CN103014760A - Production method of electrolytic manganese metal - Google Patents
Production method of electrolytic manganese metal Download PDFInfo
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Abstract
The invention discloses a production method of electrolytic manganese metal, which sequentially comprises the following steps: (1) simultaneously adding mixed ore powder of manganese dioxide ores, sulfurous iron ores and manganese carbonate ores and sulfuric acid into a leaching combination tank, heating to 90-95 DEG C, performing leaching combination reaction for 4-6 hours, and performing solid-liquid separation to obtain a rough manganese sulfate solution; (2) performing two-stage purification on the rough manganese sulfate solution to remove impurities, wherein in the primary purification process, SDD or BaS is added for impurity removal, and then aluminum sulfate is added for purification; and in the secondary purification process, 10-30% of deep impurity removal agent is added, and then ammonium sulfide is added for zinc removal; reacting for 1-2 hours, checking and regulating the pH value to 6.0-8.0, performing pressure filtration, then transferring into a standing tank, and standing; and (3) injecting the purified manganese sulfate solution into an electrolytic tank, controlling the pH value of an electrolytic tank solution to be 7.0-8.0, and electrolyzing for at least 24 hours to obtain the electrolytic manganese metal product. According to the method disclosed by the invention, manganese ore resources are reasonably utilized, and the production cost is lowered.
Description
Technical field
The present invention relates to a kind of production method of electrolytic metal Mn, particularly the method for a kind of usefulness " many ore deposits method " leaching manganese oxide ore, manganese carbonate ore production electrolytic metal Mn.
Background technology
Electrolytic metal Mn is widely used in the fields such as metallurgy, medical science, electronics, communication.Along with the development of science and technology, the application of electrolytic manganese constantly enlarges, and market demand year increases about 15%.China's electrolytic manganese annual capacity can reach 800,000 tons, accounts for 80% of Gross World Product.For many years, most of outlet, the countries such as main exit Japan, Korea S, America and Europe of being used for of China's electrolytic manganese.
Electrolytic metal Mn is to obtain manganese salt with manganese ore through Ore Leaching, the elemental metals that send again electrolytic tank electrolysis to separate out, and the purity of electrolytic manganese is very high, and manganese content is greater than more than 99.7%, thereby mainly uses when aircraft industry, metallurgy and non-ferrous metal metallurgy.Its effect is the hardness that increases the metal material, and most widely used have mauganin, a mangal, and manganese can be put forward heavy alloyed intensity, toughness, wear resistance and erosion resistance in these alloys.Manganese is indispensable additive in the metallurgy industry, electrolytic manganese is the main raw material of producing trimanganese tetroxide after being processed into powdery, the widely used magneticsubstance original paper of electronic industry is produced with trimanganese tetroxide, and electronic industry, metallurgical industry and aerospace industry all need electrolytic metal Mn.
Manganese industry is all take manganese carbonate ore as main raw material for a long time, and the rare people of a large amount of manganese oxide-manganese carbonate ores makes inquiries, and manganese resource is abundant in the Guangxi District, occupy first of national manganese ore recoverable amount, mainly with oxidized ore, manganese carbonate ore, manganese oxide-manganous carbonate layering ore deposit exists, but two ore deposit methods, run into product S in the method production test process of many ore deposits high, power consumption is high, the problems such as heavy metal removal of impurities difficulty, therefore, be necessary to provide a kind of method that can be take manganese oxide-manganous carbonate layering ore deposit as the raw material production electrolytic metal Mn, and it is high to solve product S, power consumption is high, the problems such as heavy metal removal of impurities difficulty.
Summary of the invention
Technical problem to be solved by this invention provide a kind of can be take manganese oxide ore and manganese carbonate ore as main raw, and S and beavy metal impurity are lower in the electrolytic metal Mn that obtains.
The present invention solves the problems of the technologies described above the production method that the technical scheme that adopts provides a kind of electrolytic metal Mn, in turn include the following steps: a) mixed mineral powder and the sulfuric acid with dioxide ore for manganese, sulfurous iron ore, manganese carbonate ore joins in the leaching chemical combination groove simultaneously, heating was leached under 90～95 ℃ combination reaction 4-6 hour, got rough manganese sulfate solution through solid-liquid separation; B) described rough manganese sulfate solution is carried out the secondary-cleaned removal of impurities, in first time scavenging process, under whipped state, add first dimethylamino dithio sodium formiate (SDD) or barium sulphide (BaS) carries out removal of impurities, add again Tai-Ace S 150 and purify; Secondary-cleaned adds first the deep impurity-removing medicament of 10-30%, drops into ammonium sulfide again and dezincifies, and reacts after 1～2 hour, checks and mix up pH value 6.0～8.0, forwards to leave standstill in the groove after press filtration and leaves standstill; The described deep impurity-removing medicament that adds residual content in the groove that leaves standstill; C) manganese sulfate solution after will purifying injects electrolyzer, and control cell liquid pH value is 7.0～8.0; Electrolysis obtains Electrolytic Manganese Product at least after 24 hours.
Further, by weight 1:(0.25 of manganese oxide ore, sulfurous iron ore, manganese carbonate ore～0.4 in the described step a)): (0.2～0.3) ratio directly feeds in the leaching vat, simultaneously by 1:(0.4～0.6) ore deposit acid weight ratio allocate sulfuric acid into.
Further, leach employing groove internal steam pipe direct heating in the chemical combination groove described in the described step a).
Further, add ammonium sulfate in the heating leaching process in the described step a), make ammonium sulfate concentrations reach 100～120g/l; After Leaching reaction finished, whether the qualitative detection ferrous iron was qualified; If ferrous iron is qualitative defective, then the pH value to 5.5 of regulator solution～6.5 and add manganese oxide or hydrogen peroxide except ferrous iron, until the ferrous iron qualitative detection is qualified; Except ferrous iron qualified after, add ammoniacal liquor toward the chemical combination groove, regulate the leach liquor pH value between 6.6～7.0, whether the ferric iron of qualitative detection solution qualified subsequently; If ferric iron is defective, then adds hydrogen peroxide and transfer ammoniacal liquor to remove ferric iron until qualitative qualified.
Further, for the first time in the scavenging process, before adding SDD, regulate first the pH value of solution in the purification tank 6.0～7.0 described in the described step b).
Further, also comprise in the described step b): manganous sulfate in the groove solution, ammonium sulfate content and pH value are left standstill in detection, whether beavy metal impurity content is qualified, if it is defective to find to leave standstill the interior solution of groove, then returns two sections and purify the continuation processing until qualified.
Further, drip gac at chute in the secondary-cleaned liquid pressure-filtering process, in leaving standstill groove, add remaining deep impurity-removing medicament.
Further, described deep impurity-removing medicament is the mixture of organic medicament and inorganic medicament, makes beavy metal impurity content in the solution to 0-1mg/l; Described organic medicament is one or more in Trisodium Citrate, citric acid tricalcium, sodium oxalate, potassium oxalate, the 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid salt; Described inorganic medicament is two or more in sodium sulphite, magnesium sulfide, ferrous sulfate, the Tai-Ace S 150.
Further, in electrolyzer, use the 5-10g tin anhydride to be end selenium, and regularly change groove face liquid discharging tube position at electrolytic process.
Further, after extracting out in electrolyzer, put into immediately the manganese plate that obtains after the described step c) electrolysis the potassium bichromate solution passivation 1-3 minute, the manganese plate that passivation is good hangs in the soaking compartment and soaked 4-6 minute, soaked manganese plate leaves standstill after rinsing well with water blast gun, treat the less pusher of manganese plate face water droplet to the interior oven dry of drying baker, during oven dry, the manganese plate is shifted middle position in the case onto, control the temperature inside the box is as the criterion with manganese plate face drying at 90～100 ℃; With the manganese plate cooling of oven dry, cooled manganese plate is peeled off, is packed, and obtains the electrolytic manganese finished product.
The present invention contrasts prior art following beneficial effect: the production method of electrolytic metal Mn provided by the invention, take manganese oxide ore as oxygenant, sulfurous iron ore is reductive agent, with manganese carbonate ore as auxiliary, can take full advantage of the abundant pyrolusite resource of guest's periphery as one of main raw material, the collocation manganese carbonate ore directly method of leaching prepares manganese sulfate solution, segmentation is carried out after conventional removal of impurities and the deep purifying to manganese sulfate solution, remove beavy metal impurity such as Cu in the solution, Pb, Ni, Co, As, Sb is at≤1mg/l, reach and produce the electrolytic manganese metal solution quality standard, to rationally utilizing manganese resource, good economic benefit and social benefit have reduced production costs.
Embodiment
The production method of solution manganese metal provided by the invention, take manganese ore (manganese oxide ore) as oxygenant, sulfurous iron ore is as reductive agent, as auxiliary, pyrolusite, sulfurous iron ore, manganese carbonate ore react in sulphuric acid soln and generate manganous sulfate under hot conditions with manganese carbonate ore.In actual leaching process, a plurality of chemical reactions can occur simultaneously:
MnO
2+FeS
2+2H
2SO
4=MnSO
4+2S+FeSO
4+2H
2O…………………………（1）
11MnO
2+2FeS
2+11H
2SO
4=11MnSO
4+4SO
2+Fe
2O
3+11H
2O………………（2）
15MnO
2+2FeS
2+11H
2SO
4=15MnSO
4+Fe
2O
3+11H
2O……………………（3）
Fe
2O
3+3H
2SO
4=Fe
2(SO
4)
3+3H
2O………………………………………（4）
MnCO
3+H
2SO
4=MnSO
4+CO
2↑+H
2O……………………………………（5）
Ore pulp behind the leaching chemical combination obtains rough manganese sulfate solution through solid-liquid separation.
Rough manganese sulfate solution becomes qualified manganese sulfate solution through behind the purification and impurity removal.In the rough manganese sulfate solution, contain heavy metal and the impurity such as calcium, magnesium such as copper, lead, nickel, zinc, therefore need to carry out purification and impurity removal.At one section cleaning section, add a certain amount of SDD and barium sulphide (BaS) under the proper temperature, the conditions such as control reaction times and PH make the heavy metal ion formation sulfide precipitations such as nickel, and sulfide precipitation is removed with solution separating after press filtration.The scavenging solution of one section press filtration out carries out secondary-cleaned afterwards, adds the deep purifying medicament, except beavy metal impurities such as dezincifies, further improves the manganese sulfate solution quality.Manganese sulfate solution behind the deep purifying, then the dynamic deliming of the chute of the long distance of flowing through, magnesium are delivered to and are left standstill groove and leave standstill, and ageing of solution is removed the contamination precipitations such as calcium, magnesium, solution after leaving standstill pumps into chamber-type press filter and filters, and obtains qualified manganese sulfate solution.
Qualified manganese sulfate solution obtains Electrolytic Manganese Product after passivation, flushing, oven dry are peeled off and packed behind electrolytic tank electrolysis.At electrowinning process, electrolysis of solutions temperature is controlled at 40～44 ℃, and electrolytic process adds tin anhydride and makes anti-oxidant selenium, strict implement groove manganese, tank liquor PH, and the electrolysis production condition such as current/voltage, thus finally obtain high-quality Electrolytic Manganese Product.The manganese plate goes out groove and obtains finished product after by processing such as passivation, soaking flushing, the packings of drying, peel off, weigh.The below describes with regard to embodiment:
Embodiment 1
1, liquid processed
(1) leaches chemical combination
Joined in the leaching chemical combination groove by weight the mixed breeze of 1:0.25:0.2 (120 orders 〉=90%) by dioxide ore for manganese, sulfurous iron ore and manganese carbonate ore behind the next drying of grinding building pumping, fragmentation, the abrasive dust, be that 98% sulfuric acid adds the dilution heat of sulfuric acid that water is mixed with 100g/L with concentration, weight ratio 1:0.4 by mixed mineral powder and sulfuric acid allocates sulfuric acid into simultaneously, redox reaction 4 hours occur under 90 ℃ temperature, for guaranteeing to leach the temperature of combination reaction, adopt groove internal steam pipe direct heating.
The heating leaching process adds an amount of ammonium sulfate, makes ammonium sulfate concentrations reach solution index requirement, i.e. 100～120g/l.
After Leaching reaction finished, whether the ferrous iron in the qualitative detection solution was qualified, and the qualitative detection color is dark green when defective, and the qualitative detection color is khaki color when qualified.If ferrous iron is qualitative defective, then the pH value to 5.5 of regulator solution～6.5 and add an amount of manganese oxide or hydrogen peroxide except ferrous iron, until the ferrous iron qualitative detection is qualified.
Except ferrous iron qualified after, add ammoniacal liquor toward the chemical combination groove, regulate the leach liquor pH value between 6.6～7.0, whether the ferric iron of qualitative detection solution is qualified subsequently, extract layer is rust when defective, extract layer is transparent whites when qualified, if ferric iron is defective, then adds an amount of hydrogen peroxide and transfers ammoniacal liquor to remove ferric iron until qualitative qualified.
Leaching the chemical combination stage, the factor that affects manganese leaching yield in many ore deposits mainly contains: the full Mn grade of Manganse Dioxide, sulfurous iron ore S, Fe content and ore deposit are active, breeze granularity, the proportioning of mixed mineral powder and sulfuric acid, temperature of reaction, extraction time, stirring intensity etc.
(2) primary purification
Leaching qualified solution forwards purification tank to through press filtration and carries out primary purification, add first SDD and BaS and carry out conventional removal of impurities, add Tai-Ace S 150 again and purify, the metallic impurity such as nickel precipitate with forms such as sulfide, and solution transforms two sections purification tanks and carries out secondary-cleaned after press filtration.
Under whipped state, add SDD in one section purification tank and need react certain hour, nickel adds Tai-Ace S 150 after qualified again in the qualitative detection solution, and sufficient reacting enters two sections purifications by press filtration, and filter residue is delivered to the slag field.
Before adding SDD, the pH value that must regulate solution in the groove touches the mark, and makes pH value 6.0～7.0, otherwise impurity-eliminating effect is poor and cause SDD to waste.In addition, pressure-filtering process stirs and can not stop, and should solution in the groove be emitted fully as far as possible.
(3) two sections purifications
Secondary-cleaned adds first a part of deep impurity-removing medicament, such as the deep impurity-removing medicament of 10-30% predetermined amount, adds the specified amount ammonium sulfide again and dezincifies, and reacts after 1 hour, checks and mix up pH value 6.0～8.0, forwards to leave standstill in the groove after press filtration and leaves standstill.The organic medicament of the reasonably combined use of described deep impurity-removing medicament and inorganic medicament make in the solution the difficult beavy metal impurity content that removes below 1mg/l; Described organic medicament is one or more in Trisodium Citrate, citric acid tricalcium, sodium oxalate, potassium oxalate, the 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid salt; Described inorganic medicament is two or more in sodium sulphite, magnesium sulfide, ferrous sulfate, the Tai-Ace S 150.In the present embodiment, composition and the weight proportion thereof of described deep impurity-removing medicament are respectively: citric acid tricalcium 15～30, potassium oxalate 10～20,1-Hydroxy Ethylidene-1,1-Diphosphonic Acid salt 5～10, magnesium sulfide 5～15, ferrous sulfate 5～15.
Utilize organic medicament and heavy metal ion to form the characteristic of inner complex, under the prerequisite of not serious damage bivalent manganese concentration, the beavy metal impurities such as zinc in the manganese sulfate solution are carried out trace control.
Drip gac at chute in the secondary-cleaned liquid pressure-filtering process, add remaining deep impurity-removing medicament leaving standstill groove.
Pressing filtering liquid enters and leaves standstill groove, and manganous sulfate in the groove solution, ammonium sulfate content and pH value are left standstill in detection, whether beavy metal impurity content is qualified, if it is defective to find to leave standstill the interior solution of groove, need returns two sections purifications and do respective handling until qualified.
After the solution left standstill supernatant 24 hours, after the pressure filter press filtration, the direct pump of manganese sulfate solution carries out electrolysis production to electrolyzer.
2, electrolysis
Qualified manganese sulfate solution is injected electrolyzer, and logical direct current carries out electrolysis in solution under certain condition, and oxidizing reaction and reduction reaction occur respectively on positive plate and negative plate, obtains manganese metal at negative plate, and its reaction formula is:
Mn
2++2e=Mn↓
2H++2e=H
2↑
The specification of quality of manganous sulfate electrolytic solution is:
MnSO
4Content is up to standard;
Fe, Ni qualitative detection are without vestige;
The heavy metal detection by quantitative is qualified;
The electrolytic metal Mn specification of quality that electrolysis obtains is as follows:
S≤0.05%；
(1) electrolytic process
Check electrolyzer and electrolytic anode plate, negative plate, after confirming to meet the electrolysis requirement, beginning is filled with liquid toward electrolyzer, prepare simultaneously a small amount of tin anhydride and do end selenium use, regulated and control the tank liquor pH value 7.0～8.0, after the regulation and control of facility checkout and index were all qualified, electrolysis was carried out in energising.The bath voltage that start process control is suitable, slowly motor current is guaranteed groove condition process stabilizing.
Production method provided by the invention is in electrolysis production manganese metal process, and the tank liquor pH value is taked high value control, and electrolysis production process tank liquor PH is controlled at more than 7.5 all the time, and this and manganese carbonate ore method electrolysis production have than big difference.New liquid is that the medicament in the manganese sulfate solution can improve the high pH value control condition of cell liquid, solves too high manganese plate blackout, the manganese plate of causing of electrolytic process pH value and does not go up the problems such as manganese, can guarantee that manganese is firm on the manganese plate, surface uniform is neat under middle high pH value condition.
Electrolytic process is regularly changed groove face liquid discharging tube position, is conducive to tank liquor manganese and evenly distributes, and reduces the high manganese that causes on plate bursting and the manganese plate of local manganese inhomogeneous etc.
(2) go out groove
Many ore deposits method manganese sulfate solution electrolysis production cycle reaches 24 hours and just can go out groove.Fall first electric current when going out groove, block little new flow quantity, extract the manganese plate out by the one-in-and-one-out principle and change clean negative plate, the manganese plate of extraction is put into passivation in the passivation bucket immediately, avoids the oxidation by air of manganese metal.
3, finished product preparation
(1) passivation and immersion
The manganese plate is extracted out in the electrolyzer and is run into airborne oxygen and can generate manganese oxide at surface oxidation, affect quality product, should in time the manganese plate be put into and carry out passivation in the potassium bichromate solution, and the passivation time general control is at 1-3 minute, the best about 2 minutes.The manganese plate that passivation is good hangs out and soaked in the soaking compartment approximately 4 minutes, hangs out to deliver to the flushing post.
(2) flushing and oven dry
Soaked manganese plate is placed on rinsing area, with water blast gun flushing manganese plate, leaves standstill half a minute after the spot that copper bar and manganese plate face is residual etc. is rinsed well, treats that the less pusher of manganese plate face water droplet dries in drying baker.During oven dry, the manganese plate is shifted middle position in the case onto, and control the temperature inside the box is at 90～100 ℃, and drying time was as the criterion with manganese plate face drying about 15 minutes.The manganese plate that oven dry is good will cool off before peeling off in advance, scalds when avoiding peeling off product.
(3) peel off and pack
Before the manganese plate that cooling is good hung stripping machine, the straight manganese plate of holding was put stripping machine into and is peeled off, and the manganese sheet that strips down drops on platform, and its bunch is shoveled in the funnel.
When the manganese sheet is more in the funnel, be enclosed within the funnel end opening with packing bag, pull open the funnel lock, weight is packed in accordance with regulations, and the manganese product of gained is finished product.
Embodiment 2
1, liquid processed
(1) leaches chemical combination
Joined in the leaching chemical combination groove by weight the mixed breeze of 1:0.32:0.25 (120 orders 〉=90%) by dioxide ore for manganese, sulfurous iron ore and manganese carbonate ore behind the next drying of grinding building pumping, fragmentation, the abrasive dust, be that 98% sulfuric acid adds the dilution heat of sulfuric acid that water is mixed with 100g/L with concentration, weight ratio 1:0.5 by mixed mineral powder and sulfuric acid allocates sulfuric acid into simultaneously, redox reaction 5 hours occur under 93 ℃ temperature, for guaranteeing to leach the temperature of combination reaction, adopt groove internal steam pipe direct heating.
The heating leaching process adds an amount of ammonium sulfate, makes ammonium sulfate concentrations reach solution index requirement, i.e. 100～120g/l.
After Leaching reaction finished, whether the ferrous iron in the qualitative detection solution was qualified, and the qualitative detection color is dark green when defective, and the qualitative detection color is khaki color when qualified.If ferrous iron is qualitative defective, then the pH value to 5.5 of regulator solution～6.5 and add an amount of manganese oxide or hydrogen peroxide except ferrous iron, until the ferrous iron qualitative detection is qualified.
Except ferrous iron qualified after, add ammoniacal liquor toward the chemical combination groove, regulate the leach liquor pH value between 6.6～7.0, whether the ferric iron of qualitative detection solution is qualified subsequently, extract layer is rust when defective, extract layer is transparent whites when qualified, if ferric iron is defective, then adds an amount of hydrogen peroxide and transfers ammoniacal liquor to remove ferric iron until qualitative qualified.
Leaching the chemical combination stage, the factor that affects manganese leaching yield in many ore deposits mainly contains: the full Mn grade of Manganse Dioxide, sulfurous iron ore S, Fe content and ore deposit are active, breeze granularity, the proportioning of mixed mineral powder and sulfuric acid, temperature of reaction, extraction time, stirring intensity etc.
(2) primary purification
Leaching qualified solution forwards purification tank to through press filtration and carries out primary purification, add first SDD and BaS and carry out conventional removal of impurities, add Tai-Ace S 150 again and purify, the metallic impurity such as nickel precipitate with forms such as sulfide, and solution transforms two sections purification tanks and carries out secondary-cleaned after press filtration.
Under whipped state, add SDD in one section purification tank and need react certain hour, nickel adds Tai-Ace S 150 after qualified again in the qualitative detection solution, and sufficient reacting enters two sections purifications by press filtration, and filter residue is delivered to the slag field.
Before adding SDD, the pH value that must regulate solution in the groove touches the mark, and makes pH value 6.0～7.0, otherwise impurity-eliminating effect is poor and cause SDD to waste.In addition, pressure-filtering process stirs and can not stop, and should solution in the groove be emitted fully as far as possible.
(3) two sections purifications
Secondary-cleaned adds first a part of deep impurity-removing medicament, adds the specified amount ammonium sulfide again and dezincifies, and reacts after 1.5 hours, checks and mix up pH value 6.0～8.0, forwards to leave standstill in the groove after press filtration and leaves standstill.The organic medicament of the reasonably combined use of described deep impurity-removing medicament and inorganic medicament make in the solution the difficult beavy metal impurity content that removes below 1mg/l; Described organic medicament is one or more in Trisodium Citrate, citric acid tricalcium, sodium oxalate, potassium oxalate, the 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid salt; Described inorganic medicament is two or more in sodium sulphite, magnesium sulfide, ferrous sulfate, the Tai-Ace S 150.In the present embodiment, the composition of described deep impurity-removing medicament and weight proportion thereof are Trisodium Citrate 15～30, sodium oxalate 10～20, hydroxyl and ethylene-diphosphonic hydrochlorate 5～10, sodium sulphite 5～15, Tai-Ace S 150 5～15.
Utilize organic medicament and heavy metal ion to form the characteristic of inner complex, under the prerequisite of not serious damage bivalent manganese concentration, the beavy metal impurities such as zinc in the manganese sulfate solution are carried out trace control.
Drip gac at chute in the secondary-cleaned liquid pressure-filtering process, add remaining deep impurity-removing medicament leaving standstill groove.
Pressing filtering liquid enters and leaves standstill groove, and manganous sulfate in the groove solution, ammonium sulfate content and pH value are left standstill in detection, whether beavy metal impurity content is qualified, if it is defective to find to leave standstill the interior solution of groove, need returns two sections purifications and do respective handling until qualified.
After the solution left standstill supernatant 24 hours, after the pressure filter press filtration, the direct pump of manganese sulfate solution carries out electrolysis production to electrolyzer.
2, electrolysis
Qualified manganese sulfate solution is injected electrolyzer, and logical direct current carries out electrolysis in solution under certain condition, and oxidizing reaction and reduction reaction occur respectively on positive plate and negative plate, obtains manganese metal at negative plate, and its reaction formula is:
Mn2++2e=Mn↓
2H++2e=H2↑
The specification of quality of manganous sulfate electrolytic solution is:
MnSO4 content is up to standard;
Fe, Ni qualitative detection are without vestige;
The heavy metal detection by quantitative is qualified;
The electrolytic metal Mn specification of quality that electrolysis obtains is as follows:
S≤0.05%；
(1) electrolytic process
Check electrolyzer and electrolytic anode plate, negative plate, after confirming to meet the electrolysis requirement, beginning is filled with liquid toward electrolyzer, prepare simultaneously a small amount of tin anhydride and do end selenium use, regulated and control the tank liquor pH value 7.0～8.0, after the regulation and control of facility checkout and index were all qualified, electrolysis was carried out in energising.The bath voltage that start process control is suitable, slowly motor current is guaranteed groove condition process stabilizing.
Production method provided by the invention is in electrolysis production manganese metal process, and the tank liquor pH value is taked high value control, and electrolysis production process tank liquor PH is controlled at more than 7.5 all the time, and this and manganese carbonate ore method electrolysis production have than big difference.New liquid is that the medicament in the manganese sulfate solution can improve the high pH value control condition of cell liquid, solves too high manganese plate blackout, the manganese plate of causing of electrolytic process pH value and does not go up the problems such as manganese, can guarantee that manganese is firm on the manganese plate, surface uniform is neat under middle high pH value condition.
Electrolytic process is regularly changed groove face liquid discharging tube position, is conducive to tank liquor manganese and evenly distributes, and reduces the high manganese that causes on plate bursting and the manganese plate of local manganese inhomogeneous etc.
(2) go out groove
Many ore deposits method manganese sulfate solution electrolysis production cycle reaches 24 hours and just can go out groove.Fall first electric current when going out groove, block little new flow quantity, extract the manganese plate out by the one-in-and-one-out principle and change clean negative plate, the manganese plate of extraction is put into passivation in the passivation bucket immediately, avoids the oxidation by air of manganese metal.
3, finished product preparation
(1) passivation and immersion
The manganese plate is extracted out in the electrolyzer and is run into airborne oxygen and can generate manganese oxide at surface oxidation, affect quality product, should in time the manganese plate be put into and carry out passivation in the potassium bichromate solution, and the passivation time general control is at 1-3 minute, the best about 2 minutes.The manganese plate that passivation is good hangs out and soaked in the soaking compartment approximately 5 minutes, hangs out to deliver to the flushing post.
(2) flushing and oven dry
Soaked manganese plate is placed on rinsing area, with water blast gun flushing manganese plate, leaves standstill half a minute after the spot that copper bar and manganese plate face is residual etc. is rinsed well, treats that the less pusher of manganese plate face water droplet dries in drying baker.During oven dry, the manganese plate is shifted middle position in the case onto, and control the temperature inside the box is at 90～100 ℃, and drying time was as the criterion with manganese plate face drying about 15 minutes.The manganese plate that oven dry is good will cool off before peeling off in advance, scalds when avoiding peeling off product.
(3) peel off and pack
Before the manganese plate that cooling is good hung stripping machine, the straight manganese plate of holding was put stripping machine into and is peeled off, and the manganese sheet that strips down drops on platform, and its bunch is shoveled in the funnel.
When the manganese sheet is more in the funnel, be enclosed within the funnel end opening with packing bag, pull open the funnel lock, weight is packed in accordance with regulations, and the manganese product of gained is finished product.
Embodiment 3
1, liquid processed
(1) leaches chemical combination
Joined in the leaching chemical combination groove by weight the mixed breeze of 1:0.4:0.3 (120 orders 〉=90%) by dioxide ore for manganese, sulfurous iron ore and manganese carbonate ore behind the next drying of grinding building pumping, fragmentation, the abrasive dust, be that 98% sulfuric acid adds the dilution heat of sulfuric acid that water is mixed with 100g/L with concentration, weight ratio 1:0.6 by mixed mineral powder and sulfuric acid allocates sulfuric acid into simultaneously, redox reaction 6 hours occur under 95 ℃ temperature, for guaranteeing to leach the temperature of combination reaction, adopt groove internal steam pipe direct heating.
The heating leaching process adds an amount of ammonium sulfate, makes ammonium sulfate concentrations reach solution index requirement, i.e. 100～120g/l.
After Leaching reaction finished, whether the ferrous iron in the qualitative detection solution was qualified, and the qualitative detection color is dark green when defective, and the qualitative detection color is khaki color when qualified.If ferrous iron is qualitative defective, then the pH value to 5.5 of regulator solution～6.5 and add an amount of manganese oxide or hydrogen peroxide except ferrous iron, until the ferrous iron qualitative detection is qualified.
Except ferrous iron qualified after, add ammoniacal liquor toward the chemical combination groove, regulate the leach liquor pH value between 6.6～7.0, whether the ferric iron of qualitative detection solution is qualified subsequently, extract layer is rust when defective, extract layer is transparent whites when qualified, if ferric iron is defective, then adds an amount of hydrogen peroxide and transfers ammoniacal liquor to remove ferric iron until qualitative qualified.
Leaching the chemical combination stage, the factor that affects manganese leaching yield in many ore deposits mainly contains: the full Mn grade of Manganse Dioxide, sulfurous iron ore S, Fe content and ore deposit are active, breeze granularity, the proportioning of mixed mineral powder and sulfuric acid, temperature of reaction, extraction time, stirring intensity etc.
(2) primary purification
Leaching qualified solution forwards purification tank to through press filtration and carries out primary purification, add first SDD and BaS and carry out conventional removal of impurities, add Tai-Ace S 150 again and purify, the metallic impurity such as nickel precipitate with forms such as sulfide, and solution transforms two sections purification tanks and carries out secondary-cleaned after press filtration.
Under whipped state, add SDD in one section purification tank and need react certain hour, nickel adds Tai-Ace S 150 after qualified again in the qualitative detection solution, and sufficient reacting enters two sections purifications by press filtration, and filter residue is delivered to the slag field.
Before adding SDD, the pH value that must regulate solution in the groove touches the mark, and makes pH value 6.0～7.0, otherwise impurity-eliminating effect is poor and cause SDD to waste.In addition, pressure-filtering process stirs and can not stop, and should solution in the groove be emitted fully as far as possible.
(3) two sections purifications
Secondary-cleaned adds first a part of deep impurity-removing medicament, adds the specified amount ammonium sulfide again and dezincifies, and reacts after 2 hours, checks and mix up pH value 6.0～8.0, forwards to leave standstill in the groove after press filtration and leaves standstill.The organic medicament of the reasonably combined use of described deep impurity-removing medicament and inorganic medicament make in the solution the difficult beavy metal impurity content that removes below 1mg/l; Described organic medicament is one or more in Trisodium Citrate, citric acid tricalcium, sodium oxalate, potassium oxalate, the 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid salt; Described inorganic medicament is two or more in sodium sulphite, magnesium sulfide, ferrous sulfate, the Tai-Ace S 150.In the present embodiment, the composition of described deep impurity-removing medicament and weight proportion thereof are respectively Trisodium Citrate 15～30, potassium oxalate 10～20,1-Hydroxy Ethylidene-1,1-Diphosphonic Acid salt 5～10, sodium sulphite 5～15, Tai-Ace S 150 5～15.
Utilize organic medicament and heavy metal ion to form the characteristic of inner complex, under the prerequisite of not serious damage bivalent manganese concentration, the beavy metal impurities such as zinc in the manganese sulfate solution are carried out trace control.
Drip gac at chute in the secondary-cleaned liquid pressure-filtering process, add remaining deep impurity-removing medicament leaving standstill groove.
Pressing filtering liquid enters and leaves standstill groove, and manganous sulfate in the groove solution, ammonium sulfate content and pH value are left standstill in detection, whether beavy metal impurity content is qualified, if it is defective to find to leave standstill the interior solution of groove, need returns two sections purifications and do respective handling until qualified.
After the solution left standstill supernatant 24 hours, after the pressure filter press filtration, the direct pump of manganese sulfate solution carries out electrolysis production to electrolyzer.
2, electrolysis
Qualified manganese sulfate solution is injected electrolyzer, and logical direct current carries out electrolysis in solution under certain condition, and oxidizing reaction and reduction reaction occur respectively on positive plate and negative plate, obtains manganese metal at negative plate, and its reaction formula is:
Mn2++2e=Mn↓
2H++2e=H2↑
The specification of quality of manganous sulfate electrolytic solution is:
MnSO4 content is up to standard;
Fe, Ni qualitative detection are without vestige;
The heavy metal detection by quantitative is qualified;
The electrolytic metal Mn specification of quality that electrolysis obtains is as follows:
S≤0.05%；
(1) electrolytic process
Check electrolyzer and electrolytic anode plate, negative plate, after confirming to meet the electrolysis requirement, beginning is filled with liquid toward electrolyzer, prepare simultaneously a small amount of tin anhydride and do end selenium use, regulated and control the tank liquor pH value 7.0～8.0, after the regulation and control of facility checkout and index were all qualified, electrolysis was carried out in energising.The bath voltage that start process control is suitable, slowly motor current is guaranteed groove condition process stabilizing.
Production method provided by the invention is in electrolysis production manganese metal process, and the tank liquor pH value is taked high value control, and electrolysis production process tank liquor PH is controlled at more than 7.5 all the time, and this and manganese carbonate ore method electrolysis production have than big difference.New liquid is that the medicament in the manganese sulfate solution can improve the high pH value control condition of cell liquid, solves too high manganese plate blackout, the manganese plate of causing of electrolytic process pH value and does not go up the problems such as manganese, can guarantee that manganese is firm on the manganese plate, surface uniform is neat under middle high pH value condition.
Electrolytic process is regularly changed groove face liquid discharging tube position, is conducive to tank liquor manganese and evenly distributes, and reduces the high manganese that causes on plate bursting and the manganese plate of local manganese inhomogeneous etc.
(2) go out groove
Many ore deposits method manganese sulfate solution electrolysis production cycle reaches 24 hours and just can go out groove.Fall first electric current when going out groove, block little new flow quantity, extract the manganese plate out by the one-in-and-one-out principle and change clean negative plate, the manganese plate of extraction is put into passivation in the passivation bucket immediately, avoids the oxidation by air of manganese metal.
3, finished product preparation
(1) passivation and immersion
The manganese plate is extracted out in the electrolyzer and is run into airborne oxygen and can generate manganese oxide at surface oxidation, affect quality product, should in time the manganese plate be put into and carry out passivation in the potassium bichromate solution, and the passivation time general control is at 1-3 minute, the best about 2 minutes.The manganese plate that passivation is good hangs out and soaked in the soaking compartment approximately 6 minutes, hangs out to deliver to the flushing post.
(2) flushing and oven dry
Soaked manganese plate is placed on rinsing area, with water blast gun flushing manganese plate, leaves standstill half a minute after the spot that copper bar and manganese plate face is residual etc. is rinsed well, treats that the less pusher of manganese plate face water droplet dries in drying baker.During oven dry, the manganese plate is shifted middle position in the case onto, and control the temperature inside the box is at 90～100 ℃, and drying time was as the criterion with manganese plate face drying about 15 minutes.The manganese plate that oven dry is good will cool off before peeling off in advance, scalds when avoiding peeling off product.
(3) peel off and pack
Before the manganese plate that cooling is good hung stripping machine, the straight manganese plate of holding was put stripping machine into and is peeled off, and the manganese sheet that strips down drops on platform, and its bunch is shoveled in the funnel.
When the manganese sheet is more in the funnel, be enclosed within the funnel end opening with packing bag, pull open the funnel lock, weight is packed in accordance with regulations, and the manganese product of gained is finished product.
The production method of electrolytic metal Mn provided by the invention, take manganese oxide ore as oxygenant, sulfurous iron ore is reductive agent, with manganese carbonate ore as auxiliary, can take full advantage of the abundant pyrolusite resource of guest's periphery as one of main raw material, the collocation manganese carbonate ore directly method of leaching prepares manganese sulfate solution, segmentation is carried out after conventional removal of impurities and the deep purifying to manganese sulfate solution, remove beavy metal impurity such as Cu in the solution, Pb, Ni, Co, As, Sb is at≤1mg/l, reach and produce the electrolytic manganese metal solution quality standard, to rationally utilizing manganese resource, good economic benefit and social benefit have reduced production costs.
Although the present invention discloses as above with preferred embodiment; so it is not to limit the present invention, any those skilled in the art, without departing from the spirit and scope of the present invention; when can doing a little modification and perfect, so protection scope of the present invention is when with being as the criterion that claims were defined.
Claims (10)
1. the production method of an electrolytic metal Mn is characterized in that in turn including the following steps:
A) mixed mineral powder and the sulfuric acid with dioxide ore for manganese, sulfurous iron ore, manganese carbonate ore joins in the leaching chemical combination groove simultaneously, and heating was leached under 90～95 ℃ combination reaction 4-6 hour, got rough manganese sulfate solution through solid-liquid separation;
B) described rough manganese sulfate solution is carried out the secondary-cleaned removal of impurities, in first time scavenging process, under whipped state, add first dimethylamino dithio sodium formiate (SDD) or barium sulphide (BaS) carries out removal of impurities, add again Tai-Ace S 150 and purify; Secondary-cleaned adds first the deep impurity-removing medicament of 10-30%, drops into ammonium sulfide again and dezincifies, and reacts after 1～2 hour, checks and mix up pH value 6.0～8.0, forwards to leave standstill in the groove after press filtration and leaves standstill; The described deep impurity-removing medicament that adds residual content in the groove that leaves standstill;
C) manganese sulfate solution after will purifying injects electrolyzer, and control cell liquid pH value is 7.0～8.0; Electrolysis obtains Electrolytic Manganese Product at least after 24 hours.
2. the production method of electrolytic metal Mn according to claim 1, it is characterized in that by weight 1:(0.25 of manganese oxide ore, sulfurous iron ore, manganese carbonate ore in the described step a)～0.4): (0.2～0.3) ratio directly feeds in the leaching vat, simultaneously by 1:(0.4～0.6) ore deposit acid weight ratio allocate sulfuric acid into.
3. the production method of electrolytic metal Mn according to claim 1 is characterized in that leaching described in the described step a) and adopts groove internal steam pipe direct heating in the chemical combination groove.
4. the production method of electrolytic metal Mn according to claim 1 is characterized in that adding ammonium sulfate in the heating leaching process in the described step a), makes ammonium sulfate concentrations reach 100～120g/l; After Leaching reaction finished, whether the qualitative detection ferrous iron was qualified; If ferrous iron is qualitative defective, then the pH value to 5.5 of regulator solution～6.5 and add manganese oxide or hydrogen peroxide except ferrous iron, until the ferrous iron qualitative detection is qualified; Except ferrous iron qualified after, add ammoniacal liquor toward the chemical combination groove, regulate the leach liquor pH value between 6.6～7.0, whether the ferric iron of qualitative detection solution qualified subsequently; If ferric iron is defective, then adds hydrogen peroxide and transfer ammoniacal liquor to remove ferric iron until qualitative qualified.
5. the production method of electrolytic metal Mn according to claim 1 is characterized in that in the scavenging process first time described in the described step b), before adding SDD, regulates first the pH value of solution in the purification tank 6.0～7.0.
6. the production method of electrolytic metal Mn according to claim 1 or 5, it is characterized in that also comprising in the described step b): manganous sulfate in the groove solution, ammonium sulfate content and pH value are left standstill in detection, whether beavy metal impurity content is qualified, if it is defective to find to leave standstill the interior solution of groove, then returns two sections and purify the continuation processing until qualified.
7. the production method of electrolytic metal Mn according to claim 6 is characterized in that dripping gac at chute in the secondary-cleaned liquid pressure-filtering process, adds remaining deep impurity-removing medicament in leaving standstill groove.
8. according to claim 1 or the production method of 7 described electrolytic metal Mns, it is characterized in that described deep impurity-removing medicament is the mixture of organic medicament and inorganic medicament, make beavy metal impurity content in the solution to 0-1mg/l; Described organic medicament is one or more in Trisodium Citrate, citric acid tricalcium, sodium oxalate, potassium oxalate, the 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid salt; Described inorganic medicament is two or more in sodium sulphite, magnesium sulfide, ferrous sulfate, the Tai-Ace S 150.
9. the production method of electrolytic metal Mn according to claim 1 is characterized in that using in electrolyzer the 5-10g tin anhydride to be end selenium, and regularly changes groove face liquid discharging tube position at electrolytic process.
10. the production method of electrolytic metal Mn according to claim 1, it is characterized in that putting into immediately after the manganese plate that obtains after the described step c) electrolysis is extracted out in electrolyzer the potassium bichromate solution passivation 1-3 minute, the manganese plate that passivation is good hangs in the soaking compartment and soaked 4-6 minute, soaked manganese plate leaves standstill after rinsing well with water blast gun, treat that the less pusher of manganese plate face water droplet is to the interior oven dry of drying baker, during oven dry, the manganese plate is shifted middle position in the case onto, control the temperature inside the box is as the criterion with manganese plate face drying at 90～100 ℃; With the manganese plate cooling of oven dry, cooled manganese plate is peeled off, is packed, and obtains the electrolytic manganese finished product.
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