CN111792674A - Chemical method and process for reducing impurities of electrolytic manganese dioxide - Google Patents
Chemical method and process for reducing impurities of electrolytic manganese dioxide Download PDFInfo
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- CN111792674A CN111792674A CN202010644966.4A CN202010644966A CN111792674A CN 111792674 A CN111792674 A CN 111792674A CN 202010644966 A CN202010644966 A CN 202010644966A CN 111792674 A CN111792674 A CN 111792674A
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- manganese dioxide
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- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 title claims abstract description 128
- 239000012535 impurity Substances 0.000 title claims abstract description 21
- 238000001311 chemical methods and process Methods 0.000 title claims description 16
- 238000000034 method Methods 0.000 claims abstract description 32
- 238000005406 washing Methods 0.000 claims abstract description 29
- 239000000126 substance Substances 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 238000000926 separation method Methods 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000001914 filtration Methods 0.000 claims abstract description 17
- 239000006228 supernatant Substances 0.000 claims abstract description 17
- 238000004062 sedimentation Methods 0.000 claims abstract description 16
- 230000008569 process Effects 0.000 claims abstract description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 46
- 238000003756 stirring Methods 0.000 claims description 35
- 239000000047 product Substances 0.000 claims description 30
- 239000012065 filter cake Substances 0.000 claims description 28
- 239000003513 alkali Substances 0.000 claims description 22
- 239000000706 filtrate Substances 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 14
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 14
- 238000003801 milling Methods 0.000 claims description 14
- 238000005554 pickling Methods 0.000 claims description 10
- 230000009467 reduction Effects 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 8
- 238000004806 packaging method and process Methods 0.000 claims description 8
- 239000012043 crude product Substances 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 238000003825 pressing Methods 0.000 claims description 7
- 238000007789 sealing Methods 0.000 claims description 7
- 239000010865 sewage Substances 0.000 claims description 7
- 239000002002 slurry Substances 0.000 claims description 7
- 238000004064 recycling Methods 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 abstract description 4
- 239000002253 acid Substances 0.000 abstract description 4
- 239000011575 calcium Substances 0.000 abstract description 4
- 229910052742 iron Inorganic materials 0.000 abstract description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052791 calcium Inorganic materials 0.000 abstract description 3
- 239000007788 liquid Substances 0.000 abstract description 3
- 239000011777 magnesium Substances 0.000 abstract description 3
- 229910052749 magnesium Inorganic materials 0.000 abstract description 3
- 229910052759 nickel Inorganic materials 0.000 abstract description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 abstract description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 abstract description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052804 chromium Inorganic materials 0.000 abstract description 2
- 239000011651 chromium Substances 0.000 abstract description 2
- 238000010992 reflux Methods 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 abstract 1
- 238000010586 diagram Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000005389 magnetism Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 238000012805 post-processing Methods 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000005347 demagnetization Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/02—Oxides; Hydroxides
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention relates to the technical field of manganese dioxide preparation, in particular to a chemical method and a process for reducing impurities of electrolytic manganese dioxide. The invention adopts a chemical method to reduce impurities such as magnetic substances, calcium, magnesium and the like in electrolytic manganese dioxide, the electrolytic manganese dioxide is crushed and then is added with an acid washing process, water washing and filtration, iron, nickel, chromium and zinc parts are subjected to a series of chemical reactions, then the separation of sulfate impurities and manganese dioxide is realized by means of sedimentation, solid-liquid separation and the like, and the reflux process of supernatant liquid is recycled.
Description
Technical Field
The invention relates to the technical field of manganese dioxide manufacturing, in particular to a chemical method and a process for reducing impurities of electrolytic manganese dioxide.
Background
Manganese dioxide is used as an important lithium manganate-grade battery raw material, has the advantages of large discharge capacity, small volume, strong activity and the like, is a main development direction of the manganese industry, and has considerable current situation and prospect. The current process flow for producing electrolytic manganese dioxide is leaching → purifying → electrolyzing → post-processing, and the post-processing comprises stripping, crushing, slurrying, neutralizing, alkali washing, drying and packaging. Magnetic substances and other related impurities can be brought into raw ores, the whole purification cannot be realized in the production process, the magnetic substances are brought into products due to equipment abrasion and the like caused by the friction between the products and equipment in the processes of product peeling, crushing and the like, the magnetic substances in the products are continuously improved, and the magnetic substances of the produced products are as high as 10000ppb-28000 ppb. The product contains higher magnetic substances, which can affect the use of the downstream battery industry. The content of the magnetic substances is in direct proportion to the self-discharge rate of the battery, and the more the magnetic substances are, the more the electric quantity loss caused by self-discharge is, and the discharge performance of the battery is influenced. Part of magnetic substances such as impurity iron are easily dissolved in the electrolyte, side reaction occurs, the service life of the battery is shortened, the safety performance is reduced, and the specific capacity and the energy density are reduced.
Disclosure of Invention
The present invention is directed to a chemical method and process for reducing impurities in electrolytic manganese dioxide, which solves the problems set forth above in the background art.
A chemical method and process for reducing impurities in electrolytic manganese dioxide, comprising the steps of:
step 1: manganese oxide ore roasting reduction method or 'two-ore one-step method' is used for preparing manganese dioxide crude product;
step 2: milling the prepared manganese dioxide coarse product by a milling system to ensure that the particle size of the manganese dioxide is below 300 meshes;
and step 3: placing the milled manganese dioxide into a reaction container, adding a proper amount of sulfuric acid, heating, pickling, and stirring;
and 4, step 4: stirring for more than 2h under the condition of keeping the temperature for chemical reaction, and settling and separating;
and 5: recovering supernatant after settling separation, performing filter pressing on the underflow slurry, recovering filtrate, and washing filter cakes with water;
step 6: adding a proper amount of alkali liquor into the filter cake after washing, stirring for more than 2 hours, and then filtering and spray-washing;
and 7: and (4) after filtering, treating the filtrate in a sewage station, drying the filter cake to obtain a high-quality manganese dioxide product, and sealing and packaging.
Preferably, the mass fraction of the sulfuric acid added in the step 3 is 0.3-10%, and the heating temperature is 80-98 ℃.
Preferably, the stirring time in the step 4 is more than 2 hours, and sedimentation separation is performed by using a sedimentation device;
preferably, the supernatant in the step 5 is mainly sulfuric acid, and the concentration of the supernatant can be used for recycling in the step 1 after being adjusted;
preferably, the concentration of the alkali liquor in the step 6 is 10-50g/L, and the stirring time is more than 2 h.
Preferably, in the step 7, the water content of the filter cake (product) is below 35%, and the pH value is 5-7.
Compared with the prior art, the invention has the beneficial effects that: the elements affecting the magnetic substance are mainly Fe, Ni, Gr, Zn, etc. The invention adopts a chemical method to reduce impurities such as magnetic substances, calcium, magnesium and the like in electrolytic manganese dioxide, the electrolytic manganese dioxide is crushed and then is added with an acid washing process, water washing and filtering, a series of chemical reactions are carried out on iron, nickel, chromium and zinc parts, then the separation of sulfate impurities and manganese dioxide is realized by means of sedimentation, solid-liquid separation and the like, the reflux process of the supernatant is recycled, the method can greatly improve the product quality, the magnetic substances of the product can reach 800 plus 6000ppb, simultaneously, the proposal can reduce the magnetic substances in the manganese dioxide and simultaneously add the alkali liquor, can also effectively reduce the contents of calcium and magnesium in the manganese dioxide, compared with the traditional scheme, the scheme can effectively reduce the usage amount of the alkali liquor in the neutralization reaction and reduce the production cost through water washing.
Drawings
FIG. 1 is a process flow diagram of the present invention;
FIG. 2 is a schematic diagram of the change of magnetism reducing rate with acidity according to the present invention;
FIG. 3 is a schematic diagram showing the change of magnetism reducing rate with reaction time according to the present invention
FIG. 4 is a schematic diagram showing the change of magnetic reduction rate with pickling temperature according to the present invention.
Detailed Description
The invention discloses a chemical method and a process for reducing impurities of electrolytic manganese dioxide, and the invention is further detailed by specific examples.
The acid used in the invention is sulfuric acid, the magnetism reduction rate of manganese dioxide prepared by the reaction is influenced by the increase of the concentration of the sulfuric acid, the pickling temperature and the reaction time, and the following results are obtained after a plurality of experiments, and are specifically shown in fig. 2 and fig. 3.
As shown in FIG. 2, when the acidity is 0.3 g/1-1.2 g/l, the unit slope of the magnetic reduction rate curve is the largest, and when the acidity is more than 2.44g/l, the slope is reduced.
From FIGS. 3 and 4, it is understood that the demagnetization rate increases with the reaction time and the pickling temperature.
Thus, several sets of examples were set up for comparative experiments:
example 1
A chemical method and process for reducing impurities in electrolytic manganese dioxide, comprising the steps of:
step 1: manganese oxide ore roasting reduction method or 'two-ore one-step method' is used for preparing manganese dioxide crude product;
step 2: milling the prepared manganese dioxide coarse product by a milling system to ensure that the particle size of the manganese dioxide is below 300 meshes;
and step 3: placing the milled manganese dioxide into a reaction container, adding a proper amount of sulfuric acid, heating, pickling, and stirring;
and 4, step 4: stirring for more than 2h under the condition of keeping the temperature for chemical reaction, and settling and separating;
and 5: recovering supernatant after settling separation, performing filter pressing on the underflow slurry, recovering filtrate, and washing filter cakes with water;
step 6: adding a proper amount of alkali liquor into the filter cake after washing, stirring for more than 2 hours, and then filtering and spray-washing;
and 7: and (4) after filtering, treating the filtrate in a sewage station, drying the filter cake to obtain a high-quality manganese dioxide product, and sealing and packaging.
Wherein, the mass fraction of the sulfuric acid added in the step 3 is 0.3%, the heating temperature is 80 ℃, the stirring time in the step 4 is more than 2h, and sedimentation separation is carried out by using sedimentation equipment, the supernatant in the step 5 is mainly sulfuric acid, the concentration can be recycled in the step 1 after being adjusted, the concentration of the alkali liquor in the step 6 is 10-50g/L, the stirring time is more than 2h, the water content of the filter cake (product) in the step 7 is less than 35%, and the pH value is 5-7.
Example 2
A chemical method and process for reducing impurities in electrolytic manganese dioxide, comprising the steps of:
step 1: manganese oxide ore roasting reduction method or 'two-ore one-step method' is used for preparing manganese dioxide crude product;
step 2: milling the prepared manganese dioxide coarse product by a milling system to ensure that the particle size of the manganese dioxide is below 300 meshes;
and step 3: placing the milled manganese dioxide into a reaction container, adding a proper amount of sulfuric acid, heating, pickling, and stirring;
and 4, step 4: stirring for more than 2h under the condition of keeping the temperature for chemical reaction, and settling and separating;
and 5: recovering supernatant after settling separation, performing filter pressing on the underflow slurry, recovering filtrate, and washing filter cakes with water;
step 6: adding a proper amount of alkali liquor into the filter cake after washing, stirring for more than 2 hours, and then filtering and spray-washing;
and 7: and (4) after filtering, treating the filtrate in a sewage station, drying the filter cake to obtain a high-quality manganese dioxide product, and sealing and packaging.
Wherein, the mass fraction of the sulfuric acid added in the step 3 is 4%, the heating temperature is 80 ℃, the stirring time in the step 4 is more than 2h, and sedimentation separation is carried out by using sedimentation equipment, the supernatant in the step 5 is mainly sulfuric acid, the concentration can be recycled in the step 1 after being adjusted, the concentration of the alkali liquor in the step 6 is 10-50g/L, the stirring time is more than 2h, the water content of the filter cake (product) in the step 7 is less than 35%, and the pH value is 5-7.
Example 3
Step 1: manganese oxide ore roasting reduction method or 'two-ore one-step method' is used for preparing manganese dioxide crude product;
step 2: milling the prepared manganese dioxide coarse product by a milling system to ensure that the particle size of the manganese dioxide is below 300 meshes;
and step 3: placing the milled manganese dioxide into a reaction container, adding a proper amount of sulfuric acid, heating, pickling, and stirring;
and 4, step 4: stirring for more than 2h under the condition of keeping the temperature for chemical reaction, and settling and separating;
and 5: recovering supernatant after settling separation, performing filter pressing on the underflow slurry, recovering filtrate, and washing filter cakes with water;
step 6: adding a proper amount of alkali liquor into the filter cake after washing, stirring for more than 2 hours, and then filtering and spray-washing;
and 7: and (4) after filtering, treating the filtrate in a sewage station, drying the filter cake to obtain a high-quality manganese dioxide product, and sealing and packaging.
Wherein, the mass fraction of the sulfuric acid added in the step 3 is 0.3%, the heating temperature is 90 ℃, the stirring time in the step 4 is more than 2h, and sedimentation separation is carried out by using sedimentation equipment, the supernatant in the step 5 is mainly sulfuric acid, the concentration can be recycled in the step 1 after being adjusted, the concentration of the alkali liquor in the step 6 is 10-50g/L, the stirring time is more than 2h, the water content of the filter cake (product) in the step 7 is less than 35%, and the pH value is 5-7.
Example 4
Step 1: manganese oxide ore roasting reduction method or 'two-ore one-step method' is used for preparing manganese dioxide crude product;
step 2: milling the prepared manganese dioxide coarse product by a milling system to ensure that the particle size of the manganese dioxide is below 300 meshes;
and step 3: placing the milled manganese dioxide into a reaction container, adding a proper amount of sulfuric acid, heating, pickling, and stirring;
and 4, step 4: stirring for more than 2h under the condition of keeping the temperature for chemical reaction, and settling and separating;
and 5: recovering supernatant after settling separation, performing filter pressing on the underflow slurry, recovering filtrate, and washing filter cakes with water;
step 6: adding a proper amount of alkali liquor into the filter cake after washing, stirring for more than 2 hours, and then filtering and spray-washing;
and 7: and (4) after filtering, treating the filtrate in a sewage station, drying the filter cake to obtain a high-quality manganese dioxide product, and sealing and packaging.
Wherein, the mass fraction of the sulfuric acid added in the step 3 is 4%, the heating temperature is 95 ℃, the stirring time in the step 4 is more than 2h, and sedimentation separation is carried out by using sedimentation equipment, the supernatant in the step 5 is mainly sulfuric acid, the concentration can be recycled in the step 1 after being adjusted, the concentration of the alkali liquor in the step 6 is 10-50g/L, the stirring time is more than 2h, the water content of the filter cake (product) in the step 7 is less than 35%, and the pH value is 5-7.
Example 5
Step 1: manganese oxide ore roasting reduction method or 'two-ore one-step method' is used for preparing manganese dioxide crude product;
step 2: milling the prepared manganese dioxide coarse product by a milling system to ensure that the particle size of the manganese dioxide is below 300 meshes;
and step 3: placing the milled manganese dioxide into a reaction container, adding a proper amount of sulfuric acid, heating, pickling, and stirring;
and 4, step 4: stirring for more than 2h under the condition of keeping the temperature for chemical reaction, and settling and separating;
and 5: recovering supernatant after settling separation, performing filter pressing on the underflow slurry, recovering filtrate, and washing filter cakes with water;
step 6: adding a proper amount of alkali liquor into the filter cake after washing, stirring for more than 2 hours, and then filtering and spray-washing;
and 7: and (4) after filtering, treating the filtrate in a sewage station, drying the filter cake to obtain a high-quality manganese dioxide product, and sealing and packaging.
Wherein, the mass fraction of the sulfuric acid added in the step 3 is 8%, the heating temperature is 95 ℃, the stirring time in the step 4 is more than 2h, and sedimentation separation is carried out by using sedimentation equipment, the supernatant in the step 5 is mainly sulfuric acid, the concentration can be recycled in the step 1 after being adjusted, the concentration of the alkali liquor in the step 6 is 10-50g/L, the stirring time is more than 2h, the water content of the filter cake (product) in the step 7 is less than 35%, and the pH value is 5-7.
The results of detecting the internal weight of each group of manganese dioxide after the reaction are shown in the following table
The removal rate of calcium and magnesium ions in the final product is continuously improved along with the continuous improvement of the reflected acidity and the reflected time in the table.
Meanwhile, when different alkali liquor concentrations are used, the product PH is as follows:
the process adds one-time water washing and filtering after acid washing, so that the amount of alkali used for neutralization is greatly reduced. The alkali liquor used in the prior art is 8 percent sodium hydroxide solution, the PH requirement is 5-7, and the alkali content of the alkali liquor can be reduced to 4 percent.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and the preferred embodiments of the present invention are described in the above embodiments and the description, and are not intended to limit the present invention. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (6)
1. A chemical method and a process for reducing impurities of electrolytic manganese dioxide are characterized in that: the method comprises the following steps:
step 1: manganese oxide ore roasting reduction method or 'two-ore one-step method' is used for preparing manganese dioxide crude product;
step 2: milling the prepared manganese dioxide coarse product by a milling system to ensure that the particle size of the manganese dioxide is below 300 meshes;
and step 3: placing the milled manganese dioxide into a reaction container, adding a proper amount of sulfuric acid, heating, pickling, and stirring;
and 4, step 4: stirring for more than 2h under the condition of keeping the temperature for chemical reaction, and settling and separating;
and 5: recovering supernatant after settling separation, performing filter pressing on the underflow slurry, recovering filtrate, and washing filter cakes with water;
step 6: adding a proper amount of alkali liquor into the filter cake after washing, stirring for more than 2 hours, and then filtering and spray-washing;
and 7: and (4) after filtering, treating the filtrate in a sewage station, drying the filter cake to obtain a high-quality manganese dioxide product, and sealing and packaging.
2. The chemical process and technique of claim 1 for reducing impurities in electrolytic manganese dioxide, wherein: in the step 3, the mass fraction of the sulfuric acid added is 0.3-10%, and the heating temperature is 80-98 ℃.
3. The chemical process and technique of claim 1 for reducing impurities in electrolytic manganese dioxide, wherein: and in the step 4, the stirring time is more than 2 hours, and sedimentation separation is carried out by using sedimentation equipment.
4. The chemical process and technique of claim 1 for reducing impurities in electrolytic manganese dioxide, wherein: and in the step 5, the supernatant is mainly sulfuric acid, and the concentration can be used for recycling in the step 1 after being adjusted.
5. The chemical process and technique of claim 1 for reducing impurities in electrolytic manganese dioxide, wherein: in the step 6, the concentration of the alkali liquor is 10-50g/L, and the stirring time is more than 2 h.
6. The chemical process and technique of claim 1 for reducing impurities in electrolytic manganese dioxide, wherein: in the step 7, the water content of the filter cake (product) is below 35%, and the pH value is 5-7.
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| CN103572316A (en) * | 2013-11-07 | 2014-02-12 | 广西桂柳化工有限责任公司 | Preparation method of electrolytic manganese dioxide specially used for low-impurity battery |
| 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 |
| CN105152153A (en) * | 2015-09-22 | 2015-12-16 | 赵阳臣 | Comprehensive recycling method for leaching residues in electrolytic manganese metal production |
-
2020
- 2020-07-06 CN CN202010644966.4A patent/CN111792674A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003029148A2 (en) * | 2001-10-01 | 2003-04-10 | Erachem Comilog | Method for preparing a mixed zinc and manganese oxide |
| CN102220490A (en) * | 2011-05-06 | 2011-10-19 | 广西桂柳化工有限责任公司 | Production method of electrolytic manganese dioxide |
| CN103074496A (en) * | 2013-01-21 | 2013-05-01 | 昆明理工大学 | Method for separating and purifying magnesium dioxide from anode mud |
| CN103572316A (en) * | 2013-11-07 | 2014-02-12 | 广西桂柳化工有限责任公司 | Preparation method of electrolytic manganese dioxide specially used for low-impurity battery |
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| CN105152153A (en) * | 2015-09-22 | 2015-12-16 | 赵阳臣 | Comprehensive recycling method for leaching residues in electrolytic manganese metal production |
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Application publication date: 20201020 |