JP2011004884A - Extinguishant and flammable liquid containing extinguishing gas - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide extinguishant and flammable liquid containing extinguishing gas where extinguishing gas stably exists in the liquid in high density over a long period.SOLUTION: In the extinguishant, gas containing extinguishing gas becomes nano-sized bubbles and is mixed with liquid. Further, in the flammable liquid containing extinguishing gas, the gas containing extinguishing gas becomes nano-sized bubbles and is mixed with the flammable liquid. Preferably, the liquid comprises molecules forming hydrogen bonds and a distance of the hydrogen bonds of molecules of the liquid present in an interface with the bubbles is shorter than the distance of the hydrogen bonds when the liquid is at normal temperature and normal pressure.

Description

  The present invention relates to a fire extinguisher used to extinguish a fire in the event of a fire, and a fire extinguishing gas-containing combustible liquid that extinguishes a fire of a combustible liquid.

  Conventionally, a fire extinguisher such as a fire extinguisher, a fire hydrant, a sprinkler, and a fire truck is used to extinguish a fire. Fire extinguishing devices are designed to extinguish fires by spraying water, fire extinguishing substances, etc. In order to enhance fire extinguishing performance, fire extinguishing agents are widely used to extinguish fires using fire extinguishing agents. However, the fire extinguishing agent using the fire extinguishing powder has a problem that the scattered powder remains after the fire extinguishing and is difficult to clean. In addition, with a fire extinguisher using a gas such as a fire extinguishing gas, there is a possibility that the gas is diffused and the fire extinguisher cannot be efficiently applied to the fire source. In addition, fire extinguishing using water required a large amount of water for fire extinguishing, and the efficiency of fire extinguishing was not good. Especially for flammable liquids such as oil, it is difficult to extinguish efficiently because it is dangerous to use water for extinction.

  Patent Document 1 discloses a fire extinguishing facility that extinguishes with water in which microbubbles of inert gas are generated. According to this method, the fire can be extinguished by the two actions of the inert gas and water, and it is estimated that the fire extinguishing performance can be improved as compared with the case of only water.

  However, since the microbubbles are released as a gas in a short time and disappear, they cannot be used as a filling-type extinguishing agent used in a fire extinguisher or the like. Further, the amount of gas contained in the microbubble water is not large, and it has been difficult to sufficiently improve the fire extinguishing performance as compared with a normal fire extinguishing agent.

  In addition to flammable liquids, fire damage is likely to increase, and it is often dangerous to extinguish with water, and there is a problem that it must be extinguished with a large amount of special fire extinguishing agents. It was.

JP 2007-268186 A

  The present invention has been made in view of the above points, and provides a fire-extinguishing agent and a fire-extinguishing gas-containing combustible liquid in which a fire-extinguishing gas is stably present in a liquid at a high density for a long period of time. It is the purpose.

  The invention according to claim 1 is a fire extinguishing agent characterized in that a gas containing a fire extinguishing gas is mixed with a liquid in the form of nano-sized bubbles.

  According to the present invention, since the gas containing the fire extinguishing gas becomes nano-sized bubbles and stably exists in the liquid, the fire extinguishing gas can be held in the liquid for a long period of time. It can be used as a fire extinguisher for a stand-alone fire extinguisher. Moreover, since the fire-extinguishing gas is present in the liquid as nano-sized bubbles, the fire-extinguishing gas can be brought into contact with fire efficiently, and can be extinguished efficiently with a small amount. Moreover, it is not necessary to use a special fire extinguishing agent, and the fire extinguishing agent can be easily obtained by containing a fire extinguishing gas in the liquid. In addition, fire extinguishing can be performed without using special chemicals or powders, and the amount of liquid such as water used for extinguishing can be reduced, so that post-treatment after fire extinguishing becomes easy.

  According to a second aspect of the present invention, in the fire extinguisher, the liquid is a liquid composed of molecules that form hydrogen bonds, and the distance between the hydrogen bonds of the molecules present at the interface with the liquid bubbles is such that the liquid is at normal temperature and pressure. It is a fire extinguisher characterized by being shorter than the distance of a certain hydrogen bond.

  According to the present invention, the distance between hydrogen bonds at the bubble interface is shortened so that the bubbles can be surrounded by liquid molecules that form strong hydrogen bonds. The liquid molecules that form hydrogen bonds are strong shells. Since the air bubbles are wrapped, the air bubbles do not collapse even if they collide with each other, and can counteract the pressure from the liquid with the stress from the inside of the air bubbles, and the air bubbles containing the fire extinguishing gas disappear in the liquid It can be made to exist stably without making it unite or unite. And since this hydrogen bond is stable over a long period of time, it is possible to use a fire extinguisher in which bubbles containing a fire extinguishing gas exist stably over a long period of time. Also, nano-order-sized fire extinguishing gas bubbles can be generated at a density far exceeding the conventional level and can be stably present in the liquid.

  The invention according to claim 3 is the fire extinguisher, wherein the weight per unit volume of the fire extinguishing gas is equal to or more than the weight per unit volume of nitrogen.

  According to the present invention, the weight of the extinguishing gas is approximately equal to or more than the weight of the air, so that the extinguishing gas is floated or scattered before coming into contact with the fire. Without hesitation, a heavy fire extinguishing gas can be retained or settled and supplied to the fire source, and the fire extinguishing efficiency can be improved.

  The invention according to claim 4 is the fire extinguisher, wherein the liquid is water.

  According to this invention, a fire extinguisher can be easily obtained without using a special liquid, and can be extinguished by a synergistic effect of the fire extinguishing effect of water and the extinguishing effect of the extinguishing gas, Fire extinguishing efficiency can be further improved. Also, water molecules form a strong bond between O ... H hydrogen bonds, that is, oxygen atoms of one water molecule and hydrogen atoms of another water molecule, so that the hydrogen bond at the bubble interface becomes strong. Thus, the bubbles can be further stabilized.

  The invention according to claim 5 is the fire extinguisher characterized in that, in the fire extinguisher, the concentration of the fire extinguishing gas contained in the liquid is equal to or higher than the saturated dissolution concentration of the fire extinguishing gas with respect to the liquid.

  According to the present invention, a high-concentration extinguishing gas contained in a liquid can be used for extinguishing by holding a saturated amount of extinguishing gas or a large amount of extinguishing gas exceeding the saturated dissolution amount in the liquid. Can be further improved.

  Invention of Claim 6 is a fire extinguisher characterized by the pressure of the gas which forms the bubble in the said fire extinguisher being 0.12 Mpa or more.

  According to this invention, a stronger interface structure can be formed by maintaining bubbles at a high internal pressure, and more gas molecules can be confined. In addition, in the stationary state, a stable bubble is formed, and once an impact is applied, the interface structure of the bubble collapses due to the force of the internal pressure, and the bubble coalesces and foams to release the extinguishing gas to the outside. Therefore, this foaming can be used for fire extinguishing.

  The invention according to claim 7 is the fire extinguisher, characterized in that the fire extinguisher has a sherbet shape.

  According to the present invention, since the bubbles are mixed with the sherbet-like extinguishing agent, the fire extinguishing gas is prevented from being generated and scattered by the surrounding heat before coming into contact with the fire. Can be generated at the source of the fire and brought into contact with the fire, and the fire extinguishing efficiency can be improved. Further, since it is in the form of a sherbet, it can be reliably supplied to the fire source by injection or the like, and can be extinguished efficiently using the cooling effect of the sherbet.

  The invention according to claim 8 is the fire extinguisher characterized in that in the fire extinguisher, a thickener is contained in the liquid.

  According to the present invention, since the bubbles are mixed with the liquid containing the thickener, the bubbles are held by the viscosity, and the fire extinguishing gas is prevented from being generated and dispersed before coming into contact with the fire. It is possible to generate a trapped fire extinguishing gas at the source of the fire and bring it into contact with the fire. Also, the viscosity of the liquid is increased or adhesive force is applied, and a fire extinguishing agent is adhered and attached at the source of the fire to extinguish the fire. Since a reactive gas can be discharged, fire extinguishing efficiency can be improved.

  The invention according to claim 9 is a fire-extinguishing gas-containing combustible liquid, characterized in that a gas containing a fire-extinguishing gas is formed into nano-sized bubbles and mixed with a combustible liquid.

  According to the present invention, the gas containing the fire extinguishing gas becomes nano-sized bubbles and stably exists in the flammable liquid, so that the fire extinguishing gas can be held in the liquid for a long period of time. It is. In addition, since the fire extinguishing gas is present in the liquid as nano-sized bubbles, even if a flammable liquid is ignited or ignited, a fire is generated. Since the gas is contained, the fire can be extinguished by directly contacting the fire source with a fire extinguishing gas, and a safe fuel can be obtained. In addition, fire extinguishing can be performed without using special chemicals and powders, and even if chemicals or powders are used, the amount of chemicals and powders can be reduced, so post-extinguishment is easy. It will be. Further, when using a flammable liquid, it is only necessary to generate and release a fire extinguishing gas, and it is possible to impart fire extinguishing properties without deteriorating the properties of the liquid.

  According to the present invention, since the gas containing the fire extinguishing gas becomes nano-sized bubbles and stably exists in the liquid, the fire extinguishing gas can be held in the liquid for a long period of time. It can be used as a fire extinguishing agent for a stand-alone fire extinguishing device, and can provide a fire-safe and combustible liquid. Moreover, since the fire-extinguishing gas is present in the liquid as nano-sized bubbles, the fire-extinguishing gas can be brought into contact with fire efficiently, and can be extinguished efficiently with a small amount. In addition, fire extinguishing can be performed without using a special chemical or powder, and the amount of liquid used for extinguishing can be reduced, so that post-treatment after fire extinguishing becomes easy.

It is a perspective view which shows the outline of a mode that a combustible material is stored using the fire extinguisher of this invention. It is the schematic which shows an example of the manufacturing apparatus of a gas-liquid liquid mixture (extinguishing agent or fire extinguishing gas containing flammable liquid), (a) is the whole schematic, (b) is a partial schematic. (A)-(c) is the schematic which shows a part of manufacturing apparatus of a gas-liquid liquid mixture (extinguishing agent or fire extinguishing gas containing combustible liquid), respectively. (A)-(d) is the schematic which shows a part of manufacturing apparatus of a gas-liquid liquid mixture (extinguishing agent or a fire extinguishing gas containing combustible liquid), respectively. It is the schematic which shows a part of manufacturing apparatus of a gas-liquid liquid mixture (extinguishing agent or a fire extinguishing gas containing combustible liquid). It is the schematic which shows another example of the manufacturing apparatus of a gas-liquid liquid mixture (extinguishing agent or a fire extinguishing gas containing combustible liquid). (A), (b) is the schematic which shows a part of manufacturing apparatus of a gas-liquid mixed liquid (extinguishing agent), respectively. It is the schematic which shows another example of the manufacturing apparatus of a gas-liquid liquid mixture (extinguishing agent). It is a graph which shows the difference of the infrared absorption spectrum of the gas-liquid liquid mixture (extinguishing agent) using nitrogen and water, and nitrogen saturated water. It is a graph which shows the gas volume contained in a gas-liquid liquid mixture (extinguishing agent). It is a photograph of the gas-liquid liquid mixture (extinguishing agent) by a scanning electron microscope (SEM). It is a conceptual explanatory drawing of the gas-liquid interface of the bubble in a gas-liquid liquid mixture (extinguishing agent or a fire extinguishing gas containing combustible liquid). It is a graph which shows stability of a gas-liquid mixed liquid (extinguishing agent).

  Hereinafter, modes for carrying out the invention will be described.

  The fire-extinguishing agent and the fire-extinguishing gas-containing combustible liquid of the present invention are those in which a gas containing a fire-extinguishing gas is mixed with the liquid as nano-sized bubbles. The gas containing the fire extinguishing gas is stably present in the liquid as nano-sized bubbles, and the gas is not released and the fire extinguishing gas does not escape. Therefore, extinguishing gas can be held in the liquid for a long period of time, and can be used as a fire extinguishing agent for a filling type or a standing type extinguishing device as a fire extinguishing agent. A flammable liquid that is safe to handle can be obtained.

  The fire extinguishing gas is not particularly limited, and various fire extinguishing gases (gas) such as an inert gas can be used. For example, a fire extinguishing gas such as carbon dioxide, nitrogen, argon, neon, helium, or other rare gas can be used singly or in combination. It is also preferable to use a halide gas as the extinguishing gas. Examples of the halide gas include, for example, halon 1301 (bromotrifluoromethane), halon 1211 (bromochlorodifluoromethane), HFC-227ea (heptafluoropropane), and HFC-23 (trifluoromethane), which are gases at normal temperature and pressure. ) Etc. can be used. Further, Halon 2402 (dibromotetrafluoroethane), which is liquid at normal temperature and pressure, can be used as a gas in a heated state.

  As a gas containing a fire extinguishing gas that forms bubbles, a gas composed of this fire extinguishing gas may be used as it is, or a bubble may be formed using a gas partially containing the fire extinguishing gas. When using a fire-extinguishing gas together with other gases, the gas used in combination is preferably a gas that is not flammable or weakly flammable, such as an inert gas or air. In this case, the fire-extinguishing property is impaired. It may be contained within the range.

  Moreover, it is preferable that the weight per unit volume of the fire extinguishing gas is not less than the weight per unit volume of nitrogen. If the weight of fire extinguishing gas is heavier than air, the fire extinguishing gas may float or scatter before it comes into contact with the fire during fire extinguishing. When the weight is greater than nitrogen (molecular weight 28) and approximately equal to or greater than the weight of air (average molecular weight of air 28.8), a heavy fire extinguishing gas is retained or settled and supplied to the fire source. Can improve the fire extinguishing efficiency. Specific examples of such a fire extinguishing gas include nitrogen, argon, carbon dioxide, and the above halides.

  As the liquid, it is preferable to use a liquid composed of molecules that form hydrogen bonds. In this case, the distance between the hydrogen bonds of the molecules present at the interface with the liquid bubbles is such that the liquid is at room temperature and normal pressure (25 ° C., 1 It is preferable that the distance is shorter than the distance between hydrogen bonds at atmospheric pressure (0.1013 MPa). A hydrogen bond is a bond that stabilizes the system in a molecule that has a high electronegativity atom and a hydrogen atom, because the hydrogen atom approaches the high electronegativity atom of another molecule. . Thus, when the extinguishing agent is present under normal temperature and normal pressure conditions, the hydrogen bond distance at the bubble interface of the fire extinguishing gas becomes shorter than the normal hydrogen bond distance at normal temperature and normal pressure. The surroundings are surrounded by liquid molecules that form strong hydrogen bonds. And the liquid molecule which formed this hydrogen bond turns into a firm shell, and encloses a bubble. As a result, even if the bubbles collide with each other, they will not collapse, and the pressure from the liquid can be countered by the stress from the inside of the bubbles, so that the bubbles containing the fire extinguishing gas are extinguished or combined in the liquid. It can be held without having to. In other words, it is different from conventional bubbles that are stable with surface tension.

  The distance between the hydrogen bonds of the liquid molecules at the interface with the bubbles can be appropriately set depending on the liquid used, but is 99% or less when the distance between hydrogen bonds at room temperature and normal pressure is 100%. Is preferred. When the hydrogen bond distance falls within this range, the bubbles can be surrounded and stabilized by a hard shell of hydrogen bonds. If the distance between hydrogen bonds is longer than this, there is a possibility that bubbles cannot be stabilized and exist. Considering the interatomic distance, the lower limit of the hydrogen bond distance is 95%. The hydrogen bond distance at the bubble interface in the fire extinguisher can be calculated, for example, by analyzing the infrared absorption spectrum (IR) of the liquid in which the bubbles are mixed, as shown in the examples described later.

  By the way, a liquid having a hydrogen bond distance of the above-mentioned distance usually has a solid or hydrate crystal structure like ice. However, in the above-mentioned liquid, hydrogen having a short distance locally at the bubble interface. Bonds are formed and normal hydrogen bonds are formed in other liquids. That is, a hard shell of liquid molecules is formed by hydrogen bonds at a short distance at the bubble interface to prevent the bubbles from coalescing and disappearing, and at other than the bubble interface, liquid exists in a normal state and normal temperature At normal pressure, fluidity is ensured, and it is easy to use liquid in which stable bubbles are present.

  The bubbles contained in the liquid are nano-sized bubbles, specifically, bubbles having a diameter of 1 to 1000 nm (so-called nano bubbles). When the bubbles are nano-sized and fine, a strong bubble interface structure can be formed, and a high-concentration gas can be held in the liquid. Further, since buoyancy does not act on the nano-order size bubbles, the bubbles do not rise and separate from the liquid, so that the bubbles can exist stably over a long period of time. Even if the bubble is smaller or larger than this range, the bubble may not be stabilized. In addition, the bubble size can be measured by a scanning electron microscope (SEM), and the average particle diameter of the bubbles can be obtained by averaging the particle diameters of the bubbles obtained by the measurement. By the way, the liquid mixed with microbubbles is cloudy and can be discriminated visually. However, the liquid mixed with nanobubbles is colorless and transparent (or the color of the liquid when the liquid is colored) and can be discriminated visually. Can not. Therefore, discrimination of nano-sized bubbles is performed by SEM or density measurement.

  One of the liquids preferably used is water. In this case, the fire can be extinguished by a synergistic effect of the fire extinguishing effect of water and the extinguishing effect of the extinguishing gas, and the fire extinguishing efficiency can be improved. Further, the water molecule is a hydrogen bond of O ... H, that is, a hydrogen bond is formed between an oxygen atom of one water molecule and a hydrogen atom of another water molecule, and water is used as a fire extinguisher liquid. And this hydrogen bond in the liquid becomes strong at the bubble interface, and the bubbles of the fire extinguishing gas can be further stabilized. Further, since water is abundant in supply sources and can be obtained stably, a fire extinguisher can be easily obtained without using a special liquid. That is, the water used for the fire extinguishing agent is not limited to high-purity water, and any water can be used including water and sewage systems, ponds, seawater, and the like. That is, any material that contains water as a liquid may be used.

Further, the liquid is a liquid composed of molecules having any one or more of (halogen) -H bond and S—H bond such as O—H bond, N—H bond, F—H bond and Cl—H bond. It is also preferable. These bonds are bonds between atoms and hydrogen atoms having a sufficiently large electronegativity with respect to hydrogen atoms, such as OH ... O, NH ... N, FH ... F, and Cl-H ... Cl. (Halogen) -H (Halogen), S—H,... S, and so on, are formed, and by this hydrogen bond, bubbles can be surrounded and stabilized. A typical liquid having an O—H bond is water, but other examples include hydrogen peroxide, alcohols such as methanol and ethanol, and glycerin. Moreover, ammonia etc. can be illustrated as a liquid which has a N-H bond. Examples of those having a (halogen) -H bond include HF (hydrogen fluoride) having an F-H bond and HCl (hydrogen chloride) having a Cl-H bond. Examples of those having an S—H bond include H ₂ S (hydrogen sulfide).

  It is also preferable that the liquid is a liquid composed of molecules having a carboxyl group. The carboxyl group has a carbonyl oxygen atom with high electronegativity, and the carbonyl oxygen atom in one carboxyl group and a hydrogen atom in another carboxyl group form a strong hydrogen bond to surround the bubble. Therefore, it is possible to obtain a fire extinguisher in which bubbles are stably present. Examples of the liquid composed of molecules having a carboxyl group include carboxylic acids such as formic acid and acetic acid.

  In the case of a fire-extinguishing gas-containing combustible liquid, a combustible liquid is used as the liquid. Combustible liquids are flammable or flammable and dangerous, and should be handled with care. However, if a fire extinguishing gas is stably present in the flammable liquid, even if a fire occurs, It can be extinguished immediately. Examples of the flammable liquid include fuel and organic matter (organic solvent). Specifically, as the flammable liquid, alcohol such as methanol or ethanol is exemplified as a fuel or organic substance having hydrogen bonds, and acetic acid, propionic acid, acrylic acid, aniline, glycol or the like is exemplified as an organic solvent having hydrogen bonds. It is done. Moreover, gasoline, kerosene, light oil, etc. are mentioned as a fuel, and special flammables, such as carbon disulfide, diethyl ether, acetaldehyde, propylene oxide, are mentioned as dangerous goods. Among these, a liquid having a hydrogen bond can be suitably used as the liquid. In addition, when a fuel (liquid fuel) is used as the liquid, it becomes possible to obtain a self-extinguishing fuel described later.

  The concentration of the extinguishing gas contained in the liquid is preferably equal to or higher than the saturated dissolution concentration of the extinguishing gas with respect to the liquid. By holding a saturated dissolution amount or a large amount of fire extinguishing gas exceeding that in the liquid, it is possible to use the high concentration fire extinguishing gas contained in the liquid for extinguishing the fire, and further improve the fire extinguishing efficiency. It can be done. More preferably, a saturated dissolved amount of fire extinguishing gas is dissolved in the liquid, and the fire extinguishing gas bubbles are present in the saturated dissolving liquid. If the fire-extinguishing gas is dissolved in a saturated dissolution amount, the fire-extinguishing gas that has become bubbles can be stabilized without being dissolved and held in the liquid as bubbles. In other words, a liquid in which a gas is present in an amount greater than or equal to the saturated dissolution amount has the fire extinguishing gas dissolved at a saturated concentration in the liquid, and the bubbles do not collapse or dissolve. Can be present in the liquid. Furthermore, it is preferable that the dissolution concentration of the fire extinguishing gas is a saturated dissolution concentration. When the concentration of the extinguishing gas is increased in this manner, the bubbles can be stabilized in a state where the distance of hydrogen bonding is shortened, and when the stabilized bubbles are subjected to heat or impact, Since it is released as a gas, the fire extinguishing efficiency can be further improved. The amount of gas in the liquid can be calculated from the amount of mass change by separating the gas from the liquid as shown in the examples described later.

  The pressure of the gas forming the bubbles, that is, the internal pressure of the bubbles is preferably 0.12 MPa or more, and more preferably higher than the internal pressure of the bubbles given by the Young Laplace equation (the following equation).

Young Laplace's formula ΔP = 2σ / r
[ΔP: rising pressure inside the bubble, σ: surface tension, r: bubble radius]

When the internal pressure of the bubbles becomes such a pressure, the bubbles are maintained at a high internal pressure, and a stronger interface structure can be formed. Therefore, stable bubbles can be formed in a stationary state. On the other hand, once an impact is applied to the liquid, the interfacial structure of the bubbles collapses due to the force of the internal pressure, the bubbles coalesce and foam and release the extinguishing gas to the outside. It is something that can be done. The internal pressure of the bubbles can be calculated by fitting the total amount of gas in the liquid and the gas volume calculated from the density to the gas equation of state as shown in the examples described later.

Note that a liquid in which nano-sized bubbles are mixed has a negative zeta potential when water is used as the liquid, and the area of the bubble interface existing in a volume of 1 cm ³ is about 0.6 m ² .

As a fire extinguisher, a liquid form can be used, but a sherbet form is also preferable. That is, the liquid in which the fire-extinguishing gas bubbles are mixed is cooled while containing the bubbles to form a large number of solid particles. In this case, since the bubbles are mixed with the sherbet-like fire extinguisher, it is possible to prevent the fire extinguishing gas from being generated by the surrounding heat before being brought into contact with the fire to be dispersed. Accordingly, the trapped fire extinguishing gas can be generated at the fire source and brought into contact with the fire, and the fire extinguishing efficiency can be improved. Moreover, since it is a sherbet shape, it does not flow out and can be reliably supplied to the fire source by injection or the like as solid particles. Furthermore, the fire source can be extinguished while the fire source is cooled with a sherbet, and the fire can be extinguished efficiently. The sherbet shape may be any shape that contains solid particles, and the solid particles and liquid may be mixed. The size and shape of the individual grains are not particularly limited, but for example, a volume of about 1 mm ^{3 to} 10 cm ³ is preferable because it facilitates injection and makes it easy to come into contact with fire.

  Moreover, in a fire extinguisher, it is also preferable that the thickener is contained in the liquid. In this case, since the bubbles are mixed with the liquid in which the thickener is dissolved, the viscosity of the liquid is increased and the bubbles can be held in the liquid. Therefore, the fire extinguishing gas is prevented from being generated and dispersed before it comes into contact with the fire, and the trapped fire extinguishing gas can be generated at the source of the fire and brought into contact with the fire. If a thickener is contained, the viscosity of the liquid increases or adhesive strength is applied, and the extinguishing gas can be released by adhering and adhering the extinguishing agent at the source of the fire. Can be increased.

  The thickener is not particularly limited as long as it thickens the liquid, but a water-soluble thickener can be suitably used when the liquid is water. The concentration and viscosity of the thickener can be adjusted as appropriate.For example, the viscosity of the extinguishing agent can be held firmly while holding the bubbles firmly without disturbing the fire extinguishing agent from being brought into contact with the fire, for example. It is preferable to adjust the viscosity to such an extent that a fire extinguishing gas can be released when it comes into contact.

  Examples of thickeners include, for example, senile (cellulose) and derivatives thereof such as sodium carboxymethylcellulose (CMC) and methylcellulose (MC), and protein systems such as albumin (egg white component), casein (milk component), and pectin. Natural thickeners such as alginic acid, carrageenan, xanthan gum, guar gum, agar, starch, sodium alginate, polysaccharides, vinyl-based, vinylidene-based compounds and compounds combining these, polyester-based compounds, polyamides Examples thereof include synthetic thickeners including polymer compounds such as polymer compounds, polyether compounds, polyglycol compounds, polyvinyl alcohol compounds, polyalkylene oxide compounds, and polyacrylic acid compounds.

  The fire extinguisher of the present invention can be used as various fire extinguishing agents used in fire extinguishing devices / equipment, and can be used as fire extinguishing agents for fire extinguishers, fire hydrants, sprinklers, fire engines, fire fighting tanks, etc. . Specifically, in a fire extinguisher, it can be used as a filling fire extinguisher or filled in a tank of a fire engine or the like. In particular, in a fire extinguisher such as a fire extinguisher or a stationary fire extinguisher, the fire extinguishing gas is stably present over a long period of time as a gas bubble, so that it is possible to obtain a fire extinguishing apparatus that does not deteriorate the fire extinguishing performance. .

  In extinguishing a fire, it can be extinguished by bringing the above-mentioned extinguishing agent into contact with the fire by jetting, lowering, or throwing it in. At this time, the fire-extinguishing gas is present in the liquid as nano-sized bubbles, so that the fire-extinguishing gas is not released and scattered before it comes into contact with the fire. It can be brought into contact with fire and can be extinguished efficiently with a small amount. In addition, fire extinguishing can be performed without using a special drug or powder, and the amount of liquid such as water used for extinguishing can be reduced. Therefore, a large amount of powder or chemicals does not remain around the fire site after fire extinguishing, or the fire site does not become flooded, and post-treatment after fire extinguishing can be facilitated.

  Further, the fire extinguishing agent can be sealed in a container and used as a fire extinguishing tool placed in a place that may become a fire source, for example, a fuel storage, a hazardous material storage, a gas facility, a kitchen, or the like. In that case, the fire extinguishing gas that is held in the liquid as bubbles in a normal state is released from the liquid when the temperature rises above a predetermined temperature due to a rapid temperature rise due to a fire, and extinguishes in a place close to the fire source. Since it can be performed, it can be extinguished efficiently.

  FIG. 1 is a perspective view schematically showing a state in which a combustible material is stored using the fire extinguisher of the present invention. The combustible F is placed in a cylindrical container 101, and a cylindrical fire extinguisher container 102 in which a fire extinguisher A is sealed is arranged at the center of the circle of the container. That is, the combustible F is stored in close contact with the extinguishing agent A. The combustible F may be any of liquid, solid, and gas. In the storage of such a combustible material F, the fire extinguishing agent A is disposed in close contact with the combustible material F. Therefore, even if a fire is generated by igniting the combustible material F, the fire extinguishing agent A is extinguished. It is possible to extinguish a fire at the source of the fire and improve the fire extinguishing efficiency, and it is possible to safely store and store the combustible F. Moreover, if the container 101 is transported in this state, the combustible F can be transported safely.

  The fire-extinguishing gas-containing combustible liquid is a gas in which a fire-extinguishing gas-containing gas is mixed with a combustible liquid in the form of nano-sized bubbles. Therefore, this fire extinguishing gas works as a fire extinguishing agent and extinguishes fire when a flammable liquid such as fuel or organic solvent ignites and a fire occurs. For such flammable liquids, even if a fire occurs due to ignition or ignition, the liquid itself, which is the source of the fire, contains a fire extinguishing agent. Can be extinguished by touching. Therefore, it is possible to obtain a safe flammable liquid by preventing the fire from spreading.

  By the way, when using the fire-extinguishing gas-containing combustible liquid as fuel, for example, the fire-extinguishing gas may prevent the fuel component from burning. However, if the fire extinguishing gas is a liquid mixed in the form of nano-sized bubbles as described above, the fire extinguishing gas can be obtained by applying vibration to the fuel or heating the fuel to such an extent that a fire does not occur. Can be generated and released as a gas, and the fuel characteristics are not deteriorated. Therefore, both fire extinguishing properties and fuel properties can be achieved. As described above, the above fuel can be a self-extinguishing fuel.

  According to the fire extinguishing gas-containing combustible liquid as described above, the combustible liquid can be safely stored. That is, the above liquid can be used for a method for storing a combustible liquid. According to this storage method, even if a flammable liquid is ignited or ignited, it can be extinguished immediately because there is a fire extinguishing gas at the source of the fire, and the flammable liquid can be stored safely by increasing the fire extinguishing efficiency. Is something that can be done.

  Next, manufacture of the fire extinguisher and fire extinguishing gas containing combustible liquid of this invention is demonstrated. Both the fire extinguishing agent and the fire-extinguishing gas-containing combustible liquid can be obtained by mixing a gas containing a fire-extinguishing gas and a liquid to produce a gas-liquid mixture. Hereinafter, the production of this gas-liquid mixture will be described.

  FIG. 2 is a schematic diagram illustrating an example of a method for producing a gas-liquid mixture, and an example of an apparatus (gas-liquid mixture production apparatus) that generates the gas-liquid mixture is illustrated.

  This gas-liquid mixed liquid manufacturing apparatus is an apparatus for continuously manufacturing a gas-liquid mixed liquid by pumping liquid, taking out the liquid held at atmospheric pressure (0.1 MPa) from the liquid storage tank 12 and pumping it. A pressurizing unit 1 that pressurizes the gas, a gas supply unit 2 that supplies a gas containing a fire extinguishing gas to the pressurized liquid, and a gas-liquid mixing unit 3 that converts the supplied gas into fine bubbles and mixes with the liquid The defoaming unit 4 for removing large bubbles present in the liquid in the gas-liquid mixing unit 3 and the pressure of the liquid from which the large bubbles have been removed by the defoaming unit 4 are gradually increased without generating large bubbles. A decompression section 5 for decompressing to atmospheric pressure and a discharge section 7 for ejecting the decompressed liquid are provided, and each section is provided connected to a flow path 6.

  The pressurizing unit 1 pumps the liquid to the gas-liquid mixing unit 3 and can be constituted by, for example, a pump 11 that sucks up the liquid from the liquid storage tank 12 as in this device. It can also be constituted by a pipe that pressurizes and delivers the liquid.

  The gas supply unit 2 supplies a gas containing a fire extinguishing gas to the liquid by being connected to the flow path 6. For example, when supplying an inert gas such as nitrogen, carbon dioxide, or argon as a fire extinguishing gas, a gas supply unit 2 may be formed by connecting a cylinder filled with these gases to the flow path 6. it can. In addition, the gas supply unit 2 may be formed by connecting a carrier gas cylinder to the flow path 6 and connecting a fire extinguishing gas cylinder to the gas flow path between the carrier gas cylinder and the flow path 6. Good. The connection position of the gas supply unit 2 to the flow path 6 may be a position upstream of the gas-liquid mixing section 3 and is connected to the flow path 6 upstream of the pressurizing section 1 as in this device. Alternatively, it may be either connected to the flow path 6 on the downstream side of the pressurizing unit 1.

  The gas-liquid mixing unit 3 mixes the liquid fed under pressure and the gas injected into the liquid, and converts the gas into fine bubbles by pressurization and disperses and mixes them in the liquid. The gas-liquid mixing unit 3 can be configured by applying a stirring force by changing the cross-sectional area of the flow path, or if the liquid is flowing in the flow path 6 with the liquid being stirred, 6 can also be configured. When the gas supply unit 2 is in the flow path 6 on the upstream side of the pressurizing unit 1 as in this apparatus, the pressurizing unit 1 constituted by the pump 11 or the like may also be used as the gas-liquid mixing unit 3. When pressurization and mixing of gas and liquid are performed by the pump 11, the liquid can be rapidly pressurized and mixed, so that a gas-liquid mixture having a strong bubble interface structure can be reliably generated. Moreover, it is also preferable that the gas-liquid mixing unit 3 is constituted by a Venturi tube. In that case, the liquid can be rapidly pressurized and mixed with a simple configuration.

  In the gas-liquid mixing unit 3, the liquid and the gas are mixed under high pressure conditions. Thereby, a strong interface structure is formed around the bubble, and the bubble can be covered with the shell of the strong interface structure, and the gas can be stabilized as a fine bubble.

By the pressurization unit 1 and the gas-liquid mixing unit 3 as described above, a strong pressure is suddenly applied to the liquid into which the gas is injected, and the bubbles existing in the liquid are subdivided into fine nano-sized bubbles. And dispersed in the liquid. In addition, a strong interface structure is formed by liquid molecules at the interface of the bubbles that have become high pressure due to a sudden pressure change. At that time, when the pressurization rate ΔP ₁ / t (ΔP ₁ : pressure increase, t: time) is 0.17 MPa / sec or more, the bubbles are subdivided to generate fine nano-sized bubbles. The pressure of the gas-liquid mixed liquid when it is sent out from the gas-liquid mixing part 3 to the defoaming part 4 becomes 0.15 MPa or more, thereby generating nano-sized bubbles with a strong structure at the bubble interface Is something that can be done. In consideration of substantial pressurization conditions, the upper limit of the pressurization rate ΔP ₁ / t is 167 MPa / sec, and the upper limit of the pressure of the pressurized gas-liquid mixture is 50 MPa.

  FIG. 2B is a schematic view of the main part showing an example of a specific form of the pump 11. The pump 11 a pressurizes the liquid by the rotation of the rotating body 21, and the rotating blades 22 attached to the rotating body 21 continuously rotate to pump the pump outlet 27 through the pump passage chamber 23 from the pump inlet 26. The liquid is sent out in the direction of flow to and pressurized. In the figure, the white arrow indicates the flow direction of the liquid, and the solid line arrow indicates the rotation direction of the rotating body 21. The pump 11a includes four rotary blades 22. Further, the rotating shaft 25 of the rotating body 21 is arranged so as to be deviated toward the pump outlet 27 side from the cylindrical center of the pump wall 24 formed in a cylindrical shape, and is provided as an eccentric shaft. The volume of the second flow path chamber 23b of the pump flow path chamber 23 is formed smaller than the volume of the first flow path chamber 23a due to the eccentricity of the rotary shaft 21, and the pump flow path chamber is arranged along the liquid flow direction. The volume of 23 is gradually reduced.

Then, the liquid fed to the pump flow passage chamber 23 is pressurized is fed by rotating blades 22, large bubbles B _B due to rapid pressure changes bubbles B _N of subdivided by fine nano-sized generated . That is, the liquid sent from the first flow path chamber 23a to the second flow path chamber 23b along with the rotation of the rotating body 21 is rapidly compressed and pressurized as the volume of the pump flow path chamber 23 becomes smaller. Nano-sized bubbles _BN are generated by the pressure. Further, in the illustrated pump 11a, a shearing force is applied when the liquid passes between the inner surface of the pump wall 24 and the tip of the rotor blade 22, and the liquid is pressurized while being sheared by the clearance. At this time, the gas (large bubbles B _B ) mixed in the liquid is sheared by the shearing force applied to the liquid and becomes finer nano-sized bubbles (B _N ). The distance narrowest part between the inner surface of the pump wall 24 and the tip portion of the rotor blades 22, i.e. the clearance distance L _C is preferably 5Myuemu～2mm. Thus, according to the pump 11a using the rotator 21, it is possible to form nano-sized bubbles by shearing the gas injected into the liquid while being rapidly pressurized with the rotator 21 with a strong force. A gas-liquid mixture having a strong bubble interface structure can be generated more reliably.

  The rotational speed of the rotating body 21 of the pump 11 is preferably 100 rpm or more. At this time, it becomes 1/2 rotation or more in 0.3 seconds. By having such a rotational speed, it is possible to reliably generate nano-sized bubbles in which the hydrogen bond distance is shortened by injecting a gas having a saturation dissolution concentration or more into the liquid.

  The pressurization by the pressurizing unit 1 and the gas-liquid mixing unit 3 can be performed multiple times by providing a plurality of pressurizing units 1 or gas-liquid mixing units 3. By pressurizing the liquid a plurality of times while feeding the liquid, the pressurization can be performed by a plurality of pumps 11 and venturi pipes, and the liquid is strongly pressurized to generate a gas-liquid mixture having a strong bubble interface structure. It is something that can be done. Specifically, the pressurizing unit 1 can be configured with a pump 11 as shown in FIG. 2, and the gas-liquid mixing unit 3 can be configured with one or more pumps 11 or a venturi tube.

  The defoaming section 4 is for removing bubbles exceeding nanosize, that is, bubbles exceeding 1 μm in diameter, from the liquid in which the gas is mixed as described above. The bubbles are lifted by their own buoyancy and removed. It can be composed of a tube or the like. Since the removed bubbles become gas and accumulate on the upper part, the removed gas can be removed by the gas removing unit 8. Bubbles of a size exceeding 1 μm in diameter (micro-sized bubbles) are raised by buoyancy, so that relatively large bubbles are removed and nano-sized bubbles that are fine bubbles are present in the liquid. It is possible to obtain a stable gas-liquid mixture having a strong interface structure.

  Specifically, the defoaming section 4 can be configured as shown in FIG. (A) is formed so as to be substantially horizontal to the ground surface (on a plane substantially perpendicular to the direction of gravity) continuously with the gas-liquid mixing unit 3, and the bubbles B in the liquid Lq are It shows an example of a tubular body that is lifted up to remove bubbles B. (B) is formed so that the shape combined with the gas-liquid mixing unit 3 and the gas-liquid mixing unit 3 is a reverse L-shape when viewed from the front, and the flow direction of the liquid Lq is downward (the direction of gravity) In this example, the bubbles B are removed by raising the bubbles B in the liquid Lq to the liquid level by the buoyancy. Further, (c) is separated from the gas-liquid mixing unit 3, and the flow direction of the liquid Lq is set downward (substantially the same direction as the direction of gravity), and the bubbles B in the liquid Lq are raised to the liquid level by the buoyancy. This shows an example of a tubular body that is made to remove bubbles B.

The decompression unit 5 gradually reduces the pressure of the liquid mixed with gas to atmospheric pressure without generating large bubbles. When the liquid mixed with gas by pressurization as described above is in a high-pressure state and is discharged to the outside under atmospheric pressure as it is, bubbles in the gas-liquid mixture are combined due to a sudden pressure drop. May become a gas and be discharged from the liquid, and cavitation may occur. Therefore, the decompression unit 5 is provided, and when the gas-liquid mixture in a pressurized state is sent out, the decompression unit 5 gradually reduces the pressure to atmospheric pressure and then discharges it. The decompression unit 5 is configured to decompress while reducing the upper limit of the decompression speed ΔP ₂ / t (ΔP ₂ : decompression amount, t: time) over the entire piping while sending a liquid in which gas is mixed. ing. Thus, the gas-liquid mixture can be taken out without erasing or coalescing the nano-sized bubbles while maintaining the structure of the strong bubble interface.

The decompression unit 5 can be configured as shown in FIG. 4, and specifically, the flow path 6 in which the cross-sectional area of the flow path gradually decreases as shown in FIG. In this way, the flow path 6 in which the cross-sectional area of the flow path gradually decreases gradually, or the gas-liquid mixing in the high pressure state (P ₁ ) due to the pressure loss in which the pressurized liquid flows in the flow path 6 as in (c). The flow path 6 whose flow path length (L) is adjusted so as to reduce the pressure of the liquid gradually (P ₂ , P ₃ ,...) To the atmospheric pressure (P _n ), and (d) Thus, it can be configured by a plurality of pressure regulating valves 9 provided in the flow path 6.

For example, when the decompression unit 5 as shown in FIG. 4A or 4B is used, the flow path 6 upstream of the decompression unit 5 has an inner diameter of 20 mm, and the decompression unit 5 has a flow path length of about 1 cm to At 10 m, the inner diameter can be gradually reduced from 20 mm to 4 mm so that the cross-sectional area of the flow path can be reduced. In addition, the decompression part 5 can be set to inlet inner diameter / outlet inner diameter = about 2-10, or the inner diameter reduction | decrease value per cm can be set to about 1-20 mm. At this time, if the gas-liquid mixed solution is sent to the decompression unit 5 at a flow rate of 4 × 10 ⁻⁶ m / s or more, the decompression rate is 2000 MPa / sec or less and the pressure can be reduced by 1.0 MPa without erasing the nano-sized bubbles. The gas-liquid mixture can be depressurized to atmospheric pressure.

  The discharge part 7 discharges the decompressed liquid. As shown in FIG. 5, an extension flow path 10 can be provided between the discharge part 7 and the pressure reducing part 5 in order to ensure a sufficient liquid pushing pressure in the pressure part 1. That is, the total pressure loss including the decompression unit 5 is calculated, the pressure required to pressurize the liquid and gas in the gas-liquid mixing unit 3 by the indentation pressure from the pressurization unit 1, and the total pressure loss The extended flow path 10 may be added to the flow path 6 with the flow path length adjusted so that the pressure loss of this difference occurs. In order to secure the indentation pressure, it may be possible to provide a throttling portion or the like. However, if the indentation pressure is adjusted by the throttling portion or the like, bubbles may collapse due to a sudden pressure change. However, if the extension channel 10 is provided in this way, the gas-liquid mixture can be discharged while the bubbles are stabilized.

In the gas-liquid mixture manufacturing apparatus configured as described above, the liquid is pumped by the pressurizing unit 1, and the gas containing the fire extinguishing gas is supplied to the liquid pumped by the gas supply unit 2 and injected. To do. Then, the liquid into which the gas has been injected is pressurized by the pressurizing unit 1 and the gas-liquid mixing unit 3 at a pressurization rate ΔP ₁ / t (ΔP ₁ : pressure increase, t: time) of 0.17 MPa / sec or more. The liquid pressure is set to 0.15 MPa or more. That is, the pressure of the liquid when being sent out from the gas-liquid mixing unit 3 to the defoaming unit 4 is 0.15 MPa or more. Thereafter, after the bubbles exceeding the nano size in the gas-liquid mixed solution are removed by the defoaming part 4, the pressure reduction rate ΔP of the maximum pressure reduction rate of 2000 MPa / sec or less while sending the liquid to the pressure reduction part 5 and the flow path 6 on the downstream side. _The pressure is gradually reduced to atmospheric pressure at ₂ / t (ΔP ₂ : reduced pressure amount, t: time). As a result, a gas-liquid mixed liquid in which nano-sized bubbles are stably present can be generated.

  The flow path 6 on the downstream side of the gas-liquid mixing unit 3 can be formed in a tube having an inner diameter of about 2 to 50 mm. As a result, the gas-liquid mixture can be discharged with a relatively thick channel cross-sectional area, and the clogging of the pipe as in the case where the channel 6 is configured by a narrow path can be prevented, and the gas-liquid mixture can be used. It can be made easier.

FIG. 6 is another example of a method for producing a gas-liquid mixture, and a schematic diagram illustrating another example of a gas-liquid mixture production apparatus is illustrated. This gas-liquid mixture manufacturing apparatus is configured as a gas-liquid mixing tank 13 in which the pressurizing unit 1 and the gas-liquid mixing unit 3 are combined, and a gas containing a fire extinguishing gas is contained in the gas-liquid mixing tank 13. The injected liquid is pressurized at a pressurization rate ΔP ₁ / t (ΔP ₁ : pressure increase amount, t: time) of 0.17 MPa / sec or more to make the liquid pressure 0.15 MPa or more. A gas-liquid mixed liquid having a strong structure is produced in a batch system, and after removing large bubbles from the gas-liquid mixed liquid by the defoaming section 4, the gas-liquid mixed liquid is sent to the decompression section 5 and the pressure is reduced. The pressure is reduced to atmospheric pressure at a pressure reduction rate ΔP ₂ / t (ΔP ₂ : pressure reduction amount, t: time) at a maximum pressure reduction rate of 2000 MPa / sec or less, and the gas-liquid mixture is discharged from the discharge part 7. The gas-liquid mixing tank 13 which is a closed system is sent out and pressurized in a batch manner, and is stirred by a stirring blade 14 or the like provided in the gas-liquid mixing tank 13 so that the liquid Lq and the gas are mixed. Are mixed under high pressure conditions. Thereby, the interface structure around the bubbles can be strengthened, and the gas can be stabilized as nano-sized bubbles. Then, by sending the generated gas-liquid mixed liquid to the defoaming section 4, the decompression section 5 and the discharge section 7 configured in the same manner as the apparatus of FIG. 2, the gas-liquid mixed liquid in which nano-sized bubbles are mixed is obtained. It can be obtained.

  The gas-liquid mixture thus obtained can be used as a fire extinguisher or a fire-extinguishing gas-containing combustible liquid.

  When using as a fire extinguisher, a fire extinguisher obtained as a gas-liquid mixed solution can be sealed in a container or tank to make a fire extinguisher or a fire extinguisher. Obtainable. In that case, it is preferable that it is an airtight container. By sealing, the fire extinguishing gas can be prevented from being released as a large bubble from the fire extinguishing agent, and the fire extinguishing performance can be maintained over a long period of time.

  Moreover, when using as a fire extinguishing gas containing combustible liquid, the fire extinguishing gas containing combustible liquid obtained as a gas-liquid mixed liquid can be sealed and stored in a tank or a container. If the liquid is a fuel, when using it as a fuel, the fire-extinguishing gas-containing fuel can be removed from the fuel by vibrating it or heating it to the extent that a fire does not occur. It can be used without degrading the characteristics.

  Here, in order to obtain a sherbet-like fire extinguisher, it can be obtained by cooling the gas-liquid mixture obtained as described above.

  FIG. 7 shows an example of a method for obtaining a sherbet-like fire extinguisher, and illustrates a part of the gas-liquid mixture manufacturing apparatus.

  The apparatus shown in FIG. 7A includes a cooling unit 15 connected to the tip of the discharge port 7 in addition to the configuration of the apparatus shown in FIG. The cooling unit 15 is formed of, for example, a container having an open upper surface, and is provided with a cooling heat exchanger 16 formed of a jacket through which a refrigerant passes.

  In this apparatus, when the gas-liquid mixed solution is supplied to the cooling unit 15, the gas-liquid mixed solution is cooled by the cooling heat exchanger 16 provided in the cooling unit 15, and the sherbet-like gas-liquid mixed solution is obtained. Is generated. Here, the fire-extinguishing gas is contained in the liquid in the form of nano-sized bubbles, and the fire-extinguishing gas is supplied to the cooling unit 15 in a state where it does not escape, so that the liquid is cooled. A sherbet-like fire extinguishing agent can be efficiently produced.

  The cooling temperature of the gas-liquid mixture in the cooling unit 15 is not particularly limited. For example, when cooled at a temperature of about −15 to 3 ° C., a sherbet-like fire extinguisher in which a fire-extinguishing gas is dispersed in water is obtained. It is something that can be done. In order to obtain a sherbet shape, it is preferable to cool with stirring.

  Further, in the apparatus of FIG. 7B, in addition to the configuration of the apparatus of FIG. 2 or 6, a cooling unit 15 is provided in the flow path 6 from the decompression unit 5 to the discharge port 7. The cooling unit 15 can be formed by, for example, wrapping and attaching a cooling heat exchanger 16 around the outer periphery of a tube forming the flow path 6.

  In this apparatus, the gas-liquid mixed liquid produced in the same manner as described above is continuously sent to the cooling unit 15 through the flow path 6 and is cooled when passing through the cooling unit 15 to be extinguished in a sherbet-like form. An agent is produced. Since the gas-liquid mixture is cooled as it passes through the cooling section 15 in this way, a sherbet-like fire extinguisher can be continuously produced, and the production efficiency of the fire extinguisher is increased. It is something that can be done. In this case, the fire extinguishing agent needs to be in a fluid state when passing through or after passing through the cooling section 15, so that it is desirable that the fire extinguisher be generated as a sherbet having fluidity. The fire extinguisher generated through the cooling unit 15 may be collected in a collection container, or the fire extinguisher may be directly injected into fire and used for fire extinguishing.

  In addition, in order to obtain a fire extinguisher containing a thickener, a fire extinguisher is obtained by adding a desired amount of the thickener to the gas-liquid mixture obtained as described above and dispersing and dissolving it. Can do. Moreover, you may manufacture a fire extinguisher by adding a thickener previously to a liquid and obtaining a gas-liquid liquid mixture using a viscous liquid. At that time, if a gas-liquid mixture is produced by heating a liquid and using a liquid whose viscosity is lowered when heated as a thickener, the viscosity of the liquid at the time of production is reduced and the production is facilitated. Become.

  FIG. 8 shows an example of a method for producing a fire extinguishing agent by dissolving a thickener in a liquid and then generating a gas-liquid mixture using the liquid. In this apparatus, a liquid storage tank 12 is provided as a stirring container 17. The stirring container 17 includes a stirring means 18 for stirring a liquid such as a stirring blade and a heating means 19 for heating the stirring container 17. Is provided. The thickener is dispersed and dissolved in the liquid in the stirring container 17, and a viscous liquid is prepared in the stirring container 17. At that time, the heating means 19 heats the liquid, so that the thickener is easily dissolved, and the viscosity of the liquid is lowered to facilitate delivery to the pressurizing unit 1. The liquid containing the thickener is sequentially sent to the pressurizing unit 1, the gas-liquid mixing unit 3, the defoaming unit 4, and the decompression unit 5 in the same manner as described above to extinguish the viscous gas-liquid mixed solution. It is obtained as an agent.

  Moreover, using the gas-liquid mixing tank 13 of the apparatus of FIG. 6 as the stirring container 17, the liquid and the thickener are stirred in the gas-liquid mixing tank 13 to prepare a viscous liquid, and then the same as above. Alternatively, a gas / liquid mixture may be prepared. At that time, the gas-liquid mixing tank 13 may be heated in order to dissolve the thickener or reduce the viscosity of the liquid.

  Hereinafter, the present invention will be described with reference to examples.

[Example 1]
Using the apparatus shown in FIG. 2, a gas-liquid mixture (extinguishing agent) was produced using pure water as the liquid and various fire extinguishing gases described later as the gas. If a flammable liquid is used as the liquid in the same manner, it is possible to obtain a fire extinguishing gas flammable liquid.

  As the manufacturing apparatus, a device in which the pressurizing unit 1 and the gas-liquid mixing unit 3 are combined with a pump 11 was used. As the pump 11, a pump 11 a as shown in FIG.

The ratio of gas to liquid (the amount of gas injected into the liquid) was set to 1: 1 as a volume ratio (volume ratio). Moreover, the rotation speed of the rotary body 21 of the pump 11 was set to 1700 rpm. Under this condition, gas is injected into water at atmospheric pressure (0.1 MPa) and then pressurized at a pressure rate ΔP ₁ /t=28.3 MPa / sec. The pressure of the liquid at the time of delivery became 0.6 MPa. Under such conditions, it is considered that the gas is injected into the liquid exceeding the saturated dissolution concentration, the hydrogen bond distance is shortened, and a strong bubble interface structure is formed. This condition (pressurizing condition) is considered to be the best condition at present.

  In addition, the flow path 6 on the upstream side of the decompression unit 5 has an inner diameter of 20 mm. As the decompression unit 5, as shown in FIG. 4 (a), one having an inner diameter that gradually decreases in three stages is used. Specifically, the inner diameter is 14 mm, 8 mm, 4 mm, and each length is about 3.3 mm (decompression). The total length of the part 5 was approximately 1 cm) and was composed of three flow path pipe parts. In addition, a hose having an inner diameter of 4 mm (outer diameter of 6 mm) is used as the flow path 6 and the extension flow path 10 on the downstream side of the decompression unit 5, and the combined length of the downstream flow path 6 and the extension flow path 10 is as follows. It was set to be 2 m. Under this condition, the decompression unit 5 decompresses the liquid mixed with gas at a maximum decompression speed of 60 MPa / sec and a time of 0.0025 seconds, and further, 1 MPa / sec in the downstream channel 6 and the extension channel 10. The liquid in which the gas was mixed was reduced in pressure for 0.5 seconds, and a gas-liquid mixed liquid reduced in pressure to atmospheric pressure (0.1 MPa) was obtained from the discharge part 7 which is the tip of the hose. Note that, under such conditions, a gas-liquid mixed liquid in which gas is injected into the liquid exceeding the saturated dissolution concentration and the hydrogen bond distance is shortened and the structure of the bubble interface is strengthened can be stably generated. It is considered a thing. This condition (decompression condition) is considered to be the best condition at the present time.

[Physical properties]
Next, the physical properties of the gas-liquid mixture (extinguishing agent) of Example 1 will be described.

[Hydrogen bond distance]
FIG. 9 shows an infrared absorption spectrum of a gas-liquid mixed solution (nitrogen mixed water) using nitrogen as a gas and pure water as a liquid and nitrogen saturated water in which nitrogen is dissolved in pure water at a saturated dissolution concentration. It is a graph which shows a difference. It is known that the infrared absorption band due to the OH contraction vibration of water usually has an absorption maximum in the vicinity of 3400 cm ⁻¹ , but as shown in the graph, the gas-liquid mixture has an absorption maximum of OH contraction vibration of 3200 cm ^−. It is shifted to around ¹ . When the absorption maximum is 3400 cm ⁻¹ , the hydrogen bond distance is 0.285 nm. On the other hand, when the absorption maximum is 3200 cm ⁻¹ , the hydrogen bond distance is known to be 0.277 nm, which is shorter than the normal hydrogen bond distance under normal temperature and pressure, and is structured ice or hide. It was concluded that the water was close to the rate.

[Gas volume]
The amount of gas present as bubbles in the gas-liquid mixture using pure water as the liquid and nitrogen, argon, or carbon dioxide as the gas was measured by the following method.
(1) Various gases were mixed with pure water having a conductivity of 0.1 μS / cm at 25 ° C. to obtain a gas-liquid mixture.
(2) In order to separate large bubbles having a diameter of 1 μm or more from water, the gas-liquid mixture was allowed to stand at 25 ° C. for 1 day. As for the standing time, from the Stokes' law, the bubble rising speed: V = d ² × g / (18 × γ)
(D: bubble diameter, g: gravitational acceleration, γ: kinematic viscosity coefficient)
From this equation, the rate of rise of bubbles of 1 μm is about 2.4 × 10 ⁻⁴ m / s. For example, if the water depth of the container at the time of standing is 50 mm, Bubbles can be removed.
(3) The mass of the gas-liquid mixture was measured with an analytical balance having a minimum measured value of 1 mg.
(4) A gas-liquid mixture and a stirrer of a stirrer are placed in a PE + nylon resin vinyl bag with low gas permeability and moisture permeability, and the vinyl bag is sealed with a sealer in a state where there is no air in the bag. .
(5) Immediately after sealing, the mass of the vinyl bag in which the gas-liquid mixture was sealed was measured with an analytical balance.
(6) The vinyl bag in which the gas / liquid mixture at 25 ° C. was sealed by a hot stirrer was heated to 45 ° C., and the gas / liquid mixture was stirred for about 5 hours. By this temperature rise and stirring, fine bubbles and gas dissolved at a saturated dissolution concentration of 45 ° C. or higher were separated from the gas-liquid mixture and collected on the top of the vinyl bag.
(7) The set temperature of the hot stirrer was set to 25 ° C. at room temperature of 25 ° C., and the mixture was stirred for several hours so as to become a liquid having a saturation solubility of 25 ° C.
(8) Using an analytical balance, the mass of the vinyl bag in which gas and liquid were enclosed was measured.
(9) The mass of the gas-liquid mixture and the amount of change in the mass of the liquid caused by the buoyancy caused by the gas separated from the gas-liquid mixture by heating and stirring were obtained from three mass measurements. The mass change amount is the same as the mass of air having the same volume as the gas volume separated from the gas-liquid mixture, and the volume and mass of the separated gas can be calculated from this value.

  FIG. 10 is a graph showing the gas volume measured in this way. The lower region of each bar graph is the amount of gas that was present as the measured bubble, and the upper region is the saturated amount of gas that follows Henry's law. As shown in the graph, the amount of gas contained in the gas-liquid mixture with respect to the saturated dissolution amount was 36 times for nitrogen, 16 times for argon, and 1.9 times for carbon dioxide. Thus, the fire extinguishing agent and fire extinguishing gas-containing flammable liquid obtained as a gas-liquid mixed liquid can hold the fire extinguishing gas in the liquid at a high concentration equal to or higher than the saturated dissolution concentration. A fire extinguisher containing a fire extinguishing gas or a fire extinguishing gas-containing combustible liquid can be used for fire extinguishing.

[Bubble size]
A gas-liquid mixture produced in the same manner as above was instantly frozen, cleaved with a cutter in a vacuum, and methane / ethylene flowed through the fractured surface to discharge, producing a hydrocarbon film (replica film) with transferred irregularities. . A conductive osmium thin film was applied to the replica film, dried sufficiently, and observed with a scanning electron microscope (SEM).

  FIG. 11 is an example of a photograph observed by SEM for a gas-liquid mixture of nitrogen and pure water. Similarly, by observing a photograph, it was confirmed that when nitrogen, argon, or carbon dioxide was used as the gas, the bubble size of the gas-liquid mixture was 100 nm in diameter distribution peak. The bubbles in the gas-liquid mixture of the above gas and pure water could not be accurately detected by a particle size distribution measuring apparatus such as a dynamic scattering method using a laser.

[Internal pressure of bubbles]
The pressure inside the bubbles was calculated from the total amount of gas in the gas-liquid mixture. Table 1 shows the total amount of gas and the internal pressure of bubbles calculated from the total amount of gas in a gas-liquid mixture of nitrogen or argon and 25 ° C. pure water.

The internal pressure of the gas in the bubbles is calculated by the following method.
The equation of state of gas is
PV / T = (const)
(P: internal pressure, V: volume, T: internal temperature)
When T is constant, PV = (const)
It is represented by

And the volume of bubbles in the gas-liquid mixture can be calculated from the density of the gas-liquid mixture,
The relationship of atmospheric pressure × total gas volume = bubble internal pressure × total gas volume in liquid is established, and the internal gas pressure in the bubbles is calculated by applying the above measured gas amount to this relational expression. The pressure value is as follows.

For example, if the gas is nitrogen,
Assuming that the volume of water in 1 liter of gas-liquid mixture is w1 liter and the volume of gas in water is w2 liter,
The following relational expression holds for the volume.

w1 + w2 = 1 liter (Formula A)

In addition, the following relational expression holds for the mass.

w1 × density of water + w2 ÷ 22.4 (liter) × 28 (molecular weight) = measured mass (Formula B)
Water density: 997.1g / L for pure water at normal temperature and pressure
22.4 liters: volume of 1 mol of gas Measured mass: 988.3 as shown in Table 1

Solving the above two equations (Equations A and B),
Since w2 = 8.84 × 10 ^ (-3) is calculated,

Internal pressure of gas = atmospheric pressure x total volume of gas ÷ total volume of gas in liquid
= 0.1 x (value in Table 1) / w2
= 0.1 × 0.56 ÷ (8.84 × 10 ^ (-3))
= 6.3 MPa
It becomes.

  In the above calculation, it was assumed that the internal temperature of the bubble was constant (normal temperature), but the actual internal temperature of the bubble is also expected to be higher than the atmospheric temperature (normal temperature). It can be predicted from the gas state equation that the pressure is higher than the above calculation result.

  By the way, in general, the internal pressure of bubbles is calculated as follows. The bubbles are pressurized by the interfacial tension between the gas-liquid interface, and this interfacial tension is derived by Young Laplace's equation (the following equation).

ΔP = 2σ / r
(ΔP: rising pressure, σ: surface tension, r: bubble radius)
According to this equation, for example, in the case of a bubble having a diameter of 100 nm, the bubble internal pressure is 3 MPa.

  On the other hand, the internal pressure in the gas-liquid mixed liquid is 6.3 MPa in the case of nitrogen, for example, as shown in Table 1. In this gas-liquid mixed liquid, bubbles having a diameter of 100 nm are dispersed as shown in the SEM photograph. Therefore, it was confirmed that the bubbles of the gas-liquid mixture had an internal pressure that was about twice or more the value calculated from the Young Laplace equation. Therefore, it was concluded that a stronger interface structure was formed at the bubble interface in the gas-liquid mixture.

FIG. 12 is a conceptual explanatory diagram illustrating a mechanism by which bubbles in the gas-liquid mixture are stabilized. As shown in the drawing, a protective film M having a boundary film structure (crystal structure) is formed at the interface between the bubble B and the liquid Lq by bonding of strong water molecules such as ice or hydrate whose hydrogen bond distance is shorter than usual. Therefore, it is considered that the mass transfer between the gas and liquid was prevented, and the bubbles became stable. The internal pressure of the bubbles (nanobubbles) in the gas-liquid mixture of nitrogen and argon is about twice or more than the pressure obtained from the Young Laplace equation. As described above, the hydrogen bond distance at the bubble interface is short and the internal pressure of the bubble is increased, so that a gas-liquid mixture (fire extinguisher or fire-extinguishing gas-containing combustible liquid) in which the bubbles of the fire-extinguishing gas exist stably is obtained. Is.

[Bubble distribution]
The amount (number) of bubbles in the gas-liquid mixture was calculated from Table 1.

When the gas is nitrogen, the total amount of bubbles returned to the atmosphere (0.1 MPa) is 0.56 L, and the internal pressure of the bubbles is 6.3 MPa. Therefore, the total volume V1 of bubbles in water is assumed to change isothermally, PV From = const
V1 = 0.56 × 0.1 ÷ 6.3
It becomes.

Since the bubbles are spheres with a radius r = 50 nm, the volume V2 per bubble is
V2 = 4/3 × π × r ^ 3
It becomes.

  From the above, the number of bubbles per liter of water n = V1 ÷ V2 = 1.7 × 10 ^ 16 is calculated.

  Similarly, the number of bubbles per liter of water is calculated as 1.7 × 10 ^ 16 when the gas is argon.

[Stability]
FIG. 13 shows the supersaturation ratio of the gas abundance ratio in the gas-liquid mixture with respect to the saturated dissolution concentration when the gas-liquid mixture produced by mixing carbon dioxide with pure water is sealed in a glass bottle and stored at a constant temperature. Is a graph to be displayed. From the graph, it can be seen that the supersaturation level is 6 even after 400 hours and has hardly changed. Therefore, it was confirmed that the bubbles in the gas-liquid mixed liquid exist stably.

[Example 2]
A sherbet-like fire extinguisher Using the apparatus shown in FIG. 2, a gas-liquid mixture was prepared using water as a liquid and carbon dioxide as a gas. Next, the gas-liquid mixture was cooled at −10 ° C. using the apparatus of FIG. By sufficiently stirring after sufficiently cooling, a sherbet-like fire extinguisher containing nanobubbles and having fluidity was produced.

[Example 3]
Thickener-containing fire extinguisher Using the apparatus shown in Fig. 2, a 1wt% sodium carboxymethylcellulose aqueous solution heated to 50 ° C as the liquid, carbon dioxide as the gas, and a viscous gas-liquid mixture (fire extinguishing) Agent).

[Example 4]
Self-extinguishing fuel Using the apparatus shown in FIG. 2, a gas-liquid mixture (extinguishing fuel) was produced using methanol as the liquid and carbon dioxide as the gas.

DESCRIPTION OF SYMBOLS A Extinguishing agent 1 Pressurization part 2 Gas supply part 3 Gas-liquid mixing part 4 Defoaming part 5 Depressurization part 6 Flow path 7 Discharge part 8 Gas removal part 11 Pump 21 Rotating body

Claims (9)

  A fire extinguishing agent, wherein a gas containing a fire extinguishing gas is mixed with a liquid in the form of nano-sized bubbles.   The liquid is a liquid composed of molecules that form hydrogen bonds, and the distance between hydrogen bonds of molecules present at the interface with the liquid bubbles is shorter than the distance between hydrogen bonds when the liquid is at normal temperature and pressure. The fire extinguisher of Claim 1 characterized by the above-mentioned.   The extinguishing agent according to claim 1 or 2, wherein the weight per unit volume of the extinguishing gas is equal to or more than the weight per unit volume of nitrogen.   The extinguishing agent according to any one of claims 1 to 3, wherein the liquid is water.   The extinguishing agent according to any one of claims 1 to 4, wherein the concentration of the extinguishing gas contained in the liquid is equal to or higher than a saturated dissolution concentration of the extinguishing gas with respect to the liquid.   The fire extinguishing agent according to any one of claims 1 to 5, wherein the pressure of the gas forming the bubbles is 0.12 MPa or more.   The extinguishing agent according to any one of claims 1 to 6, wherein the extinguishing agent has a sherbet shape.   The fire extinguisher according to any one of claims 1 to 6, wherein a thickener is contained in the liquid.   A fire-extinguishing gas-containing combustible liquid, wherein a gas containing a fire-extinguishing gas is mixed with a combustible liquid in the form of nano-sized bubbles.