CN110306069A - A method of the Ti recovery from germanic acid solution, germanic lye - Google Patents
A method of the Ti recovery from germanic acid solution, germanic lye Download PDFInfo
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- CN110306069A CN110306069A CN201910615841.6A CN201910615841A CN110306069A CN 110306069 A CN110306069 A CN 110306069A CN 201910615841 A CN201910615841 A CN 201910615841A CN 110306069 A CN110306069 A CN 110306069A
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- germanic
- lye
- acid solution
- germanium
- solution
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B41/00—Obtaining germanium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- 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
- C22B7/001—Dry 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
- 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
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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
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- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
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- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
A kind of method that the present invention discloses Ti recovery from germanic acid solution, germanic lye, the method includes the following steps: germanic acid solution and lye or acid solution and germanic lye being carried out neutralization reaction, obtain presoma；The presoma is aged, be filtered, washed, dried, is calcined, GeO is obtained2The rate of recovery of powder, germanium is up to 96%.Compared with traditional depositing technology, present invention reduces process flows, improve the grade of germanium, have greatly saved production cost, improve production efficiency.
Description
Technical field
The present invention relates to metallurgical technology fields, and in particular to a method of the Ti recovery from germanic acid solution, germanic lye.
Background technique
Germanium is a kind of rare metal, nature reserves far away from gold reserves.Mode that there are two types of the extractions of germanium at present,
One is refine in germanic ore；Another is extracted back from the waste residue generated in germanium product processing, in waste liquid
Receive germanium.The grade of germanium in the former ore is extremely low, needs through multiple working procedure enriched germanium, and cost is high, energy consumption is very big；The latter's germanium
Grade it is higher, extract cost recovery it is relatively low, and recycle germanium amount it is considerable.Therefore, recycling extracts offscum containing germanium, in waste liquid
Germanium become germanium industrial system in an essential ring.
Germanic acid solution, germanic lye are the waste liquids generated in germanium single crystal process, and Ge content variation range is 0.5-
150g/L.For germanium single crystal processing enterprise, it is (useless that the germanium concentrate obtained after waste liquid precipitation process is generally sold to upstream processing enterprise
Liquid peril of transportation and transportation cost are high), the grade of germanium is higher in germanium concentrate, is worth bigger.Traditional germanium recycling uses wet process
Technique first adjusts solution ph to 1-2, uses tannin (or tannin extract) precipitation adsorption germanium afterwards, oxidizing roasting obtains germanium after filtering precipitating
Concentrate.The technique mainly has the disadvantage that: first is that tannin (or tannin extract) price used is higher, second is that dosage reaches germanium metal
30-50 times, the grade of germanium concentrate is seriously reduced, third is that germanium concentrate amount is big, calcining time is long, and energy consumption is serious.
Summary of the invention
Goal of the invention: a kind of from germanic acid solution, germanic lye present invention aims in view of the deficiencies of the prior art, providing
The method of middle Ti recovery, having reduces processing cost, improves the grade of germanium concentrate, improves processing efficiency, shortens process time
Feature.
Technical solution: a kind of method of the Ti recovery from germanic acid solution, germanic lye of the present invention, the method includes
Following step: germanic acid solution and lye or acid solution and germanic lye are subjected to neutralization reaction, obtain presoma；By the presoma
It is aged, is filtered, washed, dried, calcined, obtain GeO2Powder.
Preferably, in the germanic acid solution, solute H2GeF6, germanic amount is 1-150g/L；The lye is sodium hydroxide
Solution or potassium hydroxide solution, the concentration of the lye are 0.1-18.7mol/L.
Preferably, in the germanic acid solution, germanic amount is 50-150g/L；The concentration of the lye is 5-10mol/L.
Preferably, in the germanic lye, solute Na2GeO3, germanic amount is 1-50g/L；The acid solution is sulfuric acid or nitre
Acid or hydrochloric acid, the concentration of the acid solution are 0.1-18mol/L.
Preferably, in the germanic lye, germanic amount is 20-40g/L；The concentration of the acid solution is 5-10mol/L.
Preferably, the neutralization reaction carries out under conditions of mechanical stirring, and the rate of the stirring is 120-1000r/
Min, stirring to the pH value of solution is 5-9.
Preferably, the rate of the stirring is 200-300r/min, and stirring to the pH value of solution is 7-8.
Preferably, the time of the ageing is 1min-24h.
Preferably, the time of the ageing is 8-12h.
Preferably, the calcination temperature is 100-400 DEG C, calcination time 10-300min.
Preferably, the calcination temperature is 300-400 DEG C, calcination time 120-180min.
Compared with prior art, the invention has the benefit that
(1) present invention recovery processing is at low cost, and by controlling neutralization reaction, acquisition prepares the presoma of germanium dioxide, final to make
Standby product purity is 99.9%.
(2) product of the present invention is purer germanium dioxide, and no other precipitatings greatly improve the grade of product.
(3) present invention reduces process time, obtained product amount is few, and calcining time greatly shortens, and greatly saves
The energy.
Specific embodiment
Technical solution of the present invention is described in detail below by specific embodiment, but protection scope of the present invention is not
It is confined to the embodiment.
Embodiment 1
A method of the Ti recovery from germanic acid solution, germanic lye, the method includes the following steps: measuring containing for 500ml
Germanic acid liquid is placed in plastic beaker, and germanic amount is 1g/L, pH value 1；The sodium hydroxide solution for preparing 5mol/L, by hydroxide
Sodium solution is slowly added in germanic acid solution, while opening blender, stirring rate 1000r/min；Stop when solution pH value is 5
Sodium hydroxide is only added, and terminates to stir, obtains presoma precipitating；For 24 hours by the ageing of presoma precipitating, it then vacuumized
Filter, presoma precipitating is washed with deionized 3 times during this；Being deposited in baking oven for being filtered dry is dried, and gained dry powder is placed in horse
Not in furnace at 300 DEG C calcination time 300min, can be obtained germanium dioxide white powder, the rate of recovery of germanium is 97%.
Embodiment 2
A method of the Ti recovery from germanic acid solution, germanic lye, the method includes the following steps: measuring containing for 500ml
Germanic acid liquid is placed in plastic beaker, and germanic amount is 20g/L, pH value 1；The sodium hydroxide solution for preparing 10mol/L, by hydrogen-oxygen
Change sodium solution to be slowly added in germanic acid solution, while opening blender, stirring rate 120r/min；When solution pH value is 9
Stop that sodium hydroxide is added, and terminate to stir, obtains presoma precipitating；The presoma is precipitated into ageing 1min, is then taken out true
Sky filtering, presoma precipitating is washed with deionized 3 times during this；Being deposited in baking oven for being filtered dry is dried, and gained dry powder is set
In Muffle furnace at 400 DEG C calcination time 10min, can be obtained germanium dioxide white powder, the rate of recovery of germanium is 94%.
Embodiment 3
A method of the Ti recovery from germanic acid solution, germanic lye, the method includes the following steps: measuring containing for 500ml
Germanium lye is placed in a beaker, and germanic amount is 1g/L, pH value 13；Prepare the sulfuric acid solution of 10mol/L.Sulfuric acid solution is slow
It is added in germanic lye, while opening blender, stirring rate 200r/min.Stop that sulfuric acid is added when solution pH value is 8,
And terminate to stir.Above-mentioned resulting presoma precipitating is aged 8h, then vacuumizing filtration, presoma precipitating is spent during this
Ion water washing 3 times.Being deposited in baking oven for being filtered dry is dried, and gained dry powder is placed in Muffle furnace the calcination time at 400 DEG C
120min, can be obtained germanium dioxide white powder, and the rate of recovery of germanium is 95%.
Embodiment 4
A method of the Ti recovery from germanic acid solution, germanic lye, the method includes the following steps: measuring containing for 500ml
Germanium lye is placed in a beaker, and germanic amount is 20g/L, pH value 13；Prepare the sulfuric acid solution of 5mol/L.Sulfuric acid solution is slow
It is added in germanic lye, while opening blender, stirring rate 300r/min.Stop that sulfuric acid is added when solution pH value is 7,
And terminate to stir.Above-mentioned resulting presoma precipitating is aged 12h, then vacuumizing filtration, presoma precipitating is used during this
Deionized water is washed 3 times.Being deposited in baking oven for being filtered dry is dried, and gained dry powder is placed in Muffle furnace the calcination time at 300 DEG C
180min, can be obtained germanium dioxide white powder, and the rate of recovery of germanium is 96%.
Embodiment 5
A method of the Ti recovery from germanic acid solution, germanic lye, the method includes the following steps: measuring containing for 500ml
Germanic acid liquid is placed in plastic beaker, and germanic amount is 0.5g/L, pH value 1；The sodium hydroxide solution of 18.7mol/L is prepared, it will
Sodium hydroxide solution is slowly added in germanic acid solution, while opening blender, stirring rate 1000r/min；When solution pH value
Stop that sodium hydroxide is added when being 5, and terminate to stir, obtains presoma precipitating；For 24 hours by the ageing of presoma precipitating, then
Vacuumizing filtration, presoma precipitating is washed with deionized 3 times during this；Being deposited in baking oven for being filtered dry is dried, and gained is dry
Powder is placed in Muffle furnace the calcination time 300min at 350 DEG C, can be obtained germanium dioxide white powder, and the rate of recovery of germanium is
95%。
Embodiment 6
A method of the Ti recovery from germanic acid solution, germanic lye, the method includes the following steps: measuring containing for 500ml
Germanic acid liquid is placed in plastic beaker, and germanic amount is 150g/L, pH value 1；The sodium hydroxide solution for preparing 0.1mol/L, by hydrogen
Sodium hydroxide solution is slowly added in germanic acid solution, while opening blender, stirring rate 1000r/min；When solution pH value is 5
When stop that sodium hydroxide is added, and terminate to stir, obtain presoma precipitating；For 24 hours by the ageing of presoma precipitating, it then takes out true
Sky filtering, presoma precipitating is washed with deionized 3 times during this；Being deposited in baking oven for being filtered dry is dried, and gained dry powder is set
In Muffle furnace at 300 DEG C calcination time 300min, can be obtained germanium dioxide white powder, the rate of recovery of germanium is 94%.
Embodiment 7
A method of the Ti recovery from germanic acid solution, germanic lye, the method includes the following steps: measuring containing for 500ml
Germanium lye is placed in a beaker, and germanic amount is 0.5g/L, pH value 13；Prepare the sulfuric acid solution of 18mol/L.Sulfuric acid solution is delayed
Slowly it is added in germanic lye, while opening blender, stirring rate 200r/min.Stop that sulphur is added when solution pH value is 8
Acid, and terminate to stir.Above-mentioned resulting presoma precipitating is aged 8h, then vacuumizing filtration, presoma precipitating during this
It is washed with deionized 3 times.Being deposited in baking oven for being filtered dry is dried, and gained dry powder is placed in Muffle furnace at 400 DEG C when calcining
Between 120min, can be obtained germanium dioxide white powder, the rate of recovery of germanium is 96%.
Embodiment 8
A method of the Ti recovery from germanic acid solution, germanic lye, the method includes the following steps: measuring containing for 500ml
Germanium lye is placed in a beaker, and germanic amount is 50g/L, pH value 13；Prepare the sulfuric acid solution of 0.1mol/L.Sulfuric acid solution is delayed
Slowly it is added in germanic lye, while opening blender, stirring rate 200r/min.Stop that sulphur is added when solution pH value is 8
Acid, and terminate to stir.Above-mentioned resulting presoma precipitating is aged 8h, then vacuumizing filtration, presoma precipitating during this
It is washed with deionized 3 times.Being deposited in baking oven for being filtered dry is dried, and gained dry powder is placed in Muffle furnace at 400 DEG C when calcining
Between 120min, can be obtained germanium dioxide white powder, the rate of recovery of germanium is 95%.
As described above, must not be explained although the present invention has been indicated and described referring to specific preferred embodiment
For the limitation to invention itself.It without prejudice to the spirit and scope of the invention as defined in the appended claims, can be right
Various changes can be made in the form and details for it.
Claims (10)
1. a kind of method of the Ti recovery from germanic acid solution, germanic lye, which is characterized in that the method includes the following steps:
Germanic acid solution and lye or acid solution and germanic lye are subjected to neutralization reaction, obtain presoma；The presoma is aged,
It is filtered, washed, dries, calcines, obtain GeO2Powder.
2. the method according to claim 1, wherein in the germanic acid solution, solute H2GeF6, germanic amount is
0.5-150g/L；The lye is sodium hydroxide solution or potassium hydroxide solution, and the concentration of the lye is 0.1-18.7mol/
L。
3. according to the method described in claim 2, it is characterized in that, germanic amount is 1-20g/L in the germanic acid solution；It is described
The concentration of lye is 5-10mol/L.
4. method according to claim 1 or 2, which is characterized in that in the germanic lye, solute Na2GeO3, germanic
Amount is 0.5-50g/L；The acid solution is sulfuric acid or nitric acid or hydrochloric acid, and the concentration of the acid solution is 0.1-18mol/L.
5. according to the method described in claim 4, it is characterized in that, germanic amount is 1-20g/L in the germanic lye；It is described
The concentration of acid solution is 5-10mol/L.
6. method according to claim 1 or 2, which is characterized in that the neutralization reaction under conditions of mechanical stirring into
Row, the rate of the stirring are 120-1000r/min, and stirring to the pH value of solution is 5-9.
7. according to the method described in claim 6, stirring is extremely it is characterized in that, the rate of the stirring is 200-300r/min
The pH value of solution is 7-8.
8. method according to claim 1 or 2, which is characterized in that the time of the ageing is 1min-24h；Preferably,
The time of the ageing is 8-12h.
9. method according to claim 1 or 2, which is characterized in that the calcination temperature is 100-400 DEG C, calcination time
For 10-300min.
10. according to the method described in claim 9, calcination time is it is characterized in that, the calcination temperature is 300-400 DEG C
120-180min。
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116986626A (en) * | 2023-06-16 | 2023-11-03 | 核工业理化工程研究院 | Post-treatment method for germanium tetrafluoride to germanium dioxide reaction |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB865306A (en) * | 1959-06-25 | 1961-04-12 | Charles Lilley Horn | Metal recovery process |
| CN101476042A (en) * | 2009-01-06 | 2009-07-08 | 樊红杰 | Method for recovering indium and germanium from alkaline dirt slag |
| CN101967562A (en) * | 2010-11-23 | 2011-02-09 | 云南临沧鑫圆锗业股份有限公司 | Method for recovering germanium from silicon-germanium alloy by wet method |
| CN103614576A (en) * | 2013-11-27 | 2014-03-05 | 谈发堂 | Method for recycling germanium from germanium-containing glass |
| CN103952575A (en) * | 2014-05-13 | 2014-07-30 | 中南大学 | Method for recovering germanium from germanium-containing materials |
| CN107723467A (en) * | 2017-09-20 | 2018-02-23 | 郴州丰越环保科技有限公司 | A kind of method of high efficiente callback germanium |
-
2019
- 2019-07-09 CN CN201910615841.6A patent/CN110306069A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB865306A (en) * | 1959-06-25 | 1961-04-12 | Charles Lilley Horn | Metal recovery process |
| CN101476042A (en) * | 2009-01-06 | 2009-07-08 | 樊红杰 | Method for recovering indium and germanium from alkaline dirt slag |
| CN101967562A (en) * | 2010-11-23 | 2011-02-09 | 云南临沧鑫圆锗业股份有限公司 | Method for recovering germanium from silicon-germanium alloy by wet method |
| CN103614576A (en) * | 2013-11-27 | 2014-03-05 | 谈发堂 | Method for recycling germanium from germanium-containing glass |
| CN103952575A (en) * | 2014-05-13 | 2014-07-30 | 中南大学 | Method for recovering germanium from germanium-containing materials |
| CN107723467A (en) * | 2017-09-20 | 2018-02-23 | 郴州丰越环保科技有限公司 | A kind of method of high efficiente callback germanium |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116986626A (en) * | 2023-06-16 | 2023-11-03 | 核工业理化工程研究院 | Post-treatment method for germanium tetrafluoride to germanium dioxide reaction |
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