CN87102046A - Method with producing manganous sulphate solution from manganese dioxide ore - Google Patents
Method with producing manganous sulphate solution from manganese dioxide ore Download PDFInfo
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- CN87102046A CN87102046A CN 87102046 CN87102046A CN87102046A CN 87102046 A CN87102046 A CN 87102046A CN 87102046 CN87102046 CN 87102046 CN 87102046 A CN87102046 A CN 87102046A CN 87102046 A CN87102046 A CN 87102046A
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- manganese
- ore
- dioxide
- dioxide ore
- sulfurous iron
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Abstract
A kind of method with producing manganous sulphate solution from manganese dioxide ore is to be reductive agent with the sulfurous iron ore, directly soaks fine-graded dioxide ore for manganese with sulphuric acid soln, and its reaction formula is:
FeS
2+ MnO
2+ 2H
2SO
4=MnSO
4+ FeSO
4+ 2H
2It is 85～100 ℃ that O+2S works as temperature of reaction, and in 2～4 hours reaction times, reaction end pH value is 6.8～7 o'clock, and the leaching rate of Manganse Dioxide is greater than 90%.Ore pulp is after purification and solid-liquid separation, and manganese sulfate solution can be used as the electrolysis production manganese metal or produces other manganese.Owing to avoided the high-temperature roasting operation, simplified technology, but both save energy can reduce environmental pollution again.Directly use dioxide ore for manganese to be raw material, can make raw materials cost reduce more than 50%.
Description
The invention relates to the production technique of mn sulphate, particularly use the method for producing manganous sulphate solution from manganese dioxide ore.
In the electrochemical process of manganese, produce outside manganese metal or the manganese as electrolytic process, at first will prepare the aqueous solution that contains mn ion, because the insoluble of Manganse Dioxide in sulphuric acid soln, the method for producing manganese sulfate solution at present can reduce three kinds basically: one, manganese carbonate ore directly soaks with sulfuric acid is molten; Two, the roasting of dioxide ore for manganese high temperature reduction is soaked with sulfuric acid is molten after becoming manganese monoxide again; Three, dioxide ore for manganese mixes with sulfurous iron ore, carries out the high temperature sulfurization roasting with the vitriol oil, and water or diluted acid are molten again soaks.Above-mentioned three kinds of methods, though the leaching rate of manganese can reach 90% or higher, but method one is because the manganese carbonate ore resource-constrained, thereby cost of material height, method two and three all is manganese monoxide or the vitriol that obtains solubility by high-temperature roasting, thereby not only disposable initial cost is big, and the energy consumption height, contaminate environment.For above-mentioned reasons, cause the converted products costliness of manganese, product production and market all are restricted.
Task of the present invention is to explore one directly with the molten dioxide ore for manganese that soaks of sulfuric acid, prepares the method for manganese sulfate solution.Requirement leaching rate height, raw materials consumption is few, thereby reaches simplification technology, the purpose that reduces cost.
Content of the present invention is, according to the solubility of manganese monoxide in sulphuric acid soln, utilize resourceful dioxide ore for manganese, avoid the high-temperature roasting approach, soaking in the process with sulfuric acid is molten, adding certain does not have the reductive agent of influence to quality product, makes the reduction of Manganse Dioxide and moltenly soaks operation and finish in same equipment.
Because sulfurous iron ore is cheap, the source is abundant, and the present invention preferentially adopts sulfurous iron ore to make reductive agent, and its reaction formula is as follows:
By calculation of thermodynamics, equilibrium constant of reaction K is
K= (〔Fe
+2〕〔Mn
+2〕)/(〔H
+〕4) =10
27.23
Reaction equilibrium constant is so big, illustrates that be more satisfactory with sulfurous iron ore as reductive agent.
Because Manganse Dioxide is oxygenant, the ferrous ion in the solution is oxidized to ferric ion by following reaction formula.
Equilibrium constant of reaction K is
K= (〔Fe
+3〕
2〔Mn
+2〕)/(〔Fe
+2〕
2〔H
+〕
4) =10
15.42
When the pH value of solution was controlled at 4～7, ferric ion was with Fe(OH)
3The form precipitation.This process and manganese carbonate ore sulfuric acid is molten must add Manganse Dioxide when soaking to make oxygenant similar, this is one of existing advantage of the direct sulfuric acid leaching body of Manganse Dioxide.
The same with traditional technology, in solution, add barium sulphide or ammonium sulfide or hydrogen sulfide, make heavy metal form sulfide precipitation, thereby manganese sulfate solution is purified, its reaction formula is:
Me is heavy metals such as copper, lead, zinc, nickel, cobalt in the formula
Because it is extremely strict to the requirement of manganese sulfate solution purity that electrolytic process is produced manganese metal, the present invention is embodiment to provide electrolytic process to produce the required manganese sulfate solution of manganese metal.
Employing contains manganese more than 20%, iron 2～10%, and the dioxide ore for manganese of cupric, cobalt, nickel, and Mn-Fe ratio is greater than 3.Sulfur-bearing 34～39%, iron 27～32%, and the sulfurous iron ore of cupric, lead, zinc, nickel, cobalt, sulphur-iron ratio is greater than 1.Above-mentioned two kinds of raw materials less than 100 purpose granularities greater than 80%.Two kinds of raw materials are pressed dioxide ore for manganese: the mixed of sulfurous iron ore=1: 0.2～0.4, the sulphuric acid soln that the compound input has been prepared also can add Manganse Dioxide and sulfurous iron ore respectively then, and the limit is reinforced, and stir on the limit.The part by weight of the dioxide ore for manganese and the vitriol oil is 1: 0.5～0.8, reacted 2～4 hours, and 85～100 ℃ of temperature of reaction, the reaction end pH value is 6.8～7.The same with traditional technology, after deironing, also need add barium sulphide and Sodium Dimethyldithiocarbamate.Ore pulp is through twice press filtration, and filtrate is limpid, and the leaching rate of manganese is compared with the molten simultaneous test of soaking that does not add sulfurous iron ore greater than 90%, and leaching rate improves more than 60%.
Neutral manganese sulfate solution contains divalent manganesetion 32～40 grams per liters, and ferrous ion is less than 0.01 mg/litre, and copper, nickel, cobalt ion qualitative analysis do not have.Neutral manganese sulfate solution send electrolytic tank electrolysis to produce manganese metal.Waste electrolyte returns leaching prosess.
Reaction is to be 22 cubic metres at a volume, has to carry out in the churned mechanically line with rubber reactive tank.Reactive tank heats with open steam.
Reductive agent also can adopt the promptly common alleged sulphur concentrate of the tailings of sulfide minerals such as Floatation of Copper, lead, zinc.
With the molten method of producing manganese sulfate solution of soaking of the direct sulfuric acid of dioxide ore for manganese, simplified traditional handicraft. Process Mn-Fe ratio greater than 3 dioxide ore for manganese, the Manganese leaching rate is greater than 90%, and only cost of material is just than with the manganese carbonate ore minimizing more than 50%. Avoided high-temperature operation, but both energy savings can reduce environmental pollution again, contain other manganese resources of manganese dioxide for utilization, the present invention still has use value.
Claims (5)
1, the vitriol of manganese, particularly use the method for producing manganous sulphate solution from manganese dioxide ore, it is characterized in that being in the indissoluble dioxide ore for manganese of positive tetravalent state, do not need to give the manganese monoxide that is processed into solubility earlier, or vitriol, but directly soak fine-graded dioxide ore for manganese with sulphuric acid soln, molten soaking must add fine-graded sulfurous iron ore and make reductive agent in the process, dioxide ore for manganese, sulfurous iron ore, the vitriolic ratio can be according to the Mn-Fe ratio in the dioxide ore for manganese, and the difference of the sulphur-iron ratio in the sulfurous iron ore is carried out chemical reaction equilibrium and calculated definite.
2, method according to claim 1, it is characterized in that dioxide ore for manganese and sulfurous iron ore less than 100 purpose granularities preferably greater than 80%.
3, method according to claim 1 is characterized in that sulfurous iron ore can adopt the flotation sulfide mineral, as the tailings of Floatation of Copper, lead, zinc sulphide minerals-be the sulphur concentrate.
4, method according to claim 1, it is characterized in that under the general situation, Mn-Fe ratio in dioxide ore for manganese is greater than 3, and the sulphur-iron ratio in the sulfurous iron ore was greater than 1 o'clock, and dioxide ore for manganese, sulfurous iron ore, vitriolic ratio can be selected in the middle of 1: 0.2～0.4: 0.5～0.8.
5, method according to claim 1 is characterized in that reaction process should have stirring, and temperature is controlled at 85～100 ℃, and the terminal point pH value is 6.8～7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 87102046 CN87102046A (en) | 1987-06-23 | 1987-06-23 | Method with producing manganous sulphate solution from manganese dioxide ore |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 87102046 CN87102046A (en) | 1987-06-23 | 1987-06-23 | Method with producing manganous sulphate solution from manganese dioxide ore |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN87102046A true CN87102046A (en) | 1987-12-09 |
Family
ID=4813756
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 87102046 Pending CN87102046A (en) | 1987-06-23 | 1987-06-23 | Method with producing manganous sulphate solution from manganese dioxide ore |
Country Status (1)
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|---|---|
| CN (1) | CN87102046A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1034517C (en) * | 1992-11-02 | 1997-04-09 | 冶金工业部长沙冶研究院 | Preparation of highly pure manganese sulfate with high yield rate |
| CN100411997C (en) * | 2005-02-01 | 2008-08-20 | 桂林市孟泰矿产技术开发有限责任公司 | Method of recovering manganese sulfate from low-grade manganese carbonate and manganese oxide |
| CN101845562A (en) * | 2010-06-22 | 2010-09-29 | 陈榜龙 | Improved device and method for producing electrolytic manganese metal by two-ore method |
| CN101892384A (en) * | 2010-07-15 | 2010-11-24 | 广西有色金属集团汇元锰业有限公司 | Method for producing mercury-free alkaline manganese electrolytic manganese dioxide |
| CN103387266A (en) * | 2012-05-07 | 2013-11-13 | 何建桥 | Method for direct production of ultra-pure manganese sulfate by non-carbon reduction of manganese dioxide |
| CN103526018A (en) * | 2013-10-17 | 2014-01-22 | 桂林翔云锰业有限责任公司 | Method for producing electrolytic manganese from manganese carbonate ore with low manganese content and high iron content |
| CN111850305A (en) * | 2020-07-28 | 2020-10-30 | 昆明理工大学 | Method for leaching cobalt and manganese from manganese-rich cobalt slag |
| CN112062159A (en) * | 2020-08-04 | 2020-12-11 | 福建省连城锰矿有限责任公司 | Process for preparing electronic-grade manganese sulfate by potassium-sodium-calcium-magnesium-free method |
-
1987
- 1987-06-23 CN CN 87102046 patent/CN87102046A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1034517C (en) * | 1992-11-02 | 1997-04-09 | 冶金工业部长沙冶研究院 | Preparation of highly pure manganese sulfate with high yield rate |
| CN100411997C (en) * | 2005-02-01 | 2008-08-20 | 桂林市孟泰矿产技术开发有限责任公司 | Method of recovering manganese sulfate from low-grade manganese carbonate and manganese oxide |
| CN101845562A (en) * | 2010-06-22 | 2010-09-29 | 陈榜龙 | Improved device and method for producing electrolytic manganese metal by two-ore method |
| WO2011160578A1 (en) * | 2010-06-22 | 2011-12-29 | Chen Banglong | Method for producing electrolytic manganese metal by using two ores and apparatus thereof |
| CN101845562B (en) * | 2010-06-22 | 2013-03-20 | 陈榜龙 | Improved device and method for producing electrolytic manganese metal by two-ore method |
| CN101892384A (en) * | 2010-07-15 | 2010-11-24 | 广西有色金属集团汇元锰业有限公司 | Method for producing mercury-free alkaline manganese electrolytic manganese dioxide |
| CN103387266A (en) * | 2012-05-07 | 2013-11-13 | 何建桥 | Method for direct production of ultra-pure manganese sulfate by non-carbon reduction of manganese dioxide |
| CN103387266B (en) * | 2012-05-07 | 2015-07-15 | 何建桥 | Method for direct production of ultra-pure manganese sulfate by non-carbon reduction of manganese dioxide |
| CN103526018A (en) * | 2013-10-17 | 2014-01-22 | 桂林翔云锰业有限责任公司 | Method for producing electrolytic manganese from manganese carbonate ore with low manganese content and high iron content |
| CN111850305A (en) * | 2020-07-28 | 2020-10-30 | 昆明理工大学 | Method for leaching cobalt and manganese from manganese-rich cobalt slag |
| CN112062159A (en) * | 2020-08-04 | 2020-12-11 | 福建省连城锰矿有限责任公司 | Process for preparing electronic-grade manganese sulfate by potassium-sodium-calcium-magnesium-free method |
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