含氮量对硝化纤维素热解过程影响研究

doi:10.16265/j.cnki.issn1003-3033.2024.10.0560

中国安全科学学报 ›› 2024, Vol. 34 ›› Issue (10): 158-165.doi: 10.16265/j.cnki.issn1003-3033.2024.10.0560

含氮量对硝化纤维素热解过程影响研究

柴华¹(), 戚凯旋²^,^**()

¹ 中共中央党校(国家行政学院) 应急管理研究院,北京 100091
² 交通运输部水运科学研究院安全与应急技术研究中心,北京 100088

收稿日期:2024-06-20 修回日期:2024-08-22 出版日期:2024-12-05
通信作者:
^** 戚凯旋(1991—),男,江苏沛县人,博士,助理研究员,主要从事突发事件风险评估与应急决策、水运安全与应急技术方面的研究。E-mail: qikaixuan@wti.ac.cn。

作者简介:

柴华 (1992—),女,河南焦作人,博士,讲师,主要从事危险化学物质热风险性预测、城市风险防控、安全生产、应急管理等方面的研究。E-mail:xc30@mail.ustc.edu.cn。

基金资助:
国家重点研发计划项目(2023YFC3007305); 国家自然科学基金面上项目资助(72074196); 中央级公益性科研院所基本科研业务费专项(102409)

Study on influence of nitrogen content on nitrocellulose pyrolysis process

CHAI Hua¹(), QI Kaixuan²^,^**()

¹ Emergency Management Research Institute, Party School of the Central Committee of C.P.C (National Academy of Governance), Beijing 100091, China
² Security and Emergency Technology Research Center, China Waterborne Transport Research Institute, Beijing 100088, China

Received:2024-06-20 Revised:2024-08-22 Published:2024-12-05

摘要/Abstract

摘要：

为明确含氮量对硝化纤维素(NC)热解过程的影响,借助傅里叶变换红外光谱仪(FTIR)、热重分析(TG)-FTIR(TG-FTIR)和裂解(Py)-气相色谱(GC)/质谱分析仪,揭示不同含氮量NC的结构特征、热解特性和过程产物。结果表明: 随着含氮量的增加,NC的取代硝基数量增多,热解反应速率和反应进行程度随之增加,轻质气体比例增大且产物种类增多,高温下出现多种化学重组形式;NC的热解过程是先发生脱硝反应,再将大分子分解为小分子,然后发生碳骨架和环内氧桥断裂,通过明确不同含氮量NC的共性产物和各阶段主要的氮氧化物,建立一种基于温度划分原则的NC热解过程机制。

关键词: 含氮量, 硝化纤维素(NC), 热解过程, 结构特征, 气态产物

Abstract:

In order to study the effect of nitrogen content on pyrolysis process of NC, Fourier Transform Infrared spectrometer (FTIR), thermogravimetric analysis(TG)-FTIR and pyrolysis(Py) gas chromatography(GC)/mass spectrometry (MS) are used to reveal the structural characteristics, pyrolysis characteristics and process products of NCs with different nitrogen content. The results show that with the increase of nitrogen content, the amount of substituted nitro of NC increases, the pyrolysis reaction rate and reaction degree increase, the proportion of light gas increases and the product types increase, and a variety of chemical recombination forms appear at high temperature. In the pyrolysis process of NC, de-nitration reaction takes place first, and then large molecules are decomposed into small molecules, and then carbon skeleton and ring oxygen bridge fracture occurs. By identifying the common products of NC with different nitrogen content and the main nitrogen oxides in each stage, a mechanism of NC pyrolysis process based on the principle of temperature division is established.

Key words: nitrogen content, nitrocellulose (NC), pyrolysis process, structural characteristics, gaseous products

中图分类号:

X928.5化学物质致因事故

柴华, 戚凯旋. 含氮量对硝化纤维素热解过程影响研究[J]. 中国安全科学学报, 2024, 34(10): 158-165.

CHAI Hua, QI Kaixuan. Study on influence of nitrogen content on nitrocellulose pyrolysis process[J]. China Safety Science Journal, 2024, 34(10): 158-165.

图/表 8

图1

表1

图2

图3

图4

图5

表2

表3

参考文献 18

[1]	邵自强, 王文俊. 硝化纤维素结构与性能[M]. 北京: 国防工业出版社, 2011:1-30.
[2]	国务院调查组. 天津港“8·12”瑞海公司危险品仓库特别重大火灾爆炸事故调查报告[R]. 2016.
[3]	张任栋, 张礼敬, 陶刚. 模糊推理-组合赋权的化工工艺本质安全度研究[J]. 中国安全科学学报, 2023, 33(8): 149-155. doi: 10.16265/j.cnki.issn1003-3033.2023.08.1389
	ZHANG Rendong, ZHANG Lijing, TAO Gang. Study on intrinsic safety degree of chemical process based on fuzzy reasoning and combinatorial weighting[J]. China Safety Science Journal, 2023, 33(8): 149-155. doi: 10.16265/j.cnki.issn1003-3033.2023.08.1389
[4]	KUMITA Y, WADA Y, ARAI M, et al. A study on thermal stability of nitrocellulose[J]. Journal of the Japan Explosives Society: Explosion, Explosives and Pyrotechnics, 2002, 63(5): 271-274.
[5]	LIU Huwei, FU Ruonong. Studies on thermal decomposition of nitrocellulose by pyrolysis-gas chromatography[J]. Journal of Analytical and Applied Pyrolysis, 1988, 14(2/3): 163-169.
[6]	DAUERMAN L, TAJIMA Y A. Thermal decomposition and combustion of nitrocellulose[J]. AIAA Journal, 1968, 6(8): 1468-1473.
[7]	SHAFIZADEH F, WOLFROM M. The controlled thermal decomposition of cellulose nitrate. IV. C14-tracer experiments1, 2[J]. Journal of the American Chemical Society, 1958, 80(7): 1675-1677.
[8]	ROBERTSON R, NAPPER S S. LXXI.—The evolution of nitrogen peroxide in the decomposition of guncotton[J]. Journal of the Chemical Society, Transactions, 1907, 91:764-786.
[9]	NEVES A, ANGELIN E M, ROLDAO E, et al. New insights into the degradation mechanism of cellulose nitrate in cinematographic films by Raman microscopy[J]. Journal of Raman Spectroscopy, 2019, 50(2): 202-212.
[10]	BERTHUMEYRIE S, COLLIN S, BUSSIERE P O, et al. Photooxidation of cellulose nitrate: new insights into degradation mechanisms[J]. Journal of Hazardous Materials, 2014, 272: 137-147. doi: 10.1016/j.jhazmat.2014.02.039 pmid: 24685530
[11]	丁玎, 王昱, 纪晓慧, 等. 工作场所空气中甲醛含量快速检测方法[J]. 中国安全科学学报, 2023, 33(10): 247-252. doi: 10.16265/j.cnki.issn1003-3033.2023.10.0090
	DING Ding, WANG Yu, JI Xiaohui, et al. Rapid detection method of formaldehyde content in workplace air[J]. China Safety Science Journal, 2023, 33(10): 247-252. doi: 10.16265/j.cnki.issn1003-3033.2023.10.0090
[12]	JIN Miaomiao, LUO Nan, LI Guoping, et al. The thermal decomposition mechanism of nitrocellulose aerogel[J]. Journal of Thermal Analysis and Calorimetry, 2015, 121(2): 901-908.
[13]	RYCHL J, LATTUATI-DERIEUX A, MATISOV-RYCHL L, et al. Degradation of aged nitrocellulose investigated by thermal analysis and chemiluminescence[J]. Journal of Thermal Analysis and Calorimetry, 2011, 107(3): 1267-1276.
[14]	ZHAO Jing, XIUWEN Wang, HU Jun, et al. Thermal degradation of softwood lignin and hardwood lignin by TG-FTIR and Py-GC/MS[J]. Polymer Degradation and Stability, 2014, 108: 133-138.
[15]	武汉大学. 分析化学:第五版[M]. 北京: 高等教育出版社, 2011:234-239.
[16]	MOVASAGHI Z, REHMAN S, UR REHMAN D I. Fourier transform infrared (FTIR) spectroscopy of biological tissues[J]. Applied Spectroscopy Reviews, 2008, 43(2): 134-179.
[17]	ALON T, AMIRAV A. How enhanced molecular ions in cold EI improve compound identification by the NIST library[J]. Rapid Communications in Mass Spectrometry, 2015, 29: 2287-2292. doi: 10.1002/rcm.7392 pmid: 26522322
[18]	FAN S S, MASON D M. Properties of the system N₂O₄⇆2NO₂⇆2NO+ O₂[J]. Journal of Chemical and Engineering Data, 1962, 7: 183-186.

编号	波数/cm^-1	特征基团	相对吸光度
编号	波数/cm^-1	特征基团	NC-11.63	NC-11.92	NC-12.60
1	3 440	-OH拉伸振动	1	1	1
2	1 661	-NO₂不对称拉伸振动	1.94	2.35	3.50
3	1 279	-NO₂对称拉伸振动	1.86	2.33	3.04
4	1 159	不对称氧桥拉伸振动	0.18	0.20	0.63
5	1 067	环间C-O拉伸振动	0.57	0.65	0.59
6	1 022	环内C-O拉伸振动	0.02	0.03	0.04
7	1 002	环内C-O拉伸振动	0.10	0.14	0.41
8	836	-NO₂拉伸振动	0.94	1.13	2.66
9	746	-NO₂螺旋振动	0.13	0.15	0.66
10	688	-NO₂螺旋振动	0.09	0.10	0.42

时间/ min	产物	化学式	分子量/ (g·mol^-1)	相对峰面积占比/%
时间/ min	产物	化学式	分子量/ (g·mol^-1)	NC-11.63	NC-11.92	NC-12.60
2.42	轻质气体	—	—	66.59	75.79	88.38
8.47	1-甲基-2-吡咯烷酮	C₅H₉NO	99.13	6.29	2.40	2.07
28.74	(Z)-11-十六碳二烯酸	C₁₆H₃₀O₂	254.41	0.00	0.00	0.71
29.02	正十六烷酸	C₁₆H₃₂O₂	256.42	0.00	3.80	2.97
30.46	(E)-8-甲基-9-十四烯-1-醇乙酸酯	C₁₇H₃₂O₂	268.43	22.40	10.07	0.00
31.04	十八烷酸	C₁₈H₃₆O₂	284.48	0.00	4.31	0.95

气态产物		相对峰面积占比
气态产物		NC-11.63	NC-11.92	NC-12.60
轻质气体		55.06	69.01	69.91
含氮有机物		5.16	5.24	7.2
无氮有机物	含苯环的芳香族有机化合物	1.77	3.35	3.45
无氮有机物	脂肪族有机化合物	33.1	17.49	14.74

含氮量对硝化纤维素热解过程影响研究

Study on influence of nitrogen content on nitrocellulose pyrolysis process

RichHTML

PDF

可视化

摘要/Abstract

引用本文

使用本文

图/表 8

参考文献 18

相关文章 2

编辑推荐

Metrics

本文评价

[1]	董欣静, 蔡劲松. 事故灾难应急协同网络的结构特征及优化策略研究[J]. 中国安全科学学报, 2024, 34(10): 229-237.
[2]	卢平，鲍杰，沈兆武. 岩浆侵蚀区煤层孔隙结构特征及其对瓦斯赋存之影响分析[J]. 中国安全科学学报, 2001, 11(6): 41-.