Processing of manganous sulphate/dithionate liquors derived from manganese resource material
The process concerns hydrometallurgical processing of manganese sulphate and manganese dithionate containing liquors and recovery of water therefrom. Sodium sulphate and/or sodium dithionate containing liquors are derived from manganese sulphate and manganese dithionate containing liquids, which are then cooled to produce crystals of sodium sulphate decahydrate and sodium dithionate dehydrate. The sodium sulphate decahydrate and sodium dithionate dehydrate crystals are then heated to a temperature sufficient to decompose the sodium sulphate decahydrate crystals to form anhydrous sodium sulphate crystals, sodium dithionate hydrate crystals and water, after which water is removed from the sodium sulphate and sodium dithionate hydrate crystal. The sodium sulphate and sodium dithionate dehydrate crystals are then heated to form anhydrous sodium sulphate, sulfur dioxide and water or steam. The anhydrous sodium sulphate is then separated from the sulfur dioxide and water.
1. A process for hydrometallurgical processing of manganese sulphate and manganese dithionate containing liquors and recovery of water therefrom, comprising the steps of:
deriving sodium sulphate and/or sodium dithionate containing liquors from manganese sulphate and manganese dithionate containing liquors;
crystallizing sodium sulphate decahydrate and sodium dithionate dehydrate by cooling sodium sulphate/sodium dithionate containing liquors with or without a vacuum;
heating the sodium sulphate decahydrate and sodium dithionate dehydrate crystals to a temperature sufficient to decompose the sodium sulphate decahydrate crystals to form anhydrous sodium sulphate crystals, sodium dithionate hydrate crystals and water;
removing water from the sodium sulphate and sodium dithionate hydrate crystals;
heating the sodium sulphate and sodium dithionate dehydrate crystals to form anhydrous sodium sulphate, sulfur dioxide and water or steam; and
separating the anhydrous sodium sulphate from the sulfur dioxide and water.
2. The process of claim 1 , wherein the sodium sulphate and sodium dithionate containing liquors are filtrates or cetrifugates derived from precipitation of manganous carbonate from leached manganese resource material by reaction of manganous sulphate and manganous dithionate with a carbonate.
3. The process of claim 2 , wherein the carbonate is sodium carbonate.
4. The process of claim 3 wherein the sodium carbonate is an aqueous solution.
5. The process of claim 1 , wherein the sulfur dioxide is suitable for use in leaching manganese resource material.
6. The process of claim 1 , wherein the sodium sulphate and sodium dithionate containing liquors are nanofiltered to remove water therefrom.
7. The process of claim 1 , wherein the manganous sulphate and manganous dithionate are derived from leaching of manganese resource material with sulfuric acid and sulfurous acid.
8. The process of claim 7 , wherein the step of leaching the manganese resource material includes the use of sulfur dioxide.
9. The process of claim 1 , including the step of precipitating aluminum, arsenic, silica and iron by a pH adjustment and aeration from the manganous sulphate and manganous dithionate liquors.
10. The process of claim 1 , including the step of precipitating one or more metal impurities from the manganous sulphate and manganous dithionate liquors by sodium hydrosulphide.
11. The process of claim 9 , wherein the metal impurities comprise one or more of the following metals: zinc, copper, lead, molybdenum, nickel and cobalt.
12. The process of claim 2 including using the sulfur dioxide and water in the step of leaching.
13. The process of claim 2 , wherein manganese carbonate solids are derived along with the sodium sulfate and sodium dithionate containing liquors.
14. The process of claim 13 , wherein the manganese carbonate solids are separated from the sodium sulfate and sodium dithionate by filtration or centrifugation.
15. The process of claim 14 , wherein the manganese carbonate solids are water washed to remove soluble impurities and wherein the water washed manganous carbonate solids are reacted with a sulfuric acid to produce dithionate free manganous sulphate suitable for manganese metal electrowinning.
16. The process of claim 1 , wherein the temperature of the cooling step is −40° C. or higher at atmospheric pressure.
17. The process of claim 1 , wherein the temperature of the cooling step is −40° C. or higher under vacuum.
18. The process of claim 17 , wherein the temperature of the cooling step is 20° C. or higher.
19. The process of claim 18 , wherein the cooling temperature is approximately 29° C. at 0.0373 atmospheres in a first stage of cooling and approximately 20° C. in a second stage of cooling.
20. The process of claim 1 , wherein the step of cooling includes two stages, under vacuum, wherein the first stage produces a concentrate of sodium sulphate and/or sodium dithionate containing liquors and the second stage produces sodium sulphate decahydrate and sodium dithionate crystals from the first-stage concentrate.