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Abstract
In this study, the characteristics and performance of three commonly used catalysts used for alkaline-catalyzed transesterification i.e. sodium
hydroxide, potassium hydroxide and sodium methoxide, were evaluated using edible Canola oil and used frying oil. The fuel properties of
biodiesel produced from these catalysts, such as ester content, kinematic viscosity and acid value, were measured and compared. With
intermediate catalytic activity and a much lower cost sodium hydroxide was found to be more superior than the other two catalysts. The process
variables that influence the transesterification of triglycerides, such as catalyst concentration, molar ratio of methanol to raw oil, reaction time,
reaction temperature, and free fatty acids content of raw oil in the reaction system, were investigated and optimized. This paper also studied the
influence of the physical and chemical properties of the feedstock oils on the alkaline-catalyzed transesterification process and determined the
optimal transesterification reaction conditions that produce the maximum ester content and yield.
2006 Elsevier B.V. All rights reserved.
Keywords: Alkaline-catalyzed transesterification; Ester; Glycerol; Catalyst; Fatty acid
1. Introduction
Alkaline-catalyzed transesterification method is normally
adopted for biodiesel production. However, the biodiesel produced from oils, no matter if it is neat vegetable oil or animal fat,
is usually more expensive than petroleum-based diesel fuel
from 10% to 50%. Therefore, the high cost of biodiesel is the
major obstacle for its commercialization. It is reported that
approximately 7095% of the total cost of biodiesel production
arises from the cost of raw materials, that is, vegetable oils or
animal fats [13]. Many researchers found that biodiesel can be
produced from waste oils such as used frying oil (UFO) [48].
Thus, recycled waste oils offer a significant potential as an alternative low-cost biodiesel feedstock. However, used frying oils
from restaurants and food industries have a variety of qualities,
and possess properties different from that of neat oils. Higher
impurities of the waste oils make them different from neat vegetable oils in biodiesel production. In this study, a detailed anal-
ysis and comparison of biodiesel productions using neat ediblegrade Canola oil and UFO as feedstocks were conducted.
The main objectives of this work were to explore the relationships between the relevant reaction variables (i.e. catalyst
amount, molar ratio of methanol to raw oil, reaction temperature
and reaction time) and the product characteristics (i.e. ester
content and yield). In particular, the influence of the physical and
chemical properties of the feedstock oils on alkaline-catalyzed
transesterification process was determined. The optimal conditions for biodiesel production from neat vegetable oil and waste
recycled oils were obtained.
2. Experimental details
2.1. Materials
Two types of oil feedstocks were used in the experiment: neat
Canola oil and used frying oil (UFO). The neat Canola oil was
obtained from the supermarket while the UFO was collected from
local Chinese restaurants. The physical and chemical properties of
these two feedstock oils were analyzed and given in Table 1. The
acid value of the raw oils shown in Table 1 was determined by
884
Table 1
Physical and chemical properties of the oil feedstocks
UFO a
Property
Acid value (mg KOH/g)
Kinematic viscosity at 40 C (cSt)
Fatty acid composition (wt.%)
Myristic (C14:0)
Palmitic (C16:0)
Palmitoleic (C16:1)
Stearic (C18:0)
Oleic (C18:1)
Linoleic (C18:2)
Linolenic (C18:3)
Arachidic (C20:0)
Eicosenic (C20:1)
Behenic (C22:0)
Erucic (C22:1)
Tetracosanic (C24:0)
Mean molecular weight (g/mol)
a
2.1
35.3
<0.5
30.2
0.9
20.4
4.6
4.8
52.9
13.5
0.8
0.12
0.84
0.03
0.07
0.04
856
0.1
5.5
1.1
2.2
55
24
8.8
0.7
1.4
0.5
0.4
0.3
882
titration while the fatty acid profile in the raw oils was determined
by Gas Chromatograph (GC). Based on the profile, the mean
molecular mass of the raw oils could be obtained. The kinematic
viscosity of the raw oil was determined using an Ubbelohde glass
capillary viscometer.
As can be seen from the table, the waste oil sample has
properties much different from those of the neat oil. For example,
they possessed a much higher acid value than the neat oil indicating the presence of a large amount of free fatty acid (FFA) in
the waste oils that could not be converted to biodiesel using an
alkaline catalyst. Furthermore, the kinematic viscosity of the
waste oil is much higher than that of the neat oil.
Catalyst is used to enhance the alkaline transesterification
process. To investigate the effect of different catalysts on the
transesterification process, three types of commonly used catalysts,
i.e. sodium hydroxide (NaOH), potassium hydroxide (KOH) and
sodium methoxide (CH3ONa) were selected. All the catalysts used
were of laboratory grade.
2.2. Analyses
In this study, the purity of biodiesel product, denoted by its ester
content, is defined as the weight percentage of methyl esters in the
final product after the purification and the removal of glycerol,
excess methanol, alkaline catalyst and soap in the product mixture
(Eq. (1)). It, in fact, is a close representation of the percentage of
triglycerides converted to methyl esters. Product yield is defined as
the weight percentage of the final product (transesterified and
purified oil) relative to the weight of oil at the start (Eq. (2)). It, in
fact, indicates the final results of the competition between the main
reaction (transesterification) producing methyl esters and the side
reactions (saponification) influencing the ester yield.
Ester content
weight of ester
weight of product
Product yield
weight of product
weight of raw oil
885
Table 2
Comparison of different types of catalysts used in the transesterification of UFO
(temperature of 70 C, reaction time of 30 min, methanol/oil molar ratio of 7.5:1)
NaOH
KOH
CH3ONa
Ester content
(wt.%)
Product yield
(wt.%)
1.1
1.5
1.3
94.0
92.5
92.8
85.3
86.0
89.0
The effects of the three catalysts used on the transesterification were compared through examining the ester content in the
biodiesel product obtained. Fig. 1 presented the results of the
transesterification with different amounts of NaOH, CH3ONa
and KOH catalyst. The three catalysts exhibited similar trends on
the conversion of triglycerides to esters, but different amounts of
catalyst were required for achieving the same conversion. Maximum ester content of the biodiesel product was reached at 1.1,
1.3 and 1.5 wt.% of the catalyst concentration for NaOH,
CH3ONa and KOH, respectively. The amount of NaOH used
was smaller than those of KOH and CH3ONa for the same mass
feedstock oil, since NaOH has the smallest molar mass (40 g/
mol), followed by CH3ONa (54 g/mol) and KOH (56 g/mol).
However, in terms of molar concentration CH3ONa was about 10%
lesser than that of NaOH and KOH.
Moreover, as shown in Table 2, the biodiesel yields with
NaOH and KOH as catalyst were lower than that of CH3ONa.
This happens because during the preparation of the catalyst NaOH
(or KOH) will be added and dissolved in the anhydrous methanol
forming sodium (or potassium) methoxide together with a small
amount of water according to the following equilibrium equation:
CH3 OH NaOHor KOHCH3 ONaor CH3 OK H2 O
3
The water in the reaction system predominantly reacts with oils
(triglycerides) and the Na+ (or K+) to form sodium (or potassium)
soaps. This is the saponification reaction of triglycerides leading
to the loss of triglycerides and hence reduction in final product
yield. On the other hand, the pure CH3ONa catalyst only dissociates into CH3O and Na+ without forming any water as side
product in the reaction that will cause a drop in product yield.
3.2. Separation of intermediate products
Fig. 1. Ester content under different catalyst concentrations for the transesterification of UFO.
When the above three catalysts were used in the reaction, the
final product mixtures derived from the transesterification exhibited
some differences in their physical states. Fig. 2 illustrated the states
of the final product mixtures settled overnight, produced from the
transesterification of UFO using these catalysts.
886
Fig. 2. States of the final product mixtures settled overnight with different catalysts.
Price a (US$/ton)
a
NaOH
(purity: 99%)
KOH
(purity: 92%)
CH3ONa
(purity: 99%)
400
770
2300
887
optimal catalyst amount was 10% larger than that found in the
transesterification of neat Canola oil (1.0 wt.%), whereas corresponding maximum ester content and biodiesel yield were
lower than that of neat Canola oil. This is because the UFO has a
relatively higher acid value (i.e. 1.5% free fatty acids) and
contains more impurities than those of the neat oil. When NaOH
is added to UFO, the free fatty acids in the raw oil predominantly
react with the alkaline to form sodium based soap and water, as
shown in the reaction below:
Accordingly, the free fatty acids in the raw oil were not
converted into esters, but to side product soap. Also, some
impurities in the oil could not be converted to esters and remained
in the final product, which contributed to the lower biodiesel yield
and product purity. To compensate for the catalyst loss resulting
from the reaction with free fatty acids, an additional amount of
catalyst was needed. Consequently, the optimal NaOH concentration used in the UFO was greater than that of the neat oil. In
addition, like the case of the neat oil, the use of NaOH concentration greater than the optimal value (i.e. 1.1 wt.%) also led to
a drastic reduction in biodiesel yield for UFO (see Fig. 3b) due to
the formation of soap.
4.2. Effects of reaction time
Fig. 3. Effect of catalyst concentration on the transesterification of (a) neat
Canola oil; and (b) UFO.
Table 4
Properties of biodiesel produced under optimal reaction conditions
Feedstocks
Neat Canola
oil
Used frying
oil
1.0
45
6:1
93.5
98.0
3.6
0.08
1.1
60
7:1
88.8
94.6
4.0
0.15
888
The results analyzed by TLC for neat Canola oil were shown
in Fig. 4. The changes in product compositions with reaction
time during the transesterification of the oils and the distribution
of various components in the reaction system can be clearly
seen. When the reaction time reached 15 min, no triglyceride
(main component of raw oil) was left in the product mixture,
indicating complete conversion; only traces of mono-, diglycerides and free fatty acid could be seen in the TLC analysis.
Accordingly, a reaction time of 15 min was adequate to complete the transesterification of neat Canola oil at 70 C with the
highest achievable mixing degree of the present study. Similar
phenomenon was observed for the UFO. Considering the energy requirement of the system and the conversion rate, 15 min
was therefore a suitable reaction time to complete the reaction
at 70 C. However, as shown later, the optimum yield was
achieved at 60 C with a reaction time of 20 min.
Fig. 5 showed a plot of methyl ester formed vs. reaction time
for UFO. The results showed that the reaction was very fast in the
first few minutes, a product of more than 90% ester content was
formed within the first 5 min. After that (the time of a clear phase
being formed), the reaction slowed down and entered a slow rate
stage till the reaction equilibrium was reached eventually.
As can be observed, the ester content increased with reaction
time at the beginning, reached a maximum at a reaction time of
15 min at 70 C, and then remained relatively constant with
increasing further the reaction time. Based on this, the product
yield under the case of a reaction time larger than 15 min was
examined. The results indicated that an extension of the reaction
time from 15 min to 30 min had no significant effect on the
conversion of triglycerides, but led to a reduction in the product
yield, the yield of the product with the same ester content
decreased from 87.5% to 85.3%, dropped by about 2%. This is
because longer reaction enhanced the hydrolysis of esters (reverse reaction of transesterification), resulted in a loss of esters
as well as causing more fatty acids to form soap. More visible
soaps were observed experimentally with gradually extending
the reaction time. Accordingly, it can be concluded that the
reaction time was also a controlling factor of product yield and
extending the reaction time had a negative effect on the product
Fig. 5. Effects of reaction time on ester content and product yield for
transesterified UFO at a temperature of 70 C.
the other hand, there is very little effect on the biodiesel yield
and purity for molar ratio beyond 6:1. Moreover, it was observed that for high molar ratio a longer time was required for
the subsequent separation stage since separation of the ester
layer from the water layer becomes more difficult with the
addition of a large amount of methanol. This is due to the fact that
methanol, with one polar hydroxyl group, can work as an
emulsifier that enhances emulsion. Therefore, increasing the
molar ratio of methanol/oil beyond 6:1 did not increase the
product yield as well as the ester content, but complicated the ester
recovery process and raised the cost for methanol recovery. The
results showed that the molar ratio of alcohol to oil is another
important parameter affecting the biodiesel yield and biodiesel
purity, apart from catalyst concentration and reaction time.
As stated above, a 6:1 methanol/oil molar ratio was optimal
for the transesterification of neat Canola oil. It resulted in the
highest ester content in the product (98%) and maximum product
yield (90.4%). This result is in line with the reports of many
investigations based on neat vegetable oils [3,10,14], and this
ratio has actually been normally adopted in commercial
operations. For UFO the highest ester content and product
yield were obtained at 7:1 molar ratio (Fig. 6b), which is larger
than the 6:1 ratio of neat Canola oil. This indicated that more
methanol were required for achieving the maximum ester yield
in the transesterification of UFO. The reason for this difference
was that UFO has much higher viscosities than the neat oil (see
Table 1), more methanol increases the solubility of the oil in the
methanol and improves the contact between oil and methanol
molecules, thereby maximizes the conversion. However, a
slightly lower ester content (94%) and yield (87.5%) were
obtained as compared with the case of neat oil.
889
Fig. 7. Effect of temperature on the transesterification of (a) neat Canola oil; and
(b) UFO.
890
oil and UFO. The present optimization studies on the transesterification of UFO with an acid value of 2.1 and viscosity of
35.3 cSt, concluded that highest conversion might be achieved at
1.1 wt.% NaOH concentration, 7:1 methanol/UFO molar ratio,
60 C after 15 min of reaction time. But the maximum biodiesel
yield is 88.8 wt.%, much lower than 93.5 wt.% for neat Canola
oil with a 0.25% free fatty acid content.
4.5. A note on the final settling time
After completion of the transesterification, the reaction mixtures were allowed to cool down to room temperature to produce
two phases: crude ester phase and glycerol phase. This phase
separation generally occurred quickly and can be observed
within the first 10 min of settling, but the ester layer was opaque,
indicating that the separation was incomplete. Experimental
results showed that given enough time for complete settling, the
opaque ester phase could turn crystalline and transparent. This
complete separation could take as long as 10 to 20 h. In fact,
during the settling, the transesterification process was still going
on. Therefore, the longer the settling time, the more favorable are
the separation and the conversion.
5. Conclusions
The study on the transesterification reaction conditions of two
feedstock oils (i.e. neat Canola oil and UFO) indicated that the
type and quantity of catalyst, molar ratio of methanol to oil,
reaction temperature and reaction time were the main factors
affecting the reaction. The optimal values of these parameters for
achieving maximum conversion of triglycerides to esters
depended on the chemical and physical properties of the feedstock
oils. The following conclusions can be drawn from the study:
The ester content in the final product, which indicates the
conversion efficiency of the transesterification reaction, exhibited an asymptotic tendency with the amount of catalyst.
Excess catalyst could not enhance the conversion but led to a
marked reduction in the product yield and added extra cost to
the process.
The ester content in the final product showed an asymptotic
tendency with methanol/oil molar ratio. The reaction was
incomplete for the ratio less than the optimal value. Operating beyond the optimal ratio, both the ester content and
the product yield would not be increased but resulted in
additional cost for methanol recovery.
Higher temperature decreases the viscosities of the feedstock
oils and has a positive influence on increasing the rate of
transesterification and shortening the reaction time. However,
higher temperature also induces a negative impact on the
ester yield due to the acceleration of the saponification of
triglycerides.
Sufficient reaction time should be allowed to ensure completion of the reaction. However, excess reaction time could
not promote the conversion but favors the reverse reaction of
transesterification (i.e. hydrolysis of esters), resulting in a
reduction in the product yield.