Process for the separation of zirconium and hafnium tetrachlorides from mixtures thereof

A continuous process for the separation of zirconium and hafnium tetrachloride from mixtures thereof by selective absorption in the vapor state for recovering a zirconium tetrachloride having less than 200 ppm hafnium comprising the steps of passing the mixture of zirconium and hafnium tetrachloride in the vapor state through a contact zone in countercurrent flow with a molten solvent selected from the group consisting of an alkali metal chloroaluminate, an alkali metal chloroferrate and mixtures thereof, in which the alkali metal chloroaluminate has the formula nAlCl.sub.3.pMeCl and the alkali metal chloroferrate has the formula nFeCl.sub.3.pMeCl in which Me is an alkali metal and n and p are the number of moles and in which the ratio of n/p is maintained above .95 but below 1.30, and maintaining the temperature within the range of 250.degree.-550.degree. C. and the pressure below 5 bars in the contact zone, whereby zirconium tetrachloride is adsorbed in the solvent flowing in one direction through the contact zone while hafnium chloride continues to flow as an enriched vapor phase in the other contact zone, removing and condensing the enriched phase of hafnium tetrachloride from one end portion of the contact zone, removing the zirconium tetrachloride enriched solvent phase from the other end of the contact zone, and separating from the solvent phase a purified zirconium tetrachloride having less than 200 ppm hafnium, and said process including the step of recycling the solvent to the contact zone and adding AlCl.sub.3 when the solvent is an alkali metal chloroaluminate and FeCl.sub.3 when the solvent is an alkali metal chloroferrate, and mixtures of AlCl.sub.3 and FeCl.sub.3 when the solvent is a mixture of alkali metal chloroaluminate and alkali metal chloroferrate to maintain the molar ratio of n/p.