A 22-E ATTORNEY 3,687,638 United States Patent Office Patented Aug
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Aug. 29, 1972 U. E. G. NETZEL PROCESS FOR RECOVERING SODIUM AND SULFATE VALUES3,687,638 FROM SCHOENITE-CONVERSION END LIQUORS Filed Nov. 20, 1968 POASH PLANT SCHOENITE CONVERSION END LOUOR (25°C SCHOENTE COOLING POND (15°C) SCHOENTE RESIDUAL — BRINE — WINTER SUMMER EPSOMITE COOLING EVAPORATION POND POND (+5°C) (3O-4O°C) EPSOMTE ASTRAKANTE EPSOMTE DEPLETED EFFLUENT -- HALTE GLAUBER SALT COOLNG POND (-5°C) - - - - - - -s a a -s a GLAUBER SALT END LOUOR STORAGE POND POTASH PONDS INVENTOR. POTASSUM - CONTAINING DOUBLE SALTS OF MgSO, ULRICH E. G. NETZEL a 22-e ATTORNEY 3,687,638 United States Patent Office Patented Aug. 29, 1972 2 fate by the conversion of schoenite, it is essential that the 3,687,638 Schoenite feed material be essentially free from NaCl. PROCESS FOR RECOVERNG SODUMAND SUL. Similarly, the feed materials for the production of salt FATE VALUES FROMSCHOENITE-CONVERSION cake should be essentially free from potassium contami END LOUORS nant. Ulrich E. G. Neitzel, Ogden, Utah, assignor to Great Salt The aforementioned co-pending application Ser. No. Minerals and Chemicals Corporation, New York, 799,376, avoids the production of impure schoenite by Filed Nov. 20, 1968, ser, No. 777,359 recycling the Schoenite-conversion end liquor back to the nt. C. B01d 9/00 Solar ponds for recovery of the potassium values re U.S. C. 23-296 16 Claims O maining therein. It is economically important that the greatest possible portion of the potassium contained in the recycled end liquor be returned to the potassium ABSTRACT OF THE DISCLOSURE sulfate plant. A high-grade crystal crop, usually schoenite, is re The recycled schoenite-conversion end liquor contains covered from schoenite-conversion end liquor for re Substantial concentrations of sodium and sulfate, how cycle to the potassium sulfate plant that produces the ever, and is a convenient source of feed materials for a end liquor. The resulting residual brine is treated to Sodium sulfate plant. There is thus a need for a process recover high-sulfate, low-potassium crystal crops suitable which effects a clean recovery of sulfate minerals from Schoenite-conversion end liquor, without interfering with for use as feed material for the production of salt cake the recycling of potassium values through the potassium (sodium sulfate). Sulfate plant and the solar ponds. Commonly assigned co-pending U.S. patent applica- - - - SUMMARY OF THE INVENTION tion Ser. No. 735,840, filed June 10, 1968, discloses According to the present invention, schoenite-conver and claims a process for evaporating natural brines, such sion end liquor is first introduced to a cooling pond as those taken from the Great Salt Lake of Utah, in solar wherein it is allowed to cool sufficiently to drop a high ponds to produce potassium-containing double salts of grade Schoenite crystal crop, i.e. a crystal crop contain magnesium sulfate. Commonly assigned co-pending U.S. ing at least about 70 and typically about 85 to about 95 patent application Ser. No. 799,376, filed Feb. 14, 1969, percent by weight schoenite, the remainder being sub discloses and claims a process for treating potassium stantially all epsomite. This crystal crop is a valuable containing double salts, such as those resulting from the product even if it contains a large amount of epsomite, process of the aforementioned application Ser. No. 735, because epsomite is tolerable in and is often a preferred 840, to produce schoenite and then potassium sulfate. constituent of the feed to a potassium sulfate plant. Also produced by the treatment of these double salts is Crystallization of schoenite from the plant end liquor a Schoenite-conversion end liquor containing substantial produces a residual brine, which contains the constituents, concentrations of potassium and sulfate. This end liquor particularly the sulfate, required for producing salt cake is recycled to the solar evaporation ponds for the purpose (sodium sulfate) but is too contaminated with respect of recovering the potassium and sulfate values, even to potassium to be directly suitable as feed to a salt cake though it also contains appreciable quantities of unde plant. According to this invention, it has been found sirable constituents, notably sodium, magnesium, and 40 that, surprisingly, such residual brines may be evaporated chloride. and/or cooled to crystallize sodium-containing and sul BACKGROUND OF THE INVENTION fate-containing minerals, without crystallizing significant Field: The present invention relates to the recovery additional quantities of potassium-containing minerals. of valuable salts from natural brine and is directed to The residual brine is thus treated by appropriate cooling the recovery of feed constituents for the production of 45 or evaporation procedures to recover crystal crops rich both potassium sulfate and sodium sulfate from the in sulfate but containing essentially no potassium con schoenite-conversion end liquor effluent from a potassium taminant. These salts are excellent feed materials for sulfate plant. It specifically provides a method for re a salt cake plant. The crystallization of sulfate-containing covering sulfate-containing materials from such end liq minerals is accomplished under conditions which pro ors free from potassium. 50 duce an end liquor somewhat depleted with respect to State of the art: It is known to produce potassium sodium, but which retains substantially all of the potas sulfate from potassium-containing double salts of mag sium initially carried by the aforementioned residual nesium sulfate by procedures which involve contacting brine, together with sufficient sulfate that it remains a the double salts with a saturated sulfate solution to con suitable brine for recycle to a solar pond system em vert them to Schoenite while producing a schoenite-con 55 ployed for the production of potassium-containing double version end liquor. The schoenite is then converted to salts of magnesium sulfate. Accordingly, the process of potassium sulfate. the present invention may be applied to the recycling of It is further known to treat the schoenite-conversion schoenite-conversion end liquors produced by the cyclic end liquor in various ways to produce additional potas process disclosed in the aforesaid copending application sium salts, as well as sodium salts. U.S. Pat. No. 3,004,826, 60 Ser. No. 799,376 without significantly affecting any of for example, teaches a method whereby schoenite-con the details of said cyclic process. version end liquor is treated by dissolving ground kainite The precise manner in which the residual brine is material therein. Additional schoenite is thereby pro treated to recover feed materials for a salt cake plant duced in admixture with NaCl. The resulting mother depends upon the prevailing climate and seasonal condi liquor is discarded. In the production of potassium sul 65 tions. One procedure involves cooling of the residual 3,687,638 3 r4. brine to a temperature approaching freezing or below to level which crystallizes all of the schoenite and some crystallize epsomite, and Glauber salt. This procedure epsomite from solution. A temperature of about 15 C. is normally employed during the winter season or dur has been found consistently effective for this purpose. The ing those portions of the year when cold temperatures temperature can be varied from this point plus or minus of this kind prevail for substantial time intervals during about 5 C. without seriously adversely affecting the the night. During the portions of the season or day when remainder of the process. At higher temperatures, less evaporation conditions prevail, an alternative procedure schoenite is recovered, about 25 C. being the practical may be employed whereby a mixture of astrakanite and upper limit of temperature in most instances. Lower tem halite is produced. peratures produce proportionately more epsomite. Al The schoenite conversion end liquors treated in accord O though it is often possible to cool the conversion end ance with this invention vary widely in composition, de liquor to as low as about 10 C. without causing the pre pending upon the composition of the feed to the potas cipitation of appreciable quantities of other contaminants, sium sulfate plant. In general, any brine similar in com it is usually desired to limit the amount of epsomite in position to those resulting from the conversion of the Schoenite crystal crop to about 30 percent by weight potassium minerals to a hydrated potassium-magnesi 5 or less. um sulfate, particularly those known in the art The schoenite crystal crop resulting from the aforemen as schoenite-conversion end liquors, may be so treated. tioned cooling step may be harvested and recycled to In any event, the end liquor contains, as essential con the potassium sulfate plant which produced the initial stituents, various proportions of dissolved magnesi schoenite-conversion end liquor. The residual brine re um sulfate, potassium, sodium, and chloride. Table 1 re Sulting this step may then be treated in one or more of ports the chemical analyses, in weight percent, of vari the following alternative ways: ous simulated schoenite conversion end liquors representa (A) It may be cooled only sufficiently to cause the tive of those which result from producing schoenite from crystallization of epsomite without substantial concurrent crystal crops containing potassium-containing double salts crystallization of other salts, notably Glauber salt. The of magnesium sulfate in admixture with epsomite and so remaining brine is then separated from the epsomite and dium chloride. Table 2 reports the compositions of the cooled sufficiently to cause the crystallization of Glauber same end liquors in moles of particular dissolved salts salt. per 1,000 moles H.O. (B) It may be cooled sufficiently to cause both epsomite TABLE 1.--COMPOSITION OF SIMULATED SCHOENITE CONVERSION END LIQUORS In weight percent Mig SO K Na C End liquor: 12.8 2.78 5.72 1.35 2.05 2.65 5, 28 11.83 1.2 2.57 40 2.6 0.67 2.46 392 2.22 9, S6 2.34 3.44 2.0 9.5 2.21 3.04.