A NEW SOLUBILITY MODEL TO DESCRIBE

BIODIESEL FORMATION KINETICS

K. Gunvachai1, M. G. Hassan2, G. Shama2 and K. Hellgardt1,

1

Department of Chemical Engineering and Chemical Technology, Imperial College London UK.
Department of Chemical Engineering Loughborough University, UK.

Abstract: The development of a mathematical model that accurately describes the formation of
fatty acid methyl esters (FAMEs) (otherwise known as biodiesel) from rapeseed oil and methanol
in the presence of sodium hydroxide catalyst at temperatures in the range of 293333 K
is described. The model accounts for the existence of more than one phase at any given stages
of the reaction and for the solubilities of the reacting species in various phases. The latter were
obtained experimentally and are presented in the form of ternary phase diagrams. The model
appears to give a good t to the experimental data obtained using both batch and continuous ow
reactors.
Keywords: biodiesel; kinetics; solubility; phase diagram; transesterication.

INTRODUCTION

Correspondence to:
Dr K. Hellgardt, Department
of Chemical Engineering
and Chemical Technology,
Imperial College London,
South Kennington Campus,
London, SW7 2A2, UK.
E-mail: k.hellgardt@
imperial.ac.uk

DOI: 10.1205/psep07033
09575820/07/
$30.00 0.00
Process Safety and
Environmental Protection
Trans IChemE,
Part B, September 2007
# 2007 Institution
of Chemical Engineers

emissions from biodiesel, including carbon

monoxide,
particulate
emissions,
and
unburned hydrocarbon, are lower than those
from the conventional diesel fuel (Van
Gerpen, 2005) and therefore biodiesel could
be an effective means to reduce air pollution
in urban areas. In addition, because of its
high lubricity, biodiesel could be added to
ultra low sulphur diesel fuel, which is generally characterized by poor lubricity, in order
to improve its fuel properties (Van Gerpen,
2005). Moreover, biodiesel does not contribute to global warming because of its closed
carbon cycle: it was estimated in a life cycle
analysis that the overall carbon dioxide emissions resulting from the use of biodiesel were
reduced by 78% when compared to mineral
diesel (Sheehan, et al., 1998). Apart from
the technical view point, the use of fuel
derived from natural oils and fats would also
create a new market channel for vegetable
oils and animal fats and hopefully it would
help alleviate the oversupply problems in
some areas of the world.
Transesterication of vegetable oils with
short chain alcohols such as methanol and
ethanol in the presence of homogeneous
basic catalysts such as sodium hydroxide
(NaOH) and potassium hydroxide (KOH) has
been widely used as an industrial biodiesel
production process. The reaction comprises
three consecutive reversible steps: the formation of diglycerides, the formation of
monoglycerides and the formation of glycerol.

There is considerable interest in the direct

use of vegetable oils as well as vegetable oil
or animal fat derived biodiesel as renewable
liquid fuels (Meher et al., 2006; Boocock
et al., 1998). Whilst apparently a simple
option, there are some limitations that mitigate
against the use of vegetable oils. For
example, the viscosities of plant oils are
very much higher than those of diesel fuels
and this leads to engine-start difculties in
colder climates (Ma and Hanna, 1999). The
fuel injection systems of engines running on
vegetable oils also display a tendency to
become blocked by gummy deposits
(Srivastava and Prasad, 2000; Meher et al.,
2006). Moreover, vegetable oils do not burn
cleanly but produce aldehydes such as
acrolein as well as organic acids (Goering
et al., 1981). To overcome these problems,
vegetable oils can be converted to their
methyl esters, so called biodiesel. Biodiesel
has a viscosity of typically six to 10 times
lower than that of the vegetable oils and
does not form engine deposits or generate
harmful pollutants. Since biodiesel can be
used in diesel engines in neat form or blended
with diesel fuel with little or no engine modication, it can be considered as a potential
diesel fuel extender (Canakci and Van
Gerpen, 2003). Other advantages of biodiesel
over conventional diesel fuel have also
been identied. For instance, the exhaust
383

Vol 85 (B5) 383389

384

GUNVACHAI et al.
k1

Triglycerides CH3 OH ! Diglycerides

k2

CH3 COOR1

(1)

Diglycerides CH3 OH

k3

! Monoglycerides

k4

CH3 COOR2

(2)

Monoglycerides CH3 OH

k5

! Glycerol

k6

CH3 COOR3

(3)

Experimental Procedures

The overall reaction can be written as

Triglycerides 3CH3 OH

Generation of phase diagrams

k7

! 3CH3 COOR

k8

Glycerol

UK). Methanol of 99% purity was purchased from Fisher

Scientic Ltd (Loughborough, UK). Sodium hydroxide pellets
of 99% purity were purchased from BDH Laboratory Supplies
(Poole, UK). For the quantitative analysis of fatty acid methyl
esters using a gas chromatograph, methyl pentadecanoate of
more than 99.5% purity, methyl palmitate, methyl stearate,
methyl oleate and methyl linoleate of at least 99% purity
were purchased from Sigma-Aldrich Company Ltd
(Gillingham, UK).

(4)

Because vegetable oils and alcohols are immiscible, the initial

reaction system comprises two phasesan alcohol phase and
an oil phase. Under such conditions mass transfer would
govern the kinetics of the reaction because transesterication
must occur in the methanol phase, in which the catalyst is
dissolved. As a result, the initial rate of reaction is relatively
slow and mechanical agitation is necessary to promote a
more rapid reaction. Upon vigorous mixing, an emulsion is
formed, aided by natural surfactants present in the oil, including
free fatty acids, and lecithin (Garti, 1999; Novales et al., 2005).
Once an emulsion is formed it appears that the rate of reaction
is controlled by the solubility of the oil in the catalytically active
phase. At high conversions of the oil, the reaction system
forms a single phase and methyl esters, which act as a cosolvent, are formed. At this point simple homogeneous batch
kinetics will govern the process, and the rate of reaction is
rapid (Vincente et al., 2005; Boocock et al., 1996). As a
result, the curves of the concentrations of the nal reaction
products, i.e., methyl esters and glycerol, usually have a sigmoidal shape, which indicates a slow reaction rate at the
early stage of reaction followed by a sudden increase in the
reaction rate and nally a plateau as the reaction reaches its
equilibrium. This behaviour is typical for the autocatalytic reactions or the reactions with changing mechanisms. While the
kinetics of the reaction in the kinetically controlled region (fast
region), where the system is a homogeneous solution, can
be modelled by conventional methods, the early stage kinetics
(slow region), which is controlled by the amount of vegetable oil
dissolved in the methanol phase, must be modelled by using
the inter-solubility data between vegetable oil, methanol and
fatty acid methyl esters (FAMEs). Therefore in this study, by
constructing the ternary phase diagrams of rapeseed oil,
methanol, and FAMEs, we are able to propose a new
semi-empirical solubility model to describe the early stage
kinetics of the transesterication of commercial rape seed oil,
using sodium hydroxide as a catalyst and a molar ratio of
methanol to oil of 5 : 1. We also report here the overall rate
constants of the reaction at the reaction temperatures of 293,
313 and 333 K.

MATERIALS AND EXPERIMENTAL PROCEDURES

Materials
Rapeseed oil of food grade quality (rened and bleached)
was purchased from Sainsburys Supermarket Ltd (London,

Series of experiments were carried out to determine the

solubility of rapeseed oil in methanol at different concentrations of FAMEs at temperatures of 293, 313 and 333 K.
The FAMEs were added using a micro pipette to a stirred
mixture of methanol and oil of known composition in a
sample bottle until the onset of cloudiness was reached.
This was taken as indicating incipient phase separation.
The mixture was then allowed to stand for an hour and if
the clouding disappeared additional FAMEs were added.
The volume of FAMEs used and the composition of the
resulting mixture were plotted to form a phase diagram. In
order to validate the results generated from varying the oil
to methanol concentration, a second set of experiments
was carried out by varying the FAMEs/methanol concentration and gradually adding oil.

Batch reactor experiment

Experiments were conducted in a stirred, jacket reactor
of 1 l total capacity. Reaction temperatures were maintained
at 293, 313 or 333 K. A molar ratio of methanol to rapeseed
oil of 5 : 1 was employed and the catalyst used was sodium
hydroxide at a concentration of 5 wt% based on methanol
(approximately 1 wt% of oil). The stirrer speed was kept constant at 500 rpm for all experiments. Initial experiments
indicated that increased stirrer speeds did not substantially
affect the observed transesterication rates. To ensure that
the contents of the reactor were at the desired temperature,
the rapeseed oil (0.0005 m3) was introduced into the reactor
rst and allowed to reach the desired reaction temperature.
Then the solution of sodium hydroxide (0.002 kg) in methanol
(0.0001 m3) was added via the addition port in the top of the
reactor. Samples were taken after 2, 4, 6, 8, 10, 15, 20 and
25 min by opening the valve on the bottom of the reactor
and allowing approximately 0.00003 m3 to ow out before
retaining the sample. Each sample was placed in a sealed
container and immediately placed on ice in order to stop
the reaction. FAMEs were decanted from the lower layer of
glycerol, diluted to 10 ppm with hexane and analysed according to the procedure described later.

Continuous ow minireactor experiment

The transesterication reactions at 333 K were repeated
in a continuous ow minireactor (0.008 m ID  0.05 m, stainless steel 316), using the same molar ratio of methanol to oil
and catalyst concentration as were reported above. The
outlet of reactor was connected to a cooling loop which
was immersed in an ice bath so that the reaction was
quenched immediately once the reaction mixture exited the
reactor. An inline lter with 0.5 micron pore size (Swagelok

Trans IChemE, Part B, Process Safety and Environmental Protection, 2007, 85(B5): 383 389

SOLUBILITY MODEL TO DESCRIBE BIODIESEL

London, Hertfordshire, UK) was placed at the inlet of the
reactor to cause formation of an emulsion. The minireactor
was placed inside a Carbolite tube furnace (Carbolite Furnaces, Shefeld, UK) to control the reaction temperature
(+1 K). Methanol was pumped to the reactor system using
a dual-piston reciprocating HPLC pump (Waters Associates,
Massachusetts, USA) Whereas methanol could be pumped
with a standard chromatography pump, the high viscosity of
the oil precluded the use of a reciprocating system (with
check valves) and hence a continuous high pressure ISCO
100DM syringe pump was employed (ISCO Inc., Nebraska,
USA). The ow rates of methanol and oil were adjusted
such that the molar ratio of methanol to oil of 5 : 1 and the
space times of 0.5 to 5 min were obtained. Samples collected
from the reactor were kept overnight in a refrigerator to allow
phase separation and then analysed using the procedure
described later.

Analytical Methods
To follow the change in the reaction product concentrations
over time, the samples collected from the batch reactor and
the continuous ow reactor were analysed based on gas
chromatography technique which, for the types of the capillary columns selected, allowed the quantication of fatty
acid methyl esters. Because different models of gas chromatographs and different types of detectors were used, two
sets of standard calibration curves were constructed separately for the quantitative analysis purpose.

Batch reactor experiment

The samples were analysed using a HP 5890 gas chromatograph (Hewlett Packard, Ipswich, UK), equipped with a
TRIO-1 mass spectrometer detector (Mooreld Associates,
Manchester, UK), a HP 7673 auto-sampler and Mass Lab
1.3 software. The column used was a 30 m and 0.25 mm
Supelco polar EC-Wax (Supelco, UK, Poole, UK). Helium
was used as a carrier gas at a ow rate of 0.2 m s21. The
injector temperature was maintained at 473 K. The oven
temperature was initially held at 393 K for 1 min and then
increased at a rate of 7 K min21 to 473 K whereupon it was
held for 5 min.

Continuous ow minireactor experiment

The samples were analysed using a HP5890 gas chromatograph (Hewlett Packard, Ipswich, UK) equipped with a
0.25 mm  0.22 mm  25 m polar SGE BPX70 column
(SGE Europe Ltd, Milton Keynes, UK), a ame ionization
detector and JCL 6000 data system. Methyl pentadecanoate
was used as an internal standard. The initial oven temperature was kept constant at 448 K for 2 min and then raised
at a rate of 5 K min21 to 493 K. Helium was used as a carrier
gas and the split ratio of 100 : 1 was used. The injector and
detector temperatures were maintained at 523 K.

385

Figure 1. Mass of fatty acid methyl esters measured during rapeseed

oil transesterication at 293, 313 and 333 K for molar ratio of methanol to oil of 5 : 1 and 5 wt% NaOH in a batch reactor.

reaction to reach its highest conversion was decreased as

temperature was increased. The increase in the equilibrium
ester concentration at higher reaction temperature is due to
the fact that the equilibrium constant shifts to higher values.
It was observed that at 333 K the mass of FAMEs reached
the maximum value of 0.165  1023 kg and then decreased
after 8 min. This may be because small amounts of FAMEs
dissolved in the glycerol phase, which formed at high conversion. Higher solubility of FAMEs in glycerol at elevated temperature is possibly because, at higher energy state, FAME
molecules have a tendency to dissolve more in the glycerol
phase. The lag time corresponding to the two-phase reaction
mixture as reported by Noureddini and Zhu (1997) was not
observed in this batch experiment. This is because the reaction proceeded very rapidly especially at 333 K, where the
nal conversion was reached only 2 min (the rst data
point) after the reaction was commenced.
To study the initial reaction kinetics, it is necessary to follow
the progress of the reaction at its early stages, when two
phases exist and the reaction is promoted by the FAMEsaided dissolution of the oil in the methanol. However, the
transesterication of rapeseed oil is so rapid that, when
using a batch reactor, it prevented us from efciently perform
the sampling and the quenching of the reaction. Therefore
a tubular ow micro-reactor was constructed for carrying
out the experiments. This type of reactor not only enabled
us to obtain more data points in the solubility-controlled
region, but it also allowed an immediate quenching of the
reaction once the mixture exits the reactor. Figure 2 shows
an initial slow rate of reaction and an overall sigmoidal pattern
to the reaction time course. After leaving overnight in a

RESULTS AND DISCUSSION

Transesterification Reaction Analysis
Figure 1 shows the mass of esters produced from a batch
reactor as a function of time at the constant reaction temperatures of 293, 313 and 333 K. As expected, the time for the

Figure 2. Concentration of fatty acid methyl esters during rapeseed

oil transesterication at 333 K for molar ratio of methanol to oil of
5 : 1 and 5 wt% NaOH in a continuous ow minireactor.

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GUNVACHAI et al.

refrigerator for settling, the reaction mixtures in this region

(0.5 and 1.0 min residence time) separated into three
phases: a top layer of methanol, a middle layer of oil and a
small droplet of glycerol at the bottom. This lag is the time
needed for the concentration of the esters in the reaction
system to increase to a point at which a single phase is
formed. When the residence time was increased, a twophase system of biodiesel and glycerol was observed
which corresponds to the sudden increase in the ester concentration in Figure 2. As previously observed in the batch
experiment, the ester concentration also decreased after it
reached its maximum value.

Phase Diagrams
In order to fully follow the transesterication reaction path
within the reactor, the intersolubility data of the major reaction
components, i.e., rapeseed oil, methanol, FAME and glycerol
needed to be identied. For clearer depiction, a tetrahedron is
used to represent the reaction system (Figure 3). Each corner
is marked with each of the major constituents of the reaction
mixture. The planes of the tetrahedron that frame the composition space of the reacting mixture during the reaction
are the ternary phase diagrams of oilmethanol FAME,
oilmethanol glycerol, oil FAME glycerol and methanol
glycerol FAME and by constructing the solubility diagrams
(phase diagrams), the composition of the different phases
could be extracted and used in the solubility models.
Figure 4 shows the phase diagram of oil methanol FAME
obtained from the procedure described earlier. It is evident
that although both rapeseed oil and methanol are completely
soluble in FAME, they are almost immiscible at all temperatures studied because of the difference in polarity. However,
their intersolubility gradually increases with increasing concentration of FAME and when the concentration of FAME in
the mixture reaches approximately 55 vol%, the two-phase
mixture becomes homogeneous. As expected, the intersolubility between rapeseed oil and methanol increases with
increasing temperature.
The intersolubilities between FAME methanol glycerol,
oilglycerol MeOH and oilglycerol FAME were not determined in this study because the purpose is to investigate the
kinetics of the transesterication reaction at the initial stage
where the concentrations of the reaction products, which

Figure 4. The phase diagram of oilmethanol FAME.

are produced in the methanol phase, are relatively low.

Therefore it is reasonable to assume that all the products
stay in the methanol phase without diffusing to the oil phase.

Solubility Models for a Batch Reactor

The basis of the new model is that the solubility of the oil
in the methanol phase increases as the reaction progresses
and FAMEs are produced leading at a later stage to a single
phase system (at conversions in excess of 60%). At the
beginning of the reaction the species present are methanol
and rapeseed oil. In order to determine, which phase is dispersed and which is continuous, a correlation factor (X),
proposed by Selker and Sleicher (1965), was calculated
based on phase volume ratios, density and viscosity of
each phase. Table 1 shows the criteria for determining
types of dispersion by using the correlation factor (X).
x


QL rL mL 0:3
QH rH mH

(5)

A correlation factor of approximately 0.06 was obtained, indicating that in our case methanol is dispersed in a continuous
phase of rapeseed oil.
A number of initial assumptions were made to simplify the
model, including:
(1) None of the species is soluble in the oil phase at low
concentration. This simplies the model considerably as
it means that when a tie line is plotted on the diagram
between the two phases, the oil phase end remains at
100% oil (the left corner of the diagram). This enabled
us to modify the phase diagram of Figure 4 to the one
shown in Figure 5.
(2) None of the species are soluble in the glycerol phase,
however it is known that methanol is soluble in the

Table 1. Relationship between dispersion types and

values of the correlation factor.
Correlation factor X
,0.3
0.30.5
0.52.0
2.03.3
.3.3

Results
Light phase always dispersed
Light phase probably dispersed
Phase inversion possible
Heavy phase probably dispersed
Heavy phase always dispersed

Figure 3. The interaction of all phases within the reaction system.

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SOLUBILITY MODEL TO DESCRIBE BIODIESEL

387

Higher order reaction

kt
NTG=Me0

Figure 5. A solubility phase diagram used for the generation of the

reaction kinetics.

(3)

(4)

(5)
(6)
(7)

(8)

glycerol phase, but in the early stages of the reaction

when a two-phase emulsion exists, the concentration of
glycerol will be low. The dissolution of methanol in
glycerol could be built into an extended version of the
model.
The solubility of oil in the methanol phase is a function
of conversion. The production of FAME acts as a
solubilizing agent.
A small amount of oil is always present in the methanol
phase even at the beginning of the reaction. This is in
agreement with the phase diagrams in Figures 4 and 5.
The edge point of the triangular diagram in Figure 5
has been forced to be zero. The actual solubility can be
inferred by extrapolating the low concentrations of oil in
methanol.
The reaction only occurs in the methanol phase, where
the catalyst is dissolved.
Rates are considered with respect to the volume of
methanol only.
The reaction intermediates, i.e., diglycerides and monoglycerides are neglectedtherefore the three reaction
steps [equations (13)] can be simplied to equation (4).
This assumption is based on the fact that only FAME
and glycerol are the nal products for the overall reaction.
As a result, the rate constants calculated in this study
are for the overall reaction.
Reverse reactions are negligible because methanol is
used in excess in order to drive the reaction forward
and the reaction products formed at the early stage are
at fairly low concentrations.

dXTG
n
m
VCTG=Me
CMe=Me

(8)

The integrals on the right hand side of the equation were

calculated from the batch experimental data and plotted
against the reaction time. It was found that a reaction order
of 1.5 with respect to methanol and 1 with respect to oil
gave the best t to the experimental data (Figures 6 8).
The reaction rate constants (k) were then calculated from
the slopes of the plots and the initial concentrations of oil in
the methanol phase obtained from the extrapolation of the
phase diagram. The k values of 0.00098, 0.00309 and
0.0067 (kmol m23)21.5 s21 were obtained at reaction temperatures of 293, 313 and 333 K, respectively. The 2.5
order rate constant obtained in this study at 333 K was converted to the second order rate constant and compared
with the values for the second-order reaction (pseudo homogeneous reaction) reported in the literature (Table 2). The rate
constant obtained in this study was found to be within the
range of the gures reported in the literature. The discrepancy is probably because the reaction conditions used in
each study are even though similar but not identical and
therefore the rate constants obtained are different. The
explanation for the relatively low rate constants obtained
from this batch experiments is that these values could be
the rate constants at near equilibrium conditions as the
experimental results shows that the reaction was very fast

Figure 6. A 2.5 order (rst order with respect to oil and 1.5 order with
respect to methanol) solubility model plot of rapeseed oil at 293 K.

By taking into account the above assumptions, a solubility

model for a pseudo rst order reaction with respect to methanol for a batch reactor can be written as
kt
NTG=Me0

dXTG
VC
TG=Me
0

(6)

For second order and higher order reactions, the model

equations can be written in a similar form as
Second order reaction
kt
NTG=Me0

dXTG
VC
CMe=Me
TG=Me
0

(7)

Figure 7. A 2.5 order (rst order with respect to oil and 1.5 order with
respect to methanol) solubility model plot of rapeseed oil at 313 K.

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388

GUNVACHAI et al.

Figure 9. A segregated model for a tubular reactor.

Figure 8. A 2.5 order (rst order with respect to oil and 1.5 order with
respect to methanol) solubility model plot of rapeseed oil at 333 K.

of small intervals (Dt). Then the reaction in each time interval

can be represented by a batch reactor (Figure 10). For a
pseudo rst order reaction (the methanol in the droplets is
in great excess), the solubility model can now be written as
1 dNTG=Me
KCTG=Me
V
dt

Table 2. Rate constants of the second order transesterication

reaction reported in the literature and in this study.
Reported by
Noureddini and Zhu (1997)
Darnoko and Cheryan (2000)
Cheng et al. (2004)
Vincente et al. (2005)
This study (batch reactor)

(9)

If we further assume that the volume of the droplet is constant, the equation can then be rearranged and integrated to

Rate constant1, m3 kmol21 min21

0.0502
3.382 (originally reported as
0.036 wt%21 min21)
0.097
0.612
0.0673

Notes:
1
The reaction conditions are similar to those employed here but not
identical.
2
The numbers reported are the lowest forward rate constants.
3
The rate constant was converted from 2.5 order to the second order
by multiplying by the square root of the initial concentration of oil in
the methanol phase.

and it seemed to be complete within the rst 2 min of the

reaction course.

A Solubility Model for a Tubular Flow Reactor

To develop a solubility model for a tubular ow reactor,
a segregated model was applied (Fogler, 1992). The initial
assumptions are:
(1) When rapeseed oil and methanol enter the reactor, tiny
droplets of methanol with small amounts of dissolved oil
are formed and these droplets travel through the reactor
without coalescing together until they exit the reactor.
(2) Both reactants inside the droplets are perfectly mixed.
(3) There is no interchange of the reaction products, i.e.,
FAMEs and glycerol, between the droplets and the
continuous phase (oil phase). As the FAMEs are
formed, they promote the solubility of oil in methanol so
that the oil keeps dissolving in the methanol phase as
time progresses. Therefore each droplet behaves like a
tiny semibatch reactor with a continuous feed of oil.
(4) Each droplet spends equal time in the reactor (ideal
tubular reactor) leading to the same residence time (or
batch time for that matter).
(5) Assumptions 5 8 from the batch reactor solubility model
are also adopted.
The model can be further simplied by dividing the total
time that each droplet spends in the reactor into a number

ln

CTG=Me0
kt
CTG=Me

(10)

The rate constant (k) was calculated using a spreadsheet

technique (Microsoft Excel). A time interval (Dt) of 10 s was
used in the calculation. The total time studied was 60 s as
it was observed in the experiments that oil and methanol
were still in separate phase during this period. The initial
concentration of oil in the methanol phase (CTG/Me0) was
determined from the ternary phase diagram and the concentration of FAMEs at the beginning of each time interval (or at
the end of the previous time interval). To extrapolate the
concentration of oil at a very low concentration of FAMEs,
the ternary phase diagram was converted to a 2-D plot
by plotting the ratios of the concentrations of oil to that of
methanol versus the concentrations of FAMEs. Then
CurveExpert1.3 was used to t curves to those data. Several
mathematical models were found to give a good t to the
experimental data but the most suitable model was selected
according to two criteria. The rst criterion is that the model
must allow small amounts of oil to present in the system
even in the absence of FAMEs which is in accordance with
assumption 1. Another criterion is that the curve should be
shallow at the beginning and then followed by a steep
region which corresponds to the lag time and the sudden
surge reported in the literature as well as observed in this
study. This means that, at the beginning of the reaction, an
increase in FAME concentration has only small effect on
the solubility of oil in methanol but when the FAMEs build
up to a certain concentration, they greatly enhance the

Figure 10. Segregated model incorporating molar ux based on solubility envelope.

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SOLUBILITY MODEL TO DESCRIBE BIODIESEL

Table 3. Rate constants of the rst order transesterication reaction
reported in the literature and in this study.
Rate constant, min21

Reported by
Freedman (1986)
This study (batch reactor)
This study (continuous ow reactor)

0.7922.3731,2
0.018
1.78

Notes:
1
The reaction conditions are similar to those employed here but not
identical.
2
The numbers reported are the lowest forward rate constants.

intersolubility of the two components. It was found that

Gompertz function satised both criteria and gave a good
t to the experimental data. The boundary concentrations of
FAMEs at t 0.5 and 1 min, which were known from the
experiments, were applied and the k value of 1.78 min21
was nally obtained from the spreadsheet calculation. As
can be seen in Table 3, this value is within the same range
of the k values for the pseudo homogeneous rst order reaction reported by Freedman et al., (1986). Even though the 2.5
reaction order was found to give the best t to the batch
experimental data, an attempt was made to obtain the rst
order rate constant for comparison purpose. It was found
that, at the same reaction temperature, the k value from
the continuous ow reactor is larger than that from the
batch experiment by approximately two orders of magnitude.
This may be explained based on the hypothesis that the
kinetics of the transestercation reaction comprises three
regions: the solubility controlled region (slow), the kinetically
controlled region (fast) and the slow region as equilibrium
is approached. Even though we aimed to calculate the k
value of the rst region, by using a batch reactor, we could
not collect the data in this region because the reaction was
extremely fast. We therefore used the data in rst 4 min to
calculate the rate constant. As a result, the value obtained
in the batch experiment is actually an average of the rate
constants of the three regions.

CONCLUSION
It is quite clear form the above discussion that the use of
batch reactors to obtain kinetic data for fast transesterication reactions is awed due to the timescale of sampling
and possibly spatial variation of concentration. Continuous
mini rectors give tighter control and allow for fast intrinsic kinetics to be determined. The new solubility model described
above offers a good representation of the kinetics of vegetable oil transesterication at moderate temperatures. The
model could be developed further, for example, by considering the reaction in the oil phase and the existence of the glycerol phase, where methanol and catalyst are removed from
the reaction. In addition, soap formation and mass transfer
effects may also be taken into account. Although additional
work needs to be done to better model the complexities of
phase effects on reaction kinetics, our model goes some
way towards providing a better description of reaction kinetics
than was hitherto possible.

NOMENCLATURE
CMe/Me
CTG/Me
k

concentration of methanol in the methanol phase

concentration of oil in the methanol phase
reaction rate constant

rH
rL
m and n
NTG/Me
NTG/Me0
QH
QL
mH
mL
t
V
X
XTG

389

density of the heavy component

density of the light component
orders of the reaction
mole of oil in methanol
initial mole of oil in methanol
volume of the heavy component
volume of the light component
viscosity of the heavy component
viscosity of the light component
reaction time
volume of the reactor
correlation factor
conversion of oil

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The manuscript was received 6 March 2007 and accepted for
publication after revision 31 March 2007.

Trans IChemE, Part B, Process Safety and Environmental Protection, 2007, 85(B5): 383 389