A method of processing poor manganese ore, sludge and dust ferroalloy furnaces

 

The invention relates to the processing of the poor manganese ore, in particular, ferromanganese nodules in the Baltic sea shelf, as well as sludge and dust Ferroalloy furnaces sulfuric acid method and can be used in the production of various manganese products. The method allows to extend the range of recycled poor manganese ore, to reduce the cost and simplify the process, reduce the consumption of acid and reducing agent, to increase productivity, to obtain a pure solution of sulphate of manganese in one stage. The method comprises leaching the material with sulfuric acid in the presence of a reducing agent. In use as a reducing agent sulfite-bisulfite solutions of ammonium in the mass ratio of ammonium bisulphite to the amount of sulfuric acid 1:0,52-1,155 total normal acid reagents from the stoichiometric required amount for the formation of MnSO4entered with sulfuric acid and the recovery sulfite-bisulfite solution of ammonium equal 110-133%. The process is carried out at pH 3.5 to 5.5 and a temperature of 30-70oC. 1 table.

The invention relates to the field of chemical technology of inorganic substances, and property named the sludge and dust Ferroalloy furnaces sulfuric acid method and can be used in the production of various manganese products.

A known method of processing of manganese ores and slimes leaching of spent electrolyte containing sulfuric acid, using as the reducing sulfur dioxide to dissolve high-valent manganese oxides contained in manganese ores and slimes at a temperature of 50-80o(Agladze R. I. Rational method of treatment of manganese ores and slimes. Mining magazine, 12, 1939, S. 39).

The disadvantage of this method is the necessity of the implementation process using gaseous toxic substances, in particular sulphur dioxide, which complicates the process, it is not possible to obtain suspensions with good filtering properties, necessitates use of a large number of filtration equipment and bulky gas purification schemes worsen working conditions.

The closest technical solution of the present invention is a method of processing the mn containing dust Ferroalloy furnaces, including the leaching of mn containing material with a solution of sulfuric acid in the presence of a reducing agent, in which the reducing agent is a mixture of a solution of sodium sulfite and sulfuric acid in the ratio of 1,1-1,38:atrium 1:4.09 to 4,74 (A. C. The USSR 1054437, With 22 In 47/00, publ. 15.11.83). The process is carried out at room temperature and pH 1-3. After phase separation, the filtrate is processed by a known method.

The disadvantage of this method is the limited range of recycled mn containing products, high consumption of sulfuric acid and reductant, the need for treatment of a solution of sulphate of manganese impurities in further processing.

The technical result of the invention is the extension of the range of recycled mn containing products, cost reduction and simplification of the process, reducing consumption of sulfuric acid and reductant, increase filtration performance when separating the liquid and solid phases, obtaining pure solution of sulphate of manganese in one stage.

The technical result is achieved by a method for processing poor manganese ore, sludge and dust Ferroalloy furnaces, which comprises leaching the material with sulfuric acid in the presence of a reducing agent. In use as a reducing agent sulfite-bisulfite solutions of ammonium in the mass ratio of ammonium bisulphite to the amount of sulfuric acid 1:0,52-1,155 total normal key is acid and restorative sulfite-bisulfite solution of ammonium equal 110-133%. The process is carried out at pH 3.5 to 5.5 and a temperature of 30-70oC.

Use as a reductant, the sulfite-bisulfite solutions of ammonium produced during ammonia exhaust gas cleaning sulfuric acid production, leads to the replacement of a significant part of the road sulphuric acid on the bisulfite ion, which are oxidized by manganese, bound in manganese sulfate, and carrying out the leaching of manganese at pH 3.5 to 5.5 and a temperature of 30-70oWith allows you to get a well-divided pulp with a small amount of impurities in the liquid phase.

The essence of the process is illustrated by examples.

Example 1 1000 kg poor manganese ore, such as iron-manganese nodules containing 21% Mn, 13% Fe, 2% MgO, 2% CaO, 25% SIO, SIS2, 5.2% of Al2About3, 2% P2About5, 0.2% of SO3that 1.5% of Ctotalthat 1.4% H2O, 1.5%2Oh, 1.3% PA2Oh, 10% loss on ignition, mixed with 3184 kg of recycled water, 300 kg 95,7% sulfuric acid and 890 kg sulfite-bisulfite solution of ammonium containing 28% NH4HSO35% of (NH4)2SO3, 4% (NH4)2SO4. The total rate of acid reagents from the stoichiometric required amount of education MnS4entered with sulfuric acid leaves 1:1,155. Leaching is carried out for 3 hours at a temperature of 50oC at pH 3.5. In the gas phase is allocated 158 kg of water. The pulp in the amount 5216 kg is directed to the separation of phases. The performance of the filter on the vacuum filter is 300 kg/(m2h). The precipitate is washed with water in an amount of 1000 kg and sent for recycling. Wash water is directed to the leaching. The filtrate number 4224 kg, containing 199 kg MP (547 kg MnS4), mixed with 1446 kg of a solution of ammonium carbonate (11% CO2). The pulp in the amount of 5670 kg filtered, the precipitate washed. The filtrate is sent for processing into fertilizer. The amount of sludge 844 kg, the cake moisture of 50%. The precipitate is dried and calcined at a temperature of 650oC. the Finished product in the amount of 300 kg is a manganese concentrate and contains 63% manganese, 1.5% sulfate, the amount of manganese in the product is 189 kg

Example 2 1000 kg of ferromanganese nodules, containing 13.7% MP, 18% Fe, 1.8% of MgO, up to 1.5% CaO, 25% SIO, SIS2, 6% Al2About3, 3% P2O5and 0.5% SO3, 1,5%total, 1.4% Fromcarb, 1.5%2Oh, and 1.0% Na2About 9% loss on ignition, mixed with 3155 kg of recycled water, 196 kg 95,7% sulfuric acid and 657 kg sulfite-bisulfite solution ammonia acid reagents from the stoichiometric required amount of education nS04entered with sulfuric acid and sulfite-bisulfite solution of ammonium is 116,9%. The ratio of NH4HSO3to H2SO4is 1:0,94. Leaching is carried out for 3 hours at a temperature of 60oC at pH 4.5. In the gas phase is allocated 158 kg of water. The pulp in the amount of 4850 kg is directed to the separation of phases. Filtration performance is 250 kg/(m2h). The precipitate is washed with water in an amount of 1166 kg Wash water is directed to the leaching. The filtrate number 3589 kg, containing 130 kg MP (357 kg MnSO4), processed analogously to example 1. The final product of the number of 192 kg contains 64% manganese and 1% sulfate, the amount of manganese in the product of 124.8 kg

Example 3 1000 kg slurry Ferroalloy furnaces containing 8.9% MP, 20% Fe, 2.1% of MgO, 2% CaO, 30% SIO, SIS2, 6.2% of Al2About3, 4% P2O55% of SO350% of N2Oh, and 1.5% K2O, 1.3% of Na2O, 6% loss on ignition, mixed with 1430 kg of recycled water, 119 kg 95,7% sulfuric acid and 459 kg sulfite-bisulfite solution of ammonium containing 32% NH4HSO3, 7% (NH4)2SO3, 3% (NH4)2SO4. The total rate of acid reagents from the stoichiometric required amount of education MnS4S3to H2SO4is 1:0,77. Leaching is carried out for 3 hours at a temperature of 70oC at pH 5.5. In the gas phase is allocated 158 kg of water. The pulp in the amount of 3850 kg is directed to the separation of phases. Filtration performance is 230 kg/(m2h). The precipitate is washed with water in an amount of 1400 kg Wash water is directed to the leaching. The filtrate number 2445 kg, containing 82,7 kg MP (227 kg MnS4), processed analogously to example 1. The finished product in the amount of 125 kg contains 65% manganese and 0.8% sulfate, the amount of manganese in the finished product is 81,1 kg

Example 4 1000 kg mn containing dust Ferroalloy furnaces containing 40-42% MPtotal, 51-57% MnO2, 8% F2O3, 3,06% CaO, 1.92% Of MgO, 1,57% S, 0.37% Of P, 2.54% And Al2About3that becomes 9.97% SIO, SIS2, 0,73% N2Oh, 6,76% loss on ignition, mixed with 3000 kg of recycled water, 376-489 kg 95,7% sulfuric acid and 2273-2955 kg sulfite-bisulfite solution of ammonium containing 32% NH4HSO3, 8% (NH4)2SO3, 6% (NH4)2SO4. The total rate of acid reagents from the stoichiometric required amount of education MnS4entered with sulfuric acid, and sulfur-bisulfite carried out for 2 hours at a temperature of 30oC at pH 3.5. In the gas phase is allocated 158 kg of water. The pulp in the number 7567 kg is directed to the separation of phases. Filtration performance is 300 kg/(m2h). The precipitate is washed with water in an amount of 1000 kg of Wash water is directed to the leaching. The filtrate number 6757 kg, containing 390 kg MP (1070 kg MnS4), processed analogously to example 1. The final product of the number 589 kg contains 65% manganese and 0.5% sulfate, the amount of manganese in the product is 383 kg

The decrease in the ratio of NH4HSO3/H2SO4below 1:0,52 leads to incomplete leaching of manganese in the solution due to lack of reductant, the increase in the ratio above 1:0,94 will lead to acidification of the pulp and release into solution of impurities of iron and phosphorus. The stoichiometric reduction of the norm of acid reagents below 110% leads to decrease leaching of manganese in solution, increasing the stoichiometric rules above 133% leads to strong acidification of the pulp and the transition into the solution impurities. Lowering the pH below 3.5 to degrade the filtration properties of the pulp and leads to extraction in a solution of compounds of iron and phosphorus. Raising the pH above 5.5 leads to reduction in the degree of extraction of manganese, the temperature rise above 70oWill result in the desorption of SO2from the solution.

The table shows the comparative performance of the proposed and known methods.

As can be seen from the table, the proposed method reduces the consumption of sulfuric acid in 4-4,5 times and reductant 2-3 times due to the replacement of the solution of sulfite and sodium sulfite-bisulfite solution of ammonia, increasing the pH and temperature of the process increases from 11 to 15 times the performance of the filter, formed of pure solutions of sulphate of manganese, which do not require additional purification in the subsequent processing.

The proposed method allows to extend the range of recycled mn containing raw materials for high quality concentrate.

Claims

A method of processing poor manganese ore, sludge and dust Ferroalloy furnaces, comprising leaching the material with sulfuric acid in the presence of a reducing agent, characterized in that in use as a reducing agent sulfite-bisulfite solutions of ammonium in the mass ratio of ammonium bisulphite to the amount of sulfuric acid 1: 0,52-1,155 total normal acid reagents from stechiometric the fit-bisulfite solution of ammonium equal 110-133%, the process is carried out at pH 3.5 to 5.5 and a temperature of 30-70oC.

 

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FIELD: metal recovery, in particular noble metals from technologically proof raw materials.

SUBSTANCE: method includes raw grinding to 0.2 mm; blending with batch containing halogen salts and/or oxygen-containing salts, and mixture opening: cake cooling, leaching with simultaneous reaction pulp agitation with hot water, and metal recovery from solution and insoluble residue. Opening is carried out in electrical furnace at 100-120oC preferably at redox potential of 1.8-2.6 V, by elevating of temperature up to 450-560oC at rate of 8-10oC/min and holding for 1-7 h at highest mixture redox potential. Opened and cooled cake is grinded and leached in opened agitator.

EFFECT: environmentally friendly method with increased yield; utilization of unconventional noble and non-iron metal sources.

1 cl, 2 tbl

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