Energy & Fuels 2009, 23, 12891293

1289

Characteristics of Wax Gel Formation in the Presence of

Asphaltenes
Kyeongseok Oh* and Milind Deo
Chemical Engineering Department, UniVersity of Utah, Salt Lake City, Utah 84112
ReceiVed August 1, 2008. ReVised Manuscript ReceiVed NoVember 26, 2008

When pipelines are shutdown, waxy crude oils tend to form gels, which tend to plug the lines and stop flow.
Restart requires sufficient pressure to overcome the yield stress of gelled oils. This study examines the yield
strength of well-characterized waxy model oils at temperatures below the pour point. First, the yield stresses
of model oils were determined by the vane method at different temperatures. Yield stress values were strongly
dependent upon wax amounts and compositions, as expected. The extent of increase in yield stress values
with temperature was greater for model oils that had a higher percentage of wax. The x-intercept values obtained
from yield stress versus temperature were interpreted as no-flow points, which could be used as alternative
measures of pour points. Second, the role of asphaltenes was examined in the evolution of the yield stress as
the oil is cooled below the pour point. Asphaltene additions resulted in pour-point reductions, of up to 4 C
for additions of asphaltenes up to 0.1% (w/w). Small amounts of asphaltenes (0.01%, w/w) also played a
significant role in yield stress reduction. The concept of steric hindrance and asphaltene aggregation was adapted
to explain the yield stress reduction at the different asphaltene concentrations. At lower temperatures, as more
wax came out of solution, the slope of the yield stress versus temperature line went back to the slope of the
asphaltene-free oil, indicating the dominance of the wax networks at higher wax concentrations.

Introduction
High-molecular-weight paraffinic waxes in a crude oil start
to precipitate when the surrounding temperature is lower than
the wax appearance temperature (WAT). The terms, cloud point
and wax precipitation temperature, are often used interchangeably. Dependent upon the method used, WAT measurements
can be significantly different. Pedersen et al.1 determined WATs
with three different measurement methods: microscopy, viscosity, and differential scanning calorimetry, showing that typically
highest WAT values were observed when using the microscopic
measurement. The comparison of WAT values and the detection
limits with the different methods has also been reported
elsewhere.2 The pour point on the other hand is another
important characteristic temperature that is usually determined
by American Society for Testing and Materials (ASTM) D97.3
Flow discontinuity can occur either with wax deposition or wax
gel formation. While the wax deposition can be initiated during
flow, wax gel formation occurs under static conditions caused
by shutdown. Subsequent to shutdown, if the wax gel develops,
a certain level of pressure application upstream is necessary to
overcome the yield stress of the gel along the pipeline for
Presented at the 9th International Conference on Petroleum Phase
Behavior and Fouling.
* To whom correspondence should be addressed. Fax: (801) 585-9291.
E-mail: asphaltene@yahoo.com.
(1) Pedersen, K. S.; Skovborg, P.; Rnningsen, H. P. Wax precipitation
from North Sea crude oils. 4. Thermodynamic modeling. Energy Fuels 1991,
5, 924932.
(2) Coutinho, J. A. P.; Daridon, J.-L. The limitations of the cloud point
measurement techniques and the influence of the oil comparison on its
dectection. Pet. Sci. Technol. 2005, 23, 11131128.
(3) American Society for Testing and Materials (ASTM). Petroleum
products, lubrications. Annual Book of ASTM Standards; ASTM: West
Conshohocken, PA, 1999; section 5.

restart.4 The pressure requirement for restart has been predicted

on the basis of various rheological studies of gelled waxy
oils.5-12 Boger and co-workers11-14 discussed the existence of
three definite characteristic responses, which they categorized
as elastic, creep, and fracture when the gel was subjected to
shear. In the elastic region, the gel strength is fully recovered
after a low shear is applied to the gel regardless of the time
duration over which the shear is applied. Prior to the static yield
stress (the point at which the gel fractures), a creep region is
observed, in which the gel strength is partially recovered once
the applied stress is released. The gel breakage occurs in the
(4) Golczynski, T. S.; Kempton, E. C. Understanding wax problems leads
to deepwater flow assurance solutions. World Oil 2006, 227 (3), D7D10.
(5) Davenport, T. C.; Somper, R. S. H. The yield value and breakdown
of crude oil gels. J. Inst. Pet. 1971, 57 (554), 86105.
(6) Rnningsen, H. P. Rheological behaviour of gelled, waxy North Sea
crude oils. J. Pet. Sci. Eng. 1992, 7, 177213.
(7) Lopes da Silva, J. A.; Coutinho, J. A. P. Dynamic rheological analysis
of the gelation behavior of waxy crude oils. Rheol. Acta 2004, 43, 433
441.
(8) Singh, P.; Fogler, H. S.; Nagarajan, N. Prediction of the wax content
of the incipient wax-oil gel in a pipeline: An application of the controlledstress rheometer. J. Rheol. 1999, 43, 14371459.
(9) Venkatesan, R.; Nagarajan, N. R.; Paso, K.; Yi, Y.-B.; Sastry, A. M.;
Fogler, H. S. The strength of paraffin gels formed under static and flow
conditions. Chem. Eng. Sci. 2005, 60, 35873598.
(10) Oh, K.; Magda, J.; Deo, M. D. Yield and strength recovery of wax
gels. The 8th International Conference on Petroleum Phase Behavior and
Fouling, Pau, France, June 10-14, 2007.
(11) Chang, C.; Boger, D. V.; Nguyen, Q. D. The yielding of waxy
crude oils. Ind. Eng. Chem. Res. 1998, 37, 15511559.
(12) Wardhaugh, L. T.; Boger, D. V. The measurement and description
of the yielding behavior of waxy crude oil. J. Rheol. 1991, 35 (6), 1121
1156.
(13) Nguyen, Q. D.; Boger, D. V. Yield stress measurement for
concentrated suspensions. J. Rheol. 1983, 27 (4), 321349.
(14) Nguyen, Q. D.; Boger, D. V. Direct yield stress measurement with
the vane method. J. Rheol. 1985, 29 (3), 335347.

10.1021/ef8006307 CCC: $40.75 2009 American Chemical Society

Published on Web 12/29/2008

1290 Energy & Fuels, Vol. 23, 2009

fracture region when the loading stress is high enough to disrupt

the gel network.
The yield stress varies with temperature, stress duration time,
ramping rate of shear, and combinations of all of the above
factors. Singh et al.8 pointed out that various factors, such as
wax/oil ratio (wax amounts), molecular weight of the wax,
cooling rate, and mechanical shear history, affect wax precipitation and deposition characteristics, including gelation temperature. In particular, they reported a depression in the gelation
temperature, upon application of shear while cooling, with a
greater reduction at higher shear rates. They also compared the
effect of cooling rates (ranging from 0.8 to 0.08 C/min) on
the gelation temperatures, showing that slower cooling rates
resulted in greater reductions in yield stresses. Venkatesan et
al.9 examined the yield stresses with different cooling rates under
both quiescent and shear conditions. The highest yield value
was observed under quiescent conditions with the slowest
cooling rate. Upon application of shear, the yield stress
increased, with the highest value observed at the highest cooling
rate. Both studies8,9 used the gelation temperature as a flow
transition characteristic value instead of the pour-point measurement. The gelation temperature is usually between the WAT
and the pour point.10 A lower level of cross-linking (than that
required for the detection of the pour point) is often adequate
for gelation temperature measurement in rheological studies.
It has been shown that wax gel formation is altered in the
presence of wax inhibitors15 or asphaltenes.16,17 The influence
of the presence of asphaltenes has been examined in determining
the WAT, the gelation temperature, and yield stress. Kriz and
Andersen16 reported that a dramatic increase in both WAT and
yield stress at 0.01% (w/w) asphaltene concentrations followed
by a rapid decrease at 0.02% (w/w). They explained this through
an asphaltene aggregation concept above a certain critical
concentration. Studies of the critical concentration of asphaltenes
have been published in various other papers.18-20 The reduction
of both gelation temperature and yield stress was also observed
at increasing asphaltene concentrations.17
Yield stress is an important property of the oil from restart
considerations. It is important to understand the impact of the
composition of the oil (wax content, wax type, etc.) on WAT,
pour point, and yield stress. Because asphaltenes may coprecipitate with waxes, the consequences of the presence of
asphaltenes on properties of importance in managing flow of
waxy oils also needs to be established. It is useful to look at
yield stresses at temperatures in relation to WAT and pour point
because these are two important characteristic mixture temperatures. In this work, we focus on the measurement of yield
stresses of carefully formulated model oils with the above
considerations. It should be noted that most of the previous
rheological data7-9,15-18 were obtained from rheometers with
(15) Pedersen, K. S.; Rnningsen, H. P. Influence of wax inhibitors on
wax appearance temperature, pour point, and viscosity of waxy crude oils.
Energy Fuels 2003, 17, 321328.
(16) Kriz, P.; Andersen, S. I. Effect of asphaltenes on crude oil wax
crystallization. Energy Fuels 2005, 19, 948953.
stlund, J.-A.; Chawla, H.; Wattana, P.; Nyden,
(17) Venkatesan, R.; O
M.; Fogler, H. S. The effect of asphaltenes on the gelation of waxy oils.
Energy Fuels 2003, 17, 16301640.
(18) Groenzin, H.; Mullins, O. C. Molecular size of structure of
asphaltenes from various sources. Energy Fuels 2000, 14, 677684.
(19) Acevedo, S.; Ranaudo, M. A.; Pereira, J. C.; Castillo, J.; Fernandez,
A.; Perez, P.; Caetano, M. Thermo-optical studies of asphaltene solutions:
Evidence of solvent-solute aggregation formation. Fuel 1999, 78, 997
1003.
(20) Oh, K.; Ring, T. A.; Deo, M. D. Asphaltene aggregation in organic
solvents. J. Colloid Interface Sci. 2004, 271, 212219.

Oh and Deo
Table 1. Elemental Analysis and Molecular Weight of
Asphaltene Used in This Study
analyses

C (%)

H (%)

N (%)

S (%)

H/C

Mna

ASP (field asphaltenes)

87.13

7.33

0.79

2.81

1.01

930

Mn ) number average molecular weight.

Figure 1. Carbon number distributions of W1 and W2 determined by

SIMDIS.
Table 2. List of the Model Oils Used in This Studya
wax
ASP
TOL
wax (wt %) K (v/v) (wt %) (wt %)

model oil
10% W1-K-MO1
20% W1-K-MO1
3% W2-K-MO2
5% W2-K-MO2
5% W2-TOL-MO1
5% W2-ASP0.01-TOL-MO1
5% W2-ASP0.1-TOL-MO1

W1
W1
W2
W2
W2
W2
W2

10
20
3
5
5
5
5

3:1
3:1
3:1
3:1
0.01
0.1

10
9.99
9.9

a K, ASP, TOL, and MO represent kerosene, field asphaltene, toluene,

and mineral oil, respectively.

the cone-and-plate geometry. The measurements in this paper

were performed using a rheometer with a vane fixture.
Experimental Section
Model Oil. Various model oils were prepared by using
different combination of waxes (W1 and W2), different white
mineral oils (MO1 and MO2), deordorized kerosene (K), toluene
(TOL), and field asphaltenes (ASP). The asphaltenes were from
the Rangely field,20 in northwestern Colorado. These had been
deposited in production tubing. Elemental analysis and molecular
weight of these asphaltenes are presented in Table 1. The
compositions of waxes (W1 and W2) were measured using hightemperature gas chromatography. The carbon number distributions of W1 and W2 are shown in Figure 1. The model oils
were prepared by using the procedure introduced in prior
papers.8-10 In the case of asphaltene addition, toluene was used as
a solvent before mixing with white mineral oil. Detailed compositions are presented in Table 2.
Measurement of WAT and Pour Point. Modified ASTM
methods were used to determine WAT and pour point using a
temperature-controlled bath and a cell-type jacket for coolant
circulation. The test cell used had the same size range (33.2-34.8
mm outer diameter and 115-125 mm height) as described in the
ASTM methods (D2500 and D97). The bath temperature was set
to 0 C for all model oils, except for the 10% W1-K-MO1, to
determine both the WAT and the pour point. In the case of 10%
W1-K-MO1, the bath temperature was set to 0 C initially to

Wax Gel Formation in Asphaltenes

Energy & Fuels, Vol. 23, 2009 1291

Figure 2. Yield stresses of model oil (20% W1-K-MO1) at two

different aging times as measured by the vane method.

measure WAT and then reset to -5 C for the pour point. The
measurement was carried out at 3 C intervals at first and then in
narrower temperature intervals as the measurements became closer
to the target. WAT was determined by the appearance of cloudiness
visually at the bottom of the jar that held the oil sample. It is much
easier to determine WAT in model oils than in dark crude oils.
The pour point was determined by observing no flow when the jar
was tilted for 3 s and held horizontal for 5 s. The pour point was
defined as the temperature at 1 C higher than the temperature of
no-flow observation. WAT and pour-point measurements were
repeated 3 times to ensure reproducibility.
Yield Stress Measurements. Brookfield RVDV-II+ was used
to measure the yield stress using the vane method at different
temperatures. Built-in maximum torque of RVDV-II+ is 0.7187
mN m. The bath temperature was set at 45 C before cooling the
model oil to the designated temperature. The cooling rate was fixed
at 0.8 C/min to the designated temperature, and the torque reading
was recorded after aging the gelled oil for 1 h duration at each
temperature interval. Dimensions of the four-bladed vane spindle
were 8.026 mm (0.312 in.) in diameter and 16.053 mm (0.632 in.)
in length, with the ratio of length/diameter of 2. The inner diameter
of the jacketed cylinder was 33 mm, for preventing the slip of gelled
oil during vane rotation. The oil level placed in the vane cell was
about 60 mm. The actual temperature of the vane trajectory in the
gel was measured by an external thermocouple. The temperature
variation between the core of the gel and the outside was less than
0.3 C.

Results and Discussion

The yield stresses at different temperatures below the pour
point were measured using the vane rheometer. The results are
organized as follows: (1) effect of aging on yield stresses, (2)
dependence of yield stresses on wax amounts and compositions,
and (3) yield behavior in the presence of asphaltenes.
Nguyen and Boger13,14 derived a correlation using the vane
method between the maximum torque reading obtained from
the rheometer and the yield stress, which is shown in eq 1.
-1

[ 2 d ( Hd + 31 )]

y ) Tmax

(1)

Here, H and d represent the length (or height) of the vane blade
and diameter of the vane rotation, respectively. Tmax represents
the maximum torque reading. On the basis of the maximum
torque rating of the viscometer, the maximum yield stress that
could be measured with this arrangement was 380 Pa.
Yield Behavior of Gelled Waxy Oils. Figure 2 shows the
torque readings obtained at the vane rotation speed of 0.3 rpm

Figure 3. Yield stresses of model oils. A linear increase in yield stress

was observed for all four model oils, with the slope dependent upon
the amount and type of wax in the oil.

(the minimum). The measured torque readings are presented as

a function of the vane rotation angle. The torque values were
determined after 2, 12, and 16 h aging of the 20% W1-K-MO1
gel at 6.7 ( 0.3 C. The aging time clock began after the water
bath temperature reached the set point. The aging effect on
gelation has been reported previously by Lopez da Silva and
Coutinho.7 Their study focused on the relationship between the
gelation time and gelation temperature. Elastic and viscous
moduli were measured in the temperature range of 40-52 C
with two different oils. It was observed that the gelation time
was becoming shorter at colder temperatures. However, the
aging effect has not been fully examined with gels developed
much below the pour point. In this work, the yield stress values
increased about 7% for 2 h of aging (253 Pa) to 16 h of aging
(271 Pa). The effect of aging from 2 to 16 h was not significant
as shown in Figure 2. Only an increase of 7% (18 Pa) was
observed for the 20% W1-K-MO1 sample.
Yield stress values for the four different model oils were
determined as functions of temperature and are plotted in Figure
3. A linear increase in yield stress was observed in all model
oils as the temperature decreased in the temperature range
studied in this paper. The yield stress of the gel is a meaningful
property only at or below the pour point. It is observed from
Figure 3 that the slope is characteristic of the wax amount and
wax composition. For model oils with W1, the yield stress of
20% W1-K-MO1 is much higher than that of 10% W1-K-MO1
at the same temperature (For instance, 564 Pa for 20%
W1-K-MO1 and 42 Pa for 10% W1-K-MO1 calculated
from the regression at 2 C shown in Figure 3). The slope of
the temperature versus yield stress line is steeper for 20%
W1-K-MO1 than for 10% W1-K-MO1. Similarly, for
model oils with W2, 5% W2-K-MO2 has higher yield values
and steeper yield stress relationships at the temperature ranges
measured than those of 3% W2-K-MO2. The slopes in Figure
3 are 61.7, 30.3, 41.6, and 18.7 Pa/C for 20% W1-K-MO1,
10% W1-K-MO1, 5% W2-K-MO2, and 3% W2-K-MO2,
respectively. Wax W2 is comprised of higher molecular-weight
compounds, in general, than W1. The yield stress values of 5%
W2-K-MO2 were higher than the yield values of 20%
W1-K-MO1 in this temperature range. However, the gel
strength increased more rapidly in 20% W1-K-MO1 as the
temperature decreased. The model oil with a higher content of
higher carbon number wax shows higher yield stress values and
rapid gel strength buildup at temperatures below the pour point.
Because the temperature effect on yield stress is pronounced,

1292 Energy & Fuels, Vol. 23, 2009

Oh and Deo

Table 3. WAT, Observation Temperature of No Flow, and Pour

Point Data of Model Oils
model
oil

WAT
(C)

no flow
(C)

pour point
(C)

x intercept from
Figure 3 (C)

10% W1-K-MO1
20% W1-K-MO1
3% W2-K-MO2
5% W2-K-MO2

17
25
25
30

4
13
10
18

5
14
11
19

3.4
11.1
10.7
16.8

it can be concluded that aging time has relatively little impact

on gel yield strength below the pour point.
The x-intercept value from the yield stress versus the
temperature plot provides an alternative method of determining
the pour point. WAT, observation of no flow, pour point, and
the x-intercept values obtained by extrapolation of the yield
stress versus the temperature line from Figure 3 are summarized
in Table 3. The x-intercept values are close to the temperature
of no-flow observation during pour-point measurements but
always below the temperature measured by the ASTM method.
In the ASTM method, a series of bath temperatures ranging
from 0 C are prescribed as bath temperatures. As a result,
samples with higher pour points in general (of the order of 20
C) may undergo supercooling before the no-flow point is
reached. This may result in a slightly higher value of the pour
point. The alternative method described in the paper is one more
way of ascertaining the no-flow condition and may be particularly suitable for oils with higher wax content.
Yield Behavior in the Presence of Asphaltenes. Venkatesan
et al.17 examined the effect of the presence of asphaltenes on
the yield stress at different temperatures. They presented the
yield stress values with respect to the wax percent at different
temperatures. Significant reductions in yield stress values were
reported in the waxy oil containing asphaltenes. They observed
a linear increase in yield stress in both asphaltene-free and
asphaltene-containing samples (0.05%, w/w and 0.1%, w/w) as
temperatures decreased.
In this study, we examined the yield stress values below the
pour point in the presence of asphaltenes at low concentrations
(0.01%, w/w and 0.1%, w/w). The model oils with asphaltenes
studied in this paper are presented in Table 2. Toluene was used
as a solvent for asphaltenes. The yield stresses (as functions of
the temperature) of 5% W2-TOL-MO1 (asphaltene-free), 5%
W2-ASP0.01-TOL-MO1, and 5% W2-ASP0.1-TOL-MO1
are shown in Figure 4. When asphaltenes were added, yield
stress values were lower and the rate of increase of yield stress
with temperature decrease was lower. However, as the temper-

Figure 4. Yield behavior of model oils in the presence of asphaltenes

compared to the model oils without asphaltenes.

Table 4. WAT, Observation Temperature of No Flow, and Pour

Point Data of Asphaltene-Added Model Oils

model oil

WAT
(C)

no flow
(C)

pour
point
(C)

x intercept
from Figure
4 (C)

5% W2-MO1
5% W2-ASP0.01-TOL-MO1
5% W2-ASP0.1-TOL-MO1

33
34
35

20
19
16

21
20
17

18.8
16.9
12.6

atures decreased further, the slope of the yield stress versus

temperature line resorted to the original slope (with no asphaltene), indicating the dominance of wax structures as more wax
came out of solution. Pedersen and Rnningsen15 reported that
the wax inhibitor acts as a steric hindrance agent in the wax
network structure. Venkatesan et al.17 also interpreted the
reduction in yield stress because of asphaltene addition to a
possible hindrance on wax gel network. Observations that are
not entirely consistent with those in Figure 4 have also been
reported previously. Kriz and Andersen16 observed the highest
WAT and yield stress at the lowest concentration of asphaltenes
in their experiments (0.01%, w/w). They showed a clear
demarcation between yield stress values in oils with asphaltene
concentrations below and above the critical concentrations.
A significant decrease in oil yield stress was observed above a
certain asphaltene concentration. They interpreted this to be the
concentration necessary for flocculation of asphaltenes, at which
point asphaltenes start hindering the formation of gel networks
rather than providing sites to generate wax crystallites, resulting
in decreases of WAT and yield stress. Below the critical
concentration, they theorized that asphaltenes may even act as
nucleation sites for wax crystallization, hastening precipitation
and providing higher yield stresses. Because shear was applied
during cooling in all of their experiments, their yield stress
values were far lower than those seen in this study (of the order
of 10 Pa). In this study, we found that the yield stresses
decreased by the addition of asphaltenes, even at very low
concentrations of 0.01 wt %. Table 4 shows WAT, no-flow
point, and pour point data of 5% W2-TOL-MO1, 5%
W2-ASP0.01-TOL-MO1, and 5% W2-ASP0.1-TOL-MO1. Asphaltene additions resulted in pour-point reductions,
of up to 4 C for additions of asphaltenes up to 0.1 wt %. Small
amounts of asphaltenes (0.01 wt %) also resulted in significant
reductions of the yield stress. Asphaltenes hinder the formation
of continuous, consistent gel networks, causing reduction in yield
stress. The magnitude of yield stress reduction at 0.01 wt %
compared to 0.1 wt % indicates that asphaltene aggregation
introduces the hindrance in gel formation by reducing the wax
generation sites, which is consistent with the observations of
Kriz and Andersen.16 The slopes of the yield stress versus
temperature lines went back to the original slopes of the
asphaltene-free oils at lower temperatures. In Table 4, the
x-intercept values in model oils with asphaltenes are obtained
by the extrapolation of three data points near zero yields. The
difference between the no-flow temperatures and x-intercept
values are larger in both samples with asphaltenes. This may
be caused by the fact that the oil at temperatures between the
pour point and x intercept has negligible yield stress values but
enough gel strength to prevent the flow. This is implicit evidence
that asphaltenes intervene in the wax network during the initial
network formation, which results in gel weakness near the pour
point. This study also provides insight concerning the yield
behavior of complex mixtures. The yield stress of an oil may
be higher than predicted in the presence of asphaltene at
temperatures much below its pour point, even though asphalt-

Wax Gel Formation in Asphaltenes

enes may depress the pour point and yield stress in the vicinity
of the pour point.
Conclusions
Gel strength development at temperatures below the pour
point was examined by measuring the yield stresses of a variety
of model oils using a vane rheometer. For the model oils without
asphaltenes, the yield stress increased linearly as the temperature
decreased. The extent of increase in yield stress values was
greater for model oils that had a higher percentage of wax. A
steeper increase in yield stress values with a decrease in
temperature was observed in model oils with a higher wax
content and with the wax containing a higher carbon number
distribution. Second, the role of asphaltenes in the evolution of

Energy & Fuels, Vol. 23, 2009 1293

the yield stress was explored. With asphaltene addition, yield

stress values were reduced and the rate of increase of the yield
stress with temperature decrease was lower. However, as the
temperatures decreased further, the slope of the yield stress
versus temperature resorted to the original slope (asphaltenefree model oil), indicating the dominance of wax structures as
more wax came out of solution. The x-intercept values obtained
from yield stress versus temperature were interpreted as noflow points, which could be used as alternative measures of
pour points. However, the deviation between the no-flow point
and x-intercept values was larger in asphaltene-added model
oils.
EF8006307