Germanium tetrachloride distillation column and distillation method

Abstract

The present application relates to high-purity germanium production technical field, more specifically, it relates to a kind of germanium tetrachloride rectifying tower and rectification method.Germanium tetrachloride rectifying tower includes: front pretreatment device, rectifying device and collection device, rectifying device is equipped with multiple, multiple rectifying device is connected in series;Front pretreatment device is connected with the feed inlet of rectifying device located at the first end, the discharge port of rectifying device located at the tail end is connected with collection device;Rectifying device includes: tower kettle, tower kettle top is connected with rectifying tower column, and the top of rectifying tower column is connected with tower top condenser by buffer separation mechanism;Buffer separation mechanism is equipped with gas guide hole and condensate outlet, and the vapor in rectifying tower column enters tower top condenser through the gas guide hole of buffer separation mechanism.The present application is connected in series with multiple rectifying devices, removes organic impurities and transition metal impurities in advance before entering rectifying system, reduces subsequent separation load, and the reflux ratio of each rectifying device connected in series can be independently adjusted, to improve overall separation capacity.

Description

Technical Field

[0001] This invention relates to the field of high-purity germanium production technology, and more specifically, to a germanium tetrachloride distillation column and distillation method. Background Technology

[0002] Currently, in the production of high-purity germanium, the boiling point difference between germanium tetrachloride and impurities is typically utilized. Multiple partial vaporization and condensation cycles within the distillation column enrich the low-boiling-point germanium tetrachloride at the top of the column to obtain a high-purity product. Existing small- to medium-sized industrial-scale germanium tetrachloride distillation columns are typically 4-5 meters high, limiting their theoretical plate number and making it difficult to achieve the extremely high purity requirements of reducing transition metal impurities to below 3 ppb and hydrogen impurities to less than 1 ppm through single or multiple conventional distillations. Furthermore, the existing distillation column top condensation structures often lack effective buffer separation and directional flow design, easily leading to uncondensed gas entrainment of condensate or gas-liquid backmixing, reducing gas-liquid mass transfer efficiency. Simultaneously, the connection structures between conventional glass column sections lack sufficient flexibility and stable clamping capacity to cope with system thermal expansion and contraction and assembly stress, easily causing seal failure or glass breakage. Summary of the Invention

[0003] The summary section introduces a series of simplified concepts, which will be further explained in detail in the detailed description section. The summary section of this invention is not intended to limit the key features and essential technical features of the claimed technical solution, nor is it intended to determine the scope of protection of the claimed technical solution.

[0004] To at least partially solve the above problems, the present invention provides a germanium tetrachloride distillation column, comprising: a pretreatment device, a distillation unit, and a collection device, wherein multiple distillation units are connected in series; the pretreatment device is connected to the feed inlet of the distillation unit located at the first end, and the discharge outlet of the distillation unit located at the last end is connected to the collection device; the distillation unit includes: a reboiler, the top of which is connected to the distillation column, and the top of the distillation column is connected to a top condenser via a buffer separation mechanism; the buffer separation mechanism is provided with a gas guide hole and a condensate outlet, and the vapor in the distillation column enters the top condenser through the gas guide hole of the buffer separation mechanism; the top of the top condenser is provided with a first outlet, and the first outlet is connected to a first product condenser via a pipeline; the condensate outlet is connected to a reflux ratio controller via a first inclined pipe, the reflux ratio controller having a reflux outlet and a collection outlet, the reflux outlet being connected to the buffer separation mechanism via a second inclined pipe to return the refluxed condensate back into the distillation column, and the collection outlet being connected to a second product condenser via a pipeline.

[0005] Furthermore, the reboiler, distillation column, buffer separation mechanism, first product condenser, second product condenser, and top condenser are all made of high borosilicate glass.

[0006] Furthermore, a liquid seal bottle is installed on the pipeline between the outlet of the reflux ratio controller and the second finished product condenser. The liquid seal bottle contains a sealing liquid to form a liquid seal to prevent external air from being drawn back when the system is under negative pressure.

[0007] Furthermore, the top condenser includes: a condenser shell with a first outlet, and a condensing coil installed inside the condenser shell; the inlet and outlet of the condensing coil both extend to the outside of the condenser shell; the buffer separation mechanism includes: a buffer separation cylinder, the top and bottom of which are detachably and sealingly connected to the condenser shell and the distillation column, respectively; a partition cover integrally formed in the middle of the buffer separation cylinder, which divides the interior of the buffer separation cylinder into an upper condensation zone and a lower gas guiding zone; a top-sealed gas guiding pipe is fixed in the middle of the top of the partition cover, and a gas guiding hole is opened on the side wall of the gas guiding pipe; the condensate outlet on the side wall of the buffer separation cylinder is connected to the upper condensation zone; the horizontal height of the condensate outlet is lower than the gas guiding hole and higher than the partition cover, and is connected to the reflux ratio controller through a first inclined pipe; a second inclined pipe connected at the reflux outlet is inserted into the lower gas guiding zone so that the refluxed condensate falls back to the distillation column; a temperature measuring port is provided on the side wall of the buffer separation cylinder, and a temperature sensor inserted into the lower gas guiding zone is sealed and fixed inside the temperature measuring port.

[0008] Furthermore, the separator inside the buffer separator bulges upward from the outside to the center to form an arc surface, so that the accumulated condensate flows from the center to the condensate outlet on the side of the buffer separator.

[0009] Furthermore, the buffer separation mechanism also includes: a central guide column located inside the air guide tube, the upper end of which is fixedly connected to the bottom inverted conical column of the condensate protection shield, the condensate protection shield being positioned above the air guide tube; the lower end of the central guide column is threadedly connected to the internal threaded hole at the top of the cone; the bottom inverted conical column of the condensate protection shield is pressed into the inverted conical circular hole at the closed end of the air guide tube, the horizontal height of the bottommost point of the inverted conical column being lower than the horizontal height of the closed end of the air guide tube; the bottom of the cone is a downward-facing plane to form a primary impact surface, and the outer conical shape of the cone... The surface is provided with an annular groove, and the bottom of the annular groove is provided with several longitudinal conical through holes, the upper diameter of the longitudinal conical through holes being larger than the lower diameter; an air intake channel is formed between the outer conical surface of the cone and the inner wall of the air guide tube, which is wider at the bottom and narrower at the top. After the vapor impacts the bottom plane of the cone, it enters the air intake channel and is accelerated upward, and then enters the annular gap between the central guide column and the air guide tube, impacting the top closed end of the air guide tube; the outer wall of the central guide column is provided with a guide groove, which guides the separated liquid in the annular gap to the outer conical surface of the cone; the temperature sensor extends into the air intake channel through the side wall of the buffer separation cylinder.

[0010] Furthermore, the air guide tube and the partition cover are integrally formed; a side hole conical nozzle is fixed inside the air guide hole on the side wall of the air guide tube, the wide mouth of the side hole conical nozzle is connected to the air guide hole, and the tip is drawn inward towards the inside of the air guide tube; the buffer separation cylinder, air guide tube, partition cover and side hole conical nozzle are made of high borosilicate glass, and the condensate protection cover, central guide column and cone are made of polytetrafluoroethylene.

[0011] Furthermore, a corrosion-resistant flexible connector is used to connect the buffer separation mechanism and the top condenser of the tower. The corrosion-resistant flexible connector includes: an end seat, a screw, a tension spring, and a flexible connecting tube. The two end seats are respectively tightly and sealed to the bottom of the condenser shell and the top of the buffer separation cylinder, and the two end seats are clamped on the outside of the protruding ring at the bottom of the condenser shell and the protruding ring at the top of the buffer separation cylinder. The condenser shell and the buffer separation cylinder are sealed and connected by a flexible connecting tube. Multiple screws are evenly wound around and passed between the two end seats. The nuts threaded on the screws are clamped on the outside of one end seat, and the end of the screw is connected to the outer side of the other end seat by a tension spring sleeved on the screw.

[0012] Furthermore, the tower reactor is an integrated jacketed reactor structure, equipped with a heating circulator, which heats the material inside the tower reactor by circulating heat transfer oil through the jacket.

[0013] Furthermore, the distillation column is composed of several standard-length columns connected sequentially by detachable corrosion-resistant flexible connectors, and the columns are filled with glass spring packing. The distillation column is detachably and sealed with corrosion-resistant flexible connectors between the top of the reboiler and the distillation column, between the distillation column and the buffer separation mechanism, and between the buffer separation mechanism and the top condenser.

[0014] The present invention also provides a distillation method applied to a germanium tetrachloride distillation column as described in any of the above claims, the method comprising the following steps: S1. Pretreatment: Crude germanium tetrachloride is pre-distilled in a pretreatment unit with concentrated sulfuric acid to remove organic impurities. The pre-distillation temperature is controlled at 80-90℃ for 2-2.2 hours. The pre-distillation product is added with analytical grade hydrochloric acid and chlorine gas is introduced to complete the re-distillation to further remove transition metal impurities. The re-distillation product is added with concentrated sulfuric acid for a second digestion and distillation to further remove residual organic and metal impurities. The qualified pretreatment product is sent to the first-end distillation unit. S2. Distillation: The pretreated qualified product is continuously distilled in multiple distillation units connected in series. During distillation, the reboiler is heated to vaporize germanium tetrachloride. The reboiler temperature is controlled above 100°C. The vapor rises along the distillation column and completes gas-liquid mass transfer with the liquid refluxed at the top of the column to achieve component separation. The temperature at the top of the column is stabilized at 83-86°C. The germanium tetrachloride vapor enters the top condenser through the gas guide hole of the buffer separation mechanism for condensation. The uncondensed gas enters the first product condenser for secondary condensation and recovery through the first outlet at the top of the top condenser. The condensate flows into the reflux ratio controller through the condensate outlet of the buffer separation mechanism and the first inclined tube. The reflux ratio is controlled in the range of 4:1 to 14:1 by the reflux ratio controller, which distributes the condensate into reflux liquid and product liquid. The reflux liquid returns to the buffer separation mechanism through the reflux outlet of the reflux ratio controller and the second inclined tube and falls back to the distillation column to continue gas-liquid mass transfer. The product is collected after being cooled by the product outlet of the reflux ratio controller and the second product condenser. The product is output from the distillation unit located at the tail end. S3. Collection: The product output from the tail-end distillation unit is sent to the collection device, and after online sampling and testing to confirm that the purity meets the standard, it is stored.

[0015] Compared with the prior art, the present invention has at least the following beneficial effects: The present invention uses multiple distillation units in series, combined with pretreatment of concentrated sulfuric acid initial distillation, hydrochloric acid chlorination re-distillation, and concentrated sulfuric acid secondary digestion distillation, to remove organic impurities and transition metal impurities before entering the distillation system, reducing the subsequent separation load. The reflux ratio of each distillation unit in series can be adjusted independently, improving the overall separation capacity and helping to control transition metal impurities and hydrogen impurities at a lower level. The buffer separation mechanism forms a buffer space between the distillation column and the top condenser. The vapor is accelerated by the first-stage impact on the bottom surface of the cone, the wide-at-the-bottom-narrow-at-the-top air inlet channel, and the second-stage impact in the annular gap before being discharged through the gas guide hole. The entrained liquid droplets are knocked off and collected and refluxed through the annular groove, the conical through hole, and the guide groove. The upper condensation zone and the lower gas guide zone are separated by a separator. The reflux liquid falls directly back to the lower gas guide zone through the second inclined tube, reducing the back mixing of uncondensed gas with condensate and improving the gas-liquid mass transfer efficiency.

[0016] To make the above-mentioned objects, features and advantages of the present invention more apparent and understandable, preferred embodiments are described below in detail with reference to the accompanying drawings. Attached Figure Description

[0017] The accompanying drawings are provided to further illustrate the invention and form part of the specification. They are used in conjunction with embodiments of the invention to explain the invention and do not constitute a limitation thereof. In the drawings: Figure 1 This is a schematic diagram of the distillation apparatus of the present invention; Figure 2 This is a partial schematic diagram of the distillation apparatus of the present invention; Figure 3This is a partial cross-sectional view of the distillation apparatus of the present invention; Figure 4 This is a schematic diagram of the buffer separation mechanism of the present invention; Figure 5 A cross-sectional view of the buffer separation mechanism of the present invention. Figure 1 ; Figure 6 A cross-sectional view of the buffer separation mechanism of the present invention. Figure 2 ; Figure 7 This is a partial schematic diagram of the buffer separation mechanism of the present invention.

[0018] Icons: 1-Reboiler; 2-Distillation column; 3-Buffer separation mechanism; 301-Gas inlet; 302-Condensate outlet; 303-Buffer separation cylinder; 304-Separator cover; 305-Gas inlet pipe; 306-Temperature sensor; 307-Central guide column; 308-Condensate protective cover; 309-Conical body; 310-Annular groove; 311-Longitudinal conical through hole; 312-Gas inlet channel; 313-Side conical nozzle; 4-Top condenser; 5-First product condenser; 6-First inclined tube; 7-Reflux ratio controller; 8-Second inclined tube; 9-Corrosion-resistant flexible connector; 901-End seat; 902-Screw; 903-Tension spring; 904-Flexible connecting pipe; 905-Sheath; 10-Second product condenser; 11-Liquid seal bottle. Detailed Implementation

[0019] To enable those skilled in the art to better understand the technical solutions in this application, the technical solutions in the embodiments of this application will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of this application, and not all of the embodiments. Based on the embodiments in this application, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this application.

[0020] The following is in conjunction with the appendix Figure 1 -Appendix Figure 7 The present invention will be described in further detail below.

[0021] Example 1:

[0022] like Figures 1-7As shown, a germanium tetrachloride distillation column includes: a pretreatment unit, a distillation unit, and a collection unit. Multiple distillation units are connected in series. The pretreatment unit is connected to the inlet of the distillation unit at the first end, and the outlet of the distillation unit at the last end is connected to the collection unit. The distillation unit includes: a reboiler 1, the top of which is connected to a distillation column 2. The top of the distillation column 2 is connected to a top condenser 4 via a buffer separation mechanism 3. The buffer separation mechanism 3 has a gas guide hole 301 and a condensate outlet 302. The vapor in the distillation column 2 enters the top condenser 4 through the gas inlet 301 of the buffer separation mechanism 3. The top condenser 4 has a first outlet, which is connected to the first product condenser 5 via a pipeline. The condensate outlet 302 is connected to a reflux ratio controller 7 via a first inclined pipe 6. The reflux ratio controller 7 has a reflux outlet and a product outlet. The reflux outlet is connected to the buffer separation mechanism 3 via a second inclined pipe 8 to return the refluxed condensate back into the distillation column 2. The product outlet is connected to the second product condenser 10 via a pipeline. The reboiler 1, distillation column 2, buffer separation mechanism 3, first product condenser 5, second product condenser 10, and top condenser 4 are all made of high borosilicate glass. A liquid seal bottle 11 is installed on the pipeline between the product outlet of the reflux ratio controller 7 and the second product condenser 10. The liquid seal bottle 11 contains a sealing liquid to form a liquid seal, preventing backflow of external air when the system is under negative pressure. The reboiler 1 is an integrated jacketed reactor structure, equipped with a heating circulator. The heating circulator heats the material inside the reboiler 1 by circulating heat transfer oil through the jacket. The distillation column 2 is composed of multiple column sections connected sequentially by detachable corrosion-resistant flexible connectors 9. The column sections are filled with glass spring packing. The top of the reboiler 1 is detachably and sealed with corrosion-resistant flexible connectors 9, as are the distillation column 2 and the buffer separation mechanism 3, and the buffer separation mechanism 3 and the top condenser 4.

[0023] This invention discloses a germanium tetrachloride distillation column. Crude germanium tetrachloride, after being pretreated to remove organic and transition metal impurities, is fed into the reboiler 1 of the distillation unit located at the beginning. A heating circulator heats the material in the reboiler 1 via a jacket using heat transfer oil circulation, causing the germanium tetrachloride to vaporize. The vapor rises along the distillation column 2. The distillation column 2 is constructed by sequentially splicing several standard-length sections using corrosion-resistant flexible connectors 9. The glass spring packing filling the sections provides sufficient gas-liquid contact surface for the rising vapor and the falling liquid. The two components come into countercurrent contact on the packing surface and repeatedly undergo partial vaporization and partial condensation, achieving component separation. The rising vapor enters the buffer separation mechanism 3, and through its gas guide 301, enters the top condenser 4, where it exchanges heat with the condensing coil and condenses into condensate. The buffer separation mechanism 3 forms a buffer and gas-liquid separation space between the distillation column 2 and the top condenser 4, allowing liquid droplets entrained in the vapor to separate and fall back before entering the top condenser 4. The condensate flows out from the condensate outlet 302 of the buffer separation mechanism 3, enters the reflux ratio controller 7 through the first inclined tube 6, and is distributed by the reflux ratio controller 7 into reflux liquid and product liquid according to the set reflux ratio. The reflux liquid returns to the buffer separation mechanism 3 through the reflux outlet and the second inclined tube 8 and falls back into the distillation column 2 to continue participating in gas-liquid mass transfer. The product liquid enters the second product condenser 10 through the product outlet and pipeline for cooling and collection. Uncondensed gas in the top condenser 4 enters the first product condenser 5 through the first outlet at its top for secondary condensation and recovery. The liquid seal bottle 11 located between the product outlet of the reflux ratio controller 7 and the second product condenser 10 contains a sealing liquid to form a liquid seal. When the system is operating under negative pressure, it prevents external air from being drawn back into the product side, avoiding the hydrolysis of germanium tetrachloride by moisture to generate germanium dioxide, which would contaminate the product and block the pipeline. The product from the previous distillation unit is sent to the bottom of the next distillation unit for further distillation. After being purified in stages through multiple distillation units connected in series, the product is output from the outlet of the distillation unit at the end and sent to the collection device.

[0024] This invention utilizes multiple distillation units connected in series to compensate for the insufficient theoretical plate number of a single distillation column due to height limitations, thereby improving the overall separation capacity. Furthermore, the reflux ratio of each distillation unit can be independently adjusted, ensuring a continuous and controllable separation process. The buffer separation mechanism 3, in conjunction with the gas guide 301, creates a buffer and separation between the condensation zone at the top of the column and the rising gas flow in the distillation column 2, reducing the entrainment of condensate in uncondensed gas and gas-liquid backmixing, which is beneficial for improving gas-liquid mass transfer efficiency. The liquid seal bottle 11 prevents air backflow under negative pressure conditions, avoiding the hydrolysis of germanium tetrachloride. The first finished product condenser 5 performs secondary condensation and recovery of uncondensed gas, reducing the loss of germanium tetrachloride. The reboiler 1, distillation column 2, buffer separation mechanism 3, top condenser 4, first product condenser 5, and second product condenser 10 are all made of high borosilicate glass. The parts in contact with the materials do not contain metal components, thus avoiding metal impurities from contaminating the products. The top of the reboiler 1 and the distillation column 2, the distillation column 2 and the buffer separation mechanism 3, the buffer separation mechanism 3 and the top condenser 4, and adjacent column sections are all connected by corrosion-resistant flexible connectors 9 for detachable sealing. This facilitates disassembly, cleaning, and replacement, and also compensates for the thermal expansion and contraction of the glass components during system heating and cooling, reducing the risk of glass component breakage or seal failure due to assembly stress and thermal stress.

[0025] Example 2:

[0026] like Figures 1-7 As shown, the column top condenser 4 includes: a condenser shell with a first outlet, and a condensing coil installed inside the condenser shell; the inlet and outlet of the condensing coil both extend outside the condenser shell; the buffer separation mechanism 3 includes: a buffer separation cylinder 303, the top and bottom of which are detachably and sealingly connected to the condenser shell and the distillation column 2 respectively; a partition cover 304 integrally formed in the middle of the buffer separation cylinder 303, which divides the interior of the buffer separation cylinder 303 into an upper condensation zone and a lower gas guiding zone; a central hole is opened in the center of the partition cover 304, and a top-sealed gas guiding pipe 305 is integrally connected to the central hole, guiding... The lower end of the gas pipe 305 is connected to the lower gas guiding zone through the central hole, and the upper end is closed and extends into the upper condensation zone. A gas guiding hole 301 is provided on the side wall of the gas guiding pipe 305. The condensate outlet 302 on the side wall of the buffer separator 303 is connected to the upper condensation zone. The horizontal height of the condensate outlet 302 is lower than the gas guiding hole 301 and higher than the separator shroud 304, and it is connected to the reflux ratio controller 7 through the first inclined pipe 6. The second inclined pipe 8 connected at the reflux outlet is inserted into the lower gas guiding zone, allowing the refluxed condensate to fall back to the distillation column column 2. A temperature measuring port is provided on the side wall of the buffer separator 303, and a temperature sensor 306, inserted into the lower gas guiding zone, is sealed and fixed inside the temperature measuring port. The separator shroud 304 inside the buffer separator 303 bulges upward from the outside towards the center to form an arc surface, causing the accumulated condensate to flow from the center towards the condensate outlet 302 on the side of the buffer separator 303.

[0027] In this embodiment, the rising vapor in the distillation column 2 enters the lower gas guiding zone of the buffer separator 303. A central hole is provided in the center of the separator hood 304, and a top-sealed gas guiding pipe 305 is integrally connected to the central hole. The lower end of the gas guiding pipe 305 communicates with the lower gas guiding zone through the central hole, so the vapor in the lower gas guiding zone enters the interior of the gas guiding pipe 305 through the central hole and rises along it. The upper end of the gas guiding pipe 305 is sealed and extends into the upper condensation zone. A gas guiding hole 301 is provided on its sidewall. After rising, the vapor is laterally discharged through the gas guiding hole 301 and enters the upper condensation zone. It then rises into the condenser shell of the top condenser 4, where it exchanges heat and condenses into condensate on the outer surface of the condensing coil. A cooling medium circulates within the condensing coil, circulating through the inlet and outlet extending to the outside of the condenser shell, without contacting germanium tetrachloride. The condensate falls back to the upper condensation zone and lands on the upper surface of the separator 304. The separator 304 bulges upward from the outside to the center to form an arc surface, and the central hole is located at the highest point of the arc surface. The condensate flows along the arc surface from the center to the side of the buffer separation cylinder 303 without backflowing into the gas guide pipe 305 through the central hole. The condensate collected between the edge of the separator 304 and the inner wall of the buffer separation cylinder 303 forms a reservoir above the separator 304 because the horizontal height of the condensate outlet 302 is higher than that of the separator 304. After the liquid level rises to the condensate outlet 302, it flows into the reflux ratio controller 7 through the first inclined pipe 6. The reflux ratio controller 7 distributes it into reflux liquid and produced liquid. The reflux liquid returns to the lower gas guide zone through the reflux outlet and the second inclined pipe 8 and falls back to the distillation column 2. Since the horizontal height of the condensate outlet 302 is lower than that of the gas guide hole 301, the reservoir liquid level will not submerge the gas guide hole 301, and the rising vapor passage remains unobstructed. A temperature sensor 306 is sealed and fixed inside the temperature measuring port on the side wall of the buffer separator 303. The temperature sensor 306 is inserted into the lower gas guide zone to detect the temperature of that area. Uncondensed gas in the top condenser 4 is discharged through the first outlet at the top of the condenser shell.

[0028] The separator 304 divides the interior of the buffer separator 303 into an upper condensation zone and a lower air guiding zone, allowing the collection of condensate and the discharge of rising vapor to occur in two separate zones, reducing the entrainment and back-mixing of rising vapor and falling condensate in the same space. The air guiding pipe 305 is closed at the top and has air guiding holes 301 only on its side wall. This allows vapor to be guided laterally through the air guiding pipe 305, preventing the rising airflow from directly hitting the liquid surface of the upper condensation zone and entraining liquid droplets. Furthermore, the closed top prevents falling condensate from entering the air guiding pipe 305. The central hole is located at the highest point of the arc surface of the separator 304, allowing condensate to flow from the center to the side along the arc surface without backflowing into the air guiding pipe 305 through the central hole, ensuring that the air inlet channel and the condensate flow path do not interfere with each other geometrically. The height relationship between the vent 301, the condensate outlet 302, and the separator 304 creates a liquid reservoir of a certain height above the separator 304. This reservoir forms a liquid seal, preventing uncondensed vapor from the lower venting zone from being discharged directly through the condensate outlet 302 without blocking the upward vapor path. The curved surface of the separator 304 allows the condensate to collect from the center to the side and reach the condensate outlet 302, preventing condensate from accumulating in the middle of the separator 304. The second inclined tube 8 is inserted into the lower venting zone, allowing the reflux liquid to fall directly back to the distillation column 2 without passing through the upper condensation zone, thus avoiding disturbance to the collected condensate. The inlet and outlet of the condenser coil extend outside the condenser shell, allowing the cooling medium to circulate within the coil without contacting germanium tetrachloride, preventing leakage and contamination or hydrolysis. The temperature sensor 306 is sealed and fixed via the temperature measuring port, maintaining the airtightness of the buffer separator 303 while obtaining the temperature of the lower venting zone.

[0029] Example 3:

[0030] like Figures 1-7As shown, the buffer separation mechanism 3 also includes: a central guide column 307 located inside the air guide pipe 305, the upper end of the central guide column 307 being fixedly connected to the bottom inverted conical column of the condensate protection cover 308, the condensate protection cover 308 covering the air guide pipe 305; the lower end of the central guide column 307 being threadedly connected to the internal threaded hole at the top of the cone 309; the inverted conical column at the bottom of the condensate protection cover 308 being pressed into the inverted conical circular hole at the closed end of the air guide pipe 305, the horizontal height of the bottommost point of the inverted conical column being lower than the horizontal height of the closed end of the air guide pipe 305; the bottom of the cone 309 being a downward-facing plane to form a primary impact surface, and the outer conical surface of the cone 309 being provided with an annular groove. 310, the bottom of the annular groove 310 is provided with several longitudinal conical through holes 311, the upper diameter of the longitudinal conical through holes 311 is larger than the lower diameter; the outer conical surface of the cone 309 and the inner wall of the air guide pipe 305 form an air intake channel 312 that is wider at the bottom and narrower at the top. After the vapor hits the bottom plane of the cone 309, it enters the air intake channel 312 and is accelerated upward, and then enters the annular gap between the central guide column 307 and the air guide pipe 305 and hits the top closed end of the air guide pipe 305; the outer wall of the central guide column 307 is provided with a guide groove, which guides the separated liquid in the annular gap to the outer conical surface of the cone 309; the temperature sensor 306 extends into the air intake channel 312 through the side wall of the buffer separation cylinder 303.

[0031] In this invention, the rising vapor inside the distillation column 2 enters the interior of the gas guide pipe 305 through the central hole of the separator 304. It first impacts the downward-facing plane at the bottom of the cone 309, i.e., the first-stage impact surface, causing a sudden drop in vapor velocity and a change in flow direction. The entrained liquid droplets are separated due to inertial impact. Subsequently, the vapor enters the air intake channel 312 formed between the outer conical surface of the cone 309 and the inner wall of the gas guide pipe 305. The air intake channel 312 is wider at the bottom and narrower at the top, where the vapor is accelerated upward. The accelerated vapor enters the annular gap between the central guide column 307 and the gas guide pipe 305 and continues to rise, impacting the closed end of the top of the gas guide pipe 305 to form a second-stage impact. The remaining liquid droplets are separated again. Finally, the vapor is discharged through the gas guide hole 301 on the side wall of the gas guide pipe 305 and enters the upper condensation zone. The liquid separated by the secondary impact flows along the guide groove on the outer wall of the central guide column 307 to the outer conical surface of the cone 309, and then collects in the annular groove 310. After that, it is discharged through the longitudinal conical through hole 311 at the bottom of the annular groove 310, and then falls back to the lower gas guiding area through the central hole of the separator 304 and returns to the distillation column 2. A condensate shield 308 is installed above the vent pipe 305. The inverted conical column at its bottom is pressed into the inverted conical hole at the closed end of the vent pipe 305. The horizontal height of the bottom of the inverted conical column is lower than that of the closed end of the vent pipe 305, which can prevent the condensate falling from the upper condensation zone from entering the top area of ​​the vent pipe 305. The lower part of the outer conical surface of the cone 309 is supported at the central hole of the separator 304. The upper end of the central guide column 307 is fixedly connected to the inverted conical column, and the lower end is threadedly connected to the internal threaded hole at the top of the cone 309. Under the influence of their own weight and the impact of the falling condensate on the condensate shield 308, the condensate shield 308, the central guide column 307, and the cone 309 are pressed together from top to bottom, and the inverted conical column remains pressed into the inverted conical hole. Temperature sensor 306 extends into air intake channel 312 through the side wall of buffer separation cylinder 303 to detect the temperature of steam after primary impact separation and before secondary impact.

[0032] In this invention, the primary impact at the bottom plane of the cone 309 and the secondary impact at the closed top of the air guide pipe 305 constitute a two-stage inertial impact separation, allowing the liquid droplets entrained in the vapor to be separated step by step, resulting in more thorough separation. The air inlet channel 312 is wide at the bottom and narrows at the top, accelerating the vapor upwards within it, which not only increases the inertial effect of subsequent impact separation but also rectifyes the airflow before it enters the annular gap, making its distribution more uniform. The central guide column 307 occupies the central area of ​​the air guide pipe 305 and forms an annular gap with the inner wall of the air guide pipe 305, allowing the airflow to rise along the wall of the annular gap, extending the flow channel and increasing contact with the wall surface, which is beneficial for the aggregation and growth of fine liquid droplets on the wall surface. The guide groove guides the separated liquid in the annular gap to the outer conical surface of the cone 309, collects it through the annular groove 310, and discharges it downwards through the longitudinal conical through-hole 311, allowing the separated liquid to leave the airflow channel in a timely manner and avoid being entrained again by the rising airflow; moreover, this path directly falls back to the lower air guide area without passing through the upper condensation area, avoiding disturbance to the already collected condensate. The upper diameter of the longitudinal conical through-hole 311 is larger than the lower diameter, forming a liquid bridge within the hole. This prevents the rising airflow from short-circuiting through the through-hole and passing through the cone 309. As the liquid accumulates to a certain volume, it overcomes resistance and falls, thus balancing gas obstruction and liquid drainage. The inverted conical column and the inverted conical circular hole at the closed end of the air guide pipe 305 form a conical surface fit. The greater the condensate flow rate and the stronger the impact on the condensate protection cover 308, the tighter the compression between the inverted conical column and the inverted conical circular hole, resulting in a more reliable seal. This forms a self-tightening seal that automatically strengthens with the operating load, while preventing the introduction of metal or moving parts. The condensate protection cover 308 is positioned above the air guide pipe 305, with the bottom of its inverted conical column lower than the closed end of the air guide pipe 305. This achieves both positioning and sealing, while also preventing the falling condensate from entering the top area of ​​the air guide pipe 305. The upper end of the central guide column 307 is fixedly connected to the inverted conical column, and the lower end is threadedly connected to the cone 309, allowing the impact separation assembly to be disassembled as a whole for easy cleaning and maintenance. The temperature sensor 306 extends into the air inlet channel 312. Located after the first-stage impact separation and before the second-stage impact separation, it is less affected by the falling condensate, and the measured temperature is closer to the actual gas phase temperature at the top of the tower than that in the lower air guide zone.

[0033] Example 4:

[0034] like Figures 1-7 As shown, the air guide tube 305 and the partition cover 304 are integrally formed; a side hole conical nozzle 313 is fixed inside the air guide hole 301 on the side wall of the air guide tube 305, the wide mouth of the side hole conical nozzle 313 is connected to the air guide hole 301, and the tip of the nozzle is drawn inward towards the air guide tube 305; the buffer separation cylinder 303, the air guide tube 305, the partition cover 304 and the side hole conical nozzle 313 are made of high borosilicate glass, and the condensate protection cover 308, the central guide column 307 and the cone 309 are made of polytetrafluoroethylene.

[0035] In this invention, the gas guide pipe 305 and the partition cover 304 are integrally formed from the same high borosilicate glass blank. The central hole of the partition cover 304 directly communicates with the inner cavity of the gas guide pipe 305, and there are no assembly seams, threaded interfaces, or adhesive layers between them. As a result, the vapor flow channel from the lower gas guide area through the central hole into the gas guide pipe 305 is continuous throughout, with no steps, annular seams, or dead corners on the inner wall of the channel. The vapor does not generate local throttling or eddies when passing through the central hole. At the same time, since the gas guide pipe 305 and the partition cover 304 are made of the same material, have the same coefficient of linear expansion, and are homogeneous, no thermal stress is generated at the interface when the temperature is repeatedly raised and lowered at the operating temperature of about 83°C to 86°C at the top of the tower. This avoids the risk of loosening and cracking after thermal cycling of separate or dissimilar connections. The one-piece molding of the central hole and the air guide tube 305 also ensures a fixed coaxial relationship between them. When the lower part of the outer conical surface of the cone 309 is supported at the opening of the central hole, the air intake channel 312 between the outer conical surface of the cone 309 and the inner wall of the air guide tube 305 has a uniform circumferential width, preventing flow deviation due to assembly eccentricity. After the steam rises through the air intake channel 312 to the upper part of the inner cavity of the air guide tube 305, it must enter the upper condensation zone through the air guide hole 301. Since the air intake channel 312 is a gradually narrowing channel with a wider bottom and a narrower top, the steam is accelerated within it, resulting in a higher flow velocity at the air guide hole 301. If the air guide hole 301 is a straight hole of uniform diameter, the high-speed airflow will directly rush into the upper condensation zone in the form of a jet, impacting the surface of the condensate falling back in this area and entraining liquid droplets, causing the liquid that has been separated by the first and second stage impacts to be carried away by the airflow again, forming a secondary entrainment. In this embodiment, a side-hole conical nozzle 313 is provided inside the air guide hole 301. Its wide opening communicates with the air guide hole 301, and its tip converges towards the inside of the air guide tube 305. This allows steam to flow from inside the air guide tube 305 towards the air guide hole 301 through a gradually expanding flow channel. Within the expanding section, the steam diffuses, its velocity decreases, and its dynamic pressure is converted into static pressure. It then enters the upper condensation zone at a lower speed and in a gentler direction. The impact intensity of the airflow on the condensate surface is significantly reduced, and secondary entrainment of liquid droplets is suppressed. The tip of the side-hole conical nozzle 313 converges towards the inside of the air guide tube 305, forming a constricted throat on one side of the inner cavity of the air guide tube 305. Its outer wall gradually opens from the throat towards the air guide hole 301. After undergoing a secondary impact, the separated liquid flowing downwards along the inner wall of the air guide tube 305 impacts the outer wall of the side-hole conical nozzle 313 at the air guide hole 301. The opened conical surface guides the liquid to one side of the inner wall of the air guide tube 305 and continues to flow downwards, thus shielding it from the gas passage. Simultaneously, vapor continuously flows from the throat to the wide opening and is discharged, continuously purging liquid attempting to enter in reverse. The narrowing of the throat also creates a throttling obstruction for the liquid, preventing it from flowing back into the air guide tube 305 through the air guide hole 301 or flowing out in the opposite direction. Both the side-hole conical nozzle 313 and the air guide tube 305 are made of high borosilicate glass. Since they are made of the same material, they can be seamlessly sealed together at the air guide hole 301, without introducing adhesives. The smooth conical surface allows for self-drainage, preventing the formation of dead corners for dirt accumulation.In terms of material composition, the buffer separation cylinder 303, the air guide pipe 305, the partition cover 304, and the side hole conical nozzle 313, which constitute the buffer separation cylinder and the steam flow channel, are all made of high borosilicate glass. These four components are made of the same material and can be sealed together as a whole, ensuring that the entire steam flow channel has no other openings or seams except for the air guide hole 301. The condensate protection cover 308, the central guide column 307, and the cone 309, which constitute the detachable internal components, are made of polytetrafluoroethylene (PTFE). The coefficients of linear expansion of PTFE and high borosilicate glass differ by more than an order of magnitude. If the PTFE components are fastened to the glass components using fasteners or rigid connections, the difference in expansion between the two during heating and cooling will generate thermal stress at the connection point, potentially causing the glass components to crack. In this embodiment, the condensate shield 308, the central guide column 307, and the cone 309 are not fixed with fasteners. Instead, they are pressed together from top to bottom under their own weight and the impact of the falling condensate on the condensate shield 308. The PTFE part can freely expand and contract along the axial direction, and the difference in expansion between it and the glass part is absorbed by this unrestrained pressing relationship. The glass part is not subjected to additional stress. The slight creep of PTFE under long-term heating is compensated by the continuous gravity and the impact force of the condensate. The pressing state does not loosen with the running time.

[0036] In this invention, the inner side of the air guide hole 301 is provided with a side hole conical nozzle 313 with the tip pointing inward. This allows the upward steam to enter the upper condensation zone smoothly after being diffused and decelerated through the gradually expanding flow channel. This avoids secondary entrainment of liquid droplets caused by the high-speed jet impacting the liquid surface of the condensate, thereby improving the gas-liquid separation efficiency of the buffer separation mechanism. At the same time, the throat extending into the inner cavity of the air guide tube 305 and the open conical surface are used to shield the separated liquid flowing down the inner wall of the air guide tube 305 from the gas channel. Furthermore, the continuous outflow of steam and the throttling of the throat prevent the liquid from flowing backward through the air guide hole 301. In the same structure, bidirectional adjustment of upward airflow deceleration and downward liquid blocking and drainage is achieved. The condensate shield 308, central guide column 307, and cone 309 are made of polytetrafluoroethylene (PTFE), which has low surface energy, making it difficult for condensate to spread and form a film on its surface, and thus easier to collect and drip, further reducing liquid entrainment. PTFE also has self-lubricating properties and a certain degree of elasticity, allowing the threaded connection between the central guide column 307 and the cone 309, and the conical surface pressing between the inverted conical column and the inverted conical hole, to maintain a tight seal without metal fasteners or lubricants. The PTFE components are assembled using an unrestrained pressing method, absorbing the difference in thermal expansion between them and the glass components, and creep is automatically compensated by the operating load, avoiding the risk of glass component cracking due to heterogeneous rigid connections.

[0037] Example 5:

[0038] like Figures 1-7As shown, the buffer separation mechanism 3 and the tower top condenser 4 are connected by a corrosion-resistant flexible connector 9; the corrosion-resistant flexible connector 9 includes: end seats 901, screws 902, tension springs 903, and flexible connecting pipes 904; the two end seats 901 are respectively tightly and sealed to the bottom of the condenser shell and the top of the buffer separation cylinder 303, and the two end seats 901 are clamped on the outside of the protruding ring at the bottom of the condenser shell and the protruding ring at the top of the buffer separation cylinder 303. The end seats 901 are formed by two semi-circular clamps joined together. Both ends are bolted and locked together with nuts, so that the end seat 901 is tightly attached to the outer periphery of the bottom of the condenser shell or the top of the buffer separation cylinder 303; the condenser shell and the buffer separation cylinder 303 are sealed together by a flexible connecting tube 904; multiple screws 902 are evenly wound around the two end seats 901, and the nuts threaded on the screws 902 are locked to the outside of one end seat 901; the end of the screw 902 is connected to the outer side of the other end seat 901 by a tension spring 903 sleeved on the screw 902. The flexible connecting tube 904 can be a polytetrafluoroethylene corrugated tube.

[0039] In this invention, both the buffer separation mechanism 3 and the tower top condenser 4 are high borosilicate glass components. Neither can withstand the excessive clamping force and eccentric bending moment caused by rigid flange connections. Furthermore, if they are only connected by ground joints or sleeves, a reliable seal cannot be maintained under negative pressure conditions inside the tower. The corrosion-resistant flexible connector 9 is used to simultaneously achieve both flexible compensation and elastic clamping functions at this location. The flexible connecting pipe 904 is placed between the bottom of the condenser shell and the top of the buffer separation cylinder 303. Its two flanges respectively fit against the opposite end faces of the protruding rings at the bottom of the condenser shell and the top of the buffer separation cylinder 303. The flexible connecting pipe 904 directly forms the vapor flow channel for this section, creating a sealed connection between the condenser shell and the buffer separation cylinder 303. The inner diameter of the flexible connecting pipe 904 matches the inner diameters of the bottom of the condenser shell and the top of the buffer separation cylinder 303. The inner wall of the flow channel at the connection point is flush and continuous, without forming liquid accumulation steps or stagnant dead zones. The flexible connecting pipe 904 is a fluoroplastic corrugated pipe. Its corrugated structure allows for axial expansion and contraction and slight radial deflection, absorbing the difference in axial elongation between the cold and hot states of the glass component, coaxiality deviation during installation, and vibration displacement during operation. During assembly, the two semi-circular clamps constituting the end seat 901 are first aligned radially to the outer periphery of the bottom of the condenser shell or the top of the buffer separator 303, and then the clamps are engaged with the outer side of the protruding ring, i.e., the side of the protruding ring facing away from the flexible connecting pipe 904. The nuts on the clamps are then tightened, and the two clamps tighten towards each other, holding the glass component tightly. Because the end seat 901 has a split structure, it can be directly aligned radially from the glass component without needing to be fitted from the end of the glass component. Therefore, the assembly is not limited by the outer diameter of the protruding ring being larger than the outer diameter of the pipe body. The clamping force ensures that the inner circumferential surface of the end seat 901 adheres to the outer surface of the glass, achieving a seal, and simultaneously allows the end seat 901 to transmit axial force to the glass component it is engaged with. Multiple screws 902 are evenly arranged around and passed between two end seats 901. When the nuts on the screws 902 are tightened, the clamping force forms a closed force chain along the following path: the nut acts on the outside of one end seat 901, and is transmitted through the end seat 901 to the protruding ring it engages with. Then, the end face of the protruding ring presses against the flange at one end of the flexible connecting tube 904. Subsequently, the force is transmitted through the end face of the protruding ring at the top of the flexible connecting tube 904 and the buffer separation cylinder 303 to the other end seat 901. The outer side of the end seat 901 is compressed and sleeved on the tension spring 903 of the screw 902, and the other end of the tension spring 903 abuts against the end of the screw 902. Since the tension spring 903 is connected in series in this force chain, the clamping force borne by the flexible connecting tube 904 is determined by the elastic force of the tension spring 903, and is not linearly related to the degree of tightening of the nut: within the elastic stroke of the tension spring 903, turning the nut only changes the compression of the tension spring 903, and the clamping force changes gradually and has an upper limit. Therefore, the flexible connecting tube 904 will not be over-compressed and buckle or undergo permanent deformation.The operating temperature at the top of the tower is near the boiling point of germanium tetrachloride. The flexible connecting tube 904, under prolonged heating and continuous pressure, will experience cold flow creep. The glass components will also undergo axial expansion and contraction during heating and cooling. Both of these phenomena manifest as a slow change in the distance between the two end seats 901. Due to the low stiffness of the tension spring 903, this distance change only causes a corresponding change in the elongation of the tension spring 903, keeping the clamping force essentially constant. This ensures that the end-face sealing pressure of the flexible connecting tube 904 remains within the set range for an extended period, eliminating the need for shutdown and re-tightening. The end seats 901, screw 902, and tension spring 903 are all located around the flexible connecting tube 904 and do not participate in forming the material flow channel. The only component in contact with germanium tetrachloride vapor at the connection point is the flexible connecting tube 904. The flexible connecting pipe 904 does not use the conventional metal corrugated pipe in this field: Germanium tetrachloride has limited corrosiveness to stainless steel under strictly anhydrous conditions, but in this distillation system, during start-up and shutdown, when not fully dried after maintenance, and under conditions where poor insulation causes local wall temperatures to fall below the acid dew point, hydrogen chloride and water will form an acidic liquid film on the metal surface; the corrugated structure of the flexible connecting pipe 904 itself has residual forming stress and working stress, and austenitic stainless steel is at risk of chloride stress corrosion cracking under the combined effects of chloride ions, tensile stress, and a temperature range of 50℃~150℃. Moreover, metal ions such as iron, nickel, and chromium in the corrosion products will directly cause the product impurities to exceed the standard after entering the germanium tetrachloride, failing to meet the requirements of electronic-grade germanium tetrachloride. Therefore, the flexible connecting pipe 904, which comes into contact with germanium tetrachloride vapor, is made of fluoroplastic that is chemically inert to the above-mentioned media, while the end seat 901, screw 902, and tension spring 903 are not subject to this material restriction because they are located outside the material flow channel. Fluoroplastic corrugated pipes exhibit lower cold flow tendency and resistance to external pressure compared to metal corrugated pipes under long-term heat and pressure. Polytetrafluoroethylene (PTFE) shows a relatively pronounced cold flow tendency, while perfluoroethylene propylene (PFEP) and fusible PTFE show less. The decrease in sealing pressure caused by cold flow is overcome by the continuous compensation of the tension spring 903, while resistance to external pressure is ensured by reducing the corrugation pitch and increasing the corrugation trough wall thickness. When the flexible connecting pipe 904 is made of transparent fluoroplastics such as PFEP or fusible PTFE, the pipe body is transparent or semi-transparent, allowing direct external observation of liquid accumulation, germanium dioxide deposition, and abnormal conditions on the flanged sealing surface within the flow channel at the connection point. Furthermore, PFEP and fusible PTFE have melt flow properties, allowing the end flange of the flexible connecting pipe 904 to be heat-fused and welded to the pipe body as a single unit, resulting in a seamless sealing surface. In contrast, PTFE lacks melt flow properties, and its end flange is integrally formed from a rod.

[0040] Example 6:

[0041] like Figures 1-7As shown, the corrosion-resistant flexible connector 9 also includes: a sheath 905, which is disposed between the two end seats 901 and within the coil of the multiple screws 902. The sheath 905 covers the flexible connecting tube 904 but does not cover the multiple screws 902 and the tension spring 903. The sheath 905 includes a transparent fluoroplastic corrugated tube at the top and a high borosilicate glass tube at the bottom. The lower end of the transparent fluoroplastic corrugated tube is sealed to the upper end of the high borosilicate glass tube, and the upper end of the transparent fluoroplastic corrugated tube is sealed and fixed to the outer surface of the upper end seat 901 by a fluoroplastic sealing ring. The lower end of the glass tube is sealed and supported on the outer surface of the lower end seat 901 by a fluoroplastic spherical seat ring, and both are staggered from the nuts and tension springs 903; the bottom of the high borosilicate glass tube is provided with a drain port with a control valve, and a liquid trap is provided between the drain port and the high borosilicate glass tube. The height of the high borosilicate glass tube is not less than two-thirds of the total height of the sheath 905, so that the liquid level of the waste liquid collected in the leak collection and detection chamber is lower than the lower end of the transparent fluoroplastic corrugated pipe; the flexible connecting pipe 904, the two end seats 901 and the sheath 905 form a leak collection and detection chamber for collecting the leaked medium.

[0042] In this invention, the upper and lower ends of the sheath 905 are respectively sealed to two end seats 901, thereby forming a closed chamber surrounding the flexible connecting tube 904, i.e., a leak collection and detection chamber, between the flexible connecting tube 904, the two end seats 901, and the sheath 905. Once the flexible connecting tube 904 leaks, the leaked medium enters this chamber and is confined within it, preventing direct escape to the external environment. The sheath 905 is radially positioned within the rings of the multiple screws 902, and only covers the flexible connecting tube 904, not the multiple screws 902 and the tension spring 903. This keeps the screws 902, nuts, and tension spring 903 outside the leak collection and detection chamber. On the one hand, the adjustment of the nuts and the observation of the compression state of the tension spring 903 are not obstructed by the sheath 905; on the other hand, the leaked medium does not come into contact with the metal parts within the covered area, preventing corrosion and avoiding corrosion products from mixing into the collected leaked medium and interfering with the judgment. The sheath 905 is axially divided into upper and lower sections. The upper section is a transparent fluoroplastic corrugated tube, and the lower section is a high borosilicate glass tube. Since the axial distance between the two end seats 901 changes with the extension and contraction of the tension spring 903 and the thermal expansion and contraction of the flexible connecting pipe 904, the upper section, made of transparent fluoroplastic corrugated tube, can expand and contract axially accordingly. This allows the sheath 905 to maintain a seal at both ends without restricting the relative displacement, thus not weakening the flexible compensation capability of the corrosion-resistant flexible connector 9. The lower section, made of high borosilicate glass tube, provides a sufficiently large and shape-stable liquid collection space, facilitating the machining of a drain port and a liquid trap at its bottom. The height of the high borosilicate glass tube is not less than two-thirds of the total height of the sheath 905, ensuring that the lower part of the leak collection and detection chamber has a liquid collection volume occupying most of its height. During normal operation, the waste liquid level is confined within the high borosilicate glass tube, below the lower end of the transparent fluoroplastic corrugated tube. Therefore, the collected waste liquid only contacts the high borosilicate glass and not the transparent fluoroplastic corrugated tube. The upper end of the transparent fluoroplastic bellows is pressed against the outer side of the upper end seat 901 by a fluoroplastic sealing ring, forming a seal and fixation at the upper end of the leak collection and detection chamber. The lower end of the high borosilicate glass tube is supported on the outer side of the lower end seat 901 by a fluoroplastic spherical seat ring, forming a seal and support at the lower end of the leak collection and detection chamber. After assembly, the transparent fluoroplastic bellows maintains a certain axial compression. Its rebound force presses the fluoroplastic sealing ring against the outer side of the upper end seat 901 and the fluoroplastic spherical seat ring against the outer side of the lower end seat 901, thus forming an axial compression seal at both ends. This axial compression can also compensate for changes in the axial distance between the two end seats 901, ensuring that the sealing surfaces at both ends remain compressed during operation. The fluoroplastic spherical seat ring and the lower end seat 901 are in a spherical fit. When there is a coaxiality deviation between the two end seats 901 or angular displacement occurs during operation, the spherical fit can adaptively deflect, so that the high borosilicate glass tube only bears axial pressure and not bending moment, avoiding damage to the glass components due to off-center loading.The fluoroplastic sealing ring and the fluoroplastic spherical seat ring are radially positioned on the outer surface of the end seat 901 between the flexible connecting tube 904 and the screw 902, thus offset from the nut and tension spring 903, and do not interfere with each other during assembly and disassembly. The sheath 905 is located outside the equipment and in contact with the environment. The temperature inside the leakage collection and detection chamber is lower than the temperature of the medium inside the flexible connecting tube 904. Germanium tetrachloride leaking from the flexible connecting tube 904 enters the chamber, is cooled and condenses into liquid, flows down the inner wall of the sheath 905 and accumulates at the bottom of the borosilicate glass cylinder. If the germanium tetrachloride in the leaked medium comes into contact with the trace amount of moisture remaining in the chamber, it will hydrolyze to form germanium dioxide solid, which will also be deposited at the bottom of the borosilicate glass cylinder. Both the transparent fluoroplastic corrugated tube of the sheath 905 and the borosilicate glass cylinder are made of transparent material, and the liquid level, liquid state, and germanium dioxide deposition in the chamber can be directly observed from the outside. When waste liquid needs to be discharged from the leak collection and detection chamber, the control valve on the drain port is opened. The waste liquid accumulated at the bottom of the borosilicate glass cylinder is discharged through the drain port via the liquid trap under the combined action of gravity and the pressure inside the chamber. After the discharge is completed, the control valve is closed, and the liquid remaining in the liquid trap forms a liquid seal, isolating the leak collection and detection chamber from the external environment. This prevents continuous leakage of gas from the chamber and also prevents external air and its moisture from entering the leak collection and detection chamber through the drain port. In this invention, the sheath 905, the flexible connecting pipe 904, and the two end seats 901 together form a closed leak collection and detection chamber, so that the leakage medium from the flexible connecting pipe 904 is collected in a concentrated manner and does not escape into the external environment. This avoids the harm of germanium tetrachloride and its hydrolysis products to personnel and equipment, and allows the leakage medium to be recovered. At the same time, it provides an observable, sampleable, and measurable object for judging the sealing status of the flexible connecting pipe 904. The sheath 905 adopts a segmented structure with an upper section of transparent fluoroplastic corrugated pipe and a lower section of high borosilicate glass tube. The upper section can expand and contract with the axial distance between the two end seats 901, without interfering with the flexible compensation function of the corrosion-resistant flexible connector 9. The lower section provides a stable liquid collection volume and facilitates the installation of a drainage structure. The two sections perform their respective functions, allowing the leakage collection function and the flexible compensation function to coexist in the same location without affecting each other. The height of the high borosilicate glass tube is not less than two-thirds of the total height of the sheath 905, so that the waste liquid level is limited to the high borosilicate glass tube and below the lower end of the transparent fluoroplastic corrugated pipe. The collected waste liquid only comes into contact with the high borosilicate glass. This avoids the accumulation of waste liquid in the troughs of the corrugated pipe, eliminating the problems of difficult drainage and cleaning of trough accumulation, germanium dioxide deposition, and the potential for permeation and swelling of the fluoroplastic corrugated pipe due to long-term immersion in germanium tetrachloride, thus improving the service life of the sheath 905 and the cleanliness of repeated use. Both the transparent fluoroplastic corrugated tube and the high borosilicate glass cylinder are transparent, allowing direct observation of the liquid level, liquid state, and germanium dioxide deposition within the chamber without disassembly. The liquid can be discharged in time before it approaches the lower end of the transparent fluoroplastic corrugated tube, forming a distillation system that can be observed along the entire process together with the visual observation of the buffer separation cylinder 303.During drainage, the waste liquid accumulated at the bottom of the borosilicate glass cylinder first fills the storage trap and then is discharged through the drain port. The liquid column formed in the storage trap during drainage isolates the leakage collection and detection chamber from the external environment, preventing the gas in the chamber from leaking out in large quantities with the waste liquid, and preventing external air and its moisture from being drawn into the chamber. After drainage is completed, the control valve closes to seal the leakage collection and detection chamber. The upper end of the transparent fluoroplastic corrugated tube is sealed and fixed with a fluoroplastic sealing ring, and the lower end of the borosilicate glass cylinder is sealed and supported with a fluoroplastic spherical seat ring, forming an assembly relationship of upper fixed and lower supported. The axial compression of the transparent fluoroplastic corrugated tube provides continuous axial clamping force to the sealing surfaces at both ends and compensates for changes in the axial distance between the two end seats 901. The fluoroplastic spherical seat ring can adapt to angular deviations, so that the borosilicate glass cylinder only bears axial pressure and not bending moment, avoiding damage to the glass components due to installation coaxiality deviations or angular displacement during operation.

[0043] Example 7:

[0044] like Figures 1-7 As shown, the corrosion-resistant flexible connector 9 also includes: a humidity sensor, a hydrogen chloride sensor, a pressure sensor, and an inert gas inlet pipe; the leak collection and detection chamber is connected to an inert gas inlet pipe and an exhaust pipe. The inert gas inlet pipe introduces a constant small flow of inert gas into the leak collection and detection chamber to maintain a slight positive pressure not lower than atmospheric pressure and prevent external moisture from seeping in through the sealing interface of the flexible connector 904. When the slight positive pressure is lost, external moisture seeps in through the sealing interface of the flexible connector 904 and hydrolyzes with germanium tetrachloride. The hydrogen chloride generated by hydrolysis is discharged with the inert gas through the exhaust pipe. The humidity sensor and the hydrogen chloride sensor are located at the exhaust pipe to detect the increase in humidity and the increase in hydrogen chloride of the discharged gas relative to the introduced inert gas. The exhaust pipe is equipped with a liquid seal device or a back pressure valve to maintain the slight positive pressure in the leak collection and detection chamber and to detect leaks. When the pressure in the measuring chamber exceeds the set upper limit, the venting is opened. The exhaust pipe outlet is connected to the tail gas treatment device. The pressure sensor is set in the leak collection and detection chamber. The pressure drop detected by the pressure sensor, together with the humidity increment and hydrogen chloride increment, is used to determine whether the micro-positive pressure has failed. The pressure rise detected by the pressure sensor is used to determine whether there is an internal leak of germanium tetrachloride in the flexible connecting pipe 904. The detection signals of the humidity sensor and the hydrogen chloride sensor are used to determine the hydrolysis of germanium tetrachloride caused by the infiltration of external moisture through the sealing interface of the flexible connecting pipe 904. The germanium dioxide solid particles generated by hydrolysis enter the lower gas guide zone with the rising vapor and are captured by impact on the bottom plane of the cone 309. The temperature of the pre-condensed gas phase at the top of the tower detected by the temperature sensor 306, together with the detection signals of the humidity sensor and the hydrogen chloride sensor, is used to adjust the reflux ratio of the reflux ratio controller 7 and the air intake of the inert gas inlet pipe.

[0045] The bottom of the high borosilicate glass cylinder is integrally formed into a downward-convex funnel shape, with the drain outlet located at the lowest point of the funnel shape. The highest liquid level in the leak collection and detection chamber is no higher than half the height of the high borosilicate glass cylinder. The inlet of the inert gas inlet pipe extends to the lower part of the leak collection and detection chamber and is higher than the highest liquid level, with the inlet facing downwards to blow the inert gas onto the liquid surface at the bottom of the leak collection and detection chamber. The exhaust pipe is located at the upper part of the leak collection and detection chamber. The inlet of the inert gas inlet pipe and the exhaust pipe are staggered circumferentially in the leak collection and detection chamber so that the inert gas flows from bottom to top and circumferentially through the leak collection and detection chamber before being discharged. The outer surface of the lower end of the high borosilicate glass tube is an outer spherical surface, and the fluoroplastic spherical seat ring is provided with an inner spherical surface that fits and laps with the outer spherical surface. The outer spherical surface and the inner spherical surface form a sealing pair that allows the high borosilicate glass tube to swing around the center of the sphere for self-alignment. The transparent fluoroplastic bellows is axially pre-compressed in the assembled state, and its rebound force continuously presses the outer spherical surface against the inner spherical surface. The upper end of the high borosilicate glass tube is provided with an outer conical surface, and the lower end of the transparent fluoroplastic corrugated tube is heat-fused to a fluoroplastic transition joint. The fluoroplastic transition joint is provided with an inner conical surface that fits snugly against the outer conical surface. The transparent fluoroplastic corrugated tube is axially pre-compressed in the assembled state, and its rebound force continuously presses the inner conical surface against the outer conical surface. The taper of the outer conical surface and the inner conical surface is 1:10. The rear end of the inner hole of the fluoroplastic transition joint is integrally formed with several elastic claws. After the elastic claws pass over the large end of the outer conical surface, they rebound and lock onto the high borosilicate glass tube. Both the transparent fluoroplastic corrugated tube and the fluoroplastic transition joint are made of perfluoropropylene or fusible polytetrafluoroethylene, which can be heat-fused. An inert gas inlet pipe is equipped with a flow controller, which introduces a constant flow of inert gas into the leak collection and detection chamber to ensure that the amount of inert gas seeping into the distillation column 2 through the sealing interface of the flexible connecting pipe 904 does not exceed a set value. The pressure drop rate detected by the pressure sensor is used to characterize the degree of defect at the main sealing interface of the flexible connecting pipe 904; a larger pressure drop rate indicates a larger defect at the main sealing interface. Under normal operating conditions, the micro-positive pressure in the leak collection and detection chamber is 0.2 kPa to 0.5 kPa higher than atmospheric pressure, and the inert gas flow rate is 1 mL / min to 5 mL / min. The inert gas is nitrogen.

[0046] The corrosion-resistant flexible connector 9 also includes a controller, which is connected to the humidity sensor, hydrogen chloride sensor, and pressure sensor. The controller determines that the micro-positive pressure is effective when both the humidity increment and hydrogen chloride increment are within the set range and the pressure detected by the pressure sensor is within the set pressure range. At this time, the pressure gradient in the leak collection and detection chamber is from the inside to the outside, and external moisture cannot seep in through the sealing interface of the flexible connector 904. The controller determines that the micro-positive pressure fails when the humidity increment or hydrogen chloride increment exceeds the set range, or when the pressure drop detected by the pressure sensor exceeds the set value. When the micro-positive pressure fails, the controller outputs an alarm signal and increases the air intake of the inert gas inlet pipe. The controller determines that the flexible connector 904 has internal leakage of germanium tetrachloride when the pressure rise detected by the pressure sensor exceeds the upper limit of the set pressure range. The germanium tetrachloride that leaks into the leak collection and detection chamber has a saturated vapor pressure higher than atmospheric pressure at the distillation temperature and is heated and vaporized, causing the pressure in the leak collection and detection chamber to rise and be detected by the pressure sensor.

[0047] The buffer separation cylinder 303 is made of transparent high borosilicate glass and forms an observation section for visually judging the amount of germanium dioxide deposited. The outer surface of the buffer separation cylinder 303 is provided with scale marks for judging the thickness of germanium dioxide deposits. The germanium dioxide solid particles generated by hydrolysis enter the lower gas guiding zone with the rising vapor and are knocked off by the first-stage impact surface of the bottom plane of the cone 309. They are collected in the annular groove 310 and the longitudinal conical through hole 311 to the separator hood 304, and then discharged from the condensate outlet 302. The amount of germanium dioxide deposited, together with the increase in humidity and the increase in hydrogen chloride, are used to determine the location and extent of germanium tetrachloride hydrolysis.

[0048] Example 8:

[0049] like Figures 1-7 As shown, a distillation method is applied to a germanium tetrachloride distillation column as described in any of the above-mentioned embodiments. The method includes the following steps: S1. Pretreatment: Crude germanium tetrachloride is pre-distilled in a pretreatment unit with concentrated sulfuric acid to remove organic impurities. The pre-distillation temperature is controlled at 80-90℃ for 2-2.2 hours. The pre-distillation product is added with analytical grade hydrochloric acid and chlorine gas is introduced to complete the re-distillation to further remove transition metal impurities. The re-distillation product is added with concentrated sulfuric acid for a second digestion and distillation to further remove residual organic and metal impurities. The qualified pretreatment product is sent to the first-end distillation unit. S2. Distillation: The pretreated qualified product is continuously distilled in multiple distillation units connected in series. During distillation, the reboiler 1 is heated to vaporize germanium tetrachloride. The temperature of the reboiler 1 is controlled above 100℃. The vapor rises along the distillation column 2 and completes gas-liquid mass transfer with the liquid refluxed from the top of the column to achieve component separation. The temperature at the top of the column is stabilized at 83-86℃. The germanium tetrachloride vapor enters the top condenser 4 through the gas inlet 301 of the buffer separation mechanism 3 for condensation. The uncondensed gas enters the first product condenser 5 through the first outlet at the top of the top condenser 4 for secondary condensation. The condensate is recovered and flows into the reflux ratio controller 7 through the condensate outlet 302 of the buffer separation mechanism 3 and the first inclined tube 6. The reflux ratio controller 7 controls the reflux ratio in the range of 4:1 to 14:1, and distributes the condensate into reflux liquid and product liquid. The reflux liquid returns to the buffer separation mechanism 3 through the reflux outlet of the reflux ratio controller 7 and the second inclined tube 8 and falls back to the distillation column 2 to continue gas-liquid mass transfer. The product liquid is collected after being cooled by the product outlet of the reflux ratio controller 7 and the second product condenser 10. The product is output from the distillation unit located at the tail end. S3. Collection: The product output from the tail-end distillation unit is sent to the collection device, and after online sampling and testing to confirm that the purity meets the standard, it is stored.

[0050] After multi-stage series distillation, the product output from the tail-end distillation unit reaches extremely high purity. Once the product is fed into the collection device, the content of transition metal impurities and hydrogen impurities is monitored in real time using online sampling and testing equipment. When the test results show that the transition metal impurity content has dropped to a preset value, the product purity is confirmed to meet fiber optic or electronic grade standards, and then it is sealed and stored. If the test results fail to meet the standards, the product is returned to the front-end distillation unit for re-distillation to ensure that the finally collected product fully meets the high-purity requirements.

[0051] Although embodiments of the present invention have been disclosed above, they are not limited to the applications listed in the specification and embodiments. They can be applied to various fields suitable for the present invention. Other modifications can be easily made by those skilled in the art. Therefore, without departing from the general concept defined by the claims and their equivalents, the present invention is not limited to the specific details and illustrations shown and described herein.

Claims

1. A germanium tetrachloride distillation column, characterized in that, include: The system includes a pretreatment unit, a distillation unit, and a collection unit. Multiple distillation units are connected in series. The pretreatment unit is connected to the feed inlet of the distillation unit at the beginning, and the discharge outlet of the distillation unit at the end is connected to the collection device; the distillation unit includes: a reboiler, the top of the reboiler is connected to the distillation column, and the top of the distillation column is connected to the top condenser of the column through a buffer separation mechanism; The buffer separation mechanism is equipped with a gas guide hole and a condensate outlet. The vapor in the distillation column enters the top condenser through the gas guide hole of the buffer separation mechanism. The top of the top condenser is provided with a first outlet, which is connected to a first product condenser through a pipeline. The condensate outlet is connected to a reflux ratio controller through a first inclined tube. The reflux ratio controller has a reflux outlet and a product outlet. The reflux outlet is connected to the buffer separation mechanism through a second inclined tube to return the refluxed condensate back into the distillation column. The product outlet is connected to a second product condenser through a pipeline.

2. The germanium tetrachloride distillation column according to claim 1, characterized in that, The distillation column, the buffer separation mechanism, the first product condenser, the second product condenser, and the top condenser are all made of high borosilicate glass.

3. A germanium tetrachloride distillation column according to claim 2, characterized in that, A liquid seal bottle is installed on the pipeline between the outlet of the reflux ratio controller and the second finished product condenser. The liquid seal bottle contains a sealing liquid to form a liquid seal to prevent external air from being drawn back when the system is under negative pressure.

4. A germanium tetrachloride distillation column according to claim 2, characterized in that, The column top condenser includes: a condenser shell with a first outlet, and a condensing coil installed inside the condenser shell; the inlet and outlet of the condensing coil both extend to the outside of the condenser shell; the buffer separation mechanism includes: a buffer separation cylinder, the top and bottom of which are detachably and sealingly connected to the condenser shell and the distillation column, respectively; a partition cover integrally formed in the middle of the buffer separation cylinder, which divides the interior of the buffer separation cylinder into an upper condensation zone and a lower gas guiding zone; a top-sealed gas guiding pipe is fixed in the middle of the top of the partition cover, and a gas guiding hole is opened on the side wall of the gas guiding pipe; the condensate outlet on the side wall of the buffer separation cylinder is connected to the upper condensation zone; the horizontal height of the condensate outlet is lower than the gas guiding hole and higher than the partition cover, and is connected to the reflux ratio controller through a first inclined pipe; a second inclined pipe connected to the reflux outlet is inserted into the lower gas guiding zone to allow the refluxed condensate to fall back to the distillation column; a temperature measuring port is provided on the side wall of the buffer separation cylinder, and a temperature sensor inserted into the lower gas guiding zone is sealed and fixed inside the temperature measuring port.

5. A germanium tetrachloride distillation column according to claim 4, characterized in that, The separator inside the buffer separator bulges upward from the outside to the center to form an arc surface, so that the accumulated condensate flows from the center to the condensate outlet on the side of the buffer separator.

6. A germanium tetrachloride distillation column according to claim 5, characterized in that, The buffer separation mechanism also includes: a central guide column located inside the air guide tube, the upper end of which is fixedly connected to the bottom inverted conical column of the condensate protection shield, which covers the air guide tube; the lower end of the central guide column is threadedly connected to the internal threaded hole at the top of the cone; the bottom inverted conical column of the condensate protection shield is pressed into the inverted conical circular hole at the closed end of the air guide tube, and the horizontal height of the bottommost point of the inverted conical column is lower than the horizontal height of the closed end of the air guide tube; the bottom of the cone is a downward-facing plane to form a primary impact surface, and the outer conical surface of the cone is provided with... It has an annular groove, and the bottom of the annular groove is provided with several longitudinal conical through holes. The upper diameter of the longitudinal conical through holes is larger than the lower diameter. An air intake channel is formed between the outer conical surface of the cone and the inner wall of the air guide tube. After the vapor hits the bottom plane of the cone, it enters the air intake channel and is accelerated upward. Then it enters the annular gap between the central guide column and the air guide tube and hits the closed end of the top of the air guide tube. The outer wall of the central guide column is provided with a guide groove, which guides the separated liquid in the annular gap to the outer conical surface of the cone. The temperature sensor extends into the air intake channel through the side wall of the buffer separation cylinder.

7. A germanium tetrachloride distillation column according to claim 6, characterized in that, A side-hole conical nozzle is fixed inside the air guide hole on the side wall of the air guide tube. The wide opening of the side-hole conical nozzle is connected to the air guide hole, and the tip is tapered towards the inside of the air guide tube. The buffer separation cylinder, air guide tube, separator and side-hole conical nozzle are made of high borosilicate glass, and the condensate protection cover, central guide column and cone are made of polytetrafluoroethylene.

8. A germanium tetrachloride distillation column according to claim 7, characterized in that, The buffer separation mechanism and the top condenser are connected by a corrosion-resistant flexible connector. The corrosion-resistant flexible connector includes: an end seat, a screw, a tension spring, and a flexible connecting tube. The two end seats are respectively tightly and sealed to the bottom of the condenser shell and the top of the buffer separation cylinder, and the two end seats are clamped on the outside of the protruding ring at the bottom of the condenser shell and the protruding ring at the top of the buffer separation cylinder. The condenser shell and the buffer separation cylinder are sealed and connected by a flexible connecting tube. Multiple screws are evenly wrapped around and passed between the two end seats. The nuts threaded on the screws are clamped on the outside of one end seat. The end of the screw is connected to the outer side of the other end seat by a tension spring sleeved on the screw.

9. A germanium tetrachloride distillation column according to claim 1, characterized in that, The tower reactor is an integrated jacketed reactor structure, equipped with a heating circulator. The heating circulator heats the material inside the tower reactor by circulating heat transfer oil through the jacket.

10. A distillation method applied to a germanium tetrachloride distillation column according to any one of claims 1-9, characterized in that, The method includes the following steps: S1. Pretreatment: Crude germanium tetrachloride is pre-distilled in a pretreatment unit with concentrated sulfuric acid to remove organic impurities. The pre-distillation temperature is controlled at 80-90℃ for 2-2.2 hours. The pre-distillation product is added with analytical grade hydrochloric acid and chlorine gas is introduced to complete the re-distillation to further remove transition metal impurities. The re-distillation product is added with concentrated sulfuric acid for a second digestion and distillation to further remove residual organic and metal impurities. The qualified pretreatment product is sent to the first-end distillation unit. S2. Distillation: The pretreated qualified product is continuously distilled in multiple distillation units connected in series. During distillation, the reboiler is heated to vaporize germanium tetrachloride. The reboiler temperature is controlled above 100°C. The vapor rises along the distillation column and completes gas-liquid mass transfer with the liquid refluxed at the top of the column to achieve component separation. The temperature at the top of the column is stabilized at 83-86°C. The germanium tetrachloride vapor enters the top condenser through the gas guide hole of the buffer separation mechanism for condensation. The uncondensed gas enters the first product condenser for secondary condensation and recovery through the first outlet at the top of the top condenser. The condensate flows into the reflux ratio controller through the condensate outlet of the buffer separation mechanism and the first inclined tube. The reflux ratio is controlled in the range of 4:1 to 14:1 by the reflux ratio controller, which distributes the condensate into reflux liquid and product liquid. The reflux liquid returns to the buffer separation mechanism through the reflux outlet of the reflux ratio controller and the second inclined tube and falls back to the distillation column to continue gas-liquid mass transfer. The product is collected after being cooled by the product outlet of the reflux ratio controller and the second product condenser. The product is output from the distillation unit located at the tail end. S3. Collection: The product output from the tail-end distillation unit is sent to the collection device, and after online sampling and testing to confirm that the purity meets the standard, it is stored.

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