CN104805296A - 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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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, in particular, the present invention relates to a kind of method utilizing germanium slag to extract scattered metals indium and germanium.
Background technology
Germanium, with regard to the ability of its conduction, be better than generally nonmetal, be inferior to common metal, this is physically being called " semi-conductor ", plays an important role to the development of solid-state physics and Solid State Electronics.Such as first unicircuit is that matrix is made with germanium in the world, and germanium is as semiconductor material thereupon, and the metallurgical technology of germanium and purification techniques have also been obtained and develop rapidly.The content of germanium in the earth's crust is 7ppm, and its abundance is higher than the multiple elements such as iodine, silver, gold, arsenic, uranium, mercury.But the germanium ore deposit of almost relatively not concentrating, germanium but disperses very much, therefore, is called " dissipated metal " by people.Germanium is mixed in many lead ores, copper mine, iron ore, silver ore usually, even average just containing the germanium of about 10 grams in one ton of coal.The modern industry is produced main to reclaim in zinc sulfide ore, coal and metallurgical waste or flue dust.After the sixties in 20th century, although silicon instead of germanium dominant position in the semiconductor industry gradually, but because the electronic mobility of germanium is higher than silicon, strength ratio silicon is good, therefore germanium still dominate in high frequency, aerospace and far infrared field, especially in recent years germanium develops rapidly in the application in the fields such as radiation detector, night vision equipment, solar cell and photoconductive fiber, and current Year's consumption reaches more than 120t.Along with the continuous expansion of germanium purposes, to germanium, the purity requirement of such as germanium tetrachloride is also more and more higher, usually extraction, chlorinated distillation technique is adopted in prior art, although this treatment process can obtain highly purified germanium tetrachloride, owing to have employed multistage distillation method, not only operational difficulty, and production efficiency is lower, processing costs is higher.
Summary of the invention
In order to solve above-mentioned technical problem of the prior art, the object of the present invention is to provide a kind of method utilizing germanium slag to extract scattered metals indium and germanium.
To achieve these goals, present invention employs following technical scheme:
Utilize germanium slag to extract a method for scattered metals indium and germanium, it is characterized in that: the germanium slag obtained with vacuum distillating hard-zinc is raw material, said method comprising the steps of:
Ball milling is carried out to described germanium slag and obtains the ball milling material that particle diameter is 10 μm, then utilize sulphuric acid soln to leach;
Carry out oxidizing roasting to leaching the leached mud obtained and be broken into the broken material that particle diameter is less than 1 μm;
Chlorinated distillation is carried out to described broken material;
What obtain chlorinated distillation carries out cooling containing the gas of germanium tetrachloride and obtains thick germanium tetrachloride solution;
The hydrochloric acid soln containing saturated chlorine is utilized to carry out first time extraction to described thick germanium tetrachloride liquid;
Filter extracting the germanium tetrachloride soln using separator column obtained for the first time;
Carry out second time and extract by filtering the germanium tetrachloride soln using that the obtains hydrochloric acid soln containing saturated chlorine and obtain refining germanium tetrachloride solution;
The refining germanium tetrachloride solution obtained 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 sulphuric acid soln is 0.2 ~ 1.0 mol/L, and the consumption of sulphuric acid soln is 1.5 ~ 2.0 times of germanium slag amount.
Wherein, described oxidizing roasting is carried out under air conditions, and maturing temperature is 350 ~ 450 DEG C.
Wherein, described chlorinated distillation carries out in a kettle.; First, add the HCl containing 25 ~ 50g/L in a kettle., the H of 15 ~ 20g/L
2o
2be the acid solution of water with surplus; Then, under the condition stirred, add broken material, the mass ratio of acid solution and broken material is 3:1; Then at the temperature of 50 ~ 70 DEG C, pass into chlorine leaching, no longer absorb to the chlorine passed into; Then be warming up to 85 ~ 95 DEG C, carry out germanium tetrachloride distillation, obtain the gas containing germanium tetrachloride.
Wherein, the raffinate obtained chlorinated distillation carries out the operation of conventional extraction indium.
Wherein, use 10 mol/L containing the hydrochloric acid of saturated chlorine during first time extraction, extraction temperature is 0 ~ 10 DEG C, and extraction time is 45 ~ 60 min.
Wherein, use 12mol/L containing the hydrochloric acid of saturated chlorine during second time extraction, extraction temperature is 0 ~ 10 DEG C, and extraction time is 45 ~ 60 min.
Wherein, the stationary phase in described separator column is the silica gel that surface grafting has methacrylic acid and trioctylamine.
Wherein, described stationary phase prepares by the following method:
(1) under the condition of 80 ~ 100 DEG C, utilize the hydrochloric acid of 1 ~ 2 mol to carry out acidification to the silica-gel powder that particle diameter is 1 μm, the treatment time is 8 ~ 12 hours, and filtration after being cooled to room temperature, washing and drying obtain pretreated silica-gel powder;
(2) the pretreated silica-gel powder that step (1) obtains is added be equipped with in the vacuum reaction still of dry toluene, then under the condition of 60 ~ 80 DEG C, drip aminosilane, stirring reaction 10 ~ 12 h; Then tri-n-octyl amine is added, stirring reaction 6 ~ 8 hours; Then methacrylic acid is added, stirring reaction 6 ~ 8 hours; Then described stationary phase can be obtained through filtration, washing and drying; Wherein, the mass ratio of described pretreated silica-gel powder, aminosilane, tri-n-octyl amine and methacrylic acid is 100:10 ~ 12:12 ~ 15:3 ~ 5.
Compared with prior art, the present invention has following beneficial effect:
Technological process of the present invention be easy to control, workable, and the germanium rate of recovery is stablized, reclaim the germanium purity obtained high, and cost significantly reduces relative to continuous still battery or continuous extraction process, the purity of germanium can reach more than 99.99%, and resistivity is 10 more than Ω cm.
Accompanying drawing explanation
Fig. 1 is that the present invention utilizes germanium slag to extract the process flow sheet of scattered metals indium and germanium.
Embodiment
Below with reference to specific embodiment, the method utilizing germanium slag to extract scattered metals indium and germanium of the present invention is further elaborated, has more complete, accurate and deep understanding to help those skilled in the art to inventive concept of the present invention, technical scheme.
The technical process utilizing germanium slag to extract scattered metals indium and germanium of the present invention as shown in Figure 1.The germanium slag that method of the present invention obtains with vacuum distillating hard-zinc is for raw material, and in described germanium slag, the content of germanium is 1.3 ~ 2.0wt%, and the content of indium is 1.5 ~ 2.5wt%, and all the other are mainly other components such as plumbous and zinc.Specifically, said method comprising the steps of:
Ball milling is carried out to described germanium slag and obtains the ball milling material that particle diameter is 10 μm, then utilize sulphuric acid soln to leach; Wherein, the concentration of sulphuric acid soln is 0.2 ~ 1.0 mol/L, and the consumption of sulphuric acid soln is 1.5 ~ 2.0 times of germanium slag amount;
Carry out oxidizing roasting to leaching the leached mud obtained and be broken into the broken material that particle diameter is less than 1 μm; Wherein, described oxidizing roasting is carried out under air conditions, and maturing temperature is 350 ~ 450 DEG C;
Chlorinated distillation is carried out to described broken material; Wherein, chlorinated distillation carries out in a kettle.; First, add the HCl containing 25 ~ 50g/L in a kettle., the H of 15 ~ 20g/L
2o
2be the acid solution of water with surplus; Then, under the condition stirred, add broken material, the mass ratio of acid solution and broken material is 3:1; Then at the temperature of 50 ~ 70 DEG C, pass into chlorine leaching, no longer absorb to the chlorine passed into; Then be warming up to 85 ~ 95 DEG C, carry out germanium tetrachloride distillation, obtain the gas containing germanium tetrachloride and raffinate;
The raffinate obtained chlorinated distillation carries out the operation of conventional extraction indium;
What obtain chlorinated distillation carries out cooling containing the gas of germanium tetrachloride and obtains thick germanium tetrachloride solution;
The hydrochloric acid soln containing saturated chlorine is utilized to carry out first time extraction to described thick germanium tetrachloride liquid; Use 10 mol/L containing the hydrochloric acid of saturated chlorine during first time extraction, extraction temperature is 0 ~ 10 DEG C, and extraction time is 45 ~ 60 min;
Filter extracting the germanium tetrachloride soln using separator column obtained for the first time;
Carry out second time and extract by filtering the germanium tetrachloride soln using that the obtains hydrochloric acid soln containing saturated chlorine and obtain refining germanium tetrachloride solution; Use 12mol/L containing the hydrochloric acid of saturated chlorine during second time extraction, extraction temperature is 0 ~ 10 DEG C, and extraction time is 45 ~ 60 min;
The refining germanium tetrachloride solution obtained is hydrolyzed into germanium dioxide and is reduced to germanium.
Wherein, in embodiments of the invention 2-4, described stationary phase prepares by the following method:
(1) under the condition of 100 DEG C, utilize the hydrochloric acid of 1 mol to carry out acidification to the silica-gel powder that particle diameter is 1 μm, the treatment time is 10 hours, and filtration after being cooled to room temperature, washing and drying obtain pretreated silica-gel powder;
(2) the pretreated silica-gel powder that step (1) obtains is added be equipped with in the vacuum reaction still of dry toluene, then under the condition of 60 DEG C, drip γ-aminopropyl triethoxysilane, stirring reaction 12 h; Then tri-n-octyl amine is added, stirring reaction 8 hours; Then methacrylic acid is added, stirring reaction 6 hours; Then described stationary phase can be obtained through filtration, washing and drying; Wherein, the mass ratio of described pretreated silica-gel powder, γ-aminopropyl triethoxysilane, tri-n-octyl amine and methacrylic acid is 100:12:12:4.
In embodiments of the invention 2-4, the separator column of use is cylindric glass column, and diameter is 20mm, and column length is 30 cm, fills stationary phase obtained above under an increased pressure, and to ensure to fill evenly, tamped density is 2g/mL.
embodiment
1
The broken material preparation method used in embodiment and comparative example is as follows: carry out ball milling to germanium slag and obtain the ball milling material that particle diameter is 10 μm, then utilize sulphuric acid soln to leach; Wherein, the concentration of sulphuric acid soln is 0.5 mol/L, and the consumption of sulphuric acid soln is 2.0 times of germanium slag amount; Carry out oxidizing roasting to leaching the leached mud obtained and be broken into the broken material that particle diameter is less than 1 μm; Wherein, described oxidizing roasting is carried out under air conditions, and maturing 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 all the other are mainly other components such as plumbous and zinc and the method for foundation embodiment 1 prepares broken material.Add the HCl containing 30 g/L in a kettle., the H of 18g/L
2o
2be the acid solution of water with surplus; Then, under the condition stirred, add broken material, the mass ratio of acid solution and broken material is 3:1; Then at the temperature of 60 DEG C, pass into chlorine leaching, no longer absorb to the chlorine passed into; Then be warming up to 90 DEG C, carry out germanium tetrachloride distillation, obtain the gas containing germanium tetrachloride and raffinate; Raffinate is carried out to the operation of conventional extraction indium; Described gas cooling to the room temperature containing germanium tetrachloride is obtained thick germanium tetrachloride solution, carries out extracting and filtering.Use 10 mol/L containing the hydrochloric acid of saturated chlorine during first time extraction, utilizing brine bath to control extraction temperature is 0 ~ 10 DEG C, and extraction time is 60 min.Extract the germanium tetrachloride soln using separator column of the present invention obtained to filter, carry out dropwise operation specifically, it is 5 ~ 10ml/min that rate of addition controls, and repeats aforesaid operations 3 times by collecting the filtering solution obtained.Then, second time extracting operation is carried out.Use 12mol/L containing the hydrochloric acid of saturated chlorine during second time extraction, extraction temperature is 0 ~ 10 DEG C, and extraction time is 60 min, and the refining germanium tetrachloride that density is larger is positioned at lower floor, the refining germanium tetrachloride solution obtained is hydrolyzed into germanium dioxide, is reduced to 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 all the other are mainly other components such as plumbous and zinc and the method for foundation embodiment 1 prepares broken material.Add the HCl containing 39g/L in a kettle., the H of 18g/L
2o
2be the acid solution of water with surplus; Then, under the condition stirred, add broken material, the mass ratio of acid solution and broken material is 3:1; Then at the temperature of 60 DEG C, pass into chlorine leaching, no longer absorb to the chlorine passed into; Then be warming up to 90 DEG C, carry out germanium tetrachloride distillation, obtain the gas containing germanium tetrachloride and raffinate; The raffinate obtained chlorinated distillation carries out the operation of conventional extraction indium; Described gas cooling to the room temperature containing germanium tetrachloride is obtained thick germanium tetrachloride solution, carries out extracting and filtering.Use 10 mol/L containing the hydrochloric acid of saturated chlorine during first time extraction, utilizing brine bath to control extraction temperature is 0 ~ 10 DEG C, and extraction time is 60 min.Extract the germanium tetrachloride soln using separator column of the present invention obtained to filter, carry out dropwise operation specifically, it is 5 ~ 10ml/min that rate of addition controls, and repeats aforesaid operations 3 times by collecting the filtering solution obtained.Then, second time extracting operation is carried out.Use 12mol/L containing the hydrochloric acid of saturated chlorine during second time extraction, extraction temperature is 0 ~ 10 DEG C, and extraction time is 60 min, and the refining germanium tetrachloride that density is larger is positioned at lower floor, the refining germanium tetrachloride solution obtained is hydrolyzed into germanium dioxide, is 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 all the other are mainly other components such as plumbous and zinc and the method for foundation embodiment 1 prepares broken material.Add the HCl containing 50g/L in a kettle., the H of 20g/L
2o
2be the acid solution of water with surplus; Then, under the condition stirred, add broken material, the mass ratio of acid solution and broken material is 3:1; Then at the temperature of 60 DEG C, pass into chlorine leaching, no longer absorb to the chlorine passed into; Then be warming up to 85 DEG C, carry out germanium tetrachloride distillation, obtain the gas containing germanium tetrachloride and raffinate; The raffinate obtained chlorinated distillation carries out the operation of conventional extraction indium; Described gas cooling to the room temperature containing germanium tetrachloride is obtained thick germanium tetrachloride solution, carries out extracting and filtering.Use 10 mol/L containing the hydrochloric acid of saturated chlorine during first time extraction, utilizing brine bath to control extraction temperature is 0 ~ 10 DEG C, and extraction time is 60 min.Extract the germanium tetrachloride soln using separator column of the present invention obtained to filter, carry out dropwise operation specifically, it is 5 ~ 10ml/min that rate of addition controls, and repeats aforesaid operations 3 times by collecting the filtering solution obtained.Then, second time extracting operation is carried out.Use 12mol/L containing the hydrochloric acid of saturated chlorine during second time extraction, extraction temperature is 0 ~ 10 DEG C, and extraction time is 60 min, and the refining germanium tetrachloride that density is larger is positioned at lower floor, the refining germanium tetrachloride solution obtained is hydrolyzed into 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 10 more than 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 all the other are mainly other components such as plumbous and zinc and the method for foundation embodiment 1 prepares broken material.Add the HCl containing 30 g/L in a kettle., the H of 18g/L
2o
2be the acid solution of water with surplus; Then, under the condition stirred, add broken material, the mass ratio of acid solution and broken material is 3:1; Then at the temperature of 60 DEG C, pass into chlorine leaching, no longer absorb to the chlorine passed into; Then be warming up to 90 DEG C, carry out germanium tetrachloride distillation, obtain the gas containing germanium tetrachloride and raffinate; Raffinate is carried out to the operation of conventional extraction indium; Described gas cooling to the room temperature containing germanium tetrachloride is obtained thick germanium tetrachloride solution, carries out 4 extractions.Use 10 mol/L containing the hydrochloric acid of saturated chlorine when first time and second time extraction, utilizing brine bath to control extraction temperature is 0 ~ 10 DEG C, and extraction time is 60 min.Use 12 mol/L containing the hydrochloric acid of saturated chlorine when third time and the 4th extraction, extraction temperature is 0 ~ 10 DEG C, and extraction time is 60 min, and the refining germanium tetrachloride that density is larger is positioned at lower floor, the refining germanium tetrachloride solution obtained is hydrolyzed into germanium dioxide, is reduced to germanium.The purity of the germanium obtained 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 all the other are mainly other components such as plumbous and zinc and the method for foundation embodiment 1 prepares broken material.Add the HCl containing 30 g/L in a kettle., the H of 18g/L
2o
2be the acid solution of water with surplus; Then, under the condition stirred, add broken material, the mass ratio of acid solution and broken material is 3:1; Then at the temperature of 60 DEG C, pass into chlorine leaching, no longer absorb to the chlorine passed into; Then be warming up to 90 DEG C, carry out germanium tetrachloride distillation, obtain the gas containing germanium tetrachloride and raffinate; Raffinate is carried out to the operation of conventional extraction indium; Described gas cooling to the room temperature containing germanium tetrachloride is obtained thick germanium tetrachloride solution, carries out extracting and filtering.Use 10 mol/L containing the hydrochloric acid of saturated chlorine during first time extraction, utilizing brine bath to control extraction temperature is 0 ~ 10 DEG C, and extraction time is 60 min.Extract the germanium tetrachloride soln using separator column obtained to filter, carry out dropwise operation specifically, it is 5 ~ 10ml/min that rate of addition controls, and repeats aforesaid operations 3 times by collecting the filtering solution obtained.Then, second time extracting operation is carried out.Use 12mol/L containing the hydrochloric acid of saturated chlorine during second time extraction, extraction temperature is 0 ~ 10 DEG C, and extraction time is 60 min, and the refining germanium tetrachloride that density is larger is positioned at lower floor, the refining germanium tetrachloride solution obtained is hydrolyzed into germanium dioxide, is reduced to germanium.
In this comparative example, stationary phase prepares by the following method: first, under the condition of 100 DEG C, utilizes the hydrochloric acid of 1mol to carry out acidification to the silica-gel powder that particle diameter is 1 μm, treatment time is 10 hours, and filtration after being cooled to room temperature, washing and drying obtain pretreated silica-gel powder; Then, the pretreated silica-gel powder obtained is added and is equipped with in the vacuum reaction still of dry toluene, then under the condition of 60 DEG C, drip γ-aminopropyl triethoxysilane, stirring reaction 12 h; Then tri-n-octyl amine is added, stirring reaction 8 hours; Then described stationary phase can be obtained through filtration, washing and drying; Wherein, the mass ratio of described pretreated silica-gel powder, γ-aminopropyl triethoxysilane and tri-n-octyl amine is 100:10:15.The separator column used is cylindric glass column, and diameter is 20mm, and column length is 30cm, fills stationary phase obtained above under an increased pressure, and to ensure to fill evenly, tamped density is 2g/mL.The resistivity of the germanium obtained 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 all the other are mainly other components such as plumbous and zinc and the method for foundation embodiment 1 prepares broken material.Add the HCl containing 30 g/L in a kettle., the H of 18g/L
2o
2be the acid solution of water with surplus; Then, under the condition stirred, add broken material, the mass ratio of acid solution and broken material is 3:1; Then at the temperature of 60 DEG C, pass into chlorine leaching, no longer absorb to the chlorine passed into; Then be warming up to 90 DEG C, carry out germanium tetrachloride distillation, obtain the gas containing germanium tetrachloride and raffinate; Raffinate is carried out to the operation of conventional extraction indium; Described gas cooling to the room temperature containing germanium tetrachloride is obtained thick germanium tetrachloride solution, carries out extracting and filtering.Use 10 mol/L containing the hydrochloric acid of saturated chlorine during first time extraction, utilizing brine bath to control extraction temperature is 0 ~ 10 DEG C, and extraction time is 60 min.Extract the germanium tetrachloride soln using separator column obtained to filter, carry out dropwise operation specifically, it is 5 ~ 10ml/min that rate of addition controls, and repeats aforesaid operations 3 times by collecting the filtering solution obtained.Then, second time extracting operation is carried out.Use 12mol/L containing the hydrochloric acid of saturated chlorine during second time extraction, extraction temperature is 0 ~ 10 DEG C, and extraction time is 60 min, and the refining germanium tetrachloride that density is larger is positioned at lower floor, the refining germanium tetrachloride solution obtained is hydrolyzed into germanium dioxide, is reduced to germanium.
In this comparative example, stationary phase prepares by the following method: first, under the condition of 80 DEG C, utilizes the hydrochloric acid of 1mol to carry out acidification to the silica-gel powder that particle diameter is 1 μm, treatment time is 12 hours, and filtration after being cooled to room temperature, washing and drying obtain pretreated silica-gel powder; Then, the pretreated silica-gel powder obtained is added and is equipped with in the vacuum reaction still of dry toluene, then under the condition of 60 DEG C, drip γ-aminopropyl triethoxysilane, stirring reaction 12 h; Then methacrylic acid is added, stirring reaction 8 hours; Then described stationary phase can be obtained through filtration, washing and drying; Wherein, the mass ratio of described pretreated silica-gel powder, γ-aminopropyl triethoxysilane and methacrylic acid is 100:5:3.The separator column used is cylindric glass column, and diameter is 20mm, and column length is 30cm, fills stationary phase obtained above under an increased pressure, and to ensure to fill evenly, tamped density is 2g/mL.The resistivity of the germanium obtained is 1 ~ 3 Ω cm.
For the ordinary skill in the art, specific embodiment is just to invention has been exemplary description, and obvious specific implementation of the present invention is not subject to the restrictions described above.
Claims (9)
1. utilize germanium slag to extract a method for scattered metals indium and germanium, it is characterized in that: the germanium slag obtained with vacuum distillating hard-zinc is raw material, said method comprising the steps of:
Ball milling is carried out to described germanium slag and obtains the ball milling material that particle diameter is 10 μm, then utilize sulphuric acid soln to leach;
Carry out oxidizing roasting to leaching the leached mud obtained and be broken into the broken material that particle diameter is less than 1 μm;
Chlorinated distillation is carried out to described broken material;
What obtain chlorinated distillation carries out cooling containing the gas of germanium tetrachloride and obtains thick germanium tetrachloride solution;
The hydrochloric acid soln containing saturated chlorine is utilized to carry out first time extraction to described thick germanium tetrachloride liquid;
Filter extracting the germanium tetrachloride soln using separator column obtained for the first time;
Carry out second time and extract by filtering the germanium tetrachloride soln using that the obtains hydrochloric acid soln containing saturated chlorine and obtain refining germanium tetrachloride solution;
The refining germanium tetrachloride solution obtained is hydrolyzed into germanium dioxide and is reduced to germanium.
2. the method utilizing germanium slag to extract scattered metals indium and germanium according to claim 1, it is characterized in that: in described germanium slag, the content of germanium is 1.3 ~ 2.0wt%, the content of indium is 1.5 ~ 2.5wt%.
3. the method utilizing germanium slag to extract scattered metals indium and germanium according to claim 1, it is characterized in that: the concentration of sulphuric acid soln is 0.2 ~ 1.0 mol/L, the consumption of sulphuric acid soln is 1.5 ~ 2.0 times of germanium slag amount.
4. the method utilizing germanium slag to extract scattered metals indium and germanium according to claim 1, it is characterized in that: described oxidizing roasting is carried out under air conditions, and maturing temperature is 350 ~ 450 DEG C.
5. the method utilizing germanium slag to extract scattered metals indium and germanium according to claim 1, is characterized in that: described chlorinated distillation carries out in a kettle.; First, add the HCl containing 25 ~ 50g/L in a kettle., the H of 15 ~ 20g/L
2o
2be the acid solution of water with surplus; Then, under the condition stirred, add broken material, the mass ratio of acid solution and broken material is 3:1; Then at the temperature of 50 ~ 70 DEG C, pass into chlorine leaching, no longer absorb to the chlorine passed into; Then be warming up to 85 ~ 95 DEG C, carry out germanium tetrachloride distillation, obtain the gas containing germanium tetrachloride.
6. the method utilizing germanium slag to extract scattered metals indium and germanium according to claim 1, is characterized in that: the raffinate obtained chlorinated distillation carries out the operation of conventional extraction indium.
7. the method utilizing germanium slag to extract scattered metals indium and germanium according to claim 1, is characterized in that: use 10 mol/L containing the hydrochloric acid of saturated chlorine during first time extraction, extraction temperature is 0 ~ 10 DEG C, and extraction time is 45 ~ 60 min.
8. the method utilizing germanium slag to extract scattered metals indium and germanium according to claim 1, is characterized in that: use 12mol/L containing the hydrochloric acid of saturated chlorine during second time extraction, extraction temperature is 0 ~ 10 DEG C, and extraction time is 45 ~ 60 min.
9. the method utilizing germanium slag to extract scattered metals indium and germanium according to claim 1, is characterized in that: the stationary phase in described separator column is the silica gel that surface grafting has methacrylic acid and trioctylamine.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108007816A (en) * | 2017-12-18 | 2018-05-08 | 清远先导材料有限公司 | The detection method of active metal simple substance in a kind of hard zinc |
| CN108147375A (en) * | 2017-12-27 | 2018-06-12 | 清远先导材料有限公司 | A kind of recovery method of selenium germanium chalcogenide glass |
| CN111020204A (en) * | 2019-12-31 | 2020-04-17 | 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 |
| CN116623018A (en) * | 2023-06-27 | 2023-08-22 | 昆明冶金研究院有限公司 | Method for extracting germanium by acid burning |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108007816A (en) * | 2017-12-18 | 2018-05-08 | 清远先导材料有限公司 | The detection method of active metal simple substance in a kind of hard zinc |
| CN108147375A (en) * | 2017-12-27 | 2018-06-12 | 清远先导材料有限公司 | A kind of recovery method of selenium germanium chalcogenide glass |
| 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 |
| CN111020204A (en) * | 2019-12-31 | 2020-04-17 | 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 |
| 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 |
| CN116623018A (en) * | 2023-06-27 | 2023-08-22 | 昆明冶金研究院有限公司 | Method for extracting germanium by acid burning |
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