System for continuously preparing germane

Abstract

The system for continuously preparing germane comprises a feeding unit, a reaction unit, a separation unit and a collection unit, the feeding unit is communicated with an inert gas cylinder and a vacuum pump; the feeding unit comprises an alkali liquor feeding kettle and an acid liquor feeding kettle and is used for feeding an alkali solution and an acid solution of germanium dioxide and sodium borohydride; the reaction unit comprises a reaction kettle which is respectively connected with the two feeding kettles and is used for sequentially feeding an acid solution and an alkali solution to react to prepare germane and outputting germane crude product gas; the separation unit comprises an impurity removal tank, a copious cooling tank, an adsorption tank and a rectifying tower, the impurity removal tank is used for removing water and carbon dioxide from the germane crude product gas, the obtained primary treatment gas is subjected to copious cooling liquefaction through the copious cooling tank, and germane crude product liquid and secondary treatment gas are output; rectifying the obtained germane crude product liquid through a rectifying tower to remove impurities, and outputting germane product liquid; adsorbing and intercepting germane in the secondary treatment gas through an adsorption tank; the collecting unit comprises a collecting tank which is connected to a product liquid outlet of the rectifying tower. The system can be used for continuously preparing germane.

Description

Technical Field

[0001] The utility model belongs to the technical field of germane synthesis, and particularly relates to a system for continuously preparing germane. Background Art

[0002] Germane (GeH4) is a colorless, flammable, and highly toxic gas at room temperature and pressure, with a boiling point of -90°C. It is stable at room temperature, begins to decompose at around 280°C, and decomposes almost completely into elemental Ge and H2 at around 350°C. It reacts with alkali metals in liquid ammonia at room temperature and is insoluble in water. Germane is an important source of high-purity elemental germanium and a precursor for the silicon-germanium (Si-Ge) films used in heterojunction diode transistors. In the electronics industry, it is primarily used in the metal-organic chemical vapor deposition (MOCVD) process. As a key precursor gas for solar cells, germane is primarily used to form the green-light-absorbing intermediate layer of amorphous silicon-germanium alloys containing medium band gaps, and the red-light-absorbing bottom layer of amorphous silicon-germanium alloys with higher germanium content and narrow band gaps. In recent years, with the rapid development of the microelectronics, photovoltaic, and aerospace industries, demand for germane has been increasing.

[0003] Currently, there are two main methods for preparing germane: chemical reduction and electrolysis. Chemical reduction is the mainstream method currently used for large-scale production. Chemical reduction methods include the magnesium germanium method and the germanium dioxide method. The germanium dioxide method offers advantages such as high yield and ease of purification. However, the vast majority (over 80%) of the gas produced by this reaction is non-condensable hydrogen, which must be promptly separated from the target gas and discharged. This process can interrupt the reaction in actual production, affecting production efficiency.

[0004] CN 208200379 U discloses a germane production and purification system, but it cannot achieve continuous production. TW103141003 A discloses a method for continuous or semi-continuous production of germane. This method performs pressure swing adsorption on the untreated mixed gas produced by the reaction to separate hydrogen from other gas components including the target gas. However, because a large proportion of the target gas germane is still present in the mixed gas produced by the reaction, a large amount of adsorption material is required, resulting in increased equipment and material costs. In addition, the presence of highly polar water components in the mixed gas accelerates the decline of the adsorption performance of the adsorption material and affects the separation effect. None of the above existing technologies can effectively solve the problem of continuous production of germane.

[0005] Therefore, there is currently no process system that can achieve continuous production of germane. Utility Model Content

[0006] The purpose of the utility model is to provide a system for continuously preparing germane, which can solve the problem of continuous production of germane.

[0007] In order to achieve the purpose of this utility model, the following technical solutions are adopted:

[0008] A system for continuously preparing germane comprises a feeding unit, a reaction unit, a separation unit and a collection unit which are sequentially connected via pipelines;

[0009] The feeding unit is connected to an inert gas cylinder for purging and gas replacement of the system;

[0010] The feeding unit is also connected to a vacuum pump for evacuating the devices in the system;

[0011] The feeding unit includes an alkali solution feeding kettle and an acid solution feeding kettle, and the two are respectively connected to the reaction unit, and are used to feed the alkali solution containing germanium dioxide and sodium borohydride from the alkali solution feeding kettle to the reaction unit, and feed the sulfuric acid solution from the acid solution feeding kettle to the reaction unit;

[0012] The reaction unit includes a reactor, which is connected to the acid solution feeding kettle and the alkali solution feeding kettle respectively and is located below the two, and is used to sequentially feed sulfuric acid solution and an alkali solution containing germanium dioxide and sodium borohydride to react and prepare germanium, and output germanium crude product gas from its exhaust pipe and output waste liquid from the bottom;

[0013] The separation unit includes a removal tank, a cryogenic tank, an adsorption tank, and a distillation tower connected in sequence; wherein,

[0014] The impurity removal tank is connected to the exhaust pipe of the reactor, and is used to introduce the raw germanium product gas from the reaction unit and remove water and carbon dioxide therein by controlling the temperature to obtain a primary treated gas;

[0015] The cryogenic tank is connected to the exhaust pipe of the impurity removal tank, and is used to introduce the primary treatment gas from the impurity removal tank, and liquefy the germanium in the primary treatment gas by controlling the temperature, and output the germanium crude product liquid and the secondary treatment gas respectively;

[0016] The adsorption tank is connected to the exhaust pipe of the cryogenic tank and is provided with a molecular sieve therein for passing the secondary treated gas from the cryogenic tank to adsorb and retain the germane therein and release it periodically, and output non-condensable gas;

[0017] The distillation tower is connected to the drain pipe of the cryogenic tank, and is used to distill and remove impurities from the crude germanium product liquid from the cryogenic tank, and output the germanium product liquid;

[0018] The collecting unit includes a collecting tank, and the collecting tank is connected to the product liquid outlet of the distillation tower and is used for collecting the germane product liquid from the separation unit.

[0019] The utility model is used for a system for continuously preparing germane. Preferably, the feeding unit also includes an alkali solution dropping kettle, and the alkali solution dropping kettle is arranged on the pipeline from the alkali solution feeding kettle to the reactor, and is used to drop the alkali solution from the alkali solution feeding kettle into the reactor.

[0020] The utility model is used for a system for continuously preparing germane. Preferably, the discharge port of the alkali solution dropping kettle is provided with a pressure regulator for controlling the feeding condition of the alkali solution.

[0021] The utility model is used for a system for continuously preparing germane. Preferably, the feeding unit is also provided with a gas phase balancing pipeline, one end of the gas phase balancing pipeline is connected to the feed port of the reactor, and the other end is connected to the upper air inlet of the alkali solution dropping kettle, for balancing the pressure in the alkali solution dropping kettle and the reactor.

[0022] The utility model is used for a system for continuously preparing germane. Preferably, in the separation unit, a pipeline from the exhaust pipe of the reactor to the impurity removal tank is further provided with a condenser, a buffer tank and a compression pump that are connected in sequence, so that before the crude germane product gas from the reaction unit is sent to the impurity removal tank, it is first sent to the condenser for cooling, then to the buffer tank for buffering, and then pumped to the impurity removal tank via the compression pump.

[0023] The utility model is used for a system for continuously preparing germane, preferably,

[0024] The air inlet pipe of the impurity removal tank is inserted from the top to the bottom thereof, and the air outlet of the impurity removal tank is located at the top thereof; and / or,

[0025] The interior of the impurity removal tank is divided into an upper layer and a lower layer by a porous sieve plate. The lower layer is filled with soda lime particles for removing carbon dioxide and water from the germanium crude product gas, and the upper layer is filled with molecular sieves for further adsorption and water removal.

[0026] In the system for continuously preparing germane of the present invention, preferably, at least two layers of mesh metal partitions are disposed from bottom to top within the cryogenic tank. In the system for continuously preparing germane of the present invention, preferably, a first exhaust line is also disposed from the adsorption tank to the cryogenic tank, and a one-way valve is disposed on the first exhaust line from the adsorption tank to the cryogenic tank, for unidirectionally transporting adsorbed germane to the cryogenic tank after the adsorption tank releases it.

[0027] The utility model is used for a system for continuously preparing germane. Preferably, a one-way valve is provided on the non-condensable gas outlet pipeline of the adsorption tank for outputting the non-condensable gas therein in a one-way manner.

[0028] The utility model is used for a system for continuously preparing germane, preferably,

[0029] The reactor is provided with a temperature control device; and / or,

[0030] The alkali solution feeding kettle is provided with a temperature control device; and / or,

[0031] The acid solution feeding kettle is provided with a temperature control device; and / or,

[0032] The alkali solution dropping kettle is provided with a temperature control device; and / or,

[0033] The impurity removal tank is provided with a temperature control device; and / or,

[0034] The cryogenic tank is provided with a temperature control device; and / or,

[0035] The adsorption tank is provided with a temperature control device.

[0036] The beneficial effects of the present invention are:

[0037] The system for continuously preparing germane of the utility model has a simple structure and a reasonable design, and can realize the continuous feeding of raw materials and the timely discharge of by-product hydrogen, thereby continuously preparing germane products and realizing the continuous production of germane, and is suitable for the industrial production of germane. BRIEF DESCRIPTION OF THE DRAWINGS

[0038] Figure 1 This is a schematic structural diagram of a system for continuously preparing germane according to the present invention in one embodiment; wherein,

[0039] Alkali solution feeding kettle 101, acid solution feeding kettle 102, alkali solution dropping kettle 103, pressure regulator 104, gas phase balance pipeline 105; reactor 201; impurity removal tank 301, cryogenic tank 302, adsorption tank 303, distillation tower 304, condenser 305, buffer tank 306 and compression pump 307, first exhaust pipeline 308, non-condensable gas outlet pipeline 309; collection tank 401. DETAILED DESCRIPTION

[0040] The following further illustrates the technical solution and its effects of the present invention in conjunction with the accompanying drawings and specific embodiments. The following embodiments are intended only to illustrate the present invention and are not limited to the following embodiments or examples. Simple modifications to the present invention based on the concepts of the present invention are within the scope of protection claimed by the present invention.

[0041] like Figure 1 As shown, the system for continuously preparing germane of the present invention includes a feeding unit, a reaction unit, a separation unit and a collection unit which are sequentially connected via pipelines;

[0042] The feeding unit is connected to an inert gas cylinder for purging and gas replacement of the system;

[0043] The feeding unit is also connected to a vacuum pump for evacuating the devices in the system;

[0044] The feeding unit includes an alkali solution feeding kettle 101 and an acid solution feeding kettle 102, and the two are respectively connected to the reaction unit, for feeding an alkali solution containing germanium dioxide and sodium borohydride from the alkali solution feeding kettle 101 to the reaction unit, and feeding a sulfuric acid solution from the acid solution feeding kettle 102 to the reaction unit;

[0045] The reaction unit includes a reactor 201, which is connected to the acid solution feeding kettle 102 and the alkali solution feeding kettle 101 respectively and is located below the two, and is used to sequentially feed a sulfuric acid solution and an alkaline solution containing germanium dioxide and sodium borohydride (such as a sodium hydroxide solution of germanium dioxide and sodium borohydride, i.e., a mixed solution of germanium dioxide, sodium borohydride and sodium hydroxide) to react and prepare germanium, and outputs a crude germanium product gas from its exhaust pipe and outputs waste liquid from the bottom;

[0046] The separation unit includes a removal tank 301, a cryogenic tank 302, an adsorption tank 303, and a distillation tower 304 connected in sequence; wherein,

[0047] The impurity removal tank 301 is connected to the exhaust pipe of the reactor 201, and is used to pass the raw germanium product gas from the reaction unit and remove water and carbon dioxide therein by controlling the temperature to obtain a primary processed gas;

[0048] The cryogenic tank 302 is connected to the exhaust pipe of the impurity removal tank 301, and is used to pass the primary processed gas from the impurity removal tank 301, and liquefy the germanium in the primary processed gas by controlling the temperature, and output the germanium crude product liquid and the secondary processed gas respectively;

[0049] The adsorption tank 303 is connected to the exhaust pipe of the cryogenic tank 302 and is provided with a molecular sieve therein for passing the secondary treated gas from the cryogenic tank 302 to adsorb and retain the germane therein and release it periodically, and output non-condensable gas;

[0050] The distillation tower 304 is connected to the drain pipe of the cryogenic tank 302 and is used to distill and remove impurities from the crude germanium product liquid from the cryogenic tank 302 and output the germanium product liquid;

[0051] The collecting unit includes a collecting tank 401 , and the collecting tank 401 is connected to the product liquid outlet of the distillation tower 304 , and is used to collect the germane product liquid from the separation unit.

[0052] In the present invention, a molecular sieve is installed within the adsorption tank 303 to absorb a small amount of uncondensed germane gas carried by non-condensable gases such as hydrogen, separating the germane from the non-condensable gases. The hydrogen and other non-condensable gases then pass through a one-way valve into the hydrogen treatment system for treatment and discharge. The waste liquid discharged from the bottom of the reactor 201 is sent to the waste liquid treatment system for treatment and discharge. The inert gas in the inert gas cylinder can be helium, argon, or nitrogen.

[0053] The system for continuously preparing germane of the utility model has a simple structure and a reasonable design, and can realize the continuous feeding of raw materials and the timely discharge of non-condensable gases such as by-product hydrogen, thereby continuously producing germane products and realizing continuous production of germane, and is suitable for the industrial production of germane.

[0054] In one embodiment, the feeding unit further includes an alkali solution adding kettle 103, which is arranged on the pipeline from the alkali solution adding kettle 101 to the reactor 201, and is used to drop the alkali solution from the alkali solution adding kettle 101 into the reactor 201, thereby controlling the feeding speed and addition amount of the alkali solution, so that it is slowly fed into the sulfuric acid solution for reaction, to ensure that the germanium dioxide in the alkali solution is completely reacted to generate germane.

[0055] In one embodiment, the discharge port of the alkali solution adding kettle 103 is provided with a pressure regulator 104 for further controlling the feeding conditions of the alkali solution, such as the feeding speed and feeding amount, to ensure that the germanium dioxide in the alkali solution is completely reacted to form germane.

[0056] In one embodiment, the feeding unit is further provided with a gas phase balancing pipeline 105, one end of which is connected to the feed port of the reactor 201, and the other end is connected to the upper air inlet of the alkali solution dropping kettle 103, for balancing the air pressure in the alkali solution dropping kettle 103 and the reactor 201, so that the air pressure is balanced, so that the alkali solution is dropped at a stable speed, reducing impurities generated by uneven dropping speed.

[0057] In one embodiment, the alkali solution feeding kettle 101, the acid solution feeding kettle 102 and the alkali solution dropping kettle 103 are made of stainless steel and are lined with anti-corrosion linings.

[0058] In one embodiment, in the separation unit, a pipeline from the exhaust pipe of the reactor 201 to the impurity removal tank 301 is provided with a condenser 305, a buffer tank 306 and a compression pump 307 which are connected in sequence, so as to send the crude germanium product gas from the reaction unit to the condenser 305 for cooling, to the buffer tank 306 for buffering, and then to the compression pump 307 for pumping to the impurity removal tank 301 before the crude germanium product gas is sent to the impurity removal tank 301.

[0059] In one embodiment, the air inlet pipe of the impurity removal tank 301 is inserted from the top to the bottom thereof, and the air outlet of the impurity removal tank 301 is located at the top thereof, so that the incoming germane crude product gas is fully in contact with the inside from the bottom to the top, which helps to improve the impurity removal effect.

[0060] In one embodiment, the interior of the impurity removal tank 301 is divided into an upper layer and a lower layer by a porous sieve plate, the lower layer is filled with soda lime particles for removing carbon dioxide and water from the germane crude product gas, and the upper layer is filled with molecular sieves (such as 3A molecular sieves or 4A molecular sieves) for further adsorption and water removal.

[0061] In one embodiment, at least two layers of mesh metal partitions are provided in the cryogenic tank 302 from bottom to top, thereby increasing the contact area between the cryogenic tank 302 and the introduced gas and rapidly condensing and liquefying the germane gas.

[0062] In one embodiment, a first exhaust pipeline 308 is further provided from the adsorption tank 303 to the cryogenic tank 302, and a one-way valve is provided on the first exhaust pipeline 308 from the adsorption tank 303 to the cryogenic tank 302, which is used to transport the adsorbed germane (i.e., the released germane gas) to the cryogenic tank 302 in a one-way manner after the adsorption tank 303 releases the adsorbed germane, so as to avoid its backflow, thereby improving the separation effect and the germane yield.

[0063] In one embodiment, a one-way valve is provided on the non-condensable gas outlet pipeline 309 of the adsorption tank 303 to output the non-condensable gas therein in a one-way manner (to the hydrogen processing system) to avoid backflow, thereby improving the separation effect.

[0064] In one embodiment, the reactor 201 is provided with a temperature control device, which can control the temperature therein within the range of -10 to 50°C (such as -10°C, 0°C, 10°C, 20°C, 30°C, 40°C and 50°C and any value and range of values ​​within the range) to facilitate the reaction to generate germane.

[0065] Those skilled in the art will appreciate that, in one embodiment, the reactor 201 is further provided with a stirring device for stirring the feed liquid entering therein so that the two are evenly mixed and fully contacted, which is further conducive to the forward progress of the reaction.

[0066] In one embodiment, the alkali solution feeding kettle 101 is provided with a temperature control device for adjusting the temperature to a suitable range.

[0067] In one embodiment, the acid solution feeding kettle 102 is provided with a temperature control device for regulating the temperature within a suitable range.

[0068] In one embodiment, the alkali solution adding kettle 103 is provided with a temperature control device for adjusting the temperature to a suitable range.

[0069] In one embodiment, the impurity removal tank 301 is provided with a temperature control device, which can control the temperature therein within the range of 0 to -70°C (such as -10°C, 0°C, 10°C, 20°C, 30°C, 40°C and 50°C and any numerical value and numerical range within this range), thereby effectively removing carbon dioxide and water in the germane crude product gas.

[0070] In one embodiment, the cryogenic tank 302 is provided with a temperature control device, which can control the temperature therein within the range of -90 to -150°C (such as -90°C, -100°C, -110°C, -120°C, -130°C, -140°C and -150°C and any numerical value and numerical range within this range), thereby quickly condensing and liquefying the germane gas and achieving rapid separation of germane and non-condensable gas.

[0071] In one embodiment, the adsorption tank 303 is provided with a temperature control device, which can control the temperature therein within the range of -70 to 80°C (such as -70°C, -60°C, -50°C, -40°C, -30°C, -20°C, -10°C, 0°C, 10°C, 20°C, 30°C, 40°C, 50°C, 60°C, 70°C and 80°C and any numerical value and numerical range within this range), and effectively control the adsorption, retention and desorption and precipitation of germane by the molecular sieve therein by cooling and heating, thereby effectively separating the non-condensable gas.

[0072] The system for continuously preparing germane of the utility model has a simple structure and a reasonable design, and can realize the continuous feeding of raw materials and the timely discharge of by-product hydrogen, thereby continuously preparing germane products and realizing the continuous production of germane, and is suitable for the industrial production of germane.

[0073] Those skilled in the art understand that relevant pipelines are provided with corresponding valves to control the flow direction of materials therein. When preparing germane, the opening and closing of different valves can be used to control the feeding of alkaline solution and acid solution, and the transportation and discharge of related substances, thereby achieving continuous feeding of raw materials and timely discharge of by-product hydrogen, thereby continuously producing germane products and realizing continuous production of germane, which is suitable for industrial production of germane.

[0074] like Figure 1 As shown, the process of preparing germane using the above system is as follows:

[0075] 1. Preparation before reaction

[0076] (1) Open the relevant valves, turn on the vacuum pump and inert gas cylinder (such as He gas cylinder), and evacuate and purge the system to normal pressure in sequence; after passing the test, close all valves;

[0077] (2) Preparation of alkaline solution and acid solution, and inert gas purging and replacement

[0078] ① Prepare an alkaline solution containing germanium dioxide and sodium borohydride; for example, first add pure water to a bucket, add sodium hydroxide to the pure water, stir to dissolve, and prepare a sodium hydroxide solution with a concentration of 0.2-0.4 mol / L; then add sodium borohydride and germanium dioxide to the solution, stir to dissolve, and prepare an alkaline solution; wherein the concentration of sodium borohydride is 0.6-1.0 mol / L, and the concentration of germanium dioxide is 0.15-0.2 mol / L;

[0079] ② Prepare an acid solution, for example, by first adding pure water into a bucket, then slowly adding concentrated sulfuric acid into the pure water, stirring, and preparing a sulfuric acid solution with a concentration of 1.5-3.0 mol / L;

[0080] ③ Add the prepared alkali solution to the alkali solution feeding kettle 101, and add the prepared acid solution to the acid solution feeding kettle 102, and turn on the temperature control devices of both to control the temperature, then turn on the vacuum pump, inert gas cylinder (such as He gas cylinder) and related valves, and vacuum and purge the alkali solution feeding kettle 101 and the acid solution feeding kettle 102 in turn with inert gas to replace the pressure; after passing the test, close all valves;

[0081] 2. Preparation reaction

[0082] (1) Open the relevant valves, add the acid solution in the acid solution feeding kettle 102 to the reactor 201, and turn on the stirring device and temperature control device in the reactor 201 to control the reaction temperature within a suitable range (for example, the reaction temperature is 0° C.);

[0083] Then, the relevant valves are opened, and the alkaline solution in the alkaline solution feeding kettle 101 is added to the alkaline solution dropping kettle 103, and then dripped into the reaction kettle 201 through the pressure regulator 104 to react and generate germane, and output germane crude product gas; and the gas pressure balance in the alkaline solution dropping kettle 103 and the reaction kettle 201 is adjusted through the gas phase balance pipeline 105;

[0084] (2) closing the relevant valves and repeating step (2) in step 1 to feed the alkaline solution and the acid solution and purge and replace them with inert gas, so as to prepare for subsequent raw material replenishment to enter the reactor 201;

[0085] (3) The crude germanium product gas output from the reactor 201 is cooled by the condenser 305 and enters the buffer tank 306. Then, it is pressurized by the compression pump 307 and enters the impurity removal tank 301 through the air inlet pipe inserted from the top to the bottom. The temperature control device controls the temperature in the impurity removal tank 301 to be within a suitable range (for example, -70°C), thereby removing water and carbon dioxide from the crude germanium product gas. The primary treated gas is output to the cryogenic tank 302, and the temperature control device controls the temperature in the impurity removal tank 301 to be within a suitable range (for example, -150°C), thereby removing the impurity The germane gas is rapidly liquefied and collected at the bottom of the tank. A small amount (less than 1%) of the germane gas enters the adsorption tank 303 along with the non-condensable gas (i.e., the secondary processed gas enters the adsorption tank 303). The germane gas entering along with the non-condensable gas is adsorbed and retained by the molecular sieve in the adsorption tank 303. The non-condensable gas that is not adsorbed enters the hydrogen treatment system through the one-way valve for subsequent treatment and is then discharged. The crude germane product liquid liquefied at the bottom of the cryogenic tank 302 enters the distillation tower 304 for rectification and impurity removal, and then enters the collection tank 401 for collection and storage.

[0086] (4) The system is vacuumed and purged. Finally, the system is filled with nitrogen to normal pressure. The drain valve at the bottom of the reactor 201 is opened to discharge the waste liquid after the reaction.

[0087] The system for continuously preparing germane of the utility model has a simple structure and a reasonable design, and can realize the continuous feeding of raw materials and the timely discharge of by-product hydrogen, thereby continuously preparing germane products and realizing the continuous production of germane, and is suitable for the industrial production of germane.

Claims

1. A system for continuously preparing germane, characterized in that: The system comprises a feeding unit, a reaction unit, a separation unit and a collection unit which are sequentially connected via pipelines; The feeding unit is connected to an inert gas cylinder for purging and gas replacement of the system; The feeding unit is also connected to a vacuum pump for evacuating the devices in the system; The feeding unit comprises an alkali solution feeding kettle (101) and an acid solution feeding kettle (102), and the two are respectively connected to the reaction unit, and are used to feed the alkali solution containing germanium dioxide and sodium borohydride from the alkali solution feeding kettle (101) to the reaction unit, and to feed the sulfuric acid solution from the acid solution feeding kettle (102) to the reaction unit; The reaction unit comprises a reactor (201), which is connected to the acid solution feeding kettle (102) and the alkali solution feeding kettle (101) respectively and is located below the two, and is used to sequentially feed sulfuric acid solution and an alkali solution containing germanium dioxide and sodium borohydride to react and prepare germanium, and output germanium crude product gas from its exhaust pipe and output waste liquid from the bottom; The separation unit comprises a removal tank (301), a cryogenic tank (302), an adsorption tank (303), and a distillation tower (304) connected in sequence; wherein, The impurity removal tank (301) is connected to the exhaust pipe of the reactor (201) and is used to introduce the raw germanium product gas from the reaction unit and remove water and carbon dioxide therein by controlling the temperature to obtain a primary treated gas; The cryogenic tank (302) is connected to the exhaust pipe of the impurity removal tank (301) and is used to introduce the primary treatment gas from the impurity removal tank (301), and liquefy the germanium in the primary treatment gas by controlling the temperature, and output germanium crude product liquid and secondary treatment gas respectively; The adsorption tank (303) is connected to the exhaust pipe of the cryogenic tank (302), and a molecular sieve is provided therein for passing the secondary treated gas from the cryogenic tank (302) to adsorb and retain the germane therein and release it periodically, and output non-condensable gas; The distillation tower (304) is connected to the discharge pipe of the cryogenic tank (302) and is used to perform distillation and impurity removal on the crude germanium product liquid from the cryogenic tank (302) and output the germanium product liquid; The collecting unit includes a collecting tank (401), and the collecting tank (401) is connected to the product liquid outlet of the distillation tower (304) for collecting the germane product liquid from the separation unit.

2. The system according to claim 1, wherein: The feeding unit further includes an alkali solution adding kettle (103), which is arranged on the pipeline from the alkali solution adding kettle (101) to the reactor (201) and is used to drop the alkali solution from the alkali solution adding kettle (101) into the reactor (201).

3. The system according to claim 2, characterized in that The discharge port of the alkali solution adding kettle (103) is provided with a pressure regulator (104) for controlling the feeding of the alkali solution.

4. The system according to claim 2 or 3, characterized in that The feeding unit is also provided with a gas phase balancing pipeline (105), one end of which is connected to the feed port of the reactor (201) and the other end is connected to the upper air inlet of the alkali solution dropping kettle (103), for balancing the pressure in the alkali solution dropping kettle (103) and the reactor (201).

5. The system according to claim 4, characterized in that In the separation unit, a pipeline from the exhaust pipe of the reactor (201) to the impurity removal tank (301) is provided with a condenser (305), a buffer tank (306) and a compression pump (307) which are connected to each other. The condenser (305), the buffer tank (306) and the compression pump (307) are used to sequentially send the crude germanium product gas from the reaction unit to the condenser (305) for cooling, to the buffer tank (306) for buffering, and then to the compression pump (307) for pumping the crude germanium product gas to the impurity removal tank (301) before the crude germanium product gas is sent to the impurity removal tank (301).

6. The system according to claim 4, characterized in that The air inlet pipe of the impurity removal tank (301) is inserted from the top thereof to the bottom thereof, and the air outlet of the impurity removal tank (301) is located at the top thereof; and / or, The interior of the impurity removal tank (301) is divided into an upper layer and a lower layer by a porous sieve plate. The lower layer is filled with soda lime particles for removing carbon dioxide and water from the germane crude product gas, and the upper layer is filled with molecular sieves for further adsorption and water removal.

7. The system according to claim 4, wherein: At least two layers of mesh metal partitions are arranged in the cryogenic tank (302) from bottom to top.

8. The system according to claim 4, wherein: A first exhaust pipeline (308) is further provided from the adsorption tank (303) to the cryogenic tank (302), and a one-way valve from the adsorption tank (303) to the cryogenic tank (302) is provided on the first exhaust pipeline (308), for unidirectionally transporting the adsorbed germane into the cryogenic tank (302) after the adsorption tank (303) releases the adsorbed germane.

9. The system according to claim 4, wherein: A one-way valve is provided on the non-condensable gas outlet pipeline (309) of the adsorption tank (303) for outputting the non-condensable gas therein in a one-way manner.

10. The system according to any one of claims 2, 3 and 5-9, characterized in that The reactor (201) is provided with a temperature control device; and / or, The alkali solution feeding kettle (101) is provided with a temperature control device; and / or, The acid solution feeding kettle (102) is provided with a temperature control device; and / or, The alkali solution dropping kettle (103) is provided with a temperature control device; and / or, The impurity removal tank (301) is provided with a temperature control device; and / or, The cryogenic tank (302) is provided with a temperature control device; and / or, The adsorption tank (303) is provided with a temperature control device.

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