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Optimum temperature sequences in reactors

by Professor K. G. DENBIQH*

Rleum6-On passe en revue les travaux anterieurs de plusieurs auteurs sur les profiles de
temp&ature les plus favorables pour des reactions exothermiques reversibles et des reactions de
degrsdation.
Quelques nouveaux calculs servent B illustrer les grandes augmentations de rendement qui
peuvent Btre realis& si lon emploie la succession la plus favorable des temperatures dans des
c&s ou il faut Bviter des reactions secondaires.

Zusammenfassung-Eine kurse Ubersicht der friiheren Arbeit verschiedener Forscher iiber


reversible exothermische Reaktionen und Abwertungsreaktionen wird gegeben.
Einige neuen Berechmmgen illustrieren die grosse Zunahme der Ausbeuten, die sich in Fallen
von konkurrierenden Nebenreaktionen durch optimale Temperaturstufung erzielen Rsst.

Summary-The earlier work of various authors on the optimum temperature profiles for
reversible exothermic reactions and degradation reactions is briefly reviewed.
Some new calculations are put forward which illustrate the large increasesin yield which may be
obtained by use of an optimum sequence of temperatures in cases where there are competing side
reactions.

INTRODUCTION i.e. increase in the amount of reaction product


per unit of time and volume,
ONE OF the advantages of continuous operation, as
compared to batch, is that it is much easier to (2) improvement in the yield of the reaction, i.e.
maintain a controlled change in the variables which increase in the fraction of the reagent which is
determine the reaction rate, as reaction proceeds. converted to the desired products, due to the
Of these variables temperature is one of the most suppression of unwanted side reactions.
important and in ammonia synthesis, for example, The f%st of these has already been the subject of
valuable improvements have been achieved by several papers in the literature and will therefore
maintaining a certain optimum temperature profile be reviewed only very briefly.
along the length of the reactor. And although it is
temperature which is the theme of the present OUTPUT PROBLEMS
paper, it is worth remarking that it is not the only
The best-known example of the use of optimum
variable which may be usefully controlled. For
temperature profiles is to be found in the reversible
example, in certain nitration reactions, carried out
exothermic reactions; e.g. ammonia synthesis, sul-
in continuous stirred tank reactors in series, im-
phur dioxide oxidation and the water gas reaction
provements have been attained by making a change
between steam and carbon monoxide. For such
in the acid concentration from one tank to the next,
reactions the effect of an increase of temperature is
by means of subsidiary feeds of weaker or stronger
to reduce the value of the equilibrium constant (and
acids. In this instance, of course, the change in the
thus the maximum conversion) but also to increase
variable is stepwise rather than continuous.
the speed of the forward reaction. Thus the thermo-
The advantages which may be obtained by the
dynamic and the kinetic factors are, in a certain
use of an optimum sequence of temperatures-
sense, in opposition. Near the inlet to the tubular
which may be either stepwise or continuous-fall
reactor, where the reacting gas is still far from
into two distinct categories:
equilibrium, it is advantageous to have a high
(1) improvement in the output of the reactor- temperature in order to favour the rate of the for-
* University of Edinburgh and Heriot-Watt College. ward reaction, and near the outlet to the converter

125
Profewor K. G. DENBIGH

it is advantageous to have a rather lower temper- but that the temperature should subsequently be
ature in order to favour the equilibrium. At each diminished, as B accumulates, in order to utilize
cross section of the reactor there is thus a certain the fact that a reduction of temperature slows down
optimum temperature which maximizes the output the reaction B + C more than the reaction A + B.
of the vessel. Therefore there should again be an optimum
The matter may also be expressed as follows in sequence of temperatures, diminishing continuously
terms which are entirely kinetic: for a reversible from the inlet of the reactor. In fact the reversible
exothermic reaction the effect of an increase of reactions previously discussed are a special case of
temperature is to increase the speed of the reverse the degradation reactions with C identical with
reaction more than the forward reaction. The tem- A-i.e. B --f C becomes the reverse reaction.
perature should therefore be reduced progressively However the theory of the optimum temperature
as the amount of reaction product increases. profile for the degradation reactions is much more
For this type of reaction it is comparatively easy diflicult. It has been discussed recently by BILOUS
to set up the theory of the optimum temperature and AMUNDSON [5] and these authors have obtained
profile and to calculate the numerical value of the numerical solutions to the problem of the optimum
optimum temperature as a function of distance temperature profile by use of an electronic com-
along the reactor. The problem was first discussed puter. It seems however that there is scope for
by TEMKINand PYZE~EV[l], and subsequently by further work on this problem, for BILOUS and
DENBICH [2], ANNAESLE [3] and CALDER~ANK[4]. AMUNDSONpoint out very candidly that their own
The design of a reactor to conform to the optimum treatment leads to a peculiar paradox: namely
profile is, of course, a di&ult problem in heat trans- that there appears also to be an optimum profile of
fer but it is understood that a good approximation diminishing temperatures for the case where the
has been made in certain ammonia synthesis plants reaction A --f B has a greater temperature co-
and has resulted in a considerable increase in out- eficient than the reaction B -+ C. This is not what
put.* would be expected intuitively.
A problem of a somewhat similar character occurs
in degradation reactions, i.e. the class of reac- YIELD PROBLEMS
tions in which the required product can react fur- Under this heading we are concerned with the
ther to give waste products. Consider the sequence question whether an optimum sequence of temper-
of two irreversible reactions, atures can increase the yield of a reaction, i.e. the
A+B+C, fraction of the reagent converted to the desired
in which B is the required product and C represents product, quite irrespective of whether this sequence
a substance or substances formed by degradation. of temperatures might possibly reduce the output of
Let it be supposed that the temperature coefficient the plant.
of the reaction A --f B is positive, but is smaller In a great many organic reactions there are
than that of the reaction B + C. Intuitively it transient intermediates, There are also side reac-
seems clear that the temperature should initially tions which give rise to unwanted by-product,s,
be high, in order to accelerate the first reaction and such as carbon dioxide, tarry substances, etc. Such
thus to obtain a large output from a given volume, processes can thus be expressed symbolically:

(I) (31
+ With regard to the details of the theory, Prof. A+B-+X-+Y
AXUNDSON has pointed out to the author that eq. (39)
in reference [2] should strictly have been differentiated at
constant partial pressures, rather than at constant concen-
trations. This arises from the fact that the total pressure
!
J
(2) I
4
(4)

is approximately constant along the length of the reactor. P Q


This correction alters somewhat the form of the subsequent
equations. but does not have much effeot on the numerical where Y is the desired product, X is an intermediate
solution. (which may be either a free radical or a metastable

126
Optimumtemperatureaequenoeein reactors

molecule) and P and Q are the products of side immensely more difficult than either of the ex-
reactions. Thus, on account of the latter, the yield amples discussed under the previous heading. In-
of Y can never be lOOo/o and may be very much stead of discussing the tubular reactor, we shall
lower. On account of the cost of the raw materials, therefore suppose that the reaction process is car-
A and B, an improvement in the yield may often ried out in two continuous stirred tank reactors in
be a much more important economic factor than series. It will be shown that the problem can be
an increase in the output of a given volume of solved for such a system and that the yield can in
plant. fact be increased very considerably by holding one
It is evident that the yield is higher the greater tank at a different temperature from the other.
is the speed of reaction 1 relative to reaction 2 and of A system of this type is, of course, an entirely
reaction 3 relative to reaction 4. Ideally one should practical means of performing the reaction on the
therefore look for selective catalysts, but these are large scale-although it would be preferable to use
not easily found. As a result of practical experience more than two stirred tank reactors in series, in
in explosives production (which cannot be discussed order to reduce the total volume. However, it is
in detail), the author is convinced that a valuable probably fairly safe to generalize from the example
alternative is the use of a controlled sequence of of two tanks to the case of three or more, and the
temperatures. tubular reactor itself may be regarded as an infinite
Let it be supposed that reaction 1 has a lower sequence of stirred tank reactors, each of infinit-
temperature coefficient than reaction 2. Then as esimal volume.
far as the competition of reactions 1 and 2 are con- For simplicity, each of the four reactions will be
cerned, a low temperature will tend to increase the assumed to be first order: thus the speed of reac-
yield. Let it be supposed however that reaction 3 tions 1 and 2 will be taken as proportional to the
has a higher temperature coefficient than reaction concentration of reagent A and the speed of reac-
4. A high temperature will therefore favour the tions 3 and 4 as proportional to the concentration
conversion of X into Y rather than into Q. Thus, of X. This might occur if there is a large excess of
considering both factors together, the temperature reagent B and a large excess of the substance with
should be fairly low during the initial stages of which X reacts, e.g. the solvent, or a second mole-
reaction, whilst X is accumulating, but should be cule of B.
much higher during the later stages of reaction Let a, x and y be the stationary concentrations
when the main reactions are the conversion of X of A, X and Y in the Crst tank and let a, x and y
into Y or Q. However, since all four reactions are be the corresponding concentrations in the second
actually taking place simultaneously, although to tank. Let G be the volume rate of flow (assumed
varying extents, the temperature should be in- approximately constant, as for a liquid phase reac-
creased progressively. In brief, if the reaction were tion) and let V and V be the volumes of the react-
carried out in a tubular reactor, there would be an ing fluid in the first and second tanks respectively.
optimum temperature profile for highest yield. The mass balance equations for substances A, X
In the converse situation where the reaction 1 and Yin the first tank are
has a higher temperature coefficient than reaction 2
M, = Gu+ Vu(K,+K,) (1)
and reaction 3 has a lower temperature coeficient
than reaction 4, the optimum profile should be one Gx = V(k,a-k,x-k,x) (2)
of falling temperatures along the path of reaction.* Gy = VK,x, (3)
The full mathematical analysis of this problem
for the case of a tubular reactor, which allows a where M, is the molar feed rate of A. Similarly for
continuous variation of temperature, is certainly the second tank

l The remainingtwo CM concerningthe temperature Gu = Gu+ yu(k,+ k;) (4)


coeffioientsrequire, of course. either uniformly high or
uniformly low temperatures,and arenot of interestin the
G3e = Gx+ V(k,lu-Gx-k,x) (5)
presentdiaCllef5ion. w = Gy+ TGX. (6)
127
Professor K. G. DENBICHX

in these equations k, and k, refer to the velocity 72 = k,/k,


constants of the reaction A-j-B --f X in the first
and second tanks respectively, as determined by r4 = k;/k3
the prevailing values of the temperatures. Similarly
The yield is thus independent of the time of
with regard to k,, k, etc.
passage, V/G, in the second tank (due to the
Since the rate at which the useful product Y
assumption of virtually complete reaction) but does
leaves the system is Gy moles per unit time, the
depend on t = V/G, the time of passage in the first
yield of the reaction is
tank. Now what is being aimed at is to increase the
yield by holding the tanks at different temper-
@ = GyIM, (7)
atures. In the absence of a complete mathematical
analysis, it seems likely that the best holding time
It will now be supposed that the time of passage
under the temperature conditions of the first tank
in the second tank is large enough for reaction to
will be approximately equal to the time needed for
be virtually complete. With this assumption the
the concentration of the intermediate substance X
terms Ga and Gx in eqs. (4) and (5) respec-
to pass through its maximum. This statement has
tively can be neglected by comparison with the
not been proved, but it seems a reasonable assump-
other terms. By elimination between the above
tion and, in any case, there is complete freedom in
equations we thus obtain the following equation for
regard to the choice of t.*
the yield: From eqs. (1) and (2) :

~ ~k,{~k,Y,(l+~,)+l}(l+~,)+l+~~,~,(l+~,)
Wfa
= (l+rz)(l+~,){l+~k~(1+~,)){l+~k,~,(l+~,)) x= (9)
(8)
where t = V/G, the time of passage in the first and thus x has a maximum value at a time t ,,, given
tank, and r2 etc. denote the following ratios of bY
1
velocity constants : t, = (10)
rz = k,Ik,
~3 = W, We shall therefore choose this value oft as the time
of passage in the first tank. Substituting in eq.
r4 = k,Ik,
(8) and simplifying, we thus finally obtain the
yield as :

In the special case where the temperatures are The velocity constants are exponentially depen-
equal in the two tanks, r2 = r2 and r4 = r,; under dent on the temperature and their ratios r2, r2,
these conditions equation (11) reduces to etc. may therefore be written as the following func-
tions of T and T, the temperatures in the first and
1
CL = (12) *Since this paper was drafted, one of my Edinburgh
(1 +r,)(l+r,) colleagues, Mr. R. ARIS,h&3demonstrated that the optimum
time in the first tank is somewhat less than the time t,
and this has a maximum value at a particular used above, but the effect of this ia to increase the maxi-
temperature, which is therefore the best temper- mum yield only very slightly. The yield ia evidently not
ature for isothermal operation. very sensitive to the choice oft.

128
second tanks respectively, together with the con- seen at once that yields may be obtained which are
stants ca, b,, etc.: at least twice as large as the best value (25%) for
isothermal operation.

For known values of the bs and cs the yield of


the reaction may thus be calculated from eq. (11)
r
for any chosen temperatures T and T.
FIQ. 1.

NUMERICAL EXAMPLE
With the values of the constants as chosen above
By way of an example we shall choose there is an optimum value for T, but not for T, i.e.
c2 = 104, c, = 10-2, c, = 10 the maximum yield increases progressively with
increase of T. However by far the greater part of
b, = -3OOO, b, = 0, b, = +3000
the gain in yield may be obtained for a compara-
rhysically these values are quite reasonable; thus tively small increase in T. Thus it will be seen from
a value for b, of 3000 means that the activation the figure that a yield of 53% may be obtained by
energy of reaction 3 is about 6000 calories per mole 6xing the temperature of the f&t tank at 280 K
greater than the activation energy of reaction 4. (7 C) and the temperature of the second tank at
Consider 6rst of all the isothermal case, i.e. when 414 K (141 C). This would be entirely practicable
the tanks are maintained at the same temperature. if the reaction were carried out in a suitable solvent.
By substituting (13) in (12) and differentiating, and Although the theory has not been extended to the
using the above numerical values for the constants, case of three tanks, it may be expected that a fur-
it is found that the bc 3t temperature for isothermal ther increase of yield might be obtained, by using
operation is temperatures of, say, 300 K, 320 K and 410 K
T = 326K respectively.
and the corresponding maximum value of the iso- It may be noted that the value of the ratio ra
thermal yield, 4&, is (chosen as 1O-2 in the example above) determines
the speed of the reaction X--f Y as compared to the
0~ = 0.25 (i.e. 25%)
speed of the reaction A -+ X. Thus when this ratio
Under conditions of unequal temperatures in the is small, the formation of the intermediate X is
two tanks, the yield may be calculated numerically much more rapid than its conversion into the final
by solving eq. (11). This has been done by product Y (for equal concentrations). This implies
holding T constant at a particular value and calcu- a virtual segregation of the two reactions, i.e. for a
lating @ at various values of T; this was followed suitable choice of the time of passage, the process
by a similar solution for a second value of T, and X --t Y hardly occurs at all in the first tank, but
so on. completes itself in the second. It is clearly under
The results are shown in the figure and it will be these conditions that a difference of temperatures

129
Professor IL a. DICNBIQH

between the two tanks will have the largest effect. complex organic reactions the kinetica will not be
Conversely for large values of the ratio r,, the ex- known in s&Cent detail to make possible a
tent to which the reactions can be segregated is quantitative application of the theory. In fact the
much reduced and the temperature difference will nature of the transient intermediates themselves
thus have a smaller effect. may be quite unknown. However, it is evident that
This has been confirmed by solving eq. (11) the reaction scheme
for the same values of c,, cd, b,, b, and b, as above,
but putting c3 (= rS) equal to 1 in place of 1O-2.
The best yield was found to be only very slightly
higher than for isothermal operation, but it is of
interest that there was now an optimum temper- is a very general one, and in any process of manu-
ature (ca. 350 K) for the second tank, as well a~ facture where there is scope for the improvement of
an optimum for the first. This is aa might be the yield it will therefore be worth while to carry
expected. out a hit-ad-miss experimental trial of various
sequences of rising or falling temperatures. A
DISCUSSION method of this kind was adopted by the author and
his colleagues in the production of a certain explo-
From the above example it will be seen that very
sive by a nitration reaction, and was found to be
substantial increases in yield may be obtained by
remarkably successful.
using a controlled sequence of temperatures. This
In place of a steadily rising or falling sequence of
applies the more forcibly the greater is the speed of
optimum temperatures, it may occur that this
the reaction A + X relative to the speed of the
optimum profile itself passes through one or
reaction X + Y since this is conducive to their
more maxima or minima. This might occur if there
segregation.
is more than one intermediate in the overall reac-
Intuitively it seems likely that the advantages
tion :
of non-isothermal operation will also increase with
A+B+X+Y+Z
larger differences in the activation energies of the
main reactions as compared to the side reactions, Finally it may be worth emphasizing that a
i.e. larger magnitudes of b, and b,. These quantities tubular reactor, which allows of a continuous
were chosen as -3000 and +3000 in the above variation of temperature along its length, may be
example (i.e. differences of activation energies of expected to give appreciably better results than a
6000 calories per mole), but considerably larger sequence of continuous stirred tank reactors, since
values might occur in certain reactions. in the latter the temperature sequence is necessarily
Of course in a great many actual instances of discontinuous.

(Received: 24 November 1956)

NOTATION

a, x. 9 concentrations of substances A, X and Y in k,, k,, etc. velocity constants of reaction8 1, 2, etc. iu
first tank second tank
a, x, y concentrations of substances A, X and Y in fI, r,, etc. ratios of velocity constauta
second tank T, T temperatures in OK of first and second tauke
b,, b,, etc. constant related to difference of activation respectively
energies of reaction8 t( = V/u) time of paeaage in first tank
Cl, c, etc. ratio of non-exponential factors of reactions (;I volume rate of flow
& molar feed rate of substance A v, V volumes of fluid in first and second tanke
k,. k,, etc. velocity constants of reactions 1, 2, etc. in respectively
first tank cp reaction yield

130
Optimum temperature sequencee in renctors

REFEBENOES

[l] TEMKIN and PYZEEV; Ada Physioochim. URSS I!340 12 337.


[2] Dmmmir; Trotw. Foradoy Sot. 1944 43 362.
[3] ANNAB~; Chetn. Eng. Sci. 1962 1 146.
[4] CALnumJAuK; C%em. Eng. Proq. 1963 49 686.
[b] BILOTJ~and hflJNDSON; Chmn. Eng. SC& 19665 81,116.

DISCUSSION

Dipl. Ing. Fr. Honu: System l&bar sein soll, su den Diiferentialgleichungen fiir
Herr Prof. DENBIGH hat an einem Beispiel gezeigt, dass die Mengenstriime noch eine weitere Beziehung, die
die Ausbeute an dem gewimschten Endprodukt stark vom Optimalbedinguug, treten. Sie l&s& sioh bei n unabh&ngige
Temperaturverleuf l&rigs des Reaktionsweges abbtigen Reaktionen durch das Verschwinden einer n+l-reihigen
ksnn. Die optimale Temperaturverteilung I&& sich Determinanta ausdriicken (Abb. 2). Bei drei Reaktionen
ebenso wie fur die Ksskade such ftir das Reaktionsrohr
ohne Riickvermischung berechnen. Die Schwierigkeit F(qti, qu, q+-+Extremwe~.
dieser Rechnung hi%@ im wesentlichen nur von der
Ansahl der stoechiometrisch umabh&ngigen Reaktionen
ab (Abb. 1). aF aF aF
0
G* a4, ap,
afl
-----WV fll 62 613
-E
= 0
41 af2
121 522 423
-iiF
42 af3
xv = h(c71>
Q2,43* T) 631 632 633
aT
43
TV = fsh 42943, T)

Am Reaktorende :
Bei drei solchen Reaktionen z.B. ist der Zustand des
Reaktionegemiaches an jeder Stelle durch die Mengen- =Ofiiri# k
at&me von drei ausgew&hlten Komponenten (ql, qP, qr) br(
und durch die Temper&u feetgelegt, wenn die Mengen- =lfiri=k
strome am Eingang oder am Ausgang beksnnt sind und
LhB. 2
vom Druckebfall abgesehen wird. Aus Stoffbilansen
ergeben sich fur die Mengenstriime drei DiiIerential-
gleichungen. In ihnen bedeutet V entweder dss Volumen ist es eine vierreihige Determinante. Die Optimalbedin-
oder die Katalysatormenge von Anfang des Reaktors bis gung gilt hier fiir den allgemeinen Fall, daes nicht nur em
zu der betrachtetan Stelle. Die Funktionen auf der rechten Mengenstrom sondern eine beliebige gegebene Funktion B
Seite der Gleichungen sind die Bildungsgeschwindigkeiten der Mengenstri5me am Ausgang des Reaktors einen
der ausgewi%hltenKomponenten. Sie lassen sich leicht Extremwert annimt. Des ist eine Aufgabe. die bei mehr
angeben, wenn die Kinetik der ablaufenden Reaktionen sls einem Endprodukt und bei Rtickfiibrproblemen
bekannt ist. vorkommen kann. Die Ableitungen der Funktion F nach
Aus diesen Gleichungen ksnn man den Verlauf der Men- den MengenstrGmen am Ausgang und Null bilden die erste
genstrome und der Konsentrationen olme weiteres Zeile der Determinante. In der let&en Spalte stehen die
errechnen, wenn die Temperatur als Funktion von V Ableitungen der Bildungsgeschwindigkeiten nach der
gegeben ist. Ftir den optimalen Reaktor ist diese Temper- Temper&u. Ausserdem kommen in der Optimalbedingung
sturfunktion unbekannt und es muss daher, wenn das noch n* Hilfsfunktionen vor. die einem System von lin-

131
Professor K. G. DENBI~H

esren Differentialgleichungen mit bestimmten Rand- an jeder Stelle des Reektors erfiillt sein muss noch eine
bedingungen fiir da8 Reaktorende geniigen. weitere Optimalbedingung fiir das Reaktorende.
Hat man nur eine stoechiometrisch unabh8ngige Reak- Die erwahnten Optimalbedingtmgen sind mu notwen-
tion wie z.B. ein Gleichgewicht dige aber keine hinreichenden Bedingungen. Falls em
optimaler Reaktor ftir das formal sngembriebene Problem
A+B = c+D, iiberhaupt existiert. darm kann er in der engegebenen
Weise berechnet werden. Aber nicht jeder Losung der
dann vereinfacht sich die Determinante zu Differentialgleichungenund der Optimalbedingungen muss
em optimalter Reaktor entsprechen. Fiir eine spezielle
Aufgabe ist d&her noch eine Diskussion der L&sung
IE- 01 erforderlich.
aqe _ = 0.
Prof. K. G. DENBIQH:
5; It is dit%cult for me to comment on Dr. HORNSinterest-
ing contribution. In the short time available to him on the
platform. he had to restrict himself to presenting his
Scbliesst man den pmktisch bedeutungslosen Fall mathematics in a very schematio form. I am very much
looking forward to seeing his work when it is published.
8F
-= 0 Dr. C. VAN HEERDEN:
a!& In principle it is possible to oaloulate every system in
which the temperature level is mainly determined by the
aU8, d8nn Wird aflaT = 0. reaction heat, in which, accordingly. relatively little heat
Diese Gleichung ist seit langem bekannt, und besagt, is supplied from outside, and in which the prooess can only
dam im optimalen Reaktor an jeder Stelle die Umset- be realized after ignition.
sungsgeschwindigkeit extremal sein muss. If the st&tionary state of & reversible reaction is an
Bei mehr als einer un8bh8ngigen Reaktion kann man equilibrium condition, the tendency of the reaotion velo-
fur die Ermitthmg des optimalen Temperaturverlaufs das city to increase considerably at rising tamper8ture is
System der Differentialgleichungenfiir Mengenstriime und compensated by the counteracting effect of the reverse
Hilfsfunktionen und der Optirnalbedingungen direkt reaotion.
numerisch oder graph&h integrieren. Man beginnt mit For non-reversible reection, in which this counteracting
der Integration am Ende des Reaktors, die Optimal- effect does not exist, the conversion of one of the com-
bedingung dient dann xur Berechmmg der Temperatur ponents will become virtually complete at inoreaaing
und die restlichen Gleichungen dienen zur Ermittlung der temperature. The consequence of this circumstance for
Mengenstriime und der Hilsfunktionen an jeder Stelle. the temperature (sequence of temperature) in the reactor
Man kann Hilfsfunktionen such vor der Integration will always, to some degree, be in conflict with the desire
eliminieren und erh8lt damr Dil?erentialgleichungenfiir to realize a sequenoe of temperatures at which the reaction
die Temperatur und die Mengenstriime allein, so wie sie rate is maximum throughout.
Bilous und Amundson ftir verschiedene Beispiele abgeleitet
haben.
Statt die Gleichungen au integrieren kann man such Prof. K. G. DENBIQH:
einen angenommenen oder experimental1 ermittelten The consideration which Dr. VAN HEERDENhas brought
Temperaturverbuf mit der Optimalbedingung testen. forward represents an important limitation whenever the
Die Determinante verschwindet dann nattirlich nicht und reaction is carried out under adiabatic conditions. I would
aus dem Verlauf ihres Wertes langs des Reaktors kann remark, however, that there is no necessity for reactions to
man schliessen wie die Temperaturverteilung in dem be carried out adiabatically and whenever there are advan-
engenommenen Reaktor zu ver8ndern ist, damit er sich tages to be gained by adopting a controlled sequence of
dem optimalen Reaktor annghert. temperatures, such as I have described, it is always possi-
Wird ausser der Temperatur auoh das Reaktorvolumen ble to put heat into the system, or to remove it, in such a
bei gegebenen Durchsatz variiert, d.h. ist em Reaktor mit way as to attain the optimum sequence. In certain in-
optimalen Temperaturverlauf und Volumen gesucht, dann stances there may be practical difficulties in achieving the
tritt su der Optimalbedingung fiir die Temperatur, die optimum sequence, but I think none of principle.

132