CN103555940A - Preparation method of special electrolytic manganese dioxide for automobile power battery - Google Patents
Preparation method of special electrolytic manganese dioxide for automobile power battery Download PDFInfo
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Abstract
The invention belongs to the field of battery material processing and specifically discloses a preparation method of a special electrolytic manganese dioxide for an automobile power battery. The preparation method comprises the following steps: performing manganese sulfate leaching, neutralizing and removing iron, removing impurities for heavy metals, electrolyzing and performing post-processing; manganese oxide mineral powder, pyrite powder and industrial sulphuric acid are soaked in the presence of SO2 to prepare crude manganese sulfate liquor; iron is removed by ammonium bicarbonate liquor; heavy metals are removed by utilizing barium sulphide; a manganese dioxide semi-finished product is obtained at a positive electrode through periodic electrolysis; the special electrolytic manganese dioxide for the automobile power battery is finally obtained by post-processing. According to the preparation method disclosed by the invention, the production process is simplified, the production process efficiency is improved, and the performance of obtained products is excellent, and finally, the production cost is lowered.
Description
Technical field
The invention belongs to battery material manufacture field, specifically a kind of Low grade manganese ore that utilizes is prepared the method for automobile power cell electrolysis special Manganse Dioxide under hot conditions.
Background technology
Automobile power cell electrolysis special Manganse Dioxide is the raw material of Li-ion rechargeable pond positive electrode material.New forms of energy, novel material that anode material for lithium-ion batteries belongs to state key support originate in field.As the lithium manganate of anode material for lithium-ion batteries, owing to thering is high-performance, security and advantage cheaply, as a kind of lithium ion anode material with great potential, caused in recent years the concern of lot of domestic and foreign battery production producer.Acceleration along with economic globalization industry restructuring paces; and oil price rapid development in recent years and strict environmental protection requirement at present; exploitation and use electromobile (EV) or hybrid vehicle (HEV) all obtain general attention in countries in the world, Ge great automobile factory releases the electronic plan of exploitation one after another in the world.And the research and development of lithium-ion-power cell become the calculated most important thing of Development of EV.In fact in recent years Japan started from China in batches import EMD finished product or work in-process for scale of mass production lithium manganate.It is larger as raw material production new forms of energy novel material lithium manganate battery market has openings that future is usingd electrolytic manganese dioxide, and supply falls short of demand, has wide market outlook.
It is raw material that manganese carbonate ore or manganese oxide ore are mainly take in the production of current domestic electrolytic manganese dioxide.Due to manganous carbonate content in domestic low-grade manganese carbonate ore low (below 30%), the consumption of manganese carbonate ore and sulfuric acid is all very large, and production cost is too high; Take manganese oxide ore as raw material, and at present the main processing method adopting has after reducing roasting higher-grade manganese oxide ore to prepare manganese sulfate solution or with Low grade manganese ore and high reactivity sulfurous iron ore, redox reaction method to occur under acidic conditions with sulfuric acid to leach and directly leaches and prepare manganese sulfate solution production electrolytic manganese dioxide.After adopting reducing roasting higher-grade manganese oxide ore, direct sulfuric acid to leach is prepared manganese sulfate solution, this processing method, and the technological process of production is long, energy consumption is high, and production cost is high, and has the potential collision hazard of environmental pollution.Domestic higher-grade manganese oxide market value is high, and because long-term mining higher-grade manganese oxide ore resource is relatively exhausted, produces and be difficult to ensure.The manganese oxide aboundresources in Guangxi, most of for mining, choosing are difficult to process, discarded mine tailings and Low grade manganese ore, be characterized in that manganese metal content is low, foreign matter content is high, fully do not developed for a long time, and hindered reclaiming of mine, affect the balance of nature in mine.There is redox reaction method and directly leach manganese sulfate solution in Low grade manganese ore and high reactivity sulfurous iron ore, the processing method technological process of production of producing electrolytic manganese dioxide is short, energy consumption is low under acidic conditions, and production cost is low, good in economic efficiency.
At patent CN201110116976.1, Guangxi willow chemical industry discloses the production method that the present invention relates to a kind of electrolytic manganese dioxide, comprises the following steps: A prepares the mixed solution of thick manganous sulfate and ore pulp; B carries out neutralized ex iron to the solution of thick manganous sulfate and ore pulp; C carries out three deep purifying removal of impurities to thick manganese sulfate solution: comprise that primary purification is removed heavy metal, secondary-cleaned is removed trace element molybdenum, purified for three times and remove calcium sulfate and sal epsom; D electrolysis; E rinsing: rinsing is divided into: hot water wash acid, weak base rinsing, highly basic rinsing, hot water soda, diluted acid backwash and six steps of hot water rinsing; F abrasive dust; G blending, obtains electrolytic manganese dioxide product.The present invention is usingd Low grade manganese ore and is prepared manganese sulfate solution as main raw material, manganese sulfate solution obtains highly purified electrolytic solution after deep purifying, the mercury-free alkaline battery of production high-performance respectively electrolysis special Manganse Dioxide and automobile power cell electrolysis special Manganse Dioxide under different electrolytic conditions, electrolytic manganese dioxide foreign matter content is low, and quality product is high.Although the product quality quality that this invention obtains is high, the problems such as production cost is too high, preparation process is complicated, length consuming time, efficiency is low, method specific aim is poor that it exists.
Summary of the invention
The object of the invention is to overcome existing automobile power cell electrolysis special Manganse Dioxide preparation technology exist complicated loaded down with trivial details, preparation process time is long, efficiency is low, the problems such as method specificity is poor, provide a kind of preparation method for the special-purpose Manganse Dioxide of automobile power cell.
The solution of the present invention is by such realization: a kind of preparation method of automobile power cell electrolysis special Manganse Dioxide, and this preparation method's step comprises:
A, Leaching of manganese sulfate: granularity>=150 object manganese oxide powder, troilite powder, industrial sulphuric acid are put in leaching reactive tank according to the ratio of weight ratio 10000g:800 ~ 1500g:1500 ~ 2200g, low whipping speed is that 80 ~ 120rpm, temperature are to react 1.5 ~ 2 hours under the condition of 80 ~ 90 ℃, then stirring velocity is adjusted to 60 ~ 70rpm, temperature is 85 ~ 95 ℃, passes into sulfurous gas SO simultaneously
2gas, manganese oxide powder and sulfurous gas SO
2the ratio of gas intake is 10000g:0.5-2.0mol, and the reaction times is 1.0-1.5 hour, and leaching obtains the molten slurries of rough manganous sulfate; The manganese content of manganese oxide powder is 15 ~ 17%, and effective sulfur content in sulfurous iron ore (weight ratio) is more than 25%.
B, neutralized ex iron: under normal temperature condition, in the rough manganese sulfate solution 1 obtaining toward step a, add bicarbonate of ammonia, residual H in neutralization solution
2sO
4, making pH is 4.5, stops adding bicarbonate of ammonia, detects concentration≤10 of ferrous ion in solution
-5during mol/L, be qualified, if the concentration > of ferrous ion 10
-5mol/L, adds granularity>=300 object manganese oxide powder, until ferrous ion content is qualified in mixed solution, after ferrous ion is qualified, continuing to add bicarbonate of ammonia to adjust pH value is 6.5, detects concentration≤10 of ferric ion in mixed solution
-5during mol/L, be qualified, if the concentration > of ferric ion 10
-5mol/L, continues to add bicarbonate of ammonia, until ferric ion content is qualified in mixed solution, removes by filter ore pulp slag and obtains thick manganese sulfate solution.The bicarbonate of ammonia concentration of more than using is 0.5-2mol/L.
C, heavy metal removal of impurities: the thick manganese sulfate solution temperature that heating steps b obtains is brought up to 85-90 ℃, slowly adds barium sulphide BaS and sodium sulphite Na
2the cured blend of S, the speed that cured blend adds is 2-5g/L/min, every 30min, detect a Cu, Pb, Ni, the concentration of Co, as Cu≤3ppm, Pb≤5ppm, Ni≤3ppm, during Co≤3ppm, stop adding cured blend, add granularity>=300 object manganese oxide powder, make the concentration≤0.003ppm of elements Mo, according to the ratio of reaction soln: flocculating aids=100L:20-25g, drop into flocculating aids, after stirring 20-30min, remove by filter throw out and obtain filtrate, in filtrate, add complex polyelectrolyte particle, the complex polyelectrolyte particle adding and the ratio of filtrate are 2-5g:100L, add latter standing 1 day, obtain the manganese sulfate solution after removal of impurities.
D, electrolysis and aftertreatment: the manganese sulfate solution after the removal of impurities that step c is obtained proceeds in electrolyzer and carries out electrolysis, and electrolytic condition is: electrolysis temperature is 95-98 ℃, anodic current density 58-120A/m
2, electrolytic solution sulfuric acid H
2sO
4concentration 0.28-0.36mol/L, feed liquor manganous sulfate concentration is 0.7-1.2mol/L, electrolysing period is 7-11 days, at anode, obtains electrolytic manganese dioxide work in-process, and Manganse Dioxide work in-process obtain automobile power cell electrolysis special Manganse Dioxide finished product through rinsing, abrasive dust, removal of impurities, blending aftertreatment.
As further restriction of the present invention, described cured blend is 20%-30% sodium sulphite Na
2s solution is that 0.1 ~ 0.2L:0.8 ~ 0.9L mixes with 20%-30% barium sulphide BaS solution according to volume ratio.
As further restriction of the present invention, described flocculating aids is any in diatomite, perlite, Mierocrystalline cellulose, asbestos, Graphite Powder 99, sawdust.
As further restriction of the present invention, described complex polyelectrolyte particle is any in polyacrylamide, polymine, cationic starch, polymeric amide.
As further restriction of the present invention, described rinsing is for first washing acid neutralization with the NaOH solution of 20%-25%, to pH be 7.0-9.0, then use the sulphuric acid soln soda removal of impurities of 3%-4%, to pH be 7.0 neutrality, rinse cycle maintenance treatment temp is 80 ~ 95 ℃.The final pH 6.5 ~ 7.0 of product, also can adjust according to product demand.
As a further improvement on the present invention, described abrasive dust is for to be controlled at manganese dioxide product particle diameter between 13 ~ 15um.
The know-why that the present invention realizes is: adopt " two ore deposits add acid system " production technology, production selects Low grade manganese ore under the effect of catalyzer (sulfurous iron ore), to react with sulfuric acid through abrasive dust to prepare manganese sulfate solution (thick liquid), passes into a small amount of SO in the process of sulfuric acid dissolution manganese oxide powder
2accelerated oxidation manganese ore is dissolved into vitriol, makes its oxidation more abundant.Utilize bicarbonate of ammonia neutralization except the iron in thick manganese sulfate solution, because tradition generally adopts calcium carbonate deironing, but it easily introduces calcium ion, thereby increase the weight of later stage calcium sulfate and remove to remove pressure, and the present invention creates exploration by practice, the bicarbonate of ammonia weak caustic solution that utilizes of novelty carries out neutralized ex iron, has alleviated the later stage removal of impurities pressure of metal ion.Utilize cured blend to remove the heavy metal ion such as Cu, Pb, Ni, Co, Mo, because tradition mainly adopts BaS as cleaner, and barium sulphide price is more expensive, the existence of Ba simultaneously has interference for the last performance of product (conduction, resistance), and the present invention introduces Na on the basis of BaS
2s, one side has reduced the consumption of BaS, has also alleviated on the other hand the performance impact of BaS to product.Utilize flocculating aids, complex polyelectrolyte particle flocculation agent, accelerated the precipitation of filter cleaner and the ionic impurity of solution, preparation technology is simplified, preparation process efficiency is improved.The principal reaction formula being mainly concerned with is as follows:
Leach: MnO
2+ 2H
2sO
4+ 2e=SO
4 2-+ MnSO
4+ 2H
2o, MnO
2+ SO
2=MnSO
4.
Electrolysis: MnSO
4+ 2H
2o=MnO
2+ H
2sO
4+ H
2↑.
Removal of impurities: MnO
2+ 2Fe
2++ 4H
+=2Fe
3++ Mn
2++ 2H
2o.
Fe
3＋＋3OH
-=Fe(OH)
3?↓。Cu
2＋＋S
2-=CuS↓。
Co
2＋＋S
2-=CoS↓。Ni
2＋＋S
2-=NiS↓。
Pb
2＋＋S
2-=PbS↓。
The present invention possesses following good result:
(1) the present invention, by improving traditional electrolytic manganese dioxide " two ore deposits add acid system " production technique, introduces SO
2catalysis, bicarbonate of ammonia neutralization, not only add fast response and also alleviated the processing pressure of later stage to impurity in product, finally realize automobile power cell electrolytic manganese dioxide product and reach following requirement: 1. Manganse Dioxide>=92.50%, the content of the indexs such as impurity F e, Cu, Pb, Ni, Co, K, Na, Ca, Mg is low, Cu≤3ppm, Pb≤5ppm, Ni≤3ppm, Co≤3ppm, especially Fe requires below 10ppm, make impurity K≤0.03%, Na content is reduced to bottom line, and hydrochloric acid is not tolerant≤and 0.01%; 2. specific surface area is controlled at 35m
2/ g-40m
2/ g; 3. rinsing production technique is selected rational neutralizing agent, makes impurity K, Na content be reduced to bottom line; 4. finished particle degree requires to be controlled at 13 ~ 15 microns of left and right, and particle size distribution is concentrated.
(2) preparation method of the present invention, by introducing catalyzer, effective reaction conditions, has simplified Production Flow Chart, improves production technique efficiency, and the product performance high-quality obtaining, has finally lowered production cost.
Embodiment
Below in conjunction with embodiment, describe the preparation method of a kind of automobile power cell electrolysis special of the present invention Manganse Dioxide, these descriptions are not that content of the present invention is further limited.
Embodiment 1
A, Leaching of manganese sulfate: granularity>=150 object manganese oxide powder, troilite powder, industrial sulphuric acid are put in leaching reactive tank according to the ratio of weight ratio 10000g:1000g:2000g, low whipping speed is that 80rpm, temperature are to react 1.5 hours under the condition of 85 ℃, then stirring velocity is adjusted to 60rpm, temperature is 85 ℃, passes into sulfurous gas SO simultaneously
2gas, manganese oxide powder and sulfurous gas SO
2the ratio of gas intake is 10000g:0.5mol, and the reaction times is 1.0 hours, and leaching obtains the molten slurries of rough manganous sulfate.The manganese content of manganese oxide powder is 17%, and effective sulfur content in sulfurous iron ore (weight ratio) is 25%.
B, neutralized ex iron: under normal temperature condition, in the molten slurries of rough manganous sulfate that obtain toward step a, add bicarbonate of ammonia, residual H in neutralization solution
2sO
4, making pH is 4.5, stops adding bicarbonate of ammonia, detects concentration≤10 of ferrous ion in solution
-5during mol/L, be qualified, if the concentration > of ferrous ion 10
-5mol/L, adds granularity>=300 object manganese oxide powder, until ferrous ion content is qualified in mixed solution, after ferrous ion is qualified, continuing to add bicarbonate of ammonia to adjust pH value is 6.5, detects concentration≤10 of ferric ion in mixed solution
-5during mol/L, be qualified, if the concentration > of ferric ion 10
-5mol/L, continues to add bicarbonate of ammonia, until ferric ion content is qualified in mixed solution, removes by filter ore pulp slag and obtains thick manganese sulfate solution.
C, heavy metal removal of impurities: the thick manganese sulfate solution temperature that heating steps b obtains is brought up to 85-90 ℃, slowly adds barium sulphide BaS and sodium sulphite Na
2the cured blend of S, cured blend is 30% sodium sulphite Na
2s solution is that 0.1L:0.9L mixes with 30% barium sulphide BaS solution according to volume ratio, the speed that cured blend adds is 2.5g/L/min, every 30min, detect a Cu, Pb, Ni, the concentration of Co, as Cu≤3ppm, Pb≤5ppm, Ni≤3ppm, during Co≤3ppm, stop adding cured blend, add granularity>=300 object manganese oxide powder, make the concentration≤0.003ppm of elements Mo, according to the ratio of reaction soln: flocculating aids=100L:25g, drop into super-cell, after stirring 20min, remove by filter throw out and obtain filtrate, in filtrate, add polymeric amide complex polyelectrolyte particle, the complex polyelectrolyte particle adding and the ratio of filtrate are 3g:100L, add latter standing 1 day, obtain the manganese sulfate solution after removal of impurities.
D, electrolysis and aftertreatment: the manganese sulfate solution after the removal of impurities that step c is obtained proceeds in electrolyzer and carries out electrolysis, and electrolytic condition is: electrolysis temperature is 98 ℃, anodic current density 100A/m
2, electrolytic solution H
2sO
4concentration 0.30mol/L, feed liquor manganous sulfate concentration is 1. 0mol/L, electrolysing period is 8 days, at anode, obtains electrolytic manganese dioxide work in-process.
Aftertreatment: the NaOH alkali lye that is first 20% by concentration is washed acid neutralization, to pH be 7.5, then the sulfuric acid H that is 1%-4% by concentration
2sO
4soda removal of impurities, to pH be 6.5, it is 80 ℃ that water washing process keeps treatment temp.The particle that is particle diameter≤13um by manganese dioxide product abrasive dust again, obtains automobile power cell electrolysis special Manganse Dioxide after blending.
The product Manganse Dioxide content 93.50% that the present embodiment obtains, Cu≤3ppm, Pb≤5ppm, Ni≤3ppm, Co≤3ppm, especially Fe reaches below 10ppm, and K≤300ppm, Na≤3000ppm, Ca≤300ppm, Mg≤300ppm, Mo≤1ppm, hydrochloric acid is not tolerant≤and 0.01%, specific surface area 35m
2/ g-40m
2/ g.
Embodiment 2
A, Leaching of manganese sulfate: granularity>=150 object manganese oxide powder, troilite powder, industrial sulphuric acid are put in leaching reactive tank according to the ratio of weight ratio 10000g:800g:2200g, low whipping speed is that 100rpm, temperature are to react 2 hours under the condition of 90 ℃, then stirring velocity is adjusted to 70rpm, temperature is 90 ℃, passes into sulfurous gas SO simultaneously
2gas, manganese oxide powder and sulfurous gas SO
2the ratio of gas intake is 10000g:2.0mol, and the reaction times is 1.2 hours, and leaching obtains the molten slurries of rough manganous sulfate.The manganese content of manganese oxide powder is 15.5%, and effective sulfur content in sulfurous iron ore (weight ratio) is 28%.
B, neutralized ex iron: with the operation in embodiment 1.
C, heavy metal removal of impurities: the thick manganese sulfate solution temperature that heating steps b obtains is brought up to 90 ℃, slowly adds barium sulphide BaS and sodium sulphite Na
2the cured blend of S, cured blend is 20% sodium sulphite Na
2s solution is that 0.2L:0.8L mixes with 30% barium sulphide BaS solution according to volume ratio, the speed that cured blend adds is 4.5g/L/min, examination criteria is with embodiment 1 requirement, according to the ratio of reaction soln: flocculating aids=100L:20g, drop into sawdust flocculating aids, after stirring 25min, remove by filter throw out and obtain filtrate, in filtrate, add polyacrylamide complex polyelectrolyte particle, the complex polyelectrolyte particle adding and the ratio of filtrate are 4.5g:100L, add latter standing 1 day, obtain the manganese sulfate solution after removal of impurities.
D, electrolysis and aftertreatment: the manganese sulfate solution after the removal of impurities that step c is obtained proceeds in electrolyzer and carries out electrolysis, and electrolytic condition is: electrolysis temperature is 97 ℃, anodic current density 85A/m
2, electrolytic solution H
2sO
4concentration 0.30mol/L, feed liquor manganous sulfate concentration is 0.8mol/L, electrolysing period is 10 days, at anode, obtains electrolytic manganese dioxide work in-process.
Aftertreatment: the NaOH alkali lye that is first 25% by concentration is washed acid neutralization, to pH be 8.0, then the sulfuric acid H that is 1%-4% by concentration
2sO
4soda removal of impurities, to pH be 7.0, it is 85 ℃ that rinse cycle keeps treatment temp.The particle that is particle diameter≤15um by manganese dioxide product abrasive dust again; After blending, obtain automobile power cell electrolysis special Manganse Dioxide.
The product Manganse Dioxide content 93.00% that the present embodiment obtains, Cu≤3ppm, Pb≤5ppm, Ni≤3ppm, Co≤3ppm, especially Fe reaches below 10ppm, and K≤300ppm, Na≤3000ppm, Ca≤300ppm, Mg≤300ppm, Mo≤1ppm, hydrochloric acid is not tolerant≤and 0.01%, specific surface area 35m
2/ g-40m
2/ g.
Embodiment 3
A, Leaching of manganese sulfate: granularity>=150 object manganese oxide powder, troilite powder, industrial sulphuric acid are put in leaching reactive tank according to the ratio of weight ratio 10000g:1200g:1800g, low whipping speed is that 120rpm, temperature are to react 1.5 hours under the condition of 85 ℃, then stirring velocity is adjusted to 70rpm, temperature is 95 ℃, passes into sulfurous gas SO simultaneously
2gas, manganese oxide powder and sulfurous gas SO
2the ratio of gas intake is 10000g:1.5mol, and the reaction times is 1.5 hours, and leaching obtains the molten slurries of rough manganous sulfate.The manganese content of manganese oxide powder is 16.0%, and effective sulfur content in sulfurous iron ore (weight ratio) is more than 30%.
B, neutralized ex iron: with operational requirement in embodiment 1.
C, heavy metal removal of impurities: the thick manganese sulfate solution temperature that heating steps b obtains is brought up to 90 ℃, slowly adds barium sulphide BaS and sodium sulphite Na
2the cured blend of S, cured blend is 30% sodium sulphite Na
2s solution is that 0.1L:0.9L mixes with 20% barium sulphide BaS solution according to volume ratio, the speed that cured blend adds is 2.0g/L/min, testing requirement is with embodiment 1, according to the ratio of reaction soln: flocculating aids=100L:23g, drop into cellulose filter aid, after stirring 30min, remove by filter throw out and obtain filtrate, in filtrate, add polymine complex polyelectrolyte particle, the complex polyelectrolyte particle adding and the ratio of filtrate are 4.0g:100L, add latter standing 1 day, obtain the manganese sulfate solution after removal of impurities.
D, electrolysis and aftertreatment: the manganese sulfate solution after the removal of impurities that step c is obtained proceeds in electrolyzer and carries out electrolysis, and electrolytic condition is: electrolysis temperature is 96 ℃, anodic current density 120A/m
2, electrolytic solution sulfuric acid H
2sO
4concentration 0.28mol/L, feed liquor manganous sulfate concentration is 1.2mol/L, electrolysing period is 7 days, at anode, obtains electrolytic manganese dioxide work in-process.
Aftertreatment: the NaOH alkali lye that is first 25% by concentration is washed acid neutralization, to pH be 7.5, then the sulfuric acid H that is 1%-4% by concentration
2sO
4soda removal of impurities, to pH be 6.5, it is 90 ℃ that rinse cycle keeps treatment temp.The particle that is particle diameter≤13um by manganese dioxide product abrasive dust again; After blending, obtain automobile power cell electrolysis special Manganse Dioxide.
The product Manganse Dioxide content 93.50% that the present embodiment obtains, Cu≤3ppm, Pb≤5ppm, Ni≤3ppm, Co≤3ppm, especially Fe reaches below 10ppm, and K≤300ppm, Na≤3000ppm, Ca≤300ppm, Mg≤300ppm, Mo≤1ppm, hydrochloric acid is not tolerant≤and 0.01%, specific surface area 35m
2/ g-40m
2/ g.
Embodiment 4
A, Leaching of manganese sulfate: granularity>=150 object manganese oxide powder, troilite powder, industrial sulphuric acid are put in leaching reactive tank according to the ratio of weight ratio 10000g:1200g:1800g, low whipping speed is that 100rpm, temperature are to react 1.5 hours under the condition of 85 ℃, then stirring velocity is adjusted to 60rpm, temperature is 95 ℃, passes into sulfurous gas SO simultaneously
2gas, manganese oxide powder and sulfurous gas SO
2the ratio of gas intake is 10000g:1.0mol, and the reaction times is 1.5 hours, and leaching obtains the molten slurries of rough manganous sulfate.The manganese content of manganese oxide powder is 16.0%, and effective sulfur content in sulfurous iron ore (weight ratio) is 30%.
B, neutralized ex iron: with embodiment 1 operation.
C, heavy metal removal of impurities: the thick manganese sulfate solution temperature that heating steps b obtains is brought up to 90 ℃, slowly adds barium sulphide BaS and sodium sulphite Na
2the cured blend of S, cured blend is 25% sodium sulphite Na
2s solution is that 0.2L:0.8L mixes with 30% barium sulphide BaS solution according to volume ratio, the speed that cured blend adds is 3.0g/L/min, testing requirement is with embodiment 1, according to the ratio of reaction soln: flocculating aids=100L:25g, drop into asbestos flocculating aids, after stirring 30min, remove by filter throw out and obtain filtrate, in filtrate, add cationic starch complex polyelectrolyte particle, the complex polyelectrolyte particle adding and the ratio of filtrate are 2.0g:100L, add latter standing 1 day, obtain the manganese sulfate solution after removal of impurities.
D, electrolysis and aftertreatment: the manganese sulfate solution after the removal of impurities that step c is obtained proceeds in electrolyzer and carries out electrolysis, and electrolytic condition is: electrolysis temperature is 95 ℃, anodic current density 58A/m
2, electrolytic solution sulfuric acid H
2sO
4concentration 0.36mol/L, feed liquor manganous sulfate concentration is 0.7mol/L, electrolysing period is 12 days, at anode, obtains electrolytic manganese dioxide work in-process.
Aftertreatment: the NaOH alkali lye that is first 20% by concentration is washed acid neutralization, to pH be 8.0, then the sulfuric acid H that is 1%-4% by concentration
2sO
4soda removal of impurities, to pH be 7.0, it is 80 ℃ that rinse cycle keeps treatment temp.The particle that is particle diameter≤15um by manganese dioxide product abrasive dust again; After blending, obtain automobile power cell electrolysis special Manganse Dioxide.
The product Manganse Dioxide content 92.50% that the present embodiment obtains, Cu≤3ppm, Pb≤5ppm, Ni≤3ppm, Co≤3ppm, especially Fe reach below 10ppm, and K≤300ppm, Na≤3000ppm, Ca≤300ppm, Mg≤300ppm, Mo≤1ppm, hydrochloric acid is not tolerant≤and 0.01%, specific surface area 35m
2/ g-40m
2/ g.
Embodiment 5
A, Leaching of manganese sulfate: granularity>=150 object manganese oxide powder, troilite powder, industrial sulphuric acid are put in leaching reactive tank according to the ratio of weight ratio 10000g:1000g:2000g, low whipping speed is that 115rpm, temperature are to react 2 hours under the condition of 90 ℃, then stirring velocity is adjusted to 60rpm, temperature is 95 ℃, passes into sulfurous gas SO simultaneously
2gas, manganese oxide powder and sulfurous gas SO
2the ratio of gas intake is 10000g:1.5mol, and the reaction times is 1.5 hours, and leaching obtains the molten slurries of rough manganous sulfate.The manganese content of manganese oxide powder is 16.5%, and effective sulfur content in sulfurous iron ore (weight ratio) is 30%.
B, neutralized ex iron: with embodiment 1 operation.
C, heavy metal removal of impurities: the thick manganese sulfate solution temperature that heating steps b obtains is brought up to 90 ℃, slowly adds barium sulphide BaS and sodium sulphite Na
2the cured blend of S, cured blend is 30% sodium sulphite Na
2s solution is that 0.15L:0.85L mixes with 25% barium sulphide BaS solution according to volume ratio, the speed that cured blend adds is 5g/L/min, detection is with embodiment 1, according to the ratio of reaction soln: flocculating aids=100L:20g, drop into pearlite filtering aid, after stirring 25min, remove by filter throw out and obtain filtrate, in filtrate, add polyacrylamide complex polyelectrolyte particle, the complex polyelectrolyte particle adding and the ratio of filtrate are 5g:100L, add latter standing 1 day, obtain the manganese sulfate solution after removal of impurities.
D, electrolysis and aftertreatment: the manganese sulfate solution after the removal of impurities that step c is obtained proceeds in electrolyzer and carries out electrolysis, and electrolytic condition is: electrolysis temperature is 98 ℃, anodic current density 110A/m
2, electrolytic solution sulfuric acid H
2sO
4concentration 0.32mol/L, feed liquor manganous sulfate concentration is 1.1mol/L, electrolysing period is 8 days, at anode, obtains electrolytic manganese dioxide work in-process.
Aftertreatment: the NaOH alkali lye that is first 20% by concentration is washed acid neutralization, to pH be 7.5, then the sulfuric acid H that is 1%-4% by concentration
2sO
4soda removal of impurities, to pH be 6.5, it is 90 ℃ that rinse cycle keeps treatment temp.The particle that is particle diameter≤13um by manganese dioxide product abrasive dust again; After blending, obtain automobile power cell electrolysis special Manganse Dioxide.
The product Manganse Dioxide content 93.50% that the present embodiment obtains, Cu≤3ppm, Pb≤5ppm, Ni≤3ppm, Co≤3ppm, especially Fe reach below 10ppm, and K≤300ppm, Na≤3000ppm, Ca≤300ppm, Mg≤300ppm, Mo≤1ppm, hydrochloric acid is not tolerant≤and 0.01%, specific surface area 35m
2/ g-40m
2/ g.
The above embodiment of the present invention scheme is only can not limit the present invention to explanation of the present invention, in claim, pointed out the scope of product moiety of the present invention, component proportions, preparation method's parameter, and the scope of parameter of the present invention is not pointed out in above-mentioned explanation, therefore, in the implication suitable with claims of the present invention and any change in scope, be all considered to be in the scope that is included in claims.
The present invention is through multidigit electrolytic manganese dioxide researchist long term operation experience accumulation, and create by creative work, finally realize automobile power cell electrolytic manganese dioxide product and reach following requirement: 1. the content of the index such as impurity F e, Cu, Pb, Ni, Co, K, Na, Ca, Mg is low, Cu≤3ppm, Pb≤5ppm, Ni≤3ppm, Co≤3ppm, Mo≤1.0ppm, especially Fe reach below 10ppm; 2. specific surface area 35m
2/ g-40m
2/ g; 3. rinsing production technique is selected rational neutralizing agent, makes impurity K, Na content be reduced to bottom line; 4. finished particle degree is controlled at 13-15 micron left and right, and particle size distribution is concentrated.With respect to existing electrolytic manganese dioxide product, the present invention, by introducing catalyzer, effective reaction conditions, has simplified Production Flow Chart, improves production technique efficiency, and the product performance high-quality obtaining, has finally lowered production cost.
Claims (6)
1. a preparation method for automobile power cell electrolysis special Manganse Dioxide, is characterized in that, this preparation method's step comprises:
A, Leaching of manganese sulfate: granularity>=150 object manganese oxide powder, troilite powder, industrial sulphuric acid are put in leaching reactive tank according to the ratio of weight ratio 10000g:800 ~ 1500g:1500 ~ 2200g, low whipping speed is that 80 ~ 120rpm, temperature are to react 1.5 ~ 2 hours under the condition of 80 ~ 90 ℃, then stirring velocity is adjusted to 60 ~ 70rpm, temperature is 85 ~ 95 ℃, passes into sulfurous gas SO simultaneously
2gas, manganese oxide powder and sulfurous gas SO
2the ratio of gas intake is 10000g:0.5-2.0mol, and the reaction times is 1.0-1.5 hour, and leaching obtains the molten slurries of rough manganous sulfate;
B, neutralized ex iron: under normal temperature condition, in the molten slurries of rough manganous sulfate that obtain toward step a, add bicarbonate of ammonia, residual H in neutralization solution
2sO
4, making pH is 4.5, stops adding bicarbonate of ammonia, detects concentration≤10 of ferrous ion in solution
-5during mol/L, be qualified, if the concentration > of ferrous ion 10
-5mol/L, adds granularity>=300 object manganese oxide powder, until ferrous ion content is qualified in mixed solution, after ferrous ion is qualified, continuing to add bicarbonate of ammonia to adjust pH value is 6.5, detects concentration≤10 of ferric ion in mixed solution
-5during mol/L, be qualified, if the concentration > of ferric ion 10
-5mol/L, continues to add bicarbonate of ammonia, until ferric ion content is qualified in mixed solution, removes by filter ore pulp slag and obtains thick manganese sulfate solution;
C, heavy metal removal of impurities: the thick manganese sulfate solution temperature that heating steps b obtains is brought up to 85-90 ℃, slowly adds barium sulphide BaS and sodium sulphite Na
2the cured blend of S, the speed that cured blend adds is 2-5g/L/min, every 30min, detect a Cu, Pb, Ni, the concentration of Co, as Cu≤3ppm, Pb≤5ppm, Ni≤3ppm, during Co≤3ppm, stop adding cured blend, add granularity>=300 object manganese oxide powder, make the concentration≤0.003ppm of elements Mo, according to the ratio of reaction soln: flocculating aids=100L:20-25g, drop into flocculating aids, after stirring 20-30min, remove by filter throw out and obtain filtrate, in filtrate, add complex polyelectrolyte particle, the complex polyelectrolyte particle adding and the ratio of filtrate are 2-5g:100L, add latter standing 1 day, obtain the manganese sulfate solution after removal of impurities,
D, electrolysis and aftertreatment: the manganese sulfate solution after the removal of impurities that step c is obtained proceeds in electrolyzer and carries out electrolysis, and electrolytic condition is: electrolysis temperature is 95-98 ℃, anodic current density 58-120A/m
2, electrolytic solution sulfuric acid H
2sO
4concentration 0.28-0.36mol/L, feed liquor manganous sulfate concentration is 0.7-1.2mol/L, electrolysing period is 7-11 days, at anode, obtains electrolytic manganese dioxide work in-process, and Manganse Dioxide work in-process obtain automobile power cell electrolysis special Manganse Dioxide finished product through rinsing, abrasive dust, removal of impurities, blending aftertreatment.
2. the preparation method of automobile power cell electrolysis special Manganse Dioxide according to claim 1, is characterized in that, described cured blend is 20%-30% sodium sulphite Na
2s solution is that 0.1 ~ 0.2L:0.8 ~ 0.9L mixes with 20%-30% barium sulphide BaS solution according to volume ratio.
3. according to the preparation method of the automobile power cell electrolysis special Manganse Dioxide described in claim 1 or 2 any one, described flocculating aids is any in diatomite, perlite, Mierocrystalline cellulose, asbestos, Graphite Powder 99, sawdust.
4. the preparation method of automobile power cell electrolysis special Manganse Dioxide according to claim 3, described complex polyelectrolyte particle is any in polyacrylamide, polymine, cationic starch, polymeric amide.
5. the preparation method of automobile power cell electrolysis special Manganse Dioxide according to claim 4, described rinsing is for first washing acid neutralization with the NaOH solution of 20%-25%, to pH be 7.0-9.0, use again the sulphuric acid soln soda removal of impurities of 3%-4%, to pH be 7.0 neutrality, it is 80 ~ 95 ℃ that rinse cycle keeps treatment temp.
6. according to the preparation method of the automobile power cell electrolysis special Manganse Dioxide described in claim 4 or 5 any one, described abrasive dust is for to be controlled at manganese dioxide product particle diameter between 13 ~ 15um.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110143615A (en) * | 2019-06-19 | 2019-08-20 | 贵州红星发展大龙锰业有限责任公司 | The method that electrolytic manganese dioxide and electrolytic manganese dioxide depth remove potassium |
| CN111632940A (en) * | 2020-06-02 | 2020-09-08 | 广西汇元锰业有限责任公司 | Post-treatment rinsing method for electrolytic manganese dioxide |
| CN111807413A (en) * | 2020-06-30 | 2020-10-23 | 广东邦普循环科技有限公司 | Method for recycling manganese sulfate by using power battery |
| CN114525523A (en) * | 2021-12-31 | 2022-05-24 | 广西汇元锰业有限责任公司 | Deep impurity removal process for electrolytic manganese dioxide electrolyte |
| WO2022205535A1 (en) * | 2021-03-31 | 2022-10-06 | 广西桂柳化工有限责任公司 | Method for preparing electrolytic manganese dioxide for producing lithium manganate material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102220490A (en) * | 2011-05-06 | 2011-10-19 | 广西桂柳化工有限责任公司 | Production method of electrolytic manganese dioxide |
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| CN102220490A (en) * | 2011-05-06 | 2011-10-19 | 广西桂柳化工有限责任公司 | Production method of electrolytic manganese dioxide |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110143615A (en) * | 2019-06-19 | 2019-08-20 | 贵州红星发展大龙锰业有限责任公司 | The method that electrolytic manganese dioxide and electrolytic manganese dioxide depth remove potassium |
| CN111632940A (en) * | 2020-06-02 | 2020-09-08 | 广西汇元锰业有限责任公司 | Post-treatment rinsing method for electrolytic manganese dioxide |
| CN111807413A (en) * | 2020-06-30 | 2020-10-23 | 广东邦普循环科技有限公司 | Method for recycling manganese sulfate by using power battery |
| CN111807413B (en) * | 2020-06-30 | 2022-11-15 | 广东邦普循环科技有限公司 | Method for recycling manganese sulfate by using power battery |
| WO2022205535A1 (en) * | 2021-03-31 | 2022-10-06 | 广西桂柳化工有限责任公司 | Method for preparing electrolytic manganese dioxide for producing lithium manganate material |
| CN114525523A (en) * | 2021-12-31 | 2022-05-24 | 广西汇元锰业有限责任公司 | Deep impurity removal process for electrolytic manganese dioxide electrolyte |
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