Germanium ingot preparation system

Abstract

The utility model relates to a germanium ingot preparation system, which comprises a first push boat furnace, a second push boat furnace and a third push boat furnace, the second pusher furnace is used for melting and ingot casting the metal germanium to form a cast germanium ingot; and the zone melting furnace is used for performing zone melting on the cast germanium ingot to obtain a germanium ingot. The germanium ingot preparation system is compact in structure, continuous production and preparation of germanium ingots can be achieved, production efficiency can be improved, and cost can be reduced.

Description

Technical Field

[0001] The utility model relates to a preparation system for germanium ingots, in particular to a preparation system for high-purity germanium ingots. Background Art

[0002] As competition intensifies for the global space station and military industries, demand for high-purity germanium continues to increase. High-purity germanium is irreplaceable in both space stations (high efficiency, high voltage, and excellent temperature resistance) and the military industry (high refractive index). As the development of the global space station enters a new phase and the current global instability continues, demand for metallic germanium (especially high-purity germanium) is rapidly increasing.

[0003] The preparation of metallic germanium currently often involves hydrogen reduction of high-purity germanium dioxide. To accelerate the reduction process and shorten the reduction time, hydrogen reduction of germanium primarily relies on a continuous reduction method. However, the germanium obtained by hydrogen reduction still has a high impurity content, failing to meet product requirements and requiring further purification using zone melting. Zone melting utilizes the principle of nonequilibrium solidification to remove impurity elements with a significant difference in equilibrium distribution coefficient from indium, allowing the impurity elements to be enriched in the liquid phase and ultimately concentrated at both ends of the germanium ingot.

[0004] Traditional high-purity germanium production systems suffer from long processes, intermittent production, low product quality, and high energy consumption. The development of a shortened high-purity germanium production process is imperative. Furthermore, traditional high-purity germanium production systems typically separate the germanium dioxide hydrogen reduction process from the crude germanium regional smelting process, resulting in large land occupation and high investment, as well as additional hydrogen transportation costs. Furthermore, hydrogen transportation also presents certain safety risks, resulting in relatively high overall germanium production costs. Utility Model Content

[0005] The purpose of the utility model is to provide a germanium ingot preparation system to address the deficiencies of the prior art, so as to prepare the germanium ingot more efficiently.

[0006] The technical solutions adopted in this utility model are as follows:

[0007] A system for preparing a germanium ingot, comprising:

[0008] The first push boat furnace is used to reduce germanium dioxide to metallic germanium;

[0009] a second push boat furnace, for melting and casting the metallic germanium outputted from the first push boat furnace to form a cast germanium ingot; and

[0010] The zone melting furnace is used for zone melting the cast germanium ingot outputted from the second push boat furnace to obtain the germanium ingot.

[0011] Thus, germanium dioxide can be reduced to metallic germanium in the first pusher boat furnace. The metallic germanium is then melted and cast in the second pusher boat furnace, where it can be further reduced and purified to produce a cast germanium ingot suitable for zone melting, preparing for zone melting. The cast germanium ingot is then zone melted in the zone melting furnace, and the head and tail of the ingot are removed to produce the desired germanium ingot. This entire process can be carried out continuously, facilitating more efficient production of germanium ingots.

[0012] Furthermore, the first push boat furnace has at least two first heating zones distributed sequentially along its length, each equipped with a first temperature sensor; the second push boat furnace has at least two second heating zones distributed sequentially along its length, each equipped with a second temperature sensor. This allows for convenient monitoring and control of the temperature of each heating zone, helping to improve reduction and casting effects, and further increasing the final product qualification rate.

[0013] Furthermore, the first push boat furnace has 3-6 first heating zones distributed sequentially along its length direction; the second push boat furnace has 3-4 second heating zones distributed sequentially along its length direction.

[0014] Furthermore, each first heating zone is provided with a first heating element; each second heating zone is provided with a second heating element, so as to facilitate independent heating and temperature control of each heating zone.

[0015] Optionally, the length of the first heating zone is 800-1200 mm; optionally, the length of the second heating zone is 400-800 mm.

[0016] Furthermore, a first conveying device is provided between the first push boat furnace and the second push boat furnace to facilitate the transfer of the push boat carrying the metal germanium between the first push boat furnace and the second push boat furnace.

[0017] Furthermore, a cleaning and drying device is provided between the second push boat furnace and the zone melting furnace to clean impurities on the cast germanium ingot, thereby further improving the zone melting effect.

[0018] Furthermore, a second conveying device is provided between the second push boat furnace and the cleaning and drying device, and a third conveying device is provided between the cleaning and drying device and the zone melting furnace, thereby facilitating the transportation of the push boat carrying the cast germanium ingot.

[0019] Furthermore, the cleaning and drying device includes a pickling unit for pickling the cast germanium ingot, a water washing unit for water washing the pickled cast germanium ingot, and a microwave washing unit for microwave washing the water washed cast germanium ingot.

[0020] Furthermore, the push boat furnace is a push boat tube furnace. Optionally, the push boat is a graphite push boat.

[0021] Compared with the prior art, the present invention has the following beneficial effects:

[0022] (1) The germanium ingot preparation system of the present invention can realize the continuous production and preparation of germanium ingots, which helps to improve production efficiency and reduce costs.

[0023] (2) The germanium ingot preparation system of the present invention has a compact structure, which helps to save floor space and reduce investment costs. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 This is a simplified structural diagram of a germanium ingot preparation system of the present invention.

[0025] In the figure, 1-first push boat furnace, 2-first conveying device, 3-second push boat furnace, 4-second conveying device, 5-cleaning and drying device, 501-pickling unit, 502-water washing unit, 503-microwave washing unit, 6-third conveying device, 7-regional melting furnace. DETAILED DESCRIPTION

[0026] The present invention will be described in detail below with reference to the accompanying drawings and in conjunction with the embodiments. It should be noted that the embodiments and features of the embodiments of the present invention may be combined unless they conflict. For ease of description, the words "upper," "lower," "left," and "right" appear below merely to indicate the directions of upper, lower, left, and right in the accompanying drawings and do not limit the structure.

[0027] 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.

[0028] 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.

[0029] Example 1

[0030] See also Figure 1 , a germanium ingot preparation system, comprising:

[0031] A first push boat furnace is used to reduce germanium dioxide to metallic germanium. The first push boat furnace has five first heating zones distributed sequentially along its length, each of which is equipped with a first temperature sensor (thermocouple). The temperature of each first heating zone increases sequentially along the direction of movement of the push boat. Each first heating zone is equipped with a first heating element. The first push boat furnace is provided with a first air inlet to facilitate the input of gases such as hydrogen and nitrogen.

[0032] a second push boat furnace, disposed on the downstream side of the first push boat furnace, for melting and casting the metallic germanium to form a cast germanium ingot; the second push boat furnace has three second heating zones sequentially distributed along its length, each second heating zone is provided with a second temperature sensor (thermocouple), and the temperature of each second heating zone increases sequentially along the direction of movement of the push boat; each second heating zone is provided with a second heating element, and the second push boat furnace is provided with a first air inlet to facilitate the input of gases such as hydrogen and nitrogen; and

[0033] The zone melting furnace is arranged at the downstream side of the second push boat furnace and is used for performing zone melting on the cast germanium ingot to obtain the germanium ingot.

[0034] A first conveying device is provided between the first push boat furnace and the second push boat furnace. A cleaning and drying device is provided between the second push boat furnace and the zone melting furnace. A second conveying device is provided between the second push boat furnace and the cleaning and drying device, and a third conveying device is provided between the cleaning and drying device and the zone melting furnace. The cleaning and drying device includes a pickling unit for pickling the cast germanium ingot, a water washing unit for water washing the pickled cast germanium ingot, and a microwave washing unit for microwave washing the water washed cast germanium ingot. Optionally, industrial robots are provided between adjacent functional units in the second conveying device, the pickling unit, the water washing unit, the microwave washing unit, and the third conveying device to facilitate the transfer of materials. The push boat furnace is a push boat tube furnace.

[0035] When using the above preparation system to prepare germanium ingots, the following method can be used:

[0036] (1) The germanium dioxide material obtained after pretreatment was placed in a graphite push boat (each graphite push boat was filled with 100 g of germanium dioxide material). The material was continuously fed from one end of the first push boat furnace and sequentially passed through each first heating zone in a countercurrent hydrogen and nitrogen mixed atmosphere. The heating temperature of each first heating zone was set to 500, 650, 690, 800, and 1000°C, and the length of each first heating zone was 1000 mm. The time interval between entering the boat was 60 minutes (boat speed 6.0 mm / min). After cooling, the graphite push boat carrying metallic germanium was pushed out from the other end. The graphite push boat carrying metallic germanium was then continuously pushed into the feeding end of the second push boat furnace and sequentially passed through each second heating zone in a countercurrent hydrogen and nitrogen mixed atmosphere. The heating temperature of each second heating zone was set to 690, 800, and 1000°C, and the length of each second heating zone was 600 mm. The time interval between entering the boat was 50 minutes (boat speed 6.0 mm / min). After the completion, the graphite push boat carrying the cast germanium ingot is pushed out from the discharging end of the second push boat.

[0037] The pretreatment is as follows: first, the raw material germanium dioxide (purity of 4N-5N) is soaked and cleaned with hydrochloric acid for 3 minutes, then soaked and cleaned with deionized water for 20 minutes, and finally 2 Pa, and dried in a vacuum drying oven at 80°C for 30 min to obtain the pretreated germanium dioxide powder.

[0038] (2) The cast germanium ingot is transported to the cleaning and drying device, washed with mixed acid, washed with pure water, washed with microwave and dried in sequence, then placed in a graphite push boat and pushed into the zone melting furnace. The hydrogen flow rate is adjusted to 0.6 / min, and the alloy zone of the zone melting furnace is heated under a hydrogen protective atmosphere, and heated to 700°C at a heating rate of 5°C / min. After the temperature stabilizes, it is moved uniformly at a speed of 50mm / h until the end of the melting zone, and the heating is stopped and cooled to room temperature, and then the head and tail of the ingot are linearly cut. The cut germanium ingot is subjected to the above zone melting process for 5 more times, and the moving speed is increased from 80 to 200mm / h according to the number of zone melting.

[0039] During acid washing, the germanium ingot was soaked in a mixed acid (20 wt % HF + 80 wt % HNO 3 ) for 3 minutes to corrode the surface of the germanium ingot; during microwave washing, electronic grade deionized water was used for microwave washing.

[0040] The obtained germanium ingot was sent for GDMS testing. The results are shown in Table 1.

[0041] Table 1

[0042] Germanium dioxide content / g Germanium ingot amount / g Germanium yield / % Germanium ingot purity 100.0 68.99 99.4 6N(99.9999％)

[0043] It can be seen that high-purity germanium ingots can be obtained through the preparation system of the utility model, the recovery rate of germanium is high, and the continuous production of germanium ingots can be achieved, which helps to improve production efficiency.

[0044] The contents described in the above embodiments should be understood as these embodiments are only used to more clearly illustrate the present invention, and are not used to limit the scope of the present invention. After reading the present invention, various equivalent modifications to the present invention made by those skilled in the art fall within the scope defined by the claims attached to this application.

Claims

1. A system for preparing germanium ingots, characterized in that: include: The first push boat furnace is used to reduce germanium dioxide to metallic germanium; a second push boat furnace, for melting and casting the metallic germanium outputted from the first push boat furnace to form a cast germanium ingot; a zone melting furnace, used for performing zone melting on the cast germanium ingot outputted from the second push boat furnace to obtain a germanium ingot; Among them, a first conveying device is provided between the first push boat furnace and the second push boat furnace, a cleaning and drying device is provided between the second push boat furnace and the regional melting furnace, a second conveying device is provided between the second push boat furnace and the cleaning and drying device, and a third conveying device is provided between the cleaning and drying device and the regional melting furnace.

2. The preparation system according to claim 1, characterized in that: The first push boat furnace has at least two first heating zones distributed sequentially along its length, and each first heating zone is respectively provided with a first temperature sensor; the second push boat furnace has at least two second heating zones distributed sequentially along its length, and each second heating zone is respectively provided with a second temperature sensor.

3. The preparation system according to claim 2, characterized in that: The first push boat furnace has 3-6 first heating zones distributed sequentially along its length direction; the second push boat furnace has 3-4 second heating zones distributed sequentially along its length direction.

4. The preparation system according to claim 2, characterized in that: Each first heating zone is provided with a first heating element; each second heating zone is provided with a second heating element.

5. The preparation system according to claim 1, characterized in that: The cleaning and drying device comprises a pickling unit for pickling the cast germanium ingot, a water washing unit for water washing the pickled cast germanium ingot, and a microwave washing unit for microwave washing the water washed cast germanium ingot.

6. The preparation system according to any one of claims 1 to 4, characterized in that: The push boat furnace is a push boat tube furnace.

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