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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
1088
2.1. Materials
1C/min
2C/min
3C/min
5C/min
8C/min
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.
0
-100
-50
50
Temperature (C)
Fig. 1. Effect of the cooling rate in the DSC thermogram obtained for a crude oil.
40
1089
dC p;S dC p;SL
;
dT
dT T END
dC p;L dC p;SL
:
dT
dT WAT
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
-80
-60
-40
-20
20
40
Cp A B T C T :
2.5
Base Line
DSC Thermogram
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
1.5
1.0
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
1090
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.
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;
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
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.
1091
250
0.020
200
0.016
Weight Fraction
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
50
DSC Thermogram
Integration
WPC
Correlation
n-alkane-like
composition
SLE
New Integration
WPC
DSC Thermogram
Correlation
SLE
40
Fig. 9. Change of the n-alkane distribution curves along the iteration procedure.
Pure component
properties
30
Number C Atoms
n-alkane-like
composition
1092
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
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
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 (- - -).
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 (- - -).
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
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.
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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