Isothermal Chemical Reactor

Douglas Plaza Guingla, Ph.D.

November 5, 2019

1 Introduction

Figure 1: Picture of a CSTR

1
 The dynamics of a chemical reaction within a Continuous Stirred Tank
Reactor (CSTR) is modelled based on the mass/material balance and com-
ponent material balance. The example is originally presented in [1]. Figure
1 shows a real CSTR as to have an idea of the industrial process which will
be seen in this example.

Fi
CAi

F
CA CB CP

Figure 2: Schematic of the industrial process

The PI&D diagram of the industrial process is depicted in figure 2. The

process consists of the reaction between reactant A which is Ethylene Oxide
(EO) and reactant B which is water in large excess. Both reactants generate
the product P which is Ethylene Glycol (EG). Some assumptions are made
such as that the temperature is constant (isothermal) and the water do exists
in large excess.
The stoichiometric equation is given by:

A+B →P

The overall mass balance, considering a perfectly mixed tank, is given by:

dV (t)ρ
= fi (t)ρi − f (t)ρ
dt
The liquid-phase density is not a function of concentration thus the densities

2
are equal at the inlet and outlet. The expression is the following:
dV (t)
= fi (t) − f (t) (1)
dt
Work in molar units when writing balances in chemical reactions due to
the material concentrations. CA and CP are molar concentrations of com-
ponents A and P [moles/volume] respectively. The component material
balance equations are:
dV (t)CA (t)
= fi (t)CAi − f (t)CA (t) + V (t)rA (t) (2)
dt
dV (t)CP (t)
= −f (t)CP (t) + V (t)rP (t) (3)
dt
where rA and rP represent the rate of generation of species A and P per
unit volume. CAi is the concentration of species A in the inlet flow. Consid-
ering large excess of water (component B), thus its concentration does not
change significantly, and the reaction rate is first order with respect to the
concentration of ethylene oxide,
rA (t) = −kCA (t)
where k is the reaction rate constant, the minus sign indicates that A is
consumed in the reaction. Each mole of A reacts with a mole of B (from the
stoichiometric equation) and produces one mole of P (per unit volume) is:
rP (t) = kCA (t)
dV CA
Expanding the expression dt
:
dV (t)CA (t) dCA (t) dV (t)
= V (t) + CA (t) (4)
dt dt dt
The dynamics concentration of A is derived by combining equation 1, with
equation 2 and equation 4 as follows:
dCA (t) fi (t)
= (CAi − CA (t)) − kCA (t) (5)
dt V (t)
Similarly, the concentration of P is obtained by combining equation 1 with
3 and 4.
dCP (t) fi (t)
=− CP (t) + kCA (t)
dt V (t)

3
 The three equations governing the isothermal reactor are:

dV (t)
= fi (t) − f (t)
dt
dCA (t) fi (t)
= (CAI − CA (t)) − kCA (t)
dt V (t)
dCP (t) fi (t)
= − CP (t) + kCA (t)
dt V (t)

The model of the reactor in this case is represented by a non-linear sys-

tem. A common framework to represent non-linear systems is the state-space
representation. For the latter, it is important to define the states, inputs,
parameters and possibly the outputs. In this example the states corresponds
to X = [V (t), CA (t), CP (t)]T the inputs: U = [fi (t), f (t), CAI ] and the pa-
rameters p = [k].
The representation of the system in state space form is:
     
ẋ1 f1 (X, U, p) u1 − u2
ẋ2  = f2 (X, U, p) =  ux1 (u3 − x2 ) − p1 x2 
1
ẋ3 f3 (X, U, p) − ux11 x3 + p1 x2

For the rest of this section, a level loop is considered in the system thus
the volume remains constant and from equation 1, we have that the inlet
and outlet flows are constants Fi = F . According to this consideration, the
system is described by:

dCA (t) F
= (CAI − CA (t)) − kCA (t)
dt V
dCP (t) F
= − CP (t) + kCA (t)
dt V
Lets make some analysis around the operating conditions of the reactor in the
steady state condition (derivatives equal zero). The operating points of the
reactant concentration and product concentration are indicated as follows:
CAis
CAs = (6)
(kV /Fs ) + 1
(kV /Fs )CAis
CP s = (7)
(kV /Fs ) + 1

4
 0.5 Cas Ethylene Oxide
Cps Ethylene Glycol
0.4
Concentration [lbmol/ft3]

0.3

0.2

0.1

0.0
0.0 2.5 5.0 7.5 10.0 12.5 15.0 17.5 20.0
Residence Time (V/F) [min]
Figure 3: Concentrations behaviour according to V/F values

Fs
is the space velocity [1/time] is the number of reactor volumes that
V
change over time. It is inversely related to the fluid residence time FVs [time]
which is the average time that a fluid spends in the reactor. Figure 3 shows
the concentrations values according to the residence time. The reaction rate
constant is k = 0.311 [1/min], the constant k has been determined according
to experimental procedures with temperature fixed at 55 ◦ C.
According to figure 3, the concentration of EO (Cas) is decreased from its
initial value of 0.5 lbmol
f t3
while the residence time increase. On the other hand,
as it is expected, the concentration of EG is increased while the residence
time increase. The reason in the seen behaviour is explained considering
the physical variables involved in computation of the residence time. An
increment in the residence time means more time for the reactant A to be
consumed while the product concentration increases. Opposite behaviour is
seen when instead of analysing the concentrations against the residence time,
it is analysed against the space velocity VF .
Normally, the study of the conversion of the concentrations is also impor-

5
tant. In this sense, the concept of conversion factor is used. The conversion
is the fraction of the feed-stream component that is reacted, it is written as
follows:
CAi − CA kV /Fs
X= = (8)
CAi (kV /Fs ) + 1
The conversion is a function of the dimensionless Damkohler number ( kV Fs
).
The Damkohler number is a parameter which relates the chemical reaction
with the physical variables of the reactor. Just look at the expression where
the reaction velocity is multiplied by the residence time: k ∗ VF .
Now, let’s consider that the production department requires a total of 100
million pounds of Ethylene Glycol in a time horizon of 1 year. The questions
which arise are: What is the feed-flow rate and the volume of the reactor?.
In this section the answers to these questions are treated. Consider the feed-
stream concentration is 0.5 lbmol/ft3 , the conversion factor of ethylene oxide
into ethylene glycol is 80 %, and the molecular weight is 62 lb/lbmol.
First, we focus on the computation regarding Ethylene Glycol, since
CAi = 0.5 [lbmol/ft3 ] and the conversion is 80 % then Cp = 0.4 [lbmol/ft3 ].
With the Molecular Weight (62 lb/lbmol), Cp can be expressed in pounds.
Thus Cp = 24.8 [lb/ft3 ]. The feed-stream rate is possible to be computed by
considering the production requirements, thus:

lb f t3 year day h f t3
1 × 108 × × × × = 7.67 .
year 24.8lb 365days 24h 60min min
The volume of the reactor is computed by using equation 8 and with the
reactor flow recently computed F = 7, 67 [ft3 /lb]. The expression for the
volume is given as follows:
XF
V =
k(1 − X)

with the result 0f 98.65 ft3 which is equivalent to 738 gallons. The capacity
of reactors in the market are fixed, in this case a proper selection is a reactor
with a capacity of 1000 gallons.
As a final computation, the concentration of Ethylene Oxide is found
based on equation 8 with the following expression:

CA = CAi (1 − X) = 0.5 × 0.2 = 0.1

6
 Table 1: Operating Points
Names Values description
X 80 % Conversion from EO to EG
k 0.311 [1/min] reaction rate constant
V 98.65 [ft3 ] volume
F 7.67 [ft3 /min] feed-stream flow
CAi 0.5 [lbmol/ft3 ] Feed-stream concentration
CA 0.1 [lbmol/ft3 ] Reactant concentration EO
CP 0.4 [lbmol/ft3 ] Product concentration EG

2 Simulation
The computations found in the former section are considered as the operating
conditions/points for our simulation. Table 1 show the operating points.
The reactor has been modelled in the software package OpenMODELICA,
the code is presented as follows:

1 class C o n t r o l E S P O L . I s o t h e r m a l C h e m i c a l R e a c t o r
2 parameter Real Cai = 0 .5 ;
3 parameter Real k = 0 .311 ;
4 Real Ca ( start = 0 .1 ) ;
5 Real Cp ( start = 0 .4 ) ;
6 Real F ( start = 8 .0 ) ;
7 parameter Real V = 102 .9 ;
8 equation
9 F = if time > 1 .0 then 10 .0 else 8 .0 ;
10 der ( Ca ) = F * ( Cai - Ca ) / V - k * Ca ;
11 der ( Cp ) = k * Ca - F * Cp / V ;
12 end C o n t r o l E S P O L . I s o t h e r m a l C h e m i c a l R e a c t o r ;

As it can be seen in line 9 of the simulation code, a step signal at time 1

min is given to the input f (t) with a signal change from 8 to 10 [ft3 /min] as
it can be seen in 4. The idea behind this test is to check for the dynamics of
the chemical reaction.
Figure 5 shows an increase in the concentration of the Ethylene Oxide.

7
 F
10

9.5

8.5

8
0 5 10 15 20
time (s)

Figure 4: Step change in the input f (t)

Ca
0.12

0.115

0.11

0.105

0.1

0.095
0 5 10 15 20
time (s)

Figure 5: Response of the EO (CA ) concentration to a step change of f

Cp
0.405

0.4

0.395

0.39

0.385

0.38
0 5 10 15 20
time (s)
8
Figure 6: Response of the EG (CP ) concentration to a step change of f
 Figure 6 shows a decrease in the concentration of the Ethylene Glycol.
Although, the times units indicates seconds, in reality, the time steps are
in minutes according to the units of the variables. It is realized that both
concentrations Ca and Cp behaves time constants around 15 mins.
The reader is invited to think about the behaviour of the concentrations,
I leave the following questions open for responses:

ˆ Why the final value of CA is greater than the initial operating point?

ˆ Why the final value of CP is lower than the initial operating point?

ˆ Sketch both concentrations responses to a step down of input f (t).

References
[1] B. Wayne Bequette, Process Control: Modelling, Design and Simulation,
Prentice Hall, 2003.

[2] Tony R. Kuphaldt, Lessons in Industrial Instrumentation, Samurai Media

Limited, 2017.

Appendix
In the appendix, the code in Python which was used to generate figure 3 is
shown.

1 import numpy as np
2 from matplotlib import pyplot as plt
3
4 Cais = 0.5
5 k = 0.311
6 V_over_F = np . arange (0 ,20 ,0.1)
7 Cas = Cais /(( k * V_over_F )+1)
8 Cps = (( k * V_over_F )* Cais )/(( k * V_over_F )+1)
9 # Create a figure
10 fig = plt . figure ( figsize =(6 ,4))
11 plt . xlabel ( " Residence Time ( V / F ) [ min ] " )
12 plt . ylabel ( " Concentration [ lbmol / ft $ ^3 $ ] " )
13 plt . xlim =(0 ,20)
14 plt . ylim =(0 ,0.5)

9
15 plt . plot ( V_over_F , Cas , label = " Cas Ethylene Oxide " )
16 plt . plot ( V_over_F , Cps , ' -- ' , label = " Cps Ethylene Glycol " )
17 plt . legend ()
18 plt . grid ()

10