Determination of molecular masses for petroleum distillates by simulated distillation
Abstract
Determination of Molecular Mass (MM) for petroleum distillates is explored for selected samples via
High Temperature Simulated Distillation (HTSD). MM is determined as a by-product from routine
HTSD carried out using open wall capillary columns coated with apolar stationary phases. No sample
pre-separation into hydrocarbon group-types is required. Determined MM values were validated with results
achieved via correlations based on specific gravity and refractive index. Furthermore, determined MM with
the former methodologies were found to match mass spectrometric determinations carried out for the basic
polar components present within the studied samples. Moreover, HTSD analyzed petroleum distillates are
proposed as more representative calibration standards for size exclusion chromatographic separations, thus
opening the feasibility of extrapolating MM determination for non volatile petroleum residua.
References
Altgelt, K. H. & Boduszynski, M. M. (1994). Composition and analysis of heavy petroleum fractions. New York:
Marcel Dekker.
ASTM Standard D 2887. Test Method for Boiling Range Distribution of Petroleum Fractions by Gas Chromatography.
Annual Book of Standards, ASTM International, West Conshohocken, PA, 2010.
ASTM Standard D 2892. Test Method for Distillation of Crude Petroleum (15-Theoretical Plate Column). Annual
Book of Standards, ASTM International, West Conshohocken, PA, 2010.
ASTM Standard D 5236. Test Method for Distillation of Heavy Hydrocarbon Mixtures (Vacuum Potstill Method).
Annual Book of Standards, ASTM International, West Conshohocken, PA, 2010.
ASTM Standard D 6293. Test Method for Oxygenates and Paraffin, Olefin, Naphthene, Aromatic (O-PONA) Hydrocarbon Types in Low-Olefin Spark Ignition Engine Fuels by Gas Chromatography. Annual Book of Standards,
ASTM International, West Conshohocken, PA, 2010.
ASTM Standard D 7169. Test Method for Boiling Point Distribution of Samples with Resid such as Crude Oils and Atmospheric Resids by High Temperature Gas Chromatography. Annual Book of Standards, ASTM International, West Conshohocken, PA, 2010.
Bartle, K. D., Mulligan, M. J., Taylor, N., Martin, T.G. & Snape, C. E. (1984). Molecular mass calibration in size-exclusion chromatography of coal derivatives. Fuel, 63 (11), 1556-1560.
Boduszynski, M. M., McKay, J. F. & Latham, D. R. (1980). Asphaltenes. Where are you?. Association Asphalt Paving
Tech, 49: 123-143.
Carbognani, L. (1996). High temperature (70°C) size exclusion chromatography of petroleum waxes with ri and fid detection. J. of High Resol., 19 (10), 549-558.
Carbognani, L., Lubkowitz, J., Gonzalez & M. F., Pereira- Almao, P. (2007). High temperature simulated distillation
of athabasca vacuum residue fractions. Bimodal distributions and evidence for secondary “on-column” cracking of heavy hydrocarbons. Energy & Fuels, 21: 2831-2839.
Carbognani, L., Gonzalez, M. F. & Pereira-Almao, P. (2007). Characterization of athabasca vacuum residue
and its visbroken products. stability and fast hydrocarbon group-type distributions. Energy & Fuels, 21: 1631-1639.
Chen, J., McLean, N. & Hager, D. (2011). Prediction of molecular weight by-boiling-point distribution of middle
distillates from Gas Chromatography-Field Ionization Mass Spectrometry (GC-FIMS). Energy & Fuels, 25 (2), 719-726.
Coulombe, S. & Sawatzky, H. (1986) H.p.l.c separation and g.c. characterization of polynuclear aromatic fractions of bitumen, heavy oils and their synthetic products. Fuel, 65 (4), 552-557.
Coulombe, S. & Duquette, G. (1988). Simulated distillation and molecular weight determination by supercritical fluid chromatography. Am. Chem. Soc. Prep. Fuel Chem. Div., 33 (4), 920-926.
CRC Handbook of Chemistry and Physics. (2003-2004). 84th ed. Boca Ratón: Lide, D. R. CRC Press.
Durand, J. P., Fafet, A. & Barreau, A. (1989). Direct and automatic capillary GC analysis for molecular weight determination and distribution in crude oils and condensates up to C20. J. High. Resol. Chromatogr., 12 (4), 230-233.
Eggersten, F. T., Groennings, S. & Holst, J. (1960). Analytical disitillation by Gas Chromatography. Programmed
temperature operation. Anal. Chem., 32 (8), 904-909.
Goossens, A. G. (1996). Prediction of molecular weight of petroleum fractions. Ind. Eng. Chem. Res., 35 (3),
-988.
Green, L. E., Schmauch, L. J. & Worman, J. C. (1964). Simulated distillation by Gas Chromatography. Anal. Chem., 36 (8), 1512-1516.
Islas, C. A., Suelves, I., Herod, A. A. & Kandiyoti, R. (2002). Average masses of pitch fractions of narrow polydispersity for the calibration of sec by assessment of their MALDI-TOF mass spectra. Fuel Chem. Div. Prep., 47 (2), 638-639.
López-Linares, F., Carbognani, L., Sosa-Stull, C., Pereira- Almao, P. & Spencer, R. J. (2009). Adsorption of virgin
and visbroken residue asphaltenes over solid surfaces. 1. Kaolin, smectite clay minerals, and athabasca siltstone.
Energy & Fuels, 23: 1901-1908.
Lubkowitz, J. A. & Meneghini, R. (2002). Determination of boiling-point distribution by simulated distillation
from n-pentane throught n-tetratetracontane in 70 to 80 seconds. J. Chromatogr. Sci., 40 (5), 269-275.
Osjord, E. H., Ronningsen, H. P. & Tau, L (1985). Distribution of weight, density, and molecular weight in crude
oil derived from computerized capillary GC analysis. J. High. Resol. Chromatogr., 8 (10), 683-690.
Rogel, E. & Carbognani, L. (2003). Density estimation of asphaltenes using molecular dynamics simulations. Energy & Fuels, 17 (2), 378-386.
Smith, D. F., Schaub, T. M., Rahimi, P., Teclemariam, A., Rodgers, R. P. & Marshall, A. G. (2007). Self-association
of organic acids in petroleum and canadian bitumen characterized by low- and high-resolution mass spectrometry. Energy & Fuels, 21 (3), 1309-1316.
Speight, J. G. (2006). The chemistry and technology of petroleum. 4th ed. Florida: CRC Press, Taylor and Francis
Group.
Yau, W. W., Kirkland, J. J. & Bly, D. D. (1979). Modern size-exclusion liquid chromatography. practice of gel permeation and gel filtration chromatography. New York: John Wiley & Sons.
Yergin, D. (1991). The prize. The epic quest for oil, money and power. New York: Simon & Schuster.
Yücel, H. G. (2005). Prediction of molecular weight and density of n-alkanes (C6-C44). Analytica Chim. Acta,
(1), 94-97.
Zhan, D. & Fenn, J. B. (2000). Electrospray mass spectrometry of fossil fuels. Intl’ J. Mass Spectrom., 194 (2-3),
-208.