SPE 131272

Application of Ferrofluid for Enhanced Surfactant Flooding in EOR

Nikita Kothari, Bhavna Raina, Krishna Chandak, Venkat Iyer & Hrishikesh Mahajan, Maharashtra Institute of
Technology, Pune



Copyright 2010, Society of Petroleum Engineers

This paper was prepared for presentation at the SPE EUROPEC/EAGE Annual Conference and Exhibition held in Barcelona, Spain, 1417 June 2010.

This paper was selected for presentation by an SPE program committee following review of information contained in an abstract submitted by the author(s). Contents of the paper have not been
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Abstract:
Improved Oil Recovery (IOR), techniques offer
prospects that enhance the displacement of oil from the
reservoir, ultimately producing 30 to 60 percent, or
more, of the reservoir's original oil in place. The most
important criteria in IOR- Surfactant Flooding is to
determine if the interfacial tension (IFT) can be
reduced enough to produce incremental oil.
One of the key recovery problems in oil-
wet reservoir is overcoming the surface tension forces
that tend to bind the oil to the rock. In water wet
reservoirs, surface tension forces act to create bubbles
of oil, which can block pore passages as the bubble
resists movement in the increased surface area
associated with squeezing through the passages. These
surface tension forces are the primary reason why
reservoirs become increasingly impermeable to oil,
relative to water, as the water saturation increases.
Ferrofluids are a special category of smart
nano-materials, in particular magnetically controllable
nanofluids. The ferromagnetic nano-particles are
coated with a surfactant to prevent their agglomeration.
As a result of their composition, Ferrofluids possess a
unique combination of fluidity and the capability to
interact with a magnetic field. The addition of a
surfactant will greatly reduce the Interfacial Tension
and in water-wet reservoirs, where oil globules are
formed, ferrofluid shatters it. Also, as ferrofluid comes
in contact with the reservoir fluid, it interacts with the
crude in the reservoir & due to the presence of dipole
moment, the reservoir fluid molecules align, thus
reducing the resistance to the flow.
To sum up, reduction in Interfacial tension,
thus reducing resistance to the flow, can be easily
achieved by making use of Ferrofluid-enhanced
surfactant. Oil can be made even more polar using
Ferrofluid which will act as a better solvent for the
surfactant.

Introduction:
Ferrofluid:
A ferrofluid (FF) is a type of smart fluid. It is
a suspension of nano-sized magnetic particles in a
carrier fluid, usually a type of oil, or water. When
subjected to a magnetic field, the fluid greatly
increases its apparent viscosity, to the point of
becoming a viscoelastic solid. Importantly, the yield
stress of the fluid when in its active ("on") state can be
controlled very accurately by varying the magnetic
field intensity. Although the name may suggest
otherwise, ferrofluids do not display ferromagnetism,
since they do not retain magnetization in the absence of
an externally applied field. In fact, ferrofluids display
(bulk-scale) paramagnetism, and are often referred as
being "superparamagnetic" due to their large magnetic
susceptibility. Permanently magnetized fluids are
difficult to create at present.

Fig 1a : Ferrofluid

2 SPE 131272
Figure 1a shows a FF in a magnetic field showing
normal-field instability magnet beneath the dish when
subjected to a sufficiently strong vertical magnetic
field, the surface spontaneously forms a regular pattern
of corrugations; this effect is known as the normal-
field instability. The formation of the corrugations
increases the surface free energy and the gravitational
energy of the liquid, but reduces the magnetic energy.
The corrugations will only form above a critical
magnetic field strength, when the reduction in
magnetic energy outweighs the increase in surface and
gravitation energy terms. Ferrofluids have an
exceptionally high magnetic susceptibility and the
critical magnetic field for the onset of the corrugations
can be realised by a small bar magnet.

Fig 1b : Ferrofluid Schematic




Figure 2. Sketch of sueracted ferrofluid grain:
a) Single-layered grains;
b) Double-layered grains.

Work at Indira Gandhi Centre for Atomic
Research:

R&D programme on FFs at Indira Gandhi Centre
for Atomic Research (IGCAR), has a focus to develop
ferrofluid based emulsions (which are prepared by
shearing FF oil in the presence of a surfactants and
water) for a variety of new applications such as field-
sensing sensors, leak free sealants etc. It is possible to
use the same as an EOR fluid as well. Highly
monodispersed magnetic emulsions with droplets in
the size range of 150 to 300 nanometers have been
successfully obtained from a crude (polydispersed)
emulsion. These emulsions are very easy to manipulate
by an external magnetic field. For any system that is
colloidal in nature, a clear understanding of the forces
acting between the particles is a prerequisite to make
the system stable for sufficiently long period. Ferro-
colloids are no exception to this. The net force acting
between the colloidal particles determines the stability
of the colloidal system. A net attractive force leads to
the aggregation or clustering of particles resulting in
instability. If the net force is repulsive, the system
(EOR Fluid) remains stable. The measurement of
forces between individual colloidal particles has
remained as a challenge till the development of an
elegant force apparatus in 1994 by a group of scientists
at Centre Research Paul Pascal-CNRS in France.
Without external field, these droplets have no
permanent magnetic moments because of the random
orientation of the magnetic grains within the droplets,
due to thermal motion. An applied field induces a
magnetic dipole in each drop, causing them to form
chains. The magnitude of the magnetic dipole moment
increases with the strength of the applied field
(Electromagnetic field can be created using EM tool in
existing well) until saturation is reached. Forces of the
order of (10-13 N to 10-11 N) between individual
colloidal droplets of the size of about 200nm can exist.
The sensitivity for inter-space distance measurement is
0.1 nm.

Components of Ferrofluids :

The FF consists of three components :
1. Magnetic Particles
2. Surfactant
3. Liquid Carrier

Magnetic particles contributes to about 15 -20%
volume of the total fluid.

These surfactants prevent the nanoparticles from
clumping together. This ensures that the particles do
not form aggregates that become too heavy to be held
in suspension by Brownian motion. The magnetic
particles in an ideal ferrofluid do not settle out, even
when exposed to a strong magnetic or gravitational
field. A surfactant has a polar head and non-polar tail
(or vice versa), one of which adsorbs to the
nanoparticles, while the non-polar tail (or polar head)
sticks out into the carrier medium.

While surfactants are useful in prolonging the
settling rate in ferrofluids, they also prove detrimental
to the fluid's magnetic properties (specifically, the
fluid's magnetic saturation), which are commonly a
parameter, which users wish to maximize (this is
SPE 131272 3
typically more of a concern when dealing with
magnetorheological fluids like crude). Whether or not
the surfactant is nanosphere-based or micelle-based,
the addition of surfactants (or any other foreign
particles) decreases the packing density of the
ferroparticles while in its activated state, thus
decreasing the fluids on-state viscosity, resulting in a
"softer" activated fluid

Common ferrofluid surfactants:
The surfactants used to coat the nano-particles include,
but are not limited to:
1. Oleic acid
2. Tetramethylammonium hydroxide
3. Citric acid
4. Soy lecithin

The liquid carrier is hydrocarbon oil and it
contributes to about 80 % of the total fluid volume.

Applications:

The idea of controlling the properties of
ferrofluids with a magnetic field has led to many
innovative applications. Some of the interesting
applications relating to FFs are highlighted in this
paper. Magnetic fields can artificially impart high
specific gravity in FF and alter the fluid property like
viscosity. This property can be exploited such that
when it is used as EOR fluid with surfactant, it has an
impact on the reservoir fluid. Alteration in the reservoir
fluid property in contact with FF based surfactant may
help to get higher recovery.

Ferrofluid under the influence of a strong intensity
EM field in near wellbore area can play a dominating
role in fluid movement inside the reservoir. Under the
influence of EM waves the dipole moment alignment
of reservoir fluid will take place, leading to decrease in
reservoir fluid property like viscosity, which will
enhance the flow of reservoir fluid through porous
media.

Ferrofluid Properties:
The properties of FF will help to define the
compositon/concentration of the ferro-particles, with
respect to the required EOR fuild properties.
1. Density
2. Heat Capacity
3. Viscosity

1) Density:

A hydrometer is an instrument to measure the
density of a liquid in relation to water (specific
gravity). The bulb pulls the liquid into the hydrometer
and the notches on the glass float are values of the
specific gravity. For example, if water were measured
the specific gravity would be 1.000.

Density of Magnetic fluid:

Experimental results show that the ferrofluid has a
higher density than its carrier fluid. Density increases
as the volume fraction of solid particles increases in the
colloidal mixture. If the volume of the colloidal
mixture is assumed to be the same as the sum of all the
volumes of the components, the density is represented
as:

=
s

s
+
a
(
h
-
s
) +
f
(1-
h
)

Where,
s=solid (magnetic) phase;
a=surfactant;
f=carrier liquid;
=density;

s
=volume fraction;

h
=hydrodynamic volume concentration

In case, where the density of the solid phase is
greater than either the surfactant or carrier fluid, an
increase in the volume fraction of the solid phase will
cause an increase in the overall density. If we further
assume that the densities of the surfactant and carrier
fluid are approximately the same, the previous
equation reduces to:

=
s

s
+
f
(1-
h
)

2) Heat Capacity:

Heat capacity is determined by a calorimeter. It
can be deduced from the equation E=Mc
p
del T.E is the
energy put into the calorimeter, m is the mass of
sample in the calorimeter, Cp is the heat capacity, and
del T is the change in temperature. Data is obtained
such that Cp is the only unknown in this equation. The
mass (m) of the test liquid put into the calorimeter is
known. The energy (E) is determined by multiplying
the potential by current over the time it runs
(E=V*I*t). Temperature rise, (del T), is recorded via
the thermometer.

2a) Heat capacity of ferrofluid:

Assuming the molecular interactions greatly
exceed those of particle-particle, the heat capacity can
be represented using the mixing rule. In our case the
heat capacity of the magnetic solid is much less than
4 SPE 131272
that of the fluid or surfactant. Thus, an increase in mass
concentration of the solid particles will cause the
overall heat capacity of the ferrofluid to decline.

C = C
s

s
+ C
a
(
h
-
s
) + C
f
(1-
h
)

3) Viscosity:

The viscosity of a magnetic fluid depends on the
solid fraction, the viscosity of the carrier fluid and the
applied magnetic field (orientation as well as force).
For the determination without an applied magnetic
field any standard viscometer can be used. In addition
the viscosity can be estimated using one of the
following formulas (from Rosensweig,
Ferrohydrodynamics):

Viscosity estimation:

For small particle concentration:

=
o
*(1+2.5)

For higher particle concentration:

=
o
*(1+a+b
2
)
-1

Where,


a = -2.5 and b = (2.5
c
-1)/
c
2
where,
c
= 0.74
(Closed Package)

Cost of Ferrofluids :

The cost of ferrofluids can vary from over $30
per liter to half that depending upon the ferro particle
concentration.

Basic Concept:

The basic concept is to treat the entire process
(surface and subsurface; exploration through the entire
life of the reservoir) as a single system to be optimized
and continually improved.

Downhole information and control could be
available through higher EM field channels throughout
well construction, completion, and production.

The basic concept of this approach is that the
industry develops the capability to fully monitor and
control the way fluids are moving through a reservoir.
This is extremely challenging, but has huge
implications on recovery. FF has capability to get
traced on application of EM waves, by observing
varation in the EM wave intensity.

To improve EOR recovery it is essential to
improve sweep efficiency. This will require significant
improvement in reservoir-scale surveillance
technology and in our ability to interpret and make the
measurements. In some cases it will be possible to
improve the sweep efficiency by changing injection
and production rates; in other cases it will be necessary
to target unswept areas with infill or sidetrack wells.

Unfortunately, the observations that we can
make are not direct measurements of saturation, but
rather are related to physical properties (e.g. pressure,
temperature, impedance, electrical resistivity, and
gravity) and it is necessary to interpret the changes in
physical properties in terms of the fluid-saturation
changes. Ferro-fluid can have a mojor impact to
accompalish the same.

These physical properties are converted to
saturations using a combination of empirical equations
(e.g. Archie equation) and parameters based on core
analysis (m, n, etc.). This empirical foundation limits
the accuracy of this approach and our ability to manage
reservoirs. To interpret the observational data, we are
generally forced to run a reservoir simulator, and in
parallel, compute the saturations changes based on
observations, and thereby infer fluid movements.
Ideally this manual means of inverting the data to
infer the fluid distributions would be replaced with a
FF tracker (Change in EM distribution within the
reservoir) that predicts fluid flow.

Alkaline-surfactant flooding:

Alkali flooding was a low-cost chemical flood
because surfactant could be generated by in situ
reaction between alkali and naphthenic acids present in
crude oil. However, it was difficult to keep the
electrolyte concentration at optimal conditions because
the concentration of alkali required for propagation
was usually higher than the optimal salinity. It was
discovered that injection of a small amount of synthetic
surfactant with the alkali made it possible to have the
process pass through the optimal conditions in situ. In
addition, alkali tended to reduce the adsorption of the
synthetic surfactant and thus made it possible to inject
a low surfactant concentration.

At present, ferrofluids (magnetic fluids), stable
dispersions of magnetic materials in liquids, are widely
used systems in different applications including
technical, industrial and biomedical fields. The
stabilization of these fluids takes place after a single
layer of surfactants covers the surface of the magnetic
particles, which is enough to avoid the particle
SPE 131272 5
aggregation in various external conditions including
magnetic fields and temperature effects. The advantage
of surfactant with FF over surfactant alone is that it can
be used for reservoir temperatue upto 140
o
deg. C.
Additionally it will assist to reduce the viscosity of the
reservoir fluid. The addition of surfactants decreases
the packing density of the ferroparticles while in its
activated state. This decreases the fluids on-state
viscosity, resulting in a "softer" activatedfluid.

Ferrofluid Enhanced Surfactant:

Stabilization of ferrofluids based on polar carriers
is a more complicated problem, and a single surfactant
layer around the magnetic particles providing only
repulsion between particles in the fluids is not enough.
Recently, methods of double sterical stabilization were
developed for several classes of polar carriers. The
technique implies that after the surfactant of one type is
adsorbed on the particle surface through chemical
adsorption, the surfactant of the same or another type
(depending on the adsorption properties) is adsorbed
on the previous layer through physical adsorption.

Ferrofluid enhanced surfactant fluid:

A magnetic fluid, (MF) consists in chemical
stabilized and dispersed magnetic nanoparticles in a
carrier liquid. Based on their complex characteristics
given by the magnetic component (magnetite stabilized
with oleic acid) and the liquid carrier where this one is
dispersed (hydrocarbons, especially oil compounds),
there is the possibility to use them in separation
processes through extraction of oily compounds from
aqueous systems. This process consists in oily
component distribution between the liquid carrier of
the ferrofluid and the aqueous phase.
Rheology of Ferrofluids :

Figure 3. McTague, J. Chem. Phys., vol. 51, no. 1,
1969, p. 133-6
In the above graph we thee the magnetic field
dependence of the viscosity for magnetic field parallel
and perpendicular to flow.
Perpendicular
Parallel

The viscosity coefficients of ferrofluids can be
manipulated by external magnetic field: the so-called
magnetorheological effect. In the classical experiment
of McTague,( McTague, J. Chem. Phys., vol. 51, no. 1,
1969, p. 133-6) the rotational viscosity of a suspension
of Cobalt nanoparticles was measured with external
magentic field applied parallel and perpendicular to the
flow direction, respectively.

Ferrofluid flow in Horizontal 2D Media:

(Experimental Studies of the Flow of Ferrofluid in
Porous Media Sharon E. Borglin, George J. Moridis
and Curtism. Oldenburg Earth Sciences Division,
Lawrence Berkeley National Laboratory, University of
California, Berkeley, California 94720, U.S.A)

In order to visualize and further understand the flow of
ferrofluid in porous media, ferrofluid was mobilized
through sand beds by the application of a magnetic
field. The porous media consisted of horizontal
shallow beds (1 cm thick) of the saturated S2 sand in
trays with dimensions of 0.1m * 0.12m. After
saturating the sand-filled trays with water, the sand
surface was smoothed and left exposed. Ferrofluid was
injected into the sand to form an initial circular
ferrofluid distribution. An external field was then
applied using a stack of 5 PM magnets. Typical results
of a sand-bed experiment are shown in Figure below.

a b c

Figure 4. Horizontal movement of FF2 ferrofluid
from left to right with an initial circular injection
through water-saturated S2 sand. The dark band on
the right side of each frame indicates the location of
the 5-stacked PM magnets. Frames are at 0, 23, and
43min. (Scale is in centimeters)

Image (a) shows the initial injection of 0.5ml of
FF2 ferrofluid into the sand tray at a distance of 0.1m
from one side of the tray. The magnet was then placed
on the opposite edge of the tray (the right side in the
6 SPE 131272
image) so that the center of the sand was aligned with
the magnetic pole. Images (b) and (c) depict the
ferrofluid distribution at 23 and 43min after injection.
The ferrofluid initially follows a direct pathway toward
the center of the magnet. As the ferrofluid reaches the
end of the tray, the magnet causes the ferrofluid to pool
in a semi-circle pattern.

Experiments with larger sand trays showed a
similar pattern of movement from distances of 0.25m.
At these distances, the force on the ferrofluid is
smaller, thus causing a decrease in the velocity of the
ferrofluid. Travel time for the 0.25m experiments is on
the order of 1 week. As the fluid approaches the
magnet, the velocity increases due to the increasing
magnetic field strength and field gradient. Regardless
of the initial injection configuration of the ferrofluid,
the end configuration is the same semi-circular shape,
which is controlled by the magnetic field.
Ferrofluid flow in Horizontal 2D Media:

Properties of porous media used in the experiments:

Designation Porosity Hydraulic D10 (mm)
Conductivity, K, (m/s)
S1 0.22 1:8 * 106 0.046
S2 0.46 4:2 * 105 0.23
S3 0.33 1:5 * 103 0.45
S4 0.34 3:6 * 106 0.065

Movement of ferrofluid in a vertical cell filled
with water-saturated S3 sand was conducted to observe
the effect of the magnetic field and gravity on the
movement of a ferrofluid in porous media. The cell
consisted of two glass plates, 23 cm wide and 25 cm
tall, separated by a 0.95 cm gap. The plates were sealed
on three sides, and the top was left open. Using a
syringe, the ferrofluid was injected into the unsealed
top of the cell, 20 cm from the magnet, as shown in
next figure. The ferrofluid experienced both
gravitational and magnetic forces as it migrated
downward. In this case, magnetic forces dominated and
the final accumulation is a semi-circular pool, with a
slight but discernible asymmetry due to the effect of
gravity.

A vertical cell filled with a combination of
water-saturated S3 and S4 sand was prepared to
observe the effect of permeability variation on the flow
of ferrofluid.

The cell, same as the one described above, was
filled with 15 cm of S3 sand, followed by a 3 cm layer
of S4 sand, and topped by a 6 cm layer of S3 sand. The
band of S4 sand was placed between the ferrofluid
injection point and the magnet. The movement of
ferrofluid through the sand after a period of 4 h is
shown in Figure 5 below.

This frame shows several important features of
the flow. The first feature is that the ferrofluid pools on
top of the S4 sand, but does not penetrate it. The
ferrofluid then begins migrating by moving along the
top of the lower permeability sand. Although the
ferrofluid is flowing through the entire width of the
ferrofluid-darkened band, the flow near the vicinity of
the magnet is greatly accelerated. In the S4 sand,
ferrofluid moves laterally and downward and
accumulates around the magnet. The ferrofluid is
forming an arc-shaped configuration, similar to the one
observed in the homogeneous system, which is
unaffected by the heterogeneity of the sand. The
presence of heterogeneities affected the flow path to
the magnet, but the final configuration is independent
of these heterogeneities.


Figure 5. Movement of FF2 ferrofluid through a
vertically oriented cell filled with S3 sand. Five
stacked PM1 magnets are located on the center of the
left side. Time elapsed is approximately 75min.

(Oldenburg Earth Sciences Division, Lawrence
Berkeley National Laboratory, University of
California, Berkeley, California 94720, U.S.A)

The potential of using ferrofluids and magnets to
create consistent and predictable spherical bulbs in the
subsurface is significant because many environmental
restoration activities require precise emplacement of
liquids in heterogeneous soils and sediments.

SPE 131272 7
References:


1. J. Philip, C.B.Rao, B.Raj, An optical probe for
qualitative/quantitative evaluation of defects in
ferromagnetic materials Patents 186620 &
186574.
2. Machado, A.L.C. Petrobras Internal Report
Cenpes/Diger/Seteq. CT 060/96.1996
3. Biao, W. & Lijian, D. "Paraffin Characteristics of
Paraffinic Crude Oils in China and the Methods of
Paraffin Removal and Inhibition", paper SPE
29954 presented at the 1995, Beijing, 1995
4. Burguer, E. Striegler, T.K."Studies of Paraffin
Deposition in the Trans Alaska Pipeline". JPT,
1986(6).
Figure 6. Flow of ferrofluid through a cell filled with
a combination of S3 and S4 sands. Five stacked PM1
magnets are located on the left side of the cell. Time
elapsed is 4 h.
5. Castellan, G. W.: Physical Chemistry, Addson
Wesley Publishing Company, and Inc. 1971.
6. S. Rocha. N.O: "Efeito do Campo Magnetico Na
Deposicao de Parafinas Na Explotacao do
Petroleo" M.Sc Thesis presented at Federal
University' of Rio de Janeiro (Dept of Chemistry),
June. 1997.

The experiments described here are aimed at
investigating the potential for controlling the
emplacement of ferrofluid in subsurface porous media.
To accomplish this, the behavior of ferrofluid was
observed in the lab in real porous media systems. The
following three conclusions can be drawn:
7. Donaldson, J. D. "The Application of Magnetic
Devices to Control Scale". Tube International.
1988, 39
8. Baker, S.B., Judd. S.J. "Magnetic Amelioration of
Scale Formation", Wat. Res. Vol. 30, No. 2 pp
247-260.
1) Permanent magnets create a predictable pressure
gradient in a magnetic fluid that leads to fluid flow,
2) Ferrofluid can be held in porous media in
predictable final configurations, which are
controlled solely by the magnetic field and are
unaffected by the flow pathway, initial injection
shape, or permeability of the porous medium,
9. Burguer, E. Striegler, T.K."Studies of Paraffin
Deposition in the Trans Alaska Pipeline". JPT,
1986(6).
10. Vieira, L.C. Petrobras Internal Report
Cenpes/Diger/Seteq 047/96.1996
3) Ferrofluid exhibits only limited retention effects in
the advancing front during flow through sandy
porous media.
11. Fifth Latin American and Caribbean Petroleum
Engineering Conference and Exhibition held in Rio
de Janeiro, Brazil, 30 August-3 September 1997,
and Presentation.
The development of this technology would provide
a valuable tool for controlling liquid emplacement
through the strong holding forces of the magnet in the
subsurface.
12. Magnetic fluids and Applications Handbook
(B.Berkovski, Ed.), Beggel House, New York,
1996.
13. Jordan, A. et al., J. Mag. Mag. Mater. 225, 118
(2001).
Summary:
14. Vks, L., Bica, D., Raa, M., Balau, O., Potencz,
I., Gheorghe, D., in Micro and nanostructures
Applicable for viscous reservoir fluid (10-500cp)
compared to conventional range of oil viscosity
used in surfactant flooding.
15. (D. Dascalu et al., Eds.), pp.127-157, Ed.
Academiei Romane, Bucharest, 2001.
16. Experimental Studies of the Flow of Ferrofluid in
Porous Media Sharon E. Borglin, George J.
Moridis and Curtism. Oldenburg Earth Sciences
Division, Lawrence Berkeley National Laboratory,
University of California, Berkeley, California
94720, U.S.A.
Fluid flow can be traced and steered which will
help in increasing accuracy of displacement
efficiency calculation.
Have Better Sweep Efficiency when compared to
surfactant flooding.
It can be used to obtain petrophysical data of the
reservoir.
17. Vks, L., Raa, M., Bica, D., J. Colloid Interface
Sci. 231, 247 (2000).

18. Bica, D., Vks, L., Avdeev, M.V., Balasoiu, M.,
Marinic, O., Stoian, F.D., Susan-Resiga.