JPS62129066A - Foam fire extinguishing agent - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a fire extinguishing foam, and more specifically, a fire extinguishing foam containing a reaction product of a protein hydrolysis product and Daiichichichi salt. It is related to.

[Conventional technology]

Currently, the foam fire extinguishing agent used in Ishiura-no-ho fires is made by partially hydrolyzing keratin protein powder from cow and horse hooves and horns with a strong alkali such as sodium hydroxide or calcium hydroxide. A ferrous salt such as ferrous sulfate or ferrous chloride is added to the decomposition product as a foam stabilizer. Such foam fire extinguishers have excellent heat resistance and foam film stability, and have the advantage of being highly oil resistant at high oil temperatures, but since they contain iron salts, they do not absorb water during storage. Insoluble decomposed proteins - iron compounds, ferric hydroxide, and decomposed proteins that co-precipitate by adsorbing on ferric hydroxide precipitate, and this precipitate reduces the fire extinguishing ability and shortens the effective period of fire extinguishing foam. The disadvantage is that it only lasts about 3 to 4 years.

On the other hand, it is also known to produce a foam fire extinguishing agent with improved durability and fire extinguishing performance by reacting a partial hydrolyzate of keratin protein with a ferrous salt at 90-100°C (Japanese Patent Publication No. 11879/1989). issue). However, the fire extinguishing agent produced in this way also produces precipitates during storage, resulting in a decrease in fire extinguishing ability, and cannot be said to be a satisfactory foam fire extinguishing agent.

[Problem that the invention seeks to solve]

Therefore, in order to obtain a fire extinguishing foam that has high heat resistance, foam film stability, and especially long-term fire extinguishing performance, keratin protein partial hydrolysis products are subjected to various processing treatments or by the addition of second components. Although improvements have been made in terms of long-term storage stability, even the reaction of the protein hydrolysis product with ferrous salts is still insufficient as a long-life, high-performance fire extinguishing foam. Further, no attempt has been made to further examine the reaction product itself between the proteolytic product and the ferrous salt. However, the present inventor has repeatedly studied this reaction product and found that under the following reaction conditions, the protein hydrolysis product and ferrous ion combine to form a water-soluble chelate compound. They also discovered that this chelate compound contains a long-life, high-performance fire extinguishing agent component.

[Means/effects for solving the problem] The present inventor has proposed that the partial hydrolysis product of keratin protein and the ferrous salt be used for precipitation of ferric hydroxide and isoelectric precipitation of protein degradation products. A special chelate compound of proteolytic products and ferrous ions was obtained by reacting under conditions that do not cause ferrous ions.

Although this chelate compound is considered to be a novel compound that has not been previously known, we have completed the present invention by discovering that this chelate compound is extremely effective as an effective ingredient in fire extinguishing agents. It was also found that the molecular weight cut-off of this chelate compound has a large effect on the fire extinguishing effect.

That is, according to the present invention, keratin protein is hydrolyzed with an alkali, a ferrous salt is added to the obtained protein hydrolysis product, and ferric hydroxide precipitation and isoelectric precipitation of the protein hydrolysis product are performed. A chelate compound of a proteolytic product and ferrous ion was obtained by reacting the product under conditions that do not cause ferrous ions. From this chelate compound, a novel chelate compound having a molecular weight cut off of 300,000 or less and having a long life, high performance, and excellent fire extinguishing action can be obtained by ultra-e-filtration. It goes without saying that, for example, chelate compounds with fractionated molecules of less than 110,000 yen or less than 50,000 yen also have long life, high performance, and excellent fire extinguishing power.

Ferrous salts, which are normally added as stabilizers to fire extinguishing foams, are oxidized in the fire extinguishing agent to produce a precipitate of ferric hydroxide and adsorbed protein hydrolysis products; Isoelectric precipitates are also likely to occur, and these precipitates cause a reduction in the life of the extinguishing agent. According to the present invention, reaction conditions in which these precipitations do not occur are obtained by maintaining the pH between 7.0 and 7.5.

As the raw material for the protein hydrolysis product used in the present invention, any keratin protein source of animal or plant origin may be used, such as powder of cow and horse hooves, horns, blood, etc., microbial protein, seed powder, etc. be able to. Protein hydrolysis is carried out under conventional conditions, such as heating in water using sodium hydroxide or calcium hydroxide at a concentration of 5 to 10% by weight at a temperature of about 100 DEG C. for about 1 hour or more. After the hydrolysis is completed, it is neutralized with an inorganic acid such as hydrochloric acid or sulfuric acid, or an organic acid such as acetic acid, and then fine precipitates etc. coexisting are removed using two pieces of paper.

The protein hydrolysis product obtained in this way has a pH of 7.0~
A ferrous salt is added under the conditions of 7.5, and all of the added ferrous ions are reacted with the protein hydrolysis product to form a chelate compound of the protein hydrolysis product and ferrous ions. The chelate compound thus obtained is a fractionated molecule f
It is concentrated by ultra-e filtration using a fl'300,000 membrane, and those having a cutoff molecular weight of 300,000 or less are completely recovered in the e-liquid.

The liquid is further concentrated by reverse osmosis, heating or freeze drying, which can exclude components with a molecular weight of about 1000 or less, such as lower peptides and amino acids, which adversely affect foaming properties and hard water resistance. Or preferable.

The residue of fractionated molecules m300,000 or more remaining on the P membrane can be hydrolyzed again to reduce the molecular weight.

Examples of the ferrous salt to be reacted with the protein hydrolysis product having a molecular weight cut-off of 300,000 or less obtained as described above include ferrous sulfate and ferrous chloride.

The reaction of the protein hydrolyzate and the 1y salt according to the invention is carried out under conditions such that precipitation of ferric hydroxide and isoelectric precipitation of the protein hydrolyzate does not occur. Such reaction conditions prevent oxidation of ferrous ions,
Stir for about 3 hours at a temperature below ℃. Protein hydrolysis products and the first
Since the pH decreases due to the reaction with iron ions, a sodium hydroxide solution is added to adjust the pH to 7.0 to 7.5, followed by further stirring. When the reaction between the protein hydrolysis product and the ferrous ions is almost completed, the mixture is further stirred at 50 to 60°C for 30 minutes or more. If the pH drops below 7.0 at this point, add sodium hydroxide solution again to pH 7.0-7.
．． 5, and further warmed. Continuing these operations, by confirming that the pH becomes constant at the end, a protein hydrolysis product and a chelate compound of ferrous ions can be obtained. It will be done.

FIG. 1 is a visible spectrum diagram of a protein hydrolysis product-iron(n) chelate compound having a molecular weight cut off of 300,000 or less according to the present invention. In the figure, the solid line is the wavelength-absorbance curve of a protein hydrolysis product with a molecular weight cut-off of 300,000 or less [no iron (n) ions, nitrogen concentration 0.125 g/d (0.09 mol)], The chain line represents a protein hydrolysis product with a molecular weight cut-off of 300,000 or less - iron (n) chelate compound [iron (n) ion concentration 0.0125 gld (0,0022 mol), nitrogen concentration 0.125 g/d] It is a wavelength-absorbance curve of .

In addition, the visible spectrum of a chelate compound with a molecular weight cut off of 300,000 or less shows an increase in absorption over the entire visible region compared to the visible spectrum of a protein hydrolysis product with a molecular weight cut off 300,000 or less and the visible spectrum of ferrous sulfate ion alone. Is recognized.

This increase in absorption is apparently due to the novel chelate compound produced by the reaction of protein hydrolysis products with a molecular weight cut-off of less than 300,000 and ferrous sulfate ions. Further, in the aqueous solution of ferrous sulfate ions, absorption in the visible region is not observed. The increase in absorption in the visible region is due to the fact that the aqueous solution of the protein hydrolysis product with fractionated molecules ffl' of 300,000 or less before the reaction is a dark brown transparent liquid, but it reacts with the ferrous salt to form a chelate compound. This corresponds well to the fact that the reaction solution turns reddish-brown when it is formed.

This solution containing a chelate compound with a molecular weight cut off of 300,000 or less can be used as is, or if a precipitate has formed, after filtering the precipitate, additives commonly used in fire extinguishing foams, such as antifreeze agents, etc.
For example, glycols such as ethylene glycol and propylene glycol, clay-reducing agents such as urea, preservatives such as water-soluble salts of trichlorophenol, and foam flow agents such as saponin can be added. In particular, fluorosurfactants such as N, M, N-trimethyl, N
-3-(perfluorooctylsulfonylamino)probylammonium aniodide [08F17So2N
E((CH) N+ (CH) (-co, potassium perfluorooctyl sulfonate [C3F17S
03, potassium-N-propyl, N-perfluorooctylsulfonyl-glycinate [CF
S ON (C3H7) CH2CO0K], N-
Propyl, N-polyoxyethylene, perfluorooctyl sulfonamide [08F17SON (C3H7)
(CH2CH20)nHco, storium=3-IN
-Methyl-N-[3-(perfluorohexylsulfonylamino)propylcoamino)-1-propanesulfonate [C6F13SONH(CH2)3N(CH3)(
CH2)3SO3Na], sodium-2-fN-[2
=(berolohebutylcarbonamido)amino) -1
-ethanecarboxylate [C7F150ONH(CH
) NH(CH2) 2COONa ] has the effect of significantly improving the extinguishing action of the fire extinguisher of the present invention against petroleum, alcohol, etc.

The present invention will be explained in more detail with reference to the following examples.

Example 100 g of mixed powder of cows, horses, and hooves passed through a Tyler sieve with a mesh size of approximately 1 mm was placed in a 12 ft three-loaf flask with a reflux condenser, and 400 g of distilled water was added.
C and 20 g of sodium hydroxide were added, followed by boiling at 90° C. for 90 minutes. After completion of hydrolysis, neutralize with concentrated hydrochloric acid so that 911 becomes 7.5, pass through two papers No. 2 and 2, and filter with a 5μ1 Tl (micron) membrane filter.
Remove coexisting fine precipitates, etc. The hydrolysis product thus obtained has a ferrous iron concentration of 1.0 to 1.5.
Powdered ferrous sulfate is added to make the weight percentage. Next, in order to prevent oxidation of ferrous sulfate ions, the mixture is stirred at 20°C or lower for about 3 hours. Protein hydrolysis products and the first
Since the pH decreases due to the reaction with iron ions, a concentrated sodium hydroxide solution is added while stirring to prevent the pH decrease, and the pH is maintained at 7.0 to 7.5 at a temperature of 20°C. When the reaction between the protein hydrolysis product and the ferrous ions is almost complete, the reaction temperature is 3°C at 50-60°C to accelerate the reaction.
After itching for more than 0 minutes, it was cooled to room temperature. pH after cooling
When the pH drops to 7.0 or less, a concentrated sodium hydroxide solution is further added until the pH becomes 7.0 to 7.5, and the mixture is further heated and stirred. Finally, to confirm that the pH has become constant, use an ultrafiltration device (UHP-150, manufactured by Toyo R Paper) using a membrane with a molecular weight cutoff of 300,000 (manufactured by Amicon) to obtain a molecular weight cutoff of 300,000. The above substances were collected on the membrane, and those with a molecular weight cut-off of 300,000 or less were recovered in the t-liquid (yield of about 70~
80%). The obtained P solution was passed through a reverse osmosis device (
The mixture was concentrated to a solid content concentration of 20 to 30% using an RO-3 model (ULVAC Service Equipment). As a result, a reddish-brown transparent liquid was obtained. This liquid has a black-rimmed color.
Iron (II) is clearly different from the reaction solution of No.-11879.
)-Protein hydrolysis product chelate compound.

The performance of the solution containing the iron (n)-protein hydrolysis product chelate compound thus obtained as a fire extinguisher was tested as follows. - In a square iron combustion dish with sides of 70.7 cm and height of 40 cm (combustion area: 0.5 rrl'), 50 g of gasoline is ignited as fuel, and 5 minutes after ignition, the 396 aqueous solution of the sample is fixed. A foam aqueous solution was discharged in the form of bubbles along the wall of the combustion dish from the foam discharge nozzle onto the combustion surface at a rate of 2.5 sentences per minute.

The results are shown in the table below.

1) Protein foam fire extinguishing agent for petroleum (3%) 2) Foaming ratio is how many times the volume of the foam created when the foam aqueous solution is discharged from the foam discharge nozzle is the volume of the original foam aqueous solution. ′
−Represents budaka.

3) 2596 reduction time refers to the time required for the amount of foam aqueous solution discharged from foam due to foam destruction to become one-fourth of the original amount of the aqueous solution.

4) After extinguishing the fire, dip an ignition rod in gasoline and bring the ignited flame close to the entire surface of the foam layer covering the combustion surface to check for re-ignition.

From the results in the table, it is clear that the fire extinguishing agent according to the invention has excellent fire extinguishing performance. In addition, the fire extinguishing agent according to the present invention is based on the technical standards for fire extinguishing foam (Ministry of Home Affairs Ordinance No. 26, Showa 5).
(December 2010), which is a test in which fire extinguishing foam is kept at a temperature of 65℃ for 218 hours and then returned to room temperature, and then kept at a temperature of -18℃ for 24 hours and then returned to room temperature. When used continuously for 6 months, the commercially available protein foam fire extinguishing agent produced a large number of precipitates compared to before the deterioration test, and the foaming properties and fire extinguishing performance decreased significantly, but the foam fire extinguishing agent of the present invention did not cause precipitation. In addition, the foaming property and fire extinguishing performance did not deteriorate, and the product showed excellent performance such as long life and high performance.

〔Effect of the invention〕

The fire extinguishing agent containing a chelate compound of a protein hydrolysis product and ferrous ion according to the present invention and having a cut-off molecular weight of 300,000 or less has excellent foaming properties and fire extinguishing properties, and has a long shelf life, compared to conventional It retains its fire extinguishing performance for a longer period of time.

[Brief explanation of drawings]

FIG. 1 is a visible spectrum diagram of a protein hydrolysis product-iron(n) chelate compound having a molecular weight cut off of 300,000 or less according to the present invention. Figure 1 Wavelength (nm)

Claims (1)

[Claims] A molecular weight cutoff of 30 in a product obtained by reacting a protein hydrolysis product and a ferrous salt under reaction conditions that do not cause precipitation of ferric hydroxide or precipitation of the protein hydrolysis product.
A fire extinguishing foam characterized by containing a chelate compound of a protein hydrolysis product and ferrous ion in an amount of 1,000 or less, and other additives as necessary.