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Fuel 89 (2010) 10871094

Contents lists available at ScienceDirect

Fuel
journal homepage: www.elsevier.com/locate/fuel

Analysis of parafn precipitation from petroleum mixtures by means of DSC:

Iterative procedure considering solidliquid equilibrium equations
Baudilio Coto *, Carmen Martos, Juan J. Espada, Mara D. Robustillo, Jos L. Pea 1
Department of Chemical and Energy Technology, ESCET, Universidad Rey Juan Carlos, c/ Tulipn s/n, 28933 Mstoles (Madrid), Spain

a r t i c l e

i n f o

Article history:
Received 10 December 2008
Received in revised form 19 November 2009
Accepted 9 December 2009
Available online 22 December 2009
Keywords:
Wax precipitation
DSC thermal analysis
Solidliquid equilibrium
Flow assurance

a b s t r a c t
Wax deposition is a well known ow assurance risk in crude oil production due to temperature decrease
which depends mainly on the crude oil nature and the type and content of parafn. The prevention of this
problem requires a detailed characterization of the crude oil and the availability of reliable predictive
models.
The experimental determination and quantication of the precipitation process is quite complex and
time consuming and simpler techniques are of interest to carry out such study. Among them, differential
scanning calorimetry (DSC) technique is appropriate to develop routine essays and has been extensively
applied to determine wax appearance temperature in crude oil and fractions because the simplicity and
fast response of the technique.
However, the determination of wax precipitation curve from a quantitative DSC interpretation is usually based on pure n-alkane properties and involves some difculties. In this work, a new procedure has
been developed including the effect of the uid composition on the precipitation temperature and the
melting heat. Solidliquid equilibrium equations were introduced through a simplied thermodynamic
model in the integration procedure resulting in an iterative method combining experimental and calculated values. The nal method yields the wax appearance temperature (WAT), the full wax precipitation
curve and the estimated wax composition.
In order to validate the procedure, several crude oil fractions were used as standards due to the advantage of a narrow n-alkane distribution. Experimental characterization for the cloud point temperature,
the n-alkane distribution (determined by gas chromatography with mass detector, GCMS) and DSC
was carried out. The agreement between experimental results and those obtained from the DSC interpretation is a good check for the proposed procedure.
2009 Elsevier Ltd. All rights reserved.

1. Introduction
Waxes are mainly parafnic compounds that precipitate from
crude oils when exposed to low temperatures. The appearance of
these solids may cause different problems during oil extraction,
transport through pipelines or storage and, consequently, a great
experimental effort has been made to understand, describe and
predict the wax formation process [13].
The detailed study of wax deposition involves the experimental
determination of the Wax Appearance Temperature (WAT) and the
amount of wax precipitated as a function of temperature (wax precipitation curve, WPC). Other important parameters are the pour
point (temperature at which a crude oil or fraction stops owing)
and the cloud point (temperature at which a small solid phase
can be distinguish within a crude oil fraction).
* Corresponding author. Tel.: +34 91 4887089; fax: +34 91 4887068.
E-mail address: baudilio.coto@urjc.es (B. Coto).
1
Address: Repsol Technology Centre, 28933 Mstoles (Madrid), Spain.
0016-2361/$ - see front matter 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.fuel.2009.12.010

Crude oils are complex mixtures formed by a very high number

of compounds and the determination of the composition is very
difcult. The solubility of such different species depends on pressure, temperature and crude oil composition. Waxes can precipitate when the temperature of the crude oils decreases due to a
reduction of their solubility. These waxes are usually considered
to be heavy hydrocarbons (C20C60) mainly formed by linear n-alkanes [4] and represent the major risks in wax deposition problems. Their solubility is very low and a solid phase may appear
even when the content of heavy hydrocarbons is very low.
The modeling of the wax deposition process requires a good
knowledge of the solidliquid equilibrium involved. Different
authors have successfully developed thermodynamic models to
describe wax precipitation [1,49]. However, the scarcity of reliable complete available experimental information difcults models validation.
The study of the wax deposition process includes the development of experimental methods to determine the amount of precipitated waxes as a function of the temperature. Different methods

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B. Coto et al. / Fuel 89 (2010) 10871094

have been reported in the literature [1014], but usually present

two main limitations: the use of a solvent to dilute the crude oil
samples (which may have a remarkable inuence on the WAT value as the composition of the system is changed) and the study of
the wax precipitation at a single temperature (which makes
impossible to determine the WPC). Recently, a new wax precipitation method has been developed [15] based on a multistage fractional wax precipitation process without previous dilution of the
crude oil. This method allows obtaining the WPC for crude oils
with different wax content. However, although these experimental
methods are extremely time-consuming and cumbersome because
of manipulation of crude oil samples, they are very valuable for
understanding the wax deposition process.
To overcome these difculties mentioned above, alternative
procedures have been developed. Different experimental techniques such as differential scanning calorimetry (DSC) [4,1618],
nuclear magnetic resonance spectroscopy (NMR) [19] and Fourier-transformed infrared spectroscopy (FT-IR) [20] allows obtaining the amount of precipitated solid as a function of the
temperature.
The differential scanning calorimetry (DSC) technique has the
advantage of its simplicity and fast response which make it appropriate to develop routine essays. However, their application to
petroleum mixtures present some difculties related both to the
experimental technique and to the interpretation of the thermogram [4,18]. In this work, the optimization of several experimental
conditions was carried out and a new integration procedure has
been developed. Both the calibration and the thermogram integration were based on values for pure n-parafn. The integration procedure yields the wax appearance temperature (WAT), the wax
precipitation curve and the distribution function in weight percent
for n-alkane like compounds. The developed method was applied
to calculate both the wax appearance temperature (WAT) and
the wax precipitation curve (WPC) for different crude oil cuts,
obtaining consistent results.
The aim of this work is to provide a method to describe wax
precipitation from crude oils. This implies to determine the precipitation of waxes as well as the total amount of parafns. This allows thermodynamic models to be checked for predicting wax
deposition, and therefore, to anticipate ow assurance problems
related to precipitation of waxes.
2. Experimental

oil samples requires solving experimental difculties like the broad

and low-intensity signal, the wide temperature range to be covered
and the kinetic effects involved. Apart from that, the thermogram
interpretation present some additional difculties, mainly related
to the complexity in the determination of the baseline and the
integration procedure when a broad temperature range is studied.
In this work, experimental DSC conditions were optimized for
petroleum samples. Fig. 1 shows the cooling thermogram of a
crude oil in the temperature range between 80 and 120 C at several cooling rates. The intermediate rate, 3 C/min, was chosen in
order to reduce the kinetic effects keeping a good signal/noise ratio. In the nal optimized procedure, the temperature prole follows several steps:
(1) Previous step: Sample is heated at 3 C/min from 25 to 80 C
to completely dissolve possible solid phase and to remove
any thermal history.
(2) Cooling step: Sample is cooled down from 80 to 120 C at
3 C/min.
(3) Heating step: Sample is heated up from 120 to 80 C at the
same rate, 3 C/min.
The precipitation process during the cooling step is quite similar to the wax deposition occurring during the ow assurance studies and, in this work the cooling thermogram was used. Anyway, a
similar procedure could be applied to the heating thermogram.
Standard DSC calibration usually involves temperatures over
100 C which is far above from the range of interest in this application. In this work, a special calibration for low temperature was
carried out by using pure n-alkane within the range of n-C7 to nC18, thus covering a temperature range between 90 and 30 C.
Fig. 2 shows a plot of the pure n-alkane melting temperature determined by DSC in the cooling step against reference values [21]. A
linear calibration function was assumed which is also displayed
on Fig. 2. A small shift in the DSC measured melting temperature
in the cooling thermogram can be observed towards lower temperature values. This effect in the cooling process can be related to kinetic effects and it should be corrected by using the calibration
temperature curve.
2.3. The thermogram base line
As a wide temperature range is considered, the thermogram
baseline cannot be considered as a straight line. A special

2.1. Materials

1C/min
2C/min
3C/min
5C/min
8C/min

Heat Flow (mW)

The chemicals, suppliers and purities used for the DSC calibration were: n-C7 (Scharlau, 99%), n-C8 (Panreac, 99%), n-C12 (Alfa-Aesar, >99%), n-C16 (Alfa-Aesar, >99%), n-C18 (Fluka, P99.8%) and
Indium (Mettler Toledo).
The crude oil used in the optimization of the DSC experimental
procedure and the integration procedure was a naphtenic crude oil
from Africa provided by REPSOL. As an example of application, the
developed DSC procedure was used to study several crude oil cuts
from a naphtenic crude oil from Middle East also provided by REPSOL. Crude oil cuts studied (named according to their boiling temperature range in C) were: 130160, 160190, 190216, 240299,
299335, 335370, 370427, and 538565.

2.2. Differential scanning calorimetry

The experimental apparatus used is a DSC Mettler-Toledo
DSC822e. In DSC analysis the sample follows a temperature prole,
the heat transfer is registered, and any phase transition is quantied through the involved heat change. The application to crude

0
-100

-50

50

Temperature (C)
Fig. 1. Effect of the cooling rate in the DSC thermogram obtained for a crude oil.

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B. Coto et al. / Fuel 89 (2010) 10871094

40

1089



dC p;S dC p;SL
;

dT
dT T END

C p;L C p;SL WAT ;



dC p;L dC p;SL

:
dT
dT WAT

Temperature DSC (C)

20
0
-20

Fig. 3 shows the DSC cooling thermogram for a crude oil and the
baseline determined following the procedure described above.

-40
-60

3. Thermodynamic integration procedure

-80

3.1. Basic integration procedure

-100
-100

-80

-60

-40

-20

20

40

Melting Temperature for n-alkanes (C)

Fig. 2. Temperature calibration curve in the low temperature range obtained from
pure n-alkane compounds.

procedure was developed, which is not covered by the standard

DSC integration software.
The procedure developed in this work assumes that the sample
behaves as a usual liquid at temperatures above the WAT and as a
solid at very low temperatures under that named TEND, which is
usually set around 110 C. The meaning of such solid-like behavior represents that no further solidications are occurring. In both
extreme temperature ranges, the heat ow is exclusively related to
the heating/cooling of a one phase system and it can be tted to a
polynomial function representing the heat capacity of the system.
A second order polynomial was used for both phases:
2

Cp A B  T C  T :

Parameters A, B and C can be tted from the DSC thermogram for

both phases, yielding equations for the liquid and solid phases,
Cp,L and Cp,S, respectively. In the temperature range between TEND
and the WAT, both phases are present simultaneously and the heat
capacity is a combination of both equations. In this work, the heat
capacity of the two phase system, Cp,SL, was obtained by imposing
that heat capacity and its rst derivative is continuous both at TEND
and at the WAT:

C p;S C p;SL T END ;

2.5
Base Line
DSC Thermogram

Heat Flow (mW)

Dm Hi c  M i  T m;i ;

where for a given n-alkane i, DmHi is the molar melting heat (in
J mol1), Mi is the molecular weight (in g mol1) and Tm,i is the
melting temperature (in K). The value for parameter c (c = 0.6111)
was taken from literature [25,26]. As this linear behavior makes
easier any further calculation procedure, it was assumed for the rest
of this work.
DSC measured heat is converted into mass through Eq. (6) and
yields a precipitated mass distribution against temperature. The
cumulative sum represents the wax precipitation curve obtained
from the integration of the DSC thermogram. Fig. 4 represents
the WPC obtained by this basic integration procedure from the
thermogram represented in Fig. 3.
In the following step, the continuous variable temperature in
the mass distribution representation was converted into an integer
carbon atom number by using a correlation of pure n-alkane melting temperature vs. the number of carbon atoms. In this work, the
equation given by Won [26] was used:

T m;i a

2.0

b
;
Mi

where Tm,i is the melting temperature (in K), Mi is the molecular

weight and the parameter values are: a = 382.72 and
b = 20242.59. The obtained distribution function represents the
sample composition of precipitated n-alkane-like components and
it is plotted in Fig. 5 for the crude oil used as example.

1.5

1.0

3.2. Iterative integration procedure

0.5

0.0
-100

The difference between the DSC curve and the baseline (as
shown in Fig. 3) is a direct measurement of the total heat involved
in the phase change and can be converted into the corresponding
mass by means of the specic melting heat. As mentioned above,
the cooling process is studied, so the amount of precipitated substance can be then determined at each temperature which in fact
represents the wax precipitation curve.
In this work, the integration procedure was carried out in terms
of n-alkane components, assuming that they are the majority of the
precipitated compounds. Pure n-alkane properties from 4 to 24
carbon atoms were taken from Ref. [21] and several correlations
were checked for specic melting heat against melting temperature [2226]. The overall best agreement was found with the linear
equation given by Refs. [25] and [26] which represents an average
melting heat value for a given melting temperature:

-75

-50

-25

25

Temperature (C)
Fig. 3. DSC thermogram and calculated baseline for a crude oil.

50

The use of pure component correlations in the above procedure

is a wrong assumption and has to be corrected. The precipitation
temperature, Tp,i, at which an n-alkane precipitates in a mixture
is highly dependent on the composition and different from the
melting temperature. The melting heat has also to be modied because the displacement in the solidication temperature. There-

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B. Coto et al. / Fuel 89 (2010) 10871094

melting temperature and DpHi is the precipitation heat dependent

of the temperature through Eq. (8).
When considering no pressure effects, ideal liquid phase, and
the formation of pure component solid phases according to the
multiphase model for petroleum mixtures [28,29], the next simplied equilibrium equation can be obtained:

10

x i wi :

0
-100

-75

-50

-25

25

Temperature (C)
Fig. 4. Wax precipitation curve obtained by integration of the DSC thermogram for
a crude oil following the basic integration procedure.

0.020

Weight Fraction

0.015

0.010

0.005

0.000
0

10

20

30

40

50

Number C Atoms
Fig. 5. Distribution function (in weight fraction) of n-alkane like components
obtained from the basic integration procedure for a crude oil.

fore, melting heat capacities are needed in order to correct melting

heat values through the well known equation:

Dp Hi Dm Hi T mi

T p;i

Dm C p;i dT;

T m;i

where DpHi is the precipitation heat at the precipitation temperature Tp,i and DmCp,i is the heat capacity change in the melting process. In this work, the Pedersen correlation [27] was considered
for melting heat capacities of pure n-alkanes:
0

Dm C p;i a0 M i  b M i T;

where Mi is the molecular weight and the parameter values are:

a0 = 1.269 and b0 = 1.939103, for DmCp,i in J K1 mol1.
Thermodynamic equations of solidliquid equilibrium can be
established in terms of the function wi which is related to pure
component properties according to the following relation:

wi

fi0;s
fi0;l

exp

T mi

Dp H i
dT;
RT 2

11

That represents a straight relation between the liquid phase composition (xi) and its equilibrium temperature. When a liquid sample is cooled the solid formation for i-component, starts and
consequently this temperature represents its precipitation temperature, Tp,i. The precipitation of a component from a liquid mixture
modies the liquid composition and therefore the precipitation occurs over a temperature range. In this work we have considered as
precipitation temperature the point at which precipitation starts.
From Eqs. (10) and (11) is inferred that Tp,i and Tm,i can be very
different for typical low values of xi. For instance, in the crude oil
considered as example in this work, a composition of 0.015 wt%
in n-octane (Fig. 5) leads to a precipitation temperature about
90 C lower than the pure n-octane melting temperature. Such decrease of about 90 C in the n-octane precipitation temperature
corresponds, from Eqs. (8) and (9), to a decrease of about 85 J g1
in the specic precipitation heat, which represents a change higher
than 60%.
In order to include such a big effect of composition on precipitation properties, a procedure which combines experimental data
and calculation results is proposed. The crude oil sample, with an
n-alkane composition considered to be the n-alkane distribution
obtained from the basic integration procedure, is set well above
its WAT in order to have all the components in the liquid phase.
A step by step decrease of temperature was simulated and the solid
phase formation was computed for every component at each temperature considering the above equations and mass balance equations. Values for precipitation temperature and heat were
determined for each n-alkane.
Fig. 6 is a plot of the calculated precipitation temperature and
the melting temperature for pure n-alkanes vs. the number of carbon atoms. Fig. 7 is a plot of the specic precipitation heat against
the precipitation temperature together with the specic melting
heat against the melting temperature. As expected the precipitation temperature is much lower than the melting temperature because of the low values of the mole fractions of individual
components, and this large difference results also in a big differ-

100

Melting / Precipitation Temperature (C)

Solid (Weight %)

15

50
0
-50
-100
-150
-200

10

where fi0;s and fi0;1 are the fugacity of pure component i at the
reference state for solid and liquid phases, respectively, Tm,i is the

10

20

30

40

Number C Atoms
Fig. 6. Comparison of pure n-alkane melting temperature () and calculated
precipitation temperature (h) of n-alkanes within the studied crude oil.

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250

0.020

200

0.016

Weight Fraction

Melting / Precipitation Heat (J/g)

B. Coto et al. / Fuel 89 (2010) 10871094

150

100

0.012

0.008

0.004

50

0
-250

Iteration 0
Iteration 1
Iteration 2
Iteration 3

0.000

-200

-150

-100

-50

50

100

10

20

Melting / Precipitation Temperature (C)

50

second n-alkane distribution and a second correlation is obtained.

The process is repeated till no changes are obtained in the determined distribution function. Usually, 3 or 4 iterations are enough
to obtain convergence.
Figs. 9 and 10 show the n-alkane distribution curves and the
wax precipitation curves obtained in several iterations for the
crude oil studied.

ence between precipitation and melting heat values. However, it is

possible to see a similar trend in both plots for pure components
and for components in a mixture, new correlations can be obtained
from the computed values thus including the composition effect.
The iteration procedure described in Fig. 8 is proposed to integrate the DSC thermogram for crude oil mixtures. At the start
point, the DSC thermogram is integrated according to the basic
integration procedure and pure n-alkane correlations yielding a
rst n-alkane distribution curve. In the rst iteration step, the explained procedure to solve the SLE equations covering the whole
temperature range is carried out using as composition the obtained
rst n-alkane distribution. Values for the precipitation heat and
temperature are determined for each n-alkane in the mixture. Correlations, named rst correlation, between precipitation temperature, precipitation heat and number of carbon atoms are
determined. Experimental DSC thermogram is integrated again
using that rst correlation and a second n-alkane distribution
curve is obtained. A second iteration step is carried out with the

4. Application to crude oil cuts

Seven crude oil cuts, separated according to their boiling range,
were studied by means of the DSC technique with the experimental and integration procedure described above.
Fig. 11 shows the DSC cooling thermogram and the determined
baseline for the 190216 crude oil cut. As expected, a big difference
can be observed when it is compared with the crude oil (see Fig. 3)
as the DSC peak is narrower and its intensity higher. Similar results
could be observed for the rest of crude oil cuts, with the exception
of the heaviest ones whose signal becomes wider.

DSC Thermogram
Integration

WPC
Correlation
n-alkane-like
composition
SLE

Correlations for Precipitation Heat and

Temperature

New Integration
WPC

DSC Thermogram

Correlation
SLE

40

Fig. 9. Change of the n-alkane distribution curves along the iteration procedure.

Fig. 7. Comparison of melting heat vs. melting temperature () and calculated

precipitation heat vs. calculated precipitation temperature (h) of n-alkanes within
the studied crude oil.

Pure component
properties

30

Number C Atoms

n-alkane-like
composition

Fig. 8. Iterative procedure used for the integration of DSC thermogram.

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B. Coto et al. / Fuel 89 (2010) 10871094

20
18

14

Weight Fraction

16

Solid (Weight %)

0.20

Iteration 0
Iteration 1
Iteration 2
Iteration 3

12
10
8
6

0.15

0.10

0.05

4
2
0.00
0

-75

-50

-25

25

Temperature (C)
Fig. 10. Change of the wax precipitation curve along the iteration procedure.

10
Base Line
DSC Thermogram

Heat Flow (mW)

8
7
6
5
4
3
2
1
0
-100

-75

-50

-25

10

20

50

25

50

Temperature (C)
Fig. 11. DSC thermogram and calculated baseline for the 190216 crude oil cut.

The rst property obtained from this method is the value for the
WAT. Such value can be directly compared with the cloud point of
each sample. In this work, cloud points were determined according
to the standard procedure [ASTM 2500-05]. Table 1 lists the experimental cloud points and the WAT values determined by DSC in
this work. The agreement between both determinations is excellent taking into account that the accuracy of the standard method
ASTM 2500-05 is about 4 C and the lower limit of application is
45 C (Table 1).
Fig. 12 shows the n-alkane distribution curves obtained for the
190216 crude oil cut by the simple integration procedure (named

Table 1
Cloud points and determined WAT values for the crude oil cuts used in the present
study.
Crude oil cut

Cloud point (C)

WAT (C)

130160
160190
190216
240299
299335
335370
370427

<45
<45
<45
21
3
9
24

87.5
66.9
46.3
21.6
1.1
7.8
23.7

30

40

50

Number C Atoms
Fig. 12. Comparison of the n-alkane distribution curves for the 190216 crude oil
cut obtained by the simple integration procedure () and as a result of the iterative
procedure (- - -).

Iteration 0) and that obtained as a result of the iterative procedure.

The distribution is quite narrow showing that only a reduced number of components can precipitate. The effect of the iterative procedure is a shift of the distribution function to a higher number
of carbon atoms of the precipitated compounds. It is important
to point out the difference in the application to crude oils (see
Fig. 9), where the narrow initial distribution is also shifted to higher number of carbon atoms but simultaneously becomes much
wider describing a precipitation process with a high number of
compounds involved. Such different behavior can be considered
as a consistency of the integration procedure.
In order to verify the distribution functions calculated, they
were compared to those obtained by gas chromatography with
mass detector (GCMS). Fig. 13 shows the n-alkane distribution
curves for the 335370 crude oil cut obtained from the GCMS technique and that from DSC analysis with the iterative integration
procedure. The analysis carried out by GCMS should be considered
only approximate and non-quantitative. It is clear that the number
of carbon atoms of the n-alkane like compounds determined by
precipitation in the DSC experiments ts quite well with the number of carbon atoms of real n-alkane compounds detected by
GCMS. Even more, the weight percent for each compound deter-

0.10

0.08

Weight Fraction

0
-100

0.06

0.04

0.02

0.00
0

10

20

30

Number C Atoms
Fig. 13. Comparison of the n-alkane distribution curves for the 335370 crude oil
obtained from DSC analysis with the iterative integration procedure () and from
the GCMS technique (- - -).

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B. Coto et al. / Fuel 89 (2010) 10871094

25

Solid (Weight %)

20

15

10

0
-100

-75

-50

-25

Temperature (C)
Fig. 14. Wax precipitation curve for the 190216 crude oil cut obtained from the
simple integration procedure () and from the iterative procedure (- - -).

25

Solid (Weight %)

15

10

The authors thank REPSOL for providing the crude oil and crude
oil cut samples used in this work and for the nancial support
through the project Aseguramiento de ujo de crudos de petrleo:
estudio de la precipitacin de paranas.

References

0
-100

-50

method were shown both to study wax precipitation from crude

oils and from crude oil cuts.
A new procedure for the interpretation of the DSC thermogram
was developed. The base line was determined according to the expected functional dependency of the heat capacities with temperature for the liquid and solid phases involved. In the subsequent
integration process, an iteration procedure was implemented taking into account the effect of the composition on the melting temperature and the effect of heat capacity on the melting heat.
The iteration procedure showed good convergence with a reduced number of iterations. From the integration process, both
the wax precipitation curve and the distribution function of n-alkane like components are obtained.
As example, the developed procedure was applied to crude oil
cuts in a wide boiling temperature range. WAT values obtained
from DSC agree with experimental cloud points and in addition
the applicability range is wider.
The distribution function of n-alkane-like components obtained
is narrower for crude oil cuts than that for the whole crude oils as
expected and it is in good agreement with that obtained by GCMS
analysis.

Acknowledgements

130-160
160-190
190-216
240-299
299-335
335-370
370-427
538-565

20

1093

50

100

Temperature (C)
Fig. 15. Plot of the wax precipitation curve for all the crude oil cuts considered in
this work.

mined by both methods can be considered in good agreement.

Similar results were obtained for the other crude oil cuts.
Fig. 14 shows wax precipitation curve for the 190216 crude oil
cut obtained from the simple integration procedure and from the
iterative one. By comparing this curve with the crude oil WPC
(Fig. 10), it is possible to notice a large difference for temperatures
immediately under the WAT. A very fast increase of the precipitated solid amount is found for the crude oil cut, while for the
whole crude oil the precipitation is a progressive process. For the
same reason, the effect of the iterative procedure is more important for the crude oil than for the crude oil cuts, mainly at the lowest temperatures. Similar conclusions can be obtained for the rest
of crude oil cuts. Fig. 15 is a simultaneous plot of the wax precipitation curve for all the crude oil cuts considered in this work.

5. Conclusions
A procedure to study wax precipitation from petroleum mixtures based on the use of DSC technique was checked. Operation
conditions were optimized and a temperature calibration was carried out in the low temperature range. Good capabilities of the

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