JP2016174802A - Environmentally-friendly foam fire extinguishing agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an environmentally-friendly foam fire extinguishing agent that can satisfy sewage discharge criteria.SOLUTION: Provided is an environmentally-friendly foam fire extinguishing agent characterized by containing, as an active ingredient, a hydrocarbon-based anionic surfactant and a hydrocarbon-based ampholytic surfactant, and in which, more preferably, characterized, said hydrocarbon-based anionic surfactant is alpha olefin sulfonic acid salt represented by a general formula: RCH=CH(CH)SOZ (R is an aliphatic hydrocarbon group having 8 to 30 carbon atoms, n represents 0 to 5, and Z is an alkali metal and/or alkaline earth metal), and said hydrocarbon-based ampholytic surfactant is lauryl dimethyl aminoacetic acid betaine represented by a general formula: RNCH(CH)CHCOO(R is an aliphatic hydrocarbon group having 8 to 30 carbon atoms).

Description

  The present invention relates to a foam fire-extinguishing agent, and more particularly to an environment-friendly foam fire-extinguishing agent.

  In general, foam fire extinguishing agents are mainly used for flammable liquid fires that are less effective in fire extinguishing with water, or on the contrary, may spread the fire. It is important (for example, Patent Document 1 below).

  As this foam extinguishing agent, protein foam extinguishing agent mainly composed of hydrolyzed protein, fluorinated protein foam extinguishing agent containing fluorinated surfactant in protein foam extinguishing agent, or hydrocarbon interface Synthetic surfactant foam extinguishing agents based on activators and water film forming foam extinguishing agents based on hydrocarbon surfactants and fluorosurfactants are known.

  In addition, foam extinguishing equipment is used in large-scale facilities where there is a risk of fire due to the above flammable liquids such as oil complexes and parking lots, water supply sources, foam extinguishing agent storage tanks, water and foam extinguishing systems. It is composed of a mixer for mixing the liquid agent, a foam discharge port (foam head) for releasing air as a fire extinguishing agent while air is mixed into the mixed agent to generate bubbles.

  By the way, among the above-mentioned foam fire extinguishing agents, since the protein foam fire-extinguishing agent and the fluorine protein foam fire-extinguishing agent are accompanied by odors, the foam extinguishing agent released from the foam head of the foam extinguishing equipment installed in the parking lot in particular. In many cases, synthetic surfactant foam fire extinguishing agents and water film forming foam extinguishing agents are mainly used.

JP-A-9-173498 JP 2011-87792 A “Form head” Japan Fire Safety Center, December 1, 2000, p.22-23, 38-40

  However, these synthetic surfactant foam fire extinguishing agents and water film forming foam extinguishing agents have a high normal hexane extractable substance content and a nitrogen content, and in particular, a very high biochemical oxygen demand (BOD). For this reason, if it is discharged into the sewer, the environmental impact is high, and it exceeds the standard value of biochemical oxygen demand (BOD) of the sewage exclusion standard. It is a burden.

  In addition, the foam chemical for fire extinguishing equipment test (for example, the above-mentioned Patent Document 2) in which the biochemical oxygen demand (BOD) is kept within the sewage exclusion standard is for testing mainly used for inspection of the fire extinguishing equipment and fire fighting training. Therefore, it cannot be used for fire extinguishing equipment because it does not have the performance as a foam fire extinguishing agent according to the ministerial ordinance that defines the technical standards of the above-mentioned foam fire extinguishing agent. Does not meet the stated test criteria.

  This invention is made | formed in view of the said situation, and makes it a subject to provide the environmental consideration type | formula fire extinguisher which can satisfy the exclusion standard of sewage.

  In order to solve the above-mentioned problems, the environmentally friendly foam fire-extinguishing agent according to the present invention described in claim 1 includes a hydrocarbon anionic surfactant and a hydrocarbon amphoteric surfactant as active ingredients. To do.

The invention according to claim 2 is the invention according to claim 1, wherein the hydrocarbon-based anionic surfactant has a general formula: RCH = CH (CH ₂ ) _n SO ₃ Z (R is a carbon number of 8 to 30). An aliphatic hydrocarbon group, n is 0 to 5, Z is an alkali metal and / or alkaline earth metal), and the hydrocarbon-based amphoteric surfactant is represented by the general formula: RN It is characterized by being lauryldimethylaminoacetic acid betaine represented by ⁺ CH (CH ₃ ) ₂ CH ₂ COO ⁻ (R is an aliphatic hydrocarbon group having 8 to 30 carbon atoms).

  The invention according to claim 3 is the invention according to claim 2, wherein the active ingredient concentration of the alpha olefin sulfonate which is the hydrocarbon-based anionic surfactant is in the range of 1.3 to 3.0% by weight. It is characterized by being.

  The invention according to claim 4 is the invention according to claim 2 or 3, wherein the active ingredient concentration of the hydrocarbon amphoteric surfactant lauryldimethylaminoacetic acid betaine is 0.3 to 1.3% by weight. It is characterized by the above.

  The invention according to claim 5 is the invention according to any one of claims 2 to 4, wherein the sum of the active ingredient concentration of the alpha olefin sulfonate and the active ingredient concentration of the lauryldimethylaminoacetic acid betaine is 2. It is characterized by being in the range of 6278 to 3.8010% by weight.

  In general, the synthetic surfactant foam extinguishing agent released from the foam head is 25% or more in the expansion ratio of 6 times or more according to the ministerial ordinance (Ministry of Self-government Ordinance No. 26 of 1975) that establishes technical standards for foam extinguishing agents. Satisfy the criteria of a reduction time of 1 minute or more and a fire extinguishing time of 5 minutes or less.

  In addition, according to the test method and standard described in Non-Patent Document 1, the expansion ratio is 5 times or more in fresh water (total hardness less than 184 ppm (measured according to JIS K0101)) and hard water (total hardness of 184 ppm or more). The 25% reduction time of the foam volume satisfies the standard of 30 seconds or more.

  According to the present invention, the above-mentioned ministerial ordinance for setting technical standards for foam fire extinguishing agents satisfies the standard of foaming magnification of 6 times or more, 25% reduction time of 1 minute or more, and fire extinguishing time of 5 minutes or less, And the test standard described in the said nonpatent literature 1 can be satisfied.

  As a result, according to the present invention, it becomes possible to satisfy the sewage drainage standard, and thus solve the burden of collecting used foam extinguishing agent by the equipment owner when dealing with a fire in equipment such as a parking lot. can do.

Hereinafter, an embodiment of an environmentally friendly foam fire extinguishing agent according to the present invention will be described.
This environmentally friendly foam fire-extinguishing agent contains a hydrocarbon-based anionic surfactant and a hydrocarbon-based amphoteric surfactant as its active ingredients.

  Here, as the hydrocarbon-based anionic surfactant, alkyl ether sulfate ester salt, alpha olefin sulfonate salt, alkylbenzene sulfonic acid and its salt, alkyl sulfate ester salt, ether sulfonate salt, ether carboxylate salt, sulfosuccinic acid Salts, methyl taurate, alaninate and salts thereof, and mixtures of one or more thereof. Of these, alkyl ether sulfates and alpha olefin sulfonates are preferred.

Further, particularly preferred is an alpha olefin sulfonate represented by the general formula: RCH═CH (CH ₂ ) _n SO ₃ Z. Here, the aliphatic hydrocarbon group having 8 to 30 carbon atoms represented by R may be either saturated or unsaturated, and may be linear or branched. For example, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group, oleyl group, linoleyl group, linolenyl group, etc. Is mentioned. Among these, those having 8 to 20 carbon atoms are preferable from the viewpoint of foaming power, and a tetradecyl group is particularly preferable.

  Moreover, n in the said general formula shows the average mole number of a methyl group, and is the range of 0-5. Incidentally, if the number of added moles exceeds 5, it is not preferable because the foaming power deteriorates.

  Furthermore, Z in the above general formula represents an alkali metal, an alkaline earth metal, or a mixture of both, such as lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, radium, and 2 A mixture of more than one type can be mentioned. Of these, sodium, potassium, magnesium and calcium are preferred.

  The alpha olefin sulfonate can be prepared by alpha olefin sulfonation, but usually can be obtained as a mixture of alkenyl sulfonate and hydroxyalkane sulfonate, so that commercially available alkenyl sulfonate and It can also be obtained as a mixture of hydroxyalkane sulfonates.

  Further, as the hydrocarbon-based amphoteric surfactant, it is necessary to use one that does not inhibit the foaming property of the foaming agent of the present invention. For example, alanine type, imidazolinium betaine type, alkyl betaine type, aminopropyl betaine Type, aminodipropion type, and the like, and one or a mixture of two or more thereof.

Of these, lauryldimethylaminoacetic acid betaine represented by the general formula: RN ⁺ CH (CH ₃ ) ₂ CH ₂ COO ⁻ is particularly preferable. Here, the aliphatic hydrocarbon group having 8 to 30 carbon atoms represented by R may be either saturated or unsaturated, and may be linear or branched. Particularly preferred is a lauryl group.

  Moreover, you may use together a nonionic surfactant, a water-soluble inorganic metal salt, a water-soluble organic solvent, a water-soluble polymer, a dispersing agent etc. in the said environmental consideration type | formula fire extinguishing agent as needed. In particular, nonionic surfactants and water-soluble organic solvents have the effect of improving foam stability.

  Examples of the nonionic surfactant include alkyl ether types, alkylphenol types, alkyl ester types, and amine oxide types. Examples of water-soluble inorganic metal salts include magnesium salts (magnesium sulfate, magnesium chloride, etc.), calcium salts, and the like. (Calcium sulfate, calcium chloride, etc.).

  In addition, as the water-soluble organic solvent, it is necessary to use a solvent that does not inhibit the foaming property of the environmentally friendly foam fire extinguishing agent of the present invention. For example, cellosolve solvents (such as methyl cellosolve, ethyl cellosolve, butyl cellosolve), carbitols (Ethyl carbitol, butyl carbitol, etc.), polyoxyethylene lower alkyl ether having 3 to 10 added moles of ethylene oxide, diols (ethylene glycol, diethylene glycol, etc.), alcohols (ethyl alcohol, lauryl alcohol, etc.), etc. Can be mentioned.

  Furthermore, examples of the water-soluble polymer include cellulose derivatives (methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, etc.), polyvinyl alcohol, polyethylene glycol and the like, and examples of the dispersant include naphthalene sulfonic acid type, alkyl naphthalene sulfonic acid type. , Polycarboxylic acid type, polyacrylic acid type and the like.

  When using the environment-friendly foam fire extinguishing agent according to the present invention, in the form of an aqueous solution diluted to the use concentration in advance, this environmentally friendly type is used in the method of use by pumping or pumping by gas pressure, or in the line of fire extinguishing equipment. A method of using a foam extinguishing agent so as to be incorporated can be employed.

Hereinafter, the effects of the present invention will be described in detail with reference to examples, but the present invention is not limited thereto.
As shown in Table 1, a hydrocarbon-based anionic surfactant, sodium alpha olefin sulfonate (trade name “Lipolane LB-440”, manufactured by Lion Corp .: RCH = CH (CH ₂ ) _n SO ₃ Na (R 14) and lauryldimethylaminoacetate betaine (trade name “Amphithol 20BS”, manufactured by Kao Corporation: RN ⁺ CH (CH ₃ ) ₂ CH ₂ COO ⁻ (R Using a carbon number of 12), the pH was adjusted with 50% sulfuric acid (reagent grade 1) to prepare an environmentally friendly foam fire-extinguishing agent.

50% sulfuric acid was prepared by mixing 20 ml of water: 20 ml of sulfuric acid.
The following test was conducted by diluting 3 ml of the environmentally friendly foam extinguishing agent thus obtained to 97 ml of water.

<Exclusion criteria for sewage>
Based on the Decree No. 147 of April 22, 1959; the Sewerage Law Enforcement Ordinance, the sewage exclusion standard was tested. Table 2 shows the results.

  As can be seen from Table 2, according to the environmentally friendly foam fire extinguishing agent according to the present invention, it can be seen that the sewage law enforcement order and the sewage exclusion standard are satisfied.

  Next, using the environmentally friendly foam fire extinguishing agent shown in Table 1, the foaming test and the fire extinguishing test as a foam fire extinguishing agent were conducted using a standard foaming nozzle that complies with the ministerial ordinance stipulating the technical standards for foam extinguishing agents. did.

<Foam extinguishing agent foam test>
Test conditions Standard foam nozzle: For synthetic surfactant foam fire extinguishing agent test Foam collection container: foam sample container (capacity: 1400 ml)
Water discharge amount: 10.0L / min
Water discharge pressure: 0.7 MPa
Water temperature / temperature: 20 ± 2 ℃

For foaming, the environmentally friendly foam extinguishing agent diluted to 3% is discharged with a standard foaming nozzle for synthetic surfactant foam extinguishing agent test, and bubbles are taken into a foam sample container (capacity: 1400 ml) and its mass (g) is measured. Then, the expansion ratio was calculated by the following formula.
Foaming ratio (times) = 1400 / bubble mass (g)

The 25% reduction time measures the time until the foam collected by the above method returns to an aqueous solution of 25% of the total volume. Here, the amount of reduction until the foam reached 25% of the total volume was determined by the following equation.
25% reduction amount (g) = foam mass (g) × 25%
(Criteria) Foaming ratio 6 times or more, 25% reduction time 1 minute or more

<Foam extinguishing chemical fire extinguishing test>
In the fire extinguishing test, an environmentally friendly foam extinguishing agent diluted to 3% was discharged for 8 minutes with a standard foam nozzle for synthetic surfactant foam extinguishing agent test, and the time until extinguishing was measured.
Test conditions Standard foam nozzle: Synthetic surfactant Foam extinguishing water discharge: 10.0 L / min
Water discharge pressure: 0.7 MPa
Water temperature / temperature: 20 ± 2 ℃
Test equipment: Iron burning dish (length: 200cm, width: 200cm, depth: 30cm)
(Criteria) Emission for 8 minutes and extinguish within 5 minutes.
Table 3 shows these results.

  From Table 3, the environmentally friendly foam fire extinguishing agent according to the present invention has a foaming ratio of 6 times or more, a 25% reduction time of 1 minute or more, and a fire extinguishing time of 5 minutes, as defined in the ministerial ordinance for establishing technical standards for foam fire extinguishing agents. It can be seen that the product satisfies the standard specified within.

Therefore, in order to compare the environmentally friendly foam fire extinguishing agent according to the present invention with other foam extinguishing agents, the following tests were conducted.
First, the above-mentioned sodium alpha olefin sulfonate (trade name “Lipolane LB-440”, manufactured by Lion Corporation: RCH = CH (CH ₂ ) _n SO ₃ Na and betaine lauryl dimethylaminoacetate (trade name “Amphithol 20BS”) , Manufactured by Kao Corporation: RN ⁺ CH (CH ₃ ) ₂ CH ₂ COO ⁻ (R 12 carbon atoms), and foam extinguishing of Examples 1 to 4 and Comparative Examples 1 and 2 according to the formulation shown in Table 4 The drug was made.

  Foam combined with biochemical oxygen demand (BOD) and foam head for 3 ml of foam extinguishing agent and 97 ml of water adjusted pH with 50% sulfuric acid (reagent grade 1, Wako Pure Chemical Industries, Ltd.) Tests and fire extinguishing tests were conducted.

  The foaming test and the fire extinguishing test were performed in combination with a foam head and a foam fire extinguishing agent according to the performance evaluation of the foam head according to the test method described in Non-Patent Document 1 above.

<Foaming test>
Test condition Foam outlet: Foam head (Japan Fire Equipment Safety Center performance rating product)
Number of heads: 1 Test device: Foam sample collector (synthetic interface foam)
Foam collection container: graduated cylinder (1000ml)
Water discharge amount: 35 l / min
Water discharge pressure: 0.25 MPa
Water temperature / temperature: 20 ± 2 ℃

For foaming, the foam extinguishing agent diluted 3% is pumped with a pressurizing device, discharged using a foam head, foamed, and the foamed foam is clarified with a foam sample collector into a graduated cylinder (capacity: 1000 ml). And the mass (g) was measured, and the expansion ratio was calculated by the following formula.
Foaming magnification (times) = 1000 (ml) / mass of foam (g)

The 25% reduction time measures the time until the foam collected by the above method returns to an aqueous solution of 25% of the total volume. The amount of reduction until the foam reached 25% of the total volume was determined by the following equation.
25% reduction amount (g) = foam mass (g) × 25%
(Criteria) Foaming ratio is 5 times or more, 25% reduction time is 30 seconds or more

<Fire extinguishing test>
Test conditions
In the fire-extinguishing test, four heads were arranged in a square, and an environmentally friendly foam-extinguishing agent diluted to 3% after 1 minute of pre-combustion time was emitted for 1 minute for testing.
Foam discharge port: Foam head (Japan Fire Equipment Safety Center performance rating product)
Number of heads: 4 (square arrangement)
Water discharge amount: 35 l / min
Water discharge pressure: 0.25 MPa
Water temperature / temperature: 20 ± 2 ℃
Test equipment: Iron burning dish (length: 200cm, width: 100cm, depth: 20cm)
(Criteria) Must extinguish when radiated for 1 minute.

<Biochemical oxygen demand (BOD)>
The biochemical oxygen demand (BOD) was tested according to JIS K0102-21.
Dilution water adjustment: Add 1 ml each of liquid A, liquid B, liquid C and liquid D to 1 liter of aerated water.
Solution A: 1000 ml of 21.75 g of dipotassium hydrogen phosphate, 8.5 g of potassium dihydrogen phosphate, 44.6 g of sodium hydrogen phosphate and 12 water, and 1.7 g of ammonium chloride dissolved in water.
Solution B: 1000 ml of 22.5 g of magnesium sulfate heptahydrate dissolved in water.
Solution C: 1000 ml of 27.5 g of calcium chloride dissolved in water.
Solution D: 1000 ml of 1.6 g of iron (III) chloride hexahydrate dissolved in water.

<Adjustment of diluted sample>
Put about half of the diluted solution into a 1000 ml stoppered graduated cylinder, add the pretreated sample, and make up to 1000 ml with diluted water. Cap and mix gently. Similarly, adjust the dilution factor. A diluted sample is put in a culture bottle, one is a sample before culturing, and the other is put in a thermostat adjusted to 20 ± 1 ° C. and cultured for 5 days.

Diluted samples are prepared for 15 minutes after adjustment and those cultured for 5 days in a thermostatic bath. The dissolved oxygen is measured by the diaphragm electrode method, and the biochemical oxygen demand (BOD) is calculated by the following formula.
_{BOD = (D 1 -D 2)} / P
Where BOD: biochemical oxygen demand (mgO / l)
D ₁ : Dissolved oxygen (mgO / l) 15 minutes after preparing the diluted sample
D ₂ : Dissolved oxygen (mgO / l) of the diluted sample after culture
P: The ratio of the sample in the diluted data (sample / diluted sample).

<Diaphragm electrode method>
Sodium sulfite (25 g → 500 ml) is injected into a dissolved oxygen measuring device, and zero adjustment is performed by inserting an electrode while stirring with a magnetic stirrer. Next, dissolved oxygen saturated water is injected, and the indicated value is adjusted from “JIS K0102 Table 32.1 Saturated dissolved oxygen in water”. The sample is then injected and the biochemical oxygen demand (BOD) is measured.
Table 5 shows the results of the above test.

  From the results shown in Table 5, Examples 1 to 4 satisfy the Sewerage Law Enforcement Ordinance, the biochemical oxygen demand of the sewage exclusion standard, and the standard value of less than 600 mg / l, and are described in Non-Patent Document 1 above. It can be seen that the test method satisfies the performance of extinguishing after foam emission after 5 minutes of foaming magnification of 5 times or more, 25% reduction time of 30 seconds or more, which is the standard of foam extinguishing agent used in the foam head.

  On the other hand, in Comparative Example 1, the fire extinguishing time is 1 minute or more, and in Comparative Example 2, the biochemical oxygen demand is 600 mg / l or more, so none of the above conditions is satisfied.

  The environmentally friendly foam fire extinguishing agent according to the present invention can be used for foam extinguishing equipment such as foam heads and foam hydrants, foaming agents for fire extinguishers, and foam extinguishing agents handled by fire brigades.

Claims (5)

  An environmentally friendly foam fire-extinguishing agent comprising a hydrocarbon anionic surfactant and a hydrocarbon amphoteric surfactant as active ingredients. The hydrocarbon-based anionic surfactant is
General formula: RCH = CH (CH ₂ ) _n SO ₃ Z (wherein R is an aliphatic hydrocarbon group having 8 to 30 carbon atoms, n is 0 to 5, Z is an alkali metal and / or alkaline earth metal) Alpha olefin sulfonate
Hydrocarbon amphoteric surfactant
The lauryldimethylaminoacetic acid betaine represented by the general formula: RN ⁺ CH (CH ₃ ) ₂ CH ₂ COO ⁻ (R is an aliphatic hydrocarbon group having 8 to 30 carbon atoms) Environmentally friendly foam extinguishing agent as described.   The environmentally friendly foam fire extinguishing according to claim 2, wherein an active ingredient concentration of the alpha olefin sulfonate which is the hydrocarbon-based anionic surfactant is in the range of 1.3 to 3.0% by weight. Drug.   The environmental consideration according to claim 2 or 3, wherein an active ingredient concentration of lauryldimethylaminoacetic acid betaine, which is a hydrocarbon amphoteric surfactant, is in the range of 0.3 to 1.3% by weight. Type foam extinguishing agent.   The total of the active ingredient concentration of the alpha olefin sulfonate and the active ingredient concentration of the lauryl dimethylaminoacetic acid betaine is in the range of 2.6278 to 3.8010% by weight. Environmentally friendly foam fire extinguishing agent as described in Crab.