KR101107634B1 - Hydrogen supply apparatus, method for supplying hydrogen and hydrogen usage apparatus using the same - Google Patents

Abstract

When heat is applied, hydrogen is generated by applying heat to a hydrogen generating material that is capable of generating heat and dehydrogenation, and immediately discharges hydrogen generated from the container through a through passage formed in a wall of the container containing the hydrogen generating material. The discharged hydrogen is stored in a tank including the container, not the hydrogen generating container, and then supplied to the hydrogen using device.

Hydrogen generating substance, Hydrogen generating vessel, Hydrogen supply tank, Case, Duralumin

Description

Hydrogen supply apparatus and method, hydrogen using apparatus using the same {Hydrogen supply apparatus, method for supplying hydrogen and hydrogen usage apparatus using the same}

The technology herein relates to a hydrogen supply apparatus and method, and a hydrogen utilization apparatus using the same. The hydrogen supply device and the hydrogen supply method can be applied as a hydrogen supply device of a fuel cell and a hydrogen combustion device, which can be particularly usefully applied to automobiles.

Due to the depletion of fossil energy and environmental pollution, there is a great demand for renewable energy, and hydrogen is attracting attention as one of such alternative energy.

The fuel cell and the hydrogen combustion device use hydrogen as a reaction gas. In order to apply the fuel cell and the hydrogen combustion device to, for example, automobiles, a stable and continuous supply and storage of hydrogen is required.

In order to supply hydrogen to a device using hydrogen, a method of receiving hydrogen whenever hydrogen is required from a separate hydrogen supply station may be used.

Alternatively, the hydrogen generating device may be mounted on a hydrogen using device, and then hydrogen may be generated through the reaction of the corresponding material and supplied to the hydrogen using device.

Hydrogen supply apparatus and method which can generate hydrogen efficiently from self-heating and dehydrogenation by applying heat initially without separate solid or liquid catalyst, and can store hydrogen and supply it to hydrogen using device in low pressure and light weight way, An apparatus using hydrogen is provided.

In the embodiments of the present invention, when the heat is applied is a hydrogen generating vessel that can accommodate the hydrogen generating material that can be dehydrogenated while generating heat, a hydrogen discharge passage is formed in the wall of the hydrogen generating vessel so that the generated hydrogen is naturally discharged It provides a hydrogen generating vessel.

In embodiments of the present invention, a tank having one or more hydrogen generating vessels provided therein provides a hydrogen supply tank for storing hydrogen and naturally supplying hydrogen discharged from the hydrogen generating vessel.

In embodiments of the present invention, a power supply capable of generating heat by supplying power to the hydrogen supply tank, heating means for providing heat to the hydrogen generating material of the hydrogen generating vessel mounted on the hydrogen supply tank, and the power supply Provided is a hydrogen supply comprising a controller to control the supply of power from the apparatus.

In embodiments of the present invention, there is provided a hydrogen utilization apparatus comprising the hydrogen supply tank or hydrogen supply apparatus.

In embodiments of the present invention, generating heat by applying heat to a hydrogen generating material capable of being dehydrogenated while generating heat, and generating hydrogen through a passage formed in a wall of a container containing the hydrogen generating material. It provides a hydrogen supply method comprising the step of discharging and storing the naturally discharged hydrogen in a tank and supplying to the hydrogen using device.

According to embodiments of the present invention, all aspects of hydrogen generation, storage and supply can be made highly efficient, and the hydrogen supply tank can be maintained at low pressure and light weight. In addition, it is possible to store and supply hydrogen in a diversified manner (pressure and shape of hydrogen generating vessels and hydrogen supply tanks can vary), as well as control and low pressure of exothermic reactions during hydrogen generation from hydrogen generating materials. Operation control is easy.

Hereinafter, embodiments of the present invention will be described.

In the present specification, the hydrogen supply device includes a hydrogen generating vessel or a hydrogen supply tank.

In the present specification, a hydrogen-using device is a power generation device such as a fuel cell that receives hydrogen and generates electric power, such as a car or a hydrogen engine using hydrogen combustion energy that is driven by receiving all or a part of power from the power generation device. It includes an overall device using.

In the present specification, the natural discharge of hydrogen means that the hydrogen is discharged to the outside of the hydrogen generating vessel immediately upon generation of hydrogen without passing through a separate means (eg, a valve, a pressure gauge, etc.) for controlling the discharge of generated hydrogen.

When heat is applied, a hydrogen generating material that generates heat while being dehydrogenated may generate hydrogen by first applying heat, and then the materials may continue to generate hydrogen by self-heating even without additional heating.

For example, after the initial heat is applied using the amine borane-based compounds to induce a thermal decomposition reaction, it is possible to continuously dehydrogenation even if no further heat is provided by the exothermic reaction.

For reference, the hydrogen generation method using pyrolysis may be compared with the method using a solid catalyst or a liquid catalyst. The method using a solid catalyst or a liquid catalyst is to minimize the supply of heat energy sources required for hydrogen generation by thermal decomposition and to increase the rate of hydrogen generation. In the solid catalyst method, amine borane is supported on a solid catalyst to be dissolved in a solvent or water is used as a solvent to generate hydrogen through hydrolysis of the amine borane. In the case of liquid catalyst (acid, base, organic acid, ionic liquid) processes, hydrogen is generated through dehydrogenation of the amine borane or simultaneous dehydrogenation with a solvent.

Hydrogen generation, storage, and supply systems should be designed to generate hydrogen from pyrolysis from hydrogen-generating materials such as amine borane without the use of such catalysts or solvents, but to minimize the supply of thermal energy sources required for pyrolysis.

Considering the construction of hydrogen generation, storage and supply systems requires much consideration when the use of catalysts or solvents and the induction of hydrogen evolution through pyrolysis of hydrogen-generating materials are involved.

For example, a vessel for storing hydrogen generated during hydrogen evolution through pyrolysis of hydrogen generating materials tends to be high pressure (eg, greater than 5 atmospheres), which in its nature makes the whole system heavy and large. Moreover, the construction of high pressure vessels at light weight is a technical limitation and is extremely difficult to implement in practice.

From the point of view of practical application and commercialization of the hydrogen utilization apparatus, the low pressure, light weight, and reduction of hydrogen generation, storage and supply vessels to the apparatus is a very important problem.

In addition, it is an important consideration that the container for storing and supplying hydrogen can be transformed into various forms as well as problems such as low pressure, light weight, and reduction of the container. For example, considering the application to automobiles, it is important to properly arrange to utilize the limited space in the vehicle, to reduce the size, and to secure a certain amount of hydrogen generating capacity.

In addition, when constructing a system for generating, storing, and supplying hydrogen using a substance that generates hydrogen by exothermic reaction, consideration of a chain reaction possibility by exothermic reaction is necessary. When the unit vessels containing the hydrogen generating substance are too close to each other, the hydrogen generating reaction in the other vessel is started by the exothermic reaction in one vessel, which controls the hydrogen generating reaction and further the operation control of the hydrogen using device. Not only does it make it difficult, but it also makes it difficult for low pressure, light weight, and reduced system configurations.

The present invention has been made through repeated studies and studies based on the above considerations.

In the embodiments of the present invention, when a heat is applied, a hydrogen generating vessel capable of accommodating a hydrogen generating material capable of generating dehydrogenation while generating heat is provided as a basic unit, and is mounted on a hydrogen supply tank.

When heat (for example, 90 ° C. or more) is initially applied to the hydrogen generating material through heating means, a dehydrogenation exothermic reaction occurs from the material, and by heat from the exothermic reaction, in addition to the initial heating by the heating means, Even without providing heat, the dehydrogenation can continue to generate all possible hydrogen.

In addition, in the embodiments of the present invention, after the heat is generated, the heat generating hydrogen is generated by applying heat to the hydrogen generating material capable of dehydrogenation, and then the hydrogen generated from the vessel is formed in the wall of the container containing the hydrogen generating material. Directly discharged through, and stores the discharged hydrogen in the tank to be supplied to the hydrogen using apparatus.

Accordingly, in the case of using a resistor, which is supplied from the outside via a heating means from the outside, for example, a resistor that generates heat by receiving power from a power source, as a heating means of the hydrogen generating material, the power provided from the outside can be minimized ( For example, when a 70V power supply is connected to a resistor that is a heating means, all hydrogen that can be generated can be generated by operating the power supply for about 2 minutes or less), and the hydrogen supply device can be reduced in pressure, weight, and downsized.

As a non-limiting example of the hydrogen generating material, there are amine borane-based compounds, for example, ammonia borane (NH ₃ BH ₃ ) is preferred. As the ammonia borane, for example, a hydrogen content of 19.6% may be used.

It is preferable that the said hydrogen generating substance is solid from a viewpoint of storage in a hydrogen generating container. More preferably the solid hydrogen generating material may be formed in pellet form. The pellet has a through hole, and heating means, such as a heating rod, for providing the heat along the through hole can be passed. The heating means can here be made separable from the hydrogen generating vessel.

In order to manufacture the hydrogen generating material in a desired form, a mold may be prepared in advance, a solid hydrogen generating material may be added thereto, and then molded to form a hydrogen generating material of the corresponding shape.

In embodiments of the present invention, the vessel containing the hydrogen generating material is discharged directly without storing hydrogen. That is, hydrogen generated when hydrogen is generated from the hydrogen generating material is naturally discharged through the hydrogen discharge passage.

To this end, a passage through which the generated hydrogen is naturally discharged is formed in the wall of the hydrogen generating vessel. There is no separate gauge or valve in the passage, so hydrogen may be immediately discharged along the passage.

Forming a passage through which the hydrogen can be directly discharged to the vessel wall as described above can minimize the pressure on the hydrogen generating vessel itself, as well as reduce the pressure, light weight, and size of the entire hydrogen storage and supply tank. As mentioned above, the higher the hydrogen pressure, the larger the overall system becomes, and the more difficult it is to control the operation.

Preferably, a plurality of hydrogen discharge passages may be formed on the wall of the vessel, and the hydrogen discharge passages may be formed to be spaced apart from each other at a predetermined interval to efficiently perform hydrogen discharge and storage.

In embodiments of the present invention, the hydrogen generating vessel may have a case open at one side and blocking means for blocking an open portion of the case to receive or discharge the hydrogen generating material. In addition, the hydrogen discharge passage may be formed in the wall of the case.

The blocking means may be coupled to the case to be attached and detached. For example, a spiral groove is formed at one end of the case, and a spiral groove is formed at the blocking portion to be screwed together by engaging with each other.

The reason for this attachment and detachment is to generate all the hydrogen from the hydrogen generating material in the hydrogen generating container and then refill the hydrogen generating material with new hydrogen generating material or regenerate the used hydrogen generating material. To do so.

The material of the hydrogen generating vessel is not limited, but not only the price but also the thermal conductivity, the robustness, and the like should be particularly considered. It is preferable to configure the hydrogen generating vessel with a material having low thermal conductivity because the heat generated between adjacent hydrogen generating vessels when each hydrogen generating vessel is arranged in a plurality of hydrogen supply tanks does not require a separate heat supply by the heating means. This is to prevent the exothermic reaction. As a non-limiting example of the material of a hydrogen generating container, there are engineering plastics, SUS alloy, duralumin, etc., especially duralumin is preferable. For reference, non-limiting examples of engineering plastics include acrylonitrile butadiene styrene (ABS), polycarbonate (PC), polyamide (PA), polybutylene terephthalate (PBT), and the like. Non-limiting examples of the SUS alloy include SUS 304, SUS 316 alloy, and the like.

The hydrogen generating vessel is mounted in a hydrogen supply tank and the hydrogen discharged from the vessel may be stored in the hydrogen supply tank and then supplied to an external hydrogen utilization apparatus.

Preferably, the hydrogen generating vessel is mounted to be attachable and detachable to the hydrogen supply tank. After all the hydrogen is generated from the hydrogen generating materials in the individual hydrogen generating vessels, the hydrogen generating vessels are desorbed from the hydrogen supply tank, and the hydrogen generating vessels are filled with new hydrogen generating substances or the used hydrogen generating materials are regenerated. After refilling, the hydrogen generating vessel may be reattached to the hydrogen supply tank.

As a non-limiting example, the hydrogen generating vessel may be threaded mounted to the hydrogen supply tank. For example, when the hydrogen generating container includes a case and a blocking means for screwing in and out of the case, the spiral groove may be formed in the blocking means so as to be screwed with the hydrogen supply tank.

According to the structure which enables attachment and detachment as described above, the hydrogen generating vessel can be freely mounted, and thus not only the shape of the hydrogen supply tank but also the total tank pressure can be modified in various ways.

In one embodiment, when the hydrogen supply tank is 5 atm or less, the hydrogen generating vessel may be sealed to withstand a pressure of 5 atm or less.

When a plurality of hydrogen generating vessels are mounted in the hydrogen supply tank, the plurality of hydrogen generating vessels is preferably arranged to be spaced at regular intervals in the hydrogen supply tank.

By arranging the hydrogen generating vessels spaced apart at regular intervals in the hydrogen supply tank, even if there is no heat supply by the heating means in the other hydrogen generating vessel due to the heat generated at the hydrogen generation in one hydrogen generating vessel. It can be prevented from occurring.

In one embodiment, four hydrogen generating vessels may be arranged at an angle of 90 degrees to one another on the same plane and spaced apart from each other at regular intervals. These four hydrogen generating vessels can be defined as one set. The number of hydrogen generating vessels or the number of hydrogen generating vessel sets provided in the hydrogen supply tank may increase depending on the total capacity of the hydrogen supply tank. It is possible to increase the number of hydrogen generating vessels or the number of sets in proportion to the hydrogen capacity to be stored. For reference, when the capacity of the hydrogen supply tank is set to 2 to 3L, 20 to 40 70 cc hydrogen generating vessels (for example, 8 sets of 32 in FIG. 2A) may be provided.

The four hydrogen generating vessels in one set are preferably arranged spaced apart from each other by an interval of 1 cm or more and 5 cm or less. When the mutual separation distances of the four hydrogen generating vessels in one set are less than 1 cm, there exists a possibility that reaction may begin to generate | occur | produce without heating by a heating means to a hydrogen generating vessel by heat generation of an adjacent hydrogen generating vessel. For reference, it is not preferable to arrange two hydrogen generating vessels adjacent to each other by less than 1 cm, even if the four hydrogen generating vessels are arranged in different manners rather than making one set with 90 degrees. .

If the mutual separation distance of the hydrogen generating vessels in one set is more than 5 cm, the arrangement in the hydrogen supply tank may be difficult, and the overall tank size may be made large.

In one embodiment, the volume of the hydrogen supply tank is preferably between 2L and 70L, depending on its use. Specific dosages may vary depending on the application. For reference, it can be configured, for example, 70L when applied to automobiles.

Further, in one embodiment, the hydrogen pressure stored in the hydrogen supply tank is preferably low pressure of 5 atm or less.

The hydrogen supply tank is preferably made of a material of lightweight material, and by way of non-limiting example, it is preferably made of any one of engineering plastics, SUS alloys or duralumin.

In embodiments of the present invention, when hydrogen is generated by applying minimal heat (or electric power) to the hydrogen supply tank, the reaction of dehydrogenation proceeds by the reaction heat. Therefore, it is desirable to measure the pressure of the tank and control the energy supply (or power supply) when a certain pressure is reached based on the pressure.

Therefore, embodiments of the present invention can generate heat by supplying power to a hydrogen supply tank equipped with a hydrogen generating vessel and a heating means for providing heat to the hydrogen generating material of the hydrogen generating vessel mounted on the hydrogen supply tank. And a controller that controls the power supply and the power supply from the power supply.

The hydrogen supply tank may be connected with a pressure measuring device such as a pressure gauge or a pressure sensor for measuring the pressure in the tank. For example, a pressure gauge or sensor can be mounted directly to the hydrogen supply tank.

A safety valve can be connected to the hydrogen supply tank. If the pressure in the hydrogen supply tank exceeds a certain pressure, the safety valve may be opened to discharge hydrogen from the hydrogen supply tank.

The hydrogen supply tank may be connected to at least one of a filter device for filtering solid substances present in the gas discharged from the hydrogen supply tank or a trap device for capturing gaseous by-products of the hydrogen evolution reaction present in the gas discharged from the hydrogen supply tank. Can be. For example, the gas discharged from the hydrogen supply tank may pass through the filter device after passing through the filter device, and may pass through the filter device after passing the trap device.

A regulator may be further provided for regulating the discharge of hydrogen before the hydrogen is supplied from the hydrogen supply tank to the hydrogen utilization apparatus.

The hydrogen supply apparatus including a hydrogen supply tank etc. can be comprised as follows.

That is, the hydrogen supply device includes a pressure measuring device connected to a hydrogen supply tank, a valve connected to a hydrogen supply tank, a filter device for filtering a solid material among hydrogen-containing materials discharged through the valve, and a hydrogen-containing material discharged from the hydrogen supply tank. And a trap device to capture gaseous byproducts of the hydrogen evolution reaction. A solvent capable of dissolving the polar material may be used in the trap device, for example, water may be used. The apparatus for controlling hydrogen may further include a controller for controlling the discharge of hydrogen before discharging the hydrogen to the apparatus.

Hydrogen using device according to the embodiments of the present invention is to receive the hydrogen from the above hydrogen supply tank or hydrogen supply device to use the hydrogen to supply the combustion or to generate power or to generate power from the power generating device The device may be supplied and driven.

The hydrogen using apparatus may be a fuel cell such as a polymer electrolyte fuel cell. In addition, the hydrogen using apparatus may be a vehicle that receives power from the fuel cell.

In embodiments of the present invention, the hydrogen supply tank to the hydrogen supply device can be maintained at low pressure and light weight, and it is particularly useful to mount the fuel cell vehicle because it is easy to control the half-heat reaction and control the low pressure operation.

DETAILED DESCRIPTION Hereinafter, exemplary embodiments of the present invention will be described in more detail with reference to the drawings.

1 is a schematic view showing a hydrogen generating vessel in an exemplary embodiment of the invention.

Referring to FIG. 1, the hydrogen generating vessel has a case 10 (see FIG. 1A) capable of accommodating hydrogen generating material and blocking means 20 (see FIG. 1B) for blocking an open portion of the case. . Hydrogen generating material may be received or discharged through the open portion of the case 10. 1 illustrates a case shape in a circular columnar shape, the case shape may be variously designed according to the form of the hydrogen generating material.

A part of the wall 12 of the case is provided with a plurality of hydrogen discharge passages 11 through which hydrogen is naturally discharged.

The blocking means 20 is coupled to the case 10 so as to be attached and detached to prevent an open portion of the case, and includes, for example, a spiral groove 23 for screwing with a spiral groove 13 at one end of the case. One member (see FIGS. 1A-1C).

The blocking means 20 may be formed with a through hole, and a heating rod 40 (see FIG. 1D) that generates heat by receiving power from a heating means, for example, an external power source, passes through the through hole, and the blocking means is coupled. It can be made to exist inside the hydrogen generating container 30 in a case. The heating rod 40 may be provided with a wire 41 to be connected to a power source.

The hydrogen generating material contained in the hydrogen generating vessel 30 may be in the form of a solid pellet 5 having through holes formed therein (see FIG. 1E).

The heating rod (see FIG. 1D) as mentioned above may be present inside the case along the through hole of the hydrogen generating material in pellet form. FIG. 1F schematically shows a hydrogen generating vessel 50 in which a hydrogen generating substance 5 in pellet form is contained therein and includes a heating rod which is a heating means. The heating rod to which the electric wire 41 is connected enters the hydrogen generating vessel 50 through the through hole of the blocking means and exists along the through hole of the hydrogen generating substance in the form of pellets.

The volume of the hydrogen generating vessel 30 depends on the volume of the hydrogen supply tank to be described later, but it is possible to produce a lightweight, reduced hydrogen supply system of 7 cc to 20 cc, and to supply a low pressure hydrogen of 5 atm or less as described below. It is preferable because a tank can be formed.

As mentioned above, the hydrogen generating vessel is preferably made of a lightweight material, and as a non-limiting example, it can be made of engineering plastics, SUS alloys or duralumin, and the like, and especially duralumin is preferable in that it is strong and light.

2 is a schematic diagram showing a hydrogen supply tank in an exemplary embodiment of the invention.

Referring to FIG. 2, a hydrogen generating vessel 50 is attached to a hydrogen supply tank 100. For reference, in FIGS. 2A and 2B, which are front and cross-sectional schematic views, the wire 41 connected to the heating rod of the hydrogen generating vessel is not shown for the sake of simplicity, but FIG. 2C schematically shows the mounting state of the individual hydrogen generating vessel. The wire 41 is shown together.

The hydrogen generating container 50 may be mounted in plurality in the hydrogen supply tank 100, in which case it may be mounted to be attached and detached. For example, a spiral groove may be formed in a corresponding portion of the hydrogen supply tank 100 in which the hydrogen generating vessel 50 is mounted, and may be screwed by being engaged with the spiral groove formed in the blocking member of the hydrogen generating vessel 50. . As such, when the hydrogen generating vessel 50 is mounted to the hydrogen supply tank 100, it should be installed to withstand the pressure in the hydrogen supply tank 100. For example, when the tank 100 pressure is 5 atm or less, the hydrogen generating vessel should be sealed to withstand a pressure of 5 atm or less.

2b shows that the four hydrogen generating vessels are arranged at an angle of 90 degrees to each other on the same plane and spaced apart from each other by a distance d. As described above, when defining these four hydrogen generating vessels as one set, the hydrogen supply tank may have a plurality of sets, such as one or more sets and a plurality of sets (the number of sets depends on the volume of the hydrogen supply tank). Can be. Figure 2a schematically shows that eight sets (32 hydrogen generating vessels) are provided.

Each hydrogen generating vessel should be spaced appropriately so that a rise in temperature due to exotherm during hydrogen evolution (eg, about 150 degrees) cannot proceed with the hydrogen evolution of the surrounding solid hydrogen generating materials.

Referring again to FIG. 2B, the spacing d of the four hydrogen generating vessels is not limited, but is preferably an interval of 1 cm or more and 5 cm or less.

If it is less than 1 cm, there is a fear that a chain reaction starts to occur in the adjacent hydrogen generating vessel without providing heating by the heating means. In the case of more than 5 cm, the arrangement in the hydrogen supply tank becomes difficult, which may increase the overall tank size.

The volume of the hydrogen supply tank 100 is preferably 2L to 70L in view of light weight and reduction in size depending on the use thereof. Moreover, it is preferable to comprise the hydrogen supply tank 100 so that internal pressure may become low pressure of 5 atmospheres or less.

3 is a schematic diagram illustrating a concept of a hydrogen supply apparatus including a hydrogen supply tank in exemplary embodiments of the present invention.

Referring to FIG. 3, a pressure measuring device G is connected to the hydrogen supply tank H to measure the pressure of the hydrogen supply tank, and a safety valve S is attached to the hydrogen supply tank. The pressure measuring device G is connected to the controller C and the controller C controls the power supply from the power supply P connected with the heating means of the hydrogen supply tank based on the measured pressure.

The hydrogen-containing material generated from the hydrogen supply tank passes through the filter device F to filter out the solid material in the hydrogen-containing material.

The gaseous by-product of the hydrogen evolution reaction in the hydrogen-containing material passed through the filtering device F is captured while passing through the trap device (T). A solvent (for example, water) capable of dissolving the polar material may be used in the trap device T. The hydrogen passing through the trap device T may be discharged to the hydrogen using device via the regulating device R.

In the hydrogen supply method according to the embodiments of the present invention as described above, by using a hydrogen generating material that can generate heat and dehydrogenation by providing heat, it is possible to store and supply hydrogen in high efficiency, low pressure, light weight, and diversified manner. In addition, it is easy to control the exothermic reaction and control the low pressure operation.

The hydrogen supply apparatus or method may be usefully mounted on a fuel cell vehicle.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the contents described in the following Examples. For example, it will be understood by those skilled in the art that the specification, material, arrangement, and the like of the hydrogen generating vessel and tank described in the embodiments are described by way of example.

Example 1

As shown in FIG. 1, the hydrogen generating vessel was configured in such a manner that the case and the blocking means are provided and they are screwed together. The heating rod entered the case through a through hole formed in the blocking means and was present along the through hole of the solid pellet catalyst of ammonia borane (see FIG. 1).

32 (8 sets) of the said hydrogen generating containers comprised as mentioned above were attached to the hydrogen supply tank like FIG. 2A. The four hydrogen generating vessels in each set are 90 degrees to each other and the separation distance d is 1 cm (see FIG. 2B).

The hydrogen generating vessels each had a volume of 7 cc and made of duralumin. The volume of the hydrogen supply tank was 2.7 L and made of SUS alloy. The heating rod used a 125 Ohm resistance wire, and a 70V power source was used as the power source.

For the test in Example 1, 5 of the 32 hydrogen generating vessels were selected. The selected hydrogen generating vessel was filled with an average of 2.92 g of ammonia borane.

For reference, FIG. 2A shows two hydrogen generating vessels in the top layer. The left vessel was selected as vessel 1 among the two hydrogen generating vessels. 2a shows three hydrogen generating vessels in the second layer. The three hydrogen generating vessels were selected as vessels 2 to 4, respectively. 2a shows two hydrogen generating vessels in the third layer. The right vessel was selected as vessel 5 among the two hydrogen generating vessels.

The selected vessels 1 and 5 are on different layers but at an angle of 90 degrees in plan view and spaced apart from each other by 1 cm. Three vessels 2-4 selected in the second layer are 90 degrees to each other with a distance of 1 cm.

In power supply control (both manual control and automatic control), when a 70V power supply was used for a 125 Ohm resistance wire, the heating rod was powered for only 1 minute and 30 seconds, and all possible hydrogen was generated. There was no chain reaction by the heat of reaction in the adjacent hydrogen generating vessel. An average of 3.63 L of hydrogen was generated in the equipped hydrogen generating vessel, and the pressure in the entire tank was kept below 2 atm. This is the result of the generation of 10.35 wt% hydrogen from ammonia borane.

Table 1 below describes information such as the amount of ammonia borane (AB) in each hydrogen generating vessel and the amount of hydrogen generated.

For reference, vessels 2 to 5 are operation results using an automatic control system using a controller. The amount of ammonia borane contained in each of the containers 2 to 5 was the same. In the table below, the amounts of ammonia borane, the amount of hydrogen, and the like are displayed for the entire containers 2 to 5 without displaying the amount of ammonia borane, the amount of hydrogen, and the like for each of the containers 2-5. In the automatic control system, the controller turned off the power when the hydrogen pressure became 1.0 atm.

After automatic operation of vessels 2 to 5, this time, manual operation was performed only on vessel 1 (the vessel selected in the uppermost layer) to measure the amount of hydrogen generation. Since all hydrogen was generated 1 minute and 30 seconds after the automatic operation of vessels 2 to 5, the power was turned off after 1 minute and 30 seconds in the manual operation for vessel 1.

AB
(g) AB
(gmol) AB
(ml) AB density
(g / ml) Relative density (theoretical density = 0.78 g / ml) Hydrogen generation amount
(L) Hydrogen generation amount
(gmol;
Ideal gas
home) H ₂ / AB
Courage 1
(manual
driving) 2.97 0.10 4.01 0.74 0.95 3.37 0.14 1.46 Canister 2 ~ 5 (automatic control operation) 11.65 0.38 15.70 0.74 0.95 14.79 0.62 1.63 Average 2.92 0.48 3.94 0.74 0.95 3.63 0.76 1.59

[Example 2]

The same hydrogen generating vessel as in Example 1 (see FIG. 1) and a hydrogen supply tank (see FIGS. 2A and 2B) were used.

For the test of Example 2, four of the 32 hydrogen generating vessels were selected at the bottom of the hydrogen supply tank this time. The selected hydrogen generating vessel was filled with an average of 1.95 g of ammonia borane at low density. For reference, four (one sets) of hydrogen generating vessels shown in the bottom layer of the tank shown in FIG. 2A were selected as the respective vessels 1-4. The four hydrogen-generating vessels here are at 90 degrees to each other and the separation distance d is 1 cm.

The power supply was manually controlled as in vessel 1 of Example 1. That is, when a 70V power source was used for a 125 Ohm resistance wire, the heating rod was supplied for only 1 minute and 30 seconds, and all hydrogen that could be generated was generated.

There was no chain reaction by the heat of reaction in the adjacent hydrogen generating vessel. An average of 2.29 L of hydrogen was generated in each hydrogen generating vessel, and the pressure in the entire tank was kept below 2 atm. 9.89 wt% of hydrogen was generated from ammonia borane.

In Table 2, information such as the amount of ammonia borane (AB) and the amount of hydrogen generated in each of the hydrogen generating vessels 1 to 4 is described.

AB
(g) AB
(gmol) AB
(ml) AB density
(g / ml) Relative density (theoretical density = 0.78 g / ml) Hydrogen generation amount
(L) Hydrogen generation amount
(gmol;
Ideal gas
home) H ₂ / AB
Courage 1 1.95 0.0633 3.70 0.53 0.68 2.15 0.089 1.41 Courage 2 1.80 0.0584 3.45 0.52 0.67 2.20 0.092 1.57 Courage 3 1.82 0.0591 3.42 0.53 0.68 2.52 0.105 1.78 Courage 4 2.21 0.0717 3.96 0.56 0.72 2.29 0.095 1.33 Average 1.95 0.06 3.63 0.53 0.69 2.29 0.10 1.52

Although the above non-limiting and exemplary embodiments of the present invention have been described, the technical idea of the present invention is not limited to the accompanying drawings and the above description. It will be apparent to those skilled in the art that various forms of modifications can be made without departing from the spirit of the present invention, and furthermore, such modifications will be within the scope of the claims of the present invention.

1 is a schematic view showing a hydrogen generating vessel in an exemplary embodiment of the invention.

2 is a schematic diagram illustrating a hydrogen supply tank according to an exemplary embodiment of the present invention.

3 is a schematic diagram illustrating a concept of a hydrogen supply apparatus including a hydrogen supply tank in exemplary embodiments of the present invention.

Claims (43)

A hydrogen supply tank equipped with one or more hydrogen generating vessels, The hydrogen generating vessel is capable of accommodating a hydrogen generating substance that is dehydrogenated while generating heat when heat is applied thereto. Hydrogen discharge passage is formed on the wall of the hydrogen generating vessel so that the generated hydrogen can be discharged, The hydrogen supply tank is to store the hydrogen discharged from the hydrogen generating vessel and to supply to the outside, A plurality of hydrogen generating vessel is mounted in the hydrogen supply tank, A plurality of hydrogen generating vessels are spaced in the hydrogen supply tank to prevent hydrogen from being generated even when there is no heat supply by the heating means in the other hydrogen generating vessel due to the heat generated when the hydrogen is generated in one of the hydrogen generating vessels. Arranged to be spaced apart by The hydrogen generating vessel and the hydrogen supply tank is a hydrogen supply tank, characterized in that made of any one material of engineering plastics, SUS alloy or duralumin. The method of claim 1, A hydrogen supply tank, characterized in that a plurality of hydrogen discharge passages spaced at regular intervals are formed on the wall of the hydrogen generating vessel. The method of claim 1, Hydrogen generating material is a hydrogen supply tank, characterized in that the pellet form with a through hole. The method of claim 1, And a heating means capable of providing heat to the hydrogen generating material. The method of claim 4, wherein And a heating means generates heat by receiving power from a power source. The method of claim 4, wherein And a heating means is separable from the hydrogen generating vessel. The method of claim 1, The hydrogen generating vessel has a case open on one side; And blocking means coupled to the case to be attached and detached to prevent an open portion of the case. Hydrogen generating material can be received or discharged through the open portion of the case, A hydrogen supply tank, wherein a hydrogen discharge passage is formed in the case wall. The method of claim 7, wherein A heating means capable of providing heat to a hydrogen generating material, comprising: a heating rod powered by an external power source to generate heat, The blocking means is formed with a through hole, And a heating rod is present inside the case through the through hole formed in the blocking means. The method of claim 8, Hydrogen generating material is in the form of pellets with through holes formed, And a heating rod is present along the through hole of the hydrogen generating material in pellet form. The method of claim 7, wherein Hydrogen supply tank characterized in that the case and the blocking portion is screwed. The method of claim 1, The hydrogen supply tank, characterized in that the hydrogen generating vessel volume is 7cc to 20cc. delete The method of claim 1, The hydrogen supply tank, characterized in that the hydrogen generating material is an amine borane-based material. The method of claim 1, A hydrogen supply tank, wherein the hydrogen generating substance is ammonia borane. delete The method of claim 1, A hydrogen supply tank, characterized in that the hydrogen generating vessel is mounted so as to be attached to and detachable from the hydrogen supply tank. The method of claim 16, Hydrogen generating vessel is hydrogen supply tank, characterized in that the screw is mounted to the hydrogen supply tank. The method of claim 17, The hydrogen generating vessel has a case open on one side; And blocking means for screwing the case and preventing an open portion of the case. And said blocking means is screwed with said hydrogen supply tank. delete delete The method of claim 1, A hydrogen supply tank, characterized in that the four hydrogen generating vessels comprise a set of hydrogen generating vessels which are arranged at an angle of 90 degrees to each other on the same plane and spaced apart from each other at regular intervals. The method of claim 21, Four hydrogen generating vessels are arranged spaced apart from each other at intervals of 1 cm or more and 5 cm or less. The method of claim 1, A hydrogen supply tank, characterized by increasing the number of hydrogen generating vessels as the volume of the hydrogen supply tank increases. The method of claim 1, The hydrogen supply tank is characterized in that the volume of the hydrogen supply tank is 2L to 70L. The method of claim 1, A hydrogen supply tank having a hydrogen pressure stored in the hydrogen supply tank of 5 atm or less. delete The method of claim 1, And a pressure measuring device is connected to the hydrogen supply tank. The method of claim 1, A hydrogen supply tank, characterized in that the safety valve is connected to the hydrogen supply tank. The method of claim 1, The hydrogen supply tank includes at least one of a filter device for filtering solid substances present in the gas discharged from the hydrogen supply tank, or a trap device for trapping gaseous by-products of the hydrogen evolution reaction present in the gas discharged from the hydrogen supply tank. Hydrogen supply tank, characterized in that connected. A hydrogen supply tank according to claim 1; A power source capable of generating heat by supplying power to heating means for providing heat to the hydrogen generating material of the hydrogen generating vessel mounted on the hydrogen supply tank; And And a controller for controlling the supply of power from the power source. 31. The method of claim 30, Further comprising a pressure measuring device connected to the hydrogen supply tank, When the pressure of the pressure measuring device reaches a predetermined pressure, the hydrogen supply device characterized in that the power supply is cut off from the power supply. The method of claim 31, wherein A safety valve connected to the hydrogen supply tank; A filter device for filtering solid material among hydrogen-containing materials discharged from the hydrogen supply tank; A trap device for trapping gaseous by-products of the hydrogen evolution reaction in the hydrogen-containing material discharged through the filtering device; And And a regulating device for regulating the discharge of hydrogen discharged through the trap device. A hydrogen utilization apparatus comprising the hydrogen supply tank according to claim 1. The method of claim 33, wherein The hydrogen utilization apparatus includes a fuel cell that receives hydrogen from the hydrogen supply tank. 35. The method of claim 34, The hydrogen utilization apparatus is a hydrogen utilization apparatus that is driven by receiving all or part of power from the fuel cell. A hydrogen utilization apparatus comprising the hydrogen supply apparatus of claim 30. 37. The method of claim 36, The hydrogen utilization apparatus includes a fuel cell that receives hydrogen from the hydrogen supply apparatus. 39. The method of claim 37, The hydrogen utilization apparatus is a hydrogen utilization apparatus which is a vehicle driven by receiving all or part of power from the fuel cell. Generating heat by applying heat to a hydrogen generating material capable of dehydrogenation while generating heat; Discharging the generated hydrogen through a through passage formed in a wall of the vessel containing the hydrogen generating substance; And Storing the discharged hydrogen in a tank and supplying the discharged hydrogen to a hydrogen using device; The vessel and tank are made of any one of engineering plastic, SUS alloy or duralumin, A method for supplying hydrogen, characterized in that the pressure in the tank is maintained at 5 atm or less. 40. The method of claim 39, When the hydrogen starts to generate after the initial heat is applied, the heating is stopped and hydrogen is generated by the heat of reaction of the hydrogen generating material. 40. The method of claim 39, Measuring hydrogen pressure stored in the tank and stopping heating to the hydrogen generating material when the hydrogen pressure exceeds a predetermined pressure. 40. The method of claim 39, When the stored hydrogen pressure exceeds a predetermined pressure, the hydrogen supply method characterized in that for opening the safety valve of the tank to discharge hydrogen. delete

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