CN103011294B - Preparation method of manganese tetraoxide - Google Patents
Preparation method of manganese tetraoxide Download PDFInfo
- Publication number
- CN103011294B CN103011294B CN201210547731.9A CN201210547731A CN103011294B CN 103011294 B CN103011294 B CN 103011294B CN 201210547731 A CN201210547731 A CN 201210547731A CN 103011294 B CN103011294 B CN 103011294B
- Authority
- CN
- China
- Prior art keywords
- washing
- preparation
- trimanganese tetroxide
- manganese
- sulfate solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a preparation method of manganese tetraoxide, which comprises the following steps: a, heating a manganese sulfate solution, adding ammonia water to take reaction, precipitating the reactant, filtering and washing the sediment; b, adding water into the sediment washed in the step a to mix, controlling the liquid-solid ratio to be 3-10 cubic meters to 1 ton, heating the mixture and controlling the temperature at 80-150 DEG C, utilizing the ammonia water to regulate pH value to be 8-12, and controlling the reaction time to be 1-6 hours; after reaction, filtering and washing the reactant; and c, roasting the solid substances which are obtained by washing and filtering in the step b under inert gas shielding at the temperature of 200-800 DEG C for 1-6 hours; and after roasting, cooling, washing, filtering and drying the roasted substances to obtain the manganese tetraoxide product. Compared with the prior art, the preparation method can reduce the raw material cost, simplify the technical processes, and deeply purify and remove sulfur by combination of a wet method and a fire refining process, so as to ensure the quality of the manganese tetraoxide final product.
Description
Technical field
The invention belongs to manganic compound synthesis technical field, be specifically related to a kind of preparation method of high purity trimanganese tetroxide.
Background technology
High-purity mangano-manganic oxide is the important raw and processed materials of synthetic soft magnetic manganese-zinc ferrite.Its preparation method mainly contains: roasting method, reduction method, oxidation style and electrolytic process.The current production of China all adopts electrolytic metal Mn suspension oxidation style substantially.It is that to take pure electrolytic metal Mn sheet be raw material, utilizes air or oxygen to make oxygenant, prepares a kind of method of trimanganese tetroxide under certain temperature and additive concentration.The trimanganese tetroxide specific surface area that the method makes is generally at 4～7m
2/ g, technique is relatively simple, and shortcoming is that foreign matter content is higher, and contains impurity element selenium in the raw material electrolytic manganese adopting, and in Mn-Zn ferrite pre-burning and sintering circuit selenium, can be oxidized and volatilize, and production unit and atmospheric environment are had to certain influence.And the method adopts electrolytic metal Mn as raw material, and cost is higher.
Therefore, from raw ore without electrolytic manganese operation, prepare trimanganese tetroxide and become very necessary.In recent years, adopt manganese salt solution thermal oxidation method to prepare trimanganese tetroxide both at home and abroad, this method is under alkaline condition, add certain additive control current potential, with the oxyhydroxide that air or oxygen is bivalent manganese in manganese sulfate solution or manganese by the sulphuric leachate of manganese ore, be oxidized to a kind of preparation method of trimanganese tetroxide.Due to without electrolysis, saved complicated manganese electrolysis process, saved the electric energy of the approximately 7000kw.h that 1 ton of electrolytic metal Mn of every production consumes, in addition the main raw material(s) using is manganese ore, sulfuric acid and ammoniacal liquor, their wide material sources, and inexpensive, thereby be considered to the most rising a kind of preparation method always.But this method subject matter is that in gained trimanganese tetroxide, sulphur content is high, does not reach GB requirement.Chinese patent CN1821091A increases by a hydrothermal treatment consists process on this basis, alkali formula manganous sulfate is converted into manganous hydroxide and has reduced sulphur content.But two kinds of methods all need to add air or oxygen oxidation, because the oxidizing potential of oxygen is high, for fear of manganese, generate many oxide, need add additive control current potential.Reagent consumption and gas consumption have been increased.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of preparation method of high purity trimanganese tetroxide.
The technical solution adopted for the present invention to solve the technical problems is: the preparation method of trimanganese tetroxide, comprises the steps:
A, by manganese sulfate solution heating, then add ammoniacal liquor reaction, after precipitation, filter, washing;
B, the precipitation after step a washing is added to water size mixing, control liquid-solid ratio is 3～10m
3︰ 1t, and add 80～150 ℃ of thermal control temperature, with ammoniacal liquor, controlling pH value is 8～12, reaction times 1～6h; After reaction, filter, wash;
C, the solid matter obtaining by step b washing, after filtering carry out roasting, 200～800 ℃ of maturing temperatures, roasting time 1～6h in the situation that of protection of inert gas; Roasting by cooling, washing, filter, obtain trimanganese tetroxide product after dry.
Wherein, in aforesaid method step b, control liquid-solid ratio is 4～8m
3︰ 1t, and add 90～130 ℃ of thermal control temperature, with ammoniacal liquor, controlling pH value is 9～11, reaction times 3～6h.
Wherein, in aforesaid method step c, 400～800 ℃ of maturing temperatures, roasting time 2～6h.
Wherein, in aforesaid method step a, described manganese sulfate solution is containing manganese 10～120g/L.
Wherein, in aforesaid method step a, described manganese sulfate solution is to be obtained through sulfuric acid to leach, removal of impurities by manganese ore.
Further, described manganese sulfate solution is containing Ca < 10mg/L, Mg < 50mg/L, Si < 10mg/L, Na < 50mg/L, K < 10mg/L, heavy metal < 10mg/L.
Wherein, in aforesaid method step a, by the temperature of manganese sulfate solution heating, it is 40～60 ℃.
Wherein, in aforesaid method step a, the concentration of described ammoniacal liquor is 6～15%, adds that to make the pH value of solution after ammoniacal liquor be 9～11.
Wherein, in aforesaid method step c, described rare gas element is nitrogen or argon gas.
The invention has the beneficial effects as follows: the oxide compound of manganese has various ways, generate single trimanganese tetroxide, must be controlled at certain potentials, blowing air or dioxygen oxidation, because oxidizing potential is high, must add additive.And precipitation (being precipitation of hydroxide) after at high temperature hydrothermal treatment step a washing of the present invention, rationally control liquid-solid ratio, temperature of reaction, pH value and reaction times, utilize a small amount of dioxygen oxidation adsorbing in solution, do not need to pass into large quantity of air or oxygen, oxidizing potential can be not too high, do not need to add additive control current potential, can generate single trimanganese tetroxide; Simultaneously; solid matter (trimanganese tetroxide primary products) after step b is washed, filtered is under protection of inert gas; solid phase high-temperature heat treatment again; control maturing temperature and time; the content that can very effectively control calcium in product, magnesium and sulphur, finally reaches the object of preparing high-purity mangano-manganic oxide.The present invention has reduced raw materials cost with respect to prior art, has simplified processing step, and in conjunction with wet method and the sulphur removal of pyrogenic process deep purifying, final trimanganese tetroxide quality is protected.
Embodiment
Below by embodiment, the present invention is further described.
The preparation method of trimanganese tetroxide of the present invention, comprises the steps:
A, by manganese sulfate solution heating, then add ammoniacal liquor reaction, after precipitation, filter, washing;
B, the precipitation after step a washing is added to water size mixing, control liquid-solid ratio is 3～10m
3︰ 1t, and add 80～150 ℃ of thermal control temperature, with ammoniacal liquor, controlling pH value is 8～12, reaction times 1～6h; After reaction, filter, wash;
C, the solid matter obtaining by step b washing, after filtering carry out roasting, 200～800 ℃ of maturing temperatures, roasting time 1～6h in the situation that of protection of inert gas; Roasting by cooling, washing, filter, obtain trimanganese tetroxide product after dry.
Step b of the present invention rationally controls liquid-solid ratio, temperature of reaction, pH value and reaction times, utilize a small amount of dioxygen oxidation adsorbing in solution, do not need to pass into large quantity of air or oxygen, oxidizing potential can be not too high, do not need to add additive control current potential, can generate single trimanganese tetroxide.Step c is under protection of inert gas; solid phase high-temperature heat treatment, controls maturing temperature and time again, can very effectively control the content of calcium in product, magnesium and sulphur; step b integrating step c dual function of the present invention, finally reaches the object of preparing high-purity mangano-manganic oxide.Step b of the present invention adds thermal control temperature at 80～150 ℃, it will be understood by those skilled in the art that the mode that can heat by encloses container when temperature is greater than 100 ℃ reaches.
Preferably, in aforesaid method step b, control liquid-solid ratio is 4～8m
3︰ 1t, and add 90～130 ℃ of thermal control temperature, with ammoniacal liquor, controlling pH value is 9～11, reaction times 3～6h.
Preferably, in aforesaid method step c, 400～800 ℃ of maturing temperatures, roasting time 2～6h.
Preferably, in aforesaid method step a, described manganese sulfate solution is containing manganese 10～120g/L.
Preferably, for the cost that further economizes in raw materials, in aforesaid method step a, described manganese sulfate solution is to be obtained through sulfuric acid to leach, removal of impurities by manganese ore.
Preferably, too high on impact of the present invention for fear of foreign matter content, described manganese sulfate solution is containing Ca < 10mg/L, Mg < 50mg/L, Si < 10mg/L, Na < 50mg/L, K < 10mg/L, heavy metal < 10mg/L.
Preferably, in aforesaid method step a, by the temperature of manganese sulfate solution heating, it is 40～60 ℃; Be heated to the particle form generation that this temperature is conducive to manganous hydroxide.
Preferably, in aforesaid method step a, the concentration of described ammoniacal liquor is 6～15%, adds that to make the pH value of solution after ammoniacal liquor be 9～11.Controlling pH value, to be less than 11 object be control calcium, magnesium addition, and when pH value is higher than 11 time, calcium magnesium is easily precipitated out, and causes in product calcium-magnesium content too high, do not reach requirement, but the precipitation of the too low manganese of pH value is incomplete.
Preferably, in aforesaid method step c, described rare gas element is nitrogen or argon gas.
Below by embodiment, the specific embodiment of the present invention is described further, but therefore protection scope of the present invention is not limited among embodiment.
Embodiment mono-
To purify qualified (is Ca < 10mg/L, Mg < 50mg/L, Si < 10mg/L, Na < 50mg/L, K < 10mg/L, heavy metal < 10mg/L afterwards, the manganese sulfate solution 5L that manganese concentration down together) is 40g/l, put into reactor, be heated to 30 ℃, slowly add 6% ammonia precipitation process, controlling endpoint pH is 8 again.Precipitate rear filtration, with after deionized water wash 5 times, filter cake has been transferred in another reactor, added deionized water to size mixing, liquid-solid ratio is 8:1, reheats 85 ℃, controls pH value 9, after hydrothermal treatment consists 6h, filter, use deionized water wash 3 times, obtain trimanganese tetroxide primary products.By trimanganese tetroxide primary products, in nitrogen protection situation, 600 ℃ of roasting 3h desulfurization in-depths, process again.Through cooling, washing, filter, obtain high-purity mangano-manganic oxide product after dry, product index is: Mn:71.85%, SiO
2: 0.01%, CaO:0.008%, MgO:0.009%, Na
2o:0.004%, K
2o:0.003%, F
2o
3: 0.06%, S:0.035%, Se: nothing.
Embodiment bis-
The manganese sulfate solution 5L that manganese concentration after purification is qualified is 60g/l, puts into reactor, is heated to 50 ℃, more slowly adds 8% ammonia precipitation process, and controlling endpoint pH is 9.Precipitate rear filtration, with after deionized water wash 3 times, filter cake has been transferred in another reactor, added deionized water to size mixing, liquid-solid ratio is 5:1, reheats 95 ℃, controls pH value 11, after hydrothermal treatment consists 3h, filter, use deionized water wash 3 times, obtain trimanganese tetroxide primary products.By trimanganese tetroxide primary products, in nitrogen protection situation, 400 ℃ of roasting 4h desulfurization in-depths, process again.Through cooling, washing, filter, obtain high-purity mangano-manganic oxide product after dry, product index is: Mn:71.05%, SiO
2: 0.008%, CaO:0.008%, MgO:0.008%, Na
2o:0.005%, K
2o:0.003%, F
2o
3: 0.07%, S:0.045%, Se: nothing.
Embodiment tri-
The manganese sulfate solution 5L that manganese concentration after purification is qualified is 100g/l, puts into reactor, is heated to 70 ℃, more slowly adds 12.5% ammonia precipitation process, and controlling endpoint pH is 10.Precipitate rear filtration, with after deionized water wash 2 times, filter cake has been transferred in another reactor, added deionized water to size mixing, liquid-solid ratio is 6:1, reheats 130 ℃, controls pH value 11, after hydrothermal treatment consists 2h, filter, use deionized water wash 3 times, obtain trimanganese tetroxide primary products.By trimanganese tetroxide primary products, in nitrogen protection situation, 700 ℃ of roasting 2h desulfurization in-depths, process again.Through cooling, washing, filter, obtain high-purity mangano-manganic oxide product after dry, product index is: Mn:72.05%, SiO
2: 0.01%, CaO:0.007%, MgO:0.009%, Na
2o:0.003%, K
2o:0.004%, F
2o
3: 0.03%, S:0.047%, Se: nothing.
Embodiment tetra-
The manganese sulfate solution 5L that manganese concentration after purification is qualified is 80g/l, puts into reactor, is heated to 60 ℃, more slowly adds 15% ammonia precipitation process, and controlling endpoint pH is 9.5.Precipitate rear filtration, with after deionized water wash 3 times, filter cake has been transferred in another reactor, added deionized water to size mixing, liquid-solid ratio is 4:1, reheats 120 ℃, controls pH value 9, after hydrothermal treatment consists 4h, filter, use deionized water wash 1 time, obtain trimanganese tetroxide primary products.By trimanganese tetroxide primary products, in nitrogen protection situation, 800 ℃ of roasting 1h desulfurization in-depths, process again.Through cooling, washing, filter, obtain high-purity mangano-manganic oxide product after dry, product index is: Mn:71.36%, SiO
2: 0.008%, CaO:0.01%, MgO:0.01%, Na
2o:0.005%, K
2o:0.004%, F
2o
3: 0.065%, S:0.019%, Se: nothing.
Embodiment five
The manganese sulfate solution 5L that manganese concentration after purification is qualified is 60g/l, puts into reactor, is heated to 50 ℃, more slowly adds 6% ammonia precipitation process, and controlling endpoint pH is 8.5.Precipitate rear filtration, with after deionized water wash 3 times, filter cake has been transferred in another reactor, added deionized water to size mixing, liquid-solid ratio is 5:1, reheats 90 ℃, controls pH value 10, after hydrothermal treatment consists 6h, filter, use deionized water wash 3 times, obtain trimanganese tetroxide primary products.By trimanganese tetroxide primary products, in nitrogen protection situation, 600 ℃ of roasting 4h desulfurization in-depths, process again.Through cooling, washing, filter, obtain high-purity mangano-manganic oxide product after dry, product index is: Mn:71.27%, SiO
2: 0.009%, CaO:0.01%, MgO:0.008%, Na
2o:0.007%, K
2o:0.008%, F
2o
3: 0.05%, S:0.028%, Se: nothing.
Embodiment six
The manganese sulfate solution 5L that manganese concentration after purification is qualified is 120g/l, puts into reactor, is heated to 60 ℃, more slowly adds 12% ammonia precipitation process, and controlling endpoint pH is 10.Precipitate rear filtration, with after deionized water wash 5 times, filter cake has been transferred in another reactor, added deionized water to size mixing, liquid-solid ratio is 5:1, reheats 120 ℃, controls pH value 9, after hydrothermal treatment consists 3h, filter, use deionized water wash 3 times, obtain trimanganese tetroxide primary products.By trimanganese tetroxide primary products, in nitrogen protection situation, 300 ℃ of roasting 6h desulfurization in-depths, process again.Through cooling, washing, filter, obtain high-purity mangano-manganic oxide product after dry, product index is: Mn:71.59%, SiO
2: 0.009%, CaO:0.007%, MgO:0.008%, Na
2o:0.008%, K
2o:0.005%, F
2o
3: 0.08%, S:0.05%, Se: nothing.
Claims (7)
1. the preparation method of trimanganese tetroxide, is characterized in that comprising the steps:
A, by manganese sulfate solution heating, then add ammoniacal liquor reaction, after precipitation, filter, washing; Described manganese sulfate solution is containing manganese 10～120g/L; The concentration of described ammoniacal liquor is 6～15%, adds that to make the pH value of solution after ammoniacal liquor be 9～11;
B, the precipitation after step a washing is added to water size mixing, control liquid-solid ratio is 3～10m
3︰ 1t, and add 80～150 ℃ of thermal control temperature, with ammoniacal liquor, controlling pH value is 8～12, reaction times 1～6h; Washing after reaction, filtration;
C, the solid matter obtaining by step b washing, after filtering carry out roasting, 200～800 ℃ of maturing temperatures, roasting time 1～6h in the situation that of protection of inert gas; Roasting by cooling, washing, filter, obtain trimanganese tetroxide product after dry.
2. the preparation method of trimanganese tetroxide according to claim 1, is characterized in that: in step b, control liquid-solid ratio is 4～8m
3︰ 1t, and add 90～130 ℃ of thermal control temperature, with ammoniacal liquor, controlling pH value is 9～11, reaction times 3～6h.
3. the preparation method of trimanganese tetroxide according to claim 1, is characterized in that: in step c, and 400～800 ℃ of maturing temperatures, roasting time 2～6h.
4. according to the preparation method of the trimanganese tetroxide described in claim 1,2 or 3, it is characterized in that: in step a, described manganese sulfate solution is to be obtained through sulfuric acid to leach, removal of impurities by manganese ore.
5. the preparation method of trimanganese tetroxide according to claim 4, is characterized in that: described manganese sulfate solution is containing Ca < 10mg/L, Mg < 50mg/L, Si < 10mg/L, Na < 50mg/L, K < 10mg/L, heavy metal < 10mg/L.
6. according to the preparation method of the trimanganese tetroxide described in claim 1,2 or 3, it is characterized in that: in step a, by the temperature of manganese sulfate solution heating, be 40～60 ℃.
7. according to the preparation method of the trimanganese tetroxide described in claim 1,2 or 3, it is characterized in that: in step c, described rare gas element is nitrogen or argon gas.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210547731.9A CN103011294B (en) | 2012-12-17 | 2012-12-17 | Preparation method of manganese tetraoxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210547731.9A CN103011294B (en) | 2012-12-17 | 2012-12-17 | Preparation method of manganese tetraoxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103011294A CN103011294A (en) | 2013-04-03 |
| CN103011294B true CN103011294B (en) | 2014-08-13 |
Family
ID=47960477
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210547731.9A Active CN103011294B (en) | 2012-12-17 | 2012-12-17 | Preparation method of manganese tetraoxide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103011294B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106848295B (en) * | 2017-02-20 | 2020-05-05 | 北京理工大学 | Manganese oxide, preparation method thereof and aluminum ion battery |
| CN111807414B (en) * | 2020-06-18 | 2022-06-17 | 贵州金瑞新材料有限责任公司 | Method for producing fluorine-free ultrapure manganese sulfate monohydrate by using basic salt method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1083803C (en) * | 1998-04-17 | 2002-05-01 | 段希圣 | Roasting process of preparing very pure mangano-manganic oxide and its use |
| CN1821091A (en) * | 2006-03-03 | 2006-08-23 | 北京科技大学 | Process for preparing mangano-mangaic oxide using mangenese salt hydrothermal oxidizing method |
| CN102786095A (en) * | 2012-08-16 | 2012-11-21 | 青川县青云上锰业有限公司 | Method for preparing manganous manganic oxide |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5678482B2 (en) * | 2010-06-01 | 2015-03-04 | 東ソー株式会社 | Manganese oxide and method for producing the same |
-
2012
- 2012-12-17 CN CN201210547731.9A patent/CN103011294B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1083803C (en) * | 1998-04-17 | 2002-05-01 | 段希圣 | Roasting process of preparing very pure mangano-manganic oxide and its use |
| CN1821091A (en) * | 2006-03-03 | 2006-08-23 | 北京科技大学 | Process for preparing mangano-mangaic oxide using mangenese salt hydrothermal oxidizing method |
| CN102786095A (en) * | 2012-08-16 | 2012-11-21 | 青川县青云上锰业有限公司 | Method for preparing manganous manganic oxide |
Non-Patent Citations (9)
| Title |
|---|
| Chi-Chang Hu et al..Low-Temperature Hydrothermal Synthesis of Mn3O4 and MnOOH Single Crystals: Determinant Influence of Oxidants.《Chem. Mater.》.2008,第20卷(第9期),第2890-2894页. |
| JP特開2011-251862A 2011.12.15 |
| Low-Temperature Hydrothermal Synthesis of Mn3O4 and MnOOH Single Crystals: Determinant Influence of Oxidants;Chi-Chang Hu et al.;《Chem. Mater.》;20080416;第20卷(第9期);第2890-2894页 * |
| 杨则恒等.系列纳米结构锰氧化物的水热合成.《无机化学学报》.2008,第24卷(第10期),第1695-1700页. |
| 用硫酸锰溶液直接制备四氧化三锰反应机理的研究;陈德胜等;《冶金研究》;20061231;270-273页 * |
| 硫酸锰在氨性介质中制备四氧化三锰的研究;邹兴等;《中国锰业》;20091130;第27卷(第4期);第4-6、19页 * |
| 系列纳米结构锰氧化物的水热合成;杨则恒等;《无机化学学报》;20081031;第24卷(第10期);第1695-1670页 * |
| 邹兴等.硫酸锰在氨性介质中制备四氧化三锰的研究.《中国锰业》.2009,第27卷(第4期),第4-6、19页. |
| 陈德胜等.用硫酸锰溶液直接制备四氧化三锰反应机理的研究.《冶金研究》.2006,270-273页. |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103011294A (en) | 2013-04-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100357361C (en) | Method for preparing high purity iron oxide yellow and iron oxide red using titanium dioxide byproduct ferrous sulfate | |
| CN110331288B (en) | Method for selectively extracting lithium from waste lithium iron phosphate material | |
| CN104118893B (en) | One utilizes titanium white waste acid manufacture level magnesium sulfate method | |
| CN103101935B (en) | Method for preparing lithium carbonate from coal ash | |
| CN107188149B (en) | A kind of technique of LITHIUM BATTERY high-purity nm ferric phosphate | |
| CN102220478B (en) | Preparation method for vanadium pentoxide | |
| CN108149022B (en) | A kind of method of vanadium slag blank roasting ammonium vanadium extraction | |
| CN102070198A (en) | Method for preparing high-purity manganese sulfate and high-purity manganese carbonate by reduction leaching of pyrolusite through scrap iron | |
| CN103011297A (en) | Method for production of high purity manganese sulfate by using pyrolusite as raw material | |
| CN103011296B (en) | Production process for high purity manganese sulfate through reduction with pyrolusite powder as raw material | |
| CN106611841A (en) | Method for preparing nickel-cobalt-manganese ternary material precursor by using nickel-cobalt slag material | |
| CN100497183C (en) | Method for preparing zirconium oxide powder from zircon | |
| CN107954474A (en) | A kind of method that vanadium product and chromium sulfate basic are produced using vanadium chromium solution | |
| CN102020299A (en) | Method for producing industrial activated aluminum oxide from pulverized fuel ash | |
| CN114684801B (en) | Method for preparing high-purity ferric phosphate by using pyrite cinder | |
| CN103387266B (en) | Method for direct production of ultra-pure manganese sulfate by non-carbon reduction of manganese dioxide | |
| CN102502722A (en) | Preparation method of high-purity magnesium oxide | |
| CN115196676A (en) | Preparation method of high-purity vanadium pentoxide suitable for vanadium electrolyte | |
| CN106348319A (en) | Method for utilizing serpentine for preparing high-purity magnesium oxide | |
| CN102220499B (en) | Roasting-leaching method of fine vanadium slags | |
| CN103074496A (en) | Method for separating and purifying magnesium dioxide from anode mud | |
| CN105110784B (en) | Method for preparing manganese zinc ferrite by using artificial rutile mother liquor | |
| CN103011294B (en) | Preparation method of manganese tetraoxide | |
| CN103011295B (en) | Reduction method for producing manganese tetroxide | |
| CN101774648A (en) | Method for preparing high-purity iron oxide and trisodium phosphate by ferro-phosphorus alkalization process |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |