微米/纳米PMMA粉尘爆炸抑制过程中压力特性与热化学动力学的相关性

郭瑞; 李南; 张新燕; 张延松; 徐畅; 张公妍; 赵兴; 解雨萱; 韩喆林

doi:10.11883/bzycj-2023-0058

微米/纳米PMMA粉尘爆炸抑制过程中压力特性与热化学动力学的相关性

doi: 10.11883/bzycj-2023-0058

郭瑞^1,,
李南¹,
张新燕^{1, 2, 3, ,},
张延松^{1, 2, 3},
徐畅¹,
张公妍¹,
赵兴¹,
解雨萱¹,
韩喆林¹

1.
山东科技大学安全与环境工程学院，山东青岛 266590
2.
山东科技大学矿山灾害预防控制省部共建国家重点实验室培育基地，山东青岛 266590
3.
青岛市生产安全火灾事故智能控制工程中心，山东青岛 266590

基金项目: 国家自然科学基金（51904170, 51974179）；山东省自然科学基金（ZR2018BEE006, ZR2019MEE118）

详细信息

作者简介:
郭　瑞（1997－　），女，硕士研究生，gr9709242021@163.com

通讯作者:
张新燕（1987－　），女，博士，副教授，xyzhang_safety@sdust.ecu.cn

中图分类号: O383
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- 被引次数: 0
出版历程
- 收稿日期: 2023-02-23
- 修回日期: 2023-04-23
- 网络出版日期: 2023-04-28
- 刊出日期: 2023-12-12

Correlation between pressure characteristics and thermochemical kinetics during suppression of micro/nano PMMA dust explosion

GUO Rui^1
,,
LI Nan¹,
ZHANG Xinyan^{1, 2, 3
, ,},
ZHANG Yansong^{1, 2, 3},
XU Chang¹,
ZHANG Gongyan¹,
ZHAO Xing¹,
XIE Yuxuan¹,
HAN Zhelin¹

1.
College of Safety and Environmental Engineering, Shandong University of Science and Technology, Qingdao 266590, Shandong, China
2.
Mine Disaster Prevention and Control-Ministry of State Key Laboratory Breeding Base, Shandong University of Science and Technology, Qingdao 266590, Shandong, China
3.
Qingdao Intelligent Control Engineering Center for Production Safety Fire Accident, Qingdao 266590, Shandong , China

摘要

摘要: 为了揭示微米/纳米PMMA (polymethyl methacrylate)粉尘爆炸的抑制机理，利用同步热分析仪和20 L爆炸试验装置，对微米/纳米PMMA粉尘在抑爆粉剂NaHCO₃干预下的热解动力学特性和爆炸特性展开了实验研究，分析了惰化爆炸混合体系的爆炸压力特性参数与热化学动力学参数的相关性，并探讨了基于热化学动力学的粉尘爆炸抑制机理。结果表明：NaHCO₃通过物理化学协同抑制作用影响了微米/纳米PMMA粉尘的热解及氧化进程，提高了爆炸混合体系的活化能，减弱了爆炸强度；且抑爆剂粒度越小、添加比例越大，爆炸混合体系的表观活化能越大；与最大爆炸压力相比较，最大爆炸压力上升速率对爆炸体系活化能的敏感度较高，而纳米PMMA粉尘对爆炸混合体系活化能的敏感度大于微米PMMA粉尘，抑爆效果也更显著。
- 粉尘爆炸 /
- 抑爆机理 /
- 热化学动力学 /
- 爆炸强度 /
- 相关性
Abstract: To reveal the explosion suppression mechanism of micron/nano polymethyl methacrylate (PMMA) dusts, the synchronous thermal analyzer and the 20-L explosion test device were used to test the pyrolysis oxidation characteristics and the explosion overpressure evolution characteristics of micro/nano PMMA dust under the intervention of NaHCO₃. Coats-Redfern method was used to calculate the kinetic parameters for the rapid pyrolysis of 30 μm and 100 nm PMMA and micro/nano mixtures, and the correlation between pressure characteristics and thermochemical kinetics during suppression of micro/nano PMMA dust explosion was analyzed, and then the suppression mechanism of dust explosion based on thermochemical kinetics was discussed by establishing the physical model of suppression mechanism of NaHCO₃ on micro/nano PMMA dust explosions. The results show that the pyrolysis oxidation processes of 30 μm and 100 nm PMMA dusts are suppressed by NaHCO₃, and the apparent activation energy and pre-exponential factor are increased. The maximum explosion pressure and the maximum explosion pressure rise rate of both micro- and nano-PMMA dusts are decreased obviously. In the pyrolysis stage of the mixture system, the suppression effect of NaHCO₃ is mainly dominated by physical suppression, including the cooling effect of both pyrolysis reaction and products as well as the dilution effect on the concentration of combustible reactant. In the oxidation stage of the mixture system, the suppression effect of NaHCO₃ is mainly dominated by chemical suppression. The free radicals are absorbed by the active groups NaOH, forming the Na↔NaOH suppression cycle. And for explosion suppressant, the smaller the particle size and the larger the adding mass ratio, the greater the apparent activation energy E of explosion mixture system, and the more significant the suppression effect. It is worth noting that compared with the maximum explosion pressure, the sensitivity of explosion pressure rise rate to the E increment of explosion mixture system is great, and nano-PMMA dust is more sensitive to the E increment of explosion mixture system than micro-PMMA dust, and the corresponding suppression effect of NaHCO₃ on nano-PMMA dust is more significant.
- dust explosion /
- explosion suppression mechanism /
- thermochemical kinetic /
- explosion intensity /
- correlation

HTML全文

图 1 30 μm和100 nm PMMA粉尘的粒度分布

Figure 1. Particle size distribution characteristics of 30 μm and 100 nm PMMA dusts

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图 2 微米/纳米混合粉尘的扫描电镜图像

Figure 2. Scanning electron microscope images of micro/nano mixed dusts

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图 3 同步热分析仪

Figure 3. A synchronous thermal analyzer

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图 4 20 L爆炸测试装置

Figure 4. A 20-L explosion test device

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图 5 30 μm、100 nm PMMA及质量分数37% NaHCO₃干预下的微米/纳米PMMA混合粉尘的热分析曲线

Figure 5. Thermal analysis curves of 30 μm, 100 nm PMMA dusts and micro/nano mixed dusts with 37% NaHCO₃

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图 6 30 μm、100 nm PMMA及添加NaHCO₃的微米/纳米混合粉尘的热解转化率

Figure 6. Pyrolysis conversion rates of 30 μm and 100 nm PMMA dusts as well as micro/nano mixed dusts with NaHCO₃

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图 7 30 μm与100 nm PMMA粉尘爆炸最大爆炸压力和最大爆炸压力上升速率的对比

Figure 7. Comparisons of the maximum explosion pressures and the maximum explosion pressure rise rates between 30 μm and 100 nm PMMA dusts

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图 8 53 μm NaHCO₃的质量分数对30 μm和100 nm PMMA粉尘爆炸特性参数的影响

Figure 8. Effect of mass fraction of 53 μm NaHCO₃ on the explosion characteristic parameters of 30 μm and 100 nm PMMA dust

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图 9 不同粒度NaHCO₃对最适爆炸浓度下30 μm和100 nm PMMA粉尘爆炸特性参数的影响

Figure 9. Effect of particle size of NaHCO₃ on the explosion characteristic parameters of 30 μm and 100 nm PMMA dusts at the optimal explosion concentration

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图 10 微米/纳米PMMA粉尘爆炸抑制过程中压力特性与热化学动力学的相关性

Figure 10. Correlation between pressure characteristics and thermochemical kinetics during suppression of micro/nano PMMA dust explosion

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图 11 NaHCO₃对微米/纳米PMMA粉尘爆炸抑制机理物理模型

Figure 11. Suppression mechanism of NaHCO₃ on micro/nano PMMA dust explosion

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表 1 30 μm和100 nm PMMA及不同质量添加比例的NaHCO₃干预下微米/纳米混合粉尘的热分析参数

Table 1. Thermal analysis parameters of 30 μm and 100 nm PMMA dusts as well as micro/nano mixed dustswith different mass ratios of NaHCO₃

样品	热解反应持续时间/min		失重率/%	平均热解反应速率/(%∙min⁻¹)
样品	快速热解阶段	慢速热解阶段	失重率/%	平均热解反应速率/(%∙min⁻¹)
30 μm PMMA	128	140	100	0.37
30 μm PMMA+37% NaHCO₃	98	426	70.5	0.13
30 μm PMMA+54% NaHCO₃	96	429	63.1	0.12
100 nm PMMA	122	62	100	0.54
100 nm PMMA+37% NaHCO₃	115	386	74.8	0.15
100 nm PMMA+54% NaHCO₃	113	388	66.0	0.13

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表 2 30 μm PMMA及添加NaHCO₃的微米混合粉尘在不同升温速率下的动力学参数

Table 2. Kinetic parameters of 30 μm PMMA and micro mixed dusts with NaHCO₃ at different heating rates

样品	升温速率/（K∙min⁻¹）	活化能/（kJ∙mol⁻¹）	指前因子/min⁻¹	机理函数
30 μm PMMA	5	219.82	2.75×10¹⁹	F4模型
	10	209.43	6.89×10¹⁸	F4模型
	15	224.23	2.18×10²⁰	F4模型
平均值		217.83	8.41×10¹⁹
30 μm PMMA+NaHCO₃	5	277.27	5.95×10²³	F3模型
	10	265.22	3.37×10²²	F3模型
	15	263.01	1.01×10²²	F3模型
平均值		268.50	2.13×10²³

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表 3 100 nm PMMA及添加NaHCO₃的纳米混合粉尘在不同升温速率下的动力学参数

Table 3. Kinetic parameters of 100 nm PMMA and nano-mixed dusts with NaHCO₃ at different heating rates

样品	升温速率/(K∙min⁻¹)	活化能/(kJ∙mol⁻¹)	指前因子/min⁻¹	机理函数
100 nm PMMA	5	179.67	9.25×10¹⁴	F2模型
	10	190.56	8.45×10¹⁵	F2模型
	15	199.20	5.26×10¹⁶	F2模型
平均值		189.81	2.07×10¹⁶
100 nm PMMA+NaHCO₃	5	252.66	2.67×10²²	F4模型
	10	244.63	2.48×10²¹	F4模型
	15	255.93	3.65×10²¹	F4模型
平均值		251.07	1.09×10²²

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参考文献(29)

[1]	曾文茹, 李疏芬, 周允基, 等. 聚甲基丙烯酸甲酯热氧化降解的化学动力学研究 [J]. 化学物理学报, 2003, 16(1): 64–68. DOI: 10.3969/j.issn.1674-0068.2003.01.013. ZENG W R, LI S F, ZHOU Y J, et al. Chemical kinetics on thermal oxidative degradation of PMMA [J]. Chinese Journal of Chemical Physics, 2003, 16(1): 64–68. DOI: 10.3969/j.issn.1674-0068.2003.01.013.
[2]	FATEH T, RICHARD F, ROGAUME T, et al. Experimental and modelling studies on the kinetics and mechanisms of thermal degradation of polymethyl methacrylate in nitrogen and air [J]. Journal of Analytical and Applied Pyrolysis, 2016, 120: 423–433. DOI: 10.1016/j.jaap.2016.06.014.
[3]	VIGNES A, KRIETSCH A, DUFAUD O, et al. Course of explosion behaviour of metallic powders: from micron to nanosize [J]. Journal of Hazardous Materials, 2019, 379: 120767. DOI: 10.1016/j.jhazmat.2019.120767.
[4]	YUAN Z, KHAKZAD N, KHAN F, et al. Dust explosions: a threat to the process industries [J]. Process Safety and Environmental Protection, 2015, 98: 57–71. DOI: 10.1016/j.psep.2015.06.008.
[5]	WEI L J, SU M Q, WANG K, et al. Suppression effects of ABC powder on explosion characteristics of hybrid C₂H₄/polyethylene dust [J]. Fuel, 2022, 310: 122159. DOI: 10.1016/j.fuel.2021.122159.
[6]	AMYOTTE P R. Some myths and realities about dust explosions [J]. Process Safety and Environmental Protection, 2014, 92(4): 292–299. DOI: 10.1016/j.psep.2014.02.013.
[7]	WANG Q H, YANG S P, JIANG J C, et al. Flame propagation and spectrum characteristics of CH₄-air gas mixtures in a vertical pressure relief pipeline [J]. Fuel, 2022, 317: 123413. DOI: 10.1016/j.fuel.2022.123413.
[8]	YANG J, LI Y H, YU Y, et al. Experimental investigation of the inerting effect of CO₂ on explosion characteristics of micron-size Acrylate Copolymer dust [J]. Journal of Loss Prevention in the Process Industries, 2019, 62: 103979. DOI: 10.1016/j.jlp.2019.103979.
[9]	YANG J, YU Y, LI Y H, et al. Inerting effects of ammonium polyphosphate on explosion characteristics of polypropylene dust [J]. Process Safety and Environmental Protection, 2019, 130: 221–230. DOI: 10.1016/j.psep.2019.08.015.
[10]	ADDAI E K, GABEL D, KRAUSE U. Experimental investigations of the minimum ignition energy and the minimum ignition temperature of inert and combustible dust cloud mixtures [J]. Journal of Hazardous Materials, 2016, 307: 302–311. DOI: 10.1016/j.jhazmat.2016.01.018.
[11]	JIANG H P, BI M S, PENG Q K, et al. Suppression of pulverized biomass dust explosion by NaHCO₃ and NH₄H₂PO₄ [J]. Renewable Energy, 2020, 147: 2046–2055. DOI: 10.1016/j.renene.2019.10.026.
[12]	HUANG C Y, CHEN X F, YUAN B H, et al. Suppression of wood dust explosion by ultrafine magnesium hydroxide [J]. Journal of Hazardous Materials, 2019, 378: 120723. DOI: 10.1016/j.jhazmat.2019.05.116.
[13]	ZHANG X Y, GAO W, YU J L, et al. Flame propagation mechanism of nano-scale PMMA dust explosion [J]. Powder Technology, 2020, 363: 207–217. DOI: 10.1016/j.powtec.2019.12.056.
[14]	ZHANG X Y, GAO W, YU J L, et al. Effect of flame propagation regime on pressure evolution of nano and micron PMMA dust explosions [J]. Journal of Loss Prevention in the Process Industries, 2020, 63: 104037. DOI: 10.1016/j.jlp.2019.104037.
[15]	ZHANG X Y, YU J L, YAN X Q, et al. Flame propagation behaviors of nano- and micro-scale PMMA dust explosions [J]. Journal of Loss Prevention in the Process Industries, 2016, 40: 101–111. DOI: 10.1016/j.jlp.2015.12.010.
[16]	ZHOU J H, LI B, MA D Q, et al. Suppression of nano-polymethyl methacrylate dust explosions by ABC powder [J]. Process Safety and Environmental Protection, 2019, 122: 144–152. DOI: 10.1016/j.psep.2018.11.023.
[17]	ZHOU J H, JIANG H P, ZHOU Y H, et al. Flame suppression of 100 nm PMMA dust explosion by KHCO₃ with different particle size [J]. Process Safety and Environmental Protection, 2019, 132: 303–312. DOI: 10.1016/j.psep.2019.10.027.
[18]	GAN B, LI B, JIANG H P, et al. Suppression of polymethyl methacrylate dust explosion by ultrafine water mist/additives [J]. Journal of Hazardous Materials, 2018, 351: 346–355. DOI: 10.1016/j.jhazmat.2018.03.017.
[19]	GAO W, MOGI T, SUN J H, et al. Effects of particle thermal characteristics on flame structures during dust explosions of three long-chain monobasic alcohols in an open-space chamber [J]. Fuel, 2013, 113: 86–96. DOI: 10.1016/j.fuel.2013.05.071.
[20]	GAO W, ZHONG S J, MOGI T, et al. Study on the influence of material thermal characteristics on dust explosion parameters of three long-chain monobasic alcohols [J]. Journal of Loss Prevention in the Process Industries, 2013, 26(1): 186–196. DOI: 10.1016/j.jlp.2012.10.007.
[21]	LIU A H, CHEN J Y, HUANG X F, et al. Explosion parameters and combustion kinetics of biomass dust [J]. Bioresource Technology, 2019, 294: 122168. DOI: 10.1016/j.biortech.2019.122168.
[22]	LI Q Z, ZHANG G Y, ZHENG Y N, et al. Investigation on the correlations between thermal behaviors and explosion severity of aluminum dust/air mixtures [J]. Powder Technology, 2019, 355: 582–592. DOI: 10.1016/j.powtec.2019.07.090.
[23]	JIANG H P, BI M S, GAO Z H, et al. Effect of turbulence intensity on flame propagation and extinction limits of methane/coal dust explosions [J]. Energy, 2022, 239: 122246. DOI: 10.1016/j.energy.2021.122246.
[24]	JIANG H P, BI M S, HUANG L, et al. Suppression mechanism of ultrafine water mist containing phosphorus compounds in methane/coal dust explosions [J]. Energy, 2022, 239: 121987. DOI: 10.1016/j.energy.2021.121987.
[25]	YAN X Q, YU J L. Dust explosion venting of small vessels at the elevated static activation overpressure [J]. Powder Technology, 2014, 261: 250–256. DOI: 10.1016/j.powtec.2014.04.043.
[26]	Explosive atmospheres: Part 20-2: Material characteristics: Combustible dusts test methods: Technical Corrigendum 1: ISO/IEC 80079-20-2: 2016/Cor 1: 2017 [S]. Geneva: International Electrotechnical Commission, 2017.
[27]	张公妍, 张延松, 陈昆, 等. 模式拟合法和无模式函数法对月桂酸热解行为及机理的研究 [J]. 日用化学工业, 2021, 51(4): 265–271. DOI: 10.3969/j.issn.1001-1803.2021.04.001. ZHANG G Y, ZHANG Y S, CHEN K, et al. Study on the behavior and mechanism of pyrolysis of lauric acid by model-fitting and model-free methods [J]. China Surfactant Detergent & Cosmetics, 2021, 51(4): 265–271. DOI: 10.3969/j.issn.1001-1803.2021.04.001.
[28]	ZHANG G Y, ZHANG Y S, HUANG X W, et al. Effect of pyrolysis and oxidation characteristics on lauric acid and stearic acid dust explosion hazards [J]. Journal of Loss Prevention in the Process Industries, 2020, 63: 104039. DOI: 10.1016/j.jlp.2019.104039.
[29]	曾文茹, 李疏芬, 周允基. 快速升温条件下聚甲基丙烯酸甲酯的燃烧机理 [J]. 高分子材料科学与工程, 2003, 19(6): 183–186. DOI: 10.16865/j.cnki.1000-7555.2003.06.047. ZENG W R, LI S F, ZHOU Y J. Study of the combustion mechanism of poly (methyl methacrylate) [J]. Polymer Materials Science and Engineering, 2003, 19(6): 183–186. DOI: 10.16865/j.cnki.1000-7555.2003.06.047.