Hydrometallurgical Processing of Phosphates

The term phosphate beneficiation often conjures up visions of processing technologies that physically separate the phosphate rock from some impurity and do not result in a change in the chemical nature of the phosphate rock. However, when we consider hydrometallurgical processing as a phos¬phate beneficiation technique we have to include all chemical treatments that convert phosphate rock into a more useful product. With most of the phosphate rock mined being used for fertilizer pro¬duction, the best known and most widely employed hydrometallurgical process is wet process phospho¬ric acid manufacture. In general, all phosphate rocks are so insoluble that there is no physical treat¬ment that will allow the phosphate content to be used by vegetation in a timely manner. However, after chemical treatment, 100% of the phosphate is readily available for vegetation nutrition. If there is a chemical beneficiation process that could be considered the standard method of treat¬ing phosphate rock it would have to be the wet pro¬cess for phosphoric acid production. In this process finely ground phosphate is reacted with sulfuric acid to give phosphoric acid and phosphogypsum. The phosphogypsum crystals are removed from the phosphoric acid solution and discarded; the phos¬phoric acid is further processed to give the finished fertilizer product. The primary reason that this pro¬cess was adopted so widely is because the phosphogypsum solid that is formed can be easily separated from the phosphoric acid, thereby removing the calcium portion of the phosphate rock and the sul¬fate portion of the sulfuric acid. Other acids have been used to treat phosphate rock but nitric acid is the only other acid used commercially. Nitric acid gives a mixture of phos¬phoric acid and nitrates that can be further pro¬cessed into N-P fertilizers, but the range of N/P grades that can be produced is limited. Hydrochlo¬ric acid has been used to react with phosphate rock, and it can be used to generate a pure phos¬phoric acid but only after solvent extraction to separate the calcium chloride from the phosphoric acid. And then there is the problem of what to do with the calcium chloride. The acid that has received the most attention as a substitute for sulfuric acid is phosphoric acid. In this process, the phosphoric acid reacts with the phosphate rock to give a mono-calcium phosphate solution. This process does not dissolve all the impurities in the phosphate rock, and these solids can be removed from the solution before sulfuric acid is added to convert the soluble calcium to insoluble phosphogypsum. Despite all the claimed advantages, this process has not found favor. A suc¬cessful application of this process to treat some of the lower grade phosphate rocks being used today would seem to have some distinct advantages. Other beneficiation schemes have been pro¬posed or practiced on specific phosphate rocks on a limited scale. These include calcination followed by water leaching to remove lime, weak acid