CN103818965A - Phosphorous removal method for manganous sulfate produced from high-phosphorus rhodochrosite - Google Patents
Phosphorous removal method for manganous sulfate produced from high-phosphorus rhodochrosite Download PDFInfo
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- CN103818965A CN103818965A CN201410105085.XA CN201410105085A CN103818965A CN 103818965 A CN103818965 A CN 103818965A CN 201410105085 A CN201410105085 A CN 201410105085A CN 103818965 A CN103818965 A CN 103818965A
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- sulfate solution
- rhodochrosite
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Abstract
The invention provides a phosphorous removal method for manganous sulfate produced from high-phosphorus rhodochrosite. The phosphorous removal method comprises the steps of (1), at the room temperature, adding ferrous sulfate and a hydrogen peroxide solution to a manganous sulfate solution produced from high-phosphorus rhodochrosite to form a mixed solution, and then carrying out an oxidization reaction in a stirring state, (2) adding stronger ammonia water to the mixed solution obtained in the step (1) to regulate the pH value to the range from 3 to 5, and then thoroughly stirring under the room temperature to obtain a mixed slurry, and (3) standing and precipitating the mixed slurry obtained in the step (2), and then filtering and separating, and obtaining the filtrate, namely, a low-phosphorus manganous sulfate solution. Compared with the prior art, the phosphorous removal method is capable of effectively avoiding the problems of complex operation, high energy consumption and/or pollution on the environment possibly caused by phosphorous removal during mineral separation, and also has the advantages of mild reaction conditions and relatively lower cost.
Description
Technical field
The present invention relates to the method that manganese sulfate solution to being produced by high phosphorus rhodochrosite carries out dephosphorization treatment.
Background technology
Manganese metal (Mn) is a kind of essential industry raw material, and electrolytic process is one of method obtaining manganese metal.Its basic step is, first take manganese ore as raw material, to add sulfuric acid to make containing manganese leaching liquid---manganese sulfate solution after being pulverized; Then this manganese sulfate solution after processing, removal of impurities is carried out to electrolysis as electrolytic solution, to obtain manganese metal.China's manganese ore mostly is lean ore, and detrimental impurity phosphorus content is higher.Due in electrolytic process, phosphorus content is too high, not only can make anode potential greatly increase, oxygen evolution, and current efficiency declines, the rapid corrosion damage of anode, and then cause on cathodic metal manganese tray efficiency low; And can cause manganese metal return molten and cause financial loss.In addition, the phosphorus in electrolytic solution can enter in manganese metal product with the form of phosphorus manganic compound, causes manganese metal Quality Down, if set it as one of steelmaking feed, also will affect the quality of steel.So, for various high-phosphorus manganeses (manganese ore that phosphorus content is high), before being prepared into and can be used as manganese sulfate solution used for electrolyte, also must remove phosphorus wherein as far as possible.In prior art, also truly had the method for much carrying out dephosphorization (dephosphorization) for different types of high-phosphorus manganese, but in these methods, some operations energy consumption more complicated, that have is higher, have may be to environment.Especially, these methods are all carried out in the ore dressing stage, and have be only applicable to pyrolusite.In the case of originally can be used as manganese sulfate solution used for electrolyte as raw material is prepared into take high phosphorus rhodochrosite, if still adopt prior art to carry out an ore dressing processing to high phosphorus rhodochrosite more, can make the cost that finally obtains low-phosphorous manganese sulfate solution greatly increase.
Summary of the invention
The object of the invention is, provide that a kind of technique is simple, energy consumption is low, pollution-free, and the phosphorus removing method of the made manganese sulfate solution of its lower-cost high phosphorus rhodochrosite.
For realizing described object, the phosphorus removing method of the made manganese sulfate solution of a kind of like this high phosphorus rhodochrosite is provided, it is characterized in that, the method has the following steps:
(1) under room temperature condition, in steel basin, pack the manganese sulfate solution made by high phosphorus rhodochrosite into, then add hydrogen peroxide solution that ferrous sulfate, massfraction are 30% with composition mixing solutions; Then under whipped state, carry out oxidizing reaction;
Wherein, the phosphorus concentration of manganese sulfate solution between 2.5～3.2g/l, mol ratio=1.0～2 of phosphorus in iron ion and manganese sulfate solution in ferrous sulfate: 1, mol ratio=0.5～1.25 of iron ion in hydrogen peroxide and ferrous sulfate: 1;
(2) in step (1) gained mixing solutions, add strong aqua to regulate pH value to 3～5, then fully stir to obtain mixed slurry at ambient temperature;
(3) standing, settling step (2) gained mixed slurry, then filters, separates, and gained filtrate is low-phosphorous manganese sulfate solution.
From scheme, can find out, the present invention be directed to and use after sulfuric acid to leach high phosphorus rhodochrosite, obtain phosphorous too high manganese sulfate solution and carry out dephosphorization processing.Phosphorus in this manganese sulfate solution, mainly exist with phosphoric acid salt (orthophosphoric acid salt and a small amount of pyrophosphate salt) form of solubility, in step (1), add ferrous sulfate and hydrogen peroxide solution and form mixing solutions, to carry out after oxidizing reaction, the part ferrous iron (Fe in mixing solutions
2+) will be oxidized to the ferric iron (Fe of nascent state
3+), can allow part pyrophosphate (P simultaneously
2o
7 4-) be converted into ortho-phosphoric acid root (PO
4 3-).In step (2), slowly add strong aqua (NH
3h
2o) regulate after pH value, can allow on the one hand the unoxidized ferrous iron of ferric iron Buddhist monk and phosphate radical form the calcium phosphate precipitation of insoluble; On the other hand, the ferric iron generation intense hydrolysis of nascent state in mixing solutions, and there is each polyreaction in hydrolysis, generate the multinuclear hydroxo complex with longer linear structure, as Fe
2(OH)
2 4+, Fe
3(OH)
4 5+can be with mode and the phosphate radical generation coprecipitation phenomena of absorption, complexing Deng, the hydroxo complex of these iron content, then by precipitate and separate, phosphorus is removed.This has just guaranteed the reliable separation of calcium phosphate precipitation and the manganese sulfate solution of insoluble.So, in the filtrate of step (3) gained, be just the low-down manganese sulfate solution of phosphorus content.Compared with prior art, because the present invention has been placed on the process of removing phosphorus in manganese sulfate solution, and with high phosphorus rhodochrosite be raw material to prepare manganese sulfate solution itself be the indispensable step of preparing electrolytic solution, and other impurity outside dephosphorization have also been got rid of in large quantities in this step.So, compared with prior art, not only effectively avoided dephosphorization in the time of ore dressing and may problem, the problem includes: operation is more complicated, energy consumption is higher and/or problem to environment, but also the mild condition that responds, the relatively low advantage of cost.
Below in conjunction with embodiment, the present invention is described further.
Embodiment
The phosphorus removing method of the made manganese sulfate solution of high phosphorus rhodochrosite, is characterized in that, the method has the following steps:
(1) under room temperature condition, in steel basin, pack the manganese sulfate solution made by high phosphorus rhodochrosite into, then add ferrous sulfate (FeSO
47H
2o) hydrogen peroxide (H that, massfraction is 30%
2o
2) solution with composition mixing solutions; Then under whipped state, carry out oxidizing reaction (guarantee the fully churning time of oxidation, conventionally only want 3～5min);
Wherein, the phosphorus concentration of manganese sulfate solution between 2.5～3.2g/l, mol ratio=1.0～2 of phosphorus in iron ion and manganese sulfate solution in ferrous sulfate: 1, mol ratio=0.5～1.25 of iron ion in hydrogen peroxide and ferrous sulfate: 1;
(2) in step (1) gained mixing solutions, add strong aqua to regulate pH value to 3～5, then fully stir at ambient temperature to obtain mixed slurry (time that guarantee to stir fully, mixes, only needs 30min～45min conventionally);
(3) standing, settling step (2) gained mixed slurry (conventionally, staticly settling 30min), then filters, separates, and gained filtrate is low-phosphorous manganese sulfate solution.
The experimental verification that the present invention has passed through to do in laboratory, verification step is identical with the step of above-mentioned embodiment.The result is shown in proof list.
Before and after checking, all adopt GB/T1515-2002 " the mensuration phosphorus molybdenum blue spectrophotometric method of manganese ore phosphorus content " to measure the phosphorus concentration of manganese sulfate solution, then calculate respectively tp removal rate.(note: in proof list, " first phosphorus concentration " is the starting point concentration of the manganese sulfate solution made by high phosphorus rhodochrosite, " n(Fe/P) " represent in ferrous sulfate the ratio of the mol ratio of phosphorus in iron ion and manganese sulfate solution, " H
2o
2: Fe " represent the mol ratio of iron ion in hydrogen peroxide and ferrous sulfate, " residual phosphorus concentration (mg/l) " refers to the phosphorus concentration of the manganese sulfate solution after each routine confirmatory experiment finishes.
Proof list:
From above-mentioned each example, can find out, the clearance of phosphorus of the present invention has all reached more than 98%, and the effect of checking example 4 is the poorest, but the minimum requirements to its phosphorus content still can meet electrolytic metal Mn time of its manganese sulfate solution.
Special instruction, in the time that the present invention is verified, for the impact of test on manganese in manganese sulfate solution, also adopt the ferrous ammonium sulfate titration in GB/T1506-2002 " mensuration potentiometric titration and the ferrous ammonium sulfate titration of manganese ore manganese content ", measured the manganese content (the manganese concentration before checking is respectively between 30～34g/l) in the manganese sulfate solution before and after checking.Result shows, the manganese loss in manganese sulfate solution is all little, and manganese loss maximum is checking example 3, but its loss does not exceed 8% yet.The purity higher (there is no that phosphorus manganic compound exists) of the manganese metal obtaining due to the manganese sulfate solution electrolysis with after the inventive method dephosphorization, therefore, the purity of collateral security manganese metal and comprehensive benefit, the present invention be suitable for industrial.
Claims (1)
1. the phosphorus removing method of the made manganese sulfate solution of high phosphorus rhodochrosite, is characterized in that, the method has the following steps:
(1) under room temperature condition, in steel basin, pack the manganese sulfate solution made by high phosphorus rhodochrosite into, then add hydrogen peroxide solution that ferrous sulfate, massfraction are 30% with composition mixing solutions; Then under whipped state, carry out oxidizing reaction;
Wherein, the phosphorus concentration of described manganese sulfate solution between 2.5～3.2g/l, mol ratio=1.0～2 of phosphorus in iron ion and described manganese sulfate solution in ferrous sulfate: 1, mol ratio=0.5～1.25 of iron ion in hydrogen peroxide and ferrous sulfate: 1;
(2) in step (1) gained mixing solutions, add strong aqua to regulate pH value to 3～5, then fully stir to obtain mixed slurry at ambient temperature;
(3) standing, settling step (2) gained mixed slurry, then filters, separates, and gained filtrate is low-phosphorous manganese sulfate solution.
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|---|---|---|---|
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104480308A (en) * | 2015-01-02 | 2015-04-01 | 重庆大学 | Dephosphorizing method for acid vanadium leached solution |
| CN104894374A (en) * | 2015-06-05 | 2015-09-09 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for carrying out phosphorus removal on acidic vanadium-containing solution |
| CN108220600A (en) * | 2018-01-19 | 2018-06-29 | 重庆大学 | The minimizing technology of phosphorus in a kind of acidity vanadium leachate |
| CN110819797A (en) * | 2019-11-21 | 2020-02-21 | 武汉理工大学 | Carbonate mineral leaching method |
| CN110983054A (en) * | 2019-12-31 | 2020-04-10 | 贵州合众锰业科技有限公司 | Method for separating and recovering cobalt and nickel from manganese sulfate solution |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103224263A (en) * | 2013-04-28 | 2013-07-31 | 重庆科技学院 | Method for deep removal of phosphorus from high phosphorus iron ore dephosphorization wastewater |
-
2014
- 2014-03-20 CN CN201410105085.XA patent/CN103818965A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103224263A (en) * | 2013-04-28 | 2013-07-31 | 重庆科技学院 | Method for deep removal of phosphorus from high phosphorus iron ore dephosphorization wastewater |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104480308A (en) * | 2015-01-02 | 2015-04-01 | 重庆大学 | Dephosphorizing method for acid vanadium leached solution |
| CN104894374A (en) * | 2015-06-05 | 2015-09-09 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for carrying out phosphorus removal on acidic vanadium-containing solution |
| CN108220600A (en) * | 2018-01-19 | 2018-06-29 | 重庆大学 | The minimizing technology of phosphorus in a kind of acidity vanadium leachate |
| CN110819797A (en) * | 2019-11-21 | 2020-02-21 | 武汉理工大学 | Carbonate mineral leaching method |
| CN110983054A (en) * | 2019-12-31 | 2020-04-10 | 贵州合众锰业科技有限公司 | Method for separating and recovering cobalt and nickel from manganese sulfate solution |
| CN110983054B (en) * | 2019-12-31 | 2021-07-27 | 贵州合众锰业科技有限公司 | Method for separating and recovering cobalt and nickel from manganese sulfate solution |
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Application publication date: 20140528 |