Patented Apr. 18, 1950 2,504,130 R UNITED STATES PATENT OFFICE 2,504,130 PROCESS OF MAKING ALKALINE EARTH MEAL PERMANGANATES Theodore Jaskowiak, La Salle, Ill., assignor to Carus Chemical Company, a corporation of Illinois No Drawing. Application October 12, 1945, Serial No. 622,086 8 Claims. (C. 23-58) 1. 2 This invention relates to a method of forming desired permanganate such as, for example, cal alkaline earth permanganates from aluminum cium, barium or strontium, by reaction with the permanganate and more particularly to the corresponding oxide, hydroxide or carbonate. formation of such alkaline earth permanganates The required oxide, hydroxide, or carbonate or in a series of reactions starting with potassiul any admixture and/or sequence thereof, is added permanganate, and passing through aluminum in Water solution or in any form in suitable pro permanganate. portions to the aluminum permanganate solu The production of these permanganates, in tion, or the aluminum permanganate solution pure form, has heretofore been a matter of ex may be added to the oxide etc., or the two may treme difficulty and expense. The prior art is O be added to one or the other concurrently. In summarized in Wilson et al. Patent 1,544,115. In the case of the more stable permanganates, as, addition to the methods there suggested for the for example, calcium, barium and strontium this production of calcium permanganate, a disin reaction is preferably carried out at or near the fecting solution including aluminum perman boiling temperature. In general care should be ganate is described in British Patent 10,015 of taken to use only such amounts of oxide, etc., 1884, this solution being prepared by the inter as to react completely, without adding an excess, action of aluminum sulfate and potassium per With the aluminum permanganate solution in manganate, the resulting mixture being Said to accordance with the equation: comprise aluminum permanganate and alumi num sulfate. No attempt was made to obtain 20 an aluminum permanganate of greater purity or concentration. Upon completion of this reaction, the perman I have now discovered that by proper Con ganate Solution is separated from the precipi trol of reacting ingredients and reaction ten tated Solids as by filtration. The resulting solu peratures, potassium permanganate and alumi 25 tion is one of Substantially the pure perman num sulfate, and a limited amount of Water will ganate desired, together with small amounts of react according to the following equation: Sulfate and potassium ions. This solution may be used as Such or it may further be processed to yield a Solution of higher concentration and to produce a solution substantially pure and 30 greater purity or it may be processed to yield a suitable for use in producing the aforementioned Solid crystalline product. permanganates, while nearly all potassium Will To obtain a solution of greater concentration be removed as crystallized potassium aluminum and higher purity the permanganate solution is sulfate. It is to be understood that Only Suffi concentrated by evaporation either at atmos cient water is added to produce a concentrated pheric pressure or under reduced pressure, when solution of aluminum permanganate. Prefer Sulfates will crystallize out progressively as the ably this involves the addition of ingredients in concentration rises, these sulfates usually being the following proportions: the lower hydrates. AS the concentration in Pounds creaseS SOme potassium permanganate also crys 40 tallizes out, especially upon cooling the concen Potassium permanganate ------172 trated solution. Aluminum sulfate 18H2O ------500 The maximum concentration obtainable varies Water ------500 with the different permanganates, depending In this reaction a Small excess of aluminum Sul upon their solubilities. For example, calcium fate may be used, depressing further the solubil permanganate may be concentrated to a con ity of potassium salts and not interfering greatly tent of 75% to 80% Ca(MnO4)2.4H2O and a spe with further use of the resulting solution. cific gravity of 1.700 to 1.750 at room tempera Aluminum permanganate is unstable, espe tures. cially at higher temperatures and the reaction Some permanganates such as calcium being mixture should preferably be maintained at all 50 very Soluble prove to be extremely difficult to times below 80° C. Upon cooling to effect crys crystallize in stable form; the crystals obtained tallization, the maSS is filtered or the potassium being in the hydrated form, often dissolve in aluminum Sulfate is removed in any other Suit their contained Water of crystallization when sub able manner. The resulting aluminum perman jected to temperatures but little higher than the ganate solution is then employed to produce the 55 usual room or atmospheric temperatures. To 2,504,130 3 4. produce a stable permanganate such as these, in 3. The method as set forth in claim 1 in which dry form, the concentrated filtered or clarified the metalis barium. solution of Such a permanganate is further evap 4. The method as set forth in claim 1 in which orated at temperatures preferably below 100° C. the metal is strontium. until the water content is reduced to an amount 5. The method of forming an alkaline earth. corresponding to 4 moles of water for calcium permanganate which comprises reacting potas permanganate, at which point the Solution or sium permanganate and aluminum sulfate in the melt is allowed to solidify into a solid crystalline presence of Sufficient Water to produce a con mass by suitable means such as sheeting, flak centrated solution of aluminum permanganate, ing, etc. O said reaction being conducted at a temperature Permanganates such as barium and strontium, not substantially above 80° C., separating out though having a rather high solubility in Water, substantially all potassium aluminum Sulfate, will, after concentration, yield well definable then reacting with the aluminum permanganate crystals which can be separated and kept as Such. Solution a member of the class consisting of an The invention described and claimed herein is oxide, hydroxide and carbonate of an alkaline related to those described and claimed in my co earth metal at a temperature above 80 C. to and pending applications, Serial Nos. 622,085 and including the boiling point of the solution, and 622,087, filed October i2, 1945. recovering the alkaline earth permanganate. The foregoing detailed description has been 6. The method as set forth in claim 5 in which given for clearness of understanding only, and no 20 the metal is calcium. m unnecessary limitations should be understood 7. The method as set forth in claim 5 in which therefron. the metal is barium. What I claim as new, and desire to Secure by 8. The method as set forth in claim 5 in Which Letters Patent, is: the metal is strontium. 1. The method of forming an alkaline earth. THEODORE JASKOWEAK. . metal permanganate, which comprises reacting a solution of aluminum permanganate With a REFERENCES CTED member of the class consisting of an oxide, hy The following references are of record in the droxide and carbonate of an alkaline earth metal file of this patent: at a temperature above 80 C. to and including 30 the boiling point of the solution, and recovering FOREIGN PATENTS the alkaline earth metal permanganate. Number Country Date 2. The method as set forth in claim 1 in which 10,015 Great Britain ------1884 the metal is calcium.