CN103757228B - The leaching method of pyrolusite - Google Patents
The leaching method of pyrolusite Download PDFInfo
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- CN103757228B CN103757228B CN201310736455.5A CN201310736455A CN103757228B CN 103757228 B CN103757228 B CN 103757228B CN 201310736455 A CN201310736455 A CN 201310736455A CN 103757228 B CN103757228 B CN 103757228B
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- China
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- pyrolusite
- leaching
- sulfuric acid
- add
- nitric acid
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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 cogongrass powder, 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 cogongrass powder 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 leach liquor is oxidized.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 cogongrass powder 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 cogongrass powder 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 cogongrass powder 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 cogongrass powder 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 cogongrass powder, 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 cogongrass powder (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 97.8%.
Embodiment 2: by 10kg pyrolusite powder (containing manganese 55.5%, Fe
2o
36.7%, particle diameter 180 order) and cogongrass powder (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 99.0%.
Claims (1)
1. the leaching method of a pyrolusite, the cogongrass powder 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 leach liquor, 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 cogongrass powder 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.
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CN201310736455.5A CN103757228B (en) | 2013-12-29 | 2013-12-29 | The leaching method of pyrolusite |
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CN201310736455.5A CN103757228B (en) | 2013-12-29 | 2013-12-29 | The leaching method of pyrolusite |
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CN103757228A CN103757228A (en) | 2014-04-30 |
CN103757228B true CN103757228B (en) | 2016-01-20 |
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Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3780159A (en) * | 1972-06-23 | 1973-12-18 | Diamond Shamrock Corp | Process for recovering manganese values from low grade oxidized manganese containing ores |
EP0013098A1 (en) * | 1978-12-20 | 1980-07-09 | Sherritt Gordon Mines Limited | Removal of manganese ions from zinc and manganese containing solutions |
CN1058201A (en) * | 1991-04-22 | 1992-01-29 | 黄石市能源综合科学技术研究所 | The novel process of wet producing manganese sulfate from two kinds of mine |
CN1127726A (en) * | 1995-05-19 | 1996-07-31 | 赵培岭 | Method for producing manganese sulfate using waste residue from production of potassium permanganate |
CN1861815A (en) * | 2005-05-14 | 2006-11-15 | 广西汇元锰业有限公司 | Process of continuously leaching manganese oxide ore |
CN102358917A (en) * | 2011-07-10 | 2012-02-22 | 重庆大学 | Method for leaching manganese sulfate from low grade pyrolusite |
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 CN201310736455.5A patent/CN103757228B/en not_active Expired - Fee Related
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3780159A (en) * | 1972-06-23 | 1973-12-18 | Diamond Shamrock Corp | Process for recovering manganese values from low grade oxidized manganese containing ores |
EP0013098A1 (en) * | 1978-12-20 | 1980-07-09 | Sherritt Gordon Mines Limited | Removal of manganese ions from zinc and manganese containing solutions |
CN1058201A (en) * | 1991-04-22 | 1992-01-29 | 黄石市能源综合科学技术研究所 | The novel process of wet producing manganese sulfate from two kinds of mine |
CN1127726A (en) * | 1995-05-19 | 1996-07-31 | 赵培岭 | Method for producing manganese sulfate using waste residue from production of potassium permanganate |
CN1861815A (en) * | 2005-05-14 | 2006-11-15 | 广西汇元锰业有限公司 | Process of continuously leaching manganese oxide ore |
CN102358917A (en) * | 2011-07-10 | 2012-02-22 | 重庆大学 | Method for leaching manganese sulfate from low grade pyrolusite |
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 |
---|
氧化锰矿还原浸出工艺技术研究进展;李进中等;《中国锰业》;20111128;第29卷(第4期);1-7 * |
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