CN103451674B - The production method of electrolytic metal Mn - Google Patents
The production method of electrolytic metal Mn Download PDFInfo
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Abstract
The invention provides a kind of production method of electrolytic metal Mn, comprising: provide manganese electrolyte, described manganese electrolyte comprises electrolysis additive, and described electrolysis additive comprises the composition of following weight percent: the antioxidant of 15% ~ 26%; The surfacing agent of 2% ~ 3%, described surfacing agent is contain the natural organic high-molecular of amino and carboxyl or contain the synthetic organic polymer of amino and carboxyl; The crystal formation changing agent of 40% ~ 70%, described crystal formation changing agent is low sulfur compounds and at least one in low price phosphorus compound; The complexing agent of 12% ~ 32%; Described manganese electrolyte is carried out electrolysis, obtains electrolytic metal Mn.In the present invention, described electrolysis additive is a kind of without selenium additive, when carrying out electrolytic metal Mn and producing, can low selenium electrolytic manganese product be obtained, and have and only use the electrolytic efficiency be close during selenium additive, simultaneously, the relative selenium additive of described electrolysis additive is more cheap, and production cost is lower.
Description
Technical field
The present invention relates to manganese metal production technical field, particularly a kind of production method of electrolytic metal Mn.
Background technology
Manganese is the metallic element that a kind of activity is very high, and its standard potential is-1.182V.Manganese and manganese alloy are one of indispensable important source material such as Iron And Steel Industry, aluminium alloy industry, magnetic material industry and chemical industry.At present, the refinement mode of manganese metal mainly contains pyrogenic process and wet method two kinds.Wherein, pyrogenic process, also referred to as hot method, comprises electro-silicothermic process and thermite process, and the purity of its manganese metal produced is no more than 95% ~ 98%; And wet method mainly refers to electrolytic process, the purity of the manganese metal prepared by electrolytic process can more than 99.7% ~ 99.9%, and the manganese metal of this purity is called as electrolytic metal Mn.Owing to having high purity and low impurity, electrolytic metal Mn is now successful and be widely used in the every field such as smelting iron and steel, nonferrous metallurgy, electronic technology, chemical industry, environment protection, food sanitation, welding electrode industry and space industry.
Now, electrolytic process produces the major way having become manganese metal and produced.Electrolytic process is produced can be divided into two main process: liquid processed and electrolysis, wherein, liquid processed be namely produce out qualified can electrolysis containing mn ion solution, generally comprise the operations such as leachings, removal of impurities, coarse filtration, smart filtration and interpolation electrolysis additive; Namely electrolysis is that obtained by liquid processed qualified can the passing into electrolyzer containing mn ion solution and carry out electrolysis of electrolysis, obtains electrolytic metal Mn.
In electrolytic process production process, if do not add suitable electrolysis additive, electrolytic manganese solution can only obtain hydrogen and oxygen.So, in order to can manganese metal be obtained, usually adopt selenium additive to be electrolysis additive at present.Selenium additive refers to containing selenium compound, and can reduce the precipitation of hydrogen in electrolytic manganese process, electrolytic manganese electrolytic efficiency is 70% ~ 75%, and electrolysis result of use is better.But, selenium additive itself has certain toxicity, and expensive, and its price is 500,000 yuan/ton ~ 1,000,000 yuan/ton, often produce the selenium additive that one ton of manganese needs 1 kilogram ~ 2 kilograms, production cost is caused to remain high, meanwhile, in ordinary process electrolytic process, the amount of mixing the selenium of manganese metal is about 0.02% ~ 0.05%, this also can cause the decline of product purity to a certain extent, affects the use properties of product, can not meet the demand of special dimension to high pure metal manganese.
Summary of the invention
In order to solve above technical problem, the invention provides a kind of production method of electrolytic metal Mn, production method provided by the invention, while guarantee electrolytic efficiency, without the need to using selenium additive, can improve product quality, reduces production cost.
The invention provides a kind of production method of electrolytic metal Mn, comprising:
There is provided manganese electrolyte, described manganese electrolyte comprises electrolysis additive, and described electrolysis additive comprises the composition of following weight percent:
The antioxidant of 15% ~ 26%;
The surfacing agent of 2% ~ 3%, described surfacing agent is contain the natural organic high-molecular of amino and carboxyl or contain the synthetic organic polymer of amino and carboxyl;
The crystal formation changing agent of 40% ~ 70%, described crystal formation changing agent is low sulfur compounds and at least one in low price phosphorus compound;
The complexing agent of 12% ~ 32%;
Described manganese electrolyte is carried out electrolysis, obtains electrolytic metal Mn.
Preferably, the concentration of described antioxidant in manganese electrolyte is 1ppm ~ 100ppm.
Preferably, the concentration of described surfacing agent in manganese electrolyte is 0.1ppm ~ 10ppm.
Preferably, the concentration of described crystal formation changing agent in manganese electrolyte is 0.1ppm ~ 10ppm.
Preferably, the concentration of described complexing agent in manganese electrolyte is 1ppm ~ 100ppm.
Preferably, the preparation method of described manganese electrolyte comprises:
Manganese ore is carried out successively roughly grind, fine grinding, leaching, removal of impurities, pH value adjustment and coarse filtration, obtain manganese electrolyte stoste;
Described manganese electrolyte stoste is carried out successively ageing, essence is filtered and electrolysis additive adds, and obtains manganese electrolyte.
Preferably, the pH value of the manganese electrolyte stoste after described pH value adjustment is 6 ~ 10.
Preferably, the time of described ageing is 2 hours ~ 48 hours.
Preferably, the temperature of described electrolysis is 30 DEG C ~ 50 DEG C.
Preferably, described electrolysis is undertaken by the pulse power, and the waveform of the described pulse power is square wave, and virtual voltage is 4.0V ~ 5.0V, and pulse peak height is 4.5V ~ 10V, and dutycycle is 30% ~ 100%, and frequency is 500Hz ~ 20000Hz.
Compared with prior art, first production method provided by the invention provides manganese electrolyte, and described manganese electrolyte comprises electrolysis additive, and described electrolysis additive comprises the composition of following weight percent: the antioxidant of 15% ~ 26%; The surfacing agent of 2% ~ 3%, described surfacing agent is contain the natural organic high-molecular of amino and carboxyl or contain the synthetic organic polymer of amino and carboxyl; The crystal formation changing agent of 40% ~ 70%, described crystal formation changing agent is low sulfur compounds and at least one in low price phosphorus compound; The complexing agent of 12% ~ 32%; Then, described manganese electrolyte is carried out electrolysis by the present invention, obtains electrolytic metal Mn.In the present invention, described electrolysis additive is a kind of without selenium additive.The present invention, when carrying out electrolytic metal Mn and producing, can obtain low selenium electrolytic manganese product, and has and only use the electrolytic efficiency be close during selenium additive, and meanwhile, the relative selenium additive of described electrolysis additive is more cheap, can reduce the production cost of electrolytic manganese.In addition, described electrolysis additive has good adaptive faculty to the manganese ore raw material containing magnesium, calcium.Experiment shows, when the present invention carries out electrolytic metal Mn production, electrolytic efficiency can reach 70% ~ 75%, and in product, selenium content is less than 0.0001%.
Embodiment
In order to understand the present invention further, below in conjunction with embodiment, the preferred embodiment of the invention is described, but should be appreciated that these describe just for further illustrating the features and advantages of the present invention, instead of limiting to the claimed invention.
The invention provides a kind of electrolysis additive produced for electrolytic metal Mn, comprise the composition of following weight percent:
The antioxidant of 15% ~ 26%;
The surfacing agent of 2% ~ 3%, described surfacing agent is contain the natural organic high-molecular of amino and carboxyl or contain the synthetic organic polymer of amino and carboxyl;
The crystal formation changing agent of 40% ~ 70%, described crystal formation changing agent is low sulfur compounds and at least one in low price phosphorus compound;
The complexing agent of 12% ~ 32%.
When using electrolysis additive provided by the invention, using a small amount of selenium additive or can electrolytic metal Mn produced under not using the condition of selenium additive completely, thus the purity of electrolytic metal Mn can improved, also can reduce production cost.
In the present invention, described electrolysis additive comprises the antioxidant that weight percent is 15% ~ 26%, preferably comprises the antioxidant that weight percent is 18% ~ 24%.Described antioxidant is preferably the small organic molecule containing aldehyde radical, is more preferably one or more in oxalic acid, formic acid and xitix.
Described electrolysis additive comprises the surfacing agent that weight percent is 2% ~ 3%, preferably comprises the surfacing agent that weight percent is 2.2% ~ 2.8%.Described surfacing agent is contain the natural organic high-molecular of amino and carboxyl or contain the synthetic organic polymer of amino and carboxyl, is preferably at least one in gelatin and guar gum, is more preferably guar gum.In embodiments of the present invention, described surfacing agent can be the different gelatin of hydrolysis degree or guar gum.
Described electrolysis additive comprises the crystal formation changing agent that weight percent is 40% ~ 70%, preferably comprises the crystal formation changing agent that weight percent is 50% ~ 60%.Described crystal formation changing agent is low sulfur compounds and at least one in low price phosphorus compound, and wherein, described low sulfur compounds is preferred sulphite, is more preferably at least one in ammonium sulphite and S-WAT; Described low price phosphorus compound is preferably phosphite, is more preferably at least one in ammonium phosphite and sodium phosphite.In one embodiment of the invention, described crystal formation changing agent is the mixture of ammonium sulphite and sodium phosphite.
Described electrolysis additive comprises the complexing agent that weight percent is 12% ~ 32%, preferably comprises the complexing agent that weight percent is 15% ~ 30%.Described complexing agent is preferably small molecules organic amine, is more preferably one or more in quadrol, trolamine and hexamethylenetetramine.
Described electrolysis additive is a kind of without selenium additive, wherein each composition comprehensive action, the object replacing or partly replace selenium additive completely can be reached, solve the production without selenium or low selenium electrolytic metal Mn in ultrafine high-purity powder production process, reduce the expensive Cost Problems using hypertoxicity selenium additive simultaneously.
In the present invention, described electrolysis additive directly can add use, also can make solution and add use.
The invention provides a kind of electrolysis additive mixed solution produced for electrolytic metal Mn, comprise:
Electrolysis additive mentioned above;
Water.
Accordingly, the invention provides the preparation method of described electrolysis additive mixed solution, comprising:
Antioxidant, surfacing agent, crystal formation changing agent and complexing agent are dissolved respectively, obtains aqueous antioxidant solution, the surfacing agent aqueous solution, the crystal formation changing agent aqueous solution and complexing agent aqueous solution;
Described aqueous antioxidant solution, the surfacing agent aqueous solution, the crystal formation changing agent aqueous solution and complexing agent aqueous solution are mixed, obtains the electrolysis additive mixed solution produced for electrolytic metal Mn.
First each composition dissolves by the embodiment of the present invention respectively becomes the aqueous solution, and the content of each composition as mentioned before.Wherein, the temperature that described antioxidant, crystal formation changing agent and complexing agent carry out dissolving respectively is preferably 0 ~ 50 DEG C, is more preferably 10 DEG C ~ 40 DEG C.The temperature that described surfacing agent carries out dissolving is preferably 30 DEG C ~ 120 DEG C, is more preferably 50 DEG C ~ 100 DEG C.
After dissolving, the embodiment of the present invention carries out constant volume in volumetric flask.In the present invention, the concentration of described aqueous antioxidant solution is preferably 0.1g/mL ~ 0.15g/mL; The concentration of the described surfacing agent aqueous solution is preferably 0.0005g/mL ~ 0.001g/mL; The concentration of the described crystal formation changing agent aqueous solution is preferably 0.15g/mL ~ 0.3g/mL, is more preferably 0.18g/mL ~ 0.25g/mL; The concentration of described complexing agent aqueous solution is preferably 0.08g/mL ~ 0.2g/mL, is more preferably 0.09g/mL ~ 0.18g/mL.
Then, the embodiment of the present invention is even by each aqueous solution in proportion again, obtains electrolysis additive mixed solution.In one embodiment of the invention, the electrolysis additive mixed solution of preparation 100mL, the volume ratio of described antioxidant, surfacing agent, crystal formation changing agent and complexing agent can be 20mL:30mL:30mL:20mL.
During use, described electrolysis additive mixed solution and manganese electrolyte preferably add by the present invention by a certain percentage, can obtain High Pure Electrolytic Manganese.In embodiments of the present invention, the electrolysis additive mixed solution of above-mentioned 100mL can as the additive of the manganese electrolyte of 2000mL.
In the present invention, the described electrolysis additive for electrolytic metal Mn production can be used alone, and produces ultrafine high-purity powder; Also can with selenium additive by a certain percentage with the use of, produce low selenium electrolytic manganese.
About replacing selenium additive completely, namely using and only using without selenium additive, the invention provides a kind of production method of electrolytic metal Mn, comprising:
There is provided manganese electrolyte, described manganese electrolyte comprises electrolysis additive, and described electrolysis additive comprises the composition of following weight percent:
The antioxidant of 15% ~ 26%;
The surfacing agent of 2% ~ 3%, described surfacing agent is contain the natural organic high-molecular of amino and carboxyl or contain the synthetic organic polymer of amino and carboxyl;
The crystal formation changing agent of 40% ~ 70%, described crystal formation changing agent is low sulfur compounds and at least one in low price phosphorus compound;
The complexing agent of 12% ~ 32%;
Described manganese electrolyte is carried out electrolysis, obtains electrolytic metal Mn.
This production method provided by the invention is a kind of less energy-consumption ultrafine high-purity powder production technology, this technology improves the quality of electrolytic manganese without selenium additive mainly through using, namely on the basis close to common quality electrolytic metal Mn production cost, produce high pure metal manganese.
First the embodiment of the present invention provides the manganese electrolyte containing electrolysis additive, and described electrolysis additive is the mentioned above electrolysis additive produced for electrolytic metal Mn.
In one embodiment of the invention, the preparation method of described manganese electrolyte specifically comprises:
Manganese ore is carried out successively roughly grind, fine grinding, leaching, removal of impurities, pH value adjustment and coarse filtration, obtain manganese electrolyte stoste;
Described manganese electrolyte stoste is carried out successively ageing, essence is filtered and electrolysis additive adds, and obtains manganese electrolyte.
The embodiment of the present invention take manganese ore as raw material, and described manganese ore adopts this area to commonly use.Described manganese ore obtains manganese ore stone flour after corase grind, fine grinding, and described corase grind, fine grinding are technique means well known to those skilled in the art, and the present invention there is no particular restriction.
Then, the manganese ore stone flour obtained carries out leaching by the embodiment of the present invention, removal of impurities, pH value adjustment and coarse filtration, obtain manganese electrolyte stoste.
Wherein, described leaching is technique means well known to those skilled in the art, can react, and supplemental acid is to reacting completely, and obtains manganese leach liquor for manganese ore powder and the anolyte containing acid.
By described manganese leach liquor adjusted to ph after removal of impurities, now, the pH value of manganese electrolyte stoste controlled after the adjustment of described pH value is preferably 6 ~ 10, is more preferably 6 ~ 8, current efficiency good during to guarantee electrolysis.In addition, also will control the concentration of ammonium sulfate, general control, at 110g/L ~ 130g/L, can keep pH value to stablize, also increase electroconductibility.The present invention is not particularly limited described removal of impurities, the auxiliary agent that adjusted to ph adopts this area conventional.
After coarse filtration, obtain manganese electrolyte stoste, the present invention is not particularly limited described coarse filtration, the press filtration can commonly used for this area.
After obtaining manganese electrolyte stoste, it is carried out essence and filters by the embodiment of the present invention after ageing, then adds electrolysis additive, obtains qualified manganese electrolyte.
Wherein, the present invention is not particularly limited described ageing, can leave standstill, preferably adding flocculation agent and leaving standstill for electrolytic solution stoste good for coarse filtration being placed in deposit groove.The time of described ageing is preferably 2 hours ~ 48 hours, is more preferably 10 hours ~ 30 hours.
Carry out the processing sequence of filtering after ageing more further, namely carry out essence and filter, the present invention filters described essence and is not particularly limited.
Finally add electrolysis additive, obtain manganese electrolyte.Described electrolysis additive is without selenium additive, and the namely mentioned above electrolysis additive produced for electrolytic metal Mn, comprises the composition of following weight percent:
The antioxidant of 15% ~ 26%;
The surfacing agent of 2% ~ 3%, described surfacing agent is contain the natural organic high-molecular of amino and carboxyl or contain the synthetic organic polymer of amino and carboxyl;
The crystal formation changing agent of 40% ~ 70%, described crystal formation changing agent is low sulfur compounds and at least one in low price phosphorus compound;
The complexing agent of 12% ~ 32%.
In described electrolysis additive, the content of each composition as mentioned before, does not repeat them here.Manganese metal optimum concn general requirement of in electrolytic process itself is 14g/L ~ 16g/L; And in electrolytic solution, allowing the content of manganese to be 10g/L ~ 40g/L, the concentration of additive is preferably 50mg/L ~ 150mg/L.
The effect of additive is mainly by the impact of its concentration in the electrolytic solution in process of production, little with the relation of the content of manganese metal.In described manganese electrolyte, the concentration of described antioxidant in manganese electrolyte is preferably 1ppm ~ 100ppm, is more preferably 10ppm ~ 80ppm; The concentration of described surfacing agent in manganese electrolyte is preferably 0.1ppm ~ 10ppm, is more preferably 1ppm ~ 8ppm; The concentration of described crystal formation changing agent in manganese electrolyte is preferably 0.1ppm ~ 10ppm, is more preferably 1ppm ~ 8ppm; The concentration of described complexing agent in manganese electrolyte is preferably 1ppm ~ 100ppm, is more preferably 10ppm ~ 80ppm.
After obtaining manganese electrolyte, the embodiment of the present invention is passed in electrolyzer carries out electrolysis, obtains electrolytic metal Mn.
In the present invention, the equipment that adopts of described electrolysis and mode are well known to those skilled in the art.Micropump can be used in electrolytic process to be circulated by the manganese electrolyte in single electrolyzer, and control to carry out electrolysis under certain temperature, pH value condition.The temperature of described electrolysis is preferably 30 DEG C ~ 50 DEG C, is more preferably 35 DEG C ~ 45 DEG C; The pH value of described electrolysis is preferably 7.0 ~ 7.5.
In one embodiment of the invention, described electrolysis is carried out preferably by the pulse power, and the waveform of the described pulse power is square wave, and virtual voltage is 4.0V ~ 5.0V; Pulse peak height is 4.5V ~ 10V, is preferably 5V ~ 8V; Dutycycle is 30% ~ 100%, is preferably 50% ~ 90%; Frequency is 500Hz ~ 20000Hz, is preferably 1000Hz ~ 10000Hz.The present invention adopts this Novel pulse electrolysis power technology, can improve electrolytic efficiency, reduces energy consumption.
Existing use is not only 60% containing the electrolytic efficiency of additive electrolytic manganese of selenium is the highest, and the power consumption of the high pure metal manganese production technique existed at present is about 10000 KWhs/ton.And by this technique of the present invention, the electrolytic efficiency of whole electrolytic process can improve about 10% than having high pure metal manganese production technique at present, can 70% ~ 75% be reached, and the power consumption of High Pure Electrolytic Manganese can be reduced to 6000 KWhs/ton ~ 7000 KWhs/ton from 10000 KWhs/ton.
The production method of the electrolytic metal Mn without selenium additive that this interpolation of the present invention is relatively cheap is the High Pure Electrolytic Manganese production decision of a kind of less energy-consumption, low cost, it can obtain High Pure Electrolytic Manganese, the content of manganese metal is greater than 99.9%, selenium content is less than 0.0001%, and there is the electrolytic efficiency of 70% ~ 75%, production cost is lower, solves the problem of high energy consumption high cost in High Pure Electrolytic Manganese production process.In addition, existing for having ultrafine high-purity powder production technique at present, the manganese ore raw material of this technique to high magnesium, calcium contents also has good adaptive faculty.
In order to understand the present invention further, be specifically described below in conjunction with the production method of embodiment to electrolytic metal Mn provided by the invention.
Embodiment 1
Take oxalic acid as antioxidant, be dissolve under the condition of 30 DEG C in temperature by 10g oxalic acid, and carry out constant volume in 100mL volumetric flask, obtain aqueous antioxidant solution;
Take guar gum as surfacing agent, be dissolve under the condition of 80 DEG C in temperature by 0.1g guar gum, after being cooled to room temperature, in 100mL volumetric flask, carry out constant volume, obtain the surfacing agent aqueous solution;
Take ammonium sulphite as crystal formation changing agent, be dissolve under the condition of 30 DEG C in temperature by 30g ammonium sulphite, and carry out constant volume in 100mL volumetric flask, obtain the crystal formation changing agent aqueous solution;
Take quadrol as complexing agent, be dissolve under the condition of 30 DEG C in temperature by 10mL quadrol, and carry out constant volume in 100mL volumetric flask, obtain complexing agent aqueous solution;
According to the ratio of 20mL:30mL:30mL:20mL, described aqueous antioxidant solution, the surfacing agent aqueous solution, the crystal formation changing agent aqueous solution and complexing agent aqueous solution are mixed, obtain the electrolysis additive mixed solution that 100mL produces for electrolytic metal Mn, namely without the selenium additive aqueous solution.
100 kilograms of manganese ores are carried out roughly grind, fine grinding, obtain the manganese ore stone flour of more than 300 orders; Then described manganese ore stone flour and the anolyte containing acid are reacted, and supplemental acid is to reacting completely, now acid content is less than 2g/L, obtains manganese leach liquor; Be 6 by described manganese leach liquor adjusted to ph after removal of impurities, and to control ammonium sulfate concentrations be 120g/L; Through 3 press filtrations, obtain manganese electrolyte stoste; Add flocculation agent to described manganese electrolyte stoste, leave standstill and carry out ageing in 24 hours; Filter after ageing, then add the described electrolysis additive mixed solution produced for electrolytic metal Mn, obtain manganese electrolyte.Wherein, the consumption of described electrolysis additive mixed solution is the 5%(volume ratio of manganese electrolyte), namely 100mL electrolysis additive mixed solution can as the additive of 2000mL manganese electrolyte.
Described manganese electrolyte is passed into electrolyzer, uses the pulse power to carry out electrolysis, obtain High Pure Electrolytic Manganese.In electrolytic process, use micropump to be circulated by the manganese electrolyte in single electrolyzer, and control temperature is 38 DEG C ~ 42 DEG C, pH value is 7.0 ~ 7.5.The optimum configurations of the pulse power is: voltage is 4.2V, and current density is 380A/m2, and frequency is 10000Hz, and dutycycle is 85%.
After electrolysis completes, the selenium content of gained electrolytic metal Mn is less than 0.0001%, and Fe content is more than 99.9%, and electrolytic efficiency is 75% ~ 80%.
Embodiment 2
Take xitix as antioxidant, be dissolve under the condition of 30 DEG C in temperature by 15g xitix, and carry out constant volume in 100mL volumetric flask, obtain aqueous antioxidant solution;
Take guar gum as surfacing agent, be dissolve under the condition of 80 DEG C in temperature by 0.1g guar gum, after being cooled to room temperature, in 100mL volumetric flask, carry out constant volume, obtain the surfacing agent aqueous solution;
With the mixture of ammonium sulphite and sodium phosphite for crystal formation changing agent, 10g ammonium sulphite and 5g sodium phosphite are dissolved under temperature is the condition of 30 DEG C, and carry out constant volume in 100mL volumetric flask, obtain the crystal formation changing agent aqueous solution;
Take trolamine as complexing agent, be dissolve under the condition of 30 DEG C in temperature by 15mL trolamine, and carry out constant volume in 100mL volumetric flask, obtain complexing agent aqueous solution;
According to the ratio of 20mL:30mL:30mL:20mL, described aqueous antioxidant solution, the surfacing agent aqueous solution, the crystal formation changing agent aqueous solution and complexing agent aqueous solution are mixed, obtain the electrolysis additive mixed solution that 100mL produces for electrolytic metal Mn, namely without the selenium additive aqueous solution.
100 kilograms of manganese ores are carried out roughly grind, fine grinding, obtain the manganese ore stone flour of more than 300 orders; Then described manganese ore stone flour and the anolyte containing acid are reacted, and supplemental acid is to reacting completely, now acid content is less than 2g/L, obtains manganese leach liquor; Be 6 by described manganese leach liquor adjusted to ph after removal of impurities, and to control ammonium sulfate concentrations be 120g/L; Through 3 press filtrations, obtain manganese electrolyte stoste; Add flocculation agent to described manganese electrolyte stoste, leave standstill and carry out ageing in 24 hours; Filter after ageing, then add the described electrolysis additive mixed solution produced for electrolytic metal Mn, obtain manganese electrolyte.Wherein, the consumption of described electrolysis additive mixed solution is the 5%(volume ratio of manganese electrolyte), namely 100mL electrolysis additive mixed solution can as the additive of 2000mL manganese electrolyte.
Described manganese electrolyte is passed into electrolyzer, uses the pulse power to carry out electrolysis, obtain High Pure Electrolytic Manganese.In electrolytic process, use micropump to be circulated by the manganese electrolyte in single electrolyzer, and control temperature is 38 DEG C ~ 42 DEG C, pH value is 7.0 ~ 7.5.The optimum configurations of the pulse power is: voltage is 4.2V, and current density is 380A/m2, and frequency is 10000Hz, and dutycycle is 80%.
After electrolysis completes, the selenium content of gained electrolytic metal Mn is less than 0.0001%, and Fe content is more than 99.9%, and electrolytic efficiency is 75% ~ 80%.
Embodiment 3
Take oxalic acid as antioxidant, be dissolve under the condition of 30 DEG C in temperature by 15g oxalic acid, and carry out constant volume in 100mL volumetric flask, obtain aqueous antioxidant solution;
Take guar gum as surfacing agent, be dissolve under the condition of 80 DEG C in temperature by 0.1g guar gum, after being cooled to room temperature, in 100mL volumetric flask, carry out constant volume, obtain the surfacing agent aqueous solution;
With ammonium sulphite and sodium phosphite for crystal formation changing agent, 10g ammonium sulphite and 5g sodium phosphite are dissolved under temperature is the condition of 30 DEG C, and carry out constant volume in 100mL volumetric flask, obtain the crystal formation changing agent aqueous solution;
Take trolamine as complexing agent, be dissolve under the condition of 30 DEG C in temperature by 15mL trolamine, and carry out constant volume in 100mL volumetric flask, obtain complexing agent aqueous solution;
According to the ratio of 20mL:30mL:30mL:20mL, described aqueous antioxidant solution, the surfacing agent aqueous solution, the crystal formation changing agent aqueous solution and complexing agent aqueous solution are mixed, obtain the electrolysis additive mixed solution that 100mL produces for electrolytic metal Mn, namely without the selenium additive aqueous solution.
100 kilograms of manganese ores are carried out roughly grind, fine grinding, obtain the manganese ore stone flour of more than 300 orders; Then described manganese ore stone flour and the anolyte containing acid are reacted, and supplemental acid is to reacting completely, now acid content is less than 2g/L, obtains manganese leach liquor; Be 6 by described manganese leach liquor adjusted to ph after removal of impurities, and to control ammonium sulfate concentrations be 120g/L; Through 3 press filtrations, obtain manganese electrolyte stoste; Add flocculation agent to described manganese electrolyte stoste, leave standstill and carry out ageing in 24 hours; Filter after ageing, then add the described electrolysis additive mixed solution produced for electrolytic metal Mn, obtain manganese electrolyte.Wherein, the consumption of described electrolysis additive mixed solution is the 5%(volume ratio of manganese electrolyte), namely 100mL electrolysis additive mixed solution can as the additive of 2000mL manganese electrolyte.
Described manganese electrolyte is passed into electrolyzer, uses the pulse power to carry out electrolysis, obtain High Pure Electrolytic Manganese.In electrolytic process, use micropump to be circulated by the manganese electrolyte in single electrolyzer, and control temperature is 38 DEG C ~ 42 DEG C, pH value is 7.0 ~ 7.5.The optimum configurations of the pulse power is: voltage is 4.2V, and current density is 380A/m2, and frequency is 2400Hz, and dutycycle is 85%.
After electrolysis completes, the selenium content of gained electrolytic metal Mn is less than 0.0001%, and Fe content is more than 99.9%, and electrolytic efficiency is 75% ~ 78%.
Embodiment 4
Take xitix as antioxidant, be dissolve under the condition of 30 DEG C in temperature by 15g xitix, and carry out constant volume in 100mL volumetric flask, obtain aqueous antioxidant solution;
Take guar gum as surfacing agent, be dissolve under the condition of 80 DEG C in temperature by 0.1g guar gum, after being cooled to room temperature, in 100mL volumetric flask, carry out constant volume, obtain the surfacing agent aqueous solution;
Take ammonium sulphite as crystal formation changing agent, be dissolve under the condition of 30 DEG C in temperature by 10g ammonium sulphite, and carry out constant volume in 100mL volumetric flask, obtain the crystal formation changing agent aqueous solution;
Take trolamine as complexing agent, be dissolve under the condition of 30 DEG C in temperature by 15mL trolamine, and carry out constant volume in 100mL volumetric flask, obtain complexing agent aqueous solution;
According to the ratio of 20mL:30mL:30mL:20mL, described aqueous antioxidant solution, the surfacing agent aqueous solution, the crystal formation changing agent aqueous solution and complexing agent aqueous solution are mixed, obtain the electrolysis additive mixed solution that 100mL produces for electrolytic metal Mn, namely without the selenium additive aqueous solution.
100 kilograms of manganese ores are carried out roughly grind, fine grinding, obtain the manganese ore stone flour of more than 300 orders; Then described manganese ore stone flour and the anolyte containing acid are reacted, and supplemental acid is to reacting completely, now acid content is less than 2g/L, obtains manganese leach liquor; Be 6 by described manganese leach liquor adjusted to ph after removal of impurities, and to control ammonium sulfate concentrations be 120g/L; Through 3 press filtrations, obtain manganese electrolyte stoste; Add flocculation agent to described manganese electrolyte stoste, leave standstill and carry out ageing in 24 hours; Filter after ageing, then add the described electrolysis additive mixed solution produced for electrolytic metal Mn, obtain manganese electrolyte.Wherein, the consumption of described electrolysis additive mixed solution is the 3%(volume ratio of manganese electrolyte).
Described manganese electrolyte is passed into electrolyzer, uses the pulse power to carry out electrolysis, obtain High Pure Electrolytic Manganese.In electrolytic process, use micropump to be circulated by the manganese electrolyte in single electrolyzer, and control temperature is 38 DEG C ~ 42 DEG C, pH value is 7.0 ~ 7.5.The optimum configurations of the pulse power is: voltage is 4.2V, and current density is 380A/m2, and frequency is 10000Hz, and dutycycle is 85%.
After electrolysis completes, the selenium content of gained electrolytic metal Mn is less than 0.0001%, and Fe content is more than 99.9%, and electrolytic efficiency is 75% ~ 78%.
As seen from the above embodiment, when the present invention carries out electrolytic metal Mn production, electrolytic efficiency can reach 70% ~ 75%, and in product, selenium content is less than 0.0001%.Show that production method provided by the invention is while guarantee electrolytic efficiency, without the need to using selenium additive, thus improving product quality, reducing production cost.
The explanation of above embodiment just understands method of the present invention and core concept thereof for helping.It should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention, can also carry out some improvement and modification to the present invention, these improve and modify and also fall in the protection domain of the claims in the present invention.
Claims (10)
1. a production method for electrolytic metal Mn, comprising:
There is provided manganese electrolyte, described manganese electrolyte comprises electrolysis additive, and described electrolysis additive comprises the composition of following weight percent:
The antioxidant of 15% ~ 26%;
The surfacing agent of 2% ~ 3%, described surfacing agent is contain the natural organic high-molecular of amino and carboxyl or contain the synthetic organic polymer of amino and carboxyl;
The crystal formation changing agent of 40% ~ 70%, described crystal formation changing agent is low sulfur compounds and at least one in low price phosphorus compound;
The complexing agent of 12% ~ 32%;
Described manganese electrolyte is carried out electrolysis, obtains electrolytic metal Mn.
2. production method according to claim 1, is characterized in that, the concentration of described antioxidant in manganese electrolyte is 1ppm ~ 100ppm.
3. production method according to claim 1, is characterized in that, the concentration of described surfacing agent in manganese electrolyte is 0.1ppm ~ 10ppm.
4. production method according to claim 1, is characterized in that, the concentration of described crystal formation changing agent in manganese electrolyte is 0.1ppm ~ 10ppm.
5. production method according to claim 1, is characterized in that, the concentration of described complexing agent in manganese electrolyte is 1ppm ~ 100ppm.
6. production method according to claim 1, is characterized in that, the preparation method of described manganese electrolyte comprises:
Manganese ore is carried out successively roughly grind, fine grinding, leaching, removal of impurities, pH value adjustment and coarse filtration, obtain manganese electrolyte stoste;
Described manganese electrolyte stoste is carried out successively ageing, essence is filtered and electrolysis additive adds, and obtains manganese electrolyte.
7. production method according to claim 6, is characterized in that, the pH value of the manganese electrolyte stoste after described pH value adjustment is 6 ~ 10.
8. production method according to claim 6, is characterized in that, the time of described ageing is 2 hours ~ 48 hours.
9. production method according to claim 1, is characterized in that, the temperature of described electrolysis is 30 DEG C ~ 50 DEG C.
10. production method according to claim 1, is characterized in that, described electrolysis is undertaken by the pulse power, the waveform of the described pulse power is square wave, and virtual voltage is 4.0V ~ 5.0V, and pulse peak height is 4.5V ~ 10V, dutycycle is 30% ~ 100%, and frequency is 500Hz ~ 20000Hz.
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