A Consistent Thermodynamic Model for

Predicting Combined Wax-Hydrate in

Petroleum Reservoir Fluids
A.R. TABATABAEI, A. DANESH, B. TOHIDI,a AND A.C. TODD
Department of Petroleum Engineering, Heriot-Watt University,
Riccarton, Edinburgh EH14 4AS, United Kingdom

ABSTRACT: Low oil prices and the competitive nature of the oil industry world-
wide demand more cost-effective techniques in the development and operation
of offshore reservoirs. Extended-reach gathering networks and transportation
of unprocessed well streams by subsea pipelines are two attractive options that
could have significant impact in the development of marginal oil/gas fields.
These subsea pipelines are prone to wax and/or hydrate formation that can
potentially block the pipelines and lead to serious safety and operational prob-
lems. Wax and hydrate formation are both examples of solid deposition. They
are modelled conventionally and are studied independently. In this work we
describe a wax model that has been developed based on regular solution theo-
ry. The wax model was successfully coupled with an existing hydrate model.
The integrated wax-hydrate model is capable of predicting five phase equilib-
ria (i.e., water, liquid hydrocarbon, vapor, wax, and hydrate) as well as pre-
dicting the effect of wax formation on the hydrate phase boundary and vice
versa. The results show that a reliable wax-hydrate model can minimize the
risks involved in the transportation of fluids prone to wax and hydrate forma-
tion. The model can be used as a powerful tool in the design and operation of
subsea and arctic pipelines and production facilities.

INTRODUCTION

Petroleum waxes are complex mixtures of high molecular weight saturated

hydrocarbons, predominantly paraffins. Hydrates are crystalline compounds that
form at elevated pressures and low temperatures when water is in contact with spe-
cific light gases. In order for the wax to be formed at typical operating conditions,
there is a need for fairly high molecular weight hydrocarbons, usually above C16. For
the hydrate formation, the existence of light hydrocarbons or gases such as N2 or
CO2 with the presence of water is necessary.
The majority of crude oil and gas condensate fluids contain a certain proportion
of heavy hydrocarbon compounds that may precipitate as a waxy solid phase if the
fluid is cooled below a certain temperature. Wax precipitation may take place at a
temperature far above the freezing point of water, and is therefore a potential prob-
lem when petroleum mixtures are transported in pipelines (e.g., subsea), or treated
in a process plant. Wax formation usually leads to increased fluid viscosity, whereas

aTelecommunication. Voice: +44 131 451 3672; fax: +44 131 451 3127.
bahman.tohidi@pet.hw.ac.uk

392
TABATABAEI et al.: CONSISTENT THERMODYNAMIC MODEL 393

wax deposition generally results in an increase in pipeline roughness and reduction

in effective cross sectional area. Therefore, wax formation/deposition results in an
increase in pressure drop. When designing pipelines and separation plant it is, there-
fore, of importance to be able to determine the conditions under which wax precip-
itation takes place, and the amount of wax likely to form.
Gas hydrates are crystalline compounds formed by a combination of water with
suitably sized gas molecules. The amount of gas absorbed depends on the pressure
and composition of the gas, thus the composition of a gas hydrate is not constant.
The hydrates resemble ice but unlike ice they can form at temperatures well above
ice point. These compounds have been studied in detail by Sloan.1
To date many studies have been conducted on waxes and hydrates separately.
These studies have addressed problems related to only one of the two solid phases.
Although the characteristics of waxes and gas hydrates are very different, it is known
that the formation of one will affect the thermodynamics and kinetics of the other.
The objective of this paper is to develop a thermodynamic model that is capable of
predicting wax and hydrate phase equilibria, as well as the impact of wax formation
on gas hydrates and vice versa.
In this work, the regular solution theory model,2,3 has been used for the wax
phase modelling. A cubic equation of state (EoS) has been used to model water, liq-
uid hydrocarbon, and vapor phases. Solid solution theory has been employed to
model the hydrate phase.4,5

WAX MODELLING

For a system to be at equilibrium (vapor, liquid, solid) from a thermodynamic

viewpoint, the chemical potential of each component throughout the system must be
uniform. Hence, for an isothermal system the fugacity of each component through-
out the system must be the same. Details of hydrocarbon, water, vapor, and hydrate
modelling are discussed elsewhere.4,5 We briefly discuss modelling of wax phases
here.
The distribution of component i in the solid wax phase can be derived by using
the uniformity concept. The fugacity of each component in the solid (wax) phase
( f iS ) is defined by:
P S
v i dP
f iS = γ iS s i f ioS exp ∫ -----------
- , (1)
RT
0
where γ is the activity coefficient, s is the mole fraction, v is the molar volume, R is
the universal gas constant, and f is the fugacity. The superscript S refers to the solid
phase, superscript o to the standard state and subscript i to the component index.
The standard state fugacity of solid is related to the standard state fugacity of liq-
uid of the same component.6
 f ioL ∆h if ∆C P, i
- = ----------  1 – ------- + ---------------  1 – ------- + ln ------- ,
T T T
ln  -------- (2a)
 fi oS RT  Ti f  R  T if T if 
where Tf is the fusion temperature, ∆hf is the heat of fusion and ∆C P = C PL – C PS (CP
is the heat capacity and superscripts L and S refer to liquid and solid, respectively). In
394 ANNALS NEW YORK ACADEMY OF SCIENCES

this work the standard state fugacity of liquid has been calculated by using a cubic
EoS. The activity coefficient has been calculated from the regular solution theory as
RT ln γ i = v i ( δ i – δ ) 2 , (2b)
where δ = ∑i φ i δ i , and φ i = s i v i ⁄ ∑ j s j v j is the volume fraction of component i.
As shown in (2), the fusion temperature, T f, and the heat of fusion, ∆hf, as well as
the solubility parameters (δ) are required in order to calculate the fugacity of each
component in the solid (wax) phase(s). In this work, based on the available experi-
mental data,7–9 new equations for T f, ∆h f, and (δ) of each components were devel-
oped as
D
T f = A + BC n + CC n2 + ------ + E ln C n (3)
Cn

∆h f = A + BT f M + C ( T f M ) 2 + D ( T f M ) 3 + E ln ( T f M ) (4)
e ( A + BT r + C T r2 + DT r P c )
δ S = ------------------------------------------------------- (5)
EP c
where A, B, C, D, E, and F are constants, given in TABLES 1 to 3. Cn is the carbon
number, M is the molecular weight and Tr is the reduced temperature, (T/Tc). Also,
T f is in K, ∆hf is in Kcal/mole and δ is in (cal/cc)1/2. The comparison of the experi-
mental data7 with predicted T f and ∆hf by different correlations, including those
developed in this work, are presented in F IGURES 1 and 2, respectively. These corre-
lations are mostly valid for carbon numbers above C10 to around C45. As demon-
strated in the figures, classifying hydrocarbon components by odd/even, the latent

TABLE 1. Coefficients of Equation (3)

Carbon A B C D E
numbers
α − 426.659 − 16.560 0.1238 690.670 326.469
β 156.871 − 2.086 0.01223 − 775.598 76.219

TABLE 2. Coefficients of Equation (4)

Carbon A B C D E
numbers
α − 1.843 1.886 × 10–1 − 2.016 × 10–4 — 7.284 × 10–1
β 4.520 3.741 × 10–1 − 2.317 × 10−3 6.903 × 10−6 − 2.901

TABLE 3. Coefficients of Equation (5)

Carbon A B C D E
numbers
α 5.670 − 12.401 − 1.342 0.1602 0.025
β 3.573 − 3.749 − 4.399 0.2151 0.053
TABATABAEI et al.: CONSISTENT THERMODYNAMIC MODEL 395

FIGURE 1. Comparison between experimental and correlated T f from different

authors and this work.

FIGURE 2. Comparison between experimental and correlated ∆hf from different

authors and this work.
396 ANNALS NEW YORK ACADEMY OF SCIENCES

heat of fusion and the fusion temperature were best predicted by the correlations de-
veloped in this work.

RESULTS AND DISCUSSION

The wax model developed was used to predict the wax appearance temperature
(WAT), the lowest temperature at which no solid (wax) can form, as well as the
amount of wax formed in a number of multicomponent systems. F IGURE 3 shows
experimental10 and predicted WAT for a binary mixture of C6–C18. The predictions
from our model are in good agreement with the experimental data.
FIGURE 4 presents the measured11 and predicted amount of wax for a stock tank
oil with a reported WAT of 289.15 K. As shown in the figure, the experimental and
predicted WAT and the amount of wax are in good agreement, demonstrating the
reliability of the developed model. The heavy parts of the fluid were characterized
by using a semi-continuous approach.12 A gamma distribution function was used to
describe the continuous part.12
FIGURE 5 presents the experimental3 and predicted amount of wax formed in a
three-phase (wax–liquid hydrocarbon–vapor) system. This North Sea gas conden-
sate mixture was reported to have a WAT of around 309 K at 13.61 atm.3 The untuned
model predicts a WAT of 313 K, slightly over-predicting the amount of wax formed.
The model was tuned by adjusting the fusion temperature, T f, of the heavy hydrocar-
bons, and the error in predicting the WAT was reduced to less than 0.5 K. As shown
in the FIGURE 5, the tuned model gives reliable predictions on the amount of wax
formed.
Generally, hydrocarbon systems are prone to both hydrates (when water is
present) and wax formation (when heavier hydrocarbons are present). It is known

FIGURE 3. Experimental and predicted WAT for binary mixture of C 6H14 and C18H38.
TABATABAEI et al.: CONSISTENT THERMODYNAMIC MODEL 397

FIGURE 4. Comparison between experimental and predicted amount of wax for a

stock tank oil at 1 atm WAT = 289.15 K.

that the formation of one phase will affect the kinetics and thermodynamic behavior
of the other. The formation of gas hydrates removes lighter components of the fluid,
which could reduce the solubility of waxy compounds in it, affecting the phase
boundary of wax. On the other hand, wax formation will remove heavier compounds,
increasing the concentration of lighter compounds in the remaining fluid, affecting

FIGURE 5. Comparison of predicted amount of wax before and after tuning T f for a
North Sea GC at 13.61 atm.
398 ANNALS NEW YORK ACADEMY OF SCIENCES

the hydrate phase boundary. More importantly, although beyond the scope of this
work, it is likely that any wax or hydrate formation will provide a necessary nucle-
ation site for other solid deposition, promoting the formation of hydrate or wax by
reducing the required super-saturation. Traditionally, waxes and hydrates have been
investigated separately. One of the objectives of this work was to develop an inte-
grated wax–hydrate model, capable of predicting the impact of wax formation on the
hydrate phase boundary (and vice versa) for different hydrocarbon systems.
The wax model developed, in this study is based on regular solution theory. The
wax model uses the activity coefficient to solve the fugacities of solid (wax) compo-
nents. The vapor and liquid phase calculations have been performed using a cubic
EoS. The hydrate calculations are based on the Parrish and Prausnitz13 approach of
the extended van der Waals and Plateeuw thermodynamic model.14 The wax model
was successfully coupled with the existing hydrate model. The equality of the fugac-
ities for each component in different phases were considered as the equilibrium con-
ditions.12 The resulting thermodynamic model was used to simulate different
production scenarios, investigating a number of systems prone to wax and hydrate
formation.

TABLE 4. The calculated composition and the amount of the five-phases for volatile oil
at 280 K and 14.64 bar
Component z x1 x2 y h s
C1 0.3863 0.0004 0.0362 0.8160 0.0676 0.0000
C2 0.0626 0.0001 0.0358 0.1232 0.0141 0.0000
C3 0.0312 0.0000 0.0453 0.0413 0.0298 0.0000
i-C4 0.0055 0.0000 0.0151 0.0055 0.0053 0.0000
n-C4 0.0076 0.0000 0.0337 0.0082 0.0014 0.0000
iC5 0.0030 0.0000 0.0204 0.0018 0.0000 0.0000
nC5 0.0049 0.0000 0.0354 0.0024 0.0000 0.0000
C6-C10 0.0356 0.0000 0.2493 0.0008 0.0000 0.1163
C11-C15 0.0228 0.0000 0.1300 0.0000 0.0000 0.1214
C16-C19 0.0124 0.0000 0.0684 0.0000 0.0000 0.0695
C20+ 0.0864 0.0000 0.3303 0.0000 0.0000 0.6928
water 0.3417 0.9995 0.0002 0.0007 0.8818 0.0000
L1 L2 V H W
0.1076 0.1069 0.4466 0.2651 0.0738
z, overall mole fraction;
x1, mole fractions in liquid-water;
x2, mole fractions in liquid-hydrocarbon;
y, mole fractions in vapor;
h, mole fractions in hydrate;
s, mole fractions in wax.
L1, L2, V, H, and W are mole fraction of water, liquid hydrocarbon, vapor, hydrate, and wax,
respectively.
TABATABAEI et al.: CONSISTENT THERMODYNAMIC MODEL 399

TABLE 5. Prediction of wax and hydrate mole fractions for different cases of a volatile
oil at 280 K and 14.64 bar
Mole fractions No wax No hydrate All included
L2 0.2024 0.2041 0.1069
V 0.4308 0.4190 0.4466
L1 0.1551 0.3421 0.1076
W — 0.0348 0.0738
H 0.2117 — 0.2651
N OTE: L1, L2, V, H, and W are mole fraction of water, liquid hydrocarbon, vapor, hydrate, and
wax, respectively.

A typical phase behavior as predicted by the developed wax-hydrate model for a

volatile oil is presented in TABLE 4. The model is capable of predicting the amount
and composition of different equilibrated phases, including wax and hydrate. The
errors associated with predicting a multiphase equilibria with a wax only or hydrate
only model, in comparison with an integrated wax-hydrate model, are presented in
TABLE 5. In making our predictions the same volatile oil has been used. As shown in
TABLE 5, the predictions from the hydrate only or wax only model could exhibit sig-
nificant deviations in comparison with the combined wax-hydrate model, a fact that
causes problems in transportation.
To further investigate the effect of wax formation on the hydrate phase equilibria
and vice versa, two different mixtures were studied. Mixture-1 was rich in C1 and
C2, with around 90% (in mole) light components, whereas Mixture-2 was rich in
heavier compounds, with more than 50% (in mole) C7+. Initially the hydrate and wax
phase boundaries for the two oils were predicted, using the original composition.
Next, at a chosen point (T, P), inside the wax or hydrate region, the wax or hydrate
formed that was removed from the system and the hydrate and wax phase boundaries
for the remaining system were recalculated. These two mixtures were chosen be-
cause of their characteristics, they represented two diverse cases. In one case the
light components are dominant (i.e., the hydrate forming components dominates)
and in the other case the wax forming components are dominant. Hence, these results
cover the two extreme cases of the reservoir fluids, and result in understanding the
impact of wax formation on hydrates and vice versa.
FIGURE 6 presents the effect of wax removal at three different temperatures and
pressures for Mixture-1 (rich in lights), it can be seen that no major changes were
observed in the hydrate phase boundary. When the hydrates were removed, a large
reduction in the wax free zone of the remaining fluid was observed. The tests on
the Mixture-2 (rich in heavies) show almost a reversal phenomenon. As shown in
FIGURE 7, when hydrates were removed the reduction in wax free zone was very
small. On the other hand, the removal of wax had much greater impact on the hydrate
phase boundary of the remaining fluid, in comparison with Mixture-1. The impact
was found to be a function of the temperature and pressure of wax removal condi-
tions. The study showed a maximum shift of 1.5 K at 150 bar in the hydrate phase
400 ANNALS NEW YORK ACADEMY OF SCIENCES

FIGURE 6. Comparison of the effect of the wax on hydrate or vice-versa for mixture-1.

FIGURE 7. Comparison of the effect of the wax on hydrate or vice-versa for mixture-2
(heavier oil).
TABATABAEI et al.: CONSISTENT THERMODYNAMIC MODEL 401

boundary of Mixture-2, whereas the maximum shift in the wax phase boundary of
Mixture-1 was more than 10 K at 180 bar.
In a pipeline wax (or hydrate) formation will remove heavy (light) components
from a reservoir fluids. According to the results of this study, this will affect the
hydrate (or wax) phase boundary of the remaining fluid a fact that should be taken
into account.

CONCLUSIONS

In this study a wax model based on regular solution theory was developed and
tested on binary mixtures and multicomponent multiphase systems. In all cases we
have been able to predict both the wax appearance temperature (WAT) and the
amount of wax with good accuracy. It has been shown that the presence of both solid
phases can significantly alter the amount of solidification of the phases and hence
increases the transportation problems.
The wax model was successfully coupled with an existing hydrate model. It has
been demonstrated that the model is capable of predicting the five phase (liquid
hydrocarbon–liquid water–vapor–wax–hydrate) equilibria.
The resulting model was employed to investigate the impact of wax deposition on
the hydrate phase equilibria and vice versa. Two oil systems (with different concen-
trations of light and heavy hydrocarbons) that are prone to hydrate and wax forma-
tion were investigated. For the systems investigated, the results showed that wax
formation has little effect on the hydrate free zone of the remaining fluids. For light
systems, hydrate formation could have significant impact on the wax phase boundary
of the remaining fluid.

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