CN103031450B - A kind of method of purification of gallium - Google Patents
A kind of method of purification of gallium Download PDFInfo
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- CN103031450B CN103031450B CN201210586911.8A CN201210586911A CN103031450B CN 103031450 B CN103031450 B CN 103031450B CN 201210586911 A CN201210586911 A CN 201210586911A CN 103031450 B CN103031450 B CN 103031450B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention provides a kind of method of purification of gallium, comprise the following steps: purify in advance, liquid metal gallium is put into the single devices with pickle solution and carry out stirring reaction, adopt ultrasonic vibration simultaneously, initial gross separation goes out the sponge gallium impurity in liquid gallium; Freezing and crystallizing, carries out Freeze crystallization by the liquid metal gallium after initial gross separation, removes beavy metal impurity in gallium; Pickling, is placed on heat fused in described single devices by the gallium after Freeze crystallization, and adds pickling liquid and stir, and stirs after terminating and is separated with sponge gallium by gallium by ultrasonic vibration; Packaging, after being completed by acid pickling step, isolated gallium is packed.The present invention better can realize refining effect, and purification schemes is simple, is easy to automatic control, and safety and environmental protection economizes on electricity, and without the need to specific installation, and then reduces enterprise cost.
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's developing rapidly multiple industry research and development such as green energy resource illumination LED distensibility demand and solar electrical energy generation, in the world 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.High purity gallium is produced for raw material carries out purification with industrial gallium, and by industrial gallium quality influence comparatively greatly, therefore the quality of industrial gallium quality product directly determines high-purity production cost and quality for its quality of producing and cost.
Along with market supply competition is more and more fiery, produce the specification of quality of high purity gallium enterprise to industrial gallium more and more higher, more and more stricter, beyond the requirement of national standard, such as, the purity of same gallium reaches 4N, and a lot of customer requirement copper content is lower than 5-6ppm, and metallic lead constituent content is lower than 3-4ppm etc.And current existing method of purification, adopt single method to realize the purification of gallium, and this method of purification brings larger difficulty to the enterprise producing 4N gallium.Because enterprise, in order to meet the need of market, just need to take a lot of single method to process variant production, not only consumes chemical reagent and electric energy, and increase gallium loss, increase the production cost of enterprise, quality product also not easily ensures.
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 technical problem urgently to be resolved hurrily.
Summary of the invention
The technical problem to be solved in the present invention is the method for purification how providing a kind of gallium, can reduce enterprise cost, realize method of purification simple to operate, to be easy to control, safety and environmental protection while guarantee refining effect.
For solving the problems of the technologies described above, the invention provides a kind of method of purification of gallium, comprising the following steps:
Pre-purification, puts into the single devices with pickle solution by liquid metal gallium and carries out stirring reaction, adopt ultrasonic vibration simultaneously, and initial gross separation goes out the sponge gallium impurity in liquid gallium; Freezing and crystallizing, carries out Freeze crystallization by the liquid metal gallium after initial gross separation, removes beavy metal impurity in gallium; Pickling, is placed on heat fused in described single devices by the gallium after Freeze crystallization, and adds pickling liquid and stir, and stirs after terminating and is separated with sponge gallium by gallium by ultrasonic vibration; Packaging, after being completed by acid pickling step, isolated gallium is packed.
Preferably, described freezing and crystallizing step is repeatedly.
Preferably, in described pre-purification step, the purity of described liquid metal gallium is the thick gallium of 2N-3N metal.
Preferably, in described freezing and crystallizing step, described freezing temp is between-1 DEG C to 30 DEG C.
Preferably, the purity of the gallium after being separated in described acid pickling step is 4N-5N.
Preferably, the temperature in described single devices is 40 DEG C-50 DEG C.
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 first carrying out pre-purification step, light metal in thick gallium and heavy metal initial gross separation are gone out, carry out Freeze crystallization again, further the beavy metal impurity in the gallium after tentatively separating is separated, then by acid pickling step, the sponge gallium in gallium is separated, thus realizes purification object; Whole working method is simple, is easy to automatic control, and safety and environmental protection economizes on electricity, and without the need to specific installation, and after making to purify by the method, the quality of gallium obtains more effective guarantee.
Accompanying drawing explanation
In order to be illustrated more clearly in the embodiment of the present invention and technical scheme of the prior art, be briefly described to the accompanying drawing used required in embodiment and description of the prior art below, apparently, accompanying drawing in the following describes is only some embodiments of the present invention, for those of ordinary skill in the art, under the prerequisite not paying creative work, other accompanying drawing can also be obtained according to these accompanying drawings.
Fig. 1 is the schema of the method for purification of a kind of gallium provided by the invention.
Embodiment
Below by engaging the accompanying drawing in the embodiment of the present invention, be clearly and completely described the technical scheme in the embodiment of the present invention, obviously, described embodiment is only the present invention's part embodiment, instead of whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art, not making the every other embodiment obtained under creative work prerequisite, belong to the scope of protection of the invention.
Please refer to shown in Fig. 1, 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, comprise the following steps:
Pre-purification, liquid towards gallium is put into single devices and is added pickle solution pickling, adopts ultrasonic vibration simultaneously, and initial gross separation goes out the sponge gallium impurity in liquid gallium, and described sponge gallium impurity includes the impurity such as light metal and heavy metal;
Freezing and crystallizing, carries out Freeze crystallization by the liquid metal gallium after initial gross separation, removes beavy metal impurity in gallium;
Pickling, is placed on heat fused in described single devices by the gallium after Freeze crystallization, and adds pickling liquid and stir, and stirs after terminating and is separated with sponge gallium by gallium by ultrasonic vibration;
Packaging, after being completed by acid pickling step, isolated gallium is packed.
Particularly, first, 2N-3N liquid metal gallium (namely content is the thick gallium of liquid metal of 9.9%-99.9%) is placed in single devices, using 3-5N(99.9%-99.999%) analytical pure hydrochloric acid join in single devices as pickling liquid, sufficient stirring reaction is carried out to the 2N-3N liquid metal gallium in single devices, the temperature in single devices is kept to be 40-50 DEG C, simultaneously, open ultrasonic vibration apparatus to vibrate the liquid metal gallium in single devices, and then initial gross separation goes out the impurity such as light metal in liquid gallium and heavy metal.
Secondly, carry out Freeze crystallization to the liquid metal gallium after initial gross separation, the temperature of freezing and crystallizing remains between-1-30 DEG C, after liquid gallium partial coagulation, isolates beavy metal impurity; Also after liquid gallium solidifies, solid gallium can be taken out and melt, repeat the removal that 3-5 time freezing and crystallizing step realizes beavy metal impurity.
Then, gallium after Freeze crystallization is placed on heat fused in single devices, single devices temperature is now 40-50 DEG C, simultaneously, in this single devices, add pickling liquid stir, while stirring or after stirring terminates, by ultrasonic vibration, gallium is separated with sponge gallium, obtains the gallium of 4N-5N.
Finally, the gallium of 4N-5N is packed.
Foregoing of the present invention is the gallium that the thick gallium of metal of 2N-3N is purified to 4N-5N by 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 safety and environmental protection economizes on electricity, and without the need to specific installation, gallium purity 4N-5N quality is guaranteed, and this method is for some heavy metal, and such as 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 DEG C-50 DEG C.
The method of purification of a kind of gallium provided by the invention, pickle solution is the pure hydrochlorate of 3N-5N.
It should be noted that, the temperature of above-mentioned pickle solution and single devices is only best a kind of embodiment, and the present invention is not limited to foregoing.
Example 1
The method of purification of a kind of gallium provided by the invention:
(1) liquid for 3N 100 kilograms of galliums are placed in single devices, add 3N analytical pure hydrochloric acid, open stirring and carry out sufficient stirring reaction 1 hour, temperature 40-50 DEG C in maintenance equipment, after stirring reaction terminates, open ultrasonic vibration apparatus liquid towards gallium and carry out vibration layering, isolate sponge gallium; Or while stirring reaction, carry out ultrasonic vibration, isolate the impurity elements such as sponge man further.
(2) the liquid metal gallium after separation is carried out Freeze crystallization, temperature remains between 20-30 DEG C, after the about 40-45% weight of liquid gallium part is solidified, solid is taken out and melts, repeat 3 freezing and crystallizing melting processes to purify, this step is mainly to isolate beavy metal impurity further.
(3) gallium after freezing and crystallizing is put into above-mentioned single devices and repeat (1) process, but the process of this repetition pickling, is isolate gallium and sponge gallium, finally obtains the gallium that purity is high.
(4) last, be that the gallium of 4N-5N is packed by the purity obtained.
Example 2
The method of purification of a kind of gallium provided by the invention:
(1) liquid for 3N 100 kilograms of galliums are placed in single devices, add 4N analytical pure hydrochloric acid, open stirring and carry out sufficient stirring reaction 2 hours, temperature 40-50 DEG C in maintenance equipment, after stirring reaction terminates, open ultrasonic vibration apparatus liquid towards gallium and carry out vibration layering, isolate the metallic impurity elements such as sponge gallium; Or while stirring reaction, carry out ultrasonic vibration, removing foreign matter element.
(2) the liquid metal gallium after separation is carried out Freeze crystallization, temperature remains between 10-15 DEG C, after the about 45-50% weight of liquid gallium part is solidified, solid is taken out and melts, repeat 3 freezing and crystallizing melting processes to purify, this step is mainly to isolate beavy metal impurity further.
(3) gallium after freezing and crystallizing is put into above-mentioned single devices and repeat (1) process, but the process of this repetition pickling isolates gallium and sponge gallium, finally obtains the gallium that purity is high.
(4) last, be that the gallium of 4N-5N is packed by the purity obtained.
Example 3
Of the present invention:
(1) liquid for 3N 100 kilograms of galliums are placed in single devices, add 5N analytical pure hydrochloric acid, open stirring and carry out sufficient stirring reaction 3 hours, temperature 40-50 DEG C in maintenance equipment, after stirring reaction terminates, open ultrasonic vibration apparatus liquid towards gallium and carry out vibration layering, isolate the impurity elements such as sponge gallium; Or while stirring reaction, carry out ultrasonic vibration, isolate the impurity elements such as sponge gallium further.
(2) the liquid metal gallium after separation is carried out Freeze crystallization, temperature remains between-1 DEG C-8 DEG C, after the about 35-40% weight of liquid gallium part is solidified, solid is taken out and melts, repeat 3 freezing and crystallizing melting processes to purify, this step is mainly to isolate beavy metal impurity further.
(3) gallium after freezing and crystallizing is put into above-mentioned single devices and repeat (1) process, but the process of this repetition pickling isolates gallium and sponge gallium, finally obtains the gallium that purity is high.
(4) last, be that the gallium of 4N-5N is packed by the purity obtained.
Here is 3 example test results
The foregoing is only the preferred implementation of the method for purification of a kind of gallium provided by the invention, do not form limiting the scope of the present invention.Number of components in this embodiment is not limited to the mode adopted in embodiment, and any any amendment done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within claims of the present invention.
Claims (6)
1. a method of purification for gallium, is characterized in that, comprises the following steps:
Pre-purification, puts into the single devices with pickle solution by liquid metal gallium and carries out stirring reaction, adopt ultrasonic vibration simultaneously, and initial gross separation goes out the sponge gallium impurity in liquid gallium;
Freezing and crystallizing, carries out Freeze crystallization by the liquid metal gallium after initial gross separation, and remove beavy metal impurity in gallium, described freezing temp is between 8 DEG C to 30 DEG C;
Pickling, is placed on heat fused in described single devices by the gallium after Freeze crystallization, and adds pickling liquid and stir, and stirs after terminating and is separated with sponge gallium by gallium by ultrasonic vibration;
Packaging, after being completed by acid pickling step, isolated gallium is packed.
2. method of purification according to claim 1, is characterized in that, described freezing and crystallizing step is repeatedly.
3. method of purification according to claim 2, is characterized in that, in 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 1, is characterized in that, the purity of the gallium after being separated in described acid pickling step is 4N-5N.
5. method of purification according to claim 4, is characterized in that, the temperature in described single devices is 40 DEG C-50 DEG C.
6. method of purification according to claim 5, is characterized in that, the concentration of described pickling liquid is 3-5N analytical pure hydrochloric acid.
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| 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 |
| CN111363933B (en) * | 2020-03-16 | 2022-05-13 | 广西大学 | Production equipment and method of 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 |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85100163A (en) * | 1985-04-01 | 1986-07-30 | 山东铝厂 | A kind of method of from the decomposition nut liquid of alumina producing, extracting gallium |
| CN1775972A (en) * | 2005-12-09 | 2006-05-24 | 韶关市华韦实业有限公司 | Technology for extracting Gallium metal from lead-zine tail ore slug smelting by extracting-electrolytic method |
| CN101177741A (en) * | 2007-12-11 | 2008-05-14 | 冯峰 | Method for producing 4N metal gallium |
| CN101717868A (en) * | 2009-12-01 | 2010-06-02 | 南京中锗科技股份有限公司 | Method for comprehensively recovering indium and gallium from distilled waste acid containing indium and gallium |
| CN102071328A (en) * | 2010-12-09 | 2011-05-25 | 中国铝业股份有限公司 | Method for purifying defective gallium produced by resin adsorption method |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2714684B2 (en) * | 1989-03-17 | 1998-02-16 | 千代田化工建設株式会社 | Purification method of metallic gallium |
| JPH11269569A (en) * | 1998-03-24 | 1999-10-05 | Furukawa Co Ltd | Gallium refining |
| CN102140583A (en) * | 2011-02-15 | 2011-08-03 | 江苏大学 | Method for purifying metal melt by combining power ultrasonic field and electric field |
-
2012
- 2012-12-28 CN CN201210586911.8A patent/CN103031450B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85100163A (en) * | 1985-04-01 | 1986-07-30 | 山东铝厂 | A kind of method of from the decomposition nut liquid of alumina producing, extracting gallium |
| CN1775972A (en) * | 2005-12-09 | 2006-05-24 | 韶关市华韦实业有限公司 | Technology for extracting Gallium metal from lead-zine tail ore slug smelting by extracting-electrolytic method |
| CN101177741A (en) * | 2007-12-11 | 2008-05-14 | 冯峰 | Method for producing 4N metal gallium |
| CN101717868A (en) * | 2009-12-01 | 2010-06-02 | 南京中锗科技股份有限公司 | Method for comprehensively recovering indium and gallium from distilled waste acid containing indium and gallium |
| CN102071328A (en) * | 2010-12-09 | 2011-05-25 | 中国铝业股份有限公司 | Method for purifying defective gallium produced by resin adsorption method |
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