Fuel Processing Technology 87 (2006) 883 890

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Transesterification of neat and used frying oil:

Optimization for biodiesel production
D.Y.C. Leung , Y. Guo
Department of Mechanical Engineering, the University of Hong Kong, Pokfulam Road, Hong Kong, China
Received 5 January 2006; received in revised form 8 June 2006; accepted 12 June 2006

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 ysis and comparison of biodiesel productions using neat edible-

Alkaline-catalyzed transesterification method is normally
adopted for biodiesel production. However, the biodiesel pro-
duced 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 al-
ternative 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 veg-
etable oils in biodiesel production. In this study, a detailed anal-
Corresponding author. Tel.: +852 28597911; fax: +852 28585415.
E-mail address: ycleung@hku.hk (D.Y.C. Leung).
0378-3820/$ - see front matter 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.fuproc.2006.06.003
grade Canola oil and UFO as feedstocks were conducted.
The main objectives of this work were to explore the rela-
tionships 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 condi-
tions 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 D.Y.C. Leung, Y. Guo / Fuel Processing Technology 87 (2006) 883890

Table 1 The composition of methyl ester in biodiesel was determined

Physical and chemical properties of the oil feedstocks using a HP 6890 Series II Gas Chromatograph with a 3365/IIGC-
Property UFO a Neat Canola oil ChemStation and a flame ionization detector. The capillary
Acid value (mg KOH/g) 2.1 <0.5 column was a HP-INNOWax (Cross-Linked PEG) column with a
Kinematic viscosity at 40 C (cSt) 35.3 30.2 length of 30 m, a film thickness of 0.5 m and an internal diameter
Fatty acid composition (wt.%) of 0.32 mm. Helium was used as carrier gas and also as an
Myristic (C14:0) 0.9 0.1
auxiliary gas for the FID. One micro-liter of each sample was
Palmitic (C16:0) 20.4 5.5
Palmitoleic (C16:1) 4.6 1.1 injected manually. The internal standard quantitative calculation
Stearic (C18:0) 4.8 2.2 was chosen with methyl heptadecanoate as the internal standard.
Oleic (C18:1) 52.9 55 As a supplement to GC analysis, thin layer chromatography
Linoleic (C18:2) 13.5 24 (TLC) was also used for qualitatively analyzing the presence of
Linolenic (C18:3) 0.8 8.8
mono-, di- and triglyceride in the product, which indicates the
Arachidic (C20:0) 0.12 0.7
Eicosenic (C20:1) 0.84 1.4 extent of transesterification. TLC was performed on glass plates
Behenic (C22:0) 0.03 0.5 coated with silica gel HF254 (Merck). The developing solvent
Erucic (C22:1) 0.07 0.4 was hexane and diethyl ether. Phosphomolybdic acid dissolved
Tetracosanic (C24:0) 0.04 0.3 in ethanol was used for visualization.
Mean molecular weight (g/mol) 856 882
a
Samples have been pretreated by filtering and dehydration before analysis. 2.3. Methods

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 in-
dicating 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.
weight of ester
Ester content
weight of product
weight of product
Product yield
weight of raw oil
In our previous mixing intensity study [9,10], the degree of
mixing of the reactants is found to be an important factor that
affects the transesterification rate and the product yield. In this
study, the mixing degree of the reaction system was kept at the
maximum extent of the present experimental equipment. It was
achieved by using a small amount of feedstock oil (200 g) and a
relatively large reactor (1 l capacity). The operation was carried
out at a maximum stirring speed of 1100 rpm in the first stage of
reaction (10 min), and a lower stirring speed of 600 rpm in the
subsequent stage (5 min).
Used frying oil of 200 g was first filtered by cloth to remove
bits of food residues, and then placed in a beaker equipped with
a magnetic stirrer and a thermometer. Under agitation, the raw
oil was heated up to a desired temperature on a heating plate. A
fixed amount of fleshly prepared NaOHMethanol solution was
added into the oils, taking this moment as the starting time of the
reaction. When the reaction reached the preset reaction time,
heating and stirring were stopped. The products of reaction were
allowed to settle overnight producing two distinct liquid phases:
crude ester phase at the top and glycerol phase at the bottom.
The crude ester phase separated from the bottom glycerol phase
was then washed by cold or warm deionized water several times
until the washed water became clear. The excess methanol and
water in ester phase were then removed (or recycled) by evap-
oration under atmospheric condition. After being weighted (for
product yield calculation), the final product was analyzed by
GC to determine its ester content (i.e. purity of product). The
virgin Canola oil does not need to be filtered prior to tran-
sesterification as is required for the waste oil.
The reaction was investigated step by step. The optimal value
of each parameter involved in the process was determined while
the rest of the parameters were kept constant. After each optimal
was attained, this value was adopted for the optimization of the
next parameter. It should be noted that once the reaction takes
1
place, it would continue even at room temperature, as long as the
catalyst residues still exist in the product mixture, which is
believed to be favorable for biodiesel production. In the present
2
experiments, when heating was finished, no acid was added into
 D.Y.C. Leung, Y. Guo / Fuel Processing Technology 87 (2006) 883890
the product mixture to neutralize the catalyst residues and to stop
the reaction at once, but rather the catalyst residues were kept in
the mixture, and experienced a long settling time together with the
mixture, so that a better conversion was obtained due to this
extended reaction time. The reaction would stop completely when
water washing was finished, because all the catalyst residues in the
product mixture have been removed during this process. The pH
value of the product and the washed water was all 7 at that time.
Therefore, in order to compare the product yield under different
reaction conditions, the product mixtures were allowed to settle for
the same period (i.e. 15 h) and washed with the same washing time
(about 1 h) so that all conditions for the experiments were the same
except for the variables being studied.
3. Choice of alkaline catalysts
Three alkaline catalysts sodium hydroxide (NaOH),
potassium hydroxide (KOH) and sodium methoxide (CH3ONa),
all of which are commonly used for alkaline-catalyzed transester-
ification research, were selected for this study. To evaluate the
performance of each of these catalysts, the transesterification of
the UFO with methanol was carried out with the use of individual
catalyst under identical molar ratio of methanol to oil (7.5:1),
reaction temperature (70 C), reaction time (30 min) and subject
to the same degree of mixing.
It should be noted that the process with an acid-catalyzed
pretreatment step to convert the free fatty acid (FFA) in oils to
esters followed by an alkaline-catalyzed step to convert the
triglycerides to esters is recommended by many researchers for
converting the waste oils with higher FFA content into biodiesel.
However, this process is more complex in the instrumentation
(because of the addition of a pretreatment unit) than the alkaline-
catalyzed process, thereby resulting in an increase in equipment
and operating costs. Therefore, the alkaline-catalyzed process,
with fewer and simpler process equipment units, is commonly
used in an industrial process. However, the alkaline-catalyzed
process is sensitive to FFA content of the feedstock oils. Many
published papers [911] suggested that alkaline catalysts could
only be applied when FFA content in the oils or fats is less than
Fig. 1. Ester content under different catalyst concentrations for the transester-
ification of UFO.
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)
Concentration of the catalyst Ester content Product yield
(wt.%, by weight of crude oil) (wt.%) (wt.%)
NaOH 1.1 94.0 85.3
KOH 1.5 92.5 86.0
CH3ONa 1.3 92.8 89.0
1.0%. In Hong Kong, most UFOs discarded by the restaurants
usually have a relatively lower FFA content (ranging from 0.20%
to 1.5%). Therefore, one of the aims of this study is to investigate
the commercial feasibility of using UFO as a feedstock to produce
biodiesel by alkaline-catalyzed process.
3.1. Amount of catalysts
The effects of the three catalysts used on the transesterifica-
tion 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. Max-
imum 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 dis-
sociates 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
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 D.Y.C. Leung, Y. Guo / Fuel Processing Technology 87 (2006) 883890
Fig. 2. States of the final product mixtures settled overnight with different catalysts.
For NaOH or CH3ONa catalyst, after settling overnight the
product mixture separated into two layers: crude ester layer in
liquid state (upper layer) and glycerol layer (lower layer) (Fig. 2a).
As known, glycerol is a viscous liquid at ambient temperature and
pressure. When more and more solid soaps sank to the bottom, a
mixture of glycerol and soap in solid state was formed after
settling overnight. Thus, the separation of the top crude ester layer
from the bottom glycerol layer had to be decanted or drawn out
from the top of the separation unit, and could not flow out directly
from the bottom of the separation unit.
Different from the other two catalysts, for KOH catalyst, the
product mixture separated into two liquid layers after settling
overnight: crude ester layer on top and glycerol layer at the bottom
(Fig. 2b). Due to the fact that potassium soap is softer than sodium
soap, its residues which formed during the transesterification
reaction, do not, like sodium soaps, sink onto the glycerol layer at
the bottom but suspend in the crude ester layer, thus resulting in a
viscous glycerol layer. Therefore, for the separation of the ester
layer from the glycerol layer in industrial production, using KOH
as catalyst is undoubtedly more convenient and simpler in the
process as well as apparatus than using NaOH or CH3ONa as
catalyst since the glycerol layer in liquid state can be removed
easily by direct outflowing from the bottom of the separation unit.
Due to this reason, KOH is commonly used for producing bio-
diesel using waste recycled oil feedstock.
3.3. Cost of catalysts
Table 3 compared the unit price of the three catalysts used in
this study. As can be observed NaOH is much cheaper than the
other two catalysts in the market. Comparing the performance and
cost of the three catalysts, NaOH was found to be more superior
than CH3ONa and KOH due to its lower price and smaller amount
Table 3
Unit price of catalyst as of 2005
NaOH KOH CH3ONa
(purity: 99%) (purity: 92%) (purity: 99%)
Price a (US$/ton) 400 770 2300
a
Prices are quoted from companies in China.
of catalyst required. Therefore, NaOH is most commonly used in
the market and was chosen for the rest of the study.
4. Optimization of process parameters
4.1. Effects of catalyst concentration
The concentration of the catalyst was the first parameter
studied. The effect of NaOH concentration on the transester-
ification of the neat Canola oil and UFO was investigated with its
concentration varying from 0.5 to 1.6 wt.% (based on the weight
of raw oil). The operation conditions during the whole reaction
process were fixed at: reaction temperature of 70 C, reaction
time of 30 min and molar ratio of methanol to oil at 7.5:1.
Experimental results (Fig. 3) showed that the changes in
ester content with catalyst concentration followed an asymptotic
curve for all the oil samples. As the NaOH concentration in-
creased, the conversion of triglyceride, as well as the ester
content also increased. Insufficient amount of NaOH resulted in
incomplete conversion of triglycerides into the esters as in-
dicated from its lower ester content. The ester content reached
an optimal value when the NaOH concentration reached a
certain level, and remained relatively constant with a further
increase in catalyst concentration. Table 4 shows the optimal
ester content and the concentration of NaOH to achieve this
level for the two oil feedstocks. For neat Canola oil, a NaOH
concentration of 1.0 wt.% was adequate to complete the con-
version of triglycerides into methyl esters. Further increase in
catalyst concentration neither enhances further conversion
nor raises the ester content. Based on this observation, the
product yield under the cases of excess NaOH concentrations
(> 1.0 wt.%) was examined. It can be seen from Fig. 3a that
when the NaOH concentration was increased from 1.0 wt.% to
1.6 wt.%, the yield of the biodiesel product (with a purity of
98 wt.%) dropped from 85 wt.% to 65 wt.%, a reduction of
20 wt.%. Large amounts of soaps were observed during the
experiment as excess NaOH catalyst was added, which was
responsible for the yield reduction. This is because addition of
excess alkaline catalyst (NaOH) caused more triglycerides par-
ticipating in the saponification reaction with NaOH producing
more soap, thereby reducing the ester yield.
 D.Y.C. Leung, Y. Guo / Fuel Processing Technology 87 (2006) 883890 887

optimal catalyst amount was 10% larger than that found in the
transesterification of neat Canola oil (1.0 wt.%), whereas cor-
responding 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 concen-
tration 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 con-
centration 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.
Maximum ester content was obtained at 1.0 wt.% NaOH
concentration, with reasonably high yield. These were identified
to be the optimal values for transesterifying neat Canola oil.
Excess NaOH catalyst had very little effect on the ester content,
but led to a marked reduction in the product yield and also
added extra cost to the process for removing the excess catalyst
and soaps at the post-treatment stage of product purification. As
a whole, the catalyst concentration had a large effect on the
purity and yield of biodiesel obtained, and should be controlled
accurately and carefully.
For UFO the optimal NaOH concentration was 1.1 wt.%,
which produced a maximum ester content of 94.6 wt.%. This
Our previous mixing intensity study [12,13] indicated that the
reaction time required for the completion of the alkaline-catalyzed
transesterification reaction depends not only on the reaction
temperature, but also on the degree of mixing in the process. The
reaction rate of transesterification increases with increasing tem-
perature and mixing degree. The reaction time of the transester-
ification reaction conducted at 70 C was optimized with the
highest achievable mixing degree and an excess molar ratio of
methanol to oil (7.5:1) with the optimal NaOH concentration at 1.0
and 1.1 wt.% for neat Canola oil and UFO, respectively.

Table 4
Properties of biodiesel produced under optimal reaction conditions
Feedstocks
Neat Canola Used frying
oil oil
Catalyst (NaOH) concentration (wt.%) 1.0 1.1
Reaction temperature (C) 45 60
Methanol/oil molar ratio 6:1 7:1
Maximum biodiesel yield (wt.%) 93.5 88.8
Ester content (wt.%) 98.0 94.6
Kinematic viscosity of biodiesel at 40 C (cSt) 3.6 4.0
Fig. 4. TLC results of product composition at different reaction times for
Acid value of biodiesel (mg KOH/g) 0.08 0.15
transesterified Canola oil.
888 D.Y.C. Leung, Y. Guo / Fuel Processing Technology 87 (2006) 883890

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-, di-
glycerides and free fatty acid could be seen in the TLC analysis.
Accordingly, a reaction time of 15 min was adequate to com-
plete 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 ener-
gy 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 Fig. 6. Effect of methanol/oil molar ratio on the transesterification of (a) neat
decreased from 87.5% to 85.3%, dropped by about 2%. This is Canola oil; and (b) UFO.
because longer reaction enhanced the hydrolysis of esters (re-
verse reaction of transesterification), resulted in a loss of esters yield. The optimal reaction time for the transesterification of
as well as causing more fatty acids to form soap. More visible UFO is 15 min at 70 C with the maximum mixing degree
soaps were observed experimentally with gradually extending currently available, which is similar to that of neat Canola oil.
the reaction time. Accordingly, it can be concluded that the
reaction time was also a controlling factor of product yield and 4.3. Effects of molar ratio of methanol to oil
extending the reaction time had a negative effect on the product
In order to study the effect of molar ratio on ester content and
yield of the transesterification, experiments were conducted
with various molar ratios of methanol to oil in the range of 3:1 to
11:1. The optimized catalyst concentration and reaction time as
obtained in the previous sections were adopted. Fig. 6 showed
the results of these experiments, which exhibited an asymptotic
trend for the ester content and yield. For the stoichiometric
transesterification reaction, three moles of methanol are re-
quired per mole of triglyceride to yield three moles of fatty
methyl esters and one mole of glycerol. The theoretical molar
ratio of methanol to triglyceride should therefore be 3:1. How-
ever, as shown in Fig. 6a, maximum ester yield was obtained at
a molar ratio of 6:1 for neat Canola oil. This higher molar ratio
than the stoichiometric value resulted in a greater ester con-
version and could ensure complete reaction. When the ratio was
increased from 3:1 to 6:1, the ester content raised from 80.3% to
Fig. 5. Effects of reaction time on ester content and product yield for 98.0%, while the yield rose from 78.7% to 90.0%. Therefore,
transesterified UFO at a temperature of 70 C. the reaction was incomplete for a molar ratio less than 6:1. On
 D.Y.C. Leung, Y. Guo / Fuel Processing Technology 87 (2006) 883890 889

the other hand, there is very little effect on the biodiesel yield
and purity for molar ratio beyond 6:1. Moreover, it was ob-
served 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.
on the product yield for the transesterification of neat oil. The
reason for this is that higher temperature accelerates the side
saponification reaction of triglycerides. But, obviously, the
temperature effect was smaller than that of catalyst concentration.
Unlike the neat oil, the maximum product yield obtained from
UFO was achieved at a higher temperature, i.e. 60 C (Fig. 7b).
The high temperature could be due to the higher viscosity of UFO,
compared to the neat oil (Table 1). Higher temperature could
accelerate the saponification of triglycerides, and had a negative
effect on the product yield, but could lead to a drastic decrease in
viscosity of UFO that is favorable to increase the solubility of the
oil in the methanol and improve the contact between oil and
methanol molecules, thereby reaching a better conversion of
triglycerides. Therefore, for the UFO, the optimal reaction tem-
perature of 60 C was, in fact, a result of the competition between
the main transesterification reaction and the side saponification
reaction.
Table 4 summarized the optimal conditions and respective
properties of the biodiesel product produced from neat Canola

4.4. Effects of reaction temperature

To determine the effect of reaction temperature on methyl

esters formation, the transesterification reaction was carried out
under the optimal conditions obtained in the previous section
(i.e. 6:1 methanol/oil molar ratio and 1.0 wt.% NaOH concentration
for neat oil; 7:1 methanol/oil molar ratio and 1.1 wt.% NaOH
concentration for UFO). The experiments were conducted at
temperatures ranging from 30 to 70 C. The effect of reaction
temperature on the product yield and reaction time was presented in
Fig. 7.
Experimental results showed that the transesterification
reaction could proceed within the temperature range studied
but the reaction time to complete the reaction varied signi-
ficantly with reaction temperature. It can be seen that a high
product yield could be achieved even at room temperature but
the reaction time would be substantially increased. It was also
observed that for neat oil the maximum yield occurred at a
lower temperature range between 40 and 45 C. When tem-
perature was reduced from 70 C to 45 C, the product yield can
be increased from 90.4% to 93.5%, enhanced by about 3%, but
the reaction time for completion of the transesterification was
prolonged from 15 min to 60 min due to a lower reaction rate at
45 C. This significant increase in ester yield at a lower tem- Fig. 7. Effect of temperature on the transesterification of (a) neat Canola oil; and
perature indicated that higher temperature had a negative impact (b) UFO.
890 D.Y.C. Leung, Y. Guo / Fuel Processing Technology 87 (2006) 883890
oil and UFO. The present optimization studies on the tran-
sesterification 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 mix-
tures 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, ex-
hibited 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. Op-
erating 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 com-
pletion 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.
Among all operational variables studied, catalyst amount and
methanol/oil ratio showed greater influences on the ester
formation than reaction temperature and reaction time in the
reaction stage.
The optimal amount of NaOH catalyst for the transester-
ification of the waste oil feedstock was greater than that of
neat oil due to their higher free fatty acid content but the ester
contents in the products were lower due to the presence of
impurities in the recycled waste oils.
Higher reaction temperature (i.e. >50 C) had a negative
impact on the product yield for neat oil, but had a positive
effect for waste oils with higher viscosities.
Optimal reaction for the transesterification of UFO with an
acid value of 2 and viscosity of 35 cSt could be achieved at
60 C for a reaction time of 20 min, 1.1 wt.% NaOH and 7:1
molar ratio of methanol/UFO. For commercial edible Canola
oil, the optimal conditions were 4045 C for a reaction time
of 60 min, 1.0 wt.% NaOH and 6:1 molar ratio of methanol/oil.
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