Low-temperature liquid nitrogen device and high-pressure polymerization device

Abstract

The present application relates to a kind of high-pressure polymerization reaction low-temperature liquid nitrogen device, belong to high-pressure new material preparation technical field, circular cryogenic container pressurization is easy to fail when polymerizing, heat leakage is serious, one of the problems such as not enough liquid raw material is loaded into the sample cavity of high-pressure polymerization reaction device.The low-temperature liquid nitrogen device is composed of upper rectangular parallelepiped and lower cylinder, the axis of the cylinder is different from the distance of the opposite two sides of the rectangular parallelepiped.The low-temperature liquid nitrogen device of the present application can greatly reduce the heat leakage at the bottom of the low-temperature liquid nitrogen container, thereby ensuring the slow evaporation of liquid nitrogen, more cooling for the cooling part of anvil. Long time cooling can be carried out, and the main body of the press will not be supercooled due to heat leakage during the experiment. The refrigeration effect caused by heat absorption from the external environment and heat leakage from the bottom of the low-temperature liquid nitrogen container has been balanced.

Description

Technical Field

[0001] This invention relates to the field of high-pressure new material preparation technology, and in particular to a cryogenic liquid nitrogen device for cryogenic liquefaction and encapsulation of gaseous raw materials. Background Technology

[0002] The synthesis of large-volume fluid samples requires a top-and-bottom pressurization method designed based on the principle of large support. This is because the mechanical structure of top-and-bottom pressurization provides a large horizontal space in the high-pressure region, facilitating the placement of cryogenic environments and the loading and control of gaseous feedstocks. Furthermore, the radial pressure gradient generated by uniaxial pressurization is negligible for low-hardness materials. Based on this, the GH-type press was developed specifically for the research and development of high-energy-density energetic materials.

[0003] The principle of the high-pressure cryogenic gas liquefaction and encapsulation technology of the GH type press is as follows: The gaseous raw material is liquefied using cryogenic cooling and enters the sealed cavity between the upper and lower anvils in a cooled composite anvil structure. A pressure slightly higher than atmospheric pressure ensures the cavity is filled. The sealed cavity contains a perforated sheet-like metal gasket. The GH type press compresses the upper and lower anvils, ensuring tight contact between the anvil surfaces and the gasket, thereby sealing the liquid gaseous raw material to be filled into the sample cavity. The GH type press mainly includes the press body, sealing device, gas introduction device, and cooling device.

[0004] In the microgram-level polymerized carbon monoxide (p-CO) experiment, the sample was encapsulated in a diamond anvil cell. The outer diameter and height of the entire diamond anvil cell did not exceed 50 mm, and pressure was applied mechanically by rotation. All parts were unaffected by the low-temperature environment and remained operational. Therefore, the entire device could be easily enclosed in a cryostat, which could be immersed in liquid nitrogen to achieve gas liquefaction and pressurization. However, for a 100-ton GH press, the overall weight and size are relatively large, and the GH press uses a hydraulic system for pressurization. Therefore, it is not possible to cool the entire GH press device to liquid nitrogen temperature as in the microgram-level sample development. Summary of the Invention

[0005] Based on the above analysis, the present invention aims to provide a cryogenic liquid nitrogen device for use in high-pressure polymerization reactors, in order to solve one of the problems of existing circular cryogenic containers that are prone to failure in pressurization during polymerization, have serious heat leakage, and cannot load sufficient liquid raw materials into the sample chamber of the high-pressure polymerization reactor.

[0006] In a first aspect, the present invention provides a cryogenic liquid nitrogen device for high-pressure polymerization reaction, the cryogenic liquid nitrogen device being composed of an upper cuboid and a lower cylinder, wherein the axis of the cylinder is at a different distance from two opposite sides of the cuboid.

[0007] Furthermore, the upper surface of the cuboid has an open structure.

[0008] Furthermore, the opening is a liquid nitrogen inlet.

[0009] Furthermore, the cryogenic liquid nitrogen device is wrapped with an insulation layer on the outside.

[0010] Furthermore, the upper cuboid and the lower cylinder are integrally formed structures.

[0011] Furthermore, the high-pressure polymerization reaction cryogenic liquid nitrogen device is made of sheet metal.

[0012] Secondly, the present invention provides a high-pressure polymerization reactor, including the aforementioned cryogenic liquid nitrogen device.

[0013] Furthermore, the device also includes an upper anvil, an upper anvil, a lower anvil, and a lower anvil seat;

[0014] The upper anvil and upper anvil are located within the cuboid, while the lower anvil and lower anvil seat are located within the cylinder.

[0015] Furthermore, the device also includes a sealing ring disposed between the upper anvil and the lower anvil;

[0016] The sealing ring is located within the cuboid of the cryogenic liquid nitrogen device.

[0017] Furthermore, the device also includes a sealing gasket disposed within a sealing ring. Compared with the prior art, the present invention can achieve at least one of the following beneficial effects:

[0018] (1) The cryogenic liquid nitrogen device of the present invention can significantly reduce heat leakage at the bottom of the cryogenic liquid nitrogen container, thereby ensuring the slow evaporation of liquid nitrogen and allowing it to be used more for cooling the anvil section. It can perform long-term cooling without causing the compressor body to become too cold due to heat leakage during the experiment. The cooling effect caused by the compressor body absorbing heat from the external environment and the heat leakage from the bottom of the cryogenic liquid nitrogen container can be balanced. The cryogenic liquid nitrogen device can realize the loading of gaseous samples, which is a prerequisite for subsequent high-pressure polymerization reactions.

[0019] (2) The sealing ring in the high-pressure polymerization reactor of the present invention can realize the liquefaction and encapsulation of gaseous raw material samples and realize the high-pressure polymerization reaction of gaseous raw materials, filling the gap in the prior art. The device of the present invention has good sealing performance and will not have the problem of gas leakage. The gasket design ensures that it is not easy to crack and be damaged. The design of the sealing ring and the upper and lower anvils improves the compression ratio of the reaction chamber. The liquid nitrogen cooling device has high cooling efficiency, which reduces the pressure module to the liquid nitrogen temperature and makes the addition of liquid nitrogen operation convenient.

[0020] In this invention, the above-described technical solutions can be combined with each other to achieve more preferred combinations. Other features and advantages of this invention will be set forth in the following description, and some advantages may become apparent from the description or be learned by practicing the invention. The objects and other advantages of this invention can be realized and obtained from what is particularly pointed out in the description and drawings. Attached Figure Description

[0021] The accompanying drawings are for illustrative purposes only and are not intended to limit the invention. Throughout the drawings, the same reference numerals denote the same parts.

[0022] Figure 1 This is a cross-sectional schematic diagram of a high-pressure polymerization reactor according to the present invention;

[0023] Figure 2 This is a schematic diagram of the sealing ring assembly of the present invention;

[0024] Figure 2-1 This is a physical image of the sealing ring of the present invention;

[0025] Figure 3 This is a schematic diagram of the sealing gasket structure of the present invention;

[0026] Figure 3-1 This is a physical image of the sealing gasket of the present invention;

[0027] Figure 4 This is a schematic diagram of the cryogenic liquid nitrogen device of the present invention;

[0028] Figure 5 This is a schematic diagram of the assembly structure of the cryogenic liquid nitrogen device of the present invention;

[0029] Figure 6 This is a front view of the circular cryogenic liquid nitrogen device in Comparative Example 1 of the present invention;

[0030] Figure 7 This is the state when the upper and lower anvils begin to contact in Comparative Example 2 of the present invention;

[0031] Figure 8 This is the state of the upper and lower anvils of Comparative Example 2 of the present invention when they are compressed to their limits;

[0032] Figure 9 This is a schematic diagram of the beryllium copper soft metal ring in Comparative Example 2 of the present invention;

[0033] Figure 10 Photographs of a garbage can showing a broken square gasket and a puncture point during a test using existing technology;

[0034] Figure 11 This is a structural schematic diagram of a square box sheet metal part according to the present invention;

[0035] Figure 12 This is a schematic diagram of a cylindrical sheet metal part according to the present invention;

[0036] Figure 13 This is a schematic diagram of a round-bottom sheet metal part according to the present invention;

[0037] Figure 14 This invention relates to a rectangular parallelepiped formed by welding a square box sheet metal part.

[0038] Figure 15 This invention relates to a cylindrical structure formed by welding a cylinder.

[0039] Figure label:

[0040] 1-Upper anvil, 11-Upper anvil seat, 12-Upper pad, 13-First concentric ring, 14-First top pad, 15-Second top pad, 2-Lower anvil, 21-Lower anvil seat, 22-Second concentric ring, 3-Upper heat insulation sheet, 4-Lower heat insulation sheet, 5-Sealing ring, 51-Groove, 52-Gas duct, 53-Round hole, 54-Sealing gasket, 55-Opening, 56-Temperature sensor, 57-Temperature sensor placement part, 6-Cryogenic liquid nitrogen device, 61-Cuboid, 62-Cylinder, 63-First side, 64-Second side, 7-Upper anvil fixing sleeve, 8-Positioning ring, 9-Press, 10-Glass fiber insulation ring, 101-Beryllium copper soft metal ring. Detailed Implementation

[0041] The preferred embodiments of the present invention will now be described in detail with reference to the accompanying drawings, which constitute a part of the present invention and are used together with the embodiments of the present invention to illustrate the principles of the present invention, but are not intended to limit the scope of the present invention.

[0042] A specific embodiment of the present invention, such as Figure 1 and 4 As shown, a high-pressure polymerization cryogenic liquid nitrogen device 6 is disclosed. The cryogenic liquid nitrogen device 6 consists of an upper cuboid 61 and a lower cylinder 62. The distances from the axis of the cylinder 62 to the opposite first side 63 and second side 64 of the cuboid 61 are different.

[0043] In existing technologies, cryogenic liquid nitrogen devices are circular cryogenic containers, which are relatively compact. However, during actual gas liquefaction and encapsulation experiments, the press is prone to frosting, frequently resulting in failure to pressurize and causing experimental failure. Research has revealed that this phenomenon is related to the structure of the cryogenic liquid nitrogen device. Based on this, the present invention features an original design for the cryogenic liquid nitrogen device 6 and its related structures. Using the cryogenic liquid nitrogen device 6 of the present invention, the press will not experience frosting.

[0044] The cryogenic liquid nitrogen device of this invention features an asymmetrical structure with a cuboid top and a cylinder bottom. This not only facilitates the addition of liquid nitrogen but also significantly reduces heat leakage at the bottom of the cryogenic liquid nitrogen container, ensuring slow evaporation of the liquid nitrogen and allowing it to be used more for cooling the anvil. Prolonged cooling is possible without the compressor body becoming too cold due to heat leakage during the experiment. The cooling effect caused by heat absorption from the external environment and heat leakage from the bottom of the cryogenic liquid nitrogen container is balanced. The cryogenic liquid nitrogen device can also load gaseous samples, a prerequisite for subsequent high-pressure polymerization reactions.

[0045] In one specific embodiment, the upper surface of the cuboid 61 is an open structure.

[0046] In one specific embodiment, the cryogenic liquid nitrogen device 6 is wrapped with an insulation layer.

[0047] In one specific implementation, the upper cuboid and the lower cylinder are integrally formed structures.

[0048] In one specific embodiment, the high-pressure polymerization reaction cryogenic liquid nitrogen device is fabricated from sheet metal.

[0049] Another specific embodiment of the present invention, such as Figure 1-5 As shown, a high-pressure polymerization reactor is disclosed, including the aforementioned cryogenic liquid nitrogen device. Specifically, the device, from top to bottom, includes an upper heat insulation plate 3, an upper pad 12, an upper anvil seat 11, an upper anvil 1, a lower anvil 2, a lower anvil seat 21, and a lower heat insulation plate 4 arranged concentrically. A sealing ring 5 is provided between the upper anvil 1 and the lower anvil 2, and a sealing gasket 54 is provided inside the sealing ring 5. The upper anvil seat 11, the upper anvil 1, the sealing ring 5, the lower anvil 2, and the lower anvil seat 21 are arranged in the cryogenic liquid nitrogen device 6. The cryogenic liquid nitrogen device 6 is composed of an upper cuboid 61 and a lower cylinder 62. The distance from the axis of the cylinder 62 to the two opposite sides of the cuboid 61 is different. The upper anvil seat 11, the upper anvil 1, and the sealing ring 5 are located inside the cuboid 61, and the lower anvil 2 and the lower anvil seat 21 are located inside the cylinder 62.

[0050] Compared with the prior art, the sealing ring 5 in the high-pressure polymerization reactor of the present invention can realize the liquefaction and encapsulation of gaseous raw material samples and realize the high-pressure polymerization reaction of gaseous raw materials, filling the gap in the prior art. In addition, the device of the present invention has good sealing performance and will not have the problem of gas leakage. The gasket design ensures that it is not easy to crack or be damaged. The liquid nitrogen cooling device has high cooling efficiency, which reduces the pressure module to liquid nitrogen temperature and makes the addition of liquid nitrogen operation convenient.

[0051] In a specific implementation, such as Figure 2 and 2-1As shown, the sealing ring 5 has a groove 51 on both its upper and lower surfaces, and an indium wire is correspondingly arranged in the groove 51.

[0052] Specifically, such as Figure 1 In use, the device of this invention employs a press to apply pressure at the lower end of the device, causing the upper anvil 1, sealing gasket 54, and lower anvil 2 to come into contact and form a cavity for the raw material reaction. The diameter of the indium wire is matched with the depth and width of the groove 51, which provides a fixed position for the indium wire. When the upper anvil 1, sealing gasket 54, and lower anvil 2 begin to contact, the indium wire is compacted in the groove 51, allowing them to fit tightly together. This seals the sealing ring 5 with the upper and lower anvils, forming a chamber between the upper and lower anvils 1 and 2 to hold liquefied gas. The sealing ring 5, through the deformation of the indium wire, creates a sealed environment at the contact surfaces with the upper and lower anvils 1 and 2, thus preventing gas or liquid leakage. Furthermore, a first top pad 14 and a second top pad 15 are provided at the upper end of the press and the upper heat insulation sheet 3. These top pads reduce the stress on the upper heat insulation sheet 3, minimizing damage.

[0053] Because sealing through metal-to-metal bonding in low-temperature tests requires extremely high precision in both the machining and assembly of components, and the difference in thermal expansion coefficients between different metals at low temperatures makes controlling the seal during cooling is difficult. Indium has good ductility at low temperatures; therefore, the sealing ring of this invention is made of aluminum with a thickness of 2mm, and indium wire serves as the sealing layer. When the high-pressure polymerization reactor is under high pressure, aluminum, being soft, easily deforms under pressure. At this time, the indium wire in the groove 51, in conjunction with the sealing ring 5, provides a seal.

[0054] The study found that the thickness of the sealing ring 5 has a significant impact on the high-pressure polymerization reaction. When the sealing ring is too thick, a large portion of the pressure applied by the apparatus is consumed in the sealing ring, resulting in insufficient pressure acting on the anvil surfaces of the upper anvil 1 and lower anvil 2, as well as on the sample, thus preventing the polymerization phase transition from completing. Conversely, when the sealing ring 5 is too thin, it is prone to cracking, damage, and leakage.

[0055] In a specific implementation, such as Figure 2 As shown, the sealing ring 5 is provided with two air guide pipes 52 fixedly connected. In a further preferred embodiment, the air guide pipes 52 are welded to the sealing ring 5. Welding can prevent air leakage.

[0056] It should be noted that the two gas guide pipes 52 are the inlet pipe and the outlet pipe, respectively. The function of the inlet pipe is to introduce the gaseous raw material into the sealed cavity formed by the sealing ring 5 and the upper and lower anvils during the sample loading stage, and cool it down until the gaseous raw material begins to liquefy in it, gradually filling the high-pressure cavity of the polymerization reaction and the sealed cavity formed by the entire aluminum sealing ring 5. After the sample is sealed, the remaining liquid in the sealed cavity will gradually vaporize during the heating process and be discharged from the sealed cavity along the outlet pipe. The discharged gas is recycled to the gas cylinder through the post-processing gas path or directly discharged to the outside through the fume hood.

[0057] Specifically, the air guide tube 52 is made of aluminum, and its diameter is 1 / 16 inch to 3 mm, preferably 3 mm. The air guide tube 52 is made of the same material as the sealing ring 5, and the same strength can reduce the possibility of breakage at the weld.

[0058] In a specific implementation, such as Figure 5 As shown, the two gas guide pipes 52 are arranged in a spiral shape in the cryogenic liquid nitrogen device 6.

[0059] It should be noted that during the experiment, the inventors discovered that the gas pressure inside the aluminum sealing ring 5 changed drastically during the cooling process, and the temperature inside the sealing ring 5 hovered around the liquefaction temperature for a long time, making it impossible to further reduce the temperature to achieve gas liquefaction. This is because the introduced gas is directly blown onto the already liquefied raw material. Therefore, placing the gas inlet pipe 52 in a spiral shape within the cryogenic liquid nitrogen device 6 extends the length of the inlet pipe, allowing it to be fully immersed in liquid nitrogen. This enables the raw material gas to liquefy prematurely within the inlet pipe and flow into the sealing ring in liquefied form. Similarly, the spiral shape of the outlet pipe increases the cooling area of ​​the gas, which is more conducive to gas liquefaction.

[0060] In a specific implementation, such as Figure 2 As shown, the included angle between the air inlet pipe and the air outlet pipe on the circular surface where the sealing ring is located is 90°.

[0061] It should be noted that the inlet and outlet pipes are set at 90° because the high-pressure polymerization reactor described in this invention needs to be fixed to the press base. Setting it at 90° facilitates the experimental operation, makes gas path connection easier, and improves operational convenience. It also facilitates the spiral arrangement of the inlet and outlet pipes.

[0062] In a specific implementation, such as Figure 2 As shown, a temperature sensor 56 is installed inside the sealing ring 5.

[0063] Specifically, the temperature sensor 56 consists of two PT100 temperature sensors, which are placed above and below the sealing gasket 54 during p-CO sample synthesis. They can display the temperature gradient distribution in the vertical direction within the sealing ring 5 cavity, and thus infer the amount of liquid sample generated.

[0064] It should be noted that holes are drilled in the side wall of the sealing ring 5, and the leads of two PT100 temperature sensors are led out through the side wall of the sealing ring 5. At the same time, the PT100 temperature sensors are connected to a digital source meter, and the resistance value of the PT100 temperature sensors is read by the computer, thereby calculating the real-time temperature inside the sealing ring 5.

[0065] In a specific implementation, such as Figure 3 and 3-1 As shown, the sealing gasket 54 has a circular structure, and two inwardly recessed openings 55 are provided on the sealing gasket 54 corresponding to the two air guide tubes 52. A temperature sensor placement part 57 is provided on the sealing gasket 54 corresponding to the temperature sensor 56.

[0066] It should be noted that the cavity (circular hole 53) in the middle of the sealing gasket 54 is the high-pressure chamber for the raw materials to react.

[0067] In one specific embodiment, the thickness of the sealing gasket 54 matches the height of the sealing ring 5, and the outer diameter of the sealing gasket 54 matches the inner diameter of the sealing ring 5, so that the sealing gasket 54 fits inside the sealing ring 5.

[0068] It should be noted that the thickness of the sealing gasket 54 needs to match the height of the aluminum sealing ring 5. Ideally, when the sealing ring 5 is compacted, the upper and lower anvils after sealing are almost close to the sealing gasket 54 but there is still a small gap. The liquefied material flows into the high-pressure cavity in the middle of the sealing ring 5 through the gap. At this time, only a slight pressure needs to be applied to make the upper and lower anvils close with the sealing gasket 54 to achieve the encapsulation of the liquefied material.

[0069] The outer diameter of the sealing gasket 54 matches the inner diameter of the sealing ring 5, ensuring that the sealing gasket 54 does not undergo radial displacement during the cryogenic liquefaction and sample encapsulation process. The inlet and outlet pipes are located at two openings 55, thus not affecting their normal operation.

[0070] Specifically, the diameter of the circular hole 53 in the center of the sealing gasket 54 is 6mm, the outer diameter of the sealing gasket 54 is 53.7mm, and the thickness is 1mm. Preferably, the material of the sealing gasket 54 is T301 stainless steel. The inner diameter of the sealing ring is 54mm, and the outer diameter is 58mm.

[0071] In a preferred embodiment, the central hole 53 of the gasket is much smaller than the outer diameter of the gasket 54 in order to prevent the gasket 54 from cracking from the hole 53 toward the edge under pressure.

[0072] In the existing technology, the sealing gasket 54 is a square shape with a central hole, measuring 30mm × 30mm × 1mm, with a hole diameter of 6mm. During testing, it sometimes cracks in a certain direction and ejects fragments outwards, posing a significant safety hazard. For example... Figure 10 The image shows a trash can where the sealing gasket of the previously used device broke and ejected fragments. After numerous tests, the sealing gasket of this invention did not exhibit the phenomenon of cracking from any direction and ejecting fragments outwards.

[0073] The sealing gasket 54 and the sealing ring 5 are matched in all directions. Therefore, as long as the position of the sealing ring 5 is fixed and it is concentrically arranged with the anvil surfaces of the upper and lower pressure anvils, the sealing gasket 54 will be fixed in a position concentric with the anvil surfaces. In addition, the large-sized circular sealing gasket 54 fills a considerable portion of the sealing ring cavity, and only a small amount of raw material gas needs to be liquefied each time to fill the cavity in the middle of the sealing gasket 54, which greatly saves the gas required for each test.

[0074] Furthermore, the annular structure of the present invention and the gasket 54 with two inwardly recessed openings 55 not only allow for the installation of the air inlet pipe and the air outlet pipe, but also provide a suitable fit.

[0075] The sealing gasket is made of T301 stainless steel, but a softer material can also be used, as long as the material can withstand a certain pressure. This can reduce the pressure loss of the high-pressure polymerization reactor and make the high-pressure test easier to perform. Secondly, the sealing gasket 54 also has sufficient strength to withstand the radial pressure inside the sample chamber.

[0076] In one specific embodiment, the cryogenic liquid nitrogen device 6 consists of an upper cuboid 61 and a lower cylinder 62, wherein the upper surface of the cuboid 62 is an open structure.

[0077] It needs to be explained, such as Figure 4 and 5As shown, the cryogenic liquid nitrogen device 6 is a one-piece structure consisting of a cuboid 61 on top and a cylinder 62 at the bottom. The distances from the axis of the cylinder 62 to the opposite first side 63 and second side 64 of the cuboid 61 are different, forming an asymmetrical structure. Positioning the end of the cylinder 62 with the larger distance from the cuboid side towards the outside facilitates the pouring of liquid nitrogen through the top opening during the experiment. Simultaneously, the relatively large cuboid structure can hold more cryogenic liquid nitrogen, reducing the need for frequent refills. Furthermore, the gas delivery pipe 52 can be more partially immersed in the cryogenic liquid, allowing the gas to be cooled and liquefied by the liquid nitrogen as it passes through the pipe 52, thereby increasing the efficiency of gas liquefaction.

[0078] In one specific embodiment, the cryogenic liquid nitrogen device 6 is wrapped with an insulation layer. This can further reduce the rate of liquid nitrogen evaporation and improve the cooling efficiency of the upper and lower anvil sections.

[0079] Specifically, the lower anvil 21 and the lower heat insulation plate 4 are respectively positioned above and below the bottom surface of the cylinder 62 below the cryogenic liquid nitrogen device 6. The lower heat insulation plate 4 is placed directly in the groove of the press 9. A positioning ring 8 is provided between the cylinder 62 of the cryogenic liquid nitrogen device 6 and the groove of the press 9 to separate the cylinder and the press. In this invention, the outer diameters of the upper anvil 1 and the upper anvil seat 11 are the same, and the outer diameters of the lower anvil 2 and the lower anvil seat 21 are the same. The upper anvil 1, the upper anvil seat 11, the lower anvil 2, and the lower anvil seat 21 are all assembled from multiple modules.

[0080] In a specific implementation, such as Figure 1 As shown, the upper anvil 1 and upper anvil seat 11 are set inside the first concentric ring 13 of copper, and the lower anvil 2 and lower anvil seat 21 are set inside the second concentric ring 22 of copper. The upper heat insulation sheet 3, the upper pad 12, the upper anvil seat 11 and the upper anvil 1 are provided with an upper anvil fixing sleeve 7 on the outside. The upper anvil fixing sleeve 7 is made of glass fiber, which can reduce heat leakage.

[0081] It should be noted that the use of copper concentric rings and upper pressure anvil fixing sleeves 7 is to ensure that all components are set concentrically.

[0082] In one specific embodiment, a heat-insulating material layer is further provided between the outer side of the lower anvil 21 and the cylinder 62. This layer is used to isolate the cryogenic liquid container from heat transfer to the press body.

[0083] The cryogenic liquid nitrogen device 6 of this invention can perform long-term cooling. During the experiment, the compressor body temperature will not become too cold due to leakage. The cooling effect caused by the compressor body absorbing heat from the external environment and the heat leakage from the bottom of the cryogenic liquid nitrogen device 6 can be balanced. Liquid nitrogen can also be injected into the container conveniently and quickly. During the experiment, the compressor body will not show obvious frost, and there is no pressurization failure caused by the compressor being too cold.

[0084] In one specific embodiment, the surfaces of the upper anvil 1 and lower anvil 2 that contact the sealing gasket 54 are both flat planar structures. The sealing ring body and the groove therein seal with the upper and lower anvils. The sealing ring forms a chamber between the upper anvil 1 and lower anvil 2 to hold liquefied gas. The sealing ring 5 and the contact surfaces with the upper and lower anvils 1 and lower anvil 2 form a sealed environment through the deformation of the indium wire. The indium wire is compacted in the groove 51 to achieve a tight fit. The sealing gasket 54 is fitted inside the sealing ring 5. After sealing, the upper and lower anvils are almost close to the sealing gasket but still have a small gap. The liquefied material flows into the high-pressure cavity in the middle of the sealing ring through the gap. Only a slight pressure is needed to close the upper and lower anvils with the sealing gasket, thus encapsulating the liquefied material.

[0085] It should be noted that the high-pressure polymerization reactor of the present invention can be used to polymerize carbon monoxide, etc. The heat leakage at the bottom of the cryogenic liquid nitrogen container in this invention refers to the total heat transfer power of the bottom and sides of the cylinder.

[0086] The technical solution of the present invention will be further explained below with reference to specific embodiments.

[0087] Example 1

[0088] like Figure 1 and 4 As shown, a cryogenic liquid nitrogen device 6 for high-pressure polymerization reaction is disclosed. The cryogenic liquid nitrogen device 6 consists of an upper cuboid 61 and a lower cylinder 62. The distances from the axis of the cylinder 62 to the opposite first side 63 and second side 64 of the cuboid 61 are different. The upper surface of the cuboid 61 is an open structure, and the cryogenic liquid nitrogen device 6 is wrapped with an insulation layer.

[0089] Example 2

[0090] like Figure 11-15 The sheet metal fabrication method for the cryogenic liquid nitrogen device described in Example 1 is as follows:

[0091] (1) Cut the stainless steel plates according to the drawings to obtain square box sheet metal parts (see drawings). Figure 11 ), cylindrical sheet metal parts (see) Figure 12 ) and round-bottomed sheet metal parts (see Figure 13The square box sheet metal part has a round hole cut into it, and the distance from the center of the round hole to two opposite sides of the cuboid is different.

[0092] (2) Bend the four sides of the square box sheet metal part at 90°. After bending, weld the gaps at the sides to ensure that the welds are leak-proof, forming a cuboid, such as... Figure 14 As shown;

[0093] (3) The cylindrical sheet metal part is formed into a cylindrical structure along its long side, and the joint gaps are welded, such as... Figure 15 As shown, the cylindrical structure has an outer diameter of 82mm and an inner diameter of 80mm, which matches the size of the circular hole at the bottom of the cuboid. The cylindrical structure and the edge of the circular hole are then welded together.

[0094] (4) Weld the upper end of the cylindrical structure to the cuboid and the lower end of the cylindrical structure to the round bottom sheet metal part to obtain the sheet metal part of the initial formed cryogenic liquid nitrogen container.

[0095] The diameter of the round-bottom sheet metal part is 80mm, which matches the inner diameter of the cylindrical structure, and it is aligned and welded to the cylindrical structure along the edge of the round bottom.

[0096] (5) Cut the welded joints in the sheet metal parts of the pre-formed cryogenic liquid nitrogen container, remove the weld points, pour in water, verify that all weld points are leak-proof, and complete the processing. If there is leakage, it is necessary to repair the welding and clean the weld points again to obtain the cryogenic liquid nitrogen device.

[0097] Example 3

[0098] This embodiment of a high-pressure polymerization reactor includes the cryogenic liquid nitrogen apparatus of Embodiment 1, specifically as follows: The apparatus includes an upper heat insulation plate 3, an upper pad 12, an upper anvil seat 11, an upper anvil 1, a lower anvil 2, a lower anvil seat 21, and a lower heat insulation plate 4, arranged concentrically from top to bottom. A sealing ring 5 is provided between the upper anvil 1 and the lower anvil 2, and a sealing gasket 54 is provided inside the sealing ring 5. The upper anvil seat 11, the upper anvil 1, the sealing ring 5, the lower anvil 2, and the lower anvil seat 21 are arranged in the embodiment. In the cryogenic liquid nitrogen device 6 of Example 1, the cryogenic liquid nitrogen device 6 is composed of an upper cuboid 61 and a lower cylinder 62. The distance from the axis of the cylinder 62 to the two opposite sides of the cuboid 61 is different. The upper pressure anvil 11, the upper pressure anvil 1 and the sealing ring 5 are located in the cuboid 61, and the lower pressure anvil 2 and the lower pressure anvil seat 21 are located in the cylinder 62. The surfaces of the upper pressure anvil 1 and the lower pressure anvil 2 that contact the sealing gasket 54 are both flat planar structures.

[0099] The upper surface of the cuboid 61 is an open structure. The cryogenic liquid nitrogen device is wrapped with an insulation layer. Specifically, the lower anvil 21 and the lower heat insulation plate 4 are respectively positioned above and below the bottom surface of the cylinder 62 below the cryogenic liquid nitrogen device 6. The lower heat insulation plate 4 is placed directly in the groove of the press 9. A positioning ring 8 is provided between the cylinder 62 of the cryogenic liquid nitrogen device 6 and the groove of the press 9 to separate the cylinder and the press. In this embodiment, the upper anvil 1 and the upper anvil seat 11 have the same outer diameter, and the lower anvil 2 and the lower anvil seat 21 have the same outer diameter. The inner diameter of the cylinder is 80mm, the outer diameter is 82mm, the distance between the side wall of the cylinder and the inner wall of the press is 7mm, the thickness of the lower heat insulation plate 4 is 8mm, and the material of the lower heat insulation plate 4 is glass fiber.

[0100] Specifically, the sealing ring 5 has a groove 51 on both its upper and lower surfaces, and an indium wire is correspondingly arranged in the groove 51. An inlet pipe and an outlet pipe are welded to the sealing ring 5. The included angle between the inlet pipe and the outlet pipe on the circular surface of the sealing ring is 90°. The inlet pipe and the outlet pipe are arranged in a spiral shape within the cryogenic liquid nitrogen device 6, and both the inlet pipe and the outlet pipe have a diameter of 3 mm.

[0101] In this embodiment, the sealing ring 5 is made of aluminum with a thickness of 2mm.

[0102] Example 4

[0103] The high-pressure polymerization reactor in this embodiment is the same as that in Embodiment 3, except that, as Figure 3 As shown, the sealing gasket 54 has a circular ring structure. Two inwardly recessed openings 55 are provided on the sealing gasket 54 corresponding to the two gas guide tubes 53. A temperature sensor placement part 57 is provided on the sealing gasket 54 corresponding to the temperature sensor 56. The two temperature sensors 56 are respectively located on the upper and lower sides of the sealing gasket 54, allowing the measurement of the temperature distribution in the vertical direction of the middle chamber of the sealing ring 5, thereby reflecting the degree of raw material liquefaction.

[0104] Specifically, holes are drilled in the side wall of the sealing ring 5, and the leads of two PT100 temperature sensors are led out through the side wall of the sealing ring 5. At the same time, the holes are bonded with epoxy resin to maintain a sealed state. The PT100 temperature sensors are connected to a digital source meter, and the resistance value of the PT100 temperature sensors is read by a computer to calculate the real-time temperature inside the sealing ring.

[0105] In a further embodiment, the thickness of the sealing gasket 54 matches the height of the sealing ring 5, with the gasket thickness being 1 mm and the sealing ring height being 6.5 mm. The outer diameter of the sealing gasket 54 matches the inner diameter of the sealing ring 5, so that the sealing gasket 54 fits inside the sealing ring 5. The diameter of the circular hole 53 in the center of the sealing gasket 54 is 6 mm, and the outer diameter of the sealing gasket 54 is 53.7 mm.

[0106] Example 5

[0107] The high-pressure polymerization reactor in this embodiment is the same as that in embodiment 3, except that the upper anvil 1 and the upper anvil seat 11 are set inside the first concentric ring 13 of copper, and the lower anvil 2 and the lower anvil seat 21 are set inside the second concentric ring 22 of copper. The upper heat insulation sheet 3, the upper pad 12, the upper anvil seat 11 and the upper anvil 1 are provided with an upper anvil fixing sleeve 7. The upper anvil fixing sleeve 7 is made of glass fiber, which can reduce heat leakage. A heat insulation material layer is also provided between the outer side of the lower anvil seat 21 and the cylinder 62.

[0108] Comparative Example 1

[0109] The cryogenic liquid nitrogen device in this comparative example differs from that in Example 1, specifically in that it consists of two cylinders, an upper cylinder and an lower cylinder, as shown below. Figure 6 As shown. When assembled in a high-pressure polymerization reactor, the lower anvil 2 and lower anvil seat 21 are located in the lower cylinder, which is directly nested in the groove of the press 9. The outer diameter of the lower cylinder (90mm) matches the inner diameter of the groove in the press 9 (92mm). No positioning ring is provided between the lower cylinder and the press. The lower heat insulation sheet 4 is 8mm thick with 1mm thick side edges, and is made of fiberglass. The side wall of the lower cylinder is 1mm away from the side wall of the press 9. A 6mm high fiberglass insulation ring 10 is provided on the outer side of the upper end of the lower cylinder. The lower cylinder without the insulation ring has a height of 16mm.

[0110] Comparative Example 2

[0111] The high-pressure polymerization apparatus in this comparative example is the same as that in Example 4, except that both the upper anvil 1 and the lower anvil 2 have an inwardly concave structure in the middle, and a beryllium copper soft metal ring 101 is disposed between the upper anvil 1 and the lower anvil 2. Figure 9 As shown, when the upper anvil 1 and the lower anvil 2 are squeezed, the beryllium copper is easily deformed, the beryllium copper soft metal ring 101 deforms, forming a sealing structure, the inward concave structure on the upper anvil 1 and the lower anvil 2 fits with the step surface inside the beryllium copper soft metal ring 10, and the cavity in the middle of the beryllium copper soft metal ring and the inward concave structure in the middle of the upper anvil 1 and the lower anvil 2 together constitute the sample reaction chamber.

[0112] like Figure 7This refers to the state before compression occurs when the concave structures of the upper anvil 1 and lower anvil 2 begin to contact the external beryllium copper soft metal ring 101. Figure 8 This refers to the state when the upper anvil 1 and the lower anvil 2 are compressed to their limits.

[0113] Experimental Example 1

[0114] The thermal conductivity of glass fiber is 0.40 W / (m·K), while that of air is 0.023 W / (m·K). The heat transfer power is directly proportional to the contact area and inversely proportional to the distance.

[0115] Calculate the heat transfer power at the bottom of the cylinder and the heat transfer power along the sides of the cylinder in Example 3;

[0116] The heat transfer power at the bottom of the cylinder in the cryogenic liquid nitrogen device is calculated as follows:

[0117] 0.4W / (m·k) × area (3.14 × 80 × 80 / 4mm) 2 ) / Distance (8mm) × Temperature difference (300-77K)

[0118] =56.02W;

[0119] The lateral heat transfer power of the cylinder consists of two parts: glass fiber heat transfer and air heat transfer. The air part has a height of 21 mm, and the glass fiber contact part has a height of 1 mm.

[0120] The heat transfer power of glass fiber is calculated as follows:

[0121] 0.4W / (m·k) × area (3.14 × 82 × 1mm) 2 ) / Distance (7mm) × Temperature difference (300-77K)

[0122] =3.28W;

[0123] The air heat transfer power is calculated as follows:

[0124] 0.023W / (m·k) × area (3.14 × 82 × 21 mm) 2 ) / Distance (7mm) × Temperature difference (300-77K)

[0125] =3.96W;

[0126] Lateral heat transfer through the cylinder = heat transfer power from glass fiber and air = 3.28W + 3.96W = 7.24W.

[0127] In Example 3, the total heat transfer power of the cylinder in the cryogenic liquid nitrogen device is 56.02W + 7.24W = 63.26W.

[0128] The heat transfer power at the bottom of the cylinder in the cryogenic liquid nitrogen device of Comparative Example 1 is calculated as follows:

[0129] 0.4W / (m·k) × area (3.14 × 92 × 92 / 4mm) 2 ) / Distance (8mm) × Temperature difference (300-77K)

[0130] =74.08W.

[0131] The heat transfer power on the side of the cylinder below the cryogenic liquid nitrogen device in Comparative Example 1 was calculated as follows: Lateral heat transfer includes two parts: glass fiber heat transfer and air heat transfer. The air part is 16 mm high, and the glass fiber contact part is 6 mm high.

[0132] Glass fiber heat transfer power:

[0133] 0.4W / (m·k) × area (3.14 × 92 × 6 mm) 2 () / distance (1mm) × temperature difference (300-77K) = 154.61W;

[0134] Air heat transfer power:

[0135] 0.023W / (m·k) × area (3.14 × 92 × 16 mm) 2 ) / Distance (1mm) × Temperature difference (300-77K)

[0136] =23.71W;

[0137] The total lateral heat transfer power is 154.61W + 23.71W = 178.32W.

[0138] In Comparative Example 1, the total heat transfer power of the lower cylinder in the cryogenic liquid nitrogen device is 74.08W + 178.32W = 252.4W.

[0139] The comparison shows that the total heat transfer power of the lower cylinder of the cryogenic liquid nitrogen device in Comparative Example 1 (252.4W) is greater than that of the cylinder of the cryogenic liquid nitrogen device in Example 3 (63.26W), indicating that the cryogenic liquid nitrogen device of the present invention can reduce heat leakage.

[0140] Experimental Example 2

[0141] (1) The compression ratio of the reaction chamber of Comparative Example 2 sample was calculated as follows:

[0142] After calculation, such as Figure 7 As shown, the volume of the reaction chamber of the sample before compression was 80.34 mm. 3 .like Figure 8 As shown, when compressed to its limit, the volume of the sample reaction chamber is 46.41 mm². 3 .

[0143] The sample chamber compression ratio is calculated as follows:

[0144] (1 - Volume of reaction chamber after compression / Volume of reaction chamber before compression) × 100% = (1 - 46.41 / 80.34) × 100% = 42.23%.

[0145] (2) The compressibility of the reaction chamber in Example 4 was calculated as follows:

[0146] In Example 4, the sample reaction chamber is the circular hole 53 on the sealing gasket 54. Before compression, the volume of the reaction chamber is V = 3.14 × 3 × 3 × 1 = 28.26 mm. 3 After extreme compression, the upper and lower anvil surfaces are in direct contact, and the volume of the reaction chamber is 0.

[0147] Calculate the sample chamber compressibility as follows: (1 - Volume after compression / Volume before compression) × 100%

[0148] = (1 - 0 / 28.26) × 100% = 100%.

[0149] Under extreme compression conditions, by comparing the compression ratios of the reaction chambers in Example 4 and Comparative Example 2, it can be seen that the compression ratio of the reaction chamber of the present invention is greater. Since the high compression ratio makes it easier for the raw materials to meet the phase change requirements, it is beneficial for the reaction to proceed. High-pressure polymerization reactions of gaseous raw materials usually involve a large proportion of volume shrinkage. This device has significant advantages for high-pressure reactions of gaseous raw material samples with high compression ratios.

[0150] Experimental Example 3

[0151] The p-CO sample was synthesized using the high-pressure polymerization apparatus described in Example 4. CO gas entered the sample chamber through gas delivery tube 52. The sample chamber had a diameter of 6 mm, a height of 1 mm, and a volume of 3.14 × 3 × 3 × 1 = 28.26 mm². 3 The density of liquid CO is 0.8 g / cm³. 3 Therefore, the amount of sample sealed in the sample chamber was 22.608 mg. Under the action of oil pressure of 18000 psi (about 120 tons), the pressure was maintained for 12 hours. After depressurization, 6.2 mg of p-CO solid was obtained, so the reaction yield was 27.4%.

[0152] The above description is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any changes or substitutions that can be easily conceived by those skilled in the art within the scope of the technology disclosed in the present invention should be included within the scope of protection of the present invention.

Claims

1. A high-pressure polymerization reactor, characterized in that, The device also includes an upper pressure anvil, an upper pressure anvil, a lower pressure anvil, a lower pressure anvil base, and a cryogenic liquid nitrogen device; The cryogenic liquid nitrogen device consists of an upper cuboid and a lower cylinder. The distances from the axis of the cylinder to the two opposite sides of the cuboid are different. The upper cuboid and the lower cylinder are integrally formed. The cryogenic liquid nitrogen device is made of sheet metal. The upper anvil and upper anvil are located within the cuboid, and the lower anvil and lower anvil seat are located within the cylinder. A positioning ring is provided between the cylinder of the cryogenic liquid nitrogen device and the groove of the press to separate the cylinder and the press. A heat insulation material layer is also provided between the outer side of the lower anvil and the cylinder.

2. The high-pressure polymerization reactor according to claim 1, characterized in that, The upper surface of the cuboid is an open structure.

3. The high-pressure polymerization reactor according to claim 2, characterized in that, The opening is a liquid nitrogen inlet.

4. The high-pressure polymerization reactor according to claim 1, characterized in that, The cryogenic liquid nitrogen device is wrapped with an insulation layer on the outside.

5. The high-pressure polymerization reactor according to claim 1, characterized in that, The device further includes a sealing ring disposed between the upper and lower anvils; The sealing ring is located within the cuboid of the cryogenic liquid nitrogen device.

6. The high-pressure polymerization reactor according to claim 5, characterized in that, The device also includes a sealing gasket disposed within a sealing ring.

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