Energy Fuels 2011, 25, 568–572 : DOI:10.

1021/ef101213x
Published on Web 01/18/2011

Study of Live Oil Wax Precipitation with High-Pressure Micro-Differential

Scanning Calorimetry†
Priyanka Juyal,‡ Tran Cao,‡ Andrew Yen,‡ and Rama Venkatesan*,§
‡
Nalco Energy Service, 7705 Highway 90-A, Sugar Land, Texas 77478, United States, and
§
Chevron Energy Technology Company, 1400 Smith Street, Houston, Texas 77002, United States

Received September 7, 2010. Revised Manuscript Received December 3, 2010

For live oils, the effect of pressure (amount of dissolved gas) on the wax appearance temperature (WAT)
can be quite pronounced. Here, we describe the use of high-pressure micro-differential scanning
calorimetry (HP-μDSC) as an effective technique to determine the WAT for live oils. The effect of increas-
ing equilibration time on WAT is described and compared to predictions from a thermodynamic model.

Introduction measure of the crystallization behavior of a crude oil.9-12 At

Paraffins can precipitate out of a crude oil during produc-
tion operations when the oil is cooled because of heat loss to
the surroundings. The deposition of paraffinic waxes in
pipelines poses a significant challenge during petroleum
production.1-5 Ensuing production losses because of down-
time and remediation operations may cost millions of dollars
and even lead to abandoning of off-shore wells.6-8 As the oil
industry expands into deeper offshore oil and gas prospects,
flow assurance takes on a new shift driven by the combination
of a hostile environment, challenging fluid properties, and
system reliability targets in deep-water production systems.
The problem of wax deposition increases in severity in extreme
subsea environments, where the surrounding temperature is
colder and because of the deployment of subsea tie-backs over
longer distances. In such remote environments, the cost of
remediation also increases manifold.
An understanding of the rheology and crystallization be-
havior of the crude oil is critical to manage wax deposition
during oil production, transportation, and end-use applica-
tions. Wax appearance temperature (WAT) is an important
†
Presented at the 11th International Conference on Petroleum Phase
Behavior and Fouling.
*To whom correspondence should be addressed. E-mail:
vrama@chevron.com.
(1) Roenningsen, H. P.; Bjoerndal, B.; Hansen, A. B.; Pedersen, W. B.
Energy Fuels 1991, 5 (6), 895–908.
(2) Pauly, J. P.; Daridon, J. L.; Coutinho, J. A. P. Fluid Phase Equilib.
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(3) Thanh, N. X.; Hsieh, M.; Philip, R. P. Org. Geochem. 1999, 30,
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(6) Nguyen, A. D.; Fogler, H. S.; Sumaeth, C. Ind. Eng. Chem. Res.
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Pasteur, U. L.; Behar, E. Proceedings of the 68th Annual Technical
Conference and Exhibition; Houston, TX, Oct 3-6, 1993; SPE 26549.
temperatures lower than the WAT, the paraffin molecules in a
crude oil start to precipitate as wax crystals, which is the first
step toward both wax gelation and deposition. The WAT and
amount of wax precipitated at temperatures below the WAT
are thus important indicators in determining if wax deposition
and gelation will occur. Estimation of the WAT and amount
of wax precipitated is crucial information for the design of
flow lines and the production system and also the wax control
strategy. Several procedures are employed to study wax phase
transitions in crude oil systems, such as viscometry,1,13-15
cross-polar microscopy (CPM),1,13 differential scanning cal-
orimetry (DSC),10,13,15 densitometry,16 near-infrared (NIR)
spectroscopy,11,17 centrifugation, and filtration, that provide
information on the WAT and amount of wax precipitated as a
function of the temperature.12 Most of these techniques
measure the WAT of dead crude oil; the effects of the pres-
sure and amount of dissolved gas in the live oil are not
taken into account. The effect of the pressure on wax pre-
cipitation for reservoir fluids with a high gas/oil ratio (GOR)
can be quite pronounced.18-23 The lighter components at
reservoir conditions are able to dissolve a significant amount
of wax molecules. Both the WAT and amount of wax
precipitated will be reduced with an increasing amount of
(13) Kok, M. V.; Letoffe, J. M.; Claudy, P.; Martin, D.; Garcin, M.;
Volle, J. L. Fuel 1996, 75, 787–790.
(14) Singh, P.; Fogler, H. S.; Nagarajan, N. J. Rheol. 1999, 43, 1437–
1459.
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(16) Kruka, V. R.; Cadena, E. R.; Long, T. E. J. Pet. Technol. 1995,
47, 681–687.
(17) Alex, R. F.; Fuhr, B. J.; Klein, L. L. Energy Fuels 1991, 5, 866–
868.
(18) Brown, T. S.; Niesen, V. G.; Erickson, D. D. Proceedings of the
69th Annual Technical Conference and Exhibition; New Orleans, LA, Sept
25-28, 1994; SPE 28505.
(19) Pan, H.; Firoozabadi, A. Proceedings of the Annual Technical
Conference and Exhibition; Denver, CO, Oct 6-9, 1996; SPE 36740.
(20) Coutinho, J. A. P. Proceedings of the 13th European Petroleum
Conference; Aberdeen, Scotland, Oct 29-31, 2002; SPE 78324.
(21) Daridon, J.; Pauly, J.; Coutinho, J. A. P.; Montel, F. Energy
Fuels 2001, 15, 730–735.
(22) Pauly, J.; Daridon, J.; Coutinho, J. A. P.; Dirand, M. Fuel 2005,
84, 453–459.
(23) Tackett, J. E. Comparison of Cloud Point Methods, DeepStar
Report (CTR 907); DeepStar: Houston, TX, 1997.

r 2011 American Chemical Society 568 pubs.acs.org/EF

Energy Fuels 2011, 25, 568–572 : DOI:10.1021/ef101213x Juyal et al.

dissolved gas. Quantifying these values with reasonable con- Table 1. Composition of the STO
fidence is important in appropriately designing flow assurance component mole percentage molecular weight
strategies for new field development as well as mitigating
problems in existing operations. The improvisation of routi- C3 1.69
nely used laboratory techniques to detect wax crystallization i-C4 0.97
n-C4 3.36
or the development of new methods that are more repre- i-C5 3.14
sentative of live oil is important. Thus, to obtain accurate n-C5 4.20
estimates of the live oil WAT and assess the risk for wax C6 7.46 86.2
deposition, these experiments must be performed at the right C7 11.51 96.0
C8 12.80 107.0
operating conditions. C9 8.81 121.0
A project sponsored by DeepStar a few years ago provided a C10þ 46.06 237.1
recommendation of using at least two independent methods
for measuring the WAT of a crude oil because of the uncer-
tainties associated with different techniques.23 Typically, DSC
and CPM are the most widely used methods in the industry to
determine the WAT of stock tank (dead) oil. DSC involves
measuring the heat transition as the first wax crystal appears in
the crude oil, when the crude oil is cooled under isobaric
conditions.1,11,13,15,24-27 WAT is characterized by the appear-
ance of an exothermic peak in the DSC thermogram. CPM
involves visual observation of the appearance of wax crystals
when the sample is cooled on a microscopic slide and observed
under polarized light. Other techniques, such as viscometry,
are also often used. In measurement of WAT with a viscometer
or rheometer, the temperature where the viscosity profile of the
crude oil at constant shear deviates from Arrhenius-type
behavior is taken as the WAT.
Although the effect of the pressure on the WAT and amount
of wax precipitated is well-recognized, there have not been
many studies concerning the correlation of the pressure on the
propensity of live oil wax crystallization.18-22,26,27 This study Figure 1. n-Paraffin composition of the crude oil.
describes the use of high-pressure micro-differential scanning
calorimetry (HP-μDSC) as a reliable technique to evaluate Table 2. Synthetic Gas Blend Composition
wax precipitation from crude oil under live oil conditions. The component mole percentage
WAT as well as the amount of wax precipitated has been
N2 0.1
measured, and the effects of the equilibration time on the gas CO2 1.8
uptake, cooling rate, and sample loading are enunciated. The C1 73.6
influence of the gas components on the onset crystallization C2 12.4
temperature of a light crude oil with high GOR has been C3 7.7
measured and compared to results from conventional DSC i-C4 1.4
n-C4 3.1
and CPM, as well as thermodynamic models.
Figure 1. The total amount of n-paraffins above C20 (n-C20þ)
Experimental Section was about 3.2% by weight on a STO basis.
A synthetic gas blend was prepared to match the flashed gas
Model and Crude Oil Systems. A model wax/oil system was composition from the live oil. Table 2 reports the composition of
used to benchmark the experimental results. The system consists the synthetic gas blend. This gas was recombined with the STO
of a food-grade wax with a n-paraffin carbon number distribu- to form the live oil under various saturation pressures.
tion ranging from n-C20 to n-C40 dissolved in light mineral oil CPM. CPM is a visual technique to determine the WAT based
(Aldrich). on the appearance of wax crystals upon cooling. The crude oil
A volatile light crude oil [44° American Petroleum Institute sample (STO) was prepared by initially heating the sample well
(API)] was used to study the effect of the pressure on the WAT. above the expected WAT and homogenizing to ensure dissolution
The reservoir fluid has a GOR of about 3000 standard cubic feet/ of all waxes. The sample was then loaded onto a temperature-
stock tank barrel (scf/stb). The stock tank oil (STO) was used to controlled microscope stage and cooled slowly. The temperature
determine the WAT and rheology properties at atmospheric at which the first wax crystals were observed under the CPM was
conditions. Table 1 shows the composition of the STO. taken as the WAT.
The n-paraffin distribution of the STO was determined by Rheology. A TA Instruments AR-G2 rheometer was used to
high-temperature gas chromatography (HTGC) and is shown in determine the viscosity and other rheological properties of the oil
at ambient pressure. Rheology results were used as another check
(24) Sandra, C.; Veronique, R.; Behar, E. Proceedings of the Interna- on the WAT. It is necessary to perform the rheological experi-
tional Symposium on Oilfield Chemistry; Houston, TX, Feb 18-21, 1997, ments at a low shear rate to minimize degradation of the wax
SPE 37239. crystals under shear. The sample was cooled from a temperature
(25) Letoffe, J. M.; Claudy, P.; Garcin, M.; Volle, J. L. Fuel 1995, 74 well above the WAT at a cooling rate of 1 °C/min. The tempera-
(1), 92–95. ture at which the viscosity deviates from the Newtonian Arrhe-
(26) Vieira, L. C.; Buchuid, M. B.; Lucas, E. F. Energy Fuels 2010, 24
(4), 2208–2212. nius-type behavior was taken as the WAT.
(27) Vieira, L. C.; Buchuid, M. B.; Lucas, E. F. Energy Fuels 2010, 24 DSC. A DSC 910S Thermal Analyst 2100 (TA Instrument)
(4), 2213–2220. was employed to measure the WAT of the model oil as well as
569
Energy Fuels 2011, 25, 568–572 : DOI:10.1021/ef101213x
the crude oil. The WAT was determined at the onset of the DSC
exotherm. The sample was scanned from 90 to -20 °C at a scan
rate of 2 °C/min.
HP-μDSC. A Setaram HP-μDSC VII was used in the anal-
ysis. The HP-μDSC sample cells are composed of a Hastelloy
C276 material and have a 0.5 cm3 sample capacity. The pressure
Figure 2. HP-μDSC thermogram of the model oil system at ambient
pressure.
Figure 3. Amount of wax as a function of the temperature.
Figure 4. DSC thermogram of crude oil used in this study.
570
Juyal et al.
inside the sample cell can be controlled by means of a high-
pressure gas panel, which can work up to 1000 bar (14504 psi).
Pressure can be regulated with better than 1% accuracy. A
pump is used for controlling the pressure inside the cell and was
used to charge the sample with desired pressure ranges. Peltier
elements are used for cooling/heating the cells at the desired rate.
A schematic of the Setaram HP-μDSC VII is described in the
published literature.28,29
In this study, the samples were charged with pressure ranging
from 250 to 4000 pounds per square inch (psi). The rate of cooling
was maintained at 2 °C/min. The crude oil was homogenized at
60 °C in a temperature-controlled oven for 1 h and shaken prior to
starting each run, to ensure complete dissolution of wax. Approxi-
mately 200-210 mg of the crude oil (STO) was then added to the
cell, followed by pressurization using the high-pressure gas panel
to the desired pressure of the gas blend. The sample was heated to
65 °C and allowed to saturate with the gas for 4, 24, and 48 h. The
cell is then cooled at 2 °C/min to a temperature of -10 °C.
Precipitation Model. Different models were used to predict the
WAT and precipitated wax content of the model oil and crude oil
systems based on the compositional analysis of the oil and wax. In
this paper, we have used two different software packages for the
predictions: Multiflash from Infochem and PVTsim from Calsep.
Multiflash model developed by Coutinho and coworkers20,30
implements detailed n-paraffin composition information to di-
rectly predict the WAT and amount of wax precipitated. On the
other hand, PVTsim typically needs some tuning to match the
atmospheric pressure WAT; it can then be used to predict the
WAT of live oils at various saturation pressures.
Results and Discussion
Model Oil. The accuracy of HP-μDSC was tested with a
model oil system at ambient pressure. The model oil used in the
study is 10% model wax in mineral oil. Figure 2 shows the
thermogram of the model oil system recorded from HP-μDSC
at ambient pressure. The measured WAT was compared to
measurements using a conventional DSC and CPM. The WAT
was measured at about 97 °F with HP-μDSC and 96 °F with
CPM. The measured WAT also concurs with that from the
conventional DSC. These results confirm that the results from
HP-μDSC are well within acceptable limits.
The amount of wax precipitated as a function of the tem-
perature was inferred from the area under the DSC exotherm
Energy Fuels 2011, 25, 568–572 : DOI:10.1021/ef101213x
and compared to that calculated from the Multiflash thermo-
dynamic model. Figure 3 reports the amount of wax precipi-
tated as a function of the temperature for the model oil system.
HP-μDSC quantifies about 9% of wax precipitation as the
Figure 5. Viscosity profile of the crude oil under study.
Figure 6. Wax precipitation from the crude oil (DSC and model results).
Figure 7. WAT of the crude oil as a function of the equilibration time at 1000 psia, as measured with HP-μDSC.
571
Juyal et al.
system cools from 95 to 0 °F. This is in reasonable agreement
with the theoretical prediction from the model. This confirms
the accuracy of HP-μDSC for quantifying wax crystalliza-
tion. The WAT of the model oil was also tested under
pressure exerted by an inert gas (N2) to check the validity
of the results under pressure. The WAT with 1000 psi of N2
gas pressure was measured to be the same as the WAT under
ambient pressure conditions. The amount of wax precipi-
tated also remains essentially unchanged in the presence of
N2 gas, which is expected, because N2 would not dissolve
paraffin molecules (Figure 3). Thus, the HP-μDSC results
under pressure were also confirmed to be accurate.
Crude Oil. After confirmation with the model oil, the crude
oil system was tested, initially at atmospheric pressure and
then under pressure with synthetic gas. A conventional DSC
was first used to determine the WAT and wax content of the
STO. The DSC thermogram displayed in Figure 4 shows two
distinct wax crystallization events for this oil. The WAT is
Energy Fuels 2011, 25, 568–572 : DOI:10.1021/ef101213x
Figure 8. Comparison of WAT from the thermodynamic model and
HP-μDSC.
measured to be about 37 °C (98.6 °F) and closely matches with
the CPM result of 38 °C (∼100 °F). A lower crystallization
onset (“WAT-2”) occurs at about 26 °C (∼79 °F).
Low shear rheology methods were also used to identify the
WAT even for oils with relatively low wax content. WAT can
be determined from rheological measurement as the point on
the viscosity versus temperature graph at which deviation
from linearity occurs as the temperature is lowered. The low
shear rheological measurement for the crude oil is detailed in
Figure 5. The viscosity of the crude oil shows departure from
the linear behavior at around 37 °C, the WAT. A bigger
departure is noticed at around 26 °C, which corresponds to a
second crystallization event, the “WAT-2”. Thus, the second
crystallization event is confirmed with the rheology of the
crude. The WAT and second crystallization, “WAT-2”, eval-
uated with rheological data are in agreement with the DSC
results.
The data from DSC were used to determine the amount of
wax precipitated as a function of the temperature, similar to
the model oil results shown in Figure 3. Figure 6 shows the
results from DSC and the predictions from the PVTsim model
after tuning for WAT. Modeling with Multiflash using the
detailed n-paraffin composition analysis produced similar
results in terms of overall wax precipitation, but the second
crystallization event (“WAT-2”) was not readily observed.
HP-μDSC was then used to determine the WAT of the live
oil at various pressures. The synthetic gas was used to pressure
the oil in the DSC. Equilibration was performed at 65 °C
(149 °F), well above the WAT of the STO. Because gas
dissolution is limited by diffusion, the equilibration time was
expected to have an effect on the amount of gas dissolved in
the oil. Various equilibration times were studied, and the effect
on the WAT was observed.
WAT as a function of the equilibration time at a constant
pressure of 1000 psi is reported in Figure 7. It is observed that
both WAT and WAT-2 decrease significantly with an increasing
(28) Gupta, A.; Lachance, J.; Sloan, E. D., Jr.; Koh, C. A. Chem. Eng.
Sci. 2008, 63, 5848–5863.
(29) Parlou€er, P. L.; Dalmazzone, C.; Herzhaft, B.; Rousseau, L.;
Mathonat, C. J. Therm. Anal. Calorim. 2004, 78, 165–172.
(30) Coutinho, J. A. P. Fluid Phase Equilib. 1999, 157, 447.
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Figure 9. Comparison of the second crystallization temperature
shows an overprediction by the model.
equilibration time under 1000 psi of synthetic gas pressure. As
the equilibration time increases, a greater volume of gas
diffuses into the crude oil; hence, the WAT reduces with an
increasing equilibration time. As the equilibration time reached
about 2 days (48 h), the system moved toward equilibrium
saturation.
Similar results for WAT and WAT-2 (a decreasing trend
with an increasing equilibration time) were observed for higher
pressures as well. These results clearly suggest that more gas
diffusion into the sample leads to dissolution of the paraffin
and, hence, reduction in the WAT.
The above HP-μDSC measurements of live oil WAT were
compared to thermodynamic model results. Figure 8 shows
the effect of the equilibration time on the gas uptake and WAT
of the crude oil in comparison to the thermodynamic model.
As can be seen, the HP-μDSC data move closer to the model
prediction results as the equilibration time increases. At 48 h
of equilibration, the data match well with the model results.
This confirms that the results from HP-μDSC are reasonably
accurate provided that equilibrium is reached in the system.
Figure 9 shows the comparison of the second crystal-
lization temperature (“WAT-2”) determined from HP-
μDSC to those inferred from the model. In this case, the
model tends to overpredict the WAT-2 as compared to the 48
h HP-μDSC results. This indicates that the model may not
predict the wax precipitation curve correctly at higher pres-
sures and may require further tuning. This is currently under
investigation and may be addressed in a future publication.
Conclusions
Using a model oil system and a crude oil, it has been shown
that HP-μDSC can be used to accurately measure the WAT of
dead as well as live oils. The results in the STO case were
confirmed with independent measurements, such as conven-
tional DSC, CPM, and rheology. In the case of the live oil
system, the HP-μDSC results were compared favorably to
modeling results. The effects of the saturation pressure and
equilibration time on the WAT have also been enunciated.
Acknowledgment. The authors thank Nalco Company and
Chevron for the permission to present the results of this research
study. Conventional DSC analysis was performed by L. A.
Washington of Chevron Energy Technology Company.