乌醋溶液中乌洛托品含量的近红外光谱温度校正模型的研究
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摘要
乌洛托品-醋酸(HA-HAc)溶液是制备奥克托今(HMX)的重要原材料。为了快速测定HA-HAc溶液中HA的含量,利用近红外(NIR)光谱技术,加入温度因子,建立了HA定量分析的温度校正模型。讨论了温度、光谱预处理方法对模型的影响。结果表明,温度会影响该溶液的吸光度,含温度因子的模型的平均相对误差减小了81.74%,模型准确度提高;光谱预处理可以消除外界因素对红外谱图采集的干扰,有利于提高建模的准确度,最佳预处理方法为一阶导数+Norris-derivative法。温度校正模型的评价参数为:相关系数R2=0.9997,均方差RMSEC=0.0388、内部交互验证均方差RMSECV=0.0441,预测均方差RMSEP=0.0350;模型的重复性标准偏差为0.0153%,此方法重复性为0.1298%,显示该法可用于HA-HAc溶液中HA含量的快速测定。
Hexamethylenetetramine-acetic acid( HA-HAc) solution is an important raw material for preparing Octogen( HMX). In order to rapidly determine the HA content in HA-HAc solution,the temperature calibration model of quantitatively analyzing HA was established by near-infrared( NIR) spectroscopy technology and adding temperature factor. The effect of temperature and spectral pretreatment method on the model was discussed. Results show that temperature will affect the absorbance of the solution,the average relative error of the model with temperature factor is reduced by 81.74%,and the accuracy of the model is improved. The spectral pretreatment can eliminate the interference of external factors to infrared spectrum collection,which is beneficial to improve the accuracy of modeling. The best pretreatment method is the first derivative + Norris-derivative method. The evaluation parameters of the temperature correction model are correlation coefficient R2=0.9997,the root-mean square error of correlation RMSEC = 0.0388,the root-mean square error of cross-validation RMSECV = 0. 0441,and the root-mean square error of prediction RMSEP = 0.0350. The standard deviation of model repeatability is 0.0153% and the repeatability of this method is 0.1298%,revealing that the method can be used for fast determination of HA content in HA-HAc solution.
Hexamethylenetetramine-acetic acid( HA-HAc) solution is an important raw material for preparing Octogen( HMX). In order to rapidly determine the HA content in HA-HAc solution,the temperature calibration model of quantitatively analyzing HA was established by near-infrared( NIR) spectroscopy technology and adding temperature factor. The effect of temperature and spectral pretreatment method on the model was discussed. Results show that temperature will affect the absorbance of the solution,the average relative error of the model with temperature factor is reduced by 81.74%,and the accuracy of the model is improved. The spectral pretreatment can eliminate the interference of external factors to infrared spectrum collection,which is beneficial to improve the accuracy of modeling. The best pretreatment method is the first derivative + Norris-derivative method. The evaluation parameters of the temperature correction model are correlation coefficient R2=0.9997,the root-mean square error of correlation RMSEC = 0.0388,the root-mean square error of cross-validation RMSECV = 0. 0441,and the root-mean square error of prediction RMSEP = 0.0350. The standard deviation of model repeatability is 0.0153% and the repeatability of this method is 0.1298%,revealing that the method can be used for fast determination of HA content in HA-HAc solution.
引文
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[2]李全良,王建龙,陈军.一段反应时间对HMX制备的影响[J].含能材料,2007,15(2):112-113.LI Quan-liang,WANG Jian-long,CHEN Jun.Effect of the first reaction time on the preparation of HMX[J].Chinese Journal of Energetic Materials(Hanneng Cailiao),2007,15(2):112-113.
[3]王菊香,申刚,邢志娜,等.近红外光谱快速测定混胺组分含量[J].分析化学,2004,2(4):459-463.WANG Ju-xiang,SHEN Gang,XING Zhi-na,et al.Determination of triethylamine and xylidine in mixed amine by near-infrared spectroscopy[J].Chinese Journal of Analytical Chemistry,2004,2(4):459-463.
[4]解国玲,任芊,董守龙,等.近红外光谱技术在含能材料成分分析中的建模研究[J].火炸药学报,2003,26(4):78-80.XIE Guo-ling,REN Qian,DONG Shou-long,et al.Study on modeling of multicomponent analysis in propellants products with NIR spectroscopy[J].Chinese Journal of Explosives&Propellant,2003,26(4):78-80.
[5]苏鹏飞,张皋,温晓燕,等.近红外漫反射光谱法快速测定混合炸药组分含量[J].火炸药学报,2008,31(5):62-65.SU Peng-fei,ZHANG Gao,WEN Xiao-yan,et al.Determination of the component in composite explosive by near infrared diffuse reflectance spectroscopy[J].Chinese Journal of Explosives&Propellant,2008,31(5):62-65.
[6]Hardmeyer E K.Stabilizer determination in solid propellant using near infrared spectroscopy[C]∥30th Propellant Development and Characterization Subcommittee Meeting,Colorado:CPIA,2002:129-135.
[7]温晓燕,苏鹏飞,刘红妮,等.近红外漫反射光谱法测定硝化棉含氮量的数值模拟及实验研究[J].火炸药学报,2014,37(6):87-90.WEN Xiao-yan,SU Peng-fei,LIU Hong-ni,et al.Numerical simulation and experimental study on the nitrogen content in nitrocellulose by near infrared diffuse reflectance spectroscopy[J].Chinese Journal of Explosives&Propellants,2014,37(6):87-90.
[8]温晓燕,谯娟,刘红妮,等.近红外光谱法测定HMX中α-HMX杂质晶形的含量[J].火炸药学报,2016,39(3):61-65.WEN Xiao-yan,QIAO Juan,LIU Hong-ni,et al.Determination ofα-HMX impurity content in HMX by near infrared spectroscope[J].Chinese Journal of Explosives&Propellants,2016,39(3):61-65.
[9]周帅,邓国栋,王志强,等.近红外光谱法快速检测单基发射药中的二苯胺含量[J].火炸药学报,2016,39(3):95-100.ZHOU Shuai,DENG Guo-dong,WANG Zhi-qiang,et al.Fast determination of diphenylamine content in single-base gun propellant by near infrared spectroscope[J].Chinese Journal of Explosives&Propellants,2016,39(3):95-100.
[10]蒋忠亮,张皋,苏鹏飞,等.HMX含量实时检测NIRS模型的建立与优化[J].火炸药学报,2014,37(1):66-69.JIANG Zhong-liang,ZHANG Gao,SU Peng-fei,et al.Establishment and optimization of NIRS model for real-time detection of HMX content[J].Chinese Journal of Explosives&Propellant,2014,37(1):66-69.
[11]王菊香,邢志娜,申刚,等.光谱预处理和波长选择对混胺燃料各指标近外光谱定量分析结果的影响比较[J].计算机与应用化学,2013,30(1):39-42.WANG Ju-xiang,XING Zhi-na,SHEN Gang,et al.Effects ofspectral preprocessing and wavelength selection on content determination in mixed-amine by NIR spectroscopy[J].Computers and Applied Chemistry,2013,30(1):39-42.
[12]尹作柱,邓国栋,朱陈森,等.火药吸收药中硝化棉含量快速检测方法[J].火炸药学报,2014,37(6):79-82.YIN Zuo-zhu,DENG Guo-dong,ZHU Chen-sen,et al.A rapid detection method of the NC content in gunpowder intermediate[J].Chinese Journal of Explosives&Propellant,2014,37(6):79-82.
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[15]陆婉珍.现代近红外光谱分析技术(第二版)[M].北京:中国石化出版社,2006:38-46.LU Wan-zhen.Modern near infrared spectroscopy analytical technology(second edition)[M].Beijing:China Petrochemical Press,2006:38-46.
[16]姚冰洁.中红外技术在HMX制备过程中应用研究[D].北京:北京理工大学,2011.YAO Bing-jie.Application study on the preparation of octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine(HMX)by mid-infrared spectroscopy[D].Beijing:Beijing Institute of Technology,2011.
[17]于晓菲.HMX制备过程快速分析研究[D].北京:北京理工大学,2011.YU Xiao-fei.Analysis study on the preparation process of octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine(HMX)[D].Beijing:Beijing Institute of Technology,2011.
[18]Williams P C,Sobering D C.Comparison of commercial near infrared transmittance and reflectance instruments for analysis of whole grains and seeds[J].Journal of Near Infrared Spectroscopy,1993,1(1):25-32.
[19]江泽慧,费本华,杨忠.光谱预处理对近红外光谱预测木材纤维素结晶度的影响[J].光谱学与光谱分析,2007,27(3):435-438.JIANG Ze-hui,FEI Ben-hua,YANG zhong.Effects of spectral pretreatment on the prediction of crystallinity of wood cellulose using near infrared spectroscopy[J].Spectroscopy and Spectral Analysis,2007,27(3):435-438.
[20]王远辉,黎庆涛,姜毅,等.在线检测白砂糖近红外光谱的预处理方法研究[J].食品科技,2009,34(8):283-286.WANG Yuan-hui,LI Qing-tao,JIANG Yi,et al.Study on near infrared spectrum pretreatment of on-line white granulated sugar determination[J].Food Science and Technology,2009,34(8):283-286.