CN104805296B - Method for extracting scare metal indium and germanium by germanium slag - Google Patents
Method for extracting scare metal indium and germanium by germanium slag Download PDFInfo
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- CN104805296B CN104805296B CN201510252678.3A CN201510252678A CN104805296B CN 104805296 B CN104805296 B CN 104805296B CN 201510252678 A CN201510252678 A CN 201510252678A CN 104805296 B CN104805296 B CN 104805296B
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Abstract
The invention relates to a method for extracting scare metal indium and germanium by germanium slag, and belongs to the technical field of chemical metallurgy. According to the method, the germanium slag obtained through hard zinc vacuum distillation is used as raw materials. The method comprises the following steps that the germanium slag is subjected to ball milling to obtain ball milling materials; then, a sulfuric acid solution is used for leaching; the obtained leach slag is subjected to oxidizing roasting and is crushed into crushing materials; the crushing materials are subjected to chloridizing distillation; gas obtained after the chloridizing distillation is cooled to obtain a crude germanium tetrachloride solution; the crude germanium tetrachloride solution is subjected to primary extraction; the obtained germanium tetrachloride solution is filtered through a separation column; the germanium tetrachloride solution obtained after the filtering is subjected to secondary extraction to obtain a refined germanium tetrachloride solution, and the refined germanium tetrachloride solution is hydrolyzed into germanium dioxide and is reduced into germanium. The method has the advantages that the technical process can be easily controlled; the operability is high; in addition, the germanium recovery rate is stable; in addition, the cost is obviously reduced; and the electrical resistivity of the obtained germanium is higher than 10 ohm cm.
Description
Technical field
The invention belongs to the technical field of chemical metallurgy, more particularly, it relates to a kind of dilute using the extraction of germanium slag
Dispersed metallic indium and the method for germanium.
Background technology
Germanium, for its conductive ability, better than typically nonmetallic, is inferior to common metal, and this is physically being referred to as " half
Conductor ", the development to solid-state physics and Solid State Electronics plays an important role.For example first integrated circuit is exactly with germanium in the world
Make for matrix, as semi-conducting material, the metallurgical technology of germanium and purification technique are also developed rapidly germanium therewith.Germanium exists
Content in the earth's crust is 7ppm, and its abundance is higher than the multiple elements such as iodine, silver, gold, arsenic, uranium, hydrargyrum.However, almost not comparing
The germanium ore deposit concentrated, germanium but disperses very much, therefore, is known as " dissipated metal ".Germanium be generally mixed in many lead ores, copper mine,
In iron mine, silver ore, even the average just germanium containing 10 grams about in one ton of coal.The modern industry produces mainly with zinc sulfide ore, coal
And reclaim in metallurgical waste or flue dust.Although silicon gradually instead of germanium in semi-conductor industry after the sixties in 20 century
In dominant position, but because the electron mobility of germanium is higher than silicon, strength ratio silicon is good, therefore in high frequency, Aero-Space and remote
In infrared regime, germanium still occupies leading position, especially in recent years germanium radiation detector, night vision device, solaode and
The application in the fields such as optical fiberss develops rapidly, and current Year's consumption reaches more than 120t.With the continuous expansion of germanium purposes, right
The purity requirement of germanium, such as germanium tetrachloride also more and more higher, in prior art generally using extraction, chlorinated distillation technique although
This processing method is obtained in that highly purified germanium tetrachloride, but due to employing multistage distillation method, not only operating difficultiess, and
Production efficiency is relatively low, and processing cost is higher.
Content of the invention
In order to solve above-mentioned technical problem of the prior art, it is an object of the invention to provide a kind of extracted using germanium slag
Scattered metals indium and the method for germanium.
To achieve these goals, present invention employs technical scheme below：
A kind of utilization germanium slag extract scattered metals indium and germanium method it is characterised in that：Obtained with vacuum distillating hard-zinc
Germanium slag is raw material, the method comprising the steps of：
Described germanium slag is carried out with ball milling and obtains the ball milling material that particle diameter is 10 μm, then leached using sulfuric acid solution；
Carry out oxidizing roasting and be broken into the broken material that particle diameter is less than 1 μm to leaching the leached mud obtaining；
Chlorinated distillation is carried out to described broken material；
The gas containing germanium tetrachloride that chlorinated distillation is obtained carries out cooling and obtains thick germanium tetrachloride solution；
Described thick germanium tetrachloride liquid is carried out extracting for the first time using the hydrochloric acid solution containing saturation chlorine；
The germanium tetrachloride solution that first time is obtained by extraction is filtered using detached dowel；
The germanium tetrachloride being filtrated to get solution is carried out second extracting and obtaining using the hydrochloric acid solution containing saturation chlorine
Refined germanium tetrachloride solution；
The refined germanium tetrachloride solution obtaining is hydrolyzed into germanium dioxide and is reduced to germanium.
Wherein, in described germanium slag, the content of germanium is 1.3 ~ 2.0wt%, and the content of indium is 1.5 ~ 2.5wt%.
Wherein, the concentration of sulfuric acid solution is 0.2 ~ 1.0 mol/L, and the consumption of sulfuric acid solution is the 1.5 ~ 2.0 of germanium slag amount
Times.
Wherein, described oxidizing roasting is carried out under air conditionses, and sintering temperature is 350 ~ 450 DEG C.
Wherein, described chlorinated distillation is carried out in a kettle.；First, add the HCl containing 25 ~ 50g/L in a kettle.,
The H of 15 ~ 20g/L2O2Acid solution with balance of water；Then, add the matter of broken material, acid solution and broken material under conditions of stirring
Amount ratio is 3：1；Then it is passed through chlorine leaching at a temperature of 50 ~ 70 DEG C, to the chlorine being passed through not re-absorption；Then heat to 85
~ 95 DEG C, carry out germanium tetrachloride distillation, obtain the gas containing germanium tetrachloride.
Wherein, residual liquid chlorinated distillation being obtained carries out the operation of the extraction indium of routine.
Wherein, contain the hydrochloric acid of saturation chlorine when extracting for the first time using 10 mol/L, extraction temperature is 0 ~ 10 DEG C, during extraction
Between be 45 ~ 60 min.
Wherein, contain the hydrochloric acid of saturation chlorine when extracting for second using 12mol/L, extraction temperature is 0 ~ 10 DEG C, during extraction
Between be 45 ~ 60 min.
Wherein, the fixing phase in described detached dowel has the silica gel of methacrylic acid and trioctylamine for surface grafting.
Wherein, described fixing phase is prepared by the following method and obtains：
（1）Under conditions of 80 ~ 100 DEG C, the hydrochloric acid using 1 ~ 2 mol is that 1 μm of silica white is acidified to particle diameter
Process, process time is 8 ~ 12 hours, is filtered, washed and dried the silica white obtaining pretreatment after being cooled to room temperature；
（2）By step（1）The silica white of the pretreatment obtaining adds equipped with the vacuum response kettle of dry toluene, Ran Hou
Under conditions of 60 ~ 80 DEG C, Deca amino silane, stirring reaction 10 ~ 12 h；It is subsequently adding tri-n-octyl amine, stirring reaction 6 ~ 8 is little
When；It is subsequently adding methacrylic acid, stirring reaction 6 ~ 8 hours；It is then passed through being filtered, washed and dried and can get described fixation
Phase；Wherein, the mass ratio of the silica white of described pretreatment, amino silane, tri-n-octyl amine and methacrylic acid is 100：10~12：
12~15：3~5.
Compared with prior art, the invention has the advantages that：
Technical process of the present invention is easily controllable, workable, and the germanium response rate is stable, reclaims the germanium obtaining
Purity is high, and cost significantly reduces with respect to continuous still or continuous extraction process, the purity of germanium can reach 99.99% with
On, resistivity is more than 10 Ω cm.
Brief description
Fig. 1 utilizes germanium slag to extract the process chart of scattered metals indium and germanium for the present invention.
Specific embodiment
Below with reference to specific embodiment, the method using germanium slag extraction scattered metals indium and germanium of the present invention is done
Further elucidated above, with help those skilled in the art the inventive concept of the present invention, technical scheme are had more complete, accurately and
Deep understanding.
Utilization germanium slag of the present invention extracts scattered metals indium and the technological process of germanium is as shown in Figure 1.The side of the present invention
As raw material, in described germanium slag, the content of germanium is 1.3 ~ 2.0wt% to the germanium slag that method is obtained with vacuum distillating hard-zinc, and the content of indium is 1.5
~ 2.5wt%, remaining is mainly other component such as lead and zinc.Specifically, the method comprising the steps of：
Described germanium slag is carried out with ball milling and obtains the ball milling material that particle diameter is 10 μm, then leached using sulfuric acid solution；Its
In, the concentration of sulfuric acid solution is 0.2 ~ 1.0 mol/L, and the consumption of sulfuric acid solution is 1.5 ~ 2.0 times of germanium slag amount；
Carry out oxidizing roasting and be broken into the broken material that particle diameter is less than 1 μm to leaching the leached mud obtaining；Wherein, institute
State oxidizing roasting to carry out under air conditionses, and sintering temperature is 350 ~ 450 DEG C；
Chlorinated distillation is carried out to described broken material；Wherein, chlorinated distillation is carried out in a kettle.；First, in a kettle.
Add HCl, the H of 15 ~ 20g/L containing 25 ~ 50g/L2O2Acid solution with balance of water；Then, add under conditions of stirring and break
Particle, acid solution is 3 with the mass ratio of broken material：1；Then it is passed through chlorine leaching at a temperature of 50 ~ 70 DEG C, to the chlorine being passed through
Not re-absorption；Then heat to 85 ~ 95 DEG C, carry out germanium tetrachloride distillation, obtain the gas containing germanium tetrachloride and residual liquid；
The residual liquid that chlorinated distillation is obtained carries out the operation of the extraction indium of routine；
The gas containing germanium tetrachloride that chlorinated distillation is obtained carries out cooling and obtains thick germanium tetrachloride solution；
Described thick germanium tetrachloride liquid is carried out extracting for the first time using the hydrochloric acid solution containing saturation chlorine；When extracting for the first time
Contain the hydrochloric acid of saturation chlorine using 10 mol/L, extraction temperature is 0 ~ 10 DEG C, extraction time is 45 ~ 60 min；
The germanium tetrachloride solution that first time is obtained by extraction is filtered using detached dowel；
The germanium tetrachloride being filtrated to get solution is carried out second extracting and obtaining using the hydrochloric acid solution containing saturation chlorine
Refined germanium tetrachloride solution；The hydrochloric acid of saturation chlorine is contained using 12mol/L, extraction temperature is 0 ~ 10 DEG C, extraction when extracting for second
The time is taken to be 45 ~ 60 min；
The refined germanium tetrachloride solution obtaining is hydrolyzed into germanium dioxide and is reduced to germanium.
Wherein, in embodiments of the invention 2-4, described fixing phase is prepared by the following method and obtains：
（1）Under conditions of 100 DEG C, the hydrochloric acid using 1 mol is that 1 μm of silica white carries out acidification to particle diameter,
Process time is 10 hours, is filtered, washed and dried the silica white obtaining pretreatment after being cooled to room temperature；
（2）By step（1）The silica white of the pretreatment obtaining adds equipped with the vacuum response kettle of dry toluene, Ran Hou
Under conditions of 60 DEG C, Deca gamma-aminopropyl-triethoxy-silane, stirring reaction 12 h；It is subsequently adding tri-n-octyl amine, stirring reaction
8 hours；It is subsequently adding methacrylic acid, stirring reaction 6 hours；Be then passed through being filtered, washed and dried can get described solid
Determine phase；Wherein, the quality of the silica white of described pretreatment, gamma-aminopropyl-triethoxy-silane, tri-n-octyl amine and methacrylic acid
Than for 100：12：12：4.
In embodiments of the invention 2-4, the detached dowel of use is cylindric glass column, a diameter of 20mm, and column length is
30 cm, fill fixing phase obtained above under an increased pressure, and to ensure filling uniformly, packed density is 2g/mL.
Embodiment 1
Used in embodiment and comparative example, broken preparation method for material is as follows：Ball milling carried out to germanium slag obtain particle diameter be
10 μm of ball milling material, is then leached using sulfuric acid solution；Wherein, the concentration of sulfuric acid solution is 0.5 mol/L, and sulphuric acid is molten
The consumption of liquid is 2.0 times of germanium slag amount；To leach the leached mud that obtains carry out oxidizing roasting and be broken into particle diameter be 1 μm with
Under broken material；Wherein, described oxidizing roasting is carried out under air conditionses, and sintering temperature is 400 DEG C.
Embodiment 2
In the present embodiment, in described germanium slag, the content of germanium is 1.36wt%, and the content of indium is 1.72wt%, and remaining is mainly
Other component such as lead and zinc simultaneously prepares broken material according to the method for embodiment 1.Add in a kettle. containing 30 g/L's
The H of HCl, 18g/L2O2Acid solution with balance of water；Then, add the matter of broken material, acid solution and broken material under conditions of stirring
Amount ratio is 3：1；Then it is passed through chlorine leaching at a temperature of 60 DEG C, to the chlorine being passed through not re-absorption；Then heat to 90 DEG C,
Carry out germanium tetrachloride distillation, obtain the gas containing germanium tetrachloride and residual liquid；Residual liquid is carried out with the operation of the extraction indium of routine；By institute
State gas cooling to the room temperature containing germanium tetrachloride and obtain thick germanium tetrachloride solution, extracted and filter.Make when extracting for the first time
Contain the hydrochloric acid of saturation chlorine with 10 mol/L, control extraction temperature to be 0 ~ 10 DEG C using brine bath, extraction time is 60 min.Extraction
The germanium tetrachloride solution obtaining is filtered using the detached dowel of the present invention, specifically carries out dropwise operation, rate of addition
It is controlled to 5 ~ 10ml/min, repeat aforesaid operations 3 times by collecting the filtering solution that obtains.Then, carry out second extraction
Operation.The hydrochloric acid of saturation chlorine is contained using 12mol/L, extraction temperature is 0 ~ 10 DEG C, and extraction time is 60 when extracting for second
Min, the larger refined germanium tetrachloride of density is located at lower floor, and the refined germanium tetrachloride solution obtaining is hydrolyzed into germanium dioxide, also
Originally it was germanium.
Embodiment 3
In the present embodiment, in described germanium slag, the content of germanium is 1.62wt%, and the content of indium is 1.81wt%, and remaining is mainly
Other component such as lead and zinc simultaneously prepares broken material according to the method for embodiment 1.Add in a kettle. containing 39g/L's
The H of HCl, 18g/L2O2Acid solution with balance of water；Then, add the matter of broken material, acid solution and broken material under conditions of stirring
Amount ratio is 3：1；Then it is passed through chlorine leaching at a temperature of 60 DEG C, to the chlorine being passed through not re-absorption；Then heat to 90 DEG C,
Carry out germanium tetrachloride distillation, obtain the gas containing germanium tetrachloride and residual liquid；The residual liquid that chlorinated distillation is obtained carries out carrying of routine
Take the operation of indium；The described gas cooling containing germanium tetrachloride to room temperature is obtained thick germanium tetrachloride solution, is extracted and filter.
Contain the hydrochloric acid of saturation chlorine when extracting for the first time using 10 mol/L, control extraction temperature to be 0 ~ 10 DEG C using brine bath, extraction
Time is 60 min.The germanium tetrachloride solution being obtained by extraction is filtered using the detached dowel of the present invention, specifically carries out dripping
Add operation, rate of addition is controlled to 5 ~ 10ml/min, repeats aforesaid operations 3 times by collecting the filtering solution that obtains.Then,
Carry out second extracting operation.The hydrochloric acid of saturation chlorine is contained using 12mol/L, extraction temperature is 0 ~ 10 DEG C when extracting for second,
Extraction time is 60 min, and the larger refined germanium tetrachloride of density is located at lower floor, by the refined germanium tetrachloride solution hydrolysis obtaining
Become germanium dioxide, be reduced to germanium.
Embodiment 4
In the present embodiment, in described germanium slag, the content of germanium is 1.98wt%, and the content of indium is 2.36wt%, and remaining is mainly
Other component such as lead and zinc simultaneously prepares broken material according to the method for embodiment 1.Add in a kettle. containing 50g/L's
The H of HCl, 20g/L2O2Acid solution with balance of water；Then, broken material, acid solution and broken material are added under conditions of stirring
Mass ratio is 3：1；Then it is passed through chlorine leaching at a temperature of 60 DEG C, to the chlorine being passed through not re-absorption；Then heat to 85
DEG C, carry out germanium tetrachloride distillation, obtain the gas containing germanium tetrachloride and residual liquid；The residual liquid that chlorinated distillation is obtained carries out routine
Extract the operation of indium；The described gas cooling containing germanium tetrachloride to room temperature is obtained thick germanium tetrachloride solution, is extracted and mistake
Filter.Contain the hydrochloric acid of saturation chlorine when extracting for the first time using 10 mol/L, control extraction temperature to be 0 ~ 10 DEG C using brine bath, extraction
The time is taken to be 60 min.The germanium tetrachloride solution being obtained by extraction is filtered using the detached dowel of the present invention, specifically carries out
Dropwise operation, rate of addition is controlled to 5 ~ 10ml/min, repeats aforesaid operations 3 times by collecting the filtering solution that obtains.So
Afterwards, carry out second extracting operation.The hydrochloric acid of saturation chlorine is contained using 12mol/L, extraction temperature is 0 ~ 10 when extracting for second
DEG C, extraction time is 60 min, and the larger refined germanium tetrachloride of density is located at lower floor, by the refined germanium tetrachloride solution water obtaining
Solution becomes germanium dioxide, is reduced to germanium.
In an embodiment of the present invention, the purity of germanium can reach more than 99.99%, and resistivity is more than 10 Ω cm.
Comparative example 1
In this comparative example, in described germanium slag, the content of germanium is 1.36wt%, and the content of indium is 1.72wt%, and remaining is mainly
Other component such as lead and zinc simultaneously prepares broken material according to the method for embodiment 1.Add in a kettle. containing 30 g/L's
The H of HCl, 18g/L2O2Acid solution with balance of water；Then, add the matter of broken material, acid solution and broken material under conditions of stirring
Amount ratio is 3：1；Then it is passed through chlorine leaching at a temperature of 60 DEG C, to the chlorine being passed through not re-absorption；Then heat to 90 DEG C,
Carry out germanium tetrachloride distillation, obtain the gas containing germanium tetrachloride and residual liquid；Residual liquid is carried out with the operation of the extraction indium of routine；By institute
State gas cooling to the room temperature containing germanium tetrachloride and obtain thick germanium tetrachloride solution, carry out 4 extractions.For the first time and second extracts
When using 10 mol/L contain saturation chlorine hydrochloric acid, using brine bath control extraction temperature be 0 ~ 10 DEG C, extraction time be 60
min.The hydrochloric acid of saturation chlorine is contained using 12 mol/L, extraction temperature is 0 ~ 10 DEG C, during extraction when third time and the 4th extraction
Between be 60 min, the larger refined germanium tetrachloride of density be located at lower floor, the refined germanium tetrachloride solution obtaining is hydrolyzed into dioxy
Change germanium, be reduced to germanium.The purity of the germanium obtaining is 99.98%, and resistivity is 3 ~ 6 Ω cm.
Comparative example 2
In this comparative example, in described germanium slag, the content of germanium is 1.36wt%, and the content of indium is 1.72wt%, and remaining is mainly
Other component such as lead and zinc simultaneously prepares broken material according to the method for embodiment 1.Add in a kettle. containing 30 g/L's
The H of HCl, 18g/L2O2Acid solution with balance of water；Then, add the matter of broken material, acid solution and broken material under conditions of stirring
Amount ratio is 3：1；Then it is passed through chlorine leaching at a temperature of 60 DEG C, to the chlorine being passed through not re-absorption；Then heat to 90 DEG C,
Carry out germanium tetrachloride distillation, obtain the gas containing germanium tetrachloride and residual liquid；Residual liquid is carried out with the operation of the extraction indium of routine；By institute
State gas cooling to the room temperature containing germanium tetrachloride and obtain thick germanium tetrachloride solution, extracted and filter.Make when extracting for the first time
Contain the hydrochloric acid of saturation chlorine with 10 mol/L, control extraction temperature to be 0 ~ 10 DEG C using brine bath, extraction time is 60 min.Extraction
The germanium tetrachloride solution obtaining is filtered using detached dowel, specifically carries out dropwise operation, and rate of addition is controlled to 5 ~
10ml/min, repeats aforesaid operations 3 times by collecting the filtering solution that obtains.Then, carry out second extracting operation.Second
The hydrochloric acid of saturation chlorine is contained using 12mol/L, extraction temperature is 0 ~ 10 DEG C, and extraction time is 60 min, and density is relatively during secondary extraction
Big refined germanium tetrachloride is located at lower floor, the refined germanium tetrachloride solution obtaining is hydrolyzed into germanium dioxide, is reduced to germanium.
In this comparative example, fixing phase is prepared by the following method and obtains：First, under conditions of 100 DEG C, using 1mol
Hydrochloric acid be that 1 μm of silica white carries out acidification to particle diameter, process time is 10 hours, filters, washing after being cooled to room temperature
With the silica white being dried to obtain pretreatment；Then, will be anti-equipped with the vacuum of dry toluene for the silica white addition of the pretreatment obtaining
Answer in kettle, then under conditions of 60 DEG C, Deca gamma-aminopropyl-triethoxy-silane, stirring reaction 12 h；Just it is subsequently adding three
Octylame, stirring reaction 8 hours；It is then passed through being filtered, washed and dried and can get described fixing phase；Wherein, described pretreatment
Silica white, gamma-aminopropyl-triethoxy-silane and tri-n-octyl amine mass ratio be 100：10：15.The detached dowel using is circle
Column glass column, a diameter of 20mm, column length is 30cm, fills fixing phase obtained above under an increased pressure, to ensure to fill out
Fill uniformly, packed density is 2g/mL.The resistivity of the germanium obtaining is 3 ~ 5 Ω cm.
Comparative example 3
In this comparative example, in described germanium slag, the content of germanium is 1.36wt%, and the content of indium is 1.72wt%, and remaining is mainly
Other component such as lead and zinc simultaneously prepares broken material according to the method for embodiment 1.Add in a kettle. containing 30 g/L's
The H of HCl, 18g/L2O2Acid solution with balance of water；Then, add the matter of broken material, acid solution and broken material under conditions of stirring
Amount ratio is 3：1；Then it is passed through chlorine leaching at a temperature of 60 DEG C, to the chlorine being passed through not re-absorption；Then heat to 90 DEG C,
Carry out germanium tetrachloride distillation, obtain the gas containing germanium tetrachloride and residual liquid；Residual liquid is carried out with the operation of the extraction indium of routine；By institute
State gas cooling to the room temperature containing germanium tetrachloride and obtain thick germanium tetrachloride solution, extracted and filter.Make when extracting for the first time
Contain the hydrochloric acid of saturation chlorine with 10 mol/L, control extraction temperature to be 0 ~ 10 DEG C using brine bath, extraction time is 60 min.Extraction
The germanium tetrachloride solution obtaining is filtered using detached dowel, specifically carries out dropwise operation, and rate of addition is controlled to 5 ~
10ml/min, repeats aforesaid operations 3 times by collecting the filtering solution that obtains.Then, carry out second extracting operation.Second
The hydrochloric acid of saturation chlorine is contained using 12mol/L, extraction temperature is 0 ~ 10 DEG C, and extraction time is 60 min, and density is relatively during secondary extraction
Big refined germanium tetrachloride is located at lower floor, the refined germanium tetrachloride solution obtaining is hydrolyzed into germanium dioxide, is reduced to germanium.
In this comparative example, fixing phase is prepared by the following method and obtains：First, under conditions of 80 DEG C, using 1mol
Hydrochloric acid be that 1 μm of silica white carries out acidification to particle diameter, process time is 12 hours, filters, washing after being cooled to room temperature
With the silica white being dried to obtain pretreatment；Then, will be anti-equipped with the vacuum of dry toluene for the silica white addition of the pretreatment obtaining
Answer in kettle, then under conditions of 60 DEG C, Deca gamma-aminopropyl-triethoxy-silane, stirring reaction 12 h；It is subsequently adding methyl
Acrylic acid, stirring reaction 8 hours；It is then passed through being filtered, washed and dried and can get described fixing phase；Wherein, described pre- place
The mass ratio of the silica white, gamma-aminopropyl-triethoxy-silane and methacrylic acid of reason is 100：5：3.Use detached dowel be
Cylindric glass column, a diameter of 20mm, column length is 30cm, fills fixing phase obtained above under an increased pressure, to ensure
Uniformly, packed density is 2g/mL for filling.The resistivity of the germanium obtaining is 1 ~ 3 Ω cm.
For the ordinary skill in the art, specific embodiment is simply exemplarily described to the present invention,
Obviously the present invention implements and is not subject to the restrictions described above.
Claims (8)
1. a kind of utilization germanium slag extract scattered metals indium and germanium method it is characterised in that：The germanium being obtained with vacuum distillating hard-zinc
Slag is raw material, the method comprising the steps of：
Described germanium slag is carried out with ball milling and obtains the ball milling material that particle diameter is 10 μm, then leached using sulfuric acid solution；
Carry out oxidizing roasting and be broken into the broken material that particle diameter is less than 1 μm to leaching the leached mud obtaining；
Chlorinated distillation is carried out to described broken material；
The gas containing germanium tetrachloride that chlorinated distillation is obtained carries out cooling and obtains thick germanium tetrachloride solution；
Described thick germanium tetrachloride liquid is carried out extracting for the first time using the hydrochloric acid solution containing saturation chlorine；
The germanium tetrachloride solution that first time is obtained by extraction is filtered using detached dowel；Fixing phase in described detached dowel is table
Face is grafted with the silica gel of methacrylic acid and trioctylamine；
The germanium tetrachloride being filtrated to get solution is carried out second extracting and being refined using the hydrochloric acid solution containing saturation chlorine
Germanium tetrachloride solution；
The refined germanium tetrachloride solution obtaining is hydrolyzed into germanium dioxide and is reduced to germanium.
2. utilization germanium slag according to claim 1 extract scattered metals indium and germanium method it is characterised in that：Described germanium slag
The content of middle germanium is 1.3～2.0wt%, and the content of indium is 1.5～2.5wt%.
3. utilization germanium slag according to claim 1 extract scattered metals indium and germanium method it is characterised in that：Sulfuric acid solution
Concentration be 0.2～1.0mol/L, the consumption of sulfuric acid solution is 1.5～2.0 times of germanium slag amount.
4. utilization germanium slag according to claim 1 extract scattered metals indium and germanium method it is characterised in that：Described oxidation
Roasting is carried out under air conditionses, and sintering temperature is 350～450 DEG C.
5. utilization germanium slag according to claim 1 extract scattered metals indium and germanium method it is characterised in that：Described chlorination
Distillation is carried out in a kettle.；First, the HCl containing 25～50g/L, the H of 15～20g/L are added in a kettle.2O2And surplus
Acid solution for water；Then, add broken material under conditions of stirring, acid solution is 3 with the mass ratio of broken material：1；Then 50～
It is passed through chlorine leaching, to the chlorine being passed through not re-absorption at a temperature of 70 DEG C；Then heat to 85～95 DEG C, carry out germanium tetrachloride
Distillation, obtains the gas containing germanium tetrachloride.
6. utilization germanium slag according to claim 1 extract scattered metals indium and germanium method it is characterised in that：Chlorination is steamed
Evaporate the operation that the residual liquid obtaining carries out the extraction indium of routine.
7. utilization germanium slag according to claim 1 extract scattered metals indium and germanium method it is characterised in that：Extract for the first time
The hydrochloric acid of saturation chlorine is contained using 10mol/L, extraction temperature is 0～10 DEG C, extraction time is 45～60min when taking.
8. utilization germanium slag according to claim 1 extract scattered metals indium and germanium method it is characterised in that：Extract for second
The hydrochloric acid of saturation chlorine is contained using 12mol/L, extraction temperature is 0～10 DEG C, extraction time is 45～60min when taking.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510252678.3A CN104805296B (en) | 2015-05-19 | 2015-05-19 | Method for extracting scare metal indium and germanium by germanium slag |
Applications Claiming Priority (1)
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| CN108147375B (en) * | 2017-12-27 | 2020-12-25 | 清远先导材料有限公司 | Method for recovering selenium-germanium-sulfur glass |
| CN111020204B (en) * | 2019-12-31 | 2020-11-27 | 耒阳市焱鑫有色金属有限公司 | Oxygen-enriched side-blown furnace smelting method for preparing chlorinating agent from secondary resource containing arsenic, iron and rare-dispersion elements |
| CN113403488A (en) * | 2021-06-22 | 2021-09-17 | 扬州宁达贵金属有限公司 | Method for recovering germanium from copper-lead-zinc-arsenic-germanium material |
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