PYX在DMF中的溶析结晶动力学  

Dilution Crystallization Kinetics of PYX in DMF

作　　者：罗西 刘红妮[1] 赵娟[1] 常海[1] 栾洁玉[1] 周文静[1] LUO Xi;LIU Hong-ni;ZHAO Juan;CHANG Hai;LUAN Jie-yu;ZHOU Wen-jing(Xi′an Modern Chemistry Research Institute,Xi′an 710065,China)

机构地区：[1]西安近代化学研究所,陕西西安710065

出　　处：《火炸药学报》2023年第9期803-810,I0001,共9页Chinese Journal of Explosives & Propellants

基　　金：National Natural Science Foundation of China(No.21805226)。

摘　　要：为了优化及放大2,6-二苦氨基-3,5-二硝基吡啶(PYX)的溶析结晶工艺,在以DMF为溶剂、H_(2) O为反溶剂的结晶体系下开展了PYX的溶析结晶动力学研究。首先采用激光动态法测定了PYX在DMF纯溶剂和DMF-H_(2) O二元溶剂中的溶解度曲线,建立了相应的溶解度模型;确定了PYX的晶体生长类型,测定了PYX在结晶过程中的晶体生长及成核速率,建立了相应的结晶动力学模型,在此基础上分析了PYX结晶动力学的影响因素及规律。结果表明,PYX在DMF纯溶剂和不同体积比的DMF-H_(2) O二元溶剂中的溶解度随温度的升高而增大,随H_(2) O含量的增加而减小,不同溶剂中Apelblat模型对溶解度拟合结果的相关系数均大于0.99。PYX的晶体生长类型为粒度无关生长,晶体生长及成核活化能分别为8.33×10^(3) J/mol和1.01×10^(4) J/mol,过饱和比对于晶体生长速率的指数为6.73,搅拌强度、过饱和比、悬浮密度对于晶体成核速率的指数分别为0.27、7.16、0.14。PYX晶体生长及成核速率均随温度的升高而增大,随过饱和比的增大而增大,且升高温度或增大过饱和比更有利于PYX晶体成核。相比于过饱和比,搅拌强度、悬浮密度对PYX晶体成核速率的影响较小,增大搅拌强度或悬浮密度不利于PYX晶体生长。For the optimization and scale-up of the dilution crystallization process of 2,6-dipicrylamino-3,5-dinitropyridine(PYX),the dilution crystallization kinetics of PYX was studied in the crystallization system with DMF as the solvent and H_(2) O as the anti-solvent.Firstly,the solubility curves of PYX in DMF pure solvent and DMF-H_(2) O binary solvent were measured by with laser dynamic method,by which the corresponding solubility models were established.And then,the crystal growth type of PYX was determined.The crystal growth and nucleation rates of PYX in the dilution crystallization process were measured,and the corresponding crystallization kinetics models were established.On this basis,the effect factors and laws of the crystallization kinetics of PYX were analyzed.The results show that the solubility of PYX in DMF pure solvent and DMF-H_(2) O binary solvent with different volume ratios increases with increasing temperature,and decreases with increasing H_(2) O content.The solubility of PYX in different solvents was fitted by Apelblat model,where the correlation coefficients of the fitting results are all greater than 0.99.The crystal growth type of PYX is particle size independent growth.The crystal growth and nucleation activation energy of PYX are 8.33×10^(3) J/mol and 1.01×10^(4) J/mol,respectively.The index of supersaturation ratio to crystal growth rate is 6.73.The stirring strength,supersaturation ratio and suspension density to crystal nucleation rate are 0.27,7.16 and 0.14,respectively.The crystal growth and nucleation rates of PYX increase along with the increase of temperature and supersaturation ratio.Also,the increase of temperature or supersaturation ratio is more conducive to the crystal nucleation of PYX.Compared with the supersaturation ratio,the stirring intensity and suspension density have less effect on the crystal nucleation rate of PYX,and increasing the stirring intensity or suspension density is detrimental to the crystal growth of PYX.

关 键 词：物理化学 PYX DMF 溶解度 结晶动力学 

分 类 号：TJ55[兵器科学与技术—军事化学与烟火技术] O65[理学—分析化学]