Heat transfer assembly for hydration reaction, hydrate reactor and hydrate reaction system

Abstract

A hydrate reactor (1) and a system using the reactor (1) are disclosed. The reactor (1) comprises a vertical pressure vessel-shaped cylindrical body (100) with a gas-liquid mixture inlet (101) at the bottom, a hydrate discharge port (102) at the top, and a liquid drain port (103) at the bottom. The cylindrical body (100) is also provided with a heat transfer assembly (110) in the center of the cylindrical body (100), which includes a plurality of six-sided honeycomb-shaped channels with inclined walls. The inclined walls of the honeycomb-shaped channels conduct and dissipate heat of hydration during the process of hydrate formation as the gas-liquid mixture passes through the honeycomb-shaped channels. The presence of the heat transfer assembly (110) in the reactor effectively increases the contact time between the gas and liquid, which is more favorable for rapid transfer of the heat of hydrate formation, thereby increasing the efficiency of hydrate formation.

Description

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of Chinese Patent Application No. 202211347070.5, filed on October 31, 2022, the contents of which are incorporated herein by reference. [Technical Field]

[0002] The present invention relates to the technical field of hydrate production, and more particularly to a heat transfer assembly, a hydrate reactor and a system using the reactor. [Background technology]

[0003] Hydrates are cage-like crystalline inclusion compounds in which water molecules form cage-like crystals through hydrogen bonding, and gas molecules are enclosed in the crystal lattice. Carbon dioxide hydrate is a special inclusion compound formed by water and carbon dioxide under low-temperature and high-pressure conditions. One cubic meter of carbon dioxide hydrate can store 160 to 180 cubic meters of carbon dioxide gas. Natural gas hydrate is an ice-like substance formed by methane molecules surrounded by water molecules. It is also known as flammable ice and can be formed at 0°C and a pressure of only 30 atmospheres. Under standard conditions, one unit volume of natural gas hydrate can produce up to 164 units of methane gas upon decomposition, making it an important potential resource for the future.

[0004] Hydrates have a wide range of applications, but require low temperatures and high pressures for their reaction. Therefore, overcoming the slow hydrate formation rate and accelerating its formation rate are key to the practical application of hydrate technology. Currently, the most common methods for promoting rapid hydrate formation in laboratories are divided into physical and chemical methods. Physical enhancement is the main enhancement method in various gas hydrate formation processes. Among these physical enhancement methods, spraying is a reliable, controllable, effective, and energy-efficient method. However, the biggest drawback of spraying is that a hydrate layer forms on the surface of the droplets during the falling process, and the heat of formation accumulates inside the droplets, inhibiting further hydrate formation. Hydrate reactors commonly used in the prior art mix gas and liquid to form a spray, and a metal plate is placed on the opposite side of the nozzle to transfer and diffuse the heat of formation. However, experimental results have shown that this method does not have a clear cooling effect, and the liquid quickly drips off the baffle, resulting in a short contact time between the gas and liquid and a slow hydrate formation rate.

[0005] Therefore, there is an urgent need for a hydrate reactor and system using the same that overcomes the problems of the prior art, such as short gas-liquid contact time and slow heat transfer for hydrate formation.

[0006] The information disclosed in this Background is intended only to enhance understanding of the general background of the present invention and should not be taken as an admission or in any way suggesting that the information constitutes prior art already known to those skilled in the art. Summary of the Invention [Problem to be solved by the invention]

[0007] An object of the present invention is to provide a hydrate reactor and a system using the reactor in which a heat transfer assembly is provided within the reactor, thereby effectively increasing the contact time between gas and liquid, which is more advantageous for rapidly transferring the heat of hydrate formation, thereby increasing the efficiency of hydrate formation.

[0008] Another object of the present invention is to provide a hydrate reaction system in which, after the hydration reaction has been carried out for a predetermined period of time, the liquid supply line and the rinse line can be switched to rinse the heat transfer assembly in the reactor with the liquid discharged from the bottom of the hydrate reactor. [Means for solving the problem]

[0009] In order to achieve the above object, according to a first aspect of the present invention, there is provided a hydrate reactor comprising: a cylindrical body having a vertical pressure vessel structure with a gas-liquid mixture supply port at the bottom, a hydrate discharge port at the top, and a liquid drain port at the bottom; and a heat transfer assembly provided in the center of the cylindrical body, which includes a plurality of six-sided honeycomb-shaped channels with inclined walls, wherein the gas-liquid mixture passes through the honeycomb-shaped channels to produce hydrates, and the inclined walls of the honeycomb-shaped channels conduct and dissipate heat of hydration.

[0010] Furthermore, in the above technical solution, the heat transfer assembly includes multi-stage honeycomb plates spaced apart from one another from bottom to top, and the six-sided honeycomb channels are provided in each stage of the honeycomb plate.

[0011] Furthermore, in the above technical solution, the inclination directions of the wall surfaces of the honeycomb channels of two adjacent honeycomb plates among the multi-stage honeycomb plates are different, forming a zigzag flow direction of the gas-liquid mixture.

[0012] Furthermore, in the above technical solution, the multi-stage honeycomb plate includes a first stage honeycomb plate, a second stage honeycomb plate, and a third stage honeycomb plate arranged in order from bottom to top, and the thickness of the honeycomb plate and the hole diameter of the honeycomb channels of the honeycomb plate increase with each stage, and the inclination angle of the wall surfaces of the honeycomb channels decreases with each stage.

[0013] Furthermore, in the above technical solutions, the thickness of the first-stage honeycomb plate may be set to 5-10 cm, and the inclination angle of the wall surfaces of the first-stage honeycomb channels may be set to 10°-45°. The thickness of the second-stage honeycomb plate may be set to 5-15 cm, and the inclination angle of the wall surfaces of the second-stage honeycomb channels may be set to 30°-60°. The thickness of the third-stage honeycomb plate may be set to 8-25 cm, and the inclination angle of the wall surfaces of the third-stage honeycomb channels may be set to 45°-80°.

[0014] Furthermore, in the above technical solution, the hydrate reactor further includes a rotary ejector, which is disposed between the gas-liquid mixed supply port and the heat transfer assembly, and has a structure combining an impeller and an orifice plate, and is driven to rotate by the gas pressure when the impeller mixes and supplies the gas and liquid, and can cut the gas into small bubbles in a spiral shape and inject them through the orifice plate.

[0015] Furthermore, in the above technical solution, an inlet of a liquid flow ejector may be provided above the heat transfer assembly, and the liquid flow ejector is used to receive the drained liquid from the bottom of the cylinder and rinse the heat transfer assembly after the hydration reaction has been carried out for a predetermined time.

[0016] According to a second aspect of the present invention, there is provided a hydrate reaction system including the hydrate reactor according to any one of the above aspects, and further including an effluent backwash unit that pressurizes effluent from the bottom of the cylindrical body of the hydrate reactor and pumps it into a buffer tank, and that injects the effluent into the heat transfer assembly in the cylindrical body by a liquid flow ejector to rinse the heat transfer assembly after the hydration reaction has been carried out for a predetermined time.

[0017] Furthermore, in the above technical solution, the system further includes: a gas supply unit for supplying a high-pressure gas source required for the hydration reaction; a liquid supply unit for supplying a cooling water source and a hydrate promoter at the initial stage of the hydration reaction; and a gas-liquid mixing unit for receiving and mixing the high-pressure gas source, the cooling water source and the hydrate promoter, and then sending them to the supply port of the hydrate reactor.

[0018] Furthermore, in the above technical solution, the liquid supply unit includes a low-temperature constant temperature bath for supplying a circulating refrigerant for cooling the water source and the hydrate promoter, and a heat exchanger for exchanging heat between the refrigerant and the water source and the hydrate promoter to obtain a cooling liquid required for the hydration reaction.

[0019] Furthermore, in the above technical solution, the liquid circulation pump used in the wastewater backwash unit selectively drives two circulation loops, which are a liquid supply line and a rinse line, respectively. The liquid supply line is a circulation loop between the drain port and the supply port of the cylinder, and the rinse line is a circulation loop between the drain port and the inlet of the liquid flow ejector.

[0020] Furthermore, in the above technical solution, the system further includes a gas circulation pump for pumping the gas after the hydration reaction from the top gas outlet of the hydrate reactor cylinder to the gas supply line for gas circulation.

[0021] Furthermore, in the above technical solution, the gas outlet is provided with a safety valve and a pressure sensor to maintain the necessary high pressure environment in the hydrate reactor.

[0022] The present solution also provides a heat transfer assembly for a hydration reaction, which includes a plurality of honeycomb plates stacked vertically, each honeycomb plate having a plurality of honeycomb channels, the extension direction of the honeycomb channels being inclined at an angle to the vertical direction, and in any two adjacent honeycomb plates, the inclination direction of the honeycomb channels of the lower honeycomb plate is different from the inclination direction of the honeycomb channels of the upper honeycomb plate.

[0023] In some embodiments, in a projection plane perpendicular to the stacking direction of the honeycomb plates, the angle formed by the extension paths of the honeycomb channels of adjacent honeycomb plates is 90 to 180 degrees.

[0024] In some embodiments, of any two adjacent honeycomb plates, the inclination direction of the honeycomb channels of the lower honeycomb plate is opposite to the inclination direction of the honeycomb channels of the upper honeycomb plate.

[0025] In some embodiments, of any two adjacent honeycomb plates, the thickness of the lower honeycomb plate is smaller than the thickness of the upper honeycomb plate, and / or the pore size of the lower honeycomb channel is smaller than the pore size of the upper honeycomb channel.

[0026] In some embodiments, of any two adjacent honeycomb plates, the inclination angle of the honeycomb channels of the lower honeycomb plate is greater than the inclination angle of the honeycomb channels of the upper honeycomb plate.

[0027] In some embodiments, the heat transfer assembly includes a first stage honeycomb plate, a second stage honeycomb plate, and a third stage honeycomb plate arranged from bottom to top, wherein the ratio of the inner diameter of the honeycomb channels of the first stage honeycomb plate to the overall diameter is 1:20-50, the ratio of the inner diameter of the honeycomb channels of the second stage honeycomb plate to the overall diameter is 1:18-40, and the ratio of the inner diameter of the honeycomb channels of the third stage honeycomb plate to the overall diameter is 1:15-30.

[0028] In some embodiments, the first-stage honeycomb plate has a thickness of 5 to 10 cm, and the honeycomb channels of the first-stage honeycomb plate have an inclination angle of 10° to 45°; the second-stage honeycomb plate has a thickness of 5 to 15 cm, and the honeycomb channels of the second-stage honeycomb plate have an inclination angle of 30° to 60°; and the third-stage honeycomb plate has a thickness of 8 to 25 cm, and the honeycomb channels of the third-stage honeycomb plate have an inclination angle of 45° to 80°.

[0029] In some embodiments, the plurality of honeycomb plates are spaced apart.

[0030] In another aspect, the solution comprises: a cylindrical body having a vertical pressure vessel structure, the cylindrical body having a gas-liquid mixed supply port at the bottom, a hydrate discharge port at the top, and a liquid drain port at the bottom; and a heat transfer assembly for hydration reaction according to the above-mentioned solution means, which is provided in the central part of the cylindrical body.

[0031] In some embodiments, the hydrate reactor further includes a rotary ejector disposed between the gas liquid mixed inlet and the heat transfer assembly, the rotary ejector including an orifice plate and a rotatable impeller disposed below the orifice plate, the impeller rotating to cut the gas into small bubbles that can be ejected through the orifice plate.

[0032] In some embodiments, the rotary ejector includes a housing mounted to the orifice plate and a supply pipe connected to the housing.

[0033] In some embodiments, a liquid flow ejector inlet is provided in a portion of the side wall of the cylinder above the heat transfer assembly, and the liquid flow ejector is configured to receive drainage from the bottom of the cylinder to rinse the heat transfer assembly.

[0034] The present solution also includes the hydrate reactor described in the above solution, The hydrate reaction system further includes an effluent backwash unit that pressurizes effluent from the bottom of the hydrate reactor cylinder and transports it to a buffer tank, and further injects the effluent into the heat transfer assembly in the cylinder using a liquid flow ejector to rinse the heat transfer assembly after the hydration reaction has been carried out for a predetermined period of time.

[0035] In some embodiments, the system further comprises: a gas supply unit for supplying a high-pressure gas source necessary for the hydration reaction; a liquid supply unit for supplying a cooling water source and a hydrate promoter at the beginning of the hydration reaction; and a gas-liquid mixing unit that receives and mixes the high-pressure gas source, the cooling water source, and a hydrate promoter before delivering them to the feed inlet of the hydrate reactor.

[0036] In some embodiments, the liquid supply unit comprises: a low-temperature constant temperature bath for supplying a circulating refrigerant for cooling the water source and the hydrate promoter; and a heat exchanger for exchanging heat between the refrigerant and a water source and a hydrate promoter to obtain the cooling liquid required for the hydration reaction.

[0037] In some embodiments, the liquid circulation pump used in the drain backwash unit is configured to selectively drive two circulation loops, which are a liquid supply line and a rinse line, respectively, the liquid supply line being the circulation loop between the drain outlet and the supply inlet of the cylinder, and the rinse line being the circulation loop between the drain outlet and the inlet of the liquid flow ejector.

[0038] In some embodiments, the system further comprises: The hydrate reactor further includes a gas circulation pump for pumping the gas after the hydration reaction from the top gas outlet of the cylinder to a gas supply line for gas circulation.

[0039] In some embodiments, the gas outlet is equipped with a safety valve and a pressure sensor to maintain the required high pressure environment within the hydrate reactor. [Effects of the Invention]

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

[0041] 1) In the present invention, hydration heat is conducted through the honeycomb channels of the heat transfer assembly. Due to the heat imbalance in the six-sided structure of the honeycomb channels, the hydration heat generated on one side is conducted to the other four sides, gradually dispersing and transferring the heat. Therefore, for the same heat, the heat exchange area with the liquid increases, and the heat exchange per unit area per unit time decreases, improving the heat exchange efficiency.

[0042] 2) The present invention uses a three-tier honeycomb plate design. Specifically, the thickness of the honeycomb plate and the diameter of the honeycomb channels increase with each tier, and the inclination angle of the honeycomb channel walls decreases with each tier. This results in the overall heat transfer assembly structure having a broken-line shape with three varying angles. This structure allows the gas in the feedstock to first collide with the inclined wall of the first tier honeycomb plate to form crystal nuclei. The gas impact then causes small crystal nuclei to collide with the inclined walls of the second and third tier honeycomb plates, respectively, and continue to rise. The extended wall surface with each tier increases the contact time between the gas and liquid phases, ensuring more time for crystal growth. The gradually increasing inner diameter of the honeycomb and the gradually decreasing angle with the vertical direction facilitates the passage of crystals and effectively prevents growing crystals from clogging the channels.

[0043] 3) The rotary ejector of the present invention uses gas pressure to push the impeller, increasing the spiral force of the gas and injecting the gas in the form of small bubbles from the scattered injection holes. During the hydration reaction, the more turbulent the gas and liquid, the faster the hydrate formation rate. Increasing the mass transfer rate between the gas and liquid can effectively shorten the induction time for crystal nuclei. Hydrate nucleation mainly occurs at the gas-liquid interface, and the high gas concentration at the interface creates a region suitable for gas preconcentration. Combining the rotary ejector of the present invention with a heat transfer assembly increases the turbulence and instantaneous gas concentration, accelerating the hydrate nucleation rate and further promoting hydrate formation. The inclined inner walls of the multi-stage honeycomb plate allow the injected gas to accumulate in this region, increasing the instantaneous concentration and favoring hydrate nucleation.

[0044] 4) The hydrate reaction system of the present invention can effectively rinse the heat transfer assembly through the rinse line formed by the effluent backwash unit. A buffer tank is provided within the effluent backwash unit to temporarily store liquid and lower the liquid level in the hydrate reactor. After the hydrate has reacted for a predetermined time, the valve of the liquid supply line is closed and the valve of the rinse line is opened to allow the liquid to flow into the rinse line. At this time, the internal pressure is reduced as the liquid is discharged from the reactor cylinder, and the liquid is pressurized and sprayed, resulting in a slight temperature increase. The liquid sprayed onto the heat transfer assembly causes the hydrates adhering to its surface to fall off or break down in the reverse direction, effectively improving the efficiency and effectiveness of the rinse.

[0045] The above description is merely a summary of the technical solution of the present invention. In order to make the technical solution of the present invention more clearly understood and to enable it to be implemented in accordance with the content of the specification, and to make the above and other objectives, technical features and advantages of the present invention more comprehensible, one or more preferred embodiments will be given below and described in detail with reference to the drawings. [Brief explanation of the drawings]

[0046] [Figure 1] FIG. 1 is a schematic diagram of the connections of the hydrate reaction system of the present invention. [Figure 2-A] FIG. 1 is a schematic diagram of the appearance of a hydrate reactor of the present invention. [Figure 2-B] FIG. 1 is a cross-sectional schematic diagram of a hydrate reactor of the present invention. [Figure 3-A] 2 is a cross-sectional schematic view of the inlet end face of the first stage honeycomb plate of the heat transfer assembly of the present invention. FIG. [Figure 3-B] FIG. 2 is a cross-sectional schematic view of the inlet end face of the second stage honeycomb plate of the heat transfer assembly of the present invention. [Figure 3-C] FIG. 3 is a cross-sectional schematic view of the inlet end face of the third-stage honeycomb plate of the heat transfer assembly of the present invention. [Figure 4] 1 is a partial perspective schematic view of a heat transfer assembly of the present invention; [Figure 5-A] 1 is a perspective view of the appearance of a rotary ejector according to the present invention; [Figure 5-B] 1 is a cross-sectional view of the inside of a rotary ejector according to the present invention; DETAILED DESCRIPTION OF THE INVENTION

[0047] Hereinafter, specific embodiments of the present invention will be described in detail with reference to the drawings, but it should be understood that the scope of protection of the present invention is not limited by the embodiments.

[0048] Unless expressly stated otherwise, throughout the specification and claims, the term "comprises" or variations thereof, such as "comprises" or "comprising," is to be understood to include the stated elements or components and not to exclude other elements or components.

[0049] For convenience of description, spatially relative terms such as "below," "below," "below," "above," "above," and the like may be used herein to describe the relationship of one element or feature to another element or feature in the drawings. It should be understood that spatially relative terms are intended to include different orientations of objects during use or operation other than those depicted in the drawings. For example, if an object in a figure is inverted, an element described as being "below" or "below" another element or feature would be oriented "above" said element or feature. Thus, the exemplary term "below" may include both an orientation of below and above. Objects may have other orientations (rotated 90 degrees or other orientations) and should be interpreted accordingly with the spatially relative terms used herein.

[0050] As used herein, terms such as "first" and "second" are intended to distinguish between two different elements or portions, and are not intended to limit a specific location or relative relationship. In other words, in some embodiments, terms such as "first" and "second" may be interchangeable. Example 1

[0051] The present solution provides a heat transfer assembly for hydration reactions, which includes a plurality of honeycomb plates stacked vertically, each honeycomb plate having a plurality of honeycomb channels, the extension direction of the honeycomb channels being inclined at an angle to the vertical direction, and in any two adjacent honeycomb plates, the inclination direction of the honeycomb channels of the lower honeycomb plate is different from the inclination direction of the honeycomb channels of the upper honeycomb plate.

[0052] The cross-sectional shape of the honeycomb channels may be various shapes such as triangular, square, circular, hexagonal, etc., but is preferably hexagonal.

[0053] Adjacent honeycomb plates may be tightly joined together or may be spaced apart from one another.

[0054] Here, in a projection plane perpendicular to the stacking direction of the honeycomb plates, the angle formed by the extension paths of the honeycomb channels of adjacent honeycomb plates is 90 to 180 degrees. The projection of the extension direction of the honeycomb channels on the projection plane perpendicular to the stacking direction is a straight line, and the angle formed by the projection lines of the honeycomb channels of adjacent honeycomb plates is 90 to 180 degrees.

[0055] Here, of any two adjacent honeycomb plates, the inclination direction of the honeycomb channels of the lower honeycomb plate is opposite to the inclination direction of the honeycomb channels of the upper honeycomb plate, i.e., the angle between the projection lines of the honeycomb channels is 180 degrees, and the channels of multiple honeycomb plates form broken line channels.

[0056] In any two adjacent honeycomb plates, the thickness of the lower honeycomb plate is smaller than that of the upper honeycomb plate, and / or the pore diameter of the lower honeycomb channel is smaller than that of the upper honeycomb channel. As the gas-liquid mixture flows from bottom to top, the inner diameter of the channel also gradually increases, thereby reducing the resistance to the gas-liquid mixture and increasing the thickness of the honeycomb plate in turn, thereby appropriately extending the residence time.

[0057] Here, the inclination angle of the honeycomb channels of the lower honeycomb plate between any two adjacent honeycomb plates is greater than the inclination angle of the honeycomb channels of the upper honeycomb plate, and the inclination angles decrease in order, thereby reducing the resistance to the gas-liquid mixture.

[0058] Here, the heat transfer assembly is provided with a first stage honeycomb plate 111, a second stage honeycomb plate 112, and a third stage honeycomb plate 113 arranged from bottom to top, and the ratio of the inner diameter of the honeycomb channel of the first stage honeycomb plate 111 to the overall diameter is 1:20 to 50, the ratio of the inner diameter of the honeycomb channel of the second stage honeycomb plate 112 to the overall diameter is 1:18 to 40, and the ratio of the inner diameter of the honeycomb channel of the third stage honeycomb plate 113 to the overall diameter is 1:15 to 30.

[0059] Here, the thickness of the first stage honeycomb plate 111 is 5 to 10 cm, the inclination angle of the first stage honeycomb channels 1111 of the first stage honeycomb plate 111 is 10° to 45°, the thickness of the second stage honeycomb plate 112 is 5 to 15 cm, the inclination angle of the second stage honeycomb channels 1121 of the second stage honeycomb plate 112 is 30° to 60°, the thickness of the third stage honeycomb plate 113 is 8 to 25 cm, and the inclination angle of the third stage honeycomb channels 1131 of the third stage honeycomb plate 113 is 45° to 80°.

[0060] Here, the plurality of honeycomb plates are arranged at intervals. For example, the plurality of honeycomb plates may be arranged at equal intervals or may be arranged at different intervals. Example 2

[0061] As shown in Figures 2-A and 2-B, this embodiment provides a hydrate reactor 1 for producing hydrates of a single-component gas or a mixed-component gas. The hydrate reactor 1 includes at least a cylinder 100 and a heat transfer assembly 110. The cylinder 100 is a vertical pressure vessel structure, and a gas-liquid mixed supply inlet 101 is provided at the bottom of the cylinder. A hydrate outlet 102 is provided at the top of the cylinder, and the hydrate outlet 102 is inclined downward along the horizontal direction and connected to external piping via a butt-welded flange, facilitating the discharge of the produced hydrate to the hydrate slurry tank 7 (see Figure 1). A liquid drain 103 is provided at the bottom of the cylinder and connected to external piping via a butt-welded flange. In this embodiment, a gas outlet 105 is further provided at the top of the cylinder, and a safety valve and a pressure sensor 106 are provided at the gas outlet 105. The safety valve is sealed and connected via a butt-welded flange. The heat transfer assembly 110 may be disposed in the center of the cylindrical body 100 and welded to the cylindrical body as a whole. The outer circumferential surface of the heat transfer assembly 110 is bonded to the inner circumferential surface of the cylindrical body 100, thereby allowing the heat transfer assembly 110 to transfer heat to the cylindrical body 100 and release it to the outside. The heat transfer assembly 110 includes a plurality of six-sided honeycomb channels with inclined walls, and the inclined walls of the honeycomb channels conduct and release the heat of hydration during the process of hydrate formation when the gas-liquid mixture passes through the honeycomb channels.

[0062] In the present invention, the heat of hydration generated by the reaction is effectively transferred to the outside by the heat transfer assembly 110 installed within the cylindrical body 100. Through research, the inventors discovered that the main means of heat transfer within the honeycomb are heat transfer through the sidewalls of the honeycomb channels and heat exchange by radiation between the honeycomb's inner surfaces. Further experiments demonstrated that a six-sided honeycomb structure increases the contact area between the metal and gas per unit space compared to conventional baffles, thereby effectively dissipating the heat of hydration per unit area. Because each side of the honeycomb is connected to the other four sides and the honeycomb channels have inclined walls, the heat contacting the six sides is different, resulting in heat imbalance. The heat of hydration generated on one side is conducted to the other four sides, gradually dispersing and transferring the heat. This increases the heat exchange area with the liquid for the same heat, reducing the heat exchange per unit area per unit time and improving heat exchange efficiency.

[0063] Furthermore, as shown in FIG. 2-B, preferably, but not exclusively, the heat transfer assembly of this embodiment includes multi-stage honeycomb plates arranged at intervals from bottom to top, with the six-sided honeycomb channels provided in each honeycomb plate. In the multi-stage honeycomb plate, the inclination directions of the honeycomb channel walls of adjacent two honeycomb plates are different (see FIG. 4), forming a zigzag flow direction of the gas-liquid mixture. Furthermore, in this embodiment, the multi-stage honeycomb plate may be divided into three stages, including a first-stage honeycomb plate 111, a second-stage honeycomb plate 112, and a third-stage honeycomb plate 113 arranged in order from bottom to top. Preferably, but not exclusively, the thickness of the honeycomb plate and the hole diameter of the honeycomb channels of the honeycomb plate increase with each stage (see FIG. 2-B and FIGS. 3-A to 3-C), and the inclination angle of the honeycomb channel walls decreases with each stage (see FIG. 4). Specifically, the thickness of the first-stage honeycomb plate 111 may be set to 5 to 10 cm, and the inclination angle of the wall surfaces 1112 of the first-stage honeycomb channels may be set to 10 to 45 degrees. The thickness of the second-stage honeycomb plate 112 may be set to 5 to 15 cm, and the inclination angle of the wall surfaces 1122 of the second-stage honeycomb channels may be set to 30 to 60 degrees. The thickness of the third-stage honeycomb plate 113 may be set to 8 to 25 cm, and the inclination angle of the wall surfaces 1132 of the third-stage honeycomb channels may be set to 45 to 80 degrees.

[0064] In this embodiment, the gas-liquid mixture enters through the supply port 101 at the bottom. During the hydration reaction, the cylinder is filled with sufficient liquid (i.e., the cooling water source and the hydrate promoter), and the heat transfer assembly 110 is immersed in this liquid. After the hydration reaction is completed, the hydrate floats on the liquid surface and is discharged through the hydrate discharge port 102. At the same time, the gas-liquid mixture continuously enters through the supply port 101 at the bottom of the cylinder, and thus hydrate is continuously produced. In this embodiment, a three-tier honeycomb plate is designed. In particular, the thickness of the honeycomb plate and the pore size of the honeycomb channels of the honeycomb plate increase with each tier, and the inclination angle of the honeycomb channel walls decreases with each tier. As a result, the structure of the entire heat transfer assembly presents a polygonal line shape with three stages of change in angle. With this structure, the gas in the feedstock first collides with the inclined wall of the first-stage honeycomb plate 111 to form crystal nuclei. The impact of the gas then causes small crystal nuclei to collide with the inclined wall of the second-stage honeycomb plate 112 and the third-stage honeycomb plate 113, respectively, and continue to rise. By extending the wall surface with each stage, the contact time between the gas and liquid phases increases, ensuring more time for crystal growth. The honeycomb inner diameter gradually increases, and the angle with the vertical gradually decreases, allowing the crystals to pass through more easily and effectively preventing the growing crystals from clogging the channels.

[0065] 2-B and 5-A and 5-B, the hydrate reactor of this embodiment may preferably, but not limited to, further include a rotary ejector 120, which is provided between the gas-liquid mixed supply inlet 101 and the heat transfer assembly 110. The rotary ejector 120 has a cylindrical hollow structure as a whole, and is a structure combining an impeller and an orifice plate, the impeller 121 is provided inside the housing, the upper side of the rotary ejector 120 in FIG. 2-B is the orifice plate, and the orifice plate has spray holes 122 arranged in a scattered manner, and a supply pipe 123 is connected to the supply inlet 101 of the cylindrical body 100. The impeller 121 may be driven to rotate by the gas pressure in the supplied gas-liquid mixture, cutting the gas into small bubbles in a spiral pattern and injecting them through an orifice plate, but of course the impeller 121 may also be driven by an external power source such as a motor.

[0066] In this embodiment, the rotary ejector uses gas pressure to push the impeller, increasing the spiral force of the gas and injecting the gas in the form of small bubbles through the scattered injection holes. During the hydration reaction, the more turbulent the gas and liquid, the faster the hydrate formation rate. Increasing the mass transfer rate between the gas and liquid effectively shortens the induction time for crystal nucleation. Therefore, the use of the rotary ejector in addition to the heat transfer assembly of this embodiment increases the turbulence and instantaneous gas concentration, accelerating the hydrate nucleation rate and further promoting hydrate formation. Hydrate nucleation mainly occurs at the gas-liquid interface, and the high gas concentration at the interface creates a region suitable for gas pre-concentration. The inclined inner walls of the multi-stage honeycomb plate allow the injected gas to accumulate in this region, increasing the instantaneous concentration and favoring hydrate nucleation.

[0067] 2-A and 2-B, a liquid flow ejector inlet 104 may be provided on the sidewall of the cylindrical body 100 and above the heat transfer assembly 110, and the liquid flow ejector 6 (see FIG. 1) is used to receive the discharged liquid from the bottom of the cylindrical body after the hydration reaction has occurred for a predetermined time, and to rinse the heat transfer assembly 110. The liquid discharged from the bottom is subjected to work by the booster pump (i.e., the liquid circulation pump 5) and the liquid flow ejector 6, causing a slight increase in temperature, and the effects of the pressure, temperature increase, and injection force cause the hydrates adhering to the surface of the heat transfer assembly 110 to fall off or break down in the reverse direction, thereby achieving a cleaning effect. Example 3

[0068] As shown in FIG. 1 , this embodiment provides a hydrate reaction system, which includes the hydrate reactor of Example 1 and further includes a wastewater backwash unit. The wastewater backwash unit includes a liquid outlet valve 8, a liquid circulation pump 5, a rinse line valve 9, a buffer tank 18, and a liquid flow ejector 6. These devices and pipelines form a circulation loop (i.e., a rinse line) with the reactor 1 cylinder. The wastewater backwash unit pressurizes the wastewater from the bottom of the hydrate reactor cylinder and transports it to the buffer tank 18. After the hydration reaction has been performed for a predetermined period of time, the liquid flow ejector 6 injects the wastewater into the heat transfer assembly in the cylinder to rinse the heat transfer assembly. Specifically, referring to FIG. 1 , the liquid circulation pump 5 is connected to a wastewater port 103 at the bottom of the hydrate reactor by the liquid outlet valve 8. Both ends of the buffer tank 18 are connected to the inlet of the liquid flow ejector 6 and the outlet of the liquid circulation pump 5, respectively. A rinse line valve 9 is provided at the outlet of the liquid circulation pump. The pipe of the buffer tank 18 may have a diameter of 35 to 45 cm, with the pipe diameters at the water inlet and outlet at both ends being the same, and can be used to temporarily store liquid and lower the liquid level in the hydrate reactor 1. The outlet of the liquid flow ejector 6 is connected to an ejector interface 104 on the side of the hydrate reactor (see FIG. 2-A), and a rinse line formed by the effluent backwash unit in this embodiment can rinse the heat transfer assembly in the hydrate reactor when the pressure in the hydrate reactor is lowered.

[0069] As shown in FIG. 1, the system of this embodiment further includes a gas supply unit, a liquid supply unit, and a gas-liquid mixing unit. The gas supply unit includes a gas source 2 and a first gas valve 11 and is used to supply the high-pressure gas required for the hydration reaction. The gas source 2 is connected to the gas supply port of the gas-liquid mixing unit 3 via the first gas valve 11 and piping, and supplies gas of a predetermined concentration and pressure to the hydrate reactor of the present invention. The liquid supply unit includes a water storage tank 19, a water pump 12, and an outlet flow valve 13 and is used to supply a cooling water source and a hydrate promoter at the initial stage of the hydration reaction. The gas-liquid mixing unit has a gas-liquid mixing chamber, and liquid (i.e., the cooling water source and the hydrate promoter) pressurized by the water pump 12 enters the mixing chamber together with the gas, where they are mixed and then sprayed at high speed into the supply port of the hydration reactor cylinder.

[0070] As shown in FIG. 1 , the liquid supply unit further includes a low-temperature bath 14 and a heat exchanger 4. The low-temperature bath 14 is used to supply a circulating refrigerant for cooling the water source and the hydrate promoter. The heat exchanger 4 exchanges heat between the refrigerant and the water source and the hydrate promoter to obtain the cooling liquid required for the hydration reaction. Specifically, the hot material line in the heat exchanger is connected to the drain port at the bottom of the hydrate reactor and the liquid supply port of the gas-liquid mixing unit 3, and the cold material line is connected to the low-temperature bath 14. The temperature of the liquid in the piping is lowered by circulating the refrigerant. In this embodiment, there is another circulation loop (i.e., a liquid supply line) between the drain and the supply inlet of the hydrate reactor, and the two circulation loops consisting of the liquid supply line and the rinse line are driven by the same liquid circulation pump, and the corresponding valves can be turned on for specific circulation loops, i.e., in the normal hydration reaction process, the liquid supply line valve 10 is opened, while the rinse line valve 9 is opened when the heat transfer assembly needs to be cleaned.

[0071] Furthermore, as shown in FIG. 1, the system of this embodiment further includes a gas circulation pump 16 for pumping the gas after the hydration reaction from the gas outlet at the top of the hydrate reactor cylinder to the gas supply line, and a second gas valve 15 and a third gas valve 17 are provided on the lines at both ends of the gas circulation pump 16, respectively, and are controlled to circulate the gas for use.

[0072] The system of this embodiment effectively rinses the heat transfer assembly through a rinse line consisting of a effluent backwash unit. A buffer tank is provided within the effluent backwash unit to temporarily store liquid and lower the liquid level in the hydrate reactor. After the hydrate reaction has proceeded for a predetermined period of time, the valve on the liquid supply line is closed and the valve on the rinse line is opened to allow liquid to flow into the rinse line. During this process, the internal pressure in the reactor cylinder is reduced by the discharge of liquid, and the liquid is pressurized and sprayed, resulting in a slight temperature increase. The liquid sprayed onto the heat transfer assembly reversely removes or destroys hydrates adhering to its surface, effectively improving the efficiency and effectiveness of the rinse. Example 4

[0073] In this example, a hydrate reaction is carried out using the hydrate reactor and a system using the reactor described in Example 3. Here, the thickness of the first-stage honeycomb plate of the hydrate reactor may be 5 cm, and the inclination angle of the wall surfaces of the first-stage honeycomb channels may be set to 15°. The thickness of the second-stage honeycomb plate may be set to 10 cm, and the inclination angle of the wall surfaces of the second-stage honeycomb channels may be set to 30°. The thickness of the third-stage honeycomb plate may be set to 20 cm, and the inclination angle of the wall surfaces of the third-stage honeycomb channels may be set to 45°. The reaction pressure is 3 MPa, and the reaction temperature is 10°C. Comparative Example 1

[0074] In the reactor described in Example 4, the heat transfer assembly was changed to a baffle, where the baffle had an inclination angle of 60°C, and used in the system of Example 3 to carry out the hydrate reaction. The reaction pressure was 3 MPa and the reaction temperature was 10°C.

[0075] (Table 1) Reaction data [Table 1]

[0076] The above descriptions of specific exemplary embodiments of the present invention are for the purposes of explanation and illustration only. These descriptions are not intended to limit the present invention to the particular forms disclosed, and it is apparent that many modifications and variations are possible based on the above teachings. The purpose of selecting and describing the exemplary embodiments is to explain certain principles of the present invention and its practical applications, thereby enabling those skilled in the art to realize and utilize various exemplary embodiments and various choices and variations of the present invention. So-called simple modifications, equivalent changes, and modifications made to the above exemplary embodiments should also fall within the scope of protection of the present invention. [Explanation of symbols]

[0077] 1. Hydrate Reactor 100 cylinder 101 Supply port 102 Hydrate outlet 103 Drainage port 104 Ejector Interface 105 Gas outlet 106 Safety valves and pressure sensors 110 Heat Transfer Assembly 111 First stage honeycomb plate 1111 First stage honeycomb channel 1112 Wall of the first stage honeycomb channel 112 Second stage honeycomb plate 1121 Second stage honeycomb channel 1122 Wall of the second stage honeycomb channel 113 Third stage honeycomb plate 1131 Third stage honeycomb channel 1132 Wall of the third stage honeycomb channel 120 Rotary Ejector 121 Impeller 122 Injection hole 123 Supply pipe 2. Gas Source 3 Gas-liquid mixing unit 4 Heat exchanger 5 Liquid Circulation Pump 6 Liquid flow ejector 7. Hydrate Slurry Tank 8 Liquid Outlet Valve 9 Rinse line valve 10 Liquid supply line valve 11 First gas valve 12 Water pump 13 Outlet flow valve 14 Low temperature constant temperature bath 15 Second gas valve 16 Gas circulation pump 17 Third gas valve 18 Buffer Tank 19 Water Tank

Claims

1. 1. A heat transfer assembly for a hydration reaction, comprising: A heat transfer assembly for a hydration reaction, comprising a plurality of honeycomb plates stacked vertically, each honeycomb plate having a plurality of honeycomb channels, the extension direction of the honeycomb channels being inclined at an angle to the vertical direction, and between any two adjacent honeycomb plates, the inclination direction of the honeycomb channels of the lower honeycomb plate is different from the inclination direction of the honeycomb channels of the upper honeycomb plate.

2. 2. The heat transfer assembly for hydration reactions according to claim 1, wherein, in a projection plane perpendicular to the stacking direction of the plurality of honeycomb plates, an angle formed by the extension paths of the honeycomb channels of adjacent honeycomb plates is 90 to 180 degrees.

3. 2. The heat transfer assembly for a hydration reaction according to claim 1, wherein, of any two adjacent honeycomb plates, the inclination direction of the honeycomb channels of the lower honeycomb plate is opposite to the inclination direction of the honeycomb channels of the upper honeycomb plate.

4. 2. The heat transfer assembly for a hydration reaction according to claim 1, wherein, of any two adjacent honeycomb plates, the thickness of the lower honeycomb plate is smaller than the thickness of the upper honeycomb plate, and the pore size of the honeycomb channels on the lower side is smaller than the pore size of the honeycomb channels on the upper side.

5. 2. The heat transfer assembly for a hydration reaction according to claim 1, wherein, of any two adjacent honeycomb plates, the inclination angle of the honeycomb channels of the lower honeycomb plate is larger than the inclination angle of the honeycomb channels of the upper honeycomb plate.

6. 2. The heat transfer assembly for a hydration reaction according to claim 1, wherein the heat transfer assembly comprises a first stage honeycomb plate, a second stage honeycomb plate, and a third stage honeycomb plate arranged from bottom to top, wherein the ratio of the inner diameter of the honeycomb channel of the first stage honeycomb plate to the overall diameter is 1:20 to 50, the ratio of the inner diameter of the honeycomb channel of the second stage honeycomb plate to the overall diameter is 1:18 to 40, and the ratio of the inner diameter of the honeycomb channel of the third stage honeycomb plate to the overall diameter is 1:15 to 30.

7. 7. The heat transfer assembly for a hydration reaction according to claim 6, wherein the thickness of the first-stage honeycomb plate is 5 to 10 cm, and the inclination angle of the honeycomb channels of the first-stage honeycomb plate is 10° to 45°, the thickness of the second-stage honeycomb plate is 5 to 15 cm, and the inclination angle of the honeycomb channels of the second-stage honeycomb plate is 30° to 60°, and the thickness of the third-stage honeycomb plate is 8 to 25 cm, and the inclination angle of the honeycomb channels of the third-stage honeycomb plate is 45° to 80°.

8. 2. The heat transfer assembly for a hydration reaction according to claim 1, wherein the honeycomb plates are spaced apart.

9. 1. A hydrate reactor comprising: a cylindrical body having a vertical pressure vessel structure, the cylindrical body having a gas-liquid mixed supply port at the bottom, a hydrate discharge port at the top, and a liquid drain port at the bottom; and the heat transfer assembly for hydration reaction according to any one of claims 1 to 8, which is provided in the central part of the cylindrical body.

10. The hydrate reactor comprises:

10. The hydrate reactor of claim 9, further comprising a rotary ejector disposed between the gas-liquid mixed supply port and the heat transfer assembly, the rotary ejector comprising an orifice plate and a rotatable impeller disposed below the orifice plate, the impeller rotating to cut the gas into small bubbles that can be ejected through the orifice plate.

11. 11. The hydrate reactor of claim 10, wherein the rotary ejector includes a housing mounted on the orifice plate and a supply pipe connected to the housing.

12. 10. The hydrate reactor of claim 9, wherein a liquid flow ejector inlet is provided in a portion of the sidewall of the cylinder above the heat transfer assembly, and the liquid flow ejector is configured to receive drainage from the bottom of the cylinder to rinse the heat transfer assembly.

13. 1. A hydrate reaction system comprising: The hydrate reactor according to any one of claims 9 to 12, A hydrate reaction system characterized by further comprising an effluent backwash unit that pressurizes effluent from the bottom of the hydrate reactor cylinder and transports it to a buffer tank, and further injects the effluent into the heat transfer assembly in the cylinder using a liquid flow ejector to rinse the heat transfer assembly after the hydration reaction has been carried out for a predetermined period of time.

14. The system comprises: a gas supply unit for supplying a high-pressure gas source necessary for the hydration reaction; a liquid supply unit for supplying a cooling water source and a hydrate promoter at the beginning of the hydration reaction; 14. The hydrate reaction system of claim 13, further comprising a gas-liquid mixing unit that receives and mixes the high-pressure gas source, the cooling water source, and a hydrate promoter before delivering them to the feed inlet of the hydrate reactor.

15. The liquid supply unit includes: a low-temperature constant temperature bath for supplying a circulating refrigerant for cooling the water source and the hydrate promoter; 15. The hydrate reaction system according to claim 14, further comprising a heat exchanger for exchanging heat between the refrigerant and a water source and a hydrate promoter to obtain a cooling liquid required for the hydration reaction.

16. The hydrate reaction system according to claim 13, characterized in that the liquid circulation pump used in the effluent backwash unit is configured to selectively drive two circulation loops, the two circulation loops being a liquid supply line and a rinse line, respectively, the liquid supply line being the circulation loop between the effluent outlet and the supply inlet of the cylinder, and the rinse line being the circulation loop between the effluent outlet and the inlet of the liquid flow ejector.

17. The system comprises:

14. The hydrate reaction system according to claim 13, further comprising a gas circulation pump for pumping the gas after the hydration reaction from the top gas outlet of the hydrate reactor cylinder to a gas supply line for gas circulation.

18. 18. The hydrate reaction system according to claim 17, wherein the gas outlet is provided with a safety valve and a pressure sensor for maintaining a necessary high-pressure environment in the hydrate reactor.

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