全二维气相色谱-高分辨飞行时间质谱分析LCO中芳烃化合物
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摘要
采用全二维气相色谱-高分辨飞行时间质谱(GC×GC/HR-TOF MS)对催化裂化轻循环油(LCO)中的芳烃化合物进行详细表征。通过质谱图解析、沸点信息和标准物质保留时间对比,结合仪器高分辨率的优势,确定LCO中的主要芳烃类型及结构。对相同Z值、但类型不同的芳烃在总离子流色谱图中的峰面积进行归一化计算,结合SH/T 0606—2005法测定结果,得到不同类型芳烃在LCO中的含量。结果表明:LCO中除含有Z值为-6的烷基苯类、Z值为-12的萘类和Z值为-18的菲类和蒽类化合物外,还含有Z值为-8的芳烃包含茚满类和四氢萘类化合物,以茚满类为主;Z值为-10的芳烃主要为茚类,含有少量的二环烷基苯类;Z值为-14的芳烃包含联苯类、苊类和二苯并呋喃类化合物,以苊类为主;Z值为-16的芳烃主要为芴类,不含苊烯类化合物。该方法可以提供更为详细的芳烃类型和单体化合物的分子组成信息。
Comprehensive two-dimensional gas chromatography coupled with high resolution time of flight mass spectrometry(GC×GC/HR-TOF MS) was employed for the characterization of aromatics in light cycle oil(LCO). Identification of aromatic hydrocarbons was carried out by mass spectrum analysis, through comparing with boiling point information and retention time of standard reference materials. High resolution of GC×GC/HR-TOF MS was also used for the above aromatics identification. The main types of aromatics and their chemical structures in LCO were determined. The content of aromatics that had the same Z value but different types, can be obtained by normalized peak areas and hydrocarbon types data which was provided by the SH/T 0606—2005 method. Experimental results show that the aromatics in the LCO include alkylbenzenes(Z=-6), naphthalenes(Z=-12), anthracenes and phenanthrenes(Z=-18). Besides the above aromatics, it was also identified indans and tetralins(Z value of-8), in which indanes are dominant; indenes and a small amount of dinaphthenebenzenes(Z value of-10); biphenyls and acenaphthenes(Z value of-14), in which acenaphthenes are dominant; and fluorenes(Z value of-16). Acenaphthylenes were not detected in the LCO. The developed method can provide detailed information of aromatic types and the molecular composition of monomer compound.
Comprehensive two-dimensional gas chromatography coupled with high resolution time of flight mass spectrometry(GC×GC/HR-TOF MS) was employed for the characterization of aromatics in light cycle oil(LCO). Identification of aromatic hydrocarbons was carried out by mass spectrum analysis, through comparing with boiling point information and retention time of standard reference materials. High resolution of GC×GC/HR-TOF MS was also used for the above aromatics identification. The main types of aromatics and their chemical structures in LCO were determined. The content of aromatics that had the same Z value but different types, can be obtained by normalized peak areas and hydrocarbon types data which was provided by the SH/T 0606—2005 method. Experimental results show that the aromatics in the LCO include alkylbenzenes(Z=-6), naphthalenes(Z=-12), anthracenes and phenanthrenes(Z=-18). Besides the above aromatics, it was also identified indans and tetralins(Z value of-8), in which indanes are dominant; indenes and a small amount of dinaphthenebenzenes(Z value of-10); biphenyls and acenaphthenes(Z value of-14), in which acenaphthenes are dominant; and fluorenes(Z value of-16). Acenaphthylenes were not detected in the LCO. The developed method can provide detailed information of aromatic types and the molecular composition of monomer compound.
引文
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[12]押淼磊,李昱茜,王怡程,等.全二维气相色谱-飞行时间质谱(GC×GC/TOF MS)对比研究不同燃料油中烷烃芳烃的谱图特征[J].环境化学,2016,35(5):933-940.(YA Miaolei,LI Yuqian,WANG Yicheng,et al.Comparative research on the spectral characteristic of alkane and aromatic hydrocarbon in different fuel oil by GC×GC/TOF MS[J].Environmental Chemical,2016,35(5):933-940.)
[13]蔡新恒,龙军,王乃鑫,等.催化裂化柴油中多环芳烃加氢转化的分子水平表征[J].石油学报(石油加工),2017,33(3):403-410.(CAI Xinheng,LONG Jun,WANG Naixin,et al.Molecular characterization and transformation of PAHs in the hydrotreating process of light cycle oil[J].Acta Petrolei Sinica(Petroleum Processing Section),2017,33(3):403-410.)
[14]汪文虎,秦延龙.烃类物理化学数据手册[M].第1版.北京:烃加工出版社,1990.
[15]MIKI Y,SUGIMOTO Y.Analysis of recycle solvent in coal liquefaction(II).Acenaphthene and biphenyl derivatives[J].Journal of the Fuel Society of Japan,1998,77(3):213-222.
[16]MORGAN T J,GEORGE A,LVAREZ P,et al.Characterization of molecular mass ranges of two coal tar distillate fractions(creosote and anthracene oils)and aromatic standards by LD-MS,GC-MS,Probe-MS and size-exclusion chromatography[J].Energy&Fuels,2008,22(5):3275-3292.
[17]辛利,杨朝合,冯翔,等.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[J].分析化学,2017,45(4):489-494.(XIN Li,YANG Chaohe,FENG Xiang,et al.A method of qualitative and quantitative analysis on fluid catalytic cracking full range gasoline by comprehensive two-dimensional gas chromatography coupled with time-of-flight mass spectrometry[J].Chinese Journal of Analytical Chemistry,2017,45(4):489-494).
[2]林玉,李怿,白正伟,等.高效液相色谱-光电二极管阵列检测法测定柴油中芳烃的类型[J].色谱,2008,26(2):250-253.(LIN Yu,LI Yi,BAI Zhengwei,et al.Determination of aromatic hydrocarbon types in diesel oil using high performance liquid chromatography with photodiode array detection[J].Chinese Journal of Chromatography,2008,26(2):250-253.)
[3]隋芝宇,张永惠,王梦迪.荧光指示吸附法测量柴油馏分芳烃含量[J].广州化工,2014,42(11):145-146.(SUI Zhiyu,ZHANG Yonghui,WANG Mengdi.Fluorescent indicator adsorption method to measure the aromatic content of diesel fractions[J].Guangzhou Chemical Industry,2014,42(11):145-146.)
[4]陈旺轩.加氢裂化柴油芳烃含量测定方法的改进[J].广东化工,2008,36(2):81-83.(CHEN Wangxuan.Improvement of the aroma contents determination method in hydrogen cracking diesel oil[J].Guangdong Chemical Industry,2008,36(2):81-83.)
[5]太史剑瑶,程仲芊,凌凤香.超临界流体色谱法测定柴油芳烃含量[J].当代化工,2014,43(10):2199-2202.(TAISHI Jianyao,CHENG Zhongqian,LINGFengxiang.Determination of aromatic content in diesel oil by supercritical fluid chromatography[J].Contemporary Chemical Industry,2014,43(10):2199-2202.)
[6]DOSSEH G,ROUSSEAU B,FUCHS A H.Identification of aromatic molecules in intermediate boiling crude oil fractions by 2Dn.m.r.spectroscopy[J].Fuel,1991,70(5):641-646.
[7]中国石油化工集团公司.中间馏分烃类组成测定法(质谱法):SH/T 0606-2005[S].北京:中国石化出版社,2005.
[8]徐延勤,祝馨怡,刘泽龙,等.固相萃取-气相色谱-飞行时间质谱测定柴油中烯烃的碳数分布[J].石油学报(石油加工),2010,26(3):431-436.(XU Yanqin,ZHU Xinyi,LIU Zelong,et al.Characterization of alkenes in diesel by solid phase extraction and GC field ionization time-of-flight high-resolution mass spectrometry[J].Acta Petrolei Sinica(Petroleum Processing Section),2010,26(3):431-436.)
[9]TRAN T C,LOGAN G A,GROSJEAN E,et al.Use of comprehensive two-dimensional gas chromatography/time-of-flight mass spectrometry for the characterization of biodegradation and unresolved complex mixtures in petroleum[J].Geochimica et Cosmochimica Acta,2010,(74):6468-6484.
[10]áVILA B M F,PEREIRA R,GOMES A O,et al.Chemical characterization of aromatic compounds in extra heavy gasoil by comprehensive two-dimensional gas chromatography coupled to time-of-flight mass spectrometry[J].Journal of Chromatography A,2011,1218(21):3208-3216.
[11]王汇彤,翁娜,张水昌,等.全二维气相色谱/飞行时间质谱对原油芳烃分析的图谱识别[J].科学通报,2010,55(21):2124-2130.(WANG Huitong,WENG Na,ZHANG Shuichang,et al.Identification of petroleum aromatic fraction by comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometer[J].Chinese Sci Bull,2010,55(21):2124-2130.)
[12]押淼磊,李昱茜,王怡程,等.全二维气相色谱-飞行时间质谱(GC×GC/TOF MS)对比研究不同燃料油中烷烃芳烃的谱图特征[J].环境化学,2016,35(5):933-940.(YA Miaolei,LI Yuqian,WANG Yicheng,et al.Comparative research on the spectral characteristic of alkane and aromatic hydrocarbon in different fuel oil by GC×GC/TOF MS[J].Environmental Chemical,2016,35(5):933-940.)
[13]蔡新恒,龙军,王乃鑫,等.催化裂化柴油中多环芳烃加氢转化的分子水平表征[J].石油学报(石油加工),2017,33(3):403-410.(CAI Xinheng,LONG Jun,WANG Naixin,et al.Molecular characterization and transformation of PAHs in the hydrotreating process of light cycle oil[J].Acta Petrolei Sinica(Petroleum Processing Section),2017,33(3):403-410.)
[14]汪文虎,秦延龙.烃类物理化学数据手册[M].第1版.北京:烃加工出版社,1990.
[15]MIKI Y,SUGIMOTO Y.Analysis of recycle solvent in coal liquefaction(II).Acenaphthene and biphenyl derivatives[J].Journal of the Fuel Society of Japan,1998,77(3):213-222.
[16]MORGAN T J,GEORGE A,LVAREZ P,et al.Characterization of molecular mass ranges of two coal tar distillate fractions(creosote and anthracene oils)and aromatic standards by LD-MS,GC-MS,Probe-MS and size-exclusion chromatography[J].Energy&Fuels,2008,22(5):3275-3292.
[17]辛利,杨朝合,冯翔,等.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[J].分析化学,2017,45(4):489-494.(XIN Li,YANG Chaohe,FENG Xiang,et al.A method of qualitative and quantitative analysis on fluid catalytic cracking full range gasoline by comprehensive two-dimensional gas chromatography coupled with time-of-flight mass spectrometry[J].Chinese Journal of Analytical Chemistry,2017,45(4):489-494).