Michaelian Kirk H, Yuan Hongqi, Hall Robert H, Bulmer J Tim
Natural Resources Canada, CANMET Energy Technology Centre-Devon, 1 Oil Patch Drive, Suite A202, Devon, Alta., Canada T9G 1A8.
Spectrochim Acta A Mol Biomol Spectrosc. 2005 Nov;62(1-3):582-91. doi: 10.1016/j.saa.2005.01.022.
Four techniques for the reduction or elimination of fluorescence from Raman spectra of Syncrude process samples were examined in this study. These methods are based on the retrieval of Raman bands from differential, or derivative spectra. Differential data were generated by subtracting similar spectra of a given sample obtained in three ways: (a) shifted detection utilizing an array detector and two successive spectrometer settings; (b) shifted excitation (dispersive Raman) where the two spectra are recorded using neighbouring laser lines and ordinary photon counting; (c) shifted excitation (FT-Raman) in which the laser frequency is changed in software before acquisition of the second spectrum. In addition to these differential techniques, derivative spectra were acquired directly with a dispersive Raman system by modulating the wavelength during scanning. These fluorescence rejection methods were applied to two groups of Syncrude Sweet Blend distillation fractions. For light gas oils (boiling range, 195-343 degrees C) the ratio of monocyclic and bicyclic aromatic species was determined and bands due to aliphatic CH(n) groups were characterized. Heavy gas oils (343-524 degrees C) yielded bands that allowed quantitation of monocyclic, bicyclic and total aromatic groups. Bands due to aliphatics were also identified for the heavy gas oils. These results constitute a significant advance compared to the information obtainable using conventional dispersive and FT-Raman spectroscopy for the analysis of hydrocarbon distillation fractions.
本研究考察了四种降低或消除Syncrude工艺样品拉曼光谱中荧光的技术。这些方法基于从差分光谱或导数光谱中检索拉曼谱带。差分数据是通过以下三种方式对给定样品的相似光谱进行减法运算生成的:(a) 使用阵列探测器和两个连续的光谱仪设置进行偏移检测;(b) 偏移激发(色散拉曼),其中使用相邻激光线和普通光子计数记录两个光谱;(c) 偏移激发(傅里叶变换拉曼),在采集第二个光谱之前在软件中改变激光频率。除了这些差分技术外,还通过在扫描过程中调制波长,使用色散拉曼系统直接获取导数光谱。这些荧光抑制方法应用于两组Syncrude Sweet Blend蒸馏馏分。对于轻质瓦斯油(沸程为195 - 343℃),测定了单环和双环芳烃物种的比例,并对脂肪族CH(n)基团产生的谱带进行了表征。重质瓦斯油(343 - 524℃)产生的谱带可用于定量单环、双环和总芳烃基团。还鉴定了重质瓦斯油中脂肪族产生的谱带。与使用传统色散和傅里叶变换拉曼光谱分析烃类蒸馏馏分可获得的信息相比,这些结果有了显著进展。