Available online at www.sciencedirect.

com

Fuel 87 (2008) 1789–1798

www.fuelfirst.com

Esterification of free fatty acids in waste cooking oils

(WCO): Role of ion-exchange resins
Nalan Özbay, Nuray Oktar *, N. Alper Tapan
Faculty of Engineering and Architecture, Department of Chemical Engineering, Gazi University, 06570 Maltepe, Ankara, Turkey

Received 3 October 2007; received in revised form 17 December 2007; accepted 19 December 2007
Available online 15 January 2008

Abstract

Although WCO plays a crucial role for the economical production of biodiesel, free fatty acid (FFA) level in the nature of WCO cause
saponification problems during transesterification. Acidic ion-exchange resins can be used to decrease WCO free fatty acid level. In this
study, activities of resins (Amberlyst-15 (A-15), Amberlyst-35 (A-35), Amberlyst-16 (A-16) and Dowex HCR-W2) in direct FFA ester-
ification were examined in the temperature range of 50–60 °C and the effect of catalyst amount (1–2 wt%) on FFA conversion was also
analyzed. FFA conversion increased with increasing reaction temperature and catalyst amount. Order of catalytic activities was found as
A-15 > A-35 > A-16 > Dowex HCR-W2. This was related to the size of average pore diameters and magnitude of BET surface area.
Ó 2007 Elsevier Ltd. All rights reserved.

Keywords: Biodiesel; Esterification; Ion-exchange resins

1. Introduction Biodiesel can be produced by transesterification,

Since fossil fuels increase greenhouse gas emissions and
cause global warming, the use of alternative resources like
biofuels are more pronounced everyday. For example,
European Community has decided to replace at least
5.75% of the yearly consumed fossil fuels by biofuels, by
the year 2010. The use of these biofuels does not contribute
to the growth of greenhouse gases (2003/30/EC directive)
[1].
As an alternative to fossil fuels, biofuels must be techni-
cally feasible, economically competitive, environmentally
acceptable, and readily available [2]. Regarding these prop-
erties, biodiesel has been widely recognized as a promising
biofuel. On the other hand, biodiesel is usually more expen-
sive than petroleum-based diesel fuel when it is produced
from vegetable oils or animal fats [3].
*
Corresponding author. Tel.: +90 312 2317400 2556; fax: +90 312
2308434.
E-mail address: nurayoktar@gazi.edu.tr (N. Oktar).
whereby oil reacts with low molecular weight alcohols [4].
Generally, alkaline catalysts (like sodium hydroxide), are
used with low FFA content oils to catalyze transesterifica-
tion reaction.
Biodiesel can also be produced from waste cooking oils
(WCO) [5–14]; it is being tested for diesel engine perfor-
mance [15,16] and has similar performance with biodiesel
produced from fresh vegetable oils. In spite of its low cost,
WCO pretreatment is still a problem [17] due to its high
free fatty acid level. Lately, Canakci and Van Gerpen
developed a two step pretreatment reaction that reduces
the acid level of the high FFA feedstocks to <1% [18].
Transesterification of WCO feedstocks with FFAs (lar-
ger than 0.5%) cause an undesired saponification reaction.
In order to eliminate this problem, alternative acid
catalysts can be employed [19]. When strong liquid acid
catalysts (sulfuric acid, hydrofluoric acid, and p-toluenesul-
fonic acid) are used, they are less sensitive to FFA conver-
sion during transesterification. In addition, the rate of
reaction is slow and higher reaction temperatures are
required. On the other hand, if solid acid catalysts like

0016-2361/$ - see front matter Ó 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.fuel.2007.12.010
1790 N. Özbay et al. / Fuel 87 (2008) 1789–1798

Nomenclature

A acidity (gOA/goil) MWOA molecular weight of oleic acid (g/mol)

CNaOH concentration of NaOH (mol/L) msample weight of sample (g)
VNaOH volume of solution consumed during titration
(mL)

ion-exchange resins, zeolites and superacids like sulphated 2. Experimental

zirconia and niobium acid [20] are used, they could prevent
corrosion [21], their separation is easy, and also high FFA 2.1. Materials
conversions can be achieved [22].
Ion-exchange resins are commonly used for esterifica- Three WCO batches were obtained from university caf-
tion [23–26] and transesterification reactions [27]. They eterias in ANKARA and filtered to remove impurities. The
have a gel type structure of microspheres that form a mac- acidities of the feedstocks were 0.47, 0.42 and 0.41 wt%.
roporous polymer [28]. Conventional ion-exchange resins Analytic grade methanol was purchased from Merck
are composed of copolymers of divinylbenzene (DVB), sty- Chemicals for esterification reaction. Commercial strong
rene and sulfonic acid groups [being the active site acidic ion-exchange resins (A-15 (Merck), A-35 (Rohm
(Brønsted acidity)]. Polymer structure of resin is character- and Haas), A-16 (Fluka) and Dowex HCR-W2 (Merck))
ized by the content of the crosslinking component (DVB),
which determines surface area and pore size distribution of
the resin [29]. 60
The aim of this study is to compare activities of different A-15
50 A-35
strong acidic ion-exchange resins like Amberlyst-15,
A-16
Amberlyst-35, Amberlyst-16 and Dowex HCR-W2 for 40
Dowex HCR-W2
FFA esterification in WCO and examine the effect of cata-
lyst amount, reaction temperature and reaction time on the 30
esterification.
20

10

0
Table 1 Surface area Porosity (%) Average pore Ion exchange Particle
Characteristics of ion-exchange resins m2/g diameter (nm) capacity diameter
Property A-15 A-35 A-16 Dowex (meq/g) (nmx10)
HCR-W2
Fig. 1. Properties of ion exchange resins.
Structure MR MR MR G
Matrix Styrene– Styrene– Styrene– Styrene–
divinyl- divinyl- divinyl- divinyl-
benzene benzene benzene benzene 0.45
Form H+ H+ H+ H+
0.4 STM
Crosslinking level H H L L
Exchange capacity 5.2d 5.2c 4.8c 4.8e ITM
0.35
(meq/g)
Surface area (m2/g) 53c 50c 30c – 0.3
Acidity (wt%)

Porosity (%) 33a 29a 25b –

0.25
Average pore 30c 30c 25c –
diameter (nm) 0.2
Particle diameter 0.74f 0.15–0.25g 0.38–0.45g >1.2 (%2)e
(mm) <0.42h 0.15
(%1)e
0.1
MR: macroreticular structure, G: gel type polymer, H: high, L: low.
a 0.05
[27].
b
[29].
c 0
[30]. 0 50 100
d
[31]. Reaction Time (min)
e
[32].
f
[33]. Fig. 2. Comparison of different acidity test methods with Dowex HCR-
g
[34]. W2 (at 60 °C and 2 wt% catalyst amount). STM: standard titration
h
[35]. method, ITM: indirect titration Method.
 N. Özbay et al. / Fuel 87 (2008) 1789–1798 1791

100 Table 2
Comparison of strong acid ion-exchange resins for FFA esterification at
90
A-15 50 and 60 °C
80 A-35 T (°C) Catalyst XFFA (%)
A-16
70 amount (wt%)
A-15 A-35 A-16 Dowex HCR-W2
Swelling (%)

Dowex HCR-W2
60
50 1 25.4 23.0 22.1 20.8
50 2 32.6 30.6 29.9 24.2
60 1 37.2 36.5 34.1 30.4
40
2 45.7 41.9 40.1 34.7
30
Reaction time = 3 h. XFFA: conversion of FFAs in WCO.
20

10
that A-15 has superior physical properties with respect to
0 others.
45 50 55 60 65

Temperature ( oC)

Fig. 3. Swelling (%) of different types of catalysts at 50–60 °C. 2.2. FFA esterification

were used as solid acidic catalysts. Amberlyst and Dowex Esterification reactions were performed in a three-necked
HCR-W2 resins (in wet form) were dried in an oven for batch reactor (total volume 1000 ml) equipped with a reflux
12 h after washing with methanol at 110 °C and 105 °C, condenser to avoid alcohol vaporization. The three-necked
respectively. Physical properties of ion-exchange resin cat- reactor was immersed in a constant temperature water bath
alysts are summarized in Table 1. It is clearly seen in Fig. 1 equipped with a temperature controller. A plate type

50 50

45 45

40 40

35 35
FFA Conversion, (%)

FFA Conversion, (%)

30 30

25 25

20 20

15 A-15 15 A-15
A-35 A-35
10 10
A-16 A-16
5 Dowex HCR-W2 5 Dowex HCR-W2

0 0
0 50 100 150 200 0 50 100 150 200
Reaction Time (min) Reaction Time (min)

c 50 d 50

45 45

40 40
FFA Conversion, (%)

35 35
FFA Conversion, (%)

30 30

25 25

20 20

15 A-15 15 A-15
A-35 10 A-35
10
A-16 A-16
5 5
Dowex HCR-W2 Dowex HCR-W2
0 0
0 50 100 150 200 0 50 100 150 200
Reaction Time (min) Reaction Time (min)

Fig. 4. Comparison of different types of catalysts (Initial FFA levels are 0.47 (at A-15 and A-16) and 0.41 (at A-35 and Dowex HCR-W2), 20 vol%
methanol, (a) 50 °C, 1 wt% catalyst, (b) 60 °C, 1 wt% catalyst, (c) 50 °C, 2 wt% catalyst, (d) 60 °C, 2 wt% catalyst.
1792 N. Özbay et al. / Fuel 87 (2008) 1789–1798

magnetic stirrer was used to control the stirring rate of the 99.9% (Merck)). Phenolphthalein indicator was used to
reaction mixture. In order to eliminate external mass trans- determine pH change during esterification reaction. Aque-
fer effects, the stirring speed was adjusted to 1500 rpm ous solution of 0.01 N NaOH were used as a titrant. Acid-
which was much higher than values indicated in the litera- ity (A) was determined according to the equation given
ture [36]. Esterification reactions were carried out in the below:
temperature range of 50–60 °C. Resin catalysts (1 and C NaOH V NaOH MWOA
2 wt%) and 20 vol.% methanol were used in the reaction A¼ 100ðwt%Þ ð1Þ
msample 1000
mixture [37]. Sampling were done manually at reaction
times of 3, 5, 10 min and every 20 min after that. In Eq. (1) the subscript ‘‘OA” refers to oleic acid which is a
In our esterification experiments, after each sampling of type of FFA.
the reaction mixture (10 g) the new FFA concentration The conversion of FFA can be determined from the
value was evaluated based on the remaining part of the equation given below:
reaction mixture. A i  At
FFA conversion ð%Þ ¼  100 ð2Þ
Ai
2.3. Titration analysis In Eq. (2) the subscript ‘‘i” refers to initial acidity level
and ‘‘t” refers to the acidity at certain reaction time.
Reactant (WCO) and reaction mixture were analyzed by In addition to the standard analysis method, indirect
standard titration method for the evaluation of free fatty titration method in aqueous-alcohol media (described else-
acid level [1]. Before titration, a certain amount of sample where [38]) was also used (with Dowex HCR-W2 (60 °C,
(10 g) was dissolved in diethyl ether (with a purity of 2 wt%)) in order to double check the validity of acidity lev-
99.9% (Merck)) and ethanol mixture (with a purity of els during reaction.

35 35

30 30

25
FFA Conversion, (%)

FFA Conversion, (%)

25

20 20

15 15
1 wt% catalyst 1 wt% catalyst

10 2 wt% catalyst 10 2 wt% catalyst

non-catalyzed non-catalyzed
5 5

0 0
0 50 100 150 200 0 50 100 150 200
Reaction Time (min) Reaction Time (min)

c 35
d 35

30 30
FFA Conversion, (%)

FFA Conversion, (%)

25 25

20 20

15 15
1 wt% catalyst 1 wt% catalyst
10 10
2 wt% catalyst 2 wt% catalyst

5 non-catalyzed 5 non-catalyzed

0 0
0 50 100 150 200 0 50 100 150 200
Reaction Time (min) Reaction Time (min)

Fig. 5. Effect of amount of catalyst at 50 °C (A-15 (a), A-35 (b), A-16 (c), Dowex HCR-W2 (d)). Initial FFA levels are 0.47 (at A-15 and A-16), 0.41 (at A-
35, Dowex HCR-W2 and non-catalyzed), 20 vol% methanol.
 N. Özbay et al. / Fuel 87 (2008) 1789–1798 1793

2.4. Swelling experiments
Before analyzing the effect of swelling on activities of
catalysts, the swelling capacities were determined as
described below:
Amberlysts (A-15, A-35, A-16) and Dowex HCR-W2
catalysts were dried in an oven at 110 °C and 105 °C,
respectively. Then 0.5 cm3 of treated resin was placed into
a measured tube. Methanol was added into the tube and
tempered at 50–60 °C in temperature controlled water bath
for 2 h. The change of the ion-exchange resin volume was
recorded. Percentage of swelling at room temperature
was calculated according to the following equation:
swollen volume ðcm3 Þ
Swelling ð%Þ ¼
initial volume ðcmÞ
ined and to see the reproducibility of the results FFA acid-
ity during reaction was confirmed by two different test
methods. And also the relation between some physical
properties like crosslinking level and swelling capacity
was confirmed.
3.1. Validation of two different WCO acidity test methods
The FFA acidity of WCO (during esterification with
Dowex HCR-W2 (60 °C, 2 wt%) acidic resin) was con-
firmed by indirect titration method in aqueous-alcohol
media [38] and standard titration method [1]. The agree-
ment between these two test methods can be seen in Fig. 2.
3
 100 ð3Þ
3.2. Swelling capacity of ion-exchange resins

3. Results and discussion
In this part of the study, the effect of reaction parame-
ters (the amount and type of acidic ion exchange resin
and reaction temperatures) on FFA conversion were exam-
The degree of crosslinking determines the rigidity of the
resin and the extent of swelling in the presence of a polar
component. Resins with lower crosslinking have higher
swelling capacity [30]. Fig. 3 indicates the swelling capacity
of resins at 50 and 60 °C in pure methanol. The literature

50 50

45 45

40 40
FFA Conversion, (%)

FFA Conversion, (%)

35 35

30 30

25 25

20 1 wt% catalyst 20 1 wt% catalyst

15 2 wt% catalyst 15 2 wt% catalyst
10 non-catalyzed 10 non-catalyzed
5 5

0 0
0 50 100 150 200 0 50 100 150 200
Reaction Time (min) Reaction Time (min)

c 50 d 50
45 45
40 40
FFA Conversion, (%)

FFA Conversion, (%)

35 35
30 30

25 25

20 20
1 wt% catalyst 1 wt% catalyst
15 15
2 wt% catalyst 2 wt% catalyst
10 10
non-catalyzed non-catalyzed
5 5

0 0
0 50 100 150 200 0 50 100 150 200
Reaction Time (min) Reaction Time (min)

Fig. 6. Effect of amount of catalyst at 60 °C. (A-15 (a), A-35 (b), A-16 (c), Dowex HCR-W2 (d)) Initial FFA levels are 0.47 (at A-15 and A-16), 0.41 (at A-
35, Dowex HCR-W2 and non-catalyzed reaction), 20 vol% methanol.
1794 N. Özbay et al. / Fuel 87 (2008) 1789–1798

data for crosslinking level in Table 1 and the order of swell-
ing capacities in Fig. 3 confirms the relation given above.
3.3. Comparison of different ion-exchange resins
It is generally known that lower crosslinking levels will
cause higher swelling of ion-exchange resins [39]. Besides
in spite of lower swelling capacity, if the ion-exchange resin
has high pore diameter it will let FFA molecules enter into
the inner surface of the catalyst and will increase esterifica-
tion rate [39]. In Table 1, the structural characteristics of A-
15, A-35, A-16, Dowex HCR-W2 are given. Although A-15
has the highest crosslinking level and the lowest swelling
capacity as expected (Fig. 3.) since it has a high pore diam-
eter and superior physical properties (surface area) than
others, it would exhibit highest FFA conversions as seen
in Table 2. Finally it can be said that, high average pore
diameters (with high BET surface area) has more dominant
effect than low crosslinking level in esterification reaction.
FFA conversion for different catalysts are shown in
Fig. 4. It is seen from this figure the catalytic activities of
resins can be arranged as A-15 > A-35 > A-16 > Dowex
HCR-W2. As described above, this order of catalytic activ-
ities is related with the size of average pore diameters and
magnitude of BET surface area (Table 1).
3.4. The effect of catalyst amount
At constant reaction temperature, acidity (increase in
FFA conversion) decreased with increasing catalyst
amount. In the case of non-catalyzed reaction, almost no
esterification was observed (Figs. 5 and 6). In the previous
studies [5,6,13,40,41] similar behaviour was also reported.
3.5. The effect of temperature
When esterification reactions were carried out at tem-
peratures less than the boiling point of methanol (50–
60 °C) and at atmospheric pressure, the FFA conversions
were 46% maximum. The advantage of this process may
be that lower operating temperatures and pressures are
required unlike previous works [42,43].
The effect of temperature on the FFA conversion at dif-
ferent catalyst amounts (1 and 2 wt%) is presented in Figs.

40 40

35 35

30 30
FFA Conversion, (%)
FFA Conversion, (%)

25 25

20 20

15 15

10 10
50 °C 60 °C 50 °C 60 °C
5 5

0 0
0 50 100 150 200 0 50 100 150 200
Reaction Time (min) Reaction Time (min)

c 40
d 40

35 35

30 30
FFA Conversion, (%)
FFA Conversion, (%)

25 25

20 20

15 15

10 50 °C 60 °C 10 50 °C 60 °C

5 5

0 0
0 50 100 150 200 0 50 100 150 200
Reaction Time (min) Reaction Time (min)

Fig. 7. Effect of reaction temperature on conversion of FFA (1 wt% of A-15 (a), A-35 (b), A-16 (c), Dowex HCR-W2 (d)). Initial FFA levels are 0.47 (at
A-15 and A-16), 0.41 (at A-35, Dowex HCR-W2), 20 vol% methanol.
 N. Özbay et al. / Fuel 87 (2008) 1789–1798 1795

7 and 8. Because of the increase in reaction rate and equi-
librium constant for an endothermic reaction, it was seen
that FFA levels decreased with increasing reaction temper-
ature. This behaviour was independent of the type and
amount of catalyst [5,40].
3.6. Effect of catalyst type on reaction rate
The rate of change of FFA conversion can be seen in
Figs. 9 and 10, it was seen that the reaction rate drops to
zero after 40 min for all type of catalysts. In the literature,
the FFA esterification reaction is completed in 15 min for
homogenous catalyst (H2SO4) [44] and 100 min for Relite
CFS (acidic ion exchange polymeric resin) [41].
3.7. Maximum performance level comparison with
conventional catalyst
All the experiments were conducted with an initial FFA
concentration of 2.54 mol/L. After the esterification reac-
tion FFA conversions were observed as 45% maximum at
60 °C for 2 wt% A-15 catalyst. In the literature, Sendziki-
ene et al. [44] have achieved nearly 50% conversion for
1% homogenous acidic catalyst (H2SO4) at 50 °C, so it is
clearly seen that A-15 heterogenous catalyst can take place
of conventional homogenous catalyst. Since the perfor-
mance levels of the two types of catalysts mentioned above
are comparable, it is believed that they will show resem-
blance at higher FFA levels.
3.8. The role of internal diffusion on reaction rate
In order to understand the effect of internal diffusion, an
additional run was performed on finely powdered (<6 lm)
A-15, A-16, A-35, Dowex HCR-W2 catalysts (2 wt%) at
60 °C reaction temperature. In Fig. 11 it can be seen that
there is no significant difference (<10%) in FFA conver-
sions between powdered and particle catalysts. In addition,
as we have mentioned before (in Fig. 1) A-15 has better
physical properties (particle diameter, surface area etc.)
than the other type of resins which may decrease the inter-
nal mass transfer resistance.

50 50

45 45

40 40
FFA Conversion, (%)
FFA Conversion, (%)

35 35

30 30

25 25

20 20

15 15

10 50 °C 60 °C 10 50 °C 60 °C

5 5

0 0
0 50 100 150 200 0 50 100 150 200
Reaction Time (min) Reaction Time (min)

c 50
d 50

45 45

40 40

35 35
FFA Conversion, (%)

FFA Conversion, (%)

30 30

25 25

20 20

15 15

10 50 °C 60 °C 10 50 °C 60 °C

5 5

0 0
0 50 100 150 200 0 50 100 150 200
Reaction Time (min) Reaction Time (min)

Fig. 8. Effect of reaction temperature on conversion of FFA (2 wt% of A-15 (a), A-35 (b), A-16 (c), Dowex HCR-W2 (d)). Initial FFA levels are 0.47 (at
A-15 and A-16), 0.41 (at A-35, Dowex HCR-W2 and non-catalyzed reaction), 20 vol% methanol.
1796 N. Özbay et al. / Fuel 87 (2008) 1789–1798

0,035 0,035

0,03 0,03

0,025 0,025
50 °C 60 °C 50 °C 60 °C

(wt%/min)

(wt%/min)
Δ(FFA)/Δ t

Δ(FFA)/Δ t
0,02 0,02

0,015 0,015

0,01 0,01

0,005 0,005

0 0
0 50 100 150 200 0 50 100 150 200
t (min) t (min)

c 0,035
d 0,035

0,03 0,03

0,025 0,025
50 °C 60 °C 50 °C 60 °C
(wt%/min)

(wt%/min)
Δ(FFA)/Δ t

Δ(FFA)/Δ t
0,02 0,02

0,015 0,015

0,01 0,01

0,005 0,005

0 0
0 50 100 150 200 0 50 100 150 200
t (min) t (min)

Fig. 9. The rate of change of FFA conversion (1 wt% catalyst; A-15 (a), A-35 (b), A-16 (c), Dowex HCR-W2 (d)).

0,045 0,035

0,04
0,03
0,035
0,025
0,03 50 °C 60°C 50 °C 60°C
(wt%/min)

(wt%/min)
Δ(FFA)/Δt

Δ(FFA)/Δt

0,025 0,02

0,02 0,015

0,015
0,01
0,01
0,005
0,005

0 0
0 50 100 150 200 0 50 100 150 200
t (min) t (min)

0,035 d 0,035

0,03 0,03
50 °C 60°C 50 °C 60°C
0,025 0,025
(wt%/min)

(wt%/min)

0,02
Δ(FFA)/Δt
Δ(FFA)/Δt

0,02

0,015 0,015

0,01 0,01

0,005 0,005

0 0
0 50 100 150 200 0 50 100 150 200
t (min) t (min)

Fig. 10. The rate of change of FFA conversion (2 wt% catalyst; A-15 (a), A-35 (b), A-16 (c), Dowex HCR-W2 (d)).
 N. Özbay et al. / Fuel 87 (2008) 1789–1798 1797

80 80

70 70

60 60

FFA Conversion, (%)

FFA Conversion, (%)

50 50

40 40

30 30
Powder Particle Powder Particle
20 20

10 10

0 0
0 50 100 150 200 0 50 100 150 200
Reaction Time (min) Reaction Time (min)

c 80

70

60
FFA Conversion, (%)

50

40

30

20
Powder Particle

10

0
0 50 100 150 200

Reaction Time (min)

Fig. 11. Evolution of FFA conversion as a function of time for different runs ( powder, j particle).

4. Conclusions References

Highest FFA conversion (45.7%) was obtained over [1] Pasias S, Barakos N, Alexopoulos C, Papayannakos N. Heteroge-
strong acidic macroreticular ion-exchange resin A-15 at neously catalyzed esterification of FFAs in vegetable oils. Chem Eng
Technol 2006;29:1365–71.
60 °C with 2 wt% catalyst amount. FFA conversion [2] Srivastava A, Prasad R. Triglycerides-based diesel fuels. Renew Sust
increased with increasing temperature and increasing cata- Energy Rev 2000;4:111–31.
lyst amount. All resin catalysts were active for esterifica- [3] Leung DYC, Guo Y. Transesterification of neat and used frying oil:
tion. Superiority of physical properties of resins may be a Optimization for biodiesel production. Fuel Process Technol
2006;87:883–90.
dominant factor for higher catalytic activity. Comparable
[4] Lopez DE, Goodwin JG, Bruce DA, Lotero E. Transesterification of
performance level of A-15 catalyst with conventional cata- triacetin with methanol on solid acid and base catalysts. Appl Catal
lyst makes it the best probable candidate among A-15, A-Gen 2005;295:97–105.
A-16, A-35, Dowex HCR-W2 catalysts for FFA esterifica- [5] Marchetti JM, Miguel VU, Errazu AF. Heterogeneous esterifica-
tion. Commercial strong acidic ion exchange resins can be tion of oil with high amount of free fatty acids. Fuel 2007;86:
used for esterification of FFA in WCO. 906–10.
[6] Wang Y, Ou S, Liu P, Xue F, Tang S. Comparison of two different
processes to synthesize biodiesel by waste cooking oil. J Mol Catal A-
Acknowledgements Chem 2006;252:107–12.
[7] Zheng S, Kates M, Dubé MA, McLean DD. Acid-catalyzed
The authors gratefully acknowledge Prof. Dr. Gulsen production of biodiesel from waste frying oil. Biomass Bioenergy
2006;30:267–72.
Dogu (Gazi University, Department of Chemical Engineer-
[8] Mohamad IAW, Al-Shyoukh AO. Experimental evaluation of the
ing) for giving her valuable advice and comment through- transesterification of waste palm oil into biodiesel. Biores Technol
out this work. N. Ozbay was awarded scholarships by 2002;85:253–6.
Scientific and Technical Research Council of Turkey [9] Leung DYC. Development of a clean biodiesel fuel in Hong Kong
(TUBITAK-BIDEB;_ 2228). using recycled oil. Water Air Soil Poll 2001;130:277–82.
1798 N. Özbay et al. / Fuel 87 (2008) 1789–1798
[10] Tomasevic AV, Siler-Marinkovic SS. Methanolysis of used frying oil.
Fuel Process Technol 2003;81:1–6.
[11] Supple B, Howard-Hildige R, Gonzalez-Gomez E, Leahy JJ. The
effect of steam treating waste cooking oil on the yield of methyl ester.
J Am Chem Soc 2002;79:175–8.
[12] Felizardo P, Correia MJN, Raposo I, Mendes JF, Berkemeier R,
Bordado JM. Production of biodiesel from waste frying oils. Waste
Manage 2006;26:487–94.
[13] Wang Y, Ou S, Liu P, Zhang Z. Preparation of biodiesel from waste
cooking oil via two-step catalyzed process. Energy Convers Manage
2007;48:184–8.
[14] Çetinkaya M, Karaosmanoğlu F. A new application area for used
cooking oil originated biodiesel: generators. Energy Fuel 2005;19:
645–52.
[15] Mittelbach M, Tritthart P. Diesel fuel derived from vegetable oils, III.
Emission tests using methyl esters of used frying oil.. J Am Oil Chem
Soc 1988;65:1185–7.
[16] Wu WH, Foglia TA, Marmer WN, Dunn RO, Goering CE, Briggs
TE. Low-temperature property and engine performance evaluation of
ethyl and isopropyl esters of tallow and grease. J Am Oil Chem Soc
1998;75:1173–7.
[17] Dorado MP, Ballesteros E, Arnal JM, Gómez J, Giménez FJL.
Testing waste olive oil methyl ester as a fuel in a diesel engine. Energy
Fuel 2003;17:1560–5.
[18] Canakci M, Van Gerpen J. Biodiesel production from oils and fats
with high free fatty acids. Trans ASAE 2001;44:1429–36.
[19] Kulkarni MG, Dalai AK. Waste cooking oil – an economical
source for biodiesel: a review. Ind Eng Chem Res 2006;45:
2901–13.
[20] Peters TA, Benes NE, Holmen A, Keurentjes JTF. Comparison of
commercial solid acid catalysts for the esterification of acetic acid
with butanol. Appl Catal A-Gen 2006;297:182–8.
[21] Viviana Silva MTM, Rodrigues AE. Kinetic studies in a batch reactor
using ion exchange resin catalysts for oxygenates production: role of
mass transfer mechanisms. Chem Eng Sci 2006;61:316–31.
[22] Lotero E, Liu Y, Lopez DE, Suwannakarn K, Bruce DA, Goodwin
JG. Synthesis of biodiesel via acid catalysis. Ind Eng Chem Res
2005;44:5353–63.
[23] Chen X, Xu Z, Okuhara T. Liquid-phase esterification of acrylic acid
with 1-butanol catalyzed by solid acid catalysts. Appl Catal A–Gen
1999;180:261–9.
[24] Heidekum A, Harmer MA, Hoelderich WF. Addition of carboxylic
acids to cyclic olefins catalyzed by strong acidic ion exchange resins. J
Catal 1999;181:217–22.
[25] Liu WT, Tan CS. Liquid-phase esterification of propionic acid with n-
butanol. Ind Eng Chem Res 2001;40:3281–6.
[26] Yadav GD, Thathagar MB. Esterification of maleic acid with ethanol
over cation exchange resin catalysts. React Funct Polym 2002;52:
99–110.
[27] Reis SCM, Lachter ER, Nascimento RSV, Rodrigues Jr JA, Reid
MG. Transesterification of Brazilian vegetable oils with methanol
over ion-exchange resins. J Am Oil Chem Soc 2005;82:661–5.
[28] Chakrabarti A, Sharma MM. Cationic ion exchange resins as
catalyst. React Polym 1993;20:1–45.
[29] Pääkkönen PK, Krause AOI. Diffusion and chemical reaction in
isoamylene etherification within a cation-exchange resin. Appl Catal
A-Gen 2003;245:289–301.
[30] Honkela ML, Root A, Lindblad M, Krause AOI. Comparison of ion
exchange resin catalysts in the dimerisation of isobutene. Appl Catal
A-Gen 2005;295:216–23.
[31] Dogu T, Boz N, Aydın E, Oktar N, Murtezaoglu K, Dogu G. DRIFT
Studies for the reaction and adsorption of alcohols and isobutylene
on acidic resin catalysts and the mechanism of ETBE and MTBE
synthesis. Ind Eng Chem Res 2001;40:5044–51.
[32] The Dow Chemical Company, Product Information, Dowex HCR-W2.
[33] Cruz VJ, Izquierdo JF, Cunill F, Tejero J, Iborra M, Fite C. Acid ion-
exchange resins catalysts for the liquid-phase dimerization/etherifica-
tion of isoamylenes in methanol or ethanol presence. React Funct
Polym 2005;65:149–60.
[34] Paakkonen PK, Krause AOI. Comparative study of TAME synthesis
on ion-exchange resin beads and a fibrous ion-exchange catalyst.
React Funct Polym 2003;55:139–50.
[35] Słomkiewicz PM. The gas phase n-propyl-tert-butyl ether synthesis.
Appl Catal A-Gen 2006;313:74–85.
[36] Gemma V, Mercedes M, Jose A, Alfredo E. Kinetics of sunflower oil
methanolysis. Ind Eng Chem Res 2005;44:5447–54.
[37] Ramadhas AS, Jayaraj S, Muraleedharan C. Biodiesel production
from high FFA rubber seed oil. Fuel 2005;84:335–40.
[38] Kardash E, Tur’yan YI. Acid value determination in vegetable oils by
indirect titration in aqueous-alcohol media. Croat Chem Acta
2005;78:99–103.
[39] Klepacova K, Mravec D, Bajus M. tert-Butylation of glycerol
catalysed by ion-exchange resins. Appl Catal A-Gen 2005;294:141–7.
[40] Berrios M, Slies J, Martin MA, Martin A. A kinetic study of the
esterification of free fatty acids (FFA) in sunflower oil. Fuel
2007;86:2383–8.
[41] Tesser R, Serio MD, Guida M, Nastasi M, Santacesaria E. Kinetics
of oleic acid esterification with methanol in the presence of triglyc-
erides. Ind Eng Chem Res 2005;44:7978–82.
[42] Barnwal BK, Shrama MP. Prospects of biodiesel production from
vegetable oils in India. Renew Sust Energy Rev 2005;9:363–78.
[43] Kocsisová T, Cvengroš J, Lutišan J. High-temperature esterification
of fatty acids with methanol at ambient pressure. Eur J Lipid Sci
Technol 2005;107:87–92.
[44] Sendzikiene E, Makareviciene V, Janulis P, Kitrys S. Kinetics of free
fatty acids esterification with methanol in the production of biodiesel
fuel. Eur J Lipid Sci Technol 2004;106:831–6.