Fluorine-free environmentally friendly foam fire extinguishing agent composition, fluorine-free environmentally friendly foam fire extinguishing agent, preparation method and application thereof

Abstract

The present invention relates to the technical field of foam fire extinguishing agents, and discloses a fluorine-free environmentally friendly foam fire extinguishing agent composition, a fluorine-free environmentally friendly foam fire extinguishing agent, and a preparation method and application thereof. The composition includes the following components that are stored independently or mixed in two or more: a first surfactant, a second surfactant, a foam stabilizer, an anti-burning agent, a co-solvent, a flame retardant, and water; the second surfactant is a combination of sodium dodecyl sulfate and cocoamidopropyl betaine with a mass ratio of 1:1-5. Using the composition provided by the present invention, a foam fire extinguishing agent with a small surface tension, strong hydrophilicity, strong foam stabilizing ability, short fire extinguishing time, and environmental friendliness can be prepared.

Description

Technical Field

[0001] The present invention relates to the technical field of foam fire extinguishing agents, and particularly relates to a fluorine-free environmentally friendly foam fire extinguishing agent composition, a fluorine-free environmentally friendly foam fire extinguishing agent, and a preparation method and application thereof. Background Art

[0002] The core component of traditional aqueous film-forming foam fire extinguishing agents, perfluorooctane sulfonate (PFOS), has serious environmental pollution problems such as poor degradability and toxicity. Although the addition amount of fluorocarbon surfactants in aqueous film-forming foam fire extinguishing agents is low, once a large-scale fire occurs, the extensive use of aqueous film-forming foam fire extinguishing agents will cause irreparable ecological disasters.

[0003] With the increasingly strict national environmental protection laws and policies, domestic and foreign researchers have started to develop new, highly efficient, and degradable PFOS substitutes to reduce the environmental hazards caused by the use of foam fire extinguishing agents. In addition to fluorocarbon surfactants, surfactants also include two major categories: hydrocarbon surfactants and silicone surfactants.

[0004] Among them, hydrocarbon surfactants have serious deficiencies in terms of reducing surface tension performance. At most, they can only reduce the surface tension of water to about 30 mN / m, making the spreading coefficient less than zero and making it difficult to quickly spread into a film on the burning oil surface.

[0005] Most silicone surfactants are composed of polydimethylsiloxane as the hydrophobic main chain, with one or more silicone polar groups connected in the middle or at the end. Their hydrophobic properties are stronger than those of hydrocarbon surfactants, and they have excellent surface activity (surface tension is about 20 - 30 mN / m). At the same time, silicone surfactants have excellent high and low temperature resistance, good spreading properties, and low toxicity and environmental friendliness. Developing highly efficient and environmentally friendly foam fire extinguishing agents using silicone surfactants can fundamentally solve the potential environmental problems of fluorocarbon surfactants, which is of great significance.

[0006] CN106075792A discloses a highly efficient and environmentally friendly foam fire extinguishing agent, whose formula consists of a composite surfactant, an organic solvent, a stabilizer, an anti-burning agent, a chelating agent, a preservative, and water. The foam performance of this foam fire extinguishing agent can meet national standards, but due to the poor hydrophilic ability of the silicone surfactant, a high content of organic solvent is used, and there are still problems with poor environmental protection performance and fire extinguishing performance.

[0007] Therefore, developing a silicone surfactant that can be used in foam fire extinguishing agents and has strong hydrophilic ability and high surface activity is of great significance to the field of fire extinguishing agents. Summary of the Invention

[0008] One of the objectives of the present invention is to solve the problem of poor surface activity and hydrophilic performance of silicone surfactants in the prior art.

[0009] Another objective of the present invention is to solve the problem of poor environmental protection performance of aqueous film-forming foam extinguishing agents in the prior art.

[0010] To achieve the above objectives, the first aspect of the present invention provides a fluorine-free environmentally friendly foam extinguishing agent composition, which comprises the following components stored independently or in combination of two or more:

[0011] A first surfactant, a second surfactant, a foam stabilizer, an anti-burning agent, a co-solvent, a flame retardant, and water;

[0012] The second surfactant is a combination of sodium dodecyl sulfate and cocamidopropyl betaine with a mass ratio of 1:1 - 5;

[0013] Based on the total mass of the composition, the content of the first surfactant is 0.5 - 5 wt%, the content of the second surfactant is 5 - 30 wt%, the content of the foam stabilizer is 0.2 - 3 wt%, the content of the anti-burning agent is 1 - 6 wt%, the content of the co-solvent is 1 - 5 wt%, the content of the flame retardant is 4 - 10 wt%, and the content of water is 50 - 80 wt%;

[0014] The first surfactant is prepared by a method comprising the following steps:

[0015] S1. In the presence of a catalyst, allyl polyoxyalkylene epoxy ether and polymethylhydrogensiloxane are subjected to Reaction I to obtain epoxy polyether modified silicone oxide;

[0016] S2. In the presence of a solvent, the epoxy polyether modified silicone oxide and sodium bisulfite are subjected to Reaction II.

[0017] The second aspect of the present invention provides a method for preparing a fluorine-free environmentally friendly foam extinguishing agent, which comprises: mixing the components in the composition described in the first aspect.

[0018] The third aspect of the present invention provides a fluorine-free environmentally friendly foam extinguishing agent prepared by the method described in the second aspect.

[0019] The fourth aspect of the present invention provides the application of the fluorine-free environmentally friendly foam extinguishing agent described in the third aspect in class B fires of flammable liquids in the petrochemical field.

[0020] The present invention combines a sulfonic acid group anionic organosilicon surfactant and a specific type of anionic hydrocarbon surfactant, and cooperates with a foam stabilizer, a fire retardant, a co-solvent, a flame retardant and water to form a fire extinguishing agent composition. The fire extinguishing agent prepared with this composition has the characteristics of low surface tension, strong hydrophilicity, strong foam stabilizing ability, short fire extinguishing time, and environmental friendliness. Description of the Drawings

[0021] Figure 1 It is an infrared spectrogram of the sulfonic acid group anionic organosilicon surfactant obtained in Preparation Example 1 of the present invention. Detailed Description of the Invention

[0022] In the ranges disclosed herein, the endpoints and any values are not limited to the exact ranges or values, and these ranges or values should be understood to include values close to these ranges or values. For numerical ranges, the endpoint values of each range, between the endpoint values of each range and individual point values, and between individual point values can be combined with each other to obtain one or more new numerical ranges, and these numerical ranges should be regarded as specifically disclosed herein.

[0023] In the present invention, unless otherwise specified, the room temperature or normal temperature both represent 25±2°C.

[0024] As described above, the first aspect of the present invention provides a fluorine-free environmentally friendly foam fire extinguishing agent composition, which composition includes the following components stored independently or in a mixture of two or more:

[0025] A first surfactant, a second surfactant, a foam stabilizer, a fire retardant, a co-solvent, a flame retardant and water;

[0026] The second surfactant is a combination of sodium dodecyl sulfate and cocoamidopropyl betaine with a mass ratio of 1:1-5;

[0027] Based on the total mass of the composition, the content of the first surfactant is 0.5-5 wt%, the content of the second surfactant is 5-30 wt%, the content of the foam stabilizer is 0.2-3 wt%, the content of the fire retardant is 1-6 wt%, the content of the co-solvent is 1-5 wt%, the content of the flame retardant is 4-10 wt%, and the content of water is 50-80 wt%;

[0028] The first surfactant is prepared by a method including the following steps:

[0029] S1. In the presence of a catalyst, allyl polyoxyalkylene epoxy ether and polymethylhydrogensiloxane are subjected to Reaction I to obtain epoxy polyether modified organosiloxane;

[0030] S2. React the epoxy group polyether modified silicone with sodium bisulfite in the presence of a solvent in Reaction II.

[0031] Preferably, in step S1, the conditions of Reaction I include at least: the temperature is 70 - 90 °C and the time is 4 - 6 h.

[0032] Preferably, in step S1, the catalyst is a heterogeneous solid Pt - based catalyst, and the heterogeneous solid Pt - based catalyst includes a carrier and metallic Pt loaded on the carrier.

[0033] Preferably, in step S1, in the catalyst, the carrier is alumina.

[0034] Preferably, in step S1, in the catalyst, based on the total mass of the catalyst, the loading amount of metallic Pt is 0.1 - 0.5 wt%.

[0035] Preferably, in step S1, relative to 1 g of allyl polyoxyalkylene epoxy ether, the dosage of the polymethylhydrogensiloxane is 0.1 - 1 g, and the dosage of the catalyst in terms of metallic Pt is 0.01 - 0.1 g.

[0036] Preferably, in step S2, the conditions of Reaction II include at least: the temperature is 80 - 100 °C and the time is 2 - 6 h.

[0037] Preferably, in step S2, relative to 1 g of sodium bisulfite, the dosage of the epoxy group polyether modified silicone is 0.1 - 1 g, and the dosage of the solvent is 1 - 5 g.

[0038] Preferably, in step S2, the solvent is isopropanol and / or water.

[0039] According to a particularly preferred specific embodiment of the present invention, the preparation steps of the first surfactant include:

[0040] In a reactor equipped with a thermometer and a stirrer, add allyl polyoxyalkylene epoxy ether, isopropanol and polymethylhydrogensiloxane. While maintaining the temperature at 70 - 90 °C and stirring, add the heterogeneous solid Pt - based catalyst, and continue stirring and maintaining the temperature for 4 - 6 h to obtain the epoxy group polyether modified silicone. While maintaining the temperature and stirring, add sodium bisulfite, isopropanol and water, and react at 80 - 100 °C for 2 - 6 h. Among them, relative to 1 g of allyl polyoxyalkylene epoxy ether, the dosage of the polymethylhydrogensiloxane is 0.1 - 1 g, and the dosage of the heterogeneous solid Pt - based catalyst in terms of metallic Pt is 0.01 - 0.1 g; relative to 1 g of sodium bisulfite, the dosage of the epoxy group polyether modified silicone is 0.1 - 1 g, and the dosage of the solvent is 1 - 5 g.

[0041] Preferably, based on the total mass of the composition, the content of the first surfactant is 1-3 wt%, the content of the second surfactant is 10-25 wt%, the content of the foam stabilizer is 0.4-1.5 wt%, the content of the anti-burning agent is 2-6 wt%, the content of the co-solvent is 1.5-4.5 wt%, the content of the flame retardant is 5-8 wt%, and the content of water is 60-75 wt%.

[0042] Preferably, the second surfactant is a combination of sodium dodecyl sulfate and cocamidopropyl betaine with a mass ratio of 1:1-3. The inventors found that by adopting the specific implementation manner in this preferred case, the prepared fire extinguishing agent has more excellent fire extinguishing ability.

[0043] Preferably, the foam stabilizer is xanthan gum and / or polyethylene glycol.

[0044] More preferably, the foam stabilizer is a combination of xanthan gum and polyethylene glycol with a mass ratio of 1:1.5-3. The inventors found that by adopting the specific implementation manner in this preferred case, a fire extinguishing agent with stronger foam stabilizing ability and shorter fire extinguishing time can be prepared.

[0045] According to a particularly preferred specific implementation manner, the weight-average molecular weight of the polyethylene glycol is 15000-20000.

[0046] Preferably, the anti-burning agent is urea. The inventors found that by adopting the specific implementation manner in this preferred case, a fire extinguishing agent with stronger foam stabilizing ability, longer anti-burning time and shorter fire extinguishing time can be prepared.

[0047] Preferably, the co-solvent is selected from at least one of ethylene glycol, diethylene glycol butyl ether, and isobutanol.

[0048] More preferably, the co-solvent is a combination of ethylene glycol and diethylene glycol butyl ether with a mass ratio of 1:0.3-1.

[0049] Preferably, the flame retardant is selected from at least one of sodium silicate, silica sol, and diammonium hydrogen phosphate.

[0050] As mentioned above, the second aspect of the present invention provides a method for preparing a fluorine-free environmentally friendly foam fire extinguishing agent, which includes: mixing the components in the composition described in the first aspect.

[0051] Preferably, the operation of mixing the components in the composition includes the following steps:

[0052] (1) Perform a first mixing of the first surfactant, the second surfactant, the anti-burning agent, the flame retardant, and water to obtain a first mixed solution;

[0053] (2) Mix the first mixed solution, the foam stabilizer and the cosolvent to obtain a second mixed solution, adjust the pH value of the second mixed solution to 7.5 - 8.5, and then let it stand.

[0054] Preferably, in step (1), the conditions of the first mixing and the second mixing are the same or different, and each independently includes: the temperature is 10 - 40°C, more preferably 20 - 30°C; the time is 20 - 60 min, more preferably 30 - 60 min; the stirring speed is 200 - 1500 rpm, preferably 600 - 1000 rpm.

[0055] In the present invention, in step (2), there is no special requirement for the standing time, as long as it can meet the requirements of the present invention. Exemplarily, the standing time can be 30 - 60 min.

[0056] In the present invention, in step (2), there is no special requirement for the reagent and method for adjusting the pH value of the fourth mixed solution, as long as the pH value of the system can be adjusted to 7.5 - 8.5. Exemplarily, a pH regulator can be used to adjust the pH value of the fourth mixed solution. Among them, the pH regulator can be citric acid.

[0057] As described above, the third aspect of the present invention provides a fluorine-free environmentally friendly foam fire extinguishing agent prepared by the method described in the second aspect.

[0058] As described above, the fourth aspect of the present invention provides the application of the fluorine-free environmentally friendly foam fire extinguishing agent described in the third aspect in class B fires of flammable liquids in the petrochemical field.

[0059] The present invention will be described in detail below through examples. In the following examples, unless otherwise specified, various raw materials used are commercially available products.

[0060] Allyl polyoxyalkylene epoxy ether: The brand is PB97617, purchased from Guangdong Wengjiang Chemical Reagent Co., Ltd.;

[0061] Polymethylhydrogensiloxane: The brand is E080709, purchased from Sigma-Aldrich Chemical Technology (Shanghai) Co., Ltd.;

[0062] Catalyst: Heterogeneous solid Pt-based catalyst, and its preparation method is as follows:

[0063] Weigh 5.4 g of AlCl3·6H2O, add 75 mL of deionized water, and stir in a constant-temperature water bath at 30 °C (stirring speed is 200 rpm). Add 5.4 g of polyethylene glycol and continue stirring until a transparent solution is formed. Slowly add ammonia water (concentration is 28 wt%) to this solution until the pH value of the solution reaches 9. Continue stirring for 12 h, then filter, wash 3 times with clear water, dry in an oven at 40 °C for 12 h, and then calcine at 550 °C for 6 h to obtain alumina;

[0064] Immerse 1 g of the alumina obtained above in 2 mL of a H2PtCl6·6H2O solution with a concentration of 10 g / L. After standing for 3 h, dry in an oven at 40 °C for 6 h, and calcine in an air atmosphere at 350 °C for 3 h;

[0065] The first surfactant: polyether-modified polydimethyl organosilicon surfactant, with the brand number 2293, purchased from Guangzhou Slok Polymer Co., Ltd.;

[0066] The second surfactant: sodium dodecyl sulfate, purchased from Shandong Kunxiang Chemical Technology Co., Ltd.;

[0067] The second surfactant: cocamidopropyl betaine, purchased from Henan Tianfu Chemical Co., Ltd.;

[0068] The second surfactant: sodium lauryl polyoxyethylene ether sulfate, with the molecular formula RO(CH2CH2O) n -SO3Na, where n = 2 and R is a straight-chain dodecyl group, purchased from Shanghai Bangcheng Chemical Co., Ltd.;

[0069] The anti-burning agent: urea, purchased from Sinopharm Chemical Reagent Co., Ltd.;

[0070] The anti-burning agent: polyacrylamide, with a molecular weight of 3.0×10 6 , purchased from Henan Zhongbang Environmental Protection Technology Co., Ltd.;

[0071] The flame retardant: silica sol, purchased from Yantai Hengxin Chemical Technology Co., Ltd.;

[0072] The foam stabilizer: xanthan gum, purchased from Shandong Jiayu Chemical Co., Ltd.;

[0073] The foam stabilizer: polyethylene glycol, with a weight-average molecular weight of 20000, purchased from Sinopharm Chemical Reagent Co., Ltd.;

[0074] The co-solvent: ethylene glycol, purchased from Sinopharm Chemical Reagent Co., Ltd.;

[0075] The co-solvent: diethylene glycol butyl ether, purchased from Sinopharm Chemical Reagent Co., Ltd.;

[0076] In the following examples, isopropyl alcohol, sodium bisulfite, chloroplatinic acid, and citric acid are all analytical pure chemical reagents.

[0077] Preparation Example 1

[0078] This preparation example is used to illustrate the preparation of the first surfactant (sulfonic acid group anionic organosilicon surfactant).

[0079] In a three-necked flask equipped with a reflux condenser, a stirrer, and a thermometer, nitrogen was introduced at an initial flow rate of 500 mL / min. After blowing out the air from the flask, the flow rate was adjusted to 85 mL / min. At a temperature of 80 °C, 16.4 g of allyl polyoxyalkylene epoxy ether, 7.2 g of isopropyl alcohol, and 3.2 g of polymethylhydrogensiloxane were added. Stir at 200 rpm for 5 min, add 0.5 g of a solid Pt-based catalyst (0.2 wt% of metal Pt supported on alumina), continue to stir while maintaining the temperature for 6 h, and obtain a light yellow transparent liquid (epoxy polyether modified organosiloxane) by vacuum distillation. Then, 3.1 g of isopropyl alcohol and 2.3 g of water were added to the three-necked flask simultaneously. After stirring at 200 rpm for 5 min, 1.8 g of sodium bisulfite was added, and the temperature was raised to 90 °C. After reacting for 4 h, the reaction was stopped, and the sulfonic acid group anionic organosilicon surfactant A1 was obtained by vacuum distillation.

[0080] The surface tension of the above-mentioned sulfonic acid group anionic organosilicon surfactant was tested: the surface tension of the sulfonic acid group anionic organosilicon surfactant with a mass fraction of 0.1 wt% was 19.7 mN / m, and the contact angle was 18°; while the surface tension before modification was 21.3 mN / m, and the contact angle was 72°.

[0081] The present invention exemplarily provides an infrared spectrum of the sulfonic acid group anionic organosilicon surfactant prepared as described above, as shown in Figure 1 .

[0082] From Figure 1 it can be seen that at 635 cm -1 there appears a stretching vibration peak of the C-C-S bond connected to -SO3.

[0083] Example 1

[0084] This example provides a method for preparing a fluorine-free environmentally friendly foam fire extinguishing agent, which includes:

[0085] (1) At room temperature, 20 g of the sulfonic acid group anionic organosilicon surfactant A1 obtained in the above preparation example, 60 g of sodium dodecyl sulfate, 80 g of cocamidopropyl betaine, 50 g of urea, 60 g of silica sol, and 663 g of water were stirred at 800 rpm for 30 min to obtain a first mixed solution uniformly.

[0086] (2) At room temperature, the first mixed solution, 2 g of xanthan gum, 5 g of polyethylene glycol, 20 g of ethylene glycol, and 20 g of diethylene glycol butyl ether are stirred at 800 rpm for 30 min to obtain a second mixed solution. Then, 20 g of a citric acid solution with a concentration of 40 wt% is added, and stirring is continued for 5 min. After standing for 30 min, a fluorine-free environmentally friendly foam fire extinguishing agent S1 is obtained.

[0087] Unless otherwise specified, Examples 2 - 5 are carried out using the same procedure as in Example 1, except that the formulations of the fluorine-free environmentally friendly foam fire extinguishing agents used are different. For details, see Table 1.

[0088] Comparative Example 1

[0089] A fluorine-free environmentally friendly foam fire extinguishing agent is prepared according to the method of Example 1, except that an equal mass of polyether-modified polydimethyl organosilicon surfactant is used to replace the sulfonic acid group anionic organosilicon surfactant.

[0090] Comparative Example 2

[0091] A fluorine-free environmentally friendly foam fire extinguishing agent is prepared according to the method of Example 1, except that the second surfactant used is 140 g of sodium dodecyl sulfate.

[0092] Comparative Example 3

[0093] A fluorine-free environmentally friendly foam fire extinguishing agent is prepared according to the method of Example 1, except that the second surfactant used is 60 g of sodium dodecyl sulfate and 80 g of fatty alcohol polyoxyethylene ether sulfate.

[0094] Table 1

[0095]

[0096]

[0097] Table 1 (continued)

[0098]

[0099] Test Example

[0100] The fluorine-free environmentally friendly foam fire extinguishing agents prepared in the examples and comparative examples are subjected to performance tests, including tests on pH value, freezing point, foaming multiple, 25% liquid separation time, and fire extinguishing performance. The specific test results are shown in Table 2.

[0101] Equipment used during the test: pH meter, thermometer, freezing point determinator, foam generation system, foam collector, drainage determinator, balance, stopwatch, round, conical-bottom steel oil pan (inner diameter: 565 mm, depth 150 mm, oil pan area is 0.25 m 2 ), steel anti-burning tank (inner diameter 120 mm, depth 80 mm), 144B round steel oil pan (inner diameter: 2400 mm, depth 200 mm, oil pan area is 4.52 m 2 ), 144B steel anti-burning tank (inner diameter 300 mm, depth 150 mm).

[0102] pH value measurement method: (1) Calibrate the pH meter with pH buffer; (2) Take 30 mL of the foam extinguishing agent product and pour it into a dry and clean 50 mL beaker. Immerse the electrode in the foam liquid and measure the pH value at (20±2)°C; (3) Repeat the test once, and take the average of the two test results as the pH value of the foam extinguishing agent.

[0103] Freezing point measurement method: Conduct according to item 5.2.3 "Freezing point" in GB 15308-2006 "Foam Extinguishing Agent".

[0104] Measurement methods for expansion ratio and 25% drainage time: Refer to item 5.8 "Expansion ratio and 25% drainage time of low-expansion foam liquid" in GB 15308-2006 "Foam Extinguishing Agent".

[0105] The specific steps for the fire extinguishing performance test of the 21B round, conical-bottom steel oil pan are as follows: (1) Prepare a foam solution by mixing the extinguishing agent product and water in a ratio of 6:94 and fill it into the foam solution storage tank; (2) Apply a pressure of (0.7±0.03) MPa to the foam solution storage tank and adjust the 7 mm flow regulator so that the foam flow rate in the straight direction is 725-775 g / min; (3) Adjust the position of the foam gun so that the applied foam exactly falls in the center of the oil pan; (4) Add 9 L of fuel (solvent oil for rubber industry No. 120) to the oil pan and 1 L of fuel to the anti-burning tank, and place them in a safe place. After adding the fuel, ignite the oil pan within 5 minutes, pre-burn for 60 s, and start supplying foam; (5) Record the moment when the flame is completely extinguished, which is the fire extinguishing time. (6) Continue to supply foam after the flame is extinguished. Stop supplying foam after the total foam supply time reaches 180 s and wait for 60 s. Place the anti-burning tank containing 1 L of fuel in the center of the oil pan and ignite it, and record the 25% anti-burning time.

[0106] Test steps for the fire extinguishing performance of the 144B round steel oil pan: Execute according to item 5.10.5 "Test for extinguishing non-water-soluble liquid fuel fire with multi-expansion foam liquid" in GB15308-2006 "Foam Extinguishing Agent";

[0107] The specific steps are as follows: (1) First, prepare a foam solution by mixing the fire extinguishing agent product and water in a ratio of 6:94, and fill it into the foam solution storage tank; (2) Apply a pressure of (0.7 ± 0.03) MPa to the foam solution storage tank, and adjust the flow rate of the foam gun so that the foam flow rate is 11.4 L / min; (3) Place the 144B oil pan on the ground and keep it horizontal, with the oil pan in the downwind direction of the foam gun, and add 90 L of water to completely cover the bottom of the pan; (4) Place the foam gun horizontally and 1 ± 0.05 m above the fuel surface, so that the center of the foam jet hits the center axis of the baffle and is 0.5 ± 0.1 m above the fuel surface; (5) Add 144 L of fuel (solvent oil for rubber industry No. 120) to the oil pan, and add 2 L of fuel to the anti-burning tank, and place it on the downwind side of the oil pan; (6) Ignite the oil pan within 5 min after adding the fuel, pre-burn for (60 ± 5) s, start supplying foam, and record the fire extinguishing time; (7) After supplying foam for 300 s, wait for 300 s, place the anti-burning tank containing 2 L of fuel in the center of the oil pan and ignite it, and record the 25% anti-burning time.

[0108] Table 2

[0109]

[0110] It can be seen from the results in Table 2 that the fluorine-free environmentally friendly foam fire extinguishing agent prepared in the embodiments of the present invention has a moderate pH value and freezing point, excellent foaming multiple, a relatively long 25% liquid separation time, can successfully extinguish the 21B oil pan fire, has a long anti-burning time, all greater than 600 s, and the fire extinguishing performance meets the national standards; while the fire extinguishing agents prepared in Comparative Examples 1-3 have a longer fire extinguishing time and poor anti-burning performance.

[0111] The fire extinguishing agent prepared in Example 1 was used to extinguish the 144B oil pan fire. The test results showed that the fire extinguishing time for extinguishing the 144B oil pan fire was 1'32", and the anti-burning time was 11'25", and the fire extinguishing performance met the national standards.

[0112] The preferred embodiments of the present invention have been described in detail above. However, the present invention is not limited thereto. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solutions of the present invention, including any other suitable combination of each technical feature. These simple modifications and combinations should also be regarded as the content disclosed by the present invention and fall within the protection scope of the present invention.

Claims

1. A fluorine-free environmentally friendly foam fire extinguishing agent composition, characterized in that, The composition comprises the following components stored independently or in combination of two or more: A first surfactant, a second surfactant, a foam stabilizer, a combustion inhibitor, a co-solvent, a flame retardant, and water; The second surfactant is a combination of sodium dodecyl sulfate and cocoamidopropyl betaine with a mass ratio of 1:1 - 5; Based on the total mass of the composition, the content of the first surfactant is 0.5 - 5 wt%, the content of the second surfactant is 5 - 30 wt%, the content of the foam stabilizer is 0.2 - 3 wt%, the content of the combustion inhibitor is 1 - 6 wt%, the content of the co-solvent is 1 - 5 wt%, the content of the flame retardant is 4 - 10 wt%, and the content of water is 50 - 80 wt%; The first surfactant is prepared by a method comprising the following steps: S1. In the presence of a catalyst, allyl polyoxyalkylene epoxy ether and polymethylhydrogensiloxane are subjected to Reaction I to obtain epoxy polyether modified silicone; S2. In the presence of a solvent, the epoxy polyether modified silicone and sodium bisulfite are subjected to Reaction II.

2. The composition according to claim 1, wherein In step S1, the conditions of Reaction I include at least: temperature of 70 - 90 °C, time of 4 - 6 h; and / or, In step S1, the catalyst is a heterogeneous solid Pt-based catalyst, and the heterogeneous solid Pt-based catalyst comprises a carrier and metal Pt supported on the carrier; and / or, In step S2, the conditions of Reaction II include at least: temperature of 80 - 100 °C, time of 2 - 6 h.

3. The composition according to claim 1 or 2, wherein Based on the total mass of the composition, the content of the first surfactant is 1 - 3 wt%, the content of the second surfactant is 10 - 25 wt%, the content of the foam stabilizer is 0.4 - 1.5 wt%, the content of the combustion inhibitor is 2 - 6 wt%, the content of the co-solvent is 1.5 - 4.5 wt%, the content of the flame retardant is 5 - 8 wt%, and the content of water is 60 - 75 wt%.

4. The composition according to claim 1 or 2, wherein The second surfactant is a combination of sodium dodecyl sulfate and cocoamidopropyl betaine with a mass ratio of 1:1 - 3.

5. The composition according to claim 1 or 2, wherein The foam stabilizer is xanthan gum and / or polyethylene glycol.

6. The composition according to claim 5, wherein, The foam stabilizer is a combination of xanthan gum and polyethylene glycol with a mass ratio of 1:1.5 - 3.

7. The composition according to claim 6, wherein, The combustion inhibitor is urea.

8. The composition according to claim 1 or 2, wherein The co-solvent is selected from at least one of ethylene glycol, diethylene glycol monobutyl ether, and isobutanol.

9. The composition according to claim 8, wherein The co-solvent is a combination of ethylene glycol and diethylene glycol monobutyl ether with a mass ratio of 1:0.3 - 1.

10. The composition according to claim 1 or 2, wherein The flame retardant is selected from at least one of sodium silicate, silica sol, and diammonium hydrogen phosphate.

11. A method for preparing a fluorine-free environmentally friendly foam fire extinguishing agent, characterized in that, The method includes: mixing the components in the composition according to any one of claims 1 - 10.

12. The method according to claim 11, wherein, The operation of mixing the components in the composition includes the following steps: (1) First mix the first surfactant, the second surfactant, the combustion inhibitor, the flame retardant, and water to obtain a first mixed solution; (2) Mix the first mixed solution, the foam stabilizer and the cosolvent for a second time to obtain a second mixed solution, and adjust the pH value of the second mixed solution to 7.5 - 8.5 and then let it stand.

13. The method according to claim 12, wherein In step (1), the conditions of the first mixing and the second mixing are the same or different, and each independently includes: The temperature is 10 - 40 °C, the time is 20 - 60 min, and the stirring speed is 200 - 1500 rpm.

14. The method according to claim 13, wherein In step (1), the conditions of the first mixing and the second mixing are the same or different, and each independently includes: The temperature is 20 - 30 °C, the time is 30 - 60 min, and the stirring speed is 600 - 1000 rpm.

15. A fluorine-free environment-friendly foam fire extinguishing agent prepared by the method according to any one of claims 12 - 14.

16. Application of the fluorine-free environment-friendly foam fire extinguishing agent according to claim 15 in class B fires of flammable liquids in the petrochemical field.

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