J Nanopart Res (2017) 19:132
DOI 10.1007/s11051-017-3826-6
RESEARCH PAPER
Amine functionalized magnetic nanoparticles for removal
of oil droplets from produced water and accelerated magnetic
separation
Saebom Ko & Eun Song Kim & Siman Park &
Hugh Daigle & Thomas E. Milner & Chun Huh &
Martin V. Bennetzen & Giuliano A. Geremia
Received: 22 November 2016 / Accepted: 8 March 2017
# Springer Science+Business Media Dordrecht 2017
Abstract Magnetic nanoparticles (MNPs) with surface
coatings designed for water treatment, in particular for
targeted removal of contaminants from produced water
in oil fields, have drawn considerable attention due to
their environmental merit. The goal of this study was to
develop an efficient method of removing very stable,
micron-scale oil droplets dispersed in oilfield produced
water. We synthesized MNPs in the laboratory with a
prescribed surface coating. The MNPs were
superparamagnetic magnetite, and the hydrodynamic
size of amine functionalized MNPs ranges from 21 to
255 nm with an average size of 66 nm. The initial oil
content of 0.25 wt.% was reduced by as much as 99.9%
Electronic supplementary material The online version of this
article (doi:10.1007/s11051-017-3826-6) contains supplementary
material, which is available to authorized users.
S. Ko (*) : H. Daigle : C. Huh
Department of Petroleum and Geosystems Engineering,
University of Texas, Austin, TX, USA
e-mail: saebomko@austin.utexas.edu
E. S. Kim : T. E. Milner
Department of Biomedical Engineering, University of Texas,
Austin, TX, USA
S. Park
Department of Civil, Architectural and Environmental
Engineering, University of Texas, Austin, TX, USA
M. V. Bennetzen
Maersk Oil Corporate, Københavnsområdet, Denmark
G. A. Geremia
Maersk Oil Research and Technology Centre, Doha, Qatar
in separated water. The electrostatic attraction between
negatively charged oil-in-water emulsions and positive-
ly charged MNPs controls, the attachment of MNPs to
the droplet surface, and the subsequent aggregation of
the electrically neutral oil droplets with attached MNPs
(MNPs-oils) play a critical role in accelerated and effi-
cient magnetic separation. The total magnetic separation
time was dramatically reduced to as short as 1 s after
MNPs, and oil droplets were mixed, in contrast with the
case of free, individual MNPs with which separation
took about 36∼72 h, depending on the MNP concentra-
tions. Model calculations of magnetic separation veloc-
ity, accounting for the MNP magnetization and viscous
drag, show that the total magnetic separation time will
be approximately 5 min or less, when the size of the
MNPs-oils is greater than 360 nm, which can be used as
an optimum operating condition.
Keywords Produced water treatment . Oil removal .
Superparamagnetic nanoparticles . Magnetic separation .
Aggregation
Introduction
Water shortages and imbalance of water demand and
supply are a serious issue worldwide (WWAP 2015).
Recently, intensifying energy production activities, such
as unconventional oil and gas production, have required
a high water demand, resulting in an increasing compe-
tition for fresh water with other necessary human activ-
ities (Arnold et al. 2004; Gregory et al. 2011; Jacobs
132 Page 2 of 14
2016; Vengosh et al. 2014). Along with the increasing
demand for fresh water for oil and gas production, a
significant volume of water is also produced during oil
recovery, as much as 20 times the volume of produced
oil, which requires treatment and safe disposal (Olsson
2015). Produced water management is one of the largest
oilfield operational expenditures (Plebon 2006).
Produced water contains highly stable micron-
size dispersed oil, which makes water treatment
difficult. Conventional technologies currently
employed to treat produced water, such as gas flo-
tation, coalescers, gravity oil separation, mem-
branes, and chemical oxidation (Fakhru’l-Razi
et al. 2009), have difficulty in removing such dis-
persed oil to meet the requirements for discharging
or re-injection, as water quality standards and regu-
lations become more and more stringent (Helland
et al. 2008). Therefore, there have been increasing
efforts to find an efficient and cost-effective tech-
nology to treat produced water and reduce water
demand (Fakhru’l-Razi et al. 2009).
The oil and gas industry is currently interested in using
nanotechnology for oilfield operations. The main advan-
tage of nanotechnology is the size of nanoparticles (NPs),
whose diameters range from 1 to 100 nm, giving them a
very large surface area per unit mass. A number of review
papers on nanotechnology applications in oil and gas
production have been published (Amanullah and
Ramasamy 2014; Bennetzen and Mogensen 2014; El-
Diasty and Ragab 2013; Kapusta et al. 2011; Ko and
Huh 2017; Kong and Ohadi 2010; Krishnamoorti 2006;
Matteo et al. 2012; Mokhatab et al. 2006; Pourafshary
et al. 2009; Saggaf 2008; Vipulanandan et al. 2015). The
nanotechnology applications under development, in par-
ticular for the use of silica and iron oxide NPs, include CO2
foam for enhanced oil recovery (EOR) (Worthen et al.
2015), enhanced reservoir imaging (Rahmani et al.
2015), heavy oil mobilization, rheology control, hydrate/
wax deposition prevention in pipes (Mehta et al. 2014),
produced water treatment in upstream and downstream
operations (Ko et al. 2014, 2016), and desalination
(Wang et al. 2014, 2017).
Among a wide variety of NPs, the use of
superparamagnetic iron oxide NPs has drawn particular
attention due to their unique properties (Ko and Huh
2017). Various magnetic nanoparticle (MNP) surface coat-
ing materials and methods have been developed for appro-
priate use in the oilfield (Bagaria et al. 2013; Wang et al.
2014; Yoon et al. 2011, 2012). The most widely
J Nanopart Res (2017) 19:132
investigated MNPs for produced water treatment are mag-
netite (Fe3O4) and maghemite (γ-Fe2O3) (Ko et al. 2014,
2016; Wang et al. 2013, 2014, 2017). Surface-
functionalized MNPs can be adsorbed on a dispersed oil
droplet through surface interactions between droplets and
the surface-coated MNPs. The interactions can be con-
trolled by using different surface coatings on the MNPs,
depending on the surface charge state and the salinity and
pH of the water.
The main advantage of the use of MNPs to remove
dispersed oil droplets from produced water is their quick
response to move in a desired direction with an application
of an external magnetic field. Similar high-gradient mag-
netic separation (HGMS) technology has been commonly
applied in the mining and other industries for many years
to separate magnetic minerals, for example, Fe, Co, and Ni
(Yavuz et al. 2009). It is important that the magnetic force
be greater than other competing forces, such as the viscous
drag force and gravitational force, to accomplish high
recovery of magnetic particles. Using surface engineered
MNPs, HGMS has recently been applied in more compli-
cated separation in various fields, including the separation
of cells and proteins in biomedicine, as well as removal of
radionuclides, heavy metals, and nonpolar organic contam-
inants from water in environmental engineering (Moeser
et al. 2002).
Previously, we proved the concept that surface-coated
MNPs could remove oil droplets of synthetic oil from de-
ionized water (DIW) and developed a force balance model
to predict the separation velocity of MNPs attached on the
droplet when subjected to a magnetic field gradient (Ko
et al. 2014; Prigiobbe et al. 2015a, b). As an extension of
the above study, we report here on the synthesis and
surface modification of MNPs the evaluation of crude oil
separation from seawater by MNPs and the prediction of
magnetic separation velocity and time. We also made
detailed visual observations of the dynamics of oil-water
separation, employing optical and fluorescent microscopy,
for a mechanistic understanding of the oil-water separation
process.
Materials and experimental methods
Synthesis and surface fabrication of MNPs
The co-precipitation (co-ppt) method was used to synthe-
size MNPs under alkaline conditions. An aqueous mixture
of FeCl2∙4H2O (Fisher Scientific, ACS grade) and
J Nanopart Res (2017) 19:132
FeCl3∙6H2O (Fisher Scientific, ACS grade) at a molar ratio
of 1:2 was dissolved in ultra-purified DIW, followed by the
addition of citric acid (monohydrate, Fisher Scientific,
ACS grade) as a stabilizer. NH4OH (20%, Fisher Scientif-
ic, TraceMetal™ grade) was quickly added to the mixture
after the mixture temperature reached 90 °C, while vigor-
ously mixing under nitrogen purging. Black particles were
immediately precipitated. The mixing continued for 2 h at
90 °C in a nitrogen atmosphere. The mixture was then
cooled down to room temperature in an ice bath while
stirring. The particles were collected by a permanent mag-
net and washed 4–5 times with DIW.
The silanization process was employed to graft the MNP
surface with amine using 3-amino propyltriethoxysilane (3-
APTES) (Acros Organic, ≥99%) (Bagaria et al. 2013; Wang
et al. 2014; Xue et al. 2014). After 1 h hydrolysis of 3-
APTES in acidic solution (pH∼4.6) of glacial acetic acid
(Fisher Scientific, ACS grade), pH was adjusted to around 8,
followed by adding re-dispersed MNPs dropwise to hydro-
lyzed 3-APTES solution. The mixing continued for 24 h at
65 °C. The mixture was then cooled down to room temper-
ature while stirring. Amine functionalized MNPs (A-MNPs)
were collected by a permanent magnet and washed three
times with DIW.
Polyacrylic acid (PAA, Sigma Aldrich, 8 kDa) was
grafted on the surface of A-MNPs (Wang et al. 2014).
After activating the carboxylic group of PAA to conju-
gate with the primary amine group on A-MNPs using 1-
ethyl-3-(3-dimethylaminopropyl) carbodiimide (Sigma
Aldrich), the mixture was mixed for 24 h at room
temperature. PAA grafted A-MNPs (PAA-MNPs) were
collected by a permanent magnet and washed three
times with DIW. The process of MNP synthesis and
surface fabrication is summarized in Fig. 1.
Oil droplet removal
An oil-in-water (O/W) emulsion containing 5 wt.%
crude oil of the total acidic number of 0.15, 2.9, and
4.5 was produced using a sonifier gun for 20 min at 40%
Fig. 1 The process of MNP synthesis and surface fabrication
Page 3 of 14 132
amplitude after increasing pH to ∼10 to dissolve the
alkaline soap components from oil. The employed
method to generate the O/W emulsion in this study
was established in our lab through trial and error to
make small and stable emulsions. The O/W emulsion
was diluted tenfold with DIW, American Petroleum
Institute (API) standard brine (2% calcium chloride
and 8% sodium chloride), and synthetic seawater
(SSW, Ricca Chemical Company) to make 0.5 wt.%
oil, followed by pH adjustment to ∼8.2. Various vol-
umes of A-MNPs or PAA-MNPs were added to 1.6 mL
of 0.5 wt.% O/W emulsion. Then, water was added to
make a total volume of 3.2 mL. After the mixtures of A-
MNPs or PAA-MNPs and emulsion shaken on an orbital
shaker, the mixture was placed on a 1″ × 1″ × 1/2″ block
nickel-plated neodymium-iron boron permanent magnet
to separate oil droplets with attached A-MNPs or PAA-
MNPs from water. The magnetic field strength varied
from 0.44 T in the middle of the magnet to 0.76 T on the
edge. A schematic illustration of oil droplet removal,
modified from Ko et al. (2014), is shown in Fig. 2.
Dynamics of magnetic separation of MNPs
After dying O/W emulsions with fluorescent lipid of
ammonium 1,2-dioleoyl-sn-glycero-3-
phosphoethanolamine-N-(lissamine rhodamine B sulfo-
nyl) (Avanti Polar Lipids), the movement of MNPs-oils
separating from water was observed using fluorescent
microscopy (Zeiss Axiovert 200 M Widefield) with and
without an external magnetic field. The permanent mag-
net with the size of 1/8-in. cube and the magnetic
strength of 50 mT was used as an external magnetic
field to let oil droplet separation process continue for a
reasonable time to make a movie. The progress of MNP
aggregation after oil droplet attachment was observed
using an optical microscope (Nikon). The size of aggre-
gated MNPs was measured using a ruler on microscopic
images and converted to a corresponding actual size
based on a length of a ruler bar on the images. Magnetic
132 Page 4 of 14
Fig. 2 Schematic illustration of batch experiment setup for oil droplet removal using MNPs (modified from Ko et al. (2014))
separation of oil droplets with attached MNPs from
water was continuously monitored with an automatic
camera, and images were taken at a certain interval until
the level of the interface between clear water and MNPs
remained the same.
Experimental analyses
Sizes and zeta potentials of synthesized and surface-
fabricated MNPs were measured in DIW at room tem-
perature with dynamic light scattering (DLS, Zetasizer
Nano ZS, Malvern Instrument). Zeta potentials of crude
oil and oil droplet-attached MNPs were also measured
with DLS. Morphology of MNPs was observed using
transmission electron microscopy (TEM, FEI Tecnai
TEM-Electron), operated at 80 kV on a carbon grid
coated with Cu. All measurements were carried out with
about 100-fold diluted samples in DIW.
Oil concentrations in separated water were measured
by chemical oxygen demand (COD)/closed reflux, col-
orimetric method (Cleceri et al. 1998). Chloride inter-
feres with the COD measurement through reaction with
catalysts for oxidation reactions of organic components
of a sample, resulting in the formation of precipitate.
J Nanopart Res (2017) 19:132
Measurement
of oil content in
separated
clean water
Therefore, in the case of oil droplet removal experiments
in brine solution, oil concentration from separated water
was measured using UV-VIS spectrophotometer at a
wavelength of 400 nm after extracting oil from separat-
ed brine solution with methylene chloride (Fischer Sci-
entific, Stabilized/ACS grade, ≥99.5%) (Tellez et al.
2005).
Percent removal of oil (R) was determined as
ðC 0 −C Þ
R¼  100; ð1Þ
C0
where C0 = oxygen demand in 0.25 wt.% of crude oil
(mg O2/L) for COD measurement or oil content in brine
solution (wt.%) and C = oxygen demand in separated
water (mg O2/L) or oil content in separated brine solu-
tion (wt.%).
Fe concentrations in MNPs after synthesis and sur-
face fabrication were measured using inductively
coupled plasma optical emission spectrometry (ICP-
OES, Agilent 710-ES) at a wavelength of 283.204 nm.
NPs were dissolved in 30% (by mass) nitric acid (Fisher
Scientific, TraceMetal™ grade), and then diluted in
DIW by 10 times to reduce nitric acid concentration to
J Nanopart Res (2017) 19:132
less than 4 wt.%, which is the allowable concentration of
nitric acid for ICP.
Modeling for magnetic separation of MNPs
We modified a previously developed mathematical
model for the magnetic separation of MNPs (Ko
et al. 2014; Prigiobbe et al. 2015a, b) to estimate
the total time and velocity of magnetic separation
of MNPs attached on oil droplets. Considering
Newton’s second law,
∂vd
!


!
!
md ⋅ ¼ F b þ F drag þ F m ;
∂t
 

!
F b ¼ V d ρd −ρ f g;


!
F drag ¼ −3πηd d vd ;

! h i
F m ¼ ðm⋅∇BÞ ¼ V p ðχp −χ f Þ=2 μ0 ∇B2 ;
where md is the total mass of an oil droplet and MNPs
attached on it; vd is the magnetic separation velocity of

!
an oil droplet with attached MNPs; F b is the buoyancy


!
!
force; F drag is the drag force; F m is the magnetic force;
Vd is the volume of oil droplet (m3); ρd and ρf are the
densities of the oil droplet and of water (kg/m3), respec-
tively; g is the gravitational acceleration (m/s2); ∇B is
the external magnetic field gradient (T/m); m is the
magnetic dipole moment (N•m/T); Vp is the volume of
aggregated MNPs adsorbed on an oil droplet (m3); χp
and χf are the volume magnetic susceptibilities of the
NP and of water, respectively (unitless); and μ0 is mag-
netic permeability of air or vacuum (V•s/(A•m));
The velocity (m/s) of magnetic separation of MNP
aggregates which cover an oil droplet (MNPs-oil) (vd ) is
derived from the force balance (Eq. (2)), expressed as
  h  
V p ðχp −χ f Þ
vd ¼ 1 3πηdp =2 μ0 ∇B2 þ V d ρd −ρ f g ;
where η is the fluid viscosity (N•s/m ) and dp is the
3
diameter of an oil droplet covered with MNP
aggregates.
Page 5 of 14 132
To simplify the mathematical model, we assume:
a. MNP aggregates behave as a solid, single, spherical
particle;
b. There is no interaction between MNP aggregates;
c. The applied external magnetic field is strong enough
to magnetize MNPs to saturation level;
d. The magnetic field is homogeneous on the surface
of the permanent magnet (0.44 T);
e. The exact value of vd is time-varying velocity. Ac-
celeration of the particle, however, decreases imme-
diately, and the velocity reaches terminal velocity
due to its nano-size (Kuhn et al. 2006). Since it
reaches to the terminal velocity instantaneously,
ð2Þ
the system is quasi-steady state such that the mag-
netic separation velocity between two finite time
segments is constant, i.e., ∂v∂td ¼ 0.
ð3Þ
ð4Þ Experiment results and discussion
MNP characterization
ð5Þ
Hydrodynamic sizes of citrate-stabilized MNPs and
A-MNPs measured with DLS were 51 and 66 nm,
respectively. Zeta potential of citrate-stabilized
MNPs and A-MNPs at pH 8.2 was −41 mV and
+26 mV in DIW, respectively, which indicates the
successful functionalization of amine. The surface
charge of A-MNPs is positive due to protonation
of the terminal primary amine group (−NH2) at
pH 8.2, for which the pKa value is 10.66. The
pH point of zero charge (pHPZC) of A-MNPs was
around pH 10.6. According to previous work by
Wang et al. (2014), the hydrodynamic size and
zeta potential of PAA-MNPs were 152 nm and
−38 mV at pH 7, respectively. The surface charge
of PAA-MNPs is negative due to the negative
charge on oxygen (−COO−) after conjugating car-
boxylic acid groups of PAA to the terminal amine
 i of A-MNPs. The negative value of zeta potential
confirms the successful surface grafting of PAA on
MNPs.
ð6Þ
TEM images showed a small degree of aggre-
gation of MNPs and A-MNPs, whose individual
particle diameter was around 10 nm (Fig. 3).
MNPs are known to form small aggregates, which
132 Page 6 of 14
Fig. 3 TEM images and the DH (a)
distribution of MNPs. a TEM
images of MNPs. b TEM images
of A-MNPs. c DH distribution of
MNPs and A-MNPs. Average
DHs for MNPs and A-MNPs are
51 and 66 nm, respectively
(c)
remain stable once formed to minimize high sur-
face energy by strong magnetic dipole-dipole at-
tractions along with Van der Waals forces (Gupta
and Gupta 2005).
X-ray diffraction patterns of MNPs and A-MNPs
followed the characteristics of magnetite (Wang
et al. 2014). This showed that synthesized iron oxide
NPs were magnetite and polymer surface coating did
not change the crystallinity of iron oxide NPs. For
both MNPs and A-MNPs, high saturation magneti-
zation (Ms) values of approximately 90 emu/g Fe3O4
were obtained, and the Langevin curves showed the
absence of hysteresis, indicating that they are
superparamagnetic NPs (Fonnum et al. 2005;
Mehta et al. 2014; Wang et al. 2017; Yoon et al.
2011, 2012). APTES is a small molecule whose
molecular weight is 221.37 g/mol. As shown in
DLS measurements, the size difference between
MNP and A-MNP is about 15 nm. Due to the
similar particle sizes of MNP and A-MNP, Ms values
were determined to be similar.
J Nanopart Res (2017) 19:132
(b)
50 nm 50 nm
Oil droplet removal
An O/W emulsion in DIW with an initial oil content of
0.25 wt.% was reacted in various Fe concentrations of
A-MNPs and PAA-MNPs. Figure 4 shows the compar-
ison of percent removal of three different oils of
TAN = 0.15, 2.9, and 4.5, after reacting with 0.875 g/L
Fe of A-MNPs for 5 min at pH 8.2. The percent re-
movals of oil droplets with TAN = 0.15, 2.9, and 4.5
from DIW were 99.5, 97.9, and 96.4%, respectively. A-
MNPs having the opposite surface charge to oil droplets
were successfully attracted to and attached on negative-
ly charged oil droplets, resulting in neutralized surface
charge and making MNPs-attached oil droplets stick
together and form larger MNPs-oil droplet aggregates.
This allows efficient magnetic separation of MNPs-
attached oil droplets from water, which can be seen from
Eq. (6) with a large Vp. A larger value of TAN corre-
sponds to a greater acidity of crude oil. The greater the
negative surface charge density, the greater the particle
stability due to the stronger electrostatic repulsive
J Nanopart Res (2017) 19:132
Fig. 4 The comparison of the percent removal of different types
of crude oils in API, SSW, and DIW, after oil and A-MNPs, are
mixed. Fe concentration of A-MNP is 0.875 g/L. pH of A-MNP is
8.2. Initial oil content in water is 0.25 wt.%
forces. TAN 4.5 oil, having the greatest acidity among
three crude oils tested, will require the greatest amount
of A-MNPs to have the same level of removal efficiency
as the other lower TAN oils. Reacted with the same
amount of A-MNPs, the percent removal of TAN 4.5
O/W emulsion was slightly lower than that of the other
two. However, this amount of A-MNPs added to the
three different oils was sufficient to remove almost all
oil from water.
In API brine and SSW, the percent removals of oil
droplets were similar, regardless of the oil type (Fig. 4).
The percent removals of three different oils of
TAN = 0.15, 2.9, and 4.5 ranged from 98.9 to 99.6 in
API brine and from 98.2 to 99.2 in SSW after mixing A-
MNP and O/W emulsions overnight. The percent re-
movals of oil droplets were similar in the same condi-
tions of solution pH of 8.2 and Fe concentrations of
0.875 g/L.
The negatively charged PAA-MNPs were also mixed
with the TAN 2.9 and 4.5 oil dispersions, to investigate
whether the electrostatic interaction is indeed the major
interaction mechanism to remove oil droplets from wa-
ter. As seen in Fig. 5a, 0.25 wt.% O/W emulsion of TAN
2.9 and 4.5 oils remained untreated after mixing with
2 g/L PAA-MNPs overnight. Unreacted PAA-MNPs
(i.e., no oil attached) were collected at the bottom of
the reactor after magnetic separation. Zeta potentials of
TAN 2.9 and 4.5 oil droplets were −69 and −74 mV at
pH 8.2, respectively. This confirmed that the negatively
charged PAA-MNPs (−38 mV) and oil droplets repel
each other, causing oil droplets to remain in water even
after magnetic separation. In contrast with PAA-MNPs,
Fig. 5b shows clear water after magnetic separation
using A-MNPs whose surface charge is positive
Page 7 of 14 132
(+26 mV zeta potential). The major interaction mecha-
nism to separate oil droplets from water is therefore the
electrostatic attraction, which is consistent with previous
work by Ko et al. (2014, 2016).
The effects of Fe concentration of A-MNPs on oil
droplet removal are presented in Fig. 6. The initial oil
content of 0.25 wt.% was rapidly reduced to near zero
within 5 min after mixing with 1.75 and 0.875 g/L of Fe
in A-MNPs, while half of the initial oil content still
remained in separated water 15 min after mixing with
0.438 g/L of Fe. It took almost 3 h to remove oil droplets
from water to near zero concentration using 0.438 g/L of
Fe (see Fig. 6). It appears that the amount of terminal
amine groups available would be proportional to Fe
concentration, resulting in a greater density of surface
charge on MNPs. The kinetics of oil droplet removal
from water with 0.438 g/L Fe were slower than with
1.75 and 0.875 g/L Fe.
Figure 7 shows the reduction of oil content (TAN 2.9
and 4.5) in SSW with respect to mixing time between oil
droplets and A-MNPs. Initial oil content of TAN 2.9 and
4.5 O/W emulsions was 0.25 wt.%, and Fe concentra-
tion of A-MNPs was 0.875 g/L. The kinetics of oil
removal in SSW were slower than in DIW. The TAN
2.9 and 4.5 oil contents in separated SSW were reduced
to 0.037 and 0.17 wt.% from 0.25 wt.%, respectively,
after 5 min of mixing between A-MNPs and O/W emul-
sion; the oil contents were reduced to almost zero in
DIW (refer to Fig. 4). Ions present in SSW could inter-
fere with the interaction between oil droplets and A-
MNPs, competing with oil droplets for reactive sites of
A-MNPs. In addition, ions surrounding A-MNPs reduce
the thickness of the electrical double layer, reducing
particle stability. However, the amount of A-MNPs
added to the oil-in-SSW emulsions was enough to re-
move greater than 95% in 20 min for TAN 2.9 oil and in
60 min for TAN 4.5 oil.
Microscope observation of magnetic separation
Optical microscope images of TAN 2.9 O/W emulsion
are shown in Fig. 8a. The size of the spherical oil
droplets ranges from 0.2 to 10 μm. The progress of A-
MNP aggregation and oil droplet attachments with time
is shown in Fig. 8b. The hydrodynamic size of A-MNPs
by itself ranged from 21 to 255 nm with some degree of
aggregation already existing as shown in Fig. 3b. Opti-
cal microscope images show significant aggregation of
MNPs and oil droplets. The image in the middle of
132 Page 8 of 14
(a) PAA-MNP
Fig. 5 Photo images of oil droplet separation from water using
different surface charged MNPs. a TAN 2.9 (left) and 4.5 (right)
O/W emulsion (0.25 wt.% oil) and PAA-MNPs (2.0 g/L Fe). PAA-
MNPs are shown at the bottom of the reactor where a permanent
Fig. 8b, which was taken after 5 min of mixing, shows a
glimpse of coalesced oil (nude color objects) underneath
MNP aggregates (brown objects). There are also several
oil droplets not covered by MNPs in the image, some of
which seem to have been attached to MNPs due to the
increased MNP size, but the size of the MNPs might not
be large enough to be seen by optical microscopy. The
various sizes of coalesced oil droplets are also shown
around MNP aggregates and are believed to be present
within them as well.
The positively charged A-MNPs successfully over-
come the stabilization energy barrier between oil drop-
lets by neutralizing their charge, making them stick
together and grow into flocs, which can then easily be
magnetically separated from water. The proper contact
time in the rapid-mix chamber during the coagulation
process in the water treatment is typically 1 to 3 min to
produce larger particles, while insufficient mixing
Fig. 6 Reduction of TAN 2.9 oil content in separated water with
respect to mixing time between oil droplet and A-MNPs in differ-
ent Fe concentrations of A-MNPs at pH 8.2. Initial oil content in
water is 0.25 wt.%
J Nanopart Res (2017) 19:132
(b) A-MNP
magnet is placed. b TAN 2.9 O/W emulsion (0.25 wt.% oil) and A-
MNPs (0.875 g/L Fe). MNPs-oils were collected at the right-hand
side of the reactor where a permanent magnet is placed
results in incomplete particle growth. In our case, larger
aggregates of MNPs-attached oil droplets were formed
within 1 min after mixing them on an orbital shaker
table. Microscope observations indicate that the oil
droplet removal process using MNPs occurs very
rapidly.
As shown in Fig. 9 of the snapshot of the video clip,
fluorescent dye-tagged oil droplets were illuminated.
Smaller and brighter oil droplets are shown in the upper
layer of microscope-focus area and bigger and dimmer
in the lower layer. Before placing a permanent magnet,
most of oil droplets were slowly floating in the sample
chamber except a few whose size are big enough to be
settle down by the gravitational force. As soon as the
magnet was placed on the right-hand side, oil droplets
were quickly moved to the right (see the video clip in the
supplementary material).
Fig. 7 Reduction of oil content of TAN 2.9 and 4.5 in separated
SSW water with respect to mixing time between oil droplet and A-
MNPs. Initial oil content in water is 0.25 wt.%. Fe concentration of
A-MNPs is 0.875 g/L. pH of A-MNPs is 8.2
J Nanopart Res (2017) 19:132 Page 9 of 14 132

(a)

(b)

1min 5min 60min

Mixing time between oil droplets and A-MNP
Fig. 8 Optical microscope observations of oil droplets and MNP aggregates attached to oil droplets. a 0.25 wt.% O/W emulsion before
mixed with A-MNPs. b MNP aggregates attached on oil droplets after mixed with oil droplets for a certain time

Modeling magnetic separation
Determination of magnetic separation velocity and time
of free A-MNPs without oil
The progress of magnetic separation of MNPs by itself
was monitored continuously using a digital camera
every 10 min until the level of the interface between
the clear water and the particles was stationary, shown in
Fig. 10a. The complete water and MNP separation took
36 h for 0.438 g/L Fe, 60 h for 0.875 g/L Fe, and 72 h for
1.75 g/L of Fe. The interface between water and MNPs
started to appear at the top and bottom of the left-hand
side after a half hour, and it was clearly seen 2 h after

(a) (b)

Fig. 9 a Snapshot of the separation of fluorescent dye-tagged oil Fluorescent dye-tagged oil droplets are only shown in the image.
droplets with MNPs attached in action captured by fluorescent b The configuration of the fluorescent microscopy
microscopy (see a movie file in the supporting material).
132 Page 10 of 14
magnetic separation was started. The hydrodynamic size
of A-MNPs ranges from 21 to 255 nm with an average
size of 66 nm. About 91% of A-MNPs fell into the size
range of 28∼140 nm. As seen in the water-phase color of
images in Fig. 10a, most of the A-MNPs were collected
within 12 h.
The velocity and separation time for MNPs of differ-
ent (equivalent) sizes were estimated using Eq. (6).
Figure 10b shows a conceptual model of the system
(a)
(b)
Model System
L1 =1.5 cm : MNP
B = 0.44T
(d)
Fig. 10 a Images of magnetic separation progress with time
(0.435 g/L of Fe in A-MNP). b Conceptual model of the system.
c Analytical simulation results of magnetic separation velocity as a
function of normalized distance of z/L at various MNP sizes
J Nanopart Res (2017) 19:132
for the analytical simulation. Figure 10c, d presents
analytical simulation results of magnetic separation ve-
locity and time as a function of normalized distance of z/
L at various MNP sizes corresponding to DLS size
measurements using Eq. (6). The magnetic field induced
by a permanent magnet was described using the analyt-
ical solution derived by Ravaud and Lemarquand
(2009), and it matched well with measured values
Prigiobbe et al. (2015a). The parameter values used for
(c)
corresponding to DLS size measurement using Eq. (6). d Analyt-
ical simulation results of magnetic separation time as a function of
normalized distance of z/L at various MNP sizes corresponding to
DLS size measurement using Eq. (6)
J Nanopart Res (2017) 19:132
model calculations are listed in Table 1. The gravitation-
al velocity of 9.88 10−9 m/s is calculated for the average
size (66 nm) of A-MNPs, and the settling time by
gravity alone to the bottom of a reactor from the top of
water (2.8 cm) is 787 h. However, with the magnetic
force, it will take 2.7 h to collect 66 nm A-MNPs from
the left (the furthest from a magnet, z = 1) to the right
(the closest to a magnet, z = 0) in the model system,
where the total travel distance (L) is 1.5 cm, as shown in
Fig. 10b. Figure 10c, d shows the analytical simulation
results of the magnetic separation velocity and time of
A-MNPs as a function of the normalized particle travel
distance of z/L where particle sizes range from 24 to
240 nm. As particles get closer to the magnet, the
velocity of particles increases due to the larger magnetic
field gradient. The estimated total collection time is in
the range of 0.2 to 20 h, depending on the particle size.
The simulation results show some deviation from the
experimental results mainly because the electrostatic
interaction between particles is not considered in this
model. The greater the Fe concentrations of A-MNPs,
the greater the electrostatic force that the magnetic field
has to overcome. This model prediction provides the
approximate particle separation velocity and time at
each travel distance.
Determination of magnetic separation velocity and time
of MNPs-oils
Figure 11a shows the progress of magnetic separation of
MNPs-oils, which is continuously monitored at a certain
interval using a digital camera. The velocity and sepa-
ration time for MNPs-oils of different (equivalent) sizes
were estimated using Eq. (6), and the analytical
Table 1 Parameter values used for the model calculations
Parameter Value
A-MNP Average diameter, dp (m) 66 × 10−9
Density, ρp (kg/m )
3
5.17 × 103
Volume magnetic susceptibility, χp 5.03
Magnetic permeability of air, μ0 (T•m/ 1.26 × 10−6
A)
Oil Density, ρd (kg/m3) 0.973 × 103
droplet
Water Viscosity, η 1.00 × 10−3
Density, ρf (kg/m )
3
1.00 × 103
Volume magnetic susceptibility, χf −9.05 × 10−6
Page 11 of 14 132
simulation results are presented in Fig. 11b. These cal-
culations are more accurate than the ones for free A-
MNPs, because the charges of particles are neutralized
or reduced, resulting in negligible electrostatic forces.
The magnetic separation of MNPs-oils was monitored
using automatic camera at a certain time interval. When
0.875 g/L Fe of A-MNPs was reacted for 15 min with O/
W emulsion containing 0.25 wt.% oil with TAN 2.9,
MNPs-oils were collected almost instantly, and clear
water was obtained as shown in Fig. 5a. Unlike the
images shown in Fig. 10a, where the greater portion of
particles was collected at the top of the reactor due to the
stronger magnetic field at the top, there were no particles
at the top of the magnet. Because particles get bigger as
shown in Fig. 8c, the gravitational force also has an
effect on particles. For example, 255 μm MNPs-oils
will settle down to the bottom in 0.2 s by gravity alone.
Interestingly, when 1.75 g/L Fe of A-MNPs were
reacted with O/W emulsion, the magnetic separation
time depended on the mixing time, as shown in
Fig. 11a. This might be caused by free MNPs which
are not attached on oil droplets. However, as the mixing
time increases, the probability of collision increases
between free MNPs and between free MNPs and
MNPs-oils. As a result, the particles might get more
aggregated, and magnetic separation time gets shorter.
After A-MNPs were reacted with oil droplets for 5 min,
it took about 10 h to collect all particles magnetically.
When A-MNPs were reacted with oil droplets for
120 min, it took about only 5 min for complete magnetic
separation. Based on the calculation of velocity and total
time in the model system, the size of particles might be
grown to be greater than 360 nm, the total magnetic
separation time of which is approximately 5 min
(Fig. 11b). This result suggests that the concentration
ratio of MNPs and oil and the mixing time could be the
most important variables to get quick and effective oil
droplet separations from water.
Conclusions
Positively charged, in-house synthesized MNPs effec-
tively removed negatively charged oil droplets by as
much as 99.5% after 5 min of mixing between MNPs
and oil. The greater than 95% of initial oil content of
0.25 wt.% oil-in-SSW emulsion was removed within
20 min for TAN 2.9 oil and within 60 min for TAN
4.5 oil with 0.875 g/L Fe of A-MNPs. TAN 2.9 oil
132 Page 12 of 14
(a)
(b)
Fig. 11 a Images of magnetic separation progress of MNPs-oils at
different reaction time between oil droplets and A-MNPs as
1.75 g/L of Fe at pH 8.2. b Analytical simulation of the change
droplets was successfully removed by greater than 99%
with as low as 0.438 g/L Fe of A-MNPs. The kinetics of
oil droplet removal in SSW were slower than in DIW.
Based on microscope observations, the electro-
static attraction between negatively charged oil and
positively charged MNPs controls, the attachment
of MNPs to oil droplets, and the subsequent ag-
gregation of the neutralized MNPs-attached oil
droplets play a critical role in accelerated and
efficient oil droplet removal and magnetic
J Nanopart Res (2017) 19:132
of the total magnetic separation time of MNPs-oils as a function of
a MNP aggregate diameter in the range of 90 to 360 nm in the
model system using Eq. (6)
separation. Thus, the total magnetic separation
time was dramatically reduced to as short as 1 s.
Model calculations of magnetic separation velocity
show that the velocity of free A-MNPs depends critical-
ly on the magnetic field gradient and the particle size.
The total magnetic separation time of free A-MNPs
ranged from 0.2 to 20.4 h, depending on the particle
size. Contrary to the results with free A-MNPs, the total
magnetic separation took approximately 5 min where
the size of MNPs-attached oil droplet was grown to be
J Nanopart Res (2017) 19:132
greater than 360 nm after 2 h of mixing between oil
droplets and 1.75 g/L Fe of A-MNPs.
Removal of highly stable dispersed oil produced
during oil recovery processes is very challenging, espe-
cially in offshore operations where limited space does
not allow equipment with long residence time. The
expense of such treatment is also one of the largest
oilfield operating costs. The application of MNPs for
the oil and water separation process is a promising
technology, because it can be designed as a compact
system that generates less hazardous sludge. The MNPs-
based method of oilfield fluids separation reported here
is a potentially green, promising technology. Our work
has provided underlying mechanisms and critical pa-
rameters for optimization of the process.
Acknowledgements The authors would like to thank Dr. Qing
Wang at Rice University for the discussions and help in synthesis
and characterization of MNPs and Maersk Oil Management for
permission to publish this work.
Compliance with ethical standards This study was funded by
the Maersk Oil in Doha, Qatar, and the Nanoparticles for Subsur-
face Engineering Industrial Affiliates Program at the University of
Texas at Austin (member companies: Baker-Hughes, Nissan
Chemical, and Foundation CMG).
Conflict of interest The authors declare that they have no con-
flict of interest.
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