WO2014203935A1 - 消火剤および消火方法 - Google Patents
消火剤および消火方法 Download PDFInfo
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- WO2014203935A1 WO2014203935A1 PCT/JP2014/066168 JP2014066168W WO2014203935A1 WO 2014203935 A1 WO2014203935 A1 WO 2014203935A1 JP 2014066168 W JP2014066168 W JP 2014066168W WO 2014203935 A1 WO2014203935 A1 WO 2014203935A1
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- Prior art keywords
- fire extinguishing
- extinguishing agent
- metallocene
- fire
- ferrocene
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- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D1/00—Fire-extinguishing compositions; Use of chemical substances in extinguishing fires
- A62D1/0028—Liquid extinguishing substances
- A62D1/005—Dispersions; Emulsions
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- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D1/00—Fire-extinguishing compositions; Use of chemical substances in extinguishing fires
- A62D1/0007—Solid extinguishing substances
- A62D1/0014—Powders; Granules
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- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D1/00—Fire-extinguishing compositions; Use of chemical substances in extinguishing fires
- A62D1/0028—Liquid extinguishing substances
- A62D1/0035—Aqueous solutions
- A62D1/0042—"Wet" water, i.e. containing surfactant
Definitions
- the present invention relates to a novel fire extinguishing agent and a fire extinguishing method.
- Fire extinguishing is usually classified into four types: suppression, cooling, suffocation, and removal, and extinguishing agents are developed according to their characteristics. Suppressing fire extinguishing, in particular, captures radicals generated in the combustion system and stops the chain reaction of combustion, and has the advantage of using a small amount of extinguishing agent compared to other types of fire extinguishing. So far, fire extinguishing agents containing ammonium phosphate and halon have been developed.
- Patent Document 1 discloses a fire extinguisher composition containing 25% by mass or more of ferrocene or a derivative thereof.
- Patent Document 2 discloses a microcapsule containing a fire extinguisher composition containing an iron-containing compound such as ferrocene and an inert gas source. As described above, utilization of metallocene as a fire extinguishing agent is expected.
- the present invention provides a fire extinguishing agent comprising a metallocene and a dispersion medium, wherein the metallocene is dispersed in the dispersion medium.
- the metallocene is preferably ferrocene.
- the content of the metallocene is preferably 70 ppm by mass to 20% by mass.
- the said dispersion medium is at least 1 sort (s) chosen from the group which consists of a nonflammable liquid and a nonflammable powder.
- the dispersion medium is a nonflammable liquid and the content of the metallocene is 70 to 160 ppm by mass.
- the said dispersion medium is water and also contains a dispersing agent.
- the said dispersing agent is a nonionic surfactant.
- the concentration of the surfactant is preferably 1 to 7 times the critical micelle concentration.
- the time after the production of the fire extinguisher is plotted on the horizontal axis, and the dispersion stability of the metallocene in the fire extinguisher is expressed as the slope when the reciprocal of the turbidity of the fire extinguisher is plotted on the vertical axis.
- the degree is preferably 1 to 20.
- the dispersion medium is an incombustible powder and the content of the metallocene is 550 ppm by mass to 20% by mass.
- the dispersion medium is ammonium sulfate, magnesium sulfate, potassium sulfate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, potassium phosphate, sodium chloride, potassium chloride, magnesium oxide, silicon dioxide, and It is preferably at least one selected from the group consisting of alumina.
- this invention provides the fire extinguishing method characterized by including the process of supplying a fire extinguisher to a combustion thing in the first term.
- FIG. 3 is a particle size distribution diagram of ground ferrocene (1) used in the production of fire extinguishing agents in Examples 1 to 4.
- 1 is a schematic view showing an apparatus for evaluating the fire extinguishing ability of a fire extinguishing agent used in Examples 1 to 4 and Comparative Example 1.
- FIG. 6 is a graph showing the evaluation results of fire extinguishing ability of fire extinguishing agents in Examples 1 to 4 and Comparative Example 1.
- FIG. 4 is a particle size distribution diagram of ground ferrocene (2) used in the production of fire extinguishing agents in Examples 5 to 12.
- FIG. 3 is a particle size distribution diagram of ground ferrocene (3) used in the production of fire extinguishing agents in Examples 5 to 12.
- FIG. 4 is a particle size distribution diagram of ground ferrocene (4) used in the production of fire extinguishing agents in Examples 5 to 12.
- 6 is a graph showing evaluation results of fire extinguishing ability of fire extinguishing agents in Examples 5 to 8 and Comparative Example 2.
- the fire extinguishing agent according to the present invention contains a metallocene and a dispersion medium , and exhibits stable fire extinguishing ability when the metallocene is dispersed in the dispersion medium.
- the metallocene contained in the fire extinguishing agent has a sandwich structure in which a metal atom is sandwiched between two cyclopentadienyl rings (C 5 H 5 ⁇ ), and may be a known one. Examples thereof include iron, nickel, cobalt, chromium, manganese, vanadium, ruthenium, osmium, and the like, and other ligands may be further coordinated in addition to the cyclopentadienyl ring. Examples of other ligands include acetylacetones, pentamethylcyclopentadiene, benzenes and the like.
- biscyclopentadienyl metal compounds include [Fe (C 5 H 5 ) 2 ] (ferrocene), [Ni (C 5 H 5 ) 2 ] (nickelocene), [Co (C 5 H 5) 2] (cobaltocene), [Cr (C 5 H 5) 2] ( chromocene), [Mn (C 5 H 5) 2] ( Manganosen), [V (C 5 H 5) 2] ( vanadocene ), [Ru (C 5 H 5 ) 2 ] (ruthenocene), [Os (C 5 H 5 ) 2 ] (osmocene), etc.
- ferrocene is a low toxic and inexpensive point. Is preferred.
- the metallocene preferably has a median diameter of 5 to 80 ⁇ m, more preferably 10 to 70 ⁇ m. Since the metallocene is in such a fine particle form, the dispersibility in water becomes higher.
- the “median diameter” means a particle diameter at 50% accumulation when a volume-based cumulative particle size distribution curve is created from a particle size distribution measured using a laser diffraction scattering particle size distribution measuring device. Means (D 50 ). Further, the metallocene preferably has an abundance ratio of particles of 200 ⁇ m or less of 90% by volume or more.
- the metallocene contained in the fire extinguishing agent may be only one kind, or two or more kinds, and when there are two or more kinds, the combination and ratio can be arbitrarily selected according to the purpose.
- the proportion of ferrocene in the total mass of the metallocene is preferably 1% by mass or more, more preferably 10% by mass or more, and more preferably 50% by mass or more. More preferably.
- the metallocene content in the fire extinguishing agent is preferably 70 mass ppm to 20 mass%, more preferably 80 mass ppm to 10 mass%, and particularly preferably 100 mass ppm to 1 mass%. .
- the fire extinguishing agent becomes more excellent in fire extinguishing ability.
- Metallocene like conventional ammonium dihydrogen phosphate (NH 4 H 2 PO 4 ), captures radicals generated in the combustion system and stops the chain reaction of combustion, thereby suppressing the combustion effect (extinguishing ability) ). And the content of metallocene is not less than the lower limit, so that the metallocene combustion suppression effect is more remarkably exhibited.
- metallocene is itself a combustible compound. Therefore, when the metallocene content is not more than the above upper limit value, the combustion of the metallocene itself is suppressed, and the combustion suppression effect is more remarkably exhibited. Thus, the fire extinguisher has an excellent fire extinguishing ability in a range where the content of metallocene is extremely small.
- the dispersion medium used in the present invention is preferably at least one selected from the group consisting of a nonflammable liquid and a nonflammable powder.
- nonflammable means that it does not react with oxygen, and is not particularly limited as long as it is a liquid or powder that does not react with oxygen.
- the dispersion medium is preferably low corrosive and low toxic.
- the non-flammable liquid used as the dispersion medium is water.
- the water used in the present invention is not particularly limited as long as it does not include the kind and amount of impurities that impede the function as a fire extinguishing agent. From the viewpoint of cost and availability, it is preferable to use general tap water.
- the content of the metallocene is preferably 70 to 160 ppm by mass, more preferably 80 to 140 ppm by mass, and 90 to 130 ppm by mass. It is particularly preferred.
- the fire extinguisher of the present invention preferably further contains a dispersant.
- a dispersing agent will not be specifically limited if it has the effect
- well-known various surfactant can be used as a dispersing agent.
- the surfactant may be any of an anionic surfactant, a cationic surfactant, and a nonionic surfactant.
- anionic surfactant examples include sulfates such as sodium lauryl sulfate and sulfonates such as sodium alkylbenzene sulfonate.
- cationic surfactant examples include quaternary ammonium salts such as dodecyltrimethylammonium chloride.
- nonionic surfactants include glycerin fatty acid esters, sucrose fatty acid esters, sorbitan fatty acid esters, and acetylene alcohols.
- acetylene alcohols are those having a triple bond (C ⁇ C) between carbon atoms and at least one hydroxyl group.
- the surfactant is preferably a nonionic surfactant, more preferably an acetylene alcohol, from the viewpoint that the fire extinguishing ability of the fire extinguisher becomes higher, and the following general formula (A) Particularly preferred are acetylene alcohols (hereinafter sometimes abbreviated as “surfactant (A)”).
- surfactant (A) those in which at least one of m and n is not 0 are ethylene oxide adducts to the hydroxyl groups of different types of surfactants (A) in which m and n are both 0.
- R 1 and R 2 each independently represent a hydrogen atom or a lower alkyl group, and m and n are each independently an integer of 0 or more.
- R 1 and R 2 are preferably each independently an alkyl group having 1 to 6 carbon atoms, and n and m are each independently 0 or an integer of 1 to 30. preferable. Further, m + n is preferably 1 to 50, and more preferably 1 to 30. The case where m + n is 10 is particularly preferable because the dispersibility of the metallocene in the fire extinguisher is particularly excellent, and the fire extinguishing agent expresses more excellent fire extinguishing ability.
- surfactant (1) For surfactant (A) where m + n is 10, Surfynol 465 (sold by Nissin Chemical Industry Co., Ltd., hereinafter abbreviated as “surfactant (1)”) is commercially available. Further, among the surfactants (A), those in which m and n are both 0 are commercially available as Surfynol 104 (sold by Nissin Chemical Industry Co., Ltd.).
- surfactant (2) As used by Nissin Chemical Industry Co., Ltd., Olphine E1020 (sold by Nissin Chemical Industry Co., Ltd., hereinafter abbreviated as “surfactant (3)”), Olphine PD201 (sold by Nissin Chemical Industry Co., Ltd., hereinafter “ (Surfactant (4) ”may be abbreviated). All of these are nonionic surfactants per se or contain nonionic surfactants.
- the dispersant contained in the fire extinguishing agent may be only one type, or two or more types, and when there are two or more types, the combination and ratio can be arbitrarily selected according to the purpose.
- the content of the dispersant in the fire extinguishing agent is preferably 0.05 to 2.0% by mass, and more preferably 0.1 to 1.5% by mass. When the content of the dispersant is in such a range, the dispersibility of the metallocene in the fire extinguisher is further improved.
- the concentration of the surfactant in the fire extinguishing agent is preferably 1 to 7 times the critical micelle concentration (cmc), and is 1.5 to 7 times. More preferred is 2 to 7 times.
- the critical micelle concentration can be measured using a D bracket surface tension meter (manufactured by Ito Seisakusho).
- the dispersibility of the metallocene in the extinguishing agent is further improved by the concentration of the surfactant being not less than the above lower limit.
- the concentration of the surfactant is 7 times or less of the critical micelle concentration, the extinguishing ability of the extinguishing agent is further enhanced while suppressing excessive use of the surfactant.
- Metallocene is a compound with high fat solubility, and when used alone, its solubility in water is extremely low. Therefore, in a fire extinguisher using water as a medium, problems such as sedimentation and agglomeration are unavoidable, and are inherently unsuitable as components, and as described above, conventionally used as a vapor or an organic solvent solution, The fire fighting ability has been verified.
- the metallocene is preferably in the form of fine particles, and by further using a dispersant, it is possible to disperse in water. For example, by adjusting conditions such as the type and amount of the dispersant, It is also possible to further improve the dispersibility. As a result, stable quality can be realized as a fire extinguisher, in which sedimentation or aggregation of metallocene is suppressed slightly or completely.
- the extinguishing agent is expressed as a slope when plotting the time after manufacturing the extinguishing agent on the horizontal axis and plotting the reciprocal of the turbidity of the extinguishing agent on the vertical axis.
- the dispersion stability coefficient of the metallocene is preferably from 0 to 20, more preferably from 0 to 10, and even more preferably from 0 to 1.
- the dispersion stability of the metallocene is plotted by plotting the time (minutes) after the production of the fire extinguishing agent on the horizontal axis (x axis) and the reciprocal of turbidity (NTU ⁇ 1 ) on the vertical axis (y axis). Is the slope of the linear approximation. Since the reciprocal of the turbidity corresponds to the transparency, the dispersion stability coefficient can be rephrased as the amount of change of the transparency with time. Therefore, the smaller this value is, the higher the stability of the dispersion system is, and the less the aggregation occurs.
- the content of the metallocene is preferably 550 mass ppm to 20 mass%, more preferably 800 mass ppm to 10 mass%, It is particularly preferably 1,000 ppm to 1% by mass.
- the particle size of the noncombustible powder is not particularly limited as long as the metallocene can be uniformly dispersed. For example, a metallocene having an average particle size in the above-described range can be used.
- the fire extinguisher may contain other components such as a dye, a pigment, and a pH adjuster, as long as the effects of the present invention are not impaired.
- the other components contained in the fire extinguishing agent may be only one type, or two or more types, and in the case of two or more types, the combination and ratio can be arbitrarily selected according to the purpose.
- the content of the other components in the fire extinguishing agent is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 3% by mass or less.
- the fire extinguishing agent can be obtained by mixing metallocene, a dispersion medium, a dispersing agent, and other components as necessary, and sufficiently dispersing the metallocene.
- the method for dispersing the metallocene at the time of blending is not particularly limited, and may be appropriately selected from known methods.
- a method of irradiating the mixture containing the respective components such as metallocene with ultrasonic waves to disperse is preferable from the viewpoint of higher dispersion effect.
- the frequency is preferably 10 to 100 kHz.
- the dispersion temperature of the metallocene at the time of blending when using a nonflammable liquid as the dispersion medium is not particularly limited as long as the metallocene is sufficiently dispersed and each blending component does not deteriorate, but it is 20 ° C. because the dispersion effect of the metallocene is higher.
- the above is preferable.
- the higher the dispersion temperature, the higher the dispersion effect of the metallocene, and the dispersion temperature is more preferably 25 ° C. or more, and 35 ° C. or more. More preferably, it is particularly preferably 45 ° C. or higher.
- the dispersion temperature is preferably 70 ° C. or lower, more preferably 60 ° C. or lower, from the viewpoint that the deterioration suppressing effect of each blending component is higher.
- the dispersion time of the metallocene at the time of blending when a non-flammable liquid is used as the dispersion medium is not particularly limited as long as each compounding component does not deteriorate, and may be performed until the metallocene is sufficiently dispersed, for example, 10 to 60 minutes. be able to.
- the mixing method in the case of using incombustible powder as the dispersion medium is not particularly limited as long as the metallocene can be uniformly dispersed, but for example, a mill method such as a ball mill and various stirring methods can be applied.
- the dispersion medium used in the present invention may be a mixture of the above-mentioned non-flammable liquid and non-flammable powder.
- the mixing ratio in this case may be appropriately adjusted according to the method of using the extinguishing agent, but the mixture in this case may be a solution or a slurry.
- the fire extinguishing agent is preferably stored and used after being filled in a container similar to a known fire extinguishing agent such as a metal.
- the fire extinguisher can stably maintain a state in which the metallocene is sufficiently dispersed after production, but if necessary, a normal mixing operation is performed before use, and the fire extinguishing ability is more stably expressed. Yes, the dispersion operation may be performed again before use.
- the present invention also provides a fire extinguishing method characterized by including a step of supplying the fire extinguishing agent to a combustion product.
- the fire extinguisher of the present invention can be in various forms such as a slurry form and a powder form as well as a solution form such as an aqueous solution.
- the fire can be extinguished.
- the fire extinguisher using the fire extinguisher has a container filled with the fire extinguisher and a discharge means such as an injection nozzle for discharging the fire extinguisher provided in association with the container.
- the said extinguishing agent expresses high fire extinguishing capability by making it contact the combustion thing of a fire extinguishing object like a well-known extinguishing agent.
- the extinguishing agent may be sprayed as it is, or the extinguishing agent may be sprayed in a mist form, and may be appropriately adjusted according to the form of combustion.
- the extinguishing agent may be contacted by any method, but in the case of an oil fire and an electric fire, it is preferable to spray the extinguishing agent in the form of a mist.
- a method of discharging the fire extinguisher of the present invention to a fire site can be mentioned.
- a method of discharging the fire extinguisher of the present invention to a fire site can be mentioned.
- the method of spraying by human power using the spray from the sky, the water discharge from a fire engine, a bucket, etc. can be used.
- the method of extinguishing with an oil fire extinguisher and an aerosol-type simple fire extinguishing tool is mentioned to the oil fire represented by tempura oil.
- Example 1 ⁇ Manufacture of fire extinguishing agent> (pulverization of ferrocene)
- ferrocene Commercially available ferrocene was pulverized in an agate mortar, passed through a sieve with an opening of 100 ⁇ m, and further passed through a sieve with an opening of 50 ⁇ m to select what remained on the sieve (hereinafter abbreviated as “ground ferrocene (1)”).
- the ground ferrocene (1) was imaged using an optical microscope (“DMI-300B” manufactured by Leica), and the area of the ground ferrocene (1) was measured using image analysis software (“ImageJ ver. 1.45”).
- the fire extinguishing ability of the obtained fire extinguishing agent was evaluated using the evaluation apparatus shown in FIG.
- the evaluation apparatus 1 shown here includes a fire extinguishing agent holding unit 11 that holds an extinguishing agent to be evaluated, a nozzle 14 that sprays the extinguishing agent, a pipe 13 that connects the extinguishing agent holding unit 11 and the nozzle 14, and a pipe 13.
- a pump 12 for transferring the fire extinguishing agent from the fire extinguishing agent holding unit 11 to the nozzle 14 and a combustion product holding unit 15 for holding the combustion product sprayed with the fire extinguishing agent are roughly configured.
- the nozzle 14 can spray the liquid with a divergence angle ⁇ of 60 ° at the maximum.
- maintenance part 15 is a container-shaped thing with the internal diameter D of 83 mm.
- N-heptane (80 mL) was held as a liquid combustible material in the combustion material holding unit 15 of the evaluation apparatus 1 and adjusted so that the distance H between the liquid level at the top and the tip of the nozzle 14 was 50 cm. . Then, n-heptane was ignited and allowed to stand for 20 seconds to stabilize the flame, and the fire extinguisher obtained above was sprayed from the nozzle 14 at a flow rate of about 240 mL / min. The state of n-heptane was visually observed until 45 seconds after the start of spraying of the fire extinguishing agent.
- Example 2 As shown in Table 1, a fire extinguisher was produced in the same manner as in Example 1 except that the concentration of ground ferrocene (1) was 125 ppm instead of 100 ppm, and the fire extinguishing ability was evaluated. The results are shown in Table 1 and FIG.
- Example 3 As shown in Table 1, a fire extinguisher was produced in the same manner as in Example 1 except that the concentration of ground ferrocene (1) was changed to 150 ppm instead of 100 ppm, and the fire extinguishing ability was evaluated. The results are shown in Table 1 and FIG.
- Example 4 As shown in Table 1, a fire extinguisher was produced in the same manner as in Example 1 except that the concentration of ground ferrocene (1) was changed to 75 ppm instead of 100 ppm, and the fire extinguishing ability was evaluated. The results are shown in Table 1 and FIG.
- Example 1 As shown in Table 1, a fire extinguisher was produced by the same method as in Example 1 except that the pulverized ferrocene (1) was not used, and the fire extinguishing ability was evaluated. The results are shown in Table 1 and FIG.
- Example 5 ⁇ Manufacture of fire extinguishing agent> (pulverization of ferrocene) Using a planetary ball mill, commercially available ferrocene was wet crushed for 45 minutes at 400 rpm to obtain crushed ferrocene (hereinafter abbreviated as “crushed ferrocene (2)”). Using a laser diffraction particle size distribution analyzer (“SALD-7000” manufactured by Shimadzu Corporation), the particle size distribution of the ground ferrocene (2) was measured, and a particle size distribution diagram was prepared. The particle size distribution chart at this time is shown in FIG. From the results of FIG. 4, it was confirmed that this pulverized ferrocene (2) was bimodal having a small peak in the vicinity of the particle size of 0.2 ⁇ m in addition to the main peak, and the median diameter was 10.4 ⁇ m.
- SALD-7000 laser diffraction particle size distribution analyzer
- the pulverized ferrocene (3) is abbreviated in the same manner as in the case of the above pulverized ferrocene (2).
- the particle size distribution was measured to create a particle size distribution diagram.
- the particle size distribution chart at this time is shown in FIG. From the results of FIG. 5, it was confirmed that this pulverized ferrocene (3) has a sharp particle size distribution and a median diameter of 11.4 ⁇ m.
- the amount of each of the pulverized ferrocenes (2) to (4) added at this time was adjusted so that the concentration in the dispersion was 100 ppm.
- the addition amount of surfactant (1) was adjusted so that the density
- the critical micelle concentration of the surfactant (1) was previously measured using a D bracket surface tension meter (manufactured by Ito Seisakusho).
- the fire extinguishing ability of the obtained fire extinguishing agent was evaluated in the same manner as in Example 1 using the evaluation apparatus shown in FIG. However, as the evaluation apparatus 1, a combustion substance holding part 15 having an inner diameter D of 82 mm is used, and the distance H between the upper liquid level of n-heptane held here and the tip part of the nozzle 14 is 60 cm. It adjusted so that it might become. Then, n-heptane was ignited and allowed to stand for 10 seconds to stabilize the flame, and the fire extinguisher obtained above was sprayed from the nozzle 14 at a flow rate of about 250 mL / min.
- Example 6 As shown in Table 2, Example 5 was used except that surfactant (2) ("Surfinol 485" manufactured by Nissin Chemical Industry Co., Ltd.) was used instead of surfactant (1) as a dispersant. A fire extinguisher was manufactured in the same manner and its fire fighting ability was evaluated. In addition, the addition amount of surfactant (2) was adjusted so that the density
- Example 7 As shown in Table 2, it is the same as Example 5 except that surfactant (3) (“Olfin E1020” manufactured by Nissin Chemical Industry Co., Ltd.) was used as the dispersant instead of surfactant (1).
- the fire extinguishing agent was manufactured by the method, and the fire extinguishing ability was evaluated.
- the addition amount of surfactant (3) was adjusted so that the density
- Example 8 As shown in Table 2, in place of the surfactant (1) as the dispersant, the surfactant (4) (“Olfin PD201” manufactured by Nissin Chemical Industry Co., Ltd.) was used, except that the same as in Example 5. The fire extinguishing agent was manufactured by the method, and the fire extinguishing ability was evaluated. In addition, the addition amount of surfactant (4) was adjusted so that the density
- Example 5 there was almost no difference in the fire extinguishing time in all the fire extinguishing operations when any of the pulverized ferrocenes (2) to (4) was used (the variation was small).
- the shortest fire extinguishing time was 0.8 seconds
- the average fire extinguishing time was 1.2 seconds
- the standard deviation (SD) was 0.4.
- the average fire extinguishing time was 1.2 seconds and the standard deviation (SD) was 0.4.
- Example 9 ⁇ Manufacture of fire extinguishing agent and evaluation of dispersibility> [Example 9] As shown in Table 3, in a 100 mL Erlenmeyer flask, ground ferrocene (2), ground ferrocene (3) or ground ferrocene (4), water (100 mL), surfactant (1) as a dispersant, surfactant After adding the agent (2), the surfactant (3) or the surfactant (4) and setting the temperature to 30 ° C., 40 ° C. or 50 ° C., further irradiating with ultrasonic waves (40 kHz) for 20 minutes, A fire extinguisher was obtained.
- Table 3 As shown in Table 3, in a 100 mL Erlenmeyer flask, ground ferrocene (2), ground ferrocene (3) or ground ferrocene (4), water (100 mL), surfactant (1) as a dispersant, surfactant After adding the agent (2), the surfactant (3) or the surfact
- the added amount of ground ferrocene (2) to (4) was adjusted so that the concentration in the dispersion was 20 ppm. Further, the addition amount of the surfactants (1) to (4) was adjusted so that the concentration in the dispersion was 1 time, 2 times or 5 times the critical micelle concentration (cmc). The critical micelle concentration of the surfactants (1) to (4) was previously measured using a Dvol surface tension meter. Subsequently, the fire extinguisher immediately after production was allowed to stand at room temperature for 20 minutes, and then the dispersibility of ferrocene (ground ferrocene (2) to (4)) was visually evaluated according to the following criteria. The results are shown in Table 3.
- Example 10 Except for the conditions shown in Table 4, a fire extinguisher was produced in the same manner as in Example 9, and the dispersibility of ferrocene was evaluated. The results are shown in Table 4.
- Example 11 Except for the conditions shown in Table 5, a fire extinguisher was produced in the same manner as in Example 9, and the dispersibility of ferrocene was evaluated. The results are shown in Table 5.
- Example 12 Except for the points shown in Table 6, a fire extinguisher was produced in the same manner as in Example 9, and the dispersibility of ferrocene was evaluated. The results are shown in Table 6.
- Example 13 ⁇ Manufacture of fire extinguishing agent> (pulverization of ferrocene)
- ferrocene Commercially available ferrocene was pulverized in an agate mortar, passed through a sieve with an opening of 250 ⁇ m, further passed through a sieve with an opening of 180 ⁇ m, and the one remaining on the sieve (hereinafter abbreviated as “crushed ferrocene (5)”) was selected. .
- the median diameter of the ground ferrocene (5) measured by the same method as in Example 1 was 30.9 ⁇ m.
- Extinguishing agents with different ferrocene concentrations shown in Table 7 were prepared by uniformly mixing the pulverized ferrocene (5), ammonium sulfate (median diameter: 22.2 ⁇ m) with a ball mill.
- a fire extinguishing test was conducted using the following model that complies with the ministerial ordinance (September 17, 1966, Ministry of Autonomy Ordinance No. 27) that determines the technical standards for fire extinguishers.
- Flame model B-1 Fire pan 0.2m 2
- Fuel n-heptane fire model A-0.5 36 cedars
- the distance between the model during combustion and the tip of the nozzle 14 of the fire extinguisher was set to 1 to 2 m, and a fire extinguisher was sprayed toward the model to evaluate whether fire extinguishing was possible. When the fire could be extinguished within 10 seconds and it did not reignite, it was determined that the digestion was complete. Table 7 shows the results when the fire was extinguished and the case where the fire could not be extinguished.
- the present invention can be used as a fire extinguisher.
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Abstract
Description
特許文献1には、フェロセンやその誘導体を25質量%以上含有する消火剤組成物が開示されている。また、特許文献2には、フェロセンなどの鉄含有化合物と不活性ガス源とを含む消火剤組成物が収容されているマイクロカプセルが開示されている。
以上のように、メタロセンの消火剤としての利用が期待されている。
本発明は上記事情に鑑みてなされたものであり、メタロセンを用いた、消火能力に優れる新規の消火剤を提供することを課題とする。
本発明は、メタロセン及び分散媒を含有し、前記メタロセンが前記分散媒中に分散していることを特徴とする消火剤を提供する。
本発明の消火剤においては、前記メタロセンがフェロセンであることが好ましい。
本発明の消火剤においては、前記メタロセンの含有量が70質量ppm~20質量%であることであることが好ましい。
本発明の消火剤においては、前記分散媒が、不燃性の液体及び不燃性の粉体からなる群より選ばれる少なくとも1種であることが好ましい。
本発明の消火剤においては、前記分散媒が、不燃性の液体であって、前記メタロセンの含有量が、70~160質量ppmであることが好ましい。
本発明の消火剤においては、前記分散媒が水であり、さらに分散剤を含むことが好ましい。
本発明の消火剤においては、前記分散剤がノニオン系界面活性剤であることが好ましい。
本発明の消火剤においては、前記界面活性剤の濃度が臨界ミセル濃度の1~7倍であることが好ましい。
本発明の消火剤においては、横軸に消火剤製造後の時間をプロットし、縦軸に消火剤の濁度の逆数をプロットした際の傾きとして表わされる、前記消火剤中におけるメタロセンの分散安定度が1~20であることが好ましい。
本発明の消火剤においては、前記分散媒が不燃性の粉体であって、前記メタロセンの含有量が、550質量ppm~20質量%であることが好ましい。
本発明の消火剤においては、前記分散媒が、硫酸アンモニウム、硫酸マグネシウム、硫酸カリウム、リン酸二水素アンモニウム、リン酸水素二アンモニウム、リン酸カリウム、塩化ナトリウム、塩化カリウム、酸化マグネシウム、二酸化ケイ素、及びアルミナからなる群より選ばれる少なくとも1種であることが好ましい。
また、本発明は、前期消火剤を燃焼物に供給する工程を含むことを特徴とする、消火方法を提供する。
このようなメタロセンのうち、ビスシクロペンタジエニル金属化合物としては、[Fe(C5H5)2](フェロセン)、[Ni(C5H5)2](ニッケロセン)、[Co(C5H5)2](コバルトセン)、[Cr(C5H5)2](クロモセン)、[Mn(C5H5)2](マンガノセン)、[V(C5H5)2](バナドセン)、[Ru(C5H5)2](ルテノセン)、[Os(C5H5)2](オスモセン)等が例示でき、これらの中でも、低毒性でかつ安価である点などから、フェロセンが好ましい。
また、メタロセンは、200μm 以下の粒子の存在比率が90体積%以上であることが好ましい。
前記消火剤はこのように、メタロセンの含有量が極めて少ない範囲において、優れた消火能力を有する。
前記界面活性剤は、アニオン界面活性剤、カチオン界面活性剤及びノニオン界面活性剤のいずれでもよい。
カチオン界面活性剤としては、塩化ドデシルトリメチルアンモニウム等の第4級アンモニウム塩が例示できる。
ノニオン界面活性剤としては、グリセリン脂肪酸エステル、ショ糖脂肪酸エステル、ソルビタン脂肪酸エステル、アセチレンアルコール類が例示できる。ここで、「アセチレンアルコール類」とは、炭素原子間の三重結合(C≡C)と少なくとも1つの水酸基とを有するものである。
また、界面活性剤(A)のうち、m及びnが共に0であるものも、市販品としてサーフィノール104(日信化学工業社販売)が入手可能である。
消火剤が含有する前記その他の成分は、1種のみでもよいし、2種以上でもよく、2種以上である場合、その組み合わせ及び比率は、目的に応じて任意に選択できる。
消火剤における前記その他の成分の含有量は、10質量%以下であることが好ましく、5質量%以下であることがより好ましく、3質量%以下であることが特に好ましい。
配合時のメタロセンの分散方法は特に限定されず、公知の方法から適宜選択すればよい。例えば、分散媒として水等の不燃性液体を用いる場合、分散効果がより高い点から、メタロセン等の前記各成分を含む混合物に対して、超音波を照射して分散させる方法が好ましく、このときの周波数は、10~100kHzであることが好ましい。
また、前記消火剤は、製造後、メタロセンが十分に分散された状態を安定して維持できるが、必要に応じて使用前に通常の混合操作を行うことで、より安定して消火能力を発現でき、使用前に再度分散操作を行ってもよい。
前記消火剤は、公知の消火剤と同様に、消火対象の燃焼物に接触させることで、高い消火能力を発現する。消火剤を燃焼物に接触させるときには、例えば、消火剤をそのまま散布してもよいし、消火剤を霧状にして噴霧してもよく、燃焼の形態に応じて適宜調節すればよい。例えば、普通火災の場合には、消火剤を如何なる方法で接触させてもよいが、油火災及び電気火災の場合には、消火剤を霧状にして噴霧することが好ましい。
また、天ぷら油に代表される油火災には、粉末消火器やエアゾール式簡易消火用具により消火する方法が挙げられる。
市販品のフェロセンをメノウ乳鉢で粉砕し、目開き100μmのふるいにかけ、さらに目開き50μmのふるいにかけて、このふるい上に残ったもの(以下、「粉砕フェロセン(1)」と略記する)を選別した。光学顕微鏡(Leica社製「DMI-300B」)を用いて、この粉砕フェロセン(1)を撮像し、画像解析ソフト(「ImageJ ver. 1.45」)を用いて粉砕フェロセン(1)の面積を測定して、相当する粒径を算出し、粒度分布を求め、粒度分布図を作成した。このときの粒度分布図を図1に示す。
図1の結果から、粉砕フェロセン(1)のメジアン径は、65μmであることが確認された。
100mLのメスフラスコに、粉砕フェロセン(1)と、水(100mL)と、分散剤として界面活性剤(1)(日信化学工業社製「サーフィノール465」)とを添加し、温度を50℃とした後、さらに超音波(40kHz)を20分間照射して、十分に内容物を分散させ、均一な分散物とした消火剤を得た。なお、表1に示すように、このときの粉砕フェロセン(1)の添加量は、分散物中での濃度が100ppmとなるように調節した。
また、界面活性剤(1)の添加量は、分散物中での濃度が0.2質量%となるように調節した。
図2に示す評価装置を用いて、得られた消火剤の消火能力を評価した。
ここに示す評価装置1は、評価対象の消火剤を保持する消火剤保持部11と、消火剤を噴霧するノズル14と、消火剤保持部11及びノズル14を連結する配管13と、配管13の途中に間挿され、消火剤保持部11からノズル14へ消火剤を移送するためのポンプ12と、消火剤が噴霧される燃焼物を保持する燃焼物保持部15と、を備えて概略構成されている。そして、ノズル14は、広がり角θを最大で60°として液体を噴霧できるようになっている。また、燃焼物保持部15は、内径Dが83mmの容器状のものである。
以上の消火操作を合計で5回以上行い、消火剤の消火能力を評価した。
結果を表1及び図3に示す。なお、表1中の消火能力の評価結果として記載した○、△、×は、それぞれ以下の意味を有する。
○:すべての消火操作で、噴霧開始から45秒以内に消火でき、消火時間が極めて短時間であった。
△:すべての消火操作で、噴霧開始から45秒以内に消火でき、消火時間が短時間であった。
×:すべての消火操作で、噴霧開始から45秒以内に消火できなかった。
表1に示すように、粉砕フェロセン(1)の濃度を100ppmに代えて125ppmとした点以外は、実施例1と同じ方法で消火剤を製造し、その消火能力を評価した。結果を表1及び図3に示す。
表1に示すように、粉砕フェロセン(1)の濃度を100ppmに代えて150ppmとした点以外は、実施例1と同じ方法で消火剤を製造し、その消火能力を評価した。結果を表1及び図3に示す。
表1に示すように、粉砕フェロセン(1)の濃度を100ppmに代えて75ppmとした点以外は、実施例1と同じ方法で消火剤を製造し、その消火能力を評価した。結果を表1及び図3に示す。
表1に示すように、粉砕フェロセン(1)を用いなかった点以外は、実施例1と同じ方法で消火剤を製造し、その消火能力を評価した。結果を表1及び図3に示す。
一方、比較例1では、消火剤がフェロセンを含有していないため、消火能力が認められず、同時に界面活性剤(1)が消火能力を有していないことが確認され、これは、実施例1~4の優れた消火能力が粉砕フェロセン(1)によるものであることを裏付けた。
遊星型ボールミルを用いて、市販品のフェロセンを45分間、400rpmで湿式粉砕して、粉砕フェロセン(以下、「粉砕フェロセン(2)」と略記する)を得た。レーザー回折式粒度分布測定装置(島津製作所社製「SALD-7000」)を用いて、この粉砕フェロセン(2)の粒度分布を測定し、粒度分布図を作成した。このときの粒度分布図を図4に示す。
図4の結果から、この粉砕フェロセン(2)は、メインピーク以外に粒径0.2μm付近に小さいピークを有する二峰性であり、メジアン径が10.4μmであることが確認された。
図5の結果から、この粉砕フェロセン(3)は、粒度分布がシャープな形状であり、メジアン径が11.4μmであることが確認された。
図6の結果から、この粉砕フェロセン(4)は、粒度分布がブロードな形状であり、メジアン径が21.5μmであることが確認された。
100mLの三角フラスコに、粉砕フェロセン(2)、粉砕フェロセン(3)又は粉砕フェロセン(4)と、水(100mL)と、分散剤として界面活性剤(1)とを添加し、温度を50℃とした後、さらに超音波(40kHz)を20分間照射して、十分に内容物を分散させ、均一な分散物とした消火剤を得た。なお、表2に示すように、このときの粉砕フェロセン(2)~(4)のそれぞれの添加量は、分散物中での濃度が100ppmとなるように調節した。また、界面活性剤(1)の添加量は、分散物中での濃度が0.4質量%となるように調節した。界面活性剤(1)の臨界ミセル濃度は、あらかじめデュヌイ表面張力計(伊藤製作所製)を用いて測定しておいた。
図2に示す評価装置を用いて、実施例1の場合と同様に、得られた消火剤の消火能力を評価した。ただし、評価装置1としては、燃焼物保持部15の内径Dが82mmであるものを用い、ここに保持したn-ヘプタンの上部の液面と、ノズル14の先端部との距離Hを60cmとなるように調節した。そして、n-ヘプタンに着火し、10秒間そのまま放置して、火炎を安定させ、ここへ、上記で得られた消火剤をノズル14から約250mL/分の流量で噴霧した。そして、消火剤の噴霧開始から20秒後までn-ヘプタンの状態を目視観察した。
以上の消火操作を合計で5回以上行い、消火剤の消火能力を評価した。結果を図7に示す。
表2に示すように、分散剤として界面活性剤(1)に代えて、界面活性剤(2)(日信化学工業社製「サーフィノール485」)を用いた点以外は、実施例5と同じ方法で消火剤を製造し、その消火能力を評価した。なお、界面活性剤(2)の添加量は、分散物中での濃度が0.2質量%となるように調節した。結果を図7に示す。
表2に示すように、分散剤として界面活性剤(1)に代えて、界面活性剤(3)(日信化学工業社製「オルフィンE1020」)を用いた点以外は、実施例5と同じ方法で消火剤を製造し、その消火能力を評価した。なお、界面活性剤(3)の添加量は、分散物中での濃度が0.2質量%となるように調節した。結果を図7に示す。
表2に示すように、分散剤として界面活性剤(1)に代えて、界面活性剤(4)(日信化学工業社製「オルフィンPD201」)を用いた点以外は、実施例5と同じ方法で消火剤を製造し、その消火能力を評価した。なお、界面活性剤(4)の添加量は、分散物中での濃度が0.2質量%となるように調節した。結果を図7に示す。
従来の消火剤である強化液(主成分:炭酸カリウム)の消火能力を、実施例5と同じ方法で評価した。結果を図7に示す。
一方、実施例6~8では、実施例5よりも消火時間に差が見られたものの、いずれもすべての消火操作で、消火剤の噴霧開始から20秒以内に消火できた。また、フェロセンの粒径が消火剤の消火能力に影響を与えていることを示唆するデータは得られなかった。
また、実施例6~8では、粉砕フェロセンの分散の度合いが大きいほど、消火時間のばらつきが抑制されることが確認された。
一方、比較例2では、平均消火時間が12.9秒であり、標準偏差(SD)は5.9であって、実施例5~8よりも明らかに消火能力が劣っていた。
表3に示すように、100mLの三角フラスコに、粉砕フェロセン(2)、粉砕フェロセン(3)又は粉砕フェロセン(4)と、水(100mL)と、分散剤として界面活性剤(1)、界面活性剤(2)、界面活性剤(3)又は界面活性剤(4)とを添加し、温度を30℃、40℃又は50℃とした後、さらに超音波(40kHz)を20分間照射して、消火剤を得た。このとき、粉砕フェロセン(2)~(4)の添加量は、分散物中での濃度が20ppmとなるように調節した。また、界面活性剤(1)~(4)の添加量は、分散物中での濃度が臨界ミセル濃度(cmc)の1倍、2倍又は5倍となるように調節した。
界面活性剤(1)~(4)の臨界ミセル濃度は、あらかじめデュヌイ表面張力計を用いて測定しておいた。
次いで、製造直後の消火剤を室温で20分間静置した後、フェロセン(粉砕フェロセン(2)~(4))の分散性を下記基準に従って目視評価した。結果を表3に示す。
(分散性の評価基準)
○:フェロセンが安定して分散した。
△:若干量のフェロセンが沈降したが、評価可能な分散液を得た。
×:超音波の照射時からフェロセンが分散しなかった。
表4に示す条件とした点以外は、実施例9と同じ方法で消火剤を製造し、フェロセンの分散性を評価した。結果を表4に示す。
表5に示す条件とした点以外は、実施例9と同じ方法で消火剤を製造し、フェロセンの分散性を評価した。結果を表5に示す。
表6に示す条件とした点以外は、実施例9と同じ方法で消火剤を製造し、フェロセンの分散性を評価した。結果を表6に示す。
市販品のフェロセンをメノウ乳鉢で粉砕し、目開き250μmのふるいにかけ、さらに目開き180μmのふるいにかけて、このふるい上に残ったもの(以下、「粉砕フェロセン(5)」と略記する)を選別した。実施例1と同様の方法で測定した粉砕フェロセン(5)のメジアン径は、30.9μmであった。
粉砕フェロセン(5)と、硫酸アンモニウム(メジアン径:22.2μm)とボールミルにて均一に混合することにより、表7に示す異なるフェロセン濃度の消火剤を調製した。
硫酸アンモニウムのみ又は得られた消火剤1.0kgを市販のABC粉末用加圧式4型消火器(ヤマトプロテック社製、型番YP-4)に充填して、消火剤の消火能力を評価した。
火炎模型B-1:火皿0.2m2、燃料n-ヘプタン
火災模型A-0.5:杉材36本
燃焼中の模型と消火器のノズル14の先端部との距離を1~2mとして、模型に向けて消火剤を噴射し、消火の可否を評価した。10秒以内で消火でき、かつ、再燃しない場合に完全に消化されたと判定した。消火できた場合を○とし、消火できなかった場合を×として、結果を表7に示す。
11 消火剤保持部
12 ポンプ
13 配管
14 ノズル
15 燃焼物保持部
θ ノズルからの消火剤の広がり角
H 液状可燃物の液面とノズルの先端部との距離
D 燃焼物保持部の内径
Claims (12)
- メタロセン及び分散媒を含有し、前記メタロセンが前記分散媒中に分散していることを特徴とする消火剤。
- 前記メタロセンがフェロセンであることを特徴とする請求項1に記載の消火剤。
- 前記メタロセンの含有量が70質量ppm~20質量%であることを特徴とする請求項1又は2に記載の消火剤。
- 前記分散媒が、不燃性の液体及び不燃性の粉体からなる群より選ばれる少なくとも1種であることを特徴とする請求項1~3のいずれかに記載の消火剤。
- 前記分散媒が、不燃性の液体であって、前記メタロセンの含有量が、70~160質量ppmであることを特徴とする請求項1~4のいずれかに記載の消火剤。
- 前記分散媒が水であり、さらに分散剤を含むことを特徴とする請求項5に記載の消火剤。
- 前記分散剤がノニオン系界面活性剤である請求項6に記載の消火剤。
- 前記界面活性剤の濃度が臨界ミセル濃度の1~7倍である請求項7に記載の消火剤。
- 横軸に消火剤製造後の時間をプロットし、縦軸に消火剤の濁度の逆数をプロットした際の傾きとして表わされる、前記消火剤中におけるメタロセンの分散安定度が1~20である請求項1~8に記載の消火剤。
- 前記分散媒が不燃性の粉体であって、前記メタロセンの含有量が、550質量ppm~20質量%であることを特徴とする請求項1~3のいずれかに記載の消火剤。
- 前記分散媒が、硫酸アンモニウム、硫酸マグネシウム、硫酸カリウム、リン酸二水素アンモニウム、リン酸水素二アンモニウム、リン酸カリウム、塩化ナトリウム、塩化カリウム、酸化マグネシウム、二酸化ケイ素、及びアルミナからなる群より選ばれる少なくとも1種である、請求項10に記載の消火剤。
- 請求項1~11のいずれかに記載の消火剤を燃焼物に供給する工程を含むことを特徴とする、消火方法。
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US (1) | US9782616B2 (ja) |
EP (1) | EP3012000B1 (ja) |
JP (1) | JP5967598B2 (ja) |
KR (1) | KR101786402B1 (ja) |
CN (1) | CN105339052B (ja) |
WO (1) | WO2014203935A1 (ja) |
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KR101654579B1 (ko) * | 2016-04-11 | 2016-09-06 | 주식회사 라인안전산업 | 소화성능이 우수한 강화액 소화약제 및 그 제조방법 |
CN107551443B (zh) * | 2017-09-17 | 2020-05-12 | 江山海维科技有限公司 | 一种abc干粉灭火剂的制备方法 |
CN111494862A (zh) * | 2020-05-07 | 2020-08-07 | 山东世洁环保科技有限公司 | 一种食用油灭火剂 |
KR102553229B1 (ko) * | 2022-10-19 | 2023-07-07 | 주식회사 에스제이코리아21 | 전기 이동 장치의 배터리 화재 진화용 방재액 |
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- 2014-06-18 KR KR1020167001040A patent/KR101786402B1/ko active IP Right Grant
- 2014-06-18 WO PCT/JP2014/066168 patent/WO2014203935A1/ja active Application Filing
- 2014-06-18 JP JP2015522957A patent/JP5967598B2/ja not_active Expired - Fee Related
- 2014-06-18 CN CN201480034663.3A patent/CN105339052B/zh not_active Expired - Fee Related
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Also Published As
Publication number | Publication date |
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EP3012000A4 (en) | 2017-03-01 |
US20160114203A1 (en) | 2016-04-28 |
KR101786402B1 (ko) | 2017-10-17 |
KR20160019955A (ko) | 2016-02-22 |
EP3012000A1 (en) | 2016-04-27 |
US9782616B2 (en) | 2017-10-10 |
JPWO2014203935A1 (ja) | 2017-02-23 |
JP5967598B2 (ja) | 2016-08-10 |
EP3012000B1 (en) | 2018-02-21 |
CN105339052B (zh) | 2017-09-01 |
CN105339052A (zh) | 2016-02-17 |
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