Fuel 98 (2012) 194–202

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Fuel
journal homepage: www.elsevier.com/locate/fuel

Biodiesel production based on heterogeneous process catalyzed

by solid waste coral fragment
Wuttichai Roschat a, Mattana Kacha a, Boonyawan Yoosuk b, Taweesak Sudyoadsuk a, Vinich Promarak a,⇑
a
Center for Organic Electronic and Alternative Energy (COEA), Department of Chemistry and Center for Innovation in Chemistry, Faculty of Science, Ubon Ratchathani University,
Warinchumrap, Ubon Ratchathani 34190, Thailand
b
National Metal and Materials Technology Center (MTEC), 114 Thailand Science Park, Phahonyothin Road, Klong 1, Klong Luang, Pathumthani 12120, Thailand

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

Article history: We present an environmentally friendly, efficient, simple heterogeneous transesterification process com-
Received 7 November 2011 bining palm oil, soybean oil, rice bran oil, and waste cooking oil with methanol to make a biodiesel and
Received in revised form 8 April 2012 glycerol by-product using calcined waste coral fragments in solid form as a catalyst. Under optimum
Accepted 9 April 2012
reaction conditions, the coral fragments calcined at 700 °C for 1 h; catalyst/oil ratio of 100 wt.%; metha-
Available online 22 April 2012
nol/oil molar ratio of 15:1; reaction temperature of 65 °C with a constant stirring are able to transesterify
oils to a biodiesel product with a FAME yield over 98% in 2 h. The catalyst can be easily separated from the
Keywords:
reaction mixture by pouring off the reaction solution and can be reused several times with consistent
Biodiesel
Glycerol
results. Biodiesel and glycerol products without any treatment and cleansing show a high quality product
Heterogeneous process in which fuel properties of the biodiesel meet all EN 14214 standards for bio-auto fuels.
Solid catalyst Ó 2012 Elsevier Ltd. All rights reserved.
Coral fragment

1. Introduction removal of these catalysts is costly, time consuming and generates

Since the potential shortages and rise of petroleum prices, and
ever-increasing environmental concerns, a search for alternative
renewable fuels has drawn numerous intentions [1]. Biodiesel, a
clean renewable fuel derived from biological sources, is a promis-
ing candidate for a diesel fuel substitute because it can be used
in any diesel-engine vehicle without the need for modification
and produces fewer amounts of polluting emissions. Biodiesel is
chemically a fatty acid methyl ester (FAME) and can be produced
from a direct transesterification of vegetable oils or animal fat,
where the corresponding triglycerides react with methyl alcohol
in the presence of a catalyst forming glycerol as a by-product
[2,3]. Nowadays, the costs of the triglyceride starting material
and production process represent the majority of the price of bio-
diesel. The high triglyceride quality is always in demand with food
producers. Therefore, the utilization of the glycerol by-product of
biodiesel production would significantly improve the economic as-
pect of overall biodiesel production. Glycerol is one of the most
versatile and valuable known chemicals and has a wide variety
of uses and applications such as food, pharmaceutical, and cos-
metic, coating and other industries. Currently, homogeneous
process catalyzed by sodium or potassium hydroxide is a common
and efficient method for biodiesel production [4] though the
⇑ Corresponding author. Tel.: +66 4535 3400x4510; fax: +66 4535 3422x4510.
E-mail addresses: pvinich@ubu.ac.th, pvinich@gmail.com (V. Promarak).
large amounts of waste water. In addition, crude glycerol by-prod-
ucts have very low value due to high impurities such as other cat-
alysts, soap, methanol and water. Purifying the crude glycerol by
means of filtration, chemical additions, fractional vacuum distilla-
tion, bleaching, deodoring, and ion exchange yields various com-
mercial and technical grades, however, it is costly, especially for
medium and small biodiesel producers.
Therefore, there is a need for a milder, environmentally friendly
and integrated process producing cost-efficient biodiesel and high-
quality glycerol. The use of a heterogeneous catalyst [5] is a key
technology to overcome such problems. The low end of pipe costs,
energy savings, high efficiency, and selectivity are especially strong
driving forces behind the development of new green and sustain-
able technologies. Heterogeneous catalysts offer significant advan-
tages of simple isolation from the reaction, requiring no cleansing
with water, very little environmental pollution, and the possibility
to be reused and recycled. Many of them have been investigated
including metal oxides [6], calcined hydrotalcites [7], zeolites [8],
and anion exchanged resins [9]. However, good yields of biodiesel
in mild condition are achieved mainly by the catalysts in powder
form [10]. Moreover, the scaling up of this process to an industrial
system with fixed based reactors would be impossible due to the
high pressure drop occurring along the reactor, and removal of a
powder catalyst from biodiesel is also extremely difficult with
batch reactor. Therefore, in order to develop a heterogeneous cat-
alyst with practical industrial applications, it is necessary to search

0016-2361/$ - see front matter Ó 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.fuel.2012.04.009
 W. Roschat et al. / Fuel 98 (2012) 194–202
for a catalyst with high activity in particle, pellet or bulk solid form.
To date, there is a rare report on high conversion of biodiesel pro-
duction using bulk solids as catalyst [11,12].
Among the metal oxides, calcium oxide (CaO) is one of the sol-
ids that have shown high transesterification activity in mild reac-
tion condition with high stability, non-toxic and low cost [13,14].
CaO is generally prepared from calcium carbonate (CaCO3) or cal-
cium hydroxide (Ca(OH)2) as raw materials. Moreover, using natu-
ral calcium sources as raw materials for generating CaO could
eliminate the wastes and at the same time produce a catalyst with
high cost effectiveness [15]. CaO powder prepared from several
natural calcium wastes has been used in transesterification of oils
excluding coral [15–18]. Waste coral fragments are a natural cal-
cium source and is a highly porous material. The use of CaO derived
from a coral fragment in a bulk solid form could be an effective
way for practical, low cost industrial biodiesel production. Herein,
we present an environmentally friendly, efficient, simple transe-
sterification process using calcined waste coral fragments as a bulk
solid catalyst. Several parameters are investigated including calci-
nation time of the catalyst, catalyst/oil ratio, methanol/oil molar
ratio, type of oil and FAA quantity, and reuse and recycle of the cat-
alyst. The fuel properties of the biodiesel and purity of glycerol are
evaluated using standard methods.
2. Experimental
2.1. Materials and catalyst preparation
Waste coral fragments collected from Andaman Sea in Krabi
province, Thailand, were cut into small pieces (0.5–1.0 cm3)
(Fig. 1A), cleaned with water several times and air-dried for 24 h.
The coral fragment catalyst was then prepared by calcination at
700 °C in air (refer to TG/DTA results) with calcination times of
0.5, 1.0 and 1.5 h. Palm oil (FFA of 0.28 mg KOH g1), soybean oil
(FFA of 0.18 mg KOH g1), rice bran oil (FFA of 0.1 mg KOH g1)
and waste cooking oil (FFA of 1.15 mg KOH g1) were obtained
from commercial sources in Thai market. FFAs (free fatty acids)
content of oil was determined by reported method [19]. The ana-
lytical grade methanol purchased from Fluka was used in this
work. Hammett indicators such as phenolphthalein, thymolphtha-
lein, indigo carmine, 2,4-dinitroaniline, and 4-nitroaniline of AR
grade were obtained from Aldrich and Fluka. DowexÒ 50WX8
ion-exchange resin was obtained from Acros.
2.2. Material characterization
Themogravimetric analysis (TG) was carried out on a Rigaku TG-
DTA 8120 thermal analyzer under air flow condition with a temper-
ature ramp rate of 10 °C/min. X-ray diffraction (XRD) was analyzed
by a PHILIPS X’Pert-MDP X-ray diffractometer using Cu Ka radiation
(k = 1.5418 Å) at 1400 W, 40 kV and 35 mA in the scanning angle
(2h) of 20–80° with resolution of 0.04° at counting step of 1 s/step.
X-ray fluorescence was determined by a PHILIPS MagiX wavelength
dispersive X-ray Fluorescence (XRF) spectrophotometer with 1 kW
Rh Ka radiation. Fourier transforms infrared (FTIR) spectra were
measured on a Perkin–Elmer FTIR spectroscopy spectrum RXI spec-
trometer in the range of 400–4000 cm1 with resolution of 4 cm1.
Potassium bromide (KBr) was used as a matrix. 1H nuclear magnetic
resonance (1H NMR) spectra were recorded on a Brüker AVANCE
300 MHz spectrometer with tetramethylsilane (TMS) as the internal
reference using CDCl3 as a solvent in all cases.
Pore volume of the catalyst was measured by water adsorption
method [20]. Typically, calcined coral fragment preheated in an
oven at 110 °C for 24 h with accurate weight (0.6–0.8 g) was boiled
in distilled water (100 ml) in a 250 ml beaker for 2 h. The beaker
195
was kept at room temperature for 24 h to attain a maximum water
adsorption. The coral fragment was carefully removed from water
and weighted. The amount adsorbed water was calculated from a
weight difference, which was then converted to a total pore vol-
ume (cm3 g1). The triplicate experiments were performed.
The Hammett indicators used were phenolphthalein (pKa = 9.3),
thymolphthalein (pKa = 9.9), indigo carmine (pKa = 12.2), 2,4-dini-
troaniline (pKa = 15) and 4-nitroaniline (pKa = 18.4). Typically, 1–2
pieces of the catalyst were mixed with 5 mL of a solution of Ham-
mett indicators in methanol and allowed to sit for at least 10 min.
After the equilibration, the color of the catalyst was noted. The ba-
sic strength of the catalyst was taken to be higher than the weakest
indicator that underwent a color change and lower than the stron-
gest indicator that underwent no color change.
2.3. Transesterification procedure
The transesterification was carried out in a batch reactor. A mix-
ture of methanol and catalyst at a designated amount in a 250 ml
2-neck round bottom flask equipped with a reflux condenser was
heated at 65 °C for 2 h, and then a preheated 50 ml of oil was
added. The reaction mixture was heated for the required reaction
times without stir unless mentioned. To follow the reaction pro-
gress, the solution mixture of 0.5 ml was sampled, and then exces-
sive amount of methanol was evaporated in an oven before
analysis of biodiesel yield. The conversion of the oil to methyl es-
ters was determined in term of %FAME as a function of time by nu-
clear magnetic resonance (NMR). The biodiesel yield was
calculated from the ratio of the integrations of the 1H NMR signals
of the methoxy protons (CH3OA) in the methyl ester at chemical
shifts of 3.68 ppm (singlet peak) and methylene protons (ACH2A)
of all triglycerides at chemical shifts of 2.30 ppm (triplet peak),
according to the following equation [21]:
 
2ACH3
%FAME ¼  100
3ACH2
ACH3 is the integration value of the methoxy protons and ACH2 is the
integration value of the methylene protons. The factors 3 and 2 de-
rive from the number of attached protons at the methoxy and
methylene carbons, respectively.
It should be noted that the triplicate experiments were per-
formed, and the errors of %FAME contents were typically within
±0.5 %. After completion of the reaction, the solution mixture
was simply separated from a catalytic solid by pouring off from
the reaction vessel. The liquid product obtained was heated in an
oven (60–70 °C) or rotary evaporated to remove the excess meth-
anol, and then settled in a separating funnel. The upper phase con-
sisted of biodiesel product (FAME) and the lower phase contained
the glycerol by-product. Biodiesel was filtered through a cotton
wool filter and corrected without any treatment and cleaning
processes.
In order to examine the potential reutilization of the catalyst,
reuse and recycling of used catalyst was tested to check its capacity
to provide the same catalytic activity. For reuse experiment, the so-
lid catalyst recovered by filtration was directly used as the catalyst
for the repeated reactions. The repeated reactions were run under
the same reaction conditions to the last reaction. For recycling
experiments, deactivated catalyst was regenerated by washing
with acetone to remove all remaining reactants, drying at 110 °C
in an oven and calcining at 700 °C for 1 h. Furthermore, the leach-
ing of the catalyst was also tested by removing the solid catalysts
from the reaction solution after reaction time of 2 h, and then the
reaction (a remained liquid mixture) was allowed to progress un-
der the same conditions.
196 W. Roschat et al. / Fuel 98 (2012) 194–202

(B) -6
(A) 100

90
-4

Weight %
80

DTA (µg/s)
70
-2

Uncalcined Calcined 60
coral fragment coral fragment

50 0

100 200 300 400 500 600 700 800

o
Temperature ( C)
(C)
(D)
Calcined coral
Calcined coral, 1.5 h 523 Ca-O

Calcined coral, 1.0 h Uncalcined coral

Transmission (a.u.)
Intensity (a.u.)

Calcined coral, 0.5 h

Ca(OH)2

Uncalcined coral
3637 O-H

Ca(OH)2 529 Ca-O

CaO

CaO
CaCO3
calcite CaCO3 (calcite) 2920 C=O 1787 C=O
2519 C=O 1480 C=O 713 C=O
856 C=O
20 30 40 50 60 70 80 4000 3500 3000 2500 2000 1500 1000 500
2 Theta (degree) Wavenumber (cm-1)

Fig. 1. (A) Pictures of uncalcined and calcined coral fragments. (B) TG/DTA thermograms of coral fragments. (C) Powder XRD patterns and (D) IR spectra of CaCO3, CaO,
Ca(OH)2 and coral fragments calcined at 700 °C in open air with calcination times of 0 (pristine), 0.5, 1.0 and 1.5 h.

To determine the acceptability of this biodiesel product, it was
tested for standard fuel properties, which are methyl ester content,
viscosity, flash point, acid number, density, water content, total
contamination and copper strip corrosion, by the American Society
for Testing and Material (ASTM) methods. Purity of glycerol by-
product was analyzed according to the International Standards
Organizing (ISO) and British Standards Institution (BS) methods.
Analysis of leaching calcium ion from the catalyst in the obtained
biodiesel and glycerol was performed by the atomic absorption
spectrophotometric (AAS) method according to the report proce-
dure [22].
Removal of the soluble calcium ion in the obtained biodiesel
was performed using commercially available cation-exchange res-
ins. The resin was repeatedly immersed in methanol to remove
moisture, and then was packed into a chromatography column.
The oil was funneled into the column at room temperature.
3. Results and discussion
3.1. Catalyst preparation and characterization
TG/DTA analysis of the coral fragment revealed a 44% weight
loss at temperatures between 600–740 °C, where carbon dioxide
(CO2) was removed from calcium carbonate (CaCO3) to give CaO
(Fig. 1B). Therefore, high temperature above 600 °C was required
to transform CaCO3 (pristine coral) to CaO (catalytic coral). From
the view point of preparation time and energy consumption, the
temperature of 700 °C was selected as a suitable condition to gen-
erate the catalyst while the calcination time was varied. The coral
fragments, after being calcined at 700 °C for 0.5, 1.0, and 1.5 h,
showed porous structure like the uncalcined (pristine) sample
(Fig. 1A). A high porosity catalyst is a key requirement to achieve
high conversion efficiency for heterogeneous process, thereby high
surface areas or high catalytic sites are necessary. As this catalyst
was a microporous material, its surface area was determined as
the total pore volume by water adsorption method, which was
0.172 ± 0.012 cm3 g1. As illustrated in Fig. 1C, XRD patterns of
all the calcined coral fragments were identical, and displayed clear
and sharp peaks agreeing to a single crystalline phase of CaO. Tiny
XRD peaks identical to incompletely calcined CaCO3 were detected
in the sample with short calcination time of 30 min. Weak XRD
peaks matching to Ca(OH)2 patterns were observed in all calcined
samples, which might arise from a hydration of CaO by moisture
during storage of the samples. This phenomenon has been ob-
served in other forms of CaO and it is intense in case of powder
CaO [23]. It should be noted that the activated CaO was rapidly hy-
drated, and hence in order to prevent deterioration of the catalyst
reaction must be taken with extreme care to avoid any contact of
the CaO with room air. The diffraction pattern of the uncalcined
sample showed sharp peaks agreeing to calcite CaCO3. Its IR
spectrum also showed absorption bands of the CO2 3 group which
were identical to those of the CaCO3 (Fig. 1D). The IR spectra of cal-
cined samples revealed an absorption band corresponding to the
 W. Roschat et al. / Fuel 98 (2012) 194–202
stretching mode of the CaO at 523 cm1 with no absorption bands
of CO23 group being observed. These results indicated that all
CaCO3 in the samples (calcined for 1 and 1.5 h) was completely
transformed to CaO, which can be hydrolyzed by moisture to
Ca(OH)2 by a prolonged exposure to open air. Elemental composi-
tion analysis of all calcined samples with XRF spectroscopy indi-
cated that they were composed of mainly CaO 91.9 wt.%, SiO2
2.0 wt.%, SO3 0.6 wt.%, SrO 1.9 wt.% and other oxides 3.6 wt.%.
The strengths of the basic sites of all calcined coral fragments mea-
sured by the Hammett indicator method were found to possess H_
values in the range of 13.0–15.0, as evidenced by their ability to ef-
fect a color change with 2,4-dinitroaniline (pKa = 15), while the H_
value of uncalcined coral fragment was less than 8.0–10.0, as no
color change was observed with phenolphthalein (pKa = 9.3).
3.2. Catalyst properties in transesterification
In heterogeneous transesterification of oil (mixed triglyceride)
with methanol catalyzed by CaO, such triglyceride was transesteri-
fied to di- and mono-glycerides, subsequently to FAME (biodiesel).
The basic site of the CaO catalyst is generally known to be active spe-
cies in catalytic process and the amount of the basic sites should de-
pend on the surface area. During the reaction, the calcium
methoxide species, Ca(OCH3)2, was reported to form on the surface
of the CaO catalyst, and enhanced the transesterification reaction
between triglyceride and methanol. Due to the high surface area
of powder CaO catalyst, around 3–10 wt.% of the catalyst is gener-
ally required for a complete transesterification of oil. In our case,
the CaO catalyst is in bulk solid form (size of 0.5–1.0 cm3) having
a surface area significantly lower than that of the powder, thus high-
er catalyst loading is required. As the loading amount of the catalyst
was increased from 70 wt.% to 100 wt.%, the reaction time required
to complete a transformation of all triglycerides to biodiesel with
FAME exceeding 96% decreased (Fig. 2). The reaction with
100 wt.% of the catalyst reached a completion in 4 h. The result
was basically related to the amount of the catalytic surface area.
However, when the loading amount of the catalyst was higher than
100 wt.%, the reaction time required to complete a reaction in-
creased. It was noticed that from this point the amount of the cata-
lyst exceeded the amount oil and methanol. This might lead to the
reactants (methanol vapor) trapped inside micropores of the cata-
lyst resulting in a decrease in the amount of methanol available
for the reaction, thereby lower conversion efficiency. Therefore,
100
80
60
%FAME
Amount of the catalyst
40
(wt% catalyst/oil)
70%
80%
20 100%
130%
150%
0 0
0 4 8 12 16 20 24
Time (h)
Fig. 2. Effects of loading amount of the catalyst on the %FAME: palm oil, catalyst
(calcined at 700 °C for 1 h); methanol/oil molar ratio (15:1); reaction temperature
(65 °C) without stir.
197
the optimum load of the catalyst in the present study is 100 wt.%
(50 g of the catalyst to 50 g of oil).
From the view point of preparation time and energy consump-
tion, the catalyst calcined for 30 min was employed. The result re-
vealed a clear decline in catalytic activity and the reaction was
completed (FAME >95%) in a longer time of 7 h compared with
the catalyst calcined for 1 h (Fig. 3). This might be because the
sample calcined at 700 °C for 30 min has a lower amount of cata-
lytic CaO as mentioned earlier. Moreover, this could be clearly seen
from the reaction catalyzed by uncalcined catalyst, showing little
to no catalytic activity for transesterification. Accordingly, the
reaction using catalyst calcined 700 °C for 1.5 h was performed
with an expectation of improvement in catalytic activity and reac-
tion time due to the CaO catalyst should be completely formed.
Unfortunately, a slight decline of the catalyst activity was observed
and FAME exceeding 95% was reached in 5 h. This would be due to
a prolonged calcination process which brought about the sintering
of the catalyst and thus the lowering of the surface area. The
shrinkage of the catalyst grains would eventually suppress the ac-
tive sites. Therefore, the optimum calcination condition in the
present study is at temperature of 700 °C for 1 h. However, the
higher temperature is not preferable due to the severe sintering
rate and the high energy consumption.
The influence of the reaction conditions on the transesterifica-
tion of palm oil, such as methanol/oil molar ratio and stirring the
reaction, was investigated. The methanol/oil ratio is one of the
most important factors affecting the yield of biodiesel. Although
stoichiometric ratio requires three moles of methanol for each
mole of oil, the transesterification is commonly carried out with
an extra amount of methanol in order to shift the equilibrium to-
wards the direction of methyl ester formation. According to Centi-
kaya et al., for example, transesterification was insufficient at the
molar ratios of methanol/oils below 5:1 [24]. Additionally, the
methanol/oil ratio is associated with operating parameters such
as the type of catalyst used and the quality of oils. The effect of
methanol/oil molar ratio on the transesterification was investi-
gated and found that the reaction advanced faster by increasing
the methanol/oil molar ratio from 12:1 to 15:1 (Fig. 4). In fact
the higher amount of methanol shifted the reaction equilibrium
to the forward direction by promoting the formation of methoxide
species on CaO surface. However, further increase in methanol/oil
molar ratio up to 18:1 and 21:1 did not promote the reaction. It
was considered that the glycerol would largely dissolve in exces-
sive methanol and subsequently inhibited the reaction of methanol
100
80
60
%FAME
Calcination time
1.5 h
1.0 h
40 0.5 h
0 h (Uncalcined)
20
0 4 8 12 16 20 24
Time (h)
Fig. 3. Effects of calcination time on the %FAME: catalyst (100 wt.%, calcined at
700 °C); methanol/oil molar ratio (15:1); reaction temperature (65 °C) without stir.
198 W. Roschat et al. / Fuel 98 (2012) 194–202

100
100

80
80

60

%FAME
60
%FAME

Rice bran oil

(FFA 0.10 mg KOH/g(oil))
40 40 Soybean oil
(FFA 0.18 mg KOH/g(oil))
Palm oil
Methano/oil ratio (FFA 0.28 mg KOH/g(oil))
20 12:1 20
Waste cooking oil
15:1 (FFA 1.15 mg KOH/g(oil))
18:1
0 21:1 0

0 2 4 6 8 10 0 2 4 6 8 10 12
Time (h) Time (h)

Fig. 4. Effects of methanol/oil molar ratio on the %FAME: catalyst (100 wt.%, Fig. 6. Effects of type of oil and FAA quantity in oil on the %FAME: catalyst
calcined at 700 °C for 1 h); reaction temperature (65 °C) without stir. (100 wt.%, calcined at 700 °C for 1 h); methanol/oil molar ratio (15:1); reaction
temperature (65 °C) with stir.

with oil and catalyst. The optimum methanol/oil molar ratio in the
present reaction is 15:1, which is more than double of the practical
methanol/oil molar ratio (6:1) for homogeneous process.
The effect of stirring the reaction mixture was also investigated.
The separation phase between hydrophilic methanol and hydro-
phobic oil and between both liquid reactants and solid catalyst
are generally known to be major problems of lowering a conver-
sion of reaction in the heterogeneous process. Therefore, combin-
ing the reaction mixture by stirring would promote the
transesterification. As depicted in Fig. 5, the reaction with a con-
stant stirring progressed at a faster rate and FAME yield over 98%
was accomplished within 2 h, which was only 30 min slower than
that of the typical heterogeneous transesterification of palm oil
catalyzed by CaO powder [22].
To investigate a versatile catalytic activity of the coral fragment
catalyst, many kinds of oils including palm oil (FFA of 0.28 mg KOH
g1), soybean oil (FFA of 0.18 mg KOH g1), rice bran oil (FFA of
0.1 mg KOH g1) and waste cooking oil (FFA of 1.15 mg KOH g1)
were used in biodiesel synthesis. It was found that the source of
oils (triglyceride) and the amount of free fatty acid (FFA) in the
oil had no effect on the conversion efficiency of the catalyst
(Fig. 6). In all cases, FAME exceeding 98% was achieved within
100
80
60
%FAME
2 h. Moreover, no soap formation was observed in the transesteri-
fication of waste cooking oil (high FFA oil). It was noticed that the
initial rates of the reaction were reduced as the amount of FFA in
oil increased. At a reaction time of 1 h, FAME was formed in
descending order as follows: rice bran oil (42.6%) > soybean oil
(36.4%) >palm oil (23.0%) > waste cooking oil (16.7%). In spite of
the transesterification activity of calcined coral fragment is not as
efficient as that of CaO powder and KOH catalysts. However, this
can be compensated because the coral fragment-based CaO has a
major advantage of easy separation of biodiesel product from the
reaction mixture. Moreover, this catalyst presents good catalytic
activity in a bulk solid form, opening the possibility to perform a
continuous catalytic process for biodiesel production in both slurry
and fixed bed configuration reactors, with the capability to use
cooking oil as an inexpensive feedstock, which will contribute to
the elimination of a residue together with the production of
biodiesel.
3.3. Reuse, recycle and stability of catalyst
The recycling of the catalyst is an important factor for the eco-
nomical application of coral fragments as heterogeneous catalyst
for biodiesel production. It is also vital to ensure that the active
species are not leached from the solid catalyst. The reusability
was checked by using the catalyst without any further activation.
The results (Fig. 7) indicated that the coral fragment catalyst with-
out any further activation could be reused up to five times and
more than 94% of FAME reached within 2 h with no obvious loss
of activity. After that the activity of this catalyst was gradually re-
duced. The catalyst was completely deactivated after being used

more than 10 times. The deactivation of this catalyst might be

due to damage of the active sites on its surface. This damage could
40 With stir result from impurities or from the reactions or the hydration of
Without stir CaO to form Ca(OH)2 which then undergoes carbonation to CaCO3
over the time, because the reactants contain a little amount of
20
water and the reaction was carried out in an open air. The IR and
XRD patterns of the deactivated catalyst showed peaks consistent
0 to CaCO3 as illustrated in Fig. 8. These results were in agreement
with the data reported by Granados et al. [23], and Lanas and
0 2 4 6 8 10 12 Álvarez [25] who also found that CaCO3 developed at the expense
Time (h) of Ca(OH)2. This indicated that hydration of an activated CaO might
Fig. 5. Effects of stirring reaction on the %FAME: palm oil, catalyst (100 wt.%,
not be the main deactivating process as in fact the surface state of
calcined at 700 °C for 1 h); methanol/oil molar ratio (15:1); reaction temperature the working catalyst must be fully hydroxylated but the carbon-
(65 °C). ation of the Ca(OH)2 formed completely eradicated the catalyst.
 W. Roschat et al. / Fuel 98 (2012) 194–202 199

100 another preheated flask, then the reaction was allowed to proceed
New catalyst under the same conditions and the %FAME was monitored. As illus-
1st Recycle catalyst trated in Fig. 9, it was found that no significant increased in %FAME
80 after the catalyst was removed from the reaction. The increase of
%FAME in the early stage after removing of the catalyst, which
reached a constant yield of 30% after 30 min, might come from
60
the reaction of remaining methoxide anion formed during the
%FAME

presence of the catalyst with the triglycerides. However, a slight

40 dissolution of CaO in the reaction media or the leaching of active
species from the surface of the solids cannot be fully discarded
since some research groups have pointed out that slight amounts
20 of CaO were dissolved and transformed into calcium diglyceroxide
by combining with a glycerol by-product during transesterification
[23,27,28]. Kouzu et al. has mentioned that the transesterification
0
was catalyzed not only on basic sites on the surface of the CaO cat-
0 2 4 6 8 10 alyst, but also by the soluble substance [22]. Therefore, the amount
Reused time of soluble substances leaching away from the catalyst was esti-
mated from ions contained in biodiesel and glycerol by-product
Fig. 7. Effects of reuse and recycle of the catalyst on the %FAME: catalyst (100 wt.%,
and compared with that of CaO powder. As shown in Table 1, cal-
calcined at 700 °C for 1 h); methanol/oil molar ratio (15:1); reaction temperature
(65 °C) with stir. cium contents in the biodiesel and glycerol obtained without any
treatment and cleaning processes were 109 and 904 ppm, respec-
tively, for the coral fragment, and 309 and 2439 ppm, respectively,
(A) for the CaO powder. The lower soluble ions content in the products
Absorption intensity (a.u.)

Deactivated coral
from coral fragment catalyst can be rationalized by a bulk solid
form of the catalyst. This indicates that it is more stable to the
Uncalcined coral leaching process than other forms. The calcium content in biodiesel
from both catalysts was somewhat higher than the EN14124 stan-
dard that limits the calcium content in biodiesel to 5 ppm. How-
CaCO3 (calcite) ever, removal of the soluble substance of this magnitude from
the biodiesel can be achieved by cation-exchange resin. Kouzu et
al. also demonstrated that the sulfonated resin efficiently removed
calcium ion from biodiesel with the estimated purification ability
4000 3500 3000 2500 2000 1500 1000 500
of 400 ml oil per 1 ml resin [22]. Indeed, the calcium content of
Wavenumber (cm-1)
the obtained biodiesel that passed through a column packed with
Dowex cation-exchange resin was close to 0 ppm (purification
(B) ability of 200 ml oil/ml resin) (Table 1). Therefore, with the help
of this purification technique, calcined coral fragments can be uti-
Intensity (a.u.)

Uncalcined coral
lized as efficient heterogeneous catalysts for biodiesel production.
Deactivated coral
3.4. Biodiesel and glycerol properties

CaCO3 In the view point of using this coral fragment catalyst in practi-
cal industrial biodiesel production, a primary investigation on
20 30 40 50 60 70 80
100
2 Theta (degree)

Fig. 8. (A) IR spectra and (B) XRD patterns of the deactivated catalyst compared
with CaCO3. 80

However, the catalyst could be regenerated just by simple calcina- 60

%FAME

tion. After activation, the regenerated coral fragment could be re-

used for three times with more than 95% of FAME reached
within 2 h. Therefore, coral fragment catalysts can be reused and 40
regenerated. Many research groups have also recently demon-
strated that the CaO in powder forms can be reutilized several
times [26]. These results stress the possibility of using CaO in bulk 20
solid form as a catalyst when compared with CaO powder and KOH
dissolved in methanol.
Since some calcium ions were found in biodiesel obtained from 0
in

in

in

in

in

in

heterogeneous process catalyzed by powder CaO [22,27] and in

m

m
0

10

30

60

90

general CaO is slightly soluble in methanol (0.035 wt.%) [28], this

12

factor was taken into consideration in our case. In an attempt to Reaction time (after removing the catalyst) (min)
clarify this point the quenching and leaching tests were performed Fig. 9. Effects of reaction time after removing the catalyst at 30 min on the %FAME:
in which the reaction was carried out in the same manner. After a catalyst (100 wt.%, calcined at 700 °C for 1 h); methanol/oil molar ratio (15:1);
30 min reaction, a liquid mixture was transferred carefully to reaction temperature (65 °C) with stir.
200 W. Roschat et al. / Fuel 98 (2012) 194–202

Table 1
Fuel properties of biodiesel obtained from the upper phase of the separation without any treatment and cleaning process.

Fuel propertiesa Standardk Trakarnpruk [29]/Gao [30]/Baroutian [11] This worko

b
Density 860–900 877/–/877 874
Kinematic viscosityc 3.5–5.0 4.5/4.37/5.16 4.33
Flash pointd >120 142/150/188 238
Acid numbere <0.5 0.20/0.3/0.33 0.25
Water contentf <0.050 –/0.039/– 0.025
Copper strip corrosion Number 1 –/–/– Number 1
Methyl ester contentg 96.5 97.9/99/– 96.8
Oxidation numberh >6 –/–/– 12.68
Total contaminationi <24 –/–/– 7.0 ± 0.6
Calcium contentj 5 309 ± 0.1m 109 ± 0.3 (1.1 ± 0.5)n
a
Preformed by biodiesel testing unit, the National Science and Technology Development Agency, Thailand.
b
@15 °C (kg m3).
c
@ 40 °C (cSt).
d
°C.
e
mg KOH g1 oil.
f
%w/w oil.
g
%.
h
hour.
i
mg/kg (ppm).
j
ppm g1 oil.
k
EN 14214 standard.
m
Using CaO powder as catalyst.
n
After purification by cation-exchange resin.
o
Palm oil.

medium scale biodiesel production from palm oil (5 L) was carried
out using small scale optimum conditions: catalyst calcined at
700 °C for 1 h; catalyst/oil ratio of 100 wt.%; methanol/oil molar ra-
tio of 15:1; reaction temperature of 65 °C without stirring. The
transesterification reaction progressed slower than a small scale
reaction (50 ml) and a complete conversion with FAME of 98%
was attained within 8 h, which was twice longer than that of a nor-
mal small scale reaction (Fig. 10). However, we considered that
with optimum reaction conditions and with stirring, the transeste-
rification of oil to biodiesel would proceed faster. It is essential to
note that the biodiesel product and glycerol by-product were cor-
rected by simply pouring off from the reaction vessel followed by
filtering through a cotton wool filter without any treatment and
cleaning processes. Any excess methanol was rotary evaporated,
and biodiesel product and glycerol by-product were allowed to iso-
late in separating funnels. Fuel properties of biodiesel were evalu-
ated according to the ASTM methods and compared with biodiesels
100
80
60
%FAME
prepared from palm oil by other investigators [11,29,30]. The re-
sults are summarized in Table 1. The biodiesel product had a den-
sity of 0.874 g/ml which was slightly higher than that of diesel fuel
(0.83 g/ml). According to EN 14214, the minimum acceptable pur-
ity for biodiesel is 96.5% of methyl esters. The biodiesel produced
had somewhat higher methyl ester content of 96.8%. The flash
point in this study was 238 °C, which was much higher than that
of the compared results and biodiesel obtained from other oils.
The water content in biodiesel product was 0.025 %w/w, which
was lower than the limit of standard diesel and biodiesels prepared
by other heterogeneous catalysts. The viscosity of the obtained bio-
diesel was 4.33 cSt, which was slightly lower than that of the com-
pared results. The acid value in this study was 0.25 mg KOH/g
indicating less content of free fatty acid in the biodiesel product.
The total contamination defined as the insoluble material retained
after the filtration of a heated biodiesel over a standardized 0.8 lm
filter was 7.0 ± 0.6 mg/kg, which was fairly lower than the limit of
standard requirement. Referring to EN 14214 standards for bio-
auto fuels, the biodiesel obtained from this study was found to
be within the limits in terms of methyl ester content, density, vis-
cosity, flash point, acid value and water content, and in accordance
with other investigators.
The properties of the by-product of this biodiesel production
without any treatment and cleaning process was briefly evaluated
according to the International Standards Organizing (ISO) and Brit-

ish Standards Institution (BS) methods indicating good-quality

crude glycerol compared to crude glycerol obtained from CaO pow-
40 der and KOH catalysts (Table 2, Fig. 11). The attained glycerol was
clear viscous with odorless and color body of light pale. The UV–Vis
spectra in transmission mode displayed percent transmission (%T)
20
over 97% in visible region (400–800 nm). The IR spectra were iden-
tical to that of the 99.5% pure glycerol sample. As a result, to purify
0 this glycerol to higher grades, chemically pure (CP) and United
States Pharmacopeia (USP), might be simply accomplished by
0 2 4 6 8 10 extraction with hexane, ion removal by activated carbon adsorp-
Time (h) tion followed by distillation, thereby high-value glycerol. Full
investigations are in progress. The value of crude glycerol in the
Fig. 10. Effects of reaction time on the %FAME: 5L scale reaction, catalyst (100 wt.%,
calcined at 700 °C for 1 h); methanol/oil molar ratio (15:1); reaction temperature marketplace generally depends on its quality as determined by
(65 °C) without stir. the ease of its subsequent refining.
 W. Roschat et al. / Fuel 98 (2012) 194–202 201

Table 2
Properties of glycerol obtained from the lower phase of the separation with further heated in an oven (70–80 °C) for 24 h followed by filtration through a cotton wool filter.

Properties Standard Catalyst/oil

Coral fragment/palmd Coral fragment/sunflowerd CaO powder/palme KOH/palme
a
Glycerol content (%) 95 68 78 44 23
Total ash (%) 10b 0.302 0.022 0.12 5.38
Sulfated ash (%) 0.01a 0.026 0.010 0.45 4.22
pH – 7.32 7.72 7.82 10.34
Density (g cm3) 1.26c 1.18 1.20 1.10 <1.00
Calcium content (ppm/g) 5a 904 ± 0.7 – 2439 ± 0.9 –
Color Water-whitec Light pale Light pale Light pale Brown
a
Pharmaceutical grade.
b
Crude glycerol from soap manufacture.
c
Pure glycerol.
d
Using optimum conditions.
e
Using literature methods [5,16,17].

Coral/sunflower oil
(A) 100 (B)
Coral/palm oil
80
Pure glycerol
%Transmittance

%Transmittance
60 CaO powder/palm oil

CaO powder/palm oil

KOH/palm oil
40 KOH/palm oil
Pure glycerol
Coral/palm oil
Coral/sunflower oil
20

0
200 300 400 500 600 700 800 4000 3500 3000 2500 2000 1500 1000 500
Wavelength (nm) Wavenumber (cm-1)

Fig. 11. UV–Vis and IR spectra of by-product glycerol obtained without any treatment and cleaning processes.

4. Conclusion Acknowledgements

In summary, we have demonstrated that solid catalysts derived
from calcination of waste coral fragments can be utilized as effi-
cient heterogeneous solid catalysts for transesterification of many
kinds of oils to biodiesel. The reaction under optimum conditions
of catalyst calcined at 700 °C for 1.0 h; catalyst/oil ratio of
100 wt.%; methanol/oil molar ratio of 15:1; reaction temperature
of 65 °C with a constant stirring yields biodiesel with a FAME
exceeding 98% in 2 h. The catalyst can be easily separated from
the reaction mixture by simple filtration and can be used several
times with consistent activity. Biodiesel and glycerol products
without any treatment and cleaning processes show high quality
with fuel properties of the biodiesel meet all EN 14214 standard.
The calcined coral fragment presents good catalytic activity in a
bulk solid form, opening the possibility to perform a continuous
catalytic process for biodiesel production with batch reactor. The
utilization of this good-quality glycerol together with the natural
availability of the coral fragment and the capability to use a residue
as cooking oil as inexpensive feedstock would supplementary im-
prove the economic aspect of overall biodiesel production based
on this catalyst, producing cost-efficient biodiesel. The catalyst,
therefore, displays high potential as solid catalyst for practical,
environmentally friendly, and low cost industrial biodiesel and
glycerol production. For people in rural areas or developing coun-
tries, this process could be an effective way to obtain cheap energy
sources. Full investigation on an industrial scale of biodiesel and
glycerol production based on this catalyst is on-going in our
laboratory.
This work was supported by the Thailand Research Fund
(IUG5180010), Strategic Scholarships for Frontier Research Net-
work for Research Groups (CHE-RES-RG50) funded by the Office
of the Higher Education Commission, Thailand. We acknowledge
the scholarship support from the Thailand Graduate Institute of
Science and Technology (TGIST) to Mr. Wuttichai Roshchat and
Center for Innovation in Chemistry (PERCH-CIC).
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