CET 97
DOI: 10.3303/CET2297050
Paper Received: 29 June 2022; Revised: 11 September 2022; Accepted: 12 September 2022
Please cite this article as: Baharudin A.N., Risal A.R., Zakaria R., Idress M., Redzuan F.R., 2022, Molecular Characteristics of Fatty Acid Methyl
Ester (FAME) in Waxy Crude as Flow Improver, Chemical Engineering Transactions, 97, 295-300 DOI:10.3303/CET2297050
CHEMICAL ENGINEERING TRANSACTIONS
VOL. 97, 2022
A publication of
The Italian Association
of Chemical Engineering
Online at www.cetjournal.it
Guest Editors: Jeng Shiun Lim, Nor Alafiza Yunus, Jiří Jaromír Klemeš
Copyright © 2022, AIDIC Servizi S.r.l.
ISBN 978-88-95608-96-9; ISSN 2283-9216
Molecular Characteristics of Fatty Acid Methyl Ester (FAME)
in Waxy Crude Oil as a Flow Improver
Ameer Naqiuddin Baharudina, Abdul Rahim Risala,*, Rozana Zakariab, Mazlin
Idressc, Farah Rosmaniza Redzuana
aSchool of Chemical and Energy Engineering, Universiti Teknologi Malaysia (UTM), Malaysia
bSchool of Civil Engineering, Universiti Teknologi Malaysia (UTM), Malaysia
cDepartment of Petroleum Engineering, Universiti Teknologi PETRONAS, Malaysia
abdulrahimrisal@utm.my
Mitigation of wax deposition is of major interest, especially in the oil and gas industry, to minimize the flow
assurance and production problems. In view of financial savings, the currently established method still has more
opportunities to improve, particularly in a green technology sector in compliance with a stringent environmental
policy. Therefore, a cost-efficient and environmentally friendly alternative method is required in handling waxy
crude oil. This paper describes the investigation of Fatty Acid Methyl Ester (FAME) as a waxy crude oil flow
improver via changes in wax particles' growth and aggregation rate through molecular dynamics simulation
using Biovia Materials Studio. The molecular dynamics simulation shows an increase in the wax molecules'
interaction energy from an average of 851 kcal/mol to 972 kcal/mol. Similarly, kinetic energy increases from an
average of 629 kcal/mol to 675 kcal/mol. The mean square displacement also increases from 3.195 angstrom2
to 6.007 angstrom2. There is also an increase in the radial distribution function by having a higher probability of
finding particles in the presence of FAME. The results indicate that FAME reduces the wax particles' growth and
aggregation rate, mitigating the wax depositions and improving the waxy crude oil flow.
1. Introduction
The main problem when dealing with waxy crude oil is wax deposition. Wax deposition in production tubing
strings or transmission pipelines reduces the oil production rate and decreases total oil production. The wax
deposition is initiated when the crude oil temperature is lower than the pour point temperature, where the paraffin
content starts to solidify and then gradually deposited inside the tubing and the pipes. Severe wax deposition
induces high operating costs of wax removal (White et al., 2018). The problem needs to be solved immediately
to prevent a continuous decline in the oil production rate. Many mechanisms lead to wax deposition, such as
molecular and thermal diffusion (Aiyejina et al., 2011), Brown diffusion (Liu et al., 2020), shear dispersion (Yang
et al., 2020), and shear stripping (Olajire, 2021). The deposited wax removal includes mechanical and chemical
techniques (Yao et al., 2022).
One of the common approaches to removing wax deposition is using mechanical removal techniques such as
flowline pingging, rod and wireline scrappers, and free-floating piston scrappers, but the execution cost of this
method is too expensive and incur longer non-productive time (NPT) (Olajire, 2021). Furthermore, in oil and gas
production, mechanical removal techniques have a high risk of damaging reservoir formation (Anisuzzaman et
al., 2018). The implementation of flow improvers has been applied for many years, having its first application
completed to decrease pressure loss during the commencement of fluid pumping into fracture-tight formations
(Almond, 1989). The flow improvers have interacting elastic macromolecules and macrostructures during
turbulent flow conditions (Fink, 2016). Many flow improvers are currently used, and each brings different
functions and mechanisms (Sivakumar et al., 2018), such as copolymers as flow improvers are capable of
retarding the wax crystal's interaction and halting the aggregation process. However, the efficiency of
copolymers depends on their content and physical and chemical properties in the solution, such as the cetane
number, aromatic content and type, polymer composition, and polymer density (Sadiku-Agboola et al., 2011).
295
The bio-based pour-point depressants are also suitable improvers due to having both hydrophobic and
hydrophilic natures, reducing the interfacial and surface tension when dealing with fluids with different polarities
(El-Sheshtawy and Khidr, 2016). Lastly, nano-hybrid pour-point depressants can also be considered one of the
flow improvers capable of reducing the solidifying point of crude oil and having long-term stability compared to
other surfactants' pour-point depressants (He et al., 2016). Worthy to note that the application of pour point
depressant is still limited to the type of crude oil and depressant as well as the concentration of depressants
(Yao et al., 2022).
One of the potential elucidations is the utilization of Fatty Acid Methyl Ester (FAME), biodiesel derived from
renewable sources as wax deposition inhibitors and flow improvers. FAME productions commonly used
catalyzed transesterification of waste cooking, animal fats or tallows, soya oil, rapeseed oil, sunflower oil, and
palm oil (Vyas et al., 2010). FAME is one of the types of fatty acid esters that have recently been considered an
alternative energy source in the form of biodiesel. In this study, palm oil-based FAME is chosen because of its
resource abundance, as Malaysia is one of the largest palm oil-producing countries. This study observes the
changes in the waxy crude oil before and after FAME is added and validates the implementation of FAME as a
wax retarder and flow improver using molecular dynamic simulations.
2. Methodology
The experiment methodology includes identifying the materials, sample preparation, molecular dynamic
simulation, and comparing the results.
2.1 Identification of materials
The medium used for testing would be waxy Dulang Crude Oil due to its high wax content (22% w/w) and
relatively high pour point of 34 °C (Hassan and Ismail, 1988). As for the FAME, the fatty acid component is
extracted from palm oil. The catalyst for FAME production is sodium hydroxide.
2.2 Sample preparation
FAME was prepared using homogeneous alkali-catalyzed transesterification with sodium hydroxide as the
catalyst. Later, FAME is mixed with the crude oil using a magnetic mixer. Before the molecular dynamics
simulations, the crude oil components were analyzed using Gas Chromatography-Mass Spectrometry (GSMS)
to identify the average carbon compound inside the paraffin. The average carbon compound was calculated
using Eq (1) based on the weighted average method.
𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴 𝐶𝐶𝐴𝐴𝐴𝐴𝐶𝐶𝐶𝐶𝐶𝐶 𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶 = 𝑆𝑆𝑆𝑆𝑆𝑆 𝑜𝑜𝑜𝑜 𝑁𝑁(𝐴𝐴𝐴𝐴𝑆𝑆𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴)
𝑆𝑆𝑆𝑆𝑆𝑆 𝑜𝑜𝑜𝑜 𝐴𝐴𝐴𝐴𝑆𝑆𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴
(1)
2.3 Molecular dynamics simulation
The molecular dynamics were simulated using the Biovia Materials Studio. This software predicts and
comprehends the materials' atomic and molecular structure connections and their properties and behavior
based on comprehensive modeling and simulation environment after the average carbon compound was
determined. Initially, the simulator built the molecules based on the 80:20 concentration ratio of Dulang Crude
Oil and FAME paraffin content. Then, the molecules were quantified by converting the produced molecules into
amorphous stages.
2.4 Making comparison
Lastly, the interaction energy sum of potential and kinetic energy, Mean Square Displacement (MSD), and
Radial Distribution Function (RDF) were simulated using the build-in forcite tools in Biovia Materials Studio for
the solvent-free paraffin was compared with the paraffin and FAME mixture.
3. Results and discussion
3.1 Gas chromatography results
The gas chromatography method identified the composition of each component of the sample. The gas
chromatography results of waxy Dulang crude oil is as in Table 1. The average carbon compound was calculated
using Eq(1) and then benchmarked to the reported relative retention time in the literature. Table 1 shows that
the average carbon composition in the paraffin content of Dulang Crude Oil is C-22. The calculated average
carbon composition was later applied in the molecular dynamics simulation to build the paraffin molecule model.
296
Table 1: Calculation of the average carbon composition in the paraffin content of Dulang Crude Oil
Retention
Time (m)
Stoppage
Time(m)
Relative
RT
(Calculated)
Relative
RT
(Literatu
re
Review)
N-
Carb
on
Abundanc
e
Ratio N
(Abundance
)
62.988 65 0.97 0.96 34 0.113 0.362 3.842
60.599 65 0.93 0.93 33 0.118 0.378 3.894
58.625 65 0.90 0.91 32 0.356 1.140 11.392
56.92 65 0.88 0.89 31 0.480 1.537 14.880
55.428 65 0.85 0.86 30 0.855 2.738 25.650
53.978 65 0.83 0.84 29 0.935 2.994 27.115
52.478 65 0.81 0.81 28 1.583 5.069 44.324
50.884 65 0.78 0.78 27 1.465 4.691 39.555
49.263 65 0.76 0.75 26 1.928 6.173 50.128
47.548 65 0.73 0.73 25 2.058 6.590 51.450
45.777 65 0.70 0.70 24 2.202 7.051 52.848
43.904 65 0.68 0.66 23 2.134 6.833 49.082
41.955 65 0.65 0.63 22 2.325 7.445 51.150
39.89 65 0.61 0.60 21 2.345 7.509 49.245
37.694 65 0.58 0.57 20 2.538 8.127 50.760
35.325 65 0.54 0.53 19 2.286 7.320 43.434
32.743 65 0.50 0.49 18 2.306 7.384 41.508
29.854 65 0.46 0.45 17 2.357 7.547 40.069
26.498 65 0.41 0.40 16 2.166 6.935 34.656
22.406 65 0.35 0.36 15 0.681 2.180 10.215
Sum of Abundance 31.231
Sum of N(Abundance) 695.197
Average Carbon Compound 22
3.2 Molecular structure design, geometrical optimization, and dynamic interaction energy
After the molecular structures of FAME and Paraffin C-22 were built as per Figures 1a and 1b, the molecules
were quantified by making them into amorphous stages with frames. Figures 2a and 2b show the amorphous
stages of Paraffin C-22 and a mixture of Paraffin C-22 and FAME, while interaction energy between molecules
is shown in Table 2.
Figure 1: Molecular structure of a) Fatty Acid Methyl Ester (FAME) and b) Paraffin C-22
Figure 2: The amorphous stages of a) Paraffin C-22 only and b) Paraffin C-22 and FAME
(a) (b)
(a) (b)
297
Table 2: The calculated interaction energy for Paraffin C-22
Paraffin C-22 Paraffin C-22 + FAME
Fram
es
Total
Energy
(kcal/mol
)
Non-
bond
Energy
(kcal/mol
)
Van
Der
Waals
(kcal/m
ol)
Electrost
atic
(kcal/mol
)
Total
Energy
(kcal/mol
)
Non-
bond
Energy
(kcal/m
ol)
Van Der
Waals
(kcal/mol)
Electrostati
c (kcal/mol)
1 -815.7 -335.8 -212.4 -116.2 -844.9 -563.9 -91.4 -464.9
2 -868.3 -373.2 -222.1 -143.9 -946.2 -665.5 -128.4 -529.6
3 -866.7 -368.5 -230.8 -130.5 -1026.4 -681.4 -123.6 -550.1
4 -859.0 -360.0 -214.5 -138.3 -924.6 -635.1 -102.9 -524.6
5 -850.2 -345.3 -225.0 -113.2 -912.9 -643.9 -106.3 -530.1
6 -853.7 -363.6 -218.4 -138.1 -1,002.5 -668.3 -119.3 -541.4
7 -879.7 -386.0 -226.3 -152.6 -833.2 -556.6 -46.1 -502.9
8 -821.3 -344.1 -208.6 -128.5 -878.4 -651.9 -126.9 -517.5
9 -851.5 -378.9 -211.1 -160.6 -982.7 -673.3 -128.2 -537.5
Avg -851.8 -361.7 -218.8 -135.8 -928.0 -637.8 -108.1 -522.1
The negative value indicates that the molecule is experiencing attractive forces mainly because of opposite
charges (Kumar and Manik, 2016). The result also shows the increase in total attraction forces when FAME is
added, indicating that FAME acts as a wax crystal modifier instead of a dispersant, and this proves that FAME
reacts and modifies the growth of wax. Despite increasing the attraction energy, the total Van Der Waals
interaction energy decreases due to the retarded growth of wax particles hence, higher effective surface area.
Table 3 shows the analysis and calculation of total energy, enthalpy, temperature, and pressure for Paraffin C-
22 before and after FAME is added.
Table 3: Total energy, enthalpy, temperature, and pressure of Paraffin C-22
Paraffin C-22 Paraffin C-22 + FAME
Initial Final Average Initial Final Average
Potential Energy
(kcal/mol)
-151.543 -201.795 -204.064 -452.986 -443.122 -391.995
Kinetic Energy
(kcal/mol)
576.494 627.022 629.585 606.695 730.581 675.210
Total Enthalpy
(kcal/mol)
1,219.671 1,624.341 1,432.801 1,654.178 1,609.543 1,466.966
Temperature (K) 298.000 324.119 325.444 298.000 358.851 331.653
Pressure (GPA) 1.121 1.692 1.421 1.882 1.658 1.485
Based on Table 3, an increase in every calculated parameter proves that adding FAME increases the crude oil
fluidity and decreases its viscosity, making it easier to flow. According to Lennard-Jones' theory, the negative
potential energy suggests that the particles are experiencing the attractive force, and the potential energy
decreases as the molecules are attracted closer. Typically, the displacement between two particles in a liquid
is infinite. Anything less than infinity is considered to have negative potential energy. For example, the
interactions between two distanced particles, no matter how weak, still correspond to negative potential energy.
So, the total potential energy for the interaction of given particles is negative for liquid.
3.3 Mean square displacement and radial distribution function
Mean Square Displacement (MSD) is a method implemented to describe the random movement of particles in
a specific amount of time according to Eq (2) (Masiren et al., 2016).
MSD = |x(t) − x(0)|2 (2)
where x(t)=current position,x(0)=initial position.
From the MSD results, the distance of the particles' motion and the conditions of the particles can be determined.
Table 5 compares the mean square displacement of Paraffin C-22 and the mixture of Paraffin C-22 and FAME
in angstrom2, while Figure 3 shows the MSD versus time.
298
Figure 3a and 3b show a linear trend of MSD with time, indicating a pure diffusion between particles. Table 4
shows that the distance increases in every direction when FAME is added, demonstrating that the particles
inside the crude oil move faster for the mixture of paraffin and FAME, indicating that FAME lessens the Dulang
crude oil viscosity and enhances the fluidity.
Figure 3: Mean Square Displacement a) without FAME b) with FAME
Table 4: Comparison of Mean Square Displacement (MSD) between only paraffin and the paraffin and FAME
mixture
XX YY ZZ XY XZ YZ Total
Paraffin C-22 1.104 1.081 1.010 0.104 0.100 -0.043* 3.195
Paraffin C-22 and FAME 1.691 2.221 2.094 -0.279* 0.229 -0.125* 6.007
Negative values indicate negative displacement
Radial Distribution Function (RDF), which measures the probability of finding any particle at a certain distance
from a reference particle based on RDF = 4πr2 (p(r) – p (0)) where p(r) is particle concentration radius and p(0)
is bulk particle concentration., further confirms the effect of FAME as an oil flow improver (Dimitroulis et al.,
2015). Based on Figure 4a and 4b, as distances increase, the number of peaks increases, and the peak intensity
decrease. It is shown that the peaks in the paraffin and FAME mixture have a higher probability of finding
particles at shorter distances than the solvent-free paraffin, while at a longer radius, the presence of particles is
lesser, proving that FAME acts as an effective wax crystal modifier. FAME increases the bonding between
compressed particles and forms a lattice structure to restrict the growth of wax. If FAME acts as a dispersant,
the peaks at the further distance should have a higher probability, but that does not show in this case.
Figure 4: Radiation Distribution Function a) without FAME b) with FAME
-0.5
0
0.5
1
1.5
2
2.5
3
3.5
0 1 2 3 4 5
M
ea
n
Sq
ua
re
D
is
pl
ac
em
en
t
(A
ng
st
ro
m
2 )
Time (ps)
TOTAL XX YY
ZZ XY XZ
YZ
-1
0
1
2
3
4
5
6
7
0 1 2 3 4 5
M
ea
n
Sq
ua
re
D
is
pl
ac
em
en
t
(A
ng
st
ro
m
2 )
Time (ps)
TOTAL XX
YY ZZ
XY XZ
0
2
4
6
8
10
12
14
0 2 4
g(
r)
r (Angstrom)
(a) (b)
(a) (b)
0
2
4
6
8
10
12
14
0 2 4
g(
r)
r (Angstrom)
299
4. Conclusion
This study has corroborated the implementation of FAME as a solvent to mitigate and prevent wax deposition.
The results obtained from the tests and simulations confirm that FAME can act as a wax crystal modifier that
reduces crude oil viscosity indicated by increased interaction and kinetic energy, which correspond to more
crude oil mobility and less viscosity. The MSD increments and higher RDF in the presence of FAME prove that
the crude oil particles move faster. In conclusion, FAME is an excellent wax crystal modifier and effective flow
improver.
Acknowledgments
The authors hereby extend their appreciation to the Malaysia Ministry of Higher Education and Universiti
Teknologi Malaysia (UTM) for financing this research under UTM Encouragement Grant (Ref:
QJ130000.2651.18J65). Sincere appreciation to the authors and researcher from Universiti Teknologi Malaysia
(UTM) and extended thanks to Universiti Teknologi PETRONAS (UTP), co-authors, and everyone who has been
involved directly or indirectly for assisting and supporting this study.
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