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Chinese J. Chem. Eng.

, 14(5) 685—689 (2006)

Thermodynamic Modeling of Wax Precipitation in Crude Oils*


CHEN Wuhua(陈五花) and ZHAO Zongchang(赵宗昌)**
School of Chemical Engineering, Dalian University of Technology, Dalian 116012, China

Abstract Most of the crude oils contain waxes which precipitate when temperature drops, resulting in deposition
in pipelines and production equipment. It is necessary to set up a model which can predict the wax appearance tem-
perature and the amount of solid precipitated in the different conditions. A modified thermodynamic solid-liquid
equilibrium model to calculate wax precipitation in crude oil systems has been developed recently. The assumption
that precipitated waxes consist of several solid phases is adopted in this research, and the solid-solid transition is
also considered in the modified model. The properties of the pseudo-components are determined by using empirical
correlations. New correlations for properties of solid-solid and solid-liquid transitions are also established in this
work on the basis of the data from the literature. The results predicted by the proposed model for three crude oil
systems are compared with the experimental data and the calculated results from the literature, and good agreement
is observed.
Keywords waxy crude oil, solid-solid transition, solid-liquid equilibrium, thermodynamic model, wax precipita-
tion

1 INTRODUCTION compound that did not mix with other solid phases.
Crude oils are mixture of light and heavy hydro- However, studies on crystal structure in recent years
carbons. The components in crude oils can be classi- reveal that the miscibility of n-paraffins in a solid state
fied into paraffin, naphthene and aromatic compo- depends strongly on differences in molecular sizes (i.e.
nents[1]. Though the non-n-alkane components in carbon number). An n-paraffin mixture with a signifi-
crude oils are minor, it is essential to consider the in- cant carbon number difference appears to form eutec-
fluence of non-alkane components in the model since tic solids, whereas an n-paraffin mixture with a con-
their properties, such as fusion temperature and fusion secutive carbon number distribution forms a single
enthalpy, are much different from paraffin. The solu- orthorhombic solid solution[6]. So the assumption of
bility of each component of crude oils depends on the the multi-solid phase approach is not consistent with
temperature and composition of the system. When the real wax crystal behavior. Therefore,the model pro-
temperature of crude oil drops, the solubility of the posed by LiraGaleana et al.[5] is questionable for sys-
heavy fractions would be reduced and they will pre- tems that consist of compounds of similar molecular
cipitate in forms of wax and asphaltene first[2]. There sizes.
are problems caused by wax precipitation, such as the In this paper, the solid-solid transitions are used
change in the flow behavior of crude oil from Newto- to explain the multi-solid phase behavior of waxes
nian to non-Newtonian, the decrease of production before melting. New correlations have been estab-
rates, the increase of energy consumed and the failure lished to present the properties of solid solid transi-
of facilities. These problems are major concerns in the tions as functions of carbon number, considering the
production and transportation of crude oils. In petro- difference between odd and even carbon numbers. The
leum industry, methods[3,4] such as thermal treatment
fusion enthalpies of n-paraffin have different correla-
of pipelines, use of chemical inhibitors, etc., are used
tions based on the different crystal solid liquid transi-
to prevent wax precipitation. Of course, all of the
tions which were mentioned in Broadhurst’s paper[7]
methods increase operating expenses. A model that
can predict the conditions in which solids will pre- and new correlations have been established for them
cipitate and the amount of solids formed at different in this paper. Molecular thermodynamics along with
conditions can be used as a fundamental tool in pre- regular solution theory is used to describe the SLE
venting the solid precipitation. (solid-liquid equilibrium) system. Reliable experi-
In 1996, LiraGaleana et al.[5] presented a wax mental data for WAT (wax appearance temperature)
thermodynamic model in which a multi-solid phase and the amount of wax precipitated for three crude
approach was used for description of wax solids. This oils under several different temperature conditions
approach assumed that precipitated wax consisted of from the literature are used to validate the new wax
several solid phases, and each solid phase was a pure thermodynamic model.

Received 2005-07-25, accepted 2006-03-02.


* Supported by the National Natural Science Foundation of China (No.10272029).
** To whom correspondence should be addressed. E-mail: zczhao55@163.com
686 Chinese J. Ch. E. (Vol. 14, No.5)

2 THERMODYNAMIC MODELING The solubility parameters of other compound


2.1 Solid-liquid equilibrium modeling classes are estimated by the correlations proposed by
When the solid and liquid phases are in thermo- Leelavanichkul et al.[11] as follows.
dynamic equilibrium, the fugacity of component i in For naphthenic components:
solid phase and liquid phase must be the same δ iL = 8.7 − exp ( 2.219195 − 0.54907 mi0.3 ) (12)
f i L = f iS (1)
For aromatic components:
The fugacity in the solid phase, based on solid solu-
tion theory, is expressed by δ iL = 8.8 − exp ( 2.219195 − 0.54907mi0.3 ) (13)
⎛ P ViSdP ⎞ The solubility parameters of components i in
fiS = γ iS xiS fi oS exp ⎜
⎜ 0 RT ⎟⎟
⎝ ⎠
∫ (2)
solid solution, which is based on a cohesive energy
concept, can be written as[11]
Similarly, the fugacity in the liquid phase is 0.5
⎛ P Vi L dP ⎞ ⎛ ΔH if ⎞
δ iS =⎜ + δ iL2 ⎟
fi L = γ iL xiL fi oL exp ⎜
⎜ 0 RT ⎟⎟
⎝ ⎠
∫ (3) ⎜ V
⎝ i


(14)

By combining Eqs.(1), (2) and (3) the criterion of


equal fugacities can be expressed as 2.3 Density and molar volume
xiS γ iL fi oL ⎛ p Vi L − ViS ⎞ The liquid phase density diL,25 can be calculated
xiL
=
γ i fi
S oS
exp ⎜⎜
⎝ 0 RT
∫ dP ⎟


(4) from the following correlations proposed by Leela-
vanichkul et al.[11]
The volume differences between solid and liquid For paraffin components:
in crude oils are less than 10%[8]; so under low and
moderate pressures, the volume difference has little diL,25 = 0.815 + 0.06272 × 10−4 mi − 13.06 mi (15)
influence on the liquid-solid equilibrium. For this rea- For naphthenic components:
son the exponential term is neglected in this model
diL,25 = 0.865 + 0.06272 × 10−4 mi − 13.06 mi (16)
and the equilibrium relation can be simplified to
xiS γ iL fi oL For aromatic components:
= (5) diL,25 = −0.03ln mi + 1.02 (17)
xiL γ iS fi oS
The ratio of standard-state fugacity of sub- The molar volume of each component can be
cooled liquid to solid can be calculated from the calculated using knowledge of molecular weight and
following correlations[9]: density by
fi oL ⎡ ΔH if ⎛ T ⎞ ΔH it ⎛ T ⎞ Vi L = ViS = mi diL,25 (18)
= exp ⎢ ⎜ 1− f ⎟ + ⎜1 − t ⎟ −
⎢⎣ RT ⎝ Ti ⎠ RT ⎝ Ti ⎠
oS
fi
2.4 Properties of solid-liquid and solid-solid tran-
1 Ti f
1 Ti f
Δc pi ⎤ sitions
RT ∫ T
Δc pi dT +
R ∫ T T
dT ⎥
⎥⎦
(6) Won[12] proposed the following fusion correla-
tions for normal paraffins:
Ti f = 374.5 + 0.02617mi − 20172 mi (mi≤450g·mol 1)
with -

Δc pi = c Lpi − cSpi = 1.2739mi − 1.9467 × 10−3 miT (7) (19)


Ti = 411.4 − 32326 mi (mi>450g·mol ) (20)
f -1

2.2 Activity coefficients calculation The fusion enthalpies of paraffins can be calcu-
The activity coefficients for the solid and liquid lated from the correlations proposed in this work.
phases can be written in terms of the solubility pa- These correlations are developed based on the data
rameters based on regular solution theory: listed in Broadhurst’s paper[7]. In 1962, Broadhurst[7]
( ) ViS (δ mS − δ iS )
2
Vi L δ mL − δ iL
2
reported about the solid phase behavior of the normal
ln γ iL = ln γ iS = (8) paraffins and pointed out that when the temperature of
RT RT crude oil is lower than WAT, the solid phases of all
∑φ δ
δ mL = L L
i i ∑φ δ
δ mS = S S
i i (9) n-paraffins with more than nine carbon atoms in the
chain consist of four distinct crystal structures: hex-
(∑ x V ) = x V (∑ x V )
−1 −1
φiL = xiLVi L L L
i i φiS S S
i i
S S
i i (10) agonal, triclinic, monoclinic and orthorhombic. He
The solubility parameters in liquid state can be characterized the solid-liquid transitions of n-alkanes
calculated from a correlation proposed by Riazi and as follows: existing triclinic liquid transition for the
Al-Sahhaf[10] for paraffin components in crude oils: even paraffins from C10H22 to C20H42, orthorhombic
liquid transition for all normal paraffins above C40H82
δ iL = 8.6 − exp ( 2.219195 − 0.54907 mi0.3 ) (11) and hexagonal liquid transition for other n-paraffins.
October, 2006
Thermodynamic Modeling of Wax Precipitation in Crude Oils 687

Similarly, the solid-solid transitions for n-paraffins n-paraffins with odd carbon number:
were characterized as follows: orthorhombic hexago- 9 ≤ Cn ≤ 43
nal transition for the odd paraffins from C9H20 to
C43H88 and triclinic or monoclinic hexagonal transi- Ti t = 0.0039Cn3 − 0.4249Cn2 + 17.2812Cn + 93.1012
tion for the even paraffins from C22H46 to C42H86. Odd (26)
even differences are resulted from reasonable differ- ΔH i = 39805.146 − 6180.1417Cn +
t

ences in end group packing.


Consequently, the fusion enthalpies of the 347.9015Cn2 − 4.9602Cn3 (27)
n-alkanes have different correlations according to the n-paraffins with even carbon number:
number of carbon atoms and the odd or even carbon 22 ≤ Cn ≤ 42
number in the chain and established as follows.
Ti t = 0.0032Cn3 − 0.3249Cn2 + 12.7811Cn + 157.1936
n-paraffins with odd carbon number:
(28)
7< Cn <21 ΔH if = 0.5754miTi f (21)
ΔH i = 44019.633 − 6181.7767Cn +
t
n-paraffins with even carbon number:
8≤ Cn <22 ΔH if = 0.8064miTi f (22) 348.7432Cn2 − 4.9661Cn3 (29)
n-paraffins with all carbon number: The fusion properties of non-n-alkane compo-
nents are calculated from the following correlations
21≤ Cn <38 ΔH if = 0.4998miTi f (23) proposed by LiraGaleana et al.[5]:
Cn ≥38 ΔH if = 0.6741miTi f (24) Ti f = 333.46 − 419.01exp(−0.00855mi ) (30)
[9]
In Ji’s model , the fusion enthalpies were also For naphthenic components:
divided into several parts. However, this segmentation
ΔH if = 0.2216miTi f (31)
cannot match their crystal structures correctly and the
results calculated from correlations differ from the The following correlation developed by Pan et
experimental data[7] a lot. The correlation for fusion al.[5] is used to estimate the change in heat of fusion
enthalpies of n-paraffins proposed by Won[12] was for aromatic components:
adopted in most models. So this paper compares the ΔH if = 47.04Ti f (32)
mean squared deviation (MSD) between the experi- −
For C7 components, the properties of hydrocar-
mental data and calculated ones based on three models. bons have been given in the literature. However, for
From the data listed in Table 1, it can be seen that the C7+ fractions, their properties are estimated from all of
MSD using the present correlation is the best among the above correlations.
the three models.
2.5 Computational process
Table 1 The comparison of MSD among three models
(1) Initialize the system and input data xi and
Model MSD
Won model 1.959×108
mi for each component, including Tif 、ΔH if 、d and V
Ji model 2.572×108 for C7− components;
present model 1.689×107 (2) The first iteration, estimate first solid mole
fraction=0.5, γ iL = γ iS = 1.0 ;
The MSD is defined as follows: (3) Calculate initial solid liquid equilibrium con-
stant (KSL) objective function and its derivative;
1 50
MSD = ∑
n i =7
(ΔH ifexp − ΔH ifcal ) 2 (25) (4) Calculate next solid phase mole fraction, S;
(5) Calculate component mole fractions in liquid
The properties for solid-solid transition have not and solid phases;
been regressed into correlations in many papers. Ma (6) Calculate parameters: molar volumes, volume
and Guo[13] and Ji et al.[9] did this work in their model. fractions and solubility parameters for solid and liquid
However, in Ma’s paper the correlations were just es- phases;
tablished for odd normal parafins, and in Ji’s paper the (7) Calculate activity coefficients for solid and
latent heats for transitions were correlated with the liquid phases;
product of molecular weight and fusion temperature (8) Calculate next KSL objective function and its
using a linear function. The data listed in Corriou’s derivative;
paper[14] indicated that the enthalpies of the solid-solid (9) Check whether the sum of objective function
transition are a function of the carbon number and the is less than 0.001; if yes, calculate solid mass percent
curve is parabola instead of beeline. Several of each component and total mass percent solid, if not
third-order polynomial functions have been estab- return to (4).
lished in this model. Here, the objective function and its derivative are

Chinese J. Ch. E. 14(5) 685 (2006)


688 Chinese J. Ch. E. (Vol. 14, No.5)

calculated by sites, such as solid, corrosion products, play a great


(
⎡ xi KiSL − 1 ) ⎤ role in deposition of wax in under- saturated fluids.
Fobj = ∑ ⎢
(
⎢⎣1 + S KiSL − 1

) ⎥⎦ 3.2 Amount of wax
At a given temperature, the wax mass percent
⎧ ⎫
⎪ xi ( KiSL − 1)
2
d( Fobj ) ⎪ that precipitates from crude oil is calculated for 1 mol
dS
=− ∑ ⎨
⎪ ⎡1 + S ( KiSL − 1) ⎤ ⎪
2 ⎬ (33) of mixtures from
NS
⎩ ⎢⎣ ⎥⎦ ⎭
total precipitated mass
∑m
j =1
j ⋅ xSj ⋅ S

3 MODELING RESULTS AND DISCUSSION Wax mass % = = N

∑m ⋅ x
mass of crude oil
In order to prove the accuracy of the present i i
modified model of wax precipitation in crude oils, the i =1
experimental data for the WAT and the amount of wax (34)
precipitated for three crude oils under several tem- The mass percent of solids precipitated as a func-
perature conditions obtained by Leelavanichkul et tion of temperature for crude oils A, B, and C are
[11]
al. are used to compare with the results predicted presented in Figs.1, 2, and 3, respectively. From the
by the Leelavanichkul model and the present modified figures, we find out that the predicted amount of solid
model, respectively. The three crude oils have detailed precipitated with the present model is more in
compositional characterization[11] including a total of agreement with the experimental data than the
148 pseudocomponents for each crude oil. These Leelavanichkul model. Good predicting results benefit
pseudocomponents are determined based on carbon from taking account of the solid-solid transitions of
number ranges and hydrocarbon group types. The paraffins and establishing new correlations for solid
light end fractions ( C7− ) are attributed to single carbon solid transition and fusion enthalpies in the present
number. Each carbon number of the solvent fractions model.
(C7—C25) is classified into paraffin, naphthene and
aromatic fractions. The solute fractions, which include
C26 — C50 are differentiated as saturate (n-alkane,
non-n-alkane) and aromatic fractions. Finally the
+
heavy fractions are lumped into one C50 fraction,
two resin fractions, and three asphaltene fractions. All
the components of oil mixtures cannot be identified
since crude oils are the mixtures of thousands of dif-
ferent components. Therefore, the lumping charac-
terization is usually for predicting the thermodynamic Figure 1 Wax precipitation as a function of temperature
properties of the crude oils. These characterization for crude oil A
data are used as input for the modeling of solids pre- ◆ experiment; —— modified model;
cipitation at present research. ---- Leelavanichkul model

3.1 WAT
Table 2 shows the comparison between WAT
from experiment, the results predicted from the Lee-
lavanichkul model and present modified model. It can
be seen that the results predicted by the present model
shows slightly higher values than the experimental
results and the deviations are within experimental er-
ror. But then, Hamouda and Viken[16] reported that the
Figure 2 Wax precipitation as a function of temperature
wax get deposited in the pipeline at a higher tempera- for crude oil B
ture than those measured in the laboratory since pipe- ◆ experiment; —— modified model;
line wall roughness and the presence of nucleation ---- Leelavanichkul model

Table 2 Experimental WAT data and model predictions for crude oils
Sample Experimental results Leelavanichkul model Deviation Present model Deviation
crude oil A 298.2K 298.6K 0.4K 301.3K 3.1K
crude oil B 295.2K 293.4K -1.8K 295.4K 0.2K
crude oil C 294.2K 296.0K 1.8K 297.8K 3.6K

October, 2006
Thermodynamic Modeling of Wax Precipitation in Crude Oils 689

f fusion
L liquid phase
o standard-state
S solid phase
t solid-solid transition
Subscripts
m average value

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Figure 3 Wax precipitation as a function of temperature
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Superscripts

Chinese J. Ch. E. 14(5) 685 (2006)

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