CN101307462A - Deironing method for ferric manganese ore by leaching method - Google Patents
Deironing method for ferric manganese ore by leaching method Download PDFInfo
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- CN101307462A CN101307462A CNA200810012335XA CN200810012335A CN101307462A CN 101307462 A CN101307462 A CN 101307462A CN A200810012335X A CNA200810012335X A CN A200810012335XA CN 200810012335 A CN200810012335 A CN 200810012335A CN 101307462 A CN101307462 A CN 101307462A
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Abstract
The invention relates to a method for leaching and deferrization of ferric manganese ore, which solves the problem that slurry is thick and difficult to filter in the procedure of leaching and deferrization during the process of using Western Liaoning manganous carbonate ore to produce electrolytic manganese metals. The method is to add anolyte which is enough to immerse materials into a combination tank. The method is characterized in that: sulfuric acid and manganous carbonate powdered ore are added into the combination tank in turn at first and then manganese dioxide powdered ore is added subsequently; stirring is performed continuously during the charging process, and simultaneously the solution temperature is maintained to between 80 and 95 DEG C; ammonia is added into the solution until the Ph is between 6 and 7; finally whether to add ammonium sulphate and the addition of the ammonium sulphate are determined according to the concentration of the ammonium sulphate in the solution. By adoption of the method, the electrolytic manganese metals can be produced by utilization of the manganous carbonate ore and manganese oxide ore in the Western Liaoning which are cheap and easy to obtain; after neutralization treatment, sigma Fe in the solution is less than 0.001 gram per liter, and the leaching efficiency of manganese is over 80 percent; and all the index requirements are met.
Description
Technical field
The invention belongs to and produce the electrolytic metal Mn technical field, is the method that leaches deironing in the raw material production electrolytic metal Mn process with west of Liaoning manganese ore particularly.
Background technology
The producer of domestic production electrolytic metal Mn mostly concentrates on ground such as Hunan, Guizhou, Sichuan, Guangxi at present, all uses southern manganese ore in each manufacturer production, comprises that manganese carbonate ore and dioxide ore for manganese are raw material.It leaches iron removal is to add the anolyte that is enough to make the material infiltration earlier in the chemical combination jar, sulfuric acid and manganous carbonate breeze is added in the chemical combination jar successively again, carries out the leaching reaction of manganese, and manganese is with Mn
2+Form enters solution, and meanwhile, the iron in the manganese carbonate ore is also leached, with Fe
2+Form enters solution.Added the manganous carbonate breeze 1-2 hour or add after the longer time dioxide ore for manganese as oxygenant with Fe
2+Be oxidized to Fe
3+, add ammoniacal liquor then, with Fe
3+Form with Fe (OH) 3 precipitates down, enters the slag phase, and after filtering, solution separates with slag, and mn ion enters solution, and iron enters the slag phase, reaches the deironing purpose.Because the iron level in the southern manganese ore is all very low, most of between 1%~3%, handle than being easier to; My company is located in West Liaoning, and we use the geographic manganese carbonate ore in Chaoyang (the Mn 17-22%, the ∑ Fe 10-16% that wherein contain weight percent), and resource is abundanter, but Fe content higher, be difficult for removing.If with reference to the leaching deironing operation steps of southern manganese ore, in the chemical combination jar, add sulfuric acid and manganous carbonate breeze successively earlier, carry out the leaching reaction of manganese, the iron in the manganese carbonate ore is also leached simultaneously, with Fe
2+Form enters solution.After adding the manganous carbonate breeze 1----2 hour or the longer time back add dioxide ore for manganese as oxygenant, with Fe
2+Be oxidized to Fe
3+Because this moment, leaching process finished [Fe in the solution
2+] concentration reached 15g/L-30g/L, add ammoniacal liquor neutralization then, moment generates lot of F e (OH)
3, very easily the form colloid, make slip thickness, solid-liquid be difficult to separate, cause production process to continue, final technology can't be got through.
Summary of the invention:
To produce the slip thickness that exists at the leaching iron removal step in the electrolytic metal Mn process, the problem of filtration difficulty in order solving, to propose following technical scheme with the high west of Liaoning manganese carbonate ore of iron-holder.
A kind of ferric manganese ore leaches the method for deironing, in the chemical combination jar, add the anolyte that is enough to make the material infiltration, its special character is to add earlier sulfuric acid and west of Liaoning manganous carbonate breeze in the chemical combination jar successively, and then add the Manganse Dioxide breeze, constantly stir in the reinforced process, keep 80 ℃~95 ℃ of solution temperatures, Fe after the above-mentioned raw materials reaction, in the solution
2+Add ammoniacal liquor during≤0.001g/L to PH=6~7, according to the concentration of ammonium sulfate in the solution, whether decision adds ammonium sulfate and add-on thereof at last.
In order to guarantee the nitrogen balance of system, and save ammonia volume, in aforesaid method, add add earlier before the ammoniacal liquor in the manganese slag to PH=2~5, replacing partial ammonia water is as the neutralizing agent deironing.
The Mn 17%---22%, the ∑ Fe 10-16% that contain weight percent in the manganese carbonate ore of the above-mentioned west of Liaoning.
The manganese slag is the slag that manganese in smelting produces in above-mentioned, wherein contains the Mn 18% of weight percent---20%, CaO 33%---36%, MgO 4%---6%.
The present invention has following advantage:
1, by adjusting deironing preoxidation operational condition, with joining day of dioxide ore for manganese by original interval 1-2 hour, change to after adding the manganous carbonate breeze and and then add.Like this can be along with Fe
2+Enter solution, at any time it is oxidized to Fe
3+, at high temperature generate pyrrhosiderite (FeOOH) or ammonium jarosite (NH at any time
4) Fe
3(SO
4)
2(OH)
6Precipitation is unlikely to make Fe
2+Or Fe
3+Be accumulated to too high concentration, thereby reduced formation ferric hydroxide colloid (Fe (OH)
3) probability, make that to leach the slurry filtration performance good.Experiment shows, ∑ Fe<0.001g/L in the solution after the process neutralizing treatment, and the requirement that all touches the mark, thereby, do not have technology and product quality problem with the raw material of west of Liaoning manganese ore as the production electrolytic metal Mn.
2, raw material sources are extensive, can utilize west of Liaoning manganese carbonate ore cheap and easy to get and manganese oxide ore to produce electrolytic metal Mn.
3, the manganese leaching yield is more than 80%.
4, do not increase other technological process.
Embodiment
Embodiment 1
A kind of ferric manganese ore leaches the method for deironing, to 210m
3The chemical combination jar in fill 60m
3Anolyte after, drop into manganous carbonate breeze, manganous chloride breeze, ammonium sulfate, add sulfuric acid, add ammoniacal liquor again and to the reinforced process of PH=6.7, constantly stir, keep 80 ℃~95 ℃ of temperature of reaction simultaneously.Take a sample and send the press filtration operation after qualified.The addition sequence of various raw materials is: add sulfuric acid and manganous carbonate breeze successively earlier in the chemical combination jar, and then add the Manganse Dioxide breeze, the reaction back adds ammoniacal liquor, adds ammonium sulfate at last.
Embodiment 2
A kind of ferric manganese ore leaches the method for deironing, to 210m
3The chemical combination jar in fill 70m
3Anolyte after, drop into 16.5 tons of manganous carbonate breezes, 8.2 tons Manganse Dioxide breeze, 12.5 tons ammonium sulfate, add 14.465 tons in sulfuric acid, the manganese slag is to PH=2 in adding, add ammoniacal liquor again to PH=6.7, constantly stir in the reinforced process, in the chemical combination jar, feed steam simultaneously, keep 80~90 ℃ of chemical combination temperature, take a sample and deliver to the press filtration operation after qualified.The addition sequence of various raw materials is: add sulfuric acid and manganous carbonate breeze successively earlier in the chemical combination jar, and then add the Manganse Dioxide breeze, manganese slag and ammoniacal liquor during the reaction back adds add ammonium sulfate at last.
Embodiment 3
A kind of ferric manganese ore leaches the method for deironing, to 210m
3The chemical combination jar in fill 60m
3Anolyte after, drop into 16.5 tons of manganous carbonate breezes, 8.2 tons Manganse Dioxide breeze, 11.5 tons ammonium sulfate, add 13.4 tons in sulfuric acid, the manganese slag is to PH=5 in adding, add ammoniacal liquor again to PH=6.6, constantly stir in the reinforced process, in the chemical combination jar, feed steam simultaneously, keep 80~85 ℃ of chemical combination temperature.Take a sample and deliver to the press filtration operation after qualified.The addition sequence of various raw materials is: add sulfuric acid and manganous carbonate breeze successively earlier in the chemical combination jar, and then add the Manganse Dioxide breeze, manganese slag and ammoniacal liquor during the reaction back adds add ammonium sulfate at last.
Claims (2)
1, a kind of ferric manganese ore leaches the method for deironing, in the chemical combination jar, add the anolyte that is enough to make the material infiltration, it is characterized in that in the chemical combination jar, adding successively earlier sulfuric acid and west of Liaoning manganous carbonate breeze, and then add the Manganse Dioxide breeze, constantly stir in the reinforced process, keep 80 ℃~95 ℃ of solution temperatures, Fe after the above-mentioned raw materials reaction, in the solution
2+Add ammoniacal liquor during≤0.001g/L to PH=6~7, according to the concentration of ammonium sulfate in the solution, whether decision adds ammonium sulfate and add-on thereof at last.
2, a kind of ferric manganese ore according to claim 1 leaches the method for deironing, it is characterized in that adding add earlier before the ammoniacal liquor in the manganese slag to PH=2~5, replacing partial ammonia water is as the neutralizing agent deironing.
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CNA200810012335XA CN101307462A (en) | 2008-07-16 | 2008-07-16 | Deironing method for ferric manganese ore by leaching method |
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CNA200810012335XA CN101307462A (en) | 2008-07-16 | 2008-07-16 | Deironing method for ferric manganese ore by leaching method |
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Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101892383A (en) * | 2010-06-30 | 2010-11-24 | 重庆大学 | Reinforced leaching de-ironing device and de-ironing method of manganese ore slurry |
CN102094124A (en) * | 2011-03-10 | 2011-06-15 | 中信锦州金属股份有限公司 | Method for producing electrolytic metal manganese and application thereof |
CN102140650A (en) * | 2011-03-10 | 2011-08-03 | 中信锦州金属股份有限公司 | Method and application for producing electrolytic manganese by using novel oxidizing agent for removing iron |
CN102534215A (en) * | 2010-12-08 | 2012-07-04 | 中国环境科学研究院 | Method for purifying and deferrizing electrolytic manganese leach solution |
CN103509955A (en) * | 2013-07-17 | 2014-01-15 | 中信大锰矿业有限责任公司 | Two ore combined process for treatment of laterite nickel ore and pyrolusite |
CN104404568A (en) * | 2014-12-15 | 2015-03-11 | 中信大锰矿业有限责任公司大新锰矿分公司 | Method for producing electrolytic manganese metal with manganese carbonate ore |
CN107586951A (en) * | 2017-08-11 | 2018-01-16 | 四川大学 | A kind of method that manganese, iron isochronous resources utilize in low-grade manganese carbonate ore |
CN108060300A (en) * | 2017-12-15 | 2018-05-22 | 广西新振锰业集团有限公司 | A kind of electrolytic manganese metal raw material mixes throwing deferrization process |
-
2008
- 2008-07-16 CN CNA200810012335XA patent/CN101307462A/en active Pending
Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101892383A (en) * | 2010-06-30 | 2010-11-24 | 重庆大学 | Reinforced leaching de-ironing device and de-ironing method of manganese ore slurry |
CN102534215A (en) * | 2010-12-08 | 2012-07-04 | 中国环境科学研究院 | Method for purifying and deferrizing electrolytic manganese leach solution |
CN102534215B (en) * | 2010-12-08 | 2013-10-23 | 中国环境科学研究院 | Method for purifying and deferrizing electrolytic manganese leach solution |
CN102094124B (en) * | 2011-03-10 | 2013-11-20 | 中信锦州金属股份有限公司 | Method for producing electrolytic metal manganese and application thereof |
CN102140650B (en) * | 2011-03-10 | 2013-10-16 | 中信锦州金属股份有限公司 | Method and application for producing electrolytic manganese by using novel oxidizing agent for removing iron |
CN102140650A (en) * | 2011-03-10 | 2011-08-03 | 中信锦州金属股份有限公司 | Method and application for producing electrolytic manganese by using novel oxidizing agent for removing iron |
CN102094124A (en) * | 2011-03-10 | 2011-06-15 | 中信锦州金属股份有限公司 | Method for producing electrolytic metal manganese and application thereof |
CN103509955A (en) * | 2013-07-17 | 2014-01-15 | 中信大锰矿业有限责任公司 | Two ore combined process for treatment of laterite nickel ore and pyrolusite |
CN103509955B (en) * | 2013-07-17 | 2016-01-20 | 中信大锰矿业有限责任公司 | The technique of two ore deposit integrated process process red soil nickel ores and pyrolusite |
CN104404568A (en) * | 2014-12-15 | 2015-03-11 | 中信大锰矿业有限责任公司大新锰矿分公司 | Method for producing electrolytic manganese metal with manganese carbonate ore |
CN107586951A (en) * | 2017-08-11 | 2018-01-16 | 四川大学 | A kind of method that manganese, iron isochronous resources utilize in low-grade manganese carbonate ore |
CN107586951B (en) * | 2017-08-11 | 2018-10-26 | 四川大学 | A kind of method that manganese, iron isochronous resources utilize in low-grade manganese carbonate ore |
CN108060300A (en) * | 2017-12-15 | 2018-05-22 | 广西新振锰业集团有限公司 | A kind of electrolytic manganese metal raw material mixes throwing deferrization process |
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