ChemicdEngineering Science. 1972, Vol. 27, pp. 497-509. Pergamon Press.

Printed in Great Britain

Distribution of residence times and contact times in packed bed

reactors: influence of the chemical reaction
P. ORTH* and K. SCHUGERL
Institut fur Technische Chemie der Technischen Universitlt Hannover, Hannover, Germany

(Firsf received 23 Mnrch 197 1; in revisedform 18 June 197 1)

Abstract-The distributions of residence times, DRTs, and contact times, DCTs, were measured for
ethene reacting with hydrogen, and the ethane thus formed on a palladium catalyst supported on
aluminium silicate in an isothermal packed bed reactor at temperatures between 60 and 200°C.
The reaction strongly influences the DRTs and DCTs of the reactant and product molecules. The
temperature dependence of the DRTs and DCTs of ethane and ethene were investigated with and
without chemical reaction at nearlv constant conversion. The results are explained quantitatively by
means of a generahsed time delay model.

INTRODUCTION APPARATUS AND EXPERIMENTAL

DURING passage through a packed bed
ITS
reactor, a molecule spends its time alternately
in the gas phase and on the surface of the catalyst.
The length of time which the molecules spend in
the gas phase and on the surface can be estimated
experimentally using tracer techniques.
The commonly used distribution of residence
times (DRT) covers the time spent on the surface
as well as in the gas phase, whereas with a non
adsorbing tracer the DRT includes only the gas
phase[l].
The difference of the residence times of ad-
sorbing and non-adsorbing tracers gives the
residence time of the molecules on the catalyst
surface, the so called contact time.
Nauman et a/.[ I] used this principle to develop
a method for the estimation of the distribution of
contact times (DCT) of adsorbing tracers. They
measured the DRTs of one strongly adsorbing
and a weakly adsorbing component in a fluidised
bed. In the present work the DRTs of three
components (two strongly adsorbing and one
non-adsorbing) were measured simultaneously
by a fast response detector (mass spectrometer)
and the DCTs were evaluated by the method of
Nauman et al. for both of the adsorbing com-
ponents, i.e. the reactant and the product mole-
cules of the same reaction in a packed bed
reactor.
PROCEDURE
The apparatus is shown schematically in Fig. 1.
The reactor was built with an annular catalyst
bed O-6 cm wide, 5 cm dia. and 270 cm long which
enabled the reactor bed temperature to be held
constant to within +O-5°C. The catalyst consisted
of 130 g of aluminium silicate (8.82% A&O, and
78.1% SiO,) and had the following physical
properties: surface area 365 m”/g, pore volume
O-356 ml/g, mean pore radius 39 A, particle dia.
200-250 pm, true solid density 2.2 1 g/cm”, bulk
density 0.685 gJcm3.
The magnetic valve (3) was used for the step-
function-input of the tracer mixture and the
magnetic valve (5) for the pulse input with a
pulse length of O-1 sec.
The sample was extracted downstream of the
cooler (8) by a four channel mass spectrometer
(Varian MAT, Bremen, Type GD 150/4).
The intensities of the masses 4 (helium), 28
(ethene) and 30 (ethane) were measured simul-
taneously as a function of time. Although the
electron accelerator voltage of the ion source was
only 30 eV mass 28 was still obscured by the
fragmentation of ethane. A compensator was
built which eliminated the fraction of the 28-
peak which originated from the ethane content
[2]. Three output channels of the mass spectro-
meter were loaded directly into a data processing

*P. Orth is now with the VEBA-Chemie AG, 466 Gelsenkirchen-Buer.

497
 P. ORTH and K. SCHUGERL

MS

Fig. 1. Experimental setup. l-lb, needle valves; 2-2b, capillary flowmeters; 3, magnetic valve; 4, precision
pressure controller; 5, magnetic valve; 6, preheater; 7, reactor; 8, cooler; 9, thermostat; 10, flow meter; 11,
thermocouple; MS, mass spectrometer sampling.

unit (Fig. 2). Up to 500 digital values were used
from each channel for computing one DRT. The
fourth channel was used as code channel.
The measurements without chemical reaction
were carried out with aluminium silicate support
material alone, and the investigations of the
influence of the chemical reaction with palladium
on aluminium silicate.
The latter measurements were all carried out
with the same amount of palladium catalyst but
in one series (case A) the Pd catalyst was limited
to a differential volume (a disc shape bed with
small volume) at the entrance of the bed, and in
the second series (case B) the Pd catalyst was
distributed uniformly in the whole bed.
In case A no reaction takes place during the
flow of molecules through the reactor except of
the first differential volume.
For case B the reaction occurs during the
passage of the molecules along the bed (Fig. 3).
Therefore comparison of the DCTs measured in
series A (without reaction in the bed) and series
B (with reaction in the bed) makes it possible to
evaluate the influence of the chemical reaction
on the DCTs. During the measurements with
reaction the conversion could be kept almost
constant, since the temperature dependences of
rate constant and mean contact time are nearly
equal and therefore the conversion is tempera-
ture independent (see below).
The DCTs of ethene and the overall DCTs of
ethane were calculated by means of the measured
DRTs of ethene, ethane and helium with and
without reaction.

RESIDENCE TIME DISTRIBUTION MODELS

Fig. 2. Data processing unit. 1, mass spectrometer; 2,
channel selection unit; 3, time control unit; 4, trigger unit for
the magnetic valves; 5, constant voltage source to channel
coding unit; 6, DC amplifier; 7, digital voltmeter; 8, interface
to tape perforator; 9, tape perforator: IO, addressing unit.
498
Three models were used to evaluate model
parameters: a one dimensional (l-D-) diffusion
model (without and with adsorption process), a
simple cell model and a time delay model.
 Packed bed reactors

In case A In case B
(no reaction in the bed) (reaction in the bed)
co CO

lzl
x-0

X= 0
X=L
Length coordinate

Concentration
Reactor
of
entrance
Reactor exit
x x=L
CL

ethene
C

L
x-0
c(x)

Length coordinate x
x-L
CL

c0 Concentration of ethene in feed

Fig. 3. Course of the reaction.

1 -D-difusion model same moments, if Bo 9 1:

The common diffusion model with cylindrical
symmetry explains the broadening of the DRT b!iLI 1. /!I&2 and be_ l2
by an axial mixing process which can be de- 7 ’ 72 Bo
scribed by the mass balance:
Simple cell model
One can describe the overall transient
(1) behaviour of an isothermal reactor by its weight
function g(t) which is defined as:
The model parameters are the flow rate u and
the coefficient of axial mixing M, which are Y(t) = s(r) * x(t) (3)
constant throughout the bed.
Since in a packed bed the first term on the i.e. the output signal y(t) is a convolution of the
right side of Eq. (1) is much smaller than the input signal x(t) with the weight function.
second term, the boundary conditions at the The weight function can be represented by a
entrance and at the exit of the reactor do not series of discrete stages each of them with the
influence the DRT significantly and one can use same weight function g, (t) :
the conditions for an open system. The solution
of Eq. (1) is given by
g,(f) =$aexp C-e,) (4)

1 (2)
c(e)
-= 1 Bo(1 -e)’
exp -
CO 2heIBo [ 48 where 8r = ?/T~. For II equal stages the DRT of
the system can be described by:
with the independent variable 8 = t/r and the
parameters c(t)
-= nn. P-l exp (-t2e)
P(n-- l)! (5)
co
Bo = uLIM and r = Llu[3].
since the DRT and the weight function are equal
Equation (2) and all the other solutions have the (i.e. the input function is a delta function).
499
 P. ORTH andI K. SCHijGERL

The first and second moments are: whereg,(t) = s(t-to) = s(f+) (9)
t+ = t-to
!%=i and b&L (W
i- r2 n r3 n2 ’ to is the minimum residence time.

Time delay model Hence

Buffham et a/.[41 have developed a time delay
model which is actually a generalised cell model
g(t+) =

t+
ew C-((.~~+f+b)l
li (OLYf+‘tD)
(10)
R=l n!(n-l)!
with a parallel series of equal stages (Fig. 4).
Each of the stages has the same weight function if the probability p. is neglected.
and each of the series of stages is characterised The moments of Eq. (10) are [4], [2] :
by the probability p,, (n = 0, 1,2,. . .) that a flow
element passes it. If one assumes that each of the /.L; = t,+cYx. to
adsorption steps on the surface delays the tracer (104
molecules by the weight function, I*2 = 2cY.x. g.

CONTACT TIME DISTRIBUTION-

gD(t) = d * exp (-f),), with 0, = t/r, (6) APPLICATION TO REACTING GASES

The reduced contact time 0, was calculated

and that the probability that the molecules suffer using the correlation for the response curves of
n adsorption steps p,, follows a Poisson distribu- a step input.
tion,
8, = fads - fined .
(11)
pn = q - exp (-CLX) (7) Tads - Tinert
n.
The residence times of the adsorbing and non-
then the following total weight function results:
adsorbing components are tads and tinert respec-
tively, and rads and Tinertare the mean values of
g(t) =&L(l) * i Pn . sD(t>*” (8) tadsand tinert, defined as:
n=o
7=- 1 m c(t) dt. (12)
co I 0
PC
The reduced mean contact time is defined:
PI 9,(t)

7ads - Tinert _-
_ 712
pz i?= (13)
Tinert Tinert
Output
x(t) p3 ^ y(t)
For pulse input the DCT was characterised by
9,(t) p4 its moments:

(14)
-_o-_o- - -_o--o_

1
For a first order reaction with the rate constant
Fig. 4. Time delay model. k the fraction of reactant remaining in the output

500
 Packed bed reactors

of the reactor can be calculated using Eq. (15): and with chemical reaction from Eq. (17a)

c
-= mexp
CO J 0
(-kt)f(t) dr (15)
and
where t is the residence time andf(t) is the DRT
of the reactant molecules in the reactor. The
DRT should be described by the time dealy
model: for03 % kt,+ 1.

exp (-(WC+ r+/t,) m (a_~r+/t~)~ RESULTS

f(t+)= t+ 2 n!(n-l)! (16) Without reaction
Since the input functions were to a good
with the moments: approximation delta functions, the first and
second moments and the model parameters were
CL;= to+axtD (164 calculated directly from the experimental curves.
p; = 2t~%x. (16b) The DRTs were then recalculated using Eq. (2)
for the diffusion model and compared with the
The DRT will be modified by the reaction accord- measured ones (Fig. 5).
ing to Eq. (17): The agreement between the recalculated and
measured curves is fairly good for high tempera-
fR(t+) = exp [-k(t++t,)]f(t+). (17)

The moments of Eq. (17) are [2]: 2.0

Temp. 200 *C
I-5
c 0 H* Bo- 50.8
I-0
(174

2t,ffx
for cwcs &,+I. (17b) 2.5
P2R = (kt,+ 1)”

The delay time model can also be used to the

description of the DCT, if one considers the
time t+ = t - to in a more general way (i.e. [5])

2.0 Temp. 120.C

&= tads - fin&*
I5
C,“, 80-99.7
= I.0
By that the first moment (16a) of the DCT can
0.5
be converted into Eq. (18a)
2.5

k ads = h in& + WtD 2.0

or (18a) I3
c
Plc = A ads- Pl inert = WtD I.0

0.5

and the second moment ( 16b) into Eq. (18b): 0 20 40 120 140

kc = 1-12
ads- P2 inert= 2tD*a (18b) Fig. 5. Fitting of the DRTs to the 1D-diffusion model.

501
 P. ORTH and K. SCHUGERL

tures, but very poor for ethene and ethane at low recalculated and compared with the measured
temperatures. ones (Fig. 7). For all of the temperatures and
The extension of the l-D-diffusion model by components an excellent agreement between the
an adsorption-term according to Chao et a1.[63 measured and recalculated curves was found.
did not improve the quality of fitting. The ratio (a) of the lateral. flow along the bed
The model parameter n of the cell model was with length of x to the throughput flow rate
calculated from Eq. (5a) and the DRT was depends only slightly on the temperature and the
recalculated using Eq. (5). Figure 6 shows a properties of the tracer. It has an average value
comparison of the measured and recalculated of 12.4.
curves. Again the agreement is only satisfactory Figure 8 shows the reduced mean contact time
for high temperatures. At low temperatures the & as function of the temperature of the bed for
model can not be used. ethane and ethene. I?~depends exponentially on
the temperature. At low temperatures the ratio
0.10 of mean contact time 7c to the mean residence
008 time of non-adsorbing component Tinertis as high
0.06 as 3. The mean contact time 7c does not depend
c :n-24 r -21,7s
0.04 6 n-49 r .29,81 on the flow rate and the mean residence time Tinert
GIG? . :n-44 T-30,6*
of the non-adsorbing component does not depend
0 on the temperature.
0.10
OOB Figure 9 shows the second moment b,, of the
0.06 Temp.
160-c DCT as function of the inverse temperature.
c :n-24 r-23.6*
The width of the DCT increases exponentially
OQ4 ‘“-50 T-36.6s
0.02
:n- 40 T -39,3r with decreasing temperature. At low tempera-
0 tures the mean contact time is large and the DCT

006 n-25 r-25,9%

c n- 42 r-49,5s
0.04 :“- 37 r-56,% c

002

Fig. 6. Fittingof the DRTs to the simplecell model.

c
Similar results for the diffusion and cell models
are to be expected because for large 12(or Bo)
there is a definite connection between the model
parameters: n = Bol2.
The model parameters (cyx) and to of the time c
delay model were calculated from the first and
second moments of the measured curves and the
time to was evaluated directly from the measure-
ments. Using these parameters the DRTs were Fig. 7. Fitting of the DRTs to the time delay model.

502
 Packed bed reactors

6C

4c

2c

IC
: f

I I I I 1 1 1 I I
f
2.1 2.2 2.3 2.4 2.5 2.6 2-7 2-6 2.8

f x 103. k-’
4

Fig. 8. Reduced mean contact time & as function of the

inverse temperature.
0 (3-b 2
A C,H,.

I I I I I I I
0 2.2 2.4 2.6 2.6 3.0 3.2 ? 4

$x103

Fig. 10. First moments of the DCTs for ethane and ethene
with and without reaction
0 ethane without reaction
0 ethane with reaction
A ethene without reaction
A ethene with reaction.

case A without reaction: pi, ethane< & ethene

and for case B with reaction: at high temperatures
I
2.3 2.4 2.5 2.6 2.7 2.6 /-bMhane ’ /&ethene;

$x103, k-’
whereas with decreasing temperatures the differ-
Fig. 9. Second moment of the DCT of ethene hLzcas function ence gradually disappears, so that at low tempera-
of the inverse temperature. tures

is very broad. The DRT is controlled by the

DCT alone. With increasing temperature the
width of the DCT deminishes more rapidly than In a differential reactor the reactant molecules
its mean value. Therefore at high temperatures appear first. The difference between the first
the DCT has only a weak influence on the DRT. moments of the DRTs of reactant and product
molecules is as great that the two peaks appear
at the exit of the reactor completely separated.
With reaction In case A the packed bed is in series with a
Figure 10 shows the first moments of the DCTs differential reactor. Therefore the product mole-
for ethene and ethane. One finds for cules enters the packed bed later than the
503
 P. ORTH and K. SCHiiGERL

reactant molecules, i.e.

With increasing bed length this difference

gradually disappears. At a given length the first
moments are equal and by further increase of the
bed length the ethane peak overtakes the ethene
peak and therefore at the exit one finds:

In a differential reactor the product molecules I I I I I I I I

are delayed, because they are formed from 2.1 2.2 23 2.4 2.5 2% 2.7 29 2.9

reactant molecules which are adsorbed on the $xI03, k-’

surface. In the packed bed which is in series with

Fig. 11. Second moments of the DCTs for ethane and ethene
the differential reactor, this difference gradually with and without reaction
disappears because of the influence of the pure 0 ethene without reaction
adsorption-desorption process (ethene is more 0 ethene with reaction
A ethane without reaction
strongly adsorbed on the surface than ethane). A ethane with reaction.
In case B and at high temperatures the adsorp-
tion-desorption process is rapid, therefore the
difference between the first moments of the furthermore
DCTs of reactant and product molecules is not for ethene A A s b B at all temperatures and
obscured by the purely physical process. With
decreasing temperature the influence of the ad- for ethane bA < bB at high temperatures. With
sorption-desorption process gradually becomes decreasing temperature this difference gradually
dominant and the difference between the first decreases, the moments become equal and at low
moments disappears. temperatures one finds:
Furthermore, Fig. 10 shows that

&CA > pier, for ethene and

t-&A =Si&l for ethane, i.e.
the chemical reaction shifts the DCTs of non-
converted ethene and produced ethane to lower
and higher values respectively.
Figure 11 shows the second moments of the
DCTs of ethane and ethene. One can recognize
that for
case A without reaction: bethene > kethane; with
decreasing temperature the difference de-
minishes, and for
case B with reaction: bethene <<bethane; with
decreasing temperature the difference increases,
passes a maximum and then decreases again;
504
Typical changes in the shape of the integral
DCTs of ethene and ethane are shown in Figs.
12 and 13 for case B (with reaction) for different
temperatures. The DCTs are symmetrical only
at low temperatures. With increasing temperature
they gradually become asymmetrical. With
reference to their asymmetry the DCT of ethene
is approximately the mirror image of the DCT of
ethane.
From Figs. 10 to 13 the following conclusions
can be made. The strong temperature depen-
dence of the moments of the DCTs of ethene and
ethane is preserved if chemical reaction occurs.
The probability for chemical reaction is higher
for ethene molecules which have spent more time
 Packed bed reactors

in the adsorbed state and have longer contact

times than the average. Therefore, ethene mole-
cules which have a relatively high contact time
will be preferentially converted.
06
The effect of the chemical reaction is there-
c for to reduce the mean contact time and the
-& width of the DCT of non-converted ethene mole-
0.4
cules and to make the distribution asymmetrical,
especially at higher temperatures. With increas-
o-2 ing temperature the DCT of ethene becomes
gradually narrower. At 200°C nearly all of the
0 02 04 06 I.0 I.2
ethene molecules which were adsorbed and
therefore have a finite contact time are apparently
8,
converted. Only the ethene molecules which
Fig. 12. Integral distribution of contact times of non-con- were adsorbed only for very short time and
verted ethene molecules at temperatures
200°C 0
therefore have nearly zero contact time leave
120°C A the reactor unconverted. The width of the DCT
60°C 0. and all of its moments are nearly zero at this
temperature. The reduced DCT can be approxi-
mated by an ideal delta function and the inte-
0.6
grated reduced DCT by an ideal step function
(Fig. 12).
0.6
The explanation of the overall DCTs of
ethane is more complicated, since the molecules
0.4
which appear at the reactor exit as ethane have
spent a fraction of their residence time as ethene
0.2 before their conversion.
The probability that they were converted at a
given age t or at a given distance from the exit
0 02 0.4 0.6 0.6 I-O I.2
x = ut is given by

-c(t) = exp (-kt).

CO

Therefore most of the molecules are converted

0.6 at a fairly early stage near the entrance of the
reactor.
At high temperatures the first as well as the
second moments of the overall DCTs of ethane
are higher with chemical reaction than without
because of the time-lag caused by the reaction.
With decreasing temperature the purely physical
process gradually compensates the effect of the
Fig. 13. Integral distribution of contact times of converted chemical lag. At low temperatures the first
ethane molecules at temperatures moments of the DCTs of ethane with and without
200°C 0
120°C A reaction are equal.
60°C 0. The explanation of the remarkable asymmetry
505

C.E.S. Vol. 21 No. 3 - D

 P. ORTH and K. SCHiiGERL
of the DCTs of ethene and ethane molecules
(Figs. 12 and 13) is possible, if one considers
the time lag of ethane molecules with respect to
ethene molecules at the exit of a differential
reactor (Fig. 14a) and the relative shift of ethene
and ethane peaks in an integral reactor (Fig. 14b).
51
._ Time lag
‘0
L
E
s i& _
?I Ethane ,Ethene
0
::
s The apparent energies of activation
B N-L
Time
(a)
Time
(b)
Fig. 14. (a) Distribution of residence times of ethene and
ethane molecules at the exit of a differentialreactor. (b)
Distribution of residence times of ethene and ethane mole-
cules at the exit of an integralreactor.
COMPARISON OF THE MODEL PARAMETERS
The overall mean residence time T of the gas in
packed bed reactor consists of the mean contact
time r, and the mean time rjnert, which the
particles spent in reactor in non-adsorbed state.
The time delay of particles is caused by pore
diffusion and adsorption. Because only the ad-
sorption depends strongly on the temperature,
the “apparent energies of activation” [8] of the
contact time TVand of the delay times r, and tDc
should be identical.
7c was measured as difference of T and rinert,
r, was calculated from the ratio of the lirst and
second moments of the DRT according to the
506
residence time delay model (see Eq. (16)):
According to the contact time delay model r,
can be calculated from the moments of the DCf
(see Eq. (18)):
--- 1
(21)
P2c 2’D,’
of rcr to and
&, are:
Erc = 5-l kcallmol for ethene
ET, = 4.3 kcal/mol for ethane
EtD = 3.6 kcal/mol for ethene
EtD,= 4.5 kcal/mol for ethene.
Since rc was evaluated directly from the first
moments of the DRTs, E,_ should be more
accurate than Et, and EtD . fitDcis closer to E, c
P
than Et,.
On the other hand the rate constant k can be
calculated from Eq. (22) according to the
residence time delay model from the correspond-
ing DRTs with and without reaction:
k=2 /&--fO
--- /-G-f0
(22)
( P2R P2 )*
The hydrogenation of ethene on the same
catalyst (palladium catalyst on aluminium silicate
support) under the same conditions as used here
was investigated earlier and found to be an
apparent first order reaction[7]. Therefore the
equations developed for first order reactions can
be applied to the reaction investigated.
Table 1 shows k calculated from Eq. (22) as
function of the temperature.
It can readily be seen that k is nearly constant,
i.e. EI, = 0. In contrary with k the rate constant
 Packed bed reactors

Table 1

S[oC] 60 80 100 120 140 160 180 200

k[s-‘1 O-32 O-38 040 0.43 O-45 O-45 O-45 O-43

k, which is calculated from Eq. (23) from the
DCTs with and without reaction according to
the contact time delay model
k, = 2(!+$5)
(23)
depends on the temperature. The apparent energy to describe the complex process in the catalytic
of activation Eke of kc amounts (Fig. 15):
same conversion. Therefore the influence of the
temperature could be separated from that of the
conversion.
In contrary with (kcTc) the product (kt,)
deminishes with increasing temperature in dis-
agreement with the experimental findings. There-
fore the contact time delay model is more suitable
bed reactor than the residence time delay model.

Ek, = 6.35 kcal/mol. MEASUREMENTS IN STATIONARY OPEN

FLOW vs. BATCH (CLOSED LOOP) REACTORS
Not only the rate constant but also the mean
contact time can depend strongly on the tem-
perature.
If the rate constant k+ of a first order hetero-
geneous catalytic reaction is evaluated in a
stationary open flow packed bed reactor by
means of the dependence of the conversion on
the flow rate F, and/or mean residence time
T+ = V/F, at different temperatures, the apparent
activation energy Ek++of k+ includes the tem-
perature dependences of kc as well as 7,:

Ek+ = &, - &.

However, the rate constant k++, which is

fX103
Fig. 15. Rate constant kc calculated from Eq. (23) as function
of the inverse temperature.
Between 60 and 180°C the temperature de-
pendences of kc and 7c (and/or to) are nearly
equal, but have different signs[81. Therefore the
product (kp,) and/or (k,t,) is nearly independent
of the temperature. In accordance with this the
conversion should change only slightly with the
temperature. The experiments confirm this.
Because of the slight temperature dependence of
the conversion, most of the DRT and DCT
measurements could be carried out at about the
507
evaluated in a batch (closed loop) packed bed
reactor by means of the time dependence of the
conversion, does not include the influence of the
contact time T=.Therefore the apparent energy of
activation Ek+ of k++ should be identical with
Ek, and it should be possible to evalute ET, the
“apparent energy Of activation” Of T, as the
difference of Ek” and Ek+:
ETc= Eke+- E,+ . (24)
The hydrogenation and tritiation of ethene in a
closed loop and open flow packed bed reactors
on the same catalyst were investigated earlier [7].
By Eq. (24) following “apparent energies of
 P. ORTH and K. SCHUGERL

activations” ET, of the contact time T, were Et, “apparent energy of activation” of fD,
evaluated from these measurements: kcal/mol
EtDc “apparent energy of activation” of tDc7
E_ = 3.6 kcal/mol (hydrogenation) kcal/mol
J% “apparent energy of activation” of T,,
E,c = 3.7 kcal/mol (tritiation). kcal/mol
f(t) distribution of residence times, DRT
CONCLUSIONS L(t) distribution of contact times, DCT
It is reasonable to separate the time, which the g(r) weight function of the system
particles spend in a packed bed catalytic reactor, k rate constant evaluated by means of the
in two parts: the residence time in the gas phase, DRT, l/set
which is nearly independent of the temperature k, rate constant evaluated by means of the
and depends on the flow rate, and the contact DCT, l/set
time, which is independent of the flow rate and k+ rate constant evaluated in stationary
strongly depends on the temperature. open flow reator by stationary
The generalised time model (contact time delay measurements, Vsec
model) treats these two times separately. The kit rate constant evaluated in batch (closed
application of this model to the catalytical loop) reactor, l/set
hydrogenation of ethene in a packed bed reactor L length of the reactor, cm
was successful in a wide temperature range. The A4 coefficient of axial mixing, cm*/sec
results show that the contact time is significantly n number of stages
influenced by the chemical reaction but the Pll probability that the molecules pass the
strong temperature dependence of the contact series with n stages
time is preserved during the reaction. t time, set
Because of this strong temperature dependence tD delay time calculated from DRT, set
of the contact time the separate estimation of the fDC
delay time calculated from DCT, set
contact time and the rate constant for stationary to residence time without any delay, set
open flow heterogeneous packed bed reactors is t+ = t-to, set
recommended. tc= fads - contact time, set
finert

T temperature in reactor, K
Acknowledgement-The authors gratefully acknowledge the u flow rate, cmlsec
financial support of the Deutsche Fors&ungsgemein&haft, x length of the bed, cm
Bundesminister fib Bildung und Wissenschaft and Max-
Buchner-Stiftung. x(t) input function
y(t) output function

NOTATION Greek symbols

Bo = ux/M Bodenstein number (lateral flow per unit length)/(through-
c concentration, mol/cm3 put flow rate), cm-’
co concentration at t = 0, mol/cm3 first moment of the time distribution
Ek apparent energy of activation of k, kcal/ above the origin, set
mol second moment above the first moment,
E,+ apparent energy of activation of k+, set*
kcal/mol mean residence time, set
E k++ apparent energy of activation of k++, mean contact time, set
kcal/mol mean residence time in a stage, set
E k, apparent energy of activation of k,, kcal/ reduced time = t/T
mol temperature, “C
508
 Packed bed reactors

Subscripts c evaluated from the contact time dis-

A case A (without reaction) tribution
B case B (with reaction) ethane measured with ethane
R measured with reaction ethene measured with ethene
ads adsorbing component inert non-adsorbing component

REFERENCES
VI NAUMANN E. B. and COLLINGE C. N., Chem. Engng Sci. 1968 23 1309.13 17.
PI ORTH P., Dissertation, Technical University of Hannover 1970.
[31 LEVENSPIEL 0. and SMITH W. K., Chem. Engng Sci. 1957 6 227.
[41 BUFFHAM B. A., GIBILARO L. G. and KROPHOLLER H. W., Chem. EnanaSci. 1969 24 7.
[51 BUFFHAM B. A. and GIBILARO L. G., Chem. EngngJ. 1970 132. - -
[61 CHAO R. and HOELSCHER H. E..AJ.Ch.EJI 1966 12 271.
[71 GARTNER E., Dissertation, Hannover 1968.
[81 FRENKEL J., Z. Physik 1924 26 117.

Resume-On mesure les distributions des temps de residence, DRT, et des temps de contact, DCT,
dans le cas de l’ethylene reagissant avec de l’hydrogene; on mesure tgalement l’ethane ainsi formee
dans un catalyseur palladium support6 par du silicate d’aluminium dans un reacteur muni dun lit
gami isotherme a des temperatures ahant de 60 a 200°C.
La reaction intluence fortement les DRT et DCT du corps reagissant et des molecules des produits
resultants. La dependance des DRT et DCT, de l’ethane et de l’ethylea la temperature est Ctudiee
avec et sans reaction chimique et avec un rendement presque constant. On explique quantitativement
les resultats a l’aide dun modele generalise de retardement du temps.

Zusammenfassung - Die Verweilzeit- und Kontaktzeitverteilungen wurden gemessen fiir Athylen,

das mit Wasserstoff reagiert, und Athan, das wahrend der Reaktion entsteht, auf einem Palladium
Katalysator auf Aluminiumsilikat-Tmger in einem isothermen Festbettreaktor in einem Temperatur-
bereich von 60 bis 200°C.
Die Reaktion beeinfluat die Verweilzeit- und Kontaktzeitverteilungen der Reaktionsteilnehmer-
und -produktmolekiile wesentlich. Die Temperaturabhlngigkeit der Verweilzeit- und Kontaktzeit-
verteilungen von Athylen und Athan wurden ohne und mit chemischer Reaktion bei nahe konstantem
Umsatz untersucht. Die Ergebnisse werden mit Hilfe eines verallgemeinetten Zeitverzogerungs-
modells quantitativ ausgewertet und gedeutet.

509