SPE 153602
Unusual Asphaltene Phase Behavior of Fluids from Lake Maracaibo,
Venezuela
Doris L. Gonzalez, SPE, Schlumberger-Reservoir Sampling and Analysis USA; Martha E. Garcia, SPE, PDVSA
Petroregional del Lago Venezuela; Omar Diaz, SPE, Schlumberger-Reservoir Sampling and Analysis Venezuela
Copyright 2012, Society of Petroleum Engineers
This paper was prepared for presentation at the SPE Latin American and Caribbean
Petroleum Engineering Conference held in Mexico City, Mexico, 16–18 April 2012.
This paper was selected for presentation by an SPE program committee following review
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Abstract
Reservoir fluids from Lake Maracaibo have reportedly
caused asphaltene operational problems ranging from
plugging of wellbores, pipelines and flowlines to clogging
of surface facilities (Garcia et al, 2001). Production of
fluids from some part of the region has been dramatically
reduced due to asphaltene precipitation and deposition
(Vasquez, 2010).
Asphaltene and wax precipitation is a serious problem in
production, transport and processing of reservoir fluids.
Of particular concern are the effects of asphaltene
precipitation and their potential to disrupt production due
to deposition in the near-wellbore regions and production
tubulars. This phenomenon is directly influenced by
changes in temperature, pressure and composition.
Commonly, low temperatures increase the probability of
asphaltene precipitation; however, experimental studies
on the fluid under study demonstrated unusual asphaltene
phase behavior.
This project involved experimental studies on fluid phase
behavior as part of a formation damage investigation. The
main challenges with fluids from the Maracaibo area are
the relative high H2S content (1-3%), high reservoir
temperature (270F) and the asphaltenic nature of the
crudes.
In this study, the asphaltene precipitation envelope was
determined using Near Infrared (NIR) Solid Detection
System (SDS), High Pressure Microscope (HPM),
Particle Size Analysis (PSA) and gravimetric techniques.
As expected, a significant amount of asphaltene was
observed to precipitate during depressurization. However,
reversibility of the precipitated asphaltene was also
observed below the bubble point and during re-
pressurization.
What was unusual about this fluid was the unconventional
asphaltene precipitation onset conditions found at low
temperatures. For most crude oils worldwide, asphaltene
precipitation onset pressure increases at lower
temperatures; however, the fluids considered in this work
have shown a non typical behavior wherein the asphaltene
onset pressure decreases with decreasing temperature.
Such behavior was earlier presented by Ting et al, 2003
on the Maracaibo oils; however, no reports have been
published since.
Introduction
The Maracaibo basin of western Venezuela is considered
one of the most oil prolific areas in the world (Goddard et
al, 2002). The petroleum production in this region began
around 1911 when several oil seeps were found, however,
it was only after 1946 that the first wells were drilled and
produced. Later, in 1970, new developments were
completed and commercial exploitation started in 1982.
The field evaluated in this study is located in the western
and central parts of the basin (see Figure 1). The field
covers an area of 798.6 km2 and includes a total of 116
wells. It has three main producing zones from the
Miocene, Eocene and Cretaceous ages, with depths
ranging from 8,000 ft to 17,500 ft true vertical depth
(TVD). Since 2006, the field has been operated by
Petroregional del Lago, a joint venture formed by
Petroleos de Venezuela-PDVSA (60%) and Shell (40%)
The reservoir under study in this work was discovered in
1974 in the Cretaceous with depths ranging from 15,000
to 17,000 ft TVD. Original oil in place was originally
estimated to be 1.946 billion barrels with recoverable
reserves of 195 million barrels. The initial reservoir
pressure was determined at 11,500 psi with a bubble point
pressure of 2,611 psi
2 SPE 153602

transport of reservoir fluids with high H2S content and

The average hydrocarbon gravity is 28API and the
producing gas-oil ratio (GOR) is 580 SCF/bbl. Currently,
there are 14 active wells and the production mechanism is
primary drive fluid expansion. Actual reservoir conditions
are 4,760 psi and 270F. The daily production rate is
11,434 bopd with a water cut of 0.3%.
were then shipped to the laboratory for analysis.
Preliminary evaluation of dead oil samples, followed by
pressure and temperature studies on live bottomhole
fluids provide important information about the
compositional characteristics and stability of the fluids
under study. The flow assurance evaluation revealed the
unusual phase behavior of the reservoir fluid in terms of
asphaltene precipitation tendency.

Bottomhole Crude Oil PVT Analysis

Measurements to characterize the reservoir fluid included

GOR, API, composition, constant composition expansion
(CCE) at reservoir and two lower temperatures,
differential liberation and live oil viscosity. Detailed fluid
properties and fluid compositions are summarized in
Tables 1 and 2 respectively.

Table 1 - Fluids Properties Summary

Reservoir Fluid
Reservoir Conditions
Pressure, psia 4,760
Figure 1 - Lake Maracaibo in Venezuela
Temperature, F 271
Depth, ft 15,800
Petroregional del Lago - PDVSA and Schlumberger
Bubble Point Pressure
jointly investigated the phase behavior of reservoir fluids
from the west part of the Maracaibo Lake. The particular Bubble Point Pressure at Tres, psia 2,902
well under study in this work was recompleted in 2004. Bubble Point Pressure at 182F, psia 2,568
Previous studies showed that the reservoir fluid was
unstable with respect to asphaltene precipitation at both Bubble Point Pressure at 94F, psia 1,922
reservoir temperature and at lower temperatures. Gas-Oil-Ratio
Unusually, the fluid exhibits a decrease in the asphaltene
GOR - Single-state flash (SCF/stb) 700
onset pressure as temperature decreases.
Total Differential Liberation GOR (SCF/stb) 908
Thermodynamic modeling approaches typically predict Properties at Reservoir Conditions
asphaltene onset pressures to increase as temperature
Viscosity, cP 0.59
reduces on the basis of most of the experimental data
-6
available (Jamaluddin et al., 2001; Buenrostro-Gonzalez Compressibility, 10 /psi 7.9
et al, 2004; Hassanvand et al, 2012). The data presented Density, g/cc 0.759
here indicate that this is not always the case and therefore
present a significant challenge for existing fluid behavior Properties at Saturation Conditions
models and understanding. Viscosity, cP 0.50
-6
Compressibility, 10 /psi 15.3

Experimental Density, g/cc 0.701

FVF – Single Stage Flash, at Pres & Tres 1.491
Laboratory experiments were carried out as part of a
Properties at 60F
formation damage study investigating asphaltene
precipitation in the Maracaibo Lake reservoir. Two Molar mass 243.3
bottomhole oil samples were selected for compositional, API – Single Stage STO 28.1
PVT and flow assurance analyses. Pressurized
monophasic fluid samples were collected at 15,800 ft and Density, g/cc 0.887
270F using a Single Phase Reservoir Sampler (SRS). Gas Gravity 1.013
Upon retrieval to surface, the sampled fluids were
transferred into Single Phase Bottles (SSB’s), suitable for
SPE 153602 3

Table 2 - Oil fluid composition (mole %)

Dead Oil Experiments
Flashed Flashed Monophasi
Component MW
Gas Liquid c Fluid Dead oil samples flashed from the pressurized samples
Carbon Dioxide 44.01 5.97 0.00 3.55 were used for the Saturates-Aromatics-Resins-
Hydrogen 34.08 1.18 0.00 0.70 Asphaltenes (SARA) analysis using a modified version of
Sulfide the ASTM D4124 method as implemented by
Nitrogen 28.01 0.53 0.00 0.31
Methane 16.04 54.77 0.00 32.55 Schlumberger Oilphase-DBR. The results of this analysis
Ethane 30.07 14.17 0.00 8.42
are summarized in Table. 3.
Propane 44.10 11.32 0.43 6.90
Table 3 - SARA Analysis (wt %)
I - Butane 58.12 1.69 0.22 1.10
N - Butane 58.12 4.68 1.05 3.21 SARA contents (% w/w) Crudes with no or
I - Pentane 72.15 1.64 1.00 1.38 few problems - de
Boer, 1995
N - Pentane 72.15 2.00 1.63 1.85
Saturates 53.0 < 62 wt%
N - Hexanes 84.00 1.31 3.96 2.38
M-C-Pentane 84.16 0.13 0.70 0.36 Aromatics 28.1 >26 wt%
Benzene 78.11 0.04 0.26 0.13 Resins 13.9 >11 wt%
Cyclohexane 84.16 0.06 0.51 0.24 Asphaltenes (n-C7) 3.6 > 3 wt%
N - Heptanes 96.00 0.35 4.44 2.01 Inorganic 1.4
M-C-Hexane 98.19 0.05 1.01 0.44
Toluene 92.14 0.02 0.83 0.35 Utilizing the SARA data and the de Boer criteria for
N - Octanes 107.00 0.08 5.42 2.25 asphaltene stability (de Boer et al, 1995) the reservoir
E-Benzene 106.17 0.00 0.40 0.16 fluid was expected to have no tendency to precipitate
M/P-Xylene 106.17 0.00 0.98 0.40 asphaltene.
O-Xylene 106.17 0.00 0.31 0.13
N - Nonanes 121.00 0.01 5.51 2.24
Asphaltene Pre-screening based on de Boer Plot
C10 134.00 0.00 6.42 2.61
C11 147.00 0.00 5.60 2.27
The de Boer plot is a method to screen crude oils for their
C12 161.00 0.00 4.81 1.95 tendency to precipitate asphaltenes based on the
C13 175.00 0.00 4.87 1.97 asphaltene solubility model derived from Flory and
C14 190.00 0.00 4.09 1.66 Huggins polymer theory and adopted by Hirschberg (de
C15 206.00 0.00 3.75 1.52 Boer et al, 1995). It evaluates the loss of asphaltene
C16 222.00 3.21 1.30 solubility as a reservoir fluid sample is depressurized.
C17 237.00 2.88 1.17 This screen is a cross-plot of in situ density and the
C18 251.00 2.72 1.11 degree of undersaturation with respect to gas (the
C19 263.00 2.69 1.09 difference between reservoir and saturation pressures).
C20 275.00 2.31 0.94 According to de Boer, asphaltene precipitation depends
C21 291.00 2.06 0.83
on the degree of super saturation created by the pressure
drop during production.
C22 300.00 1.97 0.80
C23 312.00 1.83 0.74 The de Boer plot was generated with fluids with no
C24 324.00 1.65 0.67 asphaltene problems and fluids with severe problems
C25 337.00 1.56 0.63 from the North Sea and Kuwait that present the typical
asphaltene phase behavior in which the precipitation onset
C26 349.00 1.40 0.57
pressure increases as temperature decreases.
C27 360.00 1.38 0.56
C28 372.00 1.31 0.53 The fluid in Maracaibo Lake is slightly undersaturated
C29 382.00 1.22 0.49 indicating a very stable fluid in the “No Problem” region
of the de Boer plot (Figure 2); however, the lab
C30+ 626.77 13.60 5.52
techniques used in this work (NIR/HPM/PSA) show that
Total 100.00 100.00 100.00
the fluid is very close to its precipitation onset and
MW 29.34 243.30 116.12
mitigation measurements should be consider in the near
Mole Ratio 0.5944 0.4056 future.
4 SPE 153602
12000
Pres = 4,760psia
10000 Pb = 2,902 psia
Undersaturation (Pres-Pb)
8000
Severe Problems
6000
4000
2000
0 Orig Asphal
0.5 0.6
In situ density
Figure 2 - The de Boer Plot – Pre-Screening
Gravimetric Test
Gravimetric tests were performed to determine the
asphaltene precipitation onset. In this technique,
asphaltenes are solubilized in the live oil at a pressure
above the upper asphaltene onset pressure (Jamaluddin et
a1, 2001). Below the upper asphaltene onset pressure,
asphaltenes will precipitate and grow in size. Larger
particles will segregate and settle at the bottom of the cell
due to gravity. The asphaltene concentration in the
supernatant fluid will decrease with decreasing pressure
indicating the asphaltene precipitation boundary.
Upon further reduction in pressure, the precipitated
asphaltenes may re-dissolve and the asphaltene content of
the supernatant phase will begin to increase. As such, the
gravimetric method can determine both the upper and
lower boundaries of the asphaltene phase envelope. The
accuracy of this method is limited by the accuracy of the
asphaltene content measurements, the pressure steps
selection and time for particles to settle. Most reservoir
fluids laboratories follow the IP-143 asphaltene content
method. In this standardized procedure the uncertainty in
the asphaltene content measurement is around 0,05 %
(w/w) for asphaltene content below 1% and above 0.1
%(w/w) for asphaltene content greater than 1%.
Gravimetric tests at 271°F, 182°F and 94°F were
performed on Maracaibo’s live fluid. Results of
asphaltene contents (n-heptane insolubles) as a function
of pressure are presented in Figure 3. It can be seen that
the value of the upper asphaltene onset pressure decreases
at lower temperatures; bubble points are observed
between 2,000 psi and 3,000 psi; and, the asphaltene
lower onsets are found around 1,000 psi.
5.0
4.5
4.0
3.5
Error Bar = 0.3wt%
3.0
Asphaltene Content, wt%
2.5
No Problem
Region 2.0
1.5
1.0 271F 182F 94F
Pb 271F Pb 182F Pb 94F
Fluid from Maracaibo Lake 0.5 AOP 271F AOP 182F AOP 94F
0.0
0.7 0.8 0.9 1 0 1000 2000 3000 4000 5000 6000 7000 8000 9000 10000 11000
Pressure, psia
Figure 3 - Gravimetric Measurements
Asphaltene Precipitation Onset (AOP) Measurements
Prior to the AOP measurements, the live reservoir fluid
was conditioned at temperature and pressure reservoir
conditions for five days to ensure sample homogeneity.
The conditioned fluid was pre-filtered using a 0.2 micron
silver filter during the isobaric and isothermal charge to
the cell to remove any impurities from the fluid. The
onset of asphaltene precipitation for the reservoir black oil
fluid was measured by pressure depletion using the solids
detection system (SDS).
The SDS test is performed in a visual PVT cell equipped
with fiber optic light transmission probes (source and
detector) mounted across the windows. The measurement
principle of the SDS is based on the transmittance of a
laser light at a fixed wavelength in the near infrared (NIR)
range through the test fluid while the pressure, the
temperature or the fluid composition is changed. Laser
beam transmittance is directly affected when solid
particles are formed in the fluid.
Concurrent with the transmittance measurement, pictures
of the fluid are taken to the fluid with a high pressure
microscope (HPM) connected to the bottom of the PVT
cell through a small sapphire window. The HPM
photographs help explain the observed NIR trend and
provide visual evidence (at the microscopic level) of the
agglomeration of asphaltenes during the isothermal
depressurization process. The HPM photographs are also
analyzed to measure the particle size distribution of the
precipitated asphaltene particles.
A detailed description of these techniques can be found in
Jamaludin et al., 2001.
SPE 153602 5

The measured asphaltene precipitation curve at 271F

is shown in Figure 4; the NIR light transmittance is
superimposed to the HPM photographs taken during the
test. The corresponding PSA (analysis of the HPM micro-
photographs) is shown in Figure 5.

1.E-03

4,200 psia 4,500 psia 7,000 psia 10,000 psia

1.E-04
Transmitted Light, mW

1.E-05
800 psia
Depressurization
1.E-06
1,000 psia
3,000 psia
Asphaltene onset pressure:
1.E-07 4,500 psia at 271 ºF
2,000 psia
2,500 psia

1.E-08
0 1000 2000 3000 4000 5000 6000 7000 8000 9000 10000 11000
Pressure, psia

Figure 4 - NIR+HPM during de-pressurization at 271ºF

Referring to these figures, it can seen there is a slight

increase in light transmittance observed during the initial
depressurization process due to a reduction of the fluid
density; no increase in particle size was observed during
this stage.

At approximately 4,500psia, particle formation caused

the light transmittance to decrease. This point of initial
light transmittance decrease is defined as the upper
asphaltene onset pressure.

Upon ongoing reduction in pressure, the precipitated

particles grew in concentration and size. The bubble point
pressure of the sample was detected around 3,000 psia at
271°F. Below the bubble point pressure, it can seen that
the asphaltene particle concentration and size decrease as
the asphaltenes were re-dissolve in the reservoir fluid.

Figure 5 – PSA+HPM during de-pressurization at 271ºF

6 SPE 153602

Similar measurements were performed at 182F and 94F

and are summarized in Figures 6 through 9.
1.E-03

1.E-04 4,000 psia 4,500 psia 7,000 psia

Transmitted Light, mW

1.E-05

1.E-06
400 psia
3,800 psia
Depressurization
1.E-07

1,500 psia
1.E-08 3,000 psia
Asphaltene onset pressure:
1.E-09 2,000 psia 4,200 psia at 182 ºF
2,500 psia
1.E-10
0 1000 2000 3000 4000 5000 6000 7000 8000 9000 10000 11000
Pressure, psia

Figure 6 - NIR+HPM during de-pressurization at 182ºF

At 182°F, the upper asphaltene onset was observed at

approximately 4,200 psia and the bubble point was
observed at around 2,500 psia.

1.E-03

1.E-04
3,500 psia 4,000 psia 7,000 psia 10,000 psia
Transmitted Light, mW

1.E-05

1.E-06 500 psia

Depressurization
1.E-07
900 psia 3,000 psia

1.E-08
Asphaltene onset pressure:
3,700 psia at 94 ºF
1.E-09
1,500 psia 2,000 psia

1.E-10
0 1000 2000 3000 4000 5000 6000 7000 8000 9000 10000 11000
Pressure, psia

Figure 7 - NIR+HPM during de-pressurization at 94ºF

At 94°F, the upper asphaltene onset pressure was

observed at 3,700 psia and the bubble point pressure was
detected around 2,000 psia.

Figures 8 and 9 present the particle size distribution

obtained by analyzing the HPM micro-photographs at
182°F and 94°F respectively.

Figure 8 - PSA+HPM during de-pressurization at 182ºF

SPE 153602 7

Table 4 - AOPs and Pbs for the Maracaibo

Lake Fluid
Temperature - ºF AOP - psia Pb - psia

271 4,500 2,902

182 4,200 2,568
94 3,700 1,922

5000
Reservoir Condition in 2011
4500
4000 Asphaltene Onset Curve
3500

Pressure, psia
3000
2500
2000
Experimental bubble point pressures
1500
1000
500
0
0 100 200 300 400 500 600 700 800 900 1000
Temperature, F

Figure 10 - Asphaltene Phase Envelope

The measurements indicate that that the reservoir fluid

will precipitate asphaltene during primary depletion;
asphaltene precipitation is anticipated as the temperature
and pressure decrease during normal production from
reservoir pressure and temperature to surface conditions.
It is noted that a reduction in temperature at constant
pressure will actually improve the asphaltene solubility in
the oil.

Temperature Effect

The solubility parameter of the reservoir fluid decreases

as pressure depletes from reservoir conditions to the
bubble point because the oil density decreases and makes
asphaltenes less stable.

Changes in temperature also affect the oil solubility

Figure 9 - PSA+HPM during de-pressurization at 94ºF
The experimental measurements show that the upper
asphaltene onset pressure decreases as temperature is
reduced from 271F to 182F and further to 94F. The
experimental results are summarized in Table 4 and the
asphaltene phase envelope is shown in Figure 10.
parameter. Typical asphaltene onset measurements show
an increase in asphaltene onset pressure as temperature is
reduced. An example of this typical behavior is shown in
Hassavand (Hassavand et al., 2012). A reduce in
temperature increases the oil density but at the same time
decreases the entropy of the solution, resulting in a
counter balancing effect (Ting, 2003). However, these
Maracaibo Lake fluids present a non-typical behavior in
which the asphaltene onset decreases as temperature is
reduced.
8 SPE 153602

Reversibility Behavior
1.E-03

The measurements describes above showed asphaltene re-

1.E-04
disolution below the bubble point at each of the three 4,000 psia 6,000 psia 8,000 psia 10,000 psia
temperatures, 271°F, 182°F and 94°F. (Figures 4 to 9).

Transmitted Light, mW
1.E-05

The asphaltene particles that appeared at the onset

1.E-06
pressure and grew as saturation pressure was approached, 800 psia
redisolve into the live fluid as pressure decreases below Depressurization
1.E-07 Pressurization
the bubble point. As the evolved gas moves out of
solution, the equilibrium oil becomes a better solvent for 3,000 psia
1.E-08
the precipitated asphaltene particles. Around 500 psi, the
NIR transmitted signal increases its value indicating re-
1.E-09
dissolution of the aggregates. The PSA technique shows a 1,800 psia 2,500 psia
corresponding decrease in size and count of particles at
low pressures in agreement with the HPM micro- 1.E-10
0 1000 2000 3000 4000 5000 6000 7000 8000 9000 10000 11000
photograph (Figures 5, 8 and 9). Below the bubble point,
Pressure, psia
there is a net increase in density and solubility parameter
when pressure decreases due to the release of lighter
Figure 12 - NIR + HPM during re-pressurization at 182F
hydrocarbons from the oil. The oil therefore becomes a
better solvent for asphaltenes (Ting, 2003).

In addition to the re-dissolution of the asphaltene at low Re-pressurization experiments show evidence of (at least
pressure (lower asphaltene onset pressure), it was of partial) reversibility of asphaltene precipitation
interest in this work to establish whether the asphaltenes confirming previous studies by Hammami et al in 2001.
would re-dissolve at the upper asphaltene pressure. This
reversibility behavior was studied in this work by
completing an isothermal re-pressurization of the
reservoir fluid from 500 psi to 10,000 psi for the test
temperatures of 271 and 182 F. The results of the
analysis are summarized in Figures 11 and 12. It can be
seen that the NIR transmitted light (red line in Figure 11)
followed a close path to the depressurization trajectory
indicating asphaltene re-dissolution. This signal showed
some hysteresis around the bubble point region but
closely matched the trend above the AOP. The
corresponding HPM microphotographs and PSA graphs
are depicted in Figures 11 to 13.
1.E-03

6,000 psia 8,000 psia

4,000 psia 10,000 psia
1.E-04
Transmitted Light, mW

840 psia
1.E-05

1.E-06 Depressurization
Pressurization

1.E-07

3,000 psia

1.E-08
0 1000 2000 3000 4000 5000 6000 7000 8000 9000 10000 11000
Pressure, psia

Figure 13 - PSA from HPM during re-pressurization at

Figure 11 - NIR + HPM during re-pressurization at 271F 271ºF
SPE 153602
Asphaltene Precipitation Modeling
Predictions of asphaltene onset at reservoir pressure and
temperature conditions represent a challenge for
asphaltene modeling. In this work, the Cubic plus
Association (CPA) equation of state model was used to
predict asphaltene precipitation.
Asphaltene Modeling using the Cubic EoS
The CPA-EOSs are simple models that have been
developed to describe asphaltene phase behavior.
However, the major limitation of cubic equations is that
they cannot describe adequately the phase behavior of
mixtures of molecules with large size disparities and they
are unable to accurately calculate their liquid densities
(Burke et al., 1990; Kawanaka et al., 1991; Mannistu et
al., 1997).
The additional association term in the CPA describe the
association of asphaltene molecules and their solvation by
resin molecules. The interactions between asphaltenes and
asphaltenes-resins are characterized by additional
association parameters (Li and Firoozabadi, 2009;
Edmonds et al, 1999).
Figure 14 shows the upper and lower asphaltene boundary
predicted by a commercial CPA-EoS. This tool is based
on the Peng-Robinson cubic EoS and requires crude oil
composition and experimental high pressure onset
measurements to draw the boundary lines.
Figure 14 - Asphaltene phase behavior prediction using
Cubic Plus Association (CPA) equation of state
9
The prediction for the Maracaibo fluid was obtained by
initially tuning the model to the measured PVT properties
of the reservoir fluid; saturation pressures, molecular
weights and densities were used to obtain the V-L phase
envelope.
The asphaltene onset boundary was automatically
predicted by the software using the AOP measurement at
271F as a tuning point. However, the model could not
converge when a second onset measurement at lower
temperature was added considered to the tuning data set.
Prediction of asphaltene precipitation of the fluid under
study was not possible using more that one experimental
measurement.
Conclusions
 Asphaltene precipitation studies made at reservoir
conditions revealed that the asphaltenes of the
Maracaibo fluid are expected to precipitate during oil
primary oil depletion; the upper asphaltene
precipitation onset is near to the bottomhole pressure
of the well.
 The asphaltene precipitation onset of the Maracaibo
reservoir fluid exhibited and unusual behavior in
which the asphaltene precipitation onset decreased as
temperature was reduced.
 The gravimetric method provides the upper and lower
boundaries of the asphaltene phase envelope
comparable to measurements obtained from NIR-
HPM-PSA techniques. The accuracy of this method
is limited by the accuracy of the asphaltene content
measurements, the pressure steps selection and time
for particles to settle.
 Reversibility measurements indicate that precipitated
asphaltene will go back into solution below the
bubble point for the Maracaibo fluid.
 Reversibility of asphaltene precipitation by re-
pressurization is also possible as shown by the
experiments performed in this work.
 Asphaltene precipitation prediction was not possible
using a cubic plus association EoS models.
Acknowledgements
The authors would like to thank PetroRegional del Lago
and Schlumberger for the permission to publish this
paper. We also would like to thank John Nighswander and
Artur Stankiewicz for their valuable comments.
10 SPE 153602

Nomenclature Jamaluddin, A.K.M.; Creek, J.; Kabir, C.S.; McFadden, J.D.;

D’Cruz, D.; Manakala, J.; Joshi, N.; Ross, B.. 2001. A
AOP = Asphaltene Onset Pressure Comparison of Various Laboratory Techniques to Measure
API = American Petroleum Institute Thermodynamic Asphaltene Instability. SPE 72154.
ASTM = American Society for Testing and Materials Kawanaka, S., P., Park S. J. and Mansoori, G. A. 1991. Organic
CCE = Constant Composition Expansion Deposition from Reservoir Fluids: A. Thermodynamic
Predictive Technique, SPE Reservoir Engineering, 185.
CPA = Cubic Plus Association Li, Z. and Firoozabadi, A. 2010. Modeling Asphaltene
EoS = Equation of State Precipitation by n-Alkanes from Heavy Oils and Bitumens
GOR = Gas-Oil-Ratio Using Cubic-Plus-Association Equation of State. Energy
HPM = High Pressure Microscope Technique Fuels 24, 1106–1113: ef9009857.
MW = Molecular Weight Mannistu, K. D., Yarranton, H. W. and Masliyah, J. H. 1997.
NIR = Near Infrared Solubility Modeling of Asphaltenes In Organic Solvents,
PSA = Particle Size Analysis Technique Energy and Fuels, 11, 615.
PVT = Pressure-Volume-Temperature Ortiz, J. L. 2011. Development of Heavy Oil Offshore Lake
PC-SAFT=Perturbed Chain – Statistical Association Fluid Maracaibo Field Using Slug Gas Lift: A Case History. SPE
143920.
Theory Ting, D. and Cornelisse, P. M. W. 2003. Shell. An experimental
PDVSA = Petroleos de Venezuela S.A. and modeling study on asphaltene precipitation and wax
PVT = Pressure Volume Temperature formation in live oil systems The 4th International Conference
SARA = Saturates, Aromatics, Resins, Asphaltenes on Petroleum Phase Behaviour and Fouling. Norway.
SDS = Solids Detection System Ting, D. L. 2003. Thermodynamic Stability and Phase Behavior
SSB = Single Phase Bottle of Asphaltenes in Oil and of other Highly Asymmetric
SRS = Single Phase Reservoir Sampler Mixtures, Ph.D. dissertation, Rice University, Houston, USA.
TVD = True Vertical Depth Vasquez, V. 2010. Evaluation of Sand Control Completion
Alternatives and Asphaltene Deposition Treatments in the
Area 2 Sur Field Maracaibo Lake Venezuela. SPE 130559.
References
Buenrostro-Gonzalez, E.; Galeana-Lira, C.; Gil-Villegas, A.;
Wu, J. 2004. Asphaltene Precipitation in Crude Oils: Theory
and Experiments. AIChE Journal, Vol. 50, No. 10.
Burgos, G.; Buijse, M.; Fonseca, E.; Brady, M. and Olvera, R.
2005. Acid fracturing in Lake Maracaibo: How Continuous
Improvements Kept on Raising the Expectation Bar. SPE
96531.
Burke, N. E., Hobbs, R. E. and Kashou, S. F. 1990.
Measurement and Modeling of Asphaltene Precipitation,
Journal of Petroleum Technology, 42, 1440.
De Boer, R.B.; Leerloyer, K.; Eigner, M.P.R. and van Bergen,
A.R.D. 1995. Screening of Crude Oils for Asphaltene
Precipitation: Theory, Practice, and the selection of Inhibitors.
SPE Production and Facilities.
Edmonds, B.; Moorwood, R.A.S.; Szczepanski, R.; Zhang, X.;
Heyward, M.; Hurle, R. 1999. Measurement and Prediction of
Asphaltene Precipitation from Live Oils. Presented at the
Third Symposium on Colloid Chemistry in Oil Production.
Garcia, M. C., Chiaravallo, N. 2001. Asphaltene Deposition
Control in Lake Maracaibo Crude Oil production. SPE 65009.
Goddard, D. A. and Talukdar, S. C. 2002. Cretaceous Fine-
Grained Mudstones of the Maracaibo Basin, Venezuela Gulf
Coast Association of Geological Societies Transaction, Vol.
52. Siltstone Symposium.
Hammami, A.; Phelps, C. H. and Monger-McClure, T. 2000.
Asphaltene Precipitation from Live Oils: An Experimental
Investigation of Onset Conditions and Reversibility. Energy
& Fuels 14, 14-18.
Hassanvand, M., Shahsavani, B. and Anooshe, A. 2012. Study
of temperature effect on asphaltene precipitation by visual and
quantitative methods. Journal of Petroleum Technology and
Alternative Fuels. Vol. 3(2), pp. 8-18.
IP-143/04 Determination of Asphaltenes (heptane Insolubles) in
Crude Petroleum and Petroleum Products.
Jamaluddin, A. K. M.; Joshi, N.; Iwere, F.; Gurnipar, O. 2001.
An Investigation of Asphaltene Instability under Nitrogen
Injection. SPE 74393.