WO2017154732A1 - Device for decomposing ammonia, and device for manufacturing hydrogen gas - Google Patents

Abstract

The present invention relates to: a device for decomposing ammonia, having an ammonia decomposer, an ammonia feeder communicated with the ammonia decomposer via a connecting duct, an ammonia sensor (a1), a shut-off switch (b1) for receiving a signal from the ammonia sensor (a1) and shutting off the supplying of ammonia to the ammonia decomposer, and a casing (I), at least the ammonia feeder, the ammonia sensor (a1), and the shut-off switch (b1) being provided inside the casing (I); and a device for manufacturing hydrogen gas which has the device for decomposing ammonia.

Description

Ammonia decomposition device and hydrogen gas production device

The present invention relates to an ammonia decomposition apparatus and a hydrogen gas production apparatus having the ammonia decomposition apparatus.

Generate carbon dioxide to solve problems such as the risk of exhaustion of fossil fuels due to mass consumption of fossil fuels due to the increase in the world population, mass consumption of electric energy, and concerns about global warming due to an increase in carbon dioxide. It is expected to shift to a society that uses renewable energy (solar heat, sunlight, geothermal, wind power, etc.) that does not use it with high efficiency. Renewable energy is used by converting it into electric energy, but it is difficult to store and transport large quantities of energy because of its low energy density.
Hydrogen energy has been proposed as a clean secondary energy of the above-mentioned renewable energy. Since hydrogen is a secondary energy that does not generate carbon dioxide and can be stored and transported, construction of a hydrogen society using hydrogen energy is expected. However, hydrogen is a gas at normal temperature and normal pressure, and requires a very low temperature or a high pressure of several tens of MPa or more in order to transport it at a high density. Therefore, in recent years, the use of ammonia has attracted attention as a chemical substance (hydrogen carrier) that can easily store and transport hydrogen.
Ammonia is easily liquefied at 20 ° C and 0.857 MPa, liquid ammonia has a very high weight hydrogen density of 17.8% by weight, and volume hydrogen density is 1.5 to 2.5 times that of liquid hydrogen. A hydrogen carrier.
As described above, ammonia is excellent as a hydrogen carrier, but it has a bad odor, is a substance that is highly irritating to mucous membranes, and is lighter than air and easily dissolved in water. It is strictly limited by regulations. Therefore, strict measures to prevent leakage of ammonia are required when using ammonia.

For example, Patent Document 1 discloses a forced exhaust means for sucking indoor gas containing ammonia leaked from equipment and exhausting it from the room in an indoor ventilation device provided with equipment such as a refrigerator using ammonia refrigerant. And a water spray chamber for collecting the gas discharged from the forced exhaust means, and a water spray means for spraying water onto the gas in the water spray chamber provided in the water spray chamber. Is described.
Patent Document 2 discloses an ammonia absorption refrigerator that includes a safety valve that opens at a predetermined pressure or more, an exhaust passage provided on the downstream side of the safety valve, and an ammonia treatment agent installed in the exhaust passage. A safety device for an ammonia absorption refrigerator is described in which a closed container surrounding the refrigerator is installed so as to be able to communicate via the safety valve.
Further, Patent Document 3 discloses a cold water heat exchanger, a hot water heat exchanger, an absorber, a refrigerant vapor generator, a switch, except for an indoor heat exchanger and an outdoor heat exchanger of an absorption refrigerator that uses ammonia as a refrigerant. An ammonia absorption refrigerator comprising: a sealed container that hermetically encloses a valve, a rectifier, and the like; and an ammonia leakage detection unit installed in at least one of an ammonia refrigerant path and a heat medium path that exchanges heat with the ammonia refrigerant. Safety devices are described.
Further, in Patent Document 4, when ammonia is applied as a refrigerant of a refrigeration / air-conditioning facility, ammonia gas leaked from a refrigeration unit of the facility is subjected to a detoxification process before being released into the atmosphere. Ammonia gas leaked from the unit is guided to a closed space such as a scrubber or a cooling tower through a duct, where salt is generated by carbon dioxide gas and water, and detoxification treatment is performed. The harm system is described.

JP-A-5-31370 JP-A-6-94336 Japanese Patent No. 6-94338 JP 2001-347127 A

However, Patent Documents 1 to 4 all relate to equipment using ammonia as a refrigerant, and do not mention an ammonia decomposition apparatus and a hydrogen gas production apparatus.
As described above, when hydrogen gas is produced using ammonia as a hydrogen carrier, ammonia is decomposed under high temperature conditions. Also, when ammonia is used for hydrogen gas production, a larger amount of ammonia is required than when ammonia is used as a refrigerant, and even if ammonia leaks, the raw material for the ammonia decomposer There is a risk that ammonia will continue to be supplied. Therefore, safety improvements are required when ammonia decomposition is performed and when hydrogen gas is produced by decomposing ammonia.
The present invention has been made under such circumstances, an ammonia decomposing apparatus capable of suppressing hydrogen leakage into the atmosphere and safely decomposing raw material ammonia to obtain hydrogen gas, and the ammonia It aims at providing the hydrogen gas manufacturing apparatus which has a decomposition device.

As a result of intensive research to achieve the above object, the inventors of the present invention have confirmed that the ammonia decomposition apparatus has an ammonia supply device that supplies ammonia to the ammonia decomposition device, an ammonia detector, and an interruption that interrupts the supply of ammonia. It has been found that the above-mentioned problem can be solved by having a casing in which a container is installed.
The present invention has been completed based on such findings.

That is, the present invention provides the following [1] to [17].
[1] An ammonia decomposer, an ammonia supplier communicated with the ammonia decomposer via a connecting pipe, an ammonia detector (a1), and a signal received from the ammonia detector (a1) to receive the ammonia decomposer A circuit breaker (b1) for shutting off ammonia supply to the casing, and a casing (I),
The ammonia decomposition apparatus, wherein the casing (I) includes at least the ammonia supply device, the ammonia detector (a1), and the circuit breaker (b1).
[2] The ammonia decomposing apparatus according to [1], further including a casing (II) in which the ammonia decomposing unit is installed.
[3] The ammonia decomposing apparatus according to [1] or [2], further including a transmitter (c1) that transmits a signal from the ammonia detector (a1).
[4] The casing (II) receives ammonia signals from the ammonia detector (a2) or the ammonia detector (a2) and the ammonia detector (a2), and supplies ammonia from the ammonia supplier to the ammonia decomposer. The ammonia decomposing apparatus according to the above [2] or [3], wherein a circuit breaker (b2) for interrupting is installed.
[5] The ammonia decomposing apparatus according to [4], further including a transmitter (c2) that transmits a signal from the ammonia detector (a2).
[6] The ammonia decomposition according to any one of [2] to [5], wherein the casing (II) is provided outside the casing (I), and the casing (II) does not include the casing (I). apparatus.
[7] The ammonia decomposing apparatus according to any one of [2] to [5], wherein the casing (I) includes the casing (II).
[8] The ammonia decomposition apparatus according to any one of [2] to [7], wherein the casing (II) and the casing (I) are in contact with each other through an isolation wall.
[9] Ammonia decomposition according to any one of [1] to [8], wherein the casing (I) has an ammonia abatement device (d1) that operates by receiving a signal from the ammonia detector (a1). apparatus.
[10] The above (4) to [9], wherein the casing (II) further includes an ammonia abatement device (d2) that operates by receiving a signal from the ammonia detector (a2). Ammonia decomposition equipment.
[11] The ammonia decomposition apparatus according to any one of [1] to [10], wherein the casing (I) is a sealed container or a sealed chamber.
[12] The ammonia decomposition apparatus according to any one of [2] to [11], wherein the casing (II) is a sealed container or a sealed chamber, or a container or a device chamber having a supply pipe and a delivery pipe.
[13] The ammonia decomposition apparatus according to any one of [2] to [12], wherein the casing (II) includes a hydrogen gas detector (e1).
[14] The ammonia decomposition apparatus according to [13], further including a transmitter (f1) that transmits a signal from the hydrogen gas detector (e1).
[15] Ammonia in the mixed gas supplied from the ammonia decomposer and the ammonia decomposer according to any one of [1] to [14] and the ammonia decomposer connected via a connecting pipe A hydrogen gas production apparatus comprising an ammonia removal apparatus for removal and a hydrogen gas purification apparatus communicating with the ammonia removal apparatus via a connecting pipe.
[16] A fuel cell using hydrogen gas obtained from the hydrogen gas production apparatus according to [15].
[17] A transport aircraft equipped with the fuel cell according to [16].

According to the present invention, there is provided an ammonia decomposing apparatus capable of suppressing hydrogen leakage into the atmosphere and safely decomposing ammonia to obtain hydrogen gas, and a hydrogen gas producing apparatus having the ammonia decomposing apparatus. can do.

It is the schematic which shows an example of the ammonia decomposition apparatus of this invention. It is the schematic which shows an example of the ammonia decomposition apparatus of this invention. It is the schematic which shows a suitable example of the ammonia decomposition apparatus of this invention. It is the schematic which shows a suitable example of the ammonia decomposition apparatus of this invention. It is the schematic which shows a suitable example of the ammonia decomposition apparatus of this invention. It is the schematic which shows a suitable example of the ammonia decomposition apparatus of this invention. It is the schematic which shows a suitable example of the ammonia decomposition apparatus of this invention. It is the schematic which shows a suitable example of the ammonia decomposition apparatus of this invention. It is the schematic which shows a suitable example of the ammonia decomposition apparatus of this invention. It is the schematic which shows a suitable example of the ammonia decomposition apparatus of this invention. It is the schematic which shows a suitable example of the ammonia decomposition apparatus of this invention. It is the schematic which shows a suitable example of the ammonia decomposition apparatus of this invention. It is the schematic which shows an example of the hydrogen gas manufacturing apparatus of this invention.

Hereinafter, the present invention will be described in detail, but the present invention is not limited to the embodiments described below.

[Ammonia decomposition equipment]
As shown in FIG. 1 or 2, the ammonia decomposing apparatus of the present invention includes an ammonia decomposing unit 2, an ammonia supplying unit 1 communicated with the ammonia decomposing unit 2 through a connecting pipe p1, and an ammonia detector (a1). And a circuit breaker (b1) that receives a signal from the ammonia detector (a1) and shuts off the supply of ammonia to the ammonia decomposer 2, and a casing (I), and the casing (I) supplies at least ammonia. A device 1, an ammonia detector (a1) and a circuit breaker (b1) are installed.
In the ammonia decomposing apparatus, in particular, when ammonia leaks in the stage until ammonia is introduced into the ammonia decomposing unit 2 from the ammonia supplier 1, the amount of ammonia leaking is larger than when ammonia leaks out in the stage after ammonia decomposing. Become. Therefore, as shown in FIG. 1, it is necessary to isolate at least the ammonia supplier 1, the ammonia detector (a1), and the circuit breaker (b1) from the outside by the casing (I). In the embodiment shown in FIG. 1, when ammonia leaks from the equipment or equipment installed in the casing (I), the ammonia detector (a1) detects the leakage of ammonia and sends a signal to the circuit breaker (b1). Send. Next, the breaker (b1) that has received the signal from the ammonia detector (a1) blocks the supply of ammonia to the ammonia decomposer 2. And since these each apparatus is installed in casing (I), it becomes possible to interrupt | block the leakage of ammonia to the exterior of casing (I).

Further, in the embodiment shown in FIG. 2, the ammonia decomposer 2 is also installed in the casing (I), and therefore, when the raw ammonia leaks from the ammonia decomposer 2 or the mixed gas (hereinafter, referred to as the raw ammonia) is decomposed. Even if ammonia leaks as simply “mixed gas”), the ammonia detector (a1) detects the leakage of ammonia and immediately supplies ammonia to the ammonia decomposer 2 as described above. It can be interrupted by the circuit breaker (b1).
The mixed gas obtained by decomposing the raw material ammonia is transported out of the ammonia decomposing apparatus, for example, by a mixed gas transport pipe p11 shown in FIGS. 1 and 2, and sent to the next process or collected in a storage container or the like.

Hereinafter, examples of preferred embodiments of the ammonia decomposing apparatus of the present invention and examples of preferred embodiments of each device, apparatus, and each equipment included in the ammonia decomposing apparatus will be described in order. It is not limited to the aspect mentioned later.

The ammonia decomposing apparatus of the present invention preferably further includes a casing (II) in which the ammonia decomposing unit 2 is installed in the above-described embodiment. As the suitable mode, for example, the mode shown in FIG. 3 or FIG. 4 can be cited.
The reaction for decomposing the raw material ammonia to obtain hydrogen gas is usually carried out under high temperature conditions. By separating the ammonia decomposer 2 from the space in which the ammonia supplier 1 is installed by the casing (II), even if the raw ammonia leaks in the casing (I), the leaked raw ammonia is at a high temperature. It is possible to suppress contact with the ammonia decomposing unit 2 operating in the above and exposure to a high temperature environment around the ammonia decomposing unit 2.

Further, for example, in the case of an embodiment having the casing (I) and the casing (II), from the viewpoint of dealing with ammonia leakage and equipment malfunction for each casing, as shown in FIG. It is preferable that it is provided outside of I) and the casing (II) does not include the casing (I).
In the case of the embodiment shown in FIG. 3, for example, when the above-described malfunction occurs in the casing (I), only the casing (I) is disconnected from the ammonia decomposition apparatus, and the leaked ammonia is treated or the malfunctioned equipment is repaired. It can be performed. Therefore, for example, when it is used as an ammonia decomposition apparatus that can be loaded on a hydrogen station or a fuel cell vehicle, the portion related to the casing (I) is made into one unit, for example, when a problem occurs in the unit related to the casing (I). , Replacing the unit relating to the casing (I) with a new unit (hereinafter, the corresponding method is simply referred to as “unit replacement correspondence”. In this case, for example, a large-sized hydrogen station or the like, the casing (I) When such a unit cannot be transported, units related to a plurality of casings (I) are installed, and when trouble occurs, raw ammonia is supplied from the unit related to another casing (I) to the casing (II). Including switching the line and continuing ammonia decomposition operation). Without long stop pneumoniae cracker, the more efficiently can perform the decomposition of ammonia. The same applies when a problem occurs in the casing (II).

Although details will be described later, it is preferable to completely prevent leakage of ammonia to the outside by using the casing (I) and / or the casing (II) as a sealed container in order to replace the unit. As a result, the ammonia trapped inside the casing can be processed using an appropriate method after being moved to a safe place. Therefore, for example, it is not necessary to perform dangerous processing in a place where the above-described hydrogen station is installed or where a fuel cell vehicle is used, and an ammonia decomposition apparatus and a hydrogen gas production apparatus having the ammonia decomposition apparatus are used. Safety can be further improved. Furthermore, the ammonia decomposition apparatus capable of unit replacement can be suitably used in facilities that require continuous operation, such as a hydrogen station, in that the time required to stop the ammonia decomposition apparatus can be shortened by unit replacement.
Further, when the casing (I) and / or the casing (II) is used as an airtight container so that the leakage of ammonia to the outside can be completely prevented, for example, installation of an ammonia detoxifying device described later is unnecessary or temporary. As a simple facility that can cope with this situation, the ammonia decomposition apparatus and the entire hydrogen gas production apparatus having the apparatus can be made compact.

From the viewpoint of making the entire ammonia decomposing apparatus more compact, as shown in FIG. 4, the casing (I) may be an embodiment in which the casing (II) is provided. In this case, unlike the above-described unit replacement correspondence, when a failure occurs in either the casing (I) or the casing (II), it is possible to replace the casing in which the failure has occurred.

Similarly, from the viewpoint of making the entire ammonia decomposing apparatus more compact, and from the viewpoint of reducing and preventing leakage of ammonia from the connecting pipe existing between the casing (I) and the casing (II), for example, as shown in FIG. Thus, it is preferable that the casing (I) and the casing (II) are in contact with each other via the isolation wall W. Further, from the viewpoint of performing the unit replacement described above, it is more preferable that at least two or more separation walls W be separable so that the casing (I) and the casing (II) can be separated.
Which mode of providing the casing (II) outside or inside the casing (I) is selected depending on the situation in which the ammonia decomposing apparatus is used, the size of each device, apparatus and equipment that can be used in the present invention. It can be appropriately selected according to the cost and the like.

Moreover, as an example of a suitable aspect when the ammonia decomposing apparatus has a casing (II), the casing (II) has an ammonia detector (a2), or a signal from the ammonia detector (a2) and the ammonia detector (a2). It is preferable to provide a circuit breaker (b2) that cuts off the ammonia supply from the ammonia supply device 1 to the ammonia decomposition device 2, and for example, as shown in FIG. It is more preferable to provide a breaker (b2) that receives signals from the vessel (a2) and the ammonia detector (a2) and cuts off the supply of the raw material ammonia from the ammonia supplier 1 to the ammonia decomposer 2.
By setting it as the said aspect, even when ammonia leaks not only in casing (I) but in casing (II), detection of ammonia is possible.
The ammonia detector (a2) may transmit a signal to the circuit breaker (b1) instead of transmitting a signal to the circuit breaker (b2). In that case, even if the ammonia decomposition apparatus does not have the circuit breaker (b2), it is possible to interrupt the supply of the raw material ammonia to the ammonia decomposition apparatus by the circuit breaker (b1).
Furthermore, the ammonia detector (a2) may transmit a signal to the circuit breaker (b1) simultaneously with transmitting a signal to the circuit breaker (b2). In that case, if the circuit breaker (b2) does not operate, the supply of the raw material ammonia to the ammonia decomposer can be blocked by the circuit breaker (b1).
Further, when the circuit breakers (b1) and (b2) are provided, the ammonia detectors (a1) and (a2) are independently connected to the circuit breakers (b1) and (b) in the casing (I) and the casing (II), respectively. It is possible to set a threshold value for the concentration of atmospheric ammonia when transmitting a signal to (b2) and / or blocking. For example, the ammonia detector (a2) installed in the casing (II) with respect to the threshold value of the atmospheric ammonia concentration when the ammonia detector (a1) installed in the casing (I) shuts off the circuit breaker (b1). ) May set the ammonia concentration threshold value low when the circuit breaker (b1) and / or (b2) is interrupted. Therefore, it becomes possible to cope with the environment in each casing and the operating conditions of each device and each device, and the safety when using the ammonia decomposing apparatus and the hydrogen gas production apparatus having the ammonia decomposing apparatus can be further improved. .

Further, a signal from the ammonia detector (a1) is transmitted to the circuit breaker (b1) to cut off the supply of the raw material ammonia and also to the ammonia decomposer 2 to stop the operation of the ammonia decomposer 2. It is more preferable that it is an aspect. Similarly, in the case of having an ammonia detector (a2), a signal from the ammonia detector (a2) is transmitted to the circuit breaker (b1) and / or the circuit breaker (b2) to cut off the supply of ammonia and More preferably, it is also possible to transmit to the cracker 2 and stop the operation of the ammonia cracker 2.
In addition to such an embodiment, or independently, when the ammonia detector (a1) and / or the ammonia detector (a2) detects the leaked ammonia, the raw material ammonia gas to the ammonia decomposer 2 May be provided with a device capable of temporarily switching the supply to the supply of forced exhaust gas or the like.
In these aspects, it is possible to avoid a situation in which the cracker continues to operate at a high temperature in a state where the raw material ammonia is not supplied, and the safety as the ammonia decomposing apparatus can be further improved.

The ammonia decomposing apparatus according to the present invention is the above-described embodiment, and further includes a transmitter (c1) that transmits a signal from the ammonia detector (a1) and a signal from the ammonia detector (a2). It is preferable to have at least one selected from the group consisting of transmitters (c2) to transmit.
The transmitters (c1) and (c2) may be independently provided in the casing (I) or the casing (II), and may be provided outside the casing (I) or the casing (II). Also good.
As an example of the aspect having the transmitters (c1) and (c2), for example, as shown in FIG. 7, the transmitter (c1) is installed inside the casing (I), while the transmitter Examples of (c2) include an aspect in which the high-temperature ammonia decomposer 2 is provided outside the casing (II) in which the ammonia decomposer 2 is provided.
Moreover, you may use one transmitter which integrated the function of the transmitters (c1) and (c2). That is, a method of receiving signals from a plurality of detectors with a single transmitter and transmitting individual data to a monitoring center described later may be used. In that case, for example, the transmitter (c1) may also serve as the transmitter (c2).
In such a case, even if there is only one transmitter, the ammonia decomposing apparatus is regarded as having the transmitters (c1) and (c2).

The transmitters (c1) and (c2) are independently installed in devices that exist outside the ammonia decomposition apparatus, for example, in the operation monitoring center, on the signals received from the ammonia detectors (a1) and (a2). It plays a role of transmitting a signal to a receiver (hereinafter also simply referred to as “monitoring center”).
In addition, the aspect at the time of including the ammonia decomposition | disassembly apparatus and monitoring center of this invention can also be called an ammonia leak monitoring system.
Transmission of the signal to the monitoring center as installed outside the ammonia decomposition apparatus may be wired or wireless and can be selected as appropriate. For example, when the ammonia decomposing apparatus is used at a hydrogen station or the like, a method of transmitting a signal by wire (for example, an optical fiber) to a monitoring center installed in a site where the hydrogen station or the like is installed or in a remote place can be mentioned. In addition, when the ammonia decomposing apparatus is loaded on a transporter (for example, a fuel cell vehicle) equipped with a fuel cell, which will be described later, a signal from a transmitter wired and / or wirelessly to a monitoring center loaded on the airframe. In addition to the monitoring center installed on the safety management center that is independent from the monitoring center on which the aircraft is loaded, or a base station that is connected to the safety management center by wire. There is a method of transmitting a signal.
In addition, each of the above-described ammonia detectors, transmitters, receivers installed in the operation monitoring center, etc. is not limited to the function of signal transmission or reception, but can receive and transmit signals in both directions. It may be a device. In this case, since each device becomes a communicable facility, not only the operation conditions of the internal device of the ammonia decomposition device are monitored from the outside of the ammonia decomposition device, but also the operation of each device is controlled according to the operation status. It is also possible to do.

The ammonia decomposing apparatus according to the present invention is the above-described embodiment, and further includes an ammonia detoxifying apparatus (d1) that operates by receiving a signal from the ammonia detector (a1), and an ammonia detector (a2). ) May receive at least one selected from the group consisting of an ammonia abatement device (d2) that operates in response to the signal from.
The ammonia abatement devices (d1) and (d2) may be independently installed in the casing (I) or the casing (II), respectively, and installed outside the casing (I) or the casing (II). It may be.
As an example of the embodiment having the ammonia detoxifying devices (d1) and (d2), for example, as shown in FIG. 8, the ammonia detoxifying device (d1) is installed inside the casing (I), and A mode in which the ammonia abatement device (d2) is installed inside the casing (II) can be mentioned.
Moreover, as another example of the aspect having the ammonia detoxifying devices (d1) and (d2), for example, as shown in FIG. 9, the ammonia detoxifying device (d1) is installed inside the casing (I). On the other hand, the ammonia detoxifying device (d2) may be provided outside the casing (II) in which the high-temperature decomposer 2 is installed.
Moreover, you may use one ammonia abatement apparatus which integrated the function of the ammonia abatement apparatuses (d1) and (d2). That is, a method of receiving signals from a plurality of detectors and operating the ammonia abatement apparatus with a single ammonia abatement apparatus may be used. In this case, for example, the ammonia abatement device (d1) can also serve as the ammonia abatement device (d2).
In such a case, even if there is only one ammonia abatement apparatus, the ammonia decomposition apparatus is regarded as having an ammonia abatement apparatus (d1) and (d2).

When an ammonia abatement device is provided outside the casing (I) or the casing (II), for example, as shown in FIG. 9, which is an example in which an ammonia abatement device is installed outside the casing (II), There is an embodiment in which the harmful device (d2) is provided in a casing (III) different from the casing (II), and the casing (II) and the casing (III) are communicated with each other by a connecting pipe p2. In the case of the embodiment of FIG. 9, when sealing the inside of the safety valve or the casing (II) that operates by receiving a signal from the ammonia detector (a2) in the connecting pipe p2, it is necessary to prevent the leakage of ammonia. A facility (for example, a facility having a pressure-sensitive safety valve, a blower, etc.) for sending ammonia gas leaked automatically due to an increase in internal pressure into the casing (III) may be provided.

Moreover, as an example of a suitable aspect in the case of having the casing (II), the casing (II) preferably includes a hydrogen gas detector (e1). For example, as shown in FIG. 10, the casing (II) However, it is more preferable to provide a hydrogen gas detector (e1) capable of transmitting a signal to the circuit breaker (b2).
By adopting this mode, it becomes possible to detect hydrogen gas even when hydrogen gas leaks in the casing (II), and safety when using an ammonia decomposing apparatus and a hydrogen gas producing apparatus having the ammonia decomposing apparatus. Can be improved more.
The hydrogen gas detector (e1) may transmit a signal to the circuit breaker (b1) instead of transmitting a signal to the circuit breaker (b2). In that case, even if the ammonia decomposing apparatus does not have the circuit breaker (b2), the supply of the raw material ammonia to the ammonia decomposing unit can be interrupted by the circuit breaker (b1).
Furthermore, the hydrogen gas detector (e1) may transmit a signal to the circuit breaker (b1) simultaneously with transmitting a signal to the circuit breaker (b2). In that case, if the circuit breaker (b2) does not operate, the supply of the raw material ammonia to the ammonia decomposer can be blocked by the circuit breaker (b1).
Further, a signal from the hydrogen gas detector (e1) is transmitted to the circuit breaker (b1) and / or the circuit breaker (b2) to cut off the supply of the raw material ammonia, and also transmitted to the ammonia decomposing unit 2, It is more preferable that the operation of the ammonia decomposer 2 can be stopped.
The ammonia detector may have a function of detecting the hydrogen gas. For example, when the ammonia detector (a2) also has a hydrogen gas detection function, even if there is only one such detector, the ammonia decomposition device has an ammonia detector (a2) and a hydrogen gas detector ( It is considered to be an embodiment having e1).

Moreover, when the ammonia decomposition apparatus of this invention is an aspect which has the hydrogen gas detector (e1) mentioned above, it may have further the transmitter (f1) which transmits the signal from a hydrogen gas detector (e1). preferable.
The transmitter (f1) may be installed inside the casing (II), or may be installed outside the casing (II).
As an example of the aspect having the transmitter (f1), for example, as shown in FIG. 11, the transmitter (f1) is provided outside the casing (II) in which the ammonia decomposer 2 having a high temperature is provided. The embodiment mentioned is mentioned.
Moreover, the method of transmitting a signal from the hydrogen gas detector (e1) to the transmitter (f1) may be wired or wireless. The viewpoint of selecting wired or wireless is the same as the viewpoint described above with respect to the ammonia detector and the transmitter that transmits a signal from the ammonia detector.
In addition, the hydrogen gas detector and the transmitter that transmits the signal from the hydrogen gas detector, including the receiver installed in the operation monitoring center and the like described above, can only transmit or receive signals. Not only the function but also a device capable of bidirectionally receiving and transmitting signals may be used. In this case, since each device becomes a communicable facility, not only the operation conditions of the internal device of the ammonia decomposition device are monitored from the outside of the ammonia decomposition device, but also the operation of each device is controlled according to the operation status. It is also possible to do.

A method of transmitting signals from the ammonia detectors (a1) and (a2) and the hydrogen gas detector (e1) to each device may be wired or wireless. From the viewpoint of reliably transmitting and receiving signals when there is a device or apparatus that is affected by radio wave interference when using wireless, and from the viewpoint of cost when the ammonia decomposition device is small, wired It is preferable that
On the other hand, since it is difficult to be restricted by the internal wiring method, etc., it is wireless because it is not necessary to consider the problem of the wiring section when a communication trouble occurs due to equipment problems from the viewpoint of increasing the degree of freedom of each device or device installation location. It is preferable to use radio from the viewpoint of being able to cope with replacement of only the machine.
Note that the transmitters (c1), (c2), and (f1) described above may be integrated into one transmitter. That is, a method may be used in which signals from a plurality of detectors are received by a single transmitter and individual data is transmitted to the monitoring center. In that case, for example, the transmitter (c1) may also serve as the transmitter (c2) and / or (f1).
In this case, even if the number of the transmitters is one, it is considered that the ammonia decomposition apparatus has transmitters (c1), (c2), and (f1).

Hereinafter, examples of preferable modes of each device, each device, and each facility described above will be sequentially described. However, preferable modes of each device, each device, and each facility used in the present invention are limited to modes described later. It is not a thing.

<Case (I)>
The casing (I) is not particularly limited, but is preferably a sealed container or a sealed chamber. By using a sealed container or a sealed chamber, it is possible to perform unit replacement and the like more safely when performing the unit replacement described above. In addition, in the case where the ammonia decomposer is not installed, it is possible to completely separate the environment that has become hot due to the operation of the ammonia decomposer and the environment in the casing (I). The safety of the ammonia decomposition apparatus can be further improved. Examples of the casing material include iron; carbon steel; stainless steel; nickel; titanium; nickel alloys such as Inconel (registered trademark), Monel (registered trademark), and Hastelloy (registered trademark). On the other hand, it is preferable to use a relatively stable material.

<Connecting piping>
The material and form of the connection pipe can be appropriately selected in consideration of the flow rate and pressure of ammonia to be handled, the installation environment of the connection pipe, and the like. Examples of the material include iron, carbon steel, stainless steel, nickel, titanium, nickel alloys such as Inconel (registered trademark), Monel (registered trademark), and Hastelloy (registered trademark). It is preferable to use a stable material.
Further, from the viewpoint of preventing leakage of ammonia gas from the connecting pipe, it is preferable to use a pipe having a multiple structure such as a double pipe or a triple pipe. In the case of a pipe having a multiple structure, for example, by passing ammonia into a space inside a space constituted by the outermost wall and one inner wall (hereinafter also simply referred to as “inner pipe”), Even if ammonia leaks from the pipe, it is possible to prevent the ammonia from leaking outside the connecting pipe. In addition, a medium is sealed between the internal pipe and the outer wall (in some cases, the inner wall), and the pH of the medium (water as a medium in this case) or a change in pressure (as a medium in this case, Nitrogen gas, helium gas, inert gas such as argon gas, etc.) can be detected by the ammonia detector.

<Mixed gas transport piping>
The mixed gas transport pipe is used for transporting the mixed gas obtained by decomposing the raw material ammonia with an ammonia decomposer, and is not particularly limited. For example, the same pipe as the connecting pipe can be used, The preferred embodiment is also the same.

<Case (II)>
The casing (II) is not particularly limited, but is preferably a sealed container or a sealed chamber, or a container or device chamber having a feed pipe p3 and a feed pipe p4 as shown in FIG. Moreover, as a material of casing (II), the thing similar to the said casing (I) can be used, for example, The suitable aspect is also the same.

(Feed piping)
Although the said supply piping is not specifically limited, For example, the thing similar to the said connection piping can be used, The suitable aspect is also the same. The said supply piping can be used suitably as a supply piping at the time of sending out forced exhaust gas etc. in casing (II), for example.

(Sending pipe)
Although the said delivery piping is not specifically limited, For example, the thing similar to the said connection piping can be used, The suitable aspect is also the same. The delivery pipe can be suitably used as a delivery pipe when, for example, forced exhaust gas fed from the feed pipe is sent out of the casing (II) into the casing (II).
When the casing (II) is equipped with a supply pipe and a supply pipe, forced exhaust gas can flow through the casing (II), and the safety when ammonia or hydrogen gas generated by ammonia decomposition leaks out is further improved. It is possible to make it.
Further, by providing an ammonia detector and / or a hydrogen gas detector, which will be described later, on the delivery pipe side, the leakage of these gases may be detected.
Moreover, you may enable it to remove the ammonia in the gas forcibly discharged | emitted from a delivery pipe by providing the ammonia elimination apparatus mentioned later on the delivery pipe side.
Examples of the forced exhaust gas include inert gas such as nitrogen gas, helium gas or argon gas; air; water vapor; A forced exhaust gas containing at least one selected from these gases is preferred, a forced exhaust gas mainly comprising at least one selected from these gases is more preferred, and at least one selected from these gases It may be a forced exhaust gas consisting of only. Moreover, in order to reduce the influence on the decomposition temperature of the ammonia decomposer, the forced exhaust gas may be brought into contact with the ammonia decomposer after being heated once.

<Ammonia decomposer>
The ammonia decomposing unit is used for decomposing raw material ammonia supplied from an ammonia supplying unit to be described later to obtain hydrogen.
The decomposition of ammonia can be expressed as the following formula (a).
2NH ₃ → N ₂ + 3H ₂ (a)
This reaction is a chemical equilibrium reaction, and the higher the temperature, the better the ammonia conversion rate. At 400 ° C., the ammonia conversion rate is about 99%.

In order to decompose the raw material ammonia to obtain hydrogen gas, it is preferable to use a catalyst for promoting the ammonia decomposition reaction of the formula (a) (hereinafter also referred to as “ammonia decomposition catalyst”). The ammonia decomposition catalyst has catalytic activity for the ammonia decomposition reaction represented by the formula (a) and is not particularly limited. For example, a base metal transition metal (iron, cobalt, nickel, molybdenum, etc.) And catalysts containing rare earths (such as lanthanum, cerium and neodymium) and noble metals (such as ruthenium, rhodium, iridium, palladium and platinum) as compositions. The base metal transition metal can be used as a simple metal, alloy, nitride, carbide, oxide, composite oxide, the rare earth can be used as an oxide, both the base metal transition metal and the rare earth , Alumina, silica, magnesia, zirconia, titania and the like can be supported on a carrier having a high specific surface area. The noble metal system can also be used by being supported on a carrier having a high specific surface area such as alumina, silica, magnesia, zirconia, titania and the like. Further, a small amount of the noble metal system may be contained in the base metal transition metal and / or the rare earth system. These ammonia decomposition catalysts may be used alone or in combination of two or more.

Further, the temperature condition of the ammonia decomposition reaction for decomposing the raw material ammonia to obtain hydrogen gas is preferably 300 ° C. or higher and 800 ° C. or lower. And even if it is a stainless steel (SUS) material having a heat-resistant temperature of 600 ° C. or less, the viewpoint that it can be used as a material for equipment (containers, pipes, etc.) used for the ammonia decomposition reaction and the ammonia conversion rate are improved. In view of the above, the temperature condition for the decomposition reaction of the raw material ammonia is more preferably 450 ° C. or higher, further preferably 500 ° C. or higher, more preferably 600 ° C. or lower, and further preferably 550 ° C. or lower.
The pressure condition during the raw material ammonia decomposition reaction is preferably 0.005 MPa (abs) or more, preferably 50 MPa (abs) or less, more preferably 25 MPa (abs) or less, and even more preferably 10 MPa (abs). ) Or less, more preferably 5.0 MPa (abs) or less. Further, from the viewpoint of improving the ammonia conversion rate, it is preferably 1.0 MPa (abs) or less, more preferably 0.75 MPa (abs) or less, and further preferably 0.50 MPa (abs) or less. From the same viewpoint, the pressure condition is preferably 0.01 MPa (abs) or more, more preferably 0.05 MPa (abs) or more, and still more preferably 0.10 MPa (abs) or more.

Further, when the raw material ammonia is decomposed under the conditions of 450 ° C. or higher and 600 ° C. or lower to achieve a high ammonia conversion rate, among the examples of the ammonia decomposition catalyst, at least selected from the group consisting of nickel, ruthenium and rhodium. It is preferable to use a catalyst containing one kind, and it is more preferable to use a catalyst containing ruthenium (ruthenium-based catalyst).

From the viewpoint described above, the ammonia decomposing unit is preferably an ammonia decomposing unit capable of satisfying these ammonia decomposing conditions, and examples thereof include a decomposing unit such as a fixed bed type decomposing unit and a fluidized bed type decomposing unit. . The ammonia decomposer includes a container filled with the ammonia decomposition catalyst, a heating device for controlling the heating of the container, a thermometer for measuring the temperature of the container, a pressure gauge for measuring the inlet pressure of the container, ammonia It is preferable that a cooling device for cooling control of the mixed gas after decomposition is provided. Furthermore, it may have a function capable of urgently stopping the operation based on a seismic device due to seismic motion and only the operating force of the seismic device or a signal from the seismic device. Moreover, it is preferable that the material of each device and each part used in the ammonia decomposer is relatively stable against ammonia and hydrogen. For example, stainless steel; nickel; titanium; Inconel (registered trademark), Monel (registered) (Trademark), nickel alloys such as Hastelloy (registered trademark), etc. can be used.

<Ammonia feeder>
The ammonia feeder is not particularly limited as long as it is a device that can supply raw ammonia to the ammonia decomposer. For example, a liquefied ammonia tank and / or a liquefied ammonia cylinder, and a vaporizer for vaporizing liquefied ammonia Examples thereof include an ammonia feeder having an (evaporator). Furthermore, facilities for managing the storage temperature of liquefied ammonia cylinders (eg, temperature control device) and / or equipment for temporarily storing ammonia vaporized by the vaporizer (eg, accumulator or tank), etc. You may have. For example, it is preferable to have devices such as a pressure regulating valve that controls the pressure of the vaporized ammonia gas, a pressure gauge that measures the outlet pressure of the pressure regulating valve, and a mass flow controller that controls supply of ammonia gas in a predetermined amount. Moreover, you may have the mechanical emergency shut-off valve which interrupts | blocks supply of ammonia only with the operating force of the pump, the seismic device by earthquake motion, and the said seismic device.

<Ammonia detectors (a1) and (a2)>
The ammonia detectors (a1) and (a2) are not particularly limited. For example, an ammonia gas detector that automatically sucks the gas in the casing (I) or (II) and measures the ammonia concentration in the air, As will be described later, when the inside of the casing (I) or (II) is sealed, a pressure gauge that detects a pressure increase in the closed system due to ammonia leakage may be used as the ammonia detector.
Examples of the detection method of the ammonia gas detector include a semiconductor type, a catalytic combustion type, an electrochemical type, a constant potential electrolysis type, and a heat conduction type. In addition, ammonia may be detected by a device such as a pH measurement device, a GC (Gas Chromatography) device, or an FT-IR (Fourier Transform Infrared Spectroscopy) measurement device.
Since the relative vapor density of ammonia is 0.59 (air = 1), it easily rises in the air in the casing (I) or (II) when leaked as ammonia gas. For this reason, the ammonia gas detector is preferably provided in the upper part of the space in each casing.
Also, if there is a risk of ammonia leaking as liquid ammonia, the leaked ammonia is dissolved in water, and the pH rise of the aqueous solution in which the ammonia is dissolved is checked with a pH meter to prevent ammonia leakage. It may be detected.
Similarly, the same applies to the case where ammonia leaked out as ammonia gas is dissolved in water or the like and the aqueous solution in which the ammonia is dissolved is inspected. As a method of dissolving the leaked ammonia in water or the like, a method of dissolving ammonia gas or liquid ammonia leaked into the liquid such as water introduced into the multiple pipe such as the double pipe or triple pipe described above, or leaked Examples of the method include a method in which ammonia gas is used as an aqueous solution in which ammonia is dissolved using facilities such as a cleaning tower and a (wet) scrubber described later. In addition to the method of confirming with a pH meter, for example, an aqueous solution in which the ammonia is dissolved is extracted from a drain tube, etc., and the leakage of ammonia can be visually confirmed using an acid-base indicator such as a litmus paper or a phenolphthalein solution. May be.
In addition, in the case where a plurality of ammonia detectors are provided as the ammonia detectors (a1) and (a2), for example, from the viewpoint that the leakage location can be identified easily and quickly, for example, a location where ammonia leakage is a concern and It is preferable to provide in the vicinity.
In addition to transmitting a signal to at least one selected from the group consisting of a circuit breaker, an ammonia abatement device, and a transmitter, which will be described later, the ammonia detector transmits a signal to the ammonia decomposer and operates the ammonia detector. It is preferable to use one that can be controlled and stopped. When trouble occurs, the ammonia decomposer is also stopped at the same time, so safety can be further improved.

<Hydrogen gas detector (e1)>
The hydrogen gas detector (e1) is not particularly limited. For example, the hydrogen gas detector (e1) that automatically sucks the gas in the casing (II) and measures the concentration of the hydrogen gas in the air, as will be described later. When sealing the inside of the casing (II), a pressure gauge that detects an increase in pressure in the closed system due to hydrogen gas leakage may be used as the hydrogen gas detector.
Examples of the detection method of the hydrogen gas detector (e1) include a semiconductor method, a catalytic combustion method, an electrochemical method, a constant potential electrolysis method, and a heat conduction method. Moreover, you may detect hydrogen gas with apparatuses, such as GC apparatus.
Since the relative vapor density of hydrogen gas is 0.07 (air = 1), when hydrogen gas leaks out, it tends to rise in the air in the casing (II), so these hydrogen gas detectors are It is preferable to provide the upper part of the space in the casing (II). Or, as will be described later, when the casing (II) has a delivery pipe that can send out, for example, forced exhaust gas, the hydrogen gas detector is provided in the delivery pipe or at the outlet of the delivery pipe. Also good.
When providing a plurality of hydrogen gas detectors, it is preferable to provide, for example, at a location where leakage is a concern and in the vicinity thereof, from the viewpoint that the leakage location can be easily and quickly identified.
The hydrogen gas detector transmits a signal to the ammonia decomposing unit in addition to transmitting a signal to one or more selected from the group consisting of a circuit breaker, an ammonia abatement device, and a transmitter, which will be described later. It is preferable to use one that can control and stop operation. When trouble occurs, the ammonia decomposer is also stopped at the same time, so safety can be further improved.

<Circuit breaker (b1)>
The circuit breaker (b1) is not particularly limited as long as it is a device that can receive a signal from the ammonia detector (a1) and cut off the supply of ammonia to the ammonia decomposing device. Examples include a shutoff valve that shuts off the supply of ammonia gas in a connecting pipe that connects the feeder and the ammonia decomposing unit, and a device that shuts off the supply of ammonia inside the ammonia supplier.
Examples of the shut-off valve include a pneumatic shut-off valve and an electric shut-off valve. The material of the member used for the circuit breaker is preferably relatively stable against ammonia and hydrogen. For example, stainless steel; nickel; titanium; Inconel (registered trademark), Monel (registered trademark), Hastelloy (registered) A nickel alloy such as a trademark);
As an apparatus for shutting off the supply of ammonia inside the ammonia feeder, for example, when using an ammonia feeder having the above-described liquefied ammonia tank, cylinder, etc., a device that shuts off or rapidly cools the liquefied ammonia (for example, , A device that switches hot water to cold water, a device that cuts off the supply of steam, and a temperature regulator itself when heated and vaporized by an electric heater or the like. In addition, shut off the main valve of the ammonia container (for example, a liquefied ammonia storage tank or cylinder), the tank that temporarily stores vaporized ammonia, etc., and shut off the introduction of ammonia into the connection pipe. A device (such as a shut-off valve provided in the connecting pipe introduction part) is included.

In addition, for example, when ammonia leakage occurs in the casing (II), for the purpose of interrupting the supply of the raw material ammonia to the ammonia decomposer installed in the casing (II), Alternatively, it may be a switching valve for switching the flow path of the raw material ammonia from the ammonia feeder. In this case, the raw material ammonia may be introduced into a tank or the like for storing ammonia that is temporarily excessively supplied, and further, an ammonia condenser or the like is provided at the tip thereof to liquefy the ammonia and supply the ammonia again. It may be returned to the vessel.
From the viewpoint of further improving the safety of the ammonia decomposing apparatus, even if the supply of the raw ammonia is temporarily shut off using the switching valve in the connecting pipe, the supply of the raw ammonia from the ammonia feeder itself Is preferably stopped. Therefore, from the viewpoint of further improving the safety of the ammonia decomposing apparatus, it is preferable to have both the shut-off valve and a device that stops the supply of ammonia gas from the ammonia supplier itself. Thereby, at the time of leakage, the shutoff valve is closed and the ammonia gas supply itself from the ammonia supplier can be stopped.

<Circuit breaker (b2)>
The circuit breaker (b2) is not particularly limited. For example, the circuit breaker (b2) is the same as the circuit breaker (b1) except that the circuit breaker (b1) can be operated regardless of whether or not a signal is received from the ammonia detector (a1). Furthermore, there is a shutoff valve that shuts off the supply of the mixed gas in the transport pipe p11 that transports the mixed gas obtained by decomposing ammonia by the ammonia decomposer.

<Transmitters (c1), (c2) and (f1)>
Transmitters (c1), (c2), and (f1) are independent of each other, reducing the influence of the environment (temperature, pressure, etc.) in the casing (I) and / or the casing (II), and more reliably to the outside. From the viewpoint of transmitting a signal, it is preferably provided outside the casing (I) and the casing (II). On the other hand, when the influence from the external environment is more concerned, the transmitters (c1), (c2) and (f1) are independently installed in the casing (I) and the casing (II), respectively. Alternatively, the transmitter itself installed outside the casing (I) and the casing (II) is preferably further surrounded by a casing (for example, a waterproof casing).
The transmitters (c1), (c2) and (f1) have a function of receiving a signal from the ammonia detector and / or hydrogen gas detector and transmitting the signal to an external monitoring center or the like. If it is, it will not specifically limit.

<Ammonia detoxification devices (d1) and (d2)>
The ammonia detoxifying devices (d1) and (d2) are not particularly limited as long as they are devices that operate by receiving a signal from the ammonia detector and are capable of detoxifying the leaked ammonia. For example, an apparatus that can receive a signal from an ammonia detector and remove the ammonia in the air by taking in the air in the casing is preferable only when the ammonia concentration in each casing exceeds a threshold value.
Examples of the ammonia abatement apparatus include a metal salt that reacts with ammonia to form a complex such as calcium chloride or copper chloride, or an apparatus that treats ammonia with an acid such as sulfuric acid or hydrogen sulfate, a washing tower, Examples thereof include an apparatus for spraying water onto ammonia gas in the air using equipment such as a wet scrubber, recovering it as ammonia water, an apparatus for detoxifying by burning ammonia, and an apparatus for oxidizing and decomposing ammonia with a catalyst.
Also, for example, a device that adsorbs ammonia using an adsorbent that adsorbs ammonia, such as zeolite, activated carbon, alumina, silica, and composite oxide, and ammonia as a salt such as ammonium hydrogen carbonate by contacting carbon dioxide and water with ammonia. Examples of the ammonia abatement device include a device for fixing ammonia, a device for removing ammonia by adsorbing, fixing, isolating, etc., such as a bubble spraying device for covering the surface of liquefied ammonia with bubbles.
Among these, from the viewpoint of making the ammonia decomposing apparatus compact, an apparatus that removes ammonia preferably using an adsorbent, a metal salt, an acid or the like can be mentioned.

<Other facilities, equipment and devices>
The ammonia decomposing apparatus of the present invention is an ammonia abatement apparatus capable of detoxifying trace amounts of ammonia regardless of whether or not a signal can be received from an alarm device or an ammonia detector, in addition to the above-described facilities, devices, and apparatuses. You may have the circuit breaker which can interrupt | block supply of raw material ammonia irrespective of the presence or absence of the signal from a seismic sensor and the said ammonia detector.
Examples of the alarm device include an alarm device that receives a signal from the ammonia detector and warns the outside. Unlike the case where each transmitter transmits a signal to, for example, an external monitoring center installed at a location distant from the ammonia decomposer to notify the abnormality, the alarm device is provided with an ammonia decomposer. An alarm can be sounded at that location, and the danger can be immediately notified around the ammonia decomposing unit.
An ammonia detoxification device capable of detoxifying trace amounts of ammonia regardless of whether a signal is received from an ammonia detector is, for example, adsorption capable of adsorbing the above-mentioned ammonia in the casing (I) or (II) Examples thereof include a device that is always brought into contact with the agent.
As a circuit breaker capable of shutting off the supply of raw material ammonia regardless of whether or not a signal is received from the ammonia detector, for example, other than being able to shut off the supply of raw material ammonia regardless of whether or not the signal is received from the ammonia detector Is the same as that exemplified in the circuit breaker that receives the signal from the ammonia detector and cuts off the supply of ammonia, and the mechanical emergency cut-off that cuts off the supply of ammonia only by the operating force of the seismic sensor Examples include valves. A signal from the ammonia detector in the event that a failure occurs in the signal receiving function of the circuit breaker that receives the signal from the ammonia detector and shuts off the ammonia supply, or the circuit breaker itself cannot shut off the ammonia supply. Regardless of whether or not it is received, a circuit breaker capable of shutting off the supply of raw material ammonia by other means such as signal transmission from the outside can be operated. In addition, even when an electrical system trouble occurs in the event of an earthquake or the like, emergency shutdown can be performed immediately, so safety can be improved.

Moreover, the connection part of each equipment, for example, the connection part of various pipings, such as a flange part, or the connection part of various piping and each apparatus or each apparatus, is enclosed with a casing different from casing (I) or (II). Further, an ammonia detector or a hydrogen gas detector may be provided in the vicinity of the sealed portion or the connecting portion.
Moreover, it is more preferable that each of the above-described devices, devices, and facilities has an explosion-proof structure.

Further, each aspect and preferred aspect relating to the above-described ammonia decomposition apparatus are not limited to the above-mentioned and later-described aspects. For example, the ammonia decomposition apparatus of the present invention includes the above-described devices, specifically, Ammonia detectors, circuit breakers, transmitters that send signals from ammonia detectors, ammonia abatement devices that operate by receiving signals from ammonia detectors, hydrogen gas detectors, and signals from hydrogen gas detectors You may have each apparatus of the transmitter to perform, and other apparatuses, and each installation, such as the above-mentioned connection piping and a casing, individually or in combination.
Further, in the ammonia decomposition apparatus according to one aspect of the present invention, the examples described with respect to each device, each device, and each facility described above, and preferable examples thereof are independently described with respect to other devices, devices, and facilities. Any of them can be combined arbitrarily.
In addition, one or more types selected from the group consisting of equipment, devices, and equipment arbitrarily selected from the examples, preferred examples, and the like described with respect to the above-described equipment, devices, and equipment are each independently other equipment, devices, and equipment. It can combine with the 1 type or more chosen from the group which consists of the apparatus, apparatus, and equipment arbitrarily selected from the illustration described regarding the 1 type or more chosen from the group which consists of, the preferable illustration, etc.
As an example of a specific embodiment, it has casings (I) and (II) that are in contact with each other through an isolation wall, the casing (II) is provided outside the casing (I), and the ammonia feeder is A pressure gauge that measures the pressure of the liquefied ammonia cylinder and the cylinder, a pressure regulating valve that controls the pressure of the ammonia gas, a pressure gauge that measures the outlet pressure of the pressure regulating valve, and a mass flow controller for controlling supply of ammonia gas in a predetermined amount A container filled with an ammonia decomposition catalyst, a heating device for controlling the heating of the container, a thermometer for measuring the temperature of the container, a pressure gauge for measuring the inlet pressure of the container, Has a cooling device for cooling control of the mixed gas after ammonia decomposition, and the connecting pipe connecting these is a double pipe, which is an ammonia feeder, ammonia Detector (a1), circuit breaker (b1), transmitter (c1) and ammonia abatement device (d1) are in casing (I), ammonia decomposer, ammonia detector (a2), circuit breaker (b2), hydrogen A gas detector (e1) and an ammonia abatement device (d2) are installed in the casing (II), and the casing (II) further includes a supply pipe, a supply pipe, a transmitter (c2), and a transmitter (f1). Attached modes are listed.

Moreover, the mixed gas obtained by decomposing ammonia with the ammonia decomposing apparatus of the present invention is a mixed gas containing hydrogen gas, nitrogen gas, and residual ammonia gas as described above.
The ammonia content in the mixed gas is preferably 2,000 mol ppm or less, more preferably 1,500 mol ppm or less, still more preferably 1,000 mol ppm or less with respect to the total amount of the mixed gas.

[Hydrogen gas production equipment]
The hydrogen gas production apparatus according to one aspect of the present invention includes ammonia in a mixed gas that communicates with the ammonia decomposing apparatus of the present invention and the ammonia decomposing unit through a connecting pipe and is supplied from the ammonia decomposing unit. And a hydrogen gas purifying device communicating with the ammonia removing device through a connecting pipe.
As an example of the hydrogen gas producing apparatus, as shown in FIG. 13, the ammonia decomposing unit 10 according to the above-described embodiment of the ammonia decomposing unit 10 communicates with the ammonia decomposing unit 2 through the connecting pipe p12, and the ammonia decomposing unit. 2 is a hydrogen gas production apparatus 100 having an ammonia removal apparatus 20 that removes ammonia in the mixed gas supplied from 2 and a hydrogen gas purification apparatus 30 that communicates with the ammonia removal apparatus 20 via a connecting pipe p23.
Here, the connecting pipe p12 corresponds to the mixed gas transport pipe p11 described above, and the mixed gas transport pipe p11 is used as a pipe for connecting the ammonia decomposer 2 and the ammonia removing device 20.
Further, the hydrogen gas purified by the hydrogen gas purification device 30 can be transported by, for example, a hydrogen gas transport pipe p31 shown in FIG. 13 and collected in a storage container or the like, or directly supplied to the fuel cell.
Hereinafter, preferred embodiments of the hydrogen gas production apparatus which is one embodiment of the present invention and preferred embodiments of each apparatus, each device, and each equipment included in the hydrogen gas production apparatus will be sequentially described. The suitable aspect of the hydrogen gas manufacturing apparatus which is one aspect | mode is not limited to the aspect mentioned later.

<Ammonia decomposition device>
The ammonia decomposing apparatus included in the hydrogen gas production apparatus according to one aspect of the present invention is the same as the above-described ammonia decomposing apparatus of the present invention, and the preferred embodiment thereof is also the same.

<Ammonia removal device>
The ammonia removal apparatus included in the hydrogen gas production apparatus according to one embodiment of the present invention is not particularly limited as long as it can remove ammonia in the mixed gas obtained by decomposing ammonia, but the ammonia concentration in the mixed gas is preferably It is an apparatus capable of removing ammonia so as to be 1.0 mol ppm or less, more preferably 0.1 mol ppm or less.
Further, when producing hydrogen gas for a transport machine (for example, an automobile, a motorcycle, a forklift, etc.) equipped with a fuel cell described later, it is preferably 0.10 mol ppm or less, more preferably 0.08 mol ppm or less, Preferably, it is an apparatus that can remove ammonia so that it becomes 0.075 mol ppm or less.
Here, in the present specification, when “mol%” or “mol ppm” is described as each component composition in a gas (gas), it is synonymous with “volume%” or “volume ppm”.
Examples of the ammonia removing apparatus that can be used in the present invention include a container filled with an ammonia removing material, a heating apparatus for controlling heating of the container, and a cooling apparatus for controlling cooling. The ammonia removal material is not particularly limited as long as it can remove ammonia in the mixed gas. For example, an adsorbent such as zeolite, activated carbon, alumina, silica, composite oxide; by acid-base reaction with ammonia Examples include acids for removing ammonia; metal salts that react with ammonia to form a complex such as calcium chloride or copper chloride; and the like.
Among these ammonia removing materials, an adsorbent is preferable from the viewpoint of recyclability. Among the adsorbents, zeolite is preferable from the viewpoint of adsorption ability.

As the zeolite, for example, a structure code consisting of three alphabets defined by the International Zeolite Association is ANA, CHA, ERI, GIS, KFI, LTA, NAT, PAU, YUG, DDR, AFI, ATO, Examples thereof include zeolite having a crystal structure represented by BEA, CON, FAU, GME, LTL, MOR, MTW, OFF, CLO, VFI, AET, CFI, and DON.

The adsorption temperature when using an adsorbent such as zeolite, activated carbon, alumina, silica, and composite oxide as the ammonia removing material is preferably from −10 ° C. to 50 ° C. from the viewpoint of efficiently adsorbing ammonia. More preferably, it is 0 degreeC or more and 30 degrees C or less. The pressure during adsorption when using the adsorbent is preferably 0.005 MPa (abs) or more, preferably 50 MPa (abs) or less, more preferably 25 MPa (abs) or less, and even more preferably 10 MPa. (Abs) or less, more preferably 5.0 MPa (abs) or less. Further, from the viewpoint of energy cost reduction related to adsorption, it is preferably 1.00 MPa (abs) or less, more preferably 0.10 MPa (abs) or less, and the adsorption pressure is preferably 0. 0.01 MPa (abs) or more, more preferably 0.05 MPa (abs) or more, and still more preferably 0.08 MPa (abs) or more.
The acid for removing ammonia is not particularly limited as long as it can remove ammonia by an acid-base reaction with ammonia, and examples thereof include sulfuric acid and hydrogen sulfate.
Further, as one aspect of the ammonia removal apparatus, from the viewpoint that the ammonia removal material can be regenerated with a regeneration gas, an adsorbent regeneration gas for regenerating the adsorbent is further supplied. It is preferable to have a supply pipe and a supply pipe for sending the regeneration gas.
The adsorbent regeneration gas is preferably a gas containing at least one selected from the group consisting of an inert gas such as nitrogen gas, helium gas or argon gas, and air, and at least one selected from the group consisting of these gases. A gas mainly composed of seeds is more preferable, and a gas composed of at least one selected from the group consisting of these gases may be used. Further, the adsorbent regeneration gas may or may not contain a gas such as hydrogen gas, ammonia or water vapor.

<Hydrogen gas purification equipment>
Although the hydrogen gas refinement | purification apparatus which the hydrogen gas manufacturing apparatus which is 1 aspect of this invention has is not specifically limited, For example, the apparatus using one of the following methods is mentioned.
For example, a gas to be treated is introduced into a container filled with a substance that selectively adsorbs a specific component from a gas, such as zeolite (the type of the zeolite is not particularly limited), activated carbon, etc., and the pressure is increased or decreased for separation. Examples thereof include a pressure swing method (PSA method), a temperature swing method in which separation is performed by raising and lowering the temperature, and a pressure / temperature swing method in which pressure and temperature are respectively swung. As a hydrogen gas purification apparatus for performing these treatments, a container filled with zeolite, a pressure increasing apparatus for introducing a gas treated in the ammonia removing apparatus into the container and increasing the pressure, and a pressure reducing apparatus for reducing the pressure, It is preferable to have.
In addition, for example, the pressure is increased by a compressor, etc., the nitrogen in the gas is liquefied at a cryogenic temperature by a gas-liquid separator and separated from hydrogen and gas-liquid, and the separated hydrogen gas is passed through an adsorption purification tower to remove residual nitrogen. Examples thereof include a removal method and a membrane separation method using a palladium permeable membrane.
In the case of supplying hydrogen that can be used as a fuel cell vehicle hydrogen gas, it is preferable that hydrogen gas for a fuel cell vehicle satisfying the composition defined in the international standard ISO 14687-2 can be obtained. . When producing the hydrogen gas for fuel cell vehicles, the ammonia content in the hydrogen gas for fuel cell vehicles is preferably 0.10 mol ppm or less, more preferably 0.08 mol ppm or less, and even more preferably 0.075. Molar ppm or less.

<Connecting piping>
The connection pipe used in the hydrogen gas production apparatus according to one aspect of the present invention is not particularly limited. For example, the same connection pipe as the above-described ammonia decomposition apparatus of the present invention can be used, and a preferable aspect thereof. Is the same.

<Hydrogen gas transportation piping>
The hydrogen gas transport pipe is used for transporting the hydrogen gas produced by the hydrogen gas production apparatus, and is not particularly limited. For example, the same pipe as the connection pipe can be used, and a preferable aspect thereof is also used. It is the same.

<Other facilities, equipment and devices>
The hydrogen gas production apparatus of the present invention removes impurities other than hydrogen gas such as nitrogen gas from the mixed gas, for example, before and after the ammonia removal apparatus or before the hydrogen gas purification apparatus, in addition to the above-described apparatuses. You may have a device for. As the apparatus, for example, an apparatus similar to that described in the hydrogen gas purification apparatus can be used.
Further, for example, a hydrogen gas detector, an alarm device, a seismic device due to seismic motion, and a mechanical emergency shut-off valve that blocks leakage of hydrogen gas only by the operating force of the seismic device may be provided.
Also, a shutoff valve that shuts off the supply of the mixed gas obtained by decomposing the raw material ammonia in a connecting pipe that connects the ammonia decomposer and the ammonia removing device, the ammonia removing device, and the hydrogen gas purifying device And a shutoff valve that shuts off the supply of purified hydrogen gas in the connecting pipe connecting the two.

It is more preferable that each of the aforementioned devices, apparatuses, and facilities used in the hydrogen gas production apparatus of the present invention has an explosion-proof structure.
The hydrogen gas production apparatus of the present invention may have each device, each device, and each facility described above alone or in combination of two or more.
In addition, in the hydrogen gas production apparatus according to one embodiment of the present invention, the examples described for each device, each device, and each facility described above, and preferable examples thereof are independently described for other devices, devices, and equipment. Any of them can be combined arbitrarily.
In addition, one or more types selected from the group consisting of equipment, devices, and equipment arbitrarily selected from the examples, preferred examples, and the like described with respect to the above-described equipment, devices, and equipment are each independently other equipment, devices, and equipment. It can combine with the 1 type or more chosen from the group which consists of the apparatus, apparatus, and equipment arbitrarily selected from the illustration described regarding the 1 type or more chosen from the group which consists of, the preferable illustration, etc.
As an example of a specific aspect, the ammonia decomposing apparatus is the ammonia decomposing apparatus of the preferred aspect specifically described above, and the ammonia removing apparatus is a container filled with an ammonia removing material, and for controlling the heating of the container. A heating device and a cooling device for controlling cooling; a container filled with zeolite by the hydrogen gas refining device; a pressure increasing device and a pressure reducing device for introducing the gas treated by the ammonia removing device into the container and increasing the pressure; There is a mode in which a decompression device is provided, the connecting pipe connecting them is a double pipe, and both the ammonia removing device and the hydrogen gas purifying device are installed in the casing.

[Uses of ammonia decomposition equipment and hydrogen gas production equipment]
As described above, by using the ammonia decomposition apparatus of the present invention and the hydrogen gas production apparatus of the present invention, ammonia can be decomposed more safely, and hydrogen gas can be produced more safely. Furthermore, the hydrogen gas production apparatus having the ammonia decomposing apparatus of the present invention can automatically cut off the supply of ammonia and effectively reduce or prevent the leakage of ammonia outside the casing even when ammonia leaks. It becomes possible.
Therefore, for example, when ammonia leaks, it is not preferable to use an ammonia decomposing device or hydrogen gas production device in a place where it takes time for humans to respond on site, or to deal with ammonia leaking on site In addition, it is possible to move the ammonia decomposition apparatus or hydrogen gas production apparatus to a dedicated facility for processing.
For example, an infrastructure facility (for example, a hydrogen station) for supplying hydrogen gas for a transport aircraft equipped with a fuel cell, or a portable hydrogen gas fuel supply facility loaded with the fuel cell on a transport device equipped with a fuel cell, It is mentioned as a suitable use example of the ammonia decomposition apparatus of this invention and / or the hydrogen gas manufacturing apparatus of this invention.
Furthermore, the fuel cell using the hydrogen gas obtained from the hydrogen gas production apparatus of the present invention can be mounted on various transport aircraft. As the mounting method, the fuel cell can be mounted alone or can be mounted together with the hydrogen gas production apparatus of the present invention.
Here, “transport aircraft” includes ships, air transports, and vehicles, and the vehicles include railway vehicles, automobiles, two-wheeled vehicles, and industrial vehicles. The automobile includes a vehicle capable of traveling on a public road, such as a private vehicle; a business vehicle such as a bus or a taxi. The industrial vehicle includes, for example, a forklift.

The ammonia decomposing apparatus is used for infrastructure equipment (for example, a hydrogen station) for supplying hydrogen gas for a transport aircraft equipped with a fuel cell; or for a transport device (for example, a ship, an air transport machine, and the vehicle) equipped with a fuel cell. It can be suitably used as an ammonia decomposing apparatus used for portable hydrogen gas fuel supply equipment to be loaded;
Similarly, the hydrogen gas production apparatus includes the infrastructure equipment; or a portable hydrogen gas fuel supply equipment loaded on a portable hydrogen gas fuel supply equipment loaded on a transport machine equipped with a fuel cell; Can be suitably used.

DESCRIPTION OF SYMBOLS 10 Ammonia decomposition | disassembly apparatus 1 Ammonia supply device 2 Ammonia decomposition device p1, p2 Connection piping p11 Mixed gas transport piping a1, a2 Ammonia detector b1, b2 Circuit breaker I Casing (I)
II Casing (II)
III Casing (III)
W Separation wall c1, c2 Transmitter for transmitting signal from ammonia detector d1, d2 Ammonia detoxifying device e1 Hydrogen gas detector f1 Transmitter for transmitting signal from hydrogen gas detector p3 Feeding piping p4 Delivery piping p12 , P23 Connecting piping 20 Ammonia removal device 30 Hydrogen gas purification device p31 Hydrogen gas transport piping 100 Hydrogen gas production device

Claims (17)

1. Ammonia decomposing unit, ammonia supplying unit communicated with the ammonia decomposing unit via a connecting pipe, ammonia detector (a1), and ammonia detector (a1) receiving signals from the ammonia decomposing unit A circuit breaker (b1) for cutting off the supply and a casing (I);
   The ammonia decomposition apparatus, wherein the casing (I) includes at least the ammonia supply device, the ammonia detector (a1), and the circuit breaker (b1).
2. Furthermore, the ammonia decomposing apparatus according to claim 1, further comprising a casing (II) in which the ammonia decomposing unit is installed.
3. The ammonia decomposing apparatus according to claim 1 or 2, further comprising a transmitter (c1) for transmitting a signal from the ammonia detector (a1).
4. The casing (II) receives the signal from the ammonia detector (a2), or the ammonia detector (a2) and the ammonia detector (a2), and shuts off the ammonia supply from the ammonia supplier to the ammonia decomposer. The ammonia decomposition apparatus according to claim 2 or 3, wherein a circuit breaker (b2) is provided.
5. The ammonia decomposing apparatus according to claim 4, further comprising a transmitter (c2) for transmitting a signal from the ammonia detector (a2).
6. The ammonia decomposing apparatus according to any one of claims 2 to 5, wherein the casing (II) is provided outside the casing (I), and the casing (II) does not include the casing (I).
7. The ammonia decomposing apparatus according to any one of claims 2 to 5, wherein the casing (I) includes the casing (II).
8. The ammonia decomposing apparatus according to any one of claims 2 to 7, wherein the casing (II) and the casing (I) are in contact via an isolation wall.
9. The ammonia decomposing apparatus according to any one of claims 1 to 8, wherein the casing (I) has an ammonia detoxifying apparatus (d1) that operates by receiving a signal from the ammonia detector (a1).
10. The ammonia decomposing apparatus according to any one of claims 4 to 9, wherein the casing (II) further includes an ammonia abatement apparatus (d2) that operates by receiving a signal from the ammonia detector (a2).
11. The ammonia decomposition apparatus according to any one of claims 1 to 10, wherein the casing (I) is a sealed container or a sealed chamber.
12. The ammonia decomposing apparatus according to any one of claims 2 to 11, wherein the casing (II) is an airtight container or an airtight chamber, or a container or an apparatus room having a supply pipe and an output pipe.
13. The ammonia decomposition apparatus according to any one of claims 2 to 12, wherein the casing (II) includes a hydrogen gas detector (e1).
14. The ammonia decomposing apparatus according to claim 13, further comprising a transmitter (f1) for transmitting a signal from the hydrogen gas detector (e1).
15. The ammonia decomposing apparatus according to any one of claims 1 to 14, and ammonia removal that communicates with the ammonia decomposing unit through a connecting pipe and removes ammonia in a mixed gas supplied from the ammonia decomposing unit. A hydrogen gas production apparatus comprising a device and a hydrogen gas purification device communicating with the ammonia removal device via a connecting pipe.
16. A fuel cell using hydrogen gas obtained from the hydrogen gas production apparatus according to claim 15.
17. A transport aircraft equipped with the fuel cell according to claim 16.

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