Effects of Seeding Selection through Recycled Crystal Classification on Crystal Size Distribution (CSD) for Copper Sulfate Pentahydrate

"The Freeport-McMoRan Sierrita Crystal Plant produces Copper (II) Sulfate Pentahydrate (CuSO4·5H2O) through a series of cooling crystallizers. In this process, high supersaturation and unwanted spontaneous nucleation promote fine crystals. Seeding through recycled crystal classification can manipulate the crystal size distribution (CSD) for larger crystals. Proper selection of the crystallizer for seeding can prevent spontaneous nucleation and promote final crystal size. This study shows when seeding temperature is closer to the crystallizer temperature, suspension densities in the crystallizers are promoted and overall CSD shifts to a larger size of crystals. INTRODUCTION Figure 1 shows an overview of the crystallization process. The in-plant feed flow, called Pregnant Mother Liquor (PML), enters the first crystallizer and is subsequently cooled through a series of four crystallizers. Specific temperatures are targeted for each crystallizer to ensure the crystallization process is operating within the metastable zone (MSZ). The discharged flow from crystallizer #5 then enters two cyclones. The overflow from the cyclones contains smaller crystals providing seed crystals for crystallizer #5. The underflow from the cyclones begins the drying process. The overflow from crystallizer #5 enters cyclone #3 for removal of fine crystals and seeding purposes. The underflow from cyclone #3 has the capability to provide seed crystals for crystallizer #1 or crystallizer #2. The overflow leaves the system as Spent Mother Liquor (SML). Undersize crystals dissolve into the PML and return back to crystallizer #1.THEORIES AND METALLURGICAL TESTS Seeding requires an understanding of the crystal size, solution temperature and amount of crystals that enter the crystallizers (1). For the seed crystal size, classified crystal seeds can prevent fine crystals returning back into the system which eventually leads to excessive agglomeration (2). Proper selection of the crystallizer can ensure seeding at an appropriate temperature. Seeding at a temperature much lower or higher than the saturation temperature promotes spontaneous nucleation. Typically, seeding between 4-5°F below the saturation temperature is acceptable (5). A general rule of thumb is to add the seed crystals at the temperature between the solubility curve and the metastable zone. An experiment conducted by Mettler-Toledo AutoChem, Inc. indicates seeding close to the solubility curve rather than the metastable zone promotes a lower supersaturation and nucleation rate but yields a higher growth rate and a greater number of larger crystals (1). The amount of seed crystals can not only change the suspension density but also narrows the width of the MSZ in the crystallizers. An experiment conducted by Jaroslav Nyvlt reports with the crystals absent, the maximum allowable undercooling is 6.3 degrees at a cooling rate, 5°C/hour. With the presence of crystals, it narrows the MSZ width to 2.2 degrees (4). Industrial crystallizers normally operate at suspension densities between 15% and 25% by mass. When suspension densities are lower than 15%, it increases the risk of primary nucleation and the probability of incrustations; on the other hand, if the suspension densities are greater than 25%, it can cause a greater attrition rate and increase the probability of deposits (6). Moreover, operating suspension densities between 15% and 25% are also sufficient to minimize supersaturation rate which promotes crystal growth over nucleation (2, 6)."