CN109534388A - A kind of preparation method of high-purity germanium dioxide - Google Patents
A kind of preparation method of high-purity germanium dioxide Download PDFInfo
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- CN109534388A CN109534388A CN201910023629.0A CN201910023629A CN109534388A CN 109534388 A CN109534388 A CN 109534388A CN 201910023629 A CN201910023629 A CN 201910023629A CN 109534388 A CN109534388 A CN 109534388A
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- preparation
- metal powder
- germanium
- germanium metal
- hydrogen peroxide
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G17/00—Compounds of germanium
- C01G17/02—Germanium dioxide
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Oxygen, Ozone, And Oxides In General (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The present invention discloses a kind of preparation method of high-purity germanium dioxide, comprising the following steps: germanium metal powder is mixed with water, heating；Hydrogen peroxide is added and carries out oxidation reaction, filtering obtains filtrate；Filtrate, crystallization is concentrated, obtains germanic acid crystallization；Germanic acid crystallization in the case where being passed through inert gas conditions carry out cracking reaction to get；The preparation method, low in cost, process is simple, friendly to environment and operator, and process cycle is short, and obtained germanium dioxide purity is high, whiteness is high, not chloride ion-containing.
Description
Technical field
The present invention relates to metallurgical technology fields, and in particular to a kind of preparation method of high-purity germanium dioxide.
Background technique
Germanium dioxide molecular formula germanium dioxide, molecular weight 104.64, physical behavior be white powder or colourless crystallization, at present
It is widely used in infrared acquisition, high-tech areas and the national defence such as optical fiber doping simultaneously can be used for spectrum analysis and partly lead
Body material etc. is a kind of strategic material with high application value.
There are two types of the existing main methods for preparing germanium dioxide:
One is thermal process, i.e., oxygen is passed through in electric arc furnaces, high-temperature oxydation germanium powder is to be made germanium dioxide.Existing fire
Law technology has the disadvantages that
1, electric arc furnaces cost is high, an electric arc furnaces often cost it is hundreds of thousands of more than, small business powerlessly undertakes.
2, thermal process energy consumption is high, and use cost is expensive.
3, the oxygen being passed through is 4N (99.99%) or the high purity oxygen gas of 5N (99.999%), expensive.
Two be wet processing, i.e. hydrolysis germanium tetrachloride, then Pintsch process.Existing Wet technique also has following lack
Point:
1, germanium tetrachloride is expensive, and the mainstream preparation method of germanium tetrachloride is to be closed in a heated condition with germanium with chlorine
At, it is with high costs, and pollution is very big, it is harmful to operator.
2, the fusing point of germanium tetrachloride is -49.5 DEG C, is fuming liquids, highly volatile under room temperature, and have severe toxicity, to operator
Member is harmful.
2, the chloride ion content in germanium dioxide being prepared using germanium tetrachloride is high, this performance shadow to germanium dioxide
It rings big.
Summary of the invention
In view of this, low in cost, process is simple, right this application provides a kind of preparation method of high-purity germanium dioxide
Environment and operator are friendly, and process cycle is short, and obtained germanium dioxide purity is high, whiteness is high, not chloride ion-containing.
In order to solve the above technical problems, technical solution provided by the invention is a kind of preparation method of high-purity germanium dioxide,
The following steps are included:
(1) germanium metal powder is mixed with water, heating；
(2) hydrogen peroxide is added and carries out oxidation reaction, filtering obtains filtrate；
(3) filtrate, crystallization is concentrated, obtains germanic acid crystallization；
(4) germanic acid crystallization in the case where being passed through inert gas conditions carry out cracking reaction to get.
Preferably, germanium metal powder is 4N germanium metal powder.
Preferably, the germanium metal powder is 100 mesh~200 mesh powders made of germanium metal.
Preferably, germanium metal powder and water weight ratio are 3.0-5.0:1.
Preferably, the hydrogen peroxide is 30wt% hydrogen peroxide.
Preferably, the oxidation reaction process temperature is 90 DEG C or more.
Preferably, the weight ratio of the hydrogen peroxide and germanium metal powder is 2.6~3.0:1.
Preferably, the step (2) specifically includes: being gradually added hydrogen peroxide and carries out oxidation reaction, clarifies to solution colour
It is transparent, stop that hydrogen peroxide is added, filtering obtains filtrate.
Preferably, the step (2) specifically includes: being gradually added hydrogen peroxide and carries out oxidation reaction, clarifies to solution colour
It is transparent, stop that hydrogen peroxide is added, filtering obtains filtrate.
Preferably, the step (2) specifically includes: hydrogen peroxide is added and ammonium hydroxide carries out oxidation reaction, filtering is filtered
Liquid.
Preferably, the ammonium hydroxide is 5wt% ammonium hydroxide.
Preferably, the step (3) specifically includes: concentration filtrate, natural cooling crystallization obtain germanic acid crystallization.
Preferably, the inert gas is nitrogen or argon gas.
Preferably, the inert gas flow velocity being passed through is 0.5~1.5L/min.
Preferably, the cracking reaction process cracking temperature is 450~550 DEG C.
Preferably, described cracking reaction process pyrolysis time 8 more than hour.
Compared with prior art, detailed description are as follows by the application:
The present invention provides a kind of preparation methods of high-purity germanium dioxide, are raw material, dioxygen only with germanium metal powder, water
Water is oxidant, and cracking reaction process is passed through inert gas, and low in cost, process is simple, friendly to environment and operator, work
The skill period is short, and the germanium dioxide purity is high reached, purity can reach 99.99% or more, and whiteness is high, not chloride ion-containing.
Further, the present invention first mixes germanium metal powder and water, prevents initial reaction excessively violent；The present invention
Oxidation reaction process controls the speed that hydrogen peroxide is added, and avoids reaction excessively violent.Germanium metal powder of the present invention is germanium metal system
At 100 mesh~200 mesh powders ensure that oxidation reaction process reaction speed, can be added in step (2) oxidation reaction process
Ammonia and Ge4+Complex ion is formed, the two, which is mutually promoted, carries out reaction, improves reaction speed.
Specific embodiment
It is right combined with specific embodiments below in order to make those skilled in the art more fully understand technical solution of the present invention
The present invention is described in further detail.
Embodiment 1
It is a kind of preparation method of high-purity germanium dioxide, comprising the following steps:
(1) water is added in reaction kettle, opens stirring, then puts into the germanium metal powder among reaction kettle, heating is anti-
Answer kettle；
(2) it is gradually added hydrogen peroxide and carries out oxidation reaction, to solution colour clear, stop that hydrogen peroxide is added, filter,
Obtain filtrate；It is gradually added hydrogen peroxide according to real-time condition, avoids reaction excessively violent；
(3) filtrate is concentrated, obtains stopping heating for filtrate volume, concentrate is transferred to 5~35 DEG C of items in polyethylene can
Natural cooling crystallization under part obtains germanic acid crystallization；
(4) germanic acid crystallization in the case where being passed through inert gas conditions carry out cracking reaction to get.
Wherein,
The germanium metal powder is 100 mesh~200 mesh powders made of 4N germanium metal.
The water is ultrapure water.
Germanium metal powder and water weight ratio are 3.0-5.0:1.
Heating reaction kettle to reactor temperature is 90~95 DEG C.
The hydrogen peroxide is 30wt% hydrogen peroxide.
The weight ratio of the hydrogen peroxide and germanium metal powder is 2.6~3.0:1.
The inert gas is nitrogen or argon gas.
The inert gas flow velocity being passed through is 0.5~1.5L/min.
The cracking reaction process cracking temperature is 450~550 DEG C.
8~10h of cracking reaction process pyrolysis time.
The high-purity germanium dioxide purity that above-mentioned preparation method obtains can reach 99.99% or more, and whiteness is high, and yield reaches
98% or more.
Embodiment 2
The present embodiment and the difference of embodiment 1 are only that:
(2) reaction kettle is heated, hydrogen peroxide is gradually added and ammonium hydroxide carries out oxidation reaction and stops to solution colour clear
Hydrogen peroxide is only added, filters, obtains filtrate；It is gradually added hydrogen peroxide and ammonium hydroxide according to real-time condition, avoids reaction excessively violent；
The ammonium hydroxide is 5wt% ammonium hydroxide.
The present embodiment preparation method step (2) oxidation reaction speed is faster than 1 step of embodiment (2) oxidation reaction speed.?
To high-purity germanium dioxide purity can reach 99.99% or more, whiteness is high, and yield reaches 98% or more.
Embodiment 3
The present embodiment the difference from embodiment 1 is that:
The germanium metal powder is 20 mesh~80 mesh powders made of 4N germanium metal.The present embodiment preparation method step
(2) oxidation reaction is slow compared with 1 step of embodiment (2) oxidation reaction, or even does not react.
Embodiment 4
The present embodiment and the difference of embodiment 2 are only that:
The germanium metal powder is 10 mesh~50 mesh powders made of 4N germanium metal
The present embodiment preparation method, which obtains germanium dioxide purity, can reach 99.99% or more, and whiteness is high, and yield reaches 98%
More than.
Embodiment 5
The present embodiment the difference from embodiment 1 is that:
Heating reaction kettle to reactor temperature is 80~85 DEG C.The present embodiment preparation method step (2) oxidation reaction compared with
1 step of embodiment (2) oxidation reaction is slow, or even does not react.
The above is only the preferred embodiment of the present invention, it is noted that above-mentioned preferred embodiment is not construed as pair
Limitation of the invention, protection scope of the present invention should be defined by the scope defined by the claims..For the art
For those of ordinary skill, without departing from the spirit and scope of the present invention, several improvements and modifications can also be made, these change
It also should be regarded as protection scope of the present invention into retouching.
Claims (10)
1. a kind of preparation method of high-purity germanium dioxide, which comprises the following steps:
(1) germanium metal powder is mixed with water, heating；
(2) hydrogen peroxide is added and carries out oxidation reaction, filtering obtains filtrate；
(3) filtrate, crystallization is concentrated, obtains germanic acid crystallization；
(4) germanic acid crystallization in the case where being passed through inert gas conditions carry out cracking reaction to get.
2. preparation method according to claim 1, which is characterized in that germanium metal powder is 4N germanium metal powder.
3. preparation method according to claim 1, which is characterized in that the germanium metal powder is 100 made of germanium metal
Mesh~200 mesh powders.
4. preparation method according to claim 1, which is characterized in that germanium metal powder and water weight ratio are 3.0-5.0:
1。
5. preparation method according to claim 1, which is characterized in that the oxidation reaction process temperature is 90 DEG C or more.
6. preparation method according to claim 1, which is characterized in that the weight ratio of the hydrogen peroxide and germanium metal powder is
2.6~3.0:1.
7. preparation method according to claim 1, which is characterized in that the step (2) specifically includes: being gradually added dioxygen
Water carries out oxidation reaction, to solution colour clear, stops that hydrogen peroxide is added, filtering obtains filtrate.
8. preparation method according to claim 1, which is characterized in that the inert gas is nitrogen or argon gas.
9. preparation method according to claim 1, which is characterized in that the inert gas flow velocity being passed through be 0.5~
1.5L/min。
10. preparation method according to claim 1, which is characterized in that the cracking reaction process cracking temperature be 450~
550℃。
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN114702060A (en) * | 2022-05-13 | 2022-07-05 | 广东先导稀材股份有限公司 | Preparation method of germanium dioxide capable of being rapidly dissolved in ethylene glycol |
| CN115536055A (en) * | 2022-09-27 | 2022-12-30 | 昆明理工大学 | Method for preparing germanium dioxide from zinc hydrometallurgy inorganic germanium slag |
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| JP2015105226A (en) * | 2013-12-03 | 2015-06-08 | 三菱マテリアル株式会社 | Method for producing germanium oxide |
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| JP2015105226A (en) * | 2013-12-03 | 2015-06-08 | 三菱マテリアル株式会社 | Method for producing germanium oxide |
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| CN106365129A (en) * | 2016-08-29 | 2017-02-01 | 石棉阔山新材料科技有限公司 | High-purity tellurium dioxide preparation method and device |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN114702060A (en) * | 2022-05-13 | 2022-07-05 | 广东先导稀材股份有限公司 | Preparation method of germanium dioxide capable of being rapidly dissolved in ethylene glycol |
| CN115536055A (en) * | 2022-09-27 | 2022-12-30 | 昆明理工大学 | Method for preparing germanium dioxide from zinc hydrometallurgy inorganic germanium slag |
| CN115536055B (en) * | 2022-09-27 | 2023-08-18 | 昆明理工大学 | Method for preparing germanium dioxide from zinc hydrometallurgy inorganic germanium slag |
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Application publication date: 20190329 |