International Journal of Chemical, Molecular, Nuclear, Materials and Metallurgical Engineering Vol:6, No:7, 2012
understanding the mechanisms of mobilization and displacement of years because of its unique characteristics. Due to small
entrapped oil blobs by lowering interfacial tension both at the droplet size, they are not subject to gravity-driven separation
macroscopic and microscopic level. In order to investigate the owing to the density differences of the two phases. In the year
efficiency of oil-water nanoemulsion in enhanced oil recovery
1970, a new concept on emulsion has been developed based
(EOR), experiments were performed to characterize the emulsion in
terms of their physicochemical properties and size distribution of the on the emulsion characteristics. This new class of emulsions is
dispersed oil droplet in water phase. Synthetic mineral oil and a series known as nanoemulsion and sometimes miniemulsion or
of surfactants were used to prepare oil-in-water emulsions. ultrafine emulsion. On account of the dispersed phase droplet
Characterization of emulsion shows that it follows pseudo-plastic size, nanoemulsions are translucent or transparent, like the
behaviour and drop size of dispersed oil phase follows lognormal well known microemulsions. Emulsions and microemulsions
distribution. Flooding experiments were also carried out in a are well known in oil and gas industry. Nanoemulsions
sandpack system to evaluate the effectiveness of the nanoemulsion as containing oilfield chemicals may become in wide
displacing fluid for enhanced oil recovery. Substantial additional applications to well treatments (scale inhibition, fracture
recoveries (more than 25% of original oil in place) over conventional
acidizing etc.), flow assurance (multiple additive packages),
water flooding were obtained in the present investigation.
and deposit removal/clean-up. Their long-term stability and
Keywords—Nanoemulsion, Characterization, Enhanced Oil
ease of preparation from a concentration precursor are
Recovery, Particle Size Distribution compatible with oilfield logistics requirements. Emulsions are
thermodynamically unstable, disperse multiphase system of
I. INTRODUCTION two or more insoluble liquids [4] and microemulsions are
isotropic, transparent or translucent, thermodynamically stable
T HE conventional method of exploration and production of
oil might not be able to keep up the increasing energy
demands of the growing population. Therefore, the oil and gas
mixtures of oil and water which from spontaneously in the
presence of surfactant and/or cosurfactant [5]-[7].
Stability and characteristics of nanoemulsions depend upon
industry is facing difficult challenges and it needs
the preparation methodology, the order of addition of the
technological innovations to successfully meet the energy
components and the nature of the phases generated during the
demands. Nanotechnology can offer some unique solutions to
emulsification process and nanoemulsion do not form
mitigate these challenges. Nanotechnology has the potential to spontaneously [8]-[11]. Nanoemulsions, though
transform EOR mechanism and processes. It represents the thermodynamically unstable, can display noticeable kinetic
development and application of materials, methods, and stability. In fact, the small size of the dispersed droplets
devices, in which critical length scale is on the order of 1-100 eliminates separation processes based on density difference.
nm. Proven a game changer for exploiting fossil-based fuels Due to small size of nanoemulsion droplets they favour
and, over the next 30 years, nanotechnology will be a critical Ostwald ripening, a mechanism by which the fluid contained
component in developing fossil-based energy technologies [1]. in the smaller drops with highest interfacial energy is
transferred to larger drops, ultimately leading to coarsening of
the emulsion. For nonionic surfactants particle size
distribution are influenced by HLB (Hydrophile-Lypophile
Balance) values in nanoemulsion systems. The characteristics
of emerging nanotechnology that attract immense interest for
Ajay Mandal is Associate Professor at Petroleum Engineering Department, oil field applications include the resistance of nanoemulsions
Indian school of Mines, Dhanbad, Jharkhand, India-826004.(Phone: +91-326-
2235485; fax: +91-326-2296632; E-mail: mandal_ajay@hotmail.com). to sedimentation and creaming, which should translate to no
Achinta Bera is a Senior Research Fellow at Petroleum Engineering separation in storage tanks or during transport through
Department in Indian School of Mines, Dhanbad, India-826004. (E-mail: chemical feed lines.
achintachm@gmail.com).
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International Journal of Chemical, Molecular, Nuclear, Materials and Metallurgical Engineering Vol:6, No:7, 2012
The droplet size of nanoemulsions are smaller than the pore In the first step a concentrated precursor was prepared and
throats in gravel packs and in reservoir matrix rock, meaning in the second step the amount of oil necessary to obtain the
the good infectivity and penetration without filtration should desired final concentration was added. Initially to obtain the
be possible. precursor a mixture of surfactant, oil and brine was stirred
The objectives of the present study are the formation and using magnetic stirrer. The nanoemulsion then was prepared
characterization of nanoemulsion that are stable at the by adding additional oil phase to this concentrated precursor
reservoir temperature. The formation of stable nanoemulsion with gentle stirring.
using minimum amount of surfactant is the biggest challenge
for its use in enhanced oil recovery. In order to investigate the 3. Particle Size Measurement
efficiency of oil-water nanoemulsion in enhanced oil recovery The particle size distribution for the nanoemulsions prepared
(EOR), experiments were performed to characterize the with four different nonionic surfactants was measured
nanoemulsion in terms of their physicochemical properties and approximately 5 hrs after the preparation by a laser diffraction
size distribution of the dispersed oil droplet in water phase. method of Zetasizer Ver. 6.00 (Malvern Instruments Ltd.,
Synthetic mineral oil and a series of surfactants were used to Worcestershire, UK). The droplet size distribution
prepare oil-in-water emulsions. Thus, a complete study on determination was based on the best fit between the
physicochemical properties of nanoemulsion comprising of experimental measurements and the Mie theory. The software
nonionic Tergitol surfactants, brine, and mineral oil have been used a reflective index (RI) of 1.465 (SBO) and a dispersant
International Science Index, Chemical and Molecular Engineering Vol:6, No:7, 2012 waset.org/Publication/10032
investigated. A series of flooding experiments have been RI of 1.33 (water) during the measurement. Nanoemulsions
performed using the prepared nanoemulsion. The additional were diluted in distilled water to a droplet concentration of
recoveries were calculated by material balance. Encouraging less than about 0.05 wt% (to eliminate multiple scattering
results with additional recovery more than 22% of original oil effects), and gently stirred (to increase the homogeneity) prior
in place above the conventional water flooding have been to measurement. Drops of nanoemulsion were introduced into
observed. the sample presentation until the concentration reached the
optimum one, indicated by the instrument. All the experiments
II.EXPERIMENTAL SECTION were conducted at 25°C. Along with this, after preparation of
A. Materials nanoemulsions, the morphology droplets were captured by an
Four nonionic surfactants such as Tergitol 15-S-5 electron microscope (Olympus, BX2 Series) and analyzed by
(MW=415), Tergitol 15-S-7 (MW=515), Tergitol 15-S-9 image processing software (DP2-BSW).
(MW=584) and Tergitol 15-S-12 (MW=738) (HLB values are
10.6, 12.1, 13.3, and 14.7 respectively) were procured from 4. Experimental Apparatus and Methods for Nanoemulsion
Sigma-Aldrich, Germany. All the surfactants are 99.9 % pure Flooding
in nature. Mineral oil (98% pure) was used as organic phase The experimental apparatus is composed of a sand pack
and procured from Nice Chemicals, India. Sodium Chloride holder, cylinders for chemical slugs and crude oil, positive
(NaCl) with 99% purity was used for preparation of brines and displacement pump, measuring cylinders for collecting the
it was supplied by Qualigens Fine Chemical, India. The crude samples. The detail of the apparatus is shown in Fig 1. The
oil sample collected from Ahmadabad oil field was used in the displacement pump is one set of Teledyne Isco syringe pump.
flooding experiment. Reverse osmosis water from Millipore Control and measuring system is composed of different
water system (Millipore SA, 67120 Molshein, France) was
pressure transducers and a computer. The physical model is
used for preparation of solutions.
homogeneous sand packing model vertically positive rhythm.
B. Experimental Procedures The model geometry size is L= 35 cm and r= 3.5 cm.
1. Determination of Critical Micelle Concentration of the Sandpack flood tests were employed for the evaluation of the
surfactants effectiveness of microemulsion flooding. For uniform
Measurement of surface tension is very much useful sandpacks, 60−70 mesh sand was poured in to the coreholder
supplementary test method for determination of critical which was vertically mounted on a vibrator and filled with
micelle concentration (CMC). It is particularly useful when corresponding brines for different floodings. The coreholder
only very small quantities of an experimental surfactant are was fully filled at a time and was vibrated for one hour. The
available. In the present study surface tension of the different wetpacked sandpack was flooded with the heavy oil until
concentrated surfactant solutions were measured by a water production ceased (water cut was less than 1%). The
programmable tensiometer (Kruss GmbH, Germany, model: initial water saturation was determined on the basis of mass
K20 EasyDyne) under atmospheric pressure by the Du Noüy balance. The wetpacked sandpack was flooded with the Crude
ring method. During the measurement, the experimental oil at 400 psig to irreducible water saturation. The initial water
temperature was maintained at 298 K. The platinum ring was saturation was determined on the basis of mass balance.
thoroughly cleaned with acetone and flame-dried before each
Waterflooding was conducted horizontally at a constant
measurement. In all cases the standard deviation did not
injection flow rate. The same injection flow rate was used for
exceed ±0.1 mN/m.
all the displacement tests of this study. After water flooding,
~0.5 PV nanoemulsion slug was injected followed by ~2.0 PV
2. Preparation of Nanoemulsion
water injection as chase water flooding.
Nanoemulsions were prepared by high energy emulsification
method consisting of two steps.
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The same methods are followed for different nanoemulsion where, RFTotal = Total recovery factor (%), RFSM = Recovery
systems at various salinities. factor obtained by secondary method (%), RFTM = Recovery
The effective permeability to oil (ko) and effective factor obtained by tertiary method (%).
permeability to water (kw) were measured at irreducible water
saturation (Swi) and residual oil saturation (Sor), respectively, III. RESULTS AND DISCUSSION
using Darcy’s law equation. The permeability of the sand A. Critical Micelle Concentration of the surfactants
packs was assessed with the Darcy equation, Eq. (1), used It is well known that the surfactants reduce the surface
with fluid flow in porous materials. For a horizontal linear tension of water by getting adsorbed on the liquid–gas
system, flow rate is related with permeability as follow: interface. The critical micelle concentration (CMC), one of the
(1) main parameters for surfactants, is the concentration at which
surfactant solutions begin to form micelles in large amount
[12]. Surface tensions of the above three surfactants (Tergitol
where, q is volumetric flow rate (cm3/sec.), A is total cross-
15-S-5, Tergitol 15-S-7, Tergitol 15-S-9, and Tergitol 15-S-
sectional area of the sand pack (cm2), µ is the fluid viscosity 12) solutions at different concentrations were measured and
(CP), is the pressure gradient (atm/cm) and k is plotted as a function of concentration in Fig. 2. The
Permeability in Darcy. concentration at the inflexion point of the curve is critical
micelle concentration. For ethoxylated nonionic surfactant
International Science Index, Chemical and Molecular Engineering Vol:6, No:7, 2012 waset.org/Publication/10032
70
Tergitol 15-S-5
65 Tergitol 15-S-7
Tergitol 15-S-9
60 Tergitol 15-S-12
Surface Tension, mNm-1
55
Fig. 1 Schematic diagram of experimental set-up for Nanoemulsion
Flooding in sandpacks 50
45
5. Calculation of Oil Recovery by Nanoemulsion Flooding
40
The recovery factor was calculated by two methods, either
using a secondary oil displacement procedure or by means of a 35
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However, in each case only % intensity vs. particle size Tergitol 429.456 0.498 0.908 14.44
distribution curves has been shown for clarity. Usually size 15-S-5
effects are due to significant colloidal interaction between Tergitol 305.607 0.387 0.949 50.00
particles, that is to say when the particles are considerably 15-S-7
smaller than 10 nm. Two different factors are acting behind Tergitol 226.582 0.755 0.958 43.21
the droplet size distribution: firstly the particle deformability 15-S-9
decreases with droplet size and secondly the width of the Tergitol 22.812 0.538 0.957 49.59
15-S-12
droplet size distribution usually also decreases with droplet
size. In case of low HLB value (10.6), nanoemulsion shows
the Z-average diameter of 429.456 nm which is greater than
that of nanoemulsions with high HLB values (Z-average
diameters are 305.607 nm, 226.582 nm, and 22.812 nm for
HLB values of 12.1, 13.3, and 14.7 respectively). The Z-
average diameter is the mean hydrodynamic diameter and is
calculated according to the International Standard on dynamic
light scattering ISO13321. The Z-average diameter is intensity
weighted and is therefore sensitive to the presence of large
International Science Index, Chemical and Molecular Engineering Vol:6, No:7, 2012 waset.org/Publication/10032
25
Tergitol 15-S-5
Tergitol 15-S-7
50
Tergitol 15-S-9
Tergitol 15-S-12
20
0
Intensity, %
15 10 11 12 13 14 15
HLB value of Nonionic Surfactants
10
Fig. 5 Relation between Z-average diameters (nm) vs. HLB values
of nonionic surfactants
5
0
-200 0 200 400 600 800 1000 1200 1400
Particle Size (r), nm
TABLE I
RESULTS OF THE PARTICLE SIZE MEASUREMENTS OF THE NANOEMULSIONS
Sample Z- PDI Intercept Peak
Name Average Vol. %
diameter r.nm
(nm)
Fig. 6 Microscopic images of nanoemulsions prepared with
surfactants (a) Tergitol 15-S-9
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C.Nanoemulsion Flooding and Recovery The small droplet size of the nanoemulsion can help it to
The sand pack was flooded with nanoemulsion slug after penetrate into pore throats in gravel packs and in reservoir
water flooding and the Fig. 7 shows the oil recovered with matrix rock. Therefore, mobilization of oil in pore throats
pore volume injected into sand pack. The figure of waterflood would be easier and consequently recovery efficiency
oil recovery shows an early breakthrough and channel flow increases. The mechanism results in a reduced water mobility
which caused much lower oil recovery. During injection of that improves both vertical and areal sweep efficiency. The
nanoemulsion slug, water-cut declines gradually, and then additional recovery of oil over water flooding is 22.62, 22.90,
again reaches 100 % at the end of flooding. After the injection and 23.30 % when the nanoemulsion slugs with Tergitol 15-S-
of nanoemulsion slug, the trapped oil droplets or ganglions are 7, Tergitol 15-S-9, and Tergitol 15-S-12 were used
mobilized due to a reduction in interfacial tension between oil respectively. However, the proper design of the nanoemulsion
and water. The coalescence of these drops leads to a local slug should be performed by feasibility analysis, considering
increase in oil saturation. Behind the oil bank, the surfactant the operating costs and market value of the crude.
now prevents the mobilized oil from being retrapped.
110
The effectiveness of the nanoemulsion at different brine
100
concentration on enhanced oil recovery was tested with three
90
sets of flooding experiments performed in the sandpack
TABLE I
POROUS MEDIA PROPERTY AND OIL RECOVERY BY NANOOEMULSION FLOODING
Expt. No. Porosity Permeability, k Design of chemical Recovery of oil Additional Saturation, % PV
& (Darcy) slug for flooding after water recovery (% Swi Soi Sor
Surfactants flooding at 95% OOIP)
used kw ko (Swi) water cut
(Sw=1) (%OOIP)
1 (Tergitol 38.665 4.837 0.032 0.5PV Nanoemulsion 50.71 22.62 18.52 80.9 18.7
15-S-7) + Chase water
2 (Tergitol 38.665 4.669 0.028 0.5 PV Nanoemulsion 51.62 22.90 17.50 82.5 20.4
15-S-9) + Chase water
3 (Tergitol 39.586 4.449 0.025 0.5 PV Nanoemulsion 51.5 23.30 17.28 85.7 20.2
15-S-12) + Chase water
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ACKNOWLEDGMENT
The authors gratefully acknowledge the financial assistance
provided by University Grant Commission [F. No. 37-
203/2009(SR)], New Delhi to the Department of Petroleum
Engineering, Indian School of Mines, and Dhanbad, India.
Thanks are also extended to all individuals associated with the
project.
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[3] P. L. J. Zitha, Smart fluids in the oilfield, Exploration & Production: The
Oil & Gas Review, pp. 66–68, 2005.
[4] J. L. Salager, Pharmaceutical Emulsions and Suspensions: cap. 2,
Formation Concept for the Emulsion Maker, F. Nielloud, G. Marti-
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