CN103160856A - Preparation method of high-purity gallium - Google Patents
Preparation method of high-purity gallium Download PDFInfo
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- CN103160856A CN103160856A CN2011104230117A CN201110423011A CN103160856A CN 103160856 A CN103160856 A CN 103160856A CN 2011104230117 A CN2011104230117 A CN 2011104230117A CN 201110423011 A CN201110423011 A CN 201110423011A CN 103160856 A CN103160856 A CN 103160856A
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Abstract
The invention provides a preparation method of high-purity gallium. The method comprises preparing a sodium hydroxide solution with a prescribed concentration and a temperature higher than a melting point of the gallium as an electrolyte, filling the prepared electrolyte into an electrolytic tank, preparing the gallium raw material as a positive plate and a negative plate of the electrolytic tank, respectively putting the positive plate and the negative plate into an anode area and a cathode area of the electrolytic tank, starting electrolytic cycle of the electrolytic tank for direct current electrolysis so as to obtain electrolyzed gallium at the cathode region, taking out the electrolyzed gallium at the cathode region after the direct current electrolysis, and then putting in a crystallization groove with a temperature lower than the melting point of the gallium for crystallization, thereby obtaining the crystallized gallium. The preparation method of the high-purity gallium provided by the invention combines the electrolysis and the crystallization, and thus has advantages of low impurity content in products, high product qualified rate, simple preparation technology, low investment, and improved production capacity for single set of equipment, and is energy saving and environmental protective.
Description
Technical field
The present invention relates to a kind of preparation method of high pure metal, relate in particular to a kind of preparation method of high purity gallium.
Background technology
Gallium is the silvery white metal, and ordination number is 31, and relative atomic mass is 69.7233, belongs to IIIA family, and solid gallium is pewter, and liquid-gallium is silvery white, and fusing point only has 29.8 ℃, and the boiling point of gallium is higher, and when becoming solid by liquid, volume can increase 3.2%.The chemical property of gallium is more stable, reacts with oxygen and water hardly at normal temperatures, and gallium has both sexes, is dissolved in bronsted lowry acids and bases bronsted lowry.Have the ability that absorbs neutron due to gallium, can play the effect of controlling number of neutrons and speed of response in reactor, contribute for the mankind use atomic energy.Gallium has the sealing liquid that very low vapour pressure can be used as vacuum unit, because gallium has very strong reflection potential, can be used as the reflective mirror of high-quality.Gallium can be used as alloy and improves wear resistance.Gallium compound is widely used the catalyzer in analytical chemistry, organic chemistry and medicine.High purity gallium is widely used mobile communication, band optical fiber communication, PC, telstar etc. as making electronics device and epitaxial wafer and the photoelectron devices such as gallium arsenide, gan, gallium phosphide and low melting alloy.In recent years, gallium was applied to semiconductor material, was described as " grain of semiconductor material ".
At present, the preparation approach for preparing high purity gallium both at home and abroad mainly contains two kinds: the one, and, make with extra care by various process for purification and obtain high purity gallium as raw material with the industrial crude gallium; The 2nd, the various gallium waste materials that contain that produce in the semiconductor material production process are removed impurity component as raw material by several different methods, directly are recovered to high purity gallium.disclose a kind of electrolysis-crystallization method in the Chinese patent CN85102460 of authorization on November 15th, 1989 bulletin and prepared high purity gallium, this preparation method is as raw material with rough gallium, refined gallium with molten is carried out electrolysis as negative electrode, after the gallium that obtains 6N purity on negative electrode, carry out Crystallization Separation at the anticathode gallium, the last high purity gallium to 7N, the method electrolysis Anodic and negative electrode are molten state, not to be easy to control in actual mechanical process, the comparison in equipment that uses is complicated, its suitability for industrialized production is implemented relatively suffering, operational condition is harsher.The method that disclosed Chinese patent application publication number CN1619018A proposition combined with low-temperature electrolytic and zone melting on May 25th, 2005, although can prepare the above high purity product of 7N, but the production time is longer, production cost is higher, be not suitable for scale operation, therefore application is restricted.
Summary of the invention
In view of the deficiency in background technology, the object of the present invention is to provide a kind of preparation method of high purity gallium, it makes, and the product foreign matter content is low, product percent of pass is high.
Another object of the present invention is to provide a kind of preparation method of high purity gallium, it can be simplified preparation technology, less investment and then improve single complete equipment production capacity and energy-conserving and environment-protective.
In order to reach purpose of the present invention, the preparation method who the invention provides a kind of high purity gallium comprises step: the preparation normality and temperature higher than the sodium hydroxide solution of gallium fusing point as electrolytic solution; The electrolytic solution of preparation is packed in electrolyzer; Gallium material is made as positive plate and the negative plate of described electrolyzer; Described positive plate and described negative plate are respectively charged in the positive column and cathodic area of described electrolyzer; Start the electrolysis cycle of described electrolyzer, carry out dc electrolysis, to obtain cathodic area electrolysis gallium in described cathodic area; After dc electrolysis is completed, described cathodic area electrolysis gallium is taken out and send be placed in the crystallizer tank of temperature lower than the gallium fusing point, carrying out crystallization, thereby obtain the crystallization gallium.
Beneficial effect of the present invention is as follows.
The preparation method of high purity gallium of the present invention is by adopting electrolysis-crystallization associating, makes that the product foreign matter content is low, product percent of pass is high.
The preparation method of high purity gallium of the present invention is by adopting electrolysis-crystallization associating, and preparation technology simplifies, less investment, and single complete equipment production capacity improves, and energy-conserving and environment-protective.
Description of drawings
Fig. 1 has provided the schema according to the preparation method of high purity gallium of the present invention.
Wherein, description of reference numerals is as follows:
S1, S2, S3, S4, S5, S6, S7 step
Embodiment
Describe preparation method and the embodiment of high purity gallium of the present invention in detail below in conjunction with accompanying drawing.
At first preparation method according to high purity gallium of the present invention is described.
Comprise step according to the preparation method of high purity gallium of the present invention: the preparation normality and temperature higher than the sodium hydroxide solution of gallium fusing point as electrolytic solution (step S1); With the electrolytic solution of preparation pack into (step S2) in electrolyzer; Gallium material is made as positive plate and the negative plate (step S3) of described electrolyzer; Described positive plate and described negative plate are respectively charged in the positive column and cathodic area of described electrolyzer (step S4); Start the electrolysis cycle of described electrolyzer, carry out dc electrolysis, to obtain cathodic area electrolysis gallium (step S5) in described cathodic area; After dc electrolysis is completed, described cathodic area electrolysis gallium is taken out and send be placed in the crystallizer tank of temperature lower than the gallium fusing point, carrying out crystallization, thereby obtain crystallization gallium (step S6).
In step S1, the massfraction of described sodium hydroxide solution is 10～40%.
In step S1, the temperature of sodium hydroxide solution is 30～60 ℃.
In step S5, the current density of described dc electrolysis is 50～600A/m
2The required direct current of described dc electrolysis can be undertaken by the rectifier that is arranged on the electrolytic tank electrolysis circulation path.
In step S6, the temperature of described crystallizer tank is 25～28 ℃.The temperature of crystallizer tank is controlled and can be undertaken by crystallizer tank is placed in cooling bath.
In step S6, the crystallization time of described cathodic area electrolysis gallium is 8～12h.
In step S6, can be with stirring when described cathodic area electrolysis gallium carries out crystallization in described crystallizer tank, and stirring velocity is preferably 20～30rps.
In step S6, described cathodic area electrolysis gallium carries out crystallization in described crystallizer tank percent crystallization in massecuite is 70～80%.
In the preparation method according to high purity gallium of the present invention, preferably, also can comprise step: the crystallization gallium that obtains is cleaned (step S7).Wherein, described cleaning can be adopted hydrochloric acid, and massfraction is 3%～5%.
Next, embodiment according to the preparation method of high purity gallium of the present invention is described.
Embodiment 1
The preparation sodium hydroxide solution is as electrolytic solution, and the massfraction of sodium hydroxide is 10%, and the temperature of sodium hydroxide solution is 30 ℃; The current density of the dc electrolysis of electrolyzer is 50A/m
2The temperature of crystallizer tank is 25 ℃, and stirring velocity is 20rps, and crystallization time is 8h, and percent crystallization in massecuite is 70%; The crystal gallium that obtains is cleaned respectively, and scavenging solution is the hydrochloric acid soln of massfraction 5%.
Embodiment 2
The preparation sodium hydroxide solution is as electrolytic solution, and the massfraction of sodium hydroxide is 20%, and the temperature of solution is 30 ℃; The current density of the dc electrolysis of electrolyzer is 100A/m
2The temperature of crystallizer tank is 25 ℃, and stirring velocity is 20rps, and crystallization time is 8h, and percent crystallization in massecuite is 70%; The crystal gallium that obtains is cleaned respectively, and scavenging solution is the hydrochloric acid soln of massfraction 4%.
Embodiment 3
The preparation sodium hydroxide solution is as electrolytic solution, and the massfraction of sodium hydroxide is 30%, and the temperature of solution is 39 ℃; The current density of the dc electrolysis of electrolyzer is 200A/m
2The temperature of crystallizer tank is 26 ℃, and stirring velocity is 22rps, and crystallization time is 10h, and percent crystallization in massecuite is 80%; The crystal gallium that obtains is cleaned respectively, and scavenging solution is the hydrochloric acid soln of massfraction 3%.
Embodiment 4
The preparation sodium hydroxide solution is as electrolytic solution, and the massfraction of sodium hydroxide is 40%, and the temperature of solution is 50 ℃; The current density of the dc electrolysis of electrolyzer is 300A/m
2The temperature of crystallizer tank is 25 ℃, and stirring velocity is 30rps, and crystallization time is 11h, and percent crystallization in massecuite is 75%; The crystal gallium that obtains is cleaned respectively, and scavenging solution is the hydrochloric acid soln of massfraction 5%.
Embodiment 5
The preparation sodium hydroxide solution is as electrolytic solution, and the massfraction of sodium hydroxide is 40%, and the temperature of solution is 60 ℃; The current density of the dc electrolysis of electrolyzer is 600A/m
2The temperature of crystallizer tank is 28 ℃, and stirring velocity is 30rps, and crystallization time is 12h, and percent crystallization in massecuite is 78%; The crystal gallium that obtains is cleaned respectively, and scavenging solution is the hydrochloric acid soln of massfraction 5%.
Provide at last the test result of above-described embodiment.Product adopts icp ms (ICP-MS) to detect that (manufacturer is PE company, model is: DRC-II), the testing conditions of this equipment is: temperature is 18 ℃-28 ℃, and relative humidity is 30-70%, and cleanliness factor is 1000 grades.
The detection principle of this instrument is: the icp ms detection mode: element to be measured enters mass analyzer with the positive charge form after ionizing through plasma high-temperature, and the difference according to the mass/charge ratio is received by detector, produces signal.Signal and this element signal ratio of reference material that element to be measured produces draw constituent content to be measured.
Table 1 has provided the test result of embodiment 1-5, and its specimen is taken from the crystal gallium that each corresponding embodiment obtains.As seen from Table 1, the foreign matter content of the crystal gallium of the present invention's acquisition is low.And embodiment 1-5 all acquires standard compliant 5N gallium.
Foreign matter content (the unit: ppm) of the sample of table 1 embodiment 1-5
Claims (10)
1. the preparation method of a high purity gallium, is characterized in that, comprises step:
The preparation normality and temperature higher than the sodium hydroxide solution of gallium fusing point as electrolytic solution;
The electrolytic solution of preparation is packed in electrolyzer;
Gallium material is made as positive plate and the negative plate of described electrolyzer;
Described positive plate and described negative plate are respectively charged in the positive column and cathodic area of described electrolyzer;
Start the electrolysis cycle of described electrolyzer, carry out dc electrolysis, to obtain cathodic area electrolysis gallium in described cathodic area;
After dc electrolysis is completed, described cathodic area electrolysis gallium is taken out and send be placed in the crystallizer tank of temperature lower than the gallium fusing point, carrying out crystallization, thereby obtain the crystallization gallium.
2. the preparation method of high purity gallium according to claim 1, is characterized in that, the massfraction of described sodium hydroxide solution is 10～40%.
3. the preparation method of high purity gallium according to claim 1, is characterized in that, the temperature of described sodium hydroxide solution is 30～60 ℃.
4. the preparation method of high purity gallium according to claim 1, is characterized in that, the current density of described dc electrolysis is 50～600A/m
2
5. the preparation method of high purity gallium according to claim 1, is characterized in that, the temperature of described crystallizer tank is 25～28 ℃.
6. the preparation method of high purity gallium according to claim 1, is characterized in that, the crystallization time of described cathodic area electrolysis gallium is 8～12h.
7. the preparation method of high purity gallium according to claim 5, is characterized in that, when described cathodic area electrolysis gallium carries out crystallization in described crystallizer tank, with stirring, and stirring velocity is 20～30rps.
8. the preparation method of high purity gallium according to claim 6, is characterized in that, described cathodic area electrolysis gallium carries out crystallization in described crystallizer tank percent crystallization in massecuite is 70～80%.
9. the preparation method of high purity gallium according to claim 1, is characterized in that, also comprises step: the crystallization gallium that obtains is cleaned.
10. the preparation method of high purity gallium according to claim 9, is characterized in that, described cleaning employing massfraction is 3～5% hydrochloric acid soln.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107338455A (en) * | 2017-09-01 | 2017-11-10 | 江西德义半导体科技有限公司 | The electrolysis unit and method of a kind of high purity gallium |
| CN110344081A (en) * | 2019-06-24 | 2019-10-18 | 北京科技大学 | A kind of method that wet chemistry-electrochemistry refining prepares high purity gallium |
| CN112111758A (en) * | 2020-09-07 | 2020-12-22 | 中铝矿业有限公司 | Preparation process of low-iron 4N gallium |
| CN113355701A (en) * | 2021-05-28 | 2021-09-07 | 广东先导稀材股份有限公司 | Method for separating and recovering silver and gallium |
| CN113549955A (en) * | 2021-07-08 | 2021-10-26 | 中南大学 | Crude gallium electrolytic refining device and method |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107338455A (en) * | 2017-09-01 | 2017-11-10 | 江西德义半导体科技有限公司 | The electrolysis unit and method of a kind of high purity gallium |
| CN110344081A (en) * | 2019-06-24 | 2019-10-18 | 北京科技大学 | A kind of method that wet chemistry-electrochemistry refining prepares high purity gallium |
| CN110344081B (en) * | 2019-06-24 | 2020-11-27 | 北京科技大学 | Method for preparing high-purity gallium by wet chemical-electrochemical combined refining |
| CN112111758A (en) * | 2020-09-07 | 2020-12-22 | 中铝矿业有限公司 | Preparation process of low-iron 4N gallium |
| CN112111758B (en) * | 2020-09-07 | 2023-01-31 | 中铝矿业有限公司 | Preparation process of low-iron 4N gallium |
| CN113355701A (en) * | 2021-05-28 | 2021-09-07 | 广东先导稀材股份有限公司 | Method for separating and recovering silver and gallium |
| CN113549955A (en) * | 2021-07-08 | 2021-10-26 | 中南大学 | Crude gallium electrolytic refining device and method |
| CN113549955B (en) * | 2021-07-08 | 2022-05-20 | 中南大学 | Crude gallium electrolytic refining device and method |
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Effective date of registration: 20180621 Address after: 404100 Chongqing Wanzhou Jing Kai District Peak Garden (Wanzhou Jing Kai District) Patentee after: Viking microelectronic Limited by Share Ltd Address before: 511500 Industrial Zone, wo Yun town, Qingxin County, Qingyuan, Guangdong (beside the fish dam road) Patentee before: Guangdong Vital Rare Material Co., Ltd. |
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