Thorium Production

Thorium is distributed widely in igneous rock such as granites, pegmatites, and gneisses. It composes 0.00020.001 wt.% of the Earths crust which makes it approximately as abundant as lead. However, unlike lead, thorium and its compounds do not undergo the same hydrothermal reactions that form large, concentrated mineral deposits. Thoriums maximum concentration in igneous rocks is rarely higher than 1%. Natural erosion and alluvial classication does provide isolated deposits of increased thorium values as the mineral monazite. Such deposits containing 3 10% thorium are found throughout the world but the most notable were in Brazil, India, and later in the USA, the former USSR, Asia, Africa, Australia, and Europe. The mineral values most commonly associated with these monazite-bearing sands are rare-earth oxides, titanium, gold, and silica. Monazite sands are processed by complete dissolution into sulfuric acid at 200 mC to produce a monazite sulfate solution from which the thorium can be selectively crystallized. This takes about 1 h if the sands are ne (325 mesh). The rare-earth minerals and thorium are precipitated from the sulfate solution by raising the pH to 1 with NH OH. The thorium is then % dissolved from the precipitate with HNO and concen$ trated by solvent extraction using tributyl phosphate. Thorium may also be concentrated from monazite sands by caustic digestion at 150 mC and 4050% NaOH for several hours to form a hydrous metal oxide solution. This solution is crystallized, dried, and dissolved in HCl from which it is precipitated at pH 5.8 by NaOH addition to produce a uranium- and thorium-bearing cake. This cake is then dissolved into HNO and processed as described above. $ Thorium oxide cannot be reduced with carbon at manageable temperatures so the production of thorium must be accomplished by metallothermic reduction of the oxide or the electrolytic reduction of thorium halides. The following successful processing methods have reported. 1. Thorium Fluoride Reduction ThF is formed by the precipitation of thorium oxalate % from thorium nitrate solutions. The oxalate is then

calcined to form the oxide which is then uorinated by: 4HFjThO l ThF j2H O # % # The ThF may be reduced with calcium or made into % ThF :KF that can be melted with NaCl, and KCl and % reduced by electrolyses at 800 mC. The addition of ZnCl to the calciumion bomb proves useful in three ways:# (i) The reduction of the ZnCl provides ad# ditional heat, (ii) the formed CaCl acts as a ux for # the CaF which normally melts at nearly 1400 mC, and # (iii) the zinc produced forms a low melting point alloy with the thorium. The resulting ZnTh button is removed from the sealed bomb lined with CaO or MgO and is puried by vaporizing the zinca vacuum. Thorium made by direct calciumion is generally vacuum arc rened.

2. ThO2 Reduction Thorium oxide may be reduced in an inert atmosphere bomb using calcium and a CaCl ux. The resulting mixture is cleaned by leaching in# a dilute acetic acid solution followed by water washing to yield a high purity thorium powder that can be formed by powder metallurgy processing.

3. ThCl4 Reduction The tetrachloride may be reduced with sodium, potassium, magnesium, or calcium. However, unless the TiCl is rst rened by distillation, residual oxide and % oxychlorides will result in oxygen impurity in the product. This is not a problem when calcium is used but is when magnesium is used. One advantage of magnesium reduction is that a solid magnesium thorium alloy is formed rather than a ne powdered product. S. M. Howard

Copyright ' 2001 Elsevier Science Ltd. All rights reserved. No part of this publication may be reproduced, stored in any retrieval system or transmitted in any form or by any means : electronic, electrostatic, magnetic tape, mechanical, photocopying, recording or otherwise, without permission in writing from the publishers. Encyclopedia of Materials : Science and Technology ISBN: 0-08-0431526 pp. 93489348 1