Article

pubs.acs.org/IECR

The Phase Behavior Eect on the Kinetics of Transesterication

Reactions for Biodiesel Production
Stephen N. Csernica and James T. Hsu*
Deparment of Chemical Engineering, Lehigh University, 111 Research Drive, Bethlehem, Pennsylvania 18015, United States

ABSTRACT: The phase behavior eect on the kinetics of transesterication reactions is investigated in this study. First, the
partition coecient of the catalyst, KOH, was determined. It was found that the vast majority of the catalyst resides in the
methanol phase; thus this phase is taken as the primary reaction volume. Mass transfer studies of soybean oil triglycerides show
that triglycerides are in fact soluble in methanol. Additionally, it is shown that the rate of mass transfer and the equilibrium
concentration of triglycerides in methanol increase with increasing methyl ester concentration. Establishing the methanol phase
as the primary reaction volume facilitated the thorough investigation of the rate-limiting step. First, the terms mass transfer control
and reaction control are nally dened for transesterication reactions. Once properly dened, it is shown that the sigmoidal, or S-
shaped, methyl ester production curve that is so often observed is not necessarily caused by a transition from a mass transfer
controlled regime to a reaction controlled regime, as is so often speculated in the literature. Rather, it is shown that the cause of
the acceleration, regardless of the rate-limiting step, is caused by a transition from a two-phase system to a single-phase system.

INTRODUCTION
Biodiesel, also known as fatty acid methyl esters, is a possible
alternative to petroleum-based diesel fuel due to its numerous
ecological advantages. Biodiesel is often produced by the
transesterication of triglycerides from vegetable oils with a
short-chained alcohol, most commonly methanol, in the
presence of a catalyst. Many dierent catalysts have been
reported, ranging from the common homogeneous alkaline and
acidic catalysts, to various heterogeneous catalysts.14
Initially, the transesterication reaction system contains two
nearly immiscible phases: the triglyceride-rich oil phase and the
alcohol phase. It has been hypothesized that the reaction is
initially mass transfer controlled due to the low miscibility of
the two reactant phases and subsequently slow initial reaction
rate.37 Noureddini and Zhu hypothesized that the reaction
rate transitions from the mass transfer controlled regime to a
faster reaction controlled regime since the methyl ester
production curve displays a sigmoidal shape.4 They noted
that when samples were extracted during the kinetically slow
regime, i.e., what they called the mass transfer controlled
regime, the reactants separated into two distinct phases.
However, when samples were extracted during the kinetically
fast regime, i.e., what they called the reaction controlled regime,
the components existed as a single phase. They suggested that
the methyl esters act as a mutual solvent for the reactants and
allow for the formation of single phase; other authors have
suggested similar hypotheses.49
Similar studies have been carried out to determine the
relationship between the reaction rate and agitation inten-
sity.4,6,10 It is generally observed that the eect of mixing is
most signicant during the initial stages of the reaction. When
the mixing is strong, the initial lag in methyl ester production
disappears.4,6 This presumably is due to the increased mass
transfer that results from high agitation. Boocock et al. also
showed that the initial lag in the methyl ester curve disappears
when butanol is selected as the alcohol source.7 This is because
the butanolsoybean oil system is completely miscible.
Additionally, many authors have reported the use of cosolvents,
such as tetrahydrofuran, dimethyl ether, and propane, to obtain
single-phase systems.7,1113 It should be noted that while
successfully increasing the mixing between the oil and alcohol,
the addition of cosolvents adds additional costs to the nal
purication of the methyl esters.
It should be noted, however, that most of the hypotheses put
forward attempting to describe the phase behavior of
transesterication reactions have been qualitative in nature.
Unfortunately, the terms mass transfer control and reaction
control have never been clearly dened for transesterication
reactions, and thus much ambiguity remains with regard to the
rate-limiting step. The hypothesis that suggests that the overall
rate transitions from a mass transfer controlled regime to a
reaction controlled regime is based on incomplete and
insucient physical evidence. The majority of the studies
describing the phase behavior of these reactions assume the
transition occurs simply because the two reactant phases are
highly immiscible and an initial lag in the methyl ester
production is often observed. High immiscibility and a lagging
reaction rate do not necessarily imply mass transfer control, as
will be shown in this study. For example, a sigmoidal methyl
ester production curve, i.e., one that displays an initially slow
rate followed by a fast acceleration, can be obtained for the
transesterication reaction between the highly immiscible
components soybean oil and methanol while the rate is
exclusively under reaction control, even with minimal mixing.
Not surprisingly, there have also been many dierent kinetic
studies reported for transesterication reactions.4,9,1416 The
most common kinetic system found in the literature appears to
Received: January 12, 2012
Revised: March 8, 2012
Accepted: April 14, 2012

XXXX American Chemical Society A dx.doi.org/10.1021/ie300116p | Ind. Eng. Chem. Res. XXXX, XXX, XXXXXX
Industrial & Engineering Chemistry Research
be that presented by Freedman et al.14 This kinetic model is
based on three consecutive, reversible, second-order reactions.
A triglyceride rst reacts with methanol to form a diglyceride
and a methyl ester; the diglyceride reacts with more methanol
to form a monoglyceride and a second methyl ester; nally, the
monoglyceride reacts with more methanol to form the
byproduct glycerol and a third methyl ester. Overall, 3 mol of
methyl esters are produced for every mole of triglyceride
consumed. Freedman et al. also proposed a fourth possible
reaction termed a shunt mechanism, in which three molecules of
methanol react simultaneously with a triglyceride to form three
molecules of methyl esters without forming the intermediate
species. Noureddini and Zhu reported that the inclusion of the
shunt mechanism in the transesterication kinetics is
unnecessary, however.4 In contrast, Darnoko and Cheryan
reported kinetics that were second order with respect to the tri-,
di-, and monoglyceride species.9 A variety of other kinetic
studies have been reported that consider the eect of mass
transfer limitations.5,15 Other studies even consider the eect of
the formation of the methoxide ion in the reaction between
methanol and the catalyst species.16
Based on the complicated biphasic nature of the trans-
esterication reaction systems, as well as the ambiguity
surrounding the rate-limiting step, it is not surprising that so
many diering kinetic studies exist. Unfortunately, there still
exists much uncertainty when it comes to the physical
understanding of these systems. The objective of this study,
therefore, is to develop simple and fundamental experiments
that provide a better understanding of the complicated nature
of the two-phase system and its eects on the transesterication
reaction kinetics. A signicant portion of this study will be
spent on properly dening mass transfer control and reaction
control for transesterication reaction systems and to
demonstrate what the denitions physically signify within the
system. An experimental setup was designed specically for
obtaining the necessary data required to show what it means to
be under mass transfer control or reaction control and how
these controlling mechanisms aect the overall reaction rate.
MATERIALS AND METHODS
Materials. Rened soybean oil, methanol, and HPLC-grade
2-propanol were purchased from Sigma-Aldrich (St. Louis,
MO). Potassium hydroxide (KOH) pellets (88%) were
obtained from local chemical storage.
Experimental Setup. All transesterication experiments in
this study were carried out in a thin graduated cylinder
maintained at 60 C as shown in Figure 1. This experimental
setup was carefully designed so that the phases would exist as
distinct layers, with the methanol phase resting on top of the
triglyceride-rich oil phase. The mixing that was selected was
unique in that each phase was mixed independently so that the
contents of each phase could be assumed homogeneous and yet
the phases would still remain as distinct layers. This setup
allowed for the interfacial area between the two phases to be
held constant; it is simply the cross-sectional area of the
cylinder. It should be stressed that the experimental design was
constructed to gain a fundamental understanding of trans-
esterication systems, not for a commercialized process.
HPLC Instrumentation. HPLC analyses were performed
with an Agilent Technologies (Santa Clara, CA) 1200 Series
HPLC equipped with a vacuum degasser, quaternary pump,
autosampler, temperature controlled column compartment, and
UV detector.17 The analysis of the transesterication reaction
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Figure 1. Experimental setup for transesterication reactions.
samples was carried out using isocratic elution with a mobile
phase consisting of 50% methanol + 50% 2-propanol.
Separation was achieved using a ZORBAX Eclipse XDB-C18
column (150 4.6 mm, 5 m i.d.). The column temperature
was maintained at 35 C, and detection was carried out using a
wavelength of 205 nm.
Determination of K+ Partition Coecient. The presence
of the K+ ion was determined by use of a Vernier (Beaverton,
OR) conductivity probe (Model CON-BTA). To calibrate the
probe, solutions of 0.125, 0.25, 0.5, and 1.0 M KOH in
methanol were prepared. The samples were diluted by a factor
of 10 prior to measurement due to the range of the conductivity
probe (020 000 S/cm).
The transesterication experiments were conducted in the
experimental setup shown in Figure 1. First, a known quantity
of soybean oil was preheated to the reaction temperature.
Potassium hydroxide (1 wt % of the soybean oil) was dissolved
in the appropriate amount of methanol, which depended on the
molar ratio. Methanol-to-oil molar ratios of 6:1, 10:1, 20:1, and
40:1 were studied; the methanol/KOH mixture was also
preheated to the reaction temperature. Once at the desired
temperature, the methanol was added to the soybean oil. The
contents were brought to complete mixing for 30 s, and then
the phases were allowed to separate for 10 min. After 10 min, a
sample was withdrawn from each phase for analysis.
The analysis of the methanol phase proceeded as follows: 0.5
mL was diluted in 4.50 mL of fresh methanol and the
conductivity of this solution was measured with the
conductivity probe. The analysis of the soybean oil phase
proceeded as follows: rst, a 1 mL sample of the phase was
washed with 5 mL of fresh methanol to leach out any potassium
ions dissolved in the oil phase. The mixture was centrifuged for
10 min at 10 000 rpm using a Beckman-Coulter Avanti J-E
centrifuge (Brea, CA). The conductivity of the methanol wash
was then measured. Any conductivity reading in the resulting
methanol wash was attributed to potassium ions leached from
the oil phase. A second wash of the oil phase was conducted to
ensure all ions had been leached out in the rst wash (it was
observed that one wash was sucient to leach out all ions). The
Industrial & Engineering Chemistry Research
conductivity of the oil phase was measured indirectly this way
because of the nonconducting properties of the oil. Even with
some ions present, direct measurement of the oil phase
provides zero conductivity reading.
Determination of Mass Transfer Coecient. To
determine the mass transfer coecient, kL, of soybean oil
triglycerides into methanol, the experimental setup shown in
Figure 1 was used. As mentioned, the surface area, a, between
the two phases is constant and known, thus allowing the mass
transfer coecient to be calculated. Various agitation speeds
were studied; however, the maximum speed was limited by the
phase boundary: the agitation speed was increased only up to
the point at which the phases would remain as two distinct
layers with a constant interfacial area.
First, a known quantity of soybean oil and methanol were
added to the cylinder at room temperature. A methanol-to-
soybean oil molar ratio of 40:1 was selected for ease of
experimentation. They were brought to 60 C by immersing
the cylinder in a constant-temperature water bath. During this
preheating period, in which there was no mixing, it was
inevitable that a small quantity of soybean oil triglycerides
would diuse into the methanol phase. A sample of the
methanol phase was therefore withdrawn after the desired
temperature was reached; the concentration of triglycerides in
this sample was taken as the initial data point, cTG,0.
The convective mass transfer equation, as dened by Seader
and Henley, can be written according to
dNTG(t )
* c TG(t ))
= kLa(c TG
dt
where NTG is the total moles of triglycerides, cTG * is the
concentration of triglycerides at the soybean oil/methanol
interface, and cTG(t) is the concentration of triglycerides in the
bulk of the methanol phase at a given time t.18 It was
experimentally determined that the equilibrium concentration
of soybean oil triglycerides in methanol at T = 60 C, cTG,eq, is
10.03 mol/m3. A binary phase diagram of soybean oil and
methanol can be found in Figure 2, and the methanol phase
compositions can be found in Table 1. It is assumed that the
concentration of triglycerides at the interface, c*TG, comes to
equilibrium with the methanol rapidly; therefore, the value of
cTG * cTG(t))/(cTG
* will be set equal to cTG,eq. A plot of ln((cTG
cTG,0)) versus t should yield a straight line with a slope =
Figure 2. Binary phase diagram of soybean oil and methanol.
Article
Table 1. Soybean Oil and Methanol LiquidLiquid Binary
Phase Mixtures: Methanol Phase Compositions at Increasing
Temperatures
temp (C) methanol (g/g) triglycerides (g/g) triglycerides (mol/m3)
20 0.996 0.004 3.66
40 0.992 0.008 6.80
60 0.988 0.012 10.03
kLa/VM, where VM is the methanol volume. At any given time
t, the concentration of triglycerides in methanol, cTG(t), can be
measured by the HPLC.
Determination of Rate-Limiting Step. As mentioned,
due to the high immiscibility of soybean oil and methanol, it is
often hypothesized that the reaction is initially mass transfer
controlled.37 There is, however, still much ambiguity with
regard to the rate-limiting step in these reactions. Therefore,
experiments were again carried out in the experimental setup
shown in Figure 1 to determine whether the rate of reaction is
mass transfer or reaction controlled. The most important
variables that aect the rate-limiting step are the catalyst
concentration and mixing rate. The eect of catalyst
concentration at constant agitation speed will be the
predominant focus of this paper. The eect of agitation speed
will be briey discussed at the end of the study. For any given
experiment, a known quantity of soybean oil and an appropriate
amount of methanol with dissolved KOH were rst preheated
separately to 60 C. Once at the desired temperature, the
methanol/KOH mixture was added to the soybean oil. Unless
otherwise stated, the agitation speed was selected so that the
initial conditions of each experiment were such that each
reactant phase existed as a distinct liquid layer with a constant
initial interfacial area between the phases.
RESULTS
K+ Partition Coecient. The calibration of the con-
ductivity probe with various KOH/methanol solutions was rst
carried out. Additionally, since glycerol forms as a byproduct of
the transesterication reaction and remains predominantly in
the methanol phase due to strong hydrophilic interactions, it
must be determined if the presence of glycerol has any eect on
the conductivity reading. Methanol solutions containing equal
* amounts of potassium ions with various amounts of glycerol
were prepared, and the conductivity of these solutions was
measured. It was observed that the conductivity measurements
were linear within the potassium ion concentration range
studied. It was also determined that glycerol has a negligible
eect of the conductivity measurement of the potassium ions in
methanol.
Next, the partitioning of the potassium ion between the oil
and methanol phases during the transesterication reactions
was determined. The partition coecient of the potassium ions
is dened as the ratio of the concentration of potassium ions in
the methanol phase to the concentration of ions in the soybean
oil phase:
c K+,MeOH
K K+ =
c K+,SBO
As mentioned, four dierent methanol-to-soybean oil molar
ratios were tested: 6:1, 10:1, 20:1, and 40:1. The conductivity
measurements of the methanol phase, the soybean oil phase,
and the resulting partition coecients for each molar ratio
studied can be found in Table 2. From the data it is evident that
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Table 2. Partition Coecient of Potassium Catalyst during
Transesterication Reactionsa
cK+ (mol/m3)
MeOH:SBO molar ratio MeOH phase SBO Phase KK+
6:1 928 31.27 29.67
10:1 466 11.56 40.29
20:1 221 0.800 275.64
40:1 110 0.145 755.00
a
At 540 rpm; mixing time = 30 s; settling time = 10 min; T = 60 C;
KOH = 1.0 wt % of SBO.
the potassium ions are predominantly found in the methanol
phase. This is not surprising considering the polar nature of
methanol and glycerol. This is consistent with previous studies
on catalyst distributions.19,20
From this point on, the methanol phase will be taken as the
primary reaction volume since the catalyst remains predom-
inantly in this phase. Therefore, in order for the trans-
esterication reaction to proceed, triglyceride molecules must
be transferred to this phase. To better understand this part of
the reaction, simple experiments were designed to investigate
the mass transfer between soybean oil and methanol.
Determination of Mass Transfer Coecient. As
mentioned, experiments measuring the mass transfer coecient
of soybean oil triglycerides into methanol were carried out
using the experimental setup shown in Figure 1. For these
experiments, all agitation speeds employed were low enough
that the system consisted of two distinct liquid phases with the
methanol phase sitting on top of the soybean oil triglyceride
phase. As mentioned, the maximum agitation speed studied was
limited to the point just before the phases began to mix and the
surface area was no longer equal to the cross-sectional area of
the cylinder. The concentration of triglycerides in methanol as a
function of time and agitation speed can be found in Figure 3.
Figure 3. Concentration of triglycerides in methanol as a function of
time at dierent mixing speeds (MeOH:SBO = 40:1; T = 60 C).
As mentioned, a plot of ln((cTG* cTG(t))/(cTG
* cTG,0)) versus
t should yield a straight line with slope = kLa/VM. These plots
can be found in Figure 4. Using the data in Figure 4, along with
the known values of a and VM, the mass transfer coecient, kL,
for the transfer of soybean oil triglycerides into methanol was
calculated for each agitation speed studied; the values are given
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* cTG(t))/(cTG
Figure 4. Plot of ln((cTG * cTG,0)) vs t to determine
kLa/VM for triglycerides into methanol as a function of agitation speed
(MeOH:SBO = 40:1; T = 60 C).
in Table 3. As expected, the values of the mass transfer
coecient increase with increasing agitation.
Table 3. Mass Transfer Coecient, kL, of Soybean Oil
Triglycerides into Methanol at Various Mixing Speeds (T =
60 C)
rpm kL (m/s)
100 1.46 105
140 3.87 105
180 4.86 105
It is important to note that these mass transfer studies were
conducted between essentially pure triglycerides and methanol.
During transesterication reactions, however, biodiesel methyl
esters are continually accumulating in the system. It has been
reported that methyl esters can enhance the solubility and
mixing of the phases, but very little physical data exist.
Therefore, the mass transfer of triglycerides into methanol at
increasing methyl ester compositions was studied. It was rst
observed that the presence of methyl esters increased the
equilibrium concentration of triglycerides in methanol. Next,
experiments were conducted to measure the mass transfer
cocient in the presence of methyl esters. It was observed that
fatty acid methyl esters increase the overall rate of mass
transfer, as can be seen from Figure 5. Values for the
equilibrium concentration of triglycerides in methanol, along
with values of the mass transfer coecient, both as functions of
increasing methyl ester concentration, can be found in Table 4.
From these data, it is evident that the presence of methyl esters
increases both the solubility of triglycerides in methanol and
the mass transfer coecient. This supports the claim that
methyl esters act to enhance the mixing between the two
reactant phases.
From these experiments it was determined that the
maximum agitation speed employable in the experimental
setup shown in Figure 1 while still maintaining a constant
interfacial surface area between pure methanol and pure
soybean oil triglycerides was 180 rpm. Unless otherwise stated,
180 rpm will therefore be employed for the remainder of the
experiments in this study. This ensures that the initial
conditions of each experiment will be such that there exist
Industrial & Engineering Chemistry Research Article

dc TG,M(t ) dc TG,M(t )
<
dt MT dt R (3)

To experimentally compare the rates of mass transfer and

reaction, the primary reaction volume, i.e., the methanol phase,
was sampled and its contents were analyzed. Mass transfer
control is signied by the absence of soybean oil triglycerides in
the methanol phase. When this result is observed, it is because
triglycerides react to form biodiesel methyl esters as soon as
they enter the methanol phase; thus only methyl esters are
detected. The term mass transfer control is thus used to signify
that the overall rate of methyl ester production is physically
limited by the rate of triglyceride mass transfer into the
methanol phase.
On the other hand, the transesterication reaction rate is
Figure 5. Plot of ln((c*TG cTG(t))/(c*TG cTG,0)) vs t to determine dened as being under reaction control when the rate of mass
kLa/VM for triglycerides into methanol as a function of fatty acid transfer of triglycerides into methanol is greater than the
methyl ester concentration (MeOH:SBO = 40:1; T = 60 C; 180 reaction rate of triglycerides to form methyl esters:
rpm).
dc TG,M(t ) dc TG,M(t )
Table 4. Equilibrium Triglyceride Concentration in >
Methanol, cTG
* , and Mass Transfer Coecient of dt MT
dt R (4)
Triglycerides into Methanol, kL, at Increasing Methyl Ester
Concentrationsa When this occurs, triglycerides will be detected in the methanol
phase because the rate of mass transfer is now greater than the
FAME (wt % MeOH) * (mol/m3)
cTG kL (m/s)
rate of reaction. This allows triglycerides to accumulate in the
0.0 10.03 4.86 105 reaction volume. Thus, the term reaction control is used to
5.0 12.43 9.66 105 signify that the overall rate of methyl ester production is
10.0 14.04 1.44 104 physically limited by the instrinsic reaction rate between the two
a
MeOH:SBO = 40:1; 180 rpm; T = 60C. reactant species. This does not mean that the rate of mass
transfer has no eect on the overall rate; rather, it emphasizes
the fact that the instrinsic reaction rate is not great enough to
consume all of the triglycerides as they enter the reaction
volume; thus an accumulation of reactants in the reaction
two distinct reactant phases with a constant interfacial surface volume occurs.
area between them. To experimentally investigate the rate-limiting step, the
Mass Transfer Control vs Reaction Control. Now that transesterication reaction was again carried out in the
information regarding the mass transfer of triglycerides into the experimental setup shown in Figure 1. A series of experiments
reaction volume has been obtained, the rate-limiting step can be were carried out in which the catalyst concentration in the
investigated more thoroughly. Before the results are presented, methanol phase was at 1.0, 0.5, 0.25, 0.125, 0.0625, and 0.03125
it is prudent to dene what is means for the transesterication wt % of the soybean oil. These weight percents correspond to
reaction rate to be mass transfer controlled and reaction methanol phase molar concentrations of 96, 48, 24, 12, 6, and 3
controlled. First, the rates of the triglyceride mass transfer mM, respectively. The goal of the experiment was to keep
(MT) into the methanol phase and the triglyceride reaction reducing the catalyst concentration until triglyceride species
(R) inside the methanol phase will be dened as were detected in the methanol phase. The catalyst concen-
dc TG,M(t ) k a tration at which the triglyceride species are rst detected is the
= L (c TG,M
* c TG,M(t )) point at which the rate-limiting step transitions from mass
dt MT
VM (1) transfer control to reaction control. It should be noted that
when a sample was withdrawn from the reaction volume it was
dc TG,M(t ) immediately neutralized with 1.0 M HCl to stop the reaction.
= kc TG,M(t )
dt R (2)
Thus, any triglycerides present in the methanol phase will not
continue to react once withdrawn from the reaction vessel. The
Again, cTG,M refers to the triglyceride concentration in the chromatograms shown in Figure 6 visually illustrate the
methanol phase; this is not necessarily the same value as the transition of the rate-limiting step. It can be seen that when
total concentrations of triglycerides in the system. Dier- the catalyst concentration in the methanol phase is 1.0 wt % of
entiating between the rates of triglyceride mass transfer into the the soybean oil at a 40:1 methanol-to-oil molar ratio, no
methanol phase and the triglyceride reaction to form methyl triglycerides are detected in the methanol phase, only methyl
esters facilitates dening mass transfer control and reaction esters. This clearly indicates that at this catalyst concentration
control as well as the ability to identify which one limits the rate the overall rate is under mass transfer control. As the catalyst
at any given time. The transesterication reaction rate is concentration is reduced down to 0.0625 wt % of the soybean
dened as being under mass transfer control when the mass oil, triglycerides are clearly present in the methanol phase. This
transfer rate into the methanol phase is less than the reaction indicates that the mass transfer rate is now greater than the
rate of triglycerides to form methyl esters; thus reaction rate, thus allowing triglycerides to accumulate in the
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Figure 6. Transition of the transesterication reaction rate from mass transfer control to reaction control as a function of decreasing catalyst
concentration, cKOH (MeOH:SBO = 40:1; T = 60 C; tR = 1 min; 180 rpm; TG = triglycerides; DG = diglycerides; MG = monoglycerides; FAME =
fatty acid methyl esters).

methanol phase. Under these conditions the overall rate is

clearly under reaction control.
Mass Transfer Controlled Regime. Now that the terms
mass transfer control and reaction control for transesterication
reactions have been clearly dened, along with the development
of a simple experimental method for determining which
mechanism is limiting, the transesterication reaction rates
under both mass transfer control and reaction control can be
analyzed and compared. To reiterate, the agitation speed
employed here was 180 rpm, ensuring that the initial conditions
are such that two distinct liquid phases with a constant
interfacial area are present. First, the reaction rate under mass
transfer control will be analyzed. Since no triglycerides are
detected in the methanol phase under mass transfer control,
data from two separate experiments will be compared, as shown
in Figure 7. The triglyceride data points were obtained when no
catalyst was present in the methanol phase; thus the slope of Figure 7. Comparison of initial rate of mass transfer of triglycerides
this line is the rate of the triglyceride mass transfer (these data into methanol and initial rate of methyl ester production (MeOH:SBO
are also present in Figure 3, 180 rpm). The methyl ester data = 40:1; T = 60 C; 180 rpm).
points were obtained when potassium hydroxide at a
concentration of 1.0 wt % of the soybean oil was present in
the methanol phase. From Figure 6, it is clear that at this
catalyst concentration the reaction is under mass transfer approximately 3 times the rate of the triglyceride mass transfer
control and thus no triglycerides will be detected in the (slopes of 1.32 and 0.41 mol m3 min1), as is predicted by the
methanol phase. The slope of the line through the methyl ester reaction stoichiometry. The discrepancy between the absolute
data points is thus the initial rate of methyl ester production values of the triglyceride and methyl ester concentrations is due
when the reaction is under mass transfer control. As can be to the initial mixing that occurs when methanol with dissolved
seen, the observed rate of methyl ester production is catalyst is added to soybean oil.
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As the reaction progresses under mass transfer control, the
observed rate of methyl ester production in the methanol phase
begins to accelerate, as shown in Figure 8. The rst change in
Figure 8. Concentration of triglycerides and methyl esters in the
methanol phase during the transesterication reaction under mass
transfer control (MeOH:SBO = 40:1; T = 60 C; KOH = 1.0 wt % of
SBO; 180 rpm; , transition from mass transfer control to reaction
control; |, transition from two-phase system to single-phase system).
the reaction rate, as signied by an increase in the slope of the
methyl ester production rate, occurs at 105 min. At this time
triglycerides become detected in the methanol phase due to the
increased rate of mass transfer, which has been shown to
increase with increasing methyl ester concentration. Thus it can
be said that under the present conditions the overall rate has
transitioned from mass transfer control to reaction control.
Interestingly, however, at t = 105 min the system still remains
as two distinct layers, i.e., phases. However, as the time
increases beyond t = 105 min, small droplets of the triglyceride
phase begin to form in the methanol phase and the reaction
volume begins to appear as an emulsion with an ever-increasing
quantity of triglycerides. It should be reinforced that the
agitation speed was maintained constant throughout; the
increased mixing between the phases results purely from
chemical changes in the system.
It should be stressed that the fact that the rate-limiting step
has transitioned from mass transfer control to reaction control
does not mean that mass transfer no longer has an eect on the
overall rate. Rather, it means that the overall rate is now limited
by the instrinsic reaction rate instead of the mass transfer rate.
No longer is it possible for the catalyst to consume all of the
triglycerides as they enter the reaction volume, and thus there is
an accumulation of reactants in the reaction volume. This trend
can be observed by the data in Figure 8 after t = 105 min. After
this time, the overall rate can be seen to be slowly accelerating
until nally, after an additional 45 min under reaction control,
the rate reaches its maximum value at t = 150 min. It is clearly
evident that the beginning of the acceleration in the overall rate
directly corresponds to the time when the triglyceride
concentration in the methanol phase begins to increase, i.e.,
after t = 105 min, and that the time of the maximum rate
corresponds to the time when the triglyceride concentration in
the methanol is at a maximum, i.e., at t = 150 min. As
mentioned, at times beyond t = 105 min the reaction volume
begins to appear as an emulsion with an ever-increasing
quantity of triglycerides in the form of small droplets
surrounded by the bulk methanol. The maximum rate is
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reached when the two-phase system passes through the
emulsion stage and completes a phase transition to a single-
phase system. Thus, as mentioned, the mass transfer rate still
has an aect on the overall rate under reaction control; as the
mass transfer increases, so too does the overall rate. This is
because the methyl ester production rate is directly propor-
tional to the concentration of triglycerides in the methanol
phase. The reason for the use of the term reaction control,
however, has to do with the fact that the mass transfer rate is
now greater than the rate of reaction; i.e., the mass transfer rate
no longer limits the overall rate. Rather, the overall rate is
limited by the instrinsic reaction rate between the two reactant
species, as is evident by the fact that triglyceride species begin
to accumulate in the reaction volume after t = 105 min.
Reaction Controlled Regime. Now that it has been
veried that when the transesterication reaction rate is initially
under mass transfer control it transitions to reaction control, it
can be compared to the behavior of the rate exclusively under
reaction control. When a catalyst concentration is selected so
that the rate starts under reaction control (see Figure 6), the
initial concentration of triglycerides in the methanol phase is no
longer zero. Rather, the triglycerides begin to accumulate in the
methanol phase during the initial stages of the reaction, as
shown in Figure 9 when a catalyst concentration of 0.0625 wt %
Figure 9. Concentration of triglycerides and methyl esters in the
methanol phase during the transesterication reaction under reaction
control (MeOH:SBO = 40:1, T = 60 C; KOH = 0.0625 wt % of SBO;
180 rpm; |, transition from two-phase system to single phase system).
of SBO is selected. The triglyceride concentration in the
methanol phase is dependent on the competing rates of mass
transfer into the methanol phase and the reaction to form
methyl esters. If the catalyst concentration were to be increased,
the triglyceride concentration in methanol would eventually
reach zero and the reaction rate would be back under mass
transfer control.
When the reaction-controlled rate is allowed to run to
completion, a similar acceleration in the overall rate of methyl
ester production is observed, as also shown in Figure 9. The
fact that the system has been under reaction control the entire
time and still displays a sigmoidal methyl ester production
curve proves that the accelerating rate is not necessarily caused
by a transition from mass transfer control to reaction control.
The maximum acceleration in the methyl ester rate occurs
again as the system transitions from a two-phase system to a
single-phase system, in this case at t = 270 min. As previously
mentioned, when this phase transition occurs, the triglyceride
Industrial & Engineering Chemistry Research
concentration in the methanol phase surges and the reaction
rate increases proportionally. As emphasized for the data in
Figure 8, it should be stressed that the reason that the data in
Figure 9 are dened as reaction control is because the intrinsic
reaction rate is limiting the overall rate of methyl ester
production. Clearly, the rate of mass transfer aects the overall
rate throughout the entirety of the reaction in Figure 9;
however, at no point is the rate of mass transfer limiting the
overall rate. There is always an accumulation of triglycerides in
the reaction volume, and thus the term reaction control is
applied throughout. Aside from starting under reaction control,
the only other dierence between the data in Figures 8 and 9 is
the time at which the systems transition from two phases to a
single phase, which is due to the dierent catalyst
concentrations used. Lower catalyst concentrations will take a
greater amount of time to produce a sucient quantity of
methyl esters to cause the phase transition.
Eect of Mixing on the Rate-Limiting Step. It has now
been clearly established that at constant agitation speed the
catalyst concentration has a direct eect on the rate-limiting
step. High catalyst concentrations result in mass transfer
control, while low catalyst concentrations result in reaction
control. The catalyst concentration, however, is not the only
variable that aects the rate-limiting step. Whereas the catalyst
concentration directly aects the reaction rate, the agitation
speed directly aects the mass transfer rate; this will have some
eect on the rate-limitng step. The rate of mass transfer is
proportional to the surface area between the two phases. As
agitation is increased, the surface area between the two phases
increases. This results in an increase in the mass transfer rate of
triglycerides into methanol. As a result, the overall rate is forced
into the direction of reaction control. This is shown in Figure
10, where it can be seen that, at any given catalyst
Figure 10. Eect of agitation speed on the initial concentration of
triglycerides present in the methanol phase (MeOH:SBO = 40:1; T =
60 C; KOH = 1.0 wt % of SBO; tR = 1 min).
concentration, the amount of triglycerides in the methanol
phase increases with increasing agitation.
At agitation speeds that result in complete emulsication, as
seen by the 540 rpm data points in Figure 10, it is very clear
that oil triglycerides are present in the methanol phase right
from the very beginning of the reaction, and thus, based on the
H dx.doi.org/10.1021/ie300116p | Ind. Eng. Chem. Res. XXXX, XXX, XXXXXX
Article
denitions of mass transfer control and reaction control, the
rate is under reaction control. As was seen in Figures 8 and 9,
high concentrations of triglycerides in the methanol phase
result in a correspondingly high reaction rate.
Phase Behavior Eect on the Kinetics of Trans-
esterication Reactions. The fact that the transesterication
reaction accelerates under both mass transfer control and
reaction control is intriguing for a variety of reasons. Most
importantly, it suggests that the acceleration of the methyl ester
production is not necessarily caused by a change in the rate-
limiting step, which is often claimed in the literature. Rather,
the acceleration is caused by a phase transition from two phases
to a single phase. If the concentrations of the intermediate
species are assumed to remain relatively low throughout the
reaction, the methyl ester rate can be approximated according
to
dc FAME,M dc TG,M
3
dt dt (5)
The rate of change of the triglyceride concentration within
the methanol phase with time, dcTG,M/dt, has already been
dened for the competing cases of mass transfer control and
reaction control, as found in eqs 1 and 2, respectively.
Therefore, the methyl ester production rates under both mass
transfer and reaction control can be approximated accordingly:
dc FAME,M kLa
= 3 (c TG,M
* c TG,M)
dt MT VM (6)
dc FAME,M
= 3kc TG,M
dt R (7)
Again, cFAME,M and cTG,M refer to the concentrations in the
methanol phase. Equation 7 can only be used to approximate
the reaction rate constant, k, when the system is under reaction
control. As has been shown, reaction control may exist for the
entire length of the reaction or only a portion of the reaction; it
depends on the conditions selected.
The reaction rate constant was determined using eq 7 for the
data collected during the reaction controlled regime of Figure 8
(i.e., after t = 105 min); a value of k = 1.43 min1 was obtained.
Since the mass transfer coecient, kL, has previously been
determined, eqs 6 and 7 can then be used to predict the methyl
ester production curve as the rate-limiting step changes from
mass transfer control to reaction control. The comparison
between the experimental and theoretical methyl ester
production rates when catalyst concentration is at 1.0 wt %
of SBO can be seen in Figure 11. The reaction rate constant for
the data in Figure 9, in which the catalyst concentration is
0.0625 wt % of SBO, was similarly determined using eq 7; a
value of k = 0.57 min1 was obtained. At this catalyst
concentration, the entire data set was under reaction control.
The comparison between the experimental and theoretical
methyl ester rates for this data set is shown in Figure 12.
Since the maximum reaction rate, regardless of the initial
rate-limiting step, occurs as the system transitions from two
phases to a single phase, it is important to analyze this phase
transition. In doing so, the solubility parameter of the methanol
phase will be examined. By denition, the solubility parameter
of pure component i, i, is the square root of the cohesive
energy density of pure component i in the pure state.21
Industrial & Engineering Chemistry Research
Figure 11. Comparison of experimental and theoretical methyl ester
concentrations when the transesterication reaction starts in mass
transfer control and transitions to reaction control (MeOH:SBO =
40:1; T = 60 C; KOH = 1.0 wt % of SBO; 180 rpm; , transition from
mass transfer control to reaction control).
Figure 12. Comparison of experimental and theoretical methyl ester
concentrations when the transesterication reaction is under reaction
control the entire time (MeOH:SBO = 40:1; T = 60 C; KOH =
0.0625 wt % of SBO; 180 rpm).
(Ev)i 1/2
i =
Vi
The cohesive energy density is a measure of the strength of
intermolecular forces holding molecules together in the liquid
state per unit volume of liquid. It is dened as the ratio of the
latent energy of vaporization of a pure component, (Ev)i, to
the molal volume of that component, Vi. According to King, a
general rule is that components or phases with solubility
parameters diering by greater than 3 (cal/cm3)1/2 will form
two separate liquid phases. As can be seen from Table 5, the
solubility parameters of the initial reactant phases dier by 6.5
(cal/cm3)1/2 and thus two liquid phases are observed. This
behavior is similarly observed when analyzing biodiesel,
glycerol, and methanol ternary phase diagrams.24
As the transesterication reaction proceeds, however,
triglycerides and especially methyl esters continue to
accumulate in the methanol phase. This has the eect of
lowering the volume average solubility parameter, , of the
methanol phase, given by
I dx.doi.org/10.1021/ie300116p | Ind. Eng. Chem. Res. XXXX, XXX, XXXXXX
Article
Table 5. Solubility Parameters for Components in
Transesterication Reactions
component i ((cal/cm3)1/2)
glycerol 16.822
methanol 14.422
methyl oleate 8.322
soybean oil 7.923
R
j = 1 jVjxj
= R
j = 1 Vjxj
where j is the solubility parameter of pure component j, Vj is
the molar volume of component j, and xj is the mole fraction of
component j. As the average solubility parameter of the
methanol phase falls, its value moves closer to that of soybean
oil. Additionally, there is likely some methanol and methyl ester
species that transfer from the methanol phase into the soybean
oil phase; this would raise the volume average solubility
parameter of this phase. Eventually the solubility parameters of
the two phases become close enough that the system
transitions from two phases to a single phase.
CONCLUSION
The phase behavior eect on the kinetics of transesterication
reactions for biodiesel production has been thoroughly
investigated. First, the partition coecient of the potassium-
based catalyst was determined. These results clearly indicate
that the majority of the catalyst resides in the methanol phase.
Thus, the methanol phase was established as the primary
reaction volume for transesterication reactions with homoge-
neous potassium based catalysts. Once the methanol phase was
taken as the primary reaction volume, it was established that
triglycerides must transfer into this phase to react. It was shown
that both the equilibrium concentration of soybean oil
triglycerides in methanol and the rate at which the triglycerides
were transferred into methanol increase with increasing methyl
ester concentration.
Next, mass transfer control and reaction control were clearly
dened for transesterication reactions. The reaction was
dened as being under mass transfer control when the rate of
mass transfer of triglycerides into the methanol phase was less
than the rate of reaction of triglycerides to form methyl esters;
i.e., the mass transfer rate limits the overall rate. On the other
hand, the reaction was dened as being under reaction control
when the rate of mass transfer of triglycerides into the
methanol phase is greater than the rate of reaction of
triglycerides to form methyl esters; i.e., the intrinsic reaction
rate limits the overall rate.
Once these terms were properly dened, the overall
transesterication rate under mass transfer and reaction control
were compared. This comparison revealed the overall rate
undergoes an acceleration regardless of the rate-limiting step.
This proves that the acceleration is not caused by a change in
the rate-limiting step. Rather, the acceleration is caused by a
phase transition from two phases to a single phase. When this
occurs, the triglyceride concentration in the methanol phase
surges, which directly increases the rate of methyl ester
production. It is believed that the transition from two phases to
a single phase occurs when the volume-average solubility
parameter of the methanol phase is reduced by the increasing
concentration of methyl esters.
Industrial & Engineering Chemistry Research

Article

AUTHOR INFORMATION (19) Zhou, W.; Boocock, D. G. B. Phase Distributions of Alcohol,

Glycerol, and Catalyst in the Transesterication of Soybean Oil. J. Am.
Corresponding Author Oil Chem. Soc. 2006, 83, 1047.
*Tel.: (610) 758-4257. Fax: (610) 758-5057. E-mail: jth0@ (20) Chiu, C. W.; Go, M. J.; Suppes, G. J. Distribution of Methanol
lehigh.edu. and Catalysts Between Biodiesel and Glycerin Phases. AIChE J. 2005,
51, 1274.
Notes (21) King, C. J. Separation Processes, 2nd ed.; McGraw-Hill: New
The authors declare no competing nancial interest. York, 1980.

(22) Yaws, C. L. Chemical Properties Handbook; McGraw-Hill: New

ACKNOWLEDGMENTS
This project has been partially nanced by a grant from the
Commonwealth of Pennsylvania Department of Community
and Economic Development through the Pennsylvania Infra-
structure Technology Alliance (PITA).
York, 1999.
(23) King, J. W. Determination of the Solubility Parameter of
Soybean Oil by Inverse Gas Chromatography. Lebensm.-Wiss. Technol.
1995, 28, 190.
(24) Csernica, S. N.; Hsu, J. T. Reverse-Phase Ternary Phase
Diagram, Tie Lines, and Plait Point for Commercial Biodiesel

GlycerolMethanol. Ind. Eng. Chem. Res. 2011, 50, 1012.

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