Environmental Science and Pollution Research (2022) 29:44255–44270

https://doi.org/10.1007/s11356-022-19009-0

RESEARCH ARTICLE

Application of α‑MnO2 nanoparticles for residual oil mobilization

through surfactant polymer flooding
Himanshu Kesarwani1 · Vartika Srivastava2 · Ajay Mandal3 · Shivanjali Sharma1   · Abhay Kumar Choubey2

Received: 10 October 2021 / Accepted: 28 January 2022 / Published online: 7 February 2022
© The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature 2022

Abstract
Injection of surfactant and polymer slug is among the most effective chemical enhanced oil recovery processes. The only
problem encountered with the surfactant polymer (SP) flooding is the loss of surface-active agents that reduce the efficiency
of surfactants in the chemical slug. Various attempts to modify SP flooding have been made previously so that the surfactant
loss due to adsorption could be reduced. Nanoparticles (NPs) are one of the most effective ways of reducing surfactant
adsorption as surfactant particles are held in the liquid phase by nanoparticles, resulting in lower surfactant losses due to
adsorption. However, the high cost of the NPs limits their use on the field scale. To encounter this problem, the present study
focuses on the application of the manganese dioxide NPs, synthesized through a green route that is economically viable.
These NPs are found to be cost-effective as compared to commercially available NPs as well as the synthesis of these NPs
does not require the use of toxic chemicals. The 1000 ppm NPs effectively reduced the surfactant adsorption by 46%. The
surface tension was lowered from 29.4 to 26.1 mN/m when 1000 ppm NPs were applied to 2500 ppm surfactant solution.
Also, the nanoparticles were found to increase the viscosity of the chemical slug by increasing the solid particles present in
the slug. The sand pack flooding experiments were carried out to assess the crude oil mobilization ability of the NPs assisted
SP flooding. The oil recovery was found to increase from 5% of the original oil in place, resulting in ~ 75% of the crude oil
recovery, which was only ~ 70% when NPs were not introduced into the system.

Keywords  Adsorption · Nanoparticles · Enhanced oil recovery (EOR) · Polymer · Surfactant

Introduction injection (Ahmadi 2018). To retrieve the residual oil in

place, SP flooding uses the processes of lowering interfacial
Surfactant polymer (SP) flooding is among the finest tertiary tension (IFT) and wettability modification, as well as con-
recovery techniques which requires surfactant and polymer trolling the mobility ratio (Mandal et al. 2016; Gbadamosi
to be injected in the reservoir followed by the chase water et al. 2019a). The optimum composition of the chemical
slug, which alters the rock fluid properties to the desired
values, is very much important from both the scientific and
Responsible Editor: Angeles Blanco economic points of view. The IFT between the injection
fluid and displaced fluid is decreased when the surfactant is
* Ajay Mandal applied (Druetta et al. 2019). It has been found that surface-
ajay@iitism.ac.in
active agents can minimize IFT up to < 0.01 mN/m (Rosen
* Shivanjali Sharma et al. 2005). The reduction of IFT causes a decrease in the
ssharma@rgipt.ac.in
capillary pressure as well as an increase in the capillary
1
Department of Petroleum Engineering and Geo Engineering, number (Nca) (Gregersen et al. 2013). Reduction in capil-
Rajiv Gandhi Institute of Petroleum Technology, lary forces makes it simpler for the injection fluid to displace
Jais 229304, India crude oil from the smaller capillaries. Apart from lowering
2
Department of Basic Science and Humanities, Rajiv Gandhi the capillary pressure, a reduction in IFT could lead to the
Institute of Petroleum Technology, Jais 229304, India formation of the microemulsion among injection fluid and
3
Enhanced Oil Recovery Laboratory, Department crude oil. Thus, oil production becomes the movement of a
of Petroleum Engineering, Indian Institute of Technology single fluid (oil/water emulsion), which is relatively easier.
(ISM), Dhanbad 826004, India

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44256 Environmental Science and Pollution Research (2022) 29:44255–44270

Surface-active agents often interfere with wettability or NPs for the adsorption reduction of the anionic surfactant
the fluid's ability to bind to rock surfaces (Karnanda et al. and have successfully reduced the adsorption of surfactant
2013). The persistent oil film present on rock surfaces is dis- from 28 to 16% (Venancio et al. 2020). Saxena et al. have
rupted as the wettability of the rock is changed to water-wet. used the alumina and silica NPs for the adsorption reduction
This leads to the formation of a bigger and mobile oil drop- of the synthesized soap nut oil surfactant and reported posi-
lets that are easier to displace from the pore spaces by injec- tive effects of the NPs on the surfactant adsorption reduction
tion fluid and thereby recovering more oil from the reservoir on different mineralogical surfaces (Saxena et al. 2019a).
(Gbadamosi et al. 2019a). The wettability can be categorized Silica NPs have been used to minimize the surfactant loss
by the contact angle of the fluid that it makes with the solid on rock surfaces (Wu et al. 2017). An additional oil recov-
surface. A shift in the wettability to water-wet enhances the ery of 4.68% was reported when NPs were combined with
microscopic displacement efficacy (Pal et al. 2018). the surfactant solution. Apart from aiding in the reduction
Polymer mixing with the chemical slug improves the vis- of surfactant adsorption, NPs have also been used for their
cosity of displacing fluid which decreases the viscous fin- ability to reduce the IFT. Yekeen et al. used several NPs and
gering of the more mobile fluid (Kumar and Mandal 2017). looked at how NPs influenced the IFT reduction between
The addition of polymer to the chemical slug increases the the surfactant + NP solution and n-decane solution (Yekeen
viscosity of water (chemical slug), lowering the injection et al. 2019). They have obtained promising results for the
fluid’s mobility and resulting in a desirable mobility ratio application of NPs in the oil industry as an additive for IFT
value (Kurnia et al. 2020). Desirable mobility ratio helps in reduction.
displacing the crude oil from the pore spaces by providing It can be concluded from the previous work that the NPs
better macroscopic efficiency. can be used in the oil industry for the performance improve-
Even the addition of surfactant and polymer does not ment of surfactant flooding. However, the primary concern
make this technique perfect. The problem of loss of sur- that arises with the application of NPs on such a large scale
factant still remains a major disadvantage. Adsorption is a is its cost-effectiveness. Due to their high price, their appli-
surface phenomenon in which a surfactant molecule gets cation to the field scale is minimal. To address this prob-
attached to the rock surfaces. The surfactant's adsorption lem, the current research focuses on the use of NPs with the
decreases its activity, and more surfactant would be required surfactant, which is synthesized using a green path. Ficus
to achieve the same result (ShamsiJazeyi et al. 2014). Hence, retusa leaf extract was used to develop manganese dioxide
it is suggested to reduce the adsorption of the surfactant as NPs. The advantage of using F. retusa for the synthesis is
much as possible. The application of nanoparticles (NPs) to that F. retusa is a non-seasonal plant and is therefore avail-
encounter this problem up to some extent is not new (Gbada- able throughout the year. Besides being readily available at
mosi et al. 2019b). NPs have been used by the researcher in all times, the plant does not require much attention or cost
the past to overcome the adsorption losses of the surfactant to grow and flourish and propagation rate is also high. These
on the rock surfaces (Ahmadi and Shadizadeh 2012, 2013; features assist the easy availability of the raw material (i.e.,
Zargartalebi et al. 2014; Saxena et al. 2019a). Due to their plant leaves) for the synthesis of nanoparticles.
small sizes, the NPs tend to have a greater surface area and Nanoparticles synthesized through green route are far
possess high surface charge density (Beg et al. 2019, 2022). superior in physical and chemical properties as compared
The addition of even a small quantity of NP has a favorable to that of the one synthesized through other chemical meth-
impact upon reduction of loss of surfactant. ods involving complex chemical reaction etc. Furthermore,
A lot of researchers have used the NPs along with the green synthesis process does not involve the use of toxic
surfactant to reduce the loss of surfactant (Kesarwani et al. chemicals for the fabrication of nanomaterials and does not
2022). Rezk and co-workers have used the zinc oxide NPs produce other by-product impurities which are produced
(~ 50 nm) as an additive with a surfactant to minimize the unwantedly during the chemical reaction process. Further-
IFT among the crude oil and NPs dispersed in surfactant more, it is neither energy consuming and massive frame-up
solution (Rezk and Allam 2019a). They have reported a sig- including elaborated instrumentation, reactors etc. nor does
nificant reduction of 25 mN/m in the IFT value and almost it involve the use of costly materials. The simple setup of the
8% additional oil recovery when zinc oxide NPs were used experimentation makes this method economically beneficial.
instead of surfactant only. In another research, iron oxide Not only is the synthesis of these NPs cost-effective, but
had been used for the asphaltene precipitation for the carbon it is also environmentally friendly. However, physical and
dioxide injection (Kazemzadeh et al. 2015). Ehtesabi et al. chemical methods can also be used for the synthesis of these
have used the titanium oxide NPs for the additional crude oil NPs (Nugroho and Kim 2014; Liu et al. 2016), but there
recovery (Ehtesabi et al. 2015). With just 0.01 wt.% of NPs are several disadvantages associated with these methods,
dispersed in slug for core flooding, an additional oil recovery such as the use of toxic and corrosive chemicals as reduc-
of 14% was recorded. Venancio et al. have used the silica ing and stabilizing agent (Pugazhvadivu et al. 2013), severe

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Environmental Science and Pollution Research (2022) 29:44255–44270 44257

reaction conditions, and use of organic solvents which has Synthesis of manganese dioxide NPs
an adverse effect on health on prolonged exposure. There-
fore, it is beneficial to fabricate these nanomaterials using Manganese oxide possesses characteristic physical and
natural resources. chemical properties. These properties have been exten-
The present study focuses on the application of manga- sively explored and utilized by researchers over the past
nese dioxide NPs in crude oil mobilization. Now, Manganese few years (Xu et al. 2004; Wang et al. 2017; Dawadi et al.
(Mn) exists in nature in various oxidation states and forms 2020). For the synthesis, approximately 50  g of prop-
oxides such as MnO, M ­ nO2, and complex compounds like erly crushed leaves of F. retusa was boiled with deion-
­Mn2O3, ­Mn3O4, and M ­ n5O9. Out of all these compounds, ized water. The aqueous extract obtained was decanted
­MnO2 is of vital importance because of its multi-function- and filtered using a 0.2-µm membrane filter. Aqueous
ality. The phase and polymorphism of ­MnO2 is regulated extract (100 mL) of leaves was steadily poured in 200 mL
by several factors such as concentration of reactant, reac- of 0.1 M potassium permanganate solution. The solution
tion time, pH, and temperature. Nowadays, M ­ nO2 is being was thickened to black paste and subsequently exposed to
utilized in several fields such as catalysis, energy storage, 800 °C for 2 h. The α-MnO2 powder was then scratched
electrochemical reactions, and water treatment process off and used for further experiments. The schematic for
(Andreozzi et al. 1996; Luo et al. 2006; Fei et al. 2008; the process of synthesis of the NP is depicted in Fig. 1.
Jaganyi et al. 2013; Bing et al. 2017). Our previous studies
have reported the synthesis and characterization of the NPs
used for the present study (Srivastava and Choubey 2021). Surface tension measurement
The current work is focused on the effect of the α-MnO2
nanoparticle’s concentration on the critical micelle concen- Kyowa DY-500 was used to obtain the surface tension
tration (CMC) of the surface-active agent. The surfactant of various samples using a Wilhelmy plate. The experi-
loss was examined as a function of NP concentration. Con- ments were performed at 30 °C at ambient pressure condi-
tact angle on different rock surfaces and IFT with crude oil tions. In the petri dish used for the experiment, the sample
was measured to investigate the NP’s impact on wettability (~ 15 mL) was carefully poured. A standard platinum plate
and IFT stabilization. The viscosity of the solution contain- was carefully hanged on the hook attached with the torsion
ing surfactant at CMC, 1000 ppm polymer, and the NPs of balance. The plate was moved upward automatically until
varying concentration was investigated. Finally, the chemi- it partially submerges into the solution. The surface ten-
cal slug’s oil mobilization potential composed of different sion of the solution is determined using the force used to
concentrations of the NPs was studied. pull the plate from the liquid/air interface. The equipment
has a precision of 0.01 mN/m, and the tests were repeated
three times to reduce the error and ensure repeatability.
The surface tension of NPs at various concentrations (100,
Experimental section 500, and 1000 ppm) mixed with a surfactant solution was
measured. The impact on surface tension as a function of
Materials temperature, surfactant, and NP concentration was studied.

SD-Fine Chemicals Pvt Ltd provided potassium perman-

ganate ­(KMnO4) with a molecular weight of 158.034 g/ Adsorption of surfactant
mol and purity of > 99.5%. Sodium dodecyl sulfate (SDS)
of molecular weight 288.372 g/mol and purity > 99% was Conductivity experiments were carried out to investigate
obtained from Rankem Chemicals. SNF (Floerger, France) the amount of surfactant loss on surfaces of rock. A refer-
provided the industrial-grade polyacrylamide (PAM) poly- ence plot of conductivity to surfactant concentration was
mer used in the experiment. Toluene, purity 99% which was drawn. Afterward, 1 g of 40–60 mesh sand particles was
used as a solvent, was acquired from Molychem Pvt Ltd. mixed with a surfactant solution. For all measurements,
Crude oil with a viscosity of 2.43 mPa.s at 60 °C after degas- the amount of sand particles mixed with the fixed sur-
sing and a total acid value of 1.02 mg KOH/g was obtained factant volume was kept constant. After a time span of
from Ankaleshwar Field ONGC Ltd, India. Deionized water 24 h, the sand particles were centrifuged using the Thermo
used for the sample preparation of conductivity 0.055 µS/cm Scientific centrifuge for 30 min at 4500 rpm. The sur-
at 30 °C was collected from the Elga Lab water purifier. All factant solution’s conductivity was measured again, and
other chemicals used for the experiment were of analytical the previously drawn standard curve was used to obtain
grade and were procured from SD-Fine Chemicals Pvt Ltd, the corresponding value of the surfactant concentration
India. present in the solution. The amount of surfactant loss on

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44258 Environmental Science and Pollution Research (2022) 29:44255–44270

Fig. 1  Schematic of the synthe-

sis of the ­MnO2 nanoparticles

the sand surface was calculated using Eq. (1) (Ahmadi and pump, which was flowed inside the tubing by maintaining
Shadizadeh 2013). a constant flow rate of 0.001 mL/min. As the liquid comes
NP concentration in the surfactant solution was varied into contact with the solid sand pellet surface, it forms a
(100, 500, and 1000 ppm) to examine NP’s influence on the shape of a sessile drop (Gupta et al. 2021). The image
loss of surfactant on sand particles. A distinct reference plot of the drop was captured using the camera and analyzed
for the conductivity as a function of the surfactant concen- with the ImageJ software. Contact angles were examined
tration was used for a different solution later to obtain the as a function of surfactant concentration, NP concentra-
difference in the concentration of surfactant remaining in tion, contact surface, and time. All the measurements were
the solution. repeated thrice to verify the repeatability of the findings.
Similarly, the surface at which the surfactant particles The complete experiment was performed at 30 °C tem-
were adsorbed was changed to investigate mineralogy’s role perature and ambient pressure conditions.
on surfactant adsorption. Sandstone, dolomite, and benton-
ite particles were used to understand the effect of different
minerals on adsorption. The sand particles and dolomite of Rheology of the chemical slug
the same size (40–60 mesh) whereas bentonite particles in
amorphous form were used. The impact of time and tem- Viscometry of slug (surfactant and polymer) was stud-
perature was also investigated on the surfactant adsorption. ied using the Anton Paar compact rheometer (MCR-52).
A double gap pressure assembly (DG35.12) was used for
Wsol
[ ]/
A = (Ci − Cf ) ∗ 1000 (1) the viscometry analysis. Shear rate was varied from 1 to
Wsand
5000 ­s−1 to analyze its effect on the viscosity of the slug
where Ci and Cf are surfactant concentration initially and (Hashmet et al. 2014). The NP’s impact on the viscosity
finally (ppm); Wsol is mass of solution (g); Wsand is sand par- was studied by varying the NP concentration (100, 500,
ticle’s mass (g); A is surfactant loss on rock surface (mg/g). and 1000 ppm). The impact of heat on the viscosity was
also explored. To analyze the viscosity, a sample (~ 5 mL)
Contact angle measurement was carefully taken in the cup using Pasteur pipette and
the bob was lowered to align appropriately with the cup
Contact angle measurements were carried out to explore (Kesarwani et  al. 2021c). The parts of the rheometer
the tendency to adhere the liquid on the sand surface. The were carefully cleaned with distilled water before every
surfactant solution was first filled inside the displacement measurement.

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Environmental Science and Pollution Research (2022) 29:44255–44270 44259

Particle size of the NPs brine that remained in the sand pack. The permeability of
the injection fluid was evaluated as per Darcy’s equation
The size of the NPs was investigated using the Malvern (Hashmet et al. 2014). Crude oil was then flooded in the
Zetasizer Nano-ZS. The NPs first dispersed in the deion- sand pack with the same flow rate until the brine inside the
ized water using the sonicator were used to measure their sand pack was wholly displaced. The crude oil volume used
hydrodynamic diameter. A standard beam of laser light of to saturate the sand pack is known as the initial oil saturation
wavelength 633 nm was used to measure the diffusion of or original oil in place (OOIP). Connate water saturation
the NPs dispersed in deionized water. The Stokes–Einstein is described as the difference between OOIP and the total
equation was used to obtain the average hydrodynamic diam- pore volume of the sand pack. After the crude oil injection,
eter of the NP. For the measurement, a disposable cuvette the sand pack was left for 24 h to ensure the oil wettability
was filled up to less than half of its height. The analysis was of the sand pack. Next, water injection (brine at 1 mL/min)
carried out at ambient conditions. was carried out to recover the OOIP, which is the secondary
oil recovery. A 0.5 pore volume (PV) of slug comprising
Sand pack flooding experiments 1000 ppm polymer, surfactant at CMC, and nanoparticle of
varying concentration was flooded into the sand pack, which
A conventional flooding experiment methodology was was again followed by the chase water flooding at the same
applied to carry out the sand pack flooding experiments rate to recover the additional oil from the sand pack.
(Hashmet et al. 2014; Kesarwani et al. 2021a) The sand pack
was made using normal beach sand (40–60 mesh). The sand
particles were first washed with the distilled water several Results and discussion
times to remove clay particles or any other impurity pre-
sent in the sand and then dehydrated in the oven overnight Surface tension
at 105 °C temperature. By ramming the cleaned and dried
sand particles into a sand pack holder (length 30 cm; diam- One of the most critical factors affecting oil mobilization
eter 2.54 cm), the sand pack was formed. Brine (1 wt.% in the reservoir is surface tension (Sakthivel et al. 2015).
NaCl) was used to saturate the sand pack while preparing. Surface tension is defined as the imbalance in the forces
The brine volume used to prepare the sand pack was used experienced by the liquid phase molecules, which are at the
as the pore volume of the sand pack. After the sand pack surface. This arises due to the molecules’ forces from the
was packed correctly, the flow lines were attached, connect- bulk to shrink its surface area (Campbell 2015). Surface ten-
ing the syringe pump, accumulators, and the sand pack. A sion is directly proportional to the IFT, which is the imbal-
conventional flooding experimental setup was used for the ance in the forces acting at the two liquids’ interface. IFT is
flooding in the sand pack (Fig. 2). The syringe pump was inversely proportional to the capillary number (Nc = µv/γ).
first filled with the brine, which was flowed (1 mL/min) So, the higher the capillary number, the higher the oil recov-
through the sand pack. The brine was flooded into the sand ery would be. Hence, it becomes critical to minimize the
pack until it was fully saturated with brine. The porosity surface forces to the lowest possible value to achieve better
of the porous media was calculated using the amount of oil mobilization. The surface-active forces were observed to

Fig. 2  Experimental setup for

sand pack flooding experiment

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44260 Environmental Science and Pollution Research (2022) 29:44255–44270

be decreased as the surfactant concentration was increased 500 ppm, and 1000 ppm, respectively (Fig. 3b). A lower IFT
(Fig. 3a). The surface tension decreased from 72.3 to 31.5 value is desirable for the oil mobilization from the smaller
mN/m as surfactant concentration in solution was increased pore spaces. The results showing the synergistic effect of
from 0 to 2500 ppm, respectively. This may be due to the the addition of NPs with the surfactant are consistent with
surfactant molecules adsorbing at the liquid surface, caus- the studies done previously (Harikrishnan et al. 2017; Ma
ing the force to be stabilized (Bera et al. 2014). This trend is et al. 2019).
consistent with the previous studies where surface tension
was explored at various concentrations of surface-active CMC measurement of surfactant
agents (Babu et al. 2015; Yuan et al. 2015). There was no
major difference in surface tension value as the surfactant The most crucial parameter while using the surfactant is the
concentration in the solution was increased above 2500 ppm. CMC, which was obtained using conductivity measurement.
This may be due to the system’s free surfactant molecules The conductivity of the aqueous solution is determined by
being micellized. Above CMC (2500 ppm), micelle for- the solution’s ionic strength, which increased as the amount
mation of free surfactant molecules starts which does not of surfactant added to the solution was increased (Fig. 4a).
affect surface tension (Kumar et al. 2016). The addition of The surfactant’s CMC was determined by a sharp differ-
2500 ppm of the surfactant minimized the IFT up to 5.42 ence in slope of conductivity versus surfactant concentration
mN/m measured at 30 °C. plot. This could be attributed to the surfactant’s micelliza-
As the NPs were introduced in the surfactant solution tion after a certain concentration, after which the number of
of concentration 2500 ppm, the surface tension was further surfactant-free molecules remained fixed, but the number of
reduced. As NPs (100, 500, and 1000 ppm) were added surfactant micelles present in the solution increases (Ahmadi
to 2500 ppm of surfactant solution, surface acting forces and Sheng 2016). As a result, the ratio of surfactant micelles
dropped to 29.4, 27.1, and 26.1 mN/m, respectively. This to free surfactant molecules in the solution increases. Conse-
may be explained by the NPs’ adsorption at the liquid sur- quently, the steepness of the plot decreases, giving a turning
face due to their high surface energy owing to their smaller point that is identified as CMC. At 30 °C, the CMC of the
size (Cheraghian and Hendraningrat 2016; Pillai and Mandal SDS used in the experiment was 2462 ppm.
2020). The long hydrophobic chain of the surfactant could Temperature rise caused an increase in CMC of SDS.
make the solution hydrophobic, resulting in the adsorption As the temperature was elevated from 30 °C to 50 °C and
of the NPs at the surface (Saien and Bahrami 2016; Kumar 70 °C, CMC of SDS increased from 2462 to 2576 ppm and
and Mandal 2019; Pal et al. 2019, 2020). The low concentra- 2669 ppm (Fig. 4b). This may be because a rise in tempera-
tion of the NPs has been reported to reduce the IFT because ture increases the water’s solubility. Another possible expla-
of its adsorption at the interface, whereas higher concentra- nation for the same could be the increase in particle motion
tion tends to migrate surfactant molecules from the bulk in the liquid phase due to higher kinetic energy at elevated
phase (Mohajeri and Hemmati 2015); due to this, NPs were temperatures. This would raise the electrostatic interaction
added in smaller concentrations in the surfactant solution among the surfactant particles, as a result of which the delay
of fixed concentration. The IFT of the 2500-ppm surfactant in the micellization would have occurred. These findings are
solution and the crude oil was decreased from 5.42 mN/m in line with a previous work (Khoshnood et al. 2016).
to 3.31 mN/m, 0.98 mN/m, and 0.05 mN/m as the NPs’ NPs have a significant impact on the CMC of surfactant.
concentration in the solution was increased to 100 ppm, CMC of surfactant was found to decrease from 2462 to

Fig. 3  a Surface tension of the

surfactant solution; b IFT of the
surfactant solution (2500 ppm)
with the variation of NP’s
concentration

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Fig. 4  a Conductivity as a function of surfactant concentration; b effect of temperature on the CMC of surfactant; c effect of nanoparticle con-
centration on the CMC of the surfactant

2374  ppm, 2282  ppm, and 2147  ppm corresponding to corresponding to dolomite and bentonite. The high value
the NP concentration of 0 ppm, 100 ppm, 500 ppm, and of adsorption in dolomite could be because of the intense
1000 ppm, respectively, in the solution (Fig. 4c). As the NPs attraction between opposite charged surfactant and surface
were dispersed in surfactant solution, electrostatic repulsion (Iyota et al. 2010). In contrast, for bentonite, high adsorp-
among the SDS particles’ charged heads decreased (Ahmadi tion values could be explained by the higher surface area
et al. 2016). The addition of NPs could improve the aque- offered by the adsorption sites due to smaller particle size
ous solution’s ionic strength. (Eftekhari et al. 2020). It has and complex charge distribution in the clay particles that
been found in previous research that increasing the ionic play an essential role in the surfactant adsorption process
concentration of the surfactant solution decreases the CMC (Ma et al. 2013). The adsorption of the surfactant is gener-
of surfactant (Tanford 1980; Umlong and Ismail 2005). ally governed by the electrostatic interaction when the sur-
factant concentration is lower. In contrast, it is governed by
Adsorption of surfactant the weak hydrophobic interaction among long hydrocarbon
chains of surfactant molecules at a concentration higher
Effect of the mineralogy on surfactant loss than the CMC (Zhang and Somasundaran 2006). The results
obtained in the present study are consistent with the previous
Surfactant adsorption on rock surfaces that exceeds a cer- study (Saxena et al. 2019a).
tain threshold is unacceptable. It decreases the efficacy of
surfactants to balance the interfacial forces among the res- Effect of NPs on the surfactant loss
ervoir fluids and injection fluid (Benzagouta et al. 2013).
Loss of surfactant is majorly affected by the surfactant type Three different concentrations of the NPs (100, 500, and
and surface charge possessed by reservoir rock. Adsorption 1000 ppm) were dispersed in surfactant solution of vary-
of the surfactant solution (500–4000 ppm) on three different ing concentrations (500–4000 ppm) and its adsorption on
adsorption surfaces (sand particles, dolomite, and benton- the sand particles was investigated for 1 day keeping the
ite) was explored up to 24 h at 30 °C. Surfactant adsorption temperature at 30 °C. The loss of surfactant was found to
for the anionic surfactant in the case of sand particles was decrease as NPs were dispersed in the solution. Surfactant
found to be 1.81 mg/g, which increased up to 15.40 mg/g, adsorption was lowered by up to 8.58%, 25.10%, and
corresponding to 500 and 2500 ppm of SDS, respectively 45.67% when 100 ppm, 500 ppm, and 1000 ppm of NPs
(Fig. 5a). This may be explained by the rise in free surfactant were dispersed with 2500 ppm SDS solution, respectively
molecules with surfactant concentration (Ahmadi and Shadi- (Fig. 5b). The adsorption of surfactant particles on the NP’s
zadeh 2012). However, after the CMC value, the surfactant surface occurred by creating a surface cluster and NPs (Wu
loss due to adsorption did not increase significantly (Ahmadi et al. 2017). The cluster remains in the bulk phase instead
and Sheng 2016). of engaging with rock surface, which reduces the loss of
The loss of surfactant was observed to be more when surfactant (Yekeen et al. 2017). Another possible explana-
the adsorption surface was dolomite and bentonite than that tion for the surfactant adsorption reduction could be the
of sand particles. The surfactant adsorption values corre- adsorption of the nanoparticles on the rock surface, result-
sponding to 2500 ppm of SDS were 37.02 and 38.04 mg/g ing in fewer sites for the surfactant to get adsorbed. Previous

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44262 Environmental Science and Pollution Research (2022) 29:44255–44270

Fig. 5  Adsorption of the
surfactant: a effect of mineral-
ogy; b effect of nanoparticle
concentration; c effect of time;
d effect of temperature

research reporting the reduction of the surfactant adsorption limited adsorption sites, an increase in the surfactant adsorp-
upon introducing the NPs in the bulk solution corroborates tion results in filling all the sites available for adsorption
these results (Saxena et al. 2019b). by the surface-active agents leading to the reduction of the
adsorption rate with an increase in the exposure time. Previ-
Effect of contact time on surfactant loss ous studies corroborate these results (Ahmadi et al. 2012;
Ahmadi and Shadizadeh 2015).
Since the chemical slug injected in the reservoir is in con-
tact with the reservoir for a longer period, it becomes criti- Effect of temperature on the surfactant adsorption
cal to investigate the exposure time’s role on the surfactant
adsorption. For this, sand particles were used as adsorbents Another parameter that affects surfactant adsorption is tem-
and the loss of surfactant solution of varying concentration perature. Since the subsurface temperature is often higher
(500–4000 ppm) was monitored at 30 °C. As the rock sur- than the ambient temperature, the loss of surfactant solu-
face exposure to the surfactant molecules was increased, the tion at various concentrations (500–4000 ppm) on sand par-
surfactant adsorption was found to be increased. The sur- ticles at elevated temperature in the presence of NPs was
factant adsorption increased from 8.37 mg/g to 9.87 mg/g, explored up to 24 h. The surfactant adsorption was found
11.46 mg/g, 12.69 mg/g, and further 13.57 mg/g as the expo- to be reduced from 8.37 mg/g to 7.54 mg/g and 6.62 mg/g
sure time was increased from 1 to 2 days, 3 days, 4 days, corresponding to 30 °C to 50 °C and 70 °C, respectively,
and 5 days, respectively, at 2500 ppm of surfactant in the for 2500 ppm surfactant and 1000 ppm NPs (Fig. 5d). At
solution with 1000 ppm of NPs (Fig. 5c). This could be elevated temperatures, particles become more active and
because of the rise in the adsorption of surfactant particles possess higher kinetic energy (Belhaj et al. 2019). Higher
as a single layer on the rock’s surface with increased con- kinetic energy would result in the surfactant molecule
tact time. However, the rate with which the loss of surface- motion, and the surfactant would stay in the bulk phase;
active agent was increasing decreased, corresponding to a consequently, their adsorption would be reduced. Since res-
longer contact time duration. This may be demonstrated by ervoir temperature is usually high, it would provide an edge,
the limited adsorption sites for surface-active agents. Due to as the surfactant adsorption would be lower in the subsurface

13
Environmental Science and Pollution Research (2022) 29:44255–44270 44263

temperature condition than that of the surface temperature

leading to lower surfactant losses. The results are consistent
with the earlier study (Ziegler and Handy 1981).
The proposed mechanism for the adsorption reduction
for surfactants with NPs is the interaction of surfactants
with NPs. Surfactant molecules form micelles with poly-
mer chains intermingled in between (Fig. 6a). Few poly-
mer chains and surfactant particles get adsorbed on sand
surfaces. The electrostatic repulsion between the charged
surfactant particles causes surfactant adsorption on sand par-
ticles. However, the introduction of NPs in the surfactant
polymer solution results in the formation of micelles stuffed
with the NPs (cluster of surfactant and NPs), intermingled
with the polymer chain. This intermingling keeps most
surfactant particles in the bulk phase rather than interact-
ing with the rock surface, thereby reducing the surfactant
adsorption (Fig. 6b).
Fig. 7  Contact angle of the surfactant solution of varying concentra-
tion on the sandstone surface
Wetting characteristics

The wetting behavior of the rock is one of the most vital surface-active agents at the solid–liquid interface at higher
variables that affect the crude oil recovery. These wetting surfactant concentration (Zdziennicka and Jańczuk 2010).
characteristics of the rock were inspected by performing The interaction of surfactant molecules at the solid–liquid
contact angle study. Contact angle on different surfaces interface would have increased at higher surfactant con-
with different NPs concentrations was explored. The con- centration resulting in the lower contact angle values with
tact angle of surfactant solution at various concentrations higher surfactant concentration (Zdziennicka and Jańczuk
on the sand pellet surface was observed to decrease as the 2010; Kumar et al. 2016). The contact angle for distilled
surfactant amount dissolved in water was increased. A simi- water was obtained as 108°, which decreased up to 94.5°
lar pattern was also observed in the dynamic contact angle in 600 s. The rise in surfactant concentration reduced the
(after 600 s). However, contact angles at 600 s were found contact angle up to 46° at 2500 ppm of surfactant concen-
to be lower than that at 0 s (Fig. 7). The contact angle reduc- tration in the solution. However, no substantial difference in
tion could be explained by the high surface activity of the the contact angle was found as the surfactant concentration

Fig. 6  Schematic for the mechanism responsible for the surfactant adsorption reduction on the sandstone surface: a in absence of NPs; b in pres-
ence of NPs

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44264 Environmental Science and Pollution Research (2022) 29:44255–44270

was increased further. This could be explained by the satura- on non-polar parts of crude oil, exposing the hydrophilic
tion of the surface of the rock with surfactant (Kumar et al. charged head of surfactant, making it water-wetting rock sur-
2016; Kesarwani et al. 2021b). A decrease in contact angle face. In the dolomite surface, the same process is responsible
from 108 to 46° demonstrates the change in the oil-wet sand for the wettability shift (Gupta and Mohanty 2011; Jarrahian
surface’s wettability to water-wet. The modification of wetta- et al. 2012). The results obtained in the present study are
bility from oil-wet is crucial as it could contribute to higher consistent with the previous ones (Al-Anssari et al. 2017;
oil recovery from the reservoir. Hou et al. 2018).
As the NPs were introduced with the 2500 ppm of the
surfactant solution and their concentration was varied, the Flow behavior of chemical slug
contact angle was found to reduce further for the same rock
surface. The contact angle for sand surface was found to The fluid inside the permeable reservoir follows a tortuous
reduce from 47° to 43°, 39°, and 34° as the NP’s concentra- path, making it essential to understand its flow behavior over
tion was increased from 0 ppm to 100, 500, and 1000 ppm, a wide range of shear rates (Nwonodi et al. 2020). Viscom-
respectively, in 2500 ppm of surfactant solution (Table 1). etry of slug composed of a fixed concentration of polymer
This could be explained by NP’s adsorption on the solid–liq- and surfactant was investigated over a shear rate ranging
uid interface (Bera et al. 2020). Similar was the case with from 1 to 5000 ­s−1. The viscosity of the slug was found to
different surfaces. The contact angle for positively charged be reduced with a higher shear rate. The viscosity of the slug
dolomite surface was found to be reduced from 56° to 52°, composed of 1000 ppm PAM and 2500 ppm SDS decreased
49°, and 46° as the NP’s concentration in the 2500 ppm sur- from 112 to 3.7 mPa.s corresponding to 5 and 5000 ­s−1 shear
factant solution was increased from 0 ppm to 100, 500, and rate (Fig. 8a), which shows the shear-thinning (pseudoplas-
1000 ppm, respectively. In contrast, the same for the ben- tic) behavior of the chemical slug (Roumpea et al. 2017).
tonite surface was found to be 53°, 49°, 46°, and 42° at the This could be attributed to the weakening of the complex
same concentration. long polymeric chain (Iwasaki et al. 1991). As the shear rate
The mechanisms responsible for the wettability modifi- was increased, the polymeric chain’s entanglement became
cation can be explained either by the mineralogy, crude oil weaker, resulting in the reduction of the slug’s viscosity. The
composition, or surfactant type. For an anionic surfactant, reduction in the viscosity was gradual when the shear rate
hydrophobic interaction could be held accountable for the was low. However, at a higher shear rate, the entanglement
change in wettability. In contrast, the same in the case of of polymer chains would have become weaker, resulting in
positively charged surfactant head group could be the ion- a higher viscosity reduction rate.
pair formation. The hydrophobic interaction mechanism is As the NPs were introduced in the surfactant and poly-
also known as the surfactant adsorption mechanism. The mer solution, the viscosity of the slug was amplified. The
hydrophobic tail of the surface-active agent interacts with solution’s viscosity increased from 14 mPa.s to 15 mPa.s,
the non-polar part (carboxylic group) of crude oil, which is 17 mPa.s, and 19 mPa.s as the amount of NP dispersed in the
adsorbed on the oil-wet surface (Salehi et al. 2008; Hou et al. solution was increased from 0 to 100, 500, and 1000 ppm,
2015). This leads to the adsorption of surface-active agents respectively, at a 100 ­s−1 shear rate. The increase in the

Table 1  Contact angle data S. No Surfactant concentration (ppm) Contact surface Nanoparticle con- Contact angle
for the different surfaces centration (ppm) (°)
with different nanoparticle
concentrations 0 s 600 s

1 2500 Sandstone 0 47 40
2 100 43 35
3 500 39 30
4 1000 34 26
5 Dolomite 0 56 49
6 100 52 46
7 500 49 42
8 1000 46 39
9 Bentonite 0 53 46
10 100 49 42
11 500 45 38
12 1000 42 35

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Environmental Science and Pollution Research (2022) 29:44255–44270 44265

Fig. 8  Viscosity as a function of
shear rate: a effect of nano-
particle concentration on the
surfactant polymer solution; b
effect of temperature

solution’s viscosity could be because of a rise in the amount 2013). Achieving the lowest IFT is one of the prime objec-
of solid particles present in the solution that would offer tives during surfactant polymer flooding in the study. Lower
higher resistance to the flow leading to an increase in the IFT would result in a higher capillary number, which would
viscosity (Mahbubul et al. 2012). However, no change in the result in providing better residual oil mobilization. Also, the
pseudoplastic behavior of the solution was observed with the surface morphological analysis of the α-MnO2 nanoparticles
nanoparticle addition. was determined using the FESEM images (Fig. 9).
The temperature had an inverse effect on the viscosity Also, the rheological property has been improved
of the chemical slug. The viscosity of the slug was found (Sect. 3.5) with the addition of the NPs (Lu and Fan 2008).
to be reduced with an increase in the temperature. The vis- An increase in the viscosity of the chemical slug would
cosity of a slug containing 1000 ppm polymer, 2500 ppm result in better macroscopic sweep efficiency (Rezk and
surfactant, and 1000 ppm nanoparticles was decreased from Allam 2019b). Furthermore, due to the smaller size, the
6.1 mPa.s to 5.7 mPa.s and 4.8 mPa.s as the solution was NPs have a large surface free energy (Abbas et al. 2008)
heated from 30 °C to 50 °C and 70 °C, respectively (Fig. 8b). as well as they would offer greater electrostatic repulsion
This could be attributed to the distortion of the long, com- between other NPs resulting in the adsorption of the NPs at
plex weak polymeric chain with temperature (Hashmet et al. a solid–liquid interface (Brown et al. 2013). Because of this,
2014; Kumar et al. 2016). These results are consistent with the surfactant adsorption was reduced (Sect. 3.3.2). Conse-
the studies conducted earlier (Otsubo 1994; Kopperud et al. quently, this would aid in modifying the wetting behavior of
1998; Ariffin et al. 2016).

Particle size and FESEM analysis

The chemical slug’s characteristics are affected by the size

of the NPs added to it. The size of NP dispersed in the slug
was investigated by performing the DLS experiment. The
average hydrodynamic particle size of the nanoparticle was
found to be 141 nm. Only one peak around 122 nm was
obtained. The zeta potential value of the NP dispersed in the
deionized water was found to be − 21.2 mV which increased
to − 33.6 mV, suggesting that the NP formed a stable disper-
sion in surfactant solution. This could be explained by the
NP’s surfactant synergy. The NPs dispersed in the surfactant
solution interacted with the surfactant molecules forming
the nanoparticle stuffed surfactant micelle, which would
remain in the bulk phase resulting in stable dispersion of
NP. The addition of smaller NPs had a favorable effect on
the chemical slug’s interfacial property. This could be due
to NP’s adsorption at the liquid surface, which reduced the
IFT between the crude oil and chemical slug (Brown et al. Fig. 9  FESEM image of α-MnO2

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44266 Environmental Science and Pollution Research (2022) 29:44255–44270

the surface from oil-wet rock to water-wet (Sect. 3.4) (Bhui-

recovery (%
yan et al. 2015; Rezk and Allam 2019b).

Tertiary recover y Total oil

OOIP)

70.25
71.46
73.04
74.76
Oil recovery and pressure drop studies

The oil mobilization ability of a slug containing sur-

factant, polymer, and NPs in various concentrations was

(% OOIP)
explored using a traditional sand pack flooding technique.
The porosity and permeability for each run were calcu-

22.75
24.39
25.25
27.46
lated, and various flooding parameters were evaluated as
given in Table 2. The average porosity for the sand pack
was found to be ~ 34%, whereas the permeability for water

Recovery with water

injection (% OOIP)
and oil was found to be ~ 700 and ~ 320 mD, respectively.
For all cases, the amount of oil recovered from water injec-
tion was ~ 47.3% (Fig. 10a). However, the residual oil was
mobilized using the slug of different compositions, which

47.51
47.07
47.79
47.31
resulted in different oil recoveries. When no nanoparticle
was introduced in the surfactant polymer slug, the tertiary
oil recovery was found to be 22.75% of the OOIP. As the

29.75
28.54
26.96
25.25
NPs were introduced in the slug, the oil recovery value expe-

Sor
rienced a gradual increase with the rise in the amount of
NP dispersed in the slug. With NP concentration, the ter-

76.63
78.24
77.27
77.57
tiary oil recovery from the sand pack was increased from

Saturation (%)
Soi
22.75% to 24.39%, 25.25%, and 27.46%. A decrease in IFT
with NP concentration could be the reason for higher oil

23.37
21.76
22.73
22.43
recovery (Sect. 3.1). The surfactant adsorption was found

Swi
to be minimum for 1000 ppm NP concentration with the
slug (Sect. 3.3.2). This would increase the surfactant effi-

0.5 PV (SP slug + 1000 ppm NPs)

ciency. Higher surfactant efficiency because of lesser loss of

0.5 PV (SP slug + 100 ppm NPs)

0.5 PV (SP slug + 500 ppm NPs)
surfactant and reduction in the IFT would result in a better 0.5 PV (SP slug + 0 ppm NPs)
microscopic displacement of the crude oil. Another possible
Chemical slug containing

explanation for improved oil recovery could be the shift in

the wettability of sand particles after the treatment with a
chemical slug. The change in wetting behavior of reservoir
rock would lead to the distortion of the oil layer adhered to
the surface. The smaller immobile oil droplets would merge
to form a mobile oil phase that would contribute to higher
oil recovery. The amount of the oil left in the sand pack was
reduced up to a minimum value of 25.25% for 1000 ppm NP
Ko at Soi

concentration in the chemical slug (RUN 4).

Table 2  Experimental data for sand pack flooding

The pressure drop showed a similar profile during water

305
344
323
331

flooding for all cases due to similar injection fluid character-

istics. From 1.5 to 2 PV (NPs dispersed in SP slug), chemi-
Kw at Sw = 1

cal was injected with different viscosity values (Sect. 3.5).

K (mD)

As the slug’s viscosity was increased, the pressure drop

662
734
711
703

values were found to increase (Fig. 10b). After 2PV, as the

injection fluid was again changed to the lower viscosity fluid,
the pressure drop values started to decrease and stabilized at
Φ (%)

33.82
33.95
34.21
34.08

some value after the breakthrough of the chase water. The

pressure drop value was found to be higher, corresponding
to a greater amount of oil recovered. This may be due to
Run No

the formation of a larger oil bank in front of the chemi-

cal slug. The larger the oil bank, the greater would be the
1
2
3
4

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Environmental Science and Pollution Research (2022) 29:44255–44270 44267

Fig. 10  Sand pack flooding

experiments: a effect of nano-
particles on the oil recovery; b
pressure drop as a function of
the fraction of the pore volume
of the injection fluid

resistance experienced by it, which would result in higher SS: supervision, validation, project administration.
pressure drop values. No change in the pressure drop value AKC: reviewing and editing.
was experienced when there was a breakthrough of the chase
Funding  No external source of funding was used for this project.
water, meaning no further oil could be recovered from the
sand pack (Pillai et al. 2018). Data availability  The authors will make available the data and
associated protocols promptly available to readers without undue
qualifications.

Conclusions Declarations 
The laboratory application of α-MnO2 NPs was explored Consent to participate and publish  All authors confirm their participa-
for crude oil mobilization. The NPs successfully reduced tion in this study, have read the final manuscript, and have given their
the amount of surfactant loss on the sand particle surface consent for the publication of this study.
by 8.58%, 25.11%, and 45.67%, corresponding to a rise
in NP concentration from 100 to 500 ppm and 1000 ppm, Conflict of interest  The authors declare no competing interests.
respectively, in a surfactant solution of 2500 ppm. The NPs
used for the study reduced the IFT among the crude oil and
surfactant solution from 5.42 to 0.05 mN/m. Apart from
this, NPs helped in shifting the wetting behavior to a pref- References
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