CN106906364B - The process of Ti recovery from germanic fluorine containing corrosion liquid - Google Patents
The process of Ti recovery from germanic fluorine containing corrosion liquid Download PDFInfo
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- CN106906364B CN106906364B CN201710131082.7A CN201710131082A CN106906364B CN 106906364 B CN106906364 B CN 106906364B CN 201710131082 A CN201710131082 A CN 201710131082A CN 106906364 B CN106906364 B CN 106906364B
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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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- 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 process of Ti recovery from germanic fluorine containing corrosion liquid is related to technical field of wet metallurgy, specially a kind of to sink germanium fluorine removal, the method for silica fluorine removal using boric acid from germanic fluorine containing corrosion liquid come the process of Ti recovery.The process of Ti recovery from germanic fluorine containing corrosion liquid of the invention, it is characterised in that simultaneously using boric acid and silica is added, heating volatilization removes fluorine and precipitate enriched germanium and carrys out Ti recovery metal the process.Fluoride removing rate of the present invention is up to 78% or more, it is finally transferred to fluorine-containing less than 0.05% in germanic slag and the raffinate in chlorinated distillation step, precipitating obtains germanium cinder grade up to 25% or more, the germanium rate of recovery can reach 95% or more before being wherein transferred to chlorinated distillation, and the loss late of germanium metal is less than 1.2% during entire fluorine removal；Wherein the part supernatant waste liquid after fluorine removal carries out the secondary heavy germanium processing of circulation and stress.In the chlorinated distillation for carrying out germanic slag and raffinate, the steam rate of germanium can reach 98% or more, be able to satisfy manufacturing technique requirent.
Description
Technical field
The present invention relates to technical field of wet metallurgy, specially one kind is removed from germanic fluorine containing corrosion liquid using the heavy germanium of boric acid
Fluorine, silica fluorine removal method carry out the process of Ti recovery from germanic fluorine containing corrosion liquid of Ti recovery.
Background technique
Germanium belongs to rare scattering elements, occupies an important position in defense military and modern science and technology, and optical fiber is logical
Credit germanium, infrared optics germanium, used in electronic industry germanium, Medicines and Health Product germanium, superconductor germanium, photoelectric source germanium etc. are all
Important use of the germanium in every field.And germanium resource is limited, the germanium resource amount that can be exploited as germanium mine is even more seldom, institute
With will germanium smelt and process of manufacture in the germanium waste material, the waste liquid that generate carry out germanium recycling, to realize germanium waste material, germanium waste liquid
Germanium resource is of great significance.
Often along with the generation largely containing germanium waste material, waste liquid, rear end is more arrived in the processing of germanium product for the smelting and production and processing of germanium
The more complicated multiplicity of germanic waste recovery generated.Wherein, chemistry corruption is carried out to metal surfaces such as metal germanium ingots in processing
It has used the mixed acid of hydrofluoric acid and nitric acid to carry out oxidation processes when erosion polishing, has just produced high fluorine-containing, germanic corrosive liquid, because
Corrosive liquid is fluorine-containing excessively high, and the corrosion distillation equipment such as rectifying cannot directly adopt chlorization distillation method processing, therefore this is caused fluorine-containing to contain
The processing of germanium corrosive liquid is difficult, and germanium cost recovery is high.
Summary of the invention
To be solved by this invention is exactly that existing height is fluorine-containing, germanic corrosive liquid can corrode distillation rectifying device, causes to handle
Difficulty, the high problem of germanium cost recovery are provided one kind and are removed from germanic fluorine containing corrosion liquid using the heavy germanium fluorine removal of boric acid, silica
The method of fluorine carrys out the process of Ti recovery.
The process of Ti recovery from germanic fluorine containing corrosion liquid of the invention, it is characterised in that the process is adopted simultaneously
With boric acid and silica is added, heating volatilization removes fluorine and precipitates enriched germanium and carrys out Ti recovery metal, and specific process step is such as
Under:
Step 1: taking appropriate germanic fluorine containing corrosion waste liquid, it is put into polytetrafluoroethylcontainer container, measures what the corrosive liquid contained
Fluorine content and Ge content, the fluorine quality being calculated in waste liquid is A and germanium quality is B, and the boric acid and quality that addition quality is C are
The silica of D stirs evenly after mixing, polytetrafluoroethylcontainer container is connect with exhaust gas reception device, in exhaust gas reception device
Dilute hydrochloric acid equipped with 1-2mol/L is as exhaust gas receiving liquid；
Second step heats polytetrafluoroethylcontainer container, continues to stir to promote the progress chemically reacted in solution, heated solution
For temperature to 80-90 DEG C, the duration of heat is 15-30 min；
Third step after heating, takes the supernatant liquor part in polytetrafluoroethylcontainer container, remaining residual night, residue and
Exhaust gas receiving liquid is spare；
4th step, appropriate germanic fluorine containing corrosion waste liquid is added in clear liquid in third step, repeats the first step, second step process, will
Raffinate, the residue that obtained raffinate, residue is obtained with third step are mixed；
5th step, residue, the raffinate obtained after the 4th step is mixed are transferred in distillation reaction bottle, are added 10mol/L's
Concentrated hydrochloric acid passes through conventional chlorinating distillating method Ti recovery metal.
The boric acid quality C is 1.5 to 3 times of the fluorine quality A in waste liquid, and silica quality D is the fluorine in waste liquid
0.2 to 0.4 times of quality A.
The reaction equation of above-mentioned process are as follows:
3F-+H3BO3+3H+ = BF3↑+3H2O ... ... ... (1)
4F-+SiO2+4H+ = SiF4↑+2H2O ... ... ... ... (2).
The exhaust gas receiving liquid is the dilute hydrochloric acid solution of 1-2mol/L.
The process of Ti recovery from germanic fluorine containing corrosion liquid of the invention, step is simple, and convenient and practical, fluoride removing rate can
Up to 78% or more, be finally transferred to it is fluorine-containing less than 0.05% in germanic slag and the raffinate in chlorinated distillation step, precipitating obtain germanium slag product
Position is up to 25% or more, wherein being transferred to the germanium rate of recovery before chlorinated distillation can reach 95% or more, and germanium metal during entire fluorine removal
Loss late less than 1.2%；Wherein the part supernatant waste liquid after fluorine removal carries out the secondary heavy germanium processing of circulation and stress.It is germanic in progress
In the chlorinated distillation of slag and raffinate, the steam rate of germanium can reach 98% or more, be able to satisfy manufacturing technique requirent.Preferably solve
The recycling problem of germanium in germanic fluorine containing corrosion liquid.
Specific embodiment
Embodiment 1: a kind of process of the Ti recovery from germanic fluorine containing corrosion liquid, using addition boric acid and titanium dioxide
Silicon, heating volatilization remove fluorine and precipitate enriched germanium and carry out Ti recovery metal, the specific process steps are as follows:
Step 1: taking the germanic fluorine containing corrosion liquid of 500mL, it is put into polytetrafluoroethylcontainer container, measures the fluorine that the corrosion contains
Content and Ge content are respectively 45.80g/L and 26.45 g/L, and it is 22.9g that fluorine quality, which is calculated, and germanium quality is 13.225g,
Boric acid 45.80g and silica 4.58g is added, is stirred evenly after mixing, polytetrafluoroethylcontainer container and exhaust gas reception device are connected
It connects, the exhaust gas receiving liquid equipped with the dilute hydrochloric acid solution that 200mL concentration is 1mol/L in exhaust gas reception device；
Second step heats polytetrafluoroethylcontainer container, continues to stir the generation to promote solution reaction, heated solution temperature is extremely
80-90 DEG C, duration of heat 15min；
Third step after heating, takes the supernatant liquor part in polytetrafluoroethylcontainer container, remaining residual night, residue and
Exhaust gas receiving liquid is spare；Waste gas containing fluoride receiving liquid is cooled to room temperature, is settled in 250 mL volumetric flasks, exhaust gas receiving liquid is detected
In germanic, fluorinated volume；By residue precipitating raffinate and precipitation slag separation, germanic, fluorinated volume therein is detected respectively.Testing result:
The 0.53% of the germanic total germanium of 2.80 g/L, Zhan in exhaust gas receiving liquid, 79.98 % of the fluorine-containing total fluorine of 73.26 g/L, Zhan；Precipitate raffinate
In the germanic total germanium of 12.5 g/L, Zhan 3%, the 0.040% of the fluorine-containing total fluorine of 28.75 g/L, Zhan；Fluorine-containing 1.98%, germanium in precipitating residue
Grade is up to 29.43%；
4th step, appropriate germanic fluorine containing corrosion liquid is added in clear liquid in third step, repeats the first step, second step process, will
To raffinate, the residue raffinate, the residue that are obtained with third step mixed, calculate that fluoride removing rate is 80% and heavy germanium rate is accordingly
95%, the germanium rate of recovery is 96%；
5th step, residue, the raffinate obtained after the 4th step is mixed are transferred in cucurbit, and the dense salt of 10mol/L is added
Acid, by traditional chlorinated distillating method Ti recovery metal, steam rate is up to 98.5%.
Embodiment 2: a kind of process of the Ti recovery from germanic fluorine containing corrosion liquid, using addition boric acid and titanium dioxide
Silicon, heating volatilization remove fluorine and precipitate enriched germanium and carry out Ti recovery metal, the specific process steps are as follows:
Step 1: taking the germanic fluorine containing corrosion liquid of 500mL, it is put into polytetrafluoroethylcontainer container, measures the fluorine that the corrosion contains
Content and Ge content are respectively 51.83 g/L and 28.99 g/L, and it is 25.915g that fluorine quality, which is calculated, and germanium quality is
14.495g is added boric acid 38.873g and silica 7.77g, stirs evenly after mixing, by polytetrafluoroethylcontainer container and exhaust gas
Reception device connects, and the exhaust gas receiving liquid that 200mL concentration is 2 mol/L dilute hydrochloric acid solutions is housed in exhaust gas receiving device；
Second step heats polytetrafluoroethylcontainer container, continues to stir the generation to promote solution reaction, heated solution temperature is extremely
80-90 DEG C, duration of heat 30min；
Third step after heating, takes the supernatant liquor part in polytetrafluoroethylcontainer container, remaining raffinate, residue and
Exhaust gas receiving liquid is spare；Waste gas containing fluoride receiving liquid is cooled to room temperature, is settled in 250 mL volumetric flasks, exhaust gas receiving liquid is detected
In germanic, fluorinated volume；By residue precipitating raffinate and precipitation slag separation, germanic, fluorinated volume therein is detected respectively.Testing result:
The 0.45% of the germanic total germanium of 2.61 g/L, Zhan in exhaust gas receiving liquid, the 80.01% of the fluorine-containing total fluorine of 82.94 g/L, Zhan；Precipitate raffinate
In the germanic total germanium of 14.29 g/L, Zhan 3.45%, the 0.056% of the fluorine-containing total fluorine of 41.43 g/L, Zhan；It is fluorine-containing in precipitating residue
1.77%, germanic grade is up to 31.3%；
4th step, appropriate germanic fluorine containing corrosion liquid is added in clear liquid in third step, repeats the first step, second step process, will
To raffinate, the residue raffinate, the residue that are obtained with third step mixed, calculate that fluoride removing rate is 80% and heavy germanium rate is accordingly
95%, the germanium rate of recovery is 97%；
5th step, residue, the raffinate obtained after the 4th step is mixed are transferred in cucurbit, and concentrated hydrochloric acid is added, passes through biography
It unites chlorinated distillation method Ti recovery metal, steam rate is up to 98.8%.
Claims (2)
1. a kind of process of the Ti recovery from germanic fluorine containing corrosion liquid, it is characterised in that the process is using addition boric acid
And silica, heating volatilization, it removes fluorine and precipitates enriched germanium and carry out Ti recovery metal, the specific process steps are as follows:
Step 1: taking appropriate germanic fluorine containing corrosion liquid, it is put into polytetrafluoroethylcontainer container, measures the germanic fluorine containing corrosion liquid and contain
Fluorine content and Ge content, the fluorine quality being calculated in germanic fluorine containing corrosion liquid is A and germanium quality is B, and it is C that quality, which is added,
The silica that boric acid and quality are D, stirs evenly after mixing, polytetrafluoroethylcontainer container is connect with exhaust gas reception device, gives up
Exhaust gas receiving liquid is housed in gas receiving device；
Second step heats polytetrafluoroethylcontainer container, continues to stir the generation to promote solution reaction, heated solution temperature to 80-
90 DEG C, the duration of heat is 15-30 min；
Third step after heating, takes the supernatant liquor part in polytetrafluoroethylcontainer container, remaining raffinate, residue and exhaust gas
Receiving liquid is spare；
4th step, appropriate germanic fluorine containing corrosion liquid is added in clear liquid in third step, the first step, second step process is repeated, by what is obtained
Raffinate, the residue that raffinate, residue are obtained with third step are mixed；
5th step, residue, the raffinate obtained after the 4th step is mixed are transferred in cucurbit, and the concentrated hydrochloric acid of 10mol/L is added, and are led to
Cross traditional chlorinated distillating method Ti recovery metal；
In the above-mentioned first step, boric acid quality C is 1.5 to 3 times of the fluorine quality A in waste liquid, and silica quality D is in waste liquid
0.2 to 0.4 times of fluorine quality A.
2. as described in claim 1 from germanic fluorine containing corrosion liquid Ti recovery process, it is characterised in that it is described useless
Gas receiving liquid is the dilute hydrochloric acid solution of 1-2mol/L.
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| CN109097603B (en) * | 2018-09-12 | 2020-11-06 | 云南临沧鑫圆锗业股份有限公司 | Process method for recovering germanium from germanium wafer deep processing waste acid |
| CN110453097B (en) * | 2019-09-17 | 2021-12-17 | 广东先导稀材股份有限公司 | Method for distilling and extracting germanium from fluorine-containing germanium concentrate |
Citations (4)
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| CN101418373A (en) * | 2008-09-16 | 2009-04-29 | 云南临沧鑫圆锗业股份有限公司 | Method for extracting germanium from chlorinated distillation slag |
| CN103757422A (en) * | 2014-02-19 | 2014-04-30 | 云南东昌金属加工有限公司 | Method for recovering germanium from germanium-containing multi-metal material |
| CN104818397A (en) * | 2015-05-19 | 2015-08-05 | 河北工程大学 | Method for extracting germanium from coal |
| CN105821224A (en) * | 2016-06-06 | 2016-08-03 | 云南临沧鑫圆锗业股份有限公司 | Method for extracting germanium in low-grade germanium concentrates through fluoride roasting process |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES2325292B1 (en) * | 2008-02-28 | 2010-06-24 | Universidad De Sevilla | PROCEDURE FOR THE RECOVERY OF GERMANIUM IN DISSOLUTION BY COMPLEXING AND USING ION EXCHANGE RESINS. |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101418373A (en) * | 2008-09-16 | 2009-04-29 | 云南临沧鑫圆锗业股份有限公司 | Method for extracting germanium from chlorinated distillation slag |
| CN103757422A (en) * | 2014-02-19 | 2014-04-30 | 云南东昌金属加工有限公司 | Method for recovering germanium from germanium-containing multi-metal material |
| CN104818397A (en) * | 2015-05-19 | 2015-08-05 | 河北工程大学 | Method for extracting germanium from coal |
| CN105821224A (en) * | 2016-06-06 | 2016-08-03 | 云南临沧鑫圆锗业股份有限公司 | Method for extracting germanium in low-grade germanium concentrates through fluoride roasting process |
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Effective date of registration: 20191224 Address after: 430000 No.9, Guanggu Avenue, Donghu Development Zone, Wuhan City, Hubei Province Patentee after: WUHAN YUNJINGFEI OPTICAL FIBER MATERIAL CO., LTD. Address before: 650000 Yunnan province Lincang Linxiang District busy River Street busy River Community magpie nest Group No. 168 Co-patentee before: Yunnan Dongchang Metal Processing Co.,Ltd. Patentee before: Yunnan Lincang Xinyuan Germanium Co., Ltd. |
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Effective date of registration: 20220531 Address after: 677000 No. 168, magpie nest group, mangpan community, mangpan street, Linxiang District, Lincang City, Yunnan Province Patentee after: YUNNAN LINCANG XINYUAN GERMANIUM INDUSTRY Co.,Ltd. Patentee after: Yunnan Dongchang metal processing Co., Ltd Address before: 430000 No. 9, Guanggu Avenue, Donghu Development Zone, Wuhan City, Hubei Province Patentee before: WUHAN YUNJINGFEI OPTICAL FIBER MATERIAL Co.,Ltd. |