Combination of Equations (18) and (20) gives

For convenience, Figure 12 plots

(1 + g;)
as a function of B.
Equation (21) reduces to E* ED"as /3 + O and E* + nK7' as
-+

p + which are proper limiting forms.

T h e dashed line on Figure 10 is thc prediction o f 1q:quatioii
(1 5) for the initial conditions and temperature variation of
Run 3 3 .

Acknowledgment
The early portion of this research was sponsored by Texas Butadiene
and Chemical Corporation and the final portion by National Science
Foundation Grant GP 376. The computations were done at the M.1.T.
Computation Center.
References
Nomenclature
( 1 ) Howninn. W. 13.. Sc.11. Thrsi.;. Chcm. En$?.. h1.I.T. ( l95J ).
A particlv radius, f t .
= ( 2 I Weisz,P. H., and Prater, C.1).. Advancc.s i n Catalpi.;. 6 ( 1954 I .
( 0 ) Hagrrhanrnrr, W'. A.. and L w . H., Triins. ASME. 69, 779 ( 1947 ).
C, bulk oxygen concentration
= ( 4 I Haldc~miin,R . 11.. and Hiitty, h1.C.. J . Phy.;. Clicwi., 63, 489 ( 19.501.
9 = effective clilfusivity, ft.*/hr. ( 5 ) Johnson, hl. E'. L., and !vl21ayl;nid, I I . C., Irid. Ens. CIi<m.. 47, 127
(l9:55).
E, = actiLVation cnergv, B.t.ii./Ib. niolc ( 6 ) Pasing, W. F., A.1.CIi.E. Jorirn;il, 2, 71 (19.56).
E* = apparent activation energy
e = retardation factor, diiiiensionlcss * * *

Experimental Verification of the Mathematical

Model for a Continuous Stirred.Tank Reactor'
RlCHARD I. KERMODE' and WlLLlAM F . S T E V E N S :

This paper reports the dynamic behavior of a particular
continuous stirred-tank reactor system, which has been
investigated in detail both experimentally and o n an analog
computer. The t w o sets of data were taken under compar-
able conditions to facilitate comparison. The reaction
between formaldehyde and ammonia was chosen for study,
because of its high heat of reaction and its signifirant
reaction rate at room temperature. Agrerment between the
experimental data and the computer results was quite good,
with most deviations being explainable as arising from the
use of an approximate form for the kinetic rate exprrssion.
Lr comportement dynamiqur d'un r&acteurcontinu avec
agitation, suite i I'dtude diiaillir tant expiriment;rle qut-
mathbmatique i I'aide d'nne caIeuIatrice analcbgique, est
prCaenti.. Ida roniparaison e s t possible car leu t1onnht.s sont
prises sous des conditions similaires. On a choisi la ri.aetiun
entre la formaldihyde et I'ammoniar i r a u w d r la fnrte
chaleur de ri.action ct do taux d r ri.artion suli~t:inticlB la
tenipbrature anibiante. Ides rCsultats thdoriques 4.1 esl&ri-
mentuux sont en acrord et 1;i majorit6 drs d b v h t i o n * s'rx-
pliqurnt par I'utilisation d'one rxprrwsion approximiitivt.
du taux de ri.action.

\\ere i i i o r c easily solved. I Io\\.cvcr, such P procedure inti-oduccs

D tiring the past few years, research in process dynamics
has emphasized the dc\&pmcnt and use of mathcmatical
models for many types of chemical engineering cq~iil~iiiciit",'~:l).
Most of these niodcls have involved non-linear differential
equations, which ofrcn arc very dificult to solve. In sonic cases,
the original equations \vcre linearized t)y expanding each of the
non-linear ternis in a 'Taylor's sctics and truncating after t\vo
terms, after which the resulting linear differential equations
...............................................................................
'Manuscript rcwioed May 5; acceptcsd lunc 22, 1964.
Tarnegie Institute of Technology. Pittsburgh, Pa., U.S.A.
3Northwcstcrn Uniccrsity, Eoanston, I l l . , U.S.A.
Contribution from Northwestern Unioersity. Eoamton, I l l . , U.S.A.
dout)ts a s to the applical)ilit!. of the solution ot)taincd from the
linear prol)lciii a s a solution to the origin;il iioii-Iiiicar diffcrcntial
equation, cspcciall!. in the rcgion f.u. rcniovcd from tlic oi-iginal
stcadv state.
l'hc best general incthoti for solving non-lincar oi-din;ir\,
differential equations o f the t!.pc that arise in process (i! n.inii&
studies involves the use o l an xialog coiiipiitcr. \ \ itli s t a n h d
non-lincar components (iiiultipiicrs, tiinction gciicr;itors. ere.).
a niodcrn analog computer is capt)lc ot' solving almost mi\.
non-lincar differential equation s>'stciii \\it11 good accurac\'.
Hence, it should be possible to prc'iict the d!.naiiiic t)chavi;r

The Cnrtadinn Journnl of Cherriicnl Engineering, A p r i l , 1965


0
oo-\ 0 --!
0 O
0
L L-
JW 1200 uoo
.
RECIPROCAL TEMFZRATLUE PI( XlO'l
3403
Figure 1-Experimental valuer of reaction rate conrtent.
of any piece of process equipment, if a good mathematical model
is available for analysis.
The present paper summarizes the results of an experimental
investigation of the dynamic behavior of a particular continuous
stirred-tank reactor, along with an analog computer solution
of the non-linear dynamic model of the reactor system('). The
two sets of data were taken under comparable conditions to
facilitate comparison and evaluation of the accuracy of the
mathematical model. The reaction between formaldehyde and
ammonia to give hexamine was chosen for study, because of
its high heat of reaction and its significant reaction rate at room
temperature. This reaction follows the stoichiometric relation,
4NHs + 6HCHO + N,(CHz)s +
6Hz0. A major part of
the investigation involved the measurement of kinetics data and
heats of reaction for the reaction being studied, after which the
reactor system was operated in the unsteady state to give a
phase plane plot. Subsequent analog computer analysis of the
mathematical model then gave results which could be compared
to the experimental data.
Experimental Work
The reaction system studied in the laboratory consisted of
a small stainless steel reactor, equipped with an internal heat
exchanger('). Since it was assumed that perfect mixing took
place in the reactor, several precautions were taken to insure this.
Four evenly spaced baffles helped the mixing. The impellers
on the mixer shaft were twisted in a manner to prevent circulation
in one direction. In addition, the reactant inlets and outlet were
positioned to prevent channeling. The speed of the impeller
was about 1800 r.p.m. and the mixer power was very high
with respect to the reactor volume. Reactants were fed con-
tinuously, through metering orifices, and the product was
removed by displacement. The reactor temperature was
recorded continuously, and the reactor concentration was
followed by withdrawing periodic samples from the outlet
stream. These were neutralized in a known excess of acetic
acid and analyzed for formaldehyde by a srandard procedure(Q.
The first part of the experimental work was the determination
of kinetics data and heats of reaction. These were obtained
while operating the reactor at steady state. Although hexamine
has been produced from formaldehyde and ammonia for many
years, little basic data were available in the literature, except
for some reaction rate studies carried out at much lower re-
actant concentration~(~.7.8).
The kinetics and heat of reaction data obtained in the present
study, over a range of inlet compositions, are presented in
Figures 1 and 2. Reaction rate measurements at temperatures
below 25°C. gave reaction velocity constants which seem to
be somewhat erratic. In addition, the heat of reaction appears
to change by about 50% over the temperature range examined.
These results are probably due to the existence of several
The Canadian Journal of Chemical Enginseriw, April, 1965
a .-
i!
I
i
. !
10 30 40 so
I
TEMPERATURE CC)
Figure %Heat of readon data-formaldehyde plm am-
monia to five hexaxnine.
simultaneous reactions, some of which may be reversible, rather
than the single, irreversible reaction assumed in correlating the
data. Therefore, it was decided that statistically fitted straight
lines would be used to represent both sets of data, as indicated
on the two plots.
The second portion of the experimental work consisted of
an examination of the transient behavior of the reactor. The
following four independent variables were stepped, both simul-
taneously and one at a time: inlet reactant temperature, cooling
water temperature, cooling water flow rate, and total reactant
flow. Experimental data resulting from these studies are plotted
on Figures 3, 4, 5 and 6.
In obtaining the experimental data for the phase plane plot
of Figure 3, the reactor was first filled with formaldehyde
solution of the desired temperature and composition. At time
t = 0, the recorder was started and all variables were stepped
to their desired values. If each independent variable was always
stepped to the same value, then the final steady-state composition
and temperature in the reactor should always have been the same.
As can be seen from the plot of the data, this came very close to
being true. It should be noted that some of the lines on Figure
3 appear to cross each other. This is quite as expected, since
a three-dimensional phase plot is necessary to describe completely
the system under study because of its three dependent variables-
temperature and two compositions.
Figures 4,s and 6 present the results of conventional transient
analysis, with one variable being stepped at a time. The data
were obtained by first bringing the system to the steady state
mrres nding to the center point on Figure 3, and then stepping
one op"the variables to a new value. The composition and tem
ature history of the reactor are presented for the period rom F-
the instant of the step to the attainment of a new steady state.
Development of Mathematical Model
In the original derivation of the equations, several simplifying
assumptions were made('). These include: perfect mixing in
the reactor, no heat losses, all physical properties the same as
water, a thirdader, irreversible reaction, and reaction velocity
constant given by the Arrhenius equation. Equations (1) and
( 2 ) are the two mass balances.
69
 130-

120- ...... COMPUTER RESULTS

+AV a 0 0 EXPERIMENTAL RESULTS

110-

IOO-

-
U
g 090-
.
A

:0 8 0 - ---__
0
L, 06
-
0 70-
TOYE (MINUTES)
0
0
* 060- Figure &Experimental results-step of cooling water flow
rate.
z
e
050-
0
x
=: 0 4 0 -
0 30-
T,, S I E R STEP
El
€2
10 9
25P I
.
€3 31 8 A
020- c* 365.
€5 *50 D
I,. .
C !
0 10-

-
4 4 0.

420t
I
.- €3 !
0 OOL
E2

2 360
-- --- __ ~ --,
Figure 3-Phase plane plot-xperimental and computer 3401

results. $ 3201
3oot
0- I
i
2
L~
3 4
A _ _
5 6
---I I - * - % ~

TlYE (YINUTLSI

If a log mean A 7 is used, the cooling water outlet temper-

ature appears, which is not readily available. T,, was eliminated Figure %Experimental results-step of inlet formaldehyde
by the manipulation shown in Ikpations (4) to (8). temperature.

\Vhen all of the numbers representing the physical quantities

in Kquations ( I ) , ( 2 ) and ( 3 ) are substituted, lquations ( I Z ) ,
( I 3 ) and (14) result. These equations,

10 d CA = +2.49 - 1.226C~- 200r.. . . . .

~
(12)
dr

- Tci
T__ dCp
- (,.\I . .............. , . . . (6 ) 10 - = +.1.87 - 1.226Cl. - 300r. . . . . . , . .(13)
T Tc. ~
dr
d 7'
r" - 1 ~~ ~~ = $35.90 -- 0.1225T - 20r(0.1210T - 18.87) ~-
( Tco - T<,)= ~

If
( f - 7'ct). . . . . . . . . . . .( 7 ) dr
0.1051(T - 293.2) . . . , . . . . . . (14)
along with the rare expression, were programmed on the analog
computer(4). T h e equations were speeded up bv a factor of
20, to keep the total computer time low. T h e computer results
The heat of reaction has been approximated by the straight arc presented in Figures 3, 7, 8 and 9 . In all cases, the same
dotted line shown in Figure 2 . The equation for this line is runs were made as were carried out experimentally.
shown below :
-AHA = 16.61 X lOJ + 0.1210(T - 293.2) X l o 3 . .. . ( 9 ) Comparison of Results
expressed in calories per gram mole of ammonia reacted. The In trying to compare the two sets of data, some difficulty
expression for the reaction velocity constant is given by lqua- was experienced in defining "good agreement". The computer
tion (10). results had an internal consistency which was lacking in the
3090
~
system data. &is an example, the computer always started at
k = 1.42 X 10%- exactly the same composition and temperature. T h e actual
data, however, had a certain amount of scatter in the steady
The reaction rate expression is Fquation ( 1 1). state composition and temperature before a variable was stepped,
I = kcAcF*. . . . . . . . . . . . . . . . . . .(11) even when all conditions appeared to be the same from run to run.

70 The Canadian Journal of Chemical Eng.ineering, April, 1965

 1
,.I
1 " " " " "

::
0 66

52 ~
eC I SECOND
so 0
'
*not
;.so /
_ -0 2
J -
.
.0
84
w 42 0
BI

BZ

83

32 0
3 0 Oo
I 2 3 4 5 6 I B 9 80
TIME (MINUTES 1

Figure 7 -Computer results -step of cooling water flow

Figure &Experimental results-step of total reaetant flow. rate.
1

i
TlYE (MINUTES1

Figure &Computer results-step of inlet formaldehyde Figure 9-Computer results-step of total reactant flow.
temperatures.

It has already been noted that sonic of the phase planc
trajectories cross in the actual system data. This is also present
in the computer results, and can bc explained in the same manner
as beforc. From Figure 3, it can be seen that the ratc of conver-
sion of formaldehyde at lour temperatures (below 25'(:.) is not
as rapid for the simulated system as for the rcal system. This
is clearly shown by comparing the maximum height of compar-
able trajectories. In all cases, the computer compositions reached
a higher valuc. This means that the computer predicts a lower
reaction ratc, which is not surprising considering the limited
amount of kinetics data. . i t teniperatures below 25"(:., thc
straight line approximation used for thc computer simulation
is considerably different from the actual ratc constant data,
1:igure I . At thc higher rcnipcratures (25°C. and above), a
similar deviation is present, but not in all the trajectories o r to
the same extent.
T h e steady state agreemcnt bctwecn thc cxperimental and
computer results is within the accuracy of the analog computer.
T h e steady state as predicted by the computer is 37.3'C. and
0.637 moles of formaldehyde per liter. If all the results for the
actual runs are averaged, the tcmperature and composition in
the reactor are 36.1 'C. and 0.640 moles of formaldehyde per
liter, respectively. T h e ( x - y ) plotter used in this study reads
somewhat in error, such that, if the lowest temperature wcre
set exactly, then the upper temperatures would be at least
I.O°C. high. A t 3 7 O C . , a correction of 0.4OC. was subtracted
from the plotter reading before comparison, but this correction
has not been applied to the drawings.
For the case of a step of cooling water flow rate, the scatter
of the composition data is very small, and the agreement between
thc computer and experimental results is very good. Once again,
the major disagrcemcnt is at t = 0. -411 the final experimental
steady state temperatures are within 1 "C.of the comparable
computer run, some being virtually the same, as can be seen by
reference to Figures 4 and 7.
Figures 5 and 8 show rhc results of stcpping the inlet
formaldehyde trmperature. Both sets of results show a time
lag before a change in composition takes place. T h e temperature
comparison does not seem to be as good as in previous runs.
T h e final steady state difference between runs L<1 and E S is
only 8OC. This smaller total diffcrence tends to magnify the
effect of scatter at t = 0.
T h c final step investigated was a step of the total reactant
How, Figures 6 and 9. Each reactant was stepped by the samc
amount at the samc time, thus keeping the mixed inlet coniposi-
tion the same. T h e diffcrence between rhesc runs cannot be
accounted for by analysis o r computer errors. In examining
the differences, the most plausible explanation is inadequate
kinetic dam. T h c computer predicts a steady-statc composition
of 0.470 moles of formaldehyde per liter for run B3, Figure 9.
T h e actual data give 0.608 moles of formaldehyde per liter
for the same run. Although the differcncc in composition is
significant, the difference in conversion is very small. Thus,
one might expect that the temperature agreement would be
better, and this is exactly what Figures 6 and 9 show.
In examining the computer results, it is apparent that the
computer always predicts a greater change in concentration
than the actual data do. O n e method of explaining the large
computer k is to examine the batch kinetics data. T h e normal
method for utilizing batch data is to plot concentration versus

T h e Canadian Journal of Chentical Engineering, April, 1965

time at various temperatures. Evaluation of the two constants
in the Arrhenius equation requires that conversion data at two
temperatures be available. As an example, knowing the con-
versions at time t, for different temperatures, and the general
rate expression, an equation can be developed that will predict
the conversion for any temperature at a given time. It is
important to remember that the rate expression must be correct,
and the reaction velocity constant must be represented by the
.4rrhenius equation. ,411 the previous data, including the kinetics
data, were taken with the same retention time in the reactor.
In the series of runs where the total reactant flow was stepped,
a different retention time resulted. The reaction velocity
constants were all determined at one retention time. If the
constant based on another retention time were different, then
the computer results would not agree with the experimental data.
Unfortunately, no additional data are available to confirm these
conclusions; however, when the complex nature of the kinetics
is considered, the conclusions do not seem unlikely.
To summarize, the transient data agree very well for all
the cases where the conditions of the steps are such that they
do not alter the conditions under which the kinetic data were
determined. For the two cases where this is not true, the phase
plane plot and the step of total reactant flow, the agreement
might be improved by more complete kinetic information. The
stirred tank reactor has flexibility in determining kinetic data.
In addition, heat of reaction data are obtained with no additional
work. This gives an added check on the accuracy of the model
for an exothermic or endothermic reaction.
Conclusion
This study has compared the results of an experimental
investigation of the unsteady behavior of a continuous stirred-
tank reactor system with the data from a companion analog
computer solution using a mathematical model for the reaction
system in question. The constants, such as the overall hear
transfer coefficient, heats of reaction, etc., necessary to program
the mathematical model were all evaluated by operating the
system at steady state. The values of thcsc constants proved
to be very satisfactory for dynamic comparison of the modcl
and system. As has been previously mentioned, the kinetics
data were the most questionable part of the work. These dara
are very important, as they account for most of the non-linearitics
CORRECTION
Operating Lines in Cascade Separation of Binary Mixtures
S-T.HWANG and KARL KAMMERMEYER
Equation ( 2 2 ) on page 39 of the February 1965 issue
of T h e Canadian Journal of Cheinical Engineering should
contain a plus sign rather than a minus sign, and should
read as follows:
Y"+l = yu..
:(jYj)
I-1 +1
72
in the system. Good kinetics data are at best difficult to obtain,
and represent the most important part of most reactor designs.
However, even with limited kinetic data, the present work
has confirmed the usefulness of the conventional mathematical
model for predicting the dynamic behavior of a chemical reactor.
Nomenclature
A = area of the heat exchanger, cni.z
C, = heat capacity of a n y stream in or out of the reactor,
1 cal./gm.'K.
C, = heat capacity of the cooling water, 1 cal./gm."K.
EIR = energy of activation divided bv R. 3086°K.
-AH +
= heatof reaction. 16.61 X lo3 0.1210 ( T - 293.2) X
lo3 cal./gm. moie of ammonia'reacted '
= reaction velocity constant, 2-
C" c2
= frequency factor, 1.419 X lo3
= inlet ammonia concentration, 4.06 moles/liter
= concentration of ammonia in the reactor, moles/liter
= inlet formaldehyde concentration, 6.32 moles/liter
= c o n c e n t r a t i o n of f o r m a l d e h y d e i n t h e r e a c t o r ,
moles/li ter
= inlet ammonia flow rate, 1.50 cc./sec.
= inlet formaldehyde flow rate, 1.50 cc./sec.
= inlet cooling water flow rate, 2.65 cc./sec.
= reaction rate, gm. moles of ammonia converted/liter ser.
= density of all streams, 1 gm./cc.
= a n y temperature, OK.
= inlet cooling water temperature, 293.2"K.
= outlet cooling water temperature, "K.
= inlet ammonia temperature, 293.2"K.
= inlet formaldehyde temperature, 293.2"K.
= time, seconds
= speeded-up time, t/20
= overall heat transfer coefficient, cal./cm.* "K. sec.
= reactor volume, 490 cc.
References
Kermode, R . I., M.S. Thesis, Northwestern Univ., Evanston, Ill.
(1959).
Kermode, R . 1. and Stevens, M'. F., Can. J. Chem. Eng., 81 (1961).
van Heerden, C., Ind. Eng. Chem., 45, 6, 1242 (1953).
Kermode, R . 1.. Ph.D. Thesis, Northwestern Univ., Evanston, 111.
(1962).
Bose, S.. J. Indian Chem. Sac.. 34, 6 6 3 (1957).
Bauer, E. and Ruetschi, W., Helv. Chim. Acta. 24, 7 5 4 (1941).
Boyd, M. L. and Winkler, C. A,, Can. J . Research, 25B, 3 8 7 (1947).
Richmond, H. H., hlyres, G. S . and Wright, G. F., J. Am. Chem.
Sac., 70, 3659 (1948).
* * *
. . . (22)
Editor.
The Canadian Journal of Chemical Engineering, April, 1965