Renewable Energy 113 (2017) 697e705

Contents lists available at ScienceDirect

Renewable Energy
journal homepage: www.elsevier.com/locate/renene

Response surface methodology for the optimum production of

biodiesel over Cr/Ca/g-Al2O3 catalyst: Catalytic performance and
physicochemical studies
Nur Fatin Sulaiman, Wan Azelee Wan Abu Bakar*, Rusmidah Ali
Department of Chemistry, Faculty of Science, Universiti Teknologi Malaysia, 81310, UTM, Skudai, Johor, Malaysia

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

Article history: Attention continues to be focused on biomass as a very promising alternative source of renewable
Received 16 November 2016 materials for energy production. This research focused on the use of a heterogeneous base alkaline earth
Received in revised form metal oxide incorporated with a transition metal oxide catalyst supported on gamma alumina oxide
29 May 2017
varied with different temperatures, Cr loading and number of alumina coatings that make the biodiesel
Accepted 1 June 2017
easily separated, low cost and environmental friendly. The physicochemical properties of Cr/Ca(10:90)/g-
Available online 2 June 2017
Al2O3 catalyst calcined at 700
C investigated by BET surface area and CO2-TPD indicated high surface
area, 164.32 m2/g and higher basicity, 3.38 mmol/g, respectively. FESEM-EDX mapping showed the ho-
Keywords:
Response surface methodology
mogeneous distribution of each element presence in Cr/Ca(10:90)/g-Al2O3 catalyst was well-distributed
Biodiesel and indicated that the Cr/Ca has a higher dispersion on the surface of the g-Al2O3. The response surface
Bimetallic oxide methodology was used to optimize the catalytic activity of Cr/Ca/g-Al2O3 catalyst for transesterication
Catalytic activity of biodiesel from low-grade cooking oil. The most important variable for biodiesel yield was the calci-
Transesterication nation temperature of the catalyst followed by the Cr loading and the number of alumina coatings. The
experimental value achieved with 93.10% conversion of biodiesel closely agreed with the predicted result
from RSM and validated the ndings of response surface optimization.
2017 Elsevier Ltd. All rights reserved.

1. Introduction
Recently, a substantial quantity of research has been conducted
to develop a new renewable and sustainable energy resource that
might function as a substitute for petroleum. Biodiesel is commonly
used in standard diesel engines and it is different from the vege-
table oils used to fuel converted diesel engines. Otherwise, it can
also be used as a low carbon alternative to heating oil. Fuels pro-
duced from renewable biomass can reduce the greenhouse gas
emissions, pollution, deforestation and the rate of biodegradation.
Biodiesel is free of sulphur and aromatic as it is non-toxic and
biodegradable that can produce lower exhaust emissions [1].
Environmental concerns in fossil fuel depletion intensied the
search for alternate fuel from renewable resources. Many re-
searchers have pointed out an important drawback related to the
use of homogeneous catalysts in biodiesel production. When the oil
* Corresponding author.
E-mail addresses: nurfatinsulaiman@gmail.com (N.F. Sulaiman), wazelee@kimia.
fs.utm.my (W.A. Wan Abu Bakar), rusmidah@kimia.fs.utm.my (R. Ali).
that contain fatty acids react with the homogeneous catalyst, it will
form soaps as unwanted by-products, hence requiring more
expensive separation processes. Therefore, there is currently a shift
towards the development of industrial processes for biodiesel
production using solid catalysts. Solid based catalysts have been
considered as an alternative to homogeneous base catalysts due to
several advantages where the catalysts are not dissolved or
consumed in the reaction. Therefore, it can be easily separated from
the product, regenerated and reused in a continuous process. In
addition, less maintenance is needed to lower separation costs as
the solid catalysts are non-corrosive.
Early studies on the heterogeneously catalysed trans-
esterication were focused on the catalysis by single metal oxides
[2]. Calcium oxide is the most frequently applied metal oxide
catalyst for biodiesel preparation due to its cheap price, relatively
high basic strength and less environmental impacts. However, it is
necessary to increase the basic strength of single metal oxide cat-
alysts and hence, mixed metal oxides are synthesized. Therefore, in
this study, base heterogeneous catalytic reaction by using alkaline
earth metal oxide incorporate with a transition metal oxide that has
not been extensively explored was introduced in biodiesel

http://dx.doi.org/10.1016/j.renene.2017.06.007
0960-1481/ 2017 Elsevier Ltd. All rights reserved.
698 N.F. Sulaiman et al. / Renewable Energy 113 (2017) 697e705
production due to the environmental constraints and simplica-
tions in the existing process.
Gamma aluminium oxide has been widely used as a support of
active species in industrial processes due to its high thermal sta-
bility and specic surface area (as high as 300 m2/g), mesopore size
of 5e15 nm, pore volume of 0.60 cm3/g and ability to be shaped into
pellets [3]. Hence, in this work, calcium nitrate and chromium ni-
trate as environmentally friendly and cheap precursor were used to
synthesis a high performance solid base catalyst that consists of Cr/
Ca supported on g-alumina. To our best knowledge, the utilization
of wet impregnation method to synthesize Cr/Ca/g-Al2O3 catalysts
for the transesterication of biodiesel has not been revealed yet.
The activity of a solid catalyst was highly correlated with the
concentration of active sites on the catalyst [4]. In this study, the
activity of the catalyst for transesterication reaction was opti-
mized using response surface methodology (RSM). RSM is a useful
statistical technique which has been applied in research into
complex variable processes. It employs multiple correlation ana-
lyses as tools to assess the effects of two or more independent
variables on the dependent variable. No literature was found on the
optimization of transesterication reaction over Cr/Ca/g-Al2O3
catalyst using RSM. Thus, in this research, RSM modelling was used
to determine the optimum processing conditions which could lead
to the maximum production of biodiesel through trans-
esterication of low-grade cooking oil over Cr/Ca/g-Al2O3 catalyst.
2. Experimental
2.1. Materials
The low-grade cooking oil was obtained from local market.
Calcium nitrate tetrahydrate, Ca(NO3)2$4H2O, chromium(III) nitrate
nanohydrate, Cr(NO3)3$9H2O, gamma alumina oxide (beads), g-
Al2O3, methanol, CH3OH and n-hexane, C6H14 were purchased from
Merck. All chemicals and solvents were used without further
purication.
2.2. Catalyst preparation
The bimetallic oxide catalysts were prepared by using wet
impregnation method supported on Al2O3 (specic area 253 m2/g
and 3e5 mm bead diameter). Cr(NO3)3.9H2O as a dopant was dis-
solved into 5 mL of distilled water according to the dopant ratio to
based. About 5.0 g of Ca(NO3)2$4H2O as a based metal oxides were
dissolved into 5 mL of distilled water. Both based and dopant so-
lutions were mixed together. Then, 5.0 g of g-Al2O3 that is most
widely used as support material was dipped into the precursor
solution within 1 h varied with 1e5 times of coating respectively.
The g-Al2O3 beads act as support and were immersed into the
catalyst solution for 15 min per coating. After coating, g-Al2O3
beads were aging at ambient room temperature and followed by at
temperature of 80e90
C in the oven for 24 h to remove water and
to allow good coating of the metal on the surface of the supported
catalysts. Then, the samples were calcined at a temperature of 600,
700 and 800
C for 5 h using a ramp rate of 5
C/min to eliminate all
the metal precursor impurities.
2.3. Catalyst characterization
The prepared catalysts were characterized using multi-point
Brunauer Emmett Teller (BET), Field Emission Scanning Electron
Microscopy (FESEM), Energy Dispersive X-ray (EDX) and CO2-
Temperature Programmed Desorption (CO2-TPD). The nitrogen
adsorption analysis of the catalyst was studied using Micromeritics
ASAP 2010. Prior to analysis, the 0.2e0.3 g of powder sample was
degassed at 120
C and the dead space removed by vacuum pump
to cool the sample to room temperature. The specic surface area
and pore size distribution were calculated from the adsorption
curve according to the BrunauerEmmettTeller method.
FESEM-EDX analysis was accomplished by using Philips XL 40
microscope with energy of 5.0 kV coupled with EDX analyser and
bombarded using an electron gun with tungsten lament under
25 kV resolutions to get the required magnication image. EDX was
used in this study to determine the elemental composition on the
submicron scale. The supported catalyst sample was attached by
carbon tape on special platform called stub, coated with platinum
using a platinum sputter at 101 Mbar using a Bio Rad Polaron
Division SEM coating system machine. The sample was bombarded
using an electron gun with a tungsten lament under 25 kV reso-
lutions in order to get the required magnication image.
Next, CO2-TPD was done using Micromeritics Autochem 2920.
The 0.04e0.05 g of catalyst sample was placed in a quartz U-tube
(internal diameter 10 mm) and was cleaned under helium ow
for 20 mL/min at 150
C for 1 h. Prior to analysis, the temperature
was ramped down to 40
C. The CO2 gas was then ow continuously
through the sample at 40
C for 1 h to pre-saturate the active sites
with CO2. The gas ow was changed to helium gas (20 mL/min) for
another 1 h at 80
C to remove weak physisorbed CO2 from the
surface of the samples. The temperature subsequently ramped
down to 40
C before the TPD step. The TPD was then carried out by
ramping the temperature to 1000
C at 10
C/min while, the TPD
response was recorded.
2.4. Catalytic reaction and product analysis
About 1.2 g of the prepared catalyst, 18.5 g of methanol and
20.0 g of low-grade cooking oil were added into a two-necked
round bottom ask and reuxed at 65 5
C for 3 h to complete
the transesterication reaction. The parameter for trans-
esterication reaction was selected based on the catalytic screening
that gave high conversion of biodiesel. The mixture was centrifuged
at 3000 rpm for 10 min to separate the solid catalyst from the so-
lution. Three layers were obtained after the centrifugation. An
excess of methanol was at the top layer, a biodiesel at middle layer
and the bottom layer was catalyst samples and glycerol. The bio-
diesel was collected for further characterization. The product ob-
tained was analyzed using GC-FID, equipped with a SP-2560
capillary column (100 m  0.25 mm x 0.20 mm) and helium as a
carrier gas. The column temperature program was as follows: the
initial temperatures was 140
C for 5 min and the rst rate was 4
C/
min up to 240
C for 15 min. The injector and detector temperatures
was set up at 260
C. The chromatogram results were conrmed in
the presence of the biodiesel composition such as palmitic acid
(C16:0), palmitoleic acid (C16:1), stearic acid (C18:0), oleic acid
(C18:1), linoleic acid (C18:2) and linolenic acid (C18:3). The iden-
tied composition was compared with Supelco 37 component
FAME mix standards.
2.5. Reusability testing over Cr/Ca(10:90)/g-Al2O3 catalyst
The transesterication reaction of low-grade cooking oil was
conducted under optimized condition (65
C reaction temperature,
1:18 oil to methanol ratio with 6 wt% of Cr/Ca(10:90)/g-Al2O3
catalyst loading for 3 h reaction time). The reusability of Cr/
Ca(10:90)/g-Al2O3 catalyst for transesterication of biodiesel was
examined in the subsequent run without further treatment.
2.6. Experimental design
In this research, RSM was performed in order to validate the
 N.F. Sulaiman et al. / Renewable Energy 113 (2017) 697e705 699

predicted value of optimization parameters from RSM with the Table 2

value obtained from experimental results. In this work, experi- The catalytic performance of alumina supported calcium oxide based catalysts with
chromium as a dopant.
ments were designed by Design-Expert Software Version 7.1.6 us-
ing a BoxeBehnken Design (BBD) to investigate the effect of the Catalyst Calcination Number of Dopant ratio Biodiesel
parameters on the catalyst activity for biodiesel production and to temperature (
C) alumina coatings to based conversion (%)

obtain a design model equation to predict the optimum catalyst Al2O3 e e e 12.50
preparation conditions. There are three numeric factors that were Ca/g- 600 1 e 79.50
Al2O3 3 76.70
included in this part and each factor was varied over 3 levels. The
5 85.00
levels of those independent variables were based on experimental 700 1 e 76.80
parameters which were calcination temperature (X1), number of 3 80.90
alumina coatings (X2) and Cr loading (X3). The percentage conver- 5 80.70
800 1 74.70
sion of biodiesel was chosen as responses. A total of 17 experiments e
3 78.60
was designed and performed in random order and its coded levels 5 84.80
are displayed in Table 1. A second-order polynomial was used as an Cr/Ca/g- 600 1 10:90 80.80
empirical model that describes the response surface (Eq. (1)). Al2O3 20:80 81.50
30:70 82.00
X X X
Y b0 biXi biiXi2 bijXiXj (1) 3 10:90 89.60
20:80 85.20
30:70 87.20
Next, the validity of the design model was tested by using
5 10:90 78.10
analysis of variance called ANOVA. It was performed based on the 20:80 85.40
proposed model to determine the interaction between the process 30:70 78.60
variables and response [5]. The signicant model must be referred Cr/Ca/g- 700 1 10:90 83.90
Al2O3 20:80 82.70
to the F-value (Fischer variation ratio) and p-value (signicant
30:70 82.10
probability value) whereby the p-value of selected model should be 3 10:90 93.10
less than 0.05% and insignicant of lack of t. Insignicant lack of t 20:80 89.40
is most required as signicant lack of t indicates that there might 30:70 89.20
be contributions in the regressor-response relationship that are not 5 10:90 89.00
20:80 84.60
accounted for by the model. Furthermore, the coefcient of deter-
30:70 80.60
mination (R2) must be close to 1 indicating the better correlation Cr/Ca/g- 800 1 10:90 81.50
between the experiment and the predicted values [6]. Finally, two- Al2O3 20:80 82.00
dimensional contour plots and three-dimensional response surface 30:70 81.70
3 10:90 82.40
plots were drawn in order to visualize the individual and the
20:80 83.20
interaction between the effects of the independent variables to- 30:70 82.10
wards the conversion of biodiesel [7,8]. 5 10:90 82.40
20:80 82.30
30:70 81.80
3. Results and discussion

3.1. Catalytic performance ASTM D664 standard. The TAN value, 1.14 mg KOH/g of low-grade
cooking oil was recorded that exceeded 0.50 mg KOH/g which is
The catalytic activity of Cr/Ca/g-Al2O3 catalysts were investi- not suitable for use as fuel for vehicles. Thus, in this study, the Cr/
gated by transesterication of low-grade cooking oil to biodiesel. Ca/g-Al2O3 were used as a catalyst to convert free fatty acids in low-
The free fatty acids (FFA) contained in low-grade cooking oil was grade cooking oil to fatty acid methyl esters (FAME) also known as
veried by using total acid number (TAN) analysis according to biodiesel.
Table 2 shows the catalytic performance of alumina supported
Table 1
calcium oxide based catalysts with chromium as a dopant. Ac-
The coded and uncoded level of the independent variables. cording to the results in Table 2, Ca/g-Al2O3 catalyst gave only
85.00% conversion of biodiesel at 600
C with 5 times alumina
No. Factor variables (coded and uncoded)
coatings. In this study, chromium, Cr was added to the Ca/g-Al2O3
Standard X1: calcination X2: number of alumina X3: Cr loading catalyst to investigate the effect on Cr on catalytic trans-
temperature (
C) coatings (times) (wt.%)
esterication of low-grade cooking oil to biodiesel in the presence
1 1 (600) 1 (1) 0 (10) of three different parameters. By adding 10 wt% of Cr to the Ca/g-
1 (800) 1 (1)
2 0 (10)
Al2O3 catalyst to form Cr/Ca/g-Al2O3 catalyst calcined at 700
C, the
3 1 (600) 1 (5) 0 (10)
4 1 (800) 1 (5) 0 (10)
conversion of biodiesel was slightly increased to 93.10%.
5 1 (600) 0 (3) 1 (0) The catalytic performance decreased with increasing of Cr
6 1 (800) 0 (3) 1 (0) loading from 20 to 30 wt% onto Ca/g-Al2O3 due to the poor in-
7 1 (600) 0 (3) 1 (20) teractions between the active basic metal oxide and its support
8 1 (800) 0 (3) 1 (20)
material. This proved that there was an optimum limit for dopant
9 0 (700) 1 (1) 1 (0)
10 0 (700) 1 (5) 1 (0) ratio in order to enhance the catalytic transesterication reaction.
11 0 (700) 1 (1) 1 (20) An excessive Cr loading (>10 wt%) would form bulky metal parti-
12 0 (700) 1 (5) 1 (20) cles which lead to the agglomeration on the catalyst surface. The
13 0 (700) 0 (3) 0 (10) agglomeration blocked the pores and caused a reduction in the
14 0 (700) 0 (3) 0 (10)
15 0 (700) 0 (3) 0 (10)
active sites, hence decreased the catalytic activity. From this
16 0 (700) 0 (3) 0 (10) observation, the optimum conditions for Cr/Ca/g-Al2O3 catalyst
17 0 (700) 0 (3) 0 (10) obtained with 3 times number of alumina coatings, 10:90 dopant
700 N.F. Sulaiman et al. / Renewable Energy 113 (2017) 697e705

92.79
95
87.51

Percentage conversion of
90 85.59 84.93

biodiesel (%)
84.29
85
78.29
80

75

70
1 2 3 4 5 6

Fig. 1. Reusability testing over Cr/Ca(10:90)/g-Al2O3 catalyst calcined at 700
C for 5 h.

Table 3 will lead to the increasing of particle size of the catalyst and thus,
BET multipoint analysis data for g-Al2O3 and Cr/Ca(10:90)/g-Al2O3 calcined at the surface area will be reduced [9].
different temperatures for 600, 700 and 800
C for 5 h.
The pore volume and size contributed to the higher catalytic
Catalyst Calcination BET Surface Area Pore Volume Pore activity of transesterication reaction. The relationship between
Temperature (
C) (m2/g) (cm3/g) Size () these two factors was inversely proportional to each other. The pore
g-Al2O3 e 77.50 0.27 e volume of Cr/Ca(10:90)/g-Al2O3 catalyst increased from 0.39 to
Cr/Ca(10:90)/ 600 196.46 0.39 79.71 0.44 cm3/g when the calcination temperature was increased from
g-Al2O3 700 164.32 0.44 106.59
600 to 700
C and decreased to 0.31 cm3/g when calcined at 800
C.
800 95.88 0.31 129.91
Therefore, Cr/Ca(10:90)/g-Al2O3 calcined at 700
C was the poten-
tial catalyst due to its high surface area and bigger pore volume that
will lead to a rise in the number of active sites. A combination of
ratio to based and calcined at 700
C gave the maximum conversion
larger pore volume and smaller pore size with high surface area
of biodiesel.
allowed different type, length and diameter of triglycerides to enter
the pores of the catalyst and provides enough surface site for
3.2. Reusability testing over Cr/Ca(10:90)/g-Al2O3 catalyst transesterication reaction.
Fig. 2 depicts the nitrogen adsorption-desorption isotherms for
The Cr/Ca(10:90)/g-Al2O3 catalyst calcined at 700
C was tested Cr/Ca(10:90)/g-Al2O3 catalyst at different calcination temperatures
several times in order to study the reusability of the catalyst. It was of 600, 700 and 800
C respectively. According to IUPAC classi-
tested by using the same catalyst until the catalyst was deactivated. cation, all samples displayed Type III sorption isotherms, indicating
Fig. 1 shows the trend plot of reusability testing over Cr/Ca(10:90)/ that the catalysts were typically in mesoporous structure due to the
g-Al2O3 catalyst. It can be seen that the conversion of biodiesel over presence of hysteresis loop type H3. As the calcination temperature
the fresh catalyst was 92.79%. The biodiesel conversion exceeded increased, the hysteresis loop in the relative pressure was narrower
84% through fth reuse. In the sixth testing, the conversion of from P/P0 0.45e1(600 and 700
C) to P/P0 0.6e1(800
C) which
biodiesel was decreased to 78.29% due to the catalyst deactivation. explained that the degree of mesoporosity was higher at lower
The slight decrease of catalytic activity was attributed to the slight calcination temperature and may provide more inner surface areas
decrease of strength and amount of basic sites of used Cr/Ca(10:90)/ and active sites to the catalyst.
g-Al2O3 catalyst. According to the Mahlambi et al. [10], g-Al2O3 support exhibit
Type IV nitrogen adsorption-desorption isotherm with type H1

3.3. Catalyst characterization

3.3.1. Brunauer Emmett Teller (BET)

Table 3 summarizes the surface area, pore volume and pore size
for Cr/Ca(10:90)/g-Al2O3 catalysts at different calcination temper-
atures. As can be seen from Table 3, it was found that increasing the
calcination temperature could cause the decreasing in the surface
area. The Cr/Ca(10:90)/g-Al2O3 catalyst calcined at 600
C gave the
highest BET surface area of 196.46 m2/g as compared to the cata-
lysts calcined at 700
C which gave of 164.32 m2/g.
This is due to the decrease number of micropores in the samples,
as indicated by the increased of pore size. The BET surface area
decreased drastically to 95.88 m2/g when the catalyst was calcined
at 800
C due to the partial collapse of the pore structure after its Fig. 2. Nitrogen adsorption-desorption isotherms for Cr/Ca(10:90)/g-Al2O3 catalyst at
contact with the catalyst at the higher calcination temperature. It different calcination temperatures of 600, 700 and 800
C for 5 h respectively.

hysteresis loop, which suggested the presence of mesopores or
micropores based on IUPAC classication. This type of isotherm
describes the process of nitrogen adsorption on the adsorbent
surface [10]. These results indicated that the addition of Cr and Ca
towards g-Al2O3 support may lead to the production of new pores,
therefore, increases its surface area. The BJH pore size distributions
of the catalysts are represented in Fig. 3. The trend of the catalysts
showed relatively broad pore size distributions in which it was
higher in the pore volume for pore size below 30 nm.
3.3.2. Field Emission Scanning Electron Microscopy (FESEM)
Fig. 4 shows that an increase in calcination temperature from
600 to 800
C leads to the formation of aggregates and agglomer-
ates with undened shapes and mixture of larger and smaller
particles size. However, when the calcination temperature reached
at 800
C, it showed more agglomeration and their catalyst surfaces
were densely packed. It is due to the sintering effect that occurred
during the calcination process, hence form larger particle size. It
was assumed that the dense packed surface of catalyst leads to the
reduction of surface area as well as the catalytic activity perfor-
mance. Oh et al. [11] and Rosid et al. [12] proposed that the well-
dened morphology of the catalyst surface was highly correlated
with the calcination temperatures of catalysts [11,12].
3.3.3. Energy Dispersive X-ray (EDX)
Table 4 shows the chemical compositions expressed as weight
percentage over Cr/Ca(10:90)/g-Al2O3 catalyst obtained from EDX
analysis. The composition of the Al was determined to be around
47.00e52.00 wt% over all the catalysts prepared. Meanwhile, the
composition of Cr/Ca(10:90)/g-Al2O3 catalyst calcined at various
calcination temperatures showed slight differences with its original
composition. The detected Cr content increased from 0.50 wt% at
temperature of 600
C to 0.60 and 1.50 wt% at calcination tem-
perature of 700 and 800
C respectively. This was probably due to
the increase of particle size and the agglomeration of Cr particles
that occurred on the surface of the catalyst after being calcined at
higher temperature [13]. The composition for Cr and Ca elements
was the highest for Cr/Ca(10:90)/g-Al2O3 catalyst calcined at 700
C
compared with others that acted as active species and may lead to
the highest catalytic activity for transesterication reaction.
The distribution of the elements on the surface of Cr/Ca(10:90)/
g-Al2O3 catalyst calcined at 700
C is depicted in Fig. 5. As can be
dV/dlog(w) Pore Volume (cm3/g)
0.50
0.45
0.40
0.35
0.30
0.25
0.20
0.15
0.10
0.05
0.00
0 5
Fig. 3. Pore size distributions of Cr/Ca(10:90)/g-Al2O3 catalyst measured with N2 adsorption at different calcination temperatures of 600, 700 and 800
C for 5 h respectively.
N.F. Sulaiman et al. / Renewable Energy 113 (2017) 697e705 701
seen, each element, Cr and Ca in Cr/Ca(10:90)/g-Al2O3 catalyst was
well-distributed and indicated that the catalyst has a higher
dispersion and homogeneous characteristics on the surface of the
catalyst. This has contributed to the highest catalytic activity for
transesterication reaction of biodiesel.
3.3.4. CO2-Temperature Programmed Desorption (CO2-TPD)
The presence of basic sites on the surface of the prepared
catalyst which can be measured using CO2-TPD inuenced the
catalytic activity of transesterication process. The number of CO2
molecules adsorbed per unit surface area can be considered as a
measure of the amount of basic sites on the surface [14]. The
measurement of the basic sites strength was categorized according
to the specied temperature range. Fig. 6 illustrates the CO2-TPD
plot for Cr/Ca(10:90)/g-Al2O3 catalyst at calcination temperatures
of 600, 700 and 800
C respectively. It showed that three signicant
peaks were observed due to the highest amount of weak and
moderate basic sites.
The amount of the total basic sites calculated for Cr/Ca(10:90)/g-
Al2O3 catalysts were increased when the calcination temperature
was increased from 600 to 700
C which were 2.64032 mmol/g to
3.38146 mmol/g respectively. However, the total basic sites were
decreased when the calcination temperature of the Cr/Ca(10:90)/g-
Al2O3 catalyst reached at 800
C which was 2.61311 mmol/g. This
observation was supported with BET results where Cr/Ca(10:90)/g-
Al2O3 calcined at 700
C was the potential catalyst due to its high
surface area leading to increase number of active sites.
Table 5 shows CO2 desorbed temperature and amount of Cr/
Ca(10:90)/g-Al2O3 catalysts at calcination temperatures of 600, 700
and 800
C for 5 h derived from CO2-TPD. Based on the temperature
range for CO2 desorption on Cr/Ca(10:90)/g-Al2O3 catalysts calcined
at 700
C, two types of basic sites which were weak and moderates
sites have been identied that assigned to CO2 adsorbed on the Cr/
Ca species. The area for the second and last peaks were much larger
and showed higher level of intensity that implying more Cr/Ca
active sites were present as CO2 adsorption sites in Cr/Ca(10:90)/g-
Al2O3 catalysts.
The coordination of CO2 onto metal oxide has different energies
which causes different desorption proles. The lowest desorption
temperature was due to desorption of the weakest bonding mode
of CO2 onto the catalyst surface. The broad peaks area at 261.2 and
327.2
C indicated higher basicity surface of catalyst due to the
600C
700C
800C
10 15 20 25 30 35 40 45 50
Pore Width (nm)
702 N.F. Sulaiman et al. / Renewable Energy 113 (2017) 697e705

(a) (b)

135 nm

110 nm 107 nm
119 nm

(c)

157 nm

Fig. 4. FESEM micrographs of Cr/Ca(10:90)/g-Al2O3 calcined at temperatures of (a) 600
C, (b) 700
C and (c) 800
C for 5 h with magnication 20000 and scale bar 2 mm.

Table 4 It can be seen that the degree of freedom values (F-test) for the
Elemental composition by EDX analysis of Cr/Ca (10:90)/Al2O3 catalyst. model was found to be 14005.65 which implied that the model was
Catalyst Calcination Loading (wt.%) signicant. From the F-value and low p-value (<0.05) obtained, the
Temperature (
C) model that was used showed statically signicant for conversion of
Al O Cr Ca
biodiesel. The predicted R2 value of 0.9999 is in line with the
Cr/Ca(10:90)/g-Al2O3 600 52.20 45.50 0.50 1.80
adjusted R2 value of 0.9999. The R2 of 0.9999 indicates that the
700 47.20 47.90 0.60 4.40
800 51.10 44.90 1.50 2.50 regression model represented 99.99% of the experimental results
and only about 0.01% of the variability in the response was not
explained by this model [16]. From the results in Table 6, the
many CO2 desorbed on the basic sites of catalyst [15]. Consequently, squared effect of calcination temperature of Cr/Ca/g-Al2O3 catalyst
Cr/Ca(10:90)/g-Al2O3 catalysts calcined at 700
C gave the best was the most inuential parameter which achieved 41983.23 F-
catalytic activity due to the highest conversion of biodiesel. value followed with squared effect of Cr loading (35503.23) and the
less importance parameter of squared effect of the number of
alumina coatings (22842.47).
3.4. The optimization of Cr/Ca(10:90)/g-Al2O3 catalyst by RSM Furthermore, the three-dimensional response surfaces of con-
version of biodiesel towards independent variables are shown in
The results of the optimal conditions achieved from lab exper- Fig. 7. Based on the gure, the relationship between the effects of
iments were veried with the predicted value of RSM. There are two variables on the conversion of biodiesel when the third vari-
three factors that were taken into consideration towards percent- able remained constant in its zero level was determined. Fig. 7a
age conversion of biodiesel using of Cr/Ca(10:90)/g-Al2O3 catalyst shows the percentage conversion of biodiesel as a function of
which are calcination temperature (X1), number of alumina coat- calcination temperature and number of alumina coatings, while the
ings (X2) and Cr loading (X3). The nal quadratic equation on the Cr loading was kept constant at 10 wt%. It can be seen that the
design model with these three independent variables and the conversion of biodiesel using Cr/Ca/g-Al2O3 catalyst increased with
dependent responses (Y) is presented in Eq. (2). The predicted value an increasing in calcination temperature and number of alumina
of biodiesel conversion obtained from the model is recorded in coatings until the maximum conversion was achieved. Further
Table 1. These values are in good agreement with the actual value increased in calcination temperature and number of alumina
achieved from the experimental results. Table 6 shows the results coatings would cause the decreasing of conversion of biodiesel.
of ANOVA analysis from this model. Meanwhile, Fig. 7b represents the effect of calcination temper-
ature and Cr loading as dopants towards the conversion of biodiesel
Y 93.14e0.76*X1 e 0.16*X2 2.20*X3 0.42*X1*X2 e 1.15*X1*X3 while, the number of alumina coatings remained at 3 times. It can
e 0.05*X2*X3 e 5.91*X21 e 4.36*X22 e 5.43*X23 (2)
 N.F. Sulaiman et al. / Renewable Energy 113 (2017) 697e705 703

(a) (b)

Al O

(c) (d)

Ca C

Fig. 5. EDX mapping image prole of Cr/Ca(10:90)/g-Al2O3 catalyst calcined at 700
C for 5 h [(a: alumina compound), (b: oxygen compound), (c: calcium species), (d: chromium
species)].

Fig. 6. CO2-TPD curves for Cr/Ca(10:90)/g-Al2O3 catalyst at calcination temperature of 600, 700 and 800
C for 5 h respectively.

Table 6
Table 5
ANOVA results of the response surface quadratic model for percentage conversion of
CO2 desorbed temperature and amount of Cr/Ca(10:90)/g-Al2O3 catalysts at different
biodiesel.
calcination temperatures of 600, 700 and 800
C for 5 h derived from CO2-TPD.
Source Freedom degree Sum of squares Mean squares F-value p-value
Calcination temperature Temperature of desorbed Quantity of desorbed
of catalyst (
C) peak CO2 (
C) CO2 (mmol/g) Model 9 441.18 49.02 14005.65 <0.0001a
X1 1 4.65 4.65 1328.93 <0.0001
600 125.5 0.20200
X2 1 0.21 0.21 60.36 0.0001
222.3 2.43832
X3 1 38.72 38.72 11062.86 <0.0001
700 146.3 0.73139
X1X2 1 0.72 0.72 206.43 <0.0001
261.2 1.71247
X1X3 1 5.29 5.29 1511.43 <0.0001
327.2 0.93760
X2X3 1 0.01 0.01 2.86 0.1348
800 149.1 0.56303
X21 1 146.94 146.94 41983.23 <0.0001
258.7 2.05008
X22 1 79.95 79.95 22842.47 <0.0001
X23 1 124.26 124.26 35503.23 <0.0001
Residual 7 0.025 0.0035
Lack of t 3 0.013 0.004167 1.39 0.3678b
be seen that the Cr loading had signicant effect on the conversion
Pure error 4 0.012 0.003
of biodiesel since increasing the Cr loading as dopant to based Total 16 441.20
would increase the conversion of biodiesel until achieving the
R-Sq 0.9999, R-Sq (adj) 0.9999, R-Sq (pred) 0.9995.
optimum value. Furthermore, in Fig. 7c, it shows that the conver- a
Signicant.
sion of biodiesel was also inuenced by Cr loading and number of b
Not signicant.
alumina coatings while calcination temperature was kept constant
704 N.F. Sulaiman et al. / Renewable Energy 113 (2017) 697e705
(a)
(b)
(c
Fig. 7. 3-D surface plots of conversion of biodiesel as a function of (a) calcination temperature and number of alumina coatings, (b) calcination temperature and Cr loading as
dopant, (c) Cr loading as dopant and number of alumina coatings.
at 700
C.
Therefore, the important degree of these parameters follows the
order of calcination temperature > Cr loading as dopant > number
of alumina coatings which also can be evaluated in Table 6. In order
to obtain the optimum condition for this model, the lower and
upper limit of each variable was adjusted to achieve the maximum
conversion of biodiesel. Therefore, the optimum condition achieved
from this model was 11.25 wt% of Cr loading as dopant with
calcination temperature of 696.5
C and 2.92 times of alumina
coatings. The estimation conversion of biodiesel was high with
93.30%. An additional experiment was conducted under the opti-
mum conditions to conrm the agreement of the model and the
experimental results. The experimental value achieved with 93.10%
conversion of biodiesel closely agreed with the predicted result
from RSM and hence validated the ndings of response surface
optimization.
4. Conclusion
The modication of the Ca/g-Al2O3 catalyst by adding Cr as a
dopant could exhibit excellent catalytic activity. The optimum
operating conditions of 11.25 wt% of Cr loading as dopant with
calcination temperature of 696.5
C and 2.92 times of alumina
coatings would be the ideal conditions for the catalytic activity on
the conversion of biodiesel that gave 93.30% by using Cr/Ca/g-Al2O3
catalyst. From the analysis, the calcination temperatures and Cr
loading as a dopant play an important role in catalytic activity study
as veried by BoxeBehnken experimental design. Verication ex-
periments conrmed the validity of the predicted model in which
the optimum conditions for catalyst obtained with 3 times number
 N.F. Sulaiman et al. / Renewable Energy 113 (2017) 697e705
of alumina coatings, 10:90 dopant ratio to based and calcined at
700
C gave the maximum conversion of biodiesel, 93.10%. BET and
CO2-TPD data supported the results which gave high surface area,
164.32 m2/g and highest total amount of basic sites, 3.38 mmol/g
respectively, that inuenced the catalytic activity of trans-
esterication process. EDX mapping for each element in Cr/
Ca(10:90)/g-Al2O3 catalyst was well-distributed and indicated that
the Cr/Ca has a higher dispersion on the surface of g-Al2O3.
Acknowledgment
The authors would like to thank the Ministry of Education,
Malaysia and Universiti Teknologi Malaysia (UTM) for their nan-
cial funding through FRGS Grant Vote No 4F740 and MOSTI for
MyBrain15 scholarship.
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