In-situ crystallization device for Bruker 7mm probe as well as preparation method and application of in-situ crystallization device

Abstract

The invention discloses an in-situ crystallization device for a Bruker 7mm probe as well as a preparation method and application of the in-situ crystallization device, and belongs to the field of catalysis. The in-situ crystallization device comprises a pipe body and a cover; the open end of the pipe body and the cover are combined through threads and sealed through an O-shaped ring. The in-situ crystallization device provided by the invention has the characteristics of high temperature resistance, high pressure resistance and corrosion resistance, and solves the problem that in-situ characterization is difficult in the molecular sieve crystallization process. The manufacturing method is simple in process and low in cost, and large-scale production and commercialization can be achieved.

Description

Technical Field

[0001] The present application relates to an in-situ crystallization device for a Bruker 7mm probe, its preparation method and application, belonging to the field of catalysis. Background Art

[0002] High-resolution solid-state nuclear magnetic resonance technology is one of the most important means in the existing solid material characterization, and is widely used in the fields of chemistry, chemical engineering, biology, materials, etc.

[0003] Molecular sieves are widely used in the fields of catalysis, adsorption and separation, etc. due to their shape-selective catalytic selectivity and suitable adjustable acidity. In-depth study of the crystallization mechanism of molecular sieves and then pre-synthesis design is of great significance for preparing molecular sieves with excellent application properties.

[0004] Currently, the widely used molecular sieves are often synthesized under hydrothermal conditions. The characteristics of the hydrothermal process are that the synthesis raw materials are mixed and stirred in a certain proportion to form a gel, the gel is injected into a reaction kettle, and after encapsulation, the molecular sieve is crystallized at a certain temperature. During this process, under the autogenous pressure of water, through the structure-directing effect of inorganic / organic templating agents, after a certain period of crystallization, molecular sieves are generated. According to the change of relative crystallinity, crystallization is mainly divided into three stages: under the combined action of the autogenous pressure of water and the organic templating agent, nucleation centers are formed, and this process is the induction period of crystallization; with the progress of heating, the crystals gradually grow, and the relative crystallinity of the molecular sieve rises sharply; finally, the reaction system reaches the dissolution-crystallization equilibrium of the molecular sieve, and the relative crystallinity no longer rises, that is, the apparent crystallization is completed.

[0005] Therefore, in-situ nuclear magnetic resonance characterization of the molecular sieve crystallization process is of great significance for studying the molecular sieve crystallization mechanism. The difficulties in in-situ nuclear magnetic resonance characterization of the molecular sieve crystallization process are: 1. The heat resistance of the instrument; 2. The pressure resistance of the instrument; 3. The alkali corrosion resistance of the instrument. Currently, a variety of instruments / instrument accessories have been applied to the in-situ characterization of the molecular sieve crystallization process, but the application systems of these instruments are concentrated in the medium temperature range (65-120°C) and the pressure is concentrated in the low pressure range (less than 2 bar).

[0006] Currently, there is only one report on an in-situ crystallization device and its application for studying the crystallization mechanism of molecular sieves using a Bruker-Biospin 7 mm probe. Ivanova I.I et al. (Ivanova I, Kolyagin Y, Kasyanov I, et al. Time-Resolved In-Situ MAS NMR Monitoring of the Nucleation and Growth of Zeolite BEA Catalysts under Hydrothermal Conditions[J]. Angew. Chem., Int. Ed. 2017, 56, 15344-15347) disclosed an in-situ crystallization device with a two-layer structure made of various polymer materials, which can be used to study the crystallization mechanism of BEA molecular sieves at 150 °C. However, the above in-situ crystallization device has a complex structure and uses many materials, which limits its application in the study of the crystallization mechanism of molecular sieves. Summary of the Invention

[0007] Aiming at the problems existing in the prior art, the purpose of the present invention is to provide an in-situ crystallization device for a Bruker-Biospin 7 mm probe, its preparation method and application. The in-situ crystallization device provided by the present invention has the characteristics of high temperature resistance, pressure resistance and alkali corrosion resistance.

[0008] According to the first aspect of the present application, an in-situ crystallization device for a Bruker 7 mm probe is provided.

[0009] An in-situ crystallization device for a Bruker 7 mm probe, the in-situ crystallization device includes a tube body and a lid;

[0010] The open end of the tube body and the lid are combined by threads and sealed by an O-ring.

[0011] The in-situ crystallization device for a Bruker-Biospin 7 mm probe has a tubular structure, is composed of a tube body and a lid, is combined by threads and sealed by an O-ring.

[0012] The in-situ crystallization device is made of organic polymer materials.

[0013] Optionally, the total height of the tube body is 10-13.5 mm;

[0014] The diameter of the tube body is 5.0-5.5 mm;

[0015] The thickness of the tube body is 0.9-1.7 mm.

[0016] Preferably, the overall height of the tube body is 12 to 13 mm;

[0017] The thickness of the tube body is 1.2 to 1.5 mm.

[0018] Optionally, the thickness of the lid is 1.5 to 2.0 mm.

[0019] Preferably, the thickness of the lid is 1.7 to 1.9 mm.

[0020] Optionally, the inner diameter of the O-ring is 1.5 to 3.0 mm;

[0021] The wire diameter of the O-ring is 0.3 to 1.0 mm.

[0022] Preferably, the inner diameter of the O-ring is 2.0 to 2.5 mm;

[0023] The wire diameter of the O-ring is 0.4 to 0.6 mm.

[0024] Optionally, the in-situ crystallization device is made of an organic polymer material.

[0025] Optionally, the organic polymer material is selected from at least one of polyether ether ketone (PEEK), polyimide (PI), polytetrafluoroethylene (PTFE), and polymethyl methacrylate (PMMA).

[0026] Optionally, the material of the O-ring is selected from at least one of natural rubber, synthetic rubber, silicone rubber, and perfluoroether material.

[0027] Optionally, the total weight of the in-situ crystallization device is 0.37 to 0.39 g;

[0028] Among them, the total weight includes the masses of the tube body, the lid, and the O-ring.

[0029] Optionally, the thread model of the in-situ crystallization device is M3.

[0030] Specifically, the overall height of the tube body is 13 mm, the diameter is 5.2 mm, the thickness is 1.5 mm, and the total weight is 0.38 g. The inner diameter of the O-ring is 2.5 mm, and the wire diameter is 0.5 mm.

[0031] According to the second aspect of the present application, a preparation method of the above-mentioned in-situ crystallization device is provided.

[0032] The preparation method of the above-mentioned in-situ crystallization device includes the following steps:

[0033] S1. Cut the organic polymer rod-shaped material on a lathe to a specified diameter to obtain a rough blank of the material;

[0034] S2. Cut and mill the rough material blank to obtain a tube body and a lid;

[0035] S3. Tap the tube body and the lid;

[0036] S4. Polish and trim the tapped tube body and lid, and after assembly, an in-situ crystallization device is obtained.

[0037] According to the third aspect of the present application, an application of the above-mentioned in-situ crystallization device is provided.

[0038] The application of the above-mentioned in-situ crystallization device in the in-situ characterization of the molecular sieve crystallization mechanism, and the rotation scenario applied is a 7mm solid magic angle spinning nuclear magnetic resonance probe of Bruker Biospin Corporation and its supporting zirconia rotor, and the magic angle spinning rate range is 2000 - 5000Hz.

[0039] Optionally, the experimental temperature of the application is 0 - 220°C.

[0040] Optionally, the experimental pH value of the application is pH 7 - 14.

[0041] The beneficial effects that the present application can produce include:

[0042] The in-situ crystallization device for Bruker 7mm probe provided by the present application has the advantages of temperature resistance, pressure resistance, and alkali corrosion resistance, can be applied to any 7mm-sized solid nuclear magnetic resonance probe, and has application universality. It has the advantage of stable rotation during use. The manufacturing method has a simple process and low cost, and can be mass-produced and commercialized. Description of the Drawings

[0043] Figure 1 Schematic diagram of the in-situ crystallization device used in the manufacturing process of Example 1.

[0044] Figure 2 Physical photo of the in-situ crystallization device manufactured in Example 1.

[0045] Figure 3 Physical photo of the O-ring used in the in-situ crystallization device manufactured in Example 1.

[0046] Figure 4 Physical photo of the assembly process of the in-situ crystallization device manufactured in Example 1 combined with the Bruker-Biospin 7mm probe rotor.

[0047] Figure 5 Special instrument photo for testing the stable rotation state of the in-situ crystallization device manufactured in Example 1.

[0048] Figure 6The rotational speed photos of the in-situ crystallization device manufactured for Example 1 during stable rotation.

[0049] Figure 7 The rotational speed photos of the in-situ crystallization device manufactured for Examples 2 - 5 during stable rotation.

[0050] Figure 8 The pictures of relevant literature of the in-situ crystallization device for Comparative Examples 1 - 3.

[0051] Figure 9 The measured spectrogram of Application Example 1. Detailed implementation manners

[0052] The present application will be described in detail below in conjunction with examples, but the present application is not limited to these examples.

[0053] Unless otherwise specified, the raw materials in the examples of the present application are all purchased through commercial channels.

[0054] Unless otherwise specified, the test methods are all conventional methods, and the instrument settings are all the settings recommended by the manufacturer.

[0055] The present invention provides an in-situ crystallization device for a Bruker - Biospin 7mm probe, which has a tubular structure and is composed of a tube body and a lid, and is combined by threads and sealed by an O-ring.

[0056] In the present invention, the organic polymer material of the in-situ crystallization device is preferably one or more of polyetheretherketone (PEEK), polytetrafluoroethylene (PTFE), and polymethyl methacrylate (PMMA), and more preferably polyetheretherketone.

[0057] In the present invention, the material of the O-ring for sealing the in-situ crystallization device is preferably one or more of natural rubber, synthetic rubber, silicone rubber, and perfluoroether material. More preferably, it is perfluoroether material.

[0058] In the present invention, the total height of the in-situ crystallization device is preferably 10.0 - 13.5 mm, more preferably 12.0 - 13.0 mm; the thickness of the tube body is preferably 0.9 - 1.7 mm, more preferably 1.2 - 1.5 mm; the thickness of the lid is preferably 1.5 - 2.0 mm, more preferably 1.7 - 1.9 mm; the inner diameter of the O-ring is preferably 1.5 - 3.0 mm, more preferably 2.0 - 2.5 mm; the wire diameter of the O-ring is preferably 0.3 - 1.0 mm, more preferably 0.4 - 0.6 mm.

[0059] The present invention provides a preparation method of the in-situ crystallization device described in the above technical solution, including the following steps:

[0060] 1) Cut, mill, tap, and polish the material to obtain the parts of the in-situ crystallization device;

[0061] 2) Assemble the parts of the in-situ crystallization device to obtain the in-situ crystallization device.

[0062] In the present invention, the material is cut, milled, and polished to obtain the parts of the in-situ crystallization device and then assembled to obtain the in-situ crystallization device.

[0063] In the present invention, the manufacturing process of the in-situ crystallization device preferably includes the following steps:

[0064] 1) Cut the rod-shaped organic polymer material on a lathe to a specified diameter to obtain a rough blank of the material;

[0065] 2) Cut and mill the rough blank to obtain a tube body and a lid;

[0066] 3) Tap the tube body and the lid;

[0067] 4) Polish and trim the tapped tube body and lid, and after assembly, obtain the in-situ crystallization device.

[0068] In the present invention, there is no special limitation on the machine tool used for cutting and milling, and equipment well-known to those skilled in the art can be used, such as a manual machine tool or a numerical control machine tool;

[0069] In the present invention, there is also no special limitation on the tool material used for cutting and milling, and equipment well-known to those skilled in the art can be used, such as a stainless steel tool or a diamond tool.

[0070] In the present invention, there is no special limitation on the tool used in the tapping process, and equipment well-known to those skilled in the art can be used, such as a threading tool or a wire picking tool.

[0071] In the present invention, there is no special limitation on the tool used for polishing the tube body and the lid, and equipment well-known to those skilled in the art can be used, such as sandpaper or polishing paste.

[0072] The present invention provides the application of the in-situ crystallization device described in the above technical solution or the in-situ crystallization device obtained through the above technical solution in the study of the molecular sieve crystallization mechanism.

[0073] In the present invention, the in-situ crystallization device is tested before use, and the main test items are temperature resistance, pressure resistance, alkali corrosion resistance, and rotation test.

[0074] In the present invention, the specific process of the temperature resistance test is as follows: Weigh and record the relevant parts of the in-situ crystallization device, and use a heating device to heat the in-situ crystallization device to the temperature to be measured and keep it at that temperature for a certain period of time. In the present invention, the temperature to be measured is preferably 60 - 220 °C, more preferably 170 °C. In the present invention, the heat preservation time is preferably 2 - 48 hours, more preferably 24 hours. After cooling, weigh the parts again using the same tools as above.

[0075] In the present invention, in the temperature resistance test part, there is no special limitation on the tool for weighing the in-situ crystallization device, and any device well-known to those skilled in the art can be used, such as a balance or an electronic balance. In the present invention, there is also no special limitation on the tool for heating the in-situ crystallization device, and any device well-known to those skilled in the art can be used, such as an oven or a sand bath. In the present invention, there is no special limitation on the cooling process either, and any method well-known to those skilled in the art can be used, such as natural cooling.

[0076] In the present invention, the specific process of the pressure resistance test is as follows: Weigh and record the relevant parts of the in-situ crystallization device, inject water into the in-situ crystallization device, assemble and seal the in-situ crystallization device according to the above technical solution, and weigh the in-situ crystallization device after injecting water again using the same tools as above. Use a heating device to heat the in-situ crystallization device after injecting water to the temperature to be measured. In the present invention, the temperature to be measured is preferably 60 - 220 °C, more preferably 170 °C. In the present invention, the heat preservation time is preferably 2 - 48 hours, more preferably 24 hours. After cooling, weigh the in-situ crystallization device after injecting water again using the same tools as above. After weighing, open the in-situ crystallization device after injecting water for visual confirmation.

[0077] In the present invention, in the pressure resistance test part, there is no special limitation on the water to be injected, and any water well-known to those skilled in the art can be used, such as distilled water or ultrapure water. There is no special limitation on the tool for weighing the in-situ crystallization device, and any device well-known to those skilled in the art can be used, such as a balance or an electronic balance. In the present invention, there is also no special limitation on the tool for heating the in-situ crystallization device, and any device well-known to those skilled in the art can be used, such as an oven or a sand bath. In the present invention, there is no special limitation on the cooling process either, and any method well-known to those skilled in the art can be used, such as natural cooling.

[0078] In the present invention, the specific process of the alkali corrosion resistance test is as follows: Weigh and record the relevant parts of the in-situ crystallization device, and soak the in-situ crystallization device in a sodium hydroxide solution for a period of time. In the present invention, the concentration of the sodium hydroxide solution is preferably 0 - 2 mol / L, more preferably 1 mol / L. In the present invention, the soaking time is preferably 2 - 48 hours, more preferably 24 hours. After soaking, wash the parts with water and weigh the parts again using the same tools as above.

[0079] In the present invention, there are no special limitations on the tools for alkali soaking of the in-situ crystallization device, and equipment well-known to those skilled in the art can be used, such as beakers or reaction kettles. There are no special limitations on the water used for washing the parts, and water well-known to those skilled in the art can be used, such as distilled water or ultrapure water.

[0080] In the present invention, the specific process of the rotation test is as follows: Assemble the relevant parts of the in-situ crystallization device into the in-situ crystallization device, combine the device with a 7 mm zirconia rotor produced by Bruker-Biospin, and conduct a rotation test using a 7 mm rotational speed test device produced by Bruker-Biospin. The spin rate is preferably 2000 - 5000 Hz, more preferably 3500 - 4500 Hz.

[0081] In the present invention, in the rotation test part, the tool for testing the rotational speed of the in-situ crystallization device is limited to a special rotational speed test device manufactured by Bruker-Biospin; in the present invention, in the rotation test part, the tool for driving the in-situ crystallization device is limited to a special device manufactured by Bruker-Biospin, with the model being MAS-II or MAS-III, and the preferred model is MAS-III; in the present invention, the tool for testing the rotational speed of the in-situ crystallization device is limited to the TOPSPIN software produced by Bruker-Biospin, but there are no special limitations on the specific version of the software, and versions familiar to those skilled in the art can be used, such as TOPSPIN 3.0, TOPSPIN 4.0.9, TOPSPIN 4.1.1, or TOPSPIN 4.3.0, etc.

[0082] The present invention also provides the application of the in-situ crystallization device described in the above technical solution in the in-situ characterization of the molecular sieve crystallization mechanism.

[0083] In the present invention, the application conditions of the in-situ crystallization device in the in-situ characterization of the molecular sieve crystallization mechanism include: the magnetic field strength of the solid nuclear magnetic resonance spectrometer of Bruker-Biospin Corporation used should be 9.4 - 18.7 Tesla (400 - 800 MHz instrument), the rotor size of the probe is limited to 7 mm, and the specific model of the probe is preferably a 7 mm DVT, 7 mm WVT, 7 mm MASCAT or 7 mm LASERMAS probe, more preferably a 7 mm MASCAT probe; the rotor material is limited to zirconia. The tool for driving the in-situ crystallization device is limited to a special equipment manufactured by Bruker-Biospin Corporation, with the model being MAS-II or MAS-III, and the preferred model is MAS-III; the rotation rate (Spin Rate) is preferably 2000 - 5000 Hz, more preferably 3500 - 4500 Hz. The data acquisition system is limited to the nuclear magnetic resonance spectrometer cabinet manufactured by Bruker-Biospin Corporation, and the specific model is preferably AVANCE III, AVANCE III HD or AVANCE NEO, more preferably AVANCE NEO; there is no special limitation on the pulse sequence for testing, and according to the testing requirements, sequences well-known to those skilled in the art can be used, such as zg, cp, cp90, hpdec, Hetcor or mp3qzqf, etc.

[0084] Example 1

[0085] As shown Figure 1 In a numerically controlled lathe, a rod-shaped material made of PEEK is cut with a stainless steel tool bit to a diameter of 5.21 mm to obtain a rough blank of the material; the rough blank of the material is cut to a length of 10.97 mm, and then milled on a milling machine with a stainless steel milling cutter to make a tube body with an inner diameter of 2.0 mm, an outer diameter of 5.2 mm, and a wall thickness of 1.6 mm; the rough blank of the material is cut to a length of 4.7 mm, and then cut on a lathe to make a lid with a thickness of 1.9 mm and a thread length of 2.8 mm. The tube body and the lid are tapped with a wire-picking tool and a threading tool, and the thread model is M3. The tube body and the lid are polished with sandpaper to obtain the in-situ crystallization device.

[0086] As can be seen Figure 2 from the figure, the in-situ crystallization device is cylindrical and consists of a tube body, a lid and an O-ring. As can be seen Figure 3 from the figure, the O-ring is made of perfluoroether material. Figure 4 Figure [ID number not clear] is a physical photo of the assembly process of the in-situ crystallization device manufactured in Example 1 combined with the Bruker-Biospin 7 mm probe rotor. As can be seen Figure 4 from the figure, the in-situ crystallization device and the rotor can be well combined.

[0087] Temperature resistance test of the in-situ crystallization device obtained in Example 1:

[0088] Take the in-situ crystallization device obtained in Example 1, weigh the tube body, cap and O-ring with an electronic balance and record. Use an oven to heat Example 1 to 170 °C and keep it warm for 24 hours. After cooling, weigh Example 1 with the electronic balance again.

[0089] Before heating: 0.3846 g, after heating: 0.3844 g. From the experiment, it can be seen that Example 1 has heat-resistant properties.

[0090] Pressure resistance test of the in-situ crystallization device obtained in Example 1:

[0091] Take the in-situ crystallization device obtained in Example 1, weigh the tube body, cap and O-ring with an electronic balance and record. Inject water into the in-situ crystallization device obtained in Example 1, combine Example 1 according to the above technical solution and seal it, and weigh it again with an electronic balance and record. Use an oven to heat the in-situ crystallization device obtained in Example 1 to 170 °C and keep it warm for 24 hours. After cooling, weigh the in-situ crystallization device obtained in Example 1 filled with water with the electronic balance again. After weighing, open Example 1 for visual confirmation.

[0092] Mass of the empty in-situ crystallization device obtained in Example 1: 0.3844 g, mass of the in-situ crystallization device obtained in Example 1 after filling with water: 0.3904 g, mass of the in-situ crystallization device filled with water after heating and cooling: 0.3898 g. Open the in-situ crystallization device obtained in Example 1 and visually confirm that there is still water. From the experiment, it can be seen that the water mass loss of the in-situ crystallization device obtained in Example 1 is within 10%. Measure 3 times repeatedly, and the water mass losses are 8%, 10% and 6% respectively, all within the weighing error range, indicating that it has pressure resistance properties.

[0093] Alkali corrosion resistance test of the in-situ crystallization device obtained in Example 1:

[0094] Take the in-situ crystallization device obtained in Example 1, weigh the tube body, cap and O-ring with an electronic balance and record. Take 2.0 g of flaky NaOH solid and mix it with 50 mL of ultrapure water to obtain a 1 mol / L sodium hydroxide solution. Put the in-situ crystallization device obtained in Example 1 into a beaker, inject the above sodium hydroxide solution, and soak it for 24 hours. After soaking, wash the in-situ crystallization device obtained in Example 1 with water, and weigh the parts with an electronic balance again.

[0095] Mass of the in-situ crystallization device obtained in Example 1 after drying: 0.3848 g, amount of sodium hydroxide solution: 15.0 mL. Mass of the in-situ crystallization device obtained in Example 1 after soaking, washing, and drying: 0.3851 g. From the experiment, it can be seen that within the weighing error range, the in-situ crystallization device obtained in Example 1 has alkali corrosion resistance.

[0096] Rotation test of the in-situ crystallization device obtained in Example 1:

[0097] Take the in-situ crystallization device obtained in Example 1, combine the in-situ crystallization device obtained in Example 1 with a 7 mm zirconia rotor produced by Bruker-Biospin, and conduct a rotation test with a 7 mm rotational speed test device produced by Bruker-Biospin. The MAS-III control unit is used to control the rotation system, and the software version is TOPSPIN 4.1.1. The spin rate starts from 2000 Hz and increases step by step by 100 Hz each time until 5000 Hz. If the rotational speed changes from red to green within one minute, it is judged that the rotation is stable; otherwise, the spin rate at the last stable time is used as the final data. Figure 5 Photo of the special instrument for testing the rotation stability state of the in-situ crystallization device manufactured in Example 1. Figure 6 Photo of the rotational speed of the in-situ crystallization device manufactured in Example 1 when it is rotating stably. It can be seen from Figure 6 that the in-situ crystallization device manufactured in Example 1 can rotate stably at 4500 Hz.

[0098] Examples 2 - 5

[0099] Examples 2 - 5 were manufactured according to the drawings of Example 1. The differences from Example 1 are that their lengths, diameters, and the O-rings used are slightly different, and the differences are listed in Table 1.

[0100] Table 1 Properties and rotation stability rates of Examples 2 - 5

[0101]

[0102] Figure 7 Photo of the rotational speed of the in-situ crystallization devices manufactured in Examples 2 - 5 when they are rotating stably. It can be seen from Figure 7 that the stable rotation rates of Examples 2 - 5 are not the same, but all are in the range of 3500 - 5000 Hz.

[0103] Comparative Example 1

[0104] According to the literature "Shi J, Anderson W, Direct Observation of Zeolite A Synthesis by in Situ Solid-State NMR[J], Chem. Mater. 1996, 8, 369 - 375", an in-situ crystallization device made of polytetrafluoroethylene was used, and a Bruker MSL-400 type solid nuclear magnetic resonance spectrometer was used for testing at a rotation rate of 2100 Hz at 65 °C to characterize the crystallization mechanism of zeolite A.

[0105] Comparative Example 2

[0106] According to the literature "Zhao Z, Xu S, Bao X, et al, In Situ High Temperature High Pressure MAS NMR Study on the Crystallization of AlPO4-5[J], J. Phys. Chem. C 2016, 120, 1701 - 1708", an in-situ crystallization device made of zirconia was used. Under weakly alkaline conditions, a Varian 300 MHz NMR type nuclear magnetic resonance spectrometer was used at a rotation rate of 4000 Hz at 150 °C to characterize the crystallization mechanism of AlPO4-5 type zeolite.

[0107] Comparative Example 3

[0108] According to the literature "Ivanova I, Kolyagin Y, Kasyanov I, et al. Time-Resolved In Situ MAS NMR Monitoring of the Nucleation and Growth of Zeolite BEA Catalysts under Hydrothermal Conditions[J]. Angew. Chem., Int. Ed. 2017, 56, 15344 - 15347", a double-layer in-situ crystallization device made of various polymers was used, and a Bruker AVANCE-II 400 type nuclear magnetic resonance spectrometer was used at rotation rates of 5000 Hz at 135 °C and 150 °C to characterize the crystallization mechanism of BEA type zeolite.

[0109] Figure 8 The pictures of the in-situ crystallization devices given in the literatures of Comparative Examples 1 - 3 are shown. It can be seen that the structures of the above in-situ crystallization devices are complex and the types of materials used are numerous.

[0110] Application Example 1

[0111] The mordenite crystallization mechanism was studied using the in-situ crystallization device fabricated in Example 1. The specific process is as follows:

[0112] Under magnetic stirring, 0.47 g of sodium hydroxide was dissolved in 0.8 mL of water. Then, 0.36 g of sodium aluminate and 16.1 mL of water were added successively, and the mixture was stirred for 10 min. After that, 2.45 g of fumed silica was added and stirring was continued for 30 min to obtain a mordenite synthesis gel (where the molar composition of the gel was Na2O:Al2O3:SiO2:H2O = 6.3:1:8.2:381). The gel was transferred into the in-situ crystallization device and sealed. The in-situ crystallization device was assembled with a 7 mm zirconia rotor and placed in a 7 mm MASCAT probe. Then, under the control of the MAS-III control unit, the in-situ crystallization device was rotated driven by self-pressurized nitrogen. The specific rotation speed started from 2000 Hz, increased by 100 Hz each time, with an interval of 1 minute each time, until the rotation speed reached 4000 Hz. Then, through the carrier gas, starting from 25 °C, it increased by 5 °C each time, with an interval of 2 minutes each time, until 170 °C. At 170 °C, 23 Na and 27 Al were tested.

[0113] Figure 9 This is the measured spectrum of Application Example 1. It can be seen from the spectrum that 27 the chemical shift of Al jumped from 80 ppm to 60 ppm after the start of crystallization, while 23 the chemical shift of Na gradually changed from 0 ppm to -16 ppm. From Figure 9 this, it can be known that the in-situ crystallization device can realize the study of the mordenite crystallization mechanism.

[0114] The above are only several embodiments of the present application and do not impose any form of limitation on the present application. Although the present application is disclosed with preferred embodiments as above, it is not intended to limit the present application. Any person skilled in the art, without departing from the scope of the technical solution of the present application, making some changes or modifications using the disclosed technical content is equivalent to equivalent implementation cases and all fall within the scope of the technical solution.

Claims

1. An in-situ crystallization device for a Bruker 7mm probe, characterized in that, The in-situ crystallization device includes a tube body and a lid; The open end of the tube body and the lid are combined by threads and sealed with an O-ring.

2. The in-situ crystallization device according to claim 1, characterized in that, The total height of the tube body is 10 - 13.5 mm; The diameter of the tube body is 5.0 - 5.5 mm; The thickness of the tube body is 0.9 - 1.7 mm; Preferably, the total height of the tube body is 12 - 13 mm; The thickness of the tube body is 1.2 - 1.5 mm.

3. The in-situ crystallization device according to claim 1, characterized in that, The thickness of the lid is 1.5 - 2.0 mm; Preferably, the thickness of the lid is 1.7 - 1.9 mm.

4. The in-situ crystallization device according to claim 1, characterized in that The inner diameter of the O-ring is 1.5 - 3.0 mm; The wire diameter of the O-ring is 0.3 - 1.0 mm; Preferably, the inner diameter of the O-ring is 2.0 - 2.5 mm; The wire diameter of the O-ring is 0.4 - 0.6 mm.

5. The in-situ crystallization device according to claim 1, wherein, The in-situ crystallization device is made of an organic polymer material; Preferably, the organic polymer material is selected from at least one of polyether ether ketone, polyimide, polytetrafluoroethylene, and plexiglass; The material of the O-ring is selected from at least one of natural rubber, synthetic rubber, silicone rubber, and perfluoroether material.

6. The in-situ crystallization device according to claim 1, wherein, The total weight of the in-situ crystallization device is 0.37 - 0.39 g; Among them, the total weight includes the mass of the tube body, the lid, and the O-ring.

7. The in-situ crystallization device according to claim 1, characterized in that The thread model of the in-situ crystallization device is M3.

8. A method for preparing the in-situ crystallization device according to any one of claims 1 to 7, characterized in that, It includes the following steps: S1. Cut the organic polymer rod-shaped material on a lathe to a specified diameter to obtain a rough blank of the material; S2. Cut and mill the rough blank of the material to obtain the tube body and the lid; S3. Tap the tube body and the lid; S4. Polish and trim the tapped tube body and lid, and after assembly, the in-situ crystallization device is obtained.

9. Use of the in-situ crystallization device according to any one of claims 1 to 7 in in-situ characterization of the molecular sieve crystallization mechanism, characterized in that, The rotation scenario applied is a 7 mm solid magic angle spinning nuclear magnetic resonance probe of Bruker Biospin Corporation and its supporting zirconia rotor, and the magic angle spinning rate range is 2000 - 5000 Hz.

10. The application according to claim 9, characterized in that, The experimental temperature applied is 0 - 220 °C; Preferably, the experimental pH value applied is pH 7 - 14.

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