A temperature control device and a gas hydrate reactor, a generation system and a method thereof

Abstract

The present invention discloses a temperature control device and a reactor, a generation system and a method for gas hydrate thereof. The temperature control mechanism body is in a natural gas atmosphere, a nanofluid flows downward along a wall through an outlet and contacts with the natural gas to generate gas hydrates, a cooling structure for absorbing heat released when gas hydrates are generated is embedded in the temperature control mechanism body, the cooling structure timely absorbs the generated heat of the reaction, so that the temperature of the wall is constant, so as to ensure that gas hydrates can be stably and effectively generated on the wall, a scraper for peeling off the gas hydrates generated on the wall is provided on the wall, the gas hydrates generated and attached on the wall can be scraped away by the scraper in time, and the gas hydrates generated before will not affect the heat exchange between the nanofluid flowing out along the wall and the wall. The present invention strengthens the heat and mass transfer process of the gas-liquid two-phase, greatly improves the generation rate of the gas hydrate, and realizes the rapid and continuous preparation of the gas hydrate.

Description

Technical Field

[0001] The present invention relates to the field of hydrate preparation, and in particular to a temperature control device and a reactor, a generation system and a method for gas hydrate thereof. Background Art

[0002] Ideal gas hydrates have strong gas storage capacity, high safety factor and low economic cost. They are not only the most promising way to store and transport natural gas, but also have broad application prospects in the fields of carbon dioxide capture and storage, seawater desalination, gas separation, energy storage and refrigeration. Therefore, research on the rapid generation of gas hydrates is of great significance to improving the utilization rate of petrochemical resources and optimizing my country's energy structure. However, the current hydrate synthesis technology is difficult to break through the bottleneck of slow generation speed and low gas storage density, which makes the large-scale commercial application of hydrate technology face arduous challenges. The generation of gas hydrates is a complex multi-phase and multi-component interphase heat and mass transfer problem. In terms of heat transfer, the hydrate generation process is an exothermic process. Rapid removal of reaction heat can increase the driving force of the reaction. Therefore, the stronger the heat dissipation capacity of the system, the more conducive to the reaction. In terms of mass transfer, hydrates are preferentially generated at the gas-liquid interface. Therefore, increasing the gas-liquid contact area can effectively promote gas-liquid two-phase heat and mass transfer, enhance the generation rate of hydrates and the ability to complex gas molecules. It can be seen that improving the heat dissipation capacity of the system and continuously updating the gas-liquid contact interface are crucial to the rapid generation of hydrates.

[0003] However, as far as the current research status is concerned, traditional means of enhancing hydrate formation have failed to fundamentally solve the key problems of insufficient mass transfer and untimely heat transfer. For example, although dynamic enhancement technologies such as mechanical stirring, spraying, and bubbling can enhance gas-liquid contact by introducing mechanical disturbances, as hydrates gradually form, hydrates are easily attached to the stirring blades and the inside of the reaction chamber in the stirring method, resulting in poor gas-liquid mixing effect and increased energy consumption; the efficiency of heat transfer from the inside of the reaction chamber to the outside in the spraying method is low, and the heat accumulation generated by the reaction will inhibit the continued formation of hydrates; the orifice plate that generates microbubbles in the bubbling method is easily blocked by hydrates, and the reaction rate slows down. Static enhancement technologies such as ice powder contact method, thermodynamic promoter method, kinetic promoter method, porous medium method, and nanoparticle method can effectively increase the gas storage density of hydrates, but the hydrate generation rate is far from industrial demand, and the existing experimental scale is too small, and there is an amplification effect that cannot be ignored.

[0004] Patent document CN112062177A discloses a desalination device based on the method of rotating gas hydrate separation, and the desalination device can be used to continuously produce fresh water in single-line / dual-line operation. If gas is introduced into the stainless steel container, seawater is injected into the cylindrical porous medium from the water inlet; under certain temperature and pressure conditions, hydrate crystals nucleate at the porous medium-net-gas interface and grow toward the gas phase; the rotary scraper separates the generated hydrates; the hydrates collected in the decomposition zone are decomposed by thermal stimulation of the heating jacket, and the fresh water is collected to the height of the liquid level gauge, and the control valve is opened to discharge into the water tank; and the decomposition process of the hydrate absorbs heat, and the seawater is pre-cooled and introduced into the cylindrical porous medium. The present invention generates hydrates in the seawater environment in a stainless steel container, separates the hydrates on the surface of the cylindrical porous medium by a rotary scraper, and uses heating to decompose the hydrates to obtain desalinated fresh water. However, the combination of gas and seawater is not sufficient, the cooling is insufficient, and the separation of the rotary scraper is poor. Summary of the invention

[0005] The purpose of the present invention is to provide a temperature control device and a reactor, a generation system and a method for gas hydrate thereof to solve the problems existing in the above-mentioned prior art. Nanofluid contacts natural gas along the wall to generate gas hydrate. The cooling structure on the inner side of the wall absorbs the heat of reaction in time and keeps the temperature of the wall constant. The scraper matched with the wall scrapes away the gas hydrate attached to the wall in time, thereby strengthening the heat and mass transfer process of the gas-liquid two phases, greatly improving the generation rate of gas hydrate, and realizing rapid and continuous preparation of gas hydrate.

[0006] To achieve the above-mentioned purpose, the present invention provides the following solution: The present invention provides a temperature control device, comprising a temperature control mechanism body, the temperature control mechanism body is in a natural gas atmosphere, a liquid storage device for nanofluid is provided above the temperature control mechanism body, the outlet of the liquid storage device is toward the wall surface of the temperature control mechanism body, the nanofluid flows downward along the wall surface through the outlet and contacts with the natural gas to generate gas hydrates, a cooling structure for absorbing heat released when gas hydrates are generated is embedded in the temperature control mechanism body, and a scraper for peeling off the gas hydrates generated on the wall surface is provided on the wall surface.

[0007] Preferably, the cooling structure comprises a phase change material and a heat exchange pipeline for cooling the phase change material, and the heat exchange pipeline is coiled in the phase change material.

[0008] Preferably, a temperature sensor for monitoring the wall temperature is provided on the temperature control mechanism body, and an electric control valve for adjusting the flow of the coolant according to the monitoring value of the temperature sensor is provided on the heat exchange pipeline.

[0009] Preferably, the outlet is in a flat-mouth structure, and the flat-mouth structure extends horizontally along the wall surface.

[0010] Preferably, the temperature control mechanism body is a vertical cylindrical structure, the wall surface is the inner peripheral wall surface and the outer peripheral wall surface of the vertical cylindrical structure, and the scraper is provided on the inner peripheral wall surface and the outer peripheral wall surface along the circumferential rotation.

[0011] A gas hydrate reactor is also provided, comprising a reactor shell and a plurality of vertical cylindrical structures arranged inside the reactor shell, wherein the vertical cylindrical structures are coaxial and spaced apart from each other, the liquid storage device is provided with a plurality of outlets respectively facing the inner circumferential wall surface and the outer circumferential wall surface of each vertical cylindrical structure, the nanofluid flows downward along the corresponding inner circumferential wall surface and the outer circumferential wall surface through each of the outlets, and the reactor shell is provided with an air inlet for natural gas to enter the interior thereof.

[0012] Preferably, a discharge port is provided at the bottom of the reactor shell, and the vertical cylindrical structures are arranged above the discharge port at intervals and are all connected to the discharge port.

[0013] A gas hydrate generation system is also provided, comprising the reactor shell and a liquid supply mechanism, a gas supply mechanism and a separator arranged on the outside thereof, the liquid supply mechanism is connected to the liquid storage tank, the gas supply mechanism is connected to the gas inlet, the separator is connected to the discharge port, the separator is used to separate the natural gas, nanofluid and gas hydrate discharged through the discharge port, the separator is connected to the liquid supply mechanism and the gas supply mechanism through a recovery pipeline, respectively, and the separator is connected to a gas hydrate storage tank for storing gas hydrates.

[0014] Preferably, the reactor shell is equipped with a pressure control mechanism, which includes a gas inlet regulating valve arranged between the gas supply mechanism and the gas inlet, a gas pressure sensor arranged in the reactor shell, and a gas outlet regulating valve arranged between the separator and the gas supply mechanism, and the openings of the gas inlet regulating valve and the gas outlet regulating valve are adapted to the detection values ​​of the gas pressure sensor.

[0015] A method for generating gas hydrate is also provided, comprising the following steps:

[0016] Temperature control: Control the temperature of the cooling pipe to cool the inside of the reactor shell, the inner wall and the outer wall of the vertical cylindrical structure to the preset value;

[0017] Gas intake: Start the gas supply mechanism to pass natural gas into the reactor shell, and adjust the opening of the gas inlet regulating valve and the gas outlet regulating valve according to the detection value of the gas pressure sensor, so that the gas pressure in the reactor shell is maintained at the preset value;

[0018] Liquid inlet: start the liquid supply mechanism, let the nanofluid enter the liquid storage device, and flow downward along the inner wall and outer wall of the vertical cylindrical structure in the form of a thin film through the outlet of the liquid storage device;

[0019] Reaction: The nanofluid contacts the natural gas in the reactor shell during its downward flow to form gas hydrates. The phase change material in the vertical cylindrical structure absorbs the heat released during the formation of gas hydrates. The cooling pipe replenishes the coldness for the phase change material to maintain the temperature of the inner and outer walls at the preset value.

[0020] Discharge: After the temperature rise signal of the inner and outer walls is collected, the scraper is turned on to peel off the gas hydrate attached to the inner and outer walls, so that it is discharged from the reactor shell together with the unreacted nanofluid;

[0021] Separation: In the separator, the escaped natural gas returns to the gas supply mechanism, the nanofluid circulates to the liquid supply mechanism, and then flows into the reactor shell, and the gas hydrate enters the hydrate storage tank.

[0022] Compared with the prior art, the present invention has achieved the following technical effects:

[0023] First, the temperature control mechanism body is in a natural gas atmosphere, a nanofluid liquid storage device is provided above the temperature control mechanism body, the outlet of the liquid storage device faces the wall of the temperature control mechanism body, the nanofluid flows downward along the wall through the outlet and contacts with the natural gas to generate gas hydrates, a cooling structure for absorbing heat released when gas hydrates are generated is embedded in the temperature control mechanism body, the cooling structure timely absorbs the heat of reaction, so that the temperature of the wall is constant, so as to ensure that gas hydrates can be stably and effectively generated on the wall, a scraper for peeling off the gas hydrates generated on the wall is provided on the wall, the gas hydrates generated and attached on the wall can be scraped away by the scraper in time, the gas hydrates generated before will not affect the subsequent heat exchange between the nanofluid flowing out along the wall and the wall, and will not affect the subsequent generation of gas hydrates, the present invention strengthens the heat and mass transfer process of gas-liquid two phases, greatly improves the generation rate of gas hydrates, and realizes the rapid and continuous preparation of gas hydrates.

[0024] Second, the cooling structure includes a phase change material and a heat exchange pipeline for cooling it. The heat exchange pipeline is coiled in the phase change material. After the phase change material absorbs heat and completely changes from a solid phase to a liquid phase, the phase change material begins to heat up, and the flow rate of the coolant in the heat exchange pipeline increases to replenish the cold capacity for the phase change material. It can also absorb the hydration reaction heat in time to keep the reaction wall temperature constant, thereby ensuring the efficiency of gas hydrate formation.

[0025] Thirdly, the outlet has a flat-mouth structure, which extends horizontally along the wall. The flat-mouth structure limits the outflow shape of the nanofluid, so that it flows down in a thin film and then contacts with natural gas to form gas hydrates. Limiting the nanofluid to a thin film structure can not only ensure rapid and effective film heat exchange and rapid generation of gas hydrates, but also avoid the nanofluid flowing directly downward without having time to generate gas hydrates, thereby increasing the amount of nanofluid circulation and inevitably causing losses.

[0026] Fourth, the vertical cylindrical structures are coaxial and spaced apart, the liquid storage device is provided with a plurality of outlets facing the inner circumferential wall and the outer circumferential wall of each vertical cylindrical structure respectively, the nanofluid flows downward along the corresponding inner circumferential wall and the outer circumferential wall through each outlet, the reactor shell is provided with an air inlet for natural gas to enter the interior thereof, a plurality of groups of vertical cylindrical structures are arranged in the reactor and spaced apart, the generation of gas hydrate on one vertical cylindrical structure does not affect the other vertical cylindrical structure, thereby increasing the generation rate of gas hydrate and realizing efficient and continuous production of gas hydrate.

[0027] Fifth, the liquid supply mechanism is connected to the liquid storage device, the gas supply mechanism is connected to the gas inlet, and the separator is connected to the discharge port. The separator is used to separate the natural gas, nanofluid and gas hydrate discharged through the discharge port. The separator is connected to the liquid supply mechanism and the gas supply mechanism through a recovery pipeline, respectively, and the separator is connected to a gas hydrate storage tank for storing gas hydrates. The escaping gas phase is returned to the gas supply mechanism through the separator, and the liquid phase circulates to the liquid supply mechanism and then flows back into the reactor. The solid hydrate enters the gas hydrate storage tank, which ensures the circulation of natural gas and nanofluid, improves the collection efficiency of gas hydrates, and reduces the waste of raw materials. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative labor.

[0029] Figure 1 It is the structural diagram of the reaction kettle of the present invention;

[0030] Figure 2 It is a schematic diagram of the cooperation between the vertical cylindrical structure and the scraper blade of the present invention;

[0031] Figure 3 This is a schematic diagram of the design of the heat exchange pipeline in the vertical cylindrical structure of the present invention;

[0032] Figure 4A schematic diagram of a generation system of the present invention;

[0033] Among them, 1-liquid inlet, 2-screw shaft, 3-motor, 4-liquid distributor, 5-fixed partition, 6-vertical cylindrical structure, 7-scraper, 8-connecting rod, 9-rotating shaft, 10-air inlet, 11-discharge port, 12-phase change material, 13-heat exchange pipeline, 14-nanofluid storage tank, 15-reactor shell, 16-refrigeration device, 17-gas cylinder, 18-buffer tank, 19-compressor, 20-separator, 21-gas hydrate storage tank, 22-gas inlet regulating valve, 23-gas outlet regulating valve. DETAILED DESCRIPTION

[0034] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0035] The purpose of the present invention is to provide a temperature control device and a reactor, a generation system and a method for gas hydrate thereof to solve the problems existing in the above-mentioned prior art. Nanofluid contacts natural gas along the wall to generate gas hydrate. The cooling structure on the inner side of the wall absorbs the heat of reaction in time and keeps the temperature of the wall constant. The scraper matched with the wall scrapes away the gas hydrate attached to the wall in time, thereby strengthening the heat and mass transfer process of the gas-liquid two phases, greatly improving the generation rate of gas hydrate, and realizing rapid and continuous preparation of gas hydrate.

[0036] In order to make the above-mentioned objects, features and advantages of the present invention more obvious and easy to understand, the present invention is further described in detail below with reference to the accompanying drawings and specific embodiments.

[0037] Please refer to Figures 1 to 4The present invention provides a temperature control device, including a temperature control mechanism body, the temperature control mechanism body is in a natural gas atmosphere, preferably a natural gas jet device is used to jet natural gas toward the temperature control mechanism body, or preferably the temperature control mechanism body is arranged in a closed tank body, and the tank body is inflated by the natural gas jet device, a nanofluid liquid storage device is arranged above the temperature control mechanism body, the outlet of the liquid storage device faces the wall surface of the temperature control mechanism body, the nanofluid flows downward along the wall surface through the outlet and contacts with the natural gas to generate gas hydrate, and a cooling device is embedded in the temperature control mechanism body to absorb the heat released when the gas hydrate is generated The structure of the present invention is that the cooling structure absorbs the heat of reaction in time, so that the temperature of the wall surface is constant, so as to ensure that gas hydrates can be stably and effectively generated on the wall surface. A scraper 7 is provided on the wall surface for peeling off the gas hydrates generated on the wall surface. The gas hydrates generated and attached on the wall surface can be scraped away by the scraper 7 in time. The gas hydrates generated previously will not affect the subsequent heat exchange between the nanofluid flowing out along the wall surface and the wall surface, that is, it will not affect the subsequent generation of gas hydrates. The present invention strengthens the heat and mass transfer process of the gas-liquid two-phase, greatly improves the generation rate of gas hydrates, and realizes the rapid and continuous preparation of gas hydrates. Preferably, in the process of the nanofluid flowing downward, the flow rate of the nanofluid can be changed by controlling the flow rate of the outlet, so that the flow rate of the nanofluid is adapted to the speed of the generation of gas hydrates by combining with natural gas, thereby ensuring the generation efficiency of gas hydrates, avoiding excessive flow of the nanofluid, and excessive nanofluid flowing out before reacting, and avoiding too small flow of the nanofluid, resulting in limited efficiency of gas hydrate generation. Preferably, the movement of the scraper 7 is driven by a movable mechanism, and the action time of the scraper 7 is determined by the gas hydrate formation situation collected by the data acquisition system. Specifically, after the computer collects the signal of the wall temperature rise, the movable mechanism is turned on to make the scraper work to scrape off the gas hydrate attached to the wall, and then from the perspective of enhancing heat and mass transfer, the heat of formation is quickly removed, the reaction temperature is accurately controlled, the hydrate slurry is efficiently collected, and the gas-liquid interface is updated in time, thereby increasing the hydrate generation rate and realizing efficient and continuous production of gas hydrates.

[0038] Among them, the nanofluid is obtained by mixing the dried carbon nanotube particles with the surfactant solution (SDS) by the "two-step method" and then ultrasonically dispersing the ZnO nanofluid. Specifically, the rich specific surface area of ​​carbon nanotubes greatly increases the gas-liquid contact area, and its good thermal conductivity enhances the heat dissipation capacity of the reaction system. At the same time, SDS can effectively prevent the agglomeration of nanoparticles, and can effectively reduce the interfacial tension and strengthen the hydrogen bonding between water molecules. Therefore, the nanofluid obtained by compounding the two can actively promote gas-liquid two-phase heat and mass transfer, greatly shorten the induction period of hydrate nucleation, and greatly enhance the hydrate formation kinetics and gas storage capacity.

[0039] Furthermore, the cooling structure includes a phase change material 12 and a heat exchange pipeline 13 for cooling the phase change material 12. The heat exchange pipeline 13 is coiled in the phase change material 12. After the phase change material 12 absorbs heat and completely changes from a solid phase to a liquid phase, the phase change material 12 begins to heat up, and the flow rate of the coolant in the heat exchange pipeline 13 increases to replenish the cold capacity for the phase change material 12. It can also absorb the hydration reaction heat in time to keep the reaction wall temperature constant, thereby ensuring the formation efficiency of gas hydrates.

[0040] Furthermore, a temperature sensor for monitoring the wall temperature is provided on the temperature control mechanism body, and an electric control valve for adjusting the coolant flow rate according to the monitoring value of the temperature sensor is provided on the heat exchange pipeline 13. Preferably, the temperature sensor is buried inside the wall. Preferably, the heat exchange pipeline 13 is connected to the coolant inlet and outlet of the refrigeration device 16 through the insulation pipe, and the temperature control process includes the phase change material 12 being able to absorb the heat of the hydration reaction in time to keep the wall temperature constant, and the temperature adjustment process when the hydrate generation amount is too large. Specifically, after the phase change material 12 absorbs heat and completely changes from the solid phase to the liquid phase, the phase change material 12 begins to heat up, the temperature sensor transmits the signal of the wall temperature change to the data acquisition system, and the computer increases the flow rate of the coolant in the cooling coil to supplement the cold for the phase change material 12. Through the cooperation of the temperature sensor and the heat exchange pipeline 13, the real-time monitoring of the wall temperature is realized, and the wall temperature is accurately adjusted to the set temperature to ensure that the temperature driving force for hydrate generation is constant.

[0041] Furthermore, the outlet is in a flat mouth structure, which extends horizontally along the wall surface. The flat mouth structure limits the outflow shape of the nanofluid, so that it flows down in a thin film shape, and then contacts with natural gas to generate gas hydrates. Limiting the nanofluid to a thin film structure can not only ensure the rapid and effective heat exchange of the film, and can quickly generate gas hydrates, but also avoid the nanofluid flowing directly down before it has time to generate gas hydrates, increasing the amount of nanofluid circulation and inevitably causing losses. And combined with controlling the flow rate of the nanofluid, it ensures that the gas-liquid two phases have sufficient contact area and contact time.

[0042] Further, the temperature control mechanism body is a vertical cylindrical structure 6, and the wall surface is the inner circumferential wall surface and the outer circumferential wall surface of the vertical cylindrical structure 6. The inner circumferential wall surface and the outer circumferential wall surface are both provided with scrapers 7 for circumferential rotation, and the movement mode of the scrapers 7 is driven by the screw of the motor 3. Preferably, the inner circumferential wall surface and the outer circumferential wall surface of the vertical cylindrical structure 6 are made of wear-resistant stainless steel, and the inner circumferential wall surface and the outer circumferential wall surface are treated with hydrophobicity to ensure smooth flow of the nanofluid. In addition, preferably, a plurality of outlets are evenly distributed along the circumference of the vertical cylindrical structure 6, so that the nanofluid can flow down along the circumferential wall of the entire vertical cylindrical structure 6, thereby improving the generation efficiency of gas hydrates.

[0043] Furthermore, a gas hydrate reactor is provided, comprising a reactor shell 15 and a plurality of vertical cylindrical structures 6 arranged inside the reactor shell. The preferred height-to-diameter ratio of the reactor shell 15 is 1:2-4, so as to ensure that the vertical cylindrical structure 6 can be effectively placed in the reactor shell 15 and complete the generation of gas hydrates. The inner and outer peripheral walls of the vertical cylindrical structure 6 can provide a place for the gas hydrate reaction, increase the gas-liquid contact area, and make full use of the space inside the reactor shell 15. The vertical cylindrical structures 6 are coaxial and spaced apart, and the liquid storage device is provided with a plurality of split The outlets on the inner and outer walls of each vertical cylindrical structure 6 are respectively directed to the outlets. The preferred liquid storage device is a liquid distributor 4 to ensure that the nanofluid can flow out evenly from each outlet. The nanofluid flows downward along the corresponding inner and outer walls through each outlet. The reactor shell 15 is provided with an air inlet 10 for natural gas to enter the interior thereof. Multiple groups of vertical cylindrical structures 6 are arranged in the reactor and are arranged at intervals. Gas hydrates are generated on one vertical cylindrical structure 6 without affecting another vertical cylindrical structure 6, thereby increasing the generation rate of gas hydrates and realizing efficient and continuous production of gas hydrates. Preferably, the air inlet 10 is arranged at a position near the bottom of the side wall of the reactor shell 15, specifically below the vertical cylindrical structure 6, so that the natural gas can fill the reactor shell 15 from bottom to top, so that when the nanofluid flows down along the inner and outer walls, it contacts with the natural gas flowing upstream to generate gas hydrates, which can improve the efficiency of gas hydrate generation.

[0044] Preferably, there are three groups of vertical cylindrical structures 6 and three groups of scrapers 7 in the reactor shell 15, the three groups of vertical cylindrical structures 6 include vertical cylindrical structure I, vertical cylindrical structure II, and vertical cylindrical structure III, the three groups of scrapers 7 include scrapers I, scrapers II, and scrapers III, and the three groups of vertical cylindrical structures 6 are connected by a fixed partition 5 to maintain their spaced sleeve state, and preferably the three groups of scrapers 7 are fixed together on the spiral shaft 2 located at the axis of the vertical cylindrical structure 6, the spiral shaft 2 extends coaxially with the vertical cylindrical structure 6, and the spiral shaft 2 rotates to drive each scraper 7 to move synchronously along the same direction. The corresponding vertical cylindrical structure 6 rotates circumferentially. Specifically, the spiral shaft 2 connects each scraper 7 through a rotating shaft 9. The adjacent scrapers 7 are reinforced by a connecting rod 8. The scraper I is located inside the vertical cylindrical structure I and fits with the inner wall of the vertical cylindrical structure I in the vertical direction. The scraper II is located between the vertical cylindrical structures I and II, and fits with the outer wall of the vertical cylindrical structure I and the inner wall of the vertical cylindrical structure II in the vertical direction. The scraper III is located between the vertical cylindrical structures II and III, and fits with the inner wall of the vertical cylindrical structure II in the vertical direction. Preferably, the liquid guide groove of the liquid uniform distributor is distributed in an annular shape, and contacts with the inner and outer walls of the vertical cylindrical structures I and II and the inner wall of the vertical cylindrical structure III, respectively. A liquid inlet 1 is provided at the top of the reactor shell 15, and the liquid uniform distributor is connected to the liquid inlet 1.

[0045] Furthermore, a discharge port 11 is provided at the bottom of the reactor shell 15, and each vertical cylindrical structure 6 is arranged at intervals above the discharge port 11 and is connected to the discharge port 11, so that the gas hydrates on the inner and outer walls of the vertical cylindrical structure 6 are scraped off and directly collected at the discharge port 11, so that the gas hydrates, nanofluids that have not reacted in time, and gases are quickly discharged from the reactor shell 15.

[0046] Furthermore, a gas hydrate generation system is provided, comprising a reactor shell 15 and a liquid supply mechanism, a gas supply mechanism and a separator 20 arranged outside the reactor shell, the device comprising a hydrate generation module, a temperature control module, a pressure control module, a hydrate slurry separation module, a gas supply system, a liquid supply system and a data acquisition system. The liquid supply mechanism is connected to the liquid storage, the gas supply mechanism is connected to the gas inlet 10, the separator 20 is connected to the discharge port 11, the separator 20 is used to separate the natural gas, nanofluid and gas hydrate discharged from the discharge port 11, the separator 20 is connected to the liquid supply mechanism and the gas supply mechanism through a recovery pipeline, and the separator 20 is connected to a gas hydrate storage tank 21 for storing gas hydrates, the escaping gas phase is returned to the gas supply mechanism through the separator 20, the liquid phase circulates to the liquid supply mechanism, and then flows back into the reactor, and the solid hydrate enters the gas hydrate storage tank 21, which ensures the circulation of natural gas and nanofluid, improves the collection efficiency of gas hydrates, and reduces the waste of raw materials. The gas supply system includes a gas cylinder 17, a gas buffer tank 18, a one-way valve, and a compressor 19; the liquid supply system includes a nanofluid storage tank 14, a nanofluid one-way valve, and a circulation pump;

[0047] Furthermore, the reactor shell 15 is equipped with a pressure control mechanism, which includes a gas inlet regulating valve 22 arranged between the gas supply mechanism and the gas inlet 10, a gas pressure sensor arranged in the reactor shell 15, and a gas outlet regulating valve 23 arranged between the separator 20 and the gas supply mechanism. The openings of the gas inlet regulating valve 22 and the gas outlet regulating valve 23 are adapted to the detection values ​​of the gas pressure sensor. Among them, the gas inlet regulating valve 22 is arranged at the outlet of the compressor 19, and the gas outlet regulating valve 23 is arranged at the gas outlet of the separator 20.

[0048] Furthermore, a method for generating gas hydrate is provided, comprising the following steps:

[0049] Temperature control: Control the temperature of the cooling pipe to cool the interior of the reactor shell 15 and the inner and outer walls of the vertical cylindrical structure 6 to a preset value; specifically, first start the refrigeration device 16 to cool the interior of the reactor shell 15 through the heat exchange pipe 13 in the vertical cylindrical structure 6;

[0050] Air intake: Start the gas supply mechanism to pass natural gas into the reactor shell 15, and adjust the opening of the gas inlet regulating valve 22 and the gas outlet regulating valve 23 according to the detection value of the gas pressure sensor, so that the gas pressure in the reactor shell 15 is maintained at a preset value; specifically, start the compressor 19 to pressurize the natural gas in the natural gas buffer tank 18 and take in air from the bottom of the reactor shell 15;

[0051] Liquid inlet: Start the liquid supply mechanism, let the nanofluid enter the liquid storage tank, and flow downward along the inner and outer walls of the vertical cylindrical structure 6 in the form of a thin film through the outlet of the liquid storage tank; specifically, start the circulation pump, the solution in the nanofluid storage tank enters the reactor from the top, flows downward along the wall of the vertical cylindrical structure 6 through the action of the liquid uniform distributor, and contacts the gas in the reactor shell 15;

[0052] Reaction: During the downward flow of the nanofluid, it contacts the natural gas in the reactor shell 15 to form gas hydrates. The phase change material 12 in the vertical cylindrical structure 6 absorbs the heat released during the formation of the gas hydrates. The cooling pipe supplements the phase change material 12 with cold energy to maintain the temperature of the inner wall and the outer wall at a preset value. Specifically, the absolute pressure in the reactor is maintained at 2-10 MPa and the temperature is maintained at 265-273 K. The natural gas reacts with the nanofluid to form gas hydrates.

[0053] Discharge: After the signal of the temperature rise of the inner and outer walls is collected, the scraper 7 is turned on to peel off the gas hydrates attached to the inner and outer walls, so that they are discharged from the reactor shell 15 together with the unreacted nanofluid; specifically, the phase change material 12 in the vertical cylindrical structure 6 can timely absorb the heat released during the hydrate formation process, and at the same time, the heat exchange pipeline 13 located inside the vertical cylindrical structure 6 timely replenishes the cold capacity for the phase change material 12 to maintain the wall temperature at the set temperature. When the computer collects the signal of the wall temperature rise, the motor 3 is turned on to make the scraper work. Under the action of the scraper 7, the hydrates attached to the wall are peeled off and discharged from the reactor together with the unreacted nanofluid. When the pressure in the reactor is lower than the set value, each valve is controlled to continuously supply gas to the system until the system reaches the set value;

[0054] Separation: In the separator 20, the escaped natural gas returns to the gas supply mechanism, the nanofluid circulates to the liquid supply mechanism, and then flows into the reactor shell 15, and the gas hydrate enters the hydrate storage tank.

[0055] Adaptive changes made according to actual needs are all within the protection scope of the present invention.

[0056] It should be noted that it is obvious to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above, and that the present invention can be implemented in other specific forms without departing from the spirit or essential features of the present invention. Therefore, the embodiments should be regarded as exemplary and non-restrictive from any point of view, and the scope of the present invention is defined by the appended claims rather than the above description, and it is intended that all changes falling within the meaning and scope of the equivalent elements of the claims are included in the present invention. Any reference numerals in the claims should not be regarded as limiting the claims involved.

[0057] The present invention uses specific examples to illustrate the principles and implementation methods of the present invention. The above examples are only used to help understand the method and core ideas of the present invention. At the same time, for those skilled in the art, according to the ideas of the present invention, there will be changes in the specific implementation methods and application scope. In summary, the content of this specification should not be understood as limiting the present invention.

Claims

1. A temperature control device, characterized in that: The invention comprises a temperature control mechanism body, wherein the temperature control mechanism body is in a natural gas atmosphere, a liquid storage device of nanofluid is arranged above the temperature control mechanism body, the outlet of the liquid storage device faces the wall surface of the temperature control mechanism body, the nanofluid flows downward along the wall surface through the outlet and contacts the natural gas to generate gas hydrate, a cooling structure for absorbing heat released when the gas hydrate is generated is embedded inside the temperature control mechanism body, and a scraper for peeling off the gas hydrate generated on the wall surface is arranged at the wall surface; the temperature control mechanism body is a vertical cylindrical structure, the wall surface is the inner peripheral wall surface and the outer peripheral wall surface of the vertical cylindrical structure, and the scraper is arranged on the inner peripheral wall surface and the outer peripheral wall surface along the circumferential rotation; The cooling structure comprises a phase change material and a heat exchange pipeline for cooling the phase change material, wherein the heat exchange pipeline is coiled in the phase change material; The outlet is in a flat-mouth structure, and the flat-mouth structure extends horizontally along the wall surface, so that the outflow shape of the nanofluid is in a film shape.

2. The temperature control device according to claim 1, characterized in that: The temperature control mechanism body is provided with a temperature sensor for monitoring the wall temperature, and the heat exchange pipeline is provided with an electric control valve for adjusting the flow of the coolant according to the monitoring value of the temperature sensor.

3. A gas hydrate reactor using the temperature control device according to claim 1 or 2, characterized in that: The invention comprises a reactor shell and a plurality of vertical cylindrical structures arranged inside the reactor shell, wherein the vertical cylindrical structures are coaxial and spaced apart from each other, the liquid storage device is provided with a plurality of outlets facing the inner peripheral wall and the outer peripheral wall of each vertical cylindrical structure respectively, the nanofluid flows downward along the corresponding inner peripheral wall and the outer peripheral wall through each outlet, and the reactor shell is provided with an air inlet for natural gas to enter the interior thereof.

4. The gas hydrate reactor according to claim 3, characterized in that: A discharge port is provided at the bottom of the reactor shell, and each of the vertical cylindrical structures is arranged above the discharge port at intervals and is communicated with the discharge port.

5. A gas hydrate generation system using the gas hydrate reactor according to claim 3 or 4, characterized in that: The reactor shell includes a liquid supply mechanism, a gas supply mechanism and a separator arranged on the outside thereof, wherein the liquid supply mechanism is connected to the liquid storage tank, the gas supply mechanism is connected to the gas inlet, the separator is connected to the discharge port, and the separator is used to separate the natural gas, nanofluid and gas hydrate discharged through the discharge port. The separator is connected to the liquid supply mechanism and the gas supply mechanism through a recovery pipeline, respectively, and the separator is connected to a gas hydrate storage tank for storing gas hydrates.

6. The gas hydrate generation system according to claim 5, characterized in that: The reactor shell is equipped with a pressure control mechanism, which includes a gas inlet regulating valve arranged between the gas supply mechanism and the gas inlet, a gas pressure sensor arranged in the reactor shell and a gas outlet regulating valve arranged between the separator and the gas supply mechanism, and the openings of the gas inlet regulating valve and the gas outlet regulating valve are adapted to the detection values ​​of the gas pressure sensor.

7. A method for generating gas hydrate using the gas hydrate generation system according to claim 5 or 6, characterized in that: The process includes the following: Temperature control: Control the temperature of the heat exchange pipeline and cool the inside of the reactor shell, the inner wall and the outer wall of the vertical cylindrical structure to the preset value; Gas intake: Start the gas supply mechanism to pass natural gas into the reactor shell, and adjust the opening of the gas inlet regulating valve and the gas outlet regulating valve according to the detection value of the gas pressure sensor, so that the gas pressure in the reactor shell is maintained at the preset value; Liquid inlet: start the liquid supply mechanism, let the nanofluid enter the liquid storage device, and flow downward along the inner wall and outer wall of the vertical cylindrical structure in the form of a thin film through the outlet of the liquid storage device; Reaction: During the downward flow of the nanofluid, it contacts the natural gas in the reactor shell to form gas hydrates. The phase change material in the vertical cylindrical structure absorbs the heat released during the formation of gas hydrates. The heat exchange pipeline replenishes the phase change material with cold energy, so that the temperature of the inner and outer walls is maintained at the preset value. Discharge: After the temperature rise signal of the inner and outer walls is collected, the scraper is turned on to peel off the gas hydrate attached to the inner and outer walls, so that it is discharged from the reactor shell together with the unreacted nanofluid; Separation: In the separator, the escaped natural gas returns to the gas supply mechanism, the nanofluid circulates to the liquid supply mechanism, and then flows into the reactor shell, and the gas hydrate enters the hydrate storage tank.

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