CN101892384A - Method for producing mercury-free alkaline manganese electrolytic manganese dioxide - Google Patents
Method for producing mercury-free alkaline manganese electrolytic manganese dioxide Download PDFInfo
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Abstract
The invention discloses a method for producing mercury-free alkaline manganese electrolytic manganese dioxide, which comprises the following steps of: (1) mixing manganese oxide ore and iron pyrite, adding the mixture and sulfuric acid into a continuous leaching tank formed by connecting 1 to 7 stirring leaching tanks in series simultaneously and forming one-stage or multistage continuous leaching, and performing a process reaction at the temperature of between 90 and 95 DEG C for 3 to 4 hours to obtain solution of manganese sulfate; (2) purifying the solution of manganese sulfate for impurity removal; and (3) after performing ultrafiltration on the purified solution of manganese sulfate, heating the solution of manganese sulfate by a plate-type heat exchanger to 90 to 100 DEG C, allowing the solution to enter a head tank and adding a prepared suspending agent and a foaming agent simultaneously, supplying the mixture to each electrolytic bath through a pipeline, and electrolyzing to obtain the mercury-free alkaline manganese electrolytic manganese dioxide. The method has the advantages of wide adaptability of the manganese oxide ore, short process flow, low production cost and the like.
Description
Technical field
The present invention relates to a kind of production method of mercury-free alkaline manganese electrolytic manganese dioxide, the method that the manganese oxide ore of the ultralow grade of particularly a kind of usefulness " two ore deposit methods " leaching is produced mercury-free alkaline manganese electrolytic manganese dioxide.
Background technology
Alkaline Mn cell is as performance in the battery industry and the high-power battery of price than the best, have characteristics such as stable operating voltage, big electric current continuous discharge, excellent property, period of storage long (can reach 3～5 years), low-temperature performance and leak resistance are good, welcome by domestic and international consumers in general.Produce the used main raw material of alkaline Mn cell---mercury-free alkaline manganese electrolytic manganese dioxide, the annual consumption in its whole world surpasses 300,000 tons, and annual with the speed increase more than 10%, has vast market prospect.
Produce in the technology of electrolytic manganese dioxide at present, being raw material with manganese carbonate ore or manganese oxide ore mainly, in smelting production process, is raw material with homemade manganese carbonate ore, because of manganous carbonate content in the ore low (below 30%), cause that the manganese ore consumption is very big, production cost is too high; With the manganese oxide ore is raw material, the main at present processing method that adopts leaches system liquid or produces electrolytic manganese dioxide with " two ore deposit methods " after the reducing roasting manganese oxide ore is arranged, and leach this processing method of system liquid after adopting the reducing roasting manganese oxide ore, have that technical process is long, production cost is high, and easily to shortcomings such as plant area's surrounding enviroment pollute; With high-grade manganese oxide ore is that raw material, usefulness " two ore deposit methods " are produced electrolytic manganese dioxide, be that dioxide ore for manganese leaches system liquid together with the reductive agent sulfurous iron ore, because adopting, present domestic manganese metallurgy industry manganese ore is interrupted extract technology, promptly only in leaching vat, directly the manganese ore dissolving is entered solution, this technology is that grade exists leaching yield low at the ore below 25% to low-grade manganese, shortcomings such as the turnover time of material between equipment is long, and number of devices increase and utilization ratio are low; And employed such higher-grade manganese resource (grade is more than 25%) reduces day by day, will be difficult to keep permanent production.The Guangxi manganese ore resources is abundant, but major part is a low-grade manganese stone, is characterized in that manganese content is low, foreign matter content is high, is not fully developed for a long time.
Summary of the invention
It can be main raw with ultralow grade manganese oxide ore that technical problem to be solved by this invention provides a kind of, produces the method for mercury-free alkaline manganese electrolytic manganese dioxide with " two ore deposit methods ".
The present invention solves the problems of the technologies described above the production method that the technical scheme that adopts provides a kind of mercury-free alkaline manganese electrolytic manganese dioxide, in turn include the following steps: (1) is mixed the back with manganese oxide ore and is successively put in the continuous leaching vat that are composed in series by 1～7 leaching vat that stirring simultaneously with sulfuric acid with sulfurous iron ore, form one or more levels continuous leaching, the process reaction temperature is controlled at 90～95 ℃, in about 3～4 hours of reaction times, get manganese sulfate solution; (2) manganese sulfate solution is carried out purification and impurity removal; (3) manganese sulfate solution after will purifying is through behind the ultrafiltration, after being heated to 90～100 ℃ ℃, plate-type heat exchanger enters header tank, add suspension agent and the whipping agent for preparing simultaneously, be conducted to each electrolyzer by pipeline, electrolytic condition is: electrolyte temperature is 100～103 ℃, and anodic current density is 80～85A/m
2, bath voltage is 2.2～3.5V, electrolysing period is 12～20 days, obtains mercury-free alkaline manganese electrolytic manganese dioxide after the electrolysis.
In the production method of above-mentioned mercury-free alkaline manganese electrolytic manganese dioxide, manganese oxide ore and sulfurous iron ore directly feed in the continuous leaching vat in 1: 0.24 ratio in the described step 1, simultaneously by 1: 0.47 ore deposit acid than allocating sulfuric acid and waste electrolyte into.
In the production method of above-mentioned mercury-free alkaline manganese electrolytic manganese dioxide, the tail washings of described waste electrolyte after from step 3 electrolysis.
In the production method of above-mentioned mercury-free alkaline manganese electrolytic manganese dioxide, after the leaching reaction is finished in the described step 1, remove potassium ion earlier, adopt neutralization to remove the iron processes deironing again, it is 6～6.5 that the deironing later stage adds lime powder regulator solution PH, and in about 3～4 hours of reaction times, temperature is 90～95 ℃.
In the production method of above-mentioned mercury-free alkaline manganese electrolytic manganese dioxide, adopt two sections continuous purification technologies that manganese sulfate solution is carried out purification and impurity removal in the described step 2, manganese sulfate solution enters one section continuous purification and adds calcium polysulfide, controlled temperature is at 60 ℃, solution enters two sections and purifies earlier through the dynamic deliming of chute, magnesium, after deliver to and leave standstill groove, left standstill 32 hours, make ageing of solution, calcium, magnesium addition precipitation are removed.
In the production method of above-mentioned mercury-free alkaline manganese electrolytic manganese dioxide, the thick product of anode electrolysis Manganse Dioxide that in the described step 3 electrolysis is obtained is crushed to the particle of 6～8mm, enter rinse tank, adopt three grades of rinsing process of washing-alkali cleaning-washing, the temperature of first and second rinsing alkali lye is 60～70 ℃, and last rinse water temperature is 80～90 ℃, and rinse cycle is about 40 hours, rinsing liquid all adopts the steam direct heating, after reach the electrolytic manganese dioxide of required granularity through abrasive dust.
In the production method of above-mentioned mercury-free alkaline manganese electrolytic manganese dioxide, carry out homogenizing to adopting close phase mode of movement to send into the gravity type boat davit mixing silo through the electrolytic manganese dioxide behind the abrasive dust, the blending time is about 16 hours.
The present invention contrasts prior art following beneficial effect: the production method of mercury-free alkaline manganese electrolytic manganese dioxide provided by the invention, with ultralow grade manganese oxide ore as main raw material, use " two ore deposit methods " directly to leach the manganese in the ultralow grade manganese oxide ore, it is assorted to obtain carrying out behind the manganese sulfate solution deeply purifying and removing, again the electrolysis production mercury-free alkaline manganese electrolytic manganese dioxide.Can use the grade of manganese oxide ore to be reduced to 16%, and the manganese oxide ore that the production technique that adopts is not only low to grade, the source is complicated is suitable for, high-grade manganese oxide ore is suitable for too, therefore, have manganese oxide ore wide adaptability, advantage such as technical process is short, production cost is low, can make full use of the abundant low-grade manganese oxide ore in Guangxi and produce the mercury-free alkaline manganese electrolytic manganese dioxide product, to rationally utilize manganese resource, the good economic benefits that reduced production costs and social benefit.
Description of drawings
Fig. 1 is the process flow sheet of the embodiment of the invention.
Embodiment
The invention will be further described below in conjunction with drawings and Examples.
Embodiment 1
To be 44.54% troilite powder mix by 1: 0.24 dried proportion manganese oxide powder, the sulphur content that will contain manganese 14.32%, with concentration is that 98% sulfuric acid adds the dilution heat of sulfuric acid that water is mixed with 100g/L, mixed oxidation manganese powder and troilite powder and the sulfuric acid for preparing successively join in the continuous leaching vat in 1: 0.47 ratio simultaneously, and constantly stir simultaneously, leaching vat are made up of leaching vat continuously, form one-level and leach continuously, the useful volume of leaching vat is 1m
3, the groove temperature is 95 ℃, to come out to leach the reaction times from leaching vat be 3 hours from being dosed into feed liquid, pH value reaches at 3～3.5 o'clock and shows that leaching reaction finishes, constantly stir in the reaction process, effusive feed liquid enters in the placed in-line with it neutralizing well from leaching vat, and the useful volume of neutralizing well is 1.5m
3, add lime powder again and carry out neutralization reaction continuously, control pH value be 6.0, the reaction times is 3 hours, the filtrate after the neutralization after filtration, filter residue is sent to the slag field, rough manganese sulfate solution.Rough manganese sulfate solution contains heavy metal and impurity such as calcium, magnesium such as copper, cobalt, nickel, lead, adopts two sections continuous purification Technologies, and rough manganese sulfate solution enters one section continuous purification and adds calcium polysulfide, controlled temperature is at 60 ℃, filter residue is sent to the slag field, and solution enters two sections and purifies earlier through the dynamic deliming of chute, magnesium, after deliver to and leave standstill groove, left standstill 32 hours, make ageing of solution, calcium, magnesium addition precipitation are removed, get the POV manganese solution, filter residue is sent to the slag field, and filtrate is sent to electrolysis.
Refining qualified manganese sulfate solution is through ultrafiltration, be heated to through plate-type heat exchanger 90 ℃ to after enter header tank and carry out suspension electrolysis.Add suspension agent and the whipping agent for preparing simultaneously, electrolyte temperature is 100 ℃, and anodic current density is 81A/m
2, bath voltage is 2.4V, and electrolysing period is 12 days, by peeling off the thick product of Manganse Dioxide on the anode, through the particle of crusher in crushing to 6～8mm, enters rinse tank again, and the useful volume of each rinse tank is 1m
3, three grades of rinsing process of employing washing-alkali cleaning-washing, the temperature of first and second rinsing alkali lye is 60 ℃, and last rinse water temperature is 80 ℃, and rinse cycle is 40 hours, and rinsing liquid all adopts the steam direct heating.Electrolytic manganese dioxide after the rinsing is sent to the pendulum type ring roll pulverizer abrasive dust and collects product powder (granularity-325 order), for eliminating product quality variance, guarantee the homogeneity of product, adopt close phase mode of movement to send the gravity type boat davit mixing silo to carry out the homogenizing blending about 16 hours, make qualified mercury-free alkaline manganese type manganese dioxide product.
Embodiment 2
To be 40.54% troilite powder mix by 1: 0.24 dried proportion manganese oxide powder, the sulphur content that will contain manganese 15.56%, with concentration is that 98% sulfuric acid adds the dilution heat of sulfuric acid that water is mixed with 100g/L, mixed oxidation manganese powder and troilite powder and the sulfuric acid for preparing successively join in the continuous leaching vat in 1: 0.47 ratio simultaneously, and constantly stir simultaneously, leaching vat are to be composed in series by three leaching vat continuously, form three grades and leach continuously, the useful volume of each leaching vat is 1m
3Feed liquid enters in the third stage leaching vat after entering second stage leaching vat again, each groove temperature is 93 ℃, to come out to leach the reaction times from third stage leaching vat be 3.5 hours from being dosed into feed liquid, constantly stir in the reaction process, effusive feed liquid enters in the placed in-line with it neutralizing well from three grades of leaching vat, and the useful volume of neutralizing well is 1.5m
3, add lime powder again and carry out neutralization reaction continuously, control pH value be 6.3,3.5 hours reaction times, the filtrate after the neutralization after filtration, filter residue is sent to the slag field, rough manganese sulfate solution.Rough manganese sulfate solution contains heavy metal and impurity such as calcium, magnesium such as copper, cobalt, nickel, lead, adopts two sections continuous purification Technologies, and rough manganese sulfate solution enters one section continuous purification and adds calcium polysulfide, controlled temperature is at 60 ℃, filter residue is sent to the slag field, and solution enters two sections and purifies earlier through the dynamic deliming of chute, magnesium, after deliver to and leave standstill groove, left standstill 32 hours, make ageing of solution, calcium, magnesium addition precipitation are removed, get the POV manganese solution, filter residue is sent to the slag field, and filtrate is sent to electrolysis.
Refining qualified manganese sulfate solution is through ultrafiltration, be heated to through plate-type heat exchanger 95 ℃ to after enter header tank and carry out suspension electrolysis.Add suspension agent and the whipping agent for preparing simultaneously, electrolyte temperature is 102 ℃, and anodic current density is 83A/m
2, bath voltage is 2.9V, and electrolysing period is 15 days, by peeling off the thick product of Manganse Dioxide on the anode, through the particle of crusher in crushing to 6～8mm, enters rinse tank again, and the useful volume of each rinse tank is 1m
3, three grades of rinsing process of employing washing-alkali cleaning-washing, the temperature of first and second rinsing alkali lye is 65 ℃, and last rinse water temperature is 85 ℃, and rinse cycle is 40 hours, and rinsing liquid all adopts the steam direct heating.Electrolytic manganese dioxide after the rinsing is sent to the pendulum type ring roll pulverizer abrasive dust and collects product powder (granularity-325 order), for eliminating product quality variance, guarantee the homogeneity of product, adopt close phase mode of movement to send the gravity type boat davit mixing silo to carry out the homogenizing blending about 16 hours, make qualified mercury-free alkaline manganese type manganese dioxide product.
Embodiment 3
To be 47.44% troilite powder mix by 1: 0.24 dried proportion manganese oxide powder, the sulphur content that will contain manganese 13.58%, with concentration is that 98% sulfuric acid adds the dilution heat of sulfuric acid that water is mixed with 100g/L, mixed oxidation manganese powder and troilite powder and the sulfuric acid for preparing successively join in the continuous leaching vat in 1: 0.47 ratio simultaneously, and constantly stir simultaneously, leaching vat are to be composed in series by seven leaching vat continuously, form seven grades and leach continuously, the useful volume of each leaching vat is 1m
3Feed liquid enters in the 3rd to the 7th grade of leaching vat after entering second stage leaching vat again, each groove temperature is 95 ℃, to come out to leach the reaction times from the 7th grade of leaching vat be 4 hours from being dosed into feed liquid, constantly stir in the reaction process, effusive feed liquid enters in the placed in-line with it neutralizing well from seven grades of leaching vat, and the useful volume of neutralizing well is 1.5m
3, add lime powder again and carry out neutralization reaction continuously, control pH value be 6.5, the filtrate after the neutralization after filtration, filter residue is sent to the slag field, rough manganese sulfate solution.Rough manganese sulfate solution contains heavy metal and impurity such as calcium, magnesium such as copper, cobalt, nickel, lead, adopts two sections continuous purification Technologies, and rough manganese sulfate solution enters one section continuous purification and adds calcium polysulfide, controlled temperature is at 60 ℃, filter residue is sent to the slag field, and solution enters two sections and purifies earlier through the dynamic deliming of chute, magnesium, after deliver to and leave standstill groove, left standstill 32 hours, make ageing of solution, calcium, magnesium addition precipitation are removed, get the POV manganese solution, filter residue is sent to the slag field, and filtrate is sent to electrolysis.
Refining qualified manganese sulfate solution enters header tank and carries out suspension electrolysis through ultrafiltration after being heated to 100 ℃ through plate-type heat exchanger.Add suspension agent and the whipping agent for preparing simultaneously, electrolyte temperature is 103 ℃, and anodic current density is 85A/m
2, bath voltage is 3.5V, and electrolysing period is 20 days, by peeling off the thick product of Manganse Dioxide on the anode, through the particle of crusher in crushing to 6～8mm, enters rinse tank again, and the useful volume of each rinse tank is 1m
3, three grades of rinsing process of employing washing-alkali cleaning-washing, the temperature of first and second rinsing alkali lye is 70 ℃, and last rinse water temperature is 85 ℃, and rinse cycle is 40 hours, and rinsing liquid all adopts the steam direct heating.Electrolytic manganese dioxide after the rinsing is sent to the pendulum type ring roll pulverizer abrasive dust and collects product powder (granularity-325 order), for eliminating product quality variance, guarantee the homogeneity of product, adopt close phase mode of movement to send the gravity type boat davit mixing silo to carry out the homogenizing blending about 16 hours, make qualified mercury-free alkaline manganese type manganese dioxide product.
Three kinds of embodiment obtain manganese dioxide product leading indicator MnO
2〉=91.0%, Fe≤60ppm, Cu≤5ppm, Pb≤5ppm, Ni≤5ppm, Co≤5ppm, Mo≤0.5ppm, As≤0.5ppm, Sb≤0.5ppm, K≤200ppm.
Though the present invention discloses as above with preferred embodiment; right its is not in order to qualification 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 (7)
1. the production method of a mercury-free alkaline manganese electrolytic manganese dioxide is characterized in that in turn including the following steps:
(1) manganese oxide ore being mixed the back with sulfurous iron ore successively puts in the continuous leaching vat that are composed in series by 1～7 leaching vat that stirring with sulfuric acid simultaneously, form one or more levels continuous leaching, the process reaction temperature is controlled at 90～95 ℃, in about 3～4 hours of reaction times, gets manganese sulfate solution;
(2) manganese sulfate solution is carried out purification and impurity removal;
(3) manganese sulfate solution after will purifying is through behind the ultrafiltration, after being heated to 90～100 ℃, plate-type heat exchanger enters header tank, add suspension agent and the whipping agent for preparing simultaneously, be conducted to each electrolyzer by pipeline, electrolytic condition is: electrolyte temperature is 100～103 ℃, and anodic current density is 80～85A/m
2, bath voltage is 2.2～3.5V, electrolysing period is 12～20 days, obtains mercury-free alkaline manganese electrolytic manganese dioxide after the electrolysis.
2. the production method of mercury-free alkaline manganese electrolytic manganese dioxide according to claim 1, it is characterized in that manganese oxide ore and sulfurous iron ore in the described step 1 directly feed in the continuous leaching vat in 1: 0.24 ratio, simultaneously by 1: 0.47 ore deposit acid than allocating sulfuric acid and waste electrolyte into.
3. the production method of mercury-free alkaline manganese electrolytic manganese dioxide according to claim 2 is characterized in that the tail washings after described waste electrolyte is from step 3 electrolysis.
4. the production method of mercury-free alkaline manganese electrolytic manganese dioxide according to claim 1, after it is characterized in that the leaching reaction is finished in the described step 1, remove potassium ion earlier, adopt neutralization to remove the iron processes deironing again, it is 6～6.5 that the deironing later stage adds lime powder regulator solution PH, in about 3～4 hours of reaction times, temperature is 90～95 ℃.
5. the production method of mercury-free alkaline manganese electrolytic manganese dioxide according to claim 1, it is characterized in that adopting in the described step 2 two sections continuous purification technologies that manganese sulfate solution is carried out purification and impurity removal, manganese sulfate solution enters one section continuous purification and adds calcium polysulfide, controlled temperature is at 60 ℃, solution enters two sections and purifies earlier through the dynamic deliming of chute, magnesium, after deliver to and leave standstill groove, left standstill 32 hours, make ageing of solution, calcium, magnesium addition precipitation are removed.
6. the production method of mercury-free alkaline manganese electrolytic manganese dioxide according to claim 1, it is characterized in that the thick product of anode electrolysis Manganse Dioxide that in the described step 3 electrolysis is obtained is crushed to the particle of 6～8mm, enter rinse tank, adopt three grades of rinsing process of washing-alkali cleaning-washing, the temperature of first and second rinsing alkali lye is 60～70 ℃, last rinse water temperature is 80～90 ℃, rinse cycle is about 40 hours, rinsing liquid all adopts the steam direct heating, after reach the electrolytic manganese dioxide of required granularity through abrasive dust.
7. the production method of mercury-free alkaline manganese electrolytic manganese dioxide according to claim 6 is characterized in that carrying out homogenizing to adopting close phase mode of movement to send into the gravity type boat davit mixing silo through the electrolytic manganese dioxide behind the abrasive dust, and the blending time is about 16 hours.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102279887A CN101892384B (en) | 2010-07-15 | 2010-07-15 | Method for producing mercury-free alkaline manganese electrolytic manganese dioxide |
| PCT/CN2011/077011 WO2012006935A1 (en) | 2010-07-15 | 2011-07-09 | Method for producing mercury-free alkaline-manganese type electrolyzed manganese dioxide |
| JP2013518940A JP5764207B2 (en) | 2010-07-15 | 2011-07-09 | Method for producing electrolytic manganese dioxide for mercury-free alkaline manganese batteries |
| US13/521,952 US20130037416A1 (en) | 2010-07-15 | 2011-07-09 | Method for producing mercury-free alkaline-manganese type electrolyzed manganese dioxide |
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| Application Number | Priority Date | Filing Date | Title |
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| CN2010102279887A CN101892384B (en) | 2010-07-15 | 2010-07-15 | Method for producing mercury-free alkaline manganese electrolytic manganese dioxide |
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| CN101892384A true CN101892384A (en) | 2010-11-24 |
| CN101892384B CN101892384B (en) | 2011-09-21 |
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| US (1) | US20130037416A1 (en) |
| JP (1) | JP5764207B2 (en) |
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| WO2012006935A1 (en) * | 2010-07-15 | 2012-01-19 | 广西有色金属集团汇元锰业有限公司 | Method for producing mercury-free alkaline-manganese type electrolyzed manganese dioxide |
| CN102560526A (en) * | 2011-12-23 | 2012-07-11 | 苏州大学 | Preparation method of high-power electrolytic manganese dioxide |
| CN103074490A (en) * | 2013-01-09 | 2013-05-01 | 广西有色金属集团汇元锰业有限公司 | Purification method in electrolytic metal manganese production process by multi-mine method |
| CN103205772A (en) * | 2013-04-15 | 2013-07-17 | 广西有色金属集团汇元锰业有限公司 | Method for producing electrolytic manganese dioxide |
| CN103560240A (en) * | 2013-11-07 | 2014-02-05 | 广西桂柳化工有限责任公司 | Preparation method of special electrolytic manganese dioxide for mercury-free alkaline battery |
| CN103643252A (en) * | 2013-12-05 | 2014-03-19 | 中信大锰矿业有限责任公司大新锰矿分公司 | Suspending agent for manganese dioxide electrolysis |
| CN103710541A (en) * | 2013-12-24 | 2014-04-09 | 柳州豪祥特科技有限公司 | Wet process for producing electrolytic manganese dioxide |
| CN104928709A (en) * | 2015-06-24 | 2015-09-23 | 上海微智知识产权服务有限公司 | Electrolytic system of manganese dioxide and production method of manganese dioxide |
| CN106480471A (en) * | 2016-11-04 | 2017-03-08 | 柳州高新区欧亚自动化设备有限责任公司 | EMD Continuous leaching process chemical combination groove pH value control device and its control method |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN115094441A (en) * | 2022-07-14 | 2022-09-23 | 广西桂柳新材料股份有限公司 | Production method of electrolytic manganese dioxide for lithium battery |
| CN115724470B (en) * | 2022-09-26 | 2024-05-07 | 广西科技师范学院 | Purification method of manganese sulfate solution |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN87102046A (en) * | 1987-06-23 | 1987-12-09 | 桂阳县电解锰厂 | Method with producing manganous sulphate solution from manganese dioxide ore |
| CN1861815A (en) * | 2005-05-14 | 2006-11-15 | 广西汇元锰业有限公司 | Process of continuously leaching manganese oxide ore |
| CN101456594A (en) * | 2007-12-14 | 2009-06-17 | 杜祖德 | Method for preparing manganese sulfate by using low grade manganese mud |
| CN101550556A (en) * | 2009-04-01 | 2009-10-07 | 广西靖西县一洲锰业有限公司 | Preparation method of electrolytic manganese dioxide for alkaline zinc-manganese battery |
Family Cites Families (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1874827A (en) * | 1931-05-12 | 1932-08-30 | Burgess Battery Co | Production of manganese dioxide |
| US2424958A (en) * | 1943-08-31 | 1947-08-05 | Dorr Co | Process of electrodepositing a manganese dioxide compound |
| US3348912A (en) * | 1963-09-23 | 1967-10-24 | Utah Construction & Mining Co | Method of preparing manganese sulfate from pyrite reduced manganese dioxide ores |
| JPS5121959B1 (en) * | 1969-06-16 | 1976-07-06 | ||
| JPS49197A (en) * | 1972-04-21 | 1974-01-05 | ||
| JPS5216880B2 (en) * | 1973-09-20 | 1977-05-12 | ||
| DE2949791A1 (en) * | 1979-12-11 | 1981-06-19 | Krupp Polysius Ag, 4720 Beckum | STORAGE AND MIXING SILO FOR SCHUETTGUT |
| JPS5988324A (en) * | 1982-11-12 | 1984-05-22 | Japan Metals & Chem Co Ltd | Method for purifying manganese sulfate solution for electrolytic manganese dioxide |
| JPS60103192A (en) * | 1983-11-09 | 1985-06-07 | Japan Metals & Chem Co Ltd | Treatment of material accumulated in electrolytic cell |
| JPS60236458A (en) * | 1984-05-10 | 1985-11-25 | Toshiba Battery Co Ltd | Battery containing no mercury |
| US4549943A (en) * | 1984-11-01 | 1985-10-29 | Union Carbide Corporation | Suspension bath and process for production of electrolytic manganese dioxide |
| JPS6244586A (en) * | 1985-08-20 | 1987-02-26 | Toshiba Battery Co Ltd | Production of electrolyzed manganese dioxide for battery |
| CN1027294C (en) * | 1991-06-04 | 1995-01-04 | 上海钢铁研究所 | Ti-alloy anode for electrolysis of MO2 |
| JP3493835B2 (en) * | 1995-10-16 | 2004-02-03 | 松下電器産業株式会社 | Method for producing manganese dioxide and alkaline dry battery using the same |
| US6589693B1 (en) * | 1999-08-05 | 2003-07-08 | Eveready Battery Company, Inc. | High discharge electrolytic manganese dioxide and an electrode and alkaline cell incorporating the same |
| JP4730488B2 (en) * | 2000-04-04 | 2011-07-20 | 東ソー株式会社 | Method for producing manganese ore processed product |
| DE60143686D1 (en) * | 2000-09-01 | 2011-02-03 | Tosoh Corp | Electrolytic manganese dioxide powder and process for its preparation |
| JP3553541B2 (en) * | 2001-11-26 | 2004-08-11 | 三井金属鉱業株式会社 | Method for producing positive electrode active material for battery and electrolytic manganese dioxide, and battery |
| US6896817B2 (en) * | 2002-04-15 | 2005-05-24 | Gregory S. Bowers | Essentially insoluble heavy metal sulfide slurry for wastewater treatment |
| CN1907866A (en) * | 2005-08-01 | 2007-02-07 | 李忠红 | Method of preparing manganomanganic oxide directly by manganese ore |
| WO2009120384A2 (en) * | 2008-03-28 | 2009-10-01 | Siemens Water Technologies Corp. | Hybrid aerobic and anaerobic wastewater and sludge treatment systems and methods |
| CN101684562A (en) * | 2008-09-28 | 2010-03-31 | 熊一言 | Liquid making technique for manganese oxide ore |
| CN101892384B (en) * | 2010-07-15 | 2011-09-21 | 广西有色金属集团汇元锰业有限公司 | Method for producing mercury-free alkaline manganese electrolytic manganese dioxide |
-
2010
- 2010-07-15 CN CN2010102279887A patent/CN101892384B/en active Active
-
2011
- 2011-07-09 US US13/521,952 patent/US20130037416A1/en not_active Abandoned
- 2011-07-09 WO PCT/CN2011/077011 patent/WO2012006935A1/en active Application Filing
- 2011-07-09 JP JP2013518940A patent/JP5764207B2/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN87102046A (en) * | 1987-06-23 | 1987-12-09 | 桂阳县电解锰厂 | Method with producing manganous sulphate solution from manganese dioxide ore |
| CN1861815A (en) * | 2005-05-14 | 2006-11-15 | 广西汇元锰业有限公司 | Process of continuously leaching manganese oxide ore |
| CN101456594A (en) * | 2007-12-14 | 2009-06-17 | 杜祖德 | Method for preparing manganese sulfate by using low grade manganese mud |
| CN101550556A (en) * | 2009-04-01 | 2009-10-07 | 广西靖西县一洲锰业有限公司 | Preparation method of electrolytic manganese dioxide for alkaline zinc-manganese battery |
Non-Patent Citations (1)
| Title |
|---|
| 《电池》 19901231 张植勤 电解二氧化锰 第45页左栏第10行-第49页左栏第9行 1-4 第20卷, 第6期 2 * |
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| WO2012006935A1 (en) * | 2010-07-15 | 2012-01-19 | 广西有色金属集团汇元锰业有限公司 | Method for producing mercury-free alkaline-manganese type electrolyzed manganese dioxide |
| CN102560526A (en) * | 2011-12-23 | 2012-07-11 | 苏州大学 | Preparation method of high-power electrolytic manganese dioxide |
| CN102560526B (en) * | 2011-12-23 | 2015-03-25 | 苏州大学 | Preparation method of high-power electrolytic manganese dioxide |
| CN103074490B (en) * | 2013-01-09 | 2014-03-12 | 广西有色金属集团汇元锰业有限公司 | Purification method in electrolytic metal manganese production process by multi-mine method |
| CN103074490A (en) * | 2013-01-09 | 2013-05-01 | 广西有色金属集团汇元锰业有限公司 | Purification method in electrolytic metal manganese production process by multi-mine method |
| CN103205772B (en) * | 2013-04-15 | 2015-07-08 | 广西有色金属集团汇元锰业有限公司 | Method for producing electrolytic manganese dioxide |
| CN103205772A (en) * | 2013-04-15 | 2013-07-17 | 广西有色金属集团汇元锰业有限公司 | Method for producing electrolytic manganese dioxide |
| CN103560240A (en) * | 2013-11-07 | 2014-02-05 | 广西桂柳化工有限责任公司 | Preparation method of special electrolytic manganese dioxide for mercury-free alkaline battery |
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| CN103643252A (en) * | 2013-12-05 | 2014-03-19 | 中信大锰矿业有限责任公司大新锰矿分公司 | Suspending agent for manganese dioxide electrolysis |
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| CN103710541A (en) * | 2013-12-24 | 2014-04-09 | 柳州豪祥特科技有限公司 | Wet process for producing electrolytic manganese dioxide |
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| CN104928709A (en) * | 2015-06-24 | 2015-09-23 | 上海微智知识产权服务有限公司 | Electrolytic system of manganese dioxide and production method of manganese dioxide |
| CN104928709B (en) * | 2015-06-24 | 2017-04-12 | 广西有色金属集团汇元锰业有限公司 | Electrolytic system of manganese dioxide and production method of manganese dioxide |
| CN106480471A (en) * | 2016-11-04 | 2017-03-08 | 柳州高新区欧亚自动化设备有限责任公司 | EMD Continuous leaching process chemical combination groove pH value control device and its control method |
| CN106480471B (en) * | 2016-11-04 | 2018-05-22 | 柳州高新区欧亚自动化设备有限责任公司 | EMD Continuous leaching process chemical combination slot pH value control devices and its control method |
| 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 |
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| CN111620355A (en) * | 2020-06-03 | 2020-09-04 | 四川兴晟锂业有限责任公司 | Method for removing potassium ions in potassium hydroxide solution |
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Also Published As
| Publication number | Publication date |
|---|---|
| CN101892384B (en) | 2011-09-21 |
| JP5764207B2 (en) | 2015-08-12 |
| US20130037416A1 (en) | 2013-02-14 |
| WO2012006935A1 (en) | 2012-01-19 |
| JP2013538936A (en) | 2013-10-17 |
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Address after: 546138 888 Meibin Road, Mayor of Laibin, Guangxi Zhuang Autonomous Region Patentee after: Guangxi Huiyuan Manganese Industry Co., Ltd. Address before: No. 58 Mei Lu, Mayor of Laibin, Guangxi Zhuang Autonomous Region Patentee before: Guangxi Non-Ferrous Metals Group Huiyuan Manganese Industry Co., Ltd. |