Journal of Petroleum Science and Engineering 168 (2018) 542–545

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Journal of Petroleum Science and Engineering

journal homepage: www.elsevier.com/locate/petrol

Wax appearance temperature (WAT) determinations of different origin T

crude oils by differential scanning calorimetry
Mustafa Verşan Köka,∗, Mikhail A. Varfolomeevb, Danis K. Nurgalievc
a
Petroleum and Natural Gas Engineering Dept., Middle East Technical University, Dumlupinar Bulvari, 06800, Ankara, Turkey
b
Department of Physical Chemistry, Kazan Federal University, Kremlevskaya str. 18, 420008, Kazan, Russia
c
Institute of Geology and Petroleum Technologies, Kazan Federal University, Kremlevskaya str. 18, 420008, Kazan, Russia

A R T I C LE I N FO A B S T R A C T

Keywords: In this research, wax appearance temperatures (WAT) of eight different crude oils from south-eastern region of
Crude oil Turkey were determined by differential scanning calorimetry. The experiments were performed at a heating/
Wax appearance temperature cooling-rate of 2 °C/min from 60 to −20 °C It was observed that the wax appearance temperature of different
Wax content origin crude oils was varied between 14.2 and 37.8 °C depending on the API gravity and wax content. It was also
Differential scanning calorimetry
observed that the crude oils have enthalpy of precipitation ranging from −3.42 to +6.39 mW and melting
Rheology
enthalpy from – 2.5 to +7.46 mW, respectively.

1. Introduction
Crude oil is a complex mixture of hundreds of different chemical
species consisting mostly of hydrocarbons known as paraffin's. In gen-
eral, this paraffin's align as long straight chain molecules, branched or
cyclic structures. It is known that paraffin wax produced from crude oil
consists primarily of long chain, saturated hydrocarbons with carbon
chain lengths of C18 to C75, which is referred to as macro-crystalline
wax.
The wax appearance temperature (WAT), also known as the cloud
point, is an important characteristic to evaluate the possible wax pre-
cipitation of a given fluid. It is defined as the temperature at which a
crude oil first precipitates. The techniques used to determine the WAT
are visual, cold finger, cross-polarized microscopy, light transmittance
and ultrasonic methods. Another method for WAT determination is
using differential scanning calorimetry (DSC).
In general, DSC measures the heat flow from or to the sample when
the sample is heated or cooled. Since crystallization will give out heat,
it will show up in the DSC curve as an exothermic peak during cooling
process. Since crystallization will give out heat, it will show up in the
DSC curve as an exothermic peak during cooling. DSC is also useful to
optimize chemical treatment parameters for cost-effective wax control,
including selecting optimal wax crystal modifier and treatment for-
mulation.
Depending on the geographic source and origin of crude oil, the
amount of wax contained and wax appearance temperature varies
(Table 1). In crude oils, when the temperature decreases, the dispersed
paraffin's begin to align together and when this process continues the
paraffin's form a solid crystalline wax structure and reaches a tem-
perature where it precipitates out of the crude oil. This temperature is
called wax appearance temperature (WAT). The wax appearance tem-
perature, also known as the cloud point, is an important characteristic
to evaluate the possible wax precipitation of a given fluid. On the other
hand, as it is known, thermal methods are quite popular to determine
the cloud point of petroleum fluids due to the high enthalpies of crys-
tallization of the paraffin's (Elsharkawy et al., 2000; Won, 1986).
WAT of crude oils determined by DSC, thermos-microscopy, rheo-
metry and other techniques has been studied by many authors. Bruning
et al. (Bruning, 1990) studied the rheological properties of crude oils
and concluded that the paraffin precipitation increases the system ap-
parent viscosity, promoting complete loss of fluidity, depending on oil
composition and temperature. On the other hand, Kruka et al. (Kruka
et al., 1995) described the change e in the rheological behaviour is
associated with formation and growth of paraffin crystals in the
medium. Hansen et al. (1993) studied the wax appearance temperatures
of crude oils by optical microscopy, viscometer and DSC under different
experimental conclusions and concluded that DSC technique can pro-
vide values for WAT that are lower than other techniques. Taraneh
et al. (2008) studied the inhibition of the crystallization and the melting
point of crude oil samples using the rheological properties and de-
termined that the improvement of the flow depends on the molecular
weight and the amount of asphaltene in the sample. Lucas et al. (1993)
studied the effect of additive on the pour point of the crude oils using a
new procedure adapted from the ASTM method, which consist in the

∗
Corresponding author.
E-mail addresses: kok@metu.edu.tr (M.V. Kök), mikhail.varfolomeev@kpfu.ru (M.A. Varfolomeev), danis.nourgaliev@kpfu.ru (D.K. Nurgaliev).

https://doi.org/10.1016/j.petrol.2018.05.045
Received 4 August 2017; Received in revised form 5 March 2018; Accepted 16 May 2018
Available online 18 May 2018
0920-4105/ © 2018 Elsevier B.V. All rights reserved.
M.V. Kök et al. Journal of Petroleum Science and Engineering 168 (2018) 542–545

Table 1
Properties of middle east crude oils (Elsharkawy et al., 2000).
Crude Oil Density (gr/cc) Viscosity (cp) MW Wax Content (%) WAT (oC)

Crude Oil-1 0.8859 1200 279 5.54 36

Crude Oil-2 0.8964 992 301 9.67 38
Crude Oil-3 0.8810 475 288 6.50 34
Crude Oil-4 0.8752 95.9 238 3.63 38
Crude Oil-5 0.9495 48 419 14.7 36
Crude Oil-6 0.9084 9.8 324 5.02 37
Crude Oil-7 0.8851 4.5 297 6.40 32

Table 2
Properties of crude oils.
Crude Oil API Gravity (oAPI) Viscosity (cp) Pour Point (oC) Wax Content (%wt) Asphaltene Content (%wt)

Crude Oil-1 37.2 1.2 −18 4.8 2.23

Crude Oil-2 31.0 2.0 −15 4.1 1.98
Crude Oil-3 27.3 2.4 −13 2.2 4.18
Crude Oil-4 26.7 5.7 −10 5.7 5.72
Crude Oil-5 24.1 6.5 −7 6.1 7.31
Crude Oil-6 22.9 7.6 −4 8.3 7.64
Crude Oil-7 14.9 28.0 +11 7.3 11.70
Crude Oil-8 11.8 420 +14 5.6 13.12

Fig. 1. DSC curves of crude Oil-1 (cooling).

Fig. 2. DSC curves of crude Oil-1 (heating).

determination of WAT when oil flow is not effected by gravity action
only. Jiang et al. (2001) conclude that wax appearance temperature
determinations by DSC method indicate lower values than the real ones,
mainly for crude oils with low paraffin content. Kane et al. (2004)
measured the steady viscosities under various shear rates and at con-
stant temperatures, aiming to understand the rheological behaviour of
crude oils and concluded that rheological modifications were attributed
to changes in morphology of small paraffin crystallites in agreement
with transmission electron microscopy observations. Kok. t. al (Kok
et al., 1996, 1997, 1999; Letoffe et al., 1995). studied WAT of crude oils
using different techniques such as viscometer, thermomicroscopy and
differential scanning calorimetry They concluded that DSC technique

543
M.V. Kök et al.
Table 3
Wax apperance temperature -WAT- (oC) and Enthalpy (mW) of Crude oils.
Crude Oil WAT (oC) WDT (oC)
Crude Oil-1 17.3 29.3
Crude Oil-2 20.2 33.5
Crude Oil-3 19.6 31.8
Crude Oil-4 33.7 35.9
Crude Oil-5 14.2 28.7
Crude Oil-6 16.5 31.4
Crude Oil-7 27.7 37.0
Crude Oil-8 37.8 30.0
can indicate WAT values for crude oils with low paraffin content. An-
other important result derived was that the WAT determined by DSC
technique was dependent on the paraffin distribution of crude oils. On
the other hand, comparison between predicted and measured results
showed that measured WAT values by DSC compare very well with that
predicted from the model for most crudes.
The aim of this research was to investigate the wax appearance
temperatures of different origin crude oil samples from south-eastern
part of Turkey, using differential scanning calorimetry (DSC) technique.
This is the first study to determine the WAT of Turkish crude oils from
this location. From this point of view, it is important to know the WAT
of these crude oils for transportation and storage processes. At the same
time, the aim was to assess the variations in the behaviour of crude oil
in heating and cooling processes which is also important during oil
production, transport through pipelines or storage.
2. Experimental
In this research, wax appearance temperature (WAT) of eight crude
oils from south-eastern region of Turkey, were determined using dif-
ferential scanning calorimetry (DSC). Properties of crude oil samples
was given in Table 2.
Wax content of crude oils was determined to represent the total
amount of wax and a similar procedure to that proposed by Burger et al.
(Burger et al., 1981) was carried out. In this procedure, crude oil is
dissolved in n-pentane and stirred during 30 min. Acetone (acetone/n-
pentane ratio 3:1) is added to the mixture and cooled down to 253K for
24 h. The solid phase present in the oil is separated by filtration in a
Buchner funnel using a glass micro-fibre Whatman filter No 934. The
solid phase is re-dissolved in n-hexane in order to remove asphaltenes.
After solvent removal, the final product is weighted (IP 389).
Before the DSC experiments, all the crude oils were thermally pre-
treated to 70 °C in closed containers to ensure complete dissolution of
all solid phase, then the closed container was left to cool to environ-
mental temperature. Dry nitrogen gas is purged through the DSC cell,
and the cooling is accomplished with a liquid-nitrogen cooling-acces-
sory. All the experiments were carried out by heating the crucible to
60 °C and keeping the temperature for 1 min, and then cooling it at a
cooling-rate of 2 °C/min from 60 to −20 °C. A 10 mg thermally pre-
treated crude oil specimen was then transferred into an aluminum
crucible, which was then sealed and weighed (ASTM® D2500). Three
parallel runs were made and averaged results were used to improve
precision. Calibration for temperature and heat flow is carried out using
the melting point and the heat of melting high purity metal indium.
Indium was chosen because it has known melting temperatures and
enthalpies of fusion.
3. Results and discussion
In DSC analysis, as the crude oil sample is cooled from the maximum
temperature, the heat trace measures the energy at each temperature.
In order to locate the wax appearance temperature, only the cool down
portion of the heat flow curve is selected. Once the paraffin's align
544
Journal of Petroleum Science and Engineering 168 (2018) 542–545
Enthalpy of Precip. (mW) Enthalpy of Dissol. (mW)
+2.25 +3.48
- 0.33 +0.45
- 3.42 - 2.15
+1.50 +2.27
+1.12 +2.90
+6.39 +7.46
+5.85 +6.75
+3.13 +3.96
themselves and begin to form crystals, energy in the form of heat is
given off. At this point, the exothermic reaction of crystallization is
recorded (Hansen et al., 1988). This temperature was determined to be
the wax appearance temperature (WAT). In other words, to calculate
the WAT, the onset temperature of the first peak has been considered
which is the intersection of the baseline and the tangent at the first peak
inflection point where, the exothermal peak corresponds to the crys-
tallization and hence precipitation of solid particles of wax during the
cooling process. In other words, WAT is taken as the onset temperature
of exothermic peak. At the same time, wax dissolution temperatures
(WDT) is taken as the temperature at which all the precipitated wax has
been dissolved into the oil matrix during the heating process. It is the
temperature corresponding to the endothermal peak on the DSC curve
during heating temperature scanning (Ronningsen et al., 1991).
Figures-1 and 2 show the conventional DSC traces of crude oils
obtained on cooling/heating processes in the temperature range of −20
to +60 °C, respectively. It was observed that the wax appearance
temperature of different origin crude oils was varied between 14.2 and
37.8 °C. The crude oils described in this study have a WDT ranging from
27.7 to 35.9 °C. It was observed that, the wax dissolution temperatures
(WDT) of crude oils was higher than wax appearance temperatures
(WAT) of crude oils studied (Table 3). Ronningsen et al. (Pedersen
et al., 1991a) reported that WDT is 5–28 °C higher than WAT for North
Sea Crude oils. They concluded that this difference between WAT and
WDT might be caused by undercooling and overheating that result in
non-equilibrium conditions during fast temperature scanning (Letoffe
et al., 1995; Hansen et al., 1991).
In the second part of the analysis, the thermodynamic quantity
equivalent to the total heat content of the crude oils were also de-
termined. Table 3 shows measured enthalpy of precipitation and en-
thalpy of dissolution for the crude oil samples. The total energy released
during cooling or heating process is proportional to the area between
the base line and the exothermal peak or endothermal peak, respec-
tively. It was observed that the crude oils have enthalpy of precipitation
ranging from −3.42 to +6.39 mW and melting enthalpy from - 2.5 to
+7.46 mW. For comparison, Middle East crudes have enthalpy of
precipitation ranging from 47.5 to 66.3 J/g and melting enthalpy from
60.5 to 78.6 J/g., respectively (Elsharkawy et al., 2000). 1Pedersen
et al. (1991b) and Pedersen (1995) presented a thermodynamic model
to predict the wax formation at different conditions and concluded that
the model successfully matches the experimental data for wax deposi-
tion for the North Sea crudes. Hamouda et al. (Hamouda and Viken,
1993) reported that the wax deposited in the pipeline at a higher
temperature, than those measured in the laboratory since pipeline wall
roughness and/or the presence of nucleation sites, such as solid, cor-
rosion products, play a great role for deposition of wax from under
saturated fluids.
It is found that the dissolution enthalpy is higher than the corre-
sponding enthalpy of precipitation. Heat released during wax crystal-
lization is the highest for crude oil-6, followed by crude oil-7 and the
lowest is detected for crude oil-3. These values indirectly correspond to
the amount of wax in the crude oils that crude oil-3 has the least
amount of wax. Throughout the study, no direct relations were found
M.V. Kök et al.
between the oAPI gravity of crude oils and wax appearance tempera-
tures.
4. Conclusions
In this research, wax appearance/dissolution temperatures of crude
oils from south-eastern region of Turkey have been characterized by
differential scanning calorimetry. Our measurements indicate that the
WDT is somewhat higher than the WAT for all of the crude oil samples
studied. Results also indicate that wax appearance temperature of dif-
ferent origin crude oils was varied between 14.2 and 37.8 °C. It was also
observed that the crude oil-3 has the highest enthalpy of precipitation
that corresponds to the lowest wax content.
Acknowledgement
This work has been performed according to the Russian Government
Program of Competitive Growth of Kazan Federal University.
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