JP7364834B2 - Hydrogen generation separation device - Google Patents

Description

The present invention relates to a hydrogen generator, which has a function of catalytically decomposing ammonia using ammonia gas as a hydrogen supply source, and uses high-temperature decomposition gas generated by ammonia decomposition to heat a hydrogen separation membrane to a separation operating temperature. The present invention relates to a hydrogen separation module and a hydrogen generation/separation device that have the function of permeating and separating hydrogen gas in cracked gas using a hydrogen separation membrane.

Hydrogen is considered important as a next-generation clean energy alternative to conventional thermal and nuclear power generation.In addition to water electrolysis, hydrogen can be used for steam conversion from various raw material gases such as methane, propane gas, and city gas. Efforts are being made to develop various technologies, such as methods for separating and extracting hydrogen gas depending on its quality, and methods using catalyst technology using organic hydrides.

In particular, the method of separating and extracting hydrogen gas by steam reforming has the advantage of being able to efficiently generate only hydrogen gas with extremely high purity.For example, hydrogen gas can be selectively permeated and separated using palladium alloys or palladium-copper alloys. Metal thin film materials that can be produced are used in hydrogen separation modules and hydrogen production equipment.

For example, a cylindrical housing container includes a hydrogen separation member that is incorporated almost coaxially inside the housing, and the separation membrane member is configured to substantially isolate its upstream and downstream sides to form a processing chamber therein. A cup-shaped device with a lid on the top is used.

A gas fluid to be treated as a raw material is introduced into the processing chamber from an inlet introduced from outside the system, and only hydrogen gas contained in the fluid to be treated is generated by permeation separation in the hydrogen separation member, The obtained hydrogen gas is sent to the next process from the outlet, while the residual gas remaining in the processing chamber and the unreacted fluid to be treated are separately taken out from the recovery port. It is configured.

By the way, with such hydrogen separation technology, hydrogen gas can be easily separated and extracted from the raw material gas fluid, but the reaction requires heating the raw material gas to a predetermined reaction temperature of, for example, about 400 to 500°C. is necessary. Heating methods include, for example, heating separately in a preliminary stage and then supplying it in-line, and, for example, by providing an external heater placed on the outer periphery of the cylindrical module so as to envelop the entire module. ing. (For example, Patent Documents 1 to 3)

Japanese Unexamined Patent Publication No. 2015-171705 Japanese Unexamined Patent Publication No. 2005-44709 Japanese Unexamined Patent Publication No. 2004-75442

However, in each of these prior art techniques, it is difficult to obtain a good supply condition for the raw material gas to be introduced into the separation membrane material to be permeated and separated, and it is easy to cause stagnation or partial supply unevenness. In addition to not being able to provide a uniform and efficient supply throughout the module, the heating process requires a separate heating means or an external heating method in which a heating device is placed outside to wrap the module. In addition to requiring a larger heating means, energy efficiency also increases heat loss, resulting in an increase in the size of the separation membrane module itself. Improvements are required in terms of gas flow characteristics and heating characteristics. .

In view of the above problems, the present invention utilizes ammonia gas as a hydrogen supply source, mixes an oxygen-containing gas such as air with this to generate ammonia raw material gas, and decomposes the ammonia into the ammonia raw material gas. A catalyst is applied to decompose the ammonia in the raw material gas, a part of the hydrogen gas generated by the decomposition reaction is oxidized, and the high-temperature gas after ammonia decomposition (ammonia decomposition By adopting a method of heating the hydrogen separation membrane using generated gas), there is no need to use a new external heat source to heat the hydrogen separation membrane, reducing heat loss and suppressing the increase in size of the separation membrane module itself. The purpose of the present invention is to provide a hydrogen separation module and a hydrogen generation device that are capable of uniformly and efficiently supplying ammonia raw material gas and have excellent usability.

That is, the invention according to claim 1 of the present invention includes a housing container, a cylindrical first flow path for circulating ammonia raw material gas supplied from outside the system into the housing container, and a first flow path in the first flow path. an ammonia decomposition catalyst filled concentrically; a heat insulating member disposed concentrically on the inner circumferential side of the first channel; a cooling pipe disposed spirally on the outer circumferential side of the first channel; A storage space for temporarily storing gas fluid after decomposition processing at the end of the flow path, and a hydrogen separation space concentrically arranged on the inner circumferential side of the heat insulating member to separate hydrogen gas from the ammonia decomposition product gas. a second flow path formed by a cylindrical inner pipe arranged concentrically on the inner peripheral side of the hydrogen separation member and for circulating the ammonia decomposition product gas in the storage space, and a partition wall of the inner pipe. and the hydrogen separation member, and the hydrogen gas separated by the hydrogen separation member is circulated outside through the fourth flow path formed between the heat insulation member and the hydrogen separation member. This is a hydrogen generation and separation device incorporating a hydrogen separation module, which is characterized in that the hydrogen gas is separated and the exhaust gas after hydrogen gas separation is circulated to the outside through a third flow path.

The invention according to claim 2 is that the ammonia decomposition catalyst has an operating temperature range of 200°C to 500°C and is capable of generating hydrogen gas, and the invention according to claim 3 is a catalyst that can generate hydrogen gas. The invention according to claim 4 provides a cooling pipe so that the temperature of the exhaust gas in the exhaust pipe is maintained at 400 to 500°C. ), the volume of the third flow path (V3) and the volume of the storage space 12 (Vt) are each in the relationship of V1<Vt≦V2≦V3. be.

The invention according to claim 5 provides a hydrogen separation member comprising a hydrogen permeable membrane having a hydrogen permeation separation function, and a laminated structure product including a metal buffer sheet and a metal porous plate that wrap the outer surface of one of the membranes and provide pressure-resistant support. This is a hydrogen generation and separation device with a built-in hydrogen separation module, characterized in that it is constructed of a metal or ceramic buffer sheet containing an oxygen scavenger and having fine pores on the other outer surface.

In the present invention, an ammonia decomposition catalyst and a first flow path are provided along the inner surface of the partition wall of the housing container, and cooling piping is provided in a spiral shape on the outer surface of the partition wall of the housing container in the first flow path portion, so that the volume is larger than that of the first flow path. The ammonia decomposition product gas is It has the advantage of cooling the hydrogen separation membrane and heating the hydrogen separation membrane within its operating temperature range.

That is, the ammonia raw material gas introduced with this configuration is decomposed by the ammonia decomposition catalyst disposed in the first flow path, and the generated ammonia decomposition product gas of 500 to 700°C is transferred to the second flow path, which is provided with cooling piping on the outer surface. The ammonia decomposition product gas is stored in the storage space while being cooled through the first channel, and then undergoes pseudo-adiabatic expansion through the storage space, second flow channel, and third flow channel to transfer the ammonia decomposition product gas to the operating temperature range of the hydrogen separation membrane. The hydrogen is cooled to 400 to 500°C and fed to the hydrogen separation member without retention.

Further, according to the invention of claim 5 of the present application, oxidative deterioration of the hydrogen separation membrane is suppressed, and hydrogen can be efficiently generated.

From the above, by suppressing the heat loss while the ammonia decomposition product gas flows through the equipment, it is possible to save energy by eliminating the need for a new external heat source or large hydrogen separation membrane module to heat the hydrogen separation membrane. It is possible to generate hydrogen as desired.

1 is a schematic configuration diagram of a hydrogen generation and separation device according to the present invention. A cross-sectional view of a heat insulating member. FIG. 3 is a cross-sectional view of a hydrogen separation member. A sectional view taken along the line A-A in FIG. 1. A sectional view taken along the line B-B in FIG. 1. A sectional view taken along the line C-C in FIG. 1. A sectional view taken along the line D-D in FIG. 1. The area diagram of the 1st flow path to the 4th flow path, and a retention space in a hydrogen generation separator. The figure regarding the ammonia decomposition raw material gas supply control method in a hydrogen generation separator. FIG. 2 is a schematic configuration diagram of a hydrogen generation and separation device according to another embodiment. An example of application of the hydrogen generation separation device according to the present invention to a VOC decomposition device.

DESCRIPTION OF THE PREFERRED EMBODIMENTS A hydrogen generation and separation apparatus, which is the best embodiment of the present invention, will be described below with reference to FIGS. 1 to 11. Here, FIG. 1 is a configuration diagram showing a schematic configuration of the hydrogen generation and separation device of this embodiment, FIG. 2 is a sectional view of a heat insulating member of a hydrogen separation module, and FIG. 3 is a sectional view of a hydrogen separation member. , FIG. 4 is a cross-sectional view taken along line A-A in FIG. 1, FIG. 5 is a cross-sectional view taken along line B-B in FIG. 1, FIG. 6 is a cross-sectional view taken along line C-C in FIG. 1, and FIG. 7 is a cross-sectional view taken along line D-D in FIG. FIG. 8 is a diagram showing the areas from the first flow path to the fourth flow path and the storage space in FIG. 1 is a cross-sectional view of the entire hydrogen generation and separation device different from that shown in FIG. 1, and FIG. 11 is an example of application of the present invention to a VOC decomposition device.

As shown in FIG. 1, the hydrogen generation and separation device 1 of this embodiment includes a housing container 2 having thermal conductivity, and a cylindrical first flow for circulating ammonia raw material gas supplied from outside the system into the housing container 2. a RuO2/γ-Al2O3 catalyst (aluminum oxide supported ruthenium oxide catalyst) which is the ammonia decomposition catalyst 4 filled concentrically in the first flow path 11, and a RuO2/γ-Al2O3 catalyst (aluminum oxide supported ruthenium oxide catalyst) filled concentrically in the first flow path A heat insulating member 9 arranged, a cooling pipe 6 arranged concentrically on the outer peripheral side of the first flow path 11 for cooling the ammonia decomposition product gas, and a gas fluid after the decomposition treatment at the end of the first flow path 11. a storage space 12 for temporarily storing (gas produced by ammonia decomposition); and a hydrogen separation member 10 arranged concentrically on the inner peripheral side of the heat insulating member 9 to separate hydrogen gas from the gas produced by ammonia decomposition; A second flow path 13 is disposed concentrically on the inner circumferential side of the hydrogen separation member 10 and is formed by an inner pipe 8 for circulating gas after ammonia decomposition in the storage space 12, and a partition wall of the inner pipe 8. A third flow path 14 is provided between the hydrogen separation member 10 to expose the ammonia decomposition product gas to the hydrogen separation member 10, and a heat insulation member 9 is provided to allow the hydrogen gas separated by the hydrogen separation member to flow outside. A fourth flow path 15 is provided and configured between the hydrogen separation member 10 and the fourth flow path 15 .

That is, as shown in FIG. 1, the hydrogen generation/separation device 1 of this embodiment includes an ammonia gas introduction pipe 3, an inner pipe 8, and a heat insulating member in a housing container 2 in which a cooling pipe 6 is provided on the outer periphery of the housing container 2. 9. It has a structure in which a hydrogen separation module 7 constituted by a hydrogen separation member 10, a hydrogen gas discharge pipe 16, an exhaust gas accumulation pipe 17 after hydrogen separation, and an exhaust gas discharge pipe 18 is housed.

FIG. 2 is a cross-sectional view of the heat insulating member 9 in the hydrogen separation module 7 from the ammonia gas introduction pipe 3 side (upstream side) to the exhaust gas discharge pipe 18 side (downstream side). The heat insulating member 9 in the hydrogen separation module 7 is a heat insulating material stretched over the structural material 22 by the structural material 22 of the hydrogen separation module, a heat insulating material fixing claw 23 formed continuously from the structural material 22, and a heat insulating material sheet 24. It has a structure in which the sheet 24 is fixed with heat insulating material fixing claws 22. Note that the material of the structural member 22 of the hydrogen separation module may be any heat-resistant material that does not deform at a high temperature of 700° C., and is preferably a metal such as iron, stainless steel, or copper, or ceramics. Further, the heat insulating material may also be made of a material that can withstand high temperatures of 700°C, and is preferably made of rock wool, ceramics, or the like. Note that if the thickness of the heat insulating member 9 is too thin, the inside of the hydrogen separation module 7 will be heated to a predetermined temperature or higher due to the heat generated due to the oxidation reaction of hydrogen generated by ammonia decomposition, and if it is too thick, it will be difficult to make the device more compact. Therefore, a thickness of about 5 to 15 mm is preferable.

FIG. 3 is a sectional view of the hydrogen separation member 10 in the hydrogen separation module 7 from the ammonia gas introduction pipe 3 side (upstream side) to the exhaust gas discharge pipe 18 side (downstream side). The hydrogen separation member 10 is a thin hydrogen separation membrane made of a specific metal material that has a function of selectively permeating hydrogen gas contained in the ammonia decomposition product gas (X). Hydrogen separation membranes with a permeation function include, for example, palladium metal, vanadium metal, alloy materials of these metals such as palladium-copper alloy, palladium-silver alloy, vanadium-nickel alloy, and zirconium-nickel amorphous alloy. Thin film materials such as those made by et al.

The thickness of the hydrogen separation membrane is, for example, preferably 5 to 50 μm, but is not limited thereto. The size and shape of the hydrogen separation member 10 are taken into consideration depending on its purpose of use and processing capacity. For example, a cylindrical product with a circular cross section is formed to have a diameter of 10 to 300 mm and a length of 50 to 1000 mm.

When using the thin hydrogen separation membrane, as disclosed in JP-A-2017-192930, the ammonia decomposition product gas (X) is supplied in a pressurized state with a constant load pressure applied from the inner circumferential side. Therefore, as shown in Fig. 3, the outer periphery of the hydrogen separation membrane is covered with a single layer or multiple layers of an enveloping member 27 consisting of a punching plate (perforated plate) 25 and a buffer sheet 26 to withstand the load pressure. It has the structure that you get. The buffer sheet 26 may be a sintered nonwoven sheet made of a corrosion-resistant metal fiber material such as stainless steel, nickel metal, or nickel alloy, or a sheet prepared by mixing and molding powders of these corrosion-resistant metals.

However, the hydrogen separation membrane is oxidized in the presence of oxygen, and its hydrogen permeability deteriorates accordingly, so in order to suppress this, the ammonia decomposition gas containing oxygen and water vapor in the hydrogen separation member 10 comes into contact with the hydrogen separation membrane. An oxygen scavenger-containing buffer sheet 29 is coated on the inner peripheral side. The oxygen scavenger-containing buffer sheet 29 may be made of a nonwoven sintered fabric made of a composite material of a corrosion-resistant metal fiber material such as the above-mentioned stainless steel, nickel metal, or nickel alloy, and a corrosive metal fiber material capable of removing oxygen such as iron. A single layer or a plurality of sheets formed by mixing and forming powders of these corrosion-resistant metals and corrosive metals are used. As a result, it is possible to provide a certain degree of flexibility and elasticity as well as workability, weldability, etc., and to exhibit an oxygen scavenging function.

In addition, in the outer peripheral side buffer sheet 26 and the inner peripheral side buffer sheet 29 containing an oxygen removing agent of the hydrogen separation membrane 28, the interface between these buffer sheet layers and the hydrogen separation membrane is, for example, provided with a material having the same function as the buffer sheet. It is also possible to arrange a metal screen mesh or the like to form a composite laminated material with a multilayer structure, and apply the composite laminated material as the hydrogen separation member 10. The screen mesh prevents the filaments constituting both buffer sheets 26 and 29 from sticking to the hydrogen separation membrane 28, and makes it possible to secure a flow path for the separated and permeated hydrogen.

As the punching plate 25, for example, as disclosed in JP-A-2008-246430, a perforated metal plate having small holes punched out at approximately equal intervals is employed.

The form of the hydrogen separation member 10 is such that the above-described composite laminated material or metal powder mixed molded sheet is used on the outer circumferential side and the inner circumferential side of the hydrogen separation membrane 28, and the ammonia decomposition product gas (X) is passed through the inner circumference. When the hydrogen separation membrane 28 is supplied from the side toward the outer circumferential side, the hydrogen separation membrane 28 can be pushed outward by the supply pressure of the ammonia decomposition product gas (X), and the hydrogen separation membrane 28 can be temporarily wrinkled or loosened. Even if there is a problem, the supply pressure is always maintained at a predetermined tension, and the supply pressure is protected by the enveloping member 27 with sufficient pressure resistance, so that breakage and the like can be prevented. Therefore, the hydrogen separation membrane 28, the punching plate 25, the buffer sheet 26, etc., and the oxygen scavenging agent-containing buffer sheet 29 can be used in a stacked state in which they are simply stacked on top of each other, or, for example, in whole or in part. It is also possible to use them as an integral piece by bonding them together in advance.

The hydrogen separation member 10 has both end edges connected to a holding member 21A located at the start point of the third flow path 14 on the ammonia decomposition product gas inflow side in the hydrogen separation module 7 and at the end point of the third flow path 14 on the exhaust gas discharge side. They are each fixed to the respective holding members 21B without leakage.

The decomposition process of ammonia raw material gas by the hydrogen generation and separation device 1 will be explained using FIG. 1 in a case where the RuO2/γ-Al2O3 catalyst is used as the ammonia decomposition catalyst 4. The ammonia raw material gas introduced into the hydrogen generation and separation device 1 through the ammonia gas introduction pipe 3 is decomposed into ammonia by the ammonia decomposition catalyst 4 (RuO2/γ-Al2O3 catalyst) filled in the first flow path 11, as shown in FIG. The ammonia decomposition product gas is heated to 500 to 700°C by the heat generated when a part of the hydrogen gas generated in this decomposition reaction is oxidized to produce water, and the decomposed gas is heated to 500 to 700°C. and then passes through the second flow path 13 in the inner pipe 8 of the hydrogen separation module 7 and collides with the partition wall of the module 7, and then between the partition wall of the inner pipe 8 and the hydrogen separation member 10. Hydrogen gas present in the cracked gas is introduced into a third flow path 14 formed between the heat insulating member 9 and the hydrogen separation member 10 and passes through the hydrogen separation member 10 to form a fourth flow path formed between the heat insulating member 9 and the hydrogen separation member 10. 15, after which the hydrogen gas is collected and discharged through a hydrogen gas discharge pipe 16. Further, the exhaust gas after the hydrogen gas has been separated moves from the third flow path 14, is collected by the exhaust gas collection pipe 17, and is discharged through the exhaust gas discharge pipe 18.

The RuO2/γ-Al2O3 catalyst described above is an ammonia decomposition catalyst described in Patent No. 6566662, but the ammonia decomposition catalyst can also be made of transition metal-based metals such as Fe, Co, Ni, Mo, and Ru, alloys, and nitrides. It is possible to use metals, carbides, oxides, composite oxides, rare earth metals such as La, Ce, and Nd, and oxides thereof.

Further, the ammonia decomposition catalyst can be used by being supported on a honeycomb carrier formed of ceramics such as cordierite.

Cross-sectional views in the direction from the ammonia gas inlet pipe 3 to the exhaust gas discharge pipe 18 (the cooling pipe 6 is omitted) in the hydrogen generation and separation apparatus 1 are shown in FIGS. 4 to 7. FIG. 4 is a cross-sectional view taken along the line A-A in FIG. 1, and is a cross-sectional view when the hydrogen separation module 7 is arranged within the housing container 2. The space created between the partition wall of the housing container 2 and the heat insulating member 9 of the hydrogen separation module 7 is defined as a first flow path 11, and the ammonia decomposition catalyst 4 supported on the honeycomb carrier is disposed in the first flow path 11. In the separation module 7, the space created between the heat insulating member 9 and the hydrogen separation member 10 placed inside this is a fourth flow path 15, and the space between the hydrogen separation member 10 and the inner tube placed inside this The space created between the tubes 8 and 8 will be referred to as a third flow path 14, and the space in the inner tube 8 will be referred to as a second flow path 13.

FIG. 5 is a cross-sectional view taken along the line B-B in FIG. 1, and is a diagram showing the positional relationship between the housing container 2 and the hydrogen separation module 7 at a position closer to the exhaust gas discharge pipe 18 than the position of the cross-sectional view taken along the line A-A in FIG. be. The space created between the partition wall of the housing container 2 and the heat insulating member 9 of the hydrogen separation module 7 is defined as the first flow path 11, and as in the case of FIG. The space created between the hydrogen separation member 10 placed on the inside is referred to as a fourth flow path 15, and the space created between the hydrogen separation member 10 and the inner tube 8 placed on the inside thereof is referred to as a third flow path 14. , the space of the inner tube 8 is defined as a second flow path 13.

6 and 7 are a sectional view taken along the line C-C and a sectional view taken along the line D-D in FIG. FIG. The exhaust gas accumulation pipe section 17 shown in FIG. 6 is a conduit for guiding the hydrogen-separated exhaust gas that has passed through the third flow path 14 to the exhaust gas discharge pipe 18. In the exhaust gas accumulation pipe section 17, a plurality of exhaust gas accumulation pipes may be directly connected to the exhaust gas discharge pipe 18, or a plurality of exhaust gas accumulation pipes may all be connected in front of the exhaust gas discharge pipe 18 as shown in FIG. It is also possible to provide an exhaust gas reservoir shaped to cover the exhaust gas collection pipe.

Furthermore, as shown in FIG. 8, the hydrogen generation and separation device 1 shown in FIG. Let V2 be the volume of the internal space (second flow path) of the inner tube 8, and let V3 be the volume of the space (third flow path) created between the hydrogen separation member 10 and the partition wall of the inner tube 8 located inside it. , if the volume of the space (storage space 12) between the downstream end of the housing container 2 and the downstream end of the hydrogen separation module 7 minus the exhaust gas accumulation pipe section 17 is Vt, then V1< This hydrogen generation and separation device is characterized by the relationship of Vt≦V2≦V3. Due to the pseudo adiabatic expansion effect produced by configuring the flow path and the storage space in such a volumetric relationship, it is possible to lower the temperature of the decomposed gas generated by ammonia decomposition by volumetrically expanding it.

As for the method of cooling the ammonia decomposition product gas in the hydrogen generation/separation device 1, in addition to the method described in the previous section, it is also possible to adopt a method of cooling the ammonia decomposition product gas by flowing a refrigerant through the cooling piping 6. For example, there is a method of using water or oil as the refrigerant.

Further, as a method for controlling the temperature of the ammonia decomposition product gas, it is also possible to adopt a method of adjusting the mixing ratio of ammonia gas and oxygen (air) in the ammonia raw material gas and the flow rate of the mixed gas. This is because it is necessary to adjust the temperature of the ammonia decomposition product gas in the hydrogen separation member 10 to within 400 to 500°C, which is the operating temperature of the hydrogen separation membrane 28. On the side, a temperature sensor (1) 19 provided on the downstream side of the ammonia decomposition catalyst 4 and a temperature sensor (2) 20 provided on the inner circumference of the exhaust gas discharge pipe 20 measure the temperature at the time of ammonia decomposition product gas generation and the temperature after hydrogen separation. The temperature when the exhaust gas is discharged is measured, the temperature data is sent to the control unit 35 shown in FIG. This is a method of supplying fuel to the hydrogen generation and separation device 1 by adjusting the mixing ratio of ammonia gas and oxygen (air) in the ammonia raw material gas and the flow rate of the raw material gas using the supply device 36.

The cooling method of the hydrogen generation and separation device 1 of this embodiment is basically a method of cooling by flowing a refrigerant through the cooling piping 6 as shown in FIG. 1, but as shown in FIG. It is also possible to provide an air cooling system by providing a heat sink 37 instead of the cooling pipe 6 on the outside.

Note that the air-cooled hydrogen generation and separation device 1 can also be used as a heater because it radiates heat to the outside air. For example, as shown in FIG. 11, a multi-stage hydrogen generation and separation device 39 in which a plurality of hydrogen generation and separation devices 1 are stacked in a VOC catalytic decomposition device 38 is installed in the ammonia heater section 40, so that the VOC ( When decomposing volatile organic compounds) with the VOC decomposition catalyst 41, the catalyst 41 can be used as a VOC heating heater for heating the catalyst 41 with VOC to a decomposition operating temperature.

1 Hydrogen generation separation device
2 Housing container
3 Ammonia gas introduction pipe
4 Ammonia decomposition catalyst
5 Ammonia decomposition catalyst fixing jig
6 Cooling piping
7 Hydrogen separation module 8 Inner pipe 9 Heat insulating member 10 Hydrogen separation member 11 First flow path 12 Storage space 13 Second flow path 14 Third flow path 15 Fourth flow path 16 Hydrogen gas discharge pipe 17 Exhaust gas accumulation pipe section 18 Exhaust gas discharge pipe 19 Temperature sensor (1)
20 Temperature sensor (2)
21A, 21B Holding member 22 Hydrogen separation module structural material 23 Fixing claw 24 Heat insulating sheet 25 Punching plate 26 Buffer sheet 27 Enveloping member 28 Hydrogen separation membrane 29 Oxygen removing agent compounded buffer sheet 30 Volume of first flow path V1
31 Volume of retention space Vt
32 Volume of second flow path V2
33 Volume of third flow path V3
34 Volume of the fourth flow path V4
35 Control section 36 Gas mixing/supply device 37 Heat sink 38 VOC decomposition device 39 Multi-stage hydrogen generation and separation device 40 Ammonia heater section 41 VOC decomposition catalyst 42 Catalytic decomposition processing section

Claims (5)

In a hydrogen generation and separation device that generates and separates hydrogen gas using a mixed gas of ammonia gas and oxygen-containing gas as a raw material,
The hydrogen generation and separation device includes a housing container;
A cylindrical first flow path for circulating the mixed gas supplied from outside the system in the container;
an ammonia decomposition catalyst filled concentrically within the cylindrical flow path;
a heat insulating member disposed concentrically on the inner peripheral side of the cylindrical flow path;
A cooling pipe arranged on the outer peripheral side of the first flow path to cool the ammonia decomposition product gas;
a storage space for temporarily storing gas fluid after decomposition processing at the end of the cylindrical flow path;
a hydrogen separation member disposed concentrically on the inner peripheral side of the heat insulating member to separate hydrogen gas from the ammonia decomposition product gas;
a second flow path formed by a cylindrical inner pipe that is arranged concentrically on the inner peripheral side of the hydrogen separation member and allows the ammonia decomposition product gas in the storage space to flow;
a third flow path formed between the partition wall of the inner tube and the hydrogen separation member;
Equipped with
Flowing the hydrogen gas separated by the hydrogen separation member to the outside through a fourth flow path formed between the heat insulation member and the hydrogen separation member,
and circulating the exhaust gas after hydrogen gas separation to the outside through a third flow path.
A hydrogen generation and separation device equipped with a built-in hydrogen separation module. The hydrogen generation and separation apparatus according to claim 1, wherein the ammonia decomposition catalyst has an operating temperature range of 200° C. to 500° C. and is a catalyst capable of generating hydrogen gas. The hydrogen generation and separation apparatus according to claim 1, further comprising a cooling pipe for passing a refrigerant so that the temperature of the exhaust gas in the exhaust gas discharge pipe is maintained at 400 to 500°C. The volume (V1) in the first flow path, the volume (V2) in the second flow path, the volume (V3) in the third flow path, and the volume (Vt) in the storage space 12 are each such that V1<Vt≦V2≦V3. The hydrogen generation/separation device according to claim 1, wherein The hydrogen separation member is composed of a laminated structure consisting of a hydrogen permeable membrane having a hydrogen permeation separation function, a metal buffer sheet and a metal porous plate that wrap one outer surface and provide pressure-resistant support, and the other outer surface has a hydrogen permeable membrane. 2. The hydrogen generation and separation device according to claim 1, which is constructed of a metal or ceramic buffer sheet containing an oxygen scavenger and having micropores.

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