CN101988154A - New technology for preparing electrolytic manganese metal solution and recycling iron by reducing pyrolusite with iron scraps - Google Patents
New technology for preparing electrolytic manganese metal solution and recycling iron by reducing pyrolusite with iron scraps Download PDFInfo
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- CN101988154A CN101988154A CN2010105350338A CN201010535033A CN101988154A CN 101988154 A CN101988154 A CN 101988154A CN 2010105350338 A CN2010105350338 A CN 2010105350338A CN 201010535033 A CN201010535033 A CN 201010535033A CN 101988154 A CN101988154 A CN 101988154A
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Abstract
The invention discloses a new technology for preparing manganese sulfate solution which is used for electrolyzing manganese metal and recycling iron through the atmospheric pressure leaching of pyrolusite and iron scraps. The technology comprises the following steps: adding pyrolusite in a certain concentration of sulphuric acid solution, mixing evenly; adding iron scraps used as the reductant in a reaction tank, performing mechanical agitation for 1h-3h under different reaction temperatures to obtain reaction leachate; according to the changes of the reaction time and the pH value, adding heavy calcium carbonate and ammonia water in turn to adjust the pH value of the solution to 6.3-6.7; then adding sodium N,N-dimethyl dithiocarbaminate (SDD) to remove impurities such as heavy metal ions and purify; filtering, adding additive to obtain manganese sulfate solution used for electrolyzing manganese; and recycling iron from filter residue through alkali leaching and acid leaching to produce polyferric sulfate. The invention has the advantage that iron scraps are used as the reductant which have wide sources and rich raw materials and can be leached out under the atmospheric pressure; and iron scraps can be recycled to produce the water purification agent and have great economic benefit.
Description
Technical field
The present invention relates to a kind of be reductive agent with the waste iron filing, normal pressure leaches the manganese sulfate solution be used for electrolytic metal Mn from pyrolusite novel process, the novel process that exploitation is simultaneously reclaimed iron and produced bodied ferric sulfate belongs to the hydrometallurgy field.
Background technology
Waste iron filing produces in mechanical workout or machinofacture process, and waste iron filing just can be used as industrial chemicals or production chemical product through after the oil removal treatment, turns waste into wealth, and reduces the waste of resource.China all will produce a large amount of waste iron filings every year, a lot of recycling becomes particularly important owing to utilizing improper or directly abandoning as byproduct, not only can increase economic added value, and be the development trend of comprehensive utilization of waste materials, meet the strategy of sustainable development.
At present, the reductive agent that is used as pyrolusite mainly contains sulfurous iron ore, sulfurous gas, ferrous sulfate, cane molasses alcohol slops etc., the suitability for industrialized production that has, and what have is also carrying out the test of theory study and Small Scale Industry.Comprehensive various bibliographical information, pyrolusite reduction preparation manganous sulfate mainly contains following several method:
1, reduction roasting method: with pyrolusite and reductive agent (C, CO, H
2, CH
4Deng) reaction, tetravalence manganese is reduced to bivalent manganese, the bivalent manganese that reduction obtains is dissolved in sulphuric acid soln, and through purification and impurity removal, finally producing various manganese is product, is a traditional technology.But this technological equipment investment is big, and big energy-consuming produces a large amount of waste gas waste residues in process of production, and is seriously polluted, and country prohibites time technology and uses.
2, two ore deposit single stage method: with a certain proportion of pyrolusite, sulfurous iron ore pulverize mix after, leach with sulfuric acid, can make the Manganse Dioxide in the pyrolusite be reduced to manganous sulfate, compare reduction roasting method and save the high-temperature roasting operation, simplified apparatus and technical process thereof, the price of sulfurous iron ore is lower, and wide material sources reduce cost, but the manganese leaching yield of two ore deposit single stage method is low, filter residue is many, and the purification and impurity removal difficulty is difficult to obtain qualified electrolytic manganese solution.
3, sulfurous gas lixiviation process: sulfurous gas directly is passed in the pulp bucket that pyrolusite is housed reduces, be a kind of sophisticated technology, in leaching reaction process, produce the by product manganous dithionate, influence the quality of product, so far also not in industrial widespread use.
A kind of gray manganese ore leaching out process as Chinese patent application 200610122400.5, adopting the cane molasses alcohol slops is reductive agent, the leach liquor that stirring reaction 0.5-4h obtains reacting under 50-98 ℃ of temperature, but cane molasses alcohol easily produces organism in reaction, introduced new impurity in the solution, organism is difficult for purifying to be removed.And for example a kind of of Chinese patent application 200710151596.5 produces the method for manganous sulfate by manganese oxide ore, and adopting ferrous sulfate or sulphur is reductive agent, reacts under certain temperature and pressure, though this technology is comparatively ripe, manganese leaching yield height, cost height, the quantity of slag is big, the filtering and impurity removing difficulty.
Summary of the invention
The purpose of this invention is to provide the novel process that pyrolusite and waste iron filing normal pressure leach the manganese sulfate solution that is used for electrolytic metal Mn, it uses waste iron filing as reductive agent, not only technical process is simple relatively, mild condition, speed of response is fast, the leaching yield height of manganese is pollution-free in the pyrolusite, and filter residue can be recycled production water purification agent bodied ferric sulfate.
For achieving the above object, embodiment of the present invention are: a kind of waste iron filing reducing pyrolusite prepares electrolytic manganese metal solution and reclaims the novel process of iron, may further comprise the steps:
(1) pyrolusite is dropped in the reactor, the anolyte that produces when adding distilled water or electrolytic manganese, the weight proportion of the anolyte that produces when pyrolusite and distilled water or electrolytic manganese is 1:5.0 ~ 15.0;
(2) under mechanical stirring, add the vitriol oil and ammonium sulfate in the reactor, make that sulfuric acid concentration reaches 100-200g/L in the mixed solution, ammonium sulfate concentrations reaches 100 ~ 200g/L;
(3) add waste iron filing, leach reaction 0.5 ~ 1h in 25 ~ 60 ℃ of following mechanical stirring of temperature, reaction 1-2h is leached in elevated temperature to 70 ~ 100 a ℃ continuation, impels material reaction complete;
(4) water-ground limestone of adding pyrolusite weight 10% ~ 25% after reacting completely, is pH value to 6.3 ~ 6.7 of 20% ~ 28% ammoniacal liquor regulator solution with concentration again;
(5) 0.2% ~ 1.5% of adding pyrolusite weight Sodium dimethyldithiocarbamate 40min, reaction 0.5 ~ 1h, removal of impurities removing heavy metals ion filters cooling, adds tin anhydride in the filtrate, obtains being directly used in the manganese sulfate solution of electrolytic manganese.
(6) after filtration back gained filter residue and distilled water mix in the step (5), under 50 ~ 90 ℃ of temperature of reaction, add calcium oxide or calcium hydroxide or both mixtures, mechanical stirring reaction 0.5 ~ 1.5h, filtration washing, the filter residue of gained adds dilute sulphuric acid and leaches reaction 0.5 ~ 1h at normal temperatures, filters and obtains ferrum sulfuricum oxydatum solutum, obtains bodied ferric sulfate through underpressure distillation.
In the step (2), the mol ratio of Manganse Dioxide is 1.2 ~ 2.8:1 in the vitriol oil of adding and the pyrolusite.
In the step (2), churned mechanically speed is 800 ~ 2500r/min.
In the step (3), the mol ratio of Manganse Dioxide is 0.5 ~ 1.5: 1 in the waste iron filing of adding and the pyrolusite.
In the step (5), the tin anhydride concentration of adding is 0.02 ~ 0.08g/L.
In the step (6), the mol ratio of calcium oxide or calcium hydroxide or both mixtures and waste iron filing is 0.5 ~ 2.5: 1.
In the step (6), churned mechanically speed is 400 ~ 1000r/min.
In the step (6), the concentration of dilute sulphuric acid is 1.0 ~ 4.5mol/L.
In the process of electrolysis production manganese metal, manganese sulfate solution there is strict requirement, not only the acidity of solution will maintain certain scope, and the content of other metal ions is also had strict restriction.Generally speaking, the foreign matter content in the solution requires: iron is less than 0.2mg/L, and cobalt is less than 0.5 mg/L, nickel is less than 1 mg/L, and silicon is less than 10 mg/L, and copper is less than 0.5 mg/L, if the pH value of solution or the heavy metal ion of solution exceed standard, in the process of electrolytic manganese, might cause the anti-molten of manganese.The invention provides the manganese sulfate solution that is used for electrolysis production manganese.The present invention has realized the novel process with waste iron filing is made reductive agent, extraction can be used for the manganese sulfate solution of electrolysis production manganese from pyrolusite, extraction temperature is divided into two sections, make that Manganse Dioxide leaches in the short period of time in the pyrolusite, the leaching yield of manganese is more than 95%, and slag manganese content is below 1%.The present invention has following advantage:
1, compare with traditional technology, simplify technical process, mild condition, speed of response is fast, just can leach under normal pressure.
2, with adopt the cane molasses alcohol slops to do former dose to compare, in the reaction leaching process, can not produce organism, the removal of impurities ratio of subsequent solution be easier to and electrolysis unaffected.
3, the leaching yield height of manganese in the pyrolusite is pollution-free, and filter residue can be recycled and produce the water purification agent bodied ferric sulfate, and inclusion-free is discharged to outward in the environment, is a green production process, for low-grade pyrolusite development of resources new application approach.
Embodiment
Embodiment 1: pyrolusite contains manganese 33.15%.
The pyrolusite that will contain manganese 33.15% joins in the reactor that can hold 500 milliliters, it is 10:1 that adding distil water makes its liquid-solid ratio, under the condition of mechanical stirring intensity 1000r/min, adding the vitriol oil in the reactor makes its concentration reach 100g/L, ammonium sulfate concentrations reaches 100g/L, the temperature that mixes the afterreaction still is elevated to 30 ℃, the mol ratio 1:0.6 that presses Manganse Dioxide and waste iron filing in the pyrolusite adds waste iron filing, be warmed up to 70 ℃ behind the reaction 60min and continue reaction 60min, keep adding water-ground limestone successively under the temperature-resistant condition and ammoniacal liquor is regulated pH value 6.5, add SDD and remove heavy metal, carrying out slag liquid separates, the manganese leaching yield is 96.12%, and slag contains manganese 0.5%.The solution non-shock chilling that obtains, adding tin anhydride solid makes content reach 0.03g/L and is the manganese sulfate solution that is used for electrolytic manganese production, and filter residue, distilled water mixes the back temperature and is raised to 60 ℃ in reactor, it is 1:1 that the adding calcium oxide makes the mol ratio of its add-on and waste iron filing, under the condition of mechanical stirring intensity 400r/min, react 60min, carry out filtration washing, the filter residue of gained adds an amount of 1.5mol/L dilute sulphuric acid and leaches reaction 30min at normal temperatures, solution filters and obtains ferrum sulfuricum oxydatum solutum, can obtain qualified polyaluminum sulfate iron product through underpressure distillation again.
Embodiment 2 pyrolusites contain manganese 33.15%
The pyrolusite that will contain manganese 33.15% joins in the reactor that can hold 500 milliliters, the anolyte that produces when adding electrolytic manganese (anolyte main component: Mn
2+11.0g/L, sulfuric acid 31.5 g/L, ammonium sulfate 90 g/L) making its liquid-solid ratio is 8:1, under the condition of mechanical stirring intensity 1500r/min, adding the vitriol oil in the reactor makes its concentration reach 150g/L, ammonium sulfate concentrations reaches 100g/L, the temperature that mixes the afterreaction still is elevated to 40 ℃, the mol ratio 1:1.2 that presses Manganse Dioxide and waste iron filing in the pyrolusite adds waste iron filing, is warmed up to 100 ℃ behind the reaction 60min and continues reaction 60min, keeps adding water-ground limestone and ammoniacal liquor adjusting pH value 6.3 successively under the temperature-resistant condition, add SDD and remove heavy metal, carry out slag liquid and separate, the manganese leaching yield is 95.02%, and slag contains manganese 0.8%.The solution non-shock chilling that obtains, adding tin anhydride solid makes content reach 0.07g/L and is the manganese sulfate solution that is used for electrolytic manganese production, and filter residue, distilled water mixes the back temperature and is raised to 80 ℃ in reactor, it is 2:1 that adding calcium hydroxide makes the mol ratio of its add-on and waste iron filing, under the condition of mechanical stirring intensity 900r/min, react 30min, carry out filtration washing, the filter residue of gained adds an amount of 2.5mol/L dilute sulphuric acid and leaches reaction 30min at normal temperatures, solution filters and obtains ferrum sulfuricum oxydatum solutum, can obtain qualified polyaluminum sulfate iron product through underpressure distillation again.
Embodiment 3 pyrolusites contain manganese 33.15%
The pyrolusite that will contain manganese 33.15% joins in the reactor that can hold 500 milliliters, it is 13:1 that adding distil water makes its liquid-solid ratio, under the condition of mechanical stirring intensity 2000r/min, adding the vitriol oil in the reactor makes its concentration reach 200g/L, ammonium sulfate concentrations reaches 100g/L, the temperature that mixes the afterreaction still is elevated to 60 ℃, the mol ratio 1:1.0 that presses Manganse Dioxide and waste iron filing in the pyrolusite adds waste iron filing, be warmed up to 90 ℃ behind the reaction 60min and continue reaction 60min, keep adding water-ground limestone successively under the temperature-resistant condition and ammoniacal liquor is regulated pH value 6.7, add SDD and remove heavy metal, carry out the separation of slag liquid, the manganese leaching yield is 98.41%, and slag contains manganese 1%.The solution non-shock chilling that obtains, adding tin anhydride solid makes content reach 0.08g/L and is the manganese sulfate solution that is used for electrolytic manganese production, and filter residue, distilled water mixes the back temperature and is raised to 70 ℃ in reactor, it is 1.5:1 that the mixture of adding calcium oxide and calcium hydroxide makes the mol ratio of its add-on and waste iron filing, under the condition of mechanical stirring intensity 600r/min, react 45min, carry out filtration washing, the filter residue of gained adds an amount of 4.2mol/L sulfuric acid and leaches reaction 60min at normal temperatures, solution filters and obtains ferrum sulfuricum oxydatum solutum, can obtain qualified polyaluminum sulfate iron product through underpressure distillation again.
Claims (9)
1. a waste iron filing reducing pyrolusite prepares electrolytic manganese metal solution and reclaims the novel process of iron, it is characterized in that, may further comprise the steps:
(1) pyrolusite is dropped in the reactor, the anolyte that produces when adding distilled water or electrolytic manganese, the weight proportion of the anolyte that produces when pyrolusite and distilled water or electrolytic manganese is 1:5.0 ~ 15.0;
(2) under mechanical stirring, add the vitriol oil and ammonium sulfate in the reactor, make that sulfuric acid concentration reaches 100-200g/L in the mixed solution, ammonium sulfate concentrations reaches 100 ~ 200g/L;
(3) add waste iron filing, leach reaction 0.5 ~ 1h in 25 ~ 60 ℃ of following mechanical stirring of temperature, reaction 1-2h is leached in elevated temperature to 70 ~ 100 a ℃ continuation, impels material reaction complete;
(4) water-ground limestone of adding pyrolusite weight 10% ~ 25% after reacting completely, is pH value to 6.3 ~ 6.7 of 20% ~ 28% ammoniacal liquor regulator solution with concentration again;
(5) 0.2% ~ 1.5% of adding pyrolusite weight Sodium dimethyldithiocarbamate 40min, reaction 0.5 ~ 1h, removal of impurities removing heavy metals ion filters cooling, adds tin anhydride in the filtrate, obtains being directly used in the manganese sulfate solution of electrolytic manganese.
2. a kind of waste iron filing reducing pyrolusite according to claim 1 prepares electrolytic manganese metal solution and reclaims the novel process of iron, it is characterized in that, after gained filter residue and distilled water mix after filtering in the step (5), under 50 ~ 90 ℃ of temperature of reaction, add calcium oxide or calcium hydroxide or both mixtures, mechanical stirring reaction 0.5 ~ 1.5h, filtration washing, the filter residue of gained adds dilute sulphuric acid and leaches reaction 0.5 ~ 1h at normal temperatures, filtration obtains ferrum sulfuricum oxydatum solutum, obtains bodied ferric sulfate through underpressure distillation.
3. a kind of waste iron filing reducing pyrolusite according to claim 1 prepares electrolytic manganese metal solution and reclaims the novel process of iron, it is characterized in that, in the step (2), the mol ratio of Manganse Dioxide is 1.2 ~ 2.8:1 in the vitriol oil of adding and the pyrolusite.
4. waste iron filing reducing pyrolusite according to claim 1 prepares the novel process of electrolytic manganese metal solution, it is characterized in that, in the step (2), churned mechanically speed is 800 ~ 2500r/min.
5. a kind of waste iron filing reducing pyrolusite according to claim 1 prepares electrolytic manganese metal solution and reclaims the novel process of iron, it is characterized in that, in the step (3), the mol ratio of Manganse Dioxide is 0.5 ~ 1.5: 1 in the waste iron filing of adding and the pyrolusite.
6. a kind of waste iron filing reducing pyrolusite according to claim 1 prepares electrolytic manganese metal solution and reclaims the novel process of iron, it is characterized in that the concentration of the tin anhydride of adding is 0.02 ~ 0.08g/L.
7. a kind of waste iron filing reducing pyrolusite according to claim 2 prepares electrolytic manganese metal solution and reclaims the novel process of iron, it is characterized in that the mol ratio of calcium oxide or calcium hydroxide or both mixtures and waste iron filing is (0.5 ~ 2.5): 1.
8. a kind of waste iron filing reducing pyrolusite according to claim 2 prepares electrolytic manganese metal solution and reclaims the novel process of iron, it is characterized in that churned mechanically speed is 400 ~ 1000r/min.
9. a kind of waste iron filing reducing pyrolusite according to claim 2 prepares electrolytic manganese metal solution and reclaims the novel process of iron, it is characterized in that the concentration of dilute sulphuric acid is 1.0 ~ 4.5mol/L.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102605186A (en) * | 2011-10-10 | 2012-07-25 | 云南建水锰矿有限责任公司 | Method for producing manganese sulfate from manganese-rich slag through atmospheric pressure leaching |
| CN103451423A (en) * | 2013-09-04 | 2013-12-18 | 宁夏天元锰业有限公司 | Solution preparation method of electrolytic manganese metal |
| CN103469246A (en) * | 2013-09-04 | 2013-12-25 | 宁夏天元锰业有限公司 | Iron removal method in production of manganese metal through electrolysis |
| CN103469247A (en) * | 2013-09-04 | 2013-12-25 | 宁夏天元锰业有限公司 | Method for reducing ammonia consumption in production of electrolytic manganese metal |
| CN103540773A (en) * | 2013-11-07 | 2014-01-29 | 广西桂柳化工有限责任公司 | Method for preparing manganese sulfate by utilizing manganese oxide |
| CN103555959A (en) * | 2013-11-07 | 2014-02-05 | 广西桂柳化工有限责任公司 | Technology for comprehensively recycling leaching residue in production of electrolytic manganese metal and manganese dioxide |
| CN103937999A (en) * | 2014-04-23 | 2014-07-23 | 北京科技大学 | Method and device for extracting metal manganese from ferromanganese through vacuum distillation |
| CN104762466A (en) * | 2015-04-17 | 2015-07-08 | 北京矿冶研究总院 | Liquid preparation method for producing electrolytic manganese or manganese dioxide from low-grade manganese oxide ore |
| CN104862501A (en) * | 2015-05-07 | 2015-08-26 | 张安良 | Chemical clean beneficiation and accessory recycling process of lean manganese ore |
| CN105668641A (en) * | 2016-03-04 | 2016-06-15 | 东北大学 | Method for preparing manganese sulfate solution by directly roasting pyrolusite with sulfuric acid |
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| CN102605186A (en) * | 2011-10-10 | 2012-07-25 | 云南建水锰矿有限责任公司 | Method for producing manganese sulfate from manganese-rich slag through atmospheric pressure leaching |
| CN103451423A (en) * | 2013-09-04 | 2013-12-18 | 宁夏天元锰业有限公司 | Solution preparation method of electrolytic manganese metal |
| CN103469246A (en) * | 2013-09-04 | 2013-12-25 | 宁夏天元锰业有限公司 | Iron removal method in production of manganese metal through electrolysis |
| CN103469247A (en) * | 2013-09-04 | 2013-12-25 | 宁夏天元锰业有限公司 | Method for reducing ammonia consumption in production of electrolytic manganese metal |
| CN103540773A (en) * | 2013-11-07 | 2014-01-29 | 广西桂柳化工有限责任公司 | Method for preparing manganese sulfate by utilizing manganese oxide |
| CN103555959A (en) * | 2013-11-07 | 2014-02-05 | 广西桂柳化工有限责任公司 | Technology for comprehensively recycling leaching residue in production of electrolytic manganese metal and manganese dioxide |
| CN103937999A (en) * | 2014-04-23 | 2014-07-23 | 北京科技大学 | Method and device for extracting metal manganese from ferromanganese through vacuum distillation |
| CN103937999B (en) * | 2014-04-23 | 2015-09-23 | 北京科技大学 | A kind of vacuum distilling ferromanganese extracts method and the device of manganese metal |
| CN104762466A (en) * | 2015-04-17 | 2015-07-08 | 北京矿冶研究总院 | Liquid preparation method for producing electrolytic manganese or manganese dioxide from low-grade manganese oxide ore |
| CN104762466B (en) * | 2015-04-17 | 2017-01-11 | 北京矿冶研究总院 | Liquid preparation method for producing electrolytic manganese or manganese dioxide from low-grade manganese oxide ore |
| CN104862501A (en) * | 2015-05-07 | 2015-08-26 | 张安良 | Chemical clean beneficiation and accessory recycling process of lean manganese ore |
| CN105668641A (en) * | 2016-03-04 | 2016-06-15 | 东北大学 | Method for preparing manganese sulfate solution by directly roasting pyrolusite with sulfuric acid |
| CN105668641B (en) * | 2016-03-04 | 2017-06-20 | 东北大学 | A kind of method that sulfuric acid roasting direct pyrolusite prepares manganese sulfate solution |
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