Ian David Lockhart Bogle and Michael Fairweather (Editors), Proceedings of the 22nd European

Symposium on Computer Aided Process Engineering, 17 - 20 June 2012, London.

© 2012 Elsevier B.V. All rights reserved

Multiobjective Optimization in Distillation with

Reactor-Side for Hydrodesulfurization Process of
Diesel
Erick Y. Miranda-Galindoa, Juan G. Segovia-Hernándeza, Salvador Hernández-
Castroa, Adrián Bonilla-Petricioletb and Gade Pandu Rangaiahc

a
Universidad de Guanajuato, Campus Guanajuato, Division de Ciencias Naturales y
Exactas, Departamento de Ingenieria Quimica, Noria Alta S/N, Guanajuato, Gto.,
36050, Mexico
b
Instituto Tecnológico de Aguascalientes, Departamento de Ingeniería Química,
Aguascalientes, 20256, México
c
National University of Singapore, Department of Chemical & Biomolecular
Engineering, Engineering Drive 4, 117576, Singapore

Abstract
The distillation reactor-side has been proposed to remove sulfur compounds of diesel.
The design and optimization of a hydrodesulfurization process involve the selection of
the configuration and the operating conditions to minimize the total annual cost, CO2
emissions and the amount of sulfur compounds. In general, the optimal design of
hydrodesulfurization process is a highly non-linear and multivariable multiobjective
optimization problem, with the presence of both continuous and discontinuous design
variables. In particular, stochastic multiobjective optimization algorithms are capable of
solving, robustly and efficiently, challenging optimization problems, and they appear to
be a suitable alternative for the design and optimization of complex process schemes. In
this study, we have implemented a multi-objective optimization method to obtain the
design and optimization of three distillation reactor-side in the hydrodesulfurization
process. The results obtained in the Pareto Fronts indicate competition between total
annual cost, CO2 emissions and the amount of sulfur compounds of the
hydrodesulfurization process. These Pareto Fronts are useful to identify proper
conditions for the operation of this process. In general, the reduction of the amount of
sulfur compounds increases the TAC and CO2 emissions. However, we can identify
operating conditions where the TAC can be reduced.

Keywords: hydrodesulfurization process, multiobjective optimization, Pareto Front.

1. Introduction

The design of new processes in the chemical engineering industry takes into account
policies of process intensification, which can be defined as any chemical engineering
development that leads to a substantially smaller, cleaner, and more energy-efficient
technology. One example of process intensification is the minimization of total annual
cost (TAC), which is associated with lower energy consumption, lower greenhouse gas
emissions, miniaturization of process equipment, multipurpose equipment, safety
operations, and others (Moulijn et al., 2008). In particular, hydrodesulfurization (HDS)
“Multiobjective Optimization in Distillation with Reactor-Side in the
Hydrodesulfurization Process of Diesel” 683

process is widely used to remove sulfur found in diesel. Conventional HDS processes
basically consist of a reaction system where the organic sulfur compounds react with
hydrogen to obtain organic compounds and hydrogen sulfide besides to a separation
system to remove compounds of diesel and a recirculation system (Kabe et al., 1999). A
key aspect in the HDS process is the operation of the reactor, which has been widely
studied in the literature (Song and Ma, 2003; Schmitz et al., 2004). On the other hand,
several authors have studied and analyzed different technological alternatives for HDS
processes involved in the diesel production (Taylor and Krishna, 2000; Viveros-Garcia
et al., 2004). We have used a multiobjective optimization (MOO) approach to study and
analyze the competition between TAC, CO2 emissions and the amount of sulfur
compounds of the HDS process in diesel production (Plaza-Rosas, 2008). In particular,
we have analyzed three cases of study with different process configuration. These
process configurations are reported in Figure 1.

Figure 1. Configurations of the DRS for HDS process of diesel: (a) distillation-reaction,
(b) distillation-reaction with a side stream, and (c) distillation-reactor side.

2. Problem statement
Feed composition (F1) is a hydrocarbon mixture of C11-C16 parafffin’s with four
organo-sulfur compounds: thiophene (Th), benzothiophene (BT), dibenzothiophene
(DBT) and 4,6-dimethyldebenzothiphene (4,6-DMDBT). The design targets are to
obtain in the top of the column Th and DBT, respectively, and in the bottom DBT and
4, 6-DMDBT, to react with hydrogen (F2, F3). We used the next kinetic expressions
reported for modeling this system: Th, Van Parijs and Froment (1986); BT, Van Parijs
et al. (1986); DBT, Froment et al. (1994); 4,6-DMDBT, Vanrysselberg (1998). Also, we
have employed the Peng-Robinson EoS as thermodynamic model to calculate the
vapor-liquid equilibrium.

3. Description of multiobjective optimization method

In this study, we have used a multiobjective optimization method based on differential
evolution with taboo list (MODE-TL). Specifically, MODE-TL includes classical
differential evolution steps, adaptation for multiple objectives (selection of individuals
for subsequent generations), taboo list and taboo check, and a convergence criterion
based on the number of generations (Sharma and Rangaiah, 2010). According to
684 E. Miranda-Galindo et al.

Sharma and Rangaiah (2010), a population of NP individuals with D-dimension

(number of decision variables) is initialized randomly inside the bounds on decision
variables. A mutant vector is generated by adding the scaled difference of two randomly
selected individuals with another randomly chosen individual. Elements of this mutant
vector compete with those of target vector, with probability Cr to generate trial vector.
Taboo list concept of Taboo Search is used in the multiobjective optimization method to
avoid the revisit of search space by keeping a record of recently visited points. Taboo
list is randomly initialized using the initial population and continuously updated with
the newly generated trial individuals. This taboo check is implemented in the generation
step of trial vector, and the new trial individual is generated repeatedly until it is not
near to any individual in the taboo list. Objective functions and constraints are evaluated
for this new trial individual. Total NP trial individuals are generated by the repetition of
above steps. The newly generated NP trial vectors are combined with the parent
population to form a combined population with total 2NP individuals. This combined
population undergoes non-dominated sorting and ranking accordingly. Individuals with
the same non-dominated rank are further ranked on the basis of crowding distance. The
first (best) NP individuals are used as the population in the subsequent generation
(Sharma and Rangaiah, 2010). This multiobjective optimization method has been used
in this study.

4. Optimization strategy
In order to optimize the DRS involved in the HDS process, we used a MODE-TL
algorithm coupled to Aspen ONE Aspen Plus. Specifically, for process design of these
separation schemes, we have performed a multiobjective optimization where TAC, CO2
emissions and the amount of sulfur compounds are the optimization targets.

Table 1. Optimization variables of DRS of HDS process

Scheme Scheme Scheme
Continuous Discrete
(a) (b) (c)
Temperature in F1, TF X X X X
Number of stages in column C, NC X X X X
Feed stage in column C, NF X X X X
Pressure in column C, PC X X X X
Distillate rate in column C, DC X X X X
Reflux ratio in column C, RC X X X X
Temperature in HEX1, THEX1 X X X X
Pressure in HEX1, PHEX1 X X X X
Temperature in HEX2, THEX2 X X X X
Pressure in HEX2, PHEX2 X X X X
Hydrogen flow in F2, HF2 X X X X
Hydrogen flow in F3, HF3 X X X X
Catalyst in reactor R1, CR1 X X X X
Catalyst in reactor R2, CR2 X X X X
Product stage of the side stream S1 in
column C, NS1 X X
Product flow of the side stream S1 in
column C, FS1 X X
Product stage of the side stream S2 in
column C, NS2 X X X
Product flow of the side stream S2 in
column C, FS2 X X X
“Multiobjective Optimization in Distillation with Reactor-Side in the
Hydrodesulfurization Process of Diesel” 685

This design problem is challenging due to the presence of both continuous and
discontinuous decision variables subject to several constraints. Details of this MOO
problem are given in Table 1. In the present study, TAC is estimated as the sum of the
annual operation cost and annualized investment cost for the process. The investment
costs of equipment are estimated by the method suggested by Guthrie, while CO2
emissions are calculated by the technique proposed by Gadalla et al. (2005). For the
DRS used in the HDS process, the multiobjective optimization problem can be stated as
follows:

min (TAC, CO2 emissions, sulfur compounds) (2)

subject to inequality constraints reported in Table 2 for each DRS scheme.

Table 2. Constraints of the multiobjective optimization problem in HDS process.

Constrains Scheme (a) Scheme (b) Scheme (c)
NC > NF X
NC> NS2 > NF X
NC> NS2 > NF > NS1 X
NS2  NF X
NS2  NF  NS1 X

The parameter tuning improves the convergence of stochastic methods. For the
stochastic optimization we used 100 individuals and 500 generations. The values for
parameters are: CR=0.3, A=0.5, tr= 0.02, tls=50. The initial point of MOO is created
randomly in the feasible region.

5. Results and conclusions

In this section, we report the Pareto fronts obtained for the three DRS schemes in the
HDS process. It is important to recall that the Pareto front of these schemes includes
three objectives. We can observe the diversity of optimal designs and the relationship
between the three objective functions, Figure 2. With illustrative purposes, Table 3
shows selected solutions obtained from Pareto Fronts for different DRS schemes in the
HDS process.

 Scheme (a)  Scheme (b)  Scheme (c)

Figure 2. TAC as a function of CO2 emissions and the amount of sulfur compounds for
DRS schemes in the HDS process.

It is important to remark that the reduction of sulfur compounds is the most important
objective in the design of this process. In general, the reduction of the amount of sulfur
686 E. Miranda-Galindo et al.

compounds increases the TAC and CO2 emissions. However, we can identify proper
operating conditions where TAC can be significantly reduced. Therefore, these trades-
offs of TAC and CO2 emissions call for careful consideration for the design of this
process in diesel production.

Table 3. Selected solutions of Pareto fronts for each scheme in the HDS process
TAC CO2 emissions Sulfur compounds
($/year) (TON/year) (Kg/sec)
2,348,440.20 9,936.16 2.4660E-03
Scheme (a) 458,239.27 4,257.71 1.8756E-01
606,810.77 3,811.47 2.0752E-01
1,628,912.91 14166.123 3.0154E-03
Scheme (b) 470,123.417 5,683.32 2.3255E-01
584,893.824 4,372.92 2.7148E-01
1,656,164.50 27,491.22 2.6518E-06
Scheme (c) 502,262.25 6,201.09 2.1985E-01
712,353.75 4,470.03 2.7333E-01

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