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pubs.acs.org/IECR

Computer Simulation of Fatty Acid Esterification in Reactive

Distillation Columns
Guilherme Duenhas Machado, Donato A. G. Aranda, Marcelo Castier,,|| Vladimir Ferreira Cabral,*, and
L
ucio Cardozo-Filho

Departamento de Engenharia Qumica, Universidade Estadual de Maring
a, Av. Colombo 5790, Maring
a, PR, 87020-900, Brazil
Departamento de Engenharia Qumica, Escola de Qumica
Universidade Federal do Rio de Janeiro, Av. Hor
acio Macedo 2030,
Rio de Janeiro, RJ, 21941-909, Brazil

Chemical Engineering Program, Texas A & M University at Qatar, PO Box 23874, Doha, Qatar

ABSTRACT: This work presents computational steady-state simulations of fatty acid esters (biodiesel) production in a reactive
distillation column. Reaction rates were considered explicitly in the model of each stage. The procedures and formulation used here
were initially validated by comparison of simulations results obtained in this work with data available in the literature. Two new cases
for fatty acid esters (biodiesel) production are simulated. In both of them, conversions close to 99% are possible with the proper
choice of operating conditions, as shown by sensitivity analyses. The simulations results obtained here can be useful for the proper
design of processes that use reactive distillation columns for biodiesel production.

INTRODUCTION
Investments in renewable energy sources are increasingly
important due to economic issues and the problem of global
warming.1,2 Biodiesel (fatty acid alkyl esters) is a biodegradable
fuel produced from renewable sources. Recent studies3,4 show
that biodiesel can be a viable substitute for fossil diesel. Biodiesel
can be obtained by esterication or by transesterication using
homogeneous or heterogeneous reaction systems.5
13 Recent
studies14,15 show that the production of methyl esters of biodiesel
by transesterication reaction can be improved by the use of
metoxides as catalyst. In such papers the authors state that the use
of these catalysts can reduce the occurrence of the saponication
reaction. Recently, the noncatalytic reaction, using alcohol under
supercritical conditions at high temperatures and pressures, has
been investigated as an alternative method for fatty acid esters
production.16
20
Homogeneous transesterication of vegetable oils has been
the method most frequently used to produce biodiesel.21,22
However, this technique has several drawbacks, especially in
relation to the content of free fatty acids (FFA) and water in the
feedstock specication. In this process, saponication is undesired
but may occur depending on the reaction conditions and the free
acid content of the vegetable oil used. The existence of FFA and
water content in the reaction bulk favor soap generation, which
inhibits the separation of the alkyl esters and glycerol, and
contributes to emulsion formation during the washing step.23,24
As ways of overcoming the limitations of the conventional
process, alternative catalysts and chemical reactions can be
evaluated. The use of heterogeneous catalysis can be an alternative to conventional homogeneous catalysis. Production processes that use heterogeneous catalysis have the following
benets: (1) better removal of the catalyst and easy separation
of products, (2) high purity of glycerol, and (3) elimination of the
alkaline catalyst neutralization step.25
27
r 2011 American Chemical Society

Moreover, considering alternative types of chemical reactions,

hydroestericationhydrolysis followed by estericationis
very promising, with commercial biodiesel plants successfully
using this technology (e.g., Biobrax, in the Brazilian state of
Bahia). This strategy has two steps (hydrolysis and esterication)
and uses any fat material as raw material because hydrolysis
converts the fat in FFA. The biodiesel and glycerin produced in
this process have very high purity when compared with the
current method used to produce biodiesel. Niobium oxide
(Nb2O5) can be used as catalyst for both hydrolysis and
esterication steps in biodiesel production.28,29
The esterication of FFA with short-chain alcohols is another
way to produce biodiesel. In these processes, a previous step of
hydrolysis of oils and fats is used as a pretreatment to increase the
FFA concentration producing a more complete conversion. Such
a step increases the range of raw materials usable for biodiesel
production. Studies show that this reaction of fatty acid esterication is faster and occurs in a single step, unlike the three
stages of the transesterication of triglycerides.30,31 A catalytic
process for the heterogeneous esterication of fatty acids was
developed32 and the technology was applied in a 12 000 ton/year
biodiesel plant in Bel
em-PA-Brazil that started up in April 2005.
This procedure, however, still requires steps of chemical
reaction and products separation. This process could be even
more attractive if it could be run in a single integrated step, in
which reaction and separation occur in a single device, as in a
reactive distillation column.
Heterogeneously catalyzed reactive distillation oers advantages over the homogeneously catalyzed process. The synthesis of
methyl acetate by Eastman Chemicals using reactive distillation is
Received: November 17, 2010
Accepted: July 6, 2011
Revised:
July 4, 2011
Published: July 06, 2011
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Figure 1. Schematic of each theoretical stage along the reactive

distillation column.

regarded as a textbook example of this process. The process costs

were reduced (80%) by removing units and performing heat
integration. The conventional process, composed of 11 dierent
steps carried out in 28 pieces of equipment, was replaced by a single,
highly integrated reactive distillation column.33
35
The potential applicability of reactive distillation for biodiesel
production has motivated several publications such as those of
Silva et al.,36 He et al.,37 and especially those of Kiss et al.21,38
43
In this way, the objective of this work is to present new computer
simulations of fatty acid alkyl esters production in reactive
distillation columns. The simulation data obtained here can be
useful to develop and optimize processes to produce biodiesel
using hydroesterication. In the simulations, the formulation
used assumes steady-state operation and the reaction rates are
considered explicitly in the model of each stage. In the rst
example presented here, the formulation used in this work is
validated by comparing its results with experimental data and
simulations results available in the literature.56 Next, two new
simulations results of biodiesel production by esterication are
presented using kinetic data of fatty acid esterication that
employ niobium oxide as heterogeneous catalyst.44,45

METHODOLOGY
Reviews about the approaches used in these models of reactive
distillation columns are available in the literature.46,47 In this
paper, we assume steady-state operation and consider the reaction rates explicitly in the model of each stage. In all cases, for
simplicity, the Murphree eciency of separation was set equal to
100%. The same assumptions were used by Chen et al.46 and
Alfradique and Castier.47
The methodology takes additional considerations into account, analogous to the reactive distillation column using chemical equilibrium. Such considerations are detailed below. In the
energy balance, the heat of reaction is considered negligible when
compared to the value of heat of vaporization. There is heat
transfer in the reboiler and in the condenser, but the interior
stages of the column are adiabatic. The chemical reactions occur
only in the liquid phase and are controlled by chemical kinetics.
The possibility of vapor
liquid
liquid equilibrium (VLLE) is
not considered in the thermodynamic modeling. The occurrence
of VLLE has a strong dependence on the temperature and, for
most systems at a given pressure, there is a temperature above
which two liquid phases do not form. In all the simulations, the
assumption is that the operating temperatures along the reactive
distillation columns prevent the formation of two liquid phases.
Besides, the kinetic models used in the examples 2 and 3 are
obtained from experiments.44,45 These experiments were conducted under temperatures ranging from 150 to 200 C and, in

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this range, the occurrence of two dierent liquid phases was not
observed.
We consider pseudo-homogeneous kinetics that does not
account for the inuence of adsorption as a possible limiting
step to reaction rate. Each stage is considered as a continuous
stirred-tank reactor (CSTR). The stream of liquid and vapor
leaving the stages are in phase equilibrium, the vapor phase has
ideal gas behavior, and the liquid phase is considered as a
nonideal solution. Models of excess Gibbs free energy describe
the liquid phase behavior.
The general stage scheme used in this work is shown in
Figure 1:
The mass balance of component i on stage j is
f mi,j R j 1nIIi, j Zj 1nIi, j

nIIi, j 1 nIi, j
1 Fi, j

nr

i, kk, j 0
k1

where (Rj + 1)nIIi,j is the molar liquid ow rate of component i

leaving stage j, RjnIIi,j is its ow in the liquid sidestream, and nIIi,j is
its ow that reaches the next stage. (Zj + 1)nIi,j is the molar ow
rate of component i in the vapor leaving stage j, ZjnIi,j is its ow
rate in the vapor sidestream, and nIi,j is its ow rate that reaches
the next stage. In eq 1, Fi,j is the ow rate of of component i in the
feed stream to stage j, i,k is the stoichiometric coecient of
component i in reaction k, k,j is the extent of reaction k in stage j,
and nr represents the number of independent chemical reactions.
Assuming that the streams leaving each stage are in phase
equilibrium and the fugacity coecient in the vapor phase, the
Poynting factor, and the fugacity coecient of saturated vapor
are equal to 1, the isofugacity criteria is:
eq

f i, j lnxIi, j Pj
lnxIIi, j IIi, j Psat

i, j 0

where xIi,j and xIIi,j are the mole fractions of component i in the vapor
and liquid streams leaving stage j, Pj is the pressure of stage j, Psat
i,j is
the saturation pressure of component i on stage j and IIi,j is the
activity coecient of component i in the liquid phase leaving stage j.
The rate of reaction expression is used as follows:
!
nc
xIIi, j
r
3
f k, j ln kk, j Ri, k ln II
ln k, j 0
vj
i

where vIIj is the molar volume assuming an ideal liquid solution in

stage j, kk,j is the kinetic constant of reaction k in stage j, Ri,k is the
kinetic order of component i in reaction k. For kinetic data
correlated as function of activities, eq 3 becomes:
f rk, j ln kk, j

nc

i Ri, klnxIIi, j IIi, j
ln k, j 0

The energy balance in stage j is:

f hj R j 1H IIj Zj 1H Ij

H IIj 1 H Ij
1 H Fj Q j 0

where (Zj + 1)HjI and (Rj + 1)HjII are the enthalpy ow rates of
the vapor and liquid streams leaving stage j, and Qj is the rate of
heat added in each stage. HFj is the enthalpy ow rate of the feed
stream to stage j.
An additional equation species the behavior of the condenser and reboiler, based on a variable Ej, which is dened as
the ratio between the molar ow of vapor and liquid leaving
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Table 1. Ej Parameter Values for Each Mode of Operation of

Condenser and Reboiler
reboiler (stage 1)
partial

condenser (stage N)

total

partial

total

Z1 = 0

Z1 6 0

ZN = 0

ZN = 0

R1 = 0

R1 = 0

RN = 0

RN 6 0

E1 6 0

E1f

EN 6 0

EN = 0

stage j:
f vlj Zj 1

nc

nc

nIi, j
Ej Rj 1 i 1 nIIi, j 0
i1

For condensers and reboilers, the value of Ej is specied as

shown in Table 1. For each internal stage of the column, the value
of Ej is calculated.
The equations and unknowns are organized as described in
detail elsewhere.47,48 The formulation adopted here uses the
Newton
Raphson method to solve the mass and energy balances, phase equilibrium equations, rates of reaction equations,
and additional equations needed to match the number of degrees
of freedom. The Thermath package49 was used to obtain Fortran
subroutines that implement these equations and their derivatives
with respect to the process variables and the excess Gibbs free
energy model used in the simulation. The Fortran program used
in this work has about 10 800 lines of code.

THERMODYNAMIC MODELING
The calculation of thermodynamic properties is a key point in
simulating distillation, as this operation is based on the separation
of vapor and liquid phases. Ideal vapor phase is assumed (fugacity
coecient equal to unity) and the liquid phase is modeled
using excess Gibbs free energy equations such as UNIFAC,50
UNIQUAC,51 and UNIFAC Dortmund.52
The molar enthalpies of the liquid (hL) and vapor (hV) were
calculated using the following equations:
Z T
nc
L
xi
cLp, i dT hE
7
h

i1

h
V

nc

i1

T ref

Z
vap
yi hi

T ref

cLp, i dT

where hvap
i is the molar enthalpy of vaporization of component i
L
the molar
in the system, hE is the molar excess enthalpy, and cp,i
specic heat of component i in the liquid phase. The reference
temperature (Tref) used was 298.15 K. The Antoine equation53
was used to calculate the vapor pressure
ln Psat A

B
T C

The molar enthalpy of vaporization was calculated using the

Clausius
Clapeyron equation as follows:
dln Psat
10
dT
L
) and the parameters
The values of specic heat of liquids (cp,i
of Antoine equation were obtained from NIST54 and DIPPR55
databases.
vap

hi

Figure 2. Schematic of the reactive distillation column in all cases.

RESULTS AND DISCUSSION

This section presents three examples of fatty acid esterication
in reactive distillation columns. The rst example validates the
methodology used in this work by comparison of its results with
other simulations and experimental data available in the
literature.
The next two examples present new simulations of fatty acid
esterication. In Example 2, the simulations show the conventional operation of a reactive distillation column, while in
Example 3 the simulations try to reproduce the concept of
reactive absorption. In both cases, we use kinetic data of fatty
acid esterication using a niobium oxide catalyst.44,45 The
reactive distillation column setup shown in Figure 2 is used in
all simulations performed in this paper. The liquid phase was
modeled by the UNIFAC DORTMUND model45 in all cases.
Example 1: Esterification of Decanoic Acid with Methanol.
Steinigeweg and Gmehling56 studied this system experimentally.
Thus, these experimental data will be used to validate the
mathematical modeling applied in this work. Kiss et al.38
40
used the Aspen Plus software to simulate the same system in
reactive distillation columns. In those works, the authors used a
reaction kinetics model that considered metal oxides such as
niobic acid, sulfated zirconia, sulfated titania, and sulfated tin
oxide as catalyst.
Here, the esterication of decanoic acid (1) with methanol (2)
producing methyl decanoate (3) and water (4) is given by the
following stoichiometric relationship:
C9 H19 COOH CH 3 OH S C9 H19 COOCH 3 H2 O
1

11
The chemical reaction of esterication is considered to be of
rst order with respect to decanoic acid and methanol. The
inverse reaction (hydrolysis) is considered to be of rst order
with respect to methyl decanoate and water. These assumptions
are the same as those employed by Steinigeweg and Gmehling56
to develop a pseudo-homogeneous reaction rate model dependent on the activity of reagents:
r

RT 2

1 1 dni
k1 a1 a2
k
1 a3 a4
mcat vi dt

12

The catalyst used was a strongly acid ion-exchange resin

commercially called Amberlyst 15. The constants of the rate
equation for the catalyst according to the Arrhenius equation are
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Table 2. Specications of the Reactive Distillation Column

for Example 1
variable

specications

pressure
stages
condenser

all stages

1.0132 bar

total

20
stage 20

reboiler

partial

stage 1

reux ratio

condenser

0.5

reactive zone

stages 7
14
Katapak-SP packing lled with

catalyst

189.6 g

Amberlyst 15 resin
feed 1

0.250 (gmol/min)

stage 14

1.0132 bar, 331.19 K

decanoic acid
feed 2

0.483 (gmol/min))

stage 06

1.0132 bar, 337.65 K

Figure 3. Liquid phase composition along the reactive distillation column of

Example 1: Comparison of simulation results with experimental and simulated data.56

methanol

Table 3. Comparison between Simulation Results for Example 1 and Data from Literature56

top

bottom

liquid phase

Steinigeweg and

this

mole fraction

Gmehling (2003) experimental

work

0.000

0.000

0.000

0.716

0.760

0.763

0.000

0.000

0.000

0.277

0.240

0.237

1
2

0.366
0.303

0.428
0.220

0.511
0.103

0.303

0.332

0.386

0.001

0.000

temperature stage 1

0.000

363.53

363.49

stage 11

347.28

338.83

stage 20

341.27

341.39

42.99

42.99

conversion (% - decanoic acid)

given by the following:56




68710J=gmol
5
k1 9:1164 10 exp
mol=gs, TK
RT


k
1

In the extremes (top and bottom of the column), the results

are in excellent agreement with the experimental values. More
pronounced deviations occur in the intermediate stages. These
dierences between the simulation results of this study and the
literature56 can be attributed to some modeling issues. Here, eq 12,
a pseudo-homogeneous model, is used to model the reaction rate,
while the cited literature results are based on a heterogeneous
model that considers adsorption as a limiting step.
Figure 4 shows that the esterication reaction is favored close
to the feed location of fatty acid. This region has the highest
temperature of the reactive zone.
The good agreement between the simulation results and the
literature data suggests that the methodology adopted here
is valid.
Example 2: Esterification of Oleic Acid with Methanol. De
Pietre et al.55 and Alvarez et al.56 studied this reaction system with
emphasis on the development of catalysts.
This example evaluates a reactive distillation column for the
esterication of oleic acid (1) with methanol (2) producing
methyl oleate (3) and water (4) according to the following
stoichiometric relationship:
C17 H33 COOH CH 3 OH S C17 H33 COOCH 3 H2 O
1

13



64660J=gmol
1:4998 104 exp
mol=gs, TK
RT

14
The simulated column had 20 stages (reboiler, 18 adiabatic
plates, and condenser). The specications of the feed are
presented in Table 2.
The liquid phase was modeled by the UNIFAC DORTMUND
model.45 Table 3 shows the results obtained in the simulations of
this work.
Figure 3 shows the mole fraction proles in the liquid phase. In
general, the proles obtained in this work show the same
tendency as the experimental and simulation data available.
The largest deviations occur between stages 2 and 15. Figure 4
shows the temperature and the extents of the esterication
(direct) and hydrolysis (reverse) reactions along the column.

15
The chemical reaction of esterication is considered as second
order with respect to oleic acid and of zeroth order with respect
to methanol. It is assumed that the reverse reaction (hydrolysis)
does not occur, i.e., the esterication is irreversible. Gonc) alves44
used these assumptions in the development of a pseudo-homogeneous kinetic model as function of reagent concentration, as
follows:
r

1 1 dni
kC1 2
mcat vi dt

16

where C1 is the concentrations (gmol/L) of oleic acid in the

reaction mixture. Data for the kinetics of this reaction were
obtained from the cited experimental work. The kinetic constant in eq 16 is given by the Arrhenius equation:
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Figure 4. Temperature prole and extents of reaction along the reactive

distillation column of Example 1.

Figure 5. Composition prole in the liquid phase along the reactive

distillation column of Example 2.

Table 4. Specications of the Reactive Distillation Column

for Example 2
variable

specications

pressure

all stages

stages

1.0132 bar
15

condenser

total

stage 15

reboiler
reux ratio

partial
condenser

stage 1
0.001

reactive zone

stages 6
12

catalyst

niobium oxide powder

14.0 kg

feed 1

97.15(gmol/min)

stage 13

1.0132 bar, 418.1 K

oleic acid
feed 2

98.12 (gmol/min))

stage 06

1.0132 bar, 338.6 K

methanol


k 1:13exp



27209J=gmol
L=g cat min gmol, TK
RT

17
The simulated column has 15 stages: 1 reboiler, 13 adiabatic
plates, and 1 condenser. The specications of the feed are
presented in Table 4.
Figure 5 shows the proles of the liquid phase mole fractions
and Figure 6 shows the temperature and extent of the esterication reaction along the column.
The results of Figure 5 show that, in the liquid phase, the mole
fractions of the least volatile components, oleic acid and methyl
oleate, are higher at the bottom of the column. In the same gure,
the mole fraction of oleic acid decreases rapidly in the region
close to its feed stage, where a large rate of product formation
(methyl oleate) also occurs.
The temperature prole presented in Figure 6 is similar to that
of the previous example. The reactive zone presents higher
temperatures than neighboring stages where the reaction rates
are negligible. The highest temperature in the reactive zone is
close to the feed location of oleic acid, which is fed at a
temperature of 418 K. The conversion obtained was 97.1% and
can possibly be increased by adding more reactive stages to the
reactive zone of the simulated column.

Figure 6. Temperature prole and extents of reaction along the reactive

distillation column of Example 2.

Example 3: Esterification of Lauric Acid with Ethanol. Silva

et al.36 studied experimentally a system similar to this example,
and Kiss et al.38 used the Aspen Plus software to simulate this
system in reactive distillation columns. In the latter work, the
authors modeled the reaction kinetics considering different types
of catalyst (ion-exchange resins, calcium, and metal oxides). In all
cases, the authors simulated the conventional operation of a
reactive distillation column.
In the previous cases simulated here, the conventional operation of a reactive distillation column was used too. Reagents enter
the column as liquids and the heat transfer rate in the reboiler is
high in all cases, favoring the exposure of the product to high
temperatures in the reboiler. However, according to Kiss,40 it is
better to have a lower temperature prole in the column to
prevent thermal degradation of the fatty esters product.
With this motivation, in this example, we use a strategy that
minimizes the heat load in the reboiler. Therefore, ethanol is fed
at a temperature close to its saturation.
The esterication of lauric acid (1) with ethanol (2) producing
ethyl laurate (3) and water (4) follows the equation:

C11 H23 COOH C2 H5 OH S C11 H23 COOC2 H5 H2 O

1

18
The esterication reaction was considered to be of rst order
with respect to concentrations of lauric acid and ethanol, while
the inverse reaction (hydrolysis) follows a rst order kinetic with
respect to the concentrations of ethyl laurate and water. From
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Table 5. Specications of the Reactive Distillation Column

for Example 3
variable
pressure

specications
all stages

1.0132 bar

stages
condenser

total

20
stage 20

reboiler

partial

stage 1

reux ratio

condenser

0.002

reactive zone

stages 6
17

catalyst

niobium oxide powder

54.5 kg

feed 1

109.80(gmol/min)

stage 18

1.0132 bar, 480.15 K

lauric acid
98.12 (gmol/min))

feed 2

stage 06

Figure 7. Composition prole in the liquid phase along the reactive

distillation column of Example 3.

1.0132 bar, 351.15 K

ethanol

these assumptions, Le~ao45 proposed the following pseudohomogeneous model:

r

1 1 dni
k1 C1 C2
k
1 C3 C4
mcat vi dt

19

The constants k1 and k
1 in eq 19 obey the Arrhenius equation

as follows:



35027:62J=gmol
k1 1:54637 102 exp
L=g cat min gmol, TK
RT

20
k
1 7:323 exp

Figure 8. Temperature prole and extents of reaction along the reactive

distillation column of Example 3.




35005:81J=gmol
L=g cat min gmol, TK
RT

21
In this case, the column has 20 stages: 1 reboiler, 18 adiabatic
stages, and 1 condenser. The feed specications are presented in
Table 5.
Figure 7 shows the prole of the mole fractions in the liquid
phase of all compounds. Figure 8 shows the temperature prole
and extents of reaction along the column.
From Figure 7, we verify that the bottom product has a
signicant amount of ethanol. This is due to the lower heat
transfer rate used in the reboiler. Such heat transfer rate only
provides the heat needed for ethanol evaporation. In this
situation, almost all water is removed from the top as desired.
In Figure 8, the temperature in the reactive zone has maximum
value between stages 6 and 17. This range of conditions favors
the esterication reaction compared to the hydrolysis reaction,
because the kinetic constant k1 is higher than the kinetic constant
k
1 (see eqs 20 and 21).
In this example, the temperature at the bottom of the reactive
distillation column simulated is signicantly lower when compared to the previous case (Figure 6). This is due to the strategy
used in this example to minimize the heat tranfer rate in the
reboiler thus turning the case into a reactive absorption column.
This approach tends to reduce utilities consumption in the
column and prevent degradation of the ester formed in the
chemical reaction.

Figure 9. Composition surface of ethyl laurate (3) in the liquid phase of

the column simulated in Example 3: Eect of reux ratio.

Sensitivity Analysis. The influence of some variables such as

reflux ratio, number of stages, and the heat-tranfer rate in the
reboiler was observed.
In the sensitivity analysis of the reux ratio, such parameter
had its value xed between 0.002 and 10 for a column with 15
stages. In case the number of stages, we analyzed columns with
15
23 theoretical stages, while for heat-tranfer rate in the
reboiler, values between 1.35 and 10.5 MJ/min were used in a
column with 15 theoretical stages.
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Figure 12. Conversion of lauric acid versus reboiler heat transfer rate in
Example 3.
Figure 10. Temperature surface along the reactive distillation column
in Example 3: Eect of reux ratio.

Figure 11. Temperature surface along the reactive distillation column

in Example 3: Eect of reboiler.

The manipulation of the reboiler heat transfer rate was done

indirectly. In this case, the relationship between the vapor and
liquid in the reboiler (E1) was changed in order to obtain a
specic value of heat transfer rate in the reboiler (QR).
Figure 9 shows the ester mole fraction in the liquid phase along
the reactive distillation column as function of the reux ratio and
Figure 10 presents the temperature as function of the reux ratio.
Figures 11 and 12 present results for the variation of heat
transfer rate in the reboiler along the simulated column. Figure 13
exhibits the relationship between lauric acid conversion and
number of theoretical stages.
The increase in the reux ratio in the condenser increases the
water concentration in the reactive zone, favoring the hydrolysis
reaction (eq 21). Figure 9 shows that higher concentrations of
ethyl laurate are obtained in the bottom product when lower
values of reux ratio are used in the column. The increase of the
water concentration in the reactive zone also causes the decrease
in the temperature prole mainly in the reactive zone, as shown
in Figure 10.
From Figure 12, it is veried that an 8-fold increase in the heat
transfer rate in the reboiler increases lauric acid conversion by
only 2.4%, while there is a considerable increase in temperature in
this equipment, varying in the range of 382
531 K approximately

Figure 13. Conversion of lauric acid versus number of stages in

Example 3.

(see Figure 11). As the risk of product degradation raises with

higher bottom product temperature, increasing the heat transfer
rate in the reboiler is not advisible. It is preferable to use a heat
exchanger for preheating the alcohol stream before entering the
reactive distillation column. This procedure reduces the heat
transfer in the reboiler and may avoid exposing the bottom
product to high temperatures.
Figure 13 shows that an increase in the number of stages
increases the conversion of lauric acid. The column with 20
theoretical stages converts 98.7% of the lauric acid. This value is
higher than the minimum purity of 96.5% required by the
Brazilian laws for trading fatty acid esters (biodiesel).

CONCLUSIONS
In this work, fatty acid esterication in reactive distillation
columns was simulated computationally. The results obtained
here showed good agreement with experimental and simulated
data available in literature, validating the simulation procedures.
The second and third examples presented new simulation data of
fatty acid esterication in reactive distillation columns. In the
third example, a sensitivity analysis permitted determination of
suitable conditions for column operation. With these operating
conditions, conversions above 98% were obtained, which are
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Industrial & Engineering Chemistry Research

higher than the legal purity requirements for biodiesel trading in
Brazil. This mode of operation minimizes the heat transfer rate in
the reboiler, simulating the operation of a reactive absorption
column. As remarked by Kiss,40 in such equipment, the absence
of a reboiler tends to lower the xed and variable costs compared
with those of a reactive distillation column. However, economic
studies must be performed because some articles show that
reactive distillation is not of economic advantage although
equipment may be reduced. The techniques and procedures
presented here can be used for the design and optimization of
biodiesel production using reactive distillation.

AUTHOR INFORMATION
Corresponding Author

*Tel.: +55-4432614749. Fax: +55-4432614774. E-mail: vladimir@

deq.uem.br.
)

Present Addresses

On leave from the Federal University of Rio de Janeiro, Brazil.

ACKNOWLEDGMENT
This work was supported by CNPq (Grant 145465/2010-1)
and CAPES.
NOMENCLATURE
A, B, C = constants of Antoine equation
ai = activity of component i
Ci = molar concentration of component i
L
= liquid heat capacity of component i
cp,i
Ej = relation between the liquid and vapor streams in stage j
Fi,j = molar ow rate of the feed stream of component i to stage j
fi,jeq = phase equilibrium function of component i in stage j
fi,jm = mass balance function of component i in stage j
fjh = energy balance function at each stage
fjlv = function relating the liquid and vapor streams
r
fk,j
= chemical equilibrium function
I
Hj = total enthalpy of stream I at stage j
HIj+1 = total enthalpy of stream I at stage j+1
hE = molar excess enthalpy
hV = molar enthalpy of vapor stream
hL = molar enthalpy of liquid stream
HFj = total enthalpy ow rate of feed stream to stage j
kk,j = rate constant of reaction k in each stage j
mcat = catalyst mass per reactive stage
nIi,j = molar ow rate of component i in stream I of stage j
nIIi,j = molar ow rate of component i in stream II of stage j
Psat
i,j = saturation pressure of component i in stage j
Pj = pressure at stage j
Q j = heat load to stage j
R = universal gas constant
Rj = liquid side stream fraction at stage j
Tj = temperature at stage j
vIIj = liquid molar volume at stage j
xIi,j = mole fraction of component i in stream I of stage j
xIIi,j = mole fraction of component i in stream II of stage j
Zj = vapor side stream fraction at stage j

ARTICLE

Greek letters

Ri,k = kinetic order of component i in reaction k

IIi,j = activity coecient of component i in stream II of stage j
i,k = stoichiometric coecient of component i in reaction k
k,j = extent of reaction k at stage j
Subscripts/Superscripts

L, II = liquid
V, I = vapor
sat = saturation
i = component
k = reaction
F = feed
j = stage/component

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NOTE ADDED AFTER ASAP PUBLICATION

The version of this paper that was published ASAP July 28,
2011, was missing some text corrections. The revised version was
published August 9, 2011.

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