be very high (-180 g REO/L). Therefore aqueous solutions with concentrations of 100140 g REO/L can be used. It makes the equipment required for the process very compact. Even though considerable published information is available on the extraction behavior of these solvents, the details of solvent extraction processes actually practiced in the industry are kept well-guarded. Rare earth producers all over the world including Indian Rare Earths Ltd. follow almost identical methods for separation of rare earths using solvent extraction
Shaji E & Pradeepkumar AP (Eds) 2014 Mineral Resources of Kerala Trivandrum: Dept of Geology Univ of Kerala ISBN 978-81-923449-0-4 32

Narayanan P et al.

Rare earthsresources, processing, and uses

techniques. Mixer settler assemblies involving hundreds of stages are used for effective separation. As compared to ion exchange, solvent extraction has the advantage of being fast, continuous and works on more concentrated solutions, and it is economical for handling large quantities of materials. Although ion exchange is regarded as a superior technique for the production of extremely high pure materials, commercial production of materials at 99.9% or even 99.99% purity with solvent extraction has been possible. The solvent extraction technology is presently used for commercial scale separation of rare earths.

Applications of rare earths

Rare earths are used in a variety of applications in oil refinery, automobile, space technology, television, computers, mobile phones, auto exhaust catalysts, glass polishing, ceramics, and metallurgy. Neodymium and samarium are extensively used for the production of NdFeB and SmCo magnets. The uses of rare earths for different applications are given in Fig. 2.

Conclusions

Indian Rare Earths Ltd. is at the forefront for producing various rare earth compounds of high purity using solvent extraction techniques. Kerala, being a rich source of monazite ore, has tremendous potential for processing and producing rare earth compounds of very high purity to meet national and international requirements.

Shaji E & Pradeepkumar AP (Eds) 2014 Mineral Resources of Kerala Trivandrum: Dept of Geology Univ of Kerala ISBN 978-81-923449-0-4 33