Hybrid hydrogen supply system and hybrid hydrogen supply method

Abstract

The invention discloses a mixed hydrogen supply system and a mixed hydrogen supply method. A hybrid hydrogen supply system according to an embodiment may include: a compressed hydrogen supply system configured to store compressed hydrogen gas supplied from an external hydrogen charging station, and selectively supply the hydrogen gas to a fuel cell; and a solid state hydrogen supply system configured to generate hydrogen gas through a chemical reaction of a chemical hydride, and selectively supply the generated hydrogen gas to the fuel cell.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to and the benefit of Korean Patent Application No. 10-2023-0162948, filed on November 22, 2023, which is incorporated herein by reference in its entirety. Technical Field

[0003] The present invention relates to a hybrid hydrogen supply system and a hybrid hydrogen supply method. More specifically, the present invention relates to such a hybrid hydrogen supply system and a hybrid hydrogen supply method, which can use both a compressed hydrogen storage system and a solid-state hydrogen storage system. Background Art

[0004] Due to the depletion of fossil energy and environmental pollution, there is a high demand for renewable alternative energy. Therefore, hydrogen has attracted attention as such an alternative energy.

[0005] Fuel cells and hydrogen combustion devices use hydrogen as a reaction gas. Stable and continuous hydrogen supply technology is required in order to apply fuel cells and hydrogen combustion devices to vehicles and various electronic products.

[0006] A scheme of receiving hydrogen from a hydrogen charging station (hereinafter referred to as a "compressed hydrogen supply scheme") may be adopted, wherein the hydrogen charging station is separately installed so as to supply hydrogen to the device when hydrogen is needed. In such a scheme, compressed hydrogen may be used.

[0007] However, a scheme for generating hydrogen by the following method (hereinafter referred to as the "solid-state hydrogen supply scheme") may also be adopted: an acidic aqueous solution, an acidic catalyst, or water and an acidic catalyst are injected into the solid hydride stored in the dehydrogenation reactor to supply hydrogen to a fuel cell or a hydrogen combustion device.

[0008] In the compressed hydrogen supply scheme, before the hydrogen is exhausted, the vehicle moves to an external hydrogen filling station, or a mobile hydrogen filling station moves to the vehicle to be filled with hydrogen so that hydrogen can be supplied to the vehicle. Therefore, when the hydrogen is exhausted, the vehicle must move to the hydrogen filling station to refill hydrogen.

[0009] In the solid hydrogen supply scheme, when the solid hydride reacts at room temperature / pressure, impurity gases may be mixed in the initial reaction, and boil-off gas containing water vapor may also be included due to the heating reaction. Therefore, in addition to pure hydrogen, impurities and / or water vapor may also be supplied to the fuel cell or hydrogen combustion device, which may adversely affect the durability of the fuel cell or hydrogen combustion device.

[0010] The above information disclosed in this Background section is only for enhancement of understanding of the background of the invention. Therefore, the Background section may contain information that does not form the prior art that is already known to a person of ordinary skill in the art. Summary of the invention

[0011] The present invention provides a hybrid hydrogen supply system and a hybrid hydrogen supply method, which can use a compressed hydrogen supply solution and a solid hydrogen supply solution.

[0012] In one embodiment of the present invention, a hybrid hydrogen supply system may include a compressed hydrogen supply system configured to store compressed hydrogen supplied from an external hydrogen filling station and selectively supply the compressed hydrogen to a fuel cell. The hybrid hydrogen supply system further includes a solid-state hydrogen supply system configured to generate hydrogen through a chemical reaction of a chemical hydride and selectively supply the generated hydrogen to a fuel cell.

[0013] In some embodiments, a compressed hydrogen supply system may include: at least one compressed hydrogen tank configured to store compressed hydrogen gas; and a first pressure regulator disposed downstream of the compressed hydrogen tank.

[0014] In some embodiments, the solid-state hydrogen supply system may include: an acidic aqueous solution tank configured to store an acidic aqueous solution; and at least one dehydrogenation reactor configured to store a chemical hydride and selectively receive the acidic aqueous solution stored in the acidic aqueous solution tank to produce hydrogen. The solid-state hydrogen supply system may also include a heat regulating device configured to regulate the temperature of the dehydrogenation reactor.

[0015] In some embodiments, the solid hydrogen supply system may further include a purification device configured to discharge impurity gases within the dehydrogenation reactor.

[0016] In some embodiments, the purification device may include: a first purification pipe configured to connect the compressed hydrogen tank and the dehydrogenation reactor fluid; and a second purification pipe configured to connect the dehydrogenation reactor and an external fluid. The purification device may also include: a first purification valve disposed in the first purification pipe between the compressed hydrogen tank and the dehydrogenation reactor; and a second purification valve disposed in the second purification pipe downstream of the dehydrogenation reactor.

[0017] In some embodiments, the purification device may further include a vacuum pump disposed in the second purification pipe downstream of the second purification valve.

[0018] In some embodiments, the hybrid hydrogen supply system may further include a buffer tank configured to temporarily store the hydrogen generated by the dehydrogenation reactor.

[0019] In some embodiments, the hybrid hydrogen supply system may further include a booster pump disposed between the buffer tank and the compressed hydrogen tank.

[0020] In some embodiments, the buffer tank may be a compressed hydrogen tank of a compressed hydrogen supply system.

[0021] In some embodiments, the solid hydrogen supply system may further include: a back pressure regulator disposed upstream of the buffer tank; a hydrogen rectification device disposed upstream of the back pressure regulator; and a second pressure regulator disposed downstream of the buffer tank.

[0022] Another embodiment of the present invention provides a hybrid hydrogen supply method using a compressed hydrogen supply system and a solid-state hydrogen supply system. The hybrid hydrogen supply method may include: executing a first mode when a first condition is met, in which hydrogen is supplied to a fuel cell from a compressed hydrogen supply system; and executing a second mode when a second condition is met, in which hydrogen is supplied to a fuel cell from a solid-state hydrogen supply system. The method may further include: executing a third mode when a third condition is met, in which hydrogen is supplied to a fuel cell from both a solid-state hydrogen supply system and a compressed hydrogen supply system.

[0023] In some embodiments, the first condition may be satisfied when all reactants of the dehydrogenation reactor in the solid-state hydrogen supply system are consumed. Alternatively, the first condition may be satisfied when the amount of hydrogen stored in the compressed hydrogen tank of the compressed hydrogen supply system is less than a set amount and the storage capacity of the compressed hydrogen tank is equal to or greater than the total hydrogen production in the solid-state hydrogen supply system.

[0024] In some embodiments, the second condition may be met when the hydrogen stored in the compressed hydrogen tank of the compressed hydrogen supply system is completely exhausted, when the amount of hydrogen produced by the solid-state hydrogen supply system meets the amount of hydrogen required by the fuel cell, or when the storage capacity of the buffer tank of the solid-state hydrogen supply system is equal to or greater than the total hydrogen produced in the dehydrogenation reactor.

[0025] In some embodiments, the third condition may be met when the flow rate of hydrogen generated by the dehydrogenation reactor of the solid-state hydrogen supply system deviates from the set range, the storage capacity of the buffer tank of the solid-state hydrogen supply system is less than the total hydrogen production generated by the dehydrogenation reactor of the solid-state hydrogen supply system, or the time required to increase the pressure of the hydrogen stored in the buffer tank to a level equal to or greater than the set pressure of the pressure regulator is equal to or greater than the set time.

[0026] In some embodiments, the first mode may include supplying hydrogen stored in a compressed hydrogen tank of the compressed hydrogen supply system to the fuel cell. In addition, the first mode may include supplying hydrogen from the solid hydrogen supply system to the fuel cell when the internal pressure of the compressed hydrogen tank is less than the set pressure.

[0027] In some embodiments, the second mode may include performing a purification process of the dehydrogenation reactor of the solid hydrogen supply system when the purification condition is met. In addition, the second mode may include: supplying hydrogen from the solid hydrogen supply system to the fuel cell; and when the internal pressure of the dehydrogenation reactor is less than the set pressure, supplying hydrogen from the compressed hydrogen tank of the compressed hydrogen supply system to the fuel cell.

[0028] In some embodiments, performing the purification process may include: supplying hydrogen stored in a compressed hydrogen tank of a compressed hydrogen supply system to a dehydrogenation reactor of a solid hydrogen supply system; and discharging a mixed gas of impurity gas and hydrogen from the dehydrogenation reactor to the outside.

[0029] In some embodiments, the third mode may include performing a purification process of a dehydrogenation reactor of the solid-state hydrogen supply system when the purification mode is satisfied. The third mode may also include: supplying hydrogen from the solid-state hydrogen supply system to the fuel cell; and when the pressure of the hydrogen stored in the buffer tank of the solid-state hydrogen supply system is lower than the set pressure of the pressure regulator disposed downstream of the buffer tank, supplying hydrogen stored in the compressed hydrogen tank of the compressed hydrogen supply system to the fuel cell. In addition, the third mode may include supplying hydrogen from the solid-state hydrogen supply system to the fuel cell when the pressure of the hydrogen stored in the buffer tank is higher than the set pressure of the pressure regulator disposed downstream of the buffer tank.

[0030] In some embodiments, performing the purification process may include supplying hydrogen stored in a compressed hydrogen tank of a compressed hydrogen supply system to a dehydrogenation reactor of a solid hydrogen supply system, and discharging a mixed gas of impurity gas and hydrogen from the dehydrogenation reactor to the outside.

[0031] According to the embodiment, hydrogen is supplied to the fuel cell through the compressed hydrogen supply system and the solid hydrogen supply system so that hydrogen is stably supplied to the fuel cell even when there is an emergency in the compressed hydrogen supply system or the solid hydrogen supply system.

[0032] Furthermore, the generation of impurity gases can be minimized through the purge process of the dehydrogenation reactor.

[0033] In addition, the effects that can be obtained or predicted by the embodiments of the present invention are disclosed directly or implicitly in the detailed description of the embodiments of the present invention. In other words, various effects predicted according to the embodiments of the present invention are disclosed in the detailed description described below. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] These drawings are for describing the embodiments of the present invention, and thus the technical spirit of the present invention should not be interpreted as being limited to the drawings.

[0035] Figure 1 is a circuit diagram showing the configuration of a hybrid hydrogen supply system according to the embodiment.

[0036] Figure 2 is a block diagram showing the configuration of a hybrid hydrogen supply system according to the embodiment.

[0037] Figures 3 to 6 is a flowchart illustrating a method of a hybrid hydrogen supply system according to an embodiment.

[0038] The above referenced drawings are not particularly drawn to scale, but should be understood to show various features of the basic principles of the invention that are simplified to a certain extent. For example, the specific design features of the present invention (including specific size, direction, position and shape) should be determined in part by the specific intended application and use environment.

[0039] Description of Reference Numerals

[0040] 10: Detector

[0041] 20: Controller

[0042] 30: Fuel Cells

[0043] 100: Compressed hydrogen supply system

[0044] 110: Compressed hydrogen tank

[0045] 120: First pressure regulator

[0046] 130: Booster pump

[0047] 200: Solid Hydrogen Supply System

[0048] 210: Acidic aqueous solution tank

[0049] 220: Dehydrogenation reactor

[0050] 230: Heat regulating device

[0051] 231: Storage tank

[0052] 232: Cooling pump

[0053] 233: Heat exchanger

[0054] 234: Cooling pipe

[0055] 240: Purification Device

[0056] 241: First purification tube

[0057] 242: Second purification tube

[0058] 243: First purge valve

[0059] 244: Second purge valve

[0060] 245: Vacuum pump

[0061] 250: Buffer tank

[0062] 260: Back pressure regulator

[0063] 270: Distillation unit

[0064] 280: Second pressure regulator

[0065] 300: discharge pipe. DETAILED DESCRIPTION

[0066] The term used in this article is only used to describe specific embodiments, and is not intended to limit the present invention. As used in this article, the singular form is also intended to include the plural form, unless they are clearly indicated differently by the context. It should be understood that when the terms "including" and / or "comprising" are used in the present invention, the terms "including" and / or "comprising" are intended to indicate that there are mentioned features, numerical values, steps, operations, constituent elements and / or components. However, these terms do not exclude the existence or addition of one or more other features, numerical values, steps, operations, constituent elements, components and / or combinations thereof. As used in this article, the term "and / or" includes any combination or all combinations of the relevant enumeration items.

[0067] In addition, it should be understood that one or more of the following methods or aspects thereof can be performed by one or more controllers. The term "controller" can refer to a hardware device including a memory and a processor. The memory is configured to store program instructions, and the processor is specifically programmed to execute program instructions so as to perform one or more processes described in more detail below. As disclosed herein, a controller can control the operation of a unit, module, component, device, or the like. In addition, as recognized by those of ordinary skill in the art, it should be understood that the following methods can be performed by a device including a controller and one or more other components.

[0068] In addition, the controller of the present invention can be implemented as a non-volatile computer-readable recording medium, which includes executable program instructions executed by a processor. Examples of computer-readable recording media include read-only memory (ROM), random access memory (RAM), compact disk (CD) ROM, magnetic tape, floppy disk, flash drive, smart card and optical data storage device, but are not limited to this. The computer-readable recording medium is also distributed throughout the computer network, and the program instructions can be stored and executed by a distribution scheme such as a telematics server or a controller area network (CAN).

[0069] The present invention is described in detail so that it can be easily carried out by those skilled in the art in the art to which the present invention belongs. However, the present invention can be implemented in various different forms and is not limited to the embodiments described herein.

[0070] In order to clearly describe the present invention, parts irrelevant to the description are omitted, and the same elements are denoted by the same reference numerals throughout the present invention.

[0071] In addition, since the size and thickness of each component shown in the drawings are arbitrarily shown for convenience of explanation, the present invention is not particularly limited to the size and thickness of each component. In addition, in order to clearly show each part and region, the thickness is exaggerated.

[0072] Suffixes such as “module” and / or “unit” of components used in the following present invention are given or mixed in consideration of making the present invention easy to understand, and have no distinguished meaning or role of their own.

[0073] Furthermore, in describing the disclosed embodiments, a detailed description of related known technologies has been omitted when it is determined that the detailed description makes the gist of the embodiments of the present invention unclear.

[0074] In addition, the accompanying drawings are provided to easily help understand the embodiments disclosed in the present invention, and the technical spirit disclosed in the present invention is not limited by the accompanying drawings. It should be understood that the present invention includes all modifications, equivalents and substitutes included in the spirit and technical scope of the present invention.

[0075] Terms including general numerals (eg, first and second) are used to describe various constituent elements, but the constituent elements are not limited by the terms.

[0076] In the following description, expressions described in the singular may be construed as singular or plural unless an explicit expression such as "a" or "an" is used.

[0077] These terms are only used to distinguish one component from another.

[0078] In the flowcharts described with reference to the drawings, the order of operations may be changed, a plurality of operations may be combined, or any operation may be divided, and a specific operation may not be performed.

[0079] When the controller, component, device, element, part, unit, module, etc. of the present invention is described as having a purpose or performing an operation, function, etc., the controller, component, device, element, part, unit or module should be considered herein as "configured to" meet the purpose or perform the operation or function. The controller, component, device, element, part, unit, module, etc. can each be implemented separately or included as part of the device together with a processor and a memory (e.g., a non-volatile computer-readable medium).

[0080] Hereinafter, a hybrid hydrogen supply system according to an embodiment is described in detail with reference to the accompanying drawings.

[0081] Figure 1 is a circuit diagram showing the configuration of a hybrid hydrogen supply system according to the embodiment.

[0082] like Figure 1 As shown, the hybrid hydrogen supply system according to the embodiment may include a compressed hydrogen supply system 100 and a solid hydrogen supply system 200 .

[0083] The compressed hydrogen supply system 100 may store hydrogen gas supplied from an external hydrogen charging station (not shown) and supply the hydrogen gas to the fuel cell 30 .

[0084] The compressed hydrogen supply system 100 may store compressed hydrogen supplied from an external hydrogen charging station, and selectively supply the stored compressed hydrogen to the fuel cell 30. The solid hydrogen supply system 200 may generate hydrogen through a chemical reaction of a chemical hydride, and selectively supply the generated hydrogen to the fuel cell 30. The hydrogen exhausted from the compressed hydrogen supply system 100 and the hydrogen exhausted from the solid hydrogen supply system 200 may be fluidly connected through the exhaust pipe 300. The hydrogen flowing through the exhaust pipe 300 may be supplied to the fuel cell 30.

[0085] The compressed hydrogen supply system 100 may include at least one compressed hydrogen tank 110 and a first pressure regulator 120 .

[0086] The compressed hydrogen tank 110 may receive hydrogen from an external hydrogen charging station (not shown) and temporarily store the received hydrogen. The stored hydrogen may be selectively supplied to the fuel cell 30.

[0087] The first pressure regulator 120 may be provided downstream of the compressed hydrogen tank 110, and regulates the pressure of the hydrogen gas supplied from the compressed hydrogen tank 110 to the fuel cell 30. When the internal pressure of the compressed hydrogen tank 110 is less than the set pressure of the first pressure regulator 120, the hydrogen gas stored in the compressed hydrogen tank 110 is not supplied to the fuel cell 30. When the internal pressure of the compressed hydrogen tank 110 is greater than the set pressure of the first pressure regulator 120, the pressure of the hydrogen gas stored in the compressed hydrogen tank 110 is reduced to the set pressure of the first pressure regulator 120. The hydrogen gas is then supplied to the fuel cell 30.

[0088] The solid hydrogen supply system 200 may generate hydrogen gas through a chemical reaction of a chemical hydride (hereinafter, referred to as a “reactant” as necessary), and the generated hydrogen gas may be selectively supplied to the fuel cell 30 .

[0089] To this end, the solid hydrogen supply system may include an acidic aqueous solution tank 210 , at least one dehydrogenation reactor 220 , a heat conditioning device 230 , and a buffer tank 250 .

[0090] The acidic aqueous solution tank 210 may store an acidic aqueous solution, and the stored acidic aqueous solution may be selectively supplied to the dehydrogenation reactor 220. An aqueous solution pump may be provided between the acidic aqueous solution tank 210 and the dehydrogenation reactor 220. The acidic aqueous solution stored in the acidic aqueous solution tank may be pumped by the aqueous solution pump and supplied to the dehydrogenation reactor 220.

[0091] The acidic aqueous solution tank 210 may have a corrosion-resistant protective film such as a Teflon coating to prevent corrosion of the acidic aqueous solution. The acidic aqueous solution shortens the half-life by adjusting the pH of the chemical hydride to promote the dehydrogenation reaction.

[0092] The acid may be an inorganic acid, such as sulfuric acid, nitric acid, phosphoric acid, boric acid or hydrochloric acid. The acid may also be an organic acid, such as heteropolyacids, acetic acid, formic acid, maleic acid Citric acid, tartaric acid, ascorbic acid Lactic acid, oxalic acid, succinic acid Taurine or a mixture thereof. Formic acid has a molecular weight smaller than that of hydrogen ions, which can reduce the weight of the system, and formic acid is safer than hydrochloric acid in a high concentration state, so formic acid (HCOOH) can be used.

[0093] Phosphoric acid, which is a weak acid, can be kept at a low pH under set conditions and can be used relatively safely. In addition, the collected carbon dioxide can be obtained by hydrogenation, which is an important substance in terms of carbon dioxide recovery / recycling. In addition, formate is converted into bicarbonate by dehydrogenation reaction, which can further obtain hydrogen.

[0094] The dehydrogenation reactor 220 may generate hydrogen through a chemical reaction of a chemical hydride and an acidic aqueous solution.

[0095] The dehydrogenation reactor 220 may be composed of a high temperature and high pressure container so that the dehydrogenation reaction can be achieved under high temperature and high pressure conditions. For example, the dehydrogenation reactor 220 may have a cylindrical, spherical, cuboid or polygonal columnar shape. In particular, the dehydrogenation reactor 220 may have a cylindrical shape.

[0096] The solid chemical hydride may be in any of the forms of powder, granules, beads, microcapsules and pellets, for example.

[0097] The chemical hydride can be any compound that hydrolyzes and produces hydrogen and a hydrolyzate, which may include, for example, sodium borohydride (NaBH4), lithium borohydride (LiBH4), potassium borohydride (KBH4), ammonium borohydride (NH4BH4), ammonia borane (NH3BH3), tetramethylammonium borohydride ((CH3)4NH4BH4), sodium aluminum hydride (NaAlH4), lithium aluminum hydride (LiAlH4), potassium aluminum hydride (KAlH4), calcium borohydride (Ca(BH4)2), magnesium borohydride (Mg(BH4)2), sodium gallium hydride (NaGaH4), lithium gallium hydride (LiGaH4), potassium gallium hydride (KGaH4), lithium hydride (LiH), calcium hydride (CaH2), magnesium hydride (MgH2) or a mixture thereof.

[0098] Since the hydrogen generation reaction in the dehydrogenation reactor 220 is a heating reaction, a heat regulating device 230 is provided to cool the reaction heat.

[0099] The heat conditioning device 230 may include a storage tank 231 storing heat medium and a cooling pump 232 pumping the heat medium stored in the storage tank 231 and supplying the pumped heat medium to the dehydrogenation reactor 220. The heat conditioning device 230 may further include a heat exchanger 233 for cooling the heat medium heated by the dehydrogenation reactor 220.

[0100] The storage tank 231, the cooling pump 232, the dehydrogenation reactor 220 and the heat exchanger 233 are fluidly connected by a cooling pipe 234 through which the heat medium flows. The heat medium stored in the storage tank 231 circulates in the cooling pump 232, the dehydrogenation reactor 220 and the heat exchanger 233, and flows back to the storage tank 231.

[0101] The heat medium flowing through the cooling pipe 234 may include at least any one of a water-like liquid refrigerant, an oil-like liquid refrigerant, a fluorine-based gas refrigerant, and an inorganic compound-based gas refrigerant.

[0102] The cooling pump 232 may be an electric water pump (EWP) that pumps heat medium by electricity.

[0103] The heat exchanger 233 may be an air-cooled or water-cooled radiator, or a plate-type heat exchanger 233. As required, the heat exchanger 233 may be used together with an air-conditioning compressor provided in the vehicle.

[0104] The hydrogen generated by the dehydrogenation reactor 220 may be temporarily stored in the buffer tank 250. A separate buffer tank 250 is not provided in the solid hydrogen supply system 200, but the buffer tank 250 may be replaced by the compressed hydrogen tank 110 of the compressed hydrogen supply system 100. When the dehydrogenation reactor 220 is replaced, the residual hydrogen stored in the buffer tank 250 may be discharged to the outside.

[0105] A back pressure regulator 260 may be provided between the dehydrogenation reactor 220 and the buffer tank 250 (or downstream of the dehydrogenation reactor 220). In addition, a second pressure regulator 280 may be provided downstream of the buffer tank 250. When the internal pressure of the buffer tank 250 is less than the set pressure of the second pressure regulator 280, the hydrogen stored in the buffer tank 250 is not supplied to the fuel cell 30. When the pressure of the hydrogen stored in the buffer tank 250 increases to the set pressure of the second pressure regulator 280, the hydrogen is supplied to the fuel cell 30.

[0106] In order to stably extract hydrogen from the dehydrogenation reactor 220, the boiling point (100° C. to 400° C.) of the reactants is adjusted by increasing the internal pressure of the reaction vessel of the dehydrogenation reactor 220 to a specific pressure (e.g., 1 to 350 bar) to minimize the phase change of the reactants. To this end, a back pressure regulator 260 and a second pressure regulator 280 are arranged downstream of the dehydrogenation reactor 220 to adjust the internal pressure of the reaction vessel of the dehydrogenation reactor 220.

[0107] In this case, hydrogen generated from the inside of the reaction vessel of the dehydrogenation reactor 220 may be temporarily stored in the buffer tank 250 at a pressure almost the same as the internal pressure of the reaction vessel of the dehydrogenation reactor 220 through the back pressure regulator 260 until the second pressure regulator 280 is opened to take out hydrogen from the buffer tank 250. Therefore, hydrogen can be stored in the buffer tank 250 at a pressure similar to the internal pressure of the dehydrogenation reactor 220 without applying separate energy.

[0108] A rectification device 270 that removes impurities generated from the inside of the dehydrogenation reactor 220 may be provided between the dehydrogenation reactor 220 and the buffer tank 250 (or downstream of the dehydrogenation reactor 220 ).

[0109] When the hydride and the acidic aqueous solution react with each other in the dehydrogenation reactor 220, carbon monoxide and moisture may be generated as byproducts. When the carbon monoxide and moisture generated as byproducts are supplied to the fuel cell 30, the durability of the fuel cell 30 may be deteriorated.

[0110] The rectification device 270 may include a methane generator (not shown) for removing carbon monoxide contained in hydrogen and / or a gas / liquid separator (not shown) for removing moisture.

[0111] When hydrogen is produced by the dehydrogenation reaction of the hydride and the acidic aqueous solution in the dehydrogenation reactor 220, the methane generator converts the carbon monoxide produced as a byproduct into methane. In the methane generator, the carbon monoxide is converted into methane when the gas of hydrogen and carbon monoxide discharged from the dehydrogenation reactor 220 passes through the catalyst. The catalyst of the methane generator may contain at least one of nickel (NI), ruthenium (Ru), cobalt (Co), rhodium (RH) and iron (Fe). The solid catalyst may be, for example, any type of particles, beads, microcapsules and pellets.

[0112] The gas / liquid separator can separate the excess water contained in the hydrogen.

[0113] When the hydride is recharged into the dehydrogenation reactor 220, external air may flow into the dehydrogenation reactor 220. Alternatively, a set amount of product may be generated in the dehydrogenation reactor 220, and impurity gas may flow into the dehydrogenation reactor 220 when the re-reaction is achieved.

[0114] Thus, when the external air flows into the dehydrogenation reactor 220, a situation may be formed in which impurity gases such as carbon monoxide are easily generated in addition to hydrogen due to any overheating generated inside the dehydrogenation reactor 220. Therefore, there may be a problem that it is difficult to generate pure hydrogen due to the impurity gases flowing into the dehydrogenation reactor 220.

[0115] In order to prevent such a problem, the hybrid hydrogen supply system according to the embodiment may be provided with a purification device 240 for discharging the impurity gas in the dehydrogenation reactor 220 to the outside. The purification device 240 may discharge the impurity gas in the dehydrogenation reactor 220 to the outside through hydrogen at a set pressure or higher, or discharge the impurity gas in the dehydrogenation reactor 220 to the outside through a vacuum pump 245.

[0116] To this end, the purification device 240 may include a first purification pipe 241, which fluidically connects the compressed hydrogen tank 110 of the compressed hydrogen supply system 100 and the dehydrogenation reactor 220 of the solid hydrogen supply system 200. The purification device 240 may also include: a second purification pipe 242, a first purification valve 243, and a second purification valve 244, wherein the second purification pipe 242 connects the dehydrogenation reactor 220 and an external fluid; the first purification valve 243 is disposed in the first purification pipe 241 between the compressed hydrogen tank 110 and the dehydrogenation reactor 220; and the second purification valve 244 is disposed in the second purification pipe 242 downstream of the dehydrogenation reactor 220. As needed, a vacuum pump 245 may be disposed in the purification pipe downstream of the second purification valve 244.

[0117] The first purge valve 243 may include a solenoid valve and / or a third pressure regulator.

[0118] When purification is required in the dehydrogenation reactor 220 (e.g., recharging of hydride in the dehydrogenation reactor 220), pure hydrogen gas at room pressure or higher stored in the compressed hydrogen tank 110 is supplied to the dehydrogenation reactor 220 through the first purification pipe 241 to purify the interior of the dehydrogenation reactor 220 with pure hydrogen gas. The purification process may be performed for a period of time (e.g., 1 second to 1 minute) in which the internal pressure of the dehydrogenation reactor 220 is set to room pressure or higher.

[0119] The mixed gas of the impurity gas (eg, external air, etc.) and the hydrogen gas in the dehydrogenation reactor 220 of the solid hydrogen supply system 200 is discharged to the outside through the second purification pipe 242 through the purification process.

[0120] When the dehydrogenation reactor 220 is pressurized by hydrogen after the purification process, the dehydrogenation reactor 220 may be pressurized at a set pressure (eg, 2 bar) or more.

[0121] When there is not enough hydrogen in the compressed hydrogen tank 110 for purging the dehydrogenation reactor 220 , the vacuum pump 245 may be used to purge the interior of the dehydrogenation reactor 220 .

[0122] A boost pump 130 may be provided between the buffer tank 250 and the compressed hydrogen tank 110. The boost pump 130 may pressurize the hydrogen stored in the buffer tank 250 and supply the pressurized hydrogen to the compressed hydrogen tank 110. Therefore, the hydrogen stored in the buffer tank 250 may be stored in the compressed hydrogen tank 110 at a pressure equal to or greater than the reaction pressure in the dehydrogenation reactor 220 by the boost pump 130.

[0123] In addition, a fourth pressure regulator (not shown) may be provided downstream of the first pressure regulator 120 and the second pressure regulator 280 .

[0124] The hybrid hydrogen supply system according to the embodiment may include a controller 20 which controls each component of the hybrid hydrogen supply system based on operation information detected by the detector 10 .

[0125] The controller 20 may be implemented as one or more processors operated by a set program. The memory of the controller 20 stores program instructions programmed to execute each step of the hybrid hydrogen supply method according to the embodiment through one or more processors.

[0126] The controller 20 may control operations of the compressed hydrogen supply system 100 and the solid hydrogen supply system 200 .

[0127] The detector 10 may include: a first flow sensor (not shown), a second flow sensor (not shown), and a first pressure sensor (not shown), the first flow sensor (not shown) measuring the amount of reactants of the dehydrogenation reactor 220; the second flow sensor (not shown) measuring the amount of hydrogen stored in the compressed hydrogen tank 110; and the first pressure sensor (not shown) measuring the pressure of the hydrogen stored in the compressed hydrogen tank 110. The detector 10 may also include: a third flow sensor (not shown), a second pressure sensor (not shown), a fourth flow sensor (not shown), and a third pressure sensor (not shown), the third flow sensor (not shown) measuring the amount of hydrogen stored in the buffer tank 250; the second pressure sensor (not shown) measuring the pressure of the hydrogen stored in the buffer tank 250; the fourth flow sensor (not shown) measuring the flow rate of hydrogen generated by the dehydrogenation reactor 220; and the third pressure sensor (not shown) measuring the internal pressure of the dehydrogenation reactor 220.

[0128] Hereinafter, the actuation of the hybrid hydrogen supply system according to the embodiment is described in detail with reference to the accompanying drawings.

[0129] Figure 3 is a flowchart illustrating a method of controlling a hybrid hydrogen supply system according to an embodiment.

[0130] like Figure 3 As shown, the hybrid hydrogen supply system according to the embodiment may be selectively actuated in any one of the first mode, the second mode, and the third mode.

[0131] When the first condition (S10) is satisfied, the first mode (S20) is executed.

[0132] The first mode is a mode in which hydrogen is preferentially supplied from the compressed hydrogen supply system 100 to the fuel cell 30. When the first condition is satisfied, the hybrid hydrogen supply system may be activated in the first mode.

[0133] The first condition may be satisfied when hydrogen cannot be produced from the solid-state hydrogen supply system 200 (e.g., all reactants of the dehydrogenation reactor 220 are exhausted), or when the amount of hydrogen stored in the compressed hydrogen tank 110 of the compressed hydrogen supply system 100 is less than a set amount and the storage capacity of the compressed hydrogen tank 110 is equal to or greater than the total hydrogen production in the solid-state hydrogen supply system 200.

[0134] When the second condition (S30) is satisfied, the second mode (S40) is executed.

[0135] The second mode is a mode in which hydrogen is preferentially supplied from the solid hydrogen supply system 200 to the fuel cell 30. When the second condition is satisfied, the hybrid hydrogen supply system may be actuated in the second mode.

[0136] The second condition may be satisfied when the hydrogen stored in the compressed hydrogen tank 110 of the compressed hydrogen supply system 100 is completely consumed. Alternatively, the second condition may be satisfied when the amount of hydrogen generated by the solid hydrogen supply system 200 can satisfy the amount of hydrogen required by the fuel cell 30. The second condition may also be satisfied when the storage capacity of the buffer tank 250 of the solid hydrogen supply system 200 is equal to or greater than the total amount of hydrogen generated in the dehydrogenation reactor 220.

[0137] When the third condition (S50) is satisfied, the third mode (S60) is executed.

[0138] Furthermore, the third mode is a mode when hydrogen of the compressed hydrogen supply system 100 and hydrogen of the solid hydrogen supply system 200 are mixed with each other, thereby supplying hydrogen to the fuel cell 30. When the third condition is satisfied, the hybrid hydrogen supply system may be activated in the third mode.

[0139] The third condition may be satisfied when the flow rate of hydrogen generated by the dehydrogenation reactor 220 of the solid hydrogen supply system 200 deviates from the set range (e.g., when the flow rate of hydrogen generated by the dehydrogenation reactor 220 is not constant). Alternatively, the third condition may be satisfied when the storage capacity of the buffer tank 250 of the solid hydrogen supply system 200 is less than the total amount of hydrogen generated by the dehydrogenation reactor 220 of the solid hydrogen supply system 200. This occurs when the time required to increase the pressure of the hydrogen stored in the buffer tank 250 to be equal to or greater than the set pressure of the second pressure regulator 280 is equal to or greater than the set time (i.e., the time period required to increase the internal pressure of the buffer tank 250 to be equal to or greater than the set pressure of the second pressure regulator 280).

[0140] refer to Figure 4When the first mode is executed, hydrogen is supplied from the compressed hydrogen supply system 100 to the fuel cell 30. In other words, the hydrogen stored in the compressed hydrogen tank 110 is supplied to the fuel cell 30 (S110). In this case, the hydrogen is supplied to the fuel cell 30 at a pressure set by the first pressure regulator 120.

[0141] The controller 20 determines whether the internal pressure of the compressed hydrogen tank 110 is less than a set pressure (e.g., 16 bar) (S120). When the internal pressure of the compressed hydrogen tank 110 is less than the set pressure, the hydrogen supply through the compressed hydrogen supply system 100 is stopped, and hydrogen is supplied to the fuel cell 30 from the solid hydrogen supply system 200 (S130).

[0142] The controller 20 determines whether the internal pressure of the dehydrogenation reactor 220 is less than the set pressure (S140). When the internal pressure of the dehydrogenation reactor 220 is less than the set pressure, the supply of hydrogen through the solid hydrogen supply system 200 is stopped (S150).

[0143] Thus, the hydrogen stored in the compressed hydrogen tank 110 is preferentially supplied to the fuel cell 30 in the first mode. Thereafter, when the hydrogen stored in the compressed hydrogen tank 110 is completely consumed, hydrogen is supplied to the fuel cell 30 through the solid hydrogen supply system 200.

[0144] When the reactants of the dehydrogenation reactor 220 of the solid hydrogen supply system 200 are completely consumed, the supply of hydrogen to the fuel cell 30 is stopped.

[0145] refer to Figure 5 When the second mode is executed, the controller 20 determines whether the purification condition is satisfied (S210). When the dehydrogenation reactor 220 is replaced, the purification condition may be satisfied.

[0146] When the purification condition is satisfied, the purification process of the dehydrogenation reactor 220 is performed (S220).

[0147] In this case, the first purge valve 243 is turned on, and the hydrogen stored in the compressed hydrogen tank 110 is supplied to the dehydrogenation reactor 220 through the first purge pipe 241. When the purge of the dehydrogenation reactor 220 is completed, the second purge valve 244 is turned on, and the mixed gas of the impurity gas and the hydrogen of the dehydrogenation reactor 220 is discharged to the outside through the second purge pipe 242.

[0148] When the amount of hydrogen stored in the compressed hydrogen tank 110 is less than the set amount (when the amount of hydrogen is insufficient to perform the purification process), the second purification valve 244 is turned on and the vacuum pump 245 is actuated. The impurity gas in the dehydrogenation reactor 220 is discharged to the outside by the actuation of the vacuum pump 245.

[0149] The interior of the dehydrogenation reactor 220 is filled with hydrogen stored in the compressed hydrogen tank 110 of the compressed hydrogen supply system 100 at a set pressure or higher through a purification process. Therefore, the interior of the dehydrogenation reactor 220 is maintained with pure hydrogen or maintained in a vacuum state. Pure hydrogen can be generated by a chemical reaction of the reactants in the dehydrogenation reactor 220.

[0150] Hydrogen is supplied to the fuel cell 30 from the solid hydrogen supply system 200 (S230). In other words, hydrogen is generated by a chemical reaction of the chemical hydride stored in the dehydrogenation reactor 220 and the acidic aqueous solution, and the generated hydrogen is stored in the buffer tank 250. In addition, the hydrogen stored in the buffer tank 250 is supplied to the fuel cell 30. In this case, the pressure of the hydrogen stored in the buffer tank 250 is reduced according to the set pressure of the second pressure regulator 280 provided downstream of the buffer tank 250, and then the hydrogen is supplied to the fuel cell 30.

[0151] The controller 20 determines whether the internal pressure of the dehydrogenation reactor 220 is less than a set pressure (S240).

[0152] When the internal pressure of the dehydrogenation reactor 220 is less than the set pressure, the supply of hydrogen through the solid hydrogen supply system 200 is stopped. In addition, hydrogen is supplied from the compressed hydrogen supply system 100 to the fuel cell 30. In other words, the hydrogen stored in the compressed hydrogen tank 110 of the compressed hydrogen supply system 100 is supplied to the fuel cell 30 (S250).

[0153] The controller 20 determines whether the internal pressure of the compressed hydrogen tank 110 is less than a set pressure (S260).

[0154] When the internal pressure of the compressed hydrogen tank 110 is less than the set pressure, the supply of hydrogen gas through the compressed hydrogen supply system 100 is stopped (S270).

[0155] In other words, in the second mode, hydrogen generated by the dehydrogenation reactor 220 of the solid hydrogen supply system 200 is preferentially supplied to the fuel cell 30. Thereafter, when hydrogen generation by the solid hydrogen supply system 200 is terminated, hydrogen is supplied to the fuel cell 30 by the compressed hydrogen supply system 100.

[0156] refer to Figure 6 When the third mode is executed, the controller 20 determines whether the purification condition is satisfied (S310). When the dehydrogenation reactor 220 is replaced, the purification condition may be satisfied.

[0157] When the purification condition is satisfied, the purification process of the dehydrogenation reactor 220 is performed (S320).

[0158] In this case, the first purge valve 243 is turned on, and the hydrogen stored in the compressed hydrogen tank 110 is supplied to the dehydrogenation reactor 220 through the first purge pipe 241. When the purge of the dehydrogenation reactor 220 is completed, the second purge valve 244 is turned on, and the mixed gas of the impurity gas and the hydrogen of the dehydrogenation reactor 220 is discharged to the outside through the second purge pipe 242.

[0159] When the amount of hydrogen stored in the compressed hydrogen tank 110 is less than the set amount (when the amount of hydrogen is insufficient to perform the purification process), the second purification valve 244 is turned on and the vacuum pump 245 is actuated. The impurity gas in the dehydrogenation reactor 220 is discharged to the outside by the actuation of the vacuum pump 245.

[0160] The interior of the dehydrogenation reactor 220 is charged with hydrogen stored in the compressed hydrogen tank 110 of the compressed hydrogen supply system 100 at a set pressure or higher through a purification process. Therefore, the interior of the dehydrogenation reactor 220 is maintained with pure hydrogen or maintained in a vacuum state, and pure hydrogen can be generated by a chemical reaction of the reactants within the dehydrogenation reactor 220.

[0161] Hydrogen is supplied to the fuel cell 30 from the solid hydrogen supply system 200. In other words, the hydrogen generated by the dehydrogenation reactor 220 of the solid hydrogen supply system 200 is supplied to the fuel cell 30 (S330). In this case, the set pressure of the second pressure regulator 280 is set to be greater than the set pressure of the first pressure regulator 120. Therefore, the pressure of the hydrogen stored in the buffer tank 250 is reduced to the set pressure of the second pressure regulator 280 by the second pressure regulator 280, and then the hydrogen stored in the buffer tank 250 is supplied to the fuel cell 30.

[0162] When the pressure of the hydrogen gas stored in the buffer tank 250 is lower than the set pressure P2 of the second pressure regulator 280 ( S340 ), the supply of the hydrogen gas supplied from the solid hydrogen supply system 200 to the fuel cell 30 is stopped.

[0163] In addition, hydrogen is supplied from the compressed hydrogen supply system 100 to the fuel cell 30 (S350). In this case, the pressure of the hydrogen stored in the compressed hydrogen tank 110 is reduced to the set pressure of the first pressure regulator 120, and then the hydrogen stored in the compressed hydrogen tank 110 is supplied to the fuel cell 30.

[0164] When the pressure of the hydrogen stored in the buffer tank 250 is higher than the set pressure of the second pressure regulator 280 due to the hydrogen generation in the dehydrogenation reactor 220 (S360), the supply of hydrogen from the compressed hydrogen supply system 100 to the fuel cell 30 is stopped. Instead, hydrogen is supplied from the solid hydrogen supply system 200 to the fuel cell 30 (S330).

[0165] In this way, when the internal pressure of the buffer tank 250 is higher than the set pressure of the second pressure regulator 280, hydrogen can be supplied from the solid hydrogen supply system 200 to the fuel cell 30, and when the internal pressure of the compressed hydrogen tank 110 is higher than the set pressure of the first pressure regulator 120, hydrogen can be supplied from the compressed hydrogen supply system 100 to the fuel cell 30. In other words, hydrogen is supplied from the solid hydrogen supply system 200 and the compressed hydrogen supply system 100 to the fuel cell 30 until the reactants of the dehydrogenation reactor 220 are exhausted and the hydrogen of the compressed hydrogen tank 110 is exhausted.

[0166] Through the hybrid hydrogen supply system according to the embodiment, hydrogen gas may be stably supplied to the fuel cell 30 from the compressed hydrogen supply system 100 or the solid hydrogen supply system 200 .

[0167] In addition, through the purification process of the dehydrogenation reactor 220, the generation of impurity gas in the dehydrogenation reactor 220 may be minimized.

[0168] Although preferred embodiments of the present invention have been described above, the present invention is not limited thereto. Various modifications may be made within the scope of the claims, the detailed description of the invention and the drawings without departing from the scope of the invention as defined in the appended claims.

Claims

1. A hybrid hydrogen supply system, comprising: a compressed hydrogen supply system configured to store compressed hydrogen gas supplied from an external hydrogen charging station and selectively supply the compressed hydrogen gas to the fuel cell; as well as A solid-state hydrogen supply system is configured to generate hydrogen gas through a chemical reaction of a chemical hydride and selectively supply the generated hydrogen gas to a fuel cell.

2. The hybrid hydrogen supply system according to claim 1, wherein: The compressed hydrogen supply system comprises: at least one compressed hydrogen tank configured to store compressed hydrogen gas; and A first pressure regulator is disposed downstream of the compressed hydrogen tank.

3. The hybrid hydrogen supply system according to claim 2, wherein: The solid hydrogen supply system comprises: an acidic aqueous solution tank configured to store the acidic aqueous solution; at least one dehydrogenation reactor configured to store a chemical hydride and selectively receive an acidic aqueous solution stored in an acidic aqueous solution tank to generate hydrogen gas; and A heat regulating device is configured to regulate the temperature of the dehydrogenation reactor.

4. The hybrid hydrogen supply system according to claim 3, wherein: The solid hydrogen supply system further comprises: The purification device is configured to discharge the impurity gas in the dehydrogenation reactor.

5. The hybrid hydrogen supply system according to claim 4, wherein: The purification device comprises: a first purge tube configured to fluidly connect the compressed hydrogen tank and the dehydrogenation reactor; a second purge pipe configured to connect the dehydrogenation reactor to an external fluid; A first purge valve disposed in a first purge pipe between the compressed hydrogen tank and the dehydrogenation reactor; and The second purge valve is arranged in the second purge pipe downstream of the dehydrogenation reactor.

6. The hybrid hydrogen supply system according to claim 5, wherein: The purification device further comprises: A vacuum pump is disposed in the second purification pipe downstream of the second purification valve.

7. The hybrid hydrogen supply system according to claim 3, further comprising: A buffer tank is configured to temporarily store hydrogen generated by the dehydrogenation reactor.

8. The hybrid hydrogen supply system according to claim 7, further comprising: The boost pump is arranged between the buffer tank and the compressed hydrogen tank.

9. The hybrid hydrogen supply system according to claim 7, wherein: The buffer tank is a compressed hydrogen tank of a compressed hydrogen supply system.

10. The hybrid hydrogen supply system according to claim 7, wherein: The solid hydrogen supply system further comprises: a back pressure regulator disposed upstream of the buffer tank; a hydrogen rectification device, which is arranged upstream of the back pressure regulator; and A second pressure regulator is disposed downstream of the buffer tank.

11. A hybrid hydrogen supply method using a compressed hydrogen supply system and a solid hydrogen supply system, the hybrid hydrogen supply method comprising: When a first condition is satisfied, a first mode is executed, in which hydrogen is supplied to the fuel cell from a compressed hydrogen supply system; When the second condition is satisfied, a second mode is executed, in which hydrogen is supplied from the solid hydrogen supply system to the fuel cell; The third mode is executed when the third condition is satisfied, in which hydrogen is supplied to the fuel cell while the solid hydrogen supply system and the compressed hydrogen supply system are mixed with each other.

12. The mixed hydrogen supply method according to claim 11, wherein: The first condition is met when: When all reactants in the dehydrogenation reactor of the solid hydrogen supply system are exhausted; or When the amount of hydrogen stored in the compressed hydrogen tank of the compressed hydrogen supply system is less than the set amount and the storage capacity of the compressed hydrogen tank is equal to or greater than the total hydrogen generation amount in the solid hydrogen supply system.

13. The mixed hydrogen supply method according to claim 11, wherein: The second condition is satisfied when: When the hydrogen stored in the compressed hydrogen tank of the compressed hydrogen supply system is exhausted; When the amount of hydrogen produced by the solid hydrogen supply system meets the amount of hydrogen required by the fuel cell; or When the storage capacity of the buffer tank of the solid hydrogen supply system is equal to or greater than the total hydrogen production in the dehydrogenation reactor.

14. The mixed hydrogen supply method according to claim 11, wherein: The third condition is satisfied when: When the flow rate of hydrogen generated by the dehydrogenation reactor of the solid hydrogen supply system deviates from the set range; When the storage capacity of the buffer tank of the solid hydrogen supply system is less than the total hydrogen production of the dehydrogenation reactor of the solid hydrogen supply system; or When the time required to increase the pressure of the hydrogen gas stored in the buffer tank to be equal to or greater than the set pressure of the second pressure regulator is equal to or greater than the set time.

15. The mixed hydrogen supply method according to claim 11, wherein: The first mode includes: supplying hydrogen gas stored in a compressed hydrogen tank of a compressed hydrogen supply system to the fuel cell; When the internal pressure of the compressed hydrogen tank is lower than the set pressure, hydrogen is supplied from the solid hydrogen supply system to the fuel cell.

16. The mixed hydrogen supply method according to claim 11, wherein: The second mode includes: When the purification conditions are met, a purification process of the dehydrogenation reactor of the solid hydrogen supply system is performed; supplying hydrogen gas to the fuel cell from a solid hydrogen supply system; When the internal pressure of the dehydrogenation reactor is lower than the set pressure, hydrogen is supplied from the compressed hydrogen tank of the compressed hydrogen supply system to the fuel cell.

17. The mixed hydrogen supply method according to claim 16, wherein: The decontamination process includes: supplying hydrogen gas stored in a compressed hydrogen tank of a compressed hydrogen supply system to a dehydrogenation reactor of a solid hydrogen supply system; The mixed gas of the impurity gas and hydrogen gas in the dehydrogenation reactor is discharged to the outside.

18. The mixed hydrogen supply method according to claim 11, wherein: The third mode includes: When the purge mode is satisfied, a purge process of a dehydrogenation reactor of a solid hydrogen supply system is performed; supplying hydrogen gas to the fuel cell from a solid hydrogen supply system; When the pressure of the hydrogen stored in the buffer tank of the solid hydrogen supply system is lower than the set pressure of the pressure regulator provided downstream of the buffer tank, supplying the hydrogen stored in the compressed hydrogen tank of the compressed hydrogen supply system to the fuel cell; When the pressure of the hydrogen gas stored in the buffer tank is higher than the set pressure of a pressure regulator provided downstream of the buffer tank, hydrogen gas is supplied from the solid hydrogen supply system to the fuel cell.

19. The mixed hydrogen supply method according to claim 18, wherein: The decontamination process includes: supplying hydrogen gas stored in a compressed hydrogen tank of a compressed hydrogen supply system to a dehydrogenation reactor of a solid hydrogen supply system; The mixed gas of the impurity gas and hydrogen gas in the dehydrogenation reactor is discharged to the outside.

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