CN104773761B - A kind of calcium removal methods of electrolytic manganese dioxide - Google Patents
A kind of calcium removal methods of electrolytic manganese dioxide Download PDFInfo
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Abstract
The invention belongs to battery material manufacture field, be specifically related to a kind of calcium removal methods of electrolytic manganese dioxide.The method comprises the following steps: high calcium electrolytic manganese dioxide powder is put into electrolytic solution, soaks, and controls the temperature of immersion, time and pH value, filters; Dry, pulp; Neutralization: add alkali adjust ph, control temperature and time; Dry.Through process of the present invention, effectively can remove the calcium in high calcium electrolytic manganese dioxide, improve product purity.
Description
Technical field
The invention belongs to battery material manufacture field, be specifically related to a kind of calcium removal methods of electrolytic manganese dioxide.
Background technology
Electrolytic manganese dioxide (EMD) is the depolarizer of excellent battery, compared with the drying battery that it and natural electric discharge Manganse Dioxide are produced, there is large, active strong, the feature such as volume is little, the life-span is long, stable operating voltage, low-temperature performance and leak resistance are good of loading capacity, mix the drying battery that 20-30%EMD makes and than entirely use natural MnO
2its loading capacity of the drying battery made can improve 50-100%, 50-70%EMD is mixed in high-performance chlorinated zinc battery, its loading capacity can improve 2-3 doubly, all with the alkaline Mn cell that EMD makes, its loading capacity can improve 5-7 doubly, and therefore electrolytic manganese dioxide becomes the very important raw material of one of battery industry.
Physical condition electrolytic manganese dioxide, except as except the main raw material of battery, is also widely used in the fields such as metallurgy, medical science, electronics, communication.As: make the raw material in oxygenant, Mn-Zn ferrite soft magnetic materials in fine chemistry industry production process.Electrolytic manganese dioxide is owing to having very strong catalysis, oxidation/reduction, ion-exchange and adsorptive power, treated and shaping after, be the comprehensive excellent water purification filtrate of a kind of performance, compared with the conventional water purification filtrate such as activated carbon, zeolite, there is the ability of stronger decolouring and removal metal.
The production of current domestic electrolytic manganese dioxide mainly with manganese carbonate ore or manganese oxide ore for raw material.With the development of Iron And Steel Industry, manganese goods industry is also flourish, and the Technology therefrom extracting manganese in low-grade manganese is also more and more rich and varied, as H
2o
2lixiviation process, oxalic acid infusion process, glucose lixiviation process, rice bran lixiviation process etc.But the electrolytic manganese dioxide grade obtained is lower, and various metals content impurity is high, especially calcium contents, have a strong impact on the quality of electrolytic manganese dioxide.The consumption of manganese carbonate ore and sulfuric acid is all very large simultaneously, and production cost is too high.
Patent 021500851 discloses a kind of deep-purifying method of manganese sulfate solution.It is a kind of method of the element such as deep purifying Potassium, molybdenum, iron, cobalt, nickel, copper from manganese sulfate solution, the present invention uses full carbonic acid liquid, introducing NaOH, BaS, diatomite process solution, regulate addition and order of addition in conjunction with practical situation.The pH value range of this invention setting is very large, can not meet high-quality electrolytic solution demand.Precipitation process is not thorough, is difficult to removing calcium ion with this intermediate processing.
Summary of the invention
An object of the present invention is a kind of calcium removal methods of electrolytic manganese dioxide, comprise the following steps:
(1) high calcium electrolytic manganese dioxide powder is put into electrolytic solution, soak, control the temperature of immersion, time and pH value, filter;
(2) dry, pulp;
(3) neutralize: add alkali adjust ph, control temperature and time;
(4) dry.
Electrolytic solution in described step (1) is the mixing solutions of sulfuric acid and manganous sulfate;
The mol ratio of described manganous sulfate and sulfuric acid is 1:450000 ~ 2:1.
The temperature of carrying out of described immersion is 30 ~ 95 DEG C, preferably 40 ~ 75, and the time is 20 ~ 180, preferred 30-100 minute.
Described immersion control ph below 4.5, preferably less than 3.0.
Described filtration adopts vacuum filtration.
The pulp liquid that described pulp uses is water or the aqueous solution.
In described N-process, regulate pH to 4.5 ~ 7.0, preferred 5.0-5.8; Temperature is 40-70 DEG C; Time length is 30-100 minute.
In described N-process, the alkali added is sodium hydroxide; Described naoh concentration is 0.5 ~ 3mol/L.
Described bake out temperature is 60 ~ 120 DEG C; Time 60-180 minute.
Dilute sulphuric acid in the present invention in electrolytic solution, manganous sulfate, can effectively obtain pure electrolytic manganese dioxide.Pass through the control of immersion and time-temperature, remove the calcium ion in solution, remove other heavy metal ion simultaneously.Twice drying course can effectively collect pure electrolytic manganese dioxide.N-process add the potential of hydrogen that can adjust solution, obtain the electrolytic manganese dioxide solution of more high-quality.Technique of the present invention is simple, requires low, suitable for mass production to mechanical means.
Embodiment
embodiment 1
(1) high calcium electrolytic manganese dioxide powder is put into electrolytic solution, in electrolytic solution, the mol ratio of sulfuric acid and manganous sulfate is 1:600, and soak, temperature is 60 DEG C, and the time is 60 minutes.Vacuum filtration, control ph is below 3.0;
(2) put into oven for drying, temperature is 110 DEG C.Time is 120 minutes.Add water pulp;
(3) neutralize: add 1mol/L sodium hydroxide, adjust ph is 5.5, and control temperature is 60 DEG C, and the time length is 60 minutes;
(4) put into oven for drying, temperature is 110 DEG C.Time is 120 minutes.
embodiment 2
(1) high calcium electrolytic manganese dioxide powder is put into electrolytic solution, in electrolytic solution, the mol ratio of sulfuric acid and manganous sulfate is 2:1, and soak, temperature is 40 DEG C, and the time is 100 minutes.Vacuum filtration, control ph is below 4.5;
(2) put into oven for drying, temperature is 60 DEG C.Time is 180 minutes.Add aqueous solution pulp;
(3) neutralize: add 0.5mol/L sodium hydroxide, adjust ph is 5.0, and control temperature is 70 DEG C, and the time length is 30 minutes;
(4) put into oven for drying, temperature is 120 DEG C.Time is 60 minutes.
embodiment 3
(1) high calcium electrolytic manganese dioxide powder is put into electrolytic solution, in electrolytic solution, the mol ratio of sulfuric acid and manganous sulfate is 1:450000, and soak, temperature is 75 DEG C, and the time is 30 minutes.Vacuum filtration, control ph is below 3.0.
(2) put into oven for drying, temperature is 120 DEG C.Time is 120 minutes.Add aqueous solution pulp;
(3) neutralize: add 3mol/L sodium hydroxide, adjust ph is 5.8, and control temperature is 40 DEG C, and the time length is 100 minutes;
(4) put into oven for drying, temperature is 90 DEG C.Time is 180 minutes.
embodiment 4
(1) high calcium electrolytic manganese dioxide powder is put into electrolytic solution, in electrolytic solution, the mol ratio of sulfuric acid, manganous sulfate is 1:500, and soak, temperature is 95 DEG C, and the time is 20 minutes.Vacuum filtration, control ph is below 4.0.
(2) put into oven for drying, temperature is 110 DEG C.Time is 115 minutes.Add water pulp;
(3) neutralize: add 1mol/L sodium hydroxide, adjust ph is 4.5, and control temperature is 40 DEG C, and the time length is 70 minutes;
(4) put into oven for drying, temperature is 110 DEG C.Time is 130 minutes.
embodiment 5
(1) high calcium electrolytic manganese dioxide powder is put into electrolytic solution, in electrolytic solution, the mol ratio of sulfuric acid, manganous sulfate is 1:80000, and soak, temperature is 30 DEG C, and the time is 45 minutes.Vacuum filtration, control ph is below 4.5.
(2) put into oven for drying, temperature is 110 DEG C.Time is 140 minutes.Add aqueous solution pulp;
(3) neutralize: add 2.5mol/L sodium hydroxide, adjust ph is 7.0, and control temperature is 64 DEG C, and the time length is 50 minutes;
(4) put into oven for drying, temperature is 110 DEG C.Time is 112 minutes.
embodiment 6
(1) high calcium electrolytic manganese dioxide powder is put into electrolytic solution, in electrolytic solution, the mol ratio of sulfuric acid, manganous sulfate is 1:3000, and soak, temperature is 56 DEG C, and the time is 180 minutes.Vacuum filtration, control ph is below 2.5.
(2) put into oven for drying, temperature is 110 DEG C.Time is 160 minutes.Add water pulp;
(3) neutralize: add 1.5mol/L sodium hydroxide, adjust ph is 5.8, and control temperature is 62 DEG C, and the time length is 45 minutes;
(4) put into oven for drying, temperature is 110 DEG C.Time is 165 minutes.
comparative example 1
(1) high calcium electrolytic manganese dioxide powder is put into electrolytic solution, electrolytic solution is sulfuric acid, and soak, temperature is 15 DEG C, and the time is 5 minutes.Vacuum filtration, control ph is less than 6.0.
(2) put into oven for drying, temperature is 50 DEG C.Time is 130 minutes.Add water pulp;
(3) neutralize: add 1mol/L sodium hydroxide, adjust ph is 8.5, and control temperature is 70 DEG C, and the time length is 20 minutes;
(4) put into oven for drying, temperature is 180 DEG C.Time is 250 minutes.
Use identical high calcium electrolytic manganese dioxide powder, detect embodiment 1, embodiment 2, comparative example 1 and comparative example 2(patent 021500851 embodiment 1) deliming effect, measure calcium contents and Mg content.Result is as follows:
Table 1
As shown in table 1, the embodiment of the present application 1 and embodiment 2, calcium contents and Mg content are far below comparative example 1 and comparative example 2, and deliming Be very effective, can obtain pure electrolytic manganese dioxide.
Above-mentioned detailed description is illustrating for one of them possible embodiments of the present invention, and this embodiment is also not used to limit the scope of the claims of the present invention, and the equivalence that all the present invention of disengaging do is implemented or changed, and all should be contained in the scope of technical solution of the present invention.
Claims (4)
1. a calcium removal methods for electrolytic manganese dioxide, is characterized in that, comprises the following steps:
High calcium electrolytic manganese dioxide powder is put into electrolytic solution, soaks, control the temperature of immersion, time and pH value, filter;
Dry, pulp;
Neutralization: add alkali adjust ph, control temperature and time;
Dry;
Electrolytic solution in described step (1) is the mixing solutions of sulfuric acid and manganous sulfate;
The mol ratio of described sulfuric acid and manganous sulfate is 1:450000 ~ 2:1;
The temperature of carrying out of described immersion is 40 ~ 75 DEG C; Time is 30 ~ 100 minutes;
Described immersion control ph is below 3.0;
In described N-process, regulate pH to 5.0-5.8; Temperature is 40-70 DEG C; Time length is 30-100 minute;
In described N-process, the alkali added is sodium hydroxide; Described naoh concentration is 0.5 ~ 3mol/L.
2. the calcium removal methods of electrolytic manganese dioxide as claimed in claim 1, is characterized in that, described filtration adopts vacuum filtration.
3. the calcium removal methods of electrolytic manganese dioxide as claimed in claim 1, is characterized in that, the pulp liquid that described pulp uses is water or the aqueous solution.
4. the calcium removal methods of electrolytic manganese dioxide as claimed in claim 1, it is characterized in that, described bake out temperature is 60 ~ 120 DEG C, 60 ~ 180 minutes time.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5078889A (en) * | 1989-02-28 | 1992-01-07 | Csa Division, Lake Industries, Inc. | Selective removal of contaminants from water sources using inorganic media |
| CN101372362A (en) * | 2008-10-16 | 2009-02-25 | 湖南化工研究院 | Preparation and use of high quality chemical manganese bioxide |
| CN103572317A (en) * | 2013-11-07 | 2014-02-12 | 广西桂柳化工有限责任公司 | Method for refining electrolytic manganese dioxide product |
| CN103572314A (en) * | 2013-11-07 | 2014-02-12 | 广西桂柳化工有限责任公司 | Edulcoration treatment method of electrolytic manganese dioxide semi-finished products |
-
2015
- 2015-04-15 CN CN201510177312.4A patent/CN104773761B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5078889A (en) * | 1989-02-28 | 1992-01-07 | Csa Division, Lake Industries, Inc. | Selective removal of contaminants from water sources using inorganic media |
| CN101372362A (en) * | 2008-10-16 | 2009-02-25 | 湖南化工研究院 | Preparation and use of high quality chemical manganese bioxide |
| CN103572317A (en) * | 2013-11-07 | 2014-02-12 | 广西桂柳化工有限责任公司 | Method for refining electrolytic manganese dioxide product |
| CN103572314A (en) * | 2013-11-07 | 2014-02-12 | 广西桂柳化工有限责任公司 | Edulcoration treatment method of electrolytic manganese dioxide semi-finished products |
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