RI 3002 A Study of the Properties of Texas Polyhalite Pertaining to the Extraction of Potash

"The discovery of large deposits of polyhalite (K2S04.MgS04.2CaSO4.2H2O) in Texas has led to an investigation of possible industrial proecsses for the extraction of potash from this material. This mineral was first discovored in small quantities in the European potash deposits in or about the year 1800. Chemists fire thought it to be a form of calcium sulphate, but a more accurate analysis by Strohmiyer indicated the composition as given by the above formula.The decomposition of polytalite by aster is very slow and results in the formation of a layer of gypsum at the surface of the polyhalite which retarts the solution of the potaseium and magnesium sulphates. To obtain a substantial yield of K2S04 in solution it is necessary to use large amounts of water at room temperature, for he concentration of K2S04 is limited by the low solubility of syngonite (K2S04.CaS04.H2O) whereas at 100º C. several days boiling are necessary to obtain more than a 6 per cent K2S04 solution even when finely powdered polyhalite is employed.In 1854 H. Rose discovered that calcination, followed by leaching with water, resulted in a larger extraction of the potassium and magnesium sulphates, as compared with leaching without precalcination. During the course of a series of investigations concerning formation of oceanic salt deposits, Van't Hoff and his pupils obtained sufficient data to construct the equilibrium diagram for the system K+Mg+SO4--Ca++.H2O for 25° C. and for 83° C. These data are very well summarized. in the International Critical Tables' and by Boeke and Eitel. From a consideration of the diagrams for 83º C. one would conclude that an extraction of polyhalite with moderate amounts of water at 33º C. would result in a solution whose maximum concentration of K2So4 would be about 3.6 grams per 100 grams of water and of M2SO; about 4.0 grams per 100 grams of water, corresponding to equilibriumwith the solid phases: Polyhalite potassiam-calcium pentasulphate and anhydrite.The fact that it has been found possible to obtain as high as 11.4 grams of K2S04 per 100 grams of water (see table 6) and an equivalent amount of MgSo4 (8.1 grams per 100 grams of water was obtained corresponding to a ratio K2/Mg of 0.98; indicates that the formation of these complex salts is very slow. To be sure, this results was obtained at 100° C. instead of 83º C. However, the work of Anderson and Nestall 9 on the double salts of calcium and potassium sulphates at 100º C. indicates that the diagram at 100º C. C. would not be greatly different from that at 83º C. This slow rate of approach to equilibrium when combined with precalcination of,of polyhzli-,a is the 17,asis of some of the more p:olisinE methods of extracting potash from polyhalite."