A hydrate circulation reactor and a hydrate circulation reaction method

Abstract

The application provides a hydrate circulation reactor and a hydrate circulation reaction method. The hydrate circulation reactor comprises a multi-bin reaction main body, a sealing top cover and a plurality of alveolar hydrate balls. The multi-bin reaction main body comprises a generation bin, an intermediate bin and a decomposition bin arranged coaxially from top to bottom, and a gate valve type isolation door is arranged between two adjacent bins. The end of the generation bin and the end of the decomposition bin are respectively provided with a sealing top cover. The alveolar hydrate ball is an independent reaction medium which can be recycled. When the hydrate circulation reactor completes a round of reaction period and is reset by overall overturning, the alveolar hydrate ball passes through the generation bin, the intermediate bin and the decomposition bin in sequence by gravity, completes one-way circulation flow between the generation bin, the intermediate bin and the decomposition bin, and realizes quasi-continuous operation of hydrate generation, transfer, decomposition and alveolar hydrate ball circulation. The application realizes quasi-continuous operation of the gas capture and release process.

Description

Technical Field

[0001] This invention relates to the field of hydrate resource development and technology application, and more specifically, to a hydrate recycling reactor and a hydrate recycling reaction method. Background Technology

[0002] Gas hydrates are a class of cage-like crystalline compounds formed by hydrogen bonds between gaseous guest molecules (such as CO2, CH4, etc.) and water molecules under low temperature and high pressure conditions. Due to their high gas storage density (1 volume of hydrate can store approximately 160-180 volumes of gas) and significant component selectivity, hydrate technology has important applications in carbon dioxide capture and storage (CCUS), solid-state storage and transportation of natural gas, greenhouse gas emission reduction, and separation of mixed gases.

[0003] To move this technology from laboratory research to practical industrial application, it is urgent to overcome the capacity bottleneck of traditional intermittent operation and construct a dynamic operating process that can simulate continuous feeding and discharging in an industrial setting. In existing technologies, homogeneous hydrates are generated by reciprocating stirring of the entire reactor, but this is essentially a single-reactor intermittent operation. Generation and decomposition share the same temperature and pressure chamber, resulting in significant thermal inertia losses during temperature rise and fall, and preventing continuous operation. Other solutions propose using nested generation and decomposition chambers, combined with an oil-blocking and permeable membrane and water / diesel emulsion for continuous separation. However, this relies on a booster pump-driven emulsion circulation. Although the solid hydrate is discharged through an overflow hole, the interface separation between the liquid emulsion and solid hydrate remains incomplete. Furthermore, the oil-blocking and permeable membrane is fixed to the inner wall of the generation chamber, preventing the reaction medium (water) from being independently recycled. Each reaction cycle requires the consumption or additional replenishment of emulsion, resulting in high system complexity and operating costs. Summary of the Invention

[0004] The purpose of this invention is to provide a hydrate recycling reactor and a hydrate recycling reaction method to solve the technical problem that the reaction medium cannot be independently and completely recycled in the prior art.

[0005] To achieve the above objectives, the technical solution adopted by the present invention is as follows: On one hand, the present invention provides a hydrate recycling reactor, comprising: The multi-compartment reaction body includes a generation compartment, an intermediate compartment, and a decomposition compartment arranged coaxially from top to bottom. Pressure decoupling and selective communication are achieved between the generation compartment and the intermediate compartment, and between the intermediate compartment and the decomposition compartment, through gate valve-type isolation doors. The sealing top cover is provided at the ends of both the generation chamber and the decomposition chamber; Multiple alveolar hydrated balls, which serve as recyclable independent reaction media, are used in the hydrate circulation reactor to sequentially pass through the generation chamber, the intermediate chamber, and the decomposition chamber by gravity when the reactor is flipped and reset after completing one reaction cycle. This completes a unidirectional circulation flow between the generation chamber, the intermediate chamber, and the decomposition chamber, achieving a quasi-continuous operation of hydrate generation, transfer, decomposition, and alveolar hydrated ball circulation.

[0006] According to the hydrate circulation reactor described above, the alveolar hydrate ball includes an outer shell layer, the outer shell layer having an internal reaction chamber for encapsulating a predetermined proportion of water or hydrate promoter solution; The outer shell has a microporous structure that allows gas molecules to diffuse freely through, while locking liquid water and hydrate products inside the internal reaction chamber.

[0007] According to the hydrate circulation reactor described above, the gate valve isolation door adopts a flat sliding sealing structure; The diameter of the alveolar hydration ball is smaller than the through-hole diameter of the gate valve isolation door when it is open, and larger than the sealing gap of the gate valve isolation door when it is closed, so as to ensure that the alveolar hydration ball can pass smoothly when the gate valve isolation door is open and is not clamped or damaged when it is closed.

[0008] According to the hydrate circulation reactor described above, the outer wall of the generation chamber is covered with a cooling jacket, which is used to control the temperature inside the generation chamber within the generation window range of gas hydrates.

[0009] According to the hydrate circulation reactor described above, the intermediate chamber is equipped with a pressure balancing pipeline. The pressure balancing pipeline is used to make the pressure of the two adjacent chambers the same before the gate valve isolation door is opened. The intermediate chamber serves as a gas-locking buffer chamber to achieve a pressure gradient transition between the high-pressure collection environment of the generation chamber and the normal-pressure release environment of the decomposition chamber.

[0010] According to the hydrate circulation reactor described above, the generation chamber is equipped with a gas injection valve, which is used to introduce raw material gas into the generation chamber. And / or, the decomposition chamber is equipped with an exhaust valve for discharging gases released during the decomposition of hydrates.

[0011] According to the hydrate circulation reactor described above, the hydrate circulation reactor further includes a temperature sensor and a pressure sensor. The temperature sensor and the pressure sensor are installed in the generation chamber, the intermediate chamber, and the decomposition chamber to monitor the temperature and pressure in the generation chamber, the intermediate chamber, and the decomposition chamber.

[0012] On the other hand, the present invention also provides a hydrate recycling reaction method, applied to the hydrate recycling reactor described above, comprising: System initialization and precooling: The alveolar hydration bulbs pre-filled with liquid water or accelerator solution are loaded into the generation chamber and sealed. The generation chamber is precooled, and the entire hydrate circulation reactor is evacuated or gas-purged. High-pressure capture and hydrate formation: High-pressure raw material gas is injected into the generation chamber. Gas molecules pass through the outer shell and enter the internal reaction chamber, where they undergo a hydration reaction with water to form solid hydrates. Pressure equalization and transfer: The pressure in the intermediate chamber is adjusted to match that in the generation chamber through the pressure balancing pipeline, and the gate valve isolation door is opened in sequence, so that the alveolar hydration bulbs fall into the intermediate chamber and the decomposition chamber in sequence under the action of gravity. Confined space release and gas recovery: The hydrate is decomposed at normal temperature and pressure in the decomposition chamber. The released high-purity gas is discharged and collected through the exhaust valve, and the water produced by decomposition is locked inside the alveolar hydration bulb. Mechanical inversion and alveolar hydration bulb circulation: After the gas is released, the hydrate circulation reactor is inverted so that the decomposition chamber is on top. The gate valve isolation door is opened so that the alveolar hydration bulb falls back into the generation chamber under the action of gravity, thus completing the alveolar hydration bulb circulation.

[0013] According to the hydrate recycling reaction method described above, the pressure equalization transfer step includes: The pressure in the intermediate chamber is increased to match that in the production chamber through the pressure balancing pipeline. The pressure balancing pipeline is then closed, and the gate valve isolation door between the production chamber and the intermediate chamber is opened, allowing the alveolar hydration ball to fall into the intermediate chamber. Close the gate valve isolation door, reduce the pressure in the intermediate chamber to zero, and then open the gate valve isolation door between the intermediate chamber and the decomposition chamber. The alveolar hydration ball falls into the decomposition chamber.

[0014] According to the hydrate circulation reaction method described above, the steps of mechanical inversion and alveolar hydrate bulb circulation include: After inverting the hydrate circulation reactor, each gate valve isolation door is opened in sequence, allowing all the alveolar hydrated balls to fall back into the generation chamber under the action of gravity. Close all gate valve isolation doors and reverse the hydrate circulation reactor back to its original working direction; After evacuating the hydrate circulation reactor, the next cycle begins directly.

[0015] The beneficial effects of the hydrate recycling reactor and hydrate recycling reaction method provided by the present invention are at least as follows: (1) The hydrate circulation reactor provided by the present invention organically combines four features: alveolar hydrated ball as an independent recirculating carrier, three compartments vertically connected in series + gate valve pressure decoupling, intermediate compartment air-locking buffer pressure balance, and overall mechanical flipping reset. The alveolar hydrated ball solves the problem of solid phase transport, the gate valve isolation door + intermediate compartment solves pressure decoupling, and the overall flipping solves medium reflux. All four are indispensable. Only after combination can a truly pump-free, medium-loss-free, pressure gradient-controlled, and heat space-decoupled quasi-continuous hydrate reaction device be realized.

[0016] (2) The hydrate circulation reactor provided by the present invention is low in energy consumption, easy to operate and stable in performance. It is a three-stage vertical reaction system based on gravity-driven flipping. The independent pressure and temperature control of each functional area is achieved through two sets of gate valve isolation doors. The alveolar hydrate ball is used as the core reaction medium. By vertically connecting the generation chamber, intermediate chamber and decomposition chamber, the intermediate chamber plays a role in gas lock buffering under the premise of maintaining the high pressure capture environment of the generation chamber and the release environment of the decomposition chamber. This allows the reaction medium to flow smoothly by relying on the gravitational potential energy, achieving quasi-continuous operation of gas capture and release process. At the same time, the pressure balance mechanism of the intermediate chamber is used to ensure the stability of system operation. The reaction medium is recycled and reused in the closed system by mechanically flipping the entire reactor by 180 degrees. This greatly simplifies the hydrate circulation reactor and improves the integration of the experimental device.

[0017] (3) This invention utilizes alveolar hydration balls to achieve physical isolation between the gas and liquid phases, thereby transforming the problem of traditional hydrate slurry being difficult to transport into the free fall of the rigid alveolar hydration balls under gravity, fundamentally solving the industry problem of solid product accumulation and pipeline blockage.

[0018] (4) The present invention completely decouples the temperature control systems of the generation chamber and the decomposition chamber through spatial temperature partitioning design, and physically isolates the collection stage and the release stage, thereby achieving physical isolation of the gas and liquid phases. This avoids the huge thermal inertia energy consumption generated by the single-pot equipment during frequent heating and cooling, and greatly improves thermal efficiency.

[0019] (5) This invention achieves quasi-continuous operation of gas capture and release process through decoupling control of three chambers and gravity flipping design, which significantly shortens the single experimental cycle and improves the system integration and controllability of experimental operation. Attached Figure Description

[0020] To more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0021] Figure 1 A three-dimensional structural schematic diagram of the hydrate circulation reactor provided by the present invention; Figure 2 A schematic cross-sectional view of the hydrate circulation reactor provided by the present invention; Figure 3 The control principle diagram of the hydrate circulation reactor provided by the present invention; Figure 4 A flowchart of the hydrate recycling reaction method provided by the present invention.

[0022] The following are the labeling elements in the figure: 100. Hydrate Circulation Reactor; 10. Multi-compartment Reactor Body; 11. Generation Chamber; 111. Gas Injection Valve; 12. Intermediate Chamber; 13. Decomposition Chamber; 131. Exhaust Valve; 20. Sealed Top Cover; 30. Alveolar Hydration Sphere; 31. Outer Shell; 32. Internal Reaction Chamber; 40. Gate Valve Isolation Door; 50. Pressure Balance Piping; 60. Controller; 70. Temperature Sensor; 80. Pressure Sensor. Detailed Implementation

[0023] To make the technical problems to be solved, the technical solutions, and the beneficial effects of the present invention clearer, the present invention will be further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention.

[0024] It should be noted that when a component is referred to as "fixed to" or "set on" another component, it may be directly or indirectly located on that other component. When a component is referred to as "connected to" another component, it may be directly or indirectly connected to that other component. The terms "upper," "lower," "left," "right," "front," "rear," "vertical," "horizontal," "top," "bottom," "inner," and "outer," etc., indicate orientations or positions based on the accompanying drawings, and are for ease of description only, and should not be construed as limiting the technical solution. The terms "first" and "second" are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of technical features. "A plurality" means two or more, unless otherwise explicitly defined.

[0025] Please see Figures 1 to 3 This embodiment provides a hydrate circulation reactor 100, including a multi-compartment reaction body 10, a sealed top cover 20, multiple alveolar hydrate balls 30, and a controller 60.

[0026] The multi-compartment reaction body 10 includes a generation compartment 11, an intermediate compartment 12, and a decomposition compartment 13 arranged coaxially from top to bottom. The generation compartment 11, intermediate compartment 12, and decomposition compartment 13 form a vertical three-section structure. Pressure decoupling and selective communication are achieved between the generation compartment 11 and the intermediate compartment 12, and between the intermediate compartment 12 and the decomposition compartment 13, through gate valve-type isolation doors 40. The controller 60 is electrically connected to the gate valve-type isolation doors 40 to automatically control the opening and closing of the gate valve-type isolation doors 40. It should be understood that this embodiment can be expanded into four or more multi-stage series compartments according to processing capacity requirements, using gradient pressure release to improve gas purity.

[0027] The ends of the generating chamber 11 and the decomposition chamber 13 are each provided with a sealing top cover 20 to seal the generating chamber 11 and the decomposition chamber 13. That is, it includes a first sealing top cover and a second sealing top cover. The first sealing top cover is used to seal the generating chamber 11 and the second sealing top cover is used to seal the decomposition chamber 13.

[0028] The alveolar hydrate spheres 30, serving as recyclable independent reaction media, are used in the hydrate circulation reactor 100 after a reaction cycle. During the overall inversion and reset, the alveolar hydrate spheres 30, aided by gravity, sequentially pass through the generation chamber 11, the intermediate chamber 12, and the decomposition chamber 13, completing a unidirectional circulation among these chambers. This achieves a quasi-continuous operation of hydrate generation, transfer, decomposition, and circulation of the alveolar hydrate spheres 30. It should be understood that the alveolar hydrate spheres 30 can also be replaced with ellipsoids, polyhedra, or regular cylindrical capsules.

[0029] The working principle and beneficial effects of the hydrate circulation reactor 100 provided in this embodiment are as follows: (1) The hydrate circulation reactor 100 provided by the present invention organically combines four features: alveolar hydrate ball 30 as an independent recirculating carrier, three compartments vertically connected in series + gate valve pressure decoupling, intermediate compartment air-locking buffer pressure balance, and overall mechanical flipping reset. The alveolar hydrate ball 30 solves the problem of solid phase transportation, the gate valve isolation door + intermediate compartment solves the pressure decoupling, and the overall flipping solves the medium backflow. All four are indispensable. Only after combination can a truly pump-free, medium-loss-free, pressure gradient-controlled, and heat space-decoupled quasi-continuous hydrate reaction device be realized.

[0030] (2) The hydrate circulation reactor 100 provided in this embodiment is low in energy consumption, easy to operate and has stable performance. It is a three-stage vertical reaction system based on gravity-driven flipping. The independent pressure and temperature control of each functional area is achieved through two sets of gate valve isolation doors 40. The alveolar hydrate ball 30 is used as the core reaction medium. By vertically connecting the generation chamber 11, intermediate chamber 12 and decomposition chamber 13, under the premise of maintaining the high pressure capture environment of generation chamber 11 and the release environment of decomposition chamber 13, the intermediate chamber 12 plays the role of gas lock buffer, so that the reaction medium can flow smoothly by relying on the gravitational potential energy, and the gas capture and release process is quasi-continuous. At the same time, the pressure balance mechanism of intermediate chamber 12 is used to ensure the stability of system operation. The reactor is mechanically flipped 180 degrees (it can be manually flipped, or driven by electric servo, pneumatic swing cylinder, or the reactor can be designed as a circumferential rotating cylinder structure to further improve the automation of circulation switching), the reaction medium is recycled and reused in the closed system, which greatly simplifies the hydrate circulation reactor 100 and improves the integration of the experimental device. It should be understood that, in addition to the proposed 180-degree overall rotation to achieve an "hourglass" cycle, this embodiment can also use an internal turntable structure to switch the position of the compartment, or use a vertical lifting mechanism to send the bottom alveolar hydration ball 30 back to the top compartment.

[0031] (3) In this embodiment, the alveolar hydration ball 30 is used to achieve physical isolation between the gas and liquid phases, thereby transforming the problem of traditional hydrate slurry being difficult to transport into the free fall of the rigid alveolar hydration ball 30 under gravity, fundamentally solving the industry problem of solid product accumulation and pipeline blockage.

[0032] (4) In this embodiment, the temperature control systems of the generation chamber 11 and the decomposition chamber 13 are completely decoupled by the spatial temperature partition design, the physical space of the collection stage and the release stage is isolated, and the physical isolation of the gas and liquid phases is achieved. This avoids the huge thermal inertia performance loss generated by the single-pot equipment during frequent heating and cooling, and greatly improves the thermal efficiency.

[0033] (5) This embodiment achieves quasi-continuous operation of gas capture and release process through decoupling control of three chambers and gravity flipping design, which significantly shortens the single experiment cycle and improves the system integration and controllability of experimental operation.

[0034] In one embodiment, see Figure 1 and Figure 2The alveolar hydration ball 30 includes an outer shell layer 31, which is composed of a rigid support skeleton and a hydrophobic and breathable polymer membrane (e.g., a material similar to a waterproof jacket membrane). The outer shell layer 31 has an internal reaction chamber 32, which is used to encapsulate a predetermined proportion of water or a hydrate promoter solution. The predetermined proportion of water and hydrate is loaded into the internal reaction chamber 32 to control the hydrate formation rate and gas storage density.

[0035] In one embodiment, the outer shell layer 31 has a microporous structure that allows gas molecules (such as methane and carbon dioxide) to diffuse freely. This microporous structure allows gas molecules to diffuse through while trapping liquid water and hydrate products within the internal reaction chamber 32. The size of the liquid water or hydrate products is much larger than that of gas molecules, and the micropores are much smaller than the size of the liquid water or hydrate products; therefore, the liquid water or hydrate products are physically contained within the internal reaction chamber 32. Optionally, the pore size of the microporous structure is 0.1 nm to 10 nm, allowing gas molecules to diffuse freely while blocking liquid water molecules through the internal reaction chamber due to hydrophobic interactions.

[0036] In one embodiment, the diameter of the alveolar hydration ball is smaller than the through-hole diameter of the gate valve isolation door when it is open, and larger than the sealing gap of the gate valve isolation door when it is closed, so as to ensure that the alveolar hydration ball can pass smoothly when the gate valve isolation door is open and is not clamped or damaged when it is closed.

[0037] In one embodiment, see Figure 1 and Figure 2 The gate valve-type isolation gate 40 adopts a flat sliding sealing structure, which has extremely high airtightness. This flat sliding sealing structure ensures reliable sealing while significantly reducing friction and wear. Specifically, the gate valve-type isolation gate 40 adopts a flat sliding sealing structure, which includes a valve body frame, a horizontally sliding metal flat valve core, elastic sealing rings (such as fluororubber O-rings or metal C-rings) on the upper and lower sides of the valve core, and a pneumatic / electric actuator to drive the horizontal movement of the valve core. When the valve core is in the closed position, the preload applied by the actuator presses the upper and lower sealing rings against the valve seat sealing surface, forming a double seal. When the valve core is in the open position, it slides horizontally out of the chamber passage, allowing the alveolar hydrated ball 30 to pass freely under gravity. Compared to ball valves or butterfly valves, this structure avoids shearing and squeezing of the alveolar hydrated ball 30 during valve core rotation, and the sliding direction is perpendicular to the falling direction of the alveolar hydrated ball 30, thus not affecting gravity flow.

[0038] In one embodiment, the outer wall of the generation chamber 11 is covered with a cooling jacket, which is used to control the temperature inside the generation chamber 11 within the generation window range of gas hydrates, that is, the cooling jacket can perform precise temperature control.

[0039] In other embodiments, a serpentine heat exchange tube can be built into the generation chamber 11 or a semiconductor heating and cooling plate can be embedded in the chamber wall to achieve precise temperature control.

[0040] In one embodiment, see Figure 1 and Figure 2 The intermediate chamber 12 is equipped with a pressure balancing pipeline 50, which is electrically connected to the controller 60. The pressure balancing pipeline 50 is used to ensure that the pressure of adjacent chambers is equal before the gate valve isolation door 40 is opened. The intermediate chamber 12 acts as an airlock buffer chamber, realizing a pressure gradient transition between the high-pressure collection environment of the generation chamber 11 and the normal-pressure release environment of the decomposition chamber 13, avoiding sudden increases or decreases in pressure. By setting gate valve isolation doors 40 between each chamber and matching them with a pressure balancing mechanism (pressure balancing pipeline 50), the gate valve isolation doors 40 realize the quota transfer of materials between different temperature and pressure environments.

[0041] In one embodiment, see Figure 1 and Figure 2 The generating chamber 11 is equipped with an injection valve 111, which is used to introduce raw material gas into the generating chamber 11. The decomposition chamber 13 releases the captured gas from the hydrates in the alveolar hydration bulb 30 by heating and depressurizing. The decomposition chamber 13 is equipped with an exhaust valve 131, which is used to discharge the gas released by the decomposition of hydrates.

[0042] In one embodiment, the inner walls of the generation chamber 11, intermediate chamber 12 and decomposition chamber 13 are provided with guiding slopes or funnel-shaped guiding structures, so that the alveolar hydration balls 30 automatically converge to the gate valve isolation door 40 under the action of gravity.

[0043] In one embodiment, see Figure 1 and Figure 2 The hydrate circulation reactor 100 further includes a temperature sensor 70 and a pressure sensor 80. The temperature sensor 70 and the pressure sensor 80 are installed in the generation chamber 11, the intermediate chamber 12 and the decomposition chamber 13. The temperature sensor 70 and the pressure sensor 80 are electrically connected to the controller 60 for automatically monitoring the temperature and pressure in the generation chamber 11, the intermediate chamber 12 and the decomposition chamber 13.

[0044] Please see Figure 4 This embodiment also provides a hydrate recycling reaction method applied to the hydrate recycling reactor 100 described above, comprising: Step S100, System initialization and precooling: The alveolar hydration ball 30 prefilled with liquid water or accelerator solution is loaded into the generation chamber 11 and sealed. The generation chamber 11 is precooled, and the entire hydrate circulation reactor 100 is evacuated or gas-purified.

[0045] Specifically, alveolar hydration bulbs 30 pre-filled with liquid water or accelerator solution are loaded into the generation chamber 11, and the generation chamber 11 is sealed by covering it with a first sealing top cover. The cooling jacket covering the outer wall of the generation chamber 11 is opened by the control system to pre-cool the inside of the generation chamber 11 to the target reaction temperature. The entire hydrate circulation reactor 100 is evacuated or replaced with the target gas to eliminate interference from impurity gases.

[0046] Step S200, High-pressure capture and hydrate generation: High-pressure raw material gas is injected into the generation chamber 11. Gas molecules pass through the outer shell layer 31 and enter the internal reaction chamber 32, where they undergo a hydration reaction with water to generate solid hydrates.

[0047] Specifically, high-pressure raw material gas is injected into the generation chamber 11 through the gas injection valve 111 to the predetermined experimental pressure; Driven by the pressure difference, gas molecules pass through the hydrophobic and breathable rigid shell of the alveolar hydration bulb 30 and enter the internal reaction chamber 32, where they undergo a hydration reaction with water. The pressure and temperature of the generation chamber 11 are maintained stable until the internal reaction chamber 32 of the alveolar hydration ball 30 completes gas capture and conversion into solid hydrate.

[0048] Step S300, pressure equalization and transfer: The pressure of the intermediate chamber 12 is adjusted to be consistent with that of the generation chamber 11 through the pressure balancing pipeline 50, and the gate valve isolation door 40 is opened in sequence, so that the alveolar hydration ball 30 falls into the intermediate chamber 12 and the decomposition chamber 13 in sequence under the action of gravity.

[0049] Specifically, after the pressure in the intermediate chamber 12 is increased to the same level as that in the generating chamber 11 through the pressure balancing pipeline 50, the balancing pipeline is closed, and the gate valve isolation door 40 between the generating chamber 11 and the intermediate chamber 12 is opened. The alveolar hydration ball 30 slides from the generating chamber 11 to the intermediate chamber 12 by gravity and then the gate valve isolation door 40 is closed. Close the gate valve isolation door 40, reduce the pressure of the intermediate chamber 12 to zero, open the gate valve isolation door 40 between the intermediate chamber 12 and the decomposition chamber 13, and the alveolar hydration ball 30 falls into the decomposition chamber 13 by gravity.

[0050] Step S400, confined space release and gas recovery: The hydrate is decomposed at room temperature and pressure in the decomposition chamber 13. The released high-purity gas is discharged and collected through the exhaust valve 131, and the water produced by decomposition is locked inside the alveolar hydration ball 30.

[0051] Specifically, the decomposition chamber 13 is always at normal temperature and pressure. The hydrates in the alveolar hydration sphere 30 decompose at normal temperature and pressure, releasing high-purity gas. Due to the interception effect of the outer shell layer 31, the water produced by decomposition is still locked in the internal reaction chamber 32 of the alveolar hydration sphere 30. High-purity gas is discharged and collected through the exhaust valve 131 at the bottom.

[0052] Step S500, Mechanical inversion and circulation of alveolar hydrated bulb 30: After the gas is released, the hydrate circulation reactor 100 is inverted as a whole, so that the decomposition chamber 13 is on top, and the gate valve isolation door 40 is opened so that the alveolar hydrated bulb 30 falls back to the generation chamber 11 under the action of gravity, thus completing the circulation of alveolar hydrated bulb 30.

[0053] Specifically, after the gas in the decomposition chamber 13 is released and the alveolar hydration bulb 30 returns to a liquid water state, the pressure in the three chambers of generation chamber 11, intermediate chamber 12 and decomposition chamber 13 is reduced to zero, the hydrate circulation reactor 100 is reversed so that the decomposition chamber 13 is at the top, and the two gate valve isolation doors 40 are opened so that the alveolar hydration bulb 30 falls back into the generation chamber 11. After completion, close all gate valve isolation doors 40, flip it over again, and reverse the hydrate circulation reactor 100 back to its original working direction; After the hydrate circulation reactor 100 is evacuated, the hydrate circulation reactor 100 can proceed to the next cycle.

[0054] Throughout the hydrate circulation reaction process, no external booster pump is required to drive the circulation of the reaction medium, and no water or reaction medium needs to be added during the circulation process.

[0055] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A hydrate circulation reactor, characterized in that, include: A multi-compartment reaction body, comprising a generation compartment, an intermediate compartment, and a decomposition compartment arranged coaxially from top to bottom, wherein gate valve-type isolation doors are provided between the generation compartment and the intermediate compartment, and between the intermediate compartment and the decomposition compartment; The sealing top cover is provided at the ends of both the generation chamber and the decomposition chamber; Multiple alveolar hydration balls, which serve as recyclable independent reaction media, are used in the hydrate circulation reactor for overall inversion and reset after completing one reaction cycle. The alveolar hydration balls pass through the generation chamber, the intermediate chamber, and the decomposition chamber in sequence by gravity, completing a unidirectional circulation flow between the generation chamber, the intermediate chamber, and the decomposition chamber, thus realizing a quasi-continuous operation of hydrate generation, transfer, decomposition, and alveolar hydration ball circulation.

2. The hydrate circulation reactor according to claim 1, characterized in that, The alveolar hydration ball includes an outer shell layer having an internal reaction chamber for encapsulating a predetermined proportion of water or a hydration promoter solution. The outer shell has a microporous structure that allows gas molecules to diffuse freely, while locking liquid water and hydrate products inside the internal reaction chamber.

3. The hydrate circulation reactor according to claim 1, characterized in that, The gate valve type isolation door adopts a flat sliding sealing structure; The diameter of the alveolar hydration ball is smaller than the orifice diameter of the gate valve isolation door when it is open, and larger than the sealing gap of the gate valve isolation door when it is closed.

4. The hydrate circulation reactor according to claim 1, characterized in that, The outer wall of the generation chamber is covered with a cooling jacket, which is used to control the temperature inside the generation chamber within the generation window range of gas hydrates.

5. The hydrate circulation reactor according to claim 1, characterized in that, The intermediate chamber is equipped with a pressure balancing pipeline, which is used to make the pressure of the two adjacent chambers equal before the gate valve isolation door is opened. The intermediate chamber serves as a gas-locking buffer chamber, realizing a pressure gradient transition between the high-pressure collection environment of the generation chamber and the normal-pressure release environment of the decomposition chamber.

6. The hydrate circulation reactor according to claim 1, characterized in that, The generating chamber is equipped with an injection valve, which is used to introduce raw material gas into the generating chamber. And / or, the decomposition chamber is equipped with an exhaust valve for discharging gases released during the decomposition of hydrates.

7. The hydrate circulation reactor according to claim 1, characterized in that, The hydrate circulation reactor also includes a temperature sensor and a pressure sensor. The temperature sensor and the pressure sensor are installed in the generation chamber, the intermediate chamber, and the decomposition chamber to monitor the temperature and pressure in the generation chamber, the intermediate chamber, and the decomposition chamber.

8. A hydrate recycling reaction method, applied to the hydrate recycling reactor according to any one of claims 1 to 7, characterized in that, include: System initialization and precooling: The alveolar hydration bulbs pre-filled with liquid water or accelerator solution are loaded into the generation chamber and sealed. The generation chamber is precooled, and the entire hydrate circulation reactor is evacuated or gas-purged. High-pressure capture and hydrate formation: High-pressure raw material gas is injected into the generation chamber. Gas molecules pass through the outer shell and enter the internal reaction chamber, where they undergo a hydration reaction with water to form solid hydrates. Pressure equalization and transfer: The pressure in the intermediate chamber is adjusted to match that in the generation chamber through the pressure balancing pipeline, and the gate valve isolation door is opened in sequence, so that the alveolar hydration bulbs fall into the intermediate chamber and the decomposition chamber in sequence under the action of gravity. Confined space release and gas recovery: The hydrate is decomposed at normal temperature and pressure in the decomposition chamber. The released high-purity gas is discharged and collected through the exhaust valve, and the water produced by decomposition is locked inside the alveolar hydration bulb. Mechanical inversion and alveolar hydration bulb circulation: After the gas is released, the hydrate circulation reactor is inverted so that the decomposition chamber is on top. The gate valve isolation door is opened so that the alveolar hydration bulb falls back into the generation chamber under the action of gravity, thus completing the alveolar hydration bulb circulation.

9. The hydrate recycling reaction method according to claim 8, characterized in that, The step of equalizing and transferring voltage includes: The pressure in the intermediate chamber is increased to match that in the production chamber through the pressure balancing pipeline. The pressure balancing pipeline is then closed, and the gate valve isolation door between the production chamber and the intermediate chamber is opened, allowing the alveolar hydration ball to fall into the intermediate chamber. Close the gate valve isolation door, reduce the pressure in the intermediate chamber to zero, and then open the gate valve isolation door between the intermediate chamber and the decomposition chamber. The alveolar hydration ball falls into the decomposition chamber.

10. The hydrate recycling reaction method according to claim 8, characterized in that, The steps of mechanical inversion and alveolar hydration bulb circulation include: After inverting the hydrate circulation reactor, each gate valve isolation door is opened in sequence, allowing all the alveolar hydrated balls to fall back into the generation chamber under the action of gravity. Close all gate valve isolation doors and reverse the hydrate circulation reactor back to its original operating direction; After evacuating the hydrate circulation reactor, the next cycle begins directly.

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