Pergamon Chemical Enaineerin0 Science, Vol. 50, No. 19, pp.

3115-3123, 1995
Copyright © 1995 Elsevier Science Ltd
Printed in Great Britain. All rights reserved
0000-0000/95 $9.50 + 0.00
0009-2509(95)00116-6

THERMAL REGIMES IN COCURRENTLY COOLED

FIXED-BED REACTORS

D. O. BORIO*, V. BUCALA and J. A. PORRAS

Planta Piloto de Ingenieria Quimica, UNS-CONICET, 12 de octubre 1842, (8000) Bahia Blanca, Argentina
(First received 26 October 1994; revised manuscript received and accepted 14 March 1995)

Abstract--Seven different thermal regimes can be achieved when an exothermic first-order reaction takes
place in a cocurrently cooled fixed-bed reactor. All the regimes are feasible in reactors where the inlet
temperature of the coolant is different from that of the reacting stream. New thermal regimes were found;
they are qualitatively very different from those commonly reported in the literature (e.g. max-
imum-minimum, or minimum-maximum profiles, cold-spot regime). Based on a pseudohomogeneous
plug-flow model, the conditions of existence for all the regimes, as well as guidelines to select the operating
conditions to achieve the desired profile properly are presented. The diversity of feasible regimes can be very
useful to track optimum thermal profiles required to solve practical optimization problems.

1. INTRODUCTION the reactor design. A technically simpler solution is to

One of the most common arrangements to carry out
highly exothermic reactions is the multitubular fixed-
bed reactor, in which the catalyst is packed in the
tubes, and the heat-transfer medium circulates ex-
ternally around the tubes. The first section of the
tubes, packed with either inert solid or catalyst, is
basically used to preheat the gaseous mixture up to
the reaction temperature. Along this section, the cool-
ant fluid (a molten salt or an organic heat transfer
liquid) performs as a heating medium until the reac-
tant temperature reaches that of the coolant. Consid-
ering this reactor design, usually three basic cooling
schemes have been studied: countercurrent, perfectly
mixed coolant, and cocurrent. Borio et al. (1989a, b)
have demonstrated that, for equivalent production
rates, the cocurrent operation is the one which leads
to the lowest values for the maximum temperature
and parametric sensitivity. In addition, a given yield
can be obtained with the smallest reactor length, pro-
vided an adequate selection for the coolant flowrate is
made. These conclusions were confirmed in an indus-
trial reactor for o-xylene oxidation by Nikolov and
Anastasov (1989).
It is well known that the reaction course (and con-
sequently the final conversion and selectivity or yield)
is strongly dependent on the temperature profile de-
veloped inside the reactor. The most obvious way to
influence the reaction path, although technically the
most complex solution, is to arrange a number of
different heat-transfer medium circuits so as to
achieve a stepwise approximation of an optimum tern-
perature profile (Eigenberger, 1992). However, the de-
sirable solution should not require major changes in
*Corresponding author,
3115
manipulate the inlet temperatures of the gas and cool-
ant streams, as well as the coolant flowrate. Adequate
changes of these operating variables allow to achieve
axial thermal profiles, i.e. thermal regimes, very differ-
ent from the hot-spot profiles usually found in prac-
rice. This is particularly valid when a cocurrent cool-
ing scheme is selected. In fact, for equal feed and
coolant inlet temperatures Soria L6pez et al. (1981)
found a characteristic cocurrent thermal regime where
the temperature always increases along the reactor
length: the pseudoadiabatic operation. For the same
case, Ravella and de Lasa (1987) derived the condi-
tions to obtain the pseudoadiabatic regime at all
radial tube positions. The pseudoadiabatic operation
has been experimentally confirmed in pilot plant
fixed-bed reactors [Ravella et al. (1987, 1989) and
Simard et al. (1991) among others], as well as in an
industrial unit (Nikolov and Anastasov, 1989). De
Lasa et al. (1989) developed expressions to predict the
operating conditions admitting the pseudoadiabatic
operation when the inlet temperature of the coolant is
different from that of the reacting stream. If the inlet
temperatures and the coolant flowrate are properly
selected, the cocurrent configuration also allows to
obtain an isothermal operation (Degnan and Wei,
1979, 1980).
Summarizing, for the cocurrent scheme the condi-
tions of existence of three different thermal regimes
have been previously derived: hot spots, isothermal
and pseudoadiabatic operations. However, if the op-
crating conditions of a fixed-bed reactor are ad-
equately selected, it will be shown that a cocurrent
coolant scheme leads to seven different thermal re-
gimes. For an irreversible pseudo first-order reaction,
the conditions of existence of all the feasible thermal
regimes will be here presented. Simple expressions will
be used to predict them and also to exclude infeasible
operations. This enormous operating flexibility, at-
3116 D.O. BORIOet al.
tainable with minor changes in the current reactor expression is obtained:
design, can be useful:
B C B C
- - t o improve the reactor stability, i.e. to achieve T + ~pa + ~ T c = To + ~ pA0 + ~ TCo (4)
lower maximum temperature and parametric Considering that when z--*oo the reactor temper-
sensitivity for the same production rate (Bucalfi ature approaches that of the cooling fluid and the
et al., 1994), reactant is exhausted (To = Tc~, and PA = 0), from
- - t o closely track the optimal thermal profile eq. (4)we have
(which maximizes yield or selectivity) when mul- B C
tiple reactions take place (Bucal~i, 1991), and To + ~PA0 + ~TCo
- - t o change over time the shape of the temperature T~ C (5)
profile to follow the catalyst deactivation (Eigen- 1 + --
b e r g e r , 1992). D
Equation (5) is a generalization of the expression for
2. MATHEMATICALM O D E L Too reported by Soria L6pez et al. (1981), who studied
The basic pseudohomogeneous plug-flow model is the particular case of To = Tco. Using eqs (4) and (5),
used to represent the behavior of a cocurrently cooled eq. (2) can be rearranged as
multitubular fixed-bed react°r' where a pseud° first- dT I DI
order exothermic reaction occurs. The values of the ~ = BpA k~ exp ( - - a / T ) -- -- (C + D ) ( T - Too).
parameters adopted in the calculations, as well as the
reaction rate expression, correspond to an industrial (6)
reactor where air oxidation of o-xylene to phthalic This equation will be very useful to discuss the
anhydride is carried out (van Welsenaere and conditions of existence of the thermal regimes.
Froment, 1970; Sofia L6pez et al., 1981). The charac-
teristics of this reactor and the kinetic and thermo- a. CHARACTERIZATIONOF TEMPERATUREEXTREMES
dynamic parameters are reported in Table 1. The A necessary condition for existence of a local ex-
three differential equations expressing the steady-state treme in the temperature profile at a finite value of
mass balance and the steady-state heat balances in-
z = Zm is dT/dzl~, = 0. Therefore, from eq. (6)
side and outside the catalytic bed are:
(C + D)(Tm -- T~o)
dpA PA, = . (7)
d-~-= - A p A k ~ e x p ( - a / T ) (1) BIko~exp(_a/T,.) D7
L --_1
dT
d-~ = BpA k~ e x p ( - a / T ) - C(T--Tc) (2) To characterize a local temperature extreme, the
sign of the second derivative has to be studied. Thus,
dTc differentiating eq. (6) and evaluating at z = z.,
d"--f-= D ( T - - Tc) (3) dZT -ABpA,.k~exp(-a/T.)
where for z = 0, PA = Pao, T = To and Tc = Tco. ~ z, =
Combining eqs (1)-(3), and integrating from the v nq
reactor inlet to any axial position z, the following xlk~exp(-a/T,.)-AI. (8)

The sign of the second derivative is given by the

Table 1. Physical properties and data used in the simulation sign of factor between brackets in eq. (8). Conse-
quently, a maximum occurs when
a (K) 13,636
k~ (kmol/kg~.tkPa 2 s) 11.080 a
M(kg/kmol) 29.48 T,, > ln(Ak~/D)" (9)
P(kPa) 101.3
pb(kg/m 3) 1300 Moreover, as the reactant concentration at z = z~,
Gg(kg/m2 s) 1.301 has to be positive (PAre > 0), from eq. (7) the inequal-
AH (kJ/kmol) - 1,284,488
Cpg(kJ/kg K) 1.045 ity T , > Too must also be verified.
c~(kJ/kgK) 1.300 Conversely, when the local temperature extreme
pBo(kPa) 21,07 corresponds to a minimum,
t, 3000
a
d,(m) 0.025 Tm < (10)
1 In (Ak~/D)
U (kW/m2 K) (Crider and Foss,
1 d, 1 1965) and the condition T , < Too must be satisfied.
h~ + ~ + h~ From eqs (9) and (10) follows that the temperature
h~, k,,: calculated using the correlations derived by Yagi and value
Kunii (1957, 1960)
h~t: estimated from equations reported by Kern (1950) Tz - In (Ak~/D)
a (11)
 Thermal regimes in cocurrently cooled fixed-bed reactors 3117
represents the lower boundary for the maxima and the 2.o i
upper value for the minima. It is interesting to note c ~ c
that eq. (11), which defines the limiting temperature i'¢ i
for the general case of To ~ Too, coincides with the ,,
limiting temperature derived by Soria L6pez et al. 1.5 i, , A i B D
(1981) for To = Tco. Once the kinetic parameters and ~ i ,' '~
the reactor geometry are defined, the 7", value can be ~ ',, ~ I
modified varying the feed and/or the coolant flow- ~ Bil,
/ / , i,
rates. ~ 1.o ,,

4. T H E R M A L REGIMES: C O N D I T I O N S OF E X I S T E N C E [ , '~ r , ~ ,
The conditions of existence of each of the different 0.5 1 ~ ~' : : ~'
",i", :: G,=1.3Oll Kglm ~
operating regimes will be defined by means of four ,i ,,i i: we=50 Kgls
} '~ : Tc°= 618.23 K
v a r i a b l e s : t h e i n l e t r e a c t a n t s temperature (To), t h e Tc. T,\ii"J~i"i~},: L= Z va
temperature as z ~ oo given by eq. (5), Too,the limiting o.o ~--~--, , ,
temperature defined by eq. (I1), T, and the slope of 610 630 640 650 660 670 660
620
the axial thermal profile at z = 0, So, which can be T(K)
evaluated from eq. (2) as follows: Fig. 1. Hot-spot profiles in the p ^ - T plane: ( ) reactor
So = BpAO k~o exp (--a/To) -- C(To - Tco). (12) temperature, (- - -) coolant temperature.
Two cases which can be assigned to different de-
signs of the preheating section will be considered.
2.0
4.1. To <~ Tco A
G,=l.3011 Kg~m z s
We= zo K g / s l
TOo= 610 ~ !
The case To = Tco approximately holds for indus- ~ L= 2 m i
trial reactors where the inlet section of the tubes is x.5 ! ~ r
packed with inert solid. On the other hand, T o < T c o ~ ~ i ! ~ i
covers the case where the inert solid has been removed ~" n i F
and replaced by catalyst particles. From eq.(12) ~ ic',, i
S0 will be always positive, provided that To~<Tco. ~ 1.0 ~,,~\~ ~
For this case two different thermal profiles (hot spots
or pseudoadiabatic operation) which have been exten- c ' , ~,, ',, ,.,, ",,i
sively studied in the literature can be obtained. ""\ ",',~''\ ",k ",~, "~
0,6

4.1.1. H o t - s p o t regime. This is the thermal profile "',,"....

'.. \ ~, I'
usually found in the industrial practice. The condi- T~o.,.~ '':' "\ I
tions of existence of this regime are: o.o ~ , ",~ "i .i T'
560 666 6~0 6~6 ' ' 660
So > O, Too > Tt (13) T(K)
Typical hot-spot trajectories are illustrated in
Fig. 1. In all curves, solid lines correspond to trajecto- Fig. 2. Pseudoadiabatic trajectories in the pA-T plane:
( ) reactor temperature, (- - -) coolant temperature.
ries developed inside reactor tubes (L = 2 m) . The
dotted lines represent the extension of these trajecto-
ries beyond the reactor length until PA = 0 (i.e. 7", for To ~< Tco. Particularly, trajectory A is a limiting
T = Too). Some representative coolant temperature
profiles have also been included, they are plotted curve. All the limiting curves must satisfy the follow-
using dashed lines. This representation will also be ing relationship:
used in Fig. 2, and Figs 4-8. Curves A and B of Fig. 1 B C
satisfy the conditions To < Tco and To =Tco, respec- To + ~ pAO + ~TCo
tively. Due to the critical characteristics of the hot Too = C = T~ (15)
spots, several parametric sensitivity criteria for cocur- 1+
rently cooled reactors have been proposed to prevent
runaway (Soria L6pez et al., 198l; Henning and P6rez, These limiting curves represent the boundaries be-
1986; Hosten and Froment, 1986; Bauman et al., 1990). tween pseudoadiabatic and hot-spot regimes. Operat-
ing at these conditions, any increase in PAO, To, or
4.1.2. Pseudoadiabatic operation. To find a pseudo- Tco leads to T~o > T~, therefore a temperature max-
adiabatic temperature profile the following relation- imum at a finite axial reactor position will appear. It is
ships must be simultaneously satisfied: worthwhile to note that eq. (15) represents a generaliz-
So > 0, Too ~< Tt, To < Tl. (14) ation of the formula derived by Sofia L6pez et al.
(1981) for the particular case of To = Tco.
Curves A, B and C in Fig. 2 illustrate At this point it is appropriate to refer to the work
pseudoadiabatic operations in the phase plane pa vs. by de Lasa et al. (1989). They developed a criterion to
3118 D.O. BoRIo et al.
Table 2, T, and (PAo)Svalues calculated from eqs (11) and (15) of this work, and from expressions
derived by de Lisa et al. (1989)

TO(K) Tco (K) TI(K) Tj (K), de Lisa (PA0)~(kPa) (PA0)I(kPa), de

from eq. (11) et al. (1989) from eq. (15) Lisa et al. (1989)

540 620 662.88 688.73 1.6515 2.5296

600 620 662.88 673.31 1.5057 1.8600
610 620 662.88 668.93 1.4814 1.6869
620 620 662.88 662.88 1.4571 1.4571
630 620 662.88 650.16 1.4328 1.0003

Note: Data used in the calculations: Wc = 20 kg/s; Go = 1.3011 kg/m 2 s; A = 6.2868E7 kgcat kPa 2
s/m kmol; B = 2.5877E10 kgcatkPa K s/m kmol; C = 10.5396 m- ~ D = 0.8117 m- ~.

predict operating conditions admitting pseudoadia- 720

batic operations when To ~ Tco, apparently along ,;'
similar lines as those discussed here. However, the 700 ,' ',
expression they reported to calculate T~, which de- ,' ',
pends on the inlet temperatures, is not correct. In fact, ,' ',
that expression fails to predict the T~ value for those 8no ,' ,
conditions where To = Tco is not satisfied. As it is ~ vr' ,,
shown in Table 2, bigger errors in the prediction of ~" 660- ..............i / /
T~ are observed as the difference between To and Tco
increases. Therefore, the limiting conditions (i.e. the ,'
initial conditions (pAO)I, (To)I or (Tco)z to reach a given 64o- //
,2" rc.=azolql/s
We=20 X
limiting operation) are erroneously predicted. For )/ G,--I.3Oll Kl~/m s

To < Tco, the (pAo)z values are overestimated, whereas 6zo- /

for To > Tco the (pao)l values are underestimated. The
wrong prediction is demonstrated in Fig. 3, where
limiting curves predicted by both criteria are present-
ed. The solid line represents the limiting curve whose
(PAO)I value was calculated using eqs (11) and (15). The
(PAO)Z value for the dashed curve was predicted by
means of the criterion reported by de L i s a et al.
(1989). For this case, the limiting inlet partial pressure
was overestimated and therefore a hot-spot profile
was obtained instead of a limiting curve (Arandes and
de Lisa, 1995).
4.2. To > Tco
To satisfy this operating condition, the reactant
mixture must be preheated by means of a heating
medium in an external heat exchanger located before
the reactor inlet (Bucahi, 1991; Bucal~i et al., 1994).
For To > T c o , the sign of So is now undetermined,
depending on the difference between both inlet tem-
peratures [see eq. (12)]. If the reactor is designed sat-
isfying the condition To > Tco, in addition to the hot
spot and pseudoadiabatic regimes, five other thermal
profiles can be achieved,
4.2.1. Hot-spot re#ime. This regime (described in the
previous section) can also be obtained when
To > Tco, provided the same conditions as the case
discussed in Section 4.1 are satisfied, i.e.
So>O, To~> Tz
Curves C and D in Fig. 1 illustrate this operation,
4.2.2. Pseudoadiabatic operation. The condition of
existence of this operation are also defined by eq. (14).
800
o.0 t.b z.b a.0
z (m)
Fig. 3. Comparison between limiting curves predicted by
eqs(ll) and (15) of this work ( Tl = 662.88 K
(PAo)~= 1.4814kPa) and by the expressions derived by de
Lisa et al. (1989) (- - T~ = 668.93 K, (PAo)~= 1.6869 kPa).
Curve D in Fig. 2 is an example of a pseudoadiabatic
trajectory where the condition To > Tco is satisfied.
Again, the limiting conditions are defined by eqs (11)
and (15).
4.2.3. Maximum-minimum profiles. If the reactor is
cocurrently cooled and the following conditions are
satisfied:
So > 0, Too < Ti, To > Tt (16)
thermal profiles qualitatively different from those re-
ported in the literature can be reached. They exhibit
two local extremes: a hot spot and a m i n i m u m (or
cold-spot) downstream. Three illustrative examples of
this regime are shown in Fig. 4. Thermal profiles of
this kind have high hot-spots and parametric sensi-
tivities, therefore they should be taken into account in
the development of parametric sensitivity criteria for
cocurrently cooled reactors.
If the inlet coolant temperature is cool enough (so
that the heat withdrawal rate is higher than the heat
production rate, i.e. So < 0) three different thermal
regimes can be obtained: cold spots, decreasing ther-
mal profiles and m i n i m u m - m a x i m u m profiles.
 Thermal regimes in cocurrently cooled fixed-bed reactors 3119
2.0 2.0
~c--= 1.3011
20 Kg/sK g / m ~ s ~c--= l20
' 3 0 1Kg/s
1iKg/m~ s
To°= 610 K ~ TOo=610 K
L= 2m ~, A ~ L= 2m
, \

', \\ \

' :'c (/:: \, , \\ i

0.5 ~ :: ', 0.5 i" D i

' : .......ii...... ......

i;c. ,i .... , .......... i T
' ~ - ~ - -- 0.0 ~ - - ~
600 620 640 660 680 760 720 740 600 610 620 630 640 650 660 6'70 680
T(K) T(K

Fig. 4. Maximum-minimum profiles in the pA-T plane: Fig. 5. Cold-spot trajectories in the pA-T plane: ( - - - - )
( --) reactor temperature, (- - -) coolant temperature, reactor temperature, (- - -) coolant temperature.

4.2.4. Cold-spot regime. Necessary conditions to have 4.0 ~ i ~t T,

a cold-spot regime are exactly opposed to those re- a.5 ~ A

quired to achieve a hot-spot profile, i.e. 3.0 i, i,~' i~ i ' # /

So<0, T ~ < Ts. (17) ~ !,
Several cold-spot trajectories are shown in Fig. 5. ~ z.5 :, : B

Downstream the minimum, the temperature increases ~, z.0

monotonically. This is an expected behavior. Indeed, i i c
the conditions found at any point located down- 1.5
stream the m i n i m u m (which could be considered as
the inlet point for the reminder of the tube), satisfy the 1.0
inequalities given by eq. (14) (conditions of existence ~ : 1.30it200
Kg/sKg/m2 s
Tco= 590 K
of pseudoadiabatic operations). 0.5 ~ L= 2 rn
This regime can be considered as an interesting /, To°
alternative to operate fixed-bed reactors when 0.0580
~ - xi 600 , 6~0 , 6~0 ' ~660 ' 680
exothermic irreversible reactions are carried out. In T(K)
fact, due to the shape of these thermal profiles it is
possible to b o u n d the maximum temperature inside Fig. 6. Decreasing thermal profiles in the pA-T plane:
(- ) reactor temperature, (- - -) coolant temperature.
the reactor by the value of To or To (see Fig. 5). In
other words, T(z) <~max(To, T~). By modifying the
operating conditions, these bounds for the maximum
temperature can be selected a priori, z.o

4.2.5. Decreasing thermal profiles. This well known ! , c

regime is characterized by a continuous temperature ~.5 ',
decrease along the reactor length. Its conditions of ~
existence are:

So<O, T~ >I Tl, To> Tl. (18) c~ 1.0

\
F o u r decreasing profiles are shown in Fig. 6.

4.2.6. Minimum-maximum profiles. If So < 0 the ther- o.~ 1 ~rzc--"

= 1120.3011Kg/sKg/mes i/
. TCo= 610 K /
mal profiles can also exhibit two extremes. In fact, if L= 2 m '........... ~i/
the following conditions are satisfied: , ',. !ii~
l:'il
i Tco : Tt 21ii I
So < 0, Too > Ta, To < Tl (19) o.o "~°" "'\~
600 610 620 630 640 650 660 670 680
the thermal trajectories will present a m i n i m u m fol- T(K)
lowed by a maximum. Different m i n i m u m - m a x i m u m Fig. 7. Minimum-maximum profiles in the pA-T plane:
profiles are illustrated in Fig. 7. (- ) reactor temperature, (- - -) coolant temperature.

CES SO-19-H
3120 D.O. BORIO et al.
4.2.7. Isothermal operation. This regime was pre- eq. (20), it can be concluded that the temperature at
dicted and experimentally verified by Degnan and which the reactor operates isothermally coincides
Wei (1979, 1980). Isothermal operations have to sat- with the limiting temperature defined by eq. (11). In
isfy simultaneously the two following equalities: Fig. 8 three isothermal operations are shown, corres-
T ~ = T~, To = Tt. (20) ponding to three different values of Wc.

If the initial conditions satisfy eq. (20), from eq. (6) it 5. INFEASIBLE THERMAL PROFILES
is obvious that dT/dz = 0 at any axial position. F r o m
F o r exothermic irreversible first-order reactions
taking place in a cocurrently cooled reactor, only the
z.s - seven thermal profiles discussed above are feasible. To
G,= L3011 I~/m ~ ~ demonstrate why trajectories of other types are in-
wol= lO0 Kg/s feasible, simple analytical tools can be used. Many
Wez= 50i Kg/s
2.0 - 2~, 2 TOol=We2=
25i606.04Kg/SK hypothetical profiles can be thought, however just
TOo~= 609.1z K a few will be discussed here. Figure 9 shows several
'~' Teo~= 630.15 K
L= 2 m! schematic temperature profiles. Figure 9(a) illustrates
1.5 i a hot-spot profile whose maximum temperature is
~, , , i lower than T~ (curve 1), and a cold-spot profile where
", I ' : T,, > Tz (curve 2). Both operations cannot be achieved
1.0 4:
", ',i in practice because they violate eqs (9) and (10). In
', ~, ~ Fig. 9(b) two m a x i m u m - m i n i m u m profiles are pre-
' b'" :l '( sented, representing cases where To = T, (curve 1) and
0.5 i ...... i To < Tl (curve 2). Each of these curves should inter-
...~ ..... ~ .... sect twice the T~ value, initially with a positive slope
o.6 ~ ~ ~ ~ ~ =--- and then with a negative one. However, eq. (6) for
600 620 640 660 680 T = T~ becomes
T(K)
Fig. 8. Isothermal operations in the pA-T plane: ( _ _ ) --d__T_ = (C + D ) ( T o ~ - Tt). (21)
reactor temperature, (- - -) coolant temperature. UZ T=T l

T T
II I

1, 5

z z
Figure 9a Figure 9b

T T

T,..................
i ~ J 1-,
z g
Figure 9c Figure 9d
Fig. 9. Examples of infeasible thermal profiles.
 Thermal regimes in cocurrently cooled fixed-bed reactors
Since Too and Tt are unique for a given trajectory,
the sign of eq. (21) is either positive or negative, but it
cannot assume both signs. Curves 1 and 2 of Fig. 9(b)
are therefore infeasible. Analogously, this argument
can be used to exclude curves 1 and 2 in Fig. 9(c)
(infeasible m i n i m u m - m a x i m u m profiles) and any tra-
jectory with three temperature extremes, as those pro-
sented in Fig. 9(d).
6. PREDICTION OF THERMAL REGIMES:
ZONES
The conditions of existence of the thermal regimes
presented above can be summarized in a Pao-To
plane. Three curves can be drawn to divide the whole
plane into particular operating zones. These curves
are the locus of the following equations that can be
evaluated a priori:
C (To - T c o )
So = 0, i.e. from eq. (12) pAo = Bko~ exp ( - a l T o ) (22)
Too = T~, i.e. from eqs (5) and (11)
3121
the chosen values of Gg, We, and Tco, no matter what
values for the inlet variables (PAo, To) are selected. If
Wc is increased from 10 to 40 kg/s, keeping the re-
maining operating conditions constant, the min-
i m u m - m a x i m u m zone vanishes because Tt decreases
(Fig. 11). Conversely, the pseudoadiabatic region
reaches its maximum area. The same effect occurs for
cold-spot and m a x i m u m - m i n i m u m zones. When Wc
is further increased e.g. up to l l0kg/s, the max-
OPERATING i m u m - m i n i m u m zone vanishes while the region of
decreasing thermal profiles appears (Fig. 12). More-
over, the zones where pseudoadiabatic and cold-spot
regimes occur have considerably diminished. For even
higher coolant flowrates, Tt can be lower than Tco.
Consequently, the cold-spot and isothermal opera-
tions will not be achieved. Finally, as it is well known,
for extremely high coolant fiowrates [where Tc(z) can
be assumed as a constantJ T~ ~ 0. Under these condi-
tions the reactor can only be operated at two different
regimes: either hot-spot or decreasing thermal pro-
files.

PAO=~ 1+~ ln(Ako~/D) 5To° -~To e.5 ~

(23) z.o
a
To = Tz, i.e from eq. (11), To = ln(Ak~/O)" (24)
"~ 1.5
Figure 10 depicts the operating zones determined
by eqs (22)-(24), for a given set of values of Gg, We, .~
and Tco. This is a useful representation, because each ~ t.o
zone satisfies the conditions of existence of a particu-
lar thermal regime. As already discussed, for To ~< Tco 0.5
only two regimes can be obtained: hot-spot and I ~o,.....
pseudoadiabatic operations. O n the other hand, for
To > T c o and the selected operating conditions, six o.o5 0 0 600 700 800
regimes can be achieved. Particularly, the isothermal To (K)
operation is located at the point where eqs (22)-(24)
are simultaneously satisfied. It must also be noticed Fig. 11. Operating zones for the thermal regimes in the
that decreasing thermal profiles cannot be found for PAo-To plane (Tco = 610 K; Wc = 40 kg/s; Ga = 1.3011
kg/m 2 s).

2.5
2.5 I

2.0 ~ T°=T' ;~.0 To=T¢

~=Te ~ 1.5
"~ 1.5 i2~

1,0

O.5 ~ ,l!,~ IIIIhl

i ii~ I¸~¸ ,;i
il II rllJLiirllJrllJrllll
E 0.5

0.0 ' J J~ ' - ~ ~ ~ 500 600 700 800

500 600 700 800
To (X) To (K)

Fig. 10. Operating zones for the thermal regimes in the Fig. 12. Operating zones for the thermal regimes in the
PAo-To plane (Tco = 610 K; Wc = 10 kg/s; Gg = 1.3011 pAo-To plane (Tco -- 610 K; Wc = ll0 kg/s; Gg = 1.3011
kg/m 2 s). kg/m 2 s).
3122
Tco is also an important operating variable to de-
terminethermal regimes. Figure 13 shows its influence
on the operating zones. For fixed values of Gg and Wc,
changes in Tco do not modify Ts, but strongly affect
the curves defined by eqs (22) and (23). Increasing Tco
pseudoadiabatic and maximum-minimum regions
are reduced, while the hot-spot area becomes larger,
The zone where So < 0 is reduced as Tco increases,
The minimum-maximum zone appearing for
Tco = 590 K tends to disappear for higher inlet cool-
ant temperatures. For Tco values higher than 610 K
the decreasing thermal profiles became possible (e.g.
curve corresponding to T c o = 630 K, Fig. 13). Only
hot-spots and decreasing thermal profiles can be ob-
tained when Tco > T~ (see curve corresponding to
Tco = 655 K, Fig. 13).
Another important conclusion can be obtained
from Figs 10-13. As already discussed, limiting curves
given by eq. (15) represent the boundaries between
pseudoadiabatic and hot-spot operations. However,
other limitin 9 curves also satisfy expression (15). These
curves may be considered as the boundaries between
minimum-maximum and cold-spot zones (see
Fig. 10), or between hot-spot and maximum-min-
imum operations (see Figs 10 and 11), or between
decreasing and cold-spot zones (Fig. 12). Moreover, if
the additional constraint To = Tl is imposed, operat-
ing conditions satisfying eq. (15) lead to isothermal
profiles, which from this point of view can also be
considered as limiting curves. Therefore, the operating
conditions leading to an isothermal operation derived
by Degnan and Wei (1979) and the limiting conditions
for To = Tco reported by Soria L6pez et al. (1981),can
be seen as particular cases of the general analysis
performed in the present paper,
7. CONCLUSIONS
The cocurrent design has demonstrated to be very
powerful to influence the shape of the reactor temper-
ature profile, specially in the range where the condi-
4.0 -[ s~.9 t " T**--T,
~ - ~ 'I
a.5 - - - - - L ~
3.0 If
- -\ ~ - - ~
~ U overall heat transfer coefficient, kW/m 2 K
2.0 1 ' " ' " "':~''
l., ~ i f r
.a.o ......
0.5
0.0
500 600 760
T. (K)
Fig. 13. Influence of Tc0 on the operating zones
(Tc~ = 590 K; Tc~ = 610 K; Tc~ = 630 K; Tco*= 655 K,
Wc = 40 kg/s; Gg = 1.3011 kg/m 2 s).
D.O. BOR10et al.
tion To > Tco is satisfied. In fact, the cocurrent cool-
ant flow allows to achieve seven different regimes,
which can be very useful to track optimum thermal
profiles required to solve practical optimization prob-
Ictus.
A priori expressions have been derived to predict
the existence of all the feasible thermal regimes for the
general case of To and Tc0 independently fixed.
The PAo-To plane was used to illustrate how the
operating zones are influenced by changing the main
operating variables. This representation is also useful
to determine the operating conditions leading to the
sought thermal profile.
The present results were obtained assuming a plug-
flow pseudohomogeneous model and a first-order ki-
netics. These simple models were selected in order to
analyze and present the discovered phenomena at the
simplest possible level. The analysis here presented
can be considered as a starting point to further studies
involving more complex kinetics (other reaction or-
ders, reversible and/or multiple reactions) and more
detailed reactor models.
NOTATION
a [E/R]
A [pbPMpgo/Gg]
B [ p b ( - AH)pBo/Gocpg]
cp specific heat, kJ/kg K
C [4U/d~Ggcpg]
dt tube diameter, m
D [ n d t t , U / W c c~] o
E activation energy, kJ/kmol
G specific mass flowrate, kg/m 2 s
he~tshell-side heat transfer coefficient, kW/mZ K
hw internal wall heat transfer coefficient, kW/m 2 K
koc preexponential factor, kmol/s kgca, kPa 2
ker effective radial thermal conductivity, kW/m K
M molecular weight of gaseous mixture, kg/kmol
p partial pressure, kPa
P total pressure, kPa
R universal gas constant, kJ/kmol K
S (dT/dz), K / m
t, numberofreactortubes
T temperature inside reactor tubes, K
5°,`
~-,2" ~
Tc temperature of cooling fluid, K
T~ temperature inside reactor tubes at axial position
Wc cooling mass flowrate, kg/s
~ z axial coordinate, m
Greek letters
, . AH heat of reaction, kJ/kmol
~- r~c=r/
p density, kg/m 3
800 Subscripts
A o-xylene
b bed
B second component (oxygen)
9 gas
 Thermal regimes in cocurrently cooled fixed-bed reactors
l limiting
m relative extreme (maximum or minimum)
0 at axial position, z = 0
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