Dehydrogenation reaction system and its control method

Abstract

An exemplary embodiment of this disclosure provides a dehydrogenation reaction system comprising: a dehydrogenation reactor configured to generate hydrogen gas through a chemical reaction between an aqueous chemical hydride solution and an acidic aqueous solution; an acid storage tank configured to store acid supplied to the dehydrogenation reactor; a chemical hydride storage tank configured to store an aqueous chemical hydride solution containing a neutralizing agent supplied to the dehydrogenation reactor; and a controller configured to supply a first predetermined amount of water and a second predetermined amount of acidic aqueous solution to the dehydrogenation reactor, and, after supplying water and acidic aqueous solution to the dehydrogenation reactor, supply the aqueous chemical hydride solution to the dehydrogenation reactor at a first predetermined flow rate.

Description

[0001] Cross-reference to related applications This application claims priority and interest in Korean Patent Application No. 10-2024-0197978, filed with the Korean Intellectual Property Office on December 27, 2024, and Korean Patent Application No. 10-2025-0133703, filed with the Korean Intellectual Property Office on September 17, 2025, the entire contents of which are incorporated herein by reference. Technical Field

[0002] The disclosed subject matter relates to a dehydrogenation reaction system and a control method thereof, and more specifically, to a dehydrogenation reaction system and a control method capable of improving hydrogen purity by minimizing byproducts generated during the dehydrogenation reaction. Background Technology

[0003] Due to the depletion of fossil fuels and environmental pollution, the demand for renewable and alternative energy sources is growing, and hydrogen is gaining attention as a potential alternative energy source.

[0004] Both fuel cells and hydrogen combustion devices use hydrogen as the reactant gas, but a stable and continuous supply of hydrogen is crucial for their application in vehicles and various electronic products.

[0005] Hydrogen can be supplied to the hydrogen utilization unit from a separate hydrogen supply station. Compressed hydrogen or liquefied hydrogen can be used in this method.

[0006] To supply hydrogen to fuel cells or hydrogen combustion devices, an acidic aqueous solution is injected into a chemical hydride stored in a reaction vessel to produce hydrogen. During the reaction of the chemical hydride with the acidic aqueous solution, byproducts such as carbon monoxide are generated.

[0007] If byproducts generated during the dehydrogenation reaction, such as carbon monoxide, are transported to hydrogen supply targets, such as fuel cells, the fuel cells may experience deactivation problems.

[0008] Therefore, techniques to improve hydrogen purity by suppressing the generation of byproducts (such as carbon monoxide) during the dehydrogenation reaction may be useful.

[0009] The information disclosed in this background section is only for providing background information for this disclosure and may therefore include information that does not constitute prior art. Summary of the Invention

[0010] This article provides a dehydrogenation reaction system and its control method, which is configured to improve the purity of hydrogen by suppressing the amount of carbon monoxide produced during the dehydrogenation reaction.

[0011] An exemplary embodiment of this disclosure provides a dehydrogenation reaction system including a dehydrogenation reactor configured to generate hydrogen gas through a chemical reaction between an aqueous chemical hydride solution and an acidic aqueous solution. The system also includes an acid storage tank configured to store acid supplied to the dehydrogenation reactor; a chemical hydride storage tank configured to store an aqueous chemical hydride solution containing a neutralizing agent supplied to the dehydrogenation reactor; and a controller configured to supply the dehydrogenation reactor with a first predetermined amount of water and a second predetermined amount of the acidic aqueous solution. After supplying water and the acidic aqueous solution to the dehydrogenation reactor, the controller can supply the aqueous chemical hydride solution to the dehydrogenation reactor at a first predetermined flow rate.

[0012] In some exemplary embodiments, the system may also include a water storage tank configured to store water supplied to the dehydrogenation reactor.

[0013] In some exemplary embodiments, if the internal temperature of the dehydrogenation reactor is higher than a first predetermined temperature, the controller can be configured to supply the dehydrogenation reactor with an aqueous solution of chemical hydride at a second predetermined flow rate lower than the first predetermined flow rate.

[0014] In some exemplary embodiments, if the internal temperature of the dehydrogenation reactor is higher than a first predetermined temperature, the controller may be configured to (e.g., additionally) supply water to the dehydrogenation reactor.

[0015] In some exemplary embodiments, after a third predetermined amount of chemical hydride is supplied to the dehydrogenation reactor, when the internal temperature of the dehydrogenation reactor is equal to or higher than a second predetermined temperature, the controller can be configured to additionally supply water to the dehydrogenation reactor.

[0016] In some exemplary embodiments, after a third predetermined amount of chemical hydride is supplied to the dehydrogenation reactor, when the internal temperature of the dehydrogenation reactor is lower than a second predetermined temperature, the controller can be configured to discharge the product of the dehydrogenation reactor into a product storage tank.

[0017] In some exemplary embodiments, the molar ratio of the acidic aqueous solution to water supplied to the dehydrogenation reactor is within a predetermined range.

[0018] In some exemplary embodiments, the molar ratio within a predetermined range can be from about 20 mol% to about 50 mol%.

[0019] In some exemplary embodiments, a thermal management device is disposed within a chemical hydride storage tank and configured to maintain the temperature of the chemical hydride storage tank within a predetermined temperature range.

[0020] In some exemplary embodiments, the predetermined temperature range can be from about 5 °C to about 20 °C.

[0021] In some exemplary embodiments, the thermal management device may include at least one of the following: a cooling coil disposed inside the chemical hydride storage tank, a cooling jacket disposed outside the chemical hydride storage tank, or a cooling bath configured to contain the chemical hydride storage tank.

[0022] In some exemplary embodiments, the operating temperature of the reaction between the acidic aqueous solution and the chemical hydride aqueous solution in the dehydrogenation reactor can be maintained at about 120°C or below.

[0023] An exemplary embodiment of this disclosure provides a method for controlling a dehydrogenation reaction system. The method may include: supplying a first predetermined amount of water to a dehydrogenation reactor; supplying a second predetermined amount of an acidic aqueous solution to the dehydrogenation reactor; and, after supplying the water and the acidic aqueous solution to the dehydrogenation reactor, supplying an aqueous solution of a chemical hydride containing a neutralizing agent to the dehydrogenation reactor at a first predetermined flow rate.

[0024] In some exemplary embodiments, the method may further include: determining whether the internal temperature of the dehydrogenation reactor exceeds a first predetermined temperature; and when the internal temperature of the dehydrogenation reactor exceeds the first predetermined temperature, supplying an aqueous solution of chemical hydride to the dehydrogenation reactor at a second predetermined flow rate lower than the first predetermined flow rate.

[0025] In some exemplary embodiments, the method may further include: determining whether a third predetermined amount of chemical hydride aqueous solution has been supplied to the dehydrogenation reactor; after supplying the third predetermined amount of chemical hydride aqueous solution to the dehydrogenation reactor, determining whether the internal temperature of the dehydrogenation reactor is lower than a second predetermined temperature; and based on the internal temperature of the dehydrogenation reactor, discharging the product of the dehydrogenation reactor to a product storage tank or additionally supplying water to the dehydrogenation reactor.

[0026] In some exemplary embodiments, the method may further include discharging the product of the dehydrogenation reactor into a product storage tank if the internal temperature of the dehydrogenation reactor is lower than a second predetermined temperature.

[0027] In some exemplary embodiments, the method may further include supplying additional water to the dehydrogenation reactor if the internal temperature of the dehydrogenation reactor is equal to or higher than a second predetermined temperature.

[0028] In some exemplary embodiments, the molar ratio of the acidic aqueous solution to water supplied to the dehydrogenation reactor is within a predetermined range.

[0029] In some exemplary embodiments, the molar ratio within a predetermined range can be from about 20 mol% to about 50 mol%.

[0030] In some exemplary embodiments, the chemical hydride storage tank can maintain a predetermined temperature range.

[0031] In some exemplary embodiments, the predetermined temperature range may be from about 5 °C to about 20 °C.

[0032] According to an exemplary embodiment, by first injecting an acidic aqueous solution into the dehydrogenation reactor and then injecting a chemical hydride aqueous solution, the generation of byproducts (such as carbon monoxide) that may occur during the reaction between the acidic aqueous solution and the chemical hydride aqueous solution can be minimized.

[0033] Furthermore, the effects that can be obtained or are expected to be obtained by the exemplary embodiments of this disclosure are described in detail below. Attached Figure Description

[0034] The accompanying drawings are intended as a reference for describing this disclosure and should not be construed as limiting this disclosure.

[0035] Figure 1 A schematic diagram of the construction of a dehydrogenation reaction system according to an exemplary embodiment is shown.

[0036] Figure 2A , 2B Figures 2C and 2C show a schematic diagram of the construction of a thermal management device according to an exemplary embodiment.

[0037] Figure 3 A flowchart of a control method for a dehydrogenation reaction system according to an exemplary embodiment is shown.

[0038] Figure 4A and Figure 4B Experimental results are shown to validate the first method of injecting acidic aqueous solutions and chemical hydrides.

[0039] Figure 5A and Figure 5B Experimental results are shown to validate a second method involving the injection of acidic aqueous solutions and chemical hydrides.

[0040] Figure 6 Experimental results are shown to validate a third method involving the injection of acidic aqueous solutions and chemical hydrides.

[0041] Figure 7A and 7B The experimental results are presented in graphs to identify factors that influence carbon monoxide formation.

[0042] Figure 8 A description is shown Figure 7A and 7B A view of part of the experimental results.

[0043] Figure 9 It shows the basis Figure 7A and 7B The experimental results shown illustrate the relationship between the amount of H2O injected and the maximum amount of CO generated.

[0044] Figure 10A , 10B 10C and 10D show the demonstration Figure 7A and 7B The graph shows a portion of the experimental results.

[0045] Figure 11 A description is shown Figure 7A and 7B The chart shows some of the experimental results.

[0046] The accompanying drawings are not drawn to scale, but are simplified representations of various features to illustrate the basic principles of this disclosure. Certain design features of this disclosure (e.g., specific dimensions, orientations, locations, and shapes) may depend in part on the intended application and environment of use. Detailed Implementation

[0047] The terminology used herein is for describing specific exemplary embodiments and is not intended to limit the scope of this disclosure. Unless the context otherwise requires, the singular forms used herein also include the plural forms. The terms “comprising” and / or “including” as used herein specify the presence of the stated features, integrals, steps, operations, elements, and / or components, but do not exclude the presence or addition of one or more other features, integrals, steps, operations, elements, components, and / or combinations thereof. The term “and / or” as used herein includes any one or all combinations of the associated listed items.

[0048] Furthermore, one or more of the following methods or aspects may be performed by at least one controller. The term "controller" may refer to a hardware device that includes memory and a processor.

[0049] Memory is used to store program instructions, and a processor (e.g., is specifically programmed to execute the program instructions, thereby performing one or more processes described in more detail below. As described herein, a controller can control the operation of the units, modules, components, devices, or similar elements described herein. Furthermore, the following methods can be performed by a device that includes a controller and one or more other components.

[0050] Furthermore, the controller disclosed herein can be implemented as a non-transitory computer-readable recording medium containing 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).

[0051] The present disclosure will be described in more detail below with reference to the accompanying drawings, which illustrate embodiments of the present disclosure. However, the described embodiments of the present disclosure may be modified in various (e.g., different) ways without departing from the spirit or scope of the present disclosure.

[0052] For the purpose of describing this disclosure, the same numbers are used throughout the specification to denote the same or similar components.

[0053] Furthermore, since the dimensions and thicknesses of the various structures shown in the accompanying drawings are for convenience, this disclosure is not necessarily limited to the structures shown, and for the purpose of illustrating certain parts and areas, the thickness may be shown in an enlarged manner.

[0054] The terms “module” and / or “unit” used for components in the following description are for convenience in describing this specification only. Therefore, these terms do not in themselves have a distinguishing meaning or function from each other.

[0055] The accompanying drawings are intended to aid in understanding the exemplary embodiments disclosed in this specification and should not be construed as part of this specification. This disclosure includes, for example, all modifications, equivalents, and substitutions without departing from it.

[0056] Terms including ordinal numbers (e.g., first, second, etc.) will be used to describe various components, and these terms should not be interpreted as limitations on these components. These terms are used to distinguish one component from other components.

[0057] In the following description, unless explicitly stated as “single” or “one”, the singular form can be understood as either singular or plural.

[0058] In the flowchart described with reference to the accompanying drawings, the order of operations can be changed, multiple operations can be combined, some operations can be split, and one or more operations may not be executed.

[0059] In the following, the dehydrogenation reaction according to an exemplary embodiment will be described in detail with reference to the accompanying drawings.

[0060] Figure 1 A schematic diagram of the construction of a dehydrogenation reaction system according to an exemplary embodiment is shown.

[0061] like Figure 1 As shown, the dehydrogenation reaction system according to an exemplary embodiment may include a water storage tank 10, an acid storage tank 20, a chemical hydride storage tank 30, a dehydrogenation reactor 40, a hydrogen storage tank 50, and a product storage tank 60.

[0062] Water storage tank 10 is used to store water, which can be (e.g., selectively) supplied to dehydrogenation reactor 40. A water valve 13 can be installed in the water supply line 11 that fluidly connects water storage tank 10 and dehydrogenation reactor 40, allowing water to be supplied to dehydrogenation reactor 40 by opening and closing the water valve 13. Furthermore, a water pump 15 can be installed in the water supply line 11, allowing water stored in water storage tank 10 to be pressurized and supplied to dehydrogenation reactor 40.

[0063] Acid storage tank 20 can store acid (hereinafter referred to as "FA") and / or acidic aqueous solution. The acid and / or acidic aqueous solution stored in acid storage tank 20 can be (e.g., selectively) supplied to dehydrogenation reactor 40. An acid valve 23 can be installed in the acid supply line 21 that fluidly connects acid storage tank 20 and dehydrogenation reactor 40. The acidic aqueous solution can be supplied to dehydrogenation reactor 40 by opening and closing the acid valve 23. In addition, an acid pump 25 can be installed in the acid supply line 21. The acidic aqueous solution stored in acid storage tank 20 can be pressurized by acid pump 25 and supplied to dehydrogenation reactor 40.

[0064] Acid storage tank 20 can form a corrosion-resistant protective film, such as a Teflon coating, to prevent acid corrosion. Acid promotes dehydrogenation reactions by adjusting the pH of chemical hydrides, thereby shortening their half-life.

[0065] The acids applicable to this document can be inorganic acids, such as sulfuric acid, nitric acid, phosphoric acid, boric acid, or hydrochloric acid; heteropoly acids; organic acids, such as acetic acid, formic acid, malic acid, citric acid, tartaric acid, ascorbic acid, lactic acid, oxalic acid, succinic acid, or taurine, and / or mixtures thereof. Formic acid (HCOOH) can be used because its lower molecular weight relative to hydrogen ions helps reduce the overall weight of the system, and it is (e.g., superior) safer than hydrochloric acid under high concentration conditions.

[0066] Formic acid, as a weak acid, can be stably maintained at a low pH under predetermined conditions, thus enabling (e.g., ensuring) relatively safe use. Furthermore, because captured carbon dioxide can be obtained through hydrogenation, carbon dioxide may be a key substance in terms of recovery and recycling. Additionally, formate can be converted to bicarbonate through dehydrogenation, in which additional hydrogen gas can be obtained.

[0067] The chemical hydride storage tank 30 can store chemical hydrides in aqueous solution form, and the stored chemical hydride aqueous solution (hereinafter referred to as "SBH aqueous solution") can be (e.g., selectively) supplied to the dehydrogenation reactor 40. A chemical hydride valve 33 can be installed in the chemical hydride supply line 31 connecting the chemical hydride storage tank 30 and the dehydrogenation reactor 40. The chemical hydride aqueous solution can be supplied to the dehydrogenation reactor 40 by opening and closing the chemical hydride valve 33. Furthermore, a chemical hydride pump 35 can be installed in the chemical hydride supply line 31, and the chemical hydride aqueous solution stored in the chemical hydride storage tank 30 can be pressurized by the chemical hydride pump 35 and supplied to the dehydrogenation reactor 40.

[0068] Chemical hydrides can be dissolved in water and provided as an aqueous solution. An alkaline neutralizing agent, such as NaOH, NaBO2, KOH, LiOH, or CsOH, can be added to the aqueous solution of the chemical hydride to prevent it from reacting with water.

[0069] To reduce the carbon monoxide byproduct generated during the reaction of chemical hydrides with acidic aqueous solutions, it may be useful (e.g., necessary) to slow down the hydrolysis reaction of chemical hydrides in aqueous solutions.

[0070] To slow down the hydrolysis of chemical hydrides in aqueous solutions, methods such as adjusting the pH value and controlling the temperature of the chemical hydride aqueous solution can be used.

[0071] When chemical hydrides are stored in chemical hydride storage tank 30 before reacting with acidic aqueous solution, the pH value can be increased by adding alkaline substances (such as NaOH, NaBO2, KOH, LiOH, or CsOH), thereby delaying the hydrolysis reaction. As the amount of alkaline substance added increases, it generates more heat of neutralization during reaction with the acidic aqueous solution, causing the internal temperature of the dehydrogenation reactor 40 to rise, which may increase the amount of carbon monoxide generated.

[0072] To avoid or minimize these problems, the amount of alkaline substances added can be reduced by lowering the temperature of the chemical hydride storage tank 30 when storing chemical hydrides. However, if the temperature of the chemical hydride storage tank 30 is lowered too much, the solubility of the chemical hydride may decrease. Therefore, the temperature of the chemical hydride storage tank 30 should be maintained within a predetermined temperature range (e.g., approximately 5 to 20 °C).

[0073] The chemical hydride storage tank 30 may include a thermal management device. This thermal management device is designed to maintain the temperature of the chemical hydride storage tank 30 within a predetermined temperature range.

[0074] See Figure 2A and Figure 2BThe thermal management device can be a cooling coil 37 installed inside the chemical hydride storage tank 30. Coolant (or heat transfer oil) can circulate within the cooling coil 37, and the temperature of the chemical hydride storage tank 30 can be controlled by the circulation of the coolant (or heat transfer oil). The cooling coil 37 can be installed in a coil shape inside the chemical hydride storage tank 30 (see [link]). Figure 2A It can also be arranged in a U-shape inside the chemical hydride storage tank 30 (see...). Figure 2B ).

[0075] See Figure 2C The thermal management device can be a cooling jacket 38 installed outside the chemical hydride storage tank 30. The coolant (or heat transfer oil) can circulate within the cooling jacket 38, and the temperature of the chemical hydride storage tank 30 can be controlled by the circulation of the coolant (or heat transfer oil).

[0076] Alternatively, the thermal management device may be a cooling bath 38 that houses the chemical hydride storage tank 30. A coolant (or heat transfer oil) may circulate within the cooling bath 38, and the temperature of the chemical hydride storage tank 30 may be controlled by the circulation of the coolant (or heat transfer oil).

[0077] The dehydrogenation reactor 40 can produce hydrogen through a chemical reaction between a chemical hydride and an acidic aqueous solution.

[0078] The dehydrogenation reactor 40 can be configured as a high-temperature, high-pressure vessel to provide (e.g., such that) the dehydrogenation reaction takes place under high-temperature, high-pressure conditions. For example, the dehydrogenation reactor 40 can be spherical, cuboid, or polygonal prism-shaped; in one exemplary embodiment, the dehydrogenation reactor 40 can be cylindrical.

[0079] The high-pressure hydrogen generated in the dehydrogenation reactor 40 can be selectively stored in the hydrogen storage tank 50. A hydrogen discharge line 51 connecting the dehydrogenation reactor 40 and the hydrogen storage tank 50 can be equipped with a hydrogen back pressure regulator 55, and a hydrogen valve 53 can be installed upstream of the hydrogen back pressure regulator 55. The high-pressure hydrogen generated in the dehydrogenation reactor 40 can be supplied to the hydrogen storage tank 50 according to the opening and closing of the hydrogen valve 53. The high-pressure hydrogen stored in the hydrogen storage tank 50 can be supplied to a high-pressure injection target.

[0080] To extract hydrogen from the dehydrogenation reactor 40 stably, the internal pressure of the reaction vessel of the dehydrogenation reactor 40 can be increased to a predetermined level (e.g., about 500 bar), thereby adjusting the boiling point of the reactants (e.g., from about 100 °C to about 400 °C) and minimizing the phase change of the reactants. The internal pressure of the reaction vessel of the dehydrogenation reactor 40 can be controlled by installing a hydrogen back pressure regulator 55 downstream of the dehydrogenation reactor 40.

[0081] The products generated by the dehydrogenation reaction in the dehydrogenation reactor 40 can be stored in the product storage tank 60. The product discharge line 61 connecting the dehydrogenation reactor 40 and the product storage tank 60 can be equipped with a product valve 63, which can discharge the products generated in the dehydrogenation reactor 40 into the product storage tank 60 according to the opening and closing of the product valve 63.

[0082] The reactants in the dehydrogenation reactor 40 react to generate hydrogen gas. As the amount of hydrogen gas increases, the internal pressure of the dehydrogenation reactor 40 can (e.g., gradually) increase. When the internal pressure of the dehydrogenation reactor 40 reaches a predetermined pressure, the hydrogen gas can be discharged into the hydrogen storage tank 50. As the hydrogen gas in the dehydrogenation reactor 40 is discharged into the hydrogen storage tank 50, the internal pressure of the dehydrogenation reactor 40 decreases. When (e.g., all) the reactions in the dehydrogenation reactor 40 are complete and (e.g., all) the hydrogen gas has been discharged into the hydrogen storage tank 50, the product in the dehydrogenation reactor 40 can be discharged into the product storage tank 60, and at the same time, the pressure inside the dehydrogenation reactor 40 decreases (e.g., drops).

[0083] For example, when the chemical hydride is NaBH4 and the acid is HCOOH, a dehydrogenation reaction as shown in reaction formula 1 will occur.

[0084] [Reaction Formula 1] NaBH4 + 0.5HCOOH + (3.5)H2O → 0.5NaHCO2 + 0.25(Na2B4O7·5H2O) + 4H2 +0.5H2O For example, the products may include NaHCO2, Na2B4O7·5H2O, and H2O, which are generated by dehydrogenation reactions.

[0085] Meanwhile, the dehydrogenation reaction system according to the exemplary embodiment may include a controller for supplying an acidic aqueous solution to the dehydrogenation reactor 40, (e.g., subsequently) supplying a liquid chemical hydride to the dehydrogenation reactor 40, discharging hydrogen from the dehydrogenation reactor 40 to a hydrogen storage tank 50 when the internal pressure of the dehydrogenation reactor 40 reaches a predetermined pressure, and discharging the product generated in the dehydrogenation reactor 40 to a product storage tank 60 after the dehydrogenation reaction is completed.

[0086] The controller may be implemented by one or more processors that operate according to a predetermined program (e.g., instructions), and the controller’s memory may store program instructions that are programmed to perform each operation (e.g., instructions) of the dehydrogenation reaction system control method of this disclosure by one or more processors.

[0087] Meanwhile, the dehydrogenation reaction system according to the exemplary embodiment may include: a temperature sensor for detecting the internal temperature of the dehydrogenation reactor 40; a first mass sensor for measuring the mass of water stored in the water storage tank 10; a second mass sensor for measuring the mass of acid stored in the acid storage tank 20; and a third mass sensor for measuring the mass of an aqueous solution of chemical hydride containing a neutralizing agent stored in the chemical hydride storage tank 30.

[0088] The temperature of the dehydrogenation reactor 40 measured by the temperature sensor, the mass of water measured by the first mass sensor, the mass of acid measured by the second mass sensor, and the mass of the chemical hydride aqueous solution measured by the third mass sensor can be transmitted to the controller.

[0089] In the following, a control method for a dehydrogenation reaction system according to an exemplary embodiment will be described in detail with reference to the accompanying drawings.

[0090] Figure 3 A flowchart of a control method for a dehydrogenation reaction system according to an exemplary embodiment is shown.

[0091] See Figure 3 The controller can determine whether the weight of water stored in water tank 10 is less than a first reference value (e.g., about 200 g), whether the weight of acid stored in acid tank 20 is less than a second reference value (e.g., about 100 g), and / or whether the weight of the chemical hydride aqueous solution containing a neutralizing agent stored in chemical hydride tank 30 is less than a third reference value (e.g., about 600 g) (S10).

[0092] In one exemplary embodiment, the first to third reference values ​​may each represent the respective weight of reactants required for a single reaction cycle in the dehydrogenation reactor 40.

[0093] If the weight of water stored in water tank 10 is less than the first reference value, or the weight of acid stored in acid tank 20 is less than the second reference value, or the weight of the chemical hydride aqueous solution containing neutralizing agent stored in chemical hydride tank 30 is less than the third reference value, the controller may output an error message and terminate the operation.

[0094] In operation S10, if the weights of water, acid and chemical hydride are all equal to or greater than their respective reference values, the controller may supply a first predetermined amount of water (e.g., about 50 g) and a second predetermined amount of acid (e.g., about 85 g) to the dehydrogenation reactor 40 (S20).

[0095] The controller can open the water valve 13 in the water supply line 11 and run the water pump 15 to supply water from the water storage tank 10 to the dehydrogenation reactor 40. In addition, the controller can open the acid valve 23 in the acid supply line 21 and run the acid pump 25 to supply acid from the acid storage tank 20 to the dehydrogenation reactor 40.

[0096] The acid supplied to the dehydrogenation reactor 40 can be provided at a molar ratio relative to water within a predetermined range. This predetermined molar ratio can be from about 20 mol% to about 50 mol%.

[0097] After water and acid are supplied to the dehydrogenation reactor 40, the controller can supply the dehydrogenation reactor 40 with an aqueous solution of chemical hydride containing a neutralizing agent at a first predetermined flow rate (e.g., about 30 ml / min) (S30).

[0098] The controller can open the chemical hydride valve 33 located in the chemical hydride supply line 31 and run the chemical hydride pump 35 to supply the chemical hydride aqueous solution from the chemical hydride storage tank 30 to the dehydrogenation reactor 40.

[0099] The controller can determine whether the amount of chemical hydride aqueous solution supplied to the dehydrogenation reactor 40 exceeds a third predetermined amount (e.g., about 500 g) (S40).

[0100] If the amount of chemical hydride aqueous solution supplied to the dehydrogenation reactor 40 is less than a third predetermined amount, the controller can determine whether the internal temperature of the dehydrogenation reactor 40 exceeds a first predetermined temperature (e.g., about 160 °C) (S50).

[0101] In operation S50, if the internal temperature of the dehydrogenation reactor 40 exceeds a first predetermined temperature, the controller can reduce the flow rate of the chemical hydride aqueous solution supplied to the dehydrogenation reactor 40 to a second predetermined flow rate (e.g., approximately 20 mL / min) and supply it to the dehydrogenation reactor 40 (S51). By reducing the supply flow rate of the chemical hydride aqueous solution, the reaction temperature of the acidic aqueous solution with the chemical hydride aqueous solution within the dehydrogenation reactor 40 (or the internal temperature of the dehydrogenation reactor 40) can be reduced. By reducing the reaction temperature within the dehydrogenation reactor 40 (or the internal temperature of the dehydrogenation reactor 40), the yield of byproducts (e.g., carbon monoxide) generated from the reaction of the acidic aqueous solution with the chemical hydride aqueous solution can be minimized, and the purity of hydrogen can be improved.

[0102] Alternatively, the controller can supply an additional predetermined amount of water (e.g., about 10 g) to the dehydrogenation reactor 40 (S51). The reaction between the acidic aqueous solution and the chemical hydride occurring in the dehydrogenation reactor 40 can be exothermic. Therefore, by supplying additional water to the dehydrogenation reactor 40, the internal temperature of the dehydrogenation reactor 40 can be reduced, thereby minimizing the production of byproducts (e.g., carbon monoxide) from the reaction between the acidic aqueous solution and the chemical hydride aqueous solution, and the purity of the hydrogen can be increased (e.g., improved).

[0103] In operation S50, if the internal temperature of the dehydrogenation reactor 40 is lower than a first predetermined temperature, the controller may (e.g., continuously) supply the dehydrogenation reactor 40 with an aqueous solution of chemical hydride, or may supply the aqueous solution of chemical hydride at a first predetermined flow rate.

[0104] In operation S40, if the supply of the chemical hydride aqueous solution to the dehydrogenation reactor reaches a third predetermined amount (e.g., 500 g), the controller can stop supplying the chemical hydride aqueous solution to the dehydrogenation reactor (40) (S60). At this time, the controller can close the chemical hydride valve 33 and stop the operation of the chemical hydride pump 35.

[0105] The controller can determine whether the internal temperature of the dehydrogenation reactor 40 is lower than a second predetermined temperature (e.g., about 80°C) (S70). The second predetermined temperature can be lower than the first predetermined temperature.

[0106] If the internal temperature of the dehydrogenation reactor 40 is equal to or higher than the second predetermined temperature, the controller can supply additional water to the dehydrogenation reactor 40 (S71). The controller can open the water valve 13 provided on the water supply line 11 and run the water pump 15 to supply water from the water storage tank 10 to the dehydrogenation reactor 40.

[0107] If the internal temperature of the dehydrogenation reactor 40 is lower than the second set temperature, the controller can discharge the product generated in the dehydrogenation reactor 40 to the product storage tank 60 (S80). The controller can also open the product valve 63 located in the product supply line 61.

[0108] The product generated in dehydrogenation reactor 40 may be in slurry form, and processing this product can be challenging when the temperature of dehydrogenation reactor 40 is high. Therefore, the temperature of the product can be reduced by supplying additional water to dehydrogenation reactor 40, and then the product can be recovered.

[0109] According to an exemplary embodiment, an acidic aqueous solution can be first supplied to the dehydrogenation reactor 40, followed by a progressive supply of an aqueous solution of a chemical hydride containing a neutralizing agent to initiate the dehydrogenation reaction. This process minimizes the formation of byproducts (e.g., carbon monoxide) that may occur during the reaction of the chemical hydride aqueous solution with the acidic aqueous solution, thereby increasing (e.g., improving) the purity of hydrogen. This document provides a principle for increasing (e.g., improving) the purity of hydrogen by first introducing an acidic aqueous solution into the dehydrogenation reactor 40.

[0110] There are three exemplary methods for introducing reactants into the dehydrogenation reactor 40.

[0111] The first method is to add an acidic aqueous solution to a solid chemical hydride (NaBH4 (solid) ← formic acid + H2O (solution)). The second method is to add an acidic aqueous solution to an aqueous solution of a chemical hydride containing a neutralizing agent (NaBH4 + NaOH + H2O (solution) ← formic acid + H2O (solution)). The third method is to add an aqueous solution of a chemical hydride containing a neutralizing agent to an acidic aqueous solution (formic acid + H2O (solution) ← NaBH4 + NaOH + H2O (solution)).

[0112] Each method will be described in detail through experiments below.

[0113] The first method provides a high hydrogen storage density (e.g., about 5 wt% to about 6 wt% of H2). When using a small-capacity reactor to deal with a high-pressure system, local over-reaction may occur due to poor flowability. Furthermore, if a second reaction is carried out after the first reaction, handling the residues and residual hydrogen may be difficult.

[0114] The first method of injecting acidic aqueous solution and chemical hydride was experimentally verified.

[0115] The experimental conditions for the first method are as follows: the dehydrogenation reactor 40 has a capacity of 370 mL, 100 g of chemical hydride is used, and an acidic aqueous solution (FA solution) equivalent to 4 equivalents of chemical hydride is added. The injection rate of the acidic aqueous solution is 4 mL / min.

[0116] See Figure 4A As shown in the figure, the external temperature of the dehydrogenation reactor 40 exhibits localized high-temperature and low-temperature zones, indicating that localized overreaction has occurred inside the reactor 40, and some unreacted areas exist. Therefore, the non-uniformity of the chemical hydride reaction and the temperature gradient can make controlling the reaction rate and temperature challenging.

[0117] See Figure 4BAs shown in the figure, increasing the reaction temperature in dehydrogenation reactor 40 increases the likelihood of generating gaseous impurities (e.g., carbon monoxide (CO) and / or methane (CH4)). Furthermore, it can be demonstrated (e.g., it has been confirmed) that reactions involving solid-phase chemical hydrides (NaBH4) result in insufficient reactant flowability.

[0118] In the second approach, the use of large amounts of initial chemical hydride (NaBH4) may result in excessive heat of reaction, making it challenging to control the reaction and potentially leading to hazardous situations.

[0119] The second method of injecting acidic aqueous solution and chemical hydride was experimentally verified.

[0120] The experimental conditions for the second method are as follows: 300 mg of an aqueous solution of chemical hydride, and an acidic aqueous solution equivalent to 4 equivalents of chemical hydride (FA solution) (see...). Figure 5A ) or water (H2O) (see Figure 5B After being injected into the reactor, the system was heated at a rate of 0.2 °C / min, and the heat production and hydrogen conversion rate were measured.

[0121] See Figure 5A It can be determined that a rapid reaction occurs (e.g., immediately) in the dehydrogenation reactor 40 after the injection of acidic aqueous solution (FA). Furthermore, see... Figure 5B It can be determined that a sudden reaction occurs in the dehydrogenation reactor 40 when a (e.g., a specific) threshold temperature is reached.

[0122] This may be due to an excess of reactants (SBH and H2O) within the reactor, which triggers a rapid reaction when threshold conditions (e.g., temperature, catalyst) are reached. Therefore, in large-scale dehydrogenation systems with limited heat dissipation capacity, the temperature may rise more rapidly, posing challenges to reaction control.

[0123] The third method offers an improvement by providing (e.g., enabling) control over the reaction temperature and rate through a reaction between a liquid-phase aqueous chemical hydride solution and a liquid-phase acidic aqueous solution. Furthermore, this method enables temperature control, thereby preventing (or minimizing) the formation of gaseous impurities such as carbon monoxide (CO) and / or methane (CH4). Moreover, the residue produced after the reaction of the aqueous chemical hydride solution with the acidic aqueous solution is (e.g., entirely) liquid, thus the resulting product is (e.g., easily) treatable.

[0124] The third method of injecting acidic aqueous solution and chemical hydride was verified through experiments.

[0125] The experimental conditions for the third method are as follows: the dehydrogenation reactor 40 has a capacity of 370 mL, and the chemical hydride aqueous solution consists of 25 wt% sodium borohydride (SBH), 5 wt% sodium hydroxide (NaOH), and 70 wt% water (H2O). The chemical hydride aqueous solution is injected at a rate of 20 mL / min for 10 minutes, equivalent to 50 g of SBH, and the preheating temperature is 60 °C. The hydrogen conversion rate is approximately 85%, based on a hydrogen density of approximately 3.3 wt% for the reactants.

[0126] See Figure 6 It can be confirmed that the reaction temperature between the acidic aqueous solution and the chemical hydride can be controlled below 120 °C. That is, the operating temperature of the reaction between the acidic aqueous solution and the chemical hydride aqueous solution in the dehydrogenation reactor can be maintained at 120 °C or below. Therefore, by controlling the reaction temperature below 120 °C, the formation of gaseous byproducts such as carbon monoxide (CO) can be minimized. Furthermore, due to the high water equivalent and the fact that (e.g., all) reactants are (e.g., completely) liquids, it can be confirmed that the products are recyclable (e.g., easily recovered).

[0127] Therefore, the third method offers improved controllability of reaction temperature and rate because it involves a reaction between a liquid-phase acidic aqueous solution and a liquid-phase chemical hydride. Furthermore, the ability to control the reaction temperature minimizes the formation of byproducts such as carbon monoxide (CO) and methane (CH4). Additionally, the product of the reaction between the acidic aqueous solution and the chemical hydride is also liquid-phase, thus allowing for convenient handling of the product.

[0128] Based on these experimental results, it can be confirmed that the third method offers improvements in providing (e.g., ensuring) reaction stability and control / system continuity. For example, under high pressure conditions, a fixed-bed reactor can be used to reduce hydrogen loss and provide (e.g., ensure) safety; therefore, the third method, where both reactants and products are in the liquid phase, is an improvement. Accordingly, in one embodiment, reaction stability and control / system continuity can be ensured by first injecting an acidic aqueous solution followed by an aqueous solution of a chemical hydride.

[0129] The following section describes a method for reducing the generation of carbon monoxide (CO) byproducts in the third method provided herein.

[0130] In the third method, experiments are conducted by varying seven parameters to determine the most important factors affecting (e.g., influencing) carbon monoxide (CO) generation, while measuring hydrogen conversion rate, hydrogen density, reactor peak temperature, and maximum CO concentration.

[0131] See Figure 7A and 7BThe seven variables include: (A) the concentration of the chemical hydride aqueous solution (SBH concentration); (B) the concentration of the neutralizing agent (NaOH concentration); (C) the amount of excess formic acid injected (excess FA); (D) the initial reaction temperature; (E) the injection rate of the SBH aqueous solution; (F) the amount of water pre-loaded into the reactor (FA aqueous solution concentration); and (G) the internal pressure of the reactor.

[0132] Here, the injection volume of the SBH aqueous solution is approximately 100 g, and the injection volume of the pre-filled acidic aqueous solution can be determined based on the amount of SBH aqueous solution.

[0133] In addition, the SBH aqueous solution contains NaOH (a neutralizing agent) to prevent SBH from reacting with water. During the reaction, in order for acid catalysis to occur, the amount of acidic aqueous solution injected can (e.g., must) exceed the amount of NaOH contained in the SBH aqueous solution. Therefore, the amount of formic acid (FA) injected in excess of the amount required for the reaction with the SBH aqueous solution (equivalent to the amount of NaOH contained in the SBH aqueous solution) can be defined as the excess FA injection volume.

[0134] See Figure 7A and 7B A review of the experimental results summarizing the peak temperature and carbon monoxide (CO) production showed that, under normal conditions, CO production increases dramatically when the temperature exceeds approximately 160 °C.

[0135] However, despite peak temperatures exceeding 160 °C, some experiments (e.g., anomalous cases) exhibited significantly lower levels of carbon monoxide (CO) production. These anomalous experiments were confirmed to have typically used aqueous formic acid (FA) instead of 100% formic acid, resulting in lower concentrations of the acid catalyst (see [link to relevant documentation]). Figure 8 For reference, the concentration of formic acid (FA) aqueous solution in Experiment #17 was 26.7 mol%, while the concentration of formic acid aqueous solution in Experiments #0, #1 and #18 was 31.8 mol%.

[0136] Figure 9 The maximum carbon monoxide (CO) production is shown as a function of the amount of water (H2O) loaded in the reactor. It has been confirmed that loading water (H2O) and formic acid (FA) simultaneously (e.g., #0 and #1) results in a decrease in carbon monoxide (CO) production compared to the case without water (#(-1)).

[0137] See the “P” mark in the figure. Figure 9 In Experiment #17, despite a low concentration of formic acid (FA), the production of carbon monoxide (CO) was relatively high, suggesting that multiple secondary factors may have contributed to this (e.g., anomalous) result. See Figure 10 for more details. Figure 11 .

[0138] See Figure 9 In the "Q" and "S" regions, some experiments (#2 and #3) showed lower carbon monoxide (CO) production despite higher formic acid (FA) concentrations and the absence of added water (H2O). This appears to be due to a significant decrease in peak temperature or the combined effect of other minor factors. Another factor could be the lower concentration of the SBH aqueous solution, which may result in a relatively slower reaction rate.

[0139] See Figure 9 In the "R" region, despite the low concentration of formic acid (FA), experiment #4 showed an unusually high maximum carbon monoxide (CO) production, suggesting that multiple secondary factors may have contributed to this (e.g., the anomalous) result. Another factor appears to be the increased amount of sodium hydroxide (NaOH), which led to an acid-base neutralization reaction between NaOH and FA, thus triggering the initial exothermic reaction.

[0140] See Figure 10A , 10B 10C and 10D and Figure 11 Experiment #17 showed that despite a relatively low formic acid (FA) concentration, its cumulative CO production was similar to that of Experiments #9 and #12. In Experiments #9 and #12, the higher FA concentrations in the initial stages of SBH aqueous solution injection led to accelerated reaction, and it is understandable (e.g., believed) that the resulting transient exothermic reaction promoted carbon monoxide (CO) formation. In Experiment #17, despite the lower FA concentration, the use of a large amount of NaOH resulted in a continuous release of heat from the neutralization reaction with FA, thus maintaining a higher reaction temperature and continuously producing small amounts of CO throughout the reaction. Experiment #17 indicated that the reaction temperature remained above 160 °C for most of the reaction time.

[0141] Based on these experimental results, it can be concluded that the key factor affecting carbon monoxide (CO) formation is the temperature of the dehydrogenation reactor 40, which is directly or indirectly affected by the reactant concentration and the amount of neutralizing agent (NaOH). Changes in reactant concentration lead to corresponding changes in reaction kinetics, thereby affecting the local or overall thermal conditions of the reactor.

[0142] The concentration of the SBH aqueous solution as a reactant can be up to 25 wt% to maintain a liquid phase; while the concentration range of formic acid (FA) is wider, from 0 to 100 wt%, and therefore has a greater impact on the reaction temperature. The temperature effect associated with the neutralizing agent NaOH may (e.g., only) originate from the acid-base neutralization reaction (e.g., rather than from the exothermic hydrogen generation), and since the chemical hydride aqueous solution containing NaOH is stored in a chemical hydride tank (30), the temperature of which is controlled within a specific range (e.g., 5 °C to 20 °C) by a temperature control unit, it may be unnecessary (e.g., excessive) to add the neutralizing agent, thereby minimizing its thermal effects.

[0143] In summary, the (e.g., critical) factors influencing carbon monoxide (CO) generation are likely reactor temperature and formic acid (FA) concentration. Therefore, in one exemplary embodiment, the amount of carbon monoxide (CO) generated during the reaction of the acidic aqueous solution with the chemical hydride can be minimized by controlling the injection rate of the chemical hydride or by adding additional water to the dehydrogenation reactor 40 to ensure the reactor temperature does not exceed a first set temperature (e.g., 160 °C) and maintaining the molar ratio of the acidic aqueous solution within a predetermined range (e.g., 20 mol% to 50 mol%).

[0144] As described herein, in SBH compressor systems operating under high pressure conditions, liquefaction of SBH can reduce (e.g., to reduce) hydrogen loss and byproduct formation, and improve (e.g., enhance) reactivity.

[0145] While liquefaction of SBH itself can improve flowability and provide (e.g., enable) continuous reaction, thereby reducing hydrogen loss and providing (e.g., enhance) reactivity, reaction temperature and byproduct formation can still be (e.g., significantly) affected by reactant mixing conditions and injection sequence.

[0146] When the injection sequence of the acidic aqueous solution and the chemical hydride aqueous solution, the concentration of the acidic aqueous solution (e.g., from about 20 mol% to about 50 mol%), and the storage conditions of the chemical hydride aqueous solution (e.g., from about 5 °C to about 20 °C) described in this disclosure are adopted, the thermal effect of acid-base neutralization can be mitigated, local temperature rise due to water endothermic reaction can be avoided, thereby maintaining (e.g., uniformly) a stable reaction temperature and reducing the formation of side reactions and related byproducts.

[0147] Experimental results show that, depending on the conditions used, the effect of reducing side reactions (e.g., the effect of ) can vary by tens of times.

[0148] As described herein, in one exemplary embodiment, the concentration of formic acid (FA) in the acidic aqueous solution can range from about 20 mol% to about 50 mol%. The amount of formic acid (FA) used can be determined by the concentration of NaOH in the SBH aqueous solution and the molar ratio of SBH to FA. The concentration of NaOH can be reflected in the amount of NaOH added to the SBH aqueous solution for neutralization with FA, while the molar ratio of SBH to FA is used to provide (e.g., define) the amount of FA required (e.g., necessary) for the reaction with SBH.

[0149] exist Figure 7A and 7B For example, when the NaOH concentration is 1 wt%, the excess FA is 0.5%, and the water content is 100 g, the FA concentration can be approximately 21 mol%. Furthermore, when the NaOH concentration is 7 wt%, the excess FA is 0.5%, and the water content is 50 g, the FA concentration can be approximately 48 mol%. Therefore, based on experimental conditions, the concentration of formic acid (FA) can be determined to be in the range of 20 mol% to 50 mol%.

[0150] Although this disclosure has been described in conjunction with exemplary embodiments, it should be understood that this disclosure is not limited to the disclosed embodiments, but rather is intended to cover various modifications and equivalent settings.

Claims

1. A dehydrogenation reaction system, comprising: A dehydrogenation reactor configured to generate hydrogen gas through a chemical reaction between an aqueous solution of a chemical hydride and an acidic aqueous solution; An acid storage tank, configured to store acid supplied to the dehydrogenation reactor; A chemical hydride storage tank is configured to store an aqueous solution of chemical hydride containing a neutralizing agent supplied to the dehydrogenation reactor; as well as A controller includes a memory storing computer-executable instructions, and at least one processor configured to access the memory and execute the instructions, wherein the instructions include: A first predetermined amount of water and a second predetermined amount of acidic aqueous solution are supplied to the dehydrogenation reactor; as well as, After supplying the water and the acidic aqueous solution to the dehydrogenation reactor, the chemical hydride aqueous solution is supplied to the dehydrogenation reactor at a first predetermined flow rate.

2. The dehydrogenation reaction system according to claim 1 further includes: A water storage tank is configured to store water supplied to the dehydrogenation reactor.

3. The dehydrogenation reaction system according to claim 2, wherein: If the internal temperature of the dehydrogenation reactor is higher than a first predetermined temperature The instructions also include supplying the chemical hydride aqueous solution to the dehydrogenation reactor at a second predetermined flow rate, wherein the second predetermined flow rate is lower than the first predetermined flow rate.

4. The dehydrogenation reaction system according to claim 2, wherein: If the internal temperature of the dehydrogenation reactor is higher than a first predetermined temperature The instructions also include supplying additional water to the dehydrogenation reactor.

5. The dehydrogenation reaction system according to claim 3, wherein: After supplying a third predetermined amount of chemical hydride aqueous solution to the dehydrogenation reactor, when the internal temperature of the dehydrogenation reactor is equal to or higher than the second predetermined temperature, The instructions also include supplying additional water to the dehydrogenation reactor.

6. The dehydrogenation reaction system according to claim 3, wherein: After supplying a third predetermined amount of chemical hydride aqueous solution to the dehydrogenation reactor, when the internal temperature of the dehydrogenation reactor is lower than the second predetermined temperature, The instructions also include discharging the products from the dehydrogenation reactor into a product storage tank.

7. The dehydrogenation reaction system according to claim 2, wherein: The molar ratio of the acidic aqueous solution to water supplied to the dehydrogenation reactor is within a predetermined range.

8. The dehydrogenation reaction system of claim 7, wherein, The molar ratio within the predetermined range is 20 mol% to 50 mol%.

9. The dehydrogenation reaction system according to claim 2, further comprising: A thermal management device is installed inside the chemical hydride storage tank, the thermal management device being configured to maintain the temperature of the chemical hydride storage tank within a predetermined temperature range.

10. The dehydrogenation reaction system according to claim 9, wherein: The predetermined temperature range is 5°C to 20°C.

11. The dehydrogenation reaction system according to claim 9, wherein: The thermal management device includes at least one of the following: Cooling coils installed inside the chemical hydride storage tank; A cooling jacket is installed outside the chemical hydride storage tank; or A cooling bath configured to contain the chemical hydride storage tank.

12. The dehydrogenation reaction system according to claim 1, wherein: The operating temperature for the reaction between the acidic aqueous solution and the chemical hydride aqueous solution in the dehydrogenation reactor is maintained at approximately 120°C or below.

13. A method for controlling a dehydrogenation reaction system, the method comprising: A first predetermined amount of water is supplied to the dehydrogenation reactor; A second predetermined amount of acidic aqueous solution is supplied to the dehydrogenation reactor; as well as After supplying the water and the acidic aqueous solution to the dehydrogenation reactor, an aqueous solution of chemical hydride containing a neutralizing agent is supplied to the dehydrogenation reactor at a first predetermined flow rate.

14. The control method according to claim 13, further comprising: Determine the internal temperature of the dehydrogenation reactor, and determine whether the internal temperature of the dehydrogenation reactor exceeds a first predetermined temperature; as well as When the internal temperature of the dehydrogenation reactor exceeds the first predetermined temperature, the chemical hydride aqueous solution is supplied to the dehydrogenation reactor at a second predetermined flow rate, wherein the second predetermined flow rate is lower than the first predetermined flow rate.

15. The control method according to claim 14, further comprising: Determine whether a third predetermined amount of aqueous chemical hydride solution has been supplied to the dehydrogenation reactor; After supplying the third predetermined amount of chemical hydride aqueous solution to the dehydrogenation reactor, it is determined whether the internal temperature of the dehydrogenation reactor is lower than the second predetermined temperature; as well as Based on the internal temperature of the dehydrogenation reactor, the product of the dehydrogenation reactor is discharged to a product storage tank or additional water is supplied to the dehydrogenation reactor.

16. The control method according to claim 15, further comprising: If the internal temperature of the dehydrogenation reactor is lower than the second predetermined temperature The product from the dehydrogenation reactor is then discharged into the product storage tank.

17. The control method according to claim 15, further comprising: If the internal temperature of the dehydrogenation reactor is equal to or higher than the second predetermined temperature Then additional water is supplied to the dehydrogenation reactor.

18. The control method according to claim 13, wherein: The molar ratio of the acidic aqueous solution to water supplied to the dehydrogenation reactor is within a predetermined range.

19. The control method according to claim 18, wherein: The molar ratio within the predetermined range is 20 mol% to 50 mol%.

20. The control method according to claim 13, wherein: The chemical hydride storage tank maintains a predetermined temperature range.

Images