N-甲基氧化吗啉热分解动力学分析

摘要对在纤维素溶剂中具有广泛应用的N-甲基氧化吗啉(NMMO)热分解动力学进行研究。首先利用绝热加速量热仪(ARC)开展绝热分解实验,得到NMMO在绝热条件下的初始分解温度为119.87 ℃,通过动力学计算得到反应活化能为219.7 kJ·mol^-1,为自分解一级反应。其次通过差示扫描量热仪(DSC)对NMMO进行非等温分解实验,并利用Friedman法、Flynn-Wall-Ozawa法和ASTM E698法3种动力学模型进行分解动力学计算。研究结果显示NMMO的初始分解温度为161.07~186.40 ℃,反应活化能分别为81~134、75.81~100.34 和101.92 kJ·mol^-1。最后利用风险矩阵法定量评估NMMO热分解危险等级为Ⅲ级。该研究结果为降低NMMO生产、储存和运输中发生分解反应的风险提供了理论依据。

	Service

	把本文推荐给朋友
	加入我的书架
	加入引用管理器
	Email Alert
	RSS
	作者相关文章
	高建村
	史晨光
	王薇
	刘思思
	李玉静
	王胜男

关键词：甲基氧化吗啉热分解热动力学安全评估风险矩阵

Abstract： N-methylmorpholine-N-oxide (NMMO) is widely used in cellulose solvents. In this paper, the thermal kinetics of NMMO was studied. First, the adiabatic decomposition experiment was carried out using the accelerating rate calorimeter (ARC), and the initial decomposition temperature of NMMO under adiabatic mode was 119.87 ℃. The apparent activation energy was 219.7 kJ·mol^-1 and the reaction order was 1 by kinetic calculation. Second, differential scanning calorimetry (DSC) was used to investigate the decomposition process at different heating rates, and the thermal kinetics parameters of NMMO were obtained by Friedman method, Flynn-Wall-Ozawa method and ASTM E698 method software AKTS. The initial decomposition temperature was 161.07—186.40 ℃, and the apparent activation energy of the three models were 81—134 kJ·mol^-1, 75.81—100.34 kJ·mol^-1 and 101.92 kJ·mol^-1, respectively, which were lower than those of the ARC experimental results. Finally, the risk level of NMMO thermal decomposition was three grade by the risk matrix method. The results provide theoretical basis for reducing risk in NMMO production, storage and transportation.

Keywords： N-methylmorpholine-N-oxide thermal decomposition thermal kinetics safety assessment risk matrix

Received 2022-02-20;

Corresponding Authors: 王薇,助理教授,E-mail:daqingwei1@126.com。 Email: daqingwei1@126.com

About author: 高建村(1964-),男,博士,教授,现从事应用化学和安全工程方向的研究。

引用本文:

高建村, 史晨光, 王薇, 刘思思, 李玉静, 王胜男.N-甲基氧化吗啉热分解动力学分析[J]. 化学工业与工程, 2023,40(4): 86-93

GAO Jiancun, SHI Chenguang, WANG Wei, LIU Sisi, LI Yujing, WANG Shengnan.Thermal kinetics of N-methylmorpholine-N-oxide in the decomposition process[J]. Chemcial Industry and Engineering, 2023,40(4): 86-93

[1] FINK H P, WEIGEL P, PURZ H J, et al. Structure formation of regenerated cellulose materials from NMMO-solutions[J]. Progress in Polymer Science, 2001, 26(9):1473-1524
[2] JADHAV S, LIDHURE A, THAKRE S, et al. Modified Lyocell process to improve dissolution of cellulosic pulp and pulp blends in NMMO solvent[J]. Cellulose, 2021, 28(2):973-990
[3] PROTZ R, LEHMANN A, GANSTER J, et al. Solubility and spinnability of cellulose-lignin blends in aqueous NMMO[J]. Carbohydrate Polymers, 2021, doi:10.1016/j.carbpol.2020.117027
[4] 吴翠玲, 李新平, 秦胜利, 等. 新型有机纤维素溶剂:NMMO的研究[J]. 兰州理工大学学报, 2005, 31(2):73-76 WU Cuiling, LI Xinping, QIN Shengli, et al. Study of new organic cellulose solvent:N-methyl morpholine-N-oxide (NMMO)[J]. Journal of Lanzhou University of Technology, 2005, 31(2):73-76(in Chinese)
[5] 周方越, 马云. 天津爆炸事故的分析、处理及启示[J]. 经贸实践, 2016(1):329-329 ZHOU Fangyue, MA Yun. Analysis, treatment and enlightenment of Tianjin explosion accident[J]. Economic & Trade, 2016(1):329-329(in Chinese)
[6] CYMERMAN CRAIG J, PURUSHOTHAMAN K K. An improved preparation of tertiary amine N-oxides[J]. The Journal of Organic Chemistry, 1970, 35(5):1721-1722
[7] CORREA P E, HARDY G, RILEY D P. Selective autoxidation of electron-rich substrates under elevated oxygen pressures[J]. The Journal of Organic Chemistry, 1988, 53(8):1695-1702
[8] 孟宇伯, 高殿明, 赵倩. N-甲基氧化吗啉的合成研究[J]. 精细化工, 1996, 13(3):15-17 MENG Yubo, GAO Dianming, ZHAO Qian. The synthesis study of N-methyl morpholine oxide[J]. Fine Chemicals, 1996, 13(3):15-17(in Chinese)
[9] 徐军辉, 刘羿君, 封云芳, 等. 氧化甲基吗啉的合成研究[J]. 浙江理工大学学报, 2008, 25(4):402-405 XU Junhui, LIU Yinjun, FENG Yunfang, et al. The synthesis study of N-methylmorpholine-N-oxide[J]. Journal of Zhejiang Sci-Tech University, 2008, 25(4):402-405(in Chinese)
[10] ETO I, AKIYOSHI M, MATSUNAGA T, et al. Influenceof heavy metal ion on the thermal explosion of hydrogen peroxide[J].Journal of Thermal Analysis and Calorimetry, 2006, 85(3):623-627
[11] KUMASAKI M. An explosion of a tank car carrying waste hydrogen peroxide[J]. Journal of Loss Prevention in the Process Industries, 2006, 19(4):307-311
[12] ZHANG J, MA Y, CHEN L, et al. Experimental and numerical simulation to identify the thermal hazards and hazardous scenarios of N-nitrodihydroxyethyl dinitrate[J]. Process Safety and Environmental Protection, 2021, 145:211-221
[13] ZHANG Z, LIU S, ZHANG B, et al. Runaway reaction and thermal hazards simulation of 4-amino-1, 2, 4-triazole picrate by HP-DSC and ARC[J]. Journal of Thermal Analysis and Calorimetry, 2020, 139(2):1367-1377
[14] 陈莹莹, 陈利平, 陈网桦, 等. 硝基胍溶液的热分解性能及动力学[J]. 含能材料, 2017, 25(3):257-261 CHEN Yingying, CHEN Liping, CHEN Wanghua, et al. Thermal decomposition characteristic and kinetics of nitroguanidine solution[J]. Chinese Journal of Energetic Materials, 2017, 25(3):257-261(in Chinese)
[15] LI B, LUO Y, WANG H, et al. Thermal kinetic performance and thermal safety of 3, 3'-bis-oxadiazole-5, 5'-bis-methylene dinitrate[J]. Propellants, Explosives, Pyrotechnics, 2020, 45(12):1870-1876
[16] CONG Y, WEI Z, MA X, et al. Determination of SADT and TMR_ad of 3-bromo-1-(3, 5-dichloropyridin-2-yl)-4, 5-dihydro-1H-pyrazole-5-carboxylic acid:Applying thermal decomposition kinetics[J]. Results in Chemistry, 2021, doi:10.1016/j.rechem.2021.100112
[17] 王建娜, 韩蒙蒙, 宁艳霞, 等. O-3-氯-2-丙烯基羟胺热危险性及其淬灭研究[J]. 化学工业与工程, 2022, 39(1):27-32 WANG Jianna, HAN Mengmeng, NING Yanxia, et al. Study on thermal hazard and quenching of O-(3-chloro-2-propenyl)-hydroxylamine[J]. Chemical Industry and Engineering, 2022, 39(1):27-32(in Chinese)
[18] ABRISHAMI F, CHIZARI M, ZOHARI N, et al. Study on thermal stability and decomposition kinetics of bis (2, 2-dinitropropyl) fumarate (BDNPF) as a melt cast explosive by model-free methods[J]. Propellants, Explosives, Pyrotechnics, 2019, 44(11):1446-1449
[19] BÖHMDORFER S, HOSOYA T, RÖDER T, et al. A cautionary note on thermal runaway reactions in mixtures of 1-alkyl-3-methylimidazolium ionic liquids and N-methylmorpholine-N-oxide[J]. Cellulose, 2017, 24(5):1927-1932
[20] VYAZOVKIN S, BURNHAM A K, CRIADO J M, et al. ICTAC Kinetics Committee recommendations for performing kinetic computations on thermal analysis data[J]. Thermochimica Acta, 2011, 520(1/2):1-19
[21] CAO C, LIU S. Thermal hazard characteristic evaluation of two low-temperature-reactive azo compounds under adiabatic process conditions[J]. Process Safety and Environmental Protection, 2019, 130:231-237
[22] SUN D, MIAO X, XIE C, et al. Study on thermal properties and kinetics of benzoyl peroxide by ARC and C80 methods[J]. Journal of Thermal Analysis and Calorimetry, 2012, 107(3):943-948
[23] 何志伟, 颜事龙, 刘祖亮, 等. 加速量热仪研究2, 4, 6-三氨基-3, 5-二硝基吡啶-1-氧化物的热分解[J]. 含能材料, 2015, 23(5):415-419 HE Zhiwei, YAN Shilong, LIU Zuliang, et al. Adiabatic decomposition properties of 2, 4, 6-triamino-3, 5-dinitropyridine-1-oxide by accelerating rate calorimeter[J]. Chinese Journal of Energetic Materials, 2015, 23(5):415-419(in Chinese)
[24] TOWNSEND D I, TOU J. Thermal hazard evaluation by an accelerating rate calorimeter[J]. Thermochimica Acta, 1980, 37(1):1-30
[25] PASTRÉ J, WÖRSDÖRFER U, KELLER A, et al. Comparison of different methods for estimating TMR_ad from dynamic DSC measurements with ADT 24 values obtained from adiabatic Dewar experiments[J]. Journal of Loss Prevention in the Process Industries, 2000, 13(1):7-17
[26] MUSUC A M, BIRZAN L, CRISTEA M, et al. A DSC study of new compounds based on (E)-3-(azulen-1-yldiazenyl)-1, 2, 5-oxadiazole[J].Journal of Thermal Analysis and Calorimetry, 2021, 146(4):1763-1772
[27] OZAWA T. Estimation of activation energy by isoconversion methods[J]. Thermochimica Acta, 1992, 203:159-165
[28] ASTM E698. Standard test method for Arrhenius kinetic constants for thermally unstable materials using differential scanning calorimetry and the Flynn/Wall/Ozawa method[M]. West Conshohocken, PA:ASTM International, 1999
[29] DOYLE C. Study on lifetime of energetic materials under different storage conditions[J]. J Appl Polym Sci, 1962, 6:639-645
[30] SIVAPIRAKASAM S P, NALLA MOHAMED M, SURIANARAYANAN M, et al. Evaluation of thermal hazards and thermo-kinetic parameters of a matchhead composition by DSC and ARC[J]. Thermochimica Acta, 2013, 557:13-19
[31] WU X, CHEN L, RAO G, et al. Impacts of thermal inertia factor on adiabatic decomposition of 40% mass content DCP in ethyl benzene[J]. Journal of Chemistry, 2020, 2020(2):1-8