Accepted Manuscript

Regular Article

Nanoparticle-enabled delivery of surfactants in porous media

E. Nourafkan, Z. Hu, D. Wen

PII: S0021-9797(18)30180-2
DOI: https://doi.org/10.1016/j.jcis.2018.02.032
Reference: YJCIS 23304

To appear in: Journal of Colloid and Interface Science

Received Date: 8 October 2017

Revised Date: 12 January 2018
Accepted Date: 10 February 2018

Please cite this article as: E. Nourafkan, Z. Hu, D. Wen, Nanoparticle-enabled delivery of surfactants in porous
media, Journal of Colloid and Interface Science (2018), doi: https://doi.org/10.1016/j.jcis.2018.02.032

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 Nanoparticle-enabled delivery of surfactants in porous media
E. Nourafkan1, Z. Hu1, D. Wen1,2*

1
School of Chemical and Process Engineering, University of Leeds, Leeds, LS2 9JT, UK

2
School of Aeronautic Science and Engineering, Beihang University, Beijing, P.R.China

*Corresponding author. Tel.: +44 (0)113 3431299

d.wen@leeds.ac.uk (D. Wen)

ABSTARCT

The adsorption of surfactants on the reservoir rocks surface is a serious issue in many energy
and environment related areas. Learning from the concept of drug delivery in the nano-
medicine field, this work proposes and validates the concept of using nanoparticles to deliver
a mixture of surfactants into a porous medium. In this study, TiO2 nanoparticles (NPs) are
used as carriers for a blend of surfactants mixtures including anionic alkyl aryl sulfonic acid
(AAS) and nonionic alcohol ethoxylated (EA) at the optimum salinity and composition. The
transport of NPs through a core sample of crushed sandstone grains and the adsorption of
surfactants are evaluated. By using TiO2 NPs, the adsorption of surfactant molecules can be
significantly reduced, i.e. half of the initial adsorption value. The level of surfactant
adsorption reduction is related to the NPs transport capability through the porous medium. An
application study shows that comparing to surfactant flooding alone, the total oil recovery can
be increased by 7.81% of original oil in place (OOIP) by using nanoparticle bonded
surfactants. Such work shows the promise of NP as an effective surfactant carrier, which has
many potential applications in enhanced oil recovery (EOR) and environmental remediation.

Keywords: Nanoparticles, surfactant delivery, surfactant adsorption, enhanced oil recovery.

1
1. Introduction

Energy and environment are the two main concerns of our future. The global demand of
energy is expected to increase as much as 50% in the next 20 years and the demand for oil
and gas will also increase [1, 2]. The era of finding “easy oil” is coming to an end, and future
supply will become more reliant on hydrocarbons produced from unconventional
hydrocarbon sources and enhanced oil recovery (EOR) processes. It is estimated that for
every barrel of oil we used today, there are still two barrels left in the reservoir [3]. On the
other hand, water and soil contamination is becoming a serious environmental issue due to oil
spillage and large scale use of pesticides, industrial chemicals, artificial nanoparticles (NPs)
and heavy metals etc [4, 5]. In both scenarios, oil or contaminants are trapped in the rock or
soil, i.e. a form of porous media interconnected by various-sized pores.
Many polymers or surfactants are used for EOR or soil remediation [6-9]. Among various
EOR techniques, surfactant flooding is a promising one, which relies on the injection of a
surfactant slug to reduce the interfacial tension (IFT) between oil and water, hence reducing
the fluid capillary force and mobilizing the residual oil [10-12]. On the other hand, surfactant-
enhanced aquifer remediation has shown some promise for underground water treatment [6,
13]. However, both methods suffer a common critical drawback: large adsorption of
surfactants inside porous media [14, 15]. This drawback reduces the effectiveness of the
surfactant and reduces the permeability of the porous media, making the process difficult to
operate and economically unfeasible [16, 17].
Intensive research has been conducted to understand the mechanisms of surfactant
adsorption in various porous media, which is a complex process that affected strongly by the
properties of the surfactant and the rock, their interactions, and the physic-chemical
properties of solution such as pH [18, 19], ionic strength [20, 21], solution temperature [21,
22] and rock properties [22]. A few methods have been proposed for more effective delivery
of surfactants such as using sacrificial adsorption agent (i.e. polymers) [15] or changing pH
value [23], which however has its limitations in the delivery efficiency with added cost of
sacrificial agents [15].
Using nanoparticles (NPs) is a recent development, many studies have shown that adding
NPs into a flooding fluid can alter the oil/water interfacial tension (IFT) [24] and substrate
wettability [25-27], reinforce the polymer properties [28, 29], and increase oil recovery rate
[30-32]. A few studies have suggested the use of nanoparticles for single component
surfactant delivery for oil recovery applications but with inconclusive results, especially on

2
the retention of NPs inside porous media and its relationship with surfactant adsorption [65].
This work proposes and validates the concept of using NPs for the delivery of surfactants
blends in porous media with a broad background application in energy and environmental
areas. The concept is analogy to the nanomedicine area where NPs are widely used for drug
delivery [33, 34].

Instead of delivering drugs to the targets inside a body, NPs are used to deliver chemicals
(i.e surfactant or polymer) inside a porous media either for EOR or environmental
remediation. It is hypothesised that there will have two main functions of nanoparticles: i)
deliver surfactants on its surface and reduce their adsorption on rock surface, and ii) form
some special effects in the targeting region such as oil/water interfacial tension (IFT)
modification [24], structural disjoining pressure [35] and log jamming effects [28], similar to
the effect of pure nanoparticles in EOR. A feasibility study is conducted in this work. A blend
of commercial anionic alkyl aryl sulfonic acid (AAS) and nonionic alcohol ethoxylated (EA)
surfactants is used as a realistic surfactant, and TiO2 NPs are used as the carriers. Sandstone
rocks are crushed and packed in a column for flooding studies to examine the adsorption and
retention of surfactants inside the porous media under flow conditions with and without NPs.
In addition, an application study for enhanced oil recovery is conducted by using surfactants
with and without TiO2 NPs to evaluate the effectiveness of the proposed concept.

2. Materials and Experimental Procedure

2.1. Materials and Characterization

Analytical grade materials including n-octane, sodium chloride, propyl alcohol and
Titanium (IV) oxide NPs (P25, 21 nm, ≥99.5%) were purchased from Sigma-Aldrich. The
anionic alkyl aryl sulfonic acid (AAS) was supplied by Huntsman Petrochemical LLC and
nonionic alcohol ethoxylated (EA, C12-13/7EO) was purchased by Mistral chemical
company. The brine was produced by dissolving sodium chloride (at different weight
percentage) in deionized water. Mineral oil (Keratech 24 MLP, viscosity on file is 24 mPa.s
at 40 °C) were purchased from Kerax Ltd. Sandstone rock were crushed into single grains
and, sieved into narrow grain size fractions (ASTM Standard Testing Sieves, Retsch Ltd.)
and washed with de-ionized water for several times, which was followed by settling and

3
decanting to remove all dust particles. The residual wet sand particles were dried at 80 ºC for
5 days.

The IFT and contact angle were measured by axisymmetric drop shape analysis of a
captive drive instrument (i.e., pendant drop method) using a goniometer (CAM 2008, KSV
instruments Ltd. Finland). The IFT values were determined based on the Young-Laplace
equation. The BET surface area of crushed sandstone grains (250-425 µm) was measured
using a Micromeritics TriStar 3000 gas adsorption instrument. Viscosity was measured by a
Physica Anton Paar rheometer, model MCR 301 (Cone plate CP75) at a shear range 10-1000
s-1 at 22 °C. The surface morphologies of sandstone grains were examined using a scanning
electron microscope (SEM). Elemental mapping of sandstone grains were analysed using a
scanning electron microscope (FEI Quanta 650 FEG), which was equipped with X-Max
energy dispersive X-ray detector (Oxford Instruments). Fourier transform infrared (FT-IR)
spectroscopy (Nicolet iS10 FT-IR spectrometer) was used for analysing pure and
functionalized TiO2 NPs. The morphology and size of TiO2 NPs was analyzed by
Transmission electron microscope (FEI Tecnai TF20 TEM). The conductivity of solution was
measured by a Mettler Toledo conductivity Meter (Seven2Go). Zeta potential and
Hydrodynamic size of TiO2 NPs was measured with Malvern Zetasizer ZS instrument.

2.2. Core-flooding experiments

Fig. 1a shows the experimental coreflooding set-up. A peristaltic pump (Cole-Parmer
Instrument Co. Ltd.) was used for injecting brine during the core flooding experiments. A
syringe pump (KDS 410, KD Scientific Inc. USA) was used for injecting surfactants solution
to avoid cross contamination by different samples. The concentration of TiO2 NPs in solution
was measured by an UV-spectrophotometer (Shimadzu, UV 1800). A pressure transducer
(PX409-150DWUV, Omega Engineering Ltd.), which was connected to Lab View software,
was used to measure the pressure drop during experiments. 30 g of grain samples (250-425
µm) were packed into a glass tube (ID = 2.44 cm) to create unconsolidated sand packing
columns for core flooding tests. To prevent particles migration during the test, a PTFE filter
cloth (pore size, 10 um; thickness, 25 mm) was placed at both ends of the column. The
parameters of packed sandstone grains column are listed in Table 1, where the permeability
was calculated based on Darcy’s law by using the average pressure gradient at the both ends
of the packed bed column during brine saturation (Fig. 1b).

4
 Fig. 1. (a) Experimental core flooding set-up and (b) pressure gradient at the both end of
packed bed column during brine saturation.

Table 1. Parameters in average value for packed sandstone grains column

The evaluation of optimum salinity and composition of surfactant blends is discussed in

Part 3.2.1. The core flooding experiments were divided into two parts. The first part was for
dynamic surfactant retention measurement and the second one for oil recovery evolution. In
the first part of the experiments, below procedures were used:

 Injection of 100 ml brine (4% NaCl) flooding at a flow rate of 2 ml /min (0.156
PV/min) to fully saturate the column by brine.
 Injection of 20 ml surfactants solution (4 wt% NaCl, 25% AAS-75% EA, 0.3 wt%
total surfactant concentration) or TiO2 nanofluid (surfactants solution plus 2000 ppm
NPs) at a flow rate of 0.5 ml/min (0.039 PV/min).
 Injection of 20 ml brine post flooding (4% NaCl) at a flow rate of 1 ml/min (0.078
PV/min).

At the same time, the effluent solution was flowed through a UV-visible spectroscopy
meter and was collected. The NPs effluent concentration was measured based on the
absorption of NPs for UV light at a wavelength of 450 nm. The breakthrough curves (BTCs)
of NPs in the column outlet were generated by using the relative concentration (i.e., the
effluent concentration C divided by the original sample concentration C0), against the
injection time expressed in pore volumes (PVs).

The NPs recovery was calculated as a percentage of the injected NPs for nanofluid
injection and post brine injection. Calibration curves of TiO2 NPs concentration versus UV
absorption ratio were measured with known TiO2 concentration in dispersions. The retention
of NPs on solid surface (mg/g rock and mg/m2rock) for the core flooding was then calculated
by using BTC data. Mass balance calculation was performed considering both particles eluted
from the column during core flooding and those retained in the column. The calculation
showed that the total mass of NPs that emerged from the column together with the retained
mass is higher than 95% of the initial mass. The concentration of the surfactants solution in
effluent solution and washed solution were determined by Chemical Oxygen Demand (COD)
method, which was based on the determination of the quantity of oxygen that required to

5
oxidize carbon in the surfactant in a solution. Here de-ionized water as the blank solution was
used for calibration of COD method. The surfactant amount in effluent solution was
estimated by following oxidization reaction:

a  8d  3c
Cn H a Ob N c  dCr2O7 2  (8d  c) H   nCO2  H 2O  cNH 4  2dCr 3 (2)
2
After the completion of oxidation, the amount of Cr 3+ was determined as an indirect
measure of surfactant amount [36]. The COD method was explained in “Chemical Oxygen
Demand procedure” part of supplementary document in detail.

The procedures of core flooding experiments for oil recovery were conducted as below:

 Brine saturation by injecting 20 PV of brine at the optimum salinity (4 wt% NaCl)

into a similar packed bed column at 2 ml /min (0.156 PV/min).
 Oil saturation by injecting mineral oil at a flow rate of 0.5 ml/min (0.039 PV/min)
until a desired irreducible water saturation (Swi =25%) was achieved, and the original
oil in place (OOIP) is determined by the volume of water collected.
 Brine flooding as the secondary oil recover stage was performed with a fixed flow
rate of 0.5 ml/min (0.039 PV) for 2 PV.
 Tertiary flooding by 1.3 PV surfactant slug (with and without TiO2 NPs) at a flow rate
of 0.5 ml/min (0.039 PV/min).
 Post-flooding by 1.3 PV brine injection at a flow rate of 1 ml/min (0.078 PV). The
time interview chemical flooding and post brine flooding was 12 hours to allow the
equilibrium IFT and microemulsion formation inside porous media.

The effluent liquid was collected in a 50 ml graduated cylinder marked in 0.1 ml divisions
in order to determine the amount of oil recovered (Fig. 1a).

3. Results and Discussion

3.1. Sandstone grains analysis
Fig. 2 and 3 shows an example SEM and EDX analysis of a sandstone grain respectively.
The EDX micrographs vividly show the existence of major fraction of silicate crystals and
minor fraction of aluminosilicate mineral.

6
 Fig. 2. SEM photos of sandstone particles (250-425 µm) which were used for porous media
preparation (a) a single sandstone particle (479× mag.) and (b) Surface of sandstone particle
(5424× mag.)

Fig. 3. (a) Elemental mapping of silica using energy dispersive X-ray spectroscopic and
(b) distribution of aluminium components in analyzed section.

The surface charge was obtained by electrophoresis measurements [37]. In the

measurement, rock grains below 45 µm were collected and suspended in de-ionized water.
The large particles were settled after 1 hour and the remaining suspension was centrifuged
with a relative centrifuge force (RCF) equalling to 5000 for 30 minutes. The size of particles
in suspension was estimated between 3-4 µm based on the Stokes law. The electrophoretic
mobility of particles was then measured using a Malvern zetasizer. The characteristics of
sandstone particles are shown in Table 2.

Table 2. The characterization of sandstone grains.

3.2. Functionalizing of TiO2 nanoparticles with surfactants blend

3.2.1. Optimum salinity and composition of surfactant blends
Generally in ASP/SP flooding the surfactant concentration is in the range of 0.2-1.0 wt%
[38]. In this study, the total concentration of surfactants blend (AAS-EA) was considered
equal 0.3 wt% (i.e. 0.003 g/ml). The measurement of critical micelle concentration and
producing stable surfactant blend slug are discussed in the section of “Optimum salinity and
composition of surfactant blends” of the supplementary document.

The optimum salinity of surfactants solution to reach the lowest interfacial tension (IFT)
in oil-brine systems is important for flooding processes. Optimum salinity is usually
determined by the observation of Winsor type III microemulsions formation in pipette test. In
this test, glass sample tubes (pipettes) were filled by 1 ml surfactants solution (0.3 wt% and 3
wt% concentration) of AAS-EA (equal mass) at different salinities and 1 ml n-octane.
Pipettes were sealed first at the tip and after being filled, they were sealed at the top and then
stored in oven with a constant temperature of 40 ºC. Each sample was monitored for ten days
to demonstrate the ultimate state after reaching to the equilibrium condition (Fig. 4a, b). The
largest volume of middle phase microemulsion (here approximately at 4 wt%, Fig. 4a, b)

7
indicates an optimal formulation for surfactants blend. The IFT between n-octane and
surfactants solution at different salinities are shown in Fig. 4b, which also confirmed the
optimum salinity of 4 wt%.

Fig. 4. Salinity scan of surfactants solution at 40 °C for (a) 0.3 wt%, (b) 3 wt% concentration,
and (c) IFT between n-octane and surfactants blend solutions at different salinity.

Fig. 5 shows the phase behaviour of solutions for different blend ratios of surfactants at 4
wt% salinity. According to Fig. 5a, Winsor type I is observed for EA with bluish oil in water
microemulsion and Winsor III for blend of AAS-EA, while there is not any microemulsion
formation in the absence of EA. Microemulsions with higher solubilisation parameter
belongs to the sample containing 25% AAS, which was selected as the optimum composition
for surfactants blend.

Fig. 5. Phase behaviour of surfactants solution at 4 wt% salinity for different blend ratios
of AAS-EA at 40 °C for (a) 0.3 wt% and (b) 3 wt% concentration

3.2.2. Preparation of TiO2 nanofluid

TiO2 nanofluids were prepared by mixing TiO2 nanopowders to a solution containing 0.3
wt% surfactants blend at the optimum salinity (4 wt%) and optimum composition (25%
AAS-75% EA). The NPs suspensions were homogenized by an ultra sound probe (Fisher
scientific Ltd.) running with an amplitude of 25 for 15 minutes prior to each core flooding
experiment.
The method of grafting surfactants to NPs can be classified as covalent assembly and non-
covalent adsorption. There are several types of linkage groups such as thiol, ether,
phosphonate, carboxylate, sulphate, alkene and amines, which can be introduced onto oxide
and graft to NPs with terminal OH groups [39, 40]. The proposed mechanism of grafting
AAS to TiO2 NPs surface is shown in Fig. 6. According to Fig. 6b, AAS molecule makes
hydrogen bonds to the oxide surface. Finally, condensation occurs between the Sulphate-OH
groups to form S-O-Ti bond (Fig. 6b) [40]. A similar procedure is proposed for grafting EA
molecules to surface of NPs via oxygen atom in ethoxylated group.

Fig. 6. Proposed mechanism of binding between sulfonic groups on a metal oxide surface,
(a) Surfactant molecule is ready to adsorb on the polar oxide surface of TiO 2 NPs via
hydroxyl bond of sulfonic group, (b) A hydrogen bond is formed between sulfonic groups

8
 and polar oxide surface, but still capable of moving laterally across the surface, and (c)
Finally, condensation occurs and a molecule of water is released.

The conductivity measurement was used to identify the amount of NPs that is required for
the attachment of all surfactants molecules on NP surfaces. TiO2 nanofluids (500, 1000,
1500, 2000 ppm of TiO2 NPs) were synthesised with a fixed total surfactants amount of 0.3
wt% in deionized water. The nanofluids have been kept in a dark place immobile for 20 days
for the sedimentation of NPs. The conductivity of the supernatant solution is shown in Fig. 7,
which shows that the supernatants’ conductivity decreases with the increase of particle
concentration. At a concentration of 2000 ppm TiO2, the conductivity becomes similar to
that of pure TiO2 nanofluid (i.e., without any surfactant). This shows that more and more
surfactants are bonded onto nanoparticle surfaces with the increase of nanoparticle
concentration. At 2000 ppm, there is still a small fraction of loose surfactant molecules inside
nanofluids. The concentration of 2000 ppm was selected for core flooding experiments since
higher concentrations are not more efficient for surfactant delivery. Comparison of the
conductivity data suggests that there is 5.17 wt% of surfactant molecules left in TiO2
nanofluid (2000 ppm) before the core flooding experiments, i.e., ~95% surfactants are
bonded onto nanoparticle surfaces. As a proof-of-concept study, we did not remove these free
surfactants molecules before core flooding experiments, but took all these into account in
calculating the delivery efficiency.

Fig. 7. Conductivity of supernatants of TiO2 nanofluids after the sedimentation of NPs

(different concentrations).

The zeta potential and hydrodynamic size of TiO 2 NPs was measured at -10.1 (mV) and
147 nm respectively. Fig. 8 shows the TEM and hydrodynamic size distribution of
functionalized TiO2 NPs.

Fig. 8. (a) TEM image and (b) hydrodynamic size distribution of functionalized TiO 2 NPs
in surfactant suspension.

The stability of nanoparticle dispersion against sedimentation was evaluated using a UV-
visible spectroscope. The spectrum of nanofluid (wavelength range of 200-1000 nm) was
recorded for 1.5 hour each 15 min time, which shows no change in adsorption peak pattern.

9
Therefore there was not any aggregation of sedimentation of nanoparticles during the core
flooding experiments.

3.2.3. FTIR Analysis

FTIR method was employed for analysing TiO2 NPs before and after functionalizing with
surfactants [40-42]. Samples were prepared by centrifuging 20 mL nanoparticle dispersions
for 30 hr at 10,000 rpm in an ultracentrifuge (Thermo Scientific megafuge 16R). The settled
particles were washed with 5 ml de-ionized water and dried in oven for 48 hours at 80 ºC to
remove water. Fig. 9a shows the FTIR spectra of pure surfactants, pure TiO 2 NPs and
sedimented TiO2 NPs after drying.
The absorption band observed at 1180 cm-1 for AAS and functionalized NPs is
correspondent to the stretching vibrations of SO3 group. The broad intense absorption in the
range of 600-900 cm-1 for pure TiO2 is associated with the vibrations of the bonds Ti-O and
Ti-O-Ti [43]. The vibrations observed in the 855, 946 and 1096 cm-1 for EA is attributed to
the stretches of C-O-C bond in ethoxylated group of EA [44, 45]. A strong absorption peak
was also observed at 3400 cm-1 for EA, attributed to the bending vibration of O-H.

Fig. 9. (a) FTIR spectra of pure surfactants, pure TiO2 and sedimented TiO2 NPs after drying
and (b) FTIR spectra of pure TiO2 and functionalized TiO2 NPs in aqueous phase.

Fig. 9b shows the FTIR spectra of pure TiO2 and functionalized TiO2 NPs in deionized
water. A strong absorption peak is observed at 3400 cm-1, attributed to stretching vibrations
of the hydroxyl group, which confirms the existence of hydroxyl groups on the TiO2 NPs
surface. The intensity of the absorption peak at 3400 cm-1 is significantly decreased for
functionlized TiO2 NPs compared to the pure one, which shows the decline of the surface
hydroxyl number after the modification of NPs with surfactant. Furthermore, another
absorption peak is observed at 1630 cm-1, attributed to the bending vibration of H-O-H of
water. The weak absorption bands at 1630 cm-1 for functionlized TiO2 NPs belong to H-O-H
symmetric vibration of the physisorbed water molecules on the surface of NPs, which also
confirm the successful graft of the surfactants.

3.2.4. Interfacial tension and rheological behaviour Analysis

Many studies have shown that nanoparticles alone (i.e., in absence of any stabilizer) do not
have much influence on the interfacial tension (IFT) of liquid-liquid or liquid-gas interface

10
[46,47]. . No reduction of IFT was observed even the particles were strongly attached to the
interface [47]. The effect of nanoparticles on IFT value is more complex in a ternary system
containing oil/water/emulsifier. The effect is strongly affected by the fraction of NPs at the
oil/water interface, which depends on the interaction between emulsifiers, NPs and
counterions, influenced by properties of NPs (e.g. size, hydrophilicity and hydrophobicity)
and the emulsifier (e.g. structure and Hydrophilic/Hydrophobic balance) [48-50].

Fig. 10. Dynamic IFT between TiO2 nanofluids and surfactants solution with n-octane.

Fig. 10 illustrated the dynamic IFT of TiO2 nanofluids in n-octane in comparison with
surfactants solution and pure water. Fig. 10b shows that the IFT of surfactants solution is
decreased by the diffusion of surfactants molecule to the drop surface, which starts from the
onset of drop formation in the cuvette (Fig 10c). The IFT of surfactants solution starts at
about 12.6 mN/m and approaches to the equilibrium value of 10.19, which is much lower
than that for deionized water/n-octane (52.1 mN/m, Fig 10a). For TiO2 nanofluids, the
dynamic IFT was initially higher comparing to pure surfactants solution, as the fraction of
free surfactants molecules in presence of NPs is lower and hence, they do not contribute to
the initial reduction of the IFT (Fig 10d). However, the IFT of nanofluids decreases gradually
toward the equilibrium and becomes lower than the surfactants solution. Since each NP
carries a number of surfactant molecules, it acts as a surface active agent and the IFT is
reduced due to the exchange of surfactant between NPs and the interface. Moreover, NPs
could be adsorbed on interface, which improves the stability of the droplet and reduce the IFT
(Fig 10c). However the time of diffusion and adsorption of functionalized NPs to oil/water
interface is different compared to surfactant molecules, which is consistent with the
observation from Vatanparast et al., in a ternary system of silica NPs/water/heptane [51].
The dependence of shear stress on shear rate for different surfactants solution with and
without TiO2 NPs and pure water at 25 ºC and 65 ºC is shown on Fig. 11. Despite a small
intercept on the shear stress axis due to the measurement uncertainty, all solutions clearly
show a Newtonian behaviour, similar to other observations [52, 53]. Clearly the introduction
of NPs increases the viscosity, which is an advantage for oil recovery process by improving
the mobility ratio.

11
 Fig. 11. Rheological curves of surfactants solution (0.3 wt %) in absence and presence
TiO2 NPs (0.002 g/ml) at 25 ºC and 65 ºC (a) Shear stress versus shear rate, and (b) viscosity
versus shear rate.

3.3. Core-flooding experiments

3.3.1. Surfactants blend retention inside porous media
Differential pressure profiles during different cycles of flooding are shown in Fig. 12. It
shows that the pressure difference is smaller and the pressure fluctuation is lower for NPs-
surfactants solution comparing to the surfactants solution only, which is favorited for oil
recovery applications. The main reason of such a behaviour is that the NPs cause more
uniform movement of surfactant molecules inside porous media. In contrast, for surfactants
solution only, it is generally in the form of aggregated micelles with high poly-dispersity
distribution in pores, which inevitably causes large pressure fluctuations.

Fig. 12. Differential pressure across the sandstone grains core versus time during (a)
surfactants solution flooding (0.3 wt %, 4 wt% salinity), and (b) surfactants solution flooding
containing TiO2 NPs (0.002 g/ml).

The breakthrough curve (BTCs) of TiO2 NPs as a function of PV is shown in Fig. 13.

Fig. 13. Breakthrough curves of TiO2 NPs in the effluent solution at the outlet of
sandstone particles core versus PV of injected fluid (surfactants solution containing NPs).

Large variations of NPs concentrations at the exit are observed, which is related to the
nature of the particle transport inside porous medium, as discussed below. It also shows that
certain NPs are entrained inside the core, which results in a continuous delivery of NPs in the
post-flooding by brine only. Significant amounts of NPs can be cleaned out from the cores
immediately following the brine flooding. No more NPs can be found at the exit after ~3.5
PV of post-flooding, which is similar to the results of Hu et al. study [28]. On the NPs
transport mechanisms inside a porous media, several mechanisms were proposed:
sedimentation, interception, straining and adsorption, as shown in Fig. 14 [54].

12
 Fig. 14. Schematic of different mechanisms of nanoparticle retention inside porous media
(a) straining (b) interception (c) sedimentation and (d) diffusion/adsorption (pictorial
representation not to the scale).

Sedimentation rate for spherical particle is estimated using the Stokes law, which shows
that it has a second order dependence on particle diameter. As TiO2 NPs size is small, the
sedimentation is unlikely to happen due to short residence time of particles in the packed
column and the effect of Brownian motion. Moreover, since the surface charge of sandstone
rock sample and NPs were measured as both negatively charged, the adsorption is also
unlikely to play an important role in trapping the particles. Interception is related to the
tortuosity of the porous media and surface roughness of sandstone grains [55].
The crystalline facets of sandstone particles can be observed vividly form SEM photos
(Fig. 3), which were specified by red ovals. The nanofluid could pass more uniformly over
smooth crystal facets surface comparing to the rough surfaces (e.g. amorphous surface),
which leads to lower NPs retention. Esfandyari Bayat et al. showed that the surface roughness
of a rock, in addition to the surface charge and surface chemistry, has a significance effect on
the retention of NPs. Irregular dents and bumps on limestone surface grains, as revealed by
the SEM images, affected the transport of TiO2 NPs significantly in porous media [56, 57].
Torkzaban and Bradford incorporated the role of surface roughness (both nano and micro
scale) on the retention rate into the DLVO theory, and indicated that the depth of the primary
minimum was considerably smaller on rough surfaces [58, 59].
Straining is possible to happen because of the ultra-low narrow pore throat introduced by
anomalous shape of rock grain after crushing and random packing. In those sensitive areas,
the relative size of nanoparticle ( ) and rock grains ( ) would be above the critical ratio of
0.0017 [60, 61]. Therefore, the high breakthrough ability in all rock matrix would be
attributed to negligible electrostatic adsorption and occasionally straining. The EDX mapping
results for the sample extracted from the column after the post-flooding process, show that
only small amount of nanoparticles was detected on the rock surface, verifying the negligible
electrostatic adsorption and weak interaction by adsorption/diffusion (Fig. 15).

Fig. 15. (a) SEM and (b) EDX analysis of bulk of sandstone grains which were extracted
from core holder at the end of flooding process, (surfactants solution containing TiO2 NPs).

13
 Table 3 shows the retention of TiO2 NPs and adsorption of surfactant, which were
calculated from the BTC and COD. For sandstone particle packing used, a majority of TiO2
NPs were transported through the core (84.41%), and most of the remaining was discharged
by the following post-flooding process, leading to a small retention rate of only 0.36%.

Table 3. Retention of TiO2 NPs and adsorption of surfactant in different porous media.

Table 3 shows that in absence of TiO2 NPs, the chosen surfactants have high adsorption
rate (1.44 mg/g rock) and the rate is halved after using the NPs. It is known that surfactant
adsorption is specified by the partition’s difference of surfactant molecules between the bulk
phase and the interface. The adsorption of surfactant molecule on rock is because of the
hydrocarbon tail-hydrophobic solid site interaction or hydrophilic head-hydrophilic solid site
interaction through the combination of various intermolecular forces (e.g, hydrogen bond,
electrostatic interaction or even covalent bonding) [62]. The result suggest that the blend of
AAS and EA incline to adsorb on surfaces containing Si and Al, which is consistent with the
typical chemical compositions of sandstone rock, as shown in Fig. 3.

However the adsorption of EA on sandstone rock is predominant comparing to AAS

because of two reasons. Firstly, as the surface charge of sandstone particles is negative and
the ionic head of AAS surfactant is also negative, Table 1, the repulsion force between
hydrophilic head of AAS and sandstone surface rock is higher comparing to EA. Secondly,
the AAS surfactant allocated a smaller fraction of the optimum composition of surfactants
blend (25%-part 3.2.1). Generally most of the nonionic surfactants form hydrogen bonds with
the hydroxyl groups of the rock surface through the ethylene oxide group; while ionic
surfactants form electrostatic bonds with the opposite charge mineral of the rock surface [63].
The results of Jian et al. about adsorption of ethoxylated non-ionic surfactant on a rock
containing different content of silica and clay minerals also confirm the observation of
current research [64]. They concluded that the adsorption of ethoxylated non-ionic surfactant
(C12-14E22) is increased on the rock surface containing higher fractions of silica mineral. With
attention to higher amount of EA in optimum composition (75 wt%), the formation of
hydrogen bond between EA with solid surface site is suggested to be the main factor for
surfactant adsorption amount as shown in Fig. 16.

Fig. 16. Proposed mechanism for EA surfactant adsorption on rock containing silica.

14
3.3.2. Oil recovery efficiency
In order to clarify the effects of NPs on oil recovery rate, two tertiary flooding
experiments were conducted, i.e., one with surfactants solution alone, and the other with TiO2
NPs carried surfactants (i.e., NP concentration of 2000 ppm). Fig. 17 shows that the oil
recovery efficiencies of brine flooding (4 wt% NaCl) are quite close to each other (at around
60%) for both cases, which means that the tertiary flooding started from similar residual oil
saturations. Small increase in oil recovery is observed after injecting nanofluids or surfactants
solution for ~1.5 PV. Significant increase in oil recovery is obtained following a post-brine
flooding and reaches a plateau after another 1 PV. During this stage, most of the surfactants
are flushed out. For nanoparticle-enabled delivery, the ultimate oil recovery reaches 91.66%
OOIP, which shows an increase of 7.81% OOIP comparing to the surfactants only, Table 4.

Table 4. The amount of oil recovered at different stages for flooding experiments with
different displacing fluids

Fig. 17. Tertiary oil recovery obtained by surfactants solution (0.3 wt% surfactants
concentration, 4 wt% salinity) and TiO2 nanofluid (0.3 wt% surfactants concentration, 4 wt%
salinity, 2000 ppm concentration).

Properly engineered, the functionalized NPs with surfactants are able to prevent the
surfactant molecules from adsorption on a rock surface during the transfer of molecules from
the injection well to the oil bank. However the efficiency of this concept is highly dependent
on the mobility of NPs inside the packing, which will be affected by the packing materials,
the surface change and surface properties of the grain, the nanoparticle used, as well as the
water chemistry (pH, salinity etc.), whose effects will be investigated in the future.

4. Conclusion

This work proposed a novel idea of using NPs for controlled delivery of surfactants in
porous media. The feasibility of the idea was proved in an example study by using TiO 2 NPs
to deliver a blend of commercial surfactants containing anionic alkyl aryl sulfonic acid
(AAS) and nonionic alcohol ethoxylated (EA) through a sandstone packing column. At a NP
concentration of 2000 ppm, the surfactant retention rate inside the porous medium was

15
reduced to half. The formation of hydrogen bond of EA with the substrate was suggested to
be the main factor for surfactant adsorption. By using NPs as the carriers, the direct
interaction between the surfactant groups and the rock surface was reduced, which reduced
the chance of surfactant adsorption. However the efficiency of this concept is highly
dependent on the mobility of NPs inside the packing, which will be investigated in the future
An application study shows that comparing to surfactant flooding alone, the total oil recovery
can be increased by 7.81% of original oil in place (OOIP) by using nanoparticle bonded
surfactants. Such nanoparticle-enabled delivery of chemicals could have a wide range of
potential applications for enhanced oil recovery and environment remediation.

Acknowledgement

The authors thank Mr. Timur Zaynetdinov (Huntsman Chemical, Belgium) for generously
providing us their commercial surfactant EOR products. This work was supported by
European Research Council Consolidator Grant (Grant number: 648375).

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20
5: Figure

a)

Cold stage core flooding Hot stage core flooding

Collecting of effluent for further
Pressure transducer analysis such as EOR evaluation

Glass column Heating tape

Pre-heating
Temperature controller

Peristaltic pump for

injection of brine

Syringe for injection of

chemical slug
a) Online measurement of NPs
Syringe pump concentration with UV-visible
 ΔP~6-7 psi

b)

Fig. 1. (a) Experimental core flooding set-up, and (b) pressure gradient at the both end of
packed bed column during brine saturation.

22
 Silica crystal facets

Fig. 2. SEM photos of sandstone particles (250-425 µm) which were used for porous media
preparation (a) a single sandstone particle (479× mag.) and (b) Surface of sandstone particle
(5424× mag.)

23
a)

b)

Fig. 3. (a) Elemental mapping of silica using an energy dispersive X-ray spectroscopic, (b)
distribution of aluminium components in analyzed section.

24
 0 2 4 6 8 0 2 4 6 8 wt% Salinity

a) b)

4
IFT (mN/m)

1
0 1 2 3 4 5 6
c) Salinity (wt. %)

Fig. 4. Salinity scan of surfactants solution at 40 °C for (a) 0.3 wt% (b) 3 wt% concentration,
and (c) IFT between n-octane and surfactants blend solutions at different salinity.

25
 0 2 4 6 8

wt% Salinity

a)

0 2 4 6 8
b) wt% Salinity

Fig. 5. Phase behaviour of surfactants solution at 4 wt% salinity for different blend ratio of
AAS-EA at 40 °C for (a) 0.3 wt% (b) 3 wt% concentration.

26
 Fig. 6. Proposed mechanism of binding between sulfonic groups on a metal oxide surface,
(a) Surfactant molecule is ready to adsorb on the polar oxide surface of TiO2 NPs via
hydroxyl bond of sulfonic group, (b) A hydrogen bond is formed between sulfonic groups
and polar oxide surface, but still capable of moving laterally across the surface, (c) Finally,
condensation occurs between the and a molecule of water is release.

27
 Surfactants solution

500

1000
Pure TiO2 NPs 1500
Deionizes 2000 ppm TiO2
Water
Water

Fig. 7. Conductivity of supernatants of TiO2 nanofluid after sedimentation of NPs

(different concentrations).

28
a)

b)

Fig. 8. (a) TEM image and (b) hydrodynamic size distribution of functionalized TiO2 NPs
in surfactants solution.

29
 110

100

90
Intensity (a.u.)

80

70

Pure TiO2
60 Functionalized TiO2
XOF 25S
Ethoxylated Alcohol
50
4000 3500 3000 2500 2000 1500 1000 500
-1
a) Wavenumber (cm )

120

110

100
Intensity (a.u.)

90

80

70

60
Pure TiO2 nanofluid
Functionalized TiO2 nanofluid
50
4000 3500 3000 2500 2000 1500 1000 500
-1
Wavenumber (cm )
b)
Fig. 9. (a) FTIR spectra of pure surfactants, pure TiO2 and sedimented TiO2 NPs after drying
(b) FTIR spectra of pure TiO2 and functionalized TiO2 NPs in aqueous phase.

30
 a)

c) d)

e)
b)
Fig. 10. (a) Dynamic IFT between TiO2 nanofluids and surfactants solution with n-octane (b)
dynamic IFT with zoom, (c,d,e) adsorption of surfactants and NPs on droplet surface.

31
a) b)

Fig. 11. Rheological curves of surfactants solution (0.3 wt %) in absence and presence
TiO2 NPs (0.002 g/ml) at 25 ºC and 65 ºC (a) Shear stress versus shear rate, (b) viscosity
versus shear rate.

32
 a)

b)

Fig. 12. Differential pressure across the sandstone grains core versus time during (a)
surfactants solution flooding (0.3 wt %, 4 wt% NaCl), (b) surfactants solution flooding
containing TiO2 NPs (0.002 g/ml).

33
 Fig. 13. Breakthrough curves of TiO2 NPs in the effluent solution at the outlet of
sandstone particles core versus PV of injected fluid, (surfactants solution containing NPs).

34
Fig. 14. Schematic of different mechanisms of nanoparticle retention inside porous media
(a) straining (b) interception (c) sedimentation (d) diffusion/adsorption (pictorial
representation not to the scale).

35
a) b)

Ti

Fig. 15. (a) SEM and (b) EDX analysis of bulk of sandstone grains which were extracted
from core holder at the end of flooding process, (surfactants solution containing TiO2 NPs).

36
Fig. 16. Proposed mechanism for EA surfactant adsorption on rock containing silica.

37
 Fig. 17. Tertiary oil recovery obtained by surfactants solution (0.3 wt% surfactants
concentration, 4 wt% salinity) and TiO2 nanofluid (0.3 wt% surfactants concentration, 4 wt%
salinity, 2000 ppm concentration).

38
 Table 1. Parameters in average value for packed sandstone grains column

Porous media property Value

Pore volume, Sw=1 (cc) 12.8

Porosity (vol %) 35.4

Absolute permeability (mD) 90-110

Mass of silica particles (g) 30

Liquid in the pore space (g) 12.8

Temperature (ºC) 40

Table 2. The characterization of sandstone grains.

Specific surface area Electrophoretic mobility Zeta potential Contact
(m²/g) (μmcmV-1s-1) (mV) angle
0.877 ± 0.001 -1.58 ± 0.09 -20.6 20.09

39
 Table 3. Retention of TiO2 NP and adsorption of surfactant in different porous media.

Parameter Value

Surfactant adsorption without NPs (mg/g rock) 1.44

Surfactant adsorption with NPs (mg/g rock) 0.71

Surfactant adsorption without NPs (mg/m2 rock) 1.094

Surfactant adsorption with NPs (mg/m2 rock) 0.54

Nanoparticle recovery after flooding (wt%) 84.41 %

Nanoparticle recovery after post flooding (wt%) 15.23 %

Nanoparticle retention (wt%) 0.36 %

Table 2. The amount of oil recovered at different stages, for flooding experiments with
different displacing fluids

Overall
Overall efficiency
Efficiency after Efficiency after Efficiency after efficiency
increase comparing
Displacing fluid brine flooding tertiary flooding post-flooding increase
to brine flooding
% OOIP % OOIP % OOIP percentage
% OOIP

Surfactants solution 60.41 60.93 83.85 23.44 38.9%

TiO2 nanofluid 59.37 63.54 91.66 32.29 54.4%

40
Graphical abstract

41