Chemical Engineering Journal 380 (2020) 122481

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Chemical Engineering Journal

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Porous polydivinylbenzene (PDVB) as an efficient adsorbent for T

hydrocarbons: Effect of porogens on adsorption capacity
Sathyapal R. Churiparda,b, Kempanna S. Kanakikodia,b, Dheer A. Rambhiac,
Ch. Siva Kesava Rajud, A.B. Halgeria, Nettem V. Choudaryd, Gandham Sri Ganeshd,
⁎
Raman Ravishankard, Sanjeev P. Maradura,
a
Materials Science Division, Poornaprajna Institute of Scientific Research (PPISR), Bidalur Post, Devanahalli, Bangalore 562164, Karnataka State, India
b
Graduate Studies, Manipal Academy of Higher Education, Manipal 576104, Karnataka, India
c
Department of Chemical Engineering, M.S. Ramaiah Institute of Technology, Bangalore 560045, India
d
Hindustan Petroleum Green R&D Centre (HPGRDC), KIADB Industrial Estate, Tarabahalli, Hoskote Taluk, Bengaluru 560067, Karnataka, India

H I GH L IG H T S G R A P H I C A L A B S T R A C T

• Acovery
simple approach for oil uptake/re-
is developed over a polymeric
adsorbent.
• Porogens greatly influence the por-
osity and adsorption capacities of
PDVB-EA.
• PDVB-EA displayed high oil uptake
(1600 wt%) with good recycling effi-
ciency.
• Hydrophobic & π-π interactions play a
key role in achieving high uptake ca-
pacity.
• PDVB-EA outcompetes most of the
adsorbents reported in the literature.

A R T I C LE I N FO A B S T R A C T

Keywords: A series of porous polydivinylbenzene (PDVB) adsorbents were synthesized by free radical polymerization of
Adsorption divinylbenzene in different porogenic solvents. The systematic investigation of effect of porogens on the ad-
Oil spill sorption capacity reveals that the ethyl acetate is the best porogenic solvent for adsorption of hydrocarbons. The
Porous polymer detailed characterization of PDVB polymer highlights the importance of superhydrophobicity, high surface area
Adsorbent
and pore volume in achieving enhanced adsorption of crude oil and various other hydrocarbons. Kinetics for
Superhydrophobicity
adsorption study was conducted to define the adsorption process and its mechanism. The reusability and re-
covery study demonstrated that the PDVB-EA is stable to retain its porous structure and high adsorption capacity
with > 90 wt% oil recovery. PDVB EA exemplified the selective gelation of crude oil from water/sea water with
excellent adsorption capacity (1600 wt%, crude oil). The findings observed herein are comparable with the state
of the art materials reported for oil adsorption at room temperature which is very crucial for the practical
applications. The remarkable adsorption capacity, oil recovery and reusability of PDVB-EA polymer make it a
potential adsorbent for oil spill recovery.

⁎
Corresponding author.
E-mail address: sanjeevpm@poornaprajna.org (S.P. Maradur).

https://doi.org/10.1016/j.cej.2019.122481
Received 18 March 2019; Received in revised form 24 July 2019; Accepted 10 August 2019
Available online 12 August 2019
1385-8947/ © 2019 Elsevier B.V. All rights reserved.
S.R. Churipard, et al.
1. Introduction
Water contamination by oil spill and toxic metal ions is becoming a
major threat to the environment. Petroleum products and toxic ions
released from the industries into water bodies pose severe problem to
the ecosystem for a long time. Despite of enormous remediation efforts,
recent oil spill accidents have caused death of thousands of aquatic
animals [1–8]. There are several efficient adsorbents reported for re-
moval of diverse toxic metal ions from polluted water such as conjugate
nanomaterial (CNM), novel nanocomposite materials [9,10] functional
ligand anchored nanomaterial [11], inorganic-organic based novel
nano-conjugate material [12] novel hierarchical composite adsorbent
[13], ligand immobilized nano-composite adsorbent [14], crown ether
immobilized conjugate adsorbent, ring size dependent crown ether
based adsorbents [15], novel composite nanomaterials [16,17]. Many
of these adsorbents have shown high adsorption of toxic metal ions
from the water. The adsorbents reported in literature for oil spill
cleanup are comparatively lesser in contrast to adsorbents reported for
toxic ions removal. Therefore, there is a huge demand for the devel-
opment of efficient adsorbent for oil-spill recovery.
Conventionally, the oil spill clean-up was done by in-situ burning of
oil, addition of dispersing agent to enable the natural degradation but
these techniques show poor efficiency, and cannot separate emulsions.
They may also introduce other contaminants during the cleanup process
[18,19]. The adsorptive separation on porous solids is considered as the
most powerful technique for removal of spilled oil [20]. Many con-
ventional materials such as zeolites, wool fiber, activated carbon etc.
have been used for the oil adsorption, but these materials show low
adsorption capacity, slow kinetics and exhibit non selective adsorption
due to hydrophilic nature of these adsorbents. To overcome the set-
backs of the conventional adsorbents many novel adsorbents were de-
veloped for the separation of oil-water mixtures such as superwetting
monolithic SiO2, magnetic carbon nanotube (CNT) sponges [21],
macroporous Fe/C nanocomposites [22], hydrophobic nanocellulose
aerogels [23]. However, these adsorbents show poor adsorption capa-
city, lack of recyclability and difficulty in recovering the oil. Many fire
resistant adsorbents were reported for removal of oil spill by combus-
tion recycling application [24–26]. This approach is not a viable solu-
tion for the oil-water separation as the process involves the burning of
oil during adsorbent regeneration.
Phase-selective organogels such as dipeptide-based amphiphilic
LMOG [2], and the derivatives of phase-selective organogels including
sugar‐derived [27], aromatic amino acid based organogelators [28]
were synthesized and investigated for oil spill recovery. These orga-
nogelators show high oil uptake, however the heating-cooling cycles
used to initiate the gelation is a major limitation for its practical ap-
plications. In some cases, the use of water miscible solvents (tetra-
hydrofuran, ethanol and dioxane) for gelation consumes lot of energy
and leaves toxic pollutants behind.
Recently, polymers have emerged as promising materials for ad-
sorption [29,30], catalysis [31–34] and separation applications
[35–38]. Porous polymers are better fitting candidates for many ap-
plications due to their inbuilt porosity, tuneable pore size, stability and
recyclability. These beneficial properties are very crucial for their
practical applicability [39–45]. The oil-water separation is an inter-
facial challenge; the use of hydrophobic materials are best suited to
solve this problem [46]. Hydrophobicity and oleophilicity are the two
important properties of an ideal adsorbent which is certainly pertinent
in case of porous polymers [22,47]. Polydivinylbenzene (PDVB) based
polymers and their composite materials have been synthesized by
various routes and used for the adsorption of CO2, oil recovery and
adsorption of organic pollutants from polluted water. However, there is
no detailed study on the adsorption of crude oil and various hydro-
carbon using polydivinylbenzene based polymers [48–54].
Some of the materials such as multifunctional foam [19], carbon
based aerogels [26,55], CNT aerogels [56], silicone aerogels [57], CNT
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Chemical Engineering Journal 380 (2020) 122481
sponges [58], hydrophobic polyurethane foams [59], twisted carbon
fiber (TCF) aerogel [55], spongy graphene [60], etc. are reported to
show exceptional adsorption capacities and recyclability. For instance,
the twisted carbon fiber (TCF) aerogel has shown the sorption capacity
for pump oil up to 192 times [55], the CNT sponge can absorb variety of
organic solvents with high selectivity and adsorption capacities. (180
times) [58] spongy graphene adsorbs the organic pollutants up to 86
times [60]. Regardless of their potential, these materials entail complex
synthetic procedure, for example synthesis of carbon based aerogels is
quite expensive because it involves techniques like freeze drying and
also the moulding them into large monlithic forms is very difficult for
practical applications. Moreover, the synthesis of graphene aerogel and
CNT involves harmful and expensive chemicals, complex equipments
and tedious processes which constrain their large scale applications.
Many of the aforementioned problems could be overcome by using
porous polymeric adsorbents.
The polymeric adsorbent, reported herein involves simple synthetic
approach, which excludes the use of harmful and expensive chemicals.
The room temperature adsorption by PDVB polymer avoids the use of
heating-cooling cycle and the use of harmful carrier solvents. The su-
perhydrophobicity of the PDVB polymer enables the selective adsorp-
tion of oil from sea water which is not possible with conventional ad-
sorbents that sinks in water after oil adsorption. These features of PDVB
polymer make it a potential substitute to the conventional adsorbents
for oil spill cleanup and recovery.
2. Experimental section
2.1. Materials
All the chemicals used in this study were obtained from the com-
mercial suppliers and used without further purification.
Tetrahydrofuran (THF) (SDFCL, 99.5%), acetone (Merck, 99%), ben-
zene (SDFCL, 99.5%) and ethyl acetate (EA) (Merck, 99%), n-hexane
(Avra), cyclohexane (Merck, 99%), toluene (Merck, 99.5%), m-xylene
(Merck, 99%). Divinylbenzene (TCI chemicals), azobisisobutyronitrile
(AIBN) (Avra), crude oil (BASRAH) was provided by Hindustan
Petroleum Green R & D center, Bangalore.
2.2. Synthesis of PDVB-THF polymer
In a typical synthesis, 4 g of DVB monomer was added to a 100 ml
round bottom flask containing 40 ml THF and 100 mg of AIBN as a
radical initiator. 4 g of water was added to the above mixture and
stirred at 30 °C for 3 h. Then the mixture was solvothermally treated at
100 °C for 48 h in a teflon lined autoclave to facilitate the poly-
merization of divinylbenzene (Scheme 1) [44]. Obtained material was
placed in an open vessel to allow the slow evaporation of the porogenic
solvents. The material obtained was crushed to powder and degassed at
100 °C for 3 h to remove the trapped solvents. It is designated as PDVB-
THF. Similarly, PDVB polymer was synthesized with other solvents such
as ethyl acetate (EA), dimethyl formamide (DMF), benzene (benz) and
AIBN, THF, H2O
100 °C, 48 h
Divinyl benzene Polydivinyl benzene (THF)
Scheme 1. Synthesis of PDVB-THF polymer.
S.R. Churipard, et al.
acetone (ace) without adding water as a co-porogen because of its in-
compatibility in these solvents.
2.3. Instruments and characterization
The porous properties of the PDVB polymers were determined by
nitrogen sorption measurement using BELSORP-MINI II instrument at
77 K. All the samples were degassed at 120 °C for 3 h prior to the
analysis. The specific surface area of the polymers synthesized was
determined by the Brunauer–Emmett–Teller (BET) equation. The pore
volume of the polymers was calculated from Barrett–Joyner–Halenda
(BJH) model. The FTIR analysis of all polymers were performed using
Alpha T-Bruker instrument in the wavenumber range of
4000–500 cm−1 in transmission mode by KBr pellet technique to know
the chemical properties of synthesized polymers. The thermal stability
of polymer was investigated by thermogravimetric analysis using
Shimadzu DTG-60 instrument under flowing air with the ramp rate of
10 °C min−1 from 30 °C to 800 °C. Scanning electron microscopy (SEM)
analysis was performed using Hitachi SU 3500 N SEM instrument. The
contact angle of water on PDVB-EA polymer was performed by placing
a drop of water on top of a PDVB-EA pellet. The contact angle between
the water droplet and surface of polymer was captured using a digital
camera and the image was analysed.
2.4. Liquid phase adsorption of crude oil and other hydrocarbons
In a typical procedure, a known quantity (1000 mg) of hydro-
carbon/crude oil was taken in a glass vial and it was contacted with the
PDVB polymers with occasional shaking of the glass vial. The formation
of gel (oil + adsorbent) was carefully observed and uptake capacity of
the adsorbent was calculated based on the final weight of the adsorbent
added to the vial (ESI Fig. S1). The mass of glass vial before and after
addition of adsorbent was noted to calculate weight of adsorbent. The
adsorption capacity of PDVB polymer is calculated using the following
equation:
Adsorption capacity (wt %) = weight of the hydrocarbon (g )
× 100/ weight of PDVB polymer (g )
The adsorption of crude oil was also performed in large scale to
check practical applicability of PDVB-EA polymer. In a typical experi-
ment, 1.5 L of water was taken in a 3 L glass tray and 152.8 g (182 ml)
of crude oil was added to it, then PDVB-EA polymer was slowly added
to facilitate the selective adsorption crude oil from water. The addition
of polymeric adsorbent was continued until no liquid crude oil was
observed in the tray. 8.4 g of PDVB-EA was required to adsorb 152.8 g
of crude oil. The adsorption capacity was found to be 18 times. The
crude oil forms a gel with PDVB-EA polymer and floats on water which
could be easily removed from water, the oil and polymer could be re-
covered and reused (ESI Fig. S2 and ESI Video S1).
2.5. Emulsion phase adsorption experiments for sorption kinetics
The adsorption studies were carried out in a toluene-water emul-
sion. Toluene was selected because of its low water solubility, emulsion
forming ability and its weak polar properties. The identification of to-
luene concentration in the emulsion is easy compared to the crude oil-
emulsion mixture due to the presence of various compounds in crude
oil, several peaks will be observed in GC. In order to control the
emulsion properties such as stability and concentration, a synthetic
emulsion was prepared at controlled toluene concentration by adding
5 ml of toluene to 200 ml of water and stirred vigorously at 1000 rpm.
The stability of the emulsion was maintained for a sufficient amount of
time to perform the experiments.
The synthetic emulsion was stirred at 1000 rpm and a known weight
of adsorbent PVDB-EA was added (0.1–0.25 g). The change in
3
Chemical Engineering Journal 380 (2020) 122481
concentration of the emulsion was identified by taking 1.5 ml of sample
at regular intervals of time. The toluene in the sample was extracted
with 0.5 ml of cyclohexane and the organic layer was analyzed by GC to
find out the kinetics of adsorption. The equilibrium concentration (Ce
g/g) was noted when there is no further adsorption or desorption taking
place. The uptake capacity at any point was calculated by the mass
balance qt = ((Co-Ct) × V)/m,
where Co is the initial toluene concentration (g/L),
Ct is the toluene concentration (g/L) at a particular time,
V is the volume of sample (L) and m is the mass (g) of PDVB-EA.
2.6. Recovery of crude oil from PDVB-EA polymer
PDVB-EA polymer was subjected for selective adsorption of crude
oil from water at room temperature until all crude oil is adsorbed on
PDVB-EB polymer to form a gel. The gel formed was separated from
water and washed using toluene as a stripping agent in a Buchner
funnel. The adsorbent was washed thoroughly with toluene until the
adsorbent regained its original white colour. The filtrate thus obtained
was distilled off in a rotary evaporator to separate out toluene and
crude oil. The distilled toluene was recycled back and used to recover
the crude oil from the next adsorption cycle. The crude oil recovery
was > 90% and the PDVB-EA polymer retained its high adsorption
capacities for three consecutive recycles.
2.7. Regeneration of PDVB-EA polymer
Many adsorbents reported in literature require energy intensive and
laborious regeneration procedures. In contrast, adsorbent used herein
involves simple washing with toluene and drying in hot air oven to
regenerate the material. The typical procedure involves the washing of
spent PDVB-EA polymer with excess of toluene to remove crude oil
adsorbed and it was dried in hot air oven at 100 °C for 2 h. The dried
adsorbent was reused for adsorbing crude oil for the next cycle and
again the regeneration steps are repeated to regenerate the polymer for
further use (Scheme 2). The polymer retained its adsorbing capacity for
three recycles with high efficiency which is very crucial for the practical
applications.
3. Results and discussion
3.1. Characterization
Nitrogen sorption analysis of PDVB-EA, PDVB-DMF and PDVB-THF
polymers demonstrated the pronounced hysteresis caused by the ca-
pillary condensation of liquid nitrogen in the pores of the polymers.
These materials showed very high BET surface area (590–615 m2g−1)
and BJH pore volumes (1.7–2.1 cm3/g). The total surface area and pore
volume was highest when ethyl acetate was used as the solvent,
whereas the surface area and pore volume has reduced drastically when
acetone and benzene was used as the solvent for PDVB synthesis
(Table 1). It is evident from the literature that the porogenic solvents
have significant effect on the porous properties of the polymers
[39,61–64].
The FTIR spectra of fresh and used PDVB-EA polymers are shown in
Fig. 1. The characteristic bands observed at 1105 cm−1, 1602 cm−1,
2963 cm−1 and 3020 cm−1 in the FTIR spectra of PDVB polymers are
ascribed to CeC, C]C, CeH and C]CeH stretching frequencies re-
spectively. The similar characteristic peaks were observed in spent
PDVB-EA polymer which suggests that the chemical composition of
adsorbent is retained under experimental conditions.
Thermogravimetric analysis of fresh and spent PDVB-EA has been
performed to understand the thermal changes in the material before
and after adsorption (Fig. 2). The PDVB-EA (fresh) showed the multi
step decomposition over the temperature range 25–800 °C. The initial
S.R. Churipard, et al. Chemical Engineering Journal 380 (2020) 122481

Scheme 2. Schematic representation of crude oil adsorption, recovery and reuse on PDVB-EA polymer.

Table 1
Physicochemical properties of PDVB polymers synthesized in various solvent.
Sample SBET (m2 g−1) Pore volume [Vpa] (ccg−1)

PDVB-EA 616 2.06

PDVB-DMF 591 2.09
PDVB-THF 593 1.70
PDVB-Benzene 234 0.123
PDVB-Acetone 22 0.016
Spent PDVB-EAb 595 1.79

a
From BJH method.
b
3 times recycled PDVB-EA.

Fig. 2. TGA plot of fresh and spent PDVB-EA.

Fig. 1. FTIR spectra of fresh and spent PDVB-EA.
weight loss (< 3%) below 250 °C is due to desorption of the solvent
molecules from the polymeric surface. The consequent weight loss
above 300 °C is ascribed to destruction of the polymeric framework. The
TGA analysis shows that the material is stable up to 300 °C which can be
used for adsorption application even in harsh conditions. Similar
weight loss patterns were observed for the spent PDVB-EA material. The
analysis of the spent material indicates that there are no changes in the
thermal properties of the material before and after adsorption of crude
oil.
Scanning electron microscopy (SEM) analysis of PDVB-EA (fresh &
spent) was performed to understand the morphological variations in the
material before and after adsorption studies (Fig. 3). The SEM analysis
of PDVB-EA (Fresh) reveals that the material has irregular rough mor-
phology with the disordered particles with sizes ranging from 10 µm to
125 µm. The SEM analysis of PDVB-EA (spent) showed similar mor-
phological features and particle sizes as in the fresh PDVB-EA. The
analysis showed that the material is stable to retain its original mor-
phology even after 3 adsorption cycles.
The hydrophobicity of PDVB-EA polymer was evaluated by contact
angle (CA) measurement. The contact angle of 150° was observed when
a drop of water was brought in contact with PDVB-EA surface (Fig. 4).
The CA measurement evinces that PDVB-EA polymer is super-
hydrophobic in nature which plays a crucial role in oil-water separa-
tion, as it repels water and selectively adsorbs oil with high efficiency
[45,65].
3.2. Effect of surface area/porosity on adsorption capacity of PDVB
polymers
To understand the effect of porosity on adsorption capacity, the
PDVB polymers were synthesized in various porogenic solvents and
employed for the adsorption of crude oil (Fig. 5). The PDVB-EA polymer
synthesized in ethyl acetate showed very high adsorption capacity
compared to other polymers. The high adsorption capacity of PDVB-EA
could be due to high porosity and surface area induced in the polymer
by the ethyl acetate solvent. It is evident from the literature that the

4
S.R. Churipard, et al.
Fig. 3. SEM images of A) Fresh PDVB-EA and B) Spent PDVB-EA.
Fig. 4. Contact angle measurement of PDVB-EA polymer.
Fig. 5. Effect of porosity on adsorption on crude oil adsorption of PDVB poly-
mers.
porogenic solvents have profound effect on the porous properties of the
polymers: the kind of porogens, solubility of the monomers in the
porogenic solvent and evaporation rate of solvents will greatly influ-
ence the porous properties and surface area of the polymers.
The high adsorption capacity of PDVB-EA, PDVB-DMF and PDVB-
5
Chemical Engineering Journal 380 (2020) 122481
THF is attributed to its very high surface area and pore volume
(Table 1). High surface area and pore volume enables these polymers to
uptake large amount of crude oil/hydrocarbons. The adsorption capa-
cities of PDVB-Benz and PDVB-Ace reduced drastically suggesting that
benzene and acetone are not good porogens for the polymerization of
divinylbenzene. In addition, the nitrogen sorption measurements sug-
gest that PDVB polymer does not have high porosity when benzene and
acetone are used as a solvent. The synthesized adsorbents were sub-
jected for adsorption studies of various hydrocarbons at room tem-
perature (Fig. 6). The PDVB-EA showed the highest adsorption capacity
for most of the hydrocarbons including crude oil, diesel, m-xylene,
cyclohexane and n-hexane; whereas PDVB-DMF demonstrated high
adsorption capacity for sunflower oil, 1-octene and toluene. The ad-
sorption of nitrobenzene was also performed using PDVB-EA polymer
and showed an uptake capacity of 1800 wt%. The optimization of
conditions is very important to achieve high adsorption capacities
[66–70]. The protocol developed herein demonstrates high adsorption
capacity at optimized ambient conditions which can be explored for
large scale applications.
To ensure the practical applicability of PDVB-EA polymer in actual
crude oil-spill recovery, the adsorption experiment was performed in
large scale using 152.8 g of crude oil. The adsorption capacity was
found to be 18 times in large scale adsorption experiments which
suggest that the polymer retains the high adsorption capacity even in
large scale adsorption and has a potential to be used in real oil-spill
recovery (ESI Fig. S2 and ESI Video 1).
3.3. Comparison of adsorption capacity of PDVB-EA polymer with various
adsorbents reported in literature
The adsorption capacity of PDVB-EA polymer was compared with
Fig. 6. Liquid phase adsorption of crude oil and various hydrocarbons.
S.R. Churipard, et al. Chemical Engineering Journal 380 (2020) 122481

adsorbents reported in the literature (ESI Table S1). The PDVB-EA Table 3
polymer outperformed several adsorbents reported for adsorption of Recovery of crude oil from PDVB-EA polymer.
hydrocarbons. The adsorption capacity of PDVB-EA (for crude oil) was Adsorbent Solvent Weigh of Weight of Adsorption Recovery
1600 wt% which is higher compared to the adsorbents such as swellable (PDVB-EA) system crude oil adsorbent capacity (wt (wt%)
porous PDMS, CF3-functionalised silica aerogel and HIPE xerogels. The (mg) (mg) %)
better adsorption capacity of PDVB-EA polymer is ascribed to its su-
Fresh Crude oil 16,000 1000 1600 94
perhydrophobicity, large surface area and pore volume. PDVB-EA 1st recycle Crude oil 15,930 1000 1593 93.5
polymer was proven to be a good adsorbent for series of hydrocarbons 2nd recycle Crude oil 15,240 1000 1524 90.3
such as m-xylene, sunflower oil, diesel, cyclohexane, n-hexane and to- 3rd recycle Crude oil 14,610 1000 1461 90.1
luene. The adsorption capacity of PDVB-EA polymer reported in the
present study is at par with the best adsorbents reported in the litera-
ture. Unlike many reported adsorbents, which involve complex syn-
thetic procedure, the PDVB-EA polymer is easy to synthesize and can be
used as a potential adsorbent for adsorption of various hydrocarbons at
room temperature.

3.4. Selective gelation ability of PDVB-EA in biphasic mixture

PDVB-EA was selected as the best polymeric adsorbent among the

synthesized polymers. Superhydrophobic nature of PDVB-EA polymer
was demonstrated by performing selective adsorption of hydrocarbons
from a biphasic mixture containing water/sea water (Table 2). The sea
water was prepared artificially by mixing the required amount of cor-
responding salts that mimics the exact sea water composition. PDVB-EA
showed selective gelation ability for hydrocarbons over water, it re-
tained its original adsorption capacity for hydrocarbons in biphasic Fig. 7. Adsorption isotherm.
mixture and it formed a gel with the hydrocarbons leaving behind the
water/sea-water. The gels formed were stable for inversion of glass vial
The magnitude of the exponent 1/n gives an indication of the fa-
which indicates the integrity of the gel formed by the polymer with
vorability of adsorption and its dependence on the concentration of the
hydrocarbon (ESI Fig. S1). The selective gelation ability of PDVB-EA
solution. Smaller the 1/n value, greater the heterogeneity [72]. As
polymer is attributed to its superhydrophobic nature of the polymer.
discussed by Alamo-Nole et al. a 1/n value lesser than 1 indicates that
Hence PDVB-EA polymer offers excellent wettability to various hydro-
the sorption process is independent of the adsorbate concentration
carbons due to its oleophilicity and repels water by its hydrophobic
[73]. The 1/n value for the current system is 0.067 which explains that
nature. Therefore it can be used in selective adsorption of oils from
the adsorption process is significantly independent of concentration of
water for successive recycles (Table 3).
adsorbate (Fig. 7). Kf value is related to the loading factor of the sorbent
and the high Kf value represents the high uptake capacity. Kf and n are
3.5. Adsorption isotherm and kinetics
parameter characteristics of the sorbent-sorbate system, which must be
determined by data fitting and linear regression which is used (least
To optimize the design of the adsorption process, it is important to
square method) to determine the kinetic and isotherm models. The
establish the most appropriate correlation for the equilibrium curves.
adsorption of VOCs is generally carried out by dissolving the adsorbates
They are also important in describing how the solute interrelates with
with in their solubility limits [74,75]. Since our experiments were
the adsorbent; hence empirical isotherm equations are essential for the
conducted at higher concentrations similar to hrubesh et al. [76] their
operation of adsorption systems and practical design.
range of values were used as a reference for this study (Table 4).
The Freundlich adsorption isotherm was used to fit the adsorption
In order to examine the controlling mechanism of adsorption such
data as it is the most important multisite adsorption isotherm and ac-
as mass transfer and chemical reaction, kinetic models are used to test
counts for the heterogeneity of real surfaces during adsorption. It as-
the experimental data. The kinetics of toluene emulsion can be modeled
sumes that the frequency of sites available for adsorption decreases
by the pseudo order kinetics. The pseudo second order rate gave a
exponentially with increasing free energy [71]. The Freundlich equa-
better fit to the experimental data and is represented by the equation:
tion is expressed as Qe = KfCe1/n and its linear form is expressed as: t 1 t
= 2 + Qe
Log Qe = Log Kf + 1/n × log Ce. Qt Qe K

where Qe is the weight of solute per unit weight of sorbent (g/g), where K (g/g min) is the rate constant of adsorption,
Ce is the concentration of the solute (g/g), Qt and Qe are the amount of toluene adsorbed at any time and at
n and k (g adsorbate/g sorbent) are the heterogeneity factor and equilibrium.
Freundlich capacity.

Table 2
Selective gelation ability of PDVB-EA polymer in biphasic mixtures.
Polymer Hydrocarbon mixture Weight of adsorbate (mg) Weight of adsorbent (mg) Adsorption capacity (wt%)

PDVB (EA) Crude oil + water 1000 66.45 1505

PDVB (EA) Crude oil + sea water 1000 63.86 1566
PDVB (EA) Crude oil 1000 63.37 1578
PDVB (EA) Diesel + water 1000 85.91 1164
PDVB (EA) Diesel + sea water 1000 85.47 1170
PDVB (EA) Diesel 1000 73.21 1366

6
S.R. Churipard, et al.
Table 4
Results of kinetic study.
Pseudo Second Order
wt (g) Co (g/L) Qe (g/g) k (g/g min) R2
0.25 21.675 20.57613 0.061033 0.964
A linear plot of t vs t was fit by regression and the theoretical Qe
Qt
and K values were calculated which are in the range of the experimental
values (Table 4).
3.6. Plausible adsorption mechanism
The crude oil constitutes of various hydrocarbons with different
physical properties such as viscosity, surface tension, overall size, hy-
drophobicity and polarity. The different constituents of crude oil in-
teract differently with the hydrophobic polymer which is dependent on
their physical properties. The physical properties of the various hy-
drocarbons used for adsorption studies are listed in ESI Table S2. These
compounds adsorb/interact with polymer surface by means of different
mechanisms such as hydrophobic interaction, π-π interactions and ca-
pillary action.
Adsorption due to hydrophobic interactions is generally predicted
using the hydrophobic parameters of organic chemicals such as Kow (n-
octanol-water distribution coefficient) [77,78]. Common driving me-
chanism for the adsorption of hydrophobic organics to hydrophobic
polymers is controlled by the hydrophobic interaction. This is clearly
seen as cyclohexane having a higher log Kow (log Kow = 3.44) has a
larger uptake capacity compared to toluene (log Kow = 2.69). Fur-
thermore, PDVB-EA polymer showed less difference in the uptake ca-
pacity for cyclohexane (having the higher Kow and no π electrons) and
nitrobenzene (having a lower Kow and more π electrons) value sug-
gesting the presence of other adsorption mechanism such as π- π in-
teraction along with the hydrophobic interaction (ESI Table 2) [76,79].
Crude oil contains various polar and unsaturated compounds which
have π electron clouds. The PDVB-EA structure also suggests the pre-
sence of numerous delocalized π electron conjugate systems and ad-
sorbs these organic molecules through π-π electron coupling. In con-
trast, the adsorption of gasoline and vegetable oil can occur by the
bonding between the sigma and the PDVB-EA π electrons [56].
The adsorption of compound having electron withdrawing groups
(–NO2) such as nitrobenzene increases the strength of π-π interactions.
The adsorption capacity is also dependent on the number of aromatic
rings and adsorption capacity increase with the increase in the number
of aromatic rings [80]. The rate of adsorption is dependent on viscos-
ities of the adsorbates and this effect is governed by the capillary force.
The adsorption capacity decreases with the increase in viscosity [81].
4. Conclusion
A novel porous polydivinylbenzene (PDVB) adsorbent has been
synthesized by solvothermal method and characterized by different
techniques. Contact angle measurement of PDVB-EA reveals the su-
perhydrophobic nature with contact angle of 150°. The higher uptake
capacity of PDVB-EA polymer for cyclohexane (large Kow value) and for
polar electron withdrawing nitrobenzene (lower Kow value) confirms
that both hydrophobic interactions as well as π-π interaction are the
major contributors for adsorption. The large oil-uptake capacity by
PDVB-EA, PDVB-DMF and PDVB-THF is due to high surface area and
pore volume as evident from the nitrogen sorption analysis. In contrast
to the above materials PDVB-Benz and PDVB-Ace exhibited lower ad-
sorption capacity which confirms that porogens are the key players in
generating the porosity in the polymer. The adsorption follows the
Freundlich isotherm, the Kf value is 17.9 g/g and the 1/n value was
7
Chemical Engineering Journal 380 (2020) 122481
0.0638 which shows that the adsorption process is independent of the
initial concentration of the adsorbate. The kinetic data showed a good
fit towards the pseudo second order rate equation and the rate constant
is 0.06103 g/g min. Spent adsorbent characterization and reusability
studies proven that the polymer is stable to retain its porous structure
and high uptake capacity (1600 wt%). The adsorption experiment was
performed in large scale and adsorbent retained the original adsorption
capacity which proves that the process is viable for large scale appli-
cations.
Acknowledgements
SRC acknowledges Manipal Academy of Higher Education for per-
mitting this research as a part of the Ph.D. program. SRC thanks CSIR,
India for the award of Senior Research Fellowship. Authors acknowl-
edge Admar Mutt Education Foundation (AMEF) for providing facilities
to carry out this research work. Authors thank Hindustan Petroleum
Green R & D Center (HPGRDC), Bengaluru, India for sponsoring this
project and also for providing crude oil for adsorption experiments.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.cej.2019.122481.
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