Method for preparing electrolytic manganese/electrolytic manganese dioxide by cyclically leaching manganese oxide with sulfur and calcium

Abstract

The invention discloses a method for preparing electrolytic manganese / electrolytic manganese dioxide by cyclically leaching manganese oxide with sulfur and calcium, which comprises the following steps: reducing and decomposing gypsum generated by the system to obtain sulfur dioxide and calcium oxide; leaching manganese oxide ore slurry with sulfur dioxide gas; adding an oxidant into the slurry to remove iron and aluminum ions in the slurry, and adding a heavy metal vulcanizing agent to remove heavy metal ions in the slurry; carrying out solid-liquid separation on the purified slurry, wherein the separated liquid is an electrolyte for electrolysis, and the solid-phase washing separated liquid is used for preparing manganese oxide ore slurry; sending the separated liquid to the electrolysis step to carry out electrolysis, wherein the electrolytic manganese product or electrolytic manganese dioxide product is obtained at the cathode, and an anolyte containing sulfuric acid and manganese sulfate is obtained at the anode; and adding calcium oxide, which is obtained by gypsum decomposition, into the anolyte to generate calcium slurry, and separating, wherein the solution is used for washing slag, and the solid-phase gypsum is used for preparing sulfur dioxide gas and calcium oxide by decomposition. The invention provides an environment-friendly method capable of implementing closed cycle of sulfur and calcium resources and anolyte.

Description

Technical field: [0001] The invention relates to the hydrometallurgical technology of manganese-containing raw materials, in particular to a method for preparing electrolytic manganese and electrolytic manganese dioxide by utilizing manganese oxide ore with high efficiency and low consumption of sulfur and calcium resources. Background technique: [0002] Electrolytic manganese metal has a wide range of uses. In addition to being mainly used in the iron and steel industry for refining alloy steel, such as stainless steel, special alloy steel, stainless steel electrodes, etc., it can also be used in non-ferrous alloys, chemicals, medicine, food, analysis, scientific research, etc., so manganese deficiency Most countries usually reserve it as a strategic material. At present, my country's electrolytic manganese production capacity and production capacity account for about 98% of the world's total, 83% of China's electrolytic manganese metal is used for domestic consumption, an...

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Problems solved by technology

After electrolysis of manganese sulfate solution, metal manganese or manganese dioxide is obtained at the cathode, and an anolyte containing sulfuric acid and remaining manganese sulfate is generated at the anode. containing materials-hydrometallurgical method of manganese-containing raw materials (patent number: WO2004033738)", Improved hydrometallurgical processing of manganese containing materials-improved hydrometallurgical method of manganese-containing materials (WO2005012582), Chinese patent "using pyrolusite and pH buffer Exhaust gas desulfurization method using a composite absorbent as a composite absorbent (200510021926.X)”), which not only wastes manganese resources, but also causes serious wastewater pollution; The problem of sulfur balance in the system; if the method of discarding various sulfates is adopted, it will not only waste precious sulfur resources, but also cause secondary pollution problems

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