Solvent degradation?Rössing Uranium Mine - Synopsis

Rössing Uranium Mine operates a recovery circuit with continuous ion exchange followed by solvent extraction. Serious organic degradation problems were encountered during 1985/6, 2000 and 2005 in the solvent extraction plant. The preferential loss of the tertiary amine extractant was observed during the above-mentioned period. Previous investigations revealed that the tertiary amine was breaking down to nitrosamine, which cannot take part in the exchange reaction with U3O8. A reduction in the redox potential of the solvent extraction plant feed to below 500 mV halted this preferential loss. A lot of effort has been made to try and understand the actual mechanism for nitrosamine formation. Current understanding for the degradation is that formation is due to high nitrates on the strip side of the circuit emanating from nitrates from the precipitation process using ammonia. It is the current belief that pH lower than 3.7 on the strip side results in loading of nitrates onto the solvent. If oxidizing conditions prevail on the extraction side of the solvent extraction circuit, the tertiary alamine will then degrade into nitrosamine. This phenomenon is yet to be established and verified. It has, however, been established that the above process is brought about the following conditions ?High redox potential greater than 550 mV predominately caused by a high Fe3+/Fe2+ratio (4:1) ?Perception that if Fe2+<0.5 g/lit will contribute to high redox ?High concentrations of NO-3 in the conc eluate (feed to SX)/ammonium sulphate (NO-3> 4 g/l based on historic values) ?Presence of Mo as a catalyst ?Tests also have proved that the presence of nitrous acid in a concentration of 1 g/lat 550 mV leads to formation of nitrosamines from alamine.