JP2860311B2 - Cold-resistant fire extinguisher - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a fire extinguisher, and more particularly to a neutral liquid fire extinguisher having excellent cold-resistance stability without crystal precipitation and precipitation even at -27 ° C. .

[Conventional technology]

Conventionally, fire extinguishing agents packaged in containers mainly consist of powder extinguishing agents (A, B, C powder extinguishing agents-ammonium phosphate, ammonium sulfate, etc.) and (B, C powder extinguishing agents-sodium bicarbonate ...). However, it has been pointed out that the permeability to the combustion surface at the fire site is extremely weak to the water-based fire extinguishing agent, which causes a risk of re-flammability and that the fire-extinguishing work is difficult due to poor transparency at the fire site.

As a water-based fire extinguishing agent, an enhancer extinguishing agent (potassium carbonate,
(Aqueous solution of potassium bicarbonate) is now widely used, but it is strongly alkaline and has a fire-extinguishing capacity of 3 or more, which is about class A-1 of general fire, its fire-extinguishing ability is extremely small, and it requires a large amount of discharge. . In addition, it is not necessarily safe for humans and animals due to its strong alkalinity (about PH 11-13). Therefore, a neutral-enhancing liquid fire extinguishing agent has been requested and developed, but a neutral and high-extinguishing fire extinguishing agent has advantages and disadvantages, and there are also problems that must be solved in practical use. Many.

Ammonium phosphate, which is suitable as a neutral fire extinguishing agent, has good solubility in water, and its aqueous solution shows almost neutral pH (approximately pH 6.5 to 8). However, there is a defect that shows unstable properties at low temperature (5 ° C. or less below freezing point). In other words, the cold resistance stipulated in the ministerial ordinance is a condition that can be used even at -20 ° C. In order to satisfy this condition, it must have fluidity even at -23 ° C. Requires the addition of large amounts of antifreeze and freezing point depressants. However, as antifreeze and freezing point depressant, Class 4 second petroleum,
Since dangerous substances belonging to the third petroleum are used, the conditions used in the operating temperature range of -20 ° C to 40 ° C stipulated by ministerial ordinance have difficulties in terms of volatilization and ignition,
As a fire extinguishing agent, there is a drawback in terms of reduced ability in use in the event of a fire.

Therefore, ammonium phosphate is hardly used as a water-based fire extinguishing agent, and the present technology is used exclusively as a powder fire extinguishing agent.

[Problems to be solved by the invention]

As described above, the powder extinguishing agent has a problem of re-combustion and the like because it does not have a temperature lowering effect by cooling water with respect to a combustion material at a fire site and has a wet permeability.
However, there is a problem in the cold resistance that can be used and the flammability of antifreeze and freezing point depressant. In addition, those with strong alkalinity have problems such as hindrance to humans and animals.

In view of these circumstances, the present invention has been developed for the purpose of providing a neutral water-based fire extinguishing agent excellent in cold resistance at -20 ° C.

[Means for solving the problem]

The present invention solves the above problems and achieves the object. (1) A fire extinguisher in which aminotrimethylenephosphonic acid neutralized with caustic potassium is added as an anti-cold stabilizer to an aqueous solution of ammonium phosphate.

(2) A fire extinguisher obtained by adding ethylene glycol and dimethyl triglycol as antifreezing agents to an aqueous solution of ammonium phosphate.

(3) Ethylene glycol and dimethyl triglycol are added as antifreezing agents to the ammonium phosphate aqueous solution,
A fire extinguisher to which quanidine sulfamate and ammonium bromide are added as flame retardants.

Taking the technical measures of that.

That is, in the present invention, cold resistance, flame retardancy, disaster prevention, neutrality, and an increase in fire extinguishing efficiency are achieved while selecting ammonium phosphate as an aqueous fire extinguishing agent.

[Action]

The present invention configured as described above has the following operation.

7-12% by weight of ammonium phosphate as a fire extinguishing agent,
The aqueous solution dissolved in water is neutral (pH 6.5 to 8) and adheres to and penetrates the fire combustion area, lowering the temperature, and lowers the temperature due to true catalysis by NH ₄ ions, thermal decomposition, and cooling by water. It extinguishes oxygen and extinguishes fire.

Aminotrimethylenephosphonic acid neutralized with caustic potash
Addition of 1.5 to 2.5% by weight has the effect of suppressing crystal growth of the aqueous solution of ammonium phosphate at a low temperature and stabilizing the flow properties.

Ethylene glycol has an effect of suppressing coagulation of an aqueous solution of ammonium phosphate at a low temperature and maintaining fluidity.

Guanidine sulfamate and ammonium bromide, when added together, have an effect of making the antifreeze agent non-flammable and flame-retardant at a temperature of 40 ° C. or higher of the antifreeze.

〔Example〕

 An embodiment of the present invention will be described.

Basic experiment (a) Various drugs and results of attempts to make them transparent ◎ Ethylene glycol 5ml / 100ml transparent ◎ Glycerin Same as above ◎ Propylene glycol Same as above ○ Polyethylene glycol PEG 200,300,400,600,100 are all cloudy ○ Carboxymethylcellulose (CMC) Low concentration cloudy ◎ Dimethyltriglycol Transparency Basic experiment (b) As a surfactant, the results of transparency and freezing test using betaine-type amphoteric surfactant and F-based surfactant are as shown in the following table.

Basic experiment (c) Cold-resistance test The results of the cold-resistance test of a single product or a mixture are shown in the following table.

As described above, except for K ₂ CO and KHCO ₃ , both have poor cold resistance, but CH ₃ COONH ₄ and CH ₃ COOK show transparent gelation.

Therefore, as an inorganic freezing point depressant, the aliphatic organic chemicals CH ₃ COONH ₄ , CH ₃ COOK, CH ₃ COONa 3H ₂ O are effective neutralizing freezing point depressants because they are almost neutral, non-flammable, and highly soluble salts. It was confirmed that there was.

Basic experiment (d) The results of the cold resistance test using the freezing point depressant and antifreeze added to the formulation of experiment (b) are shown in the following table. (× frozen) As a result, the combination of EG and DMTG seems to be the best. EG20
Although the blending ratio of ml / 100 ml is good in cold resistance, it is impossible for EG alone to satisfy the standard prescribed in the ministerial ordinance, and the viscosity is very high, and there are many problems. Therefore, by using DMTG (dimethyltriglycol) together, -20 ℃
And the viscosity can be reduced.

Basic experiment (e) Addition of aminotrimethylenephosphonic acid as a property stabilizer, 1.5-2.5% as a crystal growth inhibitor, and dimethyltriglycol 5-10% as a freezing point depressant in combination with ethylene glycol in experiment (b) The property stability and cold resistance test according to were as follows.

Basic experiment (f) The measured freezing point by ammonium phosphate concentration is as follows.

[Study of Experimental Values] As can be seen from the results of the basic experiments described above, it is considered that the amount of ammonium phosphate used is 12 wt% with respect to the aqueous solution, which indicates one concentration limit. The use of the freezing point depressant and the antifreeze is also considered to be 20% by weight (−18 ° C.) as a limit of one concentration.

In the basic experiment (c), it was confirmed that ammonium acetate, potassium acetate, potassium phosphate and the like are effective as an auxiliary agent for lowering the freezing point and as a fire extinguishing agent.

It was found that by adding and mixing 0.85 to 1.15 mol of ammonium acetate, potassium phosphate and potassium acetate with 1.5 mol of ammonium phosphate, the freezing point lowering and fire extinguishing ability were remarkably improved by the synergistic effect.

Therefore, attention is focused on the fact that aminotrimethylene phosphonic acid has many possibilities for use as a crystal growth inhibitor, a deflocculant, and a dispersant for hydrolysis of an aqueous solution of ammonium phosphate at a low temperature condition of −20 ° C. or less. , 0.2 to 0.3 mol of caustic potash with respect to 0.4 to 0.5 mol of aminotrimethylene phosphonic acid, it was confirmed that fire extinguishing performance, freezing point depression, and property stability were both excellent.In addition, inorganic, organic compounds, ammonium acetate, It was found that the combination of potassium acetate and potassium phosphate as an auxiliary agent was more effective.

On the other hand, aliphatic organic chemicals guanidine sulfamate (CH
₅ N ₃ HSO ₃ NH ₂ ) and ammonium bromide (NH ₄ Br) form ethylene glycol methanol,
It was also confirmed that dimethyltriglycol has a remarkable effect as a flame retardant and a disaster prevention agent. Next, surfactants such as anionic, N-acyl-N-methyl-β-alaninate, (RCON (CH ₃ ) CH ₂ CH ₂ COONa) and sulfates By adding, more stable properties and fire extinguishing performance against oil fire (B fire) can be improved. A small amount of F-based surfactants and perfluoroalkyl potassium-based compounds are excellent as fire-extinguishing foam-developing agents, and dibasic acid ester sulfonated compounds are used as a strong penetration enhancer for combustibles. It has been recognized that the addition of 0.1 to 1% of an anionic activator containing as a main component can improve the fire extinguishing performance of a general fire (fire A) to a more excellent one.

It was also recognized that when dimethyltriglycol was added to about 5 to 10% by weight of ethylene glycol, the viscosity was lowered and the fluidity and permeability of the liquid neutral fire extinguishing agent were significantly improved.

The synergistic effect of the alaninate type + F type + dibasic ester sulfonate + dimethyltriglycol is an improvement in fire extinguishing performance due to a decrease in surface tension (18 dyn / cm or less) and interfacial tension (2 dyn / cm or less).

The most effective blending examples in the present invention are as follows.

The properties of the fire extinguisher shown in the formulation examples are as follows.

 PH (24 ℃) 7.4 Specific gravity 1.152 Viscosity 3-5cst Surface tension 18dyn / cm or less Interfacial tension 2dyn / cm or less Diffusion coefficient 5 Fire extinguishing ability A-2 / 3 B-5 / 3 Operating temperature range -25 ℃ -40 ℃ 150 hours Freezing, no similar phenomena.

As shown above, the fire extinguisher is almost neutral and has no effect on humans. The fire extinguishing ability is also 3, indicating high performance capable of coping with fires of A-2 and B-5. Crystal precipitation can be reduced to -28 ° C, and it has excellent cold resistance.

 The embodiments are summarized as follows.

1. Aminotrimethylenesulfonic acid, the instability of ammonium phosphate at low temperature, 1-hydroxyethylidene-1,1-diphosphonic acid ethylenediaminetetramethylenephosphonic acid Hexamethylenediaminetetramethylenephosphonic acid,
Diethylenetriamine pentamethylene phosphonic acid, ethylene diamine tetraacetic acid _{EDTA. (HOOCCH 2) 2 N} (CH 2) 2 N
(CH ₂ COOH) ₂ molecular weight 292.55, relative 1-hydroxyethylidene--1.1- diphosphonic acid, by adding a molar ratio corresponding to Na, it has solved.

2. Addition of aliphatic organic chemicals CH ₃ COONH ₄ and CH ₃ COOK significantly and synergistically reduced the freezing point and improved the fire extinguishing performance.

3. The combination effect of ethylene glycol and dimethyltriglycol has enabled viscosity reduction, freezing point reduction, and improvement in fluidity.

4. By adding guanidine sulfamate (CH ₅ N ₃ HSO ₃ NH ₂ ) and ammonium bromide (NH ₄ Br), it is flame retardant to ethylene glycol, dimethyl triglycol, methanol, alanine surfactants, etc. Both A and B fires are effective in preventing relapse and disaster prevention.

5. A combination of a dibasic acid ester sulfonate and a sulfate ester-based or perfluoroalkyl potassium salt enables improved permeability and adhesion effect.

6. The promotion of the wetting effect by the remarkable decrease of the surface tension by the sodium alanine N-acyl-N-methyl-β-alanine and the sulfuric acid ester type or F type perfluoroalkyl potassium.

7. Rust prevention effect by adding M-12 as an inhibitor to sodium molybdate and benzotriazole.

〔The invention's effect〕

As described in detail above, the present invention has the following excellent effects.

(1) Excellent ammonium phosphate was selected as a fire extinguishing agent, and aminotrimethylene phosphonic acid neutralized with caustic potassium was added to the aqueous solution as a cold-resistant stabilizer, so crystal precipitation was suppressed even at low temperatures below -20 ° C. A neutral water-soluble fire extinguisher with stable properties can be obtained.

(2) Since ethylene glycol and dimethyltriglycol are added as antifreezing agents to the aqueous solution of ammonium phosphate, they are cold-resistant and have low viscosity even at a low temperature of -20 ° C, so they have good fluidity and extremely stable and stable cold resistance. It can be a neutral aqueous fire extinguisher.

(3) Since guanidine sulfamate and ammonium bromide are added as a flame retardant to a fire extinguishing liquid to which ethylene glycol and dimethyl triglycol are added as an antifreeze, the fire extinguisher is fire-retardant even at a high temperature of 40 ° C or more. Excellent.

Claims (3)

(57) [Claims] 1. A fire extinguisher comprising an aqueous solution of ammonium phosphate as a main component, wherein said ammonium phosphate is in the range of 7 to 12% by weight, and 0.2 to 0.3 mol based on 0.4 to 0.5 mol of aminotrimethylene phosphonic acid. Cold stabilizer neutralized with caustic potash
A cold water-resistant fire extinguisher characterized by being added in the range of 1.5 to 2.5% by weight. 2. A fire extinguisher comprising an aqueous solution of ammonium phosphate as a main component, wherein said ammonium phosphate is in the range of 7 to 12% by weight, and 0.2 to 0.3 mol per 0.4 to 0.5 mol of aminotrimethylene phosphonic acid. Cold stabilizer neutralized with caustic potash
A cold-resistant fire extinguisher characterized by being added in the range of 1.5 to 2.5% by weight, and in the range of 5 to 20% by weight of ethylene glycol and 5 to 10% by weight of dimethyltriglycol as an antifreeze. 3. A fire extinguishing agent mainly comprising an aqueous solution of ammonium phosphate, wherein said ammonium phosphate is in the range of 7 to 12% by weight, and 0.2 to 0.3 mol based on 0.4 to 0.5 mol of aminotrimethylenephosphonic acid. Cold stabilizer neutralized with caustic potash
1.5 to 2.5% by weight, added 5 to 20% by weight of ethylene glycol and 5 to 10% by weight of dimethyltriglycol as antifreeze, and added guanidine sulfamate and ammonium bromide as flame retardants. Characterized by a cold water resistant fire extinguisher.