CN103757230A - Method for leaching pyrolusite - Google Patents
Method for leaching pyrolusite Download PDFInfo
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- CN103757230A CN103757230A CN201310736459.3A CN201310736459A CN103757230A CN 103757230 A CN103757230 A CN 103757230A CN 201310736459 A CN201310736459 A CN 201310736459A CN 103757230 A CN103757230 A CN 103757230A
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- China
- Prior art keywords
- leaching
- pyrolusite
- sulfuric acid
- nitric acid
- add
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- Manufacture And Refinement Of Metals (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a method for leaching pyrolusite. The method comprises the steps of adding pyrolusite powder with the particle size being not greater than 180 meshes and napier grass powder with the particle size being not greater than 1.5mm 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, leaching while stirring under closed conditions, exhausting reaction waste gas after leaching for a period of time, and introducing industrial pure oxygen under closed conditions, so as to oxidize a leachate.
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 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.Due to the MnO in pyrolusite
2be insoluble to sulfuric acid, need to be by reducing roasting by MnO
2be converted into MnO ability sulfuric acid leaching, but the transformation efficiency of roasting only has 85% left and right, while 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
2deng reductive agent, can directly leach pyrolusite with sulfuric acid, but leaching velocity is slow, extraction temperature is high, and leaching yield is lower.Exploitation leaching yield direct leaching method high, the fast pyrolusite of leaching velocity has larger practical value.
?
Summary of the invention
The problem leaching for current pyrolusite, 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, it is characterized in that by≤180 order pyrolusite powders and≤the napier grass powder of 1.5mm adds 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, emit reactor off-gas, then pass in confined conditions industrial pure oxygen and be oxidized night leaching.After oxidation finishes, the slurry of emitting in reactor carries out solid-liquid separation, obtains required infusion solution.The starting point concentration that is used for the mixing solutions sulfuric acid leaching is 1mol/L～4mol/L, and the starting point concentration of nitric acid is 2g/L～10g/L.The add-on of sulfuric acid is by 103%～110% of the theoretical amount that in pyrolusite, all manganese leaches.The add-on of napier grass powder is counted MnO in pyrolusite with butt
2100%～130% of quality.The temperature of whole leaching process is 40 ℃～70 ℃, and stirring velocity is 50 r/min～130 r/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 have under the condition that napier grass powder and nitric acid exists, 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 napier grass powder also generates NO, CO with nitric acid reaction
2and H
2o, the NO of generation and MnO
2(or Fe
2o
3) and H
2sO
4by previous reaction, generate MnSO
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 napier grass powder is very fast, the NO of generation and MnO
2reaction also very fast, accelerate thus whole leaching process, and realize MnO
2leach more completely.As long as control the add-on of sulfuric acid well, the amount that just can reduce Fe and enter leach liquor.But sulphuric acid 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.Pass through O
2oxidation is by Fe
2+be oxidized to Fe
3+, and then there is hydrolysis reaction, remove portion Fe.The Fe not eliminating does not need further oxidation follow-up except in Fe process.
Outstanding advantages of the present invention is: through above-mentioned series reaction, finally make the Mn in pyrolusite substantially leach completely, improved the leaching yield of Mn, reduce the wasting of resources, also to subsequent solution, do not purify and bring difficulty; 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 napier grass 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+, can simplify the follow-up scavenging process of leach liquor.Process is carried out in confined conditions, the environmental pollution of having avoided NO effusion to produce.
specific implementation method
embodiment 1: 1000g pyrolusite powder (is contained to manganese 55.5%, Fe
2o
36.7%, particle diameter 180 orders) and napier grass powder (1.5mm) 880g to add volume be in the lining titanium pressure reaction still of 10L, adding concentration is the sulphuric acid soln 6600ml of 1mol/L, the initial concentration of nitric acid of mixing solutions is 2g/L, and at 40 ℃～50 ℃, 2h is leached in airtight stirring (stirring velocity 70r/min).Then pass into O
2(relative pressure is 0.1MPa) oxidation 0.5h.According to the assay result of the leached mud after cleaning, the leaching yield of manganese is 98.4%.
Embodiment 2: 10kg pyrolusite powder (is contained to manganese 55.5%, Fe
2o
36.7%, particle diameter 180 orders) and napier grass powder (1.5mm) 10.5kg to add volume be in the lining titanium pressure reaction still of 50L, adding concentration is the sulphuric acid soln 23L of 3mol/L, the initial concentration of nitric acid of mixing solutions is 8g/L, and at 60 ℃～70 ℃, 1h is leached in airtight stirring (stirring velocity 60r/min).Then pass into O
2(relative pressure is 0.15MPa) oxidation 1h.According to the assay result of the leached mud after cleaning, the leaching yield of manganese is 99.3%.
Claims (1)
1. the leaching method of a pyrolusite, it is characterized in that by≤180 order pyrolusite powders and≤the napier grass powder of 1.5mm adds 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, leach after for some time, emit reactor off-gas, passing in confined conditions more industrial pure oxygen is oxidized leaching night, after oxidation finishes, the slurry of emitting in reactor carries out solid-liquid separation, obtain required infusion solution, the starting point concentration that is used for the mixing solutions sulfuric acid leaching is 1mol/L～4mol/L, the starting point concentration of nitric acid is 2g/L～10g/L, the add-on of sulfuric acid is by 103%～110% of the theoretical amount that in pyrolusite, all manganese leaches, the add-on of napier grass powder is counted MnO in pyrolusite with butt
2100%～130% of quality, 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, 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 |
|---|---|---|---|
| CN201310736459.3A CN103757230B (en) | 2013-12-29 | 2013-12-29 | The leaching method of pyrolusite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310736459.3A CN103757230B (en) | 2013-12-29 | 2013-12-29 | The leaching method of pyrolusite |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103757230A true CN103757230A (en) | 2014-04-30 |
| CN103757230B CN103757230B (en) | 2016-01-20 |
Family
ID=50524544
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310736459.3A Expired - Fee Related CN103757230B (en) | 2013-12-29 | 2013-12-29 | The leaching method of pyrolusite |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN101831544A (en) * | 2010-05-18 | 2010-09-15 | 中国地质科学院郑州矿产综合利用研究所 | Method for separating manganese and silver from manganese-silver ore and purifying manganese leaching solution to extract manganese sulfate |
| 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 CN201310736459.3A patent/CN103757230B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN101831544A (en) * | 2010-05-18 | 2010-09-15 | 中国地质科学院郑州矿产综合利用研究所 | Method for separating manganese and silver from manganese-silver ore and purifying manganese leaching solution to extract manganese sulfate |
| 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 |
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| CN103757230B (en) | 2016-01-20 |
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Granted publication date: 20160120 Termination date: 20161229 |