CN105907979A - Method for enriching germanium from lignite flue dust - Google Patents
Method for enriching germanium from lignite flue dust Download PDFInfo
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- CN105907979A CN105907979A CN201610252445.8A CN201610252445A CN105907979A CN 105907979 A CN105907979 A CN 105907979A CN 201610252445 A CN201610252445 A CN 201610252445A CN 105907979 A CN105907979 A CN 105907979A
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- germanium
- flue dust
- dust
- calx
- heating furnace
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/02—Working-up flue dust
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B41/00—Obtaining germanium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/001—Dry processes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
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- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a method for enriching germanium from lignite flue dust. The method comprises the following steps: 1, mixing lignite flue dust with coal powder and lime, and granulating the obtained mixture to obtain material particles; and 2, putting the material particles in a heating furnace, carrying out reducing volatilization at 1200-1500DEG C in reducing atmosphere in the heating furnace for 2-18h, and collecting dusts to obtain a germanium-rich material. The method greatly reduces the acid consumption in the subsequent wet treatment process of germanium concentrate, avoids discharge and treatment of a large amount of wastewater and waste residues, reduces the device size, and reduces the investment cost.
Description
Technical field
The present invention relates to coloured rare metal extractive technique field, in particular to a kind of side of enriched germanium from brown coal flue dust
Method.
Background technology
Germanium, as a kind of dissipated metal, is widely used in quasiconductor, electronics and optics.But, along with the use of germanium
Amount is continuously increased, and in global range, germanium resource is the most rare.
Germanium metal does not has single mineral reserve in nature, and main association is in germanic brown coal and sphalerite.At present, China is from containing
In germanium brown coal, Ti recovery mainly uses the cyclone furnaces technique that overheavy firing is volatilized, and is enriched in flue dust by germanium, then enters from flue dust
One step proposes germanium.From germanium-containing smoke dust, extract germanium mostly use chlorinated distillation technique, owing to germanium oxide dust grade is low, need to consume greatly
The hydrochloric acid of amount, tail gas absorption liquid also needs to consume the adjuvants such as large quantities of lime.Additionally, bottoms also need to carry out secondary pyrogenic process recovery,
Serious to equipment corrosion, the response rate is low.
Chinese patent " a kind of reclaim the method for germanium in brown coal flue dust " (patent No. CN104911363A) disclose a kind of utilize true
Empty reduction-chlorinated distillation technology reclaims the method for germanium in brown coal flue dust, and it is to be put together with the coke of 5-25wt% by brown coal flue dust
In vacuum furnace, at 800-1000 DEG C, carry out vacuum reduction reaction, obtain product Ge on metal, GeO and some
Impurity such as As2O3Condensed product；Then, condensed product is used chlorinated distillation, obtains pure GeCl4, its purity is 90%
Above；Then, GeCl4Hydrolysis, obtain the pure GeO of product2.But, in germanium oxide dust, germanium the most individually becomes phase, and
It is main and SiO2Combine with the oxide such as CaO and form complex compound.In germanium oxide dust, the occurrence form of germanium is directly determined
Its volatilizing and enriching technique fixed.This will be unfavorable for the direct-reduction volatilizing and enriching of germanium under lower temperature.
Summary of the invention
It is desirable to provide a kind of method of enriched germanium from brown coal flue dust, to reduce follow-up chlorinated distillation disappearing in a large number to hydrochloric acid
Consumption, avoids a large amount of waste water and the discharge of waste residue and process simultaneously, reduces cost of investment.
To achieve these goals, according to an aspect of the invention, it is provided a kind of method of enriched germanium from brown coal flue dust.
The method comprises the following steps: S1, pelletize after being mixed with fine coal and Calx by brown coal flue dust, obtains material particles；S2, will
Material particles puts into heating furnace, is reducing atmosphere in controlling heating furnace, and temperature is 1200～1500 DEG C, reduction volatilization 2～18h,
Gather dust and obtain germanium enrichment material.
Further, brown coal flue dust, fine coal, the mass ratio of Calx are 1:0.2～1:0.1～0.5.
Further, also include after being mixed with fine coal and Calx by brown coal flue dust the mixture obtained after mixing is crushed to 30～80
Purpose step.
Further, in S1, the granularity of pelletize is 12～18mm.
Further, heating furnace is closed electric furnace.
Application technical scheme, first by low-grade germanium-containingpowdery coal smoke dirt and fine coal, Calx mixing granulation, places into heating
In stove, it is reducing atmosphere in controlling heating furnace, temperature 1200～1500 DEG C, the time 2～18h, carry out reduction volatilization, in this condition
Under, the germanium in low-grade germanium-containingpowdery flue dust is volatized into gas phase with the form of germanium monoxide, then is collected by dust arrester installation, obtains germanium
The enrichment material that content is high.Use the present invention can be substantially reduced subsequent wet and process germanium concentrate acid consumption, it is to avoid a large amount of waste water and waste residue
Discharge and process, reduce equipment scale and reduce cost of investment.
Accompanying drawing explanation
The Figure of description of the part constituting the application is used for providing a further understanding of the present invention, and the present invention's is schematic real
Execute example and illustrate for explaining the present invention, being not intended that inappropriate limitation of the present invention.In the accompanying drawings:
Fig. 1 shows the schematic flow sheet of the method for enriched germanium from brown coal flue dust according to embodiments of the present invention.
Detailed description of the invention
It should be noted that in the case of not conflicting, the embodiment in the application and the feature in embodiment can be mutually combined.
Describe the present invention below with reference to the accompanying drawings and in conjunction with the embodiments in detail.
According to a kind of typical embodiment of the present invention, it is provided that a kind of method of enriched germanium from brown coal flue dust.The method include with
Lower step: S1, pelletize after brown coal flue dust is mixed with fine coal and Calx, obtain material particles；S2, puts into material particles and adds
In hot stove, being reducing atmosphere in controlling heating furnace, temperature is 1200～1500 DEG C, reduction volatilization 2～18h, gathers dust and obtains germanium enrichment
Material.
Wherein, fine coal Main Function is that the carbon monoxide of heat and the generation utilizing pulverized coal friring to be discharged makees reducibility gas, can
By regulation fine coal charge ratio, to control as weakly reducing atmosphere condition, it is to avoid the germanium dioxide in germanium oxide dust is reduced to germanium metal.
The addition of Calx primarily serves regulation slag type, reduces the effect of slag temperature.
Application technical scheme, first by low-grade germanium-containingpowdery coal smoke dirt and fine coal, Calx mixing granulation, places into heating
In stove, it is weakly reducing atmosphere in controlling heating furnace, temperature 1200～1500 DEG C, the time 2～18h, carry out reduction volatilization, at this
Under part, the germanium in low-grade germanium-containingpowdery flue dust is volatized into gas phase with the form of germanium monoxide, then is collected by dust arrester installation, obtains
The enrichment material that Ge content is high.Use the present invention can be substantially reduced subsequent wet and process germanium concentrate acid consumption, it is to avoid a large amount of waste water are with useless
The discharge of slag and process, reduce equipment scale and reduce cost of investment.
Preferably, brown coal flue dust, fine coal, the mass ratio of Calx are 1:0.2～1:0.1～0.5.
According to a kind of typical embodiment of the present invention, also include after being mixed with fine coal and Calx by brown coal flue dust obtaining after mixing
Mixture be crushed to the step of 30～80 mesh.Particle diameter is excessive is unfavorable for being fully contacted of brown coal flue dust and fine coal and Calx, particle diameter
Cross detailed rules and regulations and can increase comminution energy conssumption.Accordingly, it would be desirable to control the particle diameter of fine coal and Calx at optimum range.Preferably, pelletize in S1
Granularity be 12～18mm.Granularity is excessive or the too small volatility that all can cause germanium declines.When pellet size is excessive, along with instead
The carrying out answered, reaction product layer progressive additive, the resistance of interior external diffusion increases, can not be fully contacted with CO inside pelletizing, internal
GeO2Can not be reduced sufficiently and evaporate；Undersized then causes loss of material possibly into flue dust.According to the present invention
A kind of typical embodiment, in S2 during reduction volatilization, material at high temperature melts, by C-O reaction, CO
The floating of bubble, makes molten bath produce fierceness boiling, accelerates germanium and the reaction of carbon monoxide in germanium oxide dust so that an oxidation of generation
Germanium can quickly volatilize into gas phase.
Preferably, heating furnace is closed electric furnace.With traditional rotary kiln, vertical Rotary Kiln and the Rotary Kiln of microwave heating
Comparing, the present invention uses closed electric furnace to be remarkably improved evaporation rate of germanium.
According to a kind of typical embodiment of the present invention, the method includes same for germanium-containing smoke dust fine coal, Calx mixed by certain mass ratio
Conjunction is crushed to 30～80 mesh, makes the bead of granularity 12～18mm on disk pelletizing machine；Join in closed electric furnace, weak
In reducing atmosphere, under the conditions of 1200～1500 DEG C, react 2～18h；By adjusting electrode strengthening stirring intensity of molten pool, accelerate germanium oxide dust
Middle germanium and the reaction of carbon monoxide so that the germanium monoxide of generation can quickly volatilize into gas phase；It is cold that germanic flue gas enters dust-precipitator
But gather dust, obtain germanium enrichment material.
Beneficial effects of the present invention is further illustrated below in conjunction with embodiment.
Embodiment 1
With reference to the flow process of Fig. 1, with germanium-containing smoke dust as raw material, it is mainly composed of SiO235%, Fe15%, Al2O312%, CaO12%,
Ge0.8%, mixs homogeneously according to the quality ratio of 1:0.5:0.15 with fine coal, Calx, crushing and screening, and Control granularity is 50 mesh, then
By disk pelletizing machine pelletizing, it is thus achieved that the bead of a diameter of 15mm, sending in closed electric furnace, it is 1200 DEG C that temperature controls, and maintains
Temperature 4h, period reinforcement melting bath stirring, flue gas introduces electricity by the exhaust outlet of closed electric furnace upper end by cooling and gathers dust and cloth bag receipts
Dirt, containing Ge5.1% in dust collection powder, germanium concentration ratio 6 times, the response rate 92%.
Embodiment 2
With germanium-containing smoke dust as raw material, it is mainly composed of SiO235%, Fe15%, Al2O312%, CaO12%, Ge1%, with powder
Coal, Calx are 50 mesh according to the quality of 1:0.2:0.1 than mix homogeneously, crushing and screening, Control granularity, then make with disk pelletizing machine
Ball, it is thus achieved that the bead of a diameter of 15mm, sends in closed electric furnace, and it is 1350 DEG C that temperature controls, and maintains temperature 4h, and period adds
Strong melting bath stirring, flue gas introduces electricity by the exhaust outlet of closed electric furnace upper end by cooling and gathers dust and bag collection, contains in dust collection powder
Ge4.1%, germanium concentration ratio 4.1 times, the response rate 90.5%.
Embodiment 3
With germanium-containing smoke dust as raw material, it is mainly composed of SiO230%, Fe13%, Al2O311%, CaO10%, Ge0.5%, with powder
Coal, Calx are 80 mesh according to the quality of 1:0.2:0.15 than mix homogeneously, crushing and screening, Control granularity, then use disk pelletizing machine
Pelletizing, it is thus achieved that the bead of a diameter of 12mm, sends in closed electric furnace, and it is 1450 DEG C that temperature controls, and maintains temperature 8h, period
Strengthening melting bath stirring, flue gas introduces electricity by the exhaust outlet of closed electric furnace upper end by cooling and gathers dust and bag collection, in dust collection powder
Containing Ge5.3%, germanium concentration ratio 10.6 times, the response rate 88.3%.
Embodiment 4
With germanium-containing smoke dust as raw material, it is mainly composed of SiO240%, Fe10%, Al2O314%, CaO12%, Ge0.6%, with powder
Coal, Calx are 80 mesh according to the quality of 1:1:0.5 than mix homogeneously, crushing and screening, Control granularity, then by disk pelletizing machine pelletizing,
Obtaining the bead of a diameter of 12mm, send in closed electric furnace, it is 1500 DEG C that temperature controls, and maintains temperature 10h, and period is strengthened
Melting bath stirring, flue gas introduces electricity by the exhaust outlet of closed electric furnace upper end by cooling and gathers dust and bag collection, contains in dust collection powder
Ge6.2%, germanium concentration ratio 10.3 times, the response rate 93.5%.
As can be seen from the above description, the above embodiments of the present invention achieve following technique effect:
In germanium flue dust germanic generally 0.5～1.2%, use technical scheme to carry out reduction volatilization, germanic 3～5% can be obtained
Rich germanium material, germanium is enriched 10 times, and the response rate of germanium reaches 85～94%, and rich germanium material directly can extract germanium with salt acid distillation further.
Using technical scheme, simply, easily operate, the germanium volatilization response rate is high for technique.The method utilizing the present invention, no
But can enriched germanium further, and a large amount of consumption to hydrochloric acid of the follow-up chlorinated distillation can be substantially reduced, avoid a large amount of waste water simultaneously
Discharge with waste residue and process, reduce cost of investment.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for those skilled in the art
For, the present invention can have various modifications and variations.All within the spirit and principles in the present invention, any amendment of being made, etc.
With replacement, improvement etc., should be included within the scope of the present invention.
Claims (5)
1. the method for enriched germanium from brown coal flue dust, it is characterised in that comprise the following steps:
S1, pelletize after brown coal flue dust is mixed with fine coal and Calx, obtain material particles；
S2, puts into heating furnace by described material particles, is reducing atmosphere in controlling described heating furnace, and temperature is
1200～1500 DEG C, reduction volatilization 2～18h, gather dust and obtain germanium enrichment material.
Method the most according to claim 1, it is characterised in that described brown coal flue dust, described fine coal, the quality of described Calx
Ratio is 1:0.2～1:0.1～0.5.
Method the most according to claim 1, it is characterised in that also include after described brown coal flue dust is mixed with fine coal and Calx
The mixture obtained after mixing is crushed to the step of 30～80 mesh.
Method the most according to claim 1, it is characterised in that in described S1, the granularity of pelletize is 12～18mm.
Method the most according to claim 1, it is characterised in that described heating furnace is closed electric furnace.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610252445.8A CN105907979A (en) | 2016-04-21 | 2016-04-21 | Method for enriching germanium from lignite flue dust |
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| CN201610252445.8A CN105907979A (en) | 2016-04-21 | 2016-04-21 | Method for enriching germanium from lignite flue dust |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106801151A (en) * | 2017-01-22 | 2017-06-06 | 中国恩菲工程技术有限公司 | The method of flyash reduction melting enriched germanium |
| CN108504874A (en) * | 2018-05-03 | 2018-09-07 | 广东省稀有金属研究所 | A method of pressing separating Ge gallium in wet method replacement slag from zinc oxygen |
| CN109402409A (en) * | 2018-11-29 | 2019-03-01 | 广东省稀有金属研究所 | A method of the enriched germanium from germanic lignite cigarette ash |
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| CN101186975A (en) * | 2007-12-26 | 2008-05-28 | 锡林郭勒通力锗业有限责任公司 | Method for extracting germanium from brown coal |
| CN101831563A (en) * | 2010-05-12 | 2010-09-15 | 云南天浩稀贵金属股份有限公司 | Method for gathering and recovering indium and germanium from indium and germanium containing material by using one-step method |
| CN104862488A (en) * | 2015-04-28 | 2015-08-26 | 内蒙古科技大学 | High-temperature fire method secondary enriching method of germanium-contained dust electric arc furnace |
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2016
- 2016-04-21 CN CN201610252445.8A patent/CN105907979A/en active Pending
Patent Citations (3)
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| CN101186975A (en) * | 2007-12-26 | 2008-05-28 | 锡林郭勒通力锗业有限责任公司 | Method for extracting germanium from brown coal |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106801151A (en) * | 2017-01-22 | 2017-06-06 | 中国恩菲工程技术有限公司 | The method of flyash reduction melting enriched germanium |
| CN106801151B (en) * | 2017-01-22 | 2019-05-07 | 中国恩菲工程技术有限公司 | The method of flyash reduction melting enriched germanium |
| CN108504874A (en) * | 2018-05-03 | 2018-09-07 | 广东省稀有金属研究所 | A method of pressing separating Ge gallium in wet method replacement slag from zinc oxygen |
| CN108504874B (en) * | 2018-05-03 | 2019-10-18 | 广东省稀有金属研究所 | A method of the separating Ge gallium from zinc oxygen pressure wet process replacement slag |
| CN109402409A (en) * | 2018-11-29 | 2019-03-01 | 广东省稀有金属研究所 | A method of the enriched germanium from germanic lignite cigarette ash |
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Application publication date: 20160831 |