基于ESI FT-ICR MS对焦化蜡油窄馏分及其催化裂化液体产物中碱性含氮化合物的表征
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摘要
利用实沸点蒸馏装置对辽河焦化蜡油进行窄馏分切割,并利用电喷雾傅里叶变换离子回旋共振质谱对窄馏分及其催化裂化液体产物中的碱性含氮化合物进行表征,分别获得随馏分沸点的升高碱性含氮化合物的分布规律和在反应过程中的迁移规律。结果表明,不同窄馏分中都以N1类碱性含氮化合物为主,N1O1类次之,其它类型的相对丰度均较低;随馏分沸点的升高,DBE>10的N1类碱性含氮化合物的总相对丰度明显增加,但其侧链所含碳原子数逐渐减小;DBE<10的N1类碱性含氮化合物的总相对丰度变化不大,但其侧链所含碳原子数显著增加;经过催化裂化反应,不同窄馏分所得液体产物中N1类碱性含氮化合物的结构分布差异显著变小,DBE<10的N1类碱性含氮化合物对催化剂活性位的毒害作用最大。
Liaohe coker gas oil( CGO) was cutted by true boiling point distillation. In order to get the changing rule following with the rising boiling point and transformation in the reaction process,the basic nitrogen compounds in narrow fractions and catalytic cracking products were characterized by Electrospray Ionization Fourier Transform Ion Cyclotron Resonance Mass Spectrometry( ESI FT-ICR MS). The results show that the N1 class basic nitrogen compounds are dominant in all the fractions,the relative abundances of other basic nitrogen compounds are so small except the N1O1 class. The relative abundances of N1 class basic nitrogen compounds with DBE > 10 increase significantly with the rising boiling point,but the carbon number of side chains decreases slightly. The relative abundances of N1 class basic nitrogen compounds with DBE < 10 change little,but the carbon number of side chains increases significantly. The distribution of N1 class basic nitrogen compounds in liquid catalytic cracking products derived from different fractions becomes similar. The basic nitrogen compounds with DBE < 10 play a key role in the deactivation of catalytic cracking catalyst.
Liaohe coker gas oil( CGO) was cutted by true boiling point distillation. In order to get the changing rule following with the rising boiling point and transformation in the reaction process,the basic nitrogen compounds in narrow fractions and catalytic cracking products were characterized by Electrospray Ionization Fourier Transform Ion Cyclotron Resonance Mass Spectrometry( ESI FT-ICR MS). The results show that the N1 class basic nitrogen compounds are dominant in all the fractions,the relative abundances of other basic nitrogen compounds are so small except the N1O1 class. The relative abundances of N1 class basic nitrogen compounds with DBE > 10 increase significantly with the rising boiling point,but the carbon number of side chains decreases slightly. The relative abundances of N1 class basic nitrogen compounds with DBE < 10 change little,but the carbon number of side chains increases significantly. The distribution of N1 class basic nitrogen compounds in liquid catalytic cracking products derived from different fractions becomes similar. The basic nitrogen compounds with DBE < 10 play a key role in the deactivation of catalytic cracking catalyst.
引文
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[3]侯芙生.加工劣质原油对策讨论[J].当代石油石化,2007,15(2):1-6.
[4]Caeiro G,Costa A F,Cerqueira H S,et al.Nitrogen poisoning effect on the catalytic cracking of gasoil[J].Applied Catalysis.A General,2007,320(3):8-15.
[5]Cerqueira H S,Caeiro G,Costa L,et al.Deactivation of FCC catalysts[J].Journal of Molecular Catalysis.A Chemical,2008,292(1/2):1-13.
[6]陈小博,沈本贤,孙金鹏,等.焦化蜡油中碱性氮化合物的ESI FT-ICR MS表征及其催化裂化反应特性[J].石油炼制与化工,2013,44(7):22-27.
[7]Schaub T M,Hendrickson C L,Quinn J P,et al.Instrumentation and method for ultrahigh resolution field desorption ionization fourier transform ion cyclotron resonance mass spectrometry of nonpolar species[J].Analytical Chemistry,2005,77(5):1317-1324.
[8]史权,张亚和,徐春明,等.石油组分高分辨质谱分析进展与展望[J].中国科学:化学,2014,44(5):694-700.
[9]Qian K,Rodgers R P,Hendrickson C L,et al.Reading chemical fine print:Resolution and identification of 3000nitrogen-containing aromatic compounds from a single electrospray ionization Fourier transform ion cyclotron resonance mass spectrum of heavy petroleum crude oil[J].Energy&Fuels,2001,15(2):492-498.
[10]Stanford L A,Kim S,Rodgers R P,et al.Characterization of compositional changes in vacuum gas oil distillation cuts by electrospray ionization Fourier transform-ion cyclotron resonance(FT-ICR)mass spectrometry[J].Energy&Fuels,2006,20(4):1664-1673.
[11]Chen X,Li T,Liu Y,et al.Characterization of nitrogen compounds in vacuum residue and their structure comparison with coker gas oil[J].China Petroleum Processing&Petrochemical Technology,2014,16(3):33-41.
[12]Shi Q,Xu C,Zhao S,et al.Characterization of basic nitrogen species in coker gas oils by positive-ion electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry[J].Energy&Fuels,2010,24(1):563-569.
[13]Klein G C,Angstr9m A,Rodgers R P,et al.Use of saturates/aromatics/resins/asphaltenes(SARA)fractionation to determine matrix effects in crude oil analysis by electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry[J].Energy&Fuels,2006,20(2):668-672.
[14]Chen X,Shen B,Sun J,et al.Characterization and comparison of nitrogen compounds in hydrotreated and untreated shale oil by electrospray ionization(ESI)Fourier transform ion cyclotron resonance mass spectrometry(FTICR MS)[J].Energy&Fuels,2012,26(3):1707-1714.
[15]李楠,王斌,杨朝合,等.页岩油中碱性氮化物对催化裂化反应的阻滞作用及其结构表征[J].石油炼制与化工,2016,47(1):11-16.
[16]L Yingrong,W Wei,H Qiuling,et al.Characterization of basic nitrogen aromatic species obtained during fluid catalytic cracking by Fourier transform ion cyclotron resonance mass spectrometry[J].China Petroleum Processing and Petrochemical Technology,2012,14(2):18-24.
[17]Kim S,Rodgers R P,Marshall A G.Truly“exact”mass:Elemental composition can be determined uniquely from molecular mass measurement at 0.1 m Da accuracy for molecules up to 500 Da[J].International Journal of Mass Spectrometry,2006,251(2):260-265.
[18]朱玉霞.催化裂化微反评价液体产品的组成[J].石油化工,2003,32(8):708-712.
[19]于道永,徐海,阙国和,等.碱氮化合物喹啉催化裂化转化规律的研究[J].燃料化学学报,2004,32(1):43-47.
[20]徐春明,杨朝合.石油炼制工程[M].4版.北京:石油工业出版社,2009:298-301.