CN105200453A - Preparation process of electrolytic refined high-purity manganese - Google Patents
Preparation process of electrolytic refined high-purity manganese Download PDFInfo
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- CN105200453A CN105200453A CN201510697939.2A CN201510697939A CN105200453A CN 105200453 A CN105200453 A CN 105200453A CN 201510697939 A CN201510697939 A CN 201510697939A CN 105200453 A CN105200453 A CN 105200453A
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Abstract
The invention belongs to the technical field of wet-method electrolytic metal manganese, and particularly relates to a preparation process of electrolytic refined high-purity manganese. The high-purity manganese with the purity more than or equal to 99.999 percent is prepared by further purifying a manganese sulfate solution and secondarily electrolyzing, refining and purifying metal manganese. The preparation process comprises the following steps: (1) purifying the manganese sulfate solution to remove impurities, and removing the impurities in an ion exchanging manner; (2) primarily electrolyzing and refining, controlling the electrolytic process parameter, electrolyzing a diaphragm by utilizing an insoluble anode to obtain a primary metal manganese product; (3) secondarily electrolyzing, refining and purifying, and taking the primary metal manganese product as an anode to prepare the smooth high-purity manganese having metal glossiness. The process effectively overcomes the difficulty in purification in the high-purity manganese preparation process, the effect for further removing impurities is obvious, the operation is simple, and the purity of the prepared high-purity manganese is more than or equal to 99.999 percent by virtue of GDMS full-element analysis.
Description
Technical field
The invention belongs to wet method electrolysis manganese metal technical field, particularly the preparation technology of the high-purity manganese of a kind of electrorefining.
Background technology
In structured material field of metallurgy, the application of electrolytic metal Mn and function do not have too large change, but along with the technical progress of metallurgical industry, the new trend of metallurgy manganese proposes special requirement to the becoming more meticulous of Electrolytic Manganese Product, variation, and the demand of colored metallurgical industrial to Special Metal manganese constantly increases.Manganese system power battery anode material, the particularly fast development of CoNiMn tertiary cathode material, propose strict quality requirements to high-purity containing manganic compound, as important high-purity base mateiral containing manganic compound, the market requirement of high pure metal manganese also increases year by year.
Patent documentation Japanese Unexamined Patent Publication 2002-285373 publication describes a kind of manufacture method of high purity manganese, ion exchange purification is carried out to Manganous chloride tetrahydrate aqueous solution application resin, then purified by a galvanic deposit, manganese metal is prepared in vacuum melting (the vapour pressure difference according to metal), the purity preparing manganese is not mentioned in the literature, must carry out strict control to the discharge of chlorine in process, extension is produced has certain limitation simultaneously; Patent CN103114303A carries out secondary-cleaned by adding additive, three pressure-sizing filter purifying electrolysis liquid, then by electrolytic preparation manganese metal, in literary composition but and the purity of not mentioned manganese metal and complicated operation; Patent CN104040030A, by after carrying out pickling to manganese primary material, makes the raw material manganese of more than 1% residual in the solution to primary material lixiviate, utilizes this vat liquor electrolytic preparation to obtain the manganese metal of 99.9% purity; Also describe and obtain high purity manganese by vacuum-sublimation method of purification by solid phase manganese, complicated operation; " development prospect of electrolytic metal Mn process deeply industry " in " nation manganese industry " describes some enterprises and utilizes middle frequency furnace that the purification of impurity thing is removed in violent for electrolytic metal sheet melting, be broken into block after ingot casting to sell as metal manganese ingot product, because its energy consumption is high, added value is lower, the market requirement becomes little, and the development utilizing manganese metal sheet to produce ingot shape manganese product is subject to very large restriction.
At present, in the preparation method of Traditional high purity manganese, technique is too loaded down with trivial details, and the purity of manganese metal maintains the scope lower than 99.99%, there is the drawback that grade is not high.
Summary of the invention
Not enough for prior art, the invention provides the preparation technology of the high-purity manganese of a kind of electrorefining.
This preparation technology takes solution purification process integration re-electrolysis refinery practice, prepares high-purity manganese, comprises the following steps:
1), after manganous sulfate dissolves, regulate PH=4-6, carry out ion-exchange by ion exchange column, impurity F e, Co, Ni, Cu, Pb in deep purifying manganese sulfate solution;
2) through step 1) purification after manganese sulfate solution, regulate PH=6.5-8.5, enter electrolyzer, utilize insoluble anode to carry out diaphragm electrolysis, obtain one-level manganese metal product;
3) step 2) in one-level manganese metal product make anode, carry out re-electrolysis Refining, prepare high-purity manganese of metalluster.
Step 1) in, during deep purifying, manganese sulfate solution successively by 2 to multiple ion-exchange column combination that ion exchange resin is housed, select two or more ion exchange resin in CH90 resin cation (R.C.), D851 resin cation (R.C.), D804 resin and WDA918 resin in ion-exchange column combination.
Step 2) in, in the manganese sulfate solution after described purification, any one foreign matter content in Fe, Co, Ni, Cu, Pb is no more than 1mg/L.
Step 2) described in insoluble anode be titanium or graphite, make negative electrode with titanium.
Step 2) described in barrier film be homogeneous-phase anion film, effectively intercept impurity cationic and deposit on negative electrode; Described anionic membrane is installed on diaphragm frame, and diaphragm frame is positioned over the cathodic area in electrolyzer, and negative electrode is placed in diaphragm frame.Inside maintaining diaphragm frame, liquid level is higher than liquid level 5cm outside diaphragm frame.
Step 2) in electrolysis temperature be 25-30 DEG C, control current density is 200-400A/m
2.
Step 3) in, electrolytic solution is step 2) described in purification after manganese sulfate solution, regulate PH=6.0-8.0.
Step 3) in, electrolysis temperature is 25-30 DEG C, and control current density is 200-400A/m
2.
Purity >=99.99% of the one-level manganese metal product that aforesaid method prepares; High-purity manganese purity >=99.999% prepared, high-purity manganese surfacing, impulse-free robustness.
Beneficial effect of the present invention is: the present invention takes solution purification process integration re-electrolysis refining to prepare high-purity manganese, solution deep impurity-eliminating effect is obvious, workable, re-electrolysis refining significantly improves the purity of manganese product, process operation is simple, the high purity more than 99.999% of product manganese, is beneficial to the extension industrial production of carrying out high-purity manganese.
Accompanying drawing explanation
Fig. 1 is preparation technology's general flow chart of the high-purity manganese of a kind of electrorefining of the present invention;
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention will be further described.It is emphasized that following explanation is only exemplary, instead of in order to limit the scope of the invention and apply.
Embodiment 1:
Manganese sulfate solution utilizes dilute sulphuric acid regulator solution PH=4, and solution is successively by being equipped with the ion exchange column of CH90 resin and the ion exchange column of D804 resin being housed, circulation removal of impurities 24h.Solution before and after purification is analyzed through ICPMS, and foreign matter content is as shown in table 1:
Impurity analysis in table 1 cleansing soln
Manganese sulfate solution after purification, regulates PH=7.0, temperature T=25 DEG C, utilizes corrosion-resistant recycle pump to be sent to electrolyzer and carry out diaphragm electrolysis, and in diaphragm frame, liquid level is higher than the outer liquid level 5cm of diaphragm frame, and current density is 200A/m
2, obtain the first class product of electrolytic metal Mn, analyze through GDMS, total purity of manganese is 99.998%, and foreign matter content is as shown in table 2.
Table 2 first class product impurity analysis
One-level manganese metal product makes anode, and negative electrode made by titanium plate, carries out re-electrolysis, regulates Electrolytic conditions: the manganese sulfate solution after purification is electrolytic solution, control PH=6.0, and current density is 200A/m
2, electrolysis temperature is 25 DEG C.The high-purity manganese obtained carries out GDMS analysis, and its purity reaches 99.9992%, and total impurities content < 10ppm, impurity analysis is as shown in table 3.
The high-purity manganese product impurity analysis of table 3
Embodiment 2:
Manganese sulfate solution with dilute sulphuric acid regulate acidity PH=6, solution successively by be equipped with CH90 resin ion exchange column, the ion exchange column of D851 resin is housed and the ion exchange column of WDA918 resin is housed, circulation removal of impurities 48h.Solution before and after resin purification is analyzed through ICPMS, and foreign matter content is as shown in table 4.
Table 4 cleansing soln impurity analysis
Manganese sulfate solution after purification, regulates PH=8.0, temperature T=30 DEG C, utilizes corrosion-resistant recycle pump to be sent to electrolyzer and carry out diaphragm electrolysis, and in diaphragm frame, liquid level is higher than diaphragm frame outer liquid level 5cm, current density=400A/m
2, obtain electrolytic metal Mn first class product, product is analyzed through GDMS, and total purity of manganese is 99.997%, and foreign matter content is as shown in table 5.
Table 5 first class product impurity analysis
One-level manganese metal product makes anode, and negative electrode made by titanium plate, carries out the high-purity manganese of re-electrolysis synthesis, and adjustment Electrolytic conditions is: the manganese sulfate solution after purification is electrolytic solution, control PH=8.0, and current density is 400A/m
2, electrolysis temperature is 30 DEG C, and galvanic deposit product carries out GDMS analysis, and high-purity manganese purity reaches 99.9993%, and foreign matter content is as shown in table 6.
The high-purity manganese impurity analysis of table 6
Claims (10)
1. a preparation technology for the high-purity manganese of electrorefining, is characterized in that, takes solution purification process integration re-electrolysis refinery practice, prepares high-purity manganese, comprise the following steps:
1), after manganous sulfate dissolves, regulate PH=4-6, carry out ion-exchange by ion exchange column, impurity F e, Co, Ni, Cu, Pb in deep purifying manganese sulfate solution;
2) through step 1) purification after manganese sulfate solution, regulate PH=6.5-8.5, enter electrolyzer, utilize insoluble anode to carry out diaphragm electrolysis, obtain one-level manganese metal product;
3) step 2) in one-level manganese metal product make anode, carry out re-electrolysis Refining, prepare high-purity manganese of metalluster.
2. the preparation technology of the high-purity manganese of a kind of electrorefining according to claim 1, it is characterized in that, step 1) in, during deep purifying, manganese sulfate solution successively by 2 to multiple ion-exchange column combination that ion exchange resin is housed, select two or more ion exchange resin in CH90 resin cation (R.C.), D851 resin cation (R.C.), D804 resin and WDA918 resin in ion-exchange column combination.
3. the preparation technology of the high-purity manganese of a kind of electrorefining according to claim 1, is characterized in that, step 2) in, in the manganese sulfate solution after described purification, any one foreign matter content in Fe, Co, Ni, Cu, Pb is no more than 1mg/L.
4. the preparation technology of the high-purity manganese of a kind of electrorefining according to claim 1, is characterized in that, step 2) described in insoluble anode be titanium or graphite, make negative electrode with titanium.
5. the preparation technology of the high-purity manganese of a kind of electrorefining according to claim 1, is characterized in that, step 2) described in barrier film be homogeneous-phase anion film, effectively intercept impurity cationic and deposit on negative electrode; Described anionic membrane is installed on diaphragm frame, and diaphragm frame is positioned over the cathodic area in electrolyzer, and negative electrode is placed in diaphragm frame.
6. the preparation technology of the high-purity manganese of a kind of electrorefining according to claim 5, is characterized in that, inside maintaining diaphragm frame, liquid level is higher than liquid level 5cm outside diaphragm frame.
7. the preparation technology of the high-purity manganese of a kind of electrorefining according to claim 1, is characterized in that, step 2) in electrolysis temperature be 25-30 DEG C, control current density is 200-400A/m
2.
8. the preparation technology of the high-purity manganese of a kind of electrorefining according to claim 1, is characterized in that, step 3) in, electrolytic solution is step 2) described in purification after manganese sulfate solution, regulate PH=6.0-8.0.
9. the preparation technology of the high-purity manganese of a kind of electrorefining according to claim 1, is characterized in that, step 3) in, electrolysis temperature is 25-30 DEG C, and control current density is 200-400A/m
2.
10. the preparation technology of the high-purity manganese of a kind of electrorefining according to claim 1, is characterized in that, purity >=99.99% of one-level manganese metal product; High-purity manganese purity >=99.999% prepared, high-purity manganese surfacing, impulse-free robustness.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105293584A (en) * | 2015-10-21 | 2016-02-03 | 广西银亿再生资源有限公司 | Method for purifying manganese sulfate solution |
| CN105967238A (en) * | 2016-05-09 | 2016-09-28 | 信丰华锐钨钼新材料有限公司 | High efficiency purification method of ammonium tungstate solution with high Mo content by using special resin |
| CN108179441A (en) * | 2017-12-26 | 2018-06-19 | 广西生富锑业科技股份有限公司 | A kind of production method of high purity antimony |
| CN110257852A (en) * | 2019-06-19 | 2019-09-20 | 贵州红星发展大龙锰业有限责任公司 | Mother liquor re-electrolysis prepares the method and high potential EMD of high potential EMD |
| CN113737220A (en) * | 2021-09-30 | 2021-12-03 | 宁波创致超纯新材料有限公司 | Electrolytic preparation method of high-purity manganese |
| CN113957482A (en) * | 2021-10-20 | 2022-01-21 | 宁波创致超纯新材料有限公司 | Method for preparing high-purity manganese from anolyte |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105293584A (en) * | 2015-10-21 | 2016-02-03 | 广西银亿再生资源有限公司 | Method for purifying manganese sulfate solution |
| CN105293584B (en) * | 2015-10-21 | 2017-10-20 | 广西银亿再生资源有限公司 | A kind of method of purification of sulphuric acids manganese solution |
| CN105967238A (en) * | 2016-05-09 | 2016-09-28 | 信丰华锐钨钼新材料有限公司 | High efficiency purification method of ammonium tungstate solution with high Mo content by using special resin |
| CN108179441A (en) * | 2017-12-26 | 2018-06-19 | 广西生富锑业科技股份有限公司 | A kind of production method of high purity antimony |
| CN110257852A (en) * | 2019-06-19 | 2019-09-20 | 贵州红星发展大龙锰业有限责任公司 | Mother liquor re-electrolysis prepares the method and high potential EMD of high potential EMD |
| CN113737220A (en) * | 2021-09-30 | 2021-12-03 | 宁波创致超纯新材料有限公司 | Electrolytic preparation method of high-purity manganese |
| CN113957482A (en) * | 2021-10-20 | 2022-01-21 | 宁波创致超纯新材料有限公司 | Method for preparing high-purity manganese from anolyte |
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