CN1075120C - Process for extracting manganese ore with sulfuric acid at ordinary temperature - Google Patents
Process for extracting manganese ore with sulfuric acid at ordinary temperature Download PDFInfo
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- CN1075120C CN1075120C CN97108214A CN97108214A CN1075120C CN 1075120 C CN1075120 C CN 1075120C CN 97108214 A CN97108214 A CN 97108214A CN 97108214 A CN97108214 A CN 97108214A CN 1075120 C CN1075120 C CN 1075120C
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Abstract
The present invention relates to a method for extracting manganese from manganese ore. The present invention overcomes the defects that the existing steam thermal methods have high energy consumption, low leaching rate and high cost. The method of the present invention comprises the procedures: manganese ore powder and waste electrolytic manganese solution, or waste electrolytic manganese dioxide solution, or water react with excessive added sulphuric acid after pulping, industrial pyrolusite powder, waste electrolytic manganese solution, the additive of sulfite are orderly added for further reaction, and industrial pyrolusite powder is added again for final reaction; the reaction product of manganese sulphate solution is collected from reaction solution. The method is suitable for various manufacturers which produce manganese products with manganese ore powder and sulphuric acid as raw material.
Description
The present invention relates to a kind of method of using the method, particularly a kind of extracting manganese ore with sulfuric acid at ordinary temperature of sulfuric acid to leach manganese ore.
At present, useful sulfuric acid of institute and manganese ore powder are the raw material production manganous sulfate, electrolytic metal Mn, electrolytic manganese dioxide, the manufacturer of manganese goods such as manganous carbonate, all be to adopt heat the down method abbreviation steam heat method of sulfuric acid and manganese ore reaction leaching generation manganese sulfate solution of steam, this method is not only wanted facilities such as steam boiler, pipeline, and the leaching rate of energy consumption height and manganese ore is not high yet, generally about 85%, the production cost height.
The object of the present invention is to provide a kind of technology simple, with low cost, the method for the extracting manganese ore with sulfuric acid at ordinary temperature that leaching rate is high.
The present invention finishes with following mode: the method for extracting manganese ore with sulfuric acid at ordinary temperature is to adopt following step successively:
1). the manganese ore powder is fed in the retort, the useless electrolytic manganese solution of adding retort volume 25%-50% or useless electrolytic manganese dioxide solution or water mixing break into pulpous state liquid, add by industrial strong sulfuric acid response 0.5-1.5 hour that tests out the excessive 5%-15% of the actual acid consumption of manganese ore powder again;
2). add the industrial pyrolusite powder of pressing manganese ore grain weight amount 3%-4% and reacted 0.5-1.5 hour;
3). add useless electrolytic manganese solution or useless electrolytic manganese dioxide solution or water to the retort pre-determined volume, reacted 0.5-1.5 hour;
4). adding additive is ammonium sulphite or ammonium bisulfite or S-WAT or sodium bisulfite or potassium sulfite, and supplementary additive is formaldehyde or methyl alcohol or hydrogen peroxide reaction 2-4 hour, and the additive add-on is the 0.5%-5% of manganese ore grain weight amount;
5). add the industrial pyrolusite powder of pressing manganese ore grain weight amount 5%-15% and reacted 0.5-1.5 hour, from reaction soln, collect the resultant manganese sulfate solution.
The additive that adds is that liquid state contains SO
2During 250-300g/L, its add-on is the 1.6%-5% of manganese ore grain weight amount, and when additive when being solid-state, its add-on is the 0.5%-2% of manganese ore grain weight amount.
The technical process of extracting manganese ore with sulfuric acid at ordinary temperature method of the present invention is not only simple to operate, and leaching rate height, oxidation of divalent is complete, adopt and add contained a small amount of high oxidation state manganese in the additive sulphite reduction manganese ore powder, activate the reaction of manganese carbonate ore and vitriolic simultaneously, make the manganese in the manganese ore powder be changed into manganese sulfate solution by sulfuric acid to leach dramatically, supplementary additive suppresses ferric iron and is not reduced into ferrous iron by sulfurous acid, adopt excessive sulfuric acid can guarantee that sulphite and high oxidation state manganese react smoothly, this method manganese leaching rate reaches and surpasses the steam heat law technology, additive is with low cost, and without any detrimentally affect, it produces stable to the production of back operation.It and steam heat method are relatively, steam and province have been saved except equipment such as boiler and steam-pipes, reduced production cost widely, this method be applicable to useful sulfuric acid and manganese ore powder be that the producer of raw material production manganous sulfate, manganous carbonate, electrolytic metal Mn, electrolytic manganese dioxide and all manganese goods uses.
The present invention is further detailed explanation with embodiment below:
Technical process of the present invention is:
The manganese ore powder adds the useless electrolytic manganese liquid (or useless electrolytic manganese dioxide solution or water) of part and mixes and break into pulpous state liquid → add strong sulfuric acid response → add part industry pyrolusite powder reaction → fill it up with the industrial pyrolusite powder reaction → liming of retort → addings sulphite additive reaction → adding with useless electrolytic manganese liquid to neutralize and add cleaner and additive, filtration collection resultant of reaction manganese sulfate solution.
Now contain manganese 20% with the manganese ore powder, wherein the manganese that exists with the manganous carbonate form is 19%, and the actual acid consumption that tests out the manganese ore powder is 0.55 ton of/ton ore deposit, contains manganese 12.5g/L in sulfuric acid concentration 93%, the electrolytic manganese waste liquid, contains H
2SO
4, the 20.0g/L starting material are implemented the inventive method:
Embodiment one: at 22m
3Add useless electrolytic manganese liquid total amount 20m in the volume retort
3, all leaching concentration by manganese is 2.75 tons of the charging capacitys that 40g/L calculates the manganese ore powder, calculating the vitriolic add-on by excessive 10% is 1.36 tons, can react smoothly to guarantee sulphite and high oxidation state manganese.
With 2.75 tons of manganese ore powder and 7m
3Useless electrolytic manganese liquid drops in the retort, stirs into pulpous state liquid, adds 1.36 ton 93% industrial sulphuric acid then, stirs reaction down after 1 hour, adds 100 kilograms of reactions of industrial pyrolusite powder 1 hour, adds 13m then
3Useless electrolytic manganese liquid reaction 1 hour adds the additive ammonium sulfite solution and (contains SO
2280g/L) 80 kilograms, add a small amount of high oxidation state manganese contained in the ammonium sulphite reduction manganese ore powder (as Mn0
2), activate the reaction of manganous carbonate and vitriolic simultaneously, make the manganese in the manganese ore powder be changed into manganese sulfate solution by sulfuric acid to leach dramatically, supplementary additive is content 10% methyl alcohol 200ml, reacted 2.5 hours, supplementary additive suppresses ferric iron and is not reduced into ferrous iron by sulfurous acid, and some ore deposit can not add supplementary additive, and the supplementary additive add-on is every retort (22m
3) 200-500ml adds 250 kilograms of industrial pyrolusite powders again, after reacting half an hour, detect manganese and ferrous content in the solution, ferrous content reaches≤0.01% requirement after, adding liming (calcium hydroxide) is neutralized to PH6.5-7.0 and gets final product, and this moment, the manganese sulfate solution leaching rate was generally about 95%.
Embodiment two: at 22m
3Retort in add useless electrolytic manganese liquid total amount 21m
3, all leaching concentration by manganese is that the charging capacity that 40g/L calculates the manganese ore powder is 2.89 tons, is 1.39 tons by the add-on of excessive 8% calculating industrial sulphuric acid (93%).With 2.89 tons of manganese ore powder and 7m
3After waste electrolyte drops into and stirs pulping in the retort, 1.39 tons in the sulfuric acid of adding 93%, reaction 1 hour stirs.Add 100 kilograms of industrial pyrolusite powders again, reacted 1 hour.Add useless electrolytic manganese solution 14m
3, reacted 1 hour, add ammonium sulfite solution and (contain SO
2280g/L) 100 kilograms, and add 10% methyl alcohol 200ml simultaneously, reacted 2.5 hours.Add 250 kilograms of industrial pyrolusite powders, the reaction half an hour after, manganese and ferrous content in the detection reaction resultant solution, when ferrous amount reach≤0.01% requirement after, add liming and be neutralized to PH:6.5-7.0, at this moment, the manganese sulfate solution leaching rate can reach about 95%.
Claims (2)
1. the method for an extracting manganese ore with sulfuric acid at ordinary temperature is characterized in that adopting successively following step:
1). the manganese ore powder is fed in the retort, the useless electrolytic manganese solution of adding retort volume 25%-50% or useless electrolytic manganese dioxide solution or water mixing break into pulpous state liquid, add by industrial strong sulfuric acid response 0.5-1.5 hour that tests out the excessive 5%-15% of the actual acid consumption of manganese ore powder again;
2). add the industrial pyrolusite powder of pressing manganese ore grain weight amount 3%-4% and reacted 0.5-1.5 hour;
3). add useless electrolytic manganese solution or useless electrolytic manganese dioxide solution or water to the retort pre-determined volume, reacted 0.5-1.5 hour;
4). adding additive is ammonium sulphite or ammonium bisulfite or S-WAT or sodium bisulfite or potassium sulfite, and supplementary additive is formaldehyde or methyl alcohol or hydrogen peroxide reaction 2-4 hour, and the additive add-on is the 0.5%-5% of manganese ore grain weight amount;
5). add the industrial pyrolusite powder of pressing manganese ore grain weight amount 5%-15% and reacted 0.5-1.5 hour, from reaction soln, collect the resultant manganese sulfate solution.
2. according to the method for the described extracting manganese ore with sulfuric acid at ordinary temperature of claim 1, it is characterized in that the additive that adds is that liquid state contains SO
2During 250-300g/L, its add-on is the 1.6%-5% of manganese ore grain weight amount, and when additive when being solid-state, its add-on is the 0.5%-2% of manganese ore grain weight amount.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97108214A CN1075120C (en) | 1997-09-09 | 1997-09-09 | Process for extracting manganese ore with sulfuric acid at ordinary temperature |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97108214A CN1075120C (en) | 1997-09-09 | 1997-09-09 | Process for extracting manganese ore with sulfuric acid at ordinary temperature |
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| CN1210893A CN1210893A (en) | 1999-03-17 |
| CN1075120C true CN1075120C (en) | 2001-11-21 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN97108214A Expired - Fee Related CN1075120C (en) | 1997-09-09 | 1997-09-09 | Process for extracting manganese ore with sulfuric acid at ordinary temperature |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1295355C (en) * | 2004-07-19 | 2007-01-17 | 中南大学 | Method of manufacturing electrolytic metal manganese using titanium white waste acid and manganese dioxide ore |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101260471B (en) * | 2008-04-28 | 2010-06-02 | 中国环境科学研究院 | Complete set of cleaning producing technique for extracting soluble manganese from manganese residue by using anode liquor |
| CN101880767A (en) * | 2010-06-07 | 2010-11-10 | 姚茂君 | Process for reducing leached pyrolusite ore by iron powder |
| CN103757444B (en) * | 2013-12-29 | 2015-05-13 | 四川师范大学 | Method for leaching pyrolusite |
| CN103757249A (en) * | 2013-12-29 | 2014-04-30 | 四川师范大学 | Method for leaching manganese carbonate ore |
| CN103757247A (en) * | 2013-12-29 | 2014-04-30 | 四川师范大学 | Method for leaching manganese carbonate ore |
| CN103937973B (en) * | 2014-04-16 | 2016-01-06 | 广西民族大学 | A kind of method of Organic-inorganic composite reducing pyrolusite |
| CN113088999B (en) * | 2021-03-31 | 2021-12-31 | 广西桂柳新材料股份有限公司 | Preparation method of electrolytic manganese dioxide for mercury-free alkaline zinc-manganese battery |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1086548A (en) * | 1992-11-02 | 1994-05-11 | 冶金工业部长沙冶金研究院 | Preparation of highly pure manganese sulfate with high yield rate |
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- 1997-09-09 CN CN97108214A patent/CN1075120C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1086548A (en) * | 1992-11-02 | 1994-05-11 | 冶金工业部长沙冶金研究院 | Preparation of highly pure manganese sulfate with high yield rate |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1295355C (en) * | 2004-07-19 | 2007-01-17 | 中南大学 | Method of manufacturing electrolytic metal manganese using titanium white waste acid and manganese dioxide ore |
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| CN1210893A (en) | 1999-03-17 |
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