Molecular characterization of sulfur-containing compounds in Saudi Arabia atmospheric residue

doi:10.16085/j.issn.1000-6613.2017.02.014

Abstract

Abstract: The macroscopic properties of heavy oil had been extensively studied. There are very few studies on characterizing of molecular level information. To having better understanding of the composition of heavy oil,and providing more detailed and effective information for further processing,the sulfur-containing compounds from Saudi Arabia atmospheric residue were converted to methyl sulfide salt with polarity using methyl derivatization method. Positive-ion electrospray ionization Fourier transform ion cyclotron resonance mass spectrometer(ESI FT-ICR MS)was employed to analyze the heteroatomic compounds. The results showed that the relative abundance of heteroatom compounds from high to low was:S₁,N₁,S₂,O₁S₁,N₁S₁,N₁O₁,N₁S₂,and N₁O₂. S₁ class species contained a sulfur atom that had the highest relative abundance. Among them,the relative abundance of benzothiophene homologues series(DBE=6) was the highest,followed by dibenzothiophene homologues series(DBE=9). Compared with S₁ class species,the DBE and carbon number distribution of S₂ were less. Meanwhile,S₂ class species with 9 DBE had higher relative abundance.

Key words: petroleum, atmospheric residue, sulfur-containing compounds, methyl derivatization, Fourier transform ion cyclotron resonance mass spectrometer(FT-ICR MS), chemical analysis, fuel

摘要： 目前，对于重质油的研究主要以宏观性质为主，从分子层次进行表征少有报道。为了更加深入地了解重质油的组成，为下一步的加工处理提供更加详细而有效的信息。以沙特轻质原油常压渣油（SQAR）为原料，采用甲基衍生化的方法将非极性的含硫化合物转化为带有极性的甲基硫盐，正离子模式的电喷雾电离傅里叶变换离子回旋共振质谱仪分析原料中的杂原子化合物组成。结果表明：SQAR中杂原子化合物相对丰度由高至低依次为S₁、N₁、S₂、O₁S₁、N₁S₁、N₁O₁、N₁S₂、N₁O₂。相对丰度最高的为分子中包含一个硫原子的S₁类化合物。其中，DBE=6的苯并噻吩类含量最高，其次是DBE=9的二苯并噻吩类。和S₁类化合物相比，S₂类化合物的DBE和碳数分布范围更小，DBE=9的S₂类化合物相对丰度最高。

关键词: 石油, 常压渣油, 含硫化合物, 甲基衍生化, 傅里叶变换离子回旋共振质谱, 化学分析, 燃料

CLC Number:

TE624.4

LIU Mei, LIU Jindong, ZHAO Dezhi, DUAN Linhai. Molecular characterization of sulfur-containing compounds in Saudi Arabia atmospheric residue[J]. Chemical Industry and Engineering Progree, 2017, 36(02): 502-505.

刘美, 刘金东, 赵德智, 段林海. 沙特常压渣油中含硫化合物的分子组成表征[J]. 化工进展, 2017, 36(02): 502-505.

References

[1] 高利平,刘鹏,顾涛,等. 柴油馏分中含硫化合物组成与分布特征[J]. 燃料化学学报,2009(2):183-188. GAO L P,LIU P,GU T,et al. Characterization of sulfur compounds in diesel fractions[J]. Journal of Fuel Chemistry and Technology,2009(2):183-188.
[2] 周永昌,赵锁奇. 渣油超临界萃取馏分中硫化物的分离富集研究[J]. 燃料化学学报,2005,33(3):304-308. ZHOU Y C,ZHAO S Q. Study on sulfur distribution in supercritical fluid extraction fraction of residua[J]. Journal of Fuel Chemistry and Technology,2005,33(3):304-308.
[3] PURCELL J M,MERDRIGNAC I,RODGERS R P,et al. Stepwise structural characterization of asphaltenes during deep hydroconversion processes determined by atmospheric pressure photoionization(APPI)Fourier transform ion cyclotron resonance(FT-ICR)mass spectrometry[J]. Energy & Fuels,2009,24(4):2257-2265.
[4] PURCELL J M,JUYAL P,KIM D,et al. Sulfur speciation in petroleum:atmospheric pressure photoionization or chemical derivatization and electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry[J]. Energy & Fuels,2007,21(5):2869-2874.
[5] 刘颖荣,刘泽龙,胡秋玲,等. 傅里叶变换离子回旋共振质谱仪表征VGO馏分油中噻吩类含硫化合物[J]. 石油学报(石油加工),2010,26(1):52-59. LIU Y R,LIU Z L,HU Q L,et al. Characterization of sulfur aromatic species in vacuum gas oil by Fourier transform ion cyclotron resonance mass spectrometry[J]. Acta Petrolei Sinica (Petroleum Processing Section),2010,26(1):52-59.
[6] 卢鸿,史权,马庆林,等. 傅里叶变换离子回旋共振质谱对中国高硫原油的分子组成表征[J]. 中国科学(地球科学),2014,44(1):122-131. LU H,SHI Q,MA Q L,et al. Characterization of molecular composition of high sulfur crude oil in China by Fourier transform ion cyclotron resonance mass spectrometry[J]. Scientia Sinica(Terrae),2014,44(1):122-131.
[7] LIU P,SHI Q,PAN N,et al. Distribution of sulfides and thiophenic compounds in VGO subfractions:characterized by positive-ion electrospray Fourier transform ion cyclotron resonance mass spectrometry[J]. Energy & Fuels,2011,25(7):3014-3020. DOI:http:10.1021/ef200496k.
[8] MUELLER H,ANDERSSON J T,SCHRADER W. Characterization of high-molecular-weight sulfur-containing aromatics in vacuum residues using Fourier transform ion cyclotron resonance mass spectrometry[J]. Analytical Chemistry,2005,77(8):2536-2543.
[9] 潘娜,史权,徐春明,等. 直馏柴油中硫化物甲基锍盐合成及电喷雾-高分辨质谱分析[J]. 分析化学,2010(3):413-416. PAN N,SHI Q,XU C M. Synthesis and characterization of methylsulfonium salt in diesel fraction using electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry[J]. Chinese Journal of Analytical Chemistry,2010(3):413-416.
[10] SHI Q,PAN N,LIU P,et al. Characterization of sulfur compounds in oilsands bitumen by methylation followed by positive-ion electrospray ionization and Fourier transform ion cyclotron resonance mass spectrometry[J]. Energy & Fuels,2010,24(5):3014-3019.
[11] PAYZANT J D,MOJELSKY T W,STRAUSZ O P. Improved methods for the selective isolation of the sulfide and thiophenic classes of compounds from petroleum[J]. Energy & Fuels,1989,3(4):449-454.
[12] LIU P,SHI Q,PAN N,et al. Distribution of sulfides and thiophenic compounds in VGO subfractions:characterized by positive-ion electrospray Fourier transform ion cyclotron resonance mass spectrometry[J]. Energy & Fuels,2011,25(7):3014-3020.
[13] 刘美,赵海玲,孙琦,等. 沙特常压渣油超临界流体萃取分馏宽馏分中含硫化合物的分子表征[J]. 燃料化学学报,2016(2):177-183. LIU M,ZHAO H L,SUN Q,et al. Molecular characterization of sulfur-containing compounds in the wide fractions of Saudi Arabia atmospheric residue by supercritical fluid extraction fractionation[J]. Journal of Fuel Chemistry and Technology,2016(2):177-183.
[14] 史权,董智勇,张亚和,等. 石油组分高分辨质谱的数据处理[C]//宁波:全国有机质谱学术会议,2008:246-248. SHI Q,DONG Z Y,ZHANG Y H,et al. Data processing of high-resolution mass spctra for crude oil and its distillations[C]//Ningbo:National Conference on Organic Mass Spectrometry,2008:246-248.

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