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School of Environmental Engineering, Technical University of Crete, Polytechneioupolis, GR-73100 Chania, Greece
Institute for Infrastructure and Environment, School of Engineering, The University of Edinburgh, Edinburgh EH9 3JL, United Kingdom
a r t i c l e
i n f o
Article history:
Received 17 September 2013
Revised 5 July 2014
Accepted 12 August 2014
Available online xxxx
Keywords:
Waste lard
Biodiesel
Two-step transesterication
Factorial design
a b s t r a c t
The aim of this work is to investigate a two-step homogenous catalyzed waste lard transesterication reaction for
low cost biodiesel production. For this purpose, two 23 full factorial design of experiments was applied. Six variables, namely esterication time (60120 min), H2SO4 concentration (2040 wt.%), MeOH:FFA (15:123:1),
transesterication time (3060 min), KOH concentration (12 wt.%), and MeOH:triglycerides (6:19:1), that
typically affect the production process were studied. The esterication step is signicantly affected mostly by
the reaction time and the MeOH:FFA ratio value. Specically, their increase brings a reduction of the FFA acidity.
Likewise, the transesterication step is positively affected primarily by three independent variables, namely reaction time, KOH concentration and MeOH:triglyceride ratio. Furthermore two empirical models describing evolution of the two-step transesterication reaction were developed. They can become useful tools for further
scaling-up the process by predicting its reaction yield within a 95% of condence level.
2014 International Energy Initiative. Published by Elsevier Ltd. All rights reserved.
Introduction
Recently, biodiesel has received increasing attention worldwide due
to the existing sustainable energy policy framework. Moreover, it
presents unique advantages such as being biodegradable, suitable for
domestic production and non-toxic (Ouachab and Tsoutsos, 2013;
Tsoutsos et al., 2010; van Stralen et al., 2013). On the other hand, in
comparison to petrodiesel, biodiesel has 12% lower energy content,
higher NOx emissions in the range of 1014% during combustion,
needs higher injector pressure, lower oxidation stability and higher
production cost (Atabani et al., 2012). In recent years, systematic efforts have been made to produce biodiesel through the utilization
of waste oils, such as used cooking oils (Wyse-Mason and Beckles,
2012; Math et al., 2010; Talebian-Kiakalaieh et al., 2013; Lee et al.,
2002), animal fats (Kleinov et al., 2011; Berrios et al., 2009), vegetable and rened oil products (Alamu et al., 2007; Che et al., 2012;
Sarantopoulos et al., 2009), which are used to produce a costcompetitive product.
The free fatty acid (FFA) contents of crude vegetable oils, used
cooking oils, animal fats and grease range from 0.3 to 0.7, 2 to 7, 5 to
30 and 40 to 100%, respectively. However, the high amounts of FFAs in
these low cost biodiesel feedstocks make them unsuitable for base-
http://dx.doi.org/10.1016/j.esd.2014.08.005
0973-0826/ 2014 International Energy Initiative. Published by Elsevier Ltd. All rights reserved.
Transesterication method
Transesterication tests were conducted in a 500 mL spherical
three-neck reaction ask, which was immersed in hot water bath at
50 1 C and 50 g of the esteried lard and the appropriate KOH
amount were loaded in it. The reactor was preserved under a watercooled condenser for recovering methanol vapors and under continual
magnetic stirring. Periodically (at 30 and 60 min) samples of 5 mL
were collected and their methyl-ester content was measured.
Table 1
Fatty acid prole of waste lard raw material.
Fatty acid
Class
wt.%
Myristic acid
Palmitic acid
Palmitoleic acid
Stearic acid
Oleic acid
Linoleic acid
Linolenic acid
Others
C14:0
C16:0
C16:1
C18:0
C18:1
C18:2
C18:3
1.0
21.1
1.5
11.5
40.1
21.7
1.5
2.3
111
+
0
Transesterication step
X1
X2
X3
X4
X5
X6
Time,
min
H2SO4, wt %
of FFAs
MeOH:
FFA
Time,
min
KOH, wt %
of oils
MeOH:
triglyceride
60
120
90
20
40
30
15:1
23:1
19:1
30
60
45
1
2
1.5
6:1
9:1
7.5:1
AV in AV f
100
AV in
Where AVin is the initial acidity of the waste lard (mg KOH/g), and
AVf is the acidity (mg KOH/g) of the nal mixture after the end of the
esterication step.
During the transesterication reaction process variables under
investigation were reaction time (X4), KOH concentration (X5) and
MeOH-to-oil ratio (X6). At this point it should be mentioned that the
average molecular weight of the lard was estimated based on its FFA's
prole shown at Table 1. In this factorial design the response factor is
the percentage of methyl ester production (Y2), as determined by gas
chromatography after sample purication. The above parameters were
chosen, as these are typical parameters that affect biodiesel process
production. However, the effect of all the above parameters and their
combination has not been investigated yet for the two-step biodiesel
production form waste lard. Table 3 shows all the experimental runs
performed in duplicate of the two 23 factorial designs.
A key element in the factorial design statistical procedure is the determination of the signicance of the estimated effects. A very useful
pictorial presentation of the estimated effects and their statistical importance can be accomplished using the Pareto chart of the effects.
This chart displays the absolute value of the effects in a bar chart and
draws a reference line on the chart. Any effect that extends past this reference line (corresponding to -level value) is potentially important.
On the other hand, all other effects whose values are lower than the
reference can be attributed to random statistical error. The Pareto
chart of the effects for the esterication step (response Y1) is shown in
Fig. 1. There are ve effects that are greater than the reference decision
threshold. Among them, the two most signicant ones are the time (1)
Table 3
Design matrix of the two individual 23 factorial experimental designs and the observed
response factors Y1 and Y2, during the esterication and the transesterication step
processes, respectively.
Esterication step
Transesterication step
Run order
X1
X2
X3
Y1
Run order
X4
X5
X6
Y2
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
+
0
0
+
+
+
+
+
+
+
0
+
0
+
+
+
+
+
+
0
+
+
+
92.41
84.43
77.84
92.33
89.11
75.23
89.42
86.27
89.88
94.20
88.96
72.47
86.43
88.57
71.70
93.63
88.50
83.74
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
76.4
84.3
77.2
93.9
97.2
93.9
83.2
91.4
90.8
86.2
91.2
96.8
86.9
91
85.3
84.1
a-level
A
C
AC
Term
112
B
AB
Factor Name
A
B
C
ABC
BC
10
15
20
X1
X2
X3
25
Standardized Effect
Fig. 1. Pareto chart of the effects for the esterication step for the full 23 factorial design.
White bars: positive effects; black bars: negative effects.
where Y1 is the FFA acidity reduction percentage (%), Xi are the transformed forms of the independent variables according to:
C
B
Xi
Term
A
AB
Factor Name
BC
A
B
C
ABC
5
10
15
20
Z high Z low
2
Z high Z low
2
Zi
AC
113
X4
X5
X6
25
Standardized Effect
Fig. 2. Pareto chart of the effects for the transesterication step for the full 23 factorial design. White bars: positive effects; black bars: negative effects.
Y 1 85:412
9:761
9:071
X1
X3
2
2
Table 4
Average and main effects of the independent variables and their two and higher order interactions of the two 23 factorial designs on the response factors Y1 and Y2.
Esterication step
Effect
Average effect
Main effects
X1
X2
X3
Two-factor interactions
X 1 X2
X 1 X3
X 2 X3
Three-factor interactions
X 1 X2 X 3
-level
Transesterication step
Value of
effect Y1
85.412
9.761
3.054
9.071
1.839
3.371
0.264
0.706
2.26
Effect
Average effect
Main effects
X4
X5
X6
Two-factor interactions
X 4 X5
X 4 X6
X 5 X6
Three-factor interactions
X 4 X5 X6
-level
Value of
effect Y2
88.1125
6.65
6.8
6.975
1.775
1.55
0.9
0.225
2.31
Y 2 88:1125
6:65
6:8
6:975
X4
X
X6
2
2 5
2
Where t is the reaction time (min), Cat is the KOH catalyst concentration (% wt), and MeOH is the CH3OH:triglycerides ratio. Hence, the
empirical models (4) and (6) can be a useful tool to further scale-up
the two-step biodiesel production process, within the operating points
utilized in these two full factorial designs of experiments.
Quality control
The development of biodiesel's industrial production was triggered
by extensive eld tests in running engines and vehicles so as to
determine the limits of various fuel properties. In Europe, the quality
of biodiesel is assessed under the provisions and the requirements of
quality standard EN 14214 that should be met from each biodiesel
sample so as to be a suitable substitute fossil diesel in transport sector.
Quality control was performed for the biodiesel produced under the optimum process conditions specied above (i.e. runs 4, 10 and 5, 12 for the
esterication and transesterication step, respectively), based on the
European Standard EN 14214:2003. Density at 15 C, acidity number,
methyl ester content, content of monoglycerides (MGs), diglycerides
Table 5
Quality control of produced biodiesel.
Properties
Produced biodiesel
Limits
99.4
877
0.0156
0.0005
0.0040
0.0031
0.0075
0.42
N96.5
860900
b0.8
b0.2
b0.2
b0.02
b0.25
b0.5
114
(DGs) and TGs and total and free glycerol, were determined and measured (Table 5). It should be noted that for further scaling up of biodiesel
production and its promotion in the market, all quality characteristics
specied by the European standard EN 14214 should be determined.
Conclusions
In this work, a two-step homogeneous catalyzed waste lard
transesterication reaction for biodiesel production was investigated.
For this purpose, a factorial design methodology of experiments was
utilized and six variables that typically affect the production process
were examined. The statistical signicant variables, their effects and
the higher order interaction effects on process efciency were identied. The main results drawn from this study are concluded below.
The esterication step is signicantly affected mostly by the reaction
time and the MeOH:FFA ratio value. Specically, an increase in their
level brings an increase in the FFA acidity reduction percentage. Likewise, the transesterication step is positively affected by three independent variables, namely reaction time, KOH concentration and MeOH:
triglyceride ratio, that typically affect its performance. Furthermore,
based on the statistically signicant variables, two empirical models describing evolution of the two-step biodiesel production process were
developed. This is of major importance since they are valuable tools to
further scale-up the process by computing its reaction yield. Finally, it
has to be noted that by applying the proposed two-step process, biodiesel, conformed to the European Community quality standards, can be
produced from a low cost feedstock, namely waste lard.
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