Hua Ruixiang, Li Yanyan, Liu Wei, Zheng Jincheng, Wei Haibo, Wang Jinghua, Lu Xin, Kong Hongwei, Xu Guowang
National Chromatographic R&A Center, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116011, China.
J Chromatogr A. 2003 Nov 26;1019(1-2):101-9. doi: 10.1016/j.chroma.2003.08.048.
This article reports an analytical method for separating, identifying and quantitating sulfur-containing compounds and their groups in diesel oils (170-400 degrees C) using comprehensive two-dimensional gas chromatography coupled with a sulfur chemiluminescence detector. The identification of target compounds and their groups was based on standard substances, the group separation feature and tile-effect of comprehensive two-dimensional gas chromatography. The quantitative analysis on major sulfur compounds and total sulfur was carried out based on the linear response of sulfur chemiluminescence detector and the internal standards method. The results of total sulfur determination in the samples were compared with those from ASTM D 4294 standard method, the R.S.D. percentage were <6.02%, correctness of this method can meet the industrial requirement. To the end, the method developed was used to investigate the sulfur-containing compounds in different diesel oils, the result shows that the distribution of sulfur-containing compounds in diesel oils from different process units are apparently different. The sulfur compounds in fluid catalytic cracking (FCC), residuum fluid catalytic cracking (RFCC) diesel oils mainly exist in the form of alkyl-substituted dibenzothiophenes that add up to about 40-50% of the total sulfur, while this number is only 6-8 and 20-28% in visbreaking (VB) and delayed-coking (DC) diesel oils, respectively.
本文报道了一种采用全二维气相色谱与硫化学发光检测器联用的分析方法,用于分离、鉴定和定量柴油(170 - 400℃)中的含硫化合物及其类别。目标化合物及其类别的鉴定基于标准物质、全二维气相色谱的类别分离特征和瓦片效应。主要含硫化合物和总硫的定量分析基于硫化学发光检测器的线性响应和内标法。将样品中总硫的测定结果与ASTM D 4294标准方法的结果进行比较,相对标准偏差(R.S.D.)百分比<6.02%,该方法的准确性能够满足工业要求。最后,所开发的方法用于研究不同柴油中的含硫化合物,结果表明不同工艺单元的柴油中含硫化合物的分布明显不同。流化催化裂化(FCC)、渣油流化催化裂化(RFCC)柴油中的含硫化合物主要以烷基取代二苯并噻吩的形式存在,其含量约占总硫的40 - 50%,而在减黏裂化(VB)和延迟焦化(DC)柴油中,这一比例分别仅为6 - 8%和20 - 28%。