Energy Conversion and Management 122 (2016) 535543

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Energy Conversion and Management

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

Seashell-derived mixed compounds of Ca, Zn and Al as active and stable

catalysts for the transesterification of palm oil with methanol to
biodiesel
Wayu Jindapon a, Siyada Jaiyen b, Chawalit Ngamcharussrivichai b,c,
a
Program in Petrochemistry and Polymer Science, Faculty of Science, Chulalongkorn University, Pathumwan, Bangkok 10330, Thailand
b
Fuels Research Center, Department of Chemical Technology, Faculty of Science, Chulalongkorn University, Pathumwan, Bangkok 10330, Thailand
c
Center of Excellence on Petrochemical and Materials Technology (PETROMAT), Chulalongkorn University, Pathumwan, Bangkok 10330, Thailand

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

Article history: Heterogeneous base catalysts, composed of mixed calcium, zinc and aluminium compounds (ZSA), for the
Received 6 April 2016 transesterification of palm oil with methanol to produce biodiesel as fatty acid methyl esters (FAME)
Received in revised form 4 June 2016 were prepared from waste mixed seashells in the presence of zinc nitrate and alumina via dissolution-
Accepted 6 June 2016
precipitation method. The effects of the catalyst calcination temperature on the physicochemical and
Available online 14 June 2016
catalytic properties were studied. Calcination of ZSA at 300 C generated calcium hydroxide as the main
active phase, while the formation of CaO at higher calcination temperatures contributed to the catalyst
Keywords:
basicity and catalytic activity. The catalyst calcined at 500 C (ZSA-500) possessed a calcium-rich surface
Seashells
Calcium oxide
on which nanocrystallites of CaO were dispersed. The ZSA-500 catalyst showed the highest stability to
Transesterification ambient air (relative humidity of 73%) exposure for 3 d. The loss of catalytic activity at the higher calci-
Biodiesel nation temperatures of 700 and 900 C was related to the formation of Ca12Al14O33 and the transforma-
tion of CaO to calcium carbonate during air exposure. The ZSA-500 catalyst had the highest surface area
and basicity and gave the highest FAME yield (98.0 1.60 wt%). Suitable conditions for transesterification
over ZSA-500 at 60 C were a catalyst loading of 10 wt%, methanol:oil molar ratio of 30:1 and reaction
time of 3 h. Moreover, the ZSA-500 catalyst could be reused after methanol washing to give a FAME yield
more than 96% for at least five uses.
2016 Elsevier Ltd. All rights reserved.

1. Introduction experiences soap formation, catalyst exhaustion, yield loss and

Due to environmental concerns, the substitution of conven-
tional diesel with biodiesel has been increasingly promoted world-
wide [1]. Besides being a potentially sustainably renewable raw
material, biodiesel based upon fatty acid methyl esters (FAME)
possesses similar fuel properties to petroleum diesel but it is
non-toxic and biodegradable. Moreover, biodiesel combustion pro-
duces a relatively clean exhaust gas [2,3]. Nevertheless, the pro-
duction of biodiesel via transesterification, the conventional
route, of the triglycerides in vegetable oil or animal fats with
methanol in the presence of a homogeneous base catalyst is prob-
lematic due to a large amount of alkaline wastewater discharged
from the catalyst removal step [3]. In addition, the process
Corresponding author at: Department of Chemical Technology, Faculty of
Science, Chulalongkorn University, Pathumwan, Bangkok 10330, Thailand.
E-mail address: Chawalit.Ng@chula.ac.th (C. Ngamcharussrivichai).
crude glycerol contamination [2].
Heterogeneous catalysis has attracted considerable attention
for biodiesel production by transesterification owing to the expedi-
ency of catalyst recovery, catalyst reusability, process simplicity
and the higher purity of the obtained FAME and crude glycerol
[4]. A large number of solid catalysts have been investigated for
the transesterification of model triglycerides or vegetable oils with
methanol [525]. Calcium oxide (CaO) is a promising catalyst
because of its high basicity, fast reaction rate, low toxicity and
low cost. The sources for CaO catalyst preparation are available
in abundance, for example natural calcium rocks, as calcite and
dolomite [5], and waste calcium materials, such as abalone [6],
duck eggs [7] and angel wing shell [8]. However, CaO is succes-
sively transformed to calcium methoxide and calcium glyceroxides
(Ca(C3H7O3)2) during use [9]. Although the glyceroxides were
believed to be the active phase of the pure CaO catalyst [10], their
formation contributed to homogeneous catalysis [9,10]. It is
worth noting that the solubility in methanol of Ca(C3H7O3)2, at

http://dx.doi.org/10.1016/j.enconman.2016.06.012
0196-8904/ 2016 Elsevier Ltd. All rights reserved.
536 W. Jindapon et al. / Energy Conversion and Management 122 (2016) 535543
6216 mg L
1 [10], is about 200-fold higher than that of CaO, at
28 mg L
1 [9]. Besides, a practical use of CaO as commercial biodie-
sel catalyst is limited by a fast deactivation via chemisorption of
atmospheric carbon dioxide (CO2) and moisture upon exposure
to ambient air [9,10].
Various supports have been applied to immobilize CaO to
improve the dispersion of the CaO crystallites as well as the textu-
ral properties and stability of the immobilized catalysts [1114].
Combining CaO with other metal oxides, such as those of magne-
sium (MgO) [15], zinc (ZnO) [16] and zirconium [17], as binary
mixed oxides is an effective route to improve the specific surface
area, basicity and catalytic performance of the CaO-based catalysts.
Moreover, three-component mixed oxides of Ca, Mg and Zn have
been reported to be highly active catalysts in the methanolysis of
palm kernel oil to FAME [18]. A stable CaO catalyst with an
enhanced mechanical strength was obtained by forming a Ca/Al
composite of CaO and Ca12Al14O33 at high temperatures [11],
whilst a spinel mixed ZnO and aluminium oxide (Al2O3) catalyst
was preferred in the first commercial biodiesel production plant
using heterogeneous catalysis [4].
In this study, new active solid catalysts with a higher degree of
structural stability in ambient air and during the transesterification
of vegetable oil with methanol were prepared. As an attempt
towards using more sustainable sources for the catalyst prepara-
tion, waste mixed seashells from a frozen food industry were used
as the raw material. The catalysts, composed of various types of
mixed metal compounds of Ca, Zn and Al (ZSA), were prepared
via dissolution and precipitation under acidic conditions, followed
by calcination. The effects of the calcination temperature and of
exposing the calcined catalysts to ambient air on the crystalline
structure and the catalytic activity were investigated. Overall,
despite their high catalytic activity, the optimal ZSA catalyst was
relatively stable in the humid ambient with a relative humidity
(RH) of 73%, regenerable and reusable.
2. Experimental
2.1. Materials and reagents
Waste mixed seashells of Perna viridis, Amusium pleuronectes,
Anadara granosa and Meretrix meretrix were provided by the Thai
Dolomite Co. Ltd., (Surat Thani Province, Thailand). Elemental anal-
ysis by X-ray fluorescence spectroscopy indicated the metal oxide
composition as 68.6% CaO, 0.8% silica, 0.2% Al2O3 and 0.5% MgO,
with the balance as CO2. Zinc nitrate hexahydrate (Zn(NO3)26H2O)
and Al2O3 were obtained as analytical reagent (AR) grade from Ajax
Finechem. Nitric acid (HNO3; AR grade, 70 wt%) was supplied by J.
T. Baker Macron Fine Chemicals. Refined bleached deodorized
(RBD) palm oil (edible grade) was obtained from the Chumporn
Palm Oil Industry P.L.C. (Chumporn Province, Thailand). Its fatty
acid composition and basic properties are listed in the
Supplementary Information (SI) Table S1. Other reagents used
were commercial grade (99.5%) methanol, methyl heptadecanoate
(99.5%, Fluka), N-methyl-N-(trimethylsilyl)tri-fluoroacetamide
(MSTFA) (99%, Fluka), tricaprin (99%, Sigma Aldrich), pyridine
(99.8%, Carlo Erba) and n-heptane (99.8%, Riedel-deHan).
2.2. Preparation of the ZSA catalyst by dissolution-precipitation
In a typical procedure, the waste mixed seashells were ground
and sieved to reduce their size to less than 10 lm. After pretreating
the seashells at 600 C for 2 h, they were dispersed in an aqueous
solution of Zn(NO3)26H2O previously adjusted to pH 1 with 1 M
HNO3. The white slurry formed was vigorously stirred at ambient
temperature for 120 min, and then Al2O3 powder was added to
give a 1:0.6:0.4 mass ratio of the calcined seashells: Zn(NO3)2
6H2O:Al2O3. After stirring for another 60 min, the resulting
mixture was sonicated at 40 C for 4 h until it formed a paste.
The moisture remaining in the mixture was removed by drying
in an oven at 100 C for 24 h. Finally, the dried solid was crushed
into powder (<10 lm) and calcined in a muffle furnace at the
desired temperature (300900 C) for 2 h at a heating rate of
3 C min
1. The catalyst attained was designated as ZSA-x, where
x represents the calcination temperature used.
2.3. Catalyst characterization
Elemental analysis of the waste mixed seashells was performed
using a JEOL ED-2000 energy dispersive X-ray fluorescence spec-
trometer. The crystalline phases present in the catalysts were
determined by powder X-ray diffraction (XRD) using a Rigaku
DMAX 2200/Ultima + diffractometer equipped with Cu Ka radia-
tion with a 0.02 step size at room temperature and recording
the spectra over a 2h range of 1080. The diffraction peaks were
assigned after consulting the Joint Committee on Powder Diffrac-
tion Standard (JCPDS) files. The skeletal structure and the surface
functional groups of the catalysts attained at different calcination
temperatures were identified by Fourier transform-infrared spec-
troscopy (FTIR) using a PerkinElmer Spectrum One instrument.
The samples were prepared according to the standard KBr method.
The spectra were recorded at room temperature for 64 scans over
4004000 cm
1 at a resolution of 4 cm
1. The thermal decomposi-
tion behavior of the catalysts (10 mg) was investigated by
thermogravimetric/differential thermal analysis (TG/DTA) on a
PerkinElmer Diamond thermogravimeter with a temperature ramp
rate of 8 C min
1 from room temperature to 1000 C under a dry
nitrogen (N2) flow rate of 10 mL min
1. The morphology and the
surface elements of the catalysts were analyzed by scanning elec-
tron microscopy (SEM) with energy dispersive X-ray spectrometry
(EDS) using a JEOL JSM-5800LV microscope equipped with an
Oxford Link/ISIS 300 energy dispersive X-ray spectrometer.
The total basicity of the catalyst was determined by pulse
chemisorption of CO2 using a Micromeritics AutoChem II 2920
chemisorption analyzer. The catalyst pretreatment was performed
at 300500 C, depending on the calcination temperature of the
catalyst, for 2 h under an argon (Ar) flow (50 mL min
1). Subse-
quently, a small amount of CO2 (10 vol% in Ar) was injected into
the sample as the adsorption step. The excess CO2 was then
removed from the sample by purging with an Ar flow. Both steps
were sequentially repeated until the adsorption of CO2 reached
saturation. The accumulative amount of CO2 disappearing in each
step, corresponding to the amount of basic sites, was detected with
a thermal conductivity detector (TCD). The N2 physisorption
measurements were performed on a Micromeritics ASAP 2020
surface area and porosity analyzer to determine the textural
properties of the catalysts. The samples (80 mg) were pretreated
by degassing at 300 C for 2 h. The specific surface area (SBET)
was calculated according to the Brunauer-Emmett-Teller (BET)
equation from the adsorption branch in the relative pressure of
0.020.2. The total pore volume (Vp) was estimated from the
amount of N2 adsorbed at a relative pressure of about 0.990.
2.4. Transesterification procedure
The transesterification of RBD palm oil with methanol was per-
formed in a 100-mL round bottom flask equipped with a water-
cooled condenser and a magnetic stirrer. Typically, the calcined
catalyst (1 g) was vigorously stirred in methanol (11.4 g) for
30 min, followed by the addition of the RBD palm oil (10.0 g).
The temperature of reaction mixture was maintained at 60 C
using a water bath. The amount of the catalyst was varied between
 W. Jindapon et al. / Energy Conversion and Management 122 (2016) 535543 537

5 and 15 wt% (based on the weight of palm oil) with a constant

methanol:oil molar ratio of 30:1, whilst the methanol:oil molar
ratio was varied from 20:150:1 at a constant catalyst loading of
10 wt%. After the course of reaction (13 h), the solid phase was (e)
recovered by centrifugation at 5000 rpm. The excess methanol
was removed from the products using a rotary evaporator
(HEIDOLPH LABOROTA 4003) operating at 60 C, 0.10 atm. The
remaining liquid was washed with deionized water, resulting in (d)
two-phase product. The top layer of FAME and glyceride deriva-

Intensity/ a.u.
tives was taken, dried with anhydrous Na2SO4 and diluted with
n-heptane. The FAME composition was analyzed according to the
standard method EN 14103:2003 using a Shimadzu 14B gas chro-
(c)
matograph (GC) equipped with a flame ionization detector (FID)
and a 30-m DB-Wax capillary column. Methyl heptadecanoate
was used as the reference standard. The FAME yield was calculated
according to our previous work [24]. To quantify the mono-,
(b)
di- and tri-glycerides, MSTFA was added into the liquid sample
to convert the mono- and di-glycerides to more volatile deriva-
tives. The analysis was performed following the standard EN
14105 procedure on an Agilent 7890A GC equipped with a FID (a)
and a 15-m DB-5ht capillary column. Pyridine and tricaprin were
used as the solvent and reference standard, respectively. The GC 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80
conditions for the FAME composition analysis and the glycerides 2 Theta/ degree
quantification are shown in Tables S2 and S3 (SI), respectively.
Fig. 1. XRD patterns of (a) the as-synthesized ZSA and the ZSA-x catalysts
calcined at (b) 300, (c) 500, (d) 700 and (e) 900 C. (Symbols: j = CaCO3,
H CaO, 4 = Ca(OH)2, s = Ca12Al14O33, d = ZnO, . = Zn5(OH)8(NO3)22H2O,
2.5. Reusability of the ZSA-500 catalyst h = ZnAl2O4 and = CaZn2(OH)62H2O).

To ascertain the reusability of the ZSA-500 catalyst, the spent

catalyst was recovered from the reaction mixture by centrifugation
and reused in fresh transesterification reactions of RBD palm oil
and methanol for five successive runs. In addition, the effect of
methanol washing of the spent catalyst on the subsequent FAME
yield obtained was evaluated. For spent catalyst washing, the
recovered ZSA-500 catalyst was dispersed in 50 mL of fresh metha-
nol with stirring for 15 min, followed by centrifugation to separate
the solid phase and then adding the washed catalyst into the fresh
reaction mixture without prior drying.
Similarly, the residual CaCO3 (2h = 29.5) in the ZSA-900 was
related to the adsorption of atmospheric CO2.
The as-synthesized ZSA exhibited a multi-step thermal decom-
position pattern (Fig. 2). The first weight loss stage in the differen-
tial thermogravimetric (DTG) curve (<100 C) was related to the
evaporation of residual moisture, whilst the weight losses in the
range of 120220 C were related to the Zn(OH)8(NO3)22H2O and
CaZn2(OH)62H2O decomposition, according to Eqs. (1) [26] and
(2) [27], respectively.

Zn5 OH8 NO3 2  2H2 O ! 5ZnO 2HNO3 5H2 O 1

3. Results and discussion
CaZn2 OH6  2H2 O ! CaOH2 2ZnO 4H2 O 2
The weight loss found at 256 C corresponded to the dehydra-
3.1. Catalyst characterization tion of Al(OH)3 to Al2O3. Due to the complexity of the weight loss
between 300 and 600 C, the Origin 8.5 program was applied to
The XRD patterns of ZSA before and after calcination at deconvolute the DTG peaks in this temperature range (inset;
300900 C are shown in Fig. 1. The major crystalline phases of the Fig. 2). The Ca(OH)2 derived from CaZn2(OH)62H2O (Eq. (2)) was
as-synthesized ZSA were Ca(OH)2, CaCO3 and CaZn2(OH)62H2O, decomposed at 375 C, whereas the decomposition steps observed
with small diffraction peaks of Zn5(OH)8(NO3)22H2O present. The at 395 and 515 C were related to Ca(OH)2 and Ca(NO3)2, respectively.
CaCO3 was originally present in the calcined seashells, while the
other phases were generated by the dissolution-precipitation of
calcium compounds in the acidified Zn(NO3)2 solution. The 10
ZSA-300 catalyst had ZnO as new phase, whereas Zn5(OH)8(NO3)2 700 515
5
2H2O and CaZn2(OH)62H2O were absent. After calcination at 600 0
500 C, Ca(OH)2 was dehydrated to CaO, whilst the increased inten- 395
375 -5
DTG/ g min-1

sity of the CaCO3 peaks was ascribed to recarbonation of CaO 500

Weight loss/%

-10
during the catalyst preparation under the ambient atmosphere.
400
Moreover, ZnAl2O4 and Ca12Al14O33 were generated by the solid- -15
state reactions of ZnO [4] and CaO [11] with Al2O3, respectively. 300 515 -20
When the calcination temperature was increased to >700 C, the 256 -25
200 118 166 390
CaCO3 in the waste seashells was extensively decomposed to 691 -30
CaO. The enhanced peaks of CaO, ZnO, ZnAl2O4 and Ca12Al14O33 64 197
100
-35
indicated that their large crystallites were preferentially formed
0 -40
at these high temperatures. In addition, small peaks of contaminat- 0 200 400 600 800 1000
ing Ca(OH)2 (2h = 17.9, 34.1 and 47.0) were observed in the Temperature/ C
catalysts calcined at 700900 C, which was due to rehydration
of CaO with atmospheric moisture during the XRD analysis. Fig. 2. Weight loss and DTG curves of the as-synthesized ZSA.
538 W. Jindapon et al. / Energy Conversion and Management 122 (2016) 535543

The final weight loss at 691 C was due to decarbonation of CaCO3

to CaO. The phase compositions of the as-synthesized ZSA, as
determined by TGA, revealed that more than 55 wt% of the compo- 1
nents that were present as calcium compounds could be converted 2
to CaO at temperatures around 500 C (Table S4, SI).
The FTIR spectra of the ZSA-x catalysts calcined at different tem-
peratures are shown in Fig. 3, and the corresponding assignments
are summarized in Table S5 (SI). The band at 3643 cm
1 was due to
m(OAH) of the Ca(OH)2 structure. The bands at 1428 and 875 cm
1
were ascribed to the c(CAO) and d(CAO) of CaCO3, respectively. 3
The presence of CaZn2(OH)62H2O in ZSA-300 was evidenced by
the bands at 3575 and 3507 cm
1. The band at 1348 cm
1
originated from NO
3 in the structure of Ca(NO3)2. Other bands
below 940 cm
1 were related to various metal-oxygen bands
(Table S5, SI). When the calcination temperature was increased
to 500 C, the bands corresponding to the OAH stretching of
CaZn2(OH)62H2O disappeared concomitantly with the absence of
O Ca
NO
3 . As deduced from a remarkable decrease in the CO3
2

band
intensities, CaCO3 was decomposed at temperatures >700 C. The 1
enhanced intensity of OAH stretching (3643 cm
1) observed for
ZSA-700 was related to the rehydration of CaO to Ca(OH)2 that
was favorably formed on this catalyst (Section 3.3). The decompo- Ca
Zn Al
sition of these mixed metal compounds generated a new band at
Ca
ca. 450 cm
1 that was attributed to the presence of discrete ZnO
and CaO in the lattice. Thus, the FTIR results confirmed the phase
composition of ZSA-x catalysts in agreement with the XRD and
TGA results.
The SEM image of ZSA-500, as a representative catalyst,
revealed the presence of particles with different shapes and sizes, Al Ca
O
whilst the EDS analysis of the elemental composition of the surface 2
of these particles revealed their different compositions (Fig. 4). The
small spheres with diameters in the range of 0.51.0 lm (location
No. 1 in Fig. 4), some of which were merged into or embedded in Zn
larger particles, had a Ca:Zn:Al:O atomic ratio of 11.8:1:1.8:67.4.
This was ascribed to the presence of calcium-rich compounds Ca Ca
mixed with Al2O3. The plate-like particles (location No. 2 in
Fig. 4) were Ca12Al14O33 [19], as suggested by the Ca:Zn:Al:O
atomic ratio of 5.1:1:6.6:24.3. The smaller particles (location No.
3 in Fig. 4) had a Ca:Zn:Al:O atomic ratio of 8.4:4.6:1:27.9 and so
Ca
Zn
3
(d)
O

Ca
(c) Al
Ca

(b)
%T

Fig. 4. SEM image (5000 magnification) of the ZSA-500 catalyst and the EDS
spectra from the indicated three regions of the SEM image.

(a)
were mixed oxides of Ca and Zn that would have been derived from
1045
3643

the co-precipitation of dissolved calcium species with Zn(NO3)2 in

1630

712

the solution [16]. These results indicated that the surface of the
940

570
450
822
3575

ZSA-500 catalyst was richer in calcium than the bulk composition

3507
3433

875

(Ca:Zn:Al = 2.3:1:1). It is possible that some of the calcium com-

1348
1428

pounds were dissolved from the calcined seashells and then the
dissolved calcium species (Ca2+) were reprecipitated with Zn2+
4000 3600 3200 2800 2400 2000 1600 1200 800 400
and Al2O3 to form the different Ca, Zn and Al mixed compounds.
Wavenumber/ cm-1
The physicochemical properties of the ZSA-x catalysts obtained
Fig. 3. FTIR spectra of the ZSA-x catalysts calcined at (a) 300, (b) 500, (c) 700 and after calcination at different temperatures are summarized in
(d) 900 C. Table 1. Unlike the ZSA-x catalysts calcined at temperatures
 W. Jindapon et al. / Energy Conversion and Management 122 (2016) 535543 539

Table 1
Effect of the catalyst calcination temperature on the physicochemical properties and the FAME yield obtained from different ZSA-x catalysts.

Catalysta Metal phaseb Cluster size of CaOc SBETd Vpe Dpf Basicityg Initial rate FAME yieldh
(nm) (m2 g
1) (cm3 g
1) () (lmol g
1) (gFAME g
1cat. h

1
) (wt%)
ZSA-300 CC, CH, CN, ZO, AO 25.93i 5.53 0.007 47.9 28 5.74 95.2 0.85
ZSA-500 CC, CO, ZO, ZA, AO, CA 34.14 12.68 0.019 61.7 53 3.99 98.0 1.60
ZSA-700 CC, CO, ZO, ZA, AO, CA 40.81 8.88 0.035 159.8 25 1.23 95.2 2.55
ZSA-900 CO, ZO, ZA, AO, CA 50.71 5.72 0.004 27.1 20 2.76 91.4 2.60
a
Catalysts are shown as ZSA-x, where x is the calcination temperature (C).
b
Metal phase: CC = CaCO3, CH = Ca(OH)2, CN = Ca(NO3)2, CO = CaO, ZO = ZnO, ZA = ZnAl2O4, AO = Al2O3 and CA = Ca12Al14O33.
c
Determined from the XRD patterns using Sherrers equation.
d
BET surface area.
e
Total pore volume.
f
Average pore size.
g
Determined by CO2 pulse chemisorption.
h
Reaction conditions: catalyst amount, 10 wt%; palm oil amount, 10 g; methanol:oil molar ratio, 30:1; temperature, 60 C; time, 3 h.
i
Cluster size of Ca(OH)2.

>500 C, ZSA-300 possessed mainly Brnsted basic sites of nano-
sized Ca(OH)2. From previous reports, the other metal compounds
formed at 300 C were expected to contribute a minor basicity
[20,21,28]. The highest surface area and basicity was observed in
the ZSA-500 catalyst, and this is accounted for by the transforma-
tion of Ca(OH)2 and Ca(NO3)2 to CaO nanocrystallites dispersed on
Al2O3. Our previous work demonstrated that the surface area and
basicity of ZSA-500 were higher than those of pure CaO obtained
from calcination of waste mixed seashells at 800 C [14]. It can
be seen that the ZSA-x catalysts possessed meso-scale porosities,
which should be defined as interparticle voids similarly to other
CaO-based catalysts [5,16,18]. Further increasing the calcination
temperature increased the crystallite size of CaO and decreased
the total basicity, which is due to the agglomeration of CaO clusters
at high temperatures and that the majority of large CaO crystallites
were generated directly from the decomposition of CaCO3 in the
original seashells. Moreover, a portion of CaO was consumed in
the formation of Ca12Al14O33 when the calcination was performed
at >500 C. This calcium aluminate phase has a low basicity [12],
but can improve the mechanical and chemical stability of the
calcium-based catalysts [22].
Overall, the as-synthesized ZSA consisted of Zn5(OH)8(NO3)2
2H2O, CaZn2(OH)62H2O, Ca(OH)2 and Ca(NO2)3 supported on
CaCO3 and Al2O3 (Scheme 1). When the catalyst was calcined at
300 C, Zn5(OH)8(NO3)22H2O and CaZn2(OH)62H2O were decom-
posed to give ZnO and ZnO/Ca(OH)2, respectively. At 500 C, CaO
was generated by the dehydration of Ca(OH)2 concomitantly with
the formation of ZnAl2O4 and Ca12Al14O33 on the interfaces
between the ZnO, CaO and Al2O3. The presence of both mixed oxide
phases indicated a strong interaction of the basic oxides with the
Al2O3 support. By increasing the calcination temperature to 700
and 900 C, the crystallite sizes of CaO and ZnO were enlarged
and the formation of the mixed aluminate phases was promoted.
According to the previous works [14], we believed that Ca(OH)2
and CaO are the main active phases in the transesterification with
refluxed methanol, while other metal phases should have much
less activity due to their low basicity and mild reaction conditions
used in the present study.

ZHN CZ CH/ CN ZnO ZnOCH CH/ CN

Al2O3/ CaCO3 300 C Al2O3/ CaCO3

HNO3
As-synthesized ZSA H2O
500 C H2O
NO, O2

ZnO ZnOCaO CaO ZnO ZnOCaO CaO

700 C
Al2O3/ CaO/ CaCO3 Al2O3/ CaCO3

ZnAl2O3 Ca12Al14O33 CO2 ZnAl2O3 Ca12Al14O33

900 C

ZnO ZnOCaO CaO

Al2O3/ CaO/ Ca 12 Al14O33

ZnAl2O3

Scheme 1. Model for the ZSA-x catalysts formed at different calcination temperatures. (Metal compounds: ZHN = Zn5(OH)8(NO3)22H2O, CZ = CaZn2(OH)62H2O,
CH = Ca(OH)2, CN = Ca(NO2)3).
540 W. Jindapon et al. / Energy Conversion and Management 122 (2016) 535543
3.2. Transesterification of RBD palm oil with methanol over the ZSA-x
catalysts
The ZSA-x catalysts calcined at different temperatures were
tested in the catalysis of the transesterification of RBD palm oil
with methanol to FAME. The results are summarized in Fig. 5,
whilst the initial rate of reaction and the maximum yield of FAME
attained are given in Table 1. The ZSA-300 catalyst gave the fastest
initial reaction rate, being from 1.44- to 4.67-fold faster than the
ZSA-x catalysts calcined at higher temperatures, which is presum-
ably related to the Brnsted basicity of Ca(OH)2 and the smaller
size of Ca(OH)2 clusters. However, the slowest initial rate of reac-
tion was obtained with the ZSA-700 catalyst and not the ZSA-900
one. Kouzu and co-workers reported that Ca(OH)2 was active as a
transesterification catalyst, giving a FAME yield of 93% at 3.5 h
[10]. However, the initial rate did not proportionally correlate to
the total basicity of the catalysts, suggesting that some of the basic
sites were inaccessible or hindered for the bulky triglyceride mole-
cules due to the presence of various types of metal compounds
mixed in the catalysts. The absence of a clear trend between the
basicity and activity of the catalysts is unsurprising since small
probe molecule (CO2) were used in the chemisorption measure-
ment [29]. The difference in the phase composition and the nature
and distribution of basic sites could account for the different FAME
yields obtained with time. Nevertheless, the ZSA-500 catalyst, with
the highest basicity, gave the highest FAME yield after 2 h, empha-
sizing the beneficial influence of a high surface area and high
dispersion of CaO nanocrystallites. The maximum FAME yield
attained at 3 h was ranked in the descending order: ZSA-500 >
ZSA-700 > ZSA-300 > ZSA-900. In addition, ZSA-500 gave a higher
FAME yield than the pure CaO catalyst derived from the waste
mixed seashells [14].
3.3. Stability of the ZSA-x catalysts in ambient air
To reveal the stability of the ZSA-x catalysts towards the
chemisorption of CO2 and H2O present in the atmosphere, the
ZSA-x catalysts were exposed to the ambient air (RH  73%) for
3 d, and structural changes were observed by XRD analysis
(Fig. 6). When ZSA-300 was exposed to air for 3 d, it exhibited a
decreased peak intensity of Ca(OH)2, while for the ZSA-500 catalyst
100
90
80
FAME yield / wt.%
70
60
50
40
30
20
10
0 retention of the catalytic activity (higher FAME yield) after air
0 1 2 3
Reaction time /h
Fig. 5. Dependence of the FAME yield on the reaction time in the transesterification
of RBD palm oil with methanol over the ZSA-x catalysts calcined at different
temperatures. Reaction conditions: catalyst amount, 10 wt%; palm oil amount, 10 g;
methanol:oil molar ratio, 30:1; temperature, 60 C.
the CaO phase was reduced without any significant increase in the
intensities of the CaCO3 and Ca(OH)2 phases. A remarkable change
in the crystalline structure was observed in the ZSA-700 and
ZSA-900 catalysts after the air exposure, where both had a large
amount of CaO as the major basic site before exposure but either
no or only a small amount in the ZSA-700 and ZSA-900 catalysts,
respectively, after exposure.
The chemisorption of CO2 and H2O onto CaO yields CaCO3 and
Ca(OH)2, respectively. The activation energy (Ea) determined by
previous studies suggested that hydration of CaO (Eq. (3);
Ea = 11.020.3 kJ mol
1) [30] occurs more readily than carbonation
of CaO (Eq. (4); Ea = 2433 kJ mol
1) [31]. Lanas and Alvarez
observed the transformation of CaO to CaCO3 via generation of
Ca(OH)2 in ambient atmosphere since the carbonation at low tem-
perature requires water for CO2 dissolution on the solid surface
[32]. The crystallinity and stability of resulting Ca(OH)2 and CaCO3
phases were determined by water amount and CO2 pressure.
Besides, degree of carbonation strongly depended on crystallite
size of Ca(OH)2 [33]. Since CaCO3 (36.9 cm3 g
1) has larger volume
than Ca(OH)2 (33.6 cm3 g
1) and CaO (16.9 cm3 g
1) [34], the
formation of CaCO3 via direct carbonation of Ca(OH)2 (Eq. (5))
favors on large crystals [33].
CaOs H2 Og $ CaOH2s 3
CaOs CO2g $ CaCO3s 4
CaOH2s CO2g $ CaCO3s H2 Og 5
The less perturbed structures of the ZSA-300 and ZSA-500 cata-
lysts can be explained by the dispersed small active phase crystal-
lites to which the Al2O3 surface strongly interacted. Although the
CaCO3 layer formed on the catalyst surface was expected, it was
present as an amorphous or low crystalline carbonate phase due
to small sizes of Ca(OH)2. In the ambient air, vaterite as metastable
CaCO3 polymorph was initially formed over Ca(OH)2 phase, and
then was transformed to more stable calcite [32]. The crystallinity
of vaterite formed was relatively low, and its presence was difficult
to be confirmed by XRD. The major products from the air exposure
of ZSA-700 and ZSA-900 were significantly different. ZSA-700
exhibited an extensive conversion of CaO to Ca(OH)2, whereas
CaCO3 was mainly generated on the ZSA-900 exposed to air. This
finding was in accord with the FTIR results (Fig. 3). The larger
crystallites of CaO in ZSA-900 (Table 1) should promote the direct
carbonation of Ca(OH)2 to CaCO3 [32]. Retention of some CaO
phase in ZSA-900 after the air exposure should be ascribed to the
CaCO3 occupying the Ca(OH)2 surface as impermeable layer, which
prevent diffusion of CO2 and H2O into the interior crystals [35].
Other explanation is an enhanced interaction of CaO with Al2O3 at
900 C, relating to the formation of Ca12Al14O33 in the ZSA-900 catalyst.
With respect to the FAME yields attained over the different ZSA-
x catalysts before and after the air exposure a decreased FAME
yield was observed in all cases (Fig. 7). For ZSA-300, the slight
decrease in the FAME yield of 1.4% was possibly due to the struc-
tural retention of Ca(OH)2 as an active phase. However, the FAME
yield decreased further with increasing calcination temperatures,
reaching up to a 1.18-fold or 14.2% lower yield for the ZSA-900
catalyst. The extensive transformation of CaO to CaCO3 is the likely
major cause of the catalytic activity loss, since the ZSA-900
exposed to air possessed the highest CaCO3 content. The better
exposure by the ZSA-700 catalyst than the ZSA-900 one could
relate to the higher Ca(OH)2/CaCO3 phase ratio in ZSA-700
after air exposure. This result is in accord with a previous study
that revealed a relatively large catalytic activity loss by the
conversion of CaO to CaCO3 compared to the conversion of CaO
to Ca(OH)2 [10].
 W. Jindapon et al. / Energy Conversion and Management 122 (2016) 535543 541

(A) (B)

after after

Intensity/ a.u.

Intensity/ a.u.
before before

10 20 30 40 50 60 70 80 10 20 30 40 50 60 70 80
2 Theta/ degree 2 Theta/ degree

(C) (D)
after after

Intensity/ a.u.
Intensity/ a.u.

before before

10 20 30 40 50 60 70 80 10 20 30 40 50 60 70 80
2 Theta/ degree 2 Theta/ degree

Fig. 6. Effect of air exposure on the structure change of the ZSA-x catalysts calcined at (A) 300, (B) 500, (C) 700 and (D) 900 C. (Symbols: j = CaCO3, H CaO, 4 = Ca(OH)2,
s = Ca12Al14O33, d = ZnO, . = Zn5(OH)8(NO3)22H2O, h = ZnAl2O4 and = CaZn2(OH)62H2O).

100 the calcination temperature that was used, the easier the catalysts
were separated from the reaction mixture by centrifugation
90
(data not shown). Therefore, when including the ease of catalyst
80 recovery with the catalyst stability, initial reaction rate and final
FAME yield / wt.%

FAME yield, the ZSA-500 catalyst was the selected as the most
70
suitable one for the transesterification of palm oil with methanol,
60 and so was used hereafter.
50 The effect of varying the catalyst amount and the methanol:oil
molar ratio on the FAME yield obtained over the ZSA-500 catalyst
40
in the transesterification of palm oil with methanol is shown in
30 Fig. 8. At a 30:1 methanol:oil molar ratio, the reaction rate
20 increased with increasing catalyst loading up to 10 wt% (Fig. 8A),
as expected since the amount of active sites was increased.
10 However, a catalyst loading of 15% gave a comparable FAME yield
0 after 2 h of the reaction to that with 10 wt% catalyst, suggesting
300 500 700 900 that other factors become limiting. The maximum FAME yield
Calcination temperature/ C (98.0 1.60%) was achieved at 3 h with a 10 wt% catalyst. That this
was a slightly higher FAME yield than that with a 15 wt% catalyst
Fig. 7. Effect of exposure to ambient air for 3 d on the FAME yield attained over the loading might be related to catalyst agglomeration [8,16,19]. With
ZSA-x catalysts calcined at different temperatures: ( ) before and ( ) after the a 10 wt% catalyst loading, at a 20:1 methanol:oil molar ratio, the
3-d air exposure. Reaction conditions: see Fig. 5.
FAME yield increased with time and reached 94.6 2.50 wt%
within 4 h (Fig. 8B). Increasing the methanol:oil molar ratio to
3.4. Effect of the reaction conditions on the FAME production over the 30:1 actively promoted FAME production with a faster initial reac-
ZSA-500 catalyst tion rate, and reached 98.0 1.60 wt% within 3 h. However, further
increasing the ratio to 50:1 decreased both the initial reaction rate
Generally, the recovery and regeneration of pure CaO catalysts and the final FAME yield. The effect of the methanol:oil molar ratio
is difficult due to colloid formation and the transformation of the on the FAME yield at 1 h was not as pronounced as that at 2 h. The
active phase to Ca(C3H7O3)2 that can leach out [23,25]. In the pre- amount of methanol used in this study was much higher than the
sent study, although ZSA-300 had a higher initial reaction rate and theoretical ratio, and so the excess methanol might facilitate the
stability in ambient air than the other ZSA-x catalysts, the higher removal of polar products, such as monoglycerides and glycerol,
542 W. Jindapon et al. / Energy Conversion and Management 122 (2016) 535543

100 100
90 (A) 90 (B)
80 80

FAME yield/ wt.%

FAME yield/ wt.%

70 70
60 60
50 50
40 40
30 30
20 20
10 10
0 0
0 1 2 3 4 0 1 2 3 4
Reaction time / h Reaction time / h

Fig. 8. Effect of the (A) catalyst amount and (B) methanol:oil molar ratio on the FAME yield attained over ZSA-500 in the transesterification of RBD palm oil with methanol.
Other reaction conditions: see Fig. 5.

from the catalyst surface. However, the higher excess of methanol and then decreased only slightly to 96 wt% FAME yield after five
lowered the concentration of triglycerides on the catalyst surface, uses. It is worth noting that the pure CaO catalyst obtained from
rendering a slower rate of FAME formation. In conclusion, a suit- the waste seashells calcined at 800 C exhibited more severe activ-
able transesterification condition at 60 C for the ZSA-500 catalyst ity loss: the FAME yield was dropped from 99% to 80% at the fifth
was 10 wt% catalyst with a 30:1 methanol:oil molar ratio and a repetition [14].
reaction time of 3 h. The product analysis indicated that the The XRD analysis revealed that the structures of the fresh
contents of mono-, di- and tri-glycerides were 0.02, 0.06 and ZSA-500 and the spent ZSA-500 catalysts (after five cycles with
0.01 wt%, respectively, which are lower than the glycerides content methanol washing after each cycle) were slightly different
of biodiesel standard (0.2, 0.2 and 0.2 wt%) issued by the (Fig. S1, SI). The spent catalyst exhibited a lower intensity of most
Department of Energy Business, Ministry of Energy, Thailand. peaks than that of the fresh one because of the presence of organic
substances covering the catalyst surface. Nevertheless, the small
peaks of Ca(C3H7O3)2 were observed at 2h = 8.2 and 10.1 due to
3.5. Reusability of the ZSA-500 catalyst
the reaction of CaO with glycerol [23,25]. The amount of glycerol
and glyceride derivatives remaining in the spent ZSA-500 catalyst
The spent ZSA-500 catalyst was recovered from the reaction
was less than 2.0 wt%, as quantitatively determined by TGA
mixture by centrifugation and then, with or without methanol
(Fig. S2, SI), which was much smaller than that in the spent pure
washing, reused in fresh transesterification reactions of palm oil
CaO catalyst (13.5 wt%) [14]. Thus, the active phases of the
with methanol (60 C, 3 h, 10 wt% catalyst and a 30:1 methanol:
ZSA-500 catalyst had both a good tolerance to air exposure and a
oil molar ratio) for five successive runs to ascertain its reusability
stability against glycerol adsorption and transformation to
in terms of the obtained FAME yield (Fig. 9). Without methanol
glyceroxides. The small crystallites and strong interaction of the
washing of the catalyst between uses the FAME yield decreased
CaO species dispersed on Al2O3 may be crucial factors in the
slightly with each use from 99.2% to 87.3 wt% after four and five
improvement of catalyst stability.
uses. However, when the catalyst was washed with methanol
between uses, this decreased the loss of FAME yield such that
4. Conclusions
essentially the same activity was found for the first three uses

New heterogeneous base catalysts for the transesterification of

100 RBD palm oil with methanol were successfully prepared from
waste mixed seashells via the dissolution-precipitation method.
90
The total basicity, base type and textural properties of the catalyst
80 strongly depended on the temperature at which the catalyst was
calcined. The calcination at 500 C gave the ZSA-500 catalyst with
FAME yield/wt.%

70
the highest basicity and surface area due to the enhanced disper-
60 sion of CaO, generated from thermal decomposition of Ca(OH)2,
50 CaZn2(OH)62H2O and Ca(NO3)2, on the Al2O3. As a result, the max-
imum FAME yield of 98.0 1.60 wt% was achieved over ZSA-500
40
under the suitable transesterification conditions (catalyst load-
30 ing = 10 wt% based on the weight of oil, methanol:oil molar
20 ratio = 30:1, temperature = 60 C and time = 3 h). A strong interac-
tion of the mixed oxide nanocrystallites with the Al2O3 surface
10
improved not only the catalytic stability of ZSA-500 exposed to
0 ambient air for 3 d but also the stability against the glycerol
1 2 3 4 5 adsorption and transformation of CaO to calcium glyceroxides.
Numberof repetition
Acknowledgements
Fig. 9. Reusability of the ZSA-500 catalyst recovered without and with methanol
washing in the transesterification of RBD palm oil with methanol at 60 C for 3 h
with the catalyst loading of 10 wt% and methanol: oil molar ratio of 30:1. (Symbol: The authors are grateful to the Chumporn Palm Oil Industry
= no washing, = washing with methanol). Reaction conditions: see Fig. 5. Public Company Limited and the Thai Dolomite Company Limited
 W. Jindapon et al. / Energy Conversion and Management 122 (2016) 535543
for donating the RBD palm oil and the waste seashell samples,
respectively. This research was funded by Chulalongkorn
University through the Ratchadapiseksompoch Endowment Fund
(2013), project no. CU-56-912-EN, and the PTT Public Company
Limited. Financial and technical supports from the Thailand
Research Fund (TRF) under the project no. IRG5780001 (Faculty
of Science, Chulalongkorn University), and the Center of Excellence
on Petrochemical and Materials Technology (PETROMAT),
Chulalongkorn University, are also acknowledged. The authors also
wish to express their thanks to Dr. Robert Douglas John Butcher
(Publication Counseling Unit, Faculty of Science, Chulalongkorn
University) for English language editing.
Appendix A. Supplementary material
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.enconman.2016.
06.012.
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