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Bioresource Technology 99 (2008) 74387443

Removal of free fatty acid in waste frying oil by esterication


with methanol on zeolite catalysts
Kyong-Hwan Chung a,*, Duck-Rye Chang b, Byung-Geon Park c
b

a
Center for Functional Nano Fine Chemicals, Chonnam National University, 300 Yongbong-dong, Gwangju 500-757, Republic of Korea
Solar Energy R&D Team, Gwangju Research Center, Korea Institute of Industrial Technology, 1110 Oryong-dong, Gwangju 500-480, Republic of Korea
c
Department of Food and Nutrition, Kwangju Womens University, 165 Sanjeong-dong, Gwangju 506-713, Republic of Korea

Received 1 January 2008; received in revised form 16 February 2008; accepted 20 February 2008
Available online 1 April 2008

Abstract
The removal of free fatty acid (FFA) in waste frying oil by esterication with methanol was conducted using various zeolite catalysts.
The ZSM-5 (MFI), mordenite (MOR), faujasite (FAU), beta (BEA) zeolites, and silicalite were employed with dierent Si/Al molar ratio
in the reaction. The eects of acidic properties and pore structure of the zeolite catalysts were discussed relating to the conversion of the
FFA. The MFI zeolite induced an improvement of the removal eciency of FFA by cracking to the FFA in its pore structure due to its
narrow pore mouth. The catalytic activity for FFA removal was lowered with decreasing of acid strength of the zeolites. The strong acid
sites of zeolites induced the high conversion of FFA comparatively. The acid strength and pore structure of acidic zeolites aected the
catalytic activity in FFA removal.
2008 Elsevier Ltd. All rights reserved.
Keywords: Free fatty acid removal; Esterication; Zeolite; Waste frying oil; Acidity

1. Introduction
Biodiesel is biodegradable and nontoxic, has low emission proles and so is environmentally benecial (Krawczyk, 1996). Biodiesel comprises of long chain, fatty
acid alkyl esters produced from vegetable oils or animal
fats by transesterication of the triglycerides with lower
(Schuchardt et al., 1998; Ma and Hanna, 1999; Barnwal
and Sharma, 2005; Meher et al., 2006).
Conventionally, biodiesel is produced using a homogeneous mineral acid or alkali catalysts. In addition to the
corrosion problems, these homogeneous catalyst-based
processes involve elaborate process steps for removal of
FFAs and water from the feedstock and catalyst from
the products. In acids oils, the amount of FFA varies from
3% to 40% (Srivastava and Prasad, 2000; Ma and Hanna,
1999). However, when the amount of FFAs in the feed*

Corresponding author. Tel.: +82 62 530 0328; fax: +82 62 530 1920.
E-mail address: chung-sea@hanmail.net (K.-H. Chung).

0960-8524/$ - see front matter 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biortech.2008.02.031

stocks exceeds 0.5%, they react with the homogeneous


alkali catalysts, form unwanted soap by-products and
deactivate the catalyst. Furthermore, they will make more
dicult the downstreaming separation and purication of
the biodiesel.
When an acid oil is employed, the side reaction of direct
esterication will inherently take place (Knothe et al., 2005;
Marchetti et al., 2007a; Vicente et al., 2004; Schuchardt
et al., 1998). The side reaction is of great importance due
not only to the possible increase on the biodiesel production, but also because it will aect the properties of future
biodiesel (Knothe, 2005; Geller and Goodrum, 2004; Goodrum and Geller, 2005).
There have been several reports on the use of heterogeneous base or acid catalysts for the FFA removal (Liu
et al., 2007; Takagaki et al., 2006; Cantrel et al., 2005;
Abreu et al., 2005; Suppes et al., 2004; Tesser et al., 2005;
Kim et al., 2004). Solid metal oxides of tin, magnesium
and zinc have been reported. Leaching of metal ions was
encountered in the case of basic zeolite X and ETS-10

K.-H. Chung et al. / Bioresource Technology 99 (2008) 74387443

catalysts (Suppes et al., 2004). A range of catalysts including Mg/Al hydrotalcites, alkali nitrate and alkali carbonate-loaded Al2O3, polymer resins, sulfated-tin and
zirconia oxides and tungstated-zirconia have also been
reported (Lopez et al., 2005; Jitputti et al., 2006; Furuta
et al., 2004; Karmee and Chadha, 2005; Mbaraka et al.,
2003). The double-metal cyanide complexes were also
employed in the FFA removal (Sreeprasanth et al., 2006).
The preparation of solid catalysts, however, has a complicated procedure with a high expense.
Zeolites are microporous crystalline solids with welldened structures. Generally they contain silicon, aluminum and oxygen in their framework and cations. Zeolites
are nding applications in many areas of catalysis, generating intense interest in these materials in industrial and academic laboratories. As catalysts, zeolites exhibit appreciable
acid activity with shape selective features not available in
the compositionally equivalent amorphous catalysts. More
recent research on alcoholysis has focused on the use of heterogeneous catalysts (Suppes et al., 2004). Zeolites have
been employed in biodiesel production as a heterogeneous
catalyst. However, esterication of oil has no studied on
zeolites catalysts for FFA removal.
In present study, the direct esterication reaction of the
FFA in waste frying oil with methanol was conducted
using various zeolite catalysts. The acidic properties of
the zeolites with various Si/Al molar ratios were evaluated
using NH3-temperature programmed desorption (TPD)
analysis. The catalytic activity of the zeolite catalysts was
studied on the FFA removal reaction. The eects of acidic
properties and pore structure of the zeolite catalysts were
discussed relating to the conversion of FFA.
2. Experimental
2.1. Preparation of zeolite catalysts
The MFI zeolites were synthesized with a dierent Si/Al
molar ratio through hydrothermal reaction of a synthetic
mixture composed of colloidal silica (Ludox, 40 wt%
SiO2, Aldrich), aluminum hydroxide (64 wt%, Fluka),
potassium hydroxide (80 wt%, Daejung) and deionized
water. The synthetic mixture was aged for 72 h and heated
at 190 C for 48 h. The Si/Al molar ratio of the synthesized
MFI zeolites was 50 and 350, respectively. Other MFI zeolites were purchased from Zeolyst Co.. The Na-type MFI
zeolites were treated with ammonium nitrate (>99 wt%,
Duksan) of 0.5 N at 60 C to exchange its cations to
ammonium ions. H-type MFI zeolites were obtained by
calcining them at 550 C for 6 h in air.
The MOR zeolite (Si/Al = 10) purchased from Tosoh
Co. was used as a starting material for dealumination. Acetic acid (Wako, 99%) of 6 N was employed in the preparation of the dealuminated MOR zeolite to obtain the MOR
zeolites with dierent Si/Al molar ratio. The parent MOR
zeolite was treated with the acetic acid solution for 5 h.
Reuxing time was enlarged to 12 h in order to remove

7439

more aluminum atoms from the zeolite framework. The


acid-treated MOR zeolites were carefully washed with
deionized water and dried at 100 C followed by calcining
at 500 C in air stream for 12 h. The H-type MOR zeolites
were obtained by the ion exchange according to the method
mentioned above.
The H-beta (HBEA) and H-faujasite (HFAU) zeolites
were prepared from Na-BEA zeolite (PQ Co., Si/Al = 13)
and Na-FAU zeolite (Union Carbide, Si/Al = 3) by ion
exchange with a 2 M solution of NH4NO3 (Aldrich) at
80 C. Afterwards, the samples were ltered, washed and
dried overnight at 100 C. Silicalite was synthesized according to the procedure outlined by the literature (Rimer et al.,
2004). We denote the prepared H-form zeolites as framework type code of the zeolites (HMFI, HMOR, HFAU,
HBEA) by writing their Si/Al molar ratios in the parentheses after code name.
2.2. Characterization of zeolite catalysts
The X-ray diraction (XRD) patterns of the zeolites
were recorded on an X-ray diractometer (Rigaku D/
Max Ultima III) operating under 40 kV and 40 mA with
the scan rate of 2/min. Cu ka X-ray was nickelltered.
Shapes and sizes of the zeolites were examined by a scanning electron microscope (SEM, Hitachi S-4900) and their
Si/Al molar ratios were determined using an energy dispersive X-ray attachment (EDX, NORAN Z-MAX 300 Series). Nitrogen adsorption isotherms were obtained at
liquid nitrogen temperature by an automatic volumetric
adsorption system (Mirae SI, nanoPorosity-XQ). The zeolite samples were evacuated at 150 C for 2 h prior to nitrogen adsorption.
NH3-TPD proles of the zeolites were obtained using a
chemisorption analyzer (Bel Japan, BELCAT). The zeolite
samples were activated in a helium ow at 550 C for 1 h,
then cooled to 150 C. Ammonia pulses were added to
the zeolite samples till they were saturated with it. The samples were purged with a helium ow at 150 C for 1 h to
remove physically adsorbed ammonia. The temperature
of the zeolite sample was increased to 600 C with the
ramping rate of 10 C/min. The amount of strong acid site
on the zeolite surface was dened from the peak deconvolution from 250 C to 600 C to the measured spectrum.
2.3. FFA removal by esterication with methanol
The reaction of FFA removal over the zeolite catalysts
was carried out by a batch-type reactor equipped mechanical stirrer and a water-cooled condenser. The reactants
consisted of methyl alcohol (Aldrich, 99%) and a waste frying oil obtained from chicken frying store. The molar ratio
of waste frying oil and methyl alcohol was adjusted as 1:30
according to the literature (Marchetti et al., 2007b). To
evaluate the catalytic activity for FFA removal on various
zeolite catalyst, the oleic acid (Aldrich, 99%) was added
into waste frying oil as an excess FFA reagent with

K.-H. Chung et al. / Bioresource Technology 99 (2008) 74387443

where ai is the initial acid number of the reactant and at is


the acid number of product at a t time. The acid number
of product was measured after separating from methanol
and glycerol.
2.4. Analysis
Methyl ester content in the products was measured by
GC analysis according to the EN 14103 test method (van
Gerpen et al., 2004). At rst, standard (STD) solution
was prepared as 10 mg/ml of methyl heptadecanoate
(C17:0) with heptane solution. The sample (250 mg) was
added in the standard solution (5 ml). The mixed sample
with STD solution was analyzed by GC. The methyl ester
content was determined from the equation as following:
P
A  As C s V s
Methyl ester content %
 100
2

As
m
where RA = summation of peak areas of methyl esters
(C14:0C24:1), As = peak area of methyl heptadecanoate
(STD material), Cs = concentration of STD solution
(10 mg/ml), Vs = volume of STD solution (5 ml), and
m = amount of sample (250 mg).
Acid number was determined according to ASTM D
664 by potentiometric titration. The sample was dissolved
in a mixture of toluene and isopropanol. The sample was
titrated potentiometrically with alcoholic potassium
hydroxide. The meter readings are plotted dened inections in the resulting curve. Acid number was the quantity
of base, expressed as mg KOH/g of sample, required to
titrate the sample to a specied end point. Acid number
was calculated according to the below equation (van Gerpen et al., 2004)
N acid 56:1  MA  B=W

where Nacid = acid number, M = concentration of KOH


(mol/l), A = volume of KOH used to reach end point corresponding to basic buer (ml), B = volume corresponding
to A for blank titration (ml), and W = mass of sample (g).
Kinematic viscosity of the produced biodiesel was measured according to ASTM D 445. The test was conducted
by measuring the time required for a volume of liquid to

ow under gravity through a CannonFensake style glass


capillary tube used commonly for ASTM D 445 (van Gerpen et al., 2004). Density of the products dened from specic gravity (gspec) and reference density (qref). The
equation for the density (q) is q = qref  gspec. Specic gravity was measured using a hydrometer.

3. Results and discussion


3.1. Physical and chemical properties of the zeolites
X-ray diraction patterns of the zeolites were identical
with those published in previous literature (Roboson and
Lillerud, 2001), indicating that the zeolites used in this
study were highly crystalline. Particle sizes dened from
SEM photos of FAU and MFI zeolites were around
0.5 lm, and that of MOR zeolite was slightly large, at
1.52.0 lm. On the other hand, BEA zeolite was composed
of small particles below 0.2 lm. The zeolites were selected
in this study because they had sucient external surface
and did not contain extremely large particles without activity. Furthermore, the zeolites with similar particle sizes are
suitable for the study of the eect of pore shape.
Fig. 1 shows nitrogen adsorption isotherms. Since micropores of zeolites are lled with adsorbed nitrogen even at very
low pressures, Langmuir type adsorption isotherms are usually obtained on zeolites. The isotherms of nitrogen on
HMFI(25) and HMOR(10) zeolites showed typical characteristics of Langmuir type. On the other hand, the adsorbed
amounts of nitrogen on HBEA(13) zeolite increased slightly
at 0.20.7 of relative pressure, indicating the presence of
mesopores. Large adsorption on HFAU(3) and HBEA(13)
zeolites are attributed to their large void fraction, but the
mesopores of HBEA(13) zeolite are due to the secondary
pores formed among extremely small zeolite particles.
BET surface area and structural parameters are listed in

500

: HBEA(13)

10 vol% to the oil. The removal of FFAs and production of


biodiesel on the HMFI(25) zeolite catalyst were also performed to the waste frying oil without adding of oleic acid.
The reactants were charged, and then were stirred in a
round bottom ask. The speed of stirring maintained with
600 rpm. The composition of products was analyzed by gas
chromatograph (Donam DS6200) equipped with a capillary column (HP-1, i.d.: 0.32 mm, length: 50 m, lm thickness: 0.17 lm) and a FID detector. The conversion of the
FFA was dened as the fraction of the FFA removed.
The conversion of FFA (xFFA) was determined from acid
number ratio using below equation
as  at
xFFA
 100
1
as

Adsorbed amount of nitrogen (cm /g)

7440

: HFAU(3)

400

: HMFI(25)

: HMOR(10)
: HFER(6)

300

200

100

0
0

0.2

0.4

0.6

P/P0
Fig. 1. N2 isotherms of the zeolites.

0.8

K.-H. Chung et al. / Bioresource Technology 99 (2008) 74387443

ratio ()
MFI

25

10-oxygen ring

T max

BET surface
area (m2/g)

5.1  5.5[1 0 0]
5.3  5.6[0 1 0]

413

MOR

10

12-oxygen ring
8-oxygen ring

6.5  7.0[0 0 1]
2.6  5.7[0 0 1]

419

FAU

12-oxygen ring

7.4  7.4[1 1 1]

574

BEA

13

12-oxygen ring

6.6  6.7[1 0 0]
5.6  5.6[0 0 1]

577

Table 1. MFI zeolite has a narrow pore entrance compared


with that of other zeolites.
Acidic properties of zeolites are varied with zeolite species. Although the Si/Al molar ratios of the zeolites were
controlled to be similar, their acidic properties were considerably dierent as shown in the NH3-TPD proles of
Fig. 2. The TPD technique is widely used to obtain a general feature of acidity of the catalyst (Miyamoto et al.,
2000). The amount of acid sites of the catalysts can be
determined from desorption peak area of ammonia. The
acid strength can be evaluated by the maximum peak temperature (Tmax) of desorption peak relating to the activation energy for desorption of ammonia.
The desorption peaks observed at 350550 C are attributed to strong acid sites, whereas those at 150250 C to
weak acid sites or physically adsorbed ammonia (Lonyi
and Valyon, 2001). HMOR zeolites had the largest number
of strong acid sites among the zeolites. On the other hand,
silicalite had no strong acid site. The number of strong acid
sites is varied with spatial conformations of SiOAl bonds
determined by zeolite skeletal, while the number of total
acid sites is the function of the Si/Al molar ratio. Silicalite
had only weak acid sites, and even they were also very
small.
TPD proles of HMFI zeolites with dierent Si/Al
molar ratio are represented in Fig. 3A. The strong acid sites
were signicantly decreased with decreasing of Al content

HMOR(10)

HMFI(25)
HMFI(50)
HMFI(75)
HMFI(350)

TCD response (a. u.)

Table 1
Structural and compositional properties of the zeolites
)
Zeolite Si/Al molar Pore topology
Pore size (A

7441

100

200

300

400

500

600

500

600

T max

HMOR(10)
HMOR(13)
HMOR(64)
HMOR(100)

100

200

300

400

Temperature (C)
Fig. 3. NH3-TPD proles of (A) HMFI and (B) HMOR zeolites with
dierent Si/Al molar ratio.

Table 2
Conversion of FFA and NH3-TPD properties on HMFI and HMOR
zeolites with dierent Si/Al molar ratio
Zeolite

Si/Al molar
ratioa ()

Acid amountb
(mmol/g)

Tmaxc
(C)

Conversiond
(%)

HMFI

25
50
75
350

7.9  102
4.5  102
3.8  102
0.5  102

415
395
375
360

80.6
77.1
75.3
60.6

HMOR

10
13
64
100

15.1  102
13.0  102
6.6  102
3.0  102

510
508
450
425

80.9
79.4
76.7
76.5

The values determined by EDX result.


The values determined by deconvolution of NH3-TPD spectra from
250 C to 600 C.
c
The values determined by NH3-TPD spectra.
d
The values determined by FFA removal reaction at 60 C.

TCD responce (a. u.)

HFAU(5)

HMFI(25)

silicalite

100

200

300

400

500

Temperature (C)
Fig. 2. NH3-TPD proles of the zeolites.

600

in zeolite framework as shown in Fig. 3A and Table 2. In


addition, the Tmax of strong acid site slightly shifted toward
a low temperature. Diminishing of the strong acid sites and
shifting of the Tmax toward the low temperature also
appeared considerably in the TPD proles of HMOR with
dierent Si/Al molar ratio as shown in Fig. 3B and Table 2.
However, the Tmax of all HMOR zeolites were higher than
that of HMFI(25). It means that the all HMOR zeolites

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K.-H. Chung et al. / Bioresource Technology 99 (2008) 74387443

have strong acid sites more than HMFI(25) zeolite exhibited the strongest acid strength among the HMFI zeolites.
3.2. Catalytic activities of the zeolite catalysts in the FFA
removal by esterication
The reaction took place not only esterication but also
transesterication in the study. It was conrmed from the
composition distribution of product and feedstock oil.
The composition of oleic acid and palmitic acid increased
signicantly after the reaction compared with feedstock
oil. It was dened that the linoleic acid in the feedstock disappeared nearly after the reaction. The conversion of FFA
on HMFI(25) with various reaction conditions was evaluated in the esterication of FFA with methanol. The conversion of FFA was slightly improved to 80% with increasing
of reaction temperature, but it exhibited no more increase
at above 60 C. The conversion of FFA also became higher
with increasing of loading amount of HMFI(25) zeolite.
However, it did not show a signicant increase above
1.0 g of catalyst loading. The conversion of FFA increased
with proceeding of reaction and it reached to equilibrium
after 90 min. To compare the catalytic activities of the zeolite catalysts in the FFA removal reaction, the reaction conditions were adjusted as 1.0 g of catalyst loading, 60 C of
reaction temperature, and 3 h of reaction time, hereafter.
Fig. 4 represents the catalytic activities of the FFA
removal reaction on various zeolite catalysts compared to
their acid amounts. The high conversion of FFA appeared
on HMFI(25) and HMOR(10) zeolite catalysts. Silicalite
exhibited a low conversion of FFA in the reaction since
it has only very weak acid site. The order of high conversion has a relation with acid amount of the zeolites excluding HMOR zeolites. Although HMOR(10) has a stronger
acid strength and more acid sites than those of HMFI(25)
zeolite, the conversion of HMOR(10) was similar with that
of HMFI(25). This means that there are other factors
besides the acidic properties in evaluation of FFA removal
activity on the zeolites. MFI zeolite has a small pore size
[1 0 0]) compared with that of MOR zeolite
(5.1  5.5 A
100

Conversion of FFA (%)

acid amount

0.12

60

0.09

40

0.06

20

0.03

Acid amount of zeolite (mmol/g)

0.15
conversion

80

[0 0 1]). Furthermore, its pore structure is bent


(6.5  7.0 A
as a zigzag type. On the contrary, MOR zeolite has a
straight pore channel and a wide pore entrance. The bent
pore structure of MFI zeolite can induce a cracking to a
long chain reactant like as oleic acid in its pore inside (Park
et al., 2002). However, it is dicult to expect the cracking
in MOR zeolite pore, because a wide and linear pore structure of MOR zeolite cannot split the oleic acid. At rst, the
narrow pore mouth of HMFI zeolite might interrupt the
penetration of oleic acid. Secondly, cracking of FFA in
bent pore inside might happen. Therefore, it can be surmised that the narrow pore entrance of HMFI zeolite
might aect the improvement of FFA removal conversion
more than its bent pore topology.
Conversion of FFA on HMFI zeolites decreased with
increasing of Si/Al molar ratio. As listed in Table 2, the
amount of acid site and acid strength, which evaluated
from Tmax, became lower with decreasing of Al content.
This resulted that decreasing of acidity on HMFI zeolites
induce the reducing of catalytic activity for FFA removal.
On the contrary, the HMOR zeolites exhibited practically a
similar conversion of FFA with dierent Si/Al molar ratio,
although the acidity decreased. The acid amount and acid
strength of HMOR zeolites decreased with dealumination
to the parent HMOR zeolite. However, the acid strength
of HMOR(100) zeolite was higher than those of other zeolites, that is, the Tmax of HMOR(100) was even higher than
that of HMFI(25). It seems that the strong acid sites of
HMOR zeolites induced the high conversion of FFA
comparatively.
Table 3 lists the chemical properties of the products
obtained from the reaction of waste frying oil after separation of methanol and glycerol. These are results of the
esterication of FFA in waste frying oil without addition
of excess oleic acid on HMFI(25) and HMOR(10) zeolite
catalysts. The conversion of FFA was obtained as 78%
and 80% for HMFI(25) and HMOR(10) zeolite, respectively. The conversion was similar with the result of the
study conducted by Marchetti et al. (2007a,b). They used
basic resins as a catalyst in esterication of oil.

Table 3
Chemical properties of the products obtained from FFA removal by
esterication of FFA in waste frying oil with methanol on the zeolites at
60 C and 3 h reaction time
Property

Waste frying
oil before
FFA removal

Product after
the reaction
on HMFI(25)

Product after
the reaction
on HMOR(10)

Density at 15 C
(kg/m3)

902

885

872

Kinematic viscosity at
40 C (mm2/s)

3.9

2.6

2.5

Acid number
(mg KOH/g)

1.25

0.28

0.25

Methyl ester content


(%)

27

77

81

HMFI(25) HMOR(10) HFAU(3) HBEA(13)

Silicalite

Fig. 4. Relation of conversion of FFA and acid amount of the zeolites:


reaction temperature = 60 C. Amount of catalyst = 1.0 g. Reaction
time = 3 h.

K.-H. Chung et al. / Bioresource Technology 99 (2008) 74387443

The acid number of the waste frying oil was 1.25 mg


KOH/g before the reaction. After the FFA removal reaction
to the waste oil, the acid number reduced to 0.28 mg KOH/
g, and 0.25 mg KOH/g on HMFI(25) and HMOR(10) zeolite, respectively. The acid number after FFA removal reaction was allowed within the limit of European biodiesel
qualities (van Gerpen et al., 2004). Density and kinematic
viscosity of the products were also improved to the limits
of the EN 14214. However, methyl ester contents of the
products were low to the limits. The methyl ester contents
could be improved to the limit by additional esterication
reaction for 48 h.
4. Conclusion
The zeolite catalysts were active on the esterication
reaction of FFA in waste frying oil with methanol. Conversions of FFA on HMFI(25) zeolite and HMOR zeolites
were obtained about 80% in the reaction at 60 C. In eect
of pore structure, the narrow pore entrance and bent pore
of MFI zeolite might induce the cracking of FFA in its
pore mouth and inside. The catalytic activity for FFA
removal was lowered with decreasing of acidity of HMFI
zeolites. On the contrary, the HMOR zeolites exhibited
practically a similar conversion of FFA with dierent Si/
Al molar ratio, although the acidity decreased. It seems
that the strong acid sites induced the high conversion of
FFA comparatively and the narrow pore entrance of
HMFI(25) zeolite brought on the improvement of FFA
removal. Acid strength and pore mouth size of the zeolites
aected the catalytic activity of FFA removal.
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