A device and method for sample processing and fluid filling of a high-temperature and high-pressure sealed solid nuclear magnetic resonance rotor

Abstract

The present invention provides an apparatus and method for sample processing and fluid filling of a high-temperature, high-pressure sealed solid-state nuclear magnetic resonance rotor. The apparatus includes a fluid filler and an associated gas circuit system. The fluid filler comprises a first fluid filler housing, a second fluid filler housing, a rotor sample chamber mounting seat, and a portion for rotating a sealed rotor cap. The associated gas circuit system comprises a fluid source unit, a vacuum unit, a sample processing unit, a pressure detection unit, and a fluid outlet unit. The apparatus of the present invention can perform pre-sampling of samples within a high-temperature, high-pressure, in-situ sealed solid-state nuclear magnetic resonance rotor, fluid filling with a specific atmosphere and pressure, pre-reaction, adsorption, and in-situ rotor unsealing and sealing operations.

Description

Technical Field

[0001] The present invention relates to the field of in-situ solid-state nuclear magnetic resonance technology, and in particular to a device and method for sample processing and fluid filling of a high-temperature and high-pressure sealed solid-state nuclear magnetic resonance rotor. Background Art

[0002] In situ NMR characterization of samples under controlled atmosphere can provide important information about the structure, interactions, and reaction processes of relevant components in the system under real-world conditions. When the sample system contains solid-phase components, the solid-state NMR rotor loaded with the sample typically needs to be rotated at high speeds (several thousand hertz) within the NMR spectrometer's magnetic field, driven by airflow, to average out the various anisotropic interactions in the system and obtain high-resolution NMR spectra. This poses challenges for in situ solid-state NMR observations, especially under high-temperature and high-pressure conditions. Conventional solid-state NMR spectrometers and their accompanying solid-state NMR rotors are incapable of performing in situ studies at high temperatures and high pressures. To address this issue, Zhao Zhenchao and others at the Dalian Institute of Chemical Physics, Chinese Academy of Sciences, recently developed a threaded, high-temperature and high-pressure sealed in-situ solid-state NMR rotor (patent CN202111538058.8), suitable for use in Bruker's commercial solid-state NMR probes. This invention discloses an apparatus and method for sample preparation, fluid filling at a specific atmosphere and pressure, pre-reaction, and in-situ rotor unsealing and sealing before high-temperature and high-pressure solid-state NMR sampling. Summary of the Invention

[0003] In response to the technical problems raised above, a device and method for sample processing and fluid filling of a high-temperature and high-pressure sealed solid-state nuclear magnetic resonance rotor are provided.

[0004] The technical means adopted in the present invention are as follows:

[0005] A device for sample processing and fluid filling of a high-temperature, high-pressure sealed solid-state nuclear magnetic resonance rotor comprises a fluid filler and an air circuit system. The fluid filler comprises a fluid filler housing, a rotor sample cavity fixing seat, and a portion for rotating and sealing the rotor sealing cap. The fluid filler housing is connected to the air circuit system and consists of a first fluid filler housing and a second fluid filler housing connected to each other, forming a sealed receiving chamber therein.

[0006] The rotor sample chamber fixing seat is located in the accommodating chamber and includes a rotor sleeve and a rotor clamping nut for accommodating a high-temperature and high-pressure sealed rotor. The rotor sleeve is connected to the first fluid filler housing, and the rotor clamping nut is connected to the rotor sleeve. The rotor sample chamber fixing seat fixes the high-temperature and high-pressure sealed rotor sample chamber by extrusion. After the high-temperature and high-pressure sealed rotor is inserted into the rotor sleeve, the rotor clamping nut is screwed into the outside of the rotor sleeve through a thread, and the rotor sleeve is gradually squeezed by the top surface to bite the high-temperature and high-pressure sealed rotor, thereby fixing the high-temperature and high-pressure sealed rotor.

[0007] The part for rotating the sealing rotor sealing cap is connected to the second fluid filler housing and the high-temperature and high-pressure sealing rotor sealing cap. By rotating the part for rotating the sealing rotor sealing cap, the high-temperature and high-pressure sealing rotor sealing cap is driven to perform spiral motion, thereby unsealing or sealing the high-temperature and high-pressure sealing rotor.

[0008] Furthermore, when the window is not provided, a sealing groove is provided at the relative position of the first fluid filler housing and the second fluid filler housing, and a sealing ring is placed between the sealing grooves to achieve sealing;

[0009] Alternatively, sealing is achieved by providing a sealing surface on the connecting surface of the first fluid filler housing and the second fluid filler housing;

[0010] The sealing ring is made of a polymer rubber O-ring, a metal gasket or a graphite gasket.

[0011] Furthermore, when designing a window, one or more hollow windows are provided in the first or second fluid filler housing at a height parallel to the sealed connection between the high-temperature, high-pressure sealed rotor sealing cap and the sample chamber, allowing for observation of the relative position of the high-temperature, high-pressure sealed rotor sealing cap and the sample chamber. A matching hollow liner is placed within the fluid filler housing, with first sealing grooves positioned above and below the hollow liner. Second sealing grooves are positioned at corresponding locations within the first and second fluid filler housings, with a sealing ring positioned between the first and second sealing grooves. The rotor sample chamber mount is positioned within a transparent hollow liner made of a transparent material such as glass, quartz, or polycarbonate.

[0012] Furthermore, the central axis of the rotor sleeve is hollow for accommodating a cylindrical high-temperature and high-pressure sealed rotor; the upper portion of the rotor sleeve is tapered and has a plurality of small slits; the middle portion of the rotor sleeve is provided with an external thread for connection with a rotor sleeve nut; the lower portion of the rotor sleeve is connected to the first fluid filler housing by a concave-convex matching manner;

[0013] The rotor clamping nut is a hollow body with an internal thread, the top opening of which matches the upper part of the rotor sleeve, and the bottom is connected to the middle part of the rotor sleeve through a thread;

[0014] The rotor sleeve and the rotor clamping nut are both made of a material with a certain elasticity, and the material with a certain elasticity is plastic;

[0015] The high-temperature and high-pressure sealed rotor is an in-situ solid nuclear magnetic resonance rotor with threads that can perform high-temperature and high-pressure sealing.

[0016] Furthermore, the portion for rotating the sealing rotor cap is connected to the high-temperature and high-pressure sealing rotor cap via a transition piece, and the connecting portion is concave-convex matched, and the transition piece is a plastic piece, a graphite piece, or a piece of other materials;

[0017] Alternatively, the portion for rotating the sealing rotor cap is integrally connected to the high-temperature and high-pressure sealing rotor cap by concave-convex matching;

[0018] The main body portion of the sealing cap for rotating and sealing the rotor is made of a pressure-resistant material.

[0019] Furthermore, the portion for rotating the sealing rotor sealing cap is a mechanical arm structure, a magnetic coupler structure or a rotating sealing bearing structure;

[0020] The mechanical arm structure includes a first mechanical rod with a handle on the upper portion. The first mechanical rod passes through a small hole provided on the housing of the second fluid filler. The small hole is provided with an internal thread, which matches the external thread provided in the middle of the first mechanical rod. The first mechanical rod and the second fluid filler housing are sealed by a ferrule. By rotating the first mechanical rod, the high-temperature and high-pressure sealing rotor sealing cap is driven to perform spiral motion.

[0021] The magnetic coupling structure includes a magnetic coupling with a second mechanical rod, the second mechanical rod passing through a small hole provided on the housing of the second fluid filler; the magnetic coupling is sealed by welding to the housing of the second fluid filler, or by squeezing an O-ring through a ferrule;

[0022] The portion for rotating the sealing rotor seal cap may also be connected and sealed to the second fluid filler housing by means of a rotating sealing bearing;

[0023] The portion for rotating the sealing rotor sealing cap drives a mechanical rod passing through the second fluid filler housing to rotate, thereby driving the high-temperature and high-pressure sealing rotor sealing cap to perform spiral motion, thereby unsealing or sealing the high-temperature and high-pressure sealing rotor.

[0024] Furthermore, the fluid filler is placed as a whole on a fixed frame; a plurality of holes connected to the outside are opened on the outer shell of the fluid filler for connection with the gas system and for inserting wires connected to the thermocouple and the heating blanket; the holes connected to the gas system are sealed or fluid is introduced or vacuumed by the gas system; the holes for inserting the wires are sealed by a ferrule; the thermocouple and the heating blanket are placed around the high-temperature and high-pressure sealed rotor to achieve heating and temperature measurement of the high-temperature and high-pressure sealed rotor;

[0025] The first fluid filler housing and the second fluid filler housing are connected via a plurality of threaded structures; the first fluid filler housing and the second fluid filler housing are both made of sealable and pressure-resistant materials.

[0026] Furthermore, the gas circuit system includes a fluid source unit, a vacuum unit, a sample processing unit, a pressure detection unit and a fluid outlet unit;

[0027] The fluid source unit includes a required fluid source, a pressure reducing valve connected to the required fluid source, a first two-way valve connected to the pressure reducing valve, a cold trap connected to the first two-way valve, a first three-way valve connected to the cold trap, and a flow meter and a second two-way valve connected to the first three-way valve. The cold trap is filled according to experimental requirements and the fluid passing through it to purify the required fluid. The valve bodies of the first two-way valve and the second two-way valve are ball valves or needle valves.

[0028] The vacuum unit includes a third three-way valve and vacuum pumps of various stages connected to the third three-way valve;

[0029] The sample processing unit is used to connect the fluid filler to the gas circuit system;

[0030] The pressure detection unit includes a second three-way valve connected to the sample processing unit, and a vacuum gauge and a pressure gauge connected to the second three-way valve, and the second three-way valve is switched to measure the system pressure under negative pressure or positive pressure conditions;

[0031] The fluid outlet unit is connected to the atmosphere and is connected to the third three-way valve.

[0032] The present invention also provides a method for operating a device for sample processing and fluid filling of a high-temperature and high-pressure sealed solid-state nuclear magnetic resonance rotor, comprising the following steps:

[0033] Step 1: Assemble and connect the high-temperature and high-pressure sealed rotor, fluid filler and required gas path;

[0034] Step 2: First, degas the entire device to ensure that the device is clean; at this time, open all two-way valves, switch the third three-way valve to the vacuum unit, and switch the first and second three-way valves back and forth several times;

[0035] Step 3: After the device has been degassed for a period of time to reach the required vacuum for the experiment, the sealing cap of the rotating sealed rotor of the fluid filler can be rotated to open the high-temperature and high-pressure sealed rotor to degas the sample according to the experimental needs. If the experiment does not require degassing of the sample, the high-temperature and high-pressure sealed rotor can be opened after the required fluid atmosphere is introduced into the system.

[0036] Step 4: Fill the sample with fluid, adsorb, and pre-react according to experimental needs; at this time, fill the cold trap with the corresponding medium according to experimental needs to purify the required fluid, close the third three-way valve according to experimental needs, switch the second three-way valve to the vacuum gauge or pressure gauge according to the pressure range required for adsorption, open the required fluid source and pressure reducing valve, the first two-way valve, the first three-way valve, the second two-way valve, and the flow meter according to experimental needs, and introduce the fluid to the required pressure;

[0037] Step 5: After the required fluid is introduced, close the first three-way valve and the flow meter, and perform adsorption equilibrium or pre-reaction according to experimental requirements;

[0038] Step 6: After the pre-reaction or adsorption equilibrium is completed, the portion of the fluid filler used to rotate the sealing rotor sealing cap is rotated again to seal the high-temperature and high-pressure sealed rotor in situ, and then the third three-way valve is switched to the vacuum unit or the fluid outlet unit as needed;

[0039] Step 7: Open the fluid filler, take out the high-temperature and high-pressure sealed rotor and prepare for solid-state NMR sampling.

[0040] Compared with the prior art, the present invention has the following advantages:

[0041] 1. The device and method for sample processing and fluid filling of a high-temperature, high-pressure sealed solid-state nuclear magnetic resonance rotor provided by the present invention can realize the pretreatment of samples in a high-temperature, high-pressure in-situ sealed solid-state nuclear magnetic resonance rotor before sampling, fluid filling with a specific atmosphere and pressure, pre-reaction, adsorption, and in-situ unsealing and sealing of the rotor.

[0042] 2. The device and method for sample processing and fluid filling of a high-temperature and high-pressure sealed solid-state nuclear magnetic resonance rotor provided by the present invention have excellent airtightness, and all required experimental operations are highly strictly controllable.

[0043] 3. The device and method for sample processing and fluid filling of the high-temperature and high-pressure sealed solid nuclear magnetic resonance rotor provided by the present invention are not only suitable for the first filling of the fluid, but also suitable for subsequent fluid filling according to experimental needs.

[0044] Based on the above reasons, the present invention can be widely promoted in the fields of in-situ solid-state nuclear magnetic resonance and the like. BRIEF DESCRIPTION OF THE DRAWINGS

[0045] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings described below are some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative labor.

[0046] Figure 1 Schematic diagram of the robotic arm type fluid filling reactor of the present invention.

[0047] Figure 2 This is a cross-sectional view of the robotic arm type fluid filling reactor of the present invention.

[0048] Figure 3 Schematic diagram of the rotor sleeve of the rotor sample cavity fixing seat C of the present invention.

[0049] Figure 4 Schematic diagram of the rotor ferrule nut of the rotor sample chamber fixing seat C of the present invention.

[0050] Figure 5 This is a schematic diagram of the assembly of the rotor sample cavity fixing seat C of the present invention.

[0051] Figure 6 This is a cross-sectional view of the rotor sample cavity fixing seat C after assembly.

[0052] Figure 7 Schematic diagram of the gas circuit system related to the present invention.

[0053] In the figure: A, first fluid filler housing; B, second fluid filler housing; C, rotor sample chamber fixing seat; D, part for rotating sealed rotor sealing cap; 1, hollow window hole; 2, threaded structure; 3, sealing ring; 4, hollow lining; 5, high-temperature and high-pressure sealed rotor; 6, rotor sleeve; 7, rotor sleeve nut; 8, transition piece; 9, required fluid source; 10, cold trap; 11, flow meter; 12, vacuum gauge; 13, pressure gauge; 14, hole; 15, vacuum pumps at various levels; 16, fluid outlet unit; 17, location where the gas path system is connected to the fluid filler; V1, pressure reducing valve; V2, first two-way valve; V3, first three-way valve; V4, second three-way valve; V5, third three-way valve; V6, second two-way valve. DETAILED DESCRIPTION

[0054] It should be noted that, in the absence of conflict, the embodiments and features of the embodiments of the present invention can be combined with each other. The present invention will be described in detail below with reference to the accompanying drawings and in combination with the embodiments.

[0055] In order to make the purpose, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the drawings in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. The following description of at least one exemplary embodiment is actually only illustrative and is in no way intended to limit the present invention and its application or use. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0056] It should be noted that the terms used herein are only for describing specific embodiments and are not intended to limit the exemplary embodiments according to the present invention. As used herein, unless the context clearly indicates otherwise, the singular form is intended to include the plural form. In addition, it should be understood that when the terms "comprise" and / or "include" are used in this specification, they indicate the presence of features, steps, operations, devices, components and / or combinations thereof.

[0057] Unless otherwise specifically stated, the relative arrangement of the parts and steps, numerical expressions and numerical values set forth in these embodiments do not limit the scope of the present invention. At the same time, it should be clear that, for ease of description, the sizes of the various parts shown in the drawings are not drawn according to the actual proportional relationship. The technology, methods and equipment known to those of ordinary skill in the relevant art may not be discussed in detail, but in appropriate cases, the technology, methods and equipment should be considered as part of the authorization specification. In all examples shown and discussed here, any specific value should be interpreted as being merely exemplary and not as a limitation. Therefore, other examples of the exemplary embodiments may have different values. It should be noted that similar numbers and letters represent similar items in the following figures, and therefore, once an item is defined in one figure, it does not need to be further discussed in subsequent figures.

[0058] In the description of the present invention, it should be understood that the directions or positional relationships indicated by directional words such as "front, back, up, down, left, right", "horizontal, vertical, vertical, horizontal" and "top, bottom" are usually based on the directions or positional relationships shown in the accompanying drawings. They are only for the convenience of describing the present invention and simplifying the description. Unless otherwise specified, these directional words do not indicate or imply that the device or element referred to must have a specific direction or be constructed and operated in a specific direction. Therefore, they cannot be understood as limiting the scope of protection of the present invention: the directional words "inside and outside" refer to the inside and outside relative to the outline of each component itself.

[0059] For ease of description, spatially relative terms such as "above", "above", "on the upper surface of", "above", etc. may be used herein to describe the spatial positional relationship of a device or feature to other devices or features as shown in the figures. It should be understood that spatially relative terms are intended to include different orientations of the device in use or operation in addition to the orientation described in the figures. For example, if the device in the drawings is inverted, the device described as "above other devices or structures" or "above other devices or structures" will be positioned as "below other devices or structures" or "below their position devices or structures". Thus, the exemplary term "above" can include both "above" and "below". The device can also be positioned in other different ways (rotated 90 degrees or in other orientations), and the spatially relative descriptions used here are interpreted accordingly.

[0060] In addition, it should be noted that the use of terms such as "first" and "second" to limit components is only for the convenience of distinguishing the corresponding components. Unless otherwise stated, the above terms have no special meaning and therefore cannot be understood as limiting the scope of protection of the present invention.

[0061] like Figure 1-7 The present invention provides a device for sample processing and fluid filling of a high-temperature, high-pressure sealed solid-state nuclear magnetic resonance rotor, including a fluid filler and associated gas circuit system. The present invention discloses a fluid filler and associated gas circuit system for pre-sampling sample processing, fluid filling at a specific atmosphere and pressure, pre-reaction, and in-situ rotor unsealing and sealing of a high-temperature, high-pressure, in-situ sealed solid-state nuclear magnetic resonance rotor.

[0062] The fluid filler consists of a fluid filler housing, a rotor sample chamber holder C, and a portion D for rotating and sealing the rotor cap. The fluid filler housing is composed of a first fluid filler housing A and a second fluid filler housing B, forming an internal chamber. The associated gas circuit system comprises a fluid source unit (gas source unit), a vacuum unit, a sample processing unit, a pressure detection unit, and a fluid outlet unit. The device of the present invention can perform pre-sampling of samples within a high-temperature, high-pressure, in-situ sealed solid-state nuclear magnetic resonance rotor, fluid filling at a specific atmosphere and pressure, pre-reaction, adsorption, and in-situ rotor unsealing and sealing.

[0063] The first fluid filler housing A and the second fluid filler housing B are made of sealable and pressure-resistant materials such as metal.

[0064] Part A of the first fluid filler housing (or part B of the second fluid filler housing) can be constructed with one or more hollow windows 1 of any shape, parallel to the sealed connection between the high-temperature, high-pressure sealed rotor 5's sealing cap and the sample chamber. These windows 1, located on the fluid filler housing, facilitate observation of the relative position of the sealed rotor 5's sealing cap and the sample chamber. The hollow windows 1 can be of any shape and in any number.

[0065] When a hollow window 1 is designed on the first fluid filler housing part A (or the second fluid filler housing part B), a hollow liner 4 matching the housing is placed inside the fluid filler housing. The hollow liner 4 can be made of transparent materials such as glass, quartz, polycarbonate, etc.

[0066] In the hollow window 1 design, the first and second fluid filler housings A and B are partially connected by several threaded structures 2. The interior of the hollow liner 4 is sealed by sealing rings 3 squeezed into the sealing grooves between the first fluid filler housing A and the bottom of the hollow liner 4, and between the second fluid filler housing B and the top of the hollow liner 4. Specifically, first sealing grooves are provided on the top and bottom surfaces of the hollow liner 4, and second sealing grooves are also designed at corresponding locations on the first and second fluid filler housings A and B. A sealing ring 3 is placed between the first and second sealing grooves. The first and second sealing grooves are tapered or cylindrical grooves.

[0067] The material of the sealing ring 3 can be various polymer rubber O-rings, various metal gaskets, graphite gaskets, etc. The cross section of the sealing ring 3 can be circular, square or diamond-shaped, and the material is rubber, polytetrafluoroethylene plastic, gold, silver, copper or graphite.

[0068] The first fluid filler housing part A (or the second fluid filler housing part B) can also be designed without the hollow window hole 1. In this case, the relative movement of the rotor sealing cap and the sample chamber can be determined by the rotation of the rotor sealing cap part D used for rotating the seal.

[0069] When the first fluid filler housing A (or the second fluid filler housing B) is designed without a hollow window 1, the first and second fluid filler housings A and B are connected by a plurality of threaded structures 2. Sealing is achieved by squeezing a sealing ring 3 against a sealing groove on the connecting surface of the first and second fluid filler housings A and B, or by sealing surfaces provided on the connecting surfaces of the first and second fluid filler housings A and B. Specifically, sealing grooves are designed relative to each other between the first and second fluid filler housings A and B, with the sealing ring 3 positioned between the grooves. The sealing grooves are tapered or cylindrical grooves.

[0070] The material of the sealing ring 3 can be various polymer rubber O-rings, various metal gaskets, graphite gaskets, etc.

[0071] In the design without the hollow window 1 , the rotor sample cavity holder C is placed inside the first fluid filler housing A and the second fluid filler housing B. In the design with the hollow window 1 , the rotor sample cavity holder C is placed inside the transparent hollow liner 4 .

[0072] The rotor sample cavity fixing seat C is connected to the first fluid filler housing A in a concave-convex matching manner.

[0073] The rotor sample chamber fixing seat C is composed of a rotor sleeve 6 with external threads for accommodating a high-temperature and high-pressure sealed rotor 5, and a rotor clamping nut 7 with internal threads. The high-temperature and high-pressure sealed rotor 5 is a threaded in-situ solid-state nuclear magnetic resonance rotor capable of high-temperature and high-pressure sealing.

[0074] The rotor sleeve 6 and the rotor clamping sleeve nut 7 can be made of a material with a certain elasticity, such as plastic.

[0075] The central axis of the rotor sleeve 6 is hollow and is used to place the high-temperature and high-pressure sealed rotor 5; the upper part is conical and has several small slits to give it a certain degree of deformation ability; the middle part is provided with an external thread to facilitate connection with the rotor sleeve nut 7; the lower part is connected to the first fluid filler shell A through a concave-convex matching method.

[0076] The rotor clamping nut 7 is a hollow body with an internal thread, the top opening of which matches the upper part of the rotor sleeve 6, and the bottom is connected to the middle part of the rotor sleeve 6 through threads.

[0077] The rotor sample chamber holder C secures the cylindrical high-temperature, high-pressure sealed rotor 5 sample chamber by squeezing. Specifically, after inserting the high-temperature, high-pressure sealed rotor 5 into the appropriate position of the rotor sleeve 6, the rotor clamping nut 7 is threaded onto the outside of the rotor sleeve 6. The top surface gradually squeezes the rotor sleeve 6, thereby tightening the high-temperature, high-pressure sealed rotor 5 and securing it.

[0078] The main body of the portion D of the rotary rotor sealing cap is made of a pressure-resistant material such as metal. Its connection to the sealing cap of the high-temperature, high-pressure sealed rotor 5 can be achieved through a transition piece 8 (disposed between portion D and the sealing cap, and made of plastic, graphite, or other materials). The connecting portions can be matched with each other in the concave and convex portions. Alternatively, the portion D can be directly integrated and connected to the sealing cap of the high-temperature, high-pressure sealed rotor 5 with matching concave and convex portions. Rotating portion D of the rotary rotor sealing cap drives the sealing cap of the high-temperature, high-pressure sealed rotor 5 in spiral motion, thereby unsealing or sealing the high-temperature, high-pressure sealed rotor 5.

[0079] Portion D, which rotates the sealing cap of the sealing rotor, can be designed as a magnetic coupling. Rotation of the magnetic coupling drives the spiral motion of the sealing cap of the high-temperature, high-pressure sealing rotor 5. The magnetic coupling with a mechanical rod can be welded to the second fluid filler housing B for sealing, or it can be sealed by squeezing an O-ring with a ferrule, with the mechanical rod passing through a small hole in the second fluid filler housing B.

[0080] like Figure 1 As shown, the portion D for rotating the sealing rotor cap can also be designed as a robotic arm, enabling rotation. Specifically, by rotating a mechanical rod with a handle on top, the sealing cap of the high-temperature, high-pressure sealed rotor 5 is driven to spirally move. The handle-mounted mechanical rod passes through a small hole in the second fluid filler housing B. This hole has an internal thread that mates with an external thread in the middle of the mechanical rod. The mechanical rod and the second fluid filler housing B are sealed by a ferrule.

[0081] Part D for rotating the sealing rotor sealing cap can also be designed in the form of a rotating sealing bearing, which is connected and sealed with the second fluid filler housing B through a rotating sealing bearing, and is used to rotate and drive the rotation of the mechanical rod passing through the second fluid filler housing B, thereby driving the spiral movement of the high-temperature and high-pressure sealing rotor 5 sealing cap.

[0082] Several external connection holes 14 are designed within the sealed space of the first and second fluid filler housings A and B. These holes connect to the gas system and allow for the insertion of thermocouples and heating blanket wiring. These holes 14, connected to the gas system, are used to seal, introduce the required fluid, and perform other operations such as vacuuming. The holes 14 for inserting thermocouples and heating blanket wiring are sealed with ferrules. The thermocouples and heating blanket are placed around the high-temperature, high-pressure sealed rotor 5 to heat and measure its temperature.

[0083] The fluid filler can be placed on a fixed frame as a whole.

[0084] The relevant gas circuit system consists of a fluid source unit, a vacuum unit, a sample processing unit, a pressure detection unit and a fluid outlet unit 16.

[0085] The fluid source unit includes a desired fluid source 9, a pressure reducing valve V1 connected to the desired fluid source 9, a first two-way valve V2 connected to the pressure reducing valve V1, a cold trap 10 connected to the first two-way valve V2, a first three-way valve V3 connected to the cold trap 10, and a flow meter 11 and a second two-way valve V6 connected to the first three-way valve V3. The fluid source unit is used to achieve controllable fluid supply. The cold trap 10 can be filled according to experimental needs and the fluid passing through it. It can be filled with liquid nitrogen, dry ice, and various cooling baths to purify the desired fluid. For example, when the experiment needs to remove trace water from hydrogen, an appropriate amount of liquid nitrogen can be added to the cold trap 10 to dehydrate and deoxygenate the passing hydrogen. The first two-way valve V2 and the second two-way valve V6 can use valve bodies such as ball valves and needle valves.

[0086] The vacuum unit includes a third three-way valve V5 and various stages of vacuum pumps 15 connected thereto to realize vacuuming operation of the system.

[0087] The sample processing unit connects the fluid filler to the position indicated by the number 17 of the gas system.

[0088] The pressure detection unit includes a second three-way valve V4 connected to the sample processing unit, and a vacuum gauge 12 and a pressure gauge 13 (pressure gauge) connected thereto. By switching the second three-way valve V4, the system pressure can be measured under negative pressure or positive pressure conditions.

[0089] The fluid outlet unit 16 is connected to the atmosphere and is connected to the third three-way valve V5.

[0090] Example 1

[0091] The present invention is a device for processing samples and filling fluids in a high-temperature, high-pressure sealed rotor. It can dehydrate and degas samples in a high-temperature, high-pressure sealed rotor, controllably fill fluids with a specific atmosphere from low pressure (10-4Pa) to high pressure (10MPa), pre-react at a specific temperature and atmosphere, and in-situ unseal and seal the rotor in the desired atmosphere.

[0092] The figure shows a fluid filler and its associated gas circuit system according to the present invention. The fluid filler comprises a first fluid filler housing A, a second fluid filler housing B, a rotor sample chamber holder C, and a portion D for rotating the rotor sealing cap. The associated gas circuit system comprises a fluid source unit, a vacuum unit, a sample processing unit, a pressure detection unit, and a fluid outlet unit.

[0093] (1) The first fluid filler housing A is a hollow cylinder made of stainless steel, closed at one end. Two straight, hollow windows 1 are constructed in the wall of the first fluid filler housing A, parallel to the sealing connection between the high-temperature, high-pressure sealed rotor 5 and the sample chamber. These windows are used to observe the relative position of the rotor sealing cap and the rotor chamber.

[0094] (2) A hollow, transparent quartz liner (hollow liner 4) with both ends open is placed inside the first fluid filler housing A. O-ring sealing grooves are provided on both end faces of hollow liner 4 for accommodating sealing ring 3. O-ring sealing grooves are also provided at corresponding locations in the first fluid filler housing A and the second fluid filler housing B.

[0095] (3) An air hole is provided below the hollow interior of the hollow transparent quartz lining (hollow lining 4) at the bottom of the first fluid filler housing A, which is in the relevant air path system ( Figure 7 ) is connected to the relevant gas path.

[0096] The relevant gas circuit system consists of a fluid source unit, a vacuum unit, a sample processing unit, a pressure detection unit and a fluid outlet unit 16.

[0097] The fluid source unit includes a required fluid source 9, a pressure reducing valve V1 connected to the required fluid source 9, a first two-way valve V2 connected to the pressure reducing valve V1, a cold trap 10 connected to the first two-way valve V2, a first three-way valve V3 connected to the cold trap 10, and a flow meter 11 and a second two-way valve V6 connected thereto.

[0098] The vacuum unit includes a third three-way valve V5 and various stages of vacuum pumps 15 connected thereto.

[0099] The sample processing unit connects the fluid-filled reactor to the position shown by the label 17 of the relevant gas system.

[0100] The pressure detection unit includes a second three-way valve V4 connected to the sample processing unit, and a vacuum gauge 12 and a pressure gauge 13 (pressure gauge) connected thereto.

[0101] The fluid outlet unit 16 is connected to the atmosphere and is connected to the third three-way valve V5.

[0102] (IV) When fixing the rotor sample cavity, if Figure 3-6 As shown, after inserting the high-temperature, high-pressure sealed rotor 5 containing the desired solid sample into the rotor sleeve 6, the rotor sleeve nut 7 is threaded onto the outside of the rotor sleeve 6 and gradually squeezes the rotor sleeve 6 from the top surface, thereby tightening and securing the high-temperature, high-pressure sealed rotor 5. The entire rotor (rotor sample chamber holder C) is then placed inside the hollow transparent quartz liner (hollow liner 4), and the protrusion on the bottom of the rotor sleeve 6 mates with the groove provided in the first fluid filler housing A, thereby securing the rotor sample chamber holder C.

[0103] (5) If Figure 1As shown, the portion D for rotating the sealing cap of the sealed rotor drives the spiral motion of the sealing cap of the high-temperature, high-pressure sealed rotor 5 by rotating a mechanical rod with a handle on its upper portion. The handle-mounted mechanical rod passes through a small hole in the second fluid filler housing B. This hole has an internal thread that mates with the external thread in the middle of the mechanical rod. The mechanical rod and the second fluid filler housing B are sealed by a ferrule. The bottom of the mechanical rod is shaped to match the top of the plastic part that is connected to the top of the sealing cap of the high-temperature, high-pressure sealed rotor 5, and the two are connected by a matching concave-convex connection.

[0104] (6) The first fluid filler shell A and the second fluid filler shell B are connected by a threaded structure 2, and the internal space is sealed by squeezing the sealing ring 3 placed on the sealing groove of the first fluid filler shell A and the bottom of the liner 4, and the second fluid filler shell B and the top of the liner 4 on their connecting surfaces.

[0105] (VII) The handle D of the sealing cap of the high-temperature and high-pressure sealed rotor 5 can be used to rotate the sealing cap, thereby unsealing or sealing the high-temperature and high-pressure sealed rotor 5 under a controlled atmosphere.

[0106] (VIII) During operation, after assembling and connecting the high-temperature and high-pressure sealed rotor 5, the fluid filler and the required gas path:

[0107] 1. First, degas the entire system to ensure that the system is clean. At this time, open all two-way valves, switch the third three-way valve V5 to the vacuum unit (vacuum system), and switch the first three-way valve V3 and the second three-way valve V4 back and forth several times.

[0108] 2. After the system has been degassed for a period of time and reaches the vacuum required for the experiment, according to experimental needs, you can rotate part D of the fluid filler used to rotate the sealed rotor sealing cap, open the high-temperature and high-pressure sealed rotor 5 (high-temperature and high-pressure in-situ rotor), and degas the sample; if the experiment does not require degassing of the sample, wait until the required fluid atmosphere is introduced into the system before opening the high-temperature and high-pressure sealed rotor 5.

[0109] 3. Fill the sample with fluid, perform adsorption, and perform a pre-reaction according to experimental requirements. At this point, fill the cold trap 10 with the corresponding medium to purify the required fluid. Close the third three-way valve V5 as required, and switch the second three-way valve V4 to the vacuum gauge 12 or pressure gauge 13 based on the required adsorption pressure range. Open the fluid source 9, pressure reducing valve V1, first two-way valve V2, first three-way valve V3, second two-way valve V6, and flowmeter 11 as required, and introduce the fluid to the desired pressure.

[0110] 4. After the required fluid is introduced, close the first three-way valve V3 and the flow meter 11, and perform adsorption equilibrium or pre-reaction according to experimental requirements.

[0111] 5. After the pre-reaction or adsorption equilibrium is completed, the part D of the fluid filler used to rotate the sealing rotor sealing cap is rotated again to seal the high-temperature and high-pressure sealed rotor 5 (high-temperature and high-pressure in-situ rotor) in situ, and then the third three-way valve V5 is switched to the vacuum unit or the fluid outlet unit 16 as needed.

[0112] 6. Open the fluid filler and take out the high-temperature and high-pressure sealed rotor 5 to prepare for solid-state nuclear magnetic resonance sampling.

[0113] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the above embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the above embodiments, or replace some or all of the technical features therein with equivalents. However, these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A device for sample processing and fluid filling of a high-temperature and high-pressure sealed solid-state nuclear magnetic resonance rotor, characterized in that: The invention comprises a fluid filler and an air circuit system, wherein the fluid filler comprises a fluid filler housing, a rotor sample chamber fixing seat (C), and a portion (D) for rotating and sealing a rotor sealing cap. The fluid filler housing is connected to the air circuit system and consists of a first fluid filler housing (A) and a second fluid filler housing (B) connected to each other, forming a sealed receiving chamber inside. The rotor sample cavity fixing seat (C) is located in the accommodating chamber, and includes a rotor sleeve (6) and a rotor clamping nut (7) for placing the high-temperature and high-pressure sealed rotor (5), the rotor sleeve (6) is connected to the first fluid filler housing (A), and the rotor clamping nut (7) is connected to the rotor sleeve (6); the rotor sample cavity fixing seat (C) fixes the high-temperature and high-pressure sealed rotor (5) sample cavity by extrusion, and after the high-temperature and high-pressure sealed rotor (5) is inserted into the rotor sleeve (6), the rotor clamping nut (7) is screwed into the outside of the rotor sleeve (6) through a thread, and the rotor sleeve (6) is gradually squeezed through the top surface to bite the high-temperature and high-pressure sealed rotor (5), so that the high-temperature and high-pressure sealed rotor (5) is fixed; The portion (D) for rotating the sealing rotor sealing cap is connected to the second fluid filler housing (B) and the sealing cap of the high-temperature and high-pressure sealing rotor (5), and by rotating the portion (D) for rotating the sealing rotor sealing cap, the sealing cap of the high-temperature and high-pressure sealing rotor (5) is driven to perform a spiral motion, thereby unsealing or sealing the high-temperature and high-pressure sealing rotor (5); When the window design is performed, one or more hollow window holes (1) are provided on the first fluid filler housing (A) or the second fluid filler housing (B) at a parallel height to the sealing connection between the sealing cap of the high-temperature and high-pressure sealed rotor (5) and the sample chamber, for observing the relative position of the sealing cap of the high-temperature and high-pressure sealed rotor (5) and the sample chamber; A hollow liner (4) matching the fluid filler shell is placed inside the fluid filler shell, a first sealing groove is set above and below the hollow liner (4), a second sealing groove is set at the corresponding position of the first fluid filler shell (A) and the second fluid filler shell (B), and a sealing ring (3) is placed between the first sealing groove and the second sealing groove; the rotor sample cavity fixing seat (C) is placed inside the transparent hollow liner (4); the hollow liner (4) is made of a transparent material, and the transparent material is glass, quartz or polycarbonate.

2. The device for sample processing and fluid filling of a high-temperature and high-pressure sealed solid-state nuclear magnetic resonance rotor according to claim 1, characterized in that: The central axis of the rotor sleeve (6) is hollow and is used to place a cylindrical high-temperature and high-pressure sealed rotor (5); the upper portion of the rotor sleeve (6) is tapered and has a plurality of small slits; the middle portion of the rotor sleeve (6) is provided with an external thread for connection with a rotor sleeve nut (7); the lower portion of the rotor sleeve (6) is connected to the first fluid filler housing (A) in a concave-convex matching manner; The rotor clamping nut (7) is a hollow body provided with an internal thread, the top opening of which matches the upper part of the rotor sleeve (6), and the bottom is connected to the middle part of the rotor sleeve (6) through a thread; The rotor sleeve (6) and the rotor clamping sleeve nut (7) are both made of a material with a certain elasticity, and the material with a certain elasticity is plastic; The high-temperature and high-pressure sealed rotor (5) is an in-situ solid nuclear magnetic resonance rotor with threads that can perform high-temperature and high-pressure sealing.

3. The device for sample processing and fluid filling of a high-temperature and high-pressure sealed solid-state nuclear magnetic resonance rotor according to claim 1, characterized in that: The portion (D) for rotating the sealing rotor sealing cap is connected to the sealing cap of the high-temperature and high-pressure sealing rotor (5) via a transition piece (8), and the connecting portion is concave-convex matched, and the transition piece (8) is a plastic piece or a graphite piece; Alternatively, the portion (D) for rotating the sealing rotor sealing cap is integrally connected to the sealing cap of the high-temperature and high-pressure sealing rotor (5) by concave-convex matching; The main body of the portion (D) for rotating and sealing the rotor sealing cap is made of a pressure-resistant material.

4. The device for sample processing and fluid filling of a high-temperature and high-pressure sealed solid-state nuclear magnetic resonance rotor according to claim 1 or 3, characterized in that: The portion (D) for rotating the sealing rotor cap is a mechanical arm structure, a magnetic coupler structure or a rotary sealing bearing structure; The mechanical arm structure includes a first mechanical rod with a handle on the upper portion, the first mechanical rod passing through a small hole provided on the second fluid filler housing (B), an internal thread provided in the small hole, the internal thread matching the external thread provided in the middle of the first mechanical rod, the first mechanical rod and the second fluid filler housing (B) are sealed by a ferrule; by rotating the first mechanical rod, the high-temperature and high-pressure sealing rotor (5) is driven to perform a spiral motion of the sealing cap; The magnetic coupling structure includes a magnetic coupling with a second mechanical rod, the second mechanical rod passing through a small hole provided on the second fluid filler housing (B); the magnetic coupling is sealed by welding to the second fluid filler housing (B) or by squeezing an O-ring through a ferrule; The portion (D) for rotating the sealing rotor seal cap may also be connected and sealed to the second fluid filler housing (B) by means of a rotating sealing bearing; The portion (D) for rotating the sealing rotor sealing cap drives the mechanical rod passing through the second fluid filler housing (B) to rotate, thereby driving the high-temperature and high-pressure sealing rotor (5) sealing cap to perform spiral motion.

5. The device for sample processing and fluid filling of a high-temperature and high-pressure sealed solid-state nuclear magnetic resonance rotor according to any one of claims 1 to 3, characterized in that: The fluid filler is placed as a whole on a fixed frame; a plurality of holes (14) connected to the outside are opened on the outer shell of the fluid filler for connection with the gas system and for inserting wires connected to the thermocouple and the heating blanket; the holes (14) connected to the gas system are sealed or fluid is introduced or vacuumed through the gas system; the holes (14) for inserting the wires are sealed by a ferrule; the thermocouple and the heating blanket are placed around the high-temperature and high-pressure sealed rotor (5) to achieve heating and temperature measurement of the high-temperature and high-pressure sealed rotor (5); The first fluid filler housing (A) and the second fluid filler housing (B) are connected via a plurality of threaded structures (2); the first fluid filler housing (A) and the second fluid filler housing (B) are both made of sealable and pressure-resistant materials.

6. The device for sample processing and fluid filling of a high-temperature and high-pressure sealed solid-state nuclear magnetic resonance rotor according to claim 1, characterized in that: The gas circuit system includes a fluid source unit, a vacuum unit, a sample processing unit, a pressure detection unit and a fluid outlet unit (16); The fluid source unit comprises a required fluid source (9), a pressure reducing valve (V1) connected to the required fluid source (9), a first two-way valve (V2) connected to the pressure reducing valve (V1), a cold trap (10) connected to the first two-way valve (V2), a first three-way valve (V3) connected to the cold trap (10), a flow meter (11) connected to the first three-way valve (V3), and a second two-way valve (V6); the cold trap (10) is filled according to experimental requirements and the fluid passing therethrough to purify the required fluid; the valve bodies of the first two-way valve (V2) and the second two-way valve (V6) are ball valves or needle valves; The vacuum unit comprises a third three-way valve (V5) and various stages of vacuum pumps (15) connected to the third three-way valve (V5); The sample processing unit is used to connect the fluid filler to the gas circuit system; The pressure detection unit includes a second three-way valve (V4) connected to the sample processing unit, and a vacuum gauge (12) and a pressure gauge (13) connected to the second three-way valve (V4), and the second three-way valve (V4) is switched to measure the system pressure under negative pressure or positive pressure conditions; The fluid outlet unit (16) is connected to the atmosphere and is connected to the third three-way valve (V5).

7. A method for operating the sample processing and fluid filling device for a high-temperature, high-pressure sealed solid-state nuclear magnetic resonance rotor according to any one of claims 1 to 6, characterized in that: The steps include: Step 1: Assemble and connect the high-temperature and high-pressure sealed rotor (5), the fluid filler and the required gas path; Step 2: First, degas the entire device to ensure that it is clean. At this time, open all two-way valves, switch the third three-way valve (V5) to the vacuum unit, and switch the first three-way valve (V3) and the second three-way valve (V4) back and forth several times. Step 3: After the device has been degassed for a period of time and reaches the vacuum required for the experiment, the portion (D) of the fluid filler used to rotate the sealing rotor cap can be rotated to open the high-temperature and high-pressure sealing rotor (5) to degas the sample according to the experimental needs; If the experiment does not require degassing of the sample, open the high-temperature and high-pressure sealed rotor (5) after the required fluid atmosphere is introduced into the system; Step 4: Fill the sample with fluid, adsorb, and pre-react according to experimental needs; at this time, fill the cold trap (10) with the corresponding medium according to experimental needs to purify the required fluid, close the third three-way valve (V5) according to experimental needs, switch the second three-way valve (V4) to the vacuum gauge (12) or the pressure gauge (13) according to the pressure range required for adsorption, open the required fluid source (9) and the pressure reducing valve (V1), the first two-way valve (V2), the first three-way valve (V3), the second two-way valve (V6), and the flow meter (11) according to experimental needs, and introduce the fluid to the required pressure; Step 5: After the required fluid is introduced, the flow meter (11) and the first three-way valve (V3) are closed, and adsorption equilibrium or pre-reaction is performed according to experimental requirements; Step 6: After the pre-reaction or adsorption equilibrium is completed, the portion (D) of the fluid filler used to rotate the sealing rotor seal cap is rotated again to seal the high-temperature and high-pressure sealing rotor (5) in situ, and then the third three-way valve (V5) is switched to the vacuum unit or the fluid outlet unit (16) as needed; Step 7: Open the fluid filler and take out the high-temperature and high-pressure sealed rotor (5) to prepare for solid-state NMR sampling.

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