Germanium hydride production method and germanium hydride preparation system

Abstract

The present invention provides a production method and a germanium hydride preparation system for germanium hydride. The method of the present invention is used to prepare germanium hydride, which can improve the yield of germanium hydride and is suitable for large-scale industrial production of germanium hydride. The production method comprises the following steps: (1) grinding a first portion of ammonium halide in a first grinder and purging it with hot nitrogen, then adding the magnesium germanide into the first grinder, continuing grinding and mixing to obtain material A; grinding a second portion of ammonium halide in a second grinder and purging it with hot nitrogen to obtain material B; (2) adding the material B into a reactor and mixing it with the solvent, then adding the material A into the reactor, and reacting to obtain a crude germanium hydride product; (3) refining the crude germanium hydride product to obtain a germanium hydride product.

Description

Technical Field

[0001] The invention relates to the technical field of germanium hydride preparation, and in particular to a germanium hydride production method and a germanium hydride preparation system. Background Art

[0002] Germanium hydride (Germane), also known as germane, is a colorless gas at room temperature and pressure. It does not react with water. Its chemical formula is GeH4, molecular weight is 76.7, melting point is -165℃, boiling point is -91℃. It is an inorganic compound that is stable at room temperature. It begins to decompose at about 280℃ and almost all decomposes into elemental Ge and H2 at about 350℃. It can burn in the air and emits a blue-red flame when burning, but the degree of combustion is not as intense as silane. Germanium hydride is one of the promising semiconductor industrial gases. It is mainly used for metal organic compound vapor deposition MOCVD in the semiconductor field. Its application areas also include solar cells and the preparation of heterojunction diode crystals. The synthesis methods of germanium hydride include chemical synthesis, electrochemical reduction, and plasma synthesis. The magnesium germanium method and the germanium dioxide method belong to the chemical synthesis method. In the synthesis process of the magnesium germanium method, the solvent medium used can be water or liquid ammonia. The yield of using water as the medium is less than 30%; the yield of using liquid ammonia as the medium is 60-70%, and the yields are relatively low. Patent application CN111777039A discloses a germane production process, which adopts the germanium dioxide method to produce germanium hydride. Since an aqueous solution of acid and alkali is used as a solvent, the corrosion resistance of the equipment is extremely high, the equipment investment is huge, and the liquid-liquid reaction has the characteristics of extremely fast speed and most of the volume of the product is hydrogen. Complicated operations are required to separate the product from hydrogen, and there are great safety hazards.

[0003] In short, although there are many existing methods, there are problems such as low yield, high equipment requirements, and difficult reaction control. Summary of the invention

[0004] In view of the shortcomings of the prior art, the present invention provides a production method and a germanium hydride preparation system for germanium hydride. The method of the present invention is used to prepare germanium hydride, which can improve the yield of germanium hydride and is suitable for large-scale industrial production of germanium hydride.

[0005] To achieve the purpose, the present invention provides the following technical solutions:

[0006] The present invention provides a method for producing germanium hydride. The germanium hydride is produced by reacting ammonium halide and magnesium germanide in the presence of a solvent. The production method comprises the following steps:

[0007] (1) grinding a first portion of ammonia halide in a first grinder and purging it with hot nitrogen, then adding the magnesium germanium into the first grinder, and continuing to grind and mix to obtain material A;

[0008] Grinding the second portion of the ammonium halide in a second grinder and purging with hot nitrogen to obtain material B;

[0009] (2) putting the material B into a reactor and mixing it with the solvent, and then putting the material A into the reactor to obtain a crude germanium hydride product through reaction;

[0010] (3) refining the crude germanium hydride product to obtain a germanium hydride product.

[0011] In some embodiments, the conditions for performing the grinding in the first grinder and the second grinder include independently: a temperature of 10-60° C., a pressure of 0.1-0.2 MPa, and a grinding time of, for example, 0.1-1 h;

[0012] Preferably, before the grinding in the first grinder and the second grinder, the air in the grinder is replaced with hot nitrogen respectively;

[0013] Preferably, the difference between the temperature of the hot nitrogen and the temperature in the first grinder or the second grinder is within ±5°C;

[0014] Preferably, in the first grinder or in the second grinder, the hot nitrogen is purged multiple times at intervals during the grinding process, the number of purging is preferably 2-10 times, and the interval time of each purging is preferably 5-15 minutes.

[0015] In some embodiments, in step (1), after adding the magnesium germanium, the conditions for continuing grinding include: a temperature range of 10-60° C. and a pressure range of 0.1-0.2 MPa;

[0016] The time for continuing grinding is preferably 0.1-1h.

[0017] In some embodiments, the ammonium halide is selected from one or more of ammonium chloride, ammonium bromide, and ammonium thiocyanate;

[0018] And / or, the solvent is liquid ammonia.

[0019] In some embodiments, in step (2), the feeding temperature of the solvent is -25°C to 0°C;

[0020] Preferably, in step (2), the material B and the material A are cooled to a temperature within ±3° C. of the feeding temperature of the solvent before being fed into the reactor.

[0021] In some embodiments, the molar ratio of the first part of ammonium halide to the magnesium germanium is 0.2-0.5:1;

[0022] The molar ratio of the second part of ammonium halide to the magnesium germanium is 3.5-3.8:1;

[0023] The molar ratio of the second part of ammonium halide to the solvent is 1:15-32.

[0024] In some embodiments, in step (2), the reaction is carried out at a temperature of -25°C to -10°C and a pressure of 0.1-0.2 MPa; preferably, during the reaction, the stirring speed of the reactor is 20-80 r / min;

[0025] Preferably, the top of the reactor is equipped with a condenser, and the temperature of the condenser is -40°C to -50°C.

[0026] In some embodiments, in step (3), impurities in the crude germanium hydride product are removed by the refining treatment, and the impurities include one or more of ammonia, water, digermane, non-condensable gas and other possible trace impurities;

[0027] Preferably, the refining treatment includes: first sending the crude germanium hydride product into an ammonia removal tank to absorb with water to remove ammonia therein, then sending it into a dehydration adsorber to remove moisture, then sending it into a refrigerator to remove digermane, then sending it into a cold trap to remove non-condensable gas, and then sending it into a trace impurity adsorber to remove trace impurities;

[0028] Further preferably, in the ammonia removal tank, ammonia gas in the crude germanium hydride product is converted into ammonia water, and the obtained ammonia water is sent to an ammonia water recovery device for mixing with liquid ammonia to prepare industrial-grade ammonia water.

[0029] The present invention also provides a germanium hydride preparation system for implementing the production method described above, characterized in that the preparation system comprises a first grinder, a second grinder, a reactor and a refining unit;

[0030] The first grinder is provided with a hot nitrogen inlet, and the first grinder is used to grind the first part of ammonium halide and the magnesium germanium to obtain the material A;

[0031] The second grinder is provided with a hot nitrogen inlet, and the second grinder is used to grind the second portion of ammonium halide to obtain the material B;

[0032] The reactor is used to contact and react the material A and the material B in the presence of a solvent to obtain the crude germanium hydride product;

[0033] The refining unit is used to perform a refining treatment on the crude germanium hydride product to obtain the germanium hydride product.

[0034] In some embodiments, a first feeder and a second feeder are further included; the first feeder is used to contain the material A and feed it to the reactor; the second feeder is used to contain the material B and feed it to the reactor;

[0035] And / or, the refining unit comprises an ammonia removal tank, a water removal adsorber, a refrigerator, a cold trap, a trace impurity adsorber and a product tank connected in series in sequence, and preferably also comprises an ammonia water recovery device;

[0036] The ammonia removal tank is connected to the reactor and is used to make the crude germanium hydride product contact with water to absorb and remove ammonia and obtain ammonia water;

[0037] The dehydration adsorber is connected to the ammonia removal tank and is used to remove moisture from the germanium hydride crude product after being treated by the ammonia removal tank;

[0038] The refrigerator is connected to the dehydration adsorber and is used to remove digermane from the crude germanium hydride product after being treated by the dehydration adsorber;

[0039] The cold trap is connected to the refrigerator and is used to remove non-condensable gas in the crude germanium hydride product after being treated by the refrigerator;

[0040] The trace impurity adsorber is connected to the cold trap and is used to remove trace impurities in the germanium hydride crude product after being treated by the cold trap and obtain the germanium hydride product;

[0041] The product tank is connected to the trace impurity adsorber and is used to receive the germanium hydride product;

[0042] The ammonia water recovery device is connected to the ammonia removal tank and is used to receive the ammonia water and mix it with liquid ammonia.

[0043] The technical solution provided by the present invention has the following beneficial effects:

[0044] (1) Pretreatment means are used to avoid deliquescing and deterioration of the ammonium halide raw material, and the production method of the present invention is beneficial to improving the synthesis yield and purity of germanium hydride;

[0045] (2) The production method of the present invention can be used to purify the crude product to obtain a high-purity germanium hydride product;

[0046] (3) In the preferred embodiment, the impure ammonia gas passes through an ammonia removal tank to obtain co-produced ammonia water.

[0047] The production method of the invention is easy to operate continuously and can be applicable to the large-scale production of germanium hydride products. BRIEF DESCRIPTION OF THE DRAWINGS

[0048] Figure 1 A schematic diagram of a preparation system for preparing germanium hydride in one embodiment.

[0049] Explanation of some of the figure markings: first grinder 1, second grinder 2, first feeder 3, second feeder 4, reactor 5, ammonia removal tank 6, dehydration adsorber 7, refrigerator 8, cold trap 9, trace impurity adsorber 10, product tank 11, ammonia water recovery device 12, condenser 13, liquid ammonia input pipe 14. DETAILED DESCRIPTION

[0050] In order to facilitate the understanding of the present invention, the present invention will be further described below in conjunction with examples. It should be understood that the following examples are only for a better understanding of the present invention and do not mean that the present invention is limited to the following examples.

[0051] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art to which the invention belongs. The term "and / or" as may be used herein includes any and all combinations of one or more of the associated listed items.

[0052] The top, bottom, etc. mentioned or may be mentioned in this specification are defined relative to the structures shown in the drawings. They are relative concepts and may change accordingly according to different positions and different usage conditions. In addition, the terms "first", "second", etc. are used for descriptive purposes only and cannot be understood as indicating or implying relative importance.

[0053] The present invention provides a method for producing germanium hydride. The germanium hydride is produced by reacting ammonium halide and magnesium germanide in the presence of a solvent. The production method comprises the following steps:

[0054] (1) grinding a first portion of ammonium halide in a first grinder and purging with hot nitrogen, then adding the magnesium germanium into the first grinder, and continuing to grind and mix to obtain material A;

[0055] Grinding the second portion of ammonium halide in a second grinder and purging with hot nitrogen to obtain material B;

[0056] (2) putting the material B into a reactor and mixing it with the solvent, and then putting the material A into the reactor to obtain a crude germanium hydride product through reaction;

[0057] (3) refining the crude germanium hydride product to obtain a germanium hydride product.

[0058] The inventors have found that in a preparation process for preparing germanium hydride based on the reaction of magnesium germanium and ammonium halide in a solvent, before the ammonium halide is brought into contact with the magnesium germanium, the ammonium halide is first ground and pre-treated by purging with hot nitrogen, and then the pre-treated ammonium halide and the magnesium germanium are pre-mixed and ground; before the magnesium germanium is added, a portion of the pre-treated ammonium halide is first added to the reaction system, and then the mixture of magnesium germanium and the remaining ammonium halide is added, which can effectively solve the problems of raw material deliquescence and insufficient reaction of solid materials, can significantly improve the yield of germanium hydride, and is conducive to obtaining high-purity germanium hydride in the subsequent process.

[0059] In the present invention, before the ammonium halide is contacted with magnesium germanium, it is pretreated, ground in the first grinder, and purged with hot nitrogen during grinding, which can effectively reduce the deliquesce and deterioration of ammonium chloride, and facilitate the subsequent full mixing with magnesium germanium and compounding of the two; the remaining part of the ammonium halide is ground in the second grinder and purged with hot nitrogen during grinding, which can avoid the deterioration and agglomeration of the ammonium halide; the material processing method and feeding method of the present invention are used to facilitate the full progress of the subsequent reaction and improve the yield of germanium hydride. In a preferred embodiment, the conditions for the grinding in the first grinder and in the second grinder are independently included: the temperature is 10-60°C, the pressure is 0.1-0.2Mpa, and the grinding time is, for example, 0.1-1h. In some examples, the grinding time of the second grinder is less than the grinding time of the first grinder. Preferably, before the grinding in the first grinder and the second grinder, the air in the grinder is replaced with hot nitrogen, so that the grinding is carried out in an atmosphere isolated from air. Preferably, the difference between the temperature of the hot nitrogen used and the temperature in the corresponding first grinder or the second grinder is within ±5°C, for example, ±2°C, ±5°C, etc.; preferably, in the first grinder or in the second grinder, the hot nitrogen is purged multiple times at intervals during the grinding process, and the number of purgings is preferably 2-10 times, and the interval time each time is, for example, 5-15 minutes.

[0060] Specifically, the first grinder and the second grinder may be various corresponding grinding devices that can provide a closed grinding space and can be purged with hot nitrogen. They may be grinding devices known in the art that can achieve the above functions, and there is no particular limitation on this.

[0061] In a preferred embodiment, in step (1), after adding the magnesium germanium, the conditions for continuing grinding include: a temperature range of 10-60° C., a pressure range of 0.1-0.2 MPa; and a time for continuing grinding is preferably 0.1-1 h.

[0062] In the present invention, the ammonium halide can be selected from one or more of ammonium chloride, ammonium bromide, and ammonium thiocyanate.

[0063] Some examples of chemical reactions for preparing germanium hydride are as follows:

[0064] Mg2Ge+NH4X→GeH4+MgX2+NH3(X is Cl, Br, SCN)

[0065] Preferably, the solvent is liquid ammonia; in a preferred embodiment, in step (2), the feeding temperature of the solvent is -25°C to 0°C. Preferably, in step (2), before feeding into the reactor, the material B and the material A are cooled to a temperature within ±3°C of the feeding temperature of the solvent; for example, the material B and the material A are cooled in their respective feeders to the same temperature as the solvent before feeding.

[0066] In a preferred embodiment, the molar ratio of the first part of ammonium halide to the magnesium germanium is 0.2-0.5:1;

[0067] The molar ratio of the second part of ammonium halide to the magnesium germanium is 3.5-3.8:1;

[0068] The molar ratio of the second part of ammonium halide to the solvent is 1:15-32.

[0069] In a preferred embodiment, in step (2), the reaction is carried out at a temperature of -25°C to -10°C and a pressure of 0.1-0.2 MPa; preferably, during the reaction, the stirring speed of the reactor is 20-80 r / min. Specifically, the reaction in step (2) is carried out until the pressure in the reactor is constant.

[0070] Preferably, the top of the reactor is equipped with a condenser, the temperature of the condenser is -40°C to -50°C, and the condenser is provided to prevent ammonia from escaping during the reaction.

[0071] Furthermore, in step (3), impurities in the crude germanium hydride product are removed by the refining treatment, and the impurities include ammonia, water, digermane, non-condensable gas and other trace impurities (such as methane, etc.) that may exist. The method of the present invention can be used to produce germanium hydride, which can increase the yield and improve the purity of the product. For example, a germanium hydride product with a purity of about 3.5-5N can be obtained, and a germanium hydride product with a purity of more than 5N can even be obtained.

[0072] Preferably, the refining treatment includes: first sending the crude germanium hydride product into an ammonia removal tank to absorb and remove ammonia therein with water, then sending it into a dehydration adsorber to remove moisture, then sending it into a refrigerator to remove digermane, then sending it into a cold trap to remove non-condensable gas, and then sending it into a trace impurity adsorber to remove trace impurities. Specifically, the solvent used in the ammonia removal tank is water. In some examples, the material filled in the dehydration adsorber can be a common dehydration adsorption filler in the art, such as a combination of one or more of calcium chloride or molecular sieves 3A, 4A, 5A, 13X, etc. In some examples, the refrigerator is a refrigerator with a temperature of -40°C to -85°C; the temperature of the cold trap used is -100 to -165°C, and the non-condensable gas removed by the cold trap includes, but is not limited to, hydrogen, nitrogen, etc. In some examples, the material filled in the trace impurity adsorber can be a common impurity adsorption filler in the art, such as a combination of one or more of molecular sieves 3A, 4A, 5A, 13X, etc.

[0073] Further preferably, in the ammonia removal tank, ammonia gas in the crude germanium hydride product is converted into ammonia water, and the obtained ammonia water is sent to an ammonia water recovery device, where it can be mixed with liquid ammonia and refined to obtain industrial-grade ammonia water. The method of the present invention can achieve the co-production of ammonia water while producing germanium hydride.

[0074] The present invention also provides a germanium hydride preparation system for implementing the production method described above, such as Figure 1 As shown, the preparation system includes a first grinder 1, a second grinder 2, a reactor 5 and a refining unit;

[0075] The first grinder 1 is provided with a hot nitrogen inlet (not shown in the figure), which is connected to a hot nitrogen source and is used to introduce hot nitrogen to achieve air replacement or hot nitrogen purge in the grinder; the first grinder 1 is used to grind the first part of ammonium halide and the magnesium germanium to obtain the material A;

[0076] The second grinder 2 is provided with a hot nitrogen inlet (not shown in the figure), which is connected to a hot nitrogen source and is used to introduce hot nitrogen to achieve air replacement or hot nitrogen purge in the grinder; the second grinder 2 is used to grind the second part of ammonium halide to obtain the material B;

[0077] The reactor 5 is used to make the material A and the material B contact and react in the presence of a solvent to obtain the crude germanium hydride product;

[0078] The refining unit is used to perform a refining treatment on the crude germanium hydride product to obtain the germanium hydride product.

[0079] During the grinding process in the first grinder 1, hot nitrogen can be introduced into the hot nitrogen inlet for purging as required. During the grinding process in the second grinder 2, hot nitrogen can be introduced into the hot nitrogen inlet for purging as required.

[0080] Furthermore, it also includes a first feeder 3 and a second feeder 4; the first feeder 3 is used to contain the material A and feed it to the reactor 5; the second feeder 4 is used to contain the material B and feed it to the reactor 5; preferably, material A is fed after being cooled in the first feeder to a temperature within ±3°C of the feeding temperature of the solvent in the reactor, and material B is fed after being cooled in the second feeder to a temperature within ±3°C of the feeding temperature of the solvent in the reactor. Specifically, the first and second feeders can specifically adopt a feeding device that can accurately control the feeding amount. Specifically, the reactor is provided with a liquid ammonia inlet, and the liquid ammonia inlet is connected to the liquid ammonia input pipe 14.

[0081] In some specific embodiments, the refining unit includes an ammonia removal tank 6, a water removal adsorber 7, a refrigerator 8, a cold trap 9, a trace impurity adsorber 10 and a product tank 11 connected in series in sequence, and preferably also includes an ammonia water recovery device 12;

[0082] The ammonia removal tank 6 is connected to the reactor 5 and is used to make the crude germanium hydride product contact with water to absorb and remove ammonia and obtain ammonia water;

[0083] The dehydration adsorber 7 is connected to the ammonia removal tank 6 and is used to remove moisture from the germanium hydride crude product after being treated by the ammonia removal tank 6;

[0084] The refrigerator 8 is connected to the dehydration adsorber 7 and is used to remove digermane from the crude germanium hydride product after being treated by the dehydration adsorber 7;

[0085] The cold trap 9 is connected to the refrigerator 8 and is used to remove non-condensable gas from the crude germanium hydride product after being treated by the refrigerator 8;

[0086] The trace impurity adsorber 10 is connected to the cold trap 9 and is used to remove trace impurities in the crude germanium hydride product after being treated by the cold trap 9 and obtain the germanium hydride product;

[0087] The product tank 11 is connected to the trace impurity adsorber 10 and is used to receive the germanium hydride product;

[0088] The ammonia water recovery device 12 is connected to the ammonia removal tank 6 and is used to receive the ammonia water and mix it with liquid ammonia for repeated use.

[0089] More specifically, a condenser 13 is provided at the top of the reactor 5 to prevent ammonia from escaping during the reaction.

[0090] Each specific device, element, etc. involved in the preparation system of the present invention can adopt conventional devices or elements with corresponding functions in the art, and there is no special limitation on this.

[0091] In order to better understand the technical solution of the present invention, the content of the present invention is further described below in conjunction with the embodiments, but the content of the present invention is not limited to the following embodiments.

[0092] Where specific experimental steps or conditions are not specified in the examples, the corresponding conventional experimental steps or conditions in the art can be used. The reagents or instruments used without specifying the manufacturer are all conventional products that can be purchased commercially.

[0093] The following examples adopt Figure 1 The preparation system shown is used to produce germanium hydride. Figure 1 The specific description of the preparation system shown is given in the previous description and will not be repeated here.

[0094] The raw materials used in the embodiments and comparative examples are all commercially available industrial grade raw materials.

[0095] The purity analysis of germanium hydride products is carried out in accordance with GB / T31987-2015.

[0096] Example 1

[0097] S1: First, 0.2 mol of ammonium chloride is placed in the first grinder, and the air in the first grinder is replaced with hot nitrogen. The hot nitrogen temperature is 48°C, the grinder heating temperature is 50°C, the pressure is 0.1Mpa, the heating grinding time is 20min, the speed is 40r / min, and the hot nitrogen is purged for 1min every 5min during the heating period;

[0098] Then, 1 mol of magnesium germanium was placed in the first grinder and heated and ground for 20 minutes, with the rotation speed, heating temperature, pressure and hot nitrogen purge conditions remaining unchanged;

[0099] After the above treatment, material A is obtained, and material A is transferred to the first feeder and cooled to -15°C.

[0100] S2: 3.5 mol of ammonium chloride is placed in a second grinder, and the air in the second grinder is replaced with hot nitrogen. Then, the grinding is performed under the same rotation speed, heating temperature, pressure and hot nitrogen purge conditions as those of the first grinder in step S1. The grinding time is 40 minutes. After the grinding, material B is obtained, and material B is transferred to a second feeder and cooled to -15°C.

[0101] S3: Material B is added into 55 mol of liquid ammonia at -15°C in the reactor, and then material A is added into the reactor. The reaction temperature is -20°C, the pressure is 0.15Mpa, the stirring speed of the reactor is 55r / min, and the condenser temperature is -40°C.

[0102] S4: The crude product after the reaction is collected for refining treatment, specifically, it passes through a water-containing ammonia removal tank, a water removal adsorber (filled with 3A molecular sieve), a -76°C refrigerator, a -155°C cold trap, and a trace impurity adsorber (filled with 4A molecular sieve) in sequence for impurity removal treatment, and finally obtains a germanium hydride product with a yield of 80% and a purity of 5N; during the refining process, the impure ammonia gas passes through the ammonia removal tank to obtain ammonia water with a concentration of 20wt%, and the ammonia water is recovered to the ammonia water recovery device.

[0103] Example 2

[0104] S1: First, 0.5 mol of ammonium chloride is placed in the first grinder, and the air in the first grinder is replaced with hot nitrogen. The hot nitrogen temperature is 48°C, the grinder heating temperature is 50°C, the pressure is 0.12Mpa, the heating grinding time is 20min, the speed is 40r / min, and the hot nitrogen is purged for 1min every 5min during the heating period;

[0105] Then, 1 mol of magnesium germanium was placed in the first grinder and heated and ground for 20 minutes, with the rotation speed, heating temperature, pressure and hot nitrogen purge conditions remaining unchanged;

[0106] After the above treatment, material A is obtained, and material A is transferred to the first feeder and cooled to -18°C.

[0107] S2: 3.8 mol of ammonium chloride is placed in a second grinder, and the air in the second grinder is replaced with hot nitrogen. Then, the grinding is performed under the same rotation speed, heating temperature, pressure and hot nitrogen purge conditions as those of the first grinder in step S1. The grinding time is 45 minutes. After the grinding, material B is obtained, and material B is transferred to a second feeder and cooled to -18°C.

[0108] S3: Material B is added into 117.8 mol of liquid ammonia at -18°C in the reactor, and then material A is added into the reactor. The reaction temperature is -20°C, the pressure is 0.15 MPa, the stirring speed of the reactor is 50 r / min, and the condenser temperature is -40°C.

[0109] S4: The crude product after the reaction is refined with reference to step S4 of Example 1, and finally a germanium hydride product with a yield of 83% and a purity of 5N is obtained; during the refining process, the impure ammonia gas passes through an ammonia removal tank to obtain ammonia water with a concentration of 22wt%, and the ammonia water is recovered into an ammonia water recovery device.

[0110] Example 3

[0111] S1: First, 0.3 mol of ammonium chloride is placed in the first grinder, and the air in the first grinder is replaced with hot nitrogen. The hot nitrogen temperature is 48°C, the grinder heating temperature is 50°C, the pressure is 0.13Mpa, the heating grinding time is 20min, the speed is 40r / min, and the hot nitrogen is purged for 1min every 5min during the heating period;

[0112] Then, 1 mol of magnesium germanium was placed in the first grinder and heated and ground for 20 minutes, with the rotation speed, heating temperature, pressure and hot nitrogen purge conditions remaining unchanged;

[0113] After the above treatment, material A is obtained, and material A is transferred to the first feeder and cooled to -17°C.

[0114] S2: 3.6 mol of ammonium chloride is placed in a second grinder, the air in the second grinder is replaced with hot nitrogen, and then grinding is performed using the same rotation speed, heating temperature, pressure and hot nitrogen purge conditions as the first grinder in step S1. The grinding time is 40 minutes. After the grinding is completed, material B is obtained, and material B is transferred to a second feeder and cooled to -17°C.

[0115] S3: Material B is put into 66.3 mol, -17°C liquid ammonia in the reactor, and then material A is put into the reactor. The reaction temperature is -20°C, the pressure is 0.15Mpa, the stirring speed of the reactor is 60r / min, and the condenser temperature is -40°C.

[0116] S4: The crude product after the reaction is refined with reference to step S4 of Example 1, and finally a germanium hydride product with a yield of 84% and a purity of 5N is obtained; during the refining process, the impure ammonia gas passes through an ammonia removal tank to obtain ammonia water with a concentration of 23wt%, and the ammonia water is recovered into an ammonia water recovery device.

[0117] Example 4

[0118] S1: First, 0.3 mol of ammonium bromide was placed in the first grinder, and the air in the first grinder was replaced with hot nitrogen. The hot nitrogen temperature was 48°C, the grinder heating temperature was 50°C, the pressure was 0.14Mpa, the heating grinding time was 20min, the rotation speed was 40r / min, and the hot nitrogen was purged for 1min every 5min during the heating period;

[0119] Then, 1 mol of magnesium germanium was placed in the first grinder and heated and ground for 20 minutes, with the rotation speed, heating temperature, pressure and hot nitrogen purge conditions remaining unchanged;

[0120] After the above treatment, material A is obtained, and material A is transferred to the first feeder and cooled to -15°C.

[0121] S2: 3.6 mol of ammonium bromide is placed in a second grinder, the air in the second grinder is replaced with hot nitrogen, and then grinding is performed using the same rotation speed, heating temperature, pressure and hot nitrogen purge conditions as those of the first grinder in step S1. The grinding time is 45 minutes. After the grinding is completed, material B is obtained, and material B is transferred to a second feeder and cooled to -15°C.

[0122] S3: Material B is added into 97.5 mol, -15°C liquid ammonia in the reactor, and then material A is added into the reactor. The reaction temperature is -20°C, the pressure is 0.15 MPa, the stirring speed of the reactor is 60 r / min, and the condenser temperature is -40°C.

[0123] S4: The crude product after the reaction is refined with reference to step S4 of Example 1, and finally a germanium hydride product with a yield of 85% and a purity of 5N is obtained. During the refining process, the impure ammonia gas passes through an ammonia removal tank to obtain ammonia water with a concentration of 22wt%, which is recovered into an ammonia water recovery device.

[0124] Example 5

[0125] S1: First, 0.25 mol of ammonium thiocyanate was placed in the first grinder, and the air in the first grinder was replaced with hot nitrogen. The hot nitrogen temperature was 48°C, the grinder heating temperature was 50°C, the pressure was 0.12Mpa, the heating grinding time was 20min, the rotation speed was 40r / min, and during the heating period, hot nitrogen was purged for 1min every 5min;

[0126] Then, 1 mol of magnesium germanium was placed in the first grinder and heated and ground for 20 minutes, with the rotation speed, heating temperature, pressure and hot nitrogen purge conditions remaining unchanged;

[0127] After the above treatment, material A is obtained, and material A is transferred to the first feeder and cooled to -16°C.

[0128] S2: 3.5 mol of ammonium thiocyanate is placed in a second grinder, the air in the second grinder is replaced with hot nitrogen, and then grinding is performed using the same rotation speed, heating temperature, pressure and hot nitrogen purge conditions as those of the first grinder in step S1. The grinding time is 45 minutes. After the grinding is completed, material B is obtained, and material B is transferred to a second feeder and cooled to -16°C.

[0129] S3: Material B is added into 67.5 mol of liquid ammonia at -16°C in the reactor, and then material A is added into the reactor. The reaction temperature is -20°C, the pressure is 0.15 MPa, the stirring speed of the reactor is 45 r / min, and the condenser temperature is -40°C.

[0130] S4: The crude product after the reaction is refined with reference to step S4 of Example 1, and finally a germanium hydride product with a yield of 84% and a purity of 5N is obtained; during the refining process, the impure ammonia gas passes through an ammonia removal tank to obtain ammonia water with a concentration of 22wt%, and the ammonia water is recovered to an ammonia water recovery device.

[0131] Comparative Example 1 (Compared with Example 3)

[0132] 3.9 mol of ammonium chloride was added to 66.3 mol of liquid ammonia, and then 1 mol of magnesium germanium was added to the liquid ammonia. The reaction temperature was -20°C, the pressure was 0.15 MPa, the stirring speed of the reactor was 60 r / min, and the condenser temperature was -40°C.

[0133] The crude product after the reaction was refined according to step S4 of Example 1, and finally a germanium hydride product with a yield of 73% and a purity of 4.5N was obtained; during the refining process, the impure ammonia gas passed through an ammonia removal tank to obtain ammonia water with a concentration of 20wt%, which was recovered into an ammonia water recovery device.

[0134] Comparative Example 2 (Compared with Example 5)

[0135] 3.75 mol of ammonium thiocyanate was added into 67.5 mol of liquid ammonia, and then 1 mol of magnesium germanium was added into the liquid ammonia. The reaction temperature was -20°C, the pressure was 0.15 MPa, the stirring speed of the reactor was 50 r / min, and the condenser temperature was -40°C.

[0136] The crude product after the reaction was refined according to step S4 of Example 1, and finally a germanium hydride product with a yield of 69% and a purity of 3N was obtained.

[0137] Comparative Example 3

[0138] The same amount of ammonium chloride in step S2 of embodiment 1 and ammonium chloride in step S1 are directly combined and heated and ground in the first grinder. Other operations are carried out in accordance with embodiment 1.

[0139] Experimental results: Finally, a germanium hydride product with a yield of 68% and a purity of 3N was obtained.

[0140] Comparative Example 4

[0141] The process is carried out with reference to Example 1, except that in step S3, material A is first added to the reactor, and then material B is added to the reactor. Other operations are carried out with reference to Example 1.

[0142] Experimental results: Finally, a germanium hydride product with a yield of 67.5% and a purity of 3N was obtained.

[0143] Comparative Example 5

[0144] The same method is carried out with reference to Example 1, except that: in step S1, no abrasive mixing is performed, only magnesium germanium is heated and ground in the first grinder, and all of the ammonium chloride is heated and ground in the second grinder.

[0145] Experimental results: The final germanium hydride product with a yield of 72% and a purity of 3N was obtained.

[0146] It is easy to understand that the above embodiments are only examples for clear explanation and do not mean that the present invention is limited thereto. For ordinary technicians in the relevant field, other different forms of changes or modifications can be made based on the above description. It is not necessary and impossible to list all the implementation methods here. The obvious changes or modifications derived from this are still within the protection scope of the present invention.

Claims

1. A method for producing germanium hydride, characterized in that: The germanium hydride is produced by reacting ammonium halide or ammonium thiocyanate with magnesium germanium in the presence of a solvent. The production method comprises the following steps: (1) grinding a first portion of ammonium halide or ammonium thiocyanate in a first grinder and purging with hot nitrogen, then adding the magnesium germanium into the first grinder, and continuing to grind and mix to obtain material A; Grinding the second portion of ammonium halide or ammonium thiocyanate in a second grinder and purging with hot nitrogen to obtain material B; (2) putting the material B into a reactor and mixing it with the solvent, and then putting the material A into the reactor to obtain a crude germanium hydride product through reaction; (3) refining the crude germanium hydride product to obtain a germanium hydride product.

2. The production method according to claim 1, characterized in that The conditions for performing the grinding in the first grinder and in the second grinder include independently: a temperature of 10-60° C. and a pressure of 0.1-0.2 MPa.

3. The production method according to claim 2, characterized in that: The grinding time for the grinding in the first grinder and in the second grinder is 0.1-1 h, respectively.

4. The production method according to claim 2, characterized in that: Before the grinding in the first grinder and the second grinder, the air in the grinder is replaced with hot nitrogen gas respectively.

5. The production method according to claim 2, characterized in that: The difference between the temperature of the hot nitrogen gas and the temperature in the first grinder or the second grinder is within ±5°C.

6. The production method according to claim 2, characterized in that: In the first grinder or in the second grinder, the hot nitrogen gas is purged multiple times at intervals during the grinding process.

7. The production method according to claim 6, characterized in that: The number of purges is 2-10 times; the interval between each purge is 5-15 minutes.

8. The production method according to any one of claims 1 to 7, characterized in that: In step (1), after adding the magnesium germanium, the conditions for continuing grinding include: a temperature range of 10-60° C. and a pressure range of 0.1-0.2 MPa.

9. The production method according to claim 8, characterized in that: The time for continuing grinding is 0.1-1h.

10. The production method according to any one of claims 1 to 7, characterized in that: The ammonium halide is selected from one or more of ammonium chloride and ammonium bromide; And / or, the solvent is liquid ammonia.

11. The production method according to any one of claims 1 to 7, characterized in that: In step (2), the feeding temperature of the solvent is -25°C to 0°C.

12. The production method according to claim 11, characterized in that: In step (2), before being fed into the reactor, the material B and the material A are cooled to a temperature whose difference with the feeding temperature of the solvent is within ±3°C.

13. The production method according to any one of claims 1 to 7, characterized in that: The molar ratio of the first part of ammonium halide or ammonium thiocyanate to the magnesium germanium is 0.2-0.5:1; The molar ratio of the second part of ammonium halide or ammonium thiocyanate to the magnesium germanium is 3.5-3.8:1; The molar ratio of the second part of ammonium halide or ammonium thiocyanate to the solvent is 1:15-32.

14. The production method according to any one of claims 1 to 7, characterized in that: In step (2), the reaction is carried out at a temperature of -25°C to -10°C and a pressure of 0.1-0.2 MPa.

15. The production method according to claim 14, characterized in that: In step (2), during the reaction process, the stirring speed of the reactor is 20-80 r / min.

16. The production method according to claim 14, characterized in that The top of the reactor was equipped with a condenser, the temperature of which was -40°C to -50°C.

17. The production method according to any one of claims 1 to 7, characterized in that: In step (3), impurities in the crude germanium hydride product are removed by the refining treatment, and the impurities include one or more of ammonia, water, digermane, non-condensable gas and other possible trace impurities.

18. The production method according to claim 17, characterized in that: The refining treatment includes: first sending the crude germanium hydride product into an ammonia removal tank to absorb with water to remove ammonia therein, then sending it into a dehydration adsorber to remove moisture, then sending it into a refrigerator to remove digermane, then sending it into a cold trap to remove non-condensable gas, and then sending it into a trace impurity adsorber to remove trace impurities.

19. The production method according to claim 18, characterized in that In the ammonia removal tank, ammonia gas in the crude germanium hydride product is converted into ammonia water, and the obtained ammonia water is sent to an ammonia water recovery device for mixing with liquid ammonia to prepare industrial-grade ammonia water.

20. A germanium hydride preparation system for implementing the production method according to any one of claims 1 to 19, characterized in that: The preparation system comprises a first grinder, a second grinder, a reactor and a refining unit; The first grinder is provided with a hot nitrogen inlet, and the first grinder is used to grind the first part of ammonium halide or ammonium thiocyanate and the magnesium germanium to obtain the material A; The second grinder is provided with a hot nitrogen inlet, and the second grinder is used to grind the second portion of ammonium halide or ammonium thiocyanate to obtain the material B; The reactor is used to contact and react the material A and the material B in the presence of a solvent to obtain the crude germanium hydride product; The refining unit is used to perform a refining treatment on the crude germanium hydride product to obtain the germanium hydride product.

21. The germanium hydride preparation system according to claim 20, characterized in that: It also includes a first feeder and a second feeder; the first feeder is used to contain the material A and feed it into the reactor; the second feeder is used to contain the material B and feed it into the reactor; And / or, the refining unit comprises an ammonia removal tank, a water removal adsorber, a refrigerator, a cold trap, a trace impurity adsorber and a product tank connected in series in sequence, and also comprises an ammonia water recovery device; The ammonia removal tank is connected to the reactor and is used to make the crude germanium hydride product contact with water to absorb and remove ammonia and obtain ammonia water; The dehydration adsorber is connected to the ammonia removal tank and is used to remove moisture from the germanium hydride crude product after being treated by the ammonia removal tank; The refrigerator is connected to the dehydration adsorber and is used to remove digermane from the crude germanium hydride product after being treated by the dehydration adsorber; The cold trap is connected to the refrigerator and is used to remove non-condensable gas in the crude germanium hydride product after being treated by the refrigerator; The trace impurity adsorber is connected to the cold trap and is used to remove trace impurities in the germanium hydride crude product after being treated by the cold trap and obtain the germanium hydride product; The product tank is connected to the trace impurity adsorber and is used to receive the germanium hydride product; The ammonia water recovery device is connected to the ammonia removal tank and is used to receive the ammonia water and mix it with liquid ammonia.

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