Hydrogen storage and compression system

Abstract

To provide a hydrogen storage-compression system which provides a high pressure ratio, achieves high energy efficiency and cost efficiency, and is safe.SOLUTION: A hydrogen storage-compression device includes: a casing; and a plurality of storage-compression units attached to the inside of an internal chamber of the casing. Each storage-compression unit includes a container and a metallic hydrogen compound housed in the container and configured for hydrogen storage-compression. The storage-compression container is connected to a hydrogen inlet and a hydrogen outlet for connecting to a hydrogen consuming device and a hydrogen supply source through a hydrogen gas circuit flow system. A heat management system includes a heat fluid circuit system and a heat exchanger system. The heat fluid circuit system has: a heat fluid flow circuit of a closed loop; a heat fluid which flows included in the heat fluid flow circuit; and a heat fluid pump for pumping the heat fluid in the heat fluid flow circuit.SELECTED DRAWING: Figure 3

Description

[Technical field]

[0001] The present invention relates to a metal hydride based hydrogen storage and compression system. [Background technology]

[0002] Hydrogen storage is a key step in the decarbonization of fossil fuel technologies with renewable energy.

[0003] Metal hydrides have attracted great interest in the field of hydrogen compression because many metals and alloys can reversibly absorb significant amounts of hydrogen and compress it with the addition of heat. Molecular hydrogen dissociates from the surface of the metal hydride before being absorbed. Two hydrogen atoms recombine to form molecular hydrogen upon desorption. The hydrogen absorption reaction of a material is generally exothermic (heat production), whereas the hydrogen desorption reaction is endothermic (heat absorption). Metal hydride compression systems are used as devices to supply hydrogen at the required high pressure levels, isobarically and without pulsation, by adding the heat required for desorption.

[0004] The challenges of hydrogen compression include ensuring high heat transfer rates and reaching high pressure ratios in a single system while ensuring a high level of safety. To obtain high pressure ratios given the thermodynamic behavior of metal hydride materials, a high temperature range of the system is required, i.e. a sufficiently large difference between the absorption temperature TCold and the desorption temperature THot.

[0005] Another challenge relates to maximizing the overall efficiency: energy losses associated with transient processes (heating and cooling processes) and auxiliary power consumption (pumping power) must be minimized.

[0006] The matters described in this Background Art section are created to enhance understanding of the background of the invention, and may include matters that are not prior art already known to those having ordinary skill in the art to which this technology pertains.

[0007] In view of the foregoing, it is an object of the present invention to provide a hydrogen storage and compression system that provides a high pressure ratio, while being energy efficient, cost effective and safe.

[0008] It would be advantageous to provide a hydrogen storage and compression system that is economical to operate and maintain.

[0009] It would be advantageous to provide a hydrogen storage and compression system that is reliable and compact.

[0010] The objectives of the present invention are achieved by providing a system according to various advantageous features of embodiments of the present invention. [Prior art documents] [Patent documents]

[0011] [Patent Document 1] WO2023-025657 DISCLOSURE OF THEINVENTION

[0012] Disclosed herein is a hydrogen storage-compression system having a hydrogen storage-compression device and a thermal management system. The hydrogen storage-compression device includes a casing and a plurality of storage-compression units mounted within an interior chamber of the casing. Each storage-compression unit has a container and a metal hydride configured for hydrogen storage and compression contained within the container. The plurality of storage-compression containers are interconnected by a hydrogen gas circuit flow system with a hydrogen inlet and a hydrogen outlet for connection to a hydrogen consumer and a hydrogen source.

[0013] The thermal management system includes a thermal fluid circuit system and a heat exchanger system. The thermal fluid circuit system has a closed-loop thermal fluid flow circuit, a thermal fluid contained and flowing within the thermal fluid flow circuit, and a thermal fluid pump for pumping the thermal fluid through the thermal fluid flow circuit. The thermal fluid flow circuit is coupled to the thermal fluid inlet and thermal fluid outlet of the casing for flowing the thermal fluid through the casing interior chamber around the container of the storage-compression unit for cooling or heating. The thermal fluid flow circuit is coupled to at least a first heat exchanger thermally coupled to a heating source and a second heat exchanger thermally coupled to a cooling source.

[0014] In one embodiment, the hydrogen storage-compression system further includes a control system coupled to the thermal fluid circuit system for controlling the flow of thermal fluid in the thermal fluid flow circuit through the heat exchanger. Preventing phase changes within a thermal management system is a significant advantage.

[0015] In one embodiment, the thermal management system includes a dry cooler thermally coupled to the thermal fluid flow circuit.

[0016] In one embodiment, the thermal management system includes one or more additional heat exchangers thermally coupled to the thermal fluid flow circuit. For example, the additional heat exchangers may include a waste heat recovery heat exchanger and / or an outdoor air cooling heat exchanger thermally coupled to an industrial process output.

[0017] In one embodiment, the thermal fluid is selected from any one or more of a water-ethylene glycol mixture, silicone oil, or synthetic hydrocarbon oil.

[0018] In one embodiment, the thermal fluid comprises or consists essentially of a water-ethylene glycol mixture in a ratio ranging from about 45% water:55% ethylene glycol to about 55% water:45% ethylene glycol, in another embodiment, the ratio is in the range of about 50% water-50% ethylene glycol.

[0019] In one embodiment, the metal hydride contained in the storage-compression unit is of material class AB2 having a composition of TiZryCraMnbFecNidCueVfReg, where x, y, a, b, c and d are molar ratios, Re is selected from among La and Ce, and 0.2≦x≦0.95, 0.05≦y≦0.45, 0.001≦a≦1, 0.3≦b≦2, 0.01≦c≦0.6, 0.005≦d≦1.5, 0≦e≦0.1, 0≦f≦0.5, 0.01≦g≦0.05, and a+b+c+d+e+f+g=1.9 to 2.3.

[0020] In one embodiment, the metal hydride contained in the storage-compression unit is of material class AB5 having a composition of LaxCeyMI(1-xy)NiaCobFecMd, where x, y, a, b, c, and d are molar ratios, M1 is one or more elements selected from Y, Ti, Zr, and M is selected from Cu and Mn, and 0.15≦x≦0.95, 0.05≦y≦0.85, 0≦(1-xy)≦0.1, 3.8≦a≦4.2, 0.1≦b≦1.2, 0.01≦c≦0.3, 0≦d≦0.1, and 4.8≦(a+b+c+d)≦5.15.

[0021] In one embodiment, the casing and thermal fluid flow circuit are configured to withstand an internal pressure of at least 2 bar.

[0022] In one embodiment, a control system is coupled to valves in the hydrogen gas circuit flow system and to pressure and temperature sensors coupled to the hydrogen gas circuit flow system to control the flow of hydrogen from the hydrogen source to the hydrogen storage-compression system and the flow of hydrogen from the hydrogen storage-compression system to the hydrogen consumer.

[0023] In one embodiment, each storage-compression container includes a tubular container wall having a diameter D in the range of about 1.5 cm to 10 cm. Adjacent containers of the plurality of storage-compression containers of the at least one multi-container unit are separated by a gap G having a length in the range of 0.02×D to 1×D.

[0024] In one embodiment, the diameter D of the tubular container wall of each storage-compression container is in the range of about 2 cm to 8 cm. In one example, the diameter is in the range of about 3 cm to 6 cm.

[0025] In one embodiment, the spacing G between the storage-compression containers is in the range of approximately 0.1×D to 0.5×D.

[0026] In one embodiment, the storage and compression container has a length in the range of about 60 cm to 200 cm. In one embodiment, the length is in the range of about 80 cm to 150 cm.

[0027] In one embodiment, the hydrogen storage-compression system is used in a quasi-isobaric hydrogen supply system to absorb and desorb hydrogen at elevated pressure. In one embodiment, the elevated pressure is greater than 50 bar. In one embodiment, the elevated pressure is greater than 200 bar. In one embodiment, the system is capable of desorbing hydrogen at a substantially constant pressure with minimal temperature change. In one embodiment, the temperature change may be less than 40° C. In one embodiment, the temperature change may be in the range of approximately 20° C. to 30° C.

[0028] The present invention provides a high pressure ratio while being energy efficient, cost effective and safe.

[0029] It is also economical to operate and maintain, reliable and compact.

[0030] In addition, advantages obtained or expected by the embodiments of the present invention will be directly or implicitly disclosed in the detailed description of the disclosed embodiments, i.e., various advantages expected by the embodiments of the present invention will be disclosed in the detailed description below. [Brief description of the drawings]

[0031] Additional objects and advantageous features of the present invention will become apparent from the claims, detailed description, and accompanying drawings. [Figure 1]FIG. 1 is a simplified block diagram of a hydrogen storage and compression system according to an embodiment of the present invention. [Diagram 2] FIG. 2 is a graph of pressure (bar) versus storage capacity (wt%) of a metal hydride material of a hydrogen storage and compression system according to an embodiment of the invention. [Diagram 3] FIG. 3 is a block diagram illustrating a control system for a hydrogen storage-compression system according to an embodiment of the present invention. [Figure 4a] FIG. 4a is a longitudinal cross-sectional view of a casing and a storage-compression unit of a hydrogen storage-compression system according to an embodiment of the present invention. [Figure 4b] FIG. 4b is a cross-sectional view of a casing and storage-compression unit of a hydrogen storage-compression system according to an embodiment of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0032] When a component, device, element, etc. of the present invention is described as having a purpose or performing an operation, function, etc., the component, device, or element must be considered herein to be "adapted" to achieve that purpose or perform that operation or function. Referring to the drawings, a hydrogen storage and compression system 1 includes a hydrogen storage and compression device 2 and a thermal management system 5.

[0033] The hydrogen storage-compression system 1 is connected to a hydrogen source 101 and a hydrogen consumer 102. The hydrogen source may be, for example, an electrolyser, a hydrogen network connected through a pipeline, a hydrogen trailer, or a low or high pressure hydrogen cylinder. Other possibilities include hydrogen from a steam methane reformer or a biomass gasification plant. The hydrogen consumer 102 may be, for example, a vehicle such as a car, truck, bus, or ship that uses compressed hydrogen, typically stored in a high pressure cylinder and utilized in a fuel cell or a combustion engine. Hydrogen may also be used for the production of process components (e.g. ammonia) or high temperature heat (metal processing) in combined heat and power cycles and other industrial processes.

[0034] During the desorption process, the hydrogen leaving through the compression of the metal hydrides is at high temperatures of up to 130° C. The maximum possible temperature inside the high-pressure storage tank must comply with certain requirements and safety standards during the refilling process. The hydrogen storage and compression system 1 according to an embodiment of the invention is configured to compress hydrogen at high pressure to fill the hydrogen storage tank of the hydrogen consumer 102. The pressure is typically higher than 350 bar and can even exceed up to 900 bar depending on the intended field of application of the consumer.

[0035] The hydrogen storage-compression apparatus 2 includes a casing 3 and a number of storage-compression units 4 mounted in the casing 3. Each storage-compression unit 4 has a container 20 and a metal hydride 22 provided within the container, typically in powder or granular form. The multiple containers 20 of the multiple storage-compression units 4 are interconnected by a gas circuit flow system 24 comprised of gas flow tubes and valves interconnected to a hydrogen source 101 and a hydrogen consumer 102 through a hydrogen inlet / outlet system through the wall of the casing 3. The casing 3 sealingly encloses the storage-compression units 4 and the hydrogen inlet / outlet such that liquid flowing through the internal chamber 12 of the casing 3 is isolated from the external environment surrounding the casing 3 and is sealingly contained within the casing 3.

[0036] The casing 3 and the storage-compression unit 4 may include a configuration similar to the casing and storage-compression unit described in PCT Publication WO2023-025657, except for the differences described herein, particularly with respect to the thermal management system 5, the thermal fluid 28, and the thermal fluid circuits for cooling and heating the storage-compression unit 4 mounted within the casing 3.

[0037] The casing 3 encloses an internal chamber 12 of the casing 3 within which the storage-compression unit 4 is mounted. The casing 3 includes a thermal fluid inlet 16 at one end and side of the casing 3 and a thermal fluid outlet 18 at the other end and side of the casing 3. Thus, as the thermal fluid 28 flows from the thermal fluid inlet 16 to the thermal fluid outlet 18, the thermal fluid 28 flows around the exterior of the container 20 of the storage-compression unit 4. The thermal fluid 28 flowing around and across the exterior of the container 20 serves to cool or heat the storage container 4 according to the relevant requirements of the hydrogen compression process step and the hydrogen absorption or desorption process.

[0038] Each storage-compression container 20 may include a tubular container wall having a diameter D in the range of approximately 1.5 cm to 10 cm. Adjacent containers of the plurality of storage-compression containers of the at least one multi-container unit may be separated by a gap G having a length in the range of approximately 0.02×D to 1×D.

[0039] In some embodiments, the diameter D of the tubular container wall of each storage-compression container 24 ranges from about 2 cm to 8 cm. In one embodiment, the diameter D ranges from about 3 cm to 6 cm.

[0040] In some embodiments, the spacing G between the storage-compression containers 24 ranges from 0.1×D to 0.5×D.

[0041] In some embodiments, the storage-compression container has a length in the range of about 60 cm to 200 cm. In one embodiment, the length is in the range of about 80 cm to 150 cm.

[0042] The above parameters enable the provision of a hydrogen storage-compression apparatus 2 having excellent heat transfer characteristics between the metal hydride of the storage-compression unit 4 and the thermal fluid flowing through the internal chamber 12 of the casing 3. The above parameters enable the provision of a hydrogen storage-compression apparatus 2 having a size and shape that allows it to be easily transported on a vehicle such as a truck, boat, railroad car, etc., and that allows this result to be achieved.

[0043] The thermal management system 5 includes a heat exchanger system 7 and a thermal fluid circuit system 6 interconnecting the thermal fluid inlet 16 and outlet 18 of the casing 3 to the heat exchanger system 7. The thermal fluid circuit system 6 has a thermal fluid pump 26 for pumping a thermal fluid 28 through the internal chamber 12 and the heat exchanger system 7, and has a plurality of valves V for controlling the flow of the thermal fluid 28 through the heat exchanger system 7.

[0044] The heat exchanger system 7 includes at least a first heat exchanger 30a coupled to a heating source 8 and at least a second heat exchanger 30b coupled to a cooling source 9. The heat exchanger system 7 may include additional heat exchangers, such as a waste heat recovery heat exchanger 30d and an outdoor air cooling heat exchanger 30e. The heat exchanger system 7 may further include an optional dry cooler 30c. A dry cooler 30c, also known as an air-cooled condenser or air-cooled heat exchanger, is a device used in a heat exchanger system to reject heat to or absorb heat from the surrounding air without the evaporation of water. The dry cooler 30c includes a pin-tube heat exchanger, similar to a radiator, in which heat is exchanged between a thermal fluid and the surrounding air.

[0045] In the present invention, the dry cooler 30c provides the power for cooling or heating during the heating or cooling transient phase. In particular, the dry cooler 30c is capable of heating from the absorption temperature to the ambient temperature and cooling from the desorption temperature to the ambient temperature without a cooling or heating device, thus reducing the energy consumption of the entire system.

[0046] A number of valves V interconnect the thermal fluid circuit (channels, pipes) 6 to each heat exchanger to control the flow of thermal fluid 28 through the required heat exchangers according to the process steps and requirements. A first heat exchanger 30a coupled to a heating source 8 is configured to heat the flow of thermal fluid 28 in the thermal fluid circuit system 6 to a temperature of 105° C. or higher, and in one embodiment, up to 130° C. or higher. A second heat exchanger 30b coupled to a cooling source 9 is configured to cool the thermal fluid 28 flowing in the thermal fluid circuit system 6 to a temperature of at least less than −20° C., and in one embodiment, less than −30° C.

[0047] The thermal fluid circuit system 6 is configured to withstand a maximum pressure of 2 bar in one embodiment. Thus, the thermal fluid 28 contained within the thermal fluid circuit system 6 can be circulated at up to 2 bar and maintained in liquid form at temperatures between −35° C. and +160° C. Exemplary thermal fluid compositions are described in more detail below.

[0048] The thermal management system 5 includes a control system 10 which includes a control unit coupled to the thermal fluid pump 26 and valve V and which controls the operation of the pump and various valves during the hydrogen absorption and desorption processes. The control unit is further coupled to the heat exchanger system 7 and a temperature sensor T, which is selectively coupled to a pressure sensor P for controlling the heating and cooling processes of the thermal fluid flowing through the thermal fluid circuit 6 and the casing inner chamber 12.

[0049] The pressure sensor P and / or the temperature sensor T may be coupled to the thermal fluid 28 in the internal chamber 12, and additional temperature sensors T and / or pressure sensors P may be arranged at different points according to the thermal fluid circuit system 6. The control unit of the control system 10 is further coupled to valves interconnecting the hydrogen storage-compression device 2 to the hydrogen source 101 and the hydrogen consuming device 102, the input (inflow) and output (outflow) of hydrogen between the hydrogen source 101 and the hydrogen consuming device 102, and the storage-compression unit 4 of the hydrogen storage-compression device 2.

[0050] A thermal management software module is provided in the control unit and manages the control of pumps, valves and heat exchanger systems as a function of heating or cooling requirements depending on the hydrogen absorption or desorption process and the inlet and outlet pressures between the hydrogen storage-compression device 4, the hydrogen source 101 and the hydrogen consumer device 102.

[0051] The use of a thermal fluid circulating in a closed circuit that remains as a liquid single phase at temperatures between -30°C and +130°C, typically in the range of about -20°C to about 120°C, and that can be coupled to separate heat exchangers for cooling and heating, allows efficient, safe, compact and cost-effective operation of hydrogen storage and compression systems for high pressures above 350 bar and up to about 900 bar. The use of heat exchangers coupled to a closed thermal fluid circuit can be advantageous for the coupling of external waste heat or outside air cooling units of industrial processes allowing hydrogen compression to be performed in an energy efficient manner.

[0052] Thermal Fluid Media The basic requirement of the heat transfer medium (thermal fluid) is to provide a sufficiently high rate of heat transfer within the temperature range used, which for suitable materials is between -30.0°C and 120°C. It is well known that liquids are more suitable than gases for heat transfer applications due to their higher heat capacity (density, heat capacity) and increased thermal conductivity. For simplicity, phase change is also prevented. The heat transfer medium must also have a sufficiently low viscosity, low toxicity, low corrosion and low oxidation potential to be suitable for use in the system pump. With non-pressure vessels, the flash point is also important, especially if it is within the operating temperature range of the compressor. In this case, appropriate safety devices must be provided to ensure that the vapors formed are safely vented to the atmosphere.

[0053] Based on the aforementioned requirements, different heat transfer media may be used, in one embodiment, for example, a water-ethylene glycol mixture in the same ratio (50%:50%) at a pressure of 1 bar(g) (or higher) can be used as it remains liquid at the given temperature and pressure range.

[0054] In other embodiments, the thermal fluid 28 may include or consist of thermal oil, which may be in an open enclosure (not a pressure vessel) and under atmospheric conditions. Examples of such thermal media include Therminol D-12, silicone oil, or FRAGOLTHERM 620. Different grades are possible based on the viscosity and heat transfer properties required. The following table summarizes the thermal media properties:

[0055] [Table 1]

[0056] Metal Hydride Materials In one embodiment, the metal hydride 22 contained in the storage-compression unit 4 is of material class AB2 having a typical composition of TixZryCraMnbFecNidCueVfReg.

[0057] In the composition, x, y, a, b, c and d are molar ratios, Re is selected from La and Ce, 0.2≦x≦0.95, 0.05≦y≦0.45, 0.001≦a≦1, 0.3≦b≦2, 0.01≦c≦0.6, 0.005≦d≦1.5, 0≦e≦0.1, 0≦f≦0.5, 0.01≦g≦0.05, and a+b+c+d+e+f+g=1.9-2.3.

[0058] In another embodiment, the metal hydride 22 contained in the storage-compression unit 4 is of material class AB5 with a typical composition of LaxCeyMI(1-xy)NiaCobFecMd, where x, y, a, b, c and d are molar ratios, where MI is one or more elements selected from Y, Ti, Zr, M is selected from Cu and Mn, and 0.15≦x≦0.95, 0.05≦y≦0.85, 0≦(1-xy)≦0.1, 3.8≦a≦4.2, 0.1≦b≦1.2, 0.01≦c≦0.3, 0≦d≦0.1; and 4.8≦(a+b+c+d)≦5.15.

[0059] Within the scope of the present invention, the hydrogen storage metals are not limited to AB2 or AB5 materials, but can also apply to other classes of materials that exhibit similar thermochemical behavior.

[0060] Examples of industrial application processes The hydrogen storage and compression system 1 operating in the overall cycle may include the following steps, in the order presented. Such steps may include: (i) absorption, (ii) heating, (iii) desorption, and (iv) cooling. Examples of such processes are described in more detail below. The values ​​shown correspond to examples using a thermal fluid 28 composed of a water-ethylene glycol mixture in the same ratio (50%:50%) at a pressure of 1 bar(g).

[0061] absorption Hydrogen is absorbed in the storage-compression unit 4 in an almost isobaric process from an external source. The pressure of the H2 source is typically in the range of 25 bar(g) to 40 bar(g), most commonly 35 bar(g) for a typical electrolyser. Since the absorption reaction is highly exothermic (resulting in heat release), the storage-compression unit 4 must be cooled to maintain the generated pressure below the charge pressure. The cooling power provided must also compensate for the inevitable heating due to the surrounding environment, which also tends to increase the hydrogen pressure in the developed storage-compression unit 4. This energy requirement is primarily a function of the absorption enthalpy of the metal hydride material 22, which for a suitable material is 18.0 kJ / molH2, so the energy requirement is 87 kWhth or about 2.7 kWhth / kgH2 (both values ​​include heating compensation energy).

[0062] The absorption process time requirement depends on the type of H2 source and may range from 1 to 8 hours, resulting in a cooling power of 10.9 kWth to 87 kWth. For suitable metal hydride materials, the compressor inlet fluid temperature is typically -30°C to -0°C, with typical values ​​being -25.0°C to -20°C. Typical cooling flow rate is 7.5 m3 / h. The hot fluid 28 flows through the cooling heat exchanger 30a, bypassing the dry cooler 30c and the heating heat exchanger 30b. It should be noted that since the exothermic reaction produces an inverse parabolic temperature profile within the metal hydride 22, the inlet temperature is lower than the temperature of the material PCT curve corresponding to the absorption pressure.

[0063] [Table 2]

[0064] Detachment During the desorption process, hydrogen is released from the hydrogen storage-compression device 2 to a hydrogen consuming device 102, such as a hydrogen powered vehicle, i.e., truck or bus, requiring refilling at 350 bar or more. The desorption pressure can be adjusted through the selection of the temperature of the material and heat transfer medium. The time required for refilling the vehicle affects the hydrogen desorption rate. The refill time can be anywhere from a few minutes, e.g., 5-15 minutes, to up to several hours, e.g., 3-8 hours. The desorption pressure of the storage-compression unit 4 is a function of the final mass delivered, the desorption mass flow rate, and the hydrogen temperature before entering the hydrogen powered vehicle. For example, for an application such as slow refilling at 6 kgH2 / h, the refill time for a Hyundai XCIENT truck (32 kgH2) is 5 hours and 20 minutes, the hydrogen temperature after the hydrogen cooler is -25.0°C, and the desorption pressure is 370 bar. In this case, it is advantageous to directly utilize the cooling source 9 of the thermal management system 5 of the metal hydride compressor for hydrogen cooling. Instead of increasing the desorption pressure and / or additionally decreasing the hydrogen temperature, other flow rates are possible.

[0065] As in the absorption case, maintaining a thermal fluid flow rate of 7.5 m3 / h results in an inlet temperature of 110°C required to achieve a desorption pressure of 370 bar for a given material. The total energy requirement to compensate for the cooling effect of desorption and balance the heat loss to the surroundings is 110.8 kWhth or about 3.5 kWhth / kgH2, based on a desorption enthalpy of 20.0 kJ / molH2. During this step, the thermal fluid flows through the heating heat exchanger 30b, bypassing the dry cooler 30c and the cooling heat exchanger 30a. Considering the desorption period and the energy requirements of this step, the power delivered by the heating machine is 20.8 kWth.

[0066] [Table 3]

[0067] heating Once the absorption step is complete, the storage-compression unit 4 is heated from the absorption temperature (-25.0°C) to the desorption temperature (110°C) by the thermal fluid 28 which flows initially through the dry cooler 30c and finally through the heating heat exchanger 30b. The heating involves increasing the internal pressure of the storage-compression unit 4 to 370 bar. During the initial stage of heating, the flow through the dry cooler 30c allows the temperature of the storage-compression unit 4 to increase from the absorption temperature to ambient temperature. This energy is provided essentially for free. However, a certain amount of pumping power is required for the flow of liquid through the dry cooler 30c. The total heating energy required is 5.4 kWhth / kgH2 (172.8 kWhth), of which 1.7 kWhth / kgH2 (55.1 kWhth) is provided by the dry cooler 30c, while the remaining energy 3.7 kWhth / kgH2 (117.7 kWhth) is provided by the heating heat exchanger 30b. The flow rate during the heating process is 7.5 m3 / h. To simplify the system, it is assumed that the same heating heat exchanger 30b is used for desorption. If the same electrical energy is provided to the heating heat exchanger 30b, the thermal power varies and depends on the coefficient of performance over this temperature range. The heating step time is about 5 hours and 20 minutes.

[0068] [Table 4]

[0069] cooling Following completion of desorption, the storage-compression unit 4 is cooled from the desorption temperature (110.0°C) to the absorption temperature (-25.0°C). As with the heating, all or most of the streams are initially directed through the dry cooler 30c to take advantage of the freely available ambient cooling. Upon reaching the ambient temperature, the streams are directed through the cooling heat exchanger 30a to achieve subcooling to the absorption temperature. The total cooling energy requirement is 4.7 kWhth / kgH2 (149.2 kWhth), of which 3.2 kWhth / kgH2 (101.5 kWhth) is provided by the dry cooler 30c, while the remaining energy 1.5 kWhth / kgH2 (47.7 kWhth) is provided by the cooling heat exchanger 30a. The flow rate during the cooling step is 7.5 m3 / h.

[0070] For cooling, the same cooling heat exchanger is used, resulting in a step duration of 2 hours 11 minutes.

[0071] [Table 5]

[0072] Industrial Application Examples In an application, the hydrogen storage and compression system 1 may be advantageously used as a system for refilling hydrogen-powered vehicles, such as trucks or buses, which require a refill level of 350 bar. In such applications, the outlet pressure is typically increased slightly (e.g., by 10 bar) above the pressure of the tank being refilled by selectively adjusting the heating power. In such applications, typical desorption times may be as low as 5-15 minutes. In other cases, desorption times may be as long as 60 minutes or even 180 minutes or more. In such applications, typical inlet pressure ranges are 25 bar(g) to 35 bar(g). Typical cooling temperature ranges are -15°C to -30°C. Typical heating temperature ranges are 90°C to 130°C.

[0073] In another application, the hydrogen storage and compression system 1 may be advantageously used as a system for refilling hydrogen-powered vehicles, such as large or small vehicles requiring a refill level of 700 bar. In such applications, the outlet pressure is typically increased slightly (e.g., by 10 bar) above the pressure of the tank being refilled by selectively adjusting the heating power. In such applications, typical desorption times may be as low as 5-15 minutes. In other cases, desorption times may be as long as 60 or 180 minutes or more. Typical inlet pressure ranges for such applications are 150 bar(g) to 350 bar(g). Typical cooling temperature ranges are 5°C to -30°C. Typical heating temperature ranges are 60°C to 130°C.

[0074] In another application, the hydrogen storage and compression system 1 may be advantageously used as a system for recharging trailers requiring a recharging level of 200 bar for transport or storage of hydrogen. In such applications, the outlet pressure is typically increased slightly (e.g., by 10 bar) above the pressure of the tank being recharged by selectively adjusting the heating power. In such applications, typical desorption times may be as low as 60 minutes. In other cases, desorption times may be as long as 180 minutes or even 300 minutes or more. A typical inlet pressure range for such applications is 25 bar(g) to 35 bar(g). A typical cooling temperature range is -15°C to -30°C. A typical heating temperature range is 90°C to 130°C.

Claims

1. In a hydrogen storage and compression system, Hydrogen storage-compression equipment; A thermal management system; and Control system; Including, the hydrogen storage-compression apparatus includes a casing and a plurality of storage-compression units mounted within an interior chamber of the casing, each storage-compression unit including a container and a metal hydride configured for hydrogen storage and compression contained within the container, the plurality of storage-compression containers being interconnected by a hydrogen gas circuit flow system with a hydrogen inlet and a hydrogen outlet for connection to a hydrogen consumer and a hydrogen source; The thermal management system includes a thermal fluid circuit system and a heat exchanger system; The thermal fluid circuit system includes: a closed loop thermal fluid flow circuit; a thermal fluid contained and flowing within a thermal fluid flow circuit; a thermal fluid pump for pumping the thermal fluid in the thermal fluid flow circuit; Including, The thermal fluid flow circuit is a thermal fluid inlet and a thermal fluid outlet connected to the casing for flowing a thermal fluid through the casing interior chamber around the container of the storage-compression unit for cooling or heating; coupled to at least a first heat exchanger thermally coupled to a heating source and a second heat exchanger thermally coupled to a cooling source; A control system is coupled to the thermal fluid circuit system for controlling the flow of thermal fluid in the thermal fluid flow circuit through the heat exchanger, the hydrogen storage-compression system.

2. The hydrogen storage and compression system of claim 1 , wherein the thermal management system includes a dry cooler thermally coupled to the thermal fluid flow circuit.

3. The hydrogen storage and compression system of claim 1 , wherein the thermal management system includes one or more additional heat exchangers thermally coupled to the thermal fluid flow circuit.

4. The one or more additional heat exchangers may include a heat exchanger for waste heat recovery thermally coupled to the output of an industrial process; and / or Heat exchanger for cooling outdoor air; The hydrogen storage and compression system of claim 3, comprising:

5. 10. The hydrogen storage and compression system of claim 1, wherein the thermal fluid is selected from any one or more of a water-ethylene glycol mixture, a silicone oil, or a synthetic hydrocarbon oil.

6. 10. The hydrogen storage and compression system of claim 1, wherein the thermal fluid comprises a water-ethylene glycol mixture having a water:ethylene glycol ratio in the range of 45%-55%:55%-45% or 50%:50%.

7. 2. The hydrogen storage and compression system of claim 1, wherein the metal hydride contained in the storage and compression unit is material class AB2 having a composition of TixZryCraMnbFecNidCueVfReg, where x, y, a, b, c and d are molar ratios, Re is selected from among La and Ce, 0.2≦x≦0.95, 0.05≦y≦0.45, 0.001≦a≦1, 0.3≦b≦2, 0.01≦c≦0.6, 0.005≦d≦1.5, 0≦e≦0.1, 0≦f≦0.5, 0.01≦g≦0.05, and a+b+c+d+e+f+g=1.9 to 2.

3.

8. 2. The hydrogen storage and compression system of claim 1, wherein the metal hydride contained in the storage and compression unit is material class AB5 having a composition of LaxCeyMI(1-x-y)NiaCobFeCmd, where x, y, a, b, c and d are molar ratios, M1 is one or more elements selected from Y, Ti, Zr, and M is selected from Cu and Mn, and 0.15≦x≦0.95, 0.05≦y≦0.85, 0≦(1-x-y)≦0.1, 3.8≦a≦4.2, 0.1≦b≦1.2, 0.01≦c≦0.3, 0≦d≦0.1, 4.8≦(a+b+c+d)≦5.

15.

9. 10. The hydrogen storage and compression system of claim 1, wherein the casing and the thermal fluid flow circuit are configured to withstand an internal pressure of at least 2 bar.

10. 2. The hydrogen storage-compression system of claim 1, wherein the control system is coupled to valves of the hydrogen gas circuit flow system and to pressure and temperature sensors coupled to the hydrogen gas circuit flow system, and controls the flow of hydrogen from the hydrogen source to the hydrogen storage-compression system and the flow of hydrogen from the hydrogen storage-compression system to the hydrogen consumer.

11. 2. The hydrogen storage-compression system of claim 1, wherein each storage-compression container comprises a tubular container wall having a diameter D in the range of 1.5 cm to 10 cm, and adjacent storage-compression containers among the plurality of storage-compression containers of at least one multi-container unit are separated by a gap G having a length in the range of 0.02xD to 1xD.

12. 12. The hydrogen storage and compression system of claim 11, wherein the diameter D of the tubular container wall of each storage and compression container is in the range of 2 cm to 8 cm or in the range of 3 cm to 6 cm.

13. 12. The hydrogen storage-compression system of claim 11, wherein the spacing G between the storage-compression containers is in the range of 0.1xD to 0.5xD.

14. 12. The hydrogen storage and compression system of claim 11, wherein the storage and compression container has a length in the range of 60 cm to 200 cm or in the range of 80 cm to 150 cm.

15. 2. The hydrogen storage-compression system according to claim 1, which is used in a quasi-isobaric hydrogen supply system that absorbs and desorbs hydrogen at high pressures of 50 bar or more or 200 bar or more, and desorbs hydrogen at a substantially constant pressure with a temperature change of less than 40° C. or a temperature change in the range of 20° C. to 30° C.

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