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Energy 89 (2015) 965e973

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Energy
journal homepage: www.elsevier.com/locate/energy

Biodiesel synthesis over millimetric g-Al2O3/KI catalyst


Aminul Islam a, b, Yun Hin Tauq-Yap a, b, *, Pogaku Ravindra c, Siow Hwa Teo a, b,
S. Sivasangar a, b, Eng-Seng Chan d, **
a
Department of Chemistry, Faculty of Science, University Putra Malaysia, 43400 UPM Serdang, Selangor, Malaysia
b
Catalysis Science and Technology Research Centre, Faculty of Science, University Putra Malaysia, 43400 UPM Serdang, Selangor, Malaysia
c
Centre of Materials and Minerals, School of Engineering and IT, Universiti Malaysia Sabah, 88999 Kota Kinabalu, Malaysia
d
Chemical Engineering Discipline, School of Engineering, Monash University, Jalan Lagoon Selatan, 46150 Bandar Sunway, Selangor, Malaysia

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

Article history: The use of spherical millimetric gamma-alumina (g-Al2O3) as a catalyst support for the production of
Received 4 August 2014 biodiesel from palm oil was demonstrated. The catalyst support was produced using dripping method,
Received in revised form and KI catalyst was loaded on the support using impregnation method. The highest FAME (fatty acid
23 April 2015
methyl ester) yield of 98% was obtained when the reaction was carried out under the conditions of
Accepted 11 June 2015
catalyst to oil ratio of 0.6 g (4wt.%, gcat./goil) using 0:24 gKI =ggAl2 O3 of catalyst loading, reaction time of 4 h,
Available online 2 July 2015
temperature of 60  C and methanol to palm oil molar ratio of 14:1. XRD (X-ray diffraction) analysis
showed the formation of K2O and KAlO2 phases on the KI/g-Al2O3 catalyst which were possibly the active
Keywords:
Solegel
sites for the transesterication reaction. The highest number and strength of basic sites generated from
g-alumina the solid phase reaction of the KI/g-Al2O3 catalyst loaded with 0.24 g kF/g g-Al2O3 were conrmed by
Calcination temperature programmed desorption of CO2 (CO2-TPD) analysis. The nitrogen adsorptionedesorption
Transesterication isotherms was revealed a mesoporous structure of the catalysts. The leaching of potassium species in
Biodiesel reused catalysts was observed, as veried by XRF (X-ray uorescence). KI/g-Al2O3 had a long life time and
maintained sustained activity even after being repeatedly used for 11 cycles. The biodiesel yield was
comparable to that produced from smaller catalysts. Thus, the catalyst could be potential for industrial
use, as they can be handled safely, easily separated from the process uid and used in xed bed reactor to
minimize pressure drop.
2015 Elsevier Ltd. All rights reserved.

1. Introduction KI/g-Al2O3 [5], KOH/ZrO2 [6], KNO3/Al2O3 [7] and K/KOH/g-Al2O3


[8]. Recently, the utilization of supported nano catalyst has been
The most effective way to reduce CO2 (carbon dioxide) emis- shown to be efcient for biodiesel production [9e11].
sions is to reduce fossil fuel consumption. Therefore, the biodiesel is Despite the high percentage of FAME (fatty acid methyl ester)
gaining more attention as a carbon neutral source of energy. Recent (>90%) achieved by powdered catalysts, many catalytic systems
research efforts have been directed towards the more economical have not been commercialized because of the difculties encoun-
and environmental friendly way to produce biodiesel using solid tered when trying to separate such catalysts from the reaction
catalysts [1,2]. A number of studies have been focused on using media [12]. In addition, the small particle size gives rise to several
solid basic or acidic catalyst for biodiesel production. Different problems such as high pressure drops, poor mass/heat transfer,
types of powdered solid basic catalysts ordering on a micrometer poor contact efciency and difculties in handling and separation
scale have been studied, including KI/Al2O3 [3], CaO/KI/g-Al2O3 [4] [13,14]. There are also possible health risks caused by inhalation of
small particles. Therefore, the fabrication of catalyst with macro-
scopic form could be useful for industrial applications, as reported
* Corresponding author. Department of Chemistry, Faculty of Science, University
by Wang et al. [15].
Putra Malaysia, 43400 UPM Serdang, Selangor, Malaysia. Tel.: 60 3 55145821; One of the main reasons to consider heterogeneous catalysis for
fax: 60 3 55146207. industrial processes is the ease of catalyst separation after the re-
** Corresponding author. action. Separation processes represent more than half of the total
E-mail addresses: tauq@upm.edu.my (Y.H. Tauq-Yap), chan.eng.seng@
investment in equipment for the chemical and fuel industries [16].
monash.edu (E.-S. Chan).

http://dx.doi.org/10.1016/j.energy.2015.06.036
0360-5442/ 2015 Elsevier Ltd. All rights reserved.
966 A. Islam et al. / Energy 89 (2015) 965e973

Thus, the utilization of millimetric spherical catalyst support and appropriate amount of 1N HCl, where the sol turned to a gel. The
their application in transesterication reactions will be a practical gel was then transferred dropwise by a pump at a constant ow
alternative to catalyst in powder form in view of following advan- rate (0.5 mL/min) into a liquid column consisting of parafn oil at
tages; i) easy of separation of the catalyst by simple ltration, ii) the the upper layer and ammonia solution at the bottom layer (Fig. 1).
catalyst is easy to handle and reusable for several times. In addition, Droplets of boehmite gel were formed due to the surface tension
in the design of a catalyst, the shape should also be taken into ac- effect during transiting through the oil layer and the gel droplets
count, as the shape preferably, spherical could minimize the abra- were further aged in the ammonia solution for 1 h. The parafn
sion of catalyst in the reaction medium [17]. In fact, the life time of solution column was 25 cm in height, which provided enough
the catalyst could be increased. Until now, the macroscopic (up to time for the gel drops to form spherical particles [19,20]. During
1.0 mm in diameter) magnesia-rich magnesium aluminate spinel aging, ammonia would neutralize the acid in the wet-gel beads
catalyst, such as MgO$MgAl2O4 and MgO/MgAl2O4/g-Al2O3 for and thus, the wet-gel droplets became rigid. Then, the beads were
biodiesel production have been reported by Wang et al. [15]. then dried in the air at room temperature (25  C) for 12 h and
However, the biodiesel yield was still insufcient for practical ap- were later calcined at 800  C for 3 h. The calcined beads were then
plications. For instant, biodiesel yield obtained with the catalyst impregnated with an aqueous solution of KI (potassium iodide), as
MgO$MgAl2O4 and MgO/MgAl2O4/g-Al2O3 were substantially low shown in Table 1. Finally, the bead-supported catalysts were
at 57% and 36% respectively in 10 h. calcined at 500  C for 3 h to make the catalyst active for trans-
The aim of this work was to improve the biodiesel yield from esterication reaction.
transesterication of palm oil using a spherical millimetric gamma-
alumina (g-Al2O3) catalyst support. g-Al2O3 was chosen because it 2.3. Catalyst characterization
can easily be synthesized, it possesses good support properties, and
it is commercially available. KI (potassium iodide) was used as a The shape and size analysis of the support beads were carried
model catalyst. The catalysts were prepared at different loading out by analyzing the digital images captured by a digital camera
contents, and the effects of these catalysts on the transesterication (Moticam-350, version 2.0 ML, China) installed on a stereozoom
reaction were evaluated in terms of the FAMEs yield. In addition, microscope (Stemi DV4, Carl Zeiss, Germany) using image analyzer
the characteristics of the synthesized catalysts, such as the (SigmaScan Pro 5.0, SPSS Inc). In order to measure the shape of the
morphological, structural, textural and base properties, were car- bead quantitatively, SF (sphericity factor) was used. It express the
ried out using stereozoom microscopy, XRD (X-ray diffraction), N2 divergence of a particle shape from spherical [21], where the value
adsorption/desorption isotherms and CO2-TPD (temperature-pro- zero indicates a perfect sphere and higher values indicate a greater
grammed reduction) techniques. A screening of the reaction con- degree of shape distortion. SF was calculated according to eq. (1):
ditions has been carried out by examining the effects of reaction  
time, methanol to oil molar ratio and the calcination temperature of SF Dmax  Dper Dmax Dper (1)
catalyst. Besides, the relationship between the basicity of the
catalyst and their catalytic activity in the transesterication of palm where Dmax is the maximum diameter passing through a bead
oil was also discussed. Finally, the reusability of the catalyst was centroid (mm), and Dper is the diameter perpendicular to Dmax
determined and the leachate of catalyst into the reaction product passing through the bead centroid (mm).
was veried by XRF (X-ray uorescence). The crystal structure of the catalyst was determined by Shi-
madzu diffractometer model XRD-6000 using Cu-Ka radiation. The
2. Materials and methods samples were scanned from 10 to 70 with a speed of 0.05 s1. The
peaks were analyzed with the DiffracPlus software and the phases
2.1. Materials were identied by the PDF (powder diffraction le) database
(JCPDS, International Centre for Diffraction Data).
Boehmite (AlOOH) in a powder form was provided by BASF The basicity of the catalyst was determined by temperature
Catalysis LLC, USA. Reagents used during catalyst synthesis were: programmed desorption of CO2, as described by Islam et al. [17].
hydrochloric acid, HCl (JT Baker, Mexico), ammonia solution (Sys- The experiments were performed by loading the samples (100 mg)
tem ChemAR, Malaysia), parafn oil (870 g/mL density at 20  C, in the Thermo Finnigan TPD/R/O 1100 series catalytic surface
Ajax chemicals, Australia) and potassium iodide, KI (Sigma-Aldrich, analyzer connected to a thermal conductivity detector. The samples
GmbH, Germany). Commercial edible grade palm oil was purchased were preheated to 800  C under a owing stream of helium for
from a local store (Lam soon edible oil, Malaysia). Methanol (Lab- 30 min (10  C min1, 30 mL min1). Then, the temperature was
scan Asia Co. Ltd. Thailand) was used for the transesterication decreased to 30  C under a CO2 ow for 1 h (30 mL min1) at which
reactions and hexane was purchased from Fisher Scientic, UK. the adsorption of CO2 will be carried out. Subsequently, the sample
Methyl heptadecanoate (internal standard for gas chromatography) was ushed with helium at 30  C for 30 min in order to remove any
and standard references for fatty acid methyl ester analysis were physisorbed molecules from the samples prior to the CO2 desorp-
supplied by Fluka Analytical (Buchs, Switzerland). tion analysis. The desorption of CO2 was carried out by heating the
sample up to 800  C under a helium ow (10  C min1,
2.2. Preparation of catalyst 30 mL min1) and the amount of desorbed CO2 was detected and
determined using a thermal conductivity detector.
Spherical millimetric gamma-alumina (g-Al2O3) support was The surface area and pore structure of catalysts were deter-
prepared using oil drop granulation method described in previous mined at liquid nitrogen temperature (196  C) with a Sorptomatic
publications [18e20]. Spherical millimetric gamma-alumina (g- 1990 (Thermo Finnigan Italia S.P.A) instrument. Prior to the mea-
Al2O3) support was prepared using a solegel process previously surements, the samples were degassed at 150  C under vacuum
described by Wang et al. [18]. The boehmite powder (300 g/L) was conditions until static vacuum was reached. The BET (Brunauer,
suspended in deionized water and dispersed ultrasonically by a Emmett and Teller) method was used to measure the surface area of
sonicator. The sonication process took place for 3 min at ampli- the catalysts. The BJH (Barrett, Joyner and Halenda) method was
tude of 70%. The pH of the resulting boehmite suspension prior to employed to measure the pore distribution from the desorption
drop formation was then adjusted to 1.0 by addition of an isotherm. The pore volume was calculated according to the
A. Islam et al. / Energy 89 (2015) 965e973 967

Fig. 1. Apparatus for production of millimetric catalyst.

Gurvitch method. The analysis was automatically performed by the was recovered from the reaction mixture by simple ltration. The
Thermo Finnigan Sorptomatic 1900 series nitrogen adsorption/ ltrate was then centrifuged at a relative centrifugal force of 2500 g
desorption analysis software. for 10 min, and then excessive amount of methanol was evaporated
Elemental analysis on the reused catalyst was carried out by X- before analysis of biodiesel yield.
ray uorescence in a Shimadzu EDX 720 spectrometer with a The fatty acid composition was determined by gas chromatog-
rhodium X-ray source tube. The sample was placed on powders raphy using an internal standard. The samples were analyzed by a
placed inside the sample holder using a polypropylene lm. The Shimadzu GC-14B gas chromatograph equipped with a FID (ame
analysis were performed under vacuum conditions (<45 Pa) using ionization detector) and a capillary column Rtx-65
2-channels where the X-ray source was set at 50 and 15 kV for TieU (30 m  0.5 mm  0.25 mm). The injector and detector tempera-
(Titanium eUranium) and NaeSc (SodiumeScandium) ranges, tures were 240 and 280  C, respectively. Methyl heptadecanoate
respectively and the metal oxide content of the catalysts was (0.1 g) was dissolved in 100 mL of hexane to prepare the standard
measured automatically by the instrument software. solution. In all, 0.2 g of biodiesel sample was dissolved in 10 mL of
standard solution for GC analysis and 0.5 mL sample was injected
into the GC which uses helium as a carrier gas. The chromato-
2.4. Transesterication reaction conditions
graphic prole of the mixture of the standards and the biodiesel
product was shown in Fig. 2. The content in FAME (fatty acid methyl
In a batch process, all the reactions were performed in a 50 ml
ester) yield was determined in accordance with European regulated
bafed conical ask (Corning, USA) placed in an incubator orbital
procedure EN 14103 [17]. The experiments were duplicated and
shaker equipped with a temperature controller. In a typical assay,
data shown were the average values within 2.5% errors.
palm oil 15 g, catalyst 0.6 g (4 wt.%, gcat/goil) were placed together
To calculate the biodiesel yield, the response factors, Rf for each
inside the conical ask. The molar ratio of oil and methanol was
compound have been calculated using the correspondent standard
adjusted as 1:14 according to the literature [22]. The reactions were
compound according to the Eq. (2).
performed at 60  C over a period of 4 h. During the optimization
studies, the effect of time (1e6 h), molar ratio of methanol to oil
(8e18) and catalyst loading (0.6e0:33 gKI =ggAl2 O3 ) on the FAME    
Ais Crs
yield were investigated. The reaction mixture was stirred at an Rf  (2)
Ars Cis
agitation speed of 250 rpm to allow good contact between the
catalyst and reactants. After completion of the reaction, the catalyst

Table 1
Impregnation of catalyst.

Step-1 Step-2 Step-3 Step-4 Step-5

Catalyst (g) for Catalyst (g) for Total weight of Volume of aqueous solution Calcination Total The calcinated catalyst,
1 g support 3 g of support catalyst and (ml) with catalyst and 3 g weight (g) g (catalyst support) used
support (g) of support was immersed for biodiesel production
(4 wt%, g cat./g oil)

0.06 3  0.06 0.18 3.18 4.5 Calcination of z2.5 0.6


0.15 3  0.15 0.45 3.45 4.5 impregnated catalyst 0.6
0.24 3  0.24 0.72 3.72 4.5 0.6
0.30 3  0.30 0.90 3.90 4.5 0.6
0.33 3  0.33 0.99 3.99 4.5 0.6
968 A. Islam et al. / Energy 89 (2015) 965e973

Fig. 2. Gas chromatograms of (a) standard methyl ester and (b) biodiesel product.

where, Ais area of internal standard, Cis concentration of in- reused. The same amount of palm oil and methanol were added to
ternal standard, Ars area of standard references, the recycled catalyst each time to react under the same conditions.
Crs concentration of standard references. This procedure was repeated several reaction cycles to examine the
The ME (methyl ester) was calculated using Eq. (3): extent of stability of the catalyst.

Ciss  Aif  Rf 3. Results and discussion


ME (3)
Aiss
3.1. Shape and size of g-Al2O3 beads
where, Ciss concentration of internal standard in the sample,
Aiss area of internal standard in the sample, Aif area of in- The optical photograph of the millimetric g-Al2O3 support beads
dividual FAMEs compound in the sample. are shown in Fig. 3. As evidenced by Fig. 3, the beads shape was
The biodiesel yield (%) was according to the Eq. (4): close to a sphere with a diameter of 2 mm. The SF (sphericity factor)
of the beads was 0.02 0.01 which can be considered as a spherical
total amount of methyl ester mol
Biodiesel yield % bead, as reported by Chan et al. [23].
3  charged amount of triglycerols mol
 100 3.2. Structure and basicity of catalyst
(4)
The XRD patterns of support materials g-Al2O3 and synthesized
catalysts with various loading amount are shown in Fig. 4. As can be
2.5. Catalyst reusability seen, curve (a) had a typical XRD pattern of g-Al2O3 at 2q values of
31.9 , 37.6 , 39.5 , 45.8 and 66.7 (JCPDS File No. 00-029-0063). In
Catalyst reusability test were performed by repeating the the sample with a low loading of 0:06 gKI =ggAl2 O3 (curve b) had
transesterication over an extended period of time with used cat- similar patterns, identical to that of the g-Al2O3 (31.9 , 37.6 , 39.5 ,
alysts. When the transesterication reaction was completed, the 45.8 and 66.7 ). Considering the low potassium loading amounts,
catalyst was recovered by ltration, washed with water, dried at the absence of diffraction lines of potassium compounds may be
100  C for 1 h to remove the moisture content and subsequently assigned to their high degree of dispersion in the form of a
A. Islam et al. / Energy 89 (2015) 965e973 969

calcination conditions at loadings 0.24 g/g g-Al2O3. A conclusion


has been reached by Xie and Li [3] that the KI supported alumina
catalyst can be decomposed at 500  C to form metal oxide phases,
which was referred as active sites for transesterication reaction.
These results also agree well with the results of KI/Al2O3 reported
by Xie and Zhao [25]. When the loading amount achieved
0:30 gKI =ggAl2 O3 , the characteristics peaks of g-alumina (JCPDS File
No. 00-029-0063) at 2q 66.7 and potassium iodide (JCPDS File
No. 00-004-0471) at 2q 21.7, 25.2 , 35.9 , 42.4 , 44.3 and 58.3
was appeared in the diffraction patterns (curve e) and more intense
when the KI loading was increased to 0.33 g/g-Al2O3 (curve f). This
observations could be associated with the over loading of KI on to
the g-Al2O3 support. The over loaded KI masked the metal oxide
phase and appeared in the diffraction pattern at the loading of
0.30e0.33 g/g-Al2O3.
The strength and number of basic sites of the catalysts were
analyzed by CO2-TPD. In general, the stronger the basic site of a
catalyst, the higher the temperature is needed to desorb the
Fig. 3. Optical photograph of KI/g-Al2O3 catalyst. adsorbed CO2. It has been reported that the basicity of supported
basic catalyst is dependent on the presence of oxide or/and hy-
droxide groups on the catalyst surface [26]. The TPD proles of
monolayer on the g-Al2O3 surface, or to their amounts being desorbed CO2 on KI/g-Al2O3 catalysts are shown in Fig. 5. The re-
smaller than those detectable via the XRD technique [24]. An sults showed complex desorption proles, which could be due to
alternative reason for the absence of diffraction lines of potassium the presence of a variety of basic sites of different strength. The
compounds may be due to the higher scattering factor of the K desorption peak at a temperature of 147e169  C can be attributed
cations, which is comparable to that of the Al cations in the cat- to the interaction of CO2 with the sites of weak basic strength. It has
alysts [24]. When the catalyst loading was increased to 0.15 gKI/gg- been proposed that these sites are assigned to the presence of OH
Al2O3 (curve c), the characteristic peaks of KI (JCPDS File No. 00-023- groups on the catalyst surface [26]. Moreover, strong and sharp
0493) (2q 21.7, 25.2 ) was observed implying that the amounts peaks appeared at 299e312  C, which are characteristics of CO2
of salts within its detectable limit of XRD. The diffraction lines desorption from the medium strength of basic sites. Basic sites of
(curve d) assigned to K2O (JCPDS File No. 00-023-0493) at high strength, which is related to free O2 anions located in a
2q 23.8 and 27.6 and KAlO2 phase (JCPDS File No. 00-002- particular position of the mixed oxide surface are characterized by
0897)) at 2q 38.9 appeared with the KI catalyst loading of 0.24 g/ the presence of desorption peak at 613e634  C [26].
g g-Al2O3. A similar observation was obtained in the case of KNO3/ The total number of basic sites of the catalyst is shown in Table 2.
Al2O3, where it was found that the alkali metal oxides and alkali- The total basicity was found to increase with KI loading and reached
aluminate crystalline structure were the catalytically active sites a maximum of 867 mmol/g at KI loading of 0:24 gKI =ggAl2 O3 . It was
to catalyze the transesterication reactions [7]. The KI peak could reported by Chorkendorff and Niemantsverdriet [27] that the oxide
still be detected at a loading of 0.24 g/g g-Al2O3 although the in- phases provide sufcient adsorptive sites for the probe molecules
tensities of these peaks were not as high as those observed for with acidic character (CO2). Thus, the generation of active oxide
loadings above 0.24 g/g g-Al2O3. Based on these results, it is phases such as, K2O, KAlO2 phases on KI/g-Al2O3 catalyst at 0.24 g/g
reasonable to state that only a part of the KI decomposed under

Fig. 4. XRD patterns for samples (a) g-Al2O3, (b) 0:06 g gKI =ggAl2 O3 , (c) 0:15 gKI =ggAl2 O3 , Fig. 5. CO2-TPD spectra for samples (a) g-Al2O3, (b) 0:06 g gKI =ggAl2 O3 , (c)
(d) 0:24 gKI =ggAl2 O3 , (e) 0:30 gKI =ggAl2 O3 , (f) 0:33 gKI =ggAl2 O3 . 0:15 gKI =ggAl2 O3 , (d) 0:24 gKI =ggAl2 O3 , (e) 0:30 gKI =ggAl2 O3 , (f) 0:33 gKI =ggAl2 O3 .
970 A. Islam et al. / Energy 89 (2015) 965e973

Table 2 Table 3
Effect of KI loading on basicity of KI/g-Al2O3 beads. The surface area and pore structure of KI/g-Al2O3 catalyst.

Catalyst KI loading on g-Al2O3 The amount desorbed CO2 (mmol/g catalyst) Catalyst KI loading on Surface area Pore volume Pore diameter
g-Al2O3 (m2/g) (cm3/g) (nm)
g-Al2O3 _ 19
KI/g-Al2O3 0.06 198 g-Al2O3 _ 349 1.38 11.2
0.15 318 KI/g-Al2O3 0.06 326 1.09 9.0
0.24 867 0.15 299 0.84 7.3
0.30 466 0.24 277 0.63 7.0
0.33 457 0.30 244 0.49 3.9
0.33 133 0.43 3.5

gAl2O3, as evident from XRD (Fig. 4; curve d) may desorb higher


CO2 and thus, increase the basicity. decreased when the KI loading was increased from 0.06 g to 0.33 g/
However, the decrement in basicity for both catalysts at loadings g g-Al2O3. This decrement of surface area has been previously
above 0.24 g/g g-Al2O3 was observed. These observations could be observed and attributed to the effect of catalyst deposition on the
due to the overloading of KI that saturated the g-Al2O3 surface. As a support, which resulted in partial blocking of the porous network
result, the dispersion of excess KI could mask the actives K2O, KAlO2 [29].
sites and incapacitate the function of active base site in the struc-
ture of catalyst at higher loadings. Therefore, the basicity of the
catalyst might be reduced. Similar observations have been found by 3.4. Catalytic activity
Tauq-Yap et al. [28] and reported that a decrease in basicity at high
catalyst loading was due to reduction of active bases in the struc- The activity of catalysts was evaluated in the transesterication
ture of catalyst. A mechanism has also been proposed by Xie et al. of palm oil with methanol in terms of FAME (fatty acid methyl
[7] to explain the decrease of basic sites with increasing catalyst ester) yield at different catalyst loadings, as shown in Fig. 7. When
loading. It has been suggested that the vacancies formed in the
alumina structure during the thermal treatment favours the
migration of metal K ions of KI salt to the vacant sites that sub-
sequently decompose to form basic sites. When the amount of salt
loaded on g-Al2O3 is more than the saturation uptake, it could not
likely be decomposed to create basic oxide sites on the catalyst [7].

3.3. Surface area and pore structure of catalyst

The nitrogen adsorptionedesorption isotherms and pore size


distributions of the g-Al2O3 support are shown in Fig. 6. The
isotherm corresponded to type IV according to the IUPAC classi-
cation and showed a characteristic hysteresis loop in the relative
pressure (P/P0) range 0.8e1.0 associated with capillary condensa-
tion taking place in mesopores (Fig. 6a). The pore size distributions
of the g-Al2O3 support are unimodal, with pore diameters centred
in the range 5.8e6.1 nm (Fig. 6b).
Table 3 shows the results of surface area the surface area, pore Fig. 7. Effect of catalyst loading on FAME yield. Reaction conditions: methanol/oil
volume and pore diameter of the catalysts at different loadings. As molar ratio 14:1, reaction time 4 h, reaction temperature 60  C, catalyst amount 0.6 g
evidenced by the data in Table 3, the surface area and pore volume (4wt.%, gCat./goil) and catalyst calcined at 500  C.

Fig. 6. N2 adsorptionedesorption isotherm (a) and BJH pore size distribution (b) of the millimetric g-Al2O3 beads.
A. Islam et al. / Energy 89 (2015) 965e973 971

Fig. 8. Proposed mechanism of basic catalyst [27].

the catalyst loading increased from 0.06 to 0.24, the FAME yield was
Fig. 9. Effect of reaction time on FAME yield. Reaction conditions: methanol/oil molar
increased dramatically from 51 to 98 % due to a concomitantly ratio 14:1, catalyst loading 0:24 gKI =ggAl2 O3 , reaction temperature 60  C, catalyst
remarkable increase in surface basicity in the heterogeneous amount 0.6 g (4 wt.%, gCat./goil) and catalyst calcined at 500  C.
contribution of lower concentration of KI. Beyond the loading of
0.24, a signicant decrease in basicity to 466 mmol/g catalyst (0.3 g
KI/g Al2O3), although the catalyst maintained the higher FAME yield strength, stronger bases are in general more effective to initiate the
of 90%. This phenomenon indicate that the KI compound in the transesterication of triglycerides [34]. As per the TPD-CO2 result,
catalyst can dissolved readily into the polar phase (methanol) to the higher level of base strength (curve c in Fig. 5) at a loading of
form potassium methoxide as the homogeneous contribution of 0.24 g/g g-Al2O3 might result in higher biodiesel yield compared
catalyst, thus promising biodiesel yield due to its superior mass with the other loadings.
transfer characteristics. The porous properties were shown in Table 3. The mesoporous
The trend of the FAME yield can be related to the basic sites of characteristic (i.e. 7 nm in diameter) of the support beads at
metal oxides where the maximum basicity was achieved at 0:24 gKI =ggAl2 O3 loading might also permit access of bulky mole-
0:24 gKI =ggAl2 O3 (see Table 1). The basic sites of metal oxide can cules (i.e. triglycerides) to the active sites resulting substantial in
work synergetically with Lewis acid sites constituting acid-base increase catalytic activity [35]. However, pores with diameter of
pair sites [30]. It was reported by Chorkendorff and Niemantsver- less than 5 nm were occupied in the catalysts volume in the case of
driet [27] that metal oxide provides sufcient adsorptive sites for higher loading of KI (more than 0:24 gKI =ggAl2 O3 ). If, as some
alcohol in transesterication reaction and concluded that the high workers [36] have suggested, the triglyceride molecule can be
transesterication activity of catalyst might be due to the mani- diffused into catalyst having pore diameter of more than 5 nm then,
festation of the dissociation of alcohol to RO and H on basic sites diffusion of the triglyceride molecule could be restricted when the
of metal oxide catalyst surface (Fig. 8). Thus, the high yield of bio- diameter of the catalyst was less than 5 nm and this would in turn,
diesel could be attributed to the generation of oxides phases such be decreased the catalytic activity.
as, K2O, KAlO2 phases, as evident from XRD (curve d in Fig. 4) The effect of reaction time on the FAME yield was investigated,
formed at catalyst loading of 0:24 gKI =ggAl2 O3 , which can be as shown in Fig. 9. The FAME yield increased from 11% to 98% as the
considered as active sites for transesterication reactions, as pro- reaction time was increased from 1 to 4 h and remained constant
posed by Xie and Zhao [25]. A similar observation was obtained in thereafter, indicating an equilibrium FAME yield. Fig. 10 shows the
the case of KNO3/Al2O3, where it was found that the alkali metal effect of methanol/oil molar ratio on the FAME yield. According to
oxides and alkali-aluminate crystalline structure were the catalyt-
ically active sites to catalyze the transesterication reactions [7].
Other workers [31] reported that the formation of alkali metal
oxides and alkali-aluminate crystalline structure were the catalyt-
ically active sites for transesterication reaction, although Xie et al.
[32] suggested from their work that the formation of active oxide
phase largely depends on the proper metal loading during prepa-
ration of the supported catalyst.
However, the loadings may be reached above its saturation
uptake at higher than 0:24 g=ggAl2 O3 and thus, the decomposition
of catalyst might be precluded, as evident from XRD. Therefore, the
basicity as well as the catalyst activity might be reduced. This
observation is in agreement with the results reported by Boz and
Kara [33] who concluded from their work that the high basic
strength and basicity of the catalysts could improve trans-
esterication process. It can be inferred from the foregoing dis-
cussion that the formation of the oxide phase at the loading of
0.24 g/g g-Al2O3 may contribute to higher basicity (Table 2) as well
as catalytic activity towards the transesterication reaction (Fig. 7).
In addition, the biodiesel yield could also be affected by the level Fig. 10. Effect of methanol/oil molar ratio on FAME yield. Reaction conditions: reaction
of strongly basic sites present in the catalysts. As the ability of bases time 4 h, catalyst loading 0:24 gKI =ggAl2 O3 , reaction temperature 60  C, catalyst amount
to abstract a proton from a alcohol is directly connected to the base 0.6 g (4 wt.%, gCat./goil) and catalyst calcined at 500  C.
972 A. Islam et al. / Energy 89 (2015) 965e973

Table 4
Comparison of biodiesel yield.
g h
Catalyst Reaction condition BY (%) BP Reuse catalyst References

Oil type a
RT ( C) b
Cat. (g) Oil (g) c
M/O d
Rt (h) e
BD (g) Calcination
Cycle g
BY (%)

CT ( C)
f
t(h)

KI/Al2O3 Soybean MR 0.4 16 15:1 8 15.36 500 3 96 0.12 _ _ [25]


C4H4O6HK/ZrO2 soybean 60 1 18.22 16:1 2 17.86 512 5 98.03 0.49 5 89 [37]
KOH/Al2O3 palm 60 3 100 15:1 2 91 500 3 91 0.45 _ _ [38]
Ca(NO3)2/Al2O3 palm 60 1 10 65:1 3 9.4 450 4 94 0.31 _ _ [39]
KNO3/Al2O3 palm 60 1 10 65:1 3 9.47 550 4 94.7 0.31 _ _ [39]
KF/Al2O3 sunower 75 0.25 28 4:1 2 27.44 450 2 98 0.47 4 88 [40]
Egg shell Soybean 65 0.69 23 9:1 3 21.85 800 2 95.5 0.32 13 95 [41]
CaO/Al2O3 palm 65 3 50 12:1 5 49.32 718 5 98.64 0.19 2 91 [42]
KOH/iAC palm 64 5 50 24:1 1 49 __ __ 98 0.98 3 87 [43]
KI/gAl2O3 Palm 60 0.6 15 14:1 4 14.5 500 3 98 0.24 11 79 Present study

All of the reactions were performed under atmospheric pressure.


a
Reaction temperature.
b
Catalyst used for reaction.
c
Molar ratio of methanol to oil.
d
Reaction time.
e
Biodiesel.
f
Calcination temperature of the catalyst.
g
Biodiesel yield (%) biodiesel(g)/oil (g)  100.
h
Biodiesel productivity biodiesel (g)/oil(g) time.
i
Activated carbon.

reaction stoichiometry, 3 mol of methanol are required to react 3.5. Catalyst reusability
with each mole of triglyceride, but in practice a higher molar ratio is
employed in order to drive the reaction towards completion and The stability of KI/g-Al2O3 catalyst was evaluated by performing
produce more methyl esters as product. The yield was found to the reusability test on the catalyst. Fig. 11 presents the effect of
increase considerably and reached a maximum when the meth- catalyst reuse on the FAME yield. The amount of the biodiesel yields
anol/oil molar ratio was increased to 14, beyond which no further after the 11th cycle obtained in this work was 79%, which is com-
increment in yield could be observed. The observations are in parable in biodiesel yield to that of the results obtained in previous
agreement with previous reports [37]. studies (see Table 4). The XRF results (Table 5) show that the
The comparison of the FAME yield was compiled in Table 4. The amount of K2O in the catalyst, after the rst and eleventh cycles,
results showed that the biodiesel yield produced using the spher- was 24% and 19%, respectively. This could be due to the leaching of
ical millimetric g-Al2O3 supported catalyst is comparable to that K2O from the g-Al2O3 support. It was reported by several re-
reported in the previous studies. One of the main reasons to searchers [7,25,39,44] that the activity of the alumina supported
consider heterogeneous catalysis for industrial processes is the ease catalyst such as KI, KF, HNO3, K2CO3, NaNO3, or KOH was reduced
of catalyst separation after the reaction. Therefore, the easy sepa- after successive reuse due to the leaching of active species.
ration of catalyst from process uid and the safe handling are the Although the catalyst was reused for 11 times, it showed good
two of the main rationale to select the millimetric spherical catalyst mechanical stability as the support remained spherical with no sign
for biodiesel production. of disintegration (see Fig. 12). This indicates its potential for use in
industrial environment. However, the problem with metal leaching
from the solid supported catalyst is still a major consideration due
to the cost of recovery or replacement of the catalyst. A method of
controlling metal leaching in supported solid catalysis has been
proposed by Hunter et al. [45] who concluded from their work that
stronger bond with the metal complex formed by the inclusion of
legands could be controlled leaching of the active phase from a
solid catalyst. Other workers [46] have also discussed a similar
phenomenon and have suggested that the incorporation of

Table 5
Elemental analysis of reused KI/g-Al2O3.

Component Elemental composition (%)

1st Reuse 7th Reuse 11th Reuse

Al2O3 45.964 67.162 73.62


K2O 53.319 32.296 26.14
SO3 0.58 0.435 0.16
CuO 0.087 0.067 0.04
ZnO 0.05 0.04 0.04
Fig. 11. Reusability of KI/g-Al2O3 catalyst in transesterication of palm oil. Reaction
conditions: methanol/oil molar ratio 14:1, catalyst loading 0:24 gKI =ggAl2 O3 , reaction Reaction conditions: methanol/oil molar ratio 14:1, catalyst loading
temperature 60  C, reaction time 4 h, catalyst amount 0.6 g (4 wt.%, gCat./goil) and 0:24 gKI =ggAl2 O3 , reaction temperature 60  C, reaction time 4 h, catalyst amount
catalyst calcined at 500  C. 0.6 g (4 wt.%, gCat./goil) and catalyst calcined at 500  C.
A. Islam et al. / Energy 89 (2015) 965e973 973

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