Journal of Scientific & Industrial Research

Vol. 73, February 2014, pp. 129-133

Preparation, Characterization and Application of Zeolite-based Catalyst for

Production of Biodiesel from Waste Cooking Oil
Maryam Hassani1, Ghasem D Najafpour1*, Maedeh Mohammadi1 and Mahmood Rabiee2
1

Faculty of Chemical Engineering, 2Faculty of Mechanical Engineering Noushirvani University of Technology, 47148, Iran
Received 08 October 2012; revised 24 September 2013; accepted 28 November 2013

Zeolite-based catalyst was prepared from a fine powder and kaolinite by pelletization method and used to synthesize fatty
acid methyl esters (FAME) known as biodiesel from waste cooking oil (WCO) containing high amounts of free fatty acids (FFA).
The prepared catalyst was characterized by Thermogravimetric analysis (TG/DTA), X-ray Diffraction (XRD), Fourier Transform
Infrared (FTIR) spectroscopy and Brunauer-Emmett-Teller (BET) surface area analysis. The zeolite-based catalyst was employed
to simultaneously catalyze the esterication of fatty acids and transesterication of triglycerides present in the waste oil feedstock to
biodiesel. The condition for biodiesel synthesis was optimized in terms of reaction temperature (50-85 oC), methanol/ WCO molar
ratio (2.6-6.0) and reaction time (2-10 h). Maximum triglyceride conversion of 46 % was achieved at the near optimum conditions.
These conditions were defined at reaction temperature of 70 oC, methanol/ WCO molar ratio of 5.1 and reaction time of 6 h.
Keywords: Waste cooking oil, Biodiesel, Zeolite-based catalyst, Transesterification

Introduction
Finding an alternative fuel resource for diesel is an
imperious task for humans1,2. Biodiesel is a sustainable
fuel alternative whose production has recently become a
priority for many countries and would play an important
role in diesel industry. Biodiesel offers advantages such
as being environmentally friendly fuel (less CO2
emissions, almost zero CO and sulfur emissions),
nontoxic and biodegradability with low viscosity.
Biodiesel possesses good lubricity and is renewable in
comparison to traditional petroleum diesel3,4.
Furthermore, this fuel can be used in blend form and
very small proportion of it is relatively effective in
reducing particulate emissions from engine5.
Biodiesel has been derived from various renewable
lipid sources such as vegetable oils or animal fats6. A
literature survey reveals that this lipid feedstock can be
derived from canola7, palm oil8, jatropha9, soybean10,
sunflower11, rapeseed12 and coconut13. Production of
biodiesel from highly pure oils used for cooking
purposes and methanol or ethanol as alcohol in presence
of homogeneous catalyst such as sodium or potassium
hydroxides, carbonates or alkoxides contributes to the
increase of the total manufacturing cost of biodiesel14.
Biodiesel produced from this method has a higher cost
compared to fossil fuels; approximately 1.5 times
_____________
*
Author for correspondence
Email: najafpour@nit.ac.ir

higher15. One of the effective methods for reducing the

cost of biodiesel production is the use of low quality oils
which are not suitable for human consumption and
readily available such as waste cooking oil (WCO),
animal fat and tall oil4 as well as soap stock (by-product
of vegetable oil refinery)15. These oils have low value
and there is no concern for their availability; they can be
regarded as attractive feedstock for production of
biodiesel16. Replacing homogeneous catalysts by
heterogeneous catalysts is another alternative to reduce
biodiesel production costs. Homogeneous catalytic
systems create serious downstream problems such as
difficulties in removal and separation of catalysts after
the reaction and production of huge amount of
wastewater.
Zeolites have been widely used as industrial
heterogeneous catalysts because they are inexpensive
and environmentally benign. They offer generous
surface area and high porosity17. However, application
of zeolites as catalysts for transesterification reaction
is limited by the narrow pore size of zeolites and
diffusion limitations for adsorption of triglyceride on
the active sites of zeolites. The molecular size of FFA
is comparably lower than that of triglyceride, thus,
zeolites are more effective for esterification than
transesterification reactions17. Hence, development of
mesoporous zeolites would provide great opportunity
to avoid the diffusion limitation and improvement of
transesterification of vegetable oils.

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J SCI IND RES VOL 73 FEBRUARY 2014

In this study, a mesoporous zeolite-based catalyst was

developed to carry out the transesterification reaction.
Waste cooking oil (WCO) was used as a worthless and
abundant feedstock to produce biodiesel. The effect of
several operation parameters on conversion of
triglyceride was considered and the near optimum
conditions to yield maximum FAME were defined.
Materials and Methods
Pretreatment of the waste cooking oil

WCO was collected from the university canteen.

Solid particles were removed from WCO by filtration.
The sample WCO containing water and other
impurities was centrifuged at 15000 rpm and dried for
72 h. Then, the WCO was mixed with n-hexane
(1:3 oil/ hexane, volume ratio) to remove the
remaining impurities. After 72 h, the oil was
separated from n-hexane in a Rotavapour. The
composition of fatty acids in WCO was determined
by GC-MS as summarized in Table 1.
Catalyst preparation and characterization

Fine zeolite powder was supplied by Hexagon

Synergy (M) Sdn Bhd (Kuala Lumpur, Malaysia).
The chemical composition of the powder was
determined by X-ray Fluorescence (XRF) analysis
using a Philips PW 1480 spectrometer (Table 2). In
preparation of zeolite-based catalyst poly vinyl
alcohol (PVA) and kaolinite were used as binder. In
each batch, 200 g of fine powder was used. The slurry
was obtained by mixing the fine zeolite powder, PVA
and kaolinite with proportion of 75; 15 and 10 wt%.
The slurry was mixed by a mechanical stirrer for 3 to
5 min, and then dried in an oven at 60 C over night.
The dried mixture was ground using a pestle and
mortar to a fine powder of 0.03 mm. The powder was
Table 1 Fatty acid, FFA and water content of the WCO
Fatty acid components

(%)

C 14: 0
C 16: 0
C 16: 1
C 18: 0
C 18: 1
C 18: 2
C 18: 3
FFA content
Water content

0
28.91
1.45
1.26
26.51
27.44
4.60
9.85
0.03

rehydrated by a few droplets of water and pressed

one-dimensionally under a force higher than 20 tons
to produce thin pellets (80 mm diameter and 2 mm
thickness). The pellets were then calcined in a muffle
furnace in the presence of air at 700 C for 3 h. The
calcined pellets were kept in desiccator for further
characterization and transesterification experiments.
Thermal stability of the synthesized zeolite-based
catalyst was determined by Thermogravimetric
analysis (TGA) carried out using a TG/DTA analyzer
(PL-STA-1640). Crystal structure of the developed
catalyst was investigated by wide angle X-ray
diffraction (XRD) pattern taken using a Philips 1887
diffractometer equipped with Cu K radiation at
40 kV and 30 mA in the scanning angle 2 of 2080.
The detection of surface functional groups of the catalyst
was carried out using Fourier Transform Infrared
Spectroscopy (FTIR) analysis (Shimadzu FTIR-8300).
N2 adsorption-desorption isotherms were obtained at
77 K using Micromeritics Gemini series surface area
analyzer. The surface area was measured from the
adsorption-desorption isotherm using Brunauer-EmmettTeller (BET) equation. Pore size distribution was
obtained from Barrett-Joyner-Halenda (BJH) method.
Synthesis of biodiesel

The simultaneous transesterication and esterication

of the WCO containing 9.85 wt% FFA was carried out
in the presence of prepared zeolite-based catalyst in a
round-bottom flask equipped with a reux condenser,
temperature controller and mechanical stirrer. The ask
was immersed into a water bath while the temperature
was controlled in the range of 5085 oC. Initially the
reactor was loaded with 25 g of WCO and variable
amounts of methanol. Then, fixed amount of 0.65 g
catalyst was added to the reaction vessel while stirring
speed was fixed at 600 rpm. Upon completion of the
transesterification reaction, the excess methanol was
vaporized. The catalyst was removed from the reaction
vessel by filtration and the produced mixture was
centrifuged. Upon the centrifugation, two phases were
formed, i.e. FAME in the upper layer and glycerol in the
lower layer. The glycerol phase was separated from the
FAME layer in a separating funnel. Finally, for
purification of the achieved FAME phase, the water
washing method was used to separate the glycerol from
the FAMEglycerol mixture and to obtain pure FAME.

Table 2 XRF analysis of the fine powder used as catalyst

Compound

SiO2

Al2O3

Fe2O3

CaO

Na2O

TiO2

MgO

K2O

P2O5

SO3

MnO

L.O.I

wt %

85.3

6.92

0.90

0.75

0.74

0.48

0.47

0.21

0.029

0.003

0.001

3.78

HASSANI et al: APPLICATION OF ZEOLITE-BASED CATALYST FOR COOKING OIL

The products were analyzed using GC-MS spectrometer

(Agilent 5973) equipped with a capillary column (HP-5);
Wiley libraries were used as reference databases.
Results and Discussion
Catalyst characterization

Physio-chemical properties of the prepared

zeolite-based catalyst were studied using several
analyses
before
being
implemented
in
transesterification reaction. Fig. 1 shows the TG/DTA
curves obtained for the catalyst under air. A minor
weight loss was observed in TG curve in the
temperature range of 25-250 oC which was due to the
dehydration of the sample. The main weight loss in TG
curve started at around 250 C and continued to 500 C
which was attributed to the oxidation of organic phase
and dehydroxylation of the zeolite. The two exothermic
peaks observed on the DTA curve at 279 and 424 C
represent the two-stage oxidation of organic matter
(H and C) and the formation of H2O and CO2. The
thermal degradation profiles of the catalyst further
confirm that the applied calcinations temperature was
high enough to remove the organic impurities.
The XRD pattern of the developed catalyst is
shown in Fig. 2. The XRD spectrum exhibited a well-

resolved diffraction pattern with prominent peaks at

2= 21.85, 26.80 and 35.97. All the three peaks
represent crystals with the same chemical formula but
different crystal structures. The first peak that is taller
than others is assigned to the crystal structure
cristobalite and the second peak with moderate
intensity corresponds to quartz and the third peak is
associated with tridymite structure with a probability
close to certainty. Also, three broad, but low peaks
appeared at 2= 50.29, 60.10 and 68.48 that have
same chemical formula. These peaks show patterns
for crystal phase quartz, tridymite and cristobalite,
respectively.
Fig. 3 depicts the FTIR spectrum of the zeolitebased catalyst. The sharp peaks with strong
absorption at 478 and 1102 cm1 are related to
deformation bands SiOSi18 and the perpendicular
SiO vibration bands in kaolinite19, respectively. The
peaks found at 791 and 3416 cm1 could be assigned
to bands SiOSi19,20 and OH21. Vibration bands of
the internal (inner) carbonate groups20 and AlOH
vibration band22 are represented by the peaks located
at 1400 and 1625 cm1, respectively. The peak
appeared at 625 cm1 is associated with coupled outof-plane vibration band of Al-O and Si-O18 and the
peak at 2358 cm1 is assigned to CO223. The SiO
groups exist in raw materials, AlOH groups were
created due to the mixing of H2O with zeolite and
carbonate groups and CO2 were formed as a result of
calcination.
The textural properties of the prepared catalyst
were studied by N2 adsorption adsorptiondesorption
isotherms (data not shown). According to the IUPAC
classification, the isotherm exhibited a type IV curve

Fig.1TG/DTA curves of zeolite-based catalyst

Fig. 2XRD pattern for the zeolite-based catalyst

131

Fig. 3FTIR spectrum of the zeolite-based catalyst

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J SCI IND RES VOL 73 FEBRUARY 2014

with a hysteresis loop which is an indication of

mesoporous material. The adsorption- desorption was
not a reversible process which led to the appearance
of a hysteresis loop between the curves of adsorption
and desorption. While the capillary condensation in
the mesopores occurs at a higher relative pressure
than capillary evaporation, the hysteresis loop is
observed24,25. The pore size distribution (PSD) which
represents the structural homogeneity of the
developed catalysts confirmed the mesoporous
structure (2< dP< 50 nm) of the catalyst. Based on the
analysis of the results, a BET surface area of
61.9 m2/g with mean pore diameter of 23.414 nm and
total pore volume of 0.32 cm3/g was achieved for the
prepared catalyst.
Effect of reaction parameters
Effect of reaction temperature

Reaction temperature is one of the most

influencing parameters on the rate of reaction. The
effect of temperature on the conversion of triglyceride
in biodiesel production using zeolite-based catalyst
was examined at different temperatures from 50 to
85 oC with initial WCO of 25 g, catalyst loading of
2.6 w/w%, methanol/WCO molar ratio of 5.1 and
reaction time of 6 h. The results of present
investigation are projected in Fig. 4 (a). Increase in
the reaction temperature to 70 oC improved the
triglyceride conversion after which, a decreasing trend
was observed in the conversion. Maximum
triglyceride conversion of 46.2 % was achieved at
70 oC. Although high reaction temperatures enhance
the reaction rate to produce more FAME, however,
increase of the temperature to above 70 oC which
exceeds the boiling point of methanol (65 oC)
adversely affects the conversion. In this case,
evaporation of methanol to the condenser and
condensation into the reaction vessel causes an
unstable reaction condition.

Effect of methanol/WCO molar ratio

The yield of FAME production is affected by the

methanol/oil molar ratio. Theoretically, for
transesterification of vegetable oil, three moles of
methanol is required per mole of triglyceride. Since
the transesterification is a reversible reaction, the
mole of methanol in the reaction mixture must be
excess enough to shift the equilibrium towards the
formation of FAME. In the present work, the
methanol/WCO molar ratio was optimized by varying
this molar ratio in the range of 2.6-6.0 at a fixed WCO
amount of 25 g and the reaction temperature of 70 oC.
The results are shown in Fig. 4 (b). The conversion of
triglyceride noticeably enhanced from 26 to 48% with
increase of the methanol/WCO ratio from 2.6 to 5.1,
afterward, the conversion almost leveled off. With
increase of the methanol/WCO ratio from 5.1 to 6, only
a slight improvement in the conversion of triglyceride
was observed. The excess amount of methanol is
favorable for the conversion of triglyceride to
monoglyceride. However, monoglyceride significantly
affects the solubility of glycerol in FAME, which are
naturally immiscible, and lead to the glycerolysis of
FAME and reduction of triglyceride conversion26.
Based on the achieved results and the presented
discussion, the methanol/ WCO molar ratio of 5.1 was
selected for further experiments.
Effect of reaction time

The influence of reaction time on the conversion of

triglyceride was studied in the range of 2 to 10 h with an
increment of 2 h and the results are shown in Fig. 4 (c).
As it was noted from the results, increase of the
reaction time to 6 h considerably improved the
conversion of triglyceride to around 46 %. Further
increase in the reaction time did not show notable
increase in the conversion. Such observation may be
due to the catalyst deactivation resulted from
accumulation of reactants or products in the porosity

Fig. 4Influence of (a) reaction temperature, (b) methanol/ WCO molar ratio and (c) reaction time on the conversion of triglycerid

HASSANI et al: APPLICATION OF ZEOLITE-BASED CATALYST FOR COOKING OIL

of catalyst in long reaction times. This leads to the

loss of active sites on the catalyst surface and reduces
the activity of catalyst. Therefore, the reaction time of
6 h was defined as the suitable reaction time for the
synthesis of FAME.
Conclusion
Zeolite-based catalyst was prepared from zeolite
powder, kaolinite and PVA and characterized by
TG/DTA, XRD, FTIR and BET techniques. The
ability of the developed catalyst to catalyze the
transesterification reaction was assessed in some sets
of batch experiments. WCO containing high amount
of FFA which was much cheaper than feed grade oil
was used as the substrate for biodiesel synthesis. The
transesterification reaction condition was optimized in
terms of reaction temperature, methanol/WCO molar
ratio and reaction time to improve the conversion of
triglyceride to FAME. Maximum triglyceride
conversion of 46% was attained at the near optimum
condition.
Acknowledgement
The authors gratefully acknowledge the research
committee of postgraduate studies, Noushirvani
University for the support and facilities provided in
Biotechnology research center.
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