Sublimation device
By setting a temperature gradient in the sublimation tube and using a sublimation device with a carrier gas, the problems of slow sublimation rate and low separation efficiency are solved, achieving efficient staged sublimation and purification.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Utility models(China)
- Current Assignee / Owner
- JIANGSU NATA OPTO ELECTRONIC MATERIAL CO LTD
- Filing Date
- 2026-06-10
- Publication Date
- 2026-07-21
AI Technical Summary
Existing sublimation equipment has a slow sublimation rate for substances with low vapor pressure, a slow discharge rate for substances that are easily decomposed at high temperatures, and difficulty in effectively separating impurities with different condensation points in a single process, requiring multiple purifications or mid-process shutdowns for adjustment.
A sublimation device was designed. By setting multiple sublimation zones in the sublimation tube and gradually reducing the temperature gradient along the airflow direction, the sublimation gas flow is accelerated by the carrier gas, achieving staged sublimation and avoiding mid-process shutdown for adjustment.
The sublimation rate was increased at a lower temperature, which solved the problem of slow discharge of substances that are easily decomposed at high temperatures. This enabled graded sublimation of substances with different sublimation points and improved purification efficiency.
Smart Images
Figure CN224524010U_ABST
Abstract
Description
Technical Field
[0001] This utility model belongs to the technical field of sublimation purification systems, and specifically relates to a sublimation device. Background Technology
[0002] Sublimation purification is a commonly used solid purification technique. Existing sublimation devices typically employ a method of heating and sublimating followed by condensation and collection.
[0003] In practical applications, these devices suffer from the following problems: for substances with low vapor pressure, the sublimation rate is slow, resulting in low purification efficiency; for substances that are easily decomposed at high temperatures, the sublimation temperature must be lowered to avoid decomposition, leading to a further decrease in the discharge rate. Furthermore, when impurities with different condensation points coexist in the sublimation products, existing devices struggle to achieve effective separation in a single process, often requiring multiple purification cycles or mid-process shutdowns for device adjustments.
[0004] Therefore, in order to address the aforementioned technical problems, it is necessary to provide a sublimation apparatus. Utility Model Content
[0005] The purpose of this invention is to provide a sublimation device that can accelerate sublimation gas and achieve staged sublimation.
[0006] To achieve the above objectives, the technical solution provided by a specific embodiment of this utility model is as follows:
[0007] A sublimation apparatus, the sublimation apparatus comprising:
[0008] A sublimation column, wherein the interior of the sublimation column is provided with a cavity for containing the crude product to be sublimated and purified, and the sublimation column includes an outlet at the top and an inlet at the bottom, both of which are connected to the cavity.
[0009] A first heating element is wound around the outer wall of the sublimation column;
[0010] The first temperature sensing element is disposed on the outer wall of the sublimation column and is in thermal contact with the sublimation column;
[0011] A sublimation tube is provided, the inlet end of which is connected to the outlet of the sublimation column. The sublimation tube is provided with multiple sublimation zones in sequence along the gas flow direction. At least one of the sublimation zones is provided with a second heating element around its outer wall. Along the gas flow direction, any sublimation zone with the second heating element is located upstream of any sublimation zone without the second heating element. A second temperature measuring element is provided on the outer wall of each sublimation zone with the second heating element. The set temperature of the multiple sublimation zones gradually decreases along the gas flow direction.
[0012] A carrier gas introduction component is connected to the air inlet of the sublimation column;
[0013] A vacuum system is connected to the outlet end of the sublimation tube.
[0014] In one or more embodiments of this utility model, the sublimation column includes a sublimation section and a carrier gas introduction section. The sublimation section is connected to the condensation tube, the carrier gas introduction section is connected to the carrier gas introduction assembly, the air inlet is disposed on the carrier gas introduction section, and the carrier gas introduction section and the sublimation section are not collinear.
[0015] In one or more embodiments of this utility model, the sublimation section is a vertical pipe section, the carrier gas introduction section is a curved pipe section, one end of the curved pipe section is connected to the bottom of the vertical pipe section, and the other end of the curved pipe section is provided with the air inlet.
[0016] In one or more embodiments of this utility model, the sublimation section is a vertical pipe section, the carrier gas introduction section is a horizontal straight pipe section, the bottom of the horizontal straight pipe section is perpendicularly connected to the bottom of the vertical pipe section, and the air inlet is provided at the free end of the horizontal straight pipe section.
[0017] In one or more embodiments of this utility model, the sublimation section is a vertical pipe section, the carrier gas introduction section includes a curved pipe section and a horizontal straight pipe section, one end of the curved pipe section is connected to the bottom of the vertical pipe section, the other end of the curved pipe section is connected to one end of the horizontal straight pipe section, and the air inlet is provided at the free end of the horizontal straight pipe section.
[0018] In one or more embodiments of this utility model, a pressure element is further provided inside the sublimation column.
[0019] In one or more embodiments of the present invention, the interior of the deposition tube is provided with a plurality of detachable inner tubes, the number of the inner tubes being equal to the number of the deposition zones, and each inner tube being disposed inside a corresponding deposition zone.
[0020] In one or more embodiments of the present invention, the sublimation apparatus further includes a cooling device disposed between the outlet end of the sublimation tube and the vacuum system.
[0021] In one or more embodiments of the present invention, the cooling device includes a cooling sleeve and a cooling machine connected to the cooling sleeve, wherein the cooling sleeve is fitted onto the outer wall of the downstream sublimation zone.
[0022] In one or more embodiments of this invention, the vacuum system is connected to the sublimation tube via a flexible hose.
[0023] A sealing structure is provided between the sublimation tube and the sublimation column and / or between the sublimation tube and the vacuum system.
[0024] Compared with existing technologies, the sublimation device of this invention, by introducing a carrier gas, can accelerate the flow of sublimation gas and continuously carry away vapor, thereby achieving a more ideal sublimation rate at a lower temperature. This addresses both the slow discharge of easily decomposable high-temperature substances and the problem of accelerating the sublimation of low vapor pressure substances. Simultaneously, the gradually decreasing temperature gradient set along the airflow direction in the sublimation tube allows high-condensation-point substances, the target product, and low-condensation-point substances in the sublimation vapor to be sublimated sequentially in different sublimation zones, achieving staged sublimation without the need for mid-process shutdowns for device adjustments, thus improving sublimation efficiency. Attached Figure Description
[0025] To more clearly illustrate the technical solutions in the embodiments of this utility model or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments recorded in this utility model. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.
[0026] Figure 1 This is a schematic diagram of the sublimation device in one embodiment of the present invention;
[0027] Figures 2-4 This is a schematic diagram of the sublimation column in one embodiment of the present invention;
[0028] Figure 5 This is a schematic diagram of the sublimation tube in one embodiment of the present invention.
[0029] Explanation of key figure labels:
[0030] 1 Sublimation Column
[0031] 11. Cavity
[0032] 12 air outlets
[0033] 13 Air Intake
[0034] 14 Sublimation Section
[0035] 15. Carrier gas introduction section
[0036] 151 Bend pipe section
[0037] 152 Horizontal Straight Pipe Section
[0038] 16 Pressure components
[0039] 21 First heating element
[0040] 22 First temperature sensing element
[0041] 23 Second heating element
[0042] 24 Second temperature sensing element
[0043] 3. Sublimation tubes
[0044] 31 Ninghua District
[0045] 32 Inner tube
[0046] 33 Sealing structure
[0047] 4. Cooling device
[0048] 41 Cooling sleeve
[0049] 42 Cooling machine
[0050] 5. Carrier gas introduction assembly
[0051] 51 Gas Mass Flow Controller
[0052] 52 Main Controller
[0053] 6 Vacuum System
[0054] 7. Hose. Detailed Implementation
[0055] To enable those skilled in the art to better understand the technical solutions in this disclosure, the technical solutions in the embodiments of this disclosure will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of this disclosure, and not all embodiments. Based on the embodiments in this disclosure, all other embodiments obtained by those skilled in the art without creative effort should fall within the scope of protection of this disclosure.
[0056] It should be noted that similar labels and letters in the following figures indicate similar items. Therefore, once an item is defined in one figure, it does not need to be further defined and explained in subsequent figures.
[0057] It should be noted that, unless otherwise specified, the embodiments and features described in these embodiments can be combined with each other.
[0058] The technical solution of this utility model will now be described with reference to the accompanying drawings.
[0059] Reference Figures 1-5 As shown in the figure, this utility model embodiment provides a sublimation device. The device includes a sublimation column 1, a first heating element 21, a first temperature measuring element 22, a sublimation tube 3, a carrier gas introduction assembly 5, and a vacuum system 6.
[0060] The sublimation column 1 has a cavity 11 inside for containing the crude product to be sublimated and purified. The sublimation column 1 is provided with an outlet 12 and an inlet 13 that communicate with the cavity 11, wherein the outlet 12 is located at the top and the inlet 13 is located at the bottom.
[0061] A first heating element 21 (e.g., a resistance heating wire or heating jacket) is wound around the outer wall of the sublimation column 1 to provide the heat required for sublimation. A first temperature sensing element 22 (e.g., a thermocouple or resistance temperature detector) is disposed on the outer wall of the sublimation column 1 and is in thermal contact with the sublimation column 1 to monitor the sublimation temperature in real time.
[0062] The inlet end of the sublimation tube 3 is connected to the outlet 12 of the sublimation column 1. The sublimation tube 3 is provided with multiple sublimation zones 31 in sequence along the gas flow direction.
[0063] At least one sublimation zone 31 has a second heating element 23 (e.g., a resistance heating wire or heating sleeve) wrapped around its outer wall. Along the gas flow direction, any sublimation zone 31 with a second heating element 23 is located upstream of any sublimation zone 31 without a second heating element 23. Each sublimation zone 31 with a second heating element 23 has a corresponding second temperature sensing element 24 (e.g., a thermocouple or resistance temperature detector). Simultaneously, along the gas flow direction (i.e., from the end closest to the sublimation column 1 to the end furthest from the sublimation column 1), the operating temperature of these sublimation zones 31 gradually decreases. In other words, even if one or more downstream sublimation zones 31 do not have independent heating elements, their temperature can still be maintained at the required lower temperature through natural cooling or an additional cooling device 4 (as described below), thereby ensuring the realization of the entire temperature gradient.
[0064] For example, in one specific implementation, refer to Figure 5 As shown, the sublimation tube 3 has five sublimation zones 31. The outer walls of the first four sublimation zones 31 are respectively equipped with second heating elements 23 and corresponding second temperature measuring elements 24, while the last (i.e., the fifth) sublimation zone 31 does not have a second heating element 23, and its temperature is maintained at a low level through natural heat dissipation or the cooling device 4 described below. In another embodiment, the sublimation tube 3 has three sublimation zones 31. The first two sublimation zones 31 are equipped with second heating elements 23 and corresponding second temperature measuring elements 24, while the third sublimation zone 31 does not have a second heating element 23. In yet another embodiment, all sublimation zones 31 are equipped with second heating elements 23 and corresponding second temperature measuring elements 24. In this case, all sublimation zones 31 are actively temperature-controlled by the heating elements, but still maintain a gradient of gradually decreasing temperature along the airflow direction.
[0065] In other words, regardless of whether an independent heating element is provided in each sublimation zone 31, as long as the set temperature gradually decreases along the gas flow direction (i.e., the temperature decreases further downstream), and when there are sublimation zones 31 without heating elements, all of these sublimation zones 31 without heating elements are located at the very downstream, they all fall within the protection scope of this utility model.
[0066] The carrier gas introduction assembly 5 is connected to the inlet 13 of the sublimation column 1 and is used to introduce carrier gas into the sublimation column 1. Specifically, the carrier gas introduction assembly 5 may include a gas mass flow controller 51 and a main controller 52 connected to the gas mass flow controller 51. The input terminal of the gas mass flow controller 51 is connected to a carrier gas source (e.g., a nitrogen or argon cylinder), and the output terminal of the gas mass flow controller 51 is connected to the inlet 13 of the sublimation column 1. The main controller 52 is used to adjust the setpoint of the gas mass flow controller 51, thereby achieving precise control of the carrier gas flow rate.
[0067] Vacuum system 6 is connected to the outlet end of sublimation tube 3, providing a negative pressure environment for the entire sublimation process. Vacuum system 6 can be a vacuum pump or a vacuum generator, etc.
[0068] During operation, the vacuum system 6 provides negative pressure, and the carrier gas introduction component 5 provides a controllable flow rate of carrier gas (such as nitrogen or argon). The carrier gas enters from the inlet 13 at the bottom of the sublimation column 1, flows through the heated crude product to be sublimated, and carries the vapor generated by sublimation into the condensation tube 3 from the outlet 12 at the top. Because the condensation tube 3 has a gradually decreasing temperature gradient along the gas flow direction, when the mixed vapor passes through, substances with different condensation points will condense and precipitate in their respective corresponding saturation temperature regions, achieving simultaneous separation and purification of multiple components.
[0069] By introducing a carrier gas, the flow of sublimation gas can be accelerated and the vapor can be continuously carried away, thereby achieving a more ideal sublimation rate at a lower temperature. This addresses both the slow discharge of easily decomposable substances at high temperatures and the problem of accelerating the sublimation of substances with low vapor pressure. Simultaneously, the gradually decreasing temperature gradient set along the airflow direction in the sublimation tube 3 allows high-sublimation-point substances, the target product, and low-sublimation-point substances in the sublimation vapor to be sublimated sequentially in different sublimation zones 31, achieving staged sublimation without the need for mid-process shutdowns for device adjustments, thus improving sublimation efficiency.
[0070] Preferably, to improve the sealing effect of the entire sublimation device, sealing structures 33 are provided between the sublimation tube 3 and the sublimation column 1, and between the sublimation tube 3 and the vacuum system 6 in this embodiment, to prevent vapor leakage. Preferably, the sealing structure 33 in this embodiment is a KF connector and a sealing ring. Specifically, the KF connector includes a first flange disposed at the outlet 12 of the sublimation column 1, a second flange disposed at the inlet end of the sublimation tube 3, and a clamp for locking the first and second flanges; the sealing ring (e.g., an O-ring) is disposed between the first and second flanges (i.e., within the centering ring of the KF connector). Using a KF connector and sealing ring not only meets the vacuum sealing requirements but also facilitates quick disassembly, cleaning, and maintenance.
[0071] It should be noted that the sealing structure 33 can also be made of other detachable sealing connectors (such as ISO connectors, CF flanges, etc.), as long as they can achieve a sealed connection and include the corresponding sealing rings, they can replace the aforementioned KF connectors. Furthermore, when the sealing structure 33 is only installed between the sublimation tube 3 and the sublimation column 1, or only between the sublimation tube 3 and the vacuum system 6, the sealing effect of the sublimation device can be improved to a certain extent. Therefore, these alternative solutions also fall within the protection scope of this utility model.
[0072] Preferably, in order to prolong the contact time between the carrier gas and the crude product to be sublimated, so that the carrier gas can more fully carry the vapor generated by sublimation, refer to Figures 2-4 As shown, the sublimation column 1 in this embodiment mainly includes a sublimation section 14 and a carrier gas introduction section 15. The sublimation section 14 is connected to the condensation tube 3 and is mainly used to contain and heat the crude product. The carrier gas introduction section 15 is connected to the carrier gas introduction assembly 5, and the inlet 13 is disposed on the carrier gas introduction section 15. By setting the carrier gas introduction section 15 to a non-collinear structure, the flow path length of the carrier gas in the sublimation column 1 can be increased, thereby improving the carrier gas's vapor carrying efficiency.
[0073] In one specific implementation, refer to Figure 2 As shown, the sublimation section 14 is a vertical pipe section, while the carrier gas introduction section 15 is a curved pipe section 151. One end of the curved pipe section 151 is connected to the bottom of the vertical pipe section, and its free end is provided with an air inlet 13. For example, in order to operate in a low-water, low-oxygen glove box with a limited height, while ensuring that the carrier gas can effectively purge the crude product, the entire sublimation column 1 can be in a "J" shape. The vertical section is the sublimation section 14, and the curved hook part at the bottom is the carrier gas introduction section 15. The air inlet 13 is located at the end of the "J"-shaped hook, pointing to the upper side or horizontally, which facilitates connection to the carrier gas introduction assembly 5.
[0074] In another modified embodiment, refer to Figure 3As shown, for scenarios with more limited space, the sublimation section 14 is a vertical pipe section, and the carrier gas introduction section 15 is a horizontal straight pipe section 152. The bottom of the horizontal straight pipe section 152 is perpendicularly connected to the bottom of the vertical pipe section, forming an approximate "L" shape, with an air inlet 13 located at its free end. This structure is relatively simple and easy to manufacture.
[0075] In yet another implementation, refer to Figure 4 As shown, in this embodiment, the sublimation section 14 is a vertical pipe section, and the carrier gas introduction section 15 includes a curved pipe section 151 and a horizontal straight pipe section 152. One end of the curved pipe section 151 is connected to the bottom of the vertical pipe section, and the other end is connected to one end of the horizontal straight pipe section 152. An air inlet 13 is provided at the free end of the horizontal straight pipe section 152.
[0076] The various structural designs of the carrier gas introduction section 15 (the sublimation column 1 is J-shaped, L-shaped, or a combination of bent shapes) can all enable the carrier gas to be introduced from the bottom. By increasing the length of the airflow path, the contact time between the carrier gas and the coarse product is extended, thereby allowing the carrier gas to better carry away the vapor. At the same time, the non-collinear arrangement has an additional effect, which helps to prevent the pressure components 16 (such as pressure balls) or coarse product particles placed inside the sublimation column 1 from falling into or blocking the air inlet 13 due to gravity.
[0077] Compared to the traditional straight-up-down sublimation column 1, the sublimation column 1 in this embodiment not only improves the carrier gas carrying efficiency, but also reduces the interference of solid materials on the air inlet 13, enabling the device to operate more stably for a long time, reducing the need for frequent cleaning operations, and improving ease of use.
[0078] Furthermore, in order to ensure more uniform heating of the crude product during sublimation and to promote sufficient contact with the carrier gas, refer to... Figure 1 As shown, a pressure member 16 can also be provided inside the sublimation column 1. When the sublimation column 1 is filled with a crude product to be sublimated, the pressure member 16 is placed on the upper surface of the crude product layer to be sublimated.
[0079] In a specific example, the pressure element 16 can be a heavy sphere made of quartz or ceramic. During sublimation, the heavy sphere presses against the surface of the material under its own weight. As the material sublimates and the material level drops, the heavy sphere also descends smoothly, continuously applying a certain pressure to the material below, compressing the gaps between the materials. This helps to reduce the phenomenon of less carrier gas in smaller pores due to the carrier gas preferentially flowing through larger pore channels, thereby improving the uniformity of gas-solid contact.
[0080] In another embodiment, the pressure element 16 can be designed as a pressure plate that matches the inner diameter of the sublimation column 1. Several vent holes can be formed on the pressure plate, which is also pressed against the upper surface of the material. By providing the pressure element 16, it is beneficial to mitigate the problems of sublimation rate fluctuations and uneven product purity caused by loose material or the formation of pores.
[0081] Furthermore, to facilitate the collection of purified products and reduce the risk of product contamination or loss during disassembly, refer to Figure 1 and combined Figure 5 As shown, multiple detachable inner tubes 32 are provided inside the deposition tube 3. The number of these inner tubes 32 is equal to the number of deposition zones 31, and each inner tube 32 is independently and slidably placed inside the corresponding deposition zone 31.
[0082] It should be noted that before conducting the sublimation purification experiment, the operator can sequentially push multiple clean quartz inner tubes 32 (or glass inner tubes 32) into the sublimation tube 3, aligning them with the positions of multiple sublimation zones 31. After sublimation, the target product will sublimate and deposit on the inner walls of these inner tubes 32. At this point, the operator does not need to perform complex cutting or scraping operations on the entire sublimation tube 3; they only need to open the end cap of the sublimation tube 3 and use a hook to pull out each inner tube 32 in sequence to easily obtain the sublimation products deposited in different inner tubes 32.
[0083] For example, refer to Figure 5 As shown, in this embodiment, there are 5 deposition zones 31 and 5 inner tubes 32. Of course, this application is not limited to this; in other embodiments, there may be 2, 3, or 4 deposition zones 31 and inner tubes 32, etc., all of which are within the scope of protection of this application.
[0084] This design avoids the problem in traditional devices where products directly sublimate onto the tube wall, making them difficult to scrape off or even requiring destructive disassembly to remove. Secondly, the inner tube 32 can serve as an independent container for subsequent weighing, packaging, or analysis, reducing material transfer steps and mitigating the risk of cross-contamination and product degradation from air exposure. Furthermore, for scenarios requiring continuous purification of different samples, only a clean set of inner tubes 32 needs to be replaced, improving work efficiency. This structure has significant practical value for high-purity materials (such as semiconductor precursors) that require operation in an anhydrous and oxygen-free environment.
[0085] Preferably, in order to capture any low-condensation-point impurities that may remain in the exhaust gas and reduce the pollution or impact on vacuum devices such as vacuum pumps that may be caused after entering the vacuum system 6, refer to Figure 1 As shown, the sublimation apparatus of this invention may further include a cooling device 4. The cooling device 4 is disposed on the connecting pipeline between the outlet end of the sublimation tube 3 and the vacuum system 6. In a specific embodiment, the cooling device 4 includes a cooling sleeve 41 and a cooler 42 connected thereto, the cooling sleeve 41 being fitted over the outer wall of the downstream sublimation zone 31.
[0086] For example, in the process of purifying hafnium tetrachloride, some chloride impurities with low sublimation points may exist, which cannot be completely sublimated even at the set temperature of 0°C in the last sublimation zone 31. In this case, the refrigeration unit is turned on, lowering the temperature inside the cooling sleeve 41 to -20°C or lower, allowing these low-sublimation-point impurities to sublimate on the corresponding wall of the cooling sleeve 41. Since the cooling sleeve 41 is located after all the staged sublimation zones 31, its function is equivalent to a tail gas trap.
[0087] By adding this cooling device 4, it is possible to further collect the low condensation point components in the sublimation product, which helps to improve the purity of the target product (reduce the mixing of low condensation point impurities) and also helps to protect the vacuum system 6 from the influence of condensable gases.
[0088] To provide sufficient flexibility and shock absorption at the connection points to accommodate the installation and removal of the device within the limited space of the glove box, refer to... Figure 1 As shown, this utility model uses a flexible hose 7 as the pipeline connecting the vacuum system 6 and the outlet end of the deposition tube 3.
[0089] For example, when assembling the entire sublimation apparatus, the outlet end of the deposition tube 3 is connected to one end of a stainless steel corrugated flexible tube 7 via a KF connector. The other end of the flexible tube 7 is connected to the vacuum system 6. Compared to traditional rigid glass or plastic tubing, the flexible tube 7 can withstand a certain degree of bending and torsion. Its orifice diameter is the same as the deposition tube, preventing the Venturi effect and ensuring a stable vacuum. It also facilitates tubing connections within the confined glove box, helping to reduce stress concentration and the risk of glass component damage caused by rigid connections. The flexible tube 7 can be either metal or plastic.
[0090] Meanwhile, the flexible hose 7 can isolate the mechanical vibration generated during the operation of the vacuum pump to a certain extent, reducing the amplitude of vibration transmitted to the quartz sublimation column 1 and the sublimation tube 3, thereby improving the stability and safety of the entire device during long-term operation. Especially in high-temperature sublimation processes that require continuous operation for a long time (such as 7 or 8 hours or more), this vibration isolation and flexible connection design plays a positive role in reducing the risk of device breakage due to fatigue.
[0091] The purification effect of the sublimation device of this utility model is further illustrated by specific embodiments below, but this utility model is not limited to these embodiments.
[0092] Example 1: Purification of hafnium tetrachloride.
[0093] Construct the sublimation apparatus according to the above structure and place it in a low-water, low-oxygen glove box. Add 500g of crude hafnium tetrachloride to the sublimation column, and place a weighted pellet on top of the crude product. Place the inner tubes into the sublimation tubes in sequence to complete the apparatus.
[0094] Turn on the vacuum system and set the vacuum to 0.5 kPa. Turn on the gas mass flow controller 51 to control the carrier gas (nitrogen) flow rate to 500 mL / min. Turn on the heating of the first to fourth sublimation zones and the cooling of the fifth sublimation zone, and set the temperatures of the first to fifth sublimation zones to 100℃, 80℃, 60℃, 40℃, and 0℃, respectively.
[0095] After the temperature stabilizes, turn on the sublimation column for heating, and control the temperature at around 230℃. The crude product continues to sublimate under the influence of heat, carrier gas, and vacuum. Substances with lower sublimation points tend to sublimate in the 5th sublimation zone, the target product tends to sublimate in the 2nd to 4th sublimation zones, and substances with higher sublimation points tend to sublimate in the 1st sublimation zone.
[0096] Sublimation ended after 4 hours, and heating, cooling, and vacuum were turned off. The apparatus was disassembled, and the inner tube was pulled out using a hook. A total of 325g of product was collected from the second to the fourth sublimation zone. Testing showed that the hafnium tetrachloride product had a purity of 99.9999%.
[0097] This process would take approximately 7 hours in a sublimation apparatus without carrier gas, saving 3 hours.
[0098] Example 2: Purification of indium trichloride.
[0099] The experimental procedure was the same as in Example 1, except that: the vacuum was set to 0.1 kPa, the carrier gas (argon) flow rate was 1000 mL / min, the temperatures of sublimation zones 1-5 were set to 230℃, 150℃, 100℃, 80℃, and 10℃, and the sublimation column heating temperature was controlled at approximately 380℃. The experiment ended after 7 hours, and a total of 372 g of product was collected from zones 2 to 4. Testing showed that the purity of indium trichloride was 99.999%.
[0100] This operation would take approximately 12 hours in a sublimation apparatus without carrier gas, saving 5 hours.
[0101] Example 3: Purification of molybdenum pentachloride.
[0102] The experimental procedure was the same as in Example 1, except that: the vacuum was set to 0.1 kPa, the carrier gas (nitrogen) flow rate was 300 mL / min, and the temperatures of sublimation zones 1-5 were set to 90℃, 70℃, 50℃, 30℃, and 0℃, respectively. The heating temperature of the sublimation column was controlled at approximately 175℃ (because molybdenum pentachloride decomposes above 180℃). The experiment ended after 5 hours, and a total of 280 g of product was collected from zones 2 to 4. Testing showed that the purity of the molybdenum pentachloride product was 99.9995%.
[0103] This operation would take approximately 14 hours in a sublimation apparatus without carrier gas, saving 9 hours.
[0104] This embodiment demonstrates the application of this invention in processing easily decomposed substances at high temperatures: by using carrier gas-assisted sublimation, a relatively considerable sublimation rate and yield can still be obtained even at temperatures below the decomposition temperature.
[0105] The above description is merely a preferred embodiment of the present utility model and is not intended to limit the present utility model. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present utility model should be included within the protection scope of the present utility model.
[0106] It should be noted that the structures and working principles of the resistance heating wire, heating jacket and thermocouple, which are not described in detail in this application, can all adopt existing solutions in the prior art, which can be understood and accepted by those skilled in the art, and therefore will not be described in detail.
[0107] In the description of the embodiments of this utility model, it should be understood that the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", etc., indicate the orientation or positional relationship based on the orientation or positional relationship shown in the drawings, or the orientation or positional relationship commonly used when the product is in use, or the orientation or positional relationship commonly understood by those skilled in the art. They are only used to facilitate the description of this utility model and simplify the description, and are not intended to indicate or imply that the device or component referred to must have a specific orientation, or be constructed and operated in a specific orientation. Therefore, they should not be construed as limitations on this utility model.
[0108] In the description of the embodiments of this utility model, it should also be noted that, unless otherwise explicitly specified and limited, the terms "set," "install," "connect," and "link" should be interpreted broadly. For example, they can refer to a fixed connection, a detachable connection, or an integral connection; they can refer to a direct connection or an indirect connection through an intermediate medium; and they can refer to the internal connection of two components. Those skilled in the art can understand the specific meaning of the above terms in this utility model based on the specific circumstances.
[0109] In the description of the embodiments of this utility model, it should also be noted that the terms "first" and "second" used herein do not specifically refer to any order or sequence, nor are they intended to limit this case; they are merely used to distinguish components or operations described using the same technical terms.
[0110] It will be apparent to those skilled in the art that this disclosure is not limited to the details of the exemplary embodiments described above, and that this disclosure can be implemented in other specific forms without departing from its spirit or essential characteristics. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of this disclosure is defined by the appended claims rather than the foregoing description. Thus, all variations falling within the meaning and scope of equivalents of the claims are intended to be included within this disclosure. No reference numerals in the claims should be construed as limiting the scope of the claims.
[0111] Furthermore, it should be understood that although this specification describes embodiments, not every embodiment contains only one independent technical solution. This narrative style is merely for clarity. Those skilled in the art should consider the specification as a whole, and the technical solutions in each embodiment can also be appropriately combined to form other embodiments that can be understood by those skilled in the art.
Claims
1. A sublimation apparatus, characterized in that, The sublimation apparatus includes: Sublimation column (1), the interior of the sublimation column (1) is provided with a cavity (11) for containing the crude product to be sublimated, the sublimation column (1) includes an outlet (12) at the top and an inlet (13) at the bottom, the outlet (12) and the inlet (13) are both connected to the cavity (11); The first heating element (21) is arranged around the outer wall of the sublimation column (1); The first temperature sensing element (22) is disposed on the outer wall of the sublimation column (1) and is in thermal contact with the sublimation column (1); A sublimation tube (3) is provided with its inlet end connected to the outlet (12) of the sublimation column (1). The sublimation tube (3) is provided with multiple sublimation zones (31) in sequence along the gas flow direction. At least one of the sublimation zones (31) is surrounded by a second heating element (23) on its outer wall. Along the gas flow direction, any sublimation zone (31) with the second heating element (23) is located upstream of the sublimation zone (31) without the second heating element (23). A second temperature measuring element (24) is provided on the outer wall of each sublimation zone (31) surrounded by the second heating element (23). The set temperature of the multiple sublimation zones (31) gradually decreases along the gas flow direction. The carrier gas introduction assembly (5) is connected to the air inlet (13) of the sublimation column (1); The vacuum system (6) is connected to the outlet end of the sublimation tube (3).
2. The sublimation apparatus according to claim 1, characterized in that, The sublimation column (1) includes a sublimation section (14) and a carrier gas introduction section (15). The sublimation section (14) is connected to the condensation tube (3), and the carrier gas introduction section (15) is connected to the carrier gas introduction assembly (5). The air inlet (13) is disposed on the carrier gas introduction section (15), and the carrier gas introduction section (15) and the sublimation section (14) are not collinear.
3. The sublimation apparatus according to claim 2, characterized in that, The sublimation section (14) is a vertical pipe section, and the carrier gas introduction section (15) is a curved pipe section (151). One end of the curved pipe section (151) is connected to the bottom of the vertical pipe section, and the other end of the curved pipe section (151) is provided with the air inlet (13).
4. The sublimation apparatus according to claim 2, characterized in that, The sublimation section (14) is a vertical pipe section, and the carrier gas introduction section (15) is a horizontal straight pipe section (152). The bottom of the horizontal straight pipe section (152) is perpendicular to the bottom of the vertical pipe section, and the air inlet (13) is provided at the free end of the horizontal straight pipe section (152).
5. The sublimation apparatus according to claim 2, characterized in that, The sublimation section (14) is a vertical pipe section, and the carrier gas introduction section (15) includes a curved pipe section (151) and a horizontal straight pipe section (152). One end of the curved pipe section (151) is connected to the bottom of the vertical pipe section, and the other end of the curved pipe section (151) is connected to one end of the horizontal straight pipe section (152). The air inlet (13) is provided at the free end of the horizontal straight pipe section (152).
6. The sublimation apparatus according to claim 1, characterized in that, The sublimation column (1) is also equipped with a pressure component (16).
7. The sublimation apparatus according to claim 1, characterized in that, The interior of the deposition tube (3) is provided with a plurality of detachable inner tubes (32), the number of which is equal to the number of deposition zones (31), and each inner tube (32) is located inside a corresponding deposition zone (31).
8. The sublimation apparatus according to claim 1, characterized in that, The sublimation apparatus also includes a cooling device (4), which is located between the outlet end of the sublimation tube (3) and the vacuum system (6).
9. The sublimation apparatus according to claim 8, characterized in that, The cooling device (4) includes a cooling sleeve (41) and a cooler (42) connected to the cooling sleeve (41). The cooling sleeve (41) is fitted onto the outer wall of the downstream sublimation zone (31).
10. The sublimation apparatus according to claim 1, characterized in that, The vacuum system (6) is connected to the sublimation tube (3) via a hose (7); and / or, A sealing structure (33) is provided between the sublimation tube (3) and the sublimation column (1) and / or between the sublimation tube (3) and the vacuum system (6).