CN106801151A - The method of flyash reduction melting enriched germanium - Google Patents
The method of flyash reduction melting enriched germanium Download PDFInfo
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- CN106801151A CN106801151A CN201710047580.3A CN201710047580A CN106801151A CN 106801151 A CN106801151 A CN 106801151A CN 201710047580 A CN201710047580 A CN 201710047580A CN 106801151 A CN106801151 A CN 106801151A
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- arsenic
- germanium
- germanic
- flyash
- leaching
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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
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/14—Agglomerating; Briquetting; Binding; Granulating
- C22B1/24—Binding; Briquetting ; Granulating
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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
- C22B30/00—Obtaining antimony, arsenic or bismuth
- C22B30/04—Obtaining arsenic
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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
Abstract
The invention discloses a kind of enrichment method of germanium in flyash, the method includes：(1) flyash, lime stone, iron ore are carried out into mix, to obtain mixed material；(2) mixed material is added water granulation, to obtain mixing pelletizing；(3) by fine coal, the mixing pelletizing is delivered in fuming furnace carries out reduction melting, to obtain germanic flue gas and smelting slag；(4) the germanic flue gas is sequentially passed through into waste heat recovery and cooling and purifying treatment, to obtain flue gas and germanic arsenic flue dust；(5) by the germanic arsenic flue dust by Oxidation Leaching, to obtain germanium slag and arsenic leaching solution；(6) by the arsenic leaching solution through evaporating, filtering, dry, to obtain industrial white arsenic.The method has that flyash disposal ability is big, flue dust Ge content high, cycle is short, the low advantage of energy consumption, and the germanium arsenic volatility in flyash is up to more than 99%；Germanic arsenic soot oxidation is leached and is capable of achieving the separation of germanium arsenic, and Ge content reaches more than 12% in germanium slag.
Description
Technical field
The invention belongs to field of metallurgy, specifically, the present invention relates to a kind of method of flyash reduction melting enriched germanium.
Background technology
Dissipated metal germanium acts on increasingly important in national economy, and the main association of germanium is in germanic lignite and zincblende.In
State's germanic coal rich reserves, but content is extremely low, it is widely distributed, it is difficult to high efficiency extraction germanium.In China, germanic lignite is mainly used in
Cyclone smelting is generated electricity, and most germanium are enriched in flyash in combustion.
It is high for prepared by potassium cloride-distillation-hydrolysis-reduction-zone refining that the classical wet method of current flyash puies forward germanium flow
Pure germanium.But Ge content is very low in flyash, only 0.5% or so, direct wet method carries germanium and there is reagent consumption greatly, high cost；
Environmental protection pressure is big, and the waste residue of generation, wastewater flow rate are big, high containing arsenic, it is difficult to the problems such as processing；
Germanic lignite cyclone smelting is generated electricity and classical wet method carries germanium for mature technology, and system upgrade is carried out to the two technologies
, there is high cost, technical difficulty in transformation.The embedded fine coal between germanium coal power generation and wet method carry two modular units of germanium
The secondary enriched germanium module of ash, can reduce reagent consumption, three wastes minimizing.
Therefore, it is existing to be further improved from coal ash lifting germanium technologies.
The content of the invention
It is contemplated that at least solving one of technical problem in correlation technique to a certain extent.Therefore, of the invention
One purpose is the enrichment method for proposing germanium in a kind of flyash, and the method reduction melting enriched germanium operation has at flyash
Reason ability is big, flue dust Ge content high, cycle is short, the low advantage of energy consumption, and the germanium arsenic volatility in flyash is up to more than 99%；It is germanic
Arsenic flue dust can realize that germanium arsenic is separated using hot water oxidation dearsenic technique, and Ge content reaches more than 12% in gained germanium slag.
In one aspect of the invention, the present invention proposes a kind of enrichment method of germanium in flyash.It is of the invention
Embodiment, methods described includes：
(1) flyash, lime stone, iron ore are carried out into mix, to obtain mixed material；
(2) mixed material is added water granulation, to obtain mixing pelletizing；
(3) the mixing pelletizing is supplied to fuming furnace, by fine coal by spray gun Geldart-D particle to the fuming furnace with
The mixing pelletizing carries out reduction melting, to obtain germanic flue gas and smelting slag；
(4) the germanic flue gas is sequentially passed through into waste heat recovery and cooling and purifying treatment, to obtain flue gas and germanic arsenic
Flue dust；
(5) by the germanic arsenic flue dust through superheated water Oxidation Leaching, to obtain high-grade germanium slag and arsenic leaching solution；
(6) arsenic leaching solution is dried through evaporation and concentration, centrifugal filtration, blade, to obtain industrial white arsenic.
Thus, in flyash according to embodiments of the present invention the enrichment method of germanium by by flyash and lime stone, iron ore
Stone carries out mix, is conducive to Fe and SiO in control mixed material2Mass ratio and CaO and SiO2Mass ratio, so may be used
Realize that follow-up mixing pelletizing carries out having good fusing and mobile performance during reduction melting in fuming furnace.Mixed material adds water and makes
Grain, makes pelletizing possess certain drop strength and hardness, it is ensured that will not be crushed during charging.In fuming furnace, fine coal conduct
Reducing agent and fuel, by spray gun Geldart-D particle to fuming furnace, and burning forms certain reducing atmosphere in fuming furnace.Fine coal
Germanium exists in germanium dioxide form in ash, difficult volatile oxidn.Under the conditions of fuming furnace high temperature reducing atmosphere, dioxy
Change germanium and generate germanium monoxide with reaction of carbon monoxide, diarsenic pentoxide generates low price arsenic trioxide with reaction of carbon monoxide.One
Germanium oxide and arsenic trioxide have volatile feature, while in the presence of spray gun compressed air, molten bath in fuming furnace
Strong agitation is formed, the volatilization of germanium and arsenic can be strengthened, improve the volatilization efficiency of germanium and arsenic.After reduction melting, smelting slag
It is the harmless slag without arsenic, germanic flue gas obtains germanic arsenic flue dust through waste heat recovery and cooling dust collecting system.Germanic arsenic flue dust is adopted
Use Oxidation Leaching technology, water be insoluble in using germanium dioxide, and diarsenic pentoxide it is soluble in water the characteristics of, selectivity soaks arsenic
Go out, and germanium is stayed in slag；Arsenic leachate can produce industrial white arsenic after being concentrated by evaporation, filtering, dry.The germanium slag obtained after leaching is
High-grade germanium slag.In the method flyash reduction melting enriched germanium in fuming furnace have flyash disposal ability big, cycle is short,
The low advantage of energy consumption；The smelting slag that fuming furnace reduction melting is obtained is substantially free of germanium and arsenic, can be used as construction material, to greatest extent
Improve resource utilization.Germanic arsenic fume fever water Oxidation Leaching is concentrated to give industrial white arsenic, and the germanic grade of leached mud is high, flyash
Middle germanium is further enriched with.
In addition, the enrichment method of germanium can also have following additional skill in flyash according to the above embodiment of the present invention
Art feature：
In some embodiments of the invention, in step (1), the flyash is the germanic coal obtained after coal fired power generation
Cigarette ash.Thus, it is advantageously implemented the recycling of germanium resource in fly ash.
In some embodiments of the invention, in step (1), Fe and SiO in the mixed material2Mass ratio be
(0.5~1.1)：1, CaO and SiO2Mass ratio be (0.4~0.8)：1.Thus, can make material has relatively low fusing point, and tool
There are relatively low viscosity, preferable mobility.
In some embodiments of the invention, in step (2), the granularity of the mixing pelletizing is 10~15mm, described
The moisture for mixing pelletizing is not more than 10wt%.Thus, pelletizing can be made to possess certain drop strength and hardness, it is ensured that in charging process
In will not crush.
In some embodiments of the invention, in step (3), the temperature of the reduction melting is 1150~1350 Celsius
Degree, the time is 1-4h.Thus, can further improve the efficiency of reduction melting enriched germanium.
In some embodiments of the invention, in step (5), the oxidant is hydrogen peroxide.Thus, be conducive to germanic
The leaching of arsenic in arsenic flue dust.
In some embodiments of the invention, in step (5), the mass ratio of the hydrogen peroxide and the germanic arsenic flue dust
It is (0.5~1.5)：1.Thus, the leaching of arsenic in germanic arsenic flue dust can be further conducive to.
In some embodiments of the invention, in step (5), the leaching liquid-solid ratio of the hot water Oxidation Leaching process is
(5~20):1；Extraction temperature is 25~95 degrees Celsius, and extraction time is 1~3h.Thus, germanic arsenic cigarette can be further conducive to
The leaching of arsenic in dirt.
Additional aspect of the invention and advantage will be set forth in part in the description, and will partly become from the following description
Obtain substantially, or recognized by practice of the invention.
Brief description of the drawings
Of the invention above-mentioned and/or additional aspect and advantage will become from description of the accompanying drawings below to embodiment is combined
Substantially and be readily appreciated that, wherein：
Fig. 1 is the enrichment method schematic flow sheet of germanium in flyash according to an embodiment of the invention；
Fig. 2 is the CaO-FeO-SiO of the method for the flyash reduction melting enriched germanium according to further embodiment of the present invention2
Ternary inorganic solution；
Fig. 3 is the method flow schematic diagram of the flyash reduction melting enriched germanium according to another embodiment of the invention.
Specific embodiment
Embodiments of the invention are described below in detail, the example of the embodiment is shown in the drawings, wherein from start to finish
Same or similar label represents same or similar element or the element with same or like function.Below with reference to attached
It is exemplary to scheme the embodiment of description, it is intended to for explaining the present invention, and be not considered as limiting the invention.
In one aspect of the invention, the present invention proposes a kind of enrichment method of germanium in flyash, of the invention
Embodiment, the method includes：(1) flyash, lime stone, iron ore are carried out into mix, to obtain mixed material；(2)
Mixed material is added water granulation, to obtain mixing pelletizing；(3) mixing pelletizing is supplied to fuming furnace, fine coal is passed through into spray gun
In Geldart-D particle to fuming furnace with mix pelletizing and carry out reduction melting, to obtain germanic flue gas and smelting slag；(4) by germanic cigarette
Gas sequentially passes through waste heat recovery and cooling and purifying treatment, to obtain flue gas and germanic arsenic flue dust；(5) germanic arsenic flue dust is passed through
Hot water Oxidation Leaching, to obtain high-grade germanium slag and arsenic leaching solution；(6) by arsenic leaching solution through being concentrated by evaporation, being centrifuged
Filter, blade are dried, to obtain industrial white arsenic.Inventor has found, is matched somebody with somebody by the way that flyash and lime stone, iron ore are carried out into mixing
Material, is conducive to Fe and SiO in control mixed material2Mass ratio and CaO and SiO2Mass ratio, be so capable of achieving follow-up mixing
Pelletizing and fine coal carry out having good fusing and mobile performance during reduction melting in fuming furnace.By by the mixed material system of adding water
Ball, is conducive to improving the intensity and hardness of mixed material, it is ensured that will not be crushed during charging.Fine coal is used as reducing agent and combustion
Material, is medium Geldart-D particle to fuming furnace with compressed air.Germanium exists in germanium dioxide form in flyash, difficult volatility oxygen
Compound.Under the conditions of fuming furnace high temperature reducing atmosphere, germanium dioxide generates germanium monoxide, five oxidations with reaction of carbon monoxide
Two arsenic generate low price arsenic trioxide with reaction of carbon monoxide.Germanium monoxide and arsenic trioxide have volatile feature, together
When in the presence of spray gun compressed air, in fuming furnace molten bath formed strong agitation, the volatilization of germanium and arsenic can be strengthened, improve
The volatilization efficiency of germanium and arsenic.After reduction melting, smelting slag is the harmless slag without arsenic, and germanic flue gas is through waste heat recovery and cold
But dust collecting system, obtains germanic arsenic flue dust.Germanic arsenic flue dust uses Oxidation Leaching technology, and water is insoluble in using germanium dioxide, and
The characteristics of diarsenic pentoxide is soluble in water, selectivity leaches arsenic, and germanium is stayed in slag；Arsenic leachate through be concentrated by evaporation, filtering,
Industrial white arsenic can be produced after drying.The germanium slag obtained after leaching is high-grade germanium slag.
The enrichment method of germanium is described in detail in flyash below with reference to Fig. 1 to the embodiment of the present invention.According to this hair
Bright embodiment, the method includes：
S100：Flyash, lime stone, iron ore are carried out into mix
In the step, flyash, lime stone, iron ore are carried out into mix, to obtain mixed material.Invention human hair
It is existing, mix is carried out by by flyash and lime stone, iron ore, be conducive to Fe and SiO in control mixed material2Quality
Than with CaO and SiO2Mass ratio, be so capable of achieving follow-up mixing pelletizing carries out having relatively low during reduction melting in fuming furnace
Fusing point and preferable mobile performance.
According to one embodiment of present invention, flyash is not particularly restricted, and those skilled in the art can be according to reality
Border needs to be selected, a specific embodiment of the invention, and flyash is the germanic coal obtained after coal-fired Whirl pool electric generation
Cigarette ash.Thus, it is advantageously implemented the recycling of resource.
According to still another embodiment of the invention, Fe and SiO in mixed material2Mass ratio, CaO and SiO2Mass ratio
It is not particularly restricted, those skilled in the art can be selected according to actual needs, one of the invention specific real
Example is applied, Fe and SiO in mixed material2Mass ratio can be (0.5~1.1)：1, CaO and SiO2Mass ratio can be (0.4
~0.8)：1.Inventor has found, according to CaO-FeO-SiO2Ternary inorganic solution (refers to Fig. 2), near fayalite (2FeO
SiO2, 1208 degrees Celsius of fusing point) plagioclase region in, i.e., Fe and SiO in mixed material2Mass ratio be (0.5~1.1)：1,
CaO and SiO2Mass ratio be (0.4~0.8)：In 1 regional extent, mix the fusing point of pelletizing can control 1150~
1350 degrees Celsius, namely ensure that follow-up mixing pelletizing and the fine coal melt in the range of 1150~1350 degrees Celsius has good
Mobility.Be conducive to improving the volatilization efficiency of germanium arsenic.
S200：Mixed material is added water granulation
In the step, mixed material is added water granulation, to obtain mixing pelletizing.Inventor has found, by by mixture
Expect the granulation that adds water, be conducive to increasing the intensity and hardness of mixed material, it is ensured that will not crush in charge melted process.
According to one embodiment of present invention, the moisture in the granularity of mixing pelletizing and mixing pelletizing is not limited especially
System, those skilled in the art can be selected according to actual needs, a specific embodiment of the invention, mix pelletizing
Granularity can be 10~15mm, mix pelletizing moisture can be no more than 10wt%.Thus, be conducive to increasing mixed material
Intensity and hardness, it is ensured that will not be crushed in charge melted process.
S300：Mixing pelletizing is supplied to fuming furnace, by fine coal by spray gun Geldart-D particle to fuming furnace with mix ball
Group carries out reduction melting
In the step, mixing pelletizing is supplied to fuming furnace through feeding system, fine coal passes through blowing device Geldart-D particle extremely
Fuming furnace, to obtain germanic flue gas and smelting slag.Inventor has found that germanium is main in the form of high price germanium dioxide in flyash
In the presence of, the difficult volatile oxidn of germanium dioxide, under the high temperature and reducing atmosphere condition of fuming furnace, high price germanium dioxide and
Carbon dioxide reaction generates low price germanium oxide, and high price diarsenic pentoxide generates low price arsenic trioxide with reaction of carbon monoxide, at a low price
Germanium oxide and low price arsenic trioxide have volatile feature, while under the effect such as compressed air in fuming furnace, fuming
Melt composition violent flow in stove, drives melting bath stirring, is conducive to the volatilization of low price chromium oxide and low price arsenic oxide, carries
The volatilization of germanium arsenic high is produced effects rate.After reduction melting, smelting slag is the harmless slag without arsenic.In fuming furnace, main change
Learn reaction equation as follows：
2C+O2(g)=2CO (g) (1)
C+CO2(g)=2CO (g) (2)
GeO2+ CO (g)=GeO (g)+CO2(g) (3)
As2O5+ 2CO=As2O3(g)+2CO2(g) (4)
According to flyash, lime stone, iron ore charge ratio, during fuming furnace reduction melting can adjust fine coal spray
The amount of blowing.
According to one embodiment of present invention, the temperature and time of reduction melting is not particularly restricted, art technology
Personnel can be selected according to actual needs, a specific embodiment of the invention, the temperature control of reduction melting
At 1150~1350 degrees Celsius, the time of reduction melting can be controlled in 1~4h.After reduction melting terminates, examined substantially in smelting slag
Germanium and arsenic are not detected, germanium arsenic volatilization efficiency can reach more than 99%.
S400：Germanic flue gas is sequentially passed through into waste heat recovery and cooling and purifying treatment
In the step, germanic flue gas is sequentially passed through into waste heat recovery and cooling is gathered dust treatment, to obtain flue gas and germanic
Arsenic flue dust.It should be noted that those skilled in the art can be selected the condition that cooling and purifying is processed according to actual needs
Select.
S500：By germanic arsenic flue dust through superheated water Oxidation Leaching
In the step, will contain arsenic germanium oxide dust carries out Oxidation Leaching, to obtain high-grade germanium slag and arsenic leaching solution.Invention
People has found that part arsenic and germanium exist in low oxide form in germanium oxide dust containing arsenic, and oxidant can be by a low price in leaching process
The oxides of germanium and arsenic are high oxide；Using diarsenic pentoxide is soluble in water and germanium dioxide is insoluble in the spy of water
Point, arsenic is leached in selectively containing arsenic germanium oxide dust, and germanium is stayed in slag.
The chemical equation occurred during Oxidation Leaching is as follows：
GeO+H2O2=GeO2+H2O (5)
As2O3+2H2O2=As2O5+2H2O (6)
According to one embodiment of present invention, the oxidant of Oxidation Leaching process is not particularly restricted, art technology
Personnel can be selected according to actual needs, a specific embodiment of the invention, the oxidant of Oxidation Leaching process
Can be hydrogen peroxide, thus, other impurities ion will not be introduced in leaching process.
According to still a further embodiment, hydrogen peroxide is not particularly restricted with the mass ratio of germanic arsenic flue dust, this
Art personnel can be selected according to actual needs, a specific embodiment of the invention, hydrogen peroxide with it is germanic
The mass ratio of arsenic flue dust can be (0.5~1.5)：1.Thus, the abundant leaching of arsenic in germanic arsenic flue dust is conducive to.
According to still another embodiment of the invention, the leaching liquid-solid ratio of hot water Oxidation Leaching process, extraction temperature and leaching
Time is not particularly restricted, and those skilled in the art can be selected according to actual needs, a tool of the invention
Body embodiment, it can be (5~20) to leach liquid-solid ratio：1；Extraction temperature can be 25~95 degrees Celsius, and extraction time can be 1
~3h.Thus, the abundant leaching of arsenic in germanic arsenic flue dust is conducive to.
S600：By arsenic leaching solution through evaporation and concentration, centrifugal filtration and blade dried process
It is industrial white to obtain by arsenic leaching solution through evaporation and concentration, centrifugal filtration and blade dried process in the step
Arsenic.
Below with reference to specific embodiment, present invention is described, it is necessary to explanation, these embodiments are only description
Property, and the present invention is limited never in any form.
Embodiment
With reference to Fig. 3, by flyash, lime stone, iron ore according to mass ratio 28.99：9.74：8.27 carry out mix,
Obtain mixed material.Fe and SiO in mixed material2Mass ratio be 0.75：1, CaO and SiO2Mass ratio be 0.5：1.Will be mixed
Compound material adds water mixing granulation, obtains mixing pelletizing, and the particle diameter for mixing pelletizing is 10 millimeters, and moisture is not more than 10wt%.Will be mixed
Pelletizing is closed to be supplied into fuming furnace through feeding system, fine coal through blowing device with compressed air be medium Geldart-D particle to fuming
Stove.The temperature of reduction melting is 1200 degrees Celsius, and the time is 3 hours.Germanium is main in the form of high price germanium dioxide in flyash
In the presence of, the difficult volatile oxidn of germanium dioxide, under the high temperature and reducing atmosphere condition of fuming furnace, germanium dioxide and is aoxidized
Carbon reaction generation germanium monoxide, diarsenic pentoxide generates arsenic trioxide, germanium monoxide and three oxidations two with reaction of carbon monoxide
Arsenic has volatile feature, while under the effect such as compressed air in fuming furnace, the melt composition in fuming furnace acutely flows
It is dynamic, melting bath stirring is driven, be conducive to the volatilization of low price chromium oxide and low price arsenic oxide, improve the volatilization efficiency of germanium arsenic.Through
After reduction melting, smelting slag is the harmless slag without arsenic.Germanic flue gas obtains germanic after being gathered dust through waste heat recovery and cooling
Arsenic flue dust.The volatility of germanium arsenic reaches 99%, and the flue gas of gained can be discharged directly after desulfurization.Germanic arsenic soot oxidation leaching
Go out, hydrogen peroxide is 1 with the mass ratio of germanic arsenic flue dust：1,95 degrees Celsius of extraction temperature leaches liquid-solid ratio 6.7：1, extraction time
1h.After leaching, high-grade germanium slag and arsenic leaching solution are obtained.High-grade germanium slag is germanic to reach 12%.Arsenic leaching solution is through evaporation
Concentrate, filter, dry, the white arsenic of byproduct industry is can obtain, containing arsenic trioxide 98%.
In the description of this specification, reference term " one embodiment ", " some embodiments ", " example ", " specifically show
The description of example " or " some examples " etc. means to combine specific features, structure, material or spy that the embodiment or example are described
Point is contained at least one embodiment of the invention or example.In this manual, to the schematic representation of above-mentioned term not
Identical embodiment or example must be directed to.And, the specific features of description, structure, material or feature can be with office
Combined in an appropriate manner in one or more embodiments or example.Additionally, in the case of not conflicting, the skill of this area
Art personnel can be tied the feature of the different embodiments or example described in this specification and different embodiments or example
Close and combine.
Although embodiments of the invention have been shown and described above, it is to be understood that above-described embodiment is example
Property, it is impossible to limitation of the present invention is interpreted as, one of ordinary skill in the art within the scope of the invention can be to above-mentioned
Embodiment is changed, changes, replacing and modification.
Claims (8)
1. in a kind of flyash germanium enrichment method, it is characterised in that including：
(1) flyash, lime stone, iron ore are carried out into mix, to obtain mixed material；
(2) mixed material is added water granulation, to obtain mixing pelletizing；
(3) the mixing pelletizing is supplied to fuming furnace, by fine coal by spray gun Geldart-D particle to the fuming furnace with it is described
Mixing pelletizing carries out reduction melting, to obtain germanic flue gas and smelting slag；
(4) the germanic flue gas is sequentially passed through into waste heat recovery and cooling and purifying treatment, to obtain flue gas and germanic arsenic flue dust；
(5) by the germanic arsenic flue dust through superheated water Oxidation Leaching, to obtain high-grade germanium slag and arsenic leaching solution；
(6) arsenic leaching solution is dried through evaporation and concentration, centrifugal filtration, blade, to obtain industrial white arsenic.
2. method according to claim 1, it is characterised in that in step (1), the flyash is obtained for coal fired power generation
Germanic coal cigarette ash.
3. method according to claim 1 and 2, it is characterised in that in step (1), Fe and SiO in the mixed material2
Mass ratio be (0.5~1.1)：1, CaO and SiO2Mass ratio be (0.4~0.8)：1.
4. the method according to any one of claim 1-3, it is characterised in that in step (2), the mixing pelletizing
Granularity is 10~15mm, and the moisture of the mixing pelletizing is not more than 10wt%.
5. the method according to any one of claim 1-4, it is characterised in that in step (3), the reduction melting
Temperature is 1150~1350 degrees Celsius, and the time is 1~4h.
6. the method according to any one of claim 1-5, it is characterised in that in step (5), the Oxidation Leaching mistake
The oxidant of journey is hydrogen peroxide.
7. the method according to any one of claim 1-6, it is characterised in that in step (5), the hydrogen peroxide and institute
The mass ratio for stating germanic arsenic flue dust is (0.5~1.5)：1.
8. the method according to any one of claim 1-7, it is characterised in that in step (5), the hot water oxidation leaching
The leaching liquid-solid ratio for going out process is (5~20):1；Extraction temperature is 25~95 degrees Celsius, and extraction time is 1~3h.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111575488A (en) * | 2020-05-29 | 2020-08-25 | 上海交通大学 | Method for separating, enriching and extracting arsenic, tungsten and germanium-containing waste in sections |
| CN112820357A (en) * | 2019-11-22 | 2021-05-18 | 武汉科技大学 | Arsenic solidification rate measuring method based on combustion temperature and ash melting point temperature and application |
| CN115181855A (en) * | 2022-07-06 | 2022-10-14 | 中国恩菲工程技术有限公司 | Method for producing alloy by enriching germanium from germanium-containing smelting slag |
| CN115478166A (en) * | 2021-06-16 | 2022-12-16 | 江苏宁达环保股份有限公司 | Germanium waste melting, volatilizing and enriching method |
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| CN112820357A (en) * | 2019-11-22 | 2021-05-18 | 武汉科技大学 | Arsenic solidification rate measuring method based on combustion temperature and ash melting point temperature and application |
| CN112820357B (en) * | 2019-11-22 | 2022-03-08 | 武汉科技大学 | Arsenic solidification rate measuring method based on combustion temperature and ash melting point temperature and application |
| CN111575488A (en) * | 2020-05-29 | 2020-08-25 | 上海交通大学 | Method for separating, enriching and extracting arsenic, tungsten and germanium-containing waste in sections |
| CN115478166A (en) * | 2021-06-16 | 2022-12-16 | 江苏宁达环保股份有限公司 | Germanium waste melting, volatilizing and enriching method |
| CN115181855A (en) * | 2022-07-06 | 2022-10-14 | 中国恩菲工程技术有限公司 | Method for producing alloy by enriching germanium from germanium-containing smelting slag |
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