CN102212676A - Process for producing electrolytic manganese metal by using charcoal powder to reduce and convert manganese oxide ore - Google Patents
Process for producing electrolytic manganese metal by using charcoal powder to reduce and convert manganese oxide ore Download PDFInfo
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- CN102212676A CN102212676A CN2011101065368A CN201110106536A CN102212676A CN 102212676 A CN102212676 A CN 102212676A CN 2011101065368 A CN2011101065368 A CN 2011101065368A CN 201110106536 A CN201110106536 A CN 201110106536A CN 102212676 A CN102212676 A CN 102212676A
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- manganese
- manganese oxide
- oxide ore
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Abstract
The invention discloses a process for producing electrolytic manganese metal by using charcoal powder to reduce and convert manganese oxide ore. The process comprises the following steps of: crushing and sieving the manganese oxide ore and charcoal respectively, mixing the manganese oxide ore powder and the charcoal powder uniformly in a certain ratio, putting the mixed powder into a rotary roasting furnace, reacting for 1 to 2 hours at a certain temperature under certain pressure intensity so that the manganese oxide ore is reduced into MnO, and leaching in sulfuric acid of certain concentration at a certain temperature to obtain impurity-containing manganese sulfate solution; and preparing electrolyte by the conventional process for producing electrolytic manganese, and performing electrolysis in an electrolytic bath to produce the electrolytic manganese metal. By the process, the problem of tight supply of manganese carbonate ore can be solved, the production cost is remarkably reduced, and the cost of the ore is only 1/5 of the total cost of electrolytic manganese production; and compared with the cost of the conventional production process (using manganese carbonate as a raw material), the comprehensive cost of the process can be reduced by 10 to 15 percent.
Description
Technical field
The present invention relates to a kind of production technique of electrolytic metal Mn, especially relate to a kind of carbon reducing agent that utilizes and transform the technology that manganese oxide ore is produced electrolytic metal Mn.
Background technology
China is electrolytic manganese production big country, its electrolytic manganese and thousands of families of manganese series product manufacturing enterprise, and year volume of production and marketing is above 1,000,000 tons.At present, it is raw material that electrolytic manganese production mainly adopts manganese carbonate ore, because Market competition, some place is adopted the unrest of manganese carbonate ore and is disorderly dug, adopts richness and abandon poor in addition, cause the manganese carbonate ore resource poor day by day, ore grade also drops to about 10% from original about 20%, and the ore cost of producing electrolytic manganese has accounted for more than 1/3 of total cost.Now manganese carbonate ore in the Hunan, the manganese triangle that has a common boundary of Guizhou, Chongqing has been in short supply, causes the how tame electrolytic manganese enterprise can't ordinary production or stopping production.But manganese oxide ore is not only abundant at China's reserves, and import manganese oxide ore (40%-50%) of high grade, and cost is low, is to substitute the desirable mineral resources that manganese carbonate ore is produced electrolytic metal Mn.Enterprise of a few family is arranged at present utilizing manganese oxide ore to produce the technological test of electrolytic metal Mn, mainly adopt fire reduction or wet reducing, but these two kinds of methods all can't substitute manganese carbonate ore because cost is higher.Wherein, the fire reduction conversion method is comparatively general, but because the stoving oven that a lot of manufacturer uses is to be simple and easy to make but the energy consumption reverberatory furnace bigger than high pollution, several years ago, National Development and Reform Committee has proscribed the production technique that reverberatory furnace is used for electrolytic manganese by formal decree, fire reduction adopts coal as reductive agent mostly, produces bigger SO in the roasting process
2Flue gas, and dust pollution is serious, and the consumption of coal amount is big.
Summary of the invention
Deficiency at the prior art existence, the object of the present invention is to provide a kind of carbon reducing agent that utilizes to transform the novel technique that manganese oxide ore is produced electrolytic metal Mn, it can not only substitute manganese carbonate ore with manganese oxide ore and produce electrolytic metal Mn, and energy consumption is low, it is little to pollute, reagent consumption less, production cost is low.
The present invention is achieved in that manganese oxide ore and charcoal separated pulverizing crossed the 20-100 mesh sieve, and by manganese oxide powder and carbon dust mass ratio 15: 1-35: 1 mixes, and puts into rotary roasting furnace, in 500-950 ℃ maturing temperature and 1-5 * 10
5React 1-2h under the pressure of pa, make the manganese oxide ore reduction generate MnO, use 1-2mol/L sulfuric acid again, under 20-100 ℃ of temperature, leach, obtain containing assorted manganese sulfate solution.Be electrolytic solution with manganese sulfate solution by prepared such as neutralization, purification, filtrations then, can enter electrolyzer and carry out the electrolysis production electrolytic metal Mn.
The main component of manganese oxide ore is MnO
2, Mn
2O
3, Mn
3O
4, manganese content 〉=20% (w/w).
The principal reaction equation is:
2MnO
2+C＝2MnO+CO
2↑
2Mn
2O
3+C＝4MnO+CO
2↑
2Mn
3O
4+C＝6MnO+CO
2↑
MnO+H
2SO
4＝MnSO
4+H
2O
Optimal processing parameter is: grinding particle size 100 orders of manganese oxide ore and carbon dust; Manganese content and carbon dust mass ratio are 7: 1 in the manganese oxide ore; 950 ℃ of maturing temperatures; Roasting time 2h, the transformation efficiency of manganese oxide ore all can reach 95% with this understanding.The leaching of manganous sulfate can make the leaching yield of manganese reach 98% with the 1mol/L sulphuric acid soln at normal temperatures.Because the difference of manganese content in the manganese oxide, therefore, the optimum parameter of the mass ratio of manganese ore and carbon dust is difficult to determine, so use the mass ratio of manganese content and carbon dust in the manganese oxide ore.
Beneficial effect of the present invention is: adopt carbon reducing agent to transform the novel technique that manganese oxide ore is produced electrolytic metal Mn, realize suitability for industrialized production, not only can solve manganese carbonate ore problem in short supply, and production cost is significantly reduced, wherein ore cost only accounts for about 1/5 of electrolytic manganese production total cost; If adopt import manganese oxide ore (containing Mn more than 40%), comparable employing manganese carbonate ore is produced the few last person's slag of electrolytic manganese more than 6 tons/ton product, greatly reduces the processing costs of tailings and tailings environment damage.Initial estimate adopts comprehensive cost that novel technique of the present invention produces electrolytic manganese can reduce 10%-15% than the cost of existing production technique (is raw material with the manganous carbonate), and therefore, the present invention has huge market application foreground and economic benefit.
Embodiment
Reaction among the embodiment is all carried out in homemade small-sized (about 1 liter of volume) tests with rotary roasting furnace, and manganese content test adopts ferrous ammonium sulfate titration.
Embodiment 1
Get manganese oxide ore (contain manganese 20.13%) and the 15g carbon dust of 500g and mix, put into rotary roasting furnace, 500 ℃ of temperature, pressure 1.013 * 10 through pulverizing 100 mesh sieves
5Pa, 60 rev/mins of speed of rotation, roasting 1.5 hours.Make the manganese oxide ore reduction generate MnO, with the leaching down of 1mol/L sulfuric acid normal temperature, obtain containing assorted manganese sulfate solution again.The manganese sulfate solution that is obtained is prepared as electrolytic solution by existing technology of producing electrolytic manganese with series of process such as manganese sulfate solution neutralization, purification, filtrations again, can enter electrolyzer and carry out the electrolysis production electrolytic metal Mn.After testing, the transformation efficiency of its manganese oxide is 85%, manganese leaching yield 98%.
Embodiment 2
Get manganese oxide ore (contain manganese 20.13%) and the 15g carbon dust of 500g and mix, put into rotary roasting furnace, 950 ℃ of temperature, pressure 1.013 * 10 through pulverizing 100 mesh sieves
5Pa, 60 rev/mins of speed of rotation, roasting 2 hours.Make the manganese oxide ore reduction generate MnO, use 2mo l/L sulfuric acid again,, obtain containing assorted manganese sulfate solution 35 ℃ of leachings down.The manganese sulfate solution that is obtained is prepared as electrolytic solution by existing technology of producing electrolytic manganese with series of process such as manganese sulfate solution neutralization, purification, filtrations again, can enter electrolyzer and carry out the electrolysis production electrolytic metal Mn.After testing, the transformation efficiency of manganese oxide is 95%, manganese leaching yield 98%.
Embodiment 3
Get manganese oxide ore (contain manganese 20.13%) and the 15g carbon dust of 500g and mix, put into rotary roasting furnace, 950 ℃ of temperature, pressure 1.013 * 10 through pulverizing 60 mesh sieves
5Pa, 60 rev/mins of speed of rotation, roasting 2 hours.Make the manganese oxide ore reduction generate MnO, with the leaching down of 1mol/L sulfuric acid normal temperature, obtain containing assorted manganese sulfate solution again.The manganese sulfate solution that is obtained is prepared as electrolytic solution by existing technology of producing electrolytic manganese with series of process such as manganese sulfate solution neutralization, purification, filtrations again, can enter electrolyzer and carry out the electrolysis production electrolytic metal Mn.After testing, the transformation efficiency of manganese oxide is 90%, manganese leaching yield 98%.
Embodiment 4
Get manganese oxide ore (contain manganese 45.27%) and the 33g carbon dust of 500g and mix, put into rotary roasting furnace, 950 ℃ of temperature, pressure 1.013 * 10 through pulverizing 100 mesh sieves
5Pa, 60 rev/mins of speed of rotation, roasting 1.5 hours.Make the manganese oxide ore reduction generate MnO, with the leaching down of 1mol/L sulfuric acid normal temperature, obtain containing assorted manganese sulfate solution again.The manganese sulfate solution that is obtained is prepared as electrolytic solution by existing technology of producing electrolytic manganese with series of process such as manganese sulfate solution neutralization, purification, filtrations again, can enter electrolyzer and carry out the electrolysis production electrolytic metal Mn.After testing, the transformation efficiency of manganese oxide is 85%, manganese leaching yield 98%.
Embodiment 5
Get manganese oxide ore (contain manganese 45.27%) and the 33g carbon dust of 500g and mix, put into rotary roasting furnace, 950 ℃ of temperature, pressure 1.013 * 10 through pulverizing 100 mesh sieves
5Pa, 60 rev/mins of speed of rotation, roasting 2 hours.Make the manganese oxide ore reduction generate MnO, with the leaching down of 1mol/L sulfuric acid normal temperature, obtain containing assorted manganese sulfate solution again.The manganese sulfate solution that is obtained is prepared as electrolytic solution by existing technology of producing electrolytic manganese with series of process such as manganese sulfate solution neutralization, purification, filtrations again, can enter electrolyzer and carry out the electrolysis production electrolytic metal Mn.After testing, the transformation efficiency of manganese oxide is 95%, manganese leaching yield 98%.
Embodiment 6
Get manganese oxide ore (contain manganese 45.27%) and the 33g carbon dust of 500g and mix, put into rotary roasting furnace, 950 ℃ of temperature, pressure 1.013 * 10 through pulverizing 60 mesh sieves
5Pa, 60 rev/mins of speed of rotation, roasting 2 hours.Make the manganese oxide ore reduction generate MnO, with the leaching down of 1mol/L sulfuric acid normal temperature, obtain containing assorted manganese sulfate solution again.The manganese sulfate solution that is obtained is prepared as electrolytic solution by existing technology of producing electrolytic manganese with series of process such as manganese sulfate solution neutralization, purification, filtrations again, can enter electrolyzer and carry out the electrolysis production electrolytic metal Mn.After testing, the transformation efficiency of manganese oxide is 90%, manganese leaching yield 98%.
Claims (2)
1. one kind is utilized carbon reducing agent to transform the technology that manganese oxide ore is produced electrolytic metal Mn, it is characterized in that: manganese oxide ore and charcoal separated pulverizing are crossed the 20-100 mesh sieve, by manganese oxide powder and carbon dust mass ratio 15: 1-35: 1 mixes, put into rotary roasting furnace, in 500-950 ℃ temperature and 1-5 * 10
5React 1-2h under the pa pressure, make the manganese oxide ore reduction generate MnO, be that the sulfuric acid of 1-2mol/L leaches under 20-100 ℃ of temperature with concentration again, obtain containing assorted manganese sulfate solution, manganese sulfate solution is an electrolytic solution by prepared such as neutralization, purification, filtrations then, can enter electrolyzer and carry out the electrolysis production electrolytic metal Mn.
2. a kind of carbon reducing agent that utilizes according to claim 1 transforms the technology that manganese oxide ore is produced electrolytic metal Mn, and it is characterized in that: optimal processing parameter is: manganese content and carbon dust mass ratio 7: 1,950 ℃ of maturing temperatures, roasting time 2h in grinding particle size 100 orders of manganese oxide ore and carbon dust, the manganese oxide ore; Vitriolic concentration 1mol/L.
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| CN2011101065368A CN102212676A (en) | 2011-04-27 | 2011-04-27 | Process for producing electrolytic manganese metal by using charcoal powder to reduce and convert manganese oxide ore |
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| CN2011101065368A CN102212676A (en) | 2011-04-27 | 2011-04-27 | Process for producing electrolytic manganese metal by using charcoal powder to reduce and convert manganese oxide ore |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102888510A (en) * | 2012-10-24 | 2013-01-23 | 广西天鸿鑫锰业科技有限公司 | Method for preparing manganese sulfate solution from low-grade manganese oxide by reducing leaching at normal temperature and pressure |
| CN103014320A (en) * | 2012-12-07 | 2013-04-03 | 中信大锰矿业有限责任公司 | Method for preparing manganese sulfate by using sulfur-containing carbonaceous manganese carbonate ore |
| 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 |
| CN108251646A (en) * | 2017-12-05 | 2018-07-06 | 中信大锰矿业有限责任公司大新锰矿分公司 | The method for producing manganese monoxide using activated carbon adsorption slag reduction roasting manganese oxide ore |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5232490A (en) * | 1985-11-27 | 1993-08-03 | Leadville Silver And Gold | Oxidation/reduction process for recovery of precious metals from MnO2 ores, sulfidic ores and carbonaceous materials |
-
2011
- 2011-04-27 CN CN2011101065368A patent/CN102212676A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5232490A (en) * | 1985-11-27 | 1993-08-03 | Leadville Silver And Gold | Oxidation/reduction process for recovery of precious metals from MnO2 ores, sulfidic ores and carbonaceous materials |
Non-Patent Citations (3)
| Title |
|---|
| 《中国锰业》 20100531 田宗平 硫酸锰生产新工艺的研究 第28卷, 第2期 * |
| 杨娟等: "锰矿还原技术", 《中国锰业》 * |
| 田宗平: "硫酸锰生产新工艺的研究", 《中国锰业》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102888510A (en) * | 2012-10-24 | 2013-01-23 | 广西天鸿鑫锰业科技有限公司 | Method for preparing manganese sulfate solution from low-grade manganese oxide by reducing leaching at normal temperature and pressure |
| CN103014320A (en) * | 2012-12-07 | 2013-04-03 | 中信大锰矿业有限责任公司 | Method for preparing manganese sulfate by using sulfur-containing carbonaceous manganese carbonate ore |
| 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 |
| CN108251646A (en) * | 2017-12-05 | 2018-07-06 | 中信大锰矿业有限责任公司大新锰矿分公司 | The method for producing manganese monoxide using activated carbon adsorption slag reduction roasting manganese oxide ore |
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Application publication date: 20111012 |