Energy & Fuels 2001, 15, 979-986 979

Asphaltene Precipitation from Live Crude Oil

Nikhil B. Joshi,† Oliver C. Mullins,*,‡ Abul Jamaluddin,† Jefferson Creek,§ and
Jim McFadden|
Oilphase, 2315 Schlumberger St., Houston, Texas 77023, Schlumberger-Doll Research,
Old Quarry Road, Ridgefield, Connecticut 06877, Chevron Petroleum Technology Corporation,
2811 Hayes Road, Houston, Texas 77082, and BHP Petroleum Americas Inc.,
1360 Post Oak Blvd., Houston, Texas 77056

Received February 27, 2001. Revised Manuscript Received April 23, 2001

Asphaltene precipitation from live crude oils that occurs due to pressure reduction can foul
and clog oil production equipment, at the well surface, in the borehole, and even in the subsurface
Downloaded via INDIAN INST OF TECHNOLOGY BOMBAY on August 27, 2019 at 16:59:08 (UTC).

formation, thus is of considerable interest to oil operating companies. We employ near-infrared

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(NIR) spectroscopy to characterize this asphaltene precipitation process; in particular, the

independent measurements on asphaltene flocculation of wavelength dependence of optical
scattering and of sedimentation rates are performed. Here, it is established that different
asphaltene flocs form during depressurization of crude oil. Furthermore, the initial precipitate
is probably not problematic in the production of crude oil, relaxing constraints imposed by
asphaltene considerations. Additionally, the asphaltene precipitation process is shown to be largely
reversible in the minutes time frame, but subtle irreversibilities are suggested. Compressibility
is measured using NIR techniques to validate our methods. Optical spectroscopy on optically
thin samples is found to be a powerful and indispensable tool to characterize asphaltene
precipitation.

I. Introduction laboratory definition is that they are insoluble in

Naturally occurring hydrocarbon fluids range from
dry natural gas to tar; the planning and optimization
of the production of hydrocarbon resources depends
critically on hydrocarbon type. Of special concern in
hydrocarbon production is a phase change. For instance,
crude oils at reservoir temperatures and pressures
contain significant quantities of methane and other light
components, which evolve as a separate gas phase at
reduced pressures. Consequently, proper pressure con-
trol needs to be maintained to obtain the desired
multiphase flow. (A crude oil that possesses all chemical
components including light ends in proper amounts as
found in the subsurface formation is termed a live crude
oil.)
Another phase change of great consequence in oil
production is asphaltene precipitation, which occurs in
some, although by no means all crude oils. Asphaltenes
are present in crude oils in the range of 0% to 10% or
more and have a dramatic effect on chemical and
physical properties of the crude oil. Asphaltenes1-4 are
defined according to their solubility; one standard
* Corresponding Author.
† Oilphase.
‡ Schlumberger-Doll Research.
§ Chevron Petroleum Technology Company.
| BHP Petroleum.
(1) Bitumens, Asphalts and Tar Sands; Chilingarian, G. V., Yen, T.
F., Eds.; Elsevier Scientific Pub. Co.: New York, 1978.
(2) Chemistry of Asphaltenes; Bunger, J. W., Li, N. C., Eds.; Am.
Chem Soc.: Washington, DC, 1981.
(3) Asphaltene, Fundamentals and Applications; Sheu, E. Y., Mul-
lins, O. C., Eds.; Plenum Press: New York, 1995.
(4) Structures and Dynamics of Asphaltenes; Mullins, O. C., Sheu,
E. Y., Eds.; Plenum Press: New York, 1998.
n-heptane (or some other light alkane) and soluble in
toluene. We will call this a “lab” asphaltene. This defi-
nition is useful in that it captures the most aromatic
component of crude oil. Clearly, with this operational
definition, the asphaltene fraction will constitute a
range of molecular identities. Adding to complexity, the
oil field definition of asphaltene is different; asphaltenes
are the material that precipitates from live crude oil
resulting from depressurization. We will call this a
“field” asphaltene. Finally, other carbonaceous source
materials such as coal may be used with the laboratory
definition to derive an asphaltene fraction. For coals,
asphaltenes are not the most aromatic component;
nevertheless, coal asphaltenes are interesting in their
own right5 and have been used to contrast petroleum
asphaltenes in uncovering chemical and physical prop-
erties.
Lab asphaltenes are a friable, infusible fraction of
crude oil, the most aromatic fraction of crude oil,
possessing a C:H atomic ratio of ∼1:1.1. Asphaltene
molecular weight has been controversial for 20 years
but appears to be largely resolved;6-9 petroleum as-
phaltene molecular weight is predominantly in the
range 500 amu to 1000 amu, with some modest varia-
(5) Iino, M.; Takanohashi, T. Structures and Dynamics of Asphalt-
enes; Mullins, O. C., Sheu, E. Y., Eds.; Plenum Press: New York, 1998;
Chapter 6.
(6) Boduszynski, M. W. Chemistry of Asphaltenes; Bunger, J. W.,
Li, N. C., Eds.; Am. Chem Soc.: Washington, DC, 1981; Chapter 7.
(7) Miller, J. T.; Fisher, R. B.; Thiyagarajan, P.; Winans, R. E.; Hunt,
J. E. Energy Fuels 1998, 12, 1290.
(8) Groenzin, H.; Mullins, O. C. J. Phys. Chem., A 1999, 103, 11237.
(9) Groenzin, H.; Mullins, O. C. Energy Fuels 2000, 14, 677.

10.1021/ef010047l CCC: $20.00 © 2001 American Chemical Society

Published on Web 06/06/2001
980 Energy & Fuels, Vol. 15, No. 4, 2001
tion depending on the source petroleum.9 Individual
asphaltene molecules consist of a single aromatic core
with 4-10 fused aromatic rings, with peripheral alkyl
substituents.4,7-9 Asphaltenes are enriched in hetero-
atoms, typically a few mass %. All of the nitrogen is
aromatic, pyrroles and pyridines;10 the sulfur is present
both in sulfides and thiophenes11,12 and small amounts
of sulfoxide;12 and oxygen is present (in addition to
sulfoxide) in phenols, carbonyls, and carboxylic acids.1-4
Asphaltenes are suspended as a microcolloid in crude
oil in ∼3 nm particles, stable for geologic time.1-4 Each
colloidal particle, termed a micelle, consists of one (or
perhaps multiple) “stack of pancakes” of the aromatic
sheets of separate molecules, along with associated
resins and is termed the Yen model.1-4 The resins are
thought to act as surfactants to stabilize the colloidal
suspension. Resins are the next heaviest fraction in
crude oils and compared to asphaltenes are of somewhat
lower molecular weight with smaller numbers of rings
contained in their fused ring systems.1-4 Whereas
asphaltenes are powdery, resins are tacky; this distinc-
tion is of critical importance when considering practical
matters in oil production. Both asphaltenes and resins
are known to be interfacially active for certain systems.1-4
It is important to note that this “micelle” picture has
yet to be confirmed and that other descriptions exist.13
For instance, it is not known whether the resins exist
in the “micelle” toward the exterior only as the term
micelle would imply, or are infused throughout the
asphaltene colloidal particle. Thus, caution is in order
when using the micelle picture. We think aspects of this
micelle description merit its consideration as a working
model for asphaltenes in crude oil; we hope its use
stimulates others in the field explore this model further.
Part of the interest in asphaltenes is due to their
impact on oil production. With a pressure reduction the
microcolloid can become destabilized leading to field
ashaltene precipitation. Comingling oil production from
two separate zones or wells in the oil field can also result
in precipitation of asphaltene. Only a small mass
fraction of (lab) asphaltene present in a crude oil
actually precipitates from a crude oil with pressure
reduction. Nevertheless, even a very small mass fraction
of a 10 000 barrel per day production can cause huge
deposits, for example in production tubing, which can
shut down oil production. The field asphaltene precipi-
tate can be tacky and adhere in thick deposits to
available surfaces.
Crude oils that are susceptible to pressure-induced
asphaltene precipitation are generally highly under-
saturated; that is, the subsurface formation pressure
is much higher than the bubble point; thus, the crude
oil can experience a large pressure drop without evolv-
ing gas. Once gas evolves, the light alkane fraction of
the liquid phase is reduced increasing its solvating
power, thereby stabilizing asphaltenes. In addition,
crude oils that have a few percent of asphaltene tend
(10) Mitra-Kirtley, S.; Mullins, O. C.; Chen, J.; van Elp, J.; George,
S. J.; Cramer, S. P. J. Am. Chem. Soc. 1993, 115, 252.
(11) George, G. N.; Gorbaty, M. L. J. Am. Chem. Soc. 1989, 111,
3182.
(12) Waldo, G. S.; Mullins, O. C.; Penner-Hahn, J. E.; Cramer, S.
P. Fuel 1992, 71, 53.
(13) Cimino, R.; Correra, S.; Del Bianco, A.; Lockhart, T. P. As-
phaltene, Fundamentals and Applications; Sheu, E. Y., Mullins, O. C.,
Eds.; Plenum Press: New York, 1995; Chapter 3.
Joshi et al.
to be rather compressible, thus can suffer a significant
drop of dielectric constant with a pressure decrease
reducing solvating power.14 The precipitation induced
with pressure reduction is a continuous process. The
asphaltene precipitation onset pressure demarcates the
first “appearance” of asphaltene flocs. Subsequent pres-
sure reduction is associated with a further reduction of
solvating power of the crude oil and additional material
precipitates. Because asphaltenes are already present
in crude oils as a colloidal suspension, the measured
asphaltene precipitation onset pressure will likely be a
function of how hard one looks for evidence of colloidal
particle aggregation. Furthermore, the solvating power
of the crude oil is continuously changing with pressure
reduction, one expects that the physical and chemical
properties of the asphaltene precipitate should also
change continuously, perhaps in subtle but important
ways.
Asphaltenes and resins are associated in crude oils
and exhibit complex aggregation and flocculation phe-
nomena. The polydispersity of this heavy end mixture
in part generates this complex behavior. In addition,
even isolated asphaltenes exhibit similar complex mi-
cellization, aggregation, and flocculation phenomena.
For instance, by varying the solvation power of the
solvent system, this complex behavior of asphaltenes
can be elucidated.14-16 The polydispersity within the
asphaltene fraction in part generates their complex
aggregation behavior. Essentially, the heavy end popu-
lation of crude oils represents a continuum of chemical
structures, not discrete structures as the terminology
might incorrectly imply.
Of particular interest in the oil field is the pressure
at which asphalt precipitation hinders oil production.
If asphaltene precipitation produces particles that do
not form deposits, that is, presumably, if the asphaltene
particles are not tacky, then they are not of great
concern. Furthermore, if the asphaltene particles are
small compared to diameters of flow paths (either in the
formation or in the well), then this precipitation is not
a concern and the corresponding larger pressure drop
can be utilized. Of course, larger pressure reductions
are desirable to maximize oil flow rates. Standard
laboratory analysis of asphaltene precipitation from live
crude oils consists of measuring optical scattering in an
optically thick sample at a fixed wavelength.17 This
technique was recently used to establish that field
asphaltene precipitation is (largely) reversible.17 This
provides useful information particularly as to whether
the crude oil produces any asphaltene precipitation at
all. However, for analysis of characteristics, it is far
better to analyze the scattering spectrum over a range
of wavelengths. For instance, analysis of single wave-
length data is often performed without the use of any
equations.17 In addition, it is desirable to use an
optically thin sample in order to perform quantitative
analysis. Finally, a small sample is desirable thereby
(14) Buckley, J. S.; Hirasaki, G. J.; Liu, Y.; Von Drasek, S.; Wang,
J. X.; Gill, B. S. Pet. Sci. Technol. 1998, 16, 251.
(15) Anisimov, M. A.; Yudin, I. K.; Nikitin, V.; Nikolaenko, G.;
Chernoustan, A.; Toulhoat, H.; Frot, D.; Briolant, Y. J. Phys. Chem.
1995, 99, 9576.
(16) Anderson, S. I. Fuel Sci. Technol. Int. 1994, 12, 51.
(17) Hammami, A.; Phelps, C. H.; Monger-McClure, T.; Little, T.
M. Energy Fuels 2000, 14, 14.
Asphaltene Precipitation from Live Crude Oil
allowing sedimentation rates to be measured and quan-
titatively analyzed.
In this Paper, we study the characteristics of the
asphaltene precipitate utilizing optical scattering tech-
niques as well as sedimentation rates. These indepen-
dent measurements produce similar results lending
credence to our findings. Near the asphaltene precipita-
tion onset pressure, flocs are found to remain small and
should not be problematic. With a further reduction of
pressure of 2000 psi, the flocs are found to grow large
and are likely to be very problematic in oil production
due to a suspected change in composition. It is shown
that production and resuspension of the large flocs is
reversible in the minutes time frame. There is a sug-
gestion that the initial production of smaller flocs
exhibits some irreversibility. A range of precipitate
properties is found in interim pressures. Live oil com-
pressibility was also measured to validate NIR tech-
niques. Optical spectroscopy is found to be an indispen-
sable method of analysis of asphaltene precipitation.
II. Experimental Section
A ∼200 cm3 sample of live crude oil was obtained from
Chevron. This crude oil is known to precipitate asphaltene
with pressure reduction, thus the best field practices were
required for valid sample collection and preservation. An
MDT31 (Modular Formation Dynamics Tester) was utilized for
sample collection in an openhole (uncased) producing well
section. Flowline contents within the MDT were monitored
using the OFA31 (Optical Fluid Analyzer), a visible-NIR
spectrometer, to guarantee collection of a representative
sample.18An Oilphase Single-Phase Sample bottle was utilized
to maintain formation pressure (or greater) on the sample at
all times prior to our laboratory analysis of the live crude oil.18
Asphaltene reversibility reported here and elsewhere notwith-
standing, we found that collection of a sample of this crude
oil in a bottle without pressure preservation resulted in a
sample which could not be reconstituted properly, and pro-
duced no asphaltene precipitation. Sample transfer was ac-
complished by transferring a 50 cm3 volume of the original
Chevron sample to a second high-pressure vessel with a
minimum of dead volume. This second sample bottle was then
connected to our high-pressure cell via 1 mm ID transfer lines.
The high-pressure cell was placed in a Precision Scientific
Oven (Model #31617) for temperature control. A volume of ∼15
cm3 was purged to void nonrepresentative sample which
flashed in the 2 cm3 dead volume of our cell plus transfer lines.
Replicate purges gave identical spectra. A series of experi-
mental runs were performed to validate results presented here
(until the sample was consumed). Pressure measurements
were performed with a Heise Model 901A 20 000 psi gauge
and temperature in the cell was determined using a thermo-
couple embedded in a narrow hole deep into the body of the
cell.
Prior to transfer or experimental use of the samples, the
samples were mechanically agitated for 1 h at reservoir
temperature and a pressure of ∼13 000 psi which is greater
than reservoir pressure. This precautionary restoration should
be unnecessary because the sample never experienced low
pressure, and the asphaltene never should have precipitated
prior to use of the sample. We found no evidence of asphaltene
precipitation in our single-phase sample. All sample transfers
and all experiments were performed at reservoir temperature,
75 °C.
Our high-pressure, high-temperature cell consists of an
optical path of 2 mm with an active optical measurement
(18) Crombie, A.; Halford, F.; Hashem, M.; McNeil, R.; Thomas, E.
C.; Melbourne, G.; Mullins, O. C. Oilfield Rev., Autumn, 1998.
Energy & Fuels, Vol. 15, No. 4, 2001 981
diameter of 5 mm established by the fiber optics. The fluid
height within the cell above the optical axis of interrogation
is approximately 1 cm which defines the length scale of
sedimentation. As described previously,19 this cell is connected
via fiber optics and our custom transfer optics to a research
grade Cary 5 UV-visible-NIR spectrometer. With the spec-
trometer settings we used, a spectral scan from 2500 to 800
nm takes about 4 min. This defines the minimum time frame
of our reversibility experiments on asphaltene precipitation.
The optical density of the all transfer optics and empty cell
were about 1.4 optical density (OD) units. We employed the
rear beam attenuator with 1.2 OD units to extend the linear
range in OD of the system. In addition, a standard DBR Jeffri
cell was used to measure the asphaltene precipitation onset
pressure as well to verify consistency in the asphaltene
precipitation onset pressure.
III. Theory
Light Scattering. The theory of optical scattering
(or more generally, electromagnetic wave scattering) is
a well developed field and is described in detail in many
references.20 Here we provide a very basic description
and list results relevant to this work. Optical scattering
can be divided into two distinct regimes, wavelength-
independent scattering and wavelength-dependent scat-
tering. Wavelength-independent scattering pertains
when the size of the scatterer is very large compared to
the wavelength of light. Wavelength-dependent scat-
tering pertains when the particle size is comparable or
much smaller than the wavelength of light. It is
instructive to consider the Rayleigh limit derived by
Lord Rayleigh in the late nineteenth century. For the
case of λ/2πn . r (the Rayleigh condition) where λ is
the wavelength of light and r the particle radius, n is
ratio of the discrete phase to continuous phase index of
refraction, then the scattering is purely dipolar (high-
order scattering moments are vanishing). For the Ray-
leigh condition, the scattering cross section efficiency
Qscat is given below, where Qscat is the Rayleigh cross
section divided by πr2, the geometric cross of the sphere.
Qscat is given by20
( )
27π2r4 n2 - 1 2
Qscat ) (1)
3λ4 n2 + 2
This well-known result, which accounts for the color of
the blue sky, shows that Qscat varies as (r/λ).4 This
equation accounts for the negligible optical scattering
of visible or NIR light of unaltered 3 nm asphaltene
colloidal particles in crude oil. Measurement of a (r/λ)4
dependence of scattering means that the Rayleigh
condition holds, λ/2πn . r. As the particle size ap-
proaches the wavelength of light, the scattering is still
wavelength dependent but with a smaller power than
4. For very small dielectric spheres, a closed form
expression is obtained for g, the power of (r/λ) in the
scattering efficiency.20
12(n2 - 2)R2
g)4+ (2)
5(n2 + 2) + 6(n2 - 2)R2
(19) Mullins, O. C.; Joshi, N. B.; Groenzin, H.; Daigle, T.; Crowell,
C.; Joseph, M. T.; Jamaluddin, A. Appl. Spectrosc. 2000, 54, 624.
(20) Kerker, M. The Scattering of Light and Other Electromagnetic
Radiation; Academic Press: New York, 1969.
982 Energy & Fuels, Vol. 15, No. 4, 2001 Joshi et al.

where

2πnr
R) (3)
λ
This equation is not applicable for R > 1 (which pertains
here) but is instructive to show the deviation from
Rayleigh scattering (g ) 4) as particle size grows. We
assume that there is no dispersion in the scattering
dependence on the size ratio over the wavelength range
used here.
Asphaltene flocculation is polydisperse; numerical
methods can be used to account for polydipersity within
a size range where with R ∼ 1.20,21 Reference 20 plots
the results for the power of the size ratio for different
mean sizes of particle distributions. For R < 10, the
primary effect of polydispersity is to smooth out scat-
tering resonances. For particles somewhat larger than
the wavelength of light, the dependence of light scat-
tering on wavelength is graphically provided in ref 20.
As R grows, the power of the size ratio goes to zero, but Figure 1. The spectrum of a live crude oil under reservoir
for further increases, the power actually goes negative. pressure and temperature conditions. The discrete vibrational
For particles in this intermediate range, the power of absorption bands and the continuous electronic absorption
band are evident. Two separate sample transfers give the same
the size ratio is double valued. For particles that are
spectrum validating the sample.
much bigger than then wavelength of light, the scat-
tering is independent of wavelength. Sedimentation. Sedimentation rate is a useful tool
We have presumed scattering from dielectric spheres in determining particle size. The rate of sedimentation
here. Although the index of refraction for asphaltenes is governed by the magnitude of buoyancy vs viscous
is complex, the absorption length in the NIR is rather drag; the latter is the product of particle velocity and
long and can be neglected for asphaltene particles that the viscous coefficient β which is given below:23
approach 1 µm in size. However, for 3 nm particles, the
scattering cross section drops to very low values and 6πηr
optical absorption dominates.22 β) (6)
m
Brownian Motion. In aqueous systems, colloidal
particles often remain suspended due to repulsion of like where η is the bulk viscosity. For low densities of
charges. With asphaltenes, the role of charge is not so particles where interparticle interaction is negligible,
clear, but most likely is of secondary importance. the equation which governs the rate of sedimentation
Brownian motion along with weak intermicellar bonding is24
is likely to play a predominant role, at least for
undisturbed crude oils. The relative importance of 2r2δFg
Brownian motion vs the tendency for sedimentation is
V) (7)
9η
given by the Boltzmann distribution, eq 4.23
where V is the sedimentation rate.
w(z) )
∆F mg
F kT
exp -z {
∆F mg
F kT } (4)
Results and Discussion
where z is the height above zero (defined by the Particle Size. Figure 1 shows the NIR spectrum of
container) F and ∆F are the bulk density and the density the Chevron live crude oil at a pressure of 13 600 psi
difference between the discrete phase and the bulk, and temperature of 75 °C. The spectra of two separate
respectively. m is the mass of the colloidal particle, g is purges are shown, the overlap of the spectra indicates
the standard acceleration, k is Boltzmann’s constant, T proper sample transfer. This sample is single phase; the
is temperature. The leading term is simply a normaliza- pressure is far above the asphaltene precipitation onset
tion constant. The mean value of height is obtained from pressure and thus also far above bubble point. The
eq 4 as23 visible-NIR spectral features have been described in
detail elsewhere;25,26 here we review basic features. The
kT F spectrum consists of a series of diminishing peaks with
〈z〉 ) (5)
mg ∆F decreasing wavelength coupled with a broad increasing
structureless absorption edge with decreasing wave-
eqs 4 and 5 provide the equilibrium distribution of length. The series of peaks correspond to vibrational
colloidal particles in a gravitational field but do not overtone and combination bands of the -CH2-, -CH3,
provide the rate at which equilibrium is achieved. For and CH4 groups: ∼2450 nm, the stretch+bend; ∼1725
this purpose, sedimentation rate must be considered.
(24) Holmes, H. N. Introductory Colloid Chemistry; John Wiley &
(21) Heller, W.; Tabibian, R. M. J. Phys. Chem. 1962, 66, 2059. Sons: New York, 1934.
(22) Mullins, O. C. Anal. Chem. 1990, 62, 508. (25) Henry, B. R. J. Chem. Phys. 1976, 80, 2160.
(23) Chandrasekhar, S. In Selected Papers on Noise and Stochastic (26) Mullins, O. C.; Daigle, T.; Crowell, C.; Groenzin, H.; Joshi, N.
Processes; Wax, N., Ed.; Dover Pub.: New York, 1954; Chapter 1. K. Appl. Spectrosc. 2001, 55, 197.
Asphaltene Precipitation from Live Crude Oil
Figure 2. The spectra of the live crude oil at 9000 psi, and a
time series of spectra of the crude oil at 8000 psi. The increase
in OD for the spectra at 8000 psi is due to scattering from
asphaltene precipitation. The scattering is wavelength de-
pendent and persists for long times.
nm the two-stretch; ∼1400 nm, the two-stretch+bend;
and 1190 nm, the three-stretch. The intensity of these
forbidden bands decreases with decreasing wavelength
because more vibrational quanta are excited with the
single photon.25 The shoulder at 1650 nm is due to
methane and is useful for the estimation of GOR.26
The broad increasing absorption with shorter wave-
length is due to the electronic absorption edge of the
largest aromatic ring systems.27,28 It has been shown
that this profile is not due to scattering of the asphalt-
ene colloidal suspension.22 Since the aromatic fraction
of crude oils varies, the location for this absorption edge
can occur in different spectral locations. For crude oils
containing asphaltenes, the absorption edge is in the
NIR. For light condensates, the absorption edge is in
the UV. Optical density (OD) is the sum of absorption
and scattering contributions; in addition to vibrational
and electronic absorption (where optical energy ab-
sorbed), particulates can induce optical scattering (where
the incident photon is redirected). It is the variation of
OD with optical light scattering due to asphaltene
flocculation which is of interest in this report.
Figure 2 shows the spectrum for the crude oil at a
pressure of 9000 psi, and in addition, shows a series of
spectra collected in a time sequence immediately after
the pressure was reduced from 9000 psi to 8000 psi. The
elevation of the OD at all wavelengths is evident for all
spectra at the lower pressure. This increase in OD is
due to the flocculation of asphaltenes that occurred with
the pressure reduction. The increase in OD at shorter
wavelengths is clearly greater than at longer wave-
lengths; thus, the particles that are causing the light
scattering are smaller than a wavelength. Furthermore,
the scattering is seen to persist for all spectra.
(27) Mullins, O. C.; Mitra-Kirtley, S.; Zhu, Y. Appl. Spectrosc. 1992,
46, 1405.
(28) Mullins, O. C. Structures and Dynamics of Asphaltenes; Mullins,
O. C., Sheu, E. Y., Eds.; Plenum Press: New York, 1998; Chapter 2.
Energy & Fuels, Vol. 15, No. 4, 2001 983
Figure 3. Plot of the scattering OD for 3 wavelengths for the
data plotted in Figure 2. The persistent, wavelength-dependent
scattering is evident.
Figure 3 plots the increase in OD corresponding to
Figure 2 for three wavelengths, 1100, 1600, and 2100
nm, where the increase in OD is particularly easy to
measure. The salient features of increased OD at shorter
wavelength and of long time persistence of this scat-
tering are clearly evident. There is a comparable
wavelength dependence of scattering at all times in
Figure 2. With these data, the power of wavelength is
determined to be ∼2. Assuming indices of refraction of
1.7 for asphaltenes14 and 1.38 for the live crude oil and
using graphical results from reference,20 R is found to
be 3.7 taking into account polydispersity.29 Using 2 µm
in eq 3 for the wavelength, one obtains the particle
radius to be ∼0.85 µm.
Figure 3 also shows that the rate of sedimentation is
slow. The maximum scattering is obtained in several
minutes to 10 min. At 100 min there is some evidence
of sedimentation. We can obtain an estimate of the
particle size using this rate of sedimentation. To use eq
7 we use the following estimated parameters: 140 min
as the time for the particles to settle to 1/e of the
maximum; the viscosity of the live oil at reservoir
conditions as 1 cp; the densities of asphaltene and the
live crude oil as 1 g/cm3 and 0.5 g/cm3, respectively. With
these values, one obtains the particle size to be 1.05 µm
from eq 7. This is quite close to the result obtained from
light scattering. The fact that two measurements that
rely on very different physics produce comparable
results for the particle size indicates robustness of the
measurement and analysis.
Figure 4 shows the scattering that results when the
pressure is reduced from 9000 psi to 6000 psi, a pressure
much lower than the onset pressure of 8000 psi. This
figure shows the scattering is large and is not strongly
dependent on wavelength. In addition, the scattering
is seen to decrease relatively rapidly with time. Figure
5 shows the ODs vs time for the spectra of Figure 4 at
three wavelengths. Some wavelength dependence is
evident in this figure indicating that the particles are
(29) Kerker, M. The Scattering of Light and Other Electromagnetic
Radiation; Academic Press: New York, 1969; Figure 7.16.
984 Energy & Fuels, Vol. 15, No. 4, 2001
Figure 4. The spectra of the live crude oil at 9000 psi, and a
time series of spectra of the crude oil at 6000 psi. The increase
in OD for the spectra at 6000 psi is due to scattering from
asphaltene precipitation. The scattering is largely wavelength
independent and rapidly diminishes.
Figure 5. Plot of the scattering OD for 3 wavelengths for the
data plotted in Figure 4. The scattering is largely wavelength
independent; rapid settling is evident.
not very much larger than the wavelength; nevertheless,
the wavelength dependence is much less than that seen
in Figure 3. In addition, sedimentation is much faster
for this precipitate than observed near the onset pres-
sure. The wavelength dependence of the light scattering
is comparable at all times in this figure; the power of
the wavelength is ∼0.2. Using the numerical calcula-
tions from reference 29, R is found to be ∼10. From eq
3 the particle size is 2.3 µm. Again, sedimentation rate
can be used to calculate particle size. The sedimentation
rate is 15 min for the scattering to drop to 1/e of its
maximum value. Using eq 7, the particle size is deter-
mined to be 3.2 µm. Again, we have good agreement
between the two very different measurements, light
scattering and sedimentation rate.
The initial flocs are a factor of ∼3 in radius (and ∼30
in volume) smaller than the flocs which form at lower
Joshi et al.
pressures. The large volume difference in the flocs
coupled with the large difference (2000 psi) in precipita-
tion pressures indicates that these flocs are different.
The sizes alone of flocs are not sufficient to impede the
flow of crude oil during production. However, if the flocs
are sticky, then big production problems can result. The
much larger volume of the flocs produced at lower
pressures suggests stronger binding in the floc. The
expectation is that these flocs contain more resin and
thus would be stickier.30 This must be investigated, but
the indication from our data is that different types of
flocs form at different pressures, and it is likely the
different flocs would impact crude oil production differ-
ently.
Eq 5 can be used to obtain the expectation value of
the height of asphaltene particles in the live crude oil
for different radii. For 1 micron, 〈z〉 , 1 cm meaning
the 1 µm particles will eventually settle. For the pristine
microcolloidal asphaltene suspension of particle size 3
nm, 〈z〉 ∼ 60 m. Some gravity settling of these particles
would thus be expected in large subsurface formations
especially if some aggregation takes place, for instance,
due to a light alkane charge to a reservoir containing
heavier oil.
In Figure 4, the spectrum at 9000 psi corresponds to
no asphaltene precipitation. The spectrum correspond-
ing to the longest delay time, 106 min, corresponds to
settling of almost all of the asphaltene precipitate out
of the filed of view, only a little scattering remains. It
is evident that there is almost no color change induced
by this asphaltene precipitation. It is known that the
removal of all (lab) asphaltene from a sample of crude
oil reduces the color significantly, by a factor of 2 in
some cases.22 Clearly little color change has occurred
as a result of the integrated asphaltene precipitation
from 8000 psi to 6000 psi. Consequently, it is evident
that this field asphaltene is a small fraction of the total
solvent induced or lab asphaltene contained in the
sample. Furthermore, the field asphaltene precipitate
consists partially of resin that produces the tackiness
creating problems in the oil field. The lab and field
asphaltenes are quite different materials.
Reversibility. We can determine the reversibility of
the asphaltene flocculation process by alternately col-
lecting spectra at high and low pressures. If the pressure
on the sample is reduced from 13 000 psi to 6000 psi
then increased back to 13 000 psi, within minutes of the
pressure drop, then the scattering is entirely eliminated.
In other words, the asphaltene flocs are deflocculated.
Figure 6 shows this in the following way: the spec-
trum corresponding to 13 000 psi exhibits no scattering
(dotted line). This figure also shows a spectrum im-
mediately after the pressure was reduced from 13 000
psi to 6000 psi (dashed line); significant scattering is
evident at all wavelengths. A spectral scan was then
initiated at 13 000 psi. (Spectral scans start at long
wavelength and end at short wavelength so time
proceeds right to left.) During this scan (solid line), the
pressure was decreased rapidly from 13 000 to 6000 psi;
this occurred when the wavelength was 1925 nm.
Immediately, asphaltene flocculation is observed, The
OD approaches and eventually reaches the OD of the
(30) Pan, H.; Firoozabadi, A. AIChE J. 2000, 46, 416.
(31) Trademark of Schlumberger.
Asphaltene Precipitation from Live Crude Oil
Figure 6. Figure 6 charts the reversibility of pressure-induced
asphaltene precipitation. The spectrum at 13 kpsi shows no
precipitation; the spectrum at 6 kspi exhibits significant
scattering from asphaltene flocculation. A 4 min spectral scan
(long to short wavelength with time) was performed showing
formation of asphaltene flocs with a pressure drop at a time
corresponding to 1930 nm, and showing deflocculation with
a pressure increase at a time in the scan corresponding to
1300 nm.
6000 psi scan. We then increased the pressure rapidly
to 13 000 psi; this occurred at a wavelegnth of ∼1310
nm). The OD immediately dropped and then overlaid
with the previous 13 000 psi scan. The flocs were
entirely deflocculated.
A subtle irreversibility is noted in the first depres-
surization the crude oil ever experienced. Figure 7a
shows the onset pressure obtained for a sample that had
never experienced low pressure. The onset pressure for
this sample was 8200 psi. Subsequently, the pressure
was dropped to 6000 psi, then raised within minutes to
13 000 psi deflocculating the sample. The onset pressure
for this sample was then found to be 8000 psi as shown
in Figure 7b, not 8200 psi as found for the virgin sample.
Perhaps some resin was transferred from asphaltene
flocs to the least stable asphaltene flocs that are
deficient in resin.30 Such a resin transfer would stabilize
these least stable fraction of asphaltene, thus would
produce a decrease in onset pressure.
Field Asphaltene vs Lab Asphaltene. An interest-
ing question arises as to how flocculation of field and
lab asphaltenes differ and whether lab asphaltene
flocculation is reversible as is largely true for field
asphaltene. The picture that emerges and is consistent
with successful theoretical models is as follows: as-
phaltenes are initially present in the crude oil in
micelles that are stabilized by association with resin,
probably the resin tends to locate on the surface rather
than in the bulk of the asphaltene micelle. Field
asphaltene flocculation (asphaltene induced by a pres-
sure drop on a live crude oil) results from destabilization
but not destruction of asphaltene micelles. This desta-
bilization most likely occurs due to the reduction of the
bulk oil dielectric constant. Thus, the flocs would consist
of undisrupted asphaltene micelles that have aggre-
gated. Only a small fraction of the asphaltene micelles
actually flocculate due to the subtle shift in dielectric
Energy & Fuels, Vol. 15, No. 4, 2001 985
Figure 7. (a) Initial onset pressure is 8200 psi. After one
pressure cycle the onset pressure shown in (b) reduces to 8000
psi suggesting a subtle irreversibility.
constant with pressure. If the dielectric constant is
restored by squeezing the compressible oil with an
increase in pressure, then the preserved asphaltene
micelles disaggregate restoring the original oil except
perhaps as we have suggested by some surface resin
transfer among the aggregated micelles.
On the other hand, lab asphaltenes, are formed by
addition of large dilutions of the original dead oil with
an alkane solvent, typically n-heptane. By definition,
the resins are soluble in the n-heptane while asphalt-
enes are insoluble. The large dilution acts to strip the
asphaltene micelles of their resin components, thus
altering the asphaltene micelles. The resulting precipi-
tate contains no resin. Restoration of micelles might be
accomplished perhaps with some difficulty by proper
addition and agitation of the resins with the fllocculated
and altered asphaltene miecelles. However, restoration
of these reformed micelles to their original virgin form
would be very difficult to accomplish (with certainty).
Implications on the Oil Field. The implications of
these results on the oil field are significant. Most
importantly, there are different types of asphaltene
precipitate which form with pressure reduction of live
crude oil. The initial precipitate is obviously the least
stable asphaltene and as such should be resin defi-
986 Energy & Fuels, Vol. 15, No. 4, 2001
Figure 8. An expanded view of the two-stretch overtone peak.
The increase of mass density at higher pressures results in
increased OD.
Figure 9. The spectral data in Figure 8 can be used to obtain
the compressibility.
cient.30 Consequently, the precipitate should not be very
tacky and adherent as is suggested by its inability to
continue grow in size. Essentially, this precipitate
should introduce little addition problem beyond that of
the virgin 3 nm asphaltene colloidal suspension origi-
nally present in the crude oil. The precipitate that forms
at low pressure contains more resin30 and thus is more
tacky. This asphaltene which grows in size is more likely
to adhere to available surfaces resulting in oil produc-
tion problems. Additionally, it is corroborated that the
field asphaltene and lab asphaltene are considerably
different and conclusions drawn from lab asphaltene
studies which are numerous and much easier do not
necessarily follow for field asphaltene studies.
Asphaltene precipitation is demonstrated here to be
largely reversible over a time frame of minutes, al-
though a subtle irreversibility is found. However, if a
Joshi et al.
live crude oil sample is stored at a pressure below the
onset pressure, it is quite likely that sample restoration
to the virgin state would be quite difficult. The asphalt-
ene precipitate may congeal or over time, change its
complex structure, thereby changing its precipitation
properties. Additionally, the precipitated asphaltene
might interact with other materials often present in oil
field samples such as clay, sand, or water. Restoration
might be quite difficult in such cases. Thus, the stan-
dard field procedure is mandatory maintenance of high
pressure on live crude oil samples to be used for
asphaltene studies.
Compressibility. It has been established that, for
high pressure, NIR spectra are linear in mass density
of the sample.19 Thus, NIR spectroscopy can be used to
measure fluid compressibility. Fluid compressibility (β)
gives the relative change of density with a change of
pressure.
1 ∂V
β) ( )
V ∂P T
(8)
Figure 8 shows the dependence on pressure of the peak
of the two-stretch overtone. Figure 9 plots the relative
change of the NIR absorption band integrated over the
spectral range 1600 nm to 1840 nm, vs the applied
pressure. If we presume just a linear relation of the
compressibility with pressure, we obtained a compress-
ibility of 1.306 × 10-4/atm. This value is close to the
value obtained on a separate but similar sample over
the same pressure range, β ) 1.15 × 10-4/atm which
was measured using a standard pycnometer to measure
densities. The fairly small difference in the two values
could be due to actual sample differences or could be
difference associated with the very different techniques
used to measure compressibilities. In any event, the
close agreement lends credence to our interpretations
of our spectral data.
IV. Conclusions
Asphaltenes of different characteristics are found to
precipitate from a live crude oil at different pressures.
As pressure is decreased, the initially formed flocs are
small and remain suspended; subsequent flocs formed
at lower pressures are large. Initial flocs are the least
stable and should be resin deficient, thus not very tacky.
Latter flocs are likely to have more resin and be tackier
thereby having an adverse effect on crude oil production.
In oil wells, greater pressure reduction with concomitant
greater oil production is consistent with some asphalt-
ene precipitation provided it is not the adherent type.
Field asphaltene precipitation is shown to be largely
reversible with pressure over the time frame of minutes,
with a subtle irreversibility evident. Asphaltenes in-
duced by pressure reduction on live crude oil are
contrasted to those prepared by solvent precipitation
from dead oils; these materials are not the same, yet
the single term asphaltene is used for both creating
some confusion. Finally we measure live crude oil
compressibility to validate our spectral analysis.
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