Journal of Petroleum Science and Engineering 81 (2012) 24–30

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Journal of Petroleum Science and Engineering

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Enhanced oil recovery from low permeability dolomite cores using biosurfactant
produced by a Bacillus mojavensis (PTCC 1696) isolated from Masjed-I Soleyman field
Hossein Ghojavand a, b,⁎, Farzaneh Vahabzadeh a, Alireza Khodabandeh Shahraki b
a
Department of Chemical Engineering, Amirkabir University of Technology (Tehran Polytechnic), Tehran, Iran
b
IOR Research Institute, Research and Technology Directorate, National Iranian Oil Company, Tehran, Iran

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

Article history: A Bacillus mojavensis strain (PTCC 1696) which was isolated from an Iranian oil field was used to produce a
Received 22 February 2011 lipopeptidic biosurfactant. The surface activity measurement with De Nouy ring detachment method showed
Accepted 1 December 2011 that this biosurfactant is able to reduce the surface tension of the media and interfacial tension between
Available online 16 December 2011
aqueous phase and n-hexadecane to 26.7 and 0.1 mN/m respectively. The core flooding tests were carried
out to evaluate oil recovery from carbonate reservoirs by this lipopeptidic biosurfactant. These tests were
Keywords:
biosurfactant
conducted at reservoir conditions using low permeability dolomite cores, live crude oil and reservoir forma-
dolomite tion brine. The experiments showed that the biosurfactant-assisted waterflooding method can be considered
interfacial tension as a technique for oil recovery from carbonate formations. The results obtained in this study showed the po-
oil recovery tential of the biosurfactant produced by Bacillus strains for enhanced oil recovery even from low-permeability
carbonate reservoirs.
© 2011 Elsevier B.V. All rights reserved.

1. Introduction
The oil recovery by conventional water flooding process is not
known as an effective technique in the oil-wet; especially fractured
reservoirs. Theoretically, displacement of the residual oil through
the porous media depends on the capillary number which is defined
as follows:
Viscous force μν
NC ¼ ¼ ð1Þ
Capillary force ξ enhanced oil recovery. These microbial surfactants can be produced from
where NC is the dimensionless capillary number, μ [cp] is the viscosi-
ty, ν [cm/h] is the frontal velocity and ξ [mN/m] is the interfacial ten-
sion between displacing and displaced fluids.
The oil recovery from porous media could be increased only when
the capillary number of the oil displacing fluid significantly increased.
In fractured carbonate reservoirs, surfactants can improve oil displace-
ment from the matrix blocks into the fractures by lowering capillary
forces (Austad et al., 1998; Standnes and Austad, 2003; Zhang et al.,
2006). Recently, the oil recovery from carbonates by surfactants has
been interestingly considered (Austad et al., 1998; Ayirala et al., 2006;
Babadagli, 2006; Babadagli et al., 2005; Gupta and Mohanty, 2007;
Standnes and Austad, 2000a, 2000b; Zhang and Austad, 2006). Almost
⁎ Corresponding author at: Department of Chemical Engineering, Amirkabir University
of Technology (Tehran Polytechnic), Tehran, Iran. Tel./fax: +98 21 88661308.
E-mail address: h_ghojavand@aut.ac.ir (H. Ghojavand).
all surfactants currently in use are originally derived from the petro-
leum. Therefore in spite of increasing oil prices in recent years, economy
of the surfactant injection is still critical (Babadagli, 2006; Babadagli et al.,
2005). During past few decades, many efforts have been done to in-
vestigate oil displacement by surfactant producing bacteria (Banat,
1995; Batista et al., 2006; Daoshan et al., 2004; Horowitz et al.,
1990; Joshi et al., 2008; Maudgalya et al., 2005; Yakimov et al.,
1995; Youssef et al., 2007). These efforts provided potential bacteria
and effective biosurfactants comparable to synthetic surfactants useful for
inexpensive and renewable resources (Makkar and Cameotra, 1997;
Nitschke and Pastore, 2006; Rodrigues et al., 2006) such as sugar cane
molasses with a cost lower than $ 0.5 per liter (Portilla-Rivera et al.,
2009). The economy of the commercial production of these materials is
affected by the downstream processing costs which are about 60% of
total production cost of many biological products (Mukherjee et al.,
2006). Thus, the required purity of the biosurfactants plays an important
role on economy of their commercial applications. Typically, costs of the
biosurfactants can be changed from $ 10 per mg for purified surfactin
(98% purity) in biomedical research to the $ 2–4 per kg in the emulsion
formulations for tank cleaning/oil recovery applications (Bognolo,
1999). Therefore, crude or impure biosurfactants which can be obtained
at the initial stages of recovery process can be used for environmental
and oil recovery applications in future. In addition, these applications
are eco-friendly, nontoxic and biodegradable. Therefore these materials
compared to synthetic and toxic chemicals that are dangerous to the oil
workers and environment can be led to cost saving on a long time.

0920-4105/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.petrol.2011.12.002
 H. Ghojavand et al. / Journal of Petroleum Science and Engineering 81 (2012) 24–30 25

The biosurfactants can be used alone (Maudgalya et al., 2005) or in Table 2

combination with synthetic surfactants for oil recovery applications Composition of the reservoir live crude oil.

(Daoshan et al., 2004). Reservoir oil (live oil)

In the present work, unlike other researches regarding to oil recov-
Composition Mole% Composition Mole%
ery from sandstone cores using biosurfactant injection (Daoshan et al.,
N2 0.307 C9 10.09
2004; Maudgalya et al., 2005), the dolomite cores were used and core
C1 8.582 C10 5.683
floods were also simulated to reservoir conditions with actual reservoir CO2 0.767 C11 2.961
fluids such as live crude oil and reservoir formation brine. Here, we have C2 0.814 C12 2.402
investigated efficiency of a biosurfactant produced by a Bacillus moja- H2S 0.88 C13 2.056
vensis strain (PTCC 1696) which we had isolated in previous works C3 0.781 C14 1.408
iC4 0.394 C15 1.058
(Ghojavand et al., 2008a, 2008b); for oil recovery from dolomite cores. nC4 1.545 C16 0.567
iC5 2.14 C17 0.394
2. Materials and methods nC5 2.998 C18 0.268
C6 7.795 C19 0.251
+
C7 10.36 C20 23.51
2.1. Core preparation
C8 11.99

We have obtained a type of carbonate rock from outcrop of Molecular weight = 152.79 g/g mole.

Masjed-I Soleyman (MIS) oil field at southwest of Iran. Chemical com-

position of the rock sample was analyzed by X-ray fluorescence spec-
trometer (Philips X’ Unique II). The presence of the 10% (w/w) MgO
and 40% (w/w) CaO in the rock composition showed that the pre-
pared rock was a dolomite rock. Core samples were prepared by cut-
ting rock samples into cylindrical specimens with 3.86 cm diameter.
The core samples were washed thoroughly with standard cleaning
procedure using toluene in the soxhlet device and dried in an oven
at 120 °C overnight (Babadagli, 2006). Each of the cores was encased
in Viton rubber sleeves and was placed inside stainless steel core-
holder. The core was then evacuated and flushed with brine. The ab-
solute permeability of the cores was determined by Darcy's law:
Q μL
K¼
A ΔP
where K [D]is the absolute permeability, Q [cm 3/s] is volumetric flow
rate, A [cm 2] is area of core cross section, μ [cp] is the viscosity, L [cm]
is core length and ΔP [atm] is the pressure drop of the fluid along the
length L. The absolute permeability of these cores varied from 0.19 to
0.57 mD. Properties of the cores that are used in this study are given
in Table 1.
2.2. Reservoir fluid properties
All experiments were carried out using crude oil and formation
brine which were taken from the MIS reservoir. Gas and dead oil sam-
ples were taken from well-head separator. Live crude oil was pre-
pared by recombining the gas and oil according to the gas–oil ratio
of the reservoir. The properties of the live crude oil used in this
study were gas–oil ratio of 17.6 Sm 3/Sm 3, formation volume factor
of 1.065 and oil gravity of 36 API. At reservoir temperature (42 °C),
viscosity of the live crude oil which was measured by Jefri High-
Pressure Fluid Viscometer (DB Robinson) was 1.80 and 1.91 cp at
3445 and 4134 kPa pressures respectively. Composition of the live
crude oil is listed in Table 2. The MIS formation brine which has
been used for irreducible water saturation was taken at depths of
433 to 526 m sub-sea of several oil wells in the MIS oil reservoir.
The composition of major ions in the reservoir brine is shown in
Table 3. The NaCl salinity of the brine is 240 (g/l). The brine has
total dissolved solid content (TDS) of 294 (g/l) and pH of 8.0.
2.3. Displacing fluid formulations
Oil production from very low permeability dolomite cores was in-
vestigated using various displacement fluids. Waterflooding was car-
ried out using sea water sample taken from the Persian Gulf. The sea
water analysis showed presence of following items: TDS of 45 (g/l),
NaCl salinity of 38 (g/l), and pH of 8.0. The composition of major ions
in this sea water sample is given in Table 3. Biosurfactant-mediated oil
recovery tests were either carried out using a mixture of the biosurfac-
ð2Þ
tant and co-surfactant or a mixture of the biosurfactant, co-surfactant
and a polymer. The biosurfactant produced by a Bacillus strain (PTCC
1696) was used in all experiments at concentration of ten times higher
than critical micelle concentration (CMC). Type and amount of the poly-
mer and co-surfactant which were used in all experiments of this study
were selected based on the Oklahoma MEOR group (Maudgalya et al.,
2005). Therefore, the co-surfactant of 2, 3-butanediol (Merck, Schu-
chardt, and 85662 Hohenbrunn, Germany) at concentration of 10 mM
and the polymer of partially hydrolyzed polyacrylamide (Qingdao
Great Chemical Inc., China) at concentration of 1000 ppm were used.
The addition of a low molecular weight alcohol (2, 3-butanediol) as
co-surfactant to the biosurfactant solution caused to alter the biosurfac-
tant behavior and raised the optimal salinity of the biosurfactant
(Lelanne-Cassou et al., 1993; Salter, 1978). In addition, co-surfactants
are employed in the oil displacing system to aid surfactants in solubiliz-
ing hydrocarbons, usually by stabilizing surfactant/hydrocarbon micro-
emulsions (Knickerbocker et al., 1979; Martel et al., 1993). The polymer
of partially hydrolyzed polyacrylamide was added to the biosurfactant
solution as a mobility control agent to prevent dissipation of the oil
bank before it reached the effluent end.
Table 3
Composition of the formation brine taken from the MIS oil reservoir and sea water
sample taken from the Persian Gulf used in this study.
Formation brine Sea water

Major components Concentration (g/l) Major components Concentration (g/l)

Na+ 101.625 Na+ 14.96

K+ 0.75
Table 1 Ca+ 2 6.56 Ca+ 2 0.5
Properties of the carbonate (dolomite) cores used in this study. Mg+ 2 2.6112 Mg+ 2 1.3
Cl− 163 Cl− 23.1
Core name D (cm) L (cm) K (mD) φ (%)
SO4− 2 18.21 SO4− 2 –
MIS-4-1 3.86 6.81 0.22 12.51 CO3− 2 0.008 CO3− 2 0.03
MIS-4-3 3.86 7.55 0.41 12.67 HCO3− 0.129 HCO3− 0.1
MIS-4-4 3.82 7.46 0.57 12.12 Total nitrogen 0.013
26 H. Ghojavand et al. / Journal of Petroleum Science and Engineering 81 (2012) 24–30
2.4. Microbial surfactant preparation
2.4.1. Microorganism
The bacterium used in this study was obtained from an isolation,
screening and selection program of biosurfactant producing bacteria
from the Masjed-I Soleyman oil field in the southwest of Iran
(Ghojavand et al., 2008a). Following a request from Deutsche Samm-
lung von Mikroorganismen und Zellkulturen (DSMZ) GmbH, the isolate
was subsequently identified as a B. mojavensis strain and registered
with the Persian Type Culture Collection as PTCC 1696.
2.4.2. Biosurfactant preparation
The biosurfactant producing Bacillus strain (PTCC 1696) was
streaked in a nutrient agar slant and incubated for 24 h at 40 °C. Two
loops of the culture were inoculated in 200 ml of medium E (Folmsbee
et al., 2006) in a 500 ml Erlenmeyer flask and incubated in a rotary shak-
er at 40 °C and 150 rpm overnight. The composition of medium E was
consisted of (g/l): 10 glucose, 50 NaCl, 1 (NH4)2SO4, 0.25 MgSO4, 13.9
K2HPO4, 2.7 KH2PO4, 1 NaNO3, 0.5 yeast extract and 10 ml trace salt so-
lution. Trace salt solution had the following composition (g/l): 1 EDTA, 3
MnSO4.H2O, 0.1 FeSO4.7H2O, 0.1 CaCl2.2H2O, 0.1 CoCl2.6H2O, 0.1
ZnSO4.7H2O, 0.01 CuSO4.5H2O, 0.01 AlK(SO4)2.12H2O, 0.01 H3BO3, 0.01
Na2MoO4.2H2O. An aliquot of the inoculum (5% v/v) was added to the
5 lit Erlenmeyer flasks containing 1500 ml of medium E. The flasks
were incubated on a rotary shaker incubator (120 rpm) at 40 °C for
36 h. The growth curve and surface tension trend of the culture medium
during growth of the microorganism were obtained by taking samples of
the fermentation after different time intervals. The optical density of the
samples was periodically measured at 600 nm with a spectrophotome-
ter. The bacterial cells of the samples were separated by centrifugation
(10,000 ×g at 4 °C for 10 min) and surface tensions of supernatant of
the samples were determined. At the end of fermentation, the
surfactant-containing medium was used for core flooding studies.
2.5. Surface and interfacial tension determination
Digital tensiometer (model K10ST, Krüss, Germany) was used for
measuring the surface and interfacial tension. The effectiveness of
the biosurfactant produced by strain PTCC 1696 was determined by
measuring the surface and interfacial tension of the samples at
25 °C with De Nouy ring detachment method. The interfacial tension
was measured against 15 ml overlay of n-hexadecane. The interfacial
tensions between MIS crude oil and biosurfactant solutions were
measured at MIS reservoir temperature (42 °C). Measurements of
the surface and interfacial tensions were made in triplicates and an
average number is reported in this study.
2.6. Biosurfactant concentration determination
Relative concentration of the biosurfactant in cell free culture broth
was determined by measuring the surface and interfacial tension of the
serial dilutions of the broth until the CMC was attained. The serial dilu-
tions were made by diluting of the cell free culture broth with medium
E in order to maintain chemical composition of the serial dilutions sim-
ilar to the original culture. The dilution necessary to reach the CMC that
was known as critical micelle dilution (CMD) was proportional to the
amount of biosurfactant present in the original sample (Batista et al.,
2006; Nitschke and Pastore, 2006). The amounts of the biosurfactant
in cell free broth which were used for core flooding studies were
expressed as CMC.
2.7. Experimental set-up
A schematic of the experimental equipment is given in Fig. 1. Fluid
vessels and core holder assembly were placed inside the incubator at
MIS temperature of 42 °C. The core holder unit consists of a horizontally
mounted high pressure stainless steel core holder and Viton rubber
sleeve which is used to house the core inside the core holder. The differ-
ential pressure between the input and the output of the core holder was
recorded by two transducers (WIKA model, 6 × 104 kPa). Since the
crude oil used in core flooding studies was live oil containing dissolved
gas, the back pressure was applied to maintain the crude oil at one
phase. The back pressure was set at values higher than bubble point
pressure of the crude oil (3344 kPa).
2.8. Core flooding studies
Evaluation of the biosurfactant-mediated oil recovery from very low
permeability dolomite cores was performed using core flooding experi-
ments. The core flooding studies were conducted at MIS reservoir condi-
tions. Experiments designed in this study were based on two major
strategies. In the first strategy, the mixture of biosurfactant/co-surfactant
or the mixture of biosurfactant/co-surfactant/polymer was flooded after
water flooding as tertiary flooding processes. In the second strategy,
these mixtures were injected into the cores to study the secondary re-
covery effectiveness instead of water flooding. Experimental tests were
performed by first placing the cleaned and dried core samples inside
the core holder. Each core was primarily evacuated and then 5512 kPa
of overburden pressure was applied. The core was flushed with forma-
tion brine and Darcy's law was used to determine absolute permeability
of the core. Then, live crude oil was injected into the core until no addi-
tional water was produced. Now, the core reached to the point of irre-
ducible water saturation (Swi). The average value of the Swi in the cores
used in this study was about 12.5%. The oil saturated core was either
flooded by sea water (Sow) followed by biosurfactant solutions (Sosw)
or subjected to the biosurfactant flooding directly (Sos). The flooding of
each treatment was continued until no more oil was observed in the ef-
fluent. The effluent was divided into a gas and liquid in the separator.
Then the gas goes to a gas meter and the liquid is collected in a graduated
cylinder for analysis and separation of the oil and water during each frac-
tion. The 15 ml graduated cylinders were used to measure produced liq-
uid. The volumes of the gas-free oil (stock tank oil) were measured and
then corresponding residual oil saturations into the core were deter-
mined based on the formation volume factor by the following equation:
ðIOIP−Vo Þ  Bo
 100 ð3Þ
PV
where IOIP [cm3] is initial oil in place, Vo [cm3] is the cumulative stock
tank oil production, Bo is the formation volume factor and PV [cm3] is
the pore volume.
The oil recoveries for each treatment were calculated as follows:
ð100−Swi −Sow Þ
Erw ¼  100 ð4Þ
100−Swi
ðSow −Sosw Þ
Ersw ¼  100 ð5Þ
Sow
ð100−Swi −Sos Þ
Ers ¼  100 ð6Þ
100−Swi
where Erw, Ersw and Ers [%] are oil recovery after water flooding, oil re-
covery obtained by injection of surfactant solutions after water flooding,
and oil recovery after injection of surfactant solutions, respectively. In
all experiments, the fluids were injected at rate of 20 ml/h.
3. Results
3.1. Properties of the biosurfactant solution used for core flooding studies
A typical fermentation profile of strain PTCC 1696 grown under
aerobic conditions is illustrated in Fig. 2. A maximum bacterial
 H. Ghojavand et al. / Journal of Petroleum Science and Engineering 81 (2012) 24–30
Fig. 1. Schematic of the experimental apparatus used for core flooding studies.
concentration (Amax of 3%) was obtained after 33 h and the lowest
surface tension of the broth (26.7 mN/m) was attained after 12 h.
Based on the previous works, the biosurfactant produced by PTCC
1696 was a lipopeptide (Ghojavand et al., 2008a) which was stable
at extreme conditions i.e., temperature, pH and salinity (Ghojavand
et al., 2008b). In addition, the critical micelle concentration of the bio-
surfactant was CMC 10 μg/ml (Ghojavand et al., 2008b). At the end of
fermentation in the current work, 0.1 g/l crude biosurfactant was
obtained. As shown in Fig. 3, this biosurfactant has the ability of low-
ering interfacial tension against n-hexadecane to 0.1 mN/m. This bio-
surfactant was also able to reduce interfacial tension between MIS
crude oil and sea water by two orders of magnitude. The critical mi-
celle dilution (CMD) of a cell free culture broth of strain PTCC 1696
Fig. 2. Growth curve of strain GMTB-C1-2 and surface tension reduction of culture me-
dium during aerobically growth on medium E at 42 °C.
27
cultured on medium E after 72 h (rotating at 120 rpm and 40 °C)
was ten times above the CMC (Fig. 3). The biosurfactant concentra-
tions that correspond to the CMD values are also shown in Fig. 3. In
the entire core flooding studies, the cell free broth containing biosur-
factant at concentration ten times the CMC, in addition to 10 mM 2, 3-
butanediol was used. In some experiments, 1000 ppm of PHPA was
added to the mixture as mobility control agent. This caused to in-
crease viscosity of the mixture to 1.9 cp.
3.2. Evaluation of the biosurfactant-mediated recovery from dolomite
rocks
In order to evaluate the potential of the biosurfactant produced by
Bacillus strains for oil recovery from dolomite cores, several tests
were conducted. As described in material and methods section, the
biosurfactant mixtures were used in this work to displace oil from
the cores in both of the secondary and tertiary flooding processes.
The results of these two strategies were separately described in detail
in the following sections.
3.2.1. Tertiary oil recovery using bio-surfactant solution (conventional
method)
The enhanced oil recovery experiment using biosurfactant/co-
surfactant solution was conducted at rate of 20 ml/h. The oil production
is shown in Fig. 4. As seen in this figure, after 37% PV water flooding into
the core MIS-4-1, the breakthrough occurred. At this time, the residual
oil saturation (Sor) was reduced to 63%. Water flooding resulted in re-
covery of 31.56% of initial oil in place (IOIP) and the oil saturation was
reduced to 58%. The oil recovery in this stage was due to the volumetric
sweep efficiency that occurred by water injection. However, injection of
water was continued until no more effluent oil was observed. Then, at
first a slug of the biosurfactant/co-surfactant (50% PV) was injected
28 H. Ghojavand et al. / Journal of Petroleum Science and Engineering 81 (2012) 24–30

Fig. 5. Comparison of the oil recovery from dolomite cores using biosurfactant/2,
3-butanediol and biosurfactant/2, 3-butanediol/PHPA floodings at injection rate of
20 ml/h.
Fig. 3. Surface activity properties of the cell free broth produced by strain PTCC 1696
under batch condition after 72 h (shake flask fermentation using medium E at 42 °C
free broth that is obtained by PTCC 1696 cultured on medium E after
and 120 rpm): surface and interfacial tension, critical micelle dilution.
72 h (rotating at 120 rpm and 40 °C), beside a sea water droplet that
was placed on MIS oil-coated core surface. The droplet containing bio-
surfactant was instantaneously collapsed and spread completely over
the surface, whereas around the water droplet, water/oil interfaces, on
the surface of the rock remained stable. This reduction of the interfacial
tension was similarly resulted in displacement of the oil by mobile
phase through the porous medium.

3.2.2. Secondary oil recovery using biosurfactant solutions (dilute

surfactant method)
In order to evaluate the dilute microbial surfactant methods for
oil recovery from carbonate formations, the biosurfactant-mediated
recovery was studied at secondary stage. Fig. 6 shows the oil produc-
tion by injection of biosurfactant/co-surfactant and biosurfactant/

60
Recovery (% IOIP)

Fig. 4. Production of the remaining oil after water flooding using biosurfactant/2,
3-butanediol at rate of 20 ml/h. 40

right after water flooding step. Addition of the microbial surfactant to

20
the water caused to decrease of the interfacial tension and therefore
the microscopic displacement of the residual oil was occurred. Thereaf-
ter, the water flooding again was started and the color of the effluent
was increasingly changed. But the measurable oil at the effluent was 0
negligible until injection of 70% PV water. Tertiary oil recovery after per- 0 0.5 1 1.5 2
forming this injection strategy was about 6% of IOIP. The ultimate oil re- Injection volume (PV)
covery which was provided by injection of 410% PV displacement fluids Biosurf./Cosurf. Biosurf./Cosurf./PHPA
at this experiment was 37.46% of the IOIP. The mechanism of the resid-
Fig. 6. Comparison of the oil recovery from dolomite cores using biosurfactant/2,
ual oil displacement by reducing interfacial tension through microbial 3-butanediol and biosurfactant/2, 3-butanediol/PHPA floodings at injection rate of
surfactant is shown in Fig. 5. This figure shows a droplet of the cell 20 ml/h.
 H. Ghojavand et al. / Journal of Petroleum Science and Engineering 81 (2012) 24–30
co-surfactant/PHPA; at the rate of 20 ml/h. As shown in this figure,
flooding of the biosurfactant/co-surfactant and biosurfactant/co-
surfactant/polymer resulted in 51% and 60% recovery of the IOIP re-
spectively. The residual oil saturations after injection of these mixtures
were reduced to 44.5% and 25% respectively. The breakthrough time for
injection of the biosurfactant/co-surfactant flood was observed after in-
jection of about 40% PV. This period of time was increased by adding
mobility control agent (PHPA). The breakthrough of the injected solu-
tion of biosurfactant/co-surfactant/PHPA was occurred after 84% PV
and therefore oil recovery was increased up to 60% of the IOIP.
4. Discussion
In this study, a B. mojavensis strain (PTCC 1696) which was isolated
in previous work (Ghojavand et al., 2008a) was used to produce mi-
crobial surfactant. The potential of this bio-surfactant for oil recovery
from carbonate reservoirs by surfactant/polymer flooding method
was evaluated. The surfactant/polymer flooding is a popular technique
for EOR. In this process, the polymer provides mobility control during
injection and therefore improved macroscopic sweep efficiency. On
the other hand, surfactants reduce the interfacial tension between
oil and water where surfactant solution contacts the small pockets of
the trapped oil and therefore mobilizes this trapped oil. In other
words, these latter materials were used to improve microscopic dis-
placement efficiency. In addition, in other mechanism of the enhanced
oil recovery, some of these surface active agents can be used to alter
wettability of the carbonate reservoirs. Some researches with these
surfactants for oil recovery from carbonates by spontaneous imbibi-
tion or forced imbibition have been carried out in recent years
(Austad et al., 1998; Ayirala et al., 2006; Babadagli, 2006; Babadagli
et al., 2005; Gupta and Mohanty, 2007; Standnes and Austad, 2000a,
2000b; Zhang and Austad, 2006). The use of the synthetic surfactants
in laboratory studies led to a very high efficiency of microscopic oil
displacement (Van Poolen and Associates, 1980), but economic issues
and other concerns such as environmental problems have prevented
their extensive use in EOR in the field scales. Most of the synthetic sur-
factants that were used in conventional EOR methods and other appli-
cations are petroleum based and chemically synthesized. These types
of surfactants are toxic and therefore can be caused to ecological and
environmental damages. Thus, EOR researchers are looking for cost ef-
fective materials with high productivity and environmentally safe and
nontoxic. In this regard, the biotechnology products are important be-
cause they possess advantages over the synthetic surfactants, such as
lower toxicity, biodegradability and effectiveness at a wide range of
pH and temperature values (Banat et al., 2010; Makkar et al., 2011).
These materials can be economically produced by fermentation of
the industrial wastes and waste waters.
Some of the factors that have been reported to affect the surfactant
mediated EOR are IFT value, surfactant concentration to yield an effec-
tive (higher recovery) and cost efficient process, stability at tempera-
ture and salinity (Babadagli et al., 2005). In the previous work
(Ghojavand et al., 2008b), we have investigated stability of the microbi-
al surfactant produced by B. mojavensis strain PTCC 1696 at extreme
conditions i.e., temperature, pH and salinity. On the other hand, we
have shown that in current work this bio-surfactant, lipopeptidic in na-
ture (Ghojavand et al., 2008a), has potential for oil recovery from dolo-
mite cores by forced imbibition.
The IFT measurements showed that this microbial surfactant was
able to reduce interfacial tension two orders of magnitude.
By experiments related to surfactant flooding (non-ionic, cationic
and anionic) through chalky core samples taken from Shuaiba forma-
tion, Yibal field, Oman; Babadagli et al. (2005) reported that IFT re-
duction is more important issue in the tertiary recovery process
than secondary application of surfactant solution. This finding isn't
consistent with our results for biosurfactant mediated oil recovery
from dolomite cores. We observed that the addition of the microbial
29
surfactant to the water injection at very low concentration (0.1 g/l
crude biosurfactant) can increase oil recovery at secondary stage to
higher than one half of the IOIP. Therefore, the dilute surfactant meth-
od, as a secondary oil recovery process can be considered in the oil re-
covery from carbonate reservoirs.
The importance of the surfactant imbibition processes in the oil
recovery from oil-wet reservoirs has been also demonstrated by
Austad et al. (1998), Adibhatla and Mohanty (2008) and Gupta and
Mohanty (2007). These researchers suggested that more than 60%
of the original oil can be produced by dilute surfactant imbibition.
The economy of these processes, however, is critical due to the high
cost of the surfactants (Babadagli, 2006). We believed that the econ-
omy of these processes can be improved when these materials are
substituted by the effective microbial surfactants. Some of these bio-
surfactants are able to reduce surface and interfacial tension two to
three order of magnitude and are effective at very low concentrations
(Folmsbee et al., 2006; Youssef et al., 2007). Therefore, these can be
used for oil recovery from carbonate reservoirs by biosurfactant-
assisted weterflooding process.
Many researchers studied the effect of the wettability on oil recovery
form fractured, oil-wet reservoir (Gupta and Mohanty, 2007; Standnes
and Austad, 2003; Zhang et al., 2006). The oil recovery in this reservoir
by surfactant process is different with the conventional chemical flood.
They found that the wettability alteration would be critical for these res-
ervoirs. In the current work, we haven't concentrated on the wettability
alteration by the microbial surfactants but we have done preliminary ex-
periments by contact angle measurements on both of the clean and trea-
ted cores. The cores which were used for biosurfactant flooding studies at
the previous stages were known as treated cores in contact angle tests.
We studied wettability alteration by placing a droplet of water on surface
of the cores. Typically, Fig. 7 shows the fate of a droplet of water on the
surfaces of the clean and treated cores. A water droplet forms a contact
angle of about 72° on surface of the core prior to treatment by microbial
surfactant (Fig. 7a). On the other hand, the droplet of water made a con-
tact angle about 45° on surface of the treated core (Fig. 7b). The later was
indicating wettability altering ability of the microbial surfactant that was
produced in this work. However, this wettability altering potential should
be tested by other well known tests such as USBM and Amott-Harvey and
etc. which are under studies in the future works by the authors.
By focusing on the subject of statistical data analysis and consider-
ing the heterogeneous nature of the test core, researches are needed
to provide precise conclusion to these accurate results.
In this work, we present a microbial surfactant with potential ability
to use in enhanced oil recovery. The interest in these group of surfactants
has been significantly increased recently, particularly because of sustain-
ability from renewable sources and their physicochemical properties
such as lower toxicity, biodegradability and effectiveness at a wide
range of pH and temperature values. In spite of these important factors,
their large scale production to make these types of materials applicable
to the fields is currently restricted by the high cost of production. Accord-
ing to Makkar et al. (2011), these problems can be improved by: (i) de-
velopment of the culture media based on the cheap or waste substrates
for each appropriate organism to lower the initial raw material costs in-
volved in the process, (ii) development of efficient bioprocesses and (iii)
development and use of overproducing mutant or recombinant strains
for enhanced yields.
In recent years, some researches were focused on these subjects
(Das et al., 2008; Makkar et al., 2011; Mukherjee et al., 2006).
Related to our microbial surfactant, more studies are needed on
these items for efficient production of biosurfactants to make this
product applicable to the fields.
5. Conclusions
The results of the work showed that the microbial surfactants have
potential for enhanced oil recovery applications and can be eco-friendly
30 H. Ghojavand et al. / Journal of Petroleum Science and Engineering 81 (2012) 24–30
Fig. 7. Liquid droplets on the surface of the dolomite cores; (a) cleaned core, (b) treated core by microbial surfactant.
used as good substitutes for synthetic surfactants in the future. Based on
the findings, secondary diluted microbial surfactant-mediated oil recov-
ery can be considered as a technique for oil displacement through the car-
bonate oil reservoirs. The core flooding studies showed the lipopeptide
biosurfactant produced by B. mojavensis (PTCC 1696) which was able to
reduce surface tension as low as 26.7 mN/m at low concentrations, can
be employed in these reservoirs even in the presence of high salinity
(240 (g/l) NaCl salinity). Of course, it would be necessary to make more
assessments using core flooding tests by fractured cores which are char-
acteristic of most of the carbonate reservoirs. In addition, adsorption of
this surfactant on the rock surface which was not investigated in this
study also needs to be analysis.
Acknowledgments
The authors thank the Petroleum Engineering & Development
Company (PEDEC) for the financial supports.
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