Vertical tubular stainless steel high-purity germanium dioxide reduction device

Abstract

The utility model discloses a vertical tubular stainless steel high-purity germanium dioxide reduction device which is composed of a tubular hearth, a heating furnace, a heat preservation layer, a high-purity hydrogen supply pipe, an air cooling cooler, a water cooling cooler and a gas-liquid separator. The tubular hearth is vertically arranged in the heating furnace, and a heat preservation layer is arranged outside the heating furnace; the high-purity hydrogen supply pipe penetrates through the heating furnace and is connected with the top of the tubular hearth; an air outlet pipe is arranged at the bottom of the heating furnace and is connected with an air-cooled cooler; and the air-cooled cooler is connected with the gas-liquid separator through the water-cooled cooler. The tubular hearth is vertically arranged, so that high-purity hydrogen and high-purity germanium dioxide are more fully contacted, the utilization rate and the reduction efficiency of the high-purity hydrogen are higher, the time required by the technological process is shortened, the power consumption is reduced, a high-purity hydrogen pipeline is preheated in the reaction furnace, and the production efficiency is improved. The insufficient reaction temperature caused by the fact that cold air flow directly enters the materials to take away part of heat is avoided.

Description

Technical Field

[0001] The utility model relates to the technical field of germanium material processing, in particular to a vertical tubular stainless steel high-purity germanium dioxide reduction device. Background Art

[0002] High-purity reduced metallic germanium powder typically exceeds 5N (99.999%) purity. This high-purity germanium material possesses excellent performance in the semiconductor and optoelectronic fields, making it an ideal raw material for the preparation of high-purity germanium materials. High-purity germanium is widely used in aerospace, medical, defense, communications, and materials science. Emerging technologies such as quantum computing and artificial intelligence are driving a surge in demand for high-performance semiconductor materials, driving up market demand and prices for high-purity germanium. Global annual production of high-purity germanium is relatively small, primarily concentrated in countries such as China, Belgium, Germany, and the United States. China is the world's largest germanium producer, possessing abundant germanium resources and well-developed production facilities. Although global germanium production is increasing annually, the production of high-purity germanium remains limited by extraction and purification technology and raw materials. The current method for producing high-purity germanium is usually to use a nitrogen and hydrogen mixture produced by the decomposition of ammonia in a horizontal tubular reduction furnace to reduce high-purity germanium dioxide to obtain high-purity germanium powder. The chemical reaction equation is as follows: 2H2+GeO2=2H2O+Ge. The high-purity germanium powder is then regionally melted and purified to obtain high-purity germanium metal.

[0003] However, the current intermittent horizontal quartz tubular reduction furnace for producing high-purity reduced germanium powder still has problems such as low single-unit output, low reduction efficiency, low hydrogen utilization rate, high power consumption, safety hazards, and direct emission of exhaust gas. It is necessary to research more advanced reduction devices to replace them.

[0004] First, the reduction efficiency of high-purity hydrogen is low during the reduction process, resulting in high consumption. Theoretically, 428 L of high-purity hydrogen are required to reduce 1 kg of high-purity germanium dioxide, but in actual production, the consumption of high-purity hydrogen exceeds ten times the theoretical amount. The main reason for this gap is that the currently used horizontal quartz tubular reduction furnace makes it difficult for high-purity hydrogen to fully contact high-purity germanium dioxide. Since the flow direction of the high-purity hydrogen is parallel to the surface of the high-purity germanium dioxide in the graphite boat, the high-purity hydrogen reacts with the topmost layer of high-purity germanium dioxide, and the high-purity germanium powder generated by the reaction will adhere to the surface of the high-purity germanium dioxide. At the same time, the mixed hydrogen produced by the decomposition of ammonia currently used contains one-quarter nitrogen. Due to its high specific gravity, it sinks to the surface of the high-purity germanium dioxide at the bottom of the longer reduction furnace tube during the flow process, which to a certain extent blocks the contact reaction between hydrogen and germanium dioxide. At the same time, the hydrogen floats to the upper part of the furnace tube, hindering and weakening the further reaction of the high-purity hydrogen with the high-purity germanium dioxide below. At the same time, the high-purity hydrogen flows continuously, so that some of the high-purity hydrogen moves to the tail of the furnace before it has time to react or is carried away by the nitrogen and the generated water vapor, resulting in a prolonged reduction reaction time and increased high-purity hydrogen consumption.

[0005] Secondly, there are high power consumption and low output. The power of existing equipment is 15 kW, and one process takes about 22 hours. The equipment has a long operating time and high power consumption. In addition, due to the limitations of the horizontal tubular furnace diameter and the loading capacity of the graphite boat, each furnace can only load about 2.4 kg-2.7 kg of high-purity germanium dioxide, and the daily output of a single device is relatively low.

[0006] Third, high-purity hydrogen is a Class A flammable and explosive gas with a low lower explosion limit and a wide range of explosion limits. This places significant pressure on production processes and safety management. Existing equipment often uses flexible hoses for both the inlet and outlet of high-purity hydrogen. This connection is prone to clogging, lacks safety, and is not conducive to the use of safe gas detection equipment.

[0007] Fourthly, the slightly acidic water vapor containing germanium produced by the reduction is directly discharged into the air without being recovered, which affects the surrounding environment, causes the loss of germanium, and affects the germanium recovery rate. Summary of the Invention

[0008] To solve the above-mentioned problems, the present invention provides a vertical tubular stainless steel high-purity germanium dioxide reduction device, which consists of a tubular furnace, a heating furnace, an insulation layer, a high-purity hydrogen gas supply pipe, an air-cooled cooler, a water-cooled cooler, and a gas-liquid separator. The tubular furnace is vertically arranged in the heating furnace, and an insulation layer is provided outside the heating furnace. The high-purity hydrogen gas supply pipe passes through the heating furnace and is connected to the top of the tubular furnace. An outlet pipe is provided at the bottom of the heating furnace, and the outlet pipe is connected to the air-cooled cooler. The air-cooled cooler is connected to the gas-liquid separator via a water-cooled cooler. The vertical tubular furnace is made of stainless steel and is arranged vertically. Gas enters from the upper end of the vertical tubular furnace, passes through the interior of the vertical tubular furnace from top to bottom, and then leaves from the lower end. A heating furnace is provided on the outside for heating, and an insulation layer is provided on the outside of the heating furnace. The gas feed pipeline passes through the heating furnace for preheating. A gas inlet is provided at the upper end of the vertical tubular furnace, and a gas outlet is provided at the lower end. The vertical tubular furnace has a size of φ100mm*1000mm and can be loaded with 10kg-15kg of high-purity germanium dioxide.

[0009] Furthermore, the high-purity hydrogen gas supply pipe is equipped with a ball valve and a metal rotor flowmeter. The high-purity hydrogen gas supply pipe is equipped with a ball valve and a metal rotor flowmeter. The high-purity hydrogen gas supply pipe can provide high-purity hydrogen and nitrogen gases, with a maximum gas flow rate of 50 L / min.

[0010] Furthermore, the water-cooled cooler is equipped with a coolant inlet at the bottom and a coolant outlet at the top. Both the air-cooled cooler and the water-cooled cooler are coil-type heat exchangers, made of 316L stainless steel. One end of the air-cooled cooler is connected to the vertical tubular furnace gas outlet via a pipeline, and the other end is connected to the water-cooled cooler via a pipeline. The water-cooled cooler has coolant inlets and outlets on both sides, with the upper end connected to the air-cooled cooler via a pipeline, and the lower end connected to the gas-liquid separator via a pipeline.

[0011] Furthermore, the gas-liquid separator is provided with a drain outlet at the bottom and an air outlet at the top, which is equipped with a back-pressure valve. The gas-liquid separator is made of 316L stainless steel and has an effective volume of 10L. Two interfaces are provided on the top of the separator and a drain outlet is provided at the bottom. One of the interfaces on the top of the separator is connected to the water-cooled cooler pipeline, and the other is an air outlet equipped with a back-pressure valve. The gas-liquid separator can separate gas and liquid. The gas in the separator can be discharged and recycled through the back-pressure valve to control the pressure. It can also be sampled for chromatographic analysis. The liquid in the separator can be discharged and recycled through the water outlet at the bottom.

[0012] The above-mentioned technical solution of the present invention has the following beneficial technical effects: the inner diameter of the vertical tubular furnace is increased, thereby improving the capacity of loading high-purity germanium dioxide and thus increasing the daily output of a single device. The tubular furnace is placed vertically, so that the high-purity hydrogen and high-purity germanium dioxide are in more complete contact, the utilization rate of high-purity hydrogen and the reduction efficiency are both improved, and the ratio of theoretical consumption to actual consumption of high-purity hydrogen is reduced from the original 1:10 to 1:1.1, so that the actual consumption of high-purity hydrogen is closer to the theoretical requirement. The time required for one process flow is shortened from the original 22 hours to 15 hours, shortening the process flow time and reducing power consumption. The design of preheating the high-purity hydrogen pipeline through the reactor avoids the cold air flow directly entering the material and removing some heat, which may lead to insufficient reaction temperature. It is of great significance to improve the reduction efficiency and product purity of high-purity germanium dioxide. The entire device is made of stainless steel, which further improves the durability, safety and process stability of the equipment. The germanium-containing water vapor generated by the reduction is recycled, thereby recovering more germanium without affecting the environment. BRIEF DESCRIPTION OF THE DRAWINGS

[0013] Figure 1 It is a structural diagram of a vertical tubular stainless steel high-purity germanium dioxide reduction device.

[0014] Reference numerals:

[0015] 1: High-purity hydrogen supply pipe; 2: Ball valve; 3: Metal rotor flowmeter; 4: Tubular furnace; 5: Insulation layer; 6: Heating furnace; 7: Air-cooled cooler; 8: Coolant outlet; 9: Coolant inlet; 10: Water-cooled cooler; 11: Back pressure valve; 12: Gas-liquid separator; 13: Drain outlet. DETAILED DESCRIPTION

[0016] To make the objectives, technical solutions, and advantages of the present invention more clearly understood, the present invention is further described below in conjunction with specific embodiments and with reference to the accompanying drawings. It should be understood that these descriptions are merely illustrative and are not intended to limit the scope of the present invention. Furthermore, descriptions of known structures and technologies are omitted in the following description to avoid unnecessary confusion regarding the concepts of the present invention.

[0017] like Figure 1As shown, a vertical tubular stainless steel high-purity germanium dioxide reduction device is provided, which comprises a tubular furnace 4, a heating furnace 6, an insulation layer 5, a high-purity hydrogen gas supply pipe 1, an air-cooled cooler 7, a water-cooled cooler 10, and a gas-liquid separator 12. The tubular furnace 4 is vertically arranged inside the heating furnace 6, and the insulation layer 5 is provided outside the heating furnace 6. The high-purity hydrogen gas supply pipe 1 passes through the heating furnace 6 and is connected to the top of the tubular furnace 4. An outlet pipe is provided at the bottom of the heating furnace 6, which is connected to the air-cooled cooler 7. The air-cooled cooler 7 is connected to the gas-liquid separator 12 via the water-cooled cooler 10. The vertical tubular furnace 4 is made of stainless steel and is arranged vertically. Gas enters from the upper end of the vertical tubular furnace, passes through the interior of the vertical tubular furnace 4 from top to bottom, and then exits from the lower end. The heating furnace 6 is provided on the outside for heating, and the insulation layer 5 is provided on the outside of the heating furnace 6. The gas feed line passes through the heating furnace 6 for preheating. A gas inlet is provided at the top of the vertical tubular furnace 4, and a gas outlet is provided at the bottom. The vertical tubular furnace has a size of φ100mm*1000mm and can hold 10kg-15kg of high-purity germanium dioxide.

[0018] The high-purity hydrogen gas supply pipe 1 is provided with a ball valve 2 and a metal rotor flowmeter 3. The high-purity hydrogen gas supply pipe is provided with a ball valve and a metal rotor flowmeter. The high-purity hydrogen gas supply pipe is capable of providing two gases, high-purity hydrogen and nitrogen, with a maximum gas flow rate of 50 L / min.

[0019] The water-cooled cooler 10 is equipped with a coolant inlet 9 at its lower portion and a coolant outlet 8 at its upper portion. Both the air-cooled cooler 7 and the water-cooled cooler 10 are coil-type heat exchangers, made of 316L stainless steel. One end of the air-cooled cooler is connected to the vertical tubular furnace gas outlet via a pipeline, and the other end is connected to the water-cooled cooler via a pipeline. The water-cooled cooler has coolant inlets and outlets on both sides. Its upper end is connected to the air-cooled cooler via a pipeline, and its lower end is connected to the gas-liquid separator via a pipeline.

[0020] The gas-liquid separator 12 is provided with a drain port 13 at the bottom and an air outlet at the top, which is equipped with a back-pressure valve 11. The gas-liquid separator is made of 316L stainless steel and has an effective volume of 10L. Two interfaces are provided on the top of the separator and a drain port is provided on the bottom. One of the interfaces on the top of the separator is connected to the water-cooled cooler pipeline, and the other is the air outlet, which is equipped with a back-pressure valve. The gas in the separator can be discharged for recycling through the back-pressure valve to control the pressure. The gas can also be sampled for chromatographic analysis. The liquid in the separator can be discharged through the water outlet at the bottom for recycling.

[0021] The high-purity hydrogen provided by the high-purity hydrogen supply pipe is generated by water electrolysis or photocatalytic hydrogen production.

[0022] In specific implementation, high-purity germanium dioxide is placed into and sealed in the tubular furnace 4. The ball valve 2 is opened, and the high-purity hydrogen flow rate is adjusted by adjusting the metal rotor flowmeter 3. High-purity hydrogen is then introduced through the high-purity hydrogen supply pipe 1 for approximately 20 minutes to displace the air throughout the entire apparatus. A temperature control program is then set for the heating furnace 6, divided into three phases: heating, constant temperature, and cooling. During the heating phase, the metal rotor flowmeter 3 is adjusted to reduce the high-purity hydrogen flow rate. During the constant temperature phase, the metal rotor flowmeter 3 is adjusted to increase the high-purity hydrogen flow rate to meet process requirements. During the cooling phase, nitrogen is supplied instead, and the metal rotor flowmeter 3 is adjusted to adjust the nitrogen flow rate, displacing the high-purity hydrogen throughout the apparatus. The water vapor generated during the process flows from the outlet at the lower end of the tubular furnace through a pipeline, sequentially passing through an air-cooled cooler 7 and a water-cooled cooler 10. This process is first cooled by air and then by water-cooled coolant. The coolant flows from the water inlet 9 to the water outlet 8. The water vapor condenses into water and flows along the pipeline into the gas-liquid separator 12. After the heating furnace cools to 25°C, ball valve 2 is closed to stop ventilation, and the tubular furnace door 4 is opened to obtain high-purity reduced germanium powder. Water from the gas-liquid separator can be discharged through outlet 13 for recycling, while other non-condensable gases can be discharged through backpressure valve 11 for pressure control and recycling or sampled for chromatographic analysis.

[0023] It should be understood that the above-described specific embodiments of the present invention are merely illustrative of or explanation of the principles of the present invention and do not constitute limitations of the present invention. Therefore, any modifications, equivalent substitutions, improvements, etc. made without departing from the spirit and scope of the present invention shall be included within the scope of protection of the present invention. In addition, the appended claims of the present invention are intended to cover all variations and modifications that fall within the scope and metes and bounds of the appended claims, or equivalents thereof.

Claims

1. A vertical tubular stainless steel high-purity germanium dioxide reduction device, characterized in that: It consists of a tubular furnace, a heating furnace, an insulation layer, a high-purity hydrogen supply pipe, an air-cooled cooler, a water-cooled cooler and a gas-liquid separator; the tubular furnace is vertically arranged in the heating furnace, and an insulation layer is provided outside the heating furnace; the high-purity hydrogen supply pipe passes through the heating furnace and is connected to the top of the tubular furnace; an outlet pipe is provided at the bottom of the heating furnace, and the outlet pipe is connected to the air-cooled cooler; the air-cooled cooler is connected to the gas-liquid separator through the water-cooled cooler.

2. The vertical tubular stainless steel high-purity germanium dioxide reduction device according to claim 1, characterized in that: The high-purity hydrogen gas supply pipe is provided with a ball valve and a metal rotor flowmeter.

3. The vertical tubular stainless steel high-purity germanium dioxide reduction device according to claim 1, characterized in that: The lower part of the water-cooled cooler is provided with a coolant inlet, and the upper part is provided with a coolant outlet.

4. The vertical tubular stainless steel high-purity germanium dioxide reduction device according to claim 1, characterized in that: The gas-liquid separator is provided with a drain port at the bottom and an air outlet at the top, and the air outlet is provided with a back pressure valve.

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