A method and apparatus for continuous liquid phase production of low salt high concentration aminosilane

Abstract

The application relates to the chemical technology field, and particularly discloses a method and device for continuously producing low-salt high-concentration aminosilane in liquid phase, which comprises a raw material feeding system and a reaction reflux system; the raw material feeding system comprises a first raw material storage tank, a reaction liquid intermediate tank, a reaction solvent storage tank, a first raw material premixing tank, a second raw material premixing tank and a second raw material gas cylinder; the reaction reflux system comprises a main reaction tube, a first-stage buffer tank, a second-stage buffer tank and a salt separation system; the salt separation system comprises a first-stage separator and a second-stage separator; both the first-stage separator and the second-stage separator are hydrocyclones; a flow guide grating and a rotating part are arranged on the overflow pipes of the hydrocyclones; through the design of the reaction reflux system, the product content in the reaction liquid can be higher than 50%, the use amount of the organic solvent is greatly reduced, and the energy consumption and product loss in the subsequent purification stage are reduced.

Description

Technical Field

[0001] The present invention relates to the technical field of chemical industry, and in particular to a method and device for continuously producing low-salt high-concentration aminosilane in a liquid phase. Background Art

[0002] Aminosilane compounds, such as trimethylsilane, diisopropylaminosilane, bis(diethylamino)silane, and bis(tert-butylamino)silane, are silicon-based film-forming precursors that can be deposited through ALD / CVD processes to form high-precision, nanoscale, uniform thin films, meeting the coverage requirements of high-aspect ratio structures in modern advanced semiconductor processes. The rapid development of artificial intelligence in recent years has driven a rapid increase in demand for hardware computing power, and the market's requirements for semiconductor device performance have also become increasingly stringent. Aminosilane precursors, due to their low-temperature efficiency, high reactivity, and excellent thin-film properties, have become indispensable materials for advanced semiconductor manufacturing. They are valued by major semiconductor manufacturers and are experiencing growing market demand.

[0003] Currently, most industrial aminosilane production processes use liquid phase synthesis. Specifically, chlorosilane and ammonia / amine are added to the reactor in sequence, and react in a condensed state in a reaction solvent under low temperature conditions to produce the target product and the by-product chloramine salt. This type of liquid phase synthesis reaction is usually intermittent, with high operating risks and low production capacity. Generally speaking, the amount of chloramine salt produced as a by-product of the reaction is huge. In order to maintain good fluidity of the reaction system, a large amount of solvent is required, resulting in a low concentration of reactants in the final reaction system, ultimately leading to low reaction efficiency, low yield of the target product, low concentration of the target product, and huge energy consumption for solvent recovery. Taking the conventional synthesis method of trimethylsilylamine as an example, ammonia and monochlorosilane are introduced into toluene solvent at low temperature to generate the target product and by-product salt. The amount of by-product chloramine salt generated by this reaction is 1.5 times that of the target product, and 8 to 10 times the amount of solvent of the target product is required to ensure the normal flow of the reaction system. At this time, even if all the reactants are converted into the target product, the concentration of the target product in the reaction system is less than 10%, which brings great difficulties to the enrichment of the target product in the subsequent distillation and purification stage.

[0004] Furthermore, the byproduct chloramine salts persist in the reaction system for extended periods, not only readily adsorbing the target product but also promoting its decomposition, leading to an increase in undesirable side reactions and a further decrease in product yield. Furthermore, these chloramine salts are easily decomposed, lightweight, and easily dispersed, making them easily carried over during subsequent crude product filtration or distillation, where they can diffuse throughout the reaction pipeline, potentially leading to pipeline blockage and the introduction of product impurities. This presents a significant pain point in the industry. Summary of the Invention

[0005] The object of the present invention is to provide a method and apparatus for continuous liquid phase production of low-salt, high-concentration aminosilane to address the above-mentioned deficiencies in the prior art.

[0006] In order to achieve the above object, the present invention provides the following technical solutions:

[0007] A device for continuous liquid phase production of low-salt, high-concentration aminosilane, comprising a raw material feeding system and a reaction reflux system;

[0008] The raw material feeding system includes a first raw material storage tank, a reaction liquid intermediate tank, a reaction solvent storage tank, a first raw material premixing tank, a second raw material premixing tank and a second raw material gas cylinder;

[0009] The reaction reflux system includes a main reaction tube, a primary buffer tank, a secondary buffer tank and a salt separation system;

[0010] The salt separation system includes a primary separator and a secondary separator. Both the primary separator and the secondary separator are hydrocyclones. The overflow pipes of the hydrocyclones are provided with guide grids and rotating components.

[0011] Preferably, the first raw material storage tank contains the first raw material, and the first raw material is one of ammonia, dimethylamine, methylethylamine, diethylamine, diisopropylamine, and tert-butylamine. When the first raw material is in liquid state, the first raw material storage tank is used for storage, and when the first raw material is in gaseous state, the first raw material gas cylinder is used for storage;

[0012] The second raw material gas cylinder contains a second raw material, and the second raw material is one of monochlorosilane and dichlorosilane.

[0013] Preferably, the feed ratio of the first raw material to the second raw material is a chemical reaction equivalent ratio of 1.0 to 1.2:1.

[0014] Preferably, the raw material feeding system also includes a multi-point high-frequency sampling pipeline, which is used to feed the second raw material, and the number of sampling tubes in the sampling pipeline is 4 to 20, which are radially distributed around the main reaction tube, and the sampling tube for the second raw material is at the rear end of the first raw material sampling tube.

[0015] Preferably, the inner diameter of the main reaction tube is 0.02-0.3 m, the length is 1-10 m, the inner wall is lined with polytetrafluoroethylene, the main reaction tube is a jacketed reaction tube, and the temperature inside the main reaction tube is -10-20°C.

[0016] Preferably, the bottom of each of the first-stage separator and the second-stage separator is provided with a salt slag buffer chamber and a salt slag storage tank controlled by dual pneumatic valves.

[0017] Preferably, the rotating component located on the first-stage separator has a tapered section angle of 10 to 20 degrees, and the rotating component located on the second-stage separator has a tapered section angle of 7 to 15 degrees.

[0018] Preferably, a threaded tube is rotatably provided on the guide grid plate, a rotating shaft is rotatably provided on the first-stage separator, the rotating shaft is threadedly connected to the threaded tube, the rotating shaft is fixedly connected to the rotating component, a plug-in block is slidably provided on the guide grid plate, a slot is provided on the threaded tube, and the plug-in block is plugged into the slot;

[0019] A sliding pin is slidably provided on the plug-in block, a second spring is provided between the sliding pin and the plug-in block, and two ends of the second spring are fixedly connected to the sliding pin and the plug-in block respectively;

[0020] A first spring is provided between the sliding pin and the guide grid plate, and two ends of the first spring are fixedly connected to the sliding pin and the guide grid plate respectively.

[0021] Preferably, a lifting ring is slidably provided on the first-stage separator, a lifting rod is fixedly provided on the lifting ring, an inclined groove is provided on the lifting rod, and the sliding pin is plugged into and matched with the inclined groove;

[0022] A rotating frame is fixedly provided on the rotating shaft, a rotating ring is slidably provided on the rotating frame, the rotating ring is rotatably connected to the lifting ring, a centrifugal rod is slidably provided on the rotating frame, a steel wire rope is provided between the centrifugal rod and the rotating ring, and two ends of the steel wire rope are fixedly connected to the centrifugal rod and the rotating ring respectively;

[0023] A third spring is provided between the rotating ring and the rotating frame, and two ends of the third spring are fixedly connected to the rotating ring and the rotating frame respectively.

[0024] A method for continuous liquid phase production of low-salt, high-concentration aminosilane, the method being based on the above-mentioned apparatus for continuous liquid phase production of low-salt, high-concentration aminosilane, comprising:

[0025] S1: solvent perfusion of the reaction pipeline;

[0026] S2: raw material premixing;

[0027] S3: continuous feed reaction;

[0028] S4: Product extraction.

[0029] In the above technical solution, the method and apparatus provided by the present invention for continuous liquid phase production of low-salt, high-concentration aminosilane have the following beneficial effects:

[0030] 1. Compared with the liquid phase batch preparation method used by most existing aminosilanes, this method and device realize continuous liquid phase synthesis with low operation risk and high production capacity.

[0031] 2. Through the design of the reaction reflux system, the product content in the reaction liquid can exceed 50%, which greatly reduces the use of organic solvents and reduces the energy consumption and product loss in the subsequent purification stage.

[0032] 3. Through the design of multi-point injection with small amounts of high frequency and the addition of polytetrafluoroethylene lining on the inner walls of the reactor and hydrocyclone separator, the salt concentration in the reaction liquid is greatly reduced. The salt generated in the reaction liquid is difficult to agglomerate and adsorb on the wall of the device, which greatly reduces the risk of blockage of the reaction tube.

[0033] 4. By adding rotating parts to the centrifugal chamber of the hydrocyclone separator and adding guide grids to the overflow pipe, chloramine salts can be effectively separated from the reaction solvent / product with similar density. The forced laminar flow through the guide grids makes it difficult for salt particles to remix, greatly enhancing the separation effect of the primary separator and the secondary separator.

[0034] It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the disclosure.

[0035] This application document provides an overview of various implementations or examples of the technology described in this disclosure, and is not a comprehensive disclosure of the full scope or all features of the disclosed technology. BRIEF DESCRIPTION OF THE DRAWINGS

[0036] In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments. Obviously, the drawings described below are only some embodiments described in the present invention. For ordinary technicians in this field, other drawings can also be obtained based on these drawings.

[0037] Figure 1 A schematic diagram of the overall structural principle provided by an embodiment of the present invention;

[0038] Figure 2 A schematic diagram of the structure of a separator provided in an embodiment of the present invention;

[0039] Figure 3 The embodiment of the present invention provides Figure 2 A magnified view of point A in the figure;

[0040] Figure 4 A schematic diagram of the structure of the rotating ring and the lifting ring provided in an embodiment of the present invention;

[0041] Figure 5 A schematic diagram of the guide grid structure provided by an embodiment of the present invention;

[0042] Figure 6 This is a schematic diagram of the centrifugal rod structure provided by an embodiment of the present invention.

[0043] Description of reference numerals:

[0044] 1. The first raw material storage tank;

[0045] 2. Reaction liquid intermediate tank;

[0046] 3. Reaction solvent storage tank;

[0047] 4. First raw material premixing tank;

[0048] 5. Second raw material premixing tank;

[0049] 504, injection pipeline;

[0050] 6. The first raw gas cylinder;

[0051] 7. Second raw gas cylinder;

[0052] 8. Main reaction tube;

[0053] 9. Primary separator;

[0054] 10. Primary buffer tank;

[0055] 11. Secondary separator;

[0056] 12. Secondary buffer tank;

[0057] 16. The first adsorption column;

[0058] 17. Second adsorption column;

[0059] 18. Crude product tank;

[0060] 1507, pressure gauge;

[0061] (13 / 14 / 15), solid-liquid transfer pump;

[0062] (1506 / 1606 / 507 / 407 / 205), flow meter (MFT);

[0063] (102 / 303 / 702 / 602), mass flow controller (MFC);

[0064] (1003 / 1203), liquid level gauge;

[0065] (1051 / 1101 / 1505 / 1605 / 404 / 503 / 901 / 406), regulating valve;

[0066] (905 / 1105), overflow pipe;

[0067] (1106 / 906), rotating parts;

[0068] (907 / 1107), buffer cavity;

[0069] (1108 / 908), salt slag storage tank;

[0070] (601 / 701), pressure reducing valve;

[0071] (101 / 1001 / 1002 / 1103 / 1104 / 1201 / 1202 / 1501 / 1503 / 1504 / 1601 / 1604 / 1704 / 1801 / 1802 / 201 / 203 / 204 / 301 / 302 / 401 / 403 / 405 / 501 / 505 / 801 / 903 / 904 / 803 / 1501 / 506), valves;

[0072] 910, guide grid;

[0073] 911, plug-in block;

[0074] 912, sliding pin;

[0075] 913, first spring;

[0076] 914, second spring;

[0077] 920, threaded pipe;

[0078] 921, slot;

[0079] 930, shaft;

[0080] 940, rotating frame;

[0081] 941, rotating ring;

[0082] 942, centrifugal rod;

[0083] 943, third spring;

[0084] 944, wire rope;

[0085] 950, lifting ring;

[0086] 951, lifting rod;

[0087] 952. Chute. DETAILED DESCRIPTION

[0088] To make the purpose, technical solutions, and advantages of the embodiments of the present disclosure more clear, the technical solutions of the embodiments of the present disclosure will be clearly and completely described below in conjunction with the accompanying drawings of the embodiments of the present disclosure. Obviously, the described embodiments are part of the embodiments of the present disclosure, not all of the embodiments. Based on the described embodiments of the present disclosure, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present disclosure.

[0089] Please refer to 1-6, a device for continuous liquid phase production of low-salt high-concentration aminosilane, including a raw material feeding system and a reaction reflux system; the raw material feeding system includes a first raw material storage tank 1, a reaction liquid intermediate tank 2, a reaction solvent storage tank 3, a first raw material premixing tank 4, a second raw material premixing tank 5 and a second raw material gas cylinder 7; the reaction reflux system includes a main reaction pipe 8, a primary buffer tank 10, a secondary buffer tank 12 and a salt separation system; the salt separation system includes a primary separator 9 and a secondary separator 11, both of which are cyclones, and the overflow pipe 905 of the cyclone separator is provided with a guide grid 910 and a rotating component 906, which are used to control the mixing ratio of the two raw materials and the reaction solvent / reflux reaction liquid through the first raw material premixing tank 4 and the second raw material premixing tank 5 to achieve the purpose of continuous and stable feeding; the reaction liquid intermediate tank 2 is used to store the reflux reaction liquid, and it will be mixed with the first raw material into the first raw material premixing tank 4 and circulated to the main reaction pipeline again; A DCS system is provided in the raw material feeding system for continuously and steadily regulating the feed concentration and feed amount of the two raw materials; a DCS system is provided in the reaction and reflux system for continuously and steadily regulating the crude product output, reflux amount and feed amount; the primary separator 9 and the secondary separator 11 in the salt separation system are used for graded centrifugal separation of chloramine salts, and rotating components 906 are provided in the primary separator 9 and the secondary separator 11 for increasing the centrifugal speed during separation; a primary buffer tank 10 and a secondary buffer tank 12 are provided in the reaction and reflux system to balance the liquid carrying volume during the circulation reaction process.

[0090] The first raw material storage tank 1 contains the first raw material, which is one of ammonia, dimethylamine, methylethylamine, diethylamine, diisopropylamine, and tert-butylamine. When the first raw material is liquid, the first raw material storage tank 1 is used for storage, and when the first raw material is gaseous, the first raw material gas cylinder 6 is used for storage; the second raw material gas cylinder 7 contains the second raw material, which is one of monochlorosilane and dichlorosilane. The first raw material storage tank 1 and the first raw material gas cylinder 6 are storage tanks for the first reaction raw material ammonia / amine. The storage tank 1 is used to store liquid amines, such as diethylamine, and the first raw material gas cylinder 6 is used to store gaseous amines, such as ammonia. In a single reaction, only one of the first raw material storage tank 1 and the first raw material gas cylinder 6 will be used, and the second raw material gas cylinder 7 is used to store the second reaction raw material chlorosilane, such as monochlorosilane.

[0091] The feed ratio of the first raw material to the second raw material is a chemical reaction equivalent ratio of 1.0 to 1.2:1.

[0092] The raw material feeding system also includes a multi-point high-frequency sampling pipeline 504, which is used to feed the second raw material. The number of sampling tubes in the sampling pipeline 504 is 4 to 20, which are radially distributed around the main reaction tube 8, and the sampling tube for the second raw material is at the rear end of the first raw material sampling tube.

[0093] The inner diameter of the main reaction tube 8 is 0.02~0.3m, the tube length is 1~10m, the inner wall is lined with polytetrafluoroethylene, the main reaction tube 8 is a jacketed reaction tube, and the temperature inside the main reaction tube 8 is -10~20℃. The inner diameter of the main reaction tank 8 can be set to 0.05~0.2m to improve the reaction efficiency. The main reaction tube 8 is a jacketed reaction tube, and the mold temperature controller is used to control the flow of cold oil to maintain the temperature inside the main reaction tube at -10~20℃.

[0094] The bottom of the primary separator 9 and the secondary separator 11 are both provided with a salt slag buffer chamber 907, 1107 and a salt slag storage tank 908, 1108 controlled by double pneumatic valves.

[0095] The rotating component 906 located on the first-stage separator 9 has a conical section angle of 10 to 20 degrees, and the rotating component 1106 located on the second-stage separator 11 has a conical section angle of 7 to 15 degrees.

[0096] The reaction and reflux system is provided with three solid-liquid delivery pumps 13, 14, and 15 to provide circulation power for the entire circulation pipeline; the reaction and reflux system is provided with a crude product extraction point and a reaction liquid reflux point; and the salt separation system is provided with a first adsorption column 16 and a second adsorption column 17 to absorb and dissolve trace chloramine salts in the extracted crude product.

[0097] A threaded tube 920 is rotatably provided on the guide grid plate 910, and a rotating shaft 930 is rotatably provided on the first-stage separator 9. The rotating shaft 930 is threadedly connected to the threaded tube 920, and the rotating shaft 930 is fixedly connected to the rotating component 906. A plug-in block 911 is slidably provided on the guide grid plate 910, and a slot 921 is provided on the threaded tube 920. The plug-in block 911 is plugged into the slot 921; a sliding pin 912 is slidably provided on the plug-in block 911, and a second spring 914 is provided between the sliding pin 912 and the plug-in block 911, and the two ends of the second spring 914 are respectively fixedly connected to the sliding pin 912 and the plug-in block 911; a first spring 913 is provided between the sliding pin 912 and the guide grid plate 910, and the two ends of the first spring 913 are respectively connected to the sliding pin 912 and the plug-in block 911. The guide grid plate 910 is fixedly connected; a lifting ring 950 is slidingly provided on the primary separator 9, a lifting rod 951 is fixedly provided on the lifting ring 950, an inclined groove 952 is provided on the lifting rod 951, and the sliding pin 912 is plugged into the inclined groove 952; a rotating frame 940 is fixedly provided on the rotating shaft 930, a rotating ring 941 is slidingly provided on the rotating frame 940, the rotating ring 941 is rotatably connected to the lifting ring 950, a centrifugal rod 942 is slidingly provided on the rotating frame 940, a steel wire rope 944 is provided between the centrifugal rod 942 and the rotating ring 941, and the two ends of the steel wire rope 944 are fixedly connected to the centrifugal rod 942 and the rotating ring 941 respectively; a third spring 943 is provided between the rotating ring 941 and the rotating frame 940, and the two ends of the third spring 943 are respectively The chloramine salt can be effectively separated from the reaction solvent / product with similar density by setting the guide grid 910 in the overflow pipe 905, and the salt particles are difficult to be mixed back by the forced laminar flow of the guide grid 910, thereby improving the separation effect of the hydrocyclone. During the separation process, the rotating shaft 930 rotates, driving the rotating component 906 to rotate, thereby improving the centrifugal separation effect. When the rotating component 906 speeds up, the centrifugal speed is accelerated, and the turbulence in the separation chamber is accelerated. At this time, under the action of the acceleration of the rotating shaft 930, the centrifugal rod 942 slides to both sides by centrifugal force. During the sliding process, the rotating ring 941 is pulled upward by the wire rope 944. During the upward movement, the rotating ring 941 , compress the third spring 943, and pull the lifting ring 950 and the lifting rod 951 to move upward. During the upward movement of the lifting rod 951, the inclined groove 952 presses the sliding pin 912 through the inclined surface, causing the sliding pin 912 to slide, squeezing the first spring 913 and the second spring 914. At this time, the rotating shaft 930 rotates with the threaded tube 920. When the slot 921 on the threaded tube 920 is aligned with the plug-in block 911, under the action of the second spring 914, the plug-in block 911 slides and plugs into the slot 921, and the rotation of the threaded tube 920 is restricted. At this time, the rotating shaft 930 continues to rotate, and moves the threaded tube 920 and the guide grid 910 upward through the threaded connection. When it moves up until the sliding pin 912 corresponds to the inclined groove 952,Under the action of the first spring 913, the sliding pin 912 slides into the inclined groove 952, and by pulling the second spring 914, the plug-in block 911 slides and separates from the slot 921. At this time, the rotating shaft 930 drives the threaded tube 920 to rotate and limits the height of the guide grid 910. When the rotating shaft 930 drives the rotating component 906 to speed up, the turbulence in the separation chamber is accelerated, and the guide grid 910 moves up, so that the turbulent flow enters the overflow pipe 905 and is buffered to a certain extent. The turbulent flow is then dispersed by the guide grid 910 to prevent the turbulent flow from directly entering the guide grid 910 when it is too fast, resulting in a reduction in the effect of the guide grid 910 on dispersing the turbulent flow, affecting the separation effect, and avoiding the problem of the guide grid 910 being easily blocked. After the separation is completed, the rotating shaft 93 0 stops rotating, the centrifugal force on the centrifugal rod 942 disappears, and under the rebound action of the third spring 943, the rotating ring 941, the lifting ring 950, and the lifting rod 951 move down and reset, and the centrifugal rod 942 resets. During the downward movement of the lifting rod 951, the inclined surface of the inclined groove 952 presses the sliding pin 912, and the sliding pin 912 slides, squeezing the first spring 913 and the second spring 914. After the lifting rod 951 completes its reset, the rotating shaft 930 rotates in the opposite direction. When the slot 921 on the threaded tube 920 is aligned with the plug-in block 911, the plug-in block 911 is plugged into the slot 921 under the action of the second spring 914, and the rotation of the threaded tube 920 is restricted. At this time, the rotating shaft 930 reverses, which can drive the threaded tube 920 and the guide grid plate 910 to move down and reset.

[0098] In the present invention, the first-stage separator 9 and the second-stage separator 11 have the same structure, and only the angles of the conical sections of the rotating component 906 and the rotating component 1106 are different.

[0099] The present invention also provides a method for continuous liquid phase production of low-salt, high-concentration aminosilane, which is based on the above-mentioned continuous liquid phase production device for low-salt, high-concentration aminosilane, and the method comprises:

[0100] S1: solvent perfusion of the reaction pipeline;

[0101] S2: raw material premixing;

[0102] S3: continuous feed reaction;

[0103] S4: Product extraction.

[0104] S1. Solvent perfusion in the reaction pipeline:

[0105] Before starting the reaction, the system is first primed with reaction solvent. Open the bottom outlet valve 301 and passage valve 302, 203 of the reaction solvent storage tank 3, open the liquid phase feed regulating valve 406 of the first raw material premix tank 4, add reaction solvent to the premix tank 4, and the amount of addition is 40-100% of the total volume of the entire circulating pipeline, including the main reaction tube 8, the first-stage separator 9, the second-stage separator 11, the first-stage buffer tank 10, and the second-stage buffer tank 12. If the first raw material is gaseous, first freeze the temperature of the first raw material premix tank 4 to a temperature below its boiling point by using a mold temperature machine, then open the pressure-reducing valve 601 of the gas cylinder 6, open the gas inlet valve 405 of the first raw material premix tank 4, and bubble the first raw material into the first raw material premix tank 4 through the mass flowmeter 602. If the first raw material is liquid, open the lower end outlet valve 101 of the first raw material storage tank 1, and control the first raw material feed into the first raw material premix tank 4 through the mass flowmeter 102. The reaction solvent in the first raw material premix tank 4 is mixed with 3-15% of the first raw material to form priming solvent, and the actual mixing concentration is monitored through the detection port 2. After the priming solvent is mixed, all the valves and mass flowmeters are closed, the outlet valve 801 of the main reaction tube 8 is opened, the bottom outlet valves 401, 403 of the first raw material premix tank 4 are opened, the priming solvent is added to the main reaction tube 8 by adjusting the opening degree of the regulating valve 404, when the main reaction tube 8 is primed, the solid-liquid delivery pump 13 is opened, the pump flow is controlled by adjusting the opening degree of the valve 901, and the priming solvent is delivered to the first-stage separator 9, when the first-stage separator 9 is filled with the priming solvent, the rotating part 906 is opened, the inlet valve 1001 of the first-stage buffer tank 10 is opened, the priming solvent is delivered to the first-stage buffer tank 10 through the overflow pipe 905, when the liquid level of the first-stage buffer tank 10 reaches 20-70%, the valve 1002 and the solid-liquid delivery pump 14 are opened, the pump flow is controlled by adjusting the opening degree of the regulating valve 1101, and the priming solvent is delivered to the second-stage separator 11, when the second-stage separator 11 is filled with the priming solvent, the rotating part 1106 is opened, the inlet valve 1201 of the second-stage buffer tank is opened, the priming solvent is delivered to the second-stage buffer tank 12 through the overflow pipe 1105, when the liquid level of the second-stage buffer tank 12 reaches 20-70%, the valves 1202, 1501, 1503, 803 and the solid-liquid delivery pump 15 are opened, the priming liquid is returned to the main reaction tube 8 by controlling the pump flow through the opening degree of the valve 1501, and the solvent priming of the entire main circulating pipeline is completed. After the priming is completed, the DCS system is enabled, the regulating valve 901 is interlocked to the liquid level meter 1003, the regulating valve 1101 is interlocked to the liquid level meter 1203, the opening degree of the regulating valve is adjusted through system automation control, and the liquid levels of the first-stage buffer tank 10 and the second-stage buffer tank 12 are kept in a stable state during the continuous circulation and subsequent circulation reaction process. It should be noted that if the first raw material is gaseous, the residual liquid level in the first raw material premix tank 4 should be kept above the gas bubbling pipe after the reaction solvent priming is completed.

[0106] S2. Raw material premixing:

[0107] Premixing of the first raw material: Before premixing the first raw material, first open valves 1504 and 204, open regulating valve 1505 and mass flow meter 1506, and pour the reaction solvent extraction part from the circulation pipeline into the reaction liquid intermediate tank 2 until the liquid level reaches 10-20%, then close valves 1504 and 204, close regulating valve 1505 and mass flow meter 1506; if the first raw material is gaseous, first cool the temperature of the first raw material premix tank 4 to a temperature below its boiling point through the mold temperature controller, and then open the gas cylinder 6 The pressure reducing valve 601 is opened, the air inlet valve 405 on the first raw material premixing tank 4 is opened, and the first raw material is bubbled into the first raw material premixing tank 4 through the mass flow meter 602; if the first raw material is liquid, the outlet valve 101 at the lower end of the first raw material storage tank 1 is opened, and the first raw material is fed into the first raw material premixing tank 4 through the mass flow controller 303, and the reaction solvent in the first raw material premixing tank 4 is prepared into a premixed liquid containing 10-90% of the first raw material, and the actual prepared concentration is monitored through the detection port 2.

[0108] Premixing the Second Raw Material: Open the bottom discharge valve 301 of the reaction solvent storage tank 3 and the liquid-phase feed valve 506 of the second raw material premixing tank 5. Control the solvent feed into the second raw material premixing tank 5 using the mass flow controller 303 until the liquid level in the second raw material premixing tank 5 is above the gas bubbling nozzle. Use a mold temperature controller to chill the temperature of the second raw material premixing tank 5 to a temperature below the boiling point of the second raw material. Then, open the pressure reducing valve 701 of the second raw material gas cylinder 7 and the gas-phase feed valve 505 of the second raw material premixing tank 5. Control the second raw material by bubbling into the raw material 2 premixing tank using the mass flow controller 702. Prepare a premix containing 40-80% raw material 2 in the reaction solvent of the second raw material premixing tank 7. Monitor the actual concentration through the detection port.

[0109] S3, continuous feeding reaction:

[0110] Open the outlet valve 401 of the first raw material premixing tank 4, and pass the premixed liquid into the main reaction tube 8 at a predetermined rate through the regulating valve 404 and the mass flow meter 407. Open the outlet valve 501 of the second raw material premixing tank 5, and pass the premixed liquid into the main reaction tube 8 at a predetermined rate through the multi-point injection pipeline 504 through the regulating valve 503 and the mass flow meter 507 to start the feeding reaction. At the same time, open the premixing passage of the raw material premixing stage, open the bottom valve 201 of the reaction liquid intermediate tank 2, and pass the mass flow meter 2 05 and the opening of the regulating valve 406, start to add premixed raw materials to the first raw material premixing tank 4 and the second raw material premixing tank 5, and control the feed rate of the entire continuous reaction system by activating the DCS system: (1) The first raw material mass flow controller 602 / 102 and the reaction liquid intermediate tank 2 mass flow meter 205 are interlocked with the first raw material premixing tank 4 outlet regulating valve 404, and regulate the outlet mass flow rate of the first raw material premixed liquid (mass flow meter 407) to be equivalent to the total feed rate of the first raw material and the reaction liquid intermediate tank 2. (2) The second raw material mass flow controller 702 and the reaction solvent storage tank 3 mass flow controller 303 are interlocked with the second raw material premixing tank 5 outlet regulating valve 503, and regulate the outlet mass flow rate of the second raw material premixing tank 5 to be equivalent to the total feed rate of the second raw material and the reaction solvent. (3) The first raw material mass flow controller 602 / 102, the second raw material mass flow controller 702 and the reaction solvent storage tank 3 mass flow controller 303 need to be set to the predetermined values ​​to ensure the concentration and feed rate of the feed raw materials.

[0111] The two raw materials introduced into the main reaction tube 8 come into contact and react rapidly in the main reaction tube 8 to generate the target product and the by-product chloramine salt. The salt-containing reaction liquid is sent to the primary separator 9 by the solid-liquid transfer pump 13 for coarse separation of salt particles. The salt separation effect is greater than 95% through the high-speed rotating component 906 and the overflow pipe 905 with a built-in forced layer guide grid 910. The low-salt reaction liquid separated by the primary separator 9 enters the first buffer tank 10 and is then pumped to the secondary separator 11 by the solid-liquid transfer pump 14 for further separation of salt particles. By narrowing the angle of the conical section of the rotating component 1106 of the secondary separator 11 and the higher centrifugal speed, smaller and finer salt particles are separated, and the separation effect is greater than 70%. The reaction liquid separated by the secondary separator 11 enters the second buffer tank 12. It is then pumped back to the main reaction tube 8 by the solid-liquid transfer pump 15. During this period, the amount of circulating reaction liquid extracted into the reaction liquid intermediate tank 2 is controlled by the DCS system. The pressure gauge 1507 in front of the main reaction tube 8 is interlocked with the regulating valve 1505 and the reflux mass flowmeter 1506. By extracting the excess circulating reaction liquid in the circulation pipeline into the reaction liquid intermediate tank 2, the hydraulic pressure of the circulation pipeline is controlled to be maintained in a stable state; the liquid phase composition and salt concentration of the reaction liquid coming out of the main reaction tube 8 are detected through the detection port 4, the liquid phase composition and salt concentration of the reaction liquid coming out of the first separator 9 are detected through the detection port 5, the liquid phase composition and salt concentration of the reaction liquid coming out of the second separator 11 are detected through the detection port 6, and the liquid phase composition and salt concentration of the reaction liquid coming out of the second buffer tank 12 are detected through the detection port 7 to determine whether it meets the extraction conditions. The chloramine salts accumulated at the bottom of the primary separator 9 and the secondary separator 11 are discharged through the periodic opening of the dual pneumatic valves. First, valve 903 or valve 1103 is opened to discharge the salt slag at the bottom of the conical section of the separator into the buffer chamber 907 or 1107, then valve 903 or valve 1103 is closed, and then valve 904 or valve 1104 is opened to discharge the salt slag in the buffer chamber into the salt slag storage tank 908 or salt slag storage tank 1108, and then valve 904 or valve 1104 is closed.

[0112] S4. Product extraction:

[0113] The two streams of raw materials are kept continuously and stably entering the circulation reaction, and samples are analyzed at various points on the reaction circulation pipeline every 1 hour. When the concentration of the target product detected by the detection port 7 reaches the established target concentration value and the salt content meets the standard, the product extraction begins; open valves 1601 / 1701 and 1604 / 1704, and control the product extraction flow rate through the mass flow meter 1606 and the regulating valve 1605; the extracted material is then passed through the first adsorption column 16 and the second adsorption column 17 to remove the trace chloramine salt dissolved in the crude product, and a salt-free high-concentration crude product can be obtained. The test port 8 is used to further confirm whether the produced material is qualified. If qualified, the feed valve 1801 of the crude product tank 18 is opened to produce the crude product. If unqualified, the valve 1802 is opened to return the crude product to the reaction liquid intermediate tank 2. After the product starts to be produced, the mass flow meter 205 of the reaction liquid intermediate tank 2 is automatically controlled and interlocked with the return material mass flow meter 1506 to control the return material flow rate to be equivalent to the outlet flow rate of the reaction liquid intermediate tank 2. The display value of the first raw material flow mass controller 602 / 102 is interlocked with the produced mass flow meter 1606 to control the produced flow rate.

[0114] The following are examples and comparative examples provided by the present invention:

[0115] Example 1

[0116] According to the above-described specific embodiment, the reaction was carried out using diethylamine as the first raw material, dichlorosilane as the second raw material, and n-hexane as the reaction solvent to produce the target product, bis(diethylamino)silane. The feed rate of the first raw material was 0.5456 kg / min, the feed rate of the second raw material was 0.18 kg / min, and the feed rate of the additional solvent was 0.15 kg / min. After 29 hours of total reflux cycle reaction, the crude product began to be steadily produced.

[0117] Example 2

[0118] According to the above-described specific embodiment, the reaction was carried out using ammonia as the first raw material, monochlorosilane as the second raw material, and toluene as the reaction solvent to produce the target product, trisilylamine. The feed rate of the first raw material was 0.2311 kg / min, the feed rate of the second raw material was 0.6 kg / min, and the feed rate of the additional solvent was 0.18 kg / min. After a total reflux cycle reaction time of 35 hours, the crude product began to be steadily produced.

[0119] Example 3

[0120] According to the above specific embodiment, the first raw material used was diisopropylamine, the second raw material was monochlorosilane, and the reaction solvent was diethyl ether. The reaction produced the target product, diisopropylaminosilane. The feed rate of the first raw material was 0.5755 kg / min, the feed rate of the second raw material was 0.18 kg / min, and the feed rate of the additional solvent was 0.18 kg / min. After 26 hours of total reflux cycle reaction, the crude product began to be steadily produced.

[0121] Comparative Example 1

[0122] Bis(diethylamino)silane is synthesized in a batch reactor in liquid phase. 280 kg of diethylamine, 86 kg of dichlorosilane, and 1010 kg of n-hexane are added as the first raw material, respectively. The reaction is refluxed for 12 hours, and the reaction mass is filtered to remove the chloramine salt to obtain a low-salt crude product.

[0123] Comparative Example 2

[0124] Trisilylamine is synthesized in a batch reactor in liquid phase. 101 kg of ammonia gas as the first raw material, 311 kg of monochlorosilane as the second raw material, and 1346 kg of toluene as the reaction solvent are added in one batch. After adding the materials, the mixture is refluxed for 12 hours. The reaction material is put into a filter to filter out the chloramine salt to obtain a low-salt crude product.

[0125] Comparative Example 3

[0126] Diisopropylaminosilane was synthesized in a batch reactor in liquid phase. 321 kg of diisopropylamine, 101 kg of monochlorosilane, and 1053 kg of ether were added as the first raw material, and the mixture was refluxed for 12 hours. The reaction mass was then filtered to remove the chloramine salt to obtain a crude product with low salt content.

[0127] The test results of Examples 1 to 3 and Comparative Examples 1 to 3 are shown in Table 1 below.

[0128] Table 1

[0129]

[0130] Note: ND means the content is below the detection limit of the equipment

[0131] As can be seen from the data in the above table, the method and apparatus for continuous liquid-phase production of low-salt, high-concentration aminosilane described in the present invention can significantly reduce the salt concentration in the reaction solution, and the salt content in the crude product is greatly reduced, which has met the electronic grade salt content standard. At the same time, the concentration of the target product in the crude product is greatly improved, and the yield is greatly improved.

[0132] The above description is merely illustrative of certain exemplary embodiments of the present invention. It goes without saying that those skilled in the art will be able to modify the described embodiments in various ways without departing from the spirit and scope of the present invention. Therefore, the above drawings and description are illustrative in nature and should not be construed as limiting the scope of protection of the claims.

Claims

1. A device for continuous liquid phase production of low-salt, high-concentration aminosilane, characterized in that: Including raw material feeding system and reaction reflux system; The raw material feeding system comprises a first raw material storage tank (1), a reaction liquid intermediate tank (2), a reaction solvent storage tank (3), a first raw material premixing tank (4), a second raw material premixing tank (5) and a second raw material gas cylinder (7); The reaction reflux system comprises a main reaction tube (8), a primary buffer tank (10), a secondary buffer tank (12) and a salt separation system; The salt separation system comprises a primary separator (9) and a secondary separator (11), wherein the primary separator (9) and the secondary separator (11) are both hydrocyclones, and the overflow pipes (905, 1105) of the hydrocyclones are both provided with guide grids (910) and rotating components (906, 1106); A threaded tube (920) is rotatably provided on the guide grid (910), a rotating shaft (930) is rotatably provided on the primary separator (9), the rotating shaft (930) is threadedly connected to the threaded tube (920), the rotating shaft (930) is fixedly connected to the rotating component (906), a plug-in block (911) is slidably provided on the guide grid (910), a slot (921) is provided on the threaded tube (920), and the plug-in block (911) is plugged into and matched with the slot (921); A sliding pin (912) is slidably provided on the plug-in block (911), a second spring (914) is provided between the sliding pin (912) and the plug-in block (911), and two ends of the second spring (914) are fixedly connected to the sliding pin (912) and the plug-in block (911), respectively; A first spring (913) is provided between the sliding pin (912) and the guide grid plate (910), and two ends of the first spring (913) are fixedly connected to the sliding pin (912) and the guide grid plate (910), respectively; A lifting ring (950) is slidably provided on the primary separator (9), a lifting rod (951) is fixedly provided on the lifting ring (950), an inclined groove (952) is provided on the lifting rod (951), and the sliding pin (912) is plugged into and matched with the inclined groove (952); A rotating frame (940) is fixedly provided on the rotating shaft (930), a rotating ring (941) is slidably provided on the rotating frame (940), the rotating ring (941) is rotatably connected to the lifting ring (950), a centrifugal rod (942) is slidably provided on the rotating frame (940), a steel wire rope (944) is provided between the centrifugal rod (942) and the rotating ring (941), and two ends of the steel wire rope (944) are fixedly connected to the centrifugal rod (942) and the rotating ring (941), respectively; A third spring (943) is provided between the rotating ring (941) and the rotating frame (940), and two ends of the third spring (943) are fixedly connected to the rotating ring (941) and the rotating frame (940), respectively.

2. The device for continuous liquid phase production of low-salt, high-concentration aminosilane according to claim 1, characterized in that: The first raw material storage tank (1) contains a first raw material, which is one of ammonia, dimethylamine, methylethylamine, diethylamine, diisopropylamine, and tert-butylamine. When the first raw material is in liquid form, the first raw material storage tank (1) is used for storage, and when the first raw material is in gaseous form, the first raw material gas cylinder (6) is used for storage. The second raw material gas cylinder (7) contains a second raw material, and the second raw material is one of monochlorosilane and dichlorosilane.

3. The device for continuous liquid phase production of low-salt, high-concentration aminosilane according to claim 2, characterized in that: The feed ratio of the first raw material to the second raw material is a chemical reaction equivalent ratio of 1.0 to 1.2:

1.

4. The device for continuous liquid phase production of low-salt, high-concentration aminosilane according to claim 1, characterized in that: The raw material feeding system further comprises a multi-point high-frequency sampling pipeline (504) for feeding the second raw material, and the number of sampling tubes in the sampling pipeline (504) is 4 to 20, which are radially distributed around the main reaction tube (8), and the sampling tube for the second raw material is at the rear end of the first raw material sampling tube.

5. The device for continuous liquid phase production of low-salt, high-concentration aminosilane according to claim 1, characterized in that: The main reaction tube (8) has an inner diameter of 0.02-0.3 m and a length of 1-10 m. The inner wall is lined with polytetrafluoroethylene. The main reaction tube (8) is a jacketed reaction tube, and the temperature inside the main reaction tube (8) is -10-20°C.

6. The device for continuous liquid phase production of low-salt, high-concentration aminosilane according to claim 1, characterized in that: The bottoms of the primary separator (9) and the secondary separator (11) are both provided with a salt slag buffer chamber (907, 1107) and a salt slag storage tank (908, 1108) controlled by dual pneumatic valves.

7. The device for continuous liquid phase production of low-salt, high-concentration aminosilane according to claim 1, characterized in that: The rotating component (906) located on the first-stage separator (9) has a tapered section angle of 10 to 20 degrees, and the rotating component (1106) located on the second-stage separator (11) has a tapered section angle of 7 to 15 degrees. The rotating components (906, 1106) are gradually narrowed from the outside to the inside, and the connection between the rotating components (906, 1106) and the rotating shaft (930) is tapered.

8. A method for continuous liquid-phase production of low-salt, high-concentration aminosilane, the method being implemented based on the apparatus for continuous liquid-phase production of low-salt, high-concentration aminosilane according to any one of claims 1 to 7, the method comprising: S1: solvent perfusion of the reaction pipeline; S2: raw material premixing; S3: continuous feed reaction; S4: Product extraction.

Images