CN103757273A - 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 PDFInfo
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- CN103757273A CN103757273A CN201310736425.4A CN201310736425A CN103757273A CN 103757273 A CN103757273 A CN 103757273A CN 201310736425 A CN201310736425 A CN 201310736425A CN 103757273 A CN103757273 A CN 103757273A
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- CN
- China
- Prior art keywords
- leaching
- sulfuric acid
- waste residue
- manganese carbonate
- carbonate ore
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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 high-concentration organic wastewater which does not contain benzene-ring substances 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
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.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 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 a kind of leaching yield high, leaching velocity is fast, energy consumption is low, can with the existing technique of enterprise that produces this class waste residue, the leaching method again of the waste residue that the 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 containing the high concentrated organic wastewater of benzene ring substance, do not add withstand voltage, in the reactor of resistance to sulfuric acid and nitric acid corrosion, add the mixing solutions of 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.For the sulfuric acid starting point concentration leaching, be 0.5mol/L～1mol/L, the starting point concentration of nitric acid is 2g/L～10g/L.Be used for the COD of the high concentrated organic wastewater leaching
crconcentration>=10000mg/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 high concentrated organic wastewater is with per kilogram MnO in waste residue
2add COD
cr0.20 kilogram～0.25 kilogram calculating adds.The temperature of whole leaching process is 40 ℃～70 ℃, and stirring velocity is 50 r/min～130 r/min.Extraction time is 1h～2h.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 high concentrated organic wastewater and nitric acid exists, in sulfuric acid leaching waste residue, the redox reaction of manganese can represent with general formula below:
3(C-H
xO
y)
m?+?4mHNO
3?=?4mNO?+?3mCO
2?+?zH
2O
3MnO
2?+?2NO?+?6H
+?=?3Mn
2+?+?2HNO
3?+?2H
2O
Total reaction is:
(C-H
xO
y)
m?+?2mMnO
2?+?2mH
+?=?2mMn
2+?+?mCO
2?+?zH
2O
Similarly Fe
2o
3the total reaction of leaching is:
(C-H
xO
y)
m?+?2mFe
2O
3?+?4mH
+?=?4mFe
2+?+?mCO
2?+?qH
2O
In addition Mn (OH)
2there is following chemical reaction:
Mn(OH)
2?+?H
2SO
4?=?MnSO
4?+?H
2O
Because the organism speed of response in nitric acid and high concentrated organic wastewater 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 and high concentrated organic wastewater well, the amount that just can reduce Fe and enter leach liquor.But the add-on of sulfuric acid and high concentrated organic wastewater 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+and organism, 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
(C-H
xO
y)
m?+?2mMnO
2?+?2mH
+?=?2mMn
2+?+?mCO
2?+?zH
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; 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.
specific implementation method
embodiment 1: the waste residue (containing manganese 6.2%, iron 15.1%, particle diameter 180 orders) that 2000g sulfuric acid leaching manganese carbonate ore is produced and 3.9L fermentation drug manufacture waste water are (containing COD
cr10000mg/L) with the sulfuric acid concentration of sulfuric acid and nitric acid preparation be mixing solutions 4.51L that 0.5mol/L, concentration of nitric acid are 2g/L to add volume be in the lining titanium pressure reaction still of 5L, at 40 ℃～50 ℃, 2h is leached in airtight stirring (stirring velocity 70r/min).According to the assay result of the leached mud after cleaning, the leaching yield of manganese is 97.5%.
Embodiment 2: the waste residue (containing manganese 6.2%, iron 15.1%, particle diameter 180 orders) that 20kg sulfuric acid leaching manganese carbonate ore is produced and 9.8L brewing wastewater are (containing COD
cr50000mg/L) with the sulfuric acid concentration of sulfuric acid and nitric acid preparation be mixing solutions 32L that 0.7mol/L, concentration of nitric acid are 8g/L to add volume be in the lining titanium pressure reaction still of 50L, at 55 ℃～65 ℃, 1h is leached in airtight stirring (stirring velocity 60r/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 (1)
1. the one leaching method again of the waste residue of a manganese carbonate ore generation, 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 containing the high concentrated organic wastewater of benzene ring substance, do not add withstand voltage, in the reactor of resistance to sulfuric acid and nitric acid corrosion, add the mixing solutions of 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, for the sulfuric acid starting point concentration leaching, be 0.5mol/L～1mol/L, the starting point concentration of nitric acid is 2g/L～10g/L, be used for the COD of the high concentrated organic wastewater leaching
crconcentration>=10000mg/L, the add-on of sulfuric acid is that the add-on of high concentrated organic wastewater is with per kilogram MnO in waste residue by 100%～105% of the theoretical amount that in waste residue, all manganese leaches
2add COD
cr0.20 kilogram～0.25 kilogram calculating adds, and the temperature of whole leaching process is 40 ℃～70 ℃, and stirring velocity is 50 r/min～130 r/min, and extraction time is 1h～2h, and leached mud washes with water, and washing water are used for preparing sulphuric acid soln and leach for waste residue.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310736425.4A CN103757273A (en) | 2013-12-29 | 2013-12-29 | Method for re-leaching waste residue generated through leaching manganese carbonate ore with sulfuric acid |
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|---|---|---|---|
| CN201310736425.4A CN103757273A (en) | 2013-12-29 | 2013-12-29 | Method for re-leaching waste residue generated through leaching manganese carbonate ore with sulfuric acid |
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| Publication Number | Publication Date |
|---|---|
| CN103757273A true CN103757273A (en) | 2014-04-30 |
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ID=50524587
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|---|---|---|---|
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101255495A (en) * | 2008-04-08 | 2008-09-03 | 上海电力学院 | Leaching method for recycling waste zinc-manganese alkaline dry batteries |
-
2013
- 2013-12-29 CN CN201310736425.4A patent/CN103757273A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101255495A (en) * | 2008-04-08 | 2008-09-03 | 上海电力学院 | Leaching method for recycling waste zinc-manganese alkaline dry batteries |
Non-Patent Citations (1)
| Title |
|---|
| 粟海锋等: ""硫酸-糖蜜酒精废液浸出锰矿的工艺研究"", 《高校化学工程学报》 * |
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Application publication date: 20140430 |