CN101892384A - Method for producing mercury-free alkaline manganese electrolytic manganese dioxide - Google Patents

Method for producing mercury-free alkaline manganese electrolytic manganese dioxide Download PDF

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CN101892384A
CN101892384A CN2010102279887A CN201010227988A CN101892384A CN 101892384 A CN101892384 A CN 101892384A CN 2010102279887 A CN2010102279887 A CN 2010102279887A CN 201010227988 A CN201010227988 A CN 201010227988A CN 101892384 A CN101892384 A CN 101892384A
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manganese
mercury
free alkaline
electrolytic
manganese dioxide
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CN101892384B (en
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陈奇志
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Guangxi Huiyuan Manganese Industry Co., Ltd.
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GUANGXI NON-FERROUS METALS GROUP HUIYUAN MANGANESE INDUSTRY Co Ltd
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Priority to US13/521,952 priority patent/US20130037416A1/en
Priority to PCT/CN2011/077011 priority patent/WO2012006935A1/en
Priority to JP2013518940A priority patent/JP5764207B2/en
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/04Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • C22B3/06Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
    • C22B3/08Sulfuric acid, other sulfurated acids or salts thereof
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20Treatment or purification of solutions, e.g. obtained by leaching
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/44Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B47/00Obtaining manganese
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B47/00Obtaining manganese
    • C22B47/0018Treating ocean floor nodules
    • C22B47/0045Treating ocean floor nodules by wet processes
    • C22B47/0081Treatment or purification of solutions, e.g. obtained by leaching
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00Electrolytic production of inorganic compounds or non-metals
    • C25B1/01Products
    • C25B1/21Manganese oxides
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Recycling

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

The production method of mercury-free alkaline manganese electrolytic manganese dioxide
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.
CN2010102279887A 2010-07-15 2010-07-15 Method for producing mercury-free alkaline manganese electrolytic manganese dioxide Active CN101892384B (en)

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CN2010102279887A CN101892384B (en) 2010-07-15 2010-07-15 Method for producing mercury-free alkaline manganese electrolytic manganese dioxide
US13/521,952 US20130037416A1 (en) 2010-07-15 2011-07-09 Method for producing mercury-free alkaline-manganese type electrolyzed 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

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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 for 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 cell
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
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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