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1 s2.0 S0001868614003194 Main PDF
1 s2.0 S0001868614003194 Main PDF
Historical perspective
a r t i c l e
i n f o
a b s t r a c t
Asphaltenes are considered to be the heaviest and most polar fractions of crude oils and are frequently implicated
in problems encountered during production and rening as a result of phase separation. In recent years,
considerable effort has been given to understanding the phase behaviour of these structurally heterogeneous
materials from both experimental and computational perspectives. Various experimental studies have conrmed
the long-advanced colloidal behaviour of asphaltenes in organic media, and this has inspired a number of
modelling strategies. The present review is specically concerned with advances in modelling asphaltene
phase behaviour with emphasis on the use of the statistical associating uid theory (SAFT), which it attempts
to place into the wider context of thermodynamic treatments.
2014 Elsevier B.V. All rights reserved.
Contents
1.
2.
3.
Introduction . . . . . . . . . . . . .
Lattice uid theories . . . . . . . . .
Equations of state. . . . . . . . . . .
3.1.
Cubic equations of state. . . . .
3.2.
Cubic plus association . . . . .
3.3.
Statistical associating uid theory
4.
Other approaches . . . . . . . . . . .
5.
Conclusions and future trends . . . . .
Acknowledgements . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . .
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1. Introduction
Asphaltenes have attracted much research curiosity for many years.
Interest has ranged from their chemical characterisation in order to
dene their molecular structure, to understanding their solution and
interfacial behaviour, including their aggregation and precipitation
tendencies. However, even today, many of these aspects are still open
questions where further research is needed. The main reasons for this
stem from the limited or ambiguous knowledge concerning their
characterisation.
Crude oils are complex mixtures of thousands of components [1],
which are difcult to analyse and therefore characterise [2]. The vast
amount of components existing in crude oil has led to comparison
Corresponding author.
E-mail address: s.taylor@surrey.ac.uk (S.E. Taylor).
http://dx.doi.org/10.1016/j.cis.2014.12.002
0001-8686/ 2014 Elsevier B.V. All rights reserved.
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1
3
4
5
5
6
8
9
9
9
with the amount of genes in the genome, giving rise to the use of
the words petroleome and petroleomics. The difculties in
characterising the crude oil are also evident in the case of
asphaltenes, the heaviest nondistillable fraction in crude oil, where
the characteristics of this fraction will also depend on the source
of the crude oil [3]. Generically, they are classied solely on their
solubility properties, typically as the fraction of oil that is soluble
in toluene and insoluble in n-heptane.
In the oil industry upstream and downstream operations could each
benet from a comprehensive understanding of asphaltene-related
phenomena. Over the years, many studies have shown asphaltenes to
be active at water-oil interfaces, resulting in the stabilization of oil/
water emulsions, and solid-oil interfaces, causing modications to
rock wettability (refs. [4,5] and references therein). On the other hand,
a number of problems also result from their occulation and sedimentation caused by changes in solvency [6,7].
E. Forte, S.E. Taylor / Advances in Colloid and Interface Science 217 (2015) 112
Molecule
Nanoaggregate
Cluster
(~1.5 nm)
(~2 nm)
(~5 nm)
Fig. 1. Conceptual view of the modied Yen-Mullins model. The proposed molecular structure is seen in the left image. The polycyclic aromatic hydrocarbon of the molecules is represented
by a at oval in the middle image; these can form nanoaggregates with aggregation numbers of about six which contain a single aromatic disordered stack in the interior (cf. middle
image). The latter can form clusters with aggregation number of about eight; this is represented in the right image, where the spheres depict the aromatic disordered stack in a
nanoaggregate. The lines are the (mainly) alkane substituents. Adapted from ref. [36].
E. Forte, S.E. Taylor / Advances in Colloid and Interface Science 217 (2015) 112
This approach considers the process as being irreversible and not based on solving
equilibria for the asphaltenic monomers in solution and in the colloids. No distinction is
made regarding the number of asphaltenic units in the colloids and the equilibrium is
solved only based on the resins. In the absence of resins, asphaltene molecules occulate
and precipitate in this model.
2
Micelles of different size, i.e., different aggregation numbers, are regarded as different
species. The average state of an asphaltene molecule in a micellar core is to be assumed to
be similar to its state in a pure solid asphaltene phase. In the absence of resins, asphaltenic
molecules are assumed to precipitate immediately due to the low solubility of the
asphaltene monomeric molecules in the bulk.
E. Forte, S.E. Taylor / Advances in Colloid and Interface Science 217 (2015) 112
3. Equations of state
One of the advantages in the use of equations of state is the versatility in their application, which is not restricted to a range of conditions.
Equations of state are also not limited to modelling precipitation boundaries, but can be used to describe the entire phase equilibrium diagram
of the mixture. In this section we will review the application of cubic
equations of state, cubic plus association and the statistical associating
uid theory in the eld of asphaltene precipitation.
0.25
T=273 K
T=296 K
0.20
T=273 K
T=296 K
T=323
T=323 K
0.15
0.10
0.05
0.00
0.4
0.5
0.6
0.7
0.8
0.9
Fig. 2. Fractional yield (mass ratio of precipitate after washing and drying per mass of
heavy oil) versus solvent mass fraction s for a Lloydminster heavy oil diluted with either
n-pentane or n-heptane at various temperatures. Solid curves are results using the
regular- solution model of [106] for polydisperse asphaltenes; the continuous curves
correspond to dilution with n-pentane and the discontinuous curves to dilution
with n-heptane. Symbols are experimental data at temperatures of: red squares,
273 K; green circles, 296 K; blue triangles, 273 K; purple diamonds, 296 K and orange
inverted triangles, 323 K. Curves have the same colour code at each temperature.
Adapted from ref. [106].
E. Forte, S.E. Taylor / Advances in Colloid and Interface Science 217 (2015) 112
0.8
273K
0.6
296K
323K
0.4
0.2
0.0
0.4
0.5
0.6
0.7
0.8
0.9
1.0
E. Forte, S.E. Taylor / Advances in Colloid and Interface Science 217 (2015) 112
ideal
mono
chain
assoc
where Aideal is the ideal free energy, Amono is the contribution to the free
energy due to interactions between monomers or individual segments,
Achain accounts for the possibility of chain formation, and Aassoc is the
hydrogen-bonding intermolecular association. The equation is very versatile and a testament to this is the number of many different versions of
the theory that have been developed over the years. Although differences may be subtle, the main attribute leading to the various versions
is the choice of uid of reference.
In the original SAFT formulation [173,174], molecules are modelled
as associating chains of Lennard-Jones (LJ) segments, while in a simplied treatment [177,178], associating chain molecules of hard-sphere
(HS) segments are considered, SAFT-HS, and the dispersion forces are
treated at the van der Waals mean-eld level (i.e., in the absence of
correlations between particles). The SAFT-HS approach has proved to
be successful for modelling strongly hydrogen-bonded associating systems (such as water + alkanes [179]), although is not adequate for systems where dispersion interactions are dominant. Thus, the introduction
of mixing rules for the dispersion terms [180,181] led to the SAFT-VR approach [182,183], in which the uid is described in terms of associating
4
Refs. [171,172] offer a detailed discussion about these types of theories in comparison
to physical association schemes such as those that constitute the SAFT (and CPA)
formalisms.
E. Forte, S.E. Taylor / Advances in Colloid and Interface Science 217 (2015) 112
These are the standard parameters used in SAFT frameworks, where the dispersioninteraction parameters are dened based on the Hamaker constants of the pure
components.
7
For example, average molecular weights and densities for pure asphaltene and resins
are used, from which, by considering a packing fraction in the solid range, the diameter of
asphaltene molecules can be derived. This is similar for resins, but with a packing fraction
in the liquid range.
8
As in previous work [63,210], the asphaltene model is considered to be based on a single hard-core sphere of large diameter (17 ), which may more appropriately mimic the
size of a small aggregate formed by three or four asphaltene monomeric units, instead of
a single one.
45
40
35
Precipitation on set
p / MPa
30
25
20
15
Bubble curve
10
5
0
340
360
380
400
420
T/K
Fig. 4. Precipitation onset and bubble point data of a crude oil. The symbols correspond to
experimental data [64], where the blue diamonds are asphaltene precipitation onset
points and the red circles are bubble points. The continuous curve corresponds to calculations of the bubble curve using a volume-shifted Peng-Robinson, whereas the discontinuous curve corresponds to calculations of the precipitation boundary using SAFT-VR in the
context of the McMillan-Mayer theory, following the work of Wu et al. [63,210]. Adapted
from ref. [64].
Single-phase
70
p / MPa
on that of the oil, which is obtained as a function of the density and composition. A simple model is used for the asphaltenes, considered as attractive hard-core spheres; the resins are modelled as attractive hardcore chains. Association sites are added (two in asphaltene and one in
resin molecules) to mimic aggregation through directional short-range
association. Only asphaltene-asphaltene and asphaltene-resin associations are allowed. The molecular parameters for the asphaltene and
resin components6 are estimated from average properties7 to describe,
mainly qualitatively, experimental observations regarding the effect of
temperature and composition [210]. Because the medium is treated as
a continuum, it is not possible to calculate bubble pressures. In a latter
study, a volume-shifted PR equation of state is used to evaluate
vapour-liquid equilibria and obtain the composition of oil in equilibrium
with a gas phase [63]. Such a treatment is applied to several reservoir
uids based on experimental compositional data, where heavy fractions
are divided into a set of pseudocomponents represented by a molecular
weight and liquid density. Once the composition and density of the medium (liquid phase) are determined, asphaltene precipitation (understood as liquid-liquid equilibrium) is then calculated using the SAFT
molecular model presented earlier [210]. In this study, the estimated
values for the molecular parameters are kept constant with the exception of those relating to the association interactions (i.e. the number of
association sites in the asphaltene molecules and the asphalteneasphaltene and asphaltene-resin association energies), which are adjusted to t experimental onset pressure data for each particular crude oil
considered.
The SAFT-VR equation of state has also been applied to the study of
these systems. One of these applications is the work of BuenrostroGonzalez et al. [64]. In this study, the equation is used in the framework
of the McMillan-Mayer theory following the work of Wu et al. [63,210].
Analogous molecular models for the solutes are used (i.e., asphaltenes
and resins are respectively considered as attractive hard spheres8 and
hard chains). The dispersion interactions considered are based on Sutherland potentials, where the screening effects of the medium over the
energetic interaction of the solutes are, as before, estimated based on
the corresponding Hamaker constant. As in the studies of Wu et al.
[63,210] asphaltene and resins are also considered to associate through
short-ranged anisotropic interactions, which are thought to be dominant over dispersion interactions. The parameters of the model are
based on similar estimations, whereby a good prediction of asphaltene
precipitation with different n-alkanes is obtained through parameter
adjustment to a single titration curve. The same set of parameters is
then able to predict asphaltene precipitation at high pressure, with
only little adjustment of the association parameters to a few data points.
A representative result of these predictions is shown in Fig. 4. The order
of magnitude of the estimated energetic parameters is seen to agree
well with expected values for this type of interactions reported in the
literature [44,93,211,213]. As before, a volume-shifted Peng-Robinson
equation of state is also used here to explicitly model the nature of the
oil based on a considerable number of components and pseudocomponents, and determine the properties of the medium and
bubble-point pressures at conditions of vapour-liquid equilibria.
Another application of the SAFT-VR equation to model these systems
have been presented more recently by Artola et al. [209]. The SAFT
models described up to this point have focused on describing in detail
LLE
60
Precipitation
boundary
50
40
30
20
10
0
VLE
Bubble
curve
VLLE
0
200
400
600
800
T/K
Fig. 5. Constant composition p T uid phase diagram of a crude oil (symbols correspond
to experimental data [64]) modelled with a simple lumping scheme using SAFT-VR
(continuous curves). Adapted from ref. [219].
E. Forte, S.E. Taylor / Advances in Colloid and Interface Science 217 (2015) 112
65
Original
reservoir fluid
55
p / MPa
45
+ 20 % CO2
35
+ 10% CO2
25
15
320
370
420
470
520
T/K
Fig. 6. Constant composition p T uid phase diagram of a reservoir uid (symbols correspond to experimental data [220]) modelled using PC-SAFT (blue curves). The red
curves represent the PC-SAFT calculations upon the addition of a 10% mole fraction of
CO2 and the orange curves the corresponding to the addition of a 20% mole fraction of
the same component. In all cases the continuous curves correspond to bubble curve calculations and the discontinuous to the precipitation boundary. Adapted from ref. [203].
4. Other approaches
Although outside the scope of this review, efforts in this eld have
also been presented that use integral equation theories to study
structural properties of asphaltene-containing systems [218,219].
E. Forte, S.E. Taylor / Advances in Colloid and Interface Science 217 (2015) 112
Acknowledgements
The authors are grateful for nancial support and permission to publish from BP America. EF thanks A. J. Haslam and E. A. Mller for their
useful comments on this work. We also acknowledge the editor and
the anonymous referees for their valuable suggested improvements.
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