CN104789755B - A kind of use high sulphur manganese mine clean and effective produces the method and device of manganese metal - Google Patents
A kind of use high sulphur manganese mine clean and effective produces the method and device of manganese metal Download PDFInfo
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Abstract
The invention discloses a kind of use high sulphur manganese mine clean and effective produces the method and device of manganese metal, by high sulphur manganese mine, manganese oxide mineral, lignin additive in mass ratio 1:0.1～0.8：0.01～0.8 mix homogeneously；Mixed material is continuously added to from electrical heating continuous loading/unloading type shaft furnace top, material, through preheating section, then carries out roasting in the shaft furnace thermal treatment zone, and sintering temperature is 400～700 DEG C, the furnace zone time of staying is 30～150min, and calcining is after shaft furnace cooling section by bottom continuous discharge；By calcining at 40～90 DEG C the sulphuric acid leaching 5～60min with 0.5～1.0mol/L, and leaching process to control the solid mass ratio of liquid be 3～8:1, after leaching, solid-liquid separation obtains leachate；After leachate is purified, electrolysis can get electrolytic manganese metal.The method is capable of the efficient utilization of high sulphur manganese mine, and can significantly reduce sintering temperature, and roasting process no sulfur dioxide flue gas are discharged, and has good energy-saving and emission-reduction effect, and the clean and effective of achievable high sulphur manganese mine utilizes.
Description
Technical field
The present invention relates to metallurgical technology field, it is more particularly to the side that a kind of use high sulphur manganese mine clean and effective produces manganese metal
Method and device.
Background technology
The basic characteristics of China's manganese resource are " lean, thin, miscellaneous, thin ", manganese ore grade averagely only 21.4%, big containing manganese
Manganese oxide ore in 30% and containing manganese be more than 20% manganese carbonate ore resource reserve very rare, recoverable amount is less than 20,000,000
Ton, total resources recoverable amount is less than 500,000,000 tons.With the increasingly minimizing of manganese carbonate ore and high-grade manganese oxide ore resource, low-grade
Manganese oxide ore and the focus being increasingly becoming research using technology of other complicated manganese-bearing minerals.
China has substantial amounts of high sulphur manganese mine stone, and its main occurrence form is high sulphur manganese mine, and gangue mineral is mainly sulfur ferrum
Ore deposit, lead-zinc sulfide ore etc..If reclaimed to manganese Metal using direct acidleach method, high sulphur manganese mine is met acid and can be discharged in a large number
Hydrogen sulfide gas, serious environment pollution；And manganese grade is less than 18% it is difficult to direct effectively utilizes in mineral.Many researchs
Show, the purpose of rich manganese desulfurization can be reached for high sulphur manganese mine using rotary kiln oxidizing roasting.Changsha Mining ＆ Metallurgy Inst etc. is single
Position once carried out industrial utilization exploration using rotary kiln oxidizing roasting sulfur removal technology to high sulphur manganese mine, through 1100～1150 DEG C of rotary kiln
Product (Ding Kairu, the high sulphur manganese mine industrial utilization research gratifying one-tenth of acquirement that sulfur content is 1% about can be obtained after oxidizing roasting
Really, metal mine, 1978,5：81；Mao Jufan, the research of high sulphur manganese mine desulfurization with roasting technique technique in rotary kiln, Wuhan building materials
Institute's journal, 1985,1:43-54).Wuhan University Of Technology's Peng Zhi heavily fortified point etc. adopts GTO method desulfurization, also achieves more satisfactory desulfurization
Effect, desulfurization degree reach 91.88% (Peng Zhijian, Chen Tiejun, Peng Feng, the experimental study of high sulphur manganese mine desulfurization, nation manganese industry, 2003,
21(4)：29-32；Peng Zhijian, Chen Tiejun, Wang Changan etc., the industrially desulfurized test of the primary manganese ore of Manaoshan half, nation manganese industry,
2005,23 (4)：23-26)；But a large amount of low-concentration sulfur dioxide stack gases producing during rotary kiln baking are difficult to antacid,
Easily to environment.Additionally, the unit such as Taojiang, Hunan manganese ore and institute of microbiology of the Chinese Academy of Sciences once adopted ferrous oxide sulfur
Bacillus has carried out the leaching test of high sulphur manganese mine, achieves preferable manganese leaching effect, but this technology has cycle length, biota
The big grade affected by environment that falls is not enough, limits its commercial Application (Mao Jufan, Tong Qiru, Qiu Wenfang etc., bioleaching high sulphur manganese mine
And the test of manganese spar, microorganism journal, 1979,19 (2)：166-174；Taojiang, Hunan manganese ore antibacterial soaks manganese cooperative groups, with Asia
The pilot-plant test that iron-oxidizing bacterium leaches high sulphur manganese mine and produces electrolytic manganese dioxide, metal mine, 1978,6:43-49).
Above-mentioned technological invention, the technology especially for some low-grade high sulphur manganese mines also has environmental pollution, one-tenth
The problems of the aspect such as this is higher, efficiency is low.Therefore, a kind of Novel low-consumption, low stain, the high-sulfur manganese of low cost are developed
Ore deposit recovery technology and device, are of great practical significance to the sustainable development promoting China's manganese industry.
Content of the invention
(1) technical problem to be solved
The technical problem to be solved in the present invention be how low energy consumption, low stain, low cost by high sulphur manganese mine reclaim gold
Belong to manganese, and provide a kind of use high sulphur manganese mine clean and effective to produce the method and device of manganese metal.
(2) technical scheme
In order to solve above-mentioned technical problem, the invention provides a kind of use high sulphur manganese mine clean and effective produces the side of manganese metal
Method, the method comprises the following steps：
Step one：By high sulphur manganese mine, manganese oxide mineral, lignin additive in mass ratio 1:0.1～0.8：0.01～0.8
Mix homogeneously；
Step 2：The mixed material that step one is obtained is added continuously to shaft furnace top, enters material in preheating zone first
Row preheating, then carries out roasting in the thermal treatment zone, and sintering temperature is 400～700 DEG C, and roasting time is 30～150min, will obtain
Calcining cooled down in cooling zone, by cooling calcining from shaft furnace bottom continuous discharge；
Step 3：The calcining that step 2 is obtained at 40～90 DEG C with the sulphuric acid leaching 5 of 0.5～1.0mol/L～
60min, it is 3～8 that leaching process controls the solid mass ratio of liquid:1, add a certain amount of H after leaching2O2Or MnO2Breeze Oxidation of Fe2+,
Stirring oxidation 0.5～1h, is subsequently added ammonia and is neutralized to pH 6.2-6.8 except ferrum, addition 0.1～0.5g/L Sodium Dimethyldithiocarbamate are except a huge sum of money
Belong to, solid-liquid separation is purified leachate；
Step 4：The purification leachate that step 3 is obtained, in catholyte：(NH4)2SO4, its concentration：90～110g/L,
pH：7.0～7.2,38～44 DEG C of temperature, SeO2In terms of Se：0.03～0.04g/L, cathode-current density：350～400A/m2, sun
Electrode current density：600～700A/m2, tank voltage：It is electrolysed under the conditions of 4.2～4.6V, prepared manganese metal.
Preferably, described high sulphur manganese mine main component is Manganese monosulfide., including troilite, lead-zinc sulfide ore；Described height
Alabandite contains manganese 8～30%, sulfur-bearing 2～25%.
Preferably, described manganese oxide mineral include pyrolusite, psilomelane, hausmannite, braunite, electrolytic manganese anode mud,
Oceanic multi-metal manganese nodule or useless manganese oxide catalyst etc..
Preferably, described lignin additive is the evaporation of soda processes, sulfate process or sulphite process black liquid
Concentrate, or extract one of the lignin obtaining, lignosulfonates or lignin-sulphonate or several from black liquid
Kind.
Preferably, described lignosulfonates are calcium lignosulfonate, sodium lignin sulfonate, lignin sulfonic acid potassium, wood
One or more of quality sulfonic acid magnesium, ammonium lignosulphonate.
Present invention also offers produce the device of manganese metal with high sulphur manganese mine clean and effective, described device is electrical heating continuous
Loading/unloading type shaft furnace, this shaft furnace include feed auger 1, feeding warehouse 2, boiler tube 3, support 4, heating mantle 5, heating furnace silk 6,
The portions such as coolant jacket 7, discharging spiral propeller 8, product storehouse 9, flue gas recovery device 10, pre- hot jacket 11, circulating pump 12, base 13
Part, feed auger 1 is fixed on the top of boiler tube 3, and support 4 is directly connected with base 13 with discharging spiral propeller 8, stove
Pipe 3 top and bottom are separately fixed on support 4 and discharging spiral propeller 8, and heating mantle 5 is fixed in the middle part of boiler tube 3, pre- hot jacket
11 and coolant jacket 7 be individually fixed in above heating mantle 5 on boiler tube 3 and following, pre- hot jacket is connected using circulating pump 12 and pipeline
11 and coolant jacket 7, flue gas recovery device 10 is connected to the top of boiler tube 3 by heat-resisting pipeline.Each part connects as shown in Figure 1.
Preferably, described boiler tube is divided into feed zone, preheating section, bringing-up section, cooling section and discharging section 5 part；Bringing-up section
Using the heating of external-heat power supply.
Preferably, in described cooling section, preheating section is transferred heat to using conduction oil.
Preferably, described conduction oil includes alkyl benzene-type, alkylnaphthalene type, alkyl biphenyl type, biphenyl and Biphenyl Ether eutectic
Mixture type or alkyl biphenyl ether type synthesis conduction oil or mineral oil.
Preferably, described alkyl benzene-type conduction oil is benzenoid form conduction oil.
(3) beneficial effect
High sulphur manganese mine and manganese oxide, lignin additive are carried out baking mixed by the present invention, manganese mineral are changed into solvable
In sour MnO and MnSO4It is achieved that the efficient utilization of high sulphur manganese mine resource.This method sintering temperature is only 400～700 DEG C, not only
Energy consumption is low, and under this sintering temperature, the most ore deposit phase in Ore will not melt, it is to avoid the caking of pyrolytic semlting is existing
As, calcining is not required to pulverize again and can leach under the Low acid of 0.5～1.0mol/L sulphuric acid, save acid consumption, reduce ferrum, aluminum,
The leaching of the impurity elements such as lead, reduces the consumption of follow-up neutralization precipitation agent.
The present invention carries out roasting using novel electric heating continuous feeding/discharging type shaft furnace device, and the roasting of achievable serialization is made
Industry, roasting efficiency high, energy consumption is low, and roasting process does not have the pollution gas such as sulfur dioxide to produce.This device adopts conduction oil pair
Calcining is cooled down, and conducts heat to feed, preheating material, on the one hand can avoid reoxidizing of the material such as MnO in discharging,
On the other hand then using the high temperature of conduction oil, raw material can be carried out predrying, reduce the consumption of heat.
Reduction process of the present invention adds appropriate lignin additive, on the one hand has dispersed mineral granule, avoids calcining
The effect of caking, is conducive to improving mobility and the leaching effect of mineral grain；Another aspect has prevents sulfur dioxide from escaping,
Reduce the effect of sintering temperature, economical and environmentally friendly remarkable benefit.
In sum, the present invention passes through simple process and device, in a mild condition it is achieved that environmental protection, low cost, efficiently
Rate extracts manganese from high sulphur manganese mine, and simultaneously new for the high-efficiency comprehensive utilization offer of Liginon Resource and Low grade manganese ore
Approach.
Brief description
In order to be illustrated more clearly that the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
Have technology description in required use accompanying drawing be briefly described it should be apparent that, drawings in the following description be only this
Some embodiments of invention, for those of ordinary skill in the art, on the premise of not paying creative work, acceptable
Other accompanying drawings are obtained according to these accompanying drawings.
Fig. 1 is the structural representation of electrical heating continuous loading/unloading type shaft furnace of the present invention；
Fig. 2 is the manganese metal XRD spectrum of embodiment 4 electrolytic preparation；
Fig. 3 is the manganese metal SEM picture of embodiment 4 electrolytic preparation；
Reference：1st, feed auger, 2, feeding warehouse, 3, boiler tube, 4, support, 5, heating mantle, 6, heating furnace silk,
7th, coolant jacket, 8, discharging spiral propeller, 9, product storehouse, 10, flue gas recovery device, 11, pre- hot jacket, 12, circulating pump, 13, bottom
Seat.
Specific embodiment
With reference to the accompanying drawings and examples embodiments of the present invention are described in further detail.Following examples are used for
The present invention is described, but can not be used for limiting the scope of the present invention.
The present invention is by the additive of high sulphur manganese mine, manganese oxide mineral and lignin in mass ratio 1:0.1～0.8：0.01～
0.4 mix homogeneously；
Referring to Fig. 1, by the mixed material obtaining from electrical heating continuous loading/unloading type shaft furnace top by the screw rod propulsion that feeds
Device 1 is continuously added to, and material first passes around pre- hot jacket 11, then carries out roasting in the boiler tube thermal treatment zone, sintering temperature be 400～
700 DEG C, the furnace zone time of staying is 30～150min, and calcining is by bottom discharge screw propeller 8 continuous discharge；Calcining is in cooling
Cooled down using conduction oil in set 7, preheating section and cooling section are circulated heat-shift using circulating pump 12；
By the calcining obtaining at 40～90 DEG C the sulphuric acid leaching 5～60min with 0.5～1.0mol/L, and leach
The solid mass ratio of process control liquid is 3～8:1, add a certain amount of H after leaching2O2Or MnO2Breeze Oxidation of Fe2+, stir oxidation 0.5
～1h, is subsequently added ammonia and is neutralized to pH 6.5 about except ferrum, 0.1～0.5g/L Sodium Dimethyldithiocarbamate removing heavy metals, solid-liquid separation obtains
Leachate.
After the purification of leaching liquor obtaining, in catholyte ((NH4)2SO4Concentration：90～110g/L, pH:7.0～7.2, temperature
Degree 38～44 DEG C, SeO2(in terms of Se)：0.03～0.04g/L), cathode-current density：350～400A/m2, anodic current density：
600～700A/m2, tank voltage：It is electrolysed under the conditions of 4.2～4.6V, prepared manganese metal.
In the present invention, described electrical heating continuous loading/unloading type shaft furnace by feed auger, discharging spiral propeller,
The portions such as boiler tube, heating mantle, heating furnace silk, condenser jacket, pre- hot jacket, circulating pump, feeding warehouse, product storehouse, support, flue gas recovery device
It is grouped into, wherein boiler tube is divided into feed zone, preheating section, bringing-up section, cooling section and discharging section five part, bringing-up section adopts external-heat
Power supply heats；Can achieve continuous feed and continuous discharge using feed auger and discharging spiral propeller, and can control
Charging and discharging speed；Boiler tube cooling section heat can be transferred to by preheating section using conduction oil, realize the effectively utilizes of heat.
In the present invention, the main valuable mineral of described high sulphur manganese mine is Manganese monosulfide., including or do not include troilite, sulfuration
The gangue minerals such as Pb-Zn deposits.Described high sulphur manganese mine contains manganese 8%～30%, sulfur-bearing 2%～25%.
Described lignin additive is the evaporation and concentration thing of soda processes, sulfate process or sulphite process black liquid,
Or extract one or more of the lignin obtaining, lignosulfonates or lignin cigarette sulfate from black liquid.Alkali
Catabolite containing lignin, hemicellulose and cellulose and organic acid in method or sulfate process black liquid concentrate
Deng.The main component of sulphite process black liquid concentrate is lignosulfonates, formic acid, also a small amount of acetic acid, fruit acid, list
The composition such as carbohydrate and free sulfate and sodium sulfide such as sugar and polysaccharide.Described lignosulfonates are sulfomethylated lignin
One or more of sour calcium, sodium lignin sulfonate, lignin sulfonic acid potassium, magnesium lignosulfonate, ammonium lignosulphonate.Papermaking is black
Contain substantial amounts of lignin in liquid, account for the 1%～2% of waste liquid total amount, account for the 30% about of total solid, due to cannot get fully
Using becoming the pollutant of environment for a long time, and waste substantial amounts of Liginon Resource.Contain in black liquid concentrate
Lignosulfonates, Na2S、Na2SO3、Na2S2O3Deng, if directly adopt burning method process, substantial amounts of sulfur dioxide can be produced
Flue gas.The additive containing lignin of the present invention has following obvious action effect：(1) can effectively dispersed mineral granule, keep away
Exempt from low melting point ore deposit melt in roasting process cause mineral lump, be conducive to keep roasting process Minerals mobility and
Improve leaching effect；(2) there is sulfur fixation, make sulfur more abundant with the effect of manganese oxide；(3) reduce the work of sintering temperature
With；(4) lignin that contains in black liquid, Na2S、Na2SO3、Na2S2O3Anti- with manganese oxide mineral etc. having reproducibility composition
Should, so that black liquid is comprehensively utilized, it is to avoid smoke pollution caused by direct burning black liquid papermaking.
In the present invention, described manganese oxide ore is pyrolusite, psilomelane, hausmannite, braunite, electrolytic manganese anode mud, big
In foreign many metals manganese nodule, useless manganese oxide catalyst one or more.
In the present invention, the main component of described manganese oxide is manganese dioxide, in manganese sesquioxide managnic oxide, mangano-manganic oxide one
Plant or several.
In the present invention, described conduction oil is alkyl benzene-type (benzenoid form), alkylnaphthalene type, alkyl biphenyl type, biphenyl or connection
Phenylate eutectic mixture type or alkyl biphenyl ether type synthesis conduction oil or mineral oil.
In the present invention, it is used below that described high sulphur manganese mine is crushed to 50 mesh.
In the present invention, it is used below that described manganese oxide is crushed to 50 mesh.
In the present invention, it is used below that described lignin is crushed to 20 mesh.
The know-why of the present invention is summarized as follows：Under the conditions of 400～700 DEG C of sintering temperature, high-sulfur in mixed material
Manganese ore pyrite, lignin and manganese oxide react, and are converted into MnO and MnSO of solubility4, can get manganese through sulfuric acid leaching
Leachate.
The reaction of roasting process alabandite is as follows：
MnS+4MnO2=4MnO+MnSO4
Gangue mineral troilite or lead-zinc sulfide ore also can be reacted with manganese oxide：
15MnO2+2FeS2=11MnO+4MnSO4+Fe2O3
ZnS+4MnO2=4MnO+ZnSO4
PbS+4MnO2=4MnO+PbSO4
Lignin with the reaction of manganese oxide is：
CxHyOz+(2x+y/2-z)MnO2=(2x+y/2-z) MnO+xCO2+y/2H2OCxHyOzSMe+(2x+y/2-z+4)
MnO2=(2x+y/2-z+3) MnO+MnSO4+xCO2+y/2H2O+MeO
C in formulaxHyOzRepresent lignin, CxHyOzSMe represents lignosulfonates, and Me represents calcium, sodium, potassium, magnesium or ammonia root.
Leaching process dominant response is as follows：
MnO+H2SO4=MnSO4+H2O
MnSO4=Mn2++SO4 2-
Further illustrate the present invention with embodiment below：
In embodiment, unless otherwise specified all percents refer both to mass percent.
Embodiment 1
Referring to Fig. 1, electrical heating continuous loading/unloading type shaft furnace device of the present invention, it is applied to be produced with high sulphur manganese mine clean and effective
In manganese metal.Heating mantle 5 is welded through cylinder by 4mm thickness iron plate, and by shaped steel additional reinforcement, fire door opening and closing place is stainless by high temperature
Steel makes, and prevents high temperature deformation.Burner hearth is opened in the customization of heating mantle 5 built-in ceramic alumina fiber, and high temperature 0Cr27 resistance furnace silk is pre-
It is embedded in the heating of burner hearth surrounding, liner tile and the insulation of fiber thermal insulation cotton between burner hearth and furnace shell.Thermocouple inserts from heating mantle side,
Measurement in-furnace temperature, heating mantle size：ф220*400.Heating mantle 5 side is fixed on boiler tube 3, and opposite side heating mantle can be through glue
Chain is opened, and has securing member at opening, can lock heating mantle.Boiler tube 3 is fixed on base 13, and base is the triangle of thick 200mm
Shape frame, boiler tube bottom terrain clearance is about 300mm.
Shaft furnace device boiler tube 3 is made by the thick 316L rustless steel of 5mm, a size of ф 100*1500, and top is to tapping into
Material spiral propeller, the pre- hot jacket of 400mm 11 (being connected with heating mantle 5 upper end) is arranged at boiler tube 3 top, and boiler tube 3 bottom has 400mm cold
But covered for 7 (being connected with heating mantle 5 lower end), pre- hot jacket and coolant jacket are circulated heat-shift (YD-350 using circulating pump 12
Conduction oil makees medium), discharging spiral propeller is docked in boiler tube 3 bottom, and boiler tube 3 is fixed by support 4, and boiler tube 3 scalable is upper and lower.Stove
Pipe top is connected stainless steel bend and is passed through alkali liquor absorption waste gas after being connected with heat-resisting leather hose.
Temperature control system is made up of intelligent temperature controller, heating power 6KW, and major loop is made up of three-phase 50A silicon controlled module, control
Loop processed is that upper marine products TCW-32B intelligent program instrument PID is adjusted, temperature-controlled precision ± 1 DEG C, and protection device is that leak electricity short-circuit is empty
Open, melt composition soon, control system is made up of converter, catalyst, button.Total system is arranged on independent control cabinet, by bearing
Carry power line and control line is connected with heating furnace silk 6, realize Automatic Control.
Embodiment 2
High sulphur manganese mine takes from Chenzhou, Hunan Province lead zinc flotation tailing storehouse, height argillization, and main manganese mineral is high sulphur manganese mine, contains
Sulfur mineral is mainly high sulphur manganese mine, pyrite, and the S in wherein MnS accounts for the 85% about of sulfur total amount, and its chemical composition is shown in Table 1.Oxygen
Change manganese ore sample and take from Xiangxi manganese ore, main manganese mineral is pyrolusite, its chemical composition analysis is shown in Table 1.Ore is size-reduced
To 50～400 mesh grades excessively.Operating procedure is as follows：
(1) in advance high sulphur manganese mine was crushed to 100 mesh sieves, Low grade manganese ore was crushed to 200 mesh sieves；
(2) by high sulphur manganese mine, manganese oxide ore, sodium lignin sulfonate in mass ratio 1:0.6:0.05 mix homogeneously, then by its
It is placed in electrical heating continuous loading/unloading type shaft furnace (same with embodiment 1) heating roasting, 600 DEG C of sintering temperature, the roasting time of staying
60min, firing stage sulfur loss rate 8.6%；Calcining adopts 0.8mol/L sulfuric acid leaching, 60 DEG C of extraction temperature, extraction time
30min, the leaching rate of manganese is 97.3%, and carries out chemical composition analysis to calcining and leached mud, and result is shown in Table 1 respectively.
Table 1：Sample ore chemical composition analysis
After the completion of leaching, ore pulp adds 3g/LMnO2Breeze Oxidation of Fe2+, stirring oxidation 1h, it is subsequently added ammonia and be neutralized to
PH 6.5 removes ferrum, 0.4g/L Sodium Dimethyldithiocarbamate removing heavy metals, and solid-liquid separation is purified liquid.By the leaching obtaining scavenging solution, in negative electrode
Liquid ((NH4)2SO4Concentration：100g/L, pH 7.0～7.2,40～42 DEG C of temperature, SeO2(in terms of Se)：0.04g/L), negative electrode electricity
Current density：380A/m2, anodic current density：650A/m2, tank voltage：It is electrolysed under the conditions of 4.4V, prepared manganese metal, electrolysis
Process current efficiency 68.37%, 6047 KWhs/ton of manganese of direct current consumption.
Embodiment 3
High sulphur manganese mine contains manganese 17.89%, sulfur 14.61%, and main manganese mineral is high sulphur manganese mine, manganese spar, containing sulfur minerals master
If pyrite, high sulphur manganese mine, wherein FeS2In S account for the 61% of sulfur total amount, remaining is mainly MnS；Manganese oxide ore and enforcement
Example 2 is identical.Operating procedure is as follows：
(1) in advance high sulphur manganese mine was crushed to 200 mesh sieves, Low grade manganese ore was crushed to 100 mesh sieves；
(2) by high sulphur manganese mine, manganese oxide ore, sodium lignin sulfonate in mass ratio 1:0.6:0.05 mix homogeneously, then will mix
Compound is placed in heating roasting in electrical heating continuous loading/unloading type shaft furnace reactor (same with embodiment 1), 600 DEG C of sintering temperature, roasting
Burn time of staying 45min, firing stage sulfur loss rate 7.1%；Calcining adopt 1.0mol/L sulfuric acid leaching, 60 DEG C of extraction temperature,
Extraction time 30min, the leaching rate of manganese is 99.6%.Purification of leaching liquor, Electrolytic conditions are same as Example 2, are electrolysed
Journey current efficiency 69.48%, 5994 KWhs/ton of manganese of direct current consumption.
Embodiment 4
High sulphur manganese mine and manganese oxide ore are same as Example 2, and operating procedure is as follows：
(1) in advance high sulphur manganese mine was crushed to 200 mesh sieves, Low grade manganese ore was crushed to 100 mesh sieves；
(2) by high sulphur manganese mine, manganese oxide ore, sodium lignin sulfonate in mass ratio 1:0.6:0.2 mix homogeneously, then by three
Mixture is placed in shaft furnace reactor (same with embodiment 1) and heats roasting, 600 DEG C of sintering temperature, roasting time of staying 45min,
Firing stage sulfur loss rate 1.2%；Calcining adopts 1.0mol/L sulfuric acid leaching, 60 DEG C of extraction temperature, extraction time 30min, manganese
Leaching rate be 98.6%.Purification of leaching liquor, Electrolytic conditions are same as Example 2, electrolytic process current efficiency
71.01%, 5903 KWhs/ton of manganese of direct current consumption；The manganese metal XRD spectrum of electrolytic preparation is shown in accompanying drawing 2, and manganese metal SEM picture is shown in attached
Fig. 3.
Embodiment 5
High sulphur manganese mine and manganese oxide ore are same as Example 2, and operating procedure is as follows：
(1) in advance high sulphur manganese mine was crushed to 50 mesh sieves, Low grade manganese ore was crushed to 100 mesh sieves；
(2) by high sulphur manganese mine, manganese oxide ore, calcium lignosulfonate in mass ratio 1:0.4:0.4 mix homogeneously, then by three
Mixture is placed in heating roasting in electrical heating continuous loading/unloading type shaft furnace (same with embodiment 2), 550 DEG C of sintering temperature, and roasting stops
Stay time 45min, firing stage sulfur loss rate 0.9%；Calcining adopts 1.0mol/L sulfuric acid leaching, 60 DEG C of extraction temperature, leaches
Time 60min, the leaching rate of manganese is 98.8%.Purification of leaching liquor, Electrolytic conditions are same as Example 2, electrolytic process electricity
Stream efficiency 70.63%, 5911 KWhs/ton of manganese of direct current consumption.
Embodiment 6
High sulphur manganese mine and manganese oxide ore are same as Example 2, and operating procedure is as follows：
(1) in advance high sulphur manganese mine was crushed to 100 mesh sieves, Low grade manganese ore was crushed to 200 mesh sieves；
(2) by high sulphur manganese mine, manganese oxide ore, lignin sulfonic acid potassium in mass ratio 1:0.7:0.35 mix homogeneously, then by three
Person's mixture is placed in heating roasting in electrical heating continuous loading/unloading type shaft furnace (same with embodiment 1), 500 DEG C of sintering temperature, roasting
Time of staying 45min, firing stage sulfur loss rate 0.8%；Calcining adopts 0.8mol/L sulfuric acid leaching, 80 DEG C of extraction temperature, leaching
Go out time 30min, the leaching rate of manganese is 90.8%.Purification of leaching liquor, Electrolytic conditions are same as Example 2, electrolytic process
Current efficiency 71.48%, 5899 KWhs/ton of manganese of direct current consumption.
Embodiment 7
High sulphur manganese mine is same as Example 2, and manganese oxide takes from the Xiangxi electrolytic manganese factory earth of positive pole, and main manganese mineral is
Pyrolusite, manganese grade is 49.4%, and lead grade is 4.5%, and operating procedure is as follows：
(1) in advance high sulphur manganese mine was crushed to 100 mesh sieves, the earth of positive pole was crushed to 100 mesh sieves；
(2) by high sulphur manganese mine, electrolytic manganese anode mud, calcium lignosulfonate mass ratio 1:0.3:0.3 mix homogeneously, then by three
Person's mixture is placed in heating roasting in electrical heating continuous loading/unloading type shaft furnace (same with embodiment 1), 600 DEG C of sintering temperature, roasting
Time of staying 60min, firing stage sulfur loss rate 1.3%；Calcining adopts 0.75mol/L sulfuric acid leaching, 80 DEG C of extraction temperature, leaching
Go out time 30min, the leaching rate of manganese is 95.8%.Purification of leaching liquor, Electrolytic conditions are same as Example 2, electrolytic process
Current efficiency 67.93%, 6098 KWhs/ton of manganese of direct current consumption.
Embodiment 8
High sulphur manganese mine is same as Example 2, and the earth of positive pole is same as Example 7, and operating procedure is as follows：
(1) in advance high sulphur manganese mine was crushed to 100 mesh sieves, the earth of positive pole was crushed to 200 mesh sieves；
(2) by high sulphur manganese mine, the earth of positive pole, sodium lignin sulfonate in mass ratio 1:0.2:0.5 mix homogeneously, then three is mixed
Compound is placed in heating roasting in electrical heating continuous loading/unloading type shaft furnace (same with embodiment 1), 500 DEG C of sintering temperature, and roasting stops
Time 50min, firing stage sulfur loss rate 0.7%；Calcining adopts 1.0mol/L sulfuric acid leaching, and 60 DEG C of extraction temperature, during leaching
Between 30min, the leaching rate of manganese is 98.0%.Purification of leaching liquor, Electrolytic conditions are same as Example 2, electrolytic process electric current
Efficiency 70.92%, 5999 KWhs/ton of manganese of direct current consumption.
Embodiment 9
High sulphur manganese mine is same as Example 2, and Gabon's manganese oxide ore taken from by manganese oxide ore sample ore, and main manganese mineral is soft manganese
Ore deposit, manganese grade is 45.6%, and Iron grade is 2.7%, and silicon dioxide is 10.8%, and operating procedure is as follows：
(1) in advance high sulphur manganese mine was crushed to 100 mesh sieves, Gabon's manganese ore was crushed to 200 mesh sieves；
(2) by high sulphur manganese mine, Gabon's manganese ore, calcium lignosulfonate in mass ratio 1:0.3:0.4 mix homogeneously, then by three
Mixture is placed in heating roasting in electrical heating continuous loading/unloading type shaft furnace (same with embodiment 1), 550 DEG C of sintering temperature, and roasting stops
Stay time 50min, firing stage sulfur loss rate 1.1%；Calcining adopts 1.0mol/L sulfuric acid leaching, 80 DEG C of extraction temperature, leaches
Time 30min, the leaching rate of manganese is 97.0%.Purification of leaching liquor, Electrolytic conditions are same as Example 2, electrolytic process electricity
Stream efficiency 67.90%, 6101 KWhs/ton of manganese of direct current consumption.
Embodiment 10
High sulphur manganese mine is same as Example 2, and Gabon's manganese ore is same as Example 9, and operating procedure is as follows：
(1) in advance high sulphur manganese mine was crushed to 100 mesh sieves, Gabon's manganese ore was crushed to 200 mesh sieves；
(2) by high sulphur manganese mine, Gabon's manganese ore, sodium lignin sulfonate in mass ratio 1:0.3:0.6 mix homogeneously, then by three
Mixture is placed in heating roasting in electrical heating continuous loading/unloading type shaft furnace (same with embodiment 1), 500 DEG C of sintering temperature, and roasting stops
Stay time 50min, firing stage sulfur loss rate 1.2%；Calcining adopts 0.5mol/L sulfuric acid leaching, 80 DEG C of extraction temperature, leaches
Time 45min, the leaching rate of manganese is 91.6%.Purification of leaching liquor, Electrolytic conditions are same as Example 2, electrolytic process electricity
Stream efficiency 71.13%, 5902 KWhs/ton of manganese of direct current consumption.
Embodiment 11
High sulphur manganese mine and manganese oxide ore are same as Example 2, the Hunan paper mill alkaline process concentrated black liquor that black liquid takes,
Total solid accounts for 17.67%, total alkali 46.23g/L, lignin 81.37g/L, other also falls containing hemicellulose and cellulose
Solution product and organic acid etc..Operating procedure is as follows：
(1) in advance high sulphur manganese mine was crushed to 50 mesh sieves, Low grade manganese ore was crushed to 100 mesh sieves；
(2) by high sulphur manganese mine, manganese oxide ore, black liquid concentrate in mass ratio 1:0.3:0.8 mix homogeneously, then by three
Person's mixture is placed in heating roasting in shaft furnace reactor (same with embodiment 1), 530 DEG C of sintering temperature, the roasting time of staying
60min, firing stage sulfur loss rate 1.1%；Calcining adopts 0.8mol/L sulfuric acid leaching, 70 DEG C of extraction temperature, extraction time
45min, the leaching rate of manganese is 97.9%.Purification of leaching liquor, Electrolytic conditions are same as Example 2, and electrolytic process electric current is imitated
Rate 70.55%, 5921 KWhs/ton of manganese of direct current consumption.
Embodiment 12
High sulphur manganese mine and manganese oxide ore are same as Example 2, and the Henan paper mill straw pulp black liquor that black liquid takes concentrates
Thing, total solid accounts for 21.96%, total alkali 52.47g/L, lignin 67.59g/L, other also contain polysaccharide, alcohols, organic acid,
Phenols etc..Operating procedure is as follows：
(1) in advance high sulphur manganese mine was crushed to 50 mesh sieves, Low grade manganese ore was crushed to 100 mesh sieves；
(2) by high sulphur manganese mine, manganese oxide ore, black liquid in mass ratio 1:0.3:0.7 mix homogeneously, then three is mixed
Thing is placed in heating roasting in shaft furnace reactor (same with embodiment 1), 530 DEG C of sintering temperature, roasting time of staying 60min, roasting
Stage sulfur loss rate 0.97%；Calcining adopts 0.8mol/L sulfuric acid leaching, 70 DEG C of extraction temperature, extraction time 45min, the leaching of manganese
Going out rate is 97.4%.Purification of leaching liquor, Electrolytic conditions are same as Example 2, electrolytic process current efficiency 70.08%, directly
Stream 5977 KWhs/ton of manganese of power consumption.
Embodiment 13
High sulphur manganese mine and manganese oxide ore are same as Example 2, and the Gansu paper mill straw pulp by neutral ammonium sulfite process that black liquid takes is black
Liquid concentrate, total solid accounts for 25.06%, lignin 86.53g/L.Operating procedure is as follows：
(1) in advance high sulphur manganese mine was crushed to 50 mesh sieves, Low grade manganese ore was crushed to 100 mesh sieves；
(2) by high sulphur manganese mine, manganese oxide ore, black liquid in mass ratio 1:0.4:0.75 mix homogeneously, then three is mixed
Compound is placed in shaft furnace reactor (same with embodiment 1) heating roasting, 550 DEG C of sintering temperature, roasting time of staying 60min, roasting
Burning stage sulfur loss rate 1.07%；Calcining adopt 0.8mol/L sulfuric acid leaching, 70 DEG C of extraction temperature, extraction time 45min, manganese
Leaching rate is 96.3%.Purification of leaching liquor, Electrolytic conditions are same as Example 2, electrolytic process current efficiency 70.09%,
5949 KWhs/ton of manganese of direct current consumption.
Embodiment of above is merely to illustrate the present invention, rather than limitation of the present invention.Although with reference to embodiment to this
Bright be described in detail, it will be understood by those within the art that, technical scheme is carried out various combinations,
Modification or equivalent, without departure from the spirit and scope of technical solution of the present invention, the right that all should cover in the present invention will
Ask in the middle of scope.
Claims (7)
1. a kind of high sulphur manganese mine clean and effective produces the method for manganese metal it is characterised in that the method comprises the following steps：
Step one：By high sulphur manganese mine, manganese oxide mineral, lignin additive in mass ratio 1:0.1～0.8：0.01～0.8 mixing
Uniformly；
Step 2：The mixed material that step one is obtained is added continuously to shaft furnace top, carries out material in preheating zone pre- first
Heat, then carries out roasting in the thermal treatment zone, and sintering temperature is 400～700 DEG C, and roasting time is 30～150min, by the roasting obtaining
Sand is cooled down in cooling zone, by the calcining of cooling from shaft furnace bottom continuous discharge；
Step 3：The calcining that step 2 is obtained at 40～90 DEG C with the sulphuric acid leaching 5 of 0.5～1.0mol/L～
60min, it is 3～8 that leaching process controls the solid mass ratio of liquid:1, add a certain amount of H after leaching2O2Or MnO2Breeze Oxidation of Fe2+,
Stirring oxidation 0.5～1h, is subsequently added ammonia and is neutralized to pH 6.2-6.8 except ferrum, addition 0.1～0.5g/L Sodium Dimethyldithiocarbamate are except a huge sum of money
Belong to, solid-liquid separation is purified leachate；
Step 4：The purification leachate that step 3 is obtained, in catholyte：(NH4)2SO4, its concentration：90～110g/L, pH：
7.0～7.2,38～44 DEG C of temperature, SeO2In terms of Se：0.03～0.04g/L, cathode-current density：350～400A/m2, anode
Electric current density：600～700A/m2, tank voltage：It is electrolysed under the conditions of 4.2～4.6V, prepared manganese metal.
2. use high sulphur manganese mine clean and effective according to claim 1 produces the method for manganese metal it is characterised in that described
High sulphur manganese mine main component is Manganese monosulfide., including troilite, lead-zinc sulfide ore；Described high sulphur manganese mine contains manganese 8～30%, sulfur-bearing
2～25%.
3. use high sulphur manganese mine clean and effective according to claim 1 produces the method for manganese metal it is characterised in that described
Manganese oxide mineral includes pyrolusite, psilomelane, hausmannite, braunite, electrolytic manganese anode mud, oceanic multi-metal manganese nodule or useless oxygen
Change Mn catalyst.
4. the method that the use high sulphur manganese mine clean and effective according to claims 1 to 3 any of which item produces manganese metal, it is special
Levy and be, described lignin additive is the evaporation and concentration thing of soda processes, sulfate process or sulphite process black liquid, or
One or more of the lignin obtaining, lignosulfonates or lignin-sulphonate is extracted from black liquid.
5. use high sulphur manganese mine clean and effective according to claim 4 produces the method for manganese metal it is characterised in that described
Lignosulfonates are calcium lignosulfonate, sodium lignin sulfonate, lignin sulfonic acid potassium, magnesium lignosulfonate, lignin sulfonic acid
One or more of ammonium.
6. use high sulphur manganese mine clean and effective according to claim 1 produces the method for manganese metal it is characterised in that in step
In two, the mixed material that step one is obtained is charged first to the feeding warehouse of described shaft furnace, successively again by the charging of described shaft furnace
Section, preheating section, bringing-up section, cooling section and discharging section, obtain calcining.
7. use high sulphur manganese mine clean and effective according to claim 6 produces the method for manganese metal it is characterised in that in step
In two, described bringing-up section adopts external-heat power supply to heat；Described cooling section transfers heat to preheating section using conduction oil.
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| CN105753056B (en) * | 2016-02-26 | 2017-09-29 | 中南大学 | A kind of method for preparing manganese sulfate |
| CN106222422B (en) * | 2016-08-22 | 2018-04-24 | 南昌航空大学 | One kind is rich in heavy metal biological precipitation slag short route metal smelt recovery method |
| CN106544502B (en) * | 2016-10-27 | 2018-10-09 | 中南大学 | A kind of chemistry desilication method and the application in black type iron oxide Mineral Processing For Manganese Ore |
| CN106399724B (en) * | 2016-10-27 | 2019-01-11 | 中南大学 | A kind of microwave reducing roasting and extracting method of manganese oxide ore |
| CN106835195B (en) * | 2017-02-26 | 2018-11-06 | 桂林理工大学 | A method of the low selenium composite additive electrolytic manganese of addition |
| CN107740139B (en) * | 2017-12-14 | 2019-09-27 | 六安中达信息科技有限公司 | A kind of quick recycling noble metal equipment of environmental protection based on active carbon |
| CN108441888A (en) * | 2018-05-15 | 2018-08-24 | 江西理工大学 | A kind of tin electrorefining electrolyte compound additive |
| CN108842053A (en) * | 2018-07-06 | 2018-11-20 | 中南大学 | The method of comprehensive utilization of Low grade manganese ore and electrolytic manganese crystallization double salt |
| CN108842052A (en) * | 2018-07-06 | 2018-11-20 | 中南大学 | The method of comprehensive utilization of electrolytic manganese anode slag and electrolytic manganese crystallization double salt |
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