Purification device and purification process of 72GeF4

Abstract

The invention provides a 72GeF4 purification device and a purification process, and belongs to the technical field of 72GeF4 purification. The 72GeF4 purification device comprises a filler rectifying tower, a condensation unit and a storage unit, the filler rectifying tower comprises a tower body, a reboiler, a condenser and filler, the reboiler is located at the bottom of the tower body, the condenser is located at the top of the tower body, the filler is located in the tower body, and the surface of the filler is provided with germanium metal; a gas inlet of the condensing unit is communicated with a discharge hole in the top of the tower body, and the condensing unit is configured to be capable of collecting liquid 72GeF4 and also capable of gasifying the collected liquid 72GeF4; and the storage unit is communicated with a gas outlet of the condensation unit so as to collect and store gaseous 72GeF4. By means of the purification device, high-abundance 72GeF4 can be used as a raw material, and high-abundance and high-purity 72GeF4 can be prepared from the high-abundance 72GeF4.

Description

Technical Field

[0001] This application involves 72 In the field of GeF4 purification technology, specifically, it relates to a... 72 Purification equipment and purification process for GeF4. Background Technology

[0002] Germanium tetrafluoride is a colorless gas with a molecular weight of 148.63. It solidifies immediately upon cooling at normal pressure and sublimates at -36.5°C. There are five naturally occurring stable germanium isotopes: 70 Ge 72 Ge 73 Ge 74 Ge 76 Ge, with abundances of 20.57%, 27.45%, 7.75%, 36.5%, and 7.73%, respectively. Among them, 72 In the semiconductor industry, GeF4 is mainly used in pre-amorphization implantation processes, taking into account device performance. 72 Ge abundance typically needs to be greater than 50%. However, currently high abundance... 72 GeF4 preparation technology (using germanium tetrafluoride gas centrifugation method) 72 Enrichment of Ge to prepare high-abundance... 72 GeF4 is mainly concentrated in the U.S. Isotope Development Center, the European company Urenco, and the Russian Isotope J., therefore, high abundance... 72 GeF4 currently relies heavily on imports, which makes it relatively expensive. Furthermore, the high abundance of imported GeF4... 72 GeF4 contains a significant amount of impurities (mainly including N2, O2, HF, BF3, and SiF4), making it difficult to meet the purity requirements for semiconductor applications (typically requiring a purity of 99.999%). Furthermore, existing distillation purification equipment is primarily designed for naturally abundant germanium tetrafluoride (whose... 72 The Ge abundance is approximately 27%, mainly obtained through a substitution reaction using germanium tetrachloride and fluorine gas as raw materials (correspondingly, its impurity composition also differs). Therefore, for high-abundance... 72 There is an urgent need to design a new type of distillation and purification device for GeF4. Summary of the Invention

[0003] The purpose of this application is to provide a 72 A purification apparatus and process for GeF4 were developed, which allows for the purification of high-abundance GeF4. 72 Using GeF4 as a raw material, a product with both high abundance and high purity was prepared. 72 GeF4.

[0004] The embodiments of this application are implemented as follows: Firstly, embodiments of this application provide a 72 The GeF4 purification unit includes a packed distillation column, a condenser unit, and a storage unit. The packed distillation column comprises a column body, a reboiler, a condenser, and packing material. The reboiler is located at the bottom of the column body, the condenser is located at the top of the column body, and the packing material is located inside the column body with a germanium metal surface. The inlet of the condenser unit is connected to the outlet at the top of the column body, and the condenser unit is configured to collect liquid. 72 GeF4 can also make the collected liquid 72 GeF4 is vaporized; the storage unit is connected to the outlet of the condensation unit to collect and store the gaseous state. 72 GeF4.

[0005] In the above technical solution, the packing surface in the packed distillation column has germanium metal, which can effectively remove... 72 Specifically, the impurities HF, BF3, and SiF4 in GeF4 are: (1) HF and germanium metal can react to generate GeF4 and H2. The boiling point difference between H2 and GeF4 is greater than that between HF and GeF4. The generated H2 can be easily removed by distillation, thereby effectively reducing the HF content without introducing new impurities; (2) BF3 and germanium metal can react to generate GeF4 and elemental B. Elemental B is adsorbed and retained by the packing material, thereby effectively reducing the BF3 content without introducing new impurities; (3) SiF4 and germanium metal can react to generate GeF4 and elemental Si. Elemental Si is adsorbed and retained by the packing material, thereby effectively reducing the SiF4 content without introducing new impurities. At the same time, the distillation purification process can also utilize the boiling point difference to remove the impurities. 72 Low-boiling-point impurities (such as O2, N2, etc.) and high-boiling-point impurities (such as HF, etc.) in GeF4 can be effectively removed. Therefore, with the purification apparatus provided in the embodiments of this application, high-abundance impurities can be removed. 72 Using GeF4 as a raw material, a product with both high abundance and high purity was prepared. 72 GeF4.

[0006] In some alternative implementations, the surface of the filler has a germanium metal layer.

[0007] In the above technical solution, the germanium metal on the surface of the filler exists in a layered form, so that the surface of the filler has a sufficient amount of germanium metal, thereby more effectively removing [the germanium metal]. 72 HF, BF3 and SiF4 impurities in GeF4.

[0008] In some alternative implementations, the thickness of the germanium metal layer is 5 μm to 30 μm.

[0009] In the above technical solution, the thickness of the germanium metal layer is limited to the aforementioned range. This ensures that the packing surface has sufficient germanium metal while maintaining a large overall specific surface area. The large specific surface area allows for sufficient contact and efficient mass transfer between the gas and liquid phases at the packing, thereby effectively removing… 72 Various impurities in GeF4.

[0010] In some alternative implementations, the inner walls of the packing's pore structure are also made of germanium metal.

[0011] In the above technical solution, by incorporating germanium metal into the pore structure of the packing, the germanium metal content in the packing can be further increased. Simultaneously, it allows for a larger contact area between the germanium metal and impurities, thus enabling more effective removal. 72 HF, BF3 and SiF4 impurities in GeF4.

[0012] In some alternative implementations, the tower height is 1 m to 5 m, the inner diameter of the tower is 20 mm to 50 mm, and the average diameter of the packing is 1.5 mm to 6 mm.

[0013] In the above technical solution, the tower body has the aforementioned height and inner diameter, and the packing has the aforementioned average diameter; the combination of the two can achieve a small quantity... 72 Distillation purification of GeF4.

[0014] In some alternative implementations, the reboiler includes a reboiler body, a flow guide shroud, and a reboiler shell. The shell is fitted over the reboiler body, and the outer wall of the reboiler body and the inner wall of the reboiler shell together form a liquid collection tank communicating with the tower body. The flow guide shroud is placed on top of the reboiler body.

[0015] In the above technical solution, the reboiler consists of a reboiler body, a flow guide shroud, and a reboiler shell, and is arranged in the above manner. By utilizing the space-occupying function of the reboiler body itself, when the liquid level at the reboiler is constant, this type of reboiler requires less liquid (i.e., less liquid is needed). 72 GeF4 requires fewer raw materials and is more suitable for small quantities. 72 Distillation purification of GeF4.

[0016] In some alternative implementations, the flow deflector protrudes toward the side opposite to the reboiler body.

[0017] In the above technical solution, the flow guide is designed to protrude towards the side away from the reboiler body, which can better guide the liquid into the collection tank while sealing the reboiler body.

[0018] In some alternative implementations, the outer peripheral wall of the reboiler shell is provided with a first heating element.

[0019] In the above technical solution, a first heating element is provided on the outer peripheral wall of the reboiler shell. This type of heating element has the advantages of high heating efficiency and easy installation.

[0020] In some alternative embodiments, the bottom of the reboiler body protrudes from the bottom of the reboiler shell along the axial direction of the tower body, and a second heating element is provided on the outer peripheral wall of the protruding area of ​​the reboiler body.

[0021] In the above technical solution, the bottom of the reboiler body protrudes from the bottom of the reboiler shell and a second heating element is set there. Through the combined action of the second heating element and the first heating element, the heat transfer effect at the reboiler can be improved, thereby improving the vaporization efficiency of the liquid.

[0022] In some alternative implementations, temperature sensors are provided on both the first and second heating elements, and multiple temperature sensors are distributed at intervals along the axial direction of the tower body.

[0023] In the above technical solution, the temperature sensor can monitor the liquid temperature in the reboiler in real time. At the same time, multiple temperature sensors are distributed at intervals along the axial direction of the tower body. The liquid level in the reboiler can also be monitored synchronously by measuring the temperature of the temperature sensor at different locations.

[0024] In some alternative implementations, an overflow hole is provided on the outer wall of the reboiler body, and the overflow hole is located between the first heating element and the flow guide shroud in the axial direction of the tower body.

[0025] In the above technical solution, an overflow hole is added to the reboiler body and its position is set between the first heating element and the flow guide shroud. When the liquid level at the reboiler is too high, the excess liquid above the first heating element can enter the reboiler body through the overflow hole. At this time, the second heating element at the bottom of the reboiler body can directly heat the excess liquid, and the generated gas can enter the tower body through the overflow hole, so that the excess liquid above the first heating element can also be efficiently vaporized, thereby enabling most of the liquid at the reboiler to participate in the gas-liquid circulation efficiently.

[0026] In some alternative embodiments, the condensation unit includes a first cold trap and a second cold trap spaced apart, the inlets of which are both connected to the outlet at the top of the tower. The first cold trap is configured to collect liquid. 72 GeF4 can also make the collected liquid 72 GeF4 is vaporized, and the second cold trap is configured to collect liquid impurities and vaporize them; the storage unit includes a first storage bottle and a second storage bottle spaced apart, the first storage bottle being connected to the outlet of the first cold trap for collecting and storing gaseous impurities. 72The GeF4 storage bottle is connected to the outlet of the second cold trap and is used to collect and store gaseous impurities.

[0027] In the above technical solution, the condensation unit includes a first cold trap and a second cold trap, and the storage unit includes a first storage bottle and a second storage bottle, which are arranged in the above manner. That is, the purification device has two relatively independent gas collection paths, which can collect gases from the gas. 72 GeF4 and impurities are collected in stages and independently, thereby improving the yield of the prepared product. 72 The GeF4 purity is high, and the collected impurities can be recycled, thereby reducing raw material waste and reducing environmental pressure.

[0028] In some alternative embodiments, the first cold trap includes a cold trap body, an inlet pipe, an outlet pipe, a cold trap shell, and a third heating element. The cold trap body has a collection cavity. One end of the inlet pipe is connected to the outlet and the other end extends into the collection cavity. One end of the outlet pipe is connected to the collection cavity and the other end is connected to the inlet of the first storage bottle. The third heating element extends into the collection cavity and is housed in the inlet pipe in the corresponding area. The cold trap shell is fitted over the cold trap body, and the outer wall of the cold trap body and the inner wall of the cold trap shell together form a medium cavity for conveying the heat exchange medium.

[0029] In the above technical solution, the first cold trap consists of a cold trap body, an inlet pipe, an outlet pipe, a cold trap shell, and a third heating element, and is arranged in the manner described above. The third heating element is disposed inside the inlet pipe, in a liquid state... 72 During the GeF4 collection stage, the third heating element can be heated with low power, thereby reducing... 72 There is a risk that GeF4 will rapidly solidify during the cooling and collection process at atmospheric pressure, leading to blockage of the intake pipe. 72 During the GeF4 discharge stage, the third heating element can heat the liquid at high power, thereby making the liquid... 72 GeF4 is rapidly vaporized and collected by the downstream storage bottle; in addition, the third heating element is located away from the medium chamber, which can reduce mutual interference with the heat exchange medium during the heating process. At the same time, this arrangement also makes the entire condenser have the advantages of a more compact overall structure and a smaller footprint.

[0030] In some alternative implementations, both the air intake pipe and the third heating element extend to the bottom of the cold trap body.

[0031] In the above technical solution, both the air inlet pipe and the third heating element extend to the bottom of the cold trap body, giving the fluid a large heat exchange area and sufficient heat exchange time in the collection chamber, which helps to improve the liquid state. 72 GeF4 collection efficiency and liquid 72 GeF4 excretion efficiency.

[0032] In some alternative implementations, the outer wall of the cold trap housing is also provided with an insulation layer.

[0033] In the above technical solution, an insulation layer is added to the outer wall of the cold trap shell, which can reduce the energy loss of the heat exchange medium, so that the heat exchange medium in the medium cavity and the gaseous state in the collection cavity can be effectively separated. 72 GeF4 can perform heat exchange fully and efficiently to achieve gaseous state 72 Rapid cooling and liquefaction of GeF4.

[0034] Secondly, embodiments of this application provide a 72 The purification process for GeF4 adopts the method provided in the first aspect embodiment. 72 The purification of GeF4 is carried out using a device that includes the following steps: S1. Hydrogen gas is introduced into the packed distillation column for activation treatment to remove oxide impurities on the surface of germanium metal. Then, the packed distillation column is sequentially purged with inert gas and evacuated. S2. After the evacuation treatment is completed, gaseous gas is introduced into the packed distillation column. 72 The crude GeF4 is fed until the feed rate reaches the preset value, then the feed inlet is closed and distillation is performed; S3, the condenser unit is opened to collect the liquid. 72 GeF4; then make it liquid 72 GeF4 vaporizes and opens the storage cell, allowing the gaseous state to... 72 GeF4 enters the storage unit.

[0035] In the above technical solution, the method provided by the first aspect embodiment is adopted. 72 The GeF4 purification device was used to process the gaseous phase according to the above process. 72 Crude GeF4 can be purified by distillation to obtain a product with both high abundance and high purity. 72 GeF4.

[0036] In some alternative embodiments, during the activation treatment step, the hydrogen flow rate is 0.5 L / min to 30 L / min, the treatment temperature is 100°C to 250°C, and the treatment time is 24 h to 48 h; or / and, during the inert gas purging treatment step, the inert gas flow rate is 0.5 L / min to 30 L / min, and the purging time is 4 h to 8 h; or / and, during the vacuum treatment step, until the vacuum degree in the packed distillation column is less than 30 mtorr.

[0037] In the above technical solution, limiting the hydrogen flow rate, processing temperature, and processing time in the activation step to the aforementioned ranges can effectively remove oxide impurities from the surface of germanium metal, thus facilitating the subsequent preparation of high-purity germanium. 72GeF4; By limiting the inert gas flow rate and purging time in the inert gas purging process to the above range, hydrogen and moisture in the packed distillation column can be effectively removed; The vacuuming process is carried out according to the above standards to ensure a high level of cleanliness in the packed distillation column.

[0038] In some alternative implementations, the contents are introduced into the packed distillation column. 72 In the process of producing crude GeF4, the feed rate is 0.5 kg to 10 kg and the feed flow rate is 0.1 kg / h to 5 kg / h.

[0039] In the above technical solution, 72 The minimum feed rate for crude GeF4 is as low as 0.5 kg, making it suitable for small-scale applications. 72 The distillation and purification of GeF4, while controlling the feed flow rate within the above-mentioned range, has the advantage of high feed stability.

[0040] In some alternative implementations, during the distillation process, the pressure inside the packed distillation column is 0.2 MPa to 0.3 MPa, and the pressure at the reboiler is... 72 The temperature of GeF4 is higher than that at the condenser. 72 The temperature of GeF4 and 72 The temperature difference of GeF4 is 0.1℃~1℃, where the temperature difference at the reboiler is... 72 The temperature range for GeF4 is -24.3℃ to -16.9℃, and the treatment time is 1 h to 8 h.

[0041] In the above technical solution, the pressure in the distillation process and the pressure at the reboiler are... 72 GeF4 temperature (i.e.) 72 (the temperature at which GeF4 heat exchangers are located) and the temperature at the condenser. 72 GeF4 temperature (i.e.) 72 The temperature reached at the point of heat exchange with GeF4 and the processing time are both limited within the aforementioned ranges, providing suitable distillation conditions for subsequent preparation of high-purity and high-yield products. 72 GeF4.

[0042] In some alternative embodiments, the condensation unit includes a first cold trap and a second cold trap spaced apart, the inlets of which are both connected to the outlet at the top of the tower. The first cold trap is configured to collect liquid. 72 GeF4 can also make the collected liquid 72 GeF4 is vaporized; the second cold trap is configured to collect liquid impurities and also to vaporize the collected liquid impurities; the condensation unit is opened to collect the liquid. 72The steps of GeF4 include: first, opening the second cold trap to collect liquid low-boiling-point impurities; and then, once the content of low-boiling-point impurities in the gas at the outlet meets a preset value, closing the second cold trap and opening the first cold trap to collect liquid impurities. 72 GeF4 is used until the content of high-boiling-point impurities in the gas at the outlet exceeds the preset value. Then, the first cold trap is closed and the second cold trap is opened again to collect the liquid high-boiling-point impurities.

[0043] In the above technical solution, impurities in the gas after distillation are collected in stages and independently according to the above process. 72 GeF4 can be prepared with higher purity. 72 GeF4.

[0044] In some alternative implementations, the flow rate at the outlet is 0.01 kg / h to 0.1 kg / h during the step of collecting liquid low-boiling-point impurities.

[0045] In the above technical solution, controlling the flow rate within the aforementioned range during the step of collecting liquid low-boiling-point impurities can effectively remove low-boiling-point impurities while reducing [the amount of water / water]. 72 The loss of GeF4.

[0046] In some alternative implementations, liquid is collected. 72 In the GeF4 process, the flow rate at the outlet is 0.05 kg / h to 0.5 kg / h.

[0047] In the above technical solution, liquid will be collected. 72 The flow control in the GeF4 step is within the above range, which can effectively collect... 72 GeF4 reduces the content of high-boiling-point impurities. Attached Figure Description

[0048] To more clearly illustrate the technical solutions of the embodiments of this application, the accompanying drawings used in the embodiments will be briefly introduced below. It should be understood that the following drawings only show some embodiments of this application and should not be regarded as a limitation of the scope. For those skilled in the art, other related drawings can be obtained based on these drawings without creative effort.

[0049] Figure 1 An embodiment provided in this application 72 A schematic diagram of the GeF4 purification device; Figure 2 This is a schematic diagram of a reboiler provided in an embodiment of this application; Figure 3 This is a schematic diagram of the structure of a first cold trap provided in an embodiment of this application.

[0050] Icon: 10- 72 Purification apparatus for GeF4; 100-Packed distillation column; 110-Column body; 111-Packing; 120-Reboiler; 121-Reboiler body; 1211-Overflow hole; 122-Flow guide hood; 123-Reboiler shell; 124-Collection tank; 125-First heating element; 126-Second heating element; 127-Temperature sensor; 130-Condenser; 200-Condensation unit; 210-First cold trap; 211-Cold trap body; 2111-Collection chamber; 212-Inlet pipe; 213-Outlet pipe; 214-Cold trap shell; 215-Third heating element; 216-Media chamber; 217-Media feed pipe; 218-Media outlet pipe; 220-Second cold trap; 300-Storage unit; 310-First storage bottle; 320-Second storage bottle. Detailed Implementation

[0051] To make the objectives, technical solutions, and advantages of the embodiments of this application clearer, the technical solutions of the embodiments of this application will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of this application, and not all embodiments. The components of the embodiments of this application described and shown in the accompanying drawings can generally be arranged and designed in various different configurations.

[0052] Therefore, the following detailed description of the embodiments of this application provided in the accompanying drawings is not intended to limit the scope of the claimed application, but merely to illustrate selected embodiments of the application. All other embodiments obtained by those skilled in the art based on the embodiments of this application without inventive effort are within the scope of protection of this application.

[0053] It should be noted that similar labels and letters in the following figures indicate similar items. Therefore, once an item is defined in one figure, it does not need to be further defined and explained in subsequent figures.

[0054] In the description of this application, it should be noted that the terms "upper," "lower," "inner," and "outer," etc., indicate the orientation or positional relationship based on the orientation or positional relationship shown in the accompanying drawings, or the orientation or positional relationship commonly used when the product is in use. They are used only for the convenience of describing this application and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation, and therefore should not be construed as a limitation on this application. In addition, the terms "first," "second," and "third," etc., are used only to distinguish descriptions and should not be construed as indicating or implying relative importance.

[0055] In the description of this application, it should also be noted that, unless otherwise expressly specified and limited, the terms "set up," "install," "connect," and "link" should be interpreted broadly. For example, they can refer to a fixed connection, a detachable connection, or an integral connection; they can refer to a direct connection or an indirect connection through an intermediate medium; and they can refer to the internal connection of two components. Those skilled in the art can understand the specific meaning of the above terms in this application based on the specific circumstances.

[0056] The following is an example provided in this application. 72 The purification apparatus and purification process for GeF4 are described in detail.

[0057] See Figure 1 In the first aspect, embodiments of this application provide a 72 The GeF4 purification apparatus 10 includes a packed distillation column 100, a condensation unit 200, and a storage unit 300. The packed distillation column 100 includes a column body 110, a reboiler 120, a condenser 130, and packing 111. The reboiler 120 is located at the bottom of the column body 110, the condenser 130 is located at the top of the column body 110, and the packing 111 is located inside the column body 110 with a germanium metal surface. The inlet of the condensation unit 200 is connected to the outlet at the top of the column body 110, and the condensation unit 200 is configured to collect liquid. 72 GeF4 can also make the collected liquid 72 GeF4 is vaporized; the storage unit 300 is connected to the outlet of the condensation unit 200 to collect and store the gaseous state. 72 GeF4.

[0058] It should be noted that the condensation unit 200 is added between the packed distillation column 100 and the storage unit 300 because of the gaseous state. 72 If GeF4 enters the storage unit 300 directly, it can easily cause blockage of the air inlet of the storage unit 300, making it difficult to collect properly. Therefore, a condensation unit 200 needs to be added (which can condense the liquid). 72 GeF4 vaporization) is used to provide additional pressure; at the same time, the added condensation unit 200 (which can condense the gaseous state using a low-temperature medium) is used to provide additional pressure. 72 GeF4 rapid condensation and liquefaction can also collect liquid. 72 GeF4, to achieve gaseous flow from the outlet 72 Efficient collection and concentration of GeF4.

[0059] It should be noted that the structure of the tower body 110 can be configured in accordance with conventional forms in the art. For example, the tower body 110 has a cavity, and the packing 111 is distributed at intervals along the axial direction of the tower body 110 in the cavity.

[0060] It should be noted that in the packed distillation column 100, the packing 111 is a porous structure to give it a high specific surface area.

[0061] In this application, the packing 111 in the packed distillation column 100 has germanium metal on its surface, which can effectively remove... 72 Specifically, regarding the impurities HF, BF3, and SiF4 in GeF4, (1) HF and germanium can react to generate GeF4 and H2. The boiling point difference between H2 and GeF4 is greater than that between HF and GeF4, so the generated H2 can be easily removed by distillation, thereby effectively reducing the HF content without introducing new impurities; (2) BF3 and germanium can react to generate GeF4 and elemental B, where elemental B is adsorbed and retained by packing 111, thereby effectively reducing the BF3 content without introducing new impurities; (3) SiF4 and germanium can react to generate GeF4 and elemental Si, where elemental Si is adsorbed and retained by packing 111, thereby effectively reducing the SiF4 content without introducing new impurities; at the same time, the distillation purification process can also utilize the boiling point difference to remove the impurities. 72 Low-boiling-point and high-boiling-point impurities in GeF4 can be effectively removed. Therefore, the purification apparatus provided in this application embodiment can effectively remove high-abundance impurities. 72 Using GeF4 as a raw material, a product with both high abundance and high purity was prepared. 72 GeF4.

[0062] As an example, the surface of filler 111 has a germanium metal layer.

[0063] In this embodiment, the germanium metal on the surface of the filler 111 exists in a layered form, so that the surface of the filler 111 has a relatively sufficient amount of germanium metal, thereby removing it more effectively. 72 HF, BF3 and SiF4 impurities in GeF4.

[0064] As an example, the thickness of the germanium metal layer is 5 μm to 30 μm, for example, but not limited to any point value or any range between 5 μm, 10 μm, 15 μm, 20 μm, 25 μm and 30 μm.

[0065] In this embodiment, the thickness of the germanium metal layer is limited to the aforementioned range. This ensures that the surface of the filler 111 has sufficient germanium metal while maintaining a large specific surface area for the filler 111 as a whole. This large specific surface area allows for sufficient contact and efficient mass transfer between the gas and liquid phases at the filler 111, thereby effectively removing… 72 Various impurities in GeF4.

[0066] As an example, the inner walls of the pore structure of filler 111 also have germanium metal.

[0067] In this embodiment, by utilizing the pore structure of the filler 111 to incorporate germanium metal, the germanium metal content in the filler 111 can be further increased. Simultaneously, it allows for a larger contact area between the germanium metal and impurities, thus enabling more effective removal. 72 HF, BF3 and SiF4 impurities in GeF4.

[0068] It should be noted that there are no limitations on the way germanium metal is formed on the surface of filler 111 and the inner wall of the pore structure. In this embodiment, electrolysis is used as an example, that is, filler 111 is immersed in a solution containing germanium metal salt, and then electricity is applied to reduce germanium metal ions to elemental germanium, so as to form germanium metal on the surface of filler 111 and the inner wall of the pore structure. Then, it is washed with water and dried to obtain the final product.

[0069] It should be noted that the specific process of electrolysis is not limited and can be carried out in accordance with conventional processes in this field.

[0070] As an example, the type of packing 111 is selected from at least one of θ-ring packing 111, triangular spiral packing 111 and calendered perforated plate packing 111.

[0071] As an example, the material of filler 111 is selected from at least one of stainless steel, nickel, and Hastelloy.

[0072] In this embodiment, the types and materials of the filler 111 are quite diverse, providing a wide range of feasible solutions, which facilitates the promotion and application of the technical solutions provided in this application.

[0073] It should be noted that due to high abundance 72 The relatively high cost of GeF4 raw materials makes it difficult to process high abundance in small quantities (processing volumes as low as less than 1 kg). 72 The distillation purification of GeF4 has become a current research focus. However, existing conventional distillation purification equipment is generally suitable for large-scale (typically tens or even hundreds of kilograms) distillation purification of low-abundance germanium tetrafluoride. Meanwhile, the distillation purification in packed distillation column 100 requires maintaining a suitable liquid level at the reboiler 120 at the bottom of column 110 and keeping the liquid holdup in the packing 111 at an appropriate level. This makes it difficult to directly apply conventional distillation purification equipment designed for large-scale low-abundance applications to small-scale high-abundance applications. Therefore, there is an urgent need to design a method suitable for small-scale high-abundance applications. 72 A distillation and purification apparatus for GeF4.

[0074] As an example, the height of the tower body 110 is 1 m to 5 m (e.g., but not limited to any one of the heights of 1 m, 2 m, 3 m, 4 m and 5 m or any range between any two), the inner diameter of the tower body 110 is 20 mm to 50 mm (e.g., but not limited to any one of the inner diameters of 20 mm, 30 mm, 40 mm and 50 mm or any range between any two); and / or the average diameter of the packing 111 is 1.5 mm to 6 mm (e.g., but not limited to any one of the average inner diameters of 1.5 mm, 2 mm, 3 mm, 4 mm, 5 mm and 6 mm or any range between any two).

[0075] In this embodiment, the tower body 110 has the aforementioned height and inner diameter, while the packing 111 has the aforementioned average diameter, using a small amount of high abundance... 72 In the case of GeF4, the combination of the two can maintain a suitable liquid level at the reboiler 120 at the bottom of the column 110 and keep the liquid holdup in the packing 111 at a suitable level, thereby achieving a small amount of liquid... 72 Distillation purification of GeF4.

[0076] See Figure 1 and Figure 2 As an example, the reboiler 120 includes a reboiler body 121, a flow guide 122, and a reboiler shell 123. The reboiler shell 123 is fitted over the reboiler body 121. The outer wall of the reboiler body 121 and the inner wall of the reboiler shell 123 together form a liquid collection tank 124 that communicates with the tower body 110. The flow guide 122 covers the top of the reboiler body 121.

[0077] In this embodiment, the reboiler 120 is composed of a reboiler body 121, a flow guide shroud 122, and a reboiler shell 123, and is arranged as described above. By utilizing the space-occupying function of the reboiler body 121, when the liquid level at the reboiler 120 is constant, this type of reboiler 120 requires less liquid (i.e., less liquid is needed). 72 GeF4 requires fewer raw materials and is more suitable for small quantities. 72 Distillation purification of GeF4.

[0078] See Figure 2 As an example, the flow deflector 122 protrudes toward the side opposite to the reboiler body 121.

[0079] In this embodiment, the flow guide shroud 122 is configured to protrude toward the side opposite to the reboiler body 121, which can better guide the liquid into the collection tank 124 while sealing the reboiler body 121.

[0080] It should be noted that the form and location of the heating element in the reboiler 120 are not limited, as long as it can heat the liquid in the collection tank 124.

[0081] See Figure 2 As an example, the outer peripheral wall of the reboiler shell 123 is provided with a first heating element 125.

[0082] In this embodiment, a first heating element 125 is provided on the outer peripheral wall of the reboiler shell 123. This type of heating element has the advantages of high heating efficiency and easy installation.

[0083] See Figure 2 As an example, the first heating element 125 is sleeved on the outer wall of the reboiler shell 123, that is, the first heating element 125 is integrally formed.

[0084] In other possible implementations, the first heating element 125 may also be configured as a plurality of elements and distributed circumferentially along the reboiler housing 123.

[0085] See Figure 2 As an example, in the axial direction of the tower body 110, the bottom of the reboiler body 121 protrudes from the bottom of the reboiler shell 123, and the outer peripheral wall of the protruding area of ​​the reboiler body 121 is provided with a second heating element 126.

[0086] In this embodiment, the bottom of the reboiler body 121 protrudes from the bottom of the reboiler shell 123 and a second heating element 126 is provided there. Through the combined action of the second heating element 126 and the first heating element 125, the heat transfer effect at the reboiler 120 can be improved, thereby improving the vaporization efficiency of the liquid.

[0087] See Figure 2 As an example, the second heating element 126 is sleeved on the outer wall of the reboiler body 121, that is, the second heating element 126 is integrally formed.

[0088] In other possible implementations, the second heating element 126 may also be configured as a plurality of elements and distributed circumferentially along the reboiler body 121.

[0089] See Figure 2 As an example, temperature sensors 127 are provided on both the first heating element 125 and the second heating element 126, and multiple temperature sensors 127 are distributed at intervals along the axial direction of the tower body 110.

[0090] In this embodiment, the temperature sensor 127 can monitor the liquid temperature in the reboiler 120 in real time. At the same time, multiple temperature sensors 127 are distributed at intervals along the axial direction of the tower body 110. The liquid level in the reboiler 120 can also be monitored synchronously by measuring the temperature of the temperature sensors 127 at different locations.

[0091] See Figure 2 As an example, the outer wall of the reboiler body 121 is provided with an overflow hole 1211, and in the axial direction of the tower body 110, the overflow hole 1211 is located between the first heating element 125 and the flow guide shroud 122.

[0092] In this embodiment, an overflow hole 1211 is added to the reboiler body 121 and its position is set between the first heating element 125 and the guide shroud 122. When the liquid level at the reboiler 120 is too high, the excess liquid above the first heating element 125 can enter the reboiler body 121 through the overflow hole 1211. At this time, the second heating element 126 at the bottom of the reboiler body 121 can directly heat the excess liquid. The generated gas can then enter the tower body 110 through the overflow hole 1211, so that the excess liquid above the first heating element 125 can also be efficiently vaporized, thereby enabling most of the liquid at the reboiler 120 to participate in the gas-liquid circulation efficiently.

[0093] See Figure 3 As an example, the condensation unit 200 includes a first cold trap 210 and a second cold trap 220 spaced apart. The air inlets of both the first cold trap 210 and the second cold trap 220 are connected to the discharge port at the top of the tower body 110. The first cold trap 210 is configured to collect liquid. 72 GeF4 can also make the collected liquid 72 GeF4 is vaporized, and the second cold trap 220 is configured to collect liquid impurities and vaporize them; the storage unit 300 includes a first storage bottle 310 and a second storage bottle 320 spaced apart, the first storage bottle 310 being connected to the outlet of the first cold trap 210 for collecting and storing gaseous impurities. 72 GeF4, the second storage bottle 320 is connected to the outlet of the second cold trap 220, and is used to collect and store gaseous impurities.

[0094] In this embodiment, the condensation unit 200 includes a first cold trap 210 and a second cold trap 220, and the storage unit 300 includes a first storage bottle 310 and a second storage bottle 320, and the two are arranged in the manner described above. That is, the purification device has two relatively independent gas collection paths, which can collect gas from the condensation unit 200. 72 GeF4 and impurities are collected in stages and independently, thereby improving the yield of the prepared product. 72The GeF4 purity is high, and the collected impurities can be recycled, thereby reducing raw material waste and reducing environmental pressure.

[0095] See Figure 3 As an example, the first cold trap 210 includes a cold trap body 211, an inlet pipe 212, an outlet pipe 213, a cold trap shell 214, and a third heating element 215. The cold trap body 211 has a collection chamber 2111. One end of the inlet pipe 212 is connected to the outlet and the other end extends into the collection chamber 2111. One end of the outlet pipe 213 is connected to the collection chamber 2111 and the other end is connected to the inlet of the first storage bottle 310. The third heating element 215 extends into the collection chamber 2111 and is housed within the inlet pipe 212 in the corresponding area. The cold trap shell 214 is fitted over the cold trap body 211, and the outer wall of the cold trap body 211 and the inner wall of the cold trap shell 214 together form a medium cavity 216 for conveying the heat exchange medium (by introducing a low-temperature medium into the medium cavity 216, gaseous state can be achieved through heat exchange). 72 (Rapid condensation and liquefaction of GeF4).

[0096] In this embodiment, the first cold trap 210 is composed of a cold trap body 211, an inlet pipe 212, an outlet pipe 213, a cold trap outer shell 214, and a third heating element 215, and is arranged as described above. The third heating element 215 is disposed inside the inlet pipe 212, in a liquid state... 72 During the GeF4 collection stage, the third heating element 215 can be heated with low power, thereby reducing... 72 There is a risk that GeF4 will rapidly solidify during the cooling and collection process at atmospheric pressure, potentially causing blockage of the intake manifold 212. 72 During the GeF4 discharge stage, the third heating element 215 can be heated at high power, thereby making the liquid... 72 GeF4 is rapidly vaporized and collected by the downstream storage bottle; in addition, the third heating element 215 is located away from the medium chamber 216, which can reduce mutual interference with the heat exchange medium during the heating process. At the same time, this arrangement also makes the entire condenser 130 have the advantages of a more compact overall structure and a smaller space occupation.

[0097] Understandably, the top of the cold trap housing 214 is also provided with a medium inlet pipe 217 and a medium outlet pipe 218 that communicate with the medium cavity 216.

[0098] See Figure 3 As an example, both the intake pipe 212 and the third heating element 215 extend to the bottom of the cold trap body 211.

[0099] In this embodiment, both the air inlet pipe 212 and the third heating element 215 extend to the bottom of the cold trap body 211, giving the fluid a large heat exchange area and sufficient heat exchange time in the collection chamber 2111, which helps to improve the liquid state. 72 GeF4 collection efficiency and liquid 72 GeF4 excretion efficiency.

[0100] See Figure 3 As an example, the outer wall of the cold trap housing 214 is also provided with an insulation layer.

[0101] In this embodiment, an insulation layer is added to the outer wall of the cold trap shell 214 to reduce the energy loss of the heat exchange medium, so that the heat exchange medium in the medium cavity and the gaseous state in the collection cavity 2111 can be kept in harmony. 72 GeF4 can perform heat exchange fully and efficiently to achieve gaseous state 72 Rapid cooling and liquefaction of GeF4.

[0102] It should be noted that the structure of the second cold trap 220 can be referred to the first cold trap 210, the only difference being that the air outlet of the second cold trap 220 is connected to the air inlet of the second storage bottle 320.

[0103] It should be noted that structural units or functional devices in the purification device that are not specifically described or limited can be set up in accordance with conventional selection in the field.

[0104] As an example, the purification apparatus also includes a storage bottle connected to the feed inlet of the column 110.

[0105] As an example, a filter is also provided at the discharge port of tower body 110.

[0106] Secondly, embodiments of this application provide a 72 The purification process for GeF4 adopts the method provided in the first aspect embodiment. 72 The purification of GeF4 is carried out using a device that includes the following steps: S1. Hydrogen gas is introduced into the packed distillation column for activation treatment to remove oxide impurities on the surface of germanium metal. Then, the packed distillation column is sequentially purged with inert gas and evacuated. S2. After the evacuation treatment is completed, gaseous gas is introduced into the packed distillation column. 72 The crude GeF4 is fed until the feed rate reaches the preset value, then the feed inlet is closed and distillation is performed; S3, the condenser unit is opened to collect the liquid. 72 GeF4; then make it liquid 72 GeF4 vaporizes and opens the storage cell, allowing the gaseous state to... 72 GeF4 enters the storage unit.

[0107] In this application, the method provided by the first aspect embodiment is adopted.72 The GeF4 purification device was used to process the gaseous phase according to the above process. 72 Crude GeF4 can be purified by distillation to obtain a product with both high abundance and high purity. 72 GeF4.

[0108] As an example, in the activation treatment step, the hydrogen flow rate is 0.5 L / min to 30 L / min (e.g., but not limited to any one of 0.5 L / min, 1 L / min, 5 L / min, 10 L / min, 20 L / min and 30 L / min or any range between any two), the treatment temperature is 100℃ to 250℃ (e.g., but not limited to any one of 100℃, 125℃, 150℃, 175℃, 200℃, 225℃ and 250℃ or any range between any two), and the treatment time is 24 h to 48 h (e.g., but not limited to any one of 24 h, 28 h, 30 h, 35 h, 40 h, 45 h and 48 h or any range between any two).

[0109] In this embodiment, limiting the hydrogen flow rate, processing temperature, and processing time in the activation step to the aforementioned ranges effectively removes oxide impurities from the germanium metal surface, thereby facilitating the subsequent preparation of high-purity germanium. 72 GeF4.

[0110] As an example, in the inert gas purging process, the inert gas flow rate is 0.5 L / min to 30 L / min (e.g., but not limited to any one of 0.5 L / min, 1 L / min, 5 L / min, 10 L / min, 20 L / min and 30 L / min or any range between two), and the purging time is 4 h to 8 h (e.g., but not limited to any one of 4 h, 5 h, 6 h, 7 h and 8 h or any range between two).

[0111] In this embodiment, the inert gas flow rate and purging time in the inert gas purging process are limited to the above-mentioned ranges, which can effectively remove hydrogen and moisture from the packed distillation column.

[0112] As an example, the vacuuming process continues until the vacuum level in the packed distillation column is less than 30 mtorr.

[0113] In this embodiment, the vacuuming process is carried out according to the above standards to ensure a high level of cleanliness within the packed distillation column.

[0114] As an example, introducing air into a packed distillation column 72In the step of producing crude GeF4, the feed rate is 0.5 kg to 10 kg (e.g., but not limited to any one of 0.5 kg, 1 kg, 2 kg, 4 kg, 6 kg, 8 kg and 10 kg or any range between two), and the feed flow rate is 0.1 kg / h to 5 kg / h (e.g., but not limited to any one of 0.1 kg / h, 0.5 kg / h, 1 kg / h, 2 kg / h, 3 kg / h, 4 kg / h and 5 kg / h or any range between two).

[0115] In this embodiment, 72 The minimum feed rate for crude GeF4 is as low as 0.5 kg, making it suitable for small-scale applications. 72 The distillation and purification of GeF4, while controlling the feed flow rate within the above-mentioned range, has the advantage of high feed stability.

[0116] As an example, in the distillation process, the pressure inside the packed distillation column is 0.2 MPa to 0.3 MPa (e.g., but not limited to any one of 0.2 MPa, 0.22 MPa, 0.24 MPa, 0.26 MPa, 0.28 MPa, and 0.3 MPa, or a range between any two), and the pressure at the reboiler... 72 The temperature of GeF4 is higher than that at the condenser. 72 The temperature of GeF4 and 72 The temperature difference of GeF4 is 0.1℃ to 1℃ (e.g., but not limited to any one of 0.1℃, 0.2℃, 0.4℃, 0.6℃, 0.8℃ and 1.0℃ or any range between any two), wherein the temperature at the reboiler is -24.3℃ to -16.9℃ (e.g., but not limited to any one of -24.3℃, -24℃, -23℃, -22℃, -21℃, -20℃, -19℃, -18℃ and -16.9℃ or any range between any two), and the treatment time is 1 h to 8 h (e.g., but not limited to any one of 1 h, 2 h, 4 h, 6 h and 8 h or any range between any two).

[0117] In this embodiment, the pressure in the distillation process and the pressure at the reboiler are... 72 GeF4 temperature, condenser location 72 By limiting the GeF4 temperature and processing time to the aforementioned ranges, suitable distillation conditions can be provided to obtain high-purity and high-yield products. 72 GeF4.

[0118] As an example, the condensation unit includes a first cold trap and a second cold trap spaced apart, with the inlets of both cold traps connected to the outlet at the top of the tower. The first cold trap is configured to collect liquid. 72 GeF4 can also make the collected liquid 72 GeF4 is vaporized; the second cold trap is configured to collect liquid impurities and also to vaporize the collected liquid impurities; the condensation unit is opened to collect the liquid. 72 The steps of GeF4 include: first, opening the second cold trap to collect liquid low-boiling-point impurities; and then, once the content of low-boiling-point impurities in the gas at the outlet meets a preset value, closing the second cold trap and opening the first cold trap to collect liquid impurities. 72 GeF4 is used until the content of high-boiling-point impurities in the gas at the outlet exceeds the preset value. Then, the first cold trap is closed and the second cold trap is opened again to collect the liquid high-boiling-point impurities.

[0119] In this embodiment, impurities in the gas after distillation are collected in stages and independently according to the above-described process. 72 GeF4 can be prepared with higher purity. 72 GeF4.

[0120] It should be noted that the content of impurities in the gas is determined by interval sampling combined with gas chromatography detection.

[0121] As an example, in the step of collecting liquid low-boiling-point impurities, the flow rate at the outlet is 0.01 kg / h to 0.1 kg / h, for example, but not limited to any one of 0.01 kg / h, 0.02 kg / h, 0.04 kg / h, 0.06 kg / h, 0.08 kg / h and 0.1 kg / h or any range between two.

[0122] In this embodiment, controlling the flow rate within the aforementioned range during the step of collecting liquid low-boiling-point impurities can effectively remove low-boiling-point impurities while reducing [the amount of water / water]. 72 The loss of GeF4.

[0123] As an example, liquid was collected. 72 In the GeF4 process, the flow rate at the outlet is 0.05 kg / h to 0.5 kg / h, for example, but not limited to any one of 0.05 kg / h, 0.1 kg / h, 0.2 kg / h, 0.3 kg / h, 0.4 kg / h and 0.5 kg / h or any range between two of them.

[0124] In this embodiment, the collected liquid 72 The flow control in the GeF4 step is within the above range, which can effectively collect...72 GeF4 reduces the content of high-boiling-point impurities.

[0125] It should be noted that, for 72 Unless otherwise specified or limited, the purification process of GeF4 can be carried out in accordance with conventional processes in this field.

[0126] The technical solution of this application will be described in detail below with reference to specific embodiments.

[0127] Example 1 This application provides an embodiment of a method. 72 The purification process for GeF4, using the purification apparatus provided in the first aspect embodiment, includes the following steps: S1. Hydrogen gas is introduced into a packed distillation column (3 m high, 30 mm inner diameter, and made of stainless steel) for activation treatment to remove oxide impurities on the surface of germanium metal. The packing consists of θ rings made of stainless steel with an average diameter of 2 mm. The surface of the packing has a 10 μm thick germanium metal layer, and the inner wall of the pore structure also has germanium metal. In the activation treatment step, the hydrogen flow rate is 5 L / min, the treatment temperature is 200℃, and the treatment time is 24 h. Then, the packed distillation column is purged with nitrogen gas at a flow rate of 5 L / min for 8 h. Finally, the packed distillation column is evacuated to a vacuum degree of 5 mtorr.

[0128] After the vacuuming process is completed, S2 is stored in a high-abundance environment. 72 The GeF4 storage bottle introduces gaseous gas into the packed distillation column. 72 GeF4 crude product ( 72 The abundance of GeF4 was 67.3%, and the purity was 99.9%. Specifically, the feed flow rate was 0.5 kg / h until the feed rate reached 2 kg, at which point the feed inlet was closed and distillation was performed. During the distillation process, the pressure inside the packed distillation column was 0.2 MPa, and the pressure at the reboiler was... 72 The temperature of GeF4 is -24.3℃, at the condenser... 72 The temperature for GeF4 was -25℃, and the treatment time was 4 hours.

[0129] After the total reflux of the distillation process S3 stabilizes, a low-temperature medium (-40°C refrigerant) is introduced into the medium chamber of the second cold trap, and the inlet pipe of the second cold trap is connected to the outlet of the tower. The flow rate at the outlet is 0.02 kg / h to collect liquid low-boiling-point impurities. When the content of low-boiling-point impurities in the gas at the outlet meets the preset value, the second cold trap is closed. Then, a low-temperature medium (-40°C refrigerant) is introduced into the medium chamber of the first cold trap, and the inlet pipe of the first cold trap is connected to the outlet of the tower. The flow rate at the outlet is 0.2 kg / h to collect liquid low-boiling-point impurities. 72 GeF4; until the content of high-boiling-point impurities in the gas at the outlet exceeds a preset value, close the first cold trap and stop collecting liquid. 72 GeF4; then, a low-temperature medium (-40°C refrigerant) is introduced into the medium chamber of the second cold trap, and the inlet pipe of the second cold trap is connected to the outlet of the column. The flow rate at the outlet is 0.1 kg / h to collect liquid high-boiling-point impurities until there is no gas output from the packed distillation column. After collection is completed, the introduction of the low-temperature medium into the first cold trap is stopped, and then the liquid in the collection chamber of the first cold trap is heated by a third heating element to make the liquid... 72 GeF4 vaporizes, causing the pressure inside the collection chamber to rise to 1.0 MPa. The first storage bottle is then opened to allow the gaseous state to be released. 72 GeF4 was delivered to the first storage bottle at a flow rate of 0.2 kg / h, with a yield of 97%.

[0130] It should be noted that when collecting low-boiling-point liquid impurities, liquid... 72 In the process of collecting GeF4 and liquid high-boiling-point impurities, the corresponding cold traps all use -40℃ refrigerant. This is because the main component in the collected components is still... 72 GeF4.

[0131] Example 2 This application provides an embodiment of a method. 72 The purification process for GeF4, using the purification apparatus provided in the first aspect embodiment, includes the following steps: S1. Hydrogen gas is introduced into a packed distillation column (1 m high, 20 mm inner diameter, and made of nickel) for activation treatment to remove oxide impurities from the surface of germanium metal. The packing is a triangular spiral made of nickel with an average diameter of 1.5 mm. The surface of the packing has a 5 μm thick germanium metal layer, and the inner wall of the pore structure also has germanium metal. In the activation treatment step, the hydrogen flow rate is 0.5 L / min, the treatment temperature is 100℃, and the treatment time is 48 h. Then, the packed distillation column is purged with nitrogen gas at a flow rate of 0.5 L / min for 4 h. Then, the packed distillation column is evacuated to a vacuum degree of 30 mtorr.

[0132] After the vacuuming process is completed, S2 is stored in a high-abundance environment. 72 The GeF4 storage bottle introduces gaseous gas into the packed distillation column. 72 GeF4 crude product ( 72 The abundance of GeF4 was 67.3%, and the purity was 99.9%. Specifically, the feed flow rate was 0.1 kg / h, and the feed inlet was closed after the feed rate reached 0.5 kg, followed by distillation. During the distillation process, the pressure inside the packed distillation column was 0.3 MPa, and the pressure at the reboiler was... 72 The temperature of GeF4 is -16.9℃, at the condenser... 72 The temperature for GeF4 was -17.2℃, and the treatment time was 1 h.

[0133] After the total reflux of the distillation process S3 stabilizes, a low-temperature medium (-30°C refrigerant) is introduced into the medium chamber of the second cold trap, and the inlet pipe of the second cold trap is connected to the outlet of the tower. The flow rate at the outlet is 0.01 kg / h to collect liquid low-boiling-point impurities. When the content of low-boiling-point impurities in the gas at the outlet meets the preset value, the second cold trap is closed. Then, a low-temperature medium (-30°C refrigerant) is introduced into the medium chamber of the first cold trap, and the inlet pipe of the first cold trap is connected to the outlet of the tower. The flow rate at the outlet is 0.05 kg / h to collect liquid low-boiling-point impurities. 72 GeF4; until the content of high-boiling-point impurities in the gas at the outlet exceeds a preset value, close the first cold trap and stop collecting liquid. 72 GeF4; then, a low-temperature medium (-30°C refrigerant) is introduced into the medium chamber of the second cold trap, and the inlet pipe of the second cold trap is connected to the outlet of the column. The flow rate of the outlet is 0.05 kg / h to collect liquid high-boiling-point impurities until there is no gas output from the packed distillation column. After collection is completed, the introduction of the low-temperature medium into the first cold trap is stopped, and then the liquid in the collection chamber of the first cold trap is heated by the third heating element to make the liquid... 72 GeF4 vaporizes, causing the pressure inside the collection chamber to rise to 2.0 MPa. The first storage bottle is then opened to allow the gaseous state to be released. 72 GeF4 was delivered to the first storage bottle at a flow rate of 0.05 kg / h, with a purification yield of 94%.

[0134] Example 3 This application provides an embodiment of a method. 72 The purification process for GeF4, using the purification apparatus provided in the first aspect embodiment, includes the following steps: S1. Hydrogen gas is introduced into a packed distillation column (5 m high, 50 mm inner diameter, and made of Hastelloy alloy) for activation treatment to remove oxide impurities from the surface of germanium metal. The packing consists of θ rings with an average diameter of 6 mm made of Hastelloy alloy, and the surface of the packing has a 30 μm thick germanium metal layer, and the inner wall of the pore structure also has germanium metal. In the activation treatment step, the hydrogen flow rate is 30 L / min, the treatment temperature is 250 ℃, and the treatment time is 36 h. Then, the packed distillation column is purged with nitrogen gas at a flow rate of 30 L / min for 6 h. Finally, the packed distillation column is evacuated to a vacuum degree of 20 mtorr.

[0135] After the vacuuming process is completed, S2 is stored in a high-abundance environment. 72 The GeF4 storage bottle introduces gaseous gas into the packed distillation column. 72 GeF4 crude product ( 72 The abundance of GeF4 was 67.3%, and the purity was 99.9%. Specifically, the feed flow rate was 5 kg / h until the feed rate reached 10 kg, at which point the feed inlet was closed and distillation was performed. During the distillation process, the pressure inside the packed distillation column was 0.25 MPa, and the pressure at the reboiler was... 72 The temperature of GeF4 is -20.6℃, at the condenser... 72 The temperature for GeF4 was -21℃, and the treatment time was 8 hours.

[0136] After the entire cycle of distillation in S3 has stabilized, a low-temperature medium (-35°C refrigerant) is introduced into the medium chamber of the second cold trap, and the inlet pipe of the second cold trap is connected to the outlet of the tower. The flow rate at the outlet is 0.1 kg / h to collect liquid low-boiling-point impurities. When the content of low-boiling-point impurities in the gas at the outlet meets the preset value, the second cold trap is closed. Then, a low-temperature medium (-35°C refrigerant) is introduced into the medium chamber of the first cold trap, and the inlet pipe of the first cold trap is connected to the outlet of the tower. The flow rate at the outlet is 0.5 kg / h to collect liquid low-boiling-point impurities. 72 GeF4; until the content of high-boiling-point impurities in the gas at the outlet exceeds a preset value, close the first cold trap and stop collecting liquid. 72 GeF4; then, a low-temperature medium (-35°C refrigerant) is introduced into the medium chamber of the second cold trap, and the inlet pipe of the second cold trap is connected to the outlet of the column. The flow rate of the outlet is 0.5 kg / h to collect liquid high-boiling-point impurities until there is no gas output from the packed distillation column. After collection is completed, the introduction of the low-temperature medium into the first cold trap is stopped, and then the liquid in the collection chamber of the first cold trap is heated by the third heating element to make the liquid... 72 GeF4 vaporizes, causing the pressure inside the collection chamber to rise to 1.5 MPa. The first storage bottle is then opened to allow the gaseous state to dissipate.72 GeF4 was delivered to the first storage bottle at a flow rate of 0.5 kg / h, with a purification yield of 96%.

[0137] Comparative Example 1 This application provides a comparative example. 72 The purification process for GeF4 differs from that in Example 1 only in that the surface of the packing material and the inner wall of the pore structure do not contain germanium metal, i.e., the packing material is a conventional unmodified packing material, and the purification yield is 70%.

[0138] It should be noted that in Comparative Example 1, due to poor impurity removal, the discharge port detected [illegible]. 72 The purity of GeF4 is difficult to meet above 99.999%, which makes it difficult to collect effectively, thus significantly reducing the yield.

[0139] Test case Product component testing Test method: The gaseous samples prepared in Examples 1-3 and Comparative Example 1 were respectively tested. 72 GeF4 was used as the sample, and the specific composition of each sample was tested by gas chromatography, infrared spectroscopy and mass spectrometry. The test results are summarized in Table 1.

[0140] Table 1

[0141] Referring to Table 1, the test results of Examples 1-3 and Comparative Example 1 show that by using the purification device provided in the embodiments of this application and preparing according to the purification process of the embodiments of this application, high abundance of [the substance] can be [prepared / processed]. 72 Using GeF4 as a raw material, a product with both high abundance and high purity was prepared. 72 GeF4.

[0142] The above description is merely a preferred embodiment of this application and is not intended to limit this application. Various modifications and variations can be made to this application by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of this application should be included within the protection scope of this application.

Claims

1. A kind 72 The purification apparatus for GeF4 is characterized by, include: A packed distillation column includes a column body, a reboiler, a condenser, and packing, wherein the reboiler is located at the bottom of the column body, the condenser is located at the top of the column body, and the packing is located inside the column body and the surface of the packing has germanium metal. A condensation unit, wherein the air inlet of the condensation unit is connected to the discharge outlet at the top of the tower, and the condensation unit is configured to collect liquid. 72 GeF4 can also make the collected liquid 72 GeF4 vaporization; A storage unit, connected to the outlet of the condensation unit, is used to collect and store gaseous substances. 72 GeF4.

2. As described in claim 1 72 The purification apparatus for GeF4 is characterized by, The surface of the filler has a germanium metal layer; Optionally, the thickness of the germanium metal layer is 5 μm to 30 μm; Optionally, the inner wall of the pore structure of the packing also has germanium metal; Optionally, the height of the tower body is 1 m to 5 m, the inner diameter of the tower body is 20 mm to 50 mm, and the average diameter of the packing is 1.5 mm to 6 mm.

3. As described in claim 1 or 2 72 The purification apparatus for GeF4 is characterized by, The reboiler includes a reboiler body, a flow guide shroud, and a reboiler shell. The reboiler shell is fitted over the reboiler body. The outer wall of the reboiler body and the inner wall of the reboiler shell together form a liquid collection tank that communicates with the tower body. The flow guide shroud is placed on top of the reboiler body. Optionally, the flow guide shroud protrudes toward the side opposite to the reboiler body; Optionally, the outer peripheral wall of the reboiler shell is provided with a first heating element.

4. The method according to claim 3 72 The purification apparatus for GeF4 is characterized by, Along the axial direction of the tower body, the bottom of the reboiler body protrudes from the bottom of the reboiler shell, and a second heating element is provided on the outer peripheral wall of the protruding area of ​​the reboiler body. Optionally, both the first heating element and the second heating element are provided with temperature sensors, and a plurality of the temperature sensors are distributed at intervals along the axial direction of the tower body; Optionally, the outer wall of the reboiler body is provided with an overflow hole, and the overflow hole is located between the first heating element and the flow guide shroud in the axial direction of the tower body.

5. As described in claim 1 or 2 72 The purification apparatus for GeF4 is characterized by, The condensation unit includes a first cold trap and a second cold trap spaced apart. The air inlets of both the first and second cold traps are connected to the discharge outlet at the top of the tower. The first cold trap is configured to collect liquid. 72 GeF4 can also make the collected liquid 72 GeF4 is vaporized, and the second cold trap is configured to collect liquid impurities and vaporize the collected liquid impurities; the storage unit includes a first storage bottle and a second storage bottle spaced apart, the first storage bottle being connected to the outlet of the first cold trap for collecting and storing gaseous impurities. 72 GeF4, the second storage bottle is connected to the outlet of the second cold trap, and is used to collect and store gaseous impurities.

6. The method according to claim 5 72 The purification apparatus for GeF4 is characterized by, The first cold trap includes a cold trap body, an inlet pipe, an outlet pipe, a cold trap shell, and a third heating element. The cold trap body has a collection cavity. One end of the inlet pipe is connected to the outlet and the other end extends into the collection cavity. One end of the outlet pipe is connected to the collection cavity and the other end is connected to the inlet of the first storage bottle. The third heating element extends into the collection cavity and is accommodated in the inlet pipe in a corresponding area. The cold trap shell is sleeved on the outside of the cold trap body, and the outer wall of the cold trap body and the inner wall of the cold trap shell together form a medium cavity for conveying the heat exchange medium. Optionally, both the air inlet pipe and the third heating element extend to the bottom of the cold trap body; Optionally, the outer wall of the cold trap shell is also provided with a thermal insulation layer.

7. A kind 72 The purification process of GeF4 is characterized by, Using any one of claims 1 to 6 72 The purification of GeF4 is carried out using a device that includes the following steps: S1 Hydrogen gas is introduced into the packed distillation column for activation treatment to remove oxide impurities on the surface of the germanium metal. Then, the packed distillation column is subjected to inert gas purging and vacuum treatment in sequence. S2 After the vacuuming process is completed, gaseous gas is introduced into the packed distillation column. 72 The crude GeF4 is fed until the feed rate reaches the preset value, then the feed inlet is closed and the distillation process is carried out. S3 Open the condensation unit to collect the liquid. 72 GeF4; then make it liquid 72 GeF4 vaporizes and opens the storage cell, allowing the gaseous state to... 72 GeF4 enters the storage unit.

8. The method according to claim 7 72 The purification process of GeF4 is characterized by, In the activation treatment step, the flow rate of hydrogen is 0.5 L / min to 30 L / min, the treatment temperature is 100℃ to 250℃, and the treatment time is 24 h to 48 h. Or / and, in the inert gas purging process, the inert gas flow rate is 0.5 L / min to 30 L / min and the purging time is 4h to 8h; Or / and, in the vacuuming process, until the vacuum level in the packed distillation column is less than 30 mtorr.

9. The method according to claim 7 or 8 72 The purification process of GeF4 is characterized by, The process of introducing into the packed distillation column 72 In the process of producing crude GeF4, the feed rate is 0.5 kg to 10 kg and the feed flow rate is 0.1 kg / h to 5 kg / h. Or / and, in the distillation process, the pressure inside the packed distillation column is 0.2 MPa to 0.3 MPa, and the pressure at the reboiler is... 72 The temperature of GeF4 is higher than that at the condenser. 72 The temperature of GeF4 and 72 The temperature difference of GeF4 is 0.1℃~1℃, wherein the temperature difference at the reboiler is... 72 The temperature range for GeF4 is -24.3℃ to -16.9℃, and the treatment time is 1 h to 8 h.

10. The claim 7 or 8 72 The purification process of GeF4 is characterized by, The condensation unit includes a first cold trap and a second cold trap spaced apart. The air inlets of both the first and second cold traps are connected to the discharge outlet at the top of the tower. The first cold trap is configured to collect liquid. 72 GeF4 can also make the collected liquid 72 GeF4 vaporization, the second cold trap is configured to collect liquid impurities and also to vaporize the collected liquid impurities; The condensation unit is opened to collect the liquid. 72 The steps of GeF4 include: first, opening the second cold trap to collect liquid low-boiling-point impurities; and then, once the content of low-boiling-point impurities in the gas at the outlet meets a preset value, closing the second cold trap and opening the first cold trap to collect liquid impurities. 72 GeF4, until the content of high-boiling-point impurities in the gas at the outlet is higher than a preset value, then close the first cold trap and open the second cold trap again to collect the liquid high-boiling-point impurities; Optionally, in the step of collecting liquid low-boiling-point impurities, the flow rate at the outlet is 0.01 kg / h to 0.1 kg / h; Optionally, the collected liquid 72 In the GeF4 process, the flow rate at the outlet is 0.05 kg / h to 0.5 kg / h.

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