A method and device for efficiently purifying germanium based on alloying

Abstract

The present invention belongs to the field of metallurgy technology, and in particular relates to a method and device for efficiently purifying germanium based on alloying. The device comprises a housing, a high-temperature furnace body, a feeding system, an atmosphere system, and a crystallization system. A high-purity graphite crucible is disposed within the high-temperature furnace body, and an upper heater and a lower heater are disposed on the outside of the graphite crucible. The upper end opening of the high-temperature furnace body is connected to the feeding system, including a connecting component, a sealing kit, and a feeding port. The lower end opening of the high-purity graphite crucible is connected to the crystallization system, which includes a crystallization heater arranged in an annular manner to form a crystallization hole. A material removal component and a crystallization table are disposed within the crystallization hole, and the lower end of the crystallization table is connected to a transmission shaft and a motor. The atmosphere system includes an air inlet, an air outlet, a vacuum pump, and an air path valve. This device achieves efficient purification of germanium based on the principles of impurity alloying and physical segregation. To a certain extent, it can achieve continuous purification of crude germanium. It has strong raw material applicability, low cost, and good industrial application prospects.

Description

Technical Field

[0001] The present invention belongs to the technical field of metallurgy, and in particular relates to a method and device for efficiently purifying germanium based on alloying. Background Art

[0002] Germanium is an extremely important rare earth metal, with global reserves of only 8,600 tons. However, it plays an irreplaceable role in semiconductor devices, nuclear physics detection, fiber optic communications, medical devices, and defense and military applications. Consequently, many countries, including China, have designated it as a strategic metal. Germanium's applications are closely tied to its purity. Products like infrared lenses and mirrors require a purity of 6N or higher, while semiconductor chips and transistors require a purity of 9N or higher. Therefore, germanium purification is crucial.

[0003] Traditional germanium purification methods are divided into four stages: first, the germanium-containing ore or waste is purified by pyro-roasting or wet leaching to obtain germanium concentrate; then, relatively pure germanium tetrachloride is obtained through hydrochloric acid distillation and rectification; then, reduced germanium ingots are obtained through hydrolysis and hydrogen reduction; and finally, high-purity germanium is obtained through purification methods such as zone smelting. This process is long and very complex, especially the later zone smelting stage, which has a long cycle, high energy consumption, and difficulty in removing impurities. It is worth noting that for certain elemental waste materials such as germanium cutting waste and waste germanium products, the traditional recovery method involves the front-end pyro-roasting enrichment and hydrochloric acid distillation stages. This recovery cycle is long and costly, with large germanium losses and high equipment requirements.

[0004] Therefore, it is necessary to propose a new process for efficiently and short-processing the recovery of low-grade germanium waste and to achieve high-purity preparation of germanium. Summary of the Invention

[0005] In order to overcome the deficiencies and defects mentioned in the background technology, the present invention realizes the preparation of high-purity germanium and the removal of impurities based on the principles of alloying purification and physical segregation, and provides a method and device for efficiently purifying germanium.

[0006] In an embodiment of the present invention, the present invention proposes a device for efficiently purifying germanium based on alloying, the device comprising a housing, a high-temperature furnace, a feeding system, an atmosphere system, and a crystallization system;

[0007] A high-purity graphite crucible is provided in the high-temperature furnace body, and an upper heater and a lower heater are provided outside the graphite crucible;

[0008] The upper end of the high-temperature furnace body is open, and a feeding system is connected thereto. The feeding system includes a connecting component, a sealing kit, and a feeding port.

[0009] The lower end opening of the high-purity graphite crucible is connected to a crystallization system, which includes a crystallization heater. The crystallization heater is arranged in an annular shape to form a crystallization hole. A material taking component and a crystallization table are provided in the crystallization hole. The lower end of the crystallization table is connected to a transmission shaft and a motor.

[0010] The atmosphere system comprises an air inlet, an air outlet, a vacuum pump and an air circuit valve, and the air inlet and the air outlet are arranged on the shell.

[0011] In an embodiment of the present invention, the device further comprises a control system, which is electrically connected to the upper heater, the lower heater, the crystal heater, the motor, the gas valve, and the on / off switch of the feeding port.

[0012] In the device for efficiently purifying germanium of the present invention, the upper heater and the lower heater are arranged around the outside of the graphite crucible to regulate the temperature inside the high-purity graphite crucible.

[0013] In the device for efficiently purifying germanium of the present invention, the material taking component is an oscillating device, and is tightly fitted with the lower opening of the high-purity graphite crucible.

[0014] Based on the same inventive concept, the present invention also provides a method for efficiently purifying germanium based on alloying using the above-mentioned device, comprising the following steps:

[0015] (1) Fixing a high-purity germanium seed crystal on a seed crystal table, raising the seed crystal table to the bottom of a graphite crucible via a transmission shaft so that the upper surface of the seed crystal is flush with the bottom of the crucible;

[0016] (2) fully mixing the crude germanium and the alloy metal under an inert gas protection environment, pre-baking, cooling and crushing to obtain a germanium alloy mixture material, and then feeding the germanium alloy mixture material into a high-purity graphite crucible through a feed port;

[0017] (3) exhausting the air in the high-temperature furnace body and introducing hydrogen;

[0018] (4) turning on the lower heater and the upper heater to increase the temperature in the graphite crucible so that the germanium alloy mixture material is fully melted to obtain a saturated germanium alloy melt;

[0019] (5) After the saturated germanium alloy melt stabilizes, the lower heater is adjusted to reduce the temperature of the lower end of the graphite crucible to a preset temperature value, and the temperature of the crystallization table is adjusted by the heater to allow the germanium in the saturated germanium alloy melt to crystallize and grow on the seed crystal, while the seed crystal table is controlled to move downward by the transmission shaft;

[0020] (6) When the preset crystallization amount is reached, the temperature in the graphite crucible is lowered to solidify the germanium alloy melt in the graphite crucible, and the generated high-purity germanium is taken out to obtain a high-purity germanium product.

[0021] In an embodiment of the present invention, the method further includes:

[0022] (7) Fixing the high-purity germanium seed crystal on the seed crystal table again and raising it to contact with the solidified germanium alloy melt; feeding crude germanium into the graphite crucible through the feed port; repeating steps (4)-(6) to obtain a high-purity germanium product;

[0023] (8) Repeat steps (4) to (7) to purify the crude germanium multiple times.

[0024] (9) After multiple purifications of crude germanium, the remaining alloy body in the crucible is heated and melted and discharged from the lower port of the graphite crucible. The high-purity graphite crucible is cleaned to prepare for the next set of purifications.

[0025] In the purification method of the present invention, the high-purity germanium seed crystal is high-purity germanium with a purity of 5N or above.

[0026] In the purification method of the present invention, the alloy metal is any one or more of Cu, Al, Mg, and Fe, and the molar ratio of crude germanium to the alloy metal is 0.5-3.

[0027] The purification method of the present invention includes the following technical features:

[0028] In step (4), the temperature in the graphite crucible is 900-1200° C.;

[0029] In step (5), the preset temperature value is 700-900° C.; the temperature of the crystallization table is 400-600° C., and the downward movement rate of the crystallization table is 10 mm-100 mm / h;

[0030] In step (6), the preset crystallization amount is 0.4 to 0.8 times the amount of crude germanium input.

[0031] The purification method of the present invention includes the following technical features:

[0032] In step (7), the amount of crude germanium added is the same as the amount of crude germanium in step (2);

[0033] In step (8), the number of times is less than 20 times.

[0034] Compared with the prior art, the present invention has the following beneficial effects:

[0035] (1) The present invention designs a device for efficiently purifying germanium based on the impurity alloying principle and the physical segregation principle. A high-temperature furnace body is provided to heat crude germanium and other alloy metals and control the temperature of different areas to achieve the precipitation of high-purity germanium. A crystallization table is provided at the lower end of the high-temperature furnace body to load high-purity germanium seed crystals to achieve positioned crystallization of high-purity germanium. A material-taking component is provided to separate high-purity germanium from the mixed melt. At the same time, the device can achieve multiple germanium purifications and, to a certain extent, can achieve continuous purification of crude germanium. The raw materials have strong applicability and low cost, and have good industrial application prospects.

[0036] (2) The method for purifying high-purity germanium of the present invention mainly utilizes the principle of physical segregation to achieve the preparation of high-purity germanium and the removal of impurities. Impurities such as B, P, and Si have high solubility in the germanium alloy melt and tend to be enriched in the alloy melt during the germanium crystallization process, resulting in a high-purity germanium product. In addition, germanium can form a saturated alloy with metals such as copper, aluminum, magnesium, and iron under certain ratios. The melting point of the alloy is lower than that of a single metal, and the melting point is reduced by nearly 200 to 300°C, which can greatly reduce energy consumption. The method has the advantages of a short process flow, a short cycle, simple equipment, and high purification efficiency, and can achieve efficient recovery and purification of single-element germanium waste. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings described below are some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0038] Figure 1 This is a schematic diagram of the structure of the device for efficiently purifying germanium based on alloying provided by the present invention.

[0039] [Description of Reference Numerals]

[0040] 1-high-purity graphite crucible; 2-crude germanium; 3-germanium alloy melt; 4-lower heater; 5-upper heater; 6-crystallization heater; 7-high-purity germanium; 8-drive shaft; 9-seed crystal table; 10-high-temperature furnace body; 11-housing; 12-air inlet; 13-air outlet; 14-feed port; 15-sealing kit; 16-connecting parts; 17-feeding parts. DETAILED DESCRIPTION

[0041] To facilitate understanding of the present invention, the present invention will be described in more comprehensive and detailed form below in conjunction with the accompanying drawings and preferred embodiments. However, the protection scope of the present invention is not limited to the following specific embodiments.

[0042] Unless otherwise defined, all technical terms used hereinafter have the same meanings as those generally understood by those skilled in the art. The technical terms used herein are only for the purpose of describing specific embodiments and are not intended to limit the scope of protection of the present invention.

[0043] Unless otherwise specified, various raw materials, reagents, instruments and equipment used in the present invention can be purchased from the market or prepared by existing methods.

[0044] like Figure 1 As shown, the device for efficiently purifying germanium through alloying of the present invention specifically includes: a housing, a high-temperature furnace body, a feeding system, an atmosphere system, and a crystallization system. A high-purity graphite crucible 1 is disposed within the high-temperature furnace body 10. An upper heater 5 and a lower heater 4 are disposed around the outside of the graphite crucible. The upper and lower heaters are used to control the temperature within the high-purity graphite crucible 1. The two heaters can be used to separately control the temperature at different locations within the high-purity graphite crucible 1, thereby ensuring the melt state of the melt and providing conditions for the precipitation of high-purity germanium crystals. The upper end of the high-temperature furnace body is open and is provided with a connecting component 16 and a sealing kit 15. The connecting component 16 is connected to the feeding port 14. The connecting component 16 is used to prevent damage to the sealing kit 15 due to high temperature and to collect volatile components within the high-purity graphite crucible 1. The lower opening of the high-purity graphite crucible 1 is connected to a crystallization system, which includes a crystallization heater 6. The crystallization heater 6 is arranged around a crystallization hole. A material removal component 17 and a crystallization table 9 are provided in the crystallization hole. The material removal component 17 is an oscillating device for separating the high-purity germanium product and the germanium alloy melt solid to facilitate the removal of the high-purity germanium product. At the same time, the material removal component 17 fits tightly with the lower opening of the high-purity graphite crucible 1 to ensure the sealing inside the high-purity graphite crucible 1. A transmission shaft 8 and a motor are connected to the bottom of the crystallization table 9 to control the upward and downward movement of the crystallization table 9. The atmosphere system includes an air inlet 12, an air outlet 13, a vacuum pump, and an air valve. The air inlet 2 is provided below the outer shell 12, and the air outlet 13 is provided above the outer shell 13.

[0045] The device can also be provided with a control system, which is electrically connected to the above-mentioned upper heater 5, lower heater 4, crystal heater 6, motor, gas circuit valve, feeding port opening and closing switch and other components. For example, a control panel is provided on the device, and corresponding switches and parameter setting programs can be set for each component.

[0046] Based on phase diagram analysis, theoretical calculations and experimental verification, the present invention provides a purification method using the above-mentioned device, which specifically includes the following steps:

[0047] (1) Fix the high-purity germanium seed crystal on the seed crystal table 9, and raise the seed crystal table to the bottom of the graphite crucible 1 through the transmission shaft 8 so that the upper surface of the seed crystal is flush with the bottom of the crucible to facilitate full contact between the seed crystal and the germanium alloy melt.

[0048] (2) Crude germanium and alloy metal are placed in a mixer at a molar ratio of 0.5 to 3:1, and are fully mixed in a sealed and inert gas protected environment. A germanium alloy mixture is obtained by pre-baking, cooling and crushing, and the obtained mixture is put into a high-purity graphite crucible 1 through a feed port 14.

[0049] (3) Atmosphere treatment: Close the air inlet 12 and the feed port 14, and extract the air in the container 10 through the air outlet 13, and close the air outlet 13; open the air inlet 12, and introduce high-purity hydrogen or high-purity inert gas into the high-temperature furnace body 10 to a slightly positive pressure, open the air outlet 13, and maintain a certain hydrogen gas flow rate to avoid the influence of oxygen on the germanium purification process.

[0050] (4) Turn on the lower heater 4 and the upper heater 5, and raise the temperature in the graphite crucible 1 to 900-1200° C. to fully melt the germanium alloy mixture in step (2) to obtain a saturated germanium alloy melt.

[0051] (5) After the melt in step (4) is kept stable for a period of time, heater 4 is adjusted to reduce the temperature of the lower end of the graphite crucible to 700-900°C. The temperature of the crystallization table is adjusted to 400-600°C via heater 6, so that the germanium in the saturated germanium alloy melt 3 crystallizes and grows on the seed crystal. The principle is: to reduce the solubility of germanium in the lower end melt and form a temperature gradient from top to bottom, so that germanium precipitates on the crystallization table under the guidance of the seed crystal. At the same time, the seed crystal table 9 is controlled by the transmission shaft 8 to move downward at a rate of 10 mm to 100 mm / h; this matches the crystallization rate of high-purity germanium.

[0052] (6) When the germanium crystals in step (5) grow to a certain thickness, that is, when the amount of germanium crystals reaches 0.4 to 0.8 times the amount of crude germanium, the temperature in the graphite crucible is lowered to solidify the germanium alloy melt in the graphite crucible, and the generated high-purity germanium is taken out to obtain a high-purity germanium product.

[0053] (7) New high-purity germanium seed crystals are loaded into the graphite crucible 1 through the seed crystal table 9 and raised until they come into contact with the germanium alloy melt; crude germanium is continuously fed into the graphite crucible 1 through the feed port 14, and the amount of crude germanium added is the same as that in step (2); steps (4) to (6) are repeated to obtain a high-purity germanium product.

[0054] (8) Repeat steps (4) to (7) to purify the crude germanium multiple times, the number of times being less than 20 times.

[0055] (9) After multiple purifications of crude germanium, the germanium alloy in the graphite crucible contains more impurities, which are melted by heating and discharged from the lower port of the graphite crucible. The high-purity graphite crucible is cleaned for the next set of purifications.

[0056] The above describes the specific implementation of the present application. In order to objectively illustrate the technical effects produced by the present application, the following examples and comparative examples will be used for description. Before the implementation of each example, the air tightness of the device was tested and the air tightness was good, and the temperature was calibrated. The high-purity graphite crucible was soaked in aqua regia: hydrofluoric acid with a volume ratio of 3:1 for 24 hours, and then soaked in deionized water for 24 hours. After multiple rinses, it was dried in a vacuum drying oven and taken out for use.

[0057] Example 1

[0058] Fix 5N high-purity germanium with a purity of 1.577 W on the crystallization table, and raise the seed crystal table to the bottom of the graphite crucible through the transmission shaft so that the upper surface of the seed crystal is flush with the bottom of the crucible.

[0059] 2000g of crude germanium and 1539g of iron were placed in a mixer and thoroughly crushed and mixed under an inert gas atmosphere. The crude germanium had a purity of approximately 4N5, while the iron had a purity of approximately 3N5, with a molar ratio of approximately 1:1. After pre-calcination, cooling, and crushing, the resulting germanium alloy mixture was placed into a high-purity graphite crucible through a feed port.

[0060] The feeding port was closed, the air in the furnace was completely exhausted through atmosphere treatment, and high-purity hydrogen at 1L / min was introduced into the furnace to avoid the influence of oxygen on the germanium purification process.

[0061] The control system turns on the lower and upper heaters, raising the furnace temperature to 1200°C. Simultaneously, the crystallization table temperature is controlled at 600°C to prevent the seed crystal from melting. The furnace temperature is maintained constant until the material inside is fully melted.

[0062] The heater at the lower end of the high-purity graphite crucible is controlled to lower the temperature to 900°C, and the temperature of the crystallization table is controlled to 600°C, so that the germanium in the saturated germanium alloy melt begins to crystallize and grow on the seed crystal. At the same time, the seed crystal table is controlled to move downward at a rate of 10 mm / h through the transmission shaft.

[0063] After the seed crystal table descends a certain distance, the quality of the high-purity germanium obtained at this time accounts for about 40% of the quality of the crude germanium. The temperature inside the high-purity graphite crucible is lowered to solidify the germanium alloy melt inside the graphite crucible. The generated high-purity germanium is removed by the material removal component to obtain the high-purity germanium product. Samples are taken from the top, middle and bottom positions for testing.

[0064] The results showed that the purities of the upper, middle and lower ends were 5N6, 5N8 and 5N3 respectively.

[0065] Example 2

[0066] Fix 5N high-purity germanium with a purity of 1.577 W on the crystallization table, and raise the seed crystal table to the bottom of the graphite crucible through the transmission shaft so that the upper surface of the seed crystal is flush with the bottom of the crucible.

[0067] 2000g of crude germanium and 1487g of aluminum were placed in a mixer and thoroughly crushed and mixed under an inert gas atmosphere. The crude germanium had a purity of approximately 4N5, and the aluminum used had a purity of approximately 4N5. The molar ratio of crude germanium to aluminum was approximately 0.5:1. After pre-calcination, cooling, and crushing, the resulting germanium alloy mixture was placed into a high-purity graphite crucible through a feed port.

[0068] The feeding port was closed, the air in the furnace was completely exhausted through atmosphere treatment, and high-purity hydrogen at 1L / min was introduced into the furnace to avoid the influence of oxygen on the germanium purification process.

[0069] The control system turns on the lower and upper heaters, raising the furnace temperature to 900°C. Simultaneously, the crystallization table temperature is controlled at 400°C to prevent the seed crystal from melting. The furnace temperature is maintained constant until the material inside is fully melted.

[0070] The heater at the lower end of the high-purity graphite crucible is controlled to lower the temperature to 700°C, and the temperature of the crystallization table is controlled to 400°C, so that the germanium in the saturated germanium alloy melt begins to crystallize and grow on the seed crystal. At the same time, the seed crystal table is controlled to move downward at a rate of 10 mm / h through the transmission shaft.

[0071] After the seed crystal table descends a certain distance, the quality of the high-purity germanium obtained at this time accounts for about 80% of the quality of the crude germanium. The temperature inside the high-purity graphite crucible is lowered to solidify the germanium alloy melt inside the graphite crucible. The generated high-purity germanium is removed by the material removal component to obtain the high-purity germanium product. Samples are taken from the top, middle and bottom positions for testing.

[0072] The results showed that the purities of the upper, middle and lower ends were 5N, 5N6 and 5N4 respectively.

[0073] Example 3

[0074] Fix 5N high-purity germanium with a purity of 1.577 W on the crystallization table, and raise the seed crystal table to the bottom of the graphite crucible through the transmission shaft so that the upper surface of the seed crystal is flush with the bottom of the crucible.

[0075] 2000g of crude germanium and 1750g of copper were placed in a mixer and thoroughly crushed and mixed under an inert gas atmosphere. The crude germanium had a purity of approximately 4N5, and the copper used had a purity of approximately 4N5. The molar ratio of crude germanium to copper was approximately 1:1. After pre-calcination, cooling, and crushing, the resulting germanium alloy mixture was placed into a high-purity graphite crucible through the feed port.

[0076] The feeding port was closed, the air in the furnace was completely exhausted through atmosphere treatment, and high-purity hydrogen at 1L / min was introduced into the furnace to avoid the influence of oxygen on the germanium purification process.

[0077] The control system turns on the lower and upper heaters, raising the furnace temperature to 1200°C. Simultaneously, the crystallization table temperature is controlled at 600°C to prevent the seed crystal from melting. The furnace temperature is maintained constant until the material inside is fully melted.

[0078] The heater at the lower end of the high-purity graphite crucible is controlled to lower the temperature to 750°C, and the temperature of the crystallization table is controlled to 400°C, so that the germanium in the saturated germanium alloy melt begins to crystallize and grow on the seed crystal. At the same time, the seed crystal table is controlled to move downward at a rate of 50 mm / h through the transmission shaft.

[0079] After the seed crystal table descends a certain distance, the quality of the high-purity germanium obtained at this time accounts for about 60% of the crude germanium quality. The temperature inside the high-purity graphite crucible is lowered to solidify the germanium alloy melt inside the graphite crucible. The generated high-purity germanium is removed by the material removal component to obtain the high-purity germanium product. Samples are taken from the top, middle and bottom positions for testing.

[0080] The results showed that the purities of the upper, middle and lower ends were 5N4, 5N6 and 5N3 respectively.

[0081] Example 4

[0082] Fix 5N high-purity germanium with a purity of 1.577 W on the crystallization table, and raise the seed crystal table to the bottom of the graphite crucible through the transmission shaft so that the upper surface of the seed crystal is flush with the bottom of the crucible.

[0083] 2000g of crude germanium and 224g of magnesium were placed in a mixer and thoroughly crushed and mixed under an inert gas atmosphere. The crude germanium had a purity of approximately 4N5, while the magnesium used had a purity of approximately 3N5. The molar ratio of crude germanium to magnesium was approximately 3:1. After pre-calcination, cooling, and crushing, the resulting germanium alloy mixture was placed into a high-purity graphite crucible through the feed port.

[0084] The feeding port was closed, the air in the furnace was completely exhausted through atmosphere treatment, and high-purity hydrogen at 1L / min was introduced into the furnace to avoid the influence of oxygen on the germanium purification process.

[0085] The control system turns on the lower and upper heaters, raising the furnace temperature to 1000°C. Simultaneously, the crystallization table temperature is controlled at 600°C to prevent the seed crystal from melting. The furnace temperature is maintained constant until the material inside is fully melted.

[0086] The heater at the lower end of the high-purity graphite crucible is controlled to lower the temperature to 800°C, and the temperature of the crystallization table is controlled to 400°C, so that the germanium in the saturated germanium alloy melt begins to crystallize and grow on the seed crystal. At the same time, the seed crystal table is controlled to move downward at a rate of 50 mm / h through the transmission shaft.

[0087] After the seed crystal table descends a certain distance, the quality of the high-purity germanium obtained at this time accounts for about 60% of the crude germanium quality. The temperature inside the high-purity graphite crucible is lowered to solidify the germanium alloy melt inside the graphite crucible. The generated high-purity germanium is removed by the material removal component to obtain the high-purity germanium product. Samples are taken from the top, middle and bottom positions for testing.

[0088] The results showed that the purities of the upper, middle and lower ends were 5N2, 5N7 and 5N4 respectively.

[0089] Example 5

[0090] 2000g of crude germanium and 1539g of iron were placed in a mixer and thoroughly crushed and mixed under an inert gas atmosphere. The crude germanium had a purity of approximately 4N5, while the iron had a purity of approximately 3N5, with a molar ratio of approximately 1:1. After pre-calcination, cooling, and crushing, the resulting germanium alloy mixture was placed into a high-purity graphite crucible through a feed port.

[0091] The feeding port was closed, the air in the furnace was completely exhausted through atmosphere treatment, and high-purity hydrogen at 1L / min was introduced into the furnace to avoid the influence of oxygen on the germanium purification process.

[0092] The control system turns on the lower and upper heaters, raising the furnace temperature to 1200°C. Simultaneously, the crystallization table temperature is controlled at 600°C to prevent the seed crystal from melting. The furnace temperature is maintained constant until the material inside is fully melted.

[0093] The heater at the lower end of the high-purity graphite crucible is controlled to lower the temperature to 900°C, and the temperature of the crystallization table is controlled to 600°C, so that the germanium in the saturated germanium alloy melt begins to crystallize and grow on the seed crystal. At the same time, the seed crystal table is controlled to move downward at a rate of 50 mm / h through the transmission shaft.

[0094] After the seed crystal table is lowered a certain distance, the quality of the high-purity germanium obtained at this time accounts for about 40% of the quality of the crude germanium. The temperature in the high-purity graphite crucible is lowered to solidify the germanium alloy melt in the graphite crucible. The generated high-purity germanium is taken out by the material removal component to obtain a high-purity germanium product.

[0095] The crystallization table was reloaded with seed crystals and raised until it contacted the alloy material. Another 800g of crude germanium was added to the furnace. The feed port was closed, and the air in the furnace was completely evacuated through atmosphere treatment. High-purity hydrogen was introduced into the furnace at a rate of 1 L / min. Using the same purification conditions as above, approximately 800g of high-purity germanium was obtained.

[0096] The above purification process was repeated 20 times to obtain a high-purity germanium product from the final purification. Samples were taken from the upper, middle and lower ends for testing.

[0097] The results showed that the purities of the upper, middle and lower ends were 4N6, 4N9 and 4N7 respectively.

[0098] Example 6

[0099] Fix 5N high-purity germanium with a purity of 1.577 W on the crystallization table, and raise the seed crystal table to the bottom of the graphite crucible through the transmission shaft so that the upper surface of the seed crystal is flush with the bottom of the crucible.

[0100] 2000g of crude germanium and 1487g of aluminum were placed in a mixer and thoroughly crushed and mixed under an inert gas atmosphere. The crude germanium had a purity of approximately 4N5, and the aluminum used had a purity of approximately 4N5. The molar ratio of crude germanium to aluminum was approximately 0.5:1. After pre-calcination, cooling, and crushing, the resulting germanium alloy mixture was placed into a high-purity graphite crucible through a feed port.

[0101] The feeding port was closed, the air in the furnace was completely exhausted through atmosphere treatment, and high-purity hydrogen at 1L / min was introduced into the furnace to avoid the influence of oxygen on the germanium purification process.

[0102] The control system turns on the lower and upper heaters, raising the furnace temperature to 900°C. Simultaneously, the crystallization table temperature is controlled at 400°C to prevent the seed crystal from melting. The furnace temperature is maintained constant until the material inside is fully melted.

[0103] The heater at the lower end of the high-purity graphite crucible was controlled to lower the temperature to 700°C, and the temperature of the crystallization table was controlled to 400°C, so that the germanium in the saturated germanium alloy melt began to crystallize and grow on the seed crystal. At the same time, the seed crystal table was controlled to move downward at a rate of 100 mm / h through the transmission shaft.

[0104] After the seed crystal table descends a certain distance, the quality of the high-purity germanium obtained at this time accounts for about 60% of the crude germanium quality. The temperature inside the high-purity graphite crucible is lowered to solidify the germanium alloy melt inside the graphite crucible. The generated high-purity germanium is removed by the material removal component to obtain the high-purity germanium product. Samples are taken from the top, middle and bottom positions for testing.

[0105] The results showed that the purities of the upper, middle and lower ends were 4N9, 5N2 and 5N2 respectively.

[0106] Comparative Example 1

[0107] The difference between Comparative Example 1 and Example 3 is that copper is not added as an alloying agent, and the other steps are the same as those of Example 3.

[0108] Fix 5N high-purity germanium with a purity of 1.577 W on the crystallization table, and raise the seed crystal table to the bottom of the graphite crucible through the transmission shaft so that the upper surface of the seed crystal is flush with the bottom of the crucible.

[0109] 3750 g of crude germanium was put into a mixer and fully crushed under an inert gas protection environment. The obtained material was put into a high-purity graphite crucible through a feed port.

[0110] The feeding port was closed, the air in the furnace was completely exhausted through atmosphere treatment, and high-purity hydrogen at 1L / min was introduced into the furnace to avoid the influence of oxygen on the germanium purification process.

[0111] The control system turns on the lower and upper heaters, raising the furnace temperature to 1200°C. Simultaneously, the crystallization table temperature is controlled at 600°C to prevent the seed crystal from melting. The furnace temperature is maintained constant until the material inside is fully melted.

[0112] The heater at the lower end of the high-purity graphite crucible is controlled to lower the temperature to 750°C, and the temperature of the crystallization table is controlled to 400°C, so that the germanium in the saturated germanium alloy melt begins to crystallize and grow on the seed crystal. At the same time, the seed crystal table is controlled to move downward at a rate of 50 mm / h through the transmission shaft.

[0113] After the seed crystal table descends a certain distance, the quality of the high-purity germanium obtained at this time accounts for about 60% of the quality of the crude germanium. The temperature inside the high-purity graphite crucible is lowered to solidify the germanium melt inside the graphite crucible. The generated high-purity germanium is removed by the material removal component to obtain the high-purity germanium product. Samples are taken from the top, middle and bottom positions for testing.

[0114] The results showed that the purities of the upper, middle and lower ends were 4N6, 4N8 and 4N5, respectively.

[0115] Comparative Example 2

[0116] The difference between Comparative Example 2 and Example 2 is that zinc is added as an alloying agent, and the other steps are the same as those of Example 2.

[0117] Fix 5N high-purity germanium with a purity of 1.577 W on the crystallization table, and raise the seed crystal table to the bottom of the graphite crucible through the transmission shaft so that the upper surface of the seed crystal is flush with the bottom of the crucible.

[0118] 2000g of crude germanium and 1487g of zinc were placed in a mixer and thoroughly crushed and mixed under an inert gas atmosphere. The crude germanium had a purity of approximately 4N5, and the zinc used had a purity of approximately 4N5. The molar ratio of crude germanium to zinc was approximately 0.5:1. After pre-calcination, cooling, and crushing, the resulting germanium alloy mixture was placed into a high-purity graphite crucible through a feed port.

[0119] The feeding port was closed, the air in the furnace was completely exhausted through atmosphere treatment, and high-purity hydrogen at 1L / min was introduced into the furnace to avoid the influence of oxygen on the germanium purification process.

[0120] The control system turns on the lower and upper heaters, raising the furnace temperature to 900°C. Simultaneously, the crystallization table temperature is controlled at 400°C to prevent the seed crystal from melting. The furnace temperature is maintained constant until the material inside is fully melted.

[0121] The heater at the lower end of the high-purity graphite crucible is controlled to lower the temperature to 700°C, and the temperature of the crystallization table is controlled to 400°C, so that the germanium in the saturated germanium alloy melt begins to crystallize and grow on the seed crystal. At the same time, the seed crystal table is controlled to move downward at a rate of 10 mm / h through the transmission shaft.

[0122] After the seed crystal table descends a certain distance, the quality of the high-purity germanium obtained at this time accounts for about 80% of the quality of the crude germanium. The temperature inside the high-purity graphite crucible is lowered to solidify the germanium alloy melt inside the graphite crucible. The generated high-purity germanium is removed by the material removal component to obtain the high-purity germanium product. Samples are taken from the top, middle and bottom positions for testing.

[0123] The results showed that the purities of the upper, middle and lower ends were 4N2, 4N3 and 4N1, respectively.

[0124] Analysis of the results: It can be seen from the comparative analysis of Examples 1-4, 6 and the comparative examples that after a single condensation purification, the purity of the high-purity germanium product obtained by adding alloying elements for purification is significantly higher, indicating that the addition of alloys in the present invention can increase the solubility of the melt to impurity elements and significantly reduce the enrichment of impurities in the solid phase during the germanium crystallization process. Compared with Comparative Example 1 and Comparative Example 2 and Example 2, the addition of zinc as an alloying agent has no effect on improving the purity of the germanium product, and even reduces the purity of the germanium product. It is mainly because the addition of zinc increases the concentration of zinc in the melt, resulting in an increase in the content of impurity zinc in the product. Therefore, the present invention has a significant enhancement on the germanium purification effect by adding suitable alloying elements (metal Fe, Cu, Al, Mg of the present application), which is conducive to the efficient preparation of high-purity germanium.

[0125] The above is a further detailed description of the present invention in conjunction with specific preferred embodiments, and the specific implementation of the present invention should not be considered to be limited to these descriptions. For those skilled in the art to which the present invention belongs, several simple deductions or substitutions can be made without departing from the concept of the present invention, and all of these should be considered to fall within the scope of protection of the present invention.

Claims

1. A device for efficiently purifying germanium based on alloying, characterized in that: The device includes a shell, a high-temperature furnace body, a feeding system, an atmosphere system, and a crystallization system; A high-purity graphite crucible is provided in the high-temperature furnace body, and an upper heater and a lower heater are provided on the outside of the graphite crucible; the upper heater and the lower heater are arranged around the outside of the graphite crucible to control the temperature inside the high-purity graphite crucible; The upper end of the high-temperature furnace body is open, and a feeding system is connected thereto. The feeding system includes a connecting component, a sealing kit, and a feeding port. The lower end opening of the high-purity graphite crucible is connected to a crystallization system, which includes a crystallization heater, which is arranged in an annular shape to form a crystallization hole. A material taking component and a crystallization table are provided in the crystallization hole. The lower end of the crystallization table is connected to a transmission shaft and a motor. The material taking component is an oscillating device and is tightly fitted with the lower end opening of the high-purity graphite crucible. The atmosphere system comprises an air inlet, an air outlet, a vacuum pump and an air circuit valve, and the air inlet and the air outlet are arranged on the shell.

2. The device for efficiently purifying germanium based on alloying according to claim 1, characterized in that: The device further comprises a control system, which is electrically connected to the upper heater, the lower heater, the crystal heater, the motor, and the gas circuit valve.

3. A method for purifying germanium using the device for efficiently purifying germanium based on alloying according to any one of claims 1 to 2, characterized in that: The following steps are involved: (1) Fixing a high-purity germanium seed crystal on a seed crystal table, raising the seed crystal table to the bottom of a graphite crucible via a transmission shaft so that the upper surface of the seed crystal is flush with the bottom of the crucible; (2) fully mixing crude germanium and alloy metal under an inert gas protection environment, pre-baking, cooling and crushing to obtain a germanium alloy mixture material, and feeding the germanium alloy mixture material into a high-purity graphite crucible through a feed port; (3) exhausting the air in the high-temperature furnace body and introducing hydrogen; (4) turning on the lower heater and the upper heater to increase the temperature in the graphite crucible so that the germanium alloy mixture material is fully melted to obtain a saturated germanium alloy melt; (5) After the saturated germanium alloy melt stabilizes, the lower heater is adjusted to reduce the temperature of the lower end of the graphite crucible to a preset temperature value, and the temperature of the crystallization table is adjusted by the heater to allow the germanium in the saturated germanium alloy melt to crystallize and grow on the seed crystal, while the seed crystal table is controlled to move downward by the transmission shaft; (6) When the preset crystallization amount is reached, the temperature in the graphite crucible is lowered to solidify the germanium alloy melt in the graphite crucible, and the generated high-purity germanium is taken out to obtain a high-purity germanium product.

4. The method for purifying germanium according to claim 3, wherein: The method further comprises: (7) Fixing the high-purity germanium seed crystal on the seed crystal table again and raising it to contact with the solidified germanium alloy melt; feeding crude germanium into the graphite crucible through the feed port; repeating steps (4) to (6) to obtain a high-purity germanium product; (8) Repeat steps (4) to (7) to purify the crude germanium multiple times; (9) After multiple purifications of crude germanium, the remaining alloy in the crucible is heated and melted and discharged from the lower port of the graphite crucible. The high-purity graphite crucible is cleaned and prepared for the next set of purifications.

5. The method for purifying germanium according to claim 3, wherein: The high-purity germanium seed crystal is high-purity germanium with a purity of 5N or above.

6. The method for purifying germanium according to claim 3, characterized in that: The alloy metal is any one or more of Cu, Al, Mg, and Fe, and the molar ratio of crude germanium to the alloy metal is 0.5-3.

7. The method for purifying germanium according to claim 3, characterized in that: The following technical features are included: In step (4), the temperature in the graphite crucible is 900-1200°C; In step (5), the preset temperature value is 700-900°C; the temperature of the crystallization table is 400-600°C, and the downward movement rate of the crystallization table is 10 mm-100 mm / h; In step (6), the preset crystallization amount is 0.4 to 0.8 times the amount of crude germanium input.

8. The method for purifying germanium according to claim 4, characterized in that: The following technical features are included: In step (7), the amount of crude germanium added is the same as the amount of crude germanium in step (2); In step (8), the number of times is less than 20 times.

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