CN107419115A - A kind of processing method of electrolytic manganese dioxide - Google Patents
A kind of processing method of electrolytic manganese dioxide Download PDFInfo
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- CN107419115A CN107419115A CN201710914186.5A CN201710914186A CN107419115A CN 107419115 A CN107419115 A CN 107419115A CN 201710914186 A CN201710914186 A CN 201710914186A CN 107419115 A CN107419115 A CN 107419115A
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- manganese dioxide
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B47/00—Obtaining manganese
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/02—Apparatus therefor
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction 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
- C22B3/08—Sulfuric acid, other sulfurated acids or salts thereof
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/22—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/21—Manganese oxides
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Abstract
The present invention relates to a kind of processing method of electrolytic manganese dioxide, it is used wears into pyrolusite and pyritic material after powder in proportion on blending transportation to the false bottom of the reative cell of roaster respectively, start roaster, then gases at high pressure are oriented to the false bottom from bottom to top, low-pressure gas is oriented to the false bottom from top to bottom simultaneously, leaching, purification, are purified liquid after being calcined, two sections of removal of impurities, electrolysis are carried out to scavenging solution again, obtains electrolytic manganese dioxide product.The present invention is filtered using the inside and outside axle for driving stirring rod to rotate to solution, and on the one hand the leachate that add barium sulphide can be stirred, and makes its reaction generation precipitation；On the other hand interior axle is entered filtering to leachate by lifting outer shaft, so as to which precipitation is retained in container, is achieved that stirring, filtering without other auxiliary equipments, substantially increases production efficiency.
Description
Technical field
The present invention relates to a kind of processing method of electrolytic manganese dioxide.
Background technology
Mainly include manganese oxide ore and manganese carbonate ore with industrial application value in natural manganese ore, according to the taste of manganese ore
It is internal and international at present that deep processing processing typically is carried out to it using two kinds of processes with the difference of impurity content：When pair
In objectionable impurities（Such as phosphorus, sulphur）Low high-grade ore can be directly using pyrometallurgical smelting process production Mn series alloy product or as battery
Manganese powder；Second, for most of manganese carbonate and partial oxidation manganese ore, the general serial salt using hydrometallurgical technology production manganese
Product.However, with the exploitation year by year to manganese resource, GOOD TASTE, the ANOMALY IN FINE QUALITY MANGANESE DEPOSITS increasingly depleted of low impurity, therefore, for
The research and development and utilization for the complicated manganese ore that manganese content is low, impurity content is high, which turn into, improves domestic manganese ore deep processing enterprise in the world
The key of the market competitiveness, also largely determine that can manganese ore processing industry sustainable development.Electricity is prepared existing
During solving manganese dioxide, clarification time length, production efficiency is influenceed.
The content of the invention
For above-mentioned technical problem, the present invention provides a kind of processing side for the electrolytic manganese dioxide for improving production efficiency
Method.
Technical scheme is used by the present invention solves above-mentioned technical problem：A kind of processing method of electrolytic manganese dioxide,
It uses the following steps：
（1）By pyrolusite and pyritic material wear into respectively after powder in proportion blending transportation to the false bottom of the reative cell of roaster
On, start roaster, gases at high pressure are then oriented to the false bottom from bottom to top, while low-pressure gas is oriented to institute from top to bottom
State false bottom；
（2）After the completion of roasting, Selectively leaching is carried out to the mixture after above-mentioned roasting, obtains manganese sulfate leachate；
（3）Manganese sulfate leachate is inputted to container, adds barium sulphide, starts the stirring rod being arranged on outer shaft and is stirred
Mix, precipitate solution；
（4）Outer shaft is lifted up, make to be arranged on hollow interior axle in outer shaft close to the container bottom one section exposes, in container
One section interior axle of the solution through exposing filter out precipitation；
（5）Filtrate after filtering is flowed out from interior axle inner chamber, and the filtrate of outflow enters the clarifier-tank being arranged on the downside of container, is purifying
Sodium Dimethyldithiocarbamate and filtrate reaction generation precipitation are added in pond；
（6）After the completion of reaction, the filter in purified bottom of pond portion filters precipitation, is purified liquid, then carry out two to scavenging solution
Section removal of impurities；
（7）By the solution left standstill after two sections of removal filtration, then ultrafiltration is to heating vessel in heating；
（8）The solution heated in container is delivered to diaphragm cell again, is electrolysed using sulfuric acid-manganese sulfate system, in sun
It is extremely upper to separate out manganese dioxide, by the manganese dioxide stripping of precipitation, broken, rinsing, milling, blending, obtain electrolytic manganese dioxide and produce
Product.
Preferably, 8g barium sulphides are added in every liter of manganese sulfate leachate.
Preferably, mixing time 45min.
Preferably, the interior axle bottom exposed is provided with the opening that connect with its inner chamber, be open on covered with filter screen.
Preferably, it is provided with stirring slurry in the clarifier-tank.
Preferably, the amount of Sodium Dimethyldithiocarbamate is every liter of solution 1g.
Preferably, the filter includes the seal cover board for being arranged on clarifier-tank bottom and being flexibly connected, on cover plate
It is provided with filter plate.
Preferably, two sections of removal of impurities carry out one section of removal of impurities to add potassium permanganate, then add activated carbon and carry out two
Section removal of impurities.
As can be known from the above technical solutions, the present invention is filtered using the inside and outside axle for driving stirring rod to rotate to solution, and one
Aspect can be stirred to the leachate for adding barium sulphide, make its reaction generation precipitation；On the other hand made by lifting outer shaft
Interior axle enters filtering to leachate, and so as to which precipitation is retained in container, stirring, mistake are achieved that without other auxiliary equipments
Filter, substantially increases production efficiency.
Embodiment
The present invention is described in detail below, illustrative examples of the invention and explanation are used for explaining the present invention herein, but
It is not as a limitation of the invention.
A kind of processing method of electrolytic manganese dioxide, it uses the following steps：
First, by pyrolusite and pyritic material wear into respectively after powder in proportion blending transportation to the vacation of the reative cell of roaster
On bottom, start roaster, gases at high pressure are then oriented to the false bottom from bottom to top, while be from top to bottom oriented to low-pressure gas
The false bottom.In implementation process, small porcelain bead is equipped with false bottom, is advantageous to increase the contact area of reactant, improves roasting
Effect.Gases at high pressure can be protected in roasting process to reactant, be catalyzed or directly participate in reacting, and gases at high pressure can incite somebody to action
Reactant on false bottom is blown afloat upwards so that reactant fully contacts, and further improves roasting effect.Due to using high pressure gas
Body, some inevitable reactant can be carried away by gases at high pressure, and therefore, the present invention from top to bottom leads low-pressure gas
To the false bottom, the low-pressure gas from gases at high pressure in addition to pressure is different, other aspect all sames；Low pressure gas from top to bottom
Body hits with gases at high pressure from bottom to top, can not only break up reactant, increases the contact area of reactant, and low
Body of calming the anger offsets a part of pressure of gases at high pressure, reactant is remained near false bottom, avoids reactant from leaking, is advantageous to
Improve roasting effect.
After the completion of roasting, Selectively leaching is carried out to the mixture after above-mentioned roasting, obtains manganese sulfate leachate；Again by sulphur
Sour manganese leachate is inputted to container, is added barium sulphide, is added 8g barium sulphides in about every liter manganese sulfate leachate, ensure precipitation
Generation.Then, starting the stirring rod being arranged on outer shaft to be stirred, outer shaft is driven by motor to be rotated, and realizes automation stirring,
Stir while precipitating solution；After stir about 45min, outer shaft is lifted up, makes to be arranged on the hollow interior axle in outer shaft and leans on
One section of the nearly container bottom exposes；In implementation process, the interior axle bottom exposed is provided with the opening connected with its inner chamber, opens
Mouthful upper solution in container filters precipitation through filter screen covered with filter screen, and the filtrate after filtering is from the outflow of interior axle inner chamber.
In implementation process, interior axle passes through container bottom, and can be arranged on bottom by bearing, and outer shaft is then not passed through container
Bottom, inside and outside axle can be connected by flat key etc., so as to rotate simultaneously；When outer shaft drives stirring rod rotation, outer shaft blocks interior
The opening of axle, prevent solution from being flowed out from opening.After outer shaft stops the rotation, outer shaft is lifted up, exposes opening；Now solution can be from
The filter screen of opening flows into the inner chamber of interior axle, realizes filtering.In order to prevent precipitation from blocking filter screen, in filter process, interior axle can be made
Rotation, precipitation is thrown away to interior axle outside using centrifugal force, avoid precipitation from being gathered near filter screen.Enter from the filtrate of interior axle outflow
Enter to be arranged on the clarifier-tank on the downside of container, Sodium Dimethyldithiocarbamate is added in clarifier-tank filtrate is purified.And the addition of Sodium Dimethyldithiocarbamate
For every liter of solution 1g, and the stirring slurry that can be rotated with interior axle being provided with clarifier-tank so that the solution in clarifier-tank fully precipitates,
Realize the purpose of purification.In implementation process, Sodium Dimethyldithiocarbamate heavy metal ion such as nickel and cobalt have good impurity-eliminating effect, only
The concentration of iron ion is possible to or can not reach standard during change, and this process can also be suitably added hydrogen peroxide to reach iron
Ion removes standard.
In implementation process, the filter includes the closure for being arranged on the clarifier-tank bottom and being flexibly connected
Plate, filter plate is provided with cover plate；After the completion of the solution reaction in clarifier-tank, seal cover board can be opened, makes solution through filter plate mistake
Filter filters off precipitation, is purified liquid, realizes that secondary filter cleans, greatly improves clean-up effect.From the above it can be seen that the present invention can be to electricity
The manganese sulfate solution solved in dioxy manganese metal preparation process carries out continuous impurity and purification, can not only improve production efficiency, Er Qiecao
Make convenient and simple, cost is low.Then two sections of removal of impurities are carried out to scavenging solution, specifically one section removal of impurities is that the amount for adding potassium permanganate is
Every liter of 8g, further arsenic in solution is cleaned；Two sections of removal of impurities are finally carried out, that is, the dosage for adding activated carbon is every liter of solution
0.1g, mixing time are 1 hour.Due to be there is likely to be after one section of removal of impurities in solution a small amount of ferric ion, aluminium from
Son and silicon, it can form colloid, add activated carbon can aggregated colloids reach precipitation, standing is filtered after 24 hours, obtained pure
Manganese sulfate filtrate.
Then manganese sulfate solution after above-mentioned filtering is poured into heating container, the temperature for controlling solution is 90 DEG C, Ran Houqi
Dynamic constant flow pump, is delivered to cathodic region by solution and is electrolysed, and electrolyte temperature is 100 DEG C, anodic current density 80A/m2, electricity
It is 0.5mol/L to solve molten sulfur acid concentration, and manganese sulfate concentration is 0.4mol/L, tank voltage 2.2V.After electrolysis 10 days, shelled by anode
From manganese dioxide, through crusher in crushing to demand particle, then rinsed using washing-alkali cleaning-washing process, first and second drift
The temperature of soda liquid is preferably 60 DEG C, and last rinse temperature is advisable using 80 DEG C, and rinse cycle is 40 hours or so.After rinsing
Electrolytic manganese dioxide collects the powder for meeting granularity requirements after flour mill is milled, and homogenizing blending about 16 hours, finally
It is made and meets defined manganese dioxide product.
Above-mentioned embodiment is used for illustrative purposes only, and is not limitation of the present invention, relevant technical field
Those of ordinary skill, can be so that various changes can be made and modification without departing from the spirit and scope of the present invention, therefore institute
There is equivalent technical scheme also to belong to scope of the invention.
Claims (8)
1. a kind of processing method of electrolytic manganese dioxide, it uses the following steps：
（1）By pyrolusite and pyritic material wear into respectively after powder in proportion blending transportation to the false bottom of the reative cell of roaster
On, start roaster, gases at high pressure are then oriented to the false bottom from bottom to top, while low-pressure gas is oriented to institute from top to bottom
State false bottom；
（2）After the completion of roasting, Selectively leaching is carried out to the mixture after above-mentioned roasting, obtains manganese sulfate leachate；
（3）Manganese sulfate leachate is inputted to container, adds barium sulphide, starts the stirring rod being arranged on outer shaft and is stirred
Mix, precipitate solution；
（4）Outer shaft is lifted up, make to be arranged on hollow interior axle in outer shaft close to the container bottom one section exposes, in container
One section interior axle of the solution through exposing filter out precipitation；
（5）Filtrate after filtering is flowed out from interior axle inner chamber, and the filtrate of outflow enters the clarifier-tank being arranged on the downside of container, is purifying
Sodium Dimethyldithiocarbamate and filtrate reaction generation precipitation are added in pond；
（6）After the completion of reaction, the filter in purified bottom of pond portion filters precipitation, is purified liquid, then carry out two to scavenging solution
Section removal of impurities；
（7）By the solution left standstill after two sections of removal filtration, then ultrafiltration is to heating vessel in heating；
（8）The solution heated in container is delivered to diaphragm cell again, is electrolysed using sulfuric acid-manganese sulfate system, in sun
It is extremely upper to separate out manganese dioxide, by the manganese dioxide stripping of precipitation, broken, rinsing, milling, blending, obtain electrolytic manganese dioxide and produce
Product.
2. the processing method of electrolytic manganese dioxide according to claim 1, it is characterised in that：Add in every liter of manganese sulfate leachate
Enter 8g barium sulphides.
3. the processing method of electrolytic manganese dioxide according to claim 1, it is characterised in that：Mixing time 45min.
4. the processing method of electrolytic manganese dioxide according to claim 1, it is characterised in that：The interior axle bottom exposed be provided with
Its inner chamber connection opening, opening on covered with filter screen.
5. the processing method of electrolytic manganese dioxide according to claim 1, it is characterised in that：Stirring is provided with the clarifier-tank
Slurry.
6. the processing method of electrolytic manganese dioxide according to claim 1, it is characterised in that：The amount of Sodium Dimethyldithiocarbamate is every liter of solution
1g。
7. the processing method of electrolytic manganese dioxide according to claim 1, it is characterised in that：The filter includes setting
Filter plate is provided with clarifier-tank bottom and the seal cover board of flexible connection, cover plate.
8. the processing method of electrolytic manganese dioxide according to claim 1, it is characterised in that：Two sections of removal of impurities are high to add
Potassium manganate carries out one section of removal of impurities, then adds activated carbon and carries out two sections of removal of impurities.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710914186.5A CN107419115A (en) | 2017-09-30 | 2017-09-30 | A kind of processing method of electrolytic manganese dioxide |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710914186.5A CN107419115A (en) | 2017-09-30 | 2017-09-30 | A kind of processing method of electrolytic manganese dioxide |
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| Publication Number | Publication Date |
|---|---|
| CN107419115A true CN107419115A (en) | 2017-12-01 |
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|---|---|---|---|
| CN201710914186.5A Pending CN107419115A (en) | 2017-09-30 | 2017-09-30 | A kind of processing method of electrolytic manganese dioxide |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116143185A (en) * | 2022-12-08 | 2023-05-23 | 广西汇元锰业有限责任公司 | Method for preparing high-purity cobalt sulfate from electrolytic manganese sulfide slag |
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| CN103014320A (en) * | 2012-12-07 | 2013-04-03 | 中信大锰矿业有限责任公司 | Method for preparing manganese sulfate by using sulfur-containing carbonaceous manganese carbonate ore |
| CN103695636A (en) * | 2013-12-24 | 2014-04-02 | 柳州豪祥特科技有限公司 | Preparation method of electrolytic manganese dioxide |
| CN203540443U (en) * | 2013-10-23 | 2014-04-16 | 山东正泰重工科技有限公司 | Air type agitating and proportioning machine |
| CN203923330U (en) * | 2014-05-12 | 2014-11-05 | 龙南县堉然科技有限公司 | A kind of rare earth waste reclaims just settler |
| CN204583024U (en) * | 2015-03-13 | 2015-08-26 | 广东弘和高新材料股份有限公司 | A kind of paint mixing and filter |
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2017
- 2017-09-30 CN CN201710914186.5A patent/CN107419115A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN201793760U (en) * | 2010-06-22 | 2011-04-13 | 陈榜龙 | Fluid preparation device for producing electrolytic manganese metal by adopting two-ores method |
| CN103014320A (en) * | 2012-12-07 | 2013-04-03 | 中信大锰矿业有限责任公司 | Method for preparing manganese sulfate by using sulfur-containing carbonaceous manganese carbonate ore |
| CN203540443U (en) * | 2013-10-23 | 2014-04-16 | 山东正泰重工科技有限公司 | Air type agitating and proportioning machine |
| CN103695636A (en) * | 2013-12-24 | 2014-04-02 | 柳州豪祥特科技有限公司 | Preparation method of electrolytic manganese dioxide |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116143185A (en) * | 2022-12-08 | 2023-05-23 | 广西汇元锰业有限责任公司 | Method for preparing high-purity cobalt sulfate from electrolytic manganese sulfide slag |
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Application publication date: 20171201 |