CN86101482B - Psilomelane prepares the method and the device of electroactive manganese dioxide powder - Google Patents
Psilomelane prepares the method and the device of electroactive manganese dioxide powder Download PDFInfo
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- CN86101482B CN86101482B CN86101482A CN86101482A CN86101482B CN 86101482 B CN86101482 B CN 86101482B CN 86101482 A CN86101482 A CN 86101482A CN 86101482 A CN86101482 A CN 86101482A CN 86101482 B CN86101482 B CN 86101482B
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Abstract
Psilomelane prepares the method and the device of electroactive manganese dioxide powder, first method is that the psilomelane coarse crushing with bulk becomes piece material, carries out oxide treatment, screening, sorting, strong magnetic enrichment, drying then, grinds, checks classification to make the battery manganese powder of various grades.Second method and first kind are basic identical, just oxide treatment are changed into oxidation and thermolysis are carried out simultaneously.The present invention does not use any beneficiation reagent and acid, alkali, salt.First method is suitable for lacking township and village enterprises's use of enough thermals source; Second method is suitable for the competent large and medium-sized industrial and mining enterprises of thermal source and uses.
Description
The present invention relates to psilomelane is directly changed into the method and the device of electroactive manganese dioxide powder, existing electroactive manganese dioxide powder, generally adopting the natural pyrolusite stone be rich in Manganse Dioxide is raw material, by fragmentation, washing, ball milling, operation such as dry and produce.Though its method is easy, and easy handling, the electroactive manganese dioxide powder of being produced still contains more metalliferous mineral impurity, non-metallic minerals impurity, gangue and volatile matter.It is subjected to the restriction of head grade, can't produce more high-grade product.In addition, natural pyrolusite (particularly high-grade pyrolusite) resource is day by day exhausted in many countries and regions at present, and natural psilomelane resource is extremely abundant.But psilomelane is not rich in Manganse Dioxide, and it is the mixture of oxide compound, oxyhydroxide, carbonate, silicate and the various impurity of the multiple bond valence of manganese, and dopant species is many, quantity is big.
The method and a kind of sorting unit ， And that the objective of the invention is to provide two kinds of psilomelanes to be directly changed into electroactive manganese dioxide powder overcome because of the not high drawback that can not make high-quality product of head grade, can produce product basically on demand.
The basic foundation of the first method that the present invention proposes is: in the psilomelane suboxide of manganese and oxyhydroxide can be more oxidized in oxidizing atmosphere and wet environment preferably, cracking and refinement voluntarily, and the carbonate of manganese, silicate and metalliferous mineral impurity and gangue, under these conditions mostly can be promptly not oxidized, cracking and refinement voluntarily, the volatile matter in its impurity and some nonmetallic impurity at a certain temperature can be water-soluble.
For psilomelane being prepared into electroactive manganese dioxide powder, the technical process of the first method that the present invention proposes as shown in Figure 1.
Ben Fafa comprises following eight procedures, i.e. fragmentation, oxide treatment, screening, sorting, strong magnetic enrichment, drying, grind, check classification.
When broken, oversize material is broken into fritter, its lumpiness is advisable for about 10 centimetres with diameter.When carrying out oxide treatment, material individual layer after the coarse crushing is spread on smooth, smooth, solid, the clean preferably ground (or table top) of daylighting and ventilation condition, make its natural oxidation And under air, sunlight often spray a small amount of clear water, make material keep moistening, but material is immersed in the water.Be to quicken oxidation, cracking and the refinement voluntarily of material, also must be through the conventional aluminum rake material of flapping, but must not knock material.
When sieving, with oxidation, Lie Xie And voluntarily refinement material sieve with 36 eye mesh screens.Screen overflow repeats above-mentioned oxidation operation, and screen underflow changes down step sorting operation over to.
The flow process of sorting operation is seen Fig. 2 and Fig. 3 (being the sorting unit structure iron).When material carries out sorting, six gate valves (1) shown in Figure 3 are closed.Quantitatively aforementioned screen underflow is dropped into sorting groove (4) then in batches.Open water intaking valve (7), in groove, slowly supply water.To sorting groove (4) when feeding intake, an input amount must not exceed half of groove depth.With the continuous disturbance tank liquor of aluminium matter rake.Owing to contain more organic matter in the psilomelane, this moment, tank liquor became a kind of viscosity and the bigger colloidal solution of surface tension in fact.Granularity is the material of thin (60 order), progressively floats through disturbance.Open gate valve (11), make the material of come-up overflow into shunting pond (6), at the bottom of the pond, feed steam then, the heating feed liquid with inboard steam-pipe with water.After treating the face boiling of whole pond, stop heating.Open gate valve (1), make feed liquid flow into settling bowl (5), and then open water intaking valve (10), clear water is sprayed into from the settling bowl bottom through water inlet pipe (9), stir material, quicken the dissolving of soluble impurity through straight trough (12).The water liquid of settling bowl infiltrates ponding well (3) through drainage partition wall (2).In assorting room, take out the pH value of the liquid ， And fixed time test well liquid in the ponding well (3) continuously with pump.When pH value greater than 5.5 the time, close water intaking valve (10), drain the liquid in the ponding well (3).When observation drainage partition wall does not have the infiltration phenomenon, draw the mud sample material of getting in the settling bowl (5), drop into the strong magnetic enrichment in road operation down.
In the operation of above waterpower sorting, in sorting groove (4) remaining material with finger rub with the hands to grind have tangible, general coarse grain sense, raw meal particle size reach+during 60 orders, close water intaking valve (7), draw out residue material in the groove, feed intake again.The main manganous carbonate that contains of this residue material gets final product the manganous carbonate meal that enrichment goes out to have industrial use value by the high intensity magnetic separation technology.Through chemically examine qualified after again through ball milling (otherwise returning magnetic separation again), can make qualified product.
The aforementioned mud sample material master who draws out from settling bowl (5) contains Manganse Dioxide.This thing science and technology is gone into intensity magnetic separator carry out magnetic separation.Magnetic separator adopts existing wet type tubular intensity magnetic separator, and magneticstrength is controlled at 1 * 10
4About oersted.Material has been removed exhausted most impurity (mainly being shale gangue impurity) through high intensity magnetic separation, has improved the content of Manganse Dioxide in the material greatly, will be under magnetic separation gained fine fodder input the road drying process.
When carrying out drying process, above-mentioned fine fodder thin layer stand cloth is dried on dry, smooth, clean, solid and daylighting, ground (or table top) that ventilation condition is good or dry.In drying process, use the aluminium matter rake material of often flapping, make it to be difficult for conglomeration, And can enlarge the contact surface of material and air and quicken drying, also can make it further oxidation.Material is after drying tested its moisture content value and is not more than at 1% o'clock, can enter down to go on foot to grind operation.
When grinding, adopt ball mill that material is after drying worn into desired particle size, change check classification operation then over to.
The physical and chemical inspection of electroactive manganese dioxide powder comprises following project: the discharge time (put between containing and connect the time of putting) of promptly making test cell; The Manganse Dioxide analysis of components; The nickel qualitative analysis; Soluble copper content; Iron level; Lead content; PH value is measured; Moisture determination; Particle size measurement etc.Be leading indicator the discharge time that the check classification should be made test cell with this powder, is inserted in the appropriate level of battery manganese powder by this.If because detrimental impurity is too much in the raw ore, the guiding discharge time index does not meet the requirement of battery manganese powder, then can be inserted in chemical industry or metallurgical appropriate level by Chemical Composition (mainly being Manganse Dioxide and iron and dioxide-containing silica) with manganese powder.
Second method provided by the invention is, at first adopt existing crushing mechanism to be ground into-36 purpose powders the bulk psilomelane, drop into existing fluidisation stove (also claiming fluidizing furnace) or kiln then, in stove (kiln), spray into warm air or steam (temperature is 230 ± 5 ℃) simultaneously with oxidation and thermolysis material.In this operation, the suboxide of manganese and oxyhydroxide further are oxidized to Manganse Dioxide in the raw material; Most manganous carbonate is a Manganse Dioxide by calcination.Last drying process is that material is placed in the dry kiln, feeds warm air (temperature is no more than 105 ± 5 ℃) and carries out drying.Other operation and employed device are identical with first method.Adopt its productivity of present method and work efficiency to be much better than first method.The ratio of manganous carbonate obviously descends in its product, and the ratio of Manganse Dioxide rises significantly.
The sorting unit that the present invention proposes is seen Fig. 3 (structure iron).Wherein, the 1-gate valve, 2-drainage partition wall, 3-ponding well, 4-sorting groove, the 5-settling bowl, 6-shunts the pond, 7-sorting water intaking valve, 8-spilling water passage, 9-water inlet pipe, 10-settling bowl water intaking valve, 11-gate valve, 12-straight trough.
This sorting unit comprises a sorting groove (4), and its profile is shaped as recessed parabola shaped opening, is provided with sorting water intaking valve (7) above the sorting groove (4).One side of sorting groove (4) has spilling water passage (8), and there is a gate valve (11) in its exit.Spilling water passage (8) is connected with shunting pond (6).Shunting pond (6) is a cylindrical wall and flat-bottom structure, and snakelike steam heating tube is equipped with at the bottom of its pond and inboard, and the top, pond is added with sealing cover (annotate: heating tube and sealing cover are all not shown in the drawings).Have six straight troughs (12) on the circumference in shunting pond, be connected with six settling bowls (5) respectively.Every straight trough (12) but on the gate valve (1) of a switch is housed; An inlet channel (9) is equipped with in the bottom of settling bowl (5), and a water intaking valve (10) is housed on its pipeline; There is a ponding well (3) in the outside of settling bowl (5), has drainage partition wall (2) to separate between the two.
Enter in the whole motion of separation system (device) at material, sorting groove and shunting pond are to belong to quick link, and settling bowl belongs to link at a slow speed.Sorting capability and whole productivity ， And realize continuously in order to improve, balanced production, so separation system is provided with six (or a plurality of) settling bowls, and the shunting pond of a big volume (being about three settling bowl sizes).Six settling bowls can be used alternatingly, and realize balanced production.
The first method embodiment that the present invention proposes is as follows:
Raw material occurrence: originate in the zone of oxidation of manganese ore deposit, and mainly form by manganous silicate and manganous carbonate differentiation.
The mineral of raw material constitute and Chemical Composition:
One, full manganese content: 28%
Wherein: MnO
226%
MnO 7.2%
MnCO
3 8.8%
MnSiO
32.1%
Two, metalliferous mineral impurity: iron (3%), plumbous (0.4%), zinc (3%), copper (trace), Jin Heyin (trace), nickel mineral and arsenic (0.1%) mineral such as (traces).
Three, non-metallic minerals impurity: sulphur (0.1%) and phosphorus mineral such as (0.15%).
Four, volatile matter: water (4%), organic (5%).
Five, gangue (surplus): the oxide compound of silicon, aluminium, calcium, magnesium and baryta mineral.
Raw material lumpiness: greater than 20 centimetres (diameters).
Raw material weight: 100 tons.
This raw material drops into oxide treatment behind aforementioned broken process.Oxide treatment begins screening after 48 hours.Raw material obtains 89 tons of one 36 purpose powders after oxidation and screening.After the sorting operation, obtain Manganse Dioxide coarse fodder and 10.3 tons of manganous carbonate coarse fodders of 78 tons.Adopt existing wet type tubular intensity magnetic separator (φ 560 * 400) to carry out high intensity magnetic separation then.Obtain 20.1 tons of Manganse Dioxide fine fodders (clean material) through magnetic concentration, 2.6 tons of carbonic acid manganese powders (clean material).Obtain 19.1 tons of manganese dioxide powder products, 2.5 tons of manganous carbonates behind above-mentioned fine fodder drying and the ball milling.The whole cycle is 5 days.
The main physical and chemical index of above manganese dioxide powder product is as follows:
(1), Manganse Dioxide content: 80%
(2), make the discharge performance of test cell:
Connect and put 580 minutes time
Between put 1150 minutes time
(3), iron-holder: 2%
(4), soluble copper: trace
(5), nickel qualitative analysis: redfree
(6), pH value: 5.6
(7), lead content: 0.2%
(8), moisture content: 1%
(9), granularity :-120 orders (by 98%)
Above physical and chemical index all satisfies the requirement of existing one-level battery manganese powder.
The main physical and chemical index of above-mentioned carbonic acid manganese powder product is as follows:
(1), manganous carbonate content: 75%
(2), Manganse Dioxide content: 11%
(3), granularity :-120 orders
(4), moisture content: 1%
The second method embodiment that the present invention proposes is as follows:
Raw material condition is the same.
Above-mentioned raw materials is repeatedly pulverized by existing jaw crusher, obtains 96 tons of one 36 powder materials.This material adopts existing large-scale fluidisation stove fusion, and each charging capacity is 20 tons, and every stove cycle is 1.5 hours.Obtain 90.2 tons of calcination material total amounts.Obtain 84.1 tons of Manganse Dioxide coarse fodders through the sorting operation, obtain 5.1 tons of manganous carbonate meal.Obtain 31.5 tons of Manganse Dioxide fine fodders (clean material) through strong magnetic enrichment, 2.2 tons in the smart powder of manganous carbonate (clean material).Above-mentioned fine fodder drying and ball milling obtain 28.9 tons of manganese dioxide products, 2.1 tons of manganese carbonate products.The whole production cycle is two days.
The main physical and chemical index of above manganese dioxide powder product is as follows:
(1), Manganse Dioxide content: 81%
(2), make the discharge performance of test cell:
Connect and put 580 minutes time
Between put 1150 minutes time
(3), iron-holder: 2%
(4), soluble copper: trace
(5), nickel qualitative analysis: redfree
(6), pH value: 5.6
(7), lead content: 0.2%
(8), moisture content: 0.5%
(9), granularity :-120 orders (by 98%)
Above physical and chemical index all satisfies the requirement of existing one-level battery manganese powder.
The main physical and chemical index of above-mentioned carbonic acid manganese powder product is as follows:
(1), manganous carbonate content: 76%
(2), Manganse Dioxide content: 15%
(3), granularity :-120 orders
(4), moisture content: 0.5%
First method of the present invention is suitable for lacking enough thermals source and power supply shortage, but the broad township and village enterprises of production site.
Second method of the present invention is suitable for thermal source and the competent large and medium-sized industrial and mining enterprises of electric power.
The present invention has many advantages, except that can obtaining battery manganese powder (or chemical industry, the metallurgical manganese powder of using), also can obtain by-product-industrial carbonic acid manganese powder as above-mentioned two kinds of methods.Its first method mainly adopts the wet method operation, does not have a large amount of dust from flying; In addition, it does not use any beneficiation reagent and acid, alkali, salt, so environmental pollution is few.Present method is comparatively easy, and sorting unit is simple in structure, is suitable for continuous production in enormous quantities.Present method can adopt the raw material that grade is lower, other foreign matter content is moderate to produce high level electroactive manganese dioxide powder.
Claims (4)
1, a kind of method that psilomelane is directly changed into electroactive manganese dioxide powder, it comprises coarse crushing, oxide treatment, screening, sorting, strong magnetic enrichment, dry, grind, the check classification is totally 8 procedures, it is characterized in that the stand of the piece material after coarse crushing cloth will be got well in daylighting and ventilation condition, smooth, on the clean ground (or table top), adopt clear water to spray material, and make its natural oxidation in air, cracking and voluntarily refinement stir material through the conventional aluminum rake, material through oxide treatment screens with 36 eye mesh screens, undersize material drops into sorting groove (4) in batches and carries out sorting, simultaneously continuous disturbance tank liquor, make the material of come-up overflow into shunting pond (6) with current, and to shunting pond feeding steam heating, after the heating, feed liquid flows into settling bowl (5) precipitation, water liquid then infiltrates ponding well (3) from drainage partition wall (2), when ponding well liquid pH value＞5.5, and when drainage partition wall (2) does not have the infiltration sign, draw the mud sample material of getting in the settling bowl (5) and do strong magnetic enrichment, cloth is smooth preferably in daylighting and ventilation condition through magnetic separation gained fine fodder stand, dry on the clean ground (or table top) or dry, material after drying grinds by desired granularity and makes product.
2, method according to claim 1 is characterized in that to sorting groove (4) quantitatively in batches when feeding intake, and charging capacity is no more than the sorting groove depth half.
3, a kind of device that psilomelane is directly changed into electroactive manganese dioxide powder, it is characterized in that having a sorting groove (4), its profile is shaped as recessed para-curve (or small semicircle) opening, opening part has water intaking valve (7), one side of sorting groove (4) has spilling water passage (8), there is a gate valve (11) in its exit, and spilling water passage (8) is connected with shunting pond (6).Shunting pond (6) is a cylindrical wall flat-bottom structure, and at the bottom of its pond and inboard is equipped with snakelike steam heating tube respectively.Have 6 (or many) straight troughs (12) on its circumference, be connected with 6 or a plurality of settling bowl (5) respectively.There is an inlet channel (9) settling bowl (5) inboard, and a water intaking valve (10) is housed on it, and there is a ponding well (3) in the outside, separates with drainage partition wall (2) between settling bowl (5) and the ponding well (3).Settling bowl (5) medial surface is parabola or sphere.
4, a kind of method that psilomelane directly is converted to electroactive manganese dioxide powder: its operation comprises fragmentation, calcination, sorting, strong magnetic enrichment, drying, ball milling, it is characterized in that the powder after the fragmentation must drop into calcination in fluidisation stove or the rotary kiln, in stove (kiln), spray into simultaneously the warm air or the steam of oxidation and thermolysis material, its temperature is 230 ± 5 ℃, last drying process is to utilize warm air or furnace-heated in fluidisation stove or dry kiln, and other operation is all identical with above-mentioned first method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN86101482A CN86101482B (en) | 1986-02-27 | 1986-02-27 | Psilomelane prepares the method and the device of electroactive manganese dioxide powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN86101482A CN86101482B (en) | 1986-02-27 | 1986-02-27 | Psilomelane prepares the method and the device of electroactive manganese dioxide powder |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN86101482A CN86101482A (en) | 1987-01-14 |
| CN86101482B true CN86101482B (en) | 1988-06-01 |
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ID=4801405
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN86101482A Expired CN86101482B (en) | 1986-02-27 | 1986-02-27 | Psilomelane prepares the method and the device of electroactive manganese dioxide powder |
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|---|---|
| CN (1) | CN86101482B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010023692A1 (en) * | 2008-08-30 | 2010-03-04 | Tata Steel Limited | A novel method for production of iron ore concentrates suitable for iron and steel making processes. |
| CN102040247B (en) * | 2010-11-20 | 2012-10-24 | 湖北开元化工科技股份有限公司 | Method and device for producing chemical manganese dioxide |
| CN106238199A (en) * | 2016-07-27 | 2016-12-21 | 中信大锰矿业有限责任公司大新锰矿分公司 | A kind of promote the method that natural electric discharge manganese powder puts point performance continuously |
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1986
- 1986-02-27 CN CN86101482A patent/CN86101482B/en not_active Expired
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