Article

pubs.acs.org/IECR

Dynamic Optimization of Lurgi Type Methanol Reactor Using Hybrid

GA-GPS Algorithm: The Optimal Shell Temperature Trajectory and
Carbon Dioxide Utilization
Abdulaziz Alarifi,* Zhefu Liu, Fatih Safa Erenay, Ali Elkamel, and Eric Croiset
University of Waterloo Waterloo, Ontario, Canada N2L 3G1

ABSTRACT: At present, methanol is mostly produced from syngas, derived from natural gas through steam methane reforming
(SMR). In a typical methanol production plant, unreacted syngas is recycled for mixing with natural gas and both used as fuel in
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the reformer furnace resulting in carbon dioxide (CO2) emissions from the flue gases emitted into the atmosphere. However,
CO2 can be captured and utilized as feedstock within the methanol synthesis process to enhance the productivity and efficiency.
To do so, dynamic optimization approaches to derive the ideal operating conditions for a Lurgi type methanol reactor in the
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presence of catalyst deactivation are proposed to determine the optimal use of recycle ratio of CO2 and shell coolant temperature
without violating any process constraints. In this context, this study proposes a new approach based on a hybrid algorithm
combining genetic algorithm (GA) and generalized pattern search (GPS) derivative-free methodologies to provide a sufficiently
good solution to this dynamic optimization problem. The hybrid GA-GPS algorithm has the advantage of sequentially combining
GA and GPS logics: GA, as the most popular evolutionary algorithm, effectively explore the landscape of the fitness function and
identify promising basins of the search space, whereas GPS efficiently searches existing basins in order to find an approximately
optimal solution. The simulation results showed that implementing the shell temperature trajectory derived by the proposed
approach with 5% recycle ratio of CO2 increased the production of methanol by approximately 2.5% compared to the existing
operating conditions.

1. INTRODUCTION CH4 + CO2 → 2CO + 2H 2 ΔH298K = 247.3 kJ mol−1

Carbon dioxide is the primary greenhouse gas emitted to the
atmosphere through fossil fuels (coal, natural gas, and oil)
consumption for energy supply and transportation. In addition,
many industrial processes produce CO2 emission either as a
result of fossil fuel combustion to create heat and steam and/or
as a byproduct of chemical reactions.1 For instance, steam
methane reforming (SMR) is widely used to produce syngas
from natural gas, where the reforming reaction takes place
inside catalyst filled tubes heated externally by firing fuel in a
burner located in the furnace chamber.2 Flue gases are
discharged through an exhaust at the top of furnace to a heat
recovery system where feed fuel and combustion air are
preheated, and steam is generated. In the process of burning
natural gas using air as an oxidant, the flue gas usually consists
of mostly nitrogen followed by carbon dioxide with nearly 10−
25 volume percent of the flue gas. It also contains a small
percentage of some pollutants, such as soot, carbon monoxide,
and nitrogen oxide.3 Consequently, research studies on carbon
dioxide utilization focus on developing novel approaches for
mitigating the contributions of CO2 emissions to global
warming and ocean acidification by developing beneficial uses
of CO2 in areas where geologic storage of CO2 may not be the
best solution.4 The advantage of CO2 fixation over CO2
disposal is that the production of chemicals with high economic
value is possible.5
The reaction of carbon dioxide and methane in absence of
steam (eq 1), known as dry reforming of methane (DRM), to
form syngas is the most appealing approach to convert two
inexpensive materials into useful chemical building blocks.6
(1)
A challenging problem in commercialization of the dry
reforming process is that the reaction condition is more
favorable for other side reactions such as methane decom-
position (eq 2) and boudouard equilibrium (eq 3).7
CH4 → C + 2H 2 ΔH298K = 74.8 kJ mol−1 (2)
2CO → C + CO2 ΔH298K = − 172.5 kJ mol−1 (3)
Coke deposition occurs by the exothermic boudouard reaction
and the endothermic cracking of methane, which leads to
severe catalyst deactivation and the need for premature catalyst
change-out.8,9 The CALCOR process uses a special catalyst for
reacting dry CO2 with natural gas, liquid petroleum gas (LPG),
and syngas to produce high-purity carbon monoxide that
contains less than 0.1% methane and has a H2/CO ratio as low
as 0.4.10,11 A combination of steam methane reforming and dry
methane reforming (SMR+DRM) of natural gas is a
competitive process to the conventional SMR process. SMR
+DRM produces the best syngas ratio for production of liquid
fuels with a 2−2.1 H2/CO molar ratio, whereas SMR of natural
gas produces syngas with a H2/CO molar ratio of slightly above
3.12 Regardless of its advantages, SMR+DRM process has not
been matured yet and still suffers from coking, severely
Received: August 7, 2015
Revised: November 26, 2015
Accepted: December 17, 2015
Published: December 17, 2015

© 2015 American Chemical Society 1164 DOI: 10.1021/acs.iecr.5b02918

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Industrial & Engineering Chemistry Research
Figure 1. Scheme of the methanol synthesis loop.
shortening the lifetime of the applied catalysts. Because the
DRM technology has not been widely implemented for
reducing CO2 emission, alternative approaches to address this
issue are still under ongoing investigation.13 Chemical recycling
of CO2 to renewable fuel, such as methanol, offers a future
transportation fuel.
Olah and his research group developed an improved Cu/
ZnO-based catalyst for methanol synthesis from CO2 and H2
under operating conditions and deactivation rate similar to
those of commercial catalysts for syngas-based methanol
synthesis.14,15 The first CO2-to-methanol recycling plant
(George Olah Renewable Methanol Plant) is operated in
Iceland by Carbon Recycling International (CRI).16 This plant
uses available local geothermal energy (hot water and steam) to
supply the electricity needed to produce pure H2 by water
electrolysis process with a daily capacity of 10 ton/day. The
present technologies of water electrolysis have an efficiency of
50−80% and require 50−79 KWh/kg of H2; hence, they cost
3−10 times more than steam methane reforming even with a
traditional method of generating electricity.17
The direct conversion of natural gas is more feasible and
cost-effective at an industrial level than burning the fuel to
generate electricity needed to electrolyze water and then
produce hydrogen.18 For an SMR-based methanol plant, the
H2/CO molar ratio obtained is close to 3, which is not optimal
for methanol synthesis process. Therefore, recycling CO2 back
to the reformer feed gas can be an option to increase methanol
production by adjusting the stoichiometry of the makeup gas,
which increases the reformer heat duty while reducing the
amount of wastewater discharged from the distillation system.
A case study presented by Reddy et al. showed that the
methanol plant capacity can be expanded approximately 20%
by recovering sufficient CO2 from steam reformer stack and
recycling it as feedstock to the SMR.19 However, recycling CO2
to the reformer feed-gas increases the demand for heat.
An alternative option is recycling CO2 into the syngas
compressor suction feed rather than reformer feed. In a
previous research, we have concluded that around 3%
improvement in the plant production capacity can be achieved
by injecting additional interstage CO2 into ICI’s multibed
adiabatic reactor.20 The objective of this study is to use dynamic
optimization to derive the optimal recycle ratio of CO2 and
shell temperature trajectory of an industrial methanol Lurgi
type reactor during four years of catalyst lifetime. We kept the
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recycle ratio of CO2 within the design limit of the plant
(maximum 10%) and the peak bed temperature less than or
equal to 543 K and then analyzed the effects of these variables
on the reactor performance and the catalyst activity.
2. MODEL DEVELOPMENT
Consider a midsize methanol plant, e.g., up to 2500 ton/day,
that employs a steam methane reformer with an external source
of hot gas to heat tubes in which catalytic reforming reactions
take place. The feedstock to the reformer is a mixture of steam
and natural gas with a typical steam-to-carbon ratio of 3:1 to
avoid carbon deposition on the catalyst surface.21 Steam and
methane are converted to syngas at a high temperature and an
elevated pressure. The syngas is then mixed with recycled
unreacted gas, pressurized in a compressor until the operational
pressure of methanol synthesis process is achieved, and then
fed to a water-cooled tubular reactor. The tubes packed with
catalyst are externally cooled by boiler water, and a nearly
isothermal temperature profile is formed in the catalyst bed.
This type of reactor aims at recovering the heat of methanol
synthesis reactions to the maximum possible extent in the form
of high-pressure steam. Figure 1 shows the schematic diagram
of the methanol synthesis process. Methanol synthesis from
syngas over Cu/ZnO/Al2O3 catalyst is composed of three main
equilibrium reactions:
CO + 2H 2 ⇌ CH3OH ΔH298K = − 91 kJ mol−1 (4)
CO2 + 3H 2 ⇌ CH3OH + H 2O ΔH298K = − 50 kJ mol−1
(5)
CO2 + H 2 ⇌ CO + H 2O ΔH298K = + 41 kJ mol−1 (6)
2.1. Reactor Model. The methanol synthesis reactor
studied here is a Lurgi type used in Shiraz Petrochemical
Company.22 A 1D heterogeneous reactor model is used to
simulate the performance of industrial Lurgi type methanol
reactor. It employed a two-phase model in which heat transfer
through the solid and fluid phases is considered separately.23
The continuity and energy equations for solid and fluid phases
are expressed as follows:24
DOI: 10.1021/acs.iecr.5b02918
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Continuity equations: Table 1. Feed Composition and Catalyst Specifications of

∂C ∂C Industrial Plant Methanol Synthesis Reactor
εb i = −uz i + kg, iav(Cis − Ci)
∂t ∂z parameters value
∀ z ∈ (0, L], t ∈ (0, t f ], i = 1, 2, ..., Nc (7) Feed Composition
Inlet flow rate (mol s−1) 0.64
∂Cis mole fraction %
εs = R i(Cis ,
T)− s
kg, iav(Cis
− Ci) CH3OH 0.50
∂t
CO 4.60
∀ z ∈ (0, L], t ∈ (0, t f ], i = 1, 2, ..., Nc (8) CO2 9.40
Energy equations: H2 65.90
H2O 0.04
∂T ∂T
ρf cp ,f = −uzρf cp ,f + hf av(T s − T ) CH4 10.26
∂t ∂z N2 9.30
U Design and Catalyst Specifications
+ 4 w (Tshell − T ) ∀ z ∈ (0, L], t ∈ (0, t f ] Inlet pressure (bar) 76.98
Di (9)
Length of the reactor (m) 7.022
∂T s εb 0.39
ρs cp ,s = RT(Cis , T s) − hf av(T s − T ) ρb (kg m−3) 1132
∂t
aν (m−1) 626.98
∀ z ∈ (0, L], t ∈ (0, t f ] (10) Tube inner diameter (mm) 38
Number of tubes (Ntubes) 2962
The reaction rates and heat of reactions terms are
Nrxn ⎡ PH OPCO ⎤
R i(Cis , T s) = ρb a ̃ ∑ vijrj(Cis , T s) k 2PCO2⎢1 − Keq2 P 2P ⎥
i = 1, 2, ..., Nc ⎣ H2 CO2 ⎦
j=1 (11) rRWGS = PH O
1 + K ad1 P 2 + K ad2PH0.52 + K ad3PH2O
Nrxn H2 (18)
RT(Cis , T s) = ρb a ̃ ∑ rj(Cis , T s)( −ΔHr, j(T s)) where Pi is the partial pressure of component i in bar, and the
j=1 reaction rates are calculated per kilogram of catalyst (kmol/kg
i = 1, 2, ..., Nc cat s). The parameters of the equations including the reaction
(12)
rate constants, adsorption equilibrium constants, and reaction
Boundary and initial conditions: equilibrium constants are given elsewhere.26
2.3. Deactivation Model. The sulfur components normally
Ci = Ci,in ; T = Tin @z = 0, t ∈ [0, tf ] (13) present in the natural gas feedstock must be removed to
prevent poisons and subsequent quick deactivation of the
Ci = Ci,0 ; T = T0 @t = 0, z ∈ (0, 1] (14) reforming process and methanol synthesis catalysts. Under
normal operation conditions, deactivation of Cu/Zn/Al2O3
Cis = Cis,0 ; T s = T0s @t = 0, z ∈ [0, 1] (15) catalyst is slow and only caused by thermal sintering, which
The methanol production rate can be formulated as occurs by the migration of copper crystals to larger
agglomerates.27 In preparing a fresh catalyst, it is first activated
Production = Ntubes Ac uz M wMeOH C MeOH|z = 1 (16) by reduction conventionally carried out with hydrogen. Once
In this set of equations, Ci stands for concentration of reactant i. the reduction reaction is complete, the fresh catalyst is used
The feed specifications and catalyst characteristics of methanol immediately in methanol synthesis by replacing the hydrogen
synthesis reactor are presented in Table 1. stream by syngas stream and implementing changes in pressure,
2.2. Reaction Kinetics. Three overall reactions (eqs 4−6, temperature, and space velocity, as desired. The fresh catalyst
hydrogenation of CO and CO2, and the reverse water−gas activity declines in the first 20 h by as much as 60%.28 The
shift) are possible occurred in methanol synthesis. Several adjusted deactivation model developed by Hanken was found
studies proposed kinetic models of methanol synthesis. In this to give results in good agreement with industrial operating
study, we used Langmuir−Hinshelwood−Hougen−Watson conditions.29 The rate of change in the activity of Cu/Zn/Al2O3
(LHHW) type reaction kinetic model of Brussche and Froment catalyst based on this model is given as follows:
because it is the only model based on experiments involving a ⎛ −E ⎛ 1
da 1 ⎞⎞ 5
commercial ICI 51−2 Cu/ZnO/Al2O3 catalyst that is grounded = −Kd exp⎜⎜ d ⎜ − ⎟⎟⎟ a ∀ t ∈ (0, t f ]
and diluted for the sake of preventing the diffusion resistance dt ⎝ R ⎝T TR ⎠⎠
and accurately controlling the pseudoisothermicity of the (19)
reaction.25 The corresponding rate expressions for hydro-
a −a
genation of CO and CO2 and reversed water−gas shift ã = 1 − 0
reactions are a0 (20)
⎡ 1 PH2OPCH3OH ⎤ where TR = 513 K, Ed = 91 270 J mol−1, and Kd = 0.00439 h−1
k1PCO2PH2⎢1 − K eq1 PH3 2PCO2 ⎥
⎣ ⎦ are the reference temperature, activation energy, and
rCH3OH = deactivation constant of the catalyst, respectively. An initial
⎡ PH2O 0.5 ⎤3
⎢⎣1 + K ad1 PH2 + K ad2PH2 + K ad3PH2O⎥⎦ value a (t = 0) of 0.4 was assumed. A relative activity started at
(17) 1 is used to find the reaction rate.
1166 DOI: 10.1021/acs.iecr.5b02918
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Figure 2. Temperature and concentration profiles calculated by Runge−Kutta fourth-order and explicit finite difference methods.
2.4. Simulation. A mathematical treatment of the
governing model, eqs 7−20, is carefully addressed before
solving them. Because the catalyst activity rapidly declined
within the first 20 h of start-up operation, the transient behavior
of the reactor system is not of interest to our investigation, and
the numerical solutions are performed in two consecutive
stages: steady-state stage followed by dynamic stage.
2.4.1. Steady State. The above heterogeneous model, eqs
7−18, consists of a set of partial differential equations. In
steady-state model, these equations are reduced to ordinary
differential equations (ODEs) and algebraic equations by
eliminating the left-hand sides of the equations (unsteady-state
terms) and assuming that the catalyst activity is unity. This
system of equations is initially solved by decoupling the fluid
and solid phases in such a way that the solution of system is
obtained in two consecutive stages, where the solid-phase
nonlinear algebraic equations is solved by using the powerful
Newton−Raphson method; subsequently, the obtained values
of solid-phase variables are used in the fluid-phase ODEs.
ODEs are often solved by Runge−Kutta fourth-order (RK4) or
Gear’s methods. Both methods incorporate an error control
scheme to automatically adjust the step-size, generally
providing good accuracy. Gear’s method is a more sophisticated
scheme, ensuring reliable convergence and accuracy; thus, it is
an effective method for solving a stiff ODEs system.30
Fortunately, the ODEs system considered herein is not stiff;
therefore, a RK4 scheme is applied to provide an accurate
solution with reduced computational costs. The purpose of
solving the system by this technique is to (1) determine the
initial conditions for temperature and concentrations to be used
for dynamic simulation described in the next section and (2) to
ensure that the integration step size used in the finite difference
method guaranties an acceptable accuracy of the solution and is
good enough to be adopted later to solve the dynamic
simulation. Considerable attention has been directed toward
the discretization of the convection terms and incorporation of
source terms, transfer terms, and the boundary conditions into
the numerical solution scheme. The scheme is an explicit
approximation of the ODEs system, which usually cuts down
the computational time. However, the implementation of the
explicit method leads to restrictions on the step size because of
numerical stability concerns. For discretization of the ODEs
system, we imposed the scheme to obey the following stability
condition:31
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du ⃑
= f (z , u ⃑) with u ⃑(0) = u0
dz (21)
where du ⃑ /dz are the derivatives of concentrations and
temperature with respect to space-direction in fluid phase
(eqs 7 and 9) and the Jacobian matrix of the set of functions f is
defined as
⎡ ∂f ⎤
J f = ⎢ i ⎥ , i = 1, 2, ..., Neqs , j = 1, 2, ..., Nvars
⎢⎣ ∂uj ⎥⎦ (22)
The eigenvalues λ are found using the characteristic equation of
the square matrix Jf, det(A − λI) = 0. The solution is
conditionally stable if each eigenvalue satisfies the following
test:
Re(λi) = |1 + hλi| ≤ 1 (23)
The step size (h) is chosen to be relatively small in the solution
region where the curves display much variation and to be
relatively large where the solution curves straightness out to
approach lines with a slope of almost zero.32 Before we attempt
to adopt the step-size in solving the dynamic model by using
method of lines, it is useful to compare the solutions obtained
by both approaches. It is pointed out that RK4 and FD
methods give almost identical results for all the key
components and temperature as shown in Figure 2.
2.4.2. Dynamic. As already mentioned earlier, the
heterogeneous model of tubular reactor comprises approx-
imately 15 partial differential and algebraic equations. The
method of lines has been used for solving partial differential
equations in which a forward finite difference method is used to
discretize the spatial domain with nearly 640 finite elements;
then, the resulting set of ODEs was numerically integrated
through time. Dynamic simulator code was developed using eqs
7−18, accompanied by catalyst deactivation (eqs 19 and 20) in
order to compute the reactor effluent and validate the
mathematical model with the industrial data. Table 2 shows
the predicated production rate of the reactor compared to the
plant data over an operating time frame of about 1200 days.
The dynamic simulation results match well with the industrial
data; therefore, we concurred that dynamic model with the
proposed deactivation model parameters is reliable in
predicting the reactor behavior.
DOI: 10.1021/acs.iecr.5b02918
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Table 2. Comparison between Plant Data and Predicted because it is restricted by the plant’s design flexibility. There is
Methanol Production only one path constraint; the gas temperature along the reactor
length must be below 543 K to prevent a severe deactivation
time (day) plant (ton/day) prediction (ton/day) % error
rate. The objective function J is the value of the total methanol
0 295 292 −1.01 production over the catalyst lifetime period. The proposed
100 296.5 286.6 −3.33 hybrid algorithm was used for dynamic constrained optimiza-
200 302.6 283.2 −6.41 tion of the reactor operating conditions considering the above
300 284.3 280.6 −1.30 inequality constraints.
400 277.9 278.4 0.17 2.6. Hybrid Genetic-Generalized Pattern Search
500 278.2 276.7 −0.53 Algorithm (GA-GPS) for the Optimization Problem.
600 253.0 275.0 8.69 Genetic algorithm (GA) is the most popular type of
700 274.0 273.4 −0.21 evolutionary algorithms that mimics the principle of biological
800 268.1 272.1 1.49 evolution, repeatedly modifying a sample solution population
900 275.5 270.8 −1.70 using a technique inspired by natural evolution using random
1000 274.6 269.7 −1.78 genetic operators such as mutation, selection, and crossover.33
1100 262.9 268.6 2.16 GA is widely classified as a metaheuristic optimization
1200 255.2 267.6 4.85 algorithm because of its stochastic search mechanism that
enables it to escape from local optima while exploring the
Figure 3 shows the temperature profile and deactivation rate search space for the global optimum in complex and rugged
of catalyst with respect to the reactor length and the time fitness landscapes. 34 In any metaheuristic algorithm, a
horizon according to the dynamic stage simulation results. The compromise between exploration and exploitation components
catalyst activity drops to the lowest level (<0.5 at the end of is carried out to balance the convergence rate of the algorithm
run). Consequently, the maximum reactor temperature is 534 and the likelihood of achieving the global optimality.35,36
K at the start of run and gradually decreases over time. Exploration aims to generate diverse solutions by exploring a
2.5. Problem Formulation. The task is finding the optimal large solution space, whereas exploitation narrows down the
operation strategy, namely, the shell coolant temperature search to a specific regions with high likelihood of containing a
trajectory and recycle ratio of CO2 (RCO2) fed to the reactor. good solution. During the initialization step of GA, an initial
The objective was formulated as a nonlinear dynamic population consisting of a number of individuals (NI) (each
optimization problem as follows: having a set of chromosomes or genotypes (NG) to represent
the decision variables for a particular solution) is randomly
⎡ tf ⎤ generated from the feasible search space. A fitness function is
max⎢J =
⎣ ∫0 Production(R CO2 , Tshell , t ) dt ⎥
⎦ (24) evaluated for each individual; then, the population is sorted by
descending order of the fitness values. Subsequently, the
subject to selection process considers only the fitness values regardless of
0 ≤ T ≤ 543K (25) the individuals’ genotypes. Therefore, the selection is an
exploitative operation because the mechanism does not care
0 ≤ R CO2 ≤ 0.1 (26) about the diversity of genotypes of each selected individuals but
490K ≤ Tshell ≤ 540K (27)
rather distinguishes them on the basis of their fitness values.
These selected individuals are used to perform the genetic
The production rate function is obtained by solving the partial operations: (1) mutating some individuals by replacing some of
differential equations (eq 7−20). The shell coolant temperature the existing genotypes with new genotypes. (2) Crossover
is bounded between 490 and 540 K, and the recycle ratio of (exchanging a portion of genotype) is performed between two
CO2, defined as RCO2 = FCO2/Fin, must be below or equal 0.1 individuals (parents) to create two new individuals (children).

Figure 3. Temperature and catalyst activity profiles for the reference case condition (RCO2 = 0, Tc = 524 K).

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Figure 4. Best and mean fitness values and the average distance between individuals.
Figure 5. Flowchart of hybrid GA-GPS algorithm.
Mutation and crossover are explorative operators because they
introduce new genotypes to the population and spread the new
generation over the search space with the hope of exploring
new basins.33 After enough generations, existing genotypes in
the population become similar to each other, and the mean
fitness value of the populations becomes close to the best
fitness value as illustrated in Figure 4.
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GA has been proven to be effective in escaping local optima
and finding solutions closed to the global optimum/optima for
even a very complex function. However, it shows weakness in
efficiently exploiting the existing basins in order to find the
optimal point.37 Hence, it could be much efficient to use the
output of GA as an input for a local search algorithm such as
generalized pattern search (GPS). GPS is a derivative-free
DOI: 10.1021/acs.iecr.5b02918
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Figure 6. Predicted methanol production rate at different recycle ratio of CO2 ratio associated with the optimal shell temperature trajectory.
optimization method that does not use the information about
gradient or higher derivative to search for an optimal point.38
Starting from an initial solution x0 and an initial mesh size Δm0 =
1, GPS generates a set of neighborhood points by multiplying
the current mesh size by each pattern vector. These vectors are
fixed-direction vectors and are defined by the number of
independent variables in the objective function; as in GPS, 2N
vectors consist of N positive and N negative vectors. In k
iteration, GPS algorithm polls all the mesh points by computing
their objective function values in order to find an improved
point. If the polling step fails to find an improved point, then
the mesh size will be reduced by half, Δmi+1 = 0.5Δmi , and the
current point is used for the next iteration k + 1. Otherwise,
when a successful polling takes place and an improved point is
found, then the mesh size will be doubled, Δmi+1 = 2Δmi , and the
current point is updated by the improved point for the next
iteration as shown in Figure 5.
The incorporation of a local search algorithm such as GPS is
a good strategy for improving the accuracy of the approximate
solution previously provided by the genetic algorithm. Thus, an
appropriate sequential hybridization of GA and GPS can
improve the exploitation of the basin of solution that was
already explored by GA and can lead to find, as accurately as
possible, a local optimum. To maximize methanol production,
we implemented such a GA-GPS hybrid algorithm to solve the
problem of optimizing aforementioned reactor’s operation
conditions.
The first phase of GA-GPS hybrid algorithm is exploration
via employing GA to minimize the fitness function, negative of
the total production over the catalyst lifetime (−J). GA
parameters were tuned by troubleshooting, and the number of
generations was set to 450. As indicated in Figure 4, the mean
value of the fitness function is matched up to the best fitness
value and no more diversity of individuals. Each generation has
a default population of 200 individuals, and the algorithm
begins by creating a random initial population. These
individuals represent shell temperature and recycle ratio of
CO2 at each time segment. Then, the fitness value (score) of
each individual is evaluated to select the best individuals for
mutation and crossover processes. We used stochastic universal
sampling (SUS) for the selection operation, where all
individuals’ scores are normalized and then mapped to an
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adjoining segment of a line in such a way that each individual’s
segment is equal in size to its scores. SUS generates a single
random value (specifying the starting point in [0, 1/Np] to
sample all of the solutions by selecting an individual at every 1/
Np distance where Np is the number of individuals to select.
SUS shows no bias, giving the low-scored individuals a chance
to be chosen. The next step is to generate the second
generation of population by applying mutation and crossover
on the selected individuals, where 80% of the next population is
produced by using GA’s operators (crossover and mutation)
and 20% elite individuals from the current and previous
generations. The second phase involves an exploitative search
employing GPS after receiving the best solution from GA and
using it as an initial solution for GPS. A complete polling occurs
by computing the objective function values at all mesh points
f(Xmi ) starting at the first iteration Δm0 = 1 until some
termination criteria are met (either Δmi = 10−6 or 300
iterations).
3. RESULTS AND DISCUSSION
The time horizon for the decision variables of the considered
optimization problem, shell temperature and recycle ratio of
CO2, were discretized into 16 intervals, each interval is a
quarter of a year over the catalyst lifetime (four years). The
optimization of reactor was performed in two steps: dynamic
stage optimization of shell temperature followed by simulta-
neous dynamic stage optimization of shell temperature and
recycle ratio of CO2.
3.1. Dynamic Staged Optimization of Shell Temper-
ature. For this section, the ratio of recycled CO2 directly fed to
the reactor is set as 0, 5, and 10% of the total flow rate of the
inlet stream; consequently, eq 26 is ignored. Figure 6 shows the
amount of methanol production rate associated with the
approximately optimal shell temperature trajectories derived by
the proposed GA-GPS algorithm. The proposed Tshell trajectory
improved the associated production rates for 0, 5, and 10%
recycle ratio of CO2 by 1.67, 2.53, and 1.43%, respectively,
compared to the reference case of keeping the shell
temperature constantly at 524 K. The optimal shell temperature
trajectories for these cases gradually increase with time as
expected to compensate for catalyst deactivation. In addition,
the more CO2 is fed to the system, the higher Tshell is needed to
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Figure 7. Reactor temperature and the average catalyst activity profiles at the optimal case (the optimal case: 5% recycle ratio of CO2 and shell
temperature trajectory shown in Figure 6).
Figure 8. Predicted methanol production rates associated with the optimal shell temperature and recycle ratio of CO2 trajectories.
supply more heat to the endothermic reaction (eq 6). Figure 6
shows that the optimal solution does not violate the path
temperature constraint (eq 27).
The average catalyst activity versus time from both the
reference and optimal cases is shown in Figure 7. The average
catalyst activity in the optimal case is higher than in the
reference case as the reactor is operated at lower shell
temperature during the whole lifetime cycle of the catalyst
except the last two quarters.
3.2. Simultaneous Dynamic Stage Optimization of
Shell Temperature and Recycle Ratio of CO2. For this
section, we simultaneously optimized shell coolant temperature
and recycle ratio of CO2 to maximize the production rate.
Figure 8 compares the production rates and Tshell trajectories
for the proposed solution of the simultaneous optimization
(referred to as 0−10% CO2) with those for the proposed
solution with fixed 5% recycle ratio of CO2. As shown in Figure
8, the approximately optimal production rate for the 5% CO2
and 0−10% CO2 are remarkably close to each other. This result
implies that the recycle ratio of CO2 can be kept at 5% over the
1171
Article
time horizon for operational simplicity without significantly
reducing the production rate. This way, the number of variables
can be reduced for this optimization problem from 32 to 16 by
assuming a fixed amount of recycle ratio of CO2 is utilized (5%)
to obtain the optimal production rate.
4. CONCLUSIONS
An industrial Lurgi Type Methanol Reactor reactor with
catalyst deactivation has been modeled and optimized with
respect to the shell coolant temperature and the recycle ratio of
CO2 fed to the system. The results showed that correcting the
syngas ratio of the inlet stream of the reactor system improves
the production rate by increasing CO2 recycled ratio to 5% of
recovered CO2 from the reformer flue gases. The production
rates for 0 and 5% recycled CO2 ratio cases were improved by
1.67 and 2.53%, respectively. These improvements are
equivalent to 2.73 and 4.13 million U.S. dollars based on an
average price of 400 per ton of methanol, respectively, over four
years of operation compared to the reference case (Tshell = 524
K and no extra CO2 added to the system). Because no tax is
DOI: 10.1021/acs.iecr.5b02918
Ind. Eng. Chem. Res. 2016, 55, 1164−1173
Industrial & Engineering Chemistry Research Article

collected on fossil fuel production in the region where the plant RWGS = Reverse water gas shift reaction.

■
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