Journal of Water Process Engineering 20 (2017) 226–231

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Journal of Water Process Engineering

journal homepage: www.elsevier.com/locate/jwpe

Oil removing properties of exfoliated graphite in actual produced water T

treatment
⁎
Kenji Takeuchia,b, , Hidenori Kitazawab, Masatsugu Fujishigea, Noboru Akuzawab,
Josue Ortiz-Medinab, Aaron Morelos-Gomezb, Rodolfo Cruz-Silvaa,b, Takumi Arakib,c,
Takuya Hayashia,b, Morinobu Endoa,b
a
Institute of Carbon Science and Technology, Shinshu University, 4-17-1 Wakasato, Nagano 380-8553, Japan
b
Global Aqua Innovation Center, Shinshu University, 4-17-1 Wakasato, Nagano 380-8553, Japan
c
Research Organization for Information Science & Technology, 2-32-3, Kitashinagawa, Shinagawa-ku, Tokyo 140-0001, Japan

A R T I C L E I N F O A B S T R A C T

Keywords: Removal of oil from actual produced water (composed of mainly oil and water emulsion) by exfoliated graphite
Oil (EG) was investigated. Laboratory scale sorption columns of EG could reduce the oil concentration in produced
Emulsion water from 278 and 66 mg/L to 1.2 mg/L, and undetectable, respectively. A separate experiment with TOC (total
Sorption organic carbon) demonstrated that TOC decreased from 566 mg/L in the feed solution to 1.5 mg/L in the ef-
Exfoliated graphite
fluent. Both results (oil densitometer and TOC) showed excellent ability of EG for oil removal from produced
Produced water
water. SEM and FT-IR observations confirmed the deposition of oily material on the surface of EG during the
water treatment process. TG-DTA of oil-sorbed EG showed a gradual weight decrease in the temperature range
between 100–600 °C, being considered to be the decomposition of sorbed oil. Raman spectroscopy and XRD
measurements of EG samples, before and after the treatment, indicated no structural change of EG. Molecular
dynamics simulations revealed that octadecane molecules are selectively adsorbed on the EG surface. Effect of
isomer type of octadecane molecules on the sorption energy was also discussed.

1. Introduction
The amount of produced water in the world is reported to be about
300 million barrels per year in 2011 and is increasing year by year [1],
where the term “produced water” means byproduct in the oil and gas
production plant. The amount of produced water is about 4 times that
of crude oil produced. Such a large amount of produced water must be
cleaned and reused because of not only economic reason but also for
problems concerning worldwide lack of clean, fresh water [2], en-
vironmental pollution [3] etc. In general, produced water treatment
system for oil-water separation consists of primary and secondary
treatments followed by membrane treatment [4–6]. The primary
treatment includes screening, grit removal, gravity assisted sedi-
mentation, demulsification, coagulation, adsorption, dissolved air pre-
cipitation and induced air floatation. The secondary treatment contains
the removal of dissolved components through chemical and biological
treatment. These treatments are generally required to decrease oil
content to several tenths of mg/L.
Our previous investigation demonstrated that exfoliated graphite
(EG) is able to reduce the oil concentration of engine oil-water emulsion
from 100 mg/L to 0.1-few mg/L [7]. It means that the produced water
after the EG adsorption process can be directly supplied to the mem-
brane treatment, in the produced water refining system. The usefulness
of EG for heavy oil sorption (“oil on water” or “pure oil”) was found out
at first by the research group of Inagaki and Toyoda [8–16]. They re-
ported the maximum capacity of sorption of the A-grade heavy oil
reached more than 80 times the weight of the EG [8]. Further, they
developed a lot of investigations such as effects of bulk density of EG on
the sorption behavior [9], recovery of heavy oil and recycling of EG
[10], trials for practical applications [11], mechanism of oil sorption on
EG [12], etc. Table S1 summarizes reported studies concerning oil
sorption by carbon materials, where kind of carbon materials, oil spe-
cies and state are listed in the order of published year. Oil sorption
behavior has been further investigated with carbon materials such as
carbon nanotube (nanofiber) or its composites [18,19,21,24,25], ex-
foliated graphite oxide [20], hollow carbon fibers [22], hollow carbon
beads [23], polyurethane-activated carbon composite [26], etc. in ad-
dition to EG or magnetic EG (MEG) [7–17,27–29]. These investigations
are almost related to the oil sorption in the state of “oil on water” or
“pure oil”, keeping the oil spill in mind. On the contrary, we focused on

⁎
Corresponding author at: Institute of Carbon Science and Technology, Shinshu University, 4-17-1 Wakasato, Nagano 380-8553, Japan.
E-mail address: takeuchi@endomoribu.shinshu-u.ac.jp (K. Takeuchi).

https://doi.org/10.1016/j.jwpe.2017.11.009
Received 27 December 2016; Received in revised form 31 October 2017; Accepted 12 November 2017
2214-7144/ © 2017 Elsevier Ltd. All rights reserved.
K. Takeuchi et al. Journal of Water Process Engineering 20 (2017) 226–231

the selective oil sorption from oil-water emulsion, because the oil in the
produced water generally exists in the form of emulsion [7]. The
emulsion consists of very fine mixture of oil and water such as oil in
water and water in oil [30]. Although the effectiveness of EG was
confirmed with emulsion of engine oil-water system in the previous
investigation, its applicability to actual produced water has not yet
been clarified.
The purpose of the present investigation is to confirm whether EG
sorbs oil from actual produced water or not. The produced water used
in the present investigation was provided by Niigata city, Japan, where
oil-water emulsion is naturally produced and effective method of oil-
removal is desirable. For actual produced water, oil sorption was not
succeeded by the same method used for the model produced water
(engine oil-water emulsion), where EG was put into the emulsion in a
beaker and the mixture was stirred [7]. Therefore, laboratory scale
sorption column of EG was constructed. The sorption experiments
showed that it reduces the oil concentration in produced water from
278 to 1.2 mg/L (1st run), and from 66 mg/L to undetectable (2nd run).
Similar experiment based on TOC (total organic carbon) demonstrated
that it decreased from 566 mg/L in the feed solution to 1.5 mg/L in the
effluent. These results confirmed the usefulness of EG for oil sorption
from real produced water. SEM and FT-IR observations confirmed the
deposition of oil on the surface of EG. In addition, the molecular dy-
namics simulations were performed with a model consisting of graphite
layers (EG) and octadecane molecule (oil molecule). Adsorption energy
of octadecane molecules (3 kinds of isomers: n-octadecane,
2,2,4,9,11,11-hexamethyldodecane, 5,5-butyldecane) was calculated.
The effects of isomer type and defects in graphene layers on the ad-
sorption energy were discussed.
2.3. Theoretical analysis of oil sorption behavior on EG
Molecular dynamics (MD) simulations were applied to the sorption
of octadecane (C18H38) on graphite. Octadecane was selected as a
model substance of oil in the produced water. The atom charges of
octadecane were calculated by the ab-initio quantum method at
6–31G** level, using the NWCHEM [32] package. The SPC/E water
model was used and kept at 1 atm with NPT ensemble on the basis of
the LAMMPS code [33,34]. Coulomb and van der Waals interactions
were considered. Amber Force Field [35] was used for the potential
calculation. Temperature was set at 295 K. Time step and total simu-
lation time were 1 fs and 4 ns, respectively. The periodic system was
used in the calculation. Two kinds of structure model of EG were
constructed; 3 graphene layers with defects involving OH groups
(Model 1) and 3 graphene layers without defects (Model 2). In Model 1,
the hexagon of carbon ring was removed and the dangling bonds of
carbon were terminated by OH groups. The 10 defects on top layer and
the 8 defects on the second layer were placed randomly, while bottom
layer had no defect. Three isomers of octadecane molecule (n-octade-
cane, 2,2,4,9,11,11-hexamethyldodecane and 5,5-butyldecane) were
subjected to the calculation. The energy of the oil droplet was set to be
0 J when it was in bulk water.
3. Results and discussion
3.1. Oil sorption by EG
Fig. 1 shows the experimental setup. It consists of (a) EG column, (b)

2. Materials and methods

2.1. Materials

Produced water sample was provided by Niigata prefectural office.

It is mainly composed of crude oil and water in addition to solid matters
[31]. It was filtered through a PET filter paper with pore diameter of
6 μm to remove large particles. An appropriate amount of water was
added to the filtrate. It was then emulsified by a homogenizer (Ni-
honseiki, US-300T) just before the following sorption experiment. EG
sample was provided by Toyo Tanso Co., Ltd. Apparent density, and
specific surface area of EG were 0.007 g cm−3 and 49.7 m2 g−1, re-
spectively [7].

2.2. Oil-sorption experiment by EG column

3.4 g of EG were packed into a cylinder made of polypropylene,

with inner diameter of 35.6 mm, resulting in a porous bed with ap-
parent density of 1.1 g·cm−3. The height of the EG layer was about
50 mm. Water-oil emulsion was passed through the EG column. The
effluent was collected in a glass bottle until the collected volume be-
came 100 cc. The oil concentration of feed emulsion and effluent was
determined by an oil densitometer (Horiba, OCMA-505). The total or-
ganic carbon (TOC) in feed emulsion and effluent was determined using
TOC-5000A (Shimadzu Co.). Their optical transmittance was de-
termined by a UV–vis spectroscopy system (Agilent 8453). For EG
samples taken from the EG-column, before and after oil-sorption ex-
periment, FT-IR, Raman spectroscopy and X-ray diffraction measure-
ment were carried out by NICOLET6700 (ThermoFisher Scientific),
inVa Reflex microscope/WiRE4 (Renishaw pic) and RINT2200 V/PC-SV
(Rigaku Co.), respectively. TG-DTA measurements were carried out for
EG samples taken from the EG-column, before and after the oil-sorption
experiment, under air and nitrogen atmosphere. Fig. 1. Purification of produced water by a EG column: (a) EG column; (b) supplied
produced water; (c) effluent.

227
K. Takeuchi et al.
Fig. 2. Optical transmittance of produced water before and after EG treatment.
Table 1
Oil concentration of produced water before and after EG-column treatment.
Sample No. Oil concentration (mg/L)
Before EG treatment After EG treatment
1 278 1.2
2 66 0
emulsion fed to the column and (c) effluent. The turbid feed emulsion
became clear and transparent after the EG-column treatment. The
amount of effluent in the bottle shown in Fig. 1 is about 50 ml. Even
after several experimental runs, where about 50 ml effluent was col-
lected in each run, the effluent continued being transparent. Visible
light transmittance of the feed emulsion and effluent is shown in Fig. 2,
where transmittance is plotted against wavelength of visible light. That
of the effluent is almost close to 100%, irrespective of wavelength,
while that of the feed emulsion ranges from almost 0% at around
400 nm to ∼25% at around 800 nm. This gradual increase of trans-
mittance with wave number is characteristic of Rayleigh scattering by
fine particles. Thus, the optical transmittance measurements suggested
that EG-column treatment removed oil effectively from the emulsion.
To confirm the oil concentration both in the feed emulsion and ef-
fluent, they were analyzed by the oil densitometer. Table 1 summarizes
the results. The oil concentration decreased from 278 mg/L of feed
produced water to 1.2 mg/L (1 st run) and from 66 mg/L to a value
below detection limit (2nd run). It can be considered that the oil con-
centration in the effluent depends generally on the amount of EG in the
column, oil concentration in the feed emulsion, packed density of EG in
the column, etc. Although the effect of such parameters on the oil
sorption behavior has not yet been clarified, remarkable performance of
EG is ascertained by the present experiment. In addition to the ex-
periments with densitometer, TOC (total organic carbon) in the feed
emulsion and effluent were determined in a separate experiment. It
showed TOC decreased from 566 mg/L in the feed solution to 1.5 mg/L
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Journal of Water Process Engineering 20 (2017) 226–231
in the effluent. Both results (oil densitometer and TOC) show that EG
has great possibility and is promising in the produced water treatment.
The weight change of EG before and after sorption experiment was not
determined in the present investigation. However, the amount of
sorbed oil estimated from the concentration of before and after sorption
experiment should be validated by determining the weight change of
EG before and after sorption experiment. This is still a challenge in
future work.
The effect of apparent density and specific surface area of EG on
adsorption capacity of oil has been clarified by Inagaki and Toyoda
group [9]. They found out that the maximum sorption capacity of EG
depends strongly on its bulk density. The sorbed amount of heavy oil
decreases drastically with increasing bulk density of EG. In the present
investigation, therefore, we used EG with small bulk density
(0.007 mg/cm3). They also studied the effect of BET surface area
(1–100 μm) on the sorption capacity. The sorption capacity increases
with increasing BET surface area. However, it is difficult to discuss the
sorption capacity of EG in relation to BET surface area because of the
small values of surface area and the accuracy of the measurement of
such a small surface area.
Several primary and secondary treatments are used for oil removal
from oil-water mixture. For example, da Silva et al. used the combi-
nation of induced air floatation (IAF) as primary and photo Fenton
process as secondary treatment [36]. The oil concentration of effluent
was reduced from 300 ppm to ∼35 ppm by IAF. It was further reduced
to a few ppm by the second treatment. Our EG process reduced the oil
concentration directly from 566 ppm to 1.5 ppm as noted above.
It should be noted that the sorption capacity of activated carbon is
less than that of EG. In our previous investigation [7], it was confirmed
that the oil concentration decreased from 100 mg/L to 18 mg/L after
60 min. Although the driving force of the oil sorption for the activated
carbon is the same with that of EG, the sorption ability of activated
carbon is remarkably less than that of EG. The values of surface area of
EG and activated carbon used in the experiment were 43.5 m2/g and
1176.1 m2/g, respectively. On the other hand, the values of density of
EG and activated carbon were 0.006 g/cm3 and 2.04 g/cm3, respec-
tively. Taking these data into account, the enlarged space (macro-pore)
in between graphene planes of EG is important. The activated carbon
(Palm shell activated carbon) has a lot of micro-pores (less than 2 nm)
but very small amount of larger (meso- and macro-) pores. Therefore,
the mobility of oil molecules in the pore of activated carbon is small,
inhibiting continuous oil sorption. In contrast, a lot of cavities between
graphene planes of EG allow fast diffusion (convection) of oil mole-
cules, resulting in fast sorption of large amount of oil molecules.
Fig. 3 shows SEM images of EG samples taken before and after EG-
treatment. Typical structure of EG can be seen; the graphitic layers
expand to form moderate gaps leaving the inner layers of the original
crystal exposed. The SEM image taken after oil-sorption experiment
clearly indicates deposit on the surface of graphene layers. It suggests
that exposed graphene layers of EG attract oil selectively from the
emulsion. Fig. S1a,b shows FT-IR spectra observed before and after EG-
treatment. The spectrum taken after oil-sorption experiment differs
Fig. 3. SEM images of EG: (a) original; (b) after oil
sorption.
K. Takeuchi et al.
Fig. 4. TG-DTA of EG: (a) original EG (in air); (b) taken after oil-sorption experiment (in air); (c) taken after oil-sorption experiment (in N2).
from that of original EG. Subtracted spectrum (Fig. S1c) shows signals
which are assigned to water and aromatic C]C. It suggests that the
deposit on the surface of EG involves aromatic compounds. The FTIR
spectrum of original produced water (Fig. S1d) mainly consists of me-
thylene groups (typical for petroleum oil), aromatic ring, aromatic
CeH, aromatic C]C, and methyl groups. The reason why methylene
groups, aromatic ring, aromatic CeH and methyl groups were not
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Journal of Water Process Engineering 20 (2017) 226–231
Fig. 5. MD snapshots for n-octadecane adsorbed on EG surface
(t = 4 ns) and energy for each time step: a) Model 1; b) Model 2; c)
energy trajectory of MD time step. Two kinds of structure model of EG
were constructed; 3 graphene layers with defects involving OH groups
(Model 1) and 3 graphene layers without defects (Model 2).
observed in Fig. S1c is not obvious at present. The concentration of the
emulsion used in the present investigation was 66 mg/L and 278 mg/L,
and therefore the oil concentration in the sorbed phase (in EG) can be
estimated to be less than 60,000 mg/L (i.e. 6%) at maximum according
to our previous report [7]. It may be possibly detected by FTIR. This
point should be further investigated in future work.
Fig. 4 shows TG-DTA traces of EG samples. Fig. 4a is TG-DTA of
K. Takeuchi et al.
Table 2
Values of adsorption energy (kJ) of n-octadecane, 2, 2, 4, 9, 11, 11-hexamethyldodecane
and 5, 5-buthyldecane on graphite with defects (Model 1) and without defects (Model 2).
n-octadecane 2,2, 4, 9, 11, 11- 5, 5-buthyldecane
hexamethyldodecane
Model 1 Model 2 Model 1 Model 2 Model 1 Model 2
−566 kJ −761 kJ −543 kJ −546 kJ −433 kJ −437 kJ
original EG in air. The decrease in mass was observed in the tempera-
ture region between 600 and 800 °C. In this region DTA underwent an
exothermal reaction, indicative of combustion of EG. Fig. 4b is TG-DTA
of EG sample, collected after oil-sorption experiment, in air. Gradual
weight decrease is recognized in the temperature region between
100–600 °C, attributable to the decomposition of sorbed organic ma-
terials. It also shows a weight decrease due to the combustion in the
temperature region between 600–800 °C. Fig. 4c is TG-DTA of EG
sample, collected after oil-sorption experiment, in nitrogen atmosphere.
About 14% of weight decrease was confirmed. Thus, the weight ratio of
oil to EG is estimated to be 14/86 for EG sample after the oil-sorption
experiment. Almost the same weight decrease (14%) can be seen in the
TG-DTA in air (Fig. 4b).
Fig. S2 shows Raman spectra of EG samples taken before and after
EG-column treatment. Both spectra indicate signals at 1360, 1580 and
2700 cm−1. They can be assigned to G, D and G’ bands of graphite,
respectively. Thus, Raman spectra show that the EG remains unchanged
during the oil-sorption experiment. Fig. S3 shows XRD diagrams of EG
samples taken before and after EG-column treatment. It also indicates
that graphite structure of EG remains unchanged during oil-sorption
experiment, because typical 002 and 004 peaks of graphite are solely
Fig. 6. Mean Square Displacement (MSD) of oil droplet on EG surface for 1 ns time after adsorption: a) n-octadecane; b) 2, 2, 4. 9, 11, 11-methyldodecane; c) 5-dibutyldecane.
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Journal of Water Process Engineering 20 (2017) 226–231
observed and no difference at peak position and FWHM (full width at
half maxima) can be seen.
3.2. MD simulations
Fig. 5 shows adsorption features and the evolution of the oil droplet
energy for n-octadecane. The oil droplet keeps its shape even after
adsorption for Model 1 (Fig. 5a). On the other hand, the oil droplet
collapses and spreads on the graphene surface for Model 2 (Fig. 5b).
Model 2 shows lower oil droplet energy in the adsorption state; time
average values were −566 kJ for Model 1 and −761 kJ for Model 2
(Fig. 5c). These simulations demonstrate that oil molecules tend to be
spread over EG surface, while defects, such as OH functional group, on
EG surface attracts the oil droplet and prevents its collapse by Coulomb
interaction.
Figs. S4 and S5 are the results with two isomers of octadecane
(2,2,4,9,11,11-hexamethyldodecane, 5,5-butyldecane). These mole-
cules have more complex structure than n-octadecane, so that these oil
droplets are strongly tangled. Thus, the oil droplets do not spread over
the EG surface, irrespective of Model 1 and 2 (Figs. S4a, S4b, S5a and
S5b). The values of the oil droplet energy for the adsorption are sum-
marized in Table 2.
Fig. 6 shows Mean Square Displacement (MSD) of mass center of oil
droplet after adsorption. The MSD is a measure of the deviation be-
tween the position of a molecule and some reference position. For
Model 1, oil-droplet motion is restricted on expanded graphite surface
relative to that for Model 2, where the oil droplet of Model 2 is able to
slip on expanded graphite surface. Coulomb interaction between octa-
decane and OH groups hinder the oil-droplet motion on the surface and
restrict the mobility of the oil droplets. This coulomb-interaction effect
is similarly recognized for 2,2,4,9,11,11-hexamethyldodecane, 5,5-
K. Takeuchi et al.
butyldecane. The energy of oil droplet in the adsorption state is the
lowest for n-octadecane, both in Model 1 and 2. On the other hand, it is
the highest for 5,5-butyldecane. It suggests that linear structure is ad-
vantageous for the interaction with graphene surface. For the same
molecule, graphene planes without defects (Model 2) are much more
effective for the adsorption than that with defects (Model 1).
From the MD simulation, the following sorption mechanism can be
proposed. Oil droplets are attracted toward the surface of graphene
plane by van der Waals interaction. Then water molecules in emulsion
tend to coagulate each other by hydrogen bond and exclude the less
polar octadecane molecules to the graphene surface due to hydrophobic
interaction.
4. Conclusions
The present investigation showed that column of exfoliated graphite
(EG) is able to reduce the oil concentration of actual produced water.
The oil concentration of 278 and 66 mg/L of produced water decreased
to 1.2 mg/L and undetectable, respectively. Similarly, the TOC de-
creased from 566 mg/L to 1.5 mg/L. The deposition of organic mate-
rials on the surface of EG was detected by SEM image of EG taken after
oil-sorption experiment. FT-IR and TG-DTA measurements also sup-
ported this observation. No structural change of EG during oil-sorption
was confirmed by Raman and XRD measurements. The molecular dy-
namics simulation supported the above observation. Adsorption energy
of octadecane molecules (3 kinds of isomers: n-octadecane,
2,2,4,9,11,11-hexamethyldodecane, 5,5-butyldecane) was calculated.
The oil molecules tend to spread over EG flat surface. However, defects
such as OH functional groups on the graphene surface attract oil droplet
by Coulomb interaction and prevent it spreading over EG surface.
Acknowledgement
This research was supported by the Center of Innovation Program,
“Global Aqua Innovation Center for Improving Living Standard and
Water Sustainability” from Japan Science and Technology Agency
(JST).
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in the
online version, at http://dx.doi.org/10.1016/j.jwpe.2017.11.009.
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