Journal of Environmental Management 224 (2018) 252–262

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Journal of Environmental Management

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

The adsorptive removal of chromium (VI) in aqueous solution by novel T

natural zeolite based hollow fibre ceramic membrane
Mohd Ridhwan Adama, Norliyana Mohd Salleha, Mohd Hafiz Dzarfan Othmana,∗,
Takeshi Matsuurab, Mohd Hafizi Alia, Mohd Hafiz Putehc, A.F. Ismaila, Mukhlis A. Rahmana,
Juhana Jaafara
a
Advanced Membrane Technology Research Centre (AMTEC), Universiti Teknologi Malaysia, 81310 UTM, Skudai, Johor, Malaysia
b
Department of Chemical and Biological Engineering, University of Ottawa, Ottawa, Ontario, K1N 6N5, Canada
c
Faculty of Civil Engineering (FCE), Universiti Teknologi Malaysia, 81310 UTM, Skudai, Johor, Malaysia

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

Keywords: Adsorption is one of the most efficient ways to remove heavy metal from wastewater. In this study, the ad-
Natural zeolite sorptive removal of hexavalent chromium, Cr (VI) from aqueous solution was investigated using natural zeolite,
Hollow fibre ceramic membrane (HFCM) clinoptilolite, in the form of hollow fibre ceramic membrane (HFCM). The HFCM sample was prepared using
Phase inversion phase inversion-based extrusion technique and followed by sintering process at different sintering temperatures
Sintering technique
in the range of 900–1050 °C. The fabricated HFCM was characterised using scanning electron microscopy (SEM),
Adsorption
contact angle, water permeability, and mechanical strength for all HFCMs sintered at different temperatures. The
adsorption and filtration test of Cr (VI) were performed using an in-house water permeation set up with a dead-
end cross-flow permeation test. An asymmetric structure with sponge- and finger-like structures across the cross-
section of HFCM was observed using SEM. Based on the characterisation data, 1050 °C was chosen to be the best
sintering temperature as the water permeability and mechanical strength of this HFCM were 29.14 L/m2∙h and
50.92 MPa, respectively. The performance of the HFCM in adsorption/filtration was 44% of Cr (VI) removal at
the Cr (VI) concentration of 40 mg/L and pH 4. In addition, the mathematical model was also performed in
simulating the experimental data obtained from this study. All in all, the natural zeolite-based HFCM has a
potential as a single-step Cr (VI) removal by membrane adsorption for the wastewater treatment.

1. Introduction
With the rapid growth of the global industrialisation, many pro-
blems related to the environment are emerging, which creates risks not
only to the environment, but also to the ecological systems as well as
human health. Nowadays, heavy metals are becoming among the most
hazardous pollutants in the supply and treated water and are imposing
a great harm to human health and aquatic lives due to the ability of
bioaccumulation in body and its high toxicity (Miretzky and Cirelli,
2010; Sarin and Pant, 2006). Various adverse effects related to the
mental and neurological system could be resulted by the exposure,
transportation, and accumulation of the heavy metals such as mercury,
lead, arsenic, and cadmium (Dong et al., 2017; Rehman et al., 2017). Of
all of these heavy metals, chromium is known as one of the top sixteen
major toxic contaminants that has detrimental effects on human health
(Gardea-Torresdey et al., 2000).
Chromium exists in aqueous media in two prominent oxidation state
forms namely trivalent Cr (III) and hexavalent Cr (VI) ions and these are
the most abundantly found forms of chromium in water body.
Naturally, chromium is found in the environment in the form of Cr (III).
However, the oxidation of this type of chromium have generated the Cr
(VI) ions during various industrial processes. This industrial waste
species could be toxic and can be accumulated in many physical and
chemical components in the environment. Cr (III) is said to be less toxic
than Cr (VI), and have a significant role and necessary for lipid and
sugar metabolism, making it as an essential trace element for human
and animal (Bai et al., 2015; Prasad, 2013). In addition, it is advisable
for a human to take Cr (III) of about 50–200 μg∙day−1 (Herrero-Latorre
et al., 2018). Although this species is less toxic to human as well as
essential for dietary nutrient, the excess quantities of Cr (III) may cause
damages to aquatic organism and would eventually disrupt the food
chain. Therefore, the permitted concentration of these Cr species in the
surface or potable water must be less than 0.05 mg/L (Baral and
Engelken, 2002). Meanwhile, Cr (VI) is more poisonous and is known to

∗
Corresponding author.
E-mail address: hafiz@petroleum.utm.my (M.H.D. Othman).

https://doi.org/10.1016/j.jenvman.2018.07.043
Received 29 January 2018; Received in revised form 10 July 2018; Accepted 14 July 2018
Available online 23 July 2018
0301-4797/ © 2018 Elsevier Ltd. All rights reserved.
M.R. Adam et al.
be carcinogenic and mutagenic in nature (Rojas et al., 2005). Cr (VI) is
known to be 100 times more toxic than Cr (III) due to its high water
mobility and solubility, and also because it can be easily reduced. The
carcinogenic effect of Cr (VI) can be strong by causing failure of major
organs such as kidney and liver as well as dermatitis and diarrhoea
(Mohan and Pittman Jr, 2006; Mohan et al., 2005). According to the
World Health Organization (WHO), the permissible level of chromium
in surface water bodies is 0.05 mg/L. However, its concentration in
industrial wastewater ranges from 0.5 to 270 mg/L (Ghosh, 2009). In
addition, the chromium level in water may vary depending on the
geographical and standard limits set by the law of a country. According
to the Environmental Protection Agency (EPA) and the European Union
(EU), the permitted level of Cr in water must be lower than 0.05 mg/L
(Baral and Engelken, 2002). The Indian standard of the maximum
contaminant level (MCL) of the total chromium contained in water is
set as 0.05 mg/L (Pradhan et al., 2017). For the Malaysian standards,
the allowable concentration of Cr has been limited to 0.05–0.1 mg/L,
regulated by the Malaysian Food Regulations (Azlan et al., 2012).
Therefore, the elimination of Cr (VI) becomes a vital issue as the per-
missible amount in the wastewater discharge becomes more stringent.
Many conventional treatments have been developed to remove Cr
(VI) from water bodies, including ion exchange (Rengaraj et al., 2001),
nanoparticles (Gupta et al., 2016), electrocoagulation (Akbal and
Camcı, 2011), and adsorption/filtration (Babel and Kurniawan, 2003).
For all the methods, the capital and operational costs normally set
limitations in the efficiency f the Cr (VI) removal from the wastewater.
In addition, the production of secondary wastes as well as the formation
of a large quantity of slug has further reduced the effectiveness of these
methods (Babel and Kurniawan, 2003; Hegazi, 2013). Thus, the
searching of low-cost and yet effective method in the Cr (VI) removal is
in a real demand and needs immediate attention. One of the promising
ways of contaminant removal from wastewater is by the means of
membrane separation technique.
Recently, the membrane technology has become an excellent way
for wastewater treatment due to its ability of not only separating the
contaminants from the water bodies, but also purifying the treated
water. The semipermeable property of the membranes is known to be
the special feature that only permits several elements or compounds to
pass through them. This special feature of porous membrane is ap-
plicable for many purposes such as wastewater treatment (Abbasi et al.,
2010), drinking water purification (Bellobono et al., 2005), water de-
salination (Fang et al., 2012), gas separation (Nafisi and Hagg, 2014),
and bacteria removal (Kroll et al., 2010). However, only a limited
number of studies reported on the treatment of wastewater containing
heavy metals via membrane technology.
Most of the commercially available membranes are made of poly-
meric materials. The low cost and mass production of polymer have
made the polymeric membrane widely used in the industries. Polymers
that are commonly used to fabricate polymeric membranes are poly-
vinylidene fluoride (PVDF), polysulfone (PSf), polyethersulfone (PES),
and polyacrylonitrile (PAN) (Kong and Li, 1999; Melbiah et al., 2017;
Ochoa et al., 2003; Zhang et al., 2017). However, these membranes are
functioning effectively only in the mild conditions. There are also some
other disadvantages such as inability to separate volatile compounds
and the tendency to be fouled quickly, which will eventually lower the
flux of the membrane and thus, reduce the performance. Therefore, the
attention now is moving towards the potential of the ceramic mem-
brane as an alternative to replace the polymeric membrane.
Over the past few years, many researchers have been working on the
development of ceramic membrane with low cost and yet high perfor-
mance for various applications. The superior properties of the ceramic
membrane over the polymeric membrane have made the ceramic
membrane more suitable for many applications. The exceptional re-
sistance to high temperature and pressure, low fouling effect, and high
endurance towards strong cleaning agents are among the advantages
offered by the ceramic membrane (Bader, 2007; Basumatary et al.,
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Journal of Environmental Management 224 (2018) 252–262
2016; Xu et al., 2014). Despite all these advantages, the usage of the
ceramic membrane is always redundant due to high production cost.
This could be attributed to the expensive raw materials such as alu-
mina, zirconia, titania, and silica. In addition, most of these materials
require high sintering temperature to reach a compromise between
porosity, permeability, and mechanical strength (Liu et al., 2003,
2016). This in turn could upsurge the production outlays of the mem-
branes (Hubadillah et al., 2017a, 2018). Therefore, finding the alter-
native of a low cost and highly performing membrane is of utmost ur-
gency.
Zeolite is a hydrated aluminosilicate mineral naturally found in
nature. Clinoptilolite is the most abundant source of natural zeolite
found across the globe, making it among the cheapest natural zeolite
sources in the market. This mineral is composed of symmetrically
stacked alumina and silica tetrahedra and forms an open and stable
three-dimensional structure with a negative charge (Burgess et al.,
2003). This negative charge allows for the adsorption of certain posi-
tively charged ions. Thus, this feature has made the natural zeolite a
potential heavy metal cations adsorbent. On another note, the adsorp-
tion process normally requires the contact between the adsorbate and
adsorbent for a specific time. In this process the adsorbents are nor-
mally suspended in the adsorbate solution in powder form. However,
this conventional method is favourable since the used adsorbent needs
to be separated and further cleaned for reuse (regeneration), which may
cause the loss of adsorbent particles. For that reason, a single step of
adsorption and separation should be invented to prolong the life span of
the adsorbent.
The fabrication of the zeolite-based hollow fibre ceramic membrane
(HFCM), which possesses both features of adsorption and separation, is
the main aim of this study. The hybrid process combining both ad-
sorption of Cr (VI) and the separation of the adsorbed species by fil-
tration from the feed in a single step is the novelty of this study. The
effect of the HFCM fabrication parameter, namely sintering technique,
on the physical properties and the performances of the membranes was
studied throughout this work. The cheap raw material (natural zeolite)
and the low sintering temperature will eventually produce an in-
expensive HFCM that possesses a promising adsorption capacity in the
removal of the Cr (VI) from the wastewater.
2. Materials and methods
2.1. Materials
The natural zeolite (clinoptilolite) powder (with an average particle
size of 70 μm) was purchased from Liaoning Province, China
(Shijiazhuang Mining Trade Co. Ltd.). Polyethersulfone, PESf (Radal
A300, Ameco Performance, USA), N-methyl-2-pyrrolidone, NMP (AR
grade, Qrec™) and Arlacel P135 (polyethylene glycol 30-dipolyhy-
droxystearate, Uniqema) were used as the polymer binder, dispersant,
and solvent, respectively. The fabrication of the zeolite-based hollow
fibre was performed using the phase inversion-based extrusion tech-
nique followed by sintering.
2.2. Hollow fibre ceramic membrane (HFCM)
2.2.1. Fabrication of hollow fibre membrane
Prior to the dope suspension preparation, the pre-ground natural
zeolite powder was sieved with a 36 μm sieve and was dried overnight
at 60 °C to remove all the trapped moisture. The suspension composi-
tion of the zeolite-based HFCM (45 wt.%) was 45 g of zeolite powder,
1 g of Arlacel P135 as the dispersant, 5 g of PESf as the polymer binder,
and 49 g of NMP as solvent. The HFCM spinning parameters were
10 mL/min, 15 mL/min, and 5 cm for the suspension extrusion rate,
bore fluid flow rate, and air gap distance, respectively.
The zeolite-based HFCM was fabricated via the phase inversion-
based extrusion and sintering technique. The preparation of the dope
M.R. Adam et al.
Fig. 1. Phase inversion-based extrusion of HFCM.
suspension began with dissolving Arlacel P135 (dispersant) in NMP
(solvent) under vigorous stirring. The desired amount of pre-dried
zeolite powder was then added, and the mixture was subjected to ball-
milling using NQM-2 planetary ball mill for 48 h. After adding the pre-
dried PESf (polymer binder), the milling process was continued for
another 48 h, followed by degassing under vacuum for 1 h.
The dope suspension was spun into hollow fibre by extruding
through a tube-in-orifice spinneret via syringe pump. The diameter of
the outer spinneret is 2.80 mm while the inner diameter (bore) is
0.5 mm. Tap water was used as both internal and external coagulants in
the phase inversion process. After the extrusion, the nascent fibre tra-
velled through the air-gap distance before entering the external coa-
gulant (Fig. 1), where the fibre stayed for 24 h to allow the phase in-
version process to complete.
After 24 h of immersion, the fibre precursor was air-dried at room
temperature. The precursor was then sintered at various targeted
temperatures (900–1050 °C) for 4 h. The heating and cooling rates were
set at 2 °C·min−1 throughout the process. Fig. 2 shows the sintering
profile of the zeolite-based HFCM.
2.2.2. Membrane characterisation
The viscosity of the spinning dope suspension was measured using a
viscometer (Brookfield) at shear rates of 1–100 s−1 at room tempera-
ture. The morphological behaviours of the HFCMs sintered at different
temperatures were examined using scanning electron microscopy (SEM,
Fig. 2. Sintering profile of zeolite-based HFCM.
254
Journal of Environmental Management 224 (2018) 252–262
Hitachi model TM 3000, Japan) at different magnifications. The HFCM
samples were gold-coated for 3 min under vacuum prior to the SEM
analysis.
The three-point bending machine (Instron model 3324, US) was
used to measure the mechanical strength of each HFCM. The mechan-
ical strength of the HFCM was determined using Eq. (1) (Hubadillah
et al., 2017b):
8FLDo
σF =
π (Do4 − Di4 ) (1)
where F is the maximum load at which the fracture occurred, L is the
length of span (43 mm), Do and Di are the outer and inner diameters of
the HFCM, respectively.
The water permeation experiment was done using the dead-end
crossflow permeation cell at 1 bar and the flux, F (m3/m2∙h), was cal-
culated using Eq. (2):
V
F=
At (2)
where V (m3) is the permeate volume collected during the time t (h) and
A (m2) is the exposed area of the HFCM.
2.2.3. Membrane performance
The separation of Cr (VI) from the feed aqueous solution was stu-
died via a laboratory made crossflow permeation cell with a feed
chamber of 25 mL at a flow rate of 245 mL/min. The retentate was re-
cycled to the feed reservoir of 4 L so that the concentration of Cr (VI) in
the feed could remain constant. The feed solution of pH 4, containing
40 mg/L of Cr (VI), was passed through the dead-end epoxy-coated
HFCMs with an effective area of 6.195 × 10−4 m2 (weight 0.40 g)
under the pressure of 1 bar at room temperature. The cumulative
permeate volume was measured at several intervals and the Cr (VI)
concentration in the cumulative permeate was determined using
UV–visible spectrophotometry (DR 5000: Hach, Canada). The process
was repeated using HFCM sintered at 1050 °C.
Furthermore, from the material balance of HFCM, the adsorption
capacity of the HFCM can be obtained by the following equation;
(cf − cp) Vt = wqt (3)
where cf and cp are the concentrations of Cr (VI) in the feed and cu-
mulative permeate (mg/L), respectively, w is the weight of the HFCM
(0.40 g), and qt is adsorption capacity, which is the amount of Cr (VI)
adsorbed by a unit weight of HFCM (mg/g) at time t (min) (Hubadillah
et al., 2017a). It should be noted that the size exclusion does not play
any role in the removal of Cr ion by the membrane since the size of Cr
ion is much smaller than the pore size of the membrane under study.
The mechanism is solely adsorption due to ion exchange. The qualifi-
cation of the Cr (VI) adsorption onto the HFCM surface was confirmed
by the energy dispersive X-ray (EDX: Oxford Instruments model INCA x-
act, UK). The sample before and after the adsorption process was
sputtered with platinum under vacuum for 3 min prior the EDX.
The percentage of Cr (VI) removal can be calculated using Eq. (4):
c f − cp ⎞
Percent of removal (%) = ⎜⎛ ⎟ × 100
⎝ cf ⎠ (4)
where cf and cp are the concentrations of Cr (VI) in the feed and cu-
mulative permeate (mg/L), respectively.
The experimental data obtained from this study was reproduced and
represented in the mathematical expressions. The calculation using the
modified adsorption order equations was evaluated and extrapolated to
that of the experimental findings.
M.R. Adam et al.
5 growth at higher temperature (likely to occur at 1050 °C), which
4 crostructure of the ceramic membrane (Hubadillah et al., 2016). The
Viscosity (Pa s)
3 could serve poorly as HFCM. In addition, tunnels and macrovoids were
2 of the ceramic.
1
0 Mäntylä, 2002; Qiu et al., 2009). The selection of the sintering tem-
0 20 40 60 80 100
1 As for this study, the natural zeolite will be melting around
Shear Rate (s )
Fig. 3. Rheology profile of ceramic suspension containing zeolite/Arlacel/
PESf/NMP.
3. Results and discussion
3.1. Membrane properties
3.1.1. Rheology of the ceramic suspension
Fig. 3 shows the rheological profile of the ceramic suspension con-
taining zeolite (36 μm radius)/Arlacel/PESf/NMP, which shows a non-
Newtonian behaviour. The same rheological behaviour of the ceramic
suspension has been reported earlier (Abdullah et al., 2016; Nittmann
et al., 1985). From the figure, the viscosity of 0.688 Pa s was obtained at
the shear rate of 30 s−1. According to Kingsbury and Li (2009), the
viscosity of the suspension affects the formation of the finger-like
structure across the membrane (Kingsbury and Li, 2009). They found
that a threshold viscosity of 12.1 Pa s for their alumina containing
ceramic suspension, beyond which the formation of finger-like struc-
ture is suppressed, and the sponge-like structure dominates. In the
current work, the formation of both finger- and sponge-like structures
across the membrane, as shown in the SEM images, indicates that the
viscosity value of the ceramic suspension used in this work is lower
than the reported threshold value.
3.1.2. Morphological properties of the HFCM
The morphological behaviours of the fabricated HFCMs sintered at
different temperatures are shown in Fig. 4. Both the finger- and sponge-
like structure were formed for all HFCMs. The sponge-like structure
became denser upon the increment of the sintering temperature as
shown in Fig. 4(iii). This post heat treatment of the ceramic membrane
was subsequently performed to the ceramic membrane precursor ob-
tained during the phase inversion technique. This process is an im-
portant fabrication step since it can control various physical properties
of the produced ceramic membrane namely porosity, pore size, per-
meability, mechanical strength, and physical morphologies of the
membrane (Levänen and Mäntylä, 2002; Qiu et al., 2009). The selection
of the sintering temperature should consider the melting point of the
ceramic used. As for this study, the natural zeolite melts at around
1100–1150 °C. Approaching the melting point of the ceramic material
will increase the tendency of producing a membrane with a more
packed grain structure. Although the mechanical strength will be fur-
ther increased with the increment in the sintering temperature, the
permeability of this membrane will be drastically declined. The fusion
of individual ceramic particles is enhanced as a result of faster grain
255
Journal of Environmental Management 224 (2018) 252–262
eventually reduces the pore size and densifies the membrane. A similar
result was reported on the effect of sintering temperature on the mi-
formation of finger- and sponge-like structures is justified by the visc-
osity data of the spinning dope, as discussed earlier. Further increase in
the sintering temperature resulted in a fully densified membrane which
observed across the membrane as defects. This occurrence could be
explained by the sintering temperature that was near the melting point
This heat post-treatment of the ceramic membrane is subsequently
done onto the ceramic membrane precursor obtained during the phase
inversion technique. This process is such an important fabrication step
since it can control various physical properties of the produced ceramic
membrane namely porosity, pore size, permeability, mechanical
strength and physical morphologies of the membrane (Levänen and
perature should be considering the melting point of the ceramic used.
1100–1150 °C. Approaching the melting point of the ceramic material
will be increasing the tendency of producing the membrane with the
more packed grain structure. Although the mechanical strength will be
further increased along the increment in the sintering temperature, the
permeability of this membrane will be drastically declined. Similar
findings have been recorded in the literature (Adam et al., 2017;
Hubadillah et al., 2016).
3.1.3. Mechanical strength and water permeation of the HFCM
The effect of sintering temperature on the physical properties of the
fabricated HFCM was further investigated by measuring the mechanical
strength and water permeability. Fig. 5 depicts the mechanical strength
of the HFCM at different sintering temperatures. It is obvious that the
HFCM strength has increased from 8.44 to 50.92 MPa with the incre-
ment in the sintering temperature. This is ascribed to the promotion of
grain growth process and the resulting membrane densification. The
denser membrane with more closely-packed particles contributed to the
higher strength. The highest mechanical strength achieved by the
HFCM sintered at 1050 °C was more than twice the strength of the other
membranes. A similar trend was reported where β-sialon ceramic
membrane was densified at 1650 °C to give the highest mechanical
strength (Wang et al., 2016).
Water permeability of the HFCM is strongly affected by the sintering
temperature. Fig. 6 shows the water permeation flux of the HFCM at
different sintering temperatures. The water permeation flux and the
mechanical strength are inversely proportional. The denser structure
across the membrane cross-section will result in a higher mechanical
strength. However, the closely-packed particles will eventually block
the water penetration across the membrane and therefore, reduces the
water permeation. As discussed in Section 3.1.2, the higher sintering
temperature has somehow encouraged the densification of the ceramic
particles especially in the sponge-like region. The already hindered
water diffusion across this region has further gone downhill with the
densification effect. Therefore, the higher the sintering temperature, the
lower the water permeability of the membrane. The sacrificial effect of
water permeability of the membrane over the increment in sintering
temperature is a common phenomenon in fabricating the ceramic
membrane.
3.2. Adsorptive membrane performance on Cr (VI) removal
Ion exchange process is another approach that is conventionally
used in removing contaminant cation from water. This process normally
combines the uptake of the interest species (heavy metal) through ion
exchange and adsorption process. The ion exchanger used can be either
natural or synthetic. For the case of natural ion exchanger, it normally
M.R. Adam et al.
Fig. 4. Morphological behaviour of the HFCMs sintered at (a) 900, (b) 950, (c) 1000, and (d) 1050 °C at different magnifications, respectively. Note: The sponge-like
structure is denoted as dashed-line arrow and the finger-like structure is represented by the small arrow.
comes from the minerals that are crystalline, hydrated, aluminosilicate
of alkali, or alkaline earth ions. The minerals also possess the three-
dimensional tetrahedral structure of AlO4 and SiO4 that is connected by
the shared oxygen atoms and water molecules (Pansini, 1996). The
common natural zeolites that possess ion exchange properties include
clinoptilolite, mordenite, chabazite, heulandite, laumonite, analcite,
and erionite (Montalvo et al., 2012). The ion exchange mechanism
between the exchanger and heavy metal cation is as follows:
[M−A+ ] + Cation+ ↔ [M−Cation+] + A+
solid solution solid solution
The reversible process aims the replacement of the exchanger cation
(A+) to that of heavy metal cation in the solution. The temporary
binding of the metal ions with the ion exchanger will be demolished if
further chemical treatment reaction such as acid cleaning or re-
generation process takes place.
Natural zeolites are the most important inorganic cation exchangers
that exhibit high ion exchange capacity, selectivity, and compatibility
with the natural environment. Combining the superior ion exchange
property of the natural zeolite and membrane filtration brings the idea
of the fabrication and utilisation of hollow fibre ceramic membrane
Journal of Environmental Management 224 (2018) 252–262
(HFCM) with dual functions. The ion exchange property of natural
zeolite is commonly used to remove many contaminants such as heavy
metal ions in water by adsorption in its suspended powder (adsorbent)
form. The substitution of each aluminium (Al3+) atom over the silicon
(Si4+) atoms in zeolite framework creates one negative charge on the
framework. Therefore, the higher the substitution of the aluminium
atom, the higher the negative charge of the zeolite (Nguyen and Tanner,
1998). The negative charge within the pores is balanced by the cations
(positively charged) exist on the surface of the zeolite such as Na+, K+,
(5) Ca2+, and Mg2+ (Rožić et al., 2000). These cations are bonded to the
aluminosilicate by a weaker electrostatic interaction that causes the
ability of exchange with certain cations presence in the solution (Cr6+).
Thus, this will eventually contribute to the adsorption of the Cr (VI)
ions in the wastewater. Instead, dual functions of adsorption and se-
paration can be attained in the HFCM form. Fig. 7 depicted the pro-
posed mechanism of the adsorption of Cr6+ by the natural zeolite
HFCM.
The cumulative permeate volume increased almost linearly until it
reached the initial feed volume of 25 mL in 120 min and then levelled
off from 120 to 180 min (Fig. 8). The abrupt decline in the permeation
256
M.R. Adam et al. Journal of Environmental Management 224 (2018) 252–262

60 25

Cumulative permeate volume, Vp (mL)

Flexural strength, F (MPa)

50
20

40
15

30
10
20

5
10

0
0 0 20 40 60 80 100 120 140 160 180 200
900 950 1000 1050
Contact time (min)
Sintering Temperature, ( C)
Fig. 8. HFCM cumulative permeate volume at different contact times (n = 3).
Fig. 5. Mechanical strength of the HFCM sintered at different temperatures
(n = 5).
rate is attributed to the membrane fouling that occurred by the de-
300 position of the suspended or dissolved matters on its external surfaces,
pore openings, or the spaces within the pores (Koros et al., 1996). Fig. 8
depicts the Cr (IV) concentration in the permeate (cumulative) reported
250 in the percentage of Cr (VI) removal in the permeate. The decreasing
Water Permeation, (L/m2 h)

trend in the cumulative permeate volume led to the decrease in the

adsorption capacity of the membrane. Thus, the fouling phenomenon
200 impeded the adsorption process to occur and blocked the runway of the
water, which in turn reduced both heavy metal removal and water
permeability of the membrane.
150
Fig. 9 shows the cumulative volume of Cr (VI) removal in the
permeate. The initial high Cr (VI) concentration in the permeate in-
100 dicates a very low adsorption rate at the beginning. Over time, the rate
of the adsorption increased and eventually levelled off at 180 min of the
contact time. Herein, it is worth mentioning that previous study re-
50 ported in the literature has been stated the lower feed concentration.
For example, there was study reported on the adsorption of heavy
metals by clinoptilolite zeolite as adsorbent (Zanin et al., 2017). In the
0 study the feed concentration was tested at 10 mg/L. The low con-
900 950 1000 1050
centration of feed solution thus eventually gives the highest adsorption
Sintering Temperature, ( C) capacity. In addition, another study has also reported on the adsorption
Fig. 6. Water permeation of the HFCM sintered at different temperatures at
of heavy metal using low feed concentration (Borna et al., 2016). The
1 bar for 180 min (n = 3).

50
Chromium (VI) Removal (%)

40

30

20

10

Fig. 7. The adsorption mechanism of Cr6+ onto the zeolite surface. A) tetra-
hedral arrangement of Si-O and Al-O where the substitution of Al3+ towards 0
Si4+ creating negative site; b) the neutralization of the negative site by Na+ 0 20 40 60 80 100 120 140 160 180 200
from the surface thus, creating negative site on the surface; c) the attachment of
Cr6+onto the negative site of the zeolite surface. Contact time (min)
Fig. 9. Chromium (VI) removal at different contact times (n = 3).

257
M.R. Adam et al.
10
Adsorption Capacity, qt (mg/g)
8 qt =
6
4
2 data very well and do not claim that the equation is based on any
0 control at the initial stage as proposed by Weber and Morris. Adsorption
0 20 40 60 80 100 120 140
Contact time (min)
Fig. 10. HFCM adsorption capacity at different contact times (n = 3).
study has been investigated the adsorption of Cr (VI) on low-cost Hi-
biscus Cannabinus kenaf, as a green adsorbent in the feed range of
0.5–10 mg/L. This indicated that the 40 mg/L of feed concentration
used in this study would be acceptable and reliable. To be noted, nat-
ural zeolites are the most important inorganic cation exchangers that
exhibit high ion exchange capacity, selectivity and compatibility with
the natural environment. Instead, dual functions of adsorption and se-
paration can be attained in its HFCM form. In addition, even though
there are reports on the development of the natural zeolite based
ceramic membrane for various applications, such as for the removal of
dyes and for the macrofiltration process (Choiriyah et al., 2016; Dong
et al., 2006), this study is focused on the Cr (VI) removal.
3.3. Membrane filtration/adsorption mechanism
The amount of adsorption, wqt was calculated using Eq. (3) using
the cumulative volume (Fig. 8) and the Cr (VI) concentration in the
cumulative permeate (Fig. 9) and the adsorption capacity, qt was ob-
tained by dividing by w. The results are shown in Fig. 10. The ad-
sorption capacity increased exponentially in the beginning, steadily in
the middle, and levelled off at the end. The initial exponential increase
can be explained by a self-acceleration mechanism.
The first order adsorption involves the attachment of one molecule
of adsorbate onto one adsorption site and the rate of adsorption is
proportional to the unoccupied adsorption site (qe − qt), which gives
the following equation:
qt = qe (1 − e−ka t )
where qe is the equilibrium adsorption capacity (mg/g) and ka is the
first order adsorption constant (min−1). When the adsorption occurs
between one adsorbate molecule and two vacant adsorption sites, the
rate of adsorption is proportional to (qe − qt)2, which gives the fol-
lowing equation:
t 1 t 2014). Therefore, it is expected that the HFCM should give a higher
= +
qt ka qe2 qe
where ka is the second order adsorption constant (g∙mg min ).
When the adsorption occurs between one adsorbate molecule and
one vacant adsorption site and one occupied adsorption site, the rate of
adsorption is proportional to qt(qe − qt), which gives the following
equation:
dqt
= ka (qt )(qe − qt )
dt
Journal of Environmental Management 224 (2018) 252–262
Experimental where ka is an adsorption constant with a dimension of g∙mg−1 min−1.
Calculation Integrating and rearranging Eq. (8) results in the following equa-
tion:
qe Ae qe ka (t − to)
1 + Ae qe ka (t − to) (9)
qt
where A = qe − qt
at t = to
Setting ka = 0.0066 g mg−1 min−1, qe = 8.73 mg g−1, and
A = 0.0493, the adsorption capacity values calculated using Eq. (9)
were plotted in Fig. 10 as the calculated values, which have a good
agreement with the experimental values.
Currently the self-accelerating Equation (9) fits the experimental
particular adsorption mechanism.
Another interpretation of the data is based on intraparticle diffusion
160 180 200 sites are usually present at the adsorbent surface. When the adsorption
sites at the adsorbent surface become ineffective during the high tem-
perature sintering process, only the inner adsorption sites (in the pore)
remain effective. Then there is a delay until the inner adsorption sites
become fully accessible. Since the adsorption sites on the surface of the
adsorbent surface have been changed by the heat treatment (sintering
technique), the non-affected active sites in the pore, which has rather
low efficiency compared to those in the surface, will be involved in the
adsorption process. This process is rather slow at first and gradually
increases over time until it levels off upon reaching the equilibrium
state. On the other hand, Fig. 11 represents the EDX analysis of the
outer and inner surface of the HFCM prior and upon the adsorption
process. The qualification analysis of the EDX has confirmed that the Cr
(VI) has been successfully adsorbed onto the HFCM's surface and thus,
reduced the content of this contaminant in the filtrate solution.
The better performance of an adsorption process normally correlates
to the surface area of the adsorbent. To attain the best adsorption
outcomes, the adsorbent must possess a high surface area. The higher
surface area per volume can be obtained by the finest particles com-
pared to that of bigger particles. The specific surface area of the ad-
sorbent that is normally denoted as m2·g−1 affects the adsorption ca-
pacity of an adsorbent (De Gisi et al., 2016). The adsorbent with bigger
surface area offers more active sites for the adsorption process to take
place. Therefore, the particle of natural zeolite used in this study should
be smaller to ensure a better uptake of the Cr (VI) ions from water. Also,
the sintering technique used for the fabrication of the HFCM may
change the physical properties of the ceramic. The high sintering
temperature will produce a more packed grain of the ceramic particles
thus, will eventually lower the surface area of the membrane. Hence,
the evaluation of the best sintering temperature ensuring the optimal
adsorption of Cr (VI) ions is highly required for the future study.
The adsorption of Cr (VI) has been reported in many studies. Table 1
(6) summarizes the previous studies as compared to that of this study.
Although the adsorption of Cr (VI) by HFCM shows a slightly lower in
the percentage of removal, it should be mentioned here that the feed
solution volume plays an important role in the determination of the
efficiency of the adsorption system. For example, the adsorption of Cr
(VI) using the treated saw dust shows 98% of removal with only 25 mL
of feed solution is adsorbed with 5 g of adsorbent (Itankar and Patil,
efficiency if the feed volume is reduced and the adsorbent mass is in-
(7)
creased. When it comes to the adsorption process, the volume of the
−1 −1
feed solution does play an important role in determining the effec-
tiveness of an adsorbent apart from the feed concentration. This could
be proven form the correlation between the adsorption capacity of an
adsorbent towards the volume of the feed solution via the following
equation;
(cf − cp) v
qt =
(8) w (10)
258
M.R. Adam et al. Journal of Environmental Management 224 (2018) 252–262

Fig. 11. The EDX analysis of (i) outer surface and (ii) inner surface of HFCM of (a) before adsorption and (b) after adsorption of Cr (VI).

Where qt is the adsorption capacity, cf and cp are the concentration of
the adsorbate in the feed and permeate, respectively, w is the mass of
the adsorbent and v is the volume of the feed solution.
From the correlation, it could be clearly seen that the feed volume is
directly proportional to the adsorption capacity to which determine the
adsorbent efficiency. Referring to Table 1, the variety of the adsorbents’
performances were highly relied on their adsorption capacities. For
example, the adsorption of Cr (VI) using biomass have resulted in 75%
of removal (Barrera et al., 2006). Although the removal seems higher,
the volume of the feed solution used was smaller (10 mL) and thus
possessed an adsorption capacity of 3.75 mg/g. In contrast, the ad-
sorption capacity of the treated saw dust was only 0.245 mg/g even
though the percentage of Cr (VI) was outstanding (98%) (Itankar and
Patil, 2014). In other words, even at low feed volume of 25 mL, the
amount of adsorbent needed was as much as 5 g. Inversely as in this
study, the capacity obtained experimentally was 8.52 mg/g. Theoreti-
cally, if the volume of feed is reduced to as other studies (10–25 mL),
the percent of Cr (VI) removal would be increased instantaneously

Table 1
Adsorption of Cr (VI) using different adsorbent.
Material Volume of feed (mL) Feed concentration (mg/L) Mass of adsorbent (g) Percent of Cr (VI) removal (%) Reference

Zeolite 250 40 1.0–3.0 65.45 (Upadhyay et al., 2017)

Treated saw dust 25 50 5 98 (Itankar and Patil, 2014)
Biomass 10 50 0.1 75 (Barrera et al., 2006)
Termite nest 10 20 0.1 60.8 (Araújo et al., 2013)
Biosorbent 100 100 0.1 96.8 (Liang et al., 2018)
Natural zeolite HFCM 4000 40 0.4 44 Present work
25 (expected) > 90 (expected)

259
M.R. Adam et al.
1.0
0.8
245 mL/min
0.6 150 mL/min
Ct/C
75 mL/min
0.4
0.2
0.0
0 250 500 750 1000 1250 1500 1750 2000
Time (min)
Fig. 12. Breakthrough behaviour of the Cr adsorption for different flow rate
(HFCM membrane effective surface area (3.098 10−4 m2) = 0.20 g) at 30 °C.
using the same amount of adsorbent (HFCM).
3.4. Membrane long-term breakthrough behaviour
Fig. 12 presents the long-term breakthrough behaviour have been
studied using the real wastewater containing 259 ppm or equally to
259 000 ppb Cr6+ ions. The adsorption using the adsorptive membrane
was let for the reaction for 35 continues hours to analyse the long-term
behaviour of the adsorption process. The membrane effective surface
area (3.098 10−4 m2) equivalent to 0.20 g and the feed solution volume
tested was 50 mL. This breakthrough behaviour study was imitated the
column adsorption studies and was repeated using different feed flow
rate. The obtained results are represented in the following line graphs;
The variation of the feed flow rate to the breakthrough behaviour of
the adsorptive HFCM for the removal of Cr was performed at the
membrane effective surface area (3.098 10−4 m2) equivalent of 0.20 g
and feed flow rate of 75–245 mL/min. The breakthrough behaviour of
this adsorption process is depicted in Fig. 12. Unlikely to that of bed
column adsorption process where the concentration of output at time t,
Ct was measured after the solution has passed through the bed column.
Whereas in this study, the output concentration was determined using
the filtrate produced. From the breakthrough behaviour, it was found
that the adsorptive HFCM has performed better at the lower feed flow
rate. The lower flow rate has resulted in a longer breakthrough and
exhaustive time where the saturation points were reached (Foo et al.,
2013). In addition, the exhausted time of the HFCM achieved was
prolonged upon the lowering of feed flow rate. The increasing of the
feed flow rate was also affected the adsorption performance by in-
creasing the adsorption zone speed as well as dramatically decreased
the breakthrough time and saturation time. This occurrence is mainly
due to the diffusion limitation and insufficient residence time for the Cr
solution within the membrane at the higher flow rates, thus the Cr
solution left the membrane before the equilibrium has been attained
(Hu et al., 2011).
Subsequently, the maximum Cr removal obtained using 0.20 g
membrane with 50 mL of 259 ppm Cr feed solution was 75.5%.
However, this membrane performance can be scaled up with slight
modification. One of the possible way is by increasing the membrane
effective surface area (3.098 10−4 m2) equivalent to 0.2 g. Instead of
using a single membrane, the membrane could be assembled and pre-
pared in a module form (Fig. 13). This could be possibly providing more
active sites for the adsorption and thus, promotes more adsorption
process to be occurred at the membrane interphase. Apart from the
increment in the Cr uptake, the additional membrane could also in-
crease the water flux of the treated water. Thus, more treated water can
260
Journal of Environmental Management 224 (2018) 252–262
Epoxidized
membrane
(dead-end)
Feed
solution
(NH4+
containing
water)
Retentate
(to the tank)
Filtrate
(NH4+ free water)
Fig. 13. HFCM in a module form.
be produced in term of filtrate.
3.5. Future research prospect
The improvisation of the current work can be implemented in the
future research. One of the best option for the HFCM performance en-
hancement is by controlling the HFCM production process. This is
mainly contributed by the starting zeolite powder particle size. Apart
from the larger surface area attained by the smaller particle size, the
mechanical strength of this HFCM can be further enhanced and the
water permeation can be reduced thus increased the Cr6+ uptakes by
the HFCM. On the other hand, the performance of the HFCM can be
tailored by controlling the sintering temperature. In the prospect work,
the sintering temperature range can be studied in detail and expecting
to produce HFCM with optimum water permeation and Cr6+ adsorp-
tion.
On the other hand, this technology is highly practical especially to
the developing countries. As most of these countries relying on the
agricultural based activities for their corps and economical source, the
widely application of the fertilizer eventually led to the major ammonia
contamination especially towards the drinking water sources.
Therefore, this technology is not only expected to solve this problem
but rather offer the low cost technology particularly for the developing
countries.
4. Conclusions
The natural zeolite-based hybrid adsorptive hollow fibre ceramic
membrane (HFCM) was successfully fabricated in this study. Cr (VI)
was encouragingly removed by the simultaneous adsorption and fil-
tration using a home-made cross-flow permeation cell. A sintering
temperature of 1050 °C was found the best to produce the HFCM, whose
contact angle, water permeation flux, and mechanical strength were
50.52°, 29.14 L/m2∙h and 50.92 MPa, respectively. The lower sintering
temperature used in this study compared to those required by the
commercial ceramic membrane leads to the lower cost of production.
M.R. Adam et al.
The promising performance of this hybrid adsorptive membrane is
therefore apparent by removing about 44% of the Cr (VI) ions in the
feed. The slightly low removal could be caused by the high feed con-
centration and the morphology of the HFCM. This performance can be
further enhanced by controlling the particle size of the natural zeolite,
adjusting the sintering temperature, and preconditioning of the feed
prior to the adsorption and filtration process. The HFCM also showed
self-accelerating adsorption behaviour which was interpreted by some
models and mechanisms. The membrane has a great potential to be
developed in other separation systems such as membrane contactor and
membrane distillation.
Acknowledgement
The authors would like to thank Universiti Teknologi Malaysia and
the Ministry of Education, Malaysia for the financial support through
the Higher Institution Centre of Excellent (HICoE) grant scheme
(Project number: R.J090301.7846.4J194) and UTM R&D Fund (Project
number: R.J130000.7746.4J230) and for the technical support
throughout this research.
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