CN103757229B - The leaching method of pyrolusite - Google Patents
The leaching method of pyrolusite Download PDFInfo
- Publication number
- CN103757229B CN103757229B CN201310736458.9A CN201310736458A CN103757229B CN 103757229 B CN103757229 B CN 103757229B CN 201310736458 A CN201310736458 A CN 201310736458A CN 103757229 B CN103757229 B CN 103757229B
- Authority
- CN
- China
- Prior art keywords
- leaching
- pyrolusite
- sulfuric acid
- add
- nitric acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Manufacture And Refinement Of Metals (AREA)
Abstract
The leaching method of the pyrolusite of introduction of the present invention adds in the reactor of withstand voltage, resistance to sulfuric acid and nitric acid corrosion by≤180 order pyrolusite powders and≤1.5mm walnut shell flour, add the mixing solutions of sulfuric acid and nitric acid, and carry out agitation leach in confined conditions, after leaching for some time, release reactor off-gas, then pass in confined conditions industrial pure oxygen to leaching night be oxidized.
Description
Technical field
The present invention relates to a kind of leaching method of pyrolusite.
Background technology
Pyrolusite 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.Due to the MnO in pyrolusite
2be insoluble to sulfuric acid, need MnO by reducing roasting
2be converted into MnO ability sulfuric acid leaching, but the transformation efficiency of roasting only has about 85%, when causing the pyrolusite of sulfuric acid leaching reducing roasting, the leaching yield of metal target manganese is not high, causes the wasting of resources.Although add FeS in Leaching Systems
2can directly leach pyrolusite with sulfuric acid Deng reductive agent, but leaching velocity is slow, extraction temperature is high, and leaching yield is lower.Exploitation leaching yield direct leaching method that is high, the fast pyrolusite of leaching velocity has larger practical value.
Summary of the invention
For the problem that current pyrolusite leaches, the object of the invention is to find the direct leaching method of pyrolusite that a kind of leaching yield is high, leaching velocity is fast, energy consumption is low, the walnut shell flour of≤180 order pyrolusite powders 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, add the mixing solutions of sulfuric acid and nitric acid, and carry out agitation leach in confined conditions.Leach after for some time, release reactor off-gas, then pass into industrial pure oxygen in confined conditions leaching is oxidized night.After oxidation terminates, the slurry of releasing in reactor carries out solid-liquid separation, obtains required infusion solution.Be 1mol/L ~ 4mol/L for the starting point concentration of sulfuric acid in the mixing solutions that leaches, the starting point concentration of nitric acid is 2g/L ~ 10g/L.The add-on of sulfuric acid is 103% ~ 110% of the theoretical amount leached by manganese whole in pyrolusite.The add-on of walnut shell flour counts MnO in pyrolusite with butt
2100% ~ 130% of quality.The temperature of whole leaching process is 40 DEG C ~ 70 DEG C, and stirring velocity is 50r/min ~ 130r/min.Extraction time is 1h ~ 2h.Pass into O
2oxidization time be 0.5h ~ 1h, relative pressure is 0.1MPa ~ 0.2MPa.
The object of the present invention is achieved like this: airtight and under having walnut shell flour and nitric acid existent condition, following chemical reaction mainly occurs sulfuric acid leaching pyrolusite:
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 sulfuric acid well, the amount that Fe enters leach liquor just can be reduced.But 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 pyrolusite substantially leach completely, improves the leaching yield of Mn, reduces the wasting of resources, does not also bring difficulty to subsequent solution purification; Whole leaching process is thermopositive reaction, and temperature of reaction is not high, and energy consumption is low; 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.Due in leaching process by Fe
2+oxidation is from Fe
3+, the subsequent purification process of leach liquor can be simplified.Process is carried out in confined conditions, avoids the environmental pollution that NO effusion produces.
specific implementation method
Embodiment 1: by 1000g pyrolusite powder (containing manganese 55.5%, Fe
2o
36.7%, particle diameter 180 order) and walnut shell flour (1.5mm) 880g to add volume be in the lining titanium pressure reaction still of 10L, add the sulphuric acid soln 6600ml that concentration is 1mol/L, the initial concentration of nitric acid of mixing solutions is 2g/L, and at 40 DEG C ~ 50 DEG C, 2h is leached in airtight stirring (stirring velocity 70r/min).Then O is passed into
2(relative pressure is 0.1MPa) is oxidized 0.5h.According to the assay result of leached mud after cleaning, the leaching yield of manganese is 98.1%.
Embodiment 2: by 10kg pyrolusite powder (containing manganese 55.5%, Fe
2o
36.7%, particle diameter 180 order) and walnut shell flour (1.5mm) 10.5kg to add volume be in the lining titanium pressure reaction still of 50L, add the sulphuric acid soln 23L that concentration is 3mol/L, the initial concentration of nitric acid of mixing solutions is 8g/L, and at 60 DEG C ~ 70 DEG C, 1h is leached in airtight stirring (stirring velocity 60r/min).Then O is passed into
2(relative pressure is 0.15MPa) is oxidized 1h.According to the assay result of leached mud after cleaning, the leaching yield of manganese is 99.1%.
Claims (1)
1. the leaching method of a pyrolusite, the walnut shell flour of≤180 order pyrolusite powders and≤1.5mm is it is characterized in that to 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 agitation leach in confined conditions, after leaching for some time, release reactor off-gas, pass into industrial pure oxygen to be more in confined conditions oxidized night leaching, after oxidation terminates, the slurry of releasing in reactor carries out solid-liquid separation, obtain required infusion solution, be 1mol/L ~ 4mol/L for the starting point concentration of sulfuric acid in the mixing solutions that leaches, the starting point concentration of nitric acid is 2g/L ~ 10g/L, the add-on of sulfuric acid is 103% ~ 110% of the theoretical amount leached by manganese whole in pyrolusite, the add-on of walnut shell flour counts MnO in pyrolusite with butt
2100% ~ 130% of quality, the temperature of whole leaching process is 40 DEG C ~ 70 DEG C, and stirring velocity is 50r/min ~ 130r/min, and extraction time is 1h ~ 2h, passes into O
2oxidization time be 0.5h ~ 1h, relative pressure is 0.1MPa ~ 0.2MPa.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201310736458.9A CN103757229B (en) | 2013-12-29 | 2013-12-29 | The leaching method of pyrolusite |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201310736458.9A CN103757229B (en) | 2013-12-29 | 2013-12-29 | The leaching method of pyrolusite |
Publications (2)
Publication Number | Publication Date |
---|---|
CN103757229A CN103757229A (en) | 2014-04-30 |
CN103757229B true CN103757229B (en) | 2015-11-25 |
Family
ID=50524543
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201310736458.9A Expired - Fee Related CN103757229B (en) | 2013-12-29 | 2013-12-29 | The leaching method of pyrolusite |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN103757229B (en) |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1940098A (en) * | 2006-09-21 | 2007-04-04 | 广西大学 | Gray manganese ore leaching out process |
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 |
CN102367515A (en) * | 2011-10-10 | 2012-03-07 | 云南建水锰矿有限责任公司 | Pressurizing and reductive leaching method of pyrolusite powder |
-
2013
- 2013-12-29 CN CN201310736458.9A patent/CN103757229B/en not_active Expired - Fee Related
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1940098A (en) * | 2006-09-21 | 2007-04-04 | 广西大学 | Gray manganese ore leaching out process |
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 |
CN102367515A (en) * | 2011-10-10 | 2012-03-07 | 云南建水锰矿有限责任公司 | Pressurizing and reductive leaching method of pyrolusite powder |
Non-Patent Citations (1)
Title |
---|
植物粉料—硫酸法直接浸出软锰矿的实践;杨幼平等;《中国矿业》;20010924;第10卷(第5期);54-56 * |
Also Published As
Publication number | Publication date |
---|---|
CN103757229A (en) | 2014-04-30 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN103757445B (en) | Method for leaching pyrolusite | |
CN103757229B (en) | The leaching method of pyrolusite | |
CN103757228B (en) | The leaching method of pyrolusite | |
CN103757234B (en) | The leaching method of pyrolusite | |
CN103757223B (en) | The leaching method of pyrolusite | |
CN103757224B (en) | The leaching method of pyrolusite | |
CN103757233B (en) | The leaching method of pyrolusite | |
CN103757232B (en) | The leaching method of pyrolusite | |
CN103757225B (en) | The leaching method of pyrolusite | |
CN103757236B (en) | The leaching method of pyrolusite | |
CN103757230B (en) | The leaching method of pyrolusite | |
CN103757231B (en) | The leaching method of pyrolusite | |
CN103757219B (en) | The leaching method of pyrolusite | |
CN103757227B (en) | The leaching method of pyrolusite | |
CN103757443B (en) | Method for leaching pyrolusite | |
CN103757204B (en) | The leaching method of manganese carbonate ore | |
CN103757444B (en) | Method for leaching pyrolusite | |
CN103757222B (en) | The leaching method of pyrolusite | |
CN103757267B (en) | The leaching method again of the waste residue that sulfuric acid leaching manganese carbonate ore produces | |
CN103757271B (en) | The leaching method again of the waste residue that sulfuric acid leaching manganese carbonate ore produces | |
CN103757217B (en) | The leaching method of manganese carbonate ore | |
CN103757205B (en) | The leaching method of manganese carbonate ore | |
CN103757213B (en) | The leaching method of manganese carbonate ore | |
CN103757214B (en) | The leaching method of manganese carbonate ore | |
CN103757211B (en) | The leaching method of manganese carbonate ore |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20151125 Termination date: 20161229 |
|
CF01 | Termination of patent right due to non-payment of annual fee |