CN109439909A - A method of the Ti recovery from high siliceous optical fiber production waste material - Google Patents
A method of the Ti recovery from high siliceous optical fiber production waste material Download PDFInfo
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- CN109439909A CN109439909A CN201811537883.4A CN201811537883A CN109439909A CN 109439909 A CN109439909 A CN 109439909A CN 201811537883 A CN201811537883 A CN 201811537883A CN 109439909 A CN109439909 A CN 109439909A
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- germanium
- optical fiber
- volatilization
- fiber production
- waste material
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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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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B41/00—Obtaining germanium
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention discloses a kind of methods of Ti recovery from high siliceous optical fiber production waste material, comprising the following steps: and it is (1) that the high waste material of optical fiber production containing SiGe is levigate to more than 100 mesh, vulcanizing agent is then added and is uniformly mixed granulation as diameter 1-5mm；(2) sulfiding volatilization of germanium is carried out, and collects germanium sulfide volatilization flue dust, or collect the mixed volatilization flue dust of germanium sulfide and germanium dioxide；(3) germanium-containing smoke dust of acquisition is subjected to microwave oxidizing roasting or the oxidizing roasting of other forms or directly carries out sulfuric acid oxidation leaching；(4) high germanic microwave oxidizing roasting product is directly subjected to chlorination of hydrochloric acid distillation, obtains germanium tetrachloride and is hydrolyzed to obtain germanium dioxide concentrate；(5) the low germanium-containing material of step (2) and step (3) is subjected to sulfuric acid oxidation leaching, leachate is precipitated with tannin or organic solvent extracts Extraction and enrichment germanium, produces germanium concentrate.The present invention being capable of high efficiency, at low cost the extraction separating Ge, silicon from the siliceous material up to 95% or more.
Description
Technical field
The present invention relates to the bottom slag or dross of a kind of high siliceous and germanium generated in germnium doped fiber produces, and it is therefrom low
The technology of cost high efficiency Ti recovery belongs to dilute scattered rare metal synthetical recovery field.
Background technique
Optical-fibre communications is communicated instead of traditional wire cable, and optical fiber production must mix germanium and could have communication excellent
Gesture.Dosage of the germanium in optical-fibre communications has reached 30% or more of total germanium dosage at present.Germanium is a kind of dilute scattered rare metal, geology
Reserves are limited, and purposes is wide, and value is high.Therefore Ti recovery has important economic results in society from various regenerated resources.Mix germanium
Optical fiber production can generate 5% or so bottom ash and dross, general siliceous in 95%-97%, germanic 2%-3% in the slag.Due to siliceous
Height cannot directly carry out chlorination of hydrochloric acid distillation germanium tetrachloride, mix because silicon can also be steamed with silicon tetrachloride with germanium tetrachloride, water
Germanium dioxide and precipitation of silica are generated simultaneously when solution, it can not separating Ge and silicon.Directly use sulfuric acid leaching or sulfuric acid oxidation
It leaches, due to Silica-coated germanium, germanium can not be leached.It is leached using sodium hydroxide or fluoride, obtained leachate is siliceous
It is very high, it all can not be successfully and carry out the separation of germanium silicon.Sodium hydroxide or fluoride all consume very big simultaneously, and production cost is very high, nothing
Method receives.
Summary of the invention
The present invention uses the sulfiding volatilization technology of germanium first, can from optical fiber production waste material of the height containing SiGe concentration and separation
Germanium, the mixture for obtaining germanium sulfide or germanium sulfide and germanium dioxide (be when using fuming furnace to be firstly vulcanized volatilization, then in the flue dust that volatilizees
Oxidation of sulfureted germanium obtains the germanium sulfide mixture containing incomplete oxidation based on germanium dioxide in pipeline), then carry out low-temperature oxidation roasting
It burns or directly carries out sulfuric acid oxidation leaching, then therefrom use conventional method Ti recovery.The present invention is not only in separation and concentration waste material
Germanium, and evaded the harm of a large amount of silicon.Obtain the low cost of the material, the good effect of high efficiency Ti recovery.
Technical solution of the present invention:
A method of the Ti recovery from high siliceous optical fiber production waste material, it is characterised in that: the following steps are included:
(1) the high waste material of optical fiber production containing SiGe is levigate to more than 100 mesh, vulcanizing agent being then added and be uniformly mixed that pelletize be straight
Diameter 1-5mm；It destroys crystal silicon structure and silicon wraps up germanium phenomenon；
(2) the granulation material of step (1) is subjected to the sulfiding volatilization of germanium, and collects germanium sulfide volatilization flue dust, or collect germanium sulfide
With the mixed volatilization flue dust of germanium dioxide；The sulfiding volatilization condition is S/Ge=1.2-1.3, and vulcanizing agent is vulcanized sodium or simple substance
Sulphur powder, 800-1000 DEG C of volatilization temperature, flat panel display is micro-wave oven or fuming furnace or rotary kiln；
(3) germanium-containing smoke dust for obtaining step (2) carries out microwave oxidizing roasting or the oxidizing roasting of other forms or directly carries out
Sulfuric acid oxidation leaches；
(4) the germanic microwave oxidizing roasting product of height of step (3) is directly subjected to chlorination of hydrochloric acid distillation, obtains germanium tetrachloride and carries out
Hydrolysis obtains germanium dioxide concentrate；
(5) the low germanium-containing material of step (2) and step (3) is subjected to sulfuric acid oxidation leaching, leachate tannin precipitating or organic
Solvent extraction Extraction and enrichment germanium produces germanium concentrate.
The siliceous optical fiber production waste material of height of the step (1) is siliceous 95% or more, germanic 2% or more, remaining impurity 1% with
Under bottom slag and dross.
The step (3) preferably microwave oxidizing roasting, maturing temperature are 300-500 DEG C, and Oxidation Leaching is atmospheric low-temperature sulphur
Acid solution adds hydrogen peroxide or the Oxidation Leaching or high temperature and pressure dioxygen oxidation of potassium permanganate leach.
The silicon slag that the sulfiding volatilization of the step (3) leaves is used as cement producting material after appropriately processed.
The working principle of the invention:
Although silicon and germanium belong to a major element, germanium easily generates germanium sulfide and germanium disulfide with sulphur, and silicon then not with sulphur
Directly reaction generates sulfide.The distillation volatilization temperature of the sulfide of germanium especially germanium sulfide is lower, and about 800-1000 DEG C, therefore
As long as the germanium in high SiGe raw material is exposed, do not wrapped up, and have sufficient elementary sulfur in combination, 800 DEG C or so just
Generation germanium sulfide distillation can be reacted to evaporate.As temperature increases, germanium sulfide is contacted with sulphur generates germanium disulfide, and at this moment two
Germanium sulfide does not have sublimation characteristics, but still can largely evaporate at 1000 DEG C or so.Temperature is improved again, the volatilization to germanium sulfide
It has little significance, silica can be made to melt instead, generate package phenomenon, reduce the volatility of germanium sulfide.
Silica and germanium dioxide are all the permeation bodies of microwave radiation, do not absorb microwave radiation, but vulcanized sodium, sulphur simple substance
And the germanium sulfide that reaction generates, germanium disulfide is the substance of high-selenium corn microwave radiation, therefore is vulcanized when using microwave radiation
When volatilization, sulfide selective absorbing microwave radiation only therein generates instantaneous high-temperature, generates germanium and reaction of Salmon-Saxl and vulcanizes
Germanium, and germanium sulfide continues to absorb microwave radiation, reaches the temperature of distillation and volatilization, microwave radiation transmittance is very strong, and uniformly,
The volatilization of germanium sulfide is high-efficient, will not generate excessively high localized hyperthermia, and resulting mainly germanium sulfide is conducive at subsequent handling
Reason, compared with fuming furnace, the indirect heating manner of rotary kiln and by medium progress heat transfer it is superior.With fuming furnace or rotary kiln into
Row sulfiding volatilization, due to being to be inevitably generated the oxidation of partial vulcanization germanium with fuel combustion offer heat, therefore obtain
It is the mixture of germanium sulfide and germanium oxide.Although being conducive to subsequent handling oxidizing roasting or sulfuric acid oxidation leaching, in entire sulphur
Change in volatilization there are hyperthermia and superheating phenomenon and cold center phenomenon, this all will affect sulfiding volatilization rate and more unfavorable containing germanium disulfide
In subsequent handling processing.Therefore the present invention preferably microwave radiation carries out the sulfiding volatilization of germanium and the oxidation roasting of subsequent germanium sulfide
It burns.
Specific embodiment
Embodiment: a method of the Ti recovery from high siliceous optical fiber production waste material, comprising the following steps:
Step 1, by the optical fiber production waste material (bottom slag and dross) containing high silicon it is levigate to more than 100 mesh, destroy crystal silicon structure and
Silicon wraps up germanium phenomenon；
Step 2, vulcanized sodium is added by S/Ge=1.2-1.3 in the grinding material of step 1 or sulphur powder is uniformly mixed, and pelletized and be
Diameter 1-5mm；
Step 3, the particulate material of step 2 is added in micro-wave oven or fuming furnace or rotary kiln and other sulfiding volatilization furnaces, is controlled
The sulfiding volatilization of 800-1000 DEG C of sulfiding volatilization temperature progress germanium processed；
Step 4, the sulfiding volatilization flue dust of step 3 being subjected to oxidizing roasting, control oxidizing roasting temperature is 300-500 DEG C, this
It is noted that preventing generation germanium monoxide or the distillation volatilization of germanium sulfide high temperature when material oxidizing roasting from running away in step.Also it to prevent
High-temperature generates tetragonal structure germanium and is difficult to acidleach recycling.Therefore technology controlling and process is convenient in preferably microwave oxidizing roasting.
Step 5,5% or more of step 4 high germanic oxidizing roasting product is directly carried out chlorination of hydrochloric acid distillation is four chlorinations
Germanium, then hydrolyze and obtain germanium dioxide concentrate；Low germanic oxidizing roasting product adds oxidant with sulfuric acid and carries out Oxidation Leaching, then uses
Tannin precipitating or extraction mention germanium production high-grade germanium concentrate；
Step 6, the silicon slag that the sulfiding volatilization of step 3 leaves is used as cement producting material after appropriately processed.
The bottom slag that example 1, certain enterprise produce optical fiber output contains silica 96.5%, and germanium 2.78% is first levigate extremely by its
Then 120 mesh are uniformly mixed by the addition vulcanized sodium of S/Ge=1.2 and are pelletized as diameter 2mm.It is put into micro-wave oven vulcanize and wave
Hair.Micro-wave oven operating condition is microwave radiation frequencies 2.4GHz, power 500W, 850 DEG C of in-furnace temperature, the time 20 minutes, is obtained
Sulfiding volatilization flue dust main germanic 29.1%, sulfur-bearing 18.3% contain silica 9.2%, and volatilization residue contains silica 94.5%, germanium
0.18%, evaporation rate of germanium 92.3%.
Example 2, certain optical fiber production bottom slag and dross mixture contain silica 95.2%, and germanium 3.1% is levigate to 250 mesh
It is diameter 3.5mm that sulphur powder mixed pelletization, which is added, by S/Ge=1.25 afterwards, is put into a sulfiding volatilization furnace in laboratory and uses electric heating
Sulfiding volatilization is carried out, controls 1000 DEG C of in-furnace temperature, time 2 h must vulcanize dust germanic 27.8%, and sulfur-bearing 16.5% contains two
Silica 15.8%, slag germanic 0.31%.Evaporation rate of germanium 90%.
Example 3 carries out micro-wave oven oxidizing roasting with the sulfiding volatilization flue dust of example 1, by total sulfur content requisite oxygen in raw material
110% oxidant (hydrogen peroxide) be added be uniformly mixed, be placed in micro-wave oven control microwave power 300-500W, 350 DEG C of temperature
± 10 DEG C, the time 10 minutes.Sulfur content is down to 0.5% in product of roasting, then germanium loss by roasting 0.3% directly carries out hydrochloric acid chlorine
Change distillation germanium tetrachloride, the chlorinated distillation rate of germanium is 98.7% in terms of slag.
Example 4 carries out oxidizing roasting with the sulfiding volatilization flue dust of example 2 with air oxidant in general electric furnace, control
Temperature processed is 500 DEG C, the time 60 minutes, obtains product of roasting germanic 26.2%, sulfur-bearing 1.2%, germanium loss by roasting 5.7%.Then will
Product of roasting directly carries out chlorination of hydrochloric acid distillation germanium tetrachloride, and the chlorinated distillation rate 95.3% of germanium in terms of slag, bottoms are germanic
0.85%。
Example 5, certain optical fiber production dross germanic 1.5% contain silica 97.6%, and vulcanized sodium is added by S/Ge=1.3 and mixes
Granulation is diameter 1.5mm, carries out sulfiding volatilization with use for laboratory small rotary kiln, 900 DEG C of volatilization temperature of control, the time 1.5 hours,
Sulfiding volatilization flue dust germanic 12.8% is obtained, sulfur-bearing 9.5% contains silica 6.7%, the sulfiding volatilization rate 91.2% of germanium.Then it presses
The condition of example 3 carries out microwave oxidizing roasting and chlorination of hydrochloric acid distills germanium tetrachloride, and the chlorinated distillation rate of germanium is 96.1%, distillation
Residue germanic 0.65%.
Above example is only described further with regard to the present invention, and the present invention is not limited.
Claims (4)
1. a kind of method of the Ti recovery from high siliceous optical fiber production waste material, it is characterised in that: the following steps are included:
(1) the high waste material of optical fiber production containing SiGe is levigate to more than 100 mesh, vulcanizing agent being then added and be uniformly mixed that pelletize be straight
Diameter 1-5mm；
(2) the granulation material of step (1) is subjected to the sulfiding volatilization of germanium, and collects germanium sulfide volatilization flue dust, or collect germanium sulfide
With the mixed volatilization flue dust of germanium dioxide；The sulfiding volatilization condition is S/Ge=1.2-1.3, and vulcanizing agent is vulcanized sodium or simple substance
Sulphur powder, 800-1000 DEG C of volatilization temperature, flat panel display is micro-wave oven or fuming furnace or rotary kiln；
(3) germanium-containing smoke dust for obtaining step (2) carries out microwave oxidizing roasting or the oxidizing roasting of other forms or directly carries out
Sulfuric acid oxidation leaches；
(4) the germanic microwave oxidizing roasting product of height of step (3) is directly subjected to chlorination of hydrochloric acid distillation, obtains germanium tetrachloride and carries out
Hydrolysis obtains germanium dioxide concentrate；
(5) the low germanium-containing material of step (2) and step (3) is subjected to sulfuric acid oxidation leaching, leachate tannin precipitating or organic
Solvent extraction Extraction and enrichment germanium produces germanium concentrate.
2. a kind of method of Ti recovery from high siliceous optical fiber production waste material as described in claim 1, it is characterised in that: step
(1) the siliceous optical fiber production waste material of height is siliceous 95% or more, germanic 2% or more, remaining 1% or less impurity.
3. a kind of method of Ti recovery from high siliceous optical fiber production waste material as described in claim 1, it is characterised in that: step
(3) preferably microwave oxidizing roasting, maturing temperature are 300-500 DEG C, and Oxidation Leaching is that atmospheric low-temperature sulfuric acid solution adds hydrogen peroxide
Or the Oxidation Leaching or high temperature and pressure dioxygen oxidation of potassium permanganate leach.
4. a kind of method of Ti recovery from high siliceous optical fiber production waste material as described in claim 1, it is characterised in that: step
(3) silicon slag that sulfiding volatilization leaves is used as cement producting material after appropriately processed.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201811537883.4A CN109439909B (en) | 2018-12-15 | 2018-12-15 | Method for recycling germanium from high-silicon-content optical fiber production waste |
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| CN201811537883.4A CN109439909B (en) | 2018-12-15 | 2018-12-15 | Method for recycling germanium from high-silicon-content optical fiber production waste |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| CN114606401A (en) * | 2022-01-26 | 2022-06-10 | 株洲科能新材料股份有限公司 | Chlorine-free dry method germanium recovery method |
| CN115466856A (en) * | 2022-09-27 | 2022-12-13 | 南京金美镓业有限公司 | Method for recovering germanium from germanium-containing optical fiber waste by reduction adsorption-oxidation method |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| CN114606401A (en) * | 2022-01-26 | 2022-06-10 | 株洲科能新材料股份有限公司 | Chlorine-free dry method germanium recovery method |
| CN114606401B (en) * | 2022-01-26 | 2024-04-30 | 株洲科能新材料股份有限公司 | Chlorine-free dry germanium recovery method |
| CN115466856A (en) * | 2022-09-27 | 2022-12-13 | 南京金美镓业有限公司 | Method for recovering germanium from germanium-containing optical fiber waste by reduction adsorption-oxidation method |
| CN115466856B (en) * | 2022-09-27 | 2023-10-10 | 南京金美镓业有限公司 | Method for recovering germanium from germanium-containing optical fiber waste material by reduction adsorption-oxidation method |
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