ELSEVIER

Chemical Engineering and Processing 35 (1996) 323-331

C h . m i ~
Ingin..nlll
and
Processing
An improved equation for the overall heat transfer coefficient in
packed beds
Anthony G. Dixon
Department of Chemical Engineering, Worcester Polytechnic Institute, 100 Institute Road, Worcester, MA 01609, USA
Received 8 December 1993: accepted 15 January 1996
Abstract
A one-point collocation analysis is performed on the two-dimensional pseudohomogeneous model of a fixed bed heat-
exchanger. The analysis is based on a single radial collocation point whose position depends on the wall Biot number. The
resulting improved equation for the overall heat transfer coefficient U is
1 I R, Bi +3
-=-+---
U It
w
3k
r
Bi +4
which gives an error less than 3.8% in the exact asymptotic value of U over the entire range of Bi. A formula is also given for
U', the overall heat transfer coefficient based on the difference between tube wall and bed center temperatures. The synthesis of
vinyl acetate in a fixed bed reactor was simulated. Use of the conventional one-dimensional model with the improved equation
for U, combined with the equation for U' to obtain bed center temperatures, gave predictions of acetylene conversion and bed
center temperature in good agreement with those of the two-dimensional model. A criterion for the neglect of radial temperature
gradients in a fixed bed reactor is derived which is more str ingent than criteria currently available in the literature.
Keywords: Packed beds; Heat transfer coefficient; Fixed bed reactors
1. Introduction
There must surely by now be almost as many fixed
bed reactor models in the vast literature of this subject
as there are fixed bed reactors actually in operation
around the world. Nevertheless, the continuing use of
this relatively simple, safe and easy to operate catalytic
reactory by industry has assured a parallel interest in
the development of mathematical models to predict the
reactor behavior. This interest has not abated in the last
40 years, and is perhaps fueled by the position of the
fixed bed as the prototype tubular catalytic reactor, and
point of departure for more exotic relatives, such as the
trickle bed reactor, the moving bed reactor and more
recently the fixed bed catalytic membrane reactor, to
name but a few.
The state of the art in fixed bed reactor modeling has
been periodically reviewed [I -4]. Recent trends, in the
light of higher computational capabilities, have been
towards more complex, two-dimensional, heteroge-
neous models with spatially-variable velocities and
0255-2701/95/$15.00 1996 - Elsevier Science SA All rights reserved
PII S0255-2701(96)04146-3
transport properties [5,6]. The goals of such simulations
have usually been to improve understanding of fixed
bed reactor behavior by detailed modeling of the funda-
mental phenomena occurring within the reactor. An
equally valid goal, however, is to represent a few
selected features of reactor behavior using a simple
model suitable for fast, repetitive calculations in studies
of design , control, parameter sensitivity, etc.
For these reasons, there is continued interest in the
one-dimensional pseudohomogeneous model, using an
overall tube-side heat transfer coefficient U to account
for radial heat transfer. The coefficient U depends on
many process variables, and the difficulty of finding
general empirical correlations for it has led to the
generally accepted approach of relating U to the
parameters of the two-dimensional model. The usual
relation has taken the form of a resistances-in-series
equation
(I)
324 A.G. Dixon / Chemical Engineering and Processing 35 (1996) 323-331
in which k, and h.; are independently correlated, or,
indeed, may be further related to even more fundamen-
tal parameters [3,7,8].
The factor p in Eq. (I) has been determined in
various ways. Beek and Singer [9] did not state Eq. (I)
explicitly, however a value of p= 4 is easily deduced
from their results. A rigorous derivation leading to
p= 4 was given by Froment [10], while Beek's review
[II] re-stated the earlier result more clearly, emphasiz-
ing its limitations. Crider and Foss [12] claimed that
errors of up to 27.7% in I/V were possible with p= 4,
in the limit of bed resistance control which occurs for
high values of the Biot number Bi (=hwRtlk
r
) . They
recommended P= 3.067, which gave a maximum error
in II V of 5.7%over the whole range of conditions, the
best possible with a constant value of p. Westerink et
al. [13] also preferred p = 3.06 for their predictions of
regions of parametric sensitivity of the homogeneous
one-dimensional model. In a recent experimental study,
however, Borkink and Westerterp [14] found that a
value of p= 3.7 gave the best empirical fit to their data,
for the range of Bi covered in their work.
Finlayson [15] applied one-point orthogonal colloca-
tion to the two-dimensional pseudohomogeneous model
at the root of i.e, at ,2 = 1/2, to obtain the
result p=4, and at the root of i.e. at ,2 = 1/3,
to obtain p = 3. Villadsen and Michelsen [16] pointed
out that this latter choice of collocation point was
optimal only in the limit Bi -400, which reduces the
wall boundary condition to a first kind, or Dirichlet,
condition, T = T
w
For a finite Bi, and a third kind, or
mixed, boundary condition, the optimal choice of collo-
cation point was the zero of which gave the
result p= 4. Villadsen and Michelsen [16] then devel-
oped a one-point collocation method where the posi-
tion of the collocation point depended on Bi, similar to
the earlier work of Stewart and Sorenson [17]; this will
be the point of departure for the new formula for V to
be developed below.
An alternative route to the overall heat transfer
coefficient V lies through the heterogeneous one-dimen-
sional model and its parameters V
r
and U, [18]. The
relations between U, and V
s
' and the more fundamental
and independently correlated parameters of the two-
dimensional heterogeneous model, have been provided
by the same group '[19]. Although in theory this ap-
proach is as equally valid as that of Eq. (I), it has not
found wide acceptance, probably because of the short-
age of correlations for U, and U, and the use of the
relatively unfamiliar one-dimensional heterogeneous
model with a continuous solid phase.
A slightly different approach has been adopted by
Wellauer et al. [20] and Cresswell [3], who used an
overall heat transfer coefficient V', defined with respect
to the bed center-line temperature. This coefficient was
also introduced by Froment [10]. Although the one-
dimensional model is strictly applicable only if there are
negligible radial gradients, in which case T; = T
av
and
V = V', in reality the model will undoubtedly be used
as a simplification or approximation in the presence of
radial temperature gradients, when only limited infor-
mation is of interest. Mears [21] has presented a crit-
erion for replacing a two-dimensional model by a
one-dimensional model based on making less than 5%
error in the calculated linearized average reaction rate
at the bed hot spot. It is thus anticipitated that in many
cases there will be significant differences between T;
and T
av
' and between V and V'. Wellauer et al.'s
motivation to consider V' sprang from their experimen-
tal set-up, in which the center-line' temperature was
measured by a thermocouple in a thin centered thermo-
well, a fairly common situation in pilot plant studies
[22]. It is also the center-line temperature that will give
the highest 'hot-spot' temperature in the bed, for reac-
tor safety studies. It seems more reasonable for reactor
simulations, however, to evaluate the reaction rate at
the radial average temperature T
av
, or at a suitable
average temperature to give the same radially-inte-
grated reaction rate.
In all the studies cited above, the relations for V have
been derived in the absence of chemical reaction
(Pereira Duarte et al. [19] did include a thermal source
term in their analysis, but it was assumed constant).
Several workers have argued that the one-dimensional
model cannot adequately reproduce the essential fea-
tures of the two-dimensional model unless V varies with
axial position. McGreavy and Turner [23] proposed a
semi-empirical relation for V which accounted for the
distortion in the temperature profile caused by the
chemical reaction. Sundaram and Froment [24] ana-
lyzed the empty tubular reactor, which was complicated
by the presence of a non-uniform radial velocity profile
(turbulent or laminar), and showed that the overall heat
transfer coefficient significantly depended on the reac-
tion parameters and the axial position. An even more
recent article by Westerink et al. [25] has examined the
length dependence of V. They concluded that the ap-
proach of V(z) to the asymptotic value of V depends
on the Peclet number and the Biot number, and an
empirical relation was presented for this dependence.
The empirical relation predicted the constant value of
V to within 2% for all Bi. The effect of using V(z) to
calculate axial temperature profiles was studied and
compared to calculations using constant V. It was
concluded that the axial variation of V could be
neglected for low to moderate values of Pe and Bi,
typical of either low dtld
p
cooled tubular reactors with
high flow rates or short, thick laboratory tubes at low
flow rates. There was a significant effect at high Bi and
Pe values typical of adiabatic bed reactors with high
Reynolds number. A criterion was presented for the
neglect of axial dependence.
A.G. Dixon / Chemical Engineering and Processing 35 (1996) 323-331
325
where
2. Classical development
Note that in general both overall coefficients must be
functions of x in order to match the radial energy flux
at every x. Numerical evaluation of the infinite series
gives Vex) and V'(x). At x = 0, it is easy to show that
(2)
(5)
(6)
(7)
(8)
(3)
(4)
(10)
(II)
(13)
(12)
The two-dimensional pseudohomogeneous model for
a fixed bed heat exchanger with cold incoming fluid at
x = 0, being heated from a constant temperature wall
(x> 0), is
1 0
20
1 (0
20
1(0) 00
PeAox
2
+ PeR oy2 +yoy = ox
with
o-+ 0 as x -+ - 00
e 1 as x -+ 00
oe = 0 aty = 0
oy
eo B'(
oy = 1 1 - e) at y = 1
where the axial conduction term and the axial
boundary conditions have been included for complete-
ness, and have no effect on the results developed here.
The analytical solution to Eqs. (2)-(6) has been given
by Gunn and Khalid [33] and for x> 0 it is
O(X' y) = 1 - f +
,= I 1 + A,) tlo(A,)
[

---...:1):..-xJ
x exp - 2
4
' 2
P, = 1+ A,
PeAPeR
and the eigenvalues A; satisfy the characteristic equation
BiJo(A;) = Atll(A,) (9)
V'(x)(O(x, 0) - I) = hw(O(x, 1) - I)
From this it is straight forward to evaluate eat y= 0 or
at y = I, or to obtain the radial average U.
Define overall heat transfer coefficients V (with re-
spect to bed average temperature) and V' (with respect
to bed center temperature) by
V(x)(U(x) -I) = hw(O(x, I)-I)
and
V(O) = V'(O) = h;
V(x) -+ V and V'(x) -+ V'
and as x -+ 00,
Ahmed and Fahien [26,27] demonstrated the
difficulty of accurately simulating the behavior of an
S02 oxidation reactor using the conventional one-
dimensional model with a constant overall heat transfer
coefficient, and evaluating the reaction rate at the
radial-average temperature. They developed a new
modified one-dimensional model by using a problem
specific collocation method to write the radial profiles
of conversion and temperature in terms of center-line,
wall and bed average values. A cross-sectional average
reaction rate was used. This model required five ODEs
to be integrated instead of the usual two, but gave
much improved agreement with both experimental data
and the predictions of a two-dimensional model.
Extending the earlier work of Pereira Duarte et al.
[18,19], Mascazzini and Barreto [28] provided formulas
for the fluid and solid phase overall heat transfer
coefficients of the one-dimensional heterogeneous
model, in which the thermal source term varied axially
as a function of solid temperature. They also claimed
' improved agreement with two-dimensional model cal-
culations, away from conditions of parametric sensitiv-
ity.
In a recent series of publications, Hagan and co-
workers [22,29-32] have presented a new one-dimen-
sional fixed bed reactor model, termed the a-model.
The conventional radial average temperature is re-
placed by a ' reaction-averaged' temperature T
r
, and the
overall heat transfer coefficient V is a decreasing func-
tion of the temperature rise The authors presented
impressive agreement between their one-dimensional
model and the full two-dimensional model, while the
conventional one-dimensional model did not do so well
[31]. The conventional model, however, used V from
Eq. (1) with P= 4, which may not have been the best
choice for the cases studied since Bi was in the range
7-10. Also, it may be noted that the new a-model was
somewhat more computationally expensive than the
conventional one-dimensional model, since an algebraic
equation had to be solved iteratively for a at each axial
point z.
In the present work, it will be shown that an im-
proved formula for V in terms of k, and h.; is available,
if the constant Pin Eq. (1) is allowed to vary with Bi.
This results in accurate prediction of V for the whole
range of Bi, in contrast to equations of the form of Eq.
(1), which are accurate only for a limited range of Bi. It
is then interesting to compare the predictions of the
conventional one-dimensional model with the improved
formula for V, to those of the more detailed two-
dimensional model. This comparison allows the reac-
tion engineer to judge whether improved predictive
capabilities of more complicated models are worth the
extra computational effort.
326 A.G. Dixon I Chemical Engineering and Processing 35 (/996) 323-331
The variation of V(x) and V'(x) and their approach to
asymptotic values is shown for a typical case in Fig. I.
Ulh.; is within 1% of its asymptotic value at x = 9, i.e.
after 4.5 tube diameters; U'lh.; appears to take a little
longer to reach its limiting value. The approach to the
asymptotic values will depend on the other model
parameters, however the general trend is similar.
The approach of V(x), V'(x) to constant asymptotes
coincides with large enough values of x that only the
first term of the infinite series is needed:
Note that with only one term the exponentials cancel,
removing the dependence on x; also the terms in Pi
cancel, removing the remaining dependence on PeA-
The smallest eigenvalue Al depends only on Bi, never-
theless it is inconvenient to have to solve Eq. (9) for
each Bi. The evaluation of V' also requires the calcula-
tion of Jo(A
1
) , a relation given previously [3,20]. We
seek simpler expressions that do not involve Bessel
functions.
Following Crider and Foss [12] we note that for
small values of Bi, Al is also small and we may use the
small argument approximations
, I ' iii' i I I I I
8 12 16 20
X = (zlR)
(17)
Ai At
Jo(AI ) 1-"4+64
and
AI Ai
JI(A\) (18)
Substituting these into Eq. (9) gives
(19)
1 - Bi +4
and then using Eq. (15)
V 4 1 1 s;
h
w
= Bi +4 or V = h
w
+4k
r
(20)
as obtained earlier [9,10]. Along similar lines,
V' ( 4)2 1 1 Bi +8 s,
h
w
= Bi+4 or V,= h
w
+-8-2k
r
(21)
for small Bi.
Note that if we use only two terms in Eq. (17) and
one term in Eq. (18), then Ai = 4Bi/(2 + Bi) and we
obtain
I I 1 s;
V = V' =h +2k (22)
w r
which is inaccurate even for fairly small Bi, as has been
remarked by Froment [34]. Hence V = V' only in a
(fairly poor) first approximation.
As Bi increases, Al approaches 2.4048 which is not
large enough to allow a large argument expansion of
Jo(A\). We may proceed formally by allowing h
w
00 so
that 11h
w
0 and write
1 1 s;
---+ (23)
V- h.; (Ai",,/2)k
r
where Ai"" 5.783186, to obtain a formula similar
to Eq. (20), that can be used as an approximation
for large Bi-c co. For V', write V'=hwlo(A
I
) = (krl
Rt)BiJo(A
1
) = (krIR
t)
x AIJI(A
I)
and evaluating AIJ\(A\)
yields
1 1 s;
---+
V' - h; 1.2483k
r
and comparison of Eqs. (23) and (24) again emphasizes
the difference between V and V', especially as Bi
increases.
The classical development above can yield only
expressions in the form of Eq. (1), for the limits of
Bi and Bi 00. A more flexible approach is needed
that can give an equation for the entire range of Bi.
(15)
(14)
(16)
I
4 o
1.0
0.8

.c
0.6
Ulh
w
:--
::>
.J
0.4 U'/h
-
w
::>
-----------
0.2
1-0(x,y)
_ Bi (I +PI) JO().'lY) [- PeA(PI - I)X]
- BF +Ai PI Jo(A
I)
exp 2
and then
V 1- O(x, 1) Ai
n; 1 - (J(x) = 2Bi
V' = 1 - O(x, 1) = Jo(A
1
)
s; 1- O(x, 0)
Fig. 1. Comparison of the approach to the asymptotic values of the
overall heat transfer coefficients defined with respect to bed average
temperature (V) and bed center temperature (V'). Parameter values
are PeR = 40 and Hi = 3.
3. One-point collocation development
The symmetry of the problem is reflected by the
change of variable u = y
2
giving
A.G. Dixon / Chemical Engineering and Processing 35 (1996) 323-331 327
thus
(
(I - U)(Bi/2) + 1) (H') (34)
O(x, u) = 1 - (I _ u.)(Bi/2) + 1 exp x
From this, the terms required in the definitions of V
and V' follow easily. For V' we can immediately show
o() = Bi (I _ () at u = 1 (29)
au 2
Applying one-point collocation at u = U. ' we set
1- u U - U
I
O(U)=--()I +--0
2
(30)
1- U. 1 - UJ
and substitute into Eq. (29) and solve for ()2 in terms of
0. We then collocate the differential Eq. (25) to obtain
d
2
() . d()1 () 1) 0 (31)
dx2 - PeA dx - H( ) - =
' where
H = 4PeA Bi/2 (32)
PeR(I - u,) Bi/2 + 1/(1 - U.)
Without loss of generality, we neglect axial conduction
(PeA-. 00) and solve the resulting first order ODE to
get, setting H' = H/peA
which is expected to be accurate in the limit of small Bi.
(39)
(38)
Exact
o BBiI(Bi+4)
tI 6BiI(Bi+3)
Thiswork
2 3 5 10 2 3 5 100
Bi
10
5
2
A1
2
5
3
2
0
0
2 3 5
which has the limit Ai -.6 as Bi -. 00. An approximate
formula for V' may also be found by returning to Eqs.
(16) and (17) and substituting Eq. (38), giving
V' Bi
4
+24BP +240Bi
2
+ 1152Bi +2304
h
w
= 16(BF +6Bi + 12)2
Fig. 2. Comparison of approximations for the leading eigenvalue .n
1 1 R
t
Bi +3
V =h
w
+3k
r
Bi +4 (37)
This formula reduces to Eq. (I) with P= 4 in the limit
Bi -.0, and to Eq. (1) with P= 3 in the limit Bi -. 00.
As a corollary to this result, a new approximation to
Ai is obtained
2 Bi +4
Al = 6BI BF +6Bi + 12
(33)
(25)
(26)
(27)
(28)
O. = 1- exp(H'x)
0-.0 asx-. - 00
o-. 1 as x -. 00
1 02() 4 (02() O()) eo
PeAox
2
+ PeR u au
2
+ au = ox
with
() finite at u = 0
(35)
(36)
V' O(x, I) - 1 2
h
w
= O(x, 0) - 1= Bi +2
independent of choice of collocation point, so that the
collocation method allows us to recover only the poor
first-order approximation of Eq. (22) for V'.
To obtain lJ(x), we choose Gauss-Jacobi quadrature
rather than Radau quadrature, as the boundary value
O
2
was not given directly but was approximated by
discretizing the boundary derivative; thus it is not
known to any special degree of accuracy. We obtain the
simple result lJ=
1
, and hence
V O(x, I) - 1 I
h
w
= lJ(x) - 1 = 1 +(I - u.)(Bi/2)
Choosing U. to be 1/2 or 1/3 gives Eq. (I) with p= 4
and P= 3, respectively [15J. We prefer to follow Stew-
art and Serensen [17] and Villadsen and Michelsen [16]
and choose U. = (Bi +6)/(3Bi + 12); substitution into
Eq. (36) gives our main result
4. Comparison of prediction formulas
The first test of the new formulas presented here will
be the calculation of Ai as a function of Bi. Fig. 2
shows the results from the corollary to Eq. (I) and Eq.
(15), Ai = 2PBi/(Bi +P), for the two limiting colloca-
tion cases p= 4 and p= 3, and the result of the present
work, Eq. (38). The comparison in Fig. 2 indicates that
all methods are quite accurate for low Bi, in the region
Bi < 1. For Bi > 2 the choice of the p= 4 approxima-
tion becomes less satisfactory, as noted before [12,16],
and the formula is highly inaccurate for Bi > 4-6. Both
the formula p= 3 and the present formula give good
approximations over the entire Bi range. The p= 3
formula makes errors of up to 6.3% for low and
intermediate Hi, and is very accurate for high Bi. As
expected, these results are comparable to those of
Crider and Foss [12], who obtained a maximum error
of 5.7% with P= 3.067 rather than p= 3. Our new
328 A.G. Dixon / Chemical Engineering and Processing 35 (1996) 323-331
Table I
given by Eq. (39) indicates that it is caused somewhat
Comparison of prediction formulas for U/h
w
more by the low-argument expansion of JO(A), Eq. (17),
Bi Exact This work Low Bi limit High Bi limit
than by the approximation of AI' Eq. (38). Attempts to
O?!2Bi) [Eq. (37)] 4/(Bi+4) 3/(Bi+3)
include more terms in the expansion of JO(A), however,
gave results that became limited by the AI approxima-
0.2 0.9516 0.9517 0.9524 0.9375
tion, and only a marginal improvement was obtained.
1.0 0.7885 0.7895 0.8000 0.7500
The bed-center temperature may be obtained' from
3.0 0.5332 0.5385 0.5714 0.5000
6.0 0.3499 0.3571 0.4000 0.3333
the bed-average temperature by the relation
10.0 0.2375 0.2442 0.2857 0.2307
V
20.0 0.1309 0.1353 0.1667 0.1304
(T
c
- T
w
) = V' (T
av
- Tw )
(40)
formula, Eq. (38), has an overall error less than 3.8%,
and is especially good for low and intermediate Bi < 10,
where the maximum error is less than 2.8%. The new
formula makes its worst errors at high Bi, where the
one-dimensional model is a poorer representation of the
temperatures in the bed. Eq. (38) is to be preferred for
the prediction of Af since it is very accurate in the low
to intermediate Bi region which is where most fixed bed
processes with strong heat effects will operate, i.e. at
relatively high Re.
Table I presents a comparison of the three formulas
for V/h
w
, corresponding to the three choices of colloca-
tion point in the previous section. Results are presented
for a selected set of Bi values, and the conclusions from
these results echo those from Fig. 2. Eq. (1) with P= 4
predicts Vjh
w
accurately for low Bi but is poor for
Bi > 2. Eq. (1) with P= 3 predicts Ulk; accurately for
Bi > 10 but is less good below that value. Our new
result, Eq. (37), provides a simple approximation that is
accurate to within 3.8% over the entire range of Bi.
The collocation method did not yield a good approx-
imation of U'lh.; and therefore Eq. (39) was based on
a return to the small argument expansion of Eq. (17). It
is no surprise, therefore, that the prediction results for
U'lb; that appear in Table 2 show accurate values for
low Bi and poorer performance as Bi increases. Eq. (22)
is included to confirm that it gives inaccurate values
over the entire range of BL Eq. (39) of the present work
gives the best agreement with the exact values, which
becomes progressively worse as Bi increases. The inter-
mediate Eq. (21) performs reasonably, but is still not as
good as Eq. (39). An analysis of the error in the values
Table 2
Comparison of prediction formulas for U'/h
w
Bi Exact This work Eq. (21) Eq. (22)
[loO,)] [Eq. (39)] [4/(Bi +4)]2 2/(Bi+2)
0.2 0.9071 0.9071 0.9071 0.9091
1.0 0.6429 0.6442 0.6217 0.6667
3.0 0.3466 0.3554 0.3265 0.4000
6.0 0.1957 0.2156 0.1600 0.2500
10.0 0.1218 0.1517 0.0816 0.1667
20.0 0.0620 0.1045 0.0278 0.0909
with V and V' given preferably by Eqs. (37) and (39).
The one-point collocation method does give a parabolic
radial profile, however direct use of this is equivalent to
using the inaccurate Eq. (35) for V' and is not recom-
mended. It may be noted from Tables I and 2 that
there is a definite difference in the values of Ulb; and
U'lii; at the same Bi, thus the distinction between these
two coefficients is one worth making, even for fairly
low values of Bi.
A considerable amount of earlier work has been
based on the use of u. = 1/2 as the collocation point,
including model matching studies [7,8,35]. The success
of this work, despite the inadequacies of Eq. (20) and
the use of the root of P\o.O)(u) as the collocation point,
lies in the fact that the model matching formulas for k,
and h
w
were derived for the limiting case of high Re [7]
and the predictions of k, and h
w
have generally been
combined to obtain V for processes with reasonably
high Re. Since this corresponds to low values of Bi, the
earlier work gave quite acceptable results and the use of
U
I
= (Bi +6)J(3Bi + 12) as the collocation point gave
only marginal improvement, as noted by Dixon [36].
5. Reactor simulation using improved formulas
A rigorous analysis of the one- and two-dimensional
pseudohomogeneous models with a reaction term
included will show that the lumped parameter V should
depend on the kinetics and heat of reaction. To investi-
gate this, the collocation analysis was repeated with a
reaction term present in the energy balance equation.
As is frequently done (see Mears' article [21] for exam-
ple) the reaction rate expression was linearized, which
led to the result that the reaction kinetics constants
cancelled out in the final expression for Ulh.; So to a
first approximation the same formula holds for V in
both the reacting and non-reacting cases. The approxi-
mation involved in linearizing the reaction rate expres-
sion may be questioned, but it is likely to be
appropriate given that the radial profile is represented
by a one-point collocation approximation (i.e. a
quadratic in the radial coordinate).
Herskowitz and Hagan [31] presented the results of
simulations of vinyl acetate synthesis in a tubular fixed
A.G. Dixon / Chemical Engineering and Processing 35 (1996) 323-331 329
(41)
(42)
1.0 0.8
T
w=To=455
.1K
0.4 0.6
X (=zIL)
0.2
... ----
-- 2-D
- - - 1-0 (OLD U)
1-0 (NEWU)
,
,
,
, - - --
, ".
, ",
, v
r
,
,
0-f-r-T'""T""T-r-r-T'"T"T-r-r-rT"T-r-T""'T'T"T-+
0.0
40
20
30
10
6. Criteria for the neglect of radial temperature
gradients
As mentioned above in the Introduction. Mears [21]
developed a criterion for the neglect of the radial
temperature gradients. A one-dimensional energy bal-
ance was written at the hot-spot, which allowed an
analytical solution for the temperature profile when the
reaction rate was linearized around the wall tempera-
ture. Under some reasonable assumptions. the tempera-
ture profile became parabolic. and expressions were
developed for the ratio of the cross-sectional bed-aver-
age reaction rate to the reaction rate at the wall temper-
ature. By requiring these two to be within 5% of one
another, Mears obtained criteria for the neglect of the
radial gradients, for the two cases of negligible and
significant heat transfer resistance at the wall.
The one-point collocation method was applied to the
simplified model considered by Mears and a similar
development to that explained above was carried out to
derive a general criterion in terms of the location of the
collocation point. In terms of the notation already used
in this article, the criterion is
E 1- L\HI R ~ R ; [ 4 ]
R T ~ 8k
r
1+Bi < 0.05
For the collocation point at u. = 1/2 which corresponds
to the parabolic radial profile found by Mears' approx-
imate method, Mears' result is recovered exactly.
Again, in the present notation the result is
with R; being the reaction rate at the collocation point.
which is identified with the radial-average reaction rate
R' used in Ref. [21].
Fig. 4. Model predictions of axial profiles of temperature rise at bed
center, for the vinyl acetate synthesis example, for two different
inlet/wall temperatures.
1.0 0.8 0.4 0.6
X (=zIL)
2-D
1-0 (OLD U)
1-0 (NEWU)
0.2
0.20
Z
0.18
0
0.16
Cii
c::
0.14
~ 0.12
0
U 0.10
W
Z 0.08
W
-I
0.06
~
0.04
~
0.02
0.00
0.0
Fig. 3. Model predictions of axial acetylene conversion profiles for
the vinyl acetate synthesis example, for two different inlet/wall tem-
peratures.
bed reactor. They used the conditions reported by
Valstar et al. [37], and compared a two-dimensional
model, the conventional one-dimensional model and
their new a-model. The new one-dimensional a-model
was found to agree very well with the acetylene con-
version and temperature rise given by the two-
dimensional model, but the conventional one-dimen-
sional model under-predicted both. The overall heat
transfer coefficient used in the conventional model
was given by Eq. (20), although the Biot number was
quite high, 7.22. It is interesting to investigate how
the conventional model would perform with a differ-
ent estimate of U.
The calculations of Herskowitz and Hagan [31]
have been repeated using the conventional model, for
the kinetics of Valstar et al. [37]. The kinetic expres-
sions and values of the other parameters are given in
Table I of Herskowitz and Hagan [31]. The results of
the present calculations are compared to the two-di-
mensional model in Fig. 3 for acetylene conversion.
and in Fig. 4 for the predicted centerline temperature
rise. There is good improvement in the predicted
acetylene conversion using the U value from Eq. (37),
so that the conventional one-dimensional model is
close to the two-dimensional results. The predicted
center-line temperature rise using Eqs. (39) and (40)
also improves significantly. underpredicting the hot
spot temperature by approximately four degrees. The
a-model overpredicted the temperature rise by about
two degrees [31], so that for this case in terms of
accuracy there is not a lot to choose between the
models . The overprediction of the a-model makes it
the more conservative for design purposes, and the
determination of runaway conditions. at the cost of a
little extra computation.
330 A.G. Dixon / Chemical Engineering and Processing 35 (1996) 323-331
Greek letters
P parameter, Eq. (1)
Pi parameter, Eq. (8)
AH heat of reaction, kJ mol- 1
A, ith eigenvalue, defined by Eq. (9)
A,oo value of first eigenvalue, as Bi -+ 00
o dimensionless temperature,
(T- To)/(T
w
- To)
0
1
value of 0 at collocation point UI
O
2
value of 0 at U = I
{f radially-averaged dimensionless
temperature
For the general Bi-dependent collocation point
location used in this paper, U
I
= (Bi +6)/(3Bi + 12) and
the result is
E 1- AHI [4Bi + 12 4 ]
8k
r
3Bi + 12+Bi < 0.05 (43)
As Bi becomes small, Eq. (43) reduces to Eq. (42) since
(4Bi + 12)/(3Bi + 12) -+ I. As Bi becomes larger, this
fraction tends to 4/3. The criterion of Eq. (43) is more
stringent than Mears' criterion for large values of Bi, i.e,
when the resistance to heat transfer is within the bed
rather than at the wall, and a large temperature gradient
through the catalyst bed is to be expected. It is of interest
that the vinyl acetate synthesis example of the previous
section fails by both the old and new criteria, confirming
that the discrepancies seen in Figs. 3 and 4 are reason-
able.
7. Conclusions
The new formula
I I n; Bi +3
-=-+---
V h
w
3k
rBi
+4
should be used to combine estimates of k, and b; into
an overall heat transfer coefficient V, in preference to the
previous lumped form given by Eq. (1). The new formula
is accurate for all values of Bi, and involves little or no
extra computation.
Accurate formulas were harder to obtain for
the overall heat transfer coefficient defined with
respect to bed center temperature, V'. It is recommended
that V should be used in the 10 model, calculated from
the formula directly above, and that Eqs. (39) and (40)
should be used to obtain T; for comparison with exper-
imental thermowell temperature data, from the values of
T
av
given by the one-dimensional model.
A conventional one-dimensional model with an
accurate prediction of V was used to simulate a fixed bed
reactor with moderate radial temperature gradients.
With V well-predicted, the model was nearly as accurate
compared with a two-dimensional model as the
of Herskowitz and Hagan [31], and was a little easier to
use.
An extended version of Mears' criterion for the
neglect of radial temperature gradients in a fixed bed
reactor was derived. The extended criterion reduces to
the earlier result for small values of Bi, and is more
stringent for the large values of Bi that usually give rise
to stronger radial temperature gradients.
8. Notation
Bi tube Biot number, hwRt/k
r
c
p
fluid specific heat, kJ kg K- I
P\O,O)
P\I,O)
r
R
R
t
R
'
U
V'
o,
o.
x
y
z
activation energy, kJ mol- 1
superficial mass flow rate, kg m - 2 S-I
wall heat transfer coefficient, kJ m-2 s
K-
'
dimensionless parameter, Eq. (32)
effective axial thermal conductivity, kJ
m " ' S-I K-
'
effective radial thermal conductivity, kJ
m " ' S-I K-
'
tube length, m
axial Peelet number for heat transfer,
GCpRtk
a
-I
radial Peelet number for heat transfer,
GCpRtk
r
-
1
Legendre polynomial of first order
Jacobi polynomial of first order
radial coordinate, m
gas constant, kJ mol - I K - I
tube radius, m
reaction rate per unit bed volume, mol
m-3 S-I
radial-average temperature, K
inlet temperature, K
center-line temperature, K
wall temperature, K
reaction-averaged temperature of Hagan et
al. [29], K
transformed dimensionless radial
coordinate (y2)
first radial collocation point
overall heat transfer coefficient [Eq. (10)],
kJ m-
2
S-I K-
'
overall heat transfer coefficient [Eq. (11)],
kJ m-
2
S-I K-
'
fluid-phase overall heat transfer coefficient,
kJ m-
2
S-I K-
1
solid-phase overall. heat transfer coefficient,
kJ m-
2
S-I K-
1
dimensionless axial coordinate, zlL
dimensionless axial coordinate, r/R
axial coordinate, m
A.G. Dixon / Chemical Engineering and Processing 35 (/996) 323-331 331
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