无氟泡沫灭火剂真火实验与分子动力学模拟

doi:10.11949/0438-1157.20240397

摘要/Abstract

摘要：

针对低碳醇调控碳氢和有机硅表面活性剂制备无氟泡沫灭火剂路线的广泛适用性以及小尺度灭火实验评价灭火效果的局限性，选取一种新型有机硅表面活性剂SILOK与两类碳氢表面活性剂CHX-3和SDS为关键组分，开展无氟泡沫灭火剂的复配方案设计、泡沫性能测试、真火灭火实验和分子动力学模拟。测试结果表明：CHX-3/SILOK/异丁醇和SDS/SILOK/异丁醇两类复配体系5种复配方案的无氟泡沫灭火剂均具有良好的泡沫基础性能，设计方案的表面张力为20.3~22.7 mN/m，稳泡系数为0.9617~0.9762，25%析液时间为203~238 s。相对来说，CHX-3/SILOK/异丁醇的质量分数为0.48%/0.1%/0.03%的Case5配方具有更加优良的泡沫基础性能，表面张力低，发泡性和稳泡性能良好。真火灭火实验证明：CHX-3/SILOK/异丁醇体系的Case5方案，90%控火时间仅为42 s；灭火时间最短，仅为49 s；平均灭火降温速率最大，达到了7.59℃/s。通过分子动力学模拟研究了复配体系的氢键和扩散系数，阐明了CHX-3和SDS对泡沫稳定性和表面张力的影响规律。研究成果能够为无氟泡沫灭火剂的开发、应用和推广提供数据支持和理论支撑。

关键词: 无氟泡沫灭火剂, 泡沫性能, 真火实验, 降温速率, 分子动力学, 分子间氢键

Abstract:

To address the wide applicability of the route of preparing fluorine-free foam extinguishing agent with low-carbon alcohol modulated hydrocarbon and silicone surfactants, as well as the limitation of evaluating the fire extinguishing effect in small-scale fire extinguishing experiments, a new silicone surfactant SILOK and two types of hydrocarbon surfactants CHX-3 and SDS were selected as the key basic components to carry out the design of the compounding scheme of the fluorine-free foam extinguishing agent, the foam basic performance test, real fire extinguishing experiment and molecular dynamics simulation. The test showed that the fluorine-free foam extinguishing agents of CHX-3/SILOK/isobutanol and SDS/SILOK/isobutanol with five compounding systems had good foam base performance, and the surface tension of the design scheme was in the range of 20.3—22.7 mN/m, the stabilizing coefficient of foam was in the range of 0.9617—0.9762, and the 25% drainage time was in the range of 203—238 s. But relatively speaking, the Case5 formulation which the mass fraction of CHX-3/SILOK/isobutanol is 0.48%/0.1%/0.03%, respectively, had better foam base properties, low surface tension, good foaming and stabilizing properties. True fire extinguishing experiment has proved that in the Case5 scheme of the CHX-3/SILOK/isobutanol system, 90% flame control time is only 42 s, the fire extinguishing time is the shortest, only 49 s, and the average fire cooling rate is the largest, reaching 7.59℃/s. Through molecular dynamics simulation, it was found that the hydrogen bond types, bond lengths and bond angles of the two types of complex systems were different due to the difference of hydrocarbon surfactants. The essential law of the effects of CHX-3 and SDS on foam stability and surface tension was clarified. The research results can provide data support and theoretical support for the development, application and popularization of fluorine-free foam extinguishing agent.

Key words: fluorine-free foam extinguishing agent, foam properties, true fire experiment, cooling rate, molecular dynamics, inter-molecular hydrogen bonds

中图分类号:

X 936

贾海林, 曾锦祥, 潘荣锟, 潘仕利, 周凯旋. 无氟泡沫灭火剂真火实验与分子动力学模拟[J]. 化工学报, 2024, 75(10): 3825-3834.

Hailin JIA, Jinxiang ZENG, Rongkun PAN, Shili PAN, Kaixuan ZHOU. True fire experimental and molecular dynamic simulation of fluorine-free foam extinguishing agent[J]. CIESC Journal, 2024, 75(10): 3825-3834.

图/表 16

表1 无氟泡沫灭火剂的基剂信息

Table 1 Base agent information of fluorine-free foam extinguishing agent

原材料	生产厂商	主要成分及含量	离子属性	CMC/%(质量)	平衡表面张力/(mN/m)
SILOK	广州斯洛柯高子聚合物有限公司	甲基(丙基氢氧化物、乙氧基化物)双(三甲基甲硅烷氧基)硅烷65%~70%	阴离子	0.04	21.7
SDS	广东高顺化工进出口有限公司	十二烷基硫酸钠98.5%	阴离子	0.03	29.6
CHX-3	成都科宏达科技有限公司	月桂酰胺丙基甜菜碱 45%	两性离子	0.48	28.3
异丁醇	天津市风船化剂科技有限公司	异丁醇 99%	—	—	—

图1 不同质量分数下表面张力的变化趋势

Fig.1 Variation of surface tension under different mass fraction

表2 无氟泡沫灭火剂的复配方案

Table 2 Compositional formulation of fluorine-free foam extinguishing agent

配方	SILOK	异丁醇	SDS	CHX-3	黄原胶	二乙二醇丁醚	尿素	APP	乙二醇	水
Case1	0.040%	0.100%	0.030%	—	0.004%	0.010%	0.300%	0.150%	0.150%	99.216%
Case2	0.040%	0.030%	0.030%	—	0.004%	0.010%	0.300%	0.150%	0.150%	99.286%
Case3	0.040%	0.100%	—	0.480%	0.004%	0.010%	0.300%	0.150%	0.150%	98.766%
Case4	0.100%	0.100%	—	0.480%	0.004%	0.010%	0.300%	0.150%	0.150%	98.706%
Case5	0.100%	0.030%	—	0.480%	0.004%	0.010%	0.300%	0.150%	0.150%	98.776%

图2 Foamscan型泡沫扫描仪

Fig.2 Foam scanner named Foamscan

表3 无氟泡沫灭火剂的泡沫基础性能

Table 3 Foam base property of fluorine-free foam extinguishing agent

方案	表面张力/(mN/m)	发泡高度/mm	稳泡系数	发泡倍数	25%析液时间/s
Case1	22.6	167	0.9640	5.6	206
Case2	22.7	183	0.9617	6.6	203
Case3	21.3	196	0.9695	6.9	223
Case4	20.3	187	0.9733	6.7	238
Case5	20.5	210	0.9762	7.6	236

图3 泡沫产生及灭火装置

Fig.3 Foam generation and fire extinguishing device

图4 灭火现场原貌图

Fig.4 Original drawing of fire extinguishing scene

图5 5种复配方案的灭火效能

Fig.5 Fire-fighting efficiency of five kinds of composite schemes

图6 Case1方案灭火过程的温度变化曲线

Fig.6 Temperature curve of fire-fighting process under Case1 scheme

图7 Case4方案灭火过程的温度变化曲线

Fig.7 Temperature curve of fire-fighting process under Case4 scheme

图8 Case5方案灭火过程的温度变化曲线

Fig.8 Temperature curve of fire-fighting process under Case5 scheme

图9 CHX-3、SDS、SILOK、异丁醇和水的单分子模型

Fig.9 Single-molecule model of CHX-3, SDS, SILOK, isobutanol and water

图10 两类复配体系分子动力学模拟的结构模型

Fig.10 Structural model for molecular dynamics simulation of two kinds of compound system

图11 两类体系的氢键结合情况

Fig.11 Hydrogen bond of two kinds of systems

表4 两类复配体系中的氢键键长与键角

Table 4 Hydrogen bond length and bond angle of two kinds of compound system

泡沫复配体系	与水成氢键的分子	最小键长/nm	最大键长/nm	最小键角/(°)	最大键角/(°)
CHX-3/SILOK/异丁醇体系	CHX-3	0.173	0.237	104.36	132.40
	异丁醇	0.257	0.304	108.05	134.11
	SILOK	0.232	0.311	95.18	155.08
SDS/SILOK/异丁醇体系	SDS	0.239	0.318	103.24	129.91
	异丁醇	0.248	0.308	109.02	133.87
	SILOK	0.228	0.315	96.47	148.91

图12 两类复配体系中水分子的MSD曲线

Fig.12 MSD curves of water molecules of two kinds of compound system

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