CN109055760A - A kind of method of the high arsenic germanium material Ti recovery of high zinc - Google Patents
A kind of method of the high arsenic germanium material Ti recovery of high zinc Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
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- C01—INORGANIC CHEMISTRY
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- C01G17/02—Germanium dioxide
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- C22B11/00—Obtaining noble metals
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22B15/00—Obtaining copper
- C22B15/0026—Pyrometallurgy
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0065—Leaching or slurrying
- C22B15/0067—Leaching or slurrying with acids or salts thereof
- C22B15/0071—Leaching or slurrying with acids or salts thereof containing sulfur
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- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/20—Obtaining zinc otherwise than by distilling
- C22B19/22—Obtaining zinc otherwise than by distilling with leaching with acids
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- 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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Abstract
The invention belongs to metallurgy of rare metal field, a kind of method for disclosing high arsenic germanium material Ti recovery of high zinc.The high arsenic germanium material of high zinc is crushed, after ball milling, through sour once leaching, the secondary leaching of acid, the heavy germanium of a sour immersion liquid, arrives liquid after germanium concentrate and heavy germanium；The heavy zinc of carbonate is added after to heavy germanium in liquid, controls solution terminal pH between 7~8, liquid is sent into the wastewater treatment stage after heavy zinc.The present invention is by being added the direct wet-leaching of additive, so that the arsyl in raw material originally enters slag, solves the high arsenic germanium material of high zinc and does not pass through roasting inhibition AsH3The safety problem of generation, while effectively having recycled the valuable metals such as zinc germanium, and germanium is sunk by molysite and replaces traditional tannin and sinks germanium, the production cost of germanium is greatly reduced, the productivity effect of germanium is improved, is a kind of germanium recovery method of safe green environmental protection low cost.
Description
Technical field
The invention belongs to metallurgy of rare metal fields, are related to the recycling of germanium, and in particular to a kind of high high arsenic germanium material recycling of zinc
The method of germanium.
Background technique
Germanium is a kind of eare scattered metals, in nature other than very small amount of germanium ore, almost without individually solely
Vertical germanium deposit, main preservation is in nonferrous metals ore and coal mine.Germanium has various special natures, navigates in semiconductor, aviation
The fields such as its observing and controlling, nuclear physics detecting, optical-fibre communications, infrared optics, solar battery, chemical catalyst, biomedicine have
Extensive and important application is a kind of important strategic resource.In the electronics industry, in alloy pretreatment, in optics industry
On, it is also used as catalyst.
Arsenic is widespread in nature, and the abundance of arsenic is about 2g/t in the earth's crust, and arsenic mineral existing for nature has 150
Kind, and often with sulfide minerals and the noble metal such as chalcopyrite, pyrite, magnetic iron ore, stibnite, galena, zincblende, cassiterite
Close symbiosis.
The main germanium resource in China concentrates in zincblende, is mainly distributed on the Huize, yunnan area and Guangdong Shaoguan in China
Area, so zincblende is one of the primary raw material for extracting germanium.Simultaneously usually also containing elements such as indium, arsenic in zincblende, in zinc
Pyrometallurgical smelting during indium, germanium, arsenic will be enriched with, form the material of In, Ge containing arsenic.The material component is complicated, to its into
Row material phase analysis, the material have zinc metal, iron, calcium oxide, aluminium oxide, germanium oxide, ferrosilite magnesium, silica, oxygen containing arsenic
Compound etc..This material generally contain it is relatively high, generally use hydrometallurgic recovery, but due in material contain active elemental gold
Belong to and the compounds such as arsenic, therefore often generates arsenic hydride during Ti recovery and influence the safety of operator.Mesh
The method of preceding mainstream is by making elemental metals be converted to oxide and reduce arsenic to calcination process after this material progress ore grinding
Harm, but when the leaded zinc of this material is high, during roasting can dross and make active metal be difficult complete oxidation, cause
It cannot be fully solved safety problem in process of production.
Summary of the invention
For the existing high high intractable problem of arsenic germanium material of zinc, the present invention provides a kind of high high arsenic germanium material Ti recoveries of zinc
Method, this method is easy to operate, process flow is short, can efficient valuable metals such as synthetical recovery zinc germanium lead silver, while molysite is heavy
Germanium replaces the heavy germanium of tannin, reduces production cost, provides necessary technical support to the development of germanium industry.
In order to solve the above technical problems, the invention adopts the following technical scheme:
A kind of method of the high arsenic germanium material Ti recovery of high zinc, method includes the following steps:
(1) it ball milling: using the high arsenic germanium material of high zinc as raw material, is crushed, is milled to 200 mesh or less；
(2) acid is primary leaches: the high arsenic germanium material of high zinc that step (1) obtains being done acid with acid solution and is once leached, addition is added
Agent and oxidant, primary leach of acid obtain a sour phase analysis and a sour immersion liquid；
(3) the secondary leaching of acid: carries out secondary pickling to a sour phase analysis with sulfuric acid, control end acid concentration 60~100g/L it
Between, obtain sour two immersion liquid and sour two phase analysis；
(4) the heavy germanium of a sour immersion liquid: heavy germanium agent being added into a sour immersion liquid, adjusts one immersion liquid terminal pH of acid 6~7, obtains
Liquid after germanium concentrate and heavy germanium；
(5) the heavy zinc of liquid after heavy germanium: being added the heavy zinc of carbonate, control solution terminal pH between 7~8 in liquid after to heavy germanium,
Liquid is sent into the wastewater treatment stage after heavy zinc.
Wherein, the method for the high arsenic germanium material Ti recovery of above-mentioned high zinc includes in the high high arsenic germanium material of zinc: Zn 16~
1000~2000g/t of 30wt%, Pb 18~28wt%, As 12~27wt%, Ge 1.00~1.30wt%, In.
Wherein, the method for the high arsenic germanium material Ti recovery of above-mentioned high zinc, in step (2), acid is primary when leaching, and the acid solution is sulphur
Acid solution or the secondary leachate of acid, 4~7:1 of liquid-solid ratio react 2~4h, and reaction temperature is 70~90 DEG C, and initial acidity is 60
Between~100g/L, reaction end acidity is 20~60g/L.
Wherein, the method for the high arsenic germanium material Ti recovery of above-mentioned high zinc, in step (2), the additive is containing manganese, iron, copper etc.
The compounds such as the compound with oxidisability, such as potassium permanganate, ferric sulfate, iron chloride, copper sulphate, copper chloride and copper nitrate,
The additional amount of additive is 5~10wt% of the high arsenic germanium material of high zinc.
Wherein, the method for the high arsenic germanium material Ti recovery of above-mentioned high zinc, in step (2), the oxidant is hydrogen peroxide, oxidant
Additional amount and the high arsenic germanium material of high zinc volume mass ratio (L/kg) be 1:10~20.
Wherein, the method for the high arsenic germanium material Ti recovery of above-mentioned high zinc, the concrete operations item of the secondary leaching of acid described in step (3)
Part are as follows: the liquid-solid ratio of sulfuric acid solution and a sour phase analysis is 3~5:1, and extraction temperature is 70~90 DEG C, and extraction time is 2~3h, eventually
60~100g/L of acid.
Wherein, the method for the high arsenic germanium material Ti recovery of above-mentioned high zinc, in step (3), sour two immersion liquid returns to the primary leaching of acid
Out, sour two phase analysis enter the valuable metals such as lead pyrogenic process recovery system recycling lead bronze.
Wherein, the method for the high arsenic germanium material Ti recovery of above-mentioned high zinc, germanium agent of sinking described in step (4) is trivalent iron salt, such as
The compound of the iron such as ferric sulfate, iron chloride, ferric nitrate, Fe/Ge mass ratio are 4~7:1, and reaction temperature is room temperature, reaction time
For 2~3h.Alkali can be added when adjusting one immersion liquid terminal pH of acid, such as piece alkali can be added.The germanium grade of germanium concentrate be 3~
10%, such as 3~8%；Germanium concentrate prepares germanium dioxide by distillation and hydrolysis.
Wherein, the method for the high arsenic germanium material Ti recovery of above-mentioned high zinc, in step (5), the carbonate is sodium carbonate, carbonic acid
The carbonate such as ammonium, potassium carbonate, additional amount are 1.5~2.0 times of theoretical reacting dose, and the reaction time is 1~3h.
Wherein, the method for the high arsenic germanium material Ti recovery of above-mentioned high zinc further includes liquid processing after step (6) heavy zinc: to after heavy zinc
Liquid is added biological agent and is handled, and makes heavy metal in waste water whole qualified discharge.The biological agent is known in the art system
Agent.
Compared with prior art, it the beneficial effects of the present invention are: the method for the present invention eliminates calcining process, can directly carry out
Acidic leaching, it is easy to operate, process flow is short, it solves in the high arsenic germanium material acidleach treatment process of high zinc and generates AsH3Bring peace
Full problem, at the same can efficient valuable metals such as synthetical recovery zinc germanium lead silver, zinc germanium lead silver comprehensive recovery is both greater than 90%, and
Have for solve the high efficiente callback of germanium in such slag, make full use of rare germanium resource and protection environment etc. very positive
Meaning.The heavy germanium of tannin is replaced using the heavy germanium of molysite simultaneously, production cost is reduced, necessary skill is provided to the development of germanium industry
Art is supported.
Detailed description of the invention
Fig. 1 is the process flow chart of the recovery indium germanium from high zinc high arsenic germanium material in the embodiment of the present invention 1.
Specific embodiment
Further detailed description is done to technical solution of the present invention below in conjunction with specific embodiment.The following example
It is merely illustrative the ground description and interpretation present invention, and is not necessarily to be construed as limiting the scope of the invention.It is all to be based on this hair
In the range of the technology that bright above content is realized is encompassed by the present invention is directed to protect.
Unless otherwise indicated, raw materials and reagents used in the following embodiment are commercial goods, or can be by
Perception method preparation.
Embodiment 1
By the high arsenic germanium material of high zinc (Zn:28.4wt%, Pb:26.19wt%, As:14.07wt%, Ge:1.105wt%, In:
1731g/t) goal grinding machine is milled to 200 mesh hereinafter, configuring 16m in surge tank3Additive A-potassium permanganate is added in aqueous solution
Then the high germanium material 8t of the high zinc of milled is poured into surge tank, 50m is transferred to after stirring by 400kg3In reactive tank, hydrogen peroxide is added,
Hydrogen peroxide adds 2h by 250L/h rate, and the sulfuric acid solution or the secondary leachate of acid that acid is 60g/L that begin are added into reactive tank
40m3, heating is stirred to react, and temperature is 85 DEG C, reaction time 4h, and controlling acid eventually is 40g/L, filters pressing is carried out after reaction,
Filter residue pours into the secondary leaching reactive tank of acid, and 40m is passed through into reactive tank3Sulfuric acid solution, heating is stirred to react, and temperature is 80 DEG C,
Reaction time is 2h, controls acid eventually and carries out filters pressing after reaction in 60g/L, the secondary phase analysis of acid returns lead smelting system and recycles lead
The valuable metals such as copper, the secondary leachate of acid return to the primary leaching of acid and return leaching.A sour leachate, which is squeezed into heavy germanium reactive tank, to carry out
Heavy germanium, Fe in mass ratio in reaction3+Ferric sulfate solid is added in/Ge=5:1, and normal-temperature reaction 2h, filters pressing carries out liquid after the reaction was completed
Gu separation, germanium concentrate carries out distillation hydrolysis production high-purity germanium dioxide after drying and processing, and liquid squeezes into heavy zinc slot and sunk after heavy germanium
Zinc, by 1.5 times of addition sodium carbonate of theoretical amount, liquid carries out wastewater treatment, qualified discharge after heavy zinc.Specific steps result of laboratory test is such as
Shown in Tables 1 and 2.
1 each process liquid sample result of table
| Element | Zn(g/L) | As(g/L) | Ge(g/L) |
| A sour leachate | 35.76 | 1.04 | 1.31 |
| The secondary leachate of acid | 6.01 | 2.07 | 0.33 |
| Liquid after heavy germanium | 32.15 | 0.95 | 0.089 |
| Liquid after heavy zinc | 0.71 | 0.065 |
2 slag specimen result of table
| Element | Ge (%) | Zn (%) | As (%) | Ge leaching rate (%) | Zn leaching rate (%) | As leaching rate (%) |
| Germanium concentrate | 7.58 | |||||
| Zinc carbonate | 33.81 | |||||
| The secondary leached mud of acid | 0.12 | 2.49 | 21.72 | 94.21 | 94.95 | 12.15 |
Embodiment 2
By the high arsenic germanium material of high zinc (Zn:21.39wt%, Pb:20.52wt%, As:15.69wt%, Ge:1.23wt%, In:
1923g/t) goal grinding machine is milled to 200 mesh hereinafter, configuring 16m in surge tank3Additive-iron chloride is added in aqueous solution
Then the high germanium material 8t of the high zinc of milled is poured into surge tank, 50m is transferred to after stirring by 660kg3In reactive tank, hydrogen peroxide is added,
Hydrogen peroxide adds 2h by 300L/h rate, and the sulfuric acid solution or the secondary leachate of acid that acid is 80g/L that begin are added into reactive tank
40m3, heating is stirred to react, and temperature is 85 DEG C, reaction time 4h, and controlling acid eventually is 40g/L, filters pressing is carried out after reaction,
Filter residue pours into the secondary leaching reactive tank of acid, and 40m is passed through into reactive tank3Sulfuric acid solution, heating is stirred to react, and temperature is 80 DEG C,
Reaction time is 2h, controls acid eventually and carries out filters pressing after reaction in 80g/L, the secondary phase analysis of acid returns lead smelting system and recycles lead
The valuable metals such as copper, the secondary leachate of acid return to the primary leaching of acid and return leaching.A sour leachate, which is squeezed into heavy germanium reactive tank, to carry out
Heavy germanium, Fe in mass ratio in reaction3+Ferric sulfate solid is added in/Ge=6:1, and normal-temperature reaction 2h, filters pressing carries out liquid after the reaction was completed
Gu separation, germanium concentrate carries out distillation hydrolysis production high-purity germanium dioxide after drying and processing, and liquid squeezes into heavy zinc slot and sunk after heavy germanium
Zinc, by 1.8 times of addition sodium carbonate of theoretical amount, liquid carries out wastewater treatment, qualified discharge after heavy zinc.Specific steps result of laboratory test is such as
Shown in table 3 and table 4.
3 each process liquid sample result of table
| Element | Zn(g/L) | As(g/L) | Ge(g/L) |
| A sour leachate | 31.18 | 0.84 | 1.64 |
| The secondary leachate of acid | 4.95 | 1.65 | 0.47 |
| Liquid after heavy germanium | 27.62 | 0.72 | 0.034 |
| Liquid after heavy zinc | 0.62 | 0.062 |
4 slag specimen result of table
| Element | Ge (%) | Zn (%) | As (%) | Ge leaching rate (%) | Zn leaching rate (%) | As leaching rate (%) |
| Germanium concentrate | 5.89 | |||||
| Zinc carbonate | 31.29 | |||||
| The secondary leached mud of acid | 0.16 | 2.63 | 25.32 | 92.79 | 94.17 | 8.35 |
Embodiment 3
By the high arsenic germanium material of high zinc (Zn:19.02wt%, Pb:22.35wt%, As:25.81wt%, Ge:1.08wt%, In:
1120g/t) goal grinding machine is milled to 200 mesh hereinafter, configuring 16m in surge tank3Additive-copper sulphate is added in aqueous solution
Then the high germanium material 8t of the high zinc of milled is poured into surge tank, 50m is transferred to after stirring by 600kg3In reactive tank, hydrogen peroxide is added,
Hydrogen peroxide adds 2h by 400L/h rate, and the sulfuric acid solution or the secondary leachate of acid that acid is 80g/L that begin are added into reactive tank
40m3, heating is stirred to react, and temperature is 85 DEG C, reaction time 4h, and controlling acid eventually is 30g/L, filters pressing is carried out after reaction,
Filter residue pours into the secondary leaching reactive tank of acid, and 40m is passed through into reactive tank3Sulfuric acid solution, heating is stirred to react, and temperature is 80 DEG C,
Reaction time is 2h, controls acid eventually and carries out filters pressing after reaction in 80g/L, the secondary phase analysis of acid returns lead smelting system and recycles lead
The valuable metals such as copper, the secondary leachate of acid return to the primary leaching of acid and return leaching.A sour leachate, which is squeezed into heavy germanium reactive tank, to carry out
Heavy germanium, Fe in mass ratio in reaction3+Ferric sulfate solid is added in/Ge=7:1, and normal-temperature reaction 2h, filters pressing carries out liquid after the reaction was completed
Gu separation, germanium concentrate carries out distillation hydrolysis production high-purity germanium dioxide after drying and processing, and liquid squeezes into heavy zinc slot and sunk after heavy germanium
Zinc, by 2.0 times of addition sodium carbonate of theoretical amount, liquid carries out wastewater treatment, qualified discharge after heavy zinc.Specific steps result of laboratory test is such as
Shown in table 5 and table 6.
5 each process liquid sample result of table
| Element | Zn(g/L) | As(g/L) | Ge(g/L) |
| A sour leachate | 31.46 | 0.93 | 1.38 |
| The secondary leachate of acid | 7.23 | 1.28 | 0.29 |
| Liquid after heavy germanium | 25.86 | 0.76 | 0.015 |
| Liquid after heavy zinc | 0.52 | 0.053 |
6 slag specimen result of table
| Element | Ge (%) | Zn (%) | As (%) | Ge leaching rate (%) | Zn leaching rate (%) | As leaching rate (%) |
| Germanium concentrate | 4.56 | |||||
| Zinc carbonate | 32.12 | |||||
| The secondary leached mud of acid | 0.139 | 2.12 | 39.93 | 90.91 | 93.80 | 4.1 |
It can be seen that from Examples 1 to 3, the method for the present invention is easy to operate, simple process and process are short, solves the high arsenic of high zinc
AsH is generated in germanium material acidleach treatment process3Bring safety problem, while being capable of the efficient valuable gold such as synthetical recovery zinc germanium lead bronze
Belong to, zinc germanium comprehensive recovery is both greater than 90%, has very for recycling and the protection environment etc. that solve zinc germanium in such slag
Positive meaning.Replace the heavy germanium of tannin using the heavy germanium of molysite simultaneously, reduces production cost, providing to the development of germanium industry must
The technical support wanted.
Claims (10)
1. a kind of method of the high arsenic germanium material Ti recovery of high zinc, which is characterized in that method includes the following steps:
(1) it ball milling: using the high arsenic germanium material of high zinc as raw material, is crushed, is milled to 200 mesh or less；
(2) acid is primary leaches: by the high arsenic germanium material of high zinc that step (1) obtains with acid solution do it is sour it is primary leach, be added additive and
Oxidant, primary leach of acid obtain a sour phase analysis and a sour immersion liquid；
(3) the secondary leaching of acid: carrying out secondary pickling to a sour phase analysis with sulfuric acid, control whole acid concentration between 60~100g/L,
Obtain sour two immersion liquid and sour two phase analysis；
(4) the heavy germanium of a sour immersion liquid: heavy germanium agent being added into a sour immersion liquid, adjusts one immersion liquid terminal pH of acid 6~7, it is smart to obtain germanium
Liquid after mine and heavy germanium；
(5) the heavy zinc of liquid after heavy germanium: being added the heavy zinc of carbonate, control solution terminal pH between 7~8 in liquid after to heavy germanium, heavy zinc
Liquid is sent into the wastewater treatment stage afterwards.
2. the method for the high arsenic germanium material Ti recovery of high zinc according to claim 1, which is characterized in that the high high arsenic germanium material of zinc
In include: Zn 16~30wt%, Pb 18~28wt%, As 12~27wt%, Ge 1.00~1.30wt%, In 1000~
2000g/t。
3. the method for the high arsenic germanium material Ti recovery of high zinc according to claim 1, which is characterized in that in step (2), acid is primary
When leaching, the acid solution is that sulfuric acid solution or the secondary leachate of acid, 4~7:1 of liquid-solid ratio react 2~4h, reaction temperature 70
~90 DEG C, for initial acidity between 60~100g/L, reaction end acidity is 20~60g/L.
4. the method for the high arsenic germanium material Ti recovery of high zinc according to claim 1, which is characterized in that described to add in step (2)
Add agent be containing manganese, iron, copper the compound with oxidisability, the additional amount of additive for the high arsenic germanium material of high zinc 5~10wt%.
5. the method for the high arsenic germanium material Ti recovery of high zinc according to claim 1, which is characterized in that in step (2), the oxygen
Agent is hydrogen peroxide, and the volume mass ratio (L/kg) of the additional amount of oxidant and the high arsenic germanium material of high zinc is 1:10~20.
6. the method for the high arsenic germanium material Ti recovery of high zinc according to claim 1, which is characterized in that acid described in step (3)
The concrete operations condition of secondary leaching are as follows: the liquid-solid ratio of sulfuric acid solution and a sour phase analysis is 3~5:1, and extraction temperature is 70~90
DEG C, extraction time is 2~3h, eventually 60~100g/L of acid.
7. the method for the high arsenic germanium material Ti recovery of high zinc according to claim 1, which is characterized in that in step (3), the acid
Two immersion liquid return to the primary leaching of acid, and sour two phase analysis enter the valuable metals such as lead pyrogenic process recovery system recycling lead.
8. the method for the high arsenic germanium material Ti recovery of high zinc according to claim 1, which is characterized in that sink described in step (4)
Germanium agent is trivalent iron salt, and Fe/Ge mass ratio is 4~7:1, and reaction temperature is room temperature, and the reaction time is 2~3h.
9. the method for the high arsenic germanium material Ti recovery of high zinc according to claim 1, which is characterized in that in step (5), the carbon
Hydrochlorate is at least one of sodium carbonate, ammonium carbonate, potassium carbonate, and additional amount is 1.5~2.0 times of theoretical reacting dose, reaction
Time is 1~3h.
10. the method for the high arsenic germanium material Ti recovery of high zinc according to claim 1, which is characterized in that this method further includes step
Suddenly liquid is handled after (6) heavy zinc: liquid is added biological agent and is handled after to heavy zinc, makes heavy metal in waste water whole qualified discharge.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110819806A (en) * | 2019-11-01 | 2020-02-21 | 郴州丰越环保科技有限公司 | Preparation method for preparing zinc iron sulfate flocculating agent from germanium extraction liquid |
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| CN116287733A (en) * | 2023-05-25 | 2023-06-23 | 昆明理工大学 | Method for inhibiting lead alum from adsorbing germanium in leaching process of germanium-containing zinc oxide smoke dust by ultrasonic cooperation |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110819806A (en) * | 2019-11-01 | 2020-02-21 | 郴州丰越环保科技有限公司 | Preparation method for preparing zinc iron sulfate flocculating agent from germanium extraction liquid |
| CN111041227A (en) * | 2019-11-27 | 2020-04-21 | 曲靖师范学院 | Method for removing arsenic, iron and organic matters from zinc sulfate solution obtained after germanium precipitation of zinc oxide smoke leachate |
| CN111041227B (en) * | 2019-11-27 | 2021-11-09 | 曲靖师范学院 | Method for removing arsenic, iron and organic matters from zinc sulfate solution obtained after germanium precipitation of zinc oxide smoke leachate |
| CN113215420A (en) * | 2021-04-30 | 2021-08-06 | 上海第二工业大学 | Method for recycling germanium from germanium-doped waste optical fiber |
| CN113215420B (en) * | 2021-04-30 | 2022-06-14 | 上海第二工业大学 | Method for recycling germanium from germanium-doped waste optical fiber |
| CN116287733A (en) * | 2023-05-25 | 2023-06-23 | 昆明理工大学 | Method for inhibiting lead alum from adsorbing germanium in leaching process of germanium-containing zinc oxide smoke dust by ultrasonic cooperation |
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