SPWLA 53rd Annual Logging Symposium, June 16-20, 2012

DOWNHOLE FLUID ANALYSIS AND ASPHALTENE NANOSCIENCE

FOR RESERVOIR EVALUATION MEASUREMENT
Oliver C. Mullins1, Julian Y. Zuo1, Chengli Dong2, A. Ballard Andrew1,
Hani Elshahawi2, Thomas Pfeiffer1, Myrt E. Cribbs3, Andrew, E. Pomerantz1
1. Schlumberger, 2. Shell Exploration and Production Inc., 3. Chevron North America

Society of Petrophysicists and Well Log Analysts

Copyright 2012, held jointly by the Society of Petrophysicists and Well Log
Analysts (SPWLA) and the submitting authors

straightforward to analyze by standard analytical

chemistry techniques, and there has been no
fundamental disagreement about their chemical nature.

This paper was prepared for presentation at the SPWLA 53rd Annual Logging
Symposium held in Cartagena, Colombia, June 16-20, 2012.

In stark contrast, asphaltenes have been the subject of

enormous debate; even molecular weight was disputed
by a factor of one million![1] The cost of this scientific
deficiency on all aspects of the oil industry has been
severe. For example, in reservoir engineering, reservoir
fluids are often modeled using cubic equations of state.
However, cubic equations of states were developed,
initially by Van der Waals in 1873, to treat gas-liquid
equilibria. As such, the use of a cubic EoS to treat
CCC
petroleum solids has been grossly inadequate. However,
asphaltenes cannot be ignored. One of the most
economically important hydrocarbon fluid properties,
viscosity, depends exponentially on asphaltene content.
It is the asphaltene content, after all, that gives asphalt
its desired rheology for paving materials.

ABSTRACT
In recent years, several major advances have taken
place in asphaltene science and have been codified in
the Yen-Mullins Model. Specifically, these advances
embody the characterization of the nanocolloidal
structure of asphaltenes in crude oil. They also are
applicable to surface science at the molecular level and
provide a foundation for understanding wettability. This
nanoscience also establishes the foundation for the
gravity term enabling the development of the
industrys first predictive equation of state of
asphaltene gradients in the Flory-Huggins-Zuo (FHZ)
equation of state. The FHZ equation coupled with
downhole fluid analysis (DFA) data has been used to
address major reservoir concerns including reservoir
connectivity, heavy oil columns, tar mats, and reservoir
fluid disequilibrium in many case studies. This paper
provides an overview of the developments in asphaltene
science, surface science and the development of the
FHZ EoS. We review the many classes of case studies
linking the FHZ EoS with DFA, with emphasis on the
corresponding significant improvement of capability in
each focus of study. The coupling of new science and
new technology is shown to yield tremendous
improvements in reservoir characterization.

In recent years, asphaltene science has advanced

tremendously.[2] In particular, for crude oils and
laboratory solvents, a simple picture of the asphaltene
molecular and colloidal nanoscience has emerged [3,4]
and is now [5] called the Yen-Mullins model (cf. Fig.
1). (Prof. Teh Fu Yen was the founder of modern
asphaltene science.)

INTRODUCTION
An ancient truism taught in elementary school is
matter is composed of solids, liquids and gases. True
to form, reservoir crude oils contain dissolved gases,
hydrocarbon liquids and solids, the asphaltenes.
Petroleum gases and liquids have been relatively

Fig. 1 The Yen-Mullins model; asphaltenes are

dispersed as molecules (left) in condensates, as
nanoaggreates (center) in black oils and as clusters
(right) in heavy oils.[3,4]

SPWLA 53rd Annual Logging Symposium, June 16-20, 2012

This same Eq. 1 is used to describe the reduction of the

earths atmospheric pressure (or density) with height.
The small size of air molecules yields a small gradient
of a factor of two reduction in pressure (or density) in
~5 km of height.

Figure 1 shows the predominant molecular and

colloidal species of asphaltenes in crude oil. Asphaltene
molecules are somewhat small with predominantly a
single polycyclic aromatic hydrocarbon ring (PAH) per
molecule.[3-5] The center PAH is the site of relatively
strong intermolecular attraction, while peripheral
alkanes yield steric (spatial) repulsion. This molecular
architecture dictates that the asphaltene nanoaggregate
cannot consist of more than a few molecules as
depicted in Fig. 1, and as shown by numerous
experiments.[2] Asphaltene clusters can form from
nanoaggregates again with very small aggregation
numbers (less than 10).[3,4] The Yen-Mullins model
has recently been validated in a publication with 16
coauthors from 12 different institutions.[6]

In this paper, we describe how asphaltene gradients in

reservoirs can now be readily understood within a
proper physical chemistry perspective; also tar mat
formation can be treated within this formalism. Surface
science and wettability can also now be studied with
this asphaltene science foundation. In an auspicious
development, advances in reservoir evaluation and in
asphaltene nanoscience are augmenting each other in
spite of the 13 orders of magnitude difference in size
between colloidal asphaltenes and oilfield reservoirs.
We also provide an outline of the power of this new
formalism to address many diverse reservoir concerns.
Work flows are presented to exploit this formalism
especially with DFA to evaluate reservoirs in various
settings. Areas of future focus are clarified.

All three species of asphaltenes depicted in Fig. 1 are

routinely encountered in reservoir crude oils. True
molecular solutions of asphaltene molecules are found
in condensates, while asphaltene nanoaggregates are
found at higher concentrations, such as in black oils.
Asphaltene clusters are found at even higher asphaltene
concentrations present in heavy oils or in unstable black
oils.[7,8]

RESULTS AND DISCUSSION

CCC
Interfacial Science: Much of the interfacial science
approach to crude oils and asphaltenes has been
phenomenological such as measurement of contact
angle or wettability. However, with the development of
the nanoscience model of asphaltenes shown in Fig. 1, a
1st principles approach is now all but mandated.

Asphaltene gradients can now be modeled by inclusion

of the gravity term in the Flory-Huggins model; this
new equation is now [6] known as the Flory-HugginsZuo Equation of state or FHZ EoS.[9,10] The FHZ EoS
requires accurate measurement of GOR, relative
asphaltene content and fluid density which can all be
measure by DFA.[11] For low GOR fluids such as
virtually all heavy oils, the FHZ EoS reduces
predominantly to the gravity term which is given
below.[12]








 exp 

  



1

where ODhi is the optical density from oil color

Fig. 2 Schematic representation of the results of the
first direct measurements of asphaltene molecular
orientation in Langmuir films on water. Left: model
compounds with their PAH transverse to the interfacial
plane and (blue) oxygen atoms at the interface. Right:
asphaltenes with their PAH in the interfacial plane and
their alkane substituents perpendicular to the
plane.[14]

measured at height hi in the oil column, Chi is the

corresponding asphaltene concentration, V is the
asphaltene particle size, is the density difference
between asphaltene and the bulk liquid, g is earths
gravitational acceleration, k is Botzmanns constant and
T is temperature. The optical densities are measured
using downhole fluid analysis (DFA).[13] The only
unknown in this equation is V the asphaltene particle
size; this is given in Fig.1.

SPWLA 53rd Annual Logging Symposium, June 16-20, 2012

A Langmuir film was prepared from a toluene solution

containing asphaltene nanoaggregates; a LangmuirBlodgett film was then prepared to determine the layer
thickness. Figure 3 shows the corresponding image
from Atomic force Microscopy (AFM).[15] The film
thickness determined by AFM in Fig. 3 is ~2 nm as
expected for the asphaltene nanoagggregate.[14]

Figure 2 shows results from the first direct

measurements of the molecular orientation of
asphaltenes at an asphaltene-water interface.[14] The
optical technique sum frequency generation (SFG) was
used; an IR and visible laser overlap at the interface,
undergoing nonlinear mixing and creating a UV beam.
The IR laser is tuned through vibrational resonances.
Molecular orientation is determined by controlling
polarizations of the optical beams.[14]

At higher concentrations, the asphaltene Langmuir

films are formed from asphaltene clusters. There is a
huge difference in interfacial morphology between
films formed from asphaltene nanoaggregates versus
those formed by clusters.[15]

Both asphaltenes and model compounds were

measured. Toluene solutions containing asphaltenes or
individual model compounds were placed on a water
surface, and the toluene was evaporated creating
Langmuir films. Concentrations were adjusted to yield
monolayer coverage. The film was transferred onto a
silica slide for orientation measurements (LangmuirBlodgett film). Figure 2 shows a schematic of the
results.[14] The asphaltenes are very highly aligned
with their single PAH in the plane of the interface (Fig.
2, Right). Model compounds of known chemical
structure showed a polarization with the PAH
transverse to the interfacial plane (Fig. 2, Left) due to
peripheral oxygen containing groups which seek the
interface. These pendant oxygen containing groups are
uncommon in asphaltenes. The asphaltene results from
this molecular orientation study are in strong agreement
with the asphaltene molecular architecture proposed in
Fig. 1.[14]

Fig. 4. Brewster Angle Microscopy images of Langmuir CCC

films of asphaltenes. Left: prepared from asphaltene
clusters (spreading concentration = 4 g/l). Right:
prepared
from
nanoaggregates
(spreading
concentration = 100 mg/l).[16]
Langmuir films of nanoaggregates versus clusters are
quite distinct as shown in Fig. 4.[16] Langmuir films of
asphaltene nanoaggregates on water show good
coverage and appear to be compliant while Langmuir
films of asphaltene clusters on water do not show good
coverage and appear rigid.[16] The strong contrast in
these films corresponding to nanoaggregates versus
clusters reinforces the validity of the Yen-Mullins
model.[3,4]
To be sure, asphaltene interfacial science is not a
resolved issue. Nevertheless, the value is evident of
interpreting interfacial results through the 1st principles
model in Fig. 1. Wettability and enhanced oil recovery
studies can now incorporate these new advances
thereby improving efficiency and predictability.

Fig. 3. Atomic Force Microscopy image of a LangmuirBlodgett film of asphaltene nanoaggregates. As

expected the film thickness is ~2nm and is consistent
with the Yen-Mullins model of Fig. 1.[15]

SPWLA 53rd Annual Logging Symposium, June 16-20, 2012

The concept of equilibration of reservoir fluids

mandates that the spatial distribution of the fluids,
including their composition, does not change with time.
Equilibration also mandates that small changes of
condition (e.g. T, P) yield only small changes of the
equilibrium. (This condition differentiates equilibrium
from metastability). There are many factors that can
preclude reservoir fluid equilibration. First, reservoir
fluids cannot possibly charge into reservoirs in any
equilibrated sense; the composition of the charge can
change with time, and the charge cannot initially reflect
ultimate equilibrium gradients.(ref. 13 and references
therein). In addition, reservoirs can be subject to many
dynamic processes at various points in geologic
(including recent) times. For example, a second, totally
different charge such as biogenic gas can occur. Often,
this is accompanied by some asphaltene phase change
and/or asphaltene migration. Biodegradation and water
washing can alter oil composition and grading. Leaky
seals can alter reservoir composition, shifting equilibria.
Inorganic gases such as H2S and CO2 can charge into
the reservoir at times and pathways very different than
the hydrocarbon charge.

Asphaltene Gradients: One of the primary benefits of

the Yen-Mullins model of asphaltene nanoscience is to
enable development of the first and currently only
asphlatene equation of state, the FHZ EoS, predicting
asphaltene gradients in all reservoir fluids from
condensates to mobile heavy oil.[6,7] The accurate
predictions of concentration gradients of heavy resins
as measured by DFA in a light condensate that has no
asphaltenes confirms the validity of our approach.[7] It
has now become commonplace to observe asphaltene
gradients associated with nanoaggregates in black oil.
Still, the first study of this type, the Tahiti field study,
remains the best to date because both 1) the data sets
are extensive and 2) the Tahiti crude oil is a low GOR
black oil so the gravity term dominates.[12] Without
knowing the size of the asphaltenes as given in Fig. 1, it
would have been impossible to quantify the gravity
term.

CCC
In addition, baffles can hinder equilibration and barriers
essentially preclude equilibration. Molecular diffusion
which is required to equilibrate reservoir fluids is
geologically slow at reservoir length scales.[17]
Asphaltenes, especially in colloidal species, have by far
the smallest diffusion constant of any oil component.
The enormous time required to equilibrate asphaltenes
in a reservoir is incompatible with significantly
restricted connectivity.[17] Very slow reservoir fluid
equilibration is in dramatic contrast to pressure
equilibration which is far more rapid due to the tiny
mass flow required. In many cases, the constraint of
fluid equilibration is ten million times better (more
stringent) than pressure communication to establish
reservoir connectivity.[17] Indeed, in the Tahiti
reservoir, production proved the accuracy of fluid
equilibrium to predict connectivity. Equilibration of
asphaltenes does not prove reservoir connectivity.
Nevertheless, if asphaltene equilibration, pressure
analysis and geochemistry all point to connectivity,
then probably connectivity prevails. Also, note that
connectivity does not mandate fluid equilibration.
Nevertheless, continuous fluid gradients, even if not
equilibrated, indicate connectivity. Generally more

Fig. 5. The Chevron Tahiti crude oils. The red and

blue stacked sands are each laterally connected
across the reservoir.[12]The asphaltenes in each of
these sands (and in the smaller green sand) are
equilibrated within the sand and match Eq. 1 with a
particle size of ~2 nm, the nanoaggregate.
The Tahiti study proves that the laboratory asphaltene
science that gave rise to the Yen-Mullins model can
also be applied to reservoir crude oils. Because the
GOR is low (~500 scf/bbl), the solubility term of the
FHZ EoS is small, and the asphaltene gradient becomes
dominated by the gravity term, Eq. 1. The observed
equilibration of the asphaltenes in the red and blue
sands of Fig. 5 is critical for evaluation of reservoir
connectivity. The only way for asphaltenes to be
equilibrated is for the reservoir to have good
connectivity.[17]

SPWLA 53rd Annual Logging Symposium, June 16-20, 2012

Tahiti reservoir. For heavy oils, with asphaltenes in

clusters, the gradient is ~ 50 times larger. The first field
demonstration of this was in Ecuador (cf. Fig. 7).[19]
The much larger size of the asphaltene cluster (5 nm)
compared to the nanoaggregates (2 nm) produces this
factor of 50 increase. The much larger size of the
cluster prevents thermal energy from lifting the more
massive clusters as high in the reservoir as the
nanoaggregates. Again, Eq. 1 is virtually the same as
that used to model the pressure (or density) reduction of
earths atmosphere with height. Gravity tries to pull
all air molecules down to the surface, while thermal
energy (kT) provides energy to lift the small air
molecules higher.

DFA data is needed in such cases to test dynamic fluid

models.
When the GOR is higher, then there is a gradient of
GOR, thus a gradient of the solubility term. Then, the
solubility term also becomes important in establishing
the asphaltene gradient. A recent study highlights this
fact with the corresponding data shown in Fig. 6.[18]
With a GOR in the range of 1100 scf/bbl, the
asphaltene gradient is larger than that of Tahiti;
nevertheless, the gravity term with the asphaltene
nanoaggregate (2nm) contributes to the gradient.
In the case study shown in Fig. 6, the pressure survey
indicated
compartmentalization.
However,
the
asphaltene gradient matches the FHZ EoS with ~2nm
particle size, thus indicating connectivity. Production
proved connectivity. Classic pressure surveys do have
great value in all settings as has long been known.
Nevertheless, integrating pressures with DFA surveys
along with the FHZ EoS has proven to be greater value.

x,200 x,230 x,260 x,290 x,320 x,350

CCC

X
X
X
X

Fig. 7 Asphaltene content versus height. The asphaltene

content is very high as in all heavy oils and there is a
very large asphaltene gradient in this sand a factor of
two increase in ~55 feet. The fit of Eq. 1 to the field
data gives a particle size of 5.0 nm exactly matching
expectations for clusters in Fig. 1.[19]

X
X
X
X
X
X
X
Well #5

Well #1

Well#5
A

Well D#1

Well #5

This figure shows that there is a large asphaltene

content (>10%) in this heavy oil. The GOR for this oil
is quite low, less than 100 scf/bbl. In addition, Fig. 3
shows that there is a huge asphaltene concentration
gradient, with a two-fold increase in asphaltene content
over ~55 feet. Because viscosity depends exponentially
on asphaltene content, the viscosity increase in this
column goes from 6cP at the top to 200cP at the base at
reservoir conditions. This column is high viscosity, but
below 1000 cP so might be termed mobile heavy oil
and can often be produced conventionally.[19]

Well #1

Fig. 6. A deepwater reserovir. Left: Laboratory GOR is

useful but not for establishing potential fluid gradients
here. Center: Pressure surveys indicated that the sands
in the red well and the blue wells are not connected.
Right: Asphaltene gradient in the two wells matches the
FHZ EoS with an asphaltene particle size of 2 nm.
Equilibration of asphaltenes indicates connectivity and
was proven in production.[18]
For low GOR oils, the gravity term dominates as has
been noted. For nanoaggregates, the gravity term of Eq.
1 produces an increase in asphaltene concentration of a
factor of 2 in ~1000 meters as shown in Fig. 5 for the

Figure 8 shows a very similar gradient in a mobile

heavy oil column.[20] Recently, very similar gradients
have been found in similar crude oils in Russia [21] and

SPWLA 53rd Annual Logging Symposium, June 16-20, 2012

Saudi Arabia.[22] These mobile heavy oil columns are

nearly identical in asphaltene gradients with
concomitant huge gradients in viscosity. Having similar
gradients in such diverse geographic locations does
indicate that the gradients are established by an intrinsic
oil property (Fig. 1), not by some idiosyncrasy of a
particular crude oil. In all these cases, the GOR is low,
so Eq. 1 applies with use of the cluster for the
asphaltene particle size. These heavy oil gradients are
fundamentally different than the nanoaggregate
gradients shown in Figures 5 & 6. Thus, the validity of
the Yen-Mullins model is reinforced numerous times.

Molecule

Nanoaggregate

Cluster

2~3 nm

4~6 nm

~1.5 nm

x00

Nanoaggregates
& Clusters

TVD
meters
x50

x00

Only
Nanoaggregates
x50
0.0

0.5

1.0

1.5

2.0

2.5

3.0

DFA OD at 1070 nm

Asphaltene Content

Fig. 9. A black oil that had been subjected to a late gas

and condensate charge. Modest asphaltene instability
resulted yielding some cluster formation in this black
oil.[23]
Geochemical analysis showed that the oil column in
Fig. 9 had been subjected to some gas and condensate
charging. This addition of light alkane resulted in some
modest asphaltene instability leading to cluster
formation from nanoaggregates.[23] The clusters
naturally accumulated much more towards the base of
the oil column. The point is that the asphaltene
concentration alone is not sufficient to determine
whether nanoaggregates, clusters or some mixture
prevails. The liquid phase properties of the crude oil are
an equally important factor.

Fig. 8 Mobile heavy oil, deepwater Gulf of Mexico

(from ref. [20], Fig. 5.) The gradient in this column is
almost identical to that in Fig. 7. Consequently fitting
with Eq. 1 gives a similar asphaltene cluster size.
Nanoaggregates or Clusters? A question arises as to
when a crude oil is expected to have nanoaggregates
and when it should have clusters. An oil column in
Canada helps establish that complexities can be
observed. A particular Canadian oil column was
observed to have both nanoaggregates and clusters.[23]

For example, laboratory measurements demonstrating

the transition from nanoaggregate to cluster dispersion
of asphaltenes in toluene (we call this the critical cluster
concentration) is approximately 2 to 5 grams of
asphaltenes per liter of toluene. Figure 10 clearly shows
this transition as determined by flocculation
kinetics.[24]

CCC

SPWLA 53rd Annual Logging Symposium, June 16-20, 2012

chemistry is very important in solubility. In addition, it

is plausible that the heaviest resins might play in
stabilizing the asphaltenes in crude oil.[29,30]
Asphaltene-resin interaction has been postulated for
over half a century. Some association was found
between asphaltenes and heavy resins in live black oil
centrifugation studies.[29]. Asphaltene stability is
impacted by the presence of resins.[30] Moreover, there
is no question that bulk solvency properties of the
solution impact asphaltene solubility. Thus, there
should be some dependence on the SARA fractions in
addition to asphaltene concentration for the critical
clustering concentration. This is in concert with the
significant difference of the concentration of CCC
between toluene versus crude oils.

Fig. 10 The aggregation number N as a function of

the scaled time *. Flocculation data for the addition of
n-heptane to different asphaltene/toluene solutions.
Orange circles represent data for a 10 g/L
asphaltene/toluene solution that exhibits reactionlimited aggregation (RLA). Blue squares represent data
for a 1 g/L asphaltene/toluene solution that exhibits
diffusion-limited aggregation (DLA). Red circles
represent data for a 5 g/L asphaltene/toluene solution
that exhibits crossover aggregation kinetics.[24]

At this juncture, a rough guideline is that the critical

cluster concentration in crude oils is roughly 10% mass
fraction but could vary substantially (eg 50% relative)
dependent on 1) the saturate, aromatic and resin
fractions 2) GOR and 3) whether the reservoir crude oil
had undergone mixing with light alkanes. The could
also be a temperature dependence. The clear
recommendation is to make DFA measurements to CCC
determine the asphaltene and GOR profiles vertically
and laterally in the reservoir in order to determine the
asphaltene colloidal dispersion. These gradients
establish the relevant fluid models, which in turn are
used to understand production concerns.

Figure 10 shows data acquired for different

asphaltene/toluene solutions. Upon n-heptane addition
to these solutions, asphaltenes were destabilized and
flocculated and the flocculation kinetics were
determined. Diffusion limited aggregation (DLA)
applies for floc formation from nanoaggregate
solutions; the nanoaggregates stick to each other upon
contact. Reaction limited aggregation (RLA) applies for
flocs formed from clusters. The fractal clusters need
morphological change at the interface in order to stick;
this mimics RLA.[25] Figure 10 finds the transition
from nanoaggregate to cluster at 5 g/liter in toluene.
Other studies obtain similar or slightly smaller critical
cluster concentrations.[26] The size of clusters has been
determined by various methods in addition to the field
studies shown in Figs. 7 & 8. DC-conductivity obtains
aggregation numbers less than 10.[26] Integrated small
angle x-ray scattering and small angle neutron
scattering studies also yield nanoaggregates and clusters
with similar aggregation numbers as in Fig. 1.[27,28]

Tar Mats. The treatment of asphaltenes in this paper is

within standard physical chemistry precepts. In addition
to finding similarities of crude oil columns around the
world, this formalism also treats tar mats and
corresponding oil columns within a single formalism.
Two distinct types of tar mats have been found. One
occurs at the base of a mobile heavy oil column and
represents a continuous extension of large asphaltene
gradients in the oil column, details will be discussed
elsewhere.[22] Essentially, if one were to extend
downward the asphaltene gradient present in Fig. 7, the
asphaltene content would increase to very high values
and the corresponding hydrocarbon would be immobile.
Again, this has been observed.[22]

The conclusion is that the nanoaggregate-cluster

transition occurs at ~0.5 mass% asphaltene in toluene
whereas in black crude oils such as in the Tahiti
reservoir, nanoaggregates prevail even at several
mass% asphaltene. It is no surprise that the solution

The second type of tar mat occurs at the base of a

relatively light oil column. This tar mat represents a
discontinuous increase of asphaltene content in going
from oil to tar.

SPWLA 53rd Annual Logging Symposium, June 16-20, 2012

It is now evident that treating only the gases and liquids

of reservoir fluids while ignoring the solids cannot
achieve broad scale understanding. Now that
asphaltenes are properly treated specifically with the
Flory-Huggins-Zuo EoS explicitly incorporating the
Yen-Mullins model of asphaltenes, a wide array of
reservoir concerns are being addressed in new and
exciting ways. This theoretical formalism with
specified asphaltene nanoscience falls within the
purview of standard physical chemistry, which itself is
extremely powerful. From that perspective, it is not
surprising that many enigmatic reservoir complexities
are rapidly becoming resolved in fairly simple
constructs. Understanding reservoir complexities
translates to reducing risk and cost in oil production.
Indeed, the recommendation follows that this formalism
should be utilized for virtually any reservoir fluid
complexity that is encountered. Unexpected success in
these endeavors is becoming the norm.

Fig. 11. Core sections in the oil zone (upper) and tar
zone (lower) under both visible and UV
illumination.[31] The core shows a fairly light crude oil
with brown color in the visible and bright yellowish
fluorescence. The tar zone is black under all
illumination.

REFERENCES SECTION
[1] O.C. Mullins, B. Martinez-Haya, A.G. Marshall,
Contrasting perspective on asphaltene molecular
weight; this Comment vs. the Overview of A.A. Herod,
K.D. Bartle, R. Kandiyoti, Energy & Fuels, 22, 17651773, (2008)

Figure 11 shows what happens when significant gas

charges into a reservoir containing black oil. As is
generally the case, the gas charges along the top of the
reservoir, then diffuses down into the oil column. As
the solution gas increases, asphaltene is expelled and
migrates lower in the oil column. If methane diffusion
continues over sufficient time, then the solution gas is
elevated even at the base of the oil column. This leads
to the observation in Fig. 11, the asphaltene can no
longer migrate downwards at the base of the column, so
it undergoes phase separation forming a tar mat.[31]
This process is tractable from a 1st principles approach
relying on the Yen-Mullins model and the FloryHuggins-Zuo EoS. Many oil columns have been
examined in this manner with successful accounting of
oil gradients in both equilibrium and disequilibrium
columns.[32]

[2] O.C. Mullins, E.Y. Sheu, A. Hammami, A.G.

Marshall, (Editors), Asphaltenes, Heavy Oils and
Petroleomics, Springer, New York, (2007)
[3] O.C. Mullins, The Asphaltenes, Annual Review of
Analytical Chemistry, 4, 393418, (2011)
[4] O.C. Mullins, The Modified Yen Model, Energy &
Fuels, 24, 21792207, (2010)
[5] H. Sabbah, A.L. Morrow, A.E. Pomerantz, R.N.
Zare, Evidence for Island Structures as the Dominant
Architecture of Asphaltenes, Energy & Fuels, 15971604, (2011)

CONCLUSIONS
[6] O.C. Mullins, H. Sabbah, J. Eyssautier, A.E.
Pomerantz, L. Barr, A.B. Andrews, Y. Ruiz-Morales,
F. Mostowfi, R. McFarlane, L. Goual, R. Lepkowicz, T.
Cooper, J. Orbulescu, R.M. Leblanc, J. Edwards, R.N.
Zare, Advances in Asphaltene Science and the YenMullins Model, accepted, Energy & Fuels

After a lengthy period of inexorable advance,

asphaltene science has undergone a renaissance in
recent years. This new science is being linked with the
new technology Downhole Fluid Analysis to address
long standing formerly unsolved reservoir complexities.

CCC

SPWLA 53rd Annual Logging Symposium, June 16-20, 2012

[7] J.Y. Zuo, H. Elshahawi, C. Dong, A.S. Latifzai, D.,

Zhang, O.C. Mullins, DFA Assessment of Connectivity
for Active Gas Charging Reservoirs Using DFA
Asphaltene Gradients, SPE #145438, ATCE, (2011)

[16] M.D. Lobato, J.M. Pedrosa, D. Mobius, S. Lago,

Optical characterization of asphaltenes at the air-water
interface. Langmuir 25, 137784, (2009)
[17] T. Pfeiffer, Z. Reza, D.S. Schechter, W.D.
McCain, O.C. Mullins, Fluid Composition Equilibrium;
a Proxy for Reservoir Connectivity, SPE Offshore
Europe Oil and Gas Conference and Exhibition held in
Aberdeen, UK, (2011)

[8] H. Elshahawi, R. Shyamalan, J.Y. Zuo, C. Dong,

O.C. Mullins, D. Zhang, Y. Ruiz-Morales, Advanced
Reservoir Evaluation Using Downhole Fluid Analysis
and Asphaltene Flory-Huggins-Zuo Equation of State,
Cartagena, Colombia, SPWLA, (2012)

[18] C. Dong, D. Petro, A. Latifzai, J.Y. Zuo, D.

Pomerantz, O.C. Mullins, Ron S. Hayden, Reservoir
Characterization of from Analysis of Reservoir Fluid
Property and Asphaltene Equation of State, Cartagena,
Colombia, SPWLA, (2012)

[9] D. Freed, O.C. Mullins, J. Zuo, Asphaltene

gradients in the presence of GOR gradients, Energy &
Fuels, 24 (7), pp. 3942-3949, (2010)
[10] J.Y. Zuo, D. Freed, O.C. Mullins, D. Zhang, A.
Gisolf, Interpretation of DFA Color Gradients in Oil
Columns Using the Flory-Huggins Solubility Model,
SPE 130305, Int. Oil & Gas Conf. Beijing, China, June
(2010)

[19] W. Pastor, G. Garcia, J.Y. Zuo, R. Hulme, X.

Goddyn, O.C. Mullins, Measurement and EoS
Modeling of Large Compositional Gradients in Heavy
Oils, Cartagena, Colombia, SPWLA, (2012)

[11] O.C. Mullins, D.E. Freed, J.Y. Zuo, H Elshahawi,

M.E. Cribbs, V.K. Mishra, A. Gisolf, Downhole Fluid
Analysis coupled with Asphalene Nanoscience for
Reservoir Evaluation, Presented in Perth, Australia,
SPWLA, (2010)

[20] N. R. Nagarajan, Reservoir Fluid Sampling of a

Wide Spectrum of Fluid Types Under Different CCC
Conditions: Issues, Challenges, and Solutions, IPTC,
14360, Bangkok, Thailand, 1517 November (2011)
[21] A. Tsiklakov, P. Weinheber, W. Wichers, S.
Zimin, A. Driller, R. Oshmarin, The Characterization of
Heavy Oil Reservoirs Using Downhole Fluid Analysis
to Determine Fluid Type and Reservoir Connectivity,
SPE 150697, Heavy Oil Conference & Exhibition,
Kuwait, (2011)

[12] S.S. Betancourt, F.X. Dubost, O.C. Mullins, M.E.

Cribbs, J.L. Creek, S.G. Mathews, Predicting
Downhole Fluid Analysis Logs to Investigate Reservoir
Connectivity, SPE IPTC 11488, Dubai, UAE, (2007)
[13] O.C. Mullins, The Physics of Reservoir Fluids;
Discovery through Downhole Fluid Analysis,
Schlumberger Press, (2008). The Spanish language
version of this book will be released at the SPWLA
meeting in Cartagena.

[22] D.J. Seifert, M. Zeybek, C. Dong, J.Y. Zuo, O.C.

Mullins, Black Oil, Heavy Oil and Tar In One Oil
Column
Understood
By
Simple
Asphaltene
Nanoscience, submitted ADIPEC 2012

[14] A.B. Andrews, A. McClelland, O. Korkeila, A.

Krummel, O.C. Mullins, A. Demidov, Z. Chen, Sum
frequency generation studies of Langmuir films of
complex surfactants and asphaltenes, Langmuir, 27,
6049-6058, (2011)

[23] V. Mishra, N. Hammou, C. Skinner, D.

MacDonald, E. Lehne, J. Wu, J.Y. Zuo, C. Dong, O.C.
Mullins, Downhole Fluid Analysis & Asphaltene
Nanoscience coupled with VIT for Risk Reduction in
Black Oil Production, SPE ATCE, accepted (2012)

[15] J. Orbulescu, O.C. Mullins, R.M. Leblanc, Surface

chemistry and spectroscopy of UG8 asphaltene,
Langmuir film, Part 1, Langmuir, 26(19), 15257
15264, (2010)

[24] I.K. Yudin, M.A. Anisimov, Dynamic light

scattering monitoring of asphaltene aggregation in
crude oils and hydrocarbon solutions. See Ref. 2, pp.
43966, (2007)

SPWLA 53rd Annual Logging Symposium, June 16-20, 2012

[25] Private communication, Professor William W.

Mullins, (deceased), Carnegie-Mellon University

ABOUT THE AUTHORS

[26] L. Goual, M. Sedghi, H. Zeng, F. Mostowfi, R.

McFarlane, O.C. Mullins, On the Formation and
Properties of Asphaltene Nanoaggregates and Cluster
by DC-Conductivity and Centrifugation, Fuel, 90,
2480-2490, (2011)

Dr. Oliver C. Mullins is the primary

originator of Downhole Fluid Analysis for formation
evaluation. For this, he has won several awards
including the SPE Distinguished Membership Award,
the SPWLA Distinguished Technical Achievement
Award and Distinguished Lecture three times for the
SPWLA and SPE. He authored the award winning book
The Physics of Reservoir Fluids; Discovery through
Downhole Fluid Analysis. He has co-edited 3 books
and coauthored 9 chapters on asphaltenes. He has
coauthored ~180 publications with ~2900 literature
citations. He has coinvented 77 allowed US patents. He
is Fellow of two professional societies and is Adjunct
Professor of Petroleum Engineering at Texas A&M
University.

[27] J. Eyssautier, P. Levitz, D. Espinat, J. Jestin, J.

Gummel, I. Grillo, L. Barr, Insight into Asphaltene
Nanoaggregate Structure Inferred by SAXS and SANS,
J. Phys. Chem. B, 115, 68276837, (2011)
[28] J. Eyssautier et al., Mesoscale Organization in a
Physically Separated Vacuum Residue- Comparison to
Asphaltenes in a Simple Solvent, Energy & Fuels,
2012, in press
[29] K. Indo, J. Ratulowski, B. Dindoruk, J.Gao, J.Y.
Zuo, O.C. Mullins, Asphaltene Nanoaggregates
Measured in a Live Crude Oil by Centrifugation,
Energy & Fuels, 23, 44604469, (2009)
[30] Dr. Irv Weihe, Private communication
[31] H. Elshahawi, A.S. Latifzai, Dong, J.Y. Zuo, O.C.
Mullins, Understanding Reservoir Architecture Using
Downhole Fluid Analysis and Asphaltene Science,
Presented, Colorado Springs, SPWLA, Ann., Symp.,
(2011)

Dr. Julian Youxiang Zuo is currently a

scientific advisor in reservoir engineering at
Schlumberger-DBR Technology Center. He has been
working in the oil and gas industry since 1989.
Recently, he has been leading the effort to develop and
apply the industrys first simple Flory-Huggins-Zuo
equation of state (EOS) for predicting compositional
and asphaltene gradients to address a variety of major
oilfield concerns such as reservoir connectivity, tar mat
formation, asphaltene instability, flow assurance,
nonequilibrium with late gas charging, etc. He has
authored and coauthored more than 130 technical
papers in peer-reviewed journals, conferences and
workshops. Dr. Zuo holds a Ph.D. degree in chemical
engineering from the China University of Petroleum in
Beijing.

[32] J.Y. Zuo, H. Elshahawi, C. Dong, A.S. Latifzai,

D., Zhang, O.C. Mullins, DFA Assessment of
Connectivity for Active Gas Charging Reservoirs Using
DFA Asphaltene Gradients, SPE 145438, ATCE,
(2011)

10

CCC

SPWLA 53rd Annual Logging Symposium, June 16-20, 2012

Dr. Chengli Dong is a Senior Fluid

Specialist with Shell International E&P, and previously
he was Senior Reservoir Domain Champion with
Schlumberger. He has been a key contributor on the
development of downhole fluid analysis. He conducted
extensive spectroscopic studies on live crude oils and
gases, and he led the development of interpretation
algorithms on the downhole fluid analysis tools. In
addition, Dr. Dong has extensive experience on design
and interpretation of formation testing logs as well as
their applications on reservoir characterization. He has
published more than 50 technical papers, and he coinvented 15 granted US patents, eight patent
applications and one trade secret award. He holds a BS
degree in chemistry from Beijing University, and PhD
in petroleum engineering from the University of Texas
at Austin.

Hani Elshahawi is Shell

Deepwater Technology Advisor. Previously, he led
FEAST, Shells Fluid Evaluation and Sampling
Technologies centre of excellence and before that spent
15 years in Schlumberger in over 10 countries in
Africa, Asia, and North America during which he has
held various positions in interpretation, consulting,
operations,
marketing,
and
technology
development. He holds several patents and has
authored close to a hundred technical papers in various
areas
of
petroleum
engineering
and
the
geosciences. He was the 2009-2010 president of the
SPWLA and was distinguished lecturer for the SPE and
the SPWLA 2010-2011 and is recipient of 2012
SPWLA Distinguished Technical Achievement Award.

CCC

Thomas Pfeiffer is a Senior

Reservoir Domain Champion for Schlumberger
Wireline in Stavanger. As a subject matter expert
Thomas provides technical support to wireline
formation testing services and integrates the acquired
data in reservoir engineering workflows. He coauthored 7 publications on downhole fluid analysis and
coinvented one US patent application. Thomas received
his B.S. in electrical engineering in 1996 and his M.S.
in electrical engineering in 2001 from the Technical
University of Munich, Germany. He joined
Schlumberger as a wireline field engineer in January
2002. Assigned locations include the North Sea, central
and eastern Europe and the Gulf of Mexico. In August
2009 Schlumberger sponsored his education at Texas
A&M. He received his Masters of Science in December
2010.

Dr. A. Ballard Andrews is a

principal scientist at Schlumberger-Doll research. He
spent nearly a decade working at the National
Synchrotron Light Source at Brookhaven National Lab
where he completed his PhD in Condensed Matter
Physics with the University of Texas at Austin and
pursued post-doctoral research with Bell Labs and Los
Alamos National Lab. Dr. Andrews has published over
50 articles in peer reviewed physics, chemistry and
energy journals. He has a total of 16 patents granted or
filed, and has presented at over 35 external international
conferences. He co-authored a chapter in the Handbook
of Physics and Chemistry of the Rare Earths. He also
worked for many years on computational scientific
visualization, and his work appeared in Scientific
American and Nature. Dr. Andrews is an expert on
laboratory and downhole optical fluorescence
measurements. His latest interests focus on improved
optical techniques for downhole fluid and gas
composition analysis.

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SPWLA 53rd Annual Logging Symposium, June 16-20, 2012

M. E. (Bo) Cribbs has 31 years

of Reservoir and Production Engineering experience
working for Chevron. His expertise is in general
Reservoir Engineering with emphasis in deep water
evaluations, well logging, well testing and fluid
sampling. Bos assignments have spanned the Middle
East, the Gulf of Mexico, Offshore West Africa, Offshore
Canada and Offshore Brazil. His current assignment is to
Chevrons Deepwater Gulf of Mexico Appraisal Team
working on Deep Water Exploration and Appraisal data
evaluation programs. Bo is a member of SPE, AAPG and
SPWLA and serves as an SPE Technical Editor.

CCC
Dr. Andrew E. Pomerantz is
the Geochemistry Program Manager at SchlumbergerDoll Research. His research focuses on the
development of novel techniques to characterize the
chemical composition of kerogen and asphaltenes,
including methods in mass spectrometry and X-ray
spectroscopy. That molecular information is used to
understand fundamental physical and chemical
processes in petroleum such as asphaltene
compositional grading. He graduated from Stanford
University with a PhD in chemistry in 2005 and has coauthored 30 peer-reviewed publications.

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