Study in Startup Dynamics of a Continuous Stirred Tank Reactor (CSTR)

Background
A type of reactor commonly used in industrial processing is the stirred tank operated
continuously. It is usually referred to as the continuous-stirred tank reactor (CSTR) or
backmix reactor, and is used primarily for liquid phase reactions. More specifically,
continuous stirred tanks are used for relatively slow reactions of liquids and slurries. Its
normal operation is at steady state and its assumed to be perfectly mixed.
Consequently, there is no time dependence or position dependence of the temperature, the
concentration, or the reaction rate inside the CSTR. In other words, the concentration
and temperature is the same at every point inside the reactor. Therefore, the temperature
and concentration in the exit stream are modeled as being the same as those inside the
reactor. This is an extremely helpful and important point because otherwise, in systems
where mixing is not ideal, we would not know the concentration of the exit stream using
a well-mixed model and would have to resort to other methods, such as residence-time
distributions to obtain meaningful results. (Fogler) Ideally, stirred tank reactors run most
efficiently when the liquid level is equal to the tank diameter, although at higher
pressures slimmer diameters are more economical and would decrease residence times.
The residence time along with space velocity and product distribution are usually found
from a pilot plant. Also, the CSTR can either be used by itself or, as part of a series or
battery of CSTRs. A battery of four or five in series is often used. It is also important to
note that the mixer power input to a homogeneous reaction stirred tank is usually 0.1-0.3
kW/m^3, but three times this amount when heat is to be transferred.
There are many other types of reactors currently used in industry, such as batch reactors,
semibatch reactors, tubular reactors, and fluidized-bed reactors. The choice of reactor
will depend upon a number of factors, such as the rate of reaction and the desired
conditions in which the reaction must take place. Batch reactions are conducted in stirred
tanks where the reagents are added batch-wise. They are used mostly for small daily
production rates, when the reaction times are long, or when some condition such as feed
rate or temperature must be programmed in some way. In addition, the batch reactor has
the disadvantages of high labor costs per batch and the difficulty of large-scale
production.
Semibatch reactors have essentially the same disadvantages as batch reactors, but they
have the advantages of good temperature control and the capability of minimizing
unwanted side reactions through the maintenance of a low concentration of one of the
reactants. These reactors are used for two-phase reactions in which a gas is typically
bubbled continuously through a liquid.
Tubular flow reactors, mainly plug-flow reactors (PFR) and packed-bed reactors (PBR),
are suited to high production rates at short residence times (sec. or min.) and when
substantial heat transfer is needed. They are relatively easy to maintain and they usually
produce the highest conversion per reactor volume of any of the flow reactors, but the
temperature within the reactor is difficult to control and hot spots can occur when the
reaction is exothermic. It is important to remember that depending upon the conditions in
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which the reaction is taking place, one reactor may or may not be more suitable than
another. Note that sometimes in certain situations tubular flow reactors are no better than
CSTRs. For example, in catalyst packed reactors, the residence time distribution is often
as good as that of a five-stage CSTR battery. Also, for conversion under about 95% of
equilibrium, the performance of a five-stage CSTR battery approaches plug flow.
The fluidized-bed reactor is analogous to the CSTR in that its contents, though
heterogeneous, are well mixed, resulting in an even temperature distribution throughout
the bed. Although, the fluidized-bed reactor cannot be modeled as either a CSTR or a
tubular reactor (PFR or PBR) therefore requiring a model of its own. The fluidized-bed
is a catalytic reactor that can handle large amounts of feed and solids and has good
temperature control; consequently, it is used in a large number of applications. The
catalyst particles used in fluidized beds are 0.1 mm in diameter. For the purpose of
comparison, the dimensions of the catalyst particles used in slurry and fixed beds are 1
mm and 2-5 mm in diameter respectively.
For the case of this experiment, consider the following saponification reaction (Ethyl
Acetate reacting with Sodium Hydroxide to form Sodium Acetate):
CH3COOC2H5 (aq) + Na+OH- (aq) CH3CH2OH (aq) + CH3COO-Na+ (aq)
This reaction is first order with respect to both sodium hydroxide and ethyl acetate i.e.
second order overall. The reaction carried out in the CSTR will eventually reach steady
state. The steady state conditions vary with the concentration of the reagents, flow rates,
volume of the reactor, and temperature of the reaction. This reaction has been reported1.
to have an activation energy of 39,900 J/mol and a pre-exponential factor of 1.05 x 106
L/mol sec.
1.

Mendes, A.M.; Madeira, L.M.; Magalhaes, D.; Sousa, J.M., An Integrated Chemical Engineering Lab
Experiment, Chem Eng Education 38, 168 (2004)

Information on Sensor Used

The progress of this reaction can be observed by monitoring the conductivity of the
reaction mixture as a function of time with a conductivity probe (Figure 1). The probes
function is to measure the conductivity, i.e. the ability of the solution to conduct an
electrical current between two electrodes (Figure 2). Through the help of Logger Pro
this electrical current can be measured. (Vernier manual, www.vernier.com)
Conductivity is measured in units or Siemens (S) ( historically mhos ohms-1)and can be
written in terms of resistance and the cell constant:
(conductivity, S) k = K/R
where K = cell constant (cm-1)
R = resistance (ohms)
The cell constant (K) is written in terms of area and distance: (cell constant) K = d/A
where A = area of the electrode surface
d = distance between the two electrode

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--------1 cm---------

--------1 cm---------

Figure 1 Conductivity Probe

Figure 2 electrode plates on the probe

It is important to note that typically there is much variation in the instrumentation used to
measure conductivity, but for the case of this experiment, the Vernier Conductivity Probe
will be used. Also, conductivity tests are not indicative of the types of ions present only
the amounts.
Note: The conductivity sensor has a switch to select the range of conductivities being
measured. Please make sure an appropriate range is selected before you begin
the CSTR run.
The electrical conductivity of the system is present due to the ions that form from the
reactant, sodium hydroxide (NaOH), and the product, sodium acetate (NaOCOCH3).
Initially, only NaOH contributes to the electrical conductivity, but as the reaction
proceeds, both NaOH and NaOCOCH3 will contribute. Therefore, conductivity can be
used to provide a measure of conversion. However, we must calibrate the sensor to relate
the conductivity to the relative amounts of both species present.

Theory
Fj0 moles/hr

Nj moles

E-1

Fj moles/hr

Figure 2 typical depiction of stirred tank reactor

First note that because of the overflow out, the volume of the tank remains constant.
Also we can neglect the effect of concentration on density at these dilute conditions and
so the flow out is the sum of the two flows in. Let us define the following variables:

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V = volume of the CSTR, in m3

F= inlet flow rate of the stream containing A m3/hr = inlet flow rate of stream containing
B
Fout=flow rate of the outlet stream = 2*F, since reactor volume is constant
CAi=concentration of A = NaOH in the inlet stream, mole/m3
CBi=concentration of B = NaAc in the inlet stream
CA=concentration of A in the outlet stream
CB=concentration of B in the outlet stream
Reaction rate= -kCACB moles/m3/hr, assumed to be first order with respect to A and B.
When the general mole balance equation is written for A and B we get
Accumulation of A= Input of A - Output of A Consumption of A due to reaction
Accumulation of B=Input of B Output of B - Consumption of B due to reaction
dVC A
FC Ai 2 FC A VkC ACB
dt
dVCB
FCBi 2 FCB VkC ACB
dt
Now since V is constant we can take it out of the differential and get two differential
equations to follow the changes (dynamics) in concentration of both species. The initial
conditions are;
dC A
(1)
( FC Ai 2 FC A VkC ACB ) / V ;
C A (t 0) C A0
dt
dCB
(2)
( FCBi 2 FCB VkC ACB ) / V ;
CB (t 0) CB 0
dt

Note that, by stoichiometry, the concentrations of the products sodium acetate (C) and
ethanol (D) will be equal (CC = CD). Note also that since both feed streams and the initial
reactor charge have the same 0.01 M concentration, CA + CB + CC + CD = 0.01 at all
times.
For steady state, the time derivatives in equations (1) and (2) are zero and:
FC Ai 2 FC A VkC ACB 0
FCBi 2 FCB VkC ACB 0

(3) and (4)

Since we will use equal concentration of CA and CB in the inlet stream, the concentration
in the outlet will also be equal at steady state, since according to the reaction
stoichiometry one mole of A reacts with one mole of B. Hence CAi=CBi and CA=CB. For
this particular case, equations
(3) and (4) become identical:
(steady state)
(5)
FCAi 2 FCA VkCA2 0
Our goal; Obtain the rate constant k by fitting equations (1) and (2) to the experimental
data and then obtain the steady state concentration of NaOH from equation (5).

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