CN110317962A - Manganese Wet-smelting method and manganese hydrometallurgy system - Google Patents
Manganese Wet-smelting method and manganese hydrometallurgy system Download PDFInfo
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- CN110317962A CN110317962A CN201910703551.7A CN201910703551A CN110317962A CN 110317962 A CN110317962 A CN 110317962A CN 201910703551 A CN201910703551 A CN 201910703551A CN 110317962 A CN110317962 A CN 110317962A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/02—Apparatus therefor
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/08—Sulfuric acid, other sulfurated acids or salts thereof
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B47/00—Obtaining manganese
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/06—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese
- C25C1/10—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese of chromium or manganese
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The present invention provides a kind of manganese Wet-smelting methods and manganese hydrometallurgy system.Smelting process includes successively carrying out sulfuric acid leaching and removal of impurities to manganese ore, obtains the mixed solution of containing magnesium sulfate, manganese sulfate and ammonium sulfate；Mixed solution is divided into first part and second part, electrodeposition processing is passed sequentially through to the mixed solution of first part and electrolysis is handled, obtains valuable metal manganese；Manganese precipitation process and magnesium precipitate processing are successively carried out to the mixed solution of second part, obtain manganese sediment and magnesium precipitate object；The step of manganese sediment is returned into sulfuric acid leaching.By being extracted out to a part in the mixed solution after removal of impurities, and manganese and magnesium are precipitated respectively, manganese returns to the smelting process that leaching step continues to complete manganese, and magnesium salts is then discharged in the form of sediment.This method is discharged magnesium in manganese smelting process outside reaction system in the form of precipitation slag, reduces the crystallization of magnesium to a certain extent, and then reduces the risk of blocking pipeline, improves the stability of production.
Description
Technical field
The present invention relates to field of hydrometallurgy, in particular to a kind of manganese Wet-smelting method and manganese hydrometallurgy system
System.
Background technique
As shown in Figure 1, domestic manganese hydrometallurgical processes are: main to pass through after the levigate material progress pulp of manganese is obtained manganese ore slurry
After over cure leaching-ore, removal of impurities (including except iron aluminium and removing heavy metals), it is obtained by filtration and completes liquid, then pass through technique electrodeposition output yin
Pole manganese piece (i.e. manganese cathode plate).Benefit ammonia is carried out in electrolytic deposition process, in process operation, ammonium salt and the magnesium salts after leaching are without open circuit
(i.e. ammonium salt and magnesium salts constantly generate in systems, but do not export, and are not discharged from system correspondingly), thus, it can only
In systems constantly accumulation, until reach saturation after in process system mass crystallization, not only occupy system response space, but also
Pipeline is blocked, unstable hidden danger is caused to production.Therefore, at present can only forcibly from tailings open a way ammonium salt, magnesium salts,
Manganese salt, but these ammonium salt, magnesium salts and manganese salts for coming out are all unprocessed, thus environment is caused to seriously threaten.
Summary of the invention
It is existing to solve the main purpose of the present invention is to provide a kind of manganese Wet-smelting method and manganese hydrometallurgy system
The unstable problem of manganese hydrometallurgy system production in technology.
To achieve the goals above, according to an aspect of the invention, there is provided a kind of method that manganese is smelted, this method packet
It includes: sulfuric acid leaching and removal of impurities successively being carried out to manganese ore, obtain the mixed solution of containing magnesium sulfate, manganese sulfate and ammonium sulfate；It will mixing
Solution is divided into first part and second part, passes sequentially through electrodeposition processing to the mixed solution of first part and electrolysis is handled, obtain
To valuable metal manganese；Manganese precipitation process and magnesium precipitate processing are successively carried out to the mixed solution of second part, obtain manganese sediment
With magnesium precipitate object；The step of manganese sediment is returned into sulfuric acid leaching.
Further, manganese precipitation process is carried out using mixed solution of the oxidizing process to second part, it is preferable that using oxygen
Before change method, method further includes the steps that carrying out tune pH value to the mixed solution of second part；It is further preferred that using ammonium hydroxide by pH value
It is adjusted to 6.5-9.5；It is preferred that being aoxidized in oxidizing process using oxidant, more preferable oxidant is compressed air, pure oxygen or double
Oxygen water；Preferably, the time of manganese precipitation process is 2-10h, and temperature is 40-80 DEG C.
Further, using go ammonia process carry out magnesium precipitate processing, it is preferable that using go ammonia process carry out magnesium precipitate handle it
Before, method further include: pH value adjusting is carried out to the first filtrate after manganese precipitation process, is more preferably adjusted to pH value using ammonium hydroxide
9.0-10.0；Preferably, magnesium precipitate processing is carried out using ammonium carbonate or ammonium hydrogen carbonate, obtains basic carbonate magnesium precipitate；Preferably,
The time of magnesium precipitate processing is 0.5-5h, and temperature is 40-80 DEG C.
Further, method further includes being used to recycle in removal step by magnesium precipitate object；Preferably, removal step packet
Include successively carry out except iron aluminium step and removing heavy metals step；Preferably, in the step of magnesium precipitate object is used for except iron aluminium.
Further, after carrying out magnesium precipitate processing to the mixed solution of second part, method further includes to magnesium precipitate processing
The second filtrate afterwards carries out recovery ammonia processing；Preferably, recovery ammonia handle the step of include: using milk of lime to the second filtrate into
Row causticizing reaction, and washing is filtered to reaction product, obtain the ammonium hydroxide of calcium sulphate dihydrate filter cake and the first concentration；It is preferred that
Ground, milk of lime are the milk of lime of 10-20wt%, it is preferable that the pH value of causticizing reaction is 10.0-11.0, it is preferable that causticizing reaction
Time be 0.5-2h, temperature be 40-80 DEG C.
Further, the step of recovery ammonia is handled further include: heating evaporation is carried out to ammonium hydroxide, obtains the ammonia of the second concentration
Water, it is preferable that by the ammonium hydroxide of the second concentration return in electrodeposition processing, manganese precipitation process and magnesium precipitate processing any one or it is more
In a step.
To achieve the goals above, according to the second aspect of the invention, a kind of manganese smelting system is provided, which smelts
System includes: smelting device and open circuit set, and smelting device includes the leaching unit being sequentially communicated, impurity removing unit, electrodeposition unit
And electrolysis cells；Open circuit set includes the manganese precipitation unit being sequentially communicated and magnesium precipitate unit, wherein manganese precipitation unit enters
Mouthful be arranged between impurity removing unit and electrodeposition unit, manganese precipitation unit further includes manganese circulation line, the outlet of manganese circulation line with
Leach unit connection.
Further, impurity removing unit includes being sequentially communicated except iron aluminium unit and removing heavy metals unit, magnesium precipitate unit packet
Magnesium circulation line is included, magnesium circulation line is connected with iron aluminium unit is removed.
Further, manganese smelting system further includes ammonia recovery unit, and the downstream of magnesium precipitate unit is arranged in ammonia recovery unit,
And it is connected with magnesium precipitate unit.
Further, ammonia recovery unit includes ammonia concentrator；Preferably, ammonia concentrator is connected at least one of
It is logical: electrodeposition unit, manganese precipitation unit and magnesium precipitate unit.
Apply the technical scheme of the present invention, the original Wet-smelting method on the basis of, by after removal of impurities containing manganese,
A part in the mixed solution of magnesium and ammonia is extracted out, and is precipitated respectively to manganese therein and magnesium, and wherein manganese returns to leaching
Step continues to complete the smelting process of manganese out, and magnesium salts is then discharged in the form of sediment.This method makes manganese smelting process
Middle magnesium is discharged outside reaction system in the form of precipitation slag, to reduce the crystallization of magnesium to a certain extent, and then is reduced
The risk of pipeline is blocked, and then improves the stability of production.
Detailed description of the invention
The accompanying drawings constituting a part of this application is used to provide further understanding of the present invention, and of the invention shows
Examples and descriptions thereof are used to explain the present invention for meaning property, does not constitute improper limitations of the present invention.In the accompanying drawings:
Fig. 1 shows the flow diagram of manganese smelting process in the prior art；
Fig. 2 shows the flow diagrams of provided manganese smelting process according to an embodiment of the present application；
Fig. 3 show in Fig. 2 to part manganese, magnesium, ammonia mixed solution the detailed process schematic diagram handle；
Fig. 4 shows the structural schematic diagram of provided manganese smelting system according to an embodiment of the present application；And
Fig. 5 shows the detailed construction schematic diagram of the manganese smelting system according to provided by preferred embodiment of the present application.
In above-mentioned attached drawing, there is following appended drawing reference:
10, smelting device；20, open circuit set；30, ammonia recovery unit；
11, unit is leached；12, impurity removing unit；13, electrodeposition unit；14, electrolysis cells；
21, manganese precipitation unit；22, magnesium precipitate unit；
101, manganese circulation line；102, magnesium circulation line；
121, iron aluminium unit is removed；122, removing heavy metals unit.
Specific embodiment
It should be noted that in the absence of conflict, the features in the embodiments and the embodiments of the present application can phase
Mutually combination.Below in conjunction with embodiment, the present invention will be described in detail.
As background technique is previously mentioned, magnesium and ammonia are not opened a way in existing manganese smelting process system, in systems constantly
It is accumulated by, up to the excessive concentration accumulated crystallizes out.And it is more and more with crystallizing, reaction pipeline is occupied or even stifled
Plug, causes system fluctuation of service.In order to improve above-mentioned condition, in a kind of typical embodiment of the application, one is provided
The method that kind of manganese is smelted, as shown in Fig. 2, this method comprises: successively carry out sulfuric acid leaching and removal of impurities to manganese ore, obtain magnesium sulfate,
The mixed solution of manganese sulfate and ammonium sulfate；Mixed solution is divided into first part and second part, it is molten to the mixing of first part
Liquid passes sequentially through electrodeposition processing and electrolysis processing, obtains valuable metal manganese；It is heavy that manganese is successively carried out to the mixed solution of second part
It forms sediment to handle and be handled with magnesium precipitate, obtain manganese sediment and magnesium precipitate object；Manganese sediment is returned into leaching step.
The method that the above-mentioned manganese of the application is smelted, on the basis of original Wet-smelting method, by containing after removal of impurities
There is a part in the mixed solution of manganese, magnesium and ammonia to be extracted out, and manganese therein and magnesium are precipitated respectively, wherein manganese returns
The smelting process that leaching step continues to complete manganese is returned, and magnesium salts is then discharged in the form of sediment.This method smelts manganese
Magnesium is discharged outside reaction system in the form of precipitation slag in the process, to reduce the crystallization of magnesium to a certain extent, and then is subtracted
The risk of low blocking pipeline, and then improve the stability of production.
According to the actual application, the magnesium precipitate object of discharge can return to main process system with a part, instead of part stone
Ash makees neutralizer and cleans, and the big system open loop of product formation is then made in another part.
In above-mentioned manganese smelting process, to the manganese in the mixed solution of the containing magnesium sulfate of extraction section, manganese sulfate and ammonium sulfate
There are many ways to being precipitated can specifically use existing coprecipitation mode.In a kind of preferred embodiment of the application, use
Oxidizing process carries out manganese precipitation process to the mixed solution of second part.The principle of oxidizing process precipitating manganese is: the dissolution of manganous hydroxide
Spend bigger, the manganese ion solution of low concentration adds excessive ammonia that will not precipitate.And under alkaline condition, it manganous hydroxide and does not sink
MnO (OH) of manganese ion (such as under the conditions of ammonia) the easily oxidation by air in shallow lake to tetravalent manganese2, further dehydration can obtain four
Mn 3 O precipitating.That is, directly carrying out precipitating required pH value to bivalent manganese relatively high, and use air oxidation can be with
PH value needed for reducing precipitating, and high value manganese product can be formed.
It has been observed that oxidizing process precipitating manganese needs under alkaline condition, thus in a kind of preferred embodiment, using oxygen
Before change method, the above method further includes the steps that carrying out tune pH value to the mixed solution of second part；It is preferred that using ammonium hydroxide by pH
Value is adjusted to 6.5-9.5；It is aoxidized in more preferable oxidizing process using oxidant, more preferable oxidant is compressed air, pure oxygen
Or hydrogen peroxide；It is highly preferred that the time of manganese precipitation process is 2-10h, temperature is 40-80 DEG C.
The condition of above-mentioned precipitating manganese can make the manganese ion in mixed solution precipitate relatively more thoroughly, so that manganese
The smelting yield of valuable metal manganese is higher in mine.I.e. by by part mixed solution extraction after, by magnesium therein with precipitation form
It is discharged from reaction system, after ammonia is discharged in the form of a solution, and manganese still returns in smelting system.The smelting of manganese is neither influenced in this way
Yield is refined, the crystalline polamer in former smelting system is decreased, improves the stability of production.
After the above-mentioned manganese to precipitating, then the magnesium ion in surplus solution is precipitated, specific intermediate processing can be adopted
With existing any available intermediate processing.In a kind of preferred embodiment, using go ammonia process carry out magnesium precipitate processing.
In a kind of preferred embodiment, before use goes ammonia process to carry out magnesium precipitate processing, the above method further include: right
The first filtrate after manganese precipitation process carries out pH adjusting, and pH value is more preferably adjusted to 9.0-10.0 using ammonium hydroxide.Preferably, it adopts
Magnesium precipitate processing is carried out with ammonium carbonate or ammonium hydrogen carbonate, obtains basic carbonate magnesium precipitate；Preferably, the time of magnesium precipitate processing is
0.5-5h, temperature are 40-80 DEG C.
Under the pH value condition of 9.0-10.0, the reactive mode of magnesium is precipitated are as follows:
MgSO4+2NH4OH=Mg (OH)2+(NH4)2SO4
Directly use AMMONIA TREATMENT, above-mentioned reaction can carry out, but under this reaction magnesium direct yield only 65%, also
It is to say that remaining magnesium just has no idea to recycle in the process of ammonium hydroxide tune pH value, has just gone to downstream process.If adding in the step
After entering ammonium salt, direct yield be can be improved to 90% or so.
In order to be further reduced the solid waste generated in production process to environment while improving manganese smelting production stability
Pollution, in a preferred embodiment of the present application, the above method further includes being used to recycle in removal step by magnesium precipitate object
It utilizes.Magnesium precipitate object is recycling in removal step, not only reduces waste discharge, but also reduces production energy consumption.
In a kind of preferred embodiment, as shown in Figure 1, above-mentioned removal step include successively carry out except iron aluminium step and
Removing heavy metals step；Preferably, in the step of magnesium precipitate object is used for except iron aluminium.Milk of lime (main component is used in the prior art
It is Ca (OH)2) clean, mainly iron aluminium conversion hydrate precipitating is removed.The step of above-mentioned removing heavy metals is existing
Some conventional steps, details are not described herein again.
In manganese smelting process provided herein, after carrying out magnesium precipitate processing to the mixed solution of second part, the party
Method further includes carrying out recovery ammonia processing to magnesium precipitate treated the second filtrate.It is remaining molten after carrying out precipitation process to manganese and magnesium
Ammonia in liquid still can be recycled.Due to either being walked in electrodeposition processing in the prior art step of manganese smelting process
Suddenly, it or in the step of precipitating manganese and precipitating magnesium, is required to carry out in alkaline environment, thus ammonia is recycled
Afterwards, can be used in these steps, for pH value to be adjusted.
In a kind of preferred embodiment, recovery ammonia processing the step of include: using milk of lime to the second filtrate carry out it is severe
Change reaction, and washing is filtered to reaction product, obtains the ammonium hydroxide of calcium sulphate dihydrate filter cake and the first concentration；Preferably, stone
The milk of lime that grey cream is 10-20wt%, it is preferable that the pH value of causticizing reaction is 10.0-11.0, it is preferable that causticizing reaction when
Between be 0.5-2h, temperature be 40-80 DEG C.
The reaction equation of causticizing reaction is carried out to the second filtrate using milk of lime are as follows:
Ca(OH)2+(NH4)2SO4+2H2O=CaSO4·2H2O+2NH4OH.Causticization is carried out using the milk of lime of 10-20wt%
Reaction, and the pH value of causticizing reaction is controlled within the scope of 10.0-11.0, range temperature is because of milk of lime quality at 40-80 DEG C
Concentration is too low, and the system water of bringing into is too big, and lime milk concentration is excessively high, and pump and pipeline are easy to appear problem.Correspondingly, anti-
Whether thoroughly reasonably adjusted between seasonable according to reaction.
In the step of above-mentioned recovery ammonia processing, the ammonium hydroxide of the first concentration of recycling, the usually relatively low ammonium hydroxide of concentration, if
It recycles, require supplementation with highly concentrated ammonium hydroxide or the ammonium hydroxide of recycling is concentrated.In a kind of preferred embodiment, ammonia
The step of recovery processing further include: heating evaporation is carried out to ammonium hydroxide, obtains the ammonium hydroxide of the second concentration, it is preferable that by the second concentration
Ammonium hydroxide return electrodeposition processing, manganese precipitation process and magnesium precipitate processing in any one or more steps in.
In second of the application typical embodiment, a kind of manganese smelting system is provided, as shown in figure 4, the manganese smelting
Refining system includes: smelting device 10 and open circuit set 20, wherein smelting device 10 includes the leaching unit 11 being sequentially communicated, removes
Different kinds of bonding units 12, electrodeposition unit 13 and electrolysis cells 14；Open circuit set 20 includes that the manganese precipitation unit 21 being sequentially communicated and magnesium are heavy
Shallow lake unit 22, wherein the entrance of manganese precipitation unit 21 is arranged between impurity removing unit 12 and electrodeposition unit 13, manganese precipitation unit 21
It further include manganese circulation line 101, the outlet of manganese circulation line 101 is connected to unit 11 is leached.
The system that the above-mentioned manganese of the application is smelted increases open circuit set on the basis of original hydrometallurgy device 10
20, by the way that being transferred to for sulfuric acid mixed salt solution containing manganese, magnesium and ammonia for transporting electrodeposition unit 13 after impurity removing unit 12 to is added
Open circuit set 20 in, and the manganese precipitation unit 21 being sequentially communicated and magnesium precipitate unit 22 are set in open circuit set 20, will be turned
Manganese and magnesium in the mixed solution of shifting are precipitated respectively, and manganese is returned to leaching unit 11 by manganese circulation line 101 and is relayed
The continuous smelting for completing manganese, and magnesium salts is discharged in the form of sediment in magnesium precipitate unit 22, the remaining solution containing ammonia also takes off
From former smelting device 10.Thus, magnesium and ammonia are discharged from former smelting system the manganese smelting system of the application in different forms, from
And reduce crystalline polamer and its accumulation to a certain extent, and then reduce the risk of blocking pipeline, and then improve smelting
The stability of production.
Impurity removing unit 12 in above-mentioned smelting device 10 is identical as existing impurity removing unit 12.In a kind of preferred embodiment
In, as shown in figure 5, impurity removing unit 12 includes being sequentially communicated except iron aluminium unit 121 and removing heavy metals unit 122, magnesium precipitate list
Member 22 includes magnesium circulation line 102, and magnesium circulation line 102 is connected with iron aluminium unit is removed.
In above preferred embodiment, by the way that magnesium circulation line 102 is arranged in magnesium precipitate unit 22, and pass through magnesium circulation pipe
Road 102 makes an addition to the magnesium salts in magnesium precipitate unit 22 in impurity removing equipment to neutralize with except iron aluminium unit is connected
Except iron.Certainly, the magnesium salts of precipitating obtained can be used for selling.It is rationally disposed with specific reference to actual needs.
In order to be further reduced the solid waste generated in production process to environment while improving manganese smelting production stability
Pollution, in a kind of preferred embodiment, as shown in figure 5, manganese smelting system further includes ammonia recovery unit 30, ammonia recovery unit
30 are arranged in the downstream of magnesium precipitate unit 22, and are connected with magnesium precipitate unit 22.
Specifically the setting form of ammonia recovery unit 30 is unlimited, any to can be realized the equipment or instrument recycled to ammonia
It is suitable for the application.In a kind of preferred embodiment, ammonia recovery unit 30 includes ammonia concentrator.
In order to reduce the energy consumption for realizing manganese smelting system, in a kind of preferred embodiment, as shown in figure 5, ammonia concentration is set
It is standby to be connected at least one of: electrodeposition unit 13, manganese precipitation unit 21 and magnesium precipitate unit 22.By ammonia concentrator with
It is above-mentioned it is one or more be connected to, the utilization efficiency of the ammonia of recycling can be improved, while reducing the whole energy consumption of system.
Further illustrate the beneficial effect of the application below in conjunction with specific embodiments.
Embodiment 1
Manganese ore is smelted according to method shown in FIG. 1, after sulfuric acid leaching, removal step, obtained completion liquid
Ingredient such as the following table 1:
Table 1:
| Ingredient | Concentration, g/L |
| Mn2+ | 29.46 |
| Mg2+ | 21.18 |
| (NH4)2SO4 | Saturation |
Subsequent electrodeposition processing is carried out according to process shown in Fig. 1 to the part solution in above-mentioned table 1 and electrolysis is handled.And it remains
The solution of remaining part point is handled according to Fig. 2 and process shown in Fig. 3.Heavy manganese is aoxidized first, and pH=8.5 is adjusted using ammonium hydroxide,
Oxidant uses hydrogen peroxide, sinks the manganese time for 8h, temperature is 60 DEG C.Mangano-manganic oxide filter cake is obtained after filtration washing.Return to master
Process ((in slurry step i.e. shown in FIG. 1) is leached in technique.
After heavy manganese filtering, filtrate goes ammonia process magnesium sinking, and magnesium sinking adjusts pH=9.1 using ammonium hydroxide, and ammonium carbonate or bicarbonate is added
Ammonium, use level coefficient be 1.2 (use level coefficient 1, refer to just by chemical equation measure than feed, if it is 1.2, just
It is more 20%mol on the basis of chemical equation), the magnesium sinking time is 2h, and temperature is 80 DEG C.Alkali is obtained after filtration washing
Formula magnesium carbonate filter cake.Part returns in smelting process shown in FIG. 1, as the neutralizer for removing iron.
Filtrate uses 20wt% milk of lime causticization after magnesium sinking, adjusts pH=10.5, and the causticization time is 0.5h, temperature 60
℃.Calcium sulphate dihydrate filter cake is obtained after filtration washing.
Filtrate is weak aqua ammonia, and after ammonia still process, ammonia concn can achieve 15%, returns to electrodeposition processing step shown in FIG. 1.
Embodiment 2
The solution of remainder in embodiment 1 is handled according to Fig. 2 and process shown in Fig. 3.Heavy manganese is aoxidized first,
PH=6.5 is adjusted using ammonium hydroxide, oxidant uses hydrogen peroxide, sinks the manganese time for 10h, temperature is 80 DEG C.It is obtained after filtration washing
Mangano-manganic oxide filter cake, and filter cake is returned and is leached in main technique in process (in slurry step i.e. shown in FIG. 1).
After heavy manganese filtering, filtrate goes ammonia process magnesium sinking, and magnesium sinking adjusts pH=9.0 using ammonium hydroxide, and ammonium carbonate, use level coefficient is added
It is 1.2, the magnesium sinking time is 5h, and temperature is 40 DEG C.Basic magnesium carbonate filter cake is obtained after filtration washing.Part returns shown in FIG. 1
In smelting process, as the neutralizer for removing iron.
Filtrate uses 10wt% milk of lime causticization after magnesium sinking, adjusts pH=10.0, and the causticization time is 2h, and temperature is 80 DEG C.
Calcium sulphate dihydrate filter cake is obtained after filtration washing, can be used as building materials raw material.
Filtrate is weak aqua ammonia, and after ammonia still process, ammonia concn can achieve 18%, for pH in manganese settling step shown in Fig. 3
It is worth the process adjusted.
Embodiment 3
The solution of remainder in embodiment 1 is handled according to Fig. 2 and process shown in Fig. 3.Heavy manganese is aoxidized first,
PH=9.5 is adjusted using ammonium hydroxide, oxidant uses compressed air, sinks the manganese time for 2h, temperature is 40 DEG C.It is obtained after filtration washing
Mangano-manganic oxide filter cake, and filter cake is returned and is leached in main technique in process (in slurry step i.e. shown in FIG. 1).
After heavy manganese filtering, filtrate goes ammonia process magnesium sinking, and magnesium sinking adjusts pH=10.0 using ammonium hydroxide, and ammonium hydrogen carbonate, dosage is added
Coefficient is 1.2, and the magnesium sinking time is 0.5h, and temperature is 80 DEG C.Basic magnesium carbonate filter cake is obtained after filtration washing.Part returns to Fig. 1
Shown in smelting process, as the neutralizer for removing iron.
Filtrate uses 15wt% milk of lime causticization after magnesium sinking, adjusts pH=11.0, and the causticization time is 0.5h, temperature 40
℃.Calcium sulphate dihydrate filter cake is obtained after filtration washing, can be used as building materials raw material.
Filtrate is weak aqua ammonia, and after ammonia still process, ammonia concn can achieve 16%, for pH in manganese settling step shown in Fig. 3
It is worth the process adjusted.
Embodiment 4
The solution of remainder in embodiment 1 is handled according to Fig. 2 and process shown in Fig. 3.Heavy manganese is aoxidized first,
PH=9.8 is adjusted using ammonium hydroxide, oxidant uses compressed air, sinks the manganese time for 5h, temperature is 38 DEG C.It is obtained after filtration washing
Mangano-manganic oxide filter cake, and filter cake is returned and is leached in main technique in process (in slurry step i.e. shown in FIG. 1).
After heavy manganese filtering, filtrate goes ammonia process magnesium sinking, and magnesium sinking adjusts pH=10.3 using ammonium hydroxide, and ammonium hydrogen carbonate, dosage is added
Coefficient is 1.2, and the magnesium sinking time is 0.5h, and temperature is 85 DEG C.Basic magnesium carbonate filter cake is obtained after filtration washing.Part returns to Fig. 1
Shown in smelting process, as the neutralizer for removing iron.
Filtrate uses 5wt% milk of lime causticization after magnesium sinking, adjusts pH=11.0, and the causticization time is 0.5h, and temperature is 40 DEG C.
Calcium sulphate dihydrate filter cake is obtained after filtration washing, can be used as building materials raw material.
Filtrate is weak aqua ammonia, and after ammonia still process, ammonia concn can achieve 16%, for pH in manganese settling step shown in Fig. 3
It is worth the process adjusted.
It can be seen from the above description that the above embodiments of the present invention realized the following chievements: the application
The method that above-mentioned manganese is smelted, on the basis of original Wet-smelting method, by the mixing containing manganese, magnesium and ammonia after removal of impurities
A part in solution is extracted out, and is precipitated respectively to manganese therein and magnesium, and wherein manganese returns to leaching step and continued
The smelting process of Cheng Meng, and magnesium salts is then discharged in the form of sediment.This method makes in manganese smelting process magnesium with precipitation slag
Form be discharged outside reaction system, to reduce the crystallization of magnesium to a certain extent, and then reduce the wind of blocking pipeline
Danger, and then improve the stability of production.
Above scheme provided herein, having the advantages that compared with prior art 1) realizes valuable metal extraction
Former process is docked with open circuit the effective of process, and simple process.2) whole recycling of slag can be achieved.3) ammonium hydroxide is as neutralizer,
It can be recycled.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field
For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, made any to repair
Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of method that manganese is smelted, which is characterized in that the described method includes:
Sulfuric acid leaching and removal of impurities are successively carried out to manganese ore, obtain the mixed solution of containing magnesium sulfate, manganese sulfate and ammonium sulfate；
The mixed solution is divided into first part and second part, electrodeposition is passed sequentially through to the mixed solution of the first part
Processing and electrolysis processing, obtain valuable metal manganese；
Manganese precipitation process and magnesium precipitate processing are successively carried out to the mixed solution of the second part, manganese sediment is obtained and magnesium is heavy
Starch；
The step of manganese sediment is returned into the sulfuric acid leaching.
2. the method according to claim 1, wherein using oxidizing process to the mixed solution of the second part into
Row manganese precipitation process,
Preferably, before using the oxidizing process, the method also includes the mixed solutions to the second part to adjust
The step of pH value；
It is further preferred that the pH value is adjusted to 6.5-9.5 using ammonium hydroxide；
It is preferred that being aoxidized in the oxidizing process using oxidant, the more preferable oxidant is compressed air, pure oxygen or dioxygen
Water；
Preferably, the time of the manganese precipitation process is 2-10h, and temperature is 40-80 DEG C.
3. the method according to claim 1, wherein using going ammonia process to carry out the magnesium precipitate processing,
Preferably, before use goes ammonia process to carry out the magnesium precipitate processing, the method also includes: to the manganese precipitation process
The first filtrate afterwards carries out pH value adjusting, and the pH value is more preferably adjusted to 9.0-10.0 using ammonium hydroxide；
Preferably, the magnesium precipitate processing is carried out using ammonium carbonate or ammonium hydrogen carbonate, obtains basic carbonate magnesium precipitate；
Preferably, the time of the magnesium precipitate processing is 0.5-5h, and temperature is 40-80 DEG C.
4. according to the method described in claim 3, it is characterized in that, described the method also includes the magnesium precipitate object to be used for
It is recycled in removal step；
Preferably, the removal step includes successively carrying out except iron aluminium step and removing heavy metals step；
Preferably, the magnesium precipitate object is in described the step of removing iron aluminium.
5. method according to claim 1 to 4, which is characterized in that the mixed solution of the second part
After carrying out the magnesium precipitate processing, the method also includes carrying out at recovery ammonia to the magnesium precipitate treated the second filtrate
Reason；
Preferably, the recovery ammonia handle the step of include:
Causticizing reaction is carried out to second filtrate using milk of lime, and washing is filtered to reaction product, obtains two water sulphur
The ammonium hydroxide of sour calcium filter cake and the first concentration；
Preferably, the milk of lime is the milk of lime of 10-20wt%,
Preferably, the pH value of the causticizing reaction is 10.0-11.0,
Preferably, the time of the causticizing reaction is 0.5-2h, and temperature is 40-80 DEG C.
6. according to the method described in claim 5, it is characterized in that, the step of recovery ammonia is handled further include: to the ammonia
Water carries out heating evaporation, obtains the ammonium hydroxide of the second concentration,
Preferably, the ammonium hydroxide of second concentration is returned in the electrodeposition processing, the manganese precipitation process and magnesium precipitate processing
Any one or more steps in.
7. a kind of manganese smelting system, which is characterized in that the manganese smelting system includes:
Smelting device, including leaching unit, impurity removing unit, electrodeposition unit and the electrolysis cells being sequentially communicated；
Open circuit set, the open circuit set include the manganese precipitation unit being sequentially communicated and magnesium precipitate unit, wherein the manganese precipitating
The entrance of unit is arranged between the impurity removing unit and the electrodeposition unit, and the manganese precipitation unit further includes manganese circulation pipe
Road, the outlet of the manganese circulation line are connected to the leaching unit.
8. manganese smelting system according to claim 7, which is characterized in that the impurity removing unit includes being sequentially communicated except iron
Aluminium unit and removing heavy metals unit, the magnesium precipitate unit include magnesium circulation line, and the magnesium circulation line removes iron aluminium with described
Unit is connected.
9. manganese smelting system according to claim 7, which is characterized in that the manganese smelting system further includes recovery ammonia list
Member, the downstream of the magnesium precipitate unit is arranged in the ammonia recovery unit, and is connected with the magnesium precipitate unit.
10. manganese smelting system according to claim 9, which is characterized in that the ammonia recovery unit includes ammonia concentrator；
Preferably, the ammonia concentrator is connected at least one of: the electrodeposition unit, the manganese precipitation unit and
The magnesium precipitate unit.
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| CN112939090A (en) * | 2021-05-14 | 2021-06-11 | 蜂巢能源科技有限公司 | Manganese sulfate purification and crystallization method |
| CN115108570A (en) * | 2022-06-17 | 2022-09-27 | 中南大学 | Process for preparing basic magnesium carbonate and ammonium sulfate by innocent treatment in manganese-containing wastewater |
| WO2024052760A1 (en) * | 2022-09-06 | 2024-03-14 | Manganese Metal Company (Pty) Ltd | A process for producing manganese sulphate monohydrate |
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