KR102454095B1 - Continuous hydrogen storage apparatus using liquid organic hydrogen carrier - Google Patents

Abstract

The present invention relates to an apparatus for continuously storing hydrogen in Liquid Organic Hydrogen Carriers (LOHCs). Specifically, it is a device for storing hydrogen in the liquid organic hydrogen carrier by supplying hydrogen and liquid organic hydrogen carriers (LOHCs) at the same time to the reaction part filled with the catalyst.

Description

Continuous hydrogen storage device using liquid organic hydrogen carrier {CONTINUOUS HYDROGEN STORAGE APPARATUS USING LIQUID ORGANIC HYDROGEN CARRIER}

The present invention relates to an apparatus for continuously storing hydrogen in Liquid Organic Hydrogen Carriers (LOHCs). Specifically, it is a device for storing hydrogen in the liquid organic hydrogen carrier by supplying hydrogen and liquid organic hydrogen carriers (LOHCs) at the same time to the reaction part filled with the catalyst.

As various energy and environmental problems arise due to the depletion of fossil energy resources and carbon emission, attempts to expand the use of renewable energy worldwide are expected to increase. However, since renewable energy has the disadvantage of being intermittent and difficult to predict, it should be able to store a large amount of surplus power and enable long-distance transportation. At this time, a carrier capable of reusing the stored energy is absolutely required, and hydrogen is attracting attention as the carrier.

One of the methods for large-capacity storage and long-distance transport of hydrogen is to use Liquid Organic Hydrogen Carriers (LOHCs). LOHCs can store/release hydrogen reversibly by hydrogenation/dehydrogenation reaction, and have the advantage of excellent hydrogen storage capacity compared to high volume and weight. In addition, it is positioned as an energy storage medium that can store hydrogen on a large scale enough to use the current gasoline infrastructure as it is and move efficiently.

As a prior art, a method for storing and supplying hydrogen using toluene is being studied in Japan, and a system for reversibly storing a large amount of hydrogen using a compound based on dibenzyltoluene has been developed in Germany. In addition, LOHCs using ethylcarbazole and diphenyl oxide have been developed in the United States.

A batch-type reactor is mainly used for large-capacity hydrogen storage using LOHCs, but the batch-type reactor requires a large capacity for solid-liquid separation and a stirrer that mechanically rubs the catalyst particles. There is a downside to that. In addition, due to the limitation of the size of the reactor, it is necessary to open and close the reactor for continuous exchange of reactants and products. In order to compensate for these drawbacks, technology development for a continuous reactor using a catalyst-filled fixed-bed reactor is being actively developed. In particular, since it is possible to increase the product production per unit catalyst, this technology is being applied as a method for mass production.

However, the hydrogenation reaction of LOHCs is an exothermic reaction, and as a result, a significant amount of heat is generated in the reactor. Since it is generally difficult to control the temperature of a fixed-bed reactor, if it is used for the hydrogenation of LOHCs, the temperature deviation within the reactor increases, which may decrease the efficiency of the reactor. In addition, when the reactor is enlarged, a hot spot is generated due to internal heat generation, which may adversely affect long-term durability of the reactor and safety during operation.

Another problem with reactor overheating is coking of the catalyst. Coke may be generated on the catalyst surface by thermal decomposition of hydrocarbon molecules at high temperatures, which may lead to deactivation of the catalyst.

Korean Patent Publication No. 10-2010-0011930 Korean Patent Publication No. 10-2006-0119948 Korean Patent Publication No. 10-2007-0116263 Korean Patent No. 10-1845515

The present invention can control the height or pressure of the liquid in the reactor by controlling the amounts of LOHC and hydrogen flowing into the catalyst-filled reactor. At this time, since a high yield can be obtained even when the pressure in the reactor is maintained at 10 bar or less, a large amount of hydrogen can be safely stored without being subject to the high-pressure gas safety management method.

In particular, an object of the present invention is to provide a device capable of controlling the temperature difference between the inlet and outlet of the reactor by efficiently managing the heat generated in the process of storing hydrogen by introducing a phase change medium to the outside of the reactor.

The object of the present invention is not limited to the object mentioned above. The objects of the present invention will become more apparent from the following description, and will be realized by means and combinations thereof described in the claims.

A continuous hydrogen storage device according to an embodiment of the present invention is a housing having an internal space, accommodated in the housing and spaced apart from the housing at a predetermined distance, and therein hydrogen and a liquid organic hydrogen carrier (Liquid organic) A reaction unit filled with a catalyst that promotes the reaction of a hydrogen carrier (LOHC), a hydrogen supply unit supplying hydrogen to the reaction unit, a LOHC supply unit supplying LOHC to the reaction unit, and storing the product discharged from the reaction unit It may include a storage unit.

In the continuous hydrogen storage device, a liquid phase change medium is stored in a space between the housing and the reaction unit, and the liquid phase change medium is vaporized by the heat generated from the reaction unit to vaporize the remaining internal space of the housing. It may be filling.

The housing may further include a heat insulating member provided on at least one of the inner wall and the outer wall.

The housing includes an inlet for introducing a liquid phase change medium; and an outlet for discharging the gaseous phase change medium.

The phase change medium is water; organic solvents diphenylmethane, dowtherm, marlotherm; silicone-containing hydrocarbons; It may include at least one selected from the group consisting of inorganic salts and combinations thereof.

The reaction unit may have a temperature deviation of 10° C. or less between certain points in the internal space.

The catalyst is a catalyst metal supported on a support, the catalyst metal is ruthenium (Ru), palladium (Pd), platinum (Pt), rhodium (Rh), iridium (Ir), nickel (Ni), cobalt (Co) ), copper (Cu), and at least one selected from the group consisting of combinations, wherein the support is a metal oxide silica (SiO ₂ ), alumina (Al ₂ O ₃ ), lanthanum-doped alumina (La-) Al ₂ O ₃ ), zirconium oxide (ZrO ₂ ), cerium oxide (CeO ₂ ); and carbon-based graphite, carbon nanotubes, and graphene; may include at least one of

The continuous hydrogen storage device may be one in which a plurality of reaction units are accommodated in the housing.

The reaction unit may have an internal space divided into two or more spaces by a partition wall, a catalyst may be filled in each space, and the partition wall may include a through hole through which each space is connected to each other.

The continuous hydrogen storage device may include a plurality of hydrogen storage units including the housing and the reaction unit, and the plurality of hydrogen storage units may be connected in series.

The hydrogen may be supplied to the reaction unit together with a carrier gas.

The temperature of the reaction part may be 100 °C to 200 °C.

The pressure of the reaction part may be 10 bar to 50 bar.

The hydrogen may be supplied to the reaction unit at a flow rate of 50 mL/min to 300 mL/min.

The hydrogen may be supplied to the reaction unit at a pressure of 50 bar to 60 bar.

The hydrogen may be supplied to the reaction unit at a temperature of 150 °C to 200 °C.

The LOHC may be supplied to the reaction unit at a flow rate of 0.05 mL/min to 0.2 mL/min.

The present invention is characterized in that the temperature of the reactor is uniformly controlled by introducing a phase change medium to the outside of the reactor and using evaporation and condensation of the phase change medium by heat generated during a hydrogen storage process.

The present invention is characterized in that by inserting a partition wall into the reactor, the drift phenomenon occurring inside the reactor is reduced, and at the same time, a solid-gas-liquid three-phase reaction is effectively caused to obtain a hydrogenated reactant in high yield.

The present invention is characterized in that a greater amount of hydrogen is stored in the LOHC by connecting a plurality of hydrogen storage units in series. As a result, a large amount of hydrogen can be stored in the LOHC compared to the conventional batch reactor, so it can help in the manufacture of a 1 Nm ³ (H ₂ )-100 Nm ³ (H ₂ ) class hydrogen storage device in the future.

The effects of the present invention are not limited to the above-mentioned effects. It should be understood that the effects of the present invention include all effects that can be inferred from the following description.

1 shows a continuous hydrogen storage device according to the present invention.
2 shows a hydrogen storage unit according to the present invention.
3 shows a partition wall included in the hydrogen storage unit.
4 is a result of measuring the conversion rate of the LOHC hydrogenation reaction by controlling the pressure of the reaction part in Example 1 of the present invention.
5 is a result of measuring the conversion rate of the LOHC hydrogenation reaction by controlling the flow rate of the LOHC in Example 1 of the present invention.
6 is a result of measuring the temperature according to time at each point of the hydrogen storage unit in Example 2 of the present invention.
7 is a result of measuring the conversion rate of the LOHC hydrogenation reaction when using a catalyst in which ruthenium (Ru) is supported on alumina (Al ₂ O ₃ ) in Example 3 of the present invention.
8 is a result of measuring the conversion rate of the LOHC hydrogenation reaction when using a catalyst in which ruthenium (Ru) and lanthanum oxide (LaO _x ) as a promoter are supported on alumina (Al ₂ O ₃ ) in Example 3 of the present invention .

The above objects, other objects, features and advantages of the present invention will be easily understood through the following preferred embodiments in conjunction with the accompanying drawings. However, the present invention is not limited to the embodiments described herein and may be embodied in other forms. Rather, the embodiments introduced herein are provided so that the disclosed subject matter may be thorough and complete, and that the spirit of the present invention may be sufficiently conveyed to those skilled in the art.

In describing each figure, like reference numerals have been used for like elements. In the accompanying drawings, the dimensions of the structures are enlarged than the actual size for clarity of the present invention. Terms such as first, second, etc. may be used to describe various elements, but the elements should not be limited by the terms. The above terms are used only for the purpose of distinguishing one component from another. For example, without departing from the scope of the present invention, a first component may be referred to as a second component, and similarly, a second component may also be referred to as a first component. The singular expression includes the plural expression unless the context clearly dictates otherwise.

In the present specification, terms such as “comprise” or “have” are intended to designate that a feature, number, step, operation, component, part, or combination thereof described in the specification exists, but one or more other features It is to be understood that it does not preclude the possibility of the presence or addition of numbers, steps, operations, components, parts, or combinations thereof. Also, when a part of a layer, film, region, plate, etc. is said to be “on” another part, this includes not only cases where it is “directly on” another part, but also cases where another part is in between. Conversely, when a part, such as a layer, film, region, plate, etc., is "under" another part, this includes not only cases where it is "directly under" another part, but also cases where there is another part in between.

Unless otherwise specified, all numbers, values, and/or expressions expressing quantities of ingredients, reaction conditions, polymer compositions and formulations used herein include, among other things, the numbers, values and/or expressions such that these numbers essentially occur in obtaining such values, among others. Since they are approximations reflecting various uncertainties in the measurement, it should be understood as being modified by the term "about" in all cases. Also, where the disclosure discloses numerical ranges, such ranges are continuous and inclusive of all values from the minimum to the maximum inclusive of the range, unless otherwise indicated. Furthermore, when such ranges refer to integers, all integers inclusive from the minimum to the maximum inclusive are included, unless otherwise indicated.

1 shows a continuous hydrogen storage device according to the present invention. Referring to this, the continuous hydrogen storage device is a hydrogen storage unit 100 that stores hydrogen in the LOHC by reacting a liquid organic hydrogen carrier (LOHC) with hydrogen, and hydrogen that supplies hydrogen to the hydrogen storage unit 100 It includes a supply unit 200 , a LOHC supply unit 300 for supplying LOHC to the hydrogen storage unit 100 , and a storage unit 400 for storing the product discharged from the hydrogen storage unit 100 .

2 schematically shows the hydrogen storage unit 100 . Referring to this, the hydrogen storage unit 100 includes a housing 110 having an internal space; a reaction unit 120 accommodated in the housing 110 and spaced apart from the housing 110 at a predetermined distance and filled with a catalyst 121 that promotes a reaction between hydrogen and LOHC; and a phase change medium 130 stored in a space between the housing 110 and the reaction unit 120 .

The housing 110 may include a main body 111 forming the inner space and a heat insulating member 112 provided on at least one of an inner wall and an outer wall of the main body 111 .

The shape and size of the main body 111 is not particularly limited, and it can accommodate the reaction unit 120 and can be provided in a shape and size sufficient to store the phase change medium 130 to be described later in an appropriate amount. have.

The heat insulating member 112 is a part for controlling heat exchange between the inside and outside of the housing 110 . If the heat medium phase change medium does not sufficiently remove the heat generated during the reaction, the thickness of the heat insulating member 112 may be reduced and a cooler (not shown) may be installed outside the reactor. The position and shape of the cooler are not particularly limited, and any device generally used in the technical field to which the present invention pertains may be used. Therefore, as will be described later, the temperature control of the reaction unit 120 by the phase change medium 130 becomes easier.

The reaction unit 120 is disposed to be spaced apart from the housing 110 , specifically, the main body 111 at a predetermined interval. A phase change medium 130 is provided in a space between the housing 110 and the reaction unit 120 . The phase change medium 130 will be described later.

The reaction unit 120 may be a tubular reactor, and among them, a fixed bed reactor. The reaction unit 120 may be filled with a catalyst 121 that promotes the hydrogenation reaction of the LOHC.

The catalyst 121 may have a catalyst metal supported on a support.

The catalyst metal may include at least one selected from the group consisting of Ru, Pd, Pt, Rh, Ir, Ni, Co, Cu, and combinations thereof.

The support is a metal oxide silica (SiO ₂ ), alumina (Al ₂ O ₃ ), lanthanum-doped alumina (La-Al ₂ O ₃ ), zirconium oxide (ZrO ₂ ), cerium oxide (CeO ₂ ); and carbon-based graphite, carbon nanotubes, and graphene; may include at least one of The lanthanum-doped alumina may be one in which a material containing alkali metals and alkaline earth metals (particularly, lanthanum) as promoters (particularly, lanthanum) is supported on alumina as a support.

In the reaction unit 120 , an inner space thereof is divided into two or more spaces by a partition wall 122 , and each space may be filled with a catalyst 121 .

3 illustrates the partition wall 122 . Referring to this, the partition wall 122 may include a plurality of through-holes 122a formed so that each of the separated spaces of the reaction unit 120 is connected to each other.

The partition wall 122 reduces the drift phenomenon (channeling) inside the reaction unit 120 so that the three-phase reaction of catalyst (solid)-LOHC (liquid)-hydrogen (gas) in the reaction unit 120 is slightly make it happen more effectively. As a result, the conversion rate of the hydrogenation reaction of LOHC can be high.

A plurality of the reaction units 120 may be accommodated in the housing 110 . 2 illustrates that the two reaction units 120 are accommodated in the housing 110, the present invention is not limited thereto, and more may be accommodated. Raw materials such as hydrogen and LOHC may be individually introduced into the plurality of reaction units 120 to cause hydrogenation of the LOHC.

The phase change medium 130 may exist in a liquid state 130a and a gaseous state 130b between the housing 110 and the reaction unit 120 . Specifically, a liquid phase change medium 130a is stored in a space between the housing 110 and the reaction unit 120 , and the liquid phase change medium 130a is generated by heat generated from the reaction unit 120 . ) may be vaporized to fill the remaining internal space of the housing 110 with the gaseous phase change medium 130b.

When hydrogen and LOHC at a specific temperature are introduced into the reaction unit 120 , an exothermic reaction of hydrogenation of LOHC occurs in the presence of the catalyst 121 . Heat generated by the hydrogenation reaction may be used as latent heat of evaporation of the phase change medium 130a around the reaction unit 120 to maintain a uniform internal temperature of the reaction unit 120 . Here, "latent heat of evaporation" may be defined as heat absorbed when the phase change medium 130a in the liquid state changes to the phase change medium 130b in the gaseous state without a change in temperature. Heat generated from the reaction unit 120 may be transferred to the phase change medium 130a in a liquid state. The vaporized phase change medium can be used for preheating the reactants by moving by natural convection to the top of the reactor, that is, where the reactants are introduced. Through this type of thermal circulation, the temperature of the reactor is equalized. Here, the amount of the phase change medium may be changed according to the target reactor temperature and the rate of generation of reaction heat. If the amount of the phase change medium is too small or too large, the phenomenon in which the heat of reaction removed by the phase change is removed and natural convection are suppressed, so it may be difficult to control and equalize the temperature and pressure of the reactor.

In addition, as shown in FIG. 1 , each hydrogen storage unit 100 is connected to the phase change medium storage unit 500 storing the phase change medium, and parameters such as the water level and temperature of the phase change medium 130a, the reaction unit It is also possible to control the amount of reaction heat generated by 120 to be measured in real time and to supply the phase change medium 130a to the housing 110 according to the result. Accordingly, it is possible to control the desired temperature and pressure even when the variable load of the reaction unit 120 is performed. The water level or temperature of the phase change medium 130a, the amount of reaction heat generated by the reaction unit 120, etc. may be measured by installing a sensor (not shown) capable of detecting each parameter. The opening and closing of the phase change medium storage unit 500 according to the measured value of the sensor may be performed manually or automatically through a separate control unit (not shown).

As a result, since the heat generated locally in the reaction unit 120 is absorbed as latent heat of evaporation of the phase change medium 130a in the liquid state, the temperature of the reaction unit 120 is adjusted to a temperature deviation between certain points in the internal space. It can be adjusted below 10℃.

The storage amount of the phase change medium 130a is not particularly limited, but the housing 110 and the It may be stored in a space between the reaction units 120 . The storage amount of the phase change medium 130a may be variably changed according to the amount of reaction heat generated.

The housing 110 may include an inlet 113 for introducing the liquid phase change medium 130a and an outlet 114 for discharging the gaseous phase change medium 130b. The hydrogen storage unit 100 may be operated in a state in which there is a flow of inflow and outflow of the phase change medium 130a and 130b, a state in which there is no flow, or a state in which flow-non-flow is alternately adjusted. A temperature sensor (not shown) may be installed along the inner wall of the housing 110 and/or the outer wall of the reaction unit 120 to determine and control the inflow and outflow of the phase change media 130a and 130b.

The liquid phase change medium 130a may include at least one selected from the group consisting of water, an organic solvent, silicon-containing hydrocarbons, inorganic salts, and combinations thereof.

The organic solvent is not particularly limited, but may include at least one selected from the group consisting of diphenylmethane, dowsum, malosom, and combinations thereof.

The continuous hydrogen storage device according to the present invention may include a plurality of hydrogen storage units 100 including the housing 110 , the reaction unit 120 , and the phase change medium 130 . A plurality of the hydrogen storage units 100 may be connected to each other in series/parallel. Here, 'connected in series' means a connection relationship in which the discharge of the hydrogen storage unit of the front stage flows into the hydrogen storage unit of the rear stage. 'Connected in parallel' means that the reactants are fed to multiple hydrogen storage units by a distributor. A plurality of hydrogen storage units 100 may be connected in series/parallel to store a larger amount of hydrogen in the LOHC.

The present invention is characterized in that the hydrogenation reaction of the LOHC is caused by maintaining the temperature of the reaction unit 120 at 100° C. to 200° C. and adjusting the pressure to 10 bar to 50 bar. Unlike the conventional batch reactor, hydrogenation was performed even at 10 bar or less by configuring a continuous hydrogenation reactor in which the contact between the two reactants (hydrogen and LOHC) and the catalyst can be maximized. Since this is not subject to the High-Pressure Gas Safety Management Act, there is a great advantage in reactor manufacturing, certification, and operation.

The temperature and pressure of the reaction unit 120 may be adjusted by the flow rate, pressure, temperature, etc. of hydrogen and/or LOHC flowing into the reaction unit 120 . An additional heater (not shown) may be installed in order to prevent a temperature drop for one minute of the reactor during initial startup (start-up) and variable load. In addition, a pressure regulator may be installed to change the pressure inside the reactor. In addition, by adjusting the storage amount of the phase change medium, it is possible to control the pressure and temperature of the phase change medium storage container.

The hydrogen supply unit 200 is configured to provide hydrogen to the reaction unit 120 through the hydrogen supply pipe 201 .

The hydrogen may be supplied at a flow rate of 50 mL/min to 300 mL/min, a pressure of 50 bar to 60 bar, and a temperature of 150° C. to 200° C.

Meanwhile, the hydrogen may be supplied together with a carrier gas. The carrier gas may be nitrogen (N ₂ ). The carrier gas may be mixed with the hydrogen from the carrier gas supply unit 500 through the carrier gas supply pipe 501 to move.

The LOHC supply unit 300 is configured to provide LOHC to the reaction unit 120 through the LOHC supply pipe 301 . Power required to move the LOHC in the liquid state may be obtained from the pump 302 .

The LOHC may be supplied at a flow rate of 0.05 mL/min to 0.2 mL/min.

The LOHC is not particularly limited as long as it is a liquid material capable of storing hydrogen. For example, the LOHC may include at least one selected from the group consisting of biphenyl, diphenylmethane, and combinations thereof.

The hydrogen and LOHC may be mixed and provided before being introduced into the reaction unit 120 . In addition, the temperature of the mixture may be controlled by installing a heat exchanger (HT) in the inlet pipe through which the mixture of hydrogen and LOHC moves.

Hydrogen introduced into the reaction unit 120 and the LOHC react with each other in the presence of the catalyst 121 charged in the reaction unit 120 , and the hydrogen is stored in the LOHC.

The product discharged from the reaction unit 120 is finally stored in the storage unit 400 .

The storage unit 400 may include a storage tank 401 for storing the product. The product may include hydrogenated LOHC, residual hydrogen and side reactants, and the like. The hydrogenated LOHC may be provided to a required place of use, and hydrogen and side reactants may be vented to the outside.

Meanwhile, the residual hydrogen may be mixed and circulated with raw materials such as hydrogen and LOHC before being separated from the side reactants and introduced into the reaction unit 120 through the circulation pipe 402 .

Hereinafter, another embodiment of the present invention will be described in more detail through Examples. The following examples are only examples to help the understanding of the present invention, and the scope of the present invention is not limited thereto.

Example 1

A continuous hydrogen storage device as shown in FIG. 1 was implemented. A mixture of biphenyl and diphenylmethane was used as the LOHC, and two hydrogen storage units as shown in FIG. 2 were connected in series. As the catalyst charged in the reaction part, 30 g of ruthenium (Ru) as a catalyst metal and lanthanum oxide (LaO _x ) as a co-catalyst were supported on alumina (Al ₂ O ₃ ).

Hydrogen was supplied to the reaction unit at a flow rate of 50 mL/min, and LOHC was supplied at a flow rate of 0.2 mL/min. The pressure of the reaction part was adjusted to 10 bar, 20 bar, and 30 bar, and the conversion rate of the hydrogenation reaction of LOHC was measured while maintaining the temperature of the reaction part at 120 °C, 130 °C, 150 °C, 170 °C, 200 °C and 220 °C at each pressure. The result is shown in FIG. 4 .

Referring to FIG. 4 , when the pressure of the reaction unit is adjusted to 10 bar, it can be seen that the conversion rate reaches about 80% when the temperature of the reaction unit is 130°C. If the pressure of the reaction part is further increased to 20 bar or 30 bar, the conversion rate increases, but in this case, the standards of the high-pressure gas safety management law may be violated.

On the other hand, the conversion rate of the hydrogenation reaction of LOHC was measured while the pressure of the reaction part was adjusted to 10 bar, and LOHC was lowered to 0.1 mL/min and 0.05 mL/min, respectively. The result is shown in FIG. 5 .

Referring to FIG. 5 , it can be seen that the conversion rate reaches 100% when the pressure of the reaction section is 10 bar and the temperature is 130°C. As a result, according to the present invention, it can be seen that even if the pressure of the reaction section is lowered, a conversion rate of 100% can be sufficiently achieved.

Example 2

The temperature at a certain point in the hydrogen storage unit was measured using the continuous water tank storage device of Example 1. Specifically, LOHC was supplied at a flow rate of 0.3 mL/min and a temperature of 150° C., and hydrogen was supplied at a flow rate of 50 mL/min. At this time, the temperature according to the reaction time of the inlet and outlet of the housing, and the inlet and outlet of the reaction unit at 4 points was measured. The result is shown in FIG. 6 .

Referring to FIG. 6 , it can be seen that the temperature at each point, in particular, the temperature of the reaction unit, is constantly maintained by the temperature control unit by the phase change medium.

Example 3

Using the continuous hydrogen storage device of Example 1, the type of catalyst was changed and the conversion rate of the LOHC hydrogenation reaction was measured.

First, 30 g of a catalyst in which ruthenium (Ru) was supported on alumina (Al ₂ O ₃ ) was used. The result is shown in FIG. 7 . The hydrogen supply conditions were adjusted as described in FIG. 7, and the flow rates of LOHC were adjusted to 0.2 mL/min and 0.3 mL/min, respectively.

Next, 30 g of a catalyst in which ruthenium (Ru) as a catalyst metal and lanthanum oxide (LaO _x ) as a promoter are supported on alumina (Al ₂ O ₃ ) was used. The result is shown in FIG. 8 . The hydrogen supply conditions were adjusted as described in FIG. 8, and the flow rates of LOHC were adjusted to 0.2 mL/min and 0.3 mL/min, respectively.

7 and 8, the conversion rate is high when the hydrogen supply conditions are 50 mL/min, 50 bar, and 150 ° C. In general, the catalyst metal ruthenium (Ru) and the cocatalyst lanthanum oxide (LaO _x ) A high conversion rate was measured when using a catalyst supported on alumina (Al ₂ O ₃ ).

As the experimental examples and examples of the present invention have been described in detail above, the scope of the present invention is not limited to the above-described experimental examples and examples, and the basic concept of the present invention defined in the following claims. Various modifications and improved forms used by those skilled in the art are also included in the scope of the present invention.

100: hydrogen storage unit 110: housing 111: body 112: insulating member
113: inlet 114: outlet 120: reaction unit 121: catalyst
122: partition wall 122a: through hole 130: phase change medium
200: hydrogen supply unit 201: hydrogen supply pipe
300: LOHC supply unit 301: LOHC supply pipe
400: storage unit 401: storage tank 402: circulation pipe
500: phase change medium storage unit

Claims (17)

a housing having an interior space;
a reaction unit accommodated in the housing and disposed to be spaced apart from the housing at a predetermined distance, in which a catalyst for promoting a reaction between hydrogen and a liquid organic hydrogen carrier (LOHC) is filled;
a hydrogen supply unit for supplying hydrogen to the reaction unit;
a LOHC supply unit for supplying LOHC to the reaction unit; and
Including; a storage unit for storing the product discharged from the reaction unit;
A liquid phase change medium is stored in a space between the housing and the reaction unit, and the liquid phase change medium is in direct contact with the reaction unit,
The continuous hydrogen storage device, characterized in that the liquid phase change medium is vaporized by the heat generated from the reaction unit and fills the remaining internal space of the housing. According to claim 1,
The housing is a continuous hydrogen storage device further comprising a heat insulating member or a cooler provided on at least one of the inner wall and the outer wall. According to claim 1,
The housing includes an inlet for introducing a liquid phase change medium; and an outlet for discharging the gaseous phase change medium. According to claim 1,
The phase change medium is a continuous hydrogen storage device comprising at least one selected from the group consisting of water, an organic solvent, silicon-containing hydrocarbons, inorganic salts, and combinations thereof. 5. The method of claim 4,
The organic solvent is a continuous hydrogen storage device comprising at least one selected from the group consisting of diphenylmethane, dowsum, malosom, and combinations thereof. According to claim 1,
The reaction unit is a continuous hydrogen storage device in which the temperature deviation between certain points of the internal space is 10° C. or less. According to claim 1,
In the catalyst, a catalyst metal is supported on a support, and the catalyst metal includes at least one selected from the group consisting of Ru, Pd, Pt, Rh, Ir, Ni, Co, Cu, and combinations thereof,
The support is made of silica (SiO ₂ ), alumina (Al ₂ O ₃ ), lanthanum-doped alumina (La-Al ₂ O ₃ ), zirconium oxide (ZrO ₂ ), cerium oxide (CeO ₂ ), and combinations thereof a metal oxide-based support comprising at least one selected from the group; and a carbon-based support comprising at least one selected from the group consisting of graphite, carbon nanotubes, graphene, and combinations thereof; A continuous hydrogen storage device comprising at least one of. According to claim 1,
A continuous hydrogen storage device in which a plurality of reaction units are accommodated in the housing. According to claim 1,
The reaction unit is a continuous hydrogen storage device comprising a through hole in which the inner space of the reaction unit is divided into two or more spaces by a partition wall, a catalyst is filled in each space, and the partition wall is formed through each space to be connected to each other. According to claim 1,
A continuous hydrogen storage device comprising a plurality of hydrogen storage units including the housing and the reaction unit, wherein the plurality of hydrogen storage units are connected in series. According to claim 1,
The hydrogen is a continuous hydrogen storage device that is supplied to the reaction unit together with a carrier gas. According to claim 1,
The temperature of the reaction part is a continuous hydrogen storage device of 100 ℃ to 200 ℃. According to claim 1,
The pressure of the reaction part is a continuous hydrogen storage device of 10bar to 50bar. According to claim 1,
The hydrogen is a continuous hydrogen storage device that is supplied to the reaction unit at a flow rate of 50 mL/min to 300 mL/min. According to claim 1,
The hydrogen is a continuous hydrogen storage device that is supplied to the reaction unit at a pressure of 50 bar to 60 bar. According to claim 1,
The hydrogen is a continuous hydrogen storage device that is supplied to the reaction unit at a temperature of 150 ℃ to 200 ℃. According to claim 1,
The LOHC is a continuous hydrogen storage device that is supplied to the reaction unit at a flow rate of 0.05 mL/min to 0.2 mL/min.

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