Compound fluoride-free foam extinguishing agent matched with solid flame-retardant buoyancy material for use as well as preparation method and application of compound fluoride-free foam extinguishing agent

Abstract

The invention discloses a compound fluoride-free foam fire extinguishing agent used in cooperation with a solid flame-retardant buoyancy material and a preparation method and application of the compound fluoride-free foam fire extinguishing agent, and belongs to the field of fire extinguishing agents, the compound fluoride-free foam fire extinguishing agent comprises a fluoride-free foam fire extinguishing agent body and the solid flame-retardant buoyancy material, and the mixing mass ratio of the fluoride-free foam fire extinguishing agent body to the solid flame-retardant buoyancy material is 10-20: 1, the fluoride-free foam extinguishing agent comprises the following raw materials in parts by weight: 15%-25% of a mixed solution A, 30%-50% of a mixed solution B, 0.5%-1.5% of a foam stabilizer, 0.2%-0.3% of a preservative, 0.01%-0.1% of a pH regulator, 1%-5% of a phosphorus-containing flame retardant and the balance of water, the solid flame-retardant buoyancy material comprises hollow glass beads of which the surfaces are coated with a flame retardant. The foaming agent is composed of the organic silicon surfactant and the anionic surfactant, and meanwhile, the foaming agent and the solid flame-retardant buoyancy material have a synergistic effect, so that the burning resistance and foam stabilizing capacity of the fire extinguishing agent can be greatly improved.

Description

Technical Field

[0001] The invention relates to the field of fire extinguishing agents, and in particular to a compound fluorine-free foam fire extinguishing agent used in combination with a solid flame-retardant buoyancy material, and a preparation method and application thereof. Background Art

[0002] Foam fire extinguishing agent is recognized as the most effective technical means to extinguish Class B flammable liquid fires. Foam fire extinguishing agent can be dissolved in water and relies on chemical reactions between substances or mechanical devices to produce fire-extinguishing foam. It is used in many flammable liquid fire scenes, such as refineries, airports, offshore oil drilling platforms, etc. Foam fire extinguishing agents are classified according to their foaming multiples and can be divided into low, medium and high multiple foam fire extinguishing agents. The low multiple foams with the largest demand among foam fire extinguishing agents are gradually developing towards water-film-forming foam fire extinguishing agents. The fluorocarbon surface fire extinguishing agent in its formula can greatly reduce the surface tension of aqueous liquids and the interfacial tension between gas and liquid, thereby ensuring that when extinguishing flammable liquid fires, it can quickly generate a layer of water film on the surface of the oil, and then rely on the dual effects of the water film layer and the foam layer to quickly control and extinguish the fire.

[0003] Aqueous film-forming foam fire extinguishing agents are mainly prepared with fluorocarbon surfactants and hydrocarbon surfactants as base materials, and the core component is fluorocarbon surfactants. Perfluorooctane sulfonic acid (PFOS) and its salts are the best and most common fluorocarbon surfactants. The latest research has found that fluorocarbon surfactants represented by PFOS and related salts have serious ecological destructiveness and environmental pollution problems. Because PFOS has extremely high chemical and thermal stability, it can be active in the food chain and accumulate and migrate accordingly. It is difficult to be degraded for a long time, so it will pollute the environment and seriously threaten the survival of animals and plants. In response to this problem, some scholars use short-chain fluorocarbon surfactants or fluorine-free surfactants instead of PFOS, but the fire extinguishing performance of short-chain fluorocarbon or fluorine-free surfactants is often greatly reduced. Therefore, it is of great significance to study a new type of fluorine-free, highly stable Class B foam fire extinguishing agent. Summary of the invention

[0004] Purpose of the Invention

[0005] In order to overcome the above shortcomings, the purpose of the present invention is to provide a composite fluorine-free foam fire extinguishing agent used in combination with a solid flame-retardant buoyancy material, and its preparation method and application. The fluorine-free foam fire extinguishing agent of the present invention works synergistically with the solid flame-retardant buoyancy material to greatly improve the fire resistance and foam stabilization ability of the fire extinguishing agent, thereby improving the fire extinguishing performance of the fire extinguishing agent. The material is green and environmentally friendly, and the production process of the fire extinguishing agent is simple and the production cycle is short.

[0006] Solution

[0007] To achieve the purpose of the present invention, the technical solution adopted by the present invention is as follows:

[0008] In a first aspect, the present invention provides a compound fluorine-free foam fire extinguishing agent used in combination with a solid flame retardant buoyancy material, comprising: a fluorine-free foam fire extinguishing agent and a solid flame retardant buoyancy material, wherein the mass ratio of the fluorine-free foam fire extinguishing agent to the solid flame retardant buoyancy material is 10 to 20:1, wherein:

[0009] The fluorine-free foam fire extinguishing agent comprises the following raw materials in parts by weight: 15% to 25% of mixed liquid A, 30% to 50% of mixed liquid B, 0.5% to 1.5% of foam stabilizer, 0.2% to 0.3% of preservative, 0.01% to 0.1% of pH regulator, 1% to 5% of phosphorus-containing flame retardant, and the balance is water;

[0010] Optionally, the mixed solution A includes a fluorine-free surfactant, ethylene glycol and a cosolvent;

[0011] Optionally, the mixed solution B includes an anionic surfactant, urea, alkyl polyglycoside and water;

[0012] The solid flame retardant buoyancy material comprises hollow glass microspheres with flame retardant coated on the surface.

[0013] Fluorine-free foam fire extinguishing agent and solid flame retardant buoyancy material can be used in a pre-mixed manner or re-mixed when used.

[0014] Furthermore, the mixing mass ratio of the fluorine-free foam fire extinguishing agent and the solid flame retardant buoyancy material is 10 to 15:1, wherein:

[0015] The fluorine-free foam fire extinguishing agent includes 20% to 25% of mixed liquid A, 40% to 50% of mixed liquid B, 1% to 1.5% of foam stabilizer, 0.2% of preservative, 0.05% to 0.1% of pH adjuster, 2% to 5% of phosphorus-containing flame retardant, and the balance is water;

[0016] Furthermore, in the mixed liquid A, the mass ratio of the fluorine-free surfactant, the cosolvent and ethylene glycol is 2.5-4.9:0.1-0.5:5-7, optionally 3-3.9:0.1-0.2:6-6.8; optionally, the fluorine-free surfactant includes a silicone surfactant, and optionally the silicone surfactant includes one or more of siloxane polyoxyethylene ether, dodecyl glucoside, dodecyl dimethyl betaine and cocamidopropyl betaine; optionally, the cosolvent is one of diethylene glycol butyl ether and ethyl ether.

[0017] Furthermore, in the mixed solution B, the mass ratio of anionic surfactant, alkyl glycoside, urea and water is 1-3:0.2-0.5:0.2-0.5:6-8, optionally 1-2:0.2-0.5:0.2-0.5:6-7; optionally, the anionic surfactant is one or more of sodium dodecyl sulfate, sodium α-olefin sulfonate, sodium fatty alcohol polyoxyethylene ether sulfate and α-sulfo fatty acid methyl ester.

[0018] Furthermore, the foam stabilizer includes one or more of fatty alcohol polyoxyethylene ether, xanthan gum, and guar gum;

[0019] and / or, the preservative includes one or more of sodium benzoate and potassium sorbate;

[0020] And / or, the pH adjuster includes one of citric acid and acetic acid.

[0021] Furthermore, in the solid flame retardant buoyancy material, the particle size of the glass microspheres is 10 to 250 μm, optionally 30 to 120 μm, and the density is 0.15 to 0.60 g / cm 3 .

[0022] Optionally, in the solid flame retardant buoyancy material, the flame retardant and the hollow microspheres are obtained by mixing and drying. Optionally, in the solid flame retardant buoyancy material, the flame retardant and the hollow microspheres are obtained by adding water, mixing and drying, and the water is almost evaporated during the drying process.

[0023] Optionally, the weight ratio of the hollow glass microspheres to the flame retardant is 6-7:3-4; optionally, the glass microspheres account for 60-70% of the total mass of the solid flame retardant buoyancy material.

[0024] Optionally, in the solid flame-retardant buoyancy material, the flame retardant is a phosphorus-containing flame retardant.

[0025] Optionally, in the solid flame retardant buoyancy material and / or the fluorine-free foam fire extinguishing agent, the phosphorus-containing flame retardant is independently selected from one or more of tris(2-chloroethyl)phosphate, tris(2-chloropropyl)phosphate, dimethyl methyl phosphate, and diethyl ethyl phosphate.

[0026] In a second aspect, a method for preparing the composite fluorine-free foam fire extinguishing agent used in combination with the solid flame retardant buoyancy material according to the first aspect is provided, characterized in that the method comprises the following steps:

[0027] (1) uniformly mixing the fluorine-free surfactant, ethylene glycol and cosolvent;

[0028] (2) uniformly mixing anionic surfactant, alkyl polyglycoside, urea and water;

[0029] (3) Add mixed solution A to mixed solution B and mix well; add foam stabilizer and pH adjuster and mix well;

[0030] (4) Add the preservative and the remaining water dropwise and mix well to obtain a fluorine-free foam fire extinguishing agent.

[0031] (5) Preparation of hollow glass microspheres with surface covered with flame retardant.

[0032] Further, the mixing method in step (1) comprises: mixing and stirring at room temperature for 30 min-1 h, optionally with a stirring speed of 1000-2000 r / min;

[0033] And / or, the mixing method in step (2) comprises: mixing and stirring at room temperature for 20-50 min, optionally with a stirring speed of 1000-2000 r / min;

[0034] And / or, in step (3), the mixing method is stirring, optionally stirring at room temperature for 1-2 hours, and optionally the stirring speed is 1000-2000 r / min;

[0035] And / or, in step (4), stirring at room temperature for 1-3 h, with a stirring speed of 1000-2000 r / min;

[0036] And / or, in step (5), in the solid flame retardant buoyancy material, the flame retardant and the hollow microspheres are obtained by mixing and drying, and optionally, 10 to 20% by mass of water is added when the flame retardant and the hollow microspheres are mixed (the water will be almost evaporated during drying).

[0037] In a third aspect, a method for using the composite fluorine-free foam fire extinguishing agent used in combination with the solid flame-retardant buoyancy material described in the first aspect or the fire extinguishing agent prepared by the preparation method of the second aspect is provided, wherein the solid flame-retardant buoyancy material and the fluorine-free foam fire extinguishing agent are mixed in a mass ratio of 10 to 20:1; optionally, the fluorine-free foam fire extinguishing agent and the solid flame-retardant buoyancy material are premixed or mixed during use.

[0038] In a fourth aspect, there is provided a use of the composite fluorine-free foam fire extinguishing agent used in combination with the solid flame-retardant buoyancy material described in the first aspect or the fire extinguishing agent prepared by the preparation method described in the second aspect in the preparation of a fire extinguishing agent.

[0039] Beneficial Effects

[0040] (1) The fluorine-free foam fire extinguishing agent of the present invention includes a foaming agent composed of a compound of an organic silicon surfactant and an anionic surfactant, which can synergize with the salts on the surface of the solid flame retardant buoyancy material to greatly improve the foaming multiple and foam height, thereby greatly improving the fire extinguishing performance of the fire extinguishing agent.

[0041] (2) The phosphorus-containing flame retardant in the solid flame-retardant buoyancy material of the present invention releases oxygen-containing free radicals when heated, which can capture the free radicals released by the burning matrix, thereby reducing the combustion intensity and even interrupting the combustion effect. The solid flame-retardant buoyancy material of the present invention is a micron-level lightweight material with a general particle size of 10 to 250 μm. It can be mixed with a foam fire extinguishing agent and sprayed through a spray gun to achieve the purpose of fire extinguishing. The compound fluorine-free foam fire extinguishing agent of the present invention has good fire extinguishing performance in large oil pan fire extinguishing detection. DETAILED DESCRIPTION

[0042] In order to make the purpose, technical solution and advantages of the embodiments of the present invention clearer, the technical solution in the embodiments of the present invention will be described clearly and completely below. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0043] In addition, in order to better illustrate the present invention, numerous specific details are provided in the specific embodiments below. It should be understood by those skilled in the art that the present invention can also be implemented without certain specific details. In some embodiments, raw materials, elements, methods, means, etc. well known to those skilled in the art are not described in detail, so as to highlight the main purpose of the present invention.

[0044] Unless explicitly stated otherwise, throughout the specification and claims, the term “comprise” or variations such as “include” or “comprising”, etc., will be understood to include the stated elements or components but not to exclude other elements or components.

[0045] The compound fluorine-free foam fire extinguishing agent of the present invention comprises a fluorine-free foam fire extinguishing agent and a solid flame retardant buoyancy material, and the mixing mass ratio of the two is 10 to 20:1; wherein the fluorine-free foam fire extinguishing agent comprises a mixed liquid A, a mixed liquid B, a foam stabilizer, and a phosphorus-containing flame retardant, wherein:

[0046] Mixed liquid A includes a mixed liquid of an organic silicon surfactant, a cosolvent and ethylene glycol (the weight ratio may be 2.5-4.9:0.1-0.5:5-7); the organic silicon surfactant includes one or more of siloxane polyoxyethylene ether, dodecyl glucoside, dodecyl dimethyl betaine and cocamidopropyl betaine; the cosolvent is an ether cosolvent, and may optionally include one of diethylene glycol butyl ether and ethyl ether;

[0047] Mixed liquid B includes a mixed liquid of anionic surfactant, alkyl polyglycoside, urea and water (weight ratio is 1-3:0.2-0.5:0.2-0.5:6-8); the anionic surfactant includes one or more of sodium dodecyl sulfate, sodium α-olefin sulfonate, sodium fatty alcohol polyoxyethylene ether sulfate and α-sulfo fatty acid methyl ester;

[0048] The solid flame-retardant buoyancy material includes hollow glass microspheres with flame retardants on the surface, which are obtained by mixing the hollow glass microspheres and the flame retardants (the mixing weight ratio can be 6-7:3-4) and then drying. The flame retardant includes one or more of tris(2-chloroethyl) phosphate, tris(2-chloropropyl) phosphate, dimethyl methyl phosphate or diethyl ethyl phosphate.

[0049] Example 1

[0050] A compound fluorine-free foam fire extinguishing agent, comprising a fluorine-free foam fire extinguishing agent and a solid flame retardant buoyancy material, the mass ratio of the two being 10:1; wherein:

[0051] The fluorine-free foam fire extinguishing agent includes the following components in percentage by mass: 20% of mixed liquid A, 40% of mixed liquid B, 1% of foam stabilizer, 0.2% of preservative, 0.1% of pH adjuster, 2% of phosphorus-containing flame retardant, and 36.7% of water;

[0052] The mixed solution A includes siloxane polyoxyethylene ether, diethylene glycol butyl ether and ethylene glycol in a mass ratio of 3.9:0.1:6; the mixed solution B includes sodium dodecyl sulfate, alkyl glycoside, urea and water in a mass ratio of 2:0.5:0.5:7; the foam stabilizer is fatty alcohol polyoxyethylene ether, the preservative is sodium benzoate, and the pH regulator is citric acid. The solid flame retardant buoyancy material includes 70% hollow glass microspheres and 30% tris(2-chloroethyl) phosphate.

[0053] The compound fluorine-free foam fire extinguishing agent is prepared by the following method:

[0054] Step 1, 78g of siloxane polyoxyethylene ether, 2g of diethylene glycol butyl ether and 120g of ethylene glycol were mixed and stirred at room temperature for 45min at a stirring speed of 1000-2000r / min to obtain a mixed solution A;

[0055] Step 2, 80g of sodium dodecyl sulfate, 2g of alkyl glycoside, 2g of urea and 280g of water were mixed and stirred at room temperature for 30min at a stirring speed of 1000-2000r / min to obtain a mixed solution B;

[0056] Step 3: Mix the mixed solutions prepared in step 1 and step 2, stir at room temperature for 1 hour, then add 10 g of fatty alcohol polyoxyethylene ether to the system, then add 2 g of citric acid, and stir at room temperature for 2 hours.

[0057] Step 4: Add 2 g of sodium benzoate and 367 g of water to the mixed solution obtained in step 3, and mix and stir for 2 h to obtain a fluorine-free foam fire extinguishing agent.

[0058] Step 5, preparation of solid flame retardant buoyancy material: mix 14g hollow glass microspheres (K15 from 3M Company, USA, particle size of 10-250μm) with 6g tri(2-chloroethyl) phosphate, add 5g water, stir for 3h, and then use fluidized bed drying for 3h to obtain the desired solid flame retardant buoyancy material.

[0059] When using, mix the fluorine-free foam fire extinguishing agent and solid flame retardant buoyancy material in a ratio of 10:1.

[0060] Example 2

[0061] A compound fluorine-free foam fire extinguishing agent, comprising a fluorine-free foam fire extinguishing agent and a solid flame retardant buoyancy material, the mass ratio of the two being 15:1; wherein:

[0062] The fluorine-free foam fire extinguishing agent includes the following components in percentage by mass: mixed liquid A 25%, mixed liquid B 40%, foam stabilizer 1.5%, preservative 0.2%, pH adjuster 0.05%, phosphorus-containing flame retardant 5%, water 28.25%;

[0063] The mixed solution A comprises cocamidopropyl betaine, diethylene glycol butyl ether and ethylene glycol in a mass ratio of 3:0.2:6.8, and the mixed solution B comprises sodium sulfate of fatty alcohol polyoxyethylene ether, alkyl glycoside, urea and water in a mass ratio of 2:0.5:0.5:7, wherein the foam stabilizer is xanthan gum, the preservative is potassium sorbate, and the pH regulator is citric acid. The solid flame retardant buoyancy material used in the compounding comprises 60% of hollow glass microspheres and 40% of tris(2-chloroethyl) phosphate in a mass fraction.

[0064] The compound fluorine-free foam fire extinguishing agent is prepared by the following method:

[0065] Step 1, 75g of cocamidopropyl betaine, 5g of diethylene glycol butyl ether and 170g of ethylene glycol were mixed and stirred at room temperature for 45min at a stirring speed of 1000-2000r / min to obtain a mixed solution A;

[0066] Step 2, 80g of sodium fatty alcohol polyoxyethylene ether sulfate, 2g of alkyl glycoside, 2g of urea and 280g of water were mixed and stirred at room temperature for 30min at a stirring speed of 1000-2000r / min to obtain a mixed solution B;

[0067] Step 3: Mix the mixed solutions prepared in step 1 and step 2, stir at room temperature for 1 hour, then add 15 g of xanthan gum and 2 g of citric acid into the system, and stir at room temperature for 2 hours.

[0068] Step 4: Add 5 g potassium sorbate and 282.5 g water to the mixed solution obtained in step 3, and mix and stir for 2 h to obtain a fluorine-free foam fire extinguishing agent.

[0069] Step 5, preparation of solid flame retardant buoyancy material: mix 12g hollow glass microspheres (S15 from 3M Company, USA, particle size of 10-250μm) with 8g tri(2-chloroethyl) phosphate, add 2.4g water, stir for 3h, and then use fluidized bed drying for 3h to obtain the desired solid flame retardant buoyancy material.

[0070] When in use, mix the fluorine-free foam fire extinguishing agent and the solid flame retardant buoyancy material in a ratio of 15:1. The solid flame retardant buoyancy material is a micron-level lightweight material, which can be mixed with the foam fire extinguishing agent and then sprayed out through a spray gun.

[0071] Comparative Example 1

[0072] A non-compounded fluorine-free foam fire extinguishing agent, which only includes fluorine-free foam fire extinguishing agent and does not include solid flame retardant buoyancy materials;

[0073] The fluorine-free foam fire extinguishing agent is the same as the fluorine-free foam fire extinguishing agent in Example 2 and is not compounded with the solid flame-retardant buoyancy material.

[0074] The non-compounded fluorine-free foam fire extinguishing agent is prepared by the following method:

[0075] Step 1, 75g of cocamidopropyl betaine, 5g of diethylene glycol butyl ether and 170g of ethylene glycol were mixed and stirred at room temperature for 45min at a stirring speed of 1000-2000r / min;

[0076] Step 2, 80g of fatty alcohol polyoxyethylene ether sodium sulfate, 2g of alkyl glycoside, 2g of urea and 280g of water were mixed and stirred at room temperature for 30min at a stirring speed of 1000-2000r / min;

[0077] Step 3: Mix the mixed solutions prepared in step 1 and step 2, stir at room temperature for 1 hour, then add 15 g of xanthan gum and 2 g of citric acid into the system, and stir at room temperature for 2 hours.

[0078] Step 4: Add 5 g potassium sorbate and 282.5 g water to the mixed solution obtained in step 3, and mix and stir for 2 h to obtain a fluorine-free foam fire extinguishing agent.

[0079] Comparative Example 2

[0080] A non-compounded fluorine-free foam fire extinguishing agent, comprising only a fluorine-free foam fire extinguishing agent (excluding a mixed liquid A), and excluding a solid flame retardant buoyancy material; wherein the fluorine-free foam fire extinguishing agent comprises the following components in percentage by mass: 60% of a mixed liquid B, 1.5% of a foam stabilizer, 0.2% of a preservative, 0.05% of a pH regulator, 5% of a phosphorus-containing flame retardant, and 33.25% of water;

[0081] Mixed liquid B comprises sodium polyoxyethylene fatty alcohol ether sulfate, alkyl glycoside, urea and water in a mass ratio of 2:0.5:0.5:7; the foam stabilizer is xanthan gum, the preservative is potassium sorbate, the pH adjuster is citric acid, and the phosphorus-containing flame retardant is polyphosphoric acid.

[0082] The fluorine-free non-compounded Class B foam fire extinguishing agent is prepared by the following method:

[0083] Step 1, 120g of sodium fatty alcohol polyoxyethylene ether sulfate, 3g of alkyl glycoside, 3g of urea and 420g of water were mixed and stirred at room temperature for 30min at a stirring speed of 1000-2000r / min;

[0084] Step 2: First add 15 g of xanthan gum and then add 2 g of citric acid to the system in step 1, and stir at room temperature for 2 h.

[0085] Step 3: Add 5 g potassium sorbate and 332.5 g water to the mixed solution obtained in step 3, and mix and stir for 2 h to obtain a fluorine-free foam fire extinguishing agent.

[0086] Comparative Example 3

[0087] A non-compounded fluorine-free foam fire extinguishing agent, comprising only a fluorine-free foam fire extinguishing agent (and excluding a mixed liquid B), and excluding a solid flame retardant buoyancy material; wherein the fluorine-free foam fire extinguishing agent comprises the following components in percentage by mass: 40% of mixed liquid A, 1% of a foam stabilizer, 0.2% of a preservative, 0.1% of a pH regulator, 2% of a phosphorus-containing flame retardant, and 56.7% of water;

[0088] Among them, the mixed liquid A includes silicone polyoxyethylene ether, diethylene glycol butyl ether and ethylene glycol mixed evenly in a mass ratio of 3.9:0.1:6; the foam stabilizer is fatty alcohol polyoxyethylene ether, the preservative is sodium benzoate, and the pH adjuster is citric acid.

[0089] The non-compounded fluorine-free Class B foam fire extinguishing agent is prepared by the following method:

[0090] Step 1, 156g of siloxane polyoxyethylene ether, 4g of diethylene glycol butyl ether and 240g of ethylene glycol were mixed and stirred at room temperature for 45min at a stirring speed of 1000-2000r / min;

[0091] Step 2: Add 10 g of fatty alcohol polyoxyethylene ether to the mixed solution in step 1, then add 2 g of citric acid, and stir at room temperature for 2 h.

[0092] Step 3: Add 20 g of ammonium polyphosphate, 2 g of sodium benzoate and 567 g of water to the mixed solution obtained in step 2, and mix and stir for 2 hours to obtain a foam fire extinguishing agent.

[0093] Comparative Example 4

[0094] Weigh 33g of polyether modified polysiloxane type silicone surfactant 8000, 24g of isobutyl alcohol, and 20g of diethylene glycol butyl ether respectively to form a mixed solution A; weigh 711g of water, 60g of urea, 70g of sodium dodecyl sulfate, 20g of alkyl glycoside, and 30g of water glass, and mix them evenly to form a mixed solution B; add the mixed solution B to the mixed solution A and stir; then add 10g of penetrant fatty alcohol polyoxyethylene ether and stir evenly; then add a mixed solution of 2g of xanthan gum and 12g of diethylene glycol butyl ether, and stir for 30min; then add 8g of citric acid, continue stirring for 5min, stop stirring, and obtain a fluorine-free foam fire extinguishing agent.

[0095] Performance Test:

[0096] The foaming and fire extinguishing performance of the fire extinguishing materials prepared in Example 1, Example 2, and Comparative Examples 1 to 4 were tested respectively. The foaming multiple and 25% liquid separation time of the foam fire extinguishing agent were tested according to the standard GB15308-2006 "Foam Fire Extinguishing Agent". The foam fire extinguishing agent was tested to extinguish a 144B oil pan (2.4m in diameter, 0.2m in depth, and 4.52m in area) with reference to the standards GB15308-2006 "Foam Fire Extinguishing Agent" and GB4351-2023 "Portable Fire Extinguisher". 2 , belonging to a large oil pan, the amount of fuel added is 144L) fire extinguishing time and burning resistance time (using strong release fire extinguishing test). The results are shown in Table 1.

[0097] Table 1. Foaming and fire extinguishing performance of Examples and Comparative Examples

[0098]

[0099] It can be seen from Table 1 that the compounded fluorine-free foam fire extinguishing agent of Examples 1 and 2 has excellent fire extinguishing performance for Class B fires, the fire extinguishing time during the strong release process in a large oil pan is less than 3 minutes, the anti-burning time is greater than 10 minutes, and the fire extinguishing grade is IA.

[0100] The toxicity of foam fire extinguishing agent was tested according to GB17835-2008 "Water-based fire extinguishing agent". The results are shown in Table 2.

[0101] Table 2 Safety test of Examples 1 and 2

[0102]

[0103] It can be seen from Table 2 that the fluorine-free foam fire extinguishing agents prepared in Examples 1 and 2 are highly safe and are ideal environmentally friendly foam fire extinguishing agents.

[0104] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or make equivalent replacements for some of the technical features therein. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A composite fluorine-free foam fire extinguishing agent used in conjunction with a solid flame retardant buoyancy material, characterized in that: include: Fluorine-free foam fire extinguishing agent and solid flame retardant buoyancy material, the mixing mass ratio of fluorine-free foam fire extinguishing agent and solid flame retardant buoyancy material is 10-20:1, among which, The fluorine-free foam fire extinguishing agent comprises the following raw materials in parts by weight: 15% to 25% of mixed liquid A, 30% to 50% of mixed liquid B, 0.5% to 1.5% of foam stabilizer, 0.2% to 0.3% of preservative, 0.01% to 0.1% of pH regulator, 1% to 5% of phosphorus-containing flame retardant, and the balance is water; Optionally, the mixed solution A includes a fluorine-free surfactant, ethylene glycol and a cosolvent; Optionally, the mixed solution B includes an anionic surfactant, urea, alkyl polyglycoside and water; The solid flame retardant buoyancy material comprises hollow glass microspheres with flame retardant coated on the surface.

2. The compound fluorine-free foam fire extinguishing agent according to claim 1, characterized in that: The mixing mass ratio of fluorine-free foam fire extinguishing agent and solid flame retardant buoyancy material is 10-15:1, among which: The fluorine-free foam fire extinguishing agent includes 20% to 25% of mixed liquid A, 40% to 50% of mixed liquid B, 1% to 1.5% of foam stabilizer, 0.2% of preservative, 0.05% to 0.1% of pH adjuster, 2% to 5% of phosphorus-containing flame retardant, and the balance is water.

3. The compound fluorine-free foam fire extinguishing agent according to claim 1 or 2, characterized in that: In the mixed solution A, the mass ratio of the fluorine-free surfactant, the cosolvent and the ethylene glycol is 2.5-4.9:0.1-0.5:5-7, and optionally 3-3.9:0.1-0.2:6-6.8; Optionally, the fluorine-free surfactant includes an organosilicon surfactant, and the organosilicon surfactant includes one or more of siloxane polyoxyethylene ether, dodecyl glucoside, dodecyl dimethyl betaine and cocamidopropyl betaine; Optionally, the co-solvent is one of diethylene glycol butyl ether and diethyl ether.

4. The composite fluorine-free foam fire extinguishing agent according to any one of claims 1 to 3, characterized in that: In the mixed solution B, the mass ratio of anionic surfactant, alkyl polyglycoside, urea and water is 1-3:0.2-0.5:0.2-0.5:6-8, and optionally 1-2:0.2-0.5:0.2-0.5:6-7; optionally, the anionic surfactant is one or more of sodium dodecyl sulfate, sodium α-olefin sulfonate, sodium fatty alcohol polyoxyethylene ether sulfate and α-sulfo fatty acid methyl ester.

5. The compound fluorine-free foam fire extinguishing agent according to any one of claims 1 to 4, characterized in that: The foam stabilizer includes one or more of fatty alcohol polyoxyethylene ether, xanthan gum, and guar gum; and / or, the preservative includes one or more of sodium benzoate and potassium sorbate; And / or, the pH adjuster includes one of citric acid and acetic acid.

6. The compound fluorine-free foam fire extinguishing agent according to any one of claims 1 to 5, characterized in that: In the solid flame retardant buoyancy material, the particle size of the glass microspheres is 10 to 250 μm, optionally 30 to 120 μm, and the density is 0.15 to 0.60 g / cm 3 ; Optionally, in the solid flame-retardant buoyancy material, the flame retardant and the hollow microspheres are obtained by mixing and drying; Optionally, in the solid flame-retardant buoyancy material, the flame retardant and the hollow microspheres are obtained by adding water, mixing, and drying, and the water evaporates during the drying process; Optionally, the weight ratio of hollow glass microspheres to flame retardant is 6-7:3-4; Optionally, the glass microspheres account for 60-70% of the total mass of the solid flame retardant buoyancy material; Optionally, in the solid flame-retardant buoyancy material, the flame retardant is a phosphorus-containing flame retardant; Optionally, in the solid flame retardant buoyancy material and / or the fluorine-free foam fire extinguishing agent, the phosphorus-containing flame retardant is independently selected from one or more of tris(2-chloroethyl)phosphate, tris(2-chloropropyl)phosphate, dimethyl methyl phosphate, and diethyl ethyl phosphate.

7. A method for preparing a composite fluorine-free foam fire extinguishing agent used in combination with a solid flame-retardant buoyancy material as claimed in any one of claims 1 to 6, characterized in that: The solid flame retardant buoyancy material and the fluorine-free foam fire extinguishing agent are prepared separately for mixed use, comprising the following steps: (1) uniformly mixing the fluorine-free surfactant, ethylene glycol and cosolvent; (2) uniformly mixing anionic surfactant, alkyl polyglycoside, urea and water; (3) Add mixed solution A to mixed solution B and mix well; add foam stabilizer and pH adjuster and mix well; (4) Add the preservative and the remaining water dropwise and mix well to obtain a fluorine-free foam fire extinguishing agent. (5) Prepare hollow glass microspheres with a flame retardant coated on the surface to obtain a solid flame retardant buoyancy material.

8. The preparation method according to claim 7, characterized in that: The mixing method in step (1) comprises: mixing and stirring at room temperature for 30 min-1 h, and optionally the stirring speed is 1000-2000 r / min; And / or, the mixing method in step (2) comprises: mixing and stirring at room temperature for 20-50 min, optionally with a stirring speed of 1000-2000 r / min; And / or, in step (3), the mixing method is stirring, optionally stirring at room temperature for 1-2 hours, and optionally the stirring speed is 1000-2000 r / min; And / or, in step (4), stirring at room temperature for 1-3 h, with a stirring speed of 1000-2000 r / min; And / or, in step (5), in the solid flame retardant buoyancy material, the flame retardant and the hollow microspheres are obtained by mixing and drying, and optionally, 10-20% by mass of water is added when the flame retardant and the hollow microspheres are mixed.

9. A method for using the composite fluorine-free foam fire extinguishing agent used in combination with a solid flame-retardant buoyancy material as claimed in any one of claims 1 to 6 or the fire extinguishing agent prepared by the preparation method as claimed in claim 7 or 8, characterized in that: The solid flame retardant buoyancy material and the fluorine-free foam fire extinguishing agent are mixed at a mass ratio of 10 to 20:1; optionally, the fluorine-free foam fire extinguishing agent and the solid flame retardant buoyancy material are pre-mixed or mixed during use.

10. Use of the composite fluorine-free foam fire extinguishing agent used in combination with a solid flame-retardant buoyancy material as claimed in any one of claims 1 to 6 or the fire extinguishing agent prepared by the preparation method as claimed in claim 7 or 8 in the preparation of fire extinguishing agents.

Images