Chemical Engineering Journal Advances 6 (2021) 100104

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Chemical Engineering Journal Advances

journal homepage: www.elsevier.com/locate/ceja

Review of wax deposition in subsea oil pipeline systems and mitigation

technologies in the petroleum industry
Abass A. Olajire
Industrial/Environmental Unit, Department of Pure and Applied Chemistry, Ladoke Akintola University of Technology, Ogbomoso, Nigeria

a r t i c l e i n f o a b s t r a c t

Keywords: Wax deposition in oil subsea pipeline systems is a big challenge in petroleum industry due to the frigid temper-
Wax ature of pipe walls that influences crystallization and wax deposition on the inner surface of the pipe over time
Fluidity leading to blockage. An understanding of the mechanisms and models of wax deposition process can be useful for
Deposition mechanisms
the management and planning of mitigation strategies for deposition of solid wax crystals. This article presents
Prediction models
major mechanisms and wax prediction models used for the estimation of wax deposition as well as technology
Mitigation techniques
used for mitigating wax deposition in reservoirs and flowlines.

1. Introduction C16 to C40 (n-alkanes) and crystallizes in a platelet-like or a needle-like

The tremendous increase in the production rate of waxy and heavy
crude oils (unconventional oils) due to the continuous depletion of con-
ventional oil reserves has made wax deposition in subsea pipeline to
receive considerable attention in the past few decades. These uncon-
ventional oil reserves are typically produced in deep-water zone with
extremely low temperature [1]. The production of wax deposits in sig-
nificant quantity under these favorable subsea conditions can impede
flowability of these waxy crude oils, leading to eventual production
shutdown [2]. The deposition and transformation of molecules of wax
into a wax gel that occupies the cross-section area of the pipeline in-
ner surface occur when the bulk oil temperature (BOT) falls below the
wax appearance temperature (WAT). The effective surface area for fluid
flow is reduced as a result of deposition of untreated wax, and in ex-
treme scenario completely blocks the pipeline which eventually leads
to complete production shutdown and huge financial loss to oil and gas
sector [3-5]. The continuous deposition of precipitated wax on the sur-
face of the pipeline leads to gelation of the wax, where the three stages
of phase transformation of waxy crude oil [6] including aggregation of
wax particles in the oil clusters as temperature and pressure change, the
gelation of wax layer which majorly influence poor flowability of waxy
crude oils [7] and layer-wise deposition of gel-like wax take place, re-
sulting to flowline blockage that eventually leads to complete shutdown
of production processes.
Paraffin wax is a complex mixture of high molecular weight alkanes,
consisting of straight, branched and cyclic chains in solid or liquid form
at room temperature [8–11]. The two groups of paraffin waxes in uncon-
ventional crude oil include macrocrystalline and microcrystalline waxes
[12,13], where the former has straight carbon chain length ranging from
structure while the latter has a high percentage of iso-paraffin hydrocar-
bons and naphthenic rings with carbon chain ranging from C30 to C60
and crystallizes in amorphous-like structure [14]. The structure of main
paraffin wax is given in Fig. 1.
The thorough understanding of the wax deposition prediction mod-
eling and wax contents of waxy crude oil is important for the avoidance
of various problems associated with pipeline blockage and clogging. Dif-
ferent countries have different rates of wax formation of during crude
oil production processes [15]. The characterization and composition of
waxy crude oils from different regions of the world is summarized in
Table 1, where the wax quality, API gravity, WAT and pour point were
found to exhibit a good correlation in most countries.
The huge production loss due to wax deposition in subsea pipelines
thus necessitates the need to understand the contributory factors to the
formation and stabilization of the deposited wax as well as establish-
ing mathematical models for the prediction of wax deposition. This re-
view therefore focuses on the status of current research activities and
perspectives of various research groups on the abundance, depositional
mechanisms and composition of paraffin wax in the production tubing
[16-18] as well as mitigation technologies for the prevention or reduc-
tion of depositional rate of wax in the production tubing. The various
models of wax deposition are also discussed.
2. Wax deposition mechanisms
Wax deposition mechanism involves formation, growth and deposi-
tion of solid layers on the inner surface of a pipeline. The deposition of
wax can only occur when the inner surface temperature of the pipe is be-
low the wax appearance temperature (WAT). Several mechanisms have

E-mail address: olajireaa@yahoo.com

https://doi.org/10.1016/j.ceja.2021.100104
Received 15 January 2021; Received in revised form 7 March 2021; Accepted 7 March 2021
2666-8211/© 2021 The Author. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/)
A.A. Olajire Chemical Engineering Journal Advances 6 (2021) 100104

Nomenclature Tw inner wall surface temperature, K

Tjac temperature of the jacket (°C)
Aw surface area available for wax deposition, m2 Tcf temperature of cold finger
Δ𝐶𝑝𝑖 the difference between solid and liquid state heat capac- VA molar volume of wax molecules
ities, J mol–1 K–1 ΔVi difference between the solid and liquid phase molar vol-
Cth thermal conductivity of oil, J/s.m K ume of component i
C wax concentration in crude oil, kg/m3 Vz velocity of flow, m/s
Cwb concentration of dissolved paraffin wax in the bulk fluid, V volume, m3
kg/m3 ww concentration of wax in solution, wt%
Cws concentration of the dissolved paraffin wax at the oil-gel x mole fraction
interface, kg/m3
Cw concentration of precipitated wax at the wall, kg/m3 Greeks symbol
dw inside diameter as a result of wax build-up, m 𝛾 activity coefficient
Dwo diffusivity wax in crude oil, m2 /s 𝛾s oil shear rate at the wall, s–1
Dow turbulent mass diffusion 𝛿 solubility parameter
Dw diffusion coefficient or diffusivity of liquid wax in the 𝜑 volume fraction
oil phase, m2 s–1 𝜌dep density of deposit, kg/m3
De effective diffusivity in the deposit, m2 /s 𝜌w density of the solid wax, kg m–3
DB Brownian diffusion coefficient, m2 /s 𝜌oil density of crude oil, kg/m3
Ds shear dispersion coefficient, cm s–1 , 𝜌m average density of the gas-oil mixture, kg/m3
𝑑𝐶
concentration gradient of wax (1/m) over pipe radial 𝜌p particle density, kg/m3
𝑑𝑟
coordinate r (m), 𝜌f fluid density, kg/m3
𝑑𝐶
dissolved wax concentration gradient with the temper- 𝜇 kinematic viscosity coefficient, m2 /s
𝑑𝑇
𝜇o oil dynamic viscosity coefficient, m2 /s
ature (K−1 ), (or solubility coefficient), kg/m3 K
𝑑𝑇 𝜇 solvent solvent dynamic viscosity, m2 /s or Pa s
𝑑𝑟
radial temperature gradient of the wall (K m−1 ).
𝜇f fluid viscosity m2 /s or Pa.s.
E liquid hold up, ∏
empirical relation for the rate enhancement
f fugacity, Pa ∏1
2 empirical relation for rate reduction
Fw wax fraction in the deposit, wt %
𝜃 sL liquid superficial velocity, m/s
Gzh Graetz number for heat transfer,
𝜌m average density of the gas-oil mixture (kg/m3).
Gzm Graetz number for mass transfer,
𝜆o oil thermal conductivity, J/s.m.K
ho heat transfer coefficient of crude oil, J/s. m2 K
hT heat transfer coefficient of pipe wall, J/s. m2 K Superscripts
he conductive heat transfer coefficient, J/s. m2 K L liquid
hi inner convective heat transfer coefficient, J/s. m2 . K V vapor
hw inner wall surface heat transfer coefficient, J/s.m2 . K S solid
ΔH enthalpy change, J/mol f fusion
ΔHf heat of wax solidification
Δ𝐻𝑖𝑡𝑟 enthalpy of solid-solid transition between different solid Acronyms
phases AARE average absolute relative error
km mass transfer coefficient, kg/m2 K API American petroleum institute
kf thermal conductivity of the fluid, J/ s. m. K BD Brownian diffusion
kp thermal conductivity of wax particles, J/ s.m. K BOT bulk oil temperature
ΔL pipe length of wax deposit buildup, m DWC dissolved wax concentration
M mass flux, kg EM equilibrium model
MB mass of deposited wax due to Brownian diffusion, kg EOS equation of state
MW molecular weight, g/g mol EVA ethylene vinyl acetate
mw mass of deposited wax, kg, ID internal diffusion
Ns number of solid phases IRSM improved regular solution model
N Avogadro’s number, (6.022 x 1023 mol−1 ) MD molecular diffusion
Pr Prandtl Number MM Matzain’s model
P pressure, Pa MMVA monomers octadecylacrylate (M), maleic anhydride
ri radial distance from the center to the oil-deposit inter- (M), vinyl (V) acetate (A)
face, m MS multi-solid
r particle radius, cm MWP Michigan wax predictor
RE Reynolds’s number NGS nitrogen generating system
R inner radius of pipe, m ODMA octadecylmethacrylate
R gas universal constant, J mol –1 1 K–1 OMS octadecyl methacrylate (O), maleic anhydride (M) and
t time, s styrene (S)
Ta ambient temperature, K PAA polyaminoamide
To temperature of oil at the center, K PC-SAFT perturbed chain form of the statistical associating fluid
𝑇𝑖𝑓 temperature of fusion, K theory
𝑇𝑖𝑡𝑟 transition temperature, K PEB poly(ethylene-butene)
Ti temperature of the oil-wax interface, K PE-PEP polyethylene-poly(ethylene propylene)
Tb bulk average flow temperature, K PMAs polymethacrylates

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A.A. Olajire Chemical Engineering Journal Advances 6 (2021) 100104

PMAC poly(maleic anhydride amide co-𝛼-olefin)

PMMA poly(methyl methacrylate)
PPD pour point depressant
PR EOS Peng and Robinson equation of state
RRR Rugg, Rydahl and Ronningsen
RSFV regular solution and Flory-free volume
SCN single carbon number
SD shear dispersion
SLE solid-liquid equilibrium
SR shear removal
SS solid solution
TD thermal diffusion
VLSE vapor-liquid-solid equilibrium Fig. 1. Main paraffinic wax structures.
WAT wax appearance temperature
WDT wax disappearance temperature
is the concentration gradient of wax (1/m) over the radial coordinate
of the pipe r(m), 𝑑𝐶
𝑑𝑇
is dissolved wax concentration gradient with the
been proposed to describe the formation of wax deposits on pipeline temperature (K−1 ), and 𝑑𝑇𝑑𝑟
is the radial temperature gradient of the pipe
walls. These mechanisms include molecular diffusion, shear dispersion,
wall (K m−1 ).
Brownian diffusion, gravity settling and Soret diffusion [32–36].
Wilke and Chang [38] used some experimental data points to pro-
pose an equation for the estimation of Dw as follows:
2.1. Molecular diffusion
( )0.5
𝜅𝑥𝑀𝑠𝑜𝑙𝑣𝑒𝑛𝑡 𝑇𝑎
The transport of wax in pipes is influenced by the temperature and 𝐷𝑤 = 7.4𝑥10−8 (2)
0.6
𝜇𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 𝑉𝑠𝑜𝑙𝑢𝑡𝑒
concentration gradients that are prevalent at the laminar sublayer ad-
joining to the pipe wall [37]. Molecular diffusion has been found to where, Ta and Msolvent are the absolute temperature (K)and solvent
dominate the primary mechanism at high temperature heat flow condi- molecular weight (g mol−1 ) respectively, 𝜅 is the Wilke and Chang asso-
tions typical of subsea flow line systems [32]. The cooling of the pipe ciation parameter that represents the effective solvent molecular weight
wall of a subsea pipeline below WAT leads to a temperature difference with respect to the diffusion of the molecules (𝜅 = 1 and 2.6 for non-
across the laminar sub-layer and the dissolved wax crystallizes and pre- associated solvents and water respectively), 𝜇solution is the solution dy-
cipitates out of the crude oil. Since the solubility of the wax decreases namic viscosity (cP), and Vsolute is the molar volume(cm3 mol−1 ) of wax
with the temperature, a radial concentration gradient of dissolved wax at the normal boiling point, Dw has a typical value of 10−9 m2 s−1 [38,
will be established between the bulk solution and the pipe wall, where 39].
the dissolved wax material will be transported by molecular diffusion
from the bulk medium with a higher dissolved wax concentration (DWC) 2.2. Brownian diffusion mechanism
towards the pipe wall with a lower DWC [32]. The molecular diffusion
of solid wax in oil and gas as well as the wax deposition rate can then This involves constant collision of suspended small solid waxy crys-
be modelled by using the Fick’s law of diffusion as follows [32]: tals in crude oil with thermally agitated oil molecules, resulting to
small random Brownian movements of the suspended particles [40]. The
𝑑 𝑀𝑤 𝑑𝐶 𝑑𝑇 𝑑𝐶
= 𝜌𝑤 𝐷 𝑤 𝐴 𝑤 = 𝜌𝑤 𝐷 𝑤 𝐴 𝑤 (1) Brownian motion will then lead to a net transportation of waxy crystals
𝑑𝑡 𝑑𝑇 𝑑𝑟 𝑑𝑟
towards the region of decreasing concentration (pipe wall), thus having
𝑑𝑀
where, 𝑑𝑡𝑤 is the wax deposition rate (kg/s), mw is the mass (kg) of de- a mathematical description that is similitude to diffusion [32]. The bom-
posited wax, t is the time (s),𝜌w is the density of the solid wax (kg m−3 ), bardment of the suspended precipitated wax in waxy oil flown by the
Aw is the surface area available for wax deposition (m2 ), Dw is the diffu- agitated oil molecules creates a net irregular movement of wax particles
sion coefficient or diffusivity of liquid wax in the oil phase (m2 s−1 ), 𝑑𝐶
𝑑𝑟
[32]. In the presence of concentration gradients of the solid wax, Fick’s

Table 1
Values of wax contents, API gravity, WAT, and pour point of worldwide waxy crude oil.

Region Wax content (wt%) API∗ gravity WAT (°C) Pour point (°C) Reference

China 18.25 24.2 - 43 [19]

Dulang, Malaysia 3 12.6 31 33.76 [20]
Angsi, Malaysia 2 42.6 28 33.32 [20]
South America NA∗∗ 27 36.4 9 [21]
Eastern Egyptian 3.3-4.5 - - - [22]
Upper Egypt 11.92 31.6 - 27 [23]
South East Asia 18-38 25-40 26-68 15-60 [6]
North Sea Crude oil 15 33 42 27 [24]
Venezuelan (Boscan) 4.1 - - - [24]
Russian 9.4-12.2 - - - [25]
Sudan 21.2 - - - [26]
Gulf of Mexico 7.8 [27]
Mexico (PC) 11.26 36 - -30 [28]
Mexico (IRI) 10.91 28.4 - -26 [28]
Iran 13.1 34.9 - 26 [29]
India 22.4 44.2 - 22 [30]
China (Changqing) 20.78 34 - 30 [31]
∗
API, American Petroleum Institute; ∗ ∗ NA, not available

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A.A. Olajire Chemical Engineering Journal Advances 6 (2021) 100104

law of diffusion can be used to model the final transport of deposited Table 2
wax molecules towards the decreasing concentration as follows [37]: Wax deposition mechanisms reported in the literature
[57].
𝑑 𝑀𝐵 𝑑𝐶
= 𝜌𝑤 𝐷 𝐵 𝐴 𝑤 (3)
𝑑𝑡 𝑑𝑟 Wax deposition mechanism Reference
where MB is the mass (kg) of wax deposited due to Brownian diffusion MD [34, 38, 39, 58-89]
and DB is the Brownian diffusion coefficient (m2 /s) which can be calcu- SD [90]
lated for spherical and non-interacting particles as follows [32, 41–43]: MD + SR [91-97]
MD + SD [45, 46, 52, 90, 98-100]
𝑅 𝑇𝑎 MD + ID [44, 55, 101-105]
𝐷𝐵 = (4) MD+ TD [54, 56, 106, 107]
6 𝑁 𝜋 𝜇𝑠𝑜𝑙𝑣𝑒𝑛𝑡 𝑟
MD+ BD [37, 108]
where R is the gas constant (8.314 J K-1 mol-1 ), Ta and r are the absolute SD + BD [109]
temperature (K)and the particles radius (m) respectively, 𝜇solvent andN MD + SD + BD [17,32]
are the solvent dynamic viscosity (Pa s−1 ) and the Avogadro’s number MD, molecular diffusion; BD, Brownian diffusion; SD,
(6.022 x 1023 mol−1 ). shear dispersion; SR, shear removal; TD, thermal diffu-
However, Brownian diffusion has been ignored by many researchers sion (Soret effect); ID, internal diffusion (Aging).
as a relevant mechanism for deposition of wax due to lower temperature
of the wall of the pipe compared to the bulk medium, which results to the
precipitation of higher quantity of wax components at the inner surface and deposited at the bottom of the pipe [32]. Gravity settling has been
wall of the pipe than in the bulk medium and get deposited at the pipe, classified to have insignificant contribution to wax deposition under sub-
which is in contrast to the expected Brownian movements. Nonetheless, sea flow conditions based on the experimental evidence of Burger et al.
Brownian diffusion has been found to remain a possible contributor to [32]. The settling velocity, Vg of wax particles is a measure of the bal-
the wax deposition mechanism [37, 44]. ance between the floatability and the fluid friction (viscous forces); and
is expressed as [53]:
2.3. Shear dispersion
𝑑 2 ( 𝜌𝑝 − 𝜌𝑓 ) 𝑔
𝑉𝑔 = (6)
The transportation of suspended small solid particles in a fluid in 18 𝜇𝑓
the laminar-flow motion tends occur at an average velocity towards the where, Vg is the settling velocity (m/s), d is the particle diameter (m), gis
surrounding fluid. However, the lateral motion of the particles induces the acceleration due to gravity (m/s2 ), 𝜌p is the particle density (kg/m3 ),
shearing effect on the fluid near the wall of the pipe that could con- 𝜌f is the fluid density (kg/m3 ), and 𝜇 f is the fluid viscosity (Pa.s).
tribute to resultant transportation of wax particles towards the internal
surface of the pipeline [45]. The wax crystals in the oil will migrate to- 2.5. Thermal diffusion
wards the wall and be deposited due to the lower velocity near the wall
compared to the centre of the pipe. So, the wax deposit may self- formed Thermal diffusion (also refers to Soret diffusion) deals with the de-
or mixed with already deposited wax by molecular diffusion at the wall position of wax by using temperature gradients that exist within the
of the pipe [45]. If all the wax forming components are taken together pipeline as the driving force [54]. The effect of Soret diffusion in wax
as a single pseudo component, the rate of deposition of wax due to shear deposition has been found to be negligible [55]. However, accurate
dispersion can be expressed as [32, 46]: modelling of wax deposition that accounts for thermal effects during
𝑟2 𝛾𝑠 𝐶𝑤 diffusion can be obtained if the diffusion is expressed in form of molec-
𝐷𝑠 = (5)
10 ular and thermal diffusion [56]. The temperature gradient has influence
where Ds is the shear dispersion coefficient (m s–1 ), Cw is the concentra- on the diffusion of wax particles, because the thermophoretic velocity
tion of precipitated wax at the wall and 𝛾 s is the oil shear rate at the (m/s) of the particles due to temperature gradient is expressed as [53]:
wall (s–1 ).
𝜇 ∇𝑇
The contribution of shear dispersion to wax deposition cannot be ig- 𝑣𝑇 = −𝛽 (7a)
𝜌𝑇
nored [47, 48] and it predominates over molecular diffusion at a higher
velocity of the flow [49]. Wax particles dispersing toward the wall in- The movement of the particles from the hotter to colder zone is des-
creases with increasing shear rate, thus leading to reduction in the pipe ignated with the negative sign and the proportionality constant,𝛽, can
effective diameter that causes impediment to flow [50]. This may then be obtained as follows:
lead to high pressure build-up in the pipe and high shear stress on the 𝑘𝑓
deposit thereby influencing mechanical stripping of the wax deposits 𝛽 = 0.26 (7b)
2 𝑘𝑓 + 𝑘𝑝
from the pipe wall [45]. Shear stripping was therefore suggested to be
taken into consideration in the wax deposition modelling [51]. where kf and kp are thermal conductivities (J/s.m.K), of the fluid and wax
Shear dispersion has been found to be the dominant process for tem- particles respectively.
peratures that are much lower than the cloud point while molecular The wax deposition mechanisms adopted by various research groups
diffusion is the dominant process at higher temperatures [52]. How- are summarized in Table 2. As can be seen from the table, molecular
ever, Azevedo and Teixeira [37] were of different view based on their diffusion is widely investigated and the most dominant mechanism that
experimental evidence that revealed no wax deposition under condition has been found to be responsible for the deposition of wax particles.
of zero heat flow, while deposition of wax was reported to be only pos- However, the use of molecular diffusion alone for wax deposition mod-
sible if the process is driven by a flow-induced mechanism like shear elling has been proved to give erroneous prediction of wax deposition
dispersion. Azevedo and Teixeira [37] maintained that the contribution behaviour [17], hence it is used along with the impacts of other mech-
of shear forces to the removal of wax deposits from the pipe wall is still anisms in some studies reported in the literature (Table 2).
significant.
3. Wax deposition models
2.4. Gravity settling
Wax deposition models are used to predict the severity in terms of
The precipitated solid waxy crystals are denser than the crude oil, thickness of the wax deposition and changes in the wax fraction profiles
and if the particles are non-interacting, they will settle in a gravity field over time. However, wax deposition models vary in their applicability

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A.A. Olajire Chemical Engineering Journal Advances 6 (2021) 100104

depending on factors incorporated, their different methods and assump- of wax deposit with increasing internal diffusion of more solid wax into
tions. Petroleum industry uses different models to predict the deposition deposit, depends only on mass flow diffusivity into the deposit [88].
of wax in the pipeline and tubing with the objective of calculating where Thus, the aging term is expressed as:
and frequencies at which wax build-up occurs on the inner wall of the
𝜕𝑀 𝑑 𝐹𝑤
pipe. Different wax deposition models are as discussed below: = 2 𝜋 𝑟𝑖 Δ𝐿 𝑞𝑚, 𝑎𝑔𝑖𝑛𝑔 (12a)
𝜕 𝐹𝑤 𝑑𝑡

3.1. Dynamic model The Fick’s law can be used to express the internal mass flow diffu-
sivity as follows [56]:
The dynamic model represents the mutual interactions of precipi- ( )
𝜕𝐶 ||
tated wax and the fluid in the subsea piping and is based on two mech- 𝑞𝑚, 𝑎𝑔𝑖𝑛𝑔 = −𝐷𝑒 (12b)
𝜕𝑟 ||𝑟+𝑖
anisms, which include the molecular diffusion and aging as established
by Fick’s law [110]. The calculation of the model was simplified by as- The rate of transport of solid wax fraction from the deposit interface
suming that the mass transfer between the oil and gas phases is zero or to the solid wax deposit can be obtained by substituting Eq. (12b) into
the phase change due to variation in temperature and pressure is zero. Eq. (12a) as follows:
In accordance with the molecular dispersion mechanism, if the molecu- ( )
lar mass flow (M) of the wax from the centre of pipe to the oil-deposit 𝜕𝑀 𝑑 𝐹𝑤 𝜕𝐶 ||
= 2 𝜋 𝑟𝑖 Δ𝐿 𝑞𝑚, 𝑎𝑔𝑖𝑛𝑔 = 2 𝜋 𝑟𝑖 Δ𝐿 −𝐷𝑒 (12c)
interface is taken as a function of wax deposit thickness(𝛿 = R − ri ), 𝜕 𝐹𝑤 𝑑𝑡 𝜕𝑟 ||𝑟+
𝑖
then the wax fraction of the deposit (Fw ) is expressed as:
where De is the effective diffusivity of the wax in waxy crude oil and can
𝜕𝑀 𝜕𝑀
𝑑𝑀 = 𝑑𝑟 + 𝑑 𝐹𝑤 (8) be calculated with Cussler relationship [115] as follows:
𝜕 𝑟𝑖 𝑖 𝜕 𝐹𝑤
𝐷𝑤𝑜
The derivative of Eq. (8) with time gives the rate at which the wax 𝐷𝑒 = (13a)
1 + 𝛼 2 𝐹𝑤2 ∕(1 − 𝐹𝑤 )
mass goes from the oil to the pipe wall, and is expressed as:
𝑑𝑀 𝜕𝑀 𝑑 𝑟𝑖 𝜕𝑀 𝑑 𝐹𝑤 where, 𝛼is given by the ratio of length to diameter of wax crystal parti-
= + (9a) cles in the deposit.
𝑑𝑡 𝜕 𝑟𝑖 𝑑𝑡 𝜕 𝐹𝑤 𝑑𝑡
The equivalent wax crystal ratio, 𝛼 was assumed to vary linearly with
where R is the inner radius of the pipe, ri is the radial distance from the the wax fraction [44], as shown in the equation below:
centre of the pipe to the oil-deposit interface, t is time.
The first term on the right hand side of Eq. (9a) is the build-up term 𝛼 = 1 + 𝑘𝛼 𝐹𝑤 (13b)
(qm, in ), which represents the mass flow rate of the wax that gives rise to
Substitution of Eqs. (10c) and (12c) into Eq. (9b) gives the build-up
the growth of wax deposition thickness. The second term on the right
term, which is the difference between the wax mass flow from the pipe
hand side of Eq. (9a) is the aging term (qm, aging ), which represents the
center to the oil-deposit interface and the wax mass flow diffusing into
rate of mass flow of the wax that gives rise to increase in the wax frac-
the deposit, and is expressed as:
tion. Eq. (9a) can be rearranged to give the build-up term as follows: [( ( )]
)
𝜕𝑀 𝑑 𝑟𝑖 𝜕𝐶 || 𝜕𝐶 ||
𝜕𝑀 𝑑 𝑟𝑖 𝑑𝑀 𝜕𝑀 𝑑 𝐹𝑤 = 2 𝜋 𝑟𝑖 Δ𝐿 −𝐷𝑤𝑜 − − 𝐷 (14)
= − (9b) 𝜕 𝑟𝑖 𝑑𝑡 𝜕𝑟 ||𝑟𝑖 𝑒
𝜕𝑟 ||𝑟+
𝜕 𝑟𝑖 𝑑𝑡 𝑑𝑡 𝜕 𝐹𝑤 𝑑𝑡 𝑖

The mass flow rate of the wax into the oil-deposit interface per unit When crude oil of density 𝜌oil flows through a pipe of length ΔL
time, per unit area of the pipe surface is expressed as follows: for a period of time t and the wax deposit thickness of 𝛿 = R − ri is
deposited inside the pipe, then the mass of solid wax in the deposit is
𝑑𝑀
= 2𝜋 𝑟𝑖 Δ𝐿 𝑞𝑚, 𝑖𝑛 (10a) expressed as:
𝑑𝑡
( )
The Fick’s law of diffusion that relates the mass diffusive flow(qm, in ) 𝑀 = 𝜋 𝑅2 − 𝑟2𝑖 Δ𝐿 𝜌𝑑𝑒𝑝 𝐹𝑤 (15)
to the gradient of the concentration is expressed as [111]:
where, 𝜌dep is the density of deposit, which is assumed to be the same
𝜕𝐶 || as crude oil.
𝑞𝑚, 𝑖𝑛 = −𝐷𝑤𝑜 (10b)
𝜕𝑟 ||𝑟𝑖 The partial derivative of the mass of the wax deposited with respect
The rate of mass diffusive flow into the oil-deposit interface can be to the radial distance ri can be expressed as:
obtained by substituting Eq. (10b) into Eq. (10a) as follows: 𝜕𝑀
( ) = − 2 𝜋 𝑟𝑖 Δ𝐿 𝜌𝑑𝑒𝑝 𝐹𝑤 (16a)
𝜕 𝑟𝑖
𝑑𝑀 𝜕𝐶 ||
= 2𝜋 𝑟𝑖 Δ𝐿 𝑞𝑚, 𝑖𝑛 = 2𝜋 𝑟𝑖 Δ𝐿 −𝐷𝑤𝑜 | (10c)
𝑑𝑡 𝜕𝑟 |𝑟𝑖
𝜕𝑀 𝑑 𝑟𝑖 𝑑𝑟
= − 2 𝜋 𝑟𝑖 Δ𝐿 𝜌𝑑𝑒𝑝 𝐹𝑤 𝑖 (16b)
where, ΔL is the pipe length (m) of wax deposit build-up, Dwo is the wax 𝜕 𝑟𝑖 𝑑𝑡 𝑑𝑡
diffusion coefficient or molecular diffusivity of wax in oil, and can be
The partial derivative of the mass of wax deposited with respect to
obtained by using the Hayduk-Minhas relationship [112] as follows:
mass fraction, Fw is given as:
𝑇𝑜1.47 𝜇 𝛾 ( )
𝐷𝑤𝑜 = 13.3𝑥10−12 𝑥 (11a) 𝜕𝑀
= 𝜋 𝑅2 − 𝑟2𝑖 Δ𝐿 𝜌𝑑𝑒𝑝 (17a)
𝑉𝐴0.71 𝜕 𝐹𝑤
10.2
𝛾= − 0.791 (11b) 𝜕𝑀 𝑑 𝐹𝑤 𝑑 𝐹𝑤
𝑉𝐴 = 𝜋 (𝑅2 − 𝑟2𝑖 ) Δ𝐿 𝜌𝑑𝑒𝑝 (17b)
𝜕 𝐹𝑤 𝑑𝑡 𝑑𝑡
where, To , 𝜇 o and VA are the oil temperature, oil dynamic viscosity, and
molar volume of wax molecules, respectively. Substitution of Eq. (16b) into Eq. (14) and solving them simultane-
The temperature TΔL at the pipe length, ΔL is given as [113]; ously gives:
[( ) ( )]
𝑇Δ𝐿 = 𝑇𝑎 + (𝑇𝑜 − 𝑇𝑎 ) 𝑒−(ℎ𝑜 𝜋 𝑑Δ𝐿∕𝑚̇ 𝐶) (11c) 𝑑𝑟 𝜕𝐶 || 𝜕𝐶 ||
−2 𝜋 𝑟𝑖 Δ𝐿 𝜌𝑑𝑒𝑝 𝐹𝑤 𝑖 = 2 𝜋 𝑟𝑖 Δ𝐿 −𝐷𝑤𝑜 − −𝐷𝑒
The dependency of wax deposition on temperature is expressed by 𝑑𝑡 𝜕𝑟 ||𝑟𝑖 𝜕𝑟 ||𝑟+
𝑖

Eq. (11a) [114]. The aging, which is the process of gradual hardening (18)

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A.A. Olajire Chemical Engineering Journal Advances 6 (2021) 100104

Rearrangement of Eq. (18) gives the following Eq. (19), that defines method that assumes that precipitation of wax will occur as the
the rate of change of wax deposit thickness with time as follows: solubility decreases [88, 117, 118], as follows:
[( ) ( )]
𝜕𝐶 || 𝑑𝐶 𝑑𝑇 ||
𝑑 𝑟𝑖 1 𝜕𝐶 || 𝜕𝐶 || ≈ . (25b)
= − −𝐷𝑤𝑜 − −𝐷𝑒 (19) 𝜕 𝑟𝑖 ||𝑘𝑗 𝑑𝑇 𝑑𝑟 ||𝑘𝑗
𝑑𝑡 𝜌𝑑𝑒𝑝 𝐹𝑤 𝜕𝑟 ||𝑟𝑖 𝜕𝑟 ||𝑟+𝑖
𝑑𝐶
𝑑𝑇
𝑖𝑠 𝑡ℎ𝑒 𝑠𝑜lub𝑖𝑙𝑖𝑡𝑦 𝑐𝑜𝑒𝑓 𝑓 𝑖𝑐𝑖𝑒𝑛𝑡, and the temperature gradient is de-
The increase in the rate of deposit thickness of the solid wax can be
fined as:
expressed as:
𝑑𝑇 || ℎ𝑇 (𝑇𝑘 − 𝑇𝑗 )
𝑑𝛿 𝑑 (𝑅 − 𝑟𝑖 ) 𝑑𝑟 = (26)
= = − 𝑖 (20) 𝑑𝑟 ||𝑘𝑗 𝐶𝑡ℎ
𝑑𝑡 𝑑𝑡 𝑑𝑡
The radial concentration gradient of the free-flowing fluid to the de-
Substitution of Eq. (20) into Eq. (19) gives Eq. (21) as follows:
[( posit layer is expressed as:
) ( )]
𝑑𝛿 1 𝜕𝐶 || 𝜕𝐶 || 𝜕𝐶 || 𝑑𝐶 (𝑇𝑜 − 𝑇𝑖 )
= −𝐷𝑤𝑜 − − 𝐷 (21) = ℎ𝑇 .
𝜕𝑟 ||𝑟𝑖 𝜕𝑟 ||𝑟+
(27)
𝜕𝑟 ||𝑟𝑖
𝑒
𝑑𝑡 𝜌𝑑𝑒𝑝 𝐹𝑤 𝑑𝑇 𝐶𝑡ℎ
𝑖

The first order differential equation of Eq. (21) can be solved in order where, To and Ti are the temperatures of oil at the center and at the
to determine the absolute value of the thickness of solid wax deposit as oil-wax interface respectively, hT is convective heat transfer.
follows: The shear dispersion effect is accounted for by using the heat transfer
[( ) ( )] equation to determine the temperature gradient around the pipe wall
𝑡 𝜕𝐶 || 𝜕𝐶 || where waxy gel is deposited as follows:
𝛿 = −𝐷𝑤𝑜 + 𝐷𝑒 + 𝑘1 (22a)
𝜌𝑑𝑒𝑝 𝐹𝑤 𝜕𝑟 ||𝑟𝑖 𝜕𝑟 ||𝑟+
𝑖 𝑑𝑇 || 𝑚̇ 𝐶 𝑑𝑇
= . (28a)
where, k1 is the constant of the integration. At t = 0, 𝛿 = 0, therefore, 𝑑𝑟 ||𝑟+𝑖 2 𝐶𝑡ℎ 𝜋 𝑅 𝑑Δ𝐿
k1 = 0
The pipe effective diameter is reduced due to deposition of waxy gel
The actual deposition thickness of the solid wax at time t, can be
in the pipe which eventually causes flow obstruction [50]. This may lead
modelled as follows:
[( ( )] to high pressure build-up in the pipe and high shear stress on the de-
)
𝑡 𝜕𝐶 || 𝜕𝐶 || posited wax thereby causing mechanical removal of some of the deposit.
𝛿 = −𝐷𝑤𝑜 + 𝐷 (22b)
𝜌𝑑𝑒𝑝 𝐹𝑤 𝜕𝑟 ||𝑟𝑖 𝑒
𝜕𝑟 ||𝑟+𝑖 Thus, shear stripping should not be neglected during the modelling of
wax deposition [51]. Therefore, Reynold’s number(RE ) and temperature
Similarly, the rate at which the solid wax fraction grows in the de- that respectively determine the flow regime and the precipitation rate
posit can be obtained by substituting Eq. (17b) into Eq. (12c) as follows: should be incorporated into the heat transfer equation to account for
( ) the shear stripping effect as follows:
𝑑 𝐹𝑤 𝜕𝐶 || | 𝑅𝐸 𝑃𝑟 𝑑𝑇
𝜋 (𝑅2 − 𝑟2𝑖 ) Δ𝐿 𝜌𝑑𝑒𝑝 = 2 𝜋 𝑟𝑖 Δ𝐿 −𝐷𝑒 (23a) 𝑑𝑇
𝑑𝑡 𝜕𝑟 ||𝑟+𝑖 |
|+ = . (28b)
𝑑𝑟 |𝑟𝑖 4 𝑑Δ𝐿
( )
| 2 𝜌𝑑𝑒𝑝 𝑉𝑧 𝑅
2 𝑟𝑖 −𝐷𝑒 𝜕𝐶 |
𝜕𝑟 |𝑟+ 𝑅𝐸 = (29b)
𝑑 𝐹𝑤 𝑖 𝜇
= (23b)
𝑑𝑡 (𝑅2 − 𝑟2𝑖 ) 𝜌𝑑𝑒𝑝
𝜇 𝐶𝑠
𝑃𝑟 = (29b)
Substituting R − 𝛿 = ri into eqn (23b) above will give: 𝐶𝑡ℎ
( )
| The Reynolds’s number (RE )determines the influence of fluid velocity
2 (𝑅 − 𝛿) −𝐷𝑒 𝜕𝐶 |
𝜕𝑟 |𝑟+
𝑑 𝐹𝑤 𝑖
and flow regime on wax deposition. Pr is the Prandtl number (Pr ), which
= (23c) measures the influence of viscosity on wax deposition. The temperature
𝑑𝑡 𝛿 (2𝑅 − 𝛿) 𝜌𝑑𝑒𝑝
of the fluid flowing in the pipe of length, ΔL, can be determined as
The absolute value of the solid wax fraction (Fw ) in the deposit at follows [113]:
time tcan be obtained by solving the differential equation of the growth Recalled from Eq. (11c):
rate of solid wax fraction (Eq. 23c) as follows:
( ) 𝑇(Δ𝐿) = 𝑇𝑎 + (𝑇𝑜 − 𝑇𝑎 ) 𝑒−(ℎ𝑜 𝜋 𝑑Δ𝐿∕𝑚̇ 𝐶) (29c)
2 𝑡 (𝑅 − 𝛿) 𝜕𝐶 ||
𝐹𝑤 (𝑡) = −𝐷𝑒 + 𝑘2 (24a) Differentiation of Eq. (11c) with respect to ΔLgives:
𝛿 (2 𝑅 − 𝛿) 𝜌𝑑𝑒𝑝 𝑑𝑟 ||𝑟+
𝑖
𝑑𝑇 − 2 ℎ𝑜 𝜋 𝑅 (𝑇𝑜 − 𝑇𝑎 ) −(2 ℎ 𝜋 𝑅 Δ𝐿∕𝑚̇ 𝐶)
= 𝑒 𝑜 (30)
k2 is the constant of the integration. At t = 0, Fw = 0, therefore, 𝑑Δ𝐿 𝑚̇ 𝐶
k2 = 0. Substitution of Eq. (30) in Eq. (28a) gives:
The following equation (Eq. 24b) can be used to model the actual
𝑑𝑇 | ℎ𝑜 ( )
solid wax fraction deposited at time t as follows: | 𝑇 − 𝑇𝑎 𝑒− (2 ℎ𝑜 𝜋 𝑅 Δ𝐿∕𝑚̇ 𝐶)
𝑑𝑟 |+ = 𝐶𝑡ℎ 𝑏
(31)
( ) |𝑟𝑖
2 𝑡 (𝑅 − 𝛿) 𝜕𝐶 ||
𝐹𝑤 (𝑡) = −𝐷𝑒 (24b) Thus, the deposit layer concentration gradient is given as:
𝛿 (2 𝑅 − 𝛿) 𝜌𝑑𝑒𝑝 𝑑𝑟 ||𝑟+𝑖
𝜕𝐶 || 𝑑𝐶 ℎ𝑜 ( )
= − . 𝑇 − 𝑇𝑎 𝑒− (2 ℎ𝑜 𝜋 𝑅 Δ𝐿∕𝑚̇ 𝐶) (32)
The following equation (Eq. 25a) was used by Zhenyu et al. [116] to 𝜕𝑟 ||𝑟+𝑖 𝑑𝑇 𝐶𝑡ℎ 𝑜
approximately determine the wax concentration gradient, 𝜕𝐶
𝜕𝑟
,
𝑖 The thickness of the wax deposit at time, t(s) can be obtained as
𝐶𝑘 − 𝐶𝑗 𝐶𝑘 (𝑒𝑞) − 𝐶𝑗(𝑒𝑞) follows:
𝜕𝐶 ||
= ≈ ; 𝑘 = 𝑤𝑜, 𝑗 = 𝑒 (25a)
𝜕 𝑟𝑖 ||𝑘𝑗
Recall,
𝑟𝑖 𝑟𝑖
𝜕𝐶 ||
𝑞𝑚, 𝑖𝑛 = −𝐷𝑤𝑜 (10𝑏)
The wax concentration gradient cannot be determined by 𝜕𝑟 ||𝑟𝑖
eqn (25a) because at the prediction period, ri is unknown. There- ( )
fore, 𝜕𝐶 | as defined in Eq. (25b) can be used to determine wax
𝜕 𝑟 𝑘𝑗 𝜕𝐶 ||
𝑖 𝑞𝑚, 𝑎𝑔𝑖𝑛𝑔 = −𝐷𝑒 (12𝑏)
concentration gradient, which can be approximated by the solubility 𝜕𝑟 ||𝑟+𝑖

6
A.A. Olajire Chemical Engineering Journal Advances 6 (2021) 100104

bility is difficult and cost-intensive (Edmonds et al. [94]. There are two
types of thermodynamic models based on flash condition, and these in-
clude multi-solid (MS) and solid solution (SS) thermodynamic models. In
the latter, all components were assumed to contribute to the formation
of wax, thus over-estimating the amount of wax deposited [121]. The
solid solution (SS) model utilizes two types of equation of state (EOS)
and activity coefficients simultaneously to describe the non-ideality of
the liquid state, thus making the model to be thermodynamically incon-
sistence [122]. However, the non-ideality of phases in equilibrium was
Fig. 2. Plot of correlation of field data against simulated data based on previous described by MS model by utilizing only the EOS without the need for
study [119]. any other adjustable mixture parameters, thus making the model to be
very simple, practicable and accurate.
Table 3
Correlation data between calculation and experimental
results [120]. 3.2.1. Multiple solid model (MS)
The multiple solid (MS) model considers each pure component as a
Oil sample Layer 𝜀d (%) Δd (%)
separate immiscible solid component. Thus, the fugacity of component
Oil A Layer A wax deposit 6.63 3.85 i in all phases is equal under a vapor-liquid-solid equilibrium (VLSE)
Layer B wax deposit 12.24 8.11
phase, in accordance with the following equation:
Oil B Layer A wax deposit 12.08 5.06
Layer B wax deposit 21.48 10.81
𝑓𝑖𝐿 = 𝑓𝑖𝑉 = 𝑓𝑝𝑢𝑟𝑒,
𝑆
𝑖 𝑖 = 𝑛 − 𝑁𝑠 + 1, ...... 𝑛 (34a)
𝜀d and Δd are the maximum and standard deviations
(%)
𝑓𝑖𝐿 = 𝑓𝑖𝑉 𝑖 = 1, 2, .......𝑛 − 𝑁𝑠 (34b)
Then, substitution of Eq. (27) into Eq. (10b) and Eq. (32) into
where, f, n and Nsare the fugacity, the total number of components, and
Eq. (12b) will respectively give the following:
the number of solid phases, respectively as determined by Michelsen’s
𝑑𝐶 (𝑇𝑜 − 𝑇𝑖 ) stability analysis [123], the superscript denotes the phases of the com-
𝑞𝑚, 𝑖𝑛 = −𝐷𝑤𝑜 ℎ𝑇 . (33a)
𝑑𝑇 𝐶𝑡ℎ ponent.
The fugacities of liquid and vapor phases are calculated directly by
𝑑𝐶 ℎ𝑜 ( )
𝑞𝑚, 𝑎𝑔𝑖𝑛𝑔 = −𝐷𝑒 . 𝑇 − 𝑇𝑎 𝑒− (2 ℎ𝑜 𝜋 𝑅 Δ𝐿∕𝑚̇ 𝐶) (33b) using the EOS, while the solid phase fugacity can be calculated by using
𝑑𝑇 𝐶𝑡ℎ 𝑜
the fusion properties. The corresponding variables for the pure solid can
Then, Eqs. (22b) and (24b) become: then be estimated by using fugacity and the Gibbs free energy change of
𝑡 [ ] a pure liquid compound. Different thermodynamic approaches are used
𝛿 = 𝑞 − 𝑞𝑚, 𝑎𝑔𝑖𝑛𝑔 (33c)
𝜌𝑑𝑒𝑝 𝐹𝑤 𝑚, 𝑖𝑛 in different studies for the analysis of these non-idealities. A general
expression which relates fugacity and Gibbs free energy change is as
2 𝑡 (𝑅 − 𝛿) ( )
𝐹𝑤 (𝑡) = 𝑞 (33d) given in Eq. (35), however the variation of the equation depends on the
𝛿 (2 𝑅 − 𝛿) 𝜌𝑑𝑒𝑝 𝑚, 𝑎𝑔𝑖𝑛𝑔
theoretical approach of the analysis [36, 124].
Eq. (33a-d) can be used to calculate the wax deposition thickness if ( ) ( ) ( )
the field data are known. 𝑓𝑖𝑆 Δ𝐻𝑖𝑓 𝑇 Δ𝐻𝑖𝑡𝑟 𝑇
Studies have been conducted recently by various research groups to 𝐼𝑛 = − 1− − 1−
𝑓𝑖𝐿 𝑅𝑇 𝑇𝑖𝑓 𝑅𝑇 𝑇𝑖𝑡𝑟
𝑃 𝑢𝑟𝑒, 𝑖
evaluate the reliability of dynamic model for predicting wax deposition.
𝑓 𝑓
Recently, Duan et al. [110] predicted the growth of wax deposit along 𝑇𝑖 𝑇𝑖 𝑃
1 1 Δ𝐶𝑝𝑖 Δ𝑉𝑖
the circumferential distribution as a function of time by using the devel- + Δ𝐶𝑝𝑖 𝑑 𝑇 − 𝑑𝑇 + 𝑑𝑃
oped model that is similitude to dynamic model. The model was reported 𝑅𝑇 ∫ 𝑅 ∫ 𝑇 ∫ 𝑅𝑇
𝑇 𝑇 𝑃0
to show acceptable agreement with Matzain’s experimental results for
(35)
the prediction of wax deposition thickness along the circumference of
the pipe wall. In a similar study, Obaseki and Elijah [119] predicted the
The change in heat capacity (ΔCpi ) can be calculated with the corre-
wax deposition thickness in pipeline tubing by using the dynamic model.
lation proposed by Pedersen et al. [125] as follows:
The model was reported to exhibit better performance and the simulated
result was found to be perfectly closed to the field data (Fig. 2), with an 𝐿 𝑆
Δ𝐶𝑝𝑖 = 𝐶𝑝𝑖 − 𝐶𝑝𝑖 = 𝑏1 𝑀 𝑊𝑖 + 𝑏2 𝑀 𝑊𝑖 𝑇 (36)
average percentage error of 3%. The results of the model were reported
to be useful for the determination of other parameters including effec- where, 𝑓𝑖𝑠 is the fugacity of the solid phase, Δ𝐻𝑖𝑓 and Δ𝐻𝑖𝑡𝑟 are the
tive diameter of the pipe, the real pressure drop and volumetric flow enthalpies of fusion and solid-solid transition between different solid
rate. phases respectively, ΔVi is the difference between the solid and liquid
In another study, Li et al. [120] proposed a dynamic model based on phase molar volume of component i, 𝑇𝑖𝑓 and 𝑇𝑖𝑡𝑟 are temperatures of fu-
the diffusion of wax molecules and counter-diffusion of oil molecules us- sion and the transition temperature respectively, Δ𝐶𝑝𝑖 is the difference
ing the Fick’s second law, which allowed the incorporation of the max- between solid and liquid state heat capacities at constant pressure for
imum stacking fraction and orientation order of wax crystal to obtain component i, and Ris the ideal gas constant, b1 , b2 are obtainable from
the tortuosity and diffusivity of de-waxed oil molecules. The calculated the experimental fitting. However, in the absence of experimental data
results were found to be in good agreement with experimental results b1 , b2 can be taken as:
(Table 3).
𝑏1 = 0.3033 (37a)
3.2. Thermodynamic model

Thermodynamic model has been found to be a useful tool for predict- 𝑏2 = −4.635 𝑥 10−4 (37b)
ing the wax deposition condition, particularly in places where accessi-

7
A.A. Olajire Chemical Engineering Journal Advances 6 (2021) 100104

Substitution of Eq. (36) into Eq. (35) gives: The solubility parameters of other components, such as naphthenic,
( 𝑆) ( ) ( ) aromatic and asphalt can be estimated by correlations proposed by
𝑓 Δ𝐻𝑖𝑓 𝑇 Δ𝐻𝑖𝑡𝑟 𝑇 Leelavanichkul et al. [129] as follows:
𝐼𝑛 = − 1− 𝑓 − 1 − 𝑡𝑟
𝑓 𝐿 𝑃 𝑢𝑟𝑒, 𝑖 𝑅𝑇 𝑇𝑖 𝑅𝑇 𝑇𝑖 ( )
𝛿𝑖,𝐿𝑛𝑎𝑝 = 8.7 − exp 2.219195 − 0.54907 𝑀𝑊𝑖0.3 (44b)
( 𝑓 )
𝑏 𝑀 𝑇𝑖 𝑇
+ 1 𝑖 − 1 + 𝐼𝑛 𝑓 ( )
𝑅 𝑇 𝑇 𝛿𝑖,𝐿𝑎𝑟𝑜𝑚 = 8.8 − exp 2.219195 − 0.54907 𝑀𝑊𝑖0.3 (44c)
𝑖
𝑃
𝑏2 𝑀𝑖 ⎛⎜ (𝑇𝑖 ) ⎞
𝑓 2
𝑇 Δ𝑉𝑖 ( )
+ + − 𝑇𝑖𝑓 ⎟ + 𝑑𝑃 (38) 𝛿𝑖,𝐿𝑎𝑠𝑝ℎ𝑎𝑙 = 9.3 − exp 2.219195 − 0.54907 𝑀𝑊𝑖0.3 (44d)
𝑅 ⎜ 2𝑇 2 ⎟ ∫ 𝑅𝑇
⎝ ⎠ 𝑃0
The solubility parameter of the component iin the solid phase can be
Among the equations of state, Peng Robinson equation of state is calculated as follows:
( )0 . 5
used [126]:
𝑆
Δ𝐻𝑖𝑓 𝐿2
𝑅𝑇 𝑎 𝛿𝑖 = + 𝛿𝑖 (45)
𝑃 = − (39) 𝑉
𝑉 −𝑏 𝑉 (𝑉 + 𝑏) + 𝑏(𝑉 − 𝑏)
The molar volumes of liquid and solid can be calculated with the
3.2.2. Solid solution model (SS) following expression [127]:
This model expresses the fugacities in the solid and liquid phases as
𝑀 𝑊𝑖
follows: 𝑉𝑖 = 𝑉𝑖𝐿 = 𝑉𝑖𝑆 = (46a)
𝐷𝑖,𝐿25
𝑓𝑖𝑆 (𝑝, 𝑇 , 𝑥𝑆𝑖 ) = 𝑥𝑆𝑖 𝛾𝑖𝑆 𝑓𝑃𝑆𝑢𝑟𝑒, 𝑖 (40a)
where, 𝐷𝑖,𝐿25 is the density of the liquid phase of component iat 25°C, and
is expressed as:
𝑓𝑖𝐿 (𝑝, 𝑇 , 𝑥𝐿
𝑖 ) = 𝑥𝐿 𝐿 𝐿
𝑖 𝛾𝑖 𝑓𝑃 𝑢𝑟𝑒. 𝑖 (40b)
13.06
𝐷𝑖,𝐿25 = 0.8155 + 0.6272 𝑥 10−4 𝑀 𝑊𝑖 − (46b)
𝑀 𝑊𝑖
𝐿
( 𝐿
) ( )
𝑓𝑖 𝑝, 𝑇 , 𝑥𝑖 = 𝑓𝑖𝑆 𝑝, 𝑇 , 𝑥𝑆𝑖 (40c) Molecular weight of different classes can be calculated by single car-
The criterion of equal fugacities can be obtained by the combination bon number (SCN) as follows:
of Eqs. (40 a-c) as follows: 𝑀 𝑊𝑖, 𝑝𝑎𝑓 𝑓 . = 12.01 𝐶𝑖 + 1.008 (2 𝐶𝑖 + 2) (47a)
𝑥𝑆𝑖 𝛾𝑖𝐿 𝑓𝑃𝐿𝑢𝑟𝑒, 𝑖
= (40d)
𝑥𝐿 𝛾𝑖𝑆 𝑓𝑃𝑆𝑢𝑟𝑒, 𝑖 𝑀 𝑊𝑖, 𝑛𝑎𝑝ℎ = 12.01 𝐶𝑖 + 1.008 (1.8 𝐶𝑖 ) (47b)
𝑖

A regular solution theory was used by Won [127] to determine the

activity coefficients of individual components in the liquid and sold 𝑀 𝑊𝑖, 𝑎𝑟𝑜𝑚. = 12.01 𝐶𝑖 + 1.008 𝐶𝑖 (47c)
phases. The relationship between activity coefficients and solubility pa- The ratio of fugacity of each solid component is a function of their
rameters 𝛿 i for each component is given as: fusion properties, which include melting point temperature (fusion tem-
𝑉𝑖𝐿 (𝛿̄𝐿 − 𝛿𝑖𝐿 ) perature), enthalpy of fusion and heat capacity change. The fusion prop-
2
𝐼𝑛 𝛾𝑖𝐿 = (41a) erties are different for various components, such as saturates, aromatics,
𝑅𝑇
etc., that exist in crude oil. The correlation proposed by Won [127] can
𝑉𝑖𝑆 (𝛿̄𝑆 − 𝛿𝑖𝑆 )
2 be used to express the fusion temperature as a function of molecular
𝐼𝑛 𝛾𝑖𝑆 = (41b) weight as follows:
𝑅𝑇
20172
The combination of Eqs. (41a) and (41b) gives: 𝑇𝑖,𝑓𝑝𝑎𝑟𝑎𝑓 . = 374.5 + 0.02617 𝑀 𝑊𝑖 − (48a)
𝑀 𝑊𝑖
{ }
𝛾𝑖𝐿 𝑉 𝑖 [( ) ( ) ]
The above correlation (Eq. 48a) holds for MW < 450, while for MW
= exp 𝛿̄ − 𝛿𝑖 2 − 𝛿̄ − 𝛿𝑖 2 (41c)
𝑅𝑇 𝐿 𝑆
𝛾𝑖𝑆 > 450, i.e., for waxy phase, it is converted to [130]:
The average solubility parameters can be determined as follows: 32326
∑ 𝑇𝑖,𝑓𝑝𝑎𝑟𝑎𝑓 . = 411.4 − (48b)
𝑀 𝑊𝑖
𝛿̄𝐿 = 𝜙𝐿 𝐿
𝑖 𝛿𝑖 (42a)
𝑖 The fusion temperatures of naphthalene and aromatics can also be es-
∑ timated with the correlation proposed by Pan and Firoozabadi [131] and
𝛿̄𝑆 = 𝜙𝑆𝑖 𝛿𝑖𝑆 (42b) Lira-Galena et al. [132] as follows:
𝑖
( )
𝑇𝑖, 𝑛𝑎𝑝ℎ, 𝑎𝑟𝑜𝑚. = = 333.46 − 419.01 exp −0.00855 𝑀 𝑊𝑖 (48c)
𝑥𝐿
𝑖 𝑉𝑖
𝐿
𝜙𝐿
𝑖 = ∑ 𝐿 𝐿 (43a) A correlation was developed by Won [127] for calculating the en-
𝑖 𝑥𝑖 𝑉𝑖
thalpy of fusion of paraffinic component as follows:
𝑥𝑆𝑖 𝑉𝑖𝑆
𝜙𝑆𝑖 = ∑ 𝑆 𝑆 (43b) Δ𝐻𝑖,𝑓 𝑝𝑎𝑟𝑎𝑓 . = 0.1426 𝑀 𝑊𝑖 𝑇𝑖𝑓 (49a)
𝑖 𝑥𝑖 𝑉𝑖
Dalirsefat and Feyzi [133] improved upon the above correlation
̄ 𝛿 i Vi and 𝜑i are the activity coefficient, average solubility
where, 𝛾 i , 𝛿, equation (Eq. 49a) by incorporating the effects of naphthenes and aro-
parameter, solubility parameter, molar volume and the volume fraction matics on the enthalpy of fusion as follows:
of component i respectively, superscripts S and L represent the states
Δ𝐻𝑖,𝑓 𝑝𝑎𝑟𝑎𝑓 . = 0.06599 𝑀 𝑊𝑖 𝑇𝑖𝑓 (49b)
of the phases.
A correlation was proposed by Riazi and Al-Sahhaf [128] for cal- A set of correlation which differentiates between the odd and even
culating the solubility parameter of component i in liquid solution of carbon numbers was considered by Chen et al. [130] for the estimation
paraffin in crude oil as follows: of heat of fusion as follows:
( )
𝛿𝑖,𝐿𝑝𝑓 𝑓 𝑖𝑛 = 8.6 − exp 2.219195 − 0.54907 𝑀𝑊𝑖0.3 (44a) 𝑜𝑑𝑑 (7 < 𝐶𝑛 < 21) ∶

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A.A. Olajire Chemical Engineering Journal Advances 6 (2021) 100104

Table 4
Average deviation(Δd ) of precipitated wax (wt%) [135].

Model Δd (%)
Oil# 1 Oil# 2 Oil# 3 Oil# 4

PC-SAFT model 0.304079 0.616382 0.78932 0.38124

Multiple solid model 0.686717 1.19769 1.011303 0.455587
Solid solution model 1.097626 1.082606 0.884007 0.69292

crude oil 3 and 4 while multiple solid model gave better performance
for crude 1 and 4.
In a separate study, Yang et al. [108] developed a thermodynamic
model with the new solid-solution model to predict wax precipitation,
where a combination of regular solution and Flory-free volume equa-
tion (RSFV) was used to obtain the non-ideality of liquid phase while
three different solid solution models, including regular solution (RS),
improved regular solution model (IRSM) and Wilson equation (W) were
used to describe the non-ideality of the solid phase. The experimental
data of binary, ternary, quartenary and multi-paraffins systems at atmo-
spheric pressure with temperature varying from 260 K to 350 K were
used to validate the three models. The calculation results of all the three
solid-liquid equilibrium models
(RSFV-RS, RSFV-W and RSFV-IRSW) were found to predict WDT well
Fig. 3. Agreement between the theoretical and actual results of wax deposition compared to the experimental data in the binary systems with the abso-
based on previous study [134]. lute average relative error (AARE) of less than 1% (Table 5). None of the
three thermodynamic models predicts the best WATs for different mix-
tures of the ternary systems. However, RSFV-IRSW gave the most stable
prediction accuracy with AAREs of 0.82% and 0.62% for C36 -C32 -C7 and
Δ𝐻𝑖𝑓 = 0.5754 𝑀 𝑊𝑖 𝑇𝑖𝑓 (50a)
C18 -C16 -C11 , respectively compared to RSFV-RS and RSFV-W. Also, the
most precise WDTs was predicted by RSFV-IRSW for C24 -C22 -C7 with
𝑒𝑣𝑒𝑛 (8 < 𝐶𝑛 < 22) ∶ an AARE of 0.34%. In quaternary system, RSFV-IRSW has a minimum
AARE of 0.2 while the large discrepancy between the predicted WATs
obtained from RSFV-W and the experimental data, with AARE of 1.44,
Δ𝐻𝑖𝑓 = 0.8064 𝑀 𝑊𝑖 𝑇𝑖𝑓 (50b)
was attributed to the neglect of enthalpy effect.
Recently, Mansourpoor et al. [136] developed a multi-solid thermo-
(22 < 𝐶𝑛 < 38) ∶ dynamic model using Peng and Robinson equation of state (PR EOS) to
predict wax disappearance temperature (WDT) and the model was vali-
dated with experimental data of multi-component and ternary systems.
Δ𝐻𝑖𝑓 = 0.4998 𝑀 𝑊𝑖 𝑇𝑖𝑓 (50c) Their results showed that the average absolute relative error (AARE) of
the model for ternary systems was 0.52% which was much lower among
(𝐶𝑛 > 38) ∶ the previously developed thermodynamic models. Also, the AARE of the
new model for 68 data points was found to be 0.23% with R-square value
of 0.97, indicating that the model closely agrees with the experimental
Δ𝐻𝑖𝑓 = 0.6741 𝑀 𝑊𝑖 𝑇𝑖𝑓 (50d) data. The accuracy of the model was further confirmed from the cumu-
lative distribution function which indicated that P50 values for model
The correlations proposed by Pan and Firoozabadi [131] can be used
and experimental data are almost the same. The accuracy of the model
to calculate the heat of fusion of naphthenic and aromatics as follows:
was found to increase as the average carbon number of oil mixtures in-
Δ𝐻𝑖,𝑓 𝑛𝑎𝑝ℎ. = 0.2216 𝑀 𝑊𝑖 𝑇𝑖𝑓 (51a) creases. Their findings also revealed that the proposed thermodynamic
model can accurately predict WDT of waxes in multi-component systems
and ternary mixtures.
Δ𝐻𝑖,𝑓 𝑎𝑟𝑜𝑚𝑎 = 46.89216 𝑀 𝑊𝑖 𝑇𝑖𝑓 (51b)

The process of wax deposition from crude oil has been accurately de-
scribed by thermodynamic models by various research groups. A ther-
modynamic model was proposed by Liu et al. [134] to determine cloud
point of paraffin wax and the deposited paraffin wax with lowering of
the temperature by using regular solution theory to correlate the non-
ideality and activity coefficient of the solid phase mixture. The predicted
results were found to be in good agreement with the experimental data
(Fig. 3).
A statistical thermodynamic method based on the Perturbed Chain
form of the Statistical Associating Fluid Theory (PC-SAFT) model was
developed by Meighani et al. [135] to evaluate the wax precipitation
in crude oil below the WAT. The developed PC-SAFT model proposed
was found to show less deviation from experimental data than results of
other basic models that are commonly used in the petroleum industry
(Table 4). However, solid solution model showed better performance for
3.3. Rugg, Rydahl and Ronningsen model
Rugg, Rydahl and Ronningsen (RRR) model is a multi-phase model
used for the prediction of wax deposition in production tubings [64] and
is exclusively applicable to turbulent flow alone [137]. A standard
steady state multi-phase model is used for predicting the pressure drop
and liquid hold-up along the pipeline. The deposition of wax along
the pipeline in the multi-component wax model can be estimated from
the diffusion of wax from the bulk medium towards the suface of the
pipeline due to temperature gradients and shear dispersion effect. The
variation in the inner pipe wall thickness has been attributed to the de-
position of wax [138-142]. The two mechanisms, including molecular
diffusion and shear dispersion on which RRR model is based have been
reported to enhance the wax deposition [140]. The volumetric rate of
wax deposition for a waxy component i in a molecular diffusion mech-

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A.A. Olajire Chemical Engineering Journal Advances 6 (2021) 100104

Table 5
The absolute average relative errors (%) of various systems [108].

System Composition RSFV-RS RSFV-W RSFV-IRSW

Binary systems C23 -C7 C25 -C7 C26 -C7 C28 -C7 C36 -C7 0.520.310.660.680.8 0.510.310.650.670.83 0.430.260.600.600.67
Ternary systems C24 -C22 -C7 C36 -C32 -C7 C18 -C16 -C11 0.540.70.74 0.531.010.51 0.340.820.62
Quaternary system C26 -C25 -C24 -C10 0.53 1.44 0.2
Multiple system C10 -synthetic waxy mixture (C18 to C36 ) 0.29 1.76 0.9

anism is expressed as:

𝑁𝑤𝑎𝑥 ( )
𝑑𝑖𝑓 𝑓
∑ 𝐷𝑖 𝐶𝑖𝑏 − 𝐶𝑖𝑤 𝑆𝑤𝑒𝑡 𝑀 𝑊𝑖
𝑉 𝑜𝑙𝑤𝑎𝑥 = 2 𝜋 𝑟 Δ𝐿 (52a)
𝑖=1
𝛿 𝜌𝑖

where, 𝐶𝑖𝑏 𝑎𝑛𝑑 𝐶𝑖𝑤 are respectively the molar concentrations (mole/m3 )
of the dissolved wax component i of the oil phase in the bulk and at
the wall of the pipe, Swet is the fraction of the wetted circumference and
for multi-phase flow, the wetted inner surface area depends on the local
flow regime predicted and the liquid hold-up [138], Nwax is the number
of wax components, MWi is the molecular weight of wax component
i(kg/mole), 𝜌i is the density of wax component i(kg/m3 ), 𝛿 is the thick-
ness of the sub-layer in turbulent flow, and is calculated by using Blasius
equation, D is the diffusion coefficient (m2 /s) which can be determined
from the correlation of Hayduk and Minhas [59].
Similarly, the volumetric rate of wax deposition for a shear depo-
sition effect can be calculated from the proposed correlation of Burger
et al [32] as follows:
𝑠ℎ𝑒𝑎𝑟 𝐾 ∗ 𝐶𝑤𝑎𝑙𝑙 𝛾̇ 𝐴
𝑉 𝑜𝑙𝑤𝑎𝑥 = (52b)
𝜌𝑤𝑎𝑥 Fig. 4. Algorithm for wax deposition modeling based on previous study [144].
Therefore, the total rate of increase in wax-layer thickness, 𝛿, involv-
ing both mechanisms can be expressed (Eq. 53) as follows:
rate by empirically modifying Fick’s law that fails to account for them.
𝑑𝑖𝑓 𝑓 . 𝑠ℎ𝑒𝑎𝑟
𝑉 𝑜𝑙𝑤𝑎𝑥 + 𝑉 𝑜𝑙𝑤𝑎𝑥 They added two empirical correction terms, based on their experimental
𝛿 = (53)
(1 − 𝜑) 2 𝜋 𝑟 Δ𝐿 data and the overall deposition rate of the wax was then expressed as
where, 𝜙 is the porosity of the wax deposited, which is in the range of [145]:
0.6 – 0.9 [94]. ∏ [ ]
𝑑𝛿 1 𝑑 𝑤𝑤 𝑑𝑇
The shear stress exerted by the oil that resulted to the removal of wax = ∏ 𝐷𝑜𝑤 (55)
𝑑𝑡 1 + 2 𝑑𝑇 𝑑𝑟
from the pipe wall at high velocity flow rates was not accounted for by
the RRR model. However, a dissolution model of the wax deposition where, ww is the weight percent concentration of wax in solution (wt %),
∏
on the pipe wall was implemented by the model, where dissolved wax ris the radial distance (m), Dow is the turbulent mass diffusion, 1 is the
concentration with respect temperature, dCw /dT, at respective WAT and factor related to the enhancement rate due to entrapment of oil in the
with the adjusted WDT when the temperature is above WDT are as given deposited wax layer, which also accounts for any positive deposition
∏
in the following equations [88]: rate that is not accounted for by Dow , 2 is the factor related to the
reduction rate due to shear stripping.
𝑊 𝐷𝑇 = 𝑊 𝐴𝑇 + Δ𝑇𝑑𝑖𝑠𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 (54a)
The two influential factors were defined by the following equations:
𝑑 𝐶𝑤 || ∏ 𝐶1
𝐶𝑤𝑠 = 𝐶𝑤, 𝑇𝑆 + (𝑇 − 𝑊 𝐷𝑇 ) (54b)
𝑑𝑇 ||𝑊 𝐴𝑇 𝑆 =
1 − 𝐶𝑜𝑖𝑙 ∕100
(56a)
1
where, 𝐶𝑤, 𝑇𝑆 is the concentration of the wax at the temperature of the
deposit surface TS . ∏ 𝐶
= 𝐶2 𝑁𝑆𝑅3 (56b)
In the normal diffusion equation, the adjusted Cws is used, where
2
(Cwb − Cws ) is the potential driver of the diffusion process, where melt-
ing process occurs when Cws is higher than Cwb . where, NSR is a dimensional quantity, expressed as a flow regime and
depends on Reynolds number.
3.4. Matzain model Wilke and Chang [38] gave the diffusion constant in their correla-
tion, which according to Matzain et al. [144], is insufficient to account
Matzain’s model uses thermodynamic principles of equilibrium for the proportionality constant that drives the diffusion process. Met-
model (EM), with empirical coefficients that account for the shear strip- zain et al. [144] therefore incorporated C1 , C2 , and C3 as dimension-
ping and thickness enhancement due to trapped oil in the deposit. How- less quantity which are empirically correlated from their experimental
ever, Mehta et al. [143] reported that shear stripping was less important, data for single-phase and two-phase flow regimes, and their values were
while maintaining that other mechanisms may have effect on the wax given as follows: C1 = 15.0, C2 = 0.055, and C3 = 1.4 . However,
deposition rate. The algorithm that is generally used for wax deposition C2 and C3 were found to be invariant with time due to the limited un-
modeling is schematically given below (Fig. 4). derstanding of aging. Also, Coil gives the percentage of entrapped oil in
The shear stripping reduces deposition rate while the enhancement the deposited wax (%) and is calculated as follows:
of deposition rate takes place by entrapment of oil and other mecha- ( 0.15 )
𝑁𝑅𝐸.𝑓
nisms. Matzain model tried to account for the influences of shear strip-
𝐶𝑜𝑖𝑙 = 100 1 − (57a)
ping and oil entrapment in the deposited wax layer on the deposition 8

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A.A. Olajire Chemical Engineering Journal Advances 6 (2021) 100104

Fig. 5. a. Wax deposit distribution of single phase in horizontal pipes. Fig. 5b.
Wax deposit distribution of intermittent in horizontal pipes [146]. Fig. 5c. Wax
deposit distribution of annular in horizontal pipes [146]. Fig. 5d. Wax deposit
Fig. 5. Continued
distribution of stratified smooth/waxy in horizontal pipes [146].

Stratified smooth/Wavy:
( )
𝜃
𝜌𝑜 𝐸𝑠𝐿 𝛿
𝑁𝑆𝑅 = (58d)
𝜇𝑜, 𝑓
Stratified smooth is accompanied with wax deposit on the bottom
section of the pipe with a decreasing thickness as it moves upward due
to higher transfer rates in the bottom rather than in the upward posi-
tion. Stratified and stratified wavy flows are characterized by soft and
Fig. 5. Continued
harder deposits at the bottom of the pipe and along the interface phase
respectively. The distribution of both depositions is shown below.
The shear stripping effect as illustrated in Eq. (58a-d) above depends
on the thickness of the wax layer (𝛿), flow conditions and velocity of the
fluid (𝜃 sL ). The modelling of the shear stripping is similar to the direct
dependency of reduction in deposition rate on the diffusion rate [143],
and thus the molar deposition rate for a wax forming component iwas
proposed as follows:
∏
𝐷𝑤𝑖 (𝐶𝑖𝑏 − 𝐶𝑇𝑤 ) 𝑑𝑇
Fig. 5. Continued 𝑛̇ 𝑑𝑒𝑝
𝑖 = 1
∏ . . (59a)
1+ 2 𝑇𝑏 − 𝑇𝑤 𝑑𝑟
The thermal gradient of the laminar sub-layer was expressed as fol-
( ) lows:
𝜃𝑆𝐿
𝜌𝑜 𝑑𝑤
𝐸 𝑑𝑇 (𝑇𝑏 − 𝑇𝑤 )
𝑁𝑅𝐸.𝑓 = (57b) = (59b)
𝜇𝑜, 𝑓 𝑑𝑟 𝜆𝑜

where, 𝜌o is the oil density (kg/m3 ), 𝜃 sL is the velocity of superficial liquid where, 𝜆o is the thermal conductivity of the oil (J/s.m.K), Tb and Tw are
(m/s), E is the liquid hold up, dw is the inner diameter of the pipe due the temperatures of the bulk flow and the inner wall surface respec-
to wax build-up (m), 𝜇 o, f is the viscosity of the oil (kg/ m. s). tively (K), hw is the heat transfer coefficient of the inner wall surface
The flow pattern was reported to depend on wax deposition, thus ne- (J/s.m2 .K).
cessitating the need for the authors to incorporate the effect of different The Matzain model did not directly consider the diffusion-controlled
flow regime in wax deposition in their model. Matzain et al. [144] there- crystallization and aging effect, which might have been indirectly ac-
fore derived the variables for different flow patterns as follows: counted for by the empirical constants C2 and C3 ,of Matzain model,
Single phase: which are based on the flow thickness data of single and two phases
respectively. The hardness of the deposit thickens as it ages, thus pre-
𝜌𝑜 𝜃𝑜 𝛿 vents the removal of wax deposit from the pipe wall. However, increase
𝑁𝑆𝑅 = (58a)
𝜇𝑜, 𝑓 in the hardness with further decrease in the rate of deposition as thick-
This type of flow pattern results in harder deposit, but with lower ness grows cannot be accounted for by constantsC2 and C3 in Matzain
thickness model because these constants are invariant with time. The constant
Intermittent/Bubbly: C1 adopts other mechanisms to enhance the wax deposition rate, which
( ) are not explained by the diffusion constant. Also, Matzain model did not
𝜃
𝜌𝑚 𝐸𝑠𝐿 𝛿 incorporate the effect of smearing of wax deposition in the model. The
𝑁𝑆𝑅 = (58b) strength of Matzain model lies on its ability to identify the following
𝜇𝑜, 𝑓
four major terms for the calculation of wax deposition:
where, 𝜌m is the average density of the gas-oil mixture (kg/m3 ).
• Term ‘A’ represents the modification of Fick’s law, where two em-
This flow pattern induces higher shear stress on the bottom of the
pirical correction factors are incorporated to account for influences
pipeline, leading to a thinner deposit section at the lower part of the
of reduced and enhanced rates.
pipe and harder deposit at the top, which decreases from top to bottom
• Term ‘B’ represents diffusivity coefficient, which is inversely related
of the pipe.
to the dynamic viscosity of oil, with empirical constant C1 as propor-
Annular:
( ) tionality constant.
√ 𝜃
𝜌𝑚 𝜌𝑜 𝐸𝑠𝐿 𝛿 • Term ‘C’ considers the dependency of the concentration of heavier
𝑁𝑆𝑅 = (58c) wax molecule as solute in the liquid phase on the nature of solute
𝜇𝑜, 𝑓
molecules and temperature.
This flow is uniform deposition around the pipe for the uniformly • Term ‘D’ considers the dependency of the thermal gradient of the
distributed oil over the pipe circumference [144,146, 147], but very laminar sublayer on the thermal conductivity of oil as well as the
hard deposit has been recorded in this flow pattern when compared difference between the inner and outer ambient temperature of
with others as shown below (Fig. 5c). pipeline.

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A.A. Olajire Chemical Engineering Journal Advances 6 (2021) 100104

Fig. 6. Validation of Matzain’s model with MO-02 deposition thickness (𝛿) and
flow prediction based on previous study [148].

Fig. 7. General Algorithm of Michigan model based on previous study [44].

The weaknesses of Matzain model include the following:

• The model based its experimental data only on South-Pelto oil, with-
out testing other oils, which might have different mechanistic chem-
istry.
• Limited understanding of aging of the wax because C2 and C3 are
invariant with time.
• Too many artificial turnings for a fitted model like Matzain
• Application of the model to pipes of different diameters is indifferent
• The model did not incorporate the effect of smearing of wax deposit,
which is peculiar to lowering the rate of annular flow in pipes.
• The model did not include physics of wax deposition with its asso-
ciated several constants.

The process of wax deposition from crude oil has been described re-
cently by Matzain’s models [148], where the model was tested against
experimental data points that were obtained with four different oils us-
ing flow loop facilities. Their results of validation showed that Matzain’s
model delivers satisfactory good performance on deposit wax mass and Fig. 8. Schematic of wax deposit aging based on previous study [150] (R = inner
flow predictions (Fig. 6), however it was still found to be unable to pre- pipe radius, r1 is deposit position).
dict aging mechanistically and deposition trends at large.

3.5. University of Michigan (Singh) model 𝑑𝐶 |

𝐷𝑜𝑤 | (1 − 𝜙(𝑥))
𝑑𝛿 𝑑𝑟 |𝑖
= (60a)
This model specifically focuses on the rate of aging of wax deposit 𝑑𝑡 𝜌𝑥
and the molecular diffusion mechanism [149], while it played down 𝑑𝐶 |
𝐷𝑜𝑤 | 𝜙(𝑥) 2 (𝑅 − 𝛿)
on the Brownian diffusion, shear dispersion and gravity settling for the 𝑑𝑥 𝑑𝑟 |𝑖
= (60b)
flow conditions in a pipeline system. Despite the repeated transfer of 𝑑𝑡 𝜌 𝛿 (2𝑅 − 𝛿)
molecules from bulk to oil deposit interface due to the molecular dif- where, xis the wax content of the deposit, Ris the radius of clean pipe,
fusion, not all these molecules become a part of this layer but rather 𝛼is the average aspect ratio of the wax crystal, 𝜑is the coefficient de-
continually diffusing internally in wax deposit. The general Algorithm scribing diffusion in porous network and can be calculated by Cussler
of Singh model is as given in the Fig. 7 below. et al. [115] as follows:
The Michigan model considers molecular diffusion as the main wax 1
𝜙 (𝑥) = (61)
deposition mechanism. The concentration of wax in the entrapped oil at
1 + 𝛼 2 1𝑥− 𝑥
2

the interface was found to be higher than that at the wall due to higher
interfacial temperature, which thus leads to a radial diffusive flow of Wang [151] extended the model through the addition of the shear
wax molecule towards the wall through the bulk oil medium (Fig. 8). flow of wax molecules in the deposit layer based on the shear energy
Nonetheless, not all waxes are completely transported to the deposit; principle for a single-phase flow wax deposition process as follows:
part of these accumulates in the interface, thus enabling the deposit | 𝑑 𝐸𝑆 | 𝜌𝑔𝑒𝑙
𝐽𝑠 = 𝑘𝑆 𝛼 || |
| (62)
to grow. The difference between the two radial mass flows (JA − JB ) | 𝑑𝐿 |𝑟𝑖 𝑟𝑖 𝜇 𝐹𝑤1.3
corresponds to the growth of the deposit, while the internal diffusion
where, kS is the shear coefficient, calculable from the regression analysis
mass flow (JB ) leads to increase in the wax fraction in the deposit, also 𝑑𝐸
of the laboratory data, | 𝑑𝐿𝑆 |𝑟𝑖 is the shear energy at a distance Lfrom
referred to as the aging rate of the deposit, relating to the hardening of
the initial position of the pipe when a different distance is required for
the wax deposit with increasing time.
the flow from the pipeline centre to surface sediment. The rate of wax
The only model that incorporated the effect of aging of the deposit
deposition thickness is expressed as:
in its calculation is Michigan model. The assumption which states that
|
the composition of the deposit is invariant with time was invalidated by 𝐷𝑜𝑤 𝑑𝐶 | (1 − 𝜙(𝑥)) − 𝐽𝑆
𝑑𝛿 𝑑𝑟 |𝑖
Singh et al. [150] via the model developed for laminar flow as follows: = (63)
𝑑𝑡 𝜌𝑥

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A.A. Olajire Chemical Engineering Journal Advances 6 (2021) 100104

Table 6 number lower than 100 is as follows [155]:

Boundary conditions for mass and energy
balances in the fluid. ⎛ ( )5 ⎞
⎜ 𝐺 𝑧 3 ⎟
𝑖
Coordinate Energy Mass 𝑁 𝑢𝑖 = 3.66 + 1.7813 𝑥 10−3 ⎜ ( )
⎟, 𝑖 = ℎ 𝑜𝑟 𝑚 (68)
⎜ ( )2 2 ⎟
r = r, z = 0 T = Tin C = Cin ⎜ 1 + 0.04 . 𝐺𝑧𝑖 3 ⎟
𝜕𝑇 𝜕𝐶
⎝ ⎠
r = 0, z = z 𝜕𝑟
= 0 𝜕𝑟
= 0
r = ri , z = 0 T = Tw C = Cws (T) where, Gzh and Gzm are Graetz number for heat and mass transfer,
respectively. However, the Nusselt number for the Graetz number that
is greater than 100 can be obtained with Seider and Tate correlation
If radial diffusive flow of the wax molecule towards the wall is as- [154] as follows:
sumed, the energy (64a) and mass (64b) balances of the fluid can be 1
𝑁 𝑢𝑖 = 1.24 (𝐺𝑧𝑖 ) 3 , 𝑖 = ℎ 𝑜𝑟 𝑚 (69)
expressed as follows:
[ ] The following equations can therefore be used to calculate heat and
𝜕𝑇 1 𝜕 𝜕𝑇
𝑣𝑧 = 𝑟 (𝜀ℎ𝑒𝑎𝑟 + 𝛼𝑇 ) (64a) mass transfer coefficients as follow:
𝜕𝑧 𝑟 𝜕𝑟 𝜕𝑟
𝑁 𝑢ℎ . 𝐶𝑡ℎ
[ ] ℎ𝑜 = (70a)
𝜕𝐶 1 𝜕 𝜕𝐶 ( ) 2𝑅
𝑣𝑧 = 𝑟 (𝜀𝑚𝑎𝑠𝑠 + 𝐷𝑤𝑜 ) − 𝑘𝑟 𝐶 − 𝐶𝑤𝑠 (64b)
𝜕𝑧 𝑟 𝜕𝑟 𝜕𝑟
𝑁 𝑢𝑚 . 𝐷𝑤𝑜
𝑘𝑚 = (70b)
where, 𝛼 T is the thermal diffusivity, kr is the thermal conductivity, Dwo is 2𝑅
the wax diffusivity in the oil, vz is the axial velocity, ris the radial coor- Singh et al. [44] derived a growth equation that relates the rate at
dinate, zis the axial coordinate. For laminar flow, 𝜀heat = 𝜀mass = 0, which wax is added to the gel deposit at the radial convective flow of
and for turbulent flow, the following equations (Eqs. 65a and 65b) are wax molecules from the bulk medium to the fluid-gel interface and dif-
used to correct the thermal momentum and mass diffusivities [138] as fusive flow into the gel-fluid interface as follows:
follows:
( )
𝜀ℎ𝑒𝑎𝑡 Pr 𝜀𝑚𝑜𝑚𝑒𝑛𝑡𝑢𝑚 𝑑𝑟 [ ] 𝑑 𝐶𝑤 ||
≡ (65a) 2 𝜋 𝑟𝑖 𝐹𝑤 (𝑡) 𝜌𝑔𝑒𝑙 𝑖 = 2 𝜋 𝑟𝑖 𝑘1 𝐶𝑤𝑏 − 𝐶𝑤𝑠 (𝑇𝑖 ) − 2 𝜋 𝑟𝑖 −𝐷𝑒 |
𝛼 Pr 𝑇 𝜈 𝑑𝑡 𝑑𝑟 |𝑖
(71)
𝜀𝑚𝑎𝑠𝑠 𝑆𝑐 𝜀𝑚𝑜𝑚𝑒𝑛𝑡𝑢𝑚
≡ (65b) where, De is the effective diffusivity of wax inside gel deposit, k1 and
𝐷𝑤𝑜 𝑆 𝑐𝑇 𝜈
Cwb are the mass transfer coefficient and the bulk concentration of wax
The correlation of Van Driest [152] can be used to calculate the eddy molecules respectively.
momentum diffusivity 𝜀as follows: Eq. (71) implies that the rate of growth of deposit is determined from
| 𝑑𝑉 + | the difference between wax flow to the interface in the deposit and the
𝜀𝑚𝑜𝑚𝑒𝑛𝑡𝑢𝑚 | |
= (𝐶1 𝑦+ )2 (1 − 𝑒−𝑦 ∕𝐶2 )2 | 𝑧+ |
+
(65c) fluid phase.
𝜈 | 𝑑𝑦 |
| | The process of wax deposition thickness and deposit aging from
The von Karman correlation [153] gives the velocity profile from the crude oil has been accurately described by heat and mass transfer ef-
turbulent flow. fects of University of Michigan model by various research groups in
The boundary conditions for heat and mass transfer along the radial recent times. Recently, Mahir et al. [16] used heat and mass transfer
coordinates in the fluid are as given in the table below: (Tables 6–8) kinetics to model the wax deposition mechanism in subsea oil pipeline
If the convective transport in the deposit is assumed to be negligible, by carrying out deposition experiment using a pure n-alkane and a bi-
then the expression for the mass balance that relates the rate of change nary n-alkane mixture in a modified cold finger apparatus, which al-
of wax in the gel deposit to the radial convective flow of wax molecules lowed a reliable and accurate visualization of wax deposit thickness as
from the bulk medium to the fluid-gel interface is given as [44]: a function time. Their findings revealed that the heat transfer model
accurately predicted the deposition thickness evolution of pure n − C28
( ) 𝑑 𝐹𝑤 [ ( )] at various temperatures of cold finger (Tcf )while the temperature of the
𝜋 𝜌𝑔𝑒𝑙 𝑅2 − 𝑟2𝑖 Δ𝐿 = 2 𝜋 𝑟𝑖 Δ𝐿 𝑘1 𝐶𝑤𝑏 − 𝐶𝑤𝑠 𝑇𝑖 (66)
𝑑𝑡 jacket (Tjac ) was fixed at 70°C (Fig. 7a); and at various temperatures of
where, Ris radius of the inner pipe, r and ri are the radial coordinate the jacket (Tjac )while the temperature of cold finger (Tcf ) was fixed at
and the internal radius during deposition (average radius available for 5°C (Fig. 7b) as a function time and were reported to compare well with
oil flow), Fw , k1 and 𝜌gel are the weight fraction of solid wax in the oil, the experimental observation. (Fig. 9)
the mass transfer coefficient and the wax density respectively, Cwb and In a related study, a theoretical kinetic calculation model of wax
Cws are the concentrations of wax in the bulk medium and the wax solu- deposition for crude oil heat insulated pipeline system was developed
bility in the oil solvent derived in terms of Ti respectively, and Ti is the by Sun et al. [156] based on molecular diffusion, aging and shearing
interfacial temperature obtainable from the energy balance as follows: effects on wax deposition process. The calculated values of the thickness
and wax content of the wax deposition layer in the pipe varied with time
( ) were compared with the experimental data. Their calculated values of
( ) 2 𝜋 𝑘𝑒 𝑇𝑖 − 𝑇𝑎 ( ( )) the thickness and wax content of wax deposition agree closely with the
2 𝜋 𝑟𝑖 ℎ𝑖 𝑇𝑜 − 𝑇𝑖 = ( ) − 2𝜋 𝑟𝑖 𝑘1 𝐶𝑤𝑏 − 𝐶𝑤𝑠 𝑇𝑖 Δ𝐻𝑓
𝐼𝑛 𝑅∕𝑟𝑖 experimental data at different flow rates (Fig. 8) and different ambient
(67) temperatures as a function of time. They also predicted wax deposition
thickness for the on-site pipeline system by using the wax deposition
where, Ta is the ambient temperature, ke is the effective gel thermal kinetic calculation model. Their results showed that the thickness layer
conductivity, hi is the heat transfer coefficient at the interface and ΔHf of the wax deposition increased at first and then later decreased along
is the enthalpy of wax solidification. the pipeline with time due to the difference in temperature between the
If the flow in the pipe is assumed to be laminar, the Seider and Tate centre of the oil and the deposition layer. (Fig. 10)
correlation [154], and the Hausen correlation [155] can be used to de- A numerical model was developed by Magnini, and Matar [157] to
termine the heat and mass transfer coefficients, which are valid for long investigate the dynamics of wax deposition and removal within oil trans-
and short tubes respectively [44]. The Nusselt number for the Graetz portation pipeline by treating liquid-like crude oil and solid-like deposit

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Table 7
Comparison of wax deposition models.

Model Features Reference

Dynamic model • Uses molecular diffusion and aging mechanism [110, 119, 120].
• Uses Fick’s law

Thermodynamic model
Rugg, Rydahl and Ronningsen (RRR)
• Considers the non ideality of the solid phase mixture, [134, 135, 148]
and the activity coefficients of solid phase,
• uses regular solution-molecular thermodynamic
theory
• May overpredict the wax deposition rate depending
on the oil type.
• Considers multi-phase flow system [160]
• Predicts wax deposition in an exclusive turbulent
regime.
• Not applicable to laminar flow

Matzain’s model (MM)
• Considers the shear stripping and flow regime [44, 101, 147, 148,161],
(Laminar and turbulent) effects.
• Modifies Fick’s law
• Performs better for South-Pelto oil.
• Overpredicts early fluxes and under predicts the late
time fluxes.

University of Michigan (Singh) model • Considers the effects of aging in wax deposition [156,157, 162, 163]
• works very well within laminar flow

Fig. 9. Theoretical (curves) vs. experimental (symbols) de-

posit thickness (𝛿) evolution of pure n-C28 as a function of time
(h) based on previous study [16].

Fig. 10. Validation of the model for wax deposition under

different flow rates and bathe temperature of 28°C dur-
ing wax deposition using both averages and error bars to
express the experimental results based on previous study
[156].

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A.A. Olajire Chemical Engineering Journal Advances 6 (2021) 100104

Table 8
Chemical structures of polymeric wax crystal modifiers used in petroleum industry.

Name Chemical structure References

Ethylene-vinyl acetate copolymer (EVA) [184]

Poly (methyl methacrylate) (PMMA) [185]

EVA-co-PMMA [186]

EVA-co-DMA [186]

Polyethylene-poly(ethylene-propylene) [187,188]
(PE-PEP)

Poly(ethylene–butene) (PEB) [189]

Poly(maleic anhydride amide co-𝛼-olefin) [190]

(PMAC)

Hydrophobically modified polybetaines [191]

Polyoctadecylmethacrylate (ODMA) [192]

(continued on next page)

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A.A. Olajire Chemical Engineering Journal Advances 6 (2021) 100104

Table 8 (continued)

Name Chemical structure References

Commercial phosphoric ester mixture [193]

Poly[N,N-diallyl-Noctadecylamine-alt-(maleic [194]
acid)]

Maleic anhydride-based copolymer [195-197]

Maleic anhydride-based copolymer [195-197]

Maleic anhydride-based copolymer [195-197]

Styrene maleic anhydride copolymer [23, 198]

Poly alkyl oleate-co-succinic anhydride [23, 198]

(continued on next page)

16
A.A. Olajire
Table 8 (continued)
Name Chemical structure
Polyaminoamide (PAA)
Aminated copolymers of monomers octadecyl
acrylate (M), maleic anhydride (M), and vinyl
(V) acetate (A) (MMVA)
Octadecyl methacrylate(O), maleic
anhydride(M) and styrene(S) (OMS)
as two immiscible phases separated by an interface, with each phase be-
ing considered as a bi-component mixture of wax and non-wax species.
A chemical-equilibria model was used to evaluate the deposition rate,
while the aging of deposit with time was accounted for by utilizing a
thixotropic rheological model. The model was reported to effectively
capture the dependency of deposit thickness on the Reynolds number of
the flow, with the likelihood of over-predicting the simulation results.
The authors suggested improvement in the performance of the model
through implementation of better closure relations, focusing specifically
on interfacial shear stress and the heat transfer.
3.6. Comparison of the wax deposition modelling approaches
The two major tasks performed by wax deposition models include
quantification of the total wax mass flow coming onto the cold inter-
face and distribution of this total wax into deposit aging and growth.
Dynamic model represents the mutual interactions of the precipitated
wax and the fluid in the subsea pipeline during the runtime and is pred-
icated on the molecular diffusion mechanism. The model assumed that
all wax crystals that are precipitated on the pipeline wall can form wax
deposit. The shared interactions of molecular diffusion and shear stress
dispersion were also considered by the model. On the other hand, ther-
modynamic model is predicated on the precipitation of solid wax as a
function of temperature, with the assumption of thermodynamic equi-
librium condition, which leads to a much smaller concentration gradi-
ent. Thermodynamic model cannot predict the location and the rate of
growth of the wax deposit in the pipeline. Rugg, Rydahl and Ronningsen
(RRR) is a multiphase flow model for the prediction of wax deposition
in production tubing that operates in an exclusively turbulent regime
[158] and is not applicable to laminar flow [137]. Matzain’s model
(MM) modifies the equilibrium model diffusion equation with empir-
ical correlation that accounts for shear stripping and trapped oil in the
deposit layer. The major shortcoming of Matzain model is that the em-
pirical constants inherent in this model are predicated only on South
Pelto crude experimental data, hence the model’s performance for other
oils at different operating conditions remains unclear. The molecular dif-
fusion and shear dispersion were also considered in Matzain and RRR
models as the mechanisms that cause wax deposition. However, Michi-
gan (Singh) model considers the aging effects during the deposition of
wax, and precisely predicted the growth thickness and the increase of
wax fraction in the deposit [44]. Michigan (Singh) model works very
17
Chemical Engineering Journal Advances 6 (2021) 100104
References
[199]
[19, 200]
[201]
well within laminar flow, but turbulent region requires modification of
the parameters [159]. The table below summarizes the comparison of
wax deposition models.
4. Wax mitigation techniques
Mitigation of wax formation in subsea flowlines is of significant inter-
est to the petroleum industry, in view of the enormous financial savings
that accrue from such strategy. The most effective strategy of handling
the flow assurance issues due to wax deposition is to prevent it from
occurring. Thus, different established wax mitigation strategies used in
the petroleum industry include thermal, chemical, mechanical and bio-
logical techniques. However, the success rate of any mitigation strategy
depends on the composition of the wax and the types of crude oil in the
reservoir. Therefore, in many cases, a combinatory method involving
two or more treatment techniques has been used for efficient mitiga-
tion of wax deposition. An overview of various mitigation strategies is
presented below.
4.1. Thermal techniques
Thermal techniques can be highly effective way of preventing and
removing wax deposits in the reservoir because wax deposition is highly
dependent on temperature. In this technique, heat is supplied to the
producing wells to melt and dissolve the wax deposit in order to increase
the fluidity of the oil in flowlines. However, the oil temperature should
not be too high to prevent coking of the crude oil, which could plug the
wellbore. The different thermal treatment methods are discussed below:
4.1.1. Hot oiling and hot water
Hot oiling is often utilized for dissolution and removal of wax in flow-
lines and downhole, thus prevents plugging in the wellbore and tubing.
The process involves heating of the oil to a temperature above the wax
melting point followed by pumping the hot oil down the well tubing or
casing to melt waxes that limit flowability in downhole equipment. A
dispersant is usually added to the crude oil during the hot oiling process
to increase the dispersion of the melted wax with the crude oil. However,
major shortcoming of hot oiling process is the evaporation of the lighter
components which thus reduces the market value of the produced oil
during the dewaxing operation. This technique has also been reported
to cause permeability damage if melted wax enters the formation [164].
A.A. Olajire
Hot oiling has been replaced with steam or hot water to melt the wax in
few operations, but they are rarely used due to the risk of emulsion and
corrosion problems. Water has a higher heat capacity than oil for the
same temperature, thus making the former an interesting solvent that
arrives at the site of deposition with a higher temperature and is cost-
effective. Also, water has no contaminants that may exist in oil [165].
However, the solvency effects in hot oiling cannot be provided by water,
hence necessitates the need to add surfactants to boost the dispersion of
wax into the water phase.
Steam injection into space between the tubing and the casing can
also be utilized to break up wax deposits. The formation of wax can be
prevented by applying the steam to a depth below the lowest point of
accumulation to heat the crude oil to temperatures between 55 and 65°C
for 3-6 hours.
4.1.2. Direct heating method
Direct heating involves passing a huge quantity of electric current
through the pipeline wall to generate heat that will melt the wax. The
flow assurance issue due to wax precipitation can be efficiently han-
dled with this method because it is possible to control the temperature
above the formation region. It is the most attractive and reliable option
for transportation in flowlines of deepwater field operation [166,167].
Direct heating method is generally designed in a way that the temper-
ature of the produced fluid is kept above WAT during shutdowns. The
shortcomings of this technique include the high maintenance cost of the
heating system, and the availability of an electric power supply [168].
4.1.3. Cold flow
Cold flow technology involves controlled generation of a slurry of
solid deposits such that they do not adhere to the walls of a pipeline
[169]. The wax deposition is prevented on the pipeline wall by low-
ering the temperature of the oil containing the wax to the same tem-
perature of the seawater around it, thus eliminating the temperature
gradient between the oil and the cold wall [170]. The wax will then be
moved within the bulk fluid as a solid dispersion, with negligible wax
deposition in the case of zero thermal flow, even below the WAT.
4.2. Chemical treatment method
The different types of chemicals that are commonly utilized for the
removal of wax deposition include solvents, dispersants, pour point de-
pressants and crystal modifiers. Various types of solvents that are com-
monly used include conventional solvents, green solvents and thermo-
chemical reagents. The thermochemical reagents generate heat due to
exothermic nature of its reaction when mixed with other chemical or
water in the well.
4.2.1. Solvents
Solvents are generally used to treat wax deposition in production
strings and may also be applied to remediate formation damage [171].
A specific amount of paraffinic wax can be dissolved by the solvent based
on the wax molecular weight, temperature and pressure before the sol-
vent power is completely consumed [172]. Solvents are used in locations
where the combination of water and surfactant cannot be applied. Sol-
vents are best applied to wells with a very little standing oil in the casing
above the pump [172]. Carbon tetrachloride (CCl4 ) and carbon disulfide
(CS2 ) are used as the universal solvents. Although, chlorinated hydro-
carbons are also excellent solvents for waxes [170], but they are not
generally used because of the safety and processing difficulties they cre-
ate in the produced fluid. Aromatic solvents such as toluene and xylene
are good solvents for waxes. Solvents are mostly used in large batch or
continuous treatments and their selection is predicated on the solvation
test of the wax [173].
In view of the environmental constraints of the conventional sol-
vents, green solvents such as terpene, derived from natural and renew-
able sources has been used as an alternative for wax mitigation. Terpene
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Chemical Engineering Journal Advances 6 (2021) 100104
is an unsaturated aliphatic hydrocarbon, composed of repeating five-
carbon isoprene units and is abundant in plants such as oleo-resins from
pine plant, 𝛿-limonene from orange peels while others includes turpen-
tine, citronella, carotene and many more. Terpene is environmentally
friendly, biodegradable, low toxicity, less flammable, and has high sol-
ubility power for organic deposit compared to aromatic solvents. Ter-
pene has been blended with other co-solvents for removing wax deposit
[174]. A large quantity of chemicals is required to ensure the melting of
the wax, thus making this approach not to be cost-effective and therefore
necessitates the need for the use of thermo-chemical packages method
as an alternative, where the heat liberated from exothermic reaction
is used for the melting of wax deposits in the downhole or in subsea
flowlines. The nitrogen generating system (NGS) process was pioneered
by Petrobras [114] to generate heat for the melting of wax deposits in
Campos basin through the exothermic nature of the chemical reaction
between ammonium chloride and sodium nitrite in an acidic pH as fol-
lows:
(72)
The NGS process was successfully applied in oilfields of Indian [175].
The major shortcoming of NGS process is that it is only the areas that
are in close proximity to the point of chemical injection could be treated
because the exothermic reaction will stop before reaching locations that
are far away from the chemical injection point. However, the challenge
was addressed by Halliburton through a package with a delayed effect,
the SureTherm, that was developed to control the start of the exother-
mic chemical reaction, with commencement of heat generation after a
calculated delay period [176]. The delay of the exothermic chemical re-
action would create enough time for the pumping of the chemical into
the flowline area with wax deposits where the heat generated can be
utilized to melt the wax deposits in the pipeline.
4.2.2. Wax dispersants
Wax dispersants hinder deposition of wax in oilfield by initiating a
repulsive force between particles of paraffin wax (hindering gathering
of wax nuclei into cluster) as well as between particles of paraffin wax
and the pipeline surface. Wax dispersant hinders wax deposition and re-
duces oil viscosity and lowers the gelling power of the wax. Dispersants
can assist in dispersing deposited wax into small particles that can be
transported in the oil stream. Wax deposition is hindered by continuous
application of wax dispersant or in batch treatments for remediation
purposes. Wax dispersants have very low pour point and are therefore
suitable for use in cold climates where paraffin inhibitors cannot be
used [173]. They are relatively safe and inexpensive because they are
used in low concentrations and can be formulated in both aqueous and
hydrocarbon solutions. The low-cost wax dispersants which have been
reported to exhibit poor performance on the field except if blended with
polymeric wax inhibitors include alkyl sulfonates, alkyl aryl sulfonates,
fatty amine ethoxylates and other alkoxylated products [177].
4.2.3. Pour-point depressants
They are polymeric surfactants containing an n-alkyl chains as tail
end that inhibits the formation of wax crystal, thus reducing the viscos-
ity, pour point and yield stress of the fluid. They function effectively in
the presence of water by water-wetting paraffin particles, tubing, for-
mation and flowlines. These formulations solubilize the wax and inhibit
them from agglomerating further downstream in the reservoir [172].
Pour point depressants act to lower the pour point of a mineral oil
by inhibiting the formation of three-dimensional wax networks [178],
thus improves the fluidity of crude oils. The mechanism of action of
a pour point depressant (PPD) is predicated on the interaction or co-
crystallization of its linear, non-polar structure with molecules of the
wax, while oil solidification due to aggregation of wax molecules into
three-dimensional networks is disrupted by the polar or otherwise non-
wax-like portion.
A.A. Olajire
The PPDs are commercially available in different forms, includ-
ing derivatized forms of alkyl methacrylate/acrylate copolymers, olefin
copolymers, vinyl ester copolymers, alkylated polystyrene, esters from
maleic anhydride copolymers with styrene and alkylated naphthalenes.
The PPDs that are commonly used in the lubricant industry are poly-
methacrylates (PMAs) [178-180].
4.2.4. Wax crystal modifiers
The deposition of wax is inhibited through the interference of these
polymers (wax crystal modifiers) with the crystal growth and agglom-
eration processes. Thus, the pour point, viscosity and yield value of the
crude are reduced. Therefore, modifiers are added ahead of fracturing
[172]; and they are more efficient only on continuous usage. The cri-
teria for the choice of wax crystal modifiers depends on the pour point
test, recorded viscosity vs. temperature, the cold finger test, and the
yield stress value. The effectiveness of wax crystal modifier for the treat-
ment of paraffin wax depends on the type of crude oil, chemistry of the
inhibitor, and the production conditions being treated [181]. The ro-
bustness of the chemical injection technique is sacrosanct because of
the influence of temperature and pressure on the stability of paraffin
inhibitor formulations.
The chemical structures of wax crystal modifiers are similitude to
the paraffin wax that is depositing, and examples of wax crystal modi-
fier include polymeric compounds containing one or more hydrocarbon
chains (wax-like) as the non-polar portion and a polar portion. The po-
sition of wax molecules on the crystal lattice is also occupied by wax
crystal modifiers by co-precipitating or co-crystalizing with wax through
their hydrocarbon chains. Wax crystal modifiers also interfere with the
growth and aggregation of wax crystals by creating a steric hinderance
on the crystal [182, 183] as illustrated in Fig. 6 below. (Fig. 11)
Table 5 details the commonly used polymeric wax crystal modifiers
in the petroleum industry to improve fluidity and/or inhibit wax forma-
tion tendency of waxy crude oil in subsea pipeline systems.
4.3. Mechanical treatment
This method involves the use of rod scrapers, wireline scrapers, flow-
line scrapers, free-floating piston scrapers (in gas lift wells) [170], pig-
ging flowlines and wire-lining tubing [168] to remove deposits of wax
from production tubing and flowlines. Pigging is mostly used to remove
wax in the subsea pipeline systems, where the wax is physically removed
19
Chemical Engineering Journal Advances 6 (2021) 100104
Fig. 11. Wax crystal deposition on a cold pipeline
surface(a) and co-crystallization of wax crystal
modifier with wax crystals (b) based on previous
study [170].
by scouring the flowline. Pigging must be carried out frequently to pre-
vent the build-up of large amounts of wax. If the pressure required to
push the pig through the pipeline containing a thick wax deposit in front
of pigging equipment is not enough, it might lead to flowline blockage
with eventual shutdown of production activities.
In pigging process, the subsea oil system needs to be shutdown,
injected with methanol for stabilization and blowdown and finally
restarted after the completion of pigging process. Therefore, the en-
tire pigging process may cause production shutdown of 1 to 3 days and
hence should be performed when is highly necessary because of its fi-
nancial implications. The operational cost (OPEX) of the pigging process
may be insignificant but potential financial losses associated with the
pigging process due to production shutdown might be enormous.
Therefore, pigging frequency must be significantly reduced in the
interest of having more economic benefits [202]. The choice of pig de-
pends on the properties of the wax and operating conditions while ef-
fective utilization of pigging depends on the wax deposition prediction
[170]. A complete blockage of pipeline can occur as a result of the use
of a non-suitable pig [202].
Scrapers and cutters are used extensively to remove wax deposits
from tubing because they can be economical and give minimal formation
damage [164]. Scrapers may be joined to wireline units or sucker rods to
remove wax as the producing well is pumped. However, the formation
of a wax plug as scrapped wax accumulates is a potential risk that must
be put into consideration when adopting this technique.
4.4. Biological treatment
Marine microorganisms can sorb the paraffin wax and utilize the
carbon as their source of energy which thus makes them to be effec-
tive in removing paraffin wax or at least reduce their deposition over
a certain period [170]. Biological methods of removing wax deposits
have been studied by various research groups. Sood and Lal [203] used
a bacteria strain Geobacillus TERI NSM, to degrade paraffinic crude oil
at high temperatures, low-oxygen, and low-nutrient conditions. Their
findings revealed that high-molecular weight paraffinic crudes were de-
graded while low-carbon chains are unaffected. Etoumi et al. [204] used
Pseudomonas bacteria to reduce the wax precipitation potential of waxy
crude oils. Their findings revealed that Pseudomonas species has the po-
tential to emulsify immiscible hydrocarbons like kerosene, toluene, xy-
lene and crude oil. The overall effect of treating crude oil with Pseu-
A.A. Olajire
domonas has been reported to reduce the concentration of long-chain
hydrocarbons (C22 +) [204]. They concluded that Pseudomonas species
may efficiently reduce paraffin wax deposition within the first one week,
with remarkable reduction in viscosity and effective conversion of long-
chain hydrocarbons to short ones. Although bacteria treatment is inno-
vative, it may only be used in wells that produce water and where the
bottom-hole temperature is lower than 200°F because microbes need
water for survival and do not have ability to withstand high tempera-
tures [205]. However, the method is not without its shortcomings which
include bio-corrosion or oxidation and souring, which are restricted to
wells producing water [168].
4.5. Other methods
4.5.1. EcowaveTM treatment (Baker Hughes)
This is a stimulation technology that is chemical-free and environ-
mentally friendly. The technology involves the use of high-frequency
radio waves and microwaves at low power to change molecular bonds
downhole, thus facilitating an increase in production by disrupting dam-
aging deposits to improve reservoir wettability and fluidity [206]. The
equipment consists of an Ecowave unit, tuner, antenna system and
portable power source. After appropriate choice of a well as approved
by the operator, it is then followed by the deployment of the antenna in
an annulus or tubing at the surface and attached to the Ecowave. The
system is then powered, and the treatment is commenced, which nor-
mally lasted for about 2–4 hours. The efficiency of the method has been
field-proved with increase in production rate from 20% to more than
120% and treatment durability of more than 60 days [207].
4.5.2. Ultrasonic waves treatment
Ultrasonic waves were developed by Towler et al. [208] for mitigat-
ing against wax deposition. The method is based on joining a device
capable of generating an ultrasonic frequency of 120 kHz to the pro-
duction tubing, which breaks bonds in wax molecules and prevents the
deposition of wax on the walls of production tubing. The treatment leads
to an increase in flowability rates and enhances production efficiency.
5. Future challenges of wax prediction model
Various parameters used in all the models discussed in this review
were verified against laboratory data. However, the advancement of the
data to real field cases is an issue of concern to petroleum industry due to
high level of uncertainty and empiricism on the mechanistic aspects and
models for the removal of wax deposits. Therefore, the ideal solution to
this issue is to validate the prediction models with the actual field data
when planning oil transportation in pipelines, however the collection of
good field data is cumbersome [209] which needs to be addressed in
the future for validation of these models. Investigations into field data
will also enable accurate determination of different operating conditions
including the oil types, flow conditions such as pressure, temperature,
and velocity etc occurring in real field situations. The laboratory-based
experiments and modelling must be validated with the research field
data.
Also, most reported laboratory data are associated with single phase
(oil) wax deposition, however, Leporini et al. [210] recently simulated a
multiphase system (gas-oil-water) for wax deposition, which has never
been reported in any of the laboratory tests. Therefore, there is need for
more studies on development of an appropriate mathematical model for
wax deposition in a multiphase flow regime.
There are several wax deposition models which are available in the
literature, both in commercial software and academic programs. The
OLGA package, a commercial transient multiphase simulator offers a
module that uses the models proposed by Rygg et al. [64] and Apte
et al. [66] to simulate wax deposition along with the transient multi-
phasic flow. The PVTSim package, a thermodynamic phase behaviour
simulator also offers a module that rests on the work of Lindeloff and
20
Chemical Engineering Journal Advances 6 (2021) 100104
Krejbjerg [211] to simulate wax deposition. The Michigan wax predic-
tor (MWP) was developed by Huang et al. [112] to study deposition of
wax in field-scale pipeline systems. Sevic and Grubac [212] developed
a model that used Aspen HYSYS software to simulate fluid phase be-
haviour and temperature-pressure profile composition change and wax
deposition as a function of well depth in gas -lift wells. Recently, Shahdi
and Panacharoensawad [213] developed an SP-Wax, an open-source
thermodynamic software for modelling various solid-liquid equilibrium
(SLE) characteristics of paraffin in binary and multicomponent systems.
6. Conclusions
Wax deposition that results to formation damage, flow restriction
and decreased production rate is a critical operational challenge in
petroleum industry. This review evaluated different depositional mech-
anisms and different numerical models that have been used for the
prediction of deposition of wax, which were validated experimentally.
While molecular diffusion was generally accepted by all the models as
the main deposition mechanism, the contribution of shear forces to the
accuracy of wax deposition models cannot be overemphasized. By and
large, more studies on wax prediction models should focus on complex
environments such as multiphase flow, turbulent flow etc. as well val-
idation of the models using field scale data due to large discrepancies
of the models from the field data. The review also underscores the ben-
efits of applying mitigation techniques such as thermal, chemical and
mechanical and biological techniques as well as a chemical-free and en-
vironmentally friendly stimulation technology to control wax deposition
process. However, the success rate of any mitigation strategies depends
on the composition of wax and type of crude oil in the reservoir. In many
cases, a combinatory method involving the use of two or more treatment
methods has been suggested for efficient mitigation of wax deposition.
Declaration of Competing Interests
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
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