微反应器在含能材料合成与品质提升中的应用

doi:10.16085/j.issn.1000-6613.2023-0329

摘要/Abstract

摘要：

含能材料是一类含有爆炸性基团或含有氧化剂和可燃物、能独立进行化学反应并输出能量的化合物或混合物。由于含能材料的特殊性，其合成过程具有强烈放热、对温度敏感的特点，同时，在实际应用中武器装药对含能材料的粒度控制也有很高的要求。微反应器具有传热传质效率高、安全性高、设备微型化和集成化、环境污染小等优点，十分适合于含能材料的合成过程与粒度控制，近年来成为国内外含能材料领域研究的热点与重点之一。本文第一部分介绍了硝酸酯、硝基、叠氮、氮杂环四类含能化合物的微反应合成，点明了微反应器可以显著提高合成安全性、加快合成效率和安全性；第二部分总结了微化工技术在含能材料微纳米化、球形化以及复合含能材料制备方面的应用，发现了微反应器具有粒度控制更精确、球形度高等特点。最后指出了微反应器在含能材料领域具有广阔的应用潜力，并对未来研究的重点及改进方向进行了展望。

关键词: 微反应器, 微流控技术, 含能材料, 粒度控制, 微纳米化, 球形化

Abstract:

Energetic materials are a class of compounds or mixtures containing explosive groups or oxidants and combustibles that can perform chemical reactions independently and output energy. Due to the particularity of energetic materials, the synthesis process has the characteristics of strong heat release and temperature sensitivity. At the same time, in practical applications, weapon charges also have high requirements for the particle size control of energetic materials. The microreactor has the advantages of high heat and mass transfer efficiency, high safety, miniaturization and integration of equipment, and low environmental pollution. It is suitable for the synthesis process and particle size control of energetic materials. In recent years, it has become one of the hotspots and focuses in the field of energetic materials. The first part of this paper introduces the micro-reaction synthesis of four kinds of energetic compounds, such as nitrate, nitro, azide and nitrogen heterocyclic. It is pointed out that the micro-reactor can significantly improve the synthesis safety, accelerate the synthesis efficiency and safety. The second part summarizes the application of micro-chemical technology in the preparation of micro-nanometer, spherical and composite energetic materials. It is found that the micro-reactor has the characteristics of more accurate particle size control and high sphericity. Finally, it is pointed out that the microreactor has broad application potential in the field of energetic materials, and the focus and improvement direction of future research are prospected.

Key words: microreactor, microfluidic technology, energetic materials, granularity control, micro-nanometerization, spheroidization

中图分类号:

TJ55

刘卫孝, 刘洋, 高福磊, 汪伟, 汪营磊. 微反应器在含能材料合成与品质提升中的应用[J]. 化工进展, 2023, 42(7): 3349-3364.

LIU Weixiao, LIU Yang, GAO Fulei, WANG Wei, WANG Yinglei. Application of microreactor in synthesis and quality improvement of energetic materials[J]. Chemical Industry and Engineering Progress, 2023, 42(7): 3349-3364.

图/表 23

图1 微反应器及TEGDN合成工艺

表1 2种TEGDN的合成工艺对比[33]

硝化工艺

水浴温度

/℃

硝化剂和

原料摩尔比

平均停留

时间/s

原料用量

/mL

产率

图2 PGDN与TMETN的微反应器合成流程图[37]

图3 反应溶液中不同甘油含量时LTNR粒子的晶体形貌[39]

图4 不同CTAB浓度时LTNR粒子的晶体形貌[39]

图5 制备叠氮化银（SA）的微反应器系统[47]

图6 3-甲基-4-硝基吡唑合成的微反应装置[54]

图7 反应器中不同条件下TATB的粒径分布曲线[28]

图8 微反应器和烧杯中TATB的粒径分布曲线[28]

图9 心形结构微反应器系统原理[60]

图10 多平行微流控再结晶体系的系统原理图和照片[69]

图11 AP晶体的平均粒径随超声波强度的变化[70]

图12 一种新的连续流共振声混合（CFRAM）技术 [62]

图13 CL-20空心微球表面及内部结构图[72]

图14 流速比和溶棉比对硝化棉球形发射药制备的影响[73]

图15 LA起爆药微球SEM图像及粒径分布直方图[74]

图16 不同溶剂/非溶剂流速比（Q2/Q1）条件下的HNS球化示意图[75]

图17 HNS微球形成的示意图和SEM图像[76]

图18 原始HMX和TATB/HMX复合粒子的SEM图像[83]

图19 原始HMX和TATB/HMX复合粒子的SEM图像[83]

图20 微流控平台制备纳米HNS和HNS/HMX复合材料的系统原理图[85]

图21 DAAF/HNIW复合材料制备示意图[87]

图22 微液滴约束自组装制备的B/BaCrO4复合粒子的SEM图像[(a)~(e)]及微液滴约束自组装制备B/BaCrO4复合粒子原理示意图[(f)] [88]

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