CN110938755B - Gallium purification device and method - Google Patents
Gallium purification device and method Download PDFInfo
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- CN110938755B CN110938755B CN201911141564.6A CN201911141564A CN110938755B CN 110938755 B CN110938755 B CN 110938755B CN 201911141564 A CN201911141564 A CN 201911141564A CN 110938755 B CN110938755 B CN 110938755B
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- 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
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- C—CHEMISTRY; METALLURGY
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- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B35/00—Apparatus not otherwise provided for, specially adapted for the growth, production or after-treatment of single crystals or of a homogeneous polycrystalline material with defined structure
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Abstract
The invention relates to a gallium purification device and a method, the device comprises a cooling component, a seed crystal component and a crystallization tank component, wherein the crystallization tank component is positioned under the seed crystal component and is fixedly connected with the seed crystal component, and the cooling component comprises a cooling liquid storage tank, a cooling sheath and a cooling pipe for connecting the cooling liquid storage tank and the cooling sheath; the crystallizing tank component comprises a material conveying pipe, a crystallizing tank, a discharging pipe and a diaphragm; the crystallization tank comprises a crystallization tank upper part and a crystallization tank lower part, the diaphragm is separated between the crystallization tank upper part and the crystallization tank lower part, and the material conveying pipe and the material discharging pipe are communicated with the crystallization tank; an included angle theta is formed between the upper part of the crystallization tank and the horizontal direction; the lower part of the crystallization tank forms an included angle alpha with the horizontal direction; the diameter of the horizontal section of the upper part of the crystallization tank is gradually increased from top to bottom, and the whole or part of the upper part of the crystallization tank is coated by the cooling jacket. The gallium purification device and method can provide a temperature field, crystallization is carried out in the temperature field, and the gallium crystallization process can be gradually carried out from the upper surface of the molten gallium downwards.
Description
Technical Field
The invention relates to the field of high-purity gallium preparation, in particular to a gallium purification device and method.
Background
The high-purity gallium and the compound thereof are widely applied to the high-tech field of modern equipment manufacturing such as petrochemical industry, solar photovoltaic systems, national defense aerospace, signal image processing, modern automobile industry and the like. In addition, high purity gallium is also widely used in the field of electronic devices such as low melting alloys, epitaxial wafers and optoelectronic devices. Along with the deep popularization of new concepts such as low-carbon economy, green energy and the like, the application range of high-purity gallium in the fields is expanded, and the market demand on the high-purity gallium is further continuously increased.
The existing preparation methods of high-purity gallium mainly comprise a crystallization method, a vacuum distillation method, an electrolytic refining method, a chemical extraction method, an organic compound thermal decomposition method, a gallium trichloride purification method and the like. The crystallization method is a common method for preparing high-purity metal gallium, and can effectively remove impurity elements such as lead, copper, nickel, iron and the like. Meanwhile, the energy consumption of the crystallization purification is much lower than that of the pyrolysis and other refining methods.
Chinese patent application No. CN104711438A discloses a method and apparatus for preparing high purity gallium, in which liquid high purity gallium is placed at the bottom of a container and cooled to be used as seed crystal, liquid metal gallium is poured into a cooling container to be cooled and crystallized, after complete crystallization, a heat source coil is started, the temperature and moving speed of the heat source coil are controlled, and the high purity gallium is obtained by moving from bottom to top.
The patent publication number is CN 204661809U's chinese utility model patent, provides a gallium purification crystallization system that can control crystallization environment atmosphere, through the temperature gradient of control crystallization gallium liquid, reduces the crystallization number of times, and then improves the crystallization efficiency and the purity of gallium.
Chinese patent application with patent publication No. CN103031450A, adopts acid washing pre-purification and ultrasonic vibration to primarily separate sponge gallium impurities in liquid metal gallium, and carries out freezing crystallization to remove heavy metal impurities in the metal gallium; and separating the gallium metal and the sponge gallium by ultrasonic vibration after acid washing to obtain the high-purity gallium.
The Chinese patent application with the patent application number of 200310115208.X provides a preparation method of ultra-pure metal gallium, which comprises two processes of low-temperature electrolytic purification and zone melting purification.
Chinese patent application with patent publication number CN102618734A proposes a large-scale production method for preparing high-purity gallium, which comprises the following steps: putting gallium metal seed crystals into the bottom of a crystallization container; injecting liquid metal gallium into a crystallization container; and cooling the bottom of the crystallization container to obtain the high-purity gallium.
The gallium is purified by crystallization method by utilizing the solubility difference of impurity elements in a main phase state and a non-main phase state, so that impurities are separated out or the distribution of the impurities is changed. The innovation points of the prior art of purification by the existing crystallization method mainly focus on the aspects of temperature field control, multiple methods and the like, but the problems of separation of crystallization mother liquor and crystal gallium, control of crystal growth direction and the like after crystallization are not noticed; in the existing crystallization process, crystallization is started from the bottom, and finally obtained gallium crystals are in the lower part and crystallization mother liquor is in the upper part.
In addition, the solid-liquid separation is difficult because the crystal surface is uneven and the crystallization mother liquor only accounts for about 15 percent; at present, solid-liquid separation is mostly realized by adopting a method of manually and gradually extracting upper-layer liquid by using a spoon, and after the liquid is separated out, the liquid is heated and melted, and high-purity gallium is discharged from the bottom. The above process and operation have the following problems: (1) the separation of the gallium crystal from the crystallization mother liquor is not thorough; (2) the mother liquor which is not completely decomposed is enriched with a large amount of impurities, so that the high-purity gallium is polluted; (3) the whole system is difficult to realize mechanized control; (4) the crystal growth direction is difficult to control, and the problems of entrainment and the like exist, so that the purification efficiency is not high.
In order to solve the above technical problems, the present invention proposes a new gallium purification apparatus and method.
Disclosure of Invention
The invention aims to overcome the defects and defects in the background art and provide a gallium purification device and method, which realize that the gallium crystallization process is gradually carried out from the upper surface of molten gallium downwards by controlling the crystallization temperature gradient in a mode of optimizing the combination of a cooling sleeve and a crystallization tank. Meanwhile, a membrane for solid-liquid separation and a washing liquid circulating component for tangentially feeding washing liquid are combined, so that the high-efficiency separation of the crystal gallium and the crystallized residual liquid can be realized.
In order to achieve the purpose, the invention adopts the following technical scheme: a gallium purification device comprises a cooling assembly, a seed crystal assembly and a crystallization tank assembly, wherein the crystallization tank assembly is positioned under the seed crystal assembly and is fixedly connected with the seed crystal assembly, and the cooling assembly comprises a cooling liquid storage tank, a cooling sheath and a cooling pipe for connecting the cooling liquid storage tank and the cooling sheath; the crystallizing tank component comprises a material conveying pipe, a crystallizing tank, a discharging pipe and a diaphragm; the crystallization tank comprises a crystallization tank upper part and a crystallization tank lower part, the diaphragm is separated between the crystallization tank upper part and the crystallization tank lower part, and the material conveying pipe and the material discharging pipe are communicated with the crystallization tank; an included angle theta is formed between the upper part of the crystallization tank and the horizontal direction; the lower part of the crystallization tank forms an included angle alpha with the horizontal direction; the diameter of the horizontal section of the upper part of the crystallization tank is gradually increased from top to bottom, and the whole or part of the upper part of the crystallization tank is coated by the cooling jacket.
As a further improvement of the invention, the upper part and the lower part of the crystallization tank respectively have one of a cone and a pyramid; the included angle theta ranges from 30 to 75; the included angle alpha ranges from 30 to 75.
As a further improvement of the invention, the seed crystal assembly comprises a tray rod, a rotating device, a tray rod fixing frame, a threaded connection device, a seed crystal tray and seed crystals; the seed crystal is fixed below the seed crystal plate; the seed crystal plate is clamped in the threaded connection device, two ends of the tray rod are respectively fixed on the rotating device and the seed crystal plate, the rotating device can drive the seed crystal plate to ascend or descend in the threaded connection device through the tray rod, and the seed crystal also ascends or descends along with the seed crystal plate.
As a further improvement of the invention, the gallium purification device also comprises a cover body and a washing liquid circulating component, wherein the cover body is divided into three parts, namely an upper part, a middle part and a lower part which are spaced from top to bottom; a heating lamp and a temperature controller are fixed on the middle part; the upper part forms a closed space, and the tray rod fixing frame is fixed on the inner bottom surface of the upper part; the threaded connection device, the seed crystal disk, the seed crystal, the cooling sheath and the upper part of the crystallization tank are all positioned in the middle part, and the cooling liquid storage tank is positioned outside or in the lower part of the cover body; the washing liquid circulation assembly comprises a washing liquid feeding pipe, a washing liquid discharging pipe and a washing liquid storage tank.
As a further improvement of the invention, the upper part of the crystallization tank is divided into a first part and a second part, and the second part is connected with the lower part of the crystallization tank; the first part of the whole body is completely covered by the cooling sheath, and the second part of the whole body is not covered by the cooling sheath.
The invention also provides a gallium purification method, which adopts the gallium purification device and comprises the following steps: s1, conveying the crystallization mother liquor to a crystallization tank through a conveying pipe; s2, controlling the environmental temperature of the crystallization tank by using a temperature controller; s3, contacting the lower surface of the seed crystal with the upper surface of the crystallization mother liquor; s4, starting a cooling assembly, controlling the cooling temperature, forming a certain temperature field in the crystallization tank, and starting crystallization of the crystallization mother liquor in the temperature field; s5, obtaining crystal gallium and crystallization residual liquid after crystallization, separating the crystal gallium from the crystallization residual liquid through solid-liquid separation by a diaphragm, discharging the crystallization residual liquid from a discharge pipe, and simultaneously introducing washing liquid through a washing liquid feeding pipe to further wash and remove the crystallization residual liquid on the surface of the crystal gallium; and S6, heating and melting the crystal gallium and discharging the crystal gallium from the discharging pipe to obtain the high-purity gallium.
As a further improvement of the invention, the temperature of the mother liquor of crystallization in S1 is 30-70 ℃.
As a further improvement of the invention, the seed crystal in S3 is prepared by compacting solid high-purity gallium with the purity of 6-8N.
As a further improvement of the present invention, the cooling temperature is controlled to 6 to 27 ℃ in S4.
As a further improvement of the invention, the temperature of the molten crystalline gallium in S6 is 32-45 ℃.
Compared with the prior art, the invention has the beneficial effects that: because the density of the liquid gallium is greater than that of the solid gallium, the combination mode of the upper part of the crystallization tank and the cooling sheath ensures that: under the condition of introducing cooling liquid with the same temperature and the same environmental temperature, a temperature field with gradually increased temperature from top to bottom can be formed. The crystallization is carried out in the temperature field, the gallium crystallization process can be gradually carried out from the upper surface of the molten gallium downwards, namely, the crystal gallium is always positioned above the crystallization mother liquor in the crystallization process, the high-efficiency separation of the crystal and the crystallization residual liquid can be realized, the pollution of the crystal gallium and the inaccuracy of manual separation are avoided, the purification way of the existing gallium crystallization and the separation way of the crystal gallium and the crystallization residual liquid are fundamentally changed, and the automatic control of the gallium crystallization process is more facilitated.
Drawings
FIG. 1 is a schematic view of the overall structure of a gallium purification apparatus according to the present invention.
FIG. 2 is a schematic view of the structure of a gallium purification apparatus according to the present invention.
Detailed Description
The technical solutions will be described clearly and completely in the following with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a gallium purification device 100, and the device 100 comprises a cooling component 1, a seed crystal component 2, a crystallization tank component 3, a cover body 4 and a washing liquid circulating component 5. The crystallization tank component 3 is positioned under the seed crystal component 2 and is fixedly connected with the seed crystal component 2, the washing liquid circulating component 5 is communicated with the crystallization tank component 3, and the seed crystal component 2, the crystallization tank component 3 and the washing liquid circulating component 5 are all positioned in the cover body 4.
The cooling assembly 1 comprises a cooling liquid storage tank 11, a cooling jacket 12 and a cooling pipe 13 connecting the cooling liquid storage tank 11 and the cooling jacket 12, and a cooling liquid feeding controller 14 is arranged on the cooling pipe 13 at the feeding section. Through the cooling pipe 13, a circulation of cooling liquid is formed between the cooling liquid reservoir 11 and the cooling jacket 12.
The seed crystal assembly 2 comprises a tray rod 21, a rotating device 22, a tray rod fixing frame 23, a threaded connection device 24, a seed crystal disk 25 and seed crystals 26; the seed crystal 26 is fixed below the seed crystal plate 25, and the graduated tray rod 21 plays a role in distance measurement. The tray lever fixing frame 23 functions to fix the tray lever 21. The seed crystal disk 25 is clamped in the threaded connection device 24, two ends of the tray rod 21 are respectively fixed on the rotating device 22 and the seed crystal disk 25, the rotating device 22 can drive the seed crystal disk 25 to ascend or descend in the threaded connection device 24 through the tray rod 21, and the seed crystal 26 also ascends or descends along with the seed crystal disk 25.
The crystallizing tank assembly 3 comprises a feed pipe 31, a crystallizing tank 32, a discharge pipe 33 and a diaphragm 34. The crystallization tank 32 is a place for crystallizing high-purity gallium, and the material conveying pipe 31 and the material discharging pipe 33 are both communicated with the crystallization tank 32 and are respectively used for conveying and discharging crystallization mother liquor.
The crystallization tank 32 comprises a crystallization tank upper part 32a and a crystallization tank lower part 32b, and the included angle theta formed by the crystallization tank upper part 32a and the horizontal direction is 30-75; the angle alpha formed by the lower part 32b of the crystallization tank and the horizontal direction is in the range of 30-75. The included angle theta influences the temperature gradient during crystallization; the angle α affects the outflow rate of the crystallization mother liquor or the crystallization raffinate. The upper and lower crystallization tank portions 32a and 32b have one of a conical and pyramidal structure. The upper crystallization tank portion 32a is entirely or partially covered by the cooling jacket 12.
The diaphragm 34 is partitioned between the upper crystallization tank part 32a and the lower crystallization tank part 32b, and the diaphragm 34 functions to separate solid and liquid.
In some embodiments of the present invention, the upper crystallization tank portion 32a is divided into a first portion 32a1 and a second portion 32a2, depending on whether it is covered by the cooling jacket 12 or not, and the second portion 32a2 is connected to the lower crystallization tank portion 32 b. The horizontal cross-sectional diameter of the upper part 32a of the crystallization tank gradually increases from top to bottom, the first part 32a1 is entirely covered by the cooling jacket 12, and the second part 32a2 is entirely uncovered by the cooling jacket 12. The cooling jacket 12 has a cylindrical structure with a mounting hole for placing the upper crystallization tank portion 32a or the first portion 32a1 of the upper crystallization tank portion 32 a. The upper crystallization tank portion 32a is coupled to the cooling jacket 12 in such a manner that: under the condition of introducing cooling liquid with the same temperature and the same environmental temperature, a temperature field with gradually increased temperature from top to bottom can be formed. The crystallization is performed under such a temperature field that the crystals can be grown from the top down.
The cover 4 is divided into three parts, an upper part 41, a middle part 42 and a lower part 43 which are spaced from top to bottom. A heating lamp 44 and a temperature controller 45 are fixed on the middle part 42. The upper part 41 forms a closed space, and the tray rod fixing frame 23 is fixed on the inner bottom surface of the upper part 41; the threaded connection 24, the seed plate 25, the seed crystal 26, the cooling jacket 12 and the upper crystallization tank portion 32a are all located in the middle portion 42, and the cooling liquid reservoir 11 is located outside the enclosure 4 or in the lower portion 43.
The washing liquid circulation module 5 comprises a washing liquid feed pipe 51, a washing liquid discharge pipe 52 and a washing liquid storage tank 53. In some embodiments of the apparatus, a washing liquid feed controller 51a is provided to the washing liquid feed pipe 51, and the washing liquid feed controller 51a controls the feed flow rate and the feed temperature. The washing liquid circulating component 5 adopts tangential washing liquid, and can further wash impurities contained on the surface of the gallium crystal. The lower crystallization tank portion 32b and the washing liquid storage tank 54 are located in the lower portion 43.
The cooling pipe 13, the feed delivery pipe 31, the discharge pipe 33, the washing liquid feed pipe 51 and the washing liquid discharge pipe 52 are all provided with control valves 6.
The invention also provides a gallium purification method, which adopts the gallium purification device and comprises the following steps: s1, conveying the crystallization mother liquor to a crystallization tank through a conveying pipe; s2, controlling the environmental temperature of the crystallization tank by using a temperature controller; s3, contacting the lower surface of the seed crystal with the upper surface of the crystallization mother liquor; s4, starting a cooling assembly, controlling the cooling temperature, forming a certain temperature field in the crystallization tank, and starting crystallization of the crystallization mother liquor in the temperature field; s5, obtaining crystal gallium and crystallization residual liquid after crystallization, separating the crystal gallium from the crystallization residual liquid through solid-liquid separation by a diaphragm, discharging the crystallization residual liquid from a discharge pipe, and simultaneously introducing washing liquid through a washing liquid feeding pipe to further wash and remove the crystallization residual liquid on the surface of the crystal gallium; and S6, heating and melting the crystal gallium and discharging the crystal gallium from the discharging pipe to obtain the high-purity gallium.
In certain embodiments of the invention, the temperature of the crystallization mother liquor in S1 is 30-70 ℃. The temperature of the crystallization mother liquor can not be lower than the melting point of gallium, and the energy waste can be caused by the overhigh temperature of the crystallization mother liquor.
In certain embodiments of the invention, the ambient temperature of the crystallization tank in S2 is 29-50 ℃. The ambient temperature of the crystallization tank should be slightly lower than the melting point of gallium or higher than the melting point of gallium, but too high ambient temperature also causes waste of energy.
In certain embodiments of the present invention, the seed crystals in S3 are produced by compacting solid high purity gallium having a purity of 6-8N. Furthermore, the specific process of loading the seed crystal on the seed crystal plate is as follows: and (3) putting the seed crystal plate into 7N molten gallium except the upper surface, then cooling the seed crystal plate in an environment of 10-20 ℃, crystallizing the molten gallium into the seed crystal plate under the guidance of seed crystals, and then compacting and flattening to obtain the seed crystal plate loaded with the seed crystals.
In certain embodiments of the present invention, the cooling temperature is controlled to 6-27 ℃ in S4. The cooling temperature needs to be lower than the melting point of gallium, but if the cooling temperature is too low, energy is wasted.
In certain embodiments of the invention, the washing liquid in S5 is a dilute hydrochloric acid solution with a mass fraction of 1-8%. A dilute hydrochloric acid solution with too high a mass fraction may corrode the crystallization tank, and a dilute hydrochloric acid solution with too low a mass fraction may not serve as a washing liquid.
In certain embodiments of the present invention, the temperature of the molten crystalline gallium in S6 is 32-45 ℃. The temperature of the molten crystalline gallium needs to be slightly above the melting point of gallium, and too high a temperature will result in waste of energy.
Example 1.
After a gallium purification device is installed, 4N gallium is melted at 45 ℃ to form crystallization mother liquor, the crystallization mother liquor is input into a crystallization tank through a material conveying pipe, the included angle theta formed by the upper part of the crystallization tank and the horizontal direction is 75 degrees, and the included angle alpha formed by the lower part of the crystallization tank and the horizontal direction is 30 degrees; measuring the distance from the upper liquid level of the crystallization mother liquor in the crystallization tank to the notch of the crystallization tank to be 18cm through a tray rod with scales; controlling the temperature of the closed space in the upper part of the cover body to be 50 ℃ through a temperature controller; starting a rotating device to rotate a tray rod, so that a seed crystal tray slowly moves downwards by 18cm to enable the lower surface of a seed crystal to be in contact with the upper surface of the crystallization mother liquor; starting a cooling assembly, introducing cooling liquid with the temperature of 20 ℃ into a cooling jacket, and stopping crystallization after 5 days of crystallization (the solid-liquid ratio of the crystal to the crystallization residual liquid is calculated to be 83: 17); discharging crystallization mother liquor from a discharge pipe of the crystallization tank; introducing a dilute hydrochloric acid solution with the mass fraction of 1% into a crystallization tank from a washing liquid feeding pipe in a tangential direction, and repeatedly washing for 3 times; and starting a temperature controller to ensure that the ambient temperature is 45 ℃, and discharging the molten crystallized gallium from a discharging pipe to obtain high-purity gallium with the purity of 6N.
Example 2.
After a gallium purification device is installed, 4N gallium is melted at 70 ℃ to form crystallization mother liquor, the crystallization mother liquor is input into a crystallization tank through a material conveying pipe, the included angle theta formed by the upper part of the crystallization tank and the horizontal direction is 30 degrees, and the included angle alpha formed by the lower part of the crystallization tank and the horizontal direction is 75 degrees; measuring the distance from the upper liquid level of the crystallization mother liquor in the crystallization tank to the notch of the crystallization tank to be 18cm through a tray rod with scales; controlling the temperature of the closed space in the upper part of the cover body to be 35 ℃ by a temperature controller; starting a rotating device to rotate a tray rod, so that a seed crystal tray slowly moves downwards by 18cm to enable the lower surface of a seed crystal to be in contact with the upper surface of the crystallization mother liquor; starting a cooling assembly, introducing cooling liquid with the temperature of 27 ℃ into a cooling sleeve, and stopping crystallization after 7 days of crystallization (calculating to obtain the ratio of crystals to the residual crystallization liquid to the solid-liquid ratio of 80: 20); discharging crystallization mother liquor from a discharge pipe of the crystallization tank; introducing an ultra-pure hydrochloric acid solution with the mass fraction of 3% into a crystallization tank from a washing liquid feeding pipe in a tangential direction, and repeatedly washing for 3 times; and starting a temperature controller to ensure that the ambient temperature is 35 ℃, and discharging the molten crystallized gallium from a discharging pipe to obtain the high-purity gallium with the purity of 7N.
Example 3.
After a gallium purification device is installed, 4N gallium is melted at 30 ℃ to form crystallization mother liquor, the crystallization mother liquor is input into a crystallization tank through a material conveying pipe, the included angle theta formed by the upper part of the crystallization tank and the horizontal direction is 45 degrees, and the included angle alpha formed by the lower part of the crystallization tank and the horizontal direction is 40 degrees; measuring the distance from the upper liquid level of the crystallization mother liquor in the crystallization tank to the notch of the crystallization tank to be 18cm through a tray rod with scales; controlling the temperature of the closed space in the upper part of the cover body to be 29 ℃ by a temperature controller; starting a rotating device to rotate a tray rod, so that a seed crystal tray slowly moves downwards by 18cm to enable the lower surface of a seed crystal to be in contact with the upper surface of the crystallization mother liquor; starting a cooling assembly, introducing cooling liquid with the temperature of 6 ℃ into a cooling sleeve, and stopping crystallization after 10 days of crystallization (the solid-liquid ratio of the crystal to the crystallization residual liquid is calculated to be 84: 16); discharging crystallization mother liquor from a discharge pipe of the crystallization tank; introducing an ultra-pure hydrochloric acid solution with the mass fraction of 8% into a crystallization tank from a washing liquid feeding pipe in a tangential direction, and repeatedly washing for 3 times; and starting a temperature controller to ensure that the ambient temperature is 32 ℃, and discharging the molten crystallized gallium from a discharging pipe to obtain the high-purity gallium with the purity of 7N.
Compared with the prior art, the invention has the beneficial effects that: because the density of the liquid gallium is greater than that of the solid gallium, the combination mode of the upper part of the crystallization tank and the cooling sheath ensures that: under the condition of introducing cooling liquid with the same temperature and the same environmental temperature, a temperature field with gradually increased temperature from top to bottom can be formed. The crystallization is carried out in the temperature field, the gallium crystallization process can be gradually carried out from the upper surface of the molten gallium downwards, namely, the crystal gallium is always positioned above the crystallization mother liquor in the crystallization process, the high-efficiency separation of the crystal and the crystallization residual liquid can be realized, the pollution of the crystal gallium and the inaccuracy of manual separation are avoided, the purification way of the existing gallium crystallization and the separation way of the crystal gallium and the crystallization residual liquid are fundamentally changed, and the automatic control of the gallium crystallization process is more facilitated.
Although the preferred embodiments of the present invention have been disclosed for illustrative purposes, those skilled in the art will appreciate that various modifications, additions and substitutions are possible, without departing from the scope and spirit of the invention as disclosed in the accompanying claims.
Claims (10)
1. A gallium purification device is characterized in that: the device comprises a cooling assembly, a seed crystal assembly and a crystallization tank assembly, wherein the crystallization tank assembly is positioned right below the seed crystal assembly and is fixedly connected with the seed crystal assembly, and the cooling assembly comprises a cooling liquid storage tank, a cooling sheath and a cooling pipe for connecting the cooling liquid storage tank and the cooling sheath; the crystallizing tank component comprises a material conveying pipe, a crystallizing tank, a discharging pipe and a diaphragm; the crystallization tank comprises a crystallization tank upper part and a crystallization tank lower part, the diaphragm is separated between the crystallization tank upper part and the crystallization tank lower part, and the material conveying pipe and the material discharging pipe are communicated with the crystallization tank; an included angle theta is formed between the upper part of the crystallization tank and the horizontal direction; the lower part of the crystallization tank forms an included angle alpha with the horizontal direction; the diameter of the horizontal section of the upper part of the crystallization tank is gradually increased from top to bottom, and the whole or part of the upper part of the crystallization tank is coated by the cooling jacket.
2. The gallium purification apparatus according to claim 1, wherein: the upper part and the lower part of the crystallization tank respectively have one of a cone and a pyramid; the included angle theta ranges from 30 to 75; the included angle alpha ranges from 30 to 75.
3. The gallium purification apparatus according to claim 2, wherein: the seed crystal assembly comprises a tray rod, a rotating device, a tray rod fixing frame, a threaded connecting device, a seed crystal tray and seed crystals; the seed crystal is fixed below the seed crystal plate; the seed crystal plate is clamped in the threaded connection device, two ends of the tray rod are respectively fixed on the rotating device and the seed crystal plate, the rotating device can drive the seed crystal plate to ascend or descend in the threaded connection device through the tray rod, and the seed crystal also ascends or descends along with the seed crystal plate.
4. The gallium purification apparatus according to claim 3, wherein: the gallium purification device also comprises a cover body and a washing liquid circulating component, wherein the cover body is divided into three parts, namely an upper part, a middle part and a lower part which are spaced from top to bottom; a heating lamp and a temperature controller are fixed on the middle part; the upper part forms a closed space, and the tray rod fixing frame is fixed on the inner bottom surface of the upper part; the threaded connection device, the seed crystal disk, the seed crystal, the cooling sheath and the upper part of the crystallization tank are all positioned in the middle part, and the cooling liquid storage tank is positioned outside or in the lower part of the cover body; the washing liquid circulation assembly comprises a washing liquid feeding pipe, a washing liquid discharging pipe and a washing liquid storage tank.
5. The gallium purification apparatus according to claim 4, wherein: the upper part of the crystallization tank is divided into a first part and a second part, and the second part is connected with the lower part of the crystallization tank; the first part of the whole body is completely covered by the cooling sheath, and the second part of the whole body is not covered by the cooling sheath.
6. A gallium purification method using the gallium purification apparatus according to claim 5, characterized in that: the method comprises the following steps:
s1, conveying the crystallization mother liquor to a crystallization tank through a conveying pipe;
s2, controlling the environmental temperature of the crystallization tank by using a temperature controller;
s3, contacting the lower surface of the seed crystal with the upper surface of the crystallization mother liquor;
s4, starting a cooling assembly, controlling the cooling temperature, forming a certain temperature field in the crystallization tank, and starting crystallization of the crystallization mother liquor in the temperature field;
s5, obtaining crystal gallium and crystallization residual liquid after crystallization, separating the crystal gallium from the crystallization residual liquid through solid-liquid separation by a diaphragm, discharging the crystallization residual liquid from a discharge pipe, and simultaneously introducing washing liquid through a washing liquid feeding pipe to further wash and remove the crystallization residual liquid on the surface of the crystal gallium;
and S6, heating and melting the crystal gallium and discharging the crystal gallium from the discharging pipe to obtain the high-purity gallium.
7. The gallium purification method according to claim 6, characterized in that: the temperature of the crystallization mother liquor in S1 is 30-70 ℃.
8. The gallium purification method according to claim 6, characterized in that: the seed crystal in S3 is prepared by compacting solid high-purity gallium with the purity of 6-8N.
9. The gallium purification method according to claim 6, characterized in that: in S4, the cooling temperature is controlled to be 6-27 ℃.
10. The gallium purification method according to claim 6, characterized in that: the temperature of the molten crystal gallium in S6 is 32-45 ℃.
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| CN201911141564.6A CN110938755B (en) | 2019-11-20 | 2019-11-20 | Gallium purification device and method |
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| CN201911141564.6A CN110938755B (en) | 2019-11-20 | 2019-11-20 | Gallium purification device and method |
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| CN110938755B true CN110938755B (en) | 2021-06-11 |
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| CN201911141564.6A Active CN110938755B (en) | 2019-11-20 | 2019-11-20 | Gallium purification device and method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1039064A (en) * | 1988-07-01 | 1990-01-24 | 皮奇尼铝公司 | Method by the partial coagulation gallium-purifying |
| JP2013103863A (en) * | 2011-11-15 | 2013-05-30 | Tamura Seisakusho Co Ltd | METHOD FOR PRODUCING β-Ga2O3 CRYSTAL |
| CN103147129A (en) * | 2006-11-09 | 2013-06-12 | 莫门蒂夫性能材料股份有限公司 | Method for growing a crystalline composition comprising gallium nitride |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1039064A (en) * | 1988-07-01 | 1990-01-24 | 皮奇尼铝公司 | Method by the partial coagulation gallium-purifying |
| CN103147129A (en) * | 2006-11-09 | 2013-06-12 | 莫门蒂夫性能材料股份有限公司 | Method for growing a crystalline composition comprising gallium nitride |
| JP2013103863A (en) * | 2011-11-15 | 2013-05-30 | Tamura Seisakusho Co Ltd | METHOD FOR PRODUCING β-Ga2O3 CRYSTAL |
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