CN105753056A - Method for preparing manganese sulfate - Google Patents
Method for preparing manganese sulfate Download PDFInfo
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- CN105753056A CN105753056A CN201610108330.1A CN201610108330A CN105753056A CN 105753056 A CN105753056 A CN 105753056A CN 201610108330 A CN201610108330 A CN 201610108330A CN 105753056 A CN105753056 A CN 105753056A
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- C01—INORGANIC CHEMISTRY
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- C01G45/00—Compounds of manganese
- C01G45/10—Sulfates
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Abstract
The invention provides a method for preparing manganese sulfate. The method comprises the steps of uniformly mixing manganese sulfide ore with manganese oxide ore, grinding the obtained mixed ore, roasting, preparing sulfuric acid from waste gas containing SO2, and lixiviating roasted ore from obtained sulfuric acid, so as to obtain manganese sulfate. According to the method, the content of manganese in roasted ore is high, the energy consumption is low, the production cost is low, reaction conditions are mild, the implementation is simple and reliable, and a feasible method and a reliable theoretical foundation are provided for the utilization of the domestic manganese sulfide ore.
Description
Technical field
The invention belongs to field of hydrometallurgy, relate to a kind of method producing manganese sulfate.
Background technology
Manganese sulfate is used to process the primary raw material of various manganese goods.The existing method preparing manganese sulfate mainly has wet method and pyrogenic process, and primary raw material is manganese carbonate and manganese oxide ore.Manganese carbonate is the optimum feed stock preparing manganese sulfate, but this type of raw material of China successively decreases year by year, and therefore manganese oxide ore has become as the primary raw material preparing manganese sulfate.It is known that value Mn is difficult to sulfuric acid leaching, so no matter manganese oxide ore prepares manganese sulfate with wet method or pyrogenic process, it is both needed to add reducing agent to reduce manganese valence.
Wet reducing extract technology is mainly by manganese oxide ore, sulphuric acid and a certain amount of reducing agent hybrid reaction, and at a certain temperature with water extraction, after filtering wet slag, condensing crystallizing obtains manganese sulfate.The temperature of general wet-leaching is 85 DEG C～100 DEG C.The selection that it is critical only that reducing agent of wet extraction.Hydrogen peroxide is a kind of efficient reducing agent, but has the precipitation of a large amount of oxygen in course of reaction and affect whole process.Two ore deposit solvent extraction method (application number CN87102046, application number CN91102845.5, application number 200710192613.X, application number 200710151596.5, application number 201210143876.2) in leaching process, namely add iron sulfide as reducing agent, the method reduces the grade of manganese in raw material on the one hand makes leaching cost increase, and there is substantial amounts of ferrum in leachate affects subsequent purification process simultaneously, has substantial amounts of H on the other hand in leaching process2S gas overflowing, bad environments.According to reactional equation FeS2+MnO2+2H2S04=MnSO4+FeS04+2H20+2S, also has the generation of a large amount of sulfur in course of reaction, and leached mud becomes the potential source of environmental pollution.A kind of high-sulfur manganese carbonate ore and dioxide ore for manganese utilize sulphuric acid directly leaching to prepare the method (Application Number (patent) 201510110579.1) of manganese sulfate solution, its essence be also adopt two-control region namely by manganese carbonate ore containing sulfur make reducing agent and prepare manganese sulfate.
Time prepared by pyrogenic process, first-selected coal is as reducing agent, and the method is traditional processing technology, technology maturation, and the quality of manganese sulfate is good, but the serious dust pollution of the environment of its generation, coal consumption amount is big, and the quantity of slag is big.Two ore deposit roasting methods, after pulverizing by manganese oxide ore and troilite mix, are 500 DEG C～600 DEG C in temperature, roasting 0.5～1 hour under oxidizing atmosphere, and then leaching, solid-liquid separation, leachate condensing crystallizing obtain manganese sulfate.The principle of the technique of the method is:
4FeS2+11O2+8MnO2=2Fe2O3+8MnSO4
Owing to adding a large amount of pyrite, the method causes that leaching cost is relatively larger, simultaneously because this reaction must directly generate MnSO in air atmosphere4, due to O2The restriction of concentration, MnO2Conversion ratio only have about 90%, but subsequent technique is fairly simple, and water logging condensing crystallizing just can obtain manganese sulfate.
In a kind of manganese oxide ore simultaneous removing flue gas, the method (Application Number (patent) 201510454881.9) of SOz/NOx combined extracting manganese is a kind of method of reduction roasting, and namely the Mn oxide in manganese oxide ore is selectively sulfated for water miscible manganese sulfate by SOz.
The ground such as Yunnan, province, China western part, Sichuan find a large amount of manganese glances.Early-stage Study finds, adopts the direct sulfuric acid leaching of manganese glance, can generate a large amount of H2S gas, namely using two ore deposit solvent extraction method is also have a large amount of H2S gas overflowing；By the method for oxidizing roasting, owing to atmosphere is difficult to control to, in product of roasting, the compound variation of manganese, inevitably generates manganese dioxide, and calcining adds reducing agent again in leaching process, brings many adverse effects to subsequent production.In view of manganese glance is not had to use for reference part by the above method processing manganese oxide ore, therefore the present invention wants by pyrogenic process-wet method combined technique, also provides technology and theoretical foundation for the exploitation of such manganese glance.
Summary of the invention
Processing Problems existing for manganese oxide ore and manganese glance, it is an object of the invention to provide and a kind of comprehensively utilize manganese glance and method that manganese oxide ore prepares manganese sulfate, the method is simple to operate, flow process is short, energy consumption is little, and environmental protection, economic worth are high.
To achieve these goals, a kind of method preparing manganese sulfate of the present invention, mix after manganese glance and manganese oxide ore are joined ore deposit by a certain percentage and this blending ore is carried out ore grinding, then carrying out roasting, containing SO2Waste gas prepare sulphuric acid, gained sulphuric acid again go leach calcining to prepare manganese sulfate.
Described method, during roasting, manganese glance and manganese oxide ore, when neutral atmosphere, make MnS and MnO2Redox reaction is occurred to generate MnO and SO2。
Described method, Manganese monosulfide. breeze and manganese dioxide powdered ore quality ratio are 1:2.5～1:2.8；Preferred 1:2.5～1:2.75.
Described method, reaches more than 75% by the composite ore ore grinding to-0.074mm granularity of Manganese monosulfide. breeze with manganese dioxide breeze.
Described method, calcination atmosphere is neutral, and sintering temperature is 650 DEG C～750 DEG C, and roasting time is 10-15 minute.
Neutral atmosphere and medium do not have oxygen, and at a given temperature not with material-to-be-heated or workpiece generation chemical reaction atmosphere.
Described method, product of roasting SO2For preparing sulphuric acid, prepared sulphuric acid, for the leaching of calcining, prepares manganese sulfate.
Principles of the invention is as follows: in neutral conditions, makes MnS and MnO2There is redox reaction:
3MnO2+ MnS=4MnO+SO2
The SO generated2For preparing sulphuric acid, sulphuric acid is used further to the leaching of MnO and prepares manganese sulfate:
MnO+H2SO4=2MnSO4+H2O
The substantive distinguishing features of the present invention is: must carry out the roasting of composite ore in neutral atmosphere, because if containing aerobic in atmosphere, can generate manganese sulfate during roasting, and high price manganese ore cannot be reduced, and adds reducing agent in follow-up leaching process again.The present invention controls sintering temperature at 650 DEG C～750 DEG C, MnO2In neutral atmosphere, jointly it is obtained by reacting high-purity manganese monoxide (MnO) with MnS, not directly obtains MnSO4, the SO of generation in course of reaction2For the leaching of calcining after gas antacid.Utilizing two kinds of manganese ores, in calcining, manganese is of high grade simultaneously, introduces impurity few, and manganese recovery ratio is high, leaches and purification cost is low, do not produce waste gas H2S, environmental friendliness.
Detailed description of the invention
It is further intended to the present invention, and the unrestricted present invention are described below in conjunction with embodiment.
According to described method, products obtained therefrom parameter after each operation is contrasted respectively, is illustrated the present invention.
Reference examples 1: under the oxidizing roasting sulfuric acid leaching process conditions optimized: Manganese monosulfide. breeze and manganese dioxide breeze proportioning are 1:2.75, after mixing, ore grinding to-0.074mm granularity reaches more than 75%, sintering temperature 650 DEG C, 1 hour time, leaching 2 hours with the dilute sulfuric acid that pH is 1, the leaching rate of manganese is 36%.Leaching process has a small amount of H2S gas.
Embodiment 1: be 1:2.5 in Manganese monosulfide. breeze and manganese dioxide breeze proportioning, after mixing, ore grinding to-0.074mm granularity reaches more than 75%, roasting temperature 10 minutes neutral atmosphere, 750 DEG C, leach 2 hours with the dilute sulfuric acid that pH is 1, the leaching rate of manganese is 98%, now has a small amount of H in leaching process2S gas.
Embodiment 2: be 1:2.75 in Manganese monosulfide. breeze and manganese dioxide breeze proportioning, after mixing, ore grinding reaches more than 75% to-0.074mm granularity, at the roasting temperature 10 minutes of neutral atmosphere, 750 DEG C, leaches 2 hours with the dilute sulfuric acid that pH is 1, the leaching rate of manganese is 99%, and leaching process is without H2S gas.
Embodiment 3: be 1:2.8 in Manganese monosulfide. breeze and manganese dioxide breeze proportioning, after mixing, ore grinding reaches more than 75% to-0.074mm granularity, at the roasting temperature 10 minutes of neutral atmosphere, 750 DEG C, leaches 2 hours with the dilute sulfuric acid that pH is 1, the leaching rate of manganese is 52%, and leaching process is without H2S gas.
Embodiment 4: be 1:2.75 in Manganese monosulfide. breeze and manganese dioxide breeze proportioning, after mixing, ore grinding reaches more than 75% to-0.074mm granularity, at the roasting temperature 10 minutes of neutral atmosphere, 700 DEG C, leaches 2 hours with the dilute sulfuric acid that pH is 1, the leaching rate of manganese is 97%, and leaching process is without H2S gas.
Embodiment 5: be 1:2.75 in Manganese monosulfide. breeze and manganese dioxide breeze proportioning, after mixing, ore grinding to-0.074mm granularity reaches more than 75%, roasting temperature 10 minutes neutral atmosphere, 650 DEG C, leach 2 hours with the dilute sulfuric acid that pH is 1, the leaching rate of manganese is 95%, and leaching process produces trace H2S gas.
Embodiment 6: be 1:2.75 in Manganese monosulfide. breeze and manganese dioxide breeze proportioning, after mixing, ore grinding reaches more than 75% to-0.074mm granularity, at the roasting temperature 20 minutes of neutral atmosphere, 750 DEG C, leaches 2 hours with the dilute sulfuric acid that pH is 1, the leaching rate of manganese is 99.3%, and leaching process is without H2S gas.
By above reference examples and embodiment it can be seen that adopt two ore deposit oxidizing roastings, the leaching rate of manganese is very low, and roasting time was up to more than 1 hour, present invention neutral atmosphere roasting, 10 minutes, actually within 8 minutes, also may be used.In addition, in embodiment 3, the leaching rate of manganese is only 52%, is because Manganese monosulfide. breeze and reaches 1:2.8 with manganese dioxide breeze proportioning, now can generate mangano-manganic oxide, so Manganese monosulfide. breeze compares harsh with manganese dioxide breeze conditions of mixture ratios, it is desirable to for 1:2.5～2.75.
Claims (7)
1. the method preparing manganese sulfate, it is characterised in that mix after manganese glance and manganese oxide ore are joined ore deposit by a certain percentage and this blending ore is carried out ore grinding, then carrying out roasting, containing SO2Waste gas prepare sulphuric acid, gained sulphuric acid again go leach calcining to prepare manganese sulfate.
2. method according to claim 1, it is characterised in that during roasting, manganese glance and manganese oxide ore, when neutral atmosphere, make MnS and MnO2Redox reaction is occurred to generate MnO and SO2。
3. method according to claim 2, it is characterised in that Manganese monosulfide. breeze and manganese dioxide powdered ore quality ratio are 1:2.5～1:2.8.
4. method according to claim 3, it is characterised in that Manganese monosulfide. breeze and manganese dioxide powdered ore quality ratio are 1:2.5～1:2.75.
5. method according to claim 1, it is characterised in that the composite ore ore grinding to-0.074mm granularity of Manganese monosulfide. breeze with manganese dioxide breeze is reached more than 75%.
6. the method according to claim 1 or 2 or 3 or 4 or 5, it is characterised in that calcination atmosphere is neutral, and sintering temperature is 650 DEG C～750 DEG C, and roasting time is 10-15 minute.
7. method according to claim 1, it is characterised in that product of roasting SO2For preparing sulphuric acid, prepared sulphuric acid, for the leaching of calcining, prepares manganese sulfate.
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| CN201610108330.1A CN105753056B (en) | 2016-02-26 | 2016-02-26 | A kind of method for preparing manganese sulfate |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108155376A (en) * | 2017-12-28 | 2018-06-12 | 湖南佳纳能源科技有限公司 | A kind of method for preparing anode material for lithium-ion batteries precursor |
Citations (3)
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| CN104789755A (en) * | 2015-04-23 | 2015-07-22 | 中南大学 | Method and device of utilizing high-sulfur manganese mine to cleanly and efficiently produce manganese metal |
| CN104975167A (en) * | 2015-07-24 | 2015-10-14 | 长沙矿冶研究院有限责任公司 | Method for extracting manganese from composite manganese ore composed of multiple phases containing manganese |
| CN105002380A (en) * | 2015-07-30 | 2015-10-28 | 中南大学 | Method for manganese oxide ore to synchronously remove SO2/NOx in smoke for combined extraction of manganese |
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- 2016-02-26 CN CN201610108330.1A patent/CN105753056B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104789755A (en) * | 2015-04-23 | 2015-07-22 | 中南大学 | Method and device of utilizing high-sulfur manganese mine to cleanly and efficiently produce manganese metal |
| CN104975167A (en) * | 2015-07-24 | 2015-10-14 | 长沙矿冶研究院有限责任公司 | Method for extracting manganese from composite manganese ore composed of multiple phases containing manganese |
| CN105002380A (en) * | 2015-07-30 | 2015-10-28 | 中南大学 | Method for manganese oxide ore to synchronously remove SO2/NOx in smoke for combined extraction of manganese |
Non-Patent Citations (1)
| Title |
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| 刘清华: ""二氧化锰和硫化锰两矿法制备高纯硫酸锰"", 《中国锰业》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108155376A (en) * | 2017-12-28 | 2018-06-12 | 湖南佳纳能源科技有限公司 | A kind of method for preparing anode material for lithium-ion batteries precursor |
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