CN105753056B - A kind of method for preparing manganese sulfate - Google Patents
A kind of method for preparing manganese sulfate Download PDFInfo
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- CN105753056B CN105753056B CN201610108330.1A CN201610108330A CN105753056B CN 105753056 B CN105753056 B CN 105753056B CN 201610108330 A CN201610108330 A CN 201610108330A CN 105753056 B CN105753056 B CN 105753056B
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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
- C01G45/10—Sulfates
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Abstract
The invention provides a kind of method for preparing manganese sulfate.This method matches somebody with somebody manganese glance and manganese oxide ore by a certain percentage to be mixed after ore deposit and carries out ore grinding to the blending ore, is then calcined, contains SO2Waste gas prepare sulfuric acid, gained sulfuric acid goes to leach calcining again to prepare manganese sulfate.Calcining manganese content of the present invention is high, energy consumption is low, production cost is low, reaction condition is gentle, implements simple and reliable, a kind of feasible method and reliable theoretical foundation are provided for the utilization of China's manganese glance resource.
Description
Technical field
The invention belongs to field of hydrometallurgy, it is related to a kind of method for producing manganese sulfate.
Background technology
Manganese sulfate is the primary raw material for processing various manganese products.The existing method for preparing manganese sulfate mainly have wet method and
Pyrogenic process, primary raw material is manganese carbonate and manganese oxide ore.Manganese carbonate is the optimum feed stock for preparing manganese sulfate, but the such raw material of China by
Year successively decreases, therefore manganese oxide ore has become the primary raw material for preparing manganese sulfate.It is well known that value Mn is difficult to be soaked with sulfuric acid
Go out, so no matter manganese oxide ore prepares manganese sulfate with wet method or pyrogenic process, be both needed to addition reducing agent to reduce manganese valence.
Wet reducing extract technology is mainly by manganese oxide ore, sulfuric acid and a certain amount of reducing agent hybrid reaction, certain
At a temperature of use water extraction, filtering wet slag after condensing crystallizing obtain manganese sulfate.The temperature of general wet-leaching is 85 DEG C~100 DEG C.
The key of wet extraction is the selection of reducing agent.Hydrogen peroxide is a kind of efficient reducing agent, but has a large amount of during the course of the reaction
The precipitation of oxygen and influence whole process.Two ore deposit lixiviation process (application number CN87102046, application number CN91102845.5, application
Number 200710192613.X, application number 200710151596.5, application number 201210143876.2) added i.e. in leaching process
Iron sulfide is as reducing agent, and the grade that on the one hand the method reduces manganese in raw material makes the increase of leaching cost, while in leachate
In there is substantial amounts of iron influence subsequent purification process, substantial amounts of H is on the other hand had in leaching process2S gas overflowings, environment
Badly.According to reactional equation FeS2+MnO2+2H2S04=MnSO4+FeS04+2H20+2S, also has a large amount of sulphur during the course of the reaction
The generation of sulphur, leached mud turns into the potential source of environmental pollution.A kind of high-sulfur manganese carbonate ore is straight using sulfuric acid with dioxide ore for manganese
Connect the method (Application Number (patent) 201510110579.1) that leaching prepares manganese sulfate solution, its essence be also using two-control region i.e.
Reducing agent, which is made, by the sulphur contained in manganese carbonate ore prepares manganese sulfate.
When prepared by pyrogenic process, preferred coal is as reducing agent, and the method is traditional processing technology, technology maturation, the matter of manganese sulfate
Measure, but the serious dust pollution of the environment of its generation, greatly, the quantity of slag is big for coal consumption amount.Two ore deposit roasting methods, i.e., by manganese oxide ore and sulphur iron
Ore deposit mix crush after, temperature be 500 DEG C~600 DEG C, under oxidizing atmosphere be calcined 0.5~1 hour, then leach, solid-liquid
Separation, leachate condensing crystallizing obtain manganese sulfate.The principle of the technique of this method is:
4FeS2+11O2+8MnO2=2Fe2O3+8MnSO4
This method causes to leach cost than larger due to adding a large amount of pyrite, simultaneously because this reaction must be in air
MnSO is directly generated under atmosphere4, due to O2The limitation of concentration, MnO2Conversion ratio there was only 90% or so, but subsequent technique is simpler
Single, water logging condensing crystallizing just can obtain manganese sulfate.
Method (the Application Number (patent) of SOz/NOx combined extracting manganese in a kind of manganese oxide ore simultaneous removing flue gas
201510454881.9) be reduction roasting a kind of method, i.e. Mn oxide in manganese oxide ore is by SOz is selectively sulfated
Water miscible manganese sulfate.
The ground such as China western part province Yunnan, Sichuan find a large amount of manganese glances.Early-stage Study is found, straight using manganese glance
Sulfuric acid leaching is connect, a large amount of H can be generated2S gases, i.e., be also to have a large amount of H using two ore deposit lixiviation process2S gas overflowings；Use oxidizing roasting
Method, because atmosphere is difficult to control to, in product of roasting manganese compound variation, inevitably generate manganese dioxide, roast
Sand adds reducing agent again in leaching process, and many adverse effects are brought to subsequent production.In view of handling manganese oxide ore above
Method to manganese glance part can be used for reference, therefore the present invention is want by pyrogenic process-wet method combined technique, is also such vulcanization
The exploitation of manganese ore provide technology and theoretical foundation.
The content of the invention
The problem of existing for manganese oxide ore and manganese glance processing, it is an object of the invention to provide the comprehensive profit of one kind
The method that manganese sulfate is prepared with manganese glance and manganese oxide ore, this method is simple to operate, flow is short, energy consumption is small, and environmental protection, warp
Ji value is high.
To achieve these goals, a kind of method for preparing manganese sulfate of the present invention, one is pressed by manganese glance and manganese oxide ore
Certainty ratio, which is matched somebody with somebody, to be mixed after ore deposit and carries out ore grinding to the blending ore, is then calcined, contains SO2Waste gas prepare sulfuric acid, gained
Sulfuric acid goes to leach calcining again to prepare manganese sulfate.
Described method, during roasting, manganese glance under the conditions of neutral atmosphere, makes MnS and MnO with manganese oxide ore2Occur
Redox reaction generates MnO and SO2。
Described method, manganese sulfide miberal powder is 1 with manganese dioxide breeze mass ratio:2.5~1:2.8；It is preferred that 1:2.5~
1:2.75。
Described method, manganese sulfide miberal powder and the composite ore ore grinding of manganese dioxide breeze to -0.074mm granularities are reached
More than 75%.
Described method, calcination atmosphere is neutrality, and sintering temperature is 650 DEG C~750 DEG C, and roasting time is 10-15 minutes.
Neutral atmosphere is not have oxygen in medium, and it is anti-with material-to-be-heated or workpiece not occur chemistry at a given temperature
The atmosphere answered.
Described method, product of roasting SO2For preparing sulfuric acid, prepared sulfuric acid is used for the leaching of calcining, prepares sulphur
Sour manganese.
The principle of the present invention is as follows：In neutral conditions, MnS and MnO are made2Generation redox reaction：
3MnO2+ MnS=4MnO+SO2
The SO of generation2For preparing sulfuric acid, the leaching that sulfuric acid is used further to MnO prepares manganese sulfate：
MnO+H2SO4=2MnSO4+H2O
The present invention substantive distinguishing features be:The roasting of composite ore must be carried out in neutral atmosphere, because if in atmosphere
Containing aerobic, manganese sulfate can be generated during roasting, and high price manganese ore cannot be reduced, and add reduction again in follow-up leaching process
Agent.The present invention control sintering temperature 650 DEG C~750 DEG C, MnO2Common reaction obtains high-purity one in neutral atmosphere with MnS
Manganese oxide (MnO), not directly obtains MnSO4, the SO generated in course of reaction2It is used for the leaching of calcining after gas relieving haperacidity.Simultaneously
Using two kinds of manganese ores, manganese grade is high in calcining, introduces that impurity is few, and manganese recovery ratio is high, leaches and purification cost is low, do not produce waste gas
H2S, it is environment-friendly.
Embodiment
The present invention is intended to further illustrate with reference to embodiments, is not intended to limit the present invention.
According to methods described, products obtained therefrom parameter after each process is contrasted respectively, to be illustrated the present invention.
Reference examples 1：Under oxidizing roasting-sulfuric acid leaching process conditions of optimization：Manganese sulfide miberal powder and manganese dioxide breeze
Match as 1:2.75, ore grinding to -0.074mm granularities reach more than 75% after mixing, 650 DEG C of sintering temperature, 1 hour time, use
PH is leached 2 hours for 1 dilute sulfuric acid, and the leaching rate of manganese is 36%.There is a small amount of H in leaching process2S gases.
Embodiment 1：It is 1 in manganese sulfide miberal powder and manganese dioxide breeze proportioning:2.5, ore grinding is to -0.074mm after mixing
Degree reaches more than 75%, is calcined 10 minutes at a temperature of neutral atmosphere, 750 DEG C, is leached 2 hours for 1 dilute sulfuric acid with pH, manganese
Leaching rate be 98%, now have a small amount of H in leaching process2S gases.
Embodiment 2：It is 1 in manganese sulfide miberal powder and manganese dioxide breeze proportioning:2.75, ore grinding is to -0.074mm after mixing
Degree reaches more than 75%, is calcined 10 minutes at a temperature of neutral atmosphere, 750 DEG C, is leached 2 hours for 1 dilute sulfuric acid with pH, manganese
Leaching rate be 99%, leaching process is without H2S gases.
Embodiment 3：It is 1 in manganese sulfide miberal powder and manganese dioxide breeze proportioning:2.8, ore grinding is to -0.074mm after mixing
Degree reaches more than 75%, is calcined 10 minutes at a temperature of neutral atmosphere, 750 DEG C, is leached 2 hours for 1 dilute sulfuric acid with pH, manganese
Leaching rate be 52%, leaching process is without H2S gases.
Embodiment 4：It is 1 in manganese sulfide miberal powder and manganese dioxide breeze proportioning:2.75, ore grinding is to -0.074mm after mixing
Degree reaches more than 75%, is calcined 10 minutes at a temperature of neutral atmosphere, 700 DEG C, is leached 2 hours for 1 dilute sulfuric acid with pH, manganese
Leaching rate be 97%, leaching process is without H2S gases.
Embodiment 5：It is 1 in manganese sulfide miberal powder and manganese dioxide breeze proportioning:2.75, ore grinding is to -0.074mm after mixing
Degree reaches more than 75%, is calcined 10 minutes at a temperature of neutral atmosphere, 650 DEG C, is leached 2 hours for 1 dilute sulfuric acid with pH, manganese
Leaching rate be 95%, leaching process produces micro H2S gases.
Embodiment 6：It is 1 in manganese sulfide miberal powder and manganese dioxide breeze proportioning:2.75, ore grinding is to -0.074mm after mixing
Degree reaches more than 75%, is calcined 20 minutes at a temperature of neutral atmosphere, 750 DEG C, is leached 2 hours for 1 dilute sulfuric acid with pH, manganese
Leaching rate be 99.3%, leaching process is without H2S gases.
Using two ore deposit oxidizing roastings it can be seen from above reference examples and embodiment, the leaching rate of manganese is very low, and roasting
For up to more than 1 hour, the present invention was calcined with neutral atmosphere, 10 minutes, also may be used within actually 8 minutes.In addition, embodiment
The leaching rate of manganese is only 52% in 3, is because manganese sulfide miberal powder reaches 1 with manganese dioxide breeze proportioning:2.8, it can now generate
Mangano-manganic oxide, so manganese sulfide miberal powder is compared harsh with manganese dioxide breeze conditions of mixture ratios, preferably 1：2.5~
2.75。
Claims (2)
1. a kind of method for preparing manganese sulfate, it is characterised in that manganese glance and manganese oxide ore are matched somebody with somebody after ore deposit by a certain percentage and mixed
It is even and to the blending ore carry out ore grinding, be then calcined, contain SO2Waste gas prepare sulfuric acid, gained sulfuric acid goes to leach again and roasted
Sand is to prepare manganese sulfate；
During roasting, manganese glance under the conditions of neutral atmosphere, makes MnS and MnO with manganese oxide ore2Generation redox reaction is generated
MnO and SO2；
Sintering temperature is 650 DEG C~750 DEG C, and roasting time is 10-15 minutes；
Manganese sulfide miberal powder is 1 with manganese dioxide breeze mass ratio:2.5~1:2.75.
2. according to the method described in claim 1, it is characterised in that grind manganese sulfide miberal powder and the composite ore of manganese dioxide breeze
Ore deposit to -0.074mm granularities reach more than 75%.
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| CN105753056B true CN105753056B (en) | 2017-09-29 |
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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 |
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2016
- 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 |
|---|
| "二氧化锰和硫化锰两矿法制备高纯硫酸锰";刘清华;《中国锰业》;20131130;第31卷(第4期);第30-32页 * |
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