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Department of Chemical Engineering, University of Rhode Island, Kingston, RI, 02881, USA
Published online: 13 Jun 2011.
To cite this article: Michael L. Greenfield (2011): Molecular modelling and simulation of asphaltenes and bituminous
materials, International Journal of Pavement Engineering, 12:4, 325-341
To link to this article: http://dx.doi.org/10.1080/10298436.2011.575141
1. Introduction
The bituminous materials used in paving asphalts exhibit
physical, chemical and mechanical properties that depend
on underlying chemical structure, processing conditions
and the modifiers employed. The intent of processing and
additive strategies is to alter the chemistry and phase
structure within a bitumen such that desired properties
(e.g. complex modulus jG * j, phase angle d) are obtained.
Similarly, the molecules classified as asphaltenes in
bitumen exhibit phase behaviour within bulk crude oil
such that aggregation and precipitation constrain the
temperatures and pressures over which crude oils can be
recovered and refined (Speight 1999). The goal of
understanding the physicochemical principles that control
the links among chemistry, structure and properties has
motivated work to understand interactions among saturate,
aromatic, resin and asphaltene (SARA) components within
bitumens and crude oils from a molecular perspective
using thermodynamic models and simulations. This paper
reviews such approaches in order to identify the state of the
art in describing asphaltenes and bituminous materials
using molecular scale models.
Models to be considered in this review fall in two
general classes. Molecular simulations (Allen and
Tildesley 1987, Leach 1996, Frenkel and Smit 2002) use
principles of statistical mechanics to determine properties
from the separations and orientations within packings of
*Email: greenfield@egr.uri.edu
ISSN 1029-8436 print/ISSN 1477-268X online
q 2011 Taylor & Francis
DOI: 10.1080/10298436.2011.575141
http://www.informaworld.com
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Acknowledgements
References
Aguilera-Mercado, B., et al., 2006. Mesoscopic simulation of
aggregation of asphaltene and resin molecules in crude oils.
Energy Fuels, 20, 327 338.
Allen, M.P and Tildesley, D.J., 1987. Computer simulation of
liquids. New York: Oxford University Press.
Alvarez-Ramrez, F., et al., 2004. Docking of an asphaltene
molecular model on a Fe2O3 surface, an ab initio simulated
annealing. Petroleum Science and Technology, 22, 915926.
Alvarez-Ramirez, F., Ramirez-Jaramillo, E. and Ruiz-Morales,
Y., 2006. Calculation of the interaction potential curve
between asphaltene asphaltene, asphaltene resin, and
resin resin systems using density functional theory.
Energy Fuels, 20, 195 204.
Artok, L., et al., 1999. Structure and reactivity of petroleumderived asphaltene. Energy Fuels, 13, 287 296.
Baljon, A.R.C. and Robbins, M.O., 1999. A molecular view of
bond rupture. Computational and Theoretical Polymer
Science, 9, 35 40.
Bhasin, A., et al., 2011. Use of molecular dynamics to investigate
self-healing mechanisms in asphalt binders. Journal of
Materials in Civil Engineering, 23, 485 492.
Boek, E.S., Yakovlev, D.S. and Headen, T.F., 2009. Quantitative
molecular representation of asphaltenes and molecular
dynamics simulation of their aggregation. Energy Fuels,
23, 1209 1219.
Boek, E.S., et al., 2010. Multi-scale simulation and experimental
studies of asphaltene aggregation and deposition in capillary
flow. Energy Fuels, 24, 2361 2368.
Brandt, H.C.A., et al., 1995. Thermodynamic modeling of
asphaltene stacking. Journal of Physical Chemistry, 99,
10430 10432.
Carauta, A.N.M., et al., 2005a. Conformational search and
dimerization study of average structures of asphaltenes.
Journal of Molecular Structure (Theochem), 755, 1 8.
Carauta, A.N.M., et al., 2005b. Modeling solvent effects on
asphaltene dimers. Energy Fuels, 19, 1245 1251.
Carlson, G.A. and Faulon, J., 1994. Applications of molecular
modeling in coal research. Preprints American Chemical
Society Division of Fuel Chemistry, 39 (1), 18 21.
Chapman, W.G., Jackson, G. and Gubbins, K.E., 1988. Phase
equilibria of associating fluids: chain molecules with
multiple bonding sites. Molecular Physics, 65, 1057 1079.
339
and related approaches. Industrial and Engineering Chemistry Research, 40, 2193 2211.
Mullins, O.C., 2010. The modified Yen model. Energy Fuels,
24, 2179 2207.
Mullins, O.C. and Sheu, E.Y., 1998. Structures and dynamics of
asphaltenes. New York: Plenum Press.
Mullins, O.C., et al., 2007. Asphaltenes, heavy oils, and
petroleomics. New York: Springer.
Murgich, J., 2002. Intermolecular forces in aggregates of
asphaltenes and resins. Petroleum Science and Technology,
20, 983 997.
Murgich, J., 2003. Molecular simulation and the aggregation of
the heavy fractions in crude oils. Molecular Simulation,
29, 451 461.
Murgich, J. and Strausz, O.P., 2001. Molecular mechanics of
aggregates of asphaltenes and resins of the Athabasca oil.
Petroleum Science and Technology, 19, 231 243.
Murgich, J., Rodrguez M, J. and Aray, Y., 1996. Molecular
recognition and molecular mechanics of micelles of some
model asphaltenes and resins. Energy Fuels, 10, 68 76.
Murgich, J., et al., 1998. Interatomic interactions in the
adsorption of asphaltenes and resins on kaolinite calculated
by molecular dynamics. Energy Fuels, 12, 339 343.
Murgich, J., Abanero, J.A. and Strausz, O.P., 1999. Molecular
recognition in aggregates formed by asphaltene and resin
molecules from the Athabasca oil sand. Energy Fuels, 13,
278 286.
Murgich, J., et al., 2001. A molecular mechanics-density
functional study of the adsorption of fragments of
asphaltenes and resins on the (001) surface of Fe2O3.
Petroleum Science and Technology, 19, 437 455.
Murgich, J., et al., 2002. Molecular mechanics and microcalorimetric investigations of the effects of molecular water on
the aggregation of asphaltenes in solutions. Langmuir,
18, 9080 9086.
Neurock, M. and Klein, M.T., 2000. Monte Carlo simulation of
asphaltene structure, reactivity and reaction pathways. In:
T.F. Yen and G.V. Chilingarian, eds. Asphalts and
asphaltenes. (Developments in Petroleum Science Series)
Vol. 40B. New York: Elsevier, 59 101.
Neurock, M., et al., 1990. Monte Carlo simulation of complex
reaction systems: molecular structure and reactivity in
modeling heavy oils. Chemical Engineering Science,
45, 2083 2088.
Neurock, M., et al., 1994. Molecular representation of complex
hydrocarbon feedstocks through efficient characterization
and stochastic algorithms. Chemical Engineering Science,
49, 4153 4177.
Ngai, K.L., 1999. Alternative explanation of the difference
between translational diffusion and rotational diffusion in
supercooled liquids. Journal of Physical Chemistry B, 103,
10684 10694.
Ortega-Rodriguez, A., et al., 2001. Interaction energy in Mayaoil asphaltenes: a molecular mechanics study. Petroleum
Science and Technology, 19, 245 256.
Ortega-Rodrguez, A., et al., 2003. Molecular view of the
asphaltene aggregation behavior in asphaltene resin mixtures. Energy Fuels, 17, 1100 1108.
Ortega-Rodriguez, A., et al., 2004. Stability and aggregation of
asphaltenes in asphaltene resin solvent mixtures. Energy
Fuels, 18, 674 681.
Pacheco-Sanchez, J.H., Zaragoza, I.P. and Martnez-Magadan,
J.M., 2003. Asphaltene aggregation under vacuum at
different temperatures by molecular dynamics. Energy
Fuels, 17, 1346 1355.
340
M.L. Greenfield
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