Ind. Eng. Chem. Res.

2011, 50, 11771186

1177

Mechanistic Modeling of Palmitic Acid Esterification via Heterogeneous Catalysis

Nuttapol Lerkkasemsan, Nourredine Abdoulmoumine, Luke Achenie,*, and Foster Agblevor

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Publication Date (Web): December 15, 2010 | doi: 10.1021/ie100891n

Department of Chemical Engineering and Department of Biological Systems Engineering, Virginia Polytechnic
Institute and State UniVersity, Blacksburg, Virginia 24061, United States

Biodiesel has emerged as a promising renewable and clean energy alternative to petrodiesel. While biodiesel
has traditionally been prepared through homogeneous base catalysis, heterogeneous acid catalysis has been
investigated recently due to its ability to convert cheaper but high free fatty acid content oils such as waste
vegetable oil while decreasing production cost. In this work, the esterification of free fatty acid over sulfated
zirconia and activated acidic alumina was studied experimentally in a batch reactor. The models of the reaction
over the catalysts were developed in two parts. First, a kinetic study was performed using a deterministic
model to develop a suitable kinetic expression, and the related parameters were estimated. Second, a stochastic
model was developed as a pseudo-verification of the nature of the reaction at the molecular level. The
esterification of palmitic acid obeyed the Eley-Rideal mechanism in which palmitic acid and methanol are
adsorbed on the surface for SO4/ZrO2-550 C and AcAl2O3, respectively. The coefficients of determination
of the deterministic model were 0.98, 0.99, and 0.99 for SO4/ZrO2-550 C at 40, 60, and 80 C, respectively,
and 0.99, 0.96, and 0.98 for AcAl2O3 at the same temperature. The deterministic and stochastic models were
in good agreement when the number of molecules in the system was large enough. In general for a system
consisting of few molecules, the stochastic model is suggested, whereas for a large system, the deterministic
continuum model is suggested. If computational effort is not a bottleneck, then the stochastic model could be
used in all systems.
1. Introduction
Scientific inquiry into the production of biofuels as an
alternative source of energy has increased significantly in recent
years. This trend was prompted by environmental concerns and
the growing evidence of the depletion of natural crude oil
reservoirs. Biodiesel has emerged as a renewable biofuel for
the replacement of petroleum-based diesel or petrodiesel. Its
appeal is due to the fact that it has virtually all of the desirable
properties of petroleum-based diesel while being biodegradable
and most importantly, carbon neutral.1
Biodiesel could be produced by the transesterification of
triacylglycerols through base catalysis (see Figure 1) or esterification of free fatty acids and triacylglycerols by acid catalysis
as in Figure 2. However, virtually all industrial biodiesel plants
use KOH or NaOH bases to convert refined edible vegetable
oils with methanol to its equivalent fatty acid methyl esters
(FAME) due to the faster reaction rate of homogeneous base
catalysis. In addition, in homogeneous base catalysis, feedstock
selection is key to the success and economic feasibility of
biodiesel production. Both water and free fatty contents are
crucial components in the reaction, and their concentrations must
be minimized to prevent side reactions such as saponification
and ester hydrolysis. Indeed, in the presence of water, ester
hydrolysis of fatty acids on the triacylglycerol backbone could
take place, leading to the formation of additional free fatty acids.
Free fatty acids could then react with the base catalyst to form
fatty acid soaps through saponification. According to Lotero et
al., the free fatty acid contents in the oil should be no more
than 0.5 wt % beyond which the downstream separation process
is hindered by excessive soap formation due to the saponification
side reaction.2 Therefore, while homogeneous base catalysis
achieves high biodiesel yields, it limits the choice of feedstock
* To whom correspondence should be addressed. E-mail:
achenie@vt.edu.

Department of Chemical Engineering.

Department of Biological Systems Engineering.

to refined oils due to its compliance with the criteria described

above. This limitation hinders the competitiveness of biodiesel
against petrodiesel.
It is estimated that over 80% of the production cost of
biodiesel is associated with the cost of refined vegetable oil
which is already comparable to the selling price of petrodiesel.3
Consequently, to compete on a large scale, lower cost feedstock
and simpler processing schema should be used for biodiesel
production. This objective could be achieved by using cheaper
and high free fatty acid content oil such as waste vegetable oil
and animal fat necessitating a solution for handling the free fatty
acids.
Among homogeneous processes proposed for biodiesel
production from high free fatty acid content oils, a two-stage
process where free fatty acids are first converted by acid
catalysis via esterification followed by base catalysis has been
employed to reduce the free fatty acid content to an acceptable
value.4 This approach unfortunately increases the chemical
consumption since the acid catalyst used in the first stage must
be neutralized before the second stage resulting in increased
chemical usage. While heterogeneous base catalysis could also

Figure 1. Transesterification of triacylglerol to produce three fatty acid alkyl

esters by base catalysis.

Figure 2. Esterification of a free fatty acid to an alkyl fatty acid ester by

acid catalysis.

10.1021/ie100891n 2011 American Chemical Society

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Ind. Eng. Chem. Res., Vol. 50, No. 3, 2011

be employed, such a catalyst suffers from the same limitations

as its homogeneous counterpart with low esterification activity.
Heterogeneous acid catalysts have the most merit because they
could simultaneously catalyze the conversion of both free fatty
acids and triacylglycerols while reducing the production cost
due to catalyst reusability and decrease in separation cost.
Berrios et al. reported the kinetic study of free fatty acids in
sunflower oil with sulfuric acid as the homogeneous catalyst
and modeled the reaction with pseudohomogeneous first order
for the forward reaction and second order for the reverse reaction.5 Similarly, Tesser et al. described the esterification of oleic
acid over an ion-exchange sulfonic resin by a pseudosecond
order kinetic model.6 Meunier and co-workers investigated the
esterification of palmitic acid in sunflower oil over a silicasupported Nafion resin and compared its activity with sulfated
zirconium oxide.7 These authors showed that the silica-supported
Nafion resin performed better than the zirconium oxide.
H3PW12O40 heteropolyacid was used as homogeneous catalyst
for the ethanolysis of various fatty acids with yields similar to
those obtained through the traditional sulfuric acid homogeneous
catalysis.8 SnCl2 was successfully used for the esterification of
oleic acid in soybean oil using ethanol, and the catalyst was
found to yield comparable results with homogeneous H2SO4
catalyzed reactions.9 Despite the recent surge in biodiesel
research, there are few investigations on free fatty acid esterification and even fewer investigations of the reaction mechanism
over heterogeneous catalysts.
Several models (including Langmuir-Hinshelwood and
Eley-Rideal models) were used to study the kinetics of palmitic
acid esterification on sulfated zirconium oxide and activated
acidic alumina catalysts; the models that best fit the experimental
data are reported in this article. The model selection criteria
were root-mean-square deviation, standard deviation, coefficient
of determination, and experimental intuition. Furthermore, the
Gillespie model was used to for further verification of the model.
The rest of the manuscript is organized as follows. The
experimental effort is described in section 2. This is followed
by the modeling strategy. Finally we provide and discuss the
results.
2. Experiments
Details of the experimental protocol will be published
elsewhere. Therefore, in this paper, we will provide only a brief
summary.
Materials. Zirconium oxide and activated acidic alumina
were obtained from Alfa Aeasar (Alfa Aesar, Ward Hill, MA).
Palmitic acid was purchased from Sigma Aldrich (St. Louis,
MO). Methanol, n-hexane, and acetonitrile were all purchased
from Fischer Scientific (Fair Lawn, NJ) as analytical grade
solvents and used as received.
Catalyst Preparation and Characterization. Zirconium
oxide was ground to pass through a 20 mesh and subsequently
sulfated according the procedure described in procedure described elsewhere.10 After sulfation by incipient impregnation,
the catalyst was activated at 550 C for 6 h and this material
was labeled as SO4/ZrO2-550 C. The activated acidic alumina
catalyst was used as received without sulfation but was calcined
at 550 C for 3 h before use and was labeled as AcAl2O3. The
sulfated zirconium oxide catalyst was characterized by XPS,
SEM-EDS, and BET. The acidic alumina catalyst was characterized by SEM-EDS for chemical composition, and the surface
area was provided by the supplier.
Palmitic Acid Esterification. The reaction was carried out
in a water bath maintained at the appropriate temperature. In

the reaction flask, 2.56 g (0.01 mol) of palmitic acid and 32.04
g (1 mol) of methanol were added and placed in the water bath
first to reach the desired temperature before adding the appropriate amount of catalyst. The free fatty acid to methanol
content was increased to a 1:100 molar ratio to ensure complete
immersion of palmitic acid in the reaction mixture. Furthermore,
the higher methanol content prevented palmitic acid precipitation
during sample collection, improving the accuracy of the
procedure.
3. Modeling
Deterministic Kinetic Modeling. SO4/ZrO2-550 C and
AcAl2O3 were used to perform the kinetic experiments at 40,
60, and 80 C at 10% (w/w) and 100% (w/w). Several models
(including Langmuir-Hinshelwood and Eley-Rideal models)
were tested and the ones that best fit the experimental data are
reported in this article. The total active site on SO4/ZrO2-550
C was 2.05 wt %. Owing to the lack of actual experimental
data, we employed the total active site which was measured
via chemisorption of ethylene on alumina; this was reported to
be 35% mole.11 It was assumed that an Eley-Rideal mechanism
occurred with palmitic acid on the catalyst surface and methanol
in the bulk fluid with palmitic acid as the rate-determining step.
For AcAl2O3 however, the reaction occurred between methanol
on the catalyst surface and palmitic acid in the bulk fluid with
methanol adsorption as the rate-determining step.
SO4/ZrO2 at 550 C. The reaction mechanisms of palmitic
acid esterification on sulfated zirconia were hypothesized to
follow the Eley-Rideal mechanism. The reaction consisted of
three elementary reactions as described below.
KAB

A + S S AS
KS

AS + M S ES + W
KDB

ES S E + S
Here A is palmitic acid, S is an active site on the surface, M
is methanol, W is water, E is palmitic methyl ester, AS and ES
are adsorbed intermediates. The kinetic model was built based
on following assumptions:
1. The rate of the noncatalyzed reactions could be neglected
compared to the catalyzed ones.
2. The diffusion rate of product and reactant over the catalyst
surface could be neglected.
3. There were no differences in the activity and accessibility
of sites on catalyst surface.
4. The surface reaction was the rate limiting step.
5. The adsorption and desorption of reactants and products
were fast and were therefore at equilibrium.
6. There was no palmitic methyl ester and water before the
reaction.
Based on these assumptions, the following kinetic rate law was
derived:

rate )

( ))

CWCE
KDBKS
CE
1 + KABCA +
KDB

K1 KABCACM -

where KS, KAM, and KD represent the equilibrium constants of

surface reaction, adsorption of palmitic acid, and desorption of
palmitic methyl ester, K1 ) CTks,ks is the reverse reaction rate
constant.

Ind. Eng. Chem. Res., Vol. 50, No. 3, 2011

The concentration of the reactants and products can be

expressed as
CA ) CA0(1 - X),

CM ) CA0(100 - X)

CE ) CA0X,

CW ) CA0X

Therefore, the equation can be expressed as

rate )

K1 KABCA0 (1 - X)(100 - X) 2

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1 + KABCA0(1 - X) +

( ))
CA02X2

KDBKS
CA0X
KDB

AcAl2O3 Kinetic Model. Similarly, the reaction mechanism

of palmitic acid esterification on AcAl2O3 was hypothesized to
follow the Eley-Rideal mechanism. It also consisted of three
elementary reactions as
KAM

M + S S MS
KS

MS + A S WS + E
KDW

MS S W + S
where M is methanol, S is an active site, A is palmitic acid, W
is water, E is palmitic acid ester, and MS and WS are surface
intermediates. The kinetic model was built based on the same
assumptions for SO4/ZrO2. The following kinetic rate law can
be derived:

CWCE
KDWKSKAMCA
rate )
CWCE
CE
1+
+
KDWKSCA
KDW
K1 CM -

CE ) CA0X,

From the definition of the propensity function

CW ) CA0X

Therefore, the equation can be expressed as

rate )

K1 CA0(100 - X) 1+

KDWKSKAM

CA0X2
KDWKS(1 - X)

p(, j|x, t) d)

) p0(|x, t) (1 -

CM ) CA0(100 - X)

CA0X2

In the stochastic approach, it is assumed that each reaction

proceeds independently and randomly and can occur with a
certain probability associated with the thermodynamic properties
of the reacting molecules. The stochastic chemical kinetics
describes interactions involving a discrete number of molecules.
The stochastic algorithm is appropriate when the number of
molecules in a system is small. In a given initial number of
molecules, there are many possible time evolutions, each
of which has their own probability. The summation of all the
probabilities has to be one.
There is a link between deterministic and stochastic simulation. The reaction rate constants of the deterministic simulation
can be interpreted in terms of probabilities in the stochastic
simulation. The differential equations in the deterministic
simulation are similar to the stochastic approach. The nature of
chemical reactions is stochastic.13 Each reaction is a discrete
event that takes place with a given probability. An aspect of
this simulation is that it can determine whether a proposed
reaction mechanism is consistent with observed result. The
stochastic algorithm we employed is as follows.14
1. P0(|x,t) as the probability that no reaction occurs in the
time interval [t, t + ).
2. p(,j|x,t) is the probability that the next reaction will be
the jth reaction and occur during the time interval [t + ,
t + + d).
3. X(t) ) x is the number of molecules of a given species.
4. aj(X(t)) is a propensity function of the jth reaction.
5. Vj is a state-change vector of jth reaction.
6. cj is a reaction rate constant of jth reaction.
For a small enough time step, the assumption is that what
happens over [t, t + ) is independent of what happens over[t + , t + + d).
p0( + d|x, t) ) p0(|x, t) p0(|x, t + ) d
) p0(|x, t) p0(|x, t + ) d

Here KS, KAM, KD represent the equilibrium constants of surface

reaction, adsorption of palmitic acid, and desorption of palmitic
acid methyl ester, and K1 ) CTkAM, kAM is the forward rate
constant of adsorption of methanol.
The concentration of the reactants and products can be
expressed as
CA ) CA0(1 - X),

1179

CA0X
KDW

Stochastic Simulation. Computer simulations can be vital

in investigating a chemical reaction. The simulation can aid in
the exploration of the complex dynamics of reaction with ease.
There are two approaches to consider in computer simulation,
namely deterministic and stochastic.12 The deterministic approach uses a set of differential equations to explain the time
dependence of the concentrations in the chemical system.

a (x) d)

p0( + d|x, t) ) p0(|x, t)(1 -

k)1

From the proof in ref 15

p0(, j|x, t) )

aj(x)
(a (x) e-asum(x))
asum(x) sum

Here, (aj(x))/(asum(x)) is the next reaction index which corresponds to a discrete random variable that controls the chance
of picking the jth reaction while asum(x) e-asum(x) is the time until
the next reaction and is the density function for a continuous
random variable with an exponential distribution.
Assuming good mixing and negligible surface diffusion, the
resulting algorithm can be summarized in the following
pseudocode:
1. Evaluate {ak(X(t))}kM) 1 and
M

asum(X(t)): )

a (X(t))
k

k)1

2. Draw two independent uniform (0,1) random numbers, 1

and 2.
3. Set j to be the smallest integer satisfying

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Ind. Eng. Chem. Res., Vol. 50, No. 3, 2011

a (X(t)) > a

1 sum(X(t))

k)1

4. Set

()

1
2
)
asum(X(t))
ln

5. Set

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X(t + ) ) X(t) + Vj
6. Return to step 1.
SO4/ZrO2-550 C Stochastic Simulation. There are six
subchemical reactions that occur during the esterification of
palmitic acid over SO4/ZrO2-550 C. The solution contains seven
species and X ) Xn is the number of molecules of the nth
species. The six subreactions are illustrated below:
C1

X1 + X2 98 X3

[] [] []
[] [] []

-1
1
0
-1
1
0
1
-1
-1
V1 ) 0 V2 ) 0 V3 ) -1
0
0
1
0
0
1
0
0
0

(1)

0
0
0
0
1
-1
1
0
0
V4 ) 1 V5 ) 0 V6 ) 0
-1
-1
1
-1
0
0
0
1
-1

AcAl2O3 Stochastic Simulation. The reactions are expressed

as below:
C1

X1 + X2 98 X3

(7)

a1 ) C1X1X2

(7a)

C2

a1 ) C1X1X2
C2

X3 98 X1 + X2

(1a)

X3 98 X1 + X2

(8)

a2 ) C2X2

(8a)

(2)

C3

X3 + X4 98 X5 + X6

(9)

(2a)

a3 ) C3X3X4

(9a)

X3 + X4 98 X5 + X6

(3)

X5 + X6 98 X3 + X4

(10)

a3 ) C3X3X4

(3a)

a4 ) C4X5X6

(10a)

a2 ) C 2 X2
C3

C4

C5

C4

X5 + X6 98 X3 + X4
a4 ) C4X5X6

X5 98 X7 + X2

(11)

a5 ) C5X5

(11a)

(4)

(4a)

X2 + X7 98 X5

(12)

X5 98 X7 + X2

(5)

a6 ) C6X2X7

(12a)

a5 ) C 5 X5

(5a)

C5

C6

X2 + X7 98 X5

(6)

C6

where X1 is for methanol, X2 is for the vacant sites of the catalyst,

(dm3)/(gcat min) is for methanol adsorbed on the catalyst, X is
for palmitic acid, X5 is for palmitic acid methyl ester/methanol
intermediate adsorbed on the catalyst, X6 is for palmitic acid
methyl ester and finally X7 is for water.
4. Results and Discussion

a6 ) C6X2X7

(6a)

Here X1 is for palmitic acid, X2 is for the vacant sites on the

catalyst, X3 is for the palmitic acid attached to the catalyst, X4
is for the methanol, X5 is for palmitic acid methyl ester attached
to the catalyst, X6 is for water, and X7 is for the palmitic acid
methyl ester.
In step 5, the state vectors (Vj) of reactions 1-6 are

4.1. Characterization of Catalysts. The catalysts used in

this study were characterized to determine the elemental
chemical composition and the surface area, both important
characteristics to know for future reference. The surface areas
of both catalysts are shown in Table 1. The elemental composition analysis of SO4/ZrO2-550 C and AcAl2O3 was carried
out by SEM-EDS and XPS as shown in Table 2 and Table 3.
While both techniques are adequate for elemental analysis, XPS

Ind. Eng. Chem. Res., Vol. 50, No. 3, 2011

Table 1. BET Surface of the Catalysts
SO4/ZrO2-550 C

AcAl2O3

90.9

150

Surface area (m2/g)

Table 2. Elemental Composition of SO4/ZrO2-550C

Zr
O

SEM-EDS

XPS

74.31 ( 9.39
20.99 ( 8.81

15.07 ( 3.27
48.86 ( 3.79

C
S

SEM-EDS

XPS

3.66 ( 1.55
1.04 ( 0.25

34.01 ( 4.07
2.05 ( 0.29

Table 3. Elemental Composition of AcAl2O3 by SEM-EDS

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Al
O
C

40.15 ( 0.64
54.10 ( 0.85
5.75 ( 0.55

is more surface sensitive with penetration depth of 1-10 nm.

SEM-EDS scans deeper with a penetration depth of 0.3-5 m,
therefore providing a more accurate overall elemental composition of the catalysts.
4.2. Deterministic Kinetic Modeling. The esterification of
palmitic acid with methanol on SO4/ZrO2-550 C and AcAl2O3
follows the Eley-Rideal mechanism. For SO4/ZrO2-550 C, the
reaction of adsorbed palmitic acid with methanol in bulk fluid
is the rate determining step for SO4/ZrO2-550 C (Figure 3). In
contrast, the adsorption of methanol on an active site on the
catalyst was the rate-limiting step in AcAl2O3 (Figure 4).
The disparity between the adsorbed species is attributed to
the nature of the acidic sites on the catalysts. Sulfated zirconium

Table 4. Kinetic Parameters of Palmitic Acid Esterification on

SO4/ZrO2-550C

temp (C)

K1 10-4
(g (dm3)2/
3
(gcat
min2))

KAB 10-2
(dm3/mol)

KDB
(mol/dm3)

KS 10-3 (dm3/
(gcat min))

40
60
80

3.78
16.12
51.10

59.75
26.74
13.38

2.01
2.01
9.08

4.21
19.38
92.41

Table 5. Kinetic Parameters of Palmitic Acid Esterification on

AcAl2O3

temp (C)

K1 10-4
(g (dm3)2/
3
(gcat
min2))

KAM
(dm3/mol)

KDB
(mol/dm3)

KS 10-1 (dm3/
(gcat min))

40
60
80

1.36
0.91
1.50

2.01
0.14
0.08

2.17
2.01
2.01

0.02
0.21
1.14

oxide has been reported to have Bronsted and Lewis acid. When
the reaction was carried over pure zirconium oxide, the
esterification yield was minimal therefore it was assumed that
the catalyst activity was mostly due to the Bronsted acid sites
generated by the sulfation. Activated acidic alumina however
only has Lewis acid sites. The adsorption of palmitic acid is
believed to be a nucleophilic interaction between the Bronsted
acid site and the carbonyl of the carboxylic moiety similar to
homogeneous acid catalyzed esterification. On the activated
acidic alumina however, Lewis acid sites are predominant
leading to the chemisoption of methanol. Therefore, Bronsted
acid behaves differently from Lewis acid in the esterification
of free fatty acid. The estimated kinetic parameters are reported
in Table 4 and Table 5 for SO4/ZrO2-550 C and AcAl2O3,
respectively. The coefficients of determination of the deterministic model were 0.98, 0.99, and 0.99 for SO4/ZrO2-550 C at
40, 60, and 80 C, respectively, and 0.99, 0.96, and 0.98 for
AcAl2O3 at the same temperature.
To evaluate the efficiency of the catalysts, the activation
energies were determined. The reaction rate constant is related
to the reaction temperature through the Arrhenius equation.
Therefore, the overall reaction activation energy can be calculated from equation below using the reaction rate constant:

KS ) A exp Figure 3. Esterification of palmitic acid on zirconia sulfate. Fitting of

Eley-Rideal model to experimental data for palmitic acid esterification over
SO4/ZrO2-550 C at 40, 60, and 80 C.

Figure 4. Esterification of palmitic acid on alumina. Fitting of Eley-Rideal

model to experimental data for palmitic acid esterification over SO4/ZrO2550 C at 40, 60, and 80 C.

1181

E
RT

Both the frequency factor A and the activation energy Ea were

obtained by regressing ln(KS) versus 1/T. The activation energy
of palmitic acid esterification was 70.81 kJ/mol and 93.71 KJ/
mol for SO4/ZrO2-550 C and AcAl2O3, respectively. From the
activation energy of both catalysts, SO4/ZrO2-550 C seems to
be a better catalyst in the esterification of palmitic acid which
is a free fatty acid. However, this catalyst requires sulfation
and temperature activation before use. On the other hand,
AcAl2O3 does not require sulfation, though 3 hours of heating
at 550 C is required in order remove moisture and atmospheric
carbon from the surface. Therefore, it is more convenient for
industrial use where easy-to-prepare catalysts are needed,
although the operation cost of AcAl2O3 may be higher because
of the higher activation energy requiring higher temperature.
The esterification mechanisms of palmitic acid which occur over
both SO4/ZrO2-550 C and AcAl2O3 are depicted in Figure 5
and Figure 6, respectively.
4.3. Predicted Conversion Using Deterministic Model. To
validate the models, we used the models to predict the percent
conversion at 210 and 240 min at all temperatures for all
catalysts. We then compared the predicted values with actual
experimental data.

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Figure 8. Prediction of esterification of palmitic acid on alumina.

Table 6. Reaction Parameters Determined by Stochastic Model on
SO4/ZrO2-550 C

Figure 5. Palmitic acid esterification over SO4/ZrO2-550 C.

temp k1 ((dm3/ k2 (dm3 k3 ((dm3/

k4 (dm3/ k5 ((mol/ k6 (mol/
(C)
mol)2)
/mol) (gcat min))2) (gcat min)) dm3)2)
dm3)
40
60
80

0.30
0.80
1.14

0.5
3
8.5

1.28
6.55
6.92

304.04
337.84
74.88

4.02
1
4.54

2
0.5
0.5

Table 7. Reaction Parameters Determined by Stochastic Model on

AcAl2O3
temp
(C)
40
60
80

Figure 6. Palmitic acid esterification over AcAl2O3.

Figure 7. Prediction of esterification of palmitic acid over zirconia sulfate.

As can be seen in Figure 7 and Figure 8, the deterministic

models used to predict the conversion at time greater than 180
min showed good accuracy. The values of the deterministic
models are very close to the experimental data. Therefore, these
rate law models can be used to predict the experimental data at

k1 10-2
((dm3/ k2 10-3 k3 ((dm3/
k4 (dm3/ k5 ((mol/ k6 (mol/
mol)2) (dm3/mol) (gcat min))2) (gcat min)) dm3)2)
dm3)
1.89
1.27
2.08

0.94
9.10
271.59

9.70
6.23
10.82

500.00
300.00
95.00

1.19
16.08
20.10

0.55
8.00
10.00

different temperature between 40 and 80 C and at longer

reaction time.
4.4. Results for Stochastic Kinetic Modeling. The stochastic
simulation is used as a tool for observing the nature of the
reaction which occurs over the surface of the catalysts. In
systems such as some biological processes, the reaction can be
accurately simulated using a stochastic simulation. The major
difference at the molecular level between deterministic and
stochastic is that the deterministic model makes a continuum
assumption in the concentrations, whereas the stochastic model
investigates the intrinsic nature of the reaction and therefore
considers the number of molecules that are reacting. In a
chemical reaction each individual reaction is an event that occurs
with a certain probability. From a practical point of view, the
deterministic model is easier to set up and faster in terms of
calculation compared to the stochastic model. When dealing with
a small number of molecules, the deterministic model is not
appropriate.
To observe the reactions which occur over the surface of the
catalyst, a small number of molecules in the system will be
observed. There is a link between deterministic and stochastic
simulation. The rate constant (Cj) for stochastic simulation are
estimated from kinetic parameters (kj) (Tables 6 and 7) in the
deterministic simulation as
C1 )

k1
,
nAvol

C2 ) k2,

C3 )

C4 )
In addition

k3
,
nAvol

k4
,
nAvol

C5 ) k5,

C6 )

k6
nAvol

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Figure 9. Stochastic simulation vs Eley-Rideal model on SO4/ZrO2-550 C at 40 C: (a) stochastic simulation on SO4/ZrO2-550 C; (b) compare conversion
from stochastic model vs deterministic model on SO4/ZrO2-550 C.

Figure 10. Stochastic simulation vs Eley-Rideal model on SO4/ZrO2-550 C at 60 C: (a) stochastic simulation on SO4/ZrO2-550 C; (b) compare conversion
from stochastic model vs deterministic model on SO4/ZrO2-550 C.

KAM )

k1
,
k2

KS )

k3
k4

and kDB )

k5
k6

Palmitic Acid Esterification over SO4/ZrO2-550 C. The

reaction parameters of palmitic acid esterification over SO4/
ZrO2-550 C are determined as in Table 6. Also, the results of
the stochastic simulations for SO4/ZrO2-550 C at different
temperatures are shown in Figures 9-11.
As the number of molecules in the system increased, the
stochastic simulation algorithms generated smooth graphs that
are comparable to those produced in the deterministic model.
This was also observed as the temperature increased due to
increased frequency of collision and therefore higher likelihood

of reaction. The number of molecules employed were 1800,

1200, and 600 for both SO4/ZrO2 and AcAl2O3 at temperatures
of 40, 60, and 80 C, respectively. The stochastic simulation
acts as a pseudovalidation of the Eley-Rideal mechanism. The
deterministic behavior represents the average of all these
possible stochastic evolutions. Thus we note that the deterministic model and stochastic simulation are very close as illustrated
in Figure 9 through 14 for both catalysts. Consequently, the
deterministic result should be enough to describe the mechanism
of the system. However, for other more complex catalyst such
as enzyme, the stochastic simulation could be essential in
investigating the reaction mechanisms.

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Figure 11. Stochastic simulation vs Eley-Rideal model on SO4/ZrO2-550 C at 80 C: (a) stochastic simulation on SO4/ZrO2-550 C; (b) compare conversion
from stochastic model vs deterministic model on SO4/ZrO2-550 C.

Figure 12. Stochastic simulation vs Eley-Rideal model on AcAl2O3 at 40 C: (a) stochastic simulation on AcAl2O3; (b) compare conversion from stochastic
model vs deterministic model on AcAl2O3.

Palmitic Acid Esterification over AcAl2O3. The reaction

parameters of palmitic acid esterification over AcAl2O3 were
determined as in Table 7. In addition, the results of stochastic
simulations for alumina at different temperatures are shown in
Figures 12-14.
The rate constant (Cj) can be calculate from (kj) as
C1 )

k1
, C ) k2,
nAvol 2

k3
,
nAvol
k4
, C5 ) k5,
C4 )
nAvol
C3 )

C6 )

k6
nAvol

Computational Time for Stochastic Simulations. The

computational time (in CPU seconds) for palmitic acid esterification over both systems (SO4/ZrO2-550 C and AcAl2O3) are
given in Table 8. The runs were conducted on a Intel Core2
Duo P8400 2.27 GHz computer running the VISTA operating
system. We note that the CPU time increases from 40 to 60 C
and then drops afterwardsit is not clear why this is the case.
However we conjecture that this probably has to do with the
balance between two driving forces: (a) increasing collision rate
and therefore the greater the probability that a reaction occurs
within a very short time interval and (b) the faster depletion of
reactants at higher temperatures.

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Figure 13. Stochastic simulation vs Eley-Rideal model on AcAl2O3 at 60 C: (a) stochastic simulation on AcAl2O3; (b) compare conversion from stochastic
model vs deterministic model on AcAl2O3.

Figure 14. Stochastic simulation vs Eley-Rideal model on AcAl2O3 at 80 C: (a) stochastic simulation on AcAl2O3; (b) compare conversion from stochastic
model vs deterministic model on AcAl2O3.
Table 8. CPU Time for Stochastic Simulations
Temperature [)] (C)

CPU time for

zirconia [)] (s)

CPU time for

alumina [)] (s)

40
60
80

24.2347
173.6447
0.6084

1.3728
8.7205
1.7784

5. Conclusion
We employed both deterministic and stochastic simulation
in this study. The stochastic simulation generated smooth graphs
(which are a characteristic of the deterministic simulation) as
the number of molecules in the system increased. This was also
observed as the temperature increased due to increased fre-

quency of collision and therefore higher likelihood of reaction.

These results help us to answer the question, what is the critical
number of molecules required for the stochastic simulation to
track the deterministic simulation? This would give a rough
guide as to when to employ which method. Since in general
the deterministic simulation is faster than the stochastic simulation, there would be a gain in speed if the deterministic
simulation is adequate. However if speed is of no consequence,
then the safer route is to simply employ stochastic simulation.
The second goal was to use the stochastic simulation as a
pseudovalidation of the deterministic simulation.
The results suggest that the Eley-Rideal mechanism is
appropriate to explain the reaction mechanism which occurs in

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the esterification of palmitic acid over both SO4/ZrO2-550 C

and AcAl2O3. The reaction of adsorbed palmitic acid with
methanol in bulk fluid is the rate determining step for SO4/
ZrO2-550 C. On the other hand, the adsorption of methanol
on an active site on the catalyst was the rate-limiting step in
AcAl2O3. This difference in adsorbed species is attributed the
nature of the acid sites: SO4/ZrO2-550 C has mostly Bronsted
acid sites, whereas AcAl2O3 has Lewis acid sites. Furthermore,
the deterministic model and the stochastic simulation are in good
agreement. It is therefore sufficient to use the deterministic
model for the future kinetic investigation of free fatty esterification over heterogeneous catalysts. Furthermore, we showed
that these models can be used to predict the conversion for
different times. The activation energy of SO4/ZrO2-550 C is
70.81 kJ/mol while that of AcAl2O3 is 93.70 kJ/mol indicating
that SO4/ZrO2-550 C is better in the esterification for free fatty
acids. Both SO4/ZrO2-550 C and AcAl2O3 are therefore suitable
catalysts for the conversion of high free fatty acid containing
oils such as waste cooking oil, a cheaper alternative feedstock,
for the production of renewable diesel through an environmentally friendly process. Finally, this investigation of the esterification of free fatty acids will not only help in reactor design
but could also serve as a model for further kinetic studies of
transesterification of vegetable oil to biodiesel. Moreover, the
combination of deterministic modeling and stochastic simulation
can be used as a model to study more complex catalyst such as
enzyme catalyst.
Acknowledgment
The authors duly acknowledge the Institute for Critical
Technology and Applied Science at Virginia Polytechnic
Institute and State University for funding this project.
Nomenclature
A ) palmitic acid
E ) palmitic acid methyl ester
M ) methanol
S ) catalyst active site
W ) water
CT ) total catalyst active sites
AS ) palmitic acid adsorbed on an active site
ES ) intermediate palmitic acid methyl ester on the catalyst surface
CA ) concentration of palmitic acid, M
CB ) concentration of methanol, M
CE ) concentration of palmitic acid methyl ester, M
CW ) concentration of water, M
CA0 ) initial concentration of palmitic acid, M
KAB ) adsorption parameter of palmitic acid, dm3/mol
KDB ) desorption parameter of palmitic acid, mol/dm3

KAM ) adsorption parameter of methanol, dm3/mol

KS ) equilibrium rate constant, KS ) k-S/kS
k-s ) kinetic constants of the forward reaction, dm3/(gcat min)
ks ) kinetic constants of the reverse reaction, dm3/(gcat min)
X ) conversion of palmitic acid

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ReceiVed for reView April 15, 2010

ReVised manuscript receiVed October 19, 2010
Accepted November 24, 2010
IE100891N