The purpose of this work was to explore the use of fractional evaporative crystallization as a technology that can be used to separate medium-curie waste from the Hanford Site tank farms into a high-curie waste stream, which can be sent to a Waste Treatment and Immobilization Plant (WTP), and a low-curie waste stream, which can be sent to Bulk Vitrification. Experimental semi-batch crystallizations of sodium salts from simulant solutions of double-shell tank (DST) feed demonstrated that the recovered crystalline product met the purity requirement for exclusion of cesium and nearly met the requirement on sodium recovery. Batch fractional evaporative crystallization involves the removal of multiple solutes from a feed solution by the progressive achievement of supersaturation (through evaporation) and concomitant nucleation and growth of each species. The slurry collected from each of these crystallization stages was collected and introduced to filtration and washing steps. The product crystals obtained after washing were sampled for analysis by polarized light microscopy (PLM), dried, and sieved. The PLM results aided in identification of species crystallized in each stage. Carbonation was used as a supplemental method to evaporative crystallization in order to increase the sodium recovery in DST experiments. Carbonation was necessary due to the high aluminum ion concentration in the solution, which leads to formation of a viscous gel during evaporation. This gel was avoided by reacting carbon dioxide with hydroxyl ions, which modified the system behavior. Through two stages of carbonation, each followed by evaporation, the effect of carbonation on sodium recovery was demonstrated.

South Africa is a water scarce country. The expansion of the industrial, mining, and agricultural sectors to meet the needs of South Africa’s growing population requires more water. There is therefore an urgent need to develop effective wastewater treatment processes in order to recover and reuse water. This dissertation presents the treatment of an acidic wastewater stream from a platinum refinery which at present is being disposed of by contract with a waste disposal company. The major concern in treating the acid effluent stream is the high concentration of sodium ions (18 200 mg/l) and chloride ions (104 900 mg/l). The precipitation process is used to treat wastewater, but ultimately it generates more secondary waste as a sludge. The other process that is used to treat wastewater is reverse osmosis (RO). RO is usually preferred in the last stage of the treatment because the process is more expensive as membranes need to be replaced regularly. The approach used in this research focuses on evaporating liquid, consequently concentrating the remaining solution until the ions in the solution crystallize. The liquid produced is recycled back into the platinum plant for reuse, and the remaining salt crystals are collected as the useful product. The proposed water treatment process produces dilute hydrochloric acid as the condensate and a crystallized sodium chloride rich residue. The refinery is currently disposing of around 20 000 l/day of wastewater to landfills. The proposed treatment process can recover half of the volume of the wastewater stream to the refinery, helping reduce the fresh water consumption of the process by 10 000 l/day. Furthermore, this will reduce the volume of wastewater going to disposal by a half, namely only 10 000 l/day will need to be disposed of. The amount of Cl that can be recovered is variable and depends on the quantity of chloride in the wastewater. In the two samples processed the recovery was between a 2,5 w% and 10,7 wt% aqueous HCl solution. This corresponds to a saving of between 250 to 1000 kg/day of HCl. As the concentration of the recovered solution is variable, the recycling process would need to monitor the composition of the recycled stream and make up the acid concentration to some fixed value for reuse in the prices. The production of a dilute hydrochloric acid stream should be particularly attractive to the platinum refinery as the operation of the refinery requires hydrochloric acid as a feed. Thus, by recycling the wastewater, the refinery would reduce the volume of wastewater to be disposed of thereby reducing the cost of disposal of the waste while simultaneously reducing the cost of buying fresh hydrochloric acid. The proposed recovery of liquid and recycling it back to the refinery, will also reduce the environmental impact of the refinery, and very importantly in a water scarce country, reduce the freshwater consumption of the process. / Physics / M. Sc. (Physics)

Research on salts species formed by evaporation of aqueous solution of Na2 in the early 1930s. The thermodynamic, crystallographic and many other physical and chemical properties of most of the species formed from this solution has been known for decades. However, there was no complete information or reliable data to confirm the existence of a unique double salt that is rich in sodium carbonate, up until five years ago when a research identified the double salt (~2Na ₂ CO ₃ • Na ₂ SO ₄) from the ternary system Na₂CO ₃Na₂SO ₄ H₂O. Crystallization of this double salt so called sodium sulfate dicarbonate (~2Na ₂ CO ₃ • Na ₂ SO ₄) is known to be a primary contributor to fouling heat transfer equipment in spent-liquor concentrators used in the pulp and paper industry. Therefore, understanding the conditions leading to formation of this double salt is crucial to the elimination or reduction of an industrial scaling problem. In this work, double salts were generated in a batch crystallizer at close to industrial process conditions. X-ray diffraction, calorimetry, and microscopic observation were used to investigate the stability of the salts to in-process aging, isolation and storage, and exposure to high temperature. The results show that care must be taken during sampling on evaporative crystallization. Two apparent crystal habits were detected in the formation of sodium sulfate dicarbonate; the favored habit may be determined by calcium ion impurities in the system. The results also verify that sodium sulfate dicarbonate exists as a unique phase in this system and that remains stable at process conditions of 115-200℃