An integrated hydrogen production and storage device based on hydrogen production by formic acid and a fuel cell system

Abstract

The application discloses an integrated hydrogen production and storage device based on hydrogen production from formic acid, which comprises a formic acid hydrogen production assembly, a gas compression assembly, a rectification and purification assembly, a refrigeration assembly, a heat exchange assembly, a solid-state hydrogen storage assembly and a carbon dioxide storage assembly; the formic acid hydrogen production assembly is connected with the rectification and purification assembly through the gas compression assembly; the refrigeration assembly is arranged in the rectification and purification assembly; a hydrogen buffer tank is connected with a hydrogen end of the rectification and purification assembly; a carbon dioxide gas end of the rectification and purification assembly is connected with the heat exchange assembly; one end of the heat exchange assembly is connected with the carbon dioxide storage assembly; and the other end of the heat exchange assembly is connected with the solid-state hydrogen storage assembly; and the application further discloses a fuel cell system; the highly integrated device is used for hydrogen charging of the solid-state hydrogen storage assembly after cracking and purification; the formic acid hydrogen production, hydrogen purification, carbon dioxide treatment, solid-state hydrogen charging and hydrogen storage and heat management are integrated in one device, and the total energy consumption of the whole device is reduced.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of hydrogen production, and particularly relates to an integrated hydrogen production and storage device based on formic acid hydrogen production and a fuel cell system. BACKGROUND

[0002] Hydrogen energy, as a clean and efficient energy carrier, plays an important role in the future energy structure. Solid-state hydrogen storage (such as metal hydride hydrogen storage) has the advantages of high hydrogen storage density and good safety, and is a very promising hydrogen storage method. Formic acid (HCOOH) is a safe, easy-to-store and transport liquid organic hydrogen carrier (LOHC) with a high theoretical hydrogen storage capacity (about 4.4 wt%). Hydrogen (H2) and carbon dioxide (CO2) can be produced by catalytic cracking or thermal cracking of formic acid. This provides the possibility of distributed and on-demand hydrogen production. The gas produced by formic acid cracking is a mixture of H2 and CO2 (hydrogen-rich gas).

[0003] In the prior art, formic acid hydrogen production, hydrogen purification and solid-state hydrogen storage hydrogen production processes are usually designed and implemented as independent links. On the one hand, the dispersed layout makes the overall system occupy a large space, which is difficult to adapt to distributed or mobile application scenarios. On the other hand, the energy flow of each link is disconnected, which cannot form effective integration, resulting in a large amount of energy waste and significantly reduced system operation efficiency.

[0004] Even if the components are conventionally integrated, it only stays at the physical combination level and cannot solve the core problem of energy supply and demand mismatch between components. Instead, it easily causes new defects such as severe energy fluctuations and poor adaptability, further restricting system stability and energy efficiency. SUMMARY

[0005] In order to overcome the deficiencies of the prior art, the purpose of the present application is to provide an integrated hydrogen production and storage device based on formic acid hydrogen production.

[0006] Another purpose of the present application is to provide a fuel cell system based on formic acid hydrogen production.

[0007] The purpose of the present application is achieved by the following technical solutions:

[0008] The application discloses an integrated hydrogen production and storage device based on formic acid hydrogen production, which comprises a formic acid hydrogen production assembly, a gas compression assembly, a rectification and purification assembly, a refrigeration assembly, a heat exchange assembly, a solid-state hydrogen storage assembly and a carbon dioxide storage assembly; the formic acid hydrogen production assembly is connected with the rectification and purification assembly through the gas compression assembly; the rectification and purification assembly is connected with the refrigeration assembly; the hydrogen end of the rectification and purification assembly is connected with a hydrogen buffer tank; the carbon dioxide gas end of the rectification and purification assembly is connected with the heat exchange assembly; one end of the heat exchange assembly is connected with the carbon dioxide storage assembly; the other end of the heat exchange assembly is connected with the solid-state hydrogen storage assembly.

[0009] Preferably, the heat exchange assembly comprises a heat preservation water tank, a water pipe and a thermostat, the heat preservation water tank is internally provided with a heat exchange coil and a heat exchange medium, the heat exchange coil is connected with the carbon dioxide gas end of the rectification and purification assembly, the heat preservation water tank is connected with the thermostat through the water pipe, the thermostat is connected with the solid-state hydrogen storage assembly, and a water temperature sensor is arranged in the thermostat.

[0010] Preferably, the gas compression assembly is used for pressurizing the hydrogen-rich gas to 4-6 MPa and then conveying the hydrogen-rich gas to the rectification and purification assembly.

[0011] More preferably, the gas compression assembly is used for pressurizing the hydrogen-rich gas to 4 MPa and then conveying the hydrogen-rich gas to the rectification and purification assembly.

[0012] Preferably, the rectification and purification assembly comprises a rectification tower, and specific operation parameters of the rectification tower comprise a tower top temperature of -10-5 DEG C, a tower bottom temperature of 5-10 DEG C, a theoretical tower plate number of 20-30 levels, and a reflux ratio of 0.5-1.5.

[0013] Preferably, the gas compression assembly comprises a compressor, a temperature regulator, a gas pressure sensor and a gas temperature sensor, the gas inlet end of the compressor is connected with the formic acid hydrogen production assembly, the gas outlet end of the compressor is connected with the rectification tower, the gas inlet end is provided with the gas pressure sensor and the gas temperature sensor, and the gas outlet end is provided with the temperature regulator and the gas pressure sensor.

[0014] Preferably, the solid-state hydrogen storage assembly comprises a hydrogen storage tank, a fixing frame, a fixing partition plate, a fixing bottom plate and a spring, the fixing bottom plate is fixedly connected to the bottom wall in the thermostat, the fixing bottom plate is provided with the fixing partition plate at intervals, at least one hydrogen storage tank is arranged between two adjacent fixing partition plates, the hydrogen storage tank is connected with the fixing partition plate through the fixing frame, the spring is arranged between the hydrogen storage tank, the fixing partition plate and the fixing bottom plate, a plurality of through holes are formed in the fixing partition plate and the fixing bottom plate, the hydrogen filling port of the hydrogen storage tank is connected with the hydrogen buffer tank through a pipeline, and the pipeline is provided with a gas filter and a flowmeter.

[0015] Preferably, the hydrogen storage tank adopts a metal hydride alloy material.

[0016] More preferably, the metal hydride alloy material is LaNi5 or TiFe.

[0017] Preferably, the refrigeration assembly comprises a circulating pump, a refrigeration pipe and a refrigerator, the circulating pump is arranged in the refrigeration pipe, the refrigerator is in communication with the refrigeration pipe, and a part of the refrigeration pipe is arranged inside the rectifying tower.

[0018] Preferably, the formic acid hydrogen production assembly comprises a cracking reactor, a gas-water separator and a gas buffer tank, one end of the cracking reactor is connected with a formic acid storage tank, the other end of the cracking reactor is connected with the gas-water separator, and the gas-water separator is connected with the compressor in an on-off manner through the gas buffer tank.

[0019] Preferably, the carbon dioxide storage assembly is a high-pressure gas cylinder or a low-temperature storage tank.

[0020] Preferably, the hydrogen production and storage device further comprises a control assembly, and the control assembly is electrically connected with at least one of the formic acid hydrogen production assembly, the compressor, the rectification and purification assembly, the refrigeration assembly, the heat exchange assembly, the solid-state hydrogen storage assembly and the carbon dioxide storage assembly.

[0021] A fuel cell system further comprises a fuel cell assembly, and the fuel cell assembly is in communication with the solid-state hydrogen storage assembly through a pipeline.

[0022] The present application has the following advantages and beneficial effects compared with the prior art:

[0023] (1) The present application proposes a highly integrated device for hydrogen charging of a solid-state hydrogen storage assembly by using formic acid as a hydrogen source, cracking and purification, which integrates formic acid hydrogen production, hydrogen purification, carbon dioxide treatment, solid-state hydrogen charging and storage, and heat management in one device, has a compact structure, occupies a small area, and is particularly suitable for distributed or mobile application scenarios.

[0024] (2) The device disclosed in the present application uses low-temperature carbon dioxide separated in the rectification and purification process to cool the solid-state hydrogen storage assembly, realizes energy cascade utilization and efficient heat management, not only maximally avoids the need for separately configuring a large-power refrigeration system for the solid-state hydrogen production process, but also reduces the total energy consumption of the entire device, and realizes effective recovery and cascade utilization of energy inside the device.

[0025] (3) The device disclosed in this invention takes energy flow matching as its core. It reduces energy consumption in the hydrogen production process by combining the closed-loop utilization of reaction cooling capacity with the coordinated control of pressure and temperature under all operating conditions and parameters. It achieves temperature balance by controlling the critical point pressure of CO2, and ensures the application balance of the heat-insulating water tank by regulating the flow rate and volume of the distillation column. It controls the flow rate of each heat exchanger by monitoring the temperature point. It achieves precise matching of energy demand and supply of each component, effectively offsets the energy supply and demand fluctuations in each link, and avoids the impact of energy shock when the components operate independently on the stability of the system. Attached Figure Description

[0026] Figure 1 This is a schematic diagram of the integrated hydrogen production and storage device based on formic acid hydrogen production disclosed in this invention.

[0027] Figure 2 This is a schematic diagram of the structure of a solid-state hydrogen storage component;

[0028] Figure 3 This is a schematic diagram of the external structure of the constant temperature chamber;

[0029] Figure 4 This is a schematic diagram of the control process of the control component.

[0030] The markings of the components in the attached diagram:

[0031] 10. Formic acid hydrogen production assembly; 11. Cracking reactor; 12. Gas-liquid separator; 13. Gas buffer tank; 14. Cracking pressure sensor; 15. Cracking temperature sensor; 16. First solenoid valve; 17. Heat exchanger; 20. Gas compression assembly; 21. Compressor; 22. Gas pressure sensor; 23. Gas temperature sensor; 30. Distillation and purification assembly; 31. Distillation column; 40. Refrigeration assembly; 50. Heat exchange assembly; 51. Insulated water tank; 52. Water pipe; 53. Constant temperature chamber; 54. Water temperature sensor; 60. Solid hydrogen storage assembly; 61. Hydrogen storage tank; 62. Fixing frame; 63. Fixing partition; 64. Fixing base plate; 65. Spring; 66. Hydrogen filling port; 70. Carbon dioxide storage assembly; 80. Heat exchange coil; 90. Hydrogen buffer tank; 100. Control assembly. Detailed Implementation

[0032] The invention's objective will be further described in detail below with reference to the accompanying drawings and specific embodiments. The embodiments cannot be described in detail here, but the implementation of the invention is not limited to the following embodiments.

[0033] Example 1

[0034] This invention discloses an integrated hydrogen production and storage device based on formic acid hydrogen production, including a formic acid hydrogen production component 10, a gas compression component 20, a distillation and purification component 30, a refrigeration component 40, a heat exchange component 50, a solid hydrogen storage component 60, and a carbon dioxide storage component 70.

[0035] The formic acid hydrogen production assembly 10 includes a cracking reactor 11, a gas-liquid separator 12, a gas buffer tank 13, a cracking pressure sensor 14, a cracking temperature sensor 15, a first solenoid valve 16, and a heat exchanger 17; the gas compression assembly 20 includes a compressor 21, a temperature controller, a gas pressure sensor 22, and a gas temperature sensor 23; the distillation and purification assembly 30 includes a distillation column 31; the heat exchange assembly 50 includes an insulated water tank 51, water pipes 52, and a constant temperature chamber 53; the solid hydrogen storage assembly 60 includes a hydrogen storage tank 61, a fixing frame 62, a fixing partition 63, a fixing base plate 64, a spring 65, and a hydrogen filling port 66;

[0036] The formic acid storage tank is used to store liquid formic acid for hydrogen production. The formic acid storage tank is connected to the cracking reactor 11 via pipeline. The cracking reactor 11 contains a catalyst, which includes at least one of noble metal-based catalysts and non-noble metal-based catalysts. The cracking reactor 11 is used to carry out the cracking reaction of formic acid. The cracking pressure sensor 14 and the cracking temperature sensor 15 are respectively installed in the cracking reactor 11 to detect the pressure and temperature inside the cracking reactor 11.

[0037] The pyrolysis reactor 11 is connected to the gas-liquid separator 12 through a pipeline. The gas-liquid separator 12 separates the substances after the pyrolysis reaction into gas and liquid to obtain hydrogen-rich gas. The gas-liquid separator 12 is connected to the gas buffer tank 13 through a pipeline. A heat exchanger 17 is provided between the two. After being processed by the gas-liquid separator 12, the hydrogen-rich gas is cooled and stored in the gas buffer tank 13.

[0038] Gas buffer tank 13 is connected to the inlet of compressor 21 via a pipeline. Compressor 21 is a diaphragm compressor. Gas pressure sensor 22, gas temperature sensor 23, and first solenoid valve 16 are installed on the pipeline connecting gas buffer tank 13 and compressor 21. The outlet of compressor 21 is connected to distillation column 31. A thermostat and gas pressure sensor 22 are installed between compressor 21 and distillation column 31. Compressor 21 pressurizes the hydrogen-rich gas in gas buffer tank 13 to 4 MPa and then delivers it to distillation purification component 30. First solenoid valve 16 is used to control the opening and closing of the pipeline. Gas pressure sensor 22 and gas temperature sensor 23 are used to detect the pressure and temperature of hydrogen-rich gas, respectively. The thermostat is used to adjust the temperature of hydrogen-rich gas entering distillation purification component. The operating state of compressor 21 is adjusted by control component 100 to ensure the stability and safety of gas compression process. Using diaphragm compressor 21 can effectively avoid gas contamination and improve the purity of hydrogen.

[0039] The hydrogen end of the distillation column 31 is connected to the hydrogen buffer tank 90 at the top, and the carbon dioxide gas end of the distillation column 31 is connected to the heat exchange coil 80 at the bottom. The distillation column 31 has trays or packing inside and a refrigeration jacket on the outside. A condenser is provided at the top of the column, which may be integrated inside or outside the column, and the cooling capacity is provided by the refrigeration component 40. A reboiler is provided at the bottom of the column, which mainly collects liquid CO2 in this embodiment. The specific operating parameters of the distillation column 31 include: top temperature -10~5℃, bottom temperature 5~10℃, theoretical number of trays 20-30, and reflux ratio 0.5-1.5. By setting up the distillation column 31, low-temperature carbon dioxide accumulates at the bottom of the distillation column 31, and hydrogen accumulates at the top of the distillation column 31, achieving efficient separation of hydrogen and carbon dioxide.

[0040] The refrigeration assembly 40 includes a circulating pump, refrigeration pipes, and a refrigerator. The circulating pump is installed on the refrigeration pipes to drive the flow of refrigerant within the pipes. The refrigeration pipes are used to circulate the refrigerant. The refrigerator is connected to the refrigeration pipes and is used to cool the refrigerant. A portion of the refrigeration pipes is installed inside the distillation column 31 to cool the column. Through the design of the circulating pump, refrigeration pipes, and refrigerator, the refrigeration assembly 40 provides refrigerant to the distillation column 31. The refrigerant circulates in the refrigeration pipes, is cooled by the refrigerator, and then enters the distillation column 31 to absorb heat from the hydrogen-rich gas. This enables efficient separation of H2 and CO2 under high pressure and low temperature conditions within the column, ensuring the efficient operation of the distillation process.

[0041] The heat exchange coil 80 is a spiral-wound stainless steel coil with a heat exchange area of ​​10-15 m². Part of it is located inside the insulated water tank 51. One end of the heat exchange coil 80 is connected to the carbon dioxide gas end of the distillation and purification component 30, and the other end is connected to the carbon dioxide storage component 70. The insulated water tank 51 also contains a heat exchange medium, which is water. The insulated water tank 51 is connected to the constant temperature chamber 53 via a water pipe 52. The constant temperature chamber 53 is equipped with a water temperature sensor 54. A portion of the water pipe 52 is located inside the constant temperature chamber 53, and this portion is used for heat exchange with the constant temperature chamber 53 and the hydrogen storage tank 61 to cool the hydrogen storage tank 61. Low-temperature carbon dioxide flows through the heat exchange coil 80, and after contacting the water for heat exchange and cooling, it is collected in the carbon dioxide storage component 70, which is a high-pressure gas cylinder.

[0042] In practical applications, it has been found that the design of the heat exchange coil 80 and the heat exchange medium is particularly suitable for applications requiring precise temperature control, such as thermal management in the process of solid-state hydrogen storage and production. In hydrogen refueling stations for hydrogen-powered vehicles, this design ensures that the temperature of the hydrogen storage tank 61 remains stable within the optimal operating range during the hydrogen storage process, improving the hydrogen filling rate and storage capacity while ensuring operational safety.

[0043] A fixed base plate 64 is fixedly connected to the bottom wall inside the constant temperature chamber 53. Fixed partitions 63 are spaced apart on the fixed base plate 64. At least one hydrogen storage tank 61 is placed between two adjacent fixed partitions 63. The hydrogen storage tank 61 is made of metal hydride alloy material, which has high hydrogen storage density and good safety. The hydrogen storage tank 61 is connected to the fixed partitions 63 through a fixing frame 62. There are multiple fixing frames 62. Springs 65 are provided between the hydrogen storage tank 61 and the fixed partitions 63 and the fixed base plate 64. The heat exchange medium contacts the hydrogen storage tank 61 for heat exchange. The fixed partitions 63 and / or the fixed base plate 64 have multiple through holes for the flow of the heat exchange medium inside the constant temperature chamber 53. The solid-state hydrogen storage and production components 60 work together to achieve efficient hydrogen storage and thermal management during the production process. The fixing frame 62, fixing partition 63, and fixing base plate 64 are used to fix and support the hydrogen storage tank 61, ensuring the stability and safety of the hydrogen storage process. The spring 65 buffers the movement impact of the hydrogen storage tank 61 during the hydrogen filling and transportation process, avoiding damage to the hydrogen storage tank 61. The heat exchange medium in the constant temperature box 53 effectively controls the temperature during the hydrogen filling process through contact heat exchange with the hydrogen storage tank 61, improving the hydrogen filling efficiency and safety.

[0044] The hydrogen storage tank 61 in the solid hydrogen storage assembly 60 is made of a metal hydride alloy filled with LaNi5; it has high hydrogen storage density and good safety.

[0045] In practical applications, the solid-state hydrogen storage component 60 is suitable for occasions requiring high-density, safe, and efficient hydrogen storage, such as hydrogen refueling stations for hydrogen-powered vehicles, distributed energy systems, and mobile hydrogen energy supply. Especially in hydrogen refueling stations for hydrogen-powered vehicles, this component can ensure the temperature stability of hydrogen during the hydrogen filling process, improve the hydrogen filling rate and hydrogen storage capacity, and ensure operational safety.

[0046] Multiple hydrogen storage tanks 61 have hydrogen filling ports 66 spaced apart outside the constant temperature chamber 53. The hydrogen filling ports 66 of the hydrogen storage tanks 61 are connected to the hydrogen buffer tank 90 in a switchable manner to store hydrogen separately. A gas filter and a flow meter are installed at the hydrogen filling port 66 to filter the hydrogen entering the hydrogen storage tank 61 and to measure the flow rate of the hydrogen entering the hydrogen storage tank 61.

[0047] Practical applications have shown that the combination of the hydrogen filling port 66 and the heat exchange component 50 is particularly suitable for applications requiring precise control of the hydrogen filling process, such as hydrogen refueling stations for hydrogen fuel cell vehicles, distributed energy systems, and mobile hydrogen energy supply systems. Especially in hydrogen fuel cell vehicle refueling stations, this design can ensure the purity and flow control of hydrogen during the filling process, improve the filling rate and hydrogen storage capacity, and ensure operational safety.

[0048] The control component 100 employs a PLC and is electrically connected to at least one of the formic acid hydrogen production component 10, compressor 21, distillation and purification component 30, refrigeration component 40, heat exchange component 50, solid-state hydrogen storage component 60, and carbon dioxide storage component 70. The control component 100 monitors and controls the operating status of the entire hydrogen production and storage unit, ensuring coordinated operation among the components and improving the system's operational stability and efficiency.

[0049] How to use:

[0050] Liquid formic acid in the formic acid storage tank is pumped into the cracking reactor 11, which can be filled with a suitable catalyst based on noble metals, and undergoes a cracking reaction at 80-150℃: HCOOH → H2+ CO2. The generated high-temperature hydrogen-rich gas (mainly H2 and CO2, possibly containing small amounts of unreacted formic acid, water vapor, CO, and other impurities) flows out of the cracking reactor 11 and first enters the gas-liquid separator 12 to separate the water vapor and small amount of formic acid from the hydrogen-rich gas. Then, heat exchange occurs with the cooling medium, reducing the temperature to near room temperature or slightly above. The cooled hydrogen-rich gas enters the gas buffer tank 13, where the gas pressure is approximately 0.9 MPa. The outlet of the gas buffer tank 13 is connected to the compressor 21. The compressor 21 increases the pressure of the hydrogen-rich gas from approximately 0.9 MPa to 4 MPa. The gas pressure is confirmed by a pressure sensor to prepare for subsequent cryogenic distillation. The compressed gas is then cooled to control the gas temperature, which is determined by a temperature sensor. The compressed high-pressure hydrogen-rich gas enters the lower part of the distillation column 31 from the outlet of the compressor 21. The refrigeration unit generates a cryogenic refrigerant at approximately 5°C. This refrigerant is pumped (… Figure 1 (Not shown) is conveyed to the refrigeration jacket of distillation column 31 ( Figure 1 The CO2 (not shown) circulates in the column, absorbing heat from within the column. Under high pressure (4MPa), the higher boiling point CO2 (boiling point at normal pressure -78.5℃, liquefaction temperature increases under high pressure) condenses on the trays or packing and flows downwards, accumulating at the bottom of the column to form low-temperature liquid or high-density gaseous CO2. Meanwhile, the extremely low boiling point H2 (boiling point at normal pressure -252.87℃) remains gaseous and rises along the column. After further purification by the condenser at the top of the column (condensing away the small amount of residual high-boiling point impurities), it is finally drawn from the top of the column to obtain high-purity hydrogen. The low-temperature CO2 drawn from the bottom of the distillation column 31 is introduced into the heat exchange coil 80.

[0051] Meanwhile, room temperature water is introduced into the insulated water tank 51 for heat exchange. When low temperature CO2 flows through the heat exchange coil 80, it absorbs the heat of the water in the insulated water tank 51, causing the water temperature to drop. The temperature of CO2 itself rises, and it may become gaseous or remain under high pressure. The water after heat exchange flows out from the cold water outlet and is sent to the constant temperature box 53. The heated CO2 enters the carbon dioxide storage component for storage.

[0052] High-purity hydrogen enters the hydrogen buffer tank 90 from the top pipe of the distillation column 31, and then the outlet of the hydrogen buffer tank 90 is connected to the hydrogen charging port 66, which is used to connect to the hydrogen storage tank 61. The coolant outlet of the constant temperature chamber 53 is connected to the loop inlet of the insulated water tank 51, which can form a closed or semi-open cooling cycle. When the hydrogen charging operation is performed, the solenoid valve is opened, and high-purity hydrogen is charged into the hydrogen storage tank 61, where it reacts exothermically with the hydrogen storage material. At the same time, the circulation pump used to drive the water flow in the water pipe 52 is started, pumping cold water from the insulated water tank 51 into the constant temperature chamber 53 to absorb the heat generated by the hydrogen absorption reaction, maintain the component temperature within the optimal operating range, and ensure that the hydrogen charging process is carried out quickly, efficiently, and safely. After absorbing heat, the cooling water temperature rises and flows out from the outlet of the constant temperature chamber 53, which can be circulated back to the external heat dissipation system for exchange or other cooling treatments.

[0053] The control component 100 controls the smooth operation of the entire system, ensuring the pressure, temperature, and hydrogen production of the output gas. It controls the gas compression component 20, which can confirm the pressure of the incoming and outgoing gas through pressure sensors, ensuring that the gas can be output at a pressure of 4 MPa. It then controls the distillation and purification component 30, and uses pressure and temperature sensors to monitor and ensure that the cooling capacity provided by the refrigeration component 40 is sufficient to ensure that the distillation and purification component 30 can stably separate H2 and CO2.

[0054] Example 2

[0055] This embodiment also provides a fuel cell system, which includes the above-mentioned integrated hydrogen production and storage device based on formic acid hydrogen production. The fuel cell system also includes a fuel cell assembly, which is connected to the solid hydrogen storage assembly 60 through a pipeline. The fuel cell assembly uses hydrogen to carry out an oxidation-reduction reaction to generate electricity.

Claims

1. An integrated hydrogen production and storage device based on formic acid, characterized in that, The system includes a formic acid hydrogen production assembly (10), a gas compression assembly (20), a distillation and purification assembly (30), a refrigeration assembly (40), a heat exchange assembly (50), a solid hydrogen storage assembly (60), and a carbon dioxide storage assembly (70). The formic acid hydrogen production assembly (10) is connected to the distillation and purification assembly (30) via the gas compression assembly (20). The distillation and purification assembly (30) is connected to the refrigeration assembly (40). The hydrogen end of the distillation and purification assembly (30) is connected to a hydrogen buffer tank (90). The hydrogen buffer tank (90) is connected to the solid hydrogen storage assembly (60). The carbon dioxide gas end of the distillation and purification assembly (30) is connected to the heat exchange assembly (50). One end of the heat exchange assembly (50) is connected to the carbon dioxide storage assembly (70), and the other end of the heat exchange assembly (50) is connected to the solid hydrogen storage assembly (60). The gas compression assembly (20) is used to pressurize the hydrogen-rich gas to 4-6 MPa and then deliver it to the distillation and purification assembly (30).

2. The integrated hydrogen production and storage device based on formic acid hydrogen production according to claim 1, characterized in that, The heat exchange assembly (50) includes an insulated water tank (51), a water pipe (52), and a constant temperature chamber (53). The insulated water tank (51) is equipped with a heat exchange coil (80) and a heat exchange medium. The heat exchange coil (80) is connected to the carbon dioxide gas end of the distillation and purification assembly (30). The insulated water tank (51) is connected to the constant temperature chamber (53) through the water pipe (52). The constant temperature chamber (53) is connected to the solid hydrogen storage assembly (60). The constant temperature chamber (53) is equipped with a water temperature sensor (54).

3. The integrated hydrogen production and storage device based on formic acid hydrogen production according to claim 1, characterized in that, The distillation and purification component (30) includes a distillation column (31), and the specific operating parameters of the distillation column (31) include: top temperature -10~5℃, bottom temperature 5~10℃, theoretical number of plates 20-30, and reflux ratio 0.5-1.

5.

4. The integrated hydrogen production and storage device based on formic acid hydrogen production according to claim 3, characterized in that, The gas compression assembly (20) includes a compressor (21), a thermostat, a gas pressure sensor (22), and a gas temperature sensor (23). The inlet end of the compressor (21) is connected to the formic acid hydrogen production assembly (10), and the outlet end of the compressor (21) is connected to the distillation column (31). The gas pressure sensor (22) and the gas temperature sensor (23) are installed at the inlet end, and the thermostat and the gas pressure sensor (22) are installed at the outlet end.

5. The integrated hydrogen production and storage device based on formic acid hydrogen production according to claim 2, characterized in that, The solid hydrogen storage assembly (60) includes a hydrogen storage tank (61), a fixing frame (62), a fixing partition (63), a fixing base plate (64), and a spring (65). The fixing base plate (64) is fixedly connected to the bottom wall inside the constant temperature chamber (53). The fixing base plate (64) is spaced apart from the fixing partitions (63). At least one hydrogen storage tank (61) is provided between two adjacent fixing partitions (63). The hydrogen storage tank (61) is connected to the fixing partitions (63) through the fixing frame (62). The spring (65) is provided between the hydrogen storage tank (61) and its adjacent fixing partitions (63) and fixing base plate (64). The fixing partitions (63) and fixing base plate (64) have multiple through holes. The hydrogen filling port (66) of the hydrogen storage tank (61) is connected to the hydrogen buffer tank (90) through a pipeline. The pipeline is equipped with a gas filter and a flow meter.

6. The integrated hydrogen production and storage device based on formic acid hydrogen production according to claim 4, characterized in that, The refrigeration assembly (40) includes a circulating pump, a refrigeration pipe and a refrigerator. The circulating pump is located on the refrigeration pipe, the refrigerator is connected to the refrigeration pipe, and a portion of the refrigeration pipe is located inside the distillation column (31).

7. The integrated hydrogen production and storage device based on formic acid hydrogen production according to claim 4, characterized in that, The formic acid hydrogen production assembly (10) includes a cracking reactor (11), a gas-liquid separator (12), and a gas buffer tank (13). One end of the cracking reactor (11) is connected to the formic acid storage tank, and the other end of the cracking reactor (11) is connected to the gas-liquid separator (12). The gas-liquid separator (12) is connected to the compressor (21) in a switchable manner through the gas buffer tank (13).

8. The integrated hydrogen production and storage device based on formic acid hydrogen production according to claim 4, characterized in that, It also includes a control component (100), which is electrically connected to the formic acid hydrogen production component (10), the compressor (21), the distillation and purification component (30), the refrigeration component (40), the heat exchange component (50), the solid hydrogen storage component (60), and the carbon dioxide storage component (70), respectively.

9. A fuel cell system, characterized in that, The integrated hydrogen production and storage device based on formic acid hydrogen production according to any one of claims 1 to 8, wherein the fuel cell system further includes a fuel cell assembly, and the fuel cell assembly is connected to the solid hydrogen storage assembly (60) via a pipeline.

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