硝酸羟胺的热稳定性评估及热分解机理研究<sup>*</sup>

doi:10.11896/j.issn.1005-023X.2017.04.030

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Abstract To evaluate the thermal stability of oxidizer hydroxylamine nitrate (HAN), the standard aluminum crucibles for liquid was used, and DSC measurements of hydroxylamine nitrate were performed using simultaneous thermal analysis at heating rates of 3 K/min, 4 K/min, 5 K/min. With the help of parameter values from the non-isothermal DSC curves of HAN, the thermal decomposition activation energy and pre-exponential constant were obtained by Kissinger method and Ozawa method. The self-acce-lerating decomposition temperature and thermal explosion temperature were calculated by Zhang-Hu-Xie-Li formula, Hu-Yang-Liang-Xie formula, Hu-Zhao-Gao method and Zhao-Hu-Gao method. And the most probable mechanism was studied. To study thermal decomposition mechanism, seven different paths of the thermal decomposition mechanism of hydroxylamine nitrate were designed, and density functional theory (DFT) with B3LYP/6-311++G (d, p) methods was used to carry out the kinetic analysis and thermodynamic analysis. The calculation results showed that T_SADT=370.05 K, T_be0=388.68 K,and T_bp0=397.54 K. Differential form of the most probable mechanism is 公式. Path 6, Path 5, Path 4 and Path 1 which produce NO and NO₂ were supported in priority, and Path 2, Path 7 and Path 3 which produce N₂ and N₂O were supported in secondary place. When the temperature was below 373 K, the reaction of Path 1′ could not occur spontaneously, and thermal decomposition of hydroxylamine nitrate could not be spontaneous. From the perspective of thermodynamics, it is safe for hydroxylamine nitrate storage at 370.05 K.

Key words： hydroxylamine nitrate thermal analysis thermal stability thermal decomposition mechanism density functional theory

Published: 02 May 2018

CLC number:	TJ55
	O657.33

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1 Ulas A, Boysan E. Numerical analysis of regenerative cooling in li-quid propellant rocket engines[J]. Aerospace Sci Technol,2013,24(1):187.
2 Wei C Y, et al. Thermal decomposition hazard evaluation of hydroxylamine nitrate[J]. J Hazardous Mater,2006,130:163.
3 Diez F J, Hernaiz G, Miranda J J, et al. On the capabilities of nano electrokinetic thrusters for space propulsion[J]. Acta Astronautica,2013,83:97.
4 Dheeraj A, Basu P, Tharakan T J. Prediction of gas-core vortices during draining of liquid propellants from tanks[J]. Aerospace Sci Technol,2014,32(1):60.
5 Fu J, Chen X Q, Huang Y Y. Validation of a compression mass gauge using groud tests for liquid propellant mass measurements[J]. Adv Space Res,2014,53(9):1359.
6 Technical report on hydroxylamine nitrate[R].US Department of Energy,1998.
7 Rachid A, Toshiyuki K, Yosui N, et al. Performance and deactivation of Ir-based catalyst during hydroxylamine nitrate catalytic decomposition[J]. Appl Catal A: General,2013,452:64.
8 Dan A, Laurence C, Sylvie R, et al. Catalytic and thermal decomposition of ionic liquid monopropellants using a dynamic reactor[J]. Chem Eng Process,2007,46:165.
9 Kai S K, Jitkai C, Tengku F, et al. Role of electrodes in ambient electrolytic decomposition of hydroxylamine nitrate (HAN) solutions[J]. Propulsion Power Res,2013,2(3):194.
10 Wang H T, Zhou J Y. Preparation of hydroxylamine nitrate (NH₂-OH·HNO₃) and its stabilizer[J]. Chem Propellants Polymeric Mater,2007,5(2):18(in Chinese).
汪洪涛, 周集义. 硝酸羟胺NH₂OH·HNO₃制备及其稳定剂综述[J]. 化学推进剂与高分子材料,2007,5(2):18.
11 Reshmi S, Vijayalakshmi K P, Thomas D, et al. Thermal decomposition of a diazido ester: Pyrolysis GC-MS and DFT study[J]. J Ana-lytical Appl Pyrolysis,2013,104:603.
12 Huang J B, Liu C, Tong H, et al. Theoretical studies on pyrolysis mechanism of xylopyranose[J]. Comput Theoretical Chem,2012,1001:44.
13 Liu C, Zhang Y Y, Huang X L. Study of guaiacol pyrolysis mechanism based on density function theory[J]. Fuel Process Technol,2014,123:159.
14 Wang S R, Ru B, Dai G X,et al.Pyrolysis mechanism study of mini-mally damaged hemicellulose polymers isolated from agricultural waste straw[J]. Bioresource Technol,2015,190:211.
15 Francis Stoessel. 化工工艺的热安全-风险评估与工艺设计[M]. 陈网桦, 彭金华, 陈利平, 译. 北京:科学出版社,2009:73.
16 Bao S L, Chen W H, Chen L P, et al. Identification and thermokinetics of autocatalytic exothermic decomposition of 2,4-dinitroto-luene[J]. Acta Phys Chim Sin,2013,29(3):479(in Chinese).
鲍士龙, 陈网桦, 陈利平, 等. 2,4-二硝基甲苯热解自催化特性鉴别及其热解动力学[J]. 物理化学学报,2013,29(3):479.
17 Xu L, Cui T B, Luo T L, et al. Thermal decomposition kinetics of benzoxazine-phenolic-epoxidized soybean oil copolymers[J]. Mater Rev:Res,2012,26(11):67(in Chinese).
徐丽, 崔铁兵, 雒廷亮, 等. 苯并噁嗪-酚醛-环氧豆油三元聚合体系的热分解行为研究[J]. 材料导报:研究篇,2012,26(11):67.
18 Hu R R, Gao H X, et al. Thermal safety of 1,1’-Dimethy-5,5’-azotetrazole and 2,2’-Dimethyl-5,5’-azotetrazole[J]. Chin J Energetic Mater,2011,19(2):126(in Chinese).
胡荣祖, 高红旭, 等. 1,1’-二甲基-5,5’-偶氮四唑-水合物和2,2’-二甲基-5,5’-偶氮四唑的热安全性[J].含能材料,2011,19(2):126.
19 Qi Z L, Zhang D F, Chen F X, et al. Thermal decomposition and non-isothermal decomposition kinetics of carbamazepine[J]. Russian J Phys Chem,2014,88(13):2308.
20 Zhao H A, Hu R Z, Wang X J, et al. Thermal safety of 1,3,3-Trinitroazetidine[J]. Acta Chim Sin,2009,67(22):2536(in Chinese).
赵宏安, 胡荣祖, 王喜军, 等. 1,3,3-三硝基氮杂环丁烷的热安全性[J]. 化学学报,2009,67(22):2536.
21 Lee H S, Litzinger T A. Chemical kinetic study of HAN decomposition[J]. Combustion Flame,2003,135:151.
22 Barney G S, Duval P B. Model for predicting hydroxylamine nitrate stability in plutonium process solutions[J]. J Loss Prevention Process Ind,2011,24:76.
23 Rachid A, Toshiyuki K, Noboru I, et al. New HAN-based mixtures for reaction control system and low toxic spacecraft propulsion subsystem: Thermal decomposition and possible thruster applications[J].Combustion Flame,2015,162:2686.
24 Zhang Z, Liu C, Li H J, et al. Theoretical studies of pyrolysis mechanism of xylan monomer[J]. Acta Chim Sin,2011,69(18):2099(in Chinese).
张智, 刘朝, 李豪杰, 等. 木聚糖单体热解机理的理论研究[J]. 化学学报,2011,69(18):2099.
25 Huang J B, Liu C, Wei S A, et al. Density functional theory study on the dehydration mechanism of glycerine[J]. Acta Chim Sin,2010,68(11):1043(in Chinese).
黄金保,刘朝,魏顺安,等. 丙三醇脱水反应机理的密度泛函理论研究[J]. 化学学报,2010,68(11):1043.