Thorium processing

The major commercial source of thorium is monazite, an anhydrous rare earth phosphate with the chemical formula (Ce,La,Nd,Th)PO₄. Typically, 3 to 5 percent of the metal content of monazite is thorium (in the form of thorium dioxide, ThO₂). Much of the world’s current demand for thorium metal and its compounds is satisfied by mining placers along India’s Malabar Coast, 

The dredged monazite is admixed with a variety of other minerals, including silica, magnetite, ilmenite, zircon, and garnet. Concentration is accomplished by washing out lighter minerals in shaking tables and passing the resulting monazite fraction through a series of electromagnetic separators, which separate monazite from other minerals by virtue of their different magnetic permeabilities.  

Acidic and alkaline digestion

Although monazite is very stable chemically, it is susceptible to attack by both strong mineral acids (e.g., sulfuric acid, H₂SO₄) and alkalies (e.g., sodium hydroxide, NaOH). In the acid treatment, finely ground monazite sand is digested at 155 to 230 °C (310 to 445 °F) with highly concentrated (93 percent) H₂SO₄. This converts both the phosphate and the metal content of the monazite to water-soluble species. The resulting solution is contacted with aqueous ammonia, first precipitating hydrated thorium phosphate as a gelatinous mass and then metathesizing the thorium phosphate to thorium hydroxide. Finally, the crude thorium hydroxide is dissolved in nitric acid to produce a thorium nitrate-containing feed solution suitable for final purification by solvent extraction.

In alkaline digestion, finely ground monazite sand is carefully treated with a concentrated NaOH solution at 138 °C (280 °F) to produce a solid hydroxide product. Any one of several mineral acids is then used to dissolve this solid residue. For example, treatment with hydrochloric acid yields a solution of thorium and rare earth chlorides. Conventionally, thorium is partially separated from the rare earths by addition of NaOH to the acidic chloride solution. The crude thorium hydroxide precipitate is then dissolved in nitric acid for final purification by solvent extraction.  

Solvent extraction 

For the purification of thorium from residual rare earths and other contaminants present in nitric acid feed solutions, the crude thorium nitrate concentrate is usually contacted with a solution of tributyl phosphate diluted by a suitable hydrocarbon. The resulting organic extract, containing the thorium (and any uranium that may be present), is then contacted countercurrently with a small volume of nitric acid solution in order to remove contaminating rare earths and other metallic impurities to acceptable levels. Finally, the scrubbed tributyl phosphate solution is contacted with a dilute nitric acid solution; this removes, or strips, thorium from the organic solvent into the aqueous solution while retaining uranium (if present) in the organic phase. Thermal concentration of the purified thorium nitrate solution yields a product suitable for the fabrication of gas mantles. The nitrate can also be calcined to ThO₂, which is incorporated into ceramic fuel elements for nuclear reactors or is converted to thorium metal. 

Reduction to the metal

Powdered ThO₂ can be fluorinated with gaseous hydrogen fluoride (HF), yielding thorium tetrafluoride (ThF₄). The metal is obtained by the Spedding process, in which powdered ThF₄ is mixed with finely divided calcium (Ca) and a zinc halide (either zinc chloride or zinc fluoride) and placed in a sealed, refractory-lined “bomb.” Upon heating to approximately 650 °C (1,200 °F), an exothermic reaction ensues that reduces the thorium and zinc to metal and produces a slag of calcium chloride or calcium fluoride:

After solidification, the zinc-thorium alloy product is heated above the boiling point of zinc (907 °C, or 1,665 °F) but below the melting temperature of thorium. This evaporates the zinc and leaves a highly purified thorium sponge, which is melted and cast into ingots.