JP3404454B2 - Concentrated fire extinguishing fluid and its use - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD [0001] The present invention has a neutral physical property value, little deterioration with time, can carry out an efficient fire fighting operation with a relatively small amount of water, and significantly reduces water loss. The present invention relates to a concentrated fire-extinguishing solution which suppresses the generation of bubbles during use to facilitate the treatment of the residual fire-extinguishing liquid after extinguishing the fire, and particularly to reduce the addition amount of monoethanolamine so as to eliminate the deterioration of the fire-extinguishing performance. Further, the present invention has good storability,
Moreover, it is an object of the present invention to provide a versatile extinguishing solution stock solution and a fire extinguishing agent which are convenient to carry, have good solubility in water, and can be applied to extinguishing outdoor fires such as forest fires.

[0002]

2. Description of the Related Art As a general extinguishing method, radiant spray of fresh water is carried out toward a fire source. However, with the increase in types of fire combustion materials, various extinguishing methods such as powder type or foam solution type are extinguished. Drugs have come to be used. Further, a solid fire extinguisher which has been crushed to make it easily soluble in water and mixed and dissolved before use has also been developed. More recently, liquefied fire extinguishing agents prepared from the beginning have been developed. This is mainly composed of a composition of monoethanolamine and phosphoric acid and the like, which is as already disclosed in JP-B-58-58107 or JP-B-52-37319.

[0003]

However, in the case of spraying fresh water, in the case of fire extinguishing activities of not only general houses but also multi-story buildings such as high-rise buildings and condominiums, there is a direct relationship with the fire. Water scattering, runoff, and water leakage often occur in the lower floors where there is no water, causing secondary disasters due to so-called water damage. In addition to residential fires, in areas where water access is poor, such as earthquake fires and forest fires, there is a restriction that the limited water must be used efficiently.

Further, powder-type or foam-type fire-extinguishing agents have a higher fire-extinguishing ability than the above-mentioned water, but the cost is high. Therefore, when used in large quantities, they are focused on use in special cases such as complex or aircraft fires. Is placed. In addition, solid fire extinguishing agents are mainly crushed so that they can be easily dissolved in water in the event of a large-scale fire such as a forest fire, and then those dissolved in water are sprayed from the air using a helicopter or the like. However, since it is necessary to use a dissolver for dissolving the solid matter in water, the operation is complicated and the cost is high, which is not practical.

Further, the liquefied fire extinguisher mainly composed of the composition of monoethanolamine and phosphoric acid also has a problem in stability because the physical property value of the fire extinguisher is 6 or less. There are problems such as deterioration over time due to deterioration over time and material corrosion due to long-term storage.
Therefore, attempts have been made to improve the pH to 6 or higher, but in order to adjust the pH to 6 or higher, it is necessary to add monoethanolamine in an increased amount, and as a result, the fire extinguishing performance is increased in proportion to the increase in monoethanolamine. However, the current situation is that we cannot find an appropriate solution because of the problem of a decline in the price.

[0006]

Therefore, in the present invention, so-called water loss is eliminated, post-treatment is facilitated by suppressing the generation of bubbles during use, and storage is good and convenient for transportation. Moreover, it has excellent solubility in water, and the physical properties of the concentrated liquid can be maintained at pH 6 or higher without deteriorating the fire extinguishing performance, eliminating the corrosion and aging of the material due to long-term storage, and achieving long-term stabilization. A concentrated fire-extinguishing solution and a method of using the same have been developed. Specifically, 22-33 parts by weight of phosphoric acid and 20-28 parts by weight of monoethanolamine are added to 32-44 parts by weight of water. The present invention relates to a concentrated fire-extinguishing solution obtained by adjusting the pH within the range of 6 to 8 (± 0.4) by adding 7 to 13 parts by weight of dibasic ammonium phosphate.

According to the present invention, 22 to 33 parts by weight of phosphoric acid and 2 parts of monoethanolamine are added to 32 to 44 parts by weight of water.
The present invention also relates to a concentrated fire-extinguishing solution obtained by adding 0 to 28 parts by weight and 7 to 13 parts by weight of dibasic ammonium phosphate, and further adding 0.1 to 9 parts by weight of a surfactant. Further, the present invention relates to phosphoric acid 22 to 3 for 32 to 44 parts by weight of water.
3 parts by weight and 20 to 28 parts by weight of monoethanolamine are added to make it neutral, and further diammonium phosphate 7 to
The present invention also relates to a method of using the concentrated fire extinguishing liquid, wherein 0.5 to 21 parts by weight of the concentrated extinguishing liquid added with 13 parts by weight is added to 100 parts by volume of water.

Further, according to the present invention, 22 to 33 parts by weight of phosphoric acid, 20 to 28 parts by weight of monoethanolamine, and 7 to 13 parts by weight of ammonium diphosphate are added to 32 to 44 parts by weight of water. Further surfactant 0.1-9
The present invention also relates to a method of using the concentrated fire extinguishing liquid, wherein 0.5 to 21 parts by weight of the concentrated fire extinguishing liquid added to 100 parts by volume of water is used. Further, the present invention is
To 32 to 44 parts by weight of water, 22 to 33 parts by weight of phosphoric acid and 20 to 28 parts by weight of monoethanolamine are added to make it neutral, and further 7 to 13 parts by weight of dibasic ammonium phosphate is added. The present invention also relates to a method of using a concentrated fire extinguishing solution prepared by irradiating and using the concentrated fire extinguishing solution added to water and radiating the concentrated fire extinguishing solution into fine particles.

The concentrated fire-extinguishing liquid having such a composition ratio not only significantly improves the dissolution efficiency in water due to the easy-dissolving property of monoethanolamine, but also does not change the physical properties over time or corrode the material, and is a fire-extinguishing agent. Most effective and stable pH range as pH, ie, pH: 6.0
It can be maintained in an ideal range of up to 8.0 to improve storage and transportability, and it should be diluted with water depending on the type of fire. Usually, it can be used in the same manner as the water-based fire extinguishing method, or the fire extinguishing work can be carried out by radiating the diluted solution in the state of fine particle spray.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The specific contents of the present invention will be described below. That is, in the present invention, limited water can be used effectively and efficiently for extinguishing a fire, the extinguishing efficiency is better than that of water alone, and the amount of extinguishing agents other than water can be reduced. In addition, water, phosphoric acid, monoethanolamine, and dibasic ammonium phosphate were mixed in specified amounts as the main ingredients in order to simplify the treatment of the residual fire extinguishing liquid after use and to facilitate the dilution with water. To use.

The specific component range of each composition is water:
Phosphoric acid: 22 to 33 parts by weight (89% phosphoric acid: 25 to 36 parts by weight), monoethanolamine: 20 to 28 parts by weight, and further dibasic ammonium phosphate: 7 to 32 to 44 parts by weight. -13 parts by weight. By mixing these, there is no deterioration of fire extinguishing ability, and p
It is possible to obtain a concentrated fire-extinguishing solution adjusted to an ideal range of H: 6.0 to 8.0 (± 0.4). Further, if necessary, a surfactant: 0.1 to 9 (parts by weight) is added to improve the fire extinguishing ability.

The reason for specifying the component range of each composition in the present invention described above will be specifically explained by the following experimental example [Experimental Example 1] (Regarding the minimum amount of water and the maximum addition amount of dibasic ammonium phosphate) ) Generally, it is difficult to determine each composition range in a four-component system of water, phosphoric acid, monoethanolamine, and dibasic ammonium phosphate as a component system, and it is optimal to sequentially change from a minute amount for all compositions. The stepwise experimental method of obtaining the composition results in a huge number of experiments, and it is extremely difficult to obtain the optimum value. Therefore, in this experimental example, first, in order to obtain the initial value composition system, the following composition adjustment was performed based on many experiences obtained so far.

1) Water: 26 parts by weight, phosphoric acid (89%):
As a composition system in which 23 parts by weight and 19 parts by weight of monoethanolamine were added with 6.0 parts by weight of dibasic ammonium phosphate, water phosphate MEA DAP Experiment 1 26 23 19 6 (MEA: monoethanolamine , DAP: dibasic ammonium phosphate) In this experiment 1, it took a long time to dissolve dibasic ammonium phosphate in water, which was not practical. Therefore, as a result of an examination for increasing the solubility in water,
It was found that the amount of water required was 32 parts by weight or more.

Further, based on these results, the following adjustments were made: phosphoric acid MEA DAP experiment 2 30 23 19 15 A trial preparation of a concentrated fire extinguishing solution based on this composition was made.
The cloudiness continued. Therefore, as a result of various studies on the addition amount of the dibasic ammonium phosphate, it was found that the amount should be 13 parts by weight or less. Therefore, it was clarified from the above results that the condition is that water: 32 parts by weight or more and diammonium phosphate: 13 parts by weight or less.

[Experimental Example 2] (Regarding Maximum Amount of Water and Minimum Addition Amount of Phosphoric Acid and Dibasic Ammonium Phosphate) In this Experimental Example, the optimum range was determined by confirming the fire extinguishing performance. Regarding the concentration, the concentrated liquid was diluted to 3 parts by weight with respect to water, and the fire extinguishing test was performed using the A fire model defined by the Japan Fire Fighting Test Association. The results of the experiment were as follows when the extinguishing efficiency of water alone was set to 1. Water Phosphoric acid MEA DAP efficiency experiment 3 44 23 19 13 1.3 or more

According to the results of Experiment 3, a clear improvement in the fire extinguishing ability was observed as compared with the case of using water alone. On the other hand, as a more strict condition, the amount of secondary ammonium added is expected to be as low as 6 parts by weight.
It was reduced to 1 part by weight and the optimum conditions were further studied. Hydrophosphate MEA DAP efficiency experiment 4 41 23 19 6 1.1-1.2

According to the results of Experiment 4, although the fire extinguishing ability is slightly improved, it is still insufficient. Therefore, the phosphoric acid concentration is increased to 25 parts by weight and further extinction of the fire extinguishing ability is expected to decrease. The following experiment was conducted under the condition of the amount of monoethanolamine: Hydrophosphoric acid MEA DAP efficiency experiment 5 41 25 19 6 1.1-1.2 However, since no remarkable improvement in fire extinguishing ability was observed, When the amount of ammonium diphosphate was increased to 7 parts by weight and the experiment was continued, a fire extinguishing efficiency of 1.3 or more on average (compared with water alone as 1) was confirmed. It was found that the fire extinguishing ability was clearly improved.

In view of the above results, 44 parts by weight or less of water, 22 parts by weight or more of phosphoric acid (25 to 36 parts by weight in the case of 89% phosphoric acid), and 7 parts by weight of dibasic ammonium phosphate. It became clear that it was necessary to have more than one copy.

[Experimental Example 3] (Minimum amount of monoethanolamine and maximum amount of phosphoric acid added) In this experiment, the viewpoint of determining preferable physical property values for viscosity (kinematic viscosity) and pH, which are most important in actual use. Tried more. The effect of viscosity depends on the method for diluting the concentrated liquid with water, but it is necessary to be 100 cst or less from the requirements of the apparatus. In addition, the viscosity experiment was conducted as follows under the condition that the highest viscosity was empirically expected as a system. Hydrophosphate MEA DAP Experiment 6 30 25 28 13

According to the results of Experiment 6, the kinematic viscosity was 140 and 100 cst ± 30% or more, which is not practical. Therefore, further study was conducted on the optimum amount of monoethanolamine, and as a result, 100 cst ± 30% or less. It was found that the addition amount of monoethanolamine for the purpose should be 28 parts by weight or less. Regarding the most important pH value, a study was conducted with the goal of maintaining it near the neutral range of pH: 6 or above.
Empirically, the composition system having the lowest pH value was empirically prepared as follows: Hydrophosphate MEA DAP Experiment 7 30 37 197 7

According to the results of Experiment 7, the pH was 5.4. Therefore, for safety reasons, the phosphoric acid amount was 33 parts by weight or less, and the monoethanolamine was 20 parts by weight or more. I knew I could enter. The pH value at this time was pH: 6.1 ± 0.4. Under the above conditions, an experiment using the following composition system was attempted as a condition for further increasing the pH value. Hydrophosphate MEA DAP experiment 8 30 28 28 13

According to the results of Experiment 8, pH: 8.1 ±
It was 0.4. From the results of Experiments 6 to 8 above,
It was confirmed that the lower limit of the addition amount of monoethanolamine should be 20 parts by weight or more, and the upper limit of the addition amount of phosphoric acid should be 33 parts by weight or less. Therefore, when the results of Experiments 1 to 8 are summarized, the preferable component defining range of the composition system required in the present invention is 32 <water <44, 2
2 <phosphoric acid <33, 20 <MEA <28, 7 <DAP <
It turns out that it needs to be within a very limited range of 13.

[Experimental Example 4] (Regarding Addition Amount of Concentrated Fire Extinguishing Liquid to Water and Addition Amount of Surfactant) In this experimental example, the influence of the addition of the surfactant and the extinguishing ability of the completed concentrated fire extinguishing liquid Was examined. First, since the clear improvement of the fire-extinguishing capacity is observed compared to the case of using water alone, the preferable amount of the concentrated fire-extinguishing solution added to water is as follows: water phosphate MEA DAP composition 41 33 267, and the concentrated fire-extinguishing liquid was added and mixed with 100 parts by volume of water to give a fire-extinguishing agent, and the fire-extinguishing ability was examined in an actual fire-extinguishing experiment.

Addition amount 0 0.3 0.5 1.0 Fire extinguishing ability 11 to 1.1 1.1 to 1.2 1.3 (The addition amount unit is "part by weight", and the addition amount: 0 represents the state of water only) The result is that when the concentration of the concentrated fire extinguishing solution is diluted to about 0.3 (parts by weight), no noticeable effect is observed, but when it is 0.5 (parts by weight) or more, It was found that the fire extinguishing ability was clearly improved as compared with the case of using water alone.

Next, the effect of adding a surfactant was examined. That is, the composition of the concentrated fire-extinguishing solution to which the surfactant is added is as follows, and the phosphoric acid MEA DAP composition 1 38 25 26 7 is added to the surfactant (in this example, shampoo and other commonly used obazoline LB Was used as a concentrated fire extinguishing solution, and 5 parts by weight of water was added to 100 parts by volume of water to carry out a fire extinguishing experiment, and the following results were obtained. That is, the amount of surfactant 0.05 0.1 0.5 1.0 Fire extinguishing ability 1.0 1.1 to 1.2 1.2 1.2 to 1.3 (In this case, extinguishing with only the extinguishing liquid) Based on the above results, it was known that the addition of 0.1% by weight or more of the surfactant improves the fire extinguishing ability.

Next, to the above composition 1, a surfactant was added in the range of 5 to 12 parts by weight, and the concentrated fire extinguishing solution was diluted in the range of 1 to 23 parts by weight with respect to 100 parts by volume of water. I tried using the one I did. The evaluation method was carried out by a test based on the detailed rules for the test of foam extinguishing agents of the Japan Fire Fighting Test Association. The test content shown below is that the expansion rate is 3 times or less and 25% depending on the addition amount and the dilution amount of the surfactant.
This shows the condition that the reduction time is 30 seconds or less.

[0027]                                 Surfactant amount                         0.1 5 9 12   Rare 0.5: ○ −−−− ×           1: --- --- ○ ×   Release 5: --- --- --- ---         21: --- ○○ ---   Quantity 23: × − − × ×

From the above results, when the amount of the surfactant added exceeds 9 parts by weight, the expansion coefficient exceeds 3 times, and more than 25%.
Since the% reduction time exceeds 30 seconds, it became clear that the amount of the surfactant added should be 9 parts by weight or less and the dilution amount with water should be 21 parts by weight or less. It was Further, from the results obtained so far, it is found that the preferable range of addition amount of the concentrated fire extinguishing liquid to 100 parts by volume of water is 0.5 to 21 parts by weight, and that of the surfactant is 0.1 to 9 parts by weight. It became clear.

[Experimental Example 5] (Regarding Usage of Concentrated Fire Extinguishing Solution) The concentrated fire extinguishing solution obtained by the present invention is generally used by diluting and dissolving in water, and then radiating after further diluting in water. As a method, an attempt was made to investigate a method of forming fine particles and irradiating them to a combustion body, and the following results were obtained. That is, the composition of the concentrated fire-extinguishing liquid used in this experiment is as shown in the following composition 2. Regarding the dilution ratio with respect to water, water: 100 parts by weight of concentrated fire-extinguishing liquid: 5 parts by weight of concentrated phosphoric acid MEA DAP composition 2 32 32 21 11

As a method of forming fine particles, for example, FIG.
A pressure type liquid spray device as shown in FIG.
That is, this is a cylindrical pressure vessel 1 containing 7.4 liters, a pressure gas cylinder 4 for feeding a pressurized gas into the pressure vessel 1, and a liquid in the pressure vessel 1 under pressure. From the gas cylinder 4 for pressurization, which is composed of a spray nozzle 9 for injecting the solution F into the pressure vessel 1, is filled with 5 liters of the solution F in the pressure vessel 1, and is further connected to the upper void portion 2 in the pressure vessel 1 through the pipe 3. During the process, a gas having a constant pressure is sent through the pressure regulator 5 and the gas stop valve 6 for pressurization to pressurize the gas. The pressurized solution F is ejected from a spray nozzle 9 at the tip through a pipe 7 connected to the lower portion of the pressure vessel 1 and a valve 8 for stopping the solution injection in the middle.

The results of experiments using this apparatus are shown below: Pressure (Kg.f / cm2): 8 10 15 20 Efficiency (extinguishing solution / water): 1.3 1.3 1.3 1.6 1.8 Efficiency is The value for water alone is 1.3. From the above results, at a pressure of 8 kg, the concentration is merely within the range of the effect of the concentrated liquid, and it has not yet been made into fine particles. However, it was confirmed that as the pressure was further increased, the particles gradually became finer and the efficiency (extinguishing ability) increased.

The concentrated fire-extinguishing solution of the present invention does not prevent addition of various known additives, colorants, surfactants and the like in addition to the above-mentioned basic compositions.

[0033]

The effects of the present invention can be concluded as follows for each composition range by summing up the results of the above experimental examples. That is, in the present invention, with respect to water: 32-44 parts by weight (in the case of using 89% phosphoric acid, water: 29-41 parts by weight), phosphoric acid: 22-33 parts by weight (89% phosphoric acid: 25 ~ 36 parts by weight), monoethanolamine: 20
~ 28 parts by weight, further diammonium phosphate: 7-1
It is a concentrated fire extinguishing liquid made by adding and mixing 3 parts by weight, so it does not take up much space for storage and can be easily transported, and its physical properties (pH)
Is neutral, and as a result, there is no change with time such as corrosion of the material due to long-term storage, the stability is remarkably improved, the solubility in water is good, and efficient fire extinguishing work can be performed with a small amount of water.

If a concentrated fire extinguishing solution is prepared by adding 0.19 parts by weight of a surfactant to the above composition as needed, the expansion rate is within 3 times, and the 25% reduction time is 30 seconds. It is within the range and suitable for actual use. Furthermore, a concentrated fire extinguishing solution having the above composition is added to 0.5 to 21 parts by weight with respect to 100 parts by volume of water.
When added in parts by weight, diluted and dissolved, the expansion rate is 3 times or less, and 25% reduction rate is 30 seconds or less, which meets the low foaming test standard by the Japan Fire Defense Testing Association, and efficient fire extinguishing with a small amount of water The activity can be performed, water loss is significantly reduced, and the foaming rate is low, so that the treatment of the residual extinguishing liquid after extinguishing can be facilitated.

Further, when the concentrated fire-extinguishing liquid having the above composition is diluted with water and mixed to form a solution as a fire-extinguishing agent, and this is used by radiating it in the form of fine particles, the fire-extinguishing efficiency is further improved. be able to.

[Brief description of drawings]

FIG. 1 is a schematic view of a pressurized liquid spray device.

[Explanation of symbols]

1 pressure vessel 2 void 3 pipes 4 Gas cylinder for pressurization 5 Pressure regulator 6 Gas stop valve for pressurization 7 pipes 8 Valve for stopping solution injection 9 spray nozzles F solution

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hiroyuki Takahashi 1-1-1, Shimomachiya, Chigasaki City, Kanagawa Miyata Industry Co., Ltd. (56) Reference JP-A-5-317451 (JP, A) JP A 59-151972 (JP, A) JP-A-9-135920 (JP, A) JP 58-58107 (JP, B1) JP 52-37319 (JP, B1) (58) Fields investigated (Int. Cl. ⁷ , DB name) A62D 1/00

Claims (5)

(57) [Claims] 1. Phosphoric acid 22 for 32 to 44 parts by weight of water
A concentrated fire-extinguishing solution obtained by adding ˜33 parts by weight and 20-28 parts by weight of monoethanolamine to make it neutral, and further adding 7-13 parts by weight of diammonium phosphate. 2. Phosphoric acid 22 to 32 to 44 parts by weight of water
-33 parts by weight, 20 to 28 parts by weight of monoethanolamine, 7 to 13 parts by weight of dibasic ammonium phosphate, and 0.1 to 9 parts by weight of a surfactant are further added. 3. Phosphoric acid 22 for 32 to 44 parts by weight of water
To 33 parts by weight and 20 to 28 parts by weight of monoethanolamine to make it neutral, and further add 7 to 13 parts by weight of dibasic ammonium phosphate to prepare a concentrated fire extinguishing solution for 100 parts by volume of water. 0.5 to 21 parts by weight of the concentrated fire-extinguishing solution. 4. Phosphoric acid 22 for 32 to 44 parts by weight of water
To 33 parts by weight, 20 to 28 parts by weight of monoethanolamine, 7 to 13 parts by weight of dibasic ammonium phosphate, and 0.1 to 9 parts by weight of a surfactant are further added to form a concentrated fire extinguishing solution. 0.5 for 100 parts by volume of water
Usage of the concentrated fire extinguishing solution, which is used by adding 21 parts by weight. 5. Phosphoric acid 22 for 32 to 44 parts by weight of water
To 33 parts by weight and 20 to 28 parts by weight of monoethanolamine to make it neutral, and further add 7 to 13 parts by weight of dibasic ammonium phosphate to add and mix concentrated fire extinguishing solution to water. How to use a concentrated fire extinguishing liquid that is used by radiating fine particles.