CN103757431A - 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
CN103757431A
CN103757431A CN201310736414.6A CN201310736414A CN103757431A CN 103757431 A CN103757431 A CN 103757431A CN 201310736414 A CN201310736414 A CN 201310736414A CN 103757431 A CN103757431 A CN 103757431A
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China
Prior art keywords
leaching
waste residue
sulfuric acid
manganese carbonate
carbonate ore
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CN201310736414.6A
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Chinese (zh)
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龙炳清
万旭
陈俊
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Sichuan Normal University
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Sichuan Normal University
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Priority to CN201310736414.6A priority Critical patent/CN103757431A/en
Publication of CN103757431A publication Critical patent/CN103757431A/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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  • Manufacture And Refinement Of Metals (AREA)

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 until the particle size is not greater than 180 meshes, then, adding the ground waste residue into a reaction kettle which is resistant to the corrosion of sulfuric acid and pressure, adding a sulfuric acid solution and sodium sulfite, and then, enclosing the reaction kettle and leaching while stirring.

Description

The leaching method again of the waste residue that sulfuric acid leaching manganese carbonate ore produces
Technical field
The present invention relates to the one 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 to produce the main technique of above-mentioned materials, leaches the operation operation that is absolutely necessary in this technique.Producing in 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.Waste residue generation and the volume of cargo in storage of sulfuric acid leaching manganese carbonate ore are all very large at present, and waste residue, containing manganese approximately 6%, has recovery value again.Adopt wet processing to its recycling, can rely on existing technique, the facilities and equipment of the enterprise that produces this class waste residue, 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 existing technique, the leaching method again of waste residue that sulfuric acid leaching manganese carbonate ore that facilities and equipment match produces of the enterprise that produces this class waste residue.
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 existing technique, the leaching method again of waste residue that sulfuric acid leaching manganese carbonate ore that facilities and equipment match produces of enterprise that produces this class waste residue, it is characterized in that the waste residue that sulfuric acid leaching manganese carbonate ore is produced is milled down to adds after the order of particle diameter≤180 in sulfuric acid corrosion resistant and withstand voltage reactor, add sulphuric acid soln and S-WAT, then closed reactor carries out agitation leach.The slurry of emitting after leaching finishes in reactor carries out solid-liquid separation, obtains required leach liquor.Leached mud washes with water, and the waste residue after washing send slag field to deposit.The leach liquor obtaining is for preparing the sulphuric acid soln that leaches manganese carbonate ore.The washing water that produce are for leaching the sulphuric acid soln of waste residue.The sulfuric acid of leaching process add total amount be manganese in waste residue theoretical consumption 110%～150%.Every kg waste residue adds sulphuric acid soln 2～5L.
The temperature of leaching process is 50 ℃～80 ℃, and stirring velocity is 50 r/min～130 r/min.Extraction time is 2h～4h, and the add-on of S-WAT is by MnO contained in breeze 2restore All is Mn 2+105%～120% of required theoretical amount.
The object of the present invention is achieved like this: the leached element in the waste residue that sulfuric acid leaching manganese carbonate ore produces is mainly manganese and iron, is respectively Mn (OH) 2, MnO 2and Fe (OH) 3form, under the condition that has S-WAT to exist, mainly there is following chemical reaction in the process of sulfuric acid leaching manganese carbonate ore:
Mn(OH) 2 + H 2SO 4 = MnSO 4 + 2H 2O
2Fe(OH) 3 + 3H 2SO 4 = Fe 2(SO 4) 3 + 6H 2O
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
2FeSO 4 + MnO 2 + 2H 2SO 4 = MnSO 4 + Fe 2(SO 4) 3 + 2H 2O
Because the reductibility of S-WAT is 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 MO 2reaction is consumed, and whole system is carried out under pressure-fired.Also because the reductibility of S-WAT is stronger, the Fe part that enters leach liquor is Fe 2+form, brings certain difficulty can to follow-up purification of leaching liquor, meanwhile, 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 and final waste residue washing water thereof 2+(concrete content is according to the MnO that needs reduction in manganese carbonate ore 2content, by adjusting H in the present invention 2sO 4control with S-WAT), 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; Because S-WAT is easy to and MnO 2reaction, so reduction leaching process speed is fast; In the leach liquor obtaining, contain a great deal of Fe 2+, enter after the leaching system of existing manganese carbonate ore can be by original sulfuric acid leaching manganese carbonate ore time the MnO that can not leach 2leach more completely, no longer produce new high Mn content waste residue.
specific implementation method
embodiment 1: by 1000g manganese carbonate ore leached mud (containing total manganese 6.7%, wherein tetravalence manganese 6.5%, Fe 2o 310.7%, particle diameter 180 orders) to add volume be in the stainless steel cauldron of 5L, adds sulphuric acid soln 2500ml and the S-WAT 165g of 0.6mol/L, at 60～70 ℃, 2h is leached in airtight stirring (stirring velocity 80r/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 98.8%.
Embodiment 2: by 10kg manganese carbonate ore leached mud (containing total manganese 6.7%, wherein tetravalence manganese 6.5%, Fe 2o 310.7%, particle diameter 180 orders) to add volume be in the stainless steel cauldron of 50L, adds H 2sO 4the sulphuric acid soln 35L(sulphuric acid soln of 34.5g/L is the residual electrolyte that electrolytic manganese factory produces, and raffinate is containing Mn 2+13.5g/L, H 2sO 434.5g/L) with S-WAT 1.6kg, at 50～60 ℃, 3h 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 99.1%.

Claims (3)

1. the leaching method again of the waste residue of a sulfuric acid leaching manganese carbonate ore generation, it is characterized in that the waste residue that sulfuric acid leaching manganese carbonate ore is produced is milled down to adds after the order of particle diameter≤180 in sulfuric acid corrosion resistant and withstand voltage reactor, add sulphuric acid soln and S-WAT, then closed reactor carries out agitation leach, the slurry of emitting after leaching finishes in reactor carries out solid-liquid separation, obtains required leach liquor.
2. leached mud washes with water, and the waste residue after washing send slag field to deposit, and the leach liquor obtaining is for preparing the sulphuric acid soln that leaches manganese carbonate ore, and the washing water of generation are for leaching the sulphuric acid soln of waste residue.
The sulfuric acid of leaching process add total amount be manganese in waste residue theoretical consumption 110%～150%, every kg waste residue adds sulphuric acid soln 2～5L, the temperature of leaching process is 50 ℃～80 ℃, stirring velocity is 50 r/min～130 r/min, extraction time is 2h～4h, and the add-on of S-WAT is by MnO contained in breeze 2restore All is Mn 2+105%～120% of required theoretical amount.
CN201310736414.6A 2013-12-29 2013-12-29 Method for re-leaching waste residue generated through leaching manganese carbonate ore with sulfuric acid Pending CN103757431A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20010089870A (en) * 2000-03-25 2001-10-12 문상우 Process for manufacturing mineral to be added in feed for animais from dust in electric furnace
CN1382813A (en) * 2002-03-12 2002-12-04 四川川投峨眉铁合金（集团）有限责任公司 Fully wet technology for extracting Mg from Mg contained dust
CN101956069A (en) * 2010-09-15 2011-01-26 长沙达华污泥处理科技有限公司 Method for reducing and leaching manganese from pyrolusite in sulfuric acid solution by using sludge
CN102424424A (en) * 2011-09-15 2012-04-25 陈昆先 Production method for manganese sulfate by using biological cellulose and low-grade manganese ores

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20010089870A (en) * 2000-03-25 2001-10-12 문상우 Process for manufacturing mineral to be added in feed for animais from dust in electric furnace
CN1382813A (en) * 2002-03-12 2002-12-04 四川川投峨眉铁合金（集团）有限责任公司 Fully wet technology for extracting Mg from Mg contained dust
CN101956069A (en) * 2010-09-15 2011-01-26 长沙达华污泥处理科技有限公司 Method for reducing and leaching manganese from pyrolusite in sulfuric acid solution by using sludge
CN102424424A (en) * 2011-09-15 2012-04-25 陈昆先 Production method for manganese sulfate by using biological cellulose and low-grade manganese ores

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Application publication date: 20140430