SPE-207984-MS

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A Comparative Evaluation of Thermodynamic Models for Prediction of Wax
Deposition

Jamilyam Ismailova, Aibek Abdukarimov, Bagdat Mombekov, and Dinara Delikesheva, Satbayev University; Luis E.
Zerpa, Colorado School of Mines; Zhasulan Dairov, Satbayev University

Copyright 2021, Society of Petroleum Engineers

This paper was prepared for presentation at the Abu Dhabi International Petroleum Exhibition & Conference to be held in Abu Dhabi, UAE, 15 – 18 November 2021.
The official proceedings were published online on 9 December 2021.

This paper was selected for presentation by an SPE program committee following review of information contained in an abstract submitted by the author(s). Contents
of the paper have not been reviewed by the Society of Petroleum Engineers and are subject to correction by the author(s). The material does not necessarily reflect
any position of the Society of Petroleum Engineers, its officers, or members. Electronic reproduction, distribution, or storage of any part of this paper without the written
consent of the Society of Petroleum Engineers is prohibited. Permission to reproduce in print is restricted to an abstract of not more than 300 words; illustrations may
not be copied. The abstract must contain conspicuous acknowledgment of SPE copyright.

Abstract
Wax deposition on inner surfaces of pipelines is a costly problem for the petroleum industry. This flow
assurance problem is of particular interest during the production and transportation of waxy oils in cold
environments. An understanding of known mechanisms and available thermodynamic models will be
useful for the management and planning of mitigation strategies for wax deposition. This paper presents
a critical review of wax prediction models used for estimation of wax deposition based on chemical
hydrocarbon compositions and thermobaric condition. The comparative analysis is applied to highlight
the effective mechanisms guiding the wax deposition, and how this knowledge can be used to model and
provide solutions to reducing wax deposition issues. One group of thermodynamic models assume that
the precipitated wax is a solid solution. These models are divided into two categories: ideal (Erickson and
Pedersen models) and non-ideal solutions (Won and Coutinho models). In the other group of models, the
wax phase consists of many solid phases (Lira-Galeana model).
The authors summarized the limitations of the models, evaluated, and identified ways to represent the
overview of existing thermodynamical models for predicting wax precipitation.
Within the strong demand from industry, the results of this manuscript can aid to aspire engineers and
researcher.

Introduction
Crude oil is a complex mixture of hydrocarbons, consisting of paraffins, asphaltenes, resins, aromatics,
and naphthenics (Behbahani 2016). Heavy paraffins in petroleum fluids often precipitate as waxes.
(Nasrifar 2011). Wax precipitation is a serious problem in the petroleum industry because it may result in
increasing pressure drop in pipelines, and in extreme cases may plug the wellbore, production facilities, and
transportation pipelines during oil and gas production. The change of temperature, pressure, and oil and gas
compositions may cause wax precipitation. When the fluids temperature is lower than the wax appearance
temperature (WAT), the heavy components in the oil phase will precipitate out and eventually deposit on the
pipe wall. (Zuo 2001, Yang 2016, Nasrifar 2011, Bagherinia 2016). With the growth of wax deposition, the
2 SPE-207984-MS

cost on pumping becomes more expensive and the risk for pigging plugging or pipeline blockage rises (Yang
2016). It is estimated that petroleum industry loses billions of dollars each year due to wax precipitation
and consequent productivity loss. (Sansot 2005, Nasrifar 2011). Techniques, such as, thermal treatment of
pipelines, addition of chemical inhibitors, and/or pigging, are commonly used to prevent wax accumulation.
The costs associated with such measures could be reduced significantly if accurate means to predict the wax

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precipitation conditions were available (Hong- Tohidi 2003). To design oil and gas production processes
efficiently, it is of great importance to predict the wax appearance temperatures (WAT) and the amount of
precipitated wax. Therefore, prediction of formation and precipitation conditions is of great importance in
petroleum industry.
A model that can predict the conditions in which solids will precipitate and the amount of solids formed
at different conditions can be used as a fundamental tool in preventing the solid precipitation (Chen 2006).
To assure the safety of pipeline transportation and reduce the cost of production, it is essential to establish an
accurate thermodynamic method to predict the precipitation of wax in petroleum fluids.Several predictive
thermodynamic models for paraffin phase behavior are presented in the literature. Here we present a critical
analysis of these predictive models.
Basically, there are two types of models to calculate wax deposition. One type assumes that the
precipitated wax is a solid solution.These models are divided into two categories: ideal and regular solutions.
The other type of models assumes that the precipitated phase consists of many solid phases (multi solid).
The regular solution theory was firstly employed to describe the solid-liquid equilibrium in crude oil
system by Won (1986), and a modified correlation for solubility parameter was applied to deal with the non-
ideality of solid phase. Then, Won (1989) used the combination of regular solution and the Flory-Huggins
solution theory to describe the non-ideality of the liquid phase. The new wax prediction model precisely
predicts the cloud point of waxy mixtures and the composition of precipitated wax. In 1991, Pedersen et
al. presented a wax model based on modifications to the approach by Won (1989). A modified regular
solution approach was applied to both the liquid and solid phases. The model proposed by Erickson et
al. in 1993 was a modification of that of Won (1989). The ideal solution approach was applied to solid-
liquid equilibrium (SLE) calculations. In 1995 and 1996, Coutinho et al. evaluated several approaches for
calculating activity coefficients in SLE, including the Flory–Huggins, Universal Functional Group Activity
Coefficient (UNIFAC), Flory free-volume, and entropic free-volume. In 1996, Lira-Galeana et al. presented
a wax thermodynamic model in which a multi-pure-solid approach was used for description of wax solids.
This approach assumed wax solids consisting of multiple solid phases, and each solid phase was a pure
compound. Lira-Galeana's research became the basis for the development of more advanced multi-solid
models.
The aim of this work is to, based on the results of critical analysis, identify the most suitable model for
further development of a modified thermodynamic model of wax deposition and increase the prediction
efficiency for crude oils from Kazakhstani fields.

Statement of theory and definition

In the last four decades, various thermodynamic models have been developed to calculate wax
appearance temperature (WAT) and amount of precipitated wax in a paraffinic hydrocarbon mixture. These
thermodynamic models based on the morphology of solid phase(s) were divided into two assumptions,
solid solution (SS) and multi-solid (MS). The solid solution (SS) assumption consists of the miscibility of
the solid components in the paraffinic hydrocarbon mixture, where almost all or most system components
form a single amorphous solid phase (K.W. Won 1986, 1989, J.H. Hansen 1988). It follows that one would
consider the "molecular interactions" among the components and the modeling focus would be on the "solid
phase activity coefficients". The terminology multi-solid (MS) refers to multiple crystalline solid phases,
and each crystalline solid phase is represented by a system component.
SPE-207984-MS 3

Solid solution model

At the beginning, the SS models have been used to describe solid phase behavior of metal alloys. A
common assumption is that the solid phase is a solution and its nonideality is caused by significant molecular
interactions. Won (1986) was the first researcher who applied the SS assumption to wax precipitation
problems in a paraffinic hydrocarbon mixture.

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Won (1986) proposed a new method of calculating three-phase equilibria including gas, liquid, and solid
solutions, and to consider non-idealities of solid solutions in his model he uses a new modified solubility
parameter.Based on the iso-fugacity relationship between different phases, the solid-liquid equilibrium
coefficient, , was as

(1)

where, Si and Xi stand for the mole fractions of component i in solid and liquid phases, respectively, are
activity coefficients, Tf is the fusion temperature, is the heat of fusion,∆Cpis the heat-capacity change
of fusion, and ∆V is the volume change of fusion.
A modified regular solution model was used to estimatethe activity coefficients in both liquid and solid
phases,

(2)

where Vi is the molar volume, δi is the solubility parameter, and δ is the average solubility parameter of
the mixture.
Won (1986) presented qualitatively satisfied results for a synthetic n-alkane mixture containing 41
components ranging from C1 to C40, as well as CO2 using theSoave-Redlich-Kwong equation of state
for vapor-liquid equilibria and a new "modified regular solution"theory for the liquid-solid equilibria. He
modified his earlier model by adding a combinatorial Flory-Huggins term to calculate the liquid phase
activity coefficients presented in eq. 3. Won (1989) presented a new thermodynamic correlation to predict
WAT and the composition of precipitated wax phase over a wide temperature range (210 to 320K). In
addition, a pure-solid phase for the heavier hydrocarbon component and the heat-capacity effect on the
fugacity ratio was considered.
Even with such uncertainties, the model gave qualitative results for the amount of precipitated wax
depending on the temperature with accuracy of ±3 K.
(3)
where M is the mole fraction average of Mi
By following the approach by Won (1986), many researchers have put a lot of effort into the modification
of the activity coefficient model for both liquid and solid phases. Hansen et al. (1988) proposed a Gibbs
energy model for the solid phase, obtained as a result of the processes of nucleation and growth of wax
crystals, and a Flory-Huggins model (1941) for the liquid phase. The wax appearance point (WAP) of
17 different stabilized North Sea crude oils were measured using a LABORLUX 12 microscope with
temperature control. Then, the WAT of the 17 crude oil mixtures were predicted using Won’s model (1986).
The WAT obtained using the model of Won (1986) are somewhat higher than those measured. To improve
the results, Hansen et al. (1988) carried out detailed characterization of C7+ fraction (160 pseudocomponents)
and reduced the activity coefficients (=10-10 very small compared with those calculated using Won’s model).
The experimental results are in reasonable agreement (within ±2 K) with the values predicted by the new
model.
4 SPE-207984-MS

Multi-solid model
Lira-Galeana et.al. (1996) were the first research group who proposed a multi-solid model to predict
wax precipitation in hydrocarbon mixture. The proposed method based on the assumption that pure solid
components do not mix after wax precipitation andconsiders the role of phase stability analysis that identify
the pseudo or pure components that precipitate as pure solids. The Peng-Robinson EOS was used to

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calculate the fugacity of components in the fluid phases. Authors modified the melting point temperature,
proposed by Won (1986). The asymptotic temperature relation of the proposed equation "corresponds to
the average melting temperature of heavy naphthenic and aromatic hydrocarbons with carbon numbers
above 30 (Won 1986). The enthalpy of fusion of paraffinic hydrocarbons proposed by Won (1986) was
modified due to the overestimation of the wax amount below the cloud-point temperature. The experiments
and analytical calculations were performed on binary mixture and on the multicomponent mixture. The
binary mixture results showed the improvement of analytical results after including a term for the heat
capacity of fusion. The multicomponent mixture represented by 8 crude oil samples. The experimental
results of wax precipitation characterization were matched by the analytical model results. Moreover,
the proposed method "reproduces the experimentally observed discontinuous deposition behavior of real
petroleum systems" (Lira-Galeana et al. 1996). Since now, this model is widely used in this area.
Model formulation proposed by authors
Consider a system of Ns precipitating species, and N components. The equation of phase equilibrium is
N vapor-liquid isofugacity equations
(4)
Ns liquid-solid isofugacity equations

(5)

For the non-precipitating components

(6)

For precipitating components, where all solid phases are pure

(7)

In conclusion, although prior modeling studies have shown various degrees of success in calculating
WAT and wax precipitation profile for simple n-alkane systems and oil samples, these approaches are
correlative or empirical in nature and fail to take advantages of the experimental findings on solid formation
by assuming only unary amorphous solid phase formation.
SPE-207984-MS 5

Wax prediction model chronology

Various attempts were done by researchers regarding modification and application of solid-state wax
prediction models. One of the earliest models after Won (1986) belonged to Jens H. Hansen, et al. (1988)
measured the wax appearance temperature (WAT) of 17 different stabilized North Sea crude oils using
a LABORLUX 12 microscope with temperature control. Then, the WAT’s of the 17-crude oil mixtures

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were predicted using Won’s model. The WAT obtained using the model of Won are somewhat higher than
those measured. To improve the results, the authors carried out detailed characterization of C7+ fraction and
reduced the activity coefficients. Further, to improve the calculations the authors used a group-contribution
approach to model the interaction parameters, xij. Group interaction parameters needed for three different
types of interactions (paraffin, naphthene, aromatic): PN-PN, PN-A, A-A. The authors in their model
calculated activity coefficients using following equations:
(8)
(8.1)
(8.2)
The experimental results were in reasonable agreement with the values predicted by the new modified
model.
One year later K.W. Won (1989) proposed new thermodynamic correlations to predict cloud point
temperatures and the compositions of the precipitated waxes over a wide temperature range from about 210
to 320K. Earlier, (Walsh and Mortimer, 1971; Riazi and Daubert, 1987) considered only the highest phase-
transition temperature in their model; on the other hand, the K.W. Won (1989) took the other latent heats of
phase transitions and the effect of the heat capacity change into account.

(9)

At 1991 Karen Schou and Per Skovborgpointed out the weakness of Won’s and Hensen et al. liquid –
wax phase equilibria model and improved their model by increasing significantly the solid-phase solubility
parameters. Authors consider in their model not only n-paraffines but also branched paraffines naphthenes,
and aromatics which solubility parameters are 20% higher than those of n-paraffins and taking in account the
heat capacity difference between hydrocarbons in the liquid and solid states.Additionally, enthalpy change
associated with transition in the solid material is also considered. Then, authors predicted the amount of wax
precipitated as a function of temperature at atmospheric pressure using regular solution theory for liquid and
solid phases. The liquid and solid-phase solubility parameters were assumed for paraffinic and naphthenic
components of a C7+ fraction,

(10)

The liquid-solid transition enthalpy of paraffinic components (n paraffin and isoparaffins) is also
estimated,
(11)
the liquid- and solid-phase heat capacities,
(12)
where, a4 and a5 are constants independent of component.
6 SPE-207984-MS

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Onward, Joao A. P. Coutinho (1998) proposed apredictive version of the UNIQUAC equation to model
the solid phase nonideality of paraffinic hydrocarbon mixture. The authors claimed that the current model
performs better than Wilson (1964) in predicting the phase behavior of complex paraffinic hydrocarbon
mixtures in both aliphatic and aromatic solvents, because up to now Wilson model was considered the best
model for this kind of systems. The authors adapted UNIQUAC model for solid phase, since UNIQUAC
model was developed for liquid phase. The modified version of UNIQUAC model.

(13)

(14)

(15)

Another problem using UNIQUAC model for the solid phase is the evaluation of the structural parameters
r and q. The author addressed this issue by dividing the original r and q values by the r and q for the 10
methylene units:
(16)

(17)

Then, in 1999 Jerome Pauly et al.established an EOS-GE thermodynamic model where the non-ideality
of liquid and vapor phases were described by the SRK-EOS associated with UNIFAC and for solid phase,
the predictive Wilson equation was applied.

(18)

Julian Y. Zuo (2001) et al. developed a solid-solution model for improving the representation of wax
precipitation from petroleum fluids, namely for calculating wax appearance temperatures and the amount of
precipitated wax for synthetic oils and, dead oils, live oils and gas condensates, which considers the Poynting
correction in the solid fugacity calculation, addresses the effect of increased pressure on the fugacity. The
authors used the PR EOS in the vapor and liquid phases to calculate the fugacity coefficient.

(19)

The last term on the right-hand side of equation is the Poynting correction. Pedersen, Thomassen, and
Fredenslund (1989) characterization procedure was improved to estimate the critical temperature, critical
pressure, and acentric factor of each WAT or plus fraction.
SPE-207984-MS 7

Also, correlations proposed by Won (1986) and Pan et al. (1997) are used to calculate the melting
point temperature in K and enthalpies of fusion in cal/mol for the n-paraffins and residue of subfraction
respectively
(20)

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(20.1)
(20.2)
(20.3)
At 2002 Coutinho et al.,described how their model can be used in conjunction with conventional
equations of state to perform wax equilibrium calculations for black oils. Examples are given showing how
well the model can predict both wax appearance temperature and the amount of wax precipitated at varying
temperatures with or without n-paraffin analyses. The examples include the effect of pressure on live oils.
Hong-Yan Ji et al (2003) presented a thermodynamic model for wax that considers the calculation of
fusion properties and heat capacity for n-paraffins dependent on the carbon chain length and whether carbon
numbers are odd or even. The new approach to describing paraffin wax is based on the UNIQUAC equation
and considers the effect of pressure on the phase equilibrium of wax. The proposed correlation is supported
by data on the wax disappearance temperature (WDT) for several binary and multicomponent systems.

(21)

(22)

(23)

To determine the critical parameters, suitable equations were selected based on the results of a literature
review. They found that when using SRK EoS, the correlations proposed by Riazi and Al-Sahhaf (1995) are
suitable for calculating the critical temperature and pressure, which leads to consistency between the optimal
m values for n-paraffins above C20 and below C20. When using PR EoS, the correlations proposed by Twu
(1984) are suitable for calculating the critical temperature and critical pressure for n-paraffins above C20.
The authors also used the Poynting correction to simulate high pressure conditions, which takes into
account the influence of the difference between the operating pressure (P) and the reference pressure (PO)
(24)
Sansot et al. (2005) proposed a model to describe wax formation in petroleum fluids at high pressure,
which uses a cubic equation of state coupled with a simple mixing rule on a parameter, guaranteeing the
continuity of the fugacity between the solid and fluid phases by modifying the solid activity coefficient
value through a new corrective parameter. Authors applied Pauly's (2000) solid-liquid-vapor equilibrium
prediction model to petroleum fluids and improved it by tuning with an adjustable parameter xls to take the
end effect into account.

(25)

The major asset of this last expression is to separate the nonideality and the pressure influence on the
fugacity of heavy paraffins in the waxy part.
8 SPE-207984-MS

At 2008 Chen et al. presented a thermodynamic model for predicting the deposition of paraffin in crude
oil. The modified SRK-EOS was used to describe the vapor and liquid phases, and UNIQUAC was chosen
to calculate the activity coefficients of the solid phase. In proposed model, a new method for the volume
parameter was recommended, and in the UNIQUAC, an improvement in the correlation for the evaporation
enthalpy was used. By comparing the predictions using the modified UNIQUAC model with those obtained

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from the Leelavanichkul regular solution model, and with experimental results, it is found that the modified
UNIQUAC model is superior to the Leelavanichkul regular solution model in predicting the amount of wax
precipitation.
Further, in 2011 the thermodynamic model is developed to predict the vapor–liquid, solid–liquid, solid–
vapor and solid–liquid–vapor equilibria of systems containing methane with waxy components by Nasrifara
et al (2011) in paper "Multiphase equilibria of waxy systems with predictive equations of state and a solid
solution model". The model takes the advantages of equations of state to describe the vapor and liquid
phases. The solid phase is described by Coutinho’s activity coefficient model, i.e., the solid phase is assumed
to be orthorhombic solid solution.Impact of pressure on the solid phase is included by coupling solid–liquid
Clapeyron relationship with Poynting correction factor. While no adjustable parameter is used, the model
satisfactorily predicts the phase boundaries of the synthetic and real systems resembling gas condensate
mixtures for wide ranges of pressure and temperature.
Ghanaei et al. in 2013 proposed solving the problem of increasing the ratio of liquid to solid volatility of
a pure component to a high pressure associated with the integral of the molar volume of a pure component
in liquid and solid phases during thermodynamic modeling of wax deposition at high pressure in the
work "High pressure phase equilibrium of wax: A new thermodynamic model". The authors propose to
achieve a solution to this problem by using the Clapeyron equation to establish the relationship between
the thermophysical properties and the change in the molar volume of the pure component during the phase
transition. For obtaining liquid to solid fugacity ratio of pure component at high pressure authors used study
result of Ghanaei et al. and transformed it to following equation that estimating the ratio of the fugacity of
a liquid to a solid of a pure component with an OD solid-phase transition

(26)

Juheng Yang (2016) establishedan improved regular solution model, based on the concept of regular
solution and local composition theory. In MRS, local volume fractions, both of identical molecules and
different molecules, are considered to describe the non-random molecules distribution under interaction
between molecules. The local volume fractions 4ij are considered to include the influence of interaction
energy between molecules on molecules' local distribution. A new expression for molar excess Gibbs free
energy (gE) is developed for the calculation of activity coefficients.

(27)

Comparison was made between regular Solution (RS), Wilson (W), and Modified Regular Solution
(MRS), where the latter showed the superiority of RS-MRS illustrated with better predictions ofWAT and
a solid deposition curve that proves that non-random distribution of molecules is caused by the energy of
interaction between molecules is essential for gE.
Then, (Shahdiet al. 2019) developed the open-source software (SP-Wax) for the solid–liquid equilibrium
(SLE) calculation of wax in paraffinic hydrocarbon mixture. The authors used primarily (Coutinho et
al.’s 1995) thermodynamic model and coded in their open-source software. The authors claim that
(Coutinho 1998) thermodynamic model describes the non-ideality of liquid and solid phases fairly
accurately. Moreover, the authors have been validated their SP-Wax by experimental data of five Binary
SPE-207984-MS 9

andMulticomponent system. In addition to experimental precipitation data, composition data of waxy

deposits in pipe was analyzed by SP-Wax and it shows that SP-Wax can estimate the deposit composition
especially at early time. Therefore, the authors affirm that their developed software is more reliable that
others (Zheng et al. 2013) in predicting solid-phase composition.

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Fig. 1—Algorithm of WAT procedure (after Shahdiet al 2019)

The modifications of multisolid wax prediction model after Lira-Galeana et al were performed by the list
of authors. For example, (Pan et al. 1997) investigated the effects of composition and pressure on both the
cloud point temperature (CPT) and the amount of precipitated wax. For this purpose, the wax composition
was analyzed, then the multisolid model (Lira-Galeana et al. 1996) was modified. The experimental data
on wax precipitation for four reservoir fluids were used. In this research, authors divide each undefined
component of a crude into three species: normal paraffins (N), naphthenes and iso- paraffins (P), and
aromatics (A). In addition, the correlations for estimating fusion properties for these species were developed.
(Pan et al. 1997) proposed correlation to estimate the enthalpy of fusion for aromatic species:
(28)
a new correlation for pci, for a hydrocarbon with a molecular weight of more than 300 g/mol.
(29)
Also, authors proposed to estimate the acentric factor of aromatics from
(30)
10 SPE-207984-MS

The calculated results for these four oils using the modified multisolid model were presented and
compared with data.
Then, Nichita et al. (2001) in their research consider the wax precipitation from gas condensates using
modified formulation of multisolid and solid models including the solid-state transitions and Poynting effect.
The modification of multisolid model was firstly proposed by Pan et al. (1997) by separating fractions into

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paraffins, naphthenes, aromatics. For the fusion property calculations authors used the common correlations
and suggest the new correlation for the first solid-state transition temperature:
(31)
Moreover, authors suggested correlations for the enthalpies of fusion and the solid-state transition of
normal alkanes.
For Mi>282kg/Kmol

(32)

For Mi<282kg/Kmol
(33)
The experiments were done on synthetic and natural mixtures, where the authors gave such observations:
for synthetic mixtures the good estimation of CPT was seen within MS model, SS model overestimated it;
at the same time wax amount was underestimated by MS model and overestimated by SS model; for natural
mixtures the amount of precipitated wax was overestimated by SS model.
(Vafaie-Sefti et al. 2001) developed a thermodynamic-computerized model for predicting WAT and
amount of precipitated wax in petroleum mixtures. As expressed in the introduction, almost all of the
previous models for predicting wax formation overestimated the amount of solid wax and all of them use
solid solution theory. However, overestimations of the results obtained by multisolid model are very smaller
than that of other models. In multi-solid model (Pauly et al. 1999), the amount of vapor phase in samples
(dead oils) was ignored and therefore calculations were based on liquid- solid(s) equilibrium. By considering
vapor phase in phase equilibrium, the authors modified multi-solid model, and based on this modification
they proposed a new and effective solution method for this modification, and finally their obtained results
were comparable with experimental data.
SPE-207984-MS 11

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Fig. 2—Algorithm of WAT calculation (after Vafaie-Sefti et al. 2001)

Then, (J.C.M.Escobar-Remolina2006)noted the limitations of the multisolid model due to its range of
pressures, temperatures, and compositions. To improve the weaknesses of existence multisolid models the
author proposed the concept of "Continuous model of multisolid phases for wax precipitation, i.e., it does
not settle down among components that precipitate and those that do not precipitate". The author used the
combination of multisolid precipitation with stability and material balance equation. The key factor here
the usage of the solid fraction equation that directly calculates the precipitated amount if the value higher
than zero and not precipitated when its equals to zero (Lira-Galeana et al. 1996),

(34)

The results showed good agreement with experimental data. Moreover, the comparison with Lira-Galeana
et.al.,Urgerer, Wilson model showed the better accuracy in terms of the calculation of wax appearance
temperature.
At 2007 Dalirsefat et al.used the MPR EOS in this work. The main aim was to develop a thermodynamic-
computerized model for predicting WAT and the amount of precipitated wax in petroleum mixtures. For this
purpose, the MS model which is an EOS-based thermodynamic method has been tested and modified by
adding the vapor phase which is in equilibrium with the liquid and a number of solid phases. The number
of solid phases was calculated by stability analysis. In addition, PNA analysis for wax precipitation was
performed. The physical properties of the samples are then obtained based on the PNA analysis results. At
the end, they have tuned the correlation for the enthalpy of fusion in this work.
12 SPE-207984-MS

(35)

where is in K is in calories/gmol
The modifications mentioned above have considerably improved the prediction of WAT in comparison
with the basic models of Lira-Galeana et al. and Pedersen et al.

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At 2007, Nazar et al.modified the multi-phase model of Lira-Galeana et al. (1996) and considered the
effect of phase transition enthalpy of normal alkanes in a phase equilibria calculation. The binary interaction
coefficients being used in EOS are correlated to better describe the liquid and vapor phase equilibria.
The researchers proposed correlation to estimate the heat of fusion for normal alkanes components is:
(36)
In addition, the following correlation is proposed to estimate binary interaction coefficients between two
normal alkanes:
SPE-207984-MS 13

(37)

(37.1)
(37.2)

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(37.3)
(37.4)
where Mwi and Mwj are the molecular weights of the light and heavy normal alkanes, respectively. The
kij between the normal alkane/nonnormal alkane, and the nonnormal alkane/nonnormal alkane are set to
zero.The proposed model was used to predict the cloud point temperature as well as the characteristics of the
waxy crystallized solid in a number of multi-component systems. The model is supported experimentally
by the multiple pure solid phases which exist when wax precipitation occurs. The Peng-Robinson EOS is
used for the gas-liquid equilibria and the modified multi-solid phase model presented in this work is used
to represent the solid-liquid equilibria. This proposed approach provides a remarkably good description of
the phase equilibria of different waxy mixtures in a very broad temperature region.
Ghanaei et al 2008 presented multisolid model based on activity coefficients approach by comparing the
calculation procedure. Then the results were checked within experimental procedure based on four ternary
systems. The outcomes showed the better accuracy using Wilson model (1964):

(38)

(39)

Additionally, authors stated in their paper the weakness of Lira-Galeana multisolid model in terms of
absence of solid-solid phase transition in the calculation of fugacity ratio of the solid and liquid phase for
a pure component that was improved in work of Nichita et al (2001).
Farayola et al in 2010 used as a base the model of Lira-Galeana (1996) and modified it using the Patel-
Teja three parameter EOS to model the non-ideality of liquid phase. The assumptions introduced by authors
related to the fact that C7 is the lightest component that can be found in wax phase, wax crystals are
orthorhombic and only straight chain paraffin are present. By introducing third parameter"C" the accuracy
is improved by the authors suggestion. Thereby, the three parameter EOS is
(40)

For comparison the experimental data was taken from 16 North Sea oil (Ronningsen et al 1991) and
Pedersen et al. The author’s results showed the better accuracy in comparison with PR EOS at the Lira-
Galeana et al (1996) in terms of WAT and amount of wax precipitated.
At 2012 Adeyemi et al.uses artificial neural network (ANN) to predict the WAT and to compare with the
EOS models PR, Patel Teja and SRK (Farayola 2010), thermodynamic models of Won (1989) Lira-Galeana
et al (1996). Authors used 16 hydrocarbon mixtures for the test and different combination of thermodynamic
properties as molecular weight, activation energy, density, kinematic viscosity, minimum pour point. Taking
14 SPE-207984-MS

into account that ANN ‘learns to solve the problem by developing a memory capable of associating large
number of input parameters with a resulting set of output or effects’ the authors used different combination
of input thermodynamic parameters. Then results were validated with experimental data. A Feed–Forward-
Multilayer Perceptron (FF-MLP) model was selected as a base model due to the fact that ‘FF-MLP is the
universal function approximator that relates as m-dimensional input vector x to an n-dimensional output

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vector y
(41)
After the testing the system, the combination of molecular weight, activation energy and density were
taken as a best combination with the smallest percentage of error. The minimum AAD was showed that
AAD provides the higher accuracy in comparison the above-mentioned models in terms of predicting WAT.
Johnson-Achilike et al. 2015 modified Lira-Galena et.al multisolid model (1996) using live crude oil
data from Niger Delta field. In the paper authors shows the calculation methodology with the specification
of steps to calculate the wax appearance temperature and reservoir fluid characterization. Due to the
difficulties regarding problems of getting live oil sample the paper authors used correlations obtained by
other authors. The fugacity of solid components was evaluated using correlations (Won 1986 and 1989; Lira
1996; Pan 1997; Countinho 2002). The value of calculated wax appearing temperature that was close to the
experimental results was used in further calculations. Then different values of a was used to characterize
reservoir fluid to determine best for Niger Delta oil. Two phase flash calculations and stability analysis
were performed in the paper. Overall, the authors indicated the importance of the wax deposition envelope
calculation for the reservoir management and modelling of reservoir fluid behavior.
At 2018 Mansourpoor et al.developed a multi-solid thermodynamic model to predict wax appearance
temperature (WAT) at low pressures. Paraffinic–naphthenic–aromatic (PNA) analysis was performed, and
two correlations were introduced for fusion properties of these species.
(42)
where Mw is molecular weight and "a", "b", "c", "d", and "e" are constants for PN and A species which
were optimized by Newton algorithm method and are tabulated in Tablebelow
The authors proposed fusion enthalpy equation of PN species based on average properties of these sub-
fractions.
(43)

Fig. 5—Constants for PN and A species (after Mansourpoor 2018)

There is no EOS to estimate the solid-phase behavior. Stability analysis was used in MS models to
determine all components that form as solid phase.
In this regard, predictive thermodynamic models were developed using the fugacity of pure solid and
liquid components at the same conditions.
SPE-207984-MS 15

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Fig. 6—Calculation algorithm (after Mansourpoor 2018)

At 2020 Eyitayo et al.performed the comparison between two wax appearing temperature (WAT)
correlations of Hosseinipour et al. (2019) and then suggested the new correlation for WAT as a function
of solution GOR based on the Niger Delta crude. The Hosseinipour et al. correlation based on four
pseudocomponent model, while second Hosseinipour et al. correlation based on three pseudocomponent
model. The experimental results showed the average absolute deviation (AAD) for the Hosseinipour et al.
equal to 0,017%, for three pseudocomponent model Hosseinipour et al. AAD is 0,00028%; so the authors
stated the best fit with thethree pseudocomponent model Hosseinipour et al. The correlation proposed by
authors is:
(44)
validity of equation is limited to the GORrange 1≤Rsi≤1180 scf/stb.’’
Moreover, the authors modified the Hosseinipour et al. correlation by the inclusion of C7-C9 for the carbon
range of first parameter (X1):
(45)
in which X1, X2 and X3 are the C7-C15, C16-C20 and C21-30+ contents (wt. %), respectively.
The experimental results show the good agreement with the new and modified correlations.

Results and Observations

The results of several studies are presented in Table 1 and 2, for solid-solid and multi-solid models,
respectively.
16 SPE-207984-MS

Table 1—Modifications related to solid-solid model.

Author(s) Modification Improved Results, Observations

Hansen, et al. (1988) Implemented a group-contribution approach Up to 160 pseudo components were
to model the interaction parameter, χi,j used in these calculations.The calculated
WAT in most cases within +4 K
coincide with the measured ones.

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Pedersen, et al. (1991) The following general correlations for the liquidand More precise calculation for paraffinic
solid-phase solubility parameters have been proposed and naphthenic part of a C7+ fraction.

Coutinho (1998) The new "r" and "q" values are obtained simply by dividing The proposed model performs better
theoriginal r and q values by the r and q for the 10methylene units, than (Wilson 1964) model, adequately
predictingthe phase behavior for
complex hydrocarbon mixturesin
both aliphatic and aromatic solvents.

Zuo, et al (2001) The authors proposed the equation of the fugacity Obtained a better representation
coefficient of component i in the solid phase: of phase behavior.

Coutinho, et al (2002) The researchers proposed the normal melting point temperature: Obtained more accurate results compared
to the (Wilson 1964) modeland
considered wax not a single solid solution.

and the enthalpy of melting point:

where N is a carbon number. In addition, Coutinho et al presented an

alternative equation for the wax phase based on UNIQUAC equation:

Hong-Yan Ji, et al (2003)
The authors proposed new correlations for "r" and "q" values. The accuracy of predicted WAT
for binarieslargely depends
on the reliability of values for
fusionproperties and heat capacity.
Also, fusion temperatures at increased
pressure conditions were implemented:

Correlations have been developed for calculating heat capacityas a function

of temperature and carbon number usingmeasured data for n-paraffins

Jean-Marc Sansot, In this work, bending parameters are Results provide an excellent description
et al (2005) replaced by asingle average parameter ξ of solid–fluid-phaseboundaries for
synthetic complex paraffinic mixtures
as well asfor real petroleum fluids
SPE-207984-MS
Author(s) Modification
W.H. Chen, et al (2008) The following correlations have been developedfor calculating ri and qi
Also, the fusion enthalpies of n-alkanes with
all carbon number establishedas follows:
Yang, (2016) The authors developed a new equation
of molar excess Gibbs free energy (gE)
A. Shahdi, et al (2019) The authors developed the open-source software
(SP-Wax) for the solid–liquid equilibrium (SLE)
calculation of wax in paraffinic hydrocarbon mixture.
Table 2—Modifications related to multi-solid model.
Author(s) Modification
C. Lira-Galeana et al. (1996) The authors proposed procedure to evaluate the thermodynamic
behavior during wax precipitation called multisolid model.
H. Pan, et al (1997) Pan et al. proposed correlation to estimate
the enthalpy of fusion for aromatic species:
A new correlation for pci, for a hydrocarbon with
a molecular weight of more than 300 g/mol.
and equation to estimate the acentric factor of aromatics:
Nichita et al (2001) Suggested the new correlation for the
first solid-state transition temperature:
Moreover, authors proposed correlations for the enthalpies of fusion
and the solid-state transition of normal alkanes. For Mi>282kg/Kmol
and
For Mi<282kg/Kmol
J.C.M.Escobar- The researcher developed the solid fraction equation that
Remolina (2005) directly calculates the precipitated amountif the value higher
than zero and not precipitated when its equals to zero:
17
Improved Results, Observations
Calculation the amount of wax
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precipitation more accuratelythan other
local composition models, especially
for thosecomplex crude oil systems.
Better predictions of theWAT and the
solid deposition curve, which prove
that the non-random distribution of
molecules caused by the interaction energy
between molecules is important for gE.
More accurate predicting solid-phase
compositionthan others (Zheng et al. 2013)
Improved Results, Observations
Nowadays, this model is one of the
widely used methods in this area
- the precipitated wax does not contain
aromatics. - the normal paraffins with the
same carbon number as the naphthene
precipitate first. - at high temperatures,
n-paraffins essentially constitute the
waxphase; however, at lower temperatures,
naphthene contribution becomes important.
For synthetic mixtures the good estimation
of CPT was seen within MS model, SS
model overestimated it; at the same time
wax amount was underestimated by MS
model and overestimated by SS model; for
natural mixtures the amount of precipitated
wax was overestimated by SS model.
The comparison with Lira-Galeana
et.al.,Urgerer, Wilson model showed
the better accuracy in terms of the
calculation of wax appearance point.
18
Author(s)
R. Dalirsefat, et al (2007)
A. R. Solaimany
Nazar, et al (2007)
Ghanaei et al (2008)
Ghotbi C, et al (2016)
M. Mansourpoor
et al (2018)
Eyitayo et al (2020)
E. V. Asbaghi, et al (2021)
For thepetroleum fractions, the efficient parameters are estimated as below:
Modification
The authors tuned the correlation for the enthalpy of fusion
The researchers proposed correlation to estimate the
heat of fusion for normal alkanes components is:
In addition, the following correlation is proposed to estimate
binary interaction coefficients between two normal alkanes:
A multi-solid model basedon "γ" approach has been
presented for the prediction of waxformation phenomena.
The average molecular weight of the light pseudo component is
used to estimate the corresponding PC-SAFT parameters as follow:
Two correlations were introduced for fusion properties
In addition, fusion enthalpy equation of PN species
based on average properties of these sub-fractions:
The authors suggested the new correlation for WAT as a function of
solution GOR based on the Niger Delta crude Twax = 301.43R-0.0060s
The fugacity coefficient for a component (φi):
SPE-207984-MS
Improved Results, Observations
The modifications significantly improved
WAT prediction over the models by
Lira-Galeana et al. and Pedersen et al.
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The proposed approach provides a
description of the phase equilibria
of various wax mixtures over
a very wide temperature range.
The results show that this approach
is better than the one that uses the
equation of state. In addition, the
running time of the new method is
shorter than that of the previous models.
It is demonstrated that the developed
PC-SAFT model can correlate the
wax precipitation amount better than
basic models (multiple solid and solid
solution) typically used in the industry
The results show that the melting point
and enthalpy of melting of the components
are the most important parameters
in predicting WAT. The proposed
thermodynamic model predicts well the
WAT of paraffins in multicomponent
systems, as well as in ternary mixtures.
The experimental results show the good
agreement with the new correlations.
This efficient parameterestimation
method changes the uncertain parameters
to predict precipitationbehavior more
accurately. Moreover, this study
better represented the temperature
at which each component begins to
precipitate compared to previous models.
SPE-207984-MS 19

Conclusion
Wax deposition in pipelines is one of the most crucial problems facing the oil industry. Significant capital
losses were caused by wax deposition problems due to high maintenance costs, loss of pipelines, reduced
productivity, and increased pumping capacity. The ability to accurately predict wax deposition is an
invaluable tool that can assist during the pipeline design stages as well as when planning repairs.

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The authors have attempted to provide the petroleum engineering community with an overview of various
thermodynamical models for predicting wax precipitation and believe that this manuscript may be useful
to aspiring engineers and researchers in the industry.

Acknowledgement
This paper was prepared as part of the project "Development of PVT model for prediction of wax
precipitation" AP09058452, within the framework of the competition is held on grant financing of
fundamental and applied research young scientists on scientific and (or) scientific and technical projects for
2021-2023 by Ministry of Education and Science of the Republic of Kazakhstan.

Nomenclature
C1, C2 and C3 constants
number of carbon atoms in the ith component.
phase equillibrium coefficient of solid liquid idela solutionγ
γ activity coefficient
enthalpy of phase transition
t phase transition including fusion
heat capacity change accompanied by phase transition
R universal gas constant
T temperature
x liquid-phase molar fraction
Z coordination number
q UNIQUAC structural parameter
r UNIQUAC structural parameter
λ pair interaction energy
f fugacity
P pressure
H enthalpy
R ideal gas constant
T temperature
M molecular weight
s solid mole fraction
q molecular external surface
v molar volume
τ parameter related with the characteristic energy
r molecular size
f fugacity
g Gibbs free Energy
molar volume
δ solubility parameter
φ volume fraction
20 SPE-207984-MS

s molar fraction (pure)

z molar fraction
φ fugacity coefficient feedf1, f2, f3 help variables
Λ nteraction parameter
φ fugacity coeficient

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Z compressibility factora,b,c-parameters of EOS
L number of hidden layers
WL matrix of weight for layer L
bL vector of biases for layer LTwax is the WAT (K)
Rs solution GOR (scf/stb)
ω acentric factor

Subscripts
i component
j component
0 pure component
c critical property

Superscripts
s solid
L liquid
β volume change parameter
Tr transition
m melting
f fusion
Od order-disorder
Sat saturation
f melting point
E excess
w waxy part
β volume change parameter

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