Kinetic modelling studies of heterogeneously catalyzed biodiesel synthesis reactions

Ankur Kapil, Karen Wilson, Adam F Lee, Jhuma Sadhukhan*

Centre for Process Integration, School of Chemical Engineering and Analytical Science, The
University of Manchester, Manchester, M13 9PL, UK

Cardiff School of Chemistry, Cardiff University, Main Building, Park Place, Cardiff, CF10
3AT

Author to whom correspondence should be addressed

E-mail: [email protected]
Phone : +44-161-3064396
Fax: +44 -161-236 7439

Abstract
The heterogeneously catalysed transesterification reaction for the production of biodiesel from
Triglycerides was investigated for reaction mechanism and kinetic constants. Three elementary
reaction mechanisms Eley-Rideal (ER), LangmuirHinshelwoodHougenWatson (LHHW), and
Hattori with assumptions such as quasi steady state conditions for the surface species and
methanol adsorption, and surface reactions as the rate determining steps were applied to predict
the catalyst surface coverage and the bulk concentration using a multi-scale simulation
framework. The rate expression based on methanol adsorption as the rate limiting in LHHW
elementary mechanism has been found to be statistically the most reliable representation of the
experimental data using hydrotalcite catalyst with different formulations.

Keywords: Biodiesel, transesterification, heterogeneous catalysts, elementary reaction kinetics,

hydrotalcites

1 Introduction
Biodiesel is a state-of-the-art renewable fuel produced by reacting vegetable oils, refined oils and
animal fats, containing triglycerides and free fatty acids as the main constituents, with methanol1.
The three main reactions steps in transesterification of Triglyceride with methanol are given in
Equations 1-32. In these reactions, Triglyceride (T), Diglyceride (D), and Monoglyceride (M)
react with methanol (CH3OH) to form D, M and glycerol (G) respectively along with Methyl
Oleate (MeOl), or longer chained methyl ester - depending on glyceride chain length.
T + CH3OH
D + MeOl

D + CH3OH
M + MeOl

M + CH3OH
G + MeOl

Heterogeneously catalysed transesterification reactions3, 4 that include alkali oxides5, 6, alkaline

earth oxides7-9, zeolites10, 11, and hydrotalcites12-15, are preferred over homogeneous reactions,
due to various reasons, including soap formation, catalyst loss and involvement of significantly
more number of separation steps in the latter case. Dossin et al.2, 16 introduced the kinetic studies
of MgO catalyzed transesterification of alkyl esters with methanol using ER type mechanism.
Their model is based on the following assumptions: i) adsorption of methanol as the rate
2

determining step; ii) all other reactions assumed to be in equilibrium, and iii) equal rate constants
for the forward reaction in all the three basic reactions steps (Equations 1-3). They developed a
kinetic model based on a single elementary reaction mechanism with assumption of methanol
adsorption as rate limiting step, for a single composition of MgO catalyst. Building on their
work, the scope of this work was to undertake comprehensive kinetic studies of heterogeneously
catalyzed transesterification reactions. Three mechanistic kinetic models, ER (considering
reaction of triglyceride with adsorbed methanol), LHHW (considering adsorption of triglyceride
on the catalyst surface) and Hattori (considering formation of intermediates from every
elementary reaction step), with various assumptions on rate determining steps and quasi steady
state for surface species have been analysed. The experimental results presented in Appendix A
are based upon hydrotalcites catalysts with four different formulations Mg0.81Al, Mg1.38Al,
Mg1.82Al, and Mg2.93Al, referred as MG1, MG2, MG3, and MG4, respectively14. These catalysts
are micro-porous with active sites concentrated on their surface, reducing the requirement for
bulky glyceride species diffusing through micro-pores, whilst providing rigidity through the
layered structure.
The hierarchical modelling of reactions is essential to evaluate the effect of micro scale surface
evolution on the changes in bulk concentration and vice versa and thereby validate reaction
mechanisms17. Karpov et al.18 considered the coupling of Monte Carlo with the continuum finite
element method (FEM) equations for fuel cell catalysts and binary material systems applications.
Levchenko et al.19 used multiscale Monte Carlo/ surface diffusion numerical equation to study
the growth of metal catalyst particles by deposition from a low-temperature plasma. Majumder et
al.20 developed a multiscale modelling approach combining Monte Carlo simulations with finite
difference solver. They established their method by comparison with a continuum method. The
methodology was applied to two reaction mechanism for unimolecular and bimolecular
reactions. Vlachos et al.21 applied a hierarchical multiscale simulation framework for modelbased design of experiments. The multiscale model was applied to two case studies for ammonia
decomposition on ruthenium to produce hydrogen and the water-gas shift reactions on platinum
for converting syngas to hydrogen. Raimondeau et al.22 applied multiscale simulations to study
the effect of species spatial inhomogeneity to the catalytic oxidation of CO on Pt. By adapting
these modelling tools and insights, this work aims to integrate catalytic surface kinetic Monte
Carlo (KMC)23 and bulk scale mean field (MF) simulations24 in order to validate the kinetic

parameters estimated using genetic algorithm (GA) based optimisation approach25, 26. The kinetic
parameters obtained correspond to the appropriate match between simulation and experimental
results of evolution in bulk concentrations.
The overall modelling strategy is discussed in the next section. Estimation of kinetic rate
constants using GA based optimization methodology, followed by their validation using multiscale KMC/MF simulation framework is outlined. Thereafter, ER, LHHW, and Hattori
mechanisms alongside the derivations of the kinetic rate expressions are illustrated. The results
of various mechanisms are quantitatively analysed and compared for the selection of the most
appropriate mechanism that may be valid for the whole range of formulations. Simultaneously,
the analysis may also suggest the best mechanism for individual formulations.

2 Methodology
The overall strategy for an estimation of kinetic rate constants based on a reaction mechanism is
illustrated as follows (Figure 1).
1. The rate parameters involved in an assumed mechanism were estimated using GA based
optimisation.
2. Using the rate constants obtained from step 1, the distribution of species on the surface of
a catalyst formulation as well as the changes in bulk specie concentrations were predicted
by a multi-scale KMC/MF simulation framework implemented. This framework was
used to simultaneously capture the effect of surface adsorption-reaction-desorption on the
bulk specie concentrations. An iteration of rate constants between the GA based
optimisation step and the multi-scale KMC/MF simulation step may be involved, until
the best fit of concentration profiles against experimental results is obtained.
3. The mechanism is applied to various catalyst formulations.
4. New mechanisms and assumptions were then considered for the parametric prediction
using the above two frameworks, GA based optimisation and multi-scale KMC/MF
simulation, until all three mechanisms with given assumptions are investigated.
5. Statistical reliance and comparison between mechanisms were performed. This analysis
may propose the most appropriate mechanism that may be valid for the whole range of
formulations or suggest the best mechanism for individual formulations.

Figure 1: Overall strategy to investigate into reaction mechanisms

Determination of kinetic rate constants using GA
The steps for the estimation of the rate constants by applying GA based optimization are as
follows.
1. The initial concentrations in the batch reactor (Ci(0)), size of the reactor, and batch time
are specified (Appendix A). The bounds for the rate constants kj are also provided as the
inputs to the GA (Appendix B).
2. The rate constants are decision variables and their initial values are guessed by GA using
random number generator in between their respective bounds.
3. The bulk concentration (Ci) of specie i is a function of kinetic rates (Ri), Equation 4.
i T , D, M , G, MeOl , CH 3OH

dC i
= Ri
dt

4. To account for the non-ideality of a mixture as in here, the correlation between the
activity of specie ([i]) and its concentration Ci in Equation 5 was applied. The UNIFAC
contribution method27 outlined in Appendix C was used to calculate the activity
coefficients, i . Table 1 exemplifies typical values of activity coefficients of species.

[i ] = Ci i

i T , D, M , G, MeOl , CH 3OH

5. The set of ordinary differential equations (Equation 4) was solved by ode45 solver in
MATLAB with a time gap of 1s. The bulk concentrations profiles of species in the
reactor is obtained as a function of time.
6. The GA optimization, based on the works of Bhat et al.25 and Xu et al.26, 28, implemented
in MATLAB (Appendix B) was then applied to minimise the residual sum of square
(RSSQ) of errors between the experimentally observed and the model predicted
concentrations of species (i = 1 to nspc), at subsequent time points (j = 1 to ntime), in
Equation 6, by adjusting the rate constants within their specified ranges. It is assumed
that the rate of reaction for adsorption of methanol is a low value in the range of 10-1
while that for other reaction rate constants are in 2 orders of magnitude.
ntime nspc

RSSQ =

(C ( j ) C
i

epxerimental
i

( j ))2

j =1 i =1

7. GA generates new sets of rate constants. RSSQ is re-evaluated according to Equation 6.

8. Simulations were repeated until RSSQ is <0.005 or the number of iterations exceeds the
maximum (100000).

Table 1: Activity coefficients of species

Multi-scale KMC/MF simulation framework
Once the preliminary rate constants were estimated by GA based optimisation, these parameters
were further verified using a multi-scale KMC/MF simulation framework implemented in
MATLAB (Figure 2).
1. The concentrations of species on the surface of the catalyst, and the concentrations in the
bulk were the inputs to the KMC algorithm. The surface of the catalyst was considered to
be empty at the start of a reactor run. The initial bulk concentrations were obtained from
the work of Cantrell et al.14(Appendix A).
2. The surface concentration was assumed to be constant during mean field simulation over
a small time interval dt(~1s). The bulk concentration changes were updated by the mean
field simulation of the ordinary differential equation in the bulk phase (Equation 4). The
rate of change of concentration was defined on the basis of kinetic rates in the elementary
reaction mechanism.
3. Similarly, the bulk concentration was assumed to be constant over a small time interval

dt, during which the KMC simulation on the catalyst surface was undertaken. The KMC
simulation relied upon the event probability based on their respective rate constants. The
surface concentration is advanced in time by KMC simulation23.
4. The overall time is advanced as the times for KMC and MF simulations are updated.
5. The simulation is continued for the total run time of a reactor (in this case 10800s,
Appendix A).

Figure 2: Multi-scale KMC/MF simulation framework

Three elementary reaction mechanisms, ER, LHHW and Hattori, along with the rate expressions
depending upon the assumptions on the rate determining steps and quasi steady states, are
discussed next.

ER mechanism
The elementary reactions in ER kinetic mechanism are shown in Table 2. The mechanism
involves adsorption of methanol on empty catalyst sites and reactions between adsorbed
methanol (CH3OH*) with T, D and M in the bulk to form adsorbed diglyceride (D*),
monoglyceride (M*) and glycerol (G*) respectively along with methyl oleate (MeOl).

Table 2: Elementary reactions in ER mechanism

Each of these steps can be treated as a rate determining step. The surface of the catalyst was
assumed to be homogeneous without any inert specie in all cases. The rates of generation and
consumption of bulk species in Table 2 were derived based on the assumption of quasi steady
state conditions of the surface species, in Table 3. Hence, the concentrations of the catalyst
surface species remained constant with respect to time. Additionally, the backward reaction rate
constants were neglected. k1-k7 in Table 3 represent the kinetic rate constants of the forward
reactions in 7 elementary steps in Table 2. [D ], [T ], [M ], [G ], [CH 3OH ], [MeOl ] are the activities of
diglyceride, triglyceride, monoglyceride, glycerol, methanol and methyl oleate respectively in
the bulk phase.

Table 3: Kinetic reaction rate expressions for ER quasi steady state mechanism

LHHW mechanism
The elementary reactions in LHHW kinetic mechanism are given in Table 4. The first step is the
adsorption of methanol. The main difference between ER and LHHW mechanism is the
adsorption of triglyceride on the surface of the catalyst. The adsorbed methanol and triglyceride
react with each other if they are adjacent, to produce adsorbed diglyceride and methyl oleate
respectively. Subsequently this adsorbed methanol reacts with adsorbed diglyceride or
monoglyceride to form adsorbed monoglyceride, and glycerol respectively along with methyl

oleate. Table 4 presents the expressions for equilibrium rate constants K1-K9, for the 9 elementary
reaction steps in LHHW mechanisms respectively.

Table 4: Elementary reactions in LHHW mechanism

In addition to the adsorbed species defined in ER mechanism * and T* were introduced to

represent empty site and adsorbed triglyceride on the catalyst surface, respectively. k j indicates
the forward reaction kinetic rate constants for the 9 rate determining steps, and Kj represents the
equilibrium constants of reaction j, respectively, in Table 4. The elementary reaction expressions
in Table 4 lead to the kinetic rate expressions for individual reaction steps, in Table 5.
Table 5: Elementary reaction rate expressions for LHHW mechanism with surface reaction
as rate limiting
Hattori mechanism
The elementary reactions in Hattori kinetic mechanism are provided in Table 6. Similar to
LHHW, Hattori mechanism also considers the adsorption of triglyceride on the surface of the
catalyst as a rate determining step. Hattori mechanism differs from LHHW mechanism, where in
the formation of intermediate species from the reactions between adsorbed methanol and
adsorbed triglyceride, diglyceride and monoglyceride is considered. The adsorbed methanol and
triglyceride react to form adsorbed intermediate (TsCH3OH*) and an empty site respectively.
Subsequently, the adsorbed intermediate (TsCH3OH*) decomposes into the production of
adsorbed diglyceride and bulk methyl oleate respectively. Adsorbed diglyceride, monoglyceride
and glycerol thereafter desorb from the catalyst surface into the bulk phase. TsCH3OH*,
DsCH3OH*, MsCH3OH* represent the intermediates from the reactions between adsorbed

methanol and adsorbed T, D and M respectively. The elementary reaction expressions in Table 6
result in the kinetic rate expressions in Table 7.

Table 6: Elementary reactions in Hattori mechanism

Table 7: Elementary reaction rate expressions for Hattori mechanism with methanol
adsorption as rate limiting

k j indicates the forward reaction kinetic rate constants for 11 rate determining steps, and Kj

represents the equilibrium constant of reaction j, respectively, in Table 6.

3 Results and discussions

The GA optimisation (Appendix B) and KMC/MF simulation (Figure 2) frameworks were
implemented in a PC with Pentium D CPU 3.00 GHz processor and 1GB RAM. The run time
for the convergence of one mechanism applied to a catalyst formulation is 105 minutes. Five
kinetic models based on the three elementary reaction mechanisms, ER (Table 2), LHHW (Table
4) and Hattori (Table 7) with assumptions on quasi steady state of surface species and methanol
adsorption and surface reaction as rate limiting steps were investigated, as follows.

ER quasi steady state

ER methanol adsorption as rate determining

LHHW surface reaction as rate limiting

LHHW methanol adsorption as rate limiting

Hattori methanol adsorption as rate determining

The statistical significance of a mechanism is achieved by Chi square 2 test. The results of
kinetic parameters and chi square test for statistical significance are presented in Table 8. It is
calculated as the ratio of the residual sum of the square of the errors (RSSQ) between the
predicted and the experimental values for the concentrations of the species (i = 1 to nspc), at time
points (j = 1 to ntime) and the experimental values at given data points, in Equation 7 28.
ntime nspc
2

j =1 i =1

(C ( j ) C
i

epxerimental
i

( j ))2

C iepxerimental ( j )

Table 8: Prediction of kinetic rate constants and 2 for different mechanisms and catalysts
The simulation results of ER quasi steady state mechanism (Table 3) on Mg2.93Al hydrotalcite
catalyst are illustrated in detail, while other system results are only summarised.

Results of application of ER quasi steady state mechanism to hydrotalcite catalyst Mg2.93Al

The results of kinetic parameters (k1-7) in ER quasi steady state mechanism (Table 3) on Mg2.93Al
hydrotalcite catalyst using GA and multi-scale KMC/MF simulation framework are provided in
Figure 3, Figure 4, and Figure 5 respectively. The RSSQ resulted (0.008) is higher than the
specified for GA optimisation. However, the 2 value of 0.0044 in Table 8 is smaller than 0.01
required for 99.5% level of significance (confidence) with 7 degrees of freedom, in chi square
test for statistical significance29, implying higher level of significance / applicability of the
mechanism.

Figure 3: Comparison between (a) fractional conversion of Triglyceride (T); (b) moles of
Diglyceride (D); and (c) moles of Monoglyceride (M); for Mg2.93Al hydrotalcites obtained
from ER quasi steady state model
The multi-scale simulation framework results into the time evolution of surface species, based on
which the quasi steady hypothesis assumed at the first place can be validated. The results of the
KMC/MF simulation presented in Figure 4 indicate a rapid initial change in the concentration of
the species on the surface. However, subsequently steady state surface coverage fraction of 0.05
and 0.0003 were attained by the adsorbed species M* and CH3OH*, respectively, after 1000s,
while D* and G* eventually reached to their steady states at 0.09 and 0.84 respectively, after
10,000s (Figure 4). Hence, a steady state equilibrium attained by surface species reinforces the
assumption on their quasi steady state.

Figure 4: Time evolution of surface species from KMC simulation

Figure 5 shows the evolution of catalyst surface resulted from KMC simulations. Initially the
catalyst surface lattice is made up of empty sites (.) (Figure 5 case (a)). These lattice sites are
converted into adsorbed methanol (). However, the reaction of methanol with high
concentration of triglyceride in bulk phase is fast. Hence most of the adsorbed methanol is
converted into adsorbed diglyceride (+), 97.1% in case (b) Figure 5. A fraction of the adsorbed
diglyceride is subsequently converted into adsorbed monoglyceride () and finally into glycerol
(), 25.3% of each in case (c) Figure 5 over the duration of the reaction (10800s).

10

Figure 5: Evolution of catalyst surface from KMC simulations; *(.), CH3OH*(), D*(+),
M*(), G*(). Case (a) * (100%), CH3OH*(0), D*(0), M*(0), G*(0) at t=0s; Case (b) *
(2.9%), CH3OH*(0.07%), D*(97.1%), M*(0), G*(0) at t=2000s ; Case (c) * (5.4%),
CH3OH*(0.1%), D*(43.9%), M*(25.3%), G*(25.3%) at t=10800s;
The kinetic parameters (Table 8) thus obtained by following the strategy in Figure 1 for ER quasi
steady state reaction mechanism represents the experimental observation for M2.93Al hydrotalcite
catalyst adequately. These frameworks were further applied to the other hydrotalcite catalysts
with different concentrations of Mg and Al (Appendix A).

Results of application of ER quasi steady state mechanism for all hydrotalcite catalysts
The RSSQ and 2 obtained for Mg1.82Al hydrotalcite catalyst are 0.006 and 0.0218, respectively,
indicating statistically good representation of the experimental data for Mg1.82Al hydrotalcite
catalyst. Table 8 demonstrates statistically acceptable 2 values of 0.0174, 0.0218, and 0.0044
for the hydrotalcite catalysts, Mg0.82Al, Mg1.82Al, and Mg2.93Al, respectively. However, the
results for Mg1.38Al indicate a higher value of 2 (0.2611), revealing inconsistency in predicting
the ER quasi steady state model for all four catalysts.
ER elementary reaction mechanism (Methanol adsorption as rate limiting)
From the illustration earlier, it was rational to assume methanol adsorption as a rate determining
step in the ER mechanism. The resulting mechanism was further simplified by the assumption of
equal rate constants of all the adsorption equilibrium steps, based on the work of Dossin et al.2.
The equilibrium constant for the adsorption of methanol ( K eq ) was assumed to be constant and
equal to unity. The kinetic rate expression was reduced to two parameters k f (rate of forward
reaction for adsorption of methanol), and K A (adsorption equilibrium constant for diglyceride,
monoglyceride, glycerol and methyl oleate) (Equations 8, 9, and 10). Table 8 illustrates the 2
of 0.028, 0.03, 0.1722 and 0.013 for Mg0.82Al, Mg1.38Al, Mg1.82Al, and Mg2.93Al, respectively
which is much less than 1.72 required for individual catalysts for the two parameter kinetic
model with 9 degrees of freedom at 99.5% level of fit29. The degree of freedom is the number of
experimental points (12) the number of kinetic parameters (2) -1. Hence the kinetic model
based on ER mechanism with methanol adsorption as rate limiting, can be applied to all four

11

hydrotalcite catalysts. The 2 value certainly improves for Mg1.38Al case from the quasi steady
state assumption.

[D][MeOl ]

k f [CH 3OH ] 1

K eq
[
T]

rT =

1 + K A [D ][MeOl ] + K A [MeOl ] + K A [T ] + K A [D ] + K A [M ] + K A [G ]
K

[T ]
eq

rD =

[M ][MeOl ]
k f [CH 3OH ] 1
K
eq
[D]

1 + K A [M ][MeOl ] + K A [MeOl ] + K A [T ] + K A [D ] + K A [M ] + K A [G ]
K

[D]
eq

[G ][MeOl ]
k f [CH 3OH ] 1
K
eq
[M ]

rM =

1 + K A [G ][MeOl ] + K A [MeOl ] + K A [T ] + K A [D ] + K A [M ] + K A [G ]
K

[M ]
eq

10

The lowest rate constant corresponds to methanol adsorption (kf) with values of 1.610-6,
1.7110-6, 7.3310-6 and 7.1210-6 for the four hydrotalcite catalysts, with increasing Mg
concentration, respectively, revalidating the assumption (Table 8). However, ER mechanism
assumes no adsorption for triglyceride, diglyceride, and monoglyceride in the bulk to react with
adsorbed methanol. Triglyceride, diglyceride, and monoglyceride are large molecules and
therefore their adsorption onto the catalyst surface would be difficult and hence can be regarded
as rate determining steps, such as in LHHW and Hattori mechanisms discussed as follows.
LHHW elementary reaction mechanism (Surface reaction as rate limiting)

The kinetic rate constants for LHHW mechanism comprising of elementary steps in Table 4 are
shown in Table 8. As can be seen from the results, the equilibrium reaction rate constant between
adsorbed methanol and adsorbed diglyceride (K4), is the fastest with the values of 0.37, 0.48 and
0.44 for Mg0.81Al, Mg1.38Al and Mg2.93Al respectively (in the case of Mg1.82Al reaction between
adsorbed methanol and adsorbed triglyceride (K3) is found to be the fastest with a value of 0.15).
It is consistently identified that K1, the equilibrium constant of adsorption of methanol is the

12

slowest with 5.9710-5, 0.0001, 3.310-5 and 0.0001 for all four hydrotalcite catalysts,
respectively (Table 8). 2 of 0.0061, 0.0203, 0.0092, and 0.0129 are predicted for Mg0.81Al,
Mg1.38Al, Mg1.82Al, and Mg2.93Al, respectively, which are larger than 0.00 required for ten
parameter kinetic model with 1 degree of freedom at 99.5% level of fit29. Hence the kinetic
model based on LHHW surface reaction rate limiting cannot be applied to any of the four
hydrotalcite catalysts at 99.5% level of significance.
LHHW elementary reaction mechanism (Methanol adsorption as rate limiting)

The increase in the number of kinetic rate constants although increases the degrees of freedom,
but reduces statistical reliability due to lighter fitting with experimental data. Dossin et al.2
developed a rate mechanism based on ER mechanism and adsorption of methanol as the rate
determining step. The LHHW elementary mechanism with methanol adsorption as a rate limiting
step involving three parameters, the rate coefficient for methanol adsorption k MeOH , the
adsorption equilibrium coefficient of the overall transesterification reaction K eq and the
adsorption equilibrium constant of the alcohols K A , is thus statistically more reliable than the
mechanism with the assumption of surface reaction as the rate limiting step. The kinetic rate
constants obtained are shown in Table 8. Similar to all other mechanisms, adsorption of
methanol is identified as the slowest and the rate determining step with the rate constants of
9.810-3, 1.5310-2, 1.3710-2 and 0.06, for Mg0.81Al, Mg1.38Al, Mg1.82Al and Mg2.93Al
respectively. 2 of 0.052, 0.004, 0.033, and 0.011 achieved for Mg0.81Al, Mg1.38Al, Mg1.82Al and
Mg2.93Al (Table 8) respectively is less than 1.34 required for 3 parameter models with 8 degrees
of freedom for 99.5% level of significance29. Thus, LHHW mechanism with methanol adsorption
as the rate determining step represents the given experimental observations in Appendix A,
adequately.

Hattori elementary reaction mechanism (Methanol adsorption as rate limiting)

As discussed in the previous section the formation of intermediates is an important element in

the Hattori elementary reaction model (Table 6) that differentiates it from the LHHW and ER
mechanisms. The kinetic rate constants in the Hattori mechanism with methanol adsorption as
the rate determining step are shown in the Table 8. The slowest reaction rate is the adsorption of

13

methanol (K1) as expected, with the values of 4.4510-3, 5.0910-3, 8.1110-3 and 0.014 for
Mg0.81Al, Mg1.38Al, Mg1.82Al and Mg2.93Al respectively. The fastest reaction rates are K3,
corresponding to the reaction between adsorbed methanol and adsorbed triglyceride, 0.16 and
0.58 for Mg0.81Al and Mg2.93Al and K4, the decomposition of intermediate species [TsCH3OH*]
(Table 3), 0.29 and 0.32 for Mg1.38Al and Mg1.82Al, respectively. Table 8 indicates 2 of 0.05,
0.14, 0.30 and 0.009 for the four hydrotalcite catalysts with increasing Mg concentration,
respectively. However, since the number of experimental points for this mechanism is the same
as the number of kinetic parameters, statistical significance criteria cannot be applied to this
model.
Comparison between kinetic models

In the previous section, the kinetic rate constants and the model fit 2 with the assumptions of
quasi steady state, methanol adsorption and surface reaction as rate limiting steps in ER, LHHW
and Hattori elementary reaction mechanisms, are determined in Table 8. The increase in the
number of parameters increases the complexity of the model and reduces the limit on 2 for the
statistical significance of the fit29. Hence, different models based on the statistical criterion PAB as
defined below29 are further compared.

A2
PAB =

2
B

(N n A )

11

( N nB )

Here, A2 , B2 are the Chi-square, while n A , nB are the number of parameters, for model A and B
respectively and N is the number of experimental points. If PAB is lesser than one, model A fits
the data better than model B and vice versa. The number of parameters for a model fit should be
less than the number of experimental points by at least one. Overall reaction rate determined for
Hattori elementary reaction with methanol adsorption as the rate determining step has 12
parameters which are the same as the number of experimental points. Hence, this model cannot
be used for statistical analysis of this set of experimental data.
A comparison of performance using the statistical criterion PAB between the kinetic models on the
four hydrotalcite catalysts is shown in Table 9. The least number of parameters (in this case 3)
are involved in LHHW and ER mechanisms with methanol adsorption as the rate determining

14

steps. Hence, these two mechanisms would be most recommended ones from statistical
reliability point of view. At the same time, simpler, but adequately detailed reaction kinetics
model can be integrated to multiscale reactor simulation frameworks24. By comparing the
PAB values in Table 9, the following sequences from the best performing to the worst performing

mechanisms for individual catalysts are obtained, Mg0.81Al: ER (Methanol adsorption) > LHHW
(Surface reaction) > ER (Quasi steady state) > LHHW (Methanol adsorption); Mg1.38Al: LHHW
(Methanol adsorption) > ER (Methanol adsorption) > LHHW (Surface reaction) > ER (Quasi
steady state); Mg1.82Al: LHHW (Methanol adsorption) > ER (Quasi steady state) > LHHW
(Surface reaction) > ER (Methanol adsorption); Mg2.93Al: ER (Quasi steady state) > LHHW
(Methanol adsorption) > ER (Methanol adsorption) > LHHW (Surface reaction); Hence, the
LHHW (Methanol adsorption) provides consistently better representation of the experimental
data compared to ER (methanol adsorption), except Mg0.81Al, to which ER (methanol
adsorption) applies better than any other mechanism, illustrated in Table 9. Also, considering
lower conversion resulting with lower molar fraction of Mg in hydrotalcite catalyst (Appendix
A), biodiesel reactors are expected to incorporate hydrotalcite catalysts with higher molar
fraction of Mg, in which cases LHHW with methanol adsorption as the rate determining step
adequately and reliably represents the kinetic data. It also satisfies 2 limit of 1.3429 for all four
catalysts.

Table 9: Statistical comparison between kinetic models

4 Conclusions
Three kinetic mechanisms, ER, LHHW, and Hattori, based on assumptions of quasi steady state
for the surface species and methanol adsorption and surface reaction as rate limiting steps were
investigated for biodiesel production reaction between triglyceride and methanol over
heterogeneous hydrotalcite catalyst16. These kinetic models were applied to represent four
hydrotalcite catalysts with different molar compositions of Mg and Al. Activity coefficients were
used to account for the non-ideal behaviour in this analysis. These kinetic models were observed
to give a good fit with the experimental data. The models were compared based on the chi
square 2 criteria and the number of parameters in the model. The LHHW kinetic mechanism

15

with methanol adsorption as the rate limiting step involved least number of parameters and was
identified as the best fit for the experimental data.
To account for the effect of the surface coverage on catalysts, KMC simulations were performed.
Further, mean field simulation of the bulk phase was combined with the surface KMC simulation
in order to capture both the changes in the concentration profiles in the bulk as well as on the
catalyst surface, simultaneously. The assumptions made for given mechanisms on all catalysts
were reinforced by the results of surface coverage and bulk concentration evolutions with time.
The most applicable reaction mechanism for individual catalysts was identified using the
proposed strategy. Also, statistically most reliable mechanism was identified.

Acknowledgement:

Financial support from EPSRC (EP/D04829X/1) of the UK for undertaking this research is
gratefully acknowledged.

Nomenclature

[i]

activity of specie i, mol m-3

Ci

concentration of specie i, mol m-3

Ci ( j )

concentration of specie i at time point j, mol m-3

Ciexp erimental ( j )

concentration of specie i obtained from experimental studies at time

point j, mol m-3

CH3OH*

Methanol adsorbed, dimensionless

CH3OH

Methanol bulk, dimensionless

D*

Diglyceride adsorbed, dimensionless

Diglyceride bulk, dimensionless

G*

Glycerol adsorbed, dimensionless

Glycerol bulk, dimensionless

KA

adsorption equilibrium constant of the alcohols present, m3 mol-1

Keq

equilibrium coefficient of the overall transesterification reaction,

dimensionless

kMeOH

rate coefficient for methanol adsorption, s-1

16

kj

forward reaction rate constant for elementary reaction j, variable units

Kj

Equilibrium constant for elementary reaction j, dimensionless

li

UNIFAC method parameter for specie i

M*

Monoglyceride adsorbed, dimensionless

Monoglyceride bulk, dimensionless

MeOl

Methyl Oleate bulk, dimensionless

nspc

number of species, dimensionless

ntime

total number of experimental values, dimensionless

PAB

statistical criteria to compare model A and B, dimensionless

nA

number of parameters in model A, dimensionless

nB

number of parameters in model B, dimensionless

number of experimental points, dimensionless

Qp

group area parameter

qi

molecular van der Waals surface area

rj

reaction rate for jth reaction, mol m-3

overall reaction rate expression, mol m-3

Rp

group volume

RSSQ

residual sum of squares, dimensionless

Ri

reaction rate of the specie i

RT

rate of consumption of T, mol m-3

RD

rate of consumption of D, mol m-3

RM

rate of consumption of M, mol m-3

RCH 3OH

Rate of consumption of CH 3OH , mol m-3

RG

rate of consumption of G, mol m-3

RMeOl

rate of generation of MeOl, mol m-3

si

molecular van der Waals volume

Sp

group area parameter

Triglyceride bulk, dimensionless

Te

Temperature, K

Time, s

17

v (pi )

number of p groups present in molecule i, dimensionless

xi

mole fraction of specie i, dimensionless

empty surface site, dimensionless

Symbols

iC

combinatorial factor for activity coefficient calculation, dimensionless

iR

residual factor for activity coefficient calculation, dimensionless

activity coefficient of species i, dimensionless

chi square, dimensionless

ip , aii '

group interaction parameters

segment fraction for specie i, dimensionless

area fraction for specie i, dimensionless

group residual activity coefficient, dimensionless

p(i )

residual coefficient of group p in reference solution containing only

molecules of type i, dimensionless

References

1.
Narasimharao, K.; Lee, A.; Wilson, K., Catalysts in production of biodiesel: A review.
Journal of Biobased Materials and Bioenergy 2007, 1, (1), 19-30.
2.
Dossin, T. F.; Reyniers, M. F.; Berger, R. J.; Marin, G. B., Simulation of heterogeneously
MgO-catalyzed transesterification for fine-chemical and biodiesel industrial production. Applied
Catalysis B-Environmental 2006, 67, (1-2), 136-148.
3.
Crocker, M. In Development of Heterogeneous Catalysts for Bio-diesel Production, TriState Catalysis Society Symposium, Lexington, KY, 2006; Lexington, KY, 2006.
4.
Ngaosuwan, K.; Lotero, E.; Suwannakarn, K.; Goodwin, J. G. J.; Praserthdam, P.,
Hydrolysis of Triglycerides using Solid Acid Catalysts. Industrial & Engineering Chemistry
Research 2009, 48, 4757-4767.
5.
Vyas, A. P.; Subrahmanyam, N.; Patel, P. A., Production of biodiesel through
transesterification of Jatropha oil using KNO3/Al2O3 solid catalyst. Fuel 2009, 88, (4), 625-628.
6.
Benjapornkulaphong, S.; Ngamcharussrivichai, C.; Bunyakiat, K., Al2O3-supported
alkali and alkali earth metal oxides for transesterification of palm kernel oil and coconut oil.
Chemical Engineering Journal 2009, 145, (3), 468-474.

18

7.
de Caland, L. B.; Santos, L. S. S.; de Moura, C. V. R.; de Moura, E. M., Preparation and
Study of Bimetallic Compounds Efficiency in the Synthesis of Biodiesel Fuel. Catalysis Letters
2009, 128, (3-4), 392-400.
8.
Singh, A. K.; Fernando, S. D., Transesterification of soybean oil using heterogeneous
catalysts. Energy & Fuels 2008, 22, (3), 2067-2069.
9.
Verziu, M.; Cojocaru, B.; Hu, J. C.; Richards, R.; Ciuculescu, C.; Filip, P.; Parvulescu,
V. I., Sunflower and rapeseed oil transesterification to biodiesel over different nanocrystalline
MgO catalysts. Green Chemistry 2008, 10, (4), 373-381.
10.
Brito, A.; Borges, M. E.; Otero, N., Zeolite Y as a heterogeneous catalyst in biodiesel
fuel production from used vegetable oil. Energy & Fuels 2007, 21, (6), 3280-3283.
11.
Dalai, A. K.; Kulkarni, M. G.; Meher, L. C., Biodiesel productions from vegetable oils
using heterogeneous catalysts and their applications as lubricity additives. 2006 IEEE EIC
Climate Change Conference, Vols 1 and 2 2006, 517-524.
12.
Di Serio, M.; Cozzolino, M.; Giordano, M.; Tesser, R.; Patrono, P.; Santacesaria, E.,
From homogeneous to heterogeneous catalysts in biodiesel production. Industrial & Engineering
Chemistry Research 2007, 46, (20), 6379-6384.
13.
Di Serio, M.; Ledda, M.; Cozzolino, M.; Minutillo, G.; Tesser, R.; Santacesaria, E.,
Transesterification of soybean oil to biodiesel by using heterogeneous basic catalysts. Industrial
& Engineering Chemistry Research 2006, 45, (9), 3009-3014.
14.
Cantrell, D. G.; Gillie, L. J.; Lee, A. F.; Wilson, K., Structure-reactivity correlations in
MgAl hydrotalcite catalysts for biodiesel synthesis. Applied Catalysis A-General 2005, 287, (2),
183-190.
15.
Macedo, C. C. S.; Abreu, F. R.; Tavares, A. P.; Alves, M. B.; Zara, L. F.; Rubim, J. C.;
Suarez, P. A. Z., New heterogeneous metal-oxides based catalyst for vegetable oil transesterification. Journal of the Brazilian Chemical Society 2006, 17, (7), 1291-1296.
16.
Dossin, T. F.; Reyniers, M. F.; Marin, G. B., Kinetics of heterogeneously MgO-catalyzed
transesterification. Applied Catalysis B-Environmental 2006, 62, (1-2), 35-45.
17.
Raimondeau, S.; Vlachos, D. G., Recent developments on multiscale, hierarchical
modeling of chemical reactors. Chemical Engineering Journal 2002, 90, 3.
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Karpov, E. G.; Chaichenets, S.; Liu, W. K.; Qian, D., Mechano-kinetic coupling
approach for materials with dynamic internal structure. Philosophical Magazine Letters 90, (7),
471-480.
19.
Levchenko, I.; Ostrikov, K.; Khachan, J.; Vladimirov, S. V., Growth of carbon nanocone
arrays on a metal catalyst: The effect of carbon flux ionization. Physics of Plasmas 2008, 15,
(10).
20.
Majumder, D.; Broadbelt, L. J., A multiscale scheme for modeling catalytic flow
reactors. AIChE Journal 2006, 52, (12), 4214-4228.
21.
Vlachos, D. G.; Mhadeshwar, A. B.; Kaisare, N. S., Hierarchical multiscale model-based
design of experiments, catalysts, and reactors for fuel processing. Computers & Chemical
Engineering 2006, 30, (10-12), 1712-1724.
22.
Raimondeau, S.; Vlachos, D. G., The role of adsorbate-layer nonuniformities in catalytic
reactor design: multiscale simulations for CO oxidation on Pt. Computers & Chemical
Engineering 2002, 26, (7-8), 965-980.
23.
Reese, J. S.; Raimondeau, S.; Vlachos, D. G., Monte Carlo Algorithms for Complex
Surface Reaction Mechanisms: Efficiency and Accuracy. Journal of Computational Physics
2001, 173, (1), 302-321.

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24.
Kapil, A.; Bhat, S. A.; Sadhukhan, J., Multiscale characterization framework for sorption
enhanced reaction processes. Aiche Journal 2008, 54, (4), 1025-1036.
25.
Bhat, S. A.; Sharma, R.; Gupta, S. K., Simulation and optimization of the continuous
tower process for styrene polymerization. Journal of Applied Polymer Science 2004, 94, (2),
775-788.
26.
Xu, M.; Bhat, S.; Smith, R.; Stephens, G.; Sadhukhan, J., Multi-objective optimisation of
metabolic productivity and thermodynamic performance. Computers and Chemical Engineering
2009, 33, (9), 1438-1450.
27.
Reid, R. C.; Praustnitz, J. M.; Poling, B. E., The Properties of Gases and Liquids. 4th ed.;
MacGraw-Hill, New York: 1987.
28.
Haupt, R.; Haupt, S. E., Practical Genetic Algorithms 2ed.; John Wiley & Sons Inc New
York, 2004; p 253.
29.
Kreyszig, E., ADVANCED ENGINEERING MATHEMATICS. 8 ed.; John Wiley & Sons,
Inc.: New York, 1999.

Appendix A
Experimental data

Wilson and coworkers14 developed a series of hydrotalcite catalyst with the general formulae of

[Mg

(1 x )

Al x (OH ) 2

] (CO )
x+

3 x/n

with x in a range of 0.250.55. Table 10 shows the nominal Mg:Al

ratio along with the distribution of Mg and Al in the bulk and surface of these catalysts. The
effect of increasing Mg fraction on the activity and surface area of these hydrotalcite catalysts is
shown in Table 10. With the increase in Mg content the surface area of the catalyst initially
decreases and then increases. The increase in activity with the increase in the Mg molar fraction
led to higher conversion of triglyceride and more production of methyl oleate.
The transesterification reactions were performed in stirred batch reactor at 333 K using 0.01 mol
(3 cm3) of glyceryl tributyrate and 0.3036 mol (12.5 cm3) methanol. The batch reactor was run
for 3 hours.

Table 10: Properties of hyrotalcite catalysts14

20

Appendix B
Genetic Algorithm (GA)

The GA algorithm used in this simulation is based on the studies by Bhat et al.25, Xu et al.26 and
Haupt and Haupt28. The algorithm is implemented in MATLAB.

Specify the initial inputs to the genetic algorithm. Population size is 1000, while
maximum number of iterations is 100000. The bounds of control variables (rate
constants) are specified between 10-1 and 2 orders of magnitude.

Initial chromosomes are generated, with each chromosome representing a feasible

solution in terms of decision variables.

The objective function is generated for these sets of rate constants.

The chromosomes are ranked based on the objective function.

The best x percent (50%) chromosomes are kept for the next iteration.

Generate a new set of chromosomes by mutation, crossover in remaining chromosomes.

The cost of the new chromosomes is evaluated on the objective function.

Simulations are repeated until objective function is a very low value within the expected
tolerance limits or the maximum number of iterations (100000) is exceeded.

21

Appendix C
Prediction of activity coefficients of species

In the UNIFAC method the activity coefficient ( i ) is made up of two parts: the first part
provides the contribution due to molecular shape, combinatorial factor ( iC ), and the other due to
the interaction between molecules, residual factor ( iR ), respectively 16.
12

ln i = ln iC + ln iR
ln iC = ln

+ 5qi ln i + li i
xi
xi
i

nspc

x l

13

i' i'

i'

Here, xi is the mole fraction, i and i are the segment and area fractions for specie i
respectively.
all groups

v (pi ) ln p ln p(i )

ln iR =

14

In these equations, p , p(i ) are the group residual activity coefficient and the residual coefficient
of group p in reference solution containing only molecules of type i.

i =

xi qi
i =
x i ' qi '

xi si
x i ' si '

i'

15

i'

si and qi are the measure of molecular van der Waals volume and molecular surface area

respectively.
li = 5(si qi ) (si 1)

si = v (pi ) S p qi = v (pi )Q p
p

16

S p and Q p are group volume and area parameters, v (pi ) is the number of p groups present in

molecule i. The group activity coefficient p is a function of area parameter Q p , area fraction

i and the group interaction parameter ip and aii ' . Te is the temperature.

nspc.
nspc

i pi

ln p = Q p 1 ln i ip nspc

i
i

i ' i i 'i

22

 a
ii ' = exp ii '
Te

17

23

List of figures
Figure 1: Overall methodology to determine reaction mechanisms
Figure 2: Multi-scale KMC/MF simulation methodology
Figure 3: Comparison between (a) conversion of Triglyceride (T); (b) moles of Diglyceride (D);
and (c) moles of Monoglyceride (M); for Mg2.93Al hydrotalcites obtained from ER quasi steady
state model
Figure 4: Time evolution of surface species from KMC simulation
Figure 5: Evolution of catalyst surface from KMC simulations; *(.), CH3OH*(), D*(+), M*(),
G*(). Case (a) * (100%), CH3OH*(0), D*(0), M*(0), G*(0) at t=0s; Case (b) * (2.9%),
CH3OH*(0.07%), D*(97.1%), M*(0), G*(0) at t=2000s ; Case (c) * (5.4%), CH3OH*(0.1%),
D*(43.9%), M*(25.3%), G*(25.3%) at t=10800s;

List of tables
Table 1: Activity coefficients of species
Table 2: Elementary reactions in ER mechanism
Table 3: Kinetic reaction rate expressions for ER quasi steady state mechanism
Table 4: Elementary reactions in LHHW mechanism
Table 5: Elementary reaction rate expressions for LHHW mechanism with surface reaction as
rate limiting
Table 6: Elementary reactions in Hattori mechanism
Table 7: Elementary reaction rate expressions for Hattori mechanism with methanol adsorption
as rate limiting
Table 8: Prediction of kinetic rate constants and 2 for different mechanisms and catalysts
Table 9: Statistical comparison between kinetic models
Table 10: Properties of hyrotalcite catalysts16

24

A new
hypothesis
on kinetic
mechanism

GA based
parametric
estimation

Multi-scale
KMC/ MF
simulations

Verify results in
terms of surface
coverage /
conversion profiles
with time

NO
All
mechanisms
done

YES
Statistical comparison between
mechanisms

Figure 6: Overall methodology to determine reaction mechanisms

25

Initial input
Surface concentration
Bulk concentration
Reaction data
Lattice information
t =0
Mean field simulation of bulk
time to
Update bulk concentration

KMC simulation for surface

species for time to

Update surface concentration

t = t+ to

NO
If t > total time

YES

STOP

Figure 7: Multi-scale KMC/MF simulation methodology

26

0.0035
0.9

0.003

0.8

0.0025

0.6
0.5

Diglyceride

Triglyceride Conversion

0.7

Experimental
Model

0.4

0.002

Experimental
Model

0.0015

0.3

0.001

0.2

0.0005
0.1

0
0

2000

4000

6000

8000

10000

12000

2000

4000

6000

8000

10000

12000

Time (s)

Time (s)

(a)

(b)
0.003

0.0025

Monoglyceride

0.002
Experimental

0.0015

Model

0.001

0.0005

0
0

2000

4000

6000

8000

10000

12000

Time (s)

(c)

Figure 8: Comparison between (a) conversion of Triglyceride (T); (b) moles of Diglyceride
(D); and (c) moles of Monoglyceride (M); for Mg2.93Al hydrotalcites obtained from ER
quasi steady state model

27

1
0.9

Surface coverage fraction

0.8
*
CH3OH*
D*
M*
G*

0.7
0.6
0.5
0.4
0.3
0.2
0.1
0

2000

4000

6000
Time (s)

8000

10000

12000

Figure 9: Time evolution of surface species from KMC simulation

28

250

200

150

100

50

0
50

100

150

200

250

100

150

200

250

100

150

200

250

(a)
250

200

150

100

50

0
50

(b)
250

200

150

100

50

0
50

(c)
Figure 10: Evolution of catalyst surface from KMC simulations; *(.), CH3OH*(), D*(+),
M*(), G*(). Case (a) * (100%), CH3OH*(0), D*(0), M*(0), G*(0) at t=0s; Case (b) *
(2.9%), CH3OH*(0.07%), D*(97.1%), M*(0), G*(0) at t=2000s ; Case (c) * (5.4%),
CH3OH*(0.1%), D*(43.9%), M*(25.3%), G*(25.3%) at t=10800s;

29

Table 11: Activity coefficients of species

i

T
3.15

D
0.85

M
0.49

G
0.89

CH3OH
1.01

MeOl
2.98

30

Table 12: Elementary reactions in ER mechanism

*+CH3OH

CH3OH*

(a)

CH3OH*+T
D*+MeOl

(b)

CH3OH*+D
M*+MeOl

(c)

CH3OH*+M
G*+MeOl

(d)

D*
D+*

(e)

M*
M+*

(f)

G*
G+*

(g)

18

31

Table 13: Kinetic reaction rate expressions for ER quasi steady state mechanism
Rate of
consumption of T

Rate of
consumption of D

Rate of
consumption of M

k 2 [T ]
RT =

1 + k 2 [T ] + k 3 [D ] + k 4 [M ] + k 2 [D ] + k 2 [T ] + k 4 [M ]

k1[CH 3OH ]
k6
k5
k 7

k3 [D ] k 2 [T ]
RD =

1 + k 2 [T ] + k3 [ D ] + k 4 [ M ] + k 2 [ D ] + k 2 [T ] + k 4 [ M ]

k1[CH 3OH ]
k6
k5
k7

k 4 [M ] k 3 [D ]
RM =

1 + k 2 [T ] + k 3 [D ] + k 4 [M ] + k 2 [D ] + k 2 [T ] + k 4 [M ]

k1[CH 3OH ]
k6
k5
k 7

Rate of
consumption of
CH 3OH

Rate of change for

G

RCH3OH

k7 k1[CH 3OH ]

RG =
k3 [T ] + k5 [ D ] + k7 [ M ]

Rate of generation
of MeOl

(k 5 [D] + k 3 [T ] + k 7 [M ])
=

1 + k 2 [T ] + k 3 [D] + k 4 [M ] + k 2 [D] + k 2 [T ] + k 4 [M ]

k1[CH 3OH ]
k6
k5
k 7

RMeOl

(
k 5 [D ] + k 3 [T ] + k 7 [M ])
=

1 + k 2 [T ] + k 3 [D] + k 4 [M ] + k 2 [D] + k 2 [T ] + k 4 [M ]

k1[CH 3OH ]
k6
k5
k 7

32

Table 14: Elementary reactions in LHHW mechanism

Elementary reactions
*+CH3OH
CH3OH*
T+*
T*

CH3OH*+T*
D*+MeOl*
CH3OH*+D*
M*+MeOl*
CH3OH*+M*
G*+MeOl*
MeOl+*
MeOl*
D+*
D*
M+*
M*
G+*
G*

Equilibrium reaction constants

[CH 3OH *]
[*][CH 3OH ]
[T *]
K2 =
[*][T ]
[D *][MeOl *]
K3 =
[CH 3OH *][T *]
[M *][MeOl *]
K4 =
[CH 3OH *][D *]
[G *][MeOl *]
K5 =
[CH 3OH *][M *]
[MeOl *]
K6 =
[*][MeOl ]
[D *]
K7 =
[*][D]
[M *]
K8 =
[*][M ]
[G *]
K9 =
[*][G ]
K1 =

33

Table 15: Elementary reaction rate expressions for LHHW mechanism with surface
reaction as rate limiting
Rate
Overall reaction rate
determining
reaction

*+CH3OH

CH3OH*

K 6 K 7 [D ][MeOl ]

k 2 [T ] 1
K 2 K K [CH OH ]
3 1
3

r2 =

K K [D ][MeOl ]
1 + K1 [CH 3OH ] + K 6 [MeOl ] + 6 7
+ K 7 [D ] + K 8 [M ] + K 9 [G ]
K 3 K1 [CH 3OH ]

T+*
T*

CH3OH*+T*

D*+MeOl*
CH3OH*+D*

M*+MeOl*
CH3OH*+M*

G*+MeOl*

MeOl*

K 6 K 7 [D ][MeOl ]

k1 [CH 3OH ] 1
K1 K K
[T ]
3 2

r1 =
K 6 K 7 [D ][MeOl ]

1 +
+ K 6 [MeOl ] + K 2 [T ] + K 7 [D ] + K 8 [M ] + K 9 [G ]
[T ]
K3 K 2

MeOl+*

D*
D+*

k3 K1 K 2 [CH 3OH ][T ] 1 K 7 K 6 [D ][MeOl ]

K3

r3 =
(1 + K1 [CH 3OH ] + K 6 [MeOl ] + K 2 [T ] + K 7 [D] + K 8 [M ] + K 9 [G ])2
k 4 K1 K 7 [CH 3OH ][D ] 1 K 8 K 6 [M ][MeOl ]
K4

r4 =
(1 + K1 [CH 3OH ] + K 6 [MeOl ] + K 2 [T ] + K 7 [D] + K 8 [M ] + K 9 [G ])2
k5 K1 K 8 [CH 3OH ][M ] 1 K 9 K 6 [G ][MeOl ]
K5

r5 =
(1 + K1 [CH 3OH ] + K 6 [MeOl ] + K 2 [T ] + K 7 [D] + K 8 [M ] + K 9 [G ])2
K K K [T ][CH 3OH ]

k6 3 2 1
K 6 [MeOl ]
K 7 [D ]

r6 =

K K K [T ][CH 3OH ]
1 + K1 [CH 3OH ] + 3 2 1
+ K 2 [T ] + K 7 [D ] + K 8 [M ] + K 9 [G ]
K 7 [D ]

K K K [T ][CH 3OH ]

k 7 3 2 1
K 7 [D ]
K 6 [MeOl ]

r7 =

K K K [T ][CH 3OH ]
1 + K1 [CH 3OH ] + K 6 [MeOl ] + K 2 [T ] + 3 2 1
+ K 8 [M ] + K 9 [G ]
K 6 [MeOl ]

34

M*
M+*

G*
G+*

K K K [D ][CH 3OH ]

k8 4 1 7
K 8 [M ]
K 6 [MeOl ]

r8 =

K K K [D ][CH 3OH ]
1 + K1 [CH 3OH ] + K 6 [MeOl ] + K 2 [T ] + K 7 [D ] + 4 1 7
+ K 9 [G ]
K 6 [MeOl ]

K K K [M ][CH 3OH ]

k9 5 8 1
K 9 [G ]
K 6 [MeOl ]

r9 =

K K K [M ][CH 3OH ]
1 + K1 [CH 3OH ] + K 6 [MeOl ] + K 2 [T ] + K 7 [D ] + K 8 [M ] + 5 8 1

K 6 [MeOl ]

35

Table 16: Elementary reactions in Hattori mechanism

Elementary reactions
*+CH3OH
CH3OH*
T+*
T*
CH3OH*+T*
[TsCH3OH]*+*

[TsCH3OH]*
D*+ MeOl

CH3OH*+D*
[DsCH3OH]*+*
[DsCH3OH]*
M*+ MeOl
CH3OH*+M*
[MsCH3OH]*+*
[MsCH3OH]*
G*+ MeOl
D+*
D*
M+*
M*
G+*
G*

Equilibrium reaction constants

[CH 3OH *]
[*][CH 3OH ]
[T *]
K2 =
[*][T ]
[*][TsCH 3OH *]
K3 =
[CH 3OH *][T *]
[D *][MeOl ]
K4 =
[TsCH 3OH *]
[*][DsCH 3OH *]
K5 =
[CH 3OH *][D *]
[M *][MeOl ]
K6 =
[DsCH 3OH *]
[*][MsCH 3OH *]
K7 =
[CH 3OH *][M *]
[G *][MeOl ]
K8 =
[MsCH 3OH *]
[D *]
K9 =
[*][D]
[M *]
K10 =
[*][M ]
[G *]
K11 =
[*][G ]
K1 =

36

Table 17: Elementary reaction rate expressions for Hattori mechanism with methanol
adsorption as rate limiting
Rate
Overall reaction rate

determining
reaction

*+CH3OH

CH3OH*

K9
[D][MeOl ]
k1 [CH 3 OH ] 1
K1 K K K
[T ]
4 3 2

r1 =

K9
[D][MeOl ] + K 9 [D][MeOl ] + K 10 [M ][MeOl ] + K 11 [G ][MeOl ] + K [T ] + K [D ] + K [M ] + K [G ]
1 +
2
9
10
11

[T ]
K
K
K
K4
K6
K8
4 3
2

K9
[D ][MeOl ]
k 2 [T ] 1
K 2 K K K [CH OH ]
4
3 1
3

r2 =

K 9 [D ][MeOl ] K 10 [M ][MeOl ] K 11 [G ][MeOl ]

K9
[D][MeOl ] + K [D ] + K [M ] + K [G ]
1 + K 1 [CH 3 OH ] +
+
+
+
9
10
11

K4
K6
K8
K 4 K 3 K 1 [CH 3 OH ]

T+*
T*
CH3OH*+T*

r3 =

[TsCH3OH]*

K9
k 3 K 1 K 2 [CH 3 OH ][T ] 1
[D ][MeOl ]
K3 K
4

K [D ][MeOl ] K 10 [M ][MeOl ] K 11 [G ][MeOl ]

1 + K 1 [CH 3 OH ] + 9
+
+
+ K 2 [T ] + K 9 [D ] + K 10 [M ] + K 11 [G ]
K4
K6
K8

+*
[TsCH3OH]*

D*+

r4 =

MeOl
CH3OH*+D

r5 =

[DsCH3OH]

k 4 K 3 K 2 K 1 [CH 3 OH ][T ] 1
K [D ][MeOl ]
K4 9

K [M ][MeOl ] K 11 [G ][MeOl ]
1 + K 1 [CH 3 OH ] + K 3 K 2 K 1 [CH 3 OH ][T ] + 10
+
+ K 2 [T ] + K 9 [D ] + K 10 [M ] + K 11 [G ]
K6
K8

K10
k 5 K 1 K 9 [CH 3 OH ][D] 1
[M ][MeOl ]
K5 K
6

K [D][MeOl ] K10 [M ][MeOl ] K 11 [G ][MeOl ]

1 + K1 [CH 3OH ] + 9
+
+
+ K 2 [T ] + K 9 [D] + K 10 [M ] + K 11 [G ]
K4
K6
K8

*+*
[DsCH3OH]
*
M*+

r6 =

MeOl
CH3OH*+M

r7 =

[MsCH3OH]

k 6 K 5 K 9 K 1 [CH 3 OH ][D ] 1 K 10 [M ][MeOl ]

K6

K [D ][MeOl ]
K [G ][MeOl ]
1 + K 1 [CH 3 OH ] + 9
+ K 5 K 9 K 1 [CH 3 OH ][D ] + 11
+ K 2 [T ] + K 9 [D ] + K 10 [M ] + K 11 [G ]
K
K
4
8

K 11
k 7 K 1 K 10 [CH 3OH ][M ] 1
[G ][MeOl ]
K7 K
8

K [D ][MeOl ] K 10 [M ][MeOl ] K 11 [G ][MeOl ]

1 + K 1 [CH 3OH ] + 9
+
+
+ K 2 [T ] + K 9 [D ] + K 10 [M ] + K 11 [G ]
K4
K6
K8

*+*
[MsCH3OH]
*

G*+

r8 =

k 8 K 7 K 10 K 1 [CH 3 OH ][M ] 1 K 11 [G ][MeOl ]

K8

K [D ][MeOl ] K 10 [M ][MeOl ]
1 + K 1 [CH 3 OH ] + 9
+
+ K 7 K 10 K 1 [CH 3 OH ][M ] + K 2 [T ] + K 9 [D ] + K 10 [M ] + K 11 [G ]
K4
K6

37

MeOl
D*
D+*

M*
M+*

G*
G+*

K 10 [M ][MeOl ]

k 9
K 9 [D ]
K 5 K 6 K 1 [CH 3 OH ]

r9 =

K 9 [D ][MeOl ] K 10 [M ][MeOl ] K 11 [G ][MeOl ]

K 10 [M ][MeOl ]
1 + K 1 [CH 3 OH ] +
+
+
+ K 2 [T ] +
+ K 10 [M ] + K 11 [G ]
K4
K6
K8
K 5 K 6 K 1 [CH 3 OH ]

K 11 [G ][MeOl ]

k10
K 10 [M ]
K 7 K 8 K 1 [CH 3 OH ]

r10 =

K 9 [D ][MeOl ] K 10 [M ][MeOl ] K 11 [G ][MeOl ]

K 11 [G ][MeOl ]
+
+
+ K 2 [T ] + K 9 [D ] +
+ K 11 [G ]
1 + K 1 [CH 3 OH ] +
K
K
K
K
K
K
[
CH
OH
]
4
6
8
7
8 1
3

[CH 3 OH ][M ]

k 11 K 8 K 7 K 1 K 10
K 11 [G ]
[MeOl ]

r11 =

K 9 [D ][MeOl ] K 10 [M ][MeOl ] K 11 [G ][MeOl ]

[CH 3 OH ][M ]
1 + K 1 [CH 3 OH ] +
+
+
+ K 2 [T ] + K 9 [D ] + K 10 [M ] + K 8 K 7 K 1 K 10
K4
K6
K8
[MeOl ]

38

Table 18: Prediction of kinetic rate constants and 2 for different mechanisms and
catalysts
ER quasi steady state

k
1
2
3
4
5
6
7

Mg0.81Al
1.01E-05
0.0101
0.1674
0.3307
0.0381
0.0086
0.088

Mg1.38Al
4.43E-06
0.0495
0.0271
0.4590
0.0519
0.1305
0.0031

Mg1.82Al
0.0001
0.0980
0.1186
0.0274
0.0504
0.1260
0

Mg2.93Al
0.0001
0.0390
0.1741
0.3587
0.0564
0.1579
0.0082

0.0174
0.2661
0.0218
0.0044
ER methanol adsorption as rate determining
K
Mg0.81Al
Mg1.38Al
Mg1.82Al
Mg2.93Al
kf
1.60E-06
1.71E-06
7.33E-06
7.12E-06
KA
0.0184
0.0130
0.0437
0.0206

0.0276
0.0322
0.1772
LHHW surface reaction as rate limiting
K
Mg0.81Al
Mg1.38Al
Mg1.82Al
Mg2.93Al
1
5.97E-05
1.00E-04
3.30E-05
2
0.0850
0.0533
0.1353
3
0.1613
0.1873
0.1509
4
0.3729
0.4816
0.0319
5
0.0764
0.0456
0.0307
6
0.1709
0.0128
0.0121
7
0.0006
0.0026
0.0041
8
0.0319
0.0402
0.0118
9
0.0927
0.0621
0.0399
k1
0.0195
0.0226
0.0664

0.0129

0.0001
0.1665
0.1784
0.4442
0.0326
0.0608
0.0013
0.0499
0.0522
0.0202

0.0061
0.0203
0.0092
0.0129
LHHW methanol adsorption as rate limiting
K
Mg0.81Al
Mg1.38Al
Mg1.82Al
Mg2.93Al
kf
9.80E-03
1.53E-02
1.37E-02
0.0611
KA
0.0003
0.0125
0.0223
0.0009
Keq
0.0312
0.0009
0.0013
0.0348

0.0521
0.0041
Hattori methanol adsorption as rate determining
K
1
2
3
4

0.0333

0.0114

Mg0.81Al
Mg1.38Al
Mg1.82Al
Mg2.93Al
4.45E-03
5.09E-03
8.11E-03
0.0140
0.0945
0.1376
0.0216
1.4572
0.1642
0.1607
0.1662
0.5854
0.1218
0.2941
0.3244
0.4282

39

5
6
7
8
9
10
11
k1

0.0119
0.1344
0.0186
0.0750
0.0001
0.0502
0.0644
0.0002

0.0498
0.1392
0.0073
0.0318
0.0018
0.0024
0.0637
0.0006

0.0146
0.1893
0.0684
0.0194
8.34E-05
0.0887
0.0130
8.05E-05

0.0708
0.0289
0.0639
0.0648
0.0151
0.0782
0.0115
0.0080

0.0515

0.1454

0.2988

0.0092

40

Table 19: Statistical comparison between kinetic models

Mg1.38Al
Mg0.81Al
PAB

Mg1.82Al

Mg2.93Al

ER (Methanol LHHW
adsorption)
(Methanol
adsorption)
ER (Quasi
ER (Methanol
steady state)
adsorption)
ER (Methanol
LHHW
adsorption)
(surface
reaction)
LHHW
LHHW
(Surface
(Methanol
reaction)
adsorption)
LHHW
ER
(Quasi
(Methanol
steady state)
adsorption)

0.4773

7.0169

4.7893

1.0210

1.2623

16.5059

0.2459

0.6784

0.9129

0.3168

3.8518

0.2000

0.5229

22.1496

1.2434

5.1051

1.6597

0.0086

0.8489

1.4437

41

Table 20: Properties of hyrotalcite catalysts16

Catalyst composition
Mg0.81Al

Nominal Mg:Al
ratio
1:1

Surface area
2
(m /g)

Activity/mmolmin
1
-1
.g(cat)

Glyceryl
Tributyrate
Conversion %

166.48.3

0.004

42.4

Mg1.38Al

2:1

121.96.1

0.01

49.2

Mg1.82Al

3:1

92.54.6

0.024

55.3

Mg2.93Al

4:1

104.15.2

0.025

74.8

42