CN103757247A

CN103757247A - Method for leaching manganese carbonate ore

Info

Publication number: CN103757247A
Application number: CN201310736404.2A
Authority: CN
Inventors: 龙炳清; 陈建文; 邓国海
Original assignee: Sichuan Normal University
Current assignee: Sichuan Normal University
Priority date: 2013-12-29
Filing date: 2013-12-29
Publication date: 2014-04-30

Abstract

The invention discloses a method for leaching manganese carbonate ore. The method comprises the steps of adding manganese carbonate ore powder into a reaction kettle which is resistant to the corrosion of sulfuric acid and pressure, and adding a sulfuric acid solution and sodium sulfite to leach.

Description

The leaching method of manganese carbonate ore

Technical field

The present invention relates to a kind of leaching method of manganese carbonate ore.

Background technology

Manganese carbonate ore is the important source material of producing the materials such as manganese metal, manganous sulfate, Manganse Dioxide, manganous nitrate.Wet processing is the main technique of producing above-mentioned materials, leaches the operation operation that is absolutely necessary in this technique.In producing the wet processing of manganese metal, manganous sulfate, Manganse Dioxide, substantially adopt sulfuric acid leaching system.Owing to containing certain MnO in manganese carbonate ore ₂, MnO ₂be insoluble to sulfuric acid, cause while adopting sulfuric acid leaching manganese carbonate ore, the leaching yield of metal target manganese is not high, causes the wasting of resources.Although add Fe in Leaching Systems ²⁺, the reductive agent such as glucose can improve the leaching yield of manganese, but add Fe ²⁺can increase the weight of the burden that subsequent solution purifies, add the leaching velocity of glucose etc. slower, leach energy consumption and strengthen.The leaching method that exploitation leaching yield is high, leaching velocity is fast, energy consumption is low, do not increase the manganese carbonate ore of subsequent process burden has larger practical value.

Summary of the invention

The problem leaching for current manganese carbonate ore, the object of the invention is to find that a kind of leaching yield is high, leaching velocity is fast, energy consumption is low, do not increase the leaching method of the manganese carbonate ore of subsequent process burden, it is characterized in that granularity≤180 object manganous carbonate breeze to add in sulfuric acid corrosion resistant and withstand voltage reactor, under the condition of reactor Exhaust Open and inlet close, add sulphuric acid soln to carry out the leaching of first stage, leach the CO producing ₂from venting port, discharge.Work as CO ₂when gas is substantially drained, add sodium sulfite solution, close venting port and carry out the airtight leaching of subordinate phase.After subordinate phase leaches and finishes, pass into industrial pure oxygen and be oxidized leaching, the slurry of emitting in reactor after oxidation finishes carries out solid-liquid separation, obtains required infusion solution.Leached mud washes with water, and washing water are used for preparing sulphuric acid soln for leaching, and the waste residue after washing send slag field to deposit.The sulfuric acid of leaching process add total amount be manganese in manganese carbonate ore theoretical consumption 105%～120%, sulfuric acid adds total amount to comprise newly to add contained sulfuric acid amount in the solution that returns to leaching process that sulfuric acid amount and subsequent process produce, washing water.Mn for the starting point concentration of the sulphuric acid soln sulfuric acid that leaches in required leach liquor ²⁺concentration is determined, is calculated as follows:

Mn in sulfuric acid concentration=required leach liquor ²⁺the sulphuric acid soln Mn of concentration-for leaching ²⁺starting point concentration (1)

Each concentration unit of calculating formula is mol/L.

For leach in the breeze weight of kg with for leaching the ratio in the volume of the solution of L, be called for short solid-to-liquid ratio and be calculated as follows definite:

Solid-to-liquid ratio=1: leach the required sulfuric acid total amount ÷ sulfuric acid concentration (2) of every kg breeze

In calculating formula, leach the required sulfuric acid total amount of every kg breeze in g, sulfuric acid concentration is in g/L.

The temperature of leaching process is 50 ℃～70 ℃, and stirring velocity is 50 r/min～130 r/min.The add-on of S-WAT is by MnO contained in breeze ₂restore All is Mn ²⁺103%～120% of required theoretical amount.

The extraction time of first stage is 1h～2h.The extraction time of subordinate phase is 1h～2h.It is 0.5h～1.5h that leach liquor is carried out to oxidization time, and the relative pressure of oxidising process is 0.1Mpa～0.3MPa.

The object of the present invention is achieved like this: the object of the present invention is achieved like this: the leaching process of first stage is mainly by sulfuric acid and MnCO ₃, FeCO ₃, Fe ₂o ₃there is following chemical reaction:

MnCO ₃ + H ₂SO ₄ = MnSO ₄ + CO ₂ + H ₂O

FeCO ₃ + H ₂SO ₄ = FeSO ₄ + CO ₂ + H ₂O

Fe ₂O ₃ + 3H ₂SO ₄ = Fe ₂(SO ₄) ₃ + 3H ₂O

Fe ₂(SO ₄) ₃ + 6H ₂O = 2Fe(OH) ₃ + 3H ₂SO ₄

In the first leaching stage, most MnCO ₃leached and enter solution, part Fe is leached, and along with the carrying out of leaching process, the acidity of solution reduces, and enters the part Fe of solution ³⁺hydrolysis reaction occurs to be entered in leached mud.

In the second leaching stage, except proceeding, the reaction of first stage, MnO mainly to occur ₂and Fe ³⁺reduction reaction:

MnO ₂+ Na ₂SO ₃ + H ₂SO ₄ = MnSO ₄ + Na ₂SO ₄ + H ₂O

Fe ₂(SO ₄) ₃ + Na ₂SO ₃ + H ₂O = 2FeSO ₄ +Na ₂SO ₄ + H ₂SO ₄

MnO ₂ + 2FeSO ₄ + 2H ₂SO ₄ = Fe ₂(SO ₄) ₃ + MnSO ₄ + 2H ₂O

Due to Na ₂sO ₃reductibility stronger, MnO ₂oxidisability also stronger, both are easy to occur chemical reaction, realize thus MnO ₂leach more completely.Because reaction is carried out in confined conditions, Na ₂sO ₃the SO decompositing under acidic conditions ₂by stirring, enter solution (SO ₂in solution, have certain solubleness) and MnO ₂reaction is consumed, and whole system is carried out under pressure-fired.

Because the reduction of subordinate phase is leached, the Fe in solution is partly Fe ²⁺form, unfavorable to follow-up deironing (generally adopting neutralization precipitation method), so pass into oxygen, be oxidized to Fe ³⁺.

Outstanding advantages of the present invention is: through above-mentioned series reaction, finally make the Mn in manganese carbonate ore substantially leach completely, improved the leaching yield of Mn, reduce the wasting of resources, also to subsequent solution, do not purify and bring difficulty, thereby save production cost; Due to Na ₂sO ₃be easy to and MnO ₂reaction, so reduction leaching process speed is fast, reduction leaching process carries out in confined conditions, has avoided SO ₂the environmental pollution that produces of effusion; Can be according to the needs of subsequent process, according to the grade of manganous carbonate breeze with for the Mn of the sulphuric acid soln of leaching process ²⁺concentration (Mn ²⁺rework solution by subsequent process is brought into), the sulfuric acid total concn that is used for the sulphuric acid soln of leaching process by control is carried out flexible, adapts to wide.

specific implementation method

embodiment 1: 1000g manganous carbonate breeze (is contained to bivalent manganese 25.2%, tetravalence manganese 3.1%, Fe ₂o ₃10.7%, particle diameter 180 orders) adding volume is in the stainless steel cauldron of 5L, adds the sulphuric acid soln 2700ml of 2.0mol/L, stirs (stirring velocity 80r/min) and leach 1h at 60～70 ℃.Then add Na ₂sO ₃solution 300mL is (containing Na ₂sO ₃74g), continue airtight agitation leach 1h at this temperature.After finishing, leaching passes into the airtight stirring oxidation of industrial pure oxygen 0.5h(relative pressure 0.1MPa).After finishing, oxidation carries out the washing of liquid-solid separation and leached mud.According to the assay result of the leached mud after cleaning, leach the washing of carrying out liquid-solid separation and leached mud after finishing.According to the assay result of the leached mud after cleaning, the leaching yield of manganese is 98.5%.

Embodiment 2: 10kg manganous carbonate breeze (is contained to bivalent manganese 25.2%, tetravalence manganese 3.1%, Fe ₂o ₃10.7%, particle diameter 180 orders) adding volume is in the stainless steel cauldron of 200L, the residual electrolyte that adds the sulphuric acid soln 160L(sulphuric acid soln of 0.35mol/L to be produced by electrolytic manganese factory, and raffinate is containing Mn ²⁺13.5g/L, H ₂sO ₄34.5g/L).At 50～60 ℃, stir (stirring velocity 70r/min) and leach 2h.Then add Na ₂sO ₃solution 3L is (containing Na ₂sO ₃760g), continue airtight agitation leach 2h at this temperature.After finishing, leaching passes into the airtight stirring oxidation of industrial pure oxygen 1h(relative pressure 0.3MPa).After finishing, oxidation carries out the washing of liquid-solid separation and leached mud.According to the assay result of the leached mud after cleaning, the leaching yield of manganese is 99.3%.

Claims

1. the leaching method of a manganese carbonate ore, it is characterized in that granularity≤180 object manganous carbonate breeze to add in sulfuric acid corrosion resistant and withstand voltage reactor, under the condition of reactor Exhaust Open and inlet close, add sulphuric acid soln to carry out the leaching of first stage, leach the CO producing ₂from venting port, discharge, work as CO ₂when gas is substantially drained, add sodium sulfite solution, close venting port and carry out the airtight leaching of subordinate phase, after subordinate phase leaches and finishes, passing into industrial pure oxygen is oxidized leaching, the slurry of emitting in reactor after oxidation finishes carries out solid-liquid separation, obtain required infusion solution, leached mud washes with water, washing water are used for preparing sulphuric acid soln for leaching, waste residue after washing send slag field to deposit, the sulfuric acid of leaching process add total amount be manganese in manganese carbonate ore theoretical consumption 105%～120%, the solution that returns to leaching process that sulfuric acid adds total amount to comprise newly to add sulfuric acid amount and subsequent process to produce, contained sulfuric acid amount in washing water, Mn for the starting point concentration of the sulphuric acid soln sulfuric acid that leaches in required leach liquor ²⁺concentration is determined, is calculated as follows: Mn in sulfuric acid concentration=required leach liquor ²⁺the sulphuric acid soln Mn of concentration-for leaching ²⁺starting point concentration, each concentration unit of calculating formula is mol/L, for leach in the breeze weight of kg with for leaching the ratio in the volume of the solution of L, being called for short solid-to-liquid ratio is calculated as follows definite: solid-to-liquid ratio=1: leach the required sulfuric acid total amount ÷ sulfuric acid concentration of every kg breeze, in calculating formula, leach the required sulfuric acid total amount of every kg breeze in g, sulfuric acid concentration is in g/L, the temperature of leaching process is 50 ℃～70 ℃, stirring velocity is 50 r/min～130 r/min, and the add-on of S-WAT is by MnO contained in breeze ₂restore All is Mn ²⁺103%～120% of required theoretical amount, the extraction time of first stage is 1h～2h, and the extraction time of subordinate phase is 1h～2h, and it is 0.5h～1.5h that leach liquor is carried out to oxidization time, and the relative pressure of oxidising process is 0.1Mpa～0.3MPa.