Solidification of acidic liquid waste from 99Mo isotope production

Full text: The production of the radioisotope molybdenum-99 by the fission process began at ANSTO in the late 1960's. Molybdenum-99, with a half life of 66 hours, decays by beta emission to produce technetium-99m, a metastable isotope. Technetium-99m is the most widely used medical radioisotope due to its near ideal properties, particularly the radioactive half life of only 6 hours. ANSTO has been producing generators for around 30 years for distribution to hospitals and nuclear medicine centres. These generators produce technetium-99m for medical use by decay of the contained molybdenum-99. To produce molybdenum-99, uranium dioxide pellets enriched to 2.2% 235U are irradiated in ANSTO's HIFAR reactor for about one week. The irradiated pellets are subsequently dissolved in nitric acid to allow the recovery of the molybdenum. An acidic intermediate level liquid waste results from this processing. A primary waste results from the raw leach solution (after removal of the molybdenum onto a packed alumina column) and a weaker secondary waste is produced from a series of column washing steps. The waste solution contains uranium, the majority of the other fission products and low levels of ammonia in a nitric acid solution. This liquid waste had been accumulating and stored in specially designed shielded tanks in a storage facility. A process has been developed at ANSTO to convert this intermediate level liquid waste into a crystalline solid form of considerably less volume and mass, for improved storage. The operation comprises three processing steps. The lower strength secondary waste solution first requires concentration, with the removal of water and some acid into a condensate. The condensate is chemically neutralised and treated through the conventional water treatment plant. Concentrated solution is then treated in a batch chemical process to reduce the low levels of ammonia to very low levels. The final evaporation process removes further water and acid and results in the solidification of the deammoniated product in stainless steel vessels designed for long term storage. The process was developed and commissioned through sequential steps. Initial testing was conducted on natural uranium nitrate based solutions followed by similar solutions with increasing levels of trace activity derived from the stored waste. The process was commissioned on stored liquid waste in 1999 and is now a routine operation. Initial processing through the concentration phase has been successful in removing 82-95% of the original liquor volume at a throughput rate of generally 4-4.5 L/h. The ammonia content in the acid waste had arisen principally from the addition of ammonia bearing condensate from the molybdenum extraction and initial purification process. This practice of combining these two liquid wastes is no longer continued but has resulted in an inventory of historical acid waste containing small concentrations of ammonia. A deammoniation process was developed to treat batches of concentrate before solidification. This processing step has been successful in reducing NH3-N to less than 10ppm under controlled conditions. Nitrogen oxides (NOx gasses) are a product of this chemical process and off gas is treated through a catalytic converter. Solidification to date has resulted in a product of 0.6-2.3% of the original liquor volume (or 1.7- 5.7% of the original solution weight). The solidification takes place in thick- walled once-use stainless steel vessels. The vessel is heated in a thermic oil bath with slow continuous feed of deammoniated concentrate and withdrawal of condensate. This phase is slower with throughput rates of around 1L/h decreasing to less than 0.5L/h as processing continues. When the required amount has been added to the vessel it is further heated, resulting in a product which solidifies on cooling. When this process is complete the connections to the vessel are removed and the vessel ports plugged. The vessel is then destined for further separate storage as an intermediate level solid waste. To date over 2500L of solution from storage has been treated and solidified to over 60kg of net product. This represents a significant waste minimisation initiative with a major reduction in volume and weight of radioactive waste as well as converting a stored liquid to a solid crystalline form. (author)