JP7414933B1 - High purity hydrogen production equipment and production method using ammonia - Google Patents

Abstract

The present invention provides an apparatus and method for producing high-purity hydrogen using ammonia that solves the problem of corrosion occurring in a decomposition reactor in a hydrogen production process using an ammonia decomposition reaction. A decomposition reaction section that decomposes ammonia through an ammonia decomposition reaction and discharges a reaction product containing hydrogen, nitrogen, and unreacted ammonia generated from the ammonia decomposition reaction, and a first ammonia supply section that decomposes ammonia. a combustion section that heats the decomposition reaction section by burning ammonia, a vaporizer that vaporizes liquid ammonia supplied from a second ammonia supply section, and ammonia supplied from the vaporizer via an intermediate connection line. a vaporization preheating section having a preheater for preheating hydrogen, a hydrogen supply section for supplying hydrogen to the intermediate connection line, and an adsorption purification section for separating and purifying high purity hydrogen from the reaction product. [Selection diagram] Figure 1

Description

The present invention relates to an apparatus and method, and more particularly, to an 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 (NH ₃ → N ₂ + 3H ₂ ), and is an endothermic reaction that requires approximately 46 kJ/mol of heat. shall be. This method of producing hydrogen through an ammonia decomposition reaction is widely used to produce high-purity hydrogen required in common gas-related industries or semiconductor and LCD factories.

Generally, when producing hydrogen through an ammonia decomposition reaction, ammonia at room temperature is preheated to a high temperature through heat exchange and then supplied to a decomposition reactor. The disadvantage is that it corrodes the piping and the cracking reactor, resulting in a shortened life span of the production equipment. Furthermore, if the preheater, the piping connecting the rear end of the preheater to the decomposition reactor, and the decomposition reactor are continuously exposed to high-temperature ammonia, serious corrosion problems may occur when nitriding is carried out. There is.

The technical problem to be solved by the present invention is to prevent corrosion in the preheater and the piping connecting the preheater and the decomposition reactor due to high-temperature ammonia in the hydrogen production process using an ammonia decomposition reaction. Corrosion problems occur in decomposition reactors where high-temperature ammonia flows through such piping (i.e., corrosion of the metal reactor body, the packing inside the decomposition reactor, the catalyst, etc.) ) An object of the present invention is to provide an apparatus and method for producing high-purity hydrogen using ammonia, which can solve the problem.

The technical problems to be solved by the present invention are not limited to the above-mentioned technical problems, and other unmentioned technical problems can be solved from the following description by those who are common knowledge in the technical field to which the present invention belongs. It should be clearly understandable for those who have the following.

In order to achieve the above technical problem, an apparatus for producing high purity hydrogen using ammonia according to an embodiment of the present invention decomposes ammonia through an ammonia decomposition reaction, and hydrogen generated from the ammonia decomposition reaction, a decomposition reaction section that discharges a reaction product containing nitrogen and unreacted ammonia; a combustion section that heats the decomposition reaction section by burning ammonia supplied from a first ammonia supply section; and a second ammonia supply. a vaporization preheating section having a vaporizer for vaporizing liquid ammonia supplied from the section, and a preheater for preheating the ammonia supplied from the vaporizer via the intermediate connection line; The hydrogen supply unit may include a hydrogen supply unit that supplies hydrogen, and an adsorption purification unit that separates and purifies high-purity hydrogen from the reaction product.

In an embodiment of the present invention, the hydrogen supply section includes a rear end of the decomposition reaction section, a front end or a rear end of the adsorption purification section, and a hydrogen storage section in which separated and purified high-purity hydrogen is stored. an internal supply section disposed in any one of the above, and an external supply section disposed outside the connection line through which the reaction product, the ammonia, and the high-purity hydrogen pass. You can.

In an embodiment of the present invention, the internal supply section is supplied to a first supply section that supplies a part of the reaction product discharged from the decomposition reaction section to the intermediate connection line, and to the adsorption purification section. a second supply section that supplies a portion of the reaction product to the intermediate connection line; and a third supply section that supplies a portion of the high-purity hydrogen separated and purified in the adsorption purification section and discharged to the intermediate connection line. and a fourth supply section that supplies a portion of the high-purity hydrogen stored in the hydrogen storage section 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, a plurality of different hydrogen inflow points may be provided, 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 includes a first inflow point connected to a first supply line connecting the second ammonia supply unit and the vaporizer, and a first inflow point connected to the preheater and the decomposition reaction and a second inflow point connected to a second supply line connecting the part.

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 a vaporizer that vaporizes liquid ammonia supplied from a second ammonia supply section. a step in which a hydrogen supply unit supplies hydrogen to an intermediate connecting line connecting the vaporizer and a preheater; and a step in which the preheater preheats the gaseous ammonia to cause a decomposition reaction. a step in which the combustion section burns the ammonia supplied from the first ammonia supply section to heat the decomposition reaction section; and the decomposition reaction section decomposes ammonia through the ammonia decomposition reaction. and discharging reaction products containing hydrogen, nitrogen, and unreacted ammonia; and an adsorption purification unit adsorbing and removing nitrogen and unreacted ammonia from the reaction products to separate and purify high-purity hydrogen. It may include steps.

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 section is supplied to a first supply section that supplies a part of the reaction product discharged from the decomposition reaction section to the intermediate connection line, and to the adsorption purification section. a second supply section that supplies a portion of the reaction product to the intermediate connection line; and a third supply section that supplies a portion of the high-purity hydrogen separated and purified in the adsorption purification section to the intermediate connection line. and a fourth supply section that supplies a portion of the high-purity hydrogen stored in the hydrogen storage section to the intermediate connection line.

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

In an embodiment of the present invention, the hydrogen inflow point includes a first inflow point connected to a first supply line connecting the second ammonia supply unit and the vaporizer, and a first inflow point connected to the preheater and the decomposition reaction and a second inflow point connected to a second supply line connecting the parts.

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

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

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

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

The high-purity hydrogen production apparatus and production method according to the embodiment of the present invention provides 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. By further supplying , it is possible to suppress the occurrence of corrosion in the preheater, the decomposition reaction section, and the piping connecting the rear end of the preheater and the decomposition reaction section due to high-temperature gaseous ammonia. In addition, by further supplying hydrogen to the hydrogen inflow point in addition to the space between the vaporizer and the preheater, corrosion of the decomposition reaction part due to high temperature gas phase ammonia can be prevented.

In addition, the high-purity hydrogen production apparatus and production method according to the embodiment of the present invention catalytically decomposes a part of preheated gas phase ammonia to produce hydrogen before being supplied to the decomposition reaction section. By supplying the decomposition reaction part together with gaseous ammonia, corrosion of the decomposition reaction part by high temperature gaseous ammonia can be prevented.

The effects of the present invention are not limited to the above-mentioned effects in any way, and include all effects that can be inferred from the structure of the invention described in the detailed description of the invention or the claims.

FIG. 1 is a block diagram showing an apparatus for producing high-purity hydrogen using ammonia according to an embodiment of the present invention. FIG. 2 is a block diagram showing an apparatus for producing high-purity hydrogen using ammonia according to another embodiment of the present invention. FIG. 2 is a block diagram showing an apparatus for producing high-purity hydrogen using ammonia according to yet another embodiment of the present invention. FIG. 4 is a block diagram showing a procedure for producing high-purity hydrogen using the high-purity hydrogen production apparatus using ammonia shown in FIGS. 1 to 3. FIG. FIG. 6 is a diagram showing the state before and after corrosion occurs in the decomposition reaction section due to high-temperature ammonia when hydrogen is not supplied to the intermediate connection line. FIG. 6 is a diagram showing the state before and after corrosion occurs in the decomposition reaction part due to high temperature ammonia when hydrogen is supplied to the intermediate connection line. FIG. 2 is a block diagram showing an apparatus for producing high-purity hydrogen using ammonia according to yet another embodiment of the present invention. 8 is a block diagram showing a procedure for producing high-purity hydrogen using the high-purity hydrogen production apparatus using ammonia in FIG. 7. FIG.

The present invention will be explained in detail below based on the accompanying drawings. However, this invention may be embodied in a variety of different forms and is therefore not limited to the embodiments described herein. In the drawings, in order to clearly explain the present invention, parts unrelated to the explanation are omitted, and similar parts are given similar drawing symbols throughout the specification.

Throughout the specification, when a certain part is said to be "connected (connected, contacted, combined)" with another part, this does not mean only when they are "directly connected"; This also includes cases in which they are "indirectly connected" with other members sandwiched between them. Note that when a part is said to "comprise" a certain component, this does not exclude other components, unless otherwise specified, and does not mean that it may further include other components. means.

The terminology used herein is merely used to describe particular embodiments and is not intended to limit the invention. The singular expression includes plural phrases unless the context clearly indicates otherwise. As used herein, the words "comprising" or "having" are used only to specify the presence of a feature, number, step, act, component, part, or combination thereof described in the specification. does not exclude in advance the existence or possibility of the addition of one or more other features, figures, steps, acts, components, parts or combinations thereof.

Hereinafter, embodiments of the present invention will be described in detail based on the accompanying drawings.

FIG. 1 is a block diagram showing an apparatus for producing high-purity hydrogen using ammonia according to an embodiment of the present invention. FIG. 2 is a block diagram showing an apparatus for producing high-purity hydrogen using ammonia according to another embodiment of the present invention. FIG. 3 is a block diagram showing an apparatus for producing high-purity hydrogen using ammonia according to yet another embodiment of the present invention.

Referring to FIG. 1, an apparatus 10 for producing high-purity hydrogen using ammonia (hereinafter referred to as a high-purity hydrogen production apparatus) according to an embodiment of the present invention converts ammonia ( _NH3 ) through an ammonia decomposition reaction. It may be an apparatus for producing high purity hydrogen (H ₂ ) by removing nitrogen (N ₂ ) and unreacted ammonia (NH ₃ ) from the decomposition reaction product generated from the decomposition reaction after decomposition. .

The high-purity hydrogen production device 10 includes a combustion section 100, a first ammonia supply section P10, a vaporization preheating section 200, a second ammonia supply section P20, a decomposition reaction section 300, an adsorption purification section 400, The hydrogen supply unit 500 may also be provided. Note that the high-purity hydrogen production apparatus 10 may further include a hydrogen storage section S10.

The hydrogen storage section S10 may store high-purity hydrogen separated and purified in an adsorption purification section 400, which will be described later. At this time, the hydrogen storage section S10 is described as a component incorporated in the high-purity hydrogen production apparatus 10, but the present invention is not limited to this in any way, and the hydrogen storage section S10 is It may also be a separate hydrogen storage infrastructure located outside the manufacturing apparatus 10.

The combustion section 100 can heat the decomposition reaction section 300 to a temperature necessary to decompose ammonia. The combustion part 100 is connected to the first ammonia supply part P10, and can be supplied with ammonia from the first ammonia supply part P10. The combustion section 100 can combust ammonia using air supplied from the outside, and can heat the decomposition reaction section 300 using the reaction heat generated from the ammonia. Note that the combustion section 100 can be supplied with off-gas discharged from an adsorption purification section 400, which will be described later. In such a case, the combustion section 100 can heat the decomposition reaction section 300 by burning the ammonia supplied from the first ammonia supply section P10 together with the off-gas.

The combustion section 100 can heat the decomposition reaction section 300 to a preset temperature. Here, the preset temperature may refer to the temperature required for the ammonia decomposition reaction in the decomposition reaction section 300 to start and reach a steady state, and the internal temperature of the decomposition reaction section 300 is It may be measured as a reference. At this time, the preset temperature may be, for example, 400° C. or higher.

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

The vaporizer 210 can change the phase of liquid ammonia into gaseous ammonia by vaporizing it. At this time, the vaporizer 210 may be supplied with thermal energy contained in the high temperature reaction product discharged from the decomposition reaction unit 300 to vaporize the liquid ammonia.

The preheater 220 can raise or preheat the vapor phase ammonia vaporized by the vaporizer 210. At this time, the preheater 220 may be connected to the carburetor 210 through an intermediate connection line IC. In such a case, the vaporized ammonia discharged from the vaporizer 210 may be transferred to the preheater 220 via the intermediate connection line IC. In one embodiment, the preheater 220 is supplied with heat from the exhaust gas that has been discharged from the combustion section 100 and then moved to the preheater 220 through the decomposition reaction section 300 to preheat the vapor phase ammonia. can. The preheated gas phase ammonia may be supplied to the decomposition reaction section 300 after being discharged from the preheater 220.

The decomposition reaction section 300 is supplied with ammonia from the vaporization preheating section 200, and can decompose the supplied ammonia and discharge a reaction product generated. At this time, the reaction product may include nitrogen, hydrogen, and unreacted ammonia produced from the ammonia decomposition reaction. The reaction product discharged from the decomposition reaction section 300 may be moved to the adsorption purification section 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 contain various substances that have a strong property of adsorbing gas or liquid. good.

In one embodiment, the adsorption purification unit 400 can separate and purify high-purity hydrogen using a pressure swing adsorption (PSA) method. In such a case, the adsorption purification unit 400 may include an adsorbent therein, and the reaction product may pass through the adsorption purification unit 400. When the reaction product passes through, the internal pressure of the adsorption purification section 400 may be adjusted to a preset pressure. The preset pressure may be approximately 8 atmospheres, but the present invention is not limited thereto.

In this way, nitrogen and ammonia may be adsorbed and removed by the adsorbent while the reaction product passes through the adsorption purification unit 400 where the pressure is increased to a preset value. This makes it possible to separate and purify high-purity hydrogen from the reaction product. The separated and purified high-purity hydrogen may be stored in the hydrogen storage section S10.

As described above, after hydrogen is separated and purified from the reaction product, the internal pressure of the adsorption purification unit 400 may be reduced again. In such a case, the nitrogen and ammonia adsorbed on the adsorbent will be separated again, and as a result, an off-gas containing nitrogen, ammonia, and hydrogen remaining in the adsorption purification section 400 can be generated. become. The off-gas may be discharged from the adsorption purification section 400 and supplied to the combustion section 100. In this way, the off-gas supplied to the combustion section 100 is burned together with ammonia in the combustion section 100 and can be used to heat the decomposition reaction section 300, as described above.

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

The external supply 510 may be located outside the connection line through which the reaction products, ammonia and high purity hydrogen pass. The external supply unit 510 may be a hydrogen supply tank in which hydrogen is stored. The external supply unit 510 can supply internally stored hydrogen to the intermediate connection line IC via a supply line.

The internal supply section 520 is disposed at any one of the rear end of the decomposition reaction section 300, the front end or rear end of the adsorption purification section 400, and the hydrogen storage section S10, and supplies hydrogen to the intermediate connection line IC. Can be done. Here, "front end" and "rear end" refer to components [e.g., decomposition reaction section 300 or the upstream side and the downstream side of the adsorption purification unit 400].

Specifically, the internal supply section 520 connects a first connection line C1 that connects the decomposition reaction section 300 and the vaporizer 210, a second connection line C2 that connects the vaporizer 210 and the adsorption purification section 400, and an adsorption purification section. It may be arranged in either the third connection line C3 that guides high-purity hydrogen discharged from the section 400 to the hydrogen storage section S10, or the hydrogen storage section S10. Hereinafter, the internal supply section disposed on the first connection line C1 will be referred to as the first supply section 521, the internal supply section disposed on the second connection line C2 will be referred to as the second supply section 522, and the internal supply section disposed on the second connection line C2 will be referred to as the second supply section 522. The internal supply section disposed in the connection line C3 of No. 3 is referred to as a third supply section 523, and the internal supply section disposed in the hydrogen storage section S10 is referred to as a fourth supply section 524.

The first supply unit 521 is disposed in 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. As a result, some of the hydrogen, nitrogen, and unreacted ammonia contained in the reaction products discharged from the decomposition reaction section 300 move to the intermediate connection line IC, and are supplied to the preheater 220 together with gaseous ammonia. It becomes possible to

The second supply unit 522 is disposed in 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. As a result, some of the hydrogen, nitrogen, and unreacted ammonia contained in the reaction products flowing into the adsorption purification section 400 move to the intermediate connection line IC, and are supplied to the preheater 220 together with gaseous ammonia. becomes possible.

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 in the adsorption purification unit 400 to the intermediate connection line IC. This allows purified high-purity hydrogen to be supplied to the preheater 220 together with vapor phase ammonia.

The fourth supply unit 524 is disposed in the hydrogen storage unit S10 and can supply a portion of the high-purity hydrogen stored in the hydrogen storage unit S10 to the intermediate connection line IC. This allows a portion of the stored high-purity hydrogen to be supplied to the preheater 220 together with gaseous ammonia.

On the other hand, the present invention has nothing to do with having only one internal supply section 520 among the first supply section 521, the second supply section 522, the third supply section 523, or the fourth supply section 524. The present invention is not limited to this, and two or more of the first to fourth supply sections 521, 522, 523, and 524 may be provided at the same time. Although not shown, it goes without saying that an additional internal supply section may be provided in addition to the supply sections 521, 522, 523, and 524 described above.

As described above, by supplying hydrogen (or a reaction product) to the intermediate connection line IC via the external supply section 510 or the internal supply section 520, the gaseous ammonia discharged from the vaporizer 210 is converted into hydrogen (or , reaction products) to the preheater 220. Thereby, it is possible to reduce corrosion of the decomposition reaction section 300 due to the high temperature ammonia supplied to the decomposition reaction section 300 after being preheated by the preheater 220.

Referring to FIG. 2, a high-purity hydrogen production apparatus 20 according to another embodiment of the present invention includes a combustion section 100, a first ammonia supply section P10, a vaporization preheating section 200, and a second ammonia supply section. P20, a decomposition reaction section 300, an adsorption purification section 400, and a hydrogen supply section 500. Note that the high-purity hydrogen production apparatus 10 may further include a hydrogen storage section S10. At this time, specific details of the combustion section 100, the first ammonia supply section P10, the vaporization preheating section 200, the second ammonia supply section P20, the decomposition reaction section 300, the adsorption purification section 400, and the hydrogen supply section 500 are specified. Since the features are the same or similar to those of the embodiments described above, overlapping explanations will be omitted. The following description will focus on the differences from the tenth embodiment described above.

The high-purity hydrogen production device 20 may include a hydrogen inflow point B. The hydrogen inflow point B may be a position into which hydrogen discharged from the hydrogen supply section 500 flows. At this time, the hydrogen inflow point B may be arranged at a different position from the intermediate connection line IC in the high-purity hydrogen production apparatus 20.

At least one hydrogen inflow point B may be provided. In one embodiment, a plurality of hydrogen inflow points B may be provided. The plurality of hydrogen inflow points B may be arranged at mutually different positions. In such a case, the external supply unit 510 may supply hydrogen to any 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 thereto, and the high-purity hydrogen production apparatus 20 may further include an additional inlet point (not shown). The description will focus on an embodiment in which the pure hydrogen production apparatus 20 includes first and second inflow points B10 and B20.

The first inflow point B10 may be arranged between the second ammonia supply section P20 and the vaporizer 210. More specifically, the first inflow point B10 may be arranged in the first supply line PA that leads the ammonia discharged from the second ammonia supply part P20 to the vaporizer 210. Thereby, the hydrogen that has flowed into the first supply line PA from the external supply section 510 via the first inflow point B10 is supplied to the vaporizer 210 together with the ammonia supplied from the second ammonia supply section P20. becomes possible.

The second inflow point B20 may be arranged between the preheater 220 and the decomposition reaction section 300. More specifically, the second inflow point B20 may be arranged in the second supply line PB that guides the preheated gas phase ammonia discharged from the preheater 220 to the decomposition reaction section 300. Thereby, the hydrogen that has flowed into the second supply line PB from the external supply section 510 via the second inflow point B20 can be supplied to the decomposition reaction section 300 together with the ammonia discharged from the preheater 220. become.

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

Referring to FIG. 3, a high-purity hydrogen production apparatus 30 according to yet another embodiment of the present invention includes a combustion section 100, a first ammonia supply section P10, a vaporization preheating section 200, and a second ammonia supply section P10. It may also include a section P20, a decomposition reaction section 300, an adsorption purification section 400, and a hydrogen supply section 500. Moreover, the high-purity hydrogen production apparatus 10 may further include a hydrogen storage section S10. At this time, specific details of the combustion section 100, the first ammonia supply section P10, the vaporization preheating section 200, the second ammonia supply section P20, the decomposition reaction section 300, the adsorption purification section 400, and the hydrogen supply section 500 are specified. Since the features are the same or similar to those of the embodiments described above, overlapping explanations will be omitted. The following description will focus on the differences from the tenth embodiment described above.

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

In such a case, the external supply unit 510 supplies hydrogen to the intermediate connection line IC, and in addition, supplies hydrogen to either the first inflow point B10 or the second inflow point B10. You may.

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

For example, when supplying the reaction product via the first supply section 521, the first supply section 521 supplies a part of the reaction product discharged from the decomposition reaction section 300 to the intermediate connection line IC, In addition to this, the reaction product can also be supplied to either the first inflow point B10 or the second inflow point B10. To give another example, when supplying the reaction product via the second supply section 522, the second supply section 522 supplies a portion of the reaction product flowing into the adsorption purification section 400 to the intermediate connection line IC. In addition to this, the reaction product can also be supplied to either one of the first inflow point B10 and the second inflow point B10. To give yet another example, the third supply section 523 supplies a part of the high-purity hydrogen discharged from the adsorption purification section 400 to the intermediate connection line IC, and in addition to this, the third supply section 523 supplies a part of the high-purity hydrogen discharged from the adsorption purification section 400 to the intermediate connection line IC. High-purity hydrogen can also be supplied to either one of the second inflow point B10 and the second inflow point B10. To give yet another example, the fourth supply section 524 supplies a part of the high-purity hydrogen stored in the hydrogen storage section S10 to the intermediate connection line IC, and in addition to this, the fourth supply section 524 supplies a part of the high-purity hydrogen stored in the hydrogen storage section S10 to the first inflow point B10. High-purity hydrogen can also be supplied to either one of the second inflow point B10 and the second inflow point B10.

In this way, hydrogen can be supplied not only from the external supply section 510 but also from the internal supply section 520 to the intermediate connection line IC, but also to the first inflow point B10 or the second inflow point B20. This can prevent corrosion caused by high-temperature ammonia in the "preheater 220," the "decomposition reaction section 300," and the "piping connecting the rear end of the preheater 220 to the decomposition reaction section 300."

FIG. 4 is a block diagram showing a procedure for producing high-purity hydrogen using the high-purity hydrogen production apparatus using ammonia shown in FIGS. 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 is as follows.

First, the vaporizer 210 can vaporize the liquid ammonia supplied from the second ammonia supply section P20 to change the phase into gaseous ammonia (S110). At this time, the vaporizer 210 may be supplied with thermal energy contained in the high temperature reaction product discharged from the decomposition reaction unit 300 to vaporize the ammonia.

Next, the hydrogen supply unit 500 can 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.

In one embodiment, an external supply 510 can supply hydrogen to the intermediate connection line IC. In such a case, the hydrogen supplied by the external supply unit 510 may be supplied to the preheater 220 together with the gaseous ammonia discharged from the vaporizer 210. Next, 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 section 300. The preheater 220 can supply preheated gaseous ammonia to the decomposition reaction section 300 (S130).

In another embodiment, an internal supply 520 can supply hydrogen to the intermediate connection line IC. At this time, the internal supply section 520 includes, for example, a first supply section 521, a second supply section 522, a third supply section 523, and a fourth supply section 524, and the first to fourth supply sections 521 , 522, 523, and 524, hydrogen (or reaction product) may be supplied to the intermediate connection line IC. In this way, hydrogen (or reaction product) supplied from any one of the first to fourth supply sections 521, 522, 523, and 524 is supplied to gaseous ammonia via the intermediate connection line IC. It may also be supplied to the preheater 220.

In yet another embodiment, the hydrogen supply unit 500 can supply hydrogen to a hydrogen inflow point B located at 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. Further, the hydrogen supply section 500 connects to the first inflow point B10 or the second inflow point B10 via the external supply section 510 or any one of the first to fourth supply sections 521, 522, 523, and 524. Hydrogen (or reaction product) can be supplied to the inflow point B20. Thereby, the hydrogen (or reaction product) supplied from the hydrogen supply section 500 is supplied to the decomposition reaction section 300 together with preheated gas phase ammonia, and the hydrogen (or reaction product) supplied from the second ammonia supply section P20 is This allows it to be supplied to the vaporizer 210 together with ammonia.

On the other hand, the combustion section 100 can heat the decomposition reaction section 300 to a preset temperature by burning the ammonia supplied from the first ammonia supply section P10 (S100). Specifically, the combustion unit 100 can 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 section 100 may burn the off-gas supplied from the adsorption purification section 400 together with ammonia to generate combustion heat. This allows the ammonia decomposition reaction to start in the decomposition reaction section 300. The combustion section 100 can discharge combustion exhaust gas generated from the ammonia combustion reaction to the outside of the combustion section 100 .

Next, the decomposition reaction unit 300 decomposes ammonia and discharges the reaction products generated therefrom (S140). Specifically, the decomposition reaction section 300 can decompose ammonia supplied from the vaporization preheating section 200 [or the preheater 220] using thermal energy generated by heating in the combustion section 100. Note that the decomposition reaction section 300 can supply the reaction product generated from the ammonia decomposition reaction to the adsorption purification section 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 may selectively adsorb and remove only nitrogen and ammonia using an adsorbent contained therein using a pressure swing adsorption (PSA) method. Next, the separated and purified high-purity hydrogen may be discharged and stored in the hydrogen storage section S10.

Off-gas (ie, a mixed gas of nitrogen, hydrogen, and unreacted ammonia) generated during the adsorption and purification process may be supplied to the combustion section 100. Thereby, the combustion section 100 can heat the decomposition reaction section 300 by co-firing the ammonia supplied from the first ammonia supply section P10, hydrogen and a trace amount of unreacted ammonia contained in the off-gas. Through this process, the ammonia decomposition reaction in the decomposition reaction section 300 and the adsorption and purification in the adsorption purification section 400 can continue to be performed.

FIG. 5 is a diagram showing the state before and after corrosion occurs in the decomposition reaction section due to high-temperature ammonia when hydrogen is not supplied to the intermediate connection line. FIG. 6 is a diagram showing the state before and after corrosion occurs in the decomposition reaction part due to high temperature ammonia when hydrogen is supplied to the intermediate connection line.

Referring to FIG. 5, FIG. 5(a) shows a diagram before high temperature ammonia is supplied to the decomposition reaction section 300 when hydrogen (or reaction product) is not supplied to the intermediate connection line IC and the hydrogen inflow point B. Alternatively, it shows the initial surface condition of the decomposition reaction section 300 at the time when supply starts. Further, FIG. 5(b) shows a state in which hydrogen (or reaction product) is not supplied to the intermediate connection line IC and the hydrogen inflow point B, and high temperature ammonia is supplied to the decomposition reaction section 300 for a predetermined period of time. The surface state of the decomposition reaction section 300 after a period of time (for example, 24 hours) has passed is shown. Comparing FIG. 5(a) and FIG. 5(b), it can be seen that corrosion occurred on the surface of the decomposition reaction section 300 due to the inflow of high-temperature ammonia, and the surface roughness increased. Can be done.

In comparison, referring to FIG. 6, FIG. 6(a) shows the decomposition reaction section 300 before high temperature ammonia is supplied to the decomposition reaction section 300 or at the time when the supply starts. 300 initial surface conditions are shown. FIG. 6(b) shows a state in which hydrogen (or reaction product) is supplied to the intermediate connection line IC and the hydrogen inflow point B, and high temperature ammonia is supplied to the decomposition reaction section 300 for a predetermined time ( For example, the surface state of the decomposition reaction section 300 after 24 hours has passed is shown. In this way, comparing FIG. 6(a) and FIG. 6(b) shows that when hydrogen (or reaction product) is supplied, the occurrence of corrosion on the surface of the decomposition reaction section 300 due to high temperature ammonia is suppressed. Thus, it can be confirmed that the surface condition of the decomposition reaction section 300 is maintained at the initial surface condition.

FIG. 7 is a block diagram showing an apparatus for producing high purity hydrogen using ammonia according to yet another embodiment of the present invention.

Referring to FIG. 7, a high-purity hydrogen production apparatus 30 according to yet another embodiment of the present invention includes a combustion section 100, a first ammonia supply section P10, a vaporization preheating section 200, and a second ammonia supply section P10. It may also include a section P20, a decomposition reaction section 300, an adsorption purification section 400, and a catalytic reaction section 600. Moreover, the high-purity hydrogen production apparatus 10 may further include a hydrogen storage section S10. At this time, the specific features of the combustion section 100, the first ammonia supply section P10, the vaporization preheating section 200, the second ammonia supply section P20, the decomposition reaction section 300, and the adsorption purification section 400 are as described above. Since it is the same as or similar to the embodiment, overlapping description will be omitted. The following description will focus on the differences from the tenth and twentyth embodiments described above.

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

The catalytic reaction section 600 can produce hydrogen by subjecting a portion of the preheated gaseous ammonia discharged from the preheater 220 to a catalytic decomposition reaction. At this time, examples of catalysts used in the catalytic decomposition reaction of ammonia include, but are not limited to, pellet catalysts, monolithic catalysts, and metal form catalysts. It's not a thing.

In one embodiment, in the catalytic reaction section 600, an ammonia catalytic decomposition reaction may be performed using thermal energy contained in gaseous ammonia preheated by the preheater 220. In another embodiment, the catalytic reaction section 600 may include an electric heating section (not shown). In such a case, the electric heating section may be disposed outside or inside the main body (not shown) of the catalytic reaction section 600, and may include a heat source (not shown) for generating heat and a heat source emitted from the heat source. The catalytic decomposition unit 600 may also include a heat transfer unit (for example, a hot wire) for delivering the generated heat to the main body of the catalytic decomposition unit 600. By heating the catalytic reaction section 600 by the heat source and heat transfer section of the electric heating section, the temperature inside the catalytic decomposition section 600 rises to the temperature required for the catalytic decomposition reaction of ammonia. allows ammonia to be decomposed to produce a "mixture" of ammonia, nitrogen and hydrogen.

In this way, by catalytically decomposing a part of the gas phase ammonia supplied from the catalytic reaction section 600 to the decomposition reaction section 300 to produce hydrogen and supplying it to the decomposition reaction section 300, the second ammonia supply is achieved. Ammonia supplied from section P20 can be supplied to decomposition reaction section 300 together with hydrogen produced by catalytic reaction section 600. Thereby, occurrence of corrosion in the decomposition reaction section 300 due to the ammonia decomposition reaction being performed in the decomposition reaction section 300 can be suppressed.

FIG. 8 is a block diagram showing a procedure for producing high-purity hydrogen using the high-purity hydrogen production apparatus using ammonia shown in FIG.

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

First, the vaporizer 210 may vaporize the liquid ammonia supplied from the second ammonia supply unit P20 to change its phase into gaseous ammonia (S210). At this time, the vaporizer 210 may be supplied with thermal energy contained in the high temperature reaction product discharged from the decomposition reaction unit 300 to vaporize the ammonia.

The vaporized ammonia discharged from the vaporizer 210 may then be supplied to the preheater 220. In the preheater 220 , the supplied gaseous ammonia can be heated to preheat the gaseous ammonia before being supplied to the decomposition reaction section 300 . The preheater 220 can supply preheated gaseous ammonia to the decomposition reaction section 300 (S220).

On the other hand, the combustion section 100 can heat the decomposition reaction section 300 to a preset temperature by burning the ammonia supplied from the first ammonia supply section P10 (S100). Specifically, the combustion unit 100 can 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 section 100 may burn the off-gas supplied from the adsorption purification section 400 together with ammonia to generate combustion heat. Thereby, the ammonia decomposition reaction can begin in the decomposition reaction section 200. The combustion section 100 can discharge combustion exhaust gas generated from the ammonia combustion reaction to the outside of the combustion section 100 .

Next, the catalytic reaction unit 600 may decompose the preheated gas phase ammonia to produce hydrogen (S230). Specifically, the catalytic reaction unit 600 may decompose a portion of the preheated gaseous ammonia discharged from the preheater 220 through a catalytic decomposition reaction to produce hydrogen. This allows “unreacted ammonia” discharged from the preheater 220 and “nitrogen and hydrogen” generated by the catalytic reaction section 600 to be supplied to the decomposition reaction section 300.

Next, the decomposition reaction unit 300 can decompose ammonia and discharge the reaction products generated therefrom (S240). Specifically, the decomposition reaction unit 300 may decompose ammonia that is supplied through the catalytic reaction unit 600 after being discharged from the preheater 220 . At this time, the decomposition reaction unit 300 may decompose ammonia through an ammonia decomposition reaction performed using thermal energy generated by heating of the combustion unit 100. Note that the decomposition reaction section 300 can supply the reaction product generated from the ammonia decomposition reaction to the adsorption purification section 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 may selectively adsorb and remove only nitrogen and ammonia using an adsorbent contained therein using a pressure swing adsorption (PSA) method. Next, the separated and purified high-purity hydrogen may be discharged and stored in the hydrogen storage section S10.

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

As described above, the high-purity hydrogen production apparatuses 10, 20, 30, 40 and the production method S10 according to the embodiments of the present invention include, in addition to the hydrogen supply section 500, the rear end of the decomposition reaction section 300, the adsorption purification section. By providing an internal supply section 520 at the front end or rear end of the hydrogen storage section 400 and the hydrogen storage section S10, and further supplying hydrogen from there to the intermediate connection line IC, "preheater 220", " The occurrence of corrosion in the decomposition reaction section 300 and the piping connecting the rear end of the preheater 220 and the decomposition reaction section 300 can be suppressed. In addition to the intermediate connection line IC, a hydrogen inflow point B is further provided to which hydrogen is supplied from the hydrogen supply section 500, and by further supplying hydrogen to these inflow points, the decomposition reaction by high-temperature gaseous ammonia can be carried out. The problem of corrosion that occurs in the decomposition reaction part 300 [that is, the corrosion of the metal reaction part main body constituting the decomposition reaction part 300, the filler in the decomposition reaction part 300, the catalyst, etc.] can be solved.

Furthermore, the high-purity hydrogen production apparatus 30 and production method S20 according to the embodiment of the present invention catalytically decomposes a part of the preheated gas phase ammonia to produce hydrogen before being supplied to the decomposition reaction section 300. By supplying it to the decomposition reaction section 300 together with gaseous ammonia, it is possible to prevent the above-mentioned corrosion problem in the decomposition reaction section 300 due to high temperature gaseous ammonia.

The above description of the present invention is merely for illustrative purposes, and those with ordinary knowledge in the technical field to which the present invention pertains will understand the invention without changing the technical idea or essential features of the present invention. It can be easily transformed into other concrete forms. Therefore, the embodiments described above are merely illustrative in all respects, and are not restrictive. For example, components described as unitary may be implemented in a distributed manner, and similarly, components described as distributed may also be implemented in a combined form. Good too.

The scope of the present invention is expressed by the following claims, and any changes or modifications derived from the meaning and scope of the claims and equivalent concepts thereof are also included within the scope of the present invention.

10, 20, 30, 40 High purity hydrogen production device 100 Combustion section 200 Vaporization preheating section 210 Vaporizer 220 Preheater 300 Decomposition reaction section 400 Adsorption purification section 500 Hydrogen supply section 510 External supply section 520 Internal supply section 600 Catalytic reaction section P10 First ammonia supply section P20 Second ammonia supply section S10 Hydrogen storage section IC Intermediate connection line B Hydrogen inflow point

Claims (15)

a decomposition reaction section that decomposes ammonia through an ammonia decomposition reaction and discharges a reaction product containing hydrogen, nitrogen, and unreacted ammonia generated from the ammonia decomposition reaction;
a combustion section that heats the decomposition reaction section by burning ammonia supplied from a first ammonia supply section;
a vaporization preheating section comprising: a vaporizer that vaporizes liquid ammonia supplied from a second ammonia supply section; and a preheater that preheats ammonia supplied from the vaporizer via an intermediate connection line;
a hydrogen supply unit that supplies hydrogen to the intermediate connection line;
An apparatus for producing high-purity hydrogen using ammonia, comprising: an adsorption purification section that separates and purifies high-purity hydrogen from the reaction product. The hydrogen supply section includes one of the rear end of the decomposition reaction section, the front end or rear end of the adsorption purification section, and a hydrogen storage section in which separated and purified high-purity hydrogen is stored. The ammonia according to claim 1, comprising at least one of an internal supply section disposed in the ammonia tank and an external supply section disposed outside a connection line through which the reaction product, the ammonia and the high-purity hydrogen pass. High-purity hydrogen production equipment used. The internal supply section is
a first supply section that supplies a portion of the reaction product discharged from the decomposition reaction section to the intermediate connection line; and a first supply section that supplies a portion of the reaction product that is supplied to the adsorption purification section to the intermediate connection line. a second supply section for supplying a portion of the high-purity hydrogen separated and purified in the adsorption purification section and discharged to the intermediate connection line; The apparatus for producing high-purity hydrogen using ammonia according to claim 2, further comprising at least one of a fourth supply section that supplies a portion of the high-purity hydrogen to the intermediate connection line. The apparatus for producing high-purity hydrogen using ammonia according to claim 1, wherein the hydrogen supply unit supplies hydrogen to a hydrogen inflow point located at a position different from the intermediate connection line. The hydrogen inflow points are arranged at a plurality of different locations,
The apparatus for producing high-purity hydrogen using ammonia according to claim 4, wherein the hydrogen supply unit supplies hydrogen to at least one of the plurality of hydrogen inflow points. The hydrogen inflow point is
a first inflow point connected to a first supply line connecting the second ammonia supply section and the vaporizer; and a second supply line connecting the preheater and the decomposition reaction section. The apparatus for producing high-purity hydrogen using ammonia according to claim 5, comprising at least one of a second inflow point. the vaporizer vaporizing the liquid ammonia supplied from the second ammonia supply to produce gaseous ammonia;
a hydrogen supply unit supplying hydrogen to an intermediate connection line connecting the vaporizer and the preheater;
the preheater preheating the gas phase ammonia and supplying it to the decomposition reaction section;
a combustion section heating the decomposition reaction section by burning ammonia supplied from a first ammonia supply section;
The decomposition reaction unit decomposes ammonia through an ammonia decomposition reaction and discharges reaction products including hydrogen, nitrogen, and unreacted ammonia;
A method for producing high-purity hydrogen using ammonia, characterized in that the adsorption purification section adsorbs and removes nitrogen and unreacted ammonia from the reaction product to separate and purify high-purity hydrogen. . The method for producing high-purity hydrogen using ammonia according to claim 7, further comprising the step of supplying a reaction product or hydrogen to the intermediate connection line by the internal supply section. The internal supply section is
a first supply section that supplies a portion of the reaction product discharged from the decomposition reaction section to the intermediate connection line; and a first supply section that supplies a portion of the reaction product that is supplied to the adsorption purification section to the intermediate connection line. a third supply section that supplies part of the high-purity hydrogen separated and purified in the adsorption purification section to the intermediate connection line; The method for producing high-purity hydrogen using ammonia according to claim 8, further comprising at least one of the following: a fourth supply section that supplies a portion of the hydrogen to the intermediate connection line. 8. The method for producing high-purity hydrogen using ammonia according to claim 7, further comprising the step of supplying hydrogen to a hydrogen inflow point located at a location different from the intermediate connection line. The hydrogen inflow point is
a first inlet point connected to a first supply line connecting the second ammonia supply section and the vaporizer; and a second supply line connecting the preheater and the decomposition reaction section. The method for producing high-purity hydrogen using ammonia according to claim 10, comprising at least one of the following: a second inflow point. a decomposition reaction section that decomposes ammonia through an ammonia decomposition reaction and discharges a reaction product containing hydrogen, nitrogen, and unreacted ammonia generated from the ammonia decomposition reaction;
a combustion section that heats the decomposition reaction section by burning ammonia supplied from a first ammonia supply section;
a vaporization preheating section comprising: a vaporizer that vaporizes liquid ammonia supplied from a second ammonia supply section; and a preheater that preheats ammonia supplied from the vaporizer via an intermediate connection line;
a catalytic reaction section that decomposes a portion of the preheated ammonia through a catalytic reaction to produce hydrogen;
An apparatus for producing high-purity hydrogen using ammonia, comprising: an adsorption purification section that separates and purifies high-purity hydrogen from the reaction product. The apparatus for producing high-purity hydrogen using ammonia according to claim 12, wherein the hydrogen produced in the catalytic reaction section is supplied to the decomposition reaction section. The apparatus for producing high-purity hydrogen using ammonia according to claim 12, wherein the catalytic reaction is performed using thermal energy contained in ammonia heated by the preheater. The apparatus for producing high-purity hydrogen using ammonia according to claim 12, wherein the catalytic reaction is performed using an electric heating method.

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