CN103572316A - Preparation method of electrolytic manganese dioxide specially used for low-impurity battery - Google Patents
Preparation method of electrolytic manganese dioxide specially used for low-impurity battery Download PDFInfo
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Abstract
The invention belongs to the field of battery material processing, and in particular relates to a preparation method of electrolytic manganese dioxide specially used for a low-impurity battery. The preparation method comprises the following steps: leaching manganese sulfate; neutralizing for removing iron; removing heavy metal impurities; electrolyzing; performing post-treatment, wherein manganese oxide ore powder, iron pyrite powder and industrial sulfuric acid are soaked in the presence of SO2 to prepare coarse manganese sulfate solution; iron is removed by using ammonium hydrogen carbonate solution; the heavy metals are removed by using the vulcanization mixture; periodic electrolysis is performed to obtain manganese dioxide half-finished product at an anode; the manganese dioxide half-finished product is subjected to subsequent rinsing, crushing, impurity removal and mixing to obtain the electrolytic manganese dioxide specially used for the battery. According to the method, the production flow is simplified, the production process efficiency is improved, the obtained product has excellent performances, the contents of impurities Fe, Cu, Pb, Ni, Co, K, Na, Ca, Mg and the like are low, and finally the production cost is reduced.
Description
Technical field
The invention belongs to battery material manufacture field, specifically a kind of method of utilizing Low grade manganese ore to prepare low impurity battery electrolysis special Manganse Dioxide under hot conditions.
Background technology
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 battery 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 method of utilizing Low grade manganese ore to prepare low impurity battery electrolysis special Manganse Dioxide under pressurized high-temperature condition.
The solution of the present invention is by such realization: a kind of preparation method of low impurity battery 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 60 ~ 100rpm, temperature are to react 1.5 ~ 2 hours under the condition of 80 ~ 90 ℃, then stirring velocity is adjusted to 20 ~ 50rpm, 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:2.5-5.0mol, and the reaction times is 1.0-1.5 hour, and leaching obtains the molten slurries of rough manganous sulfate.The manganese content of the manganese oxide powder that the present invention adopts is 16-20%, and effective sulfur content in sulfurous iron ore (weight ratio) is 25-30%, industrial sulphuric acid H
2sO
4>=97%.
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 that step b is obtained, 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, 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 100-120A/m
2, electrolytic solution H
2sO
4concentration 0.30-0.35mol/L, manganous sulfate concentration is 0.8-1.2mol/L, electrolysing period is 8-10 days, at anode, obtains electrolytic manganese dioxide work in-process.
First Manganse Dioxide work in-process are broken into the granularity of 20mm-40mm, then put into and in rinse tank, carry out 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, hot water wash acid temperature is controlled at 90-95 ℃, and directly in hot water, the low 0.5g/L of sulfuric acid content is qualified; Weak base rinsing temperature is controlled at 55-60 ℃, and the time is 5-8 hour; Highly basic rinsing temperature is controlled at 60-70 ℃, when pH value reaches 7.0, stops highly basic rinsing; Hot water soda temperature is controlled as 90-95 ℃, and the time is 6-7 hour; Acid backwash temperature is controlled at 90-95 ℃, and the time is 1-2 hour; Last hot water rinsing temperature is controlled at 90-95 ℃, and the time is 4-10 hour, and after rinsing, product obtains low impurity battery electrolysis special Manganse Dioxide through pulverizing, removal of impurities, blending again.
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, in described rinsing, weak base is that volume content is 10%-17% ammoniacal liquor, and highly basic is that mass content is that 20 ~ 25% potassium hydroxide solutions or mass content are 20 ~ 25% lithium hydroxide solutions.
As further restriction of the present invention, described pulverizing is that manganese dioxide product is pulverized as-200 order 95%-99% ,-325 order 70%-80%.
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 battery electrolysis special 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≤1ppm, Pb≤3ppm, Ni≤1ppm, Co≤1ppm, especially Fe reach below 30ppm, 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 30m
2/ g-32m
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 distribution range is concentrated.
(2) preparation method of the present invention produces battery electrolysis special Manganse Dioxide, by introducing catalyzer, effective reaction conditions, has simplified Production Flow Chart, and production technique efficiency is provided, and the product performance high-quality obtaining, has finally lowered production cost.
Embodiment
The preparation method who describes a kind of low impurity battery electrolysis special Manganse Dioxide of the present invention below in conjunction with embodiment, 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 70rpm, temperature are to react 1.5 hours under the condition of 85 ℃, then stirring velocity is adjusted to 25rpm, temperature is 85 ℃, passes into sulfurous gas SO simultaneously
2gas, manganese oxide powder and sulfurous gas SO
2the ratio of gas intake is 10000g:2.5mol, 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 that step b is obtained is heated to 85-90 ℃, slowly add barium sulphide BaS and sodium sulphite Na
2the cured blend of S, 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, 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 120A/m
2, electrolytic solution H
2sO
4concentration 0.35mol/L, feed liquor manganous sulfate concentration is 1.2mol/L, electrolysing period is 8 days, at anode, obtains electrolytic manganese dioxide work in-process.
First Manganse Dioxide work in-process are broken into the granularity of 20mm-40mm, then put into and in rinse tank, carry out 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, hot water wash acid temperature is controlled at 90 ℃, and directly in hot water, the low 0.5g/L of sulfuric acid content is qualified; Weak base rinsing temperature is controlled at 55 ℃, and the time is 5 hours; Highly basic rinsing temperature is controlled at 60 ℃, when pH value reaches 7.0, stops highly basic rinsing; It is 95 ℃ that hot water soda temperature is controlled, and the time is 6 hours; Acid backwash temperature is controlled at 90 ℃, and the time is 2 hours; Last hot water rinsing temperature is controlled at 90 ℃, and the time is 10 hours, and after rinsing, product obtains low impurity battery electrolysis special Manganse Dioxide through pulverizing, removal of impurities, blending again.Weak base used is that volume content is 15% ammoniacal liquor above, and highly basic is that mass content is 22.5% potassium hydroxide solution.
The product Manganse Dioxide content 93.50% that the present embodiment obtains, Cu≤1ppm, Pb≤3ppm, Ni≤1ppm, Co≤1ppm, especially Fe reach below 30ppm, make impurity K≤0.03%, and Na content is reduced to bottom line, and hydrochloric acid is not tolerant≤and 0.01%; Specific surface area 30m
2/ g-32m
2/ g; Rinsing production technique is selected rational neutralizing agent; Finished particle degree distribution range is concentrated.
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 60rpm, temperature are to react 2 hours under the condition of 90 ℃, then stirring velocity is adjusted to 30rpm, temperature is 90 ℃, passes into sulfurous gas SO simultaneously
2gas, manganese oxide powder and sulfurous gas SO
2the ratio of gas intake is 10000g:5.0mol, 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 18%, and effective sulfur content in sulfurous iron ore (weight ratio) is 26%.
B, neutralized ex iron: with the operation in embodiment 1.
C, heavy metal removal of impurities: the thick manganese sulfate solution that step b is obtained is heated to 90 ℃, slowly add barium sulphide BaS and sodium sulphite Na
2the cured blend of S, 20% sodium sulphite Na
2s solution is that 0.15L:0.85L 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 reaction soln: the ratio of flocculating aids 100L:20g drops 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, 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 105A/m
2, electrolytic solution 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.
First Manganse Dioxide work in-process are broken into the granularity of 20mm-40mm, then put into and in rinse tank, carry out 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, hot water wash acid temperature is controlled at 95 ℃, and directly in hot water, the low 0.5g/L of sulfuric acid content is qualified; Weak base rinsing temperature is controlled at 58 ℃, and the time is 5 hours; Highly basic rinsing temperature is controlled at 65 ℃, when pH value reaches 7.0, stops highly basic rinsing; It is 90 ℃ that hot water soda temperature is controlled, and the time is 6 hours; Acid backwash temperature is controlled at 95 ℃, and the time is 1 hour; Last hot water rinsing temperature is controlled at 95 ℃, and the time is 4 hours, and after rinsing, product obtains low impurity battery electrolysis special Manganse Dioxide through pulverizing, removal of impurities, blending again.Weak base used is that volume content is 12% ammoniacal liquor above, and highly basic is that mass content is 25% lithium hydroxide solution.
The product Manganse Dioxide content 93.00% that the present embodiment obtains, Cu≤1ppm, Pb≤3ppm, Ni≤1ppm, Co≤1ppm, especially Fe reach below 30ppm, make impurity K≤0.03%, and Na content is reduced to bottom line, and hydrochloric acid is not tolerant≤and 0.01%; Specific surface area 30m
2/ g-32m
2/ g; Finished particle degree distribution range is concentrated.
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 80rpm, temperature are to react 1.5 hours under the condition of 85 ℃, then stirring velocity is adjusted to 20rpm, temperature is 95 ℃, passes into sulfurous gas SO simultaneously
2gas, manganese oxide powder and sulfurous gas SO
2the ratio of gas intake is 10000g:3.0mol, 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 19%, and effective sulfur content in sulfurous iron ore (weight ratio) is more than 27%.
B, neutralized ex iron: with operational requirement in embodiment 1.
C, heavy metal removal of impurities: the thick manganese sulfate solution that step b is obtained is heated to 90 ℃, slowly add barium sulphide BaS and sodium sulphite Na
2the cured blend of S, 25% 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, 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 115A/m
2, electrolytic solution H
2sO
4concentration 0.35mol/L, manganous sulfate concentration is 1.0mol/L, electrolysing period is 9 days, at anode, obtains electrolytic manganese dioxide work in-process.
First Manganse Dioxide work in-process are broken into the granularity of 20mm-40mm, then put into and in rinse tank, carry out 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, hot water wash acid temperature is controlled at 92 ℃, and directly in hot water, the low 0.5g/L of sulfuric acid content is qualified; Weak base rinsing temperature is controlled at 57 ℃, and the time is 6 hours; Highly basic rinsing temperature is controlled at 68 ℃, when pH value reaches 7.0, stops highly basic rinsing; It is 92 ℃ that hot water soda temperature is controlled, and the time is 7 hours; Acid backwash temperature is controlled at 90 ℃, and the time is 2 hours; Last hot water rinsing temperature is controlled at 93 ℃, and the time is 7 hours, and after rinsing, product obtains low impurity battery electrolysis special Manganse Dioxide through pulverizing, removal of impurities, blending again.Weak base used is that volume content is 17% ammoniacal liquor above, and highly basic is that mass content is 20% potassium hydroxide solution.
The product Manganse Dioxide content 92.50% that the present embodiment obtains, Cu≤1ppm, Pb≤3ppm, Ni≤1ppm, Co≤1ppm, especially Fe reach below 30ppm, make impurity K≤0.03%, and Na content is reduced to bottom line, and hydrochloric acid is not tolerant≤and 0.01%; Specific surface area 30m
2/ g-32m
2/ g; Finished particle degree distribution range is concentrated.
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 50rpm, temperature is 95 ℃, passes into sulfurous gas SO simultaneously
2gas, manganese oxide powder and sulfurous gas SO
2the ratio of gas intake is 10000g:3.0mol, 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 20%, and effective sulfur content in sulfurous iron ore (weight ratio) is 28%.
B, neutralized ex iron: with embodiment 1 operation.
C, heavy metal removal of impurities: the thick manganese sulfate solution that step b is obtained is heated to 90 ℃, slowly add barium sulphide BaS and sodium sulphite Na
2the cured blend of S, 30% sodium sulphite Na
2s solution is that 0.1L:0.9L mixes with 25% 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, 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 100A/m
2, electrolytic solution H
2sO
4concentration 0.30mol/L, feed liquor manganous sulfate concentration is 0.9mol/L, electrolysing period is 8 days, at anode, obtains electrolytic manganese dioxide work in-process.
First Manganse Dioxide work in-process are broken into the granularity of 20mm-40mm, then put into and in rinse tank, carry out 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, hot water wash acid temperature is controlled at 93 ℃, and directly in hot water, the low 0.5g/L of sulfuric acid content is qualified; Weak base rinsing temperature is controlled at 60 ℃, and the time is 6 hours; Highly basic rinsing temperature is controlled at 70 ℃, when pH value reaches 7.0, stops highly basic rinsing; It is 93 ℃ that hot water soda temperature is controlled, and the time is 6 hours; Acid backwash temperature is controlled at 95 ℃, and the time is 1.5 hours; Last hot water rinsing temperature is controlled at 90 ℃, and the time is 8 hours, and after rinsing, product obtains low impurity battery electrolysis special Manganse Dioxide through pulverizing, removal of impurities, blending again.Weak base used is that volume content is 10% ammoniacal liquor above, and highly basic is that mass content is 25% lithium hydroxide solution.
The product Manganse Dioxide content 93.5% that the present embodiment obtains, Cu≤1ppm, Pb≤3ppm, Ni≤1ppm, Co≤1ppm, especially Fe reach below 30ppm, make impurity K≤0.03%, and Na content is reduced to bottom line, and hydrochloric acid is not tolerant≤and 0.01%; Specific surface area 30m
2/ g-32m
2/ g; Finished particle degree distribution range is concentrated.
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 70rpm, temperature are to react 2 hours under the condition of 90 ℃, then stirring velocity is adjusted to 30rpm, temperature is 95 ℃, passes into sulfurous gas SO simultaneously
2gas, manganese oxide powder and sulfurous gas SO
2the ratio of gas intake is 10000g:5.0mol, 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 16.5%, and effective sulfur content in sulfurous iron ore (weight ratio) is 25%.
B, neutralized ex iron: with embodiment 1 operation.
C, heavy metal removal of impurities: the thick manganese sulfate solution that step b is obtained is heated to 90 ℃, slowly add barium sulphide BaS and sodium sulphite Na
2the cured blend of S, 20% sodium sulphite Na
2s solution is that 0.2L:0.8L mixes with 20% 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, 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 105A/m
2, electrolytic solution H
2sO
4concentration 0.35mol/L, feed liquor manganous sulfate concentration is 1.2mol/L, electrolysing period is 8 days, at anode, obtains electrolytic manganese dioxide work in-process.
First Manganse Dioxide work in-process are broken into the granularity of 20mm-40mm, then put into and in rinse tank, carry out 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, hot water wash acid temperature is controlled at 95 ℃, and directly in hot water, the low 0.5g/L of sulfuric acid content is qualified; Weak base rinsing temperature is controlled at 60 ℃, and the time is 5 hours; Highly basic rinsing temperature is controlled at 70 ℃, when pH value reaches 7.0, stops highly basic rinsing; It is 90 ℃ that hot water soda temperature is controlled, and the time is 6 hours; Acid backwash temperature is controlled at 95 ℃, and the time is 2 hours; Last hot water rinsing temperature is controlled at 90 ℃, and the time is 5 hours, and after rinsing, product obtains low impurity battery electrolysis special Manganse Dioxide through pulverizing, removal of impurities, blending again.Weak base used is that volume content is 14% ammoniacal liquor above, and highly basic is that mass content is 25% potassium hydroxide solution.
The product Manganse Dioxide content 93.50% that the present embodiment obtains, Cu≤1ppm, Pb≤3ppm, Ni≤1ppm, Co≤1ppm, especially Fe reach below 30ppm, make impurity K≤0.03%, and Na content is reduced to bottom line, and hydrochloric acid is not tolerant≤and 0.01%; Specific surface area 30m
2/ g-32m
2/ g; Finished particle degree distribution range is concentrated.
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 battery electrolysis special 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≤1ppm, Pb≤3ppm, Ni≤1ppm, Co≤1ppm, especially Fe reach below 30ppm; 2. specific surface area 30m
2/ g-32m
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 distribution range is concentrated.With respect to existing electrolytic manganese dioxide product, the present invention, by introducing catalyzer, effective reaction conditions, has simplified Production Flow Chart, production technique efficiency is provided, the comprehensive utilization ratio that realizes low levels oxidation manganese ore, the product performance high-quality obtaining, has finally reduced production cost.
Claims (6)
1. a preparation method for low impurity battery 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 60 ~ 100rpm, temperature are to react 1.5 ~ 2 hours under the condition of 80 ~ 90 ℃, then stirring velocity is adjusted to 20 ~ 50rpm, 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:2.5-5.0mol, 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 that step b is obtained is heated to 85-90 ℃, slowly add 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, 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 100-120A/m
2, electrolytic solution H
2sO
4concentration 0.30-0.35mol/L, feed liquor manganous sulfate concentration is 0.8-1.2mol/L, electrolysing period is 8-10 days, at anode, obtains electrolytic manganese dioxide work in-process;
First Manganse Dioxide work in-process are broken into the granularity of 20mm-40mm, then put into and in rinse tank, carry out 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, hot water wash acid temperature is controlled at 90-95 ℃, until the low 0.5g/L of sulfuric acid content is qualified in hot water; Weak base rinsing temperature is controlled at 55-60 ℃, and the time is 5-8 hour; Highly basic rinsing temperature is controlled at 60-70 ℃, when pH value reaches 7.0, stops highly basic rinsing; Hot water soda temperature is controlled as 90-95 ℃, and the time is 6-7 hour; Acid backwash temperature is controlled at 90-95 ℃, and the time is 1-2 hour; Last hot water rinsing temperature is controlled at 90-95 ℃, and the time is 4-10 hour, and after rinsing, product obtains low impurity battery electrolysis special Manganse Dioxide through pulverizing, removal of impurities, blending again.
2. the preparation method of low impurity battery 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 low impurity battery 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 low impurity battery 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 low impurity battery electrolysis special Manganse Dioxide according to claim 4, in described rinsing, weak base is that volume content is 10%-17% ammoniacal liquor, and highly basic is that mass content is that 20 ~ 25% potassium hydroxide solutions or mass content are 20 ~ 25% lithium hydroxide solutions.
6. according to the preparation method of the low impurity battery electrolysis special Manganse Dioxide described in claim 4 or 5 any one, described pulverizing is that manganese dioxide product is pulverized as-200 order 95%-99% ,-325 order 70%-80%.
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| CN104477999A (en) * | 2014-12-25 | 2015-04-01 | 贵州大龙汇成新材料有限公司 | Method for preparing manganese sulfate by absorbing sulfur dioxide in flue gas by composite pulp |
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| CN113088998B (en) * | 2021-03-31 | 2022-08-19 | 广西桂柳新材料股份有限公司 | Preparation method of electrolytic manganese dioxide for producing lithium manganate material |
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