硅泥双阶段放热特性及临界自燃温度研究*

doi:10.16265/j.cnki.issn1003-3033.2026.03.0415

中国安全科学学报 ›› 2026, Vol. 36 ›› Issue (3): 162-170.doi: 10.16265/j.cnki.issn1003-3033.2026.03.0415

硅泥双阶段放热特性及临界自燃温度研究^*

陶润东¹(), 包志明²^,³^,⁴, 胡成²^,³^,⁴, 徐晓楠¹^,^**(), 郝天姿²^,³^,⁴, 李晶晶²^,³^,⁴

¹ 中国矿业大学(北京) 应急管理与安全工程学院, 北京 100083
² 应急管理部天津消防研究所, 天津 300381
³ 工业与公共建筑火灾防控技术应急管理部重点实验室, 天津 300381
⁴ 天津市消防安全技术重点实验室, 天津 300381

收稿日期:2025-10-06 修回日期:2025-12-28 出版日期:2026-03-31
通信作者:
^** 徐晓楠(1964—),女,辽宁辽阳人,硕士,教授,硕士生导师,主要从事阻燃材料开发及应用、消防工程理论与技术、火灾仿真模拟等研究。E-mail:xxn.pro@126.com。
作者简介:
陶润东 (2001—),男,安徽六安人,硕士研究生,主要研究方向为火灾防治。E-mail:cumtbt2001@126.com。
包志明,研究员。
胡成,副研究员。
李晶晶,副研究员。
基金资助:
中央级公益性科研院所基本科研业务费专项资金项目(2024SJ37)

Study on dual-stage exothermic characteristics and critical spontaneous combustion temperature of silicon sludge

TAO Rundong¹(), BAO Zhiming²^,³^,⁴, HU Cheng²^,³^,⁴, XU Xiaonan¹^,^**(), HAO Tianzi²^,³^,⁴, LI Jingjing²^,³^,⁴

¹ School of Emergency Management and Safety Engineering, China University of Mining and Technology (Beijing), Beijing 100083, China
² Tianjin Fire Science and Technology Research Institute of MEM, Tianjin 300381, China
³ Key Laboratory of Fire Protection Technology for Industry and Public Building, Ministry of Emergency Management, Tianjin 300381, China
⁴ Tianjin Key Laboratory of Fire Safety Technology, Tianjin 300381, China

Received:2025-10-06 Revised:2025-12-28 Published:2026-03-31

摘要/Abstract

摘要：

为解决光伏硅泥的自燃事故频发问题,通过多试验方法揭示其双阶段放热特征及临界自燃尺寸。使用恒温微量热仪分析30 ℃低温环境下硅泥的放热来源及 pH 值、粒径对放热特性的影响;借助同步热分析仪研究 40~1 300 ℃程序升温过程中硅泥的热行为,通过 Flynn-Wall-Ozawa 法求解氧化阶段活化能,以揭示高温反应机制;基于金属网篮自热试验结合 Frank-Kamenetski 理论计算不同环境温度、样品状态下硅泥的临界自燃温度与临界尺寸;提出光伏硅泥安全储运的针对性管控建议。研究结果表明:低温阶段(30 ℃),硅泥放热由硅-水反应与硅-碱反应主导,碱性环境及小粒径可使最大放热功率增至 837.5 μW,显著提升蓄热风险;高温阶段(>405 ℃),硅-氧氧化反应成为主放热源,氧化活化能从 177 kJ/mol 降至 141 kJ/mol,反应由界面化学控制转向扩散控制。烘干硅泥、含碱硅泥及小粒径硅泥的临界自燃尺寸显著降低,环境温度每升高 10 ℃,临界自燃尺寸呈倍数下降,60 ℃时堆垛临界自燃尺寸最低为 2.2 m。

关键词: 硅泥自燃, 放热特性, 临界自燃温度, pH值, 放热功率, 活化能

Abstract:

To address the frequent spontaneous combustion accidents of photovoltaic silicon sludge, a multi-experimental approach was employed to reveal its dual-stage exothermic characteristics and critical spontaneous combustion size. An isothermal microcalorimeter was used to analyze the heat release sources of silicon sludge under a low-temperature environment of 30 ℃, and to investigate the effects of pH and particle size on heat release characteristics. Simultaneous thermal analysis was applied to investigate the thermal behavior of silicon sludge during the programmed temperature rise process of 40-1 300 ℃, and the flynn-wall-ozawa method was adopted to determine the activation energy of the oxidation stage, revealing the high-temperature reaction mechanism. Based on metal basket self-heating tests and Frank-Kamenetskii theory, the critical spontaneous combustion temperature and critical size of silicon sludge under different ambient temperatures and sample states were calculated. Targeted safety control suggestions for the safe storage and transportation of photovoltaic silicon sludge were proposed. The results show that in the low-temperature stage (30 ℃), the heat release of silicon sludge is dominated by silicon-water and silicon-alkali reactions. The alkaline environment and small particle size can increase the maximum heat release power to 837.5 μW, significantly enhancing the heat accumulation risk. In the high-temperature stage (>405 ℃), the silicon-oxygen oxidation reaction becomes the main heat release source, and the oxidation activation energy decreases from 177 kJ/mol to 141 kJ/mol, with the reaction transitions from interfacial chemical control to diffusion control. The critical spontaneous combustion size of dried silicon sludge, alkali-containing silicon sludge, and silicon sludge with small particle size is significantly reduced, and for every 10 ℃ increase in ambient temperature, the critical spontaneous combustion size decreases multiplicatively. The minimum critical stacking size is 2.2 m at 60 ℃.

Key words: silicon sludge spontaneous combustion, exothermic characteristics, critical spontaneous combustion temperature, pH value, exothermic power, activation energy

中图分类号:

X932爆炸安全与防火、防爆

陶润东, 包志明, 胡成, 徐晓楠, 郝天姿, 李晶晶. 硅泥双阶段放热特性及临界自燃温度研究^*[J]. 中国安全科学学报, 2026, 36(3): 162-170.

TAO Rundong, BAO Zhiming, HU Cheng, XU Xiaonan, HAO Tianzi, LI Jingjing. Study on dual-stage exothermic characteristics and critical spontaneous combustion temperature of silicon sludge[J]. China Safety Science Journal, 2026, 36(3): 162-170.

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样品编号	1	2	3	4	5	6
硅泥状态	烘干	含水	含水	含水	烘干	烘干
硅泥粒径/目	10	10	40	100	10	10
溶液类型	—	压滤废水	压滤废水	—	NaOH溶液	NaOH溶液
水分pH值	—	偏酸性	偏酸性	—	9	11
含水率/%	—	~46	~46	~46	50	50

样品编号	1	2	3	4	5	6
最大放热功率/μW	57.2	69.2	171.7	238.5	311.2	837.5
43 h放热功率/μW	18.1	68.8	132.3	116.0	143.7	170.0

立方体网篮尺寸/mm		25	40	60
临界自燃温度θ_c/℃	样品1	189	176	159
	样品2	171	163	154
	样品3	176	162.5	147
	样品5	197.5	182	167.5

环境温度/℃		30	40	50	60
临界尺寸 2r/m	样品1	19.4	10.4	5.8	3.4
	样品2	736.2	260.5	92.4	39.5
	样品3	12.0	6.5	3.7	2.2
	样品5	33.9	17.6	9.6	5.4

硅泥双阶段放热特性及临界自燃温度研究^*

Study on dual-stage exothermic characteristics and critical spontaneous combustion temperature of silicon sludge

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