CN107858702A - A kind of production method of electrolytic manganese metal - Google Patents
A kind of production method of electrolytic manganese metal Download PDFInfo
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- CN107858702A CN107858702A CN201711251257.4A CN201711251257A CN107858702A CN 107858702 A CN107858702 A CN 107858702A CN 201711251257 A CN201711251257 A CN 201711251257A CN 107858702 A CN107858702 A CN 107858702A
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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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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/08—Sulfuric acid, other sulfurated acids or salts thereof
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/22—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition
- C22B3/24—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition by adsorption on solid substances, e.g. by extraction with solid resins
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B47/00—Obtaining manganese
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
- C23C22/58—Treatment of other metallic material
Abstract
The present invention relates to the technical field of electrolysis production manganese metal, and in particular to a kind of production method of electrolytic manganese metal, this method comprise the following steps：The passivation drying of iron removaling removing heavy metals purifying electrolysis is leached to peel off.The leaching rate of manganese can be improved by carrying out processing manganese spar using this method; it is low by adding the progress deep purifying rear impurity content such as removal of impurities medicament in the manganese sulphate solution drawn; it ensure that the quality of product; the electrolysis additive and passivator safety and environmental protection that this method uses; the injury to human body and the pollution to environment are reduced, energy consumption is greatlyd save using this method electrolytic manganese metal, reduces cost; environmental protection, and the obtained manganese metal purity of production is up to more than 99.8%.
Description
Technical field
The present invention relates to the technical field of electrolysis production manganese metal, and in particular to a kind of production method of electrolytic manganese metal.
Background technology
Manganese is indispensable additive in metallurgy industry, is the master for producing mangano-manganic oxide after electrolytic manganese processing powdering
Raw material is wanted, the widely used magnetic material original paper of electronics industry is produced with mangano-manganic oxide, electronics industry, metallurgical industry
Electrolytic manganese metal is required for aerospace industry.Electrolytic manganese metal is to obtain manganese salt, then power transmission solution through Ore Leaching with manganese ore
The elemental metals that groove electrolysis separates out, the purity of electrolytic manganese is very high, and manganese content is more than more than 99.7%, outward appearance chalybeate, in irregular
Sheet, matter is hard and crisp, and simultaneously bright, another side is coarse, is silvery white to brown, and it is in silver gray to be processed as after powder；In air
In it is oxidizable.It is high-purity due to its with the continuous improvement of productivity level, electrolytic manganese metal with the continuous development of scientific technology
Degree, low impurity feature, have succeeded and have widely applied to smelting iron and steel, nonferrous metallurgy, electronic technology, chemical industry, environment
The every field such as protection, food hygiene, welding rod industry, aerospace industry.With the development of science and technology, the application of electrolytic manganese is constantly expanded
Greatly, market demand year increases by 15% or so.China's electrolytic manganese annual capacity accounts for Gross World Product up to 800,000 tons
80%.For many years, China's electrolytic manganese is mostly used in the country such as outlet, main exit Japan, South Korea, America and Europe.
In the production technology of electrolytic manganese metal, mainly there is following several method at present, one kind is using manganese oxide ore as original
Material, roasting reduction, then through acidleach, deep purifying produces pure manganese salt solution, for electrolysis production, obtains the electricity of high-purity
Solve manganese metal；Another kind is using manganese carbonate ore as raw material, then through acidleach, iron removal by oxidation and deep purifying handles to obtain pure manganese
Salting liquid, for being electrolysed, the electrolytic manganese metal of high-purity is obtained, next to that with waste material containing manganese etc. for raw material, through acidleach, oxidation removes
Iron, and deep purifying obtain pure manganese salt solution, for being electrolysed, obtain High Pure Electrolytic Manganese.But as existing manganese ore provides
Source is increasingly deficienter, manganese taste is more and more lower, causes the increasing of electrolytic manganese metal production difficulty, cost to increase；Electrolytic manganese metal city
Field dog-eat-dog, profit margin are less and less；Substantial amounts of harmful useless filter residue is produced during electrolytic manganese metal, to environment, underground
Water pollution causes greatly harm and hidden danger.Deficiency present in existing electrolytic manganese metal production process mainly has following several
Point：1st, metal leaching rate is low, the manganese ore rate of recovery is relatively low；2nd, impurity content in obtained manganese sulphate solution is high, especially iron, copper,
The impurity such as cobalt, nickel, lead, calcium sulfate and magnesium sulfate, influence to be electrolysed the final mass of manganese product；3rd, generally using single in electrolytic manganese
One selenium dioxide is as the additive during electrolytic manganese, although selenium dioxide current efficiency is higher, in electrolytic process
Middle Se can be deposited in electrolysis manganese product so that the purity of electrolytic manganese reduces, and influences product quality, and selenium dioxide is inorganic
Toxic articles, high risks health, and seriously pollute environment；4th, it is passivated to the manganese metal semi-finished product obtained by electrolysis
When, the main component of the passivating solution used is a kind of toxicant, there is the health of operator compared with macrolesion for chromate.
The content of the invention
The purpose of the present invention is to solve the shortcomings of the prior art provide a kind of production method of electrolytic manganese metal, this method
Manganese leaching rate can be improved, impurity content is low in the manganese sulphate solution drawn, electrolysis additive and the passivator safety that this method uses
Environmental protection, the injury to human body and the pollution to environment are reduced, energy consumption is greatlyd save using this method electrolytic manganese metal, reduced
Cost, environmental protection, and the obtained manganese metal purity of production are up to more than 99.8%.
To achieve the above object, the present invention adopts the following technical scheme that：
A kind of production method of electrolytic manganese metal, comprises the following steps：
（1）Leach：Manganese spar is crushed to obtain manganese spar powder；Anolyte is put into leaching tanks, according to manganese spar powder：Anolyte
Weight ratio be 1:4 ratio adds manganese spar powder, 5-10 minutes is thoroughly mixed at 55-60 DEG C, then according to water chestnut manganese
Miberal powder：The weight ratio of acid is 1:0.5-0.6 ratio adds the concentrated sulfuric acid that mass fraction is 98%, controlling reaction temperature 65-
70 DEG C, Leach reaction 5.5-8h obtains ore pulp, and the content of spent acid is examined at the end of reaction, and ore pulp spent acid content is controlled in 2-2.5
g/L；
（2）Iron removaling：Detect the Fe in ore pulp2+Content, the Fe in ore pulp2+Content, input manganese oxide powder carry out reacting straight
To Fe2+Content ＜ 1.0g/l, then add the ammoniacal liquor that mass concentration is 10% and pH values are adjusted to 6.5, persistently keep 40-
50 minutes；Ore pulp progress first time separation of solid and liquid is obtained into rough manganese sulfate solution；
（3）Removing heavy metals：Detect precious metal constituent content i.e. [Co in rough manganese sulfate solution2+]、[Ni2+]、[Cu2+]、[Pb2 +]、[Zn2+]、[Cd2+]、[Cr3+] and [Hg2+] molar concentration；Then precipitating reagent precipitation precious metal is made with Sodium Dimethyldithiocarbamate S.D.D
Me, precipitation reaction carry out 2-3 hours；Then with filter press be filtrated to get the manganese sulfate solution after primary purification；
（4）Purification：In step（3）Activated carbon and the manganese sulfate that manganese sulfate solution weight 3% is added in obtained manganese sulfate solution are molten
Liquid weight 10-15% removal of impurities medicament carries out adsorption cleaning impurity, after depth precipitation purification 12-15 hours；Press filtration is removed slag, so
Electrolysis additive and surfactant are added in obtained solution afterwards, obtains qualified electrolyte；Described surfactant is
Neopelex；Qualified electrolyte requires that manganese content is 32-35g/L, and ammonium sulphate content is in 100-130g/L；It is described
Electrolysis additive content in the electrolytic solution control in 50-100mg/L, the content of described surfactant in the electrolytic solution
Control is in 10-20mg/L；
（5）Electrolysis：Minus plate is made using stainless steel plate, minus plate with mass fraction is first 1%-1.5% before electrolytic cell is put into
Sodium silicate solution impregnate, then place into electrolytic cell；Electrolysing period is 24 hours, 40-45 DEG C of bath temperature, pH
Value is between 7.5-8.2；
（6）Passivation：The manganese plate obtained after electrolysis, which is immediately placed in after being extracted out out of electrolytic cell in passivator solution, is passivated 3-5 points
Clock, the manganese plate being passivated is rinsed, dries, peels off and can obtain electrolytic manganese finished product.
The production method of described electrolytic manganese metal, step（1）Described in anolyte be waste liquid caused by electrolytic manganese, its
Middle Mn2+Content concn be 10-12g/L, H content concentration is 40-45g/L；NH4 +Concentration be 85-90g/L.
The production method of above-mentioned electrolytic manganese metal, step（3）In, make precipitating reagent with Sodium Dimethyldithiocarbamate S.D.D and precipitate valuable gold
Belong to Me, add Sodium Dimethyldithiocarbamate S.D.D amount, calculated as the following formula：
m(S.D.D)=2V*([Co2+]+[Ni2+]+[Pb2+]+[Cu2+]+[Zn2+]+[Cd2+]+[Hg2+])+3V*[Cr3+], in formula
m(S.D.D)It is the amount of Sodium Dimethyldithiocarbamate, unit is mole that precious metal concentration unit is mol/L, and V is the volume of solution, and unit is L,
The molal weight of Sodium Dimethyldithiocarbamate is 143 g/mol.
The production method of above-mentioned electrolytic manganese metal, step（4）In, described removal of impurities medicament is polyacrylamide, lemon
Sour sodium and aluminum sulfate press polyacrylamide:Sodium citrate:Aluminum sulfate is 3:2:The removal of impurities medicine that 1.5 part by weight is mixed to get
Agent.
The production method of above-mentioned electrolytic manganese metal, step（4）In, the preparation method of described electrolysis additive is：Press
According to hexamethylenetetramine:Polyvinyl alcohol:Benzene sulfonic acid sodium salt:Butanedioic acid:Water is 0.8-1:0.5-0.4:0.01:0.1:10 weight
Amount ratio is soluble in water by hexamethylenetetramine, polyvinyl alcohol, butanedioic acid and benzene sulfonic acid sodium salt, and 5-10 is stirred at 50-60 DEG C
Minute, it is i.e. available to be cooled to room temperature.
The production method of above-mentioned electrolytic manganese metal, step（6）In, described passivator is contained by following percentage by weight
Each raw material composition of amount：Sodium metasilicate 15~20%, citric acid 0.01%~0.03%, sodium tartrate 0.05%~
0.07%, potassium chlorate 0.05~0.1%, triethanolamine 0.01-0.03%, surplus is water.
The production method of electrolytic manganese metal of the present invention can be applied to the low product that mass fraction containing manganese is 14%~17%
In the manganese spar of position.
Beneficial effects of the present invention are：
1st, the production method of electrolytic manganese metal provided by the invention, the leaching of manganese can be improved by carrying out processing manganese spar using this method
Rate, by adding removal of impurities medicament etc., to carry out deep purifying rear impurity content low in the manganese sulphate solution drawn, ensure that the product of product
Matter, the electrolysis additive and passivator safety and environmental protection that this method uses, reduces the injury to human body and the pollution to environment, adopts
Energy consumption is greatlyd save with this method electrolytic manganese metal, reduces cost, environmental protection, and the manganese metal purity that production obtains reaches
More than 99.8%.
2nd, miberal powder is first added to electrolytic manganese anolyte at 55-60 DEG C and is thoroughly mixed 5-10 minutes then by the present invention
Add the generation of feed liquid splash phenomena when the concentrated sulfuric acid not only contributes to prevent from adding the concentrated sulfuric acid, moreover it is possible to make original ore powder in electrolytic manganese
Slow reaction is first carried out in anolyte so as to accelerate the speed and eduction rate of manganese precipitation.
3rd, the present invention eliminates iron tramp in ore pulp by adding manganese oxide powder, by adding a certain amount of Sodium Dimethyldithiocarbamate
S.D.D eliminates the precious metal element in solution, reduces the content of impurity.It is net that the present invention carries out depth to manganese sulfate solution
Change add activated carbon and removal of impurities medicament, wherein removal of impurities medicament be by for polyacrylamide, sodium citrate and aluminum sulfate according to
What certain proportion was formulated, the removal of impurities medicament can form chelate with metal ions such as Ca2+, Mg2+, therefore add the removal of impurities
The metal impurities such as Ca2+, Mg2+ in manganese sulfate solution can be carried out micro control by medicament, and the influence to bivalent manganese concentration is small, adds
The sinking speed of impurity can also be accelerated by entering the removal of impurities medicament, and it is harmful to reduce the fine particle to be suspended in solution, colloid, sulfide etc.
Influence of the impurity to electrolytic process.Impurity in the activated carbon energy adsorbent solution of addition, by adding activated carbon and removal of impurities medicament
To carrying out deep purifying, the impurity content in solution is greatly reduced, reduces influence of the objectionable impurities to electrolytic process, significantly
Electrolytic process is improved, very big effect is played to improving product yield and quality.
4th, the electrolysis additive used in the present invention is that one kind includes six first without selenium additive, the component of the electrolysis additive
Urotropine, polyvinyl alcohol and benzene sulfonic acid sodium salt butanedioic acid etc., wherein benzene sulfonic acid sodium salt can increase current efficiency, butanedioic acid can be effective
Improvement manganese sedimentation state, obtain smooth bright manganese metal etc., electrolysis additive nontoxic pollution-free of the invention, operation side
Just safety, the feature of environmental protection is good, and this additive of the invention is used to be electrolysed the generation that can reduce surface manganese knot, and current efficiency is higher, production
Product purity is high.
5th, the passivator safety and environmental protection used in the present invention, the passivator is nontoxic, simple to operate, cost is cheap, uses
Using sodium metasilicate as main component, the compound passivating agent of other a variety of organic-inorganic things is aided in, the passivator antioxygenic property is good
It is good, it is odorless, non-corrosiveness, nonirritant without chromium and other heavy metal pollution ions, significantly improve the operation of worker
Environment, reducing the discharge of harmful waste water reduces cost, reduces the discharge of harmful waste water；Metal after passivating solution processing
For manganese on the premise of original color is preferably ensured, have well passivated effect, product quality meets national production standard.
Embodiment
Embodiment 1
A kind of production method of electrolytic manganese metal, comprises the following steps：
（1）Leach：Manganese spar is crushed to obtain manganese spar powder；Anolyte is put into leaching tanks（Described anolyte is electrolysis
Waste liquid caused by manganese, wherein Mn2+Content concn be 10g/L, H content concentration is 40g/L；NH4 +Concentration be 85g/L）,
According to manganese spar powder：The weight ratio of anolyte is 1:4 ratio adds manganese spar powder, and 10 points are thoroughly mixed at 55 DEG C
Clock, then according to manganese spar powder：The weight ratio of acid is 1:0.5 ratio adds the concentrated sulfuric acid that mass fraction is 98%, control reaction
Temperature is 65 DEG C, and Leach reaction 8h obtains ore pulp, and the content of spent acid is examined at the end of reaction, and ore pulp spent acid content is controlled in 2g/
L；
（2）Iron removaling：Detect the Fe in ore pulp2+Content, the Fe in ore pulp2+Content, input manganese oxide powder carry out reacting straight
To Fe2+Content ＜ 1.0g/l, then add the ammoniacal liquor that mass concentration is 10% and pH values are adjusted to 6.5, persistently keep 40
Minute；Ore pulp progress first time separation of solid and liquid is obtained into rough manganese sulfate solution；
（3）Removing heavy metals：Detect precious metal constituent content i.e. [Co in rough manganese sulfate solution2+]、[Ni2+]、[Cu2+]、[Pb2 +]、[Zn2+]、[Cd2+]、[Cr3+] and [Hg2+] molar concentration；Then precipitating reagent precipitation precious metal is made with Sodium Dimethyldithiocarbamate S.D.D
Me, precipitation reaction are carried out 2 hours；Then with filter press be filtrated to get the manganese sulfate solution after primary purification；Use Sodium Dimethyldithiocarbamate
S.D.D makees precipitating reagent precipitation precious metal Me, adds Sodium Dimethyldithiocarbamate S.D.D amount, is calculated as the following formula：
m(S.D.D)=2V*([Co2+]+[Ni2+]+[Pb2+]+[Cu2+]+[Zn2+]+[Cd2+]+[Hg2+])+3V*[Cr3+], in formula
m(S.D.D)It is the amount of Sodium Dimethyldithiocarbamate, unit is mole that precious metal concentration unit is mol/L, and V is the volume of solution, and unit is L,
The molal weight of Sodium Dimethyldithiocarbamate is 143 g/mol；
（4）Purification：In step（3）Activated carbon and the manganese sulfate that manganese sulfate solution weight 3% is added in obtained manganese sulfate solution are molten
The removal of impurities medicament of liquid weight 10% carries out adsorption cleaning impurity, described removal of impurities medicament be polyacrylamide, sodium citrate and
Aluminum sulfate presses polyacrylamide:Sodium citrate:Aluminum sulfate is 3:2:The removal of impurities medicament that 1.5 part by weight is mixed to get；Through depth
Precipitation purification is spent after 12 hours；Press filtration is removed slag, and electrolysis additive and surfactant 12 are then added in obtained solution
Sodium alkyl benzene sulfonate, obtain qualified electrolyte；The preparation method of described electrolysis additive is：According to hexamethylenetetramine:It is poly-
Vinyl alcohol:Benzene sulfonic acid sodium salt:Butanedioic acid:Water is 0.8:0.5:0.01:0.1:10 part by weight is by hexamethylenetetramine, poly- second
Enol, butanedioic acid and benzene sulfonic acid sodium salt are soluble in water, are stirred 10 minutes at 50 DEG C, and it is i.e. available to be cooled to room temperature；Qualified electricity
Solve liquid and require that manganese content is 32-35g/L, ammonium sulphate content is in 100-130g/L；Described electrolysis additive is in the electrolytic solution
Content control in 50mg/L, the content of described surfactant in the electrolytic solution is controlled in 10mg/L；
（5）Electrolysis：Minus plate is made using stainless steel plate, minus plate is before electrolytic cell is put into first with the silicic acid that mass fraction is 1%
Sodium solution impregnates, then places into electrolytic cell；Electrolysing period is 24 hours, and 40-45 DEG C of bath temperature, pH values exist
Between 7.5-8.2；
（6）Passivation：The manganese plate obtained after electrolysis is immediately placed in passivator solution after being extracted out out of electrolytic cell and is passivated 3 minutes,
The manganese plate being passivated is rinsed, dries, peels off and can obtain electrolytic manganese finished product.Described passivator is by following weight percent
Each raw material than content forms：Sodium metasilicate 15%, citric acid 0.03%, sodium tartrate 0.05%, potassium chlorate 0.1%, three second
Hydramine 0.01%, surplus are water.
Embodiment 2
A kind of production method of electrolytic manganese metal, comprises the following steps：
（1）Leach：Manganese spar is crushed to obtain manganese spar powder；Anolyte is put into leaching tanks（Described anolyte is electrolysis
Waste liquid caused by manganese, wherein Mn2+Content concn be 11g/L, H content concentration is 42g/L；NH4 +Concentration be 88g/L）,
According to manganese spar powder：The weight ratio of anolyte is 1:4 ratio adds manganese spar powder, and 5 points are thoroughly mixed at 60 DEG C
Clock, then according to manganese spar powder：The weight ratio of acid is 1:0.6 ratio adds the concentrated sulfuric acid that mass fraction is 98%, and control is anti-
It is 70 DEG C to answer temperature, and Leach reaction 5.5h obtains ore pulp, and the content of spent acid is examined at the end of reaction, and ore pulp spent acid content is controlled
In 2.2g/L；
（2）Iron removaling：Detect the Fe in ore pulp2+Content, the Fe in ore pulp2+Content, input manganese oxide powder carry out reacting straight
To Fe2+Content ＜ 1.0g/l, then add the ammoniacal liquor that mass concentration is 10% and pH values are adjusted to 6.5, persistently keep 45
Minute；Ore pulp progress first time separation of solid and liquid is obtained into rough manganese sulfate solution；
（3）Removing heavy metals：Detect precious metal constituent content i.e. [Co in rough manganese sulfate solution2+]、[Ni2+]、[Cu2+]、[Pb2 +]、[Zn2+]、[Cd2+]、[Cr3+] and [Hg2+] molar concentration；Then precipitating reagent precipitation precious metal is made with Sodium Dimethyldithiocarbamate S.D.D
Me, precipitation reaction are carried out 2.5 hours；Then with filter press be filtrated to get the manganese sulfate solution after primary purification；It is beautiful with good fortune
Sodium S.D.D makees precipitating reagent precipitation precious metal Me, adds Sodium Dimethyldithiocarbamate S.D.D amount, is calculated as the following formula：
m(S.D.D)=2V*([Co2+]+[Ni2+]+[Pb2+]+[Cu2+]+[Zn2+]+[Cd2+]+[Hg2+])+3V*[Cr3+], in formula
m(S.D.D)It is the amount of Sodium Dimethyldithiocarbamate, unit is mole that precious metal concentration unit is mol/L, and V is the volume of solution, and unit is L,
The molal weight of Sodium Dimethyldithiocarbamate is 143 g/mol；
（4）Purification：In step（3）Activated carbon and the manganese sulfate that manganese sulfate solution weight 3% is added in obtained manganese sulfate solution are molten
The removal of impurities medicament of liquid weight 12% carries out adsorption cleaning impurity, described removal of impurities medicament be polyacrylamide, sodium citrate and
Aluminum sulfate presses polyacrylamide:Sodium citrate:Aluminum sulfate is 3:2:The removal of impurities medicament that 1.5 part by weight is mixed to get；Through depth
Precipitation purification is spent after 14 hours；Press filtration is removed slag, and electrolysis additive and surfactant 12 are then added in obtained solution
Sodium alkyl benzene sulfonate, obtain qualified electrolyte；Qualified electrolyte requires that manganese content is 32-35g/L, and ammonium sulphate content is in 100-
130g/L；The content of described electrolysis additive in the electrolytic solution is controlled in 70mg/L, and described surfactant is in electrolyte
In content control in 15mg/L；The preparation method of described electrolysis additive is：According to hexamethylenetetramine:Polyvinyl alcohol:
Benzene sulfonic acid sodium salt:Butanedioic acid:Water is 0.9:90.4:0.01:0.1:10 part by weight by hexamethylenetetramine, polyvinyl alcohol,
Butanedioic acid and benzene sulfonic acid sodium salt are soluble in water, are stirred 8 minutes at 55 DEG C, and it is i.e. available to be cooled to room temperature；
（5）Electrolysis：Minus plate is made using stainless steel plate, minus plate is before electrolytic cell is put into first with the silicon that mass fraction is 1.2%
Acid sodium solution impregnates, then places into electrolytic cell；Electrolysing period is 24 hours, and 40-45 DEG C of bath temperature, pH values exist
Between 7.5-8.2；
（6）Passivation：The manganese plate obtained after electrolysis is immediately placed in passivator solution after being extracted out out of electrolytic cell and is passivated 4 minutes,
The manganese plate being passivated is rinsed, dries, peels off and can obtain electrolytic manganese finished product.Described passivator is by following weight percent
Each raw material than content forms：Sodium metasilicate 18%, citric acid 0.02%, sodium tartrate 0.06%, potassium chlorate 0.07%, three second
Hydramine 0.02%, surplus are water.
Embodiment 3
A kind of production method of electrolytic manganese metal, comprises the following steps：
（1）Leach：Manganese spar is crushed to obtain manganese spar powder；Anolyte is put into leaching tanks（Described anolyte is electrolysis
Waste liquid caused by manganese, wherein Mn2+Content concn be 12g/L, H content concentration is 45g/L, NH4 +Concentration be 90g/L）, press
According to manganese spar powder：The weight ratio of anolyte is 1:4 ratio adds manganese spar powder, and 8 points are thoroughly mixed at 55-60 DEG C
Clock, then according to manganese spar powder：The weight ratio of acid is 1:0.5 ratio adds the concentrated sulfuric acid that mass fraction is 98%, control reaction
Temperature is 65-70 DEG C, and Leach reaction 6h obtains ore pulp, and the content of spent acid is examined at the end of reaction, and the control of ore pulp spent acid content is existed
2.5 g/L；
（2）Iron removaling：Detect the Fe in ore pulp2+Content, the Fe in ore pulp2+Content, input manganese oxide powder carry out reacting straight
To Fe2+Content ＜ 1.0g/l, then add the ammoniacal liquor that mass concentration is 10% and pH values are adjusted to 6.5, persistently keep 50 points
Clock；Ore pulp progress first time separation of solid and liquid is obtained into rough manganese sulfate solution；
（3）Removing heavy metals：Detect precious metal constituent content i.e. [Co in rough manganese sulfate solution2+]、[Ni2+]、[Cu2+]、[Pb2 +]、[Zn2+]、[Cd2+]、[Cr3+] and [Hg2+] molar concentration；Then precipitating reagent precipitation precious metal is made with Sodium Dimethyldithiocarbamate S.D.D
Me, precipitation reaction are carried out 3 hours；Then with filter press be filtrated to get the manganese sulfate solution after primary purification；Use Sodium Dimethyldithiocarbamate
S.D.D makees precipitating reagent precipitation precious metal Me, adds Sodium Dimethyldithiocarbamate S.D.D amount, is calculated as the following formula：
m(S.D.D)=2V*([Co2+]+[Ni2+]+[Pb2+]+[Cu2+]+[Zn2+]+[Cd2+]+[Hg2+])+3V*[Cr3+], in formula
m(S.D.D)It is the amount of Sodium Dimethyldithiocarbamate, unit is mole that precious metal concentration unit is mol/L, and V is the volume of solution, and unit is L,
The molal weight of Sodium Dimethyldithiocarbamate is 143 g/mol；
（4）Purification：In step（3）Activated carbon and the manganese sulfate that manganese sulfate solution weight 3% is added in obtained manganese sulfate solution are molten
The removal of impurities medicament of liquid weight 15% carries out adsorption cleaning impurity, described removal of impurities medicament be polyacrylamide, sodium citrate and
Aluminum sulfate presses polyacrylamide:Sodium citrate:Aluminum sulfate is 3:2:The removal of impurities medicament that 1.5 part by weight is mixed to get；Through depth
Precipitation purification is spent after 15 hours；Press filtration is removed slag, and electrolysis additive and surfactant 12 are then added in obtained solution
Sodium alkyl benzene sulfonate, obtain qualified electrolyte；Qualified electrolyte requires that manganese content is 32-35g/L, and ammonium sulphate content is in 100-
130g/L；The content of described electrolysis additive in the electrolytic solution is controlled in 100mg/L, and described surfactant is in electrolyte
In content control in 20mg/L；The preparation method of described electrolysis additive is：According to hexamethylenetetramine:Polyvinyl alcohol:
Benzene sulfonic acid sodium salt:Butanedioic acid:Water is 1:0.4:0.01:0.1:10 part by weight is by hexamethylenetetramine, polyvinyl alcohol, amber
Acid and benzene sulfonic acid sodium salt are soluble in water, are stirred 5 minutes at 60 DEG C, and it is i.e. available to be cooled to room temperature；
（5）Electrolysis：Minus plate is made using stainless steel plate, minus plate is before electrolytic cell is put into first with the silicon that mass fraction is 1.5%
Acid sodium solution impregnates, then places into electrolytic cell；Electrolysing period is 24 hours, and 40-45 DEG C of bath temperature, pH values exist
Between 7.5-8.2；
（6）Passivation：The manganese plate obtained after electrolysis is immediately placed in passivator solution after being extracted out out of electrolytic cell and is passivated 5 minutes,
The manganese plate being passivated is rinsed, dries, peels off and can obtain electrolytic manganese finished product.Described passivator is by following weight percent
Each raw material than content forms：Sodium metasilicate 20%, citric acid 0.01%, sodium tartrate 0.07%, potassium chlorate 0.05%, three second
Hydramine 0.03%, surplus are water.
Claims (6)
1. a kind of production method of electrolytic manganese metal, it is characterised in that comprise the following steps：
（1）Leach：Manganese spar is crushed to obtain manganese spar powder；Anolyte is put into leaching tanks, according to manganese spar powder：Anolyte
Weight ratio be 1:4 ratio adds manganese spar powder, 5-10 minutes is thoroughly mixed at 55-60 DEG C, then according to water chestnut manganese
Miberal powder：The weight ratio of acid is 1:0.5-0.6 ratio adds the concentrated sulfuric acid that mass fraction is 98%, controlling reaction temperature 65-
70 DEG C, Leach reaction 5.5-8h obtains ore pulp, and the content of spent acid is examined at the end of reaction, and ore pulp spent acid content is controlled in 2-2.5
g/L；
（2）Iron removaling：Detect the Fe in ore pulp2+Content, the Fe in ore pulp2+Content, input manganese oxide powder carry out reacting straight
To Fe2+Content ＜ 1.0g/l, add the ammoniacal liquor that mass concentration is 10% and pH values are adjusted to 6.5, persistently keep 40-50 points
Clock；Ore pulp progress first time separation of solid and liquid is obtained into rough manganese sulfate solution；
（3）Removing heavy metals：Detect precious metal constituent content i.e. [Co in rough manganese sulfate solution2+]、[Ni2+]、[Cu2+]、[Pb2 +]、[Zn2+]、[Cd2+]、[Cr3+] and [Hg2+] molar concentration；Then precipitating reagent precipitation precious metal is made with Sodium Dimethyldithiocarbamate S.D.D
Me, precipitation reaction carry out 2-3 hours；Then with filter press be filtrated to get the manganese sulfate solution after primary purification；
（4）Purification：In step（3）Activated carbon and the manganese sulfate that manganese sulfate solution weight 3% is added in obtained manganese sulfate solution are molten
Liquid weight 10-15% removal of impurities medicament carries out adsorption cleaning impurity, after depth precipitation purification 12-15 hours；Press filtration is removed slag, so
Electrolysis additive and surfactant are added in obtained solution afterwards, obtains qualified electrolyte；Described surfactant is
Neopelex；Qualified electrolyte requires that manganese content is 32-35g/L, and ammonium sulphate content is in 100-130g/L；It is described
Electrolysis additive content in the electrolytic solution control in 50-100mg/L, the content of described surfactant in the electrolytic solution
Control is in 10-20mg/L；
（5）Electrolysis：Minus plate is made using stainless steel plate, minus plate with mass fraction is first 1%-1.5% before electrolytic cell is put into
Sodium silicate solution impregnate, then place into electrolytic cell；Electrolysing period is 24 hours, 40-45 DEG C of bath temperature, pH
Value is between 7.5-8.2；
（6）Passivation：The manganese plate obtained after electrolysis, which is immediately placed in after being extracted out out of electrolytic cell in passivator solution, is passivated 3-5 points
Clock, the manganese plate being passivated is rinsed, dries, peels off and can obtain electrolytic manganese finished product.
2. the production method of electrolytic manganese metal according to claim 1, it is characterised in that step（1）Described in anode
Liquid is waste liquid caused by electrolytic manganese, wherein Mn2+Content concn be 10-12g/L, H content concentration is 40-45g/L；NH4 +
Concentration be 85-90g/L.
3. the production method of electrolytic manganese metal according to claim 1, it is characterised in that described step（3）In, use good fortune
U.S. sodium S.D.D makees precipitating reagent precipitation precious metal Me, adds Sodium Dimethyldithiocarbamate S.D.D amount, is calculated as the following formula：
m(S.D.D)=2V*([Co2+]+[Ni2+]+[Pb2+]+[Cu2+]+[Zn2+]+[Cd2+]+[Hg2+])+3V*[Cr3+], in formula
m(S.D.D)It is the amount of Sodium Dimethyldithiocarbamate, unit is mole that precious metal concentration unit is mol/L, and V is the volume of solution, and unit is L,
The molal weight of Sodium Dimethyldithiocarbamate is 143 g/mol.
4. the production method of electrolytic manganese metal according to claim 1, it is characterised in that step（4）In, described removal of impurities
Medicament is that polyacrylamide, sodium citrate and aluminum sulfate press polyacrylamide:Sodium citrate:Aluminum sulfate is 3:2:1.5 weight
The removal of impurities medicament that amount ratio is mixed to get.
5. the production method of electrolytic manganese metal according to claim 1, it is characterised in that step（4）In, described electrolysis
The preparation method of additive is：According to hexamethylenetetramine:Polyvinyl alcohol:Benzene sulfonic acid sodium salt:Butanedioic acid:Water is 0.8-1:
0.5-0.4:0.01:0.1:Hexamethylenetetramine, polyvinyl alcohol, butanedioic acid and benzene sulfonic acid sodium salt are dissolved in by 10 part by weight
In water, 5-10 minutes are stirred at 50-60 DEG C, it is i.e. available to be cooled to room temperature.
6. the production method of electrolytic manganese metal according to claim 1, it is characterised in that step（6）In, described passivation
Agent is made up of each raw material of following weight percent content：Sodium metasilicate 15~20%, citric acid 0.01%~0.03%,
Sodium tartrate 0.05%~0.07%, potassium chlorate 0.05~0.1%, triethanolamine 0.01-0.03%, surplus are water.
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| CN110684900A (en) * | 2019-10-12 | 2020-01-14 | 中信大锰矿业有限责任公司 | Method for improving manganese leaching rate in low-grade manganese ore |
| CN110804744A (en) * | 2019-11-01 | 2020-02-18 | 四川中哲新材料科技有限公司 | Production process of electrolytic manganese metal |
| CN111809047A (en) * | 2020-06-04 | 2020-10-23 | 西南科技大学 | Method for reducing electrolytic manganese slag source |
| CN112195484A (en) * | 2020-09-27 | 2021-01-08 | 遵义天磁锰业集团有限公司 | Passivation-free process for electrolytic manganese metal production and product post-treatment method |
| CN112501459A (en) * | 2020-11-17 | 2021-03-16 | 遵义天磁锰业集团有限公司 | Solution purification method for producing electrolytic manganese metal from high-sulfur manganese carbonate lean ore |
| CN113443627A (en) * | 2021-07-13 | 2021-09-28 | 四川泷邦净水材料有限公司 | Preparation and use method of activated carbon for purifying manganese sulfate solution |
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