CN103757214B - The leaching method of manganese carbonate ore - Google Patents
The leaching method of manganese carbonate ore Download PDFInfo
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- CN103757214B CN103757214B CN201310736431.XA CN201310736431A CN103757214B CN 103757214 B CN103757214 B CN 103757214B CN 201310736431 A CN201310736431 A CN 201310736431A CN 103757214 B CN103757214 B CN 103757214B
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- Prior art keywords
- leaching
- sulfuric acid
- concentration
- leaches
- leach
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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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- Inorganic Compounds Of Heavy Metals (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The leaching method of the sour manganese ore of introduction of the present invention manganous carbonate breeze and walnut shell flour is added in the lump in the reactor of withstand voltage, resistance to sulfuric acid and nitric acid corrosion, adds the leaching that sulphuric acid soln carries out the first stage, leach the CO produced
2discharge from venting port.Work as CO
2when gas is substantially drained, adds nitric acid and carry out the airtight leaching of subordinate phase.Subordinate phase passes into industrial pure oxygen and is oxidized leach liquor after leaching and terminating.
Description
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 produces the main technique of above-mentioned materials, leaches operation and be absolutely necessary operation in this technique.In the wet processing producing 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, when causing employing 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 of subsequent solution purification, the leaching velocity adding glucose is comparatively slow, leaches energy consumption and strengthens.Exploitation 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 has larger practical value.
Summary of the invention
For the problem that current manganese carbonate ore leaches, 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, the walnut shell flour of≤180 object manganous carbonate breezes and≤1.5mm is it is characterized in that to add in the reactor of withstand voltage, resistance to sulfuric acid and nitric acid corrosion in the lump, add the leaching that sulphuric acid soln carries out the first stage, leach the CO produced
2discharge from venting port.Work as CO
2when gas is substantially drained, adds nitric acid and carry out the airtight leaching of subordinate phase.Subordinate phase passes into industrial pure oxygen and is oxidized leach liquor after leaching and terminating.After oxidation terminates, release slurry and carry out solid-liquid separation, obtain required infusion solution.Leached mud washes with water, and washing water are 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 that total amount is the theoretical consumption that in manganese carbonate ore, whole manganese leaches 103% ~ 110%, sulfuric acid adds total amount and comprises the solution returning leaching process, the contained sulfuric acid amount in washing water that newly add sulfuric acid amount and subsequent process and produce.The add-on of walnut shell flour counts MnO in manganese carbonate ore with butt
2100% ~ 130% of quality.For the starting point concentration of sulfuric acid in the sulphuric acid soln that leaches by the Mn in required leach liquor
2+concentration is determined, is calculated as follows:
Mn in sulfuric acid concentration=required leach liquor
2+concentration-for Mn in the sulphuric acid soln that leaches
2+starting point concentration (1)
Each concentration unit of calculating formula is mol/L.
For leaching in the breeze weight of kg and the ratio for leaching in the volume of the solution of L, abbreviation solid-to-liquid ratio is calculated as follows to be determined:
Solid-to-liquid ratio=1: leach the sulfuric acid total amount ÷ sulfuric acid concentration (2) needed for every kg breeze
Leach sulfuric acid total amount needed for every kg breeze in calculating formula in g, sulfuric acid concentration is in g/L.
It is 2g/L ~ 8g/L by the concentration of complete soln volumeter that subordinate phase leaches the nitric acid added.
The temperature of whole leaching process is 40 DEG C ~ 70 DEG C, and stirring velocity is 50r/min ~ 130r/min.The extraction time of first stage is 2h ~ 3h.The extraction time of subordinate phase is 1h ~ 2h.Carrying out oxidization time to leach liquor is 0.5h ~ 1h, and the relative pressure of oxidising process is 0.1Mpa ~ 0.3MPa.
The object of the present invention is achieved like this: the leaching process of first stage is primarily of 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
3entered solution by leaching, 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+there is hydrolysis reaction to enter in leached mud.
In the second leaching stage, except the reaction proceeding the first stage, the following chemical reaction of main generation:
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
Other organism in walnut shell flour also generates NO, CO with nitric acid reaction
2and H
2o, NO and the MnO of generation
2(or Fe
2o
3) and H
2sO
4mnSO is generated by previous reaction
4(or FeSO
4), HNO
3and H
2o.
At oxidation stage, mainly there is Fe
2+oxidizing reaction:
4FeSO
4+O
2+2H
2SO
4=2Fe
2(SO
4)
3+2H
2O
Fe
2(SO
4)
3+3H
2O=Fe
2O
3+3H
2SO
4
Because the speed of response of nitric acid and walnut shell flour is very fast, NO and the MnO of generation
2reaction also very fast, accelerate whole leaching process thus, and realize MnO
2leach more completely.As long as control the add-on of walnut shell flour and the add-on of sulfuric acid well, the amount that Fe enters leach liquor just can be reduced.But the add-on of walnut shell flour and sulphuric acid very little, will affect the leaching yield of leaching velocity and Mn, so the leaching yield in order to ensure Mn, it is inevitable that Fe leaches.Pass through O
2oxidation is by Fe
2+be oxidized to Fe
3+, and then there is hydrolysis reaction, remove portion Fe.The Fe do not eliminated does not need further oxidation follow-up removing in Fe process.
Outstanding advantages of the present invention is: through above-mentioned series reaction, finally makes the Mn in manganese carbonate ore substantially leach completely, improves the leaching yield of Mn, reduces the wasting of resources, thus saves production cost; Because the second leaching stage and leach liquor oxidation stage are thermopositive reaction, substantially do not need additional heat, leaching process is energy-conservation; Because nitric acid is easy to react with walnut shell flour, the NO of generation is easy to again and MnO
2reaction, so leaching process speed is fast; Leaching process carries out in confined conditions, the environmental pollution that the effusion avoiding NO produces; Due in leaching process by Fe
2+oxidation is from Fe
3+, the subsequent purification process of leach liquor can be simplified.
specific implementation method
Embodiment 1: by 1000g manganous carbonate breeze (containing bivalent manganese 25.2%, tetravalent manganese 3.1%, Fe
2o
310.7%, particle diameter 180 order) and≤1.5mm walnut shell flour 49g to add volume be in the lining titanium pressure reaction still of 5L, under exhaust valve opening and the airtight condition of intake valve, add the sulphuric acid soln 2700ml of 2.0mol/L, at 60 ~ 70 DEG C, stir (stirring velocity 80r/min) leach 2h.Then nitric acid 6g is added (with HNO
3meter), continue airtight leaching 1h.After this O is opened
2intake valve passes into O
2in Oxidation Leaching liquid 0.5h(reactor, relative pressure is 0.3MPa).Leach the washing carrying out solid-liquor separation and leached mud after terminating.According to the assay result of leached mud after cleaning, the leaching yield of manganese is 98.9%.
Embodiment 2: by 10kg manganous carbonate breeze (containing bivalent manganese 25.2%, tetravalent manganese 3.1%, Fe
2o
310.7%, particle diameter 180 order) and≤1.5mm walnut shell flour 590g to add volume be in the lining titanium pressure reaction still of 150L, the residual electrolyte preparation that the sulphuric acid soln 120L(sulphuric acid soln adding 0.446mol/L under exhaust valve opening and the airtight condition of intake valve is produced by electrolytic manganese factory, raffinate is containing Mn
2+13.5g/L, H
2sO
434.5g/L).At 50 ~ 60 DEG C, stir (stirring velocity 70r/min) leach 3h.Then nitric acid 720g is added (with HNO
3meter), continue airtight leaching 2h.After this O is passed into
2in Oxidation Leaching liquid 1h(reactor, relative pressure is 0.1MPa).Leach the washing carrying out solid-liquor separation and leached mud after terminating.According to the assay result of leached mud after cleaning, the leaching yield of manganese is 99.2%.
Claims (1)
1.
a leaching method for manganese carbonate ore, is characterized in that the walnut shell flour of≤180 object manganous carbonate breezes and≤1.5mm to add in the lump in the reactor of withstand voltage, resistance to sulfuric acid and nitric acid corrosion, adds the leaching that sulphuric acid soln carries out the first stage, leach the CO produced 2 discharge from venting port, work as CO 2 when gas is substantially drained, add nitric acid and carry out the airtight leaching of subordinate phase, after subordinate phase leaches and terminates, pass into industrial pure oxygen to be oxidized leach liquor, after oxidation terminates, release slurry and carry out solid-liquid separation, obtain required infusion solution, leached mud washes with water, washing water are for preparing sulphuric acid soln for leaching, the sulfuric acid of leaching process adds total amount is the theoretical consumption that in manganese carbonate ore, whole manganese leaches 103% ~ 110%, sulfuric acid adds total amount and comprises the solution returning leaching process newly adding sulfuric acid amount and subsequent process generation, contained sulfuric acid amount in washing water, the add-on of walnut shell flour counts MnO in manganese carbonate ore with butt 2 100% ~ 130% of quality, for the starting point concentration of sulfuric acid in the sulphuric acid soln that leaches by the Mn in required leach liquor 2+ concentration is determined, is calculated as follows: Mn in sulfuric acid concentration=required leach liquor 2+ concentration-for Mn in the sulphuric acid soln that leaches 2+ starting point concentration, each concentration unit of calculating formula is mol/L, for leaching in the breeze weight of kg and the ratio for leaching in the volume of the solution of L, abbreviation solid-to-liquid ratio is calculated as follows to be determined: solid-to-liquid ratio=1: leach the sulfuric acid total amount ÷ sulfuric acid concentration needed for every kg breeze, sulfuric acid total amount needed for every kg breeze is leached in g in calculating formula, sulfuric acid concentration is in g/L, it is 2g/L ~ 8g/L by the concentration of complete soln volumeter that subordinate phase leaches the nitric acid added, the temperature of whole leaching process is 40 DEG C ~ 70 DEG C, stirring velocity is 50r/min ~ 130r/min, the extraction time of first stage is 2h ~ 3h, the extraction time of subordinate phase is 1h ~ 2h, carrying out oxidization time to leach liquor is 0.5h ~ 1h, the relative pressure of oxidising process is 0.1MPa ~ 0.3MPa.
Priority Applications (1)
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|---|---|---|---|
| CN201310736431.XA CN103757214B (en) | 2013-12-29 | 2013-12-29 | The leaching method of manganese carbonate ore |
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|---|---|---|---|
| CN201310736431.XA CN103757214B (en) | 2013-12-29 | 2013-12-29 | The leaching method of manganese carbonate ore |
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| CN103757214A CN103757214A (en) | 2014-04-30 |
| CN103757214B true CN103757214B (en) | 2015-11-25 |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1502710A (en) * | 2002-11-26 | 2004-06-09 | 中南大学 | Deep purification method of manganese sulfate solution |
| CN101070565A (en) * | 2007-06-14 | 2007-11-14 | 重庆大学 | Method for extracting high-valence manganese from manganese carbonate ore |
-
2013
- 2013-12-29 CN CN201310736431.XA patent/CN103757214B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1502710A (en) * | 2002-11-26 | 2004-06-09 | 中南大学 | Deep purification method of manganese sulfate solution |
| CN101070565A (en) * | 2007-06-14 | 2007-11-14 | 重庆大学 | Method for extracting high-valence manganese from manganese carbonate ore |
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| CN103757214A (en) | 2014-04-30 |
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Granted publication date: 20151125 Termination date: 20161229 |