A method of producing manganese dioxide

 

(57) Abstract:

The invention relates to hydrometallurgy manganese and can be used to obtain active manganese dioxide from poor carbonate manganese ores. The method includes grinding the original mn containing raw material, the leaching of manganese spent electrolyte at temperatures above 50°C, hydrolytic cleaning solution from impurities in the presence of an oxidant and sequential processing oxyhydrate a precipitate obtained by the hydrolytic treatment of rinsing water containing manganese, and lime milk to pH 6-7 and the preparation of the electrolyte. Subsequent electrolysis to produce manganese dioxide lead from the hot electrolyte on activated titanium anodes in the anode current density And 100-175/m2and a cathode current density of 300-1000 a/m2. While grinding the original mn containing raw material is carried out until a particle size of 0.1 mm, as the oxidant used manganese oxides in the waste electrolytic manganese dioxide (EDM), oxidized manganese ore or chemical concentrates. The proposed method provides obtaining of electrolytic manganese dioxide-modification with high electron is dermatologii manganese and can be used to obtain active manganese dioxide from poor carbonate manganese ores.

The prior art method for processing manganese ore with production of manganese dioxide (RF patent N 2027675, MKI C 25 B 1/00, 1992), including the production of manganese concentrate, grinding it to a maximum particle size of 100-400 μm. From the last cook 40-60% aqueous suspension of manganese concentrate, which serves to leaching in acid, followed by neutralization of the suspension with the milk of lime to pH 5.5 to 6.5. Preparation of electrolyte lead separation of liquid from solid, solid repulping in water, separating the slurry, and the aqueous phase serves on the sorption, the electrolyte is divided into two parts in the ratio 1:8-10; from the lower part of the produce crystalline salt of manganese, and most are served by electrolysis to produce manganese dioxide in the form of sludge at the anode, which is conducted in two stages, the first stage serves the electrolyte with a salt concentration of manganese 160-120 g/l, the second - 120-60 g/l, and at both stages of the electrolysis is carried out at a current density of 0.8 to 1.3 a/DM2in the pots with lid.

Described known method is complicated by the stage of obtaining manganese concentrate from the original ore, as well as two-stage electrolysis.

A method of obtaining manganese dioxide from marvanova manganese raw materials: pre - in the presence of an oxidant solution of the second stage and the second stage - the final pre-leaching partially leached feedstock after intermediate gidrotsiklonirovaniya pulp in the presence of a reducing agent regenerated electrolyte with subsequent re-classification of the pulp. According to a known method hydrolytic purification from impurities, and then subjected to electrolysis solution first (preliminary) stage of leaching.

The disadvantage of this method is complex circuit implementation, which is very time consuming to implement.

The closest in technical essence is a method of producing manganese dioxide (an Overview. Series 2, episode 1, "the Chemical enrichment of refractory manganese ores", M, 1975, dermatopharmacy, S. 29), comprising grinding the mn containing raw material, the leaching of manganese spent electrolyte at a temperature above the 50oC, hydrolytic cleaning solution from impurities in the presence of an oxidant and processing of lime milk preparation from the filtered electrolyte solution and subsequent electrolysis to produce manganese dioxide from the hot electrolyte at the anode the ID of manganese does not meet the requirements of the highest grade GOST 25823-83 (the content of manganese dioxide at least 91,65%, and each of the impurities is not more than 0,003-0,008%).

The technical result of the invention is to create a way more high-quality manganese dioxide in accordance with a high level of GOST 25823-83.

The technical result is achieved by the fact that in the known method of producing manganese dioxide, comprising grinding the mn containing raw material, the leaching of manganese spent electrolyte at a temperature above the 50oC, hydrolytic cleaning solution from impurities in the presence of an oxidant and processing of lime milk preparation from the filtered electrolyte solution and subsequent electrolysis to produce manganese dioxide from the hot electrolyte according to the invention the cleaning of impurities are consistent treatment oxyhydrate a precipitate obtained by the hydrolytic treatment of rinsing water containing manganese, and lime milk to pH 6-7, and electrolysis are on activated titanium anodes in the anode current density And 100-175/m2and cathode density 300-1000 a/m2.

Grinding the original carbonate manganese ore or concentrate lead to a particle size of 0.1 mm as the oxidant can ispolzovatblizhny manganese ore or chemical concentrates.

Leaching of finely source of carbonate manganese ore or concentrate the spent electrolyte allows almost complete transfer of manganese in the solution for one stage.

Cleaning of impurities is subjected to a pulp after leaching, or a filtered solution. The choice of cleaning depends on the direction of disposal of solid wastes, which is determined by the market conditions. With the purpose of obtaining a product for the production of pigment is hydrolytic purification of the filtered solution.

Hydrolytic purification of the pulp or the filtered solution is carried out in the presence of an oxidant. As the oxidant used oxides of manganese that can be added in the form of waste EDM (non-standard, spillages etc) that exist in industrial production, oxidized manganese ore or chemical concentrates, and oxygen. When ferrous iron is oxidized to ferric, which precipitates as hydroxide at a pH of 3-4.

Holding hydrolytic purification of the pulp or the filtered solution at pH 6-7 provides maximum precipitation of all harmful for the electrolysis of impurities: madalay to conduct final purification of these impurities due to the developed surface of iron hydroxide, that leads to higher quality EDM.

Adding oxyhydrate precipitate, obtained by the hydrolytic treatment of rinsing water and containing manganese at the stage of hydrolytic cleaning solution after leaching allows you to smoothly bring the pH to 6-7, preventing resultant deposition rates and, consequently, losses of manganese, as well as to dispose of the manganese contained therein, thereby increasing the extraction of manganese from the source of raw materials.

The electrolysis is carried out at an anode current density of 100-175 a/m2and cathode density 300-1000 a/m2. The use of activated titanium anodes allows you to raise the anodic current density of more than 100 a/m2and, consequently, to improve the performance of the electrolysis. The increase in cathodic current density increases the overpotential of hydrogen and promotes the deposition on the cathode of trace contaminants such electronegative metals, such as chromium, zinc, Nickel, iron (2+) and other, which leads to higher quality manganese dioxide, and an additional purification of the electrolyte.

The method is as follows.

Crushed to-0.1 mm original carbonate manganese ore or concentrate immediately leached when temperature is Oh acid. In the solution passes almost all the manganese and impurities, including ferrous iron.

The pulp after leaching, or a filtered solution is subjected to hydrolytic purification from impurities in the presence of an oxidant by sequential processing of oxyhydrate sediment and lime milk to pH 6-7. As the oxidant used manganese oxides as waste EDM, oxidized manganese ore or chemical concentrates, and oxygen. Oxyhydrate precipitate obtained when the hydrolytic treatment of rinsing water. When this occurs, the oxidation of divalent iron to trivalent, hydrolysis of ferric sulfate with getting iron hydroxide and precipitation of impurities.

Obtained after filtering the mn containing solution is directed to the preparation of the electrolyte and subsequent electrolysis to produce EDM. Electrolysis lead from the hot electrolyte on activated titanium anodes in the anode current density And 100-175/m2and a cathode current density of 300-1000 a/m2depending on the electrolyte composition.

The spent electrolyte, representing the regenerated sulfuric acid, return on leaching.

235,7; Zn 0,028; Pb 0,01: Cr 0,042; Cu 0,013; Ni 0,023; Co 0,007.

The manganese in the ore is represented by carbonates (calcium rhodochrosite).

Sample crushed to-0.1 mm initial ore was videlacele spent sulfuric acid electrolyte at a temperature of 60oC for 2 hours until pH 2. The composition of spent electrolyte, g/DM3: H2SO444,5; Mn 25,0; Fe 0,0005; Zn 0,0012; Pb 0,0009; Cr 0,0016; Cu 0,00016; Ni 0,0041; Co 0,0020. To make up for losses added sulfuric acid from the calculation of 277 kg/t ore. Extraction of manganese in the solution amounted to 98.1%.

The pulp after leaching was filtered. The composition of the mn containing solution, g/DM3: Mn 57,2; Fe 1,24; Ca 0,50; 2,00 Mg; Al not OBN.; Zn 0,15; Pb 0,004; Cr 0,017; Cu 0,0046; Ni 0,0448; Co 0,0158. Into the solution was introduced EDM (as oxidant) at the rate of 0.6 kg per cubic meter and then processed sequentially oxyhydrate sediment and lime milk at a temperature of 95oC to pH 6.5 with stirring and aeration air for 2 hours. Oxyhydrate precipitate obtained during the hydrolytic treatment of rinsing water, its composition, %: Mn 18,6; Fe 1,4; Ca 17,6; Mg 2,6; Al of 0.05; Zn 0,001; Pb < 0,001; Cr 0,005; Cu 0,002; 0,005 Ni; Co 0,001.

The slurry was filtered. The solution after purification from impurities had composition, g/Davila 94,25%.

From purified mn containing solution prepared electrolyte bringing manganese concentration to 50 g/DM3. The electrolysis is conducted at a temperature of 95oC, anode current density of 150 a/m2and cathode density of 1000 a/m2. The anodes were made of activated titanium grade VT1-0, the cathodes of steel, brand 06HN28MDT.

The voltage across the bath was stable - 3-4 In, the current output was 95-96% of the energy consumption of 2.6 kWh/kg

At the cathode the precipitate impurities in the amount of 0.06% of the output of the EDM. 95% of the sediment consists of insoluble calcium sulphate. Estimated sediment composition,%: Ca 24-25; Mn 1-2: 0,5 Mg; Fe of 0.1; Cu 0,1; Ni 0,3-0,5; Co ~ 1,0.

At the anode of the obtained electrolytic manganese dioxide - modification, corresponds to the highest grade GOST 25823-83 with high electrochemical activity. The resulting EDM tested in serial products of type "Corundum" on the top-Ufaley sue "Arelement showed high performance. The composition of the obtained EDM and the requirements of GOST 25823-83 shown in the table.

Thus, according to the invention obtained manganese dioxide - modification with high electrochemical activity corresponds to the highest grade GOST 25823-83.

2and a cathode current density of 300-1000 a/m2.

2. The method according to p. 1, characterized in that the grinding mn containing source of raw materials lead to a particle size of 0.1 mm

3. The method according to p. 1 or 2, characterized in that as the oxidant used manganese oxides in the waste electrolytic manganese dioxide (EDM), oxidized manganese ore or chemical concentrates.

 

Same patents:

The invention relates to methods for producing components of a fuel cell

The invention relates to the field of processing solutions physico-chemical and electrochemical technologies

The invention relates to the field of processing solutions physico-chemical and electrochemical technologies

The invention relates to a method of extracting bromine from natural waters, brines and technological solutions containing bromide and chloride ions

The invention relates to an improved process for the preparation of triftoratsetofenona, the original product for the synthesis of derivatives triftoratsetata used in fine organic synthesis, pharmaceuticals, fungicides, extractants, catalysts

The invention relates to an electrolytic method for selective extraction and recycling of silver from a solution of nitric acid, containing in the form of Ag(I)

The invention relates to a device for producing oxygen and hydrogen by electrolysis of aqueous solutions of alkali and can be used either as an element of the power system of the internal combustion engine or an apparatus for flame treatment of materials

The invention relates to a device for producing oxygen and hydrogen by electrolysis of aqueous solutions of alkali and can be used either as an element of the power system of the internal combustion engine or an apparatus for flame treatment of materials

The invention relates to electrochemistry, in particular to the improvement of the electrode is particularly useful for electrochemical processes in which the formation of gaseous products, and to methods of its regeneration

The invention relates to the field of electrochemical productions, in particular to a method of electrolysis of aqueous solutions of hydrochloric acid

The invention relates to metallurgy manganese and can be used in the hydrometallurgical processing of vysokofosforistye carbonate and mixed manganese ores and concentrates, or waste, resulting in their physical enrichment for producing enriched low-phosphorus manganese concentrate required for the production of high-grade manganese alloys or direct alloying of steel
The invention relates to hydrometallurgy manganese

The invention relates to the field of integrated utilization of technogenic raw materials, namely waste chemical current sources (CCS) margantsevskogo system, hydrometallurgical methods
The invention relates to metallurgy, and in particular to methods of obtaining manganese and can be used to obtain okuskovannogo low-phosphorus manganese concentrate

The invention relates to ferrous metallurgy, in particular to the processing of manganese nodules to obtain cobalt, copper, Nickel, manganese
The invention relates to the field of non-ferrous metallurgy, in particular to methods for preconcentration of manganese from waste water from the processing of Converter slag containing vanadium

The invention relates to metallurgy manganese and can be used in the hydrometallurgical processing of vysokofosforistye carbonate and manganese ore and waste from the production of ferromanganese to obtain manganese concentrate

The invention relates to the field of processing of secondary raw materials containing non-ferrous metals, in particular by mechanical methods of destruction stakanchikov elements manganese-zinc system type element 373, item 343

The invention relates to the metallurgy of noble metals, in particular silver refining
Up!