Bioresource Technology 128 (2013) 305309

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Bioresource Technology
journal homepage: www.elsevier.com/locate/biortech

Effect of calcination temperature on the activity of solid Ca/Al composite

oxide-based alkaline catalyst for biodiesel production
Yong-Lu Meng a,b, Bo-Yang Wang a,c, Shu-Fen Li a,, Song-Jiang Tian a, Min-Hua Zhang b,
a

Key Laboratory for Green Chemical Technology of State Education Ministry, School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, China
Key Laboratory for Green Chemical Technology of State Education Ministry, Tianjin University, R&D Center for Petrochemical Technology, Tianjin 300072, China
c
College of Pharmacy and Tianjin Key Laboratory of Molecular Drug Research, Nankai University, Tianjin 300071, China
b

h i g h l i g h t s

g r a p h i c a l a b s t r a c t

" A solid base catalyst based on

The Ca/Al composite oxide which contains Ca12Al14O33 and CaO was prepared successfully by a simple
method and used as an environmentally benign solid catalyst in the transesterication of rapeseed oil
with methanol. The effect of the calcination temperature ranging from 120 C to 1000 C on the catalytic
activity was investigated. The catalyst calcined at 600 C showed the highest activity with >94% yield of
biodiesel. The activity of the catalyst was closely related to its specic surface area and crystalline structure. In particular, the generation of crystalline Ca12Al14O33 vastly improved the catalytic activity due to
the synergistic effect between Ca12Al14O33 and CaO.

"

"

"
"

Ca12Al14O33 and CaO was developed.

The catalyst showed excellent
catalytic activity with biodiesel
yields >94%.
The effect of calcination temperature
on the catalytic activity was
investigated and optimal
temperature was determined.
Structure and properties of the
catalyst were studied.
The synergistic mechanism between
crystalline Ca12Al14O33 and CaO of
the catalyst was revealed.

a r t i c l e

i n f o

Article history:
Received 31 May 2012
Received in revised form 17 October 2012
Accepted 29 October 2012
Available online 7 November 2012
Keywords:
Biodiesel
Methyl ester
Transesterication
Heterogeneous catalyst
Ca/Al composite oxide

a b s t r a c t
A solid Ca/Al composite oxide-based alkaline catalyst containing Ca12Al14O33 and CaO was prepared by
chemical synthesis and thermal activation from sodium aluminate solution and calcium hydroxide emulsion. The effect of calcination temperatures ranging from 120 C to 1000 C on activity of the catalyst was
investigated. The catalyst calcined at 600 C showed the highest activity with >94% yield of fatty acid
methyl esters (i.e. biodiesel) when applied to the transesterication of rapeseed oil at a methanol:oil
molar ratio of 15:1 at 65 C for 3 h. Structure and properties of the catalyst were studied and the characterizations with XRD, TGA, FTIR, BET, and SEM demonstrated that the performance of the catalyst was
closely related to its specic surface area and crystalline structure. In particular, the generation of crystalline Ca12Al14O33 improved the catalytic activity due its synergistic effect with CaO.
2012 Elsevier Ltd. All rights reserved.

Corresponding authors. Tel./fax: +86 22 87894252.

E-mail address: shi@tju.edu.cn (S.-F. Li).
0960-8524/$ - see front matter 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.biortech.2012.10.152

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Y.-L. Meng et al. / Bioresource Technology 128 (2013) 305309

1. Introduction
Biodiesel is commonly produced by the transesterication of
triglycerides with methanol using homogeneous alkaline catalysts
such as NaOH and KOH (Ma and Hanna, 1999; Pinto et al., 2005;
Lotero et al., 2005.); however, production costs are rather high as
not only a number of washing and purication steps need to be
performed to meet quality requirements but also due to the equipment corrosion caused by acid and alkaline conditions (Canakci,
2007; Granados et al., 2007; Ji et al., 2006; Karmee and Chadha,
2005). Although homogeneous base processes are relatively fast
and show high conversions (Semwal et al., 2011), the generation
of wastewater is an environmental concern and it is difcult to remove the catalysts from the reaction mixture.
As heterogeneously catalyzed processes generally do not generate large amounts of wastewater and are easy to separate from
reaction mixtures, they could prove more environmentally friendly
than homogeneous catalysts (Semwal et al., 2011; Martino et al.,
2008). Particularly, solid base catalysts can allow the production
of high quality glycerol as by-production (Bournay et al., 2005).
Metal oxides (Yan et al., 2010; Furutaa et al., 2006), zeolites
(Brito et al., 2007), and hydrotalcites (Cantrella et al., 2005;
Trakarnpruk and Porntangjitlikit 2008) have been explored as heterogeneous catalysts for triglyceride transesterication. CaO has
also been investigated and was found to exhibit high activity. For
example, Kawashima et al. (2008) found that with calcium oxide
as catalyst a 90% of biodiesel yield could be achieved in the transesterication of rapeseed oil with reuxing methanol within 3 h.
Reddy et al. (2006) reported that nanocrystalline CaO showed high
catalytic activity (99% conversion) in the transesterication reaction of poultry fat and soybean oil at room temperature. Some
research has shown that soluble substance leached from CaO during
transesterication. Gryglewicz (1999) reported that CaO dissolved
slightly in methanol and formed a suspension in the reaction
mixture. The separation of CaO from biodiesel after the reaction
is very difcult due to gel formation in the lower glycerol layer
(Guo et al., 2007; Jiang et al., 2006; Yan et al., 2007). Therefore, it
is critical to develop a solid catalyst that not only possesses exceptional catalytic activity and high stability, but is also easily separable from the biodiesel product.
Wang et al., 2012 synthesized a solid Ca/Al composite oxidebased catalyst for transesterication of rapeseed oil with methanol
and showed that the catalyst calcined by 1000 C reused for at least
seven cycles with yields of the FAME maintained above 87%. The
catalyst was easily separated from the reaction mixture, as it is
insoluble in methanol and methyl esters. The present study focuses
on the effect of calcination temperature on the catalytic activity
and structure of this catalyst and compares its performance with
that of NaOH and CaO.

2. Methods

Table 1
Physical and chemical properties of the rapeseed oil.
Property

Unit

Value

Palmitic acid
Stearic acid
Oleic acid
Linoleic acid
Linolenic acid
Erucic acid
Saponication value
Acid value
Water content

wt.%
wt.%
wt.%
wt.%
wt.%
wt.%
mg KOH/g
mg KOH/g
wt.%

12
4
16
20
5
43
190.98
0.12
0.12

2.2. Catalyst preparation

An aqueous solution of sodium aluminate (NaAlO2) was prepared with 6 g of aluminum foil and 45 mL of 5 mol/mL NaOH. A
Ca(OH)2 emulsion was prepared by 7 g of calcium oxide (CaO), prepared by calcination of CaCO3, in 50 mL of distilled water. The
NaAlO2 solution and the Ca(OH)2 emulsion were mixed at a Ca:Al
molar ratio of 3:2 under 300 r/min stirring rate for 3 h at 80 C.
After the mixture was cooled to room temperature, the solid precipitate was collected through an air pump ltration. The solid
material was washed with deionized water until the pH of the
washwater was about 78. The solid was dried under airow at
120 C, followed by calcination in a mufe furnace at temperature
ranging from 400 C to 1000 C for 8 h.
2.3. Catalyst characterization
Powder X-ray diffraction (XRD) patterns of the samples were recorded on a PANAlytical XPert diffractometer using CuKa radiation (40 kV and 100 mA). The diffractograms were recorded in
the 2h ranges of 10110 with a 2 h step size of 0.02. The phases
present in the samples were identied according to the Powder
Diffraction (PDF) database (JCPDS-International Centre for Diffraction Data (ICDD), 2000).
The specic surface area of Ca/Al composite oxides catalysts
was determined by N2 adsorption at 77 K using a Micrometrics Tristar 3000 automated system. Prior to analyses, the catalysts samples were degassed at 473 K and 106 mmHg for 5 h. Specic
surface areas were calculated using the BrunauerEmmettTeller
(BET) model.
Fourier transform infrared (FTIR) spectroscopy was done on a
Nicolet 560 spectrophotometer. The FTIR spectroscopy measurements were performed by mixing samples into KBr pellets (32
scans with 5 cm1 resolution) in the range of 4000400 cm1.
Thermogravimetry differential thermal analysis (TG-DTA) was
recorded using a HCT-2 analyzer. The dried samples (prior to calcination) were heated to 1173 K from at a heating rate of 5 K min1
in an air stream.
Scanning electron microscopy (SEM) was carried out using a
XL30 SEM (Philips, Eindhoven, North Brabant, Netherlands). The
samples were coated with gold using a sputter coater.

2.1. Materials
2.4. Experimental procedures
Rapeseed oil was purchased from Xingwang Oil Corporation
(Guanghan, Sichuan, China) and its physical and chemical properties are listed in Table 1. Standard analytical reagents, such as
methyl undecanoate, methyl palmitate, methyl oleate, methyl
stearate, methyl linoleate, and methyl linolenate were purchased
from Sigma Chemical Corporation, USA. Calcium carbonate and
aluminum foil were of guarantee reagent grade (GR) and sodium
hydroxide and other chemicals were of analytical grade (AR), and
were obtained from Kewei Reagent Corporation, Tianjin, China.

Transesterication reactions were carried out in a 150 mL fourneck glass ask equipped with a stirrer, a reux methanol condenser, and an electric jacket with a thermocouple. Firstly, 45 g
of rapeseed oil and 24.5 g of methanol (molar ratio of 15:1) were
placed into the reactor, and catalyst at 6 wt.% of the rapeseed oil
was added. The reaction was carried out under a stirring rate of
270 r/min at 65 C for 3 h. The catalyst was removed from the mixture by ltration through an air pump ltration, and washed by

Y.-L. Meng et al. / Bioresource Technology 128 (2013) 305309

307

methanol. The catalyst was dried and stored in a desiccator. The ltrate was subjected to batch distillation to evaporate the excess
methanol. A standing and layering process was carried out to obtain the FAME (the lower layer) and glycerol.
2.5. Product analysis
The fatty acid methyl esters (FAME) content was determined
with a SP-2100 gas chromatograph equipped with a ame ionization detector and a H.J PEG-20 M capillary column with a lm
thickness of 0.5 lm, L  I.D. 30 m  0.32 mm. Nitrogen was used
as carrier gas, hydrogen and air were used as combustion gas.
Methyl salicylate was used as internal standard and ethyl acetate
was the solvent.
The yield of the FAME (i.e. biodiesel) was calculated by the following equation:

Yield mmactual  100%

academic

mproduct W FAMEs
moil

mproduct W FAMEs
moil
M FAMEs 3
Moil

 882:18
 100% 1:0046 
878:15

 100%

mproduct W FAMEs
moil

 100%

where WFAME is the mass concentration of methyl esters in the products, and was determined by GC. mproduct is the mass of the biodiesel
obtained by separation. moil is the mass of rapeseed oil used in the
reaction. Moil is the average mole mass of triglycerides in oils, where
its value is 882.18 g/mol determined from the acid and saponication values. MFAMEs is the average values of the mole mass of FAME
in the product, based on the stoichiometric proportion of the
transesterication, MFAMEs Moil  4MH 878:15 g=mol.
3. Results and discussion
3.1. Catalyst characterization
3.1.1. Structure of the Ca/Al composite oxide catalyst
Fig. 1 depicts the XRD patterns of the samples after thermoactivation at 120, 400, 600, 800, and 1000 C, respectively. The results
indicated that cubic calcium aluminum hydroxide (Ca3(Al(OH)6)2,
JCPDS 781532, 2h diffraction peaks at 20.069, 23.214, 30.871,
33.062, 37.098, 45.861, 52.016, and 64.324) was formed from
calcium hydroxide and sodium aluminate. When the calcination
temperature reached 400 C, the crystal structure of Ca12Al14O33
(JCPDS 702144, 2h diffraction peaks at 21.061, 34.728,
38.983, 42.879, and 48.241) emerged. Its diffraction peak intensity increased with the calcination temperature. The crystal phase
of Ca3(Al(OH)6)2 vanished at 400 C. This ndings indicated that
Ca3(Al(OH)6)2 was converted into amorphous Ca12Al14O33 and then
crystallized gradually under higher temperature. Due to the stoichiometric proportion of the decomposition reaction of Ca3
(Al(OH)6)2, 9 mol Ca(OH)2 (2h = 21.010, 39.814, 55.341, and
59.746) generates with 1 mol Ca12Al14O33 (Soro et al., 2006). A further increase in the calcination temperature above 600 C led to
the formation of CaO species with characteristic 2h diffraction
peaks at 37.597, 63.689, 63.500, 59.746, 76.201, and 80.253,
where CaO was transformed from Ca(OH)2 by dehydration. Consequently, the catalysts were composed of Ca12Al14O33 and CaO at
higher calcination temperatures (600800 C).
Thermogravimetric analysis of the uncalcined Ca/Al precursor
in air showed two noticeable weight losses of 17.5% and 7.92%
(Fig. 2). The main weight loss at 310 C resulted from loss of
water due to the thermo-decomposition of Ca3(Al(OH)6)2, while
the loss at about 455 C is assigned to the dehydration of Ca(OH)2.
These results are in agreement with those reported by Ukrainczyk
et al. (2007). The thermal transitions below 200 C was assigned to
the removal of adsorbed and chemisorbed water and the transition
at 615900 C probably corresponded to the decomposition of

Fig. 1. Powder X-ray diffraction patterns of the Ca/Al composite oxide catalysts
after calcination at different temperatures.

Fig. 2. Thermogravimetry differential thermal analysis curves of the Ca/Al composite oxide catalyst precursor.

CaCO3 formed by CaO with CO2 in the atmosphere. These observations are consistent with these from the powder XRD experiments
as structure transformations between 120400 C and 400600 C
were noted.
310 C

7Ca3 AlOH6 2 ! Ca12 Al14 O33 9CaOH2 33H2 O

455 C

CaOH2 ! CaO H2 O
FTIR spectroscopy was used to identify the structural changes of
the catalysts at molecular level during calcinating. The spectra
(Fig. 3) exhibit a broad band near 3400 cm1 due to the c (OH)
of the free and hydrogen-bonded hydroxyl groups, and another

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Y.-L. Meng et al. / Bioresource Technology 128 (2013) 305309

Fig. 3. Fourier transform infrared spectroscopy patterns of the Ca/Al composite

oxide catalysts calcined at different temperatures.

typical absorption peak at 1630 cm1 is assigned to the deformative vibration of water molecules, absorbed during compaction of
the dry powder specimens with KBr (Zawrah, 2004; Dvoranova
et al., 2002). The spectra of all the samples showed the same peak
at 1448 cm1, which is assigned to AlO stretching vibration (Chroma
et al., 2005), and the shape of these peaks became sharper with
higher calcination temperature. The broad absorption region from
750 to 930 cm1 can be assigned to AlO4 stretching vibration
(Ouahdi et al., 2005). The two sharp bands at 560 and 678 cm1
correspond to the AlO6 groups. (Ouahdi et al., 2005).
3.1.2. Surface property and topography of the Ca/Al composite oxide
catalyst
The catalyst exhibited ball-shaped particles surrounded by a
aky lm after calcination. Due to the irregular accumulation of
the aky lm, numerous large-sized pores were formed. At a calcination temperature above 600 C, agglomeration of the catalyst
particles occurred and became very pronounced at 1000 C because of high sintering.
The specic surface areas of the catalysts after calcination at 120,
400, 600, 800, and 1000 C was 2.33, 5.14, 27.36, 9.8, and 3.27 m2/g,
respectively. The increase from 5.14 m2/g to 27.36 m2/g between
calcination at 400 C and 600 C may be attributed to the loss of
structural water caused by crystalline phase transformation
(Behrens, 2009). Overall, the changes in catalyst specic surface
area with the calcination temperature were determined by the
changes in phase structure, particle size and surface morphology.
3.2. Effect of calcination temperature on catalytic activity
The catalytic activity of the Ca/Al composite oxide was compared with CaO and NaOH under the same condition that methanol:rapeseed oil molar ratio of 15:1 at 65 C for 3 h with the
catalyst dosage 6 wt.%. The results are shown in Fig. 4(a), where
the values show the average FAME yields of parallel experiment,
and the bars donate standard deviation. It indicates that the catalytic activities signicantly depended on the calcination temperature, and the optimum calcination temperature was 600 C. The
trend in calcination temperature-dependent activity parallels that

Fig. 4. Catalytic activity of different catalysts in transesterication of rapeseed oil

with methanol to produce biodiesel. (a) FAME yields achieved with Ca/Al composite
oxide catalysts calcined at different temperature; (b) FAME yields achieved with
various catalysts. (The CaO catalyst was prepared by Ca(OH)2 calcination at 800 C
and the Ca/Al composite oxide catalyst was calcined at 600 C.)

of the surface area. The increase in FAME yield of the catalyst calcined from 120 C to 400 C is possibly attributable to the development of the Ca12Al14O33 phase.
3.3. Transesterication with different catalysts
NaOH had the highest catalytic activity with a FAME yield about
96% (Fig. 4b). The Ca/Al composite oxide- and CaO-catalyzed reactions produced yields of 94.34% and 92.59%, respectively. It is possible that Ca12Al14O33 and CaO act synergistically. Since the Ca/Al
oxide composite is easier to separate from the reaction mixture
and apparently stable, it could be a better choice from an environmental and potentially also an economic point of view than NaOH
and CaO for industrial-scale biodiesel production.
4. Conclusions
A convenient and economic method for preparation of a Ca/Al
composite oxide heterogeneous catalyst for biodiesel production
was developed. The catalyst calcined at 600 C which was
composed of Ca12Al14O33 and CaO showed the highest activity with

Y.-L. Meng et al. / Bioresource Technology 128 (2013) 305309

the FAME yield >94%. There was a positive correlation between the
performance and the BET surface area of the catalysts calcined at
different temperature. The Ca/Al composite oxide has a great potential for developing green industrial-scaled biodiesel production.
Acknowledgements
The project is nancially supported by the National Natural Science Foundation of China (No.20776107 and No.21104035).
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