CN1058617A - Method for recovering germanium from solution - Google Patents
Method for recovering germanium from solution Download PDFInfo
- Publication number
- CN1058617A CN1058617A CN90104883A CN90104883A CN1058617A CN 1058617 A CN1058617 A CN 1058617A CN 90104883 A CN90104883 A CN 90104883A CN 90104883 A CN90104883 A CN 90104883A CN 1058617 A CN1058617 A CN 1058617A
- Authority
- CN
- China
- Prior art keywords
- germanium
- solution
- extraction
- stripping
- organic phase
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910052732 germanium Inorganic materials 0.000 title claims abstract description 36
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 36
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000000605 extraction Methods 0.000 claims abstract description 24
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 14
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims abstract description 5
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229940119177 germanium dioxide Drugs 0.000 claims abstract 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 12
- 238000001556 precipitation Methods 0.000 claims description 11
- NEAQRZUHTPSBBM-UHFFFAOYSA-N 2-hydroxy-3,3-dimethyl-7-nitro-4h-isoquinolin-1-one Chemical compound C1=C([N+]([O-])=O)C=C2C(=O)N(O)C(C)(C)CC2=C1 NEAQRZUHTPSBBM-UHFFFAOYSA-N 0.000 claims description 10
- 230000003301 hydrolyzing effect Effects 0.000 claims description 5
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 claims description 3
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 8
- 239000007788 liquid Substances 0.000 abstract description 4
- 238000011084 recovery Methods 0.000 abstract description 4
- 238000000926 separation method Methods 0.000 abstract description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract description 2
- 238000009854 hydrometallurgy Methods 0.000 abstract description 2
- VCYOMOBUUABXKC-UHFFFAOYSA-N [F].[Ge] Chemical compound [F].[Ge] VCYOMOBUUABXKC-UHFFFAOYSA-N 0.000 abstract 1
- 239000012074 organic phase Substances 0.000 description 17
- 229910052731 fluorine Inorganic materials 0.000 description 14
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 13
- 239000011737 fluorine Substances 0.000 description 13
- 239000003795 chemical substances by application Substances 0.000 description 9
- 239000012452 mother liquor Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 229910005793 GeO 2 Inorganic materials 0.000 description 8
- 238000004821 distillation Methods 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- 159000000013 aluminium salts Chemical class 0.000 description 3
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 3
- 230000000536 complexating effect Effects 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 239000006210 lotion Substances 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- HHFCFXJTAZTLAO-UHFFFAOYSA-N fluorogermanium Chemical compound [Ge]F HHFCFXJTAZTLAO-UHFFFAOYSA-N 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium chloride Substances Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- MFWRCAQESKCGKS-UHFFFAOYSA-N chlorogermanium Chemical compound [Ge]Cl MFWRCAQESKCGKS-UHFFFAOYSA-N 0.000 description 1
- 239000010883 coal ash Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- 230000005514 two-phase flow Effects 0.000 description 1
Classifications
-
- 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
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The recovery of germanium from solution involves hydrometallurgy, especially the recovery of germanium from solution by extraction and stripping. The present invention features that ammonia gas or ammonia water is used to hydrolyze the back extraction liquid directly to obtain coarse germanium dioxide, and the hydrolyzed mother liquid containing ammonium fluoride may be returned for reuse. The fluorine-germanium separation method is simple and has high separation efficiency. The method can improve the back extraction rate, reduce the consumption of reagents and have higher industrial use value.
Description
The present invention relates to hydrometallurgy, particularly a kind of method that from solution, reclaims germanium.
With hydroxamic acid extracted germanium from germanic dilution heat of sulfuric acid, facts have proved it is a kind of efficient and simple method." the strain smelting science and technology " fourth phase in 1985 has been done detailed argumentation to this.Reextraction germanium has three kinds of methods usually from rich germanium organic phase: (one) hydrofluoric acid or NH
4The F stripping process is with hydrofluoric acid or the ammonium fluoride solution germanium of stripping from above-mentioned rich germanium organic phase.For separating Ge from fluorine-containing anti-stripping agent, also to carry out the extraction second time with trialkylamine, carry out the second time with 8N sulfuric acid and strip.Because the secondary anti-stripping agent that obtains is still fluorine-containing higher, for the complexing fluorine, add aluminium salt (AlCl in certain Al/F ratio in the strip liquor during chlorinated distillation toward the second time
36H
2O).The GeCl that distillation obtains
4After hydrolysis, obtain GeO
2Although NH
4The back extraction ratio height of F and HF reextraction germanium, but separate in order to carry out fluoro-germanium, also need carry out the extraction second time and reextraction, technical process is long, and for the second time the strip liquor fluorine content is still up to 100 grams per liters, germanic only about 22 grams per liters, and both weight ratios are: Ge: F=1: 4.5.In addition, anti-stripping agent also need add aluminium salt complexing fluorine and could carry out smoothly later when chlorinated distillation for the second time.Because aluminium salt adds in a large number, soltion viscosity increases, and produces a large amount of bubbles during distillation, causes operational difficulty, and vinasse is thick on the other hand, can not Returning utilization, can only be as three waste discharge, and contaminate environment.Because this method chloro-germanium separation method complexity, efficient is low, and the cost height has made this method since coming out the end of the seventies, fails to obtain industrial application always.(2) ammonium hydroxide adds the ammonium sulfate reverse-extraction method, promptly uses the mixing solutions of ammoniacal liquor and ammonium sulfate, the germanium of from above-mentioned rich germanium organic phase, stripping, and the anti-stripping agent that obtains obtains GeO through evaporation concentration after the hydrolysis
2Though the etching problem that this method is floride-free, technical process is simple, but the stripping rate of germanium is low, generally has only 60%.Because stripping rate is low, in the process that recycles, can cause germanium constantly accumulation in organic phase, cause organic phase (no matter being poor organic phase or saturated organic phase) that metastable equilibrium concentration can not be arranged, extracting operation therefore can not serialization.Industrial production is difficult to realize.(3) AN stripping process is promptly used NaClO, HCl+H
2O
2, HCl+Cl
2+ H
2The above general designation of O or HCl+NaClO(AN reagent) the solution germanium of from above-mentioned rich germanium organic phase, stripping.The anti-stripping agent that obtains is through evaporation concentration, chlorinated distillation, and hydrolysis gets GeO
2Though the interference that this method is floride-free, producing also can serialization.But also there is following problem in it: 1. the hydroxamic acid loss is big.Because the hydroxamic acid poor chemical stability causes hydrolysising loss easily during back extraction.And AN reagent is a kind of very strong oxygenant, and hydroxamic acid is had very strong oxygenolysis.For example: the rich germanium organic phase of oxygen-containing nitrolic acid 3%, after the NaC-10 solution back extraction once with 30 grams per liters, the germanium percentage extraction of the poor organic phase of gained is similar to zero, illustrates that hydroxamic acid wherein decomposes fully substantially, and the wastage rate of hydroxamic acid can be considered 100%.The loss of general hydroxamic acid is at thick GeO
2Production cost in occupy very high ratio, account for 60～70%.So use AN reagent reextraction germanium production cost height.2.NaClO consume greatlyyer, one kilogram of germanium of every production will consume 10～13 kilograms NaClO, is equivalent to 80～100 kilograms of industrial clorox (containing NaClO about 12%).3. in the reextraction process, the enrichment multiple of germanium is low, and the gained anti-stripping agent just can be sent to chlorinated distillation or hydrolysis after evaporation concentration.Reason is that the oxygenolysis of AN reagent can only keep once, and its oxygenolysis is very little when stripping to the second time.Therefore the AN stripping process is only applicable to single hop reextraction operation, can not carry out multistage counter current and strip, thereby germanium concentration is lower in the anti-stripping agent.
The objective of the invention is to propose a kind of new technology, separate, Neutral ammonium fluoride can be recycled, reduce the reagent loss of extraction agent and strippant, improve the enrichment multiple of germanium to simplify fluoro-germanium.
Main points of the present invention are with hydroxamic acid extracted germanium from sulfuric acid medium, strip with Neutral ammonium fluoride, and directly logical ammonia of anti-stripping agent or ammoniacal liquor hydrolytic precipitation germanium make mother liquor return use.
NH
4F strips, and directly logical ammonia of strip liquor or ammoniacal liquor hydrolytic precipitation ultimate principle are:
Represent respectively to strip and the F-Ge sepn process in equation (1) and (2).In equation (1), NH
4The F germanium of stripping from rich germanium organic phase forms (NH
4)
2GeF
6, in equation in (2), (NH
4)
2GeF
6Hydrolysis obtains GeO
2And NH
4F, this NH
4F turns back to (1) formula and recycles.
F-Ge separates and can carry out at room temperature (15～25 ℃).Strip liquor logical ammonia or ammoniacal liquor under agitation condition are kept 10 minutes to 2 hours, so that fully be settled out thick GeO till the pH value 8.5 to 10.0 under this pH
2If pH is less than 8.5, GeO
2Precipitation can be not exclusively, and if pH is greater than 10.0, the GeO that has been settled out
2Also can dissolve.
Thick GeO
2In the fluorine-containing mother liquor also carried secretly, can wash and remove, contain germanium and fluorine in the gained washing lotion, washing lotion all turns back to the dilution operation, to replenish the solution loss that is caused in the ammonia still process process.
Wash later thick GeO
2, 120 ℃ of oven dry, its chemical constitution is (weight percent): G-e50～60, F＜0.5, Si＜1, Fe＜1～2.
In order to recycle the NH in the mother liquor of precipitation of ammonium
4F carried out ammonia still process in 10 minutes with the mother liquor of precipitation of ammonium boiling and handles, so that the pH of mother liquor of precipitation of ammonium is reduced to about 7.In the ammonia still process process, liquor capacity reduces 30% approximately, with washing lotion and distilled water mother liquor is diluted to original volume after, turn back to the back extraction operation and recycle.
Fluorine and ge content very little (germanium trace, fluorine 60 mg/litre) in the ammonia still process phlegma can be used as the mother liquor dilution and use.
Because NH
4F belongs to neutral salt, and the corrodibility of its aqueous solution is little, and equipment and materials can be selected igelite or stainless steel for use.
Fig. 1 is seen in technical process of the present invention.
Embodiment:
The organic phase composition (%, V/V): 3% hydroxamic acid+10%P
204+ 10%C
7-9Lipid acid+sulfonated kerosene
Collection stoste: coal ash leach liquor
Leach liquor is formed (grams per liter): Ge:0.352, Fe:3.6, SiO
2: 4.7, Al:2.6, pH=1.0.
In mixer-settlers, above-mentioned organic phase is carried out four sections continuous countercurrent extractions, obtain the rich germanium organic phase of germanic 1.39 grams per liters.Use 2N NH
4F solution, carrying out four sections continuous countercurrents with above-mentioned rich germanium organic phase in mixer-settlers strips, the reextraction condition is: stirring velocity: 400 rev/mins, duration of contact: 10 minutes, contact was compared: organic phase/water=1/1, two-phase flow ratio: organic phase: water=4.9: 1, the strip liquor that obtains is formed (grams per liter): Ge:6.82, F:41.3, Fe:1.13, SiO
2: 0.025, Al is little, pH=4.8.Back extraction ratio＞99%.
Above-mentioned strip liquor is fed ammoniacal liquor (containing ammonia 25%) to 30 minutes gained GeO of pH9.5 restir under agitation condition
2Precipitation is adding distil water washing more after filtering, and filter cake obtains thick GeO after the oven dry down at 120 ℃
2, its chemical constitution is (%): Ge:60 F:0.35, Fe:1.5, Si＜1.
The mother liquor of precipitation of ammonium that filtration obtains is carried out ammonia still process makes the pH of solution reduce to 7, and it is about 30% that volume reduces, and uses GeO
2Washing and water of condensation, distilled water turn back to the back extraction operation and recycle after mother liquor is diluted to original volume after with ammonia still process.
The present invention is led to ammonia and is added the thick GeO of ammoniacal liquor gained
2The chemical constitution basically identical.
The present invention has the following advantages:
1. not only the F-Ge separation is simple, easy to operate in the present invention, and separative efficiency is high. This method has been saved former NH4The extraction and back-extraction second time of F reverse-extraction method is got, and thick GeO2In fluorine content but very low, the weight ratio of germanium and fluorine only is 1: 0.02.
2. the required reagent source of reverse-extraction method of the present invention is wide, and low price reduces production cost. NH particularly4F recycles, and has economized to extract for the second time and strip, and also need not to add Al-Cl during chlorinated distillation3Complexing fluorine, reagent expense are put forward the germanium method than above three kinds of reextraction and are obviously reduced, and have more competitiveness.
3. because NH4The F strippant recycles, and the closed cycle of whole germanium-extracting technology flow process without discharging of waste liquid, does not pollute the environment. And former NH4The F reverse-extraction method is in process of extracting germanium, and many places have produced waste liquid, waste residue, and the utmost point is unfavorable for environmental protection.
4. the present invention is applicable to extensive continuity industrial production.
5. because the extraction and back-extraction second time that the present invention has saved in the former method is got, reach AlCl3The complexing fluorine is so this method rate of recovery improves. Improve about 5～10% rate of recovery.
Claims (3)
1, a kind of method that reclaims germanium from solution, with the hydroxamic acid extraction, Neutral ammonium fluoride is stripped, and it is characterized in that directly leading in the ammonium fluoride back extraction liquid ammonia or ammoniacal liquor hydrolytic precipitation and obtains thick germanium dioxide.
2,, it is characterized in that p-H=8.5～10.0 of logical ammonia or ammoniacal liquor hydrolytic precipitation by the described method of claim 1.
3,, it is characterized in that the hydrolytic precipitation time of logical ammonia or ammoniacal liquor is 10 minutes to 2 hours by the described method of claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN90104883A CN1024926C (en) | 1990-07-31 | 1990-07-31 | Method for recovering germanium from solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN90104883A CN1024926C (en) | 1990-07-31 | 1990-07-31 | Method for recovering germanium from solution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1058617A true CN1058617A (en) | 1992-02-12 |
| CN1024926C CN1024926C (en) | 1994-06-08 |
Family
ID=4878792
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN90104883A Expired - Fee Related CN1024926C (en) | 1990-07-31 | 1990-07-31 | Method for recovering germanium from solution |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1024926C (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1042147C (en) * | 1994-07-21 | 1999-02-17 | 中国科学院上海有机化学研究所 | Method for selectively extraction separating Ge |
| CN102433435A (en) * | 2011-12-27 | 2012-05-02 | 北京矿冶研究总院 | Extracting agent for extracting germanium and gallium and extracting method thereof |
| CN102703707A (en) * | 2012-06-15 | 2012-10-03 | 广西金山铟锗冶金化工有限公司 | Method for recovering indium and germanium from zinc leaching residue |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1304610C (en) * | 2005-05-17 | 2007-03-14 | 桂林矿产地质研究院 | 7815 extracting agent as germanium extracting additive and extracting method using said additive |
-
1990
- 1990-07-31 CN CN90104883A patent/CN1024926C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1042147C (en) * | 1994-07-21 | 1999-02-17 | 中国科学院上海有机化学研究所 | Method for selectively extraction separating Ge |
| CN102433435A (en) * | 2011-12-27 | 2012-05-02 | 北京矿冶研究总院 | Extracting agent for extracting germanium and gallium and extracting method thereof |
| CN102433435B (en) * | 2011-12-27 | 2014-06-25 | 北京矿冶研究总院 | Extracting agent for extracting germanium and gallium and extracting method thereof |
| CN102703707A (en) * | 2012-06-15 | 2012-10-03 | 广西金山铟锗冶金化工有限公司 | Method for recovering indium and germanium from zinc leaching residue |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1024926C (en) | 1994-06-08 |
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