CN103757274A - Method for re-leaching waste residue generated through leaching manganese carbonate ore with sulfuric acid - Google Patents

Abstract

The invention discloses a method for re-leaching waste residue generated through leaching manganese carbonate ore with sulfuric acid. The method comprises the steps of grinding the waste residue which is generated through leaching the manganese carbonate ore with sulfuric acid until the particle size is not greater than 180 meshes, then, adding the ground waste residue and grain stillage with the particle size being not greater than 1.5mm together into a reaction kettle which is resistant to pressure and the corrosion of sulfuric acid and nitric acid, adding a mixed solution of sulfuric acid and nitric acid, and leaching while stirring under closed conditions.

Description

The leaching method again of the waste residue that sulfuric acid leaching manganese carbonate ore produces

Technical field

The present invention relates to a kind of leaching method again of the waste residue of sulfuric acid leaching manganese carbonate ore generation.

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.Sulfuric acid leaching manganese carbonate ore produces at present waste residue generation and volume of cargo in storage are all very large, and waste residue, containing manganese approximately 6%, has recovery value again.Adopt wet processing can rely on existing technique, the facilities and equipment of the enterprise that produces this class waste residue to its recycling, than being easier to, implement, leaching operation is the requisite operation of wet processing, develops thus that leaching yield is high, leaching velocity is fast, energy consumption is low, can have larger practical value with the leaching method again that produces the waste residue that the existing technique of the enterprise of this class waste residue, sulfuric acid leaching manganese carbonate ore that facilities and equipment match produces.

Summary of the invention

The recycling problem of the waste residue producing for current sulfuric acid leaching 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, can with the leaching method again that produces the waste residue that the existing technique of the enterprise of this class waste residue, sulfuric acid leaching manganese carbonate ore that facilities and equipment match produces, it is characterized in that the waste residue that sulfuric acid leaching manganese carbonate ore is produced be milled down to particle diameter≤180 order after and≤1.5mm vinasse add in the reactor of withstand voltage, resistance to sulfuric acid and nitric acid corrosion in the lump.The mixing solutions that adds sulfuric acid and nitric acid, and carry out in confined conditions agitation leach.After leaching finishes, the slurry of emitting in reactor carries out solid-liquid separation, obtains required infusion solution.The infusion solution obtaining is for preparing the solution that leaches manganese carbonate ore.Starting point concentration for the mixing solutions sulfuric acid that leaches is 0.5mol/L～1mol/L, and the starting point concentration of nitric acid is 2g/L～10g/L.The add-on of sulfuric acid is by 100%～105% of the theoretical amount that in waste residue, all manganese leaches.The add-on of vinasse is counted MnO in waste residue with butt ₂100%～130% of quality.The temperature of whole leaching process is 40 ℃～70 ℃, and stirring velocity is 50 r/min～130 r/min.Leached mud washes with water, and washing water are used for preparing sulphuric acid soln and leach for waste residue.Waste residue after washing send slag field to deposit.

The object of the present invention is achieved like this: in waste residue, can leach element is mainly manganese and iron, is substantially respectively MnO ₂, Mn (OH) ₂and Fe ₂o ₃state.Airtight and have under the condition that vinasse and nitric acid exists, mainly there is following chemical reaction in sulfuric acid leaching waste residue:

nC ₆H ₁₀O ₅?+?nH ₂SO ₄?=n(C ₅H ₁₁O ₅)HSO ₄

n(C ₅H ₁₁O ₅)HSO ₄?+?nH ₂O?=?nC ₆H ₁₂O ₆?+?nH ₂SO ₄

C ₆H ₁₂O ₆?+?8HNO ₃?=?8NO?+?6CO ₂?+?10H ₂O

nC ₆H ₁₀O ₅?+?8nHNO ₃?=?8nNO?+?6nCO ₂?+?9nH ₂O

3MnO ₂?+?2NO?+?3H ₂SO ₄?=?3MnSO ₄?+?2HNO ₃?+?2H ₂O

3Fe ₂O ₃?+?2NO?+?6H ₂SO ₄?=?6FeSO ₄?+?2HNO ₃?+?5H ₂O

Total reaction is:

12nMnO ₂?+?nC ₆H ₁₀O ₅?+?12nH ₂SO ₄?=?12nMnSO ₄?+?6nCO ₂?+?17nH ₂O

12nFe ₂O ₃?+?nC ₆H ₁₀O ₅?+?24nH ₂SO ₄?=?24nFeSO ₄?+?6nCO ₂?+?29nH ₂O

In addition Mn (OH) ₂there is following chemical reaction:

Mn(OH) ₂?+?H ₂SO ₄?=?MnSO ₄?+?H ₂O

Other organism in vinasse also generates NO, CO with nitric acid reaction ₂and H ₂o, the NO of generation and MnO ₂(or Fe ₂o ₃) and H ₂sO ₄by previous reaction, generate MnSO ₄(or FeSO ₄), HNO ₃and H ₂o.

Because the speed of response of nitric acid and vinasse is very fast, the NO of generation and MnO ₂reaction also very fast, accelerate thus whole leaching process, and realize MnO in waste residue ₂leach more completely.As long as control the add-on of sulfuric acid well, just can reduce the amount that Fe enters leach liquor.Yet sulphuric acid very little, will affect the leaching yield of leaching velocity and Mn, so in order to guarantee the leaching yield of Mn, it is inevitable that Fe leaches.Enter the Fe of leach liquor ²⁺to follow-up deironing (generally adopting neutralization precipitation method), can have a negative impact.Because the manganese content in waste residue is lower, the Mn of leach liquor ²⁺concentration is on the low side, and the existing purification of leaching liquor system of the direct Entry Firm of leach liquor also exists process matching problem.The leach liquor that present method is obtained leaches the required sulphuric acid soln of manganese carbonate ore for preparing, and can, according to the needs of the existing technique of enterprise, adjust flexibly the Mn of manganese carbonate ore leach liquor ²⁺concentration, realizes the matched well with existing technique.What is more important, contains some amount Fe in the leach liquor that the present invention obtains ²⁺, enter after manganese carbonate ore leaching system, there is following chemical reaction:

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

By above-mentioned reaction during by original sulfuric acid leaching manganese carbonate ore, the MnO that can not leach ₂leach more completely, no longer produce new high Mn content waste residue.Meanwhile, Fe ²⁺be oxidized to Fe ³⁺, be conducive to follow-up purification of leaching liquor process, be equipped with completely with existing technique.

Outstanding advantages of the present invention is: through above-mentioned series reaction, the Mn in the waste residue that final sulfuric acid leaching manganese carbonate ore produces leaches substantially completely, reduces the wasting of resources, also to subsequent solution, does not purify and brings difficulty; Leaching process temperature is lower, and speed of response is very fast, and energy consumption is lower; Leach the leaching system that returns to manganese carbonate ore night, can improve the leaching yield of manganese in manganese carbonate ore, avoid producing new high manganese waste slag; Process is carried out in confined conditions, the environmental pollution of having avoided NO to overflow and produce.

specific implementation method

embodiment 1: it is in the lining titanium pressure reaction still of 5L that the waste residue that 2000g sulfuric acid leaching manganese carbonate ore is produced (containing manganese 6.2%, iron 15.1%, particle diameter 180 orders) and 125g vinasse (≤1.5mm) add volume, adding sulfuric acid concentration is the mixing solutions 4.52L that 0.5mol/L, concentration of nitric acid are 2g/L, at 40 ℃～50 ℃, 2h is leached in airtight stirring (stirring velocity 80r/min), leaches 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 96.8%.

Embodiment 2: it is in the lining titanium pressure reaction still of 50L that the waste residue that 20kg sulfuric acid leaching manganese carbonate ore is produced (containing manganese 6.2%, iron 15.1%, particle diameter 180 orders) and 1.5kg vinasse (≤1.5mm) add volume, adding sulfuric acid concentration is the mixing solutions 33L that 0.7mol/L, concentration of nitric acid are 5g/L, and at 60 ℃～70 ℃, 1h is leached in airtight stirring (stirring velocity 70r/min).After finishing, leaching 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 99.2%.

Claims (1)

1. a kind of leaching method again of the waste residue that a sulfuric acid leaching manganese carbonate ore produces, it is characterized in that the waste residue that sulfuric acid leaching manganese carbonate ore is produced be milled down to particle diameter≤180 order after and≤1.5mm vinasse add withstand voltage in the lump, in the reactor of resistance to sulfuric acid and nitric acid corrosion, the mixing solutions that adds sulfuric acid and nitric acid, and carry out in confined conditions agitation leach, after leaching finishes, the slurry of emitting in reactor carries out solid-liquid separation, obtain required infusion solution, the infusion solution obtaining is for preparing the solution that leaches manganese carbonate ore, starting point concentration for the mixing solutions sulfuric acid that leaches is 0.5mol/L～1mol/L, the starting point concentration of nitric acid is 2g/L～10g/L, the add-on of sulfuric acid is by 100%～105% of the theoretical amount that in waste residue, all manganese leaches, the add-on of vinasse is counted MnO in waste residue with butt ₂100%～130% of quality, the temperature of whole leaching process is 40 ℃～70 ℃, and stirring velocity is 50 r/min～130 r/min, and leached mud washes with water, and washing water are used for preparing sulphuric acid soln and leach for waste residue.