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Thermodynamic Prediction of Paraffin Wax Precipitation in Crude Oil

Pipelines
L. Oyekunlea; O. Adeyanjua
a
Department of Chemical Engineering, University of Lagos, Akoka-Yaba, Lagos, Nigeria

Online publication date: 02 December 2010

To cite this Article Oyekunle, L. and Adeyanju, O.(2011) 'Thermodynamic Prediction of Paraffin Wax Precipitation in
Crude Oil Pipelines', Petroleum Science and Technology, 29: 2, 208 — 217
To link to this Article: DOI: 10.1080/10916460903330163
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 Petroleum Science and Technology, 29:208–217, 2011
Copyright © Taylor & Francis Group, LLC
ISSN: 1091-6466 print/1532-2459 online
DOI: 10.1080/10916460903330163

Thermodynamic Prediction of Paraffin Wax

Precipitation in Crude Oil Pipelines

L. OYEKUNLE1 AND O. ADEYANJU1

1
Department of Chemical Engineering, University of Lagos, Akoka-Yaba,
Lagos, Nigeria

Abstract Crude oils are generally very complex chemical systems consisting pre-
dominantly of hundreds to thousands of hydrocarbon compounds from simple low-
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molecular-weight paraffins to high-molecular-weight waxes. At low temperatures these

paraffins precipitate as a wax phase, which may cause the plugging of pipes and many
other problems. In this study the cloud point and the amount of the precipitated wax
at different temperatures were determined using a modified multi-solid wax model at
stock tank conditions and at high pressure for three live crudes and synthetic oil.
The model is based on the description of the nonideality of the phases in equilibrium
using the Peng-Robinson cubic equation of state for the liquid phase with a modified a-
function and the universal quasi chemical (UNIQUAC) equation for the solid phase,
which takes into account the effects of temperature, pressure, and composition on
the wax precipitation. The model assumes the crystalline nature of wax formed.
The experimental data and model predictions reveal that the cloud point decreases
with increased pressure and increases when the crude oil is mixed with more light
hydrocarbons. The values predicted by the new model show very little deviation from
experimental data.

Keywords crude petroleum, paraffins, thermodynamic modeling, wax deposition

Deposition of crystalline paraffinic waxes is frequently encountered during the produc-

tion and transportation of crude oil and its products. In the petroleum industry, wax
precipitation causes severe operational problems by plugging the valves and the flow
lines.
One of the most important measurements that characterize the waxing potential of
fluids is the cloud point. This is the temperature at which “cloudiness” of a relatively
transparent petroleum fluid is observed upon cooling. As long as the operating temper-
ature remains above the cloud point, wax precipitation will not occur. Typically, cloud
point measurements used in industry are inadequate. The standard ASTM D2500-88 or
IP 219/82 cloud point measurement methods are only applicable for clear fluids because
they rely on visual observation of the wax crystals. For dark crude oils, cloud points are
estimated from viscometry and differential scanning calorimetry (DSC). Oftentimes, the
viscosity or DSC data are misinterpreted. A more serious problem with these methods is
that sufficient wax must crystallize before the cloud point can be detected.
A number of engineering models have been proposed for calculating oil-wax equilib-
ria (Hansen et al., 1988; Erickson et al., 1993; Prausnitz et al., 1999; Banki and Firooz-

Address correspondence to Layioye Oyekunle, Department of Chemical Engineering, Univer-

sity of Lagos, Akoka-Yaba, Lagos 101017, Nigeria. E-mail: layioyekunle@yahoo.com

208
 Prediction of Paraffin Wax Precipitation 209

abadi, 2002). Wax precipitation may occur in reservoir formation, wellbores, production
tubings, submersible pumps, surface equipment, and surface pipelines. The present study
is limited to precipitation in pipelines where the primary mechanism for wax precipitation
is thermal cooling.
Early models focused on low-pressure fluids (Pederson et al., 1991; Coutinho and
Stenby, 1996; Lira-Galeana et al., 1996). The need for a model that could describe the
wax formation in live oil at reservoir condition promoted the development of the model
for high pressures (Ungerer et al., 1995; Pan and Firoozabadi, 1997; Lindeloff et al.,
1999).

Model Development
The model of Coutinho and Stenby (1996) for dead oil is the starting point. This model
treats the solubility of paraffin as ideal and contains no effect of pressure on the solid–
liquid equilibria. The general solid–liquid equilibrium relates, for each compound, the
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fugacity of both phases in the standard state, f , with the pure component thermophysical
properties.
!
f f
f ol Hitr Titr
 
Hi Ti
KiS D ln os D 1 C 1
f RTi
f T RTitr T
! (1)
f
ls Cp T Ti
ln f
C 1
R Ti T

Equation (1) can be expressed in terms of the solid- and liquid-phase compositions
.x s ; x l / and the activity coefficients . s ; l /

f f
!
xs s Hitr Titr
 
Hi Ti
ln l l D 1 C 1
x RTi
f T RTitr T
!! (2)
f
ls Cp T T
ln f
C i 1
R Ti T

f f
where Ti and Hi are the freezing point temperature and heat of fusion, respectively.
For normal paraffins of molecular weight, MWi :

f 20172
Ti;normal D 374:5 C 0:02617  MW i (3)
MW i

For all other components,

 
f f 80CNi
Ti;non-normal D Ti;normal 90 (4)
100 C CNi
f f
Hi D Ci MW i Ti (5)

where Ci is the constant (D0.163 cal/g
K).

 210 L. Oyekunle and O. Adeyanju

Effect of Pressure
The effect of pressure on the fugacity of a pure condensed phase is given by the
equation:

fioL
   
si L .P Po / L .P Po /
D Ki D oS exp .vi viS / D KiS exp vi (6)
xi fi RT RT

where KiS is given in Eq. (1).

Previous studies show that for carbon number greater than 10, the liquid and solid
molar volumes of normal paraffins are a linear function of molecular weight (Nelson
et al., 1960). The difference between the liquid and solid molar volumes can then be
expressed as in Eq. (7):

vi D C2 M Wi (7)
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Variation of Melting Points with Pressure

At the melting point, the solid–liquid K value is given as

f f
!
Hitr Titr
 
Hi Ti
KiL D exp 1 C 1
RTi
f Tm RTitr Tm
!! (8)
f
ls Cp
 
Tm Ti .P Po /
ln f
C 1 exp vi D 1:0
R Ti Tm RT

Equation (8) can be simplified to:

f f
! !
C1 Mi Ti Ti C2 Mi .P Po /
KiL D exp 1 C D 1:0 (9)
RTm Tm RTm

Solving for the melting temperature, T , and differentiating with respect to pressure
and setting C2 D 0:17 cm3 /g, C1 D 0:163 cal/g
K and making the unit conversions
gives:
ı
d Tm C2 C
D D 0:025 (10)
dP C1 bar

Solid-Phase Fugacity
The solid-phase fugacity .fi S / is related to the liquid-phase fugacity .fi L / by:
" # " #
fi L .T; P; x/ f S .T; P / fiL .T; P /
ig
D xi i L (11)
fi fi .T; P / fiig

The ratio of the fugacity of component i in the solid phase to the fugacity of component i
in the liquid phase is the inverse of the K values defined by Eq. (6).
 Prediction of Paraffin Wax Precipitation 211

xi iL P
xi iL P D (12)
KiL
" f
!
^L
i^L
 
si L i Pvi Hi T
Ki D D Ki L D L exp exp 1 f
xi i i RT RT Ti
!#
f
Hitr Titr ls Cp
 
T T
C 1 ln C i 1 (13)
RTitr T R Ti
f T

i^L is the fugacity coefficient of component i in the liquid mixture and iL is the fugacity
of pure liquid component I ; are evaluated at the system temperature and pressure.
Equation (13) is the final solid–liquid K value for the model. All that remains is
to choose a suitable equation of state to calculate the fugacity coefficient. The Peng-
Robinson equation of state was chosen because it correlates well with experimental
solid–liquid equilibria data.
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Fusion and Transitional Properties

f f
The melting point, Ti ; the enthalpy of fusion, Hi ; and the heat capacity of fusion,
Cpi , are evaluated for P, N, A species using following correlations (Won, 1989):
f
Ti D 374:5 C 0:02617Mi 20172=Mi (14)
f f
Hi D 0:1426Mi ti (15)

The correlations used for the normal paraffins are based on the data by Cavett’s (1964)
and Marano and Holder’s (1997) approach.
f
Ti D 421:63 1936412 exp. 7:8945.Ci 1/0:07194 (16)
f
Hi D 0:00355Ci3 0:2376Ci2 7:400Ci 34:814 (17)
f
The correlations proposed by Lira-Galeana et al. (1996) were used to calculate Ti
f
for naphthenes, iso-paraffins, and aromatics species and Hi for naphthenes and iso-
paraffins.
f
Ti D 333:5 419 exp. 0:00855Mi / (18)
f f
Hi D 0:05276Mi Ti (19)

The correlation proposed by Pan and Firoozabadi (1997) was used to estimate the enthalpy
of fusion for aromatic species
f f
Hi D 11:2Ti (20)

The correlation of Pedersen et al. (1991) was used to estimate Cpi for all P, N, and A
species.
Cpi D 0:3033Mi 4:635  10 4 Mi T (21)
 212 L. Oyekunle and O. Adeyanju

Critical Properties and Acentric Factor

The work of Pan and Firoozabadi (1997) provided a general correlation for critical
properties.
CMi
Pci D A Be (22)

For hydrocarbon with molecular weight of more than 300 g/mol coefficients A, B, and
C in Eq. (22) for the P, N, and A species were obtained from Pan and Firoozabadi
(1997).
Riazi and Al-Sahhaf’s (1995) expression was used to calculate the acentric factor of
paraffins:
!D 0:000185397Ci3 C 0:0448946Ci 0:0520750 (23)

Model Validation
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The developed model was tested using the experimental data from the literature (Pan
and Firoozabadi, 1997). Four crude oil samples 1–4 of different compositions were
employed.
The modified multi-solid model developed (Eq. (11)) was used to calculate the
wax precipitation of the oil samples. The interaction coefficients between CO2 and N2
were set at 0.002, the interaction between CO2 and hydrocarbon and between N2 and
hydrocarbon given by Pan and Firoozabadi (1997) was used. The interaction coefficient
between C1 and another hydrocarbon, Cj , were estimated from the equation:

kcij D 0:0289 C 1:633  10 4 Mj (24)

The interaction between the normal alkane/non(normal alkane and the nonnormal al-
kane/normal alkane are set to zero. The interaction coefficients between two normal
alkanes Ci and Cj as proposed by Pan and Firoozabadi (1997) were calculated by:
2
kij D 6:872  10 C 3:6  10 6 Mi2 8:1  10 4 Mi 1:04  10 4 Mj (25)

where kij D 0:0 (Mi  Mj and Mi  255), and Mi and Mj are the molecular weights
of light and heavy normal alkanes, respectively.

Characterization
The two-parameter gamma distribution function (Isehunwa and Falade, 2007) was first
used to generate the molar distribution of the plus fraction of the crude (plus fraction
is the last available residue; for sample 1 oil it is C40C fraction). Then the distribution
was lumped into three to four pseudocomponents of nearly equal weight. Hydrocarbons
from C10 to the plus fraction were also lumped in groups of five consecutive carbons.
The paraffins naphthenes aromatics (PNA) distribution of the four oil samples (1–4) and
naphthenes aromatics (NA) distribution for sample 2 oil were estimated. Erickson et al.
(1993) have shown that the amount of normal paraffin follows an exponential decay with
carbon number using high-temperature gas chromatography and the amount of normal
alkanes becomes negligible at very high molecular weights. An exponential decay approx-
imation was used to estimate the distribution of normal alkanes of all pseudocomponents
for samples 1, 3, and 4. The aromatic distribution of the pseudocomponents for the four
 Prediction of Paraffin Wax Precipitation 213

crudes is approximated according to the experimental data by Jaubert (1995). It was also
assumed that the fraction is resin-like if the molecular weight is between 800 and 950
g/mol and is asphaltene-like if its molecular weight exceeds 950 g/mol. Therefore, the
amount of paraffin and naphthenes is set at zero for the heavy pseudocomponents with
molecular weight exceeding 800 g/mol.

Results and Discussion

The proposed model was tested against experimental data and cloud points were predicted
for four oil samples at different pressures. Comparisons between the model predictions
and the set of data are presented in Figures 1–3, and the percentage weight of wax
precipitation is shown in Figures 4 and 5. The various plots revealed the fact that there
is a significant effect of pressure on the cloud point and the amount of wax precipitated.
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Figure 1. Comparison of experimental data and model prediction of cloud point for sample 1.

Figure 2. Comparison of experimental data and model prediction of cloud point for sample 2.

Figure 3. Comparison of experimental data and model prediction of cloud point for sample 3.
 214 L. Oyekunle and O. Adeyanju

Figure 4. Hydrocarbon composition of oil samples at 1 bar, mol%.

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Figure 5. Plot of wax precipitated against temperature for sample 1 at different pressures.

Effect of Pressure
The Figures 1–3 show that the model predictions agree quite well with the experimental
results, with the cloud point decreasing as the pressure increases, for a liquid mixture of
fixed composition. The model predictions are a little higher than experimental results: an
average of 4.5 K for sample 1, 8.2 K for sample 2, and 4.3 K for sample 3. These are
probably due to the paraffin contents of the oil samples, especially the higher percentage
of lighter fraction in sample 2 (51.3% C1 ). The total average absolute deviation percentage
(%AAD) between the calculated and experimental data was found to be 1.44%. In
Figure 1 a smooth curve was obtained by model prediction while there is a turning
point in the experimental results. The reason for this could be due to the uncertainty of
the experimental data because no turning point was observed with Figures 2 and 3. In
both Figures 5 and 6 it is clearly revealed that wax precipitation decreases with increases
in pressure as well as temperature. This is due to the increase in solubility of heavy
fractions in the liquid phase at higher pressure. Figure 5 for oil sample 1 shows an
almost linear relationship and Figure 6 for oil sample 2 can be represented by two lines
of different slopes. These are indications that the wax contents of the oils are of different
complexities. The simple explanation is due to the higher content of light fractions (51%
C1 ) of sample 2. The plots of wax precipitated against temperature for sample 3 are very
similar to those of sample 2.

Effect of Composition
Figure 4 presents the composition of the four oil samples. The composition mainly differs
in the content of methane (C1 ) and heavy C10C components. Sample 1 contains high C10C
 Prediction of Paraffin Wax Precipitation 215

Figure 6. Plot of wax precipitated against temperature for sample 2 at different pressures.
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Figure 7. Comparison of experimental and model prediction of cloud point for oil sample 4.

components and samples 2 and 3 have high contents of methane (C1 ). Sample 4 oil has
very low light fractions but contains the largest quantity of C10C components (>70%).
The effect of composition on wax precipitation was examined by using synthetic oil
(sample 4) obtained from the literature (Pan and Firoozabadi, 1997). The effect of pure
hydrocarbon such as C3 , n-C5 , n-C7 , n-C10 , n-C12, and n-C15 on solubility of solid wax
precipitation was investigated by determining the cloud point temperature of different
mixture of the synthetic oil and about 30% each of the hydrocarbons C1 to C15. Figure 7
shows the experimental and model-predicted cloud points when various hydrocarbons are
mixed. It is noted here that the cloud point initially decreased from C1 to C5 hydrocarbons
and then increased rapidly. These results agree with the experimental data. The results
are also in line with the solubility of heavy hydrocarbon (>n-C30) in light hydrocarbon
solvents (n-C5 -n-C12; Coutinho et al., 2001).

Conclusions
A thermodynamic model has been developed to predict the effects of light ends and high
pressure on solid paraffin formation in crude oils based solely upon a detailed crude oil
compositional analysis. The model prediction was validated against some experimental
data from the literature. The model prediction for the combined effects of light ends and
pressure and the experimental data agreed to within the experimental uncertainty of the
data. The model results also show that the cloud point is strongly influenced by heavy
normal paraffins, whereas the amount of precipitated wax depends on the concentration
of n-paraffins in solution with isoparaffins, naphthenes, and aromatics. The influence of
pressure on wax formation is shown to be as important as the influence of temperature.
 216 L. Oyekunle and O. Adeyanju

The developed model can provide an appropriate description of wax precipitation over a
wide pressure range.

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Nomenclature
CNi carbon number
Cp heat capacity of fusion, cal/Kmol
 Prediction of Paraffin Wax Precipitation 217

f fugacity of pure, condensed phase, bar

ig
fi fugacity of component I as an ideal gas, bar
L
fi fugacity of component I in liquid phase, bar
fiO;L fugacity of pure component I in liquid phase, bar
fiO;S fugacity of pure component I in solid phase, bar
fiS fugacity of component I in solid phase, bar
f
Hi heat of fusion for component i, cal/mol
tr
Hi heat of transition for component I, cal/mol
K solid–liquid K value
Kij binary interaction parameter for components I and j
MWi molecular weight of component I, g mol
P pressure, bar
Po atmospheric pressure, bar
R gas constant, J/Kmol
Si mole fraction of component I in solid phase
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T temperature, K
f
Ti freezing/melting temperature for component I , K
Tm melting point temperature, K
Ttr transition point temperature, K
V volume
v molar volume
viL molar volume of component i in liquid phase, cm3 /mol
viS molar volume of component i in solid phase, cm3 /mol
v difference between liquid and solid molar volumes for component i
x mole fraction

Greek Letters
ˆ^L
i fugacity coefficient of component i in liquid mixture
ˆL
i fugacity coefficient of pure liquid component i