CN114635048A - Gallium crystal purification method - Google Patents
Gallium crystal purification method Download PDFInfo
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- CN114635048A CN114635048A CN202210470441.2A CN202210470441A CN114635048A CN 114635048 A CN114635048 A CN 114635048A CN 202210470441 A CN202210470441 A CN 202210470441A CN 114635048 A CN114635048 A CN 114635048A
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- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 title claims abstract description 186
- 229910052733 gallium Inorganic materials 0.000 title claims abstract description 186
- 239000013078 crystal Substances 0.000 title claims abstract description 74
- 238000000034 method Methods 0.000 title claims abstract description 42
- 238000000746 purification Methods 0.000 title abstract description 36
- 238000002425 crystallisation Methods 0.000 claims abstract description 130
- 230000008025 crystallization Effects 0.000 claims abstract description 127
- 239000007788 liquid Substances 0.000 claims abstract description 71
- 239000002994 raw material Substances 0.000 claims abstract description 61
- 238000003756 stirring Methods 0.000 claims abstract description 53
- 238000002844 melting Methods 0.000 claims abstract description 26
- 230000008018 melting Effects 0.000 claims abstract description 26
- 238000001816 cooling Methods 0.000 claims abstract description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 24
- 239000000498 cooling water Substances 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 230000003068 static effect Effects 0.000 abstract description 17
- 230000008878 coupling Effects 0.000 description 13
- 238000010168 coupling process Methods 0.000 description 13
- 238000005859 coupling reaction Methods 0.000 description 13
- 239000004743 Polypropylene Substances 0.000 description 8
- 239000000428 dust Substances 0.000 description 8
- 238000004781 supercooling Methods 0.000 description 8
- 238000005260 corrosion Methods 0.000 description 7
- 230000007797 corrosion Effects 0.000 description 5
- 230000001681 protective effect Effects 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 4
- 101150114468 TUB1 gene Proteins 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 1
- 229910002601 GaN Inorganic materials 0.000 description 1
- 229910005540 GaP Inorganic materials 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 229910001361 White metal Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000407 epitaxy Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- HZXMRANICFIONG-UHFFFAOYSA-N gallium phosphide Chemical compound [Ga]#P HZXMRANICFIONG-UHFFFAOYSA-N 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 238000005338 heat storage Methods 0.000 description 1
- 230000003116 impacting effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000010969 white metal Substances 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B58/00—Obtaining gallium or indium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
- C22B9/02—Refining by liquating, filtering, centrifuging, distilling, or supersonic wave action including acoustic waves
Abstract
The present disclosure provides a gallium crystallization purification method, which includes the steps of: step one, pouring liquid raw material gallium into a crystallization barrel; step two, cooling the crystallization barrel to be lower than the melting point of gallium; step three, stirring the liquid raw material gallium in the crystallization barrel to crystallize the gallium to form gallium crystals; step four, removing and stirring and fishing out a certain amount of gallium crystals after the crystallization barrel gathers a certain amount of gallium crystals; and step five, repeating the step three and the step four. The gallium crystallization purification method can improve the crystallization speed of gallium and can solve the problem that static crystallization can not be crystallized due to seed crystal melting caused by unstable temperature control.
Description
Technical Field
The disclosure relates to the technical field of gallium, and more particularly relates to a gallium crystal purification method.
Background
Gallium is a grayish blue or silvery white metal and has a melting point of only 29.8 ℃. Pure liquid gallium has a remarkable supercooling tendency, and is easily oxidized in air to form an oxide film. The method is mainly used for preparing semiconductor doping elements of gallium nitride, gallium arsenide, gallium phosphide and germanium, and the gallium with the purity of more than or equal to 7N5 is used as a source material for high-quality MBE experiment epitaxy.
The method for purifying gallium mainly comprises the following steps; the method comprises an electrolytic method, an extraction method and a crystallization method, wherein the electrolytic method and the extraction method are mainly used for purifying gallium with the purity of 1-4N (90-99.99 percent), and the crystallization method is mainly used for purifying gallium with the purity of more than 4N.
The gallium crystallization purification method mainly utilizes the low melting point and supercooling property of gallium to crystallize gallium liquid under certain conditions, thereby obtaining gallium with higher purity. The prior crystallization method generally adopts static crystallization (also known as distributed crystallization, a method of adding solid seed crystals (also called seed crystals) into liquid gallium to purify the liquid gallium crystals, and is generally used for gallium with the purity of more than 6N), but the method has the defects of slow crystallization speed and the problem that the static crystallization can not be crystallized due to the melting of the seed crystals caused by unstable temperature control.
Disclosure of Invention
In view of the problems in the background art, it is an object of the present disclosure to provide a gallium crystal purification method that can increase the crystallization rate of gallium and can solve the problem that static crystallization cannot be performed due to melting of a seed crystal caused by unstable temperature control.
Thus, in some embodiments, a method of purifying a gallium crystal comprises the steps of: step one, pouring liquid raw material gallium into a crystallization barrel; step two, cooling the crystallization barrel to be lower than the melting point of gallium; step three, stirring the liquid raw material gallium in the crystallization barrel to crystallize the gallium to form gallium crystals; step four, removing and stirring and fishing out a certain amount of gallium crystals after the crystallization barrel gathers a certain amount of gallium crystals; and step five, repeating the step three and the step four.
In some embodiments, step one is implemented as: putting the raw material gallium in a constant temperature box higher than the melting point of gallium to form liquid raw material gallium, and pouring the liquid raw material gallium into a crystallization barrel after the constant temperature is finished.
In some embodiments, the constant temperature is 45-50 ℃ and the constant temperature time is 4-6 h.
In some embodiments, step two is implemented as: and opening circulating cooling water, setting the temperature of the cooling water to be 25-28 ℃, the water flow to be 2-4L/min and the indoor temperature to be 25-28 ℃ so as to reduce the temperature of the crystallization barrel to be lower than the melting point of gallium.
In some embodiments, in the third step, the stirring speed is 15 to 20 r/min.
In some embodiments, step five is performed as: and stopping crystallization until the weight of the fished gallium crystal accounts for 85-90% of that of the liquid raw material gallium in the step one.
In some embodiments, there is further included, between step one and step two, the steps of: and pouring the dilute hydrochloric acid into a crystallization barrel containing the liquid raw material gallium, so that the dilute hydrochloric acid covers the whole liquid level of the liquid raw material gallium.
In some embodiments, the dilute hydrochloric acid is 3% to 5% dilute hydrochloric acid by volume.
In some embodiments, the level of the dilute hydrochloric acid is 2-3 cm.
The beneficial effects of this disclosure are as follows: in the gallium crystal purification method disclosed by the disclosure, the temperature of the crystallization barrel is reduced to be lower than the melting point of gallium, and the liquid raw material gallium in the crystallization barrel is stirred to crystallize the gallium into gallium crystals, so that even if the gallium is in a metastable state due to the supercooling property, the metastable state of the gallium can be broken through stirring, and the liquid raw material gallium is crystallized under the condition that the temperature in the crystallization barrel is lower than the melting point of the gallium. In other words, compared with the static crystallization of gallium in the background art, the purification method of gallium crystallization of the present disclosure solves the problem that the crystallization speed of gallium in the static crystallization is slow due to the supercooling property. In addition, in the static crystallization process, if the temperature control of crystallization of the liquid gallium raw material is unstable, the seed crystal is melted and cannot be crystallized, and the adoption of the seed crystal is avoided by stirring the gallium crystallization purification method disclosed by the invention, so that the problem that the static crystallization cannot be crystallized due to the melting of the seed crystal caused by the unstable temperature control is solved.
Drawings
FIG. 1 is a perspective view of a gallium crystal purification apparatus according to the present disclosure.
FIG. 2 is a perspective view of a rotating stirring module of the gallium crystal purification apparatus of FIG. 1.
Wherein the reference numerals are as follows:
325 leading screw nut transmission mechanism of 100 gallium crystallization purification device
D Up-down 325a screw
1 support frame on crystallization bucket 326
2 lower support of heat exchange barrel 327
3 lower limit piece of rotary stirring module 328
30 stirring rod 329 horizontal limiting piece
31 rotating electric machine 33 protective housing
32 lifting mechanism 34 dust cover
321 lifting motor 4 cooling water circulation mechanism
322 shaft coupling 5 frame
323 horizontal connecting rod U crystallization unit
324 vertical guide rod
Detailed Description
The accompanying drawings illustrate embodiments of the present disclosure and it is to be understood that the disclosed embodiments are merely examples of the disclosure, which can be embodied in various forms, and therefore, specific details disclosed herein are not to be interpreted as limiting, but merely as a basis for the claims and as a representative basis for teaching one skilled in the art to variously employ the present disclosure.
[ gallium Crystal purification apparatus ]
Referring to fig. 1, a gallium crystallization purification apparatus 100 includes a crystallization barrel 1, a heat exchange barrel 2, and a rotary stirring module 3.
The upper end of the crystallization barrel 1 is opened, and the crystallization barrel 1 is used for containing liquid raw material gallium. The heat exchange barrel 2 surrounds the crystallization barrel 1 from the outside, and the heat exchange barrel 2 is used for carrying out heat exchange with the crystallization barrel 1 and controlling the temperature in the crystallization barrel 1 to be lower than the melting point of gallium. The rotary stirring module 3 comprises a stirring rod 30, and the stirring rod 30 can extend into the crystallization barrel 1 so as to crystallize the liquid gallium raw material in the crystallization barrel 1 under stirring.
In the disclosed gallium crystallization purification device 100, the temperature in the crystallization barrel 1 is controlled to be lower than the melting point of gallium through the heat exchange barrel 2, so that the liquid raw material gallium in the crystallization barrel 1 is at the crystallization temperature, the liquid raw material gallium in the crystallization barrel 1 at the crystallization temperature is stirred through the stirring rod 30, and even if the gallium is in a metastable state due to the supercooling characteristic, the metastable state of the gallium can be broken through the stirring of the stirring rod 30, so that the liquid raw material gallium is crystallized under the condition that the temperature in the crystallization barrel 1 is lower than the melting point of the gallium. In other words, the gallium crystallization purification apparatus 100 of the present disclosure solves the problem that the rate of crystallization of gallium in the metastable state is slow due to the super-cooling property in the static crystallization, compared to the static crystallization of gallium of the background art. In addition, in the static crystallization process, if the temperature control of the crystallization of the liquid gallium raw material is unstable, the seed crystal is melted and cannot be crystallized, and the gallium crystallization purification device 100 of the present disclosure avoids the use of the seed crystal by stirring, thereby solving the problem that the static crystallization cannot be crystallized due to the unstable temperature control, which causes the melting of the seed crystal.
In one example, the crystallization barrel 1 employs a PP crystallization barrel to improve corrosion resistance. Also, in one example, the heat exchange tub 2 is a PP heat exchange tub to improve corrosion resistance. Similarly, the stirring rod 30 is a teflon stirring rod to improve corrosion resistance.
The liquid raw material gallium contained in the crystallization barrel 1 may be prepared in any suitable manner. For example, the raw material gallium (solid state) is put in an incubator higher than the melting point of gallium to form liquid raw material gallium, and after the incubation is finished, the liquid raw material gallium is poured into the crystallization barrel 1. In one example, the constant temperature is 45-50 ℃ and the constant temperature time is 4-6 h. After the constant temperature is finished, the liquid raw material gallium in the constant temperature box is poured into the crystallization barrel 1.
In one example, referring to fig. 2, the rotary stirring module 3 further includes a rotary motor 31 and a lifting mechanism 32. The rotary motor 31 is connected to the stirring rod 30, and the rotary motor 31 is used to rotationally drive the stirring rod 30. The lifting mechanism 32 is connected to the rotating motor 31, and the lifting mechanism 32 is used for driving the rotating motor 31 to lift together with the stirring rod 30.
In one example, referring to fig. 2, the lift mechanism 32 includes a lift motor 321, a coupling 322, a horizontal connecting rod 323, a vertical guide rod 324, a lead screw nut drive 325, an upper support bracket 326, and a lower support bracket 327.
The horizontal connecting rod 323 horizontally passes through the coupling 322 and is adjustably fixed to the coupling 322, and one end of the horizontal connecting rod 323 is fixedly connected to the rotating motor 31. The vertical guide rod 324 vertically passes through the coupler 322, the upper end of the vertical guide rod 324 is fixed to the upper support bracket 326, the lower end of the vertical guide rod 324 is fixed to the lower support bracket 327, and the vertical guide rod 324 is in sliding fit with the coupler 322. The screw nut transmission mechanism 325 includes a screw 325a and a nut (not shown), the screw 325a passes through the coupling 322 and the lower support 327 along the vertical direction, the upper end of the screw 325a is rotatably disposed on the upper support 326, and the nut is sleeved on the screw 325a and connected to the coupling 322. The lifting motor 321 is located below the lower support frame 327 and fixed to the lower support frame 327, and the lifting motor 321 is connected to a screw 325a of the screw nut transmission mechanism 325 to drive the lower support frame 327, the coupler 322 and the horizontal connecting rod 323 to lift and lower in the up-down direction.
The horizontal position of the stirring rod 30 relative to the crystallization barrel 1 can be adjusted through the horizontal connecting rod 323 and the rotating motor 31; through the lifting motor 321, the coupling 322, the horizontal connecting rod, the 323 vertical guide rod 324, the screw nut transmission mechanism 325, the upper support frame 326, the lower support frame 327 and the rotating motor 31, the vertical position of the stirring rod 30 relative to the crystallization barrel 1 can be adjusted, so that the positioning of the stirring rod 30 relative to the crystallization barrel 1 is realized. In addition, the components for realizing horizontal position adjustment and vertical position adjustment are integrated through the shaft coupling 322, and the compactness and the integration degree of the gallium crystal purification device 100 are improved.
In the example shown in the drawings, the horizontal connecting rods 323 are two, but not limited thereto, and the horizontal connecting rods 323 may be one or more than two.
In the example shown in the drawings, the number of the vertical guide rods 324 is two, but is not limited thereto, and the number of the vertical guide rods 324 may be one or more than two.
In one example, referring to fig. 2, the lift mechanism 32 further includes a lower stop 328. The lower stopper 328 is installed at the lower end of the vertical guide 324, and the lower stopper 328 is used for limiting the downward movement position of the coupling 322 from below, thereby preventing the stirring rod 30 from protruding into the crystallization barrel 1 to an excessive extent and impacting the upper surface of the bottom wall of the crystallization barrel 1 to damage the crystallization barrel 1.
In one example, referring to fig. 2, the lifting mechanism 32 further includes a horizontal limit 329. A horizontal stopper 329 is installed at the other end of the horizontal connecting rod 323 to horizontally position the coupling 322 between the rotary motor 31 and the horizontal stopper 329, and the horizontal stopper 329 serves to limit the longest distance of the portion of the horizontal connecting rod 323 horizontally exposed from the coupling 322, thereby preventing the stirring rod 30 from being excessively horizontally moved to collide with the inner surface of the vertical wall of the crystallization tub 1, resulting in damage to the crystallization tub 1.
In one example, referring to fig. 2, the rotary stirring module 3 further includes a protective shell 33. The protective casing 33 is provided around the rotating electric machine 31, and the protective casing 33 is used for providing corrosion protection for the rotating electric machine 31. The protective shell 33 may be PP.
In an example, referring to fig. 2, the rotary stirring module 3 further comprises a dust cover 34. The dust cover 34 is positioned between the upper support bracket 326 and the coupling 322 in the up-down direction, the vertical guide rod 324 and the lead screw 325a penetrate the dust cover 34, and the dust cover 34 can be unfolded and folded in the up-down direction. By accommodating the up-and-down movement of the coupling 322 with the dust cover 34, not only corrosion protection can be provided for the guide rod 324 and the lead screw 325a, but also dust protection can be provided for the guide rod 324 and the lead screw 325 a. The dust cover 34 may be PP.
Referring to fig. 1, in one embodiment, gallium crystal purification apparatus 100 further comprises cooling water circulation mechanism 4, cooling water circulation mechanism 4 is connected to heat exchange barrel 2, and cooling water circulation mechanism 4 is used for continuously introducing circulated cooling water into the gap between heat exchange barrel 2 and crystallization barrel 1, thereby realizing the heat exchange function between heat exchange barrel 2 and crystallization barrel 1. By adopting cooling water circulation, the heat storage performance and the flowing performance of water are fully utilized, the temperature stability of the crystallization barrel 1 can be well controlled, and the stability of the gallium crystallization amount of the liquid gallium raw material crystals at the same stirring speed of the stirring rod 30 is further improved.
Referring to fig. 1, in an embodiment, a crystallization barrel 1, a heat exchange barrel 2 and a rotary stirring module 3 constitute a crystallization unit U, and a gallium crystallization purification apparatus 100 includes a plurality of crystallization units U; gallium crystal purification apparatus 100 further comprises a frame 5, and said plurality of crystallization units U are disposed on said frame 5. Thus, the gallium crystal purification apparatus 100 can be mass-produced. For each crystallization unit U, specifically, the upper support frame 326 and the lower support frame 327 of each crystallization unit U are fixed to the frame 5.
In one example, referring to fig. 1, cooling water circulation mechanism 4 is a set and is connected to all heat exchange drums 2 of unit U for continuously passing the circulated cooling water into all heat exchange drums 2, thereby improving the structural compactness and simplifying the structure of gallium crystal purification apparatus 100.
[ method of purifying gallium Crystal ]
The gallium crystal purification method comprises the following steps: step one, pouring liquid raw material gallium into a crystallization barrel 1; step two, cooling the crystallization barrel 1 to be lower than the melting point of gallium; step three, stirring the liquid raw material gallium in the crystallization barrel 1 to crystallize the gallium to form gallium crystals; step four, removing and stirring and fishing out a certain amount of gallium crystals after the crystallization barrel 1 gathers a certain amount of gallium crystals; and step five, repeating the step three and the step four.
In one embodiment, step one is implemented as: putting the raw material gallium in a thermostat higher than the melting point of gallium to form liquid raw material gallium, and pouring the liquid raw material gallium into the crystallization barrel 1 after the constant temperature is finished. In one example, the constant temperature is 45-50 ℃ and the constant temperature time is 4-6 h.
In one embodiment, step two is implemented as: and opening circulating cooling water, setting the temperature of the cooling water to be 25-28 ℃, the water flow to be 2-4L/min and the indoor temperature to be 25-28 ℃ so as to reduce the temperature of the crystallization barrel 1 to be lower than the melting point of gallium. If the temperature of the cooling water is lower than 25 ℃, the crystallization speed is too high, and the product quality is influenced; if the temperature of the cooling water is higher than 28 ℃, crystallization is not easy.
In one embodiment, in the third step, the stirring speed is 15 to 20 r/min.
In one embodiment, step five is performed as: and stopping crystallization until the weight of the fished gallium crystal accounts for 85-90% of that of the liquid raw material gallium in the step one.
In one embodiment, in step four, the gallium crystals are fished out using an anti-corrosion strainer. The anti-corrosion colander can be a PP colander.
In one embodiment, the method further comprises the following steps between the first step and the second step: pouring the dilute hydrochloric acid into a crystallization barrel 1 containing the liquid raw material gallium so that the dilute hydrochloric acid covers the whole liquid level of the liquid raw material gallium. Because the density of the hydrochloric acid is lower than that of the gallium, the hydrochloric acid floats on the liquid level of the liquid raw material gallium in the crystallization barrel 1, the hydrochloric acid can be etched and reacted with the oxide on the liquid level of the liquid raw material gallium to dissolve the oxide, meanwhile, the hydrochloric acid can also isolate oxygen to prevent the liquid raw material gallium from being further oxidized, namely, the step is an acid sealing method, and thus the purity of the crystallized gallium is ensured. In one example, the dilute hydrochloric acid is 3% to 5% by volume (guaranteed purity). In one example, the liquid level of the dilute hydrochloric acid is 2-3 cm.
In the purification method of gallium crystal disclosed by the disclosure, the temperature of the crystallization barrel 1 is reduced to be lower than the melting point of gallium, and the liquid raw material gallium in the crystallization barrel 1 is stirred to crystallize the gallium into gallium crystal, so that even if the gallium is in a metastable state due to supercooling property, the metastable state of the gallium can be broken through stirring, and the liquid raw material gallium is crystallized under the condition that the temperature in the crystallization barrel 1 is lower than the melting point of the gallium. In other words, compared with the static crystallization of gallium in the background art, the purification method of gallium crystallization of the present disclosure solves the problem that the crystallization speed of gallium in the static crystallization is slow due to the supercooling property. In addition, in the static crystallization process, if the temperature control of crystallization of the liquid gallium raw material is unstable, the seed crystal is melted and cannot be crystallized, and the adoption of the seed crystal is avoided by stirring the gallium crystallization purification method disclosed by the invention, so that the problem that the static crystallization cannot be crystallized due to the melting of the seed crystal caused by the unstable temperature control is solved.
It is noted that the gallium crystal purification method of the present disclosure may be performed using the aforementioned gallium crystal purification apparatus 100, but is not limited thereto, and any suitable apparatus that performs the above-described functions of holding, heat exchange, stirring, and the like can be used in the gallium crystal purification method of the present disclosure.
Note that, when the aforementioned gallium crystal purification apparatus 100 is used, in step four, when the gallium crystal is to be fished out, the stirring rod 30 needs to be raised to move out of the liquid level of the liquid gallium raw material and stop stirring, and when the fishing out of the gallium crystal is finished, the stirring rod 30 is lowered into the liquid level of the liquid gallium raw material and starts stirring.
[ test ]
In the following examples, gallium crystal purification was performed using the gallium crystal purification apparatus 100 shown in fig. 1 and 2.
Example 1
Keeping the temperature of the blocky raw material gallium in a constant temperature box for 4 hours at the constant temperature of 45 ℃ to form liquid raw material gallium. After the constant temperature is finished, pouring liquid raw material gallium into a crystallization barrel 1 made of PP of the gallium crystallization purification device 100, wherein the weight of the raw material gallium is 50 kg;
preparing dilute hydrochloric acid with the volume ratio of 3%, pouring the dilute hydrochloric acid into a crystallization barrel 1, and adding the dilute hydrochloric acid to the crystallization barrel with the liquid level of 2 cm;
the circulating cooling water of the cooling water circulating mechanism 4 is started, the temperature of the cooling water is set to be 25 ℃, the water flow is set to be 4L/min, and the indoor temperature is set to be 27 ℃. Opening a stirring rod 30 of the gallium crystallization purification device 100, setting the stirring speed to be 15r/min, and automatically crystallizing gallium in the crystallization barrel 1;
after a certain amount of crystals are gathered in the crystallization barrel 1, the crystals are fished out by using a strainer made of PP (polypropylene), the stirring rod 30 is lifted to move out of the liquid level of the liquid gallium raw material, the stirring is stopped, and the stirring rod 30 is lowered below the liquid level of the liquid gallium raw material after the crystals are fished out each time. This procedure was repeated until the weight of the fished out crystals accounted for 86% of the charge (i.e. liquid gallium feed), and crystallization was stopped.
Comparative example
Keeping the temperature of the blocky raw material gallium in a thermostat red for 5 hours at the constant temperature of 50 ℃ to form liquid raw material gallium. After the constant temperature is finished, pouring liquid raw material gallium into a static crystallization tank provided with 50g of gallium seed crystal, wherein the weight of the liquid raw material gallium is 50kg, the temperature of cooling water is 26 ℃, the water flow is 3L/min, and the indoor temperature is 25 ℃, automatically crystallizing the liquid raw material gallium until the crystallization amount accounts for 90% of the feeding amount, scooping out tail liquid, and stopping crystallization.
Examples 2 to 5
The procedure of examples 2 to 5 was the same as in example 1 except for the specific parameters, and Table 1 was referred to.
The parameters of examples 1-5 and comparative examples and the crystallization time are listed in table 1.
Table 2 shows the impurity contents of the raw material (i.e., raw gallium) and the gallium crystals obtained in examples 1 to 5.
As can be seen from Table 2, examples 1 to 5 had about 6N from about 5N of the starting material.
The above detailed description describes exemplary embodiments, but is not intended to limit the combinations explicitly disclosed herein. Thus, unless otherwise specified, various features disclosed herein can be combined together to form a number of additional combinations that are not shown for the sake of brevity.
Claims (9)
1. A method for purifying gallium crystals is characterized by comprising the following steps:
step one, pouring liquid raw material gallium into a crystallization barrel (1);
step two, cooling the crystallization barrel (1) to be lower than the melting point of gallium;
step three, stirring the liquid raw material gallium in the crystallization barrel (1) to crystallize the gallium to form gallium crystals;
step four, removing and stirring and fishing out a certain amount of gallium crystals after the crystallization barrel (1) gathers a certain amount of gallium crystals;
and step five, repeating the step three and the step four.
2. The method of purifying a gallium crystal according to claim 1,
the first step is realized as follows: putting the raw material gallium in a constant temperature box higher than the melting point of gallium to form liquid raw material gallium, and pouring the liquid raw material gallium into the crystallization barrel (1) after the constant temperature is finished.
3. The method of purifying a gallium crystal according to claim 2,
the constant temperature is 45-50 ℃, and the constant temperature time is 4-6 h.
4. The method of purifying a gallium crystal according to claim 1,
the second step is realized as follows: and opening circulating cooling water, setting the temperature of the cooling water to be 25-28 ℃, the water flow to be 2-4L/min and the indoor temperature to be 25-28 ℃ so as to reduce the temperature of the crystallization barrel (1) to be lower than the melting point of gallium.
5. The method of purifying a gallium crystal according to claim 1,
in the third step, the stirring speed is 15-20 r/min.
6. The method of purifying a gallium crystal according to claim 1,
the step five is executed as: and stopping crystallization until the weight of the fished gallium crystal accounts for 85-90% of that of the liquid raw material gallium in the step one.
7. The method of purifying a gallium crystal according to claim 1,
the method also comprises the following steps between the first step and the second step: pouring the dilute hydrochloric acid into a crystallization barrel (1) containing the liquid raw material gallium so that the dilute hydrochloric acid covers the whole liquid level of the liquid raw material gallium.
8. The method of purifying a gallium crystal according to claim 7,
the dilute hydrochloric acid is 3-5% by volume.
9. The method of purifying a gallium crystal according to claim 7,
the liquid level of the added dilute hydrochloric acid is 2-3 cm.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2407948A1 (en) * | 1973-02-20 | 1974-08-22 | Monsanto Co | METHOD FOR CONCENTRATING GALLIUM |
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2022
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| US3988150A (en) * | 1975-10-03 | 1976-10-26 | Elena Leonidovna Shalavina | Process for extraction of gallium from sodium aluminate liquors |
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| CN102618734A (en) * | 2012-04-23 | 2012-08-01 | 南京金美镓业有限公司 | Large-scale production method for preparing high purity gallium |
| CN108588449A (en) * | 2018-05-29 | 2018-09-28 | 中铝矿业有限公司 | A kind of crystallization apparatus and method of high purity gallium |
| CN110938755A (en) * | 2019-11-20 | 2020-03-31 | 中南大学 | Gallium purification device and method |
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