全二维气相色谱-飞行时间质谱对催化裂化汽油的定性与定量分析
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摘要
采用全二维气相色谱-飞行时间质谱(GC×GC-TOF MS)对催化裂化汽油全馏分进行了定性与定量分析,建立了相应的分析方法。结果表明,汽油族组成中的烷烃、烯烃、环烷烃、芳烃在全二维点阵谱图中呈分区域、带状的分布特点。GC×GC-TOF MS根据催化裂化汽油组分内分子的沸点及极性差异对其进行两个维度分离,极大地避免了普通色谱法分析过程中沸点相似化合物共流的弊端,实现催化裂化汽油组分的精确分离和准确定性分析。通过引入响应因子,修正了不同性质的烃类在电离源上电离效率的差异,使得TOF对催化裂化汽油族组成的定量结果与普通气相色谱法的定量结果的相关性较好,且应用GC×GC-TOF MS方法获得了催化裂化汽油更为精确的族组成信息。GC×GC-TOF MS为催化裂化汽油精确表征提供了一种有效方法。
A method of qualitative and quantitative analysis on fluid catalytic cracking( FCC) full range gasoline by comprehensive two-dimensional gas chromatography coupled with time-of-flight mass spectrometry( GC×GC-TOF MS) was established. The results showed that paraffins,olefins,naphthenes and aromatics in FCC gasoline had regional and zonal distribution in two-dimensional contour plots. The distinctions of boiling points and polarity between different compounds were used to achieve the accurate separation and determination in GC×GC-TOF MS analysis,and consequently the co-current flow which was often present in the conventional GC analysis was greatly suppressed. The difference of ionizing efficiency between different compounds was modified by response factors,and moreover,a good quantitative dependency was found between the analysis results of GC and GC × GC-TOF MS on FCC gasoline. Due to the high separation resolution,GC×GC-TOF MS gave more accurate results about the group compositions of FCC gasoline. GC ×GC-TOF MS provided an effective way with high precision for the characterization of FCC gasoline.
A method of qualitative and quantitative analysis on fluid catalytic cracking( FCC) full range gasoline by comprehensive two-dimensional gas chromatography coupled with time-of-flight mass spectrometry( GC×GC-TOF MS) was established. The results showed that paraffins,olefins,naphthenes and aromatics in FCC gasoline had regional and zonal distribution in two-dimensional contour plots. The distinctions of boiling points and polarity between different compounds were used to achieve the accurate separation and determination in GC×GC-TOF MS analysis,and consequently the co-current flow which was often present in the conventional GC analysis was greatly suppressed. The difference of ionizing efficiency between different compounds was modified by response factors,and moreover,a good quantitative dependency was found between the analysis results of GC and GC × GC-TOF MS on FCC gasoline. Due to the high separation resolution,GC×GC-TOF MS gave more accurate results about the group compositions of FCC gasoline. GC ×GC-TOF MS provided an effective way with high precision for the characterization of FCC gasoline.
引文
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2 ZHU Yu-Qin,SI Yun-Hang,ZHU Yi-Ning,ZHANG Lin,WANG Hong-Wei,ZHANG Yu-Ling,LI Bing.Natural Gas Chemical Industry,2014,39(6):77-81朱玉琴,司云航,朱忆宁,张琳,汪宏伟,张瑜玲,李兵.天然气化工,2014,39(6):77-81
3 CAO Xiang-Hong.Chin.Petrol.Processing Petrochem.Technol.,2012,43(8):1-6曹湘洪.石油炼制与化工,2012,43(8):1-6
4 LIU Hu-Wei.Gas Chromatography Method and Application(Second edition).Beijing:Chemical Industry Press 2008:121刘虎威.气相色谱方法及应用(第二版).北京:化学工业出版社,2008:121
5 ZHU Shu-Kui,XING Jun,WU Cai-Ying.J.Anal.Sci.,2005,21(3):332-336朱书奎,邢钧,吴采樱.分析科学学报,2005,21(3):332-336
6 Schoenmakers P J,Oomen J L M M,Blomberg J,Genuit W,Velzen G.J.Chromatogr.A,2000,892(1):29-46
7 Vendeuvre C,Bertoncini F,Duval L,Duplan J L,Thiébaut D,Hennion M C.J.Chromatogr.A,2004,1056(1):155-162
8 Blomberg J,Schoenmakers P J,Beens J,Tijssen R.J.High Resol.Chromatogr.,1997,20(10):539-544
9 Flego C,Gigantiello N,Parker W O,Calemma V.J.Chromatogr.A,2010,1217(37):5872-5873
10 ZHANG Quan,XIANG Zhang-Min,CAI Kai,ZHOU Shu-Ping,GENG Zhao-Liang,GUO Yu-Shuang,CHEN Wen-Sheng.Chinese J.Anal.Chem.,2014,42(8):1124-1130张权,向章敏,蔡凯,周淑平,耿召良,郭玉双,陈文生.分析化学,2014,42(8):1124-1130
11 CHENG Quan,YANG Fang,LI Jie,LU Sheng-Yu,LAN Jin-Chang,JIANG Jin-Bin.J.Instrumental Anal.,2015,34(5):525 -531程权,杨方,李捷,卢声宇,蓝锦昌,江锦彬.分析测试学报,2015,34(5):525-531
12 NIU Lu-Na,LIU Ze-Long,ZHOU Jian,CAI Xin-Heng,TIAN Song-Bai.Chinese Journal of Chromatography,2014,32(11):1236-1241牛鲁娜,刘泽龙,周建,蔡新恒,田松柏.色谱,2014,32(11):1236-1241
13 NIU Lu-Na,LIU Ze-Long,ZHOU Jian,CAI Xin-Huan,TIAN Song-Bai.Acta Petrol.Sin.(Petrol.Proc.Sec.),2014,30(5):851-860牛鲁娜,刘泽龙,周建,蔡新恒,田松柏.石油学报(石油加工),2014,30(5):851-860
14 GUO Kun,ZHOU Jian,LIU Ze-Long.Chinese Journal of Chromatography,2012,30(2):128-134郭琨,周建,刘泽龙.色谱,2012,30(2):128-134
15 Dutriez T,Borras J,Courtiade M,Thiébaut D,Dulot H,Bertoncini F,Hennion M C.J.Chromatogr.A,2011,1218(21):3190-3199
16 Dutriez T,Courtiade M,Thiébaut D,Dulot H,Bertoncini F,Vial J,Hennion M C.J.Chromatogr.A,2009,1216(14):2905-2912
17 Zhang W,Zhu S,He S,Wang Y.J.Chromatogr.A,2015,1380:162-170
18 NIU Lu-Na,LIU Ze-Long,ZHOU Jian,CAI Xin-Heng,TIAN Song-Bai.Acta Petrol.Sin.(Petrol.Proc.Sec.),2015,31(5):1097-1102牛鲁娜,刘泽龙,周建,蔡新恒,田松柏.石油学报(石油加工),2015,31(5):1097-1102
19 Frysinger G S,Gaines R B,Ledford E B.J.High Resol.Chromatogr.,1999,22(4):195-200