Journal of Energy Chemistry 22(2013)690700

Activity and basic properties of KOH/mordenite for

transesterification of palm oil
Pisitpong Intaraponga , Sotsanan Iangthanarata , Pitchaya Phanthonga ,
Apanee Luengnaruemitchaia,b , Samai Jai-Inc
a. The Petroleum and Petrochemical College, Chulalongkorn University, Bangkok 10330, Thailand;
b. Center of Excellence on Petrochemical and Materials Technology, Chulalongkorn University, Bangkok 10330, Thailand;
c. The Royal Thai Navy, Bangkok 10700, Thailand
[ Manuscript received January 15, 2013; revised March 13, 2013 ]

Abstract
The catalytic performance of KOH/mordenite has been studied for transesterification of palm oil using a batch reactor and a packed-bed reactor
at 60 C and atmospheric pressure. The KOH/mordenite processed transesterification in the batch reactor gave the highest methyl ester yield of
96.7% under optimum conditions, while a methyl ester content over 94.5% was obtained in the packed-bed reactor. This comparison indicates
that transesterification in a batch-type reactor gives a higher methyl ester yield than that of a continuous-flow reactor. Dealumination was
found in the calcined catalysts and had a significant effect on the physical structure and chemical composition of the catalysts. Leaching of the
potassium species was negligible, whereas depositing and washing of the reacted mixture with acetone on the catalyst surface were observed
by FTIR.
Key words
transesterification; biodiesel; mordenite; KOH; solid base catalyst

1. Introduction
Biodiesel fuels from transesterification of palm oil are being considered as a kind of potential biofuel to contribute toward sustainable development of many countries, including
Thailand. The main advantages of using biodiesel as a fuel
are its renewability, biodegradability, and more eco-friendly
exhaust gases [1]. Industrial biodiesel can be produced by
a chemical reaction between triglycerides and low molecular weight alcohols, such as methanol or ethanol in the presence of a catalyst. A strong base, such as NaOH or KOH,
is generally used to produce biodiesel since it is able to promote the reaction at relatively low temperatures [2]. However, the main drawbacks of homogeneous base catalysts are
the large amount of waste water produced from the washing
step and the high energy consumption for phase separation.
These problems can be solved with the use of heterogeneous
transesterification catalysts, which offer advantages such as
prevention of side reactions and reusability of the catalysts.
A variety of solid catalystsalkaline and alkaline earth
metal oxides, various types of alkali metal compounds supported on aluminahas been examined for this reaction

[35]. Higher amounts of alkaline will result in higher basic properties, which can promote the transesterification reaction. Zeolite is one of the most used catalysts because their basic properties are enhanced when alkali metal cations are exchanged with protons and bonded with the negatively charged
framework [6,7]. KOH supported on NaY and NaX zeolite
catalysts could prevent deactivation of the catalyst and performed as a heterogeneous-like system [7,8]. Additionally,
mordenite has been explored as a catalyst for many reactions:
modification of the alkalinity on the zeolite to enhance the
electron density of the framework oxygen species and to promote the strength of molecular centers has been well documented in literature.
However, leaching of the active species into the solution
during the course of a reaction has been reported [9]. Leaching affects significantly the industrial applications and extensive leaching threatens the reusability of the catalyst. In addition, one of the drawbacks of heterogeneous catalysts is the
deactivation with time and the stability of the catalyst decreases slightly within the recycle run [10]. It has been reported that the deactivation mechanism of the heterogeneous
catalysts for transesterification can be either the leaching of

Corresponding author. Tel: +662-2184148; Fax: +662-2154459; E-mail: apanee.l@chula.ac.th

This work was supported financially by the National Metal and Materials Technology Center, Thailand, and the Center of Excellence on Petrochemical
and Materials Technology, Thailand.
Copyright2013, Dalian Institute of Chemical Physics, Chinese Academy of Sciences. All rights reserved.

Journal of Energy Chemistry Vol. 22 No. 5 2013

the active species or the adsorption of hydrocarbons onto the

basic sites.
Taking this into account, the structure of mordenite is attractive to be used as a support. It is clear that the chemical composition and basic properties of the catalyst can
play an important role in transesterification. Accordingly,
KOH/mordenite could achieve a high conversion yield and
high reusability, making it of interest to apply in biodiesel
production. In the present study, the catalytic activities of
KOH/mordenite in transesterification under mild conditions
were determined in both a batch and a packed-bed reactor
to evaluate the suitability of this catalyst. The influence of
the basic properties and physical structure on the catalytic
activity was also evaluated. Additionally, the reusability of
KOH/mordenite was investigated.
2. Experimental
2.1. Materials
Refined palm oil was obtained from the Naval Engineering Command in Thailand. Mordenite zeolite was obtained
from Zeolyst Company. Anhydrous methanol (Lab-Scan,
99.95%), potassium hydroxide (Lab-Scan), sodium sulfate
(Fisher Scientific), and heptane (Fisher Scientific, puriss p.a.,
99.5% GC) were used as chemicals for transesterification.
Methyl heptadecanoate (puriss p.a., standard for GC, 99.7%)
supplied by Fluka was used to measure the methyl ester content.
2.2. Catalyst preparation
The KOH/mordenite catalyst was prepared by an impregnation method. The pure mordenite zeolite was calcined at
600 C for 3 h. To modify the mordenite zeolite with different
amount of K loadings (5, 10, 15, 20, 25, and 30 wt%), the
mordenite zeolite was impregnated with an aqueous solution
of KOH for 24 h. Then it was dried at 110 C for 24 h before
use as a catalyst in the reaction.
2.3. Catalyst characterization
A Bruker X-ray diffractometer system (D8 Advance)
equipped with a 2.2 kW Cu anode long fine focus ceramic
was
X-ray tube for generating CuK radiation (1.5405 A)
used as an X-ray source to obtain the XRD patterns at running
conditions for the X-ray tube (40 kV and 40 mA). The detector scanned the intensity of diffracted radiation in the range of
10o to 70o (2) with a scan speed of 0.02o (2)/0.5 s.
A scanning electron microscope (SEM), Hitachi/S-4800,
was utilized to identify the microstructure and capture the micrograph of the catalyst morphology. The catalyst sample was
placed on a stub and coated with platinum in a sputtering device before being placed in the sample holder of the SEM.

691

Specific surface area and pore volume were determined

by physisorption of nitrogen at liquid temperature in a stationary mode using a Sorptomatic model 1990 instrument
(Thermo Finnigan). Before analyzing, the volatile species adsorbed on the surface were eliminated by outgassing at 300 C
for 24 h. Helium gas was used as an adsorbate for blank analysis and nitrogen gas was used as the adsorbate for analysis.
The specific surface area, pore volume, and pore size distribution were obtained by measuring the volume adsorbed
at different P/P0 values. Total pore volume was estimated
by measuring the volume of the adsorbed gas at a P/P0 of
0.99, and total micropore volume and micropore size distribution were obtained by applying the Horvath-Kawazoe method,
1983.
A Fourier transform infrared spectrophotometer (FTIR),
Thermo Nicolet Nexus 670, was used to identify the chemical functional groups of the samples. The solid samples were
ground into fine powder and mixed with potassium bromide
(KBr) and pressed. The spectra were obtained at a resolution
of 4 cm1 in the range of 4000 cm1 to 400 cm1 .
The basic properties of the samples were determined
using temperature-programmed desorption (Micromeristics
2900) of CO2 (CO2 -TPD), which was used as the probe
molecule. A 150 mg sample was degassed by heating in a
flow of helium at a rate of 10 C/min from room temperature
to 500 C for 1 h. After it was cooled to 50 C, CO2 gas was
introduced for adsorption for 1 h. To remove the physically
adsorbed CO2 gas, the sample was purged with helium gas at
a flow rate of 30 mL/min for 1 h. CO2 -TPD was performed at
the rate of 5 C/min from 30 C to 600 C.
Basic strength of the catalysts was determined using
Hammett indicators of bromthymol blue (H = 7.2), phenolphthalein (H = 9.8), 2, 4-dinitroaniline (H = 15.0), and
4-nitroaniline (H = 18.4). An estimated titration method
measured the total basic sites of the samples. Each catalyst
sample (20 mg) was shaken in 5 mL of 0.02 M aqueous HCl
for 1 h, and the remaining acid was then titrated with a standard base (0.02 M aqueous KOH).
Nuclear magnetic resonance (NMR) spectra were obtained by a Varian Inova model 400 spectrometer. 1 H, 27 Al,
and 29 Si solid-state NMR were operated at frequencies of 400,
130.32, and 99.36 MHz, respectively, and were performed at
room temperature with a spin rate of 10 kHz.
An energy dispersive X-ray fluorescence (XRF) spectrometer (Oxford model ED2000) was used to determine the
bulk composition of each catalyst. The potassium contents
of the fresh and spent catalysts were measured by XRF. The
leached potassium was determined by the total amount of
potassium that remained in the spent catalyst after being subtracted from the amount of potassium in the fresh catalyst.
Inductively coupled plasma optical emission spectrometry (ICP-OES) was carried out with a Perkin-Elmer Optima
2100 DV (Wellesley, MA). The biodiesel was diluted with
kerosene (0.1 g/g), and the glycerol was diluted with distilled
water (0.01 g/g), following the method used by Yan et al. [11].

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2.4. Transesterif ication

2.4.1. Batch experiment
One hundred grams of refined palm oil were placed in
a 500 mL three-necked flask. The vegetable oil was heated
to 60 C. Then the catalyst and methanol were added to the
three-necked flask. A magnetic stirrer was used to mix the oil,
methanol, and catalyst at 300 rpm. The reaction was carried
out until it reached the desired reaction time. The used catalysts were separated by using a suction flask. Next, the excess
methanol was distillated off with a rotary evaporator. Finally,
when the glycerol layer (bottom) was removed, the biodiesel
was analyzed by gas chromatography (GC).

not observed on the XRD patterns of the KOH/mordenite, suggesting that either the intensity of the KOH or K2 O peaks is
very low compared to the XRD patterns of the mordenite zeolite, or there are significant overlap and refractions with those
of the mordenite.

2.4.2. Packed-bed experiment

Refined palm oil and methanol were weighed and placed
into a three-necked flask and heated to 60 C. The reactor
system consisted of a stainless steel column (dimension of
2.5 cm i.d.8 cm length), equipped with a temperature controller employing a K-type thermocouple. The powder catalysts were packed into the stainless steel column and heated
to 60 C for 2 h before the reactant mixtures were fed into the
column at a rate of 11 mL/min at the bottom of the packedbed reactor. Then, the mixtures were circulated back to the
system until they reached the desired reaction time. Finally,
the products were pumped back into the flask for separation
and purification, as described in the batch reactor procedure.
2.5. Biodiesel analysis
The biodiesel was analyzed by GC (HP 5890) with a capillary column of DB-WAX (30 m0.25 mm) and equipped
with a flame ionization detector. Injection and detector temperatures were 230 C and 250 C, respectively. The oven
temperature was held at 130 C for 2 min and increased to
220 C at a heating rate of 2 C/min, and then held for 5 min.
Methyl heptadecanoate was used as an internal standard to
determine the amount of FAME. Flash point, viscosity, water,
and sulfur contents of the biodiesel products were determined
according to the EN 14214 standards.
3. Results and discussion
3.1. Inf luence of KOH loading
The XRD patterns of the mordenite and KOH/mordenite
catalysts are illustrated in Figure 1. Typical peaks of mordenite at 2 = 13.5o, 19.6o , 22.3o, 25.7o, 26.3o, 27.5o, and
30.9o are observed. When the amount of K is increased, the
XRD patterns of the 10 wt%, 15 wt%, and 20 wt% KOH samples show that the intensity of the mordenite peaks decreases
when K increases, indicating that an insignificant loss of crystallinity has occurred. However, either KOH or K2 O peaks are

Figure 1. XRD patterns of mordenite and K/mordenite catalysts. (1) mordenite, (2) 10 wt% K/mordenite, (3) 15 wt% K/mordenite, (4) 20 wt%
K/mordenite, (5) 30 wt% K/mordenite; calcined 20 wt% K/mordenite at temperature (6) 400 C, (7) 500 C, and (8) 600 C

The SEM images reveal that the mordenite and

KOH/mordenite particles are irregular in shape (10 m to
20 m) at a magnification of 1000, as shown in Figure 2(ac).
No significant difference in the morphology of the mordenite and KOH/mordenite is observed. After being loaded with
KOH, the particles seem to agglomerate.
The morphology of the 30 wt% KOH/mordenite changed
to an amorphous structure due to the damaged structure of
the mordenite support. At a magnification of 100 k (100
to 500 nm), as shown in Figure 2(jl), the images of the
mordenite exhibit a round plate shape and sharp crystallinity.
The pore diameter of the mordenite consists of straight 12membered right channels with a slightly elliptical cross section of 67 nm70 nm [12,13]. When loading KOH to 20 wt%,
the surface of the modified mordenite still exhibits round
shapes with crystallinity being almost the same as the unmodified mordenite. The round plate shape (SEM) and crystallinity (XRD) of the mordenite are not found after loading
K to 30%. An excess of potassium at 30 wt% covers all the
pores and surface of the zeolite, resulting in the growth of the
particles. The SEM results are consistent with the XRD results.
Table 1 shows surface areas of the unmodified mordenite
and the modified mordenite. The surface area of the mordenite decreases from 315.5 m2 /g to 1.4 m2 /g when the potassium

Journal of Energy Chemistry Vol. 22 No. 5 2013

content is increased to 30 wt%. The H-K cumulative pore volume curve of the pure mordenite and the modified mordenite
samples are shown in Figure 3. The pore volume of the mordenite decreases from 0.2516 cm3 /g to 0.0179 cm3 /g, which
indicates that the potassium base causes a significant decrease
in the pore volume inside the hollow pores. Moreover, the
peak width of the curves was analyzed in the range of 3 nm to

693

400 nm. Microspores were rarely found after increasing the

potassium hydroxide to 30 wt%, and the pore size distribution
of the catalyst decreased, corresponded with the decrease in
pore volume. Simultaneously, the micropore distribution was
narrowed and the surface area was greatly reduced at a high
loading of alkaline solution because the coverage of potassium
blocked the pore openings.

Figure 2. SEM images of mordenite and KOH/mordenite catalysts: (a) mordenite, (b) 20 wt% KOH/mordenite, and (c) 30 wt% KOH/mordenite: calcined
20 wt% KOH/mordenite at temperature: (d) 400 C, (e) 500 C, and (f) 600 C: (g) Fresh 20 wt% KOH/mordenite, (h) Spent 20 wt% KOH/mordenite, and (i)
Treated 20 wt% KOH/mordenite: (j) mordenite, (k) 20 wt% KOH/mordenite, (l) 30 wt% KOH/mordenite, and (m) calcined 20 wt% KOH/mordenite at 400 C

The FTIR spectra of the mordenite support and the

KOH/mordenite catalysts are shown in Figure 4. The absorption peaks at 3614 cm1 and 3460 cm1 (Figure 4(1)) are
attributed to OH-stretching associated with terminal silanol

groups and the HOH frequency of the H2 O molecule is

located at a wavenumber of 16291646 cm1 at a medium
intensity [14]. A set of strong intensity peaks at 1224 cm1
and 1046 cm1 are ascribed to the vibration of external TO4

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Pisitpong Intarapong et al./ Journal of Energy Chemistry Vol. 22 No. 5 2013

(T = Al, Si) and antisymmetrical stretching vibration of the

tetrahedral (TO bonds), respectively. The other absorption
bands of 628789 cm1 correspond to the characteristic vibration of symmetrical stretching of Si (Al)O bonds, and
the bending of OSi (Al)O is interpreted at 437 cm1 [15].
These results confirmed the functional groups and the characteristics of the pure mordenite support. For the fresh catalyst (Figure 4(2)), many absorption peaks are transformed
due to the loading of K. The reduction in intensity of the
OH stretching vibration at 3600 cm1 changes to a broad
band. In addition, the set of high intensity absorption peaks at
10001250 cm1 of the pure mordenite support is converted
into a broad peak at 8001300 cm1 for the KOH/mordenite
catalysts. It could be inferred that the impregnation of KOH
affects the structure and composition of the mordenite zeolite
support, which are indications of crystallinity loss, probably
as a consequence of dealumination.

Figure 3. Horvath-Kawazoe pore size and pore volume of mordenite and

modified mordenite catalysts

The basic properties of these catalysts are estimated by

using CO2 -TPD, as reported in Table 1. The mordenite was
exposed to CO2 at 110 C and 310 C. It did not show any desorption peaks at a high temperature, which can be attributed to
the interaction of CO2 with the occluded sodium oxide species
[16]. The intensity of the CO2 desorption peak at a low temperature decreased when a high amount of potassium content

was used. In fact, the mordenite support did not show any catalytic activity, while 20 wt% KOH/mordenite with the highest
basicity (from the titration method) showed the highest activity. The CO2 adsorption properties of the zeolites are also
influenced by the porous characteristics of the framework.
This is attributed to the different Si/Al ratios of the zeolites as
well as the amount and type of charge-balancing cations. The
Si/Al ratio of the mordenite was 9.46, which is close to Macedonia et al. [17]. The Si/Al ratio on the KOH/mordenite catalyst decreased upon treatment (from 9.46 to 9.13), suggesting
that Si has been slightly extracted out of the mordenite. Our
results correspond with those of Guisnet et al., who noted that
the decrease in crystallinity was probably due to the absence
of extraframework aluminium on the zeolite which could be
replaced by the silicon [18].

Figure 4. FTIR spectra of mordenite and KOH/mordenite catalysts: (1) mordenite, (2) fresh 20 wt% KOH/mordenite, (3) used 20 wt% KOH/mordenite,
and (4) washed 20 wt% KOH/mordenite

To clarify the correlation between the amount of potassium and the basic properties, Hammett indicators were used
to indicate the basic strength that existed on the surface of the
catalyst (Table 1). The pure mordenite had no basic properties
and the modified mordenite showed higher basic strength in

Table 1. Characterization of mordenite and KOH/mordenite catalysts

Samples
Fresh mordenite
Fresh 10 wt% KOH/mordenite
Fresh 20 wt% KOH/mordenite
Fresh 30 wt% KOH/mordenite
20 wt% KOH/mordenite calcined at 400 C
20 wt% KOH/mordenite calcined at 500 C
20 wt% KOH/mordenite calcined at 600 C
Spent 1st 20 wt% KOH/mordenite
Spent 2nd 20 wt% KOH/mordenite
Treated spent 1st 20 wt% KOH/mordenite
Treated spent 2st 20 wt% KOH/mordenite
a

Surface
area
(m2 /g)
315.5
170.28
92.86
1.4
12.7
6.8
4.5
17.2

37.8

Si/Al
ratioa
9.46

9.44
9.13

11.99

9.43

Basic
strength
(H )b
H <7.2
9.8>H >15
9.8>H >15
9.8>H >15
9.8>H >15
9.8>H >15
9.8>H >15
9.8>H >15
9.8>H >15
9.8>H >15
9.8>H >15

Measured by XRF technique; b Measured by Hammett indicators; c Batch reactor

Basicity (mmol/g)
CO2 -TPD
estimated
110 C
310 C
titration
0.049
0.014
0.180.12
0.022
0.01
2.410.23
0.0037
0.003
5.160.17
0
0
4.230.31

4.810.29

2.980.36

2.210.19

4.480.43

3.890.45

3.580.21

2.250.17

Methyl ester
yield
(%)c
0
89.0
96.7
70.1
82.6
38.1
18.1
72.3
40.2

Journal of Energy Chemistry Vol. 22 No. 5 2013

the range of 9.8>H >15 when the KOH loading was increased. This resulted in a higher conversion rate. The basic
strength value could not be used to clarify the activity of the
prepared catalysts; therefore, the basic sites of the catalyst,
measured by the approximated acid titration method, was applied. It was found that the basic sites increased with the increased KOH loading to 20 wt%. With further increasing of
KOH to 30 wt%, the basic sites decreased because the pore
structure of the mordenite collapsed, as reported previously in
the results of XRD, SEM and N2 adsorption-desorption techniques. Therefore, the highest basic sites were obtained with
the 20 wt% KOH/mordenite.
Different amounts of basic sites from CO2 -TPD and approximated titration were clearly observed. The CO2 -TPD
technique used CO2 gas as a probe molecule absorbing on
the surface of the catalyst. However, the titration techniques
used an acid solution to titrate vacancies in the solid base catalyst in the methanol solution. The acidic agent reacted with
the basic sites on the top layer and dissolved into the solution.
It could be suggested that the data of basic sites from the approximated titration could be the total basic sites of the bulk
catalyst, whereas the CO2 -TPD is equal to the amount of basic sites on the surface. Similarly, results were also found with
KNO3 /Al2 O3 that CO2 -TPD designated the amount of basic
sites exposed at the top of the overlapped structure while the
titration could represent all basic sites [19].
Earlier studies have demonstrated the potential of NMR
in elucidating dealumination of catalysts. Figure 5(a) shows
that the 1 H NMR spectrum of the mordenite zeolite peaked
at 3.62 ppm. This could be ascribed to be the bridging of
the hydroxyl group (SiOHAl) which formed H-bonding with
water molecules. Free protons from the water combine with

695

oxygen on the zeolite [20]. The oxygen molecules of water absorb physically onto the cations (Na+ ) which bonded
with oxygen on the zeolite catalyst. The FTIR result corresponds to the NMR in that the OH broad band of isolated and
bonded stretching (3650 cm1 and 30003500 cm1 ) was
found, suggesting that water molecules strongly absorbed in
the zeolite framework. After loading KOH to 20 wt%, the
peak of the spectra at 1.27 and 6.29 ppm appeared. The signal at 1.2 ppm as a trace of physically absorbed water on the
cation was originally observed by Vyalikh et al. [21]. The
shifted peak from 3.6 ppm to 6.3 ppm was found due to the
larger size of the cation. The progressively bigger cation
size diffused into the pores and the sensitive physicochemical
structure changed with the parent Na+ in the sodalite cage.
The balancing charge, therefore, occurred on the zeolite extraframework. The K+ cation exchanged with the Na+ on
the mordenite zeolite. The larger ionic radius was expected
to occupy sites I and II in the supercages. This peak shift
could also be ascribed to the electrostatic interaction bridge
of the hydroxyl proton to the adjacent framework of oxygen.
The chemical shift provided useful information in explaining
the strong K+ cation interaction with the oxygen framework,
while also displaying increased basic strength of the catalyst.
Bosch et al. [22] have noted that the basic strength could be
estimated from the proton chemical shifts which are caused
from the increasing size of the alkali-metal cation, such as
exchanging K or Cs from NaY into KY or CsNaY. Potassium
adsorption took place on the framework, thus leading to chemical shifts. With further loading of K to 30 wt%, the chemical shift increased due to a high quadrupolar interaction of
potassium.

Figure 5. (a) 1 H NMR spectra of uncalcined (1) mordenite, (2) 20 wt% KOH/mordenite, (3) 30 wt% KOH/mordenite, and calcined (4) 20 wt% KOH/mordenite;
(b) 29 Si NMR spectra of (2) uncalcined 20 wt% KOH/mordenite, and (4) calcined 20 wt% KOH/mordenite; (c) 27 Al NMR spectra of (2) uncalcined 20 wt%
KOH/mordenite, and (4) calcined 20 wt% KOH/mordenite

3.2. Inf luence of calcination temperature

XRD patterns of the samples calcined at 400, 500, and
600 C are shown in Figure 1. There are no significant

changes in diffraction angle and intensity. The SEM results

of the catalysts calcined at 400 to 600 C are illustrated in
Figure 2(df). The particles are agglomerated and irregular in
shape, with a substantial variation in particle size. The

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discrepancy that we observed between the effect of calcination

carried out on uncalcined and calcined catalysts is most likely
attributed to a slight decrease in crystallinity of the calcined
catalyst, particularly in samples calcined at a high temperature.
After calcination, there was an increase in Si/Al ratio or
decrease in Al atoms resulted from decreased anions of AlO
4
(dealumination). Removal of framework Al after calcination
caused a change in morphology and an increase in particle
size, while a decrease in surface area. Therefore, a high calcination temperature altered the Si/Al value, which in turn
changed the physical properties of the catalyst.
The effect of calcination temperature on the basic strength
(Table 1), demonstrated that no difference in basic strength
was found between the uncalcined and the calcined catalysts.
However, the total basic sites of the calcined catalysts continuously decreased from 5.16 to 2.21 mmol/g of catalyst when
the calcination temperature was increased. This could be due
to the collapse of the pore structure, as represented in Figure 2(m) using FE-SEM. Zhu et al. [23] proposed that KNO3
dispersed on zeolite has difficulty in thermal decomposition
even during evaporation at 600 C, hence only weak basic
sites are produced. It could be concluded that decomposition
of KOH under high temperatures on the mordenite leads to a
decrease in the basic sites of the catalyst.
The NMR peak of the catalyst calcined at 500 C shifted
from 6.37 ppm to 5.03 ppm (Figure 5a(4)), implying that the
basic strength of the catalyst should decrease due to a lower
electronic balance with the cation. However, the 1 H NMR
alone is inadequate for understanding the topology and crystallography of the calcined catalyst. Therefore, 29 Si and 27 Al
NMR are presented (Figure 5b and 5c). The large broad peak
at 93.3 ppm was assigned to Si(OSi)4 with a shoulder peak of
85 and 110 ppm, which could be identified to be a dipolar
magnetic interaction of protons with the Si(OSi)3 (OAl) framework [24,25]. The patterns of the calcined catalysts were
similar to the uncalcined catalysts, indicating that after calcination of the catalyst the silicon structure did not change

in the framework. Figure 6c shows that the spectrum line at

59.5 ppm refers to Al(H2 O)3+
6 [26]. This peak was found to
be tetrahedral framework aluminum atoms. After calcination,
the spectrum was reduced from 59.5 ppm to 56.2 ppm, which
accounts for the change in the aluminum framework. The aluminum atoms were not stable in the framework under high
calcination temperatures. By comparing the shifts in the 1 H
NMR results of the calcined catalyst, there was a decreased
bridging of hydroxyl, AlO H+ and the number of electron
sites which are normally generated by cooperation with the
aluminum atoms in the framework. It may be noted that the
aluminum atoms were the primary factors which were regularly involved with basic sites via the electronic charges that
were introduced in the framework through the AlO4 tetrahedral.
The basic strength of zeolites depend on the SiOAl angle, the TO distance and the OM distance (where M is an
exchanged alkaline cation) [27]. The larger size of the exchanged potassium, instead of sodium, caused a greater distance which resulted in a higher basic strength. Not only
the size of the cation diameter, but also the high amount of
potassium cations increased the basic strength due to the intense electropositivity of the counteraction in the zeolite [28].
Thus, an increased potassium loading created a rich-positively
charged surface which could quickly react with the methanol
to form methoxide.
Barthomeuf [29] proposed that the basic strength of zeolite depends on the Al location and the basic sites could be
evaluated from the number of Al in the tetrahedral framework.
Figure 6 shows the mechanism of KOH on zeolite via hydrogen bound with oxygen from adjacent alumina and silicon
sites, and from two silicon sites, respectively. Water molecule
dispersion on the AI and AII sites displayed hydrogen bonding with the oxygen framework. These peaks should actually
reveal in the range of 1.8 to 2.2 ppm. However, with interference of water in the broad peak of the AIII oxygen structure
formed with Na cations, a strong electronic effect caused it to
adhere to the positive charge of the cations. An exchange of

Figure 6. Scheme of the global basicity cluster in mordenite

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Journal of Energy Chemistry Vol. 22 No. 5 2013

cations was observed when loading K ions into the framework at the BIII site, and then an immense chemical shift
of hydroxyl groups of absorbed water in the zeolite catalyst
was from 3.62 to 6.29 ppm. In addition, some excess K ions
absorbed with oxygen from the adjacent alumina and silicon
sites and from two silicon sites, as shown in Figure 6B site
I. This resulted in a broader peak and a higher chemical shift.
However, the peak at 1.32 ppm still appeared, without interference of the spectrum from the cation. It could be attributed to
the residue of the hydrogen bond of water and the vacancy site
of oxygen on the mordenite surface (Figure 6B site II). After
calcination of the catalyst at a high temperature, dealumination or increasing of the Si/Al ratio gave rise to a downfield
shift. The reduction in alumina decreased the CIII sites in
the zeolite that had the highest electron density. The chemical environment of the AlO4 tetrahedral was considered to
be the species which created strong basic sites by looking at
the (SiO)a (AlO) sequences around any given framework aluminum molecules taken as the original [30]. The variable a
represents the number of SiO between AlO in substances for
a = (1, 2, 3, ). a = 1 represents the highest basic sites due
to close of Al atoms. The oxygen atoms (a>2) were less basic and farther from the AlO4 tetrahedral. Dealumination of
the mordenite zeolite occurred when a, or the SiO repeating
unit, was increased from 9 to 12. It could be noted that strong
basic sites were reduced since the CI and CII sites increased

instead of the CIII sites. Moreover, removal of alumina during calcination also decreased the basic sites on the mordenite
catalyst.
3.3. Batch transesterif ication reaction
Catalytic activity of the KOH/mordenite using the batch
reactor is presented in Table 2. The catalyst size varied from
1020 mesh to 4060 mesh. It was found that the size of the
catalyst had no noteworthy effect on the methyl ester yield,
suggesting that there is no limitation of reactants which can
diffuse into the pore surface of the catalysts [31]. The methyl
ester increased with the increased reaction time, and the maximum methyl ester yield of 96.7 wt% was obtained at 3 h. The
methyl ester yield remained at a nearly constant level after 4 h.
These results are similar to the results of Alexandrova et al.,
2002 [32] and Di Serio et al., 2005 [33].
The dependence of the KOH/mordenite catalyst on potassium loading was investigated. At 5 wt% of KOH, the
KOH/mordenite catalyst showed no activity. However, the
methyl ester yield increased when the KOH loading was increased from 10 wt% to 20 wt%, and it remained constant afterwards at 25 wt%. When the KOH loading was increased to
30 wt%, the methyl ester content rapidly decreased. This was
probably caused by the high KOH loading, which destroyed
the structure of the mordenite, as was observed from XRD

Table 2. Effect of process variables on transesterification of palm oil in a batch reactor

Time
(h)
1
1
1
0
1
2
3
4
5
6
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3

Size of
catalyst (mesh)
1020
2040
4060
1020
1020
1020
1020
1020
1020
1020
1020
1020
1020
1020
1020
1020
1020
1020
1020
1020
1020
1020
1020
1020
1020
1020
1020
1020
1020
1020
1020

KOH
loading (wt%)
20
20
20
20
20
20
20
20
20
20
5
10
15
20
25
30
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20

MeOH/oil
molar ratio
15 : 1
15 : 1
15 : 1
15 : 1
15 : 1
15 : 1
15 : 1
15 : 1
15 : 1
15 : 1
15 : 1
15 : 1
15 : 1
15 : 1
15 : 1
15 : 1
6:1
9:1
12 : 1
15 : 1
18 : 1
21 : 1
15 : 1
15 : 1
15 : 1
15 : 1
15 : 1
15 : 1
15 : 1
15 : 1
15 : 1

Amount of
catalyst (wt%)
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
1
2
3
4
5
6
3
3
3

Calcination
temperature ( C)

400
500
600

Methyl ester
yield (wt%)
72.81.1
72.90.9
73.11.1
0
72.81.1
86.50.9
96.71.1
94.30.9
95.20.9
95.61.4
89.01.2
92.81.2
95.20.7
96.71.1
70.11.2
70.90.4
86.60.4
91.60.5
93.70.3
96.71.1
95.70.7
88.70.6
72.30.8
92.31.3
96.71.1
93.20.8
88.60.9
82.61.8
82.60.2
38.10.8
18.10.9

698

Pisitpong Intarapong et al./ Journal of Energy Chemistry Vol. 22 No. 5 2013

and XRF. The crystal structure collapsed and the Si/Al ratio
decreased, which revealed a change in its framework structure and its physical structure. The highest methyl ester yield
(96.7%) was obtained at a KOH loading of 20 wt% on the
mordenite.
Normally, an excess amount of methanol is used to shift
the equilibrium of transesterification to the right-hand side.
When increasing the molar ratio of methanol/oil from 6 : 1
to 12 : 1, the methyl ester yield increased considerably. Beyond the molar ratio of 15 : 1, excess methanol had no significant effect on the methyl ester content. When the amount
of methanol was over 18 : 1, glycerol separation became
more difficult, thus decreasing the biodiesel yield. This phenomenon has also been found by other researchers [34]. The
maximum methyl ester content (96.7 wt%) was obtained when
the molar ratio was 15 : 1.
The amount of the catalyst was varied from 1 wt% to
6 wt% and it was found that the methyl ester content increased
when the amount of catalyst was raised from 1 to 3 wt%.
With further increasing of the catalyst amount, the methyl ester yield decreased because of a mixing problem of the reactant, the catalyst, and the product. The maximum methyl ester
yield (96.7 wt%) was obtained at 3 wt% of catalyst.
The influence of calcination temperature on the methyl
ester content was investigated within the range of 400 C
to 600 C. A decrease in catalytic activity at high calcination temperatures occurred because of the loss of potassium
species by evaporation or sublimation at temperatures above
327 C, as reported by Porter and Schoonmaker [35]. The
XRD and XRF results indicated that the structure of the mordenite changed in terms of chemical composition, which was
in accord with the results of the Hammett indicators and acid
titration. Moreover, the collapse of porosity in the zeolite led
to decreased surface area and reduced catalytic activity, as evidenced from the N2 adsorption-desorption and SEM. Thus,
the uncalcined catalysts exhibited higher activity than that of
the calcined KOH/Mordenite catalysts.
3.4. Packed-bed transesterif ication reaction
The influence of reaction time on the methyl ester
yield was studied from 0 to 8 h at conditions of 20 wt%
KOH/mordenite, methanol/oil molar ratio 15 : 1, flow rate
11 mL/min, reaction temperature of 60 C, and 12 wt% of catalyst. The methyl ester content increased between 2 and 4 h
to over 90 wt%, thereafter it remained steady between 5 h and
8 h. The maximum methyl ester content of 94.51.3 wt% was
achieved at 4 h reaction time.
The effect of the catalyst particle size of the
20%KOH/mordenite on the methyl ester yield was also investigated by varying the mesh size at >20, 2040, and
4050 mesh. It was observed that the methyl ester content
decreased with the larger particle size. The maximum methyl
ester content of 94.51.3 wt% was obtained with the mesh
size of 4050 mesh, which was the smallest size.
It is clearly seen that the batch reactor experiment had a

shorter reaction time and obtained a higher methyl ester content than the packed-bed reactor. In the batch reactor, there
was a complete dispersion of methanol and oil on the solid
surface. However, the total surface area of the catalyst in the
packed-bed reactor was not exposed to the liquid mixture, as
some parts of the surface were touching other solid catalysts,
causing a limitation of reactant exposure to the surface [36].
Consequently, the active sites on the surface might have less
contact time with the reactant.
3.5. Reusability of the catalyst
The catalytic activity and reusability of the
KOH/mordenite were investigated. The spent catalysts were
recovered by simple filtration and a remaining amount of catalyst were used to catalyze the next cycle batch. A remarkable
reduction in catalytic performance was observed, yielding
72.3 wt% and 40.2 wt% of methyl ester content in the second
and third runs for the KOH/mordenite catalyst, respectively.
Potassium leaching of the KOH/mordenite in the mixtures
was 0.096 wt% and 0.076 wt% of KOH in palm oil in the
first and second run, respectively, suggesting that the active
species were somewhat leached from the solid support.
Additionally, the leached potassium in the mixtures during the reaction was also investigated in a batch reactor using
the ICP method. The results showed that the potassium in the
biodiesel and glycerol phase under optimum conditions were
5.94 and 526.6 ppm, respectively. Most of the leached potassium ions tended to stay in the glycerol phase due to its high
polarity, as compared to the non-polar phase of the biodiesel.
It was confirmed that the leaching of potassium from the mordenite was less than 0.1 wt%.
In order to investigate the influence of the heterogeneous
system on transesterification of a 20 wt% KOH/mordenite,
the catalyst was separated at 3 h and the remaining mixture
carried out under the same reaction conditions until 6 h. Although potassium was leached from the catalyst, the methyl
ester content of 96.20.9% was still observed at 6 h, indicating that the leached potassium had insignificantly affected the
methyl ester content. Additionally, it was noted that the basic
sites of the spent catalyst was lower than that of the fresh one
by 25% in the first and second run. It seems that the amount
of basic sites should be enough to promote the activity for
transesterification in the recycle runs, whereas the activity of
the spent catalysts declined with successive runs.
The recycled catalysts were tested in the packed-bed reactor with optimum reaction parameters. Potassium leaching in
the mixture was 0.086 wt%, which was lower than that of the
potassium leaching from the batch reactor. The advantages of
a packed-bed reactor in reusing and regeneration may become
attractive because of the possibility of longer operation times
as well as no filtration would be required in the process.
The activity of the spent catalyst was further confirmed
by FTIR analysis, as depicted by Figure 4. The peak of
the spent catalysts also demonstrates new absorption peaks
as a result of oil deposition during the reaction. The new

Journal of Energy Chemistry Vol. 22 No. 5 2013

peaks are found at 2922 cm1 , 1740 cm1 , and 1160 cm1 ,
which are credited to the CH, aldehyde (C = O), and ester
(CO), respectively [3739]. Other new peaks are observed
at 1465 cm1 and 1375 cm1 , which could be attributed to
the bending absorption of the methylene (CH2 ) and methyl
(CH3 ) groups. Moreover, the spent catalysts have a higher intensity of broad band peak at 33003700 cm1 , which corresponds to the OH band of physically absorbed water on the
molecules. Nevertheless, the peaks of the mordenite support
still appeared on the spectra of the spent catalysts. Absorbed
molecules decreased the availability on the active sites, leading to a decrease in catalytic activity [40].
The spent 20%K/mordenite catalyst was washed by commercial grade acetone at a flow rate of 11 mL/min for 1 h.
Then, the spent catalyst was evaporated in an oven at 110 C
for 24 h. Although the absorption peak at 3450 cm1 decreases in relation to the removal of oil from the surface of the
catalyst (Figure 4(4)), the activity of the treated catalyst is not
as high as the fresh catalyst. On the other hand, the surface
structure of the spent catalyst is transformed once oil is deposited on the surface. The surface structure of the treated catalyst is similar to the fresh one, implying that the properties of
the spent catalyst should be revived. Moreover, from the XRD
results there were no loss in crystallinity or diffraction lines,
implying that deposition of reacted mixtures and treatment of
the solvent did not destroy the KOH/mordenite catalysts. The
disappearance of oil agglomeration led to an increase in surface area of the treated catalyst. The results indicate that the
treated catalyst exhibited low methyl ester yield (19.8%).
3.6. Fuel properties
Table 3 lists the fuel properties of the produced biodiesel
in comparison to the EN 14214 standard. The values of methyl
ester, flash point, viscosity, and water content are close to the
requirements of the EN 14214 standard. Owing to the absence of sulfur content in the biodiesel, the use of biodiesel
can reduce emissions after combustion. Thus, the 20 wt%
KOH on mordenite catalyst can be a promising catalyst for
the biodiesel industry.
Table 3. Comparison of the biodiesel and EN 14214
Parameter
Ester content
Linolenic acid methyl ester content
Viscosity at 40 C
Flash point
Water content
Sulfur content

Present
work
96.67
0.24
4.86
192
0.019
0

Biodiesel
standard
>96.5
<12.0
3.55.0
>120
<0.05
<0.02

Units
wt%
wt%
cSt
C
wt%
wt%

4. Conclusions
20%KOH/mordenite is an efficient catalyst for transesterification of palm oil with methanol, exhibiting the highest activity with methyl ester yield of 96.7 wt% among the

699

tested catalysts. The activity of the the uncalcined catalyst was

higher than that of the calcined catalyst. At high calcination
temperatures, the pore structure of the mordenite collapsed
and dealumination occurred. In addition, the basic sites decreased with increasing in calcination temperature. The leaching of the K species was relatively low from the solid support
during the reaction. Further studies need to be conducted to
investigate the reusability of the catalyst after being treated
with other solvents.
Acknowledgements
This work was supported financially by the National Metal and
Materials Technology Center, Thailand, and the Center of Excellence
on Petrochemical and Materials Technology, Thailand.

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