JP2022146893A - Disaster prevention equipment, fuel cell vehicles equipped with this disaster prevention equipment, hydrogen trailers and stationary equipment - Google Patents

Abstract

To provide a disaster prevention facility capable of preventing re-closure of a fusible safety valve and visualizing a jet fire of hydrogen released into the atmosphere.SOLUTION: A disaster prevention facility 1 for cooling a hydrogen storage container 100 with a fusible safety valve 102 in outbreak of a fire, includes a cooling water 11a for cooling the hydrogen storage container 100, a first pipe 15 for supplying the cooling water 11a, and a nozzle 14 connected to the first pipe 15 and capable of jetting the cooling water 11a toward the hydrogen storage container 100. The disaster prevention facility is configured to prevent the fusing safety valve 102 from getting wet by the cooling water 11a jetted from the nozzle 14 toward the hydrogen storage container 100.SELECTED DRAWING: Figure 1

Description

TECHNICAL FIELD The present invention relates to disaster prevention equipment for cooling a hydrogen storage container fitted with a fusible plug type safety valve in the event of a fire, a fuel cell vehicle, a hydrogen trailer, and stationary equipment equipped with this disaster prevention equipment.

Currently, "hydrogen" is becoming popular as one of the next-generation energies. Hydrogen has the characteristic of not emitting _CO2 even when used as energy. For example, hydrogen is produced in hydrogen production plants. Hydrogen produced at a hydrogen production plant is transported by a hydrogen trailer and stored in a hydrogen station. Hydrogen stored in the hydrogen station is supplied to fuel cell vehicles such as passenger cars, motorcycles, buses and trucks, and used for fuel cell power generation.

2. Description of the Related Art Hydrogen for external sale, which is used in hydrogen stations and fuel cell vehicles, is generally stored and transported in the form of compressed hydrogen filled in composite containers. Industrial hydrogen is stored and transported in the form of liquefied hydrogen cooled to -253°C. Furthermore, it is at the stage of practical use to store and transport hydrogen in the form of an organic hydride (for example, MCH: methylcyclohexane) by combining hydrogen with an organic substance such as toluene. In addition, storage and transport of hydrogen as ammonia (NH ₃ ), storage and transport of hydrogen atoms occluded by alloys, and the like have been investigated.

Here, the composite container filled with compressed hydrogen has a structure in which an aluminum liner is covered with carbon fiber reinforced plastic. If a composite container filled with compressed hydrogen encounters a fire, the heat of the fire will increase the internal pressure, and there is a danger that the composite container will explode. For this reason, the conventional composite container is provided with a fusible plug type safety valve for automatically releasing hydrogen in the container when the temperature is high.

For example, FIG. 4 of Japanese Patent Application Laid-Open No. 2015-230071 discloses a hydrogen trailer 1 having a plurality of high-pressure hydrogen containers A provided with fusible plug type safety valves Ab. As shown in FIGS. 6 to 8 of Japanese Patent Application Laid-Open No. 2015-230071, the fusible plug type safety valve Ab of each high-pressure hydrogen container A is connected to a discharge pipe 80 . When the fusible plug type safety valve Ab melts due to the high temperature at the time of fire, the hydrogen in the high-pressure hydrogen container A is released from the release pipe 80 into the atmosphere.

1 and 2 of JP-A-2017-038789, a first supply line 25 that supplies water for extinguishing a fire, and a second supply line 25 that supplies a smaller amount of water than the first supply line 25 A hydrogen station is disclosed with a supply line 26 of . When an abnormality such as a fire is detected, a sufficient amount of water is supplied from the first supply line 25 to the water spray head 24 to extinguish the fire. On the other hand, when the surface temperature of the storage tank 13 rises, a small amount of water for cooling is supplied from the second supply line 26 to the water spray head 24 .

In FIG. 1 of Japanese Patent Application Laid-Open No. 2006-271900, when hydrogen leakage from the hydrogen storage tank 2 and the hydrogen dispenser 3 is detected, mist is emitted from a plurality of mist nozzles 6 to increase the humidity in the protected area. A hydrogen station of construction is disclosed.

JP 2015-230071 A JP 2017-038789 A Japanese Patent Application Laid-Open No. 2006-271900

The operating temperature of the fusible plug type safety valve provided in the composite container is generally set to about 110°C. , Release to the atmosphere is completed in about 1 minute after the fusible plug type safety valve is activated. However, if the fusible plug type safety valve that has once been activated is submerged in cooling water or a fire extinguishing agent, the metal of the fusible plug re-solidifies, re-blocking the flow path for releasing hydrogen. For this reason, when a fire occurs, the release time of hydrogen from the container into the atmosphere is delayed, and there is a risk that the composite container will explode. If the composite container bursts, the fragments of the container will fly while still burning, causing great damage to the area around the fire site. Therefore, it is important to empty the composite container by releasing all the hydrogen in the container into the atmosphere as soon as possible after the fire starts.

On the other hand, the hydrogen in the container passes through the hydrogen release pipe from the fusible plug type safety valve and is released into the atmosphere from the outlet of the hydrogen release pipe at high pressure. If the hydrogen released from the outlet of the hydrogen release line ignites, a jet flame of hydrogen is formed. Since it is difficult to extinguish the jet flame of hydrogen discharged at high pressure, the basic countermeasure is to continue the combustion of hydrogen while monitoring it so that it does not spread. However, since the color of the flame when hydrogen is burned is almost colorless and transparent, it is difficult to visually catch the jet flame of hydrogen.

The present invention has been made in view of the above problems, and is capable of preventing re-closure of a fusible plug type safety valve, and a disaster prevention device capable of visualizing jet flames of hydrogen released into the atmosphere. The object is to provide a facility, a fuel cell vehicle, a hydrogen trailer and a stationary facility equipped with this disaster prevention facility.

(1) In order to achieve the above objects, the disaster prevention equipment of the present invention is a disaster prevention equipment for cooling a hydrogen storage container fitted with a fusible plug type safety valve in the event of a fire. a first pipe for supplying the cooling water; and a nozzle connected to the first pipe and capable of injecting the cooling water toward the hydrogen storage container. (a) the fusible plug type safety valve is not wetted by the cooling water injected from the nozzle into the hydrogen storage container;

(2) Preferably, in the disaster prevention equipment of (1) above, the nozzle is installed at a position where the fusible plug type safety valve is not exposed to the cooling water injected from the nozzle into the hydrogen storage container.

(3) Preferably, in the disaster prevention equipment of (1) or (2) above, the nozzle is installed in a direction that prevents the fusible plug safety valve from being exposed to the cooling water injected from the nozzle into the hydrogen storage container. do.

(4) Preferably, in the disaster prevention equipment according to any one of the above (1) to (3), the fusible plug type safety valve is not exposed to the cooling water injection pattern that is injected from the nozzle into the hydrogen storage container. Injection pattern.

(5) Preferably, in the disaster prevention equipment according to any one of (1) to (4) above, by providing a shield plate for blocking the cooling water splashing and/or flowing in the direction of the fusible plug type safety valve. , to prevent the fusible plug type safety valve from being exposed to water;

(6) Preferably, in the disaster prevention equipment according to any one of the above (1) to (5), a substance that imparts thickening or gelling properties to the cooling water is added to make it adhere to the surface of the hydrogen storage container. Also, the viscosity of the cooling water is increased to prevent the fusible plug type safety valve from being exposed to water.

(7) Preferably, in the disaster prevention equipment of (6) above, the substance that imparts thickening or gelling properties to the cooling water is a substance having thixotropic properties.

(8) Preferably, in the disaster prevention equipment according to any one of the above (1) to (5), the surface tension of the cooling water with respect to the surface of the hydrogen storage container is reduced by adding a substance that imparts wettability to the cooling water. to prevent the fusible plug type safety valve from being exposed to water.

(9) Preferably, in the disaster prevention equipment of (8) above, the substance that imparts wettability to the cooling water is a surfactant.

(10) Preferably, in the disaster prevention equipment according to any one of the above (1) to (9), the hydrogen released from the hydrogen storage container through the fusible plug type safety valve is mixed with a substance that causes a flame reaction. The configuration shall be such that

(11) Preferably, in the disaster prevention equipment of (10) above, a second pipe communicating with the outlet of the fusible plug type safety valve is provided, and the substance causing the flame reaction is injected near the outlet of the second pipe. This causes the hydrogen released from the hydrogen storage container to mix with the substance that causes the flame reaction.

(12) Preferably, in the disaster prevention equipment of (10) or (11) above, the substance that causes the flame reaction is an aqueous sodium chloride solution.

(13) Preferably, the disaster prevention equipment of (1) to (12) includes a fire sensor installed at the same place as the hydrogen storage container, and based on a signal from the fire sensor, the cooling water and a control unit for starting supply.

(14) In order to achieve the above objects, the fuel cell vehicle of the present invention is a fuel cell vehicle equipped with at least one hydrogen storage container fitted with a fusible plug type safety valve, wherein the above (1) to ( 13) is equipped with any of the disaster prevention equipment.

(15) In order to achieve the above objects, the hydrogen trailer of the present invention is a hydrogen trailer in which a plurality of hydrogen storage containers fitted with fusible plug type safety valves are loaded on a carrier, and the above (1) to (13) are ) is equipped with any disaster prevention equipment.

(16) In order to achieve the above object, the stationary equipment of the present invention is a stationary equipment in which at least one hydrogen storage container equipped with a fusible plug type safety valve is installed, wherein the above (1) to ( 13) is equipped with any of the disaster prevention equipment.

According to the disaster prevention equipment of the present invention, the fuel cell vehicle, the hydrogen trailer, and the stationary equipment equipped with this disaster prevention equipment, it is possible to prevent re-closure of the fusible plug type safety valve, and to prevent hydrogen released into the atmosphere. It becomes possible to visualize the jet flame. This makes it possible to prevent the hydrogen storage container from bursting when a fire occurs, and to prevent the spread of fire by visually monitoring the jet flame of hydrogen.

FIG. 1 is a schematic diagram showing disaster prevention equipment according to a first embodiment of the present invention. FIG. 2 is a schematic diagram showing disaster prevention equipment according to a second embodiment of the present invention. FIG. 3 is a schematic diagram showing disaster prevention equipment according to a third embodiment of the present invention. FIG. 4(a) is a front view of a nozzle that constitutes the disaster prevention equipment according to the first embodiment. FIG. 4(b) is a side view of the nozzle. FIG. 4(c) is a bottom view of the nozzle. FIG. 4(d) is a partially enlarged view showing the ejection angle and ejection pattern of the nozzles. FIG. 4(e) is a partially enlarged cross-sectional view showing the vicinity of the outlet of the hydrogen release pipe that constitutes the disaster prevention equipment according to the first embodiment. FIG. 4(f) is a partially enlarged cross-sectional view showing the vicinity of the outlet of the hydrogen release pipe constituting the disaster prevention equipment according to the second and third embodiments. FIGS. 5(a) to 5(c) are schematic diagrams showing shielding plates for preventing the fusible plug type safety valve from getting wet. FIG. 6(a) is a schematic diagram showing a fuel cell vehicle according to an embodiment of the present invention. FIG. 6(b) is a schematic diagram showing a hydrogen trailer according to an embodiment of the present invention. FIG. 6(c) is a schematic diagram showing a stationary installation according to an embodiment of the present invention.

DESCRIPTION OF THE PREFERRED EMBODIMENTS A disaster prevention system according to embodiments of the present invention, a fuel cell vehicle equipped with this disaster prevention system, a hydrogen trailer, and stationary equipment will be described below with reference to the drawings.

1. First Embodiment of Disaster Prevention Equipment FIG. 1 shows a disaster prevention equipment 1 according to a first embodiment of the present invention. The disaster prevention equipment 1 is for cooling the hydrogen storage container 100 in the event of a fire. It is installed in a stationary facility 4 such as a hydrogen production plant. The hydrogen storage container 100 is provided with a fusible plug type safety valve 102 for releasing hydrogen in the container when a fire occurs. The purpose of the disaster prevention equipment 1 is to prevent the hydrogen storage container 100 from bursting in the event of a fire and/or to visualize jet flames of hydrogen released into the atmosphere.

As shown in FIG. 1, the disaster prevention equipment 1 mainly consists of a first group of mechanical elements for preventing rupture of the hydrogen storage container 100 and a second group of mechanical elements for visualizing the hydrogen jet flame. Consists of a group of elements. For ease of understanding, groups of the first and second mechanical elements are conceptually divided up and down in FIG. 1 with the dashed-dotted line in FIG. However, the fire alarm 30 and the control unit 40 perform control processing for both the first and second groups of mechanical elements.

1-1. Arrangement for Preventing Explosion of Hydrogen Storage Container As shown below the dashed line in FIG. A first nozzle 14 and a first pipe 15 are included. The cooling water tank 11 stores cooling water 11a for cooling the hydrogen storage container 100 in the event of a fire. The inlet of the pump 12 is connected to the outlet of the cooling water tank 11 via the first pipe 15 . The outlet of the pump 12 is connected to the inlet of the first electric valve 13 via the first pipe 15 . The outlet of the first electric valve 13 is connected to the inlet of the first nozzle 14 via the first pipe 15 . The pump 12 and the first electric valve 13 are electrically connected to the control unit 40 and have their operations controlled by the control unit 40 . The fire detector 30 is installed within the protected area where the hydrogen storage container 100 is installed.

Fire sensor 30 detects at least one or more of heat, flame, and smoke, for example, and outputs a signal to control unit 40 . Based on the signal from the fire sensor 30 , the control unit 40 operates the pump 12 and opens the first electric valve 13 . As a result, the cooling water 11 a stored in the cooling water tank 11 is sucked by the pump 12 and injected from the first nozzle 14 into the hydrogen storage container 100 via the first pipe 15 . The cooling water 11a jetted from the first nozzle 14 cools the hydrogen storage container 100 in the event of a fire, thereby suppressing the hydrogen storage container 100 from bursting due to heating.

1-1-1. Configuration for Preventing Water Damage to the Fusible Plug Type Safety Valve Just cooling the hydrogen storage container 100 with the cooling water 11a cannot prevent the hydrogen storage container 100 from bursting. In order to prevent the hydrogen storage container 100 from rupturing, it is necessary to release all the hydrogen in the hydrogen storage container 100 into the atmosphere as soon as possible after the fire breaks out, so that the hydrogen storage container 100 is emptied. . As shown in FIG. 1, the hydrogen in the hydrogen storage container 100 is released when the fusible plug of the fusible plug safety valve 102 melts due to the heat of the fire. However, if the cooling water 11a jetted from the first nozzle 14 submerges the fusible plug safety valve 102, the melted fusible plug may be cooled and the outlet of the fusible plug safety valve 102 may be closed again. For this reason, the disaster prevention device 1 of the present embodiment is provided with the following configuration for preventing the fusible plug type safety valve 102 from being exposed to water.

1-1-2. First Nozzle The first nozzle 14 is installed in a position and in an orientation where the cooling water 11 a injected into the hydrogen storage container 100 does not wet the safety valve 102 . As shown in FIG. 1, the first nozzle 14 is installed in the center of the hydrogen storage container 100 away from the fusible plug type safety valve 102, and installed in the direction in which the cooling water 11a is injected into the center of the hydrogen storage container 100. It is

In addition, the first nozzle 14 is configured so that the cooling water 11 a that is injected to the center of the hydrogen storage container 100 has an injection angle and injection pattern that prevents the fusible plug type safety valve 102 from being wet. As shown in FIGS. 4(a) to 4(c), the tip of the first nozzle 14 is provided with a tip 14a having an injection port and a retainer 14b for holding the tip 14a. . The ejection angle and ejection pattern of the first nozzle 14 can be adjusted by the configurations of the tip 14a and retainer 14b. The tip 14a is formed with a substantially elliptical injection port and a laterally extending groove surrounding the injection port. On the other hand, the retainer 14b is formed with a pair of notches having an inverted U-shaped cross section corresponding to both ends of the laterally extending groove of the tip 14a. The ejection angle and ejection pattern of the first nozzle 14 are determined by the dimensions of these ejection ports, grooves and notches. As shown in FIG. 4(d), the injection angle of the first nozzle 14 is set within the range of 15° to 115°, for example. Also, the jet pattern of the first nozzle 14 is designed to be fan-shaped (see FIG. 1) showing a uniform flow rate distribution over almost the entire area.

1-1-3. Cooling Water The cooling water 11a jetted from the first nozzle 14 is added with a predetermined additive that affects its physical properties. For example, substances that impart thickening or gelling properties to the cooling water 11a, such as substances such as sodium alginate, cellulose, gum arabic, pectin, gelatin, and polyethylene glycol, and colloidal hydrous silicates such as smectite, bentonite, and montmorillonite. Adhesion to the hydrogen storage container 100 is improved by adding contained minerals, synthetic inorganic polymer compounds composed of colloidal hydrous silicate, thickening polysaccharides such as xanthan gum and guar gum, and the like. By adding a substance that imparts thixotropic properties, among substances that impart thickening or gelling properties, the viscosity of the cooling water 11a decreases when shear stress is applied, and increases when the shear stress is not applied. get the property to Due to such thixotropy, the viscosity of the cooling water 11a when jetted from the first nozzle 14 is reduced. After that, the viscosity of the cooling water 11a adhering to the surface of the hydrogen storage container 100 increases, and the fusible plug type safety valve 102 becomes less likely to be exposed to water.

The substance that imparts thixotropic properties to the cooling water 11a is not particularly limited. Thickening polysaccharides such as molecular compounds, xanthan gum and guar gum can be used. More preferably, thickening polysaccharides such as xanthan gum and guar gum are used. This is because polysaccharide thickeners such as xanthan gum and guar gum are used in foods and are harmless to humans and animals.

Further, for example, by adding a substance that imparts wettability to the cooling water 11a, the surface tension of the cooling water 11a adhered to the surface of the hydrogen storage container 100 is lowered, and the fusible plug type safety valve 102 is prevented from being exposed to water. good too. Substances that impart wettability include surfactants, organic solvents, alcohols, polymer compounds, fatty acids, oils and fats, dispersants, etc. Surfactants are particularly preferred. By adding the surfactant, the contact angle between the cooling water 11a and the contact surface is reduced, and the surface of the hydrogen storage container 100 is easily adhered. By reducing the surface tension of the cooling water 11a, the fusible plug type safety valve 102 is less likely to be exposed to water.

The surfactant is not particularly limited, but hydrocarbon-based surfactants are preferred from the viewpoint of suppressing adverse effects on the environment. Hydrocarbon surfactants have hydrophobic groups composed of carbon and hydrogen. Examples of hydrocarbon surfactants include hydrocarbon nonionic surfactants, hydrocarbon cationic surfactants, hydrocarbon anionic surfactants, and hydrocarbon amphoteric surfactants. Hydrocarbon-based nonionic surfactants are preferred. From the viewpoint of wettability, the hydrocarbon-based nonionic surfactant preferably has an HLB of 3 to 20, more preferably 8 to 16, as determined by the Griffin method.

Here, HLB is an acronym for Hydrophilic-Lipophilic Balance, and is a value representing the degree of affinity of a surfactant for water and oil (water-insoluble organic compounds). HLB takes a value from 0 to 20, and the closer to 0, the higher the lipophilicity, and the closer to 20, the higher the hydrophilicity. Methods of determining HLB by calculation (Atlas method, Griffin method, Davis method, Kawakami method, etc.) are known, but HLB in the present specification is a value determined by Griffin method.

When two or more surfactants are used, the HLB is a weighted average of the HLB values of each component. When two surfactants are used, the HLB is represented by the following formula.
HLB= _{N1 HLB} ^× W1 ^{+ N2} _HLB ^× W2
Here, N ¹ _HLB/ N ² _HLB : HLB of each surfactant
W ¹ · W ² : Weight fraction of each surfactant (W ¹ + W ² = 1)
Hereinafter, HLB can be obtained by the same calculation method even when the number of surfactants is three or more.

Hydrocarbon-based nonionic surfactants include polyoxyethylene alkyl ether type, polyoxyethylene alkylphenol type, polyoxyethylene alkylamine type, polyoxyethylene alkylamide type, polyoxyethylene fatty acid ester type, propylene glycol fatty acid ester type, Propylene glycol fatty acid dipolyoxyethylene lanolin ether type, aliphatic alkanolamide type, polyoxyethylene castor oil type, polyoxyethylene polyhydric alcohol type, polyhydric alcohol fatty acid ester type, polyoxyethylene polyhydric alcohol fatty acid ester type, etc. nonionic surfactants, more specifically polyoxyethylene oleyl ether, polyoxyethylene decyl ether, polyoxyethylene tridecyl ether, polyoxyethylene 2-ethylhexyl ether, polyoxyethylene lauryl ether, tristearic acid Sorbitan, polyoxyethylene castor oil and the like can be mentioned. These are commercially available, for example, as Rheodor SP-S30V from Kao Corporation, Braunon series BR-404, EN-1502 and EN-1504 from Aoki Yushi Kogyo Co., Ltd., and Fine Surf series D-1303 and TD-50. It is Hydrocarbon-based nonionic surfactants may be used singly or in combination of two or more.

Hydrocarbon cationic surfactants include, for example, monoalkylammonium chloride, dialkylammonium chloride, EO-added ammonium chloride, tetramethylammonium chloride, benzyltrimethylammonium chloride and the like. The hydrocarbon-based cationic surfactants may be used singly or in combination of two or more.

Examples of hydrocarbon-based anionic surfactants include alkyl ether sulfates, alpha olefin sulfonates, alkylbenzenesulfonic acids and salts thereof, alkyl sulfates, ethersulfonates, ether carboxylates, sulfosuccinates, Examples include methyl taurate, alaninate and salts thereof. The hydrocarbon-based anionic surfactants may be used singly or in combination of two or more.

Hydrocarbon amphoteric surfactants include, for example, alanine-type, imidazolinium betaine-type, aminopropyl betaine-type, and aminodipropion-type amphoteric surfactants. Imidazolinium betaine type amphoteric surfactants are preferred. Hydrocarbon-based amphoteric surfactants may be used singly or in combination of two or more.

Fatty acids may be linear or branched, natural or synthetic, and saturated or unsaturated, such as caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, acid, behenic acid, tallow fatty acid, oleic acid, hardened castor fatty acid, linoleic acid, palmitoleic acid, linolenic acid and the like. A fatty acid may be used individually by 1 type, or may be used in combination of 2 or more types.

Examples of the organic solvent include cellosolve solvents such as methyl cellosolve, ethyl cellosolve, and butyl cellosolve; carbitols such as ethyl carbitol and butyl carbitol; and polyoxyethylene lower alkyl ethers having 3 to 10 moles of ethylene oxide added. is mentioned. An organic solvent may be used individually by 1 type, or may be used in combination of 2 or more types.

Examples of polymer compounds include cellulose derivatives such as methyl cellulose and hydroxyethyl cellulose, polyvinyl alcohol, sodium alginate, polyvinyl ether, and polyethylene glycol. A polymer compound may be used individually by 1 type, or may be used in combination of 2 or more types.

Examples of the dispersant include naphthalenesulfonic acid-based, alkylnaphthalenesulfonic acid-based, polycarboxylic acid-based, polystyrenesulfonic acid-based, alkylamine-type, and alkylphenol-type dispersants. Dispersants may be used singly or in combination of two or more.

Examples of alcohols include lower alcohols such as methanol and ethanol, higher alcohols such as lauryl alcohol and myristyl alcohol, and polyhydric alcohols other than glycols such as glycerin and sorbitol. Alcohols may be used singly or in combination of two or more.

The oils and fats may be either natural oils or synthetic oils, and include processed oils, silicone oils, mineral oils, waxes and the like. Oils and fats may be used individually by 1 type, or may be used in combination of 2 or more types.

The cooling water 11a preferably contains a potassium salt from the viewpoint of improving fire extinguishing ability.
Potassium salts include inorganic potassium salts and organic potassium salts, and inorganic potassium salts include potassium hydroxide, potassium tetraborate, potassium nitrate, potassium carbonate, potassium sulfate, potassium phosphate, potassium hydrogen phosphate, bromide. Potassium, potassium chloride, etc., and organic potassium salts include potassium acetate, potassium stearate, potassium citrate, potassium lactate, potassium tartrate, potassium succinate, potassium malate, potassium glycolate, and the like. Potassium salts may be used singly or in combination of two or more. Among these, organic potassium salts are preferable, and potassium acetate, which is also used as a raw material for pharmaceuticals, is more preferable from the viewpoint of not violating the Industrial Safety and Health Act and suppressing the influence on the environment.

The cooling water 11a preferably contains glycols from the viewpoint of suppressing coloring and lowering the freezing point.
Glycols preferably have 2 to 10 carbon atoms, and specific examples include monoethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, ethylene glycol monobutyl ether, and ethylene glycol. monomethyl ether, ethyl glycol, ethyl diglycol, butyl glycol, propylene glycol monoethyl ether and the like. Glycols may be used singly or in combination of two or more. Among these, propylene glycol and diethylene glycol are preferable, and propylene glycol is more preferable, from the viewpoint of not violating the Industrial Safety and Health Act and suppressing the influence on the environment.

From the viewpoint of combustion resistance, the cooling water 11a preferably contains phosphoric acid esters.
Examples of phosphate esters include acidic phosphate esters such as monomethyl acid phosphate and butyl acid phosphate; phosphites such as diethyl phosphite; phosphate ester salts such as polyoxyethylene alkyl ether phosphate and alkyl phosphate. trimethyl phosphate, triethyl phosphate, tributyl phosphate, triphenyl phosphate, 2-ethylhexyldiphenyl phosphate, aliphatic phosphate amidate, and the like. Phosphate esters may be used singly or in combination of two or more. Among these, acidic phosphate esters are preferable because they do not conflict with the Industrial Safety and Health Act and have a high flame retardant effect from the viewpoint of suppressing the impact on the environment.

Furthermore, by imparting thickening, gelling, thixotropic, or wettability to the cooling water 11a jetted from the first nozzle 14, not only the fusible plug type safety valve 102 is less likely to be exposed to water, but also the hydrogen storage container 100 A water film widely covering the surface of the hydrogen storage container 100 is formed, and the cooling effect of the hydrogen storage container 100 is improved.

1-2. Configuration for Visualizing Hydrogen Jet Flame As shown above the dashed line in FIG. A valve 23, a second nozzle 24 and a second line 25 are included. In the aqueous solution tank 21, an aqueous solution to which a substance that causes a flame reaction is added, for example, an aqueous sodium chloride solution 21a is stored. The pressurized container 22 is filled with a high-pressure gas. The high-pressure gas filled in the pressurized container 22 may be air, but carbon dioxide gas, nitrogen gas, or a mixed gas thereof, which is an inert gas, is more preferable. The outlet of the pressurized container 22 is closed by a sealing plate (not shown). An initiator 22 a is attached to the outlet of the pressurized container 22 . The initiator 22 a is an electric ignition type igniter for breaking the sealing plate of the pressurized container 22 .

An outlet of the pressurized container 22 is connected to the aqueous solution tank 21 via a second pipe 25 . The outlet of the aqueous solution tank 21 is connected to the inlet of the second motor-operated valve 23 via the second pipe 25 . The outlet of the second electric valve 23 is connected to the inlet of the second nozzle 24 via the second pipe 25 . The second nozzle 24 is arranged near the outlet of the hydrogen release pipe 102a. The initiator 22a and the second electric valve 23 are electrically connected to the control unit 40 and have their operations controlled by the control unit 40 .

Based on the signal from the fire sensor 30, the control unit 40 ignites the initiator 22a and then opens the second motor-operated valve 23. As shown in FIG. By igniting the initiator 22 a , the sealing plate of the pressurized container 22 is broken, and the aqueous solution tank 21 is filled with the high pressure gas in the pressurized container 22 . As a result, the pressure in the aqueous solution tank 21 increases, and the sodium chloride aqueous solution 21a stored in the aqueous solution tank 21 is jetted from the second nozzle 24 through the second pipe 25 to the vicinity of the outlet of the hydrogen release pipe 102a.

As shown in FIG. 4(e), the sodium chloride aqueous solution 21a injected from the second nozzle 24 is mixed with the hydrogen 100a released into the atmosphere from the outlet of the hydrogen release pipe 102a. As a result, even when the hydrogen 100a released into the atmosphere from the outlet of the hydrogen release pipe 102a ignites and a jet flame of the hydrogen 100a is formed, the sodium chloride aqueous solution 21a mixed with the hydrogen 100a causes a flame reaction. and a jet flame of hydrogen 100a is visualized. Specifically, the flame-coloring reaction of the aqueous sodium chloride solution 21a colors the jet flame of hydrogen 100a yellow.

1-2-1. Aqueous Solution Additives to the aqueous solution for causing the flame reaction include water-soluble metal salts and water-soluble organic metals, and are not limited to the sodium chloride aqueous solution 21a. For example, an aqueous solution added with an alkali metal other than sodium chloride (Na), an alkaline earth metal, copper (Cu), boron (B), gallium (Ga), indium (In), thallium (Tl), or the like may be used. good. Alkali metals other than sodium chloride include lithium (Li), potassium (K), rubidium (Rb), cesium (Cs), and the like. Alkaline earth metals include magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), and the like. Aqueous solutions to which these substances are added can also cause a flame reaction to visualize the jet flame of hydrogen 100a.

1-2-2. Injection Timing of Aqueous Solution In this embodiment, the sodium chloride aqueous solution 21a is ejected based on the signal from the fire sensor 30, but the timing is not limited to this. For example, when the temperature in the protected area reaches the melting temperature (for example, 110°C ± 10°C) of the fusible plug of the fusible plug type safety valve 102, an aqueous solution for causing a flame reaction is jetted. good too. In this case, a temperature sensor is installed in the protected area, and based on the temperature detected by the temperature sensor, the controller 40 is caused to start supplying the aqueous solution. Further, for example, an aqueous solution for causing a flame reaction may be jetted based on the flow rate of the hydrogen 100a flowing through the hydrogen release pipe 102a. In this case, a flow rate sensor is installed in the hydrogen release pipe 102a, and the controller 40 is caused to start supplying the aqueous solution based on the flow rate detected by the flow rate sensor.

1-2-3. Second Nozzle The second nozzle 24 of the present embodiment has the same configuration as the first nozzle 14 shown in FIGS. 4(a) to 4(d), but is not limited to this. A nozzle having a configuration different from that of the first nozzle 14 may be used as long as it is possible to mix an aqueous solution for causing a flame reaction with the hydrogen 100a released into the atmosphere from the outlet of the hydrogen release pipe 102a. .

2. Second Embodiment of Disaster Prevention Equipment FIG. 2 shows a disaster prevention equipment 1 according to a second embodiment of the present invention. The disaster prevention equipment 1 according to the second embodiment has a configuration in which a pump 12 draws up cooling water 11a from a water source. With this configuration, the cooling water tank 11 shown in FIG. 1 is omitted. As water sources, for example, water tanks or natural sources of water such as rivers, lakes, and seas are used. Such disaster prevention equipment 1 according to the second embodiment is suitable for stationary equipment 4 such as a hydrogen station and a hydrogen production plant shown in FIG. 6(c).

Further, the disaster prevention equipment 1 according to the second embodiment has a configuration in which the outlet of the aqueous solution tank 21 is connected to the venturi pipe 26 provided near the outlet of the hydrogen release pipe 102a. With this configuration, the pressurized container 22, the initiator 22a and the second motor-operated valve 23 shown in FIG. 1 are omitted. The configuration of the venturi tube 26 is shown in FIG. 4(f). A narrowed portion 26b having a small cross-sectional area is formed in the middle of the main pipeline 26a of the venturi tube 26. As shown in FIG. A secondary pipe line 26c communicates with the constricted portion 26b. The outlet of the aqueous solution tank 21 shown in FIG.

Hydrogen 100a released from fusible plug type safety valve 102 flows through main pipeline 26a of venturi tube 26 through hydrogen release pipe 102a. When the hydrogen 100a passes through the narrowed portion 26b, the flow velocity increases and the pressure in the narrowed portion 26b decreases. As a result, the sodium chloride aqueous solution 21a in the aqueous solution tank 21 is sucked from the secondary conduit 26c to the narrowed portion 26b side and mixed with the hydrogen 100a flowing through the main conduit 26a. According to the configuration using such a venturi tube 26, without the control processing by the fire sensor 30 and the control unit 40 shown in FIG. It is possible to mix an appropriate amount of sodium chloride aqueous solution 21a.

3. Third Embodiment of Disaster Prevention Equipment FIG. 3 shows a disaster prevention equipment 1 according to a third embodiment of the present invention. The disaster prevention equipment 1 according to the third embodiment is configured to inject a fire extinguishing agent 19a into the hydrogen storage container 100 instead of the cooling water 11a shown in FIGS. The extinguishing agent 19a serves to cool the hydrogen storage container 100 and extinguish the flame in the vicinity of the hydrogen storage container 100 when a fire occurs.

The disaster prevention equipment 1 according to the third embodiment is configured to include a fire extinguishing agent undiluted solution 17 , a mixer 18 and a fire extinguishing agent tank 19 . Other configurations are the same as those of the disaster prevention equipment 1 according to the second embodiment shown in FIG. The mixer 18 mixes the water drawn from the water source with the extinguishing agent undiluted solution 17 to generate the extinguishing agent 19a. The extinguishing agent 19a produced by the mixer 18 is stored in the extinguishing agent tank 19a.

The extinguishing agent 19 a stored in the extinguishing agent tank 19 is sucked by the pump 12 and injected from the first nozzle 14 into the hydrogen storage container 100 via the first pipe 15 . The fire extinguishing agent 19a sprayed from the first nozzle 14 cools the hydrogen storage container 100 in the event of a fire, thereby suppressing the explosion of the hydrogen storage container 100 due to heating. In addition, the flame near the hydrogen storage container 100 is extinguished by the fire extinguishing agent 19a, and the ignition of the hydrogen storage container 100 is prevented.

4. Option for preventing the fusible plug type safety valve from getting wet As an option for preventing the fusible plug type safety valve 102 from getting wet in the event of a fire, a shield plate 51 as shown in FIGS. 52 may be attached to the hydrogen storage container 100 . The cooling water 11a that splashes and/or flows in the direction of the fusible plug type safety valve 102 is blocked by the shielding plates 51-52. As a result, it is possible to prevent the fusible plug type safety valve 102 from being wet with the cooling water 11a (or the fire extinguishing agent 19a in FIG. 3).

The shielding plate 51 shown in FIG. 5( a ) is a compact umbrella having an area covering the top of the fusible plug type safety valve 102 . The umbrella-shaped shielding plate 51 can block the cooling water 11a that scatters and/or flows from above the fusible plug type safety valve 102 .

The shielding plate 52 shown in FIG. 5(b) is a semi-cylindrical cover having a cross-sectional area equal to half of the hydrogen storage container 100. As shown in FIG. The semi-cylindrical cover-type shielding plate 52 can block the cooling water 11a that scatters and/or flows from above and from the side of the fusible plug type safety valve 102 .

The shielding plate 53 shown in FIG. 5( c ) is a vertical wall with a notch equal to half the cross-sectional area of the hydrogen storage container 100 . The cooling water 11a that scatters and/or flows from above and from the sides of the fusible plug type safety valve 102 can be blocked by the vertical wall-shaped shielding plate 53 .

5. Use of Disaster Prevention Equipment The disaster prevention equipment 1 of the present embodiment shown in FIGS. It can be applied to stationary equipment 4 such as a hydrogen production plant.

5-1. Fuel Cell Vehicle FIG. 6(a) shows a fuel cell vehicle 2 equipped with the disaster prevention equipment 1 of FIG. 6A, illustration of the pump 12, the first motor-operated valve 13, the pressurized container 22, the initiator 22a, the second motor-operated valve 23, and the control unit 40 that constitute the disaster prevention equipment 1 of FIG. 1 is omitted. .

Fuel cell vehicle 2 includes two hydrogen storage containers 100 . Each of the two hydrogen storage containers 100 is provided with a main valve 101 (see FIG. 1) and a fusible plug type safety valve 102 . The outlets of the two fusible plug type safety valves 102 are connected to one hydrogen release pipe 102a. The outlet of this hydrogen release pipe 102a is arranged outside the vehicle through the ceiling of the fuel cell vehicle 2 . The main valve 101 of the hydrogen storage container 100 shown in FIG. 1 is connected to the fuel cell (not shown) of the fuel cell vehicle 2 via a hydrogen supply pipe 101a.

A cooling water tank 11 and an aqueous solution tank 21 are arranged below the two hydrogen storage containers 100 . An outlet of the cooling water tank 11 is connected to one first pipe 15 . Although not shown, the pump 12 and the first electric valve 13 are connected to the middle of the first pipe 15 (see FIG. 1).

Two first nozzles 14 connected to a first pipe 15 are arranged above the two hydrogen storage containers 100 . On the other hand, the outlet of the aqueous solution tank 21 is connected to one second pipe 25 . Although not shown, the aqueous solution tank 21 is connected with an initiator 22a provided at the outlet of the pressurized container 22, and a second electric valve 23 is connected in the middle of the second pipe 25 (see FIG. 1). ). A second nozzle 24 is connected to the outlet of the second pipe 25 . The second nozzle 24 passes through the ceiling of the fuel cell vehicle 2 and is arranged near the outlet of the hydrogen release pipe 102a. Furthermore, fire detectors 30 are installed above the two hydrogen storage containers 100 .

A fire that has occurred in the fuel cell vehicle 2 is detected by the fire detector 30 . Based on the signal from the fire sensor 30 , the control unit 40 starts supplying the cooling water 11 a in the cooling water tank 11 . Thereby, the cooling water 11 a is injected from the two first nozzles 14 to the two hydrogen storage containers 100 via the first pipe 15 . The cooling water 11a jetted from each first nozzle 14 cools each hydrogen storage container 100, thereby suppressing bursting of each hydrogen storage container 100 due to heating.

On the other hand, based on the signal from the fire sensor 30, the controller 40 starts supplying the sodium chloride aqueous solution 21a in the aqueous solution tank 21. As shown in FIG. As a result, the aqueous sodium chloride solution 21a is sprayed from the second nozzle 24 through the second pipe 25 to the vicinity of the outlet of the hydrogen release pipe 102a. The sodium chloride aqueous solution 21a is mixed with the hydrogen 100a released from the outlet of the hydrogen release pipe 102a. As a result, even when the hydrogen 100a released into the atmosphere from the outlet of the hydrogen release pipe 102a ignites and a jet flame of the hydrogen 100a is formed, the sodium chloride aqueous solution 21a mixed with the hydrogen 100a causes a flame reaction. and a jet flame of hydrogen 100a is visualized.

5-2. Hydrogen Trailer FIG. 6(b) shows a hydrogen trailer 3 equipped with the disaster prevention equipment 1 of FIG. In FIG. 6B, illustration of the pump 12, the first motor-operated valve 13, the pressurized container 22, the initiator 22a, the second motor-operated valve 23, and the control unit 40 that constitute the disaster prevention equipment 1 of FIG. 1 is omitted. .

As shown in FIG. 6(b), the configuration of the disaster prevention equipment 1 installed in the hydrogen trailer 3 is the same as that of the fuel cell vehicle 2 shown in FIG. 6(a). However, the number of hydrogen storage containers 100 loaded on the hydrogen trailer 3 is larger than that of the fuel cell vehicle 2, and the capacity of one hydrogen storage container 100 is also larger than that of the fuel cell vehicle 2. For example, the hydrogen trailer 3 is loaded with 24 hydrogen storage containers 100 . The capacity of one hydrogen storage container 100 is 300 L, and the internal pressure is 45 MPa.

1 is connected to a hydrogen supply port (not shown) of the hydrogen trailer 3 via a hydrogen supply pipe 101a. Through this hydrogen supply port, hydrogen 100a is supplied from the hydrogen trailer 3 to the hydrogen storage tank of the hydrogen station. The operation of the disaster prevention equipment 1 shown in FIG. 6(b) when a fire occurs is the same as that of the fuel cell vehicle 2 shown in FIG. 6(a).

5-3. Stationary equipment The disaster prevention equipment 1 of the present embodiment is not limited to movable vehicles such as the fuel cell vehicle 2 and the hydrogen trailer 3 described above, but can also be installed in the stationary equipment 4 shown in FIG. 6(c). can. The configuration of the disaster prevention equipment 1 installed in the stationary equipment 4 is the same as that of the fuel cell vehicle 2 shown in FIG. 6(a) described above. Also, the operation of the disaster prevention equipment 1 shown in FIG. 6(c) when a fire occurs is the same as that of the fuel cell vehicle 2 shown in FIG. 6(a).

6. Effects According to the disaster prevention equipment 1 of the present embodiment, the fuel cell vehicle 2, the hydrogen trailer 3, and the stationary equipment 4 equipped with the disaster prevention equipment 1 described above, it is possible to prevent the fusible plug type safety valve 102 from being re-closed. Also, it becomes possible to visualize the jet flame of the hydrogen 100a released into the atmosphere. This makes it possible to prevent the explosion of the hydrogen storage container 100 in the event of a fire, and to prevent the spread of the fire by visually monitoring the jet flame of the hydrogen 100a.

7. Others The disaster prevention equipment of the present invention, the fuel cell vehicle, the hydrogen trailer, and the stationary equipment provided with this disaster prevention equipment are not limited to the above-described embodiments. For example, the hydrogen storage container to be protected by the disaster prevention equipment of the present invention is not limited to a tank or cylinder form such as a composite container. Also, the hydrogen stored in the hydrogen storage container is not limited to the form of compressed hydrogen. The disaster prevention equipment of the present invention can be applied to containers storing various forms of hydrogen such as liquefied hydrogen, organic hydride (eg, MCH), ammonia (NH3), and hydrogen storage alloys.

In the disaster prevention equipment 1 shown in FIGS. 1 to 3, instead of the fire detector 30, a hydrogen detector for detecting hydrogen leakage may be installed. Also, a plurality of first nozzles 14 may be installed for one hydrogen storage container 100 . The plurality of first nozzles 14 are arranged, for example, in the longitudinal direction of one hydrogen storage container 100, and installed at positions and orientations in which the fusible plug type safety valve 102 is not exposed to water.

A manual activation switch may be provided for activating the disaster prevention equipment 1 shown in FIG. A signal is transmitted to the control unit 40 by turning on the manual activation switch. This causes the pump 12 to operate and the first electric valve 13 to open. By turning on the manual activation switch, the control unit 40 opens the second motor-operated valve 23 after igniting the initiator 22a.

The pump 12 may be omitted from the disaster prevention equipment 1 shown in FIG. In this case, the cooling water tank 11 is installed higher than the first nozzle 14 , and the outlet of the cooling water tank 11 is connected to the inlet of the first motor-operated valve 13 via the first pipe 15 . According to such a configuration, the cooling water 11 a in the cooling water tank 11 can be supplied to the first nozzle 14 by pressure due to the height difference between the cooling water tank 11 and the first nozzle 14 . Also, the cooling water 11a of the cooling water tank 11 can be supplied to the first nozzle 14 by applying to the cooling water tank 11 a configuration similar to the pressurized container 22 and the initiator 22a shown in FIG.

The mixer 18 may be omitted from the disaster prevention equipment 1 shown in FIG. In this case, a fire extinguishing agent 19 a obtained by mixing water and a fire extinguishing agent undiluted solution 17 in advance is stored in the extinguishing agent tank 19 .

1 Disaster Prevention Equipment 11 Cooling Water Tank 11a Cooling Water 12 Pump 13 First Electric Valve 14 First Nozzle 14a Chip 14b Retainer 15 First Pipe 16 Orifice Pipe 17 Extinguishing Agent Undiluted Solution 18 Mixer 19 Extinguishing Agent Tank 19a Extinguishing Agent 21 Aqueous Solution Tank 21a sodium chloride aqueous solution 22 pressurized container 22a initiator 23 second motor-operated valve 24 second nozzle 24a chip 24b retainer 25 second pipe 26 venturi pipe 26a main pipe 26b throttle portion 26c sub pipe 30 fire sensor 40 controller 51, 52, 53 Shielding plate 100 Hydrogen storage container 100a Hydrogen 101 Main valve 101a Hydrogen supply pipe 102 Fusible plug type safety valve 102a Hydrogen release pipe 2 Fuel cell vehicle 3 Hydrogen trailer 4 Stationary equipment

Claims (16)

Disaster prevention equipment for cooling a hydrogen storage container equipped with a fusible plug type safety valve in the event of a fire,
cooling water for cooling the hydrogen storage container;
a first pipe for supplying the cooling water;
a nozzle connected to the first pipe and capable of injecting the cooling water toward the hydrogen storage container;
with
The disaster prevention equipment, wherein the fusible plug safety valve is not exposed to the cooling water injected from the nozzle into the hydrogen storage container. 2. The disaster prevention equipment according to claim 1, wherein the nozzle is installed at a position where the fusible plug type safety valve is not exposed to the cooling water sprayed from the nozzle to the hydrogen storage container. The disaster prevention equipment according to claim 1 or 2, wherein the nozzle is installed in a direction in which the fusible plug type safety valve does not get wet with the cooling water jetted from the nozzle to the hydrogen storage container. The disaster prevention equipment according to any one of claims 1 to 3, wherein the cooling water jetting pattern jetted from the nozzle to the hydrogen storage container is a jetting pattern in which the fusible plug type safety valve does not get wet. 5. Any one of claims 1 to 4, wherein the fusible plug type safety valve is prevented from being exposed to water by providing a shield plate for blocking the cooling water splashing and/or flowing in the direction of the fusible plug type safety valve. Fire prevention equipment described in the paragraph. By adding a substance that imparts thickening or gelling properties to the cooling water, the viscosity of the cooling water adhered to the surface of the hydrogen storage container is increased, and the fusible plug type safety valve is prevented from being exposed to water. The disaster prevention equipment according to any one of claims 1 to 5. 7. The disaster prevention equipment according to claim 6, wherein the substance that imparts thickening or gelling properties to the cooling water is a substance having thixotropic properties. By adding a substance that imparts wettability to the cooling water, the surface tension of the cooling water with respect to the surface of the hydrogen storage container is reduced, and the fusible plug type safety valve is prevented from being exposed to water. Disaster prevention equipment according to any one of the paragraphs. 9. The disaster prevention equipment according to claim 8, wherein the substance that imparts wettability to the cooling water is a surfactant. The disaster prevention equipment according to any one of claims 1 to 9, wherein the hydrogen released from the hydrogen storage container through the fusible plug type safety valve is mixed with a substance that causes a flame reaction. A second pipe that communicates with the outlet of the fusible plug type safety valve is provided, and the substance that causes the flame reaction is injected near the outlet of the second pipe, so that the hydrogen released from the hydrogen storage container is 11. The disaster prevention equipment according to claim 10, wherein the substance that causes the flame reaction is mixed. 12. The disaster prevention equipment according to claim 10 or 11, wherein the substance causing the flame reaction is an aqueous sodium chloride solution. a fire detector co-located with the hydrogen storage container;
a control unit for starting supply of the cooling water based on a signal from the fire sensor;
The disaster prevention equipment according to any one of claims 1 to 12, comprising: A fuel cell vehicle equipped with at least one hydrogen storage container fitted with a fusible plug type safety valve, the fuel cell comprising the disaster prevention equipment according to any one of claims 1 to 13. vehicle. A hydrogen trailer in which a plurality of hydrogen storage containers fitted with fusible plug type safety valves are loaded on a loading platform, the hydrogen trailer comprising the disaster prevention equipment according to any one of claims 1 to 13. . A stationary facility equipped with at least one hydrogen storage container equipped with a fusible plug type safety valve, characterized by comprising the disaster prevention facility according to any one of claims 1 to 13. Facility.

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