阅读说明：本技术 一种用于宽压力范围下原位处理和密封固体核磁测试样品的装置及系统 (Device and system for in-situ treatment and sealing of solid nuclear magnetic test sample under wide pressure range ) 是由 侯广进 龚科 刘宪春 赵侦超 包信和 于 2019-10-10 设计创作，主要内容包括：本发明涉及一种用于宽压力范围下原位处理和密封固体核磁测试样品的装置。主体为密封气路,包括气源单元,压力检测单元,样品处理单元,尾气出口单元。样品装入商业化的样品管后,放入样品处理单元的反应器中,进行脱气,吸附,反应等处理,处理后通过旋转反应器的手柄,将密封塞压入样品管密封。实现了各种气氛不同压力范围的固体核磁共振样品的处理和密封一次完成。(The invention relates to a device for in-situ treatment and sealing of solid nuclear magnetic test samples under a wide pressure range. The main body is a sealed gas circuit and comprises a gas source unit, a pressure detection unit, a sample processing unit and a tail gas outlet unit. After the sample is filled into a commercial sample tube, the sample is placed into a reactor of a sample processing unit for degassing, adsorption, reaction and the like, and after the treatment, a sealing plug is pressed into the sample tube for sealing by rotating a handle of the reactor. The treatment and sealing of the solid nuclear magnetic resonance samples in different pressure ranges in various atmospheres are completed at one time.)

1. A nuclear magnetic testing device for in-situ treatment and sealing is characterized by comprising a handle, a guide rod bracket, a bracket clamping sleeve, a base, a sealing plug fixing sleeve, a sealing plug, a sample tube and a sample tube supporting tube; the middle part of the guide rod is provided with an external thread; the guide rod bracket is provided with internal threads; the base is of a cross-shaped four-way structure, and through holes corresponding to the four-way structure are an upper hole, a lower hole, a left hole and a right hole respectively; the upper hole and the lower hole of the base are both provided with external threads; the handle is fixed on the upper part of the guide rod, and the guide rod penetrates through the guide rod bracket to enable the external thread of the guide rod to be hermetically connected with the internal thread of the guide rod bracket; the support clamping sleeve is provided with an internal thread, and the internal thread of the support clamping sleeve is hermetically connected with the external thread of the hole on the base; the guide rod bracket penetrates through the bracket clamping sleeve, and the bottom of the guide rod bracket is contacted with the hole on the base;

the sample tube supporting tube is connected with the lower hole of the base in a sealing manner; the sample tube is arranged in the sample tube carrier tube; the sealing plug fixing sleeve is positioned above the sample tube and is contacted with the sample tube, and the sealing plug is arranged in the sealing plug fixing sleeve.

2. The nuclear magnetic testing device of claim 1, wherein the sealing connection of the sealing connection is provided with a sealing ring.

3. The nuclear magnetic testing device of claim 1, further comprising a carrier press cap and a press cap core; the sample tube supporting tube penetrates through the bracket pressing cap and the pressing cap core, and the internal thread of the bracket pressing cap is connected with the external thread of the lower hole of the base; the outer side of the pressing cap core is in contact with the inner side of the lower hole of the base, and the sample tube supporting tube is connected with the lower end hole of the base in a sealing mode through the bracket pressing cap and the pressing cap core.

4. The nuclear magnetic testing device of claim 1, wherein the handle, the guide rod holder, the holder sleeve, the base, the sealing plug holder, and the sample tube support tube are made of metal, the sample tube is a commercially standard solid nuclear magnetic sample tube, and the sealing plug is made of polytetrafluoroethylene.

5. The nuclear magnetic testing device of claim 1, wherein the sealing plug is a resilient cylinder; the diameter of the cylinder is 0.1-0.2mm larger than the inner diameter of the sealing plug fixing sleeve.

6. The nuclear magnetic testing device of claim 1, wherein the sample tube support tube is a hollow cylinder open at one end, and the inner diameter of the cylinder is 0.2-0.5mm larger than the outer diameter of the sample tube.

7. The nuclear magnetic testing device of claim 1, wherein the sealing plug fixing sleeve is a hollow cylinder with an opening at the upper part and the lower part, the outer diameter of the cylinder is the same as the outer diameter of the sample tube, and the inner diameter of the cylinder is the same as the inner diameter of the sample tube.

8. The nuclear magnetic testing device of claim 7, wherein the side of the sealing plug retainer sleeve is provided with a through hole, and the through hole is located below the sealing plug.

9. A nuclear magnetic test system with in-situ treatment and sealing is characterized by comprising an air source unit, a pressure detection unit, a sample treatment unit and a tail gas outlet unit;

an air source unit: the device comprises a processing gas source, a pressure reducing valve connected with the processing gas source, a flow meter connected with the pressure reducing valve, and a first stop valve connected with the flow meter;

a pressure detection unit: the vacuum gauge comprises a first three-way valve, a vacuum gauge and a pressure gauge, wherein one side of the first three-way valve is connected with a first stop valve, and the other two sides of the first three-way valve are respectively connected with the vacuum gauge and the pressure gauge;

a sample processing unit: the nuclear magnetic testing device comprises a second stop valve, a nuclear magnetic testing device according to any one of claims 1 to 8 and a third stop valve, wherein one side of the second stop valve is respectively connected with the first three-way valve and the first stop valve through pipelines, the other side of the second stop valve is hermetically connected with a left hole of the nuclear magnetic testing device, and one side of the third stop valve is hermetically connected with a right hole of the nuclear magnetic testing device;

a tail gas outlet unit: comprises a second three-way valve, a vacuum system and a tail gas outlet; one side of the second three-way valve is connected with the other side of the third stop valve, and the other two sides of the second three-way valve are respectively connected with the vacuum system and the tail gas outlet.

10. The nuclear magnetic testing system of claim 9, wherein the left and right bores of the nuclear magnetic testing device are each secured with a ferrule.

Technical Field

The invention belongs to the field of heterogeneous catalysis and solid nuclear magnetic resonance spectrum characterization, and particularly relates to a device and a system for in-situ treatment and sealing of a solid nuclear magnetic test sample in a wide pressure range.

Background

The solid nuclear magnetic resonance is an important research means for researching heterogeneous catalytic reaction, and the characteristics of element resolution and short-range structure sensitivity have unique advantages for researching the structure and the reaction mechanism of the catalyst. For some solid samples, the sample needs to be processed, such as dehydration, adsorption, oxidation, reduction, etc., before the solid nmr experiment is performed, and the nmr test needs to be performed under the condition of isolating air or a specific atmosphere. For the sample processing and sealing techniques, the main methods reported in the literature currently include:

preparing a small ampoule bottle by a heat sealing method: and putting the solid sample into a small glass tube in advance, vacuumizing, then carrying out adsorption, reaction and other treatment, putting one end of the glass tube into liquid nitrogen after the treatment is finished, and burning, melting and sealing the thin glass tube by using flame at the other end. However, in the solid nuclear magnetic resonance test, the sample needs to rotate at a high speed, and the requirements on the strength and the uniformity of the ampoule bottle packaging are high, so the operation is difficult, and the success rate is low. The heat sealing method also does not allow for pressure control for solid sample testing that requires an atmosphere.

The samples were first processed in a common reaction tube and then transferred to a glove box under sealed conditions for loading. The method is simple to operate, but has a limited application range and can only be used for solid samples under non-specific atmosphere conditions.

The institute Liuxiong chemical physics of the institute of the academy of Chinese academy of sciences has disclosed the integrated reactor that is used for solid nuclear magnetic test sample in patent CN98238330.4, can realize can handling the sample under vacuum or various special atmospheres, the normal position is adorned appearance and is sealed, but this device is the quartz material, can't carry out sample processing under the high-pressure atmosphere condition, simultaneously because its dead volume is great, can cause gaseous waste when using enrichment gas to carry out sample adsorption or processing, restricted its use.

Disclosure of Invention

The invention solves the problems: the method overcomes the defects of the prior art, realizes the one-time completion of the treatment and the sealing of the solid nuclear magnetic resonance samples in different pressure ranges in various atmospheres, has simple operation, is suitable for the treatment of dehydration, adsorption, oxidation, reduction reaction and the like of various solid materials, and can realize the sealing under the controllable air pressure (0.01kPa-1 MPa).

The technical scheme of the invention is as follows:

the invention provides an in-situ treatment and sealing nuclear magnetic testing device which comprises a handle, a guide rod bracket, a bracket clamping sleeve, a base, a sealing plug fixing sleeve, a sealing plug, a sample tube and a sample tube supporting tube, wherein the guide rod is fixedly arranged on the base; the middle part of the guide rod is provided with an external thread; the guide rod bracket is provided with internal threads; the base is of a cross-shaped four-way structure, and through holes corresponding to the four-way structure are an upper hole, a lower hole, a left hole and a right hole respectively; the cross-shaped four-way structure shows that the upper part and the lower part of the base are provided with through holes, namely an upper hole and a lower hole which are on the same extension line and allow the guide rod to be inserted into the sealing plug fixing sleeve from the upper part; the left and the right are provided with through holes to lead the gas to pass through the base; the left and right through holes are communicated with the upper and lower through holes, so that gas can enter the sample tube supporting tube. The upper hole and the lower hole of the base are both provided with external threads; the handle is fixed on the upper part of the guide rod, the guide rod penetrates through the guide rod bracket to enable the external thread of the guide rod to be hermetically connected with the internal thread of the guide rod bracket, and the handle is connected with the guide rod to drive the guide rod to rotate; the middle external thread of the guide rod is connected with the internal thread of the guide rod bracket, so that the guide rod and the guide rod bracket can move relatively, and further the guide rod and the base can move relatively; the support clamping sleeve is provided with an internal thread, and the internal thread of the support clamping sleeve is hermetically connected with the external thread of the hole on the base; the guide rod bracket penetrates through the bracket clamping sleeve, and the bottom of the guide rod bracket is contacted with the hole at the upper end of the base;

the sample tube supporting tube is hermetically connected with a lower end hole of the base; the sample tube is arranged in the sample tube carrier tube; the sealing plug fixing sleeve is positioned above the sample tube and is contacted with the sample tube, and the sealing plug is arranged in the sealing plug fixing sleeve.

Based on the technical scheme, preferably, a sealing ring is arranged at the sealing connection part of the sealing connection, and a small sealing ring is arranged between the guide rod and the guide rod bracket, so that the guide rod and the guide rod bracket are sealed; the guide rod support penetrates through the support clamping sleeve, the bottom of the support clamping sleeve is connected with the upper end hole of the base, the internal thread of the support clamping sleeve is connected with the external thread of the top end of the base, the guide rod support is fixed on the base, and the large sealing ring is arranged between the guide rod support and the base to seal the guide rod support and the base.

Based on the technical scheme, preferably, the bracket presses the cap and presses the cap core; the lower end of the base is connected with a sample tube supporting tube, the sample tube supporting tube penetrates through the bracket pressing cap and the pressing cap core, and the internal thread of the bracket pressing cap is connected with the external thread of the lower hole of the base; the outer side of the pressing cap core is in contact with the inner side of the lower hole of the base, and the sample tube supporting tube is connected with the lower end hole of the base in a sealing mode through the bracket pressing cap and the pressing cap core.

Based on the above technical scheme, preferably, the handle, the guide rod bracket, the bracket clamping sleeve, the base, the sealing plug fixing sleeve and the sample tube support tube are made of metal materials, and the sample tube is a commercially standard solid nuclear magnetic sample tube.

Based on the technical scheme, preferably, the sealing plug is an elastic cylinder; the sealing plug is made of polytetrafluoroethylene or other materials, has certain deformability, and has a diameter slightly larger than the inner diameter of the sample tube; the diameter of the cylinder is 0.1-0.2mm larger than the inner diameter of the sealing plug fixing sleeve, so that the sealing plug can enter the sample tube through extrusion deformation, and the sealing effect is achieved. The guide rod penetrates through the base, the bottom end of the guide rod is connected with the sealing plug, and the sealing plug is pushed into the sample tube through rotating the guide rod during sealing.

Based on the above technical scheme, preferably, the sample tube supporting tube is a hollow cylinder with an opening at one end, the outer diameter of the sample tube with the inner diameter of the cylinder is 0.2-0.5mm larger, the inner diameter of the sample tube supporting tube enables the sample tube to be smoothly placed in the sample tube supporting tube, the sample tube can be fixed at the same time, the sample tube supporting tube is sequentially provided with the sealing plug fixing sleeve and the sample tube from top to bottom, and the sealing plug is arranged in the sealing plug fixing sleeve.

Based on the above technical scheme, preferably, the sealing plug fixing sleeve is a hollow cylinder with openings at the upper and lower parts, the outer diameter of the cylinder is the same as the outer diameter of the sample tube, and the inner diameter of the cylinder is the same as the inner diameter of the sample tube.

Based on above technical scheme, it is preferred that the side of the fixed cover of sealing plug is equipped with the through-hole, the through-hole is located the sealing plug below, sets up the through-hole and makes things convenient for gas to get into the sample cell from the through-hole.

The invention also provides a solid nuclear magnetic testing system for in-situ treatment and sealing in a wide pressure range, which comprises an origin unit, a pressure detection unit, a sample treatment unit and a tail gas outlet unit;

an air source unit: the device comprises a processing gas source, a pressure reducing valve connected with the processing gas source, a flowmeter connected with the pressure reducing valve, and a first stop valve connected with the flowmeter, and is used for realizing controllable gas supply;

a pressure detection unit: the vacuum gauge comprises a first three-way valve, a vacuum gauge and a pressure gauge, wherein one side of the first three-way valve is connected with a first stop valve, and the other two sides of the first three-way valve are respectively connected with the vacuum gauge and the pressure gauge; gas pressure detection from low pressure (0.01kPa-100kPa) to high pressure (1atm-4MPa) is realized by switching a first three-way valve

A sample processing unit: the nuclear magnetic testing device comprises a second stop valve, the nuclear magnetic testing device and a third stop valve, wherein one side of the second stop valve is respectively connected with a first three-way valve and the first stop valve through pipelines, the other side of the second stop valve is in sealing connection with a left hole of the nuclear magnetic testing device, and one side of the third stop valve is in sealing connection with a right hole of the nuclear magnetic testing device;

a tail gas outlet unit: comprises a second three-way valve, a vacuum system and a tail gas outlet; one side of the second three-way valve is connected with the other side of the third stop valve, the other two sides of the second three-way valve are respectively connected with the vacuum system and the tail gas outlet, and vacuumizing or tail gas discharge is realized by switching the second three-way valve.

Based on above technical scheme, preferably, right cutting ferrule is all fixed to nuclear magnetic testing device's left side hole and right hole, realizes the processing to the sample and the sealed of sample cell.

Advantageous effects

(1) The device is connected with a vacuum system, and can carry out in-situ dehydration and degassing treatment on the sample. The device of the invention has good sealing performance under vacuum condition and high pressure condition, and can realize gas treatment under wide pressure ranges of 0.01kPa-100kPa and 0.1 MPa-1 MPa by switching the pressure detector.

(2) The device can carry out sealed sampling of the sample tube under the atmosphere condition of fixed pressure, so that the sample is in a controllable atmosphere condition during sampling.

(3) The base in the device is cast integrally, the dead volume in the sealed space is small, and the treatment gas can be saved.

(4) The invention has simple installation and convenient use, is compatible with the conventional solid nuclear magnetic resonance spectrometer and a sample tube matched with the conventional solid nuclear magnetic resonance spectrometer, and can be widely applied to the research of pore materials, solid catalysts and catalytic reaction.

Drawings

FIG. 1 is a schematic diagram of the system of the present invention;

FIG. 2 is a cross-sectional view of the apparatus of the present invention;

FIG. 3 is a schematic view of the apparatus of the present invention in an assembled and disassembled state;

FIG. 4 is a solid NMR spectrum of a ZSM-22 sample with xenon adsorption equilibrium of 4atm in example 1 of the present invention at different rotation speeds¹²⁹Xe spectrum;

wherein: 1. a gas source; 2. a flow meter; 3. a vacuum gauge; 4. a pressure gauge; 5. 6, cutting the ferrule; 7. a vacuum system; 8. a tail gas outlet; v1, a pressure reducing valve; v2. a first shut-off valve; v3. a first three-way valve; v4. a second stop valve; v5. a third stop valve; v6. a second three-way valve; 9. a handle; 10. a guide bar; 11. a guide bar support; 12. a bracket clamping sleeve; 13 large sealing rings; 14. a small seal ring; 15. a base; 16. a sealing plug fixing sleeve; 17. a sealing plug; 18. a sample tube; 19. a sample tube supporting tube; 20. a bracket pressing cap; 21. and (4) pressing the cap core.

Detailed Description

The present invention will be described in detail with reference to the accompanying drawings. The invention is a device for in situ processing and sealing of solid nuclear magnetic test samples over a wide pressure range, which can dehydrate and degas the sample, then subject the sample to further processing such as adsorption, reaction, and sealing of the sample under atmospheric conditions, and then transfer the sample to a solid nuclear magnetic resonance instrument for sampling.

As shown in fig. 2 and 3, the device of the present invention comprises a handle 9, a guide rod 10, a small seal ring 14, a guide rod bracket 11, a large seal ring 13, a bracket sleeve 12, a base 15, a sample tube 18, a sample tube support tube 19, a bracket pressing cap 20, a pressing cap core 21, a sealing plug 17 and a sealing plug fixing sleeve 16; the base 15 is a cross-shaped four-way structure, the integrally cast main body is in the shape of a cuboid and comprises an upper hole, a lower hole, a left hole and a right hole which are communicated with each other, and the upper hole and the lower hole are both provided with external thread structures and are on the same extension line; the sealing plug fixing sleeve 16 is of an annular structure with an upper opening and a lower opening; the sample tube support tube 19 is a similar structure of a sample tube, cylindrical with an open upper end.

The handle 9 is connected with the guide rod 10, the external thread at the middle part of the guide rod 9 is connected with the internal thread of the guide rod support 11, a small sealing ring 14 is arranged between the guide rod 10 and the guide rod support 11, the guide rod support 11 penetrates through a support cutting sleeve 12, the bottom of the guide rod support 11 is connected with the upper hole of the base 15, a large sealing ring 13 is arranged between the guide rod support 11 and the base 15, the internal thread of the support cutting sleeve 12 is connected with the external thread of the upper hole of the base 15, the guide rod support 11 is fixed on the base 15, and the left end and the right end of the base are. The lower hole of the base 15 is connected with a sample tube supporting tube 19, the sample tube supporting tube 19 penetrates through a bracket pressing cap 20 and a pressing cap core 21, the inner thread of the bracket pressing cap 20 is connected with the outer thread of the lower hole of the base 15, the outer side of the pressing cap core 21 is connected with the inner side of the lower hole of the base 15, and the pressing cap core 21 is extruded by rotating the bracket pressing cap 20, so that the sealing effect is achieved. The sample tube supporting tube 19 is sequentially provided with a sealing plug fixing sleeve 16 and a sample tube 18 from top to bottom. A sealing plug 17 is arranged in the sealing plug fixing sleeve 16.

The system comprises a gas source unit, a pressure detection unit, a sample processing unit and a tail gas outlet unit. The specific implementation steps for degassing the sample are as follows:

transferring a certain amount of catalyst into a sample tube 18, and compacting;

loading sample tube 18 into sample tube holding tube 19;

the sealing plug 17 is arranged in the sealing plug fixing sleeve 16, and the sealing plug fixing sleeve 16 is arranged in the sample tube bracket 19 and is positioned above the sample tube 18;

rotating the handle 9 to drive the guide rod 10 to the uppermost end, sleeving the sample tube bracket 19 into a hole below the base 15, sleeving the cap pressing core 21 and the bracket pressing cap 20 on the sample tube bracket 19, and screwing down the bracket pressing cap;

according to the mode shown in figure 1, the device is connected into the air passage through the cutting sleeve 5 and the cutting sleeve 6;

the first cut valve V2 was closed, the second cut valve V4 and the third cut valve V5 were opened, the first three-way valve V3 was switched to the vacuum gauge, the second three-way valve V6 was switched to the vacuum system 7, and the degassing treatment was started.

After degassing the sample, the catalyst may be adsorbed or reacted as desired. The specific steps of carrying out gas adsorption on the sample are as follows:

the third stop valve V5 is closed, the pressure reducing valve V1 and the first stop valve V2 are opened, and the first three-way valve V3 is switched to a vacuum gauge or a pressure gauge according to the pressure range required to be absorbed;

opening the flowmeter 2, and introducing gas to the required pressure;

closing the first cut-off valve V2 to maintain adsorption equilibrium;

after adsorption balance, the handle 9 is rotated to drive the guide rod 10 to the lowest end, the sealing plug 17 is pressed into the sample tube 18, and the sample is sealed;

the second stop valve V4 is closed, the third stop valve V5 is opened, and the second three-way valve V6 is switched to the tail gas outlet;

and (4) unscrewing the bracket pressing cap 20, taking out the sample tube 18, mounting a polytetrafluoroethylene cap, and transferring to a nuclear magnetic resonance instrument for detection.

The device can also be used for reaction treatment and characterization of the catalyst after reaction, and the specific implementation steps are as follows:

performing degassing treatment according to the degassing step;

opening the pressure reducing valve V1 and the first stop valve V2, closing the first three-way valve V3, and switching the second three-way valve V6 to the exhaust gas outlet;

adjusting the flow meter to the desired flow

Starting the reaction;

after the reaction reaches the required time, the pressure reducing valve V1, the first stop valve V2 and the second stop valve V4 are closed, and the second three-way valve V6 is switched to a vacuum system to pump out redundant reaction gas;

and closing the second three-way valve, unscrewing the bracket pressing cap 20, taking out the sample tube 18, mounting a polytetrafluoroethylene cap, and transferring to a nuclear magnetic resonance instrument for detection.

Example 1

The device and the system can adsorb xenon with different pressures for researching the properties of the molecular sieve pore canal, the ZSM-22 molecular sieve is a one-dimensional straight-through pore canal, and after adsorbing the Xe, the molecular sieve is static¹²⁹The Xe NMR spectrum is affected by the anisotropy of chemical shift, so that the adsorption signal in the pore channels is widened and the resolution is reduced, as shown in FIG. 4. The method of adsorption is carried out by using the device and the system of the invention¹²⁹Xe NMR adsorption to enable magic angle spinning¹²⁹And (4) Xe NMR characterization to obtain a high-resolution nuclear magnetic resonance spectrogram, so that the pore channel property can be further analyzed. As can be seen from FIG. 4, under the conditions of static state and different magic angle rotation rates, Xe (near 180 ppm) signals adsorbed in the molecular sieve pore channels and Xe (near 0 ppm) signals in gas phase can be collected, meanwhile, under the static state, the adsorbed Xe signals show wide signals due to chemical shift anisotropy, and high-resolution isotropic adsorption signals can be obtained under the magic angle rotation conditions, which shows that the device of the invention has better sealing effect and can realize the treatment and sealing of the solid nuclear magnetic resonance sample.

The above examples are provided only for the purpose of describing the present invention, and are not intended to limit the scope of the present invention. The scope of the invention is defined by the appended claims. Various equivalent substitutions and modifications can be made without departing from the spirit and principles of the invention, and are intended to be within the scope of the invention.