A directional ultrasonic intensified intermittent rectification device and intermittent rectification method

Abstract

This invention relates to the field of batch distillation technology, specifically to a directional ultrasound-enhanced batch distillation apparatus and method. The apparatus includes a distillation vessel body, an ultrasonic generator, and an ultrasonic vibration system mounted on the outer wall of the distillation vessel body. The ultrasonic vibration system includes at least one set of transducers, each set comprising multiple transducers uniformly distributed along the axial direction of the distillation vessel body. Each transducer is electrically connected to the ultrasonic generator, and a parabolic focusing hood is connected to the front end of each transducer. The opening of each parabolic focusing hood faces the outer wall of the distillation vessel body. The ratio of the focal length of each parabolic focusing hood to the radius of the distillation vessel body is 0.5-0.75. This invention achieves directional focusing of ultrasonic energy by controlling the ratio of the focusing hood's focal length to the inner diameter of the distillation vessel. Combined with a multi-transducer array layout, it achieves a synergistic improvement in energy utilization, separation purity, and temperature uniformity.

Description

Technical Field

[0001] This invention relates to the field of batch distillation technology, specifically to a directional ultrasonic-enhanced batch distillation apparatus and a batch distillation method. Background Technology

[0002] Batch distillation is a core process for purifying electronic chemicals. Electronic chemicals require high purity (typically above 99.99%), and some are heat-sensitive (easily decomposed at high temperatures), such as high-purity organometallic compounds for semiconductors. Other electronic chemicals are prone to foaming; for example, recovered solutions of electronic-grade solvents, containing surfactants and other impurities, easily generate bubbles during distillation, affecting the efficiency and purity of the product. Currently, most medium-to-large-sized distillation vessels (50-500L) use mechanical stirring for mixing, which has the following technical drawbacks: 1. Uneven heat transfer: Mechanical stirring can easily create "heating dead zones". Local high temperatures can cause the decomposition of heat-sensitive electronic chemicals, while local low temperatures can cause the residue of light components, affecting the separation purity. 2. Interface disturbance: High-speed rotation of the agitator can easily cause violent fluctuations at the gas-liquid interface. Foam carries heavy components into the distillation column, resulting in a decrease in the purity of the light component fraction at the top of the column. Moreover, mechanical defoaming requires the use of an antifoaming net, which has limited effectiveness. 3. Material contamination: The mechanical stirring paddle comes into direct contact with the material, which can easily generate wear debris, contaminating the electronic precursor and failing to meet high purity requirements; 4. Limitations: The volume of the 50-500L vessel is relatively large. The energy attenuation of the traditional single transducer is severe, and the ultrasonic energy does not propagate in a directional manner. Some energy leakage causes noise pollution. At the same time, it is difficult to achieve uniform mixing throughout the vessel, which limits the application of ultrasound in medium and large vessels.

[0003] Chinese patent CN108499147A discloses a parallel distributed ultrasonic bubble cap tower device, but it only addresses mass transfer enhancement in the trays and does not cover directional ultrasonic transmission and sound insulation within the distillation vessel. Chinese patent CN221309583U discloses an ultrasonic generator arranged in the bottom region of a distillation column. Using ultrasonic equipment to assist in heating the bottom liquid of the distillation column, and utilizing the cavitation effect of ultrasound to atomize the bottom liquid, aims to reduce steam consumption during the distillation separation process. Its core functions are scale prevention rather than mixing enhancement, protection of heat-sensitive materials, and noise control.

[0004] Therefore, there is an urgent need to develop a directional ultrasonic distillation technology suitable for 50-500L scale, which takes into account mixing uniformity, interface stability and operational safety, to meet the separation needs of electronic chemicals. Summary of the Invention

[0005] Therefore, the present invention provides a directional ultrasound-enhanced distillation apparatus and a batch distillation method. Through a directional ultrasound structure and a multi-transducer array layout, uniform mixing and stable gas-liquid interface are achieved in the vessel, thereby improving separation efficiency and purity while avoiding material decomposition.

[0006] To address the aforementioned technical problems, the present invention provides the following technical solution: In a first aspect, this application provides an ultrasonically enhanced intermittent distillation apparatus, comprising: Distillation kettle body; An ultrasonic generator is used to generate high-frequency electrical signals; An ultrasonic vibration system is installed on the outer wall of the distillation vessel body. The ultrasonic vibration system includes at least one set of transducers. Each set of transducers includes multiple transducers evenly distributed along the axial direction of the distillation vessel body. Each transducer is electrically connected to the ultrasonic generator. A parabolic focusing hood is connected to the front end of each transducer. The opening of each parabolic focusing hood faces the outer wall of the distillation vessel body. The ratio of the focal length of each parabolic focusing hood to the radius of the distillation vessel body is 0.5-0.75:1.

[0007] Furthermore, in the batch distillation unit, When the volume of the distillation vessel body is greater than or equal to 50L and less than or equal to 200L, the number of transducer groups is 1-3, and the number of transducers in each group is 4-6. When the volume of the distillation vessel body is greater than 200L and less than or equal to 500L, the number of transducer groups is 2-5, and the number of transducers is 6-10.

[0008] Furthermore, at least one axially extending mounting groove is provided on the outer wall of the distillation vessel body, and all the ultrasonic transducers located in the same axial column are installed in the same mounting groove.

[0009] Furthermore, a damping pad is also installed between each transducer and the mounting groove.

[0010] Furthermore, the outer wall of the distillation vessel body is also provided with a heating jacket, which covers the outer wall of the distillation vessel body, and the heating jacket has an opening for clearance, through which the ultrasonic vibration system is installed on the outer wall of the distillation vessel body.

[0011] Furthermore, the intermittent distillation apparatus also includes a sound insulation protection system, which includes a sound insulation cover and a sound-absorbing layer. The sound insulation cover is located outside the distillation vessel body and houses the ultrasonic vibration system inside it. A sound-absorbing layer is provided on the inner wall of the sound insulation cover.

[0012] Furthermore, the batch distillation apparatus also includes an interface monitoring system for monitoring the gas-liquid interface height and foam height; and / or, The control system is used to adjust the ultrasonic frequency and total power density based on the ratio of the interface fluctuation amplitude to the inner diameter of the vessel and the foam height.

[0013] Secondly, this application also provides a method for batch distillation of electronic chemicals using any of the above-mentioned apparatus, comprising the following steps: S1. Add the raw material containing electronic chemicals into the distillation vessel body, controlling the amount added so that the initial liquid level is 50-70% of the volume of the distillation vessel body; S2. Under distillation operating pressure, the temperature is raised to 2-10°C below the bubble point temperature of the electronic chemical. S3. Start the ultrasonic generator and heat the mixture to above the bubble point temperature of the electronic chemical to begin distillation; S4. Detect the concentration of light components in the reactor liquid. When the concentration of the electronic chemicals in the reactor liquid drops to a set threshold, stop heating and ultrasonic treatment, and end the distillation.

[0014] Furthermore, the distillation process in step S3 includes the following process control procedures: Monitor the ratio of foam height and interface fluctuation amplitude within the distillation vessel to its inner diameter; When the foam height is less than or equal to the first preset threshold and the ratio of the interface fluctuation amplitude to the inner diameter of the vessel is less than or equal to the second preset threshold, the ultrasonic frequency is adjusted to the first preset range and the total power density is adjusted to the second preset range. When the foam height is greater than the first preset threshold and the ratio of the interface fluctuation amplitude to the inner diameter of the vessel is less than or equal to the second preset threshold, the ultrasonic frequency is adjusted to the third preset range and the total power density is adjusted to the fourth preset range. When the foam height is less than or equal to the first preset threshold and the ratio of the interface fluctuation amplitude to the inner diameter of the vessel is greater than the second preset threshold, the ultrasonic frequency is adjusted to the fifth preset range and the total power density is adjusted to the sixth preset range. When the foam height is greater than the first preset threshold and the ratio of the interface fluctuation amplitude to the inner diameter of the vessel is greater than the second preset threshold, the ultrasonic frequency is adjusted to the seventh preset range and the total power density is adjusted to the eighth preset range.

[0015] Furthermore, the first preset threshold is less than or equal to 5cm, and the second preset threshold is less than or equal to 10%. The first preset range is 40-60kHz, and the second preset range is 0.10-0.15W / cm². 2 ; The third preset range is greater than 80Hz and less than or equal to 100KHz, and the fourth preset range is greater than 0.15W / cm² and less than or equal to 0.20 / cm². The fifth preset range is greater than or equal to 30kHz and less than 40kHz; the sixth preset range is greater than or equal to 0.05W / cm² and less than 0.1W / cm². The seventh preset range is greater than 60Hz and less than or equal to 80kHz, and the eighth preset range is 0.10-0.15W / cm². Beneficial effects

[0016] 1. Directional Conveying Enhances Mixing Uniformity: By employing a parabolic focusing hood and controlling the ratio of the focusing hood's focal length to the inner diameter of the distillation vessel, directional focusing of ultrasonic energy is achieved. Combined with a multi-transducer array layout, this solves the problems of ultrasonic energy attenuation and leakage in 50-500L vessels, increasing ultrasonic energy utilization by over 40%. The entire vessel exhibits microscopically uniform mixing of materials, with a temperature field deviation ≤ ±0.5℃, preventing localized high-temperature decomposition of heat-sensitive electronic chemicals.

[0017] 2. Precise interface control and separation efficiency optimization: Directional ultrasonic energy is precisely applied to the gas-liquid interface region. Combined with intelligent adjustment of frequency and power, the gas-liquid interface state is stabilized, the amount of foam entrainment is reduced, and the purity of light component fractions is increased to over 99.99%. Cavitation effect enhances heat and mass transfer and improves energy utilization efficiency.

[0018] 3. Non-contact and pollution-free: Ultrasonic waves transmit energy directionally through the vessel wall, eliminating the need for a stirring paddle and avoiding pollution caused by contact between materials and mechanical parts, thus meeting the purification standards for electronic-grade materials.

[0019] 4. Wide adaptability: By adjusting the number of transducers, focal length and parameters of the focusing hood, it can be adapted to different scale vessels of 50-500L, and is compatible with the separation needs of various foaming and heat-sensitive electronic chemicals. Attached Figure Description

[0020] Figure 1 This is a schematic diagram of the ultrasonic-enhanced intermittent distillation apparatus of this application.

[0021] Figure 2 This is a top view of the distillation vessel body in Example 1.

[0022] Figure 3 This is a schematic diagram of the ultrasonic system and the sound insulation system in the ultrasonic-enhanced intermittent distillation apparatus of this application.

[0023] Figure 4 This is a top view of the distillation vessel body in Example 2.

[0024] Figure label: 1-Distillation column body, 2-Distillation column, 3-Ultrasonic generator, 4-Top condenser, 5-Reflux pump, 6-Reflux tank, 7-Collection tank, 11-Mounting groove, 12-Heating jacket, 13-Damping shock absorber, 14-Sound absorbing layer, 15-Sound insulation cover, 16-Transducer, 17-Parabolic focusing cover. Detailed Implementation

[0025] The present invention will now be described in detail with reference to embodiments. The principles and features of the present invention are described below with reference to embodiments. It should be noted that, unless otherwise specified, the embodiments and features described in these embodiments can be combined with each other. The embodiments given are only for explaining the present invention and are not intended to limit the scope of the present invention.

[0026] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.

[0027] Unless otherwise stated or in case of contradiction, the terms or phrases used herein shall have the following meanings: As used herein, the term "and / or" includes any and all combinations of one or more of the related listed items.

[0028] In this application, terms such as "preferred," "better," "more suitable," and "ideal" are merely used to describe implementation methods or embodiments that achieve better results, and should be understood not to limit the scope of protection of this application.

[0029] In this application, terms such as "further," "even further," and "particularly" are used to describe purposes and indicate differences in content, but should not be construed as limiting the scope of protection of this application.

[0030] In this invention, the terms "first aspect," "second aspect," "third aspect," and "fourth aspect," etc., are used for descriptive purposes only and should not be construed as indicating or implying relative importance or quantity, nor should they be construed as implicitly indicating the importance or quantity of the indicated technical features. Moreover, "first," "second," "third," and "fourth," etc., serve only as a non-exhaustive enumeration and should be understood not to constitute a closed limitation on quantity.

[0031] In this application, the technical features described in an open-ended manner include both closed technical solutions consisting of the listed features and open technical solutions that include the listed features.

[0032] In this application, numerical intervals (i.e., numerical ranges) are involved. Unless otherwise specified, the optional numerical distribution within the aforementioned numerical interval is considered continuous and includes the two endpoints of the numerical range (i.e., the minimum and maximum values), as well as every value between these two endpoints. For example, a range of t of 1-10 means that t is greater than or equal to 1 and less than or equal to 10. Furthermore, when multiple ranges are provided to describe features or characteristics, these ranges can be merged. In other words, unless otherwise specified, the ranges disclosed herein should be understood to include any and all subranges included therein.

[0033] In this application, total power density refers to the ultrasonic power per unit radiation area, and its unit is W / cm².

[0034] In this application, the interface fluctuation amplitude refers to the range of vertical oscillation of the gas-liquid interface (or liquid level) during distillation. Unlike continuous distillation, the liquid level in batch distillation continuously decreases; therefore, the fluctuation amplitude here refers to the intensity of the instantaneous liquid level's oscillation around its average position, rather than the absolute level. Methods for detecting the interface fluctuation amplitude are existing technologies and will not be elaborated here. For example, a laser level sensor can be used to monitor changes in the liquid level in real time, and then the interface fluctuation amplitude can be calculated using a PLC or DCS system. Alternatively, changes in the liquid level can be observed manually, and then the interface fluctuation amplitude can be calculated.

[0035] In ultrasonic-enhanced distillation, a specific matching relationship exists between the focal length of the focusing hood of the ultrasonic vibration system and the inner diameter of the distillation vessel. In traditional designs, the selection of the focal length typically only considers whether the focusing position falls within the target area (such as a tray or vessel wall), without taking into account the comprehensive influence of the ratio of this parameter to the vessel's geometric dimensions on the sound field distribution, spatial distribution of thermal effects, and fluid flow patterns. When the ratio of the focal length to the vessel radius is inappropriate, the following problems may occur: (1) Low energy utilization: If the focal length is too short, the ultrasonic energy will be concentrated in a small area near the vessel wall. A large amount of energy will be reflected and absorbed by the vessel wall and will not be able to act on the material inside the vessel. If the focal length is too long, the sound wave will be over-diverged before reaching the center of the vessel, and the sound intensity at the focal point will be insufficient, resulting in a weak cavitation effect.

[0036] (2) Limited separation purity: Uneven sound field distribution leads to inconsistent mass transfer enhancement. Some areas are "over-enhanced" and cause fog entrainment, while some areas are "under-enhanced" and result in low mass transfer efficiency. Overall separation efficiency improvement is limited.

[0037] (3) Poor temperature uniformity: The local accumulation of ultrasonic mechanical energy converted into heat energy can easily form "hot spots" in the focal area when the focal length and the geometry of the vessel do not match, which can destroy the temperature gradient required for distillation and aggravate the decomposition reaction of heat-sensitive components.

[0038] Through extensive theoretical analysis and experimental research, this application reveals for the first time the influence of the ratio of the focal length of the focusing hood to the inner diameter of the vessel on the overall performance of ultrasonic distillation, and proposes an optimized range of the ratio of focal length to inner diameter of the vessel, thereby achieving a synergistic improvement in energy utilization, separation purity, and temperature uniformity.

[0039] Firstly, this application provides an ultrasonically enhanced intermittent distillation apparatus. For an example, please refer to... Figures 1 to 3 As shown, an ultrasonically enhanced batch distillation apparatus for purifying electronic chemicals includes: Distillation kettle body 1; Ultrasonic generator 3 is used to generate high-frequency electrical signals; An ultrasonic vibration system is installed on the outer wall of the distillation vessel body 1. The ultrasonic vibration system includes at least one set of transducers. Each set of transducers includes multiple transducers 16 evenly distributed circumferentially along the same cross-section of the distillation vessel body. Each transducer is electrically connected to the ultrasonic generator. A parabolic focusing hood 17 is connected to the front end of each transducer. The opening of each parabolic focusing hood faces the outer wall of the distillation vessel body 1. The ratio of the focal length of each parabolic focusing hood to the inner diameter of the distillation vessel body is 0.5-0.75:1.

[0040] Understandably, the distillation vessel body of this application has a discharge port at the bottom for discharging residual liquid from the bottom. A feed port is located at the top for feeding raw materials into the distillation vessel. A vapor outlet is also provided at the top, through which the distillation vessel body is connected to the distillation column to complete the distillation separation.

[0041] Furthermore, the batch distillation apparatus also includes a distillation column 2, a condenser 4, a reflux tank 6, and a product collection tank 7 connected in sequence. The distillation column 2 is connected to the top of the distillation vessel body, the top condenser is connected to the reflux tank 6, the reflux tank 6 is connected to the distillation column 2 via a reflux pump 5, and the reflux tank 6 is connected to the product collection tank 7 via a pipeline. In some embodiments, the distillation apparatus also includes a vacuum system connected to the product collection tank 7.

[0042] In some embodiments, the body of the distillation vessel is made of high-purity stainless steel or quartz glass.

[0043] It should be noted that the "transverse interface" in the context of uniform circumferential distribution along the same cross-section of the distillation vessel body refers to a plane perpendicular to the axial direction of the distillation vessel body, that is, a plane parallel to the liquid surface. Uniform circumferential distribution means evenly spaced along the outer circumference of the distillation vessel body.

[0044] In some embodiments of this application, the ultrasonic system includes at least two sets of transducers along the height direction of the distillation vessel body, wherein each set of transducers is arranged at equal intervals along the height direction of the outer wall of the distillation vessel. In some embodiments, the interval is 0.3-0.6 times the inner diameter.

[0045] In some embodiments of this application, the transducers are arranged in multiple layers, wherein several transducers uniformly distributed circumferentially along the same cross-section of the distillation vessel body constitute a group. Several groups of transducers are arranged along the height direction of the outer wall of the distillation vessel.

[0046] Understandably, considering operational safety, mass transfer efficiency, separation effect, and operational stability, the liquid content of the distillation vessel is usually controlled at 50-70% of the vessel's volume. Therefore, to achieve better ultrasonic enhancement, the internal height of the distillation vessel corresponding to the installation position of the uppermost transducer should not exceed the liquid level height corresponding to 50% of the distillation vessel's volume.

[0047] It should be noted that the volume of the distillation vessel body refers to the maximum liquid volume that the distillation vessel body can hold.

[0048] In some embodiments, at least one axially extending mounting groove is formed on the outer wall of the distillation vessel body, and all transducers located in the same axial column of the plurality of ultrasonic transducers are mounted in the same mounting groove. To ensure focused ultrasonic energy emission, the inner wall of the mounting groove is polished.

[0049] It should be noted that the "axial direction" mentioned above refers to the height direction of the distillation vessel body.

[0050] In some embodiments of this application, in the batch distillation apparatus, when the volume of the distillation vessel body is greater than or equal to 50L and less than or equal to 200L, the number of transducer groups is 1-3, and the number of transducers in each group is 4-6. When the volume of the distillation vessel body is greater than 200L and less than or equal to 500L, the number of transducer groups is 2-5, and the number of transducers is 6-10.

[0051] In some embodiments of this application, the angle between the central axis of the transducer and the axis of the distillation vessel body is 45°-135°.

[0052] In some embodiments of this application, the total power density of the ultrasonic vibration system is 0.01-0.2 W / cm². 2 .

[0053] In some embodiments of this application, a damping pad is further installed between each transducer 16 and the mounting groove 11. In some embodiments, the damping pad has a thickness of 5-8 mm and is made of nitrile rubber.

[0054] In some embodiments of this application, the transducer end face is tightly fitted to the inner wall of the mounting groove 11 with thermally conductive silicone to ensure efficient ultrasonic wave transmission.

[0055] In some embodiments of this application, a heating jacket 12 is further provided on the outer wall of the distillation vessel body 1. The heating jacket 12 covers the outer wall of the distillation vessel body 1, and the heating jacket 12 has an avoidance opening through which the ultrasonic vibration system is installed on the outer wall of the distillation vessel body. Specifically, the heating jacket 12 can be disposed between the mounting grooves 11 to avoid the installation area of ​​the transducer 16. The heating jacket 12 can be heated by heat transfer oil or steam, with a temperature control accuracy of ±0.5℃, to avoid localized high temperatures.

[0056] In some embodiments of this application, a sound insulation and protection system is also included. This system comprises a soundproof cover 15 and a sound-absorbing layer 14. The soundproof cover 15 is located outside the distillation vessel body and houses the ultrasonic vibration system within it. The sound-absorbing layer 14 is provided on the inner wall of the soundproof cover 15. Through a triple design of "sound absorption + sound insulation + vibration reduction," the sound insulation and protection system controls the external noise during ultrasonic operation to below 85 dB(A), far below the national industrial enterprise noise hygiene standard (≤90 dB(A)), effectively reducing hearing harm to operators and improving operational safety.

[0057] In some embodiments, the soundproof cover 15 has a thickness of 5-10 mm, and can be made of cold-rolled steel sheet, for example. The distance between the soundproof cover and the outer wall of the distillation vessel body is 10-15 cm.

[0058] In some embodiments, the sound-absorbing layer 14 has a thickness of 20-30 mm, is made of glass wool or polyester fiber, and has a perforated surface. In some embodiments, for frequencies of 20-100 kHz, the sound absorption coefficient of the sound-absorbing layer is ≥0.8.

[0059] In some embodiments, for ease of maintenance, the soundproof cover 15 is also provided with an inspection door, and a sealing strip is provided at the connection between the door and the cover to ensure the integrity of the sound insulation.

[0060] In some embodiments of this application, it also includes an interface monitoring system for monitoring the gas-liquid interface height and foam height; and / or a control system for adjusting the ultrasonic frequency and total power density according to the gas-liquid interface height and foam height.

[0061] In some embodiments of this application, the interface monitoring system includes a laser level sensor installed on the side wall of the vessel for real-time monitoring of the gas-liquid interface height and a foam sensor for monitoring the foam height.

[0062] In some embodiments of this application, the control system is electrically connected to the ultrasonic generator, the heating jacket, and the interface monitoring system, respectively.

[0063] Secondly, this application also provides a method for batch distillation of electronic chemicals using the above-mentioned apparatus, comprising the following steps: S1. Add the raw material containing electronic chemicals into the distillation vessel body, controlling the amount added so that the initial liquid level is 50-70% of the volume of the distillation vessel body; S2. Under distillation operating pressure, the temperature is raised to 2-10°C below the bubble point temperature of the electronic chemical. S3. Start the ultrasonic generator and heat the mixture to above the bubble point temperature of the electronic chemical to begin distillation; S4. Detect the concentration of the electronic chemicals in the reactor liquid. When the concentration of the electronic chemicals in the reactor liquid drops to a set threshold, stop heating and ultrasonic treatment, and end the distillation.

[0064] In some embodiments, preferably, the distillation temperature in step S3 is controlled to be 0-5°C above the bubble point temperature.

[0065] In some implementations, the threshold in step S4 is less than or equal to 1 wt%.

[0066] It should be noted that in the above distillation method, "the electronic chemical" refers to the target compound to be purified by distillation. In some embodiments, the electronic chemical is an electronic precursor or an electronic-grade solvent, such as trimethylgallium or electronic-grade isopropanol. In some embodiments, the raw material containing the electronic chemical is a trimethylgallium-containing raw material or an isopropanol-containing raw material, wherein the content of trimethylgallium is 80-85 wt%, and the content of isopropanol is less than or equal to 99%.

[0067] In some embodiments of this application, step S3 distillation includes the following process control procedures: Monitor the ratio of foam height and interface fluctuation amplitude within the distillation vessel to its inner diameter; When the foam height is less than or equal to the first preset threshold and the ratio of the interface fluctuation amplitude to the inner diameter of the vessel is less than or equal to the second preset threshold, the ultrasonic frequency is adjusted to the first preset range and the total power density is adjusted to the second preset range.

[0068] When the foam height is greater than the first preset threshold and the ratio of the interface fluctuation amplitude to the inner diameter of the vessel is less than or equal to the second preset threshold, the ultrasonic frequency is adjusted to the third preset range and the total power density is adjusted to the fourth preset range. When the foam height is less than or equal to the first preset threshold and the ratio of the interface fluctuation amplitude to the inner diameter of the vessel is greater than the second preset threshold, the ultrasonic frequency is adjusted to the fifth preset range and the total power density is adjusted to the sixth preset range. When the foam height is greater than the first preset threshold and the ratio of the interface fluctuation amplitude to the inner diameter of the vessel is greater than the second preset threshold, the ultrasonic frequency is adjusted to the seventh preset range and the total power density is adjusted to the eighth preset range.

[0069] In some embodiments of this application, the first preset threshold is less than or equal to 5cm, and the second preset threshold is less than or equal to 10%. The first preset range is 40-60kHz, and the second preset range is 0.10-0.15W / cm². 2 ; The third preset range is greater than 80Hz and less than or equal to 100KHz, and the fourth preset range is greater than 0.15W / cm² and less than or equal to 0.20 / cm². The fifth preset range is greater than or equal to 30kHz and less than 40kHz, and the sixth preset range is greater than or equal to 0.05W / cm² and less than 0.10W / cm².

[0070] The seventh preset range is greater than 60Hz and less than or equal to 80kHz, and the eighth preset range is 0.10-0.15W / cm².

[0071] In some embodiments of this application, during the distillation process in step S2, when the ratio of the interface fluctuation amplitude to the inner diameter of the vessel is less than or equal to 10% and the interface foam height is less than or equal to 5 cm, the ultrasonic frequency is 40-60 kHz and the total power density is 0.10-0.15 W / cm². When the ratio of the interface fluctuation amplitude to the inner diameter of the vessel is less than or equal to 10% and the interface foam height is greater than 5cm, the ultrasonic frequency is greater than 80Hz and less than or equal to 100kHz, and the total power density is greater than 0.15W / cm² and less than or equal to 0.20W / cm². When the ratio of the interface fluctuation amplitude to the inner diameter of the vessel is greater than 10% and the interface foam height is less than or equal to 5cm, the ultrasonic frequency is greater than or equal to 30kHz and less than 40KHz, and the total power density is greater than or equal to 0.05W / cm² and less than 0.10W / cm². When the foam height inside the distillation vessel is greater than 5 cm and the ratio of the interface fluctuation amplitude to the inner diameter of the vessel is greater than 10%, the ultrasonic frequency is greater than 60 Hz and less than or equal to 80 kHz, and the total power density is 0.10-0.15 W / cm². The beneficial effects of the ultrasonic-enhanced intermittent distillation apparatus and the method of distillation using the apparatus will be illustrated below through specific embodiments.

[0072] All raw materials and reagents used in this invention were purchased from mainstream manufacturers on the market. Those without specified manufacturers or concentrations are all analytical grade raw materials or reagents that are routinely available. There are no particular restrictions as long as they achieve the intended effect. The instruments and equipment used in this embodiment were all purchased from major manufacturers on the market. There are no particular limitations as long as they achieve the intended effect. Where specific techniques or conditions are not specified in this embodiment, they shall be performed in accordance with the techniques or conditions described in the literature in this field or according to the product instructions.

[0073] Example 1 This embodiment provides a 50L batch distillation apparatus, such as... Figures 1 to 3 As shown, it includes: The distillation vessel body 1 has a volume of 50L and an inner diameter of 15cm. The outer wall of the distillation vessel body has four mounting grooves 11 for installing transducers. The four mounting grooves are evenly distributed along the circumference of the distillation vessel body. A heating jacket 12 is also fitted on the outer wall of the distillation vessel body 1 between the mounting grooves for heating the distillation vessel body.

[0074] The top of the distillation vessel is connected to a distillation column 2. The top gas outlet of the distillation column 2 is connected to a top condenser 4. The top condenser 4 is connected to a reflux tank 6. The reflux tank 6 is connected to the distillation column 2 through a reflux pump 5. The reflux tank 6 is connected to a product collection tank 7 through a pipeline. The product collection tank 7 is connected to a vacuum system.

[0075] Ultrasonic generator 3 is used to generate high-frequency electrical signals.

[0076] Ultrasonic vibration systems, such as Figure 3 As shown, the apparatus includes three sets of transducers, which are arranged at equal intervals along the height of the outer wall of the distillation vessel, with a spacing of 8 cm. The height of the inner body of the distillation vessel corresponding to the installation position of the uppermost transducer is the liquid level height corresponding to 50% of the volume of the distillation vessel body. Each set of transducers includes four transducers 16 evenly distributed along the circumference of the distillation vessel body. Each transducer 16 is installed in a mounting groove 11. A damping and shock-absorbing pad 13 is installed between the transducer 16 and the mounting groove 11. A parabolic focusing hood 17 is connected to the front end of each transducer. The opening of the parabolic focusing hood 17 faces the outer wall of the distillation vessel body. The focal length of the parabolic focusing hood 17 is 8 cm. The damping and shock-absorbing pad is made of 6 mm nitrile rubber.

[0077] A sound insulation and protection system is provided, comprising a soundproof cover 15 and a sound-absorbing layer 14. The soundproof cover 15 is located outside the distillation vessel body and houses the transducer therein. The distance between the soundproof cover 15 and the outer wall of the distillation vessel body is 10 cm. A sound-absorbing layer 14 is provided on the inner wall of the soundproof cover 15. The soundproof cover 15 is made of 6 mm cold-rolled steel plate, and the sound-absorbing layer 14 is made of 25 mm glass wool. The surface of the sound-absorbing layer is protected by a perforated plate.

[0078] The interface monitoring system includes a laser level sensor and a foam sensor installed on the inner wall of the distillation vessel to monitor the gas-liquid interface height and foam height in real time.

[0079] The PLC control system is electrically connected to the ultrasonic generator, heating jacket, and interface monitoring system. Based on the feedback from the interface monitoring system, it calculates the ratio of interface fluctuation amplitude to the inner diameter of the vessel and adjusts the ultrasonic frequency and total power density.

[0080] This device is used for the purification of electronic-grade trimethylgallium (a thermosensitive electronic precursor).

[0081] During operation, 30L of raw material is added to the distillation vessel. The raw material contains 85% trimethylgallium by mass and includes oligomers such as diisopentyl ether, diethyl ether, tetrahydrofuran, gallium trichloride, gallium chloride, magnesium chloride, lithium chloride, dimethylgallium, and methylgallium dimer, as well as small amounts of unreacted Grignard reagents and methylation byproducts. The pressure is evacuated to 0.1 mbar, and the temperature is controlled to -30℃ (trimethylgallium bubble point -25.8℃). The ultrasonic generator is started, with a frequency set to 50kHz and a total power density of 0.12 W / cm² (radiation area is the contact area between the focusing hood and the vessel wall). The ultrasonic energy is transmitted to the distillation vessel body through the focusing hood for premixing for 30 minutes. Then, the temperature is controlled to -23℃ for vacuum distillation.

[0082] During the distillation process, when the foam height inside the distillation vessel is detected to be greater than 5 cm and the ratio of the interface fluctuation amplitude to the inner diameter of the vessel is less than 10%, the control system will automatically adjust the ultrasonic frequency to 85 kHz and the total power density to 0.17 W / cm², and accurately break the bubbles through the directional cavitation effect.

[0083] When the ratio of the interface fluctuation amplitude to the inner diameter of the vessel is greater than 10% and the interface foam height is less than or equal to 5cm, the control system will automatically adjust the frequency to 35KHz and the total power density to 0.07W / cm².

[0084] When the interface fluctuation amplitude is detected to be greater than 10% of the inner diameter of the vessel and the interface foam height is greater than 5cm, the control system will automatically adjust the frequency to 65KHz and the total power density to 0.12W / cm².

[0085] When the interface fluctuation amplitude is detected to be less than or equal to 10% of the inner diameter of the vessel and the interface foam height is less than or equal to 5cm, the control system will automatically adjust the control frequency to 50KHz and the total power density to 0.12W / cm².

[0086] When the concentration of trimethylgallium in the still solution drops to 1%, distillation is stopped, and the heavy components at the bottom of the still are removed by cooling. The purified trimethylgallium is collected in a product collection tank.

[0087] Example 2 This embodiment provides a 500L batch distillation apparatus, which differs from Embodiment 1 in the structure of the distillation vessel body. Specifically, see [link to embodiment]. Figure 1 , Figure 3 and Figure 4 .

[0088] The distillation vessel body 1 has a volume of 500L and an inner diameter of 40cm. The outer wall of the distillation vessel body 1 has 10 mounting grooves 11 for installing transducers (e.g., ...). Figure 4 As shown, 10 mounting grooves 11 are evenly distributed along the circumference of the distillation vessel body; a heating jacket 12 is also fitted on the outer wall of the distillation vessel body between the mounting grooves for heating the distillation vessel body.

[0089] The top of the distillation vessel is connected to a distillation column 2. The top gas outlet of the distillation column 2 is connected to a top condenser 4. The top condenser is connected to a reflux tank 6. The reflux tank 6 is connected to the distillation column 2 via a reflux pump 5. The reflux tank 6 is connected to a product collection tank 7 via a pipeline. The product collection tank 7 is connected to a vacuum system.

[0090] Ultrasonic generator 3 is used to generate high-frequency electrical signals.

[0091] The ultrasonic vibration system includes three sets of transducers, which are evenly spaced along the height of the outer wall of the distillation vessel, with a spacing of 15cm. The height of the inner part of the distillation vessel corresponding to the installation position of the uppermost transducer is the liquid level height corresponding to 50% of the volume of the distillation vessel body. Each set of transducers includes 10 transducers 16 evenly distributed along the circumference of the distillation vessel body. Each transducer is installed in a mounting groove 11. A damping pad 13 is installed between the transducer 16 and the mounting groove 11. A parabolic focusing hood 17 is connected to the front end of each transducer. The opening of the parabolic focusing hood 17 faces the outer wall of the distillation vessel body. The focal length of the parabolic focusing hood 17 is 25cm. The damping pad is made of 8mm nitrile rubber.

[0092] A sound insulation and protection system is provided, comprising a soundproof cover 15 and a sound-absorbing layer 14. The soundproof cover 15 is located outside the distillation vessel body and houses the transducer therein. The distance between the soundproof cover 15 and the outer wall of the distillation vessel body is 15 cm. The sound-absorbing layer 14 is provided on the inner wall of the soundproof cover 15. The soundproof cover 15 is made of 8 mm cold-rolled steel plate, and the sound-absorbing layer 14 is made of 30 mm polyester fiber. The surface of the sound-absorbing layer is protected by a perforated plate.

[0093] The interface monitoring system includes a laser level sensor and a foam sensor installed on the inner wall of the distillation vessel to monitor the gas-liquid interface height and foam height in real time.

[0094] The PLC control system is electrically connected to the ultrasonic generator, heating jacket, and interface monitoring system, and adjusts the ultrasonic frequency and power based on feedback from the interface monitoring system.

[0095] This device is used for the purification of electronic-grade isopropanol.

[0096] During operation, 350L of raw material is added to the distillation vessel body. The raw material contains 99% isopropanol, and the main impurities are water and trace amounts of organic by-products (such as diisopropyl ether). The mixture is preheated to 80℃ (isopropanol bubble point 82.4℃). The ultrasonic generator is started, the frequency is set to 45kHz, and the total power density (radiation area is the contact area between the focusing hood and the vessel wall) is 0.15W / cm². The ultrasonic energy is transmitted to the distillation vessel body through the focusing hood for premixing for 60min. Then, the temperature is raised to 82.4℃ for vacuum distillation.

[0097] During the distillation process, when the foam height inside the distillation vessel is greater than 5 cm and the ratio of the interface fluctuation amplitude to the inner diameter of the vessel is less than or equal to 10%, the control system will automatically adjust the control frequency to 85 kHz and the total power density to 0.17 W / cm², and accurately break the bubbles through the directional cavitation effect.

[0098] When the ratio of the interface fluctuation amplitude to the inner diameter of the vessel is greater than 10% and the interface foam height is less than or equal to 5cm, the control system will automatically adjust the frequency to 35KHz and the total power density to 0.08W / cm².

[0099] When the ratio of the interface fluctuation amplitude to the inner diameter of the vessel is greater than 10% and the interface foam height is greater than 5cm, the control system will automatically adjust the frequency to 70KHz and the total power density to 0.13W / cm².

[0100] When the ratio of the interface fluctuation amplitude to the inner diameter of the vessel is less than or equal to 10% and the interface foam height is less than or equal to 5cm, the control system will automatically adjust the control frequency to 50KHz and the total power density to 0.15W / cm².

[0101] When the concentration of isopropanol in the reactor liquid drops to 1%, heating and ultrasonic treatment are stopped, and the heavy components at the bottom of the reactor are removed by cooling. The purified isopropanol is collected in a product collection tank.

[0102] Comparative Example 1 The difference from Example 1 is that the focal length of the focusing cover is 3cm.

[0103] Operating procedure: Vacuum was applied to a pressure of 0.1 mbar, and the temperature was controlled to -30℃ (trimethylgallium bubble point -25.8℃). The ultrasonic generator was started, with a set frequency of 50 kHz and a total power density of 0.12 W / cm² (radiation area is the contact area between the focusing hood and the vessel wall). Ultrasonic energy was transmitted to the distillation vessel body through the focusing hood for premixing for 30 minutes. Then, the temperature was controlled to -23℃ for reduced pressure distillation. When the foam height was detected to be greater than 5 cm and the interface fluctuation amplitude was less than or equal to 10% of the vessel's inner diameter, the control system automatically adjusted the frequency to 85 kHz and the total power density to 0.17 W / cm². However, the foam height remained greater than 5 cm, making precise bubble breaking impossible and indicating a control malfunction.

[0104] Comparative Example 2 The difference from Example 1 is that the focal length of the focusing cover is 13.6 cm.

[0105] Operating procedure: Vacuum was applied to a pressure of 0.1 mbar, and the temperature was controlled to -30℃ (trimethylgallium bubble point -25.8℃). The ultrasonic generator was started, with a set frequency of 50 kHz and a total power density of 0.12 W / cm² (radiation area is the contact area between the focusing hood and the vessel wall). Ultrasonic energy was transmitted to the distillation vessel body through the focusing hood for premixing for 30 minutes. Then, the temperature was controlled to -23℃ for reduced pressure distillation. When the foam height was detected to be greater than 5 cm and the interface fluctuation amplitude was less than or equal to 10% of the vessel's inner diameter, the control system automatically adjusted the frequency to 85 kHz and the total power density to 0.17 W / cm². However, the foam height remained greater than 5 cm, making precise bubble breaking impossible and indicating a control malfunction.

[0106] Experimental Example The energy utilization rate, temperature uniformity, and separation effect of the devices in Examples 1-2 and Comparative Examples 1-2 were tested according to the following methods, and the experimental results are shown in Table 1.

[0107] 1. Energy efficiency: After adding the material to the reactor, start the ultrasonic generator and record the temperature rise of the material, the current and voltage of the ultrasonic generator, and the experimental time. Calculate the energy utilization rate η using the following formula.

[0108]

[0109] T, temperature rise, unit: °C; c p Specific heat capacity of material, in J / (kg·℃) V, material volume, m 3 ; ρ, material density, kg / m³ 3 ; Welectric represents the output energy of the ultrasonic generator, where U is the voltage (V), I is the current (A), and t is the time (s).

[0110] 2. Temperature uniformity At each focusing hood location, thermocouple temperature measuring instruments are installed near the vessel wall and inside the vessel to collect material temperature data, and the temperature uniformity is calculated according to the following formula.

[0111]

[0112] U: Temperature uniformity; Tmax: The highest temperature at all measuring points, in °C; Tmin: The lowest temperature at all temperature measurement points, in °C; Tm: Arithmetic mean temperature of all temperature measurement points, in °C.

[0113] 3. Separation purity The purity of the distillation product was tested using a gas chromatograph.

[0114] 4. External noise: Measured according to GB12348-2008 standard.

[0115] Table 1 Test Results Group Focusing hood focal length to vessel radius ratio (f / R) Energy utilization rate (%) Temperature uniformity (°C) Separation purity (%) External noise (dB(A)) Example 1 0.53 86 ±0.25 99.995 78 Example 2 0.625 82 ±0.35 99.998 79 Comparative Example 1 0.2 65 ±2.5 99.91 94 Comparative Example 2 0.9 52 ±0.8 99.97 87 As shown in Table 1, the comparative experiments demonstrate that the focal length / radius ratio (f / R) of the focusing hood is the core structural parameter controlling energy distribution and interfacial behavior. An f / R ratio of 0.2 leads to excessive energy focusing near the wall, causing localized high temperatures (temperature difference +2.5℃) and material decomposition (purity 99.91%). An f / R ratio of 0.9 causes excessive energy dispersion, resulting in a sharp drop in energy utilization, decreased distillation efficiency, and reduced purity of light components. Only within the f / R range of 1 / 2 to 3 / 4 can high energy utilization, high temperature uniformity, and high separation efficiency be synergistically achieved, enabling efficient separation of heat-sensitive materials.

[0116] Obviously, the above embodiments are merely illustrative examples for clear explanation and are not intended to limit the implementation. Those skilled in the art will recognize that other variations or modifications can be made based on the above description. It is neither necessary nor possible to exhaustively list all possible implementations here. However, obvious variations or modifications derived therefrom are still within the scope of protection of this invention.

[0117] In this invention, it should be understood that the terms "longitudinal", "lateral", "up", "down", "front", "rear", "left", "right", "vertical", "horizontal", "top", "middle", "bottom", "inner", and "outer" indicate the orientation or positional relationship based on the orientation or positional relationship shown in the accompanying drawings. They are only for the convenience of describing this invention and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation. Therefore, they should not be construed as limitations on this invention.

[0118] In this invention, unless otherwise explicitly specified and limited, the terms "installation," "connection," "linking," and "fixing," etc., should be interpreted broadly. For example, they can refer to a fixed connection, a detachable connection, or an integral part; they can refer to a mechanical connection or an electrical connection; they can refer to a direct connection or an indirect connection through an intermediate medium; they can refer to the internal communication of two components or the interaction between two components, unless otherwise explicitly limited. Those skilled in the art can understand the specific meaning of the above terms in this invention according to the specific circumstances.

[0119] In this invention, unless otherwise explicitly specified and limited, "above" or "below" the second feature can mean that the first feature is in direct contact with the second feature, or that the first feature is in indirect contact with the second feature through an intermediate medium. Furthermore, "above," "over," and "on top" of the second feature can mean that the first feature is directly above or diagonally above the second feature, or simply that the first feature is at a higher horizontal level than the second feature. "Below," "below," and "under" the second feature can mean that the first feature is directly below or diagonally below the second feature, or simply that the first feature is at a lower horizontal level than the second feature.

[0120] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to limit the invention.

[0121] In the description of this specification, the references to terms such as "one embodiment," "some embodiments," "example," "specific example," or "some examples," etc., refer to specific features, structures, materials, or characteristics described in connection with that embodiment or example, which are included in at least one embodiment or example of the present invention. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples. Moreover, without contradiction, those skilled in the art can combine and integrate the different embodiments or examples described in this specification, as well as the features of different embodiments or examples.

[0122] Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention. Those skilled in the art can make changes, modifications, substitutions and variations to the above embodiments within the scope of the present invention.

Claims

1. An ultrasonically enhanced intermittent distillation apparatus, characterized in that, include: Distillation kettle body; An ultrasonic generator is used to generate high-frequency electrical signals; An ultrasonic vibration system is installed on the outer wall of the distillation vessel body. The ultrasonic vibration system includes at least one set of transducers. Each set of transducers includes multiple transducers evenly distributed along the axial direction of the distillation vessel body. Each transducer is electrically connected to the ultrasonic generator. A parabolic focusing hood is connected to the front end of each transducer. The opening of each parabolic focusing hood faces the outer wall of the distillation vessel body. The ratio of the focal length of each parabolic focusing hood to the radius of the distillation vessel body is 0.5-0.75:

1.

2. The batch distillation apparatus according to claim 1, characterized in that, In the batch distillation unit When the volume of the distillation vessel body is greater than or equal to 50L and less than or equal to 200L, the number of transducer groups is 1-3, and the number of transducers in each group is 4-6. When the volume of the distillation vessel body is greater than 200L and less than or equal to 500L, the number of transducer groups is 2-5, and the number of transducers is 6-10.

3. The batch distillation apparatus according to claim 2, characterized in that, At least one axially extending mounting groove is provided on the outer wall of the distillation vessel body, and the transducers located in the same axial column of the plurality of ultrasonic transducers are all installed in the same mounting groove.

4. The batch distillation apparatus according to claim 3, characterized in that, A damping pad is also installed between each transducer and the mounting groove.

5. The batch distillation apparatus according to claim 4, characterized in that, The outer wall of the distillation vessel body is also provided with a heating jacket, which covers the outer wall of the distillation vessel body and has an opening for clearance. The ultrasonic vibration system is installed on the outer wall of the distillation vessel body through the opening.

6. The batch distillation apparatus according to claim 1, characterized in that, It also includes a sound insulation and protection system, which includes a soundproof cover and a sound-absorbing layer. The soundproof cover is located outside the body of the distillation vessel and houses the ultrasonic vibration system inside it. A sound-absorbing layer is provided on the inner wall of the soundproof cover.

7. The batch distillation apparatus according to claim 1, characterized in that, It also includes an interface monitoring system for monitoring the gas-liquid interface height and foam height; and / or, The control system is used to adjust the ultrasonic frequency and total power density based on the ratio of the interface fluctuation amplitude to the inner diameter of the vessel and the foam height.

8. A method for batch distilling electronic chemicals using the apparatus according to any one of claims 1-7, characterized in that, Includes the following steps: S1. Add the raw material containing electronic chemicals into the distillation vessel body, controlling the amount added so that the initial liquid level is 50-70% of the volume of the distillation vessel body; S2. Under distillation operating pressure, the temperature is raised to 2-10°C below the bubble point temperature of the electronic chemical. S3. Start the ultrasonic generator and heat the mixture to above the bubble point temperature of the electronic chemical to begin distillation; S4. Detect the concentration of light components in the reactor liquid. When the concentration of the electronic chemicals in the reactor liquid drops to a set threshold, stop heating and ultrasonic treatment, and end the distillation.

9. The method according to claim 8, characterized in that, Step S3 distillation includes the following process control procedures: Monitor the ratio of foam height and interface fluctuation amplitude within the distillation vessel to its inner diameter; When the foam height is less than or equal to the first preset threshold and the ratio of the interface fluctuation amplitude to the inner diameter of the vessel is less than or equal to the second preset threshold, the ultrasonic frequency is adjusted to the first preset range and the total power density is adjusted to the second preset range. When the foam height is greater than the first preset threshold and the ratio of the interface fluctuation amplitude to the inner diameter of the vessel is less than or equal to the second preset threshold, the ultrasonic frequency is adjusted to the third preset range and the total power density is adjusted to the fourth preset range. When the foam height is less than or equal to the first preset threshold and the ratio of the interface fluctuation amplitude to the inner diameter of the vessel is greater than the second preset threshold, the ultrasonic frequency is adjusted to the fifth preset range and the total power density is adjusted to the sixth preset range. When the foam height is greater than the first preset threshold and the ratio of the interface fluctuation amplitude to the inner diameter of the vessel is greater than the second preset threshold, the ultrasonic frequency is adjusted to the seventh preset range and the total power density is adjusted to the eighth preset range.

10. The method according to claim 9, characterized in that, The first preset threshold is less than or equal to 5cm, and the second preset threshold is less than or equal to 10%. The first preset range is 40-60kHz, and the second preset range is 0.10-0.15W / cm². 2 ; The third preset range is greater than 80Hz and less than or equal to 100KHz, and the fourth preset range is greater than 0.15W / cm² and less than or equal to 0.20 / cm². The fifth preset range is greater than or equal to 30kHz and less than 40kHz; the sixth preset range is greater than or equal to 0.05W / cm² and less than 0.1W / cm². The seventh preset range is greater than 60Hz and less than or equal to 80kHz, and the eighth preset range is 0.10-0.15W / cm².

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