8.
11 Chemical Reactors: Simulation and Modeling
A. B. CORRIPIO, P. A. HOLST (1970)
B. G. LIPTÁK (1995) B. G. LAKATOS
INTRODUCTION
In order to be able to control a process, the process control
engineer must understand it and know how the process will
respond to changes in loads or other inputs. Modeling and
simulation are important tools that can be used in analysis
of physical systems and in the understanding of the function-
ing of processes. Besides, the physical equipment to be con-
trolled does not yet exist, and consequently, no experimental
data exists for them. Even if the process equipment is avail-
able for experimentation, the procedure usually is very costly,
and, consequently, it is preferred if one can use a model to
predict the behavior of the processing systems.
The fundamental models can be derived from the basic
principles and from thorough knowledge of the process. In
characterizing a processing system, one needs (1) a set of
fundamental variables describing the state of the system, and
(2) a set of equations for these variables, which describe how
the state of the given system changes with time. The dynamic
characteristics of a process, the knowledge of which is fun-
damental to designing the control systems, are described by
the dynamic models in their general time-dependent form
from which the steady-state models can be obtained as lim-
iting cases forcing the time derivatives to zero.
Model Building
In the case of a chemical reactor, several factors enter into
the model-building process. The set of physical characteris-
tics is described by the balance equations of three fundamen-
tal quantities: mass, energy, and momentum.
Reaction kinetics is the other main consideration in choos-
ing conditions for carrying out a reaction. Quantities such as
density, heat capacity, and other physical–chemical parameters
also are part of the overall model. An important element in the
overall model can be an economic submodel containing a cost
or profit objective function, useful in evaluating the possible
process variables and in optimizing the system. Statistical ele-
ments can also be incorporated into the model on the basis of
which future behavior of the system can be predicted.
Once a model has been built it can be used for examining
the process behavior, for operator training, and also for devel-
oping different control algorithms and configurations. Early
© 2006 by Béla Lipták
A. B. CORRIPIO (1985)
(2005)
predictions of the likely conditions that the reactor is approach-
ing can also be predicted from the model, thereby giving time
for the control system to correct such trends.
Steady-state simulations are often used in equipment
design. Discrete dynamic simulations serve to optimize sched-
ules, maximize production, and minimize equipment and inven-
tory requirements. Continuous dynamic simulation is useful for
improving control strategy, reducing start-up and heat-up times,
and improving on-stream times. Real-time simulation is used
both for operator training and for debugging DCS and PLC
systems, thereby providing both improved performance and
safety.
SIMULATION
All the control programs must be tested under simulated plant
conditions before the control system is connected to the pro-
cess. A step-by-step simulation and checkout must take place
in order to ensure the validity of all control strategies
designed for a particular application. Prior to the simulation,
it is usually necessary to wire to the simulator a number of
analog input signals (DC source and individual potentiome-
ters), analog output signals (DC meters), discrete input sig-
nals (AC/DC source and individual switches), and discrete
output signals (AC/DC lights).
These tools play an important role in control system
analysis and design, and are still used today to some extent.
However, these days most simulation work is carried out by
means of digital computers, which allow engineers to analyze
and design more sophisticated control strategies and systems.
Digital computers offer a lot of function blocks by means of
which practically all linear and nonlinear process and control
elements can be modeled. Although simulation with digital
computers is more effective, the methodologies of testing and
checkout of control systems are similar.
As the first step in the testing, all continuous (regulatory)
loops are tested under both open and closed conditions, while
the discrete controls are deactivated. For inherently stable
processes, usually open-loop testing (without process dynam-
ics) is adequate. Whenever dynamic process conditions must
be simulated, a program is required to generate these condi-
tions. The process variables of the models are monitored to
1711
1712 Control and Optimization of Unit Operations

determine the responses and stability of algorithms to the set means of the transfer function
point and simulated process load changes, respectively.
The next step is the simulation and checkout of the discrete  100 1 T s 
M (s ) =  + + D  E (s ) 8.11(3)
functions, namely direct on/off control, interlock control, and  PB TI s 1 + T0 s 
sequential control. Using the simulator or the simulation pro-
gram, one can imitate normal or abnormal conditions and in which all three modes can be adjusted independently.
check the system responses. If a very large number of discrete In general, the proportional band should have an overall
I/O is required in order to check a very complicated sequential adjusting effect, which leads to the practical noninteracting
control strategy, a simulator program can be generated, and controller with the transfer function
the test can be conducted in the same manner as a dynamic
test for continuous (regulatory) control described earlier. 100  1 T s 
In addition to the previously described simulation, when M (s ) =  1+ + D  E (s ) 8.11(4)
PB  TI s 1 + T0 s 
the system is fully installed in the field, a test run is recom-
mended prior to actual start-up. Modern controllers often limit the derivative action to
respond only to measured variable changes and not to rapid set-
Control System Simulation point changes, which could upset the process. This is stated in
The simulation of instrumentation and control systems includes the modified transfer function
the measuring or detecting devices, the controllers, and the
actuating or manipulating of output elements. Most measur- 100  1  T s 
M (s ) =  1+ E (s ) − D Y (s )  8.11(5)
ing devices may be simulated by one or more simple lags for PB  TI s  1 + T0 s 
dynamic representation, with added static nonlinearities for
device characteristics, sensitivity, or operating point modeling. which is of the noninteracting type.
For special functions, such as logarithmic input/output
relationships (pH measurements), the general-purpose Digital Control Simulation
function-generating units may be used, or the functions may
be generated by implicit techniques. When the measuring Digital control may be simulated directly with a discrete con-
device puts out a discontinuous (pulse-type) signal, the signal- troller, where the measured variable y(t) and the set point r(t)
generating circuits may be applied. in the time domain are sampled at fixed intervals ∆T, called
A direct, three-mode (PID) controller has the transfer sampling period, and t = nT. Denoting now the actuating error
function: by e(nT ) = y(nT ) − r(nT ), or en = yn − zn, the numerical
approximation of the controller algorithm 8.11(5) is
100  1  TD s 
M (s ) = 1 +  1 +  E (s ) 100  TD ( yn − yn−1 ) 
n

∑e
8.11(1) T
PB  TI s   1 + T0 s  ∆ mn = e + − Sn  8.11(6)
PB  n TI k
T0T 
 k =1
where (all variables are in Laplace representation)
M(s) = controller output where the term
E(s) = actuating error, E(s) = R(s) – Y(s)
Y(s) = measured (controlled) input variable ( n− k )T
n

∑
−
R(s) = set point Sn = e T0 8.11(7)
k =1
PB = proportional band
TI = integral (reset) time is due to the convolution of functions.
TD = derivative time This is referred to as the position form of the PID control
T0 = filtering (stabilizing) time constant algorithm, because the actual control output is computed. An
alternative form of this algorithm is the velocity form, in which
The filtering time constant is usually made as small as the change of the controller output from the preceding period
possible and is often a fraction of the derivative time constant is computed rather than the actual controller output itself. In
TD (such as T0 = TD /16). Often, the proportional band is this case, the velocity form corresponding to 8.11(5) becomes
replaced by the proportional gain expressed as
100  T T
100 mn − mn−1 =  1 +  en − en−1 − D
Kc = 8.11(2) PB  TI  T0T
PB

The controller transfer function in Equation 8.11(1) is of × [SSn yn − (Sn + Sn−1 ) yn−1 + Sn−1 yn− 2 ]
the interacting type, which is the common case in most indus- 
trial applications. A noninteracting controller is obtained by 8.11(8)

© 2006 by Béla Lipták


mo
Desired Limiting
Time
Response of velocity limited system
FIG. 8.11a
Velocity-limiting response.
The track-store operation is controlled by the pulse P
occurring once during each time interval T to produce an
output pulse ∆mn = mn − mn−1 of amplitude corresponding to
the desired change in the control variable.
Control Valve Simulation
The most important actuating or manipulating output element
is the control valve, which may have several distinct aspects
in computer simulation. The flow characteristics can gener-
ally be linear, equal-percentage, hyperbolic, quick opening,
or square root. The valve characteristics can be modeled by
special computer circuits or by function-generating blocks
for true representation. Additional factors, such as limiting
or backlash in valve stem movements, must be included.
The dynamic behavior of a control valve may be repre-
sented by a time lag of first or second order, with a limited
velocity in stem movement. The time lags are simulated by
lag or lag-lead elements. Velocity limiting may be expressed
by the differential equation
dx  dx 
= min  vL ; ideal  . 8.11(9)
dt  dt 
where x is the stem position, vL denotes the velocity limit,
and xideal is the input position of an ideal, unconstrained valve.
The response of a velocity-limited device is shown in
Figure 8.11a. This can respond perfectly to a driving function
as long as the maximum velocity does not exceed the limit
vL. When the velocity exceeds the limiting value, the gain of
the actuator decreases and its phase lag increases as shown
in Figure 8.11a.
REACTOR MODELS
In any production system where a chemical change is taking
place the chemical reactor is the heart of the process. The
remaining operational units of the plant serve for preparing
the reactants to make one or more products of greater value,
and for the separation, purification, and formation of the
products produced in the reactor or reactor system. Thus, the
plant efficiency hinges to a great extent on the efficient oper-
ation of the reactor.
© 2006 by Béla Lipták
8.11 Chemical Reactors: Simulation and Modeling 1713
Chemical reactors may be divided into two main catego-
ries: homogeneous and heterogeneous. In homogeneous reac-
tors only one phase, usually a gas or a liquid phase, is present.
In heterogeneous reactors two, or possibly three, phases are
present. Common examples are gas-liquid, gas-solid, liquid-
solid, liquid-liquid, and gas-liquid-solid systems. In cases
where one of the phases is a solid, it quite often serves as a
catalyst.
The basis for the mathematical model of a chemical
reactor are the fundamental physical and chemical laws such
as the conservation of mass, energy, and momentum, as well
as chemical equilibrium and chemical kinetics. The detailed
mathematical model of a process reactor, however, often con-
sists of a large number of nonlinear differential and algebraic
equations, which usually involve more information that is
relevant to the objectives of simulation and control. As a
consequence, usually simplified, reduced models are used to
model the flow conditions of process reactors.
The two basic types of flowing reactors are shown in
Figure 8.11b. In the continuous stirred tank reactor (a) the
agitator thoroughly disperses the reactants into the reaction
mixture immediately as they enter the tank. In the tubular-
flow reactor (b) there is as little mixing as possible between
the reactants, which are flowing through the tube. These two
reactors are described by the perfect mixing model and plug-
flow model, respectively. These represent the two limiting
cases of flow models.
Reaction Kinetics
The principle of chemical kinetics determines the rate at which
a reaction proceeds toward the maximum extent determined
by the chemical equilibrium. The reaction rate depends on the
concentrations of the reactants and on temperature. For gas
Reactant A Reactant B
Products
(a)
Reactant A
Products
(b)
Reactant B
FIG. 8.11b
Two basic types of flowing chemical reactors are the continuous
stirred tank (a) and the plug-flow variety (b).
1714 Control and Optimization of Unit Operations
phase reactions the concentrations are proportional to the pres-
sure, and therefore the pressure also affects the rate of reac-
tions.
In case of a homogeneous reaction:
aA + aB → qQ + sS 8.11(10)
where: “a” moles of species A react with “b” moles of
species B to produce “q” moles of species Q and “s” moles
of species S. A and B are therefore the reactants, Q and S
are the products, and a, b, c, and d stand for the corresponding
coefficients in the stoichiometric Equation 8.11(10). Such a
reaction is called irreversible, and it will stop when either
reactant is completely consumed.
For homogeneous irreversible reactions the rate of reac-
tion is measured as moles of one of the reactants transformed
per unit volume of reacting mixture and unit time:
1 dn A
rA = − 8.11(11)
V dt
where rA is the rate of consumption of reactant A, and nA
denotes the total moles of A in volume V. The rate of reaction,
however, can be expressed also in terms of other reactants
and products. Because in this case the direction of change of
species Q and S are reversed, these rates are related to rate
rA as
b q s SI system 8.314 J/(mol °K)), and T is the absolute tempera-
rB = r , rQ = − rA , rS = − rA 8.11(12)
a A a a
The reaction that does not proceed to completion is called
reversible, and it is necessary to include also the kinetics of
the reverse reaction:
aA + bB ↔ qQ + sS. 8.11(13)
The arrow pointing to the left indicates that the reaction
is reversible; i.e., both forward and reverse reactions take
place simultaneously. Therefore, the state of chemical equi-
librium is regarded as a dynamic balance between the forward
and reverse reaction.
The equations that express the rate of reaction in terms
of concentrations of the reactants and products are called the
kinetic model of the reaction. A typical model for the revers-
ible reaction represented by Equation 8.11(13) could be
 
1
rA = − k f  cαA cBβ − cQς cSσ  8.11(14)
 K 
where cA, cB, cQ, and cS are the concentrations of the corre-
sponding species in moles per unit volume. The exponents
in this expression are often equal to a, b, q, and s, respectively,
and then the reaction is said to be elementary.
If the exponents differ from the coefficients of Equation
8.11(13), the reaction is not elementary, meaning that the
© 2006 by Béla Lipták
actual mechanism of the reaction consists of a series of inter-
mediate elementary steps that are summarized by Equations
8.11(13) and 8.11(14). When the functional relationship has
the form of Equation 8.11(14), the reaction is said to be of
order α , β, ς and σ, with respect to the species, while the
orders of the forward and reverse reactions overall are α +
β and and ς + σ, respectively.
In Equation 8.11(14), parameter kf is the rate coefficient
of the forward reaction, and K is the equilibrium constant for
which the relationship
kf
K= 8.11(15)
kr
holds where kr is the rate coefficient of the reverse reaction.
For irreversible reaction kr = 0, so that K → ∞ and the second
term in parentheses in Equation 8.11(14) becomes 0.
Both the rate coefficient and the equilibrium coefficient
are functions of temperature. Experimentally, the influence
of temperature on the rate coefficient is well represented by
the Arrhenius equation
E
−
k f = k f 0e RT 8.11(16)
where E is called the activation energy of the reaction, R is
the universal gas constant (1.98 BTU/(lb-mole °R) or in the
ture of the reacting mixture.
A kinetic model is essential for the simulation of a pro-
cess reactor. The functional relationship and the parameters
are identified with the aid of reaction rate data measured in
the laboratory or pilot plant, fitting a rate equation of general
form to a set of experimental data. However, the kinetic
model does not have to be as accurate for control simulation
as it would have to be for designing the reactor.
Perfectly Mixed Flow Reactor
The essential feature of the continuous stirred tank reactor is the
assumption of complete uniformity of concentration and tem-
perature throughout the reactor volume. Because with perfect
mixing, the reactor contents are completely uniform, it is also
called the perfectly mixed flow reactor in which the conversion
takes place at unique concentration and temperature levels.
The mathematical model is developed using the principle
of the conservation of energy and mass:
 rate of   rate of   rate of 
 quantity  =  quantity  −  quantity 
 accumulation   in   out 
 rate of   rate of 
+  quantity  −  quantity  8.11(17)
 produced   consumed 
 8.11 Chemical Reactors: Simulation and Modeling 1715

cA - Concentration Equations 8.11(19) and 8.11(20) can be combined, which

Cp - Specific heat results in the equation
Reactant A
∆Hr - Heat of reaction
(Fin, CAin, Tin, rin, Cp)
T - Temperature
A- Surface area dc A Fin
U - Heat transfer coefficient = (c − c ) + rA . 8.11(22)
V - Volume
dt V Ain A
F - Volumetric flow rate
r - Density The ratio Fin /V is the reciprocal of the mean residence
(Fw, Tj, rw, Cpw)
INDICES time of the reactor, which is, in principle, the time constant
(V, cA, T, r, Cp, ∆Hr)
A - Reactant A
w - Cooling water
of the perfectly mixed reactor.
in - Input
(Vj, Tj, rw, Cpw, A, U ) The Energy Balance The energy balance equation on the
Cooling water
(Fw, Twin, rw, Cpw) reactor is written as
Product
(F, cA, T, r, Cp)
d (V ρC pT )
= Fin ρinC pinTin − F ρC pT
FIG. 8.11c dt
The parameters used in modeling a perfectly mixed flow reactor + V (− ∆Hr )rA − UA(T − Tj ) 8.11(23)
with a cooling jacket.

where T and Cp are the temperature and the mean specific

heat of the reacting mixture, and, again, index in denotes the
where the quantity may represent mass, mass of individual
corresponding input variables. (−∆Hr) denotes the heat lib-
components, and energy. Equation 8.11(17) is called balance
erated in the reaction per unit mass of A reacted, Tj is the
equation of the given quantity.
temperature of the cooling water in the jacket, A is the effec-
If an irreversible, exothermic reaction resulting in A →
tive heat-transfer surface area between the reactor and the
Product is carried out in the reactor, which is cooled by water
jacket, and U is the overall heat-transfer coefficient.
flowing through a jacket, the total mass balance in the reactor
(shown in Figure 8.11c) can be written as Assuming that the density and the specific heat are con-
stant and using similar reasoning that resulted in Equation
8.11(22), Equation 8.11(23) can be reduced to the form
d (V ρ)
= Fin ρin − Fρ 8.11(18)
dt (− ∆Hr )
dT UA
= Fin (Tin − T ) + r − (T − Tj ). 8.11(24)
where V is the volume and ρ is the mean density of the dt ρC p A V ρC p
reacting mixture, and F denotes the volumetric rate of flow.
The subscript in is referred to the inputs of the system. Finally, the energy balance on the jacket gives the equa-
If the density of the reacting mixture is not changed tion for the temperature of the jacket Tj taking the form
appreciably by the reaction (ρin = ρ), then Equation 8.11(18)
can be simplified as dTj Fw UA
= (T − Tj ) + (T − Tj ) 8.11(25)
dt V j ρwC pw w V j ρwC pw
dV
= Fin − F 8.11(19)
dt
where Fw , Cpw , and Tw are the volumetric flow rate, the
describing only the change in volume of the reacting mixture specific heat, and the inlet temperature of the cooling water,
as a function of time. respectively.
The mass balance equation on reactant A is given by
Gas Phase Reactors In gas phase reactors, the reactor pres-
d (Vc A )
= Finc Ain − Fc A + VrA 8.11(20) sure significantly affects the performance of the reactor so
dt that the description of the changes of pressure should be
included into the model. In this case the density varies with
where cA denotes the concentration of reactant A, and rA is
pressure and composition, and the flow out of the reactor
the reaction rate expressed in terms of concentration of reac-
passes through a control valve. The density usually is com-
tant A.
puted using the perfect gas law
Taking into account that

d (Vc A ) dc dV Mp
= V A + cA 8.11(21) ρ= 8.11(26)
dt dt dt RT

© 2006 by Béla Lipták

1716 Control and Optimization of Unit Operations

where M is the mean molecular weight of the reacting mix- vin vn , cAn , Tn , rn vN
ture and R is the universal gas constant. The concentration cAin cAN
Tj
of reactant A is expressed as Tin TN
rin rN
1 2 … n−1 n … N
py
cA = A 8.11(27)
RT
∆x
where yA is the mole fraction of species A.
In Equation 8.11(18), the outflow through the control FIG. 8.11e
The model of a plug flow reactor consists of a number of compart-
valve can be expressed as
ments.

p − pout
F = CV 8.11(28)
ρ carried out, is divided into a number of compartments, as is
where CV is the valve sizing coefficient, and pout is the constant
pressure controlling the out-flow. Equations 8.11(26)–
8.11(28) can be substituted into Equations 8.11(18), 8.11(20),
and 8.11(24) to express them in terms of ρ, p, yA, and T to
obtain the mathematical model of the gas phase reactor. Nat-
urally, in this case the volume of the reactor V is constant.
Plug Flow Reactor
Plug flow is a simplified and idealized view of the motion of
a fluid, whereby all the fluid elements move with a uniform
velocity along parallel streamlines. It is also assumed that
the concentrations and temperature are uniform across the
cross-sectional area of flow. Tubular reactors, such as shown
in Figure 8.11d, with very high velocities, tend to approach
plug flow conditions.
Whereas composition and temperature are functions of
time only in the perfectly mixed reactor, in the plug flow
reactor they are functions of time and distance x from the
entrance. Thus, the plug flow reactor is a distributed param-
eter system, having a dynamic model, which consists of
partial differential equations. To solve a partial differential
equation it must be approximated by a number of ordinary
differential equations. However, a special case of a model
containing N equal-size perfectly mixed tanks, called com-
partments in the present context, arranged in series forms, is
a useful and frequently used approximation of the plug flow
reactor. This method will be shown here.
The tubular reactor in Figure 8.11d, in which an irrevers-
ible, endothermic reaction A → Product is assumed to be
illustrated in Figure 8.11e. The compartments are assumed
to be connected in cascade without any back-flow. The length
of each compartment is ∆x and its volume is A∆x, where A
is the cross-sectional area of flow. As a consequence, if the
volume of the reactor is V and N compartments are used in
the modeling, then the length of a compartment is derived as
∆x = V/NA. Further, if the linear velocity of flow is denoted
by v then the volumetric velocity is Av.
The mathematical model of the system now can be devel-
oped by sequentially applying the principle expressed in
Equation 8.11(17) for each compartment. The mass balance
around the nth compartment, shown in Figure 8.11f, can be
written as
d ( A∆x ρn )
= Avn−1ρn−1 − Avn ρn , n = 1, 2 K N 8.11(29)
dt
where ρn is the mean density and vn is the mean linear velocity
of the reacting mixture in the nth compartment. For the first
compartment ρ0 = ρin and v0 = vin, where the subscript in
denotes the input variables to the reactor. In liquid phase
reactors, the density is assumed to be constant. In gas phase
reactors Equation 8.11(26) is used to compute the density
from the pressure and temperature of the compartment.
Because the parameters x and A are constant, Equation
8.11(29) can be simplified to give
d ρn 1
= (v ρ − v ρ ), n = 1, 2 K N ,
dt ∆ x n−1 n−1 n n
v0 = vin , ρ0 = ρin 8.11(30)

Tj
n vn
Tf cA, T, v vn-1 cAn
cA, n-1 Tn
cAin , Tin , vin Tn-1 rn
rn-1 Vn = A∆x
A
x ∆x

FIG. 8.11f
FIG. 8.11d The compartment model of the nth compartment of a plug flow
Plug flow reactor with heating jacket. reactor.

© 2006 by Béla Lipták

 8.11 Chemical Reactors: Simulation and Modeling 1717

The mass balance equation on reactant A becomes 8.11(34), and 8.11(35), and this set of equations can be closed
by also applying Equation 8.11(26). If the temperature of the
d ( A∆xc An ) jacket Tj cannot be considered constant, then a heat balance
= Avn−1c A,n−1 − Avnc An + A∆ xrAn , equation, similar to Equation 8.11(33) without reaction term,
dt
should be added to the model.
n = 1, 2 K N , v0 = vin , ρ0 = ρin , c A 0 = c Ain 8.11(31)
The greater the number of compartments in this compart-
ments model, the better the model approximates the distrib-
where cAn is the concentration of reactant A in the nth com- uted parameter plug flow model. However, in accordance
partment, and rAn is the reaction rate. Again, this equation with the engineering heuristics, five compartments usually
can be simplified writing are sufficient to describe the performance and behavior of
plug flow reactors.
dc An 1
= (v c − v c ) + rAn , n = 1, 2 K N ,
dt ∆ x n−1 A,n−1 n An Nonideal Flow
v0 = vin , ρ0 = ρin , c A 0 = c Ain 8.11(32)
The flow patterns of process reactors often deviate from the
ideal flow conditions of perfect mixing and plug flow. In
The Energy Balance The energy balance equation around stirred tank reactors, this can be caused by such elements in
the nth compartment takes the form real equipment as corners, baffles that can lead to stagnant
regions, or nonuniform flow paths that can induce bypassing
of fluid.
d ( A∆ x ρnC pTn )
= Avn−1ρn−1C pTn−1 − Avn ρnC pTn The way to model this type of imperfections is to divide
dt the reactor into more compartments of different volumes.
+ A∆ x (− ∆ H r )rAn + Ua∆ x(Tj − Tn ) These compartments can be connected with each other using
n = 1, 2 K N , v0 = vin , ρ0 = ρin , T0 = Tin 8.11(33) volumetric flows of different flow rates. The sum of the
volumes of the compartments must equal the volume of the
reactor. A simple model of a real stirred tank with bypassing
where a is the perimeter of the tube, so that a∆x is the heat- and dead space is shown in Figure 8.11g.
transfer area of one compartment, and Tj is the temperature The nonideal flow in tubular reactors can be modeled
of the jacket assumed to be uniform along the tube, as it takes simply by adding back-flow from a compartment to the pre-
place, for instance, in a firing box. This last equation can also ceding one in the N compartments in series model. In this
be written in simplified form manner, one can allow for some mixing in the axial direction
of the tube, as it is illustrated in Figure 8.11h.
dTn vn−1ρn−1 1 Ua Increasing the rate of back-flow, the model will approach
= (T − T ) + (− ∆ Hr )rAn + (T − T )
dt ∆ x ρn n−1 n ρnC p AρnC p j n that of the perfectly mixed reactor. In the case of fixed finite
back-flow, when the number of compartments, N, approaches
n = 1, 2 K N , v0 = vin , ρ0 = ρin , T0 = Tin 8.11(34) infinity, the model approaches the so-called plug flow with
axial dispersion model.
Often, the pressure drop in the reactor is sufficiently large Another type of nonideal flow occurs in a tubular reactor
to be necessary to account for it, instead of using an average in which the velocity, temperature, and concentration varies
value. Then the velocity from each compartment to the next across the radius of the tube. If axial symmetry is present,
can be computed by using the usual Bernoulli equation these phenomena may be modeled by assuming some velocity

Bypassing
pn − pn−1 = kF ρn vn2 + α ρn vn (vn − vn−1 ),

n = 1, 2 ... N , v0 = vin , ρ0 = ρin 8.11(35)

Input Effective Output
mixing
where the constant kF is proportional to the Fanning friction zone
factor, which can be computed using fluid dynamics corre-
lation. α is a conversion factor in the Fanning pressure drop
equation. In liquid phase reactors, the velocity can also be Dead
assumed constant, thus Equations 8.11(32), 8.11(34), and zone
8.11(35) by themselves form a closed model of the reactor.
FIG. 8.11g
Gas Phase Reactions In gas phase reactors, however, the The model of a real stirred tank reactor includes both bypassing
mathematical model consists of Equations 8.11(30), 8.11(32), and dead space components.

© 2006 by Béla Lipták

1718 Control and Optimization of Unit Operations
Forward flow: (1+R)Avn 0≤R<∞
1 2 … n−1 n … N activity, is measured as the accumulated time that has passed
∆x
Backward flow: RAvn
FIG. 8.11h
Plug flow reactor model that includes back-flow among the com-
partments.
profile along the radius that further can be combined with
diffusion of chemical species and conduction of temperature
in radial direction.
In such cases, the reactor can be divided into a number
of “rings,” and the balance equations can be written for each
of these rings. For the transfer of heat and mass between the
rings, appropriate flow models and interfacial heat and mass
transfer equations must be used.
Heterogeneous Reactors
Modeling and simulation of multiphase heterogeneous reac-
tors falls into a special category because an additional com-
plexity, namely the transfer of mass and energy between
phases, enters into the problem. In general, mass and energy
balance equations must be written for each phase, and appro-
priate interfacial transfer equations must be used for describ-
ing the transfer of reactants and products between the phases.
The transport of mass and energy inside the phases are
described by models discussed in the case of homogeneous
reactors, while the interfacial mass and heat transfers are
expressed in terms of appropriate driving forces as:
Φ A = kL (cAk − cAi ) 8.11(36)
where ΦA is the mass flux through the interface, kL is the mass
transfer coefficient, and (cAk – cAi) denotes the driving force
expressed as a difference of concentrations of species A in
the kth and ith phases. For this model, it is important to
determine the interfacial surface area between the phases,
which could be difficult. The two most significant physical
properties of the system are the solubility and the phase
equilibrium relationships.
For fast reactions and low diffusion or mass transfer rates,
the rate of mass transfer has greater influence on the rate of
chemical reactions than does the kinetics of the reaction. In
such cases, the mass transfer is the step that determines the
rate, and the reaction rate equations may be quite different
compared with the previously discussed ones.
Catalytic Reactors
In catalytic reactors, the catalyst speeds up the reaction with-
out being consumed or produced by it. The reaction rate
coefficient is then a function of the temperature, catalyst con-
© 2006 by Béla Lipták
centration, and catalyst activity or age. Catalysts frequently
lose a large portion of their activity while in operation. The
age of the catalyst, being a measure of loss of the catalyst
since the catalyst was replaced or regenerated. These values
usually are not readily available and must be determined
experimentally in order to be incorporated into the model.
When the catalyst is a solid, the additional complications
of heterogeneity arise in the modeling process. In fluid-solid
catalytic reactors, the reaction itself takes place on the surface
of the solid. For this reason, it is advantageous to have the
particles of catalyst in a porous form making a large internal
surface area available for the reaction. In this case, the rate
of transport of gas to and from the surface within the pore
structure will significantly affect the performance of the reac-
tor and has to be taken into consideration. The effectiveness
factors usually provide a useful tool to make the model of
the reactor treatable. In general, this is defined as
rate of reaction with pore diffusion resisstance
η=
rate of reaction without pore diffusiion resistance
8.11(37)
and the actual reaction rate that would be observed is
(rA )observed = η(rA )ideal 8.11(38)
where the reaction rate (rA )ideal is derived with surface condi-
tions. The effectiveness factor depends on the shape of cat-
alyst particles.
Sometimes, especially in fixed-bed catalytic reactors, the
equations can be considerably simplified by expressing the
rate of reaction on the basis of unit mass of catalyst instead
of on the basis of unit volume.
CONCLUSIONS
Presented in this section were methods for developing the
equations that describe process reactors. Because the reactor
is only one part of the total control loop, for a complete sim-
ulation of the loop, it is necessary to include the equations that
represent the temperature, level, pressure, and concentration
sensors, transmission lines, controllers, and control valves.
A reactor control simulation allows the control engineer
to tune the controllers without any loss of production or risk
of an accident. Simulation also provides the perfect tool to
train plant operators for smoother and safer start-ups. In
addition, it serves as a “live” model with which to try new
control ideas that will result in safer and more efficient oper-
ation of the reactor; it gives an insight into the behavior of
the reactor equivalent to several years of reactor operation.
This last advantage derives from the ability to look at vari-
ables in the simulation that are impossible or impractical to
measure in the process reactor.

When modeling on digital computers, one must recog-
nize the following:
1. The digital computer is a discrete time device; therefore,
all the computations required to implement must be
expressed in discrete time forms.
2. Numerical integration involves approximating continu-
ous differential equations with discrete finite difference
equations. The accuracy and stability of these approxi-
mating equations must be constantly considered.
3. Interactive environments of digital computers provide
convenient and effective tools and some kind of graphical
capabilities for modeling, simulating, and analyzing
dynamic, multidomain systems and control system
design. It lets you accurately describe, simulate, evaluate,
and refine a control system’s behavior through standard
and custom block libraries, also allowing you to develop
and build your own special process and control elements.
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© 2006 by Béla Lipták
8.11 Chemical Reactors: Simulation and Modeling 1719
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