Innovative process for fatty acid esters by dual reactive

distillation

a b s t r a c t
Catalytic reactive distillation offers new opportunities for manufacturing fatty acid
esters, involved both in biodiesel and specialty chemicals. A key problem is the
effectivewater removal in viewof protecting the solid catalyst and avoiding costly
recovery of the alcohol excess. Thiswork proposes anovel approachbased on dual
esterification of fatty acid with light and heavy alcohols, namely methanol and 2-
ethylhexanol. These two complementary reactants have an equivalent reactive
function but synergistic thermodynamic features. The setup behaves rather as
reactive absorption combined with reactive azeotropic distillation with heavy alcohol
as co-reactant andwater-separation agent. Another element of originality is the
control of the inventory of alcohols by fixing the reflux of heavy alcohol and the light
alcohol column inflow. This strategy allows achieving both stoichiometric reactant
feed rate and large flexibility in ester production. The distillation column for
recovering light alcohol from water is not longer necessary. The result is a compact,
efficient and easy-to-control multi-product reactive setup.

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
efficient 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 reactive distillation was
proposed (Omota, Dimian, & Bliek, 2003), whichmakes use of super-acid solid
catalyst, more specifically sulfated 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 consequently 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 separating the water as
top product with high yield. When the alcohol gives an azeotrope withwater, 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 formethanol,
which is by far the most interesting alcohol frommarket viewpoint.Additional
separation equipment is needed for recovering and recycling the methanol to
reaction.

The analysis of this problem by residue curve map (RCM) representation
demonstrated that quantitative water removal can be obtained bymeans of a reflux of
fatty acid instead of alcohol (Omota et al., 2003). In this case the process should be
fed with a stoichiometric 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 catalyst (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 reaction
temperature with Amberlyst could not exceed 110 C. On the contrary, using SZr
catalyst allows operating at much higher temperatures, up to 200 C, such to ensure
complete acid conversion. Note that recent superacidic resin catalysts, as Amberlyst
35TM or 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 glycerides 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 forwater removal in the esterification of
fatty acids with methanol by reactive distillation 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 parameters 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 alcohols 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 pressure. 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 separation 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
methanolwater which should be submitted to further separation. For a temperature
window of 130160 C the use of vacuum is necessary in the case of 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 simultaneously the role of reactant and mass separation agent
(MSA). Dual esterification with both heavy and light alcohol in a RD environment
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 significant. 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 23 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 lowcost 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 alcohol, 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=kCACB can be used for simulation purposes. In this case, the kinetic constants are
k1 =1.2105 exp(55,000/RT) for the esterification of lauric acid with methanol and
k2 =6104 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 fromtop being devoted towater
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 0.05m3 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 1.2m.

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, reaction rate and
temperature. The results confirm the thermodynamic analysis. The lauric acid is
consumed mostly in the upper part of 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 showtwo distinct zones. The water is entrained by 2-
ethylhexanol on the first three non-reactive stages, further condensed and removed
in decanter.Water concentration in liquid in the reaction zone can be kept lowindeed,
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 convenient 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 inmajority 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 obtainedwith 2 wt% methanol in
bottoms, but dropped below 170 C for about 6 wt% methanol.

The temperature profile is directly correlated with the column pressure. A flat profile
in the reactive zone is preferred fromcatalyst 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 pharmaceutical
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
for operation, but the purity of the bottoms is only 96.5%.

Raising the distillate rate increases the purity of ester up to maximum 98%, while the
purity of the water product is only slightly affected. Further increase leads to both
purities degradation. The diagram shows the make-up policy of methanol, which
starts from the stoichiometric value of 80 kmol/h. The optimum vapour distillate is
achieved at 113114 kmol/h corresponding to a methanol consumption of 82.3
kmol/h, only slightly above stoichiometry.

The distribution of impurities in top and bottom products is of significance too (Fig.
5). Increasing the distillate rate drops to zero all impurities in bottoms
exceptmethanol, which remains constant at 2% above 114 kmol/h. On the contrary,
further methanol excess in feed will pass only in the top product.

Regarding the reaction rate, Fig. 6 compares two situations: base-case and the
stoichiometric feed. The heavy ester formation remains in place, but the light
estermigrates froman upper position to a lower position. By stoichiometric balance
no 2EH is found in the base and no methanol in the top water. The methanol
recovery column is no longer needed.

The above results give insights about the optimal conditions for operating the
column. The central role of manipulating the reboiler duty and the reflux flow rate is
clearly identified. In the next section, we will investigate the possibility of finding a
suitable control strategy that could bring the operation close to optimum faced with
various disturbances.

5. Process dynamics and control strategy
In this section, the dynamic behavior and control aspects regarding the reactive
distillation column are investigated. The controllability 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 separationrecycle 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 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
multiplicity 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 concentration,
adjust the fresh feed of reactant somewhere in a recycle loop to keep its inventory
at a constant value.

The concepts developed for reactorseparatorrecycle systems are also applicable
to reactive distillation processes (Bildea, Omota, Dimian, & Bliek, 2004). Al-Arfaj and
Luyben (2000) discuss the pitfalls of fixing the feed rate of all reactants of a reactive
distillation column. In the followingwork (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
concentration in the distillation column.

The system investigated in the present study involves three reactants (lauric acid,
methanol and 2EH) and two reactions (esterification 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 having significant values.
Therefore, feedback will be employed for controlling alcohols inventory.

Fig. 7 presents the process flowsheet diagram used for studying process dynamics
and control implementation. With respect to Fig. 2 the following modifications can be
noted:

- 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. Themake-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 equilibrium at the top and the bottomof 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 failuremanifesting by the accumulation or depletion of one
reactant.

The above-described control structure was tested for larger disturbances, 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 thewater stream. Clearly, the control structuremust 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 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 ofmethyl-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 fromthe steady state (feed rate of lauric acid: 100 kmol/h) which
ismaintained 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 20min 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
ofwater 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 critical 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 the level control loops. For all loops, the range for the
manipulated variable was set to twice the nominal value. The gain of the feedback
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 stable 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 distillation. 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 keeping 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 practically negligible. Examining the concentration profiles
shows that two distinct reaction zones can be identified where heavy ester and
light esters are generated. The esterification withmethanol 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, fromwhichis separatedby condensation and
decanting, 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 esterification involving the
formation of azeotropes, as for ethanol and propanols. The overall result in
integrating design and process control is a compact, efficient and easy-to-control
multi-product reactive setup.