基于膜分离的HMX绿色结晶制备与表征  

Green Crystallization of HMX Based on Membrane Separation:Preparation and Characterization

作　　者：王腾 周鑫 郝世龙[1] 张树海 苟瑞君 李洪珍[1] WANG Teng;ZHOU Xin;HAO Shi-long;ZHANG Shu-hai;GOU Rui-jun;LI Hong-zhen(Institute of Chemical Materials,CAEP,Mianyang 621999,China;School of Environment and Safety Engineering,North University of China,Taiyuan 030051,China)

机构地区：[1]中国工程物理研究院化工材料研究所,四川绵阳621999 [2]中北大学环境与安全工程学院,山西太原030051

出　　处：《含能材料》2023年第1期8-17,共10页Chinese Journal of Energetic Materials

基　　金：国家自然科学基金资助(22105183)。

摘　　要：针对常规炸药结晶方法(蒸发、溶析及降温等)过饱和度均一性调控难、溶剂回收率低等问题,设计了基于压力驱动、错流过滤的有机溶剂纳滤(OSN)膜结晶装置,并用于奥克托今(HMX)的膜结晶工艺研究。探讨了关键工艺参量(温度、压力)对其结晶形态和粒度的影响,与蒸发结晶进行了晶体形貌、结构的对比。利用扫描电子显微镜(SEM)、X射线粉末衍射仪(XRD)、热重⁃差示扫描量热仪(TG⁃DSC)等方法表征了2种方法重结晶后的HMX晶体。进一步考察了纳滤膜的长期操作稳定性,并将渗透回收的溶剂进行了再次膜结晶。结果表明,通过对温度与压力的优化控制,膜结晶工艺能够获得粒度分布窄(变异系数<46%)、晶体密度高(ρavg=1.8997~1.9004 g·cm^(-3))及热稳定性优异的β⁃HMX。相较蒸发结晶,膜结晶过程中的过饱和度调控更易操作,制备的晶体形态更加均一;纳滤膜多次重复使用后,对溶剂中HMX分子的截留率仍能保持在92%以上,表现出良好的渗透选择稳定性;采用渗透回收的溶剂进行膜结晶仍能获得中值直径为34.92μm、变异系数为37.22%的β型HMX晶体,表明该技术能够实现对结晶溶剂的高效回收再利用。Aiming at the problems that the crystallization methods(evaporation,antisolvent and cooling,etc.)of the convention⁃al explosive are difficult to accurately control the uniformity of supersaturation and the low solvent recovery rate,an organic sol⁃vent nanofiltration(OSN)membrane crystallization apparatus based on pressure⁃driven and cross⁃flow filtration was designed and used to study the membrane crystallization process of 1,3,5,7⁃tetranitro⁃1,3,5,7⁃tetrazacyclooctane(HMX).The effects of key process parameters(temperature and pressure)on the crystal morphology and particle size were discussed,and the crystal morphology and structure were compared with those of evaporative crystallization.The HMX crystals after recrystallization by both methods were characterized by scanning electron microscopy(SEM),X⁃ray powder diffractometer(XRD)and thermogravimetric⁃differential scanning calorimeter(TG⁃DSC).The long⁃term operational stability of the nanofiltration membrane was further investigated,and the solvent recovered by permeation was used to re⁃crystallize.Results show that by the optimal control of temperature and pressure,the membrane crystallization process can obtainβ⁃phase HMX with narrow particle size dis⁃tribution(coefficient of variation<46%),high crystal density(ρavg=1.8997-1.9004 g·cm^(-3))and excellent thermal stability.Compared with evaporation crystallization,the supersaturation control in the membrane crystallization process is easier to oper⁃ate,and the prepared crystal morphology is more uniform.After repeated use,the rejection of HMX molecules in the solvent still remained above 92%,showing a good permeation selectivity stability.Theβ⁃phase HMX crystals with an median particle size of 34.92μm and a coefficient of variation of 37.22%can still be prepared by membrane crystallization using permeation⁃recovered solvent,indicating that this technology can realize the efficient recovery and reuse of the crystallization solvent.

关 键 词：膜结晶 有机溶剂纳滤 HMX 粒度 蒸发结晶 

分 类 号：TJ55[兵器科学与技术—军事化学与烟火技术] TQ028.8[化学工程]