CN107699714B - A method of manganese sulfate electrolyte is prepared suitable for leaching pyrolusite by sulfur dioxide - Google Patents
A method of manganese sulfate electrolyte is prepared suitable for leaching pyrolusite by sulfur dioxide Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22B47/00—Obtaining manganese
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- 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
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Abstract
The present invention proposes a kind of method suitable for leaching pyrolusite by sulfur dioxide preparation manganese sulfate electrolyte, and central scope is: it is with slurry only with a part of anolyte and whole technique pyrolusites, high-concentration sulfuric acid manganese solution is obtained after reacting with sulfur dioxide；And another part anolyte is then neutralized, manganese sulfate concentration is obtained after solid-liquor separation and the identical low-concentration sulfuric acid manganese solution of Yuanyang pole liquid；Manganese sulfate concentration can be obtained after two parts manganese sulfate solution is mixed and reach the qualified electrolyte that electrolysis requires.The utilization efficiency of sulfur dioxide and pyrolusite in leaching process can be improved in the method for the invention, reduces 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 a kind of to use leaching pyrolusite by sulfur dioxide
In manganese preparation manganese sulfate electrolyte method.
Background technique
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, 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 in size, the service life is long.Currently, electrolytic manganese and manganese dioxide mainly pass through electrolysis sulfuric acid
The mode of manganese solution obtains, therefore preparing qualified electrolyte is the important prerequisite item for producing high-quality electrolytic manganese and manganese dioxide
Part.For the preparation method of reclaiming metals manganese and the electrolyte of manganese dioxide, basic technology is identical, mainly includes manganese
The leaching of mine and two stages of purification and impurity removal of leachate.Manganese in manganese resource pyrolusite exists in the form of manganese dioxide,
Cannot be with direct reaction of sulfuric acid, method general at present is to roast at high temperature, and manganese dioxide is reduced to acid using reducing agent
Molten manganese oxide recycles sulfuric acid solution to leach to obtain manganese sulfate electrolyte.This roasting reduction technique has manganese ore grade
High requirement, when manganese ore manganese content is greater than 40%, which has some superiority, but the average grade of Chinese pyrolusite is only
It is 22%, using reduction roasting-acid leaching process, that there are reduction efficiencies is low, impurity leaching rate is big and equipment investment is larger, energy consumption is high
The problems such as, thus fail to be widely applied.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 mine.The technology has that wide adaptation range, reaction condition is mild, reaction rate is fast, manganese leaching rate height and impurity
Leach the advantages that few.
During the electrolyte for preparing electrolytic manganese or manganese dioxide using leaching pyrolusite by sulfur dioxide, pyrolusite pulp is consolidated
Liquor ratio (pyrolusite be used for anolyte with slurry) is important parameter, and the difference of solid-to-liquid ratio will remove leaching process and purification
Miscellaneous process has an impact.Wherein to the influence of leaching process: sulfur dioxide absorption efficiency is with manganese leaching rate with the increase of 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 where, 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 where, the heat for reacting release is essentially identical, and the increase of solid-to-liquid ratio can reduce the volume of ore pulp,
Reaction temperature is increased, the leaching of pyrolusite is promoted.
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 the conditions of impurity content is higher, removal of impurity with cleaner dosage
Substantially it linearly increases.But impurity content is dropped into the 1mg/L of electrolytic manganese and the requirement of manganese dioxide technique hereinafter, then requiring to remove
Miscellaneous dose of content is significantly excessive, i.e., the amount of cleaner will often reach the several times or even dozens of times of theoretical dosage.When with slurry
Solid-to-liquid ratio is lower, and the leachate volume of generation is bigger, and the dosage of cleansing phase cleaner is bigger.
It is prepared in the method for electrolytic manganese about leaching pyrolusite by sulfur dioxide at present, as disclosed in ZL201210102916.9
" sulphur calcium disclosed in " sulfur dioxide leaches manganese oxide and produces electrolytic manganese/electrolytic manganese dioxide method ", ZL201210117146.5
Circulation leaching manganese oxide prepares electrolytic manganese/electrolytic manganese dioxide method ", used electrolyte preparation method is by whole
Anolyte it is with slurry according to the condition of " in electrolyte manganese ion concentration be 35~60g/L ".The pyrolusite for being 25% with manganese content
For, when producing electrolytic manganese, manganese content is 15~20g/L in anolyte, and being electrolysed manganese content in new liquid is 35~40g/L, then
The manganese content that electrolyte preparatory phase needs to generate is 20~25g/L, and solid-to-liquid ratio (kg:L) is about 1:10, so low solid-liquid
Than the leaching for being not only unfavorable for manganese ore, it also will increase the volume of leaching manganese reactor and the power consumption of pulp conveying, increase production
Cost.
Summary of the invention
In view of the above-mentioned deficiencies in the prior art, it is an object of the present invention to which providing the new sulfur dioxide that is suitable for of one kind leaches soft manganese
Mine prepares manganese sulfate electrolyte preparation method, to improve the utilization efficiency of sulfur dioxide and pyrolusite in leaching process, reduces leaching
Out with the capital construction cost and operating cost of leachate impurity removal process.
For foregoing invention purpose of the invention, the present invention proposes that a kind of leaching pyrolusite by sulfur dioxide that is suitable for prepares sulphur
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
Low-concentration sulfuric acid manganese solution identical with Yuanyang pole liquid；Manganese sulfate concentration can be obtained after two parts manganese sulfate solution is mixed to reach
The qualified electrolyte required to electrolysis.
Method of the present invention suitable for leaching pyrolusite by sulfur dioxide preparation manganese sulfate electrolyte, concrete technology is such as
Under:
(1) with slurry: will to 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 mine needs with slurry adjusts pH to the value for being suitable for manganese leaching with calcium base neutralizer, is consolidated after sufficiently neutralizing
Liquid separation, obtains calcium sulfate and separating liquid, the whole pyrolusite needed for separating liquid and technique be configured to liquid-solid ratio be 1L/kg~
The high solid-liquid ratio pyrolusite pulp of 4L/kg；
(2) leach: using sulfur dioxide or the exhaust gas containing sulfur dioxide is reacted with step (1) resulting pyrolusite pulp, leaching
Manganese in pyrolusite out is separated by solid-liquid separation slurries after abundant Leach reaction, obtains pyrolusite slag and leachate；
(3) it neutralizes: the electrolytic manganese of remainder and manganese dioxide production anolyte calcium base neutralizer is adjusted into pH to 5
After~7, calcium sulfate and separating liquid are obtained through being separated by solid-liquid separation after sufficiently neutralizing；
(4) composition measurement: the content of heavy metal ion in separating liquid obtained by determination step (3) works as heavy metal ion content
Reach electrolyte requirement, sequentially includes the following steps:
(5a) purification and impurity removal: being added neutralizer in the leachate obtained by step (2), adjusting pH is 5.0~6.5, and is added
Oxidant makes iron ion and aluminium ion generate iron hydroxide and aluminum hydroxide precipitation, when reach iron in solution, aluminium content is less than
When the requirement of 1.0mg/L, slurries are separated by solid-liquid separation, obtain neutralizing slag and separating liquid；Then vulcanization is added into separating liquid
Agent makes beavy metal impurity ion generate sulfide precipitation and removes from solution, content of beary metal in solution is made to be less than 1.0mg/L,
The slurries containing sediment are obtained, slurries are separated by solid-liquid separation, obtain vulcanized slag and separating liquid；
(6a) merges separating liquid: separating liquid obtained by step (3) and step (5a) being mixed, qualified manganese sulfate electrolysis is obtained
Liquid；
When heavy metal ion content is more than the content that electrolyte requires in step (4) determination step (3) gained separating liquid,
It sequentially includes the following steps:
(5b) purification and impurity removal: being more than the separating liquid and step that electrolyte requires by heavy metal ion content obtained by step (2)
(3) gained leachate mixing, is added neutralizer in gained mixed liquor, and adjusting pH is 5.0~6.5, and oxidant is added, and makes iron
Ion and aluminium ion generate iron hydroxide and aluminum hydroxide precipitation, when reach iron in solution, aluminium content is less than the requirement of 1.0mg/L
When, slurries are separated by solid-liquid separation, obtain neutralizing slag and separating liquid；Then vulcanizing agent is added into separating liquid, keeps heavy metal miscellaneous
Matter ion generates sulfide precipitation and removes from solution, so that content of beary metal in solution is less than 1.0mg/L, obtains containing sediment
Slurries are separated by solid-liquid separation by slurries, obtain vulcanized slag and separating liquid, and gained separating liquid is qualified manganese sulfate electrolyte.
In above-mentioned technical proposal of the invention, gained qualification manganese sulfate electrolyte is electrolysed, by gained after electrolysis
Anolyte return step (1) forms circulation technology.
In above-mentioned technical proposal of the 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 recycled by way of being electrolysed qualified manganese sulfate solution
Reaction are as follows:
MnO2+SO2→MnSO4
The chemical reaction occurred in step (8) electrolytic process are as follows:
MnSO4+H2O→Mn↓+H2SO4+1/2O2↑ (electrolytic manganese)
MnSO4+2H2O→MnO2↓+H2SO4+H2↑ (electrolytic manganese dioxide)
By the chemical reaction during above-mentioned two it is found that in electrolytic process, the sulfate radical in manganese sulfate is converted into sulphur
Acid, and in pyrolusite leaching process, the manganese dioxide in pyrolusite is directly reacted with sulfur dioxide can be obtained manganese sulfate.Sulfuric acid
Presence can not only reduce the absorption efficiency of sulfur dioxide in leaching process, and sulfate radical content can be made to accumulate in circulating system,
Destruction system balance, therefore, the sulfuric acid generated in electrolytic process must be removed from system, selective oxidation calcium, calcium hydroxide,
Calcium carbonate etc. is used as neutralizer, can not only neutralize acidity, and generate calcium sulfate precipitation, sulfate radical is enable to remove, neutralizer
Adding manner 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↑
It is relatively fixed for pyrolusite quality with slurry in specific system in above-mentioned technical proposal of the invention, it uses
Smaller in anolyte volume with slurry, the solid-to-liquid ratio of gained pyrolusite pulp is bigger, and pyrolusite content is higher, is more conducive 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, will lead to the increase of pulp conveying power energy consumption, pyrolusite
It the problems such as reactor wall agglomeration and sulfur dioxide absorption efficiency decline, therefore is 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 and the ratio between the volume for being used for part A anolyte with slurry
Preferably 1:(1~4) (kg/L).
In above-mentioned technical proposal of the 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 system in anolyte after sulfuric acid is neutralized in step (2) 1~5, but the specific number optimized
Value need to be determined according to the specific system condition of body.
In above-mentioned technical proposal of the invention, it is calculate by the following formula in step (4) for pyrolusite total amount with slurry:
The qualification 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 above-mentioned technical proposal of the invention, purification and impurity removal process is mainly to remove to enter leachate in leaching process
Accompanying element impurity, main includes 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
It is oxidized to ferric sulfate, air, ozone, hydrogen peroxide, manganese dioxide or pyrolusite etc. can be oxidized, and ammonia is then added
The neutralizers such as water or calcium hydroxide adjust pH to 5~7, can make ferric sulfate and aluminum sulfate is converted into iron hydroxide and aluminium hydroxide is heavy
It forms sediment, specific reaction is as follows:
Fe3++3OH-→Fe(OH)3
Al3++3OH-→Al(OH)3
In the vulcanization removing heavy metals stage, due to the heavy metals such as Zn, Cu, Ni, Co, Pb in leachate can with sulphion or
Organic methylthio group generates stable sulfide precipitation, to be removed from solution by way of being separated by solid-liquid separation, therefore is added
Vulcanizing agent be the sulfide for being capable of providing sulphion or organic methylthio group, may be selected ammonium sulfide, vulcanized sodium, Sodium Dimethyldithiocarbamate, second
One or more of sulphur nitrogen.Specific reaction is as follows:
Me2++S2-(Me is heavy metal, S to → MeS2-For sulphion or organic methylthio group)
Compared with prior art, the invention has the following advantages:
1, the method for the invention is carried out only with a part of anolyte with whole pyrolusites with slurry, improves pyrolusite
Leach process in pyrolusite pulp solid-to-liquid ratio, be conducive 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
The problem of existing solid-to-liquid ratio is low, brings adverse effect to leaching process and purification and impurity removal process.
2, the method for the invention reduces the slurries that pyrolusite leaches process due to the solid-to-liquid ratio raising of pyrolusite pulp
Amount reduces equipment volume, the power for reducing slurries conveying equipment disappears on the basis of the leaching process residence time is identical
Consumption, reduces capital construction and cost of investment.
3, the method for the invention reduces the slurries amount of purification and impurity removal process due to the solid-to-liquid ratio raising of pyrolusite pulp,
The dosage for reducing cleaner, reduces reagent cost.
Detailed description of the invention
Fig. 1 is the process flow diagram of the method for the invention.
Specific embodiment
It is suitable for leaching pyrolusite by sulfur dioxide system to of the present invention below with reference to process flow chart and by embodiment
The method of standby manganese sulfate electrolyte is described in further detail.It is important to point out that embodiment below is served only for this
Invention is described further, and should not be understood as limiting the scope of the invention, fields be skillful at personnel according to
Foregoing invention content is made some nonessential modifications and adaptations to the present invention and is embodied, should still fall within of the invention
Protection scope.
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 the anolyte that pyrolusite prepares the generation of 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 for manganese in the pyrolusite of leaching
Content is 28.5% (mass percent), and manganese content is 38g/L in qualified electrolyte needed for setting, manganese recovery ratio in whole process
It must be 80%, according toIt obtains
The quality of required pyrolusite is 10 tons, is 1 according to pyrolusite quality and 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: the anolyte that electrowinning process generates is divided into two parts, respectively 30m3(part A) and 70m3
(part B)；
(2) it neutralizes: by step (1) resulting 30m3It is 3.0 that anolyte, which is adjusted to pH with calcium oxide, obtains slurries, slurries
Filters pressing separation is carried out, calcium sulfate and separating liquid are obtained；
(3) with slurry: step (2) resulting separating liquid and 10 tons of pyrolusites is with slurry, and obtaining solid-to-liquid ratio is 1:3 (kg/L)
Pyrolusite pulp；
(4) it leaches: being reacted using sulfur dioxide with step (3) resulting pyrolusite pulp, make pyrolusite leaching rate 90%,
Manganese content is 100.8g/L in leachate, obtains the slurries containing pyrolusite slag and leachate, carries out filters pressing to slurries, obtains soft
Manganese mud and leachate；
(5) it neutralizes: by step (1) resulting 70m3After (part B) anolyte adjusts pH to 6.0 with calcium hydroxide solution,
Calcium sulfate and separating liquid are obtained through being separated by solid-liquid separation；
(6) composition measurement: the ingredient of separating liquid obtained by determination step (5), concentration of heavy metal ion reach qualified electrolysis
Liquid requirement；
(7) purification and impurity removal: being added ammonium hydroxide in step (4) resulting slurries, and adjusting pH is 6.0, and is passed through air, makes molten
Iron ion and aluminium ion in liquid generate iron hydroxide and aluminum hydroxide precipitation, and slurries are centrifuged, and obtain neutralizing slag
And separating liquid；8% ammonium sulfide solution is added into separating liquid according to the amount of 20ml/L, so that beavy metal impurity is generated sulfide heavy
It forms sediment, obtains the slurries containing sediment, staticly settle, filter, obtain that heavy metal ion impurities reach electrolyte requirement, manganese ion contains
Amount is the manganese sulfate solution of 90.1g/L, which is mixed with separating liquid obtained by step (5), obtains 100m3Manganese ion
Concentration is the manganese sulfate electrolyte of 37.8g/L；
(8) it is electrolysed: being electrolysed after antioxidant selenium dioxide being added in electrolyte obtained by step (7), obtain metal
Manganese, anolyte return step (1) produce electrolyte, form 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 the anolyte that pyrolusite prepares the generation of electrolytic manganese process electrowinning process, volume 100m3, manganese content in anolyte
For 17g/L, ammonium sulphate content 120g/L, sulfuric acid concentration 35g/L, step (5) is for manganese content in the pyrolusite of leaching
17.5% (mass percent), manganese concentration is 40g/L in qualified electrolyte needed for setting, and manganese recovery ratio is in whole process
82%, according toNeeded for obtaining
The quality of pyrolusite is 16 tons, is matched according to pyrolusite quality with for the ratio between volume of anolyte with slurry for 1:2.5 (kg/L)
Slurry, then required part A anolyte volume is 40m3。
(1) anolyte distributes: the anolyte that electrowinning process generates is divided into two parts, respectively 40m3(part A) and 60m3
(part B)；
(2) it neutralizes: by step (1) resulting 40m3It is 3.5 that anolyte, which is adjusted to pH with calcium oxide, obtains slurries, slurries
Filters pressing is carried out, calcium sulfate and separating liquid are obtained；
(3) with slurry: step (2) resulting separating liquid and 16 tons of pyrolusites is with slurry, and obtaining solid-to-liquid ratio is 1:2.5 (kg/L)
Pyrolusite pulp；
(4) it leaches: being reacted using sulfur dioxide with step (3) resulting pyrolusite pulp, make pyrolusite leaching rate 92%,
Manganese content is 78.1g/L in leachate, obtains the slurries containing pyrolusite slag and leachate, carries out filters pressing to slurries, obtains soft
Manganese mud and leachate；
(5) it neutralizes: by step (1) resulting 60m3(part B) anolyte adjusts pH to 5.5 with calcium hydroxide, is starched
Liquid, centrifuge separation, obtains calcium sulfate and separating liquid；
(6) composition measurement: the ingredient of gained separating liquid in determination step (5), heavy metal ion content are more than qualified electricity
Liquid requirement is solved, which is mixed with leachate obtained by step (4), obtains 100m3Manganese ion concentration is the mixing of 41.5g/L
Liquid；
(7) purification and impurity removal: being added ammonium hydroxide in step (6) resulting mixed liquor, and adjusting pH is 5, and hydrogen peroxide is added,
Iron ion and aluminium ion in solution is set to generate iron hydroxide and aluminum hydroxide precipitation；Slurries are centrifuged, are obtained
With slag and separating liquid；Diethyldithiocarbamate is added into separating liquid according to the amount of 5g/L makes beavy metal impurity generate sulfide precipitation；It obtains
Slurries are carried out filters pressing by the slurries containing sediment, obtain that heavy metal ion impurities reach electrolyte requirement, manganese ion content is
39.4g/L manganese sulfate solution；
(8) it is electrolysed: being electrolysed after antioxidant selenium dioxide is added in electrolyte obtained by step (9), obtain manganese metal,
Anolyte return 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 the anolyte of electrolytic manganese dioxide preparation of manganese electrowinning process generation, volume 100m3,
Manganese content is 35g/L in anolyte, and sulfuric acid concentration 35g/L, step (5) is 23.5% 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 toObtain the matter of required pyrolusite
Amount is 10 tons, according to pyrolusite quality and, then required anode with slurry for 1:2 (kg/L) for the ratio between volume of anolyte with slurry
Liquid product is 20m3。
Electrolyte is prepared in accordance with the following steps:
(1) anolyte distributes: the anolyte that electrowinning process generates is divided into two parts, respectively 20m3(part A) and 80m3
(part B)；
(2) it neutralizes: by step (1) resulting 20m3It is 2.0 that anolyte, which is adjusted to pH with calcium oxide, obtains slurries, slurries
It is separated by solid-liquid separation, obtains calcium sulfate and separating liquid；
(3) with slurry: step (2) resulting separating liquid and 10 tons of pyrolusites is with slurry, and obtaining solid-to-liquid ratio is 1:2 (kg/L)
Pyrolusite pulp；
(4) it leaches: being reacted using sulfur dioxide with step (3) resulting pyrolusite pulp, obtain and contain pyrolusite slag and leaching
The slurries of liquid out carry out filters pressing to slurries, obtain pyrolusite slag and leachate, and manganese content is 110.3g/L in leachate,；
(5) it neutralizes: by step (1) resulting 80m3After (part B) anolyte adjusts pH to 5.5 with calcium hydroxide solution,
Calcium sulfate and separating liquid are obtained through filters pressing；
(6) measure content of beary metal: the ingredient of separating liquid obtained by determination step (5), concentration of heavy metal ion reach conjunction
The requirement of lattice electrolyte；
(7) purification and impurity removal: being added ammonium hydroxide in step (5) resulting slurries, and adjusting pH is 6.3, and is passed through air, makes molten
Iron ion and aluminium ion in liquid generate iron hydroxide and aluminum hydroxide precipitation, and slurries are centrifuged, and obtain neutralizing slag
And separating liquid；8% sodium sulfide solution is added into separating liquid according to the amount of 25ml/L keeps beavy metal impurity generation sulfide heavy
It forms sediment, obtains the slurries containing sediment, slurries are separated by solid-liquid separation, obtain heavy metal ion impurities and reach electrolyte requirement, manganese
Ion concentration is the manganese sulfate solution of 110.4g/L, which is mixed with separating liquid obtained by step (5), is obtained
100m3Manganese ion concentration is the manganese sulfate electrolyte of 50.1g/L；
(8) it is electrolysed: electrolyte obtained by step (7) is electrolysed, obtain electrolytic manganese dioxide, anolyte return step
(1) electrolyte is produced, circulation technology is formed.
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 the anolyte of electrolytic manganese dioxide preparation of manganese electrowinning process generation, volume 100m3,
Manganese content is 30g/L in anolyte, and sulfuric acid concentration 40g/L, step (5) is 22% (matter for manganese content in the pyrolusite of leaching
Measure percentage), set in qualified electrolyte that manganese concentration is 50g/L, manganese recovery ratio is 79.5% in whole process, according toObtain required pyrolusite
Quality is 13.3 tons, according to pyrolusite quality with it is with slurry for 1:3 (kg/L) for the ratio between volume of anolyte with slurry, then it is required
Part A anolyte volume is 40m3。
(1) anolyte distributes: the anolyte that electrowinning process generates is divided into two parts, respectively 40m3(part A) and 60m3
(part B)；
(2) it neutralizes: by step (1) resulting 40m3It is 2.5 that anolyte, which is adjusted to pH with calcium oxide, obtains slurries, slurries
Filters pressing separation is carried out, calcium sulfate and separating liquid are obtained；
(3) with slurry: step (2) resulting separating liquid and 13.3 tons of pyrolusites is with slurry, and obtaining solid-to-liquid ratio is 1:3 (kg/L)
Pyrolusite pulp；
(4) it leaches: being reacted using sulfur dioxide with step (3) resulting pyrolusite pulp, make pyrolusite leaching rate 90%,
Manganese content is 89.7g/L in leachate, obtains the slurries containing pyrolusite slag and leachate, carries out filters pressing to slurries, obtains soft
Manganese mud and leachate；
(5) it neutralizes: by step (1) resulting 60m3(part B) anolyte adjusts pH to 6.5 with calcium hydroxide, is starched
Liquid is separated by solid-liquid separation, obtains calcium sulfate and separating liquid；
(6) measure content of beary metal: the ingredient of gained separating liquid, heavy metal ion content are more than in determination step (5)
Leachate obtained by the separating liquid and step (4) is obtained 100m by qualified electrolyte requirement3Manganese ion concentration is the mixed of 53.9g/L
Close liquid；
(7) purification and impurity removal: being added ammonium hydroxide in step (6) resulting mixed liquor, and adjusting pH is 5.5, and peroxidating is added
Hydrogen makes iron ion and aluminium ion in solution generate iron hydroxide and aluminum hydroxide precipitation；Slurries are centrifuged, are obtained
Neutralize slag and separating liquid；Diethyldithiocarbamate is added into separating liquid according to the amount of 6g/L makes beavy metal impurity generate sulfide precipitation；?
To the slurries containing sediment, slurries are subjected to filters pressing, 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, obtain electrolytic manganese dioxide, anolyte return step
(1) electrolyte is produced, circulation technology is formed.
Claims (9)
1. a kind of method suitable for leaching pyrolusite by sulfur dioxide preparation manganese sulfate electrolyte, the specific process is as follows:
(1) with slurry: will to 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 mine needs with slurry adjusts pH to the value for being suitable for manganese leaching with calcium base neutralizer, sufficiently neutralizes laggard
Row is separated by solid-liquid separation, and obtains calcium sulfate and separating liquid, and it is 1L/kg that the whole pyrolusite needed for separating liquid and technique, which is configured to liquid-solid ratio,
The high solid-liquid ratio pyrolusite pulp of~4L/kg；
(2) leach: using sulfur dioxide or the exhaust gas containing sulfur dioxide is reacted with step (1) resulting pyrolusite pulp, is leached soft
Manganese in manganese ore is separated by solid-liquid separation slurries after abundant Leach reaction, obtains pyrolusite slag and leachate；
(3) it neutralizes: the electrolytic manganese of remainder and manganese dioxide production anolyte calcium base neutralizer is adjusted into pH to 5~7
Afterwards, calcium sulfate and separating liquid are obtained through being separated by solid-liquid separation after sufficiently 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, sequentially includes the following steps:
(5a) purification and impurity removal: being added neutralizer in the leachate obtained by step (2), adjusting pH is 5.0~6.5, and oxidation is added
Agent makes iron ion and aluminium ion generate iron hydroxide and aluminum hydroxide precipitation, when reach iron in solution, aluminium content is less than 1.0mg/
When the requirement of L, slurries are separated by solid-liquid separation, obtain neutralizing slag and separating liquid；Then vulcanizing agent is added into separating liquid, makes weight
Metal impurities ion generates sulfide precipitation and removes from solution, so that content of beary metal in solution is less than 1.0mg/L, obtains containing heavy
The slurries of starch, slurries are separated by solid-liquid separation, and obtain vulcanized slag and separating liquid；
(6a) merges separating liquid: separating liquid obtained by step (3) and step (5a) being mixed, qualified manganese sulfate electrolyte is obtained；
When heavy metal ion content is more than the content that electrolyte requires in the separating liquid obtained by step (4) determination step (3), by with
Lower step carries out:
(5b) purification and impurity removal: being more than the separating liquid and step (3) institute that electrolyte requires by heavy metal ion content obtained by step (2)
Leachate mixing is obtained, neutralizer is added in gained mixed liquor, adjusting pH is 5.0~6.5, and oxidant is added, and 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,
Slurries are separated by solid-liquid separation, obtain neutralizing slag and separating liquid；Then vulcanizing agent is added into separating liquid, make beavy metal impurity from
Son generates sulfide precipitation and removes from solution, so that content of beary metal in solution is less than 1.0mg/L, obtains the slurry containing sediment
Slurries are separated by solid-liquid separation by liquid, obtain vulcanized slag and separating liquid, and gained separating liquid is qualified manganese sulfate electrolyte.
2. being suitable for the method for leaching pyrolusite by sulfur dioxide preparation manganese sulfate electrolyte, feature according to claim 1
It is, is electrolysed in resulting qualified manganese sulfate electrolyte, by gained anolyte return step (1) after electrolysis, forms circulation
Technique.
3. being suitable for the method for leaching pyrolusite by sulfur dioxide preparation manganese sulfate electrolyte, feature according to claim 1
It is, the calcium base neutralizer is one of calcium oxide, calcium hydroxide, calcium carbonate.
4. being suitable for the method for leaching pyrolusite by sulfur dioxide preparation manganese sulfate electrolyte, feature according to claim 3
It is, the calcium base neutralizer is added in a manner of solid or the slurries to be configured to water.
5. according to claim 1 to described in one of 4 be suitable for leaching pyrolusite by sulfur dioxide preparation manganese sulfate electrolyte method,
It is characterized in that, the anolyte calcium base neutralizer adjusting pH in step (1) for preparing pyrolusite pulp is 1~5.
6. according to claim 1 to described in one of 4 be suitable for leaching pyrolusite by sulfur dioxide preparation manganese sulfate electrolyte method,
It is characterized in that, being calculate by the following formula in step (1) for preparing the pyrolusite gross mass dosage of pyrolusite pulp:
7. according to claim 1 to described in one of 4 be suitable for leaching pyrolusite by sulfur dioxide preparation manganese sulfate electrolyte method,
It is characterized in that, manganese sulfate concentration is 35 in the obtained manganese sulfate electrolyte for electrolysis in step (5a) and step (5b)
~70g/L.
8. according to claim 1 to described in one of 4 be suitable for leaching pyrolusite by sulfur dioxide preparation manganese sulfate electrolyte method,
It is characterized in that, oxidant described in step (5a), (5b) is one of air, ozone, hydrogen peroxide, manganese dioxide.
9. according to claim 1 to described in one of 4 be suitable for leaching pyrolusite by sulfur dioxide preparation manganese sulfate electrolyte method,
It is 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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