Carbon dioxide hydrate energy storage power generation system and method using ocean energy

Abstract

The application discloses a carbon dioxide hydrate energy storage power generation system and method using ocean energy, which comprises a hydrate generating energy storage system using deep seawater cold energy to generate carbon dioxide hydrate, a hydrate decomposing system for decomposing the generated carbon dioxide hydrate, a deep seawater cascade utilization system for further utilizing the deep seawater cold energy discharged by the hydrate generating energy storage system, and a power generation system for generating power by using high-pressure carbon dioxide gas decomposed in the hydrate decomposing system. The application utilizes small-temperature-difference heat sources such as ocean temperature difference energy to generate power without pollution, and can realize cascade utilization of the cold energy of deep seawater.

Description

Technical Field

[0001] This invention relates to the fields of hydrate utilization and cryogenic power generation, and in particular to a carbon dioxide hydrate energy storage and power generation system and method utilizing ocean energy. Background Technology

[0002] The ocean contains abundant renewable energy resources, such as tidal energy, wave energy, and ocean thermal energy conversion (OTEC). OTEC is a low-grade renewable energy source derived from solar radiation, where deep seawater is colder than surface seawater. In the low latitudes of the Pacific Ocean, the average surface seawater temperature can reach over 20°C, with temperatures increasing as latitude decreases. However, for deep seawater below 200m, the temperature drops to 1-10°C, and at depths of 800-1000m, it is 4-6°C. Fully utilizing low-temperature waste heat and OTEC resources to produce clean, green electricity will greatly help reduce fossil fuel consumption.

[0003] Traditional methods of power generation using low-temperature heat sources include the Organic Rankine Cycle and the Karina Cycle. These methods typically utilize temperature differences between 20 and 100°C and employ flammable alkanes, explosive ammonia, or fluorinated refrigerants as working fluids, resulting in poor safety and environmental friendliness. On one hand, under low-temperature, small-temperature-difference conditions, additional heat pumps and heaters are needed to increase the temperature difference for power generation, increasing the cost and complexity of the entire system. On the other hand, deep seawater, due to its constant low temperature, rich inorganic salts and minerals in a free ionized state, and sterile purity, can be used for aquaculture, agriculture and food development, medical and cosmetic applications, etc. Flammable alkanes, explosive ammonia, or fluorinated refrigerants would all damage the ecological environment of deep seawater. Therefore, using traditional low-temperature heat sources for power generation would inevitably cause harm to the marine ecosystem.

[0004] Carbon dioxide hydrate is a cage-like crystalline substance formed by carbon dioxide gas and water molecules under appropriate pressure and temperature conditions. It is a clean and environmentally friendly substance. The hollow hydrate lattice of carbon dioxide hydrate acts like a highly efficient molecular-level gas storage device, storing 160-180 m³ of gas per cubic meter. This gives the gas hydrate unique decomposition and expansion characteristics: it can obtain a large pressure difference from a small temperature change. Carbon dioxide hydrate can achieve a pressure difference of 3 MPa at a temperature difference of 10°C, and even with a temperature difference of less than 10°C, the pressure difference is still considerable. This makes it possible to generate electricity using low-temperature heat sources with small temperature differences. Furthermore, carbon dioxide hydrate can undergo a phase change above zero degrees Celsius and has a high latent heat of phase change (500 kJ / kg), making it suitable for use as an energy storage substance. Whether carbon dioxide hydrate can be applied to generate electricity using ocean energy—a low-temperature, small-temperature-difference heat source—and fully utilize deep seawater resources and the energy storage characteristics of carbon dioxide hydrate, is a technical problem that urgently needs to be solved. Summary of the Invention

[0005] This invention addresses the shortcomings of existing technologies by providing a pollution-free carbon dioxide hydrate energy storage and power generation system and method that utilizes ocean heat sources with small temperature differences to generate electricity, while simultaneously enabling the cascade utilization of deep seawater cooling capacity.

[0006] To achieve the above objectives, this invention first proposes a carbon dioxide hydrate energy storage and power generation system and method utilizing ocean energy. The system includes a hydrate generation and storage system that uses the cold energy of deep seawater to generate carbon dioxide hydrates; a hydrate decomposition system that decomposes the generated carbon dioxide hydrates; a deep seawater cascade utilization system that further utilizes the cold energy of the deep seawater discharged from the hydrate generation and storage system; and a power generation system that uses the high-pressure carbon dioxide gas decomposed within the hydrate decomposition system to generate electricity. The outlet of the hydrate generation energy storage system is connected to the hydrate decomposition system and the cooling user end via pipelines. The gas outlet of the hydrate decomposition system is connected to the air inlet of the power generation system via pipelines. The liquid outlet of the hydrate decomposition system flows back to the hydrate generation energy storage system via pipelines. The air outlet of the power generation system is connected to the inlet of the hydrate generation energy storage system via pipelines. The inlet of the heat exchange pipeline in the hydrate generation energy storage system is pumped from deep seawater by a first seawater pump, and the outlet is connected to the inlet of the deep seawater cascade utilization system via pipelines. The outlet of the deep seawater cascade utilization system is connected to the inlet of the heat exchange pipeline in the hydrate decomposition system via pipelines. The outlet of the heat exchange pipeline in the hydrate decomposition system is directly discharged into the ocean.

[0007] In this embodiment, the hydrate generation and energy storage system includes a hydrate generation tank, the hydrate decomposition system includes a hydrate decomposition tank, the deep seawater cascade utilization system includes an air conditioning system, a photovoltaic thermal system, and a deep seawater collection tank. The air conditioning system includes an air cooler, the photovoltaic thermal system includes a photovoltaic panel water cooling device, and the power generation system includes an expander and a buffer tank. The hydrate generation tank is equipped with a first temperature sensor to detect the internal temperature and a first pressure sensor to detect the internal pressure. A first heat exchange pipeline is installed inside the hydrate generation tank. An electromagnetic heat meter is installed between the inlet and outlet pipes of the first heat exchange pipeline to monitor the cumulative heat exchange. The hydrate generation tank has a hydrate outlet at the middle of one side, a water inlet at the upper part of the other side, a gas inlet at the middle part of the other side, and a gas inlet at the lower part. The hydrate decomposition tank is equipped with a second temperature sensor to detect the internal temperature and a second pressure sensor to detect the internal pressure. A second heat exchange pipeline is installed inside the hydrate decomposition tank. A hydrate inlet is located in the middle of one side of the tank, and a water outlet is located at the lower part of the other side. A gas outlet is located at the top of the hydrate decomposition tank. The hydrate outlet of the hydrate generation tank is connected to the inlet of the hydrate slurry pump via a pipeline. The outlet of the hydrate slurry pump is connected to the inlet of the first tee pipe. One outlet of the first tee pipe is connected to the inlet of the third interlock valve via a pipeline, and the other outlet is connected to the inlet of the fourth interlock valve via a pipeline. The outlet of the third interlock valve is connected to the user end of the cooling capacity via a pipeline. The outlet of the fourth interlock valve is connected to the cold side inlet of the regenerator via a pipeline. The cold side outlet of the regenerator is connected to the hydrate inlet of the hydrate decomposition tank via a pipeline. The water outlet of the hydrate decomposition tank is connected to the hot side inlet of the regenerator via a pipeline. The hot side outlet of the regenerator is connected to the water inlet of the hydrate generation tank via a first switch valve. The gas outlet of the hydrate decomposition tank is connected to the high-pressure inlet of the expander via a pipeline. The low-pressure outlet of the expander is connected to the inlet of the buffer tank. The outlet of the buffer tank is connected to the gas inlet of the hydrate generation tank via a second switch valve. The outlet of the carbon dioxide tank is connected to the inlet of the pressure control valve via a pipeline. The outlet of the pressure control valve is connected to the make-up gas inlet of the hydrate generation tank via a third switch valve. The inlet of the first heat exchange pipeline is connected to the outlet of the first seawater pump. The inlet of the first seawater pump is connected to the deep seawater intake pipe via a pipeline. The outlet of the first heat exchange pipeline is connected to the inlet of the air cooler pipeline. The outlet of the air cooler pipeline is connected to the inlet of the photovoltaic panel water cooling device. The outlet of the photovoltaic panel water cooling device is connected to the outlet of the second three-way pipe. One outlet of the second three-way pipe is connected to the inlet of the first interlock valve, and the other outlet is connected to the inlet of the second interlock valve. The outlet of the first interlock valve is connected to the inlet of the deep seawater collection tank. The outlet of the second interlock valve is connected to the inlet of the third three-way pipe via a pipeline. The other inlet of the third three-way pipe is connected to the outlet of the check valve via a pipeline. The inlet of the check valve is connected to the outlet of the second seawater pump via a pipeline. The inlet of the second seawater pump is connected to the surface seawater intake pipe via a pipeline. The outlet of the third three-way pipe is connected to the inlet of the second heat exchange pipeline. The outlet of the second heat exchange pipeline is connected to the drain pipe. The outlet of the drain pipe is located away from the deep seawater and surface seawater intake points.

[0008] In this embodiment, an accelerator solution tank is also included. The top of the hydrate generation tank is provided with an accelerator solution inlet. The outlet of the accelerator solution tank is connected to the inlet of a solution pump through a pipeline, and the outlet of the solution pump is connected to the accelerator solution inlet of the hydrate generation tank through a pipeline.

[0009] In this embodiment, the first interlock valve and the second interlock valve are mechanically interlocked, and the mechanical interlock causes one of the first interlock valve and the second interlock valve to open, while the other valve is closed. The third interlock valve and the fourth interlock valve are mechanically interlocked, and the mechanical interlock causes one of the third interlock valve and the fourth interlock valve to open, while the other valve is closed.

[0010] In this embodiment, both the first heat exchange pipeline and the second heat exchange pipeline are coiled heat exchange pipelines.

[0011] In this embodiment, the air cooler's pipe outlet and pipe inlet are connected by a connecting pipe, and a bypass regulating valve is installed on the connecting pipe.

[0012] In this embodiment, the air cooler is placed in an air-conditioned room, and a third temperature sensor is also installed in the air-conditioned room. The photovoltaic panel water-cooling device of the photovoltaic thermal system is placed on the roof of the building.

[0013] This invention also includes a method for generating electricity using carbon dioxide hydrate energy storage from ocean energy, controlled by the aforementioned energy storage and power generation system. It includes the following two working modes, a. Energy storage mode: In this state, open the first and third interlock valves, close the second and fourth interlock valves, the first and second switch valves, and shut down the hydrate slurry pump and the second seawater pump. Start the solution pump and the first seawater pump. When the reading returned by the first temperature sensor stabilizes within the target low temperature range for hydrate formation, open the third switch valve. The pressure control valve controls the carbon dioxide in the carbon dioxide tank to enter the hydrate formation tank, and hydrate begins to form in the hydrate formation tank. At the same time, the electromagnetic heat meter detects the cumulative heat exchange in the first heat exchange pipeline. When the amount of hydrate formed in the hydrate formation tank reaches the required amount for cold storage, close the third switch valve, the solution pump, and the first seawater pump to gradually stop the formation of hydrate. When the user needs to use the cold, start the hydrate slurry pump and transport the stored hydrate slurry to the user end for cold release through the pipeline. b. Power generation mode: In this state, the third and first interlock valves are closed, the second and fourth interlock valves are opened, the second seawater pump is shut down, and the air cooler and photovoltaic panel water cooling device are in operation. The solution pump and the first seawater pump are started. Deep seawater flows sequentially through the first heat exchange pipeline, the air cooler, the photovoltaic panel water cooling device, and the second heat exchange pipeline of the hydrate decomposition tank before being discharged into the ocean. The seawater preheats the hydrate decomposition tank through the second heat exchange pipeline. When the reading returned by the first temperature sensor stabilizes within the target low temperature range for hydrate formation, the third switch valve is opened, and the pressure control valve controls the carbon dioxide in the carbon dioxide gas tank to enter the hydrate formation tank. Carbon dioxide hydrate begins to form in the hydrate formation tank. The electromagnetic heat meter detects the cumulative heat exchange in the first heat exchange pipeline. When the amount of hydrate formed in the hydrate formation tank meets the power generation requirements, the hydrate slurry pump is turned on to pressurize the generated carbon dioxide hydrate and send it to the hydrate decomposition tank through the regenerator. The carbon dioxide hydrate decomposes into high-pressure carbon dioxide gas and high-temperature water in the hydrate decomposition tank. When the reading returned by the second pressure sensor on the hydrate decomposition tank stabilizes within the target pressure range for power generation, the second and first switching valves are opened. The high-pressure carbon dioxide gas separated from the carbon dioxide hydrate enters the expander, expands, and performs work to drive the generator, which then outputs electricity via a voltage regulator. The carbon dioxide gas, after performing work, passes through a buffer tank and is then returned to the hydrate generation tank via pipeline. Simultaneously, the high-temperature water separated from the carbon dioxide hydrate enters the hot side of the regenerator, preheating the hydrate slurry on the cold side of the regenerator, and is then returned to the hydrate generation tank via pipeline. This cycle repeats continuously. After the power output of the power generation system gradually stabilizes, close the pressure control valve and the third switch valve to complete the carbon dioxide gas filling.

[0014] Using the above method, since both the air conditioning system and the photovoltaic thermal system generate heat during operation, especially the photovoltaic thermal system, only a portion of the solar radiation absorbed by the photovoltaic panels can be converted into electrical energy, while the remainder is converted into heat energy, causing the photovoltaic panel temperature to rise and leading to a decrease in photoelectric conversion efficiency. Therefore, in the power generation mode, this application will utilize the cooling capacity of deep seawater to cool the air conditioning system and the photovoltaic thermal system, thereby improving the photovoltaic power generation efficiency. At the same time, it will also heat up the deep seawater, which can be used for the decomposition of carbon dioxide hydrates. In this way, the synergistic effect of inexhaustible renewable energy sources such as solar energy and ocean energy is used to realize energy utilization. On the one hand, it solves the problem that low-temperature waste heat and ocean thermal energy are difficult to recover and utilize, and the problem that the working fluid used in traditional low-temperature heat source power generation methods is not safe and environmentally friendly enough. On the other hand, it realizes the cascade utilization of the cooling capacity of deep seawater resources.

[0015] In the above embodiments, when the power generation mode is running, if the reading of the second temperature sensor on the hydrate decomposition tank is lower than the target temperature range for hydrate decomposition, the second interlock valve is closed, the first interlock valve is opened, the second seawater pump is turned on, and the second seawater pump pumps surface seawater into the second heat exchange pipeline of the hydrate decomposition tank.

[0016] When sunlight is insufficient, such as on cloudy days or at night, the air conditioning and photovoltaic thermal systems are not enough to raise the temperature of deep seawater to a sufficient level. In this case, a second seawater pump is used to extract surface seawater to decompose carbon dioxide hydrates, thereby generating electricity by utilizing the temperature difference between surface and deep seawater. This not only improves the stability of power generation but also makes full use of ocean thermal energy. By controlling the first and second interlocking valves, deep seawater is discharged into a deep seawater collection tank for subsequent use in aquaculture, agriculture and food development, medical and cosmetic applications.

[0017] In the above embodiments, the electromagnetic heat meter measures the inlet temperature, outlet temperature and outlet flow rate of the first heat exchange pipeline in real time, and calculates the heat exchange of the first heat exchange pipeline according to the preset thermodynamic calculation formula. Based on the cumulative and instantaneous heat exchange of the first heat exchange pipeline and the latent heat of phase change of the hydrate, the mass and formation rate of the generated hydrate are obtained.

[0018] The beneficial effects of this invention are as follows: (1) This invention can directly utilize ocean thermal energy, a low-temperature heat source with a small temperature difference that is difficult to utilize in traditional low-temperature power generation systems, to generate electricity, thereby achieving higher energy efficiency in a simpler system form; (2) This invention uses natural inorganic working fluids carbon dioxide and water. The generated carbon dioxide hydrate is also non-toxic and pollution-free, which can achieve safety, environmental friendliness and zero emissions, produce truly clean electricity, and help achieve the dual carbon goals. (3) While generating electricity, the present invention realizes the cascade utilization of the cold energy of deep seawater. It can not only provide cooling and power supply to air-conditioned rooms and save the cost of building air-conditioning systems, but also cool down photovoltaic panels and improve photoelectric conversion efficiency. The deep seawater that has been used can also be collected for other subsequent uses. (4) In addition to producing zero-emission electricity, the present invention can also generate and store carbon dioxide hydrate separately. By using carbon dioxide hydrate for cold storage, the storage efficiency can be greatly improved by taking advantage of the fact that carbon dioxide hydrate can undergo phase change above zero degrees and has a high latent heat of phase change. (5) The present invention can accelerate the hydrate generation rate by quantitatively adding the promoter, designing the water inlet and air inlet of the generation tank, and regulating the deep seawater flow rate, which is beneficial to matching the hydrate generation and decomposition process under continuous power generation. (6) In the power generation mode, the present invention can choose to recover the waste heat of the traditional air conditioning system and photovoltaic thermal system or utilize the ocean temperature difference according to the actual situation. In this way, through the overall coordinated work of the system, the most energy-efficient operating mode can be selected to achieve higher energy efficiency. Attached Figure Description

[0019] Figure 1 This is a schematic diagram of the structure of the present invention.

[0020] In the attached diagram: 1. Hydrate generation tank; 2. Hydrate slurry pump; 3. First seawater pump; 4. Regenerator; 5. Hydrate decomposition tank; 6. Check valve; 7. Second seawater pump; 8. Wave power generation device; 9. First interlock valve; 10. Second interlock valve; 11. Photovoltaic panel water cooling device; 12. Bypass regulating valve; 13. Air cooler; 14. Generator; 15. Voltage regulator; 16. Expander; 17. Buffer tank; 18. First switching valve; 19. Carbon dioxide gas tank; 20. Second switching valve; 21. Pressure control valve; 22. Third switching valve; 23. Deep seawater collection tank; 24. Accelerator solution tank; 25. Solution pump; 26. Third interlock valve; 27. Fourth interlock valve; 28. First pressure sensor; 29. ​​First temperature sensor; 30. Second pressure sensor; 31. Second temperature sensor; 32. Third temperature sensor; 33. Electromagnetic heat meter. Implementation

[0021] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0022] Furthermore, the technical solutions of the various embodiments of the present invention can be combined with each other, but only if they are feasible for those skilled in the art. If the combination of technical solutions is contradictory or cannot be implemented, it should be considered that such combination of technical solutions does not exist and is not within the scope of protection claimed by the present invention. Example 1

[0023] like Figure 1 As shown: A carbon dioxide hydrate energy storage and power generation system utilizing ocean energy includes: 1. A hydrate generation and energy storage system, comprising a hydrate generation tank 1, a carbon dioxide gas tank 19, a pressure regulating valve 21, a first switching valve 18, a second switching valve 20, a third switching valve 22, an accelerator solution tank 24, a solution pump 25, a third interlock valve 26, a fourth interlock valve 27, a first pressure sensor 28, and a first temperature sensor 29.

[0024] 2. Hydrate decomposition system, which includes hydrate decomposition tank 5, hydrate slurry pump 2, regenerator 4, second pressure sensor 30 and second temperature sensor 31.

[0025] 3. Deep seawater cascade utilization system, the deep seawater cascade utilization system includes a first seawater pump 3, an air conditioning system, a photovoltaic thermal system, a second interlock valve 10, a first interlock valve 9, a deep seawater collection tank 23, a check valve 6, a second seawater pump 7, and a third temperature sensor 32. The air conditioning system includes an air cooler 13, and the photovoltaic thermal system includes a photovoltaic panel water cooling device 11.

[0026] 4. Power generation system, which includes expander 16, generator 14, voltage stabilizer 15, and buffer tank 17.

[0027] The hydrate generation tank 1 is equipped with a first heat exchange pipeline. An electromagnetic heat meter 33 is installed between the inlet and outlet pipes of the first heat exchange pipeline to monitor the cumulative heat exchange. The electromagnetic heat meter 33 can measure the inlet temperature, outlet temperature, and outlet flow rate of the first heat exchange pipeline in real time, and calculate the heat exchange of the first heat exchange pipeline according to a preset thermodynamic calculation formula. Based on the cumulative and instantaneous heat exchange of the first heat exchange pipeline and the latent heat of phase change of the hydrate, the mass and generation rate of the generated hydrate can be obtained. The top of the hydrate generation tank 1 is equipped with an accelerator solution inlet. The outlet of the accelerator solution tank 24 is connected to the accelerator solution inlet of the hydrate generation tank 1 via the solution pump 25. A hydrate generation tank has a hydrate outlet located in the middle of one side, which is connected to the inlet of the hydrate slurry pump 2. The outlet of the hydrate slurry pump 2 is connected to two pipelines: one leads to the cooling user via the third interlock valve 26, and the other leads to the cold-side inlet of the regenerator 4 via the fourth interlock valve. The cold-side outlet of the regenerator 4 is connected to the hydrate inlet of the hydrate decomposition tank 5. The third interlock valve 26 and the fourth interlock valve 27 are mechanically interlocked, meaning that if one valve is opened, the other valve closes simultaneously. The hydrate inlet of the hydrate decomposition tank 5 is located in the middle of one side, and a water outlet is located at the lower part of the other side, connected to the hot-side inlet of the regenerator 4. The hot-side outlet of the regenerator 4 is connected to the water inlet of the hydrate generation tank 1 via the first switch valve 18. The water inlet of the hydrate generation tank 1 is located at the upper part opposite to its hydrate outlet. The top of the hydrate decomposition tank 5 has a gas outlet connected to the high-pressure inlet of the expander 16. The low-pressure outlet of the expander 16 is sequentially connected to the gas inlet of the buffer tank 17, the second switch valve 20, and the hydrate generating tank 1. The gas inlet of the hydrate generating tank 1 is on the same side as its water inlet and located at the bottom. A make-up gas inlet is located between the gas inlet and the water inlet. The outlet of the carbon dioxide tank 19 is connected to the make-up gas inlet of the hydrate generating tank 1 via a pressure control valve 21 and a third switch valve 22. The first pressure sensor 28 and the first temperature sensor 29 are arranged inside the hydrate generating tank to measure the pressure and temperature values ​​inside the tank, respectively. The second pressure sensor 30 and the second temperature sensor 31 are arranged inside the hydrate decomposition tank to measure the pressure and temperature values ​​inside the tank, respectively.

[0028] Both the hydrate generation tank 1 and the hydrate decomposition tank 5 have coiled heat exchange pipes in their lower parts. The inlet of the first seawater pump 3 is connected to a water intake pipe from the deep sea, and its outlet is connected to the inlet of the first heat exchange pipe of the hydrate generation tank 1. The outlet of the first heat exchange pipe of the hydrate generation tank 1 is connected to the inlet of the air cooler 13, and the outlet of the air cooler 13 is connected to the inlet of the photovoltaic panel water cooling device 11. A point is taken from each of the pipes near the inlet and outlet of the air cooler 13 for connection, and the bypass regulating valve 12 is installed on the connected pipe. The pipe connected to the outlet of the photovoltaic panel water cooling device 11 is divided into two paths: one path is connected to the inlet of the deep seawater collection tank 23 via the first interlock valve 9, and the other path is connected to the pipe connected to the inlet of the second heat exchange pipe of the hydrate decomposition tank 5 via the second interlock valve 10. The first interlock valve 9 and the second interlock valve 10 are mechanically interlocked, that is, if one valve is opened, the other valve is closed simultaneously. The inlet of the second seawater pump 7 is connected to a water intake pipe from surface seawater, and its outlet is connected to the inlet of the second heat exchange pipeline of the hydrate decomposition tank 5 via the check valve 6. The connection point between the pipe connected to the outlet of the second interlock valve 10 and the pipe connected to the outlet of the check valve 6 is located between the check valve 6 and the inlet of the second heat exchange pipeline of the hydrate decomposition tank 5. The outlet of the second heat exchange pipeline of the hydrate decomposition tank 5 is connected to a drain pipe, and the drain outlet is located far away from the deep seawater and surface seawater intake points.

[0029] Under low temperature and suitable pressure, carbon dioxide gas and water react to form low-temperature carbon dioxide hydrate in hydrate generation tank 1. The heat released during the generation process is carried away by the low-temperature deep seawater flowing in the heat exchange pipeline through indirect heat exchange. The excess water and carbon dioxide hydrate forming a hydrate slurry are stored in hydrate generation tank 1. The low temperature and low pressure environment are controlled by the flow rate of deep seawater in the heat exchange pipeline and the gas output from the carbon dioxide tank, respectively.

[0030] The first seawater pump 3 is a pump with three speed settings: high speed, medium speed, and low speed. Its speed can be adjusted according to the low-temperature environment requirements of the hydrate generation tank and the switching of system operating modes. The hydrate slurry pump 2, the first seawater pump 3, the second seawater pump 7, the solution pump 25, the bypass regulating valve 12, the first switching valve 18, the second switching valve 20, the third switching valve 22, the pressure control valve 21, the first interlock valve 9, and the third interlock valve 26 are all connected to the control system. The first pressure sensor 28, the first temperature sensor 29, the second pressure sensor 30, the second temperature sensor 31, the third temperature sensor 32, and the electromagnetic heat meter 33 are also connected to the control system. By configuring the control system, it can automatically switch operating modes based on the comparison between the parameters of the relevant temperature and pressure sensors and the set values, achieving automatic control. The carbon dioxide in the carbon dioxide tank 19 is obtained by capturing and stripping off the tail gas from a coal-fired power plant.

[0031] The low-temperature carbon dioxide hydrate slurry in the hydrate generation tank 1 is pressurized by the hydrate slurry pump 2 and then partially heats the high-temperature water produced by the hydrate decomposition in the regenerator 4. It then enters the hydrate decomposition tank 5, where it is indirectly heated by high-temperature seawater flowing in the heat exchange pipes, decomposing into high-pressure carbon dioxide gas and high-temperature water. The high-temperature water enters the regenerator, transferring some heat to the hydrate slurry, and then returns to the hydrate generation tank 1. The high-pressure carbon dioxide gas enters the expander 16, expands, and drives the generator 14 to generate electricity. The electricity generated by the generator 14 is stabilized by the voltage regulator 15 and can be used by the load or connected to the grid. The carbon dioxide gas discharged from the expander returns to the hydrate generation tank 1 after passing through the buffer tank 17 to absorb pressure fluctuations in the pipeline.

[0032] The air cooler 13 is an air conditioning surface cooler structure, placed inside the air-conditioned room. The pipes contain flowing deep seawater. Air in the room awaiting cooling passes over the surface of the air cooler's pipes via forced ventilation for convective heat exchange, transferring heat to the deep seawater inside the pipes. The cool air output from the air cooler is then delivered into the air-conditioned room through the air supply duct, achieving the air conditioning cooling effect. The third temperature sensor 32 is located in the working area of ​​the air-conditioned room.

[0033] The photovoltaic panel water cooling device 11 is placed on the roof of the building. By attaching an insulation layer with cooling pipes to the back of the photovoltaic panel, the pipes contain flowing deep seawater, which can absorb and carry away the photovoltaic heat generated by the photovoltaic module when generating electricity, thereby achieving the effect of cooling the photovoltaic panel and improving the photoelectric conversion efficiency of the photovoltaic module.

[0034] Both the hydrate formation tank and the hydrate decomposition tank are pressurized metal containers. The hydrate formation tank has a pressure-resistant viewing window at the top for easy observation of hydrate formation. The water inlet of the hydrate formation tank is designed above the gas inlet, and the water outlets are evenly distributed below the upper water pipe inside the tank. This promotes uniform mixing of carbon dioxide and water within the hydrate formation tank. Simultaneously, a solution pump can quantitatively pump the accelerator solution from the storage tank into the hydrate formation tank, thereby accelerating the hydrate formation rate and better matching the hydrate formation and decomposition processes. Example 2

[0035] The difference between this embodiment and embodiment 1 is that, in addition to the above four subsystems, this system also includes a wave energy power generation device 8. The wave energy power generation device 8 is arranged in a floating form on the nearshore sea surface. The electricity generated by the wave energy power generation device 8 is used by the hydrate slurry pump 2, the first seawater pump 3, the second seawater pump 7 and the solution pump 25. The surplus electricity is transmitted to the power grid, thereby making full use of ocean energy and improving the overall power generation efficiency of the system. Example 3

[0036] The present invention also includes a method for energy storage and power generation using carbon dioxide hydrate from ocean energy. This method utilizes the formation, decomposition, and expansion characteristics of carbon dioxide hydrate. Since the formation process of hydrate is an exothermic reaction, heat is discharged to a cold source (deep seawater) to generate carbon dioxide hydrate. Since the decomposition process of hydrate is an endothermic reaction, heat is absorbed from a heat source (deep seawater or surface seawater that has absorbed heat from indoor air and waste heat from photovoltaic panels) to decompose carbon dioxide hydrate. The high-pressure carbon dioxide gas obtained from the decomposition is used to drive an expander to generate electricity. In the process of power generation, the coldness of deep seawater is utilized in a cascade manner.

[0037] The method for generating energy using the energy storage power generation system in Example 1 includes the following two operating modes: a. Energy storage mode: In this state, the first interlock valve 9 is open, the second interlock valve 10 is closed, the third interlock valve 26 is open, the fourth interlock valve 27 is closed, the first switch valve 18 and the second switch valve 20 are closed, and the hydrate slurry pump 2 and the second seawater pump 7 are closed. The specific steps are as follows: Start the solution pump 25 to pump the designed concentration of accelerator solution from the accelerator solution tank into the hydrate generation tank 1; The first seawater pump 3 is started and adjusted to high speed, so that the extracted deep seawater flows rapidly in the heat exchange pipeline in the hydrate generation tank 1. When the reading returned by the first temperature sensor 29 stabilizes in the target low temperature range for hydrate generation, the first seawater pump 3 is adjusted to medium speed. The extracted deep seawater flows through the first heat exchange pipeline of the hydrate generation tank 1, the pipeline of the air cooler 13, and the pipeline of the photovoltaic panel water cooling device 11 before being discharged into the deep seawater collection tank for subsequent use in aquaculture, agriculture and food development, medical and beauty applications. The third switch valve 22 is opened, and the opening of the pressure control valve is adjusted by comparing the reading returned by the first pressure sensor 28 with the target pressure range for hydrate formation. This controls the carbon dioxide entering the hydrate formation tank 1 from the carbon dioxide tank 19, ensuring that the tank reaches the pressure conditions for hydrate formation and begins to generate hydrate. The hydrate formation process continues through the replenishment and pressure stabilization of the carbon dioxide tank 19, the pumping of the accelerator solution tank 24, and the flow and heat exchange of deep seawater in the first heat exchange pipeline within the hydrate formation tank 1. The generated hydrate is stored in the hydrate formation tank, which is used as a hydrate storage tank. The electromagnetic heat meter 33 detects the cumulative heat exchange in the first heat exchange pipeline. When the amount of hydrate generated in the hydrate formation tank reaches the required amount for cold storage, the third switch valve 22, the solution pump 25, and the first seawater pump 3 are closed, gradually stopping the hydrate formation. When the user needs cooling, the hydrate slurry pump 2 is turned on, and the stored hydrate slurry is transported to the user for cooling via pipeline for release. b. Power generation mode: In this state, the third interlock valve 26 is closed, the fourth interlock valve 27 is open, the first interlock valve 9 is closed, the second interlock valve 10 is open, the second seawater pump 7 is closed, and the air cooler 13 and the photovoltaic panel water cooling device 11 are in operation. That is, the air in the room that needs to be cooled passes over the surface of the air cooler pipes in the form of forced ventilation for convective heat exchange, and the photovoltaic panel receives sufficient sunlight and performs photoelectric conversion. The specific steps are as follows: Start the solution pump 25 to pump the designed accelerator solution from the accelerator solution tank into the hydrate generation tank 1, and then turn off the solution pump 25 (the amount of accelerator solution pumped in is configured according to the rated output power to be achieved by the power plant, which is existing technology and will not be elaborated on here). Start the first seawater pump 3 and adjust it to high speed so that the deep seawater extracted flows rapidly in the first heat exchange pipeline in the hydrate generation tank 1. When the reading returned by the first temperature sensor 29 stabilizes in the target low temperature range for hydrate generation, the first seawater pump 3 is adjusted to medium speed. At this time, the temperature in the air-conditioned room is adjusted by regulating the opening of the bypass regulating valve 12 and controlling the flow rate of deep seawater into the air cooler 13 pipeline, thereby achieving the supply of cooling capacity in the air-conditioned room. Specifically: when the reading of the third temperature sensor 32 is lower than the set cooling target temperature by 3°C, the opening of the bypass regulating valve is increased to reduce the flow rate of deep seawater through the air cooler, thereby reducing the heat carried away from the indoor air. When it is higher than the cooling target temperature, the opening of the bypass regulating valve is decreased, and the cycle continues. Deep seawater flows sequentially through the first heat exchange pipeline of hydrate generation tank 1, the pipeline of air cooler 13, the pipeline of photovoltaic panel water cooling device 11, and the second heat exchange pipeline of hydrate decomposition tank 5 before being discharged into the ocean. The seawater preheats the hydrate decomposition tank 5 through the second heat exchange pipeline of the hydrate decomposition tank 5.

[0038] The third switch valve 22 is opened, and the opening of the pressure control valve 21 is adjusted by comparing the reading returned by the first pressure sensor 28 with the target pressure range for hydrate formation. This controls the carbon dioxide entering the hydrate formation tank 1 from the carbon dioxide gas tank 19, so that the pressure conditions for hydrate formation are met in the tank, and carbon dioxide hydrate formation begins.

[0039] Electromagnetic heat meter 33 detects the cumulative heat exchange in the first heat exchange pipeline. When the amount of hydrate generated in the hydrate generation tank meets the power generation requirements, the hydrate slurry pump 2 is turned on to pressurize the generated hydrate slurry and send it to the hydrate decomposition tank 5 through the regenerator 4. After the hydrate slurry enters the hydrate decomposition tank 5, since the hydrate decomposition tank 5 has been preheated, it can quickly reach the high temperature decomposition conditions of the hydrate, so that the hydrate slurry sent into the hydrate decomposition tank decomposes into high-pressure carbon dioxide gas and high-temperature water.

[0040] When the reading returned by the second pressure sensor 30 on the hydrate decomposition tank 5 stabilizes within the target pressure range for hydrate decomposition power generation, the second switch valve 20 and the first switch valve 18 are opened. The high-pressure carbon dioxide gas separated from the hydrate enters the expander 16 to expand and do work to drive the generator to generate electricity, which is then output through the voltage regulator for use by the building load or grid connection. The carbon dioxide gas after doing work passes through the buffer tank 13 and enters the tank through the air inlet below the side of the hydrate generation tank 1 to complete the circulation. The high-temperature water separated from the hydrate enters the hot side of the regenerator 4 to preheat the hydrate slurry on the cold side of the regenerator 4. Then, it enters the tank through the water inlet above the side of the hydrate generation tank 1 and is sprayed onto the surface of the heat exchange pipeline through the water outlets evenly arranged above the tank to complete the circulation.

[0041] After the power output of the power generation system gradually stabilizes, the pressure control valve 21 and the third switch valve 22 are closed to complete the charging of carbon dioxide gas. At this time, the power generation process completes one cycle.

[0042] When the power generation mode is running, if there is insufficient sunlight or no cooling demand in the air-conditioned room, and the reading of the second temperature sensor 31 on the hydrate decomposition tank 5 is lower than the target temperature range for hydrate decomposition, the second interlock valve 10 is closed, the first interlock valve 9 is opened, the second seawater pump 7 is turned on, and the first seawater pump 3 is adjusted to low speed. The second seawater pump 7 pumps surface seawater into the second heat exchange pipeline of the hydrate decomposition tank 5 to realize the decomposition of hydrates in the hydrate decomposition tank 5.

[0043] At this time, the air cooler 13 or the photovoltaic panel water cooling device 11 is in an undersaturated working state, that is, the flow rate of the air cooler 13 is completely bypassed, and the photovoltaic panel receives insufficient sunlight. The deep seawater flows through the first heat exchange pipeline of the hydrate generation tank 1, the pipeline of the air cooler 13, and the pipeline of the photovoltaic panel water cooling device 11 before being discharged into the deep seawater collection tank.

[0044] When there is ample sunlight and the air-conditioned rooms require cooling, the system operates in power generation mode. The expander drives the generator to output electricity to supply the building load, while the air cooler outputs cold air, achieving combined cooling and power generation. This saves on the cost of the building's air conditioning system and improves the power generation efficiency of the photovoltaic panels.

[0045] When the cooling demand of the air-conditioned room changes, the flow rate of deep seawater entering the air cooler can be controlled by adjusting the opening of the bypass control valve, thereby regulating the cooling capacity output to the indoor air. After being extracted by the first seawater pump, the deep seawater is released in sequence through the heat exchange pipeline of the hydrate generation tank, the air cooler pipeline, and the photovoltaic panel water cooling device pipeline, thus utilizing the cooling capacity in a cascade manner. Subsequently, the deep seawater enters the heat exchange pipeline of the hydrate decomposition tank for heat exchange, using the waste heat recovered from the indoor air and photovoltaic panels for hydrate decomposition, saving the pumping power required to extract surface seawater.

[0046] When there is insufficient sunlight or no need for cooling in the air-conditioned room, the heat provided by the photovoltaic panels and air coolers is insufficient to raise the temperature of the deep seawater enough to decompose the hydrates in the hydrate decomposition tank. At this time, the second seawater pump draws warm surface seawater into the heat exchange pipeline of the hydrate decomposition tank, while the speed of the first seawater pump is reduced, and the deep seawater is discharged into the deep seawater collection tank by controlling the interlock valve. It can then be used for subsequent aquaculture, agricultural and food development, medical and cosmetic purposes.

[0047] The above are merely preferred embodiments of the present invention and do not limit the patent scope of the present invention. Any equivalent structural transformations made under the concept of the present invention using the description and drawings of the present invention, or direct / indirect applications in other related technical fields, are included within the patent protection scope of the present invention.

Claims

1. A carbon dioxide hydrate energy storage and power generation system utilizing ocean energy, characterized in that: This includes a hydrate generation and energy storage system that utilizes the cold energy of deep seawater to generate carbon dioxide hydrates, a hydrate decomposition system that decomposes the generated carbon dioxide hydrates, a deep seawater cascade utilization system that further utilizes the cold energy of deep seawater discharged from the hydrate generation and energy storage system, and a power generation system that uses the high-pressure carbon dioxide gas decomposed within the hydrate decomposition system to generate electricity. The outlet of the hydrate generation energy storage system is connected to the hydrate decomposition system and the cold energy user end through pipelines. The gas outlet of the hydrate decomposition system is connected to the air inlet of the power generation system through pipelines. The liquid outlet of the hydrate decomposition system flows back to the hydrate generation energy storage system through pipelines. The air outlet of the power generation system is connected to the inlet of the hydrate generation energy storage system through pipelines. The inlet of the heat exchange pipeline in the hydrate generation energy storage system is pumped by the first seawater pump (3) to extract deep seawater. The outlet is connected to the inlet of the deep seawater cascade utilization system through pipelines. The outlet of the deep seawater cascade utilization system is connected to the inlet of the heat exchange pipeline in the hydrate decomposition system through pipelines. The outlet of the heat exchange pipeline of the hydrate decomposition system is directly discharged into the ocean. The hydrate generation and energy storage system includes a hydrate generation tank (1), the hydrate decomposition system includes a hydrate decomposition tank (5), the deep seawater cascade utilization system includes an air conditioning system, a photovoltaic thermal system and a deep seawater collection tank (23), the air conditioning system includes an air cooler (13), the photovoltaic thermal system includes a photovoltaic panel water cooling device (11), and the power generation system includes an expander (16) and a buffer tank (17). The hydrate generating tank (1) is equipped with a first temperature sensor (29) for detecting the temperature inside the tank and a first pressure sensor (28) for detecting the pressure inside the tank. The hydrate generating tank (1) is equipped with a first heat exchange pipeline. An electromagnetic heat meter (33) for monitoring the cumulative heat exchange of the first heat exchange pipeline is installed between the inlet and outlet pipes of the first heat exchange pipeline. The hydrate generating tank (1) has a hydrate outlet in the middle of one side, a water inlet in the upper part of the other side, a gas inlet in the middle part, and a gas inlet in the lower part. The hydrate decomposition tank (5) is equipped with a second temperature sensor (31) for detecting the temperature inside the tank and a second pressure sensor (30) for detecting the pressure inside the tank. A second heat exchange pipeline is installed inside the hydrate decomposition tank (5). The hydrate decomposition tank (5) has a hydrate inlet in the middle of one side and a water outlet in the lower part of the other side. A gas outlet is installed at the top of the hydrate decomposition tank (5). The hydrate outlet of the hydrate generation tank (1) is connected to the inlet of the hydrate slurry pump (2) via a pipeline. The outlet of the hydrate slurry pump (2) is connected to the inlet of the first three-way pipe. One outlet of the first three-way pipe is connected to the inlet of the third interlock valve (26) via a pipeline, and the other outlet is connected to the inlet of the fourth interlock valve (27) via a pipeline. The outlet of the third interlock valve (26) is connected to the cold energy user end via a pipeline. The outlet of the fourth interlock valve (27) is connected to the cold side inlet of the regenerator (4) via a pipeline. The cold side outlet of the regenerator (4) is connected to the hydrate inlet of the hydrate decomposition tank (5) via a pipeline. The water outlet of the hydrate decomposition tank (5) is connected to the regenerator via a pipeline. The heat inlet of the regenerator (4) is connected to the heat side inlet, and the heat outlet of the regenerator (4) is connected to the water inlet of the hydrate generation tank (1) through the first switch valve (18). The gas outlet of the hydrate decomposition tank (5) is connected to the high pressure inlet of the expander (16) through a pipeline. The low pressure outlet of the expander (16) is connected to the inlet of the buffer tank (17). The outlet of the buffer tank (17) is connected to the gas inlet of the hydrate generation tank (1) through the second switch valve (20). The outlet of the carbon dioxide tank (19) is connected to the inlet of the pressure control valve (21) through a pipeline. The outlet of the pressure control valve (21) is connected to the make-up gas inlet of the hydrate generation tank (1) through the third switch valve (22). The inlet of the first heat exchange pipeline is connected to the outlet of the first seawater pump (3). The inlet of the first seawater pump (3) is connected to the deep seawater intake pipe via a pipeline. The outlet of the first heat exchange pipeline is connected to the inlet of the air cooler (13). The outlet of the air cooler (13) is connected to the inlet of the photovoltaic panel water cooling device (11). The outlet of the photovoltaic panel water cooling device (11) is connected to the outlet of the second three-way pipe. One outlet of the second three-way pipe is connected to the inlet of the first interlock valve (9), and the other outlet is connected to the inlet of the second interlock valve (10). The first interlock valve (9) The outlet of the third three-way pipe is connected to the inlet of the deep seawater collection tank (23). The outlet of the second interlock valve (10) is connected to the inlet of the third three-way pipe through a pipeline. The other inlet of the third three-way pipe is connected to the outlet of the check valve (6) through a pipeline. The inlet of the check valve (6) is connected to the outlet of the second seawater pump (7) through a pipeline. The inlet of the second seawater pump (7) is connected to the surface seawater intake pipe through a pipeline. The outlet of the third three-way pipe is connected to the inlet of the second heat exchange pipeline. The outlet of the second heat exchange pipeline is connected to the drain pipe. The outlet of the drain pipe is located away from the deep seawater and surface seawater intake points. The first interlock valve (9) and the second interlock valve (10) are mechanically interlocked. The mechanical interlock causes one of the first interlock valve (9) and the second interlock valve (10) to open, while the other valve is closed. The third interlock valve and the fourth interlock valve (27) are mechanically interlocked. The mechanical interlock causes one of the third interlock valve and the fourth interlock valve (27) to open, while the other valve is closed.

2. The carbon dioxide hydrate energy storage and power generation system utilizing ocean energy according to claim 1, characterized in that: It also includes an accelerator solution tank (24), the top of the hydrate generation tank (1) is provided with an accelerator solution inlet, the outlet of the accelerator solution tank (24) is connected to the inlet of the solution pump (25) through a pipeline, and the outlet of the solution pump (25) is connected to the accelerator solution inlet of the hydrate generation tank (1) through a pipeline.

3. The carbon dioxide hydrate energy storage and power generation system utilizing ocean energy according to claim 1, characterized in that: Both the first and second heat exchange pipelines are coiled heat exchange pipelines.

4. The carbon dioxide hydrate energy storage and power generation system utilizing ocean energy according to claim 1, characterized in that: The air cooler (13) has its outlet and inlet pipes connected by a connecting pipe, on which a bypass regulating valve (12) is installed.

5. The carbon dioxide hydrate energy storage and power generation system utilizing ocean energy according to claim 1, characterized in that: The air cooler (13) is placed in the air-conditioned room, and a third temperature sensor (32) is also installed in the air-conditioned room. The photovoltaic panel water cooling device (11) of the photovoltaic thermal system is placed on the roof of the building.

6. A method for generating electricity using carbon dioxide hydrates from ocean energy storage, characterized in that: Controlled using the energy storage power generation system described in claim 5. It includes the following two working modes, a. Energy storage mode: In this state, open the first interlock valve (9) and the third interlock valve (26), close the second interlock valve (10), the fourth interlock valve (27), the first switch valve (18), and the second switch valve (20), and shut down the hydrate slurry pump (2) and the second seawater pump (7). Start the solution pump (25) and the first seawater pump (3). When the reading returned by the first temperature sensor (29) is stable in the target low temperature range for hydrate formation, open the third switch valve (22). The pressure control valve (21) controls the carbon dioxide in the carbon dioxide tank (19) to enter the hydrate formation tank (1). Hydrate begins to form in the hydrate formation tank (1). At the same time, the electromagnetic heat meter detects the cumulative heat exchange in the first heat exchange pipeline. When the amount of hydrate formed in the hydrate formation tank reaches the requirement for cold storage, close the third switch valve, the solution pump and the first seawater pump to gradually stop the formation of hydrate. When the user needs to use cold, turn on the hydrate slurry pump (2) and transport the stored hydrate slurry to the cold user end through the pipeline for cold release. b. Power generation mode: In this state, the third interlock valve (26) and the first interlock valve (9) are closed, the fourth interlock valve (27) and the second interlock valve (10) are opened, the second seawater pump (7) is shut down, and the air cooler (13) and the photovoltaic panel water cooling device (11) are in operation. Start the solution pump (25) and the first seawater pump (3). The deep seawater flows through the first heat exchange pipeline, the air cooler (13), the photovoltaic panel water cooling device (11) and the second heat exchange pipeline of the hydrate decomposition tank (5) in sequence before being discharged into the ocean. The seawater preheats the hydrate decomposition tank (5) through the second heat exchange pipeline. When the reading returned by the first temperature sensor (29) stabilizes in the target low temperature range for hydrate formation, the third switch valve (22) is opened, and the pressure control valve (21) controls the carbon dioxide in the carbon dioxide gas tank (19) to enter the hydrate formation tank (1). Carbon dioxide hydrate begins to be generated in the hydrate formation tank (1). The electromagnetic heat meter (33) detects the cumulative heat exchange in the first heat exchange pipeline. When the amount of hydrate generated in the hydrate formation tank meets the power generation requirements, the hydrate slurry pump (2) is turned on to pressurize the generated carbon dioxide hydrate and send it to the hydrate decomposition tank (5) through the regenerator (4). The carbon dioxide hydrate enters the hydrate decomposition tank (5) and decomposes into high-pressure carbon dioxide gas and high-temperature water. When the reading returned by the second pressure sensor (30) on the hydrate decomposition tank (5) stabilizes within the target pressure range for power generation, the second switch valve (20) and the first switch valve (18) are opened. The high-pressure carbon dioxide gas separated from the carbon dioxide hydrate enters the expander (16) to expand and do work to drive the generator (14) to generate electricity, which is then output through the voltage regulator (15). The carbon dioxide gas after doing work passes through the buffer tank (17) and is then sent back to the hydrate generation tank (1) through the pipeline. At the same time, the high-temperature water separated from the carbon dioxide hydrate enters the hot side of the regenerator (4) to preheat the hydrate slurry on the cold side of the regenerator (4), and is then sent back to the hydrate generation tank (1) through the pipeline. This cycle continues. After the power output of the power generation system gradually stabilizes, close the pressure control valve (21) and the third switch valve (22).

7. The method for generating electricity using carbon dioxide hydrate from ocean energy according to claim 6, characterized in that: When the power generation mode is running, if the reading of the second temperature sensor (31) on the hydrate decomposition tank (5) is lower than the target temperature range for hydrate decomposition, the second interlock valve (10) is closed, the first interlock valve (9) is opened, and the second seawater pump (7) is turned on. The second seawater pump (7) pumps surface seawater into the second heat exchange pipeline of the hydrate decomposition tank (5).

8. The method for generating electricity using carbon dioxide hydrate from ocean energy according to claim 6, characterized in that: The electromagnetic heat meter (33) measures the inlet temperature, outlet temperature and outlet flow rate of the first heat exchange pipeline in real time, and calculates the heat exchange of the first heat exchange pipeline according to the preset thermodynamic calculation formula. Based on the cumulative and instantaneous heat exchange of the first heat exchange pipeline and the latent heat of phase change of the hydrate, the mass and generation rate of the generated hydrate are obtained.

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