Hybrid hydrogenation system and method

Abstract

The apparatus of this application may include: a solid-phase hydrogen supply system configured to generate hydrogen gas within a first pressure range based on a chemical reaction of a chemical hydride; a compression system configured to selectively change the pressure of the hydrogen gas generated by the solid-phase hydrogen supply system to a second pressure range exceeding the first pressure range; and a distributor configured to supply hydrogen gas from at least one of the solid-phase hydrogen supply system or the compression system to a hydrogenation target.

Description

[0001] Cross-references to related applications

[0002] This application claims priority to Korean Patent Application No. 10-2024-0186759, filed with the Korean Intellectual Property Office on December 16, 2024, the entire disclosure of which is incorporated herein by reference. Technical Field

[0003] This invention relates to hybrid hydrogen systems and methods, and more specifically, to hybrid hydrogen systems and methods capable of combining compressed hydrogen supply systems and solid-phase hydrogen supply systems. Background Technology

[0004] The content described in this background section is only intended to enhance the understanding of the background of this disclosure and should not be construed as an endorsement that it corresponds to prior art known to those skilled in the art.

[0005] Due to the depletion of fossil fuels and environmental pollution, there is a huge demand for renewable and alternative energy sources, and hydrogen is receiving increasing attention as one such alternative energy source.

[0006] Fuel cells and hydrogen combustion devices use hydrogen as a reactant gas, but in order to apply fuel cells and hydrogen combustion devices to automobiles (e.g., fuel cell vehicles) and various electronic products, a stable and continuous hydrogen supply technology can be applied.

[0007] To supply hydrogen to charging target 40 (e.g., fuel cell electric vehicles), separate hydrogen charging stations can be installed in each area, and fuel cell electric vehicles can move to the charging station to refuel with hydrogen.

[0008] Hydrogen storage tanks containing low-pressure hydrogen (e.g., 5 to 200 bar) can be supplied to hydrogen refueling stations via trailers, etc. The low-pressure hydrogen stored in the tanks can be compressed to high pressure (e.g., 875 bar) using a mechanical compressor and supplied to the hydrogen refueling target.

[0009] Mechanical compressors can be used to directly compress low-pressure hydrogen into high-pressure hydrogen (hereinafter referred to as "compressed hydrogen supply method"). However, depending on the needs (e.g., to shorten hydrogen compression time, improve compression efficiency, or ensure the durability of hydrogen refueling facilities), low-pressure hydrogen can be first compressed into medium-pressure hydrogen (e.g., 200 to 400 bar), and then compressed a second time into high-pressure hydrogen and supplied to the hydrogen refueling target.

[0010] On the other hand, it is also possible to consider a method of supplying hydrogen to hydrogenation target 40 by injecting an acidic aqueous solution, an acid catalyst, or a mixture of water and an acid catalyst into a solid-phase hydride stored in a dehydrogenation reactor to generate hydrogen (hereinafter referred to as the "solid-phase hydrogen supply method").

[0011] To refuel hydrogen stations using the compressed hydrogen supply method, separate large transport vehicles (such as trailers) are used to supply hydrogen, and separate space is used to prevent hydrogen storage tanks from the trailers from increasing carbon emissions and transportation costs.

[0012] In addition, although the solid-phase hydrogen supply method can produce high-pressure hydrogen, it has the following problems: the reactor materials and structure must be designed to withstand high pressure, and a separate device must be used for thermal management of the reactor. Summary of the Invention

[0013] This disclosure aims to provide a hybrid hydrogen refueling system and method that utilizes both compressed hydrogen supply and solid-phase hydrogen supply methods to reduce the space and transportation costs of hydrogen refueling stations and ensure durability.

[0014] The apparatus according to this disclosure may include: a solid-phase hydrogen supply system configured to generate hydrogen gas within a first pressure range based on a chemical reaction of a chemical hydride; a compression system configured to selectively change the pressure of the hydrogen gas generated by the solid-phase hydrogen supply system to a second pressure range beyond the first pressure range; and a distributor configured to supply hydrogen gas from at least one of the solid-phase hydrogen supply system or the compression system to a hydrogenation target.

[0015] In this device, the compression system may include: a hydrogen compressor configured to pressurize hydrogen produced by the solid-phase hydrogen supply system; and a hydrogen tank configured to store hydrogen pressurized by the hydrogen compressor.

[0016] In this device, the solid-phase hydrogen supply system may include: an acid aqueous solution tank configured to store an acidic aqueous solution; at least one dehydrogenation reactor configured to store chemical hydrides and selectively supply the acidic aqueous solution stored in the acid aqueous solution tank to generate hydrogen; and a cooler configured to control the temperature of at least one dehydrogenation reactor.

[0017] In this apparatus, the solid-phase hydrogen supply system may further include a purging assembly configured to discharge impurity gases from the dehydrogenation reactor. The purging assembly may include a purging pipe configured to fluidly connect the dehydrogenation reactor to an outlet located outside the solid-phase hydrogen supply system; and a purging valve disposed within the purging pipe and downstream of the dehydrogenation reactor.

[0018] In this apparatus, the purging assembly may also include a vacuum pump disposed in the purging pipe and downstream of the purging valve. The apparatus may also include a buffer tank configured to temporarily store hydrogen produced by at least one dehydrogenation reactor.

[0019] In this device, the compression system may further include a booster pump disposed between the buffer tank and the hydrogen storage tank of the compression system. In this device, the solid-phase hydrogen supply system may include a back pressure regulator disposed upstream of the buffer tank and a gas purifier disposed upstream of the back pressure regulator.

[0020] The method according to this disclosure is executed by an apparatus, which may include a compression system and a solid-phase hydrogen supply system. The method may include: determining whether the dehydrogenation reactor is undergoing a dehydrogenation reaction to generate hydrogen based on the internal pressure of the dehydrogenation reactor or the internal pressure of the buffer tank; determining whether a booster pump and a hydrogen compressor are compressing hydrogen from the buffer tank into the hydrogen storage tank based on the internal pressure of the hydrogen storage tank; and supplying hydrogen to the hydrogenation target by the following steps, based on the required charging pressure associated with the hydrogenation target: supplying hydrogen stored in the hydrogen storage tank to the hydrogenation target, or supplying hydrogen stored in the buffer tank to the hydrogenation target.

[0021] In this method, the step of determining whether the dehydrogenation reactor undergoes a dehydrogenation reaction to generate hydrogen may include: determining whether the internal pressure of the dehydrogenation reactor or the internal pressure of the buffer tank is greater than or equal to a first set pressure. The method may further include: when the internal pressure of the dehydrogenation reactor or the internal pressure of the buffer tank is less than the first set pressure, controlling the dehydrogenation reactor to undergo a dehydrogenation reaction to generate hydrogen.

[0022] The method may further include stopping the dehydrogenation reaction through the dehydrogenation reactor when the internal pressure of the dehydrogenation reactor or the internal pressure of the buffer tank is greater than or equal to a first set pressure. In this method, the step of determining whether the booster pump and hydrogen compressor are compressing hydrogen from the buffer tank into the hydrogen storage tank may include determining whether the internal pressure of the hydrogen storage tank is less than a second set pressure.

[0023] The method may further include: when the internal pressure of the hydrogen storage tank is less than the second set pressure, operating the booster pump and the hydrogen compressor to compress the hydrogen stored in the buffer tank, and storing the compressed hydrogen in the hydrogen storage tank. The method may also include: when the internal pressure of the hydrogen storage tank is greater than or equal to the second set pressure, stopping the operation of the booster pump and the hydrogen compressor.

[0024] The apparatus according to this disclosure may include: a solid-phase hydrogen generation system configured to generate hydrogen through a reaction between a solid hydrogen storage material and a reaction liquid; a storage vessel configured to receive and store the hydrogen generated by the solid-phase hydrogen generation system; a compressor configured to increase the pressure of the hydrogen from the storage vessel; a tank configured to store hydrogen compressed by the compressor; and a distributor configured to supply hydrogen from at least one of the storage vessels or tanks to a hydrogen receiving device. In this apparatus, the solid-phase hydrogen generation system may include: an acidic aqueous solution tank configured to store an acidic aqueous solution; and a dehydrogenation reactor configured to receive a chemical hydride and mix the acidic aqueous solution with the chemical hydride to generate hydrogen.

[0025] The apparatus may also include a cooling system configured to control the temperature of the dehydrogenation reactor, wherein the cooling system may include a chiller and a cooling pump. In this apparatus, a distributor may be configured to supply hydrogen from a storage container when the hydrogen receiving device's hydrogenation pressure is within a first pressure range, and to supply hydrogen from a storage tank when the hydrogenation pressure is within a second pressure range.

[0026] Furthermore, the effects that may be obtained or anticipated from the embodiments of this disclosure are disclosed directly or implicitly in the detailed description of this disclosure. That is, various effects contemplated according to this disclosure will be disclosed in the following detailed description. Attached Figure Description

[0027] Since these accompanying drawings are for reference only and are used to describe embodiments of the present disclosure, the technical concepts of the present disclosure should not be construed as being limited to the drawings.

[0028] Figure 1 An exemplary structure of a hybrid hydrogenation system according to an embodiment is shown.

[0029] Figure 2 An exemplary structure of a hybrid hydrogenation system according to an embodiment is shown.

[0030] Figure 3A and Figure 3B An embodiment of a control method for a hybrid hydrogenation system according to an example is shown.

[0031] Figure 4 An exemplary computing system (e.g., a computing device for a hybrid hydrogen refueling system, a vehicle, or any other device) is shown.

[0032] It should be understood that the above figures are not drawn to scale, but are simplified representations of various preferred features illustrating the basic principles of this disclosure. For example, specific design features of this disclosure, including particular dimensions, orientations, positions, and shapes, will be determined in part by the specific intended application and environment of use. Detailed Implementation

[0033] The terminology used herein is for the purpose of describing specific examples only and is not intended to limit this disclosure. Unless the context clearly indicates otherwise, the singular forms used herein include the plural forms as well. It should also be understood that the terms “comprising” and / or “including” as used herein specify the presence of features, numbers, steps, operations, elements, and / or components, but do not exclude the presence or addition of one or more other features, numbers, steps, operations, elements, components, and / or combinations thereof. The term “and / or” as used herein includes any one or all of the associated listed items.

[0034] For the purposes of this application and claims, when the exemplary phrases “at least one of A; B; or C” or “at least one of A, B, or C” are used, the phrase means “at least one A, or at least one B, or at least one C, or any combination of at least one A, at least one B, and at least one C.” Furthermore, exemplary phrases used herein, such as “A, B, or C,” “at least one of A, B, and C,” “at least one of A, B, or C,” etc., may refer to each listed item or all possible combinations of listed items. For example, “at least one of A or B” may refer to (1) at least one A; (2) at least one B; or (3) at least one A and at least one B.

[0035] Furthermore, it should be understood that one or more of the following methods or embodiments thereof can be performed by at least one controller. The term "controller" can refer to a hardware device including a memory and a processor. The memory is used to store program instructions, and the processor is specifically programmed to execute the program instructions, thereby performing one or more processes described in more detail below. The controller can control the operation of the units, modules, components, devices, etc., described herein. Furthermore, those skilled in the art will understand that the methods described below can be implemented by a device including a controller and one or more other components.

[0036] Furthermore, the controller disclosed herein can be implemented as a non-transitory computer-readable recording medium, comprising executable program instructions that are executed by a processor. Examples of computer-readable recording media include, but are not limited to, ROM, RAM, optical disc (CD) ROM, magnetic tape, floppy disk, flash drive, smart card, and optical data storage device. The computer-readable recording medium can also be distributed across a computer network so that program instructions can be stored and executed in a distributed manner, for example, on a telematics server or a controller area network (CAN).

[0037] As used in this specification, the terms "module" or "unit" refer to software and / or hardware components, and a "module" or "unit" performs certain operations / functions / actions. However, a "module" or "unit" should not be construed as limited to software or hardware. A "module" or "unit" may be configured to reside in addressable storage media or be executed by one or more processors. Thus, for example, a "module" or "unit" may include at least one of the following components: such as software components, object-oriented software components, class components and task components, processes, functions, properties, procedures, subroutines, program code segments, drivers, firmware, microcode, circuits, data, databases, data structures, tables, arrays, or variables. The functionality provided in a component, "module," or "unit" may be combined into a smaller number of components, "modules," or "units," or further divided into additional components, "modules," or "units."

[0038] In this disclosure, a "module" or "unit" can be implemented as a processor and a memory. "Processor" should be broadly understood to include general-purpose processors, central processing units (CPUs), microprocessors, digital signal processors (DSPs), microcontrollers, state machines, etc. In some contexts, "processor" can refer to application-specific integrated circuits (ASICs), programmable logic devices (PLDs), or field-programmable gate arrays (FPGAs). For example, "processor" can refer to a combination of processing devices, such as a combination of a DSP and a microprocessor, a combination of multiple microprocessors, a combination of one or more microprocessors with a DSP core, or any other such combination. Furthermore, "memory" should be broadly understood to include any electronic component capable of storing electronic information. "Memory" can refer to various types of processor-readable media, such as random access memory (RAM), read-only memory (ROM), non-volatile random access memory (NVRAM), programmable read-only memory (PROM), erasable programmable read-only memory (EPROM), electrically erasable programmable read-only memory (EEPROM), flash memory, magnetic or optical data storage devices, and registers. The memory can be in electronic communication with the processor when the processor is able to read information from the memory and / or record information into the memory. The memory integrated into the processor is in electronic communication with the processor.

[0039] One or more features described herein can be provided as a computer program stored in a computer-readable recording medium for execution on a computer. The medium can continuously store a computer-executable program or temporarily store the program for execution or download. Furthermore, the medium can be a variety of recording or storage devices in the form of a single hardware device or multiple combined hardware devices, and is not limited to media directly connected to a computer system, but can also be distributed across a network. Examples of such media include: magnetic media configured to store program instructions, such as hard disks, floppy disks, or magnetic tapes; optical recording media, such as CD-ROMs or DVDs; magneto-optical media, such as floppy disks; and ROM, RAM, or flash memory, etc. Other examples of such media include media or storage media managed by application stores that distribute applications or other various websites or servers that provide or distribute software.

[0040] In a hardware implementation, the processing unit for performing the technology may be implemented in one or more ASICs, DSPs, digital signal processing devices, programmable logic devices, field-programmable gate arrays, processors, controllers, microcontrollers, microprocessors, electronic devices, or computers or combinations thereof, and is designed to perform the functions described in this disclosure.

[0041] The present disclosure will now be described in detail with reference to the accompanying drawings, which illustrate embodiments of the present disclosure. Those skilled in the art will understand that the described embodiments can be modified in various ways without departing from the spirit or scope of the present disclosure.

[0042] The accompanying drawings and descriptions should be considered illustrative rather than restrictive, and similar reference numerals denote similar elements throughout the specification.

[0043] Furthermore, since the dimensions and thicknesses of the components shown in the accompanying drawings may be arbitrarily given for ease of understanding and description, this disclosure is not limited to the dimensions and thicknesses shown, and the thicknesses are exaggerated to clearly represent the individual parts and areas.

[0044] In the following description, the suffixes “module” and / or “part” used for components are given or used interchangeably for convenience in writing the specification and do not have different meanings or functions in themselves.

[0045] Furthermore, in describing the disclosed embodiments, such detailed descriptions are omitted if it is determined that a detailed description of the relevant known technologies may obscure the essential points of the embodiments disclosed herein.

[0046] The accompanying drawings are only for the purpose of helping to understand the embodiments disclosed in this specification. It should be understood that the technical concepts disclosed herein are not limited to the drawings and include all modifications, equivalents or alternatives within the scope of the concepts and techniques of this disclosure.

[0047] Although terms such as "first" and "second" are used to explain various components, these components are not limited to these terms.

[0048] Unless explicitly stated otherwise, the singular expressions described in this specification may be interpreted as singular or plural.

[0049] These terms are used only to distinguish one component from another.

[0050] The hybrid hydrogenation system according to an embodiment will be described in detail below with reference to the accompanying drawings.

[0051] Figure 1 An exemplary structure of a hybrid hydrogenation system according to an embodiment is shown. Figure 2 An exemplary structure of a hybrid hydrogenation system according to an embodiment is shown.

[0052] like Figure 1 and Figure 2 As shown, the hybrid hydrogenation system according to the embodiment may include a solid-phase hydrogen supply system 200 and a compression hydrogen supply system 100.

[0053] The compressed hydrogen supply system 100 may include at least one high-pressure hydrogen compressor 120 and a high-pressure hydrogen storage tank 110.

[0054] The high-pressure hydrogen compressor 120 can pressurize the hydrogen generated in the solid-phase hydrogen supply system 200 and supply it to the high-pressure hydrogen storage tank 110 (e.g., at a pressure of 700 bar, 875 bar, or 1000 bar).

[0055] The high-pressure hydrogen storage tank 110 can store high-pressure hydrogen gas compressed by the high-pressure hydrogen compressor 120.

[0056] The solid-phase hydrogen supply system 200 generates hydrogen through a chemical reaction of chemical hydrides (e.g., NaBH4, LiBH4, NH3BH3, or Ca(BH4)2, etc.) (hereinafter also referred to as "reactants" as needed), and can selectively supply the generated hydrogen to a hydrogen refueling target 40 (e.g., a hydrogen receiving device). In this disclosure, the hydrogen refueling target 40 may be a fuel cell electric vehicle (FCEV) (e.g., a passenger car, bus, forklift, or drone, etc.).

[0057] The solid-phase hydrogen supply system may include an acidic aqueous solution tank 210, at least one dehydrogenation reactor 220, a thermal control device 230, and a buffer tank 250 (e.g., for pressure stabilization, temporary storage, or flow regulation).

[0058] An acidic aqueous solution tank 210 stores an acidic aqueous solution and can selectively supply the stored acidic aqueous solution to a dehydrogenation reactor 220 via an acidic aqueous solution pump 212 (e.g., a diaphragm pump, peristaltic pump, or gear pump). The acidic aqueous solution pump 212 can be positioned between the acidic aqueous solution tank 210 and the dehydrogenation reactor 220. By conveying the acidic aqueous solution stored in the acidic aqueous solution tank to the dehydrogenation reactor 220 via the acidic aqueous solution pump 212 (e.g., to regulate reaction kinetics, maintain reactor pressure, or synchronize with thermal management, etc., by controlling the flow rate).

[0059] The acidic aqueous solution tank 210 can be coated with a corrosion-resistant protective film, such as a Teflon coating, a fluoropolymer liner, or a ceramic-based barrier, to prevent corrosion from the acidic aqueous solution. The acidic aqueous solution promotes the dehydrogenation reaction by adjusting the pH of the chemical hydride, thereby shortening its half-life (e.g., accelerating hydrogen release, reducing system latency, or improving reaction consistency).

[0060] The acid used in acidic aqueous solutions can be an inorganic acid, such as sulfuric acid, nitric acid, phosphoric acid, boric acid, or hydrochloric acid, or an organic acid, such as heteropoly acids, acetic acid, formic acid, malic acid, citric acid, tartaric acid, ascorbic acid, lactic acid, oxalic acid, succinic acid, or taurine, or a mixture thereof, and can be formic acid (HCOOH) because it has a smaller molecular weight relative to hydrogen ions, which can reduce the weight of the system and is safer than hydrochloric acid at high concentrations.

[0061] In the case of formic acid, it is a weak acid that can be used relatively safely because it maintains a low pH under predetermined conditions (e.g., controlled concentration, temperature, or the presence of a buffer solution). Furthermore, the captured carbon dioxide can be obtained through hydrogenation, making it an important material in carbon dioxide recovery (e.g., for use in power-to-gas systems, carbon-neutral fuel production, or closed-loop chemical cycles). Additionally, formate can be converted to bicarbonate through dehydrogenation, yielding additional hydrogen in the process (e.g., to increase yield, improve energy efficiency, or support continuous operation).

[0062] The dehydrogenation reactor 220 can produce hydrogen through a chemical reaction between a chemical hydride and an acidic aqueous solution.

[0063] The dehydrogenation reactor 220 can be configured as a high-temperature, high-pressure vessel so that the dehydrogenation reaction can be carried out under high-temperature and high-pressure conditions (e.g., 100°C to 250°C and 350 bar to 700 bar). For example, the dehydrogenation reactor 220 can be cylindrical, spherical, rectangular, or polygonal, especially cylindrical (e.g., to optimize the volume-to-surface area ratio, achieve uniform heat distribution, or simplify manufacturing).

[0064] Chemical hydrides are solid and can take the form of powder, granules, beads, microcapsules or pellets (e.g., to control reaction rate, facilitate handling or packing density).

[0065] Chemical hydrides can be any compound that hydrolyzes to produce hydrogen and hydrolysis products, for example, they can include NaBH4, LiBH4, KBH4, NH4BH4, NH3BH3, (CH3)4NH4BH4, NaAlH4, LiAlH4, KAlH4, Ca(BH4)2, Mg(BH4)2, NaGaH4, LiGaH4, KGaH4, LiH, CaH2, MgH2 or mixtures thereof (e.g., selected based on hydrogen yield, thermal stability or regeneration feasibility, etc.).

[0066] Since the hydrogen generation reaction inside the dehydrogenation reactor 220 is an exothermic reaction, a thermal control device 230 can be installed to cool the heat of reaction (e.g., to prevent overheating, maintain the optimal reaction temperature, or protect the integrity of the reactor).

[0067] The thermal control device 230 may include a cooler 231 for cooling a hot medium (e.g., a water-glycol mixture, silicone oil, or a refrigerant) and a cooling pump 232 for conveying the hot medium cooled by the cooler 231 to the dehydrogenation reactor 220.

[0068] Cooler 231 and cooling pump 232 can be fluidly connected through cooling pipe 234 through which the hot medium flows. The hot medium cooled by cooler 231 can circulate through cooling pump 232, distributor 30 and dehydrogenation reactor 220, and then flow back into cooler 231 (e.g., in a closed-loop or semi-open-loop structure).

[0069] The heat medium flowing along the cooling pipe 234 may include at least one of the following: water-based liquid refrigerant, oil-based liquid refrigerant, fluorine-based gaseous refrigerant, and inorganic compound gaseous refrigerant (e.g., ammonia, CO2, or hydrofluoroene).

[0070] The cooling pump 232 can be an electric water pump (EWP) that delivers the heat medium via electricity (e.g., using a brushless DC motor or variable speed drive).

[0071] Hydrogen generated in dehydrogenation reactor 220 can be temporarily stored in buffer tank 250 (e.g., to regulate downstream pressure, adapt to reaction cycles, or be used as an intermediate storage tank). When dehydrogenation reactor 220 is replaced, any remaining hydrogen stored in buffer tank 250 can be vented to the outside (e.g., via a controlled vent valve, purging system, or recovery line).

[0072] A back pressure regulator 260 can be installed between the dehydrogenation reactor 220 and the buffer tank 250 (or upstream of the buffer tank 250) (e.g., to manage pressure transients, prevent backflow, or ensure stable gas output). To stably extract hydrogen from the dehydrogenation reactor 220, the internal pressure of the reaction vessel of the dehydrogenation reactor 220 needs to be increased to a specific pressure (e.g., 1 to 350 bar) and the boiling point of the reactants (100°C to 400°C) controlled to minimize phase changes in the reactants (e.g., to prevent cavitation, bubbling, or premature evaporation). For this purpose, the internal pressure of the reaction vessel of the dehydrogenation reactor 220 can be controlled by installing a back pressure regulator 260 downstream of the dehydrogenation reactor 220.

[0073] A first purification device 270 for removing impurities generated inside the dehydrogenation reactor 220 can be provided between the dehydrogenation reactor 220 and the buffer tank 250 (or downstream of the dehydrogenation reactor 220, for example, through a bypass line, an inline shell, or a pre-buffered filter).

[0074] When hydrides react with acidic aqueous solutions in dehydrogenation reactor 220, carbon monoxide and water can be generated as byproducts. If the byproducts carbon monoxide and water are supplied to fuel cells, the durability of fuel cells installed in electric vehicles will be reduced (e.g., due to catalyst poisoning, electrolyte degradation, or membrane fouling).

[0075] The first purification device 270 may include a methane generator for removing carbon monoxide from hydrogen and / or a gas-liquid separator for removing moisture from hydrogen.

[0076] The methane generator converts carbon monoxide, a byproduct produced during the dehydrogenation reaction of hydrides with an acidic aqueous solution in a dehydrogenation reactor 220 to generate hydrogen, into methane (e.g., through methanation with hydrogen in the presence of a catalyst). In the methane generator, hydrogen and carbon monoxide gases exiting the dehydrogenation reactor 220 flow through a catalyst, whereby the carbon monoxide is converted into methane. The catalyst for the methane generator may include at least one of nickel (Ni), ruthenium (Ru), cobalt (Co), rhodium (Rh), and iron (Fe) (e.g., selected based on reaction temperature, catalyst lifetime, or tolerance to impurities). The catalyst is solid and may be in the form of particles, beads, microcapsules, or agglomerates (e.g., to increase surface area, enhance flow uniformity, or facilitate replacement).

[0077] Gas-liquid separators can separate excess moisture from hydrogen and discharge it to the outside (e.g., through a condensate drain pipe, membrane separator, or knockout drum).

[0078] When hydride is recharged into the dehydrogenation reactor 220, outside air may be introduced into the dehydrogenation reactor 220 (e.g., during venting, maintenance, or material change). Alternatively, when a re-reaction or partial restart occurs after a set amount of product has been generated in the dehydrogenation reactor 220 (e.g., due to incomplete sealing, ambient backflow, or purge valve malfunction), impurity gases may be introduced into the dehydrogenation reactor 220.

[0079] Thus, when external air is introduced into the dehydrogenation reactor 220, the overheating generated inside the dehydrogenation reactor 220 may create conditions that easily produce impurity gases such as carbon monoxide in addition to hydrogen. The impurity gases introduced into the dehydrogenation reactor 220 may make it difficult to produce pure hydrogen (for example, by interfering with catalytic efficiency, changing pH value, or producing side reactions).

[0080] To prevent such problems, the hybrid hydrogenation system according to the embodiment may be equipped with a purging device 240, which vents impurity gases from the dehydrogenation reactor 220 to the outside (e.g., to maintain reaction purity, restore vacuum integrity, or prevent pressure spikes, etc.). The purging device 240 may vent impurity gases from the dehydrogenation reactor 220 to the outside using hydrogen gas at a pressure higher than a set level (e.g., opening a purging valve when the internal pressure exceeds a threshold, etc.), or it may vent impurity gases from the dehydrogenation reactor 220 to the outside using a vacuum pump 245 (e.g., generating negative pressure during system shutdown, maintenance, or reactor replacement, etc.).

[0081] For this purpose, the purging device 240 may include: a purging pipe 242 that fluidly connects the dehydrogenation reactor 220 of the solid-phase hydrogen supply system 200 to an external environment; and a purging valve 244 disposed in the purging pipe 242 and downstream of the dehydrogenation reactor 220 (e.g., for controlling purging time, regulating flow rate, or isolating the reactor during exhaust). If necessary, a vacuum pump 245 and a second purification device 247 disposed in the purging pipe 242 and downstream of the purging valve 244 may also be provided to purify the impurity gases discharged through the purging pipe 242 (e.g., for removing residual CO, water vapor, or particulate matter).

[0082] The interior of the dehydrogenation reactor 220 can be purged by the negative pressure generated by the vacuum pump 245. The impurity gas discharged from the dehydrogenation reactor 220 can be purified by the second purification device 247 and discharged to the outside (e.g., discharged to a vent stack, filter housing, or safety exhaust channel).

[0083] On the other hand, a booster pump 130 can be installed between the buffer tank 250 and the high-pressure hydrogen storage tank 110. The booster pump 130 can pump hydrogen stored in the buffer tank 250 and deliver it to the high-pressure hydrogen storage tank 110 (e.g., to increase throughput, support pressure balancing, or enhance compressor input flow). Therefore, the hydrogen stored in the buffer tank 250 is delivered to the high-pressure hydrogen compressor 120 via the booster pump 130 (e.g., to maintain flow continuity, stabilize input pressure, or improve compression efficiency). The high-pressure hydrogen compressor 120 compresses the hydrogen delivered from the buffer tank 250 to a high pressure (e.g., suitable for storage applications at 700 bar, 875 bar, or 1000 bar). Hydrogen compressed to a pressure higher than the reaction pressure in the dehydrogenation reactor 220 can be stored in the high-pressure hydrogen storage tank 110 (e.g., for subsequent distribution, peak demand buffering, or transfer to a mobile storage device).

[0084] A distributor 30 for supplying hydrogen to the hydrogen refueling target 40 may be located downstream of the high-pressure hydrogen storage tank 110 and the buffer tank 250 (e.g., to selectively supply from a medium-pressure or high-pressure source based on filling demand). The distributor 30 may selectively supply high-pressure hydrogen stored in the high-pressure hydrogen storage tank 110 and medium-pressure hydrogen stored in the buffer tank 250 to the hydrogen refueling target 40 (e.g., based on user selection, preset vehicle type, or target filling level).

[0085] The hybrid hydrogenation system according to an embodiment may include a controller 20 that controls the various components of the hybrid hydrogenation system based on driving information detected by the detector 10 (e.g., sensor output, pressure reading, or system feedback).

[0086] The controller 20 may be implemented by one or more processors that operate according to a predetermined program. The memory of the controller 20 stores program instructions that are programmed to execute the various steps of the hybrid hydrogenation method according to the present disclosure by one or more processors (e.g., microcontrollers, programmable logic controllers, or embedded systems).

[0087] The controller 20 can control the operation of the compression hydrogen supply system 100 and the solid phase hydrogen supply system 200 (e.g., start / stop sequence, pressure regulation or purging time, etc.).

[0088] The detector 10 may include: a flow sensor for detecting the amount of reactants in the dehydrogenation reactor 220, a first pressure sensor for detecting the pressure in the dehydrogenation reactor 220, a second pressure sensor for detecting the pressure in the buffer tank 250, and a third pressure sensor for detecting the pressure in the high-pressure hydrogen storage tank 110 (e.g., each implemented using a MEMS sensor, a piezoresistive sensor, or a strain gauge sensor).

[0089] Figure 3A and Figure 3B An embodiment of a control method for a hybrid hydrogenation system is shown. Controller 20 determines, via detector 10, whether the amount of reactant in the dehydrogenation reactor 220 of the solid-phase hydrogen supply system is greater than or equal to a set amount (S10) (e.g., based on a threshold corresponding to the expected hydrogen yield or reaction duration).

[0090] If the amount of reactant in the dehydrogenation reactor 220 is less than the set amount, the dehydrogenation reactor 220 is replaced, or the reactant is filled into the dehydrogenation reactor 220 (S11) (e.g., using an automatic filling valve, a replaceable cartridge, or a manual refill port).

[0091] If the amount of reactants in the dehydrogenation reactor 220 is greater than or equal to the set amount, the controller 20 operates the dehydrogenation reactor 220 to generate hydrogen and stores the generated hydrogen in the buffer tank 250 (S13) (e.g., for temporary storage, flow regulation or preparation for compression into a high-pressure storage tank, etc.).

[0092] The controller 20 determines whether the internal pressure of the dehydrogenation reactor 220 is greater than or equal to a first set pressure (e.g., 350 to 700 bar), or whether the internal pressure of the buffer tank 250 is equal to or greater than the first set pressure (S20) (e.g., to decide whether to continue or pause hydrogen generation, or to initiate compression to a high-pressure storage device, etc.).

[0093] If the internal pressure of the dehydrogenation reactor 220 or the buffer tank 250 is lower than the first set pressure, the controller 20 continues to operate the dehydrogenation reactor 220 to generate hydrogen (S11) (e.g., to maintain a sufficient supply for immediate distribution or subsequent compression, etc.).

[0094] If the internal pressure of the dehydrogenation reactor 220 or the buffer tank 250 is higher than the first set pressure, the controller 20 stops the operation of the dehydrogenation reactor 220 (S23) (e.g., to prevent overpressure, ensure system safety, or optimize heat load).

[0095] In other words, the controller 20 can determine whether to operate the dehydrogenation reactor 220 based on the internal pressure of the dehydrogenation reactor 220 or the buffer tank 250 (e.g., by comparing it with a pressure threshold or a time-weighted average).

[0096] The controller 20 determines whether the internal pressure of the high-pressure hydrogen storage tank 110 is less than a second set pressure (e.g., 700 to 1000 bar, depending on the specifications of the distribution system, vehicle type, or storage scheme, etc.) (S30).

[0097] If the internal pressure of the high-pressure hydrogen storage tank 110 is lower than the second set pressure, the controller 20 operates the booster pump and the high-pressure hydrogen compressor 120 to compress the hydrogen stored in the buffer tank 250 to high pressure and store the hydrogen in the high-pressure hydrogen storage tank 110 (S31) (e.g., to replenish storage, support high-pressure vehicle charging, or maintain readiness for peak demand). In this case, before the internal pressure of the high-pressure hydrogen storage tank 110 reaches the second set pressure, the controller 20 operates the booster pump and the high-pressure hydrogen compressor 120 to compress the hydrogen stored in the buffer tank 250 to high pressure and store the hydrogen in the high-pressure hydrogen storage tank 110 (e.g., using graded control or a pressure feedback loop).

[0098] If the internal pressure of the high-pressure hydrogen storage tank 110 is higher than or equal to the second set pressure, the controller 20 stops operating the booster pump and the high-pressure hydrogen compressor 120 (S33) (e.g., to save energy, avoid overcharging or triggering an idling state, etc.).

[0099] In other words, the controller 20 can determine whether to operate the booster pump and the high-pressure hydrogen compressor 120 based on the internal pressure of the high-pressure hydrogen storage tank 110 (e.g., to maintain optimal hydrogen storage, prevent overpressure, or synchronize with the vehicle's fueling needs).

[0100] The controller 20 can supply hydrogen stored in the high-pressure hydrogen storage tank 110 to the hydrogen refueling target 40, or supply hydrogen stored in the buffer tank 250 to the hydrogen refueling target 40, based on the target charging pressure of the hydrogen refueling target 40 (e.g., depending on whether the target requires high-pressure fuel supply for long-range vehicles or medium-pressure fuel supply for light-duty applications, etc.). The target charging pressure of the hydrogen refueling target 40 can be determined by user input (S40) (e.g., via a touchscreen interface, vehicle docking signal, or preset configuration, etc.).

[0101] For example, if the target charging pressure of hydrogen refueling target 40 is in the medium-pressure range (e.g., 350 to 700 bar), controller 20 supplies hydrogen stored in buffer tank 250 to hydrogen refueling target 40 via distributor 30 (e.g., for fleet vehicles, hydrogen-powered drones, or backup power systems, etc.). If the target charging pressure of hydrogen refueling target 40 is in the high-pressure range (e.g., 700 to 1000 bar), controller 20 supplies hydrogen stored in high-pressure hydrogen storage tank 110 to hydrogen refueling target 40 via distributor 30 (e.g., for fuel supply to passenger FCEVs, commercial trucks, or large-capacity hydrogen transport modules, etc.).

[0102] In other words, controller 20 determines the target charging pressure of hydrogen refueling target 40 (S40). If the target charging pressure of hydrogen refueling target 40 is in the medium pressure range, controller 20 supplies hydrogen stored in buffer tank 250 to hydrogen refueling target 40 via distributor 30 (S41) (e.g., for applications such as industrial forklifts, light vehicles, or portable hydrogen devices). Furthermore, if the target charging pressure of hydrogen refueling target 40 is in the high pressure range, controller 20 supplies hydrogen stored in high-pressure hydrogen storage tank 110 to hydrogen refueling target 40 via distributor 30 (S43) (e.g., to ensure an appropriate fuel supply rate, meet vehicle pressure specifications, or optimize refueling efficiency).

[0103] Figure 4 An exemplary computer system (e.g., a computer device for a hybrid hydrogen refueling system, a vehicle, or any other device) is shown.

[0104] One or more controllers, processors, etc., as described herein, such as one or more components of a hybrid hydrogen refueling system, one or more components of a vehicle, and any other components and devices disclosed herein, may be provided by Figure 4 The computer system shown is implemented or embedded therein.

[0105] Computer system 1000 may include at least one processor 1100, memory 1300, user interface input device 1400, user interface output device 1500, storage 1600 and network interface 1700 interconnected with each other via bus 1200.

[0106] Processor 1100 may be a central processing unit (CPU) or a semiconductor device that processes instructions stored in memory 1300 and / or storage 1600. Both memory 1300 and storage 1600 may include various types of volatile or non-volatile storage media. For example, memory 1300 may include read-only memory (ROM) and random access memory (RAM).

[0107] A communication interface (also known as a communication device, communicator, communication module, communication unit, etc.), such as network interface 1700, allows software and / or data to be transmitted between the device and one or more external devices, and / or between one or more components of the device. A communication interface may include a receiver, transmitter, transceiver, modem, network interface and / or adapter (e.g., Ethernet adapter), radio transceiver, antenna, communication port, PCMCIA slot and card, etc. The software and data transmitted through the communication interface may be in the form of signals, which may be electrical signals, electromagnetic signals, optical signals, infrared signals, or other signals that can be received by the communication interface. These signals can be provided to the communication interface through the device's communication path, which can be implemented using, for example, wires or cables, optical fibers, cellular links, radio frequency (RF) links, and / or other communication channels. The communication interface can communicate using one or more communication protocols, such as Ethernet, Wi-Fi, Near Field Communication (NFC), Infrared Data Association (IrDA), Bluetooth, Bluetooth Low Energy (BLE), Zigbee, Long Term Evolution (LTE), New Ratio (NR), Vehicle-to-Everything (V2X), Controller Area Network (CAN), or Local Interconnect Network (LIN).

[0108] Therefore, the operation of the methods or algorithms described in conjunction with the exemplary embodiments disclosed in this specification can be directly implemented using hardware modules, software modules, or a combination of hardware and software modules executed by processor 1100. Software modules may reside on storage media (e.g., memory 1300 and / or storage 1600), such as RAM, flash memory, ROM, erasable programmable ROM (EPROM), electrically EPROM (EEPROM), registers, hard disk drives, removable disks, or optical disc-ROMs (CD-ROMs).

[0109] The storage medium can be coupled to the processor 1100. The processor 1100 can read information from the storage medium and write information to the storage medium. Alternatively, the storage medium can be integrated with the processor 1100. The processor and storage medium can be implemented using an application-specific integrated circuit (ASIC). The ASIC can be located in the user terminal. Alternatively, the processor and storage medium can be implemented as separate components in the user terminal.

[0110] The hybrid hydrogenation system according to an embodiment includes: a solid-phase hydrogen supply system that generates hydrogen in a medium-pressure range through a chemical reaction of a chemical hydride; a compression hydrogen supply system that selectively pressurizes the hydrogen generated by the solid-phase hydrogen supply system to a predetermined high-pressure range; and a distributor that selectively supplies hydrogen from the solid-phase hydrogen supply system and the compression hydrogen supply system to the hydrogenation target.

[0111] In some embodiments, the compressed hydrogen supply system may include: a high-pressure hydrogen compressor that pressurizes hydrogen generated in the solid-phase hydrogen supply system; and a high-pressure hydrogen storage tank for storing hydrogen pressurized by the high-pressure hydrogen compressor.

[0112] In some embodiments, the solid-phase hydrogen supply system may include: an acidic aqueous solution tank for storing an acidic aqueous solution; at least one dehydrogenation reactor for storing chemical hydrides and selectively supplying the acidic aqueous solution stored in the acidic aqueous solution tank to generate hydrogen; and a thermal control device for controlling the temperature of the dehydrogenation reactor.

[0113] In some embodiments, the solid-phase hydrogen supply system may further include a purging device for discharging impurity gases from inside the dehydrogenation reactor.

[0114] In some embodiments, the purging apparatus may include a purging pipe for connecting the dehydrogenation reactor fluid to the outside; and a purging valve disposed in the purging pipe and located downstream of the dehydrogenation reactor.

[0115] In some embodiments, the purging device may further include a vacuum pump disposed in the purging tube and located downstream of the purging valve.

[0116] In some embodiments, a buffer tank may also be included for temporary storage of hydrogen produced in the dehydrogenation reactor.

[0117] In some embodiments, the compressed hydrogen supply system may also include a booster pump disposed between a buffer tank and a high-pressure hydrogen storage tank.

[0118] In some embodiments, the solid-phase hydrogen supply system may further include a back pressure regulator disposed upstream of the buffer tank and a first purification device disposed upstream of the back pressure regulator.

[0119] The hybrid hydrogenation method, which includes a compressed hydrogen supply system and a solid-phase hydrogen supply system, includes: determining whether to operate the dehydrogenation reactor based on the internal pressure of the dehydrogenation reactor or buffer tank of the solid-phase hydrogen supply system; determining whether to operate the booster pump and high-pressure hydrogen compressor of the compressed hydrogen supply system based on the internal pressure of the high-pressure hydrogen storage tank of the compressed hydrogen supply system; and supplying hydrogen stored in the high-pressure hydrogen storage tank of the compressed hydrogen supply system to the hydrogenation target, or supplying hydrogen stored in the buffer tank of the solid-phase hydrogen supply system to the hydrogenation target, based on the target charging pressure of the hydrogenation target.

[0120] In some embodiments, determining whether to operate the dehydrogenation reactor may include determining whether the internal pressure of the dehydrogenation reactor or buffer tank is greater than or equal to a first set pressure.

[0121] In some embodiments, if the internal pressure of the dehydrogenation reactor or buffer tank is less than a first set pressure, the dehydrogenation reactor can be operated to generate hydrogen.

[0122] In some embodiments, if the internal pressure of the dehydrogenation reactor or buffer tank is greater than or equal to a first set pressure, the operation of the dehydrogenation reactor can be stopped.

[0123] In some embodiments, determining whether to operate the booster pump and high-pressure hydrogen compressor of the compressed hydrogen supply system may include determining whether the internal pressure of the high-pressure hydrogen storage tank of the compressed hydrogen supply system is less than a second set pressure.

[0124] In some embodiments, if the internal pressure of the high-pressure hydrogen storage tank is less than the second set pressure, the booster pump and high-pressure hydrogen compressor of the compression hydrogen supply system can be operated to compress the hydrogen stored in the buffer tank and store the hydrogen in the high-pressure hydrogen storage tank.

[0125] In some embodiments, if the internal pressure of the high-pressure hydrogen storage tank is greater than or equal to a second set pressure, the operation of the booster pump and the high-pressure hydrogen compressor can be stopped.

[0126] According to an embodiment, by first generating medium-pressure hydrogen using relatively light chemical hydrides, and then compressing the hydrogen a second time to high pressure using a compressor, the transportation costs required to supply hydrogen to hydrogen refueling stations can be reduced, and carbon emissions can be reduced.

[0127] According to embodiments of the hybrid hydrogen refueling system and method, unlike supplying hydrogen-filled storage tanks to existing hydrogen refueling stations via trailers or the like, medium-pressure hydrogen is first generated using relatively light chemical hydrides, and then the hydrogen is compressed a second time to high pressure using a compressor, thereby reducing the transportation costs required to supply hydrogen to refueling stations and reducing carbon emissions.

[0128] In addition, it can reduce the space required to park trailers equipped with hydrogen tanks at existing hydrogen refueling stations, as well as the space required to store the hydrogen tanks.

[0129] While this disclosure has been described in conjunction with embodiments now considered practical, it should be understood that this disclosure is not limited to the disclosed embodiments, but rather is intended to cover various modifications and equivalents included within the spirit and scope of the appended claims.

Claims

1. An apparatus comprising: A solid-phase hydrogen supply system configured to generate hydrogen gas within a first pressure range based on the chemical reaction of chemical hydrides; A compression system configured to selectively change the pressure of hydrogen produced by the solid-phase hydrogen supply system to a second pressure range that exceeds the first pressure range; and A distributor configured to supply hydrogen from at least one of the solid-phase hydrogen supply system or the compression system to a hydrogenation target.

2. The apparatus according to claim 1, wherein The compression system includes: A hydrogen compressor configured to pressurize the hydrogen produced by the solid-phase hydrogen supply system; and A hydrogen storage tank configured to store hydrogen gas pressurized by the hydrogen compressor.

3. The apparatus according to claim 2, wherein The solid-phase hydrogen supply system includes: An acidic aqueous solution tank, configured to store acidic aqueous solutions; At least one dehydrogenation reactor configured to store the chemical hydride and selectively supply an acidic aqueous solution stored in the acidic aqueous solution tank to generate hydrogen. and A cooling device configured to control the temperature of the at least one dehydrogenation reactor.

4. The apparatus according to claim 3, wherein The solid-phase hydrogen supply system also includes: A purging assembly configured to remove impurity gases from the dehydrogenation reactor.

5. The apparatus according to claim 4, wherein The purging assembly includes: A purge pipe configured to connect the dehydrogenation reactor fluidly to an outlet located outside the solid-phase hydrogen supply system; and A purge valve is disposed in the purge pipe and located downstream of the dehydrogenation reactor.

6. The apparatus according to claim 5, wherein The purging assembly also includes: A vacuum pump is disposed in the purge pipe and located downstream of the purge valve.

7. The apparatus according to claim 3, further comprising: A buffer tank configured to temporarily store hydrogen produced by at least one dehydrogenation reactor of the solid-phase hydrogen supply system.

8. The apparatus according to claim 7, wherein The compression system also includes: A booster pump is disposed between the buffer tank and the hydrogen storage tank of the compression system.

9. The apparatus according to claim 7, wherein The solid-phase hydrogen supply system includes: A back pressure regulator is located upstream of the buffer tank; and A gas purifier is located upstream of the back pressure regulator.

10. A method performed by an apparatus comprising a compression system and a solid-phase hydrogen supply system, the method comprising the steps of: Based on the internal pressure of the dehydrogenation reactor of the solid-phase hydrogen supply system or the internal pressure of the buffer tank of the solid-phase hydrogen supply system, determine whether the dehydrogenation reactor performs a dehydrogenation reaction to generate hydrogen. Based on the internal pressure of the hydrogen storage tank of the compression system, determine whether the booster pump and the hydrogen compressor of the compression system compress hydrogen from the buffer tank into the hydrogen storage tank; and Based on the required hydrogenation pressure associated with the hydrogenation target, hydrogen is supplied to the hydrogenation target through the following steps: Hydrogen stored in the hydrogen storage tank of the compression system is supplied to the hydrogenation target, or Hydrogen stored in the buffer tank of the solid-phase hydrogen supply system is supplied to the hydrogenation target.

11. The method of claim 10, wherein The steps for determining whether the dehydrogenation reactor performs a dehydrogenation reaction to generate hydrogen include: Determine whether the internal pressure of the dehydrogenation reactor or the internal pressure of the buffer tank is greater than or equal to the first set pressure.

12. The method of claim 11, further comprising the step of: When the internal pressure of the dehydrogenation reactor or the internal pressure of the buffer tank is less than the first set pressure, the dehydrogenation reactor is controlled to carry out a dehydrogenation reaction to generate hydrogen.

13. The method of claim 12, further comprising the step of: When the internal pressure of the dehydrogenation reactor or the internal pressure of the buffer tank is greater than or equal to the first set pressure, the dehydrogenation reaction through the dehydrogenation reactor is stopped.

14. The method of claim 10, wherein the step of determining whether the booster pump and the hydrogen compressor compress hydrogen from the buffer tank into the hydrogen storage tank comprises: Determine whether the internal pressure of the hydrogen storage tank is less than the second set pressure.

15. The method of claim 14, further comprising the step of: When the internal pressure of the hydrogen storage tank is less than the second set pressure, the booster pump and the hydrogen compressor are operated to compress the hydrogen stored in the buffer tank and store the compressed hydrogen in the hydrogen storage tank.

16. The method of claim 15, further comprising the step of: When the internal pressure of the hydrogen storage tank is greater than or equal to the second set pressure, the operation of the booster pump and the hydrogen compressor shall be stopped.

17. An apparatus comprising: A solid-phase hydrogen production system configured to generate hydrogen through a reaction between a solid-phase hydrogen storage material and a reaction liquid; A storage container configured to receive and store hydrogen produced by the solid-phase hydrogen production system; A compressor configured to increase the pressure of hydrogen from the storage container; A storage tank configured to store hydrogen gas compressed by the compressor; and A distributor configured to supply hydrogen from at least one of the storage containers or tanks to a hydrogen receiving device.

18. The apparatus of claim 17, wherein the solid-phase hydrogen production system comprises: An acidic aqueous solution tank, configured to store acidic aqueous solutions; and A dehydrogenation reactor configured to receive a chemical hydride and mix the acidic aqueous solution with the chemical hydride to produce hydrogen gas.

19. The apparatus of claim 17, further comprising a cooling device configured to control the temperature of the dehydrogenation reactor of the solid-phase hydrogen production system, wherein the cooling device comprises a cooler and a cooling pump.

20. The apparatus of claim 17, wherein the dispenser is configured to: When the hydrogen receiving device is under hydrogen pressure within a first pressure range, hydrogen is supplied from the storage container; and Hydrogen is supplied from the storage tank when the hydrogenation pressure is within the second pressure range.

Images