A skid-mounted hydrogen production, solid-state hydrogen storage and hydrogen fuel cell integrated system and operation method

Abstract

The present invention provides a skid-mounted integrated system for hydrogen production, solid-state hydrogen storage and hydrogen fuel cells and an operating method. The system includes: a skid-mounted housing, a power supply unit, a hydrogen production unit, a solid-state hydrogen storage unit, a hydrogen fuel cell unit and a central controller. The power supply unit is electrically connected to the hydrogen production unit, the solid-state hydrogen storage unit, the hydrogen fuel cell unit and the central controller respectively, and the central controller is communicatively connected to the power supply unit, the hydrogen production unit, the solid-state hydrogen storage unit and the hydrogen fuel cell unit respectively. The present invention can use AC and DC power supplies to electrolyze water to produce hydrogen after conversion by the power supply unit, use solid-state hydrogen storage materials to store and transport hydrogen, and supply hydrogen to the user end. The device is also equipped with a hydrogen fuel cell unit, which can convert the stored hydrogen into electricity and output DC and AC electricity to the outside. The skid-mounted integrated equipment has a compact layout and is easy to move. It can convert, transport and use scattered and unstable electricity, greatly improving the utilization rate of clean energy such as wind power and photovoltaics.

Description

Technical Field

[0001] The present invention relates to the technical field of hydrogen production and storage and hydrogen fuel cells, and in particular to a skid-mounted hydrogen production, solid-state hydrogen storage and hydrogen fuel cell integrated system and an operation method. Background Art

[0002] In recent years, my country's renewable energy will usher in a leapfrog development, and basically complete the construction of a clean, low-carbon, safe and efficient energy system. In the new energy system, wind power and photovoltaics will become the main force of power generation, and the core technologies related to energy storage and hydrogen energy will also achieve breakthroughs. Clean energy will replace fossil energy in the near future. Wind power and photovoltaics have gradually established their dominant position in renewable energy. In the future, most of my country's green electricity will come from wind and solar energy. In order to do a good job in the consumption of wind power and photovoltaic electricity, my country will increase technical research on grid transformation, energy storage and hydrogen energy to achieve effective consumption of wind power and photovoltaic electricity. Energy storage, one of the key technologies for the large-scale development of renewable energy, is expected to achieve rapid development along with photovoltaics and wind power. At present, mature energy storage technologies include pumped storage, compressed air storage, flywheel storage, electrochemical storage, and heat and hydrogen storage technologies. Among them, hydrogen energy is hailed as the super energy of the future. Hydrogen production requires a lot of electricity. Promoting wind power and photovoltaic hydrogen production can effectively solve the problem of electricity consumption. With the continuous development of hydrogen production technology through water electrolysis, wind power and photovoltaic hydrogen production will gradually meet commercial needs and become a new force in my country's energy substitution. The development of large-scale, highly safe, and low-cost hydrogen storage and transportation technologies is the key to the utilization of hydrogen energy. The currently widely used method of hydrogen storage and transportation is still gaseous hydrogen storage and transportation. This method has small reserves, high energy consumption, and requires high-pressure containers. There are unsafe factors such as hydrogen leakage and container explosion. Summary of the invention

[0003] The purpose of the present invention is to propose a skid-mounted integrated system of hydrogen production, solid-state hydrogen storage and hydrogen fuel cells in response to the intermittent, volatile and random nature of existing photovoltaic and wind power generation, which have varying degrees of impact on the system voltage, frequency and stability of the power grid after being connected to the grid, and the difficulty of wind power and photovoltaic power generation to be connected to the grid. The system can efficiently, safely and flexibly complete hydrogen production, hydrogen storage and power generation anytime and anywhere as needed, promote distributed off-grid utilization of electricity, build a wind power and photovoltaic hydrogen storage energy supply system, and effectively solve the problem of power consumption.

[0004] In order to solve the above technical problems, the present invention provides a skid-mounted integrated system of hydrogen production, solid-state hydrogen storage and hydrogen fuel cells, including a skid-mounted housing, a power supply unit, a hydrogen production unit, a solid-state hydrogen storage unit, a hydrogen fuel cell unit and a central controller; the power supply unit, the hydrogen production unit, the solid-state hydrogen storage unit, the hydrogen fuel cell unit and the central controller are arranged in the skid-mounted housing; the power supply unit is electrically connected to the hydrogen production unit, the solid-state hydrogen storage unit, the hydrogen fuel cell unit and the central controller respectively; the central controller is communicatively connected to the power supply unit, the hydrogen production unit, the solid-state hydrogen storage unit and the hydrogen fuel cell unit respectively; the hydrogen production unit, the solid-state hydrogen storage unit and the hydrogen fuel cell unit are connected in sequence through pipelines; the hydrogen fuel cell unit is powered by the solid-state hydrogen storage unit. The present invention integrates power supply, hydrogen production, solid-state hydrogen storage and hydrogen fuel cell devices in a skid-mounted container housing, the equipment layout is compact, easy to move, can flexibly use the electric energy generated by wind power and photovoltaic power to electrolyze water to produce hydrogen in a flexible time and location, and converts hydrogen into metal hydrides with stable chemical properties and large hydrogen carrying capacity through the solid-state hydrogen storage unit, which can transport hydrogen safely, efficiently and on a large scale. The present invention also integrates a hydrogen fuel cell unit, which can convert hydrogen stored in solid-state hydrogen storage into electrical energy, output AC power to the outside through an inverter, and can also be converted into DC power of the required voltage through a second DC transformer. After distribution by a power distributor, part of it is used to provide DC power when the solid-state hydrogen storage unit releases hydrogen, and part of it is used to output DC power to the outside. The present invention solves the problem of absorbing electricity generated by wind power and photovoltaic power, and can complete hydrogen production, hydrogen storage and power generation anytime and anywhere according to needs, transport hydrogen and transmit electricity efficiently, safely and flexibly, and promote the distributed off-grid utilization of electricity.

[0005] The solid-state hydrogen storage unit comprises a thermal insulation layer shell, a solid-state hydrogen storage material, a heating film, a hydrogen inlet, a first support plate, a second support plate, a hydrogen outlet and a temperature sensor;

[0006] The hydrogen inlet and the hydrogen outlet are symmetrically arranged at the two ends of the shell along the horizontal center line; the first support plate and the second support plate are respectively arranged in the shell and are at a certain distance from the adjacent hydrogen inlet or hydrogen outlet, that is, there is a certain accommodation space between the first support plate and the hydrogen inlet for storing hydrogen, which is convenient for the effective distribution of hydrogen; there is a certain accommodation space between the second support plate and the hydrogen outlet, and the hydrogen in the solid hydrogen storage material is collected from the hydrogen flow channel to the accommodation space, which is conducive to the continuous and stable output of hydrogen; the heating film is planar, and the heating film is tightly pressed with the solid hydrogen storage material arranged on both sides thereof to form a hydrogen storage and release unit. In order to achieve the tight pressing of the solid hydrogen storage material, a small amount of material that can play a bonding role can also be added to the solid hydrogen storage material, or a breathable material can be coated on the side of the solid hydrogen storage material away from the heating film; a plurality of hydrogen storage and release units are stacked in the cavity formed by the shell and the first support plate and the second support plate, and the number of the hydrogen storage and release units is 2-20, and the specific number depends on the design scale; the thermal insulation layer is coated on the outside of the shell;

[0007] The solid-state hydrogen storage material is provided with a probe of a temperature sensor; the central controller is respectively connected to the temperature sensor and the heating film for communication.

[0008] Furthermore, a plurality of hydrogen flow channels are provided in the horizontal direction through the first support plate, the hydrogen storage material, and the second support plate. That is, the hydrogen flow channel passes through the first support plate, the hydrogen storage material, and the second support plate in sequence, thereby connecting the hydrogen inlet and the hydrogen outlet. The cross-section of the hydrogen flow channel is circular or square. The use of such a hydrogen flow channel increases the contact area between hydrogen and the solid hydrogen storage material, increases the hydrogen flow rate, reduces the diffusion resistance of hydrogen entering the hydrogen storage material, accelerates mass transfer, further increases the hydrogen storage rate, and improves the uniformity and stability of the temperature at various locations of the hydrogen storage material, while being able to remove part of the reaction heat.

[0009] Furthermore, a coolant channel is provided between two adjacent layers of hydrogen storage and release units, and the coolant inlet and the coolant outlet are respectively provided on the end surface of the shell where the hydrogen inlet and the hydrogen outlet are not provided. The coolant in the coolant channel can timely remove the reaction heat from various places during hydrogen storage, avoid overheating of the middle part of the solid-state hydrogen storage and release device, improve the temperature stability of the hydrogen storage material, further improve the hydrogen storage efficiency, and solve the problem that the solid-state hydrogen storage and release device is difficult to scale up.

[0010] Furthermore, coolant guide plates parallel to each other are evenly arranged in the coolant channel, which can prevent the coolant from generating eddy currents and back-mixing during the flow process, thereby further improving the heat extraction efficiency.

[0011] Furthermore, a third support plate and a fourth support plate are provided at both ends of the coolant channel, and the third support plate and the fourth support plate are respectively a certain distance away from the adjacent coolant inlet and coolant outlet, and are fixedly installed on the internal cavity of the shell along the horizontal center line, so as to isolate the hydrogen and the coolant, so that the coolant is evenly distributed to each coolant channel, thereby further improving the uniformity of the coolant heat extraction.

[0012] Furthermore, a coolant flow regulating valve is provided at the coolant inlet, and the coolant flow regulating valve is communicatively connected to the central controller. The coolant flow regulating valve can control the flow of the coolant and adjust the heat load. The central controller can control the coolant flow regulating valve, thereby stably and quickly adjusting the heat load, further improving the accuracy of temperature regulation and reducing the response time.

[0013] Furthermore, a first pressure measuring port is provided on the shell at one side close to the hydrogen inlet, a second pressure measuring port is provided on the shell at one side close to the hydrogen outlet, and pressure sensors are provided on the first and second pressure measuring ports, and the pressure sensors are communicatively connected to the central controller. The pressure sensors can detect the pressure of the solid-state hydrogen storage and release unit with uniform thermal field, judge the progress of hydrogen storage and release, and further improve the efficiency and safety of hydrogen storage.

[0014] Furthermore, the hydrogen inlet is provided with a hydrogen inlet valve, the hydrogen outlet is provided with a hydrogen outlet valve 1, the outlet of the hydrogen outlet valve 1 is respectively connected with the inlet of the hydrogen outlet valve 2 and the inlet of the hydrogen circulation valve 1; the outlet of the hydrogen circulation valve 1 is connected with the heat medium inlet of the first cooler; the heat medium outlet of the first cooler is connected with the inlet of the hydrogen circulation compressor; the outlet of the hydrogen circulation compressor is connected with the heat medium inlet of the second cooler; the heat medium outlet of the second cooler is connected with the inlet of the hydrogen circulation valve 2; the outlet of the hydrogen circulation valve 2 is connected with the hydrogen inlet valve; the hydrogen inlet valve, the hydrogen outlet valve 1, the hydrogen outlet valve 2, the hydrogen circulation valve 1, and the hydrogen outlet valve 2 are respectively connected to the central controller for communication.

[0015] Hydrogen circulation can remove the heat released during hydrogen storage, and the heat can be recovered through the cooler to reduce heat loss, while reducing the hydrogen inlet temperature, which is conducive to the temperature control during the hydrogen storage stage. Hydrogen circulation can also increase the flow rate of hydrogen in the hydrogen flow channel, reduce diffusion resistance, and increase the hydrogen storage rate.

[0016] Furthermore, the cross-sectional shape of the shell includes but is not limited to one of a circle, an ellipse, a rectangle and a square. If the cross-sectional shape of the shell is a circle or an ellipse, the manufacturing cost can be saved under the same operating pressure and strength requirements.

[0017] Furthermore, the solid-state hydrogen storage material is LiMgNH, MgH2 、LaNi 5 、LaNi 4.6 Al 0.4 、LaNi 4.5 Al 0.5 、LaNi 4.5 Mn 0.5 、CaNi 5 、Ti 1.2 Mn 1.8 、TiCr 1.8 、ZrMn 2 、ZrV、TiFe、Mg 2 One or more of Ni.

[0018] Furthermore, the solid-state hydrogen storage material is preferably LiMgNH and / or MgH 2 .

[0019] Furthermore, the heating film is a carbon nanotube heating film, a carbon fiber heating film or a graphene heating film.

[0020] Furthermore, the heating film is preferably a carbon nanotube heating film.

[0021] Furthermore, the heating film has a thickness of 0.05-5 mm, preferably 0.2-2 mm.

[0022] Furthermore, the thickness of the solid hydrogen storage material after pressing is 0.5-5 cm, preferably 1-3 cm.

[0023] Furthermore, the hydrogen inlet is provided with a hydrogen inlet valve, the hydrogen outlet is provided with a hydrogen outlet valve 1, the outlet of the hydrogen outlet valve 1 is respectively connected with the inlet of the hydrogen outlet valve 2 and the inlet of the hydrogen circulation valve 1; the outlet of the hydrogen circulation valve 1 is connected with the heat medium inlet of the first cooler; the heat medium outlet of the first cooler is connected with the inlet of the hydrogen circulation compressor; the outlet of the hydrogen circulation compressor is connected with the heat medium inlet of the second cooler; the heat medium outlet of the second cooler is connected with the inlet of the hydrogen circulation valve 2; the outlet of the hydrogen circulation valve 2 is connected with the hydrogen inlet valve; the hydrogen inlet valve, the hydrogen outlet valve 1, the hydrogen outlet valve 2, the hydrogen circulation valve 1, and the hydrogen circulation valve 2 are respectively connected to the central controller for communication.

[0024] Furthermore, a plurality of temperature sensors are evenly arranged on the solid-state hydrogen storage material, and are respectively arranged in the solid-state hydrogen storage materials of different hydrogen storage and desorption units, and the temperature sensors are communicatively connected with the central controller.

[0025] Furthermore, the power supply unit includes an AC input interface, a DC input interface, a photovoltaic module, a first DC transformer, a rectifier and a battery; the photovoltaic module is electrically connected to the first DC transformer; the first DC transformer is electrically connected to the battery, the hydrogen production unit, the solid-state hydrogen storage unit and the hydrogen fuel cell unit respectively; the rectifier is electrically connected to the battery, the hydrogen production unit, the solid-state hydrogen storage unit and the hydrogen fuel cell unit respectively.

[0026] Furthermore, the hydrogen production unit is one of an alkaline water electrolysis device, a proton exchange membrane pure water electrolysis device, an anion exchange membrane water electrolysis device and a solid oxide water electrolysis device.

[0027] Furthermore, the hydrogen fuel cell unit includes an inverter and a second DC transformer.

[0028] Such a combination can flexibly match various forms of power sources such as industrial electricity, wind power, photovoltaics, etc. The built-in photovoltaic components can also supply part of the electricity when the sunlight is sufficient. The electric energy stored in the battery can provide power for the cold start of the solid-state hydrogen storage unit and hydrogen fuel power supply in the absence of external power supply.

[0029] Another object of the present invention is to disclose a method for integrated operation of hydrogen production, solid-state hydrogen storage and hydrogen fuel cell, comprising the following steps:

[0030] When producing hydrogen, the output voltage of the power supply unit and the hydrogen output flow rate of the hydrogen production unit are set on the central controller, and the hydrogen production unit is powered on to start producing hydrogen;

[0031] When storing hydrogen, the hydrogen inlet is opened, the hydrogen outlet is closed, and the hydrogen storage temperature T1 is set on the central controller. Hydrogen enters the solid-state hydrogen storage and release unit from the hydrogen inlet, flows through the accommodation space between the first support plate and the hydrogen inlet, and is evenly distributed in the solid-state hydrogen storage material through the hydrogen flow channel. As the temperature rises, hydrogen reacts with the solid-state hydrogen storage material to generate metal hydride. When the reaction temperature reaches the starting temperature T2, the central controller stops supplying power to the heating film. Since the hydrogen storage reaction is an exothermic reaction, the released reaction heat needs to remove part of the reaction heat in addition to the heat to maintain the hydrogen storage temperature stable at T1. At this time, the central controller adjusts the coolant flow regulating valve to adjust the coolant flow so that the temperature measured by the temperature sensor is stable at T1, and the solid-state hydrogen storage and release unit is kept stable and uniformly storing hydrogen. When the central controller detects that the pressure measured by the pressure sensor begins to rise rapidly, the hydrogen inlet is closed, the hydrogen production unit is closed, and the hydrogen storage is completed;

[0032] When releasing hydrogen, close the hydrogen inlet, open the hydrogen outlet, set the hydrogen release temperature T3 on the central controller, and supply power to the heating film. The temperature of the solid hydrogen storage material rises. When the temperature rises to the hydrogen release temperature T3, the solid hydrogen storage material releases hydrogen stably. The central controller controls the heating power of the heating film to stabilize the measured temperature of the temperature sensor at T3. Set the hydrogen output lower limit flow rate L1 on the central control. When the measured hydrogen outlet flow rate drops to the hydrogen output lower limit L1, and the pressure measured by the pressure sensor drops rapidly, close the hydrogen outlet and the hydrogen release is completed.

[0033] When generating electricity, the flow rate of hydrogen released by the solid-state hydrogen storage unit is set in the central controller, and the solid-state hydrogen storage unit is started to supply hydrogen to the hydrogen fuel cell unit. The hydrogen fuel cell unit generates electrical energy, and the electrical energy can be used in one or more of the following ways: converted into alternating current for external output through an inverter, converted into direct current for external output through a second direct current transformer, and provided with power for the solid-state hydrogen storage unit to release hydrogen in the absence of an external power supply and to store electricity in the battery.

[0034] Furthermore, at the beginning of hydrogen storage, the hydrogen outlet is not opened, and when the reaction temperature reaches the starting temperature T2, the hydrogen outlet is closed.

[0035] Furthermore, when storing hydrogen, first open the hydrogen inlet valve; then open the hydrogen outlet valve one, close the hydrogen outlet valve two, and open the hydrogen circulation valve one and the hydrogen circulation valve two; set the first cooler outlet temperature T4 on the central controller, and the central controller controls the first cooler refrigerant temperature or flow to stabilize the first cooler outlet temperature at T4; set the second cooler outlet temperature T5 on the central controller, and the central controller controls the first cooler refrigerant temperature or flow to stabilize the second cooler outlet temperature at T5; after the hydrogen storage is completed, close the hydrogen inlet valve, hydrogen outlet valve one, hydrogen outlet valve two, hydrogen circulation valve one and hydrogen circulation valve two.

[0036] It should be noted that in the present invention, T1, T2, T3, T4, T5 and L1 are all determined by factors such as the actual operating environment and production scale.

[0037] Furthermore, there are multiple solid-state hydrogen storage units and multiple hydrogen fuel cell units; the solid-state hydrogen storage unit is electrically connected to the hydrogen fuel cell unit and connected through a hydrogen supply pipeline; the solid-state hydrogen storage unit and the hydrogen fuel cell unit are respectively connected to the central controller for communication;

[0038] The solid-state hydrogen storage unit and the hydrogen fuel cell unit can be connected through the hydrogen supply pipeline in the following form: each of the solid-state hydrogen storage units is connected to each hydrogen fuel cell unit through a hydrogen supply pipeline. The solid-state hydrogen storage unit and the hydrogen fuel cell unit can be connected through the hydrogen supply pipeline in the following form: the solid-state hydrogen storage unit is connected to the fuel cell unit through a hydrogen supply branch pipe, a main pipe and a fuel cell branch pipe in sequence. Specifically, a plurality of solid-state hydrogen storage units are respectively connected to the main pipe through hydrogen supply branch pipes, and the main pipe is connected to a plurality of hydrogen fuel cell units through fuel cell branch pipes.

[0039] Similarly, the electrical connection between the solid-state hydrogen storage unit and the hydrogen fuel cell unit can be achieved by each of the solid-state hydrogen storage units being electrically connected to each of the hydrogen fuel cell units. The connection between the solid-state hydrogen storage unit and the hydrogen fuel cell unit through the hydrogen supply pipeline can also be achieved as follows: the solid-state hydrogen storage unit is electrically connected to the fuel cell unit through the hydrogen supply branch line, the bus and the fuel cell branch line in sequence. Specifically, multiple solid-state hydrogen storage units are electrically connected to the bus through the hydrogen supply branch line, and the bus is electrically connected to multiple hydrogen fuel cell units through the fuel cell branch line.

[0040] Furthermore, the method for operating the skid-mounted hydrogen production, solid-state hydrogen storage and hydrogen fuel cell integrated system for hydrogen release and / or power generation includes:

[0041] S1: preset the output value of the electric energy and / or hydrogen output by the system;

[0042] S2: receiving a signal indicating a start-up system, starting at least one solid-state hydrogen storage unit, and outputting start-up hydrogen; the signal is a solid-state hydrogen storage unit start-up signal or a fuel cell unit start-up signal;

[0043] S3: delivering starting hydrogen to at least one hydrogen fuel cell unit, starting the hydrogen fuel cell unit that obtains the starting hydrogen, and outputting electrical energy;

[0044] S4: delivering the electric energy to the solid-state hydrogen storage unit that has released hydrogen and / or the new solid-state hydrogen storage unit, so that the solid-state hydrogen storage unit that has released hydrogen and obtained the electric energy maintains a state of outputting hydrogen and / or starts the new solid-state hydrogen storage unit that obtains the electric energy to output hydrogen;

[0045] S5: Repeat steps S3 and / or S4 to output electrical energy or hydrogen to the outside of the system; when the output of electrical energy or hydrogen to the outside of the system reaches the output value, stop repeating steps S3 and / or S4.

[0046] Wherein, in step S3, the number of solid-state hydrogen storage units started is not less than the number of solid-state hydrogen storage units started in S2.

[0047] Further, in S5, the number of solid-state hydrogen storage units and / or hydrogen fuel cell units started each time is greater than the number of solid-state hydrogen storage units and / or hydrogen fuel cell units started last time. Specifically, the number of solid-state hydrogen storage units started each time is greater than the number of solid-state hydrogen storage units started last time. The number of solid-state hydrogen storage units and hydrogen fuel cell units started each time is greater than the number of solid-state hydrogen storage units and hydrogen fuel cell units started last time. The number of hydrogen fuel cell units started each time is greater than the number of hydrogen fuel cell units started last time.

[0048] Furthermore, before receiving a signal indicating starting the hydrogen supply system and / or the fuel cell system, the number of solid-state hydrogen storage units and / or hydrogen fuel cell units to be started each time is preset.

[0049] Further, when the signal is a hydrogen supply system start-up signal, in S5: hydrogen is output to the outside of the system;

[0050] When the signal is a fuel cell system start-up signal, in S5, electric energy is output to the outside of the system.

[0051] Further, the hydrogen supply system and / or the fuel cell system further comprises a plurality of first temperature detection units for detecting the temperature of the solid-state hydrogen storage unit;

[0052] Each first temperature detection unit is communicatively connected to the central controller;

[0053] S4 includes:

[0054] S41: before starting the solid-state hydrogen storage unit, obtain the real-time temperature of each solid-state hydrogen storage unit, and sort the temperatures of the unstarted solid-state hydrogen storage units according to the real-time temperature;

[0055] S42: determining the solid-state hydrogen storage unit to be started according to the temperature ranking of the unstarted solid-state hydrogen storage units, and transmitting electric energy to the solid-state hydrogen storage unit to be started;

[0056] Among them, the solid-state hydrogen storage unit to be started is determined according to the temperature sorting of the solid-state hydrogen storage unit, including:

[0057] According to the real-time temperature of the solid-state hydrogen storage unit, the temperature of the unactivated solid-state hydrogen storage units in the system is sorted from high to low or from low to high, so as to obtain the current startup sequence of the unactivated solid-state hydrogen storage units;

[0058] Start the multiple solid-state hydrogen storage units sequentially or simultaneously according to the number of solid-state hydrogen storage units to be started and the current start-up order of the unstarted solid-state hydrogen storage units;

[0059] Among them, the startup sequence of the unstarted solid-state hydrogen storage units is that the unstarted solid-state hydrogen storage units with higher temperatures are started first.

[0060] Furthermore, the hydrogen supply system and / or the fuel cell system further comprises a plurality of second temperature detection units for detecting the temperature of the hydrogen fuel cell units;

[0061] Each second temperature detection unit is communicatively connected to the central controller;

[0062] S1 also includes: presetting a temperature threshold of the hydrogen fuel cell unit; the temperature threshold is the upper limit temperature of the safe operation of the hydrogen fuel cell unit;

[0063] After S5, S6 is also included, and S6 includes:

[0064] S601: regularly obtaining the real-time temperature of each hydrogen fuel cell unit, and determining whether the real-time temperature of the hydrogen fuel cell unit in the startup state is less than a temperature threshold;

[0065] S602: When the judgment result is yes, stop the startup state of the hydrogen fuel cell unit; when the judgment result is no, maintain the startup state of the hydrogen fuel cell unit;

[0066] S603: when the judgment result of the a hydrogen fuel cell units in the started state is yes, starting the a hydrogen fuel cell units in the system in the unstarted state;

[0067] Wherein, a is a natural number.

[0068] Further, in S6, before starting a hydrogen fuel cell unit in the system that is in an unstarted state, the process further includes:

[0069] Sorting the hydrogen fuel cell units in an unstarted state according to the real-time temperature of each hydrogen fuel cell unit to obtain a start priority order of the hydrogen fuel cell units in an unstarted state;

[0070] Determining a number of hydrogen fuel cell units in an unstarted state to be started according to the start-up priority order of the hydrogen fuel cell units in an unstarted state;

[0071] Among them, the activation priority order of the hydrogen fuel cell units in the non-activated state is that the hydrogen fuel cell units in the non-activated state with lower temperatures are activated first.

[0072] Furthermore, the hydrogen supply system and / or the fuel cell system further comprises a plurality of gas flow detection units for detecting the flow rate of hydrogen output by the solid-state hydrogen storage unit;

[0073] Each gas flow detection unit is communicatively connected with the central controller;

[0074] S1 also includes: presetting a flow rate threshold of a minimum flow rate of hydrogen output by the solid-state hydrogen storage unit;

[0075] After S5, S6 is also included, and S6 includes:

[0076] S611: regularly obtaining the real-time output hydrogen flow rate of each solid-state hydrogen storage unit in the startup state, and determining whether the real-time output hydrogen flow rate of the solid-state hydrogen storage unit in the startup state is less than a flow threshold;

[0077] S612: When the judgment result is yes, stop the startup state of the solid-state hydrogen storage unit; when the judgment result is no, maintain the startup state of the hydrogen fuel cell unit.

[0078] S613: When the judgment result of b solid-state hydrogen storage units in the startup state is no, start b solid-state hydrogen storage units in the system that are not in the startup state; wherein b is a natural number.

[0079] Furthermore, in S6, before starting b solid-state hydrogen storage units in the system that are in an unstarted state, the method further includes:

[0080] Sorting the solid-state hydrogen storage units in an unactivated state according to the real-time temperature of each solid-state hydrogen storage unit to obtain the activation priority order of the solid-state hydrogen storage units in an unactivated state;

[0081] Determining b unactivated solid-state hydrogen storage units to be activated according to the activation priority order of the unactivated solid-state hydrogen storage units;

[0082] Among them, the activation priority order of the solid-state hydrogen storage units in the unactivated state is that the solid-state hydrogen storage units in the unactivated state with higher temperatures are activated first.

[0083] Further, in S613, starting b solid-state hydrogen storage units in the system that are in an unstarted state includes:

[0084] disconnecting the electrical connection relationship between the b solid-state hydrogen storage units in the startup state and the corresponding hydrogen fuel cell units when the judgment result is no;

[0085] An electrical connection relationship is established between the b unactivated solid-state hydrogen storage units to be activated and the corresponding hydrogen fuel cell units, so that the hydrogen fuel cell units supply power to the b unactivated solid-state hydrogen storage units to be activated.

[0086] The skid-mounted hydrogen production, solid-state hydrogen storage and hydrogen fuel cell integrated system of the present invention has a simple, compact and movable structure, can absorb scattered and unstable electricity such as wind power and photovoltaic power, and improve the utilization rate of clean energy. Compared with the prior art, it has the following advantages:

[0087] 1) The power supply unit of the present invention includes multiple power interfaces, equipped with rectification and voltage regulation devices, and can accept multiple power sources. At the same time, the device of the present invention has its own photovoltaic panel, which can generate electricity under conditions where light permits, and provide partial power supply for the device. The device integrates a solid-state hydrogen storage unit and a hydrogen fuel cell unit, and can choose to provide hydrogen or electricity to the outside as needed, expanding the utilization of clean energy. The skid-mounted method is flexible and can quickly provide hydrogen and electricity for a variety of limited conditions.

[0088] 2) The present invention adopts a planar heating film to provide heat for the solid hydrogen storage material. The heating film has a high electrothermal conversion efficiency, and the planar structure increases the heat transfer area. The temperature uniformity of the heating surface is good. Under the condition of providing the same amount of heat, the temperature of the heating surface is lower than the temperature required by the linear heating method, which is beneficial to extending the service life of the equipment and achieving a better heat transfer effect.

[0089] 3) The liquid cooling heat extraction method of the present invention can timely extract the reaction heat during hydrogen storage, avoiding the problem of temperature gradient formed by poor heat dissipation in the solid-state hydrogen storage and desorption device, thereby affecting the hydrogen storage efficiency and capacity, and solving the problem that the solid-state hydrogen storage and desorption device is difficult to scale up due to poor heat dissipation.

[0090] 4) The hydrogen circulation method adopted by the present invention during hydrogen storage can significantly reduce the hydrogen inlet temperature and recycle the reaction heat. At the same time, the hydrogen circulation increases the flow rate of hydrogen in the flow channel, reduces the diffusion resistance, increases the reaction speed, shortens the hydrogen storage time, and improves the hydrogen storage efficiency.

[0091] 5) The automated control system of the present invention can timely control temperature changes, has a short response time, and can smoothly control temperature, thereby improving the accuracy and stability of control, ensuring that the thermal field of the solid-state hydrogen storage and degassing device remains stable and uniform, improving the hydrogen storage and degassing efficiency, and reducing energy consumption.

[0092] In summary, the present invention integrates power supply, hydrogen production, solid-state hydrogen storage and hydrogen fuel cell devices in a skid-mounted container-type housing. The equipment layout is compact and easy to move. It can flexibly use the electric energy generated by wind power and photovoltaics to electrolyze water to produce hydrogen in a flexible time and place, and convert hydrogen into metal hydrides with stable chemical properties and large hydrogen carrying capacity through a solid-state hydrogen storage unit, so that hydrogen can be transported safely, efficiently and on a large scale. The present invention also integrates a hydrogen fuel cell unit, which can convert hydrogen stored in solid-state hydrogen storage into electrical energy, output AC power to the outside through an inverter, and can also be converted into DC power of the required voltage through a second DC transformer. After distribution by a power distributor, a part of it provides DC power for the solid-state hydrogen storage unit when releasing hydrogen, and a part of it outputs DC power to the outside. The present invention solves the problem of absorbing the power generated by wind power and photovoltaics, and can complete hydrogen production, hydrogen storage and power generation anytime and anywhere according to needs, efficiently, safely and flexibly transport hydrogen and transmit electricity, and promote the distributed off-grid utilization of electricity. BRIEF DESCRIPTION OF THE DRAWINGS

[0093] Figure 1 This is a front cross-sectional view of the solid-state hydrogen storage unit of Example 1.

[0094] Figure 2 It is a right side cross-sectional view of the solid-state hydrogen storage unit of Example 1.

[0095] Figure 3 This is a top view of the cross-section of the solid-state hydrogen storage unit of Example 1.

[0096] Figure 4 This is a schematic diagram of the operation flow of the solid-state hydrogen storage unit of Example 1.

[0097] Figure 5 This is a schematic diagram of the structure of the skid-mounted hydrogen production, solid-state hydrogen storage and hydrogen fuel cell integrated system of Example 1.

[0098] 1. Coolant inlet; 2. Third support plate; 3. Insulation layer; 4. Shell; 5. Solid hydrogen storage material; 6. Hydrogen flow channel; 7. Heating film; 8. Fourth support plate; 9. Coolant outlet; 10. Hydrogen inlet; 11. First support plate; 12. Second pressure measuring port; 13. Second support plate; 14. Hydrogen outlet; 15. Central controller; 16. Temperature sensor; 17. Hydrogen inlet valve; 18. Coolant flow regulating valve; 19. Coolant channel; 20. Coolant guide plate; 21. Coolant channel upper wall plate; 22. Coolant channel lower wall plate; 23. Hydrogen Gas outlet valve one; 24, hydrogen outlet valve two; 25, hydrogen circulation valve one; 26, first cooler; 27, hydrogen circulation compressor; 28, second cooler; 29, hydrogen circulation valve two; 30, skid-mounted shell; 31, power supply unit; 32, hydrogen production unit; 33, solid-state hydrogen storage unit; 34, hydrogen fuel cell unit; 35, photovoltaic module; 36, first DC transformer; 37, rectifier; 38, battery; 39, inverter; 40, second DC transformer. DETAILED DESCRIPTION

[0099] The technical solution of the present application will be described clearly and completely in conjunction with the embodiments below. Obviously, the described embodiments are part of the embodiments of the present application, not all of the embodiments. Based on the embodiments in the present application, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present application.

[0100] In the description of this patent, when an element is referred to as being "fixed to / mounted on (or similar terms)" another element, it may be directly on the other element or there may be intervening elements. When an element is considered to be "connected to" another element, it may be directly connected to the other element or there may be intervening elements at the same time. On the contrary, when an element is referred to as being "directly on" another element, there are no intervening elements.

[0101] In the description of this patent, it should be understood that the terms "front", "rear", "left", "right", "inside", "outside", etc. indicate directions or positional relationships based on the directions or positional relationships shown in the accompanying drawings, and are only for the convenience of describing this patent and simplifying the description, rather than indicating or implying that the device or element referred to must have a specific direction, be constructed and operated in a specific direction, and therefore cannot be understood as a limitation on this patent. In the description of this application below, it should be understood that "multiple" means two or more, unless otherwise clearly and specifically defined.

[0102] The following is a detailed description of an implementation of a skid-mounted hydrogen production, solid-state hydrogen storage and hydrogen fuel cell integrated system of the present invention in conjunction with the accompanying drawings.

[0103] Example 1

[0104] This embodiment discloses a skid-mounted hydrogen production, solid-state hydrogen storage and hydrogen fuel cell integrated system. Figure 1-5 As shown, it includes a skid-mounted housing 30, a power supply unit 31, a hydrogen production unit 32, a solid-state hydrogen storage unit 33, a hydrogen fuel cell unit 34 and a central controller 15; the power supply unit 31, the hydrogen production unit 32, the solid-state hydrogen storage unit 33, the hydrogen fuel cell unit 34 and the central controller 15 are arranged in the skid-mounted housing 30; the power supply unit 31 is electrically connected to the hydrogen production unit 32, the solid-state hydrogen storage unit 33, the hydrogen fuel cell unit 34 and the central controller 15 respectively, the central controller 15 is communicatively connected to the power supply unit 31, the hydrogen production unit 32, the solid-state hydrogen storage unit 33 and the hydrogen fuel cell unit 34 respectively, and the central control room 15 is wirelessly connected to the remote control terminal; the hydrogen production unit 32, the solid-state hydrogen storage unit 33 and the hydrogen fuel cell unit 34 are connected in sequence through pipelines; the hydrogen fuel cell unit 34 is electrically connected to the solid-state hydrogen storage unit 33;

[0105] The power supply unit 31 includes an AC input interface, a DC input interface, a photovoltaic module 35, a first DC transformer 36, a rectifier 37, and a battery 38; the photovoltaic module 35 is electrically connected to the first DC transformer 36; the first DC transformer 36 is electrically connected to the battery 38, the hydrogen production unit 32, the solid-state hydrogen storage unit 33, and the hydrogen fuel cell unit 34 respectively; the rectifier 37 is electrically connected to the battery 38, the hydrogen production unit 32, the solid-state hydrogen storage unit 33, and the hydrogen fuel cell unit 34 respectively.

[0106] The hydrogen production unit 32 is a proton exchange membrane pure water electrolysis device;

[0107] The hydrogen fuel cell unit 34 includes an inverter 39 and a second DC transformer 40 .

[0108] The solid-state hydrogen storage unit 33 includes a thermal insulation layer 3, a shell 4, a solid-state hydrogen storage material 5, a heating film 7, a hydrogen inlet 10, a first support plate 11, a second support plate 13, a hydrogen outlet 14 and a temperature sensor 16;

[0109] The shell of this embodiment is rectangular and its cross section is square. It can be understood that the cross section can also be circular, elliptical, rectangular, etc. If the shell cross section is circular or elliptical, the manufacturing cost can be saved under the same operating pressure and strength requirements.

[0110] The hydrogen inlet 10 and the hydrogen outlet 14 are symmetrically arranged at both ends of the shell 4 along the horizontal center line; the first support plate 11 and the second support plate 13 are respectively arranged in the shell 4, and are a certain distance away from the adjacent hydrogen inlet 10 or the hydrogen outlet 14, that is, there is a certain accommodation space between the first support plate 11 and the hydrogen inlet 10, which is used to store hydrogen and facilitate the effective distribution of hydrogen; there is a certain accommodation space between the second support plate 13 and the hydrogen outlet 14, and the hydrogen in the solid hydrogen storage material 5 is collected from the hydrogen flow channel 6 to the accommodation space, which is conducive to the continuous and stable output of hydrogen; the arrangement direction of the first support plate 11 and the second support plate 13 is perpendicular to the line connecting the hydrogen inlet 10 and the hydrogen outlet 14, that is, perpendicular to the flow direction of hydrogen.

[0111] The heating film 7 is in a planar shape, and the heating film 7 is tightly pressed with the solid hydrogen storage material 5 arranged on both sides thereof to form a hydrogen storage and release unit. The solid hydrogen storage material 5 described in this embodiment is LiMgNH. The heating film 7 is a carbon nanotube heating film. The thickness of the heating film 7 is 0.05 to 5 mm. The thickness of the solid hydrogen storage material 5 after pressing is 0.5 to 5 cm. In order to achieve the tight pressing of the solid hydrogen storage material 5, a small amount of material that can play a bonding role can also be added to the solid hydrogen storage material 5, or a breathable material can be coated on the side of the solid hydrogen storage material 5 away from the heating film 7.

[0112] Three hydrogen storage and release units are stacked in the cavity formed by the shell 4, the first support plate 11 and the second support plate 13. The thermal insulation layer 3 is coated on the outside of the shell 4;

[0113] The solid hydrogen storage material 5 is provided with a probe of a temperature sensor 16; the central controller 15 is respectively connected to the temperature sensor 16 and the heating film 7. In this embodiment, there are multiple temperature sensors 16, which are respectively provided in the solid hydrogen storage materials 5 of different hydrogen storage and release units.

[0114] The solid-state hydrogen storage and desorption method of the solid-state hydrogen storage and desorption unit of the present invention comprises the following steps: firstly, the working temperature of the solid-state hydrogen storage material is set, and the central controller controls the power of the heating film according to the signal of the temperature sensor arranged in the solid-state hydrogen storage material, so that the heating film is heated, and the solid-state hydrogen storage material tightly attached to the planar heating film is evenly heated and heated, thereby realizing stable hydrogen storage and desorption.

[0115] A plurality of hydrogen flow channels 6 are provided in the horizontal direction through the first support plate 11, the hydrogen storage material 5 and the second support plate 13. That is, the hydrogen flow channel 6 passes through the first support plate 11, the hydrogen storage material 5 and the second support plate 13 in sequence, and then connects the hydrogen inlet 10 and the hydrogen outlet 14. The cross section of the hydrogen flow channel 6 is circular or square. The use of such a hydrogen flow channel increases the contact area between hydrogen and the solid hydrogen storage material, increases the hydrogen flow rate, reduces the diffusion resistance of hydrogen entering the hydrogen storage material, accelerates mass transfer, further increases the hydrogen storage rate, improves the uniformity and stability of the temperature at various locations of the hydrogen storage material, and can remove part of the reaction heat.

[0116] A coolant channel 19 is provided between two adjacent layers of hydrogen storage and release units. The coolant channel 19 is isolated from the solid hydrogen storage material 5 by the upper wall plate 21 and the lower wall plate 22 of the coolant channel. The coolant inlet 1 and the coolant outlet 9 of the coolant channel 19 are respectively provided on the end surface of the shell where the hydrogen inlet 10 and the hydrogen outlet 14 are not provided. The coolant in the coolant channel can timely remove the reaction heat from various places during hydrogen storage, avoid overheating of the middle part of the solid hydrogen storage and release device, improve the temperature stability of the hydrogen storage material, further improve the hydrogen storage efficiency, and solve the problem that the solid hydrogen storage and release device is difficult to be large-scale.

[0117] The coolant channel is evenly provided with coolant guide plates parallel to each other, which can avoid eddy currents and back mixing of the coolant during its flow, thereby further improving the heat extraction efficiency.

[0118] A third support plate 2 and a fourth support plate 8 are provided at both ends of the coolant channel 19. The third support plate 2 and the fourth support plate 8 are respectively spaced a certain distance from the adjacent coolant inlet 1 and the coolant outlet 9, and are fixedly installed in the internal cavity of the shell along the horizontal center line to isolate the hydrogen and the coolant, so that the coolant is evenly distributed to each coolant channel, further improving the uniformity of the coolant heat extraction.

[0119] A coolant flow regulating valve is provided at the coolant inlet, and the coolant flow regulating valve is communicatively connected to the central controller 15. The coolant flow regulating valve can control the flow of the coolant and adjust the heat load.

[0120] The central controller 15 is respectively connected to the coolant flow regulating valve 18 and the temperature sensor 16. The central controller 15 can automatically adjust the heat load stably and quickly, further improve the accuracy of temperature regulation, and reduce the response time.

[0121] A first pressure measuring port is provided on the shell 4 at one side close to the hydrogen inlet 10, and a second pressure measuring port 12 is provided on the shell 4 at one side close to the hydrogen outlet 14. Pressure sensors are provided on the first pressure measuring port and the second pressure measuring port 12, and the pressure sensors are communicatively connected with the central controller 15. The pressure sensors can detect the pressure of the solid-state hydrogen storage and release unit with uniform thermal field, judge the progress of hydrogen storage and release, and further improve the hydrogen storage efficiency and safety.

[0122] In this embodiment, the solid hydrogen storage unit 33 is provided with a hydrogen circulation process as follows: Figure 4 As shown, it includes a hydrogen outlet valve 1 23, a hydrogen outlet valve 2 24, a hydrogen circulation valve 1 25, a first cooler 26, a hydrogen circulation compressor 27, a second cooler 28, and a hydrogen circulation valve 29. The first cooler 26 and the second cooler 28 include but are not limited to plate heat exchangers or tube-in-tube heat exchangers.

[0123] The hydrogen inlet 10 is provided with a hydrogen inlet valve 17, and the hydrogen outlet 14 is provided with a hydrogen outlet valve 1 23, and the outlet of the hydrogen outlet valve 1 23 is respectively connected with the inlet of the hydrogen outlet valve 2 24 and the inlet of the hydrogen circulation valve 1 25; the outlet of the hydrogen circulation valve 1 25 is connected with the heat medium inlet of the first cooler 26; the heat medium outlet of the first cooler 26 is connected with the inlet of the hydrogen circulation compressor 27; the outlet of the hydrogen circulation compressor 27 is connected with the heat medium inlet of the second cooler 28; the heat medium outlet of the second cooler 28 is connected with the inlet of the hydrogen circulation valve 2 29; the outlet of the hydrogen circulation valve 2 29 is connected with the hydrogen inlet valve 17; the hydrogen inlet valve 17, the hydrogen outlet valve 1 23, the hydrogen outlet valve 2 24, the hydrogen circulation valve 1 25, and the hydrogen circulation valve 2 29 are respectively connected to the central controller 15 for communication.

[0124] The method of using a skid-mounted hydrogen production, solid-state hydrogen storage and hydrogen fuel cell integrated system of this embodiment to produce hydrogen, store and release hydrogen, and supply power to the outside is as follows: comprising the following steps:

[0125] When producing hydrogen, the output voltage of the power supply unit is set in the central controller 15, the hydrogen production unit 32 is powered on, the hydrogen output flow rate of the hydrogen production unit 32 is set, and the hydrogen production unit 32 is started to start hydrogen production;

[0126] When storing hydrogen, the hydrogen inlet 10 is opened, the hydrogen outlet 14 is closed, and the hydrogen storage temperature T1 is set on the central controller 15. Hydrogen enters the solid-state hydrogen storage and release unit from the hydrogen inlet 10, flows through the accommodation space between the first support plate 11 and the hydrogen inlet 10, and is evenly distributed in the solid-state hydrogen storage material 5 through the hydrogen flow channel 6. The hydrogen outlet 14 is slightly opened, and the flow rate of the hydrogen outlet 14 is controlled so that the pressure measured by the pressure sensor is stable at P1. As the temperature rises, the hydrogen reacts with the solid-state hydrogen storage material 5 to generate metal hydride. When the reaction temperature reaches the starting temperature T2, the central controller 15 stops supplying power to the heating film 7. Since the hydrogen storage reaction is an exothermic reaction, the released reaction heat needs to remove part of the reaction heat in addition to the heat to maintain the hydrogen storage temperature stable at T1. At this time, the central controller 15 adjusts the coolant flow regulating valve 18 to adjust the coolant flow so that the temperature sensor 16 determines that the temperature is stable at T1, and the solid-state hydrogen storage and release unit is kept to store hydrogen stably and evenly. When the central controller 15 detects that the pressure measured by the pressure sensor begins to rise rapidly, the hydrogen inlet 10 is closed, and the hydrogen storage is completed; the hydrogen inlet valve 17 is opened; then the hydrogen outlet valve 1 23 is opened, the hydrogen outlet valve 2 24 is closed, and the hydrogen circulation valve 1 25 and the hydrogen circulation valve 2 29 are opened; the outlet temperature T4 of the first cooler 26 is set on the central controller 15, and the central controller 15 controls the refrigerant temperature or flow of the first cooler 26 to stabilize the outlet temperature of the first cooler 26 at T4; the outlet temperature T5 of the second cooler 28 is set on the central controller 15, and the central controller 15 controls the refrigerant temperature or flow of the first cooler 26 to stabilize the outlet temperature of the second cooler 28 at T5; after the hydrogen storage is completed, the hydrogen inlet valve 17, the hydrogen outlet valve 1 23, the hydrogen outlet valve 2 24, the hydrogen circulation valve 1 25 and the hydrogen circulation valve 2 29 are closed.

[0127] When releasing hydrogen, the hydrogen inlet 10 is closed, the hydrogen outlet 14 is opened, and the hydrogen release temperature T3 is set on the central controller 15. The central controller 15 supplies power to the heating film 7, and the temperature of the solid hydrogen storage material 5 rises. When the temperature rises to T3, the solid hydrogen storage material 5 releases hydrogen stably. The central controller 15 automatically controls the measured temperature of the temperature sensor 16 to be stable at T3. The hydrogen flow rate L1 is set on the central control, and the flow rate of the hydrogen outlet 14 is measured. When the hydrogen outlet flow rate drops to L1 and the pressure measured by the pressure sensor drops rapidly, the hydrogen outlet 14 is closed and the hydrogen release is completed.

[0128] During power generation, the flow rate of hydrogen released by the solid-state hydrogen storage unit 33 is set in the central controller 15, and the solid-state hydrogen storage unit 33 is started to supply hydrogen to the hydrogen fuel cell unit 34. The electricity generated by the hydrogen fuel cell can be converted into AC power of the required voltage via the inverter 39 for external output, or it can be converted into DC power of the required voltage for external output via the second DC transformer 40. At the same time, it provides power for the solid-state hydrogen storage unit to release hydrogen in the absence of an external power supply.

[0129] A skid-mounted integrated system of hydrogen production, solid-state hydrogen storage and hydrogen fuel cells according to the embodiment is adopted, and the power supply, hydrogen production, solid-state hydrogen storage and hydrogen fuel cell units are integrated in a skid-mounted container-type housing. The equipment has a compact layout and is easy to move. It can flexibly utilize the electric energy generated by wind power and photovoltaics to electrolyze water to produce hydrogen in a flexible time and location, and convert hydrogen into metal hydrides with stable chemical properties and large hydrogen carrying capacity through a solid-state hydrogen storage unit. It can transport hydrogen safely, efficiently and on a large scale. In addition, a hydrogen fuel cell unit is integrated in the device, which can convert hydrogen stored in solid-state hydrogen storage into electric energy, and output AC power to the outside through an inverter, or can be converted into DC power of the required voltage through a second DC transformer. After distribution by a power distributor, a part of it provides DC power for the solid-state hydrogen storage unit when releasing hydrogen, and a part of it outputs DC power to the outside. The problem of absorbing the electricity generated by wind power and photovoltaics is solved, and hydrogen production and storage can be completed anytime and anywhere at any power source according to needs, and hydrogen and electricity can be transported efficiently, safely and flexibly, promoting the distributed off-grid utilization of electricity.

[0130] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present application, rather than to limit it. Although the present application has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or replace some or all of the technical features therein with equivalents. However, these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present application.

Claims

1. A skid-mounted integrated system of hydrogen production, solid-state hydrogen storage and hydrogen fuel cells, characterized in that: The invention comprises a skid-mounted housing (30), a power supply unit (31), a hydrogen production unit (32), a solid-state hydrogen storage unit (33), a hydrogen fuel cell unit (34) and a central controller (15); the power supply unit (31), the hydrogen production unit (32), the solid-state hydrogen storage unit (33), the hydrogen fuel cell unit (34) and the central controller (15) are arranged in the skid-mounted housing (30); the power supply unit (31) is electrically connected to the hydrogen production unit (32), the solid-state hydrogen storage unit (33), the hydrogen fuel cell unit (34) and the central controller (15) respectively; the central controller (15) is communicatively connected to the power supply unit (31), the hydrogen production unit (32), the solid-state hydrogen storage unit (33) and the hydrogen fuel cell unit (34) respectively; the hydrogen production unit (32), the solid-state hydrogen storage unit (33) and the hydrogen fuel cell unit (34) are connected in sequence through pipelines; the hydrogen fuel cell unit (34) is electrically connected to the solid-state hydrogen storage unit (33); The solid-state hydrogen storage unit (33) comprises a thermal insulation layer (3), a shell (4), a solid-state hydrogen storage material (5), a heating film (7), a hydrogen inlet (10), a first support plate (11), a second support plate (13), a hydrogen outlet (14) and a temperature sensor (16); the hydrogen inlet (10) and the hydrogen outlet (14) are symmetrically arranged at two ends of the shell (4) along a horizontal center line; the first support plate (11) and the second support plate (13) are respectively arranged in the shell (4) and are a certain distance away from the adjacent hydrogen inlet (10) or hydrogen outlet (14); the heating film (7) and the solid-state hydrogen storage material (5) arranged on both sides thereof are tightly pressed together to form a hydrogen storage and release unit; a plurality of hydrogen storage and release units are stacked in a cavity formed by the shell (4) and the first support plate (11) and the second support plate (13); the thermal insulation layer (3) is coated on the outside of the shell (4); The solid-state hydrogen storage material (5) is provided with a temperature sensor (16); the central controller (15) is communicatively connected with the temperature sensor (16) and the heating film (7) respectively; A coolant channel (19) is provided between two adjacent layers of hydrogen storage and release units, and a coolant inlet (1) and a coolant outlet (9) are respectively provided on the end surface of the shell body where the hydrogen inlet (10) and the hydrogen outlet (14) are not provided; The coolant channel is evenly provided with coolant guide plates parallel to each other; A third support plate (2) and a fourth support plate (8) are provided at both ends of the coolant channel (19); the third support plate (2) and the fourth support plate (8) are respectively spaced a certain distance from the adjacent coolant inlet (1) and the coolant outlet (9), and are fixedly mounted on the internal cavity of the shell along a horizontal center line; The coolant inlet (1) is provided with a coolant flow regulating valve (18), and the coolant flow regulating valve (18) is communicatively connected to the central controller (15); The heating film (7) is a carbon nanotube heating film, a carbon fiber heating film or a graphene heating film.

2. The skid-mounted hydrogen production, solid-state hydrogen storage and hydrogen fuel cell integrated system according to claim 1 is characterized in that: A plurality of hydrogen flow channels (6) are provided in the first support plate (11), the hydrogen storage material (5) and the second support plate (13) in a horizontal direction.

3. The skid-mounted hydrogen production, solid-state hydrogen storage and hydrogen fuel cell integrated system according to claim 1 is characterized in that: A first pressure measuring port is provided on the shell (4) on a side close to the hydrogen inlet (10), and a second pressure measuring port (12) is provided on the shell (4) on a side close to the hydrogen outlet (14). Pressure sensors are provided on the first pressure measuring port and the second pressure measuring port (12), and the pressure sensors are communicatively connected to the central controller (15).

4. The skid-mounted hydrogen production, solid-state hydrogen storage and hydrogen fuel cell integrated system according to claim 1 is characterized in that: The solid hydrogen storage material (5) is LiMgNH, MgH2, LaNi5, LaNi 4.6 Al 0.4 、LaNi 4.5 Al 0.5 、LaNi 4.5 Mn 0.5 、CaNi5、Ti 1.2 Mn 1.8 、TiCr 1.8 , one or more of ZrMn2, ZrV, TiFe, and Mg2Ni.

5. The skid-mounted hydrogen production, solid-state hydrogen storage and hydrogen fuel cell integrated system according to claim 1 is characterized in that: The heating film (7) has a thickness of 0.05-5 mm.

6. The skid-mounted hydrogen production, solid-state hydrogen storage and hydrogen fuel cell integrated system according to any one of claims 1 to 5, characterized in that: The hydrogen inlet (10) is provided with a hydrogen inlet valve (17), and the hydrogen outlet (14) is provided with a hydrogen outlet valve 1 (23), the outlet of the hydrogen outlet valve 1 (23) being respectively connected to the inlet of the hydrogen outlet valve 2 (24) and the inlet of the hydrogen circulation valve 1 (25); the outlet of the hydrogen circulation valve 1 (25) is connected to the heat medium inlet of the first cooler (26); the heat medium outlet of the first cooler (26) is connected to the inlet of the hydrogen circulation compressor (27); the hydrogen The outlet of the circulation compressor (27) is connected to the heat medium inlet of the second cooler (28); the heat medium outlet of the second cooler (28) is connected to the inlet of the second hydrogen circulation valve (29); the outlet of the second hydrogen circulation valve (29) is connected to the hydrogen inlet valve (17); the hydrogen inlet valve (17), the first hydrogen outlet valve (23), the second hydrogen outlet valve (24), the first hydrogen circulation valve (25), and the second hydrogen circulation valve (29) are respectively connected to the central controller (15) for communication.

7. The skid-mounted hydrogen production, solid-state hydrogen storage and hydrogen fuel cell integrated system according to claim 1 is characterized in that: The power supply unit (31) comprises an AC input interface, a DC input interface, a photovoltaic module (35), a first DC transformer (36), a rectifier (37) and a storage battery (38); the photovoltaic module (35) is electrically connected to the first DC transformer (36); the first DC transformer (36) is electrically connected to the storage battery (38), the hydrogen production unit (32), the solid-state hydrogen storage unit (33) and the hydrogen fuel cell unit (34); the rectifier (37) is electrically connected to the storage battery (38), the hydrogen production unit (32), the solid-state hydrogen storage unit (33) and the hydrogen fuel cell unit (34).

8. The skid-mounted hydrogen production, solid-state hydrogen storage and hydrogen fuel cell integrated system according to claim 1 is characterized in that: The hydrogen production unit (32) is one of an alkaline water electrolysis device, a proton exchange membrane pure water electrolysis device, an anion exchange membrane water electrolysis device and a solid oxide water electrolysis device.

9. A method for integrated operation of hydrogen production, solid-state hydrogen storage and hydrogen fuel cells, characterized in that: The skid-mounted hydrogen production, solid-state hydrogen storage and hydrogen fuel cell integrated system according to any one of claims 1 to 8 comprises the following steps: When producing hydrogen, the output voltage of the power supply unit (31) and the hydrogen output flow rate of the hydrogen production unit (32) are set on the central controller (15), and the hydrogen production unit (32) is powered on to start producing hydrogen; When storing hydrogen, the hydrogen inlet (10) of the solid-state hydrogen storage and release unit is opened, the hydrogen outlet (14) is closed, and the hydrogen storage temperature T1 is set on the central controller (15). The hydrogen from the hydrogen production unit (32) enters the solid-state hydrogen storage and release unit from the hydrogen inlet (10), flows through the accommodation space between the first support plate (11) and the hydrogen inlet (10), and is evenly distributed in the solid-state hydrogen storage material (5) through the hydrogen flow channel (6). As the temperature rises, the hydrogen reacts with the solid-state hydrogen storage material (5) to generate metal hydride. When the reaction temperature reaches the starting temperature T2, the central controller (15) starts to operate. The controller (15) stops supplying power to the heating film (7). Since the hydrogen storage reaction is an exothermic reaction, the released reaction heat needs to be removed in addition to the heat required to maintain the hydrogen storage temperature at a stable temperature of T1. At this time, the central controller (15) adjusts the coolant flow control valve (18) to adjust the coolant flow rate so that the temperature measured by the temperature sensor (16) is stable at T1, thereby maintaining stable and uniform hydrogen storage in the solid-state hydrogen storage and release unit. When the central controller (15) detects that the pressure measured by the pressure sensor begins to rise rapidly, the hydrogen inlet (10) is closed, the hydrogen production unit (32) is closed, and hydrogen storage is completed. When releasing hydrogen, the hydrogen inlet (10) is closed, the hydrogen outlet (14) is opened, and the hydrogen release temperature T3 is set on the central controller (15). The central controller (15) supplies power to the heating film (7), and the temperature of the solid hydrogen storage material (5) rises. When the temperature rises to T3, the solid hydrogen storage material (5) releases hydrogen stably. The central controller (15) controls the heating power of the heating film so that the measured temperature of the temperature sensor (16) is stabilized at T3. The lower limit flow rate L1 of the released hydrogen output is set on the central controller (15). When the measured flow rate of the hydrogen outlet (14) is reduced to L1 and the pressure measured by the pressure sensor drops rapidly, the hydrogen outlet (14) is closed, and the hydrogen release is completed. When generating electricity, the flow rate of hydrogen released by the solid-state hydrogen storage unit (33) is set on the central controller (15), and the solid-state hydrogen storage unit (33) is started to supply hydrogen to the hydrogen fuel cell unit (34). The hydrogen fuel cell unit (34) generates electrical energy. The purpose of the electrical energy is to provide power for the solid-state hydrogen storage unit (33) to release hydrogen in the absence of an external power supply and to store electricity in the storage battery (38).

10. The method for integrated operation of hydrogen production, solid-state hydrogen storage and hydrogen fuel cell according to claim 9, characterized in that: The following steps are involved: When storing hydrogen, first open the hydrogen inlet valve (17); then open the hydrogen outlet valve 1 (23), close the hydrogen outlet valve 2 (24), open the hydrogen circulation valve 1 (25) and the hydrogen circulation valve 2 (29); set the outlet temperature T4 of the first cooler (26) on the central controller (15), and control the refrigerant temperature or flow of the first cooler (26) by the central controller (15) to stabilize the outlet temperature of the first cooler (26) at T4; set the outlet temperature T5 of the second cooler (28) on the central controller (15), and control the refrigerant temperature or flow of the first cooler (26) by the central controller (15) to stabilize the outlet temperature of the second cooler (28) at T5; after the hydrogen storage is completed, close the hydrogen inlet valve (17), the hydrogen outlet valve 1 (23), the hydrogen outlet valve 2 (24), the hydrogen circulation valve 1 (25) and the hydrogen circulation valve 2 (29).

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