CN206828588U - A kind of system for handling germanic lignite and copper tailings - Google Patents
A kind of system for handling germanic lignite and copper tailings Download PDFInfo
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- CN206828588U CN206828588U CN201720594366.5U CN201720594366U CN206828588U CN 206828588 U CN206828588 U CN 206828588U CN 201720594366 U CN201720594366 U CN 201720594366U CN 206828588 U CN206828588 U CN 206828588U
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Abstract
It the utility model is related to the system for handling germanic lignite and copper tailings.The system includes mixing arrangement, rotary kiln baking device, mill ore magnetic selection device, leaching device, hydrolysis device；Mixing arrangement has copper tailings entrance, petroleum coke entrance, dolomite entrance, compound outlet；Rotary kiln baking device has compound entrance, germanic lignite entrance, reducing material outlet, flue dust outlet, and compound entrance connects with compound outlet；There is mill ore magnetic selection device reducing material entrance, iron powder outlet, mill to select tailings to export, and reducing material entrance connects with reducing material outlet；Leaching device has flue dust entrance, concentrated sulfuric acid entrance, leachate outlet, lead sulfate solid discharge, and flue dust entrance connects with flue dust outlet；Hydrolysis device has leachate entrance, high-purity water inlet, germanium dioxide outlet, solution of zinc sulfate outlet, and leachate entrance connects with leachate outlet.The utility model can realize the comprehensive reutilization of the energy and material.
Description
Technical field
It the utility model is related to metallurgical technology field, and in particular to a kind of system for handling germanic lignite and copper tailings.
Background technology
Germanium is a kind of chemical element, and chemical symbol Ge, atomic number is 32, atomic weight 72.64.Germanium is in chemical element week
Positioned at the 4th cycle, group IVA in phase table.Germanium simple substance is a kind of canescence metalloid, and glossy, matter is hard, belongs to carbon family, chemistry
Property and tin of the same clan are close with silicon, not soluble in water, hydrochloric acid, dilute caustic solution, are dissolved in chloroazotic acid, concentrated nitric acid or sulfuric acid, have
Both sexes, therefore the alkali of fusing, peroxide choline, alkali nitrates or carbonate are dissolved in, it is more stable in atmosphere.In nature,
Germanium shares five kinds of isotopes：70th, 72,73,74,76, generation GeO is acted on oxygen more than 700 DEG C2, more than 1000 DEG C and hydrogen
Effect, fine powder germanium can burn in chlorine or bromine.Germanium is defect semiconductor, can make the detection of high-frequency current and the rectification of alternating current
With.In addition, germanium metal can be additionally used in infrared luminescent material, precision instrument, catalyst.The compound of germanium can be used for manufacture fluorescent plate and
The high glass of various refractive indexes.
Germanium, tin and lead belong to family together in the periodic table of elements, tin and lead it is early by ancient times it is found that and utilize, and when germanium is long
Plant-scale exploitation has all been not carried out since phase.This is not few because of content of the germanium in the earth's crust, but because germanium is ground
One of most scattered element in shell, germanic ore are less.
Method on extracting Ge element from lignite or zinc metallurgy slag in the prior art, generally existing energy consumption cost is high to ask
Topic, and fail to realize the comprehensive reutilization of the energy and element.
Utility model content
The utility model aims to provide a kind of system for handling germanic lignite and copper tailings, utilizes system of the present utility model
While germanium recovery is realized, the reducing roasting process of the heat supply material of germanic lignite burning can be utilized, and can be with
Realize the comprehensive utilization of germanic lignite and copper tailings.
The utility model provides a kind of system for handling germanic lignite and copper tailings, including the roasting of mixing arrangement, rotary kiln
Burn device, mill ore magnetic selection device, leaching device, hydrolysis device.
The mixing arrangement has copper tailings entrance, petroleum coke entrance, dolomite entrance, compound outlet.
The rotary kiln baking device has compound entrance, germanic lignite entrance, reducing material outlet, flue dust outlet.
The compound outlet of the compound entrance and the mixing arrangement connects.
There is the mill ore magnetic selection device reducing material entrance, iron powder outlet, mill to select tailings to export.The reducing material enters
The reducing material of mouth and the rotary kiln baking device, which exports, to be connected.
The leaching device has flue dust entrance, concentrated sulfuric acid entrance, leachate outlet, lead sulfate solid discharge.The cigarette
The flue dust outlet of dirt entrance and the rotary kiln baking device connects.
The hydrolysis device has leachate entrance, high-purity water inlet, germanium dioxide outlet, solution of zinc sulfate outlet.Institute
The leachate outlet for stating leachate entrance and the leaching device connects.
Preferably, cloth bag is provided with the kiln tail of the rotary kiln baking device, for collecting flue dust.
Further, said system also includes the first electrolysis melted ingot device, and there is solution of zinc sulfate entrance, zinc ingot metal to export.
The solution of zinc sulfate outlet of the solution of zinc sulfate entrance and the hydrolysis device connects.
Further, said system also includes the second electrolysis melted ingot device, and there is lead sulfate residue entrance, lead pig to export.
The lead sulfate residue entrance is connected with the lead sulfate solid discharge of the leaching device.
Using system of the present utility model when handling germanic lignite and copper tailings, can reclaim simultaneously zinc therein, lead,
Germanium metallic element, and the higher rate of recovery is respectively provided with, and heat caused by the burning of germanic lignite is farthest utilized, at reduction
The energy consumption of reason process, realize the comprehensive reutilization of the energy and material.
Brief description of the drawings
Fig. 1 is the system schematic that germanic lignite and copper tailings is handled in the utility model embodiment.
Fig. 2 is the method flow schematic diagram that germanic lignite and copper tailings are handled using system of the present utility model.
Reference in accompanying drawing is as follows：
100- mixing arrangements, 101- copper tailings entrance, 102- petroleum cokes entrance, 103- dolomites entrance, 104- compounds
Outlet；
200- rotary kiln bakings device, 201- compounds entrance, the germanic lignite entrances of 202-, 203- reducing materials outlet,
204- flue dust exports；
300- mill ore magnetic selections device, 301- reducing materials entrance, the outlet of 302- iron powders, 303- mills select tailings to export；
400- leaching devices, 401- flue dust entrance, 402- concentrated sulfuric acids entrance, the outlet of 403- leachates, 404- lead sulfates are residual
Slag exports；
500- hydrolysis devices, 501- leachates entrance, the high-purity water inlets of 502-, the outlet of 503- germanium dioxides, 504- sulfuric acid
Zinc solution exports；
600- first is electrolysed melted ingot device, 601- solution of zinc sulfate entrance, the outlet of 602- zinc ingot metals；
700- second is electrolysed melted ingot device, 701- lead sulfates residue entrance, the outlet of 702- lead pigs.
Embodiment
Below in conjunction with drawings and examples, specific embodiment of the present utility model is described in more details, with
Just the advantages of better understood when scheme of the present utility model and its various aspects.However, specific implementations described below
Mode and embodiment are for illustrative purposes only, rather than to limitation of the present utility model.
As shown in figure 1, in system of the utility model for handling germanic lignite and copper tailings, the connection between each device
Relation is：
Mixing arrangement 100 is used for uniformly mixing raw material, and it has copper tailings entrance 101, petroleum coke entrance 102, dolomite
Entrance 103, compound outlet 104.
Rotary kiln baking device 200 is used for the reduction roasting of germanic lignite and compound, its have compound entrance 201,
Germanic lignite entrance 202, reducing material outlet 203, flue dust outlet 204.Wherein, compound entrance 201 and mixing arrangement 100
The connection of compound outlet 104.Wherein, reducing material outlet 203 is arranged on the kiln hood discharge outlet of rotary kiln baking device 200.It is excellent
Choosing, cloth bag is provided with the kiln tail of rotary kiln baking device 200, cloth bag connects with flue dust outlet 204, for collecting cigarette
Dirt.
Mill ore magnetic selection device 300 be used for reducing material mill ore magnetic selection obtain iron powder, its have reducing material entrance 301,
Iron powder outlet 302, mill select tailings to export 303.Wherein, the reducing material of reducing material entrance 301 and rotary kiln baking device 200
The connection of outlet 203.
Leaching device 400 is used under the conditions of high temperature peracid leach zinc, lead, the germanium metal in flue dust, and there is flue dust to enter for it
Mouth 401, concentrated sulfuric acid entrance 402, leachate outlet 403, lead sulfate solid discharge 404.Wherein, flue dust entrance 401 and rotary kiln
The connection of flue dust outlet 204 of calciner 200.
Hydrolysis device 500 is used for the heavy germanium of hydrolysis of leachate, and it has leachate entrance 501, high-purity water inlet 502, two
Germanium oxide outlet 503, solution of zinc sulfate outlet 504.Wherein, the leachate of leachate entrance 501 and leaching device 400 exports
403 connections.
In embodiment of the present utility model, the system also includes the first electrolysis melted ingot device 600, for solution of zinc sulfate
Electrolysis, the fusing of metallic zinc, the ingot casting processing of metallic zinc obtain zinc ingot metal, and it has solution of zinc sulfate entrance 601, zinc ingot metal outlet
602.Wherein, solution of zinc sulfate entrance 601 is connected with the solution of zinc sulfate outlet 504 of hydrolysis device 500.
In embodiment of the present utility model, in addition to the second electrolysis melted ingot device 700, electrolysis for lead sulfate residue,
Fusing, the ingot casting processing of metallic lead obtain lead pig, and it has lead sulfate residue entrance 701, lead pig outlet 702.Wherein, lead sulfate
Residue entrance 701 is connected with the lead sulfate solid discharge 404 of leaching device 400.
As shown in Fig. 2 the method for germanic lignite and copper tailings is handled using system of the present utility model, including following step
Suddenly：
A, raw material mixes
By copper tailings, petroleum coke, dolomite according to mass ratio be 100：(20~30)：(5~10) it is sent into mixing arrangement,
It is well mixed to obtain compound.Water content≤8wt% of compound (wt% is mass percent).
Also, the amount of allocating for controlling petroleum coke is that C/O ratios (mol ratio of fixed carbon and oxygen in copper tailings in petroleum coke) are
(1.2~1.5)：1.
Wherein, copper tailings is the tailings that copper smelting slag obtains after flotation and recovery of copper.The water content of copper tailings be 10~
12wt%.The mass content of sulphur is 0.2~0.5% in copper tailings.The preferred Behavior of High-sulfur Petroleum Coke of petroleum coke, the wherein mass content of sulphur >=
3%.
In various embodiments, the carbon raw material that other sulfur-bearings can be selected replaces petroleum coke.
B, the reduction roasting of compound and germanic lignite
Feed the mixture into and reduction roasting is carried out in rotary kiln baking device, sprayed in roasting process via germanic lignite entrance
Blow germanic lignite to be burnt, heat is provided for the reducing roasting process of material, obtain reducing material and containing zinc, lead, germanium
Flue dust.The temperature of reduction roasting is 1300~1400 DEG C, and the time is 30~60min.
Wherein, the degree of metalization of reducing material is 80~90%, and is gone back via what is set at rotary kiln baking device kiln hood
Raw material outlet discharge.Flue dust is expelled in cloth bag via the flue dust outlet at kiln tail.Zinc from Flue Dust grade >=50%, lead grade
>=10%, germanium grade >=5%.Also, the equal ＞ 90% of the rate of recovery of Zinc from Flue Dust, lead, germanium.
In compound, dolomite adds the reduction that can promote metallic compound in copper tailings as fluxing agent.It is also, white
Contain dystectic MgO in marble, further can prevent low-melting-point material from generating, reduce the risk of rotary kiln baking device ring formation.
In reducing roasting process, the principle of germanic lignite and copper tailings comprehensive utilization is：In reducing roasting process, to return
It is blown germanic lignite in rotary kiln calcination device to be burnt, heat caused by burning is used for reducing roasting process.It is meanwhile germanic brown
Coal ash can be produced after coal combustion, coal ash continues to mix with reducing material.In reducing roasting process, the ferrosilite in copper tailings is by stone
Oil coke is reduced into metallic iron, and lead zinc in copper tailings etc. is then reduced into metallic state, and is evaporated in gaseous state, constantly produces also
Originality atmosphere.Meanwhile the germanium in coal ash is in the presence of reducing atmosphere and sulphur (sulphur in sulphur and petroleum coke in copper tailings),
Generate GeO, GeSxAnd evaporate in a gaseous form, and as the lead of volatilization, zinc flow to kiln tail, be flowed into cloth bag and received
Collection.Because the sulfide and low oxide of germanium have higher vapour pressure at a lower temperature, such as in 977K,
GeS vapour pressure is 1386Pa；During 956K, GeS2Vapour pressure be 380Pa；During 1196K, GeO vapour pressure is 1662.5Pa.
Also, the sulfide and low oxide of germanium are in neutral or weakly reducing atmosphere, easily distillation volatilization at a lower temperature.
C, in reducing material iron recovery
The reducing material that above-mentioned steps obtain is sent into mill ore magnetic selection device and carries out mill ore magnetic selection, obtains iron powder and by-product
Thing mill selects tailings.Iron grade >=90% of iron powder, the rate of recovery >=80% of iron.
Wherein, iron powder is used as steelmaking feed after briquetting, and mill selects tailings as the raw material for preparing building materials.
D, flue dust leaches
The flue dust containing zinc, lead, germanium that step B is obtained is sent into leaching device, and adds the concentrated sulfuric acid, can be by flue dust
In zinc, lead, germanium leach, and obtain the leachate containing zinc sulfate and Ge(SO).Meanwhile it can also obtain lead sulfate residue.Leaching
During going out, it is 90~98 DEG C to control temperature in leaching device, and beginning acid concentration be 120~150g/L, whole acid concentration for 40~
60g/L.Wherein, zinc, the leaching rate of lead reach more than 98%, and the leaching rate of germanium reaches more than 92%.
E, the heavy germanium of leachate hydrolysis
Leachate containing zinc sulfate and Ge(SO) is sent into hydrolysis device, and adds high purity water and is hydrolyzed, is obtained
Germanium dioxide.Wherein, the ratio of high purity water and leachate is：The mol ratio of hydrone and germanium ion in leachate is in high purity water
1.5~2:1, Ge(SO) can be fully hydrolyzed by high purity water, obtain germanium dioxide.In hydrolytic process, it can obtain using high purity water pure
The higher germanium dioxide product of degree.
Also, leachate can also obtain solution of zinc sulfate after hydrolysis process, it is molten that solution of zinc sulfate is sent into the first electrolysis
In ingot device, through electrolysis, melted ingot processing, zinc ingot metal is obtained.
Further, lead sulfate residue flue dust leaching process obtained is sent into the second electrolysis melted ingot device, through being electrolysed,
Melted ingot processing, obtains lead pig.
Melted ingot process in the utility model includes fusing, ingot casting processing procedure, also, electrolysis of the present utility model, molten
Change, ingot casting processing procedure selects common process.
Embodiment 1
Copper tailings, petroleum coke, dolomite are 100 according to mass ratio：20：5 dispensings, obtain water content after well mixed and be less than
8wt% compound.Wherein, sulfur content is 0.2wt%, water content 10wt% in copper tailings.Petroleum coke is high sulfur petroleum coke,
Its sulfur content is 5wt%.
Feed the mixture into rotary kiln baking device, and be blown germanic lignite thereto.Ge content in germanic lignite
For 10g/t.Reduction roasting reaction occurs in rotary kiln baking device for compound and germanic lignite, and sintering temperature is 1300 DEG C,
Roasting time is 60min.Reduction roasting obtains reducing material and flue dust.Wherein, the degree of metalization of reducing material is 80%, flue dust
Middle zinc grade is 50%, and lead grade is 10%, and germanium grade is 10%, also, the rate of recovery of zinc, lead, germanium is all higher than 90%.
Reducing material is sent into mill ore magnetic selection device and carries out mill ore magnetic selection, obtains Iron grade 90%, iron recovery 80%
Iron powder, and accessory substance mill select tailings.
Flue dust, which is sent into leaching device, uses sulfuric acid leaching, and temperature is 98 DEG C, and beginning acid concentration is 150g/L, and whole acid concentration is
60g/L.Zinc, the leaching rate of lead are 98.5%, and the leaching rate of germanium is 93%.Contain zinc sulfate and sulfuric acid in obtained leachate
Germanium, contain lead sulfate in residue.
Residue obtains lead pig through electrolysis, melted ingot.Leachate is sent into hydrolysis device and adds high purity water and is hydrolyzed, and obtains
To germanium dioxide.The mol ratio of hydrone and germanium ion in leachate is 1.5 in high purity water：1.The zinc sulfate that hydrolytic process obtains
Solution is electrolysed, melted ingot, obtains zinc ingot metal.
Embodiment 2
Copper tailings, petroleum coke, dolomite are 100 according to mass ratio：25：8 dispensings, obtain water content after well mixed and be less than
8wt% compound.Wherein, sulfur content is 0.4wt%, water content 11wt% in copper tailings.Petroleum coke is high sulfur petroleum coke,
Its sulfur content is 4wt%.
Feed the mixture into rotary kiln baking device, and be blown germanic lignite thereto.Ge content in germanic lignite
For 5g/t.Reduction roasting reaction occurs in rotary kiln baking device for compound and germanic lignite, and sintering temperature is 1350 DEG C, roasting
The burning time is 40min.Reduction roasting obtains reducing material and flue dust.Wherein, the degree of metalization of reducing material is 85%, in flue dust
Zinc grade is 55%, and lead grade is 10%, and germanium grade is 8%, also, the rate of recovery of zinc, lead, germanium is all higher than 90%.
Reducing material is sent into mill ore magnetic selection device and carries out mill ore magnetic selection, obtains Iron grade 91%, iron recovery 84%
Iron powder, and accessory substance mill select tailings.
Flue dust, which is sent into leaching device, uses sulfuric acid leaching, and temperature is 95 DEG C, and beginning acid concentration is 130g/L, and whole acid concentration is
50g/L.Zinc, the leaching rate of lead are 98%, and the leaching rate of germanium is 92.5%.Contain zinc sulfate and sulfuric acid in obtained leachate
Germanium, contain lead sulfate in residue.
Residue obtains lead pig through electrolysis, melted ingot.Leachate is sent into hydrolysis device and adds high purity water and is hydrolyzed, and obtains
To germanium dioxide.The mol ratio of hydrone and germanium ion in leachate is 1.8 in high purity water：1.The zinc sulfate that hydrolytic process obtains
Solution is electrolysed, melted ingot, obtains zinc ingot metal.
Embodiment 3
Copper tailings, petroleum coke, dolomite are 100 according to mass ratio：30：10 dispensings, it is low to obtain water content after well mixed
In 8wt% compound.Wherein, sulfur content is 0.5wt%, water content 12wt% in copper tailings.Petroleum coke is high-sulfur oil
Jiao, its sulfur content are 3wt%.
Feed the mixture into rotary kiln baking device, and be blown germanic lignite thereto.Ge content in germanic lignite
For 0.5g/t.Reduction roasting reaction occurs in rotary kiln baking device for compound and germanic lignite, and sintering temperature is 1400 DEG C,
Roasting time is 30min.Reduction roasting obtains reducing material and flue dust.Wherein, the degree of metalization of reducing material is 90%, flue dust
Middle zinc grade is 60%, and lead grade is 10%, and germanium grade is 5%, also, the rate of recovery of zinc, lead, germanium is all higher than 90%.
Reducing material is sent into mill ore magnetic selection device and carries out mill ore magnetic selection, obtains Iron grade 92%, iron recovery 88%
Iron powder, and accessory substance mill select tailings.
Flue dust, which is sent into leaching device, uses sulfuric acid leaching, and temperature is 90 DEG C, and beginning acid concentration is 120g/L, and whole acid concentration is
40g/L.Zinc, the leaching rate of lead are 98%, and the leaching rate of germanium is 92%.Contain zinc sulfate and Ge(SO) in obtained leachate,
Contain lead sulfate in residue.
Residue obtains lead pig through electrolysis, melted ingot.Leachate is sent into hydrolysis device and adds high purity water and is hydrolyzed, and obtains
To germanium dioxide.The mol ratio of hydrone and germanium ion in leachate is 2 in high purity water：1.The zinc sulfate that hydrolytic process obtains is molten
Liquid is electrolysed, melted ingot, obtains zinc ingot metal.
Finally it should be noted that：Obviously, above-described embodiment is only intended to clearly illustrate the utility model example,
And the restriction not to embodiment.For those of ordinary skill in the field, may be used also on the basis of the above description
To make other changes in different forms.There is no necessity and possibility to exhaust all the enbodiments.And thus
Among the obvious changes or variations amplified out is still in the scope of protection of the utility model.
Claims (4)
1. a kind of system for handling germanic lignite and copper tailings, it is characterised in that the system includes mixing arrangement, rotary kiln roasts
Burn device, mill ore magnetic selection device, leaching device, hydrolysis device；
The mixing arrangement has copper tailings entrance, petroleum coke entrance, dolomite entrance, compound outlet；
The rotary kiln baking device has compound entrance, germanic lignite entrance, reducing material outlet, flue dust outlet；It is described
The compound outlet of compound entrance and the mixing arrangement connects；
There is the mill ore magnetic selection device reducing material entrance, iron powder outlet, mill to select tailings to export；The reducing material entrance with
The reducing material outlet connection of the rotary kiln baking device；
The leaching device has flue dust entrance, concentrated sulfuric acid entrance, leachate outlet, lead sulfate solid discharge；The flue dust enters
The flue dust of mouth and the rotary kiln baking device, which exports, to be connected；
The hydrolysis device has leachate entrance, high-purity water inlet, germanium dioxide outlet, solution of zinc sulfate outlet；The leaching
The leachate outlet for going out liquid entrance and the leaching device connects.
2. system according to claim 1, it is characterised in that be provided with cloth at the kiln tail of the rotary kiln baking device
Bag, for collecting flue dust.
3. system according to claim 1, it is characterised in that also including the first electrolysis melted ingot device, have zinc sulfate molten
Liquid entrance, zinc ingot metal outlet；The solution of zinc sulfate outlet of the solution of zinc sulfate entrance and the hydrolysis device connects.
4. system according to claim 1, it is characterised in that also including the second electrolysis melted ingot device, have lead sulfate residual
Slag entrance, lead pig outlet；The lead sulfate residue entrance is connected with the lead sulfate solid discharge of the leaching device.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201720594366.5U CN206828588U (en) | 2017-05-25 | 2017-05-25 | A kind of system for handling germanic lignite and copper tailings |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201720594366.5U CN206828588U (en) | 2017-05-25 | 2017-05-25 | A kind of system for handling germanic lignite and copper tailings |
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| Publication Number | Publication Date |
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| CN206828588U true CN206828588U (en) | 2018-01-02 |
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ID=60772876
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| CN201720594366.5U Expired - Fee Related CN206828588U (en) | 2017-05-25 | 2017-05-25 | A kind of system for handling germanic lignite and copper tailings |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107058722A (en) * | 2017-05-25 | 2017-08-18 | 江苏省冶金设计院有限公司 | A kind of system and method for handling germanic lignite and copper tailings |
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2017
- 2017-05-25 CN CN201720594366.5U patent/CN206828588U/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107058722A (en) * | 2017-05-25 | 2017-08-18 | 江苏省冶金设计院有限公司 | A kind of system and method for handling germanic lignite and copper tailings |
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