Lanthanum - Production

Production

Lanthanum is most commonly obtained from monazite and bastnäsite. The mineral mixtures are crushed and ground. Monazite, because of its magnetic properties, can be separated by repeated electromagnetic separation. After separation, it is treated with hot concentrated sulfuric acid to produce water-soluble sulfates of rare earths. The acidic filtrates are partially neutralized with sodium hydroxide to pH 3-4. Thorium precipitates out of solution as hydroxide and is removed. After that, the solution is treated with ammonium oxalate to convert rare earths to their insoluble oxalates. The oxalates are converted to oxides by annealing. The oxides are dissolved in nitric acid that excludes one of the main components, cerium, whose oxide is insoluble in HNO₃. Lanthanum is separated as a double salt with ammonium nitrate by crystallization. This salt is relatively less soluble than other rare earth double salts and therefore stays in the residue.

The most efficient separation routine for lanthanum salt from the rare-earth salt solution is, however, ion exchange. In this process, rare-earth ions are adsorbed onto suitable ion-exchange resin by exchange with hydrogen, ammonium or cupric ions present in the resin. The rare earth ions are then selectively washed out by a suitable complexing agent, such as ammonium citrate or nitrilotriacetate. Lanthanum can also be separated from a solution of rare earth nitrates by liquid-liquid extraction with a suitable organic liquid, such as tributyl phosphalate. Currently, the most widely used extractant for the purification of lanthanum and the other lanthanides is the 2-ethylhexyl ester of 2-ethylhexylphosphonic acid; this has better handling characteristics than the previously used bis-2-ethylhexyl phosphate.

Lanthanum metal is obtained from its oxide by heating it with ammonium chloride or fluoride and hydrofluoric acid at 300-400 °C to produce the chloride or fluoride:

La₂O₃ + 6 NH₄Cl → 2 LaCl₃ + 6 NH₃ + 3 H₂O

This is followed by reduction with alkali or alkaline earth metals in vacuum or argon atmosphere:

LaCl₃ + 3 Li → La + 3 LiCl

Also, pure lanthanum can be produced by electrolysis of molten mixture of anhydrous LaCl₃ and NaCl or KCl at elevated temperatures.