一种基于石墨化炭黑过滤吸附处理荧光抑制和改进系统聚类分析的轻质燃油种类拉曼光谱快速识别方法  

A Fast Raman Spectroscopy Classification Method for Fuels Combining the Fluorescence Background Correction Based on GCB Preprocess and Modified Hierarchical Clustering

作　　者：喻星辰 管亮 李子存 龚应忠 马骏 许贤 YU Xing-chen;GUAN Liang;LI Zi-cun;GONG Ying-zhong;MA Jun;XU Xian(Oil Department, Army Logistical University of PLA, Chongqing 401311, China;76174 Army, Guilin Logistical Support Center, Guilin 512200, China;Military Energy and Supply Technical Service Center, Logistics Support Department of PLA, Beijing 100036, China)

机构地区：[1]陆军勤务学院 [2]桂林联勤保障中心76174部队 [3]军委后勤保障部军需能源技术服务中心

出　　处：《光谱学与光谱分析》2019年第3期807-812,共6页Spectroscopy and Spectral Analysis

基　　金：国家自然科学基金青年基金项目(21205136);军委后勤保障部军需能源局科研计划项目(YX0215J026);重庆市应用基础与前沿研究(一般)项目(cstc2014jcyjA0592);后勤工程学院研究生创新基金项目资助

摘　　要：提出了一种石墨化炭黑过滤吸附前处理抑制轻质燃油拉曼光谱荧光背景干扰的方法和一种改进的系统聚类分析算法,实现了39个样品的种类快速识别,即能自动将样品识别为0#车用柴油、 0#普通柴油、 97#车用汽油、 93#车用汽油、 90#车用汽油和3#喷气燃料等6种类型。过滤吸附处理方法是用定制的50 mg石墨化炭黑过滤吸附0.75 mL油样,然后对其进行拉曼光谱数据采集。试验结果证明:石墨化炭黑过滤吸附处理对无荧光背景干扰的3#喷气燃料和车用汽油样品拉曼光谱特征无明显影响,且能够有效抑制车用汽油和车用柴油样品的拉曼弱荧光背景干扰,以及车用汽油和普通柴油的强荧光背景干扰。改进的有监督系统聚类分析算法将普鲁克距离作为系统聚类分析中样本间相似度的评价方法;并将经典的系统聚类分析视为标准校正样品集的"建模"过程,通过计算未知样品与各类属中心向量之间的普鲁克距离,依据距离最小原则判断未知样品的类属。通过对39个具有不同拉曼荧光背景干扰特征油样的石墨化炭黑前处理和"留一法"交互验证分类识别,分析结果证明:石墨化炭黑过滤吸附前处理抑制拉曼光谱荧光背景的方法能够有效提取轻质燃油的拉曼光谱特征并应用于定性种类识别。In this article,a Raman spectroscopy classification method combining the fluorescence background rejection based on graphitized carbon black(GCB)preprocessing and modified hierarchical clustering analysis(HCA)has been put forward,by which 39 fuel samples have been classified correctly and automatically into six types of 0#automobile diesel fuel,0#general diesel fuel,97#gasoline,93#gasoline and 3#jet fuel.GCB preprocessing,during which 50mg GCB is used to filter 0.75 mL fuel sample once,has no influence on those samples which have no fluorescence background such as 3#jet fuels and gasolines and can reject effectively the weak fluorescence background of gasoline and automobile diesel fuel samples and strong fluorescence background of gasoline and general diesel fuel samples.Firstly,the Procrustes distance in the Procrustes analysis(PA)was adopted to measure the similarity between the samples for the classical HCA which was regarded as the modeling stage in the modified HCA algorithm.And the centroid vectors belonging to the different clusters were calculated according to the results of the HCA.Secondly,the types of the unknown test samples could be determined by calculating and comparing the Procrustes distances between the test samples and the centroid vectors of the clusters.The"leave-one-out"cross validation results based on the 39 samples belonging to 6 classes have shown that the GCB preprocessing is an effective fluorescence rejection method for Raman spectra of light fuels which can be applied to qualitative and quantitative analysis.

关 键 词：拉曼光谱 荧光抑制 石墨化炭黑 系统聚类分析 种类识别 轻质燃油 

分 类 号：TE622[石油与天然气工程—油气加工工程]