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Yen−Mullins Model Applies to Oilfield Reservoirs

Li Chen, Andre Bertolini, Francois Dubost, Vladislav Achourov, Soraya Betancourt, Jesus A. Cañas,
Hadrien Dumont, Andrew E. Pomerantz, and Oliver C. Mullins*

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ABSTRACT: Fluid distributions throughout oilfield reservoirs have been measured with increasing accuracy and coverage, both
vertical and laterally, in recent years. Currently, a routine observation is that, when reservoir crude oils are in thermodynamic
equilibrium, then the reservoir is a single flow unit with fluid flow communication, addressing the most important oil production risk
associated with reservoir structure. The most accurate method of determining fluid equilibration is by measurement and analysis of
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the distribution of dissolved (or suspended) asphaltenes in the oil. This analysis employs the Flory−Huggins−Zuo equation of state
(EoS) with its reliance on the Yen−Mullins model of asphaltene nanostructures. This capability has enabled the introduction of a
new technical discipline, reservoir fluid geodynamics, which provides a significant advance in the understanding of oilfield reservoirs.
Other reservoir fluid components are also measured to assess equilibration of reservoir fluids, including dissolved gas, liquid-phase
components, various biomarkers, and methane isotopic ratios. Often, there is a single species of asphaltenes in the reservoir in
accordance with the Yen−Mullins model (molecules, nanoaggregates, and clusters). However, for some reservoirs, two species of
asphaltenes are evident. These reservoirs provide a stringent test to (1) discern nanostructures of asphaltenes and (2) determine
whether there are other prominent aggregate species of asphaltenes in addition to those indicated in the Yen−Mullins model. This
paper explores five reservoirs: three of these reservoirs exhibit one dominant species; two exhibit two species of the Yen−Mullins
model; and none of the reservoirs exhibits additional species, providing validation of asphaltene nanostructures in the Yen−Mullins
model and its application with the Flory−Huggins−Zuo EoS for novel characterization of reservoirs.

■ INTRODUCTION
Asphaltene gradients in oilfield reservoirs coupled with
Thermodynamic modeling of reservoir fluids is important
for many reasons, including the need to address the significant
risk factors in deepwater and other oilfields. In the oil industry,
thermodynamic analysis are very informative regarding the
there has been an enormous problem associated with the
nanostructures of asphaltenes, as shown herein. Thermody- assessment of fluid connectivity versus compartmentalization
namic treatment of reservoir crude oils has been in use since in oilfield reservoirs prior to production.4 A reservoir can be
1974 with the introduction of the Peng−Robinson equation of similar to a kitchen sponge with porosity connected in fluid
state (EoS) or corresponding variants, which are referred to as flow or a reservoir can be resemble a spool of bubble wrap with
cubic EoS.1 Thermodynamic analysis provides both the fluid many isolated compartments, where each compartment
compositional gradients over potentially large vertical extents requires a well for drainage. Connected reservoirs are
of reservoirs as well as the phase behavior of reservoir fluids.2 economic, while highly compartmentalized reservoirs are not
Reservoir crude oils contain dissolved gas, liquids, and economic and would require too many wells to drain. An
dissolved solids (or suspended solids), the asphaltenes. The industry-wide study of 28 deepwater Gulf of Mexico reservoirs
Peng−Robinson EoS is a variant of the van der Waals EoS and showed that 75% of the reservoirs underperformed in
is most properly applied to gas−liquid equilibria. There has production rate or total recovery primarily as a result of
been extension of the cubic EoS into the phase behavior of unrecognized compartmentalization.5 Many reservoir studies
asphaltenes, for example, through the “cubic plus association” have confirmed that if the reservoir crude oils are in
(CPA) approach.3 This approach has success because often the thermodynamic equilibrium, then the reservoir is connected;
variable that matters most in asphaltene solubility is that of the it takes massive fluid compositional redistribution to
liquid or solution phase and not that of the asphaltenes. equilibrate reservoir fluids, thus requiring connectivity.4,6−17
However, all approaches using the cubic EoS or any other EoS In contrast, pressure equilibration among different compart-
for asphaltene gradients will fail unless they invoke or predict
the correct molecular and colloidal description of asphaltenes. Received: August 31, 2020
The term “asphaltene gradient” (and, by extension, other Revised: October 12, 2020
compositional gradients) is meant to convey the spatial Published: November 9, 2020
variation of the asphaltene concentration in crude oil with
position in the reservoir. Small gradients mean little variation
with position; no gradient indicates homogeneity.

© 2020 American Chemical Society https://dx.doi.org/10.1021/acs.energyfuels.0c02937

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ments requires only small mass transport and does not require
excellent connectivity in reservoirs.4−6 Pressure communica-
tion is a necessary but insufficient condition to establish flow
communication in reservoirs.
For some select reservoirs, the evaluation of solution gas
gradients using the cubic EoS can determine whether reservoir
fluids are equilibrated.18 However, for most reservoirs, the
measurement of the gas−oil ratio (GOR) and analysis with the
cubic EoS (or other solution gas theory) is insufficient to
determine whether reservoir fluids are equilibrated.6 The
problems with this approach are that (1) the cubic EoS has
many parameters; therefore, data curve fitting is often possible
beyond that of an accurate chemical model, (2) the GOR
measurement whether in the lab or downhole has a large error
bar impeding accurate gradient measurement, and (3) the
GOR gradients are often small, for example, in black oils, and
the difference between possible homogeneous initial con-
Figure 1. In the evaluation of oilfield reservoirs, both the rock
ditions and present day equilibrium cannot be determined.6 depositional setting (lower left) and post-deposition alterations
Moreover, geochemical methods are insufficient to determine (lower right) are always considered. Petroleum system analysis
reservoir fluid compositional equilibrium for many reasons. (upper left) accounts for filling the reservoir with oil among other
Geochemical methods rely on chemical components present in tasks.31 The new discipline based on asphaltene thermodynamics,
trace levels and might not reflect bulk oil properties.19 reservoir fluid geodynamics (upper right), accounts for fluid processes
Typically, ratios of very similar compounds are used for acting from trap filling to present day enabling comprehensive
geochemical purposes; these ratios should be homogeneous reservoir evaluation.6
throughout the oil column at equilibrium. However,
homogeneity is not a good constraint to establish the extent then Newton’s second law of motion cannot be solved, F = mg,
of equilibration, especially when initial conditions remain for the force F on a particle of mass m (or buoyancy mass
unknown.6 In the extensive geochemistry literature applied to VΔρ) in a gravity field g. The Yen−Mullins model has been
the oilfield, there is little thermodynamic modeling of the used with the Flory−Huggins−Zuo (FHZ) EoS to resolve the
distribution of biomarkers. Asphaltenes are quite distinct from gravity and other terms (Figure 2).6,20−22
gaseous and liquid components of crude oils, and their
thermodynamics offer the best opportunity to evaluate of the
thermodynamic condition of the reservoir crude oils.
■ ASPHALTENE NANOSTRUCTURES
Asphaltene molecular weight and architecture had been the
Asphaltene gradients are the most recent reservoir fluid subject of substantial debate, but fortunately, the uncertainties
property to be addressed by a proper thermodynamic in both are greatly reduced.45−50 A major cause for the former
treatment,20−22 and they provide the most stringent test of conflicting literature had been unrecognized asphaltene
thermodynamic equilibrium.4,6−17 Asphaltene gradients can be aggregation causing molecular weight determinations that are
measured accurately, especially through the use of in situ fluid now known to be too large.51 Molecular diffusion measure-
measurements in oil wells, referred to as “downhole fluid ments using time-resolved fluorescence depolarization
analysis” (DFA) in oilfield well logging.4 The latest generation (TRFD) gave average asphaltene molecular weights of ∼750
of well logging tools that performs DFA can measure fluid g/mol. This contradicts the former prevailing views that
gradients accurately and efficiently.23 As noted, composition- asphaltene molecules are polymeric with large molecular
ally equilibrated reservoir fluids imply reservoir connectivity. If weights, typically too large by a factor of 10 or more.52−56
reservoir fluids are not equilibrated in a connected reservoir, Other diffusion methods gave similar results as TRFD,
then frequently a fluid process can be identified in recent including fluorescence correlation spectroscopy,57−59 nuclear
geologic time that precludes equilibrium.6,12,13,24−30 The magnetic resonance (NMR),60,61 and Taylor dispersion.62
collection of the fluid processes in geologic time constitute Many mass spectrometry methods gave results similar to
the newly codified technical discipline “reservoir fluid geo- diffusion measurements, including laser desorption ionization
dynamics” (RFG) (Figure 1).6 mass spectrometry (LDI−MS) (after precluding aggregation
The evolution of reservoir rock in geologic time is always problems),63−65 electrospray ionization Fourier transform ion
considered when trying to understand present day properties cyclotron resonance mass spectrometry,66−68 laser-induced
of the reservoir. With the advent of RFG, the same workflow acoustic desorption mass spectrometry,69 tandem mass
can now be performed on reservoir fluids and provides a spectrometry,70,71 field ionization mass spectrometry,72 atmos-
powerful new means to address all manners of reservoir pheric pressure chemical ionization mass spectrometry,73 and
concerns. RFG is fundamentally a thermodynamic approach laser desorption, laser ionization mass spectrometry
and complements well with geochemistry. Indeed, use of two- (L2MS).74−79
dimensional gas chromatography (GC × GC) for chemical TRFD studies showed that asphaltenes are dominated by the
specificity of hydrocarbons,32,33 especially interpreted within a so-called “island” molecular structure with a predominance of
geochemistry context, greatly aids in understanding the molecules with a single polycyclic aromatic hydrocarbon
evolution of reservoir fluids in geologic time.6,34−42 (PAH).52−56 Asphaltene PAHs have ∼7 rings on aver-
The treatment of asphaltene gradients in reservoirs requires age,71,80−82 and asphaltenes have roughly half of the carbon
knowledge of asphaltene molecular and colloidal structures in as aromatic and half aliphatic. 83−85 Thus, the island
crude oils. Without the resolution of the size of asphaltenes, architecture is consistent with known molecular weights. The
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Figure 2. Yen−Mullins model of asphaltenes.43,44 Asphaltenes exhibit three thresholds of aggregation. At low concentrations, asphaltenes are
dispersed as a true molecular solution. In combination with the FHZ EoS, this gives the light oil model of crude oils. At moderate concentrations,
such as found in black oils, asphaltene nanoaggregates of ∼6 molecules are formed. At high concentrations, such as in heavy oils, asphaltenes form
clusters of ∼8 nanoaggregates. Examination of asphaltene gradients in oilfield reservoirs explores the accuracy of this model.

Figure 3. AFM imaging of diverse asphaltene samples.90−92 The island molecular architecture dominates all asphaltene samples. A second class of
molecules is observed denoted as “aryl-linked core”, as shown in image B1.2. Not a single archipelago molecule was observed with an aliphatic
group linking two aromatics, despite the fact that AFM methods can readily image such molecules.93,94

width of the asphaltene PAH distribution is broad, from 4 to more aromatic moieties linked by an aryl linkage (no
15 fused rings, and was first given by molecular orbital intervening alkyl carbon).90−92
calculations accounting for measured optical data.80−82,86 A third type of molecular structure had been proposed for
L2MS studies also showed that island molecular architecture asphaltenes, the “archipelago”, consisting of two or more
dominates for asphaltenes.77 In addition, L2MS has been aromatic moieties bound together with aliphatic linkages. The
shown to have fairly flat cross sections for different molecular lack of even one “archipelago” molecule imaged in any of the
types, which is a powerful benefit for determining bulk 10 diverse asphaltene samples gave rise to concerns that such
properties of a complex mixture, such as asphaltenes.78,87−89 molecules could not be imaged by these AFM methods.
Tandem mass spectrometry studies also supported the Several compounds with an archipelago molecular structure
dominance of the island architecture.71 with two aromatic moieties cross-linked with an aliphatic
Nevertheless, one picture is worth a thousand words; Figure bridge were made and easily imaged using AFM.93,94 Several
3 shows a few images of diverse asphaltenes. Ultrahigh- “alkyl-dipyrenes” were synthesized and imaged using the same
resolution images of asphaltene molecules from atomic force protocol as for the asphaltenes. The lack of observation of a
microscopy (AFM) proved the dominance of the island single archipelago in asphaltenes is because they are not
present in an appreciable concentration in asphaltenes. In
molecular architecture for 10 asphaltene samples from diverse
particular, one compound imaged without problem has two
sources with labels in parentheses, including virgin (un-
pyrene moieties linked by ethane. The ethane carbon−carbon
processed) crude oil (A1), field asphaltene deposits, vacuum bond in this molecule is very weak at 65 kcal/mol yet still has
resid from heavy oil (B1), hydroconverted product from B1 no issues with fragmentation in the AFM imaging studies.93
(B2), from steam cracker tar (C1), immature source rock Other results from extremely sensitive methods but with large
bitumen (D2), and resid from distillation of coal-derived uncertainties in relative cross sections are consistent with some
liquids.90−92 These diverse asphaltenes were obtained from quantities of aryl-linked core structures.95 In addition, the
ExxonMobil, Shell, Chevron, and Schlumberger; the con- L2MS analysis of asphaltenes is consistent with these AFM
clusions are general. In addition, specific frontier molecular imaging results with dominance of island strcutures and a
orbitals of many of these molecules were imaged using seconadry contribution of aryl-linked cores.
scanning tunneling microscopy (STM), providing a stringent AFM imaging provides direct confirmation of the overall
validation of molecular structure, particularly PAH, with structural properties of asphaltenes. In addition, the substantial
analysis of π-electron molecular orbitals.90−92 A second type variability of individual molecules is evident. The ability of
of asphaltene molecular architecture was identified as “aryl- these molecules to form a disordered PAH stack in a
linked core” at a much lower concentration, those with two or nanoaggregate is plausible. The critical nanoaggregate
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concentration (CNAC) has been measured first by high-Q

ultrasonics96,97 to be ∼10−4 mass fraction in toluene and is
consistent with multimer formation measured by fluores-
cence.98 The aggregation number of ∼7 for nanoaggregates is
shown most clearly by surface-assisted laser desorption
ionization mass spectrometry.89,99,100 Combined small-angle
X-ray scattering (SAXS) and small-angle neutron scattering
(SANS) show similar aggregation numbers and also show that
the nanoaggregate has a structure with a PAH stack in the
interior and peripheral alkanes in the exterior.101−103 Similar
values for the CNAC and aggregation number have been
obtained by direct current (DC) conductivity, 104−106
NMR,60,61,107 and centrifugation.105,108 The second hierarch-
ical aggregation threshold corresponds to cluster formation at
the critical cluster concentration (CCC) of 10−3 mass fraction,
Figure 4. Downhole fluid analysis is used to obtain accurate
which was first shown by resolving the kinetics of floc
asphaltene gradients in oilfield reservoirs.4 (A) Schematic of a
formation109,110 and was confirmed by DC conductivity105,111 wireline tool that descends in a well after drilling and acquires
and centrifugation.105,111 Both of these methods obtain cluster formation crude oil samples in “open hole” conditions prior to
aggregation numbers of <10 nanoaggregates. SANS and SAXS placement of the steel casing in the well. Two optical spectrometers
studies obtain comparable aggregation numbers for asphaltene are depicted on the flow line. (B) Photograph of the probe module of
clusters.101−103,112,113 AFM imaging also confirms the size of the Ora intelligent wireline formation testing platform, the latest
clusters.114 generation of sample acquisition and analysis tools.23
In this paper, asphaltene gradients in oil reservoirs are
examined with a focus on testing the validity of the Yen−
between the oil and asphaltenes, R is the ideal gas constant, T is the
Mullins model for reservoir crude oils. EoS modeling for the
temperature, and δa and δ are the Hildebrand solubility parameters of
different reservoirs requires independent assessment of the the asphaltene species and oil, respectively. The FHZ EoS theory is
state of equilibrium, as discussed. Some reservoirs clearly show fairly simple; there is a single chemical interaction parameter, which is
two of the species of the Yen−Mullins model providing a very the solubility parameter. The first term in the argument of the
stringent test of possible intermediate species. The origin of exponential is the gravity term, and the next two terms account for the
the existence of two species is also discussed. The overall Flory−Huggins entropy. One research topic is the entropy term for
importance of powerful yet simple thermodynamic and high GOR oils. The last term is the solubility term. For low GOR oils,
nanostructure models is emphasized. the solution phase tends to be rather invariant and the solubility term

■
is then rather invariant. For high GOR oils2 and for the case of
diffusive gas gradients,120 the oil solubility parameter can be quite
EXPERIMENTAL SECTION variable, giving rise to a large effect of the solubility term on
Measurements of asphaltene gradients vertically and laterally in asphaltene gradients. For low GOR equilibrated oils, the most
oilfield reservoirs are key. Optical density (OD) measurement of live important term for asphaltene gradients is the gravity term.
crude oils in situ in oil wells using spectrometers is the best method to The FHZ EoS is parametric in the asphaltene particle size.
measure asphaltene gradients.4 Crude oil coloration is linear in Application of this theory to oilfield reservoirs is achieved using the
asphaltene content.9,80,115,116 three species of the Yen−Mullins model. The FHZ EoS has three
Figure 4 shows the tools used for measurement of the asphaltene terms accounting for gravity, solubility, and entropy. The gravity term
gradients in oilfields. The tools descend in oil wells after drilling, and depends strongly upon the asphaltene particle size. The gravity term is
at particular depths, the probe is deployed to establish fluid flow negligible for molecules, moderate for nanoaggregates, and very large
communication with permeable zones. Fluids are pumped out of the for clusters. Consequently, asphaltene gradients in reservoirs from the
formation into the tool and collected in high-pressure bottles when gravity term readily project to the specific species of the Yen−Mullins
the fluids are sufficiently clean of any drilling fluids that entered the model. These asphaltene gradients are easily measured in oilfield
formation.117,118 Various optical spectral measurements4 along with reservoirs using DFA. When the gravity term dominates, it is readily
viscosity and density119 are measured to determine fluid properties evident which species of the Yen−Mullins model applies. Asphaltene
and composition. The new Ora platform (Figure 4B) has superior gradients induced by the solubility term depend upon the
probe and pumping technology, enabling acquisition of fluid gradients compressibility of the oil and, thus, GOR. Low GOR oils are rather
in most borehole environments.23 incompressible; consequently, the liquid properties are rather
Theory. A modified Flory−Huggins theory is used to characterize invariant with height giving rise to small gradients induced by the
gradients of asphaltenes; a gravity term is added with Archimedes solubility term. Many black oils and all heavy oils have small GOR
buoyancy in the argument of the Boltzmann distribution term. The and, thus, small gradients from the solubility term. In addition, flashed
resulting FHZ EoS20−22 is used for modeling gradients. The ratio of oils with a gas cap in shallower reservoirs also have smaller GOR and
the asphaltene content is expressed as a ratio of optical density (OD) smaller asphaltene gradients induced by the solubility term. The
at two heights, hi, in the reservoir. entropy term tends to be smaller and tends toward homogeneity, thus

ij v gΔρ(h − h ) i v y iv y
= expjjjj a + jjj a zzz − jjj a zzz
reducing gradients.

j k v {h2 k v {h1
OD(h2) Because the FHZ EoS is parametric in particle size and because the

k
2 1
different terms, especially the gravity term, are so clearly dependent
OD(h1) RT

va[(δa − δ)h2 − (δa − δ)h12 ] zyz

upon particle size, then the application of the FHZ EoS with the

zz
zz
2 particle size from the Yen−Mullins model represents an excellent test

{
− of both this simply polymer solution theory and the Yen−Mullins
RT (1) model. In addition, there are few adjustable parameters in the FHZ
EoS; the theory either works or does not. The FHZ EoS is an EoS;
where νa and ν are the molar volumes of the asphaltene species and there is no parameter for time. The FHZ EoS only applies to
oil, respectively, g is Earth’s gravity, Δρ is the density difference reservoirs that are in thermodynamic equilibrium. Many measure-

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Figure 5. (Top) Cross section of the Ivar Aasen reservoir offshore, Norway versus relative true vertical depth subsea (TVDSS) along with the
location of six wells and the many DFA stations in the Ivar Aasen reservoir.6,11,124 (Bottom) DFA data and thermal maturity versus TVDSS for
samples spanning 80 m vertically and 7 km laterally. All DFA data, except two stations (5 and 15), match the FHZ EoS for a molecular dispersion
of asphaltenes predicting connectivity for almost all of the oilfield. Three years of production coupled with pressure measurements in the field
confirm connectivity.124 The thermal maturity biomarker ratio Ts/(Ts + Tm) is consistent with equilibration for all, except points 5 and 15, in
agreement with the DFA data.

ments can be brought to bear on this question, including the cubic Yen−Mullins model. Five reservoirs are examined here, where
EoS, geochemistry, pressure, and depletion pressure for reservoirs in the determination is made which species of the Yen−Mullins
production. If equilibrated reservoirs are found to match the FHZ model exists in the reservoir crude oil. Three reservoirs have
EoS predictions made with the Yen−Mullins model, then both the
simple theory and the asphaltene structural model are reinforced. If
one species; two reservoirs have two species, where one has
equilibrated gradients are found that do not match the FHZ EoS with molecules and nanoaggregates and the other has nano-
the Yen−Mullins model, then either the FHZ EoS, the Yen−Mullins aggregates and clusters. As might be expected, there is no
model, or both are brought into question. If an equilibrated oil reservoir crude oil with molecules and clusters but no
column exhibits two or more asphaltene species, then this represents a nanoaggregates. This is expected because the ordering of
very stringent test of the Yen−Mullins model, in that no intermediary molecules, nanoaggregates, and clusters represents an order in
species are predicted in the Yen−Mullins model. stability; therefore, the most stable and least stable should not
Asphaltenes and, to a greater extent, crude oils are dominated by co-exist without the nanoaggregate of intermediate stability. In
the Hansen polarizability parameter, over and above the Hansen
polarity or hydrogen-bonding parameter. Consequently, a single
an oil reservoir, having molecules and clusters without
solubility parameter for the oil and another for the asphaltenes can be nanoaggregates would be akin to having a condensate on top
used without the need for introducing more variables, for example, of a heavy oil all in equilibrium; this makes no sense.
associated with the Hansen solubility parameters.121,122 Laboratory In addition, no intermediate, other species that differ from
measurements of the solubility parameter of asphaltenes, including the Yen−Mullins model have been observed in reservoir crude
asphaltenes sourced from materials other than crude oil, find that the oils. That is, there is no evidence in reservoirs of dimers,
solubility parameter of asphaltenes is nearly constant over all trimers, or other small multimers of asphaltene molecules that
sources.123 would be intermediate between molecules and nanoaggregates.

■ RESULTS AND DISCUSSION

The application of the FHZ EoS with constraints on the
Likewise, there is no evidence in reservoirs of dimers, trimers,
or small multimers of nanoaggregates that would be
intermediate between nanoaggregates and clusters. Finally,
asphaltene particle provided by the Yen−Mullins model has there is no evidence of asphaltene species larger than clusters
worked very well in oil reservoirs around the world at length have been detected in reservoir crude oils (besides phase-
scales up to 100 km.6 In turn, observations of asphaltene separated asphaltenes).
gradients in oil reservoirs can be instructive regarding the Asphaltene Molecules. Figure 5 shows a gradient of a
molecular and colloidal nature of asphaltenes in reservoir crude light oil; the asphaltene content of this oil is measured to be
oils. Asphaltene gradients in equilibrated reservoir crude can be <0.3%.6,11,124 The depth scale is relative, and the absolute
associated with one or occasionally two of the species in the depths are propriety. Figure 5 compares the relative asphaltene
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Figure 6. GCs of many degassed crude oils with DFA stations identified. (A) Peak assignments are shown; the prominent n-alkanes throughout yet
the greater peak heights for cyclic alkanes above nearby n-alkanes suggest minor levels of biodegradation. The prominent toluene peak indicates
minimal water washing. (B) Overall, the liquid-phase composition is very similar and, thus, consistent with equilibration. Nevertheless, the two
isolated samples 5 and 15 are also very similar in liquid-phase composition to the others.6,11,124

content of the oils to the thermal maturity given by the corresponds to a molecular dispersion of asphaltenes. The
biomarker ratio Ts/(Ts + Tm), where Ts is 18α(H)22,29,30- molecular size is 1.05 nm in diameter of an equivalent
trisneonorhopane and Tm is 17α(H)22,29,30-trinorhopane.125 sphere.11 There is no evidence of dimers, small multimers, or
The value of the biomarker ratio of ∼0.77 represents high nanoaggregates in these data. These data are consistent with a
maturity and is consistent with the low asphaltene content of simple light oil that charged into the reservoir, followed by
the oil at the formation in the source rock; thus, there is no fluid compositional equilibration within connected parts of the
indication that the oil lost asphaltenes in a complex mixing reservoir. Convection is required and can be modeled in this
process post oil generation. In other words, simplicity prevails. equilibration process over geologic time.126
The DFA gradient is small (little variation with depth), Figure 6 shows that the GCs of many degassed or dead
matching the light oil model of the FHZ EoS, which crude oil samples are very similar for both the connected parts
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of the reservoir and for the two isolated samples 5 and 15. The
primary conclusion is that differences in liquid-phase
composition are not easily observed in isolated samples within
an oilfield. Similar conclusions were drawn when examining
isolated oils in closely spaced stacked sands by both ultrahigh-
resolution mass spectrometry127 and two-dimensional gas
chromatography.39 Analysis of the asphaltene content and even
solution gas content compares components varying over a
large range of carbon numbers and is superior to examination
of components over a small range of carbon numbers.17 A
close examination of the gas chromatograms (GCs) in Figure 6
shows a slight reduction of lighter n-alkanes versus cyclic
alkanes and toluene, which is consistent with mild
biodegradation. Because the isolated samples 5 and 15 near
the oil−water contact have the same extent of biodegradation
as the others, then the biodegradation did not occur in this
reservoir but would be associated with a spill-fill scenario.6 The
substantial toluene peak indicates minimal water washing,
another possible complicating factor.
The two outliers, DFA stations 5 and 15, are most
informative. Sample 5 has roughly half of the asphaltene
content versus the bulk of the oil and is the highest maturity Figure 7. GOR in m3/m3 versus depth as measured both downhole
sample obtained, while sample 15 has 3 times the asphaltene (DFA) and in the lab. Near-infrared spectral analysis is used to
measure GOR downhole.4 The GOR data are consistent with
content as the bulk of the oil and is the lowest maturity sample equilibration matching the cubic EoS analysis. Nevertheless, the crude
obtained. This asphaltene content is matching expectations oil flashed in migration and/or in the reservoir, and there is a single
based on thermal maturity.31 In addition, the Ivar Aasen pressure gradient throughout the reservoir. Consequently, the GORs
reservoir is being charged from the Jurassic source rock in the are constrained to largely match equilibration modeling, even for
Viking graben to the west; the charge is likely very recent, isolated samples 5 and 15.
Pleistocene.128 With basin subsidence, reservoir trap filling
starts with the least mature, highest asphaltene oil and ends In summary, the reservoir crude oil is in thermodynamic
with the most mature, lowest asphaltene oil.31,125 The outliers, equilibrium as determined from composition, solution gas, and
5 and 15, show preserved initial heaviest oil in the east and geochemistry as well as inferred from connectivity proven in
preserved lightest oil in the west, matching expectations from production. In addition, isolated reservoir oil samples that are
simple petroleum system concepts.31 Sample 5 is seen to be not equilibrated are readily understandable from a simple
isolated in a small section of reservoir in the cross section of petroleum system context.
the field in Figure 5. Sample 15 has been shown to be isolated The asphaltene gradient (variation with depth) is very small
by a fracture observed in the whole core from the well. The and consistent with a molecular dispersion. It is very evident
sealing fracture is located above sample 15 and below other that a larger asphaltene particle, such as a nanoaggregate, is
samples in the same well that are equilibrated with the rest of inconsistent with this asphaltene gradient. There is no
the reservoir.11,124 For samples 5 and 15, the DFA OD data are complication from a significant GOR variation; therefore, the
shown to vary by a factor of 6, while the biomarker ratio varies observed asphaltene gradient is largely from gravity. In
by 6%, showing the excellent sensitivity of asphaltene analysis addition, the asphaltene gradient is unimodal; there is no
of oilfield reservoirs. indication of any second asphaltene particle that contributes to
The GORs of the samples in Figure 7 have been measured this gradient. This oilfield reservoir represents a stringent and
but are not that informative. The Ivar Aasen reservoir is fairly successful test of the FHZ EoS and the selection of the
shallow; therefore, the crude oils were partially flashed (gas molecule from the Yen−Mullins model.
liberated) in charging the reservoir. The evolved gas filled Asphaltene Molecules and Nanoaggregates. Large
structural highs near the charge point of the reservoir in the reservoirs have been discovered in the presalt, offshore Brazil,
west. Consequently, there is a deeper gas−oil contact in the in recent years. Many of these fields are dominated by
crest in the west than in the crest in the east, as seen in Figure lacustrine carbonate, which are older than the South Atlantic
5. Ocean and exhibit many complexities.129 Sections of these
Figure 7 shows that the solution gas is largely equilibrated. reservoirs are often highly productive, especially toward the
However, because there was pressure equilibration prior to crest.
production in this field and because the oils flashed when Figure 8 shows log data with extensive DFA surveys in 6
charging this reservoir, the GORs are constrained to closely wells in a large presalt oilfield.13,130 Wells B and C are in the
match equilibrium modeling whether connected or not. eastern crest (with the shallowest DFA stations) and are
Indeed, samples 5 and 15 largely match equilibrium modeling separated by ∼7 km. Well E is in the west crest about 15 km
within error. Sample 5 does have a slightly larger GOR in part from the wells in the east crest.
as a result of the charge complexity that it was trapped 80 m Figure 9 shows the DFA log data for six wells in a large
deeper than the gas−oil contact for the bulk of the oils, thus at presalt field, offshore Brazil. Production data confirms that
slightly higher pressure and GOR. Asphaltene analysis is wells B and C are connected. Production data also shows that
superior to solution gas analysis for determination of well E in the west crest is not connected to wells B and C in
thermodynamic equilibration of reservoir crude oils.6,17 the east crest. The distance between the crests is 15 km, and
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Figure 8. Oil well log data from a large oilfield in the presalt carbonates, offshore Brazil. DFA station locations are indicated in the last track for
each well. Other log data are track 1 (green), γ-ray; 2 (red), resistivity; 3 (blue), NMR permeability; 4 (red), γ density; and (blue), neutron. DFA
stations with horizontal bars for each station, where green is oil, white is solution gas, and blue is water. This field has a crestal area in the east with
wells B and C and a crest in the west with well E.

measurements to confirm the validity of small measured

differences. Here, 45 DFA stations were performed. It should
be understood that this represents a significant commitment
considering that these are deepwater wells; thus, there is a
natural desire to minimize time spent with the wireline tool at
depth. In addition, estimated errors in OD are shown in the
plot clarifying that measured differences for example between
well E versus wells B and C are real.
The spacing of wells B and C is 7 km but no offset in their
DFA gradients is observed. In addition to reservoir
connectivity, there are two factors that assist equilibration of
crude oil across this distance. First, the oil charge into the
reservoir is thought to have been in the Cretaceous about 100
million years ago,131,132 giving more than enough time for
equilibration processes to come to completion. The other
factor is that this reservoir has significant quantities of CO2,
resulting in a concentration of CO2 in the reservoir oil being
Figure 9. DFA log data (asphaltene gradients) for DFA stations in all ∼20 mol % with GORs in the range of 900 standard cubic feet
six wells depicted in Figure 8.6,13,130 The nearly vertical gradients in of gas per barrel of oil (scf/bbl) in the east crest.130 CO2 in the
wells B, C, and E are consistent with a molecular dispersion of presalt fields is from the mantle and consistent with rifting
asphaltenes for this light oil. Wells B and C have coincident generated from the South Atlantic Ocean.133 It is well-known
asphaltene gradients and are known to be connected from production that CO2 charge into oil reservoirs134 and aquifers134,135 can
data. At the base of well C, there is an intersection of molecular and give rise to density inversions and convection. Naturally,
nanoaggregate gradients with no intervening small multimers. The
bimodal nature of the asphaltene particle size, molecules, and
convection greatly accelerates equilibration in oil reservoirs
nanoaggregates is consistent with the Yen−Mullins model. beyond diffusive processes.6 The DFA asphaltene gradients of
the three crestal wells all exhibit the same gradient (but with an
offset east versus west) over a huge column height; this
the saddle point is much deeper in the column and known to indicates that equilibrium has been attained. Moreover,
have very poor permeability. The DFA asphaltene gradients of equilibration of the reservoir previously shown in Figure 5
wells B and C coincide and match the FHZ EoS for a over a 7 km lateral distance in ∼1 million years bodes well for
molecular dispersion, which is consistent with connectivity. equilibration for the reservoir in Figure 9 laterally over 7 km
The offset of the gradient in well E from the gradient of wells B and vertically over 1/2 km with a timeline of ∼100 million
and C is consistent with the known lack of connectivity years.
through the saddle point between the two crests. The gradient The asphaltene gradients from wells B and C are plotted in
of well E is also consistent with a molecular dispersion of Figure 10a without other gradient data from disconnected
asphaltenes. parts of the reservoir. A molecular dispersion of asphaltenes
When relatively small differences in DFA OD are analyzed as (FHZ EoS = 1 nm) extends over a combined 500 m vertical
is the case here, it is very important to make many for the two wells. Toward the base of the oil column, a
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sense, the presence of two asphaltene species in an oil column

doubles the chance that the Yen−Mullins model could fail. In
addition, no intermediary species are evident between the two
particles identified in the Yen−Mullins model. Having a
gradient that is not unimodal offers the opportunity to have
particles intermediary to those of the Yen−Mullins model. No
intermediary particles were found. Moreover, from a practical
standpoint of accounting for oilfield data within a thermody-
namic context, this reservoir clearly shows that the Yen−
Mullins model applies and that introduction of small multimer
species would only add fitting parameters without improve-
ment in accounting for asphaltene gradients. The origin of the
two different asphaltene species in the oil is likely due to the
CO2 charge into the reservoir. It is well-known that CO2 as
Figure 10. (a) Asphaltene gradients for wells B and C, which are
connected.6,13,130 The bimodal gradient of well C is consistent with a well as methane can change the nature of some or all of the
molecular dispersion of asphaltenes in most of the column and a asphaltene dispersion in reservoir crude oil.6
nanoaggregate dispersion toward the base of the column. (b) Figure 10b shows the DFA fluorescence log data, which
Fluorescence intensity is consistent with the OD data, showing mirrors the OD data. For the interval with unchanging OD, the
uniformity for the upper section and decreased fluorescence intensity fluorescence intensity is also unchanging. With increasing OD,
with increasing OD. (c) Pressure offset from a single pressure gradient the additional asphaltenes cause fluorescence quenching,
for a fluid of 0.3 psi/ft or a fluid density of ∼0.69 g/cm3, confirming decreasing the fluorescence intensity.136,137 This confirms
the light oil designation. The crude oil density is invariant in this
that the change in OD is due to light absorption and not light
column. The crude oil with nanoaggregates is immediately above the
oil−water contact at the bottom of the oil column. scattering. Figure 10c shows the excess pressure gradient for
wells B and C. The excess pressure is obtained by subtracting
the measured pressures versus depth from that obtained with a
nanoaggregate dispersion (FHZ EoS = 2 nm) is seen to extend defined pressure gradient, here 0.3 psi/ft gradient. The vertical
to higher ODs. There is a sharp change of slope at the base of excess pressure curve means that the actual pressure gradient
the molecular dispersion to a gradient characterized by the in the oil column is 0.3 psi/ft, which corresponds to the density
nanoaggregate. There is no evidence of intervening dimers, of 0.692 g/cm3 for the reservoir crude oil. Because water has a
trimers, or other small multimers. This bimodal distribution of much different density, the excess pressure shows a large
asphaltenes is consistent with the Yen−Mullins model. In a change of slope at the oil−water contact. The excess pressure

Figure 11. Reservoir with a black oil of moderate asphaltene concentration of a few percent.6,15,139 Data from two wells are shown; each well has an
upper sand and a lower sand. The FHZ EoS curves match expectations for a dispersion of asphaltene nanoaggregates. Reservoir connectivity is the
primary concern. The asphaltene gradients show that each sand contains equilibrated asphaltenes laterally, indicating lateral connectivity. The offset
of the DFA asphaltene gradients establishes that the sands are not in good communication with each other. All production data for years confirm
these predictions. All other fluid properties [GOR, density, viscosity, and Ts/(Ts + Tm)] are consistent with the asphaltene gradient analysis, but
none has the sensitivity of the asphaltenes.6,15,139

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Figure 12. Comparison of connectivity predictions from asphaltene gradient analysis and seismic image analysis.6,15,139 As discussed in Figure 11,
DFA gradients predict lateral connectivity in the upper sand and lower sand. Isopach images of the upper sand and lower sand show that both of
these sands are quite thick, averaging ≥80 ft, which is consistent with lateral connectivity. The intervening shale between these two sands is laterally
extensive, consistent with the offset in the DFA data analysis.

plot confirms that the molecular and nanoaggregate parts of The DFA data can be compared to seismic imaging analysis.
the oil column appear connected and that the nanoaggregates Seismic images can provide formation thicknesses in so-called
are just above the water. isopach image analysis. Seismic image resolution is several
Asphaltene Nanoaggregates. Many black oil reservoirs meters; therefore, sealing barriers smaller than this thickness
are characterized by nanoaggregate dispersions of asphaltenes. cannot be resolved. Nevertheless, consistency of predictions of
The earliest applications of asphaltene gradient analysis with lateral connectivity in the upper and lower sands by asphaltene
simply the gravity term of the FHZ EoS are consistent with gradient analysis can be compared to seismic imaging of bed
nanoaggregate dispersions.7−9,138 For low GOR crude oils, the thicknesses.
gravity term is the only significant term of the FHZ EoS.20−22 The prediction of lateral connectivity in each sand, the upper
A relatively recent study explored the asphaltene dispersion sand and the lower sand, shown in Figure 11 is consistent with
and many other fluid and reservoir properties as well. Here, the the isopach thickness maps of these sands, shown in Figure 12.
reservoir crude oil has several percent asphaltenes and, thus, a Each sand is shown to be ∼80 ft thick or more, which is
black oil; this matches many previous oilfield case studies of consistent with connectivity obtained from DFA analysis. For
reservoirs with black oils shown to have nanoaggregates. these assessments, production is the ultimate arbiter; data from
Nanoaggregates are presumed here and work well for fitting 3 years of production is consistent with all DFA predictions on
the asphaltene gradients with the FHZ EoS. reservoir connectivity. In addition, after production com-
Figure 11 shows two wells in an oilfield that consist of both menced, a well drilled in the central fairway (but south of a
an upper sand and a lower sand.6,15,139 The DFA gradient data scissors fault) in the seismic shale “pinchout” encountered 4 ft
match expectations for a dispersion of asphaltene nano- of shale, which is below seismic resolution. The oils in the two
aggregates, which is consistent with the asphaltene concen- sands were at different pressures as a result of the lack of
tration in these oils of several percent (and varying in connectivity coupled with oil production preferentially from
accordance with the measured DFA gradient). In addition, the the lower sand.6,15,139 This proves that the DFA interpretation
offset in asphaltene gradients between the crude oils in the of poor connectivity at best between the upper and lower sands
upper and lower sands means that they are not connected, at is correct. Asphaltene equilibration analysis for black oils with a
least not well, especially considering the small physical distance nanoaggregate dispersion of asphaltenes is a powerful method
between the sands of tens of feet. The other fluid properties are of reservoir evaluation.
consistent with lateral equilibration. For example, the ratio of Asphaltene Nanoaggregates and Clusters. Black oils
thermal maturity biomarkers, Ts/(Ts + Tm), exhibits that contain a few percent of asphaltenes can have asphaltenes
invariance within error. The measured slightly higher thermal destabilized by the addition of solution gas. The addition of
maturity in the slightly lighter crude oil in the upper sand biogenic methane and crude oil in reservoirs is very
might be real. Nevertheless, the asphaltene gradients are clear commonplace throughout the world. Biogenic gas is produced
in terms of the lack of good connectivity between the upper by microbes at temperatures less than 80 °C,140 while crude
and lower sands. Years of production with corresponding oil, which is all thermogenic, is produced by kerogen
measurements confirm these predictions from DFA asphaltene catagenesis at temperatures typically exceeding 100 °C.141
gradients with thermodynamic analysis. Thus, gas reservoirs that initially form at shallow depths can be
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Figure 13. Log and lab data from a single well in a reservoir.6,14 The oil gradient at and near the oil−water contact is shown. The asphaltene
gradient is bimodal and must be explained. The methane isotope data show that the gas is mostly primary biogenic in origin. Gas addition to oil can
destabilize asphaltenes, causing some cluster formation from nanoaggregates. The excess pressure plot proves excellent connectivity of all DFA
stations but with slight baffling of the top DFA station in the stray sand.

subsequently charged with oil after subsidence. Nevertheless, Figure 14 shows that the main sand solution gas is
gas chimneys representing seal failure and gas leaking are equilibrated and that the stray sand oil is slightly off the
observed in seismic imaging in many locations around the
world; thus, deeper biogenic gas reservoirs that have
undergone subsidence can leak gas into less deep oil reservoirs.
Figure 13 shows an example of a reservoir that first charged
with oil and then had primary biogenic gas added
subsequently.
Figure 13 shows well log and lab data from a single well in a
formation that consists of a main sand and a stray sand at the
top of the formation. The asphaltene gradient is clearly
bimodal in this single well. Fitting this curve with the FHZ EoS
will correspond to two particle sizes. First, it must be
established that this oil column is in thermodynamic
equilibrium, thus justifying use of the FHZ EoS. Second, if
Figure 14. Evaluation of solution gas shows that the oil in the main
equilibrated, it must be established whether the particles of the
sand is equilibrated but the oil in the stray sand has some extra
Yen−Mullins model are consistent with this bimodal solution gas. These data are largely consistent with good vertical
asphaltene gradient. In this process, the parameter set must connectivity, as determined from excess pressure in this depleted
be held to a minimum to obtain a physically meaningful result. reservoir.6,14
The pressure of the formation is depleted by roughly 1000
psi by production elsewhere in the field. The excess pressure equilibrium curve. Taken together with the methane isotope
plot shows that all points in the main sand have depleted the data, the conclusion is that that there is a slight excess of
same within 1 psi, which means extraordinary vertical thermogenic gas in the stray sand oil. This has been shown to
connectivity. Pressure measurement in the stray sand shows be associated with a gas washing process in this reservoir.6 Gas
slightly more pressure depletion by 30 psi, which means that washing corresponds to significant entry of gas, here primary
this sand is still well-connected to the main sand below but biogenic gas, bubbling into the reservoir oil and removing
there is a slight baffling effect by the shale layer between the thermogenic gaseous components originally in the oil, thus
main sand and stray sand. This baffling leads to slight replacing this original solution gas with the added primary
disequilibrium of some fluid parameters. For example, in the biogenic gas.6 This gas with some thermogenic component
main sand, the methane isotope values are equilibrated migrates to the original gas cap and is followed by entry of
vertically (all are the same at −67‰), while the stray sand more biogenic methane into the oil column. In time, the
value is −63‰, which shows that this location is in slight solution gas in the oil column becomes dominated by biogenic
disequilibrium compared to the main sand. methane, while the gas cap retains some thermogenic
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Figure 15. Various biomarker ratios are equilibrated throughout the oil column within measurement error. The added gas does not impact the
equilibration of these ratios.6,14

component. Indeed, this dynamic gas washing process causes Mullins model. The implication is that the cluster formation
the slight disequilibrium in solution gas as a result of the shale from nanoaggregates is associated with some asphaltene
baffle. This solution gas difference has a small effect on the instability associated with increased solution gas. To check
asphaltene distribution. this analysis, the asphaltene onset pressure (AOP) can be
Various biomarker ratios are homogeneous and consistent evaluated. This instability should be reflected in an elevated
with vertical equilibrium in this column. The added solution AOP.
gas does not affect these ratios. Equilibrium modeling for data The expected moderate asphaltene instability shown in
in this column is supported by these ratios (Figure 15). Figure 17 from gas addition to the reservoir crude oil is
Figure 16 shows equilibrium modeling in this oil column.
Excess pressure clearly shows excellent vertical connectivity in

Figure 17. Phase behavior of a sample of crude oil from this

reservoir.6 The phase envelop of the asphaltenes is close to the
reservoir pressure and temperature, which is consistent with the
Figure 16. Bimodal asphaltene gradient can be represented with 2 nm added gas causing some instability of the asphaltenes, as shown by
nanoaggregates and 5 nm clusters. The asphaltene instability was cluster formation.
caused by the addition of gas to this oil converting a fraction of
nanoaggregates to clusters.6,14 reflected in the elevated AOP. The reservoir pressure and
temperature exceed that of the phase envelope; thus, no
this column. Solution gas modeling shows that the main sand is deposited asphaltene is expected from this gas charge. This is
equilibrated but the stray sand is slightly off this equilibrium as consistent with all observations in the reservoir.14 The
a result of the baffling of the intervening shale break. Methane interpretation of an equilibrated bimodal distribution of
isotope ratios, which are strongly affected by primary biogenic asphaltenes with nanoaggregates and clusters in this oil column
gas addition, are shown to be equilibrated in the main sand and is supported.
only slightly off in the stray sand. Biomarker ratios are shown Clusters. A giant reservoir in the Middle East documents
to be homogeneous and, thus, equilibrated within error. Thus, the existence of clusters of nanoaggregates in a heavy oil
equilibrium modeling of the bimodal asphaltene gradient is column.10 Figure 18 shows the asphaltene gradient data
supported by many measurements. In addition, a vertical acquired in many wells around the 100 km periphery of the
column of 200 ft of oil can equilibrate in 1 million years by field. The inset shows a schematic of the anticlinal oil field, a
diffusion, which is quite fast for this Miocene reservoir.6 four-way seal. There is a black oil in the crest, but there is no
Figure 16 shows that equilibrium modeling the asphaltenes DFA data from the crest.
with 61% nanoaggregates and 39% clusters matches observa- Figure 18 shows a very compelling case for asphaltene
tions very well. The nanoaggregate and cluster sizes were held clusters existing in heavy oil. The factor of 10 variation of
fixed in the fitting, and the only variable is the fraction of each. asphaltene content matches the gravity term of the FHZ EoS
This analysis is consistent with and strongly supports the Yen− over the entire 100 km periphery with essentially no adjustable
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Figure 18. Asphaltene cluster gradient in a heavy oil column around a 100 km periphery of a giant oilfield in the Middle East.6,10 The asphaltene
gradient matches a gravity gradient of clusters with a factor of 10 variation of asphaltene content with no adjustable parameters.

parameters. The only variable is the size of the asphaltene FHZ EoS. The invariant ratio of the thermal maturity
cluster, and the data in Figure 18 is fit using a 5.1 nm cluster biomarkers Ts/(Ts + Tm) is consistent with equilibrium.6
size as opposed to the 5 nm nominal cluster size published The giant 10× asphaltene content difference from top to
years before this study was performed.43 There is no evidence bottom of the heavy oil column is not due to a thermal
for nanoaggregate dimers, nanoaggregate trimers, or other maturity variation. This is a low maturity oil consistent with a
small nanoaggregate multimers that could have been part of high asphaltene content.
the asphaltene dispersion. For heavy oil, the solubility term of Figure 20 examines whether biodegradation could be playing
the FHZ EoS has little variation because of the very low a role in producing the asphaltene gradient in Figures 18 and
solution gas content, as shown in Figure 19.6 Thus, this term 19. First, biodegradation can account for approximately a
factor of 3 increase in asphaltene content and not a factor of
10, as observed in this field. The factor of 3 limit increase for
asphaltene content derives from the microbes being capable of
consuming ∼2/3 of the oil but not much more.140 In any event,
the GCs presented in Figure 20 show that the oils are non-
biodegraded and are all very similar. To obtain a large gradient
of a factor of 3 increase in asphaltene content from
biodegradation, there must be a huge corresponding variation
of the GCs for the oils in the column.28
A possible contrived fitting of the massive asphaltene
gradient in Figure 18 is through the use of the cubic EoS,
with many pseudo-components representing the asphaltenes.
This treatment requires creating many different asphaltenes
within the heavy oil column of very different chemical
properties. The validity of this approach is easy to test. Figure
Figure 19. Huge asphaltene gradient is not associated with a variation 21 shows that the sulfur speciation of asphaltenes throughout
of solution gas nor thermal maturity. The saturation pressure (Psat)
and, thus, solution gas for equilibrated heavy oil is generally low and the heavy oil column is invariant;142 this result contradicts use
homogeneous as shown. There is no thermal maturity variation in this of different asphaltene pseudo-components in the treatment of
heavy oil column as shown by examination of Ts/(Ts + Tm). The the heavy oil column in Figure 18.
thermal maturity of this crude oil is low and consistent with a high In addition, Figure 22 shows the invariant molecular weight
asphaltene content. The detailed, proprietary field map has the crest and nanoaggregate aggregation number of asphaltenes which
toward the south and the bigger dip angle also toward the south. reinforce the application of the Yen−Mullins model in this
Consequently, the asphaltene-deficient points tend to be in the north, heavy oil column.99 In this application, there is a presumption
as indicated in the figure. of a single asphaltene chemistry, which applies and obeys the
hierarchical nanocolloidal structure presented in Figure 2.
can be neglected. In addition, the gravity term for clusters is far Moreover, the results in Figures 21 and 22 refute any use of
larger than the entropy term; thus, the only surviving term of multimodal asphaltene pseudo-components within a cubic EoS
interest is the gravity term, as depicted in Figure 19. to account for the giant asphaltene gradient in Figure 18.
Figure 19 shows the low and homogeneous saturation The formation of clusters indicates less stability of
pressure of the heavy oil in this field and is consistent with asphaltenes in the sense that the solubility threshold for
equilibrium and with the use of only the gravity term from the asphaltenes is being approached for this oil. This is confirmed
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Figure 20. GCs of four samples in the heavy oil column in Figures 18 and 19. There is no evidence of any biodegradation. The liquid-phase
components are essentially homogeneous, consistent with equilibrium.

However, because there is no DFA data associated with

asphaltene gradients in the crest, we cannot determine this
colloidal nature from gravity gradients.
Energetics and Entropy. Both entropy and energy are
important in aggregate formation. In addition to the energetics,
the formation of aggregates corresponds to a change in
entropy. For aqueous micelles, micelle formation is often
associated with an entropy increase; there is a greater increase
of the entropy of the water solvent than a decrease of the
solute that is aggregating.145 The CNAC and CCC exhibit
moderate to small temperature dependencies;60,111 conse-
quently, there is a considerable entropy effect in the formations
of nanoaggregates and clusters.
In aggregation of molecules to nanoaggregates, some high-
energy PAH surface is consumed in the nanoaggregate and no
longer available for interaction with the solvent. In
transitioning from nanoaggregate to cluster, higher energy
sites of the nanoaggregate are consumed (bonded and
Figure 21. Sulfur X-ray absorption near edge structure of asphaltenes.
sequestered) in the cluster and not available to the solvent.
The asphaltene sulfur speciation is invariant throughout the heavy oil
column in Figures 18 and 19, as shown in blue curves; thiophene However, nanoaggregate formation corresponds to higher
sulfur dominates.142 The asphaltene sulfur speciation is also very energy interactions and higher energies of formation than
similar for a stacked reservoir at a different depth (red curves). cluster formation. Naturally, this is consistent with the
concentrations of nanoaggregate formation and the estimations
of Gibbs free energy of formation, ΔGagg = kT ln(CNAC). The
by the existence of a tar mat with phase-separated asphaltenes nanoaggregate CNAC of the nanoaggregate is ∼10−4 M with
below the heavy oil column.143,144 The asphaltenes were added Gibbs free energy of ∼5.5 kcal/mol at room temperature. The
by convective flows of asphaltene-rich currents from higher in CCC of the cluster is ∼2 × 10−3 M with Gibbs free energy of
the column.6,143,144 As the asphaltene content exceeds several formation of ∼3.7 kcal/mol at room temperature.

■
percent in this oil, the asphaltenes form clusters. Over geologic
time an equilibrated gravity gradient of clusters is established at
the base of the oil column. As more asphaltenes are added
CONCLUSION
from upstructure, the asphaltene concentration continues to The nature of asphaltene dispersions in laboratory solvents and
climb. When the concentration exceeds ∼35% in this oil, then reservoir crude oils is largely resolved and given by the Yen−
bulk-phase instability ensues and a tar mat is formed.6,24,25 Mullins model. The ability to specify the molecular and
The section label for the reservoir in Figure 18 only colloidal particles in reservoir crude oils has brought forth
discusses clusters. Nevertheless, there is a black oil in the crest. asphaltene thermodynamics in the treatment of reservoirs. This
If the heavy oil model of asphaltene content is projected ability was required to launch the new technical discipline
upstructure above the heavy oil column in Figure 18, then the reservoir fluid geodynamics, which corresponds to the
exponential decline of asphaltenes would give a condensate of characterization of fluid processes in reservoirs over geologic
very low asphaltene upstructure. Most assuredly, this reservoir time. This discipline required asphaltene thermodynamics to
does not contain a condensate above a heavy oil delineate whether reservoirs contain equilibrated crude oils or
column.10,143,144 Instead, once the asphaltene content drops whether the crude oils are undergoing evolution over geologic
below several percent concentration, then the asphaltene time as a result of some process. A collection of these fluid
dispersion is made of nanoaggregates and not clusters. processes defines reservoir fluid geodynamics.
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Figure 22. Asphaltene molecular weights and nanoaggregate aggregation numbers are invariant throughout the heavy oil column shown in Figure
18.99 The molecular weights are measured by L2MS,74 and the nanoaggregate aggregation numbers are determined using surface-assisted laser
desorption/ionization−mass spectrometry (SALDI-MS)100 in conjunction with L2MS for the monomer weights. These data are consistent with
FHZ EoS equilibrium modeling of the heavy oil column in Figure 18. These data contradict use of the cubic EoS with many asphaltene pseudo-
components for modeling asphaltene gradients.

The trimodal nature (meaning three distinct species) of the Andre Bertolini − Schlumberger Brazil WL, Rio de Janiero,
Yen−Mullins model has been compared to reservoir crude oils Rio de Janiero 20031-170, Brazil
that are established to be equilibrated by a variety of Francois Dubost − Schlumberger Oilfield Services (OFS),
measurements. No deviation from this trimodal description Ciudad del Carmen 24130, Mexico
of asphaltenes has been found. In particular, reservoirs have Vladislav Achourov − Schlumberger Oilfield Services (OFS),
been found that exhibit two of the species in this nanostructure N-4068 Stavanger, Norway
model. These reservoirs represent stringent test cases, in that Soraya Betancourt − Schlumberger Information Solutions
possible intermediate asphaltene species in addition to those of (SIS), Houston, Texas 77056, United States
the Yen−Mullins model might have been found. No evidence Jesus A. Cañas − Schlumberger Information Solutions (SIS),
for such small multimer species is observed in any oilfield Houston, Texas 77056, United States
study; the applicability of the Yen−Mullins model for oilfield Hadrien Dumont − Schlumberger WLH, 75007 Paris, France
reservoirs is strongly supported. Exacting analysis of aggregate Andrew E. Pomerantz − Schlumberger-Doll Research,
species in crude oils might find evidence of such intermediate Cambridge, Massachusetts 02139, United States;
species. Nevertheless, from a practical standpoint, inclusion of orcid.org/0000-0003-2639-2682
such intermediate species for reservoir concerns is not Complete contact information is available at:
warranted and the corresponding increased number of https://pubs.acs.org/10.1021/acs.energyfuels.0c02937
parameters is not justified. Application of the FHZ EoS with
its reliance on the Yen−Mullins model is found to be a robust Notes
and powerful formulation to address major questions
The authors declare no competing financial interest.

■
associated with the formation and structure of oilfield
reservoirs and to address a wide range of production concerns.

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■ AUTHOR INFORMATION
Corresponding Author
L.; De Santo, I.; Pfeiffer, T.; Achourov, V.; Hingoo, N.; Zuo, J. Y.;
Mullins, O. C. DFA Connectivity Advisor: A New Workflow To Use
Measured and Modeled Fluid Gradients for Analysis of Reservoir
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Oliver C. Mullins − Schlumberger-Doll Research, Cambridge, Houston, TX, May 5−8, 2014; DOI: 10.4043/25173-MS.
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Wilkinson, T.; Winkelman, B.; Primio, R. D.; Uchytil, S.; Nagarajan, Logging Symposium; Colorado Springs, CO, May 14−18, 2011.
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