Antonis Kokossis, Michael C. Georgiadis, Efstratios N. Pistikopoulos (Eds.

)
PROCEEDINGS OF THE 33rd European Symposium on Computer Aided Process Engineering
(ESCAPE33), June 18-21, 2023, Athens, Greece
© 2023 Elsevier B.V. All rights reserved. http://dx.doi.org/10.1016/B978-0-443-15274-0.50244-4

Oligomerization Using Reactive Distillation, Design

and Model Predictive Control
Gabriel Contreras-Zarazúa1,a,b Juan José Quiroz Ramírez,a Eduardo Sánchez-
Ramirez,b Esteban Abelardo Hernández-Vargas,c Juan Gabriel Segovia-
Hernándezb
a
Country CONACyT- CIATEC, Center for Applied Innovation in Competitive
Technologies, Leon Guanajuato
b
Department of Chemical Engineering University of Guanajuato, Noria Alta S/N,36000,
Guanajuato,Gto., Mexico.
c
Department of Mathematics and Statistical Science University of Idaho, 875 Perimeter
Drive, MS 1103 Moscow
Abstract
Biojet-fuel is a promising alternative to reduce emissions in the aviation industry. The
alcohol to jet (ATJ) is considered one of the most attractive alternatives. However, the
economic feasibility is an important drawback of this process. With this in mind, the
process intensification offers an interesting alternative to improve the ATJ process.
Nevertheless, in many cases, the intensification could lead to complex equipment that are
difficult to operate. This work proposes a novel reactive catalytic distillation column to
improve the oligomerization stage of ATJ process. This intensified process was designed
using a sensitivity analysis. In order to determine the feasibility of operating this
intensified column, a control study using PI controller and model predictive control was
performed. The results showed that a reactive distillation column to intensify the
oligomerization zone is feasible. This equipment only consumes 200kW. Finally, the
control studies indicated that it is possible to operate the column using a traditional
feedback control and model predictive control techniques with good performance.

Keywords: Biojet-fuel, reactive distillation, model predictive control, process

intensification.

1. Introduction
Energy has an utmost important role in our society. Energy is used to produce almost all
the necessary commodities such as food, polymers, fertilizers. This energy employed to
produce these commodities has several forms such as electricity, natural gas, liquid fuels,
among others. In this sense, one sector that is essential for our society and which is
characterized by an intensive use of energy is the transport sector. This sector consumes
around 21% of the total energy demand annually, and its energy consumption is expected
to increase up to 130% by 2050 which also represents an increase in CO2 emissions.
Among all the transport means, the aviation sector is expected to grow the fastest,
doubling its energy consumptions and CO2 emission in the next 20 years. For this reason,
the aviation industry has proposed to reduce its CO2 emissions in order to achieve a more
sustainable aviation industry. The use of alternative biofuels for replacing oil-derived
fuels is considered by the International Air Transport Association (AITA) as the most
interesting alternative to reduce emissions (Rivas-Interian et al., 2022). These biofuels
are commonly called biojet-fuels and can be produced from biomass. Nowadays, there
1532 G. Contreras-Zarazúa et al.

are several routes to produce biojet-fuel such as Fischer-Tropsch (FT-SPK),

Hydroprocessed Esters and Fatty Acids (HEFA-SKP), Fisher-Tropsch with Aromatics
(FT-SPK/A) and Alcohol to Jet (ATJ-SPK). In this sense, the ATJ process is considered
one of the most attractive, since the alcohols are produced in abundance, offering
logistical flexibility. The ATJ process consist of three reaction steps: alcohol
dehydration, olefin oligomerization and hydrogenation. In this regard, oligomerization is
a common stage in many jet fuel production routes, such as ATJ or aqueous phase
processing. This stage is utmost importance, because it allows to achieve hydrocarbons
with the exact number of carbons required by the aviation industry. This stage has two
steps: a reaction stage in which ethylene is converted into larger hydrocarbons and a
separation stage, in which the heavy hydrocarbons are separated from the lighter ones.
This process stage is characterized by an intense use of energy, both in the reaction stage
and in the separation. Therefore, one way to reduce energy consumption and increase the
profitability of the ATJ process is through process intensification using reactive
distillation.
Nowadays, the reactive distillation has not been explored as alternative to intensify the
oligomerization zone. With this mind, this work proposes the design of a novel reactive
distillation column for the oligomerization stage of ATJ process. The design parameters
and operating conditions of the column were selected to increase the hydrocarbon
production required for aviation industry; these hydrocarbons are in the range of C8 to
C14. Since this equipment integrates the reaction and separation in a single unit and many
reactions are performed inside it, a control study was carried out to determine the
operation and control feasibility of this column. The control study consists of two parts:
a study using PI controllers, in order to analyze the column control with common
controllers in the industry. The second part is a model predictive control study in order to
compare its performance with traditional feedback control using PI controllers. The
integral absolute error (IAE) was selected as metric to quantify and compare the closed-
loop performance for both PI and MPC controllers.

2. Design of reactive distillation equipment

The ATJ process considered for this study uses ethanol as raw material. This ethanol is
dehydrated and converted to ethylene during the dehydration stage. In this work, it is only
considered the oligomerization stage thus the ethylene is the raw material considered to
this stage. Additionally, it is assumed that only linear olefins are produced during the
oligomerization, this assumption is realistic because the catalysts reported in previous
literature produce linear olefins, also it is a common practice to incorporate an
isomerization stage after oligomerization stage to generate branched hydrocarbons. On
the other hand, in this work, a catalytic distillation column is used to intensify the
oligomerization stage, it consists of a distillation column with an intermediate reactive
zone where the catalyst is placed and the whole set of reactions take place. The separation
stages are located below and above of this reaction zone. Figure 1 shows a scheme of the
reactive distillation process. The reactions that occur in the reaction zone and their
respective kinetic parameters were taken from Sánchez-Ramírez et al., 2022. It is
important to highlight, that the kinetic model corresponds to a set of elementary reactions
of second order. A ethylene feed flowrate of 2100 kg/hr was chosen according to the
information provided by Rivas-Interian et al., 2022.
Oligomerization Using Reactive Distillation, Design and Model Predictive 1533
Control

Figure 1. Intensification of oligomerization stage by catalytic reactive distillation.

The distillation column was designed and simulated in Aspen Plus using the RADFRAC
module. The selection of thermodynamic model for the simulation was performed
according to Carlson´s algorithm (Carlson, 1996). Consequently, the Soave-Redlich-
Kwong (SRK) was used as thermodynamic model to simulate the system, owing to the
mixture contains linear hydrocarbons and the pressure required for the oligomerization is
around 10-40bar. The design of the reactive distillation was performed using a sensitivity
analysis in order to achieve a suitable hydrocarbon distribution and maintain low energy
consumption. It is important to highlight, that according to Li et al., (2016), a suitable
hydrocarbon distribution corresponds to a hydrocarbon mixture in the range of C10 to
C16, being the C12 the most abundant compounds in the blend with the aim of ensuring
the suitable physiochemical properties. Finally, in order to determine the improvements
of intensification, the total annual costs of both the conventional and intensified
oligomerization process were calculated using the Guthrie´s method and data reported by
Rivas-Interian et al., 2022.

3. Control of the reactive distillation column.

Reactive distillation columns are significantly more complex process due to integration
of reaction and separation stages. The complexity of performing the separation and
reaction processes in a single equipment could result in a process that is difficult to control
and operate. Therefore, in order to evaluate the feasibility of operating this intensified
process, a control study was performed. This control study considers the implementation
of model predictive control (MPC) and compares this control strategy with traditional
feedback control strategies using PI controllers. The control schemes using both MPC
and PI controllers are shown in the Figure 2.

Figure 2. A) Control scheme using MPC B) Control scheme using PI controllers.

The integral absolute error (IAE) was chosen as metric to quantify and compare the
closed-loop performance of the PI and MPC controllers. The tunning of controllers were
1534 G. Contreras-Zarazúa et al.

carried out using the minimization of IAE method, to achieve this, disturbances of -1%
were performed on the manipulate variables of distillation column. Mathematically, the
IAE can be defined as follows:
∞
Integral of Absulote Error=
(IAE) ∫ y(t) − y
0 sp dt (1)

Where ysp is the value of the set point for the control variables, whereas y(t) is the value
of control variable at time t. It is important to mention, that the MPC controller uses a
state space (SS) model as predictor model, this state space model was obtained by
subspace identification. The subspace identification is a common method used to obtain
a dynamic model when the process is very complex (Li et al., 2021). The rigorous
simulation of Aspen Dynamics was used as plant model. The MPC control was
implemented in a hybrid platform, which links Aspen Dynamics and the Simulink
software. On the order hand, the feedback control using PI controllers was fully
implemented in Aspen Dynamics. Disturbances of -1% on manipulate variables were
done in order to compare the performance of control systems and to tune the controllers.

4. Results
This section shows the design and control results of the catalytic column. As
aforementioned, the design of reactive distillation column was performed by a sensitivity
analysis in order to obtain a suitable olefin distribution. In this case, designs for 20, 30,
and 40 stages were studied for the column. The results of the sensitivity analysis for the
reflux ratio and reboiler duty as representative cases are shown in Figure 3. Please note,
in Figure 3 as large values of reflux ratio have a positive effect on the production of C10
and C12, while more reflux ratio has a negative effect on C14. The C12 reaches a
maximum concentration in reflux ratios close to 40, while for C10 and C14 the maximum
concentrations are reached at higher and lower reflux ratios, respectively. Based on the
results, it is concluded that a reflux ratio of 43 is the most adequate, because for this value,
there is a suitable distribution of hydrocarbons, being C12 the most abundant and C10
and C14 olefins has a similar production. In addition, it was determined that a reboiler
duty of 200kW is suitable since at this point the hydrocarbon distribution is very similar
to that reported by Li et al., (2016). The sensitivity analysis was repeated for 30 and 40
stages finding that a greater number of stages does not benefit the production of more
C10, C12 and C14. The Hydrocarbon distribution found with the best design is reported
in Figure 3., also, some important design parameters are reported in Table 1. In the case
of total annual costs (TAC), the results indicated that a conventional process has TAC
$582,204.90 $/y. On the other hand, the intensified has a TAC of $511,128.62$/yr
representing savings on costs around 13% in contrast to conventional process.

Table 1. Representative design parameters for the reactive distillation column.

Design Parameter Value
Number of stages 20
Reboiler duty (kW) 200
Reflux ratio 43
Feed stage 7
Oligomerization Using Reactive Distillation, Design and Model Predictive 1535
Control

Figure 3. Design results of reactive distillation.

With respect to control results, the composition of the most abundant compound in domes
and bottoms were used as control variables. In this case, the butane (C4) and dodecane
(C12) are de most abundant compounds in the top and bottom of the column, respectively.
The composition of C4 was controlled with reflux ratio, while the composition of C12 is
controlled using the reboiler duty of bottoms. Once identified the control variables, the
tunning of controllers was performed. As aforementioned, the minimization of IAE
method was used for tuning the controllers, in this case the parameters that minimize the
IAE for the PI controllers at the top of column are 40 min for integral time and 20 for
gain whereas the parameters for the PI controller in the bottom of column are 11.443 for
gain and 70.99min integral time. In the case of MPC control, it is necessary only one
controller to control the composition at the top and bottoms of the column. In this case,
the parameters that minimize the IAE are a sample time of 3 min, control horizon of 10
intervals and prediction horizon of 50 intervals. Once the suitable parameters were
determined, the control performance for both PI and MPC controllers are compared using
their respective IAE values. The results of disturbing the reboiler duty as representative
case are shown in Figure 4 whereas the IAE value is shown in Table 2

Figure 4. Disturbances of -1% in reboiler duty.

1536 G. Contreras-Zarazúa et al.

Table 2. IAE values for disturbances on reboiler duty

C4 control loop C4 control loop C12 control loop C12 control loop
Control loop
(PI) (MPC) (PI) (MPC)
Reboiler duty
2.86E-05 0.1091 0.0010875 0.00794
disturbance

Based on the results, there is an appreciable difference between the two types of
controllers. In this case, the butene composition can be controller better using a PI
controller, having the PI controller up to 30% better performance than the MPC controller.
However, for the dodecene control loop, the performance is very similar between both
controllers. Note that the MCP control has the capability of controlling the process,
however it do not fully fits to the setpoint, being the difference small due to the tolerance
with which the objective function is solved in predictive control. However, it is concluded
that this difference is not significant and both controllers are adequate to control the
process.

5. Conclusions
In this work, a reactive distillation equipment was designed to intensify the
oligomerization stage in the ATJ process. The intensified reactive distillation column has
savings on total annuals costs of 13% in contrast to the conventional process. On the other
hand, the control studies indicated that it is possible to operate this catalytic column using
traditional control strategies, such as feedback control and other advanced control
techniques, such as model predictive control. Finally, it is concluded that both controllers
have similar performance, despite of this please note, that the PI controllers have a slight
better performance due to they returned to exactly set-point value.

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