Nitrolysis kinetics of DADN by N2O5/HNO3

doi:10.3969/j.issn.0438-1157.2013.04.021

CIESC Journal ›› 2013, Vol. 64 ›› Issue (4): 1269-1275.DOI: 10.3969/j.issn.0438-1157.2013.04.021

Previous Articles Next Articles

Nitrolysis kinetics of DADN by N₂O₅/HNO₃

HE Zhiyong¹, LUO Jun¹, LV Chunxu¹, XU Rong², LI Jinshan²

1. School of Chemical Engineering, Nanjing University of Science and Technology, Nanjing 210094, Jiangsu, China;
2. Institute of Chemical Materials, CAEP, Mianyang 621900, Sichuan, China

Received:2012-06-28 Revised:2012-10-30 Online:2013-04-05 Published:2013-04-05
Supported by:
supported by the National Natural Science Foundation of China(10976014).

N₂O₅/HNO₃体系中硝解DADN的反应动力学

何志勇¹, 罗军¹, 吕春绪¹, 徐容², 李金山²

1. 南京理工大学化工学院,江苏南京 210094;
2. 中国工程物理研究院化工材料研究所,四川绵阳 621900

通讯作者: 罗军
作者简介:何志勇(1975—),男,博士研究生,高级工程师。
基金资助:
国家自然科学基金项目(10976014)。

Abstract

Abstract: Concentrations of reactant, intermediate, product were measured by HPLC during nitrolysis of DADN(1,5-diacetyl-3,7-dinitro-1,3,5,7-tetraazacyclooctane) by N₂O₅/HNO₃ at temperatures of 303, 313, 323, and 333 K.Based on the mechanism of the nitrolysis reaction(first-order consecutive reaction), the kinetic parameters were calculated from these data obtained.The activation energies were 2.3996?10⁴ J穖ol^-1 for the first step(DADN to SEX(1-acetyl-3,5,7-trinitro-1,3,5,7-tetrazacyclooctane)) and 1.6598?10⁴ J穖ol^-1 for the second step(SEX to HMX(high melt point explosive)), and the pre-exponential factors were 2.2000?10⁴ h^-1 and 6.5178?10² h^-1, respectively.The reaction rate constant is larger for the fist step than for the second one. In order to check the intermediate in nitrolysis reaction of DADN, an experiment was carried out to separate and identify the intermediate(also by-product).The results indicate that this intermediate is SEX.

Key words: N₂O₅, DADN, SEX, HMX, nitrolysis, reaction kinetics

摘要： 采用高效液相色谱跟踪检测了不同温度条件下N₂O₅/HNO₃体系硝解DADN时反应底物、中间体和产物浓度随时间的变化情况。通过对303、313、323、333 K温度下实验数据的分析,计算得到各步的反应速率常数,并最终求得DADN到SEX和SEX到HMX两步的反应活化能分别为2.3996×10⁴ J·mol^-1和1.6598×10⁴ J·mol^-1,指前因子分别为2.2000×10⁴ h^-1和6.5178×10² h^-1。同时,通过柱分离得到的中间产物经结构鉴定为SEX,对其硝基机理进行了分析,实验证明DADN的硝解反应分两步进行,是一级连串反应过程,控制步骤是SEX到HMX。

关键词: N₂O₅, DADN, SEX, HMX, 硝解, 反应动力学

CLC Number:

O626

HE Zhiyong, LUO Jun, LV Chunxu, XU Rong, LI Jinshan. Nitrolysis kinetics of DADN by N₂O₅/HNO₃[J]. CIESC Journal, 2013, 64(4): 1269-1275.

何志勇, 罗军, 吕春绪, 徐容, 李金山. N₂O₅/HNO₃体系中硝解DADN的反应动力学[J]. 化工学报, 2013, 64(4): 1269-1275.

References 22

[1]	Ren Tesheng(任特生).Nitramine and Nitrate Ester Explosives, Chemistry and Technology(硝胺及硝酸酯炸药化学与工艺学)[M].Beijing:Weapon Industry Press, 1994:203-223
[2]	Qian Hua(钱华), Lü Chunxu(吕春绪), Ye Zhiwen(叶志文).Clean nitrating agent dinitrogen pentoxide and its application in nitration[J].Fine Chemicals(精细化工), 2006, 23:620-624
[3]	Ge Zhongxue(葛忠学), Li Minggao(李明高), Hong Feng(洪峰).Study on the lab synthesis of HMX using dinitrogen pentoxide as the nitrating agent[J].Chinese Journal of Explosives & Propellants(火炸药学报), 2002, 25:45-47
[4]	Lü Chunxu(吕春绪).Clean nitrating agent dinitrogen pentoxide and its application in nitration[J].Chinese Journal of Energetic Materials(含能材料), 2010, 18:611-617
[5]	Li Quanliang(李全良), Chen Jun(陈军).Synthesis craft of HMX from 1,5-methylene-3,7-dintrio-1,3,5,7-tetraazacyclooctane[J].Chinese Journal of Energetic Materials(含能材料), 2007, 15:509-510
[6]	Zhi Huizhen(职惠珍), Luo Jun(罗军), Feng Guang’an(封广安).An efficient method to synthesize HMX by nitrolysis of DPT with N2O5 and a novel ionic liquid[J].Chin.Chem.Lett.(中国化学快报), 2009,20:379-382
[7]	He Zhiyong, Luo Jun, Lü Chunxu.Synthesis of HMX via nitrolysis of DPT catalyzed by acidic ionic liquids[J].Central European Journal of Energetic Materials, 2011, 8:83-91
[8]	He Zhiyong(何志勇), Luo Jun(罗军), Lü Chunxu(吕春绪).Preparation of HMX by catalytic nitrolysis of DPT in AIL-N2O5-HNO3 system[J].Bull.Korean Chem. Soc., 2011, 32:2677-2682
[9]	Siele V I, Warman M, Leccacorvi J.Alternative procedures for preparing HMX[J].Propellants and Explosives, 1981, 6:67-73
[10]	Succasunna W L, Saddlebrook S N, Fair Lawn J A.Process of producing HMX in 100% yields and purity[P]:US,5124493.1992-6-23
[11]	Talawar M B, Sivabalan R, Polke B G.Establishment of process technology for the manufacture of dinitrogen pentoxide and its utility for the synthesis of most powerful explosive of today-CL-20[J].Journal of Hazardous Materials, [WTBX][WTBX]B124[WTBZ][STBZ], 2005, 24:153-164
[12]	Talawar M B, Sivabalan R, Mukundan T.Environmentally compatible next generation green energetic materials(GEMs)[J].Journal of Hazardous Materials, 2009, 161:589-607
[13]	He Zhiyong(何志勇), Luo Jun(罗军), Lü Chunxu(吕春绪).A review of preparation and application of dinitrogen pentoxide — an eco-friendly nitrating agent[J].Chinese Journal of Explosives & Propellants(火炸药学报), 2010, 33:1-5
[14]	Qian Hua(钱华).Research on the nitration by dinitrogen pentoxide[D].Nanjing:Nanjing University of Science and Technology, 2008
[15]	Lü Chunxu(吕春绪).Study progress on green nitration[J].Chinese Journal of Explosives & Propellants(火炸药学报), 2011, 34:1-8
[16]	He Zhiyong(何志勇), Luo Jun(罗军), Lü Chunxu(吕春绪).Nitration of DADN to prepare HMX in AIL-N2O5-HNO3 system[J].Chinese Journal of Explosives & Propellants(火炸药学报), 2011, 34:40-44
[17]	Fu Xiancai(傅献彩), Shen Wenxia(沈文霞), Yao Tianyang(姚天扬).Physical Chemistry(物理化学)[M].Beijing:Higher Education Press, 1989:155-187
[18]	Cai Shaoqing(蔡少卿), He Yuefeng(何月峰), Dai Qizhou(戴启洲).Kinetic model on ozonation of p-toluene sulfonic acid[J].CIESC Journal(化工学报), 2011, 62(5):1414-1420
[19]	Kahn M G, Konde E, Dossou F.Microwave-enhanced nucleophilicfluorination in the synthesis of fluoropyridyl derivative of[3,2-c]pyrazolo-corticosteroids, potential glucocorticoid receptor-mediated imaging agents[J].Bioorg. Med. Chem. Lett., 2006, 16:3454-3458
[20]	Liang Zhengyong(梁政勇).Study on technology of halogen-exchange fluorination reaction[D].Nanjing:Nanjing University of Science and Technology, 2007
[21]	Irvine J S, Robert K M, Frank H J, et al.Proton magnetic resonance data for some intermediates and products of nitrolysis of hexamethylenetetramine[J].Journal of Chemical and Engineering Data, 1973, 18:335-337
[22]	Lü Chunxu(吕春绪).Nitronium Theory(硝酰阳离子理论)[M].Beijing:Weapon Industry Press, 2006:3-5

Nitrolysis kinetics of DADN by N₂O₅/HNO₃

N₂O₅/HNO₃体系中硝解DADN的反应动力学

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

References 22

Related Articles 15

Recommended Articles

Metrics

Comments

[1]	Cheng CHENG, Zhongdi DUAN, Haoran SUN, Haitao HU, Hongxiang XUE. Lattice Boltzmann simulation of surface microstructure effect on crystallization fouling [J]. CIESC Journal, 2023, 74(S1): 74-86.
[2]	Linzheng WANG, Yubing LU, Ruizhi ZHANG, Yonghao LUO. Analysis on thermal oxidation characteristics of VOCs based on molecular dynamics simulation [J]. CIESC Journal, 2023, 74(8): 3242-3255.
[3]	Mengmeng ZHANG, Dong YAN, Yongfeng SHEN, Wencui LI. Effect of electrolyte types on the storage behaviors of anions and cations for dual-ion batteries [J]. CIESC Journal, 2023, 74(7): 3116-3126.
[4]	Jin YU, Binbin YU, Xinsheng JIANG. Study on quantification methodology and analysis of chemical effects of combustion control based on fictitious species [J]. CIESC Journal, 2023, 74(3): 1303-1312.
[5]	Chen CHEN, Qian YANG, Yun CHEN, Rui ZHANG, Dong LIU. Chemical kinetic study on coal volatiles combustion for various oxygen concentrations [J]. CIESC Journal, 2022, 73(9): 4133-4146.
[6]	Cong HE, Wenqi ZHONG, Guanwen ZHOU, Xi CHEN. Study on decomposition characteristics of cement raw meal in suspension furnace at high altitude [J]. CIESC Journal, 2022, 73(5): 2120-2129.
[7]	Min WANG, Jinlan CHENG, Xin LI, Jingjing LU, Chongxin YIN, Hongqi DAI. Delignification mechanism study of acid hydrotropes [J]. CIESC Journal, 2022, 73(5): 2206-2221.
[8]	Xiao YANG, Rui DING, Mohan LI, Zhengchang SONG. Effect of oxygen concentration on homogeneous/heterogeneous coupled reaction characteristics of methane in microchannel [J]. CIESC Journal, 2022, 73(12): 5427-5437.
[9]	Lihe ZHANG, Fan ZHANG, Changlun LI, Deping XU, Zhengang XU, Yonggang WANG. Construction and verification of BGL coal gasification kinetic model [J]. CIESC Journal, 2022, 73(10): 4668-4678.
[10]	Xiang GONG, Linsen LI, Zhao JIANG. Employing PdCo/SiO₂ catalyst in high activity dehydrogenation reaction of heterocyclic H₂ storage carrier [J]. CIESC Journal, 2022, 73(10): 4448-4460.
[11]	Xu ZHAO, Changsheng BU, Xinye WANG, Xin ZHANG, Xiaolei CHENG, Naiji WANG, Guilin PIAO. Kinetics investigation on iron-based oxygen carrier aided oxy-fuel combustion of anthracite char [J]. CIESC Journal, 2022, 73(1): 384-392.
[12]	Tingting WANG, Xi ZENG, Zhennan HAN, Fang WANG, Peng WU, Guangwen XU. Reaction characteristics and kinetics of biomass char-steam gasification in micro-fluidized bed reaction analyzer [J]. CIESC Journal, 2022, 73(1): 294-307.
[13]	Xujie CHEN, Xilei LYU, Huanhuan SHI, Liping ZHENG, Xiwen WEI, Penghui TIAN, Yuxi JIANG, Xiuyang LYU. Study on cyclodehydration of hexaric acids to 2,5- furandicarboxylic acid catalyzed with HBr-MgBr₂ [J]. CIESC Journal, 2021, 72(9): 4658-4664.
[14]	Tiantian PING, Xin YIN, Yu DONG, Shufeng SHEN. Research progress on reaction kinetics of CO₂ with amines in nonaqueous solvents [J]. CIESC Journal, 2021, 72(8): 3968-3983.
[15]	Zhenxing SONG, Xianbao CUI, Ying ZHANG, Xuemei ZHANG, Jie HE, Tianyang FENG, Jixiao WANG. Synthesis of n-hexyl acetate via reactive distillation catalyzed by mixed ionic liquids [J]. CIESC Journal, 2021, 72(8): 4155-4165.