2450 Energy & Fuels 2007, 21, 2450-2459

Acid-Catalyzed Transesterification of Canola Oil to Biodiesel under

Single- and Two-Phase Reaction Conditions
Fadi Ataya,† Marc A. Dubé,*,† and Marten Ternan†,‡
Department of Chemical Engineering, Centre for Catalysis Research and InnoVation, UniVersity of Ottawa,
161 Louis Pasteur Street, Ottawa, Ontario, K1N 6N5, Canada, and EnPross, Inc., 147 Banning Road,
Ottawa, Ontario, K2L 1C5, Canada

ReceiVed March 21, 2007. ReVised Manuscript ReceiVed May 22, 2007

Experiments were performed at ambient temperature to investigate the effects of mass transfer during the
transesterification reaction of canola oil with methanol (MeOH) to form fatty acid methyl esters using a sulfuric
acid (H2SO4) catalyst at a MeOH/oil molar ratio of 6:1. Experiments at ambient conditions resulted in reaction
rates that were slow enough to permit the effects of mass transfer on the transesterification reaction to become
more evident than at higher temperatures. For the two-phase experiments, it was postulated that the reaction
occurred at the interface between the phases where the triglycerides (TG), MeOH, and H2SO4 were in contact
with one another. The influence of mass transfer was investigated by (a) comparing a mixed versus quiescent
two-phase reaction and (b) changing a two-phase reaction to a single-phase reaction through the addition of
a solvent, tetrahydrofuran. The experiments revealed the presence of an induction period prior to the initiation
of the reaction, and some of the factors influencing the induction period were identified.

Introduction (biodiesel) and glycerol. The transesterification reaction consists

Biodiesel is a renewable fuel produced from vegetable oils,
animal fats, or grease. Its chemical structure is that of fatty acid
alkyl esters (FAAEs). Because of diminishing petroleum
reserves and the environmental consequences of exhaust gases
from petroleum-derived fuels, biodiesel has attracted attention
during the past decade as a renewable and environmentally
friendly fuel. Because biodiesel is made entirely from vegetable
oils or animal fats, it is renewable, environmentally benign,
biodegradable, contains very little sulfur, and does not contain
any polycyclic aromatic hydrocarbons or crude oil residues.
Similar to petroleum diesel, biodiesel operates in compres-
sion-ignition engines, such as those used in farm equipment
and private and commercial vehicles. Biodiesel is sometimes
used in its pure form, B100, or as a 5% (B5) or 20% (B20)
blend with petrodiesel. Minor engine modifications may be
required in older diesel engines to avoid the dissolution of
various seals when B100 biodiesel is used; however, B5 or B20
blends can be used in unmodified diesel engines. Because
biodiesel is oxygenated, it is a better lubricant than low-sulfur
petrodiesel fuel (15 ppm of S), increasing the life of engines,
and is combusted more completely.1 The addition of 1-2%
biodiesel to modern ultralow-sulfur diesel fuel can produce a
blend having suitable lubricating properties.2
The dominant biodiesel production process, transesterification,
involves the reaction of alkyl alcohol with vegetable or animal
oils in the presence of a catalyst to yield mono-alkyl esters
* To whom correspondence should be addressed. Telephone: (613) 562-
5920. E-mail: Marc.Dube@UOttawa.ca.
† University of Ottawa.
‡ EnPross, Inc.
(1) Kiss, A. A.; Dimian, A. C.; Rothenberg, G. Solid acid catalysts for
biodiesel productionsTowards sustainable energy. AdV. Synth. Catal. 2006,
348, 75.
(2) Van Gerpen, J. Biodiesel processing and production. Fuel Process.
Technol. 2005, 86, 1097.
of a number of consecutive reversible steps. When methanol
(MeOH) is the alcohol, 1 mol of triglyceride (TG) is converted
sequentially to diglyceride (DG), monoglyceride (MG), and
finally fatty acid methyl ester (FAME) and glycerol (GLY). The
overall reaction sequence for the transesterification reaction is
shown below.
Overall Reaction:
1TG + 3MeOH T 1GLY + 3FAME (1)
Stepwise Reactions:
1TG + 1MeOH T 1DG + 1FAME (2)
1DG + 1MeOH T 1MG + 1FAME (3)
1MG + 1MeOH T 1GLY + 1FAME (4)
The reaction system is essentially heterogeneous because the
nonpolar TG phase (TG is the major component) and the polar
MeOH phase (MeOH is the major component) are immiscible.3
There are several variables that influence the reaction. Increasing
the temperature increases the mutual solubility of the two
phases.4 Increasing the stirring intensity favors conversion.5
Nevertheless, significant mass-transfer limitations have been
reported even when the reaction mixture was stirred vigorously.6
An inhibition period at the beginning of the reaction has been
(3) Ma, F.; Clements, L. D.; Hanna, M. A. Biodiesel fuel from animal
fat. Ancillary studies on transesterification of beef tallow. Ind. Eng. Chem.
Res. 1998, 37, 3768.
(4) Muniyappa, P. R.; Brammer, S. C.; Noureddini, H. Improved
converison of plant oils and animal fats into biodiesel and co-product.
Bioresour. Technol. 1996, 56, 19.
(5) Noureddini, H.; Harkey, D. W.; Gutsman, M. R. A continuous process
for the glycerolysis of soybean oil. J. Am. Oil Chem. Soc. 2004, 81, 203.
(6) Boocock, D. G. B.; Konar, S. K.; Mao, V.; Sidi, H. Fast one-phase
oil-rich processes for the preparation of vegetable oil methyl esters. Biomass
Bioenergy 1996, 11, 43.

10.1021/ef0701440 CCC: $37.00 © 2007 American Chemical Society

Published on Web 06/30/2007
Acid-Catalyzed Transesterification to Biodiesel
reported in several studies.6-9 Although conversion generally
increased with the reaction time, the relationship was nonlinear
and complex.7 With basic catalysts, saponification of glycerol,
one of the products, has been reported to enhance its reaction
with the TG reactant.4 The acid-catalyzed reaction requires
significantly longer reaction times than the base-catalyzed
reaction to reach any specified conversion to biodiesel.8
The addition of a cosolvent enhances the miscibility of the
phases, resulting in a homogeneous mixture and a faster reaction
rate.6 Alternatively, ultrasonic irradiation can be used to produce
emulsions from the immiscible liquids,10 or supercritical condi-
tions can be used to promote the formation of a homogenized
medium and drastically improve reaction rates.11 The key factor
limiting the conversion of TG is the degree of solubility between
the phases.4 Stirring enhanced the contact between the phases
and was reported to facilitate the initiation of the reaction.12
Improvements to the reaction rate in two-phase biodiesel
production systems can be attained by agitation, as shown in
recent work with base catalysts.13
Currently, the industrial-scale production of biodiesel fuel
entails the use of homogeneous base catalysts, leading to fast
reaction rates and high yields. In addition to virgin vegetable
oil feedstocks, there is interest in the use of low-grade or waste
feedstocks containing a relatively high free fatty acid (FFA)
content. These feedstocks present appreciable downstream
processing problems when processed with base catalysts. The
FFAs cause the formation of soaps that inhibit the separation
of biodiesel from the glycerol.14 This is an undesirable
complication of the process that adds fixed costs associated with
the use of several separation units for the removal of the
saponified products. The merits of faster conversion with the
base-catalyzed process, compared to the acid-catalyzed process,
are therefore offset by the higher costs associated with the
required use of virgin vegetable oils having very low concentra-
tions of FFAs. Sometimes, the cost of the virgin vegetable oil
feedstock approaches that of the petrodiesel product.
In contrast, soap is not formed with acid catalysts; therefore,
lower cost feedstocks that contain large concentrations of FFA
can be converted to biodiesel.15 The construction of a batch
pilot plant using a two-step acid-catalyzed pretreatment process
to produce biodiesel from a variety of feedstocks, including
those with a high FFA content, was proven to be successful
and resulted in high ester conversion.15 Zhang et al.16 conducted
an economic assessment and sensitivity analysis of four continu-
ous processes that produced biodiesel from waste cooking oil
(7) Darnoko, D.; Cheryan, M. Kinetics of palm oil transesterification in
a batch reactor. J. Am. Oil Chem. Soc. 2000, 77, 1269.
(8) Freedman, B.; Pryde E. H.; Mounts, T. L. Variables affecting the
yields of fatty esters from transesterified vegetable oils. J. Am. Oil Chem.
Soc. 1984, 61, 1638.
(9) Noureddini, H.; Zhu, D. Kinetics of transesterification of soybean
oil. J. Am. Oil Chem. Soc. 1997, 74, 1457.
(10) Stavarache, C.; Vinatoru, M.; Nishimura, R.; Maeda, Y. Conversion
of vegetable oil to biodiesel using ultrasonic irradiation. Chem. Lett. 2003,
32, 716.
(11) Saka, S.; Kusdiana, D. Biodiesel fuel from rapeseed oil as prepared
in supercritical methanol. Fuel 2001, 80, 225.
(12) Ma, F.; Clements, L. D.; Hanna, M. A. The effect of mixing on
transesterification of beef tallow. Bioresour. Technol. 1999, 69, 289.
(13) Ataya, F.; Dubé, M. A.; Ternan, M. Single-phase and two-phase
base-catalyzed transesterification of canola oil to fatty acid methyl esters
at ambient conditions. Ind. Eng. Chem. Res. 2006, 45, 5411.
(14) Canakci, M.; Van Gerpen, J. Biodiesel production via acid catalysis.
Trans. ASAE 1999, 42, 1203.
(15) Canakci, M.; Van Gerpen, J. A pilot plant to produce biodiesel from
high free fatty acid feedstocks. Trans. ASAE 2003, 46, 945.
(16) Zhang, Y.; Dubé, M. A.; McLean, D. D.; and Kates, M. Biodiesel
production from waste cooking oil: 2. Economic assessment and sensitivity
analysis. Bioresour. Technol. 2003, 90, 229.
Energy & Fuels, Vol. 21, No. 4, 2007 2451
and from virgin vegetable oil using both acid and base catalysts.
The results demonstrated that the acid-catalyzed process using
waste cooking oil was potentially a competitive alternative to
the common base-catalyzed process. Furthermore, the price of
waste cooking oil, the price of biodiesel, and the plant capacity
were evaluated as the major factors affecting the economic
feasibility of the biodiesel production process.
The influence of process variables on the acid-catalyzed
transesterification reaction has been reported in several
studies.8,14,17-19 Freedman et al.8 and Canakci and Van Gerpen14
examined the effect of the alcohol type on the acid-catalyzed
transesterification of soybean oil at temperatures just below the
boiling points of the alcohols. The results indicated that the
effect of the reaction temperature, rather than the type of alcohol
used, dominates the rate of the reaction and dictates the time
required to achieve complete ester conversion. The effects of
the reaction temperature, molar ratio of alcohol to oil, catalyst
concentration, water content, and FFA content on the acid-
catalyzed reaction were also studied. Canakci and Van Gerpen14
showed that the ester conversion increased with an increasing
temperature, increasing molar ratio of alcohol to oil, and
increasing acid-catalyst concentration. The addition of palmitic
acid, a FFA, and water prompted significant reductions in the
conversion of the ester. Moreover, the effects observed for the
addition of palmitic acid and the addition of water were
comparable. The reaction of FFAs with alcohol produced water,
which inhibited the esterification of FFAs and the transesteri-
fication of the glycerides. Recently, Liu et al.20 reported that
water strongly inhibited the catalytic activity of the H2SO4
catalyst.
Goff et al.18 conducted a study to investigate the efficiency
of different acid catalysts at elevated temperatures under
different operating conditions and determined that H2SO4 was
the most effective catalyst for the transesterification reaction.
Experiments that produced ester yields greater than 99% were
performed at a 9:1 molar ratio of MeOH/soybean oil, 120 °C,
and 1 wt % H2SO4 catalyst (on the basis of the oil) for a reaction
time of 19 h.
Acid-catalyzed reaction kinetics have been reported in the
literature.17,19 Freedman et al.19 investigated the acid-catalyzed
butanolysis of soybean oil at an alcohol/oil molar ratio of 30:1
and a 1 wt % H2SO4 catalyst concentration at different
temperatures in the range of 77-117 °C. The results indicated
that essentially complete conversion was achieved in 20 h at
77 °C and 3 h at 117 °C. The forward reactions appeared to
follow first-order kinetics because of the large excess alcohol
requirements, while the reverse reactions followed second-order
kinetics.
Zheng et al.17 studied the acid-catalyzed transesterification
reaction kinetics of waste frying oil using MeOH/oil molar ratios
in the range of 50:1-250:1 and acid-catalyst concentrations
ranging from 1.5 to 3.5 mol % (on the basis of the oil) at
temperatures of 70 and 80 °C. The results demonstrated that
the acid-catalyzed transesterification reaction of waste frying
oil in MeOH effectively follows pseudo-first-order reaction
kinetics, provided that the molar ratio of MeOH/oil is ap-
(17) Zheng, S.; Kates, M.; Dubé, M. A.; McLean, D. D. Acid-catalyzed
production of biodiesel from waste frying oil. Biomass Bioenergy 2006,
30, 267.
(18) Goff, M. J.; Bauer, N. S.; Lopes, S.; Sutterlin, W. R.; Suppes, G. J.
Acid-catalyzed alcoholysis of soybean oil. J. Am. Oil Chem. Soc. 2004,
81, 415.
(19) Freedman, B.; Butterfield, R. O.; Pryde, E. H. Transesterification
kinetics of soybean oil. J. Am. Oil Chem. Soc. 1986, 63, 1375.
(20) Liu, J.; Lotero, E.; Goodwin, J. G. Effect of water on sulfuric acid-
catalyzed esterification. J. Mol. Catal. 2006, 245, 132.
2452 Energy & Fuels, Vol. 21, No. 4, 2007
proximately 250:1 at 70 °C or, at the reaction temperature of
80 °C, that the molar ratio is in the range of 74:1-250:1.
In this paper, a series of acid-catalyzed transesterification
reactions was performed at ambient conditions under varying
conditions of homogenization. The goal was to investigate the
effects of agitation and removal of the two-phase interface on
the conversion of TG and yield of FAME. Ambient temperature
conditions were used in an attempt to have reaction rate kinetics
that were slow enough for mass-transfer effects to constitute a
measurable fraction of the overall rate.
Experimental Section
Experiments were conducted to measure the conversions of TG
and DG in canola oil and the corresponding yields of DG, MG,
and FAME. All experiments were performed at ambient temperature
(20 °C) and pressure (1 atm) over a time period of 24 h. The
reaction mixture had a MeOH (Commercial Alcohols Incorporated)
to canola oil ratio of 6:1. The mass of canola oil used in each batch
was approximately 10 g. The feedstock canola oil was the “no-
name” brand marketed by Loeb grocery stores. Sulfuric acid
catalyst, H2SO4 (BDH, Inc.), at 3 wt % by weight of the canola oil
was used for all reactions. The reaction mixture was placed in a
120 mL vial. Vials were cylindrical in shape, with an inside
diameter of ∼38 mm and an inside length of ∼105 mm. Our
analysis showed that the reaction mixture initially contained TG,
DG, and FFA. The mass ratios of DG/TG and FFA/TG in the
feedstock were determined by high-performance liquid chroma-
tography (HPLC) to be 0.0135 and 0.0152, respectively.
Three experimental conditions were tested: the quiescent two-
phase reaction, the agitated two-phase reaction, and the agitated
single-phase reaction. For the single-phase reactions, the homoge-
neous medium was obtained by adding 20 mL of HPLC-grade
tetrahydrofuran (THF) (Sigma-Aldrich) to the reaction vials at a
volumetric ratio of 1.5:1 THF/total sample. The quiescent two-
phase reaction vials were left standing for specified times, while
the agitated two-phase reaction and agitated single-phase reaction
vials were agitated using a Labline multiwrist shaker at its maximum
frequency of 500 shakes/min for the times specified.
The analysis of the reaction products included several steps. After
the reaction, the samples were immediately washed with 20 mL of
water, resulting in a lower polar phase, which was discarded, and
an upper nonpolar phase. This upper phase was then filtered through
0.2 µm polytetrafluoroethylene syringe filters and analyzed using
HPLC according to the method reported by Dubé et al.21 HPLC
vials containing 0.04 g of sample were weighed and diluted with
THF to make up 20 mg/mL sample solutions for HPLC analysis.
The HPLC (Waters Corporation) consisted of a pump, a flow and
temperature controller, a differential refractive index detector, and
two 300 × 7.5 mm Phenogel columns of 3 µm and 100 Å pore
size (Phenomenex) connected in series. The system was operated
using Waters Millennium 32 software. HPLC-grade THF was used
as the mobile phase at a flow rate of 0.05 mL/min at 38 °C. The
sample injection loop was 200 µL, and the injected sample volume
was 20 µL. The running time required for product characterization
was approximately 60 min. Calibration curves (Dubé et al.)21 were
generated for the standards (Sigma-Aldrich): triolein (TG), diolein
(DG), monoolein (MG), methyl oleate (FAME), oleic acid (FFA),
and glycerol (GLY). The areas under the peaks in the chromato-
grams for the product samples were used together with the
calibration curves to determine the moles of the constituents (TG,
DG, MG, FFA, and FAME) present in the nonpolar phase.
The amounts of product constituents were subjected to further
computations to provide the conversions and yields of the com-
ponents used in the analysis. The moles of TG in the feedstock
were calculated from the measured number of moles of the product
(21) Dubé, M. A.; Zheng, S.; McLean, D. D.; Kates, M. A Comparison
of attenuated total reflectance-FTIR spectroscopy and GPC for monitoring
biodiesel production. J. Am. Oil Chem. Soc. 2004, 81, 599.
Ataya et al.
Figure 1. Fractional TG conversion to all products versus time, with
3 wt % H2SO4 (percent by weight of the canola oil). For all figures,
unless otherwise indicated, [ represent a quiescent two-phase reaction,
0 represent an agitated two-phase reaction, and 2 represent an agitated
single-phase reaction.
constituents plus the stoichiometry of the reactions. The moles of
DG and FFA in the feed were calculated from the moles of TG in
the feed and the DG/TG feed ratio and the FFA/TG ratio,
respectively. The moles of MeOH in the feed was 6 × (moles of
TG + moles of DG) in the feed. The moles of “MeOH in the
product” and “glycerol in the product” were calculated using the
moles of the product constituents plus stoichiometry of the reactions.
With the above information on feed and product constituents, the
conversions and yields were calculated. Standard International
Union of Pure and Applied Chemistry (IUPAC) definitions were
used for conversion (moles of feed converted/mol of feed) and yield
(moles of feed converted to a product constituent/mol of feed). The
Appendix presents all of the equations used to calculate the
conversions and yields.
Results and Discussion
The conversion of TG in the presence of 3 wt % H2SO4
catalyst was measured as a function of time for the transesteri-
fication of canola oil. Results are shown in Figure 1 for the
three different experimental regimes: the quiescent two-phase
reaction, the agitated two-phase reaction, and the agitated single-
phase reaction. The effect of agitation can be seen by comparing
the TG conversion profile for the quiescent two-phase reaction
with that for the agitated two-phase reaction. After 24 h of the
quiescent two-phase reaction, the fractional TG conversion was
less than 0.01, whereas it was greater than 0.05 for the agitated
two-phase reaction. Except for shaking, the reaction conditions
were identical in both sets of experiments. This indicated that
improved mixing had a beneficial effect on the rate of reaction.
The shaking motion causes material in the bulk of both phases
to move toward the interface, while simultaneously, material
at the interface moves to the bulk, resulting in an enhanced
interchange of material between the interface and the bulk within
each individual phase. Agitation might also increase the number
of droplets and decrease their dimensions, thereby increasing
the interfacial surface area available for reaction.
The change in conversion obtained by adding THF caused
the two-phase reaction to become a single-phase reaction and
can be seen in Figure 1. Fractional TG conversions after 24 h
reached 0.4 in the agitated single-phase system. In a single-
phase, there is no interface between phases and, therefore, there
can be no limitations because of interphase mass transfer. These
observations are consistent with the notion that mass transfer
influences the rate of reaction when an interface is present.6
Acid-Catalyzed Transesterification to Biodiesel
Figure 2. Fractional DG conversion to all products versus time, with
3 wt % H2SO4. See the caption in Figure 1.
Figure 3. Agitated two-phase reaction. Conversion of TG (XTG) and
yields of DG (YDG), MG (YMG), and FAME (YFAME) versus time at 3 wt
% H2SO4.
The conversion of DG during the transesterification of canola
oil using 3 wt % H2SO4 catalyst is shown as a function of time
in Figure 2. The negative conversions indicate that DG formation
resulting from the conversion of TG (see eq 2) exceeded DG
conversion to FAME (see eq 3). The negative fractional DG
conversion values are much less than “-1” because there is a
relatively small amount of DG initially present in the feedstock
compared to the amount of TG. DG consumption results in a
positive value for conversion, while DG production results in a
negative value. Thus, the large negative DG conversion indicates
that DG produced from the conversion of TG greatly exceeds
the DG consumed in the reaction at that point in time. Figure
3 shows the same information, but the results are reported as
positive values because DG is reported as a fractional yield and
there is a net formation of DG from the conversion of TG.
The fractional DG formation at early reaction times in the
single-phase reaction exceeded those in the two-phase reaction
(see Figure 2). This is an indication that the elimination of an
interface and thereby the elimination of interfacial mass transfer
limitations enhanced the reaction rate. A comparison of the
quiescent two-phase reaction and the agitated two-phase reaction
shows that DG formation with agitation exceeded that of the
quiescent condition, where almost 0 DG conversion or formation
took place. This demonstrates the beneficial effect of mixing
on the rate of reaction.
An induction period was observed prior to the initiation of
TG conversion in the agitated two-phase reaction (Figure 1).
The induction period is also seen in the DG conversion data
for the agitated two-phase reaction (Figure 2). However, the
Energy & Fuels, Vol. 21, No. 4, 2007 2453
DG induction period is shorter than that for TG, and the DG
conversion reaction initiates prior to that for TG (see Figures 1
and 2). The existence of a TG induction period in biodiesel
production has been reported previously.5,6,13,19 Boocock et al.6
suggested that the TG induction period was caused by the two-
phase nature of the medium. His suggestion was substantiated
by the absence of the TG induction period in the single-phase
reaction as shown in Figure 1. The end of the TG induction
period for the agitated two-phase reaction occurred at the end
of the transitions from DG formation to DG conversion and
back to DG formation (see Figure 2). The end of the TG
induction period is seen in Figure 1, and the formation-
conversion-formation transition in DG is shown in Figure 2 at
the same reaction time (∼8 h).
There were two factors that were observed to influence the
TG induction period. The first factor was agitation. The duration
of the induction period in the quiescent reaction mixture was
reduced when the reaction mixture was agitated (see Figure 1).
This is one indication that mixing or enhanced mass transfer
can affect the induction period. The second factor was the
presence of an interface between the two phases. The removal
of the interface by the addition of THF for the single-phase
reaction resulted in no induction period (see Figure 1). Similar
indications can be made with respect to the DG reaction
induction period (see Figure 2).
For the agitated two-phase reaction, there was a sudden
increase in TG conversion of almost 4% at the end of the
induction period (see Figure 1). This increase occurred simul-
taneously with the DG formation-conversion-formation transi-
tion, specifically, toward the end of the DG conversion and the
beginning of DG formation. This conversion increase accounted
for the majority of the TG conversion observed during the 24
h reaction period. A similar sudden increase in conversion was
observed during some of our other experiments.
There have been several explanations for the reaction mech-
anism. Boocock et al.6 stated that “the catalyst is located only
in the methanol phase and therefore the reaction is limited by
the oil concentration in that phase”. In contrast, Dasari et al.22
performed noncatalytic reaction studies and reported that “the
reaction is kinetically controlled because methanol is able to
diffuse into oil faster than it reacts to form methyl esters”. Both
of these explanations are based on the reaction occurring in a
bulk phase, the polar MeOH phase in one case and the nonpolar
TG phase in the other. In contrast, the beef tallow experiments
reported by Ma et al.12,23 led to observations that “without
mixing, the reaction occurred only at the interface”.12 Several
additional experiments were carried out to evaluate these three
explanations.
First, visual observations were made to further characterize
the nature of the two phases. With a MeOH/canola oil molar
ratio of 6:1, the canola oil nonpolar phase (TG-rich) occupied
a larger fraction of the total liquid volume than the polar phase
(MeOH-rich). The molecular weight of TG (885.4 g/mol) is
much greater than that of MeOH (32.04 g/mol), and their
densities are 910 and 790 kg/m3, respectively. The nonpolar
TG phase had the largest volume; therefore, it was the
continuous phase during agitation, and the droplets of dispersed
phase were composed of the polar MeOH phase. When reaction
mixtures were allowed to settle in vials, the frothy mixture that
(22) Dasari, M. A.; Goff, M. J.; Suppes, G. J. Noncatalytic alcoholoysis
kinetics of soybean oil. J. Am. Oil Chem. Soc. 2003, 80, 189.
(23) Ma, F.; Clements, L. D.; Hanna, M. A. The effects of catalyst, free
fatty acids, and water on transesterification of beef tallow. Trans. ASAE
1998, 41, 1261.
2454 Energy & Fuels, Vol. 21, No. 4, 2007
existed during agitation immediately began to separate into two
layers. The top layer occupied the smaller volume (polar MeOH
phase), while the bottom layer (nonpolar TG phase) occupied
the larger volume. Initially, both layers were emulsions. The
top layer became clear in less than 2 h, whereas the bottom
layer took more than 2 days to clarify.
Second, some of the individual feedstock components were
mixed together in an attempt to understand their degree of
immiscibility. Feedstock MeOH that contained water was mixed
with H2SO4 in the feedstock proportions, and the MeOH, H2O,
and H2SO4 components were completely miscible. Feedstock
MeOH that contained water was mixed with FFA (oleic acid)
in the feedstock proportions, and the MeOH, H2O, and FFA
components were completely miscible. Feedstock MeOH that
contained water was mixed with FFA and H2SO4 in the
feedstock proportions, and in this case, the MeOH, H2O, FFA,
and H2SO4 mixture formed an emulsion.
Liu et al.20 investigated the impact of water on the acid-
catalyzed esterification of acetic acid with methanol and
suggested that the decreased catalytic activity of the protons is
a result of the preferential solvation of the acidic species by
water over methanol. Moreover, Gileadi and Kirowa-Eisner
reported that water molecules, in the presence of methanol, act
as scavengers for protons to form H3O+ cations.24 Therefore,
in the case where MeOH, H2O, FFA, and H2SO4 were mixed
in feedstock proportions and the emulsion was formed, a core
of H3O+ cations and their sulfate anions may have formed
micelles that have FFA molecules on their exterior. The OH
end of the FFA would be adjacent to the H3O+ core and
the hydrocarbon end in the polar MeOH phase. The emulsion
would include FFA-H3O+ micelles having acid cores inside
the polar MeOH phase that are shielded from contact with
MeOH.
Third, the analysis of the canola oil feedstock showed that it
contained TG, DG, and FFA. Because the feedstock would have
had a long time for reactions between its components to come
to equilibrium, the following reaction would ensure that the
canola feedstock contained at least a small amount of water:
TG + H2O T DG + FFA (5)
Lotero et al.25 stated that the water molecules affect the catalyst
accessibility to the TG molecules and inhibit the reaction. The
presence of acid in both the dispersed and continuous phases
was confirmed by experiment. After the reaction, the polar
MeOH phase and the nonpolar TG phase were allowed to
separate. Samples of each of the phases were removed, and
titration with calcium hydroxide, Ca(OH)2, showed that both
the polar MeOH phase and the nonpolar TG phase contained
acidic species. Therefore, when H2SO4 contacts the canola oil
feedstock, micelles would be expected to form. They would
have H3O+ cores and FFA molecules at the interface, thereby
shielding them from contact with TG molecules. FFA has an
OH group on one end of a hydrocarbon chain. This would
explain how the acid would be inside the nonpolar TG phase
but be shielded from contact with the TG molecules by the
FFA-H3O+ micelles.
From the above, it is likely that, during settling, the bottom
emulsion may have consisted of FFA-H3O+ micelles in the
(24) Gileadi, E.; Kirowa-Eisner, E. Electrolytic conductivitysThe hop-
ping mechanism of the proton and beyond. Electrochim. Acta 2006, 51,
6003.
(25) Lotero, E.; Liu, Y.; Lopez, D. E.; Suwannakarn, K.; Bruce, D. A.;
Goodwin, J. G. Synthesis of biodiesel via acid catalysis. Ind. Eng. Chem.
Res. 2005, 44, 5353.
Ataya et al.
Table 1. Octanol-Water Partition Coefficients (Kow)
component log Kow
glycerol -1.8
water -1.5
methanol -0.74
oleic acid (FFA) 7.64
MG 6.04
FAME 8.02
DG 14.64
TG 23.29
nonpolar TG phase. Similarly, it is likely that, during settling,
the top emulsion may have consisted of FFA-H3O+ micelles
in the polar MeOH phase.
The acid-catalyzed esterification reaction involves contact
between the protonated FFA molecules and MeOH (see eq 6).
The polar carboxylic group in the FFA molecules interacts with
water through hydrogen bonds, thereby facilitating the FFA-
catalyst interaction and the esterification reaction.23 Therefore,
the presence of the FFA-H3O+ micelles in both phases allows
for the protonation of the carbonyl group and the formation of
the protonated carboxylic acid. This is the first step for the acid-
catalyzed esterification reaction. The second step involves the
reaction with the weak nucleophile MeOH.
FFA + MeOH T FAME + H2O (6)
The octanol-water coefficient, Kow, is the ratio of the
equilibrium concentration of a species in octanol to that in water
at a specified temperature. Kow represents the tendency of a
chemical species to partition itself between an organic and
aqueous phase. This implies that species having similar Kow
values will be miscible and vice versa. In accordance with the
Kow values for the present study (see Table 1), most of the
MeOH is expected to be in the polar MeOH phase, thereby
allowing the esterification reaction to proceed readily in that
phase, whereas the acid-catalyzed esterification reaction in the
nonpolar TG phase is limited by the concentration of MeOH in
that phase. The reaction of FFA molecules in the polar methanol
phase would probably lead to a more pronounced destabilization
or disintegration of the FFA-H3O+ micelles in the polar MeOH
phase as compared to the nonpolar TG phase, and that may
result in the difference in clarity (attributed to the removal of
FFA-H3O+ micelles), upon settling, as observed in our experi-
ments.
The reaction medium is composed of polar MeOH phase
droplets dispersed in the continuous nonpolar TG phase. On
the basis of the octanol-water partition coefficients listed in
Table 1, it is useful to speculate on the composition of each of
the phases.26 At equilibrium, the chemical potential of each
component in one of the phases will be equal to its chemical
potential in the other phase. Nevertheless, the concentration in
one phase could be much different than that in the other phase.
On the basis of the values in Table 1, it might be expected that
(a) the polar MeOH phase would contain most of the MeOH,
H2O, and GLY, (b) the nonpolar TG phase would contain most
of the TG and DG, and (c) the FFA, MG, and FAME would be
distributed between the two phases. The feed components in
the reaction (TG, DG, FFA, MeOH, H2O, and H2SO4) are
expected to be distributed accordingly. TG and DG would be
expected to be present in the nonpolar TG phase, whereas
MeOH and H2O would be expected to be present in the polar
(26) Allen, D.; Shonnard, D. Green Engineering: EnVironmentally
Conscious Design of Chemical Processes; Prentice Hall PTR: Upper Saddle
River, NJ, 2001.
Acid-Catalyzed Transesterification to Biodiesel
MeOH phase. FFA would be expected to present in both phases,
and the titration experiments performed confirmed the presence
of the acidic species in both phases.
Surfactant molecules can be dispersed as single molecules,
form aggregates or micelles, or adsorb as a film at the interface,
and a dynamic equilibrium exists between theses states, resulting
in an equal rate of adsorption and desorption.27 DG and FFA
are surface-active agents and, as such, are expected also to be
present at the interface as well as in the bulk polar and nonpolar
phases. It is expected that the FFA molecules, owing to their
chemical structure, are present at the interface because the FFA
molecules contain both a polar and nonpolar group. The DG
molecules contain one hydroxyl group each, rendering them
slightly polar, while their hydrocarbon part can keep them in
contact with the nonpolar phase. This allows the DG molecules
to also be present at the interface, in addition to the FFA
molecules. In contrast, the TG molecules are essentially nonpolar
and thereby preferentially remain in the bulk of the nonpolar
phase.
Esterification reactions are faster than transesterification
reactions. Sendzikiene et al.28 studied the kinetics of the acid-
catalyzed esterification of FFA with MeOH and reported that
the apparent reaction rate constants for the experiments carried
out at 20, 34, and 60 °C were 1.27 × 10-4, 1.63 × 10-4, and
2.33 × 10-4 s-1, respectively, whereas studies for the acid-
catalyzed transesterification reaction indicated values that
were an order of magnitude smaller.19 For example, the acid-
catalyzed transesterification of soybean oil with 1-butanol
using 1% H2SO4 at 77 °C resulted in a forward reaction
rate constant of 5.00 × 10-5 s-1 for the TG-DG reaction.19
The TG and DG conversion profiles for the two-phase reactions
show the presence of an induction period prior to the initia-
tion of the reaction, and the DG induction period is shorter
than the TG induction period (see Figures 1 and 2). FFA
conversion results have been reported elsewhere18 for the
conversion of TG using an acidic catalyst. No FFA lag or
induction period has been documented in the open literature;
in fact, FFA reaction profiles indicate an almost instantaneous
reaction of FFA.20
The acid-catalyzed transesterification reaction is a two-step
procedure that involves contact between the protonated TG
molecules and MeOH. The first step in the reaction mechanism,
similar to that of the esterification of FFA, involves protonation
of the carbonyl group of the ester by the acid catalyst, forming
a resonance-stabilized complex and converting it into a strong
electrophile. The second step involves the reaction with the weak
nucleophile, MeOH.29 It is the protonated TG molecules that
need to interact with MeOH for a reaction to occur. Contact
between the TG molecules and the FFA-H3O+ micelles may
occur in the nonpolar TG phase during agitation; however, as
a result of the limited concentration of MeOH in that phase,
the interaction between the protonated TG molecules and
MeOH would be limited in that phase and any contact between
theses species would probably occur at the interface. The
combination of experiments described above strongly supports
the “reaction at the interface” hypothesis rather than the reac-
(27) Patist, A.; Kanicky, J. A.; Shukla, P. K.; Shah, D. O. Importance
of micellar kinetics in relation to technological processes. J. Colloid Interface
Sci. 2002, 245, 1.
(28) Sendzikiene, E.; Makareviciene, V.; Janulis, P.; Kitrys, S. Kinetics
of free fatty acids esterification with methanol in the production of biodiesel
fuel. Eur. J. Lipid Sci. Technol. 2004, 106, 831.
(29) McMurry, J. Organic Chemistry, 4th ed.; Brooks/Cole Publishing
Co.: New York, 1996.
Energy & Fuels, Vol. 21, No. 4, 2007 2455
tion in either of the bulk phases. The TG and DG conversion
results are consistent with the “reaction at the interface”
hypothesis.
In the polar MeOH phase, FFA molecules (RCOOH) and the
catalyst will react with MeOH in an esterification reaction to
form FAME and water, according to eq 6. MeOH is the major
component in the polar MeOH phase and is present in excess
as a reactant. The acid-catalyzed esterification reaction is a
comparatively fast reaction. The reaction will proceed until
equilibrium is achieved. The reaction of FFA molecules within
the polar MeOH phase would result in a net decrease in the
number of FFA molecules, the number of FFA moles, and the
concentration of the FFA species in the bulk polar phase. The
difference in concentration between FFA at the interface and
FFA in the bulk is a driving force that causes some of the FFA
at the interface to transfer into the bulk polar phase. The flux
of some of the FFA molecules from the interface to the bulk
may permit the number of DG molecules at the interface to
increase. The FFA and DG species are both surfactants, and a
decrease in the interface concentration of FFA should result
in a net movement of DG molecules from the bulk nonpolar
TG phase to the interface, whereby the DG molecules will
occupy sites at the MeOH-TG interface previously occupied
by the FFA molecules that transferred in the bulk polar MeOH
phase.
Both the reaction equilibrium and phase equilibrium (mass-
transfer equilibrium) should be satisfied. FFA esterification is
a faster reaction than DG transesterification.19,28 FFA molecules
are expected to be present in the polar MeOH phase and the
protonation of the FFA species in that phase is expected to be
sterically promoted. Therefore, the FFA esterification reaction
in the polar MeOH phase is both kinetically and sterically
promoted. The octanol-water partition coefficients (see Table
1) show that FFA is expected to be more soluble in the polar
MeOH phase than DG; i.e., it is expected that the number of
FFA molecules in the polar MeOH phase is greater than the
number of DG molecules in that phase. Therefore, the DG
transesterification reaction in the polar MeOH phase is both
kinetically and sterically hindered and less likely to occur.
In the nonpolar TG phase, during agitation, the FFA-H3O+
micelles are likely to collide frequently with the TG molecules
of the continuous phase. During these collisions, an acidic
molecule may contact and associate with a TG molecule at the
FFA-H3O+ micelle-TG interface, forming a protonated TG
molecule. The TG transesterification reaction is influenced by
the concentration of MeOH in that phase.
It is likely that the reaction in eq 2 (TG + MeOH T DG +
FAME) did not occur in the first 5 h, because the data in Figure
3 show that FAME was only formed at reaction times greater
than 5 h. Rather, the reaction in eq 5 (TG + H2O T DG +
FFA) occurred (see Figure 3). Some evidence to support the
occurrence of eq 5 is the fact that the TG conversion was
identical to the DG yield during the first 5 h, as can be seen in
Figure 3. In principle, experimental FFA yield data should
provide additional insight.
In the experiments reported here, our HPLC analyses for FFA
(retention time ) 28.1 - 28.4 min) were completely normal in
the absence of FAME (retention time ) 28.6 - 28.9 min).
However, after 5 h of the reaction, the FAME concentrations
were much greater than the FFA concentrations. As a result,
the FFA peak was not detected when a much larger FAME peak
was present. The FFA analyses during the first 5 h of the
reaction time showed a net FFA conversion. As a result, the
2456 Energy & Fuels, Vol. 21, No. 4, 2007 Ataya et al.

Figure 4. Ln(1/(1 - XTG)) versus time, with 3 wt % H2SO4, where Figure 5. FFA fractional conversion versus the reaction time (in hours).
XTG is the TG fractional conversion. See the caption in Figure 1. Reaction conditions were identical to those of the agitated two-phase
experiments in Figure 1, except that 5 wt % FFA was added to the
reaction mixture.
FFA analyses of the experiments reported here did not provide
any insight about the validity of eq 5.
For a first-order reaction, a plot of ln(1/(1 - X)) as a function
The DG transesterification reaction in the polar MeOH phase of time will be linear, with a slope equal to the reaction rate
is limited by the number of DG molecules in that phase. DG constant, k. Figure 4 presents such a plot for the acid-catalyzed
molecules at the MeOH-TG interface need to be protonated biodiesel reaction with a 3 wt % H2SO4 catalyst. Kinetic reaction
prior to reaction with MeOH. Experimental analysis of the rate constants were determined for the following irreversible
nonpolar TG phase showed that the FAME yield increased single-phase reactions in the presence of THF:
simultaneously with the increase in conversion of DG or the
decrease in the yield of DG (see Figures 2 and 3). Moreover, k1 k2 k3
the FAME yield (see Figure 3) showed that there was an TG 98 DG 98 MG 98 GLY (7)
apparent induction period in the production of FAME. The + FAME + FAME + FAME
results also show that the decrease in the DG yield was followed The experimental conversion/yield data were represented
by a net increase in the yield of DG. satisfactorily using statistical regressions of the kinetic equations
An additional experiment was performed to provide insight (eqs 12-15) that were based on the irreversible reactions shown
on the time required for the FFA formation reaction, eq 6, to as eq 7. As a result, we did not introduce the additional
come to equilibrium. To circumvent the problem of the FFA parameters (rate constants) that would have been necessary to
peak being lost in the FAME shoulder, as described above, 5 include the possibility of reversible reactions. Nevertheless, it
wt % FFA was added to the reaction mixture used in the was recognized that, at larger conversions than those obtained
experiments reported here. The FFA conversions from those in this study, other workers, such as Vicente et al.,30 have
experiments are shown in Figure 5. The FFA conversion invoked a combination of both reversible and irreversible
increased sharply with time and reached its equilibrium conver- reactions.
sion after 5 h. This observation is the basis for our suggestion The expressions for the reaction rates that were integrated
that FFA equilibrium preceded DG conversion. Specifically, with their respective initial conditions are
Figure 3 shows that the FAME yield and a net DG yield both
began at reaction times in excess of 5 h. dTG
rTG ) ) -k1CTG t ) 0 CTG ) CTG0 (8)
The TG induction period, followed by the sudden increase dt
in TG conversion, is a phenomenon that we have observed in
several experiments (see Figures 1 and 3). The transesterification dDG
rDG ) ) k1CTG - k2CDG t ) 0 CDG ) CDG0 (9)
reaction between the protonated TG molecules and MeOH dt
occurs at the MeOH-TG interface. The protonation of the TG
molecules in the nonpolar TG phase, as a result of the FFA- dMG
H3O+ micelle-TG collisions during agitation in the TG rMG ) ) k2CDG - k3CMG t ) 0 CMG ) 0 (10)
dt
induction period, would increase the number of protonated TG
molecules in that phase. However, the contact between the rGLY ) k3CMG t ) 0 CMG ) 0 (11)
protonated TG molecules and MeOH at the MeOH-TG
interface is hindered because of the presence of surface-active The following expressions for the conversion of TG, XTG,
species at the interface. During the inhibition period, the and the yields of DG and MG, YDG and YMG, were derived using
FFA equilibrium, both reaction and phase, is achieved (see the method employed by Levenspiel.31 The resulting equations
Figure 5) and some of the DG molecules at the interface react (eqs 12-15) are similar to those developed by Levenspiel.31
(see Figure 2). This would increase the number of contact The difference is that a nonzero initial concentration of DG was
sites for the MeOH and protonated TG species at the inter- included in the development of eqs 12-15. As a result, the
face, and the reaction would occur. The increased number of
activated TG molecules formed during the TG induction period (30) Vicente, G.; Martinez, M.; Aracil, J.; Esteban, A. Kinetics of
sunflower oil methanolysis. Ind. Eng. Chem. Res. 2005, 44, 5447.
resulted in the sudden increase in TG conversion (see Figures (31) Levenspiel, O. Chemical Reaction Engineering, 3rd ed.; Wiley: New
1 and 3). York, 1999; pp 42-55.
Acid-Catalyzed Transesterification to Biodiesel Energy & Fuels, Vol. 21, No. 4, 2007 2457

Table 2. Rate Constants (s-1)

k1 5.55 × 10-6
k2 8.35 × 10-6
k3 1.80 × 10-6

equations used here include an additional factor, containing the

ratio of the initial feedstock DG/TG molar ratio

ln ( 1
1 - XTG )
) k1t (12)

CDG
YDG ) )
CTG0

( (() ( ) ) )
1 CDG0 k2
1- + 1 exp(-k2t) - exp(-k1t) (13)
k2 CTG0 k1
1- Figure 6. Agitated single-phase reaction. Conversion of TG (XTG) and
k1 yields of DG (YDG), MG (YMG), and FAME (YFAME) versus time at 3 wt

( )(
% H2SO4.
CMG 1 1 - exp(-k1t)
YMG ) ) - the TG molecules.13 The methoxy ion concentration is related
CTG0 k2 k1
1- 1- both to the ionization of methanol,32
k1 k3

( ( ) ) )
CDG0 k2 (1 - exp(-k2t)) CH3OH ) H+ + CH3O-
1- +1 (14) [H+ ][CH3O-]
CTG0 k1 k2
1- KMeOH ) 3 × 10-16 ) (16)
k3 [CH3OH]

( )(
CGLY k1t - 1 + exp(-k1t) and to the ionization of water
1

( )
YGLY ) ) -
CTG0 k2 k1 k1 H2O ) H+ + OH- KH2O ) 1 × 10-14 ) [H+][OH-] (17)
1- 1-
k1 k3 k2

( ( ) ) )
Equations 16 and 17 can be combined to obtain
CDG k2 (k2t - 1 + exp(-k2t))

( )
1- +1 (15)
CTG0 k1 k2 k2
1-
k3 k3
When regressions were performed, the rate constants shown
in Table 2 were obtained for the single-phase reaction. Specif-
ically, k1 was obtained using the TG conversion data in Figure
4 and eq 12; k2 was obtained using the DG yield data in Figure
6 and eq 13; and k3 was obtained using the MG yield data in
Figure 6 and eq 14. Finally, the values for k1, k2, and k3 were
used in eq 15 to predict the GLY yield. There were no adjustable
parameters in eq 15. Nonetheless, the experimental GLY values
and the predictions from eq 15 are in good agreement, as shown
in Figure 6. This agreement supports our suggestion that these
rate constants have physical meaning and are not just correlation
parameters.
The experimental data and the regression equation, eq 12,
for TG conversion are compared in Figure 4 for the single-
phase reaction. The experimental DG and MG yield data for
the single-phase reactions are compared with their respective
regression equations, in Figure 6. As indicated above, the use
of irreversible reactions provided satisfactory agreement.
The single-phase reaction with an acid catalyst and with a
basic catalyst can also be compared. A similar analysis of
reaction rates was applied to our data13 for the single-phase
reaction with a basic (NaOH) catalyst. It resulted in rate
constants that were 3 orders of magnitude larger than those in
Table 2. In both cases, the contact between TG and MeOH
would be equally intimate, because in both cases, the reaction
occurred in a single phase. Therefore, the only difference could
be the difference in the two catalysts.
The reaction that occurs with the basic catalyst is considered
to be between the methoxy ions (a reaction intermediate) and
[CH3O-] 3 × 10-16[CH3OH]
) ) constant (18)
[OH-] 1 × 10-14
This indicates that, for a constant methanol concentration, the
concentration of methoxy ions will be a constant that is
approximately 2 orders of magnitude less than the concentration
of the OH- ions that are provided by the basic catalyst.
The transesterification reaction under acid-catalyzed condi-
tions occurs between methanol and a protonated TG molecule.
According to the conventional mechanism,29 a proton is added
to one of the carbonyl oxygen atoms in the TG molecule to
form a TG cation. The concentration of protonated TG cations
is expected to be similar to that of carbenium ions, which have
concentrations33 that are generally less than the methoxy ions
calculated above. Moreover, the fact that the protonated TG
molecules are more bulky than their methoxy ion counterparts
would result in a difference in the rates of diffusion of these
reaction intermediates from the FFA-H3O+ micelle interface
through the nonpolar TG phase to the polar MeOH phase to
the interface, of course, in favor of the methoxy ion species.
The concentration of the protonated TG reaction intermediates
formed from the catalysts may also contribute to the transes-
terification reaction with acid catalysts being slower than the
transesterification reaction with basic catalysts.
TG conversion during the two-phase reaction was substan-
tially less than during the single-phase reaction, as shown in
Figure 1. A difference in the mass-transfer rate is one plausible
(32) Ballinger, P.; Long, F. A. Acid ionization constants of alcohols:
Acidities of some substituted methanols and related compounds. J. Am.
Chem. Soc. 1960, 81, 795.
(33) Bywater, S.; Worsfold, D. J. The reaction of diphenylethylenes with
boron trifluoride and water. Can. J. Chem. 1977, 55, 85.
2458 Energy & Fuels, Vol. 21, No. 4, 2007
explanation for the difference in conversions. For the agitated
single-phase reaction, the line had a steeper slope (see Figure
4). The steeper slope in the single-phase reaction was attributed
to a kinetically controlled regime. The smaller value of the slope
in the two-phase reaction suggests that mass transfer influenced
the rate of reaction for the two-phase agitated reactions (see
Figure 4). The equations for the mass transfer of TG and the
flow rate of TG from the bulk of the nonpolar TG phase to the
interface are
NTG ) kL(CTG-B - CTG-S) (19)
FTG ) NTGaVRX ) kL(CTG-B - CTG-S)aVRX (20)
and the equations for the reaction and the flow rate of TG at
the interface are
-rTG ) kRXCTG-S (21)
FTG ) -rTGVRX ) kRXCTG-SVRX (22)
Equations 20 and 22 were combined as follows:
CTG-B ) (CTG-B - CTG-S)eq 20 + (CTG-S)eq 22 )
( )
FTG FTG FTG 1 1 the single-phase reaction mixtures were greater than from the
+ ) + (23)
kLaVRX kRXVRX VRX kLa kRX
to obtain
( )
FTG 1 Progress through the various stepwise reactions (eqs 2-4)
) -rTG ) CTG-B ) kOVCTG-B (24)
VRX 1 1
+ agitated reaction in Figure 3, approximately the same values
kLa kRX
Although the nomenclature is slightly different, eq 19 is the
conventional form of the equation that is used to describe
interfacial mass transport.34 The value of the overall rate
constant, kOV, was obtained from the slope of the bold dashed
line in Figure 4. This line was based on the expression: XTG )
1 - exp(-kOVt). Then, when the value of kRX ) k1 ) 5.55 ×
10-6 s-1, the rate constant for the single-phase reaction, the
value of kLa was determined to be kLa ) 7.28 × 10-7 s-1. A
comparison of the kLa value with the kRX value suggests that
the mass-transfer phenomenon is an order of magnitude slower
than the reaction kinetic phenomenon. It is appropriate to
compare (a) the straight dot-dashed bold line (in Figure 4) for
two-phase TG conversion obtained from eq 24 that included
one mass-transfer process and one kinetic rate process and (b)
the nonlinear pointed line that represents the experimental data
for two-phase TG conversion. Because the linear equation, eq
24, does not match the nonlinear experimental data, it is possible
that the phenomena occurring are more complex than a simple
combination of one mass-transfer process and one kinetic rate
process.
Diffusion during two-phase TG conversion using an acid
catalyst can be compared with that using a base catalyst. There
are three phenomena that are pertinent. (1) We have already
noted above that during single-phase TG conversion the rate
constants with an acid catalyst are 3 orders of magnitude slower
than that with a base catalyst. (2) Similarly, the rate of two-
phase acid-catalyzed TG conversion is also much slower than
that of two-phase base-catalyzed TG conversion. (3) Both acid-
and base-catalyzed two-phase TG conversion are controlled by
(34) Bird, R. B.; Stewart, W. E.; Lightfoot, E. N. Transport Phenomena,
2nd ed.; Wiley: New York, 2002; p 545.
Ataya et al.
the reaction at the interface, which is a diffusion-influenced
phenomenon. If the same diffusion process controlled both acid
and base two-phase TG conversion, then both two-phase
processes would be expected to proceed at the same rate. An
explanation can be suggested for both acid- and base-catalyzed
reactions proceeding at the interface but at different rates. The
diffusing reaction intermediates are protonated TG molecules
in the case of acid-catalyzed two-phase TG conversion and
methoxy ions in the case of base-catalyzed two-phase TG
conversion. Because the protonated TG molecules are much
larger than the methoxy species, they will diffuse very slowly
compared to the smaller methoxy species. The result is that acid
and base catalysts produce different reaction intermediates that
diffuse at different rates.
The compositions of the transesterification products as a
function of time are shown in Figure 3 for the two-phase reaction
and in Figure 6 for the single-phase reaction. The fraction of
unreacted TG in the product is the difference between 1.0 and
the fractional TG conversion shown in the figures. The fractional
yields of DG and MG are expressed as the amount of product
formed per the amount of feedstock fed. The fractional yield
of FAME was calculated using FAME produced from the
conversion of TG, DG, or MG (see eqs 2-4) and the conversion
of FFA to FAME (see eq 6). The conversions and yields from
two-phase agitated reaction mixtures. The TG conversion and
DG, MG, and FAME yields from the single-phase agitated
reaction at 2.5 h (see Figure 6) are similar to those obtained for
the agitated two-phase reactions at 24 h (see Figure 3).
can be visualized from Figures 3 and 6. For the two-phase
were observed for TG conversion, DG yield, and FAME yield
after a 24 h reaction time. This suggests that only the first step
of the series reaction, eq 2, i.e., TG reacting to form DG and
FAME, has occurred. For the single-phase reaction in Figure
6, it is seen that, after 24 h of reaction time, the yield of FAME
exceeds the yield of DG. If the first step, eq 2, was the only
reaction occurring, the FAME and DG yields should have been
identical. Contributions to the additional FAME yields could
have been obtained from the following reactions: any conver-
sion of DG via eq 3, MG via eq 4, or FFA via eq 5 would have
produced additional FAME. These findings suggest that the
same reaction mechanism may be operating for both the single-
phase and two-phase reactions for the acid-catalyzed transes-
terification.
Conclusions
Canola oil transesterification experiments were performed as
both two-phase and single-phase reactions. For the two-phase
reaction medium, under both acid- and base-catalyzed condi-
tions, the reaction appears to occur at the interface of the two
phases. This is consistent with our experimental data.
For the single-phase medium where no mass-transfer resis-
tance occurred, reaction kinetic rate constants were determined.
The measured kinetic rate constants with an acidic catalyst (H2-
SO4) were found to be 3 orders of magnitude slower than those
with a basic catalyst (NaOH). This can be attributed to the
difference in concentration of the methoxy ions and the
protonated TG species. The differences in the kinetic rate
constants of the acid- and base-catalyzed processes can be
attributed to the difference in concentrations of the respective
ionic reaction intermediates.
For the two-phase agitated reaction, a mass-transfer coef-
ficient was calculated that was found to be 1 order of magnitude
Acid-Catalyzed Transesterification to Biodiesel Energy & Fuels, Vol. 21, No. 4, 2007 2459

smaller than the kinetic rate constant for the single-phase NMG(product)
reaction. For these cases, the differences in rates of TG YMG ) (A4)
NTG(feed) + NDG(feed)
conversion can be attributed to differences in diffusion caused
by the size of the respective ionic reaction intermediates. The FAME yield was calculated as
Acknowledgment. The authors acknowledge the BIOCAP ((NFAME(product) - (NDG(product) - NDG(feed)) - 2NMG(product) -
Canada Foundation and the Natural Sciences and Engineering
Research Council (NSERC) of Canada for financial support of this (NFFA(product) - NFFA(feed)))/3)/NTG(feed) + NDG(feed) (A5)
research.
Nomenclature
Appendix: Calculation Methodology Ca(OH)2 ) Calcium hydroxide
The fractional conversion of TG to all products was calculated DG ) Diglyceride
FAME ) Fatty acid methyl ester
from
FFA ) Free fatty acid
GLY ) Glycerol
NTG(product) H2SO4 ) Sulfuric acid
XTG ) 1 - (A1)
NTG(feed) MeOH ) Methanol
MG ) Monoglyceride
XTG is the fractional conversion of TG; NTG(product) is the NaOH ) Sodium hydroxide
TG ) Triglyceride
measured number of moles of TG in the product from the
THF ) Tetrahydrofuran
calibration curve; and NTG(feed) is the estimated original number a ) Interfacial surface area per unit volume (m2/m3)
of moles of TG in the feed, calculated from Ci ) Concentration of species (i) (mol/m3)
Ci0 ) Nonzero initial concentration of species (i) (mol/m3)
NTG(feed) ) NTG(product) + (NDG(product) - NDG(feed)) + CTG-B ) Bulk concentration of TG in the nonpolar TG phase (mol/
NMG(product) + ((NFAME(product) - (NDG(product) - NDG(feed)) - m3)
CTG-S ) Bulk concentration of TG in equilibrium with TG at the
2NMG(product) - (NFFA(product) - NFFA(feed)))/3) (A2) TG-MeOH interface (mol/m3)
FTG ) Flow rate of TG to the interface (mol/s)
NDG(feed) and NFFA(feed) are the estimated original number of moles ki ) Reaction rate constant of species (i) (s-1)
of DG and FFA in the feed, respectively, evaluated from the Ki ) Equilibrium constant of species (i)
original ratios of DG/TG and FFA/TG in the feed. NDG(product), kL ) TG side mass-transfer coefficient (m/s)
NMG(product), NFAME(product), and NFFA(product) are the measured kOV ) Overall reaction rate constant for the two-phase reaction
(s-1)
number of moles of DG, MG, FAME, and FFA in the product
kRX ) TG reaction rate constant for the single-phase reaction (s-1)
from the calibration curves, respectively. NTG ) Mass transfer of TG to the interface (mol m-2 s-1)
The yield of DG was calculated from ri ) Reaction rate of species (i) (mol m-3 s-1)
t ) time (h)
NDG(product) - NDG(feed) VRX ) Reaction volume (m3)
YDG ) (A3) Xi ) Conversion of species (i) (mol/mol)
NTG(feed) + NDG(feed)
Yi ) Yield of species (i) (mol/mol)
The yield of MG was calculated from EF0701440