KR20240033947A - Production apparatus and method for high purity hydrogen using ammonia - Google Patents

Abstract

One embodiment of the present invention includes a decomposition reaction unit for decomposing ammonia through an ammonia decomposition reaction and discharging reaction products containing hydrogen, nitrogen, and unreacted ammonia generated from the ammonia decomposition reaction, and a first ammonia supply unit. A combustion unit that burns the supplied ammonia to heat the decomposition reaction unit, a vaporizer that vaporizes the liquid ammonia supplied from the second ammonia supply unit, and a preheater that preheats the ammonia supplied from the vaporizer through an intermediate connection line. Provided is a high-purity hydrogen production device using ammonia, including a vaporization preheating unit, a hydrogen supply unit for supplying hydrogen to the intermediate connection line, and an adsorption purification unit for separating and purifying high-purity hydrogen from the reaction product.

Description

{Production apparatus and method for high purity hydrogen using ammonia}

The present invention relates to an apparatus and method, and more particularly, to a manufacturing apparatus and method for producing high purity hydrogen using ammonia.

The ammonia decomposition reaction is a reaction in which two ammonia molecules are decomposed into one nitrogen molecule and three hydrogen molecules (NH3) N2+3H2), and as an endothermic reaction, it requires about 46 kJ/mol of heat. This method of producing hydrogen through ammonia decomposition reaction is widely used to produce high-purity hydrogen needed in general gas-related industries or semiconductor and LCD factories.

Generally, when manufacturing a water tank through an ammonia decomposition reaction, ammonia at room temperature is preheated to a high temperature through heat exchange and then supplied to the decomposition reactor. The ammonia heated in this way corrodes the metal pipes and decomposition reactor through a nitriding reaction. There is a problem that the lifespan of the manufacturing device is shortened. Moreover, if nitrification progresses as the preheater, the piping connecting the preheater to the decomposition reactor, and the decomposition reactor are continuously exposed to high temperature ammonia, serious corrosion problems may occur.

The technical problem to be achieved by the present invention is to not only prevent corrosion of the preheater and the pipes connecting the preheater and the decomposition reactor due to high temperature ammonia in the hydrogen production process using the ammonia decomposition reaction, but also to prevent high temperature ammonia from occurring through these pipes. A device and method for producing high-purity hydrogen using ammonia that can solve corrosion problems occurring in a decomposition reactor into which ammonia flows (i.e., corrosion of the metal reactor body constituting the decomposition reactor, filling materials and catalysts in the decomposition reactor) is to provide.

The technical problem to be achieved by the present invention is not limited to the technical problem mentioned above, and other technical problems not mentioned can be clearly understood by those skilled in the art from the description below. There will be.

In order to achieve the above technical problem, a high-purity hydrogen production device using ammonia according to an embodiment of the present invention decomposes ammonia through an ammonia decomposition reaction, and produces hydrogen, nitrogen, and unreacted ammonia from the ammonia decomposition reaction. a decomposition reaction unit that discharges a reaction product containing a decomposition reaction unit, a combustion unit that heats the decomposition reaction unit by burning the ammonia supplied from the first ammonia supply unit, a vaporizer that vaporizes the liquid ammonia supplied from the second ammonia supply unit, and A vaporization preheating unit including a preheater for preheating ammonia supplied from the vaporizer through an intermediate connection line, a hydrogen supply unit for supplying hydrogen to the intermediate connection line, and an adsorption purification unit for separating and purifying high purity hydrogen from the reaction product. May include wealth.

In an embodiment of the present invention, the hydrogen supply unit includes an internal supply unit disposed at any one of the rear end of the decomposition reaction unit, the front or rear end of the adsorption purification unit, and the hydrogen storage unit where separated and purified high-purity hydrogen is stored. It may include at least one of an external supply unit disposed outside the connection line through which the reaction product, the ammonia, and the high-purity hydrogen pass.

In an embodiment of the present invention, the internal supply unit includes a first supply unit that supplies a part of the reaction product discharged from the decomposition reaction unit to the intermediate connection line, and a part of the reaction product supplied to the adsorption purification unit. A second supply part that supplies to the intermediate connection line, a third supply part that supplies a part of the high-purity hydrogen separated, purified and discharged from the adsorption purification unit to the intermediate connection line, and a part of the high-purity hydrogen stored in the hydrogen storage part. It may include at least one of the fourth supply units that supply to the intermediate connection line.

In an embodiment of the present invention, the hydrogen supply unit may supply hydrogen to a hydrogen inflow point located at a different location from the intermediate connection line.

In an embodiment of the present invention, the hydrogen inflow points are provided in a plurality of different ways, and the hydrogen supply unit may supply hydrogen to at least one of the plurality of hydrogen inflow points.

In an embodiment of the present invention, the hydrogen inflow point is a first inlet point connected to the first supply line connecting the second ammonia supply part and the vaporizer, and a second supply point connecting the preheater and the decomposition reaction part. It may include at least one of the second inflow points connected to the line.

In order to achieve the above technical problem, a method for producing high-purity hydrogen using ammonia according to an embodiment of the present invention includes the steps of a vaporizer generating gaseous ammonia by vaporizing liquid ammonia supplied from a second ammonia supply unit, and supplying hydrogen. Additionally, supplying hydrogen to an intermediate connection line connecting the vaporizer and the preheater, a combustion unit burning ammonia supplied from the first ammonia supply unit, and heating the decomposition reaction unit, the preheater comprising: A step of preheating ammonia and supplying it to a decomposition reaction unit, the decomposition reaction unit decomposing ammonia through an ammonia decomposition reaction and discharging a reaction product containing hydrogen, nitrogen, and unreacted ammonia, and an adsorption purification unit performing the reaction. It may include the step of adsorbing and removing nitrogen and unreacted ammonia from the product to separate and purify high-purity hydrogen.

In an embodiment of the present invention, the internal supply unit may further include supplying a reaction product or hydrogen to the intermediate connection line.

In an embodiment of the present invention, the internal supply unit includes a first supply unit that supplies a part of the reaction product discharged from the decomposition reaction unit to the intermediate connection line, and a part of the reaction product supplied to the adsorption purification unit. A second supply unit supplies a portion of the high-purity hydrogen separated and purified in the adsorption purification unit to the intermediate connection line, and a third supply unit supplies a portion of the high-purity hydrogen stored in the hydrogen storage unit to the intermediate connection line. It may include at least one of the fourth supply units that supply to the line.

In an embodiment of the present invention, the hydrogen supply unit may further include supplying hydrogen to a hydrogen inflow point located at a different location from the intermediate connection line.

In an embodiment of the present invention, the hydrogen inflow point is a first inlet point connected to the first supply line connecting the second ammonia supply part and the vaporizer, and a second supply point connecting the preheater and the decomposition reaction part. It may include at least one of the second inflow points connected to the line.

In order to achieve the above technical problem, a high-purity hydrogen production device using ammonia according to another embodiment of the present invention decomposes ammonia through an ammonia decomposition reaction, and produces hydrogen, nitrogen, and unreacted ammonia from the ammonia decomposition reaction. a decomposition reaction unit that discharges a reaction product containing a decomposition reaction unit, a combustion unit that heats the decomposition reaction unit by burning the ammonia supplied from the first ammonia supply unit, a vaporizer that vaporizes the liquid ammonia supplied from the second ammonia supply unit, and A vaporization preheating unit including a preheater for preheating ammonia supplied from the vaporizer through an intermediate connection line, a catalytic reaction unit for decomposing some of the preheated ammonia through a catalytic reaction to produce hydrogen, and the reaction product It may include an adsorption purification unit that separates and purifies high purity hydrogen.

In an embodiment of the present invention, hydrogen and nitrogen produced in the catalytic reaction unit may be supplied to the decomposition reaction unit along with unreacted ammonia.

In an embodiment of the present invention, the catalytic reaction may be carried out using the heat energy contained in ammonia heated by the preheater.

In an embodiment of the present invention, the catalytic reaction may be carried out using an electric heating method.

The high-purity hydrogen production device and production method according to embodiments of the present invention additionally supplies hydrogen from the rear end of the decomposition reaction section, the front end or rear end of the adsorption purification section, and the hydrogen storage section between the vaporizer and the preheater, thereby producing a high-temperature gaseous ammonia. Corrosion in the preheater, decomposition reaction section, and piping connecting the rear end of the preheater and the decomposition reaction section can be suppressed. In addition, by additionally supplying hydrogen to hydrogen inlet points other than between the vaporizer and the preheater, corrosion of the decomposition reaction zone due to high-temperature gaseous ammonia can be prevented.

In addition, the high-purity hydrogen production device and production method according to embodiments of the present invention produces hydrogen by catalytically decomposing part of the preheated gaseous ammonia before being supplied to the decomposition reaction section, and supplies it to the decomposition reaction section along with the gaseous ammonia. By doing so, it is possible to prevent corrosion of the decomposition reaction portion caused by high-temperature gaseous ammonia.

The effects of the present invention are not limited to the effects described above, and should be understood to include all effects that can be inferred from the configuration of the invention described in the description or claims of the present invention.

Figure 1 is a block diagram showing a high-purity hydrogen production device using ammonia according to an embodiment of the present invention.
Figure 2 is a block diagram showing a high-purity hydrogen production device using ammonia according to another embodiment of the present invention.
Figure 3 is a block diagram showing a high-purity hydrogen production device using ammonia according to another embodiment of the present invention.
FIG. 4 is a block diagram showing the steps of producing high-purity hydrogen using the high-purity hydrogen production apparatus using ammonia of FIGS. 1 to 3.
Figure 5 shows the state before and after corrosion of the decomposition reaction zone by high-temperature ammonia in the case where hydrogen is not supplied to the intermediate connection line. Figure 6 shows the state before and after corrosion of the decomposition reaction zone by high-temperature ammonia in the case where hydrogen is supplied to the intermediate connection line.
Figure 7 is a block diagram showing a high-purity hydrogen production device using ammonia according to another embodiment of the present invention.
FIG. 8 is a block diagram showing steps for producing high-purity hydrogen using the high-purity hydrogen production device using ammonia of FIG. 7.

Hereinafter, the present invention will be described with reference to the attached drawings. However, the present invention may be implemented in various different forms and, therefore, is not limited to the embodiments described herein. In order to clearly explain the present invention in the drawings, parts that are not related to the description are omitted, and similar parts are given similar reference numerals throughout the specification.

Throughout the specification, when a part is said to be "connected (connected, contacted, combined)" with another part, this means not only "directly connected" but also "indirectly connected" with another member in between. "Includes cases where it is. Additionally, when a part is said to “include” a certain component, this does not mean that other components are excluded, but that other components can be added, unless specifically stated to the contrary.

The terms used herein are only used to describe specific embodiments and are not intended to limit the invention. Singular expressions include plural expressions unless the context clearly dictates otherwise. In this specification, terms such as “comprise” or “have” are intended to indicate the presence of features, numbers, steps, operations, components, parts, or combinations thereof described in the specification, but are not intended to indicate the presence of one or more other features. It should be understood that this does not exclude in advance the possibility of the existence or addition of elements, numbers, steps, operations, components, parts, or combinations thereof.

Hereinafter, embodiments of the present invention will be described in detail with reference to the attached drawings.

Figure 1 is a block diagram showing a high-purity hydrogen production device using ammonia according to an embodiment of the present invention. Figure 2 is a block diagram showing a high-purity hydrogen production device using ammonia according to another embodiment of the present invention. Figure 3 is a block diagram showing a high-purity hydrogen production device using ammonia according to another embodiment of the present invention.

Referring to FIG. 1, a high-purity hydrogen production device (hereinafter, high-purity water tank production device) 10 using ammonia according to an embodiment of the present invention decomposes ammonia (NH 3 ) through an ammonia decomposition reaction, and then decomposes the ammonia (NH ₃ ) through an ammonia decomposition reaction. It may be a device for producing high purity hydrogen (H 2 ) by removing nitrogen (N ₂ ) and unreacted ammonia ( _{NH 3} ) from decomposition reaction products generated from the decomposition reaction.

The high-purity hydrogen production device 10 includes a combustion unit 100, a first ammonia supply unit (P10), a vaporization preheating unit 200, a second ammonia supply unit (P20), a decomposition reaction unit 300, and an adsorption unit. It may include a purification unit 400 and a hydrogen supply unit 500. In addition, the high-purity hydrogen production device 10 may further include a hydrogen storage unit (S10).

High-purity hydrogen separated and purified in the adsorption purification unit 400, which will be described later, can be stored in the hydrogen storage unit (S10). At this time, the hydrogen storage unit (S10) is described as a component included in the high-purity hydrogen production device 10, but the present invention is not limited thereto, and the hydrogen storage unit (S10) is disposed outside the high-purity hydrogen production device 10. It may also be a separate hydrogen storage infrastructure.

The combustion unit 100 can heat the decomposition reaction unit 300 to the temperature necessary to decompose ammonia. The combustion unit 100 is connected to the first ammonia supply unit (P10) and can receive ammonia from the first ammonia supply unit (P10). The combustion unit 100 can burn ammonia using air supplied from the outside and heat the decomposition reaction unit 300 using the reaction heat generated therefrom. Additionally, the combustion unit 100 may be supplied with off-gas discharged from the adsorption purification unit 400, which will be described later. In this case, the combustion unit 100 may heat the decomposition reaction unit 300 by burning the ammonia supplied from the first ammonia supply unit P10 together with the off gas.

The combustion unit 100 may heat the decomposition reaction unit 300 to a preset temperature. Here, the preset temperature may mean the temperature necessary for the ammonia decomposition reaction within the decomposition reaction unit 300 to start and reach a steady state, and may refer to the internal temperature of the decomposition reaction unit 300. It can be measured against a standard. At this time, the preset temperature may be, for example, 400°C or higher.

The vaporization preheating unit 200 can vaporize and preheat ammonia before it is supplied to the decomposition reaction unit 300. The vaporization preheating unit 200 may be connected to the second ammonia supply unit (P20). At this time, liquid ammonia may be stored in the second ammonia supply unit (P20). The vaporization preheating unit 200 may receive liquid ammonia from the second ammonia supply unit (P20). At this time, the vaporization preheating unit 200 may include a vaporizer 210 and a preheater 220.

The vaporizer 210 can phase change liquid ammonia into gaseous ammonia by vaporizing it. At this time, the vaporizer 210 can vaporize the liquid ammonia by receiving heat energy contained in the high-temperature reaction product discharged from the decomposition reaction unit 300.

The preheater 220 can increase the temperature or preheat the gaseous ammonia vaporized by the vaporizer 210. At this time, the preheater 220 may be connected to the vaporizer 210 through an intermediate connection line (IC). In this case, gaseous ammonia discharged from the vaporizer 210 may move to the preheater 220 through the intermediate connection line (IC). As an example, the preheater 220 can preheat gaseous ammonia by receiving heat from exhaust gas discharged from the combustion unit 100, passing through the decomposition reaction unit 300 and moving to the preheater 220. The preheated gaseous ammonia may be discharged from the preheater 220 and then supplied to the decomposition reaction unit 300.

The decomposition reaction unit 300 may receive ammonia from the vaporization preheating unit 200 and discharge a reaction product generated by decomposing the supplied ammonia. At this time, the reaction products may include nitrogen, hydrogen, and unreacted ammonia generated from the ammonia decomposition reaction. The reaction product discharged from the decomposition reaction unit 300 may be moved to the adsorption purification unit 400.

The adsorption purification unit 400 can separate and purify high-purity hydrogen from the reaction product of the ammonia decomposition reaction described above. The adsorption purification unit 400 may include an adsorbent. The adsorption purification unit 400 can purify high-purity hydrogen by removing nitrogen and unreacted ammonia contained in the reaction product using an adsorbent. The adsorbent may be, for example, activated carbon or zeolite, but is not limited thereto, and may include various materials that have a strong property of adsorbing gas or liquid.

As an example, the adsorption purification unit 400 can separate and purify high-purity hydrogen using a pressure swing adsorption (PSA) method. In this case, the adsorption purification unit 400 contains an adsorbent inside, and the reaction product can pass through the interior of the adsorption purification unit 400. When the reaction product passes, the internal pressure of the adsorption purification unit 400 can be adjusted to a preset pressure. The preset pressure may be about 8 atmospheres, but the present invention is not limited thereto.

In this way, while the reaction product passes through the adsorption purification unit 400 where the pressure is raised to a preset level, nitrogen and ammonia can be adsorbed and removed by the adsorbent. As a result, high-purity hydrogen can be separated and purified from the reaction product. Separated and purified high-purity hydrogen can be stored in the hydrogen storage unit (S10).

After separating and purifying hydrogen from the reaction product as described above, the internal pressure of the adsorption purification unit 400 may be reduced again. In this case, the nitrogen and ammonia adsorbed on the adsorbent are separated again, and thus off gas containing nitrogen, ammonia, and hydrogen remaining in the adsorption purification unit 400 may be generated. Off gas may be discharged from the adsorption purification unit 400 and supplied to the combustion unit 100. As described above, the off gas supplied to the combustion unit 100 is burned together with ammonia within the combustion unit 100 and can be used to heat the decomposition reaction unit 300.

The hydrogen supply unit 500 can supply hydrogen between the vaporizer 210 and the preheater 220. More specifically, the hydrogen supply unit 500 may supply hydrogen to the intermediate connection line (IC). At this time, the hydrogen supply unit 500 may include at least one of an external supply unit 510 and an internal supply unit 520.

The external supply unit 510 may be disposed outside the connection through which reaction products, ammonia, and high-purity hydrogen pass. The external supply unit 510 may be a hydrogen supply tank with hydrogen stored therein. The external supply unit 510 may supply the hydrogen stored inside to the intermediate connection line (IC) through a supply line.

The internal supply unit 520 is disposed at any one of the rear end of the decomposition reaction unit 300, the front or rear end of the adsorption purification unit 400, and the hydrogen storage unit (S10), and can supply hydrogen to the intermediate connection line (IC). there is. Here, the “front end” and “back end” refer to components (e.g., decomposition reaction unit 300 or adsorption) based on the direction in which ammonia, reaction products, or high purity hydrogen moves within the high-purity hydrogen production device 10. It may refer to the upstream and downstream sides of the purification unit 400, respectively.

Specifically, the internal supply unit 520 has a first connection line (C1) connecting the decomposition reaction unit 300 and the vaporizer 210, and a second connection line connecting the vaporizer 210 and the adsorption purification unit 400. It can be placed in either the line (C2), the third connection line (C3) that guides the high-purity hydrogen discharged from the adsorption purification unit (400) to the hydrogen storage unit (S10), or the hydrogen storage unit (S10). . Hereinafter, the internal supply part arranged in the first connection line (C1) will be referred to as the first supply part 521, the internal supply part arranged in the second connection line (C2) will be referred to as the second supply part 522, and the 3 The internal supply unit disposed in the connection line (C3) will be referred to as the third supply unit 523, and the internal supply unit disposed in the hydrogen storage unit (S10) will be referred to as the fourth supply unit 524.

The first supply unit 521 is disposed on the first connection line (C1) and can supply a portion of the reaction product discharged from the decomposition reaction unit 300 to the intermediate connection line (IC). Accordingly, part of the hydrogen, nitrogen, and unreacted ammonia contained in the reaction product discharged from the decomposition reaction unit 300 is moved to the intermediate connection line (IC), and can be supplied to the preheater 220 together with gaseous ammonia. .

The second supply unit 522 is disposed on the second connection line (C2) and can supply a portion of the reaction product supplied to the adsorption purification unit 400 to the intermediate connection line (IC). Accordingly, part of the hydrogen, nitrogen, and unreacted ammonia contained in the reaction product flowing into the adsorption purification unit 400 is moved to the intermediate connection line (IC), and can be supplied to the preheater 220 together with gaseous ammonia. .

The third supply unit 523 is disposed in the third connection line (C3) and can supply a portion of the high-purity hydrogen purified and discharged from the adsorption purification unit 400 to the intermediate connection line (IC). Accordingly, purified high-purity hydrogen can be supplied to the preheater 220 together with gaseous ammonia.

The fourth supply unit 524 is disposed in the hydrogen storage unit (S10) and can supply some of the high-purity hydrogen stored in the hydrogen storage unit (S10) to the intermediate connection line (IC). Accordingly, some of the stored high-purity hydrogen may be supplied to the preheater 220 along with gaseous ammonia.

Meanwhile, the present invention is not limited to providing only one internal supply unit 520 of the first supply unit 521, the second supply unit 522, the third supply unit 523, or the fourth supply unit 524, Two or more of the first to fourth supply units (521, 522, 523, and 524) may be provided simultaneously. In addition, although not shown in the drawings, it is of course possible to include additional internal supply units in addition to the above-mentioned supply units 521, 522, 523, and 524.

As described above, by supplying hydrogen (or reaction product) to the intermediate connection line (IC) through the external supply unit 510 or internal supply unit 520, the gaseous ammonia discharged from the vaporizer 210 is hydrogen (or reaction product). ) can be supplied to the preheater 220. As a result, it is possible to reduce corrosion of the decomposition reaction unit 300 caused by high-temperature ammonia supplied to the decomposition reaction unit 300 after being preheated by the preheater 220.

Referring to Figure 2, the high-purity hydrogen production device 20 according to another embodiment of the present invention includes a combustion unit 100, a first ammonia supply unit (P10), a vaporization preheating unit 200, and a second ammonia supply unit. It may include (P20), a decomposition reaction unit 300, an adsorption purification unit 400, and a hydrogen supply unit 500. Additionally, the high-purity hydrogen production device 10 may further include a hydrogen storage unit (S10). At this time, the combustion unit 100, the first ammonia supply unit (P10), the vaporization preheating unit 200, the second ammonia supply unit (P20), the decomposition reaction unit 300, the adsorption purification unit 400, and Since the specific features of the hydrogen supply unit 500 are the same or similar to those of the above-described embodiment, redundant description will be omitted. Hereinafter, the description will focus on the differences from the above-described embodiment (10).

The high-purity hydrogen production device 20 may include a hydrogen inlet point (B). The hydrogen inflow point (B) may be a location where hydrogen discharged from the hydrogen supply unit 500 flows in. At this time, the hydrogen inflow point (B) may be placed in a different position from the intermediate connection line (IC) within the high-purity hydrogen production device 20.

There may be at least one hydrogen inlet point (B). As an example, a plurality of hydrogen inflow points (B) may be provided. A plurality of hydrogen inflow points (B) may be arranged in different positions. In this case, the external supply unit 510 may supply hydrogen to one of the plurality of hydrogen inflow points (B) in addition to the hydrogen supplied to the intermediate connection line (IC).

The plurality of hydrogen inflow points (B) may include a first inflow point (B10) and a second inflow point (B20). The present invention is not limited to this, and the high-purity hydrogen production device 20 may further include an additional inlet point (not shown). However, for convenience of explanation, the high-purity hydrogen production device 20 includes the first and first 2 The description will focus on the embodiment provided with the inlet points (B10, B20).

The first inlet point (B10) may be disposed between the second ammonia supply unit (P20) and the vaporizer (210). More specifically, the first inlet point (B10) may be disposed in the first supply line (PA) that guides the ammonia discharged from the second ammonia supply unit (P20) to the vaporizer 210. Accordingly, hydrogen flowing into the first supply line (PA) from the external supply unit 510 through the first inflow point (B10) is supplied to the vaporizer 210 together with ammonia supplied from the second ammonia supply unit (P20). It can be.

The second inflow point (B20) may be disposed between the preheater 220 and the decomposition reaction unit 300. More specifically, the second inflow point (B20) may be disposed in the second supply line (PB) that guides the preheated gaseous ammonia discharged from the preheater 220 to the decomposition reaction unit 300. Accordingly, the hydrogen flowing from the external supply unit 510 to the second supply line (PB) through the second inflow point (B20) will be supplied to the decomposition reaction unit 300 together with the ammonia discharged from the preheater 220. You can.

As described above, the external supply unit 510 may supply hydrogen to either the first inflow point (B10) or the second inflow point (B20) in addition to supplying hydrogen to the intermediate connection line (IC). As a result, by increasing the amount of hydrogen supplied to the vaporizer 210, the preheater 220, or the decomposition reaction section 300, the decomposition reaction section 300 is corroded by the high temperature ammonia heated while passing through the vaporization preheater 200. can be reduced.

Referring to FIG. 3, the high-purity hydrogen production device 30 according to another embodiment of the present invention includes a combustion unit 100, a first ammonia supply unit (P10), a vaporization preheating unit 200, and a second ammonia It may include a supply unit (P20), a decomposition reaction unit 300, an adsorption purification unit 400, and a hydrogen supply unit 500. In addition, the high-purity hydrogen production device 10 may further include a hydrogen storage unit (S10). At this time, the combustion unit 100, the first ammonia supply unit (P10), the vaporization preheating unit 200, the second ammonia supply unit (P20), the decomposition reaction unit 300, the adsorption purification unit 400, and , Since the specific features of the hydrogen supply unit 500 are the same or similar to the above-described embodiment, redundant description will be omitted. Hereinafter, the description will focus on the differences from the above-described embodiment (10).

The high-purity hydrogen production device 30 may include both an internal supply unit 520 and a hydrogen inflow point (B). At this time, as described above, the internal supply unit 520 may include a first supply unit 521, a second supply unit 522, a third supply unit 523, and a fourth supply unit 524. And, the hydrogen inflow point (B) may include a first inflow point (B10) and a second inflow point (B20).

In this case, the external supply unit 510 may supply hydrogen to the intermediate connection line (IC) and, in addition, may supply hydrogen to either the first inflow point (B10) or the second inflow point (B10).

The internal supply unit 520 supplies hydrogen (or reaction product) from any one of the first to fourth supply units 521, 522, 523, and 524 to the intermediate connection line (IC), and in addition to the first inflow point ( Hydrogen (or reaction product) can be supplied to any one of B10) and the second inlet point (B10).

For example, when supplying a reaction product through the first supply unit 521, the first supply unit 521 supplies a portion of the reaction product discharged from the decomposition reaction unit 300 to the intermediate connection line (IC), In addition, the reaction product can be supplied to either the first inlet point (B10) or the second inlet point (B10). As another example, when supplying a reaction product through the second supply unit 522, the second supply unit 522 supplies a portion of the reaction product flowing into the adsorption purification unit 400 to the intermediate connection line (IC), and In addition, the reaction product can be supplied to either the first inlet point (B10) or the second inlet point (B10). As another example, the third supply unit 523 supplies a portion of the high-purity hydrogen discharged from the adsorption purification unit 400 to the intermediate connection line (IC), and in addition, the first inflow point (B10) and the second inflow point ( High purity hydrogen can be supplied with any one of B10). As another example, the fourth supply unit 524 supplies a portion of the high-purity hydrogen stored in the hydrogen storage unit (S10) to the intermediate connection line (IC), and in addition, the first inflow point (B10) and the second inflow point (B10) ) can supply high purity hydrogen.

In this way, not only the external supply unit 510 but also the internal supply unit 520 supplies hydrogen to the intermediate connection line (IC), and hydrogen is supplied to the first inflow point (B10) or the second inflow point (B20), It is possible to prevent corrosion of the “preheater 220,” the “decomposition reaction section 300,” and the “piping connecting the decomposition reaction section 300 from the rear end of the preheater 220” caused by high-temperature ammonia.

Figure 4 is a block diagram showing the steps of producing high-purity hydrogen using the high-purity hydrogen production apparatus using ammonia of Figures 1 to 3.

Referring to FIG. 4, a method (S10) for producing high-purity hydrogen using ammonia according to an embodiment of the present invention may be as follows.

First, the vaporizer 210 may vaporize the liquid ammonia supplied from the second ammonia supply unit (P20) and change the phase into gaseous ammonia (S110). At this time, the vaporizer 210 can vaporize ammonia by receiving heat energy contained in the high-temperature reaction product discharged from the decomposition reaction unit 300.

Next, the hydrogen supply unit 500 may supply hydrogen to the intermediate connection line (IC) (S120). Specifically, the hydrogen supply unit 500 may supply hydrogen to the intermediate connection line (IC) through either the external supply unit 510 or the internal supply unit 520.

As an example, the external supply unit 510 may supply hydrogen to the intermediate connection line (IC). In this case, hydrogen supplied by the external supply unit 510 may be supplied to the preheater 220 together with gaseous ammonia discharged from the vaporizer 210. Thereafter, in the preheater 220, the supplied gaseous ammonia and hydrogen can be heated to preheat the gaseous ammonia before being supplied to the decomposition reaction unit 300. The preheater 220 may supply preheated gaseous ammonia to the decomposition reaction unit 300 (S130).

As another embodiment, the internal supply unit 520 may supply hydrogen to the intermediate connection line (IC). At this time, the internal supply unit 520 includes, for example, a first supply unit 521, a second supply unit 522, a third supply unit 523, and a fourth supply unit 524, and first to fourth supply units ( Hydrogen (or reaction product) can be supplied to the intermediate connection line (IC) through any one of the supply units (521, 522, 523, 524). In this way, hydrogen (or reaction product) supplied from any one of the first to fourth supply parts 521, 522, 523, and 524 is supplied to the preheater 220 along with gaseous ammonia through the intermediate connection line (IC). You can.

As another embodiment, the hydrogen supply unit 500 may supply hydrogen to the hydrogen inflow point (B) located in a different position from the intermediate connection line (IC). At this time, the hydrogen inflow point (B) may include, for example, a first inflow point (B10) and a second inflow point (B20). In addition, the hydrogen supply unit 500 is supplied to the first inflow point (B10) or the second inflow point (B20) through the external supply unit 510 or any one of the first to fourth supply units (521, 522, 523, and 524). ) can supply hydrogen (or reaction product). Accordingly, the hydrogen (or reaction product) supplied from the hydrogen supply unit 500 is supplied to the decomposition reaction unit 300 together with preheated gaseous ammonia, or is supplied to the vaporizer 210 together with ammonia supplied from the second ammonia supply unit P20. ) can be supplied.

Meanwhile, the combustion unit 100 can heat the decomposition reaction unit 300 to a preset temperature by burning the ammonia supplied from the first ammonia supply unit (P10) (S100). Specifically, the combustion unit 100 may heat the decomposition reaction unit 300 to a preset temperature (eg, 400°C or higher) using combustion heat generated through the ammonia combustion reaction. At this time, the combustion unit 100 may burn the off-gas supplied from the adsorption purification unit 400 together with ammonia to generate combustion heat. Accordingly, the ammonia decomposition reaction may begin in the decomposition reaction unit 300. The combustion unit 100 may discharge combustion exhaust gas generated from an ammonia combustion reaction to the outside of the combustion unit 100.

Next, the decomposition reaction unit 300 decomposes ammonia and discharges the reaction product generated therefrom (S140). Specifically, the decomposition reaction unit 300 can decompose ammonia supplied from the vaporization preheating unit 200 (or preheater 220) using thermal energy generated by heating of the combustion unit 100. In addition, the decomposition reaction unit 300 can supply the reaction product generated from the ammonia decomposition reaction to the adsorption purification unit 400. At this time, the reaction product may be 'ammonia decomposition gas' containing hydrogen, nitrogen, and unreacted ammonia generated from the ammonia decomposition reaction.

Next, the adsorption purification unit 400 can separate and purify high-purity hydrogen from the reaction product (S150). Specifically, the adsorption purification unit 400 can receive the reaction product from the decomposition reaction unit 200 and remove nitrogen and unreacted ammonia contained in the reaction product. At this time, the adsorption purification unit 400 can selectively adsorb and remove only nitrogen and ammonia through pressure cycling adsorption (PSA) using the adsorbent contained therein. Thereafter, the separated and purified high-purity hydrogen can be discharged and stored in the hydrogen storage unit (S10).

The off gas generated during the adsorption and purification process (i.e., a mixed gas containing nitrogen, hydrogen, and unreacted ammonia) may be supplied to the combustion unit 100. Accordingly, the combustion unit 100 can heat the decomposition reaction unit 300 by co-combusting the ammonia supplied from the first ammonia supply unit P10, the hydrogen contained in the off gas, and a trace amount of unreacted ammonia. Through this process, the ammonia decomposition reaction in the decomposition reaction unit 300 and the adsorption purification in the adsorption purification unit 400 can be continuously performed.

Figure 5 shows the state before and after corrosion of the decomposition reaction zone by high-temperature ammonia in the case where hydrogen is not supplied to the intermediate connection line. Figure 6 shows the state before and after corrosion of the decomposition reaction zone by high-temperature ammonia when hydrogen is supplied to the intermediate connection line.

Referring to FIG. 5, FIG. 5(a) shows that in the case where hydrogen (or reaction product) is not supplied to the intermediate connection line (IC) and the hydrogen inlet point (B), high-temperature ammonia is supplied to the decomposition reaction unit 300. It shows the initial surface state of the decomposition reaction unit 300 before supply or at the time supply began. And, Figure 5(b) shows that high-temperature ammonia is supplied to the decomposition reaction unit 300 in a state in which hydrogen (or reaction product) is not supplied to the intermediate connection line (IC) and the hydrogen inlet point (B), thereby producing a predetermined amount of ammonia. The surface state of the decomposition reaction unit 300 is shown after time (eg, 24 hours) has passed. Comparing FIGS. 5(a) and 5(b), it can be seen that corrosion occurred on the surface of the decomposition reaction unit 300 due to the introduction of high-temperature ammonia, and the surface roughness increased.

In comparison, referring to FIG. 6, FIG. 6(a) shows the decomposition reaction section ( 300) shows the initial surface state. And, Figure 6(b) shows that in a state where hydrogen (or reaction product) is supplied to the intermediate connection line (IC) and the hydrogen inflow point (B), high-temperature ammonia is supplied to the decomposition reaction unit 300 for a predetermined period of time. The surface state of the decomposition reaction unit 300 is shown after (e.g., 24 hours). In this way, comparing Figures 6(a) and 6(b), when hydrogen (or reaction product) is supplied, the occurrence of surface corrosion of the decomposition reaction unit 300 due to high temperature ammonia is suppressed, It can be confirmed that the surface state of (300) is maintained in the initial surface state.

Figure 7 is a block diagram showing a high-purity hydrogen production device using ammonia according to another embodiment of the present invention.

Referring to FIG. 7, the high-purity hydrogen production device 30 according to another embodiment of the present invention includes a combustion unit 100, a first ammonia supply unit (P10), a vaporization preheating unit 200, and a second ammonia supply unit 100. It may include an ammonia supply unit (P20), a decomposition reaction unit 300, an adsorption purification unit 400, and a catalytic reaction unit 600. In addition, the high-purity hydrogen production device 10 may further include a hydrogen storage unit (S10). At this time, the combustion unit 100, the first ammonia supply unit (P10), the vaporization preheating unit 200, the second ammonia supply unit (P20), the decomposition reaction unit 300, and the adsorption purification unit 400. Since specific features are the same or similar to the above-described embodiments, overlapping descriptions will be omitted. Hereinafter, the description will focus on differences from the above-described embodiments 10 and 20.

The catalytic reaction unit 600 can decompose ammonia discharged from the preheater 220 and produce hydrogen. At this time, the catalytic reaction unit 600 may be provided separately from the preheater 220 and disposed between the preheater 220 and the decomposition reaction unit 300. However, the present invention is not limited to this, and although not shown in the drawings, the catalytic reaction unit 600 is configured to fill the inner space of the preheater 220 with a catalyst, or is formed in the form of a catalyst coating layer inside the preheater 220. It may be composed of:

The catalytic reaction unit 600 can produce hydrogen by decomposing a portion of the preheated gaseous ammonia discharged from the preheater 220 through a catalytic decomposition reaction. At this time, catalysts used in the catalytic decomposition reaction of ammonia may include, for example, pellet catalysts, monolithic catalysts, and metal form catalysts, but are not limited thereto.

As an example, in the catalytic reaction unit 600, an ammonia catalytic decomposition reaction may be performed using the heat energy contained in the gaseous ammonia preheated by the preheater 220. As another example, the catalytic reaction unit 600 may be provided with an electric heating unit (not shown). In this case, the electric heating unit may be installed outside or inside the main body (not shown) of the catalytic reaction unit 600, and includes a heat source (not shown) for generating heat, and heat generated from the heat source to the catalytic decomposition unit 600. ) may be provided with a heat transfer unit (e.g., a heat wire) for transferring it to the main body. As the catalytic reaction unit 600 is heated by the heat source and heat transfer unit of the electric heating unit, the internal temperature of the catalytic decomposition unit 600 rises to the temperature required for the catalytic decomposition reaction of ammonia, and ammonia is decomposed. , a 'mixture' of ammonia, nitrogen and hydrogen can be produced.

In this way, a part of the gaseous ammonia supplied from the catalytic reaction unit 600 to the decomposition reaction unit 300 is catalytically decomposed to produce hydrogen and supplied to the decomposition reaction unit 300, from the second ammonia supply unit P20. The supplied ammonia may be supplied to the decomposition reaction unit 300 together with the hydrogen produced by the catalytic reaction unit 600. Accordingly, corrosion of the decomposition reaction unit 300 as the ammonia decomposition reaction progresses in the decomposition reaction unit 300 can be suppressed.

FIG. 8 is a block diagram showing the steps of producing high-purity hydrogen using the high-purity hydrogen production device using ammonia of FIG. 7.

Referring to FIG. 8, a method (S20) for producing high-purity hydrogen using ammonia according to another embodiment of the present invention may be as follows.

First, the vaporizer 210 may vaporize the liquid ammonia supplied from the second ammonia supply unit (P20) and change the phase into gaseous ammonia (S210). At this time, the vaporizer 210 can vaporize ammonia by receiving heat energy contained in the high-temperature reaction product discharged from the decomposition reaction unit 300.

Thereafter, the gaseous ammonia discharged from the vaporizer 210 may be supplied to the preheater 220. In the preheater 220, the supplied gaseous ammonia can be heated to preheat the gaseous ammonia before it is supplied to the decomposition reaction unit 300. The preheater 220 may supply preheated gaseous ammonia to the decomposition reaction unit 300 (S220).

Meanwhile, the combustion unit 100 can heat the decomposition reaction unit 300 to a preset temperature by burning the ammonia supplied from the first ammonia supply unit (P10) (S100). Specifically, the combustion unit 100 may heat the decomposition reaction unit 300 to a preset temperature (eg, 400°C or higher) using combustion heat generated through the ammonia combustion reaction. At this time, the combustion unit 100 may burn the off-gas supplied from the adsorption purification unit 400 together with ammonia to generate combustion heat. Accordingly, the ammonia decomposition reaction may begin in the decomposition reaction unit 200. The combustion unit 100 may discharge combustion exhaust gas generated from an ammonia combustion reaction to the outside of the combustion unit 100.

Next, the catalytic reaction unit 600 can produce hydrogen by decomposing the preheated gaseous ammonia (S230). Specifically, the catalytic reaction unit 600 may produce hydrogen by decomposing some of the preheated gaseous ammonia discharged from the preheater 220 through a catalytic decomposition reaction. Accordingly, the ‘unreacted ammonia’ discharged from the preheater 220 and the ‘nitrogen and hydrogen’ generated by the catalytic reaction unit 600 can be supplied to the decomposition reaction unit 300.

Next, the decomposition reaction unit 300 decomposes ammonia and discharges the reaction product generated therefrom (S240). Specifically, the decomposition reaction unit 300 may decompose ammonia supplied after being discharged from the preheater 220 and passing through the catalytic reaction unit 600. At this time, the decomposition reaction unit 300 can decompose ammonia through an ammonia decomposition reaction that proceeds using thermal energy generated by heating of the combustion unit 100. In addition, the decomposition reaction unit 300 can supply the reaction product generated from the ammonia decomposition reaction to the adsorption purification unit 400. At this time, the reaction product may be 'ammonia decomposition gas' containing hydrogen, nitrogen, and unreacted ammonia generated from the ammonia decomposition reaction.

Next, the adsorption purification unit 400 can separate and purify high-purity hydrogen from the reaction product (S250). Specifically, the adsorption purification unit 400 can receive the reaction product from the decomposition reaction unit 200 and remove nitrogen and unreacted ammonia contained in the reaction product. At this time, the adsorption purification unit 400 can selectively adsorb and remove only nitrogen and ammonia through pressure cycling adsorption (PSA) using the adsorbent contained therein. Thereafter, the separated and purified high-purity hydrogen can be discharged and stored in the hydrogen storage unit (S10).

The off gas generated during the adsorption and purification process (i.e., a mixed gas containing nitrogen, hydrogen, and unreacted ammonia) may be supplied to the combustion unit 100. Accordingly, the combustion unit 100 can heat the decomposition reaction unit 300 by co-combusting the ammonia supplied from the first ammonia supply unit P10, the hydrogen contained in the off gas, and a trace amount of unreacted ammonia. Through this process, the ammonia decomposition reaction in the decomposition reaction unit 300 and the adsorption purification in the adsorption purification unit 400 can be continuously performed, which is the same or similar to the above-described embodiment.

As described above, the high-purity hydrogen production apparatus (10, 20, 30, 40) and production method (S10) according to the embodiments of the present invention include, in addition to the hydrogen supply unit (500), the rear end of the decomposition reaction unit (300). , an internal supply unit 520 is provided at the front or rear end of the adsorption purification unit 400 and the hydrogen storage unit S10, and hydrogen is additionally supplied from this to the intermediate connection line (IC), thereby producing high-temperature gaseous ammonia, It is possible to suppress the occurrence of corrosion in the “preheater 220,” “decomposition reaction section 300,” and “piping connecting the rear end of the preheater 220 and the decomposition reaction section 300.” In addition, in addition to the intermediate connection line (IC), there is further provided a hydrogen inlet point (B) through which hydrogen is supplied from the hydrogen supply unit 500, and hydrogen is additionally supplied to these inflow points, thereby causing decomposition by high-temperature gaseous ammonia. Corrosion problems occurring in the reaction unit 300 (i.e., corrosion of the metal reaction unit body constituting the decomposition reaction unit 300, filling materials and catalysts in the decomposition reaction unit 300) can be solved.

In addition, the high-purity hydrogen production apparatus 30 and production method (S20) according to embodiments of the present invention produce hydrogen by catalytically decomposing some of the preheated gaseous ammonia before being supplied to the decomposition reaction unit 300. By supplying the decomposition reaction unit 300 together with gaseous ammonia, the above-described corrosion problem of the decomposition reaction unit 300 caused by high-temperature gaseous ammonia can be prevented.

The description of the present invention described above is for illustrative purposes, and those skilled in the art will understand that the present invention can be easily modified into other specific forms without changing the technical idea or essential features of the present invention. will be. Therefore, the embodiments described above should be understood in all respects as illustrative and not restrictive. For example, each component described as unitary may be implemented in a distributed manner, and similarly, components described as distributed may also be implemented in a combined form.

The scope of the present invention is indicated by the claims described below, and all changes or modified forms derived from the meaning and scope of the claims and their equivalent concepts should be construed as being included in the scope of the present invention.

10, 20, 30, 40: High-purity hydrogen production device
100: Combustion unit
200: Evaporation preheating unit
210: carburetor
220: Preheater
300: Decomposition reaction unit
400: Adsorption purification unit
500: Hydrogen supply unit
510: External supply unit
520: Internal supply couple
600: Catalytic reaction unit
P10: Primary ammonia supply section
P20: Secondary ammonia supply section
S10: Hydrogen storage unit
IC: intermediate connection line
B: Hydrogen inflow point

Claims (15)

a decomposition reaction unit that decomposes ammonia through an ammonia decomposition reaction and discharges reaction products including hydrogen, nitrogen, and unreacted ammonia generated from the ammonia decomposition reaction;
a combustion unit that heats the decomposition reaction unit by burning ammonia supplied from the first ammonia supply unit;
A vaporization preheating unit including a vaporizer for vaporizing liquid ammonia supplied from the second ammonia supply unit and a preheater for preheating the ammonia supplied from the vaporizer through an intermediate connection line;
A hydrogen supply unit that supplies hydrogen to the intermediate connection line; and
An apparatus for producing high-purity hydrogen using ammonia, comprising: an adsorption purification unit that separates and purifies high-purity hydrogen from the reaction product. According to claim 1,
The hydrogen supply unit includes an internal supply unit disposed at any one of the rear end of the decomposition reaction unit, the front or rear end of the adsorption purification unit, and a hydrogen storage unit where separated and purified high-purity hydrogen is stored, and the reaction product, the ammonia, and the high-purity hydrogen. A high-purity hydrogen production device using ammonia, including at least one of an external supply unit disposed outside the connection line through which hydrogen passes. According to clause 2,
The internal supply department,
A first supply unit for supplying a part of the reaction product discharged from the decomposition reaction unit to the intermediate connection line; A second supply unit for supplying a part of the reaction product supplied to the adsorption purification unit to the intermediate connection line; A third supply unit that supplies a portion of the high-purity hydrogen separated, purified, and discharged from the adsorption purification unit to the intermediate connection line; and a fourth supply portion that supplies a portion of the high-purity hydrogen stored in the hydrogen storage unit to the intermediate connection line. ; A high-purity hydrogen production device using ammonia, comprising at least one of the following. According to claim 1,
The hydrogen supply unit is a high-purity hydrogen production device using ammonia that supplies hydrogen to a hydrogen inflow point located in a different position from the intermediate connection line. According to clause 4,
The hydrogen inflow point is provided in a plurality of different ways,
The hydrogen supply unit is a high-purity hydrogen production device using ammonia that supplies hydrogen to at least one of the plurality of hydrogen inflow points. According to clause 5,
The hydrogen inflow point is,
A first inlet point connected to a first supply line connecting the second ammonia supply unit and the vaporizer; and a second inflow point connected to a second supply line connecting the preheater and the decomposition reaction unit; A high-purity hydrogen production device using ammonia, comprising at least one of the following. A vaporizer producing gaseous ammonia by vaporizing liquid ammonia supplied from a second ammonia supply unit;
A hydrogen supply unit supplying hydrogen to an intermediate connection line connecting the vaporizer and the preheater;
The preheater preheats the gaseous ammonia and supplies it to the decomposition reaction unit;
A combustion unit combusting ammonia supplied from the first ammonia supply unit to heat the decomposition reaction unit;
Decomposing ammonia in the decomposition reaction unit through an ammonia decomposition reaction to discharge reaction products including hydrogen, nitrogen, and unreacted ammonia; and
A method for producing high-purity hydrogen using ammonia, comprising: an adsorption purification unit adsorbing and removing nitrogen and unreacted ammonia from the reaction product to separate and purify high-purity hydrogen. According to clause 7,
A method for producing high-purity hydrogen using ammonia, further comprising: an internal supply unit supplying a reaction product or hydrogen to the intermediate connection line. According to clause 8,
The internal supply department,
A first supply unit for supplying a part of the reaction product discharged from the decomposition reaction unit to the intermediate connection line; A second supply unit for supplying a part of the reaction product supplied to the adsorption purification unit to the intermediate connection line; At least one of a third supply unit supplying a portion of the high-purity hydrogen separated and purified in the adsorption purification unit to the intermediate connection line; and a fourth supply portion supplying a portion of the high-purity hydrogen stored in the hydrogen storage unit to the intermediate connection line. A method for producing high purity hydrogen using ammonia, including. According to clause 7,
A method for producing high-purity hydrogen using ammonia, further comprising: supplying hydrogen, by the hydrogen supply unit, to a hydrogen inflow point disposed in a different position from the intermediate connection line. According to claim 10,
The hydrogen inflow point is,
A first inlet point connected to a first supply line connecting the second ammonia supply unit and the vaporizer; and a second inflow point connected to a second supply line connecting the preheater and the decomposition reaction unit; A method for producing high-purity hydrogen using ammonia, comprising at least one of the following. a decomposition reaction unit that decomposes ammonia through an ammonia decomposition reaction and discharges reaction products including hydrogen, nitrogen, and unreacted ammonia generated from the ammonia decomposition reaction;
a combustion unit that burns ammonia supplied from the first ammonia supply unit to heat the decomposition reaction unit;
A vaporization preheating unit including a vaporizer for vaporizing liquid ammonia supplied from the second ammonia supply unit and a preheater for preheating the ammonia supplied from the vaporizer through an intermediate connection line;
A catalytic reaction unit that decomposes some of the preheated ammonia through a catalytic reaction to produce hydrogen; and
An apparatus for producing high-purity hydrogen using ammonia, comprising an adsorption purification unit that separates and purifies high-purity hydrogen from the reaction product. According to claim 12,
A high-purity hydrogen production device using ammonia, wherein the hydrogen produced in the catalytic reaction section is supplied to the decomposition reaction section. According to claim 12,
The catalytic reaction is a high-purity hydrogen production device using ammonia, which is carried out using heat energy contained in ammonia heated by the preheater. According to claim 12,
The catalytic reaction is a high-purity hydrogen production device using ammonia, which is carried out using an electric heating method.

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