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Contents
1 Task Assignment
Experimental Setup
3 Theoretical Fundamentals
Stability of CSTRs
4.1
4.2
6 Analysis of Experiments
7 Notation
10
8 References
12
Task Assignment
In this lab you will examine the behavior of a polytropic (ideally: adiabatic)
continuous stirred tank reactor (CSTR) in a laboratory plant. The reactor is used to
conduct the hydrolysis of acetic anhydride:
(1)
You are to determine the steady-state operating points of the reactor at various feed
temperatures and volumetric flow rates. Moreover, you are asked to compare your
experimental results with corresponding theoretical calculations.
Experimental Setup
Water
Acetic Anhydride
Flexible-Tube Pumps
Thermostat
M
I
TI
Outlet
The stirred tank reactor is equipped with a measuring device for temperature and
electrical conductivity. In order to ensure the proper feed temperature the reactants
are pumped from holding tanks through a thermostat into the CSTR. The reaction
volume is kept constant using an overflow. Finally, the reaction mixture leaves the
reactor through an outlet into a collecting vessel.
Theoretical Fundamentals
dni
= (ni,0 - ni ) +VR nij rj
dt
j
(2)
For most liquid phase reactions the molar flow rate ni can be substituted by the
volumetric flow rate V and the concentration ci (assumption: constant reaction
volume):
VR
dci
= V (ci,0 - ci ) +VR nij rj
dt
j
(3)
The available reaction volume VR in a CSTR depends on reactor size and location of
feed point and outlet. In contrast to the batch reactor VR is always constant in a
CSTR. Any density changes of the reaction mixture due to chemical reactions or
physical influences (mixing or excess effects) would result in differences between the
volumetric flow rate at the reactor entrance and the outlet.
The ratio of reaction volume to volumetric flow rate is termed (mean) hydrodynamic
residence time t :
V
t = R
(4)
V
As a rule of thumb, the reactor reaches steady state after an operating time which is
approximately five times the value of t . At the end of this period there will be no
more composition changes of the reaction mixture with time.
For reactions which are far from thermodynamical equilibrium the reaction rate can
often be represented by a power law approach:
r = k ciai
(5)
r = kcA
(6)
The temperature dependence of the rate coefficient follows the Arrhenius equation:
k = ke -EA /(RT )
(7)
VR
dcA
= V (cA,0 - cA ) -VRke -EA /(RT )cA
dt
(8)
The derivative dcA / dt can be set to zero since we are only interested in the steady
state. By introducing the conversion
X=
cA,0 - cA
cA,0
(9)
(10)
For the derivation of the energy balance we again assume the reactor to be at steady
state and that the reaction is proceeding homogeneously at constant volume. The
general energy balance for a CSTR is then
rcav
p VR
dT
= rcav
p V (T0 - T ) + UA(TH - T ) + VR rj (-DH R, j )
dt
j
(11)
r (-DH
j
R, j
(12)
0 = rcav
cA (-DH R )
p V (T0 - T ) +VRk e
(13)
Energy balance and material balance are both necessary to design the reactor, i.e. to
calculate the operating temperature when the desired reactor output is given.
Starting with the steady-state material balance (equation (3)) and invoking the
definition of conversion according to equation (9) the reaction rate can be expressed
as follows:
r=
XcA,0
(-nA )t
(14)
This rate expression can be put into the steady-state adiabatic energy balance
(equation (13)) to get a linear relationship between conversion and temperature:
X=
(-n A ) rcavp
cA,0 (-DH R )
(T - T0 )
(15)
solution of both balances which can be achieved by equating the two expressions. The
result is a so-called coupling equation which in general must be solved iteratively.
for heat generation by reaction is grouped. For the case of an irreversible first-order
reaction in an adiabatic CSTR we get
Qr V rcav
(T - T0 ) = VR (-DH R )
p
In a
VAN-HEERDEN-diagram
cA,0
ke
-EA /(RT )
-n A 1 + ke -EA /(RT )t
Qg
(16)
operating point depending on the process conditions (multiplicity of solutions for the
coupling equation). Fig. 2 shows a typical
VAN-HEERDEN-plot
Stability of CSTRs
One of the stability criterions for operating points of CSTRs is that the slope of the
straight line of heat removal must be larger than the slope of the heat generation
curve:
dQg
dQr
dT
dT
(17)
Fig. 2 illustrates this fact. If the reactor experiences small temperature perturbations
at operating point A or C , it readily returns to the original operating point (selfadjusting behavior). A rise in temperature, for instance, leads of course to a higher
reaction rate but also to a (larger) increase in heat removal. We call this mode of
reactor operation stable.
However, point B is an unstable operating point. If a small positive temperature
fluctuation occurs here, heat gets generated faster than it is removed. Therefore the
temperature rises until the reactor reaches point C . For a temperature drop the
operating point moves from point C to point A . Nevertheless, it is possible to
operate a reactor in an unstable operating point using a controller. There might be
cases where the interplay of reaction rate and selectivity can be optimal at these
points. In case of a single intersection between Qr and Qg , the corresponding operating point is always stable.
4.1
An increase of the feed temperature T0 shifts the heat removal line to the right in the
VAN-HEERDEN-diagram (for the adiabatic CSTR the intersection of Qr with the
abscissa is given by the feed temperature). Lets look at a reaction where there can be
several intersections between heat removal line and heat generation curve (see figure
3). When the cold reactor is started up with feed temperatures smaller then T0,2 only
operating points on the lower branch of the heat generation curve can be reached;
conversions achieved in the reactor are low. There is only one steady state with high
conversion and high temperature for temperatures larger than T0,2 . We call this
situation reactor ignition and the corresponding value of T0 ignition temperature.
6
The reactor will remain at a high conversion level even if the feed temperature is now
reduced to a value between T0,1 and T0,2 . If the feed temperature is reduced below
T0,1 a sudden shift to low conversions can be observed; the reactor is said to be
extinguished. This is a pronounced hysteresis behavior which can be exploited for
reactor operation.
4.2
temperature T in the vessel can only be calculated iteratively. Depict the heat
generation curve and the straight line for the heat removal in a van-Heerden-plot for
a preliminary estimation of the solution. The corresponding conversions can be
determined using equation (10) or (15). Use the following data for the hydrolysis of
acetic anhydride to determine the steady-state operating points.
r rW
1000 kg m-3
cav
p c p ,W
V
=
=
VR
0.56 l
DH R
-55.5 kJ mol-1
Numerical values for the collision factor and the activation energy should be taken
from the preceding lab experiment Estimation of Kinetic Parameters in a Batch
Reactor (remember: first-order reaction, i. e., take k and EA from the kinetic
approach with a = 1 ). Process conditions for the various operating points are
summarized in the following table:
T0 / C
VW / cm min -1
VA / cm min -1
30
40
30
60
40
40
40
60
50
40
50
60
Because of the duration of the experiments only two operating points from the above
set will be examined. The process conditions you are going to use will be chosen by
the person in charge of the laboratory work.
and conversion
X)
theoretically for two sets of process conditions (volumetric flow rates and feed
temperature) which can be chosen arbitrarily from the preceding table before
you come to the lab.
2. Fill the storage vessels (flasks) with distilled water and acetic anhydride. Then
set up the appropriate temperature and turn on the thermostat. Check all
hoses (particularly those containing acetic anhydride) for material defects and
inform the teaching assistant if you find any.
3. Adjust the volumetric flow rate of water VW using the flexible-tube pumps
and the rotameters.
4. Wait until VW is constant. Turn on and adjust the acetic anhydride flow
subsequently.
5. Measure conductivity k and temperature T in the reactor as a function of
time (roughly every 3 minutes). Check and readjust the volumetric flow rates
during your measurements if necessary.
6. The reactor has the reached steady state when temperature and conductivity
are constant (45 60 min). You can calculate the concentration of acetic acid
and therefore conversion X using calibration curves for the conductivity k
(bear in mind that the calibration constants are functions of temperature!).
Analysis of Experiments
Notation
mol m-3
concentration
cp
J kg-1 K-1
EA
J mol-1
activation energy
DH R
J mol-1
S m-1
electrical conductivity
s-1
s-1
n
Q
mol s-1
J s-1
kg m-3
density
10
reaction rate
-1
J mol K
time
temperature
-2
-1
-1
Jm s K
VR
V
m
m s
conversion
-1
Superscripts
av
average
Subscripts
feed conditions
acetic anhydride
Ac
acetic acid
generation
species index
reaction index
removal
water
11
References
[1]
[2]
Design, 3rd ed., John Wiley & Sons (2011), Sec. 10.4.
[3]
12