CN116658370A - Hydrogen-heat-power cogeneration liquid carbon dioxide energy storage system - Google Patents

Abstract

The invention relates to a liquid carbon dioxide energy storage system for combined hydrogen, heat and electricity generation. The liquid carbon dioxide energy storage system for hydrogen, heat and electricity combined generation includes: a renewable energy power generation device, an energy storage module and a hydrogen production module. The energy storage module includes a molten salt energy storage circuit, a liquid carbon dioxide energy storage circuit, a first heat exchanger and a second heat exchanger, and the hydrogen production module includes a heat transfer oil circuit and a methanol hydrogen production circuit. The renewable energy power generation device is connected to the molten salt energy storage circuit, the hot side of the first heat exchanger is connected to the molten salt energy storage circuit, the cold side of the first heat exchanger is connected to the liquid carbon dioxide energy storage circuit, and the second heat exchanger The hot side of the second heat exchanger is connected to the liquid carbon dioxide energy storage circuit, the cold side of the second heat exchanger is connected to the heat transfer oil circuit, and the heat transfer oil circuit is connected to the methanol hydrogen production circuit reactor and vaporizer. The invention utilizes the heat contained in the exhaust gas of the turbine in the energy release stage of the energy storage system to provide energy for the methanol reforming hydrogen production process, and has the advantages of low hydrogen production cost and high energy utilization rate.

Description

A liquid carbon dioxide energy storage system for combined hydrogen, heat and power generation

technical field

The invention relates to the technical field of energy storage, in particular to a liquid carbon dioxide energy storage system for combined hydrogen, heat and electricity generation.

Background technique

In response to the depletion of fossil fuels and the severe challenges brought about by the environmental problems caused by the combustion of fossil fuels, my country has vigorously developed renewable energy and continuously increased the installed capacity of renewable energy such as wind power and solar energy. However, due to the volatility and intermittent characteristics of renewable energy, its large-scale grid connection will have a great impact on the grid, threatening the stability and security of the grid. The energy storage system can achieve "peak shaving and valley filling", balance the power demand on the power generation side and the load side of the grid, reduce the impact of renewable energy on the grid, and maintain the security of the grid.

Compressed gas-liquid energy storage has great development prospects without being limited by geographical factors. The carbon dioxide working medium has a high density when it is in operation, and the components of the circulation system using carbon dioxide as the working medium are small in size, compact in structure, and low in system cost. Moreover, the temperature of liquid carbon dioxide is relatively high, and it is easier to realize liquid storage by using carbon dioxide as the working medium of the energy storage system, and the energy storage density is higher. Compared with the traditional energy storage system that uses a compressor to compress the working medium, the use of a pump to increase the pressure of the working medium can greatly reduce the compression work and improve the efficiency of the energy storage system.

Hydrogen energy is one of the important clean energy sources, and there are more and more researches on hydrogen production and utilization worldwide. Hydrogen is a clean and efficient fuel with an energy density 2.68 times that of gasoline, and water is the only product of its combustion. It is considered to be one of the most potential alternatives to fossil fuels. Under the general environment of energy conservation and emission reduction, hydrogen energy has become the most potential alternative energy in this century by virtue of its advantages of high efficiency and cleanliness. Hydrogen production technology directly affects the cost of hydrogen energy and the development of hydrogen energy. Methanol is the most potential source of hydrogen in reforming reactions. It has the advantages of simple structure, easy transportation, easy acquisition, low reforming reaction temperature, and high hydrogen content in reformed products. advantage.

The working fluid at the outlet of the turbine still has a lot of heat during the energy release stage of the liquid carbon dioxide energy storage system, and hydrogen production by methanol reforming is a strong endothermic reaction. The liquid carbon dioxide energy storage system is coupled with the methanol reforming hydrogen production system to utilize the energy storage system The heat contained in the turbine outlet working fluid in the energy release stage provides energy for the methanol reforming hydrogen production system, which can not only make the energy of the energy storage system be used reasonably, improve the operation efficiency of the energy storage system, but also reduce the operating cost of the methanol reforming hydrogen production system. However, in the related art, there is no structure that combines a liquid carbon dioxide energy storage system with methanol reforming to produce hydrogen.

Contents of the invention

The present invention aims to solve one of the technical problems in the related art at least to a certain extent.

For this reason, the embodiments of the present invention propose a liquid carbon dioxide energy storage system for combined hydrogen, heat and power generation, which has the advantages of low hydrogen production cost and high energy utilization rate.

A liquid carbon dioxide energy storage system for combined hydrogen, heat and power generation in an embodiment of the present invention includes: a renewable energy power generation device, an energy storage module, and a hydrogen production module; the energy storage module includes a molten salt energy storage circuit, a liquid carbon dioxide energy storage circuit, a first heat exchanger and a second heat exchanger, the renewable energy power generation device is connected to the molten salt energy storage circuit, and the hot side of the first heat exchanger is connected to the molten salt energy storage circuit , the cold side of the first heat exchanger is connected to the liquid carbon dioxide energy storage circuit, and the hot side of the second heat exchanger is connected to the liquid carbon dioxide energy storage circuit; the hydrogen production module includes a heat transfer oil circuit And methanol hydrogen production circuit, the methanol hydrogen production circuit includes a reactor and a gasifier, the heat transfer oil circuit and the cold side of the second heat exchanger, the tube side of the reactor and the gasifier connected to the hot side.

According to a liquid carbon dioxide energy storage system for combined hydrogen, heat and power generation in an embodiment of the present invention, when the grid load demand is low, the electric energy generated by the renewable energy power generation device cannot be connected to the grid, and the system is in the energy storage stage. The energy storage circuit stores electrical energy in the form of heat energy, and stores the electrical energy in the form of pressure energy through the liquid carbon dioxide energy storage circuit. When the grid load is high and the system is in the energy release stage, the energy stored in the energy storage stage is converted into electrical energy and supplied to the grid. At the same time, the heat transfer oil circuit can transfer the heat contained in the turbine exhaust to the heat transfer oil through the second heat exchanger. In the heat storage medium, and through the gasifier and reactor, it provides energy for the gasification of methanol raw material liquid and the hydrogen production reaction of methanol reforming. Therefore, a liquid carbon dioxide energy storage system for combined hydrogen, heat and power generation in the embodiment of the present invention can use heat transfer oil to absorb and store the heat energy of the carbon dioxide working fluid at the outlet of the turbine in the energy release stage, so as to vaporize the methanol raw material liquid and feed it to the reaction The device provides heat to maintain the progress of the methanol reforming hydrogen production reaction, so that the heat of the carbon dioxide working medium can be used reasonably and scientifically, realizing the cascade utilization of energy, and at the same time greatly reducing the production cost of hydrogen and reducing the environmental impact of the hydrogen production process Influence.

In some embodiments, the liquid carbon dioxide circuit includes a turbine, a regenerator, a condenser, a low-pressure carbon dioxide liquid storage tank, a carbon dioxide working fluid pump, a first cooler, and a high-pressure carbon dioxide liquid storage tank, and the low-pressure carbon dioxide liquid storage tank The outlet of the tank is connected to the inlet of the carbon dioxide working medium pump, the outlet of the carbon dioxide working medium pump is connected to the hot side inlet of the first cooler, and the hot side outlet of the first cooler is connected to the high pressure carbon dioxide storage liquid The tank inlet is connected, the outlet of the high-pressure carbon dioxide liquid storage tank is connected with the cold side inlet of the regenerator, the cold side outlet of the regenerator is connected with the cold side inlet of the first heat exchanger, and the second The outlet of the cold side of a heat exchanger is connected with the inlet of the turbine, the outlet of the turbine is connected with the inlet of the hot side of the second heat exchanger, and the outlet of the hot side of the second heat exchanger is connected with the inlet of the turbine. The hot side inlet of the regenerator is connected, the hot side outlet of the regenerator is connected with the inlet of the condenser, and the outlet of the condenser is connected with the inlet of the low-pressure carbon dioxide liquid storage tank.

In some embodiments, the carbon dioxide working medium pump is connected to the renewable energy generating device, and the renewable energy generating device can supply power to the carbon dioxide working medium pump; and/or, the renewable energy generating device for wind farms.

In some embodiments, the molten salt energy storage circuit includes an electric heating boiler, a high temperature molten salt storage tank and a low temperature molten salt storage tank, the renewable energy power generation device is used to supply power to the electric heating boiler, and the low temperature The outlet of the molten salt storage tank is connected to the inlet of the electric heating boiler, the outlet of the electric heating boiler is connected to the inlet of the high temperature molten salt storage tank, the outlet of the high temperature molten salt storage tank is connected to the first The inlet on the hot side of the heater is connected, and the outlet on the hot side of the first heat exchanger is connected to the inlet of the low-temperature molten salt storage tank.

In some embodiments, the heat transfer oil circuit includes a high temperature heat transfer oil storage tank, a heat transfer oil pump and a low temperature heat transfer oil storage tank, the outlet of the high temperature heat transfer oil storage tank is connected to the inlet of the heat transfer oil pump, and the heat transfer oil pump The outlet is connected to the tube-side inlet of the reactor, the tube-side outlet of the reactor is connected to the hot-side inlet of the gasifier, and the hot-side outlet of the gasifier is connected to the low-temperature heat transfer oil storage tank. The inlet is connected, the outlet of the low-temperature heat-conducting oil storage tank is connected with the cold-side inlet of the second heat exchanger, and the cold-side outlet of the second heat exchanger is connected with the inlet of the high-temperature heat-conducting oil tank.

In some embodiments, the methanol-to-hydrogen loop further includes: a feeding device, a preheater, a second cooler, a gas-liquid separator, a pressure swing adsorber, and a hydrogen storage tank, and the feeding device is used to supply Methanol raw material, the feed device is connected to the cold side inlet of the preheater, the cold side outlet of the preheater is connected to the cold side inlet of the gasifier, and the cold side outlet of the gasifier Connected to the shell side inlet of the reactor, the shell side outlet of the reactor is connected to the hot side inlet of the preheater, and the hot side outlet of the preheater is connected to the hot side of the second cooler The inlet is connected, the hot side outlet of the second cooler is connected with the inlet of the gas-liquid separator, the gas-side outlet of the gas-liquid separator is connected with the inlet of the pressure swing adsorber, and the pressure swing adsorption The outlet of the device is connected with the inlet of the hydrogen storage tank.

In some embodiments, the feeding device includes a desalted water storage tank, a methanol storage tank and a methanol raw material liquid pump, the desalted water storage tank is used for storing desalted water, the methanol storage tank is used for storing methanol, the The water in the desalted water storage tank is mixed with the methanol in the methanol storage tank according to a certain ratio, and then enters the methanol raw material liquid pump, and the outlet of the methanol raw material liquid pump is connected with the cold side inlet of the preheater.

In some embodiments, the liquid-side outlet of the gas-liquid separator is connected to the inlet of the methanol raw material liquid pump, and the liquid substances separated by the liquid-side outlet of the gas-liquid separator can be passed into the inlet of the methanol raw material liquid pump .

In some embodiments, at least one of the condenser, the first cooler and the second cooler is connected to a domestic hot water circuit.

In some embodiments, the shell side of the reactor is filled with a catalyst required for the methanol reforming hydrogen production reaction.

Description of drawings

Fig. 1 is a schematic diagram of a liquid carbon dioxide energy storage system for combined hydrogen, heat and power generation according to an embodiment of the present invention.

Reference signs:

1. Wind farm; 2. Electric heating boiler; 3. High temperature molten salt storage tank; 4. Low temperature molten salt storage tank; 5. First heat exchanger; 6. Turbine; 7. Second heat exchanger; 8. Regenerator; 9. Condenser; 10. Low-pressure carbon dioxide liquid storage tank; 11. Carbon dioxide working medium pump; 12. First cooler; 13. High-pressure carbon dioxide liquid storage tank; 14. High-temperature heat transfer oil storage tank; 15. Heat conduction Oil pump; 16. Reactor; 17. Vaporizer; 18. Low temperature heat transfer oil storage tank; 19. Desalted water storage tank; 20. Methanol storage tank; 21. Methanol raw material liquid pump; 22. Preheater; 23. The first Two coolers; 24. Gas-liquid separator; 25. Pressure swing adsorber; 26. Hydrogen storage tank.

Detailed ways

Embodiments of the invention are described in detail below, examples of which are illustrated in the accompanying drawings. The embodiments described below by referring to the figures are exemplary and are intended to explain the present invention and should not be construed as limiting the present invention.

A liquid carbon dioxide energy storage system for combined hydrogen, heat and power generation according to an embodiment of the present invention will be described below with reference to FIG. 1 .

As shown in FIG. 1 , a liquid carbon dioxide energy storage system for combined hydrogen, heat and power generation according to an embodiment of the present invention includes: a renewable energy power generation device, an energy storage module, and a hydrogen production module. The energy storage module includes a molten salt energy storage circuit, a liquid carbon dioxide energy storage circuit, a first heat exchanger 5 and a second heat exchanger 7, the renewable energy power generation device is connected to the molten salt energy storage circuit, and the first heat exchanger 5 The hot side is connected to the molten salt energy storage circuit, the cold side of the first heat exchanger 5 is connected to the liquid carbon dioxide energy storage circuit, and the hot side of the second heat exchanger 7 is connected to the liquid carbon dioxide energy storage circuit. The hydrogen production module includes a heat transfer oil circuit and a methanol hydrogen production circuit, the methanol hydrogen production circuit includes a reactor 16 and a gasifier 17, the heat transfer oil circuit and the cold side of the second heat exchanger 7, the tube side of the reactor 16 and the gasifier The hot side of 17 is connected.

According to a liquid carbon dioxide energy storage system for combined hydrogen, heat and power generation in an embodiment of the present invention, when the grid load demand is low, the electric energy generated by the renewable energy power generation device cannot be connected to the grid, and the system is in the energy storage stage. The energy storage circuit stores electrical energy in the form of heat energy, and stores the electrical energy in the form of pressure energy through the liquid carbon dioxide energy storage circuit.

When the grid load is high and the system is in the energy release stage, the energy stored in the energy storage stage is converted into electrical energy and supplied to the grid. At this stage, the heat transfer oil circuit can absorb the heat energy released by the liquid carbon dioxide energy storage circuit through the second heat exchanger 7 , it can be understood that the heat transfer oil circuit can transfer the heat contained in the exhaust gas of the turbine 6 to the heat transfer oil heat storage medium through the second heat exchanger 7, and use the gasifier 17 and the reactor 16 as the gasified methanol raw material Liquid and methanol reforming hydrogen production reaction to provide energy. Therefore, a liquid carbon dioxide energy storage system for combined hydrogen, heat and power generation in the embodiment of the present invention can use the heat transfer oil to absorb and store the heat energy of the carbon dioxide working fluid at the outlet of the turbine 6 in the energy release stage, so as to vaporize the methanol raw material liquid and transfer it to The reactor 16 provides heat to maintain the progress of the methanol reforming hydrogen production reaction, so that the heat of the carbon dioxide working medium can be used reasonably and scientifically, and the cascade utilization of energy is realized. At the same time, the production cost of hydrogen is greatly reduced, and the impact of the hydrogen production process is reduced. environmental impact.

On the other hand, a liquid carbon dioxide energy storage system for combined hydrogen, heat and power generation in the embodiment of the present invention can store the electric energy that cannot be used by the power grid as thermal energy or other forms of energy, and convert the stored energy into electrical energy. Moreover, a liquid carbon dioxide energy storage system for combined hydrogen, heat and power generation in the embodiment of the present invention uses carbon dioxide as the working medium of the energy storage system. Compared with other commonly used gases, carbon dioxide has a higher density, and using carbon dioxide as the working medium will effectively Reduce the equipment size of each component of the energy storage system, shorten the construction period of the energy storage system, and reduce the investment cost of the energy storage system.

A liquid carbon dioxide energy storage system for combined hydrogen, heat and power generation in the embodiment of the present invention stores the carbon dioxide working medium in a liquid form, which effectively reduces the volume of the container for storing the carbon dioxide working medium, greatly increases the energy storage density of the energy storage system, and effectively It reduces the investment cost of the container for storing working fluid and the floor area of the energy storage system, and reduces the construction cost of the energy storage system.

Optionally, the liquid carbon dioxide circuit includes a turbine 6, a regenerator 8, a condenser 9, a low-pressure carbon dioxide liquid storage tank 10, a carbon dioxide working medium pump 11, a first cooler 12, and a high-pressure carbon dioxide liquid storage tank 13, and the low-pressure carbon dioxide storage tank The outlet of the liquid tank 10 is connected with the inlet of the carbon dioxide working medium pump 11, the outlet of the carbon dioxide working medium pump 11 is connected with the hot side inlet of the first cooler 12, and the hot side outlet of the first cooler 12 is connected with the high pressure carbon dioxide liquid storage tank 13 The inlet is connected, the outlet of the high-pressure carbon dioxide liquid storage tank 13 is connected with the cold side inlet of the regenerator 8, the cold side outlet of the regenerator 8 is connected with the cold side inlet of the first heat exchanger 5, and the cold side inlet of the first heat exchanger 5 is connected. The side outlet is connected with the inlet of the turbine 6, the outlet of the turbine 6 is connected with the hot side inlet of the second heat exchanger 7, the hot side outlet of the second heat exchanger 7 is connected with the hot side inlet of the regenerator 8, and the return The hot side outlet of the heater 8 is connected with the inlet of the condenser 9 , and the outlet of the condenser 9 is connected with the inlet of the low-pressure carbon dioxide liquid storage tank 10 .

A liquid carbon dioxide energy storage system for combined hydrogen, heat and power generation according to an embodiment of the present invention uses a carbon dioxide working medium pump 11 to increase the pressure of carbon dioxide. Improve energy storage system efficiency.

Optionally, the molten salt energy storage circuit includes an electric heating boiler 2, a high temperature molten salt storage tank 3 and a low temperature molten salt storage tank 4, the renewable energy power generation device is used to supply power to the electric heating boiler 2, and the low temperature molten salt storage tank 4 The outlet is connected to the inlet of the electric heating boiler 2, the outlet of the electric heating boiler 2 is connected to the inlet of the high-temperature molten salt storage tank 3, the outlet of the high-temperature molten salt storage tank 3 is connected to the inlet of the hot side of the first heat exchanger 5, and the first The hot side outlet of the heat exchanger 5 is connected with the inlet of the low temperature molten salt storage tank 4 .

When the grid load demand is low, the electric energy generated by the renewable energy power generation device cannot be connected to the grid, and the system starts the energy storage process. The low-temperature molten salt in the low-temperature molten salt storage tank 4 enters the electric heating boiler 2, and the electric heating boiler 2 uses the electric energy of the renewable energy power generation device to generate heat to heat the low-temperature molten salt, and the heated low-temperature molten salt becomes high-temperature molten salt and is stored in the In the high temperature molten salt storage tank 3. At the same time, the electric energy of the renewable energy power generation device is used to drive the carbon dioxide working medium pump 11 to pressurize the low-pressure liquid carbon dioxide in the low-pressure carbon dioxide liquid storage tank 10 into high-pressure liquid carbon dioxide, and then the high-pressure liquid carbon dioxide enters the first cooler 12 to be cooled and stored in In the high-pressure carbon dioxide liquid storage tank 13, the hot water generated by the first cooler 12 is used to provide domestic hot water for residents. Through the above energy storage process, the electric energy of the renewable energy power generation device that cannot be connected to the grid is stored in the form of heat energy and pressure energy.

When the grid load demand is high, the system starts the energy release process. The high-pressure liquid carbon dioxide stored in the high-pressure carbon dioxide liquid storage tank 13 enters the regenerator 8 and is heated to a gaseous state, and then the carbon dioxide working medium enters the high-temperature molten salt stored in the high-temperature molten salt storage tank 3 in the first heat exchanger 5 The medium is further heated to increase the superheat of the carbon dioxide working medium, and the low-temperature molten salt medium that has completed the heat exchange process is stored in the low-temperature molten salt storage tank 4, and the heated carbon dioxide working medium enters the turbine 6 to do work to drive the generator to generate electricity, and then the carbon dioxide The working medium enters the second heat exchanger 7 from the outlet of the turbine 6, and the low-temperature heat-conducting oil stored in the low-temperature heat-conducting oil storage tank 18 enters the second heat exchanger 7 to absorb the heat energy of the carbon dioxide working medium and become a high-temperature heat-conducting oil stored at a high temperature. In the heat transfer oil storage tank 14, the carbon dioxide working medium that has completed the heat exchange enters the regenerator 8 for reheating, heats and vaporizes the carbon dioxide that enters the regenerator 8 from the high-pressure carbon dioxide liquid storage tank 13, and then completes the reheating process. The carbon dioxide working medium is condensed into a liquid state by the condenser 9 and stored in the low-pressure carbon dioxide liquid storage tank 10 . Through the above energy release process, the heat energy and pressure energy stored in the energy storage process are converted into electrical energy to supply power to the grid.

Optionally, the carbon dioxide working medium pump 11 is connected to a renewable energy power generation device, and the renewable energy power generation device can supply power to the carbon dioxide working medium pump 11 . For example, the renewable energy power generation device is a wind farm 1 . It can be understood that the electric energy consumed by the electric heating boiler 2 and the carbon dioxide working medium pump 11 is provided by the wind farm 1 . A liquid carbon dioxide energy storage system for combined hydrogen, heat and power generation in an embodiment of the present invention uses an electric heating boiler 2 to store wind power that cannot be connected to the grid in the form of thermal energy in a molten salt heat storage medium, which has a high heat storage temperature and effectively improves energy storage. The inlet temperature of the system turbine 6 improves the efficiency of the energy storage system.

In some embodiments, the heat transfer oil circuit includes a high temperature heat transfer oil storage tank 14, a heat transfer oil pump 15 and a low temperature heat transfer oil storage tank 18, the outlet of the high temperature heat transfer oil storage tank 14 is connected to the inlet of the heat transfer oil pump 15, and the outlet of the heat transfer oil pump 15 is connected to the The tube side inlet of the reactor 16 is connected, the tube side outlet of the reactor 16 is connected with the hot side inlet of the gasifier 17, the hot side outlet of the gasifier 17 is connected with the inlet of the low-temperature heat transfer oil storage tank 18, and the low temperature heat transfer oil storage tank 18 is connected. The outlet of the tank 18 is connected to the cold-side inlet of the second heat exchanger 7, and the cold-side outlet of the second heat exchanger 7 is connected to the inlet of the high-temperature heat transfer oil tank. It can be understood that the energy storage system for hydrogen, heat and electricity combined production of liquid carbon dioxide in the embodiment of the present invention uses heat transfer oil heat storage medium to store the exhaust heat of turbine 6, even if the energy storage system is not working in the state of energy release, the production The hydrogen module still has a stable source of heat to maintain the methanol hydrogen production reaction.

Further, the methanol-to-hydrogen production loop also includes: a feeding device, a preheater 22 , a second cooler 23 , a gas-liquid separator 24 , a pressure swing adsorber 25 and a hydrogen storage tank 26 . The feeding device is used to supply methanol raw material. The feeding device includes a desalted water storage tank 19, a methanol storage tank 20 and a methanol raw material liquid pump 21. The desalted water storage tank 19 is used for storing desalted water, and the methanol storage tank 20 is used for storing methanol. The desalted water in the desalted water storage tank is mixed with the methanol in the methanol storage tank according to a certain ratio, and then enters the methanol raw material liquid pump 21 , and the outlet of the methanol raw material liquid pump 21 is connected with the cold side inlet of the preheater 22 .

The cold-side outlet of the preheater 22 is connected with the cold-side inlet of the gasifier 17, the cold-side outlet of the gasifier 17 is connected with the shell-side inlet of the reactor 16, and the shell-side outlet of the reactor 16 is connected with the inlet of the preheater 22. The hot side inlet is connected, the hot side outlet of the preheater 22 is connected with the hot side inlet of the second cooler 23, the hot side outlet of the second cooler 23 is connected with the inlet of the gas-liquid separator 24, and the gas-liquid separator 24 The gas side outlet is connected to the inlet of the pressure swing adsorber 25 , and the outlet of the pressure swing adsorber 25 is connected to the inlet of the hydrogen storage tank 26 . The shell side of the reactor 16 is filled with the catalyst required for the methanol reforming hydrogen production reaction.

It can be understood that during the hydrogen production process, the high-temperature heat-conducting oil stored in the high-temperature heat-conducting oil storage tank 14 enters the reactor 16 and the gasifier 17 successively under the action of the heat-conducting oil pump 15, and uses the heat carried by it to maintain the methanol The reforming hydrogen production reaction proceeds and the methanol raw material liquid is vaporized, and then the heat transfer oil that completes the heat exchange is stored in the low-temperature heat transfer oil storage tank 18 . The desalted water stored in the desalted water storage tank 19 and the methanol stored in the methanol storage tank 20 are mixed according to a certain ratio to form a methanol raw material liquid, and then the methanol raw material liquid is pressurized by the methanol raw material liquid pump 21 and enters the preheater 22 for preheating. Heat, the preheated methanol raw material liquid enters the gasifier 17 and is heated and vaporized by the heat transfer oil, and the gasified raw material enters the reactor 16 and is heated by the high temperature heat transfer oil, and undergoes a reforming hydrogen production reaction under the catalytic action of the catalyst. The reacted product enters the preheater 22 to preheat the methanol raw material liquid, and then the reaction product enters the second cooler 23 to be cooled and then enters the gas-liquid separator 24. In the gas-liquid separator 24, the gaseous product enters the pressure swing adsorption The impurity therein is removed in the device 25 to obtain pure hydrogen, and then the hydrogen is stored in the hydrogen storage tank 26 to complete the methanol reforming hydrogen production process.

Optionally, the liquid side outlet of the gas-liquid separator 24 is connected to the inlet of the methanol raw material liquid pump 21, and the liquid substance separated by the liquid side outlet of the gas-liquid separator 24 can be passed into the inlet of the methanol raw material liquid pump 21, so that the liquid product Re-mixing with the methanol raw material liquid to carry out the reforming hydrogen production reaction improves the utilization rate of the raw material and reduces the loss of the raw material.

In some embodiments, at least one of the condenser 9, the first cooler 12 and the second cooler 23 is connected to a domestic hot water circuit. For example, the condenser 9, the first cooler 12, and the second cooler 23 are all connected to the domestic hot water circuit, so as to provide domestic hot water to residents or meet other daily needs, realize energy cascade utilization, and reduce surrounding Heating and heating costs for residents.

To sum up, a liquid carbon dioxide energy storage system for combined generation of hydrogen, heat and electricity according to an embodiment of the present invention has at least the following technical effects.

(1) A liquid carbon dioxide energy storage system for combined hydrogen, heat and power generation in the embodiment of the present invention uses heat conduction oil to absorb and store the heat energy of the carbon dioxide working fluid at the outlet of turbine 6 in the energy release stage to vaporize the methanol raw material liquid and send it to the reactor 16 Provide heat to maintain the progress of methanol reforming hydrogen production reaction, so that the heat of carbon dioxide working fluid at the outlet of turbine 6 can be used reasonably and scientifically, realizing cascade utilization of energy, and at the same time greatly reducing the production cost of hydrogen, and the production process has an impact on the environment greatly reduced.

(2) A liquid carbon dioxide energy storage system for combined hydrogen, heat and power generation in the embodiment of the present invention uses the carbon dioxide working medium pump 11 to increase the carbon dioxide pressure. Compared with the traditional scheme using a compressor, the use of the pump to increase the working medium pressure effectively reduces compression Power consumption, effectively improving the efficiency of the energy storage system.

(3) A liquid carbon dioxide energy storage system for combined hydrogen, heat and power generation in the embodiment of the present invention uses carbon dioxide as the working medium of the energy storage system. Compared with other commonly used gases, carbon dioxide has a higher density, and carbon dioxide is used as the working medium It will effectively reduce the equipment size of each component of the energy storage system, shorten the construction period of the energy storage system, and reduce the investment cost of the energy storage system.

(4) A hydrogen heat and power trigeneration liquid carbon dioxide energy storage system according to the embodiment of the present invention adopts an electric heating boiler 2 to store the electric energy of the wind farm 1 that cannot be connected to the grid in the form of thermal energy in the molten salt heat storage medium, and the heat storage temperature is High, effectively increase the inlet temperature of the turbine 6 of the energy storage system, and improve the efficiency of the energy storage system.

(5) A liquid carbon dioxide energy storage system for combined hydrogen, heat and power generation according to an embodiment of the present invention stores the carbon dioxide working medium in a liquid form, effectively reducing the volume of the container for storing the carbon dioxide working medium, and greatly increasing the energy storage density of the energy storage system Increased, effectively reducing the investment cost of the container for storing working fluid and the area occupied by the energy storage system, and reducing the construction cost of the energy storage system.

(6) A hydrogen heat and power trigeneration liquid carbon dioxide energy storage system according to an embodiment of the present invention uses a heat transfer oil heat storage medium to store the exhaust heat of the turbine 6, even if the energy storage system is not working under the energy release state, hydrogen production The module still has a stable heat source to maintain the methanol hydrogen production reaction.

(7) A hydrogen-heat-electricity triple-generation liquid carbon dioxide energy storage system according to an embodiment of the present invention uses the hot water generated by the cooler and condenser 9 to provide heating to surrounding residents in the form of domestic hot water or to meet other daily needs, It realizes energy cascade utilization and reduces heating and heat consumption costs of surrounding residents.

In describing the present invention, it should be understood that the terms "center", "longitudinal", "transverse", "length", "width", "thickness", "upper", "lower", "front", " Back", "Left", "Right", "Vertical", "Horizontal", "Top", "Bottom", "Inner", "Outer", "Clockwise", "Counterclockwise", "Axial", The orientation or positional relationship indicated by "radial", "circumferential", etc. is based on the orientation or positional relationship shown in the drawings, and is only for the convenience of describing the present invention and simplifying the description, rather than indicating or implying the referred device or element Must be in a particular orientation, be constructed in a particular orientation, and operate in a particular orientation, and therefore should not be construed as limiting the invention.

In addition, the terms "first" and "second" are used for descriptive purposes only, and cannot be interpreted as indicating or implying relative importance or implicitly specifying the quantity of indicated technical features. Thus, the features defined as "first" and "second" may explicitly or implicitly include at least one of these features. In the description of the present invention, "plurality" means at least two, such as two, three, etc., unless otherwise specifically defined.

In the present invention, unless otherwise clearly specified and limited, terms such as "installation", "connection", "connection" and "fixation" should be understood in a broad sense, for example, it can be a fixed connection or a detachable connection , or integrated; can be mechanically connected, can also be electrically connected or can communicate with each other; can be directly connected, can also be indirectly connected through an intermediary, can be the internal communication of two components or the interaction relationship between two components, Unless expressly defined otherwise. Those of ordinary skill in the art can understand the specific meanings of the above terms in the present invention according to specific situations.

In the present invention, unless otherwise clearly specified and limited, the first feature may be in direct contact with the first feature or the first and second feature may be in direct contact with the second feature through an intermediary. touch. Moreover, "above", "above" and "above" the first feature on the second feature may mean that the first feature is directly above or obliquely above the second feature, or simply means that the first feature is higher in level than the second feature. "Below", "beneath" and "beneath" the first feature may mean that the first feature is directly below or obliquely below the second feature, or simply means that the first feature is less horizontally than the second feature.

As used herein, the terms "one embodiment," "some embodiments," "example," "specific examples," or "some examples" mean specific features, structures, materials, or features described in connection with the embodiment or example. A feature is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the described specific features, structures, materials or characteristics may be combined in any suitable manner in any one or more embodiments or examples. In addition, those skilled in the art can combine and combine different embodiments or examples and features of different embodiments or examples described in this specification without conflicting with each other.

Although the above-mentioned embodiments have been shown and described, it can be understood that the above-mentioned embodiments are exemplary, and should not be construed as limitations on the present invention. Changes, modifications, substitutions and variations made by those skilled in the art to the above-mentioned embodiments All within the protection scope of the present invention.

Claims (10)

1. The hydrogen-heat-power cogeneration liquid carbon dioxide energy storage system is characterized by comprising a renewable energy power generation device, an energy storage module and a hydrogen production module;

the energy storage module comprises a molten salt energy storage loop, a liquid carbon dioxide energy storage loop, a first heat exchanger and a second heat exchanger, the renewable energy power generation device is connected with the molten salt energy storage loop, the hot side of the first heat exchanger is connected with the molten salt energy storage loop, the cold side of the first heat exchanger is connected with the liquid carbon dioxide energy storage loop, and the hot side of the second heat exchanger is connected with the liquid carbon dioxide energy storage loop;

the hydrogen production module comprises a heat conduction oil loop and a methanol hydrogen production loop, wherein the methanol hydrogen production loop comprises a reactor and a gasifier, and the heat conduction oil loop is connected with the cold side of the second heat exchanger, the pipe side of the reactor and the hot side of the gasifier.

2. The hydrogen-heat-power cogeneration liquid carbon dioxide energy storage system of claim 1 wherein the liquid carbon dioxide circuit comprises a turbine, a regenerator, a condenser, a low pressure carbon dioxide liquid storage tank, a carbon dioxide working fluid pump, a first cooler and a high pressure carbon dioxide liquid storage tank,

the outlet of the low-pressure carbon dioxide liquid storage tank is connected with the inlet of the carbon dioxide working medium pump, the outlet of the carbon dioxide working medium pump is connected with the hot side inlet of the first cooler, the hot side outlet of the first cooler is connected with the inlet of the high-pressure carbon dioxide liquid storage tank, the outlet of the high-pressure carbon dioxide liquid storage tank is connected with the cold side inlet of the heat regenerator, the cold side outlet of the heat regenerator is connected with the cold side inlet of the first heat exchanger, the cold side outlet of the first heat exchanger is connected with the inlet of the turbine, the outlet of the turbine is connected with the hot side inlet of the second heat exchanger, the hot side outlet of the second heat exchanger is connected with the hot side inlet of the heat regenerator, the hot side outlet of the heat regenerator is connected with the inlet of the condenser, and the outlet of the condenser is connected with the inlet of the low-pressure carbon dioxide liquid storage tank.

3. The liquid carbon dioxide energy storage system for hydrogen-heat-power cogeneration of claim 2, wherein the carbon dioxide working medium pump is connected with the renewable energy power generation device, and the renewable energy power generation device can supply power to the carbon dioxide working medium pump;

and/or the renewable energy power generation device is a wind farm.

4. The liquid carbon dioxide energy storage system of claim 1, wherein the molten salt energy storage loop comprises an electric heating boiler, a high-temperature molten salt storage tank and a low-temperature molten salt storage tank, the renewable energy power generation device is used for supplying power to the electric heating boiler, an outlet of the low-temperature molten salt storage tank is connected with an inlet of the electric heating boiler, an outlet of the electric heating boiler is connected with an inlet of the high-temperature molten salt storage tank, an outlet of the high-temperature molten salt storage tank is connected with an inlet on a hot side of the first heat exchanger, and an outlet on a hot side of the first heat exchanger is connected with an inlet of the low-temperature molten salt storage tank.

5. The liquid carbon dioxide energy storage system of claim 1, wherein the heat transfer oil circuit comprises a high temperature heat transfer oil storage tank, a heat transfer oil pump and a low temperature heat transfer oil storage tank, wherein an outlet of the high temperature heat transfer oil storage tank is connected with an inlet of the heat transfer oil pump, an outlet of the heat transfer oil pump is connected with a pipe side inlet of the reactor, a pipe side outlet of the reactor is connected with a hot side inlet of the gasifier, a hot side outlet of the gasifier is connected with an inlet of the low temperature heat transfer oil storage tank, an outlet of the low temperature heat transfer oil storage tank is connected with a cold side inlet of the second heat exchanger, and a cold side outlet of the second heat exchanger is connected with an inlet of the high temperature heat transfer oil tank.

6. The hydrogen-heat-power cogeneration liquid carbon dioxide energy storage system of claim 2, wherein the methanol-to-hydrogen loop further comprises: a feeding device, a preheater, a second cooler, a gas-liquid separator, a pressure swing adsorber and a hydrogen storage tank,

the feeding device is used for supplying methanol raw material liquid, the feeding device is connected with a cold side inlet of the preheater, a cold side outlet of the preheater is connected with a cold side inlet of the gasifier, a cold side outlet of the gasifier is connected with a shell side inlet of the reactor, a shell side outlet of the reactor is connected with a hot side inlet of the preheater, a hot side outlet of the preheater is connected with a hot side inlet of the second cooler, a hot side outlet of the second cooler is connected with an inlet of the gas-liquid separator, a gas side outlet of the gas-liquid separator is connected with an inlet of the pressure swing adsorber, and an outlet of the pressure swing adsorber is connected with an inlet of the hydrogen storage tank.

7. The liquid carbon dioxide energy storage system for hydrogen, heat and power cogeneration of claim 6, wherein the feeding device comprises a desalted water storage tank, a methanol storage tank and a methanol raw material liquid pump, the desalted water storage tank is used for storing desalted water, the methanol storage tank is used for storing methanol, water in the desalted water storage tank and the methanol in the methanol storage tank are mixed according to a certain proportion and then enter the methanol raw material liquid pump, and an outlet of the methanol raw material liquid pump is connected with a cold side inlet of the preheater.

8. The liquid carbon dioxide energy storage system for hydrogen, heat and power co-generation according to claim 7, wherein the liquid side outlet of the gas-liquid separator is connected to the methanol feed pump inlet, and liquid substances separated from the liquid side outlet of the gas-liquid separator can be introduced into the methanol feed pump inlet.

9. The hydrogen-heat and-power cogeneration liquid carbon dioxide energy storage system of claim 7 wherein at least one of the condenser, the first cooler, and the second cooler is connected to a domestic hot water circuit.

10. A hydrogen-heat and power cogeneration liquid carbon dioxide energy storage system according to any one of claims 1-9, wherein the shell side of the reactor is filled with a catalyst required for a methanol reforming hydrogen production reaction.