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Magnetic Nanoparticles for Efficient Removal of Oilfield Contaminants:

Modeling of Magnetic Separation and Validation
Valentina Prigiobbe, Stevens Institute of Technology; Saebom Ko, Qing Wang, and Chun Huh, The University of
Texas at Austin; Steven L. Bryant, University of Calgary; Martin V. Bennetzen, Maersk Oil Research and
Technology Centre, Qatar

Copyright 2015, Society of Petroleum Engineers

This paper was prepared for presentation at the SPE International Symposium on Oilfield Chemistry held in The Woodlands, Texas, USA, 1315 April 2015.

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 reviewed by the Society of Petroleum Engineers and are subject to correction by the author(s). The material does not necessarily reflect
any position of the Society of Petroleum Engineers, its officers, or members. Electronic reproduction, distribution, or storage of any part of this paper without the written
consent of the Society of Petroleum Engineers is prohibited. Permission to reproduce in print is restricted to an abstract of not more than 300 words; illustrations may
not be copied. The abstract must contain conspicuous acknowledgment of SPE copyright.

In this work, we present the study of an efficient method of separating contaminants from water
produced from oil reservoirs, using magnetic nanoparticles (MNPs). Micron-scale, highly stable oil
droplets as well as divalent cations such as Ca2 can be removed from the produced water through the
adsorption onto functionalized MNPs. The method employs MNPs to initially attach to the oil droplets or
to the cations, and then to separate them from the liquid phase using a magnetic field. After separating out
the contaminant-free water, the MNPs can be regenerated and re-used. As the collection of the
contaminant-attached MNPs by the application of magnetic field gradient is a critical step for the process,
we developed a 1D mathematical model for the description of the dynamics of the MNP collection in the
framework of the sedimentation theory. The conservation equation for MNPs is coupled with the flux
function, which accounts for not only gravity force but also magnetic force and Brownian interaction. The
model describes both the behavior of colloidal particles during settling and the enhancing effects of the
magnetic field due to attraction of MNPs towards a magnet. Simulations were compared with measure-
ments from settling tests of a suspension of MNPs.

Large volumes of water are produced during the recovery of oil, which contain significant amount of
highly stable dispersed oil as well as high concentration of cations, such as Ca2, Mg2, and Na. On one
hand, for a safe disposal of the produced water, a purification treatment is required to reach the
concentration imposed by the government regulations. For example, in U.S., zero oil content in the case
of inshore technology and a daily maximum of 72 mg/L and a 30-day average of 48 mg/L (USEPA, 2004)
in the case of offshore production. On the other hand, for the reuse of the water in oil extraction, the
presence of cations can reduce significantly the efficiency of the oil recovery. This is particularly true for
chemical flooding, where polymers are used. Cations can bind to the sites of the polymer molecular chain,
forming undesirable precipitates.
Conventional technologies for the removal of oil and cations from produced water are, e.g., gas
flotation, gravity oil separation, membrane, nanofiltration, and reverse/forwards osmosis (Ahmadum et
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al., 2009; Ling et al., 2010; Malaeb and Ayoub, 2011). All these technologies have the drawback to be
energy-intensive and require a large space for their implementation. For off-shore oil extraction, compact
and cost-effective technological solutions are highly desirable and the use of magnetic nanoparticles
(MNPs) can be a promising alternative to conventional technologies. As the MNP-based processes are
characterized by simple and cost-effective implementation and, due to their high reactivity, a small
concentration of MNP is needed. Moreover, MNPs can be effectively separated magnetically isolating the
contaminant from the water and producing a small amount of sludge making the overall process safe and
environmentally friendly. MNPs are made of a core of magnetite that is surface-coated with either an
anionic or a cationic polymer. MNPs with anionic surface are added to high-hardness brine where they
adsorb multivalent cations on their reactive surface sites. On the other hand, MNPs with cationic surface
are added to an oil-in-water emulsion for their adsorption onto the oil-water interface. In both cases, upon
adsorption, the MNPs are separated applying a high-gradient magnetic field, leaving behind the contam-
inant-free water.
In this paper, we report the development of an efficient method of separating micron-scale, highly
stable oil droplets and divalent cations such as Ca2 from the produced water and brine. The method
employs the functionalized MNPs that attach to the contaminants and then are separated by the
application of a magnetic field gradient. In order to quantitatively described the MNPs separation, we
developed a 1-D model in the framework of the sedimentation theory with a conservation equation for
MNPs and a flux function that accounts for the gravity force, the magnetic force, and Brownian
interaction. The model describes both the well-established colloid settling and the enhancing effects of the
magnetic field. The flux function was derived from settling tests and the model was validated with
The paper is divided in five sections. Initially, we introduce the process in the Background section.
Then, in Material and Methods, the nanoparticles are described and the experimental procedure for the
settling tests is reported. In section Modeling, the governing and constitutive equations of the mathemat-
ical model are explained. In Results and Discussion, the model is analyzed and compared with experi-
ments. Finally, the Conclusion is drawn.

Before we describe the modeling of the magnetic separation of MNPs and its validation, a brief overview
of the novel method of efficiently removing the Ca2 and the oil droplets from the produced water is first
provided in this section.
Magnetic Removal of Ca2
Alkaline/surfactant/polymer (ASP) flooding is a combination process in which alkaline, surfactant and
polymer are simultaneously injected at the same slug (Sheng, 2013). Due to the synergetic effect of these
three components, ASP flooding received worldwide attention in both lab-scale studies and field trials.
However, the presence of divalent cations, such as Ca2, in the hard brine, can significantly affect the
performance of this process by reacting with polymers to form precipitations irreversibly. Therefore,
removal of divalent cations from brine becomes extremely important for success of an ASP flooding.
Conventional technologies to remove divalent cations, such as thermal separation and membrane sepa-
ration, are generally labor-intensive and costly. Other than that, by considering the limited space for
offshore operation, a technology with high efficiency, low-energy consumption and easy-manipulation
will bring tremendous benefits not only to the ASP flooding process but also to other upstream operations.
Due to the large surface area, a great number of active sites and low diffusion resistance, nanoadsorbents
are considered as one of the best candidates to remove oilfield contaminates. Compared with the
traditional adsorbents, such as carbon nanotubes and nanoporous silica, magnetic adsorbents along with
the contaminates can be separated directly under the magnetic field without the need of additional
SPE-173786-MS 3

centrifugation or filtrations, which make the separation easier and faster. We are studying an efficient and
recyclable method of Ca2 removal by use of polyacrylic acid (PAA) functionalized magnetic nanopar-
ticles (PAA-IOMNPs) whose scheme is shown in Figure 1. During this process, the PAA functionalized
IOMNPs are dispersed into brine. After the adsorption equilibrium of Ca2 on the surface of PAA-
IOMNPs is reached, a magnetic field is employed to separate the nanoparticles and Ca2 from water. The
collected PAA-IOMNPs can be regenerated by re-suspending them in the acid solution to remove the
adsorbed Ca2. Therefore, such method can be considered as a highly efficient, renewable and chemically
friendly method for cation removal from brine.

Figure 1Schematic illustration describing the process of cation and oil removal by functionalized MNPs.

Magnetic Removal of Oil Droplets

The removal of highly stable dispersed oil produced during oil recovery processes is very challenging,
especially, in offshore operations where space is limited due to its long residence time to separate.
Moreover, the expense of its treatment is one of largest oil-field operating cost. The use of MNPs to
remove highly stable dispersed oil from produced water is a promising way to overcome difficulties that
the current produced water treatment technologies faced on, such as platform space constraints, hazardous
waste generations, and high energy consumption, due to the MNPs quick response to applied external
magnetic field to separate the MNP-attached oil droplets. Magnetic force can be orders of magnitude
larger than gravitational force, allowing much faster separation of MNPs attached on oil droplets from
dispersing water. A schematic of the process is reported in Figure 1. The attraction of MNPs is their
versatile and efficient surface modification through obtaining suitable polymer coating. Many researchers
developed various nanoparticle surface coating materials and methods that are appropriate for oilfield use.
The surface interaction between suitable polymer coated MNPs (SPMNPs) and contaminants can be
controlled by using different surface coating on SPMNP, depending on the surface charge state and the
salinity and pH of water and medium where oil is dispersed. Surface modified SPMNPs can be adsorbed
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on oil droplets through surface interactions between contaminants and the surface modified SPMNPs,
such as electronic attractive force. Batch-scale experiments were conducted to separate oil droplets on
which MNPs were attached from water. Experiments demonstrated that negatively charged oil droplets
was successfully separated from water using cationic surfactant or polymer coated MNPs, with oil
removal efficiency as great as 99.99%. Negatively charged MNPs did not separate negatively charged oil
droplet from water at all, indicating that the electrostatic attraction is the main interaction between oil
droplets and MNPs.
Further details about the processes are reported in Wang et al. (2014) and Ko et al. (2014).
Materials and Methods

Commercially available cationic surfactant-coated magnetic nanoparticle was used (202103 g/m3 of
magnetite as received; 1.18103 g/m3 of density, Ferrotech) to perform settling experiments. The nominal
particle diameter and particle saturation magnetization were 10 nm and 20 mT, respectively. Settling
experiments were carried out in a 3.7103dm3 glass vial of height 4.5 cm and internal diameter 1.5 cm.
Nanoparticle suspensions of height 2.8 cm, i.e., total volume 3.2103dm3, and concentration between
3.15103 and 202103 g/m3 were prepared using distilled water. They were vigorously shaken for about
1 min and then placed on the permanent magnet with a magnetic field in the direction of the gravitational
field (Figure 2). The experiments were conducted in the presence of a magnetic field generated by a cubic
permanent magnet (Ultra-High-Pull Neodymium Rectangular Magnet, McMaster-Carr, U.S.A.) of 2.54
cm length and of 0.5 T polarization. The time when the magnetic field was applied defined the beginning
of the settling test. The experiments were monitored continuously with an automatic camera (Nikon digital
SLS D7100, Nikon, U.S.A.) and images were taken every 30 minutes until steady state was reached, i.e.,
the level of the interface between the clear water and the settled solids was stationary. A ruler was placed
next to the vial to measure the height of the interface over time and a LED light panel (Light Beam
Industries, U.S.A.) was installed behind the suspension to enhance visibility. The images were analyzed
to determine the settling rate for the calculation of the flux function. Further details about the experimental
activity are given in Prigiobbe et al. (2015).

Figure 2Scheme of the experimental set-up.

Governing equations
Following the theory of batch sedimentation formulated by Kynch (1952) and then extended by Bustos
et al. (1999), we considered a suspension of monodisperse spherical superparamagnetic nanoparticles and
assumed that solid and fluid are incompressible, and there is no interaction among particles. The one
dimensional (1D) conservation law writes
SPE-173786-MS 5


for 0 z L, t 0, where L is the initial height of the solid-liquid mixture (m); n is the suspension
density (g/m3); and f(n,z) is the total mass flux function (g/m2s), given by (Shannon et al., 1964; Rhee et
al., 1986)

where v(n,z) is the velocity (m/s) of the suspension depending on the suspension density and the height

with vi(z) the velocity of either the single particle (vp(z), m/s) or single droplet (vd(z), m/s), and nmax
the maximum concentration of the settled solids (g/L). The velocity vi(z) in eq. 3 can be determined by
Newtons law considering all forces, within a viscous fluid, acting on a single magnetic particle and on
a single droplet with adsorbed magnetic nanoparticles. The expression for vi(z) are given the section
below. In eq. 1, D is the molecular diffusion coefficient (m2/s) given by the Stokes-Einstein equation for
Brownian motion

where kB is the Boltzmann constant (m2kg/(s2K)); T is the absolute temperature (K); d is the core
diameter of either a nanoparticle or a droplet (m); and is the fluid viscosity (Ns/m2). Under the
investigated conditions of 298 K and assuming the average diameter of nanoparticles floc of 140 nm and
of a droplet of 1.6 m, D is equal to 3.501012 and 2.891013 m2/s, respectively.
We solved the Riemann problem given by the following initial condition (Rhee at al., 1986; Bustos et
al., 1999; LeVeque, 2008): n(z, 0) nl if L z; n(z, 0) nr if 0 z L; n(z, 0) nmax if z 0, with
nl 0 nr nmax. Equation 1 was discretized with an explicit finite difference scheme based on the
Godunovs method to treat the nonlinear flux (LeVeque, 2008).

Constitutive equations
Settling velocity
The settling velocity of a nanoparticle and of a droplet are vectors with component along the z-axis parallel
to the direction of the gravitational field and of the largest field gradient. The settling velocity of a single
nanoparticle (vp, m/s) is given by (Prigiobbe et al., 2015)

where VP is the volume of a single nanoparticle (m3), is the fluid viscosity (Ns/m2), p and f are
the volume magnetic susceptibilities of the nanoparticle and of the fluid consisting of water containing
nanoparticles (-), 0 is magnetic permeability of air or vacuum (Vs/(Am)), B is the external magnetic
field gradient (T/m), p and f are the densities of the oil droplet and of water (kg/m3), respectively, and
g is the gravitational acceleration (m/s2).
The settling velocity of a single droplet (vd, m/s) coated with nanoparticle is instead given by (Ko et
al., 2014)
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where dd is the droplet diameter (m), VP is the total volume (m3) of the adsorbed nanoparticles onto
the droplet with VP cP Vd/p, with cp the concentration of nanoparticles per unit droplet volume (g/L),
Vd is the droplet volume (m3), d is the densities of the oil droplet (kg/m3). Figure 3 shows in parts a and
b the velocity of the single particle and of the droplet covered with nanoparticle, respectively, as a function
of distance from the magnet. Here, it is possible to see that the single particle velocity decreases much
faster with distance than the droplet velocity and that its magnitude throughout the system is 1-2 orders
of magnitude lower then vd.

Figure 3Variation of the velocity (a) of the single particle and (b) of the single droplet along the z-axis.

Further details about the modeling of enhanced settling of nanoparticles by a magnetic field as well as
on the derivation of the settling velocities are reported in our earlier works, Ko et al. (2014) and Prigiobbe
et al. (2015).

Results and Discussion

In this section, the simulation results of settling of a nanoparticle and nanoparticle-covered oil-droplet
suspension are reported and discussed. They are also compared with experimental results of tests
performed with MNPs.
The physical properties of the system considered in the calculations are listed in Table 1.
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Table 1Average values of the physical system parameters considered for the calculations.
Radius, rp (m) 6.15108
Density, p (g/m3) 1.18106
Magnetic susceptibility, p (-) 5.011
Magnetic permeability of air, 0 (Tm/A) 1.26106
Oil droplet
Radius rd, (m) 1.7106
Density d, (g/m3) 7.30105
Volume fraction of the dispersed oil droplets, (-) 0.05
Coverage, fc(-) 0.5
Viscosity, f (Pas) 1.00103
Density, f(g/m3) 1.00106
Magnetic susceptibility. f (-) -9.05106

Analysis of the settling behavior Here, the dynamics of the suspension containing nanoparticles and oil
droplets covered with nanoparticles is investigated. First, the effect of nanoparticle diameter, suspension
concentration, and magnetic field intensity on the settling behavior of a fluid with dispersed nanoparticles
is analyzed. Second, the effect of droplet size and coverage on the settling of a suspension of oil droplets
covered with nanoparticles is studied. Therefore, simulations are performed considering the single particle
settling velocity (eq. 5), for the former case, and considering the single droplet velocity (eq. 6), for the
latter one. In both types of calculations, the flux function is given by eq. 2.
Figure 4 through 6 show the concentration profiles of a nanoparticle suspension at selected values of
nanoparticle diameter, suspension concentration, and magnetic field intensity, respectively. As the particle
size increases (Figure 4), the suspension settles faster. A sharp upper front in the concentration profile
travels downwards at speed increasing with particle size, as expected given eq. 5 where vp d2.
Moreover, also the sediment bottom moves upwards faster as the diameter increases indicating that the
time required by the system to reach steady state becomes shorter. The effect of the initial concentration
is instead less important on the speed of the overall settling process. As the initial concentration of the
nanoparticles increases (Figure 5), the upper interface migrates downwards slower due to the hindering
effects among the nanoparticles. The effect of the magnetic field intensity regulated by the polarization
of the magnet is shown in Figure 6. Here, it is possible to see that the magnetic field strongly influences
the shape of the concentration profiles. At the lowest polarization of 0.001 T (Figure 6.a), the profile
resembles the behavior in classical settling were two concentration fronts (Rhee et al., 1986), one moving
downwards and the other moving upwards form. As the magnetic field increases a local minimum forms
nearby the bottom due to the large velocity of the single particle. In that location, the gradient of the
magnetic field is significant and, hence, the single particle velocity is very large, given the relationships
vp B2 in eq. 5.
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Figure 4 Effect of the nanoparticle diameter. Normalized height as a function of normalized suspension concentration after 5 hr.
(a) d 20 nm, (b) d 100 nm, (c) d 400 nm. The values of the physical properties of the system are as listed in Table 1.

Figure 5Effect of the nanoparticle suspension concentration. Normalized height as a function of normalized suspension concentra-
tion after 5 hr. (a) n/nmax 0.2, (b) n/nmax 0.5, (c) n/nmax 0.8. The values of the physical properties of the system are as listed
in Table 1.
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Figure 6 Effect of the magnetic field intensity due to magnet polarization. Normalized height as a function of normalized suspension
concentration after 5 hr. (a) J 0.001 T, (b) J 0.01 T, (c) J 0.1 T. The values of the physical properties of the system are as listed
in Table 1.

Similar analysis was carried out for the settling of oil droplet covered with nanoparticles. Figure 7
shows the concentration profiles of droplets at selected increasing values of droplet diameter, maintaining
the same mass of nanoparticles adsorbed onto the droplet surface, and, therefore, at decreasing coverage.
As the droplet size increases from the minimum measured value to the maximum one, the concentration
profiles presents an accumulation of droplets at the top of the system. The profile in Figure 7.a resembles
the behavior observed in the earlier figures (i.e., Figure 4 through 6) for the settling of a nanoparticle
suspension. In this case, the velocity is positive throughout the domain and the droplets move towards the
bottom accumulating thereafter. As the droplet size increases (Figure 7.b and c), the buoyancy due to the
gravitational force becomes more important. Particularly, far from the magnet where the magnetic field
gradient is negligible. In this part of the domain, the velocity is negative determining a migration upwards
of the particles. By increasing the coverage this behavior could be counteracted. As the coverage increases
the settling of an emulsion under the effect of a magnetic field can be adjusted, i.e., an upper interface
between clear water and emulsion moving towards the bottom of the system and a lower interface of
settled droplets moving upwards.
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Figure 7Effect of the droplet size assuming the same mass of nanoparticles have adsorbed onto the droplet surface, namely, 11013
g. Normalized height as a function of normalized number of droplets for unit volume of aqueous solution after 5 min. (a) dd 0.57
m, fc 0.5, (b) dd 1.6 m, fc 0.06, (a) dd 2.6 m, fc 0.03. The values of the physical properties of the system are as listed in
Table 1.

Comparison between the model and nanoparticle settling experiments Settling tests of a nanoparticle
suspension were performed and the behavior was recorded with a digital came over time. All tests were
conducted in a series of vials of 2.8 cm height, under the influence of magnetic field. Overall, the process
was characterized initially by the development of an interface between the clear water and the suspension,
which slowly moves towards the magnet. As the suspension is concentrated, their agglomeration occurs,
which speeds up the separation, considerably. Figure 8 reports and compares the numerical simulation
under the applied experimental condition with the images recorded during that test (Prigiobbe et al., 2015).
The upper interface in an early time and the lower interface in the later stage of the process can be
described well by the model; however, the later evolution of the upper interface does not corresponds to
the experimental observations. The recorded images show a stationary upper interface, while the color of
the nanoparticle suspension becomes lighter over time. This behavior may indicate a decrease in particle
density due to particle aggregation. Similar observations were made by De Vicente et al. (2000) and
Phenrat et al. (2007) and they ascribed this to aggregation because of particle magnetization. Part f of
Figure 8 shows also the system at steady state, which is reached at about 3.5 days.
SPE-173786-MS 11

Figure 8 Numerical simulations compared with experimental results of nanoparticle suspension settling. The value of the initial
concentration is 50.46103 g/m3 and the particle of average diameter is 142 nm. The sediment normalized height at steady state is 0.21
and it is attained at 3.5 d. No compaction of the settled solids was observed (Modified from Prigiobbe et al., 2015).

In this paper, we have presented a study for the development of an efficient method of separating divalent
cations and highly stable oil droplets from the produced water. The method employs the functionalized
magnetic nanoparticles, which attach to contaminants, and they are then separated by the application of
a magnetic field. The process is a promising alternative to conventional technologies as it is characterized
by simple and cost-effective implementation, and the MNPs can be regenerated and re-used, thereby
avoiding use of chemicals for the removal process. We implemented a 1-D mathematical model for the
description of the MNPs settling both as individual particles and adsorbed onto oil droplets. The models
were built in the framework of the sedimentation theory with a conservation equation for MNPs and a flux
function that accounts for gravity and magnetic forces. The model describes the well-established colloid
settling and also the enhancing effects of the magnetic field. It however is unable to reproduce an
intermediate stage of the separation process, probably because of the agglomeration of the nanoparticle
due to magnetization which was not included in the model.

The authors wish to thank Maersk Oil Management for permission to publish this work.

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