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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 in separated water. The electrostatic attraction between
coatings designed for water treatment, in particular for negatively charged oil-in-water emulsions and positive-
targeted removal of contaminants from produced water ly charged MNPs controls, the attachment of MNPs to
in oil fields, have drawn considerable attention due to the droplet surface, and the subsequent aggregation of
their environmental merit. The goal of this study was to the electrically neutral oil droplets with attached MNPs
develop an efficient method of removing very stable, (MNPs-oils) play a critical role in accelerated and effi-
micron-scale oil droplets dispersed in oilfield produced cient magnetic separation. The total magnetic separation
water. We synthesized MNPs in the laboratory with a time was dramatically reduced to as short as 1 s after
prescribed surface coating. The MNPs were MNPs, and oil droplets were mixed, in contrast with the
superparamagnetic magnetite, and the hydrodynamic case of free, individual MNPs with which separation
size of amine functionalized MNPs ranges from 21 to took about 36∼72 h, depending on the MNP concentra-
255 nm with an average size of 66 nm. The initial oil tions. Model calculations of magnetic separation veloc-
content of 0.25 wt.% was reduced by as much as 99.9% 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
Electronic supplementary material The online version of this
article (doi:10.1007/s11051-017-3826-6) contains supplementary MNPs-oils is greater than 360 nm, which can be used as
material, which is available to authorized users. an optimum operating condition.

S. Ko (*) : H. Daigle : C. Huh


Department of Petroleum and Geosystems Engineering,
Keywords Produced water treatment . Oil removal .
University of Texas, Austin, TX, USA Superparamagnetic nanoparticles . Magnetic separation .
e-mail: saebomko@austin.utexas.edu Aggregation
E. S. Kim : T. E. Milner
Department of Biomedical Engineering, University of Texas,
Austin, TX, USA Introduction
S. Park
Department of Civil, Architectural and Environmental Water shortages and imbalance of water demand and
Engineering, University of Texas, Austin, TX, USA supply are a serious issue worldwide (WWAP 2015).
Recently, intensifying energy production activities, such
M. V. Bennetzen as unconventional oil and gas production, have required
Maersk Oil Corporate, Københavnsområdet, Denmark
a high water demand, resulting in an increasing compe-
G. A. Geremia tition for fresh water with other necessary human activ-
Maersk Oil Research and Technology Centre, Doha, Qatar ities (Arnold et al. 2004; Gregory et al. 2011; Jacobs
132 Page 2 of 14 J Nanopart Res (2017) 19:132

2016; Vengosh et al. 2014). Along with the increasing investigated MNPs for produced water treatment are mag-
demand for fresh water for oil and gas production, a netite (Fe3O4) and maghemite (γ-Fe2O3) (Ko et al. 2014,
significant volume of water is also produced during oil 2016; Wang et al. 2013, 2014, 2017). Surface-
recovery, as much as 20 times the volume of produced functionalized MNPs can be adsorbed on a dispersed oil
oil, which requires treatment and safe disposal (Olsson droplet through surface interactions between droplets and
2015). Produced water management is one of the largest the surface-coated MNPs. The interactions can be con-
oilfield operational expenditures (Plebon 2006). trolled by using different surface coatings on the MNPs,
Produced water contains highly stable micron- depending on the surface charge state and the salinity and
size dispersed oil, which makes water treatment pH of the water.
difficult. Conventional technologies currently The main advantage of the use of MNPs to remove
employed to treat produced water, such as gas flo- dispersed oil droplets from produced water is their quick
tation, coalescers, gravity oil separation, mem- response to move in a desired direction with an application
branes, and chemical oxidation (Fakhru’l-Razi of an external magnetic field. Similar high-gradient mag-
et al. 2009), have difficulty in removing such dis- netic separation (HGMS) technology has been commonly
persed oil to meet the requirements for discharging applied in the mining and other industries for many years
or re-injection, as water quality standards and regu- to separate magnetic minerals, for example, Fe, Co, and Ni
lations become more and more stringent (Helland (Yavuz et al. 2009). It is important that the magnetic force
et al. 2008). Therefore, there have been increasing be greater than other competing forces, such as the viscous
efforts to find an efficient and cost-effective tech- drag force and gravitational force, to accomplish high
nology to treat produced water and reduce water recovery of magnetic particles. Using surface engineered
demand (Fakhru’l-Razi et al. 2009). MNPs, HGMS has recently been applied in more compli-
The oil and gas industry is currently interested in using cated separation in various fields, including the separation
nanotechnology for oilfield operations. The main advan- of cells and proteins in biomedicine, as well as removal of
tage of nanotechnology is the size of nanoparticles (NPs), radionuclides, heavy metals, and nonpolar organic contam-
whose diameters range from 1 to 100 nm, giving them a inants from water in environmental engineering (Moeser
very large surface area per unit mass. A number of review et al. 2002).
papers on nanotechnology applications in oil and gas Previously, we proved the concept that surface-coated
production have been published (Amanullah and MNPs could remove oil droplets of synthetic oil from de-
Ramasamy 2014; Bennetzen and Mogensen 2014; El- ionized water (DIW) and developed a force balance model
Diasty and Ragab 2013; Kapusta et al. 2011; Ko and to predict the separation velocity of MNPs attached on the
Huh 2017; Kong and Ohadi 2010; Krishnamoorti 2006; droplet when subjected to a magnetic field gradient (Ko
Matteo et al. 2012; Mokhatab et al. 2006; Pourafshary et al. 2014; Prigiobbe et al. 2015a, b). As an extension of
et al. 2009; Saggaf 2008; Vipulanandan et al. 2015). The the above study, we report here on the synthesis and
nanotechnology applications under development, in par- surface modification of MNPs the evaluation of crude oil
ticular for the use of silica and iron oxide NPs, include CO2 separation from seawater by MNPs and the prediction of
foam for enhanced oil recovery (EOR) (Worthen et al. magnetic separation velocity and time. We also made
2015), enhanced reservoir imaging (Rahmani et al. detailed visual observations of the dynamics of oil-water
2015), heavy oil mobilization, rheology control, hydrate/ separation, employing optical and fluorescent microscopy,
wax deposition prevention in pipes (Mehta et al. 2014), for a mechanistic understanding of the oil-water separation
produced water treatment in upstream and downstream process.
operations (Ko et al. 2014, 2016), and desalination
(Wang et al. 2014, 2017).
Among a wide variety of NPs, the use of Materials and experimental methods
superparamagnetic iron oxide NPs has drawn particular
attention due to their unique properties (Ko and Huh Synthesis and surface fabrication of MNPs
2017). Various magnetic nanoparticle (MNP) surface coat-
ing materials and methods have been developed for appro- The co-precipitation (co-ppt) method was used to synthe-
priate use in the oilfield (Bagaria et al. 2013; Wang et al. size MNPs under alkaline conditions. An aqueous mixture
2014; Yoon et al. 2011, 2012). The most widely of FeCl2∙4H2O (Fisher Scientific, ACS grade) and
J Nanopart Res (2017) 19:132 Page 3 of 14 132

FeCl3∙6H2O (Fisher Scientific, ACS grade) at a molar ratio amplitude after increasing pH to ∼10 to dissolve the
of 1:2 was dissolved in ultra-purified DIW, followed by the alkaline soap components from oil. The employed
addition of citric acid (monohydrate, Fisher Scientific, method to generate the O/W emulsion in this study
ACS grade) as a stabilizer. NH4OH (20%, Fisher Scientif- was established in our lab through trial and error to
ic, TraceMetal™ grade) was quickly added to the mixture make small and stable emulsions. The O/W emulsion
after the mixture temperature reached 90 °C, while vigor- was diluted tenfold with DIW, American Petroleum
ously mixing under nitrogen purging. Black particles were Institute (API) standard brine (2% calcium chloride
immediately precipitated. The mixing continued for 2 h at and 8% sodium chloride), and synthetic seawater
90 °C in a nitrogen atmosphere. The mixture was then (SSW, Ricca Chemical Company) to make 0.5 wt.%
cooled down to room temperature in an ice bath while oil, followed by pH adjustment to ∼8.2. Various vol-
stirring. The particles were collected by a permanent mag- umes of A-MNPs or PAA-MNPs were added to 1.6 mL
net and washed 4–5 times with DIW. of 0.5 wt.% O/W emulsion. Then, water was added to
The silanization process was employed to graft the MNP make a total volume of 3.2 mL. After the mixtures of A-
surface with amine using 3-amino propyltriethoxysilane (3- MNPs or PAA-MNPs and emulsion shaken on an orbital
APTES) (Acros Organic, ≥99%) (Bagaria et al. 2013; Wang shaker, the mixture was placed on a 1″ × 1″ × 1/2″ block
et al. 2014; Xue et al. 2014). After 1 h hydrolysis of 3- nickel-plated neodymium-iron boron permanent magnet
APTES in acidic solution (pH∼4.6) of glacial acetic acid to separate oil droplets with attached A-MNPs or PAA-
(Fisher Scientific, ACS grade), pH was adjusted to around 8, MNPs from water. The magnetic field strength varied
followed by adding re-dispersed MNPs dropwise to hydro- from 0.44 T in the middle of the magnet to 0.76 T on the
lyzed 3-APTES solution. The mixing continued for 24 h at edge. A schematic illustration of oil droplet removal,
65 °C. The mixture was then cooled down to room temper- modified from Ko et al. (2014), is shown in Fig. 2.
ature while stirring. Amine functionalized MNPs (A-MNPs)
were collected by a permanent magnet and washed three Dynamics of magnetic separation of MNPs
times with DIW.
Polyacrylic acid (PAA, Sigma Aldrich, 8 kDa) was After dying O/W emulsions with fluorescent lipid of
grafted on the surface of A-MNPs (Wang et al. 2014). ammonium 1,2-dioleoyl-sn-glycero-3-
After activating the carboxylic group of PAA to conju- phosphoethanolamine-N-(lissamine rhodamine B sulfo-
gate with the primary amine group on A-MNPs using 1- nyl) (Avanti Polar Lipids), the movement of MNPs-oils
ethyl-3-(3-dimethylaminopropyl) carbodiimide (Sigma separating from water was observed using fluorescent
Aldrich), the mixture was mixed for 24 h at room microscopy (Zeiss Axiovert 200 M Widefield) with and
temperature. PAA grafted A-MNPs (PAA-MNPs) were without an external magnetic field. The permanent mag-
collected by a permanent magnet and washed three net with the size of 1/8-in. cube and the magnetic
times with DIW. The process of MNP synthesis and strength of 50 mT was used as an external magnetic
surface fabrication is summarized in Fig. 1. field to let oil droplet separation process continue for a
reasonable time to make a movie. The progress of MNP
Oil droplet removal aggregation after oil droplet attachment was observed
using an optical microscope (Nikon). The size of aggre-
An oil-in-water (O/W) emulsion containing 5 wt.% gated MNPs was measured using a ruler on microscopic
crude oil of the total acidic number of 0.15, 2.9, and images and converted to a corresponding actual size
4.5 was produced using a sonifier gun for 20 min at 40% based on a length of a ruler bar on the images. Magnetic

Fig. 1 The process of MNP synthesis and surface fabrication


132 Page 4 of 14 J Nanopart Res (2017) 19:132

Measurement
of oil content in
separated
clean water

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 Therefore, in the case of oil droplet removal experiments
water was continuously monitored with an automatic in brine solution, oil concentration from separated water
camera, and images were taken at a certain interval until was measured using UV-VIS spectrophotometer at a
the level of the interface between clear water and MNPs wavelength of 400 nm after extracting oil from separat-
remained the same. ed brine solution with methylene chloride (Fischer Sci-
entific, Stabilized/ACS grade, ≥99.5%) (Tellez et al.
2005).
Experimental analyses Percent removal of oil (R) was determined as

Sizes and zeta potentials of synthesized and surface-


ðC 0 −C Þ
fabricated MNPs were measured in DIW at room tem- R¼  100; ð1Þ
perature with dynamic light scattering (DLS, Zetasizer C0
Nano ZS, Malvern Instrument). Zeta potentials of crude
oil and oil droplet-attached MNPs were also measured where C0 = oxygen demand in 0.25 wt.% of crude oil
with DLS. Morphology of MNPs was observed using (mg O2/L) for COD measurement or oil content in brine
transmission electron microscopy (TEM, FEI Tecnai solution (wt.%) and C = oxygen demand in separated
TEM-Electron), operated at 80 kV on a carbon grid water (mg O2/L) or oil content in separated brine solu-
coated with Cu. All measurements were carried out with tion (wt.%).
about 100-fold diluted samples in DIW. Fe concentrations in MNPs after synthesis and sur-
Oil concentrations in separated water were measured face fabrication were measured using inductively
by chemical oxygen demand (COD)/closed reflux, col- coupled plasma optical emission spectrometry (ICP-
orimetric method (Cleceri et al. 1998). Chloride inter- OES, Agilent 710-ES) at a wavelength of 283.204 nm.
feres with the COD measurement through reaction with NPs were dissolved in 30% (by mass) nitric acid (Fisher
catalysts for oxidation reactions of organic components Scientific, TraceMetal™ grade), and then diluted in
of a sample, resulting in the formation of precipitate. DIW by 10 times to reduce nitric acid concentration to
J Nanopart Res (2017) 19:132 Page 5 of 14 132

less than 4 wt.%, which is the allowable concentration of To simplify the mathematical model, we assume:
nitric acid for ICP.
a. MNP aggregates behave as a solid, single, spherical
particle;
Modeling for magnetic separation of MNPs b. There is no interaction between MNP aggregates;
c. The applied external magnetic field is strong enough
We modified a previously developed mathematical to magnetize MNPs to saturation level;
model for the magnetic separation of MNPs (Ko d. The magnetic field is homogeneous on the surface
et al. 2014; Prigiobbe et al. 2015a, b) to estimate of the permanent magnet (0.44 T);
the total time and velocity of magnetic separation e. The exact value of vd is time-varying velocity. Ac-
of MNPs attached on oil droplets. Considering celeration of the particle, however, decreases imme-
Newton’s second law, diately, and the velocity reaches terminal velocity
due to its nano-size (Kuhn et al. 2006). Since it
∂vd !  ! ! reaches to the terminal velocity instantaneously,
md ⋅ ¼ F b þ F drag þ F m ; ð2Þ
∂t 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.
!
F b ¼ V d ρd −ρ f g; ð3Þ

!
F drag ¼ −3πηd d vd ; ð4Þ Experiment results and discussion

MNP characterization
! h i
F m ¼ ðm⋅∇BÞ ¼ V p ðχp −χ f Þ=2 μ0 ∇B2 ; ð5Þ
Hydrodynamic sizes of citrate-stabilized MNPs and
where md is the total mass of an oil droplet and MNPs A-MNPs measured with DLS were 51 and 66 nm,
attached on it; vd is the magnetic separation velocity of respectively. Zeta potential of citrate-stabilized
! MNPs and A-MNPs at pH 8.2 was −41 mV and
an oil droplet with attached MNPs; F b is the buoyancy
! ! +26 mV in DIW, respectively, which indicates the
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 successful functionalization of amine. The surface
densities of the oil droplet and of water (kg/m3), respec- charge of A-MNPs is positive due to protonation
tively; g is the gravitational acceleration (m/s2); ∇B is of the terminal primary amine group (−NH2) at
the external magnetic field gradient (T/m); m is the pH 8.2, for which the pKa value is 10.66. The
magnetic dipole moment (N•m/T); Vp is the volume of pH point of zero charge (pHPZC) of A-MNPs was
aggregated MNPs adsorbed on an oil droplet (m3); χp around pH 10.6. According to previous work by
and χf are the volume magnetic susceptibilities of the Wang et al. (2014), the hydrodynamic size and
NP and of water, respectively (unitless); and μ0 is mag- zeta potential of PAA-MNPs were 152 nm and
netic permeability of air or vacuum (V•s/(A•m)); −38 mV at pH 7, respectively. The surface charge
The velocity (m/s) of magnetic separation of MNP of PAA-MNPs is negative due to the negative
aggregates which cover an oil droplet (MNPs-oil) (vd ) is charge on oxygen (−COO−) after conjugating car-
derived from the force balance (Eq. (2)), expressed as boxylic acid groups of PAA to the terminal amine
  h    i of A-MNPs. The negative value of zeta potential
V p ðχp −χ f Þ
vd ¼ 1 3πηdp =2 μ0 ∇B2 þ V d ρd −ρ f g ; confirms the successful surface grafting of PAA on
MNPs.
ð6Þ
TEM images showed a small degree of aggre-
where η is the fluid viscosity (N•s/m ) and dp is the
3
gation of MNPs and A-MNPs, whose individual
diameter of an oil droplet covered with MNP particle diameter was around 10 nm (Fig. 3).
aggregates. MNPs are known to form small aggregates, which
132 Page 6 of 14 J Nanopart Res (2017) 19:132

Fig. 3 TEM images and the DH (a) (b)


distribution of MNPs. a TEM
images of MNPs. b TEM images 50 nm 50 nm
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- Oil droplet removal
face energy by strong magnetic dipole-dipole at-
tractions along with Van der Waals forces (Gupta An O/W emulsion in DIW with an initial oil content of
and Gupta 2005). 0.25 wt.% was reacted in various Fe concentrations of
X-ray diffraction patterns of MNPs and A-MNPs A-MNPs and PAA-MNPs. Figure 4 shows the compar-
followed the characteristics of magnetite (Wang ison of percent removal of three different oils of
et al. 2014). This showed that synthesized iron oxide TAN = 0.15, 2.9, and 4.5, after reacting with 0.875 g/L
NPs were magnetite and polymer surface coating did Fe of A-MNPs for 5 min at pH 8.2. The percent re-
not change the crystallinity of iron oxide NPs. For movals of oil droplets with TAN = 0.15, 2.9, and 4.5
both MNPs and A-MNPs, high saturation magneti- from DIW were 99.5, 97.9, and 96.4%, respectively. A-
zation (Ms) values of approximately 90 emu/g Fe3O4 MNPs having the opposite surface charge to oil droplets
were obtained, and the Langevin curves showed the were successfully attracted to and attached on negative-
absence of hysteresis, indicating that they are ly charged oil droplets, resulting in neutralized surface
superparamagnetic NPs (Fonnum et al. 2005; charge and making MNPs-attached oil droplets stick
Mehta et al. 2014; Wang et al. 2017; Yoon et al. together and form larger MNPs-oil droplet aggregates.
2011, 2012). APTES is a small molecule whose This allows efficient magnetic separation of MNPs-
molecular weight is 221.37 g/mol. As shown in attached oil droplets from water, which can be seen from
DLS measurements, the size difference between Eq. (6) with a large Vp. A larger value of TAN corre-
MNP and A-MNP is about 15 nm. Due to the sponds to a greater acidity of crude oil. The greater the
similar particle sizes of MNP and A-MNP, Ms values negative surface charge density, the greater the particle
were determined to be similar. stability due to the stronger electrostatic repulsive
J Nanopart Res (2017) 19:132 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
Fig. 4 The comparison of the percent removal of different types 0.438 g/L of Fe. It took almost 3 h to remove oil droplets
of crude oils in API, SSW, and DIW, after oil and A-MNPs, are from water to near zero concentration using 0.438 g/L of
mixed. Fe concentration of A-MNP is 0.875 g/L. pH of A-MNP is Fe (see Fig. 6). It appears that the amount of terminal
8.2. Initial oil content in water is 0.25 wt.%
amine groups available would be proportional to Fe
concentration, resulting in a greater density of surface
forces. TAN 4.5 oil, having the greatest acidity among charge on MNPs. The kinetics of oil droplet removal
three crude oils tested, will require the greatest amount from water with 0.438 g/L Fe were slower than with
of A-MNPs to have the same level of removal efficiency 1.75 and 0.875 g/L Fe.
as the other lower TAN oils. Reacted with the same Figure 7 shows the reduction of oil content (TAN 2.9
amount of A-MNPs, the percent removal of TAN 4.5 and 4.5) in SSW with respect to mixing time between oil
O/W emulsion was slightly lower than that of the other droplets and A-MNPs. Initial oil content of TAN 2.9 and
two. However, this amount of A-MNPs added to the 4.5 O/W emulsions was 0.25 wt.%, and Fe concentra-
three different oils was sufficient to remove almost all tion of A-MNPs was 0.875 g/L. The kinetics of oil
oil from water. removal in SSW were slower than in DIW. The TAN
In API brine and SSW, the percent removals of oil 2.9 and 4.5 oil contents in separated SSW were reduced
droplets were similar, regardless of the oil type (Fig. 4). to 0.037 and 0.17 wt.% from 0.25 wt.%, respectively,
The percent removals of three different oils of after 5 min of mixing between A-MNPs and O/W emul-
TAN = 0.15, 2.9, and 4.5 ranged from 98.9 to 99.6 in sion; the oil contents were reduced to almost zero in
API brine and from 98.2 to 99.2 in SSW after mixing A- DIW (refer to Fig. 4). Ions present in SSW could inter-
MNP and O/W emulsions overnight. The percent re- fere with the interaction between oil droplets and A-
movals of oil droplets were similar in the same condi- MNPs, competing with oil droplets for reactive sites of
tions of solution pH of 8.2 and Fe concentrations of A-MNPs. In addition, ions surrounding A-MNPs reduce
0.875 g/L. the thickness of the electrical double layer, reducing
The negatively charged PAA-MNPs were also mixed particle stability. However, the amount of A-MNPs
with the TAN 2.9 and 4.5 oil dispersions, to investigate added to the oil-in-SSW emulsions was enough to re-
whether the electrostatic interaction is indeed the major move greater than 95% in 20 min for TAN 2.9 oil and in
interaction mechanism to remove oil droplets from wa- 60 min for TAN 4.5 oil.
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 Microscope observation of magnetic separation
2 g/L PAA-MNPs overnight. Unreacted PAA-MNPs
(i.e., no oil attached) were collected at the bottom of Optical microscope images of TAN 2.9 O/W emulsion
the reactor after magnetic separation. Zeta potentials of are shown in Fig. 8a. The size of the spherical oil
TAN 2.9 and 4.5 oil droplets were −69 and −74 mV at droplets ranges from 0.2 to 10 μm. The progress of A-
pH 8.2, respectively. This confirmed that the negatively MNP aggregation and oil droplet attachments with time
charged PAA-MNPs (−38 mV) and oil droplets repel is shown in Fig. 8b. The hydrodynamic size of A-MNPs
each other, causing oil droplets to remain in water even by itself ranged from 21 to 255 nm with some degree of
after magnetic separation. In contrast with PAA-MNPs, aggregation already existing as shown in Fig. 3b. Opti-
Fig. 5b shows clear water after magnetic separation cal microscope images show significant aggregation of
using A-MNPs whose surface charge is positive MNPs and oil droplets. The image in the middle of
132 Page 8 of 14 J Nanopart Res (2017) 19:132

(a) PAA-MNP (b) A-MNP

Fig. 5 Photo images of oil droplet separation from water using magnet is placed. b TAN 2.9 O/W emulsion (0.25 wt.% oil) and A-
different surface charged MNPs. a TAN 2.9 (left) and 4.5 (right) MNPs (0.875 g/L Fe). MNPs-oils were collected at the right-hand
O/W emulsion (0.25 wt.% oil) and PAA-MNPs (2.0 g/L Fe). PAA- side of the reactor where a permanent magnet is placed
MNPs are shown at the bottom of the reactor where a permanent

Fig. 8b, which was taken after 5 min of mixing, shows a results in incomplete particle growth. In our case, larger
glimpse of coalesced oil (nude color objects) underneath aggregates of MNPs-attached oil droplets were formed
MNP aggregates (brown objects). There are also several within 1 min after mixing them on an orbital shaker
oil droplets not covered by MNPs in the image, some of table. Microscope observations indicate that the oil
which seem to have been attached to MNPs due to the droplet removal process using MNPs occurs very
increased MNP size, but the size of the MNPs might not rapidly.
be large enough to be seen by optical microscopy. The As shown in Fig. 9 of the snapshot of the video clip,
various sizes of coalesced oil droplets are also shown fluorescent dye-tagged oil droplets were illuminated.
around MNP aggregates and are believed to be present Smaller and brighter oil droplets are shown in the upper
within them as well. layer of microscope-focus area and bigger and dimmer
The positively charged A-MNPs successfully over- in the lower layer. Before placing a permanent magnet,
come the stabilization energy barrier between oil drop- most of oil droplets were slowly floating in the sample
lets by neutralizing their charge, making them stick chamber except a few whose size are big enough to be
together and grow into flocs, which can then easily be settle down by the gravitational force. As soon as the
magnetically separated from water. The proper contact magnet was placed on the right-hand side, oil droplets
time in the rapid-mix chamber during the coagulation were quickly moved to the right (see the video clip in the
process in the water treatment is typically 1 to 3 min to supplementary material).
produce larger particles, while insufficient mixing

Fig. 6 Reduction of TAN 2.9 oil content in separated water with Fig. 7 Reduction of oil content of TAN 2.9 and 4.5 in separated
respect to mixing time between oil droplet and A-MNPs in differ- SSW water with respect to mixing time between oil droplet and A-
ent Fe concentrations of A-MNPs at pH 8.2. Initial oil content in MNPs. Initial oil content in water is 0.25 wt.%. Fe concentration of
water is 0.25 wt.% 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 every 10 min until the level of the interface between
the clear water and the particles was stationary, shown in
Determination of magnetic separation velocity and time Fig. 10a. The complete water and MNP separation took
of free A-MNPs without oil 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
The progress of magnetic separation of MNPs by itself started to appear at the top and bottom of the left-hand
was monitored continuously using a digital camera 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 J Nanopart Res (2017) 19:132

magnetic separation was started. The hydrodynamic size for the analytical simulation. Figure 10c, d presents
of A-MNPs ranges from 21 to 255 nm with an average analytical simulation results of magnetic separation ve-
size of 66 nm. About 91% of A-MNPs fell into the size locity and time as a function of normalized distance of z/
range of 28∼140 nm. As seen in the water-phase color of L at various MNP sizes corresponding to DLS size
images in Fig. 10a, most of the A-MNPs were collected measurements using Eq. (6). The magnetic field induced
within 12 h. by a permanent magnet was described using the analyt-
The velocity and separation time for MNPs of differ- ical solution derived by Ravaud and Lemarquand
ent (equivalent) sizes were estimated using Eq. (6). (2009), and it matched well with measured values
Figure 10b shows a conceptual model of the system Prigiobbe et al. (2015a). The parameter values used for

(a)

(b) (c)

Model System
L1 =1.5 cm : MNP
B = 0.44T

(d)

Fig. 10 a Images of magnetic separation progress with time corresponding to DLS size measurement using Eq. (6). d Analyt-
(0.435 g/L of Fe in A-MNP). b Conceptual model of the system. ical simulation results of magnetic separation time as a function of
c Analytical simulation results of magnetic separation velocity as a normalized distance of z/L at various MNP sizes corresponding to
function of normalized distance of z/L at various MNP sizes DLS size measurement using Eq. (6)
J Nanopart Res (2017) 19:132 Page 11 of 14 132

model calculations are listed in Table 1. The gravitation- simulation results are presented in Fig. 11b. These cal-
al velocity of 9.88 10−9 m/s is calculated for the average culations are more accurate than the ones for free A-
size (66 nm) of A-MNPs, and the settling time by MNPs, because the charges of particles are neutralized
gravity alone to the bottom of a reactor from the top of or reduced, resulting in negligible electrostatic forces.
water (2.8 cm) is 787 h. However, with the magnetic The magnetic separation of MNPs-oils was monitored
force, it will take 2.7 h to collect 66 nm A-MNPs from using automatic camera at a certain time interval. When
the left (the furthest from a magnet, z = 1) to the right 0.875 g/L Fe of A-MNPs was reacted for 15 min with O/
(the closest to a magnet, z = 0) in the model system, W emulsion containing 0.25 wt.% oil with TAN 2.9,
where the total travel distance (L) is 1.5 cm, as shown in MNPs-oils were collected almost instantly, and clear
Fig. 10b. Figure 10c, d shows the analytical simulation water was obtained as shown in Fig. 5a. Unlike the
results of the magnetic separation velocity and time of images shown in Fig. 10a, where the greater portion of
A-MNPs as a function of the normalized particle travel particles was collected at the top of the reactor due to the
distance of z/L where particle sizes range from 24 to stronger magnetic field at the top, there were no particles
240 nm. As particles get closer to the magnet, the at the top of the magnet. Because particles get bigger as
velocity of particles increases due to the larger magnetic shown in Fig. 8c, the gravitational force also has an
field gradient. The estimated total collection time is in effect on particles. For example, 255 μm MNPs-oils
the range of 0.2 to 20 h, depending on the particle size. will settle down to the bottom in 0.2 s by gravity alone.
The simulation results show some deviation from the Interestingly, when 1.75 g/L Fe of A-MNPs were
experimental results mainly because the electrostatic reacted with O/W emulsion, the magnetic separation
interaction between particles is not considered in this time depended on the mixing time, as shown in
model. The greater the Fe concentrations of A-MNPs, Fig. 11a. This might be caused by free MNPs which
the greater the electrostatic force that the magnetic field are not attached on oil droplets. However, as the mixing
has to overcome. This model prediction provides the time increases, the probability of collision increases
approximate particle separation velocity and time at between free MNPs and between free MNPs and
each travel distance. 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,
Determination of magnetic separation velocity and time it took about 10 h to collect all particles magnetically.
of MNPs-oils When A-MNPs were reacted with oil droplets for
120 min, it took about only 5 min for complete magnetic
Figure 11a shows the progress of magnetic separation of separation. Based on the calculation of velocity and total
MNPs-oils, which is continuously monitored at a certain time in the model system, the size of particles might be
interval using a digital camera. The velocity and sepa- grown to be greater than 360 nm, the total magnetic
ration time for MNPs-oils of different (equivalent) sizes separation time of which is approximately 5 min
were estimated using Eq. (6), and the analytical (Fig. 11b). This result suggests that the concentration
ratio of MNPs and oil and the mixing time could be the
Table 1 Parameter values used for the model calculations
most important variables to get quick and effective oil
Parameter Value droplet separations from water.

A-MNP Average diameter, dp (m) 66 × 10−9


Density, ρp (kg/m )
3
5.17 × 103 Conclusions
Volume magnetic susceptibility, χp 5.03
Magnetic permeability of air, μ0 (T•m/ 1.26 × 10−6 Positively charged, in-house synthesized MNPs effec-
A) tively removed negatively charged oil droplets by as
Oil Density, ρd (kg/m3) 0.973 × 103
droplet much as 99.5% after 5 min of mixing between MNPs
Water Viscosity, η 1.00 × 10−3 and oil. The greater than 95% of initial oil content of
Density, ρf (kg/m )
3
1.00 × 103 0.25 wt.% oil-in-SSW emulsion was removed within
Volume magnetic susceptibility, χf −9.05 × 10−6 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 J Nanopart Res (2017) 19:132

(a)

(b)

Fig. 11 a Images of magnetic separation progress of MNPs-oils at of the total magnetic separation time of MNPs-oils as a function of
different reaction time between oil droplets and A-MNPs as a MNP aggregate diameter in the range of 90 to 360 nm in the
1.75 g/L of Fe at pH 8.2. b Analytical simulation of the change model system using Eq. (6)

droplets was successfully removed by greater than 99% separation. Thus, the total magnetic separation
with as low as 0.438 g/L Fe of A-MNPs. The kinetics of time was dramatically reduced to as short as 1 s.
oil droplet removal in SSW were slower than in DIW. Model calculations of magnetic separation velocity
Based on microscope observations, the electro- show that the velocity of free A-MNPs depends critical-
static attraction between negatively charged oil and ly on the magnetic field gradient and the particle size.
positively charged MNPs controls, the attachment The total magnetic separation time of free A-MNPs
of MNPs to oil droplets, and the subsequent ag- ranged from 0.2 to 20.4 h, depending on the particle
gregation of the neutralized MNPs-attached oil size. Contrary to the results with free A-MNPs, the total
droplets play a critical role in accelerated and magnetic separation took approximately 5 min where
efficient oil droplet removal and magnetic the size of MNPs-attached oil droplet was grown to be
J Nanopart Res (2017) 19:132 Page 13 of 14 132

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