Chemical Engineering Science 60 (2005) 4275 4286

www.elsevier.com/locate/ces

Modeling, simulation and control of a methanol synthesis xed-bed reactor

M. Shahrokhi , G.R. Baghmisheh
Department of Chemical & Petroleum Engineering, Sharif University of Technology, P.O. Box 11365-9456, Tehran, Iran

Received 21 June 2004; received in revised form 8 November 2004; accepted 23 December 2004
Available online 18 April 2005

Abstract
In this paper, the dynamic behavior and control of the low pressure methanol synthesis xed bed reactor have been investigated. For
simulation purpose, a heterogeneous one-dimensional model has been developed. First, the reactor simulation is carried out under steady-
state condition and the effects of several parameters such as shell temperature, feed composition (especially CO2 concentration) and recycle
ratio on the methanol productivity and reactor temperature prole are investigated. Using the steady state model and a trained feedforward
neural network that calculates the effectiveness factor, an optimizer which maximizes the reactor yield has been developed. Through the
dynamic simulation, the system open loop response has been obtained and the process dynamic is approximated by a simple model. This
model is used for the PID controller tuning and the performances of xed and adaptive PID controllers are compared for load rejection and
set point tracking. Finally the proposed optimizer is coupled with a controller for online optimization and hot spot temperature protection.
2005 Elsevier Ltd. All rights reserved.

Keywords: Methanol synthesis; Fixed-bed reactor; Dynamic simulation; Adaptive PID; Temperature runaway; Feedforward neural network

1. Introduction
Chemical reactors especially xed-bed catalytic reactors
that are used in highly exothermic processes are often dif-
cult to control and it is important to predict the possibility
of hot spot and thermal runaway occurrences (Assaf et al.,
1996). This is the case when wide uctuations in tempera-
ture extremes occur from relatively minor uctuations in one
or more operating variables. Operation in the unstable re-
gions may result in poor product and temperature runaway.
The need for optimal control of chemical reactors has been
well recognized since the early 1980s, due to the increasing
cost of raw material and energy (Zhou et al., 1999). Mul-
titubular xed-bed reactors are industrially used in the low
pressure methanol synthesis from syngas. This catalytic re-
action is highly exothermic and temperature has signicant
effect on the reactors yield. In this work dynamic behavior
and control of a low pressure methanol synthesis xed-bed
reactor has been considered. Despite of the relatively simple
Corresponding author. Tel.: +98 21 6165419; fax: +98 21 6022853.
E-mail address: shahrokhi@sharif.edu (M. Shahrokhi).
0009-2509/$ - see front matter 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.ces.2004.12.051
design and the most frequently use of these types of reac-
tors, the boundaries of the system and their interactions are
quite complex and can raise complicated problems in de-
sign, safe operation, optimization and control. Modeling of
these reactors is a complex task since a system of nonlin-
ear differential equations must be solved and many transport
and chemical parameters should to be evaluated; in addition
the diffusion of gas into the solid matrix is hard to model
(Parisi and Laborde, 2001). Several authors have studied the
steady-state modeling of catalytic methanol synthesis reac-
tor at various level of complexity, but a few studies have been
done on dynamic simulations and control of methanol reac-
tor. The summary of these studies have been listed below.
Graaf et al. (1990) modeled low pressure methanol syn-
thesis using commercial CuZnAl catalyst. They showed
that commercial size of the catalyst particles exhibit intra-
particle diffusion limitations. Vanden Bussche et al. (1993),
based on a heterogeneous model, simulated the dynamic
behavior of a xed-bed methanol reactor. Their investiga-
tion includes comparison between different levels of tran-
sient modeling. Lommert et al. (2000) studied mathemat-
ical modeling of internal mass transport limitations in the
4276 M. Shahrokhi, G.R. Baghmisheh / Chemical Engineering Science 60 (2005) 4275 4286

methanol synthesis and showed that Thiele modulus con- 3. Development of the reactor model
cept with pseudo-rst-order kinetics are capable to pre-
dict the intra-particle diffusion. Lovik (2001) studied 3.1. Reactor model assumptions
modeling, estimation and optimization of the methanol
synthesis with catalyst deactivation. A rigorous pseudo- For modeling the reactor the following assumptions are
steady state modeling of methanol synthesis loop has made: (1) one-dimensional heterogeneous model is consid-
been considered in his simulation. Velardi et al. (2002) ered, (2) dispersion of mass and energy in axial and radial
investigated the feasibility of carrying out the low pres- direction are negligible, (3) the transient term is taken into
sure methanolsynthesis process in forced unsteady- account for the mass and energy balances, while the pseudo-
state conditions, using a network of three catalytic steady state condition is considered for the solid phase in
xed-bed reactors with periodical change of the inlet calculating the effectiveness factor, (4) the dynamics of the
position. catalyst deactivation is neglected because of its large time
The present paper focuses on the dynamic simulation constant.
and control of the methanol reactor. The paper is orga-
nized as follows. First the process and the related con- 3.2. Reactor mathematical model
trol loops are described. Modeling of reactor and steam
drum is considered next. For solving the equations de- One-dimensional and heterogeneous model has been con-
scribing the system behavior, the numerical methods for sidered for simulating the tubular xed-bed methanol syn-
solving nonlinear algebraic and differential equations thesis. To take into account intra particle mass diffusion, ef-
are discussed. Steady state and dynamic results are pre- fectiveness factor concept (Levenspiel, 2001; Elnashaie and
sented and nally reactor control and optimization are Elshishini, 1993; Wijngarden et al., 1998) has been used.
considered. The mass and energy equations are given below.
Component mass balance:


jxi us F 0 jx i
= 0 +
i (z)b ri Ar ,
jt F L r jz
2. Process summary
(i = key component (MeOH & CO)). (1)
The process ow sheet of the methanol synthesis loop is Energy balance:
shown in Fig. 1. The catalyst is packed in vertical tubes and
  NR 
surrounded by the boiling water. The reaction heat is trans- jT us C p,g jT 
ferred to the boiling water and steam is produced. Efcient C p,m = + b ((
H )k
k (z)rk )
jt Lr jz
heat transfer gives small temperature gradient along the re- k=1

actor. Typical operating conditions are 543 K and 80 bar. The 4Ueff
reactor temperature is controlled by controlling the pres- + (T TC ) . (2)
do
sure of the boiling water. Besides the pressure loop a level
controller is used for controlling the water level in steam
For the pressure drop, the following equation has been used
drum.
(Ergun Equation):
  
d 3 1
P = 10 Lr 1.75 + 150
dz NRe
u2s g 1 
. (3)
dp 3

In above equations
i is the effectiveness factor which can be

calculated from the following equations that must be solved
with the above equations simultaneously:
j
  j 
De 1 d 2 d Ps

Rg R p  d 
2 2 d  Ts
= b rj , (j = all component), (4)
  NR

Ke 1 d 2 d
 T s = p (
Hk )rk , (5)
Fig. 1. Flow sheet of Lurgis synthesis loop and its control strategy (Lovik, Rp2 2 d d
2001). k=1
 M. Shahrokhi, G.R. Baghmisheh / Chemical Engineering Science 60 (2005) 4275 4286 4277

 i i
ri dVp De (dPs /dr)r=Rp Table 1

i = = , Kinetic and equilibrium constants
Vp ri |Surface Rg Ts (Rp /3)p ri |Surface
(i = key component (MeOH & CO)). (6) k = A exp(B/Rg T ) A B

The Eqs. (4), (5) are written based on pseudo-steady state ka (bar 1/2 ) 0.499 17197
kb (bar 1 ) 6.62e11 124119
assumption. Regarding this assumption, it should be men-
kb 3453.38
tioned that if the rate equations are linearized and the kd (mol/kg s bar2 ) 1.07 3669
approach proposed by Szukiewicz (2001) is used, the ke (mol/kg s bar) 1.22e10 94765
maximum time constant for the diffusion-reaction equations
(including the transient term) will be about 7 s, while the K eq = 10(A/T B) A B
time constant for the composition change is around 37 s. K1 (bar 2 )
eq
3066 10.592
These observations justify the pseudo-steady state assump- eq
K2 2073 2.029
tion.
The initial and boundary conditions for the bulk phase
and the boundary conditions for the catalyst pellets are given
below. The reaction rates of methanol and carbon monoxide accord-
Boundary conditions for the bulk gas phase: ing to reactions (B) and (C) have been proposed by Vanden
Bussche and Froment (1996) and are given below:
z = 0: xi = 0, i = key component,
   
P = Pinlet , T = TInlet . (7) 1
kd PCO PH2 1 eq (PH2 O PCH3 OH /PH2 PCO2 )
Initial conditions for the bulk gas phase: K1
rB =
3 , (14)
1+kc PH2 O /PH2 +ka PH2 +kb PH2 O
t = 0, z: xi |t=0 = xi |steady state ,
T |t=0 = T |steady state . (8) eq 
ke PCO2 1 K2 (PH2 O PCO /PH2 PCO2 )
rC =
. (15)
Boundary conditions for the catalyst pellet: 1 + kc PH2 O /PH2 + ka PH2 + kb PH2 O
d i
 = 0: P |=0 = 0, i = all components, The kinetic parameters are given in Table 1.
d s
d
Ts |=0 = 0, (9)
d
4. Steam drum mathematical model
Dei d i
 = 1: P |=1 = kgi (Psi |=1 P i ),
Rp d  s To develop a steam drum model, the following assump-
Ke d tions are made: (1) in energy balance, pseudo-steady state
Ts |=1 = hf (Ts |=1 T ). (10)
Rp d  condition is considered for vapor phase, (2) energy losses via
surrounding is neglected. The dynamics of this process can
Solving the above equations for calculating the effectiveness be described by the following set of mass and energy bal-
factor is time consuming. One way to reduce the computa- ance equations for liquid and vapor phases (Luyben, 1986;
tion time is using the concept of Thiele modulus. Lommert Ramirez, 1997) and the schematic diagram of the steam
et al. (2000) have linearized the methanol reactions and used drum is shown in Fig. 2.
the concept of Thiele modulus to calculate the effectiveness
factor. The parameters of the linearized rates are adopted
by using the real rates along the reactor. Their approach is
described briey in Appendix A.
The model is completed by the kinetic equations given
by Vanden Bussche and Froment (1996) which is based on
LangmuirHinshelwood and HougenWatson mechanism.
In this kinetic model two independent reactions (hydrogena-
tion of carbon dioxide and the reverse watergas shift re-
action) out of the three following depended reactions are
considered:

(A) CO + 2H2 CH3 OH, (11)

(B) CO2 + 3H2 CH3 OH + H2 O, (12)

(C) CO2 + H2 CO + H2 O. (13) Fig. 2. The schematic diagram of the steam drum.
4278 M. Shahrokhi, G.R. Baghmisheh / Chemical Engineering Science 60 (2005) 4275 4286

Table 2 algebraic equations are integrated by TR-BDF2 method

Methods used for calculating the physicochemical properties
Property
Gassolid heat transfer co-
efcient
Gas viscosity
Gas conductivity
Binary diffusion coefcient,
component i and j
Effective diffusion coef-
cient in pellet, component i
Overall heat transfer coef-
cient gas phase to boiling
water
Water saturation pressure
Mixed gas heat capacity
Mass transfer coefcient
Gas compressibility factor
for reactor inside
Gas compressibility factor
for steam
Method
ChiltonColburn analogy (Poling
et al., 2001)
Lucas (Poling et al., 2001)
SteilThodos (Perry and Green,
1997)
FullerSchettlerGidding (FSG)
(Perry and Green, 1997)
Wilke equation (Froment and
Bischoff, 1990)
Lovik, 2001
KeenanKeyes (Perry and Green,
1997)
Ideal gas (Poling et al., 2001)
Cussler Equation (Perry and Green,
1997)
PengRobinson (Poling et al., 2001)
SoaveRedlichKwong (Poling
et al., 2001)
(Shampine, 1994). To calculate the effectiveness factor for
catalyst pellets, rst, two-point boundary differential equa-
tions for catalyst pellets are discretized by orthogonal col-
location using nite difference (Finlayson, 1980, 1972) and
then the resulting nonlinear equations have been solved by
GaussNewton and trust-region method (Coleman and Li,
1996). To decrease the computation time in dynamic simu-
lation, two other methods are tested. These techniques are:
(1) articial feedforward neural network (AFFNN) trained
with the obtained data from exact simulated system (Parisi
and Laborde, 2001), (2) the adaptive linear kinetic rate
Thiele Modulus method (ALKTM) described by Lommert
et al. (2000). Both techniques reduce the computation time
considerably. The AFFNN is faster but ALKTM has better
accuracy.
6. Steady-state simulation results
6.1. Model validation

The steady-state simulation results are compared with the

data obtained from three industrial reactors. The simula-
Continuity equation for liquid phase: tion results with corresponding industrial data are given in
d(l Vl ) Table 3. As can be seen there is a good agreement between
= m Fm W . (16) simulation results and industrial data.
dt
Through steady-state simulation the following results
Continuity equation for vapor phase: have been obtained: (1) CO2 injection to fresh syngas in-
d(v Vv ) creases the methanol productivity (Table 4), which conrms
= W  v Fv . (17) the results obtained by Skrzypek et al. (1995); (2) increas-
dt
ing the recycle ratio, increases the methanol productivity
Energy balance for liquid phase: (Table 4) and decreases the possibility of hotspot formation
d(l Vl Tc ) at the expense of increasing operation costs. As the nal
Cp,w = m Fm hm hs W + QR , (18) conversion approaches the equilibrium conversion, the ef-
dt
fect of recycle ratio on reactors yield decreases; (3) the
where W, Vv , Fv and Pv are given by the following equations:
methanol productivity and temperature prole in reactor are
W = KMT (P sat Pv ), (19) inuenced by the temperature of cooling water as shown in
Fig. 3(a, b).
z s v R g T c
Pv = , (20) To check the accuracy of the effectiveness factor ob-
MW water tained from Thiele modulus or articial network, these fac-
Vl + Vv = Vt , (21) tors are calculated and compared for simulation of reactor 1

(Table 3) as shown in Fig. 4.
Fv = Kv Pv (Pv P0 ). (22) As can be seen both methods can predict the effective-
The terms KMT and Kv are pseudo-mass transfer and con- ness factor fairly well, but the Thiele modulus method has
trol valve coefcients respectively. The methods used for a higher accuracy.
calculating the physicochemical properties needed for sim-
ulation are given in Table 2. 6.2. Steady-state optimizer

The shell temperature strongly inuences the methanol

5. Numerical method
The partial-differential equations describing the reactor
dynamics are discretized by nite difference to ordinary-
differential equations. The resulting set of differential equa-
tions, steam drum equations and catalyst pellet nonlinear
yield and reactor thermal stability. As can be seen from
Fig. 3 there is an optimum temperature that maximizes
the methanol conversion for a given feed composition.
However, the hotspot temperature constraint in reactor
must be considered for thermal stability. When the feed
composition is changed, the shell temperature should
 M. Shahrokhi, G.R. Baghmisheh / Chemical Engineering Science 60 (2005) 4275 4286 4279

Table 3
Comparison of simulation results and industrial data

Property Simulation result Industrial Simulation result Industrial Simulation result Industrial
for reactor 1 reactor 1 for reactor 2 reactor 2 for reactor 3 reactor 3

MeOH Conversion 46.08 48.85 52.62 57.18 29.84 32.67

CO Conversion 35.17 35.55 38.33 41.42 17.79 18.51
Exit temp. ( C) 249 250 253 255 253 255
Exit P(bar) 79.3 76.1 62.02 61.16 78.1 76.45

Mole%
yCO2 4.87 4.66 2.50 2.18 8.43 8.1
yCO 2.17 2.17 1.70 1.44 2.61 2.38
y H2 57.58 56.92 76.37 75.71 50.12 48.97
yCH4 27.52 27.44 13.05 13.14 31.79 33.05
yH2 O 1.49 1.88 1.36 1.74 1.99 2.48
yCH3 OH 6.37 6.92 5.02 5.49 5.06 5.82
Byproduct 0.01

Table 4 By mixing these streams with different ratios, the reactor

Effects of CO2 injection and increasing recycle ratio on methanol yield feed is generated. In Fig. 5 the feed composition can be
Simulation results for reactor 1 ( Table 3) calculated through F1 /F2 ratio.
As can be seen from Fig. 5 there are two optimal proles.
Type of change Rate of changes Increasing methanol yield
The lower temperature prole is obtained by taking into ac-
CO2 injection rate Increasing CO2 rate 5.2% count the constraint on the temperature. The higher tempera-
by factor 2 ture prole is unconstrained optimal temperature trajectory.
Recycle rate Increasing recycle ra- 4.3% For calculating the optimal shell temperature for a given
tio from 3 to 4
feed composition, an optimizer has been developed. It uses a
steady-state model to calculate the optimal temperature con-
sidering the temperature constraints. In mathematical terms
it can be stated as follows:
be changed accordingly in order to have the maximum
conversion. The optimal temperature prole obtained maxTshell J = FTout yM
out
,
for different feed compositions is shown in Fig. 5. To
change the feed composition, two streams with differ- subject to
ent compositions (F1 : yMeOH = 0, yCO = 0.2052, yH2 =
Tmax
543 K,
0.6853, yCO2 = 0.084, yH2 O = 0.005, yCH4 = 0.0205 & F2 :
yMeOH = 0.0042, yCO = 0.0232, yH2 = 0.6213, yCO2 =
0.0491, yH2 O =0.0042, yCH4 =0.298) have been considered. 505
Tshell ,

Fig. 3. Effect of cooling uid temperature on (a) methanol conversion at reactor outlet and (b) reactor temperature prole along the reactor.
4280 M. Shahrokhi, G.R. Baghmisheh / Chemical Engineering Science 60 (2005) 4275 4286
Fig. 4. Comparison of effectiveness factors obtained from three different
methods.
where FTout and yM out are reactor outlet owrate and methanol
mole fraction respectively. The rst constraint is considered
to avoid hotspot in the reactor and the second constraint
is due to required quality of the produced vapor (Lovik,
2001). In the above objective function only methanol yield
has been considered and penalty on generated steam in shell
side is set to zero. The optimization has been carried out us-
ing Golden Section Search method (MATLAB optimization
toolbox (fminbnd)). In this method the two interior points
within the total interval are so selected that the interval elim-
inated on one iteration will be of the same proportion to the
total interval. For more details the readers are referred to
Edgar and Himmelblau (1988). To handle the constraints,
rst a relatively high shell temperature is chosen and the
optimum shell temperature is calculated by using Golden
Section Search method. If the upper bound on reacting gas
temperature is satised the search is completed and the pro-
gram terminates, otherwise a smaller shell temperature is
chosen and the above calculations will be repeated.
Fig. 5. Optimal shell temperature for different feed compositions.
7. Dynamic simulation results and controller design
7.1. Open loop response
To obtain open loop response of pressure loop, step
changes in different directions with different magnitudes
are applied to steam control valve opening while the level
is being controlled. The results are shown in Fig. 6. As
can be seen the process shows nonlinear behavior. The de-
gree of nonlinearity depends on deviations from operating
conditions.
7.2. Ofine identication
In order to model the pressure dynamics, maximum
20% deviation in manipulated variable is considered and
sequences of step changes with different magnitudes are
applied to process input and the inputoutput data are col-
lected. Two different models, rst and second order, are
considered. Using the ofine least squares method, the pa-
rameters of corresponding discrete models are identied.
Having the sample time and the discrete models, the param-
eters of the corresponding continuous models are calculated
(Seborg et al., 1989). These models are given in Table 5.
7.3. PID controller tuning and adaptive PID controller
The internal model control (IMC) technique has been used
for PID controller tuning. The PID controller formula and
the controller parameters are as follows:
 
1 D s
Gc (s) = Kc 1 + + .
I s N s + 1
For the rst order model:

Kc = , I = . (23)
K p c
 M. Shahrokhi, G.R. Baghmisheh / Chemical Engineering Science 60 (2005) 4275 4286 4281

performance. To compare the performances of xed PID

with adaptive PID, an adaptive PID controller based on
IMC techniques has been designed. For online identica-
tion recursive least squares with variable forgetting factor
(Fortescue et al., 1981) is used. To describe the system dy-
namics the following ARMA model is selected.

y(k) b0 + b1 q 1
G(q) = = .
u(k) 1 + a1 q 1 + a2 q 2

The system parameters are updated as follows:

P (k 1)(k)
Fig. 6. Open loop responses of shell pressure due to step changes in (k) = (k 1) + e(k),
steam owrate.
 + T (k)P (k 1)(k)

P (k)

1 P (k1)(k)T (k)P (k1)
Table 5 = P (k1) . (25)
 +T (k)P (k1)(k)
Ofine identication results for pressure control loop

Process parameters First order model Second order model

Where (k), (k) and e(k) are given below:
kp 2.9286e 3 mPa/s l 2.9286e 3 mPa/s l
1 (s) 170 210
2 (s) 70
T (k) = (a1 (k), a2 (k), b0 (k), b1 (k)), (26)
3 (s) 40
T (k) = (y(k 1), y(k 2), u(k), u(k 1)), (27)
kp kp (3 s + 1)
Gp1 = Gp2 =
1 s + 1 (1 s + 1)(2 s + 1)
e(k) = y(k) y(k)
= y(k) T (k)(k 1). (28)

 is the forgetting factor and computed from the following

equation:
Table 6
PID controller parameters
min , 0 < min ,

Controller N (s) D (s) I (s) Kc < 1,
(k) = max e2 (k)

1
PI (Pressure loop) 0 170 5.801e2 ,
PI (Level loop) 0 300 72 (1 +  (k)P (k 1)(k))
T
PID (Pressure loop) 40 21.25 159 8.195e2 (29)

where the is the tuning parameter. To solve the above

equations some initial values should be considered for (k)
and P (k).
For second order model:
The controller transfer function is
1 + 2 3
Kc = , I = 1 + 2 3 ,
K p c 1a 1 + a1 z1 + a2 z2
1 2 D(z) =  , (30)
D = 3 , N = 3 , b1 b2
1 + 2 3
(24) (1 z1 ) 1 + z1
b1
where c is a tuning parameter. This parameter is obtained
by minimizing the integral of absolute value of the error for where a, is a tuning parameter and is given below:
set point tracking. For level loop a PI controller is considered
and its parameters are obtained by the same procedure. The a = exp(2.3Ts /Tr ), Tr = 0.9 settling time,
PID parameters are given in Table 6. Ts = sampling time. (31)
The performances of PI and PID controllers for set
point tracking are compared and shown in Fig. 7. The The performances of xed and adaptive PID for set point
simulation results indicate that PID controller has a better tracking and load rejection are compared in Figs. 8, 9. For
4282 M. Shahrokhi, G.R. Baghmisheh / Chemical Engineering Science 60 (2005) 4275 4286
Fig. 7. Comparison of PI & PID performances for pressure set point tracking, (a) shell pressure vs. time, (b) methanol owrate vs. time, (c) steam
owrate vs. time.
set point tracking several step changes are applied to the
shell pressure set point as shown in Fig. 8a and for load
rejection the feed composition has been changed according
to gures given in Table 7.
As can be seen the performance of adaptive PID is much
better than xed PID in both set point tracking and load
rejection. It should be also noted that the maximum reactor
temperature overshoot is higher for the xed PID controller
compared to adaptive PID.
8. Online optimization
When the feed composition is changed the set point
of pressure loop should be changed accordingly in or-
der to have the maximum methanol yield. To calculate
the pressure set point corresponding to feed composition
an optimizer has been developed. The optimizer receives
the feed specications in each sample time and if detects
changes, calculates the new pressure set point (and cor-
responding shell temperature) by using the steady-state
model. For simulation it is assumed that the feed compo-
sition analyzer has 200 s delay. Fig. 10 shows the above
procedure.
To evaluate the performance of the control sys-
tem coupled with the developed optimizer, two dif-
ferent loads are applied to feed composition at t =
395 and t = 1000 s. The results are shown in
Fig. 11.
The simulation results show that the optimizer has
increased the methanol yield after loads are applied to
the feed composition. As can be seen from Fig. 11(b),
the second load has caused the reactor temperature to
exceed the maximum allowable temperature for a cer-
tain period of time, but it has been decreased when
the optimizer has provided the new pressure set point.
As can be seen the optimizer provides the maximum
methanol productivity while satisfying the temperature
constraints.
9. Conclusions
In this article using conservation laws, the dynamic
behavior of a methanol reactor has been simulated.
To reduce the computation time the effectiveness fac-
tor is estimated through AFFNN and ALKTM. ALKTM
provides more accurate results but AFFNN is faster.
 M. Shahrokhi, G.R. Baghmisheh / Chemical Engineering Science 60 (2005) 4275 4286 4283

Fig. 8. Comparison of xed & adaptive PID performances for pressure set point tracking, (a) shell pressure vs. time, (b) methanol owrate vs. time, (c)
steam owrate vs. time.

Fig. 9. Comparison of xed & adaptive PID performances for feed composition changes according to Table (6). (a) Shell pressure vs. time, (b) reactor
maximum temperature vs. time, (c) steam owrate vs. time.
4284 M. Shahrokhi, G.R. Baghmisheh / Chemical Engineering Science 60 (2005) 4275 4286

Table 7 Steady-state simulation result has a good agreement with

Load applied to feed composition industrial data. Using IMC technique and system model
Mole Initial feed Feed composition Feed composition obtained from open loop response, xed PID controller
fraction composition at t = 399 s at t = 1000 s is tuned. Performances of xed and adaptive PID con-
yCO2 8.39 6.83 8.4 trollers are compared for load rejection and set point
yCO 20.48 20.48 20.48 tracking. To increase the reactor yield an optimizer has
yH2 68.40 0.72 66.5 been developed which can be coupled with the control
yCH4 2.54 0.5 4.43 system. Simulation results indicate that using the opti-
yH2 O 0.19 1.019 0.19
mizer has increased the reactor productivity and thermal
yCH3 OH 0 0 0
stability.

Notation

Ar reactor section area, m2

C p,g specic heat of uid, kJ/m3 K
C p,m mean specic heat of bed (C p,g + s (1
)Cp,s ), kJ/m3 K
Cp,s specic heat of solid, kJ/kg K
Cp,w specic heat of water, kJ/kg K
dp , do catalyst and reactor outside diameter, m
Dei effective diffusion coefcient of compo-
Fig. 10. Control system coupled with an optimizer for optimizing the nent i in the pellet, m/s
methanol yield due to changes in feed composition. F0 inlet mole owrate, mol/s

Fig. 11. The performance of control system coupled with the proposed optimizer when two subsequent changes are applied to feed composition (a) shell
pressure vs. time, (b) reactor maximum temperature vs. time, (c, d) methanol owrate vs. time.
 M. Shahrokhi, G.R. Baghmisheh / Chemical Engineering Science 60 (2005) 4275 4286 4285

Fm , Fv volume owrate of makeup water, vapor, Appendix A

m3 /s
Gc transfer function of pressure loop or con- The procedure for calculating the effectiveness factor pro-
or p
troller posed by Lommert et al. (2000) is given below. The lin-
hf gas inside heat transfer coefcient, earized methanol reaction rates are as follows:
kW/m2 K
rMethanol
= kMethanol
eq
(CH2 CMethanol /kMethanol ), (A.1)
hm mass enthalpy of makeup, J/kg
eq
hs mass enthalpy of steam, J/kg rCO = kCO (CH2 CCO /kCO ), (A.2)
ka,b,c,d reaction rate parameters eq eq
kgi mass transfer coefcient from gas to pellet where KMethanol and KCO are dened as follows:
component i  
eq CMethanol
ke effective pellet conductivity, kW/m K kMethanol = , (A.3)
CH2
Lr reactor length, m eq
 
NRe Reynolds number based on particle eq CCO
NR number of reactions kCO = . (A.4)
CH2 eq
P , PInlet , P sat bulk, reactor inlet and saturation pressure,
kPa Having reaction the rates of methanol & CO which can be
P0 steam valve discharge pressure, kPa obtained from Eqs. (14) and (15), the pseudo-kinetic con-

Psi partial pressure inside the pellet, compo- stants KMethanol and KCO are determined from equations
nent i, kPa (A.1) and (A.2). Thiele modulus is dened as
QR heat generated by reaction, W 
 eq
R p k (k + 1)
r radial coordinate in catalyst, m j
M =  j j , (j = Methanol, CO). (A.5)
rB,C j eq
reaction rate, mol/kg s 3 De kj
ri,j or k reaction rate for component i, j or k,
mol/kg s From the Thiele modulus the effectiveness factor can be cal-
Rg gas constant, kPa m3 /mol K culated from the following equation (Froment and Bischoff,
Rp catalyst radius, m 1990):
t time, s  j j j

3Sh M cosh M sinh M
T , TInlet , Tc , Ts temperature (reactor inside, reactor inlet,
j = j j j j
, (A.6)
cooling water, solid), K M 2 M cosh M + (Sh 1) sinh M
us supercial gas velocity, m/s where
Ueff effective heat transfer coefcient,
Kgi Rp
kW/m2 K Sh = j
. (A.7)
Vv,l,p,t volume (vapor, liquid, particle, total), m3 De
W water boiling rate, kg/s
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