CN101871047A - Method for reclaiming germanium from organic germanium waste liquid - Google Patents
Method for reclaiming germanium from organic germanium waste liquid Download PDFInfo
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- CN101871047A CN101871047A CN201010191424A CN201010191424A CN101871047A CN 101871047 A CN101871047 A CN 101871047A CN 201010191424 A CN201010191424 A CN 201010191424A CN 201010191424 A CN201010191424 A CN 201010191424A CN 101871047 A CN101871047 A CN 101871047A
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- germanium
- waste liquid
- organic
- cao
- reclaiming
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- 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 method for reclaiming germanium from organic germanium waste liquid. The method comprises the following steps of: adding MgCl2 and CaO into the organic germanium waste liquid in a mass ratio of MgCl2 to Ge of 20-40: 1 and in a mass ratio of CaO to Ge of 30-50: 1, adjusting pH value to between 11 and 12 by using NaOH solution, performing sedimentation of the germanium, burning the germanium sediment at the temperature of between 600 and 700 DEG C to obtain germanium concentrate containing 3.0 to 4.5 mass percent of Ge, and chloridizing and distilling the germanium concentrate to reclaim the germanium. The method for reclaiming the germanium from the organic germanium waste liquid reclaims the germanium by adopting magnesium chloride-calcium oxide sediment, reduces the using amount of magnesium chloride, reduces the production cost for reclaiming the germanium and effectively reclaims the germanium; and the reclamation rate of the germanium is over 90 percent. The method can treat 100m<3> of organic germanium waste liquid every year, reclaim over 1 ton of germanium metal and create 1.5 million of profit and tax. The method obtains good economic benefit, and establishes an effective process flow for reclaiming the germanium from the organic germanium waste liquid.
Description
Technical field
The present invention relates to the recovery method of germanium in a kind of organic germanium waste liquid.
Background technology
Contain some germanium in the waste liquid that produces in the organic germanium production process, reclaim germanium in the waste liquid, the rate of recovery of germanium only 50% with traditional chlorinated distillation technology.According to the pertinent data introduction, germanic solution can precipitate germanium and reach the purpose that reclaims germanium with villaumite.But learn that by test the organic germanium waste liquid adopts MgCl
2Precipitation germanium, the deposition rate of precipitation germanium is 75～85%, the germanium precipitation recovering effect in the waste liquid is not good.
Summary of the invention
The recovery method that the purpose of this invention is to provide germanium in the high organic germanium waste liquid of a kind of germanium rate of recovery.
The present invention adopts the germanium that adds in the auxiliary magnesium chloride precipitation of the calcium oxide waste liquid, germanium is separated with most of organic reagent, germanic throw out destroys residual organic reagent through 600～700 ℃ of calcinations, and the calcination thing reaches the purpose that reclaims germanium behind chlorinated distillation for the germanium concentrate that contains Ge=2.0～4.0% (mass percent).Concrete triturating is as follows:
1. the character of organic germanium waste liquid
Organic germanium waste liquid (addition mother liquor, hydrolysis washing lotion) is strongly-acid, wherein contains organic reagent, hydrochloric acid and germanium.Germanium is with Ge
4+Form is present in the waste liquid, and the main chemical compositions data see Table 1:
The main chemical compositions of table 1 organic germanium waste liquid
2. Selection of technological conditions
2.1 add MgCl
2The test of precipitation germanium
Investigate the MgCl that adds different amounts
2Influence to the germanium deposition rate.The test-results (see figure 1) shows: along with MgCl
2The increase of amount, the deposition rate of germanium improves.
Reaction formula is: H
2GeO
3+ MgCl
2=MgGeO
3↓+2HCl
Test conditions: pH value=11～12,90 ℃ of temperature
2.2 add the test of CaO precipitation germanium
Investigate and add the influence of the different CaO that measure the germanium deposition rate.The test-results (see figure 2) shows, along with the increase of the amount of CaO, the deposition rate of germanium improves.
Reaction formula is: H
2GeO
4+ CaO=CaGeO
3↓=H
2O
Test conditions: pH value=11～12,90 ℃ of temperature
2.3MgCl
2The test of-CaO precipitation germanium
By adding MgCl respectively
2, CaO precipitation germanium test-results learn MgCl
2Amount add as 200 times of germanium amount, the deposition rate of germanium is 85%, the CaO add-on is 140 times of germanium amount, the deposition rate of germanium is 77.5%, in these two kinds of conditions, the germanium sedimentation effect in the waste liquid is not good.Complete for the precipitation that makes germanium, carried out adding CaO and MgCl
2The test of co-precipitation germanium, test-results (see figure 3) show, add CaO, CaO: Ge (mass ratio)=45: 1, MgCl
2Add-on when being 30 times of Ge amount (mass ratio), the germanium deposition rate can reach 97%.This is because under the condition that NaOH exists, the MgCl of adding
2, the germanium in CaO and the waste liquid is with MgGeO
3↓, CaGeO 3 ↓, Na2GeO3 ↓, the form co-precipitation, the deposition rate of germanium is improved.Test conditions is as follows: pH value 11～12,90 ℃ of temperature.
2.4 temperature is to the precipitation influence test of germanium
Investigated differing temps the test-results (see figure 4) of germanium deposition rate has been shown that during precipitation germanium, along with the rising of temperature, the deposition rate of germanium improves.Test conditions is as follows: the amount that adds CaO is GaO: Ge=45: 1 (mass ratio); MgCl
2: Ge=25: 1 (mass ratio); PH=11～12
2.5pH value is to the precipitation influence test of germanium
Add MgCl
2Behind CaO,, investigate of the influence of different pH values to the germanium deposition rate with the pH value of the NaOH aqueous solution (50g/L) adjustment solution.The test-results (see figure 5) shows: the rising along with the pH value helps MgGeO
3↓, CaGeO
3↓, Na
2GeO
3↓ precipitation generate, the deposition rate of germanium is improved.Test conditions is as follows: MgCl
2: Ge (mass ratio)=25: 1; GaO: Ge (mass ratio)=45: 1; 90 ℃ of temperature.
2.7 technic index sees the following form 2
Table 2
In sum, concrete technical scheme of the present invention is:
In the organic germanium waste liquid, press mass ratio and add MgCl
2And CaO, MgCl
2: Ge=20～40: 1 (mass ratio), CaO: Ge=30～50: 1 (mass ratio), NaOH solution with 5% (percentage concentration c%) is adjusted pH value=11～12, carry out the precipitation of germanium, 80～90 ℃ of precipitation temperatures, the precipitate recovery rate of germanium＞95%, precipitation germanium can obtain to contain the germanium concentrate of Ge 3.0～4.5% (mass percent w%) through 600～700 ℃ of calcinations; Germanium concentrate reclaims germanium through chlorinated distillation, the rate of recovery of germanium＞95%; The total yield of germanium＞90% in the waste liquid.Preferably resolve the recovery problem of germanium in the organic germanium waste liquid.
The recovery method of germanium in the organic germanium waste liquid of the present invention promptly adopts magnesium chloride-calcium oxide precipitation to reclaim germanium, has reduced the consumption of magnesium chloride, has reduced the production cost that reclaims germanium, and the rate of recovery of germanium＞90% has effectively reclaimed germanium.This method can be handled organic germanium waste liquid 100m every year
3, it is surplus to reclaim 1 ton on germanium metal, contribution tax 1,500,000.Obtained favorable economic benefit; Set up effective technical process for from the organic germanium waste liquid, reclaiming germanium.
Description of drawings
Fig. 1 is MgCl of the present invention
2Add-on and germanium deposition rate graph of a relation.
Fig. 2 is CaO add-on of the present invention and germanium deposition rate graph of a relation.
Fig. 3 is MgCl of the present invention
2With the heavy germanium graph of a relation of CaO.
Fig. 4 is that temperature of the present invention influences graph of a relation to the germanium precipitation.
Fig. 5 is the influence graph of a relation of pH value of the present invention to precipitation germanium.
Fig. 6 is a process flow sheet of the present invention.
Embodiment
Embodiment 1:
At 3m
3The quality of germanium is 10.5kg in the organic germanium waste liquid, presses MgCl
2: Ge=25: 1, CaO: Ge=45: 1 mass ratio adds MgCl
2263kg and CaO 473kg treat MgCl
2Substantially dissolve fully with CaO, adjust pH value=11～12,80～90 ℃ of precipitation temperatures, the precipitate recovery rate of germanium＞95% with the NaOH solution of 5% (percentage concentration c%); Throw out in 600～700 ℃ of calcinations, obtains to contain the germanium concentrate of Ge 3.0～4.5% (mass percent) after solid-liquid separation; Germanium concentrate enters chlorinated distillation, the chlorinated distillation rate of recovery＞95% of germanium; The total yield of germanium＞90% in the waste liquid.
Embodiment 2:
At 4m
3The quality of germanium is 16.5kg in the organic germanium waste liquid, presses MgCl
2: Ge=40: 1, CaO: Ge=50: 1 mass ratio adds MgCl
2660kg and CaO 825kg treat MgCl
2Substantially dissolve fully with CaO, adjust pH value=11～12,80～90 ℃ of precipitation temperatures, the precipitate recovery rate of germanium＞95% with the NaOH solution of 5% (percentage concentration c%); Throw out in 600～700 ℃ of calcinations, obtains to contain the germanium concentrate of Ge 3.0～4.5% (mass percent) after solid-liquid separation; Germanium concentrate enters chlorinated distillation, the chlorinated distillation rate of recovery＞95% of germanium; The total yield of germanium＞90% in the waste liquid.
Embodiment 3: at 3.5m
3The quality of germanium is 12.5kg in the organic germanium waste liquid, presses MgCl
2: Ge=35: 1, CaO: Ge=30: 1 mass ratio adds MgCl
2438kg and CaO 375kg treat MgCl
2Substantially dissolve fully with CaO, NaOH solution with 5% (percentage concentration c%) is adjusted pH value=11～12,80～90 ℃ of precipitation temperatures, the precipitate recovery rate of germanium＞95% throw out in 600～700 ℃ of calcinations, obtains to contain the germanium concentrate of Ge 3.0～4.5% (mass percent) after solid-liquid separation; Germanium concentrate enters chlorinated distillation, the chlorinated distillation rate of recovery＞95% of germanium; The total yield of germanium＞90% in the waste liquid.
Embodiment 4: at 3.5m
3The quality of germanium is 9.0kg in the organic germanium waste liquid, presses MgCl
2: Ge=20: 1, CaO: Ge=40: 1 mass ratio adds MgCl
2180kg and CaO 450kg treat MgCl
2Substantially dissolve fully with CaO, NaOH solution (percentage concentration c%) with 5% (percentage concentration c%) is adjusted pH value=11～12,80～90 ℃ of precipitation temperatures, the precipitate recovery rate of germanium＞95% throw out in 600～700 ℃ of calcinations, obtains to contain the germanium concentrate of Ge 3.0～4.5% (mass percent) after solid-liquid separation; Germanium concentrate enters chlorinated distillation, the chlorinated distillation rate of recovery＞95% of germanium; The total yield of germanium＞90% in the waste liquid.
Claims (2)
1. the recovery method of germanium in the organic germanium waste liquid is characterized in that: press mass ratio and add MgCl in the organic germanium waste liquid
2And CaO, MgCl
2: Ge=20～40: 1, CaO: Ge=30～50: 1 adjusts pH value=11～12 with NaOH solution, carries out the precipitation of germanium, and precipitation germanium contains the germanium concentrate of mass percent Ge 3.0～4.5% through 600～700 ℃ of calcinations acquisitions, and germanium concentrate reclaims germanium through chlorinated distillation.
2. the recovery method of germanium in the organic germanium waste liquid according to claim 1 is characterized in that: the precipitation temperature of germanium is 80～90 ℃.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102121066A (en) * | 2011-01-24 | 2011-07-13 | 云南临沧鑫圆锗业股份有限公司 | Process for reducing consumption of hydrochloric acid during chlorination distillation of germanium-containing raw material |
| CN110921905A (en) * | 2019-12-12 | 2020-03-27 | 四川高锗再生资源有限公司 | Recovery system and method for germanium-containing liquid in production of high-purity germanium dioxide |
| CN111041246A (en) * | 2019-12-18 | 2020-04-21 | 云南驰宏国际锗业有限公司 | Process method for recovering germanium mud through reaction sedimentation |
Citations (4)
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|---|---|---|---|---|
| CN1179472A (en) * | 1996-11-25 | 1998-04-22 | 云南会泽铅锌矿 | Method for treating high-germanium alum precipitation liquid |
| CN101205572A (en) * | 2007-12-03 | 2008-06-25 | 云南驰宏锌锗股份有限公司 | Technique for extracting germanium from germanium-containing material by pressure leaching |
| US20090070900A1 (en) * | 2007-06-12 | 2009-03-12 | Alexander Cherkasky | Novel cherkasky materials and novel use of biomolecules and biomasses |
| CN101608259A (en) * | 2009-07-01 | 2009-12-23 | 云南五鑫实业有限公司 | A kind of method that improves germanium leaching yield in the germanic raw material |
-
2010
- 2010-06-04 CN CN2010101914242A patent/CN101871047B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1179472A (en) * | 1996-11-25 | 1998-04-22 | 云南会泽铅锌矿 | Method for treating high-germanium alum precipitation liquid |
| US20090070900A1 (en) * | 2007-06-12 | 2009-03-12 | Alexander Cherkasky | Novel cherkasky materials and novel use of biomolecules and biomasses |
| CN101205572A (en) * | 2007-12-03 | 2008-06-25 | 云南驰宏锌锗股份有限公司 | Technique for extracting germanium from germanium-containing material by pressure leaching |
| CN101608259A (en) * | 2009-07-01 | 2009-12-23 | 云南五鑫实业有限公司 | A kind of method that improves germanium leaching yield in the germanic raw material |
Non-Patent Citations (1)
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102121066A (en) * | 2011-01-24 | 2011-07-13 | 云南临沧鑫圆锗业股份有限公司 | Process for reducing consumption of hydrochloric acid during chlorination distillation of germanium-containing raw material |
| CN102121066B (en) * | 2011-01-24 | 2012-09-12 | 云南临沧鑫圆锗业股份有限公司 | Process for reducing consumption of hydrochloric acid during chlorination distillation of germanium-containing raw material |
| CN110921905A (en) * | 2019-12-12 | 2020-03-27 | 四川高锗再生资源有限公司 | Recovery system and method for germanium-containing liquid in production of high-purity germanium dioxide |
| CN111041246A (en) * | 2019-12-18 | 2020-04-21 | 云南驰宏国际锗业有限公司 | Process method for recovering germanium mud through reaction sedimentation |
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Denomination of invention: A method for recovering germanium from organic germanium waste liquid Effective date of registration: 20230208 Granted publication date: 20111214 Pledgee: CITIC Bank Limited by Share Ltd. Kunming branch Pledgor: YUNNAN ZHONGKE XINYUAN CRYSTALLINE MATERIAL Co.,Ltd.|YUNNAN LINCANG XINYUAN GERMANIUM INDUSTRY Co.,Ltd.|YUNNAN DONGCHANG METAL PROCESSING Co.,Ltd.|KUNMING YUNZHE HIGH-TECH Co.,Ltd. Registration number: Y2023530000003 |