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Separation and characterization of petroleum asphaltene fractions by ESI FT-ICR MS and UV-vis spectrometer

Science China Chemistry volume 56, pages 856–862 (2013)Cite this article

Abstract

Using heptane, toluene, and tetrahydrofuran (THF) as eluant, asphaltenes were fractionated into five fractions based on their polarity and solubility. The molecular composition of polar heteroatom species in both asphaltene and its fractions were analyzed by negative-ion electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR MS). The application of UV-vis spectrometer in characterizing asphaltene composition and measuring asphaltene concentration was discussed. About 11.9 wt% asphaltene components adsorbed permanently on silica gel in the extrography column after excessive elution with various solvents. In negative FT-ICR MS, the mass spectra show that acidic and neutral nitrogen-containing compounds such as N1 and N1S1 mainly existe in the first three less polar fractions, while oxygen-containing compounds such as O2, O2S, O2S2, O3, and O4 show high relative abundance in more polar fractions. These results suggest oxygen-containing compounds have stronger adsorption ability with silica gel. It was observed that the double bond equivalence (DBE) distribution of N1 class species in the fractions shifted to higher values while the carbon number shifted to smaller numbers as polarity of fractions increased. This indicates that acidic and neutral N1 compounds with longer carbon chain and less aromaticity have less polarity compared with those with shorter carbon chain and stronger aromaticity. UV-vis absorbance indicats that fractions containing the most aromatic and most polar asphaltene have better absorbance at long wavelength, while the fractions that consist of least aromatic and least polar asphatlenes show high absorbance at short wavelength.

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References

  1. Mullins O. Petroleomics and structure-function relations of crude oils and asphaltene, in asphaltene, heavy oils, and petroleomics. Mullins O, Sheu E, Hammami A. Marshall A, Editors., New York: Springer, 2007. 1–16

  2. Rudrake A, Karan K, Horton JH. A combined QCM and XPS investigation of asphaltene adsorption on metal surfaces. J Colloid Interf Sci, 2009, 332(1): 22–31

    Article  CAS  Google Scholar 

  3. Jada A, Debih H. Hydrophobation of clay particles by asphaltene adsorption. Compos Interface, 2009, 16(2–3): 219–235

    Article  CAS  Google Scholar 

  4. Trejo F, Centeno G, Ancheyta J. Precipitation, fractionation and characterization of asphaltene from heavy and light crude oils. Fuel, 2004, 83(16): 2169–2175

    Article  CAS  Google Scholar 

  5. Wattana P, Fogler HS, Yen A, Carmen Garcìa MD, Carbognani L. Characterization of polarity-based asphaltene fractions. Energ Fuel, 2004, 19(1): 101–110

    Article  Google Scholar 

  6. Tan XL, Fenniri H, Gray MR. Water enhances the aggregation of model asphaltene in solution via hydrogen bonding. Energ Fuel, 2009, 23(7): 3687–3693

    Article  CAS  Google Scholar 

  7. Acevedo S, Ranaudo MA, Escobar G, Gutiérrez L, Ortega P. Adsorption of asphaltene and resins on organic and inorganic substrates and their correlation with precipitation problems in production well tubing. Fuel, 1995, 74(4): 595–598

    Article  CAS  Google Scholar 

  8. Acevedo S, Ranaudo MA, García C, Castillo J, Fernández A, Caetano M, Goncalvez S. Importance of asphaltene aggregation in solution in determining the adsorption of this sample on mineral surfaces. Colloid Surface A, 2000, 166(1–3): 145–152

    Article  CAS  Google Scholar 

  9. Buckley JS, Liu Y. Some mechanisms of crude oil/brine/solid interactions. J Petrol Sci Eng, 1998, 20(3–4): 155–160

    Article  CAS  Google Scholar 

  10. Cosultchi A, Cordova I, Valenzuela MA, Acosta DR, Bosch P, Lara VH. Adsorption of crude oil on Na+-montmorillonite. Energ Fuel, 2005, 19(4): 1417–1424

    Article  CAS  Google Scholar 

  11. Silva UG, Melo MA, Silva AF, Farias RF. Adsorption of crude oil on anhydrous and hydrophobized vermiculite. J Colloid Interf Sci, 2003, 260(2): 302–304

    Article  Google Scholar 

  12. Dubey ST, Waxman, MH. Asphaltene adsorption and desorption from mineral surfaces. SPE Reserv Eng, 1991, 6,(3): 389–395

    CAS  Google Scholar 

  13. Dudášová D, Simon S, Hemmingsen PV, Sjöblom J. Study of asphaltene adsorption onto different minerals and clays. Colloid Surface A, 2008, 317(1–3): 1–9

    Article  Google Scholar 

  14. Kumar K, Dao E, Mohanty KK. AFM study of mineral wettability with reservoir oils. J Colloid Interf Sci, 2005, 289(1): 206–217

    Article  CAS  Google Scholar 

  15. Priest C, Stevens N, Sedev R, Skinner W, Ralston J. Inferring wettability of heterogeneous surfaces by ToF-SIMS. J Colloid Interf Sci, 2008, 320(2): 563–568

    Article  CAS  Google Scholar 

  16. Yarranton HW, Alboudwarej H, Jakher R. Investigation of asphaltene association with vapor pressure osmometry and interfacial tension measurements. Ind Eng Chem Res, 2000, 39(8): 2916–2924

    Article  CAS  Google Scholar 

  17. Rakotondradany F, Fenniri H, Rahimi P, Gawrys KL, Kilpatrick PK, Gray MR. Hexabenzocoronene model compounds for asphaltene fractions: Synthesis & characterization. Energ Fuel, 2006, 20(6): 2439–2447

    Article  CAS  Google Scholar 

  18. Acevedo S, Escobar O, Echevarria L, Gutiérrez LB, Méndez B. Structural analysis of soluble and insoluble fractions of asphaltene isolated using the pnp method. relation between asphaltene structure and solubility. Energ Fuel, 2003, 18(2): 305–311

    Article  Google Scholar 

  19. Juyal P, McKenna AM, Fan T, Cao T, Rueda-Velásquez RI, Fitzsimmons JE, Yen A, Rodgers RP, Wang J, Buckley JS, Gray MR, Allenson SJ, Creek J. Joint industrial case study for asphaltene deposition. Energ Fuel, 2013, 27(4), 1899–1908

    Article  CAS  Google Scholar 

  20. Miller JT, Fisher RB, Thiyagarajan P, Winans RE, Hunt JE. Fractionation and characterization of mayan asphaltene. Energ Fuel, 1998, 12(6): 1290–1298

    Article  CAS  Google Scholar 

  21. Shi Q, Xu CM, Zhao SQ, Chung KH, Zhang YH, Gao W. Characterization of basic nitrogen species in coker gas oils by positive-ion electrospray ionization fourier transform ion cyclotron resonance mass spectrometry. Energ Fuel, 2010, 24(1): 563–569

    Article  CAS  Google Scholar 

  22. Shi Q, Zhao SQ, Xu ZM, Chung KH, Zhang YH, Xu CM. Distribution of acids and neutral nitrogen compounds in a chinese crude oil and its fractions: Characterized by negative-ion electrospray ionization fourier transform ion cyclotron resonance mass spectrometry. Energ Fuel, 2010, 24(7): 4005–4011

    Article  CAS  Google Scholar 

  23. Zhu XC, Shi Q, Zhang YH, Pan N, Xu CM, Chung KH, Zhao SQ. Characterization of nitrogen compounds in coker heavy gas oil and its fractions by liquid chromatographic separation followed by fourier transform ion cyclotron resonance mass spectrometry. Energ Fuel, 2011, 25(1): 281–287

    Article  CAS  Google Scholar 

  24. Klein GC, Kim S, Rodgers RP, Marshall AG, Yen A. Mass spectral analysis of asphaltene. II. Detailed compositional comparison of asphaltene deposit to its crude oil counterpart for two geographically different crude oils by esi ft-icr ms. Energ Fuel, 2006, 20(5): 1973–1979

    Article  CAS  Google Scholar 

  25. Rodgers R, Marshall A. Petroleomics: Advanced characterization of petroleum-derived materials by fourier transform ion cyclotron resonance mass spectrometry (ft-icr ms), in asphaltene, heavy oils, and petroleomics. Mullins O, Sheu E, Hammami A. Marshall A. Editors. New York: Springer, 2007. 63–93

    Chapter  Google Scholar 

  26. Pinkston DS, Duan P, Gallardo VA, Habicht SC, Tan X, Qian K, Gray M, Müllen K, Kenttämaa HI. Analysis of asphaltene and asphaltene model compounds by laser-induced acoustic desorption/fourier transform ion cyclotron resonance mass spectrometry. Energ Fuel, 2009, 23(11): 5564–5570

    Article  CAS  Google Scholar 

  27. McKenna AM, Purcell JM, Rodgers RP, Marshall AG. Identification of vanadyl porphyrins in a heavy crude oil and raw asphaltene by atmospheric pressure photoionization fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry. Energ Fuel, 2009, 23(4): 2122–2128

    Article  CAS  Google Scholar 

  28. Qian K, Mennito AS, Edwards KE, Ferrughelli DT. Observation of vanadyl porphyrins and sulfur-containing vanadyl porphyrins in a petroleum asphaltene by atmospheric pressure photonionization Fourier transform ion cyclotron resonance mass spectrometry. Rapid Commun Mass Sp, 2008, 22(14): 2153–2160

    Article  CAS  Google Scholar 

  29. Marchal C, Abdessalem E, Tayakout-Fayolle M, Uzio D. Asphaltene diffusion and adsorption in modified nimo alumina catalysts followed by ultraviolet (UV) spectroscopy. Energ Fuel, 2010, 24(8): 4290–4300

    Article  CAS  Google Scholar 

  30. Saada A, Siffert B, Papirer E. Comparison of the hydrophilicity/hydrophobicity of illites and kaolinites. J Colloid Interf Sci, 1995, 174(1): 185–190

    Article  CAS  Google Scholar 

  31. Alboudwarej H, Jakher RK, Svrcek WY, Yarranton HW. Spectrophotometric measurement of asphaltene concentration. Petrol Sci Technol, 2004, 22(5): 647–664

    Article  CAS  Google Scholar 

  32. Alboudwarej H, Beck J, Svrcek WY, Yarranton HW, Akbarzadeh K. Sensitivity of asphaltene properties to separation techniques. Energ Fuel, 2002, 16(2): 462–469

    Article  CAS  Google Scholar 

  33. Long HY, Shi Q, Pan N, Zhang YH, Cui DC, Chung KH, Zhao SQ, Xu CM. Characterization of middle-temperature gasification coal tar. Part 2: Neutral fraction by extrography followed by gas chromatography-mass spectrometry and electrospray ionization coupled with fourier transform ion cyclotron resonance mass spectrometry. Energ Fuel, 2012, 26(6): 3424–3431

    Article  CAS  Google Scholar 

  34. Shi Q, Yan Y, Wu XJ, Li SY, Chung KH, Zhao SQ, Xu CM. Identification of dihydroxy aromatic compounds in a low-temperature pyrolysis coal tar by gas chromatography-mass spectrometry (GC-MS) and fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). Energ Fuel, 2010, 24(10): 5533–5538

    Article  CAS  Google Scholar 

  35. Shi Q, Pan N, Long HY, Cui DC, Guo XF, Long YH, Chung KH, Zhao SQ, Xu CM, Hsu CS. Characterization of middle-temperature gasification coal tar. Part 3: Molecular composition of acidic compounds. Energ Fuel, 2013, 27(1): 108–117

    Article  CAS  Google Scholar 

  36. Liu P, Shi Q, Chung KH, Zhang YH, Pan N, Zhao SQ, Xu CM. Molecular characterization of sulfur compounds in venezuela crude oil and its sara fractions by electrospray ionization fourier transform ion cyclotron resonance mass spectrometry. Energ Fuel, 2010, 24(9): 5089–5096

    Article  CAS  Google Scholar 

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Authors and Affiliations

  1. State Key Laboratory of Heavy Oil Processing, China University of Petroleum, Beijing, 102249, China

    ShanShan Wang, Chuang Yang, ChunMing Xu, SuoQi Zhao & Quan Shi

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  1. ShanShan Wang
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  2. Chuang Yang
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  3. ChunMing Xu
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Correspondence to ChunMing Xu or Quan Shi.

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Wang, S., Yang, C., Xu, C. et al. Separation and characterization of petroleum asphaltene fractions by ESI FT-ICR MS and UV-vis spectrometer. Sci. China Chem. 56, 856–862 (2013). https://doi.org/10.1007/s11426-013-4900-2

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  • DOI: https://doi.org/10.1007/s11426-013-4900-2

Keywords

  • asphaltene
  • FT-ICR MS
  • UV-vis
  • heavy oil