CN104232889A - Technology for producing electrolytic metal manganese from low-grade manganese mine - Google Patents
Technology for producing electrolytic metal manganese from low-grade manganese mine Download PDFInfo
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Abstract
The invention relates to a technology for producing electrolytic metal manganese from low-grade manganese mine. The technological flow comprises ore grinding, sulfuric acid pre-leach, combusting sulfur for preparing sulfur dioxide, sulfur dioxide reduction leaching, solid-liquid separation, purifying of a leaching liquid, separation of dithionate radical, production of electrolytic metal manganese, decomposition of dithionate radical, production of anhydrous sodium sulfate and recovery of production water. The technology is simple, resource is cycled for utilization, the reduction leaching rate of manganese is even up to 98%, and the recovery utilization efficiency is high.
Description
Technical field
The present invention relates to a kind of low-grade manganese and produce Process of Electrolytic Manganese.
Background technology
China's manganese resource is very abundant, by the end of the year 2005, finds out national reserves 7.46 hundred million t, wherein reserves and basic unit price 2.15 hundred million t, stock number 5.30 hundred million t.Type, based on manganese carbonate ore, accounts for 73% of total reserves, and be secondly ferrimanganic ore and manganese oxide ore, rich manganese ore only accounts for 6.4% of total reserves.In recent years, the annual manganese ore produced quantity of China about more than 1,000 ten thousand t, wherein manganese carbonate ore accounts for 45%, causes higher-grade manganese ore day by day exhausted.The manganese ore of 90% is mainly used in Iron And Steel Industry, produces mn site doping, electrolytic metal Mn etc.Along with the fast development of China's steel industry, the domestic demand to promoter manganese constantly increases.Within 2008, manganese ore import volume is surged to 758.1 ten thousand t, within 2007, increases by 14.3% on year-on-year basis, has become maximum manganese ore importer in the world.
For meeting the demand of national economy fast development, make full use of the low-grade manganese resource of China, Devoting Major Efforts To Developing utilizes low-grade manganese to become the focus of research.What current research was more is adopt reduction method to reclaim manganese, mainly contains roast reduction process and wet reducing two kinds.
1 roast reduction process
Tradition roasting reduction technique mainly adopts coal reduction roasting method, and this method reduction temperature is high, operational condition is poor, produces a large amount of flue gas, causes serious environmental pollution.For overcoming the defect that traditional coal reduction roasting method brings, realize green cleaner production, grow up several novel roast reduction process in recent years.
(1) stalk reduction roasting method
Stalk reduction roasting method is a kind of roast reduction process of improvement, first a certain amount of manganese oxide ore and stalk are placed in mortar, fully be ground, roasting 80min at 500 DEG C, in manganese ore, MnO2 is reduced into MnO, pours in beaker, add sulfuric acid by roasting after product, in water bath with thermostatic control, stir leaching, after filtration, obtain manganese sulfate solution.
In manganese oxide ore, MnO2 and reductive agent react, and value Mn are reduced into manganese at a low price:
MnO2→Mn3O4→Mn2O3→MnO
The reaction of this roasting reduction is proceed step by step, its chemical equation:
MnO2+CO→Mn3O4+CO2
Mn3O4+CO→Mn2O3+CO2
Mn2O3+CO→MnO+CO2
The net reaction of this process:
CxHyOz+MnO2→CO2+MnO+H2O
Product after reduction, with sulfuric acid to leach, the chemical reaction occurred in leaching process is mainly:
MnO+H2SO4→MnSO4+H2O
Leach liquor, again through various purification and impurity removal process, obtains pure manganese containing solution for producing other various final manganese products.Experimental studies results shows, manganese oxide ore and stalk are by weight roasting 80min at 10: 3,500 DEG C, and control rotating speed 400r/min, sulfuric acid concentration 3mol/L, leaches 40min at 50 DEG C, and the leaching rate of recovery of manganese can reach 90.2%.
Stalk is as a kind of renewable energy source, wide material sources, with low cost, and this technological operation is simple, it is low to consume energy, pollute less, reduction efficiency is higher, is suitable for suitability for industrialized production.
(2) mixed-ammonium salt roasting method
Mixed-ammonium salt roasting method is carried out on ammonium salt roasting method basis, with ammonium chloride or ammonium sulfate process manganese oxide ore.Fixedly take a certain amount of Low grade manganese ore in porcelain crucible, mix with ammonium salt by different ratios, be placed in retort furnace, roasting 1h at 450 DEG C, by slag hot water leaching after roasting, filter, obtain soluble manganese salt, for the preparation of other manganese system products.This method process Low grade manganese ore the manganese in mineral can be changed into soluble manganese salt, the reaction of generation at a certain temperature based on ammonium chloride and ammonium sulfate:
NH4Cl→NH3+HCl
(NH4)2SO4→2NH3+H2SO4
MnO2+4HCl→MnCl2+Cl2+2H2O
2MnO2+2H2SO4→2MnSO4+O2+2H2O
Although the ammonium salt roasting method rate of recovery can reach more than 80%, each reagent consumption is large, even if reagent can recycle, but causes subsequent evaporation crystallization content too large, increases production cost.And use ammonium chloride-ammonium sulfate mixed-ammonium salt calcination process Low grade manganese ore, relative to unitary system, calcining is easy to leach, and greatly can improve manganese to leach the rate of recovery, and the consumption of reagent obviously reduces, and can effectively reduce costs.
2 wet reducings
Wet method avoids high-temperature roasting operation, and is one-step leaching, simplifies technique, therefore becomes manganese in manganese oxide ore and reclaims the developing direction of extract technology.The wet method of early-stage development has two-control region, SO2 lixiviation process, calcium dithionate method etc.But all there is shortcoming in these methods, two-control region in actual applications reduction ratio and leaching yield lower, the quantity of slag is large, affects the recovery of manganese; SO2 lixiviation process side reaction impact is comparatively large, seriously polluted; The calcium dithionate method quantity of slag is large, subsequent disposal difficulty.In recent years, along with the development of manganese industry and the needs of suitability for industrialized production, wet reducing method is also in continuous renewal.
(1) waste molasses lixiviation process
Waste molasses is the by product of sugaring process, containing reducing substanceses such as abundant carbohydrates, as sucrose, glucose etc.In acid condition, the MnO2 in manganese oxide ore and the sucrose in waste molasses, glucose react, and react as follows:
24MnO2+C12H22O11+24H2SO4→24MnSO4+12CO2↑+35H2O
12MnO2+C6H12O6+12H2SO4→12MnSO4+6CO2↑+18H2O
Extraction temperature, H2SO4 concentration, extraction time and the waste molasses concentration leaching rate of recovery on manganese has impact.Best processing condition: H2SO4 concentration 2.35mol/L, waste molasses 75g/L, reaction times 2h, temperature of reaction 90 DEG C, Mn leaches the rate of recovery can reach 96.7%.
Waste molasses reducing leaching technological process is simple, material reaction fast, manganese utilization ratio is higher, can make full use of Low grade manganese ore resource.Reductive agent used is nontoxic, cheap renewable resources, reduces production cost.
(2) metallic iron direct leaching
With iron filings be reductive agent reclaim from manganese oxide ore extract manganese, the reaction of generation mainly contains:
Fe+2H+→Fe2++H2
2Fe2++MnO2+4H+→2Fe3++Mn2++2H2O
MnO2+H2SO4+H2→MnSO4+2H2O
Fe+2Fe3+→3Fe2+
3MnO2+6H2SO4+2Fe→Fe2(SO4)3+3MnSO4+6H2O
Control Leaching reaction condition: iron ore is than 1: 13, and sour ore deposit is than 0.6: 1, and liquid-solid ratio 3: 1, leaches 60min under room temperature, and grinding fineness < 0.074mm grade accounts for 80%, and the leaching rate of recovery of manganese reaches more than 97.60%.
Research shows, in acidic oxidation manganese ore slurry, directly adds sponge iron, and the tetravalent manganese in manganese oxide ore can be made to be reduced into bivalent manganese rapidly, than more effective with ferrous sulfate.By controlling reaction conditions: iron ore is than 0.8: 1, and sour ore deposit is than 3: 1, and after leaching 10min under room temperature, the leaching rate of recovery of Mn reaches 98%.And under the same conditions, use ferrous sulfate as reductive agent, and sour ore deposit ratio is brought up to 0.8, after 10min is leached in reaction, the rate of recovery of Mn is only 80%.The visible process of ferrous sulfate to reducing leaching directly adding the formation of metallic iron scene plays favourable promoter action.In fact, metallic iron lixiviation process is a kind of ferrous sulfate lixiviation process of improvement, and this is because the ferrous ion of status nascendi may have stronger reducing power.
(3) other reduction leaching process
Except the above leaching introduced is reclaimed except the method for manganese, also has the studied exploitation of many methods, as H2O2 reduction method, SO2 reduction method, sucrose or method of glucose reduction, Reduction of methanol method etc.The large multipaths of these lixiviation process is complicated, or production cost is high, or material corrosion is strong, or seriously polluted, and the recovery being not suitable for manganese in Low grade manganese ore is extracted.
Summary of the invention
For the deficiencies in the prior art, an object of the present invention is to provide a kind of low-grade manganese to produce Process of Electrolytic Manganese.Described technology process is simple, resource circulation utilization, and the reducing leaching rate of manganese even up to 98%, can recycle efficiency high.
In order to overcome the above problems, present invention employs technical scheme:
A kind of low-grade manganese produces Process of Electrolytic Manganese, its technical process comprises: ore grinding, sulfuric acid preextraction, burning Sulfur prepare sulfurous gas, sulphur dioxide reduction leaching, solid-liquid separation, purification of leaching liquor, the separation of dithionic acid root, electrolytic metal Mn production, the decomposition of dithionic acid root, anhydrous sodium sulphate is produced, and the recovery of water of productive use.
Below be described in detail:
1 ore grinding
First manganese ore enters feed bin by Grid screen, and the large lump ore on Grid screen then rolls with dozer and makes it to be forced through Grid screen and enter feed bin.Manganese ore after putting in storage enters the crushing system become with drum screen banks by hammer mill; Be crushed to below granularity 30mm, be sent to leaching system, on the sieve of drum sieve, ore deposit then turns back to hammer mill feed end.
2 sulfuric acid preextraction
Granularity is the broken manganese ore of below 30mm and the ore pulp being mixed into concentration about 12% ~ 20% containing manganese washing lotion in agitation vat returned from leached mud countercurrent washing system, add sulphuric acid soln simultaneously, under strong stirring action, broken manganese ore is crushed into fine-grannular, and the acid consumpting substance and the sulfuric acid reaction that are mainly calcium produce insoluble vitriol simultaneously.
3 burning Sulfurs prepare sulfurous gas
First Sulfur is heated to more than 115 DEG C and makes it liquefaction, then liquid Sulfur is atomized by spraying gun, and burns when excessive 20% air, generates by volume containing rare sulfur dioxide gas of 17.5%SO2,79.0%N2 and 3.5%O2.The heat discharged in Sulfur combustion processes produces steam by heat exchanger, and these steam, by condensing turbine, can produce electric power continuously.
4 sulphur dioxide reductions leach
Manganese ore slurry after persulfuric acid preextraction enters a series of plural serial stage leaching barrel arranged in notch cuttype, sulfurous gas (excessive 10%) and manganese oxide ore pulp are that reverse entering successively in each leaching barrel carries out reducing leaching reaction, make the tetravalent manganese in manganese ore be reduced into the divalent manganesetion of solubility, its main chemical reactions formula is:
Main reaction: MnO2+SO2=MnSO4
Side reaction: MnO2+2SO2=MnS2O6
During reducing leaching, control pulp density is 10%, SO2 concentration is 6%, and manganese ore granularity is 70 orders (210 μm), and sulfuric acid concentration is 0.05-0.1M.The reducing leaching rate of manganese even up to 98%, generally can reach more than 90%.
Multilevel counter-flow extraction system not only can make SO2 be fully used, and effectively can utilize the basicity of manganese ore, thus has very significant economy.As when thtee-stage shiplock leaches, 1st grade of leach liquor pH=1.2, its major impurity content is: iron 010269% (269ppm), aluminium 010102 (102ppm), arsenic 010042% (42ppm), the 2nd grade of leach liquor pH=2.2, foreign matter content just obviously have dropped, and reaching 6.3 to leach liquor pH during 3rd level, iron, aluminium and arsenic content have been reduced to all lower than 010001% (1ppm).
5 solid-liquid separation
Complete leach liquor that reducing leaching reacts later to overflow to leach liquor thickener from last step leaching barrel top and carry out solid-liquid separation.The supernatant leach liquor of this thickener is about 50g/L containing manganese, wherein the ratio of manganous sulfate and manganous dithionate is about 1: 0.16, this supernatant liquor enters purification of leaching liquor system from thickener overflow, the underflow of thickener then enters leached mud countercurrent washing system, this system is made up of, as production system recycle-water and the leached mud antikinesis of washing lotion a series of thickener arranged in notch cuttype.Leached mud filters with filter after fully washing in this system again, is namely transported to former stope and backfills, then return leaching system containing manganese washing water after filter cake washing.
In order to improve the result of use of thickener, carrying out a series of flocculation agent that adds in ore pulp and having tested, to increase solid particles sediment speed and thickener underflow concentration in ore pulp
Washing is 38% containing solid concentration, and during thickener underflow containing manganese 50g/L, when not counting the recyclable manganese of final filtration machine filter liquid, the manganese recovery ratio of leached mud countercurrent washing system can reach 99.5%.
6 purification of leaching liquor
The major impurity except manganous dithionate contained in the leach liquor that solid-liquid separation is later has iron, aluminium, arsenic and silicon, and a small amount of zinc, cobalt and copper plasma.When the pH of leach liquor is brought up to more than 5.5, and pass into air and make divalent ion be oxidized to ferric ion, now iron, aluminium, arsenic all can be reduced to lower than 1ppm, and silicon and copper content also have remarkable reduction, but regulate pH to removal zinc and cobalt then inoperative.Need to adopt sulphide precipitation to be removed for this reason, when the sulfide of depositing zinc and cobalt, should carry out under the condition of pH neutrality, and should avoid using excessive vulcanizing agent, in order to avoid cause the sulphur content in Electrolytic Manganese Product to exceed standard.
Separation-manganous carbonate the precipitator method of 7 dithionic acid roots
How removing the manganous dithionate (MnS2O6) that in sulphur dioxide reduction leaching process, side reaction produces, is a crucial technical problem of this technique.The present invention is by the manganous carbonate precipitator method, and make the manganous sulfate in leach liquor and manganous dithionate all generate manganous carbonate precipitation, sulfate radical and dithionic acid root then generate sodium salt and stay in the solution, thus mn ion and dithionic acid root are separated:
MnSO4+Na2CO3→MnCO3+Na2SO4
MnS2O6+Na2CO3→MnCO3+Na2S2O6
Gained manganous carbonate precipitation, after washing, filtering, with being dissolved containing sour anolyte of returning from electrolyzer, namely obtains the electrolytic solution of manganese sulfate solution as electrolytic metal Mn:
MnCO3+H2SO4=MnSO4+CO2
Have sulfuric acid to produce in electrolytic process due to the manganese such as electrolytic metal Mn and electrolytic manganese dioxide electrolytic production, when using manganous carbonate for raw material, what this returned generates manganous sulfate containing sour electrolysis waste solution can be used for leaching manganese carbonate ore.But, the reaction that sulphur dioxide reduction leaches manganese oxide ore is then directly generate manganous sulfate, do not need to participate in reaction according to the stoichiometric sulfuric acid of manganous sulfate, therefore leaching manganese oxide ore at employing sulphur dioxide reduction prepares in the flow process of electrolytic metal Mn or electrolytic manganese dioxide, all there is the problem of an acid balance.The manganous carbonate precipitator method that the present invention adopts both had solved the separation problem of dithionic acid root, also solved the acid balance problem in whole flow process simultaneously.
8 electrolytic metal Mns are produced
By aforementioned manganese sulfate solution again after removing the deep purifying of iron and heavy metal further, for producing the qualified feed liquor of electrolyzer of electrolytic metal Mn, the electrode materials that electrolytic process adopts is roughly the same with existing electrolytic metal Mn industrial production with processing parameter.Electrolytic process tests the Electrolytic Manganese Product purity obtained can reach more than 99.5%, and current efficiency is also suitable with industrial representative data, can reach more than 67%.
9 dithionic acid roots decompose, and anhydrous sodium sulphate is produced, and the recovery of water of productive use
Be settled out in the later solution of manganous carbonate containing a large amount of sodium sulfate and sodium hyposulfate, the anhydrous sodium sulphate byproduct becoming commercial form must be reclaimed, on the other hand, the most of water in whole production process is also present among this solution, also must be reclaimed.
In order to extract solid sodium sulfate from being settled out in the later solution of manganous carbonate, present invention employs cold method makes sodium sulfate and sodium hyposulfate form xln, because sodium sulfate has very special dissolution characteristics in aqueous, namely when temperature drops to 0 DEG C from 32 DEG C, the solubleness of sodium sulfate is reduced to original 1/10, and separates out Na2SO410H2O crystallization.Fall at the same temperature in scope, the solubleness of sodium hyposulfate in water is also reduced to original 1/3, and separates out Na2S2O62H2O crystallization.
Therefore by this principle, be first refrigerated to 0 DEG C by being settled out the later solution of manganous carbonate, then have Na2SO410H2O and Na2S2O62H2O mixed crystallization to separate out, then mixed crystallization is heated to 110 DEG C, crystal water is deviate from, continue to be heated to 267 DEG C and sodium hyposulfate is decomposed:
Na2S2O6=Na2SO4+SO2
Finally namely obtain anhydrous sodium sulphate byproduct, decomposition reaction separate out sulfur dioxide gas then turn back to leaching system use, the crystal water deviate from also recyclable enter wash water system.
Subzero fractionation goes out the later mother liquor of crystallization and carries out separating treatment through nanofiltration system.Mother liquor after crystallization is containing 11g/LNa2SO4 and 60g/LNa2S2O6, and after the filtration/inspissated process of nanofiltration membrane, the mother liquor of 35.3% is condensed to the concentrated solution containing 31.2g/LNa2SO4 and 170g/LNa2S2O6, turns back to refrigeration system recrystallize.The mother liquor of 64.7% becomes clear water through nanofiltration membrane, and enter leached mud countercurrent washing system (CCD) and use as wash water, wash water within the system manganese content raises gradually, finally turns back to leaching system, thus the recycle to extinction realizing water of productive use uses.
The present invention has the following advantages: technique is simple, resource circulation utilization, and the reducing leaching rate of manganese even up to 98%, can recycle efficiency high.
Embodiment
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art should understand, described embodiment is only help to understand the present invention, should not be considered as concrete restriction of the present invention.
Embodiment one
A kind of low-grade manganese produces Process of Electrolytic Manganese, its technical process comprises: ore grinding, sulfuric acid preextraction, burning Sulfur prepare sulfurous gas, sulphur dioxide reduction leaching, solid-liquid separation, purification of leaching liquor, the separation of dithionic acid root, electrolytic metal Mn production, the decomposition of dithionic acid root, anhydrous sodium sulphate is produced, and the recovery of water of productive use.
The composition of described low-grade manganese is (%): 48.8SiO2,0.4TiO2,10.9Al2O3,2.3Fe, 10.6Mn, 0.9MgO, 4.4CaO, 1.6Na2O, 4.6K2O, 0.1P2O5,1.7Ba.
1 ore grinding
First manganese ore enters feed bin by Grid screen, and the large lump ore on Grid screen then rolls with dozer and makes it to be forced through Grid screen and enter feed bin.Manganese ore after putting in storage enters the crushing system become with drum screen banks by hammer mill; Be crushed to below granularity 30mm, be sent to leaching system, on the sieve of drum sieve, ore deposit then turns back to hammer mill feed end.
2 sulfuric acid preextraction
Granularity is the broken manganese ore of below 30mm and the ore pulp being mixed into concentration about 12% ~ 20% containing manganese washing lotion in agitation vat returned from leached mud countercurrent washing system, add sulphuric acid soln simultaneously, under strong stirring action, broken manganese ore is crushed into fine-grannular, and the acid consumpting substance and the sulfuric acid reaction that are mainly calcium produce insoluble vitriol simultaneously.
3 burning Sulfurs prepare sulfurous gas
First Sulfur is heated to more than 115 DEG C and makes it liquefaction, then liquid Sulfur is atomized by spraying gun, and burns when excessive 20% air, generates by volume containing rare sulfur dioxide gas of 17.5%SO2,79.0%N2 and 3.5%O2.The heat discharged in Sulfur combustion processes produces steam by heat exchanger, and these steam, by condensing turbine, can produce electric power continuously.
4 sulphur dioxide reductions leach
Manganese ore slurry after persulfuric acid preextraction enters a series of plural serial stage leaching barrel arranged in notch cuttype, sulfurous gas (excessive 10%) and manganese oxide ore pulp are that reverse entering successively in each leaching barrel carries out reducing leaching reaction, the tetravalent manganese in manganese ore is made to be reduced into the divalent manganesetion of solubility
During reducing leaching, control pulp density is 10%, SO2 concentration is 6%, and manganese ore granularity is 70 orders (210 μm), and sulfuric acid concentration is 0.05-0.1M.The reducing leaching rate of manganese even up to 98%, generally can reach more than 90%.
5 solid-liquid separation
Complete leach liquor that reducing leaching reacts later to overflow to leach liquor thickener from last step leaching barrel top and carry out solid-liquid separation.The supernatant leach liquor of this thickener is about 50g/L containing manganese, wherein the ratio of manganous sulfate and manganous dithionate is about 1: 0.16, this supernatant liquor enters purification of leaching liquor system from thickener overflow, the underflow of thickener then enters leached mud countercurrent washing system, this system is made up of, as production system recycle-water and the leached mud antikinesis of washing lotion a series of thickener arranged in notch cuttype.Leached mud filters with filter after fully washing in this system again, is namely transported to former stope and backfills, then return leaching system containing manganese washing water after filter cake washing.
6 purification of leaching liquor
The pH of leach liquor is brought up to more than 5.5, and passes into air and make divalent ion be oxidized to ferric ion, now iron, aluminium, arsenic all can be reduced to lower than 1ppm, and silicon and copper content also have remarkable reduction
Then adopt sulphide precipitation to be removed, when the sulfide of depositing zinc and cobalt, should carry out under the condition of pH neutrality, and should avoid using excessive vulcanizing agent, in order to avoid cause the sulphur content in Electrolytic Manganese Product to exceed standard.
Separation-manganous carbonate the precipitator method of 7 dithionic acid roots
By the manganous carbonate precipitator method, make the manganous sulfate in leach liquor and manganous dithionate all generate manganous carbonate precipitation, sulfate radical and dithionic acid root then generate sodium salt and stay in the solution, thus mn ion and dithionic acid root are separated;
Gained manganous carbonate precipitation, after washing, filtering, with being dissolved containing sour anolyte of returning from electrolyzer, namely obtains the electrolytic solution of manganese sulfate solution as electrolytic metal Mn.
8 electrolytic metal Mns are produced
By aforementioned manganese sulfate solution again after removing the deep purifying of iron and heavy metal further, for producing the qualified feed liquor of electrolyzer of electrolytic metal Mn, the electrode materials that electrolytic process adopts is roughly the same with existing electrolytic metal Mn industrial production with processing parameter.Electrolytic process tests the Electrolytic Manganese Product purity obtained can reach more than 99.5%, and current efficiency is also suitable with industrial representative data, can reach more than 67%.
9 dithionic acid roots decompose, and anhydrous sodium sulphate is produced, and the recovery of water of productive use
Be settled out in the later solution of manganous carbonate containing a large amount of sodium sulfate and sodium hyposulfate, the anhydrous sodium sulphate byproduct becoming commercial form must be reclaimed, on the other hand, the most of water in whole production process is also present among this solution, also must be reclaimed.
In order to extract solid sodium sulfate from being settled out in the later solution of manganous carbonate, present invention employs cold method makes sodium sulfate and sodium hyposulfate form xln, first 0 DEG C is refrigerated to by being settled out the later solution of manganous carbonate, Na2SO410H2O and Na2S2O62H2O mixed crystallization is then had to separate out, again mixed crystallization is heated to 110 DEG C, crystal water is deviate from, continues to be heated to 267 DEG C and sodium hyposulfate is decomposed;
Finally namely obtain anhydrous sodium sulphate byproduct, decomposition reaction separate out sulfur dioxide gas then turn back to leaching system use, the crystal water deviate from also recyclable enter wash water system.
Subzero fractionation goes out the later mother liquor of crystallization and carries out separating treatment through nanofiltration system.Mother liquor after crystallization is containing 11g/LNa2SO4 and 60g/LNa2S2O6, and after the filtration/inspissated process of nanofiltration membrane, the mother liquor of 35.3% is condensed to the concentrated solution containing 31.2g/LNa2SO4 and 170g/LNa2S2O6, turns back to refrigeration system recrystallize.The mother liquor of 64.7% becomes clear water through nanofiltration membrane, and enter leached mud countercurrent washing system (CCD) and use as wash water, wash water within the system manganese content raises gradually, finally turns back to leaching system, thus the recycle to extinction realizing water of productive use uses.
Applicant states, the present invention illustrates detailed process equipment and process flow process of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned detailed process equipment and process flow process, namely do not mean that the present invention must rely on above-mentioned detailed process equipment and process flow process and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to equivalence replacement and the interpolation of ancillary component, the concrete way choice etc. of each raw material of product of the present invention, all drops within protection scope of the present invention and open scope.
Claims (1)
1. a low-grade manganese produces Process of Electrolytic Manganese, its technical process comprises: ore grinding, sulfuric acid preextraction, burning Sulfur prepare sulfurous gas, sulphur dioxide reduction leaching, solid-liquid separation, purification of leaching liquor, the separation of dithionic acid root, electrolytic metal Mn production, the decomposition of dithionic acid root, anhydrous sodium sulphate is produced, and the recovery of water of productive use;
(1) ore grinding
First manganese ore enters feed bin by Grid screen, and the large lump ore on Grid screen then rolls with dozer and makes it to be forced through Grid screen and enter feed bin; Manganese ore after putting in storage enters the crushing system become with drum screen banks by hammer mill; Be crushed to below granularity 30mm, be sent to leaching system, on the sieve of drum sieve, ore deposit then turns back to hammer mill feed end;
(2) sulfuric acid preextraction
Granularity is the broken manganese ore of below 30mm and the ore pulp being mixed into concentration about 12% ~ 20% containing manganese washing lotion in agitation vat returned from leached mud countercurrent washing system, add sulphuric acid soln simultaneously, under strong stirring action, broken manganese ore is crushed into fine-grannular, and the acid consumpting substance and the sulfuric acid reaction that are mainly calcium produce insoluble vitriol simultaneously;
(3) Sulfur that burns prepares sulfurous gas
First Sulfur is heated to more than 115 DEG C and makes it liquefaction, then liquid Sulfur is atomized by spraying gun, and burns when excessive 20% air, generates by volume containing rare sulfur dioxide gas of 17.5%SO2,79.0%N2 and 3.5%O2; The heat discharged in Sulfur combustion processes produces steam by heat exchanger, and these steam, by condensing turbine, can produce electric power continuously;
(4) sulphur dioxide reduction leaches
Manganese ore slurry after persulfuric acid preextraction enters a series of plural serial stage leaching barrel arranged in notch cuttype, the sulfurous gas of excessive 10% and manganese oxide ore pulp are that reverse entering successively in each leaching barrel carries out reducing leaching reaction, make the tetravalent manganese in manganese ore be reduced into the divalent manganesetion of solubility; During reducing leaching, control pulp density is 10%, SO2 concentration is 6%, and manganese ore granularity is 70 orders, and sulfuric acid concentration is 0.05-0.1M; The reducing leaching rate of manganese even up to 98%, generally can reach more than 90%;
(5) solid-liquid separation
Complete leach liquor that reducing leaching reacts later to overflow to leach liquor thickener from last step leaching barrel top and carry out solid-liquid separation; The supernatant leach liquor of this thickener is about 50g/L containing manganese, wherein the ratio of manganous sulfate and manganous dithionate is about 1: 0.16, this supernatant liquor enters purification of leaching liquor system from thickener overflow, the underflow of thickener then enters leached mud countercurrent washing system, this system is made up of, as production system recycle-water and the leached mud antikinesis of washing lotion a series of thickener arranged in notch cuttype; Leached mud filters with filter after fully washing in this system again, is namely transported to former stope and backfills, then return leaching system containing manganese washing water after filter cake washing;
(6) purification of leaching liquor
The pH of leach liquor is brought up to more than 5.5, and passes into air and make divalent ion be oxidized to ferric ion, now iron, aluminium, arsenic all can be reduced to lower than 1ppm, and silicon and copper content also have remarkable reduction;
Then adopt sulphide precipitation to be removed, when the sulfide of depositing zinc and cobalt, should carry out under the condition of pH neutrality, and should avoid using excessive vulcanizing agent, in order to avoid cause the sulphur content in Electrolytic Manganese Product to exceed standard;
(7) separation-manganous carbonate precipitator method of dithionic acid root
By the manganous carbonate precipitator method, make the manganous sulfate in leach liquor and manganous dithionate all generate manganous carbonate precipitation, sulfate radical and dithionic acid root then generate sodium salt and stay in the solution, thus mn ion and dithionic acid root are separated;
Gained manganous carbonate precipitation, after washing, filtering, with being dissolved containing sour anolyte of returning from electrolyzer, namely obtains the electrolytic solution of manganese sulfate solution as electrolytic metal Mn;
(8) electrolytic metal Mn is produced
By aforementioned manganese sulfate solution again after removing the deep purifying of iron and heavy metal further, for producing the qualified feed liquor of electrolyzer of electrolytic metal Mn, the electrode materials that electrolytic process adopts is roughly the same with existing electrolytic metal Mn industrial production with processing parameter;
(9) dithionic acid root decomposes, and anhydrous sodium sulphate is produced, and the recovery of water of productive use
Be settled out in the later solution of manganous carbonate containing a large amount of sodium sulfate and sodium hyposulfate, the anhydrous sodium sulphate byproduct becoming commercial form must be reclaimed, on the other hand, the most of water in whole production process is also present among this solution, also must be reclaimed;
Cold method makes sodium sulfate and sodium hyposulfate form xln, first 0 DEG C is refrigerated to by being settled out the later solution of manganous carbonate, Na2SO410H2O and Na2S2O62H2O mixed crystallization is then had to separate out, again mixed crystallization is heated to 110 DEG C, crystal water is deviate from, continues to be heated to 267 DEG C and sodium hyposulfate is decomposed;
Finally namely obtain anhydrous sodium sulphate byproduct, decomposition reaction separate out sulfur dioxide gas then turn back to leaching system use, the crystal water deviate from also recyclable enter wash water system;
Subzero fractionation goes out the later mother liquor of crystallization and carries out separating treatment through nanofiltration system; Mother liquor after crystallization is containing 11g/LNa2SO4 and 60g/LNa2S2O6, and after the filtration/inspissated process of nanofiltration membrane, the mother liquor of 35.3% is condensed to the concentrated solution containing 31.2g/LNa2SO4 and 170g/LNa2S2O6, turns back to refrigeration system recrystallize; The mother liquor of 64.7% becomes clear water through nanofiltration membrane, and enter leached mud countercurrent washing system (CCD) and use as wash water, wash water within the system manganese content raises gradually, finally turns back to leaching system, thus the recycle to extinction realizing water of productive use uses.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104762466A (en) * | 2015-04-17 | 2015-07-08 | 北京矿冶研究总院 | Liquid preparation method for producing electrolytic manganese or manganese dioxide from low-grade manganese oxide ore |
| CN107586951A (en) * | 2017-08-11 | 2018-01-16 | 四川大学 | A kind of method that manganese, iron isochronous resources utilize in low-grade manganese carbonate ore |
| CN110484727A (en) * | 2019-09-19 | 2019-11-22 | 中国恩菲工程技术有限公司 | The minimizing technology of manganese ion and its application in hydrometallurgy zinc metallurgy field |
| CN111111854A (en) * | 2019-12-30 | 2020-05-08 | 铜仁学院 | Manganese ore industrialization wet ball milling method based on electrolytic manganese metal system backwater |
| CN115418476A (en) * | 2022-07-26 | 2022-12-02 | 株洲精卓科技有限公司 | Method for treating low-manganese ore containing tin and product thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104762466A (en) * | 2015-04-17 | 2015-07-08 | 北京矿冶研究总院 | Liquid preparation method for producing electrolytic manganese or manganese dioxide from low-grade manganese oxide ore |
| CN104762466B (en) * | 2015-04-17 | 2017-01-11 | 北京矿冶研究总院 | Liquid preparation method for producing electrolytic manganese or manganese dioxide from low-grade manganese oxide ore |
| CN107586951A (en) * | 2017-08-11 | 2018-01-16 | 四川大学 | A kind of method that manganese, iron isochronous resources utilize in low-grade manganese carbonate ore |
| CN107586951B (en) * | 2017-08-11 | 2018-10-26 | 四川大学 | A kind of method that manganese, iron isochronous resources utilize in low-grade manganese carbonate ore |
| CN110484727A (en) * | 2019-09-19 | 2019-11-22 | 中国恩菲工程技术有限公司 | The minimizing technology of manganese ion and its application in hydrometallurgy zinc metallurgy field |
| CN111111854A (en) * | 2019-12-30 | 2020-05-08 | 铜仁学院 | Manganese ore industrialization wet ball milling method based on electrolytic manganese metal system backwater |
| CN115418476A (en) * | 2022-07-26 | 2022-12-02 | 株洲精卓科技有限公司 | Method for treating low-manganese ore containing tin and product thereof |
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