CN103011294A - Preparation method of manganese tetraoxide - Google Patents
Preparation method of manganese tetraoxide Download PDFInfo
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- CN103011294A CN103011294A CN2012105477319A CN201210547731A CN103011294A CN 103011294 A CN103011294 A CN 103011294A CN 2012105477319 A CN2012105477319 A CN 2012105477319A CN 201210547731 A CN201210547731 A CN 201210547731A CN 103011294 A CN103011294 A CN 103011294A
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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 the 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.Electrolytic metal Mn suspension oxidation style is all adopted in the present production of China basically.It is take pure electrolytic metal Mn sheet as raw material, utilizes air or oxygen to make oxygenant, a kind of method of preparation 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 that adopts, and in Mn-Zn ferrite pre-burning and the meeting oxidation of sintering circuit selenium and volatilization, production unit and atmospheric environment is had certain influence.And the method adopts electrolytic metal Mn as raw material, and cost is higher.
Therefore, prepare trimanganese tetroxide from raw ore without the electrolytic manganese operation 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, adding certain additive control current potential, is a kind of preparation method that the oxyhydroxide of bivalent manganese in the manganese sulfate solution or manganese is oxidized to trimanganese tetroxide with air or oxygen with the sulphuric leachate of manganese ore.Because without electrolysis, saved complicated manganese electrolysis process, saved the electric energy of about 7000kw.h that 1 ton of electrolytic metal Mn of every production consumes, the main raw material(s) that in addition uses 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 sulphur content is high in the gained trimanganese tetroxide, does not reach the GB requirement.Chinese patent CN1821091A increases by a hydrothermal treatment consists process on this basis, alkali formula manganous sulfate is converted into manganous hydroxide has reduced sulphur content.But two kinds of methods all need add the air or oxygen oxidation, because the oxidizing potential of oxygen is high, generate many oxide for fear of manganese, need to add the additive control current potential.Reagent consumption and gas consumption have been increased.
Summary of the invention
Technical problem to be solved by this invention provides 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, with manganese sulfate solution heating, add again the ammoniacal liquor reaction, filter after the precipitation, washing;
B, the precipitation after the step a washing is added water size mixing, the control liquid-solid ratio is 3～10m
3︰ 1t, and add 80～150 ℃ of thermal control temperature, be 8～12 with ammoniacal liquor control pH value, reaction times 1～6h; Filter after the reaction, wash;
C, the solid matter that obtains with step b washing, after filtering carry out roasting, 200～800 ℃ of maturing temperatures, roasting time 1～6h in the situation of protection of inert gas; Roasting obtains the trimanganese tetroxide product after by cooling, washing, filtration, drying.
Wherein, among the aforesaid method step b, the control liquid-solid ratio is 4～8m
3︰ 1t, and add 90～130 ℃ of thermal control temperature, be 9～11 with ammoniacal liquor control pH value, reaction times 3～6h.
Wherein, among the aforesaid method step c, 400～800 ℃ of maturing temperatures, roasting time 2～6h.
Wherein, among the aforesaid method step a, described manganese sulfate solution contains manganese 10～120g/L.
Wherein, among the 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 contains Ca＜10mg/L, Mg＜50mg/L, Si＜10mg/L, Na＜50mg/L, K＜10mg/L, heavy metal＜10mg/L.
Wherein, among the aforesaid method step a, the temperature that manganese sulfate solution is heated is 40～60 ℃.
Wherein, among the aforesaid method step a, the concentration of described ammoniacal liquor is 6～15%, and making the pH value of solution behind the adding ammoniacal liquor is 9～11.
Wherein, among the 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, and blowing air or dioxygen oxidation because oxidizing potential is high, must add additive.And the precipitation (being precipitation of hydroxide) after the 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 that adsorbs in the 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 the additive control current potential, can generate single trimanganese tetroxide; Simultaneously; solid matter (trimanganese tetroxide primary products) with step b washing, after filtering is under protection of inert gas; solid phase high-temperature heat treatment again; control maturing temperature and time; the content of calcium, magnesium and sulphur in can very effective control product finally reaches the purpose of preparation 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
The present invention is further described below by embodiment.
The preparation method of trimanganese tetroxide of the present invention comprises the steps:
A, with manganese sulfate solution heating, add again the ammoniacal liquor reaction, filter after the precipitation, washing;
B, the precipitation after the step a washing is added water size mixing, the control liquid-solid ratio is 3～10m
3︰ 1t, and add 80～150 ℃ of thermal control temperature, be 8～12 with ammoniacal liquor control pH value, reaction times 1～6h; Filter after the reaction, wash;
C, the solid matter that obtains with step b washing, after filtering carry out roasting, 200～800 ℃ of maturing temperatures, roasting time 1～6h in the situation of protection of inert gas; Roasting obtains the trimanganese tetroxide product after by cooling, washing, filtration, drying.
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 that adsorbs in the 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 the additive control current potential, can generate single trimanganese tetroxide.Step c is under protection of inert gas; solid phase high-temperature heat treatment again, control maturing temperature and time, can very effective control product in the content of calcium, magnesium and sulphur; step b integrating step c dual function of the present invention finally reaches the purpose for preparing high-purity mangano-manganic oxide.Step b of the present invention adds the thermal control temperature at 80～150 ℃, it will be understood by those skilled in the art that when temperature can to reach by the mode of encloses container heating during greater than 100 ℃.
Preferably, among the aforesaid method step b, the control liquid-solid ratio is 4～8m
3︰ 1t, and add 90～130 ℃ of thermal control temperature, be 9～11 with ammoniacal liquor control pH value, reaction times 3～6h.
Preferably, among the aforesaid method step c, 400～800 ℃ of maturing temperatures, roasting time 2～6h.
Preferably, among the aforesaid method step a, described manganese sulfate solution contains manganese 10～120g/L.
Preferably, for the cost that further economizes in raw materials, among the 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 contains Ca＜10mg/L, Mg＜50mg/L, Si＜10mg/L, Na＜50mg/L, K＜10mg/L, heavy metal＜10mg/L.
Preferably, among the aforesaid method step a, the temperature that manganese sulfate solution is heated is 40～60 ℃; Be heated to the particle form generation that this temperature is conducive to manganous hydroxide.
Preferably, among the aforesaid method step a, the concentration of described ammoniacal liquor is 6～15%, and making the pH value of solution behind the adding ammoniacal liquor is 9～11.Control pH value is control calcium, magnesium addition less than 11 purpose, and when pH value was higher than 11, calcium magnesium was precipitated out easily, causes in the product calcium-magnesium content too high, does not reach requirement, but that pH value mistake is hanged down the precipitation of manganese is incomplete.
Preferably, among the 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 the embodiment.
Embodiment one
To purify qualified (is Ca＜10mg/L, Mg＜50mg/L, Si＜10mg/L, Na＜50mg/L, K＜10mg/L, heavy metal＜10mg/L afterwards, manganese concentration down together) is the manganese sulfate solution 5L of 40g/l, put into reactor, be heated to 30 ℃, slowly add 6% ammonia precipitation process, the control endpoint pH is 8 again.Filtration after precipitation is finished behind deionized water wash 5 times, is transferred to filter cake in another reactor, adds deionized water and sizes mixing, liquid-solid ratio is 8:1, reheats 85 ℃, and control pH value is 9, filter behind the hydrothermal treatment consists 6h, use deionized water wash 3 times, obtain the trimanganese tetroxide primary products.With the trimanganese tetroxide primary products, in the nitrogen protection situation, process 600 ℃ of roasting 3h desulfurization in-depths again.Obtain the high-purity mangano-manganic oxide product after cooling, washing, filtration, drying, 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 two
Manganese concentration after purification is qualified is the manganese sulfate solution 5L of 60g/l, puts into reactor, is heated to 50 ℃, slowly adds 8% ammonia precipitation process again, and the control endpoint pH is 9.Filtration after precipitation is finished behind deionized water wash 3 times, is transferred to filter cake in another reactor, adds deionized water and sizes mixing, liquid-solid ratio is 5:1, reheats 95 ℃, and control pH value is 11, filter behind the hydrothermal treatment consists 3h, use deionized water wash 3 times, obtain the trimanganese tetroxide primary products.With the trimanganese tetroxide primary products, in the nitrogen protection situation, process 400 ℃ of roasting 4h desulfurization in-depths again.Obtain the high-purity mangano-manganic oxide product after cooling, washing, filtration, drying, 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 three
Manganese concentration after purification is qualified is the manganese sulfate solution 5L of 100g/l, puts into reactor, is heated to 70 ℃, slowly adds 12.5% ammonia precipitation process again, and the control endpoint pH is 10.Filtration after precipitation is finished behind deionized water wash 2 times, is transferred to filter cake in another reactor, adds deionized water and sizes mixing, liquid-solid ratio is 6:1, reheats 130 ℃, and control pH value is 11, filter behind the hydrothermal treatment consists 2h, use deionized water wash 3 times, obtain the trimanganese tetroxide primary products.With the trimanganese tetroxide primary products, in the nitrogen protection situation, process 700 ℃ of roasting 2h desulfurization in-depths again.Obtain the high-purity mangano-manganic oxide product after cooling, washing, filtration, drying, 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 four
Manganese concentration after purification is qualified is the manganese sulfate solution 5L of 80g/l, puts into reactor, is heated to 60 ℃, slowly adds 15% ammonia precipitation process again, and the control endpoint pH is 9.5.Filtration after precipitation is finished behind deionized water wash 3 times, is transferred to filter cake in another reactor, adds deionized water and sizes mixing, liquid-solid ratio is 4:1, reheats 120 ℃, and control pH value is 9, filter behind the hydrothermal treatment consists 4h, use deionized water wash 1 time, obtain the trimanganese tetroxide primary products.With the trimanganese tetroxide primary products, in the nitrogen protection situation, process 800 ℃ of roasting 1h desulfurization in-depths again.Obtain the high-purity mangano-manganic oxide product after cooling, washing, filtration, drying, 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
Manganese concentration after purification is qualified is the manganese sulfate solution 5L of 60g/l, puts into reactor, is heated to 50 ℃, slowly adds 6% ammonia precipitation process again, and the control endpoint pH is 8.5.Filtration after precipitation is finished behind deionized water wash 3 times, is transferred to filter cake in another reactor, adds deionized water and sizes mixing, liquid-solid ratio is 5:1, reheats 90 ℃, and control pH value is 10, filter behind the hydrothermal treatment consists 6h, use deionized water wash 3 times, obtain the trimanganese tetroxide primary products.With the trimanganese tetroxide primary products, in the nitrogen protection situation, process 600 ℃ of roasting 4h desulfurization in-depths again.Obtain the high-purity mangano-manganic oxide product after cooling, washing, filtration, drying, 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
Manganese concentration after purification is qualified is the manganese sulfate solution 5L of 120g/l, puts into reactor, is heated to 60 ℃, slowly adds 12% ammonia precipitation process again, and the control endpoint pH is 10.Filtration after precipitation is finished behind deionized water wash 5 times, is transferred to filter cake in another reactor, adds deionized water and sizes mixing, liquid-solid ratio is 5:1, reheats 120 ℃, and control pH value is 9, filter behind the hydrothermal treatment consists 3h, use deionized water wash 3 times, obtain the trimanganese tetroxide primary products.With the trimanganese tetroxide primary products, in the nitrogen protection situation, process 300 ℃ of roasting 6h desulfurization in-depths again.Obtain the high-purity mangano-manganic oxide product after cooling, washing, filtration, drying, 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 (9)
1. the preparation method of trimanganese tetroxide is characterized in that comprising the steps:
A, with manganese sulfate solution heating, add again the ammoniacal liquor reaction, filter after the precipitation, washing;
B, the precipitation after the step a washing is added water size mixing, the control liquid-solid ratio is 3～10m
3︰ 1t, and add 80～150 ℃ of thermal control temperature, be 8～12 with ammoniacal liquor control pH value, reaction times 1～6h; Filter after the reaction, wash;
C, the solid matter that obtains with step b washing, after filtering carry out roasting, 200～800 ℃ of maturing temperatures, roasting time 1～6h in the situation of protection of inert gas; Roasting obtains the trimanganese tetroxide product after by cooling, washing, filtration, drying.
2. the preparation method of trimanganese tetroxide according to claim 1, it is characterized in that: among the step b, the control liquid-solid ratio is 4～8m
3︰ 1t, and add 90～130 ℃ of thermal control temperature, be 9～11 with ammoniacal liquor control pH value, reaction times 3～6h.
3. the preparation method of trimanganese tetroxide according to claim 1 is characterized in that: among the step c, and 400～800 ℃ of maturing temperatures, roasting time 2～6h.
4. according to claim 1, the preparation method of 2 or 3 described trimanganese tetroxides, it is characterized in that: among the step a, described manganese sulfate solution contains manganese 10～120g/L.
5. according to claim 1, the preparation method of 2 or 3 described trimanganese tetroxides, it is characterized in that: among the step a, described manganese sulfate solution is to be obtained through sulfuric acid to leach, removal of impurities by manganese ore.
6. the preparation method of trimanganese tetroxide according to claim 5, it is characterized in that: described manganese sulfate solution contains Ca＜10mg/L, Mg＜50mg/L, Si＜10mg/L, Na＜50mg/L, K＜10mg/L, heavy metal＜10mg/L.
7. according to claim 1, the preparation method of 2 or 3 described trimanganese tetroxides, it is characterized in that: among the step a, be 40～60 ℃ with the temperature of manganese sulfate solution heating.
8. according to claim 1, the preparation method of 2 or 3 described trimanganese tetroxides, it is characterized in that: among the step a, the concentration of described ammoniacal liquor is 6～15%, adds that to make the pH value of solution behind the ammoniacal liquor be 9～11.
9. according to claim 1, the preparation method of 2 or 3 described trimanganese tetroxides, it is characterized in that: among the step c, described rare gas element is nitrogen or argon gas.
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| CN106848295A (en) * | 2017-02-20 | 2017-06-13 | 北京理工大学 | Mn oxide and preparation method thereof and aluminium ion battery |
| CN111807414A (en) * | 2020-06-18 | 2020-10-23 | 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 |
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| CN111807414A (en) * | 2020-06-18 | 2020-10-23 | 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 |
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