Journal of Cleaner Production 195 (2018) 79e92

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Journal of Cleaner Production

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Aragonite precipitated calcium carbonate from magnesium rich

carbonate rock for polyethersulfone hollow fibre membrane
application
Onimisi A. Jimoh a, *, Patrick U. Okoye b, Tunmise A. Otitoju c, Kamar Shah Ariffin a, **
a
School of Materials and Mineral Resources Engineering, Universiti Sains Malaysia Engineering Campus, 14300, Nibong Tebal, Pulau Pinang, Malaysia
b
School of Material Science and Engineering, Shenyang University of Technology, 110870 Shenyang, China
c
School of Chemical Engineering, Universiti Sains Malaysia Engineering Campus, 14300, Nibong Tebal, Pulau Pinang, Malaysia

a r t i c l e i n f o a b s t r a c t

Article history: A reaction-assisted synthesis using a naturally occurring dolomite and aloe vera (Aloe barbadensis Miller)
Received 21 February 2018 extract as a morphological modifier was employed for aragonite-precipitated calcium carbonate (A-PCC)
Received in revised form synthesis. The as-synthesized precipitated calcium carbonate was utilized to produce a polyethersulfone
22 May 2018
(PES) hollow fiber membrane for application of oil-in-water separation. The D-glucose extraction of Ca
Accepted 23 May 2018
Available online 23 May 2018
before precipitation reaction with CO2 dominated the influence of tainted Mg on the as-synthesized PCC
purity. The reaction was carried out via the carbonation route and 1 L/min CO2 flowrate at ambient
conditions. The aloe vera extract (5 v/v%) and unleached in situ Mg influenced the phase transformation
Keywords:
Aloe vera
from calcite and vaterite polymorphs to flower-like structure with radiating ends. The A-PCC synthesized
Aragonite polymorph using aloe vera did not require external heating, thereby representing an attractive energy-conserving
Dolomitic marble process for this type of precipitated calcium carbonate. The prepared membranes were characterized
Membrane using porosity, field-emission scanning electron microscope, hydrophilicity, mechanical properties, and
Precipitated calcium carbonate pore size. Their performances for oil-in-water filtration were evaluated. At an optimal amount of 3 wt%
aragonite PCC in the hollow fiber membrane, the permeate flux and oil rejection reached 102 kg/m2h and
>99%, respectively. Furthermore, the introduction of A-PCCs in the PES matrix improved the antifouling
properties of the composite membranes. Therefore, PES/A-PCC composite membranes are desirable in
treating wastewater and wastewater containing oil.
© 2018 Elsevier Ltd. All rights reserved.

1. Introduction Combined with other uses of calcitic marbles, a drastic depletion of

this mineral is realized. Hence, continued research on PCC synthesis
Carbonate rocks rich in calcite are a favorable choice for are focused on evolving crystal morphology or composite
industrial-scale precipitated CaCO3 (PCC) synthesis. PCC has morphology and the use of sustainable PCC raw materials.
multipurpose industrial applications, and its low production cost Similar to calcitic marbles (CaCO3), dolomitic marbles contain
has rendered it as an attractive material in paper, paint, cosmetics, considerable amount of Ca required for industrial-scale production
and pharmaceutical industries (Jimoh et al., 2017b). The synthesis of PCC. However, dolomitic marbles are tainted with Mg (primarily
of PCC via the carbonation route presents an even more viable and CaMg(CO3)2 and minor SiO2 content), which reduces the opacity
environmentally benign pathway because CO2 is employed in the and purity of PCC (Jimoh et al., 2017a). Moreover, Mg can influence
precipitation reaction. Three PCC crystal morphologies are identi- the strength or morphology of the resultant PCC. Hence, green
fied, namely, calcite (most stable), aragonite (metastable), and methods to separate Mg from Ca is required to boost the viability of
vaterite (less stable) (Jimoh et al., 2017d). As the demand for PCC PCC to ensure that dolomite can be used to produce both controlled
increases, the use of calcitic marbles will increase tremendously. shaped PCC and Mg-based products simultaneously (Somarathna
et al., 2016). The contribution and interaction of Ca and sugar in
the body to provide energy and regulate blood sugar level is an
* Corresponding author. established phenomenon in the field of medicine. Moreover, a
** Corresponding author. previous study reported the extraction or leaching of Ca in
E-mail addresses: [email protected] (O.A. Jimoh), [email protected] (K.S. Ariffin).

https://doi.org/10.1016/j.jclepro.2018.05.192
0959-6526/© 2018 Elsevier Ltd. All rights reserved.
80 O.A. Jimoh et al. / Journal of Cleaner Production 195 (2018) 79e92

List of abbreviations XRF X-ray fluorescence

A-PCC Aragonite-precipitated CaCO3 List of Symbols

CTAB Cetyltrimethylammonium bromide % Percentage
EDX Energy dispersive X-ray
C Degree Celsius
FESEM Field emission scanning electron microscope CO2 Carbon dioxide
GTE Green tea extract CaCO3 Calcium carbonate
HF Hollow fiber MgCO3 Magnesium carbonate
KBr Potassium bromide Ca(OH)2 Calcium hydroxide
LOI Loss on ignition Mg(OH)2 Magnesium hydroxide
MOL Milk of lime H2O Water
MPS Mean pore size D10 10% volume of particles with size value lower than or
PAA Polyacrylic acid equal to D10
PCC Precipitated CaCO3 D50 50% volume of particles with size value lower than or
PES Polyethersulfone equal to D50
PP Polypropylene D90 90% volume of particles with size value lower than or
PSA Particle size analysis equal to D90
P-SA Poly-2-acrylamido-2-methyl-propane sulfonic acid L Liter
PSD Particle size distribution wt% Weight percentage
PVA Polyvinyl alcohol mL Milliliters
PVDF Polyvinylidene fluoride M Mole
SLS Sodium lignosulfonate Aq Aqua solution
WCA Water contact angle S Solid
XRD X-ray diffraction G Gas

dolomitic rocks by using sucrose (Mantilaka et al., 2014, 2012). The (2012) reported that green tea extract and sodium lignosulfonate
sucrose solution efficiently leaches Ca from dolomite, resulting in influence the synthesized PCC polymorphs. In our previous work on
79% PCC yield. They observed that sucrose inhibits the formation of PCC synthesis with calcitic marble by using aloe vera extract as the
aragonite and vaterite morphologies of PCC. green morphological modifier, an aloe vera extract concentration of
The evolution of these crystal phases for task-specific PCC often 0.5 v/v% induces phase transition, thereby resulting in composite
requires additives to control morphology and particle size. Mono- (calcite and aragonite) PCC polymorph. Aloe vera extract is a
dispersed cubic and rectangular PCC were produced using small mucilaginous gel with antiprotozoal, anti-inflammatory, UV-pro-
amounts of polyvinyl alcohol, polyacrylic acid (PAA), and cetyl- tective, and immunomodulatory properties (Huang et al., 2007).
trimethylammonium bromide (CTAB) at 80
C to influence the Moreover, the shrinking properties of aloe vera can influence the
morphology and particle size (Yu et al., 2005). El-Sheikh et al. PCC particle size and restrict the size to nanometric range. In this
(2013) produced calcite PCC and morphologies that varied from study, the synthesis of morphology-controlled PCC by using natural
rhombohedral (15e35 nm) to scalenohedral (length of 2 mm and dolomitic rock via the carbonation system and by using aloe vera
diameter of 400 nm) by using CTAB as an additive. Moreover, Cheng extract as the green templating agent is reported. New evolving
et al. (2014) utilized PAA at 60
Ce80
C and CaCl2 as lime precursor shapes of PCC polymorphism are investigated. The influence of aloe
to synthesize monodispersed cubic PCC particles. Hu et al. (2009) vera extract concentration on the resultant shape and particle size
synthesized needle-like aragonite whiskers with length of ca. is also investigated.
20 mm and aspect ratio of 8e12 via a reversible reaction with In the field of membrane technology, membrane is the key to
MgCl2 and uncalcined limestone. Most of these chemical additives pressure-driven operations because it directly affects practical
contain active functional groups engrossed on the surface of the application and process efficiency (Otitoju et al., 2016). Poly-
PCC with possible toxic effects on the end user. For instance, ethersulfone (PES), polyvinylidene fluoride (PVDF), polytetra-
polyethylene glycol (PEG) has been reported to contain potential fluoroethylene, polysulfone, and polypropylene are often used to
toxic impurities, such as ethylene oxide and 1,4-dioxane (Andersen, prepare polymeric membranes due to their efficient performance.
1999). Among the aforementioned polymers, PES is a recognized poly-
The use of extracts from plants and protein-containing bio- meric material that is widely employed in the fabrication of
polymers to control crystal morphology is remarkable because they membranes for various applications. Given its high Tg of 225
C, as
act as additives in morphology modification (Kitamura et al., 2002; well as its amorphous and transparent properties, PES possesses
Onimisi et al., 2016). Precipitation tests revealed that the macro- high mechanical, hydrolytic stability, thermal, and chemical re-
molecules of proteins supports the formation of CaCO3 biominerals sistances and outstanding oxidative properties (Rahimpour et al.,
by providing the exoskeleton backbone and regulating the dy- 2012), making them ideal for the preparation of asymmetric
namics of nucleation, growth, and crystal assembly (Polowczyk membranes with different surfaces and pore sizes (Rahimpour
et al., 2016). For instance, chitosan, which is a cationic et al., 2012; Shi et al., 2007; Wang et al., 2009). However, in prac-
biopolymer with amine groups (NH2), forms a polyelectrolyte tical application such as H2O and wastewater treatments, this
complex in carboxylic acid. Then, Ca cations attracted to the performance is often compromised due to pore clogging as a result
negative charge of the carbonate ions during precipitation reaction of solute adsorption on membrane surface, thereby leading to poor
result in bond cleavages in the biopolymer structure (Declet et al., separation efficiencies. To reduce the hydrophobic nature of poly-
2016). Polyelectrolyte provides cohesion, adhesion, and the meric membranes and considerably improve application perfor-
framework between the organiceinorganic layers. Mattila et al. mance, numerous researches have introduced minerals such as
 O.A. Jimoh et al. / Journal of Cleaner Production 195 (2018) 79e92 81

SiO2, carbon nanotubes, TiO2, and Al2O3 into the polymeric matrix. 1 L/min. The reaction was stopped when the pH was approximately
For instance, Ong et al. (2015) added TiO2 into the PVDF matrix to 6.5. Afterward, the product was filtered and then oven dried at
prepare a PVDF/TiO2 HF membrane, which leads to an optimized 50
C for 12 h.
permeate flux (PF) and oil rejection of 70.48 L/m2h and 99.7%. A
study of Zhang et al. (2013) showed an improvement of oil rejection 2.2.4. Characterization of PCC
for the SiO2/PVDF membrane from 86.0% (neat membrane) to 91.2%. Field-emission scanning electron microscopy (FESEM, Carl Zeiss
Li et al. (2006a) introduced Al2O3 to fabricate tubular membrane for Supra™ 35 VP) was used to observe the morphology of the PCC
oil-in-water separation. Their results showed improved PF, products at 5 kV accelerating voltage. The Mg contents of the
whereas the oil rejection is lower than that of unmodified mem- synthesized PCC before and after D-glucose separation of Ca were
brane. On the basis of previous achievements, we first synthesized also determined with FESEM (Zeiss Supra™ 35 VP). In each case,
aragonite-precipitated CaCO3 (A-PCC) from dolomite and then readings were taken in triplicate to confirm the precision of the
doped into the PES matrix to produce a novel composite hollow readings. Given that the readings were much closer to each other,
fiber (HF) membranes. HF membranes were characterized, and the mean of three readings was obtained.
their performances during oil-in-water filtration were evaluated. The powder X-ray diffraction (XRD) studies were carried out to
We assumed that this study will accelerate the application of reveal the crystalline phases of the as-synthesized PCC samples.
dolomite and aloe vera as PCC precursors for aragonite phase The spectrum was recorded with a Bruker D8 advance diffrac-
synthesis and application as a filler in membrane for wastewater tometer by using CueKa radiation and wavelength (l) of 0.154 nm.
treatment. The spectra of the samples were analyzed using X'pert Highscore
Plus software (PANanalytical version 2.2e). Particle size distribu-
2. Material and methods tions (PSDs) (Malvern MasterSizer, model 3000, Worcestershire,
UK) after the PCC powder was redispersed in H2O were determined
2.1. Materials by laser light diffraction. The average particle size was expressed as
the vol/wt mean. The PSD was expressed in terms of the SPAN
Dolomite samples with MgO and CaO contents of 21.01% and factor, which was calculated using Eq. (1) as follows:
32.94%, respectively, were sourced locally from non-active mine at
the Emiworo area located at the central part of Nigeria. Fresh leaves Dv 90  Dv 10
of aloe vera were collected from the University Sains Malaysia en-
SPAN ¼ (1)
Dv 50
gineering campus. Glucose, (D-(þ)-glucose anhydrous) were pur-
chased from Sigma-Aldrich. For membrane preparation, PES where Dv 90, Dv 50, and Dv 10 represent the particle diameters at
(Ultrason E6020P, with molecular weight of 58,000 g/mol) was percentiles of 90, 50, and 10 of the distribution curve.
purchased from BASF and dried at 70
C in the oven for 12 h prior to
use. PEG (MWCO, 35 kDa) was purchased from Sigma-Aldrich. 1- 2.3. Membrane preparation by using various amounts of A-PCC
methyl-2-pyrrolidone (NMP) was provided by Merck, Malaysia.
N2 gas and liquid N2 were supplied by Wellgas, Malaysia. Crude oil The HF membranes were prepared via dry/wet spinning process
was obtained from Petronas, Malaysia. All chemicals were used (Otitoju et al., 2017a; b; Otitoju et al., 2017a; b). All membranes
without any purification. were prepared by blending 17.25 wt% of PES, 1.75 wt% of PEG as
pore former, and varying concentrations of A-PCC (0, 1, 2, 3, 4, and
2.2. Methods 5 wt%) in NMP at 80
C under continuous stirring speed of 550 rpm
for 14 h (Table 1). The homogenous solution was left in the dark
2.2.1Aloe vera extract preparation overnight to achieve a bubble-free solution. This solution was later
The collected leaves of aloe vera were washed with distilled H2O poured in a dope tank for the spinning process. Table 2 shows the
to remove sand and other impurities. Then, the washed leaves were spinning conditions.
cut into small pieces, and approximately 30 g of leaves were boiled The produced PES HF membranes were placed in deionized H2O
in 100 mL of distilled H2O, followed by filtration by using Whatman for 1.5 days, and H2O was concurrently replaced every 5 h to enable
filter paper. Then, the resulting filtrate was stored at 5
C until the residual solvent to be completely removed. Then, the mem-
further experiments. branes were transferred to a 50%e50% glycerol aqueous solution
and then dried in air for 5 days.
2.2.2. Preparation of calcium glucosate suspension
The dolomitic marble samples were crushed and pulverized
2.4. Characterization of membrane doped A-PCC
using a ball mill into powder with a particle size of 200 mm. Then,
the samples were calcined in a muffle furnace at a peak tempera-
2.4.1. Rheological property of dope solution
ture of 1000
C for 180 min. Approximately 40 g calcined dolomite
The viscosity levels of dope solutions were analyzed using the
was dissolved in 400 mL of 0.5 M glucose solution and stirred with
Brookfield Digital Rheometer (Model DV-III, USA) at a shear rate of
a magnetic stirrer for 2 h. Magnetic bar also helped in removing
10 s1 at 25
C.
iron impurities. The solution was filtered using a Whatman filter
paper under suction. The filtrate was obtained as soluble calcium
glucosate. Table 1
Recipes to prepare PES/A-PCC HF membranes.
2.2.3. Synthesis of PCC particles by using aloe vera extract Membrane PES PEG A-PCC NMP
A total of 0.5 M of 400 mL of soluble calcium glucosate was
PC-0 17.25 3.75 0 79
transferred into a reactor and aloe vera extract (typically 0.5e5 v/v PC-1 17.25 3.75 1 78
%; i.e., volume of aloe vera extract solution relative to the volume of PC-2 17.25 3.75 2 77
the produced Ca glucose stock solution) was added dropwise into PC-3 17.25 3.75 3 76
the solution. The mixture was stirred at 500 rpm for 10 min. Af- PC-4 17.25 3.75 4 75
PC-5 17.25 3.75 5 74
terward, CO2 gas was bubbled into the stirred mixture at a rate of
82 O.A. Jimoh et al. / Journal of Cleaner Production 195 (2018) 79e92

Table 2 The rejection of the PEG at different MWs, such as 35000,

PES Hollow fibre membrane spinning conditions. 20000, 10000, 4000, and 1500 Da, were plotted against the PEG
Spinning parameters Values Stokese Einstein diameters on a scale of lognormal probability.
Coagulation bath (
C) 25
Afterward, the results were fitted linearly by using the Eq. (5)
Bore fluid flow rate (ml/min) 1.8 below:
External coagulant Tap water
Air gap (cm) 25.5 FðRÞ ¼ y þ m ðIn Sd Þ (5)
Spinneret internal diameter (mm) 0.35
Bore fluid Distilled water where y is the intercept, and m is the slope. Ignoring the effects of
Spinneret external diameter (mm) 1
Room temperature (
C) 21e23
hydrodynamic and steric interactions between the pore and PEG,
Collection drum (rev/min) 8 the effective MPS ðmp Þ and the geometric SD ðsp Þ can be assumed to
Gear pump (rev/min) 18 have the same value as ðmd Þ and ðsd Þ, respectively (Michaels, 1980;
Relative humidity (%) 61e68
Yang et al., 2007a; b). With respect to mp and sp ; the PSD ðdp Þ can be
expressed by the probability density function given in Eq. (6) as
follows:
2.4.2. FESEM
2  2 3
The morphology of the prepared HF membranes were scanned  
with FESEM (TM 35 VP Zeiss and HITACHI Tabletop Microscope dR dp 1 6 Indp  In mp 7
¼ pffiffiffiffiffiffi exp4  2 5 (6)
instrument [TM-3000, Japan]). For cross-sectional analysis, mem- ddp dp Insp 2p 2 Insp
brane fracturing was conducted by immersing the membrane piece
in liquid N2 to acquire a detailed cross-sectioning without distor- Using the values of MPS and geometric standard deviations for
tion. To scan the membrane's surface, we aligned the piece parallel prepared membranes, the probability density function and the
on a stainless-steel stand as a membrane holder. Before observa- cumulative PSD curves can be obtained.
tion, membrane was sputter coated via a precision coating system
(Quorum-SC7620) and was applied on all membrane samples to
2.4.4. Mechanical properties
prevent any form of charge accumulation. Lastly, the sample mor-
To investigate the effects of adding different A-PCC ratios on the
phologies were observed and operated with an accelerating voltage
mechanical property of the PES HF membranes, the elongation at
of 15 kV.
break (%) and tensile strength (MPa) of HF membranes were
determined with the Instron 3366 (USA) with a load cell of 10 kN at
2.4.3. Porosity and pore size distribution room temperature. Prior to measurement, individual membrane
The membrane porosity was calculated using Eq. (2), as follows: sample were cut into 10 cm in length (at a temperature of 25
C and
relative humidity of 67%) and attached vertically to 2 clamps and
wd
rw stretched in tension with a strain rate of 5 mm/min. Their responses
þ¼ wd þ d
 100 (2)
rw rp
were documented until failure.

where þ is the porosity of the membrane (%), d is weight of the dry 2.4.5. Water contact angle (WCA) measurement
membrane (g), rp is density of the PES polymer at 1360 kg/m3, w is The WCA was measured using Rame-Hart 250-F1 goniometer
weight of wet membrane (g), and rw is density of H2O at 998 kg/m3. (USA) at ambient temperature to evaluate the hydrophilicity of the
To prepare wet membranes, seven HFs with a length of 15 cm were prepared membrane. Membrane samples were affixed parallel on a
kept in isopropanol for 72 h and then in deionized H2O for 72 h. microscope slide with a double-sided adhesive tape. Afterward,
Prior to weighing of membranes, the left-over H2O on each mem- 0.25 mL of deionized H2O was dropped on samples with a micro-
brane surface was removed via airflow. To determine the weight of syringe, and the micrograph was captured with a microscopic
the dried membrane, the wet membranes were dried in the oven camera attached to the instrument. The average WCA values of the
for 10 h at 50
C. To avoid experimental error, the average mem- 5 readings taking at different positions on each membrane sample
brane porosity was obtained from the seven fibers. at ambient temperature were calculated to reduce error.
The mean pore sizes (MPSs) and the PSDs of the HF membranes
were determined using PEG transport approach. PEG ratio was 2.4.6. Membrane performance for wastewater treatment
observed with TOC analyzer (TOC-VCPH analyzer, Shimadzu). The All membranes were soaked in ethyl alcohol for 3 h and then in
Stokes radii (Sr) of PEG can be determined using Eq. (3), as follows: deionized H2O for at least 42 h before ultrafiltration experimental
run. Membrane modules containing eight fibers with effective
Sr ¼ 16:73  1012  MW 0:557 (3) filtration length and active filtration area of 46.8 cm and of
0.0083 m2, respectively, were constructed. Prior to testing, mem-
where MW is the molecular weight of PEG (g/mol), and Sr is the branes were compressed at 2 bar by using deionized (DI) H2O. All
stokes radius of PEG. Then, the rejection of PEG can be expressed as other experiments were performed under ambient temperature,
log-normal probability function according to the size of PEG transmembrane pressure, flow rate, and filtration time of 22
C,
(Michaels, 1980), as illustrated in Eq. (4) as follows: 1.5 bar, 400 mL/min, and 3 h, respectively. Water flux (WF) was
calculated using Eq. (7) as follows:
Zy
1 InSd  Inmd
eu 2 du;
2=
R ¼ erfðyÞ ¼ pffiffiffiffiffiffi where y ¼ (4) V
2p Insd Wp ¼ (7)
∞ ADt

where R, md ; Sd ; and sd are rejection of the PEG (%), geometric where Wp , V, Dt, and A are the pure WF in (kg/m2h), permeate
mean diameter of PEG (at R ¼ 50%), diameter of PEG, geometric SD volume (kg), filtration time (h), and filtration area (m2),
of approximately md (the ratios of Sd at rejection were 84.13% and respectively.
50%), respectively. Removal of oil from waste-water is regarded as a main challenge
 O.A. Jimoh et al. / Journal of Cleaner Production 195 (2018) 79e92 83

in treatment practices (An et al., 2017). Oil-in-water emulsion was

 
prepared by mixing 500 mg crude oil in 1 L of deionized (DI) H2O. Wp  Wp2
The detailed synthesis of oil-in-water emulsion, preparation of Rir ¼  100 (12)
Wp
filtration module, and experimental procedure can be found in
previous work by (Elanchezhiyan and Meenakshi, 2016; Otitoju
et al., 2017a; b). The size distribution of oil droplets ranges from Rt ¼ Rr þ Rir (13)
0.2 to 3.5 mm with an average particle size of 1.54 mm (Fig. 1). All
membranes were tested under cross-flow mode at the same where Rt, Rir, and Rr are the total resistance, irreversible resistance,
transmembrane pressure and feed flow rate of 1.5 bar and 400 mL/ and reversible resistance, respectively.
min, respectively. The PF ðPF Þ was calculated using the same
equation used for the WF (Eq. (7)), while oil rejection can be
determined using Eq. (8) as follows:

! 3. Results and discussion

Operm
Rejection ð%Þ ¼ 1  100 (8)
Ofd 3.1. Process for Ca extraction and industrial features of the
developed technique
where Ofd (mg/L) and Operm (mg/L) are the oil contents in feed and
permeate, respectively. Fig. 2 present the overall PCC synthesis process designed to
To recover membrane, membranes were cleaned with DI H2O meet the industrial requirement. At 1000
C, the dolomite (mixture
for 30 min at 0.8 L/min. Flux recovery ratio (FRR) was determined of CaO and MgO) in the marble converts completely into calcined
using Eq. (9). The higher the FRR, the better the recovery will be. dolomite with minor impurities, such as silicate and iron that
cannot decompose at this temperature. During the mixing of
  calcined dolomite with the glucose solution, CaO reacts with
Wp2
FRR ¼  100 (9) glucose to form calcium glucosate. MgO together with silicates and
Wp
other impurities remained as precipitates in the solution, which
where Wp2 is pure WF after cleaning (kg/m2h), and Wp is the initial can be removed using centrifuge and filtration. Moreover, the
concentration of D-glucose or calcium glucosate did not influence
pure WF (kg/m2h). Meanwhile, fouling resistance of all membranes
the morphologies and phase of final PCC products.
can be estimated using Eqs. (10)e(13), as follows:
Recycling the glucose and/or unreacted CO2 back to the same
  process increases efficiency and reduces the production cost.
Wp  PF
Rt ¼  100 (10) Similarly, MgO separated from the calcined dolomite during
Wp glucose extraction of Ca can be utilized to produce Mg-based
nanomaterials, desiccant, catalyst, toxic waste absorbent, bacteri-
  cide, refractory materials, and electrical insulators (Das et al., 2007).
Wp2  PF
Rr ¼  100 (11) Moreover, aloe vera is highly soluble in glucose, which facilitates
Wp
mass transport and sufficient miscibility to effectively tailor the
shape or morphology of as-synthesized PCC.

12

10

8
Intensity (%)

0
0 1 2 3 4 5 6 7
Droplet size (µm)
Fig. 1. Size distribution of oil droplet in the oil in water emulsion for the ultra-filtration separation.
84 O.A. Jimoh et al. / Journal of Cleaner Production 195 (2018) 79e92

Emiworo Dolomite
Sample

Processing
Grinding by ball mill
Screening to 10 mm-20 mm

Calcine at temperature of
1000 oC for 180 min

Calcined
CO2 (g)
dolomite (s)

Calcium glucosate (aq) Mg (s)

Unreacted CO2 (g)

CO2 (g) Source Filtration

Glucose
Calcium glucosate (aq) Aloe vera recycle
extract

Reactor

PCC

Fig. 2. Process flow diagram for dolomite PCC synthesis.

3.2. EDAX analysis and PCC yield 82% of PCC yield under reaction conditions of 5 v/v% of initial
concentration of aloe vera, pH level of 6.5, and glucose solution
The PCC purity obtained under the best conditions of 5 v/v% of concentration of 0.5 M. Comparatively, Somarathna et al. (2016)
initial concentration of aloe vera and yields of samples 1 to 4 at reported a PCC yield of 79% by using sucrose as the Ca extractor.
different aloe vera concentrations are presented in Fig. 3 and
Table 3, respectively. As shown in Table 3, PCC yield increases 3.3. Analysis of the crystalline structures of the synthesized PCC
marginally as the aloe vera concentration increases. This result can samples
be attributed to the higher CO2 solubility in the aloe vera solution
(consisting of mainly amino acids and proteins) than that in ordi- The XRD spectrum of raw powdered dolomite carbonate rock
nary H2O (Díaz-Reinoso et al., 2006). The higher CO2 content is sample obtained from the Emiworo area is shown in Fig. 4a. The
favorable to obtain more PCC yields at higher aloe vera concen- high intensity peak at 30.97
indicates the presence of dolomite as a
trations. Hence, the high reactivity of the aloe vera extract with the prominent constituent mineral. The peak at 24.1
represents the
calcium glucosate solution and CO2 at room temperature achieves presence of low amount of calcite in the sample. The XRD pattern of
 O.A. Jimoh et al. / Journal of Cleaner Production 195 (2018) 79e92 85

(a)

keV

(b)

keV

Fig. 3. EDAX of (a) samples without D-glucose and aloe vera extract and (b) samples with D-glucose and aloe vera extract.

Table 3
Mg2þ content and PCC yields prepared from different additive concentration.

Sample name D-glucose concentration (mol dm3) Aloe-vera concentration (v/v%) Mgþ content (%) Yield (%)

1 0 0 28.60 51
2 0.5 0.5 0.26 68
3 0.5 2 0.19 79.5
4 0.5 5 0.30 81.2

each sample prepared using different aloe vera extract concentra- Santos et al., 2012; Shafiu Kamba et al., 2013). Temperature is
tion at room temperature and final pH level of 6.5 was analyzed to crucial to ensure the formation of aragonite phase in the composite
determine the presence of calcite, aragonite, and vaterite crystalline polymorph, which increases the net energy required for this phase
phases (Fig. 4bed). Fig. 4b shows that the three PCC phases, namely PCC. Hence, this phenomenon is unattractive from an industrial
calcite (104), aragonite (021, 221), and vaterite (100), are present standpoint. In addition, by using 5 v/v% of aloe vera extract, the
without the addition of aloe vera. Meanwhile, Fig. 4c reveals only aragonite phase PCC was synthesized.
calcite and aragonite phases at an aloe vera concentration of 0.5 v/v
%. As the concentration of aloe vera extract was increased to 5 v/v%, 3.4. Formation mechanism of flower-like structure with radiating
only the aragonite phase with sharp peak reflections of (021), (221), ends aragonite PCC over aloe vera extract
and (102) was observed, as shown in Fig. 4d.
Acicular calcite and aragonite CaCO3 with vast application po- Aloe vera extract contains acid proteins and polysaccharides
tentials have been synthesized by Kajiyama et al. (2014). Aragonite within the protoplast of the parenchyma cell wall matrixes.
phase PCC has been widely studied and synthesized above room Parenchymal cell walls have active hydroxyl functional groups.
temperature in the range of 35
Ce70
C (Ramakrishna et al., 2016; Microscopy study of the aloe vera leaves cell revealed that the pulp
86 O.A. Jimoh et al. / Journal of Cleaner Production 195 (2018) 79e92

102000 a)
68000

34000

900
b) 104
021
600
100 221
Intensity (a.u.)

300

0
4000

3000
c) 104

2000

1000
012

0
3400
021
d)
2550

1700
221
102
850

0
10 20 30 40 50 60
2 Theta (degrees)
Fig. 4. X-ray diffraction (XRD) pattern of PCC. (a) Dolomite, (b) without additive, (c) with 0.5 v/v% aloe-vera extract, and (d) with 5 v/v% of aloe vera extract.

consists of transparent large (1000 mm) mesophyll with a hexago- (2009) reported that needle-like aragonite can be achieved using
nal or elongated hexagonal shape (Ni et al., 2004). Previous re- Mg as a structure directing agent.
ported studies have shown that acid proteins can significantly
influence the crystallization of CaCO3 (Friedman et al., 1962; Han 3.5. Particle size of the synthesized PCC samples
et al., 2005). Bio-based additives can poison the calcite crystalli-
zation in situ and induce the transformation transit to aragonite Particle size analysis presented in Fig. 5a shows that approxi-
phase (Greer et al., 2015). Declet et al. (2016) conducted studies on mately 90% (Dv 90) of the synthesized A-PCC particles were within
PCC synthesis by using chitin, containing repeating chains of b-(1,4) the size of 3.34 mm. Meanwhile, 10% of the particles (Dv 10) was
N-acetyl glucosamine and substantial amount of H ions. The chitin 1.26 mm, and the average size (Dv 50) of the particles is 1.02 mm
as an additive revealed that amino groups could induce phase with a recorded span value of 2.04. The PCC without aloe vera
transformation from calcite polymorph to aragonite. Moreover, aloe extract (Fig. 5b) had a higher particle size, as shown in Tables 4a and
vera extract containing polysaccharides and acid proteins can in- 4b. The results showed that 90% (Dv 90) of the particle had a size of
fluence the morphology of synthesized PCC, thereby resulting in 33.5 mm, 50% (Dv 50) of particles had a size of 16.30 mm, and 10%
composite (calcite and aragonite) polymorph (Jimoh et al., 2017c). (Dv 10) of the particles had a size of 6.53 mm with a span value of
In addition, the detailed plausible formation mechanism for this 1.65. Aloe vera has been employed as a reducing agent to tailor the
type of PCC with a polycrystalline dumbbell-like structure has been synthesis of Au and Ag nanoparticle sizes in previous studies
adequately reported in our previous work. The crystal growth of the (Chandran et al., 2006; Muralikrishna et al., 2014). Therefore, the
obtained flower-like structure with radiating ends was propagated decrease in particle size is ascribed to the volume contraction/
by unleached in-situ Mg, higher concentration of aloe vera, and shrinking of the PCC particles by the resulting surface compounds
glucose that allows calcite and aragonite phase formation. Hu et al. of the aloe vera extract.
 O.A. Jimoh et al. / Journal of Cleaner Production 195 (2018) 79e92 87

12 body, thereby maintaining dispersion in flat and semigloss paints

(a) and to adjust the consistency and minimize paint sag (Ciullo, 1996).
10
3.6. SEM analysis of the PCC samples
Volume (%)

8
Fig. 6 presents SEM images of PCC particles synthesized at
6 different aloe vera extract volume concentrations. Traditionally,
PCC formed in H2O without additives are characterized by
4
rhombohedral-ordered structures composed of six facets, most of
which are microscopic epitome of the unit cells (Jimoh et al., 2016).
2
PCC formed without aloe vera extract revealed an agglomerated
0 cluster with visible calcite phase (Fig. 6a). At extract volume con-
0.01 0.1 1 10 100 1000 10000 centration of 0.5 v/v%, the morphology of the PCC was rhombo-
Particle (μm) hedral calcite and needle-like aragonite with a diameter in the
range of 1.2e1 mm. This result is contrasting to the results of the PCC
12 synthesized in the absence of aloe vera extract (Fig. 6b). Previous
studies showed that morphological modifiers can increase or
(b)
10 decrease the particle size (Alvarez and Paulis, 2017). Hence, the
reduced particle diameter range confirms the addition of aloe vera
8 and suggest possible versatility of the synthesized PCC for a variety
Volume (%)

of applications. Further increase in the extract concentration to 5 v/

6 v% transforms the aragonite PCC particle from monocrystalline
elongated phase to hierarchical morphology of flower-like struc-
4 tures with radiating ends (Fig. 6c). The formed crystal particles at 5
v/v% extract concentration have almost similar dimensions with
2 the added aloe vera concentration of 0.5 v/v%. Therefore, the
evolved particle morphology suggests that the aloe vera extract and
0 in situ Mg have significant influences on the crystalline structure of
0.01 0.1 1 10 100 1000 10000 PCC.

Particle (μm) 3.7. Viscosity of membranes

Fig. 5. Particle size distribution of the synthesized PCC (a) with aloe vera extract (b)
without aloe vera extract.
The viscoelastic properties of dope solution is a major param-
eter, which can affect the kinetics of phase inversion and spinning
process. The viscosities of all prepared dope solutions were
Table 4a measured as a function of A-PCC content (Fig. 7). As shown in the
PCC Microparticles with aloe vera extract. figure, the viscosities of the dope solutions were significantly
Particle characterization increased with the increase in A-PCC content. This reason can be
interpreted that the addition of A-PCC in the solution matrix
Dv (10) 1.26 mm
Dv (50) 1.02 mm increased the concentration of casting solution and consequently
Dv (90) 3.34 mm intensified the interacting force among the PES macromolecules,
Span 2.041 thereby resulting in the increase in the casting solution system with
Specific Surface Area 411.6 m2/kg the increase in A-PCC content.

3.8. Scanning electron microscopy analysis of the membranes

Table 4b
PCC Microparticles without aloe vera extract.
The surface and cross-sectional micrographs of composite and
Particle characterization neat HF membranes are shown in Fig. 8. The outer and inner cross-
Dv (10) 6.53 mm sections of all membranes had skin layers on both surfaces. All
Dv (50) 16.30 mm membranes displayed a similar structure consisting of asymmetric
Dv (90) 33.5 mm structure of UF membranes, a dense top layer, fully grown macro-
Span 1.653 voids at the bottom layer, and a highly porous finger-like sublayer.
Specific Surface Area 201.1 m2/kg
As observed from the surface images of the composite membranes,
A-PCC particles formed aggregates on the membrane surfaces.
These clusters were increased in number with the increase in
In addition, the result of the SEM micrographs showed smaller loading of A-PCC. Furthermore, this increase in A-PCC aggregates
particles size, which is anticipated as by laser light diffraction. This was expected to cause pore plugging during phase separation
result indicates that the measurement contained agglomerates. process especially with high A-PCC contents.
Accordingly, various polymorphs and particle sizes of synthesized
PCC have been employed for specific applications (Jimoh et al., 3.9. Influence of A-PCC content on membrane pore size and porosity
2017c). Conducted studies indicated that the PCC particles of
approximately 15 mm in diameter are more effective in rheology The pore size and porosity of membranes are presented in
modification and strengthening of sealants and adhesives Table 5. The membrane porosity was decreased upon the intro-
(Brockman et al., 2009). Meanwhile, the PCC particle size in the duction of A-PCC as the solid content was increased. Meanwhile,
range of 5e14 mm is used to control the flow properties to provide pore size was increased as the A-PCC content was increased and
88 O.A. Jimoh et al. / Journal of Cleaner Production 195 (2018) 79e92

(a)

(b)

(c)

Fig. 6. SEM of the samples obtained at different aloe vera extract concentrations: (a) without additive, (b) with added 0.5 v/v% of aloe vera, and (c) with added 5 v/v% of aloe vera.

1400 increase in membrane pore size, which may be attributed to the

increase in surface roughness. Thus, upon the addition of a small
1200 amount of A-PCC particles, dope solution with low viscosity is ob-
tained (Fig. 7). Moreover, membrane with small dense skin layer,
which can suppress the defects in the membrane, was formed.
1000
Viscosity (cP)

However, when the A-PCC content was high, the membrane with a
loose skin layer, which will cause the bubble point pressure to
800 decrease, was formed.

600
3.10. Mechanical property of PES blend membranes
400
0 1 2 3 4 5 The mechanical properties of membranes are important for
A-PCC content (wt.%) practical application (Ghasem et al., 2012). The elongation at break
and tensile strength of all membranes are presented in Table 6. As
Fig. 7. Viscosity of dope solutions with different A-PCC content. shown in the table, the tensile strength was increased from
3.12 MPa to 4.17 MPa and the elongation at break was decreased
from 15.26% to 11.57% with increasing A-PCC content from 0 to 5 wt
reached a maximum of 171 nm where the A-PCC content was 3 wt%. %. This result indicates that the introduction of A-PCC in the PES
The same trend was observed by Li et al. (2009), who found that causes a significant improvement in the membrane. This phe-
membrane porosity decreases linearly with TiO2 loading. nomenon may be the result of strong interacting force between PES
However, further increase in the A-PCC content (above 3 wt%) and A-PCC. The addition of A-PCC can serve as a cross-linker in the
decreased the pore size. A similar observation was obtained in a composite membrane to link the polymer chain, which will
study conducted by Alsalhy et al. (2013), who found that the enhance the rigidity of the polymer chain, as well as confined PES
addition of low ZnO content in the polymer matrix results in the crystallization. Thus, more energy is needed to break down the
 O.A. Jimoh et al. / Journal of Cleaner Production 195 (2018) 79e92 89

bond between PES and A-PCC. As a result, the mechanical proper-

ties was improved. With high A-PCC content of >2 wt%, significant
decrease in the elongation at break was observed. This result is
similar to that of the study conducted by Razmjou et al. (2012), who
observed that the TiO2 content of below 2 wt% provides membrane
with improved elastic behavior.

3.11. Influence of A-PCC on WCA of HF membrane

The hydrophilicity of membranes can affect PF and oil rejection.

Generally, contact angle (CA) is ineffective in estimating hydro-
philicity because CA is also dependent on the porosity, which is
driven by the capillary action (Yip et al., 2010). WCA is a clear in-
dicator of interfacial energy (IE) between water droplet and
membrane surface. The lower the CA is, the higher the IE will be,
which will lead to high hydrophilicity. The hydrophilicity of all
membranes was determined by WCA. Fig. 9 presents the dynamic
CA with different A-PCC contents, which can be influenced by
surface chemistry, roughness, and porosity. The time variation of
membrane hydrophilicity was achieved by observing the CA for
600 s. The results showed that the initial CA of the neat membrane
was higher than that of all modified membranes. The initial CA
values were 72.3 ± 2.22
, 62.7 ± 2.01
, 63.5 ± 1.75
, 62.5 ± 0.49
,
60.3 ± 045
, and 60.3 ± 0.62
for membranes PC-0, PC-1, PC-2, PC-3,
PC-4, and PC-5, respectively. In addition, the water drop diameters
of all membranes were almost constant with time. Thus, the decline
in time is caused by H2O penetrating through the membranes.
Meanwhile, the CA curve showed that the CA of the composite
membrane was decreased rapidly with the increase in the A-PCC
contents. Thus, upon the introduction of A-PCC into the PES matrix,
the membrane hydrophilicity is improved. Improved hydrophilicity
can be as a result of the effect of the A-PCC particles. In addition,
H2O molecules found within the membrane matrix tends to be
attracted and directed to pass through membrane pores, which will
improve water permeability (Otitoju et al., 2017a; b; Yang et al.,
2007a; b).

3.12. Effects of A-PCC content on membrane performance

The addition of A-PCC particles can influence the flux at least in

two aspects. Firstly, the A-PCC can increase the hydrophilicity of the
membrane, which could enhance the flux. Secondly, its effect on
the membrane morphology would affect the permeation proper-
ties. The results of pure WF of fresh and fouled membranes are
presented in Fig. 10. The pure WF (fresh membranes) increases with
increasing A-PCC content up to 3 wt% but decreases with further
addition. A maximum PWF of 180 kg/m2h was achieved when the
content of A-PCC was 3 wt%. However, upon further introduction of
A-PCC up to 5 wt% caused the PWF to decrease to 161 kg/m2h. In the
case of fouled membrane, a similar trend was observed.
Fig. 8. FESEM cross sectional structure of membrane (a) surface at 1200  , (b) cross-
section at 500  .
The relationship of the PF of membrane against varying A-PCC
contents is presented in Table 7. Evidently, the PF of the membranes
increased with the increase in the amount of A-PCC content
(0e3 wt%), which can be attributed to the improvement in

Table 5 Table 6
Influence of A-PCC content on membrane pore size and porosity. Influence of A-PCC content on mechanical property of PES blend membranes.

A-PCC content (wt.%) Pore size (nm) Porosity (%) A-PCC content (wt.%) Elongation at break (%) Tensile strength (MPa)

0 34.4 ± 1.04 77.2 ± 2.59 0 15.26 3.12

1 35.8 ± 1.75 76.3 ± 2.48 1 15.15 3.41
2 37.32 ± 1.70 75.5 ± 3.07 2 15.23 3.67
3 42.06 ± 1.30 73.3 ± 1.56 3 13.76 3.98
4 39.8 ± 1.10 72.2 ± 2.29 4 12.06 4.18
5 38.58 ± 1.18 71.5 ± 2.38 5 11.57 4.17
90 O.A. Jimoh et al. / Journal of Cleaner Production 195 (2018) 79e92

hydrophilicity due to increased membrane pore size. However,

with further increase in the A-PCC content of up to 5 wt%, the PF
was decreased. This result can be ascribed to the observed decrease
in pore size. The decrease in the PF at above 3 wt% A-PCC content
can be ascribed to the formation of thicker skin layer and pore
blockage as a result of PCC particle agglomeration on the mem-
brane surface (Fig. 8). Conducted studies revealed that excessive
loading of nanoparticles as additives in membrane matrix can
adversely affect membrane properties and performance mainly due
to the nonuniformity in particle dispersion on the membrane sur-
face (Chen et al., 2009; Jamshidi et al., 2015; Shen et al., 2011).
The results of the oil rejection for the modified and unmodified
membranes determined from Eq. (7) are presented in Table 7. The
oil rejection performance of the A-PCC membrane is comparable
with other reported HF membrane with even enhanced permeate
flux as shown in Table 8. All membrane exhibited a rejection rate of
>94% as compared with the controlled membrane of 93.9%. How-
ever, considering the PF and rejection, the PES membrane prepared
Fig. 9. Water contact angles with time of PES membranes as a function of A-PCC
content. by adding 3 wt% A-PCC was the optimum membrane because it
achieved the highest WF and superior oil rejection of above 99%. To

Fresh Membrane Fouled Membrane

180
Pure water flux (kg/m2h)

150

120

90

60

30

0
0 1 2 3 4 5
A-PCC content (wt.%)
Fig. 10. Water flux of membranes after and before membrane filtration.

Table 7
Effect of A-PCC contents on permeate flux, oil rejection and anti-fouling parameters of membranes.

A-PCC content (wt.%) Permeate flux (kg/m2h) Rejection (%) FRR (%) Rr (%) Rir (%) Rt (%)

0 49.87 93.9 61.8 13.2 38.3 51.5

1 55.08 94 82.8 33.8 17.2 51.0
2 96.58 98.6 87.4 31.2 12.6 43.8
3 102.15 99.8 86.4 31.4 11.9 43.3
4 96.20 94.3 82.8 19.5 23.8 43.3
5 91.06 96.5 70.2 5.2 38.5 43.7

Table 8
Performance comparison of A-PCC/PES HF membrane with reported HF membrane for wastewater applications.

Material Application Oil droplet (mm) TMP (bar) Permeate flux (kg/m2h) Rejection (%) Ref.

Cellulose Machine oil e 1 7.7 e Li et al. (2006b)

PVDF/P(VDF-co-CTFE)-g-PMAAg-fPEG(PVDF/AP) Hexadecane oil 1e50 3.4 ~70 98 Zhu et al. (2014)
Polyphenylene sulfone (sPPSU) Soybean oil 0.1e6 e 23.3 99.62 Li et al. (2014)
TiO2-Mullite Soybean oil 1.08 0.025 150 97 Zhu et al. (2016)
PVDF-PVP-TiO2 Cutting oil 1.08 0.5 70.48 99.7 Ong et al. (2015)
PVDF-PVP-TiO2 Cutting oil 1.08 0.5 72.2 94 Ong et al. (2014)
Sulfonated polyphenylenesulfone (PPSU) Petroleum oil e 1 ~220 95.4 Luo et al. (2015)
PES/A-PCC Crude oil 1.54 1.5 102.15 99.8 This work
 O.A. Jimoh et al. / Journal of Cleaner Production 195 (2018) 79e92 91

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that the antifouling ability of the membrane can be enhanced upon (MOL) originated from carbide lime waste and operating parameters optimi-
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energy intensive route to aragonite synthesis. tated calcium carbonate: a review. Carbonates Evaporites 1e16.
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Conflicts of interest of aloe vera (Aloe barbadensis Miller) extract as a green morphological modi-
fier. J. Clean. Prod. 150, 104e111.
We declare that there is no conflict of interest in this work. Jimoh, O.A., Otitoju, T.A., Hussin, H., Ariffin, K.S., Baharun, N., 2017d. Understanding
the precipitated calcium carbonate (PCC) production mechanism and its char-
acteristics in the liquid-gas system using milk of lime (MOL) suspension. S. Afr.
Acknowledgement J. Chem. 70.
Kajiyama, S., Nishimura, T., Sakamoto, T., Kato, T., 2014. Aragonite nanorods in
calcium carbonate/polymer hybrids formed through self-organization pro-
The second author acknowledges Postdoctoral Fellowship from cesses from amorphous calcium carbonate solution. Small 10, 1634e1641.
the Shenyang University of Technology, Shenyang, Liaoning Prov- Kitamura, M., Konno, H., Yasui, A., Masuoka, H., 2002. Controlling factors and
ince, China for their aid in this research. mechanism of reactive crystallization of calcium carbonate polymorphs from
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