CN101603181A - A kind of method of passivation-free electrolytic manganese and electrolytic metal Mn thereof - Google Patents
A kind of method of passivation-free electrolytic manganese and electrolytic metal Mn thereof Download PDFInfo
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- CN101603181A CN101603181A CNA2009101042848A CN200910104284A CN101603181A CN 101603181 A CN101603181 A CN 101603181A CN A2009101042848 A CNA2009101042848 A CN A2009101042848A CN 200910104284 A CN200910104284 A CN 200910104284A CN 101603181 A CN101603181 A CN 101603181A
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- electrolytic
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- passivation
- electrolytic metal
- manganese
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Abstract
A kind of method of passivation-free electrolytic manganese and electrolytic metal Mn thereof, this method is similar substantially to the method for prior art, and its improvement part is: add in the tin anhydride in the manganous sulfate electrolytic solution, also be added with boric acid; The proportioning of tin anhydride, boric acid and manganese sulfate solution is respectively 0.02～0.03g/L and 4～8g/L.The power supply of electrolytic process is the pulse power, and its pulse-repetition is 900～1200Hz, and dutycycle is 10～30%, and average current density is 380～420A/m
2Method by the present invention is produced electrolytic metal Mn, in its production process, saved passivation step, therefore, can enough low cost method carry out harmless treatment its waste liquid, can realize the Chrome-free discharging and the qualified discharge of waste liquid, the production cost of its electrolytic metal Mn also reduces greatly.
Description
Technical field
The present invention relates to electrolytic metal Mn and electrolysis process thereof.
Background technology
Manganese metal (Mn) is not still produced stainless steel, the important source material of high-intensity steel alloy and non-ferrous metal alloys such as copper, aluminium, and in medicine, chemical field, extensive use is arranged also.From effective utilization of product purity, Mineral resources, save the energy and environmental pollution and want multiple factor such as little to consider, adopt electrolytic method to produce manganese metal at present mostly.The electrolysis step of existing electrolytic manganese is: according to the source and the purity of raw material, at first produce qualified manganous sulfate (MnSO with different methods
4) solution, with as electrolytic solution; Add electrolysis additive---tin anhydride (SeO at this electrolytic solution then
2); Then just begin electrolysis, be deposited on the electrolytic negative plate with the manganese metal (being electrolytic metal Mn) that allows electrolysis separate out; Because the electrolytic metal Mn surface that is deposited on the electrolytic negative plate is too loose, it is very easily oxidized when it is exposed in the air, so, at present all after electrolysis step, have one usefulness chromatedsolution as passivating solution, come its electrolytic metal Mn is carried out the step of passivation; After this, just the electrolytic negative plate that has electrolytic metal Mn is taken out, wash, dry; At last, peel off down (in the form of sheets) electrolytic metal Mn sheet from electrolytic negative plate.
Though as a whole, produce the pollution level of electrolytic metal Mn with electrolytic process, much smaller more than other methods of producing manganese metal, but, owing to contain a large amount of hexavalent chromiums that environment had pollution in the above-mentioned passivation step in the deactivating solution, so relevant enterprise must carry out harmless treatment to the waste liquid after its passivation.And hexavalent chromium is decided to be a pollutant by country again---that is to say that to the harmless treatment of this waste liquid, not only difficulty is greatly but also usually can not reach the permission degree of discharge.So, the enterprise of many production electrolytic metal Mns is still arranged, often imposed a fine or order within a certain time stopping production by environmental administration because of discharging problem not up to standard.
Summary of the invention
First purpose of the present invention provide a kind of save passivation step and its product still can be not oxidized the method for passivation-free electrolytic manganese.
Second purpose of the present invention is to realize providing a kind of electrolytic metal Mn of passivation-free on the first goal of the invention basis.
The scheme that realizes first goal of the invention is a kind of like this method of passivation-free electrolytic manganese, and this method step same as the prior art comprises: 1. prepare qualified manganese sulfate solution, with as electrolytic solution; 2. in this manganese sulfate solution, add the electrolysis additive tin anhydride; 3. in electrolyzer to the manganese sulfate solution that is added with tin anhydride carry out electrolysis, to obtain being deposited on the electrolytic metal Mn on the electrolytic negative plate; 4. the electrolytic negative plate that has electrolytic metal Mn is taken out, wash, dry; At last, peel off down the electrolytic metal Mn sheet from this electrolytic negative plate.
Its improvements are:
Step 2. in, the proportioning of tin anhydride and manganese sulfate solution is 0.02～0.03g/L; Simultaneously, also be added with (also as additive) boric acid, the proportioning of this boric acid and manganese sulfate solution is 4～8g/L;
Step 3. in, the power supply of electrolytic process is the pulse power, its pulse-repetition is 900～1200Hz, dutycycle is 10～30%, average current density is 380～420A/m
2
The scheme that realizes second goal of the invention is a kind of like this electrolytic metal Mn, and this electrolytic metal Mn is with the scheme that realizes first goal of the invention---the electrolytic metal Mn sheet that the method for passivation-free electrolytic manganese is produced.
From the scheme that realizes first goal of the invention, be not difficult to find out, in the methods of the invention, saved the passivation step in the prior art (or say " operation "), just needn't adopt chromatedsolution used in the prior art, so, in the waste liquid that will discharge, just there has not been hexavalent chromium.This make to this waste liquid carry out harmless treatment, to realize Chrome-free discharging, qualified discharge, become the thing that is very easy to accomplish, so, significantly improved electrolytic manganese economic benefit of enterprises and corresponding social benefit.In electrolytic process of the present invention, utilize the pulse power and supplementary additive boric acid, can keep the surface of the electrolytic manganese that electrolysis separates out for a long time, all the time be in densification, smooth state, so, of the prior art the sort of because of too loose, and in air very easily problem of oxidation just do not existed---guaranteed conversely in the methods of the invention, can not carry out the feasibility and the reliability of Passivation Treatment it.
From the scheme that realizes second goal of the invention as can be seen because this electrolytic metal Mn is to be produced by the method for passivation-free electrolytic manganese of the present invention, so the production cost of this electrolytic metal Mn will reduce greatly.
The present invention is further illustrated below in conjunction with embodiment.
Embodiment
A kind of method of passivation-free electrolytic manganese, this method comprise the steps: 1. to prepare qualified manganous sulfate (MnSO
4) solution, with as electrolytic solution; 2. at this manganous sulfate (MnSO
4) add electrolysis additive tin anhydride (SeO in the solution
2); 3. in electrolyzer to being added with tin anhydride (SeO
2) manganous sulfate (MnSO
4) solution carries out electrolysis, to obtain being deposited on the electrolytic metal Mn on the electrolytic negative plate; 4. the electrolytic negative plate that has electrolytic metal Mn is taken out, wash, dry; At last, peel off down the electrolytic metal Mn sheet from this electrolytic negative plate.
In the present invention:
Step 2. in, tin anhydride (SeO
2) and manganous sulfate (MnSO
4) proportioning of solution is 0.02～0.03g/L; Simultaneously, also be added with boric acid (H
3BO
3), this boric acid (H
3BO
3) and manganous sulfate (MnSO
4) proportioning of solution is 4～8g/L;
Step 3. in, the power supply of electrolytic process is the pulse power, its pulse-repetition is 900～1200Hz, dutycycle is 10～30%, average current density is 380～420A/m
2
Disclose so far, for those skilled in the art, can realize the present invention fully, so, relative unit and more specifically operational details just do not given unnecessary details in this manual.
Further, in order to ensure the reliability of effect, it is better that correlation parameter is controlled at following scope.Boric acid (H
3BO
3) and manganous sulfate (MnSO
4) proportioning of solution is 5～7g/L; The pulse-repetition of described pulsed current is 1000～1100Hz, and dutycycle is 15～25%, and average current density is 390～410A/m
2
Further introduce the checking of being produced the antioxidant effect of electrolytic metal Mn sheet by the inventive method below again.
Verification method is, in following each checking example, all take electrolytic metal Mn that art methods produces and also with art methods but saved each a slice of electrolytic metal Mn of passivation step (operation); get electrolytic metal Mn a slice of the inventive method production; they are placed in the oxygen cabinet that its oxygen level is 40% (twice that is about oxygen level in the air) simultaneously; after half an hour, 8 hours, 24 hours and 60 hours, each paired observation once.Effect with check the present invention.
(annotate: two kinds of electrolytic metal Mn sheets of contrast usefulness are once and produce.Wherein, saved the electrolytic metal Mn sheet of passivation step, after electrolysis finishes, promptly in anoxia condition flushing, drying; After stripping down, be kept at rapidly in the storage box that is full of nitrogen)
Because step, process and the corresponding technology thereof of electrolytic metal Mn are well known to those skilled in the art already, so, in following checking example, the parameter relevant when all only being presented in checking with distinguishing characteristics of the present invention.
Checking example table
| The checking example | ??1 | ??2 | ??3 | ??4 | ??5 | ??6 | ??7 | ??8 |
| ??SeO 2∶MnSO 4(g/L) | ??0.02 | ??0.02 | ??0.25 | ??0.25 | ??0.02 | ??0.03 | ??0.25 | ??0.03 |
| ??H 3BO 3∶MnSO 4(g/L) | ??4 | ??5 | ??6 | ??8 | ??7 | ??6 | ??7 | ??6 |
| Pulse-repetition (Hz) | ??900 | ??1200 | ??1100 | ??1000 | ??1050 | ??1200 | ??1100 | ??1000 |
| Dutycycle (%) | ??30 | ??20 | ??15 | ??10 | ??20 | ??25 | ??25 | ??15 |
| Average current density (A/m 2) | ??380 | ??410 | ??400 | ??420 | ??390 | ??400 | ??390 | ??400 |
The electrolytic metal Mn of respectively verifying in the last table in the example, the contrast corresponding with it relatively found the back with electrolytic metal Mn: after half an hour, with art methods but saved the electrolytic metal Mn sheet of passivation step, all oxidized; After 8 hours and 24 hours, above-mentioned each the example with passivation contrast electrolytic metal Mn sheet, all do not have oxidized vestige; After 60 hours, only verify the electrolytic metal Mn sheet of example 1, the phenomenon of some oxidation stains arranged approximately, all the other each example with passivation contrast electrolytic metal Mn sheet, still not have tangible oxidized vestige.
The explanation of above-mentioned checking example is produced electrolytic metal Mn by the inventive method and is had the good oxidization resistance energy, and under the situation that coherent reference is controlled more suitably, the electrolytic metal Mn that was passivated in its antioxidant property and the prior art is just the same.Obviously, owing to saved passivation step (operation), the cost of this electrolytic metal Mn has also reduced naturally.
Claims (3)
1. the method for a passivation-free electrolytic manganese, this method comprise the steps: 1. to prepare manganese sulfate solution, with as electrolytic solution; 2. in described manganese sulfate solution, add the electrolysis additive tin anhydride; 3. in electrolyzer to the manganese sulfate solution that is added with tin anhydride carry out electrolysis, to obtain being collected at the electrolytic metal Mn on the electrolytic negative plate; 4. the described electrolytic negative plate that has electrolytic metal Mn is taken out, wash, dry; At last, peel off down the electrolytic metal Mn sheet from this electrolytic negative plate; It is characterized in that:
Step 2. in, the proportioning of described tin anhydride and manganese sulfate solution is 0.02～0.03g/L; Simultaneously, also be added with boric acid, the proportioning of this boric acid and described manganese sulfate solution is 4～8g/L;
Step 3. in, the power supply of described electrolytic process is the pulse power, its pulse-repetition is 900～1200Hz, dutycycle is 10～30%, average current density is 380～420A/m
2
2. according to the method for the described passivation-free electrolytic manganese of claim 1, it is characterized in that: the proportioning of described boric acid and manganese sulfate solution is 5～7g/L; The pulse-repetition of the described pulse power is 1000～1100Hz, and dutycycle is 15～25%, and average current density is 390～410A/m
2
3. electrolytic metal Mn, it is characterized in that: this electrolytic metal Mn is the electrolytic metal Mn sheet of producing with the method for claim 1 or 2 described passivation-free electrolytic manganeses.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2009101042848A CN101603181A (en) | 2009-07-09 | 2009-07-09 | A kind of method of passivation-free electrolytic manganese and electrolytic metal Mn thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2009101042848A CN101603181A (en) | 2009-07-09 | 2009-07-09 | A kind of method of passivation-free electrolytic manganese and electrolytic metal Mn thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101845562A (en) * | 2010-06-22 | 2010-09-29 | 陈榜龙 | Improved device and method for producing electrolytic manganese metal by two-ore method |
| CN102492958A (en) * | 2011-12-14 | 2012-06-13 | 凯里学院 | Electrolytic manganese solution containing new additive, and preparation method and application thereof |
| CN102586803A (en) * | 2012-03-27 | 2012-07-18 | 广西靖西县一洲锰业有限公司 | Method for preparing low-lead electrolytic manganese metal |
| CN106119891A (en) * | 2016-08-30 | 2016-11-16 | 中信大锰矿业有限责任公司 | A kind of energy saving technique in electrolytic manganese electrowinning process |
| CN112195484A (en) * | 2020-09-27 | 2021-01-08 | 遵义天磁锰业集团有限公司 | Passivation-free process for electrolytic manganese metal production and product post-treatment method |
-
2009
- 2009-07-09 CN CNA2009101042848A patent/CN101603181A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101845562A (en) * | 2010-06-22 | 2010-09-29 | 陈榜龙 | Improved device and method for producing electrolytic manganese metal by two-ore method |
| CN101845562B (en) * | 2010-06-22 | 2013-03-20 | 陈榜龙 | Improved device and method for producing electrolytic manganese metal by two-ore method |
| CN102492958A (en) * | 2011-12-14 | 2012-06-13 | 凯里学院 | Electrolytic manganese solution containing new additive, and preparation method and application thereof |
| CN102492958B (en) * | 2011-12-14 | 2013-12-18 | 凯里学院 | Electrolytic manganese solution containing new additive, and preparation method and application thereof |
| CN102586803A (en) * | 2012-03-27 | 2012-07-18 | 广西靖西县一洲锰业有限公司 | Method for preparing low-lead electrolytic manganese metal |
| CN106119891A (en) * | 2016-08-30 | 2016-11-16 | 中信大锰矿业有限责任公司 | A kind of energy saving technique in electrolytic manganese electrowinning process |
| CN112195484A (en) * | 2020-09-27 | 2021-01-08 | 遵义天磁锰业集团有限公司 | Passivation-free process for electrolytic manganese metal production and product post-treatment method |
| CN112195484B (en) * | 2020-09-27 | 2024-01-12 | 遵义天磁锰业集团有限公司 | Passivation-free process for electrolytic manganese metal production and product post-treatment method |
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Open date: 20091216 |