Journal of Water Process Engineering: Sciencedirect
Journal of Water Process Engineering: Sciencedirect
Journal of Water Process Engineering: Sciencedirect
A R T I C LE I N FO A B S T R A C T
Keywords: The discharges of dye-containing wastewater have predominantly been attributed to the textile industry, where
Oil palm frond methylene blue (MB) is the most commonly-used dye. The use of graphene-based adsorbents with sugar as the
Graphene shell composite natural carbon source has been reported as a new milestone; however, the sustainability of entailing sugar in
Adsorption such engineering practices is questionable. Considering the generation of agricultural waste from palm oil mills
Sustainable practice
in the context of Malaysia and the need of more sustainable carbon sources for the synthesis of graphene-based
Methylene blue
adsorbents, this study explored the synthesis of graphene shell composite (GSC), a new generation of graphene-
based adsorbents, with oil palm frond (OPF) juice as the natural carbon source and with oil palm kernel shell as
the base material. The synthesized GSC was characterized by scanning electron microscopy (SEM) and X-ray
diffraction (XRD). The adsorption performance was evaluated by studying the effect of synthetic MB solution
concentration and the GSC mass. 75.45%–99.13% removal of MB ions from synthetic MB solution after 20 h of
adsorption performance study suggested the applicability and effectiveness of the synthesized GSC in treating
dye-containing wastewater. Further kinetics analysis revealed that the interactions between GSC and MB ions
fitted the Freundlich isotherm (R2 = 0.9631-0.9689) and pseudo-second order isotherm (R2 = 0.9860-0.9980).
Such findings reflect that the uptake of MB ions by GSC was mechanistically a multilayer adsorption, in which
the MB ions approached the active sites on GSC surfaces and were continually adsorbed thereon through che-
mical bonding.
1. Introduction bodies.
The treatment of wastewater can be categorized into three groups:
Dyes are organic compounds used to impart colouration to materials biological treatment, chemical treatment, and physical treatment [8].
such as textiles, papers, and leather. The production of dye-containing Biological treatment involving the use of microorganisms is the most
wastewater has predominantly been attributed to textile manu- economical. However, the method is time-consuming, given the in-
facturing: during the dyeing process in producing colored fabric, the evitably long retention time for microbial degradation. Moreover, its
dye dissolved in water is imparted to the fabric whereas the remaining efficiency is lacking due to the complex molecular structure of MB
dye-containing water is discharged into various water bodies as was- [9,10]. As for chemical treatment, coagulation is widely used for was-
tewater [1,2]. One of the common dyes in the textile industry is me- tewater treatment [11]. Although its relative effectiveness and shorter
thylene blue (MB) due to its deep-blue appearance [3,4]. The presence operation time, chemical treatment suffers from drawbacks such as the
of MB in water bodies has been known to be hazardous. The dark-co- need for costly chemicals and difficulty in handling the resultant sludge
lored MB restricts the direct penetration of light into the water body, [12]. Lastly, physical treatment is the most feasible, effective, and
hence prohibiting the growth of aquatic life [5,6]. Additionally, the simplest wastewater-treatment method [13,14]. Adsorption, a physical-
exposure of humans to MB may cause vomiting, chest pain, hard treatment method with the use of activated carbon (AC), has been ap-
breathing, and fast heartbeat [7]. Given such complications, it is im- plied for decades in wastewater treatment. Efforts have been under-
perative to treat MB wastewater before its discharge into the water taken to replace AC with a more sustainable adsorbent, such as one
⁎
Corresponding author at: Research Centre for Sustainable Process Technology (CESPRO), Faculty of Engineering and Built Environment, Universiti Kebangsaan
Malaysia, 43600 Bangi, Selangor, Malaysia.
E-mail address: yh_teow@ukm.edu.my (Y.H. Teow).
https://doi.org/10.1016/j.jwpe.2020.101185
Received 19 December 2019; Received in revised form 2 February 2020; Accepted 11 February 2020
2214-7144/ © 2020 Elsevier Ltd. All rights reserved.
Y.H. Teow, et al. Journal of Water Process Engineering 35 (2020) 101185
synthesized from agricultural waste [15,16]. through scanning electron microscopy, SEM (ZEISS, SIGMA). Prior to
The palm oil industry is the largest agricultural industry in the SEM analysis, a thin layer of gold was coated on the synthesized
Malaysia; its 4.7 million hectares of palm oil plantations and 416 op- GSC. The SEM micrograph was captured at an accelerating voltage of 3
erating oil mills are estimated to produce 13.97 million tonnes of oil kV and at the magnification of 2.5 k×. The chemical composition on
palm frond (OPF), constituting to the largest biomass in the industry the surface of GSC was analyzed using energy dispersive X-ray spec-
[17]. OPF is produced during the pruning of oil palm fresh fruit bunch. troscopy (EDX), Oxford INCA PentaFETX3 (Oxford, UK). Meanwhile,
It is left in palm oil plantations for soil conservation. Structurally, OPF the crystallinity of the synthesized GSC was examined through the X-
has been found to comprise a high carbohydrate-rich in simple sugars ray diffraction, XRD (Bruker, German). The XRD spectrum was com-
[18]. In this regard, Gupta et al. [19] have proposed a new graphene- pleted at a 2θ scan range of 5° – 80°.
based adsorbent with superior adsorption capacity with sugar as the
natural carbon source. Besides, Khan et al. [20] had synthesized gra- 2.4. Adsorption performance study
phene sand hybrid stacked on inorganic sand support as adsorbent
using date syrup as a carbon source. It was reported that the adsorbent 2.4.1. Effect of synthetic MB solution concentration
had successfully removed > 99 % methyl violet and > 93 % congo red Synthetic MB solutions were prepared at different concentrations:
dye with an initial dye concentration of 200 mg L−1. Even though these 1.00 mg L−1, 1.50 mg L−1, 5.00 mg L−1, 10.00 mg L−1, 15.00 mg L−1,
adsorbents have shown much potential in the adsorption-based treat- and 20.00 mg L-1 [22]. For each concentration, a working volume of
ment process, the sustainability of entailing sugar and date syrup for 250 mL was added into a conical flask, to which 20 g of GSC was then
such engineering practices remains questionable. added. The conical flask with the mixture was placed on an isothermal
Considering the generation of agricultural waste from palm oil mills shaker and shaken at 200 rpm for 20 h under room temperature. The
in the context of Malaysia and the need of more sustainable carbon synthetic MB solution was sampled and analyzed at 20-min intervals for
sources for the synthesis of graphene-based adsorbents, OPF, a biomass the first 1 h, then at 1-h intervals for the next 7 h, and lastly at 2-h
waste from palm oil industry with high sugar content has the potential intervals for the following 12 h. The concentration of the solutions was
to be used as the carbon source for the synthesis of graphene-based analyzed through a UV–vis spectrophotometer at the wavelength, λmax,
adsorbent, transferring the graphene-based adsorbent synthesis process of 664 nm. The amount of MB adsorbed onto GSC at time, t, (Qt) (mg
into a more sustainable engineering practice. The objective of this study g−1) was evaluated through Eq. (1) [23].
is to explore the feasibility of OPF juice as a natural carbon source for
(Co − Ct ) V
the synthesis of graphene shell composite (GSC), a new generation of Qt =
W (1)
graphene-based adsorbents using oil palm kernel shell as the base
material. The effect of synthetic MB solution concentration and GSC where Co is the initial concentration of the synthetic MB solution (mg
mass towards the adsorption performance was studied in which the L−1), Ct is the concentration of the synthetic MB solution at time t (mg
synthetic MB solution concentration was varied from 1 mg L−1 to 20 L−1), W is the weight of GSC (g), and V is the volume of the synthetic
mg L−1. Whereas, the mass of GSC was manipulated from 5 g to 20 g. MB solution (L).
Subsequently, equilibrium isotherm and kinetic isotherm were used to
understand the adsorption mechanism pathways and to explain the 2.4.2. Effect of GSC mass
dependence of adsorbent’s surface properties towards the adsorption Four conical flasks were prepared, each with 250 mL of the syn-
performance. thetic MB solution with a concentration of 20 mg L−1. For each of the
flasks, different masses of GSC were added: 5 g, 10 g, 15 g, and 20 g
2. Materials and methods [22]. Each flask with the mixture was placed on an isothermal shaker
and shaken at 200 rpm for 20 h under room temperature. The synthetic
2.1. Materials MB solution was sampled and analyzed at 20-min intervals for the first
1 h, then at 1-h intervals for the next 7 h, and lastly at 2-h intervals for
Fresh OPF was collected from the East Mill, Sime Darby Plantation, the following 12 h. The concentration of the synthetic MB solution was
Carey Island, Malaysia. The fresh OPF was stored at 4 °C to prevent analyzed through a UV–vis spectrophotometer (λmax =664 nm). Si-
microbial biodegradation prior to the adsorption studies. Sulphuric acid milarly, the amount of MB adsorbed onto GSC at time, t, was evaluated
(H2SO4) was procured from R&M Marketing, UK, while MB was pur- through Eq. (1).
chased from Merck, Germany.
2.5. Adsorption model
2.2. GSC synthesis from OPF
2.5.1. Equilibrium isotherm
OPF was squeezed with the sugarcane machine to extract the OPF Two equilibrium isotherms (Langmuir isotherm and Freundlich
juice. Around 10 L of OPF juice was obtained through the pressing of 25 isotherm) were used in this study as most of the adsorption of organic
kg fresh OPF. Pressed OPF juice was filtered with 0.2μm Whatman pollutants –MB dye follows the Freundlich model (47 %) and Langmuir
membrane nylon filter to produce extracted OPF juice for GSC synthesis model (36 %). The remaining followed Temkin model (2.4 %), Sips
[21]. Then, 1 L OPF juice and 60 mL H2SO4 were mixed in a beaker and model (1.57 %), Dubinin-Radushkevich (D-R) model, and GAB model
heated at 260 °C for 6 h to concentrate the mixture. This resultant [24]. The Langmuir isotherm characterises the development of a mono-
concentrated mixture was then mixed with 300 g oil palm kernel shell layer adsorbate on the surface of an adsorbent, in which further ad-
(300 μ m-600 μ m) and stirred well. Subsequently, the coated oil palm sorption will not occur when the active sites on the surface have been
kernel shell was laid in the crucible and dried in the furnace with a occupied by the adsorbate. The linear Langmuir isotherm is expressed
programmed thermal setting as described in our previous research by Eq. (2) [25].
study [22]. The synthesized shell composite was then cooled to room Ce 1 C
temperature. The GSC was rinsed with distilled water to obtain neutral = + e
qe qo K c qo (2)
pH before drying in the oven.
where Ce is the concentration of the adsorbate solution at equilibrium
2.3. Characterization of the GSC (mg L−1), qe is the amount of the adsorbate adsorbed per unit mass of
the adsorbent (mg g−1), qo is the adsorption capacity of the adsorbent
The surface morphology of the synthesized GSC was examined (mg g−1), and Kc is the Langmuir constant (L mg−1).
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Y.H. Teow, et al. Journal of Water Process Engineering 35 (2020) 101185
The SEM micrograph reveals the rough and irregularly-shaped Element Weight percent (%) Atomic percent (%)
surfaces of the GSC under 2.5 k × magnification and 10 k × magni- Carbon 46.7 0.3
fication (Fig. 1). Such roughness and irregularity of the surfaces are Oxygen 30.1 0.2
advantageous for an adsorbent: they promote not only the adhesion of Silica 12.9 0.1
the adsorbate onto the active sites, but also the subsequent removal of Aluminium 4.0 0.1
Potassium 3.4 0.1
the MB ions from the synthetic MB solution [29]. Besides, the cluster
Sulfur 1.8 0.0
structure and porous nanosheet structure were observed on the GSC Sodium 1.1 0.0
surface at higher magnification. It is hypothesized that cluster structure
and porous nanosheet structure would provide higher adsorption ac-
tivity, which in good agreement with the findings obtained by Farghali
et al. [30]. Table 1 presents the elemental weight percent (wt%) ob-
tained from EDX analysis. The synthesized GSC indicated the presence
of mainly carbon, oxygen and silica with 46.7, 30.1, 12.9 wt%, re-
spectively. The EDX analysis shows a high content of carbon owing to
the conversion of carbon source in the OPF juice into graphene during
carbonization and is in agreement with the literature reported [31].
The XRD spectrum of the GSC reveals a noticeably high spike at 25°
(Fig. 2). This observation suggests that the carbon source in the OPF
juice has been converted into graphene for the synthesis of the GSC.
This finding corroborates that by Dubey et al. [23], who found that the
peak representing graphene in the XRD spectrum was observed between
20° and 27°. Besides, Fig. 2 indicates that the diffraction peaks are low
and broad, probably due to small GSC particle size and incomplete Fig. 2. XRD spectrum of GSC.
inner structure formation [32]. In addition, a small peak at 43° in-
dicates the presence of amorphous carbon with a less ordered structure,
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Y.H. Teow, et al. Journal of Water Process Engineering 35 (2020) 101185
the GSC surface [37,38]. Additionally, the strong driving force offsets
the resistance between the solid phase (GSC surface) and the aqueous
phase (synthetic MB solution) to a greater extent. On the other hand,
the time needed to attain equilibrium in the adsorption becomes pro-
gressively longer with increasing concentrations of the synthetic MB
solution [4]: 7 h for 1.00 mg L−1, 8 h for 1.50 mg L−1 and for 5.00 mg
L−1, 9 h for 10.00 mg L−1 and for 15.00 mg L−1, and 12 h for 20.00 mg
L−1. This was because the greater amount of MB ions in the synthetic
MB solutions with high concentrations necessitated a longer time for
the ions to bind and occupy the active sites available on the GSC surface
[39,40]. At the end of the 20-h adsorption, more than 80 % of the MB
ions in the synthetic MB solution were removed (Fig. 4), regardless of
the concentration of the synthetic MB solution in use. This result has
demonstrated the effectiveness of the GSC in treating dye-containing
wastewater at different concentrations. For visual inspection, photo-
graphs of the synthetic MB solutions before and after the 20-h were
Fig. 3. Amount of MB adsorbed at different times during adsorption. taken (Fig. S1). The synthetic MB solution changed into a transparent
solution after 20 h of adsorption, further suggesting the effectiveness of
supports the observation in Fig. 1 [33]. The XRD analysis has confirmed the GSC in removing MB ions from the synthetic MB solution.
the successful synthesis of GSC, a new generation graphene-based ad-
sorbents, with OPF juice as the natural carbon source and oil palm
3.2.2. Effect of the GSC mass
kernel shell as the base material.
To elucidate the effect of the GSC mass, two parameters were ex-
amined: the amount of MB adsorbed onto the GSC at different times
3.2. Adsorption performance study during adsorption (Fig. 5) and the percentage of MB removal at dif-
ferent times during adsorption (Fig. 6). As illustrated in Fig. 5, the
3.2.1. Effect of the concentration of the synthetic MB solution lower adsorption capacity was attained through the higher GSC mass
To elucidate the effect of the concentration of the synthetic MB for the adsorption, probably due to the greater number of active sites
solution, two parameters were examined: the amount of MB adsorbed which competed for the adhesion of MB ions [41,42], given the higher
onto the GSC at different times during adsorption (Fig. 3) and the GSC mass. As seen, that the amount of MB being adsorbed at time t, qt
percentage of MB removal at different times during adsorption (Fig. 4). (mg/g) for 10 g has reached stagnant stage at 14 h indicate adsorption
Fig. 3 illustrates the duration taken for the GSC to be saturated with MB equilibrium was achieved [31]. The lower adsorption capacity for
ions hence desorption/regeneration of GSC is needed as the adsorbent higher GSC mass was observed probably due to the agglomeration of
has no longer affective in adsorption beyond saturation. As seen, rapid GSC at high adsorbent concentration [43]. Additionally, the majority of
adsorption occurred in the initial stage, given the abundance of active the active sites were not fully occupied by MB ions even at the end of
sites available on the GSC surface [34,35]. This postulation is reflected the 20-h adsorption. As with the effect of the concentration of the
by the steep gradient in the adsorption profile in the initial stage of the synthetic MB solution, the time needed to attain equilibrium in the
process. With time, the active sites on the GSC surface were progres- adsorption becomes progressively shorter with increasing GSC masses:
sively occupied by the MB ions. The gradient of the adsorption profile 16 h for 5 g, 14 h for 10 g and for 15 g, and 10 h for 20 g. This was
was thus reduced and reached a plateau when equilibrium was attained because the MB ions in the synthetic MB solution could be adsorbed on
for the adsorption. The adsorption capacity is the amount of MB ions the greater number of available active sites for higher GSC masses
adsorbed onto the GSC upon equilibrium [29,36]. As presented in within a shorter time, giving rise to a shorter equilibrium time. Higher
Fig. 3, the adsorption capacity improved with increasing concentrations percentages of MB removal were achieved with increasing GSC masses
of the synthetic MB solution: the highest adsorption capacity is ex- used in adsorption [44]. This could be attributed to the greater avail-
hibited by the adsorption with the use of 20 mg L−1 synthetic MB so- ability of active sites for the removal of MB ions from the synthetic MB
lution (the highest concentration). Two reasons underlie this. Firstly, solution. Photographs of the solutions before and after the 20-h ad-
the high concentrations of the synthetic MB solution implies more MB sorption (Fig. S3) corroborated the analytical results presented in Fig. 6.
ions, and thus a stronger driving force for occupying the active sites of The deep blue color of the synthetic MB solution was greatly reduced by
Fig. 4. Percentage of MB removal at different times during adsorption. Fig. 5. Amount of MB being adsorbed at different times during adsorption.
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Y.H. Teow, et al. Journal of Water Process Engineering 35 (2020) 101185
Table 3
Pseudo-first order parameters, pseudo-second order parameters, and correlation
coefficients for the adsorption performance study in examining the effect of
concentrations of the synthetic MB solutions.
Kinetic isotherm Co (mg L−1) R2 K1 qeq,exp qeq ε%
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Y.H. Teow, et al. Journal of Water Process Engineering 35 (2020) 101185
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Y.H. Teow, et al. Journal of Water Process Engineering 35 (2020) 101185
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