CN105040038B - The method for carrying out demagging to electrolytic manganese anolyte using ammonium sulfate - Google Patents
The method for carrying out demagging to electrolytic manganese anolyte using ammonium sulfate Download PDFInfo
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- CN105040038B CN105040038B CN201510394768.6A CN201510394768A CN105040038B CN 105040038 B CN105040038 B CN 105040038B CN 201510394768 A CN201510394768 A CN 201510394768A CN 105040038 B CN105040038 B CN 105040038B
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- ammonium sulfate
- electrolytic manganese
- anolyte
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
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Abstract
A kind of method that application ammonium sulfate carries out demagging to electrolytic manganese anolyte, comprises the following steps：The electrolytic manganese anolyte that electrolytic manganese industry is produced is added in a stirred crystallization groove, then to adding ammonium sulfate solids in stirred crystallization groove, one side stirring and dissolving is while add ammonium sulfate solids, ammonium sulfate solids addition is recrystallized after finishing and separates out crystal, is filtered after crystallization reaction is abundant；Filtrate cycle after filtering is leached for electrolytic manganese chemical combination, is reclaimed the filter residue after filtering and is obtained complex salt.It is method of the present invention process is simple, easy to operate, the magnesium density in electrolytic manganese anolyte can be significantly reduced, and keep electrolytic manganese to return to anolyte purity.
Description
Technical field
The invention belongs to non-ferrous metal technical field of wet metallurgy, demagging in more particularly to a kind of electrolytic manganese production process
Method.
Background technology
In current electrolysis manganese industrial production, raw material manganese ore contains about 2% magnesia, most of in leaching operation dissolution,
And leachate is the electrolytic manganese anolyte for recycling, cause the MgSO in system4Accumulation reaches more than 150g/L, and this is to production
Many difficulties are brought, such as：（1）Increase the viscosity of electrolyte, density, conductance declines, and causes the ion in electrolyte to expand
Dissipate and hindered, tank voltage rises, current efficiency reduction, so as to reduce the production efficiency of electrolytic cell, increased energy consumption,
Increased the production cost of manganese；（2）Influence the purity and quality of manganese product；（3）Brokenly analysed in electrode, equipment and pipeline
Go out material and form crystallization, serious meeting blocks production conveyance conduit, very big difficulty is brought to operating, or even influence is normal raw
Produce.
Domestic many research workers propose the method that some electrolytic manganeses produce demagging, such as the fluoride precipitation method, oxalic acid
The precipitation method, recrystallization method etc., but have undesirable part.Oxalate precipitation method can introduce new impurity, and need to adjust solution
PH value, increased financial cost.MnF is selected in fluoride precipitation method aspect, someone's research2As precipitating reagent（Such as Liu Honggang et al.,
Calcium and magnesium [J] mining and metallurgys, 2007,16 (4) in manganous fluoride deposition removal reduction-oxidation Leaching Solution of Manganese Ore:25-28.）, in precipitation temperature
For 90 DEG C, precipitating reagent use level coefficient be 1.5, mixing time be 1h, material liquid pH value be 4.0 when, calcium and magnesium rate of deposition difference
96% and 99% is reached, sedimentation effect is very good, but the MnF that the method is used2It is required that purity is high, preparation cost is also high, and without existing
It is by MnSO into commodity, in experiment4With NH4F reaction self-controls are formed；Fluoride salt consumption excess coefficient is big simultaneously, and remaining fluorine ion contains
Amount increases, and has stronger corrosiveness to minus plate, causes the service life of minus plate to shorten.Recrystallization method is to utilize
MgSO4And MnSO4The difference of solubility, the separation for realizing magnesium manganese is separated out by crystallizing at different temperatures.But temperature is less than 100
DEG C when MgSO4-MnSO4Water system has mixed crystal to separate out when crystallizing, and causes separating effect undesirable；Although temperature can be compared with when being higher than 100 DEG C
Separate well, but there is also high energy consumption, the low shortcoming of efficiency.
Ethanol circulation is removed during the Chinese patent of Application No. CN201110024249 discloses a kind of electrolytic manganese machining process
Magnesium method, its step is：To adding absolute ethyl alcohol in electrolytic manganese anolyte, its addition 80~125 g/1, after stirring,
At 35 DEG C~55 DEG C, there are a large amount of salt precipitations to adjustment solution temperature in the magnesium sulfate in anolyte, then anolyte is separated by filtration,
Remove saturation magnesium sulfate precipitation in anolyte.Ethanol distillation can be divided by the method distilled through the solution after filtration treatment
From, realize ethanol reclaim and recycle.The shortcoming of the method is to introduce new organic matter phase, and ethanol distillation is difficult to thoroughly analysis
Go out, circular treatment operation is cumbersome, the removal rate of magnesium is not high, the loss of ammonium is also than larger during demagging.
The content of the invention
The technical problems to be solved by the invention are to overcome the shortcomings of to be mentioned and defect in background above technology, there is provided one
Kind of process is simple, it is easy to operate, the magnesium density in electrolytic manganese anolyte can be significantly reduced and to keep electrolytic manganese to return to anolyte pure
The method that the application ammonium sulfate of degree carries out demagging to electrolytic manganese anolyte.
In order to solve the above technical problems, technical scheme proposed by the present invention applies ammonium sulfate to electrolytic manganese anolyte for a kind of
The method for carrying out demagging, comprises the following steps：
The electrolytic manganese anolyte that electrolytic manganese industry is produced is added in a stirred crystallization groove, then to adding in stirred crystallization groove
Plus ammonium sulfate solids, one side stirring and dissolving is while add ammonium sulfate solids, ammonium sulfate solids addition is recrystallized after finishing and separates out knot
Brilliant thing, is filtered after crystallization reaction is abundant；Filtrate cycle after filtering is leached for electrolytic manganese chemical combination, reclaims the filter after filtering
Slag obtains complex salt.
The method that above-mentioned application ammonium sulfate carries out demagging to electrolytic manganese anolyte, it is preferred that the electrolytic manganese anolyte
Middle MnSO4Concentration is 30g/l~45g/l, MgSO4Concentration is 120g/l~200g/l, (NH4)2SO4Concentration is 70g/l~90g/
l。
The method that above-mentioned application ammonium sulfate carries out demagging to electrolytic manganese anolyte, it is preferred that the addition of the ammonium sulfate
The initial concentration control for measuring the ammonium sulfate in solution system is defined in 150g/l~250g/l.We are returned according to electrolytic manganese anode
The ammonium sulfate concentrations returned in liquid, calculating needs the new ammonium sulfate solids amount for adding, and most preferred ammonium sulfate initial concentration is about
200g/l or so.The ammonium sulfate solids of the addition are preferably technical grade sulfuric acid ammonium product or byproduct of ammonium sulfate.
The method that above-mentioned application ammonium sulfate carries out demagging to electrolytic manganese anolyte, it is preferred that the complex salt of precipitation
Crystal be six water magnesium sulfate ammoniums, the six water magnesium sulfates ammonium be by ammonium sulfate dissolve after produce sulfate ion, ammonium root from
The crystalline hydrate thing of son, magnesium ion and water composition.The molecular formula of the six water magnesium sulfates ammonium is：(NH4)2SO4·MgSO4·
6H2O, the solubility property of the complex salt crystal in water is good, can be used as the new nitrogen composite fertilizer of magnesium containing manganese, it is also possible to as
Other fertilizer materials or magnesium source material.
The method that above-mentioned application ammonium sulfate carries out demagging to electrolytic manganese anolyte, it is preferred that adopted during the stirring and dissolving
Use strong stirring mode（Preferred mixing speed is 800~2000 r/min）, and the ammonium sulfate solids addition finish after again
Continue to stir 0.5~2.0 h（More preferably 1h or so）.Due to the course of dissolution and sulfuric acid that there is ammonium sulfate in stirred crystallization groove
The crystallization process of magnesium ammonium compound salt, only after ammonium sulfate all dissolves, its utilization rate can be only achieved highest, therefore ammonium sulfate
Dissolving incipient stage selection strong stirring, increases the dissolution degree of ammonium sulfate as far as possible.
The method that above-mentioned application ammonium sulfate carries out demagging to electrolytic manganese anolyte, it is preferred that the crystallization precipitation process
Stop stirring during beginning, spontaneous nucleation reaction is carried out under static conditions, and the time control of crystallization reaction is 2.0~6.0 h（More
The preferred crystallization reaction time is 3.0h or so）.
The method that above-mentioned application ammonium sulfate carries out demagging to electrolytic manganese anolyte, it is preferred that the MnSO in the filtrate4
Concentration 25g/l~36g/l, MgSO4Concentration is 60g/l~110g/l, (NH4)2SO4Concentration is 90g/l~130g/l.The filtrate
It is the solution essentially identical with former electrolytic manganese anode rework solution component, but after crystallizing demagging, the concentration of magnesium sulfate in filtrate
Substantially reduce, ammonium sulfate concentrations significantly increase, manganese sulfate concentration is in a slight decrease, this carrying for being attributed to ammonium magnesium sulfate crystallization is damaged
Lose, the filtrate of acquisition complies fully with electrolyte and returns to the requirement for recycling.
Above-mentioned technical proposal of the invention is based primarily upon following principle：The present invention in electrolytic manganese anolyte by adding sulphur
Sour ammonium simultaneously makes it fully dissolve, this considerably increases sulfate ion and ammonium ion in solution system, substantial amounts of sulfate radical
Ion, ammonium ion and magnesium ion form compound salt crystal, and are separated out from solution system, and specific reaction equation is：
2SO4 2-+Mg2++2NH4 ++6H2O=(NH4)2SO4·MgSO4·6H2O；
The compound salt crystal for separating out has taken away the magnesium in solution, has reached the effect of demagging.In addition, the ammonium sulfate of addition is consolidated
Body can absorb heat in dissolving, the temperature of solution system is decreased, and this is more beneficial for increasing the crystallization of ammonium magnesium sulfate complex salt
Amount, improves demagging effect.
Compared with prior art, the advantage of the invention is that：
First, raw material of the invention is very simple and is easy to get, only from reagent of sulfuric acid ammonium solid, particularly preferred
Ammonium sulfate derives from other industrial byproducts（In ammonia, the ammonia absorption smeltery flue gas in sulfuric acid absorption oven gas
Sulfur dioxide etc.）When, price is more cheap and economy is more preferable.
Second, method of the present invention demagging rate is higher, and demagging rate, can effectively by electrolytic manganese anolyte up to 40%~70%
In magnesium remove, while can also increase the ammonium sulfate concentrations in cyclic electrolysis manganese anolyte.
3rd, the ammonium sulfate of present invention addition removes substantial amounts of magnesium ion as precipitating reagent, only, and does not bring it into
His new impurity, does not originally influence on manganese, acidic group, maintains the purity of cyclic electrolysis manganese anolyte.
4th, because present invention process is simple, raw material is cheap and easy to get, therefore demagging advantage of lower cost, and can also obtain can
The water magnesium sulfate ammonium of byproduct six of sale, substantially increases economic benefit.
On the whole, the method for the present invention not only process is simple, easy to operate, and greatly reduce electrolytic manganese anode
Magnesium density in rework solution, and the purity of electrolytic manganese anode rework solution is maintained, it is a kind of simple and effective electrolytic manganese anolyte
The method of middle demagging.
Specific embodiment
Embodiment 1：
A kind of method that application ammonium sulfate of the invention carries out demagging to electrolytic manganese anolyte, comprises the following steps：
（1）The electrolytic manganese anolyte that the industry of 1000ml electrolytic manganeses is produced, concentration of component therein includes：MnSO4
39.7g/l, MgSO4Concentration 187.3g/l, (NH4)2SO4Concentration 79.3g/l；Add in a stirred crystallization groove, then tied to stirring
Addition 150.0g ammonium sulfate solids, one side stirring and dissolving in brilliant groove are while addition ammonium sulfate solids, make ammonium sulfate in solution system
Initial concentration control in 214.5g/l；
（2）The stirring and dissolving of above-mentioned ammonium sulfate is using strong stirring mode, speed of agitator 1200r/min, and ammonium sulfate
Solid addition is further continued for stirring 1.5h after finishing, and stirring is recrystallized after finishing and separates out crystal, and crystallization precipitation process stops when starting
Only stir, spontaneous nucleation reaction is carried out under static conditions, and the time control of crystallization reaction is 5.0 h, after crystallization reaction is abundant
Slurry suction filtration is carried out, filtrate and filter residue is obtained；
（3）The filtrate that suction filtration is isolated contains MnSO4Concentration 32.7g/l, MgSO4Concentration 68.3g/l, (NH4)2SO4Concentration
118.6g/l, it meets electrolytic manganese and returns to the requirement that anolyte is recycled, and the chemical combination that can be directly used for electrolytic manganese leaches workshop,
Recycle；
（4）The filter residue isolated is that complex salt crystal is six water magnesium sulfate ammoniums, and the six water magnesium sulfates ammonium is by ammonium sulfate
The crystalline hydrate thing of the sulfate ion, ammonium ion, magnesium ion and the water composition that are produced after dissolving, crystal is dried, weight
It is 327.4g, can be used as the new nitrogen composite fertilizer of magnesium containing manganese.
Demagging rate can reach 64.5% during electrolytic manganese after being processed through the present embodiment method returns to anolyte.
Embodiment 2
A kind of method that application ammonium sulfate of the invention carries out demagging to electrolytic manganese anolyte, comprises the following steps：
（1）The electrolytic manganese anolyte that the industry of 1000ml electrolytic manganeses is produced, concentration of component therein includes：MnSO4Concentration
39.7g/l, MgSO4Concentration 187.3g/l, (NH4)2SO4Concentration 79.3g/l；Add in a stirred crystallization groove, then tied to stirring
Addition 75.0g ammonium sulfate solids in brilliant groove, one side stirring and dissolving addition ammonium sulfate solids on one side make ammonium sulfate in solution system
Initial concentration is controlled in 157.7g/l；
（2）Strong stirring mode is used during the stirring and dissolving of above-mentioned ammonium sulfate, speed of agitator is 850r/min, and ammonium sulfate
Solid addition is further continued for stirring 1.0 h after finishing, and stirring is recrystallized after finishing and separates out crystal, and crystallization precipitation process stops when starting
Only stir, spontaneous nucleation reaction is carried out under static conditions, and the time control of crystallization reaction is 4.0 h, after crystallization reaction is abundant
Slurry suction filtration is carried out, filtrate and filter residue is obtained；
（3）The filtrate that suction filtration is isolated contains MnSO4Concentration 35.8g/l, MgSO4Concentration 104.3g/l, (NH4)2SO4Concentration
94.4g/l, it meets electrolytic manganese and returns to the requirement that anolyte is recycled, and the chemical combination that can be directly used for electrolytic manganese leaches workshop,
Recycle；
（4）The filter residue isolated is that complex salt crystal is six water magnesium sulfate ammoniums, and the six water magnesium sulfates ammonium is by ammonium sulfate
The crystalline hydrate thing of the sulfate ion, ammonium ion, magnesium ion and the water composition that are produced after dissolving, crystal is dried, weight
It is 214.8g, can be used as the new nitrogen composite fertilizer of magnesium containing manganese.
Demagging rate can reach 44.9% during electrolytic manganese after being processed through the present embodiment method returns to anolyte.
Claims (6)
1. a kind of method that application ammonium sulfate carries out demagging to electrolytic manganese anolyte, comprises the following steps：
By electrolytic manganese industry generation containing MnSO4Concentration is 30g/l~45g/l, MgSO4Concentration is 120g/l~200g/l,
(NH4)2SO4Concentration is added in a stirred crystallization groove for the electrolytic manganese anolyte of 70g/l~90g/l, then in stirred crystallization groove
Addition ammonium sulfate solids, the addition of ammonium sulfate is controlled in 150g/l~250g/l with the initial concentration of ammonium sulfate in solution system
It is defined, strong stirring dissolving in one side is while add ammonium sulfate solids, ammonium sulfate solids addition is entered under static conditions again after finishing
Row spontaneous nucleation separates out crystal, is filtered after crystallization reaction is abundant；Filtrate cycle after filtering is soaked for electrolytic manganese chemical combination
Go out, reclaim the filter residue after filtering and obtain complex salt.
2. the method that application ammonium sulfate according to claim 1 carries out demagging to electrolytic manganese anolyte, it is characterised in that analysis
The complex salt crystal for going out is six water magnesium sulfate ammoniums, and the six water magnesium sulfates ammonium is the sulfuric acid produced after being dissolved by ammonium sulfate
The crystalline hydrate thing of radical ion, ammonium ion, magnesium ion and water composition.
3. the method that application ammonium sulfate according to claim 1 carries out demagging to electrolytic manganese anolyte, it is characterised in that
The ammonium sulfate solids addition is further continued for the h of stirring 0.5~2.0 after finishing.
4. the method that application ammonium sulfate according to claim 1 carries out demagging to electrolytic manganese anolyte, it is characterised in that
The strong stirring mode refers to that mixing speed is controlled to 800~2000 r/min.
5. the method that the application ammonium sulfate according to any one of Claims 1 to 4 carries out demagging to electrolytic manganese anolyte,
Characterized in that, the crystallization precipitation process stops stirring when starting, crystallization reaction is carried out under static conditions, and crystallization reaction
Time control is 2.0~6.0 h.
6. the method that the application ammonium sulfate according to any one of Claims 1 to 4 carries out demagging to electrolytic manganese anolyte, its
It is characterised by, the MnSO in the filtrate4Concentration 25g/l~36g/l, MgSO4Concentration is 60g/l~110g/l, (NH4)2SO4It is dense
It is 90g/l~130g/l to spend.
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| CN108164046A (en) * | 2018-01-17 | 2018-06-15 | 郑州轻工业学院 | A kind of method that high-concentration ammonia nitrogenous wastewater and recycling are handled with desulfurization wastewater |
| CN109680300B (en) * | 2019-01-31 | 2021-06-15 | 贵州大学 | Method for removing magnesium in manganese sulfate solution by double salt crystallization method |
| CN111647911B (en) * | 2020-03-27 | 2022-09-13 | 昆明理工大学 | Process for removing magnesium ions in electrolytic manganese anolyte |
| CN112553481A (en) * | 2020-12-11 | 2021-03-26 | 中南大学 | Production method of electrolytic manganese |
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|---|---|---|---|---|
| GB581370A (en) * | 1942-08-19 | 1946-10-10 | Electro Manganese Corp | Improvements in or relating to the electrowinning of manganese |
| CN1554595A (en) * | 2003-12-30 | 2004-12-15 | 尹德文 | Method for treating magnesium sulfate mather slution after producing boric acid by sulfuric acid method |
| CN102061486A (en) * | 2010-10-12 | 2011-05-18 | 重庆大学 | Method for reducing magnesium ion concentration of electrolytic manganese anolyte |
| CN102191378A (en) * | 2010-03-15 | 2011-09-21 | 贵州省环境科学研究设计院 | Electrolyte preparation process for electrolyzing manganese |
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2015
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB581370A (en) * | 1942-08-19 | 1946-10-10 | Electro Manganese Corp | Improvements in or relating to the electrowinning of manganese |
| CN1554595A (en) * | 2003-12-30 | 2004-12-15 | 尹德文 | Method for treating magnesium sulfate mather slution after producing boric acid by sulfuric acid method |
| CN102191378A (en) * | 2010-03-15 | 2011-09-21 | 贵州省环境科学研究设计院 | Electrolyte preparation process for electrolyzing manganese |
| CN102061486A (en) * | 2010-10-12 | 2011-05-18 | 重庆大学 | Method for reducing magnesium ion concentration of electrolytic manganese anolyte |
Non-Patent Citations (1)
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| "锰电解返回液结晶沉淀问题研究";韩培伟等;《铁合金》;20121231(第5期);第19-22页 * |
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