High-purity gallium stirring crystallization device and crystallization method

Abstract

The invention discloses a high-purity gallium stirring crystallization device and a crystallization method. The device comprises a heating assembly, a crystallization assembly, a cooling assembly and a magnetic stirring assembly. Wherein the heating assembly is used for heating and preserving heat of liquid gallium; the crystallization assembly is used for loading liquid gallium, and the crystallization process of the liquid gallium also occurs in the crystallization assembly; the cooling assembly is used for cooling the liquid gallium; the magnetic stirring assembly is used for stirring the liquid gallium in the crystallization assembly, and impurities in the liquid gallium are thrown away from the crystallized gallium through centrifugal force. According to the method, crystallization is started from outside to inside in the crystallization process, crystal gallium is always located outside the crystallization mother liquor in the crystallization process, wrapping cannot be formed, and efficient separation of crystals and crystallization residual liquor can be achieved. And invasion of external impurities in a traditional stirring process can be avoided through a magnetic stirring mode, so that the purity of finished gallium is improved.

Description

Technical Field

[0001] The present application relates to the technical field of high-purity gallium preparation, and in particular to a high-purity gallium stirring crystallization device and a crystallization method. Background Art

[0002] High-purity gallium and its compounds are widely used in petrochemical, solar photovoltaic systems, national defense and aerospace, signal image processing, modern automobile industry and other modern equipment manufacturing high-tech fields. In addition, high-purity gallium is also widely used in electronic devices such as low-melting alloys, epitaxial wafers and optoelectronic devices. It is foreseeable that the market demand for high-purity gallium will continue to increase further.

[0003] At present, the preparation method of high-purity gallium mainly adopts the crystallization method. The crystallization method purifies gallium by utilizing the difference in solubility of impurity elements in the main phase and the non-main phase, so that impurities are precipitated or their distribution is changed. The innovation points of the existing crystallization purification technology are mainly concentrated in aspects such as temperature field control, but no attention is paid to the separation of crystallization mother liquor and crystalline gallium after crystallization and industrial application. In addition, the existing crystallization process starts crystallization from the bottom, and the gallium crystals finally obtained are at the bottom and the crystallization mother liquor is at the top, which makes it difficult to separate the mother liquor.

[0004] In addition, due to the unevenness of the crystal surface and the fact that the crystallization mother liquor only accounts for about 15%, it is difficult to separate the solid and liquid. At present, the solid-liquid separation is mostly achieved by manually extracting the upper layer of liquid with a spoon. After the liquid is separated, the crystal is heated and melted to release high-purity gallium from the bottom. The above process and operation have the following problems: (1) The separation of crystalline gallium and crystallization mother liquor is not complete; (2) The mother liquor that has not been completely decomposed will cause contamination of high-purity gallium due to the enrichment of a large amount of impurities; (3) The entire system is difficult to achieve mechanized control; (4) The crystal growth direction is difficult to control, and there are problems such as entrainment, resulting in low purification efficiency. Summary of the invention

[0005] The purpose of the present application is to solve at least one of the technical problems existing in the prior art, and to provide a high-purity gallium stirring crystallization device and a crystallization method, which can improve the separation degree of crystalline gallium and crystallization mother liquor, and improve the purity and purification efficiency of crystalline gallium.

[0006] According to the first embodiment of the present application, a high-purity gallium stirring crystallization device is provided, comprising:

[0007] A heating component, the heating component comprising a heating pipe, a hot water inlet pipe and a hot water outlet pipe, the hot water inlet pipe and the hot water outlet pipe are respectively connected to both ends of the heating pipe;

[0008] A crystallization assembly, the crystallization assembly comprising a crystallization tube and a liquid discharge pipe, the crystallization tube is sleeved on the outside of the heating tube, and the liquid discharge pipe is connected to the bottom of the crystallization tube to discharge the crystallization mother liquid;

[0009] A cooling assembly, the cooling assembly comprising a cooling pipe, a cold water inlet pipe and a cold water outlet pipe, the cooling pipe is sleeved on the outside of the crystallization tube, and the cold water inlet pipe and the cold water outlet pipe are respectively connected to two ends of the cooling pipe;

[0010] A magnetic stirring assembly, the magnetic stirring assembly comprising a magnetic driving seat and a magnet, the magnet being placed in the crystallization tube, the magnetic driving seat driving the magnet to move in the crystallization tube by magnetic force, and being used to stir the substance in the crystallization tube;

[0011] The gallium liquid to be crystallized is injected into the crystallization tube, the heating tube heats the inner wall of the crystallization tube, and the cooling tube cools the outer wall of the crystallization tube; the magnetic drive seat drives the magnet to move in the crystallization tube to stir the gallium liquid and accelerate the separation of impurities and crystallized gallium.

[0012] According to the first aspect embodiment of the present application, further, the hot water inlet pipe is connected to the bottom of the heating pipe, and the hot water outlet pipe is connected to the top of the heating pipe.

[0013] According to the first aspect of the present application, further, the heating tube is made of polytetrafluoroethylene.

[0014] According to the first aspect embodiment of the present application, further, the cold water inlet pipe is connected to the bottom of the cooling pipe, and the cold water outlet pipe is connected to the top of the cooling pipe.

[0015] According to the first aspect of the present application, further, the cooling tube is made of polytetrafluoroethylene.

[0016] According to the first aspect embodiment of the present application, further, the drain pipe is installed with a valve to control the opening and closing of the drain pipe.

[0017] According to the first aspect embodiment of the present application, further, the heating tube is a round tube, and the crystallization tube and the cooling tube are both annular tubes.

[0018] According to a second aspect of the present application, a crystallization method based on the high-purity gallium stirring crystallization device is provided, comprising:

[0019] pouring liquid gallium into the crystallization tube;

[0020] The hot water inlet pipe is externally connected to hot water, and the hot water enters the heating tube to transfer heat to the crystallization tube;

[0021] The cold water inlet pipe is externally connected to cold water, and the cold water enters the cooling pipe to transfer cold energy to the crystallization tube;

[0022] Controlling the flow of hot water in the heating tube and the flow of cold water in the cooling tube, adjusting the ratio of heat and cold transferred to the crystallization tube, so that the crystallization mother liquor and the crystallized gallium are separated from each other;

[0023] The magnetic driving seat is turned on, and the magnet moves in the crystal tube under the action of magnetic force, thereby promoting the separation of impurity elements;

[0024] When 10-20% of the crystallization mother liquor remains, the crystallization is stopped, and the remaining gallium liquid is discharged through the liquid discharge pipe;

[0025] Increasing the flow rate ratio and temperature of hot water to melt the crystalline gallium in the crystallization tube;

[0026] Repeat the above steps several times to obtain high-purity gallium.

[0027] According to the second aspect of the present application, further, the temperature of the hot water is 35-50°C.

[0028] According to the second aspect of the present application, further, the temperature of the cold water is 15-25°C.

[0029] The beneficial effects of the embodiments of the present application include at least: the crystallization process in the present application starts from the outside to the inside, the crystalline gallium is always located outside the crystallization mother liquid during the crystallization process, and will not form a wrap, so that the crystal and the crystal residual liquid can be efficiently separated. The intrusion of external impurities in the traditional stirring process can be avoided by magnetic stirring, thereby improving the purity of the finished gallium. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] In order to more clearly illustrate the technical solutions in the embodiments of the present application, the following is a brief description of the drawings required for use in the description of the embodiments. Obviously, the drawings described are only part of the embodiments of the present application, not all of the embodiments, and those skilled in the art can also obtain other design solutions and drawings based on these drawings without creative work.

[0031] Figure 1 is a three-dimensional diagram of a high-purity gallium stirring crystallization device according to an embodiment of the first aspect of the present application;

[0032] Figure 2 This is a front view of a high-purity gallium stirring crystallization device according to an embodiment of the first aspect of the present application;

[0033] Figure 3 It is a top view of the high-purity gallium stirring crystallization device according to the first embodiment of the present application.

[0034] Figure numerals: 110 - heating pipe, 120 - hot water inlet pipe, 130 - hot water outlet pipe, 210 - crystallization tube, 220 - drainage pipe, 310 - cooling pipe, 320 - cold water inlet pipe, 330 - cold water outlet pipe, 410 - magnetic drive seat. DETAILED DESCRIPTION

[0035] This section will describe in detail the specific embodiments of the present application. The preferred embodiments of the present application are shown in the accompanying drawings. The purpose of the accompanying drawings is to supplement the description of the text part of the specification with graphics, so that people can intuitively and vividly understand each technical feature and the overall technical solution of the present application, but it cannot be understood as a limitation on the scope of protection of the present application.

[0036] In the description of the present application, it should be understood that descriptions involving orientation, such as up, down, front, back, left, right, etc., indicating orientations or positional relationships, are based on the orientations or positional relationships shown in the accompanying drawings, and are only for the convenience of describing the present application and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and therefore should not be understood as a limitation on the present application.

[0037] In the description of this application, "several" means one or more, "more" means more than two, "greater than", "less than", "exceed", etc. are understood to exclude the number itself, and "above", "below", "within", etc. are understood to include the number itself. If there is a description of "first" or "second", it is only used for the purpose of distinguishing technical features, and cannot be understood as indicating or implying relative importance or implicitly indicating the number of the indicated technical features or implicitly indicating the order of the indicated technical features.

[0038] In the description of this application, unless otherwise clearly defined, terms such as setting, installing, connecting, etc. should be understood in a broad sense, and technicians in the relevant technical field can reasonably determine the specific meanings of the above terms in this application based on the specific content of the technical solution.

[0039] At present, the preparation method of high-purity gallium mainly adopts the crystallization method. The crystallization method purifies gallium by utilizing the difference in solubility of impurity elements in the main phase and the non-main phase, so that impurities are precipitated or their distribution is changed. The innovation points of the existing crystallization purification technology are mainly concentrated in aspects such as temperature field control, but no attention is paid to the separation of crystallization mother liquor and crystalline gallium after crystallization and industrial application. In addition, the existing crystallization process starts crystallization from the bottom, and the gallium crystals finally obtained are at the bottom and the crystallization mother liquor is at the top, which makes it difficult to separate the mother liquor.

[0040] In addition, due to the unevenness of the crystal surface and the fact that the crystallization mother liquor only accounts for about 15%, it is difficult to separate the solid and liquid. At present, the solid-liquid separation is mostly achieved by manually extracting the upper layer of liquid with a spoon. After the liquid is separated, the crystal is heated and melted to release high-purity gallium from the bottom. The above process and operation have the following problems: (1) The separation of crystalline gallium and crystallization mother liquor is not complete; (2) The mother liquor that has not been completely decomposed will cause contamination of high-purity gallium due to the enrichment of a large amount of impurities; (3) The entire system is difficult to achieve mechanized control; (4) The crystal growth direction is difficult to control, and there are problems such as entrainment, resulting in low purification efficiency.

[0041] In this regard, the present application proposes a high-purity gallium stirring crystallization device and a crystallization method. The crystallization process in the present application starts from the outside to the inside. During the crystallization process, the crystalline gallium is always located outside the crystallization mother liquid and will not form a wrap, which can achieve efficient separation of the crystal and the crystallization residual liquid. The magnetic stirring method can avoid the intrusion of external impurities in the traditional stirring process, thereby improving the purity of the finished gallium.

[0042] The high-purity gallium stirring crystallization device in the embodiment of the first aspect of the present application comprises a heating component, a crystallization component, a cooling component and a magnetic stirring component. The heating component is used to heat and keep the liquid gallium warm; the crystallization component is used to load the liquid gallium, and the crystallization process of the liquid gallium also occurs in the crystallization component; the cooling component is used to cool the liquid gallium; the magnetic stirring component is used to stir the liquid gallium in the crystallization component and to throw the impurities in the liquid gallium off the crystallized gallium through centrifugal force.

[0043] Specifically, refer to Figure 1 The heating assembly includes a heating pipe 110, a hot water inlet pipe 120 and a hot water outlet pipe 130, wherein the hot water inlet pipe 120 and the hot water outlet pipe 130 are respectively connected to both ends of the heating pipe 110. The hot water inlet pipe 120 is externally connected to a hot water storage tank and guides hot water into the heating pipe 110, and the hot water outlet pipe 130 is used to discharge the hot water in the heating pipe 110 that has been cooled by heat exchange, so that a relatively constant temperature is maintained in the heating pipe 110. The hot water outlet pipe 130 is externally connected to a heating device to reheat the cooled hot water, so that the hot water can re-enter the hot water inlet pipe 120 to form a cycle.

[0044] The crystallization assembly includes a crystallization tube 210 and a drain pipe 220. The crystallization tube 210 is sleeved on the outside of the heating tube 110, so that the heating tube 110 can heat the inner wall of the crystallization tube 210. The drain pipe 220 is connected to the bottom of the crystallization tube 210 to discharge the crystallization mother liquid. The drain pipe 220 is equipped with a valve to control the opening and closing of the drain pipe 220, thereby controlling the crystallization time of the liquid gallium in the crystallization tube 210. After the crystallization is completed, the valve on the drain pipe 220 is opened to discharge the residual crystallization liquid.

[0045] The cooling assembly includes a cooling pipe 310, a cold water inlet pipe 320 and a cold water outlet pipe 330. The cooling pipe 310 is sleeved on the outside of the crystallization tube 210, so that the cooling pipe 310 can cool the outer wall of the crystallization tube 210. The cold water inlet pipe 320 and the cold water outlet pipe 330 are respectively connected to the two ends of the cooling pipe. The cold water inlet pipe 320 is externally connected to a cold water storage tank and guides the cold water into the cooling pipe 310. The cold water outlet pipe 330 is used to discharge the cold water in the cooling pipe 310 that has been heated by heat exchange, so that a relatively constant temperature is maintained in the cooling pipe 310. The cold water outlet pipe 330 is externally connected to a cooling device to re-cool the heated cold water, so that the cold water can re-enter the cold water inlet pipe 320 to form a cycle.

[0046] The magnetic stirring assembly includes a magnetic drive seat 410 and a magnet. The magnet is placed in the crystal tube 210. The magnetic drive seat 410 drives the magnet to move in the crystal tube 210 through magnetic force, and is used to stir the material in the crystal tube 210. When the magnetic drive seat 410 is started, the driving magnet rotates in the crystal tube 210, and the impurities in the liquid gallium are thrown outward, so that it is separated from the crystalline gallium more quickly, and the purity of the crystalline gallium is improved. Compared with traditional mechanical stirring equipment, the magnet is always kept in the crystal tube 210, thereby avoiding the problem of external equipment entering the crystal tube 210 and bringing in external impurities, thereby improving the purity of the finished crystalline gallium.

[0047] The working principle of the high-purity gallium stirring crystallization device is as follows: the gallium liquid to be crystallized is injected into the crystallization tube 210, the heating tube 110 heats the inner wall of the crystallization tube 210, and the cooling tube 310 cools the outer wall of the crystallization tube 210, so as to promote the separation of the liquid phase and the solid phase in the liquid gallium. Moreover, since the contact surface between the cooling tube 310 and the crystallization tube 210 is large, the crystallization efficiency of the liquid gallium in the crystallization tube 210 can be accelerated. At the same time, the magnetic driving seat 410 drives the magnet to move in the crystallization tube 210 to stir the gallium liquid and accelerate the separation of impurities and crystallized gallium.

[0048] Further, refer to Figure 2 , the hot water inlet pipe 120 is connected to the bottom of the heating tube 110, and the hot water outlet pipe 130 is connected to the top of the heating tube 110. Thus, hot water enters from the bottom of the heating tube 110, and the hot water cooled after heat exchange flows out from the top, making full use of the heat in the hot water to heat the crystallization tube 210. Specifically, the material of the heating tube 110 is polytetrafluoroethylene, which has the advantage of good thermal conductivity, making it easier to transfer heat to the crystallization tube 210 and reducing the heat loss during the transfer process.

[0049] Furthermore, the cold water inlet pipe 320 is connected to the bottom of the cooling pipe 310, and the cold water outlet pipe 330 is connected to the top of the cooling pipe 310. Thus, the cold water enters from the bottom of the cooling pipe 310, and the cold water heated after heat exchange flows out from the top, making full use of the cold water to cool the crystallization tube 210. Specifically, the material of the cooling pipe 310 is polytetrafluoroethylene, which has the advantage of good thermal conductivity, so that the cold energy is more easily transferred to the crystallization tube 210 and the loss of cold energy during the transfer process is reduced.

[0050] Specifically, refer to Figure 3 The heating tube 110 is a round tube, and the crystallizing tube 210 and the cooling tube 310 are both annular tubes.

[0051] A crystallization method based on the above-mentioned high-purity gallium stirring crystallization device in the second embodiment of the present application comprises the following steps:

[0052] S100. Pour liquid gallium into the crystal tube 210;

[0053] S200. The hot water inlet pipe 120 is connected to hot water, and the hot water enters the heating tube 110 to transfer heat to the crystallization tube 210;

[0054] S300. The cold water inlet pipe 320 is connected to cold water, and the cold water enters the cooling pipe 310 to transfer cold to the crystallization tube 210;

[0055] S400. Control the flow rate of hot water in the heating tube 110 and the flow rate of cold water in the cooling tube 310, and adjust the ratio of heat and cold transferred to the crystallization tube 210 so that the crystallization mother liquor and the crystallized gallium are separated from each other;

[0056] S500. The magnetic drive seat 410 is turned on, and the magnet moves in the crystal tube 210 under the action of magnetic force, promoting the separation of impurity elements;

[0057] S600. When 10 to 20% of the crystallization mother liquor remains, crystallization is stopped and the remaining gallium liquid is discharged through the drain pipe 220;

[0058] S700. Increase the flow rate ratio and temperature of hot water to melt the crystalline gallium in the crystallization tube 210, and the temperature of the melted crystalline gallium is 40 to 60°C;

[0059] S800. Repeat the above steps multiple times to obtain high-purity gallium.

[0060] Specifically, during the crystallization process, the temperature of the hot water in the heating tube 110 is controlled to be 35-50°C, and the temperature of the cold water in the cooling tube 310 is controlled to be 15-25°C.

[0061] The above is a specific description of the preferred implementation methods of the present application, but the invention is not limited to the embodiments. Those skilled in the art may make various equivalent modifications or substitutions without violating the spirit of the present application, and these equivalent modifications or substitutions are all included in the scope defined by the claims of the present application.

Claims

1. A high-purity gallium stirring crystallization device, characterized in that: include: A heating component, the heating component comprising a heating pipe, a hot water inlet pipe and a hot water outlet pipe, the hot water inlet pipe and the hot water outlet pipe are respectively connected to both ends of the heating pipe; A crystallization assembly, the crystallization assembly comprising a crystallization tube and a liquid discharge pipe, the crystallization tube is sleeved on the outside of the heating tube, and the liquid discharge pipe is connected to the bottom of the crystallization tube to discharge the crystallization mother liquid; A cooling assembly, the cooling assembly comprising a cooling pipe, a cold water inlet pipe and a cold water outlet pipe, the cooling pipe is sleeved on the outside of the crystallization tube, and the cold water inlet pipe and the cold water outlet pipe are respectively connected to two ends of the cooling pipe; A magnetic stirring assembly, the magnetic stirring assembly comprising a magnetic driving seat and a magnet, the magnet being placed in the crystallization tube, the magnetic driving seat driving the magnet to move in the crystallization tube by magnetic force, and being used to stir the substance in the crystallization tube; The gallium liquid to be crystallized is injected into the crystallization tube, the heating tube heats the inner wall of the crystallization tube, and the cooling tube cools the outer wall of the crystallization tube; The magnetic driving seat drives the magnet to move in the crystallization tube to stir the gallium liquid and accelerate the separation of impurities and crystallized gallium.

2. The high-purity gallium stirring crystallization device according to claim 1, characterized in that: The hot water inlet pipe is connected to the bottom of the heating pipe, and the hot water outlet pipe is connected to the top of the heating pipe.

3. The high-purity gallium stirring crystallization device according to claim 1, characterized in that: The material of the heating tube is polytetrafluoroethylene.

4. The high-purity gallium stirring crystallization device according to claim 1, characterized in that: The cold water inlet pipe is connected to the bottom of the cooling pipe, and the cold water outlet pipe is connected to the top of the cooling pipe.

5. The high-purity gallium stirring crystallization device according to claim 1, characterized in that: The cooling tube is made of polytetrafluoroethylene.

6. The high-purity gallium stirring crystallization device according to claim 1, characterized in that: The drain pipe is provided with a valve to control the opening and closing of the drain pipe.

7. The high-purity gallium stirring crystallization device according to any one of claims 1 to 6, characterized in that: The heating tube is a round tube, and the crystallization tube and the cooling tube are both annular tubes.

8. A crystallization method based on the high-purity gallium stirring crystallization device according to any one of claims 1 to 7, characterized in that: include: pouring liquid gallium into the crystallization tube; The hot water inlet pipe is externally connected to hot water, and the hot water enters the heating tube to transfer heat to the crystallization tube; The cold water inlet pipe is externally connected to cold water, and the cold water enters the cooling pipe to transfer cold energy to the crystallization tube; Controlling the flow of hot water in the heating tube and the flow of cold water in the cooling tube, adjusting the ratio of heat and cold transferred to the crystallization tube, so that the crystallization mother liquor and the crystallized gallium are separated from each other; The magnetic driving seat is turned on, and the magnet moves in the crystal tube under the action of magnetic force, thereby promoting the separation of impurity elements; When 10-20% of the crystallization mother liquor remains, the crystallization is stopped, and the remaining gallium liquid is discharged through the liquid discharge pipe; Increasing the flow rate ratio and temperature of hot water to melt the crystalline gallium in the crystallization tube; Repeat the above steps several times to obtain high-purity gallium.

9. The crystallization method according to claim 8, characterized in that: The temperature of the hot water is 35-50°C.

10. The crystallization method according to claim 8, characterized in that: The temperature of the cold water is 15-25°C.

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