CN101845562B - Improved device and method for producing electrolytic manganese metal by two-ore method - Google Patents

Improved device and method for producing electrolytic manganese metal by two-ore method Download PDF

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CN101845562B
CN101845562B CN2010102057576A CN201010205757A CN101845562B CN 101845562 B CN101845562 B CN 101845562B CN 2010102057576 A CN2010102057576 A CN 2010102057576A CN 201010205757 A CN201010205757 A CN 201010205757A CN 101845562 B CN101845562 B CN 101845562B
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manganese
ore
electrolysis
metal
leaching
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CN101845562A (en
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陈榜龙
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陈榜龙
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B47/00Obtaining manganese
    • C22B47/0018Treating ocean floor nodules
    • C22B47/0045Treating ocean floor nodules by wet processes
    • C22B47/0054Treating ocean floor nodules by wet processes leaching processes
    • C22B47/0063Treating ocean floor nodules by wet processes leaching processes with acids or salt solutions
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/04Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • C22B3/06Extraction 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
    • C22B3/08Sulfuric acid, other sulfurated acids or salts thereof
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/22Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, by thermal decomposition
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B47/00Obtaining manganese
    • C22B47/0018Treating ocean floor nodules
    • C22B47/0045Treating ocean floor nodules by wet processes
    • C22B47/0081Treatment or purification of solutions, e.g. obtained by leaching
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25CPROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C1/00Electrolytic production, recovery or refining of metals by electrolysis of solutions
    • C25C1/06Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese
    • C25C1/10Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese of chromium or manganese
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Recycling

Abstract

The invention discloses an improved device and method for producing electrolytic manganese metal by a two-ore method. The method comprises the following steps of leaching, purifying, deeply purifying and electrolyzing; and two ore raw materials for electrolyzing the manganese metal by the two-ore method are low-grade manganese oxide ores and pyrite ores respectively, wherein the low-grade manganese oxide ores are with the manganese content of 15-25%, and the pyrite ores are tailings (the pyrite ores) of the mineral dressing of non-ferrous metal ores or primary ores. The method has the advantages that a product contains C and S, has low impurity and short production flow, is used for deeply purifying a manganese sulfate solution to eliminate the influence of reductive impurities in the solution on the electrolytic process, thereby realizing the normal electrolytic production and improving the quality of products. The method especially creates ways for the development and the utilization of low-grade lean manganese oxide ores and tailings (the pyrite ores) of the mineral dressing of non-ferrous metal ore.

Description

The device and method of modified version method for producing electrolytic manganese metal by two-ore
Technical field
The present invention relates to the apparatus and method technical field of electrolytic metal Mn, particularly a kind of device and method of modified version method for producing electrolytic manganese metal by two-ore.
Background technology
In modern industry, manganese and compound thereof are applied to the every field of national economy.Wherein Iron And Steel Industry is most important field, accounts for 90%~95% with the manganese amount, mainly as reductor and the sweetening agent in ironmaking and the steelmaking process, and is used for alloying.All the other manganese of 10%~5% are used for other industrial circles; such as chemical industry (making the various manganese salts that contain), light industry (being used for battery, match, seal lacquer, soapmaking etc.), building materials industry (tinting material and the decolourant of glass and pottery), national defense industry, electronic industry; and environment protection and husbandry, etc.In a word, manganese has very important strategic position in national economy.
The application of manganese on Iron And Steel Industry is the result of various countries metallurgist unremitting effort decades.After 1875, European Countries begins to contain the spiegel of manganese 15%~30% and contain manganese and reach 80% ferromanganese with blast furnace production.Produce ferromanganese with electric furnace in 1890, produced manganese metal with thermite process in 1898, and developed electric furnace desiliconization purifying method production low carbon ferromanganese.Nineteen thirty-nine begins to produce manganese metal with electrolytic process.
The refinement mode of manganese metal mainly contains two kinds of hot method (pyrogenic process) and electrolytic process (wet method), hot method production (manganese metal) purity is no more than 95~98%, pure manganese metal then is that its purity is more than 99.7~99.9% by electrolytic process preparation (electrolytic metal Mn).Now, electrolytic process is produced has become the major way that manganese metal is produced.Electrolytic metal Mn is to obtain manganese salt, the elemental metals that send again electrolytic tank electrolysis to separate out with manganese ore through Ore Leaching.The outward appearance chalybeate is irregular sheet, and matter is hard and crisp, the one side light, another side is coarse, for silvery white to brown, be silver gray after being processed as powder; Easily oxidation in air, dissolving and displace hydrogen when meeting diluted acid, a little more than room temperature the time, but water of decomposition and releasing hydrogen gas.
In the process of electrolytic manganese, make first manganous sulfate.The production method of existing manganese sulfate solution is: with crusher manganese ore is crushed to particle below the 30mm, with dry grinding mill manganese ore is worn into one 100 purpose breezes again, again the troilite powder that contains S>=32%, granularity 80 1 100 orders, prepare according to a certain percentage with the manganese ore powder, again Jia Shui, add sulfuric acid.Through reacting by heating, deironing, removing heavy metals, neutralization, press filtration. make manganese sulfate solution.
There is following weak point in this traditional technology method:
1. producing the restriction be subjected to manganese ore content needs just can produce the manganese sulfate product that manganese content is recognized 98-99% with manganese content at the higher-grade manganese ore more than 34%, such as the manganous sulfate content that can only produce at the low-grade manganese of 10-20% with manganese content at the product below 96%;
2, production cost is high, energy consumption is high: 1 ton of manganous sulfate of every production need consume coal 1.2-1.5 ton:
3, manganese recovery ratio is low: manganese recovery ratio is only up to 60-65%.
Chinese invention patent (following is number of patent application or the patent No.) CN91102845, CN 92112673, CN 200510020913, CN 200710192608, CN 200710192613, CN 200810058946 patent documents such as grade and/or patent application document also disclose respectively several two ore deposit methods and have produced the method for electrolytic manganese and use low-grade manganese stone two ore deposit methods to produce the method for electrolytic manganese or the preparation technology of manganous sulfate, but aforesaid method has the following disadvantages:
1, do not have to solve the purification and impurity removal technology make after the manganese sulfate solution, the Technology of the manganous sulfate electrolysis production that obtains by two ore deposit methods is unstable, and Production Flow Chart length, not environmental protection, energy consumption height, production cost are high, and the yield of manganese metal is low;
2, the manganese metal product of producing with above-mentioned technology contains C, S and measures height, and purity is low;
3, in the production technology to the unexecuted deep purifying of manganese sulfate solution, do not remove that reducing impurity has reduced quality product to the impact of electrolytic process in the electrolytic solution;
4, in two ore deposit method electrolytic processes, to having relatively high expectations of sulfurous iron ore, adopt the high sulfurous iron ore of sulphur content, large to environmental influence, production cost is high;
5, the manganese metal recovery rate is low, and the rate of recovery of manganese metal only is 60%~63%.
Summary of the invention
Technical problem to be solved by this invention is, having overcome does not have to solve the manganese sulfate solution purification and impurity removal technology afterwards that makes in the prior art, the Technology of the manganous sulfate electrolysis production that obtains by two ore deposit methods is unstable, the problems such as Production Flow Chart length, not environmental protection, energy consumption is high, production cost is high, and the yield of manganese metal is low.A kind of device and method of modified version method for producing electrolytic manganese metal by two-ore is provided, successfully solved the purification and impurity removal technology of manganese sulfate solution, acquisition meets the qualified solution of electrolysis requirement, thereby the Technology that reaches electrolysis production is stable, Production Flow Chart weak point, environmental protection, energy-saving and cost-reducing, production cost is low, the metal recovery rate of manganese improves 10~15%.
For solving the problems of the technologies described above, the invention provides a kind of method of modified version method for producing electrolytic manganese metal by two-ore, said method comprising the steps of: leaching, purification, deep purifying and electrolysis;
Two kinds of ores of described two ore deposit method electrolytic metal Mns are respectively: Low grade manganese ore and low grade pyrite;
Described Low grade manganese ore is: manganese content is 15~25% manganese oxide ore;
Described low grade pyrite is: the mine tailing sulfurous iron ore of nonferrous metals ore ore dressing or primary sulfurous iron ore; Wherein, the content of sulphur is 25~30%.
The step of described leaching can comprise:
Take the manganese oxide ore of manganese content as 15~25% as raw material, choose contain S25~30%, contain Fe30~45% nonferrous metals ore mine tailing is the reductive agent raw material;
Two kinds of ores are ground to granularity 80-130 purpose breeze, and anolyte mixes, and directly is heated to 90-100 ℃ in the sulphuric acid soln of 85-120g/l; Wherein, according to ratio of weight and number manganese ore powder: troilite powder: the ratio of sulfuric acid is 1: 0.30-0.5: 0.40-0.50;
Agitation leach 2-4 hour.
The step of described purification can comprise:
The oxidation neutralized ex iron: the pulp PH value after leaching with the ammoniacal liquor adjustment is to 4.0-5.0, by containing Fe in the liquid + 2Amount add manganese ore powder Oxidation of Fe SO4 and generate Fe2 (SO) 3;
Adjust pulp PH value to 6-7 with ammoniacal liquor again, Fe2 (SO) 3 hydrolysis generate Fe (OH) 3 and are deposited in the leached mud, and ore pulp gets thick manganese sulfate solution through filter pressing;
The sulfuration removing heavy-metal impurities: described thick manganese sulfate solution adds the vulcanizing agent sulfuration and removes beavy metal impurity, liquid after press filtration obtains sulfuration.
The step of described deep purifying can comprise:
With the solution after the sulfuration purification, to adopt strong oxidizer discharge manganese powder and/or ammonium persulphate/hydrogen peroxide to make scavenging agent and carry out deep purifying, reducing impurity is removed in oxidation, makes reducing impurity be transformed into the simple substance element ion and exists in the solution;
Flocculated heavy clear 24-48 hour with Tai-Ace S 150 reagent again, behind the adding selenium, obtain the qualified new liquid of use in electrolysis after the press filtration.
The step of described electrolysis can comprise:
Solution with the deep purifying step process is crossed adds Se, is configured to: Mn18-23g/l, (NH4) 2SO4100-120g/l, the fluting liquid of Se30-50mg/l; Regulate pH value to PH7.0-7.5 with ammonia soln;
Electrolysis is carried out in energising, and strength of current raises gradually, switches on after 4-8 hour, and strength of current is raised to the setting operation value;
Electrolysing period is 24 hours.
Described electrolysis procedure control condition is preferably as follows:
Advance tank liquor: Mn35-40g/L, (NH4) 2SO4 100-120g/L PH 6.5-7.0;
Catholyte: Mn15-18g/L, (NH4) 2SO4 110-120g/L PH 6.5-7.5;
Anolyte: Mn15-18g/L, (NH4) 2SO4 110-120g/L H2SO4 38-45g/L;
Cathode current density: 340-380A/m2; Bath voltage: 4.3-4.8V;
Tank liquor temperature: 38-45 ℃;
Electrolysis additive: SeO2 contains Se 20-40mg/L;
Electrolysing period: 24 hours.
The step of described leaching can comprise:
First in leaching vat, inject anolyte, after anolyte has the first agitating vane, do not start stirrer, then begin in leaching vat, to throw in manganese ore powder and troilite powder, and add sulfuric acid, open the steam heating ore pulp, when slurry temperature reaches 90 ℃, start the clock;
Detect the Mn amount that contains of leach liquor, after containing the Mn amount and reaching the concentration of setting, leach and finish;
Wherein,
Manganese ore powder: sulfurous iron ore: the sulfuric acid mass ratio is 1: 0.3~0.5: 0.38~0.5;
Leach 90~100 ℃ of slurry temperatures;
Extraction time: the end that feeds intake, ore pulp are warmed up to 90 ℃, and the beginning timing was leached 2~4 hours.
For solving the problems of the technologies described above, the present invention also provides a kind of device of producing electrolytic metal Mn, and described device comprises: powder manufacturing apparatus, leaching plant, filtering equipment, sulfuration pond, treating pond, dark treating pond, settling pool, air compressor, adjustment bucket and electrolyzer.
Described powder manufacturing apparatus can be the Raymond mill of 3R, 4R or 5R type;
Described leaching plant can be leaching vat that paddle formula mixing component is housed;
Described electrolyzer is preferably made with the lumps of wood, in the wooden false end, arranged, the snakelike water-cooled tube that stainless steel tube is made is equipped with in the inner both sides of described electrolyzer, each electrolyzer is provided with one or more groups anode frame, be provided with negative plate N piece in each electrolyzer, positive plate N+1 piece; Wherein, N is positive integer.
Described negative plate can be stainless steel plate;
Described positive plate can be lead, antimony, tin, silver-colored quad alloy plate;
The ratio of the preferred useful area of described positive plate and negative plate useful area 0.6: 1.0;
After the described negative plate electrolysis, become negative electrode manganese plate; Described negative electrode manganese plate in use is used following method Passivation Treatment: passivator is potassium dichromate aqueous solution, concentration 3%, a negative electrode manganese of every taking-up plate when transferring groove, dip in immediately passivating solution, make the manganese metal table generate layer oxide film, reach the not oxidized blackening in air of manganese plate, do not affect quality product;
Manganese plate after the passivation is used flushing with clean water, the passivator on flush away surface, and then put into 80~100 ℃ of boiling hot water and scald, the impurity such as ammonium sulfate of crystallization on the flush away manganese plate;
Scald rear manganese plate through air-dry, peel off, obtain the sheet metal manganese product, then the packing warehouse-in;
Negative plate after the demanganize is treated to: the pole plate of non-cohesive residual manganese, and stand-by after cleaning; Be attached with and peel off to get off residual manganese plate and be put into anolyte drill traverse bubble, after residual manganese dissolve, dip in nitric acid liquid, clear water is cleaned stand-by afterwards again;
The negative plate of brightless (turn white, scared) is electroplated after the polishing stand-by.
The method of modified version method for producing electrolytic manganese metal by two-ore of the present invention and device thereof belong to pure hydrometallurgical processes, and industrial production test shows, mature production technology, and advanced technology is reliable, and quality product is high, and especially product contains C, S, and impurity is low.The traditional technology that present method and manganese oxide ore are produced electrolytic manganese compares, and has improved workman's labor condition, and Production Flow Chart is short, is in fact the producing and manufacturing technique of environmental protection and energy saving.Production practice are carried out deep purifying to manganese sulfate solution, removed in the solution reducing impurity impact of electrolytic process is normally produced thereby reach electrolysis, improve the quality of products.Present method especially is that approach has been created in the development and use of the mine tailing (sulfurous iron ore) of low-grade oxygen deprivation manganese ore and nonferrous metals ore ore dressing.Moreover low product manganese oxide ore and sulfurous iron ore source are wide, and price is low, so production cost is low, and the manganese metal recovery rate is than traditional technology raising 10~15%.
Description of drawings
Fig. 1 is the schema of modified version method for producing electrolytic manganese metal by two-ore method in the embodiment of the invention.
Embodiment
The method of method for producing electrolytic manganese metal by two-ore of the present invention is that the processing step by: ore fine grinding, batching mixing, leaching, purification, deep purifying, electrolysis carries out.Above-mentioned leaching step comprises: take manganese oxide ore as raw material, sulfurous iron ore is reductive agent, and two kinds of breezes (granularity 100% is the 80-130 order) mix with anolyte by proportioning, and directly heated and stirred leaches in sulphuric acid soln, and manganese is MnSO 4, iron is Fe 2(SO 4) 3Enter solution.The present invention has improved workman's labor condition, for approach has been created in the development and use of Low grade manganese ore and nonferrous metals ore milltailings (sulfurous iron ore).The present invention is through production test for many years, successfully solved the purification and impurity removal technology of manganese sulfate solution, acquisition meets the qualified solution of electrolysis requirement, thereby the Technology that reaches electrolysis production is stable, Production Flow Chart weak point, environmental protection, energy-saving and cost-reducing, production cost is low, the metal recovery rate of manganese improves 10~15%.
In one embodiment of this invention, method for producing electrolytic manganese metal by two-ore carries out according to the following steps:
Raw material is manganese oxide ore (Low grade manganese ore contains Mn15~25%).
Reductive agent is sulfurous iron ore (mine tailing of nonferrous metals ore ore dressing or primary sulfurous iron ore).
One, the preparation of manganese ore powder processing
1, the mechanical means of preparation manganese ore powder
Manganese ore prepares particulate manganese ore powder through ore grinding, and the Raymond mill of this process selection 3R, 4R, 5R type is powder process machinery.The machine has the size separation device, can regulate granularity and the output of output powder;
2, the granularity requirements of manganese ore powder and reductive agent
By experiment and production practice, be to produce to obtain satisfied technico-economical comparison, it be ideal that manganese ore powder and sulfurous iron ore fineness requirement 100% are crossed 80~130 mesh sieve holes;
3, the main chemical compositions of manganese ore powder and reductive agent
The main chemical compositions of manganese ore powder: require to contain Mn15~25%
The sulfurous iron ore main chemical compositions: require to contain S25~30%, Fe35~40%, other impurity element (Co, Ni, Zn, Cu etc.) content is more low better, can reduce impurity removal reagents consumption like this.
Two, the leaching of manganese ore powder liquid operation processed
1, leaching plant general introduction
Leaching vat are major equipments of this operation, for satisfying the requirement of producing 20,000 tons of production technique, have selected 7 leaching vat that paddle formula whipping appts is housed, and its volume is useful volume 300m 3/ groove), 7 (useful volume 300m have been selected 3/ groove) leaching vat are equipped with paddle formula whipping appts.
2, leach the operation of operation
The technical qualification of 2-1, leaching: established following technical qualification namely by test:
Manganese ore powder: sulfurous iron ore: sulfuric acid (mass ratio) is that 1: 0.3~0.5: 0.3~0.5. leaches 90~100 ℃ of slurry temperatures
Extraction time: the end that feeds intake, ore pulp are warmed up to 90 ℃, and the beginning timing was leached 2~4 hours.
2-2, leaching operation concrete operations: in leaching vat, inject anolyte on request first, after having the first agitating vane, anolyte do not start stirrer, then begin in leaching vat, to throw in manganese ore powder and troilite powder by measuring requirement, and add an amount of sulfuric acid by the requirement of sulfuric acid consumption, open the steam heating ore pulp, when slurry temperature reaches 90 ℃, start the clock.Process repeatedly detects the Mn amount of containing of leach liquor, after containing the Mn amount and reaching given concentration, leaches at last and finishes.
The chemical reaction of 2-3, leaching process: two ore deposit method leaching process, manganese is MnSO 4, iron is Fe 2(SO 4) 3Enter solution, other impurity element (Co, Ni, Zn, Cu etc.) also generates corresponding vitriol and enters in the solution, and leaching process belongs to very complicated heterogeneous chemical reaction, and its net reaction is
15MnO 2+2FeS 2+14H 2SO 4=15MnSO 4+Fe 2(SO 4) 3+14H 2O
MeO+H 2SO 4=MeSO 4+H 2O
MeO is heavy metal (Co, Ni, Zn, Cu etc.) oxide compound.
2-4, leaching oxidation of ore pulp neutralized ex iron: leach and finish, pulp PH value is 2.5~3.0, sampling qualitative analysis Fe 2+Ion is according to Fe 2+The content situation is adjusted pulp PH value to 4.5~5.0 with ammoniacal liquor, then drops into an amount of manganese ore powder in the leaching vat and carries out oxidation, stirs oxidation 20~30 minutes, and qualitative analysis Fe takes a sample 2+, until Fe 2+Reach qualified requirement, adjust pulp PH value to 6.0~6.5 with ammoniacal liquor again.Fe in the leach liquor under this condition 2(SO 4) 3But complete hydrolysis generates Fe (OH) 3Be deposited in and reach deironing purpose, Fe in the leached mud 2(SO 4) 3Hydrolysis is undertaken by the following formula reaction:
Fe 2(SO 4) 3+6H 2O=2Fe(OH) 3+3H 2SO 4
In the iron removal, most of heavy metal ion is hydrolytic precipitation also, impurity SiO 2In company with Fe (OH) 3Be deposited in the leached mud Mn 2+A small amount of hydrolytic precipitation is arranged, and the pulp PH value of therefore necessary fine grasp neutralized ex iron is to reduce the loss of Mn.After the oxidation of ore pulp neutralized ex iron finishes, through press filtration (filter residue send the slag field to store up), obtain the qualified leach liquor of iron content.
The specification of quality of 2-5, qualified leach liquor: it is 38~42g/l that leaching solution behind the oxidation neutralized ex iron requires to contain Mn, qualitative detection Fe 2+Be nothing.
Three, manganous sulfate leach liquor sulfuration removing heavy-metal impurities
1, device overview: filtering equipment 400m 2Four, 200m 2Four, sulfuration pond 300m 3Four, treating pond 300m 3Ten, dark treating pond 300m 3Ten, settling pool 300m 3Eight, air compressor 8m 3Two, an adjustment bucket 2m 3Three.
2, vulcanizing agent:
The vulcanizing agent that manganese sulfate solution sulfuration removing heavy-metal impurities uses has: saturated ammonium sulfide, barium sulphide (BaS), Sodium Dimethyldithiocarbamate (S.D.D), diethyldithiocarbamate etc. represent vulcanizing agent with RS.
3, the remaining beavy metal impurity (Co, Ni, Zn, Cu etc.) of manganese sulfate solution that obtains through press filtration, must add vulcanizing agent vulcanizes, and makes it generate sulfide precipitation and removes, and the main chemical reactions formula is:
MeSO 4+ RS=RSO 4+ MeS ↓ Me → expression impurity element
Sulfuration removal of impurities major technique condition, 50~65 ℃ of solution temperatures, the vulcanizing agent consumption determines that by test our actually operating (contains NH with ammonium sulfide 38%) consumption is example: every cube is come leach liquor consumption ammonium sulfide 2Kg.
Sulfuration removal of impurities concrete operations: manganese sulfate solution sulfuration removal of impurities can be carried out in special stirring truck for vulcanlzing pan, and we are added dropwise to ammonium sulfide liquid in the chute of pressing filtering liquid, the sulfuration liquid that adds ammonium sulfide liquid flows to Chu Chizai and stirred 20~30 minutes with the air compressor wind, get liquid analysis heavy metal content, after Ni, CO, Zn qualitative analysis are qualified, carry out press filtration, stack the special slag of filter residue field, and filtrate is carried out the deep purifying operation.
4, the specification of quality of liquid after the sulfuration: pressing filtering liquid requires after the sulfuration:
Contain Mn38~40g/l, Co<1mg/l, Ni<1mg/l,
Zn≤0.5mg/l,Fe<1mg/l,Cu<0.5mg/l.PH6.0~6.5.
Four, liquid deeply purifying and removing reducing impurity after the sulfuration
Contain the reducing impurity ion in the pressing filtering liquid of manganese sulfate solution sulfuration removing heavy-metal impurities, the electrolysis operation there is detrimentally affect even electrolysis can't normally be produced, seriously affect simultaneously quality product, therefore must carry out deep purifying and remove the reducing impurity ion vulcanizing rear pressing filtering liquid, making it generate the simple substance ion is suspended in the solution, then in solution, add flocculation agent, flocculate, again enter again press filtration behind the settling pool heavy clear more than 24 hours (time more long more be conducive to electrolysis).In pressure-filtering process, in liquid, add an amount of selenium, thereby obtain to meet the seminal fluid of electrolysis requirement.
1, the selection of deep purifying agent: remove that the scavenging agent of reducing impurity has a lot of strong oxidizers available in the manganese sulfate solution: such as manganese dioxide powder, ammonium persulphate, hydrogen peroxide etc., through lot of experiments research, this process choice hydrogen peroxide is that the deep purifying agent obtains satisfied techno-economic effect.
The add-on of 2, deep purifying agent (hydrogen peroxide), long-pending according to liquid after the sulfuration, add by every cubic metre of amount that adds 0.25~0.35 kilogram of hydrogen peroxide, first hydrogen peroxide is mixed with the aqueous solution of 20~40% concentration, in the pressing filtering liquid chute, filtrate flow is to storing up the pond after sulfuration in dropping, after leaving standstill 4 hours, make its abundant oxidation, make the reducing impurity ion-oxygen change into the simple substance ion, and then it is heavy clear to flocculate.
3, flocculation is heavy clear: flocculation agent is selected Tai-Ace S 150, and consumption is 0.1~0.15Kg/m 3Solution is dissolved into the aqueous solution with the Tai-Ace S 150 water first, adds to leave standstill in the pond, starts the pressure fan pneumatic blending 4~5 minutes, carries out the pressure-sizing filter when leaving standstill after 24~48 hours.Add an amount of electrolysis additive by new liquid requirement in the pressure-sizing process, concrete add-on 10~15mg/l Se meter.
4, qualified new liquid composition requires behind the deep purifying:
Mn36~40g/l, Co<1mg/l, Ni<1mg/l, Zn≤0.5~1mg/l, S 2-<2mg/l.Fe 2+Qualitative qualified.
Five, manganese sulfate solution electrolytic deposition manganese industrial practice
The electrolysis production manganese metal all is the MnSO in neutrality 4~(NH 4) 2SO 4~H 2Carry out diaphragm electrolysis in the manganese sulfate solution of O system, anode is placed in the diaphragm frame, and electrolytic process manganese is separated out at negative electrode, precipitated oxygen and a small amount of MnO on the anode 2. production practice are pressed step and are carried out.
1, fluting liquid composition requirement: Mn18~23g/l, (NH 4) 2SO 4100~120g/l, Se30~50mg/l, after PH6.5~7.5. electrolyzer is filled with fluting liquid, in each electrolyzer, fill 3~5 negative plates, begin energising and carry out electrolysis, then pile as early as possible the negative plate of all electrolyzers, supply current intensity raises by wash rice, and the 4 hours after-current intensity of switching on can rise to values for normal operation.
2, the technology condition of electrolysis procedure control:
Advance tank liquor: Mn35~40g/l, (NH 4) 2SO 4100~120g/l, Se10~15mg/l, PH6.5~7.5.
Catholyte: Mn15~18g/l, (NH 4) 2SO 4100~120g/l, Se25~30mg/l, PH6.5~7.5.
Anolyte: Mn15~18g/l, (NH 4) 2SO 4100~120g/l, H 2SO 438~45g/l.
Cathode current density 340~380A/m 2, bath voltage 4.3~4.8V, 38~45 ℃ of tank liquor temperatures, similar poles are apart from 70mm, electrolysing period 24 hours.
3, electrolytic cell assembly
3-1, electrolyzer: electrolyzer is made with the thick lumps of wood of 40mm, in the wooden false end, arranged, outage 170mm at the false end, sky is of a size of length * wide * height=3800 * 710 * 920 (mm) in the trough, the snakelike water-cooled tube that stainless steel tube is made is equipped with in trough two inboards, each electrolyzer is equipped with 5 groups of anode frames, 50 of the in-built negative plates of each electrolyzer, 51 of positive plates.
3-2, yin, yang plate plate: it is negative plate that electrolytic manganese adopts stainless steel plate: it is of a size of length * wide * thick=665 * 500 * 1.5 (mm).Selecting lead, antimony, tin, silver-colored quad alloy plate is positive plate, and the length of anode * wide * thick=665 * 470 * 7.9 (mm) has 50 holes on the pole plate, and the chi in each hole is long 86 * wide by 28.3 (mm).The ratio 0.6 of positive plate useful area and negative plate useful area: 1.0.
4, the processing of negative electrode manganese plate
4-1, accent groove: when electrolysis reaches 24 hours, need to take out the negative plate that deposits manganese, load onto simultaneously this process of stand-by negative plate (dipping in water glass liquid, water glass liquid concentration 1~3% before the dress) and claim to transfer groove, half an hour before the accent groove, by given operational condition, adjust the pH value (7.5~8.0) of tank liquor with ammoniacal liquor, and add an amount of Se, make tank liquor Se content reach 35~45mg/l. and treat that whole negative plates are got and install completely, namely transfer trough end.
The Passivation Treatment of 4-2, negative electrode manganese plate
In order to prevent manganese metal by deterioration by oxidation in the air, negative electrode manganese must carry out Passivation Treatment.Passivator is potassium dichromate aqueous solution, concentration 3%, and a negative electrode manganese of every taking-up plate dips in passivating solution immediately when transferring groove, and the manganese metal table generates layer oxide film, reaches the not oxidized blackening in air of manganese plate, affects quality product.
The manganese plate is used flushing with clean water after 4-3, the passivation, the passivator on flush away surface, and then put into 80~100 ℃ of boiling hot water and scald, the impurity such as ammonium sulfate of crystallization on the flush away manganese plate.Scald rear manganese plate through air-dry, peel off, obtain the sheet metal manganese product, then packing warehouse-in (jumbo bag packing).Quality product reaches the requirement of electrolytic manganese industry standard (YB-T051-2003) general purpose grade DJMnD level quality standard through assay.
The processing of 4-4, negative plate: the negative plate after the demanganize is processed, and depends on the circumstances: the pole plate of non-cohesive residual manganese, and stand-by after cleaning; Be attached with and peel off to get off residual manganese plate and be put into anolyte drill traverse bubble, after residual manganese dissolve, dip in nitric acid liquid, clear water is cleaned stand-by afterwards again.It is rear stand-by that brightless negative plate is electroplated polishing.
In the another embodiment of the present invention, provide the method for another kind of method for producing electrolytic manganese metal by two-ore, pressed: leaching, purification, deep purifying, electrolysis process step are carried out, wherein:
(1) leaches: 1. take Low grade manganese ore as raw material (15-25%Mn), non-ferrous metal ore mine tailing (primary sulfurous iron ore) is reductive agent (contain S20-30%, contain Fe30-35%), two kinds of breezes (granularity 100%-80-130 order) anolyte mixes, directly in sulfuric acid (85-120g/l) solution, heat (90-100 ℃) agitation leach 2-4 hour (manganese ore powder: troilite powder: sulfuric acid (weight ratio), in 1: 0.30-0.5: the ratio of 0.40-0.50, these several examples are adjusted with situation); Manganese is MnSO 4, iron is Fe 2(SO 4) 3Enter solution, leaching process belongs to complicated heterogeneous chemical reaction process, and generally acknowledged chemical reaction is pressed net reaction and carried out:
15MnO 2+2FeS 2+14H 2SO 4=15MnSO 4+Fe 2(SO 4) 3+14H 2O
(2) purify:
1. oxidation neutralized ex iron: adjust pulp PH value to 4.0-5.0, by containing Fe in the liquid with ammoniacal liquor + 2Other adds suitable manganese ore powder Oxidation of Fe SO 4Generate Fe 2(SO) 3, adjust again pulp PH value to 6.5-7.0, Fe 2(SO) 3Hydrolysis generates Fe (OH) 3Be deposited in the leached mud, ore pulp gets thick manganese sulfate solution through filter pressing;
2. sulfuration is except heavily belonging to impurity, and described thick manganese sulfate solution adds an amount of vulcanizing agent (ammonium sulfide, BaS, SDD, diethyldithiocarbamate) sulfuration and removes beavy metal impurity (Ni, Co.Zn.Cn etc.), liquid after press filtration obtains sulfuration.
(3) deep purifying:
Liquid is except reducing impurity after the sulfuration, adopt strong oxidizer discharge manganese powder, ammonium persulphate, hydrogen peroxide to make scavenging agent, oxidation is finally being carried out deep purifying with hydrogen peroxide reagent except the reducing impurity test, makes reducing impurity be transformed into the simple substance element ion and exists in the solution;
Flocculated heavy clear 24-48 hour with Tai-Ace S 150 reagent again, add the qualified new liquid that an amount of selenium (Se) obtains use in electrolysis after the press filtration.
(4) electrolysis:
1. liquid Composition Control: the Mn18-23g/l that slots, (NH 4) 2SO 4After 100-120g/l, Se30-50g/l, PH6.5-7.5, electrolyzer piled fluting liquid, every groove was put first 3~5 negative plates, and electrolysis is carried out in energising, and after negative plate was piled, strength of current raise gradually, switched on after 4 hours, and strength of current is raised to values for normal operation.
2.. the groove face management, after the energising electrolysis, strengthen electrolyzer facial canal reason: the contraposition of close inspection pole plate is correct, measures the composition of tank liquor on time, and such as Mn concentration, pH value etc. are regulated the tank liquor composition with flow quantity at any time and are reached the technical qualification requirement.
3.. electrolysis procedure control condition is as follows:
Advance tank liquor: Mn35-40g/L, (NH 4) 2SO 4100-120g/L PH 6.5-7.0;
Catholyte: Mn15-18g/L, (NH 4) 2SO 4110-120g/L PH 6.5-7.5;
Anolyte: Mn15-18g/L, (NH 4) 2SO 4110-120g/L H2SO4 38-45g/L;
Cathode current density: 340-380A/m2; Bath voltage: 4.3-4.8V;
Tank liquor temperature: 38-45 ℃;
Electrolysis additive: SeO 2, contain Se 20-40mg/L;
Electrolysing period: 24 hours.
4. electrolysis was transferred groove after 24 hours, transferred groove namely to take out the sedimentation manganese negative plate, and the stand-by negative plate of packing into carries out the next cycle electrolysis procedure.
5. long-pending manganese negative plate is processed: the long-pending manganese negative plate of taking-up, carry out immediately passivation, and prevent that product is oxidized, reduce quality, pole plate after the passivation is used first flushing with clean water, scalds again, and is rear air-dry, peels off, and gets flaked product, the packing warehouse-in.
6. quality product reaches GB (GB3418-82) quality standard.
7. the negative plate of peeling off behind the product is processed, and has the negative plate of residual manganese to put into first anolyte and soaks a moment, takes out with putting into nitric acid liquid after the flushing with clean water and soaks a moment, uses the clear water cleaned standby seam again.Without the negative plate of residual manganese, stand-by through the clear water scrub.
Among the again embodiment of the present invention, as follows operation:
Get percent of pass 100%, granularity is 80 purpose manganese ore powder and troilite powders, and in the manganese ore powder: troilite powder: the ratio of sulfuric acid=1: 0.35: 0.42 directly is heated to 90-100 ℃ in sulphuric acid soln, agitation leach 3 hours, adjusting ore pulp PH is 4.5-5.0 manganese powder Oxidation of Fe SO 4Generate Fe 2(SO) 3Adjust pulp PH value to 6-6.5 with ammoniacal liquor, Fe 2(SO) 3Hydrolysis generates Fe (OH) 3Be deposited in the leached mud, ore pulp gets thick manganese sulfate solution through filter pressing; The press filtration waste gets thick manganese sulfate solution.Described thick manganese sulfate solution is removed beavy metal impurity (Ni, Co.Zn.Cu etc.) through sulfuration, and described thick manganese sulfate solution adds the vulcanizing agent sulfuration and removes beavy metal impurity (Ni, Co.Zn.Cn etc.), liquid after press filtration obtains sulfuration.Under 55-65 ℃ of condition, carry out deep purifying with hydrogen peroxide reagent again, make reducing impurity be transformed into the simple substance element ion and exist in the solution; Flocculated heavy clear 24 hours with Tai-Ace S 150 reagent, press filtration obtains the qualified new liquid of use in electrolysis again.Obtain to reach the Electrolytic Manganese Product of GB (GB3418-82.99.7%Mn) through electrolysis.
In the fourth embodiment of the present invention, as follows operation:
Get percent of pass 100%, granularity is 90 purpose manganese ore powder and troilite powders, in the manganese ore powder: troilite powder: the ratio of sulfuric acid=1: 0.4: 0.4, directly in sulphuric acid soln, be heated to 90-100 ℃, agitation leach 3 hours, adjusting pulp PH value is 4.0~5.0, add an amount of manganese powder, with Fe 2+Ion-oxygen changes into Fe 3+Ion is adjusted pulp PH value to 6-6.5 with ammoniacal liquor, Fe 2(SO) 4Hydrolysis generates Fe (OH) 3Be deposited in the leached mud, ore pulp gets thick manganese sulfate solution through filter pressing; The press filtration waste gets thick manganese sulfate solution.Described thick manganese sulfate solution is removed beavy metal impurity (Ni, Co.Zn.Cu etc.) through sulfuration, liquid after press filtration obtains sulfuration.Under 55-65 ℃ of condition, carry out deep purifying with hydrogen peroxide reagent again, make reducing impurity be transformed into the simple substance element ion and exist in the solution; Flocculated heavy clear 32 hours with Tai-Ace S 150 reagent, press filtration obtains the qualified new liquid of use in electrolysis again.Obtain to reach the Electrolytic Manganese Product of GB (GB3418-82.99.7%Mn) through electrolysis.
In the fifth embodiment of the present invention, as follows operation:
Get percent of pass 100%, granularity is 100 purpose manganese ore powder and troilite powders, in the manganese ore powder: troilite powder: the ratio of sulfuric acid=1: 0.45: 0.45, directly in sulphuric acid soln, be heated to 90-100 ℃, agitation leach 4 hours, ore pulp is behind the oxidation neutralized ex iron.Adjust pulp PH value to 6.5, Fe with ammoniacal liquor 2(SO) 4Hydrolysis generates Fe (OH) 3Be deposited in the leached mud, ore pulp gets thick manganese sulfate solution through filter pressing, and the press filtration waste gets thick manganese sulfate solution.Described thick manganese sulfate solution adds the vulcanizing agent sulfuration and removes beavy metal impurity (Ni, Co.Zn.Cn etc.), liquid after press filtration obtains sulfuration.Under 55-65 ℃ of condition, carry out deep purifying with hydrogen peroxide reagent again, make reducing impurity be transformed into the simple substance element ion and exist in the solution; Flocculated heavy clear 48 hours with Tai-Ace S 150 reagent, press filtration obtains the new liquid of use in electrolysis again.Obtain to reach the Electrolytic Manganese Product of GB (GB3418-82.99.7%Mn) through electrolysis.
Through overtesting, each above-mentioned processing parameter is all influential to improving manganese ore transformation efficiency and minimum raw material consumption etc., wherein, with example five processing condition best, output is the highest, energy consumption is low.The product of gained after the electrolytic solution electrolysis that makes according to above-mentioned embodiment through passivation, is washed, is scalded, air-dry, peels off to get flaked product, and quality meets national standard (GB3418-82,99.7%).
Modified version method for producing electrolytic manganese metal by two-ore method of the present invention belongs to pure hydrometallurgical processes, and industrial production test showed in 2005~2009 years, mature production technology, and advanced technology is reliable, and quality product is high, and especially product contains C, S, and impurity is low.The traditional technology that present method and manganese oxide ore are produced electrolytic manganese compares, and has improved workman's labor condition, and Production Flow Chart is short, is in fact the producing and manufacturing technique of environmental protection and energy saving.Production practice are carried out deep purifying to manganese sulfate solution, removed in the solution reducing impurity impact of electrolytic process is normally produced thereby reach electrolysis, improve the quality of products.
Present method especially is that approach has been created in the development and use of the mine tailing (sulfurous iron ore) of low-grade oxygen deprivation manganese ore and nonferrous metals ore ore dressing.Moreover low product manganese oxide ore and sulfurous iron ore source are extensively, and price is low, so production cost is low, and the manganese metal recovery rate is 65%-67%.
All are above-mentioned to be primary device for carrying out said and the method thereof of this intellecture property, does not set restriction and implements this improved method and device thereof with other form.Those skilled in the art will utilize this important information, foregoing be revised, to realize similar implementation status.But all are based on modification of the present invention or transform new device, belong to the right of reservation.
The above only is preferred embodiment of the present invention, is not to be the restriction of the present invention being made other form, and any those skilled in the art may utilize the technology contents of above-mentioned announcement to be changed or be modified as the equivalent embodiment of equivalent variations.But every technical solution of the present invention content that do not break away from according to any simple modification, equivalent variations and the remodeling that technical spirit of the present invention is done above example, still belongs to the protection domain of technical solution of the present invention.

Claims (1)

1. the method for a modified version method for producing electrolytic manganese metal by two-ore is characterized in that:
Said method comprising the steps of: leaching, purification, deep purifying and electrolysis;
Two kinds of ores of described two ore deposit method electrolytic metal Mns are respectively: Low grade manganese ore and low grade pyrite;
Described Low grade manganese ore is: manganese content is the manganese oxide ore of 15-25%;
Described sulfurous iron ore is: the mine tailing of nonferrous metals ore ore dressing or primary sulfurous iron ore;
The step of described leaching comprises:
Manganese oxide ore take manganese content as 15-25% is raw material, and nonferrous metals ore milltailings sulfurous iron ore is the reductive agent raw material;
Two kinds of ores are ground to granularity 80-130 purpose breeze, mix with anolyte, directly in the sulphuric acid soln of 85-120g/l, be heated to 90-100 ℃; Wherein, according to ratio of weight and number manganese ore powder: troilite powder: the ratio of sulfuric acid is 1:0.30-0.5:0.35-0.50;
Agitation leach 2-4 hour;
The step of described purification comprises:
The oxidation neutralized ex iron: the pulp PH value after leaching with the ammoniacal liquor adjustment is to 4.0-5, by containing Fe in the liquid 2+Amount add manganese ore powder Oxidation of Fe SO 4Generate Fe 2(SO) 3
Adjust pulp PH value to 6-6.5 with ammoniacal liquor again, Fe 2(SO 4) 3Hydrolysis generates Fe(OH) 3Be deposited in the leached mud, ore pulp gets thick manganese sulfate solution through filter pressing;
The sulfuration removing heavy-metal impurities: described thick manganese sulfate solution adds the vulcanizing agent sulfuration and removes beavy metal impurity, liquid after press filtration obtains sulfuration;
The step of described deep purifying comprises:
With the solution after the sulfuration, adopt ammonium persulphate, hydrogen peroxide to make scavenging agent, reducing impurity is removed in oxidation; Making reducing impurity be transformed into the simple substance element ion exists in the solution;
Flocculated heavy clear 24-48 hour with Tai-Ace S 150 reagent again, add selenium 15-20mg/l after the press filtration after ,Obtain the qualified new liquid of use in electrolysis;
The step of described electrolysis comprises:
Solution with the deep purifying step process is crossed is configured to: Mn18-23g/l, (NH 4) 2SO 4100-120g/l, Se30-50g/l, pH value are 7~7.5 fluting liquid.
Electrolysis is carried out in energising, and strength of current raises gradually, switches on after 4-8 hour, and strength of current is raised to the setting operation value;
Electrolysing period is 24 hours;
Described electrolysis procedure control condition is as follows:
Advance tank liquor: Mn35-40 g/L, (NH 4) 2SO 4100-120 g/L PH 6.5-7.0;
Catholyte: Mn15-18 g/L, (NH 4) 2SO 4110-120 g/L PH 6.5-7.5;
Anolyte: Mn15-18 g/L, (NH 4) 2SO 4110-120 g/L H 2SO 438-45g/L;
Cathode current density: 340-380A/m 2Bath voltage: 4.3-4.8V;
Tank liquor temperature: 38-45 ℃;
Electrolysis additive: SeO 2, contain Se 25-40mg/L;
Electrolysing period: 24 hours;
The step of described leaching comprises:
First in leaching vat, inject anolyte, after anolyte has the first agitating vane, do not start stirrer, and continue to inject anolyte, then begin in leaching vat, to throw in manganese ore powder and troilite powder, and add sulfuric acid, open the steam heating ore pulp, when slurry temperature reaches 90 ℃, start the clock;
Detect the Mn amount that contains of leach liquor, after containing the Mn amount and reaching the concentration of setting, leach and finish;
Wherein,
Manganese ore powder: sulfurous iron ore: the sulfuric acid mass ratio is 1:0.3-0.5:0.35-0.5;
Leach 90-100 ℃ of slurry temperature;
Extraction time: the end that feeds intake, ore pulp are warmed up to 90 ℃, and the beginning timing was leached 2~4 hours.
CN2010102057576A 2010-06-22 2010-06-22 Improved device and method for producing electrolytic manganese metal by two-ore method CN101845562B (en)

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