High-pressure continuous flow in-situ reaction device and sampling method

Abstract

The invention discloses a high-pressure continuous flow in-situ reaction device which comprises a nuclear magnetic tube and a nuclear magnetic tube cap body which are in threaded connection, the nuclear magnetic tube cap body is provided with a first channel, a second channel and a third channel, the first channel, the second channel and the third channel are communicated through a penetrating channel, and the penetrating channel is communicated with a nuclear magnetic tube fixing hole through a fourth channel. The top end of the first channel is connected with a first port of the three-way valve through the first hose, the bottom end of the second hose is inserted from the second channel, penetrates through the nuclear magnetic tube cap body and extends to the bottom of the nuclear magnetic tube, the second hose is in sealed connection with the second channel, the top end of the second hose is connected with a second port of the three-way valve, and a third port of the three-way valve is connected with an air source. The third channel is connected with one end of a back pressure valve through a third hose, and the other end of the back pressure valve is connected with an air outlet pipeline. The invention further discloses a high-pressure continuous flow in-situ reaction sampling method, and continuous flow in-situ reaction sampling in the nuclear magnetic spectrometer is achieved.

Description

Technical Field

[0001] The present invention belongs to the field of nuclear magnetic resonance experimental technology and relates to a high-pressure continuous flow in-situ reaction device and a high-pressure continuous flow in-situ reaction sampling method. The present invention is suitable for in-situ polarization induction and observation of parahydrogen induced hyperpolarization technology under high-pressure conditions in nuclear magnetic resonance polarization technology. The present invention is also suitable for high-field nuclear magnetic resonance research scenarios such as heterogeneous catalysis, in-situ high-pressure reaction monitoring, and online flow chemistry, and realizes real-time monitoring and analysis of high-pressure reaction systems. Background Art

[0002] In modern chemical research, Nuclear Magnetic Resonance (NMR) technology, with its non-destructive and high-resolution characteristics, plays a core role in the analysis of chemical reaction mechanisms and the dynamic monitoring of reaction processes. However, its inherent disadvantage of low intrinsic sensitivity has greatly limited its application. Hyperpolarization technology can directly disrupt the distribution of atomic nuclei in the thermal equilibrium state, obtain a huge distribution number difference, and achieve an order of magnitude improvement in sensitivity. Parahydrogen-induced hyperpolarization (PHIP) is one of the important hyperpolarization techniques in NMR technology. This technology uses parahydrogen molecules as a polarization source. The core mechanism of this technology is to involve the polarization source parahydrogen molecules in the catalytic hydrogenation reaction, while maintaining the spin correlation between hydrogen atoms, breaking the symmetry between them, thereby breaking the Boltzmann distribution limitation under thermal equilibrium conditions, significantly improving the polarization intensity of the NMR signal, and effectively solving the problem of low sensitivity of traditional NMR technology.

[0003] PHIP technology primarily relies on catalytic hydrogenation to achieve polarization enhancement in the target system. This process often involves high-pressure reaction conditions and a continuous-flow catalytic reaction system. High pressure can significantly increase hydrogen solubility, accelerate the kinetics of catalytic hydrogenation, and greatly increase the density of polarized molecules, thereby increasing the PHIP signal enhancement factor. A continuous-flow system, on the other hand, maintains a dynamic, ongoing reaction process, maintaining the continuous output of polarization within the system. It also dynamically maintains the reactant concentration gradient, ensuring the hydrogenation reaction proceeds efficiently and continuously under high pressure.

[0004] However, the construction of a high-pressure continuous flow system faces multiple insurmountable technical bottlenecks. From the perspective of the structure and performance of the sealing components, traditional NMR tube caps are generally made of polytetrafluoroethylene or rubber. Their sealing design principle is based on a simple extrusion seal under static pressure, which can only meet the needs of normal pressure or low negative pressure environments. When the pressure rises, due to the limitations of the mechanical properties of the material (such as polytetrafluoroethylene's tendency to creep under high pressure and rubber materials experiencing stress relaxation), the probability of seal failure rises sharply, causing the seal to fail. In addition, existing NMR tube caps lack a dynamic pressure regulation mechanism and cannot achieve adaptive pressure control during the experiment. This makes high-pressure reactions at risk of pressure loss, which may cause leakage in the reaction system or even damage to the equipment, seriously threatening experimental safety and data accuracy.

[0005] During NMR observations, the sample is exposed to a high magnetic field. Maintaining sample stability is crucial to maintaining magnetic field uniformity. During in-situ high-pressure reactions, particularly when observing liquid samples, gas is continuously bubbled into the NMR tube through an inlet hose (with its outlet below the liquid level). Bubbling is terminated after the reaction, and NMR signal acquisition can only begin after the liquid level stabilizes. However, in actual operation, small fluctuations in the air pressure within the tube can occur due to unstable pressure control, slow closure, and air leaks. This can lead to difficulties in stabilizing the sample under observation and severely interfere with actual observations. The key to these problems lies in the inequality between the gas pressure in the inlet hose and the liquid surface pressure. For example, after the gas supply is terminated, if the gas pressure in the inlet hose is greater than the liquid surface pressure, the pressure difference will force the gas to continue to bubble into the NMR tube, disturbing the sample in the tube and making the liquid surface unstable, thereby affecting the sampling stability and data accuracy of the NMR spectrometer. If the gas pressure in the inlet hose is less than the liquid surface pressure, the pressure difference will force the liquid in the tube to flow back through the inlet hose. The liquid is sucked into the inlet channel, causing the liquid level in the NMR tube detection area to drop, reducing the sample within the sensing range of the NMR spectrometer probe coil, and seriously interfering with the sensitivity of the in-situ detection. Therefore, throughout the PHIP reaction and NMR detection process, pressure stability is crucial to maintaining the liquid level, avoiding bubbling interference, and improving signal reliability. Summary of the Invention

[0006] The purpose of the present invention is to address the above-mentioned problems existing in the prior art and to provide a high-pressure continuous flow in-situ reaction device and a high-pressure continuous flow in-situ reaction sampling method.

[0007] The present invention mainly achieves the above-mentioned purpose through the following technical means:

[0008] A high-pressure continuous-flow in-situ reaction device comprises a nuclear magnetic tube and a nuclear magnetic tube cap. The nuclear magnetic tube cap is provided with a first channel, a second channel, and a third channel arranged in parallel. The bottom ends of the first channel, the second channel, and the third channel are all connected to a through channel provided in the nuclear magnetic tube cap. The through channel is connected to a nuclear magnetic tube fixing hole through a fourth channel. The nuclear magnetic tube fixing hole is connected to the top of the nuclear magnetic tube. The top of the first channel is connected to a first port of a three-way valve through a first hose. A second hose runs through the second channel, the through channel, the fourth channel, and the nuclear magnetic tube fixing hole. The outer wall of the second hose is sealed from the inner wall of the second channel. The top of the second hose is connected to the second port of the three-way valve. The bottom end of the second hose extends to the bottom of the nuclear magnetic tube. The third port of the three-way valve is connected to a gas source. The third channel is connected to one end of a back pressure valve through the third hose. The other end of the back pressure valve is connected to an air outlet pipe.

[0009] The second hose is switched to be connected to the gas source or to the first hose through a three-way valve.

[0010] The inner diameters of the fourth channel and the nuclear magnetic tube fixing hole are larger than the outer diameter of the second hose.

[0011] The inner wall of the nuclear magnetic tube fixing hole is provided with a fixed internal thread, and the outer wall of the top of the nuclear magnetic tube is provided with a nuclear magnetic tube fixed external thread, and the fixed internal thread is threadedly connected with the nuclear magnetic tube fixed external thread.

[0012] A sealing rubber ring is provided in the fixing hole of the nuclear magnetic tube. When the top of the nuclear magnetic tube is screwed into the fixing hole of the nuclear magnetic tube, the top tube opening of the nuclear magnetic tube is tightly against the sealing rubber ring.

[0013] The bottom end of the first hose, the upper part of the second hose, and the bottom end of the third hose are sealed in the hose channels of the corresponding sealing screws, and the top end of the first channel, the top end of the second channel, and the top end of the third channel are sealed and connected to the corresponding sealing screws respectively.

[0014] The inner walls of the first channel, the second channel and the third channel are all provided with internal channel threads, and the bottom ends of the first channel, the second channel and the third channel are all provided with channel extrusion parts. The sealing screw includes a screw head, an external thread part and a screw extrusion part connected in sequence from top to bottom, and the external thread part is threadedly connected to the internal channel thread.

[0015] A high-pressure continuous flow in-situ reaction sampling method, using the above-mentioned high-pressure continuous flow in-situ reaction device, comprises the following steps: Step 1: Installation of high-pressure continuous flow in-situ reaction device; Insert the bottom end of the first hose, the upper part of the second hose, and the bottom end of the third hose into the hose channels of the corresponding sealing screws, screw the first channel, the second channel, and the third channel on the nuclear magnetic tube cap into the corresponding sealing screws respectively, connect the top end of the first hose to the first port of the three-way valve, and the second hose through the second channel, the through channel, the fourth channel, and the nuclear magnetic tube fixing hole. Connect the top end of the second hose to the second port of the three-way valve, and connect the third port of the three-way valve to the gas source. Connect the top end of the third hose to one end of the back pressure valve, and connect the other end of the back pressure valve to the gas outlet pipe. After loading the liquid or solid reactant sample into the nuclear magnetic tube, connect the nuclear magnetic tube fixing hole to the top end of the nuclear magnetic tube, and extend the bottom end of the second hose to the bottom of the nuclear magnetic tube. Finally, tighten the sealing screws. Step 2: Place the NMR tube in the probe detection area of ​​the NMR spectrometer, ensuring that the NMR tube is in the center of the detection coil; Step 3: Regulate the three-way valve to connect the gas source and the second hose, introduce gas into the nuclear magnetic tube, control the pressure in the nuclear magnetic tube to reach the set target pressure of the back pressure valve, and turn on the back pressure valve. After the reaction is completed, the reacted gas passes through the third hose connected to the third channel to reach the back pressure valve and is discharged from the back pressure valve to ensure that the pressure in the nuclear magnetic tube is stable. At this time, a continuous flow state under high pressure is maintained; after the reaction is completed, adjust the three-way valve so that the first channel is connected to the second hose, and close the gas source; wait until the bubbling of the nuclear magnetic tube stops, start the nuclear magnetic resonance spectrometer, obtain the nuclear magnetic resonance signal in real time, and obtain in-situ sampling of the reaction in the high-pressure state of the nuclear magnetic tube; Step 4. After the sampling is completed, slowly adjust the set pressure of the back pressure valve. The high-pressure gas in the NMR tube is slowly depressurized through the back pressure valve. When the pressure in the NMR tube drops to normal pressure, the pressure relief is completed.

[0016] Compared with the prior art, the present invention has the following beneficial effects:

[0017] 1. The device of the present invention is provided with multiple independent channels on the nuclear magnetic tube cap, and each channel has a clear function. The through channel is used to connect the first channel, the second channel, the third channel and the fourth channel. The first channel serves as a pressure-stabilizing channel. After the reaction is completed, the three-way valve is used to stabilize the internal pressure of the system and maintain a stable liquid level. The second and fourth channels are used to pass through the second hose to accurately introduce the gas required for the reaction. The third channel is used to discharge the gas after the reaction to maintain the continuous flow of gas in the device. The multiple channels cooperate with each other to meet the refined requirements of different experiments for gas flow and pressure control.

[0018] 2. The introduction of the pressure-stabilizing channel in the present invention can quickly adjust the system pressure at the end of the reaction, prevent the liquid level fluctuation caused by continuous bubbling at the air inlet end, and effectively avoid problems such as back suction and liquid withdrawal caused by excessive internal pressure, thereby ensuring that the liquid level in the nuclear magnetic resonance tube is always within the sensing area of ​​the nuclear magnetic resonance spectrometer probe, thereby improving the stability and accuracy of signal acquisition.

[0019] 3. The threaded fit between the NMR tube and the NMR cap, and the threaded fit between the sealing screw and the NMR cap, ensures that the NMR tube has good sealing performance under high pressure. By setting up a back pressure valve and a three-way valve, the sealing performance and pressure regulation capability of the reaction sampling tube are synergistically guaranteed, allowing the catalytic reaction to operate stably under high pressure.

[0020] 4. The present invention is equipped with a sealing rubber ring at the connection between the nuclear magnetic tube fixing hole and the nuclear magnetic tube. The sealing rubber ring is elastically deformed under pressure during the thread tightening process, fully filling the tiny gap between the contact interfaces, effectively preventing high-pressure gas leakage, and ensuring experimental safety and data reliability.

[0021] 5. The experiment is easy to operate. By controlling the gas source and adjusting the three-way valve, continuous flow and real-time sampling of the in-situ reaction can be achieved, which significantly improves the experimental efficiency. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the following briefly introduces the drawings required for describing the embodiments.

[0023] Figure 1 This is a schematic structural diagram of the high-pressure continuous flow in-situ reaction device of the present invention;

[0024] Figure 2 Schematic diagram of the structure of the nuclear magnetic tube cap;

[0025] Figure 3 This is a top view of the NMR tube cap;

[0026] Figure 4 Schematic diagram of the structure of the nuclear magnetic tube;

[0027] Figure 5 Schematic diagram of the structure of the sealing rubber ring;

[0028] Figure 6 It is a structural diagram of the sealing screw;

[0029] Among them, 1-NMR tube cap, 2-first channel, 3-second channel, 4-third channel, 5-channel internal thread, 6-NMR tube fixing hole, 7-fixed internal thread, 8-sealing rubber ring, 9-through channel, 10-NMR tube, 11-fourth channel, 12-NMR tube fixed external thread, 13-sealing screw, 14-hose channel, 15-external thread part, 16-three-way valve, 17-back pressure valve, 18-screw extrusion part, 19-channel extrusion part, 1101-first hose, 1102-second hose, 1103-third hose. Specific implementation plan

[0030] In order to facilitate those skilled in the art to understand and implement the present invention, the present invention is further described in detail below in conjunction with embodiments. It should be understood that the embodiments described herein are only used to illustrate and explain the present invention and are not used to limit the present invention.

[0031] Example 1:

[0032] like Figure 1 As shown, a high-pressure continuous flow in-situ reaction device includes a nuclear magnetic tube 10, a nuclear magnetic tube cap 1 is fixedly provided on the top of the nuclear magnetic tube 10, and a first channel 2, a second channel 3 and a third channel 4 are provided on the nuclear magnetic tube cap 1 in parallel. The bottom ends of the first channel 2, the second channel 3 and the third channel 4 are all connected to a through channel 9 provided in the nuclear magnetic tube cap 1, and the through channel 9 is connected to the nuclear magnetic tube fixing hole 6 through a fourth channel 11. The nuclear magnetic tube fixing hole 6 is connected to the top of the nuclear magnetic tube 10, and the top of the first channel 2 is connected to the first port of the three-way valve 16 through a first hose 1101. The second hose 1102 passes through the second channel 3, the channel 9, the fourth channel 11, and the nuclear magnetic tube fixing hole 6. The outer wall of the second hose 1102 is sealed against the inner wall of the second channel 3. The top of the second hose 1102 is connected to the second port of the three-way valve 16. The bottom end of the second hose 1102 extends to the bottom of the nuclear magnetic tube 10. The inner diameters of the fourth channel 11 and the nuclear magnetic tube fixing hole 6 are larger than the outer diameter of the second hose 1102. The third port of the three-way valve 16 is connected to the gas source. The third channel 4 is connected to one end of the back pressure valve 17 through the third hose 1103. The other end of the back pressure valve 17 is connected to the gas outlet pipe.

[0033] The second hose 1102 sealedly connected to the second channel 3 serves as an air inlet channel. When the three-way valve 16 is adjusted to connect the gas source with the second hose 1102, the input gas of the gas source enters the nuclear magnetic tube 10 from the second hose 1102; when the three-way valve 16 is adjusted to connect the first hose 1101 and the second hose 1102, the interior of the nuclear magnetic tube 10 is connected in sequence through the nuclear magnetic tube fixing hole 6, the fourth channel 11, the through channel 9, the first channel 2, the first hose 1101 and the second hose 1102, so that the pressure inside the second hose 1102 is consistent with the internal pressure of the nuclear magnetic tube 10, thereby solving the problem of The problem of the gas pressure in the second hose 1102 being unequal to the liquid surface pressure in the NMR tube 10 (when the NMR tube contains liquid reactants) is solved. Since the inner diameters of the fourth channel 11 and the NMR tube fixing hole 6 are larger than the outer diameter of the second hose 1102, the reacted gas passes through the NMR tube fixing hole 6, the fourth channel 11, and the through-channel 9 in sequence, and then enters the third channel 4 (during the reaction, the second hose 1102 is connected to the gas source, and the gas entering the first channel 2 is intercepted at the three-way valve 16). The third channel 4 serves as a gas outlet channel and is connected to the back-pressure valve 17. The configuration of the back-pressure valve 17 can ensure the stable output of the reacted gas.

[0034] In some embodiments, a fixed internal thread 7 is provided on the inner wall of the nuclear magnetic tube fixing hole 6, and a nuclear magnetic tube fixed external thread 12 is provided on the outer wall of the top of the nuclear magnetic tube 10. The fixed internal thread 7 is threadedly connected to the nuclear magnetic tube fixed external thread 12. Through the above arrangement, the inner wall of the nuclear magnetic tube fixing hole 6 is closely attached to the outer wall of the nuclear magnetic tube 10, ensuring the sealing of the connection and ensuring the connection stability and pressure resistance of the two under high-pressure operation.

[0035] Furthermore, a sealing rubber ring 8 is provided in the NMR tube fixing hole 6. When the top of the NMR tube 10 is screwed into the NMR tube fixing hole 6, the top end of the NMR tube 10 tightly contacts the sealing rubber ring 8, thereby achieving a sealed connection between the NMR tube 10 and the NMR tube fixing hole 6. The sealing rubber ring 8 is used to elastically deform under pressure during the thread tightening process, fully filling the tiny gap between the contact interface and forming an efficient airtight barrier. In this embodiment, the sealing rubber ring 8 is an O-ring.

[0036] Furthermore, the central axis of the second channel 3 and the central axis of the fourth channel 11 coincide with the central axis of the nuclear magnetic tube 10, so that the second hose 1102 is located on the central axis of the nuclear magnetic tube 10, making the insertion of the second hose 1102 more convenient.

[0037] Since the nuclear magnetic tube 10 operates in a high-pressure environment, sealing treatments must be performed between the top of the first channel 2 and the bottom of the first hose 1101, between the second channel 3 and the second hose 1102, and between the top of the third channel 4 and the bottom of the third hose 1103, which is achieved by using sealing screws 13.

[0038] The inner walls of the first channel 2, the second channel 3, and the third channel 4 are each provided with internal channel threads 5. The bottom ends of the first, second, and third channels 2, 3, and 4 are each provided with a channel extrusion portion 19. The sealing screw 13 comprises, from top to bottom, a screw head, an externally threaded portion 15, and a screw extrusion portion 18, which are sequentially connected. The externally threaded portion 15 is threadedly connected to the internal channel threads 5. The hose channel 14 passes through the screw head, externally threaded portion 15, and screw extrusion portion 18. The bottom end of the first hose 1101, the top of the second hose 1102, and the bottom end of the third hose 1103 are respectively disposed in the hose channels 14 of the corresponding sealing screws 13. The first, second, and third channels 2, 3, and 4 are each sealed to the corresponding sealing screws 13 through threaded connections. When the first channel 2, the second channel 3 and the third channel 4 are screwed into the corresponding sealing screws 13, the channel extrusion portion 19 squeezes the screw extrusion portion 18, so that the bottom end of the hose channel 14 becomes narrower, thereby achieving sealing between the first hose 1101, the second hose 1102, and the third hose 1103 and the corresponding sealing screws 13; thereby achieving sealed communication between the bottom end of the first hose 1101 and the bottom end of the third hose 1103 and the top end of the first channel 2 and the top end of the third channel 4, and achieving a sealed connection between the upper outer wall of the second hose 1102 and the inner wall of the second channel 3.

[0039] When sealing the hoses (the first hose 1101 , the second hose 1102 , and the third hose 1103 ) and the hose channel 14 , the channel pressing portion 19 may not be provided, and the inner diameter of the hose channel 14 may be gradually reduced from top to bottom.

[0040] In this embodiment, the sealing screw 13 is made of PEEK (polyetheretherketone).

[0041] Furthermore, the outer diameter of the nuclear magnetic tube 10 is 10 mm or 5 mm. The nuclear magnetic tube 10 can accommodate liquid or solid samples and is suitable for various in-situ reaction systems. It can also be replaced with other sizes according to specific experimental requirements.

[0042] The present invention is designed to provide a first channel 2, a second channel 3, and a third channel 4 on the nuclear magnetic tube cap 1, and to thread the nuclear magnetic tube cap 1 to the nuclear magnetic tube 10, so as to achieve precise gas delivery, high-pressure control, and in-situ sampling of the nuclear magnetic tube 10 in the nuclear magnetic resonance magnet. In terms of the dynamic pressure regulation mechanism, the present invention can adaptively regulate the pressure by adjusting the three-way valve 16 and setting the back pressure valve 17, thereby solving the problem of unstable pressure during the reaction, ensuring the dynamic balance of the pressure in the reaction system, and effectively ensuring experimental safety and data accuracy. In terms of sampling function, for example, in the catalytic hydrogenation reaction in the PHIP technology, samples in the reaction system can be collected in real time for nuclear magnetic resonance detection, providing a powerful tool for studying the reaction process and reaction mechanism, and meeting the needs of continuous flow reaction and nuclear magnetic detection under high-pressure environment.

[0043] Example 2:

[0044] A high-pressure continuous flow in-situ reaction sampling method, using the high-pressure continuous flow in-situ reaction apparatus described in Example 1, comprises the following steps:

[0045] Step 1: Installation of high-pressure continuous flow in-situ reaction device; Insert the bottom end of the first hose 1101, the upper part of the second hose 1102, and the bottom end of the third hose 1103 into the hose channels 14 of the corresponding sealing screws 13. Screw the first channel 2, the second channel 3, and the third channel 4 on the nuclear magnetic tube cap 1 into the corresponding sealing screws 13, respectively. Connect the top end of the first hose 1101 to the first port of the three-way valve 16. The second hose 1102 passes through the second channel 3, the channel 9, the fourth channel 11, and the nuclear magnetic tube fixing hole 6. Connect the top end of the second hose 1102 to the second port of the three-way valve 16. Connect the third port of the three-way valve 16 to the gas source (parahydrogen or other gas supply device). Connect the top end of the third hose 1103 to one end of the back pressure valve 17. The other end of the back pressure valve 17 is connected to the gas outlet pipe. The NMR tube 10 is a 5mm NMR tube or a 10mm NMR tube. After the liquid or solid reactant sample is loaded into the NMR tube 10, the NMR tube fixing hole 6 is connected to the top of the NMR tube 10, and the bottom end of the second hose 1102 is extended to the bottom of the NMR tube 10. Finally, each sealing screw 13 is tightened.

[0046] Step 2: Place the NMR tube 10 at the probe detection position in the NMR spectrometer, ensuring that the NMR tube 10 is at the center of the detection coil;

[0047] Step 3, obtaining continuous flow in-situ reaction sampling in the high-pressure state of the nuclear magnetic resonance tube; The three-way valve 16 is adjusted to connect the gas source with the second hose 1102, and other gases such as parahydrogen are introduced into the nuclear magnetic tube 10. The pressure in the nuclear magnetic tube 10 is controlled to reach the set target pressure of the back pressure valve 17. The back pressure valve 17 is turned on. After the reaction is completed, the reacted gas reaches the back pressure valve 17 through the third hose 1103 connected to the third channel 4 and is discharged from the back pressure valve 17 to ensure that the pressure in the nuclear magnetic tube 10 is stable and a continuous flow state is maintained at this time. After the reaction is completed, the three-way valve 16 is adjusted to connect the first channel 2 with the second hose 1102, and the gas source is closed. After the bubbling of the nuclear magnetic tube 10 stops, the nuclear magnetic resonance spectrometer is started, and the nuclear magnetic resonance signal is acquired in real time to obtain continuous flow in-situ reaction sampling in the high-pressure state of the nuclear magnetic tube 10 (the probe of the nuclear magnetic resonance spectrometer magnet is at normal pressure).

[0048] Step 4: After the sampling is completed, the set pressure of the back pressure valve 17 is slowly adjusted, and the high-pressure gas in the nuclear magnetic tube 10 is slowly depressurized through the back pressure valve 17. After the pressure in the nuclear magnetic tube 10 drops to normal pressure, the depressurization is completed.

[0049] It should be noted that the embodiments described herein are merely illustrative of the spirit of the present invention. Persons skilled in the art may make various modifications, additions, or substitutions to the described embodiments without departing from the spirit of the present invention or exceeding the scope of the appended claims.

Claims

1. A high-pressure continuous flow in-situ reaction device, comprising a nuclear magnetic resonance tube (10), characterized in that: The nuclear magnetic tube cap body (1) is provided with a first channel (2), a second channel (3) and a third channel (4) arranged in parallel on the nuclear magnetic tube cap body (1); the bottom ends of the first channel (2), the second channel (3) and the third channel (4) are all connected to a through channel (9) arranged in the nuclear magnetic tube cap body (1); the through channel (9) is connected to the nuclear magnetic tube fixing hole (6) through the fourth channel (11); the nuclear magnetic tube fixing hole (6) is connected to the top of the nuclear magnetic tube (10); the top end of the first channel (2) is connected to the first port of the three-way valve (16) through the first hose (1101); the third channel (4) is connected to the first port of the three-way valve (16) through the fourth hose (1101); The second hose (1102) passes through the second channel (3), the channel (9), the fourth channel (11), and the nuclear magnetic tube fixing hole (6). The outer wall of the second hose (1102) is sealed with the inner wall of the second channel (3). The top end of the second hose (1102) is connected to the second port of the three-way valve (16). The bottom end of the second hose (1102) extends to the bottom of the nuclear magnetic tube (10). The third port of the three-way valve (16) is connected to the gas source. The third channel (4) is connected to one end of the back pressure valve (17) through the third hose (1103). The other end of the back pressure valve (17) is connected to the gas outlet pipe.

2. A high-pressure continuous flow in-situ reaction device according to claim 1, characterized in that: The second hose (1102) is switched to be connected to the gas source or to be connected to the first hose (1101) via a three-way valve.

3. A high-pressure continuous flow in-situ reaction device according to claim 2, characterized in that: The inner diameters of the fourth channel (11) and the nuclear magnetic tube fixing hole (6) are greater than the outer diameter of the second hose (1102).

4. The high-pressure continuous flow in-situ reaction device according to claim 1, characterized in that: A fixed internal thread (7) is provided on the inner wall of the nuclear magnetic tube fixing hole (6), and a nuclear magnetic tube fixed external thread (12) is provided on the outer wall of the top of the nuclear magnetic tube (10). The fixed internal thread (7) is threadedly connected to the nuclear magnetic tube fixed external thread (12).

5. The high-pressure continuous flow in-situ reaction device according to claim 1, characterized in that: A sealing rubber ring (8) is provided in the nuclear magnetic tube fixing hole (6). When the top of the nuclear magnetic tube (10) is screwed into the nuclear magnetic tube fixing hole (6), the top end of the nuclear magnetic tube (10) is tightly against the sealing rubber ring (8).

6. A high-pressure continuous flow in-situ reaction device according to claim 3, characterized in that: The bottom end of the first hose (1101), the upper part of the second hose (1102), and the bottom end of the third hose (1103) are sealed in the hose channels (14) of the corresponding sealing screws (13), and the top ends of the first channel (2), the second channel (3), and the third channel (4) are sealed and connected to the corresponding sealing screws (13), respectively.

7. A high-pressure continuous flow in-situ reaction device according to claim 6, characterized in that: The inner wall of the first channel (2), the inner wall of the second channel (3) and the inner wall of the third channel (4) are all provided with channel internal threads (5), and the bottom ends of the first channel (2), the second channel (3) and the third channel (4) are all provided with channel extrusion parts (19). The sealing screw (13) includes a screw head, an external thread part (15) and a screw extrusion part (18) connected in sequence from top to bottom, and the external thread part (15) is threadedly connected to the channel internal threads (5).

8. A high-pressure continuous flow in-situ reaction sampling method, using the high-pressure continuous flow in-situ reaction device according to claim 6, characterized in that: The following steps are involved: Step 1: Installation of high-pressure continuous flow in-situ reaction device; Insert the bottom end of the first hose (1101), the upper part of the second hose (1102), and the bottom end of the third hose (1103) into the hose channels (14) of the corresponding sealing screws (13), and screw the first channel (2), the second channel (3), and the third channel (4) on the nuclear magnetic tube cap (1) into the corresponding sealing screws (13) respectively. The top end of the first hose (1101) is connected to the first port of the three-way valve (16), and the second hose (1102) passes through the second channel (3), the through channel (9), the fourth channel (11), and the nuclear magnetic tube fixing hole (6). The top end of the second hose (1102) is connected to the second port of the three-way valve (16), and the third port of the three-way valve (16) is connected to the gas source. The top end of the third hose (1103) is connected to one end of the back pressure valve (17), and the other end of the back pressure valve (17) is connected to the gas outlet pipe. After the liquid or solid reactant sample is loaded into the NMR tube (10), the NMR tube fixing hole (6) is connected to the top of the NMR tube (10), the bottom end of the second hose (1102) is extended to the bottom of the NMR tube (10), and finally, each sealing screw (13) is tightened; Step 2: Place the NMR tube (10) at the probe detection position in the NMR spectrometer, ensuring that the NMR tube (10) is at the center of the detection coil; Step 3, adjusting the three-way valve (16) to connect the gas source and the second hose (1102), and introducing gas into the nuclear magnetic tube (10), controlling the pressure in the nuclear magnetic tube (10) to reach the set target pressure of the back pressure valve (17), and the back pressure valve (17) is turned on. After the reaction is completed, the post-reaction gas reaches the back pressure valve (17) through the third hose (1103) connected to the third channel (4), and is discharged from the back pressure valve (17), ensuring that the pressure in the nuclear magnetic tube (10) is stable, and at this time, a continuous flow state under a high pressure state is maintained; after the reaction is completed, adjusting the three-way valve (16) so that the first channel (2) is connected to the second hose (1102), and closing the gas source; after the bubbling of the nuclear magnetic tube (10) is stopped, starting the nuclear magnetic resonance spectrometer, obtaining the nuclear magnetic resonance signal in real time, and obtaining the in-situ sampling of the reaction in the high pressure state of the nuclear magnetic tube (10); Step 4: After the sampling is completed, the set pressure of the back pressure valve (17) is slowly adjusted, and the high-pressure gas in the nuclear magnetic tube (10) is slowly depressurized through the back pressure valve (17). After the pressure in the nuclear magnetic tube (10) drops to normal pressure, the depressurization is completed.

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