CN106191473A - A kind of method of the manganese leaching rate improved in manganese spar - Google Patents
A kind of method of the manganese leaching rate improved in manganese spar Download PDFInfo
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- CN106191473A CN106191473A CN201610573314.XA CN201610573314A CN106191473A CN 106191473 A CN106191473 A CN 106191473A CN 201610573314 A CN201610573314 A CN 201610573314A CN 106191473 A CN106191473 A CN 106191473A
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- China
- Prior art keywords
- manganese
- spar
- leaching rate
- manganese spar
- sulphuric acid
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B47/00—Obtaining manganese
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/08—Sulfuric acid, other sulfurated acids or salts thereof
Abstract
A kind of method that the invention discloses manganese leaching rate improved in manganese spar, the steps include: 1) concentrated sulphuric acid and water are added in manganese spar, mass ratio is its theoretical value 1.1～1.2 times of concentrated sulphuric acid and manganese spar, water is 6～7 1 with the mass ratio of manganese spar, 55～60 DEG C it are heated under stirring, continue stirring reaction 30～60min, obtain solidliquid mixture；2) to step 1) in the solidliquid mixture that obtains adds additive cetyl trimethylammonium bromide, the quality of cetyl trimethylammonium bromide is the 0.01%～0.02% of manganese spar quality, stirring reaction 3～3.5 hours is continued at 55～60 DEG C, filter, take filtrate, obtain manganese leachate.The method is simple, easy to operate, and low cost is greatly improved manganese leaching rate, decreases the wasting of resources, adds business efficiency.
Description
Technical field
The present invention relates to hydrometallurgy field, a kind of method being specifically related to manganese leaching rate improved in manganese spar, should
Method is suitably applied the efficient leaching of low grade rhodochrosite.
Background technology
Electrolytic manganese industry is the second largest industry in China's iron and steel industry field, and wherein 90% electrolytic manganese is used for steel and iron industry,
There is the title of " without manganese not Cheng Gang ".Through the development of nearly 50 years, within 2000, China became electrolytic manganese production state the biggest in the world, disappears
Take state and exported country.In China's manganese resource, rich manganese ore only accounts for 6.4%, and poor manganese ore accounts for whole nation gross storage capacity 93.6%.Through several
The exploitation of 10 years, the whole nation average grade of mined ore of manganese ore is down to 14% by 30%.As a example by Guangxi, this district's electrolytic manganese industry 95%
Raw material is that low grade rhodochrosite (is mainly composed of MnCO3), use traditional acid leaching process, filter pressing isolation technics and equipment, entirely
Manganese comprehensive utilization ratio is only about 70%, causes the waste of manganese resource.
Traditional hydrometallurgy manganese deep process technology, directly using sulfuric acid to leach manganese spar is that electrolytic manganese is looked forward to the most both at home and abroad
The widely used production method of industry.Direct acidleach for different sources manganese spar is followed the example of, and domestic scholars is to reaction temperature, reaction
The factors such as system acid ore deposit ratio, liquid-solid ratio, stir speed (S.S.), material particles size and leaching agent concentration have carried out deep discussion, logical
Crossing process parameter optimizing can make the extraction rate of manganese reach more than 85%.
Domestic also have scholar to hindering manganese spar to leach mechanism completely and studied, MnCO3Why it is difficult to by sulfur
The reason that acid is leached completely is the high oxidation state manganese oxide being mingled in manganese spar in manganese carbonate crystal, hinders sulphuric acid and enters crystalline substance
Internal portion reacts with manganese carbonate and makes leaching incomplete.Hispanic Montero O.C. etc. the most further have studied manganese ore leaching
Go out mechanism, find product Mn in leaching process2+Not completely into solution, part Mn2+The sulfur of densification is formed in mineral surface
Silicate layer, thus hinder diffusing into one another of reactant and product, Mn2+It is the control step of whole process from the diffusion of sulphuric acid salt deposit
Suddenly.Above-mentioned research is based primarily upon the laboratory research of manganese spar acid leaching efficiency and influence factor, on affecting low grade rhodochrosite
The influence factor of acid leaching efficiency, interfacial reaction mechanism and industrial applications are still in blank.
Summary of the invention
The problem existed for above-mentioned prior art, the invention provides the side of a kind of manganese leaching rate improved in manganese spar
Method, the method is simple, easy to operate, and low cost is greatly improved manganese leaching rate, decreases the wasting of resources, adds economy
Efficiency.
Realizing the technical scheme that above-mentioned purpose of the present invention used is:
A kind of method of manganese leaching rate improved in manganese spar, comprises the steps:
1) concentrated sulphuric acid and water are added in manganese spar, concentrated sulphuric acid and mass ratio is its theoretical value 1.1～the 1.2 of manganese spar
Times, water is to be heated to 55～60 DEG C under 6～7 1, stirring with the mass ratio of manganese spar, continues stirring reaction 30～60min, obtains
Solidliquid mixture；
2) to step 1) in the solidliquid mixture that obtains adds additive cetyl trimethylammonium bromide, cetyl
The quality of trimethylammonium bromide is the 0.01%～0.02% of manganese spar quality, continues stirring reaction 3～3.5 at 55～60 DEG C
Hour, filter, take filtrate, obtain manganese leachate.
Preferably, in described manganese spar, total Fe content is 13%～15%, bivalent manganese content be 12.56%～
14.32%, tetravalent manganese content is 0.33%～0.62%, and particle diameter is 100～200 mesh, and described content refers both to mass percent and contains
Amount.
Preferably, the mass percent concentration of described concentrated sulphuric acid is 98%.
Preferably, rotating speed during stirring is 100～150rpm.
Compared with prior art, its beneficial effect and advantage are the present invention:
1, improve the surface activity of mineral grain, improve leaching reaction rate
Product Mn in leaching process2+Not completely into solution, part Mn2+The sulfate of densification is formed in mineral surface
Layer, thus hinder diffusing into one another of reactant and product.The surface activity of cetyl trimethylammonium bromide (CTMAB) is made
With, improve mineral grain surface activity, improve ore particles to hydrogen ion adsorption effect, improve leaching reaction rate, promote
Enter the leaching of manganese.
2, the dissolution of high oxidation state manganese in manganese spar is added
High oxidation state manganese oxide in manganese carbonate crystal, hinders sulphuric acid entrance crystals and reacts with manganese carbonate and make leaching
Take not exclusively, after destroying these oxides with reducing agent, completely can leach out by manganese spar at room temperature and in the short period.Ten
The acidleach of the organic component reduction to tetravalent manganese, beneficially manganese contained by six alkyl trimethyl ammonium bromides (CTMAB) is dissolved, and adds manganese
Leaching rate.
3, the sulphuric acid erosion to manganese spar surface is promoted
SEM, TEM result shows, cetyl trimethylammonium bromide (CTMAB) auxiliary leaches, and can effectively facilitate sulphuric acid pair
The erosion on manganese spar surface, reduces the surface granularity of manganese ore, increases the contact area of sulphuric acid and ore particle, improves the leaching rate of manganese.
4, reduce the surface tension of leachate, improve ore particle wettability of the surface
The addition of cetyl trimethylammonium bromide (CTMAB), significantly reduces the surface tension of leachate, improves ore deposit
Grain wettability of the surface, improves the leaching rate of manganese.
5, add ore particle surface micropore crack and soak process of osmosis
There is many micropore cracks in mineral surface, process of osmosis is that the wetting process at tiny solid hole occurs, infiltration
The driving force that process occurs is the additonal pressure that liquid surface meniscus produces.Cetyl trimethylammonium bromide (CTMAB)
Adding, hydrophobic group will be adsorbed in capillary wall, and hydrophilic group stretches in liquid, and additonal pressure can increase, and this contributes to infiltration.Cause
This, add cetyl trimethylammonium bromide (CTMAB) and be conducive to leachate infiltration between porous dehiscence gap, chemosmotic increasing
By force, the raising of manganese leaching rate can there be is certain help.
6, be conducive to solution at ore particle surface spreading, accelerate mass transport process
Adding cetyl trimethylammonium bromide (CTMAB), beneficially solution is at ore particle surface spreading, in mineral surface
Flowing velocity increases, and accelerates mass transport process, improves leaching velocity.The flow velocity accelerating solution can make the thickness of liquid film of mineral surface subtract
Little, Convention diffusion rises relatively, is conducive to leaching reaction.
7, the Concentraton gradient on liquid film both sides, ore particle surface is enhanced
Cetyl trimethylammonium bromide (CTMAB) enhances the Concentraton gradient on mineral surface liquid film both sides, strengthens molecule
Diffusion and Convention diffusion process, improve and leach reaction rate, thus improve the leaching rate of manganese.
8, the ORP current potential of Leaching Systems is improved
Add cetyl trimethylammonium bromide (CTMAB), the ORP current potential being effectively improved in Leaching Systems, promote manganese
Leach.
9, there is significant economic benefit, environmental benefit
Adding cetyl trimethylammonium bromide (CTMAB), improve the leaching of manganese, the Fe content in manganese slag is dropped
Low, improve the comprehensive utilization ratio of manganese, economize on resources, and reduce the pollution to environment.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is specifically described.
Embodiment 1
A kind of method of manganese leaching rate improved in manganese spar, comprises the steps:
1, concentrated sulphuric acid and water that mass percent concentration is 98% are added in manganese spar, concentrated sulphuric acid and the quality of manganese spar
1.1 times that ratio is its theoretical value, water is 61 with the mass ratio of manganese spar, is heated to 55 DEG C, continues under stirring (rotating speed is 110rpm)
Continuous stirring (rotating speed is 110rpm) 30min, obtains solidliquid mixture；
2, to step 1) in the solidliquid mixture that obtains adds additive cetyl trimethylammonium bromide, cetyl
The quality of trimethylammonium bromide is the 0.01% of manganese spar quality, and continuing stirring (rotating speed is 110rpm) at 55 DEG C, to react 3 little
Time, filter, take filtrate, obtain manganese leachate.
Manganese spar in the present embodiment is certain low grade rhodochrosite new greatly from Guangxi, and its total Fe content is 13.1%, bivalence
Fe content is 12.56%, and tetravalent manganese content is 0.33%, and granularity is 100～200 mesh.
Carrying out the content of the manganese in solidliquid mixture and manganese leachate knowable to detection, step 1 uses common acid system to soak
Going out manganese spar, manganese leaching rate is 89.5%, and after step 2 adds additive cetyl trimethylammonium bromide, manganese leaching rate is
95.2%, it can be seen that, the method, after adding additive cetyl trimethylammonium bromide, can be effectively improved manganese leaching rate.
Embodiment 2
A kind of method of manganese leaching rate improved in manganese spar, comprises the steps:
1, concentrated sulphuric acid and water that mass percent concentration is 98% are added in manganese spar, concentrated sulphuric acid and the quality of manganese spar
1.15 times that ratio is its theoretical value, water is 6.5 1 with the mass ratio of manganese spar, is heated to 60 under stirring (rotating speed is 120rpm)
DEG C, continue stirring (rotating speed is 120rpm) reaction 45min, obtain solidliquid mixture；
2, to step 1) in the solidliquid mixture that obtains adds additive cetyl trimethylammonium bromide, cetyl
The quality of trimethylammonium bromide is the 0.02% of manganese spar quality, continues stirring (rotating speed is 120rpm) and react 3.5 at 60 DEG C
Hour, filter, take filtrate, obtain manganese leachate.
Manganese spar in the present embodiment is from Xiushan, Chongqing low grade rhodochrosite, and its total Fe content is 14.3%, bivalence
Fe content is 13.5%, and tetravalent manganese content is 0.46%, and granularity is 100～200 mesh.
Carrying out the content of the manganese in solidliquid mixture and manganese leachate knowable to detection, step 1 uses common acid system to soak
Going out manganese spar, manganese leaching rate is 90.1%, and after step 2 adds additive cetyl trimethylammonium bromide, manganese leaching rate is
95.8%, it can be seen that, the method, after adding additive cetyl trimethylammonium bromide, can be effectively improved manganese leaching rate.
Embodiment 3
A kind of method of manganese leaching rate improved in manganese spar, comprises the steps:
1, concentrated sulphuric acid and water that mass percent concentration is 98% are added in manganese spar, concentrated sulphuric acid and the quality of manganese spar
1.2 times that ratio is its theoretical value, water is 71 with the mass ratio of manganese spar, is heated to 60 DEG C, continues under stirring (rotating speed is 150rpm)
Continuous stirring (rotating speed is 150rpm) reaction 60min, obtains solidliquid mixture；
2, to step 1) in the solidliquid mixture that obtains adds additive cetyl trimethylammonium bromide, cetyl
The quality of trimethylammonium bromide is the 0.02% of manganese spar quality, continues stirring (rotating speed is 150rpm) and react 3.5 at 60 DEG C
Hour, filter, take filtrate, obtain manganese leachate.
Manganese spar in the present embodiment is from Huayuan, Hunan low grade rhodochrosite, and its total Fe content is 14.9%, bivalence
Fe content is 14.1%, and tetravalent manganese content is 0.61%, and granularity is 100～200 mesh.
Carrying out the content of the manganese in solidliquid mixture and manganese leachate knowable to detection, step 1 uses common acid system to soak
Going out manganese spar, manganese leaching rate is 90.8%, and after step 2 adds additive cetyl trimethylammonium bromide, manganese leaching rate is
96.9%, it can be seen that, the method, after adding additive cetyl trimethylammonium bromide, can be effectively improved manganese leaching rate.
Claims (4)
1. the method for the manganese leaching rate that a kind is improved in manganese spar, it is characterised in that comprise the steps:
1) concentrated sulphuric acid and water are added in manganese spar, concentrated sulphuric acid and mass ratio is its theoretical value 1.1～1.2 times of manganese spar,
Water is to be heated to 55～60 DEG C under 6～7 1, stirring with the mass ratio of manganese spar, continues stirring reaction 30～60min, consolidate
Liquid mixture；
2) to step 1) in the solidliquid mixture that obtains adds additive cetyl trimethylammonium bromide, cetyl front three
The quality of base ammonium bromide is the 0.01%～0.02% of manganese spar quality, continues stirring reaction 3～3.5 little at 55～60 DEG C
Time, filter, take filtrate, obtain manganese leachate.
The method of the manganese leaching rate in raising manganese spar the most according to claim 1, it is characterised in that: described manganese spar
In total Fe content be 13%～15%, bivalent manganese content is 12.56%～14.32%, tetravalent manganese content be 0.33%～
0.62%, granularity is 100～200 mesh.
The method of the manganese leaching rate in raising manganese spar the most according to claim 1, it is characterised in that: described concentrated sulphuric acid
Mass percent concentration be 98%.
The method of the manganese leaching rate in raising manganese spar the most according to claim 1, it is characterised in that: rotating speed during stirring
It is 100～150rpm.
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| CN201610573314.XA CN106191473B (en) | 2016-07-20 | 2016-07-20 | A kind of method of manganese leaching rate in raising manganese spar |
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| CN201610573314.XA CN106191473B (en) | 2016-07-20 | 2016-07-20 | A kind of method of manganese leaching rate in raising manganese spar |
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| CN106191473B CN106191473B (en) | 2018-09-14 |
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|---|---|---|---|---|
| CN1453380A (en) * | 2002-04-27 | 2003-11-05 | 邹兴 | Improved process of extracting manganese from dialozite |
| CN102021346A (en) * | 2011-01-06 | 2011-04-20 | 中国环境科学研究院 | Method for recovering soluble manganese in electrolytic manganese waste residue |
| CN102643986A (en) * | 2012-04-16 | 2012-08-22 | 花垣科信新材料有限责任公司 | Method for producing electrolytic manganese by taking pyrolusite as raw material through wet method reduction leaching |
| CN102719667A (en) * | 2012-07-06 | 2012-10-10 | 北方民族大学 | Method for extracting manganese from electrolytic manganese waste residues or low-quality manganese ore by utilizing mechanochemical method and auxiliary agent thereof |
| CN103526020A (en) * | 2013-11-05 | 2014-01-22 | 广西大学 | Method for lixiviating manganese ore containing manganous silicate |
-
2016
- 2016-07-20 CN CN201610573314.XA patent/CN106191473B/en active Active
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1453380A (en) * | 2002-04-27 | 2003-11-05 | 邹兴 | Improved process of extracting manganese from dialozite |
| CN102021346A (en) * | 2011-01-06 | 2011-04-20 | 中国环境科学研究院 | Method for recovering soluble manganese in electrolytic manganese waste residue |
| CN102643986A (en) * | 2012-04-16 | 2012-08-22 | 花垣科信新材料有限责任公司 | Method for producing electrolytic manganese by taking pyrolusite as raw material through wet method reduction leaching |
| CN102719667A (en) * | 2012-07-06 | 2012-10-10 | 北方民族大学 | Method for extracting manganese from electrolytic manganese waste residues or low-quality manganese ore by utilizing mechanochemical method and auxiliary agent thereof |
| CN102719667B (en) * | 2012-07-06 | 2014-10-08 | 北方民族大学 | Method for extracting manganese from electrolytic manganese waste residues or low-quality manganese ore by utilizing mechanochemical method and auxiliary agent thereof |
| CN103526020A (en) * | 2013-11-05 | 2014-01-22 | 广西大学 | Method for lixiviating manganese ore containing manganous silicate |
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