CN111569349A - Environment-friendly degradable aqueous film-forming foam extinguishing agent and preparation method and application thereof - Google Patents
Environment-friendly degradable aqueous film-forming foam extinguishing agent and preparation method and application thereof Download PDFInfo
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- CN111569349A CN111569349A CN202010581385.0A CN202010581385A CN111569349A CN 111569349 A CN111569349 A CN 111569349A CN 202010581385 A CN202010581385 A CN 202010581385A CN 111569349 A CN111569349 A CN 111569349A
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- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D1/00—Fire-extinguishing compositions; Use of chemical substances in extinguishing fires
- A62D1/0064—Gels; Film-forming compositions
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- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D1/00—Fire-extinguishing compositions; Use of chemical substances in extinguishing fires
- A62D1/0071—Foams
- A62D1/0085—Foams containing perfluoroalkyl-terminated surfactant
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Abstract
An environment-friendly degradable aqueous film-forming foam extinguishing agent, a preparation method and application thereof, belonging to the technical field of fire extinguishing agent preparation. The environment-friendly degradable aqueous film-forming foam extinguishing agent comprises the following raw materials: fluorocarbon surfactant, foaming agent, foam stabilizer, anti-burning agent, antifreeze agent, cosolvent, preservative, chelating agent and pH regulator, and the balance of water; wherein the fluorocarbon surfactant is hexafluoropropylene oxide trimer quaternary ammonium salt and perfluoro-2, 5-dimethyl-3, 6-dioxanonanoic acid ammonium salt. The preparation method is simple, the prepared fire extinguishing agent can be rapidly degraded, has no biological accumulation, has no irritation to field firefighters in the using process, has no pollution to water and soil, and is high in environmental friendliness; meanwhile, the product has low surface tension, can be quickly spread and sealed on the surface of an oil film, and effectively inhibits oil vapor from volatilizing, thereby achieving the effects of quickly extinguishing fire and efficiently resisting burning.
Description
Technical Field
The invention belongs to the technical field of fire extinguishing agent preparation, and particularly relates to an environment-friendly degradable aqueous film-forming foam extinguishing agent, and a preparation method and application thereof.
Background
The fluorocarbon surfactant, the main component in the traditional aqueous film-forming foam extinguishing agent, has serious environmental problems, and the C8 perfluorooctyl carboxylate and sulfonate fluorocarbon surfactant are extremely stable in the environment, are difficult to hydrolyze, cannot be biodegraded and have bioaccumulation and mobility in a food chain. At present, the C8 fluorocarbon surfactant has been banned at home and abroad gradually due to the increasing environmental protection pressure. As a substitute product, the main foam extinguishing agent products at home and abroad mainly adopt C6 fluorocarbon surfactant, and have no bioaccumulation, but the degradability in the environment is still unknown.
The Chinese patent with the application number of 201610198291.9 discloses an aqueous film-forming foam extinguishing agent based on a short fluorocarbon chain, and particularly discloses that the aqueous film-forming foam extinguishing agent consists of a fluorocarbon surfactant, a hydrocarbon surfactant, a hydrophilic high polymer, an organic solvent, water and the like; the fluorocarbon surfactant is an anionic and cationic fluorocarbon surfactant compound based on short fluorocarbon chains. The molar ratio of the anionic fluorocarbon surfactant to the cationic fluorocarbon surfactant is 5:1-1: 5. The aqueous film-forming foam extinguishing agent has the advantages of low production cost, simple preparation method, environmental friendliness and quick fire extinguishing.
According to the technical scheme, the novel aqueous film-forming foam extinguishing agent is formed on the basis of the anionic fluorocarbon surfactant and the cationic fluorocarbon surfactant with short fluorocarbon chains, and has good environmental degradability. The fluorocarbon quantity is between C1 and C4, and the main problems are that the hydrophobic capacity formed by C-F bond ends is relatively poor, the surface tension of a product is relatively high, and the spreading capacity is poor compared with that of a traditional fluorocarbon surfactant.
The existing aqueous film-forming foam extinguishing agent of the short fluorocarbon chain fluorocarbon surfactant has relatively low sealing effect on an oil film and relatively poor evaporation inhibiting performance in the combustion process, so that the extinguishing efficiency is low and the anti-burning capacity is poor.
Disclosure of Invention
The technical problem to be solved is as follows: aiming at the technical problems, the invention provides an environment-friendly degradable aqueous film-forming foam fire extinguishing agent and a preparation method and application thereof, the preparation method is simple, the prepared fire extinguishing agent can be rapidly degraded, has no bioaccumulation, has no irritation to field firefighters in the using process, has no pollution to water, soil and the like, is high in environmental friendliness and low in surface tension, can be rapidly spread and sealed on the surface of an oil film, and effectively inhibits oil vapor from volatilizing, thereby achieving the effects of rapidly extinguishing fire and efficiently resisting burning.
The technical scheme is as follows: the environment-friendly degradable aqueous film-forming foam extinguishing agent comprises the following raw materials in percentage by mass: 1-6% of fluorocarbon surfactant, 10-20% of foaming agent, 1-10% of foam stabilizer, 0.1-10% of anti-burning agent, 10-30% of antifreeze agent, 3-10% of cosolvent, 0.1-1.0% of preservative, 0.1-1% of chelating agent, 0.1-1% of pH regulator and the balance of water; the fluorocarbon surfactant is hexafluoropropylene oxide trimer quaternary ammonium salt and perfluoro-2, 5-dimethyl-3, 6-dioxanonanoic acid ammonium salt, the mass percent of the hexafluoropropylene oxide trimer quaternary ammonium salt in the raw material is 0.5-3%, and the mass percent of the perfluoro-2, 5-dimethyl-3, 6-dioxanonanoic acid ammonium salt in the raw material is 0.5-3%.
Preferably, the foaming agent is at least one of alkyl glycoside, fatty alcohol-polyoxyethylene ether, cocamidopropyl betaine, ammonium lauryl sulfate salt and sodium octyldecyl sulfate.
Preferably, the foam stabilizer is at least one of triethanolamine, dodecyl dimethyl amine oxide, cocamidopropyl amine oxide and lauramidopropyl amine oxide.
Preferably, the anti-burning agent is at least one of polyethylene glycol, xanthan gum and sodium alginate.
Preferably, the antifreeze agent is ethylene glycol, the cosolvent is urea, the chelating agent is imino disuccinic acid tetrasodium salt IDS, the preservative is potassium sorbate, and the pH regulator is citric acid.
The preparation method of the environment-friendly degradable aqueous film-forming foam extinguishing agent comprises the following steps: adding an anti-burning agent and water into a reaction kettle, pre-dispersing and dissolving under high-speed stirring, adding a fluorocarbon surfactant, a foaming agent, a foam stabilizer, an antifreeze agent, a cosolvent, a preservative and a chelating agent according to the mass fraction ratio, and stirring for 1 h to ensure that the system is uniform; adding a pH regulator to regulate the pH to 6.8-7.5, uniformly stirring, and standing to obtain the product.
The application of the environment-friendly degradable aqueous film-forming foam extinguishing agent in extinguishing B-type oil fire.
Has the advantages that: 1. the foam fire extinguishing agent product has lower surface tension (less than or equal to 18 mN/m), generates fine and rich foam, can be quickly spread and sealed on the surface of an oil film, and effectively inhibits oil vapor from volatilizing, thereby achieving the effects of quickly extinguishing fire and efficiently resisting burning, and achieving the fire extinguishing performance level IA (the fire extinguishing time is less than or equal to 3min, and the burning resisting time is more than or equal to 10 min).
2. The foam extinguishing agent has strong applicability and can be applied to various fire-fighting systems and devices. The freezing point is adapted to-30 ℃ at the lowest, and is suitable for different regions. Can be mixed with seawater/fresh water, and is suitable for use in offshore and coastal areas.
3. The foam extinguishing agent has very good biodegradability, can be naturally degraded in the environment (the biodegradability is more than or equal to 95 percent), and has no bioaccumulation; all the raw materials are non-toxic and non-irritant (the death rate of the zebra fish is 0 percent), and no organic solvents such as ethylene glycol monobutyl ether and the like are added, so that the environment is not harmfully affected.
Detailed Description
The invention is further described with reference to specific examples.
Example 1
The fluorocarbon surfactant in this example was hexafluoropropylene oxide trimer quaternary ammonium salt and perfluoro-2, 5-dimethyl-3, 6-dioxanonanoic acid ammonium salt, purchased from haisfu chemical industry, samming, fujian province. The foaming agent is fatty alcohol-polyoxyethylene ether (AEO-9) and cocamidopropyl betaine, the foam stabilizer is triethanolamine and lauramidopropyl amine oxide, the anti-burning agent is polyethylene glycol (PEG-8000) and xanthan gum, the antifreeze agent is ethylene glycol, the cosolvent is urea, the chelating agent is iminodisuccinic acid tetrasodium salt, the preservative is potassium sorbate, and the pH regulator is citric acid.
The environment-friendly degradable aqueous film-forming foam extinguishing agent comprises the following raw materials in percentage by mass: 1% of hexafluoropropylene oxide trimer quaternary ammonium salt, 2% of perfluoro-2, 5-dimethyl-3, 6-dioxanonanoic acid ammonium salt, 2% of fatty alcohol polyoxyethylene ether AEO-93%, 5% of cocamidopropyl betaine, 1% of triethanolamine, 3% of lauramidopropyl amine oxide, 0.1% of polyethylene glycol PEG-80005%, 0.1% of xanthan gum, 10% of ethylene glycol, 5% of urea, 0.5% of iminodisuccinic acid tetrasodium salt, 0.5% of potassium sorbate and 0.5% of citric acid, and the balance of water.
The preparation method of the environment-friendly degradable aqueous film-forming foam extinguishing agent comprises the following steps: adding PEG-800050kg, xanthan gum 1kg and water 634kg into a reaction kettle, pre-dispersing and dissolving under high-speed stirring, weighing and adding 10kg of hexafluoropropylene oxide trimer quaternary ammonium salt, 20kg of perfluoro-2, 5-dimethyl-3, 6-dioxanonanoic acid ammonium salt, fatty alcohol polyoxyethylene ether AEO-930kg, 50kg of cocamidopropyl betaine, 10kg of triethanolamine, 30kg of laurylamidopropylamine oxide, 100kg of ethylene glycol, 50kg of urea, 5kg of potassium sorbate and 5kg of imino disuccinic acid tetrasodium salt, stirring uniformly, adding 5kg of citric acid to adjust the pH value to 6.8-7.5, stirring uniformly, and standing to obtain the product.
Example 2
The environment-friendly degradable aqueous film-forming foam extinguishing agent in the embodiment comprises the following raw materials in percentage by mass: 1% of fluorocarbon surfactant, 10% of foaming agent, 1% of foam stabilizer, 0.3% of anti-burning agent, 10% of antifreeze agent, 3% of cosolvent, 0.1% of preservative, 0.1% of chelating agent, 0.1% of pH regulator and the balance of water.
The preparation method of the environment-friendly degradable aqueous film-forming foam extinguishing agent comprises the following preparation processes: adding 2kg of xanthan gum, 1kg of sodium alginate and 744kg of water into a reaction kettle, pre-dispersing and dissolving under high-speed stirring, weighing and adding 5kg of hexafluoropropylene oxide trimer quaternary ammonium salt, 5kg of perfluoro-2, 5-dimethyl-3, 6-dioxanonanoic acid ammonium salt, 70kg of alkyl glycoside, 30kg of sodium octyldecyl sulfate, 10kg of dodecyl dimethyl amine oxide, 100kg of ethylene glycol, 30kg of urea, 1kg of potassium sorbate and 1kg of imino disuccinic acid tetrasodium salt, stirring uniformly, adding 1kg of citric acid to adjust the pH value to 6.8-7.5, stirring uniformly and standing to obtain the product.
Example 3
The environment-friendly degradable aqueous film-forming foam extinguishing agent in the embodiment comprises the following raw materials in percentage by mass: 6% of fluorocarbon surfactant, 20% of foaming agent, 10% of foam stabilizer, 10% of anti-burning agent, 30% of antifreeze agent, 10% of cosolvent, 1% of preservative, 1% of chelating agent and 0.7% of pH regulator, and the balance of water; wherein the fluorocarbon surfactant is hexafluoropropylene oxide trimer quaternary ammonium salt and perfluoro-2, 5-dimethyl-3, 6-dioxanonanoic acid ammonium salt, the mass fraction of the hexafluoropropylene oxide trimer quaternary ammonium salt is 3%, and the mass fraction of the perfluoro-2, 5-dimethyl-3, 6-dioxanonanoic acid ammonium salt is 3%.
The preparation method of the environment-friendly degradable aqueous film-forming foam extinguishing agent comprises the following preparation processes: adding PEG-20000100 kg and 113kg of water into a reaction kettle, pre-dispersing and dissolving under high-speed stirring, weighing 30kg of hexafluoropropylene oxide trimer quaternary ammonium salt, 30kg of perfluoro-2, 5-dimethyl-3, 6-dioxanonanoic acid ammonium salt, 150kg of cocamidopropyl betaine, 50kg of lauryl alcohol sulfate ammonium salt, 100kg of cocamidopropyl amine oxide, 300kg of ethylene glycol, 100kg of urea, 10kg of potassium sorbate and 10kg of imino disuccinic acid tetrasodium salt according to the mass fraction ratio, adding 7kg of citric acid after uniformly stirring, adjusting the pH value to 6.8-7.5, uniformly stirring, and standing to obtain the product.
Comparative example 1
508 kg of industrial soft water and 2kg of xanthan gum are added into a reaction kettle for pre-dissolving, and nonionic fluorocarbon surfactant YM-31660 kg, foaming agent alkylphenol polyoxyethylene ether APEO 150kg, hydrocarbon anionic surfactant SDBS 110 kg, ethylene glycol 100kg and urea 70kg are sequentially added under the condition of mechanical stirring. Fully stirring and dissolving to form a homogeneous solution, and standing to obtain a foam liquid.
Comparative example 2
534.9 kg of industrial soft water and polyethylene glycol PEG-1000050 kg are added into a reaction kettle for pre-dissolving, and amphoteric fluorocarbon surfactant FC-115740 kg, foaming agent alkyl glycoside 100kg, dodecyl betaine 100kg, ethylene glycol 100kg, urea 70kg, butyl carbitol 50kg, ethylene diamine tetraacetic acid disodium 5kg and antibacterial agent methylisothiazolinone 0.1 kg are sequentially added under the condition of mechanical stirring. Fully stirring and dissolving to form a homogeneous solution, and standing to obtain a foam liquid.
The products prepared in the examples and the comparative examples are respectively subjected to physical and chemical performance tests and standard fire extinguishing experiment tests according to GB 15308-2006 foam fire extinguishing agent. The test results are shown in the following table.
According to the formula provided by the embodiment of the invention, the prepared product can reach the highest IA level of the national standard (the strong-release fire extinguishing time is less than or equal to 3min, and the burning-resistant time is more than or equal to 10 min), can be quickly spread on the oil surface, and has the advantages of high fire extinguishing efficiency and strong burning-resistant capability.
The biodegradability experiment of the foam extinguishing agent is carried out according to GB/T21801-. Adding the foam liquid test substance into the inoculated inorganic culture medium as a unique organic carbon source, continuously stirring for 28 days under a closed constant temperature condition, absorbing CO released in the test process by using a potassium hydroxide solution, and measuring the change of air pressure in the bottle by using an instrument to obtain oxygen consumption, namely the Biochemical Oxygen Demand (BOD) of the test substance. The biodegradation rate of the foam concentrate is characterized by the ratio of Biochemical Oxygen Demand (BOD) to Chemical Oxygen Demand (COD).
According to the toxicity test method of GB 17835-2008 water-based fire extinguishing agent, zebra fish with the body length (30 +/-5) mm and the body weight (0.3 +/-0.1) g is selected as the test fingerling, and the zebra fish with the same specification and size in the same domestication pond is selected. The herds should be kept in continuously aerated water for at least two weeks prior to testing under the same environmental conditions as at the time of testing. Environmental parameters for zebra fish domestication are described in GB/T13267-1991 appendix B. During the test period, the temperature of the mixed solution is kept at (23 +/-2) DEG C, the feeding is stopped 24h before the test period, and the feeding is not carried out during the whole test period.
12mL of the foam concentrate was poured into a beaker and diluted to 2000mL with standard dilution water. 10 healthy zebra fish were placed in the chamber and kept at ambient temperature (23 + -2) deg.C for 96h, and the fish mortality was recorded. The 28d biodegradation rate and lethality results for the test subjects are shown in the following table.
Claims (7)
1. The environment-friendly degradable aqueous film-forming foam extinguishing agent is characterized by comprising the following raw materials in percentage by mass: 1-6% of fluorocarbon surfactant, 10-20% of foaming agent, 1-10% of foam stabilizer, 0.1-10% of anti-burning agent, 10-30% of antifreeze agent, 3-10% of cosolvent, 0.1-1% of preservative, 0.1-1% of chelating agent, 0.1-1% of pH regulator and the balance of water; the fluorocarbon surfactant is hexafluoropropylene oxide trimer quaternary ammonium salt and perfluoro-2, 5-dimethyl-3, 6-dioxanonanoic acid ammonium salt, the mass percent of the hexafluoropropylene oxide trimer quaternary ammonium salt in the raw material is 0.5-3%, and the mass percent of the perfluoro-2, 5-dimethyl-3, 6-dioxanonanoic acid ammonium salt in the raw material is 0.5-3%.
2. The environmental-friendly degradable aqueous film-forming foam extinguishing agent according to claim 1, wherein the foaming agent is at least one of alkyl glycoside, fatty alcohol-polyoxyethylene ether, cocamidopropyl betaine, ammonium lauryl sulfate and sodium octyldecyl sulfate.
3. The environment-friendly degradable aqueous film-forming foam fire extinguishing agent according to claim 1, wherein the foam stabilizer is at least one of triethanolamine, dodecyl dimethyl amine oxide, cocamidopropyl amine oxide and lauramidopropyl amine oxide.
4. The environment-friendly degradable aqueous film-forming foam extinguishing agent as claimed in claim 1, wherein the anti-burning agent is at least one of polyethylene glycol, xanthan gum and sodium alginate.
5. The environment-friendly degradable aqueous film-forming foam fire extinguishing agent as claimed in claim 1, wherein the antifreeze is ethylene glycol, the cosolvent is urea, the chelating agent is imino disuccinic acid tetrasodium salt, the preservative is potassium sorbate, and the pH regulator is citric acid.
6. The preparation method of the environment-friendly degradable aqueous film-forming foam extinguishing agent based on claim 1 is characterized by comprising the following steps: adding an anti-burning agent and water into a reaction kettle, pre-dispersing and dissolving under high-speed stirring, adding a fluorocarbon surfactant, a foaming agent, a foam stabilizer, an antifreeze agent, a cosolvent, a preservative and a chelating agent according to the mass fraction ratio, and stirring for 1 h to ensure that the system is uniform; adding a pH regulator to regulate the pH to 6.8-7.5, uniformly stirring, and standing to obtain the product.
7. The use of the environmentally-friendly degradable aqueous film-forming foam extinguishing agent based on claim 1 for extinguishing a group B oil fire.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112774075A (en) * | 2021-01-22 | 2021-05-11 | 江西省森智科技发展有限公司 | Green environment-friendly water-based extinguishing agent |
| CN113398522A (en) * | 2021-06-17 | 2021-09-17 | 海南飞浪消防科技有限公司 | Seawater-resistant environment-friendly aqueous film-forming foam extinguishing agent and preparation method and application thereof |
| CN114602113A (en) * | 2022-03-31 | 2022-06-10 | 珠海金禹科技有限公司 | Aqueous film-forming foam extinguishing agent and preparation method thereof |
| CN115814327A (en) * | 2021-09-17 | 2023-03-21 | 南京理工大学 | Aqueous film-forming foam extinguishing agent and preparation method thereof |
| CN117442923A (en) * | 2023-10-12 | 2024-01-26 | 中国华能集团清洁能源技术研究院有限公司 | Low-conductivity compressed air foam, preparation method and application |
| CN117925214A (en) * | 2024-03-21 | 2024-04-26 | 成都西油华巍科技有限公司 | High condensate oil resistant antifreezing foam discharging agent and preparation method and application thereof |
| CN117925214B (en) * | 2024-03-21 | 2024-05-31 | 成都西油华巍科技有限公司 | High condensate oil resistant antifreezing foam discharging agent and preparation method and application thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112774075A (en) * | 2021-01-22 | 2021-05-11 | 江西省森智科技发展有限公司 | Green environment-friendly water-based extinguishing agent |
| CN113398522A (en) * | 2021-06-17 | 2021-09-17 | 海南飞浪消防科技有限公司 | Seawater-resistant environment-friendly aqueous film-forming foam extinguishing agent and preparation method and application thereof |
| CN115814327A (en) * | 2021-09-17 | 2023-03-21 | 南京理工大学 | Aqueous film-forming foam extinguishing agent and preparation method thereof |
| CN114602113A (en) * | 2022-03-31 | 2022-06-10 | 珠海金禹科技有限公司 | Aqueous film-forming foam extinguishing agent and preparation method thereof |
| CN117442923A (en) * | 2023-10-12 | 2024-01-26 | 中国华能集团清洁能源技术研究院有限公司 | Low-conductivity compressed air foam, preparation method and application |
| CN117925214A (en) * | 2024-03-21 | 2024-04-26 | 成都西油华巍科技有限公司 | High condensate oil resistant antifreezing foam discharging agent and preparation method and application thereof |
| CN117925214B (en) * | 2024-03-21 | 2024-05-31 | 成都西油华巍科技有限公司 | High condensate oil resistant antifreezing foam discharging agent and preparation method and application thereof |
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Application publication date: 20200825 |