CN103233243B - The production method of electrolytic metal Mn - Google Patents
The production method of electrolytic metal Mn Download PDFInfo
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- CN103233243B CN103233243B CN201310129268.0A CN201310129268A CN103233243B CN 103233243 B CN103233243 B CN 103233243B CN 201310129268 A CN201310129268 A CN 201310129268A CN 103233243 B CN103233243 B CN 103233243B
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Abstract
The invention discloses a kind of production method of electrolytic metal Mn, comprise the steps: that its top feed mouth being transported to the reduction furnace vertically placed after a) manganese oxide powder and coal mixing being dried from up to down moves; B) by coal gas through being arranged on the heating agent gas burner spray combustion below reduction furnace, burning produce high-temperature flue gas in the furnace chamber of reduction furnace, rotate rising; C) the high temperature manganese monoxide after reduction by after cooling through drawing mechanism discharging, obtained manganese monoxide mineral powder; D) manganese monoxide mineral powder and sulfuric acid are carried out leaching combination reaction, obtain rough manganese sulfate solution through solid-liquid separation; E) purification and impurity removal is carried out to described rough manganese sulfate solution, after the manganese sulfate solution after purification is injected electrolyzer electrolysis, obtain Electrolytic Manganese Product.The manganese monoxide mineral powder that the present invention produces can be used as the alternative materials of producing electrolytic metal Mn, solves manganese industry and relies on the raw material of manganese carbonate ore, and significantly can reduce acid consumption and cost.
Description
Technical field
The present invention relates to a kind of production method of electrolytic metal Mn, particularly a kind of take Low grade manganese ore as the method for raw material production electrolytic metal Mn.
Background technology
Electrolytic metal Mn is widely used in the fields such as metallurgy, medical science, electronics, communication.Along with the development of science and technology, the application of electrolytic manganese constantly expands, and market demand year increases about 15%.China's electrolytic manganese annual capacity can reach 800,000 tons, accounts for 80% of Gross World Product.For many years, China's electrolytic manganese major part is used for outlet, the countries such as main exit Japan, Korea S, America and Europe.Electrolytic metal Mn obtains manganese salt with manganese ore through Ore Leaching, then the elemental metals sending electrolytic tank electrolysis to separate out, and the purity of electrolytic manganese is very high, and manganese content is greater than more than 99.7%, thus main aircraft industry, metallurgy and non-ferrous metal metallurgy time use.
Current electrolysis manganese metal is produced and is generally adopted manganese carbonate ore as raw material, there is the problems such as energy consumption is many, production cost is high, environmental pollution is large, at present, manganese carbonate ore resource is fewer and feweri, faces the rare and high cost problem of huge mineral resources with the enterprise by using manganese carbonate ore resource to produce.Reducton Leaching of Pyrolusite technique is the important research content of domestic and international manganese ore processing always, according to the difference of flow process, can be summarized as two large classes: reducing roasting-pickling process and direct reducing leaching method (wet reducing).Direct reducing leaching method, because avoiding high-temperature roasting program, simplifies technique, becomes the important research direction of manganese oxide ore reduction.But due to the demand of large-scale industrial production, direct reducing leaching method still has some limitations, the leaching slag obtained is difficult to process, so reduction roasting method is also subject to the favor of investigator always, and has had new progress.With the development of Iron And Steel Industry, manganese industry is also flourish, and the Technology therefrom extracting manganese in low-grade manganese is also more and more rich and varied, as H
2o
2lixiviation process, oxalic acid infusion process, glucose lixiviation process, rice bran lixiviation process etc.But these methods all exist certain defect, do not obtain actual industrial application.Therefore the development of necessary development of new, efficient, cheap reductive leaching technology, makes full use of for Low grade manganese ore resource and the alternative of electrolytic manganese raw material opens up new technological approaches.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of production method of electrolytic metal Mn, can be raw material with Low grade manganese ore, produces manganese monoxide mineral powder and substitutes the alternative materials of existing manganese carbonate ore as electrolytic metal Mn and electrolytic manganese dioxide.
The present invention solves the problems of the technologies described above the production method that the technical scheme adopted is to provide a kind of electrolytic metal Mn, comprise the steps: its top feed mouth being transported to the reduction furnace vertically placed after a) manganese oxide powder and coal mixing being dried by material loading scrapper conveyor and automatic distributing machine, described manganese oxide powder and coal from up to down move in the reduction tube of reduction furnace; B) by coal gas through being arranged on the heating agent gas burner spray combustion below reduction furnace, burning produce high-temperature flue gas in the furnace chamber of reduction furnace, rotate rising, at burner interval, temperature of combustion controls within the scope of 700 ~ 900 DEG C; C) through the discharging of discharging scrapper conveyor after the high temperature manganese monoxide after reduction is cooled by the cooling water tank of reduction furnace bottom, obtained finished product manganese monoxide mineral powder; D) manganese monoxide mineral powder and sulfuric acid are joined simultaneously leach in chemical combination groove, heat and carry out leaching combination reaction 4-6 hour at 90 ~ 95 DEG C, obtain rough manganese sulfate solution through solid-liquid separation; E) purification and impurity removal is carried out to described rough manganese sulfate solution, the manganese sulfate solution after purification is injected electrolyzer, control cell liquid pH value 7.0 ~ 8.0; Electrolysis obtained Electrolytic Manganese Product after at least 24 hours.
Further, described step a) in manganese oxide powder and coal dry in rotary kiln mixing, described step b) in the tail gas recycle that produces be used for heating rotary kiln.
Further, the number of described heating agent gas burner is multiple, described multiple heating agent gas burner is circumferentially spacedly distributed in the bottom of reduction furnace, described multiple heating agent gas burner sprays coal gas in turn and forms spiral flue gas, the gas injection amount of described multiple heating agent gas burner and the blanking amount of automatic distributing machine proportional.
Further, described heating agent gas burner is connected with producer gas generator, and described heating agent gas burner is rectangular nozzle, and described rectangular nozzle vertically offers rectangular tank, be provided with manual wafer type butterfly valve on rear side of described heating agent gas burner, front side is provided with sphere hard seal butterfly valve.
Further, spiral reduction tube is provided with in described reduction furnace, be provided with spiral cooling pipe in described cooling water tank, the diameter of described spiral reduction tube and spiral cooling pipe is consistent, and the pipe diameter of described spiral reduction tube and spiral cooling pipe is 200 ~ 400mm.
Further, in described step a), the weight percentage of the manganese of manganese oxide powder is 16% ~ 22%, and it is 0% ~ 10% that described manganese oxide powder and coal mix the percent water after drying.
Further, it is the powder mix of 250 ~ 350mm that described manganese oxide powder and coal first form granularity through jaw crusher, then after impact breaker formation granularity is the powder mix of 100 ~ 250mm, sends rotary kiln to; In described rotary kiln, powder mix out becomes granularity to be that the powder mix of 20 ~ 100mm is transported in reduction furnace through the bar screen of intermediate bin opening for feed, the static grizzly of discharge port and the Vibration Screen form slection on automatic distributing machine.
Further, in described step e), secondary-cleaned removal of impurities is carried out to described rough manganese sulfate solution, in first time scavenging process, under whipped state, first add dimethylamino dithiocarbonic acid sodium (SDD) or barium sulphide (BaS) carries out removal of impurities, then add Tai-Ace S 150 and purify; Secondary-cleaned first adds the deep impurity-removing medicament of 10-30%, then drops into ammonium sulfide and dezincify, and reacts after 1 ~ 2 hour, checks and mix up pH value 6.0 ~ 8.0, forwards in standing groove and leave standstill after press filtration; The deep impurity-removing medicament of residual content is added in described standing groove.
Further, drip gac at chute in described secondary-cleaned liquid pressure-filtering process, in standing groove, add remaining deep impurity-removing medicament.
Further, described deep impurity-removing medicament is the mixture of organic medicament and inorganic medicament, makes the beavy metal impurity content in solution be reduced to 0-1mg/l; Described organic medicament is one or more in Trisodium Citrate, citric acid tricalcium, sodium oxalate, potassium oxalate, 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid salt; Described inorganic medicament is two or more in sodium sulphite, magnesium sulfide, ferrous sulfate, Tai-Ace S 150.
The present invention contrasts prior art following beneficial effect: the production method of electrolytic metal Mn provided by the invention, with Low grade manganese ore and raw coal for main raw material, take full advantage of existing ore resources, realize manganese oxide ore reduction at 700-900 DEG C and can reach energy-saving and cost-reducing object, the manganese monoxide mineral powder produced, as the alternative materials of producing electrolytic metal Mn, solves manganese industry on the one hand and relies on the raw material of manganese carbonate ore; The acid consumption of secondly often producing 1 ton of electrolytic manganese in original production technology can reduce to less than 0.8 ton by about original 3 tons; 3rd buying and the transportation cost reducing manganese carbonate ore, simplifies removal of impurities flow process simultaneously, significantly reduces the production cost of electrolytic metal Mn.
Accompanying drawing explanation
Fig. 1 is the production equipment structural representation of manganese monoxide mineral powder of the present invention;
Fig. 2 is the production technological process of manganese monoxide mineral powder in the embodiment of the present invention;
Fig. 3 is the production technological process of electrolytic metal Mn in the embodiment of the present invention.
In figure:
Embodiment
Below in conjunction with drawings and Examples, the invention will be further described.
Fig. 1 is the production equipment structural representation of manganese monoxide mineral powder of the present invention.
Refer to Fig. 1, the production equipment of manganese monoxide mineral powder provided by the invention comprises the reduction furnace 8 vertically placed, the top of described reduction furnace 8 arranges automatic distributing machine 9 and material loading scrapper conveyor 10, the bottom of described reduction furnace 8 is provided with heating agent gas burner 6 and burner blower 2, and the bottom of described reduction furnace 8 is provided with cooling water tank 3 and discharging scrapper conveyor 1.The number of described reduction furnace 8 can be multiple, and described multiple reduction furnace 8 is arranged side by side.
The production equipment of manganese monoxide mineral powder provided by the invention, described material loading scrapper conveyor 10 is connected with the discharge port of intermediate bin 13 by the first chapelet 12, and the opening for feed of described intermediate bin 13 is connected with rotary kiln 16 by the second chapelet 14; The opening for feed of described intermediate bin 13 arranges bar screen and tentatively sieves filtration to powder mix, and rod gap is generally at more than 100mm; Discharge port arranges static grizzly powder mix to carry out second time and sieves filtration, and the size of mesh of static grizzly is preferably less than the rod gap of bar screen; Described automatic distributing machine 9 is arranged vibratory screening apparatus and carry out last screening filtration to the powder mix entering reduction furnace 8, the size of mesh of vibratory screening apparatus is preferably less than 100mm.Described rotary kiln 16 can arrange centrifugal induced draught fan 17, and be connected with gravitational dust collection type chimney 20.
The production equipment of above-mentioned manganese monoxide mineral powder, described heating agent gas burner 6 is connected with producer gas generator 15, described heating agent gas burner 6 is preferably rectangular nozzle, described rectangular nozzle vertically offers rectangular tank, be provided with manual wafer type butterfly valve 5 on rear side of described heating agent gas burner 6, front side is provided with sphere hard seal butterfly valve 7; The number of described heating agent gas burner 6 is multiple, and described multiple heating agent gas burner 6 is circumferentially spacedly distributed in the bottom of reduction furnace 8.
The production equipment of above-mentioned manganese monoxide mineral powder, wherein, spiral reduction tube is provided with in described reduction furnace 8, spiral cooling pipe is provided with in described cooling water tank 3, the screw diameter of described spiral reduction tube and spiral cooling pipe, pitch and pipe diameter are preferably consistent, the screw diameter of described spiral reduction tube and spiral cooling pipe is preferably 300 ~ 500mm, pitch is preferably 300 ~ 400mm, reduction tube is made by refractory materials, bore 200 ~ 400mm, preferably, diameter is about 300mm.Reduction tube is made by refractory materials.In order to ensure cooling performance, the diameter of spiral cooling pipe also can be allowed slightly larger than the diameter of spiral reduction tube.
Fig. 2 is the production technological process of manganese monoxide mineral powder in the embodiment of the present invention.
Refer to Fig. 2, the production method of electrolytic metal Mn provided by the invention, adopt method of reducing to produce breeze level manganese monoxide raw material, detailed process is as follows:
First select the weight percentage of manganese be 16% ~ 22% Low grade manganese ore powder; It is the powder mix of 250 ~ 350mm that manganese oxide powder and coal first can form granularity through jaw crusher, then after impact breaker formation granularity is the powder mix of 100 ~ 250mm, sends rotary kiln 16 drying and forewarm to and mixes; In described rotary kiln 16, the percent water of manganese oxide powder out and coal powder mix is preferably 0% ~ 10%, mixes dried powder mix and becomes granularity to be its top feed mouth that the powder mix material loading scrapper conveyor 10 of 20 ~ 100mm is transported to the reduction furnace 8 that each is vertically placed respectively through the bar screen of intermediate bin 13 opening for feed, the static grizzly of discharge port and the Vibration Screen form slection on automatic distributing machine 9.Manganese oxide powder and coal due to the effect of gravity, proper motion from top to bottom in reduction tube.
Secondly, after producer gas generator 15 is processed, obtain coal gas by feed coal, the high-temperature fuel gas that this gas burning system produces, through being arranged on low pressure eddy flow heating gas burner 6 spray combustion of reduction furnace bottom, for the reduction of manganese oxide powder provides outside heat.The high-temperature flue gas that burning produces rotates rising in the furnace chamber of reduction furnace, and manganese oxide powder is naturally descending from furnace roof.Flue gas/manganese oxide powder, in antikinesis process, completes heat exchanging process fully, and thermo-efficiency is high.At burner interval, temperature of combustion controls within the scope of 700 ~ 900 DEG C, and maximum combustion temperature more than 1000 DEG C, must not block reduction tube to avoid the generation of crossing reduction and melting and reducing of manganese oxide ore; Preferably, the tail gas that this process produces is recyclable for heating rotary kiln 16, comes pre-heating drying Manganse Dioxide breeze and coal, energy efficient.
Improve reduction efficiency to form spiral flue gas, be unlikely to again reduction and melting and reducing occurred, conventional circular high-velocity nozzle or the flat flame burner brick of hydraucone shape all can not take into account both very well.In the present invention, heating agent gas burner 6 is preferably rectangular nozzle, and described rectangular nozzle vertically offers rectangular tank and forms more uniform flame.The number of described heating agent gas burner 6 is multiple, described multiple heating agent gas burner 6 is circumferentially spacedly distributed in the bottom of reduction furnace 8, described multiple heating agent gas burner 6 sprays coal gas in turn thus forms spiral flue gas, the gas injection amount of described multiple heating agent gas burner 6 and the blanking amount of automatic distributing machine 9 preferably proportional.
Finally, through preheating and the reduction of reduction furnace, the MnO in manganese oxide ore
2fully be reduced into MnO, for preventing high temperature oxidation manganese ore to be again oxidized, the high temperature oxidation manganese ore after reduction directly enters the cooling water tank 3 be connected with reduction furnace and cools, and cooling water tank 3 is arranged on reduction furnace bottom, cooled manganese oxide ore, through discharging scrapper conveyor 1 discharging, obtains finished product manganese monoxide mineral powder; Discharging scrapper conveyor 1 just realizes Automatic continuous discharging to the spiral cooling pipe in cooling water tank 3; In the present embodiment, also can be provided with airtight hopper below spiral cooling pipe and carry out manual discharging.
Reduction coal and manganese oxide powder are in the process that reduction tube is descending, and through heat absorption and a series of reduction reactions analysing heat, fixed carbon is wherein the MnO in manganese oxide ore
2fully be reduced into MnO.
Main reaction is as follows:
2C+O
2=2CO
C+O
2=CO
2
2CO+O
2=2CO
2
C+MnO
2=CO+MnO
CO+MnO
2=MnO+CO
2
CH4+2MnO
2=CO
2+2H
2O+2MnO
Next, please refer to Fig. 3, manganese monoxide mineral powder and sulfuric acid are carried out leaching and close reaction, main chemical reactions is as follows:
MnO+H
2SO
4=MnSO
4+H
2O
The ore pulp leached after chemical combination obtains rough manganese sulfate solution through solid-liquid separation.
Rough manganese sulfate solution becomes qualified manganese sulfate solution after purification and impurity removal.In rough manganese sulfate solution, containing heavy metal and the impurity such as calcium, magnesium such as copper, lead, nickel, zinc, therefore need to carry out purification and impurity removal.At one section of cleaning section, add a certain amount of SDD and barium sulphide (BaS) under proper temperature, control the condition such as reaction times and PH, make the heavy metal ion such as nickel form sulfide precipitation, sulfide precipitation is removed with solution separating after press filtration.The scavenging solution of one section of press filtration out carries out secondary-cleaned afterwards, adds deep purifying medicament, except beavy metal impurities such as dezincifies, improves manganese sulfate solution quality further.Manganese sulfate solution after deep purifying, flow through the dynamic deliming of chute of long distance, magnesium, then deliver to standing groove and leave standstill, the contamination precipitation such as calcium, magnesium is removed by ageing of solution, solution after leaving standstill pumps into chamber-type press filter and filters, and obtains qualified manganese sulfate solution.
Qualified manganese sulfate solution, after electrolytic tank electrolysis, is peeled off through passivation, flushing, oven dry and obtains Electrolytic Manganese Product after packaging.At electrowinning process, electrolysis of solutions temperature controls at 40 ~ 44 DEG C, and electrolytic process adds tin anhydride and makes anti-oxidant selenium, strict implement groove manganese, tank liquor PH, and the electrolysis production condition such as current/voltage, thus finally obtains the Electrolytic Manganese Product of high-quality.After manganese plate goes out groove through passivation, soaking flushing, oven dry, peel off, weigh packaging etc. process after obtain finished product.Be described with regard to embodiment below:
1, liquid processed
(1) chemical combination is leached
Manganese monoxide mineral powder is joined and leaches in chemical combination groove, by concentration be 98% sulfuric acid add water and be mixed with the dilution heat of sulfuric acid of 100g/L, allocate sulfuric acid into by the mol ratio 1:1 of breeze and sulfuric acid simultaneously, redox reaction 4-6 hour is there is at the temperature of 90 DEG C, for ensureing the temperature leaching combination reaction, adopt groove internal steam pipe direct heating.
Heating leaching process adds moderate amount of sulfuric acid ammonium, makes ammonium sulfate concentrations reach solution index requirement, i.e. 100 ~ 120g/l.
After Leaching reaction terminates, whether the ferrous iron in qualitative detection solution is qualified, and time defective, qualitative detection color is dark green, and time qualified, qualitative detection color is khaki color.If ferrous iron is qualitative defective, then regulator solution pH value to 5.5 ~ 6.5 and add appropriate manganese oxide or hydrogen peroxide except ferrous iron, until ferrous iron qualitative detection is qualified.
Except ferrous iron qualified after, ammoniacal liquor is added toward chemical combination groove, regulate leach liquor pH value between 6.6 ~ 7.0, whether the ferric iron of qualitative detection solution is qualified subsequently, time defective, extract layer is rust, time qualified, extract layer is transparent whites, if ferric iron is defective, then adds appropriate hydrogen peroxide and adjusts ammoniacal liquor to remove ferric iron until qualitative qualified.
(2) primary purification
Leach qualified solution to forward purification tank to through press filtration and carry out primary purification, first add SDD and BaS and carry out conventional removal of impurities, add Tai-Ace S 150 again to purify, the metallic impurity such as nickel precipitate with forms such as sulfide, and solution transforms two sections of purification tanks and carries out secondary-cleaned after press filtration.
Under whipped state, in one section of purification tank, add SDD need react certain hour, in qualitative detection solution nickel qualified after add Tai-Ace S 150 again, enter two sections of purifications through press filtration after sufficient reacting, filter residue delivers to slag field.
Before adding SDD, the pH value of solution in groove must be regulated and touch the mark, make pH value 6.0 ~ 7.0, otherwise impurity-eliminating effect difference and cause SDD to waste.In addition, pressure-filtering process stirs and can not stop, and should be released completely by solution in groove as far as possible.
(3) two sections of purifications
Secondary-cleaned first adds a part of deep impurity-removing medicament, as the deep impurity-removing medicament of 10-30% predetermined amount, then adds specified amount ammonium sulfide and dezincifies, react after 1 hour, check and mix up pH value 6.0 ~ 8.0, forwards in standing groove and leave standstill after press filtration.The organic medicament of the reasonably combined use of described deep impurity-removing medicament and inorganic medicament, make the difficult beavy metal impurity content removed in solution be reduced to below 1mg/l; Described organic medicament is one or more in Trisodium Citrate, citric acid tricalcium, sodium oxalate, potassium oxalate, 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid salt; Described inorganic medicament is two or more in sodium sulphite, magnesium sulfide, ferrous sulfate, Tai-Ace S 150.In the present embodiment, composition and the weight proportion thereof of described deep impurity-removing medicament are respectively: citric acid tricalcium 15 ~ 30, potassium oxalate 10 ~ 20,1-Hydroxy Ethylidene-1,1-Diphosphonic Acid salt 5 ~ 10, magnesium sulfide 5 ~ 15, ferrous sulfate 5 ~ 15.
Utilize organic medicament and heavy metal ion to form the characteristic of inner complex, under the prerequisite of not serious damage bivalent manganese concentration, the beavy metal impurities such as zinc in manganese sulfate solution are carried out trace and control.
Drip gac at chute in secondary-cleaned liquid pressure-filtering process, add remaining deep impurity-removing medicament at standing groove.
Pressing filtering liquid enters standing groove, detects and leaves standstill manganous sulfate, ammonium sulphate content and pH value in groove solution, whether beavy metal impurity content is qualified, if it is defective to find to leave standstill solution in groove, need returns two sections of purifications and do respective handling until qualified.
Solution left standstill supernatant is after 24 hours, and after pressure filter press filtration, the direct pump of manganese sulfate solution carries out electrolysis production to electrolyzer.
2, electrolysis
Qualified manganese sulfate solution is injected electrolyzer, and logical direct current carries out electrolysis in solution under certain condition, and oxidizing reaction and reduction reaction occur respectively for positive plate and negative plate, negative plate obtains manganese metal, its reaction formula is:
Mn
2++2e=Mn↓
2H++2e=H
2↑
The specification of quality of manganese sulfate electrolyte is:
MnSO
4content is up to standard;
Fe, Ni qualitative detection is without vestige;
Heavy metal detection by quantitative is qualified;
The electrolytic metal Mn specification of quality that electrolysis obtains is as follows:
S≤0.05%；
(1) electrolytic process
Check electrolyzer and electrolytic anode plate, negative plate, after confirming to meet electrolysis requirement, start to fill with liquid toward electrolyzer, prepare a small amount of tin anhydride simultaneously and do end selenium use, regulated and controled tank liquor pH value 7.0 ~ 8.0, facility checkout and index regulation and control all qualified after, electrolysis is carried out in energising.Start process controls suitable bath voltage, slowly motor current, guarantees groove condition process stabilizing.
Production method provided by the invention is in electrolysis production manganese metal process, and tank liquor pH value takes high level to control, and electrolysis production process tank liquor PH controls all the time more than 7.5, and this and manganese carbonate ore method electrolysis production have bigger difference.Medicament in new liquid and manganese sulfate solution can improve cell liquid height pH value control condition, solves that electrolytic process pH value is too high causes that manganese plate turns black, the problems such as manganese do not gone up by manganese plate, can ensure that on manganese plate, manganese is firm, surface uniform is neat under middle high pH value condition.
Groove face liquid discharging tube position is exchanged in electrolytic process timing, is conducive to tank liquor manganese and is uniformly distributed, and reducing local, manganese is high causes manganese on plate bursting and manganese plate uneven.
(2) groove is gone out
The manganese sulfate solution electrolysis production cycle reaches 24 hours and just can go out groove.First fall electric current when going out groove, block little new flow quantity, extract manganese plate out by one-in-and-one-out principle and change clean negative plate, the manganese plate of extraction is put into passivation in passivation bucket immediately, avoids the oxidation by air of manganese metal.
3, finished product preparation
(1) passivation and immersion
The oxygen run into air extracted out by manganese plate in electrolyzer can generate manganese oxide at surface oxidation, affects quality product, should be put in potassium bichromate solution by manganese plate in time and carry out passivation, and passivation time general control is at 1-3 minute, and about 2 minutes best.The manganese plate that passivation is good hangs out in soaking compartment and soaks about 4 minutes, hangs out to deliver to rinse post.
(2) rinse and dry
Soaked manganese plate is placed on rinsing area, rinses manganese plate with water blast gun, rinses the spot etc. that copper bar and manganese plate face remain well rear standing half a minute, treats to dry in the less pusher of manganese plate face water droplet to drying baker.During oven dry, middle position in case shifted onto by manganese plate, and control the temperature inside the box at 90 ~ 100 DEG C, drying time about 15 minutes, is as the criterion with the face drying of manganese plate.The manganese plate of having dried will cool in advance before stripping, avoids scalding when peeling off product.
(3) peel off and pack
Before the manganese plate cooled is hung stripping machine, straight manganese plate of holding is put stripping machine into and is peeled off, and the manganese sheet stripped down drops on platform, is shoveled in funnel by its bunch.
When manganese sheet is more in funnel, be enclosed within funnel end opening with packing bag, pull open funnel lock, by predetermined weight packaging, the manganese product of gained and finished product.
Although the present invention discloses as above with preferred embodiment; so itself and be not used to limit the present invention, any those skilled in the art, without departing from the spirit and scope of the present invention; when doing a little amendment and perfect, therefore protection scope of the present invention is when being as the criterion of defining with claims.
Claims (8)
1. a production method for electrolytic metal Mn, is characterized in that, comprises the steps:
A) be transported to its top feed mouth of the reduction furnace (8) vertically placed after manganese oxide powder and coal mixing being dried by material loading scrapper conveyor (10) and automatic distributing machine (9), described manganese oxide powder and coal from up to down move in the reduction tube of reduction furnace (8);
B) by coal gas through be arranged on reduction furnace (8) below heating agent gas burner (6) spray combustion, the high-temperature flue gas that burning produces rotates rising in the furnace chamber of reduction furnace (8), at burner interval, temperature of combustion controls within the scope of 700 ~ 900 DEG C; The number of described heating agent gas burner (6) is multiple, described multiple heating agent gas burner (6) is circumferentially spacedly distributed in the bottom of reduction furnace (8), described multiple heating agent gas burner (6) sprays coal gas in turn, the gas injection amount of described multiple heating agent gas burner (6) and the blanking amount of automatic distributing machine (9) proportional; Described heating agent gas burner (6) is connected with producer gas generator (15), described heating agent gas burner (6) is rectangular nozzle, described rectangular nozzle vertically offers rectangular tank, described heating agent gas burner (6) rear side is provided with manual wafer type butterfly valve (5), and front side is provided with sphere hard seal butterfly valve (7);
C) through discharging scrapper conveyor (1) discharging after the high temperature manganese monoxide after reduction is cooled by the cooling water tank (3) of reduction furnace bottom, obtained finished product manganese monoxide mineral powder;
D) manganese monoxide mineral powder and sulfuric acid are joined simultaneously leach in chemical combination groove, heat and carry out leaching combination reaction 4-6 hour at 90 ~ 95 DEG C, obtain rough manganese sulfate solution through solid-liquid separation;
E) purification and impurity removal is carried out to described rough manganese sulfate solution, the manganese sulfate solution after purification is injected electrolyzer, control cell liquid pH value 7.0 ~ 8.0; Electrolysis obtained Electrolytic Manganese Product after at least 24 hours.
2. the production method of electrolytic metal Mn according to claim 1, it is characterized in that, described step a) in manganese oxide powder and coal dry in rotary kiln (16) mixing, described step b) in the tail gas recycle that produces be used for heating rotary kiln (16).
3. the production method of electrolytic metal Mn as claimed in claim 1, it is characterized in that, described reduction furnace is provided with spiral reduction tube in (8), described cooling water tank is provided with spiral cooling pipe in (3), the diameter of described spiral reduction tube and spiral cooling pipe is consistent, and the pipe diameter of described spiral reduction tube and spiral cooling pipe is 200 ~ 400mm.
4. the production method of electrolytic metal Mn according to claim 1, it is characterized in that, described step a) in the weight percentage of manganese of manganese oxide powder be 16% ~ 22%, described manganese oxide powder and coal mixing dry after percent water be 0% ~ 10%.
5. the production method of electrolytic metal Mn according to claim 1, it is characterized in that, it is the powder mix of 250 ~ 350mm that described manganese oxide powder and coal first form granularity through jaw crusher, then after impact breaker formation granularity is the powder mix of 100 ~ 250mm, sends rotary kiln (16) to; In described rotary kiln (16), powder mix out becomes granularity to be that the powder mix of 20 ~ 100mm is transported in reduction furnace (8) through the bar screen of intermediate bin (13) opening for feed, the static grizzly of discharge port and the Vibration Screen form slection on automatic distributing machine (9).
6. the production method of electrolytic metal Mn according to claim 1, it is characterized in that, described step e) in secondary-cleaned removal of impurities is carried out to described rough manganese sulfate solution, in first time scavenging process, under whipped state, first add dimethylamino dithiocarbonic acid sodium (SDD) or barium sulphide (BaS) carries out removal of impurities, then add Tai-Ace S 150 and purify; Secondary-cleaned first adds the deep impurity-removing medicament of 10-30%, then drops into ammonium sulfide and dezincify, and reacts after 1 ~ 2 hour, checks and mix up pH value 6.0 ~ 8.0, forwards in standing groove and leave standstill after press filtration; The deep impurity-removing medicament of residual content is added in described standing groove.
7. the production method of electrolytic metal Mn according to claim 6, is characterized in that, drips gac, add remaining deep impurity-removing medicament in standing groove in described secondary-cleaned liquid pressure-filtering process at chute.
8. the production method of electrolytic metal Mn according to claim 6, is characterized in that, described deep impurity-removing medicament is the mixture of organic medicament and inorganic medicament, makes the beavy metal impurity content in solution be reduced to 0-1mg/l; Described organic medicament is one or more in Trisodium Citrate, citric acid tricalcium, sodium oxalate, potassium oxalate, 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid salt; Described inorganic medicament is two or more in sodium sulphite, magnesium sulfide, ferrous sulfate, Tai-Ace S 150.
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| CN104404244A (en) * | 2014-12-15 | 2015-03-11 | 中信大锰矿业有限责任公司大新锰矿分公司 | Method for producing electrolytic manganese metal with manganese oxide ore |
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