Renewable Energy 107 (2017) 522e530

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Renewable Energy
journal homepage: www.elsevier.com/locate/renene

Kinetics studies of biodiesel production from waste cooking oil using

FeCl3-modified resin as heterogeneous catalyst
Yingqun Ma a, b, Qunhui Wang a, c, *, Xiaohong Sun d, Chuanfu Wu a, c, Zhen Gao a
a
Department of Environmental Engineering, University of Science and Technology Beijing, Beijing 100083, China
b
Advanced Environmental Biotechnology Centre, Nanyang Environment & Water Research Institute, Nanyang Technological University, 1 Cleantech Loop,
Singapore 637141, Singapore
c
Beijing Key Laboratory of Resource-oriented Treatment of Industrial Pollutants, University of Science and Technology Beijing, Beijing 100083, China
d
Department of Agro-biotechnology Research Center, Beijing Academy of Agricultural and Forestry Sciences, Beijing 100097, China

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

Article history: In this study, biodiesel production from waste cooking oil using FeCl3-modified resin as heterogeneous
Received 11 September 2016 catalyst were investigated. Under optimised conditions of methanol/oil molar ratio of 10:1, catalyst
Received in revised form content of 8%, reaction time of 90
C and reaction time of 120 min, a high transesterification rate of
6 January 2017
about 92% was achieved. A comprehensive kinetic model was established for the transesterification
Accepted 6 February 2017
Available online 20 February 2017
reaction, the result illustrated that the transesterification of waste cooking oil and methanol catalysed
by FeCl3-modified resin was confirmed for Rideal model, and the transesterification reaction was
verified for the first order reaction controlled by the interfacial chemical reaction diffusion. The main
Keywords:
Biodiesel
physicalechemical properties of biodiesel met the ASTM D-6751 (American Society for Testing and
FeCl3-modified resin Materials D-6751) standard. Compared with concentrated sulfuric acid catalyst, the eminent charac-
Heterogeneous catalyst teristics of reusability and operational stability made the resin catalyst more ascendant for biodiesel
Kinetic production. The results of present research showed that transesterification process catalysed by FeCl3-
modified resin was an effective and low cost technology for biodiesel industry.
© 2017 Elsevier Ltd. All rights reserved.

1. Introduction transesterification step causes equipment corrosion and generation

Biodiesel is produced by the transesterification of long chain
fatty acids derived from vegetable oils and animal fats (tri-
glycerides) with alcohols (methanol, ethanol or propanol) in pres-
ence of an appropriate catalyst [1e3]. Currently, biodiesel is
commercially produced using a homogeneous catalyst (NaOH, al-
kali catalysis; H2SO4, acid catalysis) for the transesterification pro-
cess, because of its high reaction activity and low cost [4,5].
However, the recovery of these soluble catalysts from the products
of transesterification is time consuming and difficult [6]. In addi-
tion, during the homogeneous alkali catalysis process, the free fatty
acids are readily saponified by the alkali catalysts
(RCOOH þ NaOH/RCOONa þ H2O), which not only lead to a huge
loss of catalyst, but also to an increase in biodiesel purification cost
[7]. Meanwhile, the application of homogeneous catalysis in the
* Corresponding author. Department of Environmental Engineering, University of
Science and Technology Beijing, Beijing 100083, China.
E-mail address: wangqh59@sina.com (Q. Wang).
of large volume of acidic or alkaline waste water [8]. Therefore, the
number of studies on heterogeneous catalysis in relation to bio-
diesel production is steadily increasing to address these problems
[9,10]. In heterogeneous catalysis process, the catalyst can be easily
recovered from the crude biodiesel and recycled to the process
[11,12]. Furthermore, equipment corrosion can be prevented. Many
heterogeneous catalysts for biodiesel production have been inves-
tigated in previous reports [13e15]. However, there are some fac-
tors that restrict the use of these catalysts, such as complexity in
preparation, high cost, and unstable activity of catalysts. Consid-
ering the environmental safety and cost of ion-exchange resin, it
has some advantage compared with other heterogeneous catalysts
[16]. In general, ion-exchange resins are made of a cross-linked
polymeric matrix on which the active sites for the trans-
esterification reaction are bonded. In addition, compared with
other heterogeneous catalysts, ion-exchange resin can be easily
separated from crude biodiesel because of its relatively large par-
ticle diameter (0.5e1.5 mm) [17].
Nowadays, many studies on ion-exchange resin catalysis in
relation to biodiesel production had been reported [18e20].

http://dx.doi.org/10.1016/j.renene.2017.02.007
0960-1481/© 2017 Elsevier Ltd. All rights reserved.
 Y. Ma et al. / Renewable Energy 107 (2017) 522e530
Especially is that biodiesel production from waste cooking oil using
FeCl3-modified resin as heterogeneous catalyst had been investi-
gated by our research group before and the transesterification rate
of FeCl3-modified resin as catalyst was 27.81% higher than that of
unmodified resin as catalysts, moreover, after the ninth run of
reusing modified resin, transesterification rate still could reach 73%,
the lower transesterification rate was mainly relative to the frag-
mentation and loss during the process of reaction and reusing the
catalyst, but it was only necessary to add few and new modified
resin regularly to keep high transesterification rate [21]. However,
to meet the large-scale biodiesel production, optimization of re-
action conditions and an appropriate kinetic study should be
implemented, these were not be found in previous reported.
In this study, a heterogeneous catalyst (FeCl3-modified strong
acidic syrene cation-exchange resin) was used for trans-
esterification of waste cooking oil (obtained from the restaurant of
the University of Science and Technology Beijing). Reaction condi-
tions were optimized by varying the reaction temperature, meth-
anol/oil molar ratio, catalyst amount and reaction time. A kinetic
study was also conducted and the reaction rate constant (k) and
activation energy (Ea) at various temperatures were determined.
This study provided a theoretical foundation for design of the
transesterification reactors, computer simulation of catalytic pro-
cess and large-scale biodiesel production.
2. Material and methods
2.1. Materials
Waste cooking oil was obtained from the restaurant of the
University of Science and Technology Beijing. Soybean oil and a
little animal fat (pig, beef, chicken etc.) are the raw material of the
restaurant, so the oil derived from soybean and animal fat. The
components of waste cooking oil (fatty acid) had been detected by
our research group in previous study used gas chromatograph and
mass spectrum (GCeMS), palmitic, oleic, linoleic and stearic acids
were the principal components of waste cooking oil [22]. Methanol
(purity 99.8%), ethanol (purity 95%), Sodium methoxide were pur-
chased from Sinopharm Chemical Reagent Co., Ltd. 732ion ex-
change resins were purchased from Guangfu Chemical Research
Institute (Tianjin, China) and their characteristics are shown in
Table 1. Before the experimental run, in order to remove foreign
matters, the ion exchange resin was washed by ethanol for several
times, and was dried for 12 h at 70
C in an oven so as to remove the
residual ethanol.
2.2. Modified resin preparation
Macroporous styrene type cation-exchange resin was firstly
Table 1
Characteristics of strong acidic syrene cation-exchange resin.
732ion exchange resins
Character Cation (high acidic)
Structure Macroporous
Matrix Styrene-DVB
Functional group SO2-
3 The fatty acid ester content of biodiesel was quantified using GC
Temperature (
C) Max. 120
pH range 1e14
(a) mmol/g (dry) 4.2
(b) mmol/g (wet) 1.4
Bead size (%) (0.40e1.25 mm)95
Moisture content (%) 45e50
True (g/ml) 1.26e1.29
Apparent (g/ml) 0.77e0.87
523
modified into hydrogen type cation-exchange resin following the
method in Chinese National Standard (GB/T 5476-1996) [23]. The
method to calculate the hydrogen exchange capacity was also
based on the Chinese National Standard (GB8144-87) [24]. After
testing, the exchange capacity of strong acid groups in the un-
modified hydrogen type cation-exchange resin was 2.42 mmol/g,
(i.e., the theoretical Fe load rate of the resin was 12%). FeCl3-
modified resin preparation method: Resin, FeCl3$6H2O (two times
the resin weight), and ethanol (four times the resin weight) was
placed in a dry Erlenmeyer flask equipped with a magnetic stirrer
and thermometer, the reactor temperature (78
C) was controlled
by a heater with a programmable temperature controller, the reflux
unit caused the ethanol to remain in the liquid phase for the entire
duration of the reaction. After 3 h, FeCl3-modified resin was ob-
tained. Finally, Fe load rate of resin reached 10.97%, which was
92.13% the theoretical load rate.
2.3. Transesterification process catalyzed by modified resin and
conventional homogenous catalyst
Before biodiesel synthesis, the waste cooking oil was pretreated
by the following procedure described by Ma et al. [22], First, wipe
off the bone, paper, plastic, vegetables and other debris of waste
cooking oil manually, then added the activated clay (20 g/100 g oil),
entrifugation (4000 r/min), filtration, at last, deacidification by
utilizing the method of extraction (acid value below 2 mg KOH/g)
and remove water (moisture below 0.5%). Biodiesel was syn-
thesised in a reactor by using FeCl3-modified resin as a catalyst
following the similar method described by Lang et al. [25]. The
reaction was conducted by using 99.5% excess methanol. Oil (100 g)
was placed in a dry Erlenmeyer flask equipped with a magnetic
stirrer and thermometer, and mixed with the resin catalyst and
methanol of a certain ratio, the reactor temperature was controlled
by a heater with a programmable temperature controller, the reflux
unit caused the methanol to remain in the liquid phase for the
entire duration of the reaction. When the reaction finished, the
excess of methanol in the product was recovered under vacuum at
50
C using a rotational evaporator. Afterwards, the mixture was
centrifuged at 4000 rpm for 10 min to be separated into two layers.
The upper layer was the Fatty Acid Methyl Ester (FAMEs) with
lighter color. The resin catalyst at bottom of the reactor was dec-
anted into a flask for recovering. It could be easily separated and
reused by soaking with methanol. All experiments were performed
in three repetitions. Otherwise, Single factor method was used for
optimization of the experimental parameters. Reaction tempera-
tures (60e100
C), molar ratio of methanol/oil (6:1e12:1), catalyst
amounts (5e10%) and reaction time (30e180 min) were selected
and optimized according to the previous reports [17,19,26].
The transesterification process of waste cooking oil catalyzed by
conventional acid homogenous catalyst (concentrated sulfuric acid)
was conducted in the same reactor. After optimized, main param-
eters for the reaction were as follows: 90
C for 180 min with
methanol/oil molar ratio of 10 and a catalyst amount of 10% (w/w of
oil).
2.4. Ester characterization
following the method described by Ma et al. [22]. A SHIMADZU gas
chromatograph (2014) equipped with a flame ionisation detector
and a DB-WAX column (30 m  0.25 mm  0.25 mm, Agilent) was
used. Helium was used as a carrier gas. The flow rate was 1.0 mL/
min, and the sample split ratio was 20:1. The temperature of the
injector was set to 220
C, whereas that of the detector was set to
300
C. The temperature program was as follows: initial column
524 Y. Ma et al. / Renewable Energy 107 (2017) 522e530
temperature of 120
C for 3 min, holding temperature of 220
C for
12 min and heating rate of 20
C/min. On the basis of the standard
working curve, the content of fatty acid esters in the product was
calculated. The total content of fatty acid ester is the sum of all
component contents. The ester exchange ratio was calculated as
quality of fatty acid esters in the product
Transesterification rate ¼
theory transform quality of fatty acid esters
Additionally, chemical composition of the biodiesel sample
following the method described by Ma et al. [22]. The identity and
relative composition of fatty acid methyl esters were analysed by a
DSQ type of gas chromatograph and mass spectrum equipped with
a DB-5 medium polar capillary column (30 m  0.25
mm  0.25 mm). Heliumwas used as a carrier gas. The flow rate was
1.0 mL/min, the sample split ratio was 20:1 and the inlet temper-
ature was 280
C. The temperature program was as follows: initial
column temperature of 50
C for 2 min, holding temperature of
280
C for 5 min, heating rate of 10
C/min and ion source tem-
perature of 250
C from an EI source with an electron energy of
70 eV. The scanning quality number ranged from 50 AUM to 650
AUM during NIST98 library searching.
2.5. Properties evaluation of biodiesel product
The main properties of biodiesel product were determined using
standard test methods according to the ASTM D-6751 (American
Society for Testing and Materials D-6751).
3. Results and discussion
3.1. Parameters optimization of the transesterification process
In order to study the effects of different reaction temperatures,
molar ratio of methanol/oil, the amount of catalyst and reaction
time on the transesterification rate, the transesterification pro-
cesses were carried out at different reaction conditions, the results
shown in Fig. 1. Generally speaking, the increase in temperature
would accelerate the reaction rate in endothermic reaction [26].
Fig. 1a showed that the transesterification rate improved as the
increase of temperature. However, the transesterification rate was
increased slowly over 90
C. Consider the aspect of trans-
esterification rate, stability and energy saving, the reaction tem-
perature was chosen for 90
C in the subsequent experiment. The
molar ratio of methanol/oil was an important influence factor for
the transesterification rate. In general, transesterification rate could
be improved by increasing the amounts of methanol, so the high
molar ratio of methanol/oil could enhance the transesterification
rate. Although the methanol/oil theoretical molar ratio for this re-
action was 3, the methanol/oil molar ratio had to be higher than the
theoretical value in actual reaction due to a part of methanol ap-
pears in gaseous state during the transesterification process. It was
found that the transesterification rate was nearly 92% when the
methanol/oil molar ratio of 10, and the transesterification rate
almost kept stable with further increase in the molar ratio (Fig. 1b).
Therefore, the optimal methanol/oil molar ratio was 10. As shown
in Fig. 1c, the transesterification rate improved quite with an in-
crease in the amount of catalyst. When the catalyst amount was
over 8% of oil, the transesterification rate was stable. Thus, a catalyst
amount of 8% (w/w of oil) was used for biodiesel preparation. The
reaction time was also optimized. As shown in Fig. 1d, when re-
action time was 120 min, the transesterification rate was about 92%
and hardly increased with an increase in reaction time. Thus, in the
 100% (1)
current study, the reaction time of 120 min was used for biodiesel
preparation.
The different types of utilized catalysts will affect the trans-
esterification rate and experiment conditions, such as reaction
temperatures, molar ratio of methanol/oil, the amount of catalyst
and reaction time. In the previous literature, many different kinds
of heterogeneous catalysts had been used for biodiesel production.
The reported biodiesel produced from different heterogeneous
catalysts were summarized in the Table 2. The highest trans-
esterification rate of 99.3% was obtained using Nano MgO as cata-
lyst [27], but the much higher temperature of 260
C and molar
ratio of 36:1 were needed, in turn lead to high consumption of
energy and high consumption of methanol, a toxic solvent. Use
Sr(NO3)2/ZnO as the catalyst for biodiesel production had the
similar defect in higher molar ratio of methanol/oil with trans-
esterification rate of 94.7% [28]. Although the transesterification
rate of 94.2% was achieved use CaO$ZnO as the catalyst, longer time
duration of 5 h was needed [29], what’s more, all these heteroge-
neous catalysts need to be calcinated in the high temperatures
(400e600
C) before used. In contrast, in the present study, an
transesterification rate of 92% were obtained under the unde-
manding conditions of methanol/oil molar ratio of 10:1, catalyst
content of 8%, reaction time of 90
C and reaction time of 120 min,
this was the highest transesterification rate among the other re-
ported results on biodiesel production. So it is a good approach to
utilize FeCl3-modified resin heterogeneous catalyst to produce
biodiesel, thereby obtain the higher transesterification rate and
lower energy consumption.
3.2. Kinetic study of the transesterification reaction catalysed by
FeCl3-modified resin
The transesterification reaction catalysed by FeCl3-modified
resin involves a heterogeneous catalytic reaction. This reaction
included several common stages, such as (1) external and internal
diffusion of catalyst granules, (2) adsorption of reactants, reaction
process and desorption of products (i.e., kinetic equation), so the
influence of internal and external diffusion should be eliminated
when elucidating the chemical reaction kinetics.
In regard to the external diffusion, reactants were absorbed on
the outside surface of the catalyst granule. The reactants seep into
the nearby catalyst granules and generate a laminar adsorbed layer,
which can be destroyed through strong agitation. So we investi-
gated the external diffusion effects on reaction rate with different
stirring rates. As shown in Table 3, the transesterification rate
(transesterification rate is by means synonymous of reaction rate
due to the time was constant; similarly hereinafter) did not change
when the stirring rate is higher than 200r/min; thus, the external
diffusion could be eliminated over the stirring rate of 200r/min. In
the present study, all kinetic experiments were conducted at a
stirring rate of 220 rpm to remove the effect of external diffusion.
 Y. Ma et al. / Renewable Energy 107 (2017) 522e530 525

95 95

(a) (b)
90
90

Transesterification rate (%)

Transesterification rate (%)

85

85
80

75
80

70 Molar ratio of methanol/oil;10 Reaction temperatures; 90

The amount of catalyst;8% 75 The amount of catalyst;8%
65 Reaction time;120min Reaction time;120min

60 70
60 70 80 90 100 6:1 7:1 8:1 9:1 10:1 11:1 12:1
Temperature Molar ratio of methanol/oil

94 100
(c) (d)
92 90
Transesterification rate (%)

Transesterification rate (%)

90 80

88 70

86 60

84 50
Molar ratio of methanol/oil;10 Molar ratio of methanol/oil;10
Reaction temperatures; 90 Reaction temperatures; 90
82 40
Reaction time;120min The amount of catalyst;8%
80 30
5 6 7 8 9 10 30 60 90 120 150 180
Catalyst amounts (%,w/w of oil) Time(min)

Fig. 1. Effects of parameters on transesterification rate of transesterification process.

Table 2
Biodiesel produced from different types of heterogeneous catalysts.

Heterogeneous catalyst Calcination Molar ratio of methanol/ Reaction time Temperature Catalyst amount Transesterification References
oil (h) (
C) (wt.%) rate

Nano MgO Yes 36:1 0.17 260 3.0 99.3 [27]

Sr(NO3)2/ZnO Yes 12:1 5 65 5.0 94.7 [28]
CaO$ZnO Yes 30:1 1 60 10.0 94.2 [29]
Na/hydrotalcite Yes 15:1 8 60 7 88 [30]
Zn/Al complex oxide derived from Yes 24:1 1.5 200 1.4 83.6 [31]
hydrotalcite
Mg-Al hydrotalcites Yes 6:1 4 65 1.5 90.5 [32]
KF/hydrotalcite Yes 12:1 5 65 3.0 92 [33]
KNO3/Al2O3 Yes 12:1 6 70 6 84 [34]
Eu2O3/Al2O3 Yes 6:1 8 70 10 63.2 [35]
NaX/KOH Yes 10:1 8 65 3 85.6 [36]
FeCl3-modified resin No 10:1 2 90 8 92 This study

The effects of internal diffusion on reaction rate could be confirmed by the Thiele module ðfs Þ. If fs ＜h, h ¼ 1, suggest the
expressed by catalyst effective coefficient (h), which is the ratio of effects of internal diffusion on reaction rate could be neglected. The
actual reaction rate and theoretical reaction rate (calculated ac- Thiele module ðfs Þ can be calculated using the equation,
cording to the surface reactants concentration). The h could be
sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
Kv C n1s
Table 3 fs ¼ R (2)
Effect of stirring rate on transesterification rate. Deff
Stirring rate (r/min) 100 150 200 250 300
Where R is the catalyst particle diameter, KV is the reaction rate
Transesterification rate (%) 87.37 90.65 92.06 92.18 92.25
constant, CS is the substrate concentration of catalyst external
526 Y. Ma et al. / Renewable Energy 107 (2017) 522e530
surface, Deff is the internal diffusion coefficient, and n is the reaction
order.
The molar volume under the normal boiling point can be
calculated using the Le-Bas equation, in addition, internal diffusion
coefficient of reactants can be calculated using WilkeChang equa-
tion [37], the value of Deff ¼ 4.47  105 cm2 s1 was obtained, and
then the reaction rate constant(Kv ¼ 0.0166 L mol1$min1), sub-
strate concentration (CS ¼ 0.714  103 mol mL1), reaction order
(n ¼ 2) and resin diameter (R ¼ 0.5 mm) were all substituted into
the Thiele module formula (2), and the obtained fs ¼ 0.1  1. Ac-
CH2COOR1 CH2 OH
Catalyst
CHCOOR 2 + 3R4OH CHOH
CH2COOR3 CH2 OH
cording to the relation curve of h and Thiele module [37], internal
diffusion resistance could be neglected completely.
In this experimental system, waste cooking oil and methanol
can be regarded as two kinds of reactant molecules. Thus, a double
molecular reaction model is adopted. In general, two kinds of
mechanisms are possibly generated in a double molecular reaction
of solid surface, namely, the LangmuireHinshelwood and Rideal
mechanisms. The LangmuireHinshelwood mechanism states that
two kinds of reactant molecules are adsorbed on the catalyst sur-
face simultaneously, and then forming an activated complex, finally
transforming into the product. If a maximum value appears on the
curve of the reaction rate and certain reactants concentration, it can
be ensured that the reaction is the LangmuireHinshelwood
pathway [38]. Rideal mechanism illustrates that only a kind of
reactant molecules is adsorbed on the catalyst surface, while the
other reactant molecules react with adsorbed molecules in the
liquid phase, finally yielding the product. If a limiting value appears
on the curve of the reaction rate and certain reactants concentra-
tion, the reaction pertains to the Rideal pathway [38]. J. Li et al. [39]
expounded the mechanism of transesterification reaction catalysed
by a high-acidity cation exchange resin, in which the protonation of
the carbonyl group yields a carbocation at first, after the nucleo-
philic attack of the methanol molecule, a tetrahedral intermediate
was generated, which subsequently formed into fatty acid methyl
esters (FAMEs). The reaction process was as follows:
In the reaction, triglyceride was adsorbed on the surface of
catalyst first, and methanol reacted with adsorbed triglyceride
molecules in liquid phase. According to the Fig. 1 (b), oil content
was constant, whereas alcohol content was changed. With the
increase of alcohol/oil molar ratio, the transesterification rate pre-
sented a tendency toward a limiting value. Based on the above
analysis, the reaction belongs to the Rideal pathway. Therefore, the
Rideal mechanism was chosen to describe the transesterification
reaction. In this study, a batch stirred reactor was utilized under the
optimum experimental conditions (alcohol/oil molar ratio of 10:1,
catalyst content of 8%; see Section 3.1) to investigated the variation
of transesterification rate over time (at 333 Ke363 K). The result
was shown in Fig. 2.
According to the reaction equation of transesterification:
R4 COOR 1
+ R4 COOR 2
(4)
R4 COOR 3
The reaction mechanism is as follows: (A ~ fatty acid,
B ~ methanol, C~ fatty acid ester, S ~ resin).
Adsorption of fatty acids: A þ S 4 AS
Reaction with methanol: AS þ B 4 C þ S
After the influence of internal and external diffusion was elim-
inated, reaction kinetics is found to be controlled by surface reac-
tion. Although transesterification reaction is reversible, the reaction
can be regarded as an irreversible and constant-volume reaction by
remove the generated glycerol in the reaction process, which pre-
venting the reverse reaction [40,41]. According to the Rideal
mechanism, in the case of excess methanol, the reaction rate (r) is
only related to reactant concentration (triglyceride) [42], that is,
0 m
r ¼ kCm n
A $CB ¼ k CA (5)
Where k is the Reaction rate constant, k0 ¼ k$CBn , m and n is the
reaction order of the corresponding concentration factor.
As shown in Fig. 2, the variation of transesterification rate over
time variations was obtained (under different reaction
temperatures).
The concentration of fatty acids was calculated (Table 4) ac-
cording to the transesterification rate at different times (Fig. 2).
Moreover, the relation curve between ln C and t is obtained (Fig. 3)
based on triglyceride concentration (C) at different times (t).
As depicted in Fig. 3, the ln C versus t curves (under the different
 Y. Ma et al. / Renewable Energy 107 (2017) 522e530 527

100

90

80

Transesterification ratio (%) 70

60

50

40

30 90℃
80℃
20
70℃
10 60℃
0
0 20 40 60 80 100 120 140
Time(min)
Fig. 2. Transesterification rate with time variations (under different reaction temperatures).

Table 4 reaction temperature levels) presented a linear function; thus,

Variation of triglyceride concentration over time (under the different reaction m ¼ 1 and n ¼ 0 (i.e., pseudo-first-order reaction). The reason is that
temperatures). excessive methanol is present in the reaction system (methanol/oil
Temperature (
C) Time (min) molar ratio of 10:1), and thus the transesterification rate was
20 40 60 80 100 120
irrelevant with the increase of excess methanol concentration.
Furthermore, it further validated the correctness that use the Rideal
60 0.517 0.448 0.382 0.331 0.287 0.251
mechanism to describe the transesterification reaction, namely,
70 0.513 0.414 0.345 0.285 0.238 0.203
80 0.511 0.371 0.284 0.219 0.166 0.131 r ¼ k0 CA . The linear regression equation between ln C and t,
90 0.503 0.327 0.205 0.139 0.094 0.061 linearity-dependent coefficient and the reaction rate constant (k)

0.0

-0.5

-1.0
lnC

-1.5

-2.0
90℃
80℃
-2.5 70℃
60℃
-3.0
0 20 40 60 80 100 120 140
Time(min)
Fig. 3. ln C versus t.
528 Y. Ma et al. / Renewable Energy 107 (2017) 522e530

Table 5
Linear regression equation at different reaction temperatures.

Temperature (
C) Linear regression equation Linearity-dependent coefficient k

60 Y ¼ 0.0073X  0.5176 0.9994 0.0073

70 Y ¼ 0.0093X  0.5011 0.9982 0.0093
80 Y ¼ 0.0135X  0.4303 0.9983 0.0135
90 Y ¼ 0.021X  0.2863 0.9992 0.0210

The ln k versus 1/T curve is shown in Fig. 4.

-1

-2
lnk

-3

-4

-5
y = -4.2706x + 7.8431
R² = 0.9765
-6
2.70 2.75 2.80 2.85 2.90 2.95 3.00 3.05
1000/T
Fig. 4. The relation curve of ln k and 1/T.

under different reaction temperatures was shown in Table 5.
The ln k versus 1/T curve was linear, thereby indicating that k is a
function of temperature. Given the significant effect of reaction
temperature on the rate constant, the correlation between the two
parameters was denoted using the Arrhenius plot in this study. This
plot correlates the natural logarithm of the rate constant (ln k) with
the inverse of temperature (1/T  103). Meanwhile, the activation
energy (Ea) of the transesterification reaction can also be calculated
using the Arrhenius equation:
ln k ¼ Ea / RT þ ln A
where R is the ideal gas constant and A is the pre-exponential
factor.
According to the Arrhenius equation, the slope and intercept of
the graph between ln k and 1/T  103 (Fig. 4) could give the values
of the activation energy and frequency factor. As determined from
the graph, Ea is 35.51 kJ/mol and A is 2.55  103. The activation
energy for the transesterification of waste cooking oil use FeCl3-
modified resin as catalyst fell in the range of the activation energy
obtained for the transesterification of soybean oil, i.e., 33.6 kJ/mol
to 84 kJ/mol [43], and was very close to the minimum value of
33.6 kJ/mol. What’s more, the Ea of this study was much lower than
the previous reported by Zhang et al. [41], which has a Ea of 79.1 kJ/
mol use potassium hydroxide (KOH) as catalyst and Birla [44] has a
Ea of 79 kJ/mol use calcined snail shell as catalyst, so use FeCl3-
(6) modified resin as catalyst for biodiesel production has a lower
activation energy, in turn cost less energy consumption. The rate
constant values at different temperatures are given in Table 5.
Based on the above results, the reaction temperature was proven to
be a positive factor, which is closely related to the trans-
esterification rate. The kinetic equation above was confirmed by the

Table 6
FAME profiles and contents of biodiesel samples prepared using different catalysts.

No. Relative content (%)

FeCl3-modified resin concentrated sulfuric acid

1 Palmitic acid methyl ester 27.35 27.55

2 Linoleic acid methyl ester 30.95 29.56
3 Oleic acid methyl ester 24.46 25.76
4 Stearic acid methyl ester 2.55 2.37
5 Hexadecenoic acid methyl ester 1.35 1.33
 Y. Ma et al. / Renewable Energy 107 (2017) 522e530 529

following assumption conditions: (1) in the transesterification re- homogeneous catalyst completely dissolve with the products, and
action, the reverse reaction is prevented by remove the generated was difficult to be separated and reused. At last but important, the
glycerol in the reaction process, thus the transesterification reac- FeCl3-modified resin was more easily to be separated from the
tion can be regarded as an irreversible and constant-volume reac- biodiesel than that of homogeneous catalyst, so large cost for
tion; (2) the volume of the reaction system remains approximately subsequent purification processing could be saved, on the contrary,
constant during the reaction process; (3) the loss of methanol can homogeneous catalyst need thorough washing by water and
be neglected when glycerol was removed due to the density dif- neutralization by respective acid or alkali, resulting in the need for
ference between methanol and glycerol is considerable. (4) The extra water and generation of excess wastewater, furthermore, the
existing reflux unit can guarantee the methanol to remain in the biodiesel must then be dried to remove the resultant moisture
liquid phase in the reaction process, so the loss of methanol vapor content [45]. Therefore, the cost of biodiesel production in this
also can be neglected. study is much lower than that of using vegetable oil and homo-
geneous catalyst. This study provides a good approach to utilize
waste cooking oil and FeCl3-modified resin heterogeneous catalyst
3.3. Compared with conventional technology to produce biodiesel, thereby reducing catalysts loss and promoting
waste recycling.
In order to prove that FeCl3-modified resin and conventional
acid homogenous catalyst affected the transesterification process, 3.4. Properties evaluation of biodiesel product
concentrated sulfuric acid and modified resin were used as catalyst
for biodiesel production under their own best conditions, respec- The characteristics of biodiesel were measured. As shown in
tively. As comparison, the reaction time required for the FeCl3- Table 7, all of the characteristics met the ASTM D-6751 standard.
modified resin was (120 min) shorter than that of using concen- Biodiesel produced from waste cooking oil using FeCl3-modified
trated sulfuric acid catalyst (more than 180 min), but the trans- resin heterogeneous catalyst was better in the acid value (0.06 mg
esterification rate were similar. Moreover, the chemical KOH/g) and congealing point (17
C). No mechanical impurities
compositions of biodiesel product were determined by GCeMS, and sulfur were found in the biodiesel detection process. Therefore,
and the results were listed in Table 6. It was found that the biodiesel the biodiesel produced from waste cooking oil using FeCl3-modi-
mainly contained five constituents: (1)Palmitic acid methyl ester, fied resin heterogeneous catalyst was of high quality and could be
(2)Linoleic acid methyl ester, (3) Oleic acid methyl ester, (4) Stearic considered as an ideal alternative energy sources.
acid methyl ester and (5) Hexadecenoic acid methyl ester.
Furthermore, the main contents of biodiesel using FeCl3-modified 4. Conclusion
resin catalyst were Palmitic acid methyl ester (27.35%), Linoleic acid
methyl ester (30.95%) and Oleic acid methyl ester (24.46%), there In this study, transesterification of waste cooking oil catalysed
were similarity in the FAMEs composition of biodiesel using by FeCl3-modified resin was proven to be a high-performance
concentrated sulfuric acid catalyst. Nevertheless, the reusability technology for biodiesel production.
and operational stability of resin catalyst were eminent advantages
which were different from concentrated sulfuric acid catalyst. At (1) The optimised conditions of biodiesel production from waste
last but important, the FeCl3-modified resin was more easily to be cooking oil use FeCl3-modified resin as heterogeneous cata-
separated from the biodiesel product, and large cost for subsequent lyst were as follows: alcohol/oil molar ratio of 10:1, catalyst
purification processing would be saved. Therefore, biodiesel pro- content of 8%, reaction time of 90
C and reaction time of
duction using FeCl3-modified resin heterogeneous catalyst was 120 min. The highest transesterification rate was approxi-
ascendant to that using conventional acid catalyst. mately 92%.
Since the waste cooking oil derives from the kitchen waste, and (2) A comprehensive kinetic model for the transesterification
the disposal of kitchen waste could obtain governmental subsidies process was established. A batch stirred reactor was utilized
in most countries, which makes the raw materials were much under atmospheric pressure and a temperature range of
cheaper than vegetable oil. Moreover, the reusability of the FeCl3- 333 Ke363 K. The transesterification reaction was confirmed
modified resin was well, the transesterification rate could still reach to be a first-order reaction controlled by interfacial chemical
73% when transesterification process of the 9th run was finished, reaction diffusion. After regression analysis, the activation
furthermore, it was only necessary to add few and new modified energy (Ea) was determined to be 35.51 kJ/mol, and the
resin regularly to keep high transesterification rate [21], while the frequency factor (A) was 2.55  103. The activation energy for
the transesterification of waste cooking oil was within the
activation energy range obtained for the transesterification
Table 7
Properties of biodiesel derived from FeCl3-modified resin method. of soybean oil, i.e., 33.6 kJ/mol to 84 kJ/mol.
(3) The biodiesel obtained using FeCl3-modified resin and
Property Unit Valuea,b ASTM D-6751
concentrated sulfuric acid as catalysts did not vary in terms


Density at 20 C g/mL 0.87 0.82e0.9 of FAME compositions. The compositions mainly contained
Viscosity at 40
C mm2/s 4.4 1.9e6.0 palmitic acid methyl ester, linoleic acid methyl ester, oleic
Acidvalue mgKOH/g 0.06 ＜0.8
Moisture wt% Trace 0.05
acid methyl ester, stearic acid methyl ester and hexadecenoic
Congealing point

C 15 e acid methyl ester. All indexes of biodiesel satisfy the ASTM
Sulfur % None 0.005 standards. Moreover, the FeCl3-modified resin can be easily
Heating Value MJ/kg 40.47 e separated and reused. Therefore, use FeCl3-modified resin as
Cetane number e 50 49
catalysts in the transesterification process has more advan-
Free glycerol content wt% 0.009 0.020
Total glycerin content wt% 0.067 0.240 tages than conventional acid catalysts.
Carbon residue wt% 0.09 0.3
a
Testing methods specified in ASTM D-6751.
Acknowledgements
b
Biodiesel preparation conditions: alcohol/oil molar ratio of 10:1, catalyst con-
tent of 8%, reaction time of 90
C, and reaction time of 120 min. The project was supported by the National Environmental
530 Y. Ma et al. / Renewable Energy 107 (2017) 522e530
Protection Public Welfare Science and Technology Research Pro-
gram of China (Project No.201309023) and International coopera-
tion project (2013DFG92600).
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