JP2021161006A - Ammonia-reforming type hydrogen supply device and ammonia-reforming type hydrogen supply method using the same - Google Patents

Abstract

To provide an ammonia-reforming type hydrogen supply device capable of removing ammonia from a reformed gas containing ammonia and hydrogen at a high removal rate and capable of generating nitrogen at high selectivity, without the need for a plurality of adsorbers each having an adsorbent for adsorbing the ammonia, while having high hydrogen-generating capacity.SOLUTION: An ammonia-reforming type hydrogen supply device includes: a raw material feeder for supplying ammonia as a raw material; an ammonia reformer for reforming ammonia supplied from the raw material feeder to generate a reformed gas containing hydrogen; a hydrogen purification device including an ammonia selective oxidation catalyst for oxidizing ammonia in the reformed gas supplied from the ammonia reformer; and an oxygen feeder for supplying oxygen to the hydrogen purification device. The ammonia selective oxidation catalyst comprises sepiolite and Cu carried by the sepiolite.SELECTED DRAWING: None

Description

The present invention relates to an ammonia reformed hydrogen supply device and an ammonia reformed hydrogen supply method using the same.

The use of hydrogen-fueled fuel cells is attracting attention as a clean energy source that can curb environmental pollution and global warming. In recent years, various techniques related to devices and methods for supplying hydrogen to such fuel cells have been studied. For example, Japanese Patent Application Laid-Open No. 2019-53855 (Patent Document 1) describes a reformer that reforms ammonia to generate a reformed gas containing hydrogen, and a reformer for adsorbing ammonia contained in the reformed gas. A device including a plurality of adsorbers having the adsorbent of the above is disclosed, and hydrogen is supplied to a fuel cell by using such a device. However, in the apparatus described in Patent Document 1, since a plurality of adsorbers having an adsorbent are used to remove ammonia remaining in the reformed gas, there is a problem that the apparatus becomes large in size.

Further, in Japanese Patent Application Laid-Open No. 2016-164109 (Patent Document 2), the catalyst used for oxidatively decomposing ammonia to generate hydrogen is selected from the group consisting of Ru, Co, Rh, Ir and Ni1 An ammonia oxidative decomposition catalyst having a catalyst metal of more than one species and a zeolite carrier carrying the catalyst metal is disclosed. However, this ammonia oxidative decomposition catalyst is used in an environment where hydrogen does not exist (in a hydrogen-free environment), and is not necessarily sufficient as a catalyst for removing ammonia from a reforming gas containing ammonia and hydrogen. It wasn't a thing.

Further, when ammonia is oxidatively decomposed and removed from the reformed gas containing ammonia and hydrogen by using a conventional ammonia oxidative decomposition catalyst, the following formula (1):
4NH ₃ + 3O ₂ → 2N ₂ + 6H ₂ O (1)
In addition to the nitrogen production reaction represented by, the following formula (2):
2H ₂ + O ₂ → 2H ₂ O (2)
Since the water production reaction represented by (1) proceeds competitively, the supplied oxygen is used for the reaction with hydrogen, and there is a problem that ammonia cannot be removed with a high removal rate. In particular, when a catalyst supporting a noble metal having strong oxidizing power is used as the ammonia oxidative decomposition catalyst, the water represented by the formula (2) is more than the nitrogen production reaction represented by the formula (1). Since the formation reaction proceeds preferentially, there is a problem that ammonia contained in the reforming gas is not oxidatively decomposed and remains in the reforming gas.

Therefore, if a large amount of oxygen is supplied to oxidatively decompose ammonia, the nitrogen production reaction represented by the above formula (1) can easily proceed, and the removal rate of ammonia is improved, but the above formula (2) can be used. Since many of the represented water formation reactions proceed, there is also a problem that hydrogen contained in the reforming gas is wasted and energy efficiency is lowered.

Japanese Unexamined Patent Publication No. 2019-53855 Japanese Unexamined Patent Publication No. 2016-164109

The present invention has been made in view of the above-mentioned problems of the prior art, and is expensive from a reformed gas containing ammonia and hydrogen without the need for a plurality of adsorbers having an adsorbent for adsorbing ammonia. Ammonia can be removed at a removal rate, and the nitrogen production reaction represented by the above formula (1) can be selectively proceeded, that is, nitrogen can be produced at a high selectivity, resulting in high hydrogen production. It is an object of the present invention to provide an ammonia-modified hydrogen supply device having a capability, and an ammonia-modified hydrogen supply method using the same.

As a result of diligent research to achieve the above object, the present inventors have produced hydrogen by modifying a raw material supply device for supplying ammonia as a raw material and ammonia supplied from the raw material supply device. A hydrogen purification device provided with an ammonia reformer for generating the reforming gas contained therein, an ammonia selective oxidation catalyst for oxidizing ammonia in the reforming gas supplied from the ammonia reformer, and the hydrogen purification. In an ammonia-modified hydrogen supply device including an oxygen supply device for supplying oxygen to the device, by using a catalyst containing sepiolite and Cu supported on the sepiolite as the ammonia selective oxidation catalyst. Ammonia is removed from a reformed gas containing ammonia and hydrogen with a high removal rate, and nitrogen is produced with a high selectivity, without the need for multiple adsorbers having an adsorbent for adsorbing ammonia. It has been found that this is possible and a high hydrogen generation ability is exhibited, and the present invention has been completed.

That is, the ammonia-modified hydrogen supply device of the present invention has a raw material supply device for supplying ammonia as a raw material and a reformed gas containing hydrogen by reforming the ammonia supplied from the raw material supply device. A hydrogen refiner equipped with an ammonia reformer for producing ammonia, an ammonia selective oxidation catalyst for oxidizing ammonia in the reforming gas supplied from the ammonia reformer, and oxygen being supplied to the hydrogen refiner. Oxygen supply for
The ammonia selective oxidation catalyst is a catalyst comprising sepiolite and Cu supported on the sepiolite.

Further, in the ammonia-modified hydrogen supply method of the present invention, the ammonia as a raw material is supplied from the raw material supply device to the ammonia reformer by using the ammonia-modified hydrogen supply device of the present invention. After generating the quality gas, the reforming gas and the reforming gas are supplied by supplying oxygen from the oxygen supply device to the hydrogen purification device while supplying the reforming gas from the ammonia reformer to the hydrogen purification device. The method is characterized in that hydrogen is purified by bringing the oxygen into contact with the ammonia selective oxidation catalyst and oxidizing the ammonia in the reforming gas, and the purified hydrogen is supplied.

In the ammonia-modified hydrogen supply method of the present invention, the temperature of the contact gas when the reformed gas and the oxygen are brought into contact with the ammonia selective oxidation catalyst is preferably 350 to 650 ° C., and the ammonia. The supply ratio of oxygen and ammonia when brought into contact with the selective oxidation catalyst is preferably 0.75 to 10.75 in _{terms of volume ratio ([oxygen (O 2} )] / [ammonia (NH _3)]).

It should be noted that the reason why it is possible to selectively oxidize ammonia and selectively generate nitrogen by the ammonia selective oxidation catalyst according to the present invention, which comprises sepiolite and Cu supported on the sepiolite, is not necessarily clear. However, the present inventors infer as follows. That is, first, when oxygen and the reforming gas are brought into contact with the ammonia selective oxidation catalyst, ammonia is adsorbed by the sepiolite in the ammonia selective oxidation catalyst, and the ammonia is concentrated on the sepiolite, and then the ammonia is supported on the sepiolite. It is presumed that the adsorbed ammonia reacts with oxygen due to the Cu. At this time, hydrogen in the reforming gas is less likely to be adsorbed by sepiolite, and even if it comes into contact with the ammonia selective oxidation catalyst, the HH bond is less likely to be dissociated on the metal. It is presumed that the reaction between ammonia and oxygen (the reaction represented by the formula (1)) can be preferentially triggered over the reaction represented by the formula (2). Therefore, according to the ammonia selective oxidation catalyst, it is possible to selectively oxidize ammonia and selectively generate nitrogen, and sufficiently oxidize and remove ammonia from the reformed gas to sufficiently purify hydrogen. The present inventors presume that it becomes possible to generate (gas).

According to the present invention, in an ammonia-modified hydrogen supply device and an ammonia-modified hydrogen supply method using the same, ammonia can be used without the need for a plurality of adsorbents having an adsorbent for adsorbing ammonia. Ammonia can be removed from the reforming gas containing hydrogen with a high removal rate, and nitrogen can be generated with a high selectivity, so that a high hydrogen generation ability can be exhibited.

It is a schematic diagram which shows one preferable embodiment of the ammonia reforming type hydrogen supply apparatus of this invention. It is a schematic diagram which shows the reaction tube filled with the catalyst used in an Example and a comparative example. It is a graph which shows the temperature profile of the catalyst-filled gas at the time of pretreatment and measurement in an Example and a comparative example.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings, but the present invention is not limited to the above drawings. In the following description and drawings, the same or corresponding elements may be designated by the same reference numerals, and duplicate description may be omitted.

[Ammonia reforming hydrogen supply device]
First, the ammonia-modified hydrogen supply device of the present invention will be described. The ammonia-modified hydrogen supply device of the present invention produces a raw material supply device for supplying ammonia as a raw material and a reformed gas containing hydrogen by reforming the ammonia supplied from the raw material supply device. To supply oxygen to the hydrogen refiner, a hydrogen purification device provided with an ammonia reformer for oxidizing the ammonia in the reforming gas supplied from the ammonia reformer, and an ammonia selective oxidation catalyst for oxidizing the ammonia in the reforming gas, and the hydrogen purification device. The oxygen supply device of the above is provided, and as the ammonia selective oxidation catalyst, a catalyst including sepiolite and Cu supported on the sepiolite is provided.

The ammonia selective oxidation catalyst used in the present invention is a catalyst comprising sepiolite and Cu supported on the sepiolite. Sepiolite _{is Mg 8 (H 2 O) 4} [Si 6 O 15] 2 · (OH) hydrous magnesium silicate having a chemical composition of 4 · 8H ₂ O, usually, the SiO ₂ 50-60%, MgO Is contained in an amount of 16 to 25%, and further, aluminum oxide (Al ₂ O ₃ ), iron oxide (FeO, Fe ₂ O ₃ ), calcium oxide (CaO), sodium oxide (Na ₂ O), manganese oxide (MnO), etc. Contains a small amount. Since such sepiolite has a channel structure in which they are stacked on each other and is a porous fibrous viscosity mineral, it has a large specific surface area, and is excellent in adsorption characteristics (particularly, adsorption characteristics of ammonia) and metal dispersibility. ing. Therefore, by using such sepiolite as a catalyst carrier and supporting copper, it is possible to obtain a catalyst (ammonia selective oxidation catalyst) capable of selectively adsorbing ammonia and easily oxidatively decomposing it. On the other hand, when the other metal oxides nonporous a _{(MgO, Y 2 O 3,} CeO 2, Al 2 O 3 , etc.) were used as a catalyst carrier, NH ₃ removal rate and _{N 2} selectivity is sufficiently It does not improve and is inferior in ammonia removal performance and nitrogen selectivity.

Further, in the ammonia selective oxidation catalyst used in the present invention, Cu is supported on the sepiolite. By supporting Cu on sepiolite, ammonia is selectively adsorbed on Cu and sepiolite, and the adsorbed ammonia is easily oxidized by the catalytic action of copper, so that the NH ₃ removal rate and N ₂ selectivity are improved. A catalyst having excellent ammonia removal performance and nitrogen selectivity (ammonia selective oxidation catalyst) can be obtained. Meanwhile, since the other metals (Ni, Co, etc.) catalyst supporting the sepiolite, the low oxidative decomposition activity of ammonia other metals not easily oxidized even when selectively adsorb ammonia, NH ₃ removal rate Is not improved, and the ammonia removal performance is inferior.

The amount of such Cu supported is not particularly limited, but is preferably 0.05 to 30% by mass, more preferably 0.1 to 6% by mass, based on the total amount of the ammonia selective oxidation catalyst. When the loading amount of Cu is less than the lower limit, oxidative decomposition activity of the ammonia is not sufficiently obtained, tend to NH ₃ removal rate decreases, whereas if it exceeds the upper limit, there is no change in reactivity, Cu The cost tends to be high because it wastes.

The form of the ammonia selective oxidation catalyst is not particularly limited, and the form can be appropriately changed according to the desired design. For example, a pellet-shaped substrate or a substrate having various shapes (for example, a honeycomb monolith-shaped) can be used. It can be in the form of a catalyst supported on a base material, etc.).

The method for producing such an ammonia selective oxidation catalyst is not particularly limited, and a known method can be appropriately used. For example, a known method capable of supporting a metal on a carrier can be appropriately adopted. Sepiolite is immersed in a solution in which a salt (nitrite, chloride, acetate, etc.) or Cu complex is dissolved in a solvent such as water or alcohol, and the Cu salt or Cu complex is added to sepiolite by an ion exchange method or an impregnation method. It is preferable to use a method of supporting, then removing the solvent, and further firing.

FIG. 1 is a schematic view showing a preferred embodiment of the ammonia reformed hydrogen supply device of the present invention. The ammonia reforming type hydrogen supply device 1 shown in FIG. 1 includes a raw material supply device 10, an ammonia reformer 11, a hydrogen purification device 12, an oxygen supply device 13, and gas pipes 14a to 14e. In such a device 1, the raw material supply device 10 and the ammonia reformer 11 provide a gas pipe 14a so that the raw material supply device 10 can supply ammonia (raw material) to the ammonia reformer 11. Connected via. Further, the ammonia reformer 11 and the oxygen supply device 13 are connected via a gas pipe 14b so that oxygen can be supplied to the ammonia reformer 11 from the oxygen supply device 13. Further, in such an apparatus 1, the ammonia reformer 11 and the hydrogen purification apparatus 12 provide a gas pipe 14c so that the reforming gas can be supplied from the ammonia reformer 11 to the hydrogen purification apparatus 12. It is connected via. Further, the hydrogen purification device 12 and the oxygen supply device 13 are connected via a gas pipe 14d so that oxygen can be supplied to the hydrogen purification device 12 from the oxygen supply device 13. Further, a gas pipe 14e is connected to the hydrogen purification device 12 so that the purified hydrogen can be supplied to the outside through the gas pipe 14e. The arrows shown in the gas pipes 14a to 14e in FIG. 1 conceptually indicate the direction of the gas flowing in the gas pipe (the direction in which the gas flows).

The raw material feeder 10 may be any as long as it can supply ammonia as a raw material to the ammonia reformer 11, and its design and the like are not particularly limited, and known ones can be appropriately used. Such a raw material supply device 10 may include, for example, a tank (storage container) for storing ammonia. The tank included in the raw material supply device 10 is not particularly limited, but from the viewpoint of downsizing the device and being able to supply a larger amount of ammonia, the ammonia is in a liquid state. A tank that can be stored in is preferable. As a tank capable of storing ammonia in a liquid state, for example, it is possible to store ammonia in a liquid state at room temperature (about 20 ° C to 25 ° C) and several atm (about 8.6 atm to 10 atm). Is preferable. By using a tank capable of storing such ammonia in a liquid state, it becomes possible to replenish the tank more easily.

Further, when the raw material supply device 10 is provided with a tank capable of storing ammonia in a liquid state, the raw material supply device 10 can supply the ammonia in a gaseous state to the ammonia reformer 11. It is preferable that the raw material feeder 10 further includes a vaporizer connected to the tank together with the tank so as to be possible. Such a vaporizer may be any one capable of vaporizing ammonia in a liquid state, and is not particularly limited, but can be vaporized by heating, for example, ammonia in a liquid state. A known vaporizer such as one can be used as appropriate. Further, when the raw material supply device 10 is provided with such a tank and a vaporizer, for example, the ammonia is brought into a liquid state by a pump for introducing the ammonia in a liquid state from the tank into the vaporizer. It is preferable to use a tank in which the tank to be stored in is connected to the vaporizer. By using such a raw material supply device 10, it becomes possible to supply ammonia in a gaseous state to the ammonia reformer 11 via the gas pipe 14a.

The ammonia reformer 11 is provided on the downstream side of the raw material supply device 10, and is connected to the raw material supply device 10 via a gas pipe 14a. Further, the ammonia reformer 11 is also connected to the oxygen supply device 13 via a gas pipe 14b. Therefore, in the apparatus 1 shown in FIG. 1, it is possible to supply ammonia (gas) from the raw material supply device 10 to the ammonia reformer 11, and the oxygen supply device to the ammonia reformer 11. It is also possible to supply oxygen (gas) from 13.

The configuration of such an ammonia reformer 11 is not particularly limited, and a known configuration can be appropriately used. For example, it is preferable to use one provided with a known ammonia reformer. By using the ammonia reformer 11 provided with such an ammonia reforming catalyst, the ammonia supplied from the raw material supply device 10 can be decomposed by using the ammonia reforming catalyst and contains _{hydrogen (H 2).} It is possible to efficiently generate the reformed gas to be produced. As such an ammonia reformer 11, a known container containing a known ammonia reforming catalyst or the like can be appropriately used.

Further, when the ammonia reformer 11 provided with the ammonia reforming catalyst is used, the ammonia reformer 11 is ammonia for oxidizing ammonia by a chemical reaction between ammonia and oxygen to generate heat. A combustion part (oxidation part) equipped with a combustion catalyst, and a reforming part (decomposition part) equipped with an ammonia reforming catalyst for decomposing ammonia by utilizing the heat generated in this combustion part to generate hydrogen and nitrogen. , Are preferred. By using the ammonia reformer 11 having such a combustion unit and a reforming unit, a part of ammonia supplied from the raw material supply device 10 and oxygen supplied from the oxygen supply device 13 in the combustion unit can be used. Can be brought into contact with the ammonia combustion catalyst to oxidize ammonia and generate heat, and the heat generated by the oxidation reaction is burned with ammonia in the reforming section (ammonia supplied from the raw material supply device 10). It can be used for the decomposition reaction of the rest) that was not burned by the part. As a result, it becomes possible to utilize the heat generated in the combustion part for the decomposition reaction caused by bringing ammonia into contact with the ammonia reforming catalyst, so that ammonia can be reformed to generate hydrogen more efficiently. It will be possible. In this way, by using the ammonia reformer 11 including the combustion part and the reforming part, a part of ammonia is oxidized in the combustion part and the remaining ammonia is hydrogenated in the reforming part. Ammonia can be reformed by the so-called autothermal reforming (ATR) method (it can be said that such a reformer 11 is an internal heat supply type reformer).

As the ammonia combustion catalyst used in such a combustion unit, a known catalyst that can be used for oxidizing ammonia can be appropriately used. For example, a catalyst metal (metal activity) composed of a carrier and a noble metal supported on the carrier. Points) and are preferable. Further, as the ammonia reforming catalyst used in the reforming section, a known ammonia reforming catalyst capable of reforming ammonia and decomposing it into hydrogen and nitrogen can be appropriately used, and the carrier and the carrier are not particularly limited. Those provided with a catalyst metal (metal active point) made of a noble metal supported on this carrier are preferable. The carrier used for such an ammonia combustion catalyst and an ammonia reforming catalyst is not particularly limited, and known carriers can be appropriately used, and for example, alumina, zeolite and the like can be appropriately used. Examples of the catalyst metal of the ammonia combustion catalyst include V, Cr, Mn, Fe, Co, Ni, Cu, Mo, Ru, Rh, Pd, Ag, W, Re, Os, Ir, and Pt. From the viewpoint of higher low temperature activity, V, Mn, Fe, Co, Ni, Pt, Cu and Ru are preferable. Examples of the catalyst metal of the ammonia reforming catalyst include V, Cr, Mn, Fe, Co, Ni, Cu, Mo, Ru, Rh, Pd, Ag, W, Re, Os, Ir, and Pt. Of these, Ru, Fe, Co, Ni, Mo, Rh, and Re are preferable from the viewpoint of increasing the low temperature activity. Such an ammonia combustion catalyst and an ammonia reforming catalyst may have the same configuration or different configurations. Further, the method for preparing the ammonia combustion catalyst and the ammonia reforming catalyst is not particularly limited, and known methods can be appropriately used. Further, the forms of the ammonia combustion catalyst and the ammonia reforming catalyst are not particularly limited, and the forms can be appropriately changed according to the desired design. For example, the catalyst may be supported on a honeycomb monolith-like base material or the like.

As such an ammonia reformer 11, for example, one having the combustion part on the upstream side and the reformer on the downstream side, or oxygen and ammonia circulate in the combustion part. A partition plate or the like is installed in the reformer 11 so that only ammonia flows through the reforming portion to partition the combustion portion from the reforming portion, and the heat of the combustion portion is transferred through the partition plate. Various forms can be used, such as those that can be conducted to the reformed portion. The configuration (form) of such an ammonia reformer 11 is not particularly limited, and includes a known configuration (for example, a reformer configuration (including a method of connecting a gas pipe) disclosed in Japanese Patent Application Laid-Open No. 2019-53855. ) Etc.) can be used as appropriate. Further, the configuration of the reformer 11 is not limited to the above, and for example, a heater or the like for generating heat for decomposing ammonia may be separately provided.

The hydrogen refiner 12 is provided on the downstream side of the ammonia reformer 11, and is connected to the ammonia reformer 11 via a gas pipe 14c. Further, the hydrogen purification device 12 is also connected to the oxygen supply device 13 via a gas pipe 14d. Therefore, in the apparatus 1 shown in FIG. 1, it is possible to supply the reforming gas generated by the ammonia reformer 11 from the ammonia reformer 11 to the hydrogen purification apparatus 12, and also to supply the oxygen feeder. It is also possible to supply oxygen from 13 to the hydrogen purification apparatus 12.

Such a hydrogen purification apparatus 12 may be provided as long as it includes the ammonia selective oxidation catalyst, and its configuration is not particularly limited. Therefore, the hydrogen purification apparatus 12 has the same configuration as the catalyst reaction apparatus (fixed bed flow type reactor, fluidized bed type reactor, etc.) having a known configuration except that the catalyst type is the ammonia selective oxidation catalyst. Can be used as appropriate. Further, such a hydrogen purification apparatus 12 may include a container for accommodating the ammonia selective oxidation catalyst, depending on its design. Such a container is not particularly limited, and a known container can be appropriately used.

Further, the hydrogen purification apparatus 12 may be appropriately provided with a known heat exchanger or the like so that the gas flowing in the gas pipe has an appropriate temperature. Further, in the hydrogen purification apparatus 12, in order to maintain a high catalytic activity and allow the reaction to proceed more efficiently, the temperature of the ammonia selective oxidation catalyst itself in the apparatus and the gas that comes into contact with the ammonia selective oxidation catalyst are charged. Heating means, cooling means, and the like may be appropriately provided so that the temperature and the like can be appropriately controlled.

The oxygen supply device 13 is connected to the ammonia reformer 11 and the hydrogen purification device 12 via gas pipes 14b and 14d, respectively. As such an oxygen supply device 13, a device capable of supplying a required amount of oxygen to the ammonia reformer 11 and the hydrogen purification device 12, respectively, can be used as appropriate. Further, the oxygen supply device 13 may be capable of supplying a required amount of oxygen to the ammonia reformer 11 and the hydrogen purification device 12 by supplying a gas containing oxygen (for example, air), and further. , The required amount of oxygen may be able to be supplied to the ammonia reformer 11 and the hydrogen purification device 12 alone. As described above, the oxygen supply device 13 may be any as long as it can supply oxygen as a result, and is not particularly limited, and a known device can be appropriately used, for example, a compressor, an air pump, a cylinder, and an intake air. Those equipped with a means (fan, etc.) capable of supplying gas (blowing, etc.) to a gas pipe (gas pipe for supplying oxygen gas) having a structure capable of taking in air from the mouth (fan, etc.) Housing) etc. can be used.

Further, the gas pipes 14a to 14e are not particularly limited as long as they can allow gas to flow through the pipes, and known gas pipes 14a to 14e can be appropriately used according to the size and design of the apparatus. .. Further, in order to efficiently flow the gas into the gas pipes 14a to 14e, the gas pipes 14a to 14e and other components (such as the above-mentioned ammonia reformer 11 and the hydrogen purification device 12) have a fan, an injector, and a valve. A means capable of adjusting the flow rate of the gas or the like may be appropriately provided. Further, the gas tubes 14a to 14e and other components (such as the above-mentioned ammonia reformer 11 and the hydrogen purification device 12) are provided with known heat exchangers and known so that the temperature of the gas becomes a desired temperature. The heating means, cooling means, and the like may be appropriately provided, and the design can be appropriately changed according to the type and application of the catalyst to be used.

Further, in the ammonia reforming type hydrogen supply device, in order to control the amount of oxygen used for the reaction, the temperature of the gas, and the like, in each gas pipe and at the discharge port of the reforming gas of the ammonia reformer 11. Appropriate areas such as the vicinity (near the connection between the gas pipe 14c and the ammonia reformer 11) and the vicinity of the inlet of the reformed gas of the hydrogen purification device 12 (near the connection between the gas pipe 14c and the hydrogen purification device 12). Various known sensors such as a sensor for measuring the concentration of a component (for example, hydrogen) in the gas and a sensor for measuring the temperature of the gas may be appropriately installed at the site, and from these sensors. Depending on the information, the operating status of the oxygen supply device 13, the heating means, and the like may be controlled to appropriately control the amount of oxygen supplied, the temperature of the gas, and the like. For example, when the device 1 is mounted on an automobile, a computer of a so-called engine control unit (ECU) for controlling the driving state of the engine of the automobile is used, based on data obtained from various sensors and the like. Even if the gas supply amount (flow rate), gas temperature, etc. are appropriately controlled by appropriately controlling the operating conditions of various components (oxygen supply device 13, heating means provided in some cases, etc.) included in the device 1. good.

Next, the ammonia-modified hydrogen supply method of the present invention will be described. In the ammonia-modified hydrogen supply method of the present invention, the ammonia as a raw material is supplied from the raw material supply device to the ammonia reformer by using the ammonia-modified hydrogen supply device of the present invention, and the reformed gas is supplied. By supplying oxygen from the oxygen supply device to the hydrogen purification device while supplying the reforming gas from the ammonia reformer to the hydrogen purification device, the reforming gas and the oxygen Is a method of purifying hydrogen by contacting with the ammonia selective oxidation catalyst and oxidizing the ammonia in the reforming gas, and supplying the purified hydrogen.

Hereinafter, a preferred embodiment of the ammonia-modified hydrogen supply method of the present invention will be described with reference to FIG.

In the hydrogen supply method using the ammonia reforming type hydrogen supply device shown in FIG. 1, first, ammonia as a raw material is supplied from the raw material supply device 10 to the ammonia reformer 11. The method of supplying ammonia from the raw material supply device 10 to the ammonia reformer 11 differs depending on the configuration of the raw material supply device 10, and is not particularly limited. For example, the raw material supply device 10 is described above. When a tank (storage container) for storing ammonia and a vaporizer are used, the liquid ammonia introduced into the vaporizer from the tank is vaporized (gasified) by the vaporizer, and the generated gaseous state. By introducing the ammonia of the above into the gas pipe 14a, a method of supplying gaseous ammonia from the raw material supply device 10 to the ammonia reformer 11 can be adopted.

Next, after supplying ammonia (raw material) to the ammonia reformer 11 as described above, the ammonia reforming reaction is allowed to proceed in the reformer 11. This makes it possible to generate a reformed gas in the ammonia reformer 11. The method itself for producing the reformed gas is not particularly limited, and a known method can be appropriately used. For example, in the ammonia reformer 11, the reforming gas may be generated by utilizing the known reforming reaction of ammonia in the same manner as the known reformer, and the reaction may be carried out according to the structure of the reformer. The reformed gas may be generated by appropriately adopting appropriate conditions so that Such a reforming gas has a composition different depending on the reaction form of the reforming reaction of ammonia generated in the reformer 11, but contains hydrogen, nitrogen, water and ammonia (ammonia remaining without reaction). obtain.

For example, with respect to the generation of the reformed gas, an ammonia reformer 11 is used which has the combustion portion on the upstream side and in which the gas after combustion comes into contact with the reforming portion on the downstream side. In this case, first, when ammonia is introduced into the ammonia reformer 11 via the gas pipe 14a and oxygen is introduced through the gas pipe 14b, oxygen and ammonia are burned with the ammonia in the combustion section on the upstream side. In contact with the catalyst, the following formula (1):
4NH ₃ + 3O ₂ → 2N ₂ + 6H ₂ O (1)
The reaction of oxygen and ammonia (nitrogen formation reaction) represented by is generated, nitrogen (N ₂ ) and water (H ₂ O) are generated on the upstream side, and heat is generated, and the generated heat is used. By activating the ammonia reforming catalyst in the reforming section on the downstream side, it is possible to efficiently trigger the decomposition reaction of Ammonnia (reaction that produces nitrogen and hydrogen) on the downstream side, and to generate reforming gas. Can be done. When such a reaction is used, the reformed gas obtained contains nitrogen and water generated on the upstream side and nitrogen and hydrogen generated on the downstream side, and the raw material gas remaining without reaction (the raw material gas remaining without reaction). Ammonia) may be included. When an ammonia reformer 11 having such a combustion unit and a reformer is used, the ratio of ammonia and oxygen supplied to the reformer 11 is not particularly limited, and the type and performance of the combustion unit and the reformer, etc. It may be set appropriately according to. Further, the method of supplying oxygen is not particularly limited, and oxygen may be supplied as a result by supplying air from the oxygen supply device 13.

When the ammonia reformer 11 including the reformer and the heater for supplying heat to the reformer is used, the heat from the heater can be used, so that the reaction in the combustion section is performed. It is not always necessary to utilize (combustion reaction of ammonia), and in this case, oxygen does not have to be particularly supplied to the reformer 11. When the combustion reaction of ammonia is not utilized by utilizing the heat of the heater in this way, the reformed gas produced may contain hydrogen, nitrogen and ammonia. In this way, the necessity of supplying oxygen to the ammonia reformer 11 can be appropriately changed according to the configuration of the apparatus, and the composition of the reformed gas produced as a result can be different.

In such a step of generating a reformed gas from ammonia, the reformed gas is generated from ammonia by using a known means (known reformer) capable of reforming ammonia as the ammonia reformer 11. A known method for producing can be appropriately applied, and known conditions can be appropriately adopted for the amount of ammonia and oxygen used, the temperature of the catalyst to be used, and the like. Further, in the reformer 11, a theoretical amount that can be decomposed (amount that can be theoretically decomposed in relation to the amount of catalyst, etc .: calculated in advance by mapping the relationship between the amount of catalyst and the amount of gas, etc.) When ammonia is supplied by (may be), the composition of the reformed gas to be generated may be in a state where excess hydrogen and a small amount of ammonia (ammonia that remains without reaction) are contained in the volume ratio. It is possible.

Next, after the reformed gas is generated as described above, the reformed gas is supplied from the ammonia reformer 11 to the hydrogen purification device 12 via the gas pipe 14c, and is supplied from the oxygen supply device 13 to the gas pipe. By supplying oxygen to the hydrogen purification apparatus 12 via 14d, the reformed gas and the oxygen are brought into contact with the ammonia selective oxidation catalyst to oxidize the ammonia in the reformed gas. As described above, in the present invention, after the reformed gas is generated, ammonia is oxidized by the ammonia selective oxidation catalyst provided in the hydrogen purification apparatus 12. The method of supplying oxygen used for such oxidation from the oxygen supply device 13 is not particularly limited, and oxygen may be supplied as a result by supplying air from the oxygen supply device 13.

When the reformed gas and the oxygen are brought into contact with the ammonia selective oxidation catalyst, the contact gas (mixed gas of the reformed gas and the oxygen) is used so that the reaction proceeds more efficiently depending on the type of catalyst and the like. ) Is preferably controlled, for example, the temperature of the contact gas is preferably 350 to 650 ° C, more preferably 450 to 600 ° C. If the temperature of the contact gas is less than the lower limit, it is difficult to increase the activity of Cu, and the ability to remove ammonia tends to be low. On the other hand, if the temperature exceeds the upper limit, adsorption of ammonia to Cu or sepiolite is inhibited. On the contrary, the ammonia removal performance tends to decrease.

Further, when the reforming gas and the oxygen are brought into contact with the ammonia selective oxidation catalyst, the supply ratio of oxygen and ammonia (ammonia in the reforming gas) when the reforming gas and the oxygen are brought into contact with the ammonia selective oxidation catalyst is a volume ratio ( [Oxygen (O ₂ )] / [Ammonia (NH ₃ )]) is preferably 0.75 to 10.75, and more preferably 1 to 10. If such a volume ratio is less than the lower limit, oxygen becomes insufficient and ammonia tends to remain without being oxidized. On the other hand, if the volume ratio exceeds the upper limit, excess oxygen reacts with hydrogen and is purified by a reformer. It tends to waste the hydrogen that has been produced. The method of bringing the contact gas (mixed gas) having such a volume ratio into contact with the ammonia selective oxidation catalyst is not particularly limited, and for example, a sensor capable of measuring the concentration of ammonia gas in the apparatus 1 is used. A method of checking the concentration of ammonia in the reforming gas supplied to the hydrogen purification apparatus 12 and controlling the operation of the oxygen supply device 13 so that the required amount of oxygen is supplied from the oxygen supply device 13. Can be adopted as appropriate.

Further, when the reforming gas and the oxygen are brought into contact with the ammonia selective oxidation catalyst, the flow rate of the contact gas (mixed gas of the reforming gas and the oxygen) is not particularly limited, and depending on the type of catalyst, the flow rate is not particularly limited. It may be set appropriately.

In the ammonia-modified hydrogen supply method of the present invention, hydrogen is purified by bringing the reformed gas and the oxygen into contact with the ammonia selective oxidation catalyst and oxidizing the ammonia in the reformed gas in this way. However, in the hydrogen-containing gas obtained after purification (hereinafter, for convenience, simply referred to as “purified gas” in some cases), the ammonia content is preferably 0.1 ppm or less. When the concentration of ammonia in the refined gas exceeds the above upper limit, for example, when the refined gas (hydrogen) is supplied to the PEM type (solid polymer type) fuel cell, the PEM type fuel cell tends to deteriorate. In the ammonia reforming hydrogen supply method of the present invention, the ammonia selective oxidation is carried out in consideration of the application, the overall size of the apparatus 1 itself, etc. so that the content of ammonia in the purified gas is 0.1 ppm or less. It is preferable to appropriately design and use the apparatus 1 in consideration of the relationship between the type of catalyst, the amount used thereof, the amount of gas supplied to the ammonia selective oxidation catalyst, the temperature, and the like.

Next, in this way, hydrogen is purified by bringing the reformed gas and the oxygen into contact with the ammonia selective oxidation catalyst, and then the purified hydrogen (ammonia is sufficiently removed) to the outside via the gas pipe 14e. Hydrogen) is supplied. The supply destination of hydrogen after such purification is not particularly limited, but a PEM type fuel cell can be mentioned as a suitable one.

Although the preferred embodiments of the ammonia reforming hydrogen supply device and the ammonia reforming hydrogen supply method of the present invention have been described above with reference to FIG. 1, the ammonia reforming hydrogen supply device and the ammonia reforming of the present invention have been described with reference to FIG. The type hydrogen supply method is not limited to the above embodiment. For example, in the ammonia reforming hydrogen supply device 1 shown in FIG. 1, the oxygen supply device 13 is connected to the ammonia reformer 11, but in the ammonia reforming hydrogen supply device of the present invention, the hydrogen purification device The relationship between the oxygen supply device and the hydrogen purification device 12 may be configured so that oxygen can be supplied to 12, and the piping of the gas pipe and the like is not particularly limited. Further, in the ammonia-modified hydrogen supply device 1 shown in FIG. 1, one oxygen supply device 13 is used, but in the ammonia-modified hydrogen supply device of the present invention, the number of oxygen supply devices 13 is large. The present invention is not particularly limited, and for example, two oxygen supply devices 13 may be used to connect separate oxygen supply devices 13 to the ammonia reformer 11 and the hydrogen purification device 12. Further, in the ammonia reforming hydrogen supply device 1 shown in FIG. 1, the raw material supply device 10 and the ammonia reformer 11 are connected by a single linear gas pipe 14a, but the raw material supply device 10 and the raw material supply device 10 are connected to each other. The ammonia reformer 11 may be configured so that ammonia is supplied from the raw material supply device 10 to the ammonia reformer 11, and the shape and number of gas pipes used for the supply are not particularly limited. For example, these may be connected by a plurality of gas pipes, or may be connected by a gas pipe branched from the middle. Further, when the ammonia reformer 11 includes the combustion unit and the reformer, for example, by connecting the raw material supply device 10 and the ammonia reformer 11 with a gas pipe branched from the middle, each unit is provided. The amount of ammonia supplied to the device may be adjusted. As described above, the ammonia-reformed hydrogen supply device and the ammonia-reformable hydrogen supply method of the present invention are not limited to the above-described embodiment, and the design and the like are designed according to the application, the target size, and the like. It can be changed as appropriate.

Hereinafter, the present invention will be described in more detail based on Examples and Comparative Examples, but the present invention is not limited to the following Examples.

(Example 1)
[Preparation of copper-supported sepiolite catalyst by ion exchange method]
First, sepiolite (“P-150” manufactured by Omi Mining Co., Ltd.) was heat-treated in the air at 650 ° C. for 2 hours. 20.07 g of sepiolite after the heat treatment was added to 300 ml of ion-exchanged water and stirred to prepare a sepiolite dispersion. Also, copper acetate monohydrate _{(Cu (CH 3 COO) 2} · H 2 O, manufactured by Kanto Chemical Co., Inc.) and 2.00g were dissolved in deionized water 50 ml. The obtained copper acetate aqueous solution was added dropwise to the sepiolite dispersion, and the mixture was stirred for 4.5 hours while heating at 200 ° C. using a hot plate, and then allowed to cool overnight. The obtained precipitate was collected by suction filtration, washed twice with ion-exchanged water, and then dried overnight in a dryer at 110 ° C.

Next, the obtained solid content was heat-treated at 300 ° C. for 3 hours under an atmospheric air flow of 1 L / min, and further, an H ₂ / N ₂ mixed gas air flow (H ₂ / N ₂ = 0.05 []. It was heat-treated at 500 ° C. for 5 hours under ml / min] /0.95 [ml / min]). The obtained solid powder was powder-molded, crushed and sized, and catalyst pellets (ex-Cu3 / Sep, copper-supported amount: 3% by mass, particle size: 0) on which copper was supported on sepiolite by an ion exchange method. .5-1.0 mm) was obtained.

(Example 2)
[Preparation of copper-supported sepiolite catalyst by ion exchange method]
A catalyst pellet (ex-Cu1) in which copper was supported on sepiolite by an ion exchange method in the same manner as in Example 1 except that the amount of sepiolite was changed to 21.14 g and the amount of copper acetate monohydrate was changed to 0.669 g. / Sep, copper loading amount: 1% by mass, particle size: 0.5 to 1.0 mm) was prepared.

(Example 3)
[Preparation of copper-supported sepiolite catalyst by ion exchange method]
A catalyst pellet (ex-Cu6) in which copper was supported on sepiolite by an ion exchange method in the same manner as in Example 1 except that the amount of sepiolite was changed to 20.92 g and the amount of copper acetate monohydrate was changed to 4.08 g. / Sep, copper loading amount: 6% by mass, particle size: 0.5 to 1.0 mm) was prepared.

(Example 4)
[Preparation of copper-supported sepiolite catalyst by ion exchange method]
A catalyst pellet (ex-Cu30) in which copper was supported on sepiolite by an ion exchange method in the same manner as in Example 1 except that the amount of sepiolite was changed to 21.17 g and the amount of copper acetate monohydrate was changed to 20.02 g. / Sep, copper loading amount: 30% by mass, particle size: 0.5 to 1.0 mm) was prepared.

(Example 5)
[Preparation of copper-supported sepiolite catalyst by impregnation method]
First, 20.70 g of sepiolite, which had been heat-treated in the same manner as in Example 1, was added to 300 ml of ion-exchanged water and stirred to prepare a sepiolite dispersion. Further, dissolved copper nitrate trihydrate _{(Cu (NO 3) 2 ·} 3H 2 O, Fuji Film manufactured by Wako Pure Chemical Industries, Ltd.) 2.43g of ion exchange water 50 ml. After dropping the obtained copper nitrate aqueous solution into the sepiolite dispersion, the mixture is stirred while heating at 230 ° C. using a hot plate and concentrated until it becomes a slurry, and the obtained concentrated slurry is placed in a dryer at 110 ° C. It was dried overnight.

Next, the obtained solid content was heat-treated at 300 ° C. for 3 hours under an atmospheric air flow of 1 L / min, and further, an H ₂ / N ₂ mixed gas air flow (H ₂ / N ₂ = 0.05 []. It was heat-treated at 500 ° C. for 5 hours under ml / min] /0.95 [ml / min]). The obtained solid powder was powder-molded, crushed and sized, and catalyst pellets (imp-Cu3 / Sep, copper-supported amount: 3% by mass, particle size: 0.) in which copper was supported on sepiolite by an impregnation method. 5 to 1.0 mm) was obtained.

(Comparative Example 1)
[Preparation of sepiolite pellets]
Sepiolite pellets (Sep, copper carrying amount: 0% by mass, particle size: 0.5 to 1.0 mm) were obtained in the same manner as in Example 5 except that copper nitrate trihydrate was not used.

(Comparative Example 2)
[Preparation of nickel-supported sepiolite catalyst by impregnation method]
To change the amount of sepiolite to 20.75 g, nickel nitrate hexahydrate in place of copper nitrate trihydrate _{(Ni (NO 3) 2 ·} 6H 2 O, Fuji Film manufactured by Wako Pure Chemical Industries, Ltd.) 3.145G Catalyst pellets in which nickel was supported on sepiolite by the impregnation method (imp-Ni3 / Sep, nickel support amount: 3% by mass, particle size: 0.5 to 1.0 mm) in the same manner as in Example 5 except that Was prepared.

(Comparative Example 3)
[Preparation of cobalt-supported sepiolite catalyst by impregnation method]
To change the amount of sepiolite to 20.91 g, cobalt nitrate hexahydrate in place of copper nitrate trihydrate _{(Co (NO 3) 2 ·} 6H 2 O, Fuji Film manufactured by Wako Pure Chemical Industries, Ltd.) 3.164G The catalyst pellet (imp-Co3 / Sep, cobalt-supported amount: 3% by mass, particle size: 0.5 to 1.0 mm) in which cobalt was supported on sepiolite by the impregnation method in the same manner as in Example 5 except that Was prepared.

(Comparative Example 4)
[Preparation of copper-supported magnesium oxide catalyst by impregnation method]
Impregnation was carried out in the same manner as in Example 5 except that 14.75 g of magnesium oxide (MgO, manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) was used instead of sepiolite and the amount of copper nitrate trihydrate was changed to 1.76 g. A catalyst pellet (imp-Cu3 / MgO, copper carrying amount: 3% by mass, particle size: 0.5 to 1.0 mm) in which copper was carried on magnesium oxide was prepared by the method.

(Comparative Example 5)
[Preparation of copper-supported yttrium oxide catalyst by impregnation method]
_{Same as Example 5 except that 15.04 g of yttrium oxide (Y 2} O ₃ , manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) was used instead of sepiolite, and the amount of copper nitrate trihydrate was changed to 1.79 g. Te, copper by impregnation catalyst pellets supported on yttrium oxide _{(I-Cu3 / Y 2 O} 3, copper content: 3 mass%, particle size: 0.5 to 1.0 mm) was prepared.

(Comparative Example 6)
[Preparation of copper-supported cerium oxide catalyst by impregnation method]
Using 15.00 g of cerium oxide (CeO ₂ , manufactured by Anan Kasei Co., Ltd.) instead of sepiolite, the impregnation method was carried out in the same manner as in Example 5 except that the amount of copper nitrate trihydrate was changed to 1.79 g. A catalyst pellet in which copper was supported on cerium oxide (imp-Cu3 / CeO ₂ , copper support amount: 3% by mass, particle size: 0.5 to 1.0 mm) was prepared.

(Comparative Example 7)
[Preparation of copper-supported aluminum oxide catalyst by impregnation method]
By the impregnation method in the same manner as in Example 5, 20.00 g of _{aluminum oxide (Al 2} O ₃ , manufactured by Sasol) was used instead of sepiolite, and the amount of copper nitrate trihydrate was changed to 2.50 g. A catalyst pellet (imp-Cu3 / Al ₂ O ₃ in which copper was carried on aluminum oxide, copper carrying amount: 3% by mass, particle size: 0.5 to 1.0 mm) was prepared.

<Ammonia removal performance evaluation test>
First, as shown in FIG. 2, the catalyst pellets obtained in Examples 1 to 5 or Comparative Examples 2 to 7 or the catalyst pellets obtained in Comparative Example 1 were obtained in a quartz cylindrical reaction tube 100 (inner diameter: 16 mm). 2.0 g of sepiolite pellets were filled to form a catalyst layer 101 (thickness: 20 mm, capacity: 4.0 ml), and the catalyst layer 101 was filled with quartz glass wool 102a and 102b (both thickness: 4 mm, capacity: 1). It was fixed in the central part of the reaction tube 100 by sandwiching it with (0.0 ml). The arrows in FIG. 2 indicate the flow of the gas introduced into the reaction tube 100 and the gas discharged.

Next, the reaction tube 100 to which the catalyst layer 101 is fixed is installed in the heating furnace of the fixed bed flow type reactor (“CATA-5000-6” manufactured by Best Sokki Co., Ltd.), and the model gas (NH ₃ (900 ppm)) is installed. ) + H ₂ (3.6% by volume) + H ₂ O (3.0% by volume) + O ₂ (0.4% by volume) + N ₂ (remaining)) as shown in FIG. 3 while circulating at a flow rate of 10 L / min. After the temperature of the gas entering the catalyst rises from the lower limit temperature of measurement ( _Tlow , set here at 150 ° C) to the upper limit temperature of measurement ( _High , set here at 650 ° C) at a heating rate of 40 ° C / min. It is held at the upper limit temperature ( _High ) for 5 minutes, and further _{drops from the upper limit temperature (High} ) to the lower limit temperature (T _low ) at a temperature lowering rate of -20 ° C./min, and then the lower limit temperature (T _low ). The model gas and the reaction tube 100 were heated in a heating furnace to pretreat the catalyst layer 101 so that the temperature was maintained for 10 minutes.

After that, while continuously circulating the model gas at a flow rate of 10 L / min, as shown in FIG. 3, the temperature of the catalyst-filled gas rises from the lower limit temperature ( _Tlow ) to the upper limit temperature ( _High ) at a temperature rise rate of 10 ° C. The model gas and the reaction tube 100 are heated in a heating furnace so as to rise at / min, and at each catalyst inlet / gas temperature, the components (NH ₃ , H ₂ , O ₂ and nitrogen oxides) contained in the discharged catalyst exhaust gas are oxidized. The concentration of the substance) was measured.

Based on the obtained measurement results, the following formula:
NH ₃ removal rate [%] = (C ^NH3 _in −C ^NH3 _out ) / C ^NH3 _in × 100
^{(Wherein, C} _{NH3 in} represents NH ₃ concentration in the catalyst inflow gas (volume ^fraction), _{C NH3 out} represents NH ₃ concentration of the catalyst exiting gas (volume fraction).)
It was calculated NH ₃ removal rate of each catalyst inflow gas temperature by. Table 1 shows _{the maximum value of the NH 3} removal rate and the catalyst input gas temperature T ^{NH 3} _m at this time.

Further, based on the obtained measurement results, the N ₂ selectivity at each catalyst input gas temperature was calculated as follows. That is, on the catalyst, the following formulas (1) to (3):
4NH ₃ + 3O ₂ → 2N ₂ + 6H ₂ O (1)
2H ₂ + O ₂ → 2H ₂ O (2)
4NH ₃ + 5O ₂ → 4NO + 6H ₂ O (3)
It is considered that the _{O 2} consumption reaction represented by is occurring. Of these, the amount of O ₂ consumed (volume fraction) ^CO2 _{N2 in the N 2} formation reaction represented by the above formula (1) is the following formula:
C ^O2 _N2 = 3/4 × {(C ^NH3 _in- C ^NH3 _out ) -C ^NO _out }
(In the formula, C ^{NH 3} _{in represents the NH 3} concentration (volume fraction) in the gas entering the catalyst ^{, C NH 3} _out represents the NH 3 concentration (volume fraction) in the gas discharged from the catalyst, and C ^NO _{out represents the concentration of NH 3} in the gas discharged from the catalyst. Indicates the NO concentration (volume fraction) in the gas.)
The N ₂ selectivity is calculated by the following formula:
N ₂ selectivity [%] = ^CO2 _N2 / ^CO2 _total × 100
(In the equation, ^CO2 _N2 represents the consumption of O ₂ (volume fraction) in the N ₂ ^{production reaction, and CO2} _total represents the total consumption of O ₂ (volume fraction).)
Can be calculated by Table 1, the catalyst inlet gas temperature T ^N2 _m of the thus maximum N ₂ selectivity (N ₂ maximum selectivity) of N ₂ selectivity of each catalyst inlet gas temperature that is calculated and this time Is shown.

As shown in Table 1, the catalyst (Examples 1-5) carrying a Cu sepiolite, compared to the case of sepiolite alone (Comparative Example 1), the maximum value of the NH ₃ removal rate is extremely high and, The maximum value of N ₂ selectivity was also high, and it was found that the ammonia removal performance and nitrogen selectivity were excellent.

On the other hand, the catalyst in which Ni is supported on sepiolite (Comparative Example 2) has _{the same maximum NH 3} removal rate and a lower maximum _{N 2 selectivity as compared with the case of sepiolite alone (Comparative Example 1).} No Ni-supporting effect was observed. Further, the catalyst in which Co was supported on sepiolite (Comparative Example 3) had a _{higher maximum value of N 2} selectivity and improved nitrogen selectivity _{as compared with the case of sepiolite alone (Comparative Example 1), but NH 3 was} removed. It was found that the maximum values of the rates were the same, and the ammonia removal performance was inferior to that of the catalysts obtained in Examples 1 to 5.

Further, a catalyst carrying Cu on magnesium oxide (Comparative Example 4), a catalyst carrying Cu on yttrium oxide (Comparative Example 5), a catalyst carrying Cu on cerium oxide (Comparative Example 6), and Cu on aluminum oxide _{The supported catalyst (Comparative Example 7) has a higher maximum NH 3} removal rate and N ₂ selectivity than the case of Sepiolite alone (Comparative Example 1), and has higher ammonia removal performance and nitrogen selectivity. _{Although it was improved, it was found that the maximum value of NH 3} removal rate and the maximum value of N ₂ selectivity were lower than those of the catalysts obtained in Examples 1 to 5, and the ammonia removal performance and nitrogen selectivity were inferior.

As described above, according to the present invention, ammonia is removed from the reformed gas containing ammonia and hydrogen at a high removal rate without the need for a plurality of adsorbers having an adsorbent for adsorbing ammonia. Furthermore, it becomes possible to generate nitrogen with a high selectivity.

Therefore, the ammonia-reformed hydrogen supply device of the present invention can exhibit high hydrogen generation ability, and further, the device can be miniaturized, so that hydrogen can be supplied to the fuel cell loaded in the automobile. It is useful as a device or the like.

1: Ammonia reforming type hydrogen supply device 10: Raw material supply device 11: Ammonia reformer 12: Hydrogen purification device 13: Oxygen supply device 14a to 14e: Gas pipe 100: Reaction pipe 101: Catalyst layer 102a, 102b: Glass wool

Claims (4)

A raw material feeder for supplying ammonia as a raw material,
An ammonia reformer for generating a reformed gas containing hydrogen by reforming the ammonia supplied from the raw material feeder, and
A hydrogen purification apparatus provided with an ammonia selective oxidation catalyst for oxidizing ammonia in the reforming gas supplied from the reformer.
An oxygen supply device for supplying oxygen to the hydrogen purification device and
Is equipped with
An ammonia-modified hydrogen supply device, wherein the ammonia selective oxidation catalyst is a catalyst comprising sepiolite and Cu supported on the sepiolite. Using the ammonia-modified hydrogen supply device according to claim 1, ammonia as a raw material is supplied from the raw material supply device to the ammonia reformer to generate the reformed gas, and then the reformed gas. By supplying oxygen from the oxygen supply device to the hydrogen purification device while supplying the reformed gas and the oxygen from the ammonia reformer to the hydrogen purification device, the reforming gas and the oxygen are brought into contact with the ammonia selective oxidation catalyst. A method for supplying hydrogen modified by ammonia, which comprises purifying hydrogen by oxidizing ammonia in the reforming gas and supplying the purified hydrogen. The ammonia-modified hydrogen supply method according to claim 2, wherein the temperature of the contact gas when the reformed gas and the oxygen are brought into contact with the ammonia selective oxidation catalyst is 350 to 650 ° C. The characteristic is that the supply ratio of oxygen and ammonia when brought into contact with the ammonia selective oxidation catalyst is 0.75 to 10.75 in _{terms of volume ratio ([oxygen (O 2} )] / [ammonia (NH _3)]). The ammonia-modified hydrogen supply method according to claim 2 or 3.

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