A germanium ingot refining device based on coupling of fluorinated salt assistance and reducing atmosphere

Abstract

The application provides a germanium ingot refining device based on fluorinated salt assistance and reduction atmosphere coupling, and relates to the field of metal smelting, comprising a furnace body, a closed refining reaction cavity is formed in the furnace body, an upper reaction zone and a lower reaction zone are arranged in the furnace body; a reduction gas introduction joint is connected to the top of the furnace body and connected with an external gas supply system, and is used for introducing a reducing atmosphere into the lower reaction zone; a fluorinated salt feeding component is arranged on one side of the furnace body; a mixing mechanism is arranged in the middle of the furnace body; and an exhaust system is connected to the top of the furnace body. The application realizes that the fluorinated salt solution is uniformly sprayed in the form of atomization on the surface of GeO2 raw materials or molten germanium, and solves the problems of uneven addition of fluorinated salt, small contact area and low reaction efficiency in the prior art. The atomization spraying greatly increases the reaction interface, so that the fluorination reaction is more sufficient and fast, and then the stirring of the mixing mechanism is matched, so that the reaction rate is further improved.

Description

Technical Field

[0001] This invention relates to the field of metal smelting, and more specifically, to a germanium ingot refining equipment based on the coupling of fluoride salt assistance and reducing atmosphere. Background Technology

[0002] Germanium, as an important rare and dispersed metal, is widely used in high-tech fields such as infrared optics, fiber optic communication, solar cells, and aerospace due to its excellent optical and semiconductor properties. In the production of high-purity germanium, the reduction and purification of germanium dioxide (GeO2) is a crucial step. However, the traditional hydrogen reduction method has limited ability to remove certain impurities (especially non-metallic elements such as silicon and arsenic), making it difficult to further improve the purity of germanium ingots and meet the semiconductor industry's demand for 7N-grade ultra-high-purity germanium. To improve the impurity removal rate, existing technologies have introduced fluoride salts (such as ammonium fluoride) as refining agents, utilizing their property of reacting with impurities to generate volatile fluorides to remove them.

[0003] However, the following technical challenges exist in the fluoride-assisted reduction process:

[0004] Uneven mixing: Existing feeding methods mostly involve directly adding solid salt or simply spraying it in, which results in insufficient contact between fluoride salt and GeO2 powder or molten germanium, leading to low reaction efficiency and unstable impurity removal effect.

[0005] Therefore, we have made improvements to this and proposed a germanium ingot refining equipment based on the coupling of fluoride salt assistance and reducing atmosphere. Summary of the Invention

[0006] The purpose of this invention is to provide a germanium ingot refining device based on the coupling of fluoride salt assistance and reducing atmosphere, which solves the problem of uneven mixing of fluoride salt and materials.

[0007] The application is as follows:

[0008] A germanium ingot refining apparatus based on fluoride salt-assisted and reducing atmosphere coupling, comprising:

[0009] The furnace body has a sealed refining reaction chamber inside. The furnace body is provided with an upper reaction zone and a lower reaction zone. The upper reaction zone is configured to capture impurities such as fluorides volatilized from the lower reaction zone. The lower reaction zone is configured to contain germanium dioxide raw material to be refined and fluoride salts, and is equipped with a heating device to provide the temperature required for the reduction reaction.

[0010] The reducing gas inlet connector is connected to the top of the furnace body and to the external gas supply system, and is used to introduce a reducing atmosphere into the lower reaction zone;

[0011] A fluoride salt feeding component is located on one side of the furnace body. The output end of the fluoride salt feeding component passes through one end of the furnace body and is connected to a spraying assembly. The spraying assembly is located on the top of the furnace body to spray liquid toward the furnace body.

[0012] A mixing mechanism, located in the middle of the furnace body, is used to stir and mix the mixture inside the furnace body;

[0013] An exhaust system, connected to the top of the furnace body, is configured to discharge the treated exhaust gas from the upper reaction zone.

[0014] As a preferred technical solution of this application, the heating device is an electric heating wire spirally wound on the bottom wall of the furnace body.

[0015] As a preferred technical solution of this application, the fluoride salt feeding component includes a storage container, a conveying pipeline and a supply pump, wherein the conveying pipeline connects the supply pump, the storage container and the furnace body.

[0016] As a preferred technical solution of this application, the spraying assembly includes a double-ring conduit fixedly connected to the inner wall of the furnace body. The double-ring conduit is connected to a conveying pipeline, and an atomizing nozzle is connected to the bottom of the double-ring conduit. Multiple atomizing nozzles are arranged in a ring array at the bottom of the double-ring conduit.

[0017] As a preferred technical solution of this application, the mixing mechanism includes a drive motor fixedly installed on the top of the furnace body, a stirring rod fixedly connected to the output end of the drive motor, and stirring blades fixedly connected to the outer wall of the stirring rod.

[0018] As a preferred technical solution of this application, the exhaust system includes a solenoid valve and a pressure relief valve fixedly connected to the top of the furnace body. The output end of the solenoid valve is connected to an exhaust pipe, and the output end of the pressure relief valve is connected to a connecting pipe. One end of the connecting pipe is connected to the exhaust pipe.

[0019] As a preferred technical solution of this application, the exhaust system further includes a filter assembly connected to one end of the exhaust pipe. The end of the exhaust pipe near the filter assembly is a U-shaped structure. An injection pipe is connected to the middle of the U-shaped structure. A plug is threaded to the top of the injection pipe. Alkaline absorbent liquid is injected into the U-shaped structure through the injection pipe.

[0020] As a preferred technical solution of this application, the filter assembly includes a filter cylinder and an air outlet cover threaded to the top of the filter cylinder, and the filter cylinder is filled with a biological packing layer.

[0021] As a preferred technical solution of this application, the biological filler layer is composed of multiple layers of modified polyurethane sponge filler blocks stacked together. Each layer of biological filler blocks is provided with airflow channels distributed in a grid pattern to prevent the filler from caking and reduce airflow resistance.

[0022] As a preferred technical solution of this application, the bottom of the furnace body is also provided with a pressure gauge and a feeding port, and the top of the feeding port is detachably connected with a sealing cover.

[0023] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0024] In the scheme of this application:

[0025] 1. By using a spraying assembly and a double-ring conduit, the fluoride salt solution is uniformly sprayed in an atomized form onto the surface of GeO2 raw material or molten germanium, solving the problems of uneven fluoride salt addition and small contact area leading to low reaction efficiency in existing technologies. The atomized spray significantly increases the reaction interface, making the fluorination reaction more complete and rapid. Combined with the stirring of the mixing mechanism, the reaction rate is further improved.

[0026] 2. Through the combination of the U-shaped structure and alkaline absorbent in the exhaust system, the problems of exhaust corrosion and pollution are effectively solved. The U-shaped pipe structure uses the principle of water seal or liquid seal to force the exhaust gas through the alkaline absorbent, which efficiently removes corrosive gases such as acidic hydrogen fluoride and protects the subsequent pipelines and the environment.

[0027] 3. Through the special structural design of the biological packing layer: by using multi-layer modified polyurethane sponge packing blocks and their grid-like airflow channels, while ensuring a high specific surface area to capture tiny droplets, it effectively prevents packing caking and excessive airflow resistance, thus ensuring the continuous and stable operation of the refining process. Attached Figure Description

[0028] Figure 1 A three-dimensional structural schematic diagram of a germanium ingot refining device based on the coupling of fluoride salt assistance and reducing atmosphere provided in this application;

[0029] Figure 2 A second-view structural schematic diagram of a germanium ingot refining device based on the coupling of fluoride salt assistance and reducing atmosphere provided in this application;

[0030] Figure 3 A schematic diagram of the mixing mechanism structure of a germanium ingot refining device based on the coupling of fluoride salt assistance and reducing atmosphere provided in this application;

[0031] Figure 4 A side view of a germanium ingot refining device based on the coupling of fluoride salt assistance and reducing atmosphere provided in this application;

[0032] Figure 5 A cross-sectional structural schematic diagram of a germanium ingot refining device based on the coupling of fluoride salt assistance and reducing atmosphere provided for this application;

[0033] Figure 6A schematic diagram of the structure of a fluoride salt feeding component in a germanium ingot refining equipment based on the coupling of fluoride salt assistance and reducing atmosphere, provided for this application;

[0034] Figure 7 This application provides a schematic diagram of the exhaust system structure of a germanium ingot refining equipment based on the coupling of fluoride salt assistance and reducing atmosphere.

[0035] Marked in the image:

[0036] 1. Furnace body; 11. Upper reaction zone; 12. Lower reaction zone; 13. Heating device; 14. Pressure gauge; 15. Feed port;

[0037] 2. Reducing gas inlet connector;

[0038] 3. Fluoride salt feeding component; 31. Spraying assembly; 311. Double-ring conduit; 312. Atomizing nozzle; 32. Storage container; 33. Delivery pipeline; 34. Supply pump;

[0039] 4. Mixing mechanism; 41. Drive motor; 42. Stirring rod; 43. Stirring blade;

[0040] 5. Exhaust system; 51. Solenoid valve; 52. Pressure relief valve; 53. Exhaust pipe; 54. Connecting pipe; 55. U-shaped structure; 56. Injection pipe; 57. Filter cartridge; 58. Exhaust cover; 59. Biological packing layer. Detailed Implementation

[0041] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments.

[0042] Therefore, the following detailed description of embodiments of the present invention is not intended to limit the scope of the claimed invention, but merely illustrates some embodiments of the invention. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without inventive effort are within the scope of protection of the present invention.

[0043] It should be noted that, unless otherwise specified, the embodiments and features and technical solutions in the present invention can be combined with each other.

[0044] It should be noted that similar labels and letters in the following figures indicate similar items. Therefore, once an item is defined in one figure, it does not need to be further defined and explained in subsequent figures.

[0045] In the description of this invention, it should be noted that the terms "upper," "lower," etc., indicate the orientation or positional relationship based on the orientation or positional relationship shown in the accompanying drawings, or the orientation or positional relationship commonly used when the product of this invention is in use, or the orientation or positional relationship commonly understood by those skilled in the art. These terms are only for the convenience of describing this invention and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation, and therefore should not be construed as a limitation of this invention. In addition, the terms "first," "second," etc., are only used to distinguish descriptions and should not be construed as indicating or implying relative importance.

[0046] Please see Figures 1 to 7 This invention provides a technical solution: a germanium ingot refining device based on fluoride salt-assisted and reducing atmosphere coupling, comprising:

[0047] Furnace body 1, with a sealed refining reaction chamber inside. Furnace body 1 is provided with an upper reaction zone 11 and a lower reaction zone 12. The upper reaction zone is configured to capture impurities such as fluorides volatilized from the lower reaction zone. The lower reaction zone 12 is configured to contain germanium dioxide raw material to be refined and fluoride salt, and is equipped with a heating device 13 to provide the temperature required for the reduction reaction. The heating device 13 is a heating wire spirally wound on the bottom wall of the furnace body 1, and the heating wire is connected to a temperature controller for temperature control.

[0048] A condenser can be installed in the upper reaction zone 11 to capture volatile impurities such as fluoride.

[0049] The bottom of the furnace body 1 is also equipped with a pressure gauge 14 and a feeding port 15, and the top of the feeding port 15 is detachably connected with a sealing cover.

[0050] The reducing gas inlet connector 2 is connected to the top of the furnace body 1 and to the external gas supply system, and is used to introduce a reducing atmosphere into the lower reaction zone 12.

[0051] The fluoride salt feeding component 3 is located on one side of the furnace body 1. The output end of the fluoride salt feeding component 3 passes through one end of the furnace body 1 and is connected to the spraying component 31. The spraying component 31 is located on the top of the furnace body 1 to spray liquid toward the furnace body 1.

[0052] The mixing mechanism 4 is located in the middle of the furnace body 1 and is used to stir and mix the mixture inside the furnace body 1.

[0053] The exhaust system 5 is connected to the top of the furnace body 1 and is configured to discharge the treated exhaust gas from the upper reaction zone 11.

[0054] Specifically, the spiral winding method ensures that heat is radiated evenly at the bottom, ensuring that the material is heated consistently and avoiding local overheating. The pressure gauge 14 monitors the pressure inside the furnace in real time, and the feeding port 15 facilitates the entry and exit of materials. The sealing cover and the feeding port 15 are detachably connected by bolts. The top of the furnace body 1 is connected to a reducing gas inlet connector 2 for introducing reducing gases such as hydrogen.

[0055] As a preferred embodiment, based on the above method, the fluoride salt feeding component 3 further includes a storage container 32, a conveying pipeline 33 and a supply pump 34, with the conveying pipeline 33 connecting the supply pump 34, the storage container 32 and the furnace body 1.

[0056] The spraying assembly 31 includes a double-ring conduit 311 fixedly connected to the inner wall of the furnace body 1. The double-ring conduit 311 is connected to the delivery pipeline 33. The bottom of the double-ring conduit 311 is connected to an atomizing nozzle 312. Multiple atomizing nozzles 312 are arranged in a ring array at the bottom of the double-ring conduit 311.

[0057] Specifically, when the supply pump 34 is started, the fluoride salt liquid is pumped into the double-ring conduit 311 and sprayed out from each atomizing nozzle 312, forming uniform mist droplets that cover the lower raw material layer. This design not only has a large coverage area but also produces small atomized droplets that can quickly penetrate into the gaps between materials and participate in the reaction, greatly improving refining efficiency.

[0058] As a preferred embodiment, based on the above method, the mixing mechanism 4 further includes a drive motor 41 fixedly installed on the top of the furnace body 1, a stirring rod 42 fixedly connected to the output end of the drive motor 41, and a stirring blade 43 fixedly connected to the outer wall of the stirring rod 42.

[0059] Specifically, during the refining process, the drive motor 41 drives the stirring blade 43 to rotate, forcing the melt to flow, so that the injected fluoride salt and germanium melt are fully mixed, while also promoting heat transfer and bubble rising inside the melt.

[0060] As a preferred embodiment, based on the above method, the exhaust system 5 further includes a solenoid valve 51 and a pressure relief valve 52 fixedly connected to the top of the furnace body 1. The output end of the solenoid valve 51 is connected to an exhaust pipe 53, and the output end of the pressure relief valve 52 is connected to a connecting pipe 54. One end of the connecting pipe 54 is connected to the exhaust pipe 53.

[0061] The exhaust system 5 also includes a filter assembly connected to one end of the exhaust pipe 53. The end of the exhaust pipe 53 near the filter assembly is a U-shaped structure 55. An injection pipe 56 is connected to the middle of the U-shaped structure 55. A plug is threaded to the top of the injection pipe 56. An alkaline absorbent liquid is injected into the U-shaped structure 55 through the injection pipe 56.

[0062] Specifically, when the high-temperature exhaust gas passes through the U-shaped structure 55, it is forced to pass through the alkaline liquid, where acidic gases such as HF and SiF4 are neutralized and absorbed, effectively reducing the corrosiveness of the gas. After being washed by the U-shaped structure 55, the gas enters the filter assembly.

[0063] As a preferred embodiment, based on the above method, the filter assembly further includes a filter cylinder 57 and an air outlet cover 58 threadedly connected to the top of the filter cylinder 57, and the filter cylinder 57 is filled with a biological packing layer 59.

[0064] The biological packing layer 59 is composed of multiple layers of modified polyurethane sponge packing blocks stacked together. Each layer of biological packing layer 59 has grid-like airflow channels between the packing blocks to prevent packing caking and reduce airflow resistance.

[0065] Furthermore, the gas enters the filter assembly, where the biological packing layer 59 is composed of multiple layers of modified polyurethane sponge packing blocks stacked together. Each layer of biological packing layer 59 has grid-like airflow channels between the packing blocks. This structure not only provides a huge specific surface area to adsorb residual micro-droplets and dust, but also the grid-like channels effectively prevent the packing from caking under long-term humid conditions, ensuring smooth airflow and reducing system resistance.

[0066] Specifically, during operation / use of this germanium ingot refining equipment based on fluoride salt assisted and reducing atmosphere coupling: charging: the germanium dioxide (GeO2) raw material to be refined is put into the lower reaction zone 12 through the feeding port 15, and the sealing cover is closed to ensure the furnace body is sealed.

[0067] Heating and reduction: Start the heating device 13 to heat the furnace. Introduce hydrogen into the furnace through the reducing gas inlet connector 2 to establish a reducing atmosphere. When the temperature reaches the reduction and melting temperature of GeO2, the reduction reaction begins.

[0068] Adding refining agent: When the material begins to melt or the reaction proceeds to a certain stage, the supply pump 34 is started. The fluoride salt (such as ammonium fluoride solution) in the storage container 32 is transported to the top double-ring conduit 311 through the conveying pipeline 33, and is evenly atomized and sprayed onto the surface of the material through the atomizing nozzle 312. The fluoride salt reacts rapidly with impurities in the melt (such as silicon, aluminum, etc.) to generate highly volatile fluorides.

[0069] Stirring and mixing: Simultaneously start the drive motor 41 to drive the stirring rod 42 and stirring blade 43 to rotate, mechanically stir the melt, ensure that the fluoride salt is in full contact with the melt, and accelerate the migration of impurities to the gas phase.

[0070] Exhaust gas treatment: The gas produced by the reaction (including residual hydrogen, water vapor and volatile impurities such as fluoride) rises to the upper reaction zone 11 of the furnace body. Some of the heavier impurities may condense on the cold wall. Then, the solenoid valve 51 is opened and the gas is discharged through the exhaust pipe 53. The gas first passes through the U-shaped structure 55 filled with alkaline absorbent liquid, and the acidic gas is neutralized and washed. Then the gas enters the filter cartridge 57 and is deeply filtered through the biological packing layer 59 to remove the entrained tiny droplets and particles. Finally, the clean gas is discharged or collected.

[0071] Discharge: After the reaction is complete, stop heating and gas supply, and after the furnace body cools down, remove the high-purity germanium ingots deposited at the bottom.

[0072] The above embodiments are only used to illustrate the present invention and are not intended to limit the technical solutions described herein. Although the present invention has been described in detail with reference to the above embodiments, the present invention is not limited to the specific embodiments described above. Therefore, any modifications or equivalent substitutions to the present invention, as well as all technical solutions and improvements that do not depart from the spirit and scope of the invention, are covered within the scope of the claims of the present invention.

Claims

1. A germanium ingot refining device based on fluoride salt-assisted and reducing atmosphere coupling, characterized in that, include: The furnace body (1) has a sealed refining reaction chamber inside. The furnace body (1) is provided with an upper reaction zone (11) and a lower reaction zone (12). The upper reaction zone is configured to capture impurity fluorides volatilized from the lower reaction zone. The lower reaction zone (12) is configured to contain germanium dioxide raw material to be refined and fluoride salts, and is equipped with a heating device (13) to provide the temperature required for the reduction reaction. The reducing gas inlet connector (2) is connected to the top of the furnace body (1) and connected to the external gas supply system for introducing a reducing atmosphere into the lower reaction zone (12); A fluoride salt feeding component (3) is provided on one side of the furnace body (1). The output end of the fluoride salt feeding component (3) passes through one end of the furnace body (1) and is connected to a spraying assembly (31). The spraying assembly (31) is provided on the top of the furnace body (1) to spray liquid toward the furnace body (1). The mixing mechanism (4) is located in the middle of the furnace body (1) and is used to stir and mix the mixture inside the furnace body (1); An exhaust system (5) is connected to the top of the furnace body (1) and is configured to discharge the treated exhaust gas from the upper reaction zone (11).

2. The germanium ingot refining equipment based on fluoride salt assistance and reducing atmosphere coupling according to claim 1, characterized in that, The heating device (13) is an electric heating wire spirally wound on the bottom wall of the furnace body (1).

3. The germanium ingot refining equipment based on fluoride salt assistance and reducing atmosphere coupling according to claim 1, characterized in that, The fluoride feeding component (3) includes a storage container (32), a conveying pipeline (33) and a supply pump (34), wherein the conveying pipeline (33) connects the supply pump (34), the storage container (32) and the furnace body (1).

4. The germanium ingot refining equipment based on fluoride salt assistance and reducing atmosphere coupling according to claim 1, characterized in that, The spraying assembly (31) includes a double-ring conduit (311) fixedly connected to the inner wall of the furnace body (1). The double-ring conduit (311) is connected to the conveying pipeline (33). The bottom of the double-ring conduit (311) is connected to an atomizing nozzle (312). Multiple atomizing nozzles (312) are arranged in a ring array at the bottom of the double-ring conduit (311).

5. The germanium ingot refining equipment based on fluoride salt assistance and reducing atmosphere coupling according to claim 1, characterized in that, The mixing mechanism (4) includes a drive motor (41) fixedly installed on the top of the furnace body (1), and a stirring rod (42) is fixedly connected to the output end of the drive motor (41). A stirring blade (43) is fixedly connected to the outer wall of the stirring rod (42).

6. The germanium ingot refining equipment based on fluoride salt-assisted and reducing atmosphere coupling according to claim 1, characterized in that, The exhaust system (5) includes a solenoid valve (51) and a pressure relief valve (52) fixedly connected to the top of the furnace body (1). The output end of the solenoid valve (51) is connected to an exhaust pipe (53), and the output end of the pressure relief valve (52) is connected to a connecting pipe (54). One end of the connecting pipe (54) is connected to the exhaust pipe (53).

7. The germanium ingot refining equipment based on fluoride salt assistance and reducing atmosphere coupling according to claim 6, characterized in that, The exhaust system (5) also includes a filter assembly connected to one end of the exhaust pipe (53). The end of the exhaust pipe (53) near the filter assembly is a U-shaped structure (55). The middle part of the U-shaped structure (55) is connected to an injection pipe (56). The top of the injection pipe (56) is threaded with a plug. The U-shaped structure (55) is injected with alkaline absorbent through the injection pipe (56).

8. The germanium ingot refining equipment based on fluoride salt assistance and reducing atmosphere coupling according to claim 7, characterized in that, The filter assembly includes a filter cartridge (57) and an air outlet cap (58) threaded to the top of the filter cartridge (57), the filter cartridge (57) being filled with a biological packing layer (59).

9. A germanium ingot refining device based on fluoride salt assistance and reducing atmosphere coupling according to claim 8, characterized in that, The biological filler layer (59) is composed of multiple layers of modified polyurethane sponge filler blocks stacked together. Each biological filler layer (59) has a grid-like distribution of airflow channels between the filler blocks to prevent the filler from caking and reduce airflow resistance.

10. The germanium ingot refining equipment based on fluoride salt-assisted and reducing atmosphere coupling according to claim 1, characterized in that, The bottom of the furnace body (1) is also equipped with a pressure gauge (14) and a feeding port (15), and the top of the feeding port (15) is detachably connected with a sealing cover.

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