Patented Apr. 18, 1950 : " : . . . 2,504,131

UNITED STATE2,504,131 s PATENT OFFICE PROCESS OF MAKENG ALKALIMETAL AND AMMONIUMPERMANGANATES Theodore. Jaskowiak, La Salle, Ill., assignor to Carus. Chemical Company, a corporation of Illinois . . . No Drawing. Application October 12, 1945, ". . . . . serial No. 622,087 10 Claims. (CI. 23-58) . 2 This invention relates to a method of forming ganate Such as, for example, , Sodium or other from potassium perman zinc, by reaction with the corresponding oxide, ganate, and more particularly to the formation of hydroxide or carbonate. The required oxide, hy aluminum , and the conversion droxide, or carbonate or any admixture and/or thereof into a permanganate other than potas Sequence thereof, is added in Water Solution or in sium. any form in Suitable proportions to the aluminum The production of these permanganates, in pure permanganate Solution, or the aluminum per form, with the exception of potassium perman manganate Solution may be added to the oxide, ganate, has heretofore been a matter of extreme etc., or the two may be added to one or the other difficulty and expense. The prior art is Sum O concurrently. In the case of the more stable per marized in Wilson et al. Patent 1,544,115. In manganates, as, for example, Sodium and calcium, addition to the methods there suggested for the this reaction is preferably carried out at or near production of , a disin the boiling temperature. In the case of less fecting solution including aluminum permanga stable permanganates Such as per nate is described in British Patent 10,015 of 1884, 5 manganate, this reaction must be carried out at this solution being prepared by the interaction much lower temperatures. In general, care of aluminum sulfate and potassium permanga should be taken to use only such amounts of oxide, nate, the resulting mixture being said to com etc., as to react completely, without adding an prise aluminum permanganate and aluminum excess, With the aluminum permanganate solu sulfate. No attempt was made to obtain an 20 aluminum permanganate of greater purity or tion in accordance with the equation: v concentration...... " I have now discovered that by proper control of reacting ingredients and reaction temperatures, and aluminum sulfate, 25 Upon completion of this reaction, the perman and a limited amount of water will react accord ganate Solution is Separated from the precipitated ing to the following equation: solids as by filtration. The resulting solution is one of Substantially the pure permanganate de sired, together with small amounts of sulfate and potassium . This Solution may be used to produce a solution substantially pure and Suit as Such or it may further be processed to yield a able for use in producing the aforementioned per Solution of higher concentration and greater pur manganates, while nearly all potassium will be ity Or it may be processed to yield a solid crys removed as crystallized potassium aluminum Sul talline product. fate. It is to be understood that only sufficient To obtain a solution of greater concentration water is added to produce a concentrated solution 5 and higher purity the permanganate solution is of aluminum permanganate. Preferably this in concentrated by evaporation, either at atmos volves the addition of ingredients in the following pheric pressure or under reduced pressure, when proportions: Sulfates Will crystallize out progressively as the Pounds concentration rises, these sulfates usually being Potassium permanganate------172 40 the lower hydrates. As the concentration in Aluminum sulfate 18H2O------500 creases Some potassium permanganate also crys tallizes out, especially upon cooling the concen Water ------500 trated Solution. In this reaction a small excess of aluminum Sul The maximum concentration obtainable varies fate may be used, depressing further the With the different permanganates, depending up of potassium salts and not interfering greatly with on their . For example, calcium per further use of the resulting Solution. manganate may be concentrated to a content of Aluminum permanganate is unstable, especially 75% to 80% Ca(MnO4)2.4H2O and a specific grav at higher temperatures and the reaction mixture ity of 1.700 to 1.750 at room temperatures. should preferably be maintained at all times below Some permanganates Such as calcium and 80° C. Upon cooling to affect crystallization, the sodium being very soluble prove to be extremely mass is filtered or the potassium aluminum Sulfate difficult to crystallize in stable form; the crystals is removed in any other suitable manner. The obtained, being in the hydrated form, often dis resulting aluminum permanganate Solution is solve in their contained water of crystallization then employed to produce the desired perman 55 when subjected to temperatures but little higher 2,504,18i 3 4. than the usual room or atmospheric temperatures. 4. The method of forming a permanganate of To produce a stable permanganate Such as these, the class consisting of alkali metal and an in dry form, the concentrated filtered or clarified monium permanganates, which comprises react Solution of such a permanganate is further evap ing potassium permanganate and aluminum sul orated at temperatures preferably below 100° C. fate at a temperature not greater than about 80° until the water content is reduced to an amount C. and in the presence of sufficient water to pro corresponding to 4 moles water for calcium per duce hydrated potassium aluminum Sulfate crys manganate and One mole of Water for Sodium tals and a Solution of aluminum permanganate, permanganate, at which point the solution or removing the potassium aluminum sulfate from melt is allowed to solidify into a solid crystalline Said Solution, reacting said solution of aluminum maSS by Suitable means such as sheeting, flaking, permanganate with a member of the class con etc. Sisting of an oxide, hydroxide and carbonate, at Other permanganates Such as zinc, barium, a temperature within the range extending from lithium, though having a rather high solubility about 80° C. to and including the boiling point of in Water, will, after concentration, yield well 5 the Solution, and recovering the permanganate definable Crystals which can be separated and of Said class of alkali metal and ammonium per kept as such. manganates. is here considered 5. The method as set forth in claim 4 in which (as an alkali metal permanganate and is one of the Solution of the final reaction product is con the desirable permanganates which may be pro 20 centrated so that a substantial proportion of re \duced by this process. maining potassium containing impurity is precip The invention is particularly valuable in pro itated and said impurity is removed: 'ducing alkali metal, and alkaline earth per 6. The method as set forth in claim 4, in which manganates, that is those of groups I and II of the Solution of the final reaction product is con the periodic system. 5 centrated, so that a substantial proportion of re My copending application Serial No. 622,085 maining Sulfate containing impurity is precip discloses and claims the preparation of zinc and itated and said impurity is removed. ritagnesium permanganates. My Copending ap . The method as set forth in claim 4 in Which plication Serial No. 622,086 discloses and claims the member is sodium. the preparation of alkaline earth metal per 30 8. The method as set forth in claim 4 in which manganates. the member is lithium. Specifically the invention is applicable to the 9. The method as set forth in claim 4 in which production. Of Sodium, ammonium, and lithium the member is ammonium. permanganates in group I of the periodic sys 30. The method of producing a solution of tem; to the production of alkaline earth per 35 aluminum permanganate which comprises react Iaanganates. Such as barium, calciura and stron ing potassium permanganate and aluminum sui tium permanganates; and to the production of fate at a temperature not greater than about 80° permanganates of the Sub group of group II, such C. and in the presence of sufficient water to pro aS magnesium and Zinc permanganates. duce hydrated potassium aluminum sulfate crys What I claim as new, and desire to secure by tals. and a Solution of aluminum permanganate, Letters Patent, is: and separating the potassium aluminum sulfate 1. The method of forming a permanganate of from Said solution. the class consisting of alkali metal and aim monium permanganates, which comprises react THEODORE JASKOWIAK. ing a solution of aluminum permanganate with a member of the class consisting of an oxide, REFERENCES CITED hydroxide and carbonate of an alkali metal, aim monium hydroxide and ammonium carbonate, at The following references are of record in the a temperature within the range extending from file of this patent: about 80° C. to and including the boiling point 50 FOREIGN PATENTS of the Solution, and recovering the permanganate of said class of alkali metal and ammonium per Neinber Country Date manganates. 10,015 Great Britain ------1884 2. The method as set forth in clain l in which OTHER REFERENCES the merber is Sodium. 3. The method as set forth in claim 1 in which Parkes and Mellor: "Mellor's Modern Inorganic the member is ammonium. Chenistry,' Revised Ed., page 118 (1944).