CN107699714A - A kind of method that manganese sulfate electrolyte is prepared suitable for leaching pyrolusite by sulfur dioxide - Google Patents
A kind of method that manganese sulfate electrolyte is prepared suitable for leaching pyrolusite by sulfur dioxide Download PDFInfo
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- CN107699714A CN107699714A CN201710852855.0A CN201710852855A CN107699714A CN 107699714 A CN107699714 A CN 107699714A CN 201710852855 A CN201710852855 A CN 201710852855A CN 107699714 A CN107699714 A CN 107699714A
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- manganese
- pyrolusite
- liquid
- sulfur dioxide
- manganese sulfate
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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
- C22B47/00—Obtaining manganese
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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
- C22B3/46—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes by substitution, e.g. by cementation
Abstract
The present invention proposes a kind of method that manganese sulfate electrolyte is prepared suitable for leaching pyrolusite by sulfur dioxide, and central scope is：It is with slurry only with a part of anolyte and whole technique pyrolusites, obtain high-concentration sulfuric acid manganese solution after being reacted with sulfur dioxide；And another part anolyte is then neutralized, manganese sulfate concentration is obtained after solid-liquor separation and Yuanyang pole liquid identical low-concentration sulfuric acid manganese solution；Manganese sulfate concentration is can obtain after two parts manganese sulfate solution is mixed and reaches the qualified electrolyte that electrolysis requires.The method of the invention can improve the utilization ratio of sulfur dioxide and pyrolusite in leaching process, reduce the capital construction cost and operating cost leached with leachate impurity removal process.
Description
Technical field
The invention belongs to the technical field of wet metallurgy of raw material containing manganese, and in particular to one kind leaching pyrolusite by sulfur dioxide
In manganese prepare manganese sulfate electrolyte method.
Background technology
Electrolytic manganese is the important alloying element for producing stainless steel, Aldecor, alumal, cupromanganese etc..
Electrolytic manganese dioxide is the depolarizing agent of excellent battery, and it has compared with the naturally dry cell of electric discharge manganese dioxide production
The features such as discharge capacity is big, activity is strong, small volume, long lifespan.At present, electrolytic manganese and manganese dioxide are mainly by being electrolysed sulfuric acid
The mode of manganese solution obtains, therefore prepares the important prerequisite bar that qualified electrolyte is the high-quality electrolytic manganese of production and manganese dioxide
Part.For the preparation method of reclaiming metals manganese and the electrolyte of manganese dioxide, basic technology is identical, mainly including manganese
Two stages of the leaching of ore deposit and the purification and impurity removal of leachate.Manganese in manganese resource pyrolusite exists in the form of manganese dioxide,
Can not be with direct reaction of sulfuric acid, method general at present is to be calcined at high temperature, and manganese dioxide is reduced into acid using reducing agent
Molten manganese oxide, sulfuric acid solution is recycled to leach to obtain manganese sulfate electrolyte.This roasting reduction technique has to manganese ore grade
High requirement, when manganese ore manganese content is more than 40%, the technology has some superiority, but the average grade of Chinese pyrolusite is only
For 22%, there is that reduction efficiency is low, impurity leaching rate is big and equipment investment is larger, power consumption is high using reduction roasting-acid leaching process
The problems such as, thus fail extensive use.It is a kind of soft manganese developed in recent years that sulfur dioxide liquid-phase reduction, which leaches pyrolusite,
The efficient leaching-out technique of ore deposit.The technology has that wide adaptation range, reaction condition are gentle, reaction rate is fast, manganese leaching rate is high and impurity
Leach the advantages that few.
During the electrolyte that electrolytic manganese or manganese dioxide are prepared using leaching pyrolusite by sulfur dioxide, pyrolusite pulp is consolidated
Liquor ratio (pyrolusite is with being used for anolyte with slurry) is important parameter, and the difference of solid-to-liquid ratio will be removed to leaching process and purification
Miscellaneous process has an impact.Wherein to the influence of leaching process：Increase of the sulfur dioxide absorption efficiency with manganese leaching rate with solid-to-liquid ratio
And increase, low solid-to-liquid ratio is unfavorable for the absorption of sulfur dioxide and the leaching of pyrolusite；It is certain in pyrolusite total amount and reaction time
In the case of, the increase of solid-to-liquid ratio can reduce the volume of ore pulp, reduce the volume of reactor and the power consumption of slurry conveying equipment,
And then reduce the capital construction cost and operating cost of leaching stage；Leaching pyrolusite by sulfur dioxide is exothermic reaction, in sulfur dioxide
With pyrolusite total amount it is certain in the case of, react that the heat of release is essentially identical, the increase of solid-to-liquid ratio can reduce the volume of ore pulp,
Reaction temperature is raised, promotes the leaching of pyrolusite.
Influence to purification and impurity removal process.The miscellaneous stage is being purified, no matter the impurity removal process used, the removal effect of impurity
The dosage of rate and cleaner is closely related.Under conditions of impurity content is higher, removal of impurity with cleaner dosage
Substantially linearly increase.But impurity content is dropped into electrolytic manganese and below the 1mg/L of manganese dioxide technological requirement, then requires to remove
Miscellaneous dose of content is significantly excessive, i.e., the amount of cleaner will often reach the several times even decades of times of theoretical dosage.When with slurry
Solid-to-liquid ratio is lower, and caused leachate volume is bigger, and the dosage of cleansing phase cleaner is bigger.
In the method for preparing electrolytic manganese on leaching pyrolusite by sulfur dioxide at present, as disclosed in ZL201210102916.9
" sulphur calcium disclosed in " sulfur dioxide leaches the method that manganese oxide produces electrolytic manganese/electrolytic manganese dioxide ", ZL201210117146.5
The method that circulation leaching manganese oxide prepares electrolytic manganese/electrolytic manganese dioxide ", used electrolyte preparation method is by whole
Anolyte according to " in electrolyte manganese ion concentration be 35~60g/L " condition it is with slurry.Using manganese content as 25% pyrolusite
Exemplified by, when producing electrolytic manganese, manganese content is 15~20g/L in anolyte, and it is 35~40g/L to be electrolysed manganese content in new liquid, then
Manganese content caused by electrolyte preparatory phase needs is 20~25g/L, solid-to-liquid ratio (kg:L it is about) 1:10, so low solid-liquid
Than the leaching for being not only unfavorable for manganese ore, it can also increase the volume of leaching manganese reactor and the power consumption of pulp conveying, increase production
Cost.
The content of the invention
In view of the above-mentioned deficiencies in the prior art, it is an object of the present invention to providing a kind of new sulfur dioxide that is applied to leaches soft manganese
Ore deposit prepares manganese sulfate electrolyte preparation method, to improve the utilization ratio of sulfur dioxide and pyrolusite in leaching process, reduces leaching
Go out the capital construction cost and operating cost with leachate impurity removal process.
For the foregoing invention purpose of the present invention, the present invention proposes that one kind prepares sulphur suitable for leaching pyrolusite by sulfur dioxide
The method of sour manganese electrolyte, central scope are：It is with slurry only with a part of anolyte and whole technique pyrolusites, with sulfur dioxide
High-concentration sulfuric acid manganese solution is obtained after reaction；And another part anolyte is then neutralized, manganese sulfate concentration is obtained after solid-liquor separation
With Yuanyang pole liquid identical low-concentration sulfuric acid manganese solution；Manganese sulfate concentration is can obtain after two parts manganese sulfate solution is mixed to reach
The qualified electrolyte required to electrolysis.
The method of the present invention that manganese sulfate electrolyte is prepared suitable for leaching pyrolusite by sulfur dioxide, concrete technology is such as
Under：
(1) it is with slurry：It will meet and the soft manganese of process requirements in anolyte obtained by industrial production electrolytic manganese and manganese dioxide technique
A part of anolyte of ore deposit needs with slurry, pH is adjusted to the value leached suitable for manganese with calcium base nertralizer, is consolidated after fully neutralizing
Liquid separates, and obtains calcium sulfate and separating liquid, whole pyrolusites needed for separating liquid and technique be configured to liquid-solid ratio be 1L/kg~
4L/kg high solid-liquid ratio pyrolusite pulp；
(2) leach：Using sulfur dioxide or the waste gas containing sulfur dioxide reacts with the pyrolusite pulp obtained by step (1), leaching
The manganese gone out in pyrolusite, separation of solid and liquid is carried out to slurries after abundant Leach reaction, obtains pyrolusite slag and leachate；
(3) neutralize：The electrolytic manganese of remainder and manganese dioxide production anolyte are adjusted into pH to 5 with calcium base nertralizer
After~7, calcium sulfate and separating liquid are obtained through separation of solid and liquid after fully neutralizing；
(4) composition measurement：The content of heavy metal ion, works as heavy metal ion content in separating liquid obtained by determination step (3)
Reach electrolyte requirement, carry out according to the following steps：
(5a) purification and impurity removal：Nertralizer is added in leachate obtained by step (2), regulation pH is 5.0~6.5, and is added
Oxidant, iron ion and aluminium ion is generated iron hydroxide and aluminum hydroxide precipitation, when reach iron in solution, aluminium content is less than
During 1.0mg/L requirement, separation of solid and liquid is carried out to slurries, obtains neutralizing slag and separating liquid；Then vulcanization is added into separating liquid
Agent, beavy metal impurity ion generation sulfide precipitation is removed from solution, content of beary metal in solution is less than 1.0mg/L,
The slurries containing sediment are obtained, slurries are subjected to separation of solid and liquid, obtain vulcanized slag and separating liquid；
(6a) merges separating liquid：Separating liquid obtained by step (3) and step (5a) is mixed, obtains qualified manganese sulfate electrolysis
Liquid；
When heavy metal ion content exceedes the content of electrolyte requirement in separating liquid obtained by step (4) determination step (3),
Carry out according to the following steps：
(5b) purification and impurity removal：Heavy metal ion content obtained by step (2) is exceeded to the separating liquid and step of electrolyte requirement
(3) gained leachate mixing, nertralizer is added in gained mixed liquor, regulation pH is 5.0~6.5, and adds oxidant, makes iron
Ion and aluminium ion generation iron hydroxide and aluminum hydroxide precipitation, when reach iron in solution, aluminium content is less than 1.0mg/L requirement
When, separation of solid and liquid is carried out to slurries, obtains neutralizing slag and separating liquid；Then vulcanizing agent is added into separating liquid, makes heavy metal miscellaneous
Matter ion generation sulfide precipitation removes from solution, content of beary metal in solution is less than 1.0mg/L, obtains containing sediment
Slurries, slurries are subjected to separation of solid and liquid, obtain vulcanized slag and separating liquid, gained separating liquid is qualified manganese sulfate electrolyte.
In the above-mentioned technical proposal of the present invention, the qualified manganese sulfate electrolyte of gained is electrolysed, by gained after electrolysis
Anolyte return to step (1), form circulation technology.
In the above-mentioned technical proposal of the present invention, the manganese in pyrolusite is leached by sulfur dioxide obtains manganese sulfate solution,
Then electrolytic manganese or electrolytic manganese dioxide, the chemistry occurred in leaching process are reclaimed by being electrolysed the form of qualified manganese sulfate solution
React and be：
MnO2+SO2→MnSO4
The chemical reaction occurred in step (8) electrolytic process is：
MnSO4+H2O→Mn↓+H2SO4+1/2O2↑ (electrolytic manganese)
MnSO4+2H2O→MnO2↓+H2SO4+H2↑ (electrolytic manganese dioxide)
From the chemical reaction during above-mentioned two, in electrolytic process, the sulfate radical in manganese sulfate is converted into sulphur
Acid, and in pyrolusite leaching process, the manganese dioxide in pyrolusite can obtain manganese sulfate with sulfur dioxide directly reaction.Sulfuric acid
Presence can not only reduce the absorption efficiency of sulfur dioxide in leaching process, and can accumulate in circulating system sulfate radical content,
Destruction system balance, therefore, caused sulfuric acid must remove from system in electrolytic process, selective oxidation calcium, calcium hydroxide,
Calcium carbonate etc. is used as nertralizer, can not only neutralize acidity, and produces calcium sulfate precipitation, sulfate radical is removed, nertralizer
Feed postition be solid or the slurries that are mixed with water, specific reaction is as follows：
CaO+H2SO4→CaSO4↓+H2O
Ca(OH)2+H2SO4→CaSO4↓+2H2O
CaCO3+H2SO4→CaSO4↓+H2O+CO2↑
In the above-mentioned technical proposal of the present invention, it is relatively fixed, uses for pyrolusite quality with slurry in specific system
Smaller in anolyte volume with slurry, the solid-to-liquid ratio of gained pyrolusite pulp is bigger, and pyrolusite content is higher, is more advantageous to pyrolusite
The leaching of middle manganese and the absorption of sulfur dioxide.However, when being used for, anolyte volume with slurry is too small, and pyrolusite content is got in ore pulp
Height, ore pulp is more sticky, and mobility and sulfur dioxide mass-transfer performance are poorer, can cause the increase of pulp conveying power consumption, pyrolusite
Reactor wall caking and sulfur dioxide absorption efficiency decline the problems such as, therefore to improve solid-to-liquid ratio, by anolyte in the present invention
Volume is divided into two parts, is named as A, B two parts, and pyrolusite quality is with being used for the ratio between volume of part A anolyte with slurry
Preferably 1:(1~4) (kg/L).
In the above-mentioned technical proposal of the present invention, in pyrolusite leaching process, pH values of pulp is to influence the pass of leaching process
Key factor, under conditions of differential responses temperature, sulfur dioxide concentration and pyrolusite neutral and alkali content of material, required Optimal pH is not
Together, therefore, the pH range-controllable systems in anolyte after sulfuric acid are neutralized in step (2) 1~5, but the specific number optimized
Value need to determine according to the specific system condition of body.
In the above-mentioned technical proposal of the present invention, calculated in step (4) for pyrolusite total amount with slurry by following formula：
The qualified electrolyte is the electrolyte being electrolysed.When preparing electrolytic manganese, for manganese in the electrolyte of electrolysis
Concentration control is 35~45g/L；When preparing electrolytic manganese dioxide, for manganese concentration control in the electrolyte of electrolysis for 50~
70g/L。
In the above-mentioned technical proposal of the present invention, purification and impurity removal process is mainly to remove to enter leachate in leaching process
Accompanying element impurity, it is main to include neutralizing iron removal by oxidation aluminium and vulcanization removing heavy metals.In and during iron removal by oxidation aluminium, due to
During leaching pyrolusite by sulfur dioxide, the iron in leachate mainly exists in the form of ferrous sulfate, it is therefore desirable to first by it
Being oxidized to ferric sulfate, air, ozone, hydrogen peroxide, manganese dioxide or pyrolusite etc. can be oxidized, and then add ammonia
The nertralizer such as water or calcium hydroxide adjusts pH to 5~7, can make that ferric sulfate is converted into iron hydroxide with aluminum sulfate and aluminium hydroxide sinks
Form sediment, specific reaction is as follows：
Fe3++3OH-→Fe(OH)3
Al3++3OH-→Al(OH)3
Vulcanization the removing heavy metals stage, due to the heavy metals such as Zn, Cu, Ni, Co, Pb in leachate can with sulphion or
The stable sulfide precipitation of organic methylthio group generation, so as to be removed by the form of separation of solid and liquid from solution, therefore is added
Vulcanizing agent be that the sulfide of sulphion or organic methylthio group can be provided, ammonium sulfide, vulcanized sodium, Sodium Dimethyldithiocarbamate, second may be selected
One or more in sulphur nitrogen.Specific reaction is as follows：
Me2++S2-(Me is heavy metal to → MeS, S2-For sulphion or organic methylthio group)
Compared with prior art, the invention has the advantages that：
1st, the method for the invention is carried out with slurry only with the pyrolusite of a part of anolyte and whole, improves pyrolusite
Leach process in pyrolusite pulp solid-to-liquid ratio, be advantageous to the absorption of sulfur dioxide and the leaching of manganese ore, improve sulfur dioxide and
The utilization rate of pyrolusite.Solves the preparation that leaching pyrolusite by sulfur dioxide prepares electrolyte in electrolytic manganese or manganese dioxide technique
Existing solid-to-liquid ratio is low, the problem of bringing adverse effect to leaching process and purification and impurity removal process.
2nd, the method for the invention reduces the slurries that pyrolusite leaches process due to the solid-to-liquid ratio raising of pyrolusite pulp
Amount, on the basis of process residence time identical is leached, reduces equipment volume, the power for reducing slurries conveying equipment disappears
Consumption, reduces capital construction and cost of investment.
3rd, the method for the invention is improved due to the solid-to-liquid ratio of pyrolusite pulp, reduces the slurries amount of purification and impurity removal process,
The dosage of cleaner is reduced, reduces reagent cost.
Brief description of the drawings
Fig. 1 is the process flow diagram of the method for the invention.
Embodiment
It is applied to leaching pyrolusite by sulfur dioxide system to of the present invention with reference to process chart and by embodiment
The method of standby manganese sulfate electrolyte is described in further detail.It is important to point out that following embodiment is served only for this
Invention is described further, it is impossible to be interpreted as limiting the scope of the invention, art be skillful at personnel according to
Foregoing invention content, some nonessential modifications and adaptations are made to the present invention and are embodied, should still fall within the present invention's
Protection domain.
Embodiment 1
In the present embodiment, electrolytic manganese is prepared using leaching pyrolusite by sulfur dioxide, the anolyte in step (1) is conventional two
Sulfur oxide leaches pyrolusite and prepares anolyte caused by electrolytic manganese process electrowinning process, volume 100m3, manganese sulfate in anolyte
Content (concentration) is 15g/L, ammonium sulphate content 125g/L, sulfuric acid concentration 40g/L, and step (5) is used for manganese in the pyrolusite of leaching
Content is 28.5% (mass percent), set needed for manganese content is 38g/L in qualified electrolyte, manganese recovery ratio in whole process
Must be 80%, according toObtain
The quality of required pyrolusite is 10 tons, according to pyrolusite quality with being 1 for the ratio between the volume of anolyte with slurry (solid-to-liquid ratio):
3 (kg/L) are with slurry, then required part A anolyte volume is 30m3。
Electrolyte is prepared in accordance with the following steps：
(1) anolyte distributes：Anolyte caused by electrowinning process is divided into two parts, respectively 30m3(part A) and 70m3
(part B)；
(2) neutralize：By the 30m obtained by step (1)3It is 3.0 that anolyte is adjusted to pH with calcium oxide, obtains slurries, slurries
Press filtration separation is carried out, obtains calcium sulfate and separating liquid；
(3) it is with slurry：Separating liquid obtained by step (2) and 10 tons of pyrolusites is with slurry, solid-to-liquid ratio is obtained as 1:3 (kg/L's)
Pyrolusite pulp；
(4) leach：Reacted using the pyrolusite pulp obtained by sulfur dioxide and step (3), it is 90% to make pyrolusite leaching rate,
Manganese content is 100.8g/L in leachate, obtains the slurries containing pyrolusite slag and leachate, carries out press filtration to slurries, obtains soft
Manganese mud and leachate；
(5) neutralize：By the 70m obtained by step (1)3After (part B) anolyte adjusts pH to 6.0 with aqua calcis,
Calcium sulfate and separating liquid are obtained through separation of solid and liquid；
(6) composition measurement：The composition of separating liquid, its concentration of heavy metal ion reach qualified electrolysis obtained by determination step (5)
Liquid requirement；
(7) purification and impurity removal：Ammoniacal liquor is added in the slurries obtained by step (4), regulation pH is 6.0, and is passed through air, is made molten
Slurries are centrifuged, obtain neutralizing slag by iron ion and aluminium ion generation iron hydroxide and aluminum hydroxide precipitation in liquid
And separating liquid；8% ammonium sulfide solution is added into separating liquid according to 20ml/L amount, beavy metal impurity generation sulfide is sunk
Form sediment, obtain the slurries containing sediment, staticly settle, filter, obtain that heavy metal ion impurities reach electrolyte requirement, manganese ion contains
The manganese sulfate solution for 90.1g/L is measured, the manganese sulfate solution is mixed with separating liquid obtained by step (5), obtains 100m3Manganese ion
Concentration is 37.8g/L manganese sulfate electrolyte；
(8) it is electrolysed：It is electrolysed after antioxidant selenium dioxide being added in electrolyte obtained by step (7), obtains metal
Manganese, anolyte return to step (1) production electrolyte, forms circulation technology.
Embodiment 2
In the present embodiment, electrolytic manganese is prepared using leaching pyrolusite by sulfur dioxide, the anolyte in step (1) is conventional two
Sulfur oxide leaches pyrolusite and prepares anolyte caused by electrolytic manganese process electrowinning process, volume 100m3, manganese content in anolyte
Manganese content is in the pyrolusite for being used to leach for 17g/L, ammonium sulphate content 120g/L, sulfuric acid concentration 35g/L, step (5)
17.5% (mass percent), set needed for manganese concentration is 40g/L in qualified electrolyte, manganese recovery ratio is in whole process
82%, according toNeeded for obtaining
The quality of pyrolusite is 16 tons, according to pyrolusite quality with being 1 for the ratio between volume of anolyte with slurry:2.5 (kg/L) match somebody with somebody
Slurry, then required part A anolyte volume is 40m3。
(1) anolyte distributes：Anolyte caused by electrowinning process is divided into two parts, respectively 40m3(part A) and 60m3
(part B)；
(2) neutralize：By the 40m obtained by step (1)3It is 3.5 that anolyte is adjusted to pH with calcium oxide, obtains slurries, slurries
Press filtration is carried out, obtains calcium sulfate and separating liquid；
(3) it is with slurry：Separating liquid obtained by step (2) and 16 tons of pyrolusites is with slurry, solid-to-liquid ratio is obtained as 1:2.5(kg/L)
Pyrolusite pulp；
(4) leach：Reacted using the pyrolusite pulp obtained by sulfur dioxide and step (3), it is 92% to make pyrolusite leaching rate,
Manganese content is 78.1g/L in leachate, obtains the slurries containing pyrolusite slag and leachate, carries out press filtration to slurries, obtains soft
Manganese mud and leachate；
(5) neutralize：By the 60m obtained by step (1)3(part B) anolyte adjusts pH to 5.5 with calcium hydroxide, is starched
Liquid, centrifuge, obtain calcium sulfate and separating liquid；
(6) composition measurement：The composition of gained separating liquid, its heavy metal ion content exceed qualified electricity in determination step (5)
Liquid requirement is solved, the separating liquid is mixed with leachate obtained by step (4), obtains 100m3Manganese ion concentration is 41.5g/L mixing
Liquid；
(7) purification and impurity removal：Ammoniacal liquor is added in the mixed liquor obtained by step (6), regulation pH is 5, and adds hydrogen peroxide,
Make the iron ion and aluminium ion generation iron hydroxide and aluminum hydroxide precipitation in solution；Slurries are centrifuged, in obtaining
With slag and separating liquid；Adding diethyldithiocarbamate into separating liquid according to 5g/L amount makes beavy metal impurity generate sulfide precipitation；Obtain
Slurries containing sediment, slurries are subjected to press filtration, obtain that heavy metal ion impurities reach electrolyte requirement, manganese ion content is
39.4g/L manganese sulfate solution；
(8) it is electrolysed：It is electrolysed after electrolyte obtained by step (9) is added into antioxidant selenium dioxide, obtains manganese metal,
Anolyte return to step (1) produces electrolyte, forms circulation technology.
Embodiment 3
In the present embodiment, electrolytic manganese dioxide is prepared using leaching pyrolusite by sulfur dioxide, the anolyte in step (1) is
Conventional leaching pyrolusite by sulfur dioxide prepares anolyte caused by electrolytic manganese dioxide preparation of manganese electrowinning process, volume 100m3,
Manganese content is 35g/L in anolyte, and sulfuric acid concentration 35g/L, it is 23.5% that step (5), which is used for manganese content in the pyrolusite of leaching,
(mass percent), manganese concentration is 55g/L in qualified electrolyte, sets in whole process manganese recovery ratio as 85.0%, according toThe matter of pyrolusite needed for obtaining
Measure as 10 tons, according to pyrolusite quality with being 1 for the ratio between volume of anolyte with slurry:2 (kg/L) are with slurry, then required anode
Liquid product is 20m3。
Electrolyte is prepared in accordance with the following steps：
(1) anolyte distributes：Anolyte caused by electrowinning process is divided into two parts, respectively 20m3(part A) and 80m3
(part B)；
(2) neutralize：By the 20m obtained by step (1)3It is 2.0 that anolyte is adjusted to pH with calcium oxide, obtains slurries, slurries
Separation of solid and liquid is carried out, obtains calcium sulfate and separating liquid；
(3) it is with slurry：Separating liquid obtained by step (2) and 10 tons of pyrolusites is with slurry, solid-to-liquid ratio is obtained as 1:2 (kg/L's)
Pyrolusite pulp；
(4) leach：Reacted using the pyrolusite pulp obtained by sulfur dioxide and step (3), acquisition contains pyrolusite slag and leaching
Going out the slurries of liquid, press filtration is carried out to slurries, obtains pyrolusite slag and leachate, manganese content is 110.3g/L in leachate,；
(5) neutralize：By the 80m obtained by step (1)3After (part B) anolyte adjusts pH to 5.5 with aqua calcis,
Calcium sulfate and separating liquid are obtained through press filtration；
(6) content of beary metal is determined：The composition of separating liquid, its concentration of heavy metal ion reach conjunction obtained by determination step (5)
The requirement of lattice electrolyte；
(7) purification and impurity removal：Ammoniacal liquor is added in the slurries obtained by step (5), regulation pH is 6.3, and is passed through air, is made molten
Slurries are centrifuged, obtain neutralizing slag by iron ion and aluminium ion generation iron hydroxide and aluminum hydroxide precipitation in liquid
And separating liquid；8% sodium sulfide solution is added into separating liquid according to 25ml/L amount makes beavy metal impurity generation sulfide sink
Form sediment, obtain the slurries containing sediment, slurries are subjected to separation of solid and liquid, obtain heavy metal ion impurities and reach electrolyte requirement, manganese
Ion concentration is 110.4g/L manganese sulfate solution, and the manganese sulfate solution is mixed with separating liquid obtained by step (5), obtained
100m3Manganese ion concentration is 50.1g/L manganese sulfate electrolyte；
(8) it is electrolysed：Electrolyte obtained by step (7) is electrolysed, obtains electrolytic manganese dioxide, anolyte return to step
(1) electrolyte is produced, forms circulation technology.
Embodiment 4
In the present embodiment, electrolytic manganese dioxide is prepared using leaching pyrolusite by sulfur dioxide, the anolyte in step (1) is
Conventional leaching pyrolusite by sulfur dioxide prepares anolyte caused by electrolytic manganese dioxide preparation of manganese electrowinning process, volume 100m3,
Manganese content is 30g/L in anolyte, and sulfuric acid concentration 40g/L, it is 22% (matter that step (5), which is used for manganese content in the pyrolusite of leaching,
Measure percentage), manganese concentration is set in qualified electrolyte as 50g/L, manganese recovery ratio is 79.5% in whole process, according toThe matter of pyrolusite needed for obtaining
Measure as 13.3 tons, according to pyrolusite quality with being 1 for the ratio between volume of anolyte with slurry:3 (kg/L) are with slurry, then required A
Segment anode liquid product is 40m3。
(1) anolyte distributes：Anolyte caused by electrowinning process is divided into two parts, respectively 40m3(part A) and 60m3
(part B)；
(2) neutralize：By the 40m obtained by step (1)3It is 2.5 that anolyte is adjusted to pH with calcium oxide, obtains slurries, slurries
Press filtration separation is carried out, obtains calcium sulfate and separating liquid；
(3) it is with slurry：Separating liquid obtained by step (2) and 13.3 tons of pyrolusites is with slurry, solid-to-liquid ratio is obtained as 1:3(kg/L)
Pyrolusite pulp；
(4) leach：Reacted using the pyrolusite pulp obtained by sulfur dioxide and step (3), it is 90% to make pyrolusite leaching rate,
Manganese content is 89.7g/L in leachate, obtains the slurries containing pyrolusite slag and leachate, carries out press filtration to slurries, obtains soft
Manganese mud and leachate；
(5) neutralize：By the 60m obtained by step (1)3(part B) anolyte adjusts pH to 6.5 with calcium hydroxide, is starched
Liquid, separation of solid and liquid, obtain calcium sulfate and separating liquid；
(6) content of beary metal is determined：The composition of gained separating liquid, its heavy metal ion content exceed in determination step (5)
Qualified electrolyte requirement, by leachate obtained by the separating liquid and step (4), obtains 100m3Manganese ion concentration is the mixed of 53.9g/L
Close liquid；
(7) purification and impurity removal：Ammoniacal liquor is added in the mixed liquor obtained by step (6), regulation pH is 5.5, and adds peroxidating
Hydrogen, make iron ion and aluminium ion generation iron hydroxide and aluminum hydroxide precipitation in solution；Slurries are centrifuged, obtained
Neutralize slag and separating liquid；Adding diethyldithiocarbamate into separating liquid according to 6g/L amount makes beavy metal impurity generate sulfide precipitation；
To the slurries containing sediment, slurries are subjected to press filtration, obtain that heavy metal ion impurities reach electrolyte requirement, manganese ion content is
52.1g/L manganese sulfate solution；
(8) it is electrolysed：Electrolyte obtained by step (7) is electrolysed, obtains electrolytic manganese dioxide, anolyte return to step
(1) electrolyte is produced, forms circulation technology.
Claims (9)
1. a kind of method that manganese sulfate electrolyte is prepared suitable for leaching pyrolusite by sulfur dioxide, concrete technology are as follows：
(1) it is with slurry：It will meet and the soft manganese of process requirements in anolyte obtained by industrial production electrolytic manganese and manganese dioxide electrowinning process
A part of electrolytic anode liquid of ore deposit needs with slurry, pH is adjusted to the value leached suitable for manganese with calcium base nertralizer, is fully neutralized laggard
Row separation of solid and liquid, obtains calcium sulfate and separating liquid, and it is 1L/kg that whole pyrolusites needed for separating liquid and technique, which are configured to liquid-solid ratio,
~4L/kg high solid-liquid ratio pyrolusite pulp；
(2) leach：Using sulfur dioxide or the waste gas containing sulfur dioxide reacts with the pyrolusite pulp obtained by step (1), leaches soft
Manganese in manganese ore, separation of solid and liquid is carried out to slurries after abundant Leach reaction, obtains pyrolusite slag and leachate；
(3) neutralize：The electrolytic manganese of remainder and manganese dioxide production anolyte are adjusted into pH to 5~7 with calcium base nertralizer
Afterwards, calcium sulfate and separating liquid are obtained through separation of solid and liquid after fully neutralizing；
(4) composition measurement：The content of heavy metal ion in separating liquid obtained by determination step (3), when heavy metal ion content reaches
Electrolyte requirement, is carried out according to the following steps：
(5a) purification and impurity removal：Nertralizer is added in leachate obtained by step (2), regulation pH is 5.0~6.5, and adds oxidation
Agent, iron ion and aluminium ion is generated iron hydroxide and aluminum hydroxide precipitation, when reach iron in solution, aluminium content is less than 1.0mg/
During L requirement, separation of solid and liquid is carried out to slurries, obtains neutralizing slag and separating liquid；Then vulcanizing agent is added into separating liquid, makes weight
Metal impurities ion generation sulfide precipitation removes from solution, content of beary metal in solution is less than 1.0mg/L, obtains containing heavy
The slurries of starch, slurries are subjected to separation of solid and liquid, obtain vulcanized slag and separating liquid；
(6a) merges separating liquid：Separating liquid obtained by step (3) and step (5a) is mixed, obtains qualified manganese sulfate electrolyte；
When heavy metal ion content exceedes the content of electrolyte requirement in the separating liquid obtained by step (4) determination step (3), by with
Lower step is carried out：
(5b) purification and impurity removal：Heavy metal ion content obtained by step (2) is exceeded to separating liquid and step (3) institute of electrolyte requirement
Leachate mixing is obtained, nertralizer is added in gained mixed liquor, regulation pH is 5.0~6.5, and adds oxidant, makes iron ion
Iron hydroxide and aluminum hydroxide precipitation are generated with aluminium ion, when reaching the requirement of iron in solution, aluminium content less than 1.0mg/L,
Separation of solid and liquid is carried out to slurries, obtains neutralizing slag and separating liquid；Then vulcanizing agent is added into separating liquid, make beavy metal impurity from
Son generation sulfide precipitation removes from solution, content of beary metal in solution is less than 1.0mg/L, obtains the slurry containing sediment
Liquid, slurries are subjected to separation of solid and liquid, obtain vulcanized slag and separating liquid, gained separating liquid is qualified manganese sulfate electrolyte.
2. it is applied to the method that leaching pyrolusite by sulfur dioxide prepares manganese sulfate electrolyte, its feature according to claim 1
It is, is electrolysed in the qualified manganese sulfate electrolyte of gained, by gained anolyte return to step (1) after electrolysis, forms circulation
Technique.
3. it is applied to the method that leaching pyrolusite by sulfur dioxide prepares manganese sulfate electrolyte, its feature according to claim 1
It is, the calcium base nertralizer is one kind in calcium oxide, calcium hydroxide, calcium carbonate.
4. it is applied to the method that leaching pyrolusite by sulfur dioxide prepares manganese sulfate electrolyte, its feature according to claim 3
It is, the calcium base nertralizer is added in a manner of solid or the slurries to be configured to water.
5. it is applied to the method that leaching pyrolusite by sulfur dioxide prepares manganese sulfate electrolyte according to one of Claims 1-4,
Characterized in that, the anolyte calcium base nertralizer regulation pH for being used to prepare pyrolusite pulp in step (1) is 1~5.
6. it is applied to the method that leaching pyrolusite by sulfur dioxide prepares manganese sulfate electrolyte according to one of Claims 1-4,
Characterized in that, the pyrolusite gross mass dosage for being used to prepare pyrolusite pulp in step (1) is calculated by following formula：
7. it is applied to the method that leaching pyrolusite by sulfur dioxide prepares manganese sulfate electrolyte according to one of Claims 1-4,
Characterized in that, step (5a) is 35 with manganese sulfate concentration in the manganese sulfate electrolyte for being used to be electrolysed resulting in step (5b)
~70g/L.
8. it is applied to the method that leaching pyrolusite by sulfur dioxide prepares manganese sulfate electrolyte according to one of Claims 1-4,
Characterized in that, oxidant described in step (5a), (5b) is one kind in air, ozone, hydrogen peroxide, manganese dioxide.
9. it is applied to the method that leaching pyrolusite by sulfur dioxide prepares manganese sulfate electrolyte according to one of Claims 1-4,
Characterized in that, vulcanizing agent described in step (5a, 5b) is selected from ammonium sulfide, vulcanized sodium, Sodium Dimethyldithiocarbamate and diethyldithiocarbamate.
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| CN110358936A (en) * | 2019-08-23 | 2019-10-22 | 贵州合众锰业科技有限公司 | A method of electrolytic manganese dioxide is prepared using pyrolusite |
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