基于分子组成的减压渣油聚类分析
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摘要
基于减压渣油的结焦性能受化合物类型分布的影响,将高分辨质谱分析得到的数据按照芳烃(HC)、含1个硫原子的硫化物(S1)、含2个硫原子的硫化物(S2)、含1个氮原子的氮化物(N1),按碳数的分布分成10类,并从分子组成上对71种减压渣油进行了聚类分析。结果表明:聚类分析将71种减压渣油按分子组成特点分为Ⅰ类、Ⅱ类和Ⅲ类减压渣油;为验证聚类的准确性,以减压渣油的残炭作为聚类分析结果合理性判断的依据,发现Ⅰ类减压渣油残炭最低,属于不易结焦的减压渣油;Ⅲ类减压渣油残炭最大,属于最易结焦的减压渣油;Ⅱ类减压渣油残炭高于Ⅰ类减压渣油,低于Ⅲ类减压渣油,结焦倾向居中。本研究利用聚类分析对多个减压渣油样本按分子组成进行分类,实现了FT-ICR MS数据的有效管理,为减压渣油的加工提供指导。
Coke-forming is a serious problem in vacuum residue processing,and affected by its compound classes distribution.Deepening its understanding at the molecular level is important in guiding vacuum residue processing.The detailed carbon numbers and double bond equivalent(DBE)distributions of various compounds in vacuum residues were obtained by Fourier transform ion cyclotron resonance mass spectrometry(APPI FT-ICR MS)and were grouped into 10 categories according to the carbon number distribution of the aromatic hydrocarbons,S1 compounds(single S atom in molecule),S2 compounds(two S atoms in molecule),and N1 compounds(single N atom in molecule),respectively.The cluster analysis was applied for 71 kind of vacuum residues based on above molecular group compositions.Results showed that 71 vacuum residues were divided into type I,typeⅡ,and typeⅢaccording to their molecular composition characteristics.To verify the accuracy of cluster analysis,carbon residue value of the vacuum residue was acted as the basis of rational judgment of the cluster analysis.The type I vacuum residues have the lowest carbon residue values,and is classified as less coking residue.The carbon residue value of type Ⅲ vacuum residues is the highest,belonging to coking residue.The type Ⅱvaccum residue is in the middle.This work used cluster analysis to classify vacuum residue samples based on their molecular composition,the effective management of FT-ICR MS data could be realized,and the molecular composition of vacuum residue is closely linked to its processing performance is proved.
Coke-forming is a serious problem in vacuum residue processing,and affected by its compound classes distribution.Deepening its understanding at the molecular level is important in guiding vacuum residue processing.The detailed carbon numbers and double bond equivalent(DBE)distributions of various compounds in vacuum residues were obtained by Fourier transform ion cyclotron resonance mass spectrometry(APPI FT-ICR MS)and were grouped into 10 categories according to the carbon number distribution of the aromatic hydrocarbons,S1 compounds(single S atom in molecule),S2 compounds(two S atoms in molecule),and N1 compounds(single N atom in molecule),respectively.The cluster analysis was applied for 71 kind of vacuum residues based on above molecular group compositions.Results showed that 71 vacuum residues were divided into type I,typeⅡ,and typeⅢaccording to their molecular composition characteristics.To verify the accuracy of cluster analysis,carbon residue value of the vacuum residue was acted as the basis of rational judgment of the cluster analysis.The type I vacuum residues have the lowest carbon residue values,and is classified as less coking residue.The carbon residue value of type Ⅲ vacuum residues is the highest,belonging to coking residue.The type Ⅱvaccum residue is in the middle.This work used cluster analysis to classify vacuum residue samples based on their molecular composition,the effective management of FT-ICR MS data could be realized,and the molecular composition of vacuum residue is closely linked to its processing performance is proved.
引文
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[21]邓文安,王磊,李传,等.马瑞常压渣油悬浮床加氢裂化反应生焦过程[J].石油学报(石油加工),2017,33(2):291-302
[22]刘福洲,汪文强,张静如,等.热加工过程中渣油结焦倾向的评价方法[J].石油炼制与化工,2006,37(12):53-56
[2]赵立祥,李薇,何小荣,等.热重法研究渣油的热反应性能[J].石化技术与应用,2017,35(1):19-22
[3]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
[4]Liu Tingting,Lu Jincheng,Zhao Xu,et al.Distribution of vanadium compounds in petroleum vacuum residuum and their transformations in hydrodemetallization[J].Energy Fuels,2015,29(4):2089-2096
[5]Diao Rui,Wang Wei,Wang Naixin,et al.Molecular characterization of hydrotreated atmospheric residue derived from Arabian heavy crude by GC FI?FD TOF MS and APPI FTICR MS[J].China Petroleum Processing and Petrochemical Technology,2012,14(4):80-88
[6]Zhang Tao,Zhang Linzhou,Zhou Yasong,et al.Transformation of nitrogen compounds in deasphalted oil hydrotreating:Characterized by electrospray ionization Fourier transformion Cyclotron resonance mass spectrometry[J].Energy Fuels,2013,27(6):2952-2959
[7]Marshall A G,Rodgers R P.Petroleomics:mass spectrometry returns to its roots[J].Analytical Chemistry,2005,77(1):20-27
[8]Hur M,Yeo I,Park E,Kim Y H,et al.Combination of statistical methods and Fourier transform ion cyclotron resonance mass spectrometry for more comprehensive,molecular-level interpretations of petroleum samples[J].Analytical Chemistry,2010,82(1):211-218
[9]Corilo Y E,Rowland S M,Rodgers R P.Calculation of the total sulfur content in crude oils by positive-ion atmospheric pressure photoionization fourier transform ion cyclotron resonance mass spectrometry[J].Energy Fuels,2016,30(5):3962-3966
[10]Hur M,Yeo I,Kim E,et al.Correlation of FT-ICR mass spectra with the chemical and physical properties of associated crude oils[J].Energy Fuels,2010,24(10):5524-5532
[11]许丽利.聚类分析的算法及应用[D].吉林:吉林大学,2010
[12]王景芳.模糊聚类分析在依原油特性归类中的应用[J].石油炼制与化工,1991,35(6):41-44
[13]田松柏,龙军,刘泽龙.分子水平重油表征技术开发及应用[J].石油学报(石油加工),2015,36(2):282-292
[14]范登利.残炭测定方法及数据的相关性探讨[J].石油炼制与化工,2005,36(10):61-65
[15]Li Shenghua,Liu Chenguang,Que Guohe,et al.Colloidal structures of three Chinese petroleum vacuum residues[J].Fuel,1996,75(8):1025-1029
[16]刘玲,王威,田松柏,等.渣油残炭值的定量关联分析[J].石油学报(石油加工),2018,34(3):623-628
[17]梁文杰,阙国和,陈月珠,等.我国原油减压渣油中镍、氮及残炭的分布[J].石油学报(石油加工),1993,9(3):1-9
[18]John F S,James G S.Correlation between carbon residue and molecular weight[C].Washington,DC(US):American Chemical Society,1997
[19]Gray M R.Consistency of asphaltene chemical structures with pyrolysis and coking behavior[J].Energy Fuels,2003,17(6):1566-1569
[20]Ruette F,Sierraalta A,Castells V,et al.Chemistry of carbonization—Ⅰ.A theoretical study of free radical formation from starting materials[J].Carbon,1993,31(4):645-650
[21]邓文安,王磊,李传,等.马瑞常压渣油悬浮床加氢裂化反应生焦过程[J].石油学报(石油加工),2017,33(2):291-302
[22]刘福洲,汪文强,张静如,等.热加工过程中渣油结焦倾向的评价方法[J].石油炼制与化工,2006,37(12):53-56