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Innovative process for fatty acid esters by dual

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Article in Computers & Chemical Engineering · March 2009

DOI: 10.1016/j.compchemeng.2008.09.020 · Source: DBLP

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 Computers and Chemical Engineering 33 (2009) 743–750

Contents lists available at ScienceDirect

Computers and Chemical Engineering

journal homepage: www.elsevier.com/locate/compchemeng

Innovative process for fatty acid esters by dual reactive distillation

Alexandre C. Dimian a,∗ , C.S. Bildea b , F. Omota, A.A. Kiss
a
Faculty of Science, University of Amsterdam, Nieuwe Achtergracht 166, 1018 VW Amsterdam, Netherlands
b
University POLITEHNICA of Bucharest, Department of Chemical Engineering, Str. Gh. Polizu 1, RO-011061, Bucharest, Romania

a r t i c l e i n f o a b s t r a c t

Article history: Catalytic reactive distillation offers new opportunities for manufacturing fatty acid esters, involved both
Received 31 March 2008 in biodiesel and specialty chemicals. A key problem is the effective water removal in view of protecting the
Received in revised form solid catalyst and avoiding costly recovery of the alcohol excess. This work proposes a novel approach based
14 September 2008
on dual esterification of fatty acid with light and heavy alcohols, namely methanol and 2-ethylhexanol.
Accepted 16 September 2008
These two complementary reactants have an equivalent reactive function but synergistic thermodynamic
Available online 15 October 2008
features. The setup behaves rather as reactive absorption combined with reactive azeotropic distillation
with heavy alcohol as co-reactant and water-separation agent. Another element of originality is the control
Keywords:
Conceptual design of chemical processes
of the inventory of alcohols by fixing the reflux of heavy alcohol and the light alcohol column inflow. This
Process simulation strategy allows achieving both stoichiometric reactant feed rate and large flexibility in ester production.
Reactive distillation The distillation column for recovering light alcohol from water is not longer necessary. The result is a
Fatty esters compact, efficient and easy-to-control multi-product reactive setup.
Biodiesel © 2008 Elsevier Ltd. All rights reserved.
Reactant inventory control

1. Introduction
Fatty acid esters are known from long date as high-value fine
chemicals used in cosmetics and produced traditionally by batch
processes. Today the main interest has shifted to biodiesel, whose
manufacturing at large scale asks for the development of innovative
and efficient processes. Typically the biodiesel consists of methyl
esters of different fatty acids present in natural triglycerides. Today
employing waste and non-edible raw materials is mandatory to
comply with the ecological and ethical requirements for biofuels.
Waste raw materials can contain a substantial amount of free fatty
acids (FFA), up to 100%. Accordingly, the development of an effi-
cient continuous process for fatty esters manufacturing is required
in which the use of a solid catalyst is highly desirable in order to
suppress costly chemical processing steps and waste treatment.
An innovative esterification process of fatty acids based on reac-
tive distillation was proposed (Omota, Dimian, & Bliek, 2003),
which makes use of super-acid solid catalyst, more specifically sul-
fated zirconia (SZr), capable of working at higher temperatures
from 130 to 200 ◦ C. More details about the equipment design can
be found in a recent book (Dimian & Bildea, 2008). When using a
solid catalyst, a generic problem is the removal of water, necessary
for shifting the chemical equilibrium to high conversion and con-
∗ Corresponding author.
E-mail address: a.c.dimian@uva.nl (A.C. Dimian).
sequently high ester purity, but also necessary for preserving the
catalyst activity. Several methods for enhancing the water removal
have been developed by the authors. When employing a heavy
alcohol, as 2-ethylhexanol (2EH), a favourable LLE allows separat-
ing the water as top product with high yield. When the alcohol
gives an azeotrope with water, as with propanols, finding a suitable
entrainer can solve the problem (Dimian, Omota, & Bliek, 2004).
Typically the entrainer can be a hydrocarbon, as cyclohexane, or a
light ester, or ether of the alcohol. However, this technique is not
workable for methanol, which is by far the most interesting alcohol
from market viewpoint. Additional separation equipment is needed
for recovering and recycling the methanol to reaction.
The analysis of this problem by residue curve map (RCM) rep-
resentation demonstrated that quantitative water removal can be
obtained by means of a reflux of fatty acid instead of alcohol (Omota
et al., 2003). In this case the process should be fed with a stoichio-
metric amount of methanol. As result, the column behaves rather
as reactive absorption than reactive distillation. This viewpoint
was confirmed experimentally in a laboratory column equipped
with Katapak packing hosting a resin-based Amberlyst-15TM cata-
lyst (Steinigeweg & Ghmeling, 2003). It was observed that using an
excess of methanol does not improve significantly the conversion.
Getting high acid conversion was problematic since the reac-
tion temperature with Amberlyst could not exceed 110 ◦ C. On the
contrary, using SZr catalyst allows operating at much higher tem-
peratures, up to 200 ◦ C, such to ensure complete acid conversion.
Note that recent superacidic resin catalysts, as Amberlyst-35TM or

0098-1354/$ – see front matter © 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.compchemeng.2008.09.020
744 A.C. Dimian et al. / Computers and Chemical Engineering 33 (2009) 743–750
Amberlyst-BD20TM , can work at higher temperatures. It can be
noted that the required acid conversion is determined by the purity
specifications of the ester. For example, the fatty acid conversion
should be at least of 99.95% when pharmaceutical ester quality is
required. In the case of biodiesel, the transesterification of glyc-
erides with base catalyst requires a feedstock with low free fatty
acid (FFA) content, preferably below 0.5%.
Putting in a shell, finding an effective method for water removal
in the esterification of fatty acids with methanol by reactive dis-
tillation was not solved by previous works. The water should be
eliminated quantitatively with the top product, while in bottom
product its concentration should be kept very low, typically below
1000 ppm. In addition, the occurrence of free-water phase should
be avoided in the reactive zone hosting the solid catalyst, while the
water concentration should be limited at most 2% weight. These
challenging aspects are tackled in the present study.
The paper is organized as follows. A first section presents the
conceptual design based on thermodynamic analysis in residue
curve maps, which give physical insights helping to understand
how the device works. It follows the simulation of the reactive
distillation setup. The next section discusses the operating parame-
ters from the perspective of purity specifications. Process dynamics
and control are considered in the last section. This approach allows
getting a compact and efficient design with robust controllability
properties.
2. Conceptual design
The feasibility of fatty acid esterification with individual alco-
hols may be studied by means of residue curve maps. Fig. 1 left
presents the RCM for the mixture 2-ethylhexanol (2EH)/lauric
acid/2-ethylhexanyl laurate/water, while Fig. 1 right for the mixture
methanol/lauric acid/methyl laurate/water, at atmospheric pres-
sure. Both diagrams display a large region of partial miscibility,
but with fundamental differences. For 2EH the immiscibility gap
regards both alcohol and fatty acid binary mixtures with water.
Operating the column with either alcohol or acid reflux is possible,
but for obvious reason the first is preferred. The top product will
contain a mixture alcohol/water from which quantitative separa-
tion of water is possible. Note that the solubility of 2EH in water
is very low (0.054 wt% at 25 ◦ C). However, when working above
100 ◦ C is necessary to avoid the presence of two liquid phases.
In the case of methanol the immiscibility gap embraces only the
water/acid binary, but approaching closely the methanol/water
edge. The top product is a binary mixture methanol–water which
should be submitted to further separation. For a temperature win-
dow of 130–160 ◦ C the use of vacuum is necessary in the case of
Fig. 1. RCM for dodecanoic acid esterification with 2EH (left) and methanol (right).
2EH, while pressures up to 20 bar are necessary when operating
with methanol. The dilution with alcohol of the bottom product is
necessary to avoid excessive reboiler temperature.
Superposing the two diagrams of Fig. 1 suggests how to solve
the water removal problem: adding 2EH in top could also remove
the water produced by the methanol. Thus 2EH could play simul-
taneously the role of reactant and mass separation agent (MSA).
Dual esterification with both heavy and light alcohol in a RD envi-
ronment appears attractive. Indeed, the sulfated zirconia catalyst
exhibit similar activity for both substrates. Moreover, by dilution
with inert material the catalyst activity and its distribution in the
column can be tailored to fulfil the requirements of the reactant or
MSA.
The effect of this modification on the operating pressure is sig-
nificant. Vacuum and high pressure was necessary when working
with heavy and light alcohol, respectively. By dual esterification the
operating pressure moves at low values, typically 2–3 bar, being
determined by the temperature profile maximizing the catalyst
performance in term of activity and selectivity.
It is interesting to note that the presence of fatty acid esters
of long-chain alcohols, such as of butanols or 2-ethyl-hexanol is
favourable for quality of biodiesel (Knothe et al., 2003). It increases
the cetane number and as result the combustion capability, but
does not affect the viscosity. In addition 2EH is a low cost secondary
product of n-butyraldehyde. Hence, the fatty esters of longer chain
alkyl alcohol improve the quality of biodiesel mixtures originating
from highly unsaturated feedstock, as rapeseed, palm, sunflower or
soybean oils.
3. Process flowsheet and computer simulation
Fig. 2 presents the process flowsheet. The key equipment is
the reactive distillation column (RDC). This contains in principle
three sections, upper separation, reaction and bottom separation,
to which three feeds of reactants are sent, respectively heavy alco-
hol, acid (oil) and light alcohol after preheating. Additional recovery
columns for recycling the excess of light alcohol are considered for
closing the material balance, although even a simpler flowsheet
will emerge at the end. The flowsheet was simulated by means of
AspenPlus software (AspenTech, 2007).
Kinetic data for esterification of dodecanoic acid with 2-
ethylhexanol and methanol are available from previous works
(Kiss, Dimian, & Rothenberg, 2006; Omota et al., 2003). Since
the reverse hydrolysis reaction is negligible, a simple kinetic
expression r = kCA CB can be used for simulation purposes. In this
case, the kinetic constants are k1 = 1.2 × 105 exp(−55,000/RT)
for the esterification of lauric acid with methanol and
 A.C. Dimian et al. / Computers and Chemical Engineering 33 (2009) 743–750
Fig. 2. Process flowsheet for dual fatty acid esterification.
k2 = 6 × 104 exp(−55,000/RT) for the reaction with 2-etylhexanol.
Note that the concentrations are in kmol/m3 , the activation energy
in kJ/kmol and the reaction rate is expressed kmol/(m3 h).
The thermodynamic model was Uniquac VLE for the RD section
and Unifac for LLE with interaction parameters as given in Aspen
PlusTM release 12. As in many other studies an equilibrium stage
model with liquid phase chemical kinetics can be considered as
reliable at the conceptual design stage.
Details about the RD column design are given in Table 1. The RD
column is equipped with catalytic structured packing, as Katapak-
STM from Sulzer. In the first approach the RD column has 20 stages,
the first four from top being devoted to water separation, the others
loaded with catalyst. Later the number of stages was raised to 25
for ensuring better flexibility in operation. A volumetric holdup of
0.05 m3 was assumed for each theoretical stage. This value is in
agreement with the sizing for BX packing available in Aspen Plus
when the column diameter is set at a constant value of 1.2 m.
The feed streams are preheated near the reaction temperature,
which in turn depends on the operating pressure. For example, in
a first attempt when the top column pressure is set at 1.5 bar the
reactant feeds are 100 kmol/h lauric acid at 140 ◦ C, 20 kmol/h 2-
ethylhexanol as liquid at 130 ◦ C on top stage, and 120 kmol/h liquid
methanol at the bubble point directly in the bottom.
Fig. 3 presents typical profiles of concentrations in liquid, reac-
tion rate and temperature. The results confirm the thermodynamic
analysis. The lauric acid is consumed mostly in the upper part of
745
the reaction zone, but additional trays are necessary to push the
conversion to completion. The heavy ester forms on the first three
reactive stages, while the light ester mostly in the middle part.
Accordingly, the reaction rate profiles show two distinct zones. The
water is entrained by 2-ethylhexanol on the first three non-reactive
stages, further condensed and removed in decanter. Water concen-
tration in liquid in the reaction zone can be kept low indeed, below
2 wt%.
By sensitivity analysis it was found that the reflux of heavy
alcohol is the key manipulated variable for controlling the water
content in the reactive liquid phase. Setting the reflux at a con-
venient value allows handling design uncertainties, as variable
catalyst activity, as well as operation disturbances, for example
a variation in fatty acid flow rate of about 10%. This finding was
confirmed by dynamic simulation. Moreover, fixing the reflux
flow rate is included in the control strategy proposed in this
work.
The reflux generates a recycle loop in majority of 2-ethylhexanol
around the top of the column. As discussed later, conditions can
be found to prevent it falling in bottoms. On the other side, the
excess of methanol passes preferentially in the bottom product,
but non-negligible amount can be found in the top water too. The
reboiler temperature may be varied on a large interval by means
of the content in methanol. For example a maximum temperature
of 250 ◦ C is obtained with 2 wt% methanol in bottoms, but dropped
below 170 ◦ C for about 6 wt% methanol.
746 A.C. Dimian et al. / Computers and Chemical Engineering 33 (2009) 743–750

Fig. 3. Profiles: concentration, temperature and reaction rate.

Table 1 Raising the distillate rate increases the purity of ester up to

Design details for simulating the RD set-up.
Parameter
Number of theoretical stages
Reactive stages
Lauric acid feed (kmol/h)
Methanol feed
2-Ethyl hexanol (make-up control)
Catalyst bulk density (kg/m3 )
Volume holdup per stage (m3 )
Mass catalyst per stage (kg)
Reflux flow rate (set) (kg/h)
Column diameter (m)
HETP (m)
Acid conversion (%)
Reboiler duty (set) (kW)
Condenser duty (kW)
Production (kg ester/h)
Productivity (kg ester/kg cat/h)
Bottom composition (mass fr.)
maximum 98%, while the purity of the water product is only
Value slightly affected. Further increase leads to both purities degrada-
25 including reboiler
tion. The diagram shows the make-up policy of methanol, which
20 from 5 to 24 starts from the stoichiometric value of 80 kmol/h. The optimum
vapour distillate is achieved at 113–114 kmol/h corresponding
100 kmol/h on stage 5 (3.5 bar, 150 ◦ C)
130 kmol/h directly in reboiler (4 bar, to a methanol consumption of 82.3 kmol/h, only slightly above
100 ◦ C) stoichiometry.
13.48 kmol/h in decanter (3.5 bar, The distribution of impurities in top and bottom products is of
130 ◦ C) significance too (Fig. 5). Increasing the distillate rate drops to zero
1050 all impurities in bottoms except methanol, which remains constant
0.050 (0.054 calc.) at 2% above 114 kmol/h. On the contrary, further methanol excess
in feed will pass only in the top product.
55
Regarding the reaction rate, Fig. 6 compares two situations:
2500 base-case and the stoichiometric feed. The heavy ester formation
1.2 remains in place, but the light ester migrates from an upper position
to a lower position. By stoichiometric balance no 2EH is found in
0.5
the base and no methanol in the top water. The methanol recovery
>99.99 column is no longer needed.
1750 The above results give insights about the optimal conditions for
−1492
operating the column. The central role of manipulating the reboiler
duty and the reflux flow rate is clearly identified. In the next sec-
22,333
tion, we will investigate the possibility of finding a suitable control
20.3 strategy that could bring the operation close to optimum faced with
Acid 650 ppb, H2 O 11 ppm, methyl ester various disturbances.
0.788, 2EH ester 0.174, MeOH 0.058

The temperature profile is directly correlated with the column

pressure. A flat profile in the reactive zone is preferred from catalyst
operation viewpoint. At 1.5 bar the temperature is almost constant
at 130 ◦ C, while at 3 bar it approaches 150 ◦ C. As Table 1 shows, when
working at 3.5 bar practically complete conversion of the fatty acid
is achieved and the purity specifications for the bottom product are
largely fulfilled. Note that the number of theoretical stages is raised
to 25, which ensure better flexibility and robustness in operation
too.

4. Product purity

Product purity is the most important issue, particularly in phar-

maceutical applications. As shown in Fig. 4, the purity of both
products strongly depends on the distillate flow rate. This was
selected as independent variable because it easily controllable by
the material and heat input. A minimum of 110 kmol/h is required Fig. 4. Purity of RDC products and methanol make-up as function of vapour distil-
for operation, but the purity of the bottoms is only 96.5%. late.
 A.C. Dimian et al. / Computers and Chemical Engineering 33 (2009) 743–750
Fig. 5. Impurities in top and bottom.
Fig. 6. Optimal reaction rate profile.
5. Process dynamics and control strategy
In this section, the dynamic behavior and control aspects
regarding the reactive distillation column are investigated. The con-
trollability of the system could be studied using tools from control
theory, for example indices based on a linear model. However, we
take a more practical approach and apply principles of plantwide
control to derive the structure of the control system. Then, the
performance of the control system is demonstrated by rigorous
dynamic simulation.
When several reactants are involved in the reaction–
separation–recycle systems, the strategy of controlling the
inventory of reactants is important in order to ensure stable plant
operation. This topic was studied systematically by Bildea and
Dimian (2003), Dimian and Bildea (2008), and Kiss, Bildea and
Dimian (2007) by means of nonlinear analysis. The conclusion is
that for the control of reactant inventory two strategies can be
adapted, as follows:
(1) Self-regulation strategy, when the reactant fresh feed is fixed.
This may work if the chemical reactor is large enough and the
747
per-pass conversion is high. The approach has the advantage of
setting directly the production rate, but the nonlinearity of the
plant could lead to undesired phenomena, such as state mul-
tiplicity and closed-loop instability, as well as high sensitivity
(snowball effects).
(2) Feedback control of the inventory, when the reactant inventory
is measured and a feedback control loop is implemented, with
the fresh feed as the manipulated variable. Thus, the increase
or decrease of the reactant inventory is compensated by less or
more reactant being added into the process. The strategy can
be implemented through the following steps:
• fix the reactor-inlet (recycle plus fresh feed) flow rate,
• determine the reactant inventory somewhere in the recycle
loop, by measuring appropriate level, pressure or concentra-
tion,
• adjust the fresh feed of reactant somewhere in a recycle loop
to keep its inventory at a constant value.
The concepts developed for reactor–separator–recycle systems are
also applicable to reactive distillation processes (Bildea, Omota,
Dimian, & Bliek, 2004). Al-Arfaj and Luyben (2000) discuss the pit-
falls of fixing the feed rate of all reactants of a reactive distillation
column. In the following work (Al-Arfaj & Luyben, 2002a; Al-Arfaj &
Luyben, 2002b), the authors demonstrate effective control schemes
for methyl-acetate and ETBE synthesis by reactive distillation. In
these control schemes, one reactant feed was set on flow control,
while the other reactant feed rate was used to control a concentra-
tion in the distillation column.
The system investigated in the present study involves three
reactants (lauric acid, methanol and 2EH) and two reactions (ester-
ification with light and heavy alcohols). The fatty acid conversion
is almost complete, which suggests to rely on self-regulation for
controlling the inventory of acid. On the contrary, the conversion
of alcohols is lower, both internal and external recycle rates hav-
ing significant values. Therefore, feedback will be employed for
controlling alcohols inventory.
Fig. 7 presents the process flowsheet diagram used for study-
ing process dynamics and control implementation. With respect to
Fig. 2 the following modifications can be noted:
748 A.C. Dimian et al. / Computers and Chemical Engineering 33 (2009) 743–750
Fig. 7. Final configuration and control strategy of the dual reactive distillation setup.
- the methanol recovery column (C-1) is no longer needed because
the design and control strategy will prevent methanol losses in
the top vapour;
- at the bottom of the column, a buffer vessel is included, fed with
both fresh and recycled methanol;
- methanol is fed directly as liquid in reboiler;
- heavy alcohol is fed directly in the two-phase decanter.
The following control strategy keeps the process at steady state
and is able to reject small disturbances:
1. Fresh lauric acid on flow control, according to the production
rate.
2. Fixed value for the reflux flow rate of organic phase, containing
heavy alcohol (a minimum value is required).
3. The make-up of heavy alcohol controls the level of organic-phase
in decanter.
4. Fixed value for the flow rate of methanol entering the column.
5. The make-up of methanol controls the level in the buffer vessel
containing the fresh and recycled methanol.
6. Column pressure controlled by condenser duty.
7. Temperature in the decanter controlled.
8. Water product controls the level of the water-phase in decanter.
9. Bottom product controls the level in reboiler.
It should be noted that, under this control structure, the reactants
are brought in the process in a ratio that satisfies the overall mass
balance imposed by the reaction stoichiometry and the phase equi-
librium at the top and the bottom of the reactive distillation column.
In contrast, control structures fixing the feed rates of all reactants
(acid, light- and heavy-alcohol) will not work in the presence of
small control implementation errors, the failure manifesting by the
accumulation or depletion of one reactant.
The above-described control structure was tested for larger dis-
turbances, for example a 10% increase in the acid feed flow rate.
Although the system settles in a new steady state, it was observed
that the excess of acid cannot be transformed in ester and leaves
the column with the bottom product. In a first attempt, the ratio
between the flow rates of methanol and acid entering the column,
and the ratio between the reboiler duty and the fresh acid flow
were fixed, in a feed-forward manner. This solution improves the
performance. However, when the production rate is decreased, too
much lauric acid is left in the bottom product. Moreover, when the
production rate is increased, too much methanol is sent to the top
of the column and leaves the system with the water stream. Clearly,
the control structure must employ at least a control loop concerning
product quality.
The solution employs a feedback control loop keeping constant
the temperature on the most-sensitive tray (21) by manipulating
the reboiler duty. Fig. 8 compares the temperature profiles for the
base-case, and for a 10% increase of the lauric acid flow rate with
and without temperature control.
Accurate control of the lauric acid concentration in the bottom
stream is achieved by making use of a concentration controller,
which prescribes the setpoint of the temperature controller in a
cascade structure. Keeping constant the ratios between the lauric
acid feed and the flow rate of methanol entering the column helps
keeping the reboiler temperature at a lower value. On the other
 A.C. Dimian et al. / Computers and Chemical Engineering 33 (2009) 743–750
Fig. 8. Temperature profiles along the reactive-distillation column.
hand, for the range of disturbances investigated in this study, no
significant improvement of the control performance was observed
by keeping at a constant value the ratio between lauric acid feed
and heavy alcohol reflux. It should be noted that, for the control
configuration presented here, the change of the lauric acid feed rate
leads to a change of methyl-ester production rate. In contrast, when
both ratios are constant, the change of lauric acid fee rate leads to
changes of both the methyl-ester and ethyl-hexyl ester production
rates.
Fig. 9 presents the performance of the control system for the
following scenario: the simulation starts from the steady state (feed
rate of lauric acid: 100 kmol/h) which is maintained for 0.5 h. Then,
the feed rate of lauric acid is increased to 110 kmol/h and after 1 h is
decreased to 90 kmol/h. Finally, the initial flow rate of 100 kmol/h
is restored. It can be observed that a change of the acid feed rate
results in a change of the light ester production rate having the same
magnitude, while the production rate of the heavy ester is constant.
The dynamics is fast, only 20 min being necessary to achieve the
new production rate. The amount of water obtained at the top of
the column reflects the amount of ester formed, but the dynamics is
much slower, over 1 h being necessary to reach the new stationary
value. During the entire transient period, the concentration of water
on the reactive trays remains below the 2 wt% limit.
Fig. 10 presents the temperature and the concentration of lauric
acid in the bottom stream, for the same scenario. It can be observed
that both variables remain very close to the base case values.
It should be noted that the tuning of the controllers is not crit-
ical with respect to the performance of the control system. In our
study, we set the parameters of the controllers as follows. The range
of the controlled variable was set to the nominal value ±10 ◦ C for
the temperature control loops, and the nominal value ±50% of it for
Fig. 9. Product flow rates for several changes of the lauric acid feed rate.
749
Fig. 10. Temperature and the concentration of lauric acid in the bottom stream
during production rate changes.
the level control loops. For all loops, the range for the manipulated
variable was set to twice the nominal value. The gain of the feed-
back controllers was set to 1%/%. An integration time of 20 min was
selected for the temperature controllers.
In conclusion, the control structure presented here achieves sta-
ble operation and is able to modify the throughput while keeping
the characteristics of the products at their design values.
6. Conclusions
The paper brings the innovation of using two complementary
reactants having an equivalent reactive function but compensating
synergistic thermodynamic features in catalytic reactive distilla-
tion. In particular, the problem of water removal in fatty acid
esterification with light alcohol is solved. This is needed for shifting
the acid conversion to completion and in the same time keep-
ing low the water concentration in the liquid phase, which is
required for protecting a solid catalyst against deactivation. The
method is illustrated by the esterification of dodecanoic (lauric)
acid with methanol by employing 2-ethylhexanol simultaneously
as co-reactant and mass separation agent. Super acid solid catalyst
based on sulfated zirconia, whose activity is comparable for the
two alcohols, can be used at temperatures between 130 and 200 ◦ C.
The operation takes place at moderate pressures, in contrast with
high pressure and vacuum with individual light and heavy alcohol,
respectively.
At optimal operation the highest yield and purity can be
achieved by using stoichiometric feeds in the desired ratio of fatty
esters. At this point the amount of methanol lost in top is prac-
tically negligible. Examining the concentration profiles shows that
two distinct reaction zones can be identified where heavy ester and
light esters are generated. The esterification with methanol behaves
rather as a reactive absorption. The heavy ester plays the role of a
solvent and prevents escaping methanol in the top product. On the
top stages the heavy alcohol enhances water concentration in the
vapour phase, from which is separated by condensation and decant-
ing, while heavy ester is produced in an amount proportional to the
reflux flow rate.
The paper develops an original approach in implementing a
control strategy for achieving optimal operation. This is based on
controlling the inventory of reactants by using the principle of fixed
recycle flows of co-reactants, in this case the reflux of the organic
phase and the methanol inflow to the RDC. This strategy allows
large changes in the production rate.
The above strategy is generic and can be employed for esterifi-
cation involving the formation of azeotropes, as for ethanol and
propanols. The overall result in integrating design and process
750 A.C. Dimian et al. / Computers and Chemical Engineering 33 (2009) 743–750
control is a compact, efficient and easy-to-control multi-product
reactive setup.
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