Energy Reports 8 (2022) 7800–7813

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Energy Reports
journal homepage: www.elsevier.com/locate/egyr

Research paper

Surfactant formulation for Green Enhanced Oil Recovery

∗
Ahmed Al-Ghamdi, Bashirul Haq , Dhafer Al-Shehri, Nasiru S. Muhammed,
Mohamed Mahmoud
Department of Petroleum Engineering, King Fahd University of Petroleum and Minerals, Dhahran 31261, Saudi Arabia

article info a b s t r a c t

Article history: While the world continues to rely heavily on petroleum as a primary energy source, a great fraction
Received 26 February 2022 of the oil-in-place remains inaccessible to traditional recovery means (thermal, gas, or chemical),
Received in revised form 30 May 2022 posing significant environmental consequences and high treatment costs. Green enhanced oil recovery
Accepted 31 May 2022
(GEOR) technologies, on the other hand, have generated interest in energy research as it involves the
Available online 17 June 2022
injection of specialized green fluids into reservoirs to improve sweep efficiency while also increasing
Keywords: residual oil production. Surfactant flooding, for example, has emerged as a viable green chemical EOR
Green Enhanced Oil Recovery approach in which bioproducts produced by microbial metabolic processes are introduced into the
Green surfactants reservoir to increase oil production These green surfactants (e.g., rhamnolipid, alkyl polyglycoside
Bio-surfactants (APG), and lecithin) are now being studied for their possible uses in EOR processes as they have
Rhamnolipids not been completely explored for their potential in chemical EOR. Therefore, in this study, a blend
of rhamnolipid, APG, and lecithin are considered possible formulations to investigate the efficacy of
these green surfactants in sandstone reservoirs based on phase behavior studies, interfacial tension
measurement, and core-flooding experiments. It was found that all three blends (RB, RAB, and
RL) performed well in the phase behavior study, resulting in stable middle phase microemulsions
whereas only formulation RL had an ultralow IFT reduction between oil and brine. Consequently, this
formulation (RL) performed the best of the three, with a tertiary recovery of 24% and a total recovery
of approximately 70%. These results suggest that while other blends (RB and RAB) had good EOR
potential, the third formulation (RL) is considered a more appropriate candidate for chemical EOR
with a preference for biosurfactants (rhamnolipids) application. The outcomes of this study can aid in
a better understanding of injection design methods and biosurfactant formulation selection, which is
a critical attribute for green EOR technology.
© 2022 The Author(s). Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND
license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

1. Introduction
Oil recovery methods often fall into three main categories: pri-
mary, secondary, and tertiary (Green and Willhite, 1998). Primary
recovery, where the oil is recovered using the natural energy
contained in the reservoir—energy from the solution-gas drive,
natural water drive, fluid and rock expansion, gas-cap drive, and
gravity drainage—recovers only about 35% of the original oil in
place (OOIP). Other methods, such as waterflooding or immiscible
gas injection for pressure maintenance or displacement of the
oil towards the wellhead are used as secondary methods, which
can further the recovery up to around 50%, on average (Faisal
and Almomani, 2021; Haq et al., 2022; Muhammed et al., 2020;
Said et al., 2021). Other sources suggest that the primary and
secondary recovery methods combined may recover as little as
one-third of the OOIP in a given reservoir (Perry and Philip,
∗ Corresponding author.
E-mail addresses: bhaq@kfupm.edu.sa, bhaq225@gmail.com (B. Haq).
1985). These statistics suggest that as much as 65% of residual oil
remains in the reservoir, unrecoverable by traditional methods
of recovery due to the uneconomical cost of continued secondary
recovery methods or due to the trapping mechanisms holding the
oil in place. This is where enhanced oil recovery (EOR) comes in.
EOR is the practice of injecting materials (usually fluids or
gases) into the reservoir for any purpose other than the simple
displacement of the oil. It is usually aimed at lowering the in-
terfacial tension (IFT) between the oil and the surrounding fluid,
allowing the oil to flow and reach the production well (Green and
Willhite, 1998). Various methods of releasing the trapped oil so
that it can be recovered have been researched and implemented
as tertiary oil recovery methods. Most of these methods of EOR
fall under three classifications: Thermal, chemical, or gas (Faisal
and Almomani, 2021). Thermal methods of EOR generally involve
one of three things: Hot water injection, steam injection, or in-
situ combustion for heat generation. These methods are primarily
used in reservoirs with very heavy, viscous crude oils because
heat can decrease the viscosity of the oil and the injection of

https://doi.org/10.1016/j.egyr.2022.05.293
2352-4847/© 2022 The Author(s). Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-
nc-nd/4.0/).
A. Al-Ghamdi, B. Haq, D. Al-Shehri et al.
hot water or steam can help displace it towards the production
well (Green and Willhite, 1998). The injection of miscible gases
that will interact with the oil and the reservoir surroundings is
an EOR method, separate from the immiscible gas injection used
in secondary recovery methods. Carbon dioxide, hydrocarbon
gases, nitrogen, and flue gases are often used in this type of
EOR. Chemical enhanced oil recovery involves the injection of
various chemical fluids into the reservoir, such as polymers and
surfactants. These fluids interact with the oil and the surrounding
environment through their phase behavior properties, lowering
the IFT between the oil and the displacing fluid and allowing
the trapped oil to move out of the pores of surrounding rock
formations (Green and Willhite, 1998).
Studies show that chemical EOR is a very promising tech-
nique for residual oil recovery, especially in the case of surfactant
flooding. A report compiled in 1984 by the National Petroleum
Council suggested that with technological advances, chemical
enhanced oil recovery techniques may recover up to 40% of the
total residual oil recovered through EOR processes (Broome et al.,
1984). As was mentioned previously, chemical EOR is one of
the most promising types of enhanced oil recovery. There is a
drawback to it, however; the chemicals involved in the processes
are often environmentally concerning. Over the years, the tox-
icity of traditional synthetic surfactants has become more and
more of an issue. As awareness of the environmental aspects
of our actions increases, studies and experiments determining
the effect of these actions have also become commonplace to
determine what can be changed to lessen detrimental effects to
the environment wherever possible. The case of surfactants is no
exception. It has been found that many of the surfactants used to-
day have significant toxicity to the environment, such as sodium
dodecyl sulfate (SDS), alkyl sulfates (AS), alkylpolyoxyethylene
sulphates (AES), polyoxyethylene alkyl ethers (AE), polyoxyethy-
lene alkylphenyl ethers (APE), and alkyl benzene sulfonates (ABS)
(Abd-Allah, 1995; Barbieri et al., 1998; Liwarska-Bizukojc et al.,
2005; Susmi et al., 2010). Disposing of these surfactants is often
left to wastewater treatment plants, where aerobic microbial
action is expected to break down the surfactant to the point that
it will cause no harm to the environment when the treated water
is released (Kronberg et al., 2014). Unfortunately, the surfactants
are often not readily biodegradable, which means that a large
portion of them end up in lakes, rivers, and streams, where the
pollution and its effect on aquatic life are rapidly becoming visible
(Abel, 1976, 1974; Liwarska-Bizukojc et al., 2005; Mallatt, 1985;
Pittinger et al., 1993; Romanelli et al., 2004). Studies performed
on fish that had been exposed to surfactant waste even in levels
as low as 0.5 ppm showed negative effects (Bardach et al., 1965).
The higher the concentration of the surfactants in the water,
the more significant the detrimental effects become, with high
concentrations shown to kill large numbers of fish (Lewis, 1991;
Romanelli et al., 2004).
To help determine the level of the negative impact that a
surfactant poses to the environment, several standard measures
were developed; some to measure the biodegradability of the
surfactant in the environment, and others to show what level
of surfactant would be lethal to fish, algae, and daphnia (Kron-
berg et al., 2014). As an example of biodegradability parameters,
for a surfactant to be readily biodegradable it should reach 60%
biodegradation within 28 days in laboratory tests. The toxicity
parameters are measured using LC50 and EC50 , which refer to
Lethal Concentration and Effective Concentration, respectively
(Kronberg et al., 2014). LC50 is used to measure toxicity in fish,
while EC50 is used for daphnia and algae. Toxic levels are defined
as levels below 1 mg/L after 96 h of testing on algae and fish,
and 48 h of testing on daphnia, while levels above 10 mg/L are
considered to be environmentally benign (Kronberg et al., 2014).
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Energy Reports 8 (2022) 7800–7813
It has been found that biosurfactants have lower toxicity levels
and higher biodegradability, making them a better choice for
chemical EOR processes (Georgiou et al., 1992; Poremba et al.,
1991; Zajic et al., 1977). The bacteria strains that produce these
biosurfactants can often be incubated with renewable feedstock
sources, such as molasses (Patel and Desai, 1997) which also
contributes to their ‘‘green’’ title. Also, there is the fact that their
critical micelle concentration (CMC) levels are often far lower
than those of their synthetic counterparts, meaning that less of
them will be used overall and so there will be less pollution as a
whole (Desai and Banat, 1997; Rebello et al., 2014).
Due to environmental concerns, green EOR, or GEOR, has be-
come more popular in recent years, and many scientists and
engineers have been developing and studying biochemicals for
use in EOR methods (Safdel et al., 2017). It has been documented
that various strains of bacteria living in the reservoirs can produce
biosurfactants that are just as effective, if not even more so, as
the lab-developed synthetic chemical surfactants largely in use
today (Torres et al., 2011). A summary of these biosurfactants
used with respect to EOR is presented in Table 1. Of these bio-
surfactant types, rhamnolipid (which is produced by the bacteria
strain P. aeruginosa) is the focus of this study. Other green sur-
factants, like alkyl polyglycoside (APG) and lecithin, will be used
as co-surfactants in various formulations, whereas green alcohol
(1-butanol), will be used as a co-solvent. Few studies have fo-
cused on the application of environmentally friendly surfactants
in EOR processes, and even fewer studies studied the performance
of surfactant formulations entirely made up of green products.
Hence, this study intends to bridge this knowledge gap by focus-
ing entirely on green surfactant formulations for chemical flood-
ing in sandstone reservoirs. The primary objective of this study is
to evaluate the potential of using green surfactants, such as the
biosurfactants, rhamnolipid, as well as alkyl polyglycoside (APG),
and others (Alkan et al., 2020; Amani et al., 2010), in surfactant
flooding as a means of EOR in sandstone. The alcohol (1-butanol)
will be tested for its effectiveness as a co-solvent in various
formulations. A schematic depicting the process is shown in Fig. 1.
The objectives of this study are: (1) To determine the ability
of the biosurfactant rhamnolipid; the green surfactants APG and
lecithin; and the cosolvent 1-butanol to reduce the IFT to effec-
tively low levels for EOR needs in various formulated surfactant
blends. (2) To find the optimal surfactant–cosurfactant–cosolvent
formulation for maximum EOR performance and (3) To discover
the potential of the most effective surfactant formulations to
recover an economically significant amount of residual oil via
core-flooding experiments using Berea sandstone cores. This ob-
jective will be achieved by conducting the following experiments:
Salinity scans will be performed to determine the optimum salin-
ity and study the phase behavior of the surfactant formulations
and determine the characteristic curvature (Cc) value of each
surfactant to optimize each surfactant blend. Fluid properties
experiments will be used to determine the critical micelle con-
centration (CMC) and the IFT of the various formulations, to
help determine the surfactant formulation that is best able to
achieve ultralow IFT levels. Core-flooding experiments will be
performed to estimate the recovery potential under simulated
reservoir conditions. The structure of the paper is as follows.
First, the background is presented. Thereafter, the materials and
experimental methods of the study will be described in detail. In
the following section, results, and their relevance to green EOR
will be discussed. Finally, a summary and concluding remarks, as
well as recommendations for future work, are presented.
2. Background of the study
Based on the literature survey (Alkan et al., 2020; Alvarez et al.,
2020; Amani et al., 2010; Haq et al., 2020; Patel et al., 2015;
A. Al-Ghamdi, B. Haq, D. Al-Shehri et al. Energy Reports 8 (2022) 7800–7813

Table 1
Selected biosurfactants (microbial bioproducts) used for oil recovery process.
Microorganisms Metabolites (sample Oil recovery technique Percentage tertiary References
products) recovery
Rhodococcus ruber Biosurfactants Sand package technology 25.78% (Zheng et al., 2012)
species
Acinetobacter baylyi Biosurfactants Core displacement 28.00% (Zou et al., 2014)
species experiment
Pseudomonas species Rhamnolipids Core flooding 24.40% (Lan et al., 2015)
Bacillus licheniformis Biosurfactant Sand packed column 16.60% (El-Sheshtawy et al.,
species technique 2016)
Luteimonas huabeiensis Biosurfactants Core flooding 11.00% (Ke et al., 2018)
species
Candida tropicalis Bacillus Lipopeptide surfactin Laboratory scale sand 39.80% (Ashish and
subtilis species packed column method Debnath Das, 2018)
Bacillus safensis species Biosurfactant Core flooding 13.00% (de Araujo et al., 2019)
Bacillus mojavensis Lipopeptide JF-2 Core flooding 25.00% (Haq et al., 2020)
species

Fig. 1. Schematic for the green surfactant injection process for chemical EOR.

Sarafzadeh et al., 2014), it can be noted from much of the above
literature, green surfactants are beginning to gain popularity for
their potential in EOR. However, the research in this area is
still in its early stage and further studies are required to fully
understand and utilize the potential of green surfactants. Some
of the limitations of the currently published literature regarding
the two green surfactants that will be utilized in this study are:
(a) Rhamnolipid has never been studied for effectiveness in sand-
stone core-flood EOR experiments. Most of the studies performed
on rhamnolipid are aimed at bioremediation techniques in con-
taminated soil, sand, and seawater. The efficient IFT-lowering
properties of rhamnolipid can also lend themselves well to chem-
ical EOR processes, and this possibility should be tested and
exploited.
(b) Surfactant formulations using rhamnolipid as the primary
surfactant have not been attempted, nor have there been tests
using rhamnolipid with cosolvent alcohol. Either of these options
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may produce a very effective chemical mixture for use in EOR
chemical floods.
(c) While APG surfactants have been widely studied for uses such
as laundry detergents and cleaning formulas, there are relatively
few studies focusing on APG as a possible surfactant for EOR, and
even fewer attempting to test the potential of APG in sandstone
reservoirs.
3. Materials and methodology
3.1. Materials
Chemical Selection
In the microbial enhanced oil recovery (MEOR) process, mi-
crobes produce surfactants, polymers, alcohols, acids, ketones,
and gases (Haq, 2021). Rhamnolipid is an anionic surfactant and
lecithin is a zwitterionic surfactant. Both are bio-surfactants and
are selected for this work. Alkyl polyglucoside (APG) 264 is taken
A. Al-Ghamdi, B. Haq, D. Al-Shehri et al.
Table 2
List of materials, properties, and roles.
Material
Anionic biosurfactant,
Rhamnolipid
Nonionic green surfactant, APG
®
Glucopon 600 CSUP
Lecithin
1-Butanol
NaCl (Sodium Chloride)
Table 3
List of optimized formulations and their salinity scan variations.
Name set Salinity Surfactant
(wt.%) (wt.%)
RB 1%–20% Rhamnolipid - 1%
RAB 1%–10% Rhamnolipid - 1%
RL 1%–16% Rhamnolipid - 2%
from the nonionic group because it is an environmentally friendly
synthetic surfactant. APG 264 is made from biomass such as
coconut, palm oil, corn, potato, or wheat residues. It is entirely
biodegradable with very low toxicity (Haq, 2012; Haq et al.,
2020). Microbes can also produce methanol, ethanol, and butanol
in the MEOR process. Butanol was selected for the work because it
is one of the microbial by-products and more effective than other
microbial alcohols. The crude oil used in the study was Arabian
Light with an API of 30◦ and an EACN of 11. The other materials
used as well as their properties and suppliers are listed in Table 2.
3.2. Phase behavior study
The phase behavior of various green surfactant formulations
that have been developed using the HLD concept was tested in
this part of the study using salinity scans. The Cc of the surfactants
were obtained from the literature, to begin with, and their final
numbers were determined from the results of preliminary scans.
The concentration of the surfactant, cosurfactant, and cosolvent
was fixed, and the salinity was varied in increments of 1%, with
the range of the salinity scan depending on the type of for-
mulation and the calculated HLD value of the blend. A number
of salinity scan tests were conducted (Table 3), using various
surfactant/cosurfactant/cosolvent formulations. In all cases, the
water–oil ratio (WOR) was kept at 1.
The volume of the oil and the water were measured at 5 mL
each, causing half of the sample to be in the oil phase, and a
half to be in the aqueous phase, which consisted of the brine of
varying salinity mixed with the surfactant solution. For maximum
accuracy and precision, graduated pipettes were used to measure
each component. The surfactant mixtures were prepared using
weight percent, with each component being added by weight
instead of volume. They were mixed thoroughly using a vortex
spinner until all the components were completely dissolved, then
added into glass test tubes using graduated pipettes. The crude
oil was then added, also with the use of graduated pipettes, and
each of the tubes was thoroughly shaken by hand for 30 s. After
shaking, the mixture was left to stabilize and reach equilibrium
at room temperature. Equilibrium can be considered to have been
achieved if there have been no further changes in the various
phase volumes over 24 h (Haq, 2012). The mixtures were moni-
tored carefully for changes over several days, and the final phase
volumes were then recorded and used to calculate the solubilized
volumes of oil and water based on the difference between the
initial and final volumes of each phase. Fluid properties (density
and viscosity) measurement data are given in Appendix A.
Energy Reports 8 (2022) 7800–7813
Purity Supplier Role
90.00% AGAE Tech. Primary surfactant
50%–75% BASF Corp. Cosurfactant
97.00% Fearn Cosurfactant
99.00% Sigma-Aldrich Cosolvent
99.50% Sigma-Aldrich Synthetic brine
Cosurfactant Co-solvent Oil type
(wt.%) (wt.%)
0% 3% 1-butanol Arab light crude
APG - 1% 3% 1-butanol Density at 25 ◦ C = 0.87 (g/cc)
Lecithin – 2% 0% Viscosity at 25 ◦ C = 19.8 cP
3.3. Interfacial tension measurements
The methodology of the interfacial tension (IFT) is described in
this section. Three sets of samples were prepared to measure IFT
and density. Each set represented one of the three formulations
that were chosen after the phase behavior study. Set A contained
rhamnolipid as the primary surfactant and 1-butanol as the co-
solvent alcohol. The concentration ratio of rhamnolipid to butanol
was set at 1:3, matching the concentration ratio used in the phase
behavior study. Set B consisted of rhamnolipid as the primary
surfactant, APG as the cosurfactant, and 1-butanol as the co-
solvent alcohol. The concentration ratio of the three components
was set to 1:1:3, matching the concentration used in the phase
behavior study. Set C consisted of rhamnolipid as the primary
surfactant and lecithin as the cosurfactant with a concentration
ratio of 1:1.
A spinning drop tensiometer (M6500, Grace Instrument Com-
pany) was used to measure the interfacial tension; an image of
the apparatus can be seen in Appendix A. To analyze the drop
shape, the apparatus illuminates the drop from one side and
records it with a camera from the opposite side. The accompa-
nying software determines the drop diameter from the image
obtained from the camera. The following steps were carried out
to experiment. First, the capillary tube was cleaned with distilled
water and rinsed with the sample. The sample was injected until
the capillary tube is full. Using a syringe, a drop of crude oil was
injected. Second, the capillary tube was checked for the pres-
ence of air bubbles. If present, the previous steps were repeated.
Third, the desired temperature was set and allowed to equilibrate.
Fourth, the Angular Frequency was between 3000 and 8000 rpm
to ensure that the drop length is at least four times the diameter,
and the drop outlines are not curved. Finally, the measurement of
the diameter of the oil drop was recorded from the software. The
experiment was carried out for 30 min and the IFT value at the
end of that period was calculated and saved in the instrument.
3.4. Core-flooding experiment
The core-flooding experiments are performed to attempt to
discover the likely behavior of a given surfactant inside of a
reservoir under common reservoir pressure and temperature lev-
els. The amount of oil recovered by a given surfactant during
a core flood can give a good indication of the possible tertiary
recovery under normal reservoir conditions. Three core flood tests
were performed using the surfactant formulations that displayed
the lowest IFT values in the previous fluid properties study. A
process flow diagram of the core flood experiment is presented
in Fig. 2. Detailed experimental processes and figures are given in
Appendix B.
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A. Al-Ghamdi, B. Haq, D. Al-Shehri et al. Energy Reports 8 (2022) 7800–7813

Fig. 2. Core flood process flow diagram.

Fig. 3. Rhamnolipid and 1-Butanol phase behavior.. (For interpretation of the

Fig. 4. Rhamnolipid, APG, and 1-Butanol phase behavior.. (For interpretation of
references to color in this figure legend, the reader is referred to the web version
the references to color in this figure legend, the reader is referred to the web
of this article.)
version of this article.)

4. Results and discussion

4.1. Phase behavior study
Test tube samples were prepared with 5 mL of the relevant
aqueous surfactant formulation and 5 mL of crude oil. The salinity
of the aqueous solution was varied in increments of 1%. The tubes
were mixed thoroughly. Afterward, they were left for 48 h or
more to allow the fluids to reach phase equilibrium in ambi-
ent temperature and pressure. The phase characteristics of each
system were recorded. These were the relative volume of the
aqueous phase, the middle phase, and the oleic phase. The results
of the phase behavior study are summarized below.
4.1.1. Rhamnolipid and 1-butanol
This formulation was made up of a mixture of 1% anionic
surfactant rhamnolipid and 3% 1-butanol as a cosolvent. The
salinity of the brine was varied from 1% to 20% in 1% increments.
This formulation displayed promising results, developing a dis-
tinct middle phase microemulsion in all the tubes. The optimum
salinity, calculated by the average of all tubes displaying a type III
microemulsion, was determined to be 10%. Fig. 3 shows a phase
volume fraction chart for the formulation.
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4.1.2. Rhamnolipid, APG, and 1-butanol
This formulation was made up of a mixture of 1% anionic
surfactant rhamnolipid, 1% non-ionic surfactant APG as a co-
surfactant, and 3% 1-butanol as a cosolvent. The salinity of the
brine was varied from 1% to 10% in 1% increments. A distinct
middle phase microemulsion was observed in all of the tubes
where the salinity was higher than 3%. The optimum salinity was
determined to be 7%. Fig. 4 shows a phase volume fraction chart
for the formulation.
4.1.3. Rhamnolipid and lecithin
This formulation was made up of a mixture of 2% anionic sur-
factant rhamnolipid and 2% zwitterionic surfactant lecithin. The
salinity of the brine was varied from 1% to 16% in 1% increments.
Middle phase microemulsions were observed across all tubes. The
optimum salinity was determined to be 5%. Fig. 5 shows a phase
volume fraction chart for the formulation.
4.2. Interfacial tension measurement
The IFT between the crude oil and brine was measured at
ambient temperature and found to be 23 dynes/cm. For the
A. Al-Ghamdi, B. Haq, D. Al-Shehri et al. Energy Reports 8 (2022) 7800–7813

Table 4
IFT values of the Rhamnolipid and 1-Butanol blend.
Sample Rhamnolipid 1-butanol IFT at 25 ◦ C IFT at 52 ◦ C
concentration (wt.%) concentration (wt.%) (dynes/cm) (dynes/cm)
A1 0.02 0.06 0.14407 0.13877
A2 0.04 0.12 0.24657 0.21467
A3 0.06 0.18 0.26126 0.23239
A4 0.08 0.24 0.2324 0.20326
A5 0.50 1.50 0.1842 0.18526

Fig. 5. Rhamnolipid and Lecithin phase behavior.. (For interpretation of the

references to color in this figure legend, the reader is referred to the web version
of this article.)
Fig. 6. The plot of the IFT against the Rhamnolipid and 1-Butanol blend.

surfactant formulations, the IFT values between the oil and the
various samples from the three sets were measured at both room
and reservoir temperatures.

4.2.1. IFT of rhamnolipid and 1-butanol blend

Table 4 outlines the results for the Rhamnolipid and 1-Butanol
mixture, and the IFT value is plotted against the rhamnolipid
concentration in Fig. 6. The IFT value reaches a minimum of
approximately 0.14 dyne/cm (at 25 o C) and 0.13 dyne/cm (at
52 o C) at a rhamnolipid concentration of 0.02 wt% respectively.
Thereafter, it slightly increased to approximately 0.26 dyne/cm
(at 25 o C) and 0.23 dyne/cm (at 52 o C) as the concentration of
rhamnolipid increases to 0.06 wt% respectively, before terminat-
ing at 0.18 dyne/cm for both temperature conditions. This trend
indicates that the CMC, or critical micelle concentration, for this
formulation is reached at 0.02 wt%. In addition, it is observed that
increasing the temperature from 25 ◦ C to 52 ◦ C has little effect on
the IFT value for all of the measured concentrations.
Fig. 7. The plot of the IFT against the Rhamnolipid, APG, and 1-Butanol
combination.
4.2.2. IFT of rhamnolipid, APG, and 1-butanol combination
Table 5 summarizes the results for the Rhamnolipid, APG,
and 1-Butanol combination, and the IFT value is plotted against 4.2.3. IFT of rhamnolipid and lecithin mixture
rhamnolipid concentration in Fig. 7. The IFT value drops from 23 Table 6 describes the results for the Rhamnolipid and Lecithin
dyne/cm to 0.225 dyne/cm (at 25 o C) and 0.237 dyne/cm (at 52 mixture, and the IFT value is plotted against rhamnolipid concen-
o
C) at a rhamnolipid concentration of 0.02 wt% respectively. Con- tration in Fig. 8. The IFT value reaches a minimum of approxi-
sequently, after a sudden increase in IFT value (particularly at 25 mately 0.01 dyne/cm at a rhamnolipid concentration of 0.04 wt%
o (at 25 o C and 52 o C) respectively, before a slight increase to
C), a steep fall was observed where both IFT values reached 0.16
approximately 0.77 dyne/cm (at 25 o C) and 0.88 dyne/cm (at 52
dyne/cm (at 25 o C and 52 o C, respectively) as the concentration o
C) respectively as the concentration of rhamnolipid increased
of rhamnolipid increased to 0.5 wt%. This trend indicates that the to 0.08 wt%. Despite the subsequent decrease in IFT values with
CMC for this formulation is likely to extend beyond 0.5 wt% as rhamnolipid concentration increase to 0.25 wt%, the trend, thus,
a further increase in rhamnolipid concentration could lead to a indicates that the CMC for this formulation is 0.04 wt%. Just like
further decrease. Though, it is also observed that increasing the other formulations, the effect of increasing the temperature from
temperature from 25 ◦ C to 52 ◦ C has little effect on the IFT value 25 ◦ C to 52 ◦ C has little effect on the IFT value at all of the
for all of the measured concentrations. measured concentrations.
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A. Al-Ghamdi, B. Haq, D. Al-Shehri et al. Energy Reports 8 (2022) 7800–7813

Table 5
IFT values of the Rhamnolipid, APG and 1-Butanol combination.
Sample Rhamnolipid APG 1-butanol IFT at 25 ◦ C IFT at 52 ◦ C
concentration concentration concentration (dynes/cm) (dynes/cm)
(wt.%) (wt.%) (wt.%)
B1 0.02 0.02 0.06 0.22536 0.23703
B2 0.04 0.04 0.12 0.24097 0.22819
B3 0.06 0.06 0.18 0.23831 0.22394
B4 0.08 0.08 0.24 0.22578 0.20599
B5 0.5 0.5 1.5 0.16887 0.16656

Table 6
IFT values of the Rhamnolipid and Lecithin mixture.
Sample Rhamnolipid Lecithin IFT at 25 ◦ C IFT at 52 ◦ C
concentration concentration (dynes/cm) (dynes/cm)
(wt.%) (wt.%)
C1 0.02 0.02 0.07535 0.05813
C2 0.04 0.04 0.0189 0.0181
C3 0.06 0.06 0.15116 0.07286
C4 0.08 0.08 0.77669 0.8896
C5 0.25 0.25 0.56347 0.41915

Table 7
Properties of the three Berea sandstone cores used in the core floods.
Core sample Length Diameter Pore volume (cm3 ) Dry weight Porosity Permeability
(cm) (cm) (g) (%) (mD)
1 15.2 3.8 34.04 367.41 19.75 176
2 15.1 3.8 36.31 358.77 21.20 145
3 14.9 3.8 35.14 353.34 20.79 132

Three sandstone core plugs were used in the measurement and

the properties were measured and presented in Table 7.

4.3.1. Oil recovery of the rhamnolipid and 1-butanol blend

Fig. 8. The plot of the IFT against the Rhamnolipid and Lecithin mixture.
4.3. Oil recovery performance through core flooding experiment
In this experiment, the sandstone core was fully saturated
with 3% NaCl brine and then flooded with crude oil until the
core reached residual water saturation. The oil-saturated core was
then flooded with 3% NaCl brine until it was near residual oil
saturation to simulate the water flooding process. The flooding
was stopped when only a trace amount of oil was produced, or
three pore volumes of brine had been injected. The surfactant was
a mixture of 0.5% rhamnolipid and 1.5% 1-butanol.
At the end of the oil flood, residual water saturation (Swr ) was
measured at 44.2%. After the water flooding stage was complete,
the residual oil saturation (Sor ) was 33.8% and the secondary oil
recovery was 39% of the OOIP. The surfactant flooding resulted
in an incremental oil recovery of 19.6% and a total oil recovery
of 59.1%. Finally, the post flush recovered an additional 3% which
brought the total oil recovery to 62.1%. The tertiary oil recovery
was 22.6% of the OOIP. Table 8 details the amount recovered and
fluid saturations during the different stages, and Fig. 9 shows the
total oil recovery versus the total injected pore volume during the
brine flooding, surfactant flooding, and post flush.

In this part of the study, three core-flood experiments were

conducted to test the EOR capability of three green surfactant
mixtures formulations. The first experiment was carried out to
investigate the ability of a biosurfactant/alcohol mixture to im-
prove tertiary oil recovery (TOR). The second experiment aimed
to examine the EOR performance of the previous formulation
when the green APG surfactant is added as a co-surfactant for
increased stability at high temperatures and salinity levels. The
objective of the last core flood experiment was to observe the
impact of an alcohol-free green surfactant mixture of rhamnolipid
and lecithin on EOR. In this section, the measured and observed
data collected during the three core flooding experiments will be
tabulated. In addition, the results will be presented and discussed.
7806
4.3.2. Oil recovery of the rhamnolipid, APG, and butanol combination
In this experiment, the sandstone core was fully saturated
with 3% NaCl brine and then flooded with crude oil until the
core reached residual water saturation. The oil-saturated core was
then flooded with 3% NaCl brine until it was near residual oil
saturation to simulate the water flooding process. The flooding
was stopped when only a trace amount of oil was produced, or
three pore volumes of brine had been injected. The surfactant was
a mixture of 0.5% rhamnolipid, 0.5% APG, and 1.5% 1-butanol.
At the end of the oil flood, residual water saturation (Swr ) was
measured at 42.2%. After the water flooding stage was complete,
the residual oil saturation (Sor ) was 31.5% and the secondary oil
recovery was 45.5% of the OOIP. The surfactant flooding resulted
A. Al-Ghamdi, B. Haq, D. Al-Shehri et al. Energy Reports 8 (2022) 7800–7813

Table 8
Flood results for Rhamnolipid and Butanol blend.
Formulation 1: 0.5% Rhamnolipid + 1.5% Butanol + 3% NaCl Water
Core PV Oil Soi Water flood Surfactant flood Post flood Total
(cm3 ) volume (%) recovery recovery recovery
(cm3 )
cm3 % cm3 % cm3 % %
1 34.04 19 55.8 7.49 39.40 3.73 19.60 0.57 3.00 62.10

Table 9
Flood results for Rhamnolipid, APG and Butanol combination.
Formulation 2: 0.5% Rhamnolipid + 0.5% APG + 1.5% Butanol + 3% NaCl Water
Core PV Oil Soi Water flood Surfactant flood Post flood Total
(cm3 ) volume (%) recovery recovery recovery
(cm 3 )
cm3 % cm3 % cm3 % %
2 36.31 21 57.8 9.55 45.5 0.71 3.40 1.35 6.40 55.30

Fig. 9. Oil recovery of the Rhamnolipid and Butanol blend. Fig. 10. Oil recovery of the Rhamnolipid, APG, and Butanol combination.

in a modest incremental oil recovery of 3.4% and a total oil recov-
ery of 48.9%. Finally, the post-flush recovered an additional 6.4%,
bringing the total oil recovery to 55.3%. The tertiary oil recovery
was 9.8% of the OOIP. Table 9 details the amount recovered and
fluid saturations during the different stages, and Fig. 10 shows the
total oil recovery versus the total injected pore volume during the
brine flooding, surfactant flooding, and post flush.
4.3.3. Oil recovery of the rhamnolipid and lecithin mixture
In this experiment, the sandstone core was fully saturated
with 3% NaCl brine and then flooded with crude oil until the
core reached residual water saturation. The oil-saturated core was
then flooded with 3% NaCl brine until it was near residual oil
saturation to simulate the water flooding process. The flooding
was stopped when only a trace amount of oil was produced, or
three pore volumes of brine had been injected. The surfactant was
a mixture of 0.25% rhamnolipid and 0.25% lecithin.
At the end of the oil flood, residual water saturation (Swr ) was
measured at 43.1%. After the water flooding stage was complete,
the residual oil saturation (Sor ) was 31.0% and the secondary oil
recovery was 46% of the OOIP. The surfactant flooding resulted
in an incremental oil recovery of 14.3% and a total oil recovery
of 59.9%. Finally, the post-flush recovered an additional 9.8%,
bringing the total oil recovery to 69.6%. The tertiary oil recovery
was 24% of the OOIP. Table 10 details the amount recovered and
7807
fluid saturations during the different stages, and Fig. 11 shows the
total oil recovery versus the total injected pore volume during the
brine flooding, surfactant flooding, and post flush.
4.3.4. Comparison of the three formulations
A summary of the three formulation results is shown in
Table 11. The oil recovery at the different stages, secondary
and tertiary, for the three cases is illustrated in Fig. 12. The
rhamnolipid/lecithin formulation performed best, with a TOR of
24%. The rhamnolipid/butanol formulation achieved a similar,
albeit slightly smaller, value of 22.6% for the TOR. The rhamno-
lipid/APG/butanol mixture resulted in a significantly smaller TOR
value of 9.8%.
5. Relevance of this study to GEOR
In microbial enhanced oil recovery (MEOR), the produced
metabolites by microorganisms can be used to increase the ulti-
mate oil recovery through specific approaches that is significantly
impact the physical properties of reservoirs including porosity,
permeability, wettability as well as fluid characteristics such as
viscosity, IFT, etc. (Safdel et al., 2017). Besides biosurfactants,
microbial bioproducts can be classified into six groups such
as, biopolymers, gases, acids, solvents, biomass, and emulsifiers
A. Al-Ghamdi, B. Haq, D. Al-Shehri et al. Energy Reports 8 (2022) 7800–7813

Table 10
Flood results for Rhamnolipid and Lecithin mixture.
Formulation 3: 0.25% Rhamnolipid + 0.25 Lecithin + 3% NaCl Water
Core PV (cm3 ) Oil Soi Water flood Surfactant flood Post flood Total
volume (%) recovery recovery recovery
(cm3 )
cm3 % cm3 % cm3 % %
3 35.14 20.00 56.9 9.12 45.60 2.85 14.3 1.95 9.80 69.70

Table 11
Oil recovery of the three formulations.
Core No. Formulation Oil recovery (%)
Secondary Tertiary Total
1 0.5% Rhamnolipid + 1.5% Butanol 39.4 22.6 62.1
2 0.5% Rhamnolipid + 0.5% APG + 1.5% Butanol 45.5 9.8 55.3
3 0.25% Rhamnolipid +0.25% Lecithin 45.6 24 69.6

from chemical surfactants due to these advantages. Albeit, the

Fig. 11. Oil recovery of the Rhamnolipid and Lecithin mixture.
Fig. 12. Comparison of the oil recovery for each of the three developed
formulations.
(Saravanan et al., 2020) which all influence the behavior of
reservoir fluids when injected for EOR purposes. In the case of
biosurfactants, they are extremely important because of their
biodegradability (Mohan et al., 2006), low toxicity (Safdel et al.,
2017), emulsification activity, and stability in different environ-
ments (Safdel et al., 2017). This fact differentiates biosurfactants
7808
application depends on their stability at extreme conditions of
temperature, salinity, and pH (Amani et al., 2010). Based on the
charge of the polar head group, biosurfactants are divided into
four groups namely: cationic, anionic, nonionic, and zwitterionic
(Safdel et al., 2017). This study reports the case of blending
biosurfactants with green surfactants as one of the means to min-
imize cost (Haq et al., 2020). Moreover, the practice of blending
anionic, non-ionic and zwitterionic surfactants is a technique that
has been used in the petroleum industry in EOR for a long time
(Green and Willhite, 1998). However, only a little attention had
been paid to blending green surfactants in a single formulation
to stimulate residual oil production.
Haq et al. (2020) successfully examine the effectiveness of
blending microbial by-products, bio-surfactant (JF-2), and bio-
alcohol, in recovering residual oil within sandstone rock as well
as the blending of biosurfactant (JF-2) with non-ionic green sur-
factant APG. After screening the different blends based on phase
behavior and IFT studies, only two formulations were selected for
EOR potential. The first formulation (JF-2 plus butanol) showed
low EOR potential whereas formulation 2 (JF-2 plus APG and
butanol) produced nearly 25% tertiary oil from the reservoir.
This shows that blending biosurfactant (anionic) and APG 264
(non-ionic) surfactant with butanol can boost residual oil produc-
tion due to their stable middle phase microemulsion (Haq et al.,
2020). Our study also observed a similar trend as all formulations
showed stable middle phase microemulsion. However, combining
rhamnolipid (anionic) and lecithin (zwitterionic) (i.e., formula-
tion RL) significantly influences the ultralow IFT value between
oil and water compared to other formulation blends (RB and
RAB). Even though both RB and RAB blends had stable middle
phase microemulsion, our study shows that blending biosurfac-
tant rhamnolipid with cosolvent butanol (RB) and biosurfactant
rhamnolipid with cosurfactant APG and co-solvent butanol has
low impact on EOR (due to their low IFT) compared to bio-
surfactant rhamnolipid and co-surfactant lecithin (which has an
ultra-low IFT value). In prospect, green surfactants lecithin can
be considered a very good co-surfactant option for blending.
Additionally, the selection of APG in this work is based on its
oil recovery capacity as previously studied. For instance, Iglauer
et al. performed a laboratory study of APG to examine the stability
of this non-ionic surfactant for EOR. They found that APG co-
surfactant combinations can produce very low IFT with values
largely independent of temperature and salinity (Iglauer et al.,
2009). Using a Berea sandstone core, n-octane, and a specific
formulation (Agrimul 2062/1-octanol), they were able to recover
up to 85 percent of OOIP in a core flood test (Iglauer et al.,
2009). Interestingly, our study also reported IFT values that were
independent of temperature, implying that these formulations
A. Al-Ghamdi, B. Haq, D. Al-Shehri et al. Energy Reports 8 (2022) 7800–7813

(RB, RAB, and RL) can be applicable in high temperature reser- Nomenclature
voir to produce residual oil. Additionally, our core flooding test ABS Alkyl Benzene Sulfonates
recorded significant incremental oil recovery. For instance, the AE Polyoxyethylene Alkyl Ethers
first formulation (RB) was able to achieve almost 23% tertiary AES Alkylpolyoxy Ethylene Sulfates
recovery and 62% of the OOIP whereas the second formulation APE Alkyl Phenyl Ethers
(RAB) did not perform as well as expected, with the incremental APG Alkyl Polyglycoside
oil recovery only around 10%, and total recovery of 55%. The
AS Alkyl Sulfates
third formulation (RL) however, performed the best of the three,
Cc Characteristic Curvature
with a tertiary recovery of 24% and an approximated 70% total
CMC Critical Micelle Concentration
recovery. While the two blends (RB and RAB) have good EOR
EC50 Effective Concentration (mg/L)
potential, our investigation suggests that the third formulation
EOR Enhanced Oil Recovery
(RL) is a better choice for chemical EOR with a preference for the
GEOR Green Enhanced Oil Recovery
studied biosurfactant (rhamnolipids). The findings of this study
IFT Interfacial Tension (dyne/cm)
could help with injection design methodologies and biosurfactant
LC50 Lethal Concentration (mg/L)
formulation selection, both of which are important for GEOR
NaCl Sodium Chloride
applications.
OOIP Original Oil in Place
PV Pore Volume
6. Summary and conclusions
RAB Rhamnolipid Alkyl Polyglycoside Butanol
RB Rhamnolipid Butanol
Based on the experimental investigations, the main findings of
RL Rhamnolipid Lecithin
this study are:
SDS Sodium Dodecyl Sulfate
• A surfactant formulation consisting of 1% anionic surfactant Soi Initial Oil Saturation
rhamnolipid and 3% butanol gives a stable middle phase Sor Residual Oil Saturation
microemulsion when the salinity is within the range of 1%– Swr Residual Water Saturation
20%. In addition, blending the previous formulation with TOR Tertiary Oil Recovery
1% APG shows a stable middle phase microemulsion over WOR Water Oil Ratio
a salinity range of 3%–9%. Finally, a formulation of 2% an-
ionic surfactant rhamnolipid and 2% zwitterionic surfactant CRediT authorship contribution statement
lecithin generates a stable middle phase microemulsion over
a salinity range of 1%–10%. Ahmed Al-Ghamdi: Conception and design of study, Acqui-
• The rhamnolipid/lecithin surfactant formulation reduces the sition of data, Analysis and/or interpretation of data, Writing –
interfacial tension between the crude oil and the brine to original draft. Bashirul Haq: Conception and design of study,
an ultralow value of 0.01 dynes/cm. On the other hand, the Analysis and/or interpretation of data, Writing – original draft,
formulations that consist of rhamnolipid/butanol or rham- Writing – review & editing. Dhafer Al-Shehri: Conception and
nolipid/APG/butanol lower the interfacial tension between design of study, Analysis and/or interpretation of data, Writing –
the crude oil and the brine to 0.1 dynes/cm. original draft. Nasiru S. Muhammed: Writing – review & editing.
• The temperature was found to have a negligible impact on Mohamed Mahmoud: Writing – review & editing.
the value of the measured IFT in all three of the tested
formulations. Declaration of competing interest
• The rhamnolipid/butanol and rhamnolipid/lecithin surfac-
tants formulations have been successful in recovering addi- The authors declare that they have no known competing finan-
tional amounts of oil after the waterflooding process. During cial interests or personal relationships that could have appeared
the core flooding experiments, the first formulation recov- to influence the work reported in this paper.
ered 22.6% of the OOIP while the second recovered 24% of
the OOIP. Acknowledgment
• The rhamnolipid/APG/butanol formulation was not success-
ful at recovering any significant amount of oil during the The authors appreciate the College of Petroleum Engineering
core flooding test. and Geoscience (CPG) at King Fahd University of Petroleum and
Minerals (KFUPM) for providing Startup fund SF19005 and unre-
7. Recommendations stricted access to vast academic resources which made this work
possible.
The following are recommendations for additional work: All authors approved the version of the manuscript to be
published.
• It is recommended that graduated pipettes be used in the
phase behavior studies as they provide better resolution Appendix A. Fluid properties measurements
when measuring the volume of the different phases.
• It is recommended that a real reservoir brine is used in The methodology and equipment used to measure fluid prop-
place of the NaCl solution to more accurately simulate the erties including density, viscosity, and interfacial tension (IFT) are
conditions at the reservoir. described in this section.
• It is recommended that surfactant adsorption studies be
conducted to determine the adsorption parameters for the A.1. Density measurements
surfactants used.
• It is recommended to utilize the developed simulation mod- The density of the crude oil, brine and the surfactant formu-
els to perform sensitivity analyses to investigate the effect lations at different concentrations was measured at both room
of different parameters on the performance of surfactants in temperature and at typical reservoir temperature (25 and 52 ◦ C,
core flooding experiments. respectively). Density values are required for measurement of
7809
A. Al-Ghamdi, B. Haq, D. Al-Shehri et al. Energy Reports 8 (2022) 7800–7813

Table A.1
Density of Rhamnolipid and Butanol blend.
Sample Rhamnolipid 1-Butanol Density at Density at
concentration concentration 25 ◦ C (g/cm3 ) 52 ◦ C (g/cm3 )
(wt.%) (wt.%)
A1 0.02 0.06 1.01844 1.00767
A2 0.04 0.12 1.01837 1.00750
A3 0.06 0.18 1.01823 1.00697
A4 0.08 0.24 1.01810 1.00407
A5 0.5 1.5 1.01638 1.00347

Table A.2
Density of Rhamnolipid, APG and Butanol combination.
Sample Rhamnolipid APG 1-butanol Density at Density at
concentration concentration concentration 25 ◦ C (g/cm3 ) 52 ◦ C (g/cm3 )
(wt.%) (wt.%) (wt.%)
B1 0.02 0.02 0.06 1.01838 1.00487
B2 0.04 0.04 0.12 1.01827 1.00747
B3 0.06 0.06 0.18 1.01819 1.00757
B4 0.08 0.08 0.24 1.01838 1.00766
B5 0.5 0.5 1.5 1.01688 1.00606

Table A.3
Density of Rhamnolipid and Lecithin mixture.
Sample Rhamnolipid Lecithin concentration Density at Density at
concentration (wt.%) (wt.%) 25 ◦ C 52 ◦ C
(g/cm3 ) (g/cm3 )
C1 0.02 0.02 1.01860 1.00786
C2 0.04 0.04 1.01886 1.00813
C3 0.06 0.06 1.01953 1.00813
C4 0.08 0.08 1.01904 1.00828
C5 0.25 0.25 1.01965 1.00887

Table A.4
Density of Arab light Crude and 3% NaCl.
Density at 25 ◦ C Density at 52 ◦ C
(g/cm3 ) (g/cm3 )
Crude Oil 0.86992 0.84840
Brine 1.01841 1.00135

Table A.5
Viscosity of Arab light Crude and 3% NaCl.
Sample Viscosity at 25 ◦ C Viscosity at 52 ◦ C
(cP) (cP)
Crude Oil 19.8 8.2
Brine 1.2 0.7

the interfacial tension between the oil and the surfactant for-
Fig. A.1. M6500 Spinning Drop Tensiometer.
mulations when using the spinning drop tensiometer method for
IFT measurement. Tables A.1–A.4 present the summary measure-
ments.
A.3. Interfacial tension measurements

A.2. Viscosity measurements
Table A.5 summarizes the viscosity measurements for the
crude oil and brine samples at room and reservoir temperatures.
It can be seen that the viscosity of the crude oil was reduced
significantly as the temperature increased from 25 ◦ C to 52 ◦ C.
A similar pattern was observed for the brine as well. This trend is
expected, because viscosity is strongly and inversely proportional
to temperature.
7810
The image of the spinning drop tensiometer (M6500, Grace
Instrument Company) used for IFT measurement (Fig. A.1).
Appendix B. Core flood experiment
B.1. Apparatus
The core flooding experiments were conducted using a FDES-
645Z from Coretest Systems, Inc. Fig. B.1 is a picture of the system
A. Al-Ghamdi, B. Haq, D. Al-Shehri et al.
Fig. B.1. FDES-645Z core-flooding apparatus.
Fig. B.2. FDES-645Z core-flooding apparatus, inside-oven view.
with a brief description of the main components, and Fig. B.2
displays the components that reside inside the oven along with a
short description of each. A gas cylinder was connected to the BPR
gas supply connection to provide the backpressure for the system.
In addition, a pump (from Teledyne-Isco) is used to provide the
confining pressure inside the core holder.
B.2. Core sample preparation and saturation
First, the core samples were obtained from Berea sandstone
rock. Berea was chosen because it is a standard representative
for sandstone in porous laboratory experiments in the petroleum
industry and in the literature. Then, three cores measuring 1.5
inches in diameter and 6 inches in length were cut. The dry cores
were weighed, and their length and diameter were measured.
Next, the samples were saturated with 3% NaCl brine and then
oil, and then aged for seven days.
7811
Energy Reports 8 (2022) 7800–7813
B.3. Waterflooding
The core was left to age at the previously specified pressure
and temperature conditions for a minimum of 48 h. After com-
pletion of the aging process, the flow valve for the oil was opened
and the pump was started at a rate of 0.5 mL/min until the
pressure stabilized.
After the pressure stabilized, the flow valve for the oil was
closed and the one for brine was opened. Then, the produced
brine and oil were collected in 10 mL graduated tubes.
The waterflood continued until negligible amounts of oil were
produced.
B.4. Surfactant flooding
The flow valve for the brine was closed and the one for the
surfactant was opened. The produced fluids were collected in
10 mL graduated tubes. The surfactant flood continued until a
A. Al-Ghamdi, B. Haq, D. Al-Shehri et al.
negligible amount of oil was being produced or 3 pore volumes
of surfactant had been injected.
B.5. Brine post-flood
The flow valve for the brine was opened and the one for
the surfactant was closed. The produced fluids were collected in
10 mL graduated tubes. The brine post-flush continued until a
negligible amount of oil was being produced or 3 pore volumes
of brine had been injected. The produced fluids were collected
in 10 mL graduated tubes. The surfactant flood continued until a
negligible amount of oil was being produced or 3 pore volumes
of surfactant had been injected.
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