CN113403649A - Deep purification method of electrolyte for electrolyzing metal manganese - Google Patents
Deep purification method of electrolyte for electrolyzing metal manganese Download PDFInfo
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- CN113403649A CN113403649A CN202110481769.XA CN202110481769A CN113403649A CN 113403649 A CN113403649 A CN 113403649A CN 202110481769 A CN202110481769 A CN 202110481769A CN 113403649 A CN113403649 A CN 113403649A
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
- C25C7/06—Operating or servicing
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/06—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese
- C25C1/10—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese of chromium or manganese
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Abstract
The invention belongs to the technical field of chemical engineering, and particularly relates to a deep purification method of electrolyte for electrolyzing metal manganese, which comprises the following steps: (1) adding ammonia water into a manganese sulfate solution in the electrolytic manganese metal electrolyte preparation process to adjust the pH value to 5-5.5; (2) introducing air, adding 6.5-6.8kg/m3 hydrogen peroxide and 0.19-0.21kg/m3 aluminum sulfate according to the proportion, and stirring for 4-6 h; (3) carrying out primary filter pressing; (4) neutralizing; adding ammonia water to adjust the pH value to 7.0-7.2; (5) adding hydrogen peroxide to remove iron, and adding SDD to remove heavy metals; (6) adding 0.5-0.7kg/m3 aluminum sulfate and fully stirring; (7) adding 2.7-2.9 kg/m3 active carbon for harmful impurity adsorption; (8) standing and separating; (9) and (5) secondary filter pressing. The invention improves the utilization rate of metal manganese ions, reduces the addition of auxiliary materials such as sulfuric acid and the like, reduces the treatment cost and improves the production benefit.
Description
Technical Field
The invention belongs to the technical field of chemical engineering, and particularly relates to a deep purification method of electrolyte for electrolyzing metal manganese.
Background
Since the diaphragm electrolysis method for producing the manganese metal is proposed in the 20 th century, the neutral MnSO4- (NH4)2SO4-H2O series cathode liquid is adopted to carry out diaphragm electrolysis to produce the manganese metal all over the world, and ammonia and an antioxidant must be added in the electrolysis. A large amount of free NH3 exists in the electrolyte, so that ammonia precipitation reaction is serious in the electrolytic process, and the working environment of first-line workers is severe. Because the double salts such as magnesium ammonium sulfate and the like are seriously crystallized in the electrolytic process of the electrolytic manganese metal industry, the diaphragm bag is blocked, the ion migration is hindered, and the like, the alkali of the electrolytic cell can affect the product quality and the yield.
Aiming at the problem that no effective solution exists in the prior art of double salt crystallization, the problem of diaphragm bag blockage can be improved only by increasing the tank cleaning cycle frequency, which undoubtedly increases the production cost.
Disclosure of Invention
In order to solve the technical problems, the invention provides a deep purification method of electrolyte for electrolyzing metal manganese, which enables the pH of bath solution in an electrolytic bath to be stabilized at a higher level and ensures the normal and efficient operation of electrolysis.
A deep purification method of electrolyte for electrolyzing metal manganese comprises the following steps:
(1) adding ammonia water into a manganese sulfate solution in the electrolytic manganese metal electrolyte preparation process to adjust the pH value to 5-5.5;
(2) introducing air, adding 6.5-6.8kg/m3 hydrogen peroxide and 0.19-0.21kg/m3 aluminum sulfate according to the proportion, and stirring for 4-6 h;
(3) carrying out primary filter pressing;
(4) neutralizing; adding ammonia water to adjust the pH value to 7.0-7.2;
(5) adding hydrogen peroxide to remove iron, and adding SDD to remove heavy metals;
(6) adding 0.5-0.7kg/m3 aluminum sulfate and fully stirring;
(7) adding 2.7-2.9 kg/m3 active carbon for harmful impurity adsorption;
(8) standing and separating;
(9) and (5) secondary filter pressing.
Further, in the step (1), ammonia water is added into the manganese sulfate solution to adjust the pH value, and the acidity is 1.5-1.6 g/L.
Further, before adding ammonia water to adjust the pH value in the step (4), introducing air again and stirring, and simultaneously adding 0.5-0.7kg/m3 of aluminum sulfate.
Description of the mechanism: the PH is adjusted to 5.0 before neutralization, hydrogen peroxide is added, iron and heavy metal are removed after filter pressing, and aluminum sulfate activated carbon is added for electrolysis, so that the negative effect of the acidic feed liquor on the yield of the veneer is weakened; meanwhile, the change of the treatment mode enables the yield of the veneer to reach a higher level under the condition that the liquid inlet amount is normal.
Has the advantages that: the invention improves the utilization rate of metal manganese ions, reduces the addition of auxiliary materials such as sulfuric acid and the like, reduces the treatment cost and improves the production benefit.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
Example one
A deep purification method of electrolyte for electrolyzing metal manganese comprises the following steps:
(1) adding ammonia water into a manganese sulfate solution in the process of preparing electrolytic manganese metal electrolyte to adjust the pH value, and adjusting the pH value to 5;
(2) introducing air, adding 6.5kg/m3 hydrogen peroxide and 0.19 aluminum sulfate according to the proportion, and stirring for 4 hours;
(3) carrying out primary filter pressing;
(4) neutralizing; adding ammonia water to adjust the pH value to 7.0;
(5) adding hydrogen peroxide to remove iron to micro iron, and adding SDD to remove heavy metals to a nickel-free state;
(6) adding 0.5 aluminum sulfate and fully stirring;
(7) adding 2.7 kg/m3 activated carbon for adsorbing harmful impurities;
(8) standing and separating;
(9) and (5) secondary filter pressing.
In the step (1), ammonia water is added into the manganese sulfate solution to adjust the pH value, and the acidity is 1.5 g/L.
Before adding ammonia water to adjust the pH value in the step (4), introducing air again and stirring, and simultaneously adding 0.5 kg/m3 of aluminum sulfate.
Carry out the electrolysis through above-mentioned scheme, the interior tank liquor pH level of electrolysis trough has great promotion, can stabilize about 7.3~7.4, guarantees the normal clear of electrolysis, has weakened the negative effect of acid feed liquor to veneer output.
Example two
A deep purification method of electrolyte for electrolyzing metal manganese comprises the following steps:
(1) adding ammonia water into a manganese sulfate solution in the process of preparing electrolytic manganese metal electrolyte to adjust the pH value, and adjusting the pH value to 5.5;
(2) introducing air, adding 6.8kg/m3 hydrogen peroxide and 0.21kg/m3 aluminum sulfate according to the proportion, and stirring for 6 hours;
(3) carrying out primary filter pressing;
(4) neutralizing; adding ammonia water to adjust the pH value to 7.2;
(5) adding hydrogen peroxide to remove iron, and adding SDD to remove heavy metals;
(6) 0.7kg/m3 aluminum sulfate was added and sufficiently stirred;
(7) adding 2.9 kg/m3 activated carbon for adsorbing harmful impurities;
(8) standing and separating;
(9) and (5) secondary filter pressing.
In the step (1), ammonia water is added into the manganese sulfate solution to adjust the pH value, and the acidity is 1.6 g/L.
Before adding ammonia water to adjust the pH value in the step (4), introducing air again and stirring, and simultaneously adding 0.7kg/m3 of aluminum sulfate.
Carry out the electrolysis through above-mentioned scheme, the interior tank liquor pH level of electrolysis trough has great promotion, can stabilize about 7.3~7.5, guarantees the normal clear of electrolysis, has weakened the negative effect of acid feed liquor to veneer output.
EXAMPLE III
A deep purification method of electrolyte for electrolyzing metal manganese comprises the following steps:
(1) adding ammonia water into a manganese sulfate solution in the process of preparing electrolytic manganese metal electrolyte to adjust the pH value, and adjusting the pH value to 5;
(2) introducing air, adding 6.5-6.8kg/m3 hydrogen peroxide and 0.19-0.21kg/m3 aluminum sulfate according to the proportion, and stirring for 4-6 h;
(3) carrying out primary filter pressing;
(4) neutralizing; adding ammonia water to adjust the pH value to 7.0;
(5) adding hydrogen peroxide to remove iron, and adding SDD to remove heavy metals;
(6) 0.6kg/m3 aluminum sulfate was added and sufficiently stirred;
(7) adding 2.8 kg/m3 activated carbon for adsorbing harmful impurities;
(8) standing and separating;
(9) and (5) secondary filter pressing.
Further, in the step (1), ammonia water is added into the manganese sulfate solution to adjust the pH value, and the acidity is 1.52 g/L.
Further, before the pH was adjusted by adding ammonia water in the step (4), air was again introduced and stirred while adding aluminum sulfate in an amount of 0.6kg/m 3.
Carry out the electrolysis through above-mentioned scheme, the interior tank liquor pH level of electrolysis trough has great promotion, can stabilize about 7.2~7.3, guarantees the normal clear of electrolysis, has weakened the negative effect of acid feed liquor to veneer output.
Description of the mechanism: adjusting the pH value to 5-5.5 before neutralization, adding hydrogen peroxide, removing iron and heavy metals after filter pressing, and adding aluminum sulfate activated carbon for electrolysis, so that the negative effect of acidic feed liquor on the yield of the veneer is weakened; meanwhile, the change of the treatment mode enables the yield of the single plate to reach a higher level under the condition of normal liquid inlet amount, the utilization rate of the metal manganese ions to be obviously improved, and the addition of auxiliary materials such as activated carbon, aluminum sulfate, hydrogen peroxide, sulfuric acid and the like is correspondingly reduced.
In conclusion, the invention has the following obvious advantages: the invention improves the utilization rate of metal manganese ions, reduces the addition of auxiliary materials such as sulfuric acid and the like, reduces the treatment cost and improves the production benefit.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (3)
1. A deep purification method of electrolyte for electrolyzing metal manganese is characterized in that the purification process comprises the following steps:
(1) adding ammonia water into a manganese sulfate solution in the electrolytic manganese metal electrolyte preparation process to adjust the pH value to 5-5.5;
(2) introducing air, adding 6.5-6.8kg/m3 hydrogen peroxide and 0.19-0.21kg/m3 aluminum sulfate according to the proportion, and stirring for 4-6 h;
(3) carrying out primary filter pressing;
(4) neutralizing; adding ammonia water to adjust the pH value to 7.0-7.2;
(5) adding hydrogen peroxide to remove iron, and adding SDD to remove heavy metals;
(6) adding 0.5-0.7kg/m3 aluminum sulfate and fully stirring;
(7) adding 2.7-2.9 kg/m3 active carbon for harmful impurity adsorption;
(8) standing and separating;
(9) and (5) secondary filter pressing.
2. The method for deeply purifying an electrolytic manganese metal as claimed in claim 1, wherein in the step (1), the pH of the manganese sulfate solution is adjusted to 1.5 to 1.6g/L by adding ammonia water.
3. The method for deep purification of an electrolytic solution for electrolytic manganese metal according to claim 1, wherein before the addition of ammonia water to adjust the pH in the step (4), air is again introduced and stirred while adding aluminum sulfate in an amount of 0.5 to 0.7kg/m 3.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103014760A (en) * | 2013-01-09 | 2013-04-03 | 广西有色金属集团汇元锰业有限公司 | Production method of electrolytic manganese metal |
| CN103074490A (en) * | 2013-01-09 | 2013-05-01 | 广西有色金属集团汇元锰业有限公司 | Purification method in electrolytic metal manganese production process by multi-mine method |
| CN103451423A (en) * | 2013-09-04 | 2013-12-18 | 宁夏天元锰业有限公司 | Solution preparation method of electrolytic manganese metal |
| CN106637295A (en) * | 2016-12-09 | 2017-05-10 | 宁夏天元锰业有限公司 | Purifying method for process of preparing electrolytic manganese metal electrolyte |
| JP2017178749A (en) * | 2016-03-31 | 2017-10-05 | 東ソー株式会社 | Method for producing manganese sulfate aqueous solution and method for producing manganese oxide |
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- 2021-04-30 CN CN202110481769.XA patent/CN113403649A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103014760A (en) * | 2013-01-09 | 2013-04-03 | 广西有色金属集团汇元锰业有限公司 | Production method of electrolytic manganese metal |
| CN103074490A (en) * | 2013-01-09 | 2013-05-01 | 广西有色金属集团汇元锰业有限公司 | Purification method in electrolytic metal manganese production process by multi-mine method |
| CN103451423A (en) * | 2013-09-04 | 2013-12-18 | 宁夏天元锰业有限公司 | Solution preparation method of electrolytic manganese metal |
| JP2017178749A (en) * | 2016-03-31 | 2017-10-05 | 東ソー株式会社 | Method for producing manganese sulfate aqueous solution and method for producing manganese oxide |
| CN106637295A (en) * | 2016-12-09 | 2017-05-10 | 宁夏天元锰业有限公司 | Purifying method for process of preparing electrolytic manganese metal electrolyte |
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