CN101985365A

CN101985365A - Method for manufacturing manganese carbonate

Info

Publication number: CN101985365A
Application number: CN2010102208928A
Authority: CN
Inventors: 山冈利至; 樋口直树; 成迫诚; 小林大祐
Original assignee: JX Nippon Mining and Metals Corp
Current assignee: JX Nippon Mining and Metals Corp
Priority date: 2009-07-07
Filing date: 2010-07-01
Publication date: 2011-03-16
Also published as: JP2011016668A; KR20110004288A; KR101274365B1; JP5106488B2

Abstract

The present invention provides a method for manufacturing manganese carbonate, capable of easily obtaining high-purity manganese carbonate containing less impurity, e.g. natrium, by using a strong acidity manganese solution, e.g. an extracting liquid. The method for manufacturing the manganese carbonate includes: adjusting pH value of an acidic manganese solution to 7-8, and blowing carbon dioxide to the solution to obtain the manganese carbonate containing less impurity.

Description

The manufacture method of manganous carbonate

Technical field

The invention that the present invention relates to when from the tart manganese solution, reclaiming manganese, especially notice sodium and reclaim highly purified manganous carbonate with high-recovery with manganous carbonate.

Background technology

In recent years, except the battery material of electronics, lithium-ion secondary cell and so on, in alloy and other various materials, the usage quantity of manganese is being on the increase.In these equipment, battery, material etc., manganese is not independent use, but is used in combination with other metal ingredients.Therefore, when recovery is used for the manganese of equipment, battery etc., be necessary from these metal ingredients, only to separate manganese.As being used for one of this isolating method, the method for using the acidic extraction agent is arranged, open normally used method as shown in the 2008-231522 (patent documentation 1) as the Japanese Patent spy.Yet,,, be necessary it is contacted with acid in order from extraction agent, to take out metal ingredient to water if use the acidic extraction agent.Here, for the major part with manganese contained in the extraction agent moves to water, the water that must contact with extraction agent is changed into strongly-acid.Be strongly-acid so by the resulting manganese aqueous solution of abstraction process.

For implementing to manganese oxide or manganous carbonate under the situation that pH adjusts from the acid manganese solution of acquisition like this, when for example using oxyhydroxide such as caustic soda, Ke Xingjia, the sodium of water, potassium particle concentration raise, be difficult to the manganese that reclaims under the state of impurity as target preventing to sneak into, promptly be difficult to obtain highly purified manganic compound.

Patent documentation 1: the spy opens 2008-231522

Summary of the invention

In addition, when from manganese solution, separating manganese, also consider directly or use carbonate such as yellow soda ash to adjust agent carbonic acid supplying agent with the form of its aqueous solution, make manganous carbonate generate precipitation, separate by filtration as pH with carbonate form.Yet,,, the possibility of sneaking into the sodium composition is arranged after the drying filtering because the sodium composition in the solution is entrained in the filtrate in the method.And then, as previously mentioned, when sodium in the solution having been increased by adjusting pH owing to form the condition of easy precipitated sodium, especially have in manganous carbonate, sneak into sodium may.When using a large amount of washing water, manganous carbonate is run off in filtrate for fear of sneaking into of above-mentioned sodium.So need following method, in the operation that reclaims valuable metal, only take out after the manganese, obtain highly purified manganous carbonate by the abstraction process that has used the acidic extraction agent.The present invention is a technical task with the method that obtains highly purified manganous carbonate by easy method.

Thereby,, reached following invention in order to address the above problem.(1) a kind of manufacture method of manganous carbonate comprises with ammoniacal liquor the pH of acid manganese solution is transferred to 7～8, is blown into carbonic acid gas in this solution, obtains the few manganous carbonate of impurity.(2) in the manufacture method of above-mentioned (1) described manganous carbonate, the Na in the manganous carbonate is below the 100 quality ppm.(3) in the manufacture method of above-mentioned (1) or (2) any described manganous carbonate, in being blown into the carbonic acid gas process, continue to add ammoniacal liquor, continue to keep pH 7～8, obtain the few manganous carbonate of impurity.(4) in the manufacture method of above-mentioned (3) described manganous carbonate, the Na in the manganous carbonate is below the 100 quality ppm.

According to the present invention, can obtain following effect.(1) can easily obtain the low manganous carbonate of sodium content.When (2) after extraction, from solution, reclaiming manganese, when in the stronger solution of acidity, generating manganous carbonate, can easily obtain the few manganous carbonates of impurity such as sodium.

Description of drawings

Fig. 1 represents the treatment scheme according to an embodiment of the invention.

Fig. 2 represents according to the sedimentary XRD figure shape of the manganous carbonate of an embodiment of the invention.

Embodiment

In the present invention, can use as the manganese concentration of the acid manganese liquid of raw material and be material arbitrarily.Can be reduced to about 5ppm with the manganese concentration that manganous carbonate reclaims after carbonating,, can also from dilute solution, reclaim manganous carbonate if on cost, balance each other.On the contrary,, do not see and separate out, just can be used as raw material and use as long as surpass solubleness even be the aqueous solution of high density.

Before with tart manganese liquid carbonating, adjust pH.Use ammoniacal liquor in the present invention.If be ammoniacal liquor, can avoid sneaking into of manganese metal ingredient in addition.PH is as long as be the soluble pH of carbonic acid gas.Ammoniacal liquor uses after for example preferably being adjusted into about 20～40 quality %.

Even if when pH5, also carry out carbonating, but consider that from speed of response and yield preferred pH is 7 to 8.The adjusted manganese solution of pH is carried out carbonating with carbonic acid gas.Adjustment gets final product the speed that is blown into according to the manufacturing scale.

For example, comparatively suitable about 100ml/ minute if be beaker level (PVC one カ one レベ Le), under the situation of amplifying, can be blown into to greater amount.For the carbonic acid gas that is blown into is dissolved in solution, preferably will be blown into mouth and more slightly separate.In addition, in being blown into the process of carbonic acid gas, pH reduces, and this adjustment is also preferably carried out with ammoniacal liquor.At this moment, pH also preferably maintains 7～8.This is because be fit to obtain manganous carbonate.After fully reacting, filtration, washing, drying can obtain highly purified manganous carbonate thus.

(embodiment 1)

According to treatment scheme shown in Figure 1, below an embodiment of the invention are described.Prepare the 250ml manganese aqueous solution (pH0, manganese concentration 75g/L), add the 28 quality % ammoniacal liquor of 50ml.PH after the interpolation is 7.1.In this manganese liquid, be blown into carbonic acid gas with 100ml/ minute flow.After continuing to be blown into carbonic acid gas, pH begins to descend owing to react.Therefore, slowly splash into ammoniacal liquor, so that pH maintains 7～8.For the manganese in the solution is fully reacted, being blown into of carbonic acid gas carried out 3hr.In being blown into the process of carbonic acid gas, the addition of ammoniacal liquor reaches 50ml.

Filter being blown into the throw out that generates behind the carbonic acid gas, from liquid phase separation.After drying precipitate, carry out X-ray diffraction (hereinafter referred to as XRD).The sedimentary XRD figure shape that obtains by embodiment as shown in Figure 2.Carried out XRD, the result is shown in the arrow among Fig. 2, and is consistent with the peak of manganous carbonate.During concentration by ICP luminescence assays filtrate, the concentration of manganese is 6ppm.As can be known from these results, contained manganese almost 100% can be used as manganous carbonate and is recovered in the initial manganese aqueous solution.Measure the concentration of the sodium impurity in the manganous carbonate, the result is 98 quality ppm.

(comparative example 1)

Prepare the 250ml manganese aqueous solution (pH0, manganese concentration 75g/L), add the 28 quality % ammoniacal liquor of 50ml.PH after the interpolation is 7.1.With 100ml/ minute flow, in this manganese liquid, be blown into carbonic acid gas.After continuing to be blown into carbonic acid gas, pH begins to descend owing to react.For the manganese in the solution is fully reacted, being blown into of carbonic acid gas carried out 3hr.PH is reduced to 6.Filter being blown into the throw out that generates behind the carbonic acid gas, from liquid phase separation.After drying precipitate, carried out XRD, the result is consistent with the peak of manganous carbonate.By the concentration of ICP luminescence assays filtrate, the concentration of manganese is 50g/L as a result.As can be known from these results, about 33% of contained manganese can be used as manganous carbonate and be recovered in the initial manganese aqueous solution.

(comparative example 2)

Prepare the 250ml manganese aqueous solution (pH0, manganese concentration 75g/L), add the 28 quality % ammoniacal liquor of 50ml.PH after the interpolation is 7.1.In this manganese liquid, add 50g yellow soda ash and make it to generate precipitation.The throw out that generates is filtered, from liquid phase separation.After drying precipitate, carried out XRD, the result is consistent with the peak of manganous carbonate.During concentration by ICP luminescence assays filtrate, the concentration of manganese is below the 5ppm.As can be known from these results, contained manganese almost 100% can be used as manganous carbonate and is recovered in the initial manganese aqueous solution.Measure the concentration of the sodium impurity in the manganous carbonate, the result is 5000ppm.

(comparative example 3)

Prepare the 250ml manganese aqueous solution (pH0, manganese concentration 75g/L).With 100ml/ minute flow, in this manganese liquid, be blown into carbonic acid gas.PH does not change.Do not observe sedimentary generation.By the concentration of ICP luminescence assays filtrate, the concentration of manganese is 75g/L as a result.

Claims

1. the manufacture method of a manganous carbonate is characterized in that, comprising:

With ammoniacal liquor the pH of acid manganese solution is transferred to 7～8, in this solution, be blown into carbonic acid gas, obtain the few manganous carbonate of impurity.

2. the manufacture method of manganous carbonate according to claim 1 is characterized in that, the Na in the described manganous carbonate is below the 100 quality ppm.

3. the manufacture method of manganous carbonate according to claim 1 and 2 is characterized in that, in being blown into the carbonic acid gas process, continues to add ammoniacal liquor, and continuing to keep pH is 7～8, obtains the few manganous carbonate of impurity.

4. the manufacture method of manganous carbonate according to claim 3 is characterized in that, the Na in the described manganous carbonate is below the 100 quality ppm.