CN101066777A - Prepn process of germanium dioxide powder - Google Patents
Prepn process of germanium dioxide powder Download PDFInfo
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- CN101066777A CN101066777A CN 200710023583 CN200710023583A CN101066777A CN 101066777 A CN101066777 A CN 101066777A CN 200710023583 CN200710023583 CN 200710023583 CN 200710023583 A CN200710023583 A CN 200710023583A CN 101066777 A CN101066777 A CN 101066777A
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- gecl
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Abstract
The preparation process of small size GeO2 powder includes the following steps: adding high purity GeCl4 solution in the volume ratio between GeCl4 and H2O of 1 to 5-9 into electronic level deionized water to hydrolyze in the addition speed of 30-150 ml/min while stirring in 500-1400 rpm to react at 0-15 deg.c; further stirring in 500-1000 rpm after finishing addition for 15-30 min while ultrasonic vibration in the frequency of 40 KHz and power of 50-100 W; washing produced GeO2 particle with electronic level deionized water and stoving at 150-180 deg.c to obtain small size GeO2 powder.
Description
Technical field
The present invention relates to a kind of preparation of organic catalyst, particularly a kind of germanium dioxide (GeO
2) preparation method of powder.
Background technology
Original GeO
2Powder is mainly used in reduction Ge metal, therefore its granularity is not proposed special requirement.Adopt the GeO of existing explained hereafter
2Powder particles is bigger, generally about 30 μ m.Owing in hydrolytic process, adopt stirring rake to stir, stir insufficient hydrolytic process that often causes and be difficult to carry out fully a spot of GeCl
4Be wrapped in GeO
2In the powder, simultaneously, the GeO that hydrolysis produces
2The growth phenomenon can appear reuniting, cohering in powder.Laser particle size analyzer records the GeO of gained
2Powder particles is about 30 μ m, and＜10 μ m particles are about 30%.
Along with the development of society, GeO
2Catalytic performance obtained fast using, can be used for catalytic production trevira (PET), beverage vibrin, technicolor film with the food vessel, also can be used as the bleaching catalyst of textile industry; In addition, GeO
2Constitute catalyzer jointly with other material, as an amount of GeO
2Can effectively improve TiO
2The photocatalytic activity of nanoparticle also contains GeO in the catalyzer that the adjustment of the conversion of hydrocarbon polymer, hydrogenation, dehydrogenation, gasoline fraction is used on petrochemical complex
2Composition.At present, as catalyzer GeO
2Amount take its total consumption more than 20%.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of germanium dioxide powder is with remarkable reduction GeO
2Granularity, increase its specific surface area, give full play to its katalysis.
The invention provides a kind of small size GeO
2The preparation method of powder may further comprise the steps:
With high-purity (〉=99.99%) GeCl
4Liquid, GeCl by volume
4: H
2O=1: 5～9 ratios slowly join hydrolysis in the electronic-grade deionized water, and reinforced while stirring, feed rate is 30ml/min～150ml/min; Stirring velocity is 500 commentaries on classics/min～1400 commentaries on classics/min; Temperature of reaction is 0 ℃～15 ℃; After blanking finished, stirring rake continued to stir, and stirring velocity is 500 commentaries on classics/min～1000 commentaries on classics/min; Adopt ultra-sonic oscillation when stirring after the blanking, oscillation frequency is 40KHz, hunting power 50～100W; Churning time is 15min～30min; With the GeO of electronic-grade deionized water to separating out in the whipping process
2Particle is washed, and behind 150 ℃～180 ℃ oven dry 8h～12h, can obtain GeO
2Powder.
Foregoing high-purity GeCl
4Liquid is meant the GeCl of purity 〉=99.99%
4, wherein the resistance of electronic-grade deionized water is greater than 10M Ω.
Products therefrom adopts laser particle analyzer to measure, and analytical results is as follows: D10=1.92 μ m, D50=5.03 μ m, D90=11.86 μ m,＜10.00 μ m accumulation=85.42%, s/v=16750.73cm
2/ cm
3, Dav=6.21 μ m.
Beneficial effect of the present invention is: (1) the present invention is to industrial GeCl
4GeO is produced in the solution hydrolysis
2The improvement of powder craft realizes easily; (2) GeO for preparing
2Powder particles is tiny, adopts laser particle analyzer to measure the distribution curve of its granular size, and the size that records its medium particle diameter is 5 μ m～12 μ m; The particle of＜10 μ m is about 90%; (3) under condition of the present invention, GeCl
4Because of adopting ultrasonic stirring, make stirring more abundant in the hydrolytic process, can shorten hydrolysis time, avoid GeO effectively
2Powder ball gathers, coheres the growth phenomenon; (4) promote GeCl
4Carrying out fast of hydrolysis reaction reduces not hydrolysis GeCl
4Content, help improving GeO
2The purity of powder.
Description of drawings
Fig. 1 is to use the GeO of existing Technology preparation
2Powder SEM pattern
Fig. 2 is to use the GeO of existing Technology preparation
2The distribution curve of powder particle
Fig. 3 is to use the GeO of technology preparation of the present invention
2Powder SEM pattern
Fig. 4 is to use the GeO of technology preparation of the present invention
2The distribution curve of powder particle
Embodiment
Select different GeCl for use
4GeO is produced in the solution hydrolysis
2Powder craft is operated, and concrete embodiment is as follows:
With high-purity GeCl
4Solution, GeCl by volume
4: H
2O=1: 9 ratios slowly join hydrolysis in the electronic-grade deionized water, and reinforced while stirring, feed rate is 30ml/min; Stirring velocity 1000 commentaries on classics/min; Icy salt solution circulation cooling with-10 ℃ is controlled at 10 ℃ with the hydrolytic process temperature; After blanking finished, stirring rake continued to stir, and stirring velocity is 800 commentaries on classics/min, and the ultra-sonic oscillation frequency is 40KHz, hunting power 100W, and the time is 20min; With the GeO of electronic-grade deionized water to separating out in the whipping process
2Particle is washed, and behind 180 ℃ of oven dry 8h, can obtain the GeO that medium particle diameter is 5 μ m
2Powder.
Embodiment 2
With high-purity GeCl
4Solution, GeCl by volume
4: H
2O=1: 7 ratios slowly join hydrolysis in the electronic-grade deionized water, and reinforced while stirring, feed rate is 30ml/min; Stirring velocity 1000 commentaries on classics/min; Icy salt solution circulation cooling with-10 ℃ is controlled at 10 ℃ with the hydrolytic process temperature; After blanking finished, stirring rake continued to stir, and stirring velocity is 800 commentaries on classics/min, and the ultra-sonic oscillation frequency is 40KHz, hunting power 50W, and the time is 30min; With the GeO of electronic-grade deionized water to separating out in the whipping process
2Particle is washed, and behind 180 ℃ of oven dry 8h, can obtain the GeO that medium particle diameter is 6 μ m
2Powder.
Embodiment 3
With high-purity GeCl
4Solution, GeCl by volume
4: H
2O=1: 7.5 ratios slowly join hydrolysis in the electronic-grade deionized water, and reinforced while stirring, feed rate is 50ml/min; Stirring velocity 1000 commentaries on classics/min; Icy salt solution circulation cooling with-10 ℃ is controlled at 5 ℃ with the hydrolytic process temperature; After the blanking, stirring rake continues to stir, and stirring velocity is 700 commentaries on classics/min, and the ultra-sonic oscillation frequency is 40KHz, hunting power 80W, and the time is 20min; With the GeO of electronic-grade deionized water to separating out in the whipping process
2Particle is washed, and behind 180 ℃ of oven dry 8h, can obtain the GeO that medium particle diameter is 6 μ m
2Powder.
Embodiment 4
With high-purity GeCl
4Solution, GeCl by volume
4: H
2O=1: 7 ratios slowly join hydrolysis in the electronic-grade deionized water, and reinforced while stirring, feed rate is 70ml/min; Stirring velocity 1000 commentaries on classics/min; Icy salt solution circulation cooling with-10 ℃ is controlled at 1 ℃ with the hydrolytic process temperature; After blanking finished, stirring rake continued to stir, and stirring velocity is 700 commentaries on classics/min, and the ultra-sonic oscillation frequency is 40KHz, hunting power 100W, and the time is 20min; With the GeO of electronic-grade deionized water to separating out in the whipping process
2Particle is washed, and behind 150 ℃ of oven dry 12h, can obtain the GeO that medium particle diameter is 6.5 μ m
2Powder.
Embodiment 5
With high-purity GeCl
4Solution, GeCl by volume
4: H
2O=1: 7 ratios slowly join hydrolysis in the electronic-grade deionized water, and reinforced while stirring, feed rate is 100ml/min; Stirring velocity 800 commentaries on classics/min; Icy salt solution circulation cooling with-10 ℃ is controlled at 15 ℃ with the hydrolytic process temperature; After blanking finished, stirring rake continued to stir, and stirring velocity is 700 commentaries on classics/min, and the ultra-sonic oscillation frequency is 40KHz, hunting power 80W, and the time is 20min; With the GeO of electronic-grade deionized water to separating out in the whipping process
2Particle is washed, and behind 180 ℃ of oven dry 8h, can obtain the GeO that medium particle diameter is 8 μ m
2Powder.
Embodiment 6
With high-purity GeCl
4Solution, GeCl by volume
4: H
2O=1: 7 ratios slowly join hydrolysis in the electronic-grade deionized water, and reinforced while stirring, feed rate is 100ml/min; Stirring velocity 1000 commentaries on classics/min; Icy salt solution circulation cooling with-10 ℃ is controlled at 14 ℃ with the hydrolytic process temperature; After blanking finished, stirring rake continued to stir, and stirring velocity is 700 commentaries on classics/min, and the ultra-sonic oscillation frequency is 40KHz, hunting power 50W, and the time is 30min; With the GeO of electronic-grade deionized water to separating out in the whipping process
2Particle is washed, and behind 180 ℃ of oven dry 8h, can obtain the GeO that medium particle diameter is 8.5 μ m
2Powder.
Embodiment 7
With high-purity GeCl
4Solution, GeCl by volume
4: H
2O=1: 6.5 ratios slowly join hydrolysis in the electronic-grade deionized water, and reinforced while stirring, feed rate is 150ml/min; Stirring velocity 1000 commentaries on classics/min; Icy salt solution circulation cooling with-10 ℃ is controlled at 15 ℃ with the hydrolytic process temperature; After blanking finished, stirring rake continued to stir, and stirring velocity is 700 commentaries on classics/min, and the ultra-sonic oscillation frequency is 40KHz, hunting power 100W, and the time is 20min; With the GeO of electronic-grade deionized water to separating out in the whipping process
2Particle is washed, and behind 150 ℃ of oven dry 12h, can obtain the GeO that medium particle diameter is 10 μ m
2Powder.
Embodiment 8
With high-purity GeCl
4Solution, GeCl by volume
4: H
2O=1: 7 ratios slowly join hydrolysis in the electronic-grade deionized water, and reinforced while stirring, feed rate is 140ml/min; Stirring velocity 700 commentaries on classics/min; Icy salt solution circulation cooling with-10 ℃ is controlled at 15 ℃ with the hydrolytic process temperature; After blanking finished, stirring rake continued to stir, and stirring velocity is 600 commentaries on classics/min, and the ultra-sonic oscillation frequency is 40KHz, hunting power 50W, and the time is 20min; With the GeO of electronic-grade deionized water to separating out in the whipping process
2Particle is washed, and behind 150 ℃ of oven dry 12h, can obtain the GeO that medium particle diameter is 12 μ m
2Powder.
Embodiment 9
With high-purity GeCl
4Solution, GeCl by volume
4: H
2O=1: 5 ratios slowly join hydrolysis in the electronic-grade deionized water, and reinforced while stirring, feed rate is 30ml/min; Stirring velocity 1000 commentaries on classics/min; Icy salt solution circulation cooling with-10 ℃ is controlled at 5 ℃ with the hydrolytic process temperature; After blanking finished, stirring rake continued to stir, and stirring velocity is 800 commentaries on classics/min, and the ultra-sonic oscillation frequency is 40KHz, hunting power 100W, and the time is 20min; With the GeO of electronic-grade deionized water to separating out in the whipping process
2Particle is washed, and behind 180 ℃ of oven dry 8h, can obtain the GeO that medium particle diameter is 12 μ m
2Powder.
With high-purity GeCl
4Solution, GeCl by volume
4: H
2O=1: 9 ratios slowly join hydrolysis in the electronic-grade deionized water, and reinforced while stirring, feed rate is 50ml/min; Stirring velocity 1000 commentaries on classics/min; Icy salt solution circulation cooling with-10 ℃ is controlled at 12 ℃ with the hydrolytic process temperature; After the blanking, stirring rake continues to stir, and stirring velocity is 700 commentaries on classics/min, and the ultra-sonic oscillation frequency is 40KHz, hunting power 80W, and the time is 20min; With the GeO of electronic-grade deionized water to separating out in the whipping process
2Particle is washed, and behind 180 ℃ of oven dry 8h, can obtain the GeO that medium particle diameter is 6 μ m
2Powder.
Claims (3)
1. the preparation method of a germanium dioxide powder is characterized by and may further comprise the steps:
With GeCl
4Liquid, GeCl by volume
4: H
2O=1: 5～9 ratios join hydrolysis in the electronic-grade deionized water, and reinforced while stirring, feed rate is 30ml/min～150ml/min; Temperature of reaction is 0 ℃～15 ℃; After blanking finished, stirring rake continued to stir; Adopt ultra-sonic oscillation when stirring after the blanking, oscillation frequency is 40KHz, hunting power 50～100W; Churning time is 15min～30min; With the electronic-grade deionized water germanium dioxide particle of separating out in the whipping process is washed, after 150 ℃～180 ℃ oven dry, can be obtained the germanium dioxide powder.
2. a kind of preparation method of germanium dioxide powder according to claim 1 is characterized by GeCl
4: H
2O=1: 6.5～7.5 volume ratios.
3. a kind of preparation method of germanium dioxide powder according to claim 1, it is characterized by feed rate is 100ml/min～130ml/min.
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|---|---|---|---|
| CN 200710023583 CN101066777A (en) | 2007-06-08 | 2007-06-08 | Prepn process of germanium dioxide powder |
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|---|---|---|---|
| CN 200710023583 CN101066777A (en) | 2007-06-08 | 2007-06-08 | Prepn process of germanium dioxide powder |
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| CN101066777A true CN101066777A (en) | 2007-11-07 |
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|---|---|---|---|
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014162648A (en) * | 2013-02-21 | 2014-09-08 | Dowa Metals & Mining Co Ltd | Method for producing germanium oxide |
| CN107935028A (en) * | 2017-12-21 | 2018-04-20 | 昆明汇泉高纯半导材料有限公司 | A kind of catalyst type high pu-rity germanium production method |
| CN109279646A (en) * | 2018-11-26 | 2019-01-29 | 广东先导稀材股份有限公司 | The production method of catalyst grade germanium dioxide |
| CN112456544A (en) * | 2020-12-28 | 2021-03-09 | 云南驰宏国际锗业有限公司 | Method for preparing superfine germanium dioxide by ultrasonic hydrolysis |
| 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 |
-
2007
- 2007-06-08 CN CN 200710023583 patent/CN101066777A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014162648A (en) * | 2013-02-21 | 2014-09-08 | Dowa Metals & Mining Co Ltd | Method for producing germanium oxide |
| CN107935028A (en) * | 2017-12-21 | 2018-04-20 | 昆明汇泉高纯半导材料有限公司 | A kind of catalyst type high pu-rity germanium production method |
| CN109279646A (en) * | 2018-11-26 | 2019-01-29 | 广东先导稀材股份有限公司 | The production method of catalyst grade germanium dioxide |
| CN109279646B (en) * | 2018-11-26 | 2020-12-22 | 广东先导稀材股份有限公司 | Production method of catalyst-grade germanium dioxide |
| CN112456544A (en) * | 2020-12-28 | 2021-03-09 | 云南驰宏国际锗业有限公司 | Method for preparing superfine germanium dioxide by ultrasonic hydrolysis |
| CN112456544B (en) * | 2020-12-28 | 2022-09-02 | 云南驰宏国际锗业有限公司 | Method for preparing superfine germanium dioxide by ultrasonic hydrolysis |
| 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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Open date: 20071107 |