CN103031450A - Purification method for gallium - Google Patents
Purification method for gallium Download PDFInfo
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- CN103031450A CN103031450A CN2012105869118A CN201210586911A CN103031450A CN 103031450 A CN103031450 A CN 103031450A CN 2012105869118 A CN2012105869118 A CN 2012105869118A CN 201210586911 A CN201210586911 A CN 201210586911A CN 103031450 A CN103031450 A CN 103031450A
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Abstract
The invention provides a purification method for gallium, which comprises the following steps of pre-purification, freezing crystallization, pickling, and packaging, wherein in the pre-purification step, liquid gallium is put into single equipment containing pickling liquid for stirring reaction, ultrasonic vibration is adopted, and spongy gallium impurities are separated from the liquid gallium preliminarily; in the freezing crystallization step, the liquid gallium separated preliminarily is subjected to freezing crystallization treatment, and heavy metal impurities in the gallium are removed; in the pickling step, the gallium subjected to the freezing crystallization treatment is placed into the single equipment for heating and fusing, a pickling solution is added and stirred, and the gallium is separated from spongy gallium through the ultrasonic vibration after stirring; and in the packaging step, the gallium separated after the pickling step is completed is packaged. The purification method can better achieve a purification effect; the purification flow is simple; the purification method can be automatically controlled easily, and is safe, environment-friendly and power-saving; no special equipment is required; and the enterprise cost is lowered.
Description
Technical field
The present invention relates to a kind of purification of metals method, particularly a kind of method of purification of gallium.
Background technology
Gallium is a kind of electronic material of excellent property, is described as " spine of electronic industry ", is the basic resource of new and high technology.Along with the world today to the developing rapidly of a plurality of industries such as green energy resource illumination LED distensibility demand and solar electrical energy generation research and development, in the world the high purity metal gallium demand is increased sharply.According to (GB/T1475-2005) national standard, gallium purity reaches 4N-5N and is commonly referred to industrial gallium; Purity reaches 6-7N and is commonly referred to high purity gallium.The high purity gallium production of purifying take industrial gallium as raw material, the quality of its production and cost are subjected to industrial gallium quality influence larger, and therefore the quality of industrial gallium quality product has directly determined high-purity production cost and quality.
Along with the market supply competition is more and more fiery, it is more and more higher to the specification of quality of industrial gallium to produce high purity gallium enterprise, more and more stricter, the requirement that has exceeded national standard, for example, the purity of same gallium reaches 4N, and a lot of customer requirement copper content are lower than 5-6ppm, and the metallic lead constituent content is lower than 3-4ppm etc.And present existing method of purification adopts single method to realize the purification of gallium, and this method of purification has brought larger difficulty for the enterprise that produces the 4N gallium.Because enterprise just need to take a lot of single methods to process variant production in order meeting the need of market, and has not only consumed chemical reagent and electric energy, and to increase the gallium loss, to increase the production cost of enterprise, quality product also is difficult for guaranteeing.
National standard (GB/T1475-2005)
Therefore, how to provide a kind of method of purification of gallium, can solve the problems of the technologies described above, become the technical problem that needs to be resolved hurrily.
Summary of the invention
The technical problem to be solved in the present invention is the method for purification how a kind of gallium is provided, and can reduce enterprise cost when guaranteeing refining effect, realize simple to operate, be easy to control, the method for purification of safety and environmental protection.
For solving the problems of the technologies described above, the invention provides a kind of method of purification of gallium, may further comprise the steps:
The pre-purification put into the single devices with pickle solution with the liquid metal gallium and carried out stirring reaction, adopts simultaneously ultrasonic vibration, initial gross separation to go out sponge gallium impurity in the liquid gallium; Freezing and crystallizing carries out Freeze crystallization with the liquid metal gallium after the initial gross separation, removes beavy metal impurity in the gallium; Pickling is placed on heat fused in the described single devices with the gallium behind the Freeze crystallization, and adds pickling liquid and stir, and stirs and by ultrasonic vibration gallium is separated with the sponge gallium after finishing; Pack, after acid pickling step was finished, isolated gallium was packed.
Preferably, described freezing and crystallizing step is for repeatedly.
Preferably, in the described pre-purification step, the purity of described liquid metal gallium is the thick gallium of 2N-3N metal.
Preferably, in the described freezing and crystallizing step, described freezing temp is between-1 ℃ to 30 ℃.
Preferably, the purity of the gallium after the separation is 4N-5N in the described acid pickling step.
Preferably, the temperature in the described single devices is 40 ℃-50 ℃.
Preferably, the concentration of described pickling liquid is 3-5N analytical pure hydrochloric acid.
In the method for purification of a kind of gallium provided by the invention, by carrying out first pre-purification step, light metal in the thick gallium and heavy metal initial gross separation are gone out, carry out again Freeze crystallization, beavy metal impurity in the gallium after further will tentatively separating is separated, then by acid pickling step, the sponge gallium in the gallium is separated, thereby realize the purification purpose; Whole working method is simple, is easy to automatic control, and the safety and environmental protection economize on electricity need not specific installation, and the quality of gallium has obtained more effective assurance so that purify afterwards by the method.
Description of drawings
In order to be illustrated more clearly in the embodiment of the invention and technical scheme of the prior art, the below will do to introduce simply to the accompanying drawing of required use in embodiment and the description of the Prior Art, apparently, accompanying drawing in the following describes only is some embodiments of the present invention, for those of ordinary skills, under the prerequisite of not paying creative work, can also obtain according to these accompanying drawings other accompanying drawing.
Fig. 1 is the schema of the method for purification of a kind of gallium provided by the invention.
Embodiment
The below will engage the accompanying drawing in the embodiment of the invention, and the technical scheme in the embodiment of the invention is clearly and completely described, and obviously, described embodiment only is the present invention's part embodiment, rather than whole embodiment.Based on the embodiment among the present invention, those of ordinary skills belong to the scope of protection of the invention not making the every other embodiment that obtains under the creative work prerequisite.
Please refer to shown in Figure 1ly, Fig. 1 is the schema of the method for purification of a kind of gallium provided by the invention.
The invention provides a kind of method of purification of gallium, may further comprise the steps:
The pre-purification, liquid towards gallium are put into single devices and are added the pickle solution pickling, adopt simultaneously ultrasonic vibration, and initial gross separation goes out the sponge gallium impurity in the liquid gallium, and described sponge gallium impurity has comprised the impurity such as light metal and heavy metal;
Freezing and crystallizing carries out Freeze crystallization with the liquid metal gallium after the initial gross separation, removes beavy metal impurity in the gallium;
Pickling is placed on heat fused in the described single devices with the gallium behind the Freeze crystallization, and adds pickling liquid and stir, and stirs and by ultrasonic vibration gallium is separated with the sponge gallium after finishing;
Pack, after acid pickling step was finished, isolated gallium was packed.
Particularly, at first, 2N-3N liquid metal gallium (namely content is the thick gallium of liquid metal of 9.9%-99.9%) is placed in the single devices, with 3-5N(99.9%-99.999%) analytical pure hydrochloric acid join in the single devices as pickling liquid, 2N-3N liquid metal gallium in the single devices is carried out sufficient stirring reaction, keeping the temperature in the single devices is 40-50 ℃, simultaneously, open ultrasonic vibration equipment the liquid metal gallium in the single devices is vibrated, and then initial gross separation goes out the impurity such as light metal in the liquid gallium and heavy metal.
Secondly, the liquid metal gallium after the initial gross separation is carried out Freeze crystallization, the temperature of freezing and crystallizing remains on-1-30 ℃ between, after the liquid gallium partial coagulation, isolate beavy metal impurity; Also can after liquid gallium solidifies, the solid gallium taking-up be melted, repeat the removal of 3-5 freezing and crystallizing step realization beavy metal impurity.
Then, gallium behind the Freeze crystallization is placed on heat fused in the single devices, the single devices temperature of this moment is 40-50 ℃, simultaneously, adding pickling liquid in this single devices stirs, when stirring or after stirring end, by ultrasonic vibration gallium is separated with the sponge gallium, obtain the gallium of 4N-5N.
At last, the gallium of 4N-5N is packed.
Foregoing of the present invention is to be the gallium that the thick gallium of metal of 2N-3N is purified to 4N-5N with purity, but in fact this method of purification is not limited to the thick gallium of metal of above-mentioned 2N-3N.
Method of purification flow process provided by the invention is simple, is easy to automatic control, and the safety and environmental protection economize on electricity need not specific installation, and gallium purity 4N-5N quality is guaranteed, and this method is for some heavy metal, and for example copper and plumbous heteroacid washing lotion are the pure hydrochlorate of 3N-5N.
The method of purification of a kind of gallium provided by the invention, in pre-purification and acid pickling step, the temperature of single devices remains between 40 ℃-50 ℃.
The method of purification of a kind of gallium provided by the invention, pickle solution are the pure hydrochlorate of 3N-5N.
Need to prove that the temperature of above-mentioned pickle solution and single devices only is best a kind of embodiment, the present invention is not limited to foregoing.
Example 1
The method of purification of a kind of gallium provided by the invention:
(1) the liquid 100 kilograms of galliums of 3N is placed in the single devices, add 3N analytical pure hydrochloric acid, open to stir and carried out sufficient stirring reaction 1 hour, in the maintenance equipment temperature 40-50 ℃, after stirring reaction finishes, open ultrasonic vibration equipment liquid towards gallium and vibrate layering, isolate the sponge gallium; Perhaps in stirring reaction, carry out ultrasonic vibration, further isolate the impurity elements such as sponge man.
(2) the liquid metal gallium after will separating carries out Freeze crystallization, temperature remains between 20-30 ℃, after the about 40-45% weight of liquid gallium part is solidified, the solid taking-up is melted, repeat 3 freezing and crystallizing melting processes and purify, this step mainly is further to isolate beavy metal impurity.
(3) gallium behind the freezing and crystallizing is put into above-mentioned single devices and repeated the ⑴ process, still, this repeats the process of pickling, is to isolate gallium and sponge gallium, finally obtains the high gallium of purity.
(4) last, be that the gallium of 4N-5N is packed with the purity that obtains.
Example 2
The method of purification of a kind of gallium provided by the invention:
(1) the liquid 100 kilograms of galliums of 3N is placed in the single devices, add 4N analytical pure hydrochloric acid, open to stir and carried out sufficient stirring reaction 2 hours, in the maintenance equipment temperature 40-50 ℃, after stirring reaction finishes, open ultrasonic vibration equipment liquid towards gallium and vibrate layering, isolate the metallic impurity elements such as sponge gallium; Perhaps in stirring reaction, carry out ultrasonic vibration, removing foreign matter element.
(2) the liquid metal gallium after will separating carries out Freeze crystallization, temperature remains between 10-15 ℃, after the about 45-50% weight of liquid gallium part is solidified, the solid taking-up is melted, repeat 3 freezing and crystallizing melting processes and purify, this step mainly is further to isolate beavy metal impurity.
(3) gallium behind the freezing and crystallizing is put into above-mentioned single devices and repeated the ⑴ process, but the process of this repetition pickling is to isolate gallium and sponge gallium, finally obtains the high gallium of purity.
(4) last, be that the gallium of 4N-5N is packed with the purity that obtains.
Example 3
Of the present invention:
(1) the liquid 100 kilograms of galliums of 3N is placed in the single devices, add 5N analytical pure hydrochloric acid, open to stir and carried out sufficient stirring reaction 3 hours, in the maintenance equipment temperature 40-50 ℃, after stirring reaction finishes, open ultrasonic vibration equipment liquid towards gallium and vibrate layering, isolate the impurity elements such as sponge gallium; Perhaps in stirring reaction, carry out ultrasonic vibration, further isolate the impurity elements such as sponge gallium.
(2) the liquid metal gallium after will separating carries out Freeze crystallization, temperature remains between-1 ℃-8 ℃, after the about 35-40% weight of liquid gallium part is solidified, the solid taking-up is melted, repeat 3 freezing and crystallizing melting processes and purify, this step mainly is further to isolate beavy metal impurity.
(3) gallium behind the freezing and crystallizing is put into above-mentioned single devices and repeated the ⑴ process, but the process of this repetition pickling is to isolate gallium and sponge gallium, finally obtains the high gallium of purity.
(4) last, be that the gallium of 4N-5N is packed with the purity that obtains.
The below is 3 example test results
The above only is the preferred implementation of the method for purification of a kind of gallium provided by the invention, does not consist of the restriction to protection domain of the present invention.Number of components among this embodiment is not limited to the mode that adopts among the embodiment, any any modification of doing within the spirit and principles in the present invention, is equal to and replaces and improvement etc., all should be included within the claim protection domain of the present invention.
Claims (7)
1. the method for purification of a gallium is characterized in that, may further comprise the steps:
The pre-purification put into the single devices with pickle solution with the liquid metal gallium and carried out stirring reaction, adopts simultaneously ultrasonic vibration, initial gross separation to go out sponge gallium impurity in the liquid gallium;
Freezing and crystallizing carries out Freeze crystallization with the liquid metal gallium after the initial gross separation, removes beavy metal impurity in the gallium;
Pickling is placed on heat fused in the described single devices with the gallium behind the Freeze crystallization, and adds pickling liquid and stir, and stirs and by ultrasonic vibration gallium is separated with the sponge gallium after finishing;
Pack, after acid pickling step was finished, isolated gallium was packed.
2. method of purification according to claim 1 is characterized in that, described freezing and crystallizing step is for repeatedly.
3. method of purification according to claim 2 is characterized in that, in the described pre-purification step, the purity of described liquid metal gallium is the thick gallium of 2N-3N metal.
4. method of purification according to claim 3 is characterized in that, in described freezing and crystallizing step, described freezing temp is between-1 ℃ to 30 ℃.
5. method of purification according to claim 4 is characterized in that, the purity of the gallium after separating in the described acid pickling step is 4N-5N.
6. method of purification according to claim 5 is characterized in that, the temperature in the described single devices is 40 ℃-50 ℃.
7. method of purification according to claim 6 is characterized in that, the concentration of described pickling liquid is 3-5N analytical pure hydrochloric acid.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106544530A (en) * | 2015-09-18 | 2017-03-29 | 神华集团有限责任公司 | A kind of method that metallic zinc is removed in the gallium material from high concentration |
| CN106702429A (en) * | 2016-12-22 | 2017-05-24 | 北京吉亚半导体材料有限公司 | Method for purifying and recovering caustic alkali for producing metal gallium through alkaline method |
| CN109554555A (en) * | 2018-12-27 | 2019-04-02 | 中国神华能源股份有限公司 | The method of purification and crystallization and purification device of crude metal 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 |
| CN111363933A (en) * | 2020-03-16 | 2020-07-03 | 广西大学 | Production equipment and method of high-purity gallium |
| CN115786743A (en) * | 2022-12-19 | 2023-03-14 | 广东省科学院资源利用与稀土开发研究所 | Device and method for preparing high-purity gallium |
| CN115815589A (en) * | 2022-12-26 | 2023-03-21 | 株洲科能新材料股份有限公司 | High-purity gallium particle rapid forming method |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106544530A (en) * | 2015-09-18 | 2017-03-29 | 神华集团有限责任公司 | A kind of method that metallic zinc is removed in the gallium material from high concentration |
| CN106702429A (en) * | 2016-12-22 | 2017-05-24 | 北京吉亚半导体材料有限公司 | Method for purifying and recovering caustic alkali for producing metal gallium through alkaline method |
| CN109554555A (en) * | 2018-12-27 | 2019-04-02 | 中国神华能源股份有限公司 | The method of purification and crystallization and purification device of crude metal 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 |
| CN111363933A (en) * | 2020-03-16 | 2020-07-03 | 广西大学 | Production equipment and method of high-purity gallium |
| CN115786743A (en) * | 2022-12-19 | 2023-03-14 | 广东省科学院资源利用与稀土开发研究所 | Device and method for preparing high-purity gallium |
| CN115786743B (en) * | 2022-12-19 | 2024-05-28 | 广东省科学院资源利用与稀土开发研究所 | Device and method for preparing high-purity gallium |
| CN115815589A (en) * | 2022-12-26 | 2023-03-21 | 株洲科能新材料股份有限公司 | High-purity gallium particle rapid forming method |
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