Method for liquefying ammonia gas and apparatus for liquefying ammonia gas

Abstract

Provided is a method for liquefying ammonia gas, the method comprising: a step in which ammonia gas is supplied; and a step in which the ammonia gas and a solid ammonium salt react, whereby the ammonia gas liquefies to form liquid ammonia, and the solid ammonium salt decomposes into ammonium cations and anions.

Description

Ammonia gas liquefaction method and ammonia gas liquefaction device

[0001] The present application relates to an ammonia gas liquefaction method and an ammonia gas liquefaction device, and more specifically, to an ammonia gas liquefaction method and an ammonia gas liquefaction device using a solid ammonium salt.

[0002]

[0003] The problem of global warming is becoming more serious due to the indiscriminate use of fossil fuels, which have been the most widely used to date.

[0004] Accordingly, research and development of eco-friendly energy sources is in demand, and various research and development efforts are being conducted on the production and utilization of hydrogen. For example, fuel cells powered by hydrogen are not only environmentally friendly but can also achieve energy conversion efficiency two to three times that of conventional internal combustion engines.

[0005] Accordingly, hydrogen can be applied to various fields such as electricity generation, automobiles, and ships.

[0006] Meanwhile, ammonia is in the spotlight as a raw material for forming hydrogen. For example, Korean Patent Publication No. 10-2645544 discloses a power and hydrogen production complex system capable of producing electricity and high-purity hydrogen by combining a high-temperature fuel cell based on ammonia fuel and a hydrogen purification device, wherein the system comprises a first mode in which the fuel utilization rate of the fuel cell is reduced to less than 50% when the demand for electricity is low and the demand for hydrogen is high based on the fuel utilization rate of the fuel cell at a constant fuel supply amount according to the demand for electricity and hydrogen, a second mode in which the fuel utilization rate of the fuel cell is increased to more than 50% and less than 90% when the demand for electricity is high and the demand for hydrogen is low, and a third mode in which the fuel utilization rate of the fuel cell is maintained at 50% when the demand for electricity and hydrogen are similar, and the system is operated by the flow of an air line, an ammonia line, an inert gas line, a combustible gas line, and a power line, and the combustible gas line is a combustible gas supply device that is initially required to form an operating environment of the high-temperature fuel cell at a high temperature. A combined power and hydrogen production system is disclosed, wherein combustible gas is supplied to a burner device inside a high-temperature fuel cell, ignited, and the system is heated to an operating temperature through a thermal cycle. After the fuel cell is operated, the supply of combustible gas is stopped because an additional heat source is no longer required due to the reaction heat, and the system does not have a separate ammonia thermal decomposition device.

[0007] However, in order to produce hydrogen using ammonia as a raw material, a catalyst such as ruthenium must be used at a high temperature of over 600℃ to decompose ammonia, which requires not only a large-scale device, but also a complex structure and high cost, and the hydrogen production efficiency is low.

[0008]

[0009] The technical problem to be solved by the present application is to provide an ammonia gas liquefaction method and an ammonia gas liquefaction device that can efficiently store hydrogen and easily form hydrogen when needed.

[0010] Another technical problem to be solved by the present application is to provide an ammonia gas liquefaction method and an ammonia gas liquefaction device that maximize the hydrogen production yield.

[0011] Another technical challenge that the present application seeks to solve is to provide an ammonia gas liquefaction method and an ammonia gas liquefaction device that maximize operating efficiency and safety.

[0012] The technical problems that this application seeks to solve are not limited to those described above.

[0013]

[0014] To solve the above technical problem, the present application provides a method for liquefying ammonia gas.

[0015] According to one embodiment, the method for liquefying ammonia gas may include a step of supplying ammonia gas, and a step of reacting the ammonia gas with a solid ammonium salt such that the ammonia gas is liquefied to form liquid ammonia, and the solid ammonium salt is decomposed into ammonium cations and anions.

[0016] According to one embodiment, the ammonia gas may be supplied such that the amount of the ammonia gas that reacts with the solid ammonium salt to form the liquid ammonia is 15 wt% or more and 50 wt% or less.

[0017] According to one embodiment, the liquefaction of the ammonia gas can be performed under conditions of room temperature including -35°C or higher and 50°C or lower and atmospheric pressure including 1 atm.

[0018] In one embodiment, the liquid ammonia and the ammonium cations are decomposed to form hydrogen, and the liquid ammonia and the ammonium cations that are not formed into hydrogen, and the ammonia gas formed in the process of forming the hydrogen, can be recycled.

[0019] According to one embodiment, the ammonium salt may include, as the anion, one or more selected from the group consisting of nitrate (NO3-), hexafluorophosphate (PF6-), trifluoromethanesulfonate (CF3O3S-), and thiocyanate (SCN-).

[0020] In one embodiment, the ammonium salt may include one or more selected from the group of inorganic ammonium salts including ammonium chloride (NH4Cl), ammonium sulfate ((NH4)2SO4), ammonium carbonate ((NH4)2CO3), ammonium phosphate ((NH4)3PO4), ammonium bromide (NH4Br), ammonium iodide (NH4I), ammonium fluoride (NH4F), ammonium perchlorate (NH4ClO4), ammonium fluoroborate (NH4BF4), ammonium bisulfate ((NH4)HSO4), and ammonium peroxodisulfate ((NH4)2S2O8), and zinc ammonium salts ((NH4)2ZnCl4, (NH4)2ZnSO4) dichromate It may include one or more selected from the group of metal-containing ammonium salts including ammonium ((NH4)2Cr2O7), ammonium vanadate (V) (NH4VO3), ammonium tetrathiomolybdate ((NH4)2MoS4), and ammonium hexafluorotitanate ((NH4)2TiF6), and it may include one or more selected from the group of organic ammonium salts including ammonium acetate (CH3CO2NH4) and ammonium tetraphenylborate (NH4B(C6H5)4).

[0021] In one embodiment, the ammonia gas and the solid ammonium salt may be stirred.

[0022]

[0023] To solve the above technical problem, the present application provides an ammonia gas liquefaction device.

[0024] According to one embodiment, the ammonia gas liquefaction device may include a liquefaction source forming unit including a gas inlet through which ammonia gas is introduced, a tank in which a solid ammonium salt that reacts with the ammonia gas introduced through the gas inlet to form liquid ammonia by liquefying the ammonia gas is stored, and a liquid discharge port for discharging the liquid ammonia formed in the tank.

[0025] In one embodiment, within the tank, the solid ammonium salt can be decomposed into ammonium cations and anions.

[0026] In one embodiment, the liquid ammonia and the ammonium cation may be decomposed to form hydrogen.

[0027] According to one embodiment, the ammonia gas liquefaction device may further include a gas source supply unit connected to the gas inlet to supply the ammonia gas to the liquefaction source forming unit.

[0028] According to one embodiment, the gas source supply unit controls the supply amount of the ammonia gas supplied to the liquefaction source forming unit, and can control the supply amount of the ammonia gas so that the amount of the ammonia gas liquefied and formed into the liquid ammonia by reacting with the solid ammonium salt stored in the liquefaction source forming unit is 15 wt% or more and 50 wt% or less.

[0029] According to one embodiment, the liquid ammonia and the ammonium cations not formed with the hydrogen may be recycled to the liquefaction source forming unit, and the ammonia gas formed in the process of forming the hydrogen may be recycled to the gas source supply unit or the liquefaction source forming unit.

[0030] According to one embodiment, the liquefied source forming unit can be operated under room temperature conditions including -35°C or higher and 50°C or lower and atmospheric pressure conditions including 1 atm.

[0031]

[0032] According to an embodiment of the present application, a method for liquefying ammonia gas can be provided, comprising a step of supplying ammonia gas, and a step of reacting the ammonia gas with a solid ammonium salt, thereby liquefying the ammonia gas to form liquid ammonia, and decomposing the solid ammonium salt into ammonium cations and anions.

[0033] According to an embodiment of the present application, the amount of ammonia gas supplied can be controlled.

[0034] Accordingly, according to the embodiment of the present application, not only can the rate at which the ammonia gas is converted into the liquid ammonia be fast, but also the solid ammonium salt can be decomposed into the ammonium cation and the anion, and can be substantially completely dissolved in the liquid ammonia.

[0035] In other words, according to the embodiment of the present application, as the supply amount of the ammonia gas is controlled, the ammonia gas and the solid ammonium salt can be substantially completely converted into a liquid state.

[0036] Due to this, the amount of the liquid ammonia and / or the ammonium cation provided in a liquid state can be maximized.

[0037] Accordingly, the amount of hydrogen formed by decomposition of the liquid ammonia and the ammonium cation can be maximized.

[0038] Furthermore, it has excellent stability for electrodes and can have high current density.

[0039] Additionally, according to an embodiment of the present application, the liquid ammonia and the ammonium cations not formed with the hydrogen, and the ammonia gas formed in the process of forming the hydrogen can be recycled.

[0040] This will maximize the hydrogen production yield.

[0041] In one embodiment, the hydrogen can be used as an energy source. That is, according to the embodiment of the present application, there is a technical effect that allows an eco-friendly energy source to be efficiently produced.

[0042]

[0043] FIG. 1 is a drawing for explaining an ammonia gas liquefaction device according to an embodiment of the present application.

[0044] Figure 2 is a drawing for explaining an ammonia gas liquefaction method according to an embodiment of the present application.

[0045] FIG. 3 is a drawing for explaining a gas source supply unit according to an embodiment of the present application.

[0046] FIG. 4 is a drawing for explaining a method of supplying ammonia gas to a liquefied source forming unit according to an embodiment of the present application.

[0047] FIG. 5 is a drawing for explaining a method for forming liquid ammonia in a liquefaction source forming unit according to an embodiment of the present application.

[0048] FIG. 6 is a drawing for explaining a method of forming hydrogen in a hydrogen production unit according to an embodiment of the present application.

[0049] FIG. 7 is a drawing for explaining an ammonia gas liquefaction device according to one embodiment of the present application.

[0050] FIG. 8 is a drawing for explaining an ammonia gas liquefaction device according to another embodiment of the present application.

[0051] FIG. 9 is a drawing for explaining an ammonia gas liquefaction device according to another embodiment of the present application.

[0052] Fig. 10 is a drawing for explaining a liquefied source forming unit according to an embodiment of the present application.

[0053] Fig. 11 is a graph showing linear sweep voltammetry (LSV) measurements for ammonia gas liquefaction according to Experimental Examples 1-1 to 1-5 of the present application.

[0054] Fig. 12 is a graph showing cyclic voltammetry (CV) measurements for ammonia gas liquefaction according to Experimental Examples 1-1 to 1-5 of the present application.

[0055] Fig. 13 is a graph showing current measurement in ammonia gas liquefaction according to Experimental Examples 1-1 to 1-5 of the present application.

[0056] Fig. 14 is a graph showing voltage measurements in ammonia gas liquefaction according to Experimental Examples 1-1 to 1-5 of the present application.

[0057] Figure 15 is a photograph of a liquid manufactured according to Experimental Example 2-1 of the present application.

[0058] Figure 16 is a photograph of a liquid manufactured according to Experimental Example 2-2 of the present application.

[0059] Figure 17 is a photograph of a liquid manufactured according to Experimental Example 2-3 of the present application.

[0060] Figure 18 is a photograph of a liquid manufactured according to Experimental Example 2-4 of the present application.

[0061] Figure 19 is a photograph of a liquid manufactured according to Experimental Example 2-5 of the present application.

[0062] Figure 20 is a graph showing the conversion efficiency of a liquid manufactured according to Experimental Examples 2-1 to 2-5 of the present application.

[0063] Figure 21 is a graph showing hydrogen formed according to Experimental Example 3 of the present application.

[0064]

[0065] Hereinafter, preferred embodiments of the present application will be described in detail with reference to the attached drawings. However, the technical concepts of the present application are not limited to the embodiments described herein and may be embodied in other forms. Rather, the embodiments introduced herein are provided to ensure that the disclosed content is thorough and complete and to sufficiently convey the concepts of the present application to those skilled in the art.

[0066] Also, although terms such as first, second, and third have been used to describe various components in various embodiments of this specification, these components should not be limited by these terms. These terms are only used to distinguish one component from another. Thus, what is referred to as a first component in one embodiment may be referred to as a second component in another embodiment. Each embodiment described and illustrated herein also includes its complementary embodiments. Also, the term "and / or" has been used herein to mean including at least one of the components listed before and after.

[0067] In the specification, singular expressions include plural expressions unless the context clearly dictates otherwise. In addition, terms such as "comprise" or "have" are intended to indicate the presence of a feature, number, step, component, or combination thereof described in the specification, and should not be construed as excluding the possibility of the presence or addition of one or more other features, numbers, steps, components, or combinations thereof. In addition, in the following description of the present application, if a detailed description of a related known function or configuration is determined to unnecessarily obscure the gist of the present application, such detailed description will be omitted.

[0068]

[0069] FIG. 1 is a drawing for explaining an ammonia gas liquefaction device according to an embodiment of the present application, FIG. 2 is a drawing for explaining an ammonia gas liquefaction method according to an embodiment of the present application, FIG. 3 is a drawing for explaining a gas source supply unit according to an embodiment of the present application, FIG. 4 is a drawing for explaining a method of supplying ammonia gas to a liquefaction source forming unit according to an embodiment of the present application, FIG. 5 is a drawing for explaining a method of forming liquid ammonia in a liquefaction source forming unit according to an embodiment of the present application, FIG. 6 is a drawing for explaining a method of forming hydrogen in a hydrogen production unit according to an embodiment of the present application, FIG. 7 is a drawing for explaining an ammonia gas liquefaction device according to an embodiment of the present application, FIG. 8 is a drawing for explaining an ammonia gas liquefaction device according to another embodiment of the present application, FIG. 9 is a drawing for explaining an ammonia gas liquefaction device according to another embodiment of the present application, and FIG. 10 is a drawing for explaining a liquefaction source forming unit according to an embodiment of the present application. It's a drawing.

[0070] Referring to FIG. 1, the ammonia gas liquefaction device (100) may include a gas source supply unit (10), a liquefaction source forming unit (20), and a hydrogen production unit (30).

[0071] According to one embodiment with reference to FIGS. 1, 3 and 4, the gas source supply unit (10) may include a gas tank (12) storing ammonia gas (NH3(g), 1), and a source outlet (11) communicating with a gas inlet (21) of the liquefaction source forming unit (20) to supply the ammonia gas (1) stored in the gas tank (12) to the liquefaction source forming unit (20).

[0072] According to one embodiment, the gas source supply unit (10) can control the supply amount of the ammonia gas (1) supplied to the liquefaction source forming unit (20). For example, the gas source supply unit (10) can control the supply amount of the ammonia gas (1) so that the amount of the ammonia gas (1) liquefied and formed into liquid ammonia (NH3(ℓ), 5) by reacting with the solid ammonium salt (NH4X(s), 2) stored in the liquefaction source forming unit (20) is 15 wt% or more to 50 wt% or less, more specifically, so that the amount is 27 wt% or more to 37 wt% or less. In other words, the gas source supply unit (10) can control the supply amount of the ammonia gas (1) so that the amount of the ammonia gas (1) dissolved in the liquefaction source forming unit (20) is 27 wt% or more and 37 wt% or less. More specifically, for example, the gas source supply unit (10) can control the supply amount of the ammonia gas (1) so that the amount of the ammonia gas (1) dissolved in the liquefaction source forming unit (20) is more than 27 wt% and less than 34 wt%. More specifically, for example, the gas source supply unit (10) can control the supply amount of the ammonia gas (1) so that the amount of the ammonia gas (1) dissolved in the liquefaction source forming unit (20) is 30 wt%.

[0073] Accordingly, according to the embodiment of the present application, not only can the rate at which the ammonia gas (1) is converted into the liquid ammonia (5) be fast, but also the solid ammonium salt (2) can be decomposed into ammonium cations (NH4+, 3) and anions (X-, 4) and be substantially completely dissolved in the liquid ammonia (5).

[0074] In other words, according to the embodiment of the present application, the gas source supply unit (10) controls the supply amount of the ammonia gas (1) so that the amount of the ammonia gas (1) liquefied and formed into liquid ammonia (5) is 15 wt% or more and 50 wt% or less, more specifically, 27 wt% or more and 37 wt% or less, so that the ammonia gas (1) and the solid ammonium salt (2) can be substantially completely converted into a liquid state.

[0075] According to an embodiment of the present application, in order for hydrogen (H2, 6) to be formed in the hydrogen production unit (30), a liquid raw material, i.e., ammonia and / or ammonium salt in a liquid state, may need to be provided. In other words, according to the present application, in the hydrogen production unit (30), the liquid ammonia (5) and / or the ammonium cation (3) in a liquid state may be decomposed to form the hydrogen (6).

[0076] Meanwhile, according to an embodiment of the present application, the gas source supply unit (10) controls the supply amount of the ammonia gas (1) so that the amount of the ammonia gas (1) liquefied and formed into liquid ammonia (5) is 15 wt% or more and 50 wt% or less, more specifically, 27 wt% or more and 37 wt% or less, so that the ammonia gas (1) and the solid ammonium salt (2) can be substantially completely converted into a liquid state.

[0077] Due to this, the amount of the liquid ammonia (5) and / or the ammonium cation (3) in a liquid state provided to the hydrogen production unit (30) can be maximized.

[0078] Accordingly, the amount of hydrogen (6) formed in the hydrogen production unit (30) can be maximized.

[0079] Furthermore, the stability of the electrode of the hydrogen production unit (30) can be excellent and the current density can be high.

[0080] On the other hand, unlike the embodiments of the present application, when the supply of ammonia gas is controlled so that the amount of ammonia gas liquefied and formed into liquid ammonia is less than 27 wt%, the solid ammonium salt may be incompletely dissolved in the liquid ammonia. In other words, some of the solid ammonium salt may not react with the ammonia gas, and thus, the solid ammonium salt may not be converted into a liquid phase and may still exist in a solid phase.

[0081] Accordingly, since the ammonium salt is still in a solid state, supply to the hydrogen production unit (30) may not be possible.

[0082] Accordingly, hydrogen may not be formed in the hydrogen production unit (30).

[0083] Alternatively, unlike the embodiment of the present application, if the amount of ammonia gas supplied is controlled so that the amount of ammonia gas liquefied and formed into liquid ammonia exceeds 37 wt%, the ionic conductivity of the ammonium salt reacting with the ammonia gas may decrease.

[0084] This may slow down the rate at which ammonia gas is converted to liquid ammonia.

[0085] Accordingly, the amount of hydrogen formed in the hydrogen production unit (30) may be reduced.

[0086] However, according to an embodiment of the present application, the supply amount of the ammonia gas (1) can be controlled so that the amount of the ammonia gas (1) liquefied and formed into liquid ammonia (5) is 15 wt% or more and 50 wt% or less, more specifically, 27 wt% or more and 37 wt% or less.

[0087] Due to this, the ammonia gas (1) and the solid ammonium salt (2) can be substantially completely converted into a liquid state, and accordingly, the amount of the liquid ammonia (5) and / or the ammonium cation (3) in a liquid state provided to the hydrogen production unit (30) can be maximized, and thus the amount of the hydrogen (6) formed in the hydrogen production unit (30) can be maximized. Furthermore, the stability of the electrode of the hydrogen production unit (30) can be excellent, and the current density can be high.

[0088] According to one embodiment, the gas source supply unit (10) may further include an inlet (not shown). The inlet (not shown) may be connected to the outlet (37) of the hydrogen production unit (30).

[0089] Accordingly, the gas source supply unit (10) can receive ammonia gas (1) formed in the process of forming the hydrogen (6) in the hydrogen production unit (30). In other words, according to the embodiment of the present application, the ammonia gas (1) can be recycled.

[0090] Accordingly, the ammonia gas liquefaction device (100) according to the embodiment of the present application can maximize the hydrogen production yield.

[0091] According to one embodiment with reference to FIGS. 1, 4, and 5, the liquefaction source forming unit (20) may include a gas inlet (21) through which the ammonia gas (1) flows in, a tank (22) in which the solid ammonium salt (2) that reacts with the ammonia gas (1) flowing in through the gas inlet (21) to form the liquid ammonia (5) in which the ammonia gas (1) is liquefied is stored, and a liquid discharge port (23) for discharging the liquid ammonia (5) formed in the tank (22).

[0092] According to one embodiment, the gas inlet (21) may be in communication with the source outlet (11).

[0093] Due to this, the ammonia gas (1) stored in the gas source supply unit (10) can be supplied to the tank (22) through the source outlet (11) and the gas inlet (21).

[0094] According to one embodiment, the liquefied source forming unit (20) can store the solid ammonium salt (2).

[0095] According to one embodiment, the solid ammonium salt (2) may have high solubility in the ammonia gas (1).

[0096] Due to this, hydrogen bonding between the ammonia gas (1), the ammonium cation (3), and / or the anion (4) can be facilitated.

[0097] According to one embodiment, the stronger the anion (4), the more the liquefaction of the ammonia gas (1) can be promoted. The ammonium salt (2) may include, as the anion (X-, 4), one or more selected from the group consisting of nitrate (NO3-), hexafluorophosphate (PF6-), trifluoromethanesulfonate (CF3O3S-), and thiocyanate (SCN-). However, the present invention is not limited thereto.

[0098] According to one embodiment, the liquefied source forming unit (20) can store a mixture of the solid ammonium salt (2). For example, the mixture of the solid ammonium salt (2) can include at least one of ammonium nitrate (NH4NO3), ammonium hexafluorophosphate (NH4PF6), ammonium triflate (NH4CF3SO3), and ammonium thiocyanate (NH4SCN). However, the present invention is not limited thereto. For another example, the ammonium salt (2) may include one or more selected from the group of inorganic ammonium salts including ammonium chloride (NH4Cl), ammonium sulfate ((NH4)2SO4), ammonium carbonate ((NH4)2CO3), ammonium phosphate ((NH4)3PO4), ammonium bromide (NH4Br), ammonium iodide (NH4I), ammonium fluoride (NH4F), ammonium perchlorate (NH4ClO4), ammonium fluoroborate (NH4BF4), ammonium bisulfate ((NH4)HSO4), and ammonium peroxodisulfate ((NH4)2S2O8), and zinc ammonium salts ((NH4)2ZnCl4, (NH4)2ZnSO4) dichromate It may include one or more selected from the group of metal-containing ammonium salts including ammonium ((NH4)2Cr2O7), ammonium vanadate (V) (NH4VO3), ammonium tetrathiomolybdate ((NH4)2MoS4), and ammonium hexafluorotitanate ((NH4)2TiF6), and it may include one or more selected from the group of organic ammonium salts including ammonium acetate (CH3CO2NH4) and ammonium tetraphenylborate (NH4B(C6H5)4). However, it is not limited thereto.

[0099] According to one embodiment, the liquefaction source forming unit (20) can receive the ammonia gas (1) whose supply amount is controlled from the gas source supply unit (10). For example, the liquefaction source forming unit (20) can receive the ammonia gas (1) from the gas source supply unit (10) such that the amount of the ammonia gas (1) liquefied and formed into liquid ammonia (5) by reacting with the solid ammonium salt (2) is 15 wt% or more and 50 wt% or less, more specifically, 27 wt% or more and 37 wt% or less.

[0100] Accordingly, according to the embodiment of the present application, not only can the rate at which the ammonia gas (1) is converted into the liquid ammonia (5) inside the tank (22) of the liquefied source forming unit (20) be fast, but also the solid ammonium salt (2) can be decomposed into ammonium cations (3) and anions (4) and be substantially completely dissolved in the liquid ammonia (5).

[0101] In other words, according to the embodiment of the present application, the amount of the ammonia gas (1) supplied to the liquefaction source forming unit (20) is controlled so that the amount of the ammonia gas (1) liquefied and formed into liquid ammonia (5) is 15 wt% or more and 50 wt% or less, more specifically, 27 wt% or more and 37 wt% or less, so that the ammonia gas (1) and the solid ammonium salt (2) can be substantially completely converted into a liquid state.

[0102] Due to this, the amount of the liquid ammonia (5) and / or the ammonium cation (3) in a liquid state provided to the hydrogen production unit (30) can be maximized.

[0103] Accordingly, the amount of hydrogen (6) formed in the hydrogen production unit (30) can be maximized.

[0104] Furthermore, the stability of the electrode of the hydrogen production unit (30) can be excellent and the current density can be high.

[0105] According to one embodiment, the liquefaction source forming unit (20) may be operated under room temperature and atmospheric pressure conditions when the liquid ammonia (5) is formed from the ammonia gas (1). The room temperature may include, for example, -35°C or higher to 50°C or lower, more specifically, 0°C or higher to 35°C or lower, and the atmospheric pressure may include, for example, 1 atm. In other words, the liquefaction source forming unit (20) may be operated at 0°C or higher to 35°C or lower and 1 atm.

[0106] Due to this, the present application can have superior operating efficiency and safety compared to conventional devices for liquefying ammonia gas.

[0107] Conventionally, low-temperature processes and / or high-pressure processes could be used to liquefy ammonia gas. More specifically, for example, conventionally, low-temperature processes of -60°C or higher to -30°C or lower and / or high-pressure processes of 8 atm or higher to 20 atm or lower could be used to liquefy ammonia gas.

[0108] Because of this, conventional devices for liquefying ammonia gas had the problem of requiring not only a large scale but also a complex structure and high cost.

[0109] However, according to the present application, the liquefied source forming unit (20) can be operated under room temperature and pressure conditions.

[0110] Accordingly, the present application can maximize operating efficiency and safety in forming the liquid ammonia (5) from the ammonia gas (1).

[0111] According to one embodiment, the liquefied source forming unit (20) may receive the liquid ammonia (5), the ammonium cation (3), and / or the anion (4) that is not formed from the hydrogen (6) from the hydrogen producing unit (30). In other words, according to an embodiment of the present application, the liquid ammonia (5), the ammonium cation (3), and / or the anion (4) may be recycled.

[0112] In addition, according to one embodiment, the liquefaction source forming unit (20) may receive ammonia gas (1) formed in the process of forming the hydrogen (6) in the hydrogen production unit (30). In other words, according to an embodiment of the present application, the ammonia gas (1) may be recycled.

[0113] Due to this, the ammonia gas liquefaction device (100) according to the embodiment of the present application can maximize the hydrogen production yield.

[0114] According to one embodiment, the liquefied source forming unit (20) may further include a stirring module (not shown). More specifically, the stirring module may be adjacent to the solid ammonium salt (2) stored in the tank (22). For example, when the solid ammonium salt (2) is stored in the lower portion of the tank (22), the stirring module may extend from the upper portion of the tank (22) in a downward direction. However, the present invention is not limited thereto, and the stirring module is not limited as long as it has a structure that can increase the surface area where the ammonia gas (1) and the solid ammonium salt (2) come into contact.

[0115] Accordingly, according to the embodiment of the present application, in the liquefied source forming unit (20), the ammonia gas (1) and the solid ammonium salt (2) are stirred, so that the surface area where the ammonia gas (1) and the solid ammonium salt (2) come into contact can be maximized.

[0116] Accordingly, liquefaction of the ammonia gas (1) and / or the solid ammonium salt (2) can be promoted in the liquefaction source forming unit (20).

[0117] Due to this, the ammonia gas liquefaction device (100) according to the embodiment of the present application can have excellent liquid conversion efficiency.

[0118] According to one embodiment with reference to FIGS. 1 and 6, the hydrogen production unit (30) may include a liquid inlet (31) into which the liquid ammonia (5) formed in the liquefaction source forming unit (20) flows, a housing (32) into which the liquid ammonia (5) flowing in through the liquid inlet (31) is decomposed to form hydrogen (H2, 6), and a gas discharge port (36) for discharging the hydrogen (6) formed in the housing (32).

[0119] According to one embodiment, the liquid inlet (31) may be communicated with the liquid outlet (23).

[0120] Accordingly, the liquid ammonia (5) formed in the liquefied source forming unit (20) can be supplied into the housing (32) through the liquid outlet (23) and the liquid inlet (31). In addition, the ammonium cation (3) and / or the anion (4) of the liquefied source forming unit (20) can be supplied into the housing (32) through the liquid outlet (23) and the liquid inlet (31).

[0121] According to one embodiment, the hydrogen production unit (30) may include a battery cell inside the housing (32). The battery cell may include a cathode (33), an anode (35) facing the cathode (33), and a separator (34) between the cathode (33) and the anode (35).

[0122] According to one embodiment, the cathode (33) may include a liquid inlet path communicating with the liquid inlet (31).

[0123] Accordingly, through the liquid inlet (31) and the liquid inlet path, the liquid ammonia (5), the ammonium cation (3), and / or the anion (4) can flow between the cathode (33) and the separator (34).

[0124] According to one embodiment, at the cathode (33), the liquid ammonia (5) and / or the ammonium cation (3) can be decomposed.

[0125] Due to this, the hydrogen (6) can be formed. At the cathode (33), the reaction in which the liquid ammonia (5) is decomposed to form the hydrogen (6) can follow, for example, reaction formulas 1 to 6 below.

[0126] <Reaction Scheme 1>

[0127] *NH3 + NH3 → *NH2 + NH4+ + e-

[0128]

[0129] <Reaction Formula 2>

[0130] *NH2 + 2NH3 → *H2NNH2 + NH4+ + e-

[0131]

[0132] <Reaction Formula 3>

[0133] *H2NNH + NH3 → *HNNH2 + NH4+ e-

[0134]

[0135] <Reaction Formula 4>

[0136] *HNNH2 + NH3 → *HNNH + NH4+ + e-

[0137]

[0138] <Reaction Formula 5>

[0139] *HNNH + NH3 → *NNH + NH4+ + e-

[0140]

[0141] <Reaction Formula 6>

[0142] *NNH + NH3 → *N2 + NH4+ + e-

[0143]

[0144] According to the above reaction formula 2, hydrazine (H2NNH2) containing nitrogen bonds (NN) can be formed on the surface of the cathode (33). Subsequently, the cathode (33) can lose electrons (e-) through an oxidation reaction, and hydrogen ions (H+) can be formed. The formed hydrogen ions (H+) can coexist with the ammonium cations (NH4+, 3).

[0145] According to one embodiment, the separator (34) can selectively pass the hydrogen ions (H+) to the anode (35). The hydrogen ions (H+) passing through the separator (34) can obtain electrons (e-) at the anode (35), and the hydrogen (6), i.e., hydrogen gas (H2), can be formed.

[0146] According to one embodiment, the anode (35) may include a gas discharge path communicating with the gas discharge port (36).

[0147] Accordingly, the formed hydrogen (6) can be discharged outside the housing (32) through the gas discharge path and the gas discharge port (36).

[0148] According to one embodiment, the hydrogen (6) can be used as an energy source. That is, the ammonia gas liquefaction device (100) according to the embodiment of the present application can efficiently produce an eco-friendly energy source.

[0149] According to one embodiment, the hydrogen production unit (30) may further include an outlet (37) connected to the outside of the housing (32), and the cathode (33) may further include an outlet path communicating with the outlet (37).

[0150] According to one embodiment, during the formation process of the hydrogen (6) according to the reaction formulas 1 to 6, unreacted liquid ammonia (5), the ammonium cation (3), and / or the anion (4) may remain. The liquid ammonia (5), the ammonium cation (3), and / or the anion (4) may be discharged outside the housing (32) through the outlet path and the outlet (37).

[0151] According to one embodiment, the outlet (37) may be connected to the inlet (not shown) of the gas source supply unit (20) and / or the gas inlet (21) of the liquefaction source forming unit (20).

[0152] Due to this, the ammonia gas (1), the liquid ammonia (5), the ammonium cation (3), and / or the anion (4) can be recycled.

[0153] Accordingly, the ammonia gas liquefaction device (100) according to the embodiment of the present application can maximize the hydrogen production yield.

[0154] According to one embodiment, other substances may be formed in the process in which the liquid ammonia (5) and the ammonium cation (3) are decomposed to form the hydrogen (6). The other substances may be, for example, amine (NH2(g)), nitrogen (N2(g)), etc. However, the present invention is not limited thereto. The other substances may be discharged outside the housing (32) through the outlet (37).

[0155] According to one embodiment, the cathode (33) may be formed of a material having excellent corrosion resistance. More specifically, the cathode (33) may be formed of a material that is highly resistant to reaction with the liquid ammonia (5). For example, the cathode (33) may be formed of an alloy, for example, austenitic stainless steel, for example, 316 stainless steel (SUS 316), molybdenum, or an insoluble coated metal. However, the present invention is not limited thereto.

[0156] According to one embodiment, the anode (35) may be formed of a metal or a coated metal material. For example, the anode (35) may be formed of a titanium or platinum-coated titanium material. However, the present invention is not limited thereto. Alternatively, for example, the anode (35) may be a gas diffusion electrode (GDE) or a gas diffusion layer (GDL). However, the present invention is not limited thereto.

[0157] According to one embodiment, the separation membrane (34) may be formed of a material that allows the ammonium cations (3) to pass through. Alternatively, the separation membrane (34) may be a modified membrane that allows the ammonium cations (3) to pass through. For example, the separation membrane (34) may be a Nafion membrane. However, the present invention is not limited thereto.

[0158] According to one embodiment, the liquid ammonia (5) and / or the ammonium cation (3) can be decomposed at the anode (35). In this case, the anode (35), like the cathode (33), can be formed of a material having excellent corrosion resistance. More specifically, the anode (35) can be formed of a material that is resistant to reaction with the liquid ammonia (5). For example, the anode (35) can be formed of an alloy, for example, austenitic stainless steel, for example, 316 stainless steel (SUS 316), molybdenum, or an insoluble coated metal. However, the present invention is not limited thereto.

[0159] According to one embodiment, a porous structure may further be included between the cathode (33) and the separator (34), and / or between the separator (34) and the anode (35).

[0160] According to the ammonia gas liquefaction device (100) according to the embodiment of the present application described above, hydrogen can be efficiently stored and hydrogen can be easily formed when necessary.

[0161] Due to this, the ammonia gas liquefaction device (100) has an efficient technical effect in terms of hydrogen energy storage and generation.

[0162] Referring to FIG. 7, an ammonia gas liquefaction device (100) according to an embodiment of the present application includes the gas source supply unit (10), and the gas source supply unit (10) may include a system for separating other substances mixed with the ammonia gas (1), such as amines, nitrogen, etc. The system may separate the other substances mixed with the ammonia gas (1), for example, by chemical absorption, membrane separation, and / or pressure swing adsorption. However, the present invention is not limited thereto.

[0163] Accordingly, the gas source supply unit (10) receives the ammonia gas (1) formed in the process of forming the hydrogen (6) in the hydrogen production unit (30), and when the ammonia gas (1) and the other substance are mixed, the other substance and the ammonia gas (1) are separated, and the ammonia gas (1) can be supplied to the liquefaction source formation unit (20).

[0164] Accordingly, according to the embodiment of the present application, the pure ammonia gas (1) can be recycled.

[0165] Continuing with reference to FIG. 7, an ammonia gas liquefaction device (100) according to an embodiment of the present application includes the liquefaction source forming unit (20), and the liquefaction source forming unit (20) may separately include a stirring unit in which the ammonia gas (1) and the solid ammonium salt (2) are stirred, and a storage unit in which the liquid ammonia (5), the ammonium cation (3), and / or the anion (4) in a liquid state formed by stirring the ammonia gas (1) and the solid ammonium salt (2) are stored.

[0166] Accordingly, the liquid ammonia (5), the ammonium cation (3), and / or the anion (4) in a liquid state can be prepared in advance.

[0167] Accordingly, according to the embodiment of the present application, rapid supply of the liquid ammonia (5), the ammonium cation (3), and / or the anion (4) in a liquid state to the hydrogen production unit (30) can be possible.

[0168] Continuing with reference to FIG. 7, an ammonia gas liquefaction device (100) according to one embodiment of the present application includes a hydrogen production unit (30), wherein the hydrogen production unit (30) may be a multi-cell. In other words, the hydrogen production unit (30) may include a plurality of battery cells connected to each other.

[0169] Due to this, the ammonia gas liquefaction device (100) can easily control the voltage, capacity, and / or current density at which the hydrogen (6) is produced.

[0170] Referring to FIG. 8, an ammonia gas liquefaction device (100) according to another embodiment of the present application may include a plurality of gas source supply units (10a, 10b). More specifically, according to another embodiment of the present application, a first gas source supply unit (10a) may be included that stores pure ammonia gas (1) and supplies the stored pure ammonia gas (1) to the liquefaction source forming unit (20). In addition, a second gas source supply unit (10b) may be separately included as a system that receives the ammonia gas (1) formed in the process of forming the hydrogen (6) in the hydrogen production unit (30), separates the pure ammonia gas (1) from the mixed other substances, and supplies the separated pure ammonia gas (1) to the liquefaction source forming unit (20). The second gas source supply unit (10b) can separate the other substances mixed with the ammonia gas (1), for example, by chemical absorption, membrane separation, and / or pressure swing adsorption. However, the present invention is not limited thereto.

[0171] Accordingly, the pure ammonia gas (1) can be prepared in advance.

[0172] Accordingly, according to the embodiment of the present application, rapid supply of pure ammonia gas (1) to the liquefied source forming unit (20) is possible.

[0173] Continuing with reference to FIG. 8, an ammonia gas liquefaction device (100) according to another embodiment of the present application includes the liquefaction source forming unit (20), and the liquefaction source forming unit (20) may separately include a stirring unit in which the ammonia gas (1) and the solid ammonium salt (2) are stirred, and a storage unit in which the liquid ammonia (5), the ammonium cation (3), and / or the anion (4) in a liquid state formed by stirring the ammonia gas (1) and the solid ammonium salt (2) are stored.

[0174] Accordingly, the liquid ammonia (5), the ammonium cation (3), and / or the anion (4) in a liquid state can be prepared in advance.

[0175] Accordingly, according to the embodiment of the present application, rapid supply of the liquid ammonia (5), the ammonium cation (3), and / or the anion (4) in a liquid state to the hydrogen production unit (30) can be possible.

[0176] Continuing with reference to FIG. 8, an ammonia gas liquefaction device (100) according to another embodiment of the present application includes the hydrogen production unit (30), but may further include a condenser connected between the hydrogen production unit (30) and the second gas source supply unit (10b).

[0177] Due to this, the amine (NH2) formed in the process of forming the hydrogen (6) in the hydrogen production unit (30) can be condensed through the condenser to form the liquid ammonia (5). The liquid ammonia (5) formed by condensation through the condenser can be provided to the liquefaction source formation unit (20) through the second gas source supply unit (10b) or can be provided directly to the liquefaction source formation unit (20).

[0178] Accordingly, according to the embodiment of the present application, hydrogen production efficiency can be improved.

[0179] Referring to FIG. 9, an ammonia gas liquefaction device (100) according to another embodiment of the present application includes the gas source supply unit (10), the liquefaction source forming unit (20), and the hydrogen production unit (not shown), wherein the ammonia gas (1) of the gas source supply unit (10) can be provided to the liquid ammonia (5) in which the ammonium salt (2) is dissolved in the liquefaction source forming unit (20). In addition, the ammonia gas (1), the ammonium salt (2), and / or the liquid ammonia (5) can be stirred.

[0180] Due to this, the surface area with which the ammonia gas (1), the ammonium salt (2), and / or the liquid ammonia (5) come into contact can be maximized.

[0181] Accordingly, according to the embodiment of the present application, the liquid conversion efficiency can be improved.

[0182] Referring to Fig. 10, the liquefied source forming unit (20) may have a structure that stirs the ammonia gas (1) and the solid ammonium salt (2). For example, the liquefied source forming unit (20) may have a structure that mechanically stirs the ammonia gas (1) and the solid ammonium salt (2). However, the present invention is not limited thereto.

[0183] According to one embodiment, the ammonia gas liquefaction device (100) may include a valve. More specifically, the ammonia gas liquefaction device (100) may include the valve between the gas source supply unit (10) and the liquefaction source forming unit (20), between the liquefaction source forming unit (20) and the hydrogen production unit (30), and / or between the hydrogen production unit (30) and the gas source supply unit (10).

[0184] Due to this, in the ammonia gas liquefaction device (100), there is a technical effect of facilitating the flow of the ammonia gas (1), the liquid ammonia (5), the ammonium cation (3), and / or the anion (4).

[0185] According to one embodiment, the ammonia gas liquefaction device (100) may include a control unit (not shown).

[0186] Accordingly, the control unit can control the opening and closing of the valve.

[0187] Accordingly, the flow amount of the ammonia gas (1), the liquid ammonia (5), the ammonium cation (3), and / or the anion (4) can be controlled. For example, the control unit can control the supply amount of the ammonia gas (1) so that the amount of the ammonia gas (1) liquefied and formed into the liquid ammonia (5) by reacting with the solid ammonium salt (2) is 15 wt% or more and 50 wt% or less, more specifically, 27 wt% or more and 37 wt% or less. In other words, the supply amount of the ammonia gas (1) can be controlled so that the amount of the dissolved ammonia gas (1) is 27 wt% or more and 37 wt% or less. More specifically, for example, the control unit can control the supply amount of the ammonia gas (1) so that the amount of the ammonia gas (1) dissolved is greater than 27 wt% and less than 34 wt%. More specifically, for example, the control unit can control the supply amount of the ammonia gas (1) so that the amount of the ammonia gas (1) dissolved is 30 wt%.

[0188] Accordingly, according to the embodiment of the present application, not only can the rate at which the ammonia gas (1) is converted into the liquid ammonia (5) be fast, but also the solid ammonium salt (2) can be decomposed into the ammonium cation (3) and the anion (4) and be substantially completely dissolved in the liquid ammonia (5).

[0189] In other words, according to the embodiment of the present application, the amount of the ammonia gas (1) supplied is controlled so that the amount of the ammonia gas (1) liquefied and formed into liquid ammonia (5) is 15 wt% or more and 50 wt% or less, more specifically, 27 wt% or more and 37 wt% or less, so that the ammonia gas (1) and the solid ammonium salt (2) can be substantially completely converted into a liquid state.

[0190] Due to this, the amount of the liquid ammonia (5) and / or the ammonium cation (3) provided in a liquid state can be maximized.

[0191] Accordingly, the amount of hydrogen (6) formed can be maximized.

[0192] Furthermore, the stability of the electrode of the hydrogen production unit (30) can be excellent and the current density can be high.

[0193] Alternatively, in another embodiment, the opening and closing of the valve may be manually controlled by the user.

[0194]

[0195] Hereinafter, an ammonia gas liquefaction method according to an embodiment of the present application is described. In the ammonia gas liquefaction method described below, any descriptions that overlap with those of the previously described embodiments may be omitted. However, omission of such descriptions below does not necessarily exclude such descriptions.

[0196] Referring to FIGS. 2 to 4, ammonia gas (1) can be supplied (S110).

[0197] According to one embodiment, the amount of the supplied ammonia gas (1) can be controlled. For example, the amount of the supplied ammonia gas (1) can be controlled so that the amount of the ammonia gas (1) that reacts with the solid ammonium salt (2) to be liquefied and formed into the liquid ammonia (5) is 15 wt% or more and 50 wt% or less, more specifically, 27 wt% or more and 37 wt% or less. In other words, the amount of the supplied ammonia gas (1) can be controlled so that the amount of the dissolved ammonia gas (1) is 27 wt% or more and 37 wt% or less. More specifically, for example, the amount of the supplied ammonia gas (1) can be controlled so that the amount of the dissolved ammonia gas (1) is more than 27 wt% and less than 34 wt%. More specifically, for example, the supply amount of the ammonia gas (1) can be controlled so that the amount of the ammonia gas (1) dissolved is 30 wt%.

[0198] Accordingly, according to the embodiment of the present application, not only can the rate at which the ammonia gas (1) is converted into the liquid ammonia (5) be fast, but also the solid ammonium salt (2) can be decomposed into the ammonium cation (3) and the anion (4) and be substantially completely dissolved in the liquid ammonia (5).

[0199] In other words, according to the embodiment of the present application, the amount of the ammonia gas (1) supplied is controlled so that the amount of the ammonia gas (1) liquefied and formed into liquid ammonia (5) is 15 wt% or more and 50 wt% or less, more specifically, 27 wt% or more and 37 wt% or less, so that the ammonia gas (1) and the solid ammonium salt (2) can be substantially completely converted into a liquid state.

[0200] Due to this, the amount of the liquid ammonia (5) and / or the ammonium cation (3) provided in a liquid state can be maximized.

[0201] Accordingly, the amount of hydrogen (6) formed can be maximized.

[0202] Furthermore, it has excellent stability for electrodes and can have high current density.

[0203] Continuing, referring to FIGS. 2, 4, and 5, the ammonia gas (1) and the solid ammonium salt (2) react, so that the ammonia gas (1) is liquefied to form liquid ammonia (5), and the solid ammonium salt (2) can be decomposed into ammonium cations (3) and anions (4) (S120).

[0204] According to one embodiment, the solid ammonium salt (2) may have high solubility in the ammonia gas (1).

[0205] Due to this, hydrogen bonding between the ammonia gas (1), the ammonium cation (3), and / or the anion (4) can be facilitated.

[0206] According to one embodiment, the stronger the anion (4), the more the liquefaction of the ammonia gas (1) can be promoted. The ammonium salt (2) may include, as the anion (4), one or more selected from the group consisting of nitrate (NO3-), hexafluorophosphate (PF6-), trifluoromethanesulfonate (CF3O3S-), and thiocyanate (SCN-). However, the present invention is not limited thereto.

[0207] According to one embodiment, the ammonium salt (2) may include one or more selected from the group of inorganic ammonium salts including ammonium chloride (NH4Cl), ammonium sulfate ((NH4)2SO4), ammonium carbonate ((NH4)2CO3), ammonium phosphate ((NH4)3PO4), ammonium bromide (NH4Br), ammonium iodide (NH4I), ammonium fluoride (NH4F), ammonium perchlorate (NH4ClO4), ammonium fluoroborate (NH4BF4), ammonium bisulfate ((NH4)HSO4), and ammonium peroxodisulfate ((NH4)2S2O8), and zinc ammonium salts ((NH4)2ZnCl4, (NH4)2ZnSO4) dichromate It may include one or more selected from the group of metal-containing ammonium salts including ammonium ((NH4)2Cr2O7), ammonium vanadate (V) (NH4VO3), ammonium tetrathiomolybdate ((NH4)2MoS4), and ammonium hexafluorotitanate ((NH4)2TiF6), and it may include one or more selected from the group of organic ammonium salts including ammonium acetate (CH3CO2NH4) and ammonium tetraphenylborate (NH4B(C6H5)4). However, it is not limited thereto.

[0208] In one embodiment, the solid ammonium salt (2) may be a mixture. For example, the mixture of the solid ammonium salt (2) may include at least one of ammonium nitrate (NH4NO3), ammonium hexafluorophosphate (NH4PF6), ammonium triflate (NH4CF3SO3), and ammonium thiocyanate (NH4SCN). However, the present invention is not limited thereto. For another example, the ammonium salt (2) may include one or more selected from the group of inorganic ammonium salts including ammonium chloride (NH4Cl), ammonium sulfate ((NH4)2SO4), ammonium carbonate ((NH4)2CO3), ammonium phosphate ((NH4)3PO4), ammonium bromide (NH4Br), ammonium iodide (NH4I), ammonium fluoride (NH4F), ammonium perchlorate (NH4ClO4), ammonium fluoroborate (NH4BF4), ammonium bisulfate ((NH4)HSO4), and ammonium peroxodisulfate ((NH4)2S2O8), and zinc ammonium salts ((NH4)2ZnCl4, (NH4)2ZnSO4) dichromate It may include one or more selected from the group of metal-containing ammonium salts including ammonium ((NH4)2Cr2O7), ammonium vanadate (V) (NH4VO3), ammonium tetrathiomolybdate ((NH4)2MoS4), and ammonium hexafluorotitanate ((NH4)2TiF6), and it may include one or more selected from the group of organic ammonium salts including ammonium acetate (CH3CO2NH4) and ammonium tetraphenylborate (NH4B(C6H5)4). However, it is not limited thereto.

[0209] According to one embodiment, the liquid ammonia (5) can be formed from the ammonia gas (1) under room temperature and atmospheric pressure conditions. The room temperature may include, for example, -35°C or higher to 50°C or lower, more specifically, 0°C or higher to 35°C or lower, and the atmospheric pressure may include, for example, 1 atm. In other words, the liquefaction source forming unit (20) can be operated at a temperature of 0°C or higher to 35°C or lower and a pressure of 1 atm.

[0210] Due to this, the present application can have superior operating efficiency and safety compared to conventional methods for liquefying ammonia gas.

[0211] According to one embodiment, the ammonia gas (1) and the solid ammonium salt (2) can be stirred.

[0212] Due to this, the surface area where the ammonia gas (1) and the solid ammonium salt (2) come into contact can be maximized.

[0213] Accordingly, liquefaction of the ammonia gas (1) and / or the solid ammonium salt (2) can be promoted, and the liquid conversion efficiency can be improved.

[0214] Continuing with reference to FIGS. 2 and 6, the liquid ammonia (5) and the ammonium cation (3) may be decomposed to form the hydrogen (6) (S130). The reaction in which the liquid ammonia (5) is decomposed to form the hydrogen (6) may follow, for example, the reaction formulas 1 to 6. According to the reaction formula 2, hydrazine (H2NNH2) including a nitrogen bond (NN) may be formed, and a hydrogen ion (H+) may be formed. The formed hydrogen ion (H+) may coexist with the ammonium cation (NH4+, 3).

[0215] According to one embodiment, the hydrogen ion (H+) can obtain an electron (e-) and be formed into the hydrogen (6), i.e., hydrogen gas (H2).

[0216] According to one embodiment, the hydrogen (6) can be used as an energy source. That is, according to the embodiment of the present application, an eco-friendly energy source can be efficiently produced.

[0217] Continuing, referring to FIGS. 1 to 6, the liquid ammonia (5) and the ammonium cation (3) that are not formed with the hydrogen (6), and the ammonia gas (1) formed in the process of forming the hydrogen (6) can be recycled (S140).

[0218] Due to this, the ammonia gas liquefaction device (100) according to the embodiment of the present application can maximize the hydrogen production yield.

[0219]

[0220] Below, an experimental example of the present application is described.

[0221]

[0222] Ammonia gas liquefaction according to Experimental Example 1-1 (ex1-1)

[0223] 160 ml (100 g) of ammonium thiocyanate (NH4SCN) was provided as the solid ammonium salt (2) inside the reactor, and the ammonia gas (1) was injected at a flow rate of 50 ml / min every 30 minutes for 12 hours.

[0224] At this time, the ammonia gas (1) and the ammonium salt (2) inside the reactor were stirred at 300 to 400 Rpm for 3 hours.

[0225] Ammonia gas liquefaction (ex1-1) according to Experimental Example 1-1 was performed by controlling the supply amount of the ammonia gas (1) so that the amount of the ammonia gas (1) dissolved inside the reactor was 24 wt%.

[0226]

[0227] Ammonia gas liquefaction according to Experimental Example 1-2 (ex1-2)

[0228] In the above-described Experimental Example 1-1 (ex1-1), the supply amount of the ammonia gas (1) was controlled so that the amount of the ammonia gas (1) dissolved inside the reactor was 27 wt%, and ammonia gas liquefaction (ex1-2) according to Experimental Example 1-2 was performed.

[0229]

[0230] Ammonia gas liquefaction according to Experimental Example 1-3 (ex1-3)

[0231] In the above-described Experimental Example 1-1 (ex1-1), the supply amount of the ammonia gas (1) was controlled so that the amount of the ammonia gas (1) dissolved inside the reactor was 30 wt%, and ammonia gas liquefaction (ex1-3) according to Experimental Example 1-3 was performed.

[0232]

[0233] Ammonia gas liquefaction according to Experimental Example 1-4 (ex1-4)

[0234] In the above-described Experimental Example 1-1 (ex1-1), the supply amount of the ammonia gas (1) was controlled so that the amount of the ammonia gas (1) dissolved inside the reactor was 34 wt%, and ammonia gas liquefaction (ex1-4) according to Experimental Example 1-4 was performed.

[0235]

[0236] Ammonia gas liquefaction according to Experimental Example 1-5 (ex1-5)

[0237] In the above-described Experimental Example 1-1 (ex1-1), the supply amount of the ammonia gas (1) was controlled so that the amount of the ammonia gas (1) dissolved inside the reactor was 37 wt%, and ammonia gas liquefaction (ex1-5) according to Experimental Example 1-5 was performed.

[0238]

[0239] The above-described Experimental Examples 1-1 to 1-5 can be summarized as shown in Table 1 below.

[0240] Dissolved ammonia gas (1) Ammonia gas liquefaction according to Experimental Example 1-1 (ex1-1) 24 wt% Ammonia gas liquefaction according to Experimental Example 1-2 (ex1-2) 27 wt% Ammonia gas liquefaction according to Experimental Example 1-3 (ex1-3) 30 wt% Ammonia gas liquefaction according to Experimental Example 1-4 (ex1-4) 34 wt% Ammonia gas liquefaction according to Experimental Example 1-5 (ex1-5) 37 wt%

[0241]

[0242] FIG. 11 is a graph showing linear sweep voltammetry (LSV) measurements in ammonia gas liquefaction according to Experimental Examples 1-1 to 1-5 of the present application, FIG. 12 is a graph showing cyclic voltammetry (CV) measurements in ammonia gas liquefaction according to Experimental Examples 1-1 to 1-5 of the present application, FIG. 13 is a graph showing current measurements in ammonia gas liquefaction according to Experimental Examples 1-1 to 1-5 of the present application, and FIG. 14 is a graph showing voltage measurements in ammonia gas liquefaction according to Experimental Examples 1-1 to 1-5 of the present application.

[0243] Referring to Fig. 11, in the ammonia gas liquefaction (ex1-3) according to the experimental example 1-3, it can be seen that the speed at which the ammonia gas (1) is converted into the liquid ammonia (5) is the fastest.

[0244] In addition, referring to Fig. 12, it can be seen that in the ammonia gas liquefaction (ex1-3) according to the above experimental example 1-3, the stability for the electrode is excellent and the current density is high.

[0245] Also, referring to FIGS. 13 and 14, it can be seen that in the ammonia gas liquefaction (ex1-3) according to the experimental example 1-3, the current is the highest and the voltage is the lowest.

[0246] Accordingly, according to the experimental example of the present application, when the supply amount of the ammonia gas (1) is controlled so that the amount of the ammonia gas (1) liquefied and formed into liquid ammonia (5) is more than 27 wt% and less than 34 wt%, it can be proven that the speed at which the ammonia gas (1) is converted into the liquid ammonia (5) is fast, the stability with respect to the electrode is excellent, and the current density is high.

[0247]

[0248] Ammonia gas liquefaction according to Experimental Example 2-1 (ex2-1)

[0249] 12 ml (20 g) of ammonium nitrate (NH4NO3) was provided as the solid ammonium salt (2) inside the reactor, and the ammonia gas (1) was injected at a flow rate of 50 ml / min every 30 minutes for 12 hours.

[0250] At this time, the ammonia gas (1) and the ammonium salt (2) inside the reactor were stirred at 300 to 400 Rpm for 3 hours.

[0251] Ammonia gas liquefaction (ex2-1) according to Experimental Example 2-1 was performed by controlling the supply amount of the ammonia gas (1) so that the amount of the ammonia gas (1) dissolved inside the reactor was 30 wt%.

[0252]

[0253] Ammonia gas liquefaction according to Experimental Example 2-2 (ex2-2)

[0254] In the above-described experimental example 2-1 (ex2-1), 10 ml (20 g) of ammonium hexafluorophosphate (NH4PF6) was provided as the solid ammonium salt (2), and ammonia gas liquefaction (ex2-2) according to experimental example 2-2 was performed.

[0255]

[0256] Ammonia gas liquefaction according to Experimental Example 2-3 (ex2-3)

[0257] In the above-described experimental example 2-1 (ex2-1), 130 ml (100 g) of ammonium triflate (NH4CF3SO3) was provided as the solid ammonium salt (2), and ammonia gas liquefaction (ex2-3) according to experimental example 2-3 was performed.

[0258]

[0259] Ammonia gas liquefaction according to Experimental Example 2-4 (ex2-4)

[0260] In the above-described experimental example 2-1 (ex2-1), 160 ml (100 g) of ammonium thiocyanate (NH4SCN) was provided as the solid ammonium salt (2), and ammonia gas liquefaction (ex2-4) according to experimental example 2-4 was performed.

[0261]

[0262] Ammonia gas liquefaction according to Experimental Example 2-5 (ex2-5)

[0263] In the above-described experimental example 2-1 (ex2-1), a mixture of 70 ml (50 g) of ammonium nitrate (NH4NO3) and ammonium thiocyanate (NH4SCN) in a 1:1 ratio was provided as a mixture of the solid ammonium salt (2), and ammonia gas liquefaction (ex2-5) according to experimental example 2-5 was performed.

[0264]

[0265] The above-described experimental examples 2-1 to 2-5 can be summarized as shown in Table 2 below.

[0266] Ammonium salt (2) Ammonia gas liquefaction according to Experimental Example 2-1 (ex2-1) NH4NO3 Ammonia gas liquefaction according to Experimental Example 2-2 (ex2-2) NH4PF6 Ammonia gas liquefaction according to Experimental Example 2-3 (ex2-3) NH4CF3SO3 Ammonia gas liquefaction according to Experimental Example 2-4 (ex2-4) NH4SCN Ammonia gas liquefaction according to Experimental Example 2-5 (ex2-5) NH4NO3 and NH4SCN

[0267]

[0268] FIG. 15 is a photograph of a liquid manufactured according to Experimental Example 2-1 of the present application, FIG. 16 is a photograph of a liquid manufactured according to Experimental Example 2-2 of the present application, FIG. 17 is a photograph of a liquid manufactured according to Experimental Example 2-3 of the present application, FIG. 18 is a photograph of a liquid manufactured according to Experimental Example 2-4 of the present application, FIG. 19 is a photograph of a liquid manufactured according to Experimental Example 2-5 of the present application, and FIG. 20 is a graph showing the conversion efficiency of the liquid manufactured according to Experimental Examples 2-1 to 2-5 of the present application.

[0269] Referring to FIGS. 15 to 19, according to the experimental examples 2-1 to 2-5 (ex2-1 to ex2-5), it can be observed that the ammonia gas (1) and the solid ammonium salt (2) are stirred to form a liquid phase.

[0270] Meanwhile, referring to Fig. 20, it can be seen that the conversion efficiency of forming a liquid phase is excellent in the order of Experimental Example 2-4, Experimental Example 2-5, Experimental Example 2-3, Experimental Example 2-1, and Experimental Example 2-2.

[0271] Accordingly, it can be seen that the conversion efficiency is excellent in that the liquid phase is formed in the order of ammonium thiocyanate (NH4SCN), ammonium nitrate (NH4NO3), and a mixture of ammonium thiocyanate (NH4SCN), ammonium triflate (NH4CF3SO3), ammonium nitrate (NH4NO3), and ammonium hexafluorophosphate (NH4PF6) with the solid ammonium salt (2).

[0272]

[0273] Formation of hydrogen according to Experimental Example 3 (ex3)

[0274] 30 g of ammonium thiocyanate (NH4SCN) was provided as the solid ammonium salt (2) inside the reactor, and the ammonia gas (1) was injected at a flow rate of 50 ml / min every 30 minutes for 12 hours.

[0275] At this time, the ammonia gas (1) and the ammonium salt (2) inside the reactor were stirred at 300 to 400 Rpm for 3 hours.

[0276] The supply amount of the ammonia gas (1) was controlled so that the amount of the ammonia gas (1) dissolved inside the reactor was 30 wt%, thereby forming a liquid phase containing the liquid ammonia (5) and the ammonium cation (3).

[0277] The liquid phase was provided to the battery cell including the negative electrode (33) manufactured from a platinum-titanium (Pt-Ti mesh) material and the positive electrode (35) manufactured from an iridium, ruthenium, and titanium mixed metal oxide (Ir, Ru, Ti mixed metal oxide) material, and the liquid ammonia (5) and / or the ammonium cation (3) was decomposed to form hydrogen according to Experimental Example 3 (ex3).

[0278]

[0279] Figure 21 is a graph showing hydrogen formed according to Experimental Example 3 of the present application.

[0280] Referring to Fig. 21, it can be seen that according to the experimental example 3 (ex3), the liquid ammonia (5) and / or the ammonium cation (3) is decomposed to form the hydrogen (H2, 6).

[0281] Thus, according to the experimental example of the present application, it can be proven that the hydrogen (H2, 6) is formed from the liquid ammonia (5) and / or the ammonium cation (3) formed by the reaction of the ammonia gas (1) and the solid ammonium salt (2).

[0282]

[0283] While the present application has been described in detail using preferred embodiments, the scope of the present application is not limited to the specific embodiments and should be interpreted in accordance with the appended claims. Furthermore, those skilled in the art will appreciate that numerous modifications and variations are possible without departing from the scope of the present application.

Claims

1. A step in which ammonia gas is supplied; and An ammonia gas liquefaction method comprising a step of reacting the ammonia gas with a solid ammonium salt, liquefying the ammonia gas to form liquid ammonia, and decomposing the solid ammonium salt into ammonium cations and anions.

2. In paragraph 1, The above ammonia gas, A method for liquefying ammonia gas, comprising supplying the ammonia gas so that the ammonia gas is liquefied and formed into the liquid ammonia by reacting with the solid ammonium salt in an amount of 15 wt% or more and 50 wt% or less.

3. In paragraph 1, An ammonia gas liquefaction method, wherein the liquefaction of the ammonia gas is performed under ambient conditions of a temperature of -35°C or higher and a pressure of 1 atm or lower.

4. In paragraph 1, The above liquid ammonia and the ammonium cation are decomposed to form hydrogen, A method for liquefying ammonia gas, comprising recycling the liquid ammonia and the ammonium cations not formed with the hydrogen, and the ammonia gas formed in the process of forming the hydrogen.

5. In paragraph 1, The above ammonium salt is, A method for liquefying ammonia gas, comprising one or more selected from the group consisting of nitrate (NO3-), hexafluorophosphate (PF6-), trifluoromethanesulfonate (CF3O3S-), and thiocyanate (SCN-) as the above anions.

6. In paragraph 1, The above ammonium salt is, It may include one or more selected from the group of inorganic ammonium salts including ammonium chloride (NH4Cl), ammonium sulfate ((NH4)2SO4), ammonium carbonate ((NH4)2CO3), ammonium phosphate ((NH4)3PO4), ammonium bromide (NH4Br), ammonium iodide (NH4I), ammonium fluoride (NH4F), ammonium perchlorate (NH4ClO4), ammonium fluoroborate (NH4BF4), ammonium bisulfate ((NH4)HSO4), and ammonium peroxodisulfate ((NH4)2S2O8), zinc ammonium salts ((NH4)2ZnCl4, (NH4)2ZnSO4), ammonium dichromate ((NH4)2Cr2O7), vanadic acid A method for liquefying ammonia gas, comprising one or more selected from the group of metal-containing ammonium salts including ammonium(V)(NH4VO3), ammonium tetrathiomolybdate ((NH4)2MoS4), and ammonium hexafluorotitanate ((NH4)2TiF6), and one or more selected from the group of organic ammonium salts including ammonium acetate (CH3CO2NH4) and ammonium tetraphenylborate (NH4B(C6H5)4).

7. In paragraph 1, A method for liquefying ammonia gas, comprising stirring the ammonia gas and the solid ammonium salt.

8. Gas inlet through which ammonia gas flows in; A tank storing a solid ammonium salt that reacts with the ammonia gas introduced through the gas inlet to form liquid ammonia by liquefying the ammonia gas; and An ammonia gas liquefaction device comprising a liquefaction source forming unit including a liquid discharge port for discharging the liquid ammonia formed in the tank.

9. In paragraph 8, An ammonia gas liquefaction device, wherein the solid ammonium salt is decomposed into ammonium cations and anions inside the tank.

10. In paragraph 9, An ammonia gas liquefaction device, comprising the liquid ammonia and the ammonium cations being decomposed to form hydrogen.

11. In paragraph 10, An ammonia gas liquefaction device further comprising a gas source supply unit connected to the gas inlet to supply the ammonia gas to the liquefaction source forming unit.

12. In paragraph 11, The above gas source supply unit, Controlling the supply amount of the ammonia gas supplied to the above liquefied source forming unit, An ammonia gas liquefaction device comprising controlling the supply amount of the ammonia gas so that the amount of the ammonia gas liquefied and formed into the liquid ammonia by reacting with the solid ammonium salt stored in the liquefaction source forming unit is 15 wt% or more and 50 wt% or less.

13. In paragraph 11, The liquid ammonia and ammonium cations not formed with the hydrogen are recycled to the liquefaction source forming unit, An ammonia gas liquefaction device, wherein the ammonia gas formed in the process of forming the hydrogen is recycled to the gas source supply unit or the liquefaction source forming unit.

14. In paragraph 8, An ammonia gas liquefaction device, wherein the liquefaction source forming unit is operated under ambient temperature conditions including -35°C or higher and 50°C or lower and ambient pressure conditions including 1 atm.

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