CN103757428A - Method for re-leaching waste residue generated through leaching manganese carbonate ore with sulfuric acid - Google Patents

Method for re-leaching waste residue generated through leaching manganese carbonate ore with sulfuric acid Download PDF

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Publication number
CN103757428A
CN103757428A CN201310736397.6A CN201310736397A CN103757428A CN 103757428 A CN103757428 A CN 103757428A CN 201310736397 A CN201310736397 A CN 201310736397A CN 103757428 A CN103757428 A CN 103757428A
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China
Prior art keywords
leaching
sulfuric acid
waste residue
manganese carbonate
carbonate ore
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CN201310736397.6A
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Chinese (zh)
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龙炳清
邓其军
聂付江
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Sichuan Normal University
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Sichuan Normal University
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Priority to CN201310736397.6A priority Critical patent/CN103757428A/en
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

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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 bamboo sawdust 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 bamboo bits 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 bamboo bits 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 of bamboo bits and nitric acid existence, 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 bamboo bits 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 bamboo bits 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 bamboo bits (≤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 97.0%.
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 bamboo bits (≤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 bamboo bits 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 bamboo bits 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.
CN201310736397.6A 2013-12-29 2013-12-29 Method for re-leaching waste residue generated through leaching manganese carbonate ore with sulfuric acid Pending CN103757428A (en)

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101619394A (en) * 2009-06-23 2010-01-06 四川师范大学 Method for leaching anode and cathode mixed material of waste lithium nickel manganese cobalt battery

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101619394A (en) * 2009-06-23 2010-01-06 四川师范大学 Method for leaching anode and cathode mixed material of waste lithium nickel manganese cobalt battery

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
李进中等: ""氧化锰矿还原浸出工艺技术研究进展"", 《中国锰业》 *

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Application publication date: 20140430