CN101357778B - Method for producing manganese sulfate by acid leaching under pressure of pyrolusite and pyrite - Google Patents
Method for producing manganese sulfate by acid leaching under pressure of pyrolusite and pyrite Download PDFInfo
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- CN101357778B CN101357778B CN2008100589468A CN200810058946A CN101357778B CN 101357778 B CN101357778 B CN 101357778B CN 2008100589468 A CN2008100589468 A CN 2008100589468A CN 200810058946 A CN200810058946 A CN 200810058946A CN 101357778 B CN101357778 B CN 101357778B
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- pyrolusite
- manganese
- pyrite
- leaching
- under pressure
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Abstract
The invention discloses a method for producing manganese sulfate from the acid leaching of pyrolusite and pyrite under pressure, which includes the following steps: (1) after the pyrolusite and pyrite are mixed according to the proportions of 1:0.3 to 0.5 based on the mass ratio of the pyrolusite and pyrite, sulfate with the acidity of 100 to 220g/l is adopted for size mixing; (2) after the size mixing is finished, the materials are added into an autoclave, and the pressure in the autoclave is controlled from 0.3 to 1.0MPa, and the temperature is controlled ranging from 100 to 110 DEG C for the manganese leaching reaction under pressure; after the time of reaction is for 60 to 180 minutes, the obtained material is discharged and the slag is separated from the liquid . The method can leachthe manganese in the pyrolusite within a short time under different acidities, certain pressure and high temperature and the leaching rate of the manganese is about 95 percent and the content of manganese in the slag is less than 1.5 percent.
Description
Technical field
The present invention relates to the hydrometallurgy field of manganese, more particularly, is a kind of smelting process of producing manganous sulfate under the condition of pressurization with the pyrite reducing pyrolusite.
Background technology
The traditional technology that with the pyrolusite is the raw material production manganous sulfate is reducing roasting, sulfuric acid leaching.The technology of this method has the history of decades, and technical maturity is the main method of manganous sulfate production for a long time.But this technology causes energy consumption bigger because of dry materials, fine grinding, reducing roasting etc. are arranged, and working strength of workers is bigger, carry out high-temperature service; Also can produce contaminate environment such as dust and flue gas simultaneously, and production cost is higher, economic benefit is on the low side.At present, pyrolusite directly reduces extract technology and has been applied to industrial production, and this method is a kind of comparatively ideal technology, is applicable to that large industrialized produces manganous sulfate.But pyrolusite directly reduces to leach and has following shortcoming: under normal pressure, temperature of reaction is not high, top temperature is only about 90 ℃, therefore response intensity a little less than, the reaction times is longer, and the manganese leaching yield is not high, have only about 75～85%, it is higher to cause slag to contain manganese, about 5%, has caused the loss of manganese thus; Directly reducing process is not strong to the adaptability of raw material, and is not good to more low-grade pyrolusite leaching effect.
Summary of the invention
The purpose of this invention is to provide a kind of pyrolusite and pyrite pressurized acid leaching and produce the method for manganous sulfate, it has overcome the deficiency of existing method, and the manganese leaching yield behind the pressurized acid leaching reaches more than 95%, has improved the manganese leaching yield.
Purpose of the present invention realizes by following steps: size mixing pyrolusite and pyrite after with 1:0.3～0.5 mixed by mass ratio (1) with the sulfuric acid of 100～220g/l acidity; (2) will expect after sizing mixing to add in the autoclave, control still internal pressure 0.3～1.0Mpa, temperature are pressurizeed for 100 ℃～110 ℃ and are soaked the manganese reaction, discharging behind reaction 60～180min; (3) slag liquid separates, and obtains containing manganese and is lower than 1.5% demanganize slag.Above-mentioned pyrolusite is the low-grade pyrolusite that contains manganese 20.93%～34.95%.
Principal reaction formula among the present invention is:
3MnO
2+2FeS
2+6H
2SO
4＝3MnSO
4+Fe
2(SO
4)
3+4S+6H
2O
MnO
2+FeS
2+2H
2SO
4＝MnSO
4+FeSO
4+2S+2H
2O
15MnO
2+FeS
2+14H
2SO
4＝15MnSO
4+Fe
2(SO
4)
3+14H
2O
4MnO
2+FeS
2+4H
2SO
4＝4MnSO
4+FeSO
4+S+4H
2O
Beneficial effect of the present invention is: the present invention under certain pressure and higher temperature, leaches the manganese in the pyrolusite under different acidity in the short period of time, and all about 95%, slag contains manganese all below 1.5% to the leaching yield of manganese.The technology of the present invention is compared with traditional method and is obtained beyond thought effect: carry out acidleach because of pyrolusite directly enters autoclave, acidleach extraction temperature height, directly leach manganese in the pyrolusite with sulphuric acid soln, roasting in the existing technologies such as reducing roasting acidleach and leaching etc. are concentrated on the pressurization leaching process to be finished, technical process is simplified, equipment reduces, and process intensification realizes that the efficient of manganese directly leached in the pyrolusite.Soak preparation of manganese with respect to existing pyrolusite and the direct reduction of pyrite, pressurized acid leaching can in the short period of time, realize that fast pyrolusite leaches the manganese process at higher extraction temperature, the rate of recovery height of manganese, and it is low that slag contains manganese.
Embodiment
Embodiment one: pyrolusite contains manganese 20.93%, pyrite iron content 39.52%.
The pyrolusite that will contain manganese 20.93% is that mix 1:0.3～0.4 with pyrite by the matter anharmonic ratio, size mixing with the sulphuric acid soln that contains acid 100～140g/l then, lead to the nitrogen leaching in the acidproof autoclave of sizing mixing the back to add volume being 2L, make by the titanium material, keep still internal pressure 0.3Mpa, 100 ℃～110 ℃ leachings of pressurizeing of temperature, extraction time discharging after 60 minutes, obtain after slag liquid separates: the manganese leaching yield is 94.41%, and leached mud contains manganese 1.48%.
Embodiment two: pyrolusite contains manganese 20.93%, pyrite iron content 39.52%.
The pyrolusite that will contain manganese 20.93% is that mix 1:0.4～0.45 with pyrite by the matter anharmonic ratio, size mixing with the sulphuric acid soln that contains acid 140～180g/l then, lead to the nitrogen leaching in the acidproof autoclave of sizing mixing the back to add volume being 2L, make by the titanium material, keep still internal pressure 0.3MPa, 100 ℃～110 ℃ pressurizations leachings of carrying out pyrolusite of temperature, extraction time discharging after 120 minutes, obtain after slag liquid separates: the manganese leaching yield is 95.52%, and leached mud contains manganese 1.11%.
Embodiment three: pyrolusite contains manganese 31.07%, pyrite iron content 39.52%.
The pyrolusite that will contain manganese 31.07% is that mix 1:0.4～0.45 with pyrite by the matter anharmonic ratio, size mixing with the sulphuric acid soln that contains acid 140～180g/l then, leading to nitrogen in the acidproof autoclave that the adding volume is 2L, made by the titanium material leaches, keep 100 ℃～110 ℃ of still internal pressure 0.5Mpa, temperature, carrying out the pressurization of pyrolusite leaches, extraction time discharging after 120 minutes obtains after slag liquid separates: the manganese leaching yield is 94.12%, and leached mud contains manganese 1.33%.
Embodiment four: pyrolusite contains manganese 31.07%, pyrite iron content 39.52%.
The pyrolusite that will contain manganese 31.07% is that mix 1:0.45～0.5 with pyrite by the matter anharmonic ratio, size mixing with the sulphuric acid soln that contains acid 180～220g/l then, lead to the nitrogen leaching in the acidproof autoclave of sizing mixing the back to add volume being 2L, make by the titanium material, keep 100 ℃～110 ℃ of still internal pressure 0.5Mpa, temperature, carrying out the pressurization of pyrolusite leaches, extraction time discharging after 180 minutes obtains after slag liquid separates: the manganese leaching yield is 96.45%, and leached mud contains manganese 1.03%.
Embodiment five: pyrolusite contains manganese 34.95%, pyrite iron content 39.52%.
The pyrolusite that will contain manganese 34.95% is that 1:0.5 mixes with pyrite by the matter anharmonic ratio, size mixing with the sulphuric acid soln that contains acid 180～220g/l then, leading to nitrogen in the acidproof autoclave that the adding volume is 2L, made by the titanium material leaches, keep still internal pressure 0.8Mpa, 100 ℃～110 ℃ pressurizations leachings of carrying out pyrolusite of temperature, extraction time discharging after 180 minutes, obtain after slag liquid separates: the manganese leaching yield is 94.13%, and leached mud contains manganese 1.42%.
Embodiment six: pyrolusite contains manganese 34.95%, pyrite iron content 39.52%.
The pyrolusite that will contain manganese 34.95% is that 1:0.5 mixes with pyrite by the matter anharmonic ratio, size mixing with the sulphuric acid soln that contains acid 200～220g/l then, lead to the nitrogen leaching in the acidproof autoclave of sizing mixing the back to add volume being 2L, make by the titanium material, keep 100 ℃～110 ℃ of still internal pressure 0.8Mpa, temperature, carrying out the pressurization of pyrolusite leaches, extraction time discharging after 120 minutes obtains after slag liquid separates: the manganese leaching yield is 96.15%, and leached mud contains manganese 1.30%.
Claims (1)
1. pyrolusite and pyrite pressurized acid leaching are produced the method for manganous sulfate, it is characterized in that step is as follows:
(1) containing the low-grade pyrolusite of manganese 20.93%～34.95% and pyrite sizes mixing with the sulfuric acid of 100～220g/L acidity after with 1: 0.3～0.5 mixed by mass ratio;
(2) will expect after sizing mixing to add in the autoclave, control still internal pressure is that 0.3～1.0MPa, temperature are pressurizeed for 100 ℃～110 ℃ and soaked the manganese reaction, discharging behind reaction 60～180min, and slag liquid separates.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100589468A CN101357778B (en) | 2008-09-24 | 2008-09-24 | Method for producing manganese sulfate by acid leaching under pressure of pyrolusite and pyrite |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100589468A CN101357778B (en) | 2008-09-24 | 2008-09-24 | Method for producing manganese sulfate by acid leaching under pressure of pyrolusite and pyrite |
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| Publication Number | Publication Date |
|---|---|
| CN101357778A CN101357778A (en) | 2009-02-04 |
| CN101357778B true CN101357778B (en) | 2010-08-18 |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101880062B (en) * | 2010-07-05 | 2013-02-13 | 桂阳杰鹏金牧发展有限公司 | Method for controlling colour-darkening of manganese sulfate |
| CN102220491A (en) * | 2011-06-03 | 2011-10-19 | 郭永锴 | Method for recovering manganese from manganese ore, manganese tailing and manganese slag through continuous pressurization and acid leaching process |
| CN102605188A (en) * | 2011-10-10 | 2012-07-25 | 云南建水锰矿有限责任公司 | Method for producing manganese sulfate by manganese alloy slag through pressure leaching |
| CN102703698B (en) * | 2012-07-11 | 2014-09-17 | 昆明永新瑞科技有限公司 | Wet metallurgical method for spessartite mineral |
| CN103710533B (en) * | 2013-12-24 | 2016-01-27 | 柳州豪祥特科技有限公司 | A kind of method of producing electrolytic metal Mn |
| CN103757445B (en) * | 2013-12-29 | 2015-06-17 | 四川师范大学 | Method for leaching pyrolusite |
| CN109593959A (en) * | 2018-12-24 | 2019-04-09 | 重庆工程职业技术学院 | A kind of pyrolusite and zincblende joint oxygen press acid leaching process |
| CN112777642B (en) * | 2021-01-26 | 2023-03-14 | 广西埃索凯新材料科技有限公司 | Method for preparing high-purity manganese sulfate by reducing and leaching pyrolusite by using rotary kiln slag |
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