Dehydrogenation of I-Butene into Butadiene.

Kinetics, Catalyst
Coking, and Reactor Design
Francis J. Dumez and Gilbert F. Froment'
Laboratoriurn voor Petrochernische Techniek. Rijksuniversiteit, Gent, Belgium

The kinetics of 1-butene dehydrogenation over a Cr203-AI203 catalyst between 490 and 600 OC were determined in a differential reactor. The discrimination between rival Langmuir-Hinshelwood models was based on
a sequentially designed experimental program. The kinetics of coking from butene and butadiene and the
deactivation functions for coking and for the main reaction were determined with a thermobalance. The equations derived from differential reactor results gave excellent predictions of the performance of an experimental
integral reactor. The effect of internal transport limitation was investigated. An industrial reactor was simulated
and optimized.

I. Introduction
An important fraction of the world butadiene production
is obtained by dehydrogenation of n-butane or n-butene.
This reaction is accompanied by side reactions leading to
carbonaceous deposits which rapidly deactivate the catalyst. T h e coking tendency may be limited up to a certain
extent either by diluting the feed with steam or by operating under reduced pressure. T h e second solution has been
favored. T h e butadiene production using vacuum processes
amounted to 700000 T in 1971 (Hydrocarbon Process.,
1971). With vacuum processes operating with butene as
feed, the on-stream time is limited to 7-15 min, after which
regeneration of the catalyst by burning off the coke is required. With such cycle times the heat given off by the regeneration compensates for the heat requirements of the
adiabatic dehydrogenation (Hornaday e t al., 1961; Thomas,
1970).
Vacuum processes are based upon Crz03-Al203 catalysts. Fundamental properties of such catalysts were studied by Burwell et al. (1969), Poole and MacIver (19671,
Marcilly and Delmon (1972), Masson and Delmon (1972),
Traynard e t al. (1971, 1973). These authors found that the
catalytic activity was represented by surface Cr3+ and 0'ions which are incompletely coordinated; ions of y-CrzO3A1203solid solutions were found to be the most active.
Aspects of the kinetics of butene dehydrogenation on
such catalysts were investigated by Forni e t al. (1969),
Happel e t al. (1966), and Timoshenko and Buyanov (1972).
Although the surface reaction was generally found to be
rate determining, there is little more agreement between
the results. Further, none of these studies was carried out
with particle sizes used in industrial operation. So far, no
quantitative treatment of the deactivation of the catalyst
by coke deposition has been published. Yet, without such
information no rigorous optimization of industrial operation is possible.
This paper reports on a detailed study of the kinetics of
the dehydrogenation, of the coke deposition, and of the associated catalyst decay. The effect of internal transport
limitations is investigated. Industrial operation is simulated and optimized.
11. Kinetics of the Main Reaction

11.1. Experimental Procedure and Range of Operating Variables. T h e catalyst used in this investigation was
a Cr203-Al203 catalyst containing 20 wt % Crz03 and having a surface area of 57 m2/g. Experimental checks on the

absence of partial pressure and temperature gradients in

t h e film surrounding the particle and of temperature gradients inside the particle were performed. Also, preliminary
runs were carried out in order to determine the catalyst
particle size which permits neglecting internal transport
limitation.
The kinetics of butene dehydrogenation were determined in a quartz tube inserted in an electrical furnace.
The catalyst particles, diluted with quartz particles, were
supported by a stainless steel gauze. The temperature was
controlled by two thermocouples, one in the center of the
catalyst section and one near the wall.
T h e feed stream was calibrated and dried in the classical
way, The outlet gases were analyzed by gas chromatography on a 20% propylene carbonate/chromosorb column.
Experiments were performed a t 4 temperatures: 490, 525,
560, and 600 "C. T h e butene pressure ranged from 0.02 to
0.27 atm, the hydrogen pressure from 0 to 0.10 atm, and the
butadiene pressure from 0 to 0.10 atm. Although only 1butene was fed, the outlet gases always contained a mixture
of 1-butene, cis-2-butene, and trans-2-butene close to the
equilibrium composition. Therefore, the dehydrogenation
equilibrium could be referred to butene equilibrium mixtures. In all these experiments, the conversion was kept
below 2% by adjusting the amount of catalyst and the gas
flow rates. Therefore, the reactor was considered to be differential.
Due to coke deposition the dehydrogenation rate was
found to decrease with time. T o determine the rate of the
main reaction in the absence of coke required extrapolation
to zero time. Since the first analysis was taken after 2 min,
while a run extended to 30 min, the extrapolation was no
problem.
11.2. Kinetic Analysis. Five possible reaction schemes,
shown in Table I, were derived for the main reaction. For
each of these mechanisms several rate equations may be
derived, depending upon the postulated rate-determining
step. Fifteen possible rate equations were retained. They
are listed in Table 11.
The experimental program was designed to discriminate
in an optimal way between the rival models. Sequential
procedures for optimal discrimination have been introduced by Box and Hill (1967) and by Hunter and Reiner
(1965). The methods have been applied to experimental
data, but only a posteriori, for illustrative purposes (Froment and Mezaki, 1970). The present work is probably the
first in which the experiments were actually and exclusively designed on the basis of a sequential discrimination proInd. Eng. Chem., Process Des. Dev., Vol. 15, No. 2, 1976

291

Table I. Reaction Schemes for Butene Dehydrogenation

(a) Atomic Dehydrogenation; Surface Recombination of
Hydrogen
(1) B + L = B L
(a11
(zj BL+L-ML+HL
(a2)
(3) M L + L t D L + H L
(a3)
(a4j
(4j D L = D + L
( 5 ) 2HL+ H,L + L
( 6 ) H,L + H, + L
(where B = n-butene; D = butadiene; H, = hydrogen;
M = an intermediate complex)
( b ) Atomic Dehydrogenation; Gas Phase Recombination of
Hydrogen
(1) B + L t BL
(bl)
(2) B L + L + M L + H L
(b2)
(3) M L + L t M L + H L
(b3)
(4) D L t D + L
(b4)
( 5 ) 2HL + H, + 2L
(c) Molecular Dehydrogenation
(1) B + L = B L
(cl)
( 2 ) BL + L + DL + H,L
(c2)
(3) D L + D + L
(c3)
( 4 ) H,L + H, + L
( d ) Atomic Dehydrogenation; Intermediate Complex with
Short Lifetime Surface Recombination of Hydrogen
(1) B + L + B L
(dl)
( 2 ) BL + 2L t DL + 2HL
(d2)
(3) D L + D + L
( 4 ) 2HL= H,L + L
( 5 ) H,L + H, + L
(e) Atomic Dehydrogenation; Intermediate Complex with
Short Lifetime; Gas Phase Hydrogen Recombination
(1) B + L t B L
(el)
( 2 ) BL + 2 L + DL + 2HL
(e2)
(3) D L = D + L
( 4 ) 2HL t H, + 2L
cedure. The operating conditions for an experiment were
selected on the basis of the design criterion. Then the experiment was carried out, the parameters of the models
were estimated, and the current state of adequacy of the
rival models was tested. With this information the next experiment was designed and so on, until the discrimination
was achieved. Eventually, some further experiments were
carried out to improve the significance of the parameters of
the retained model(s).
The sequential choice of experimental conditions for optimal discrimination between the rival models was based
upon the following design criterion
m

- PH,q

lPHLo
1=1, = 1

(1)

the experimental error variance obtained from each of the

rival models. This is done by means of Bartlett's x2 test
(Bartlett, 1937). The details of the procedure, the designed
operating conditions, and the evolution of the discrimination will be reported elsewhere (Dumez et al., to be published). Suffice it to mention that a t 525 "C, e.g., a total of
14 experiments, 7 of which were preliminary, i.e., required
to start the sequential design, allowed discarding all the
models except a2, b2, c2, d2, and e2, all corresponding to
surface reaction on dual sites as rate-determining step. The
differences PH,O - PH,O between these models were smaller
than the experimental error. The models a2, b2, and d2
were eliminated because they contained a t least one parameter that was not significantly different from zero a t
the 95% confidence level. Model c2, corresponding to molecular dehydrogenation and the surface reaction on dual
sites as rate determining step, led t o a fit which was slightly
superior to that of e2 and was finally retained. The same
conclusion was reached a t 490,560, and 600 "C.
I t should be pointed out here how efficient sequential
design procedures for model discrimination are. A classical
experimental program, less conscious of the ultimate goal,
would no doubt have involved a much more extensive experimental program.
The parameters of model c2 were estimated by minimizing

for all the data 1 = 1, . . . , N a t the four temperature levels.

This involves nonlinear regression. Indeed, the expression
for r ~ according
0
to model c2 is

in which the adsorption equilibrium constants KB,KH,and

K D are related to the equilibrium constants of the steps of
the reaction in the following way
(4)
Statistical tests indicated that the adsorption equilibrium
constants were not significantly temperature dependent.
The rate coefficient ~ H obeyed
O
the Arrhenius temperature
depend en ce
kHo

= AH' exp(-EH/RT)

(5)

Reparameterization according to

If'

where PH,O represents the estimated value of the reaction

rate according to model i, and D is the divergence between
the predicted rates. T h e double summation ensures that
each model is taken in turn as a reference. Given n - 1 experiments the n t h experiment was performed in the differential reactor a t those values of p ~p , ~and
, p~ which maximized D. A grid is selected for possible combinations of
p ~p , ~and
, p~ within the operability region. From previous experience on constructed examples the criterion (1)
was shown to lead to the same experiments as the Box-Hill
criterion that accounts for the variances.
T h e state of model adequacy was tested by means of a
criterion proposed by Hosten and Froment (to be published). The underlying idea is that the minimum sum of
squares of residuals divided by the appropriate number of
degrees of freedom is an unbiased estimate of the experimental error variance for the correct mathematical model
only. For all other models this quantity is biased due to a
lack of fit of the model. The criterion for adequacy therefore consists in testing the homogeneity of the estimates of
292

Ind. Eng. Chem., Process Des. Dev., Vol. 15.No. 2, 1976

AH' = AH" exp(EH/RT,)

(6)

with T, the average temperature, facilitated the estimation. The values of the parameters and their standard deviations are given in Table 111. The Arrhenius plot for ~ H O
is given in Figure 1. The dots represent the parameter
values obtained from a treatment of the data per temperature.
111. Kinetics of Coking
The kinetics of coking and the deactivation functions for
coking and for the main reaction were determined by
means of a Cahn RH thermobalance. The catalyst was
placed in a stainless steel basket suspended a t one balance
arm. The temperature was measured in two positions by
thermocouples placed just below the basket and between
the basket and the quartz tube surrounding it.
The temperature in the coking experiments ranged from
480 to 630 "C, the butene pressure from 0.02 to 0.25 atm,
and the butadiene pressure from 0.02 to 0.15 atm. Individ-

Table 11. Rate Equations for Butene Dehydrogenation

'Ha

Table 111. Kinetic Coefficients and Adsorption Constants

of Butene Dehydrogenation
Parameter

Value

Approx.
std dev

AHO(T, = 815.36 K )

0.2697
2 9236
1.727
3.593
38.028

0.0298
732
0.342
0.641
6.165

EH

KB
KH
KD

ual components as well as mixtures of butene and butadiene, butene and hydrogen, and butadiene and hydrogen'
were fed. The hydrogen pressure range was 0-0.15 atm.
Coke deposition on the basket itself was always negligible.
The deactivation function for coking was determined
from the experimental coke vs. time curves as described
below. Coke was shown to be deposited from both butene

and butadiene, while hydrogen exerted an inhibiting effect.

An example of the coke content of the catalyst as a function of time is given in Figure 2. Since the thermobalance is
a differential reactor, operating a t point values of the partial pressures and the temperature, the decrease in the rate
of coking observed with increasing coke content reflects the
deactivating effect of coke. The rate equation for coke formation therefore has to include a deactivation function,
multiplying the rate in the absence of coke.
dCc
dt

-= rcO pc

(7)

rco is the initial coking rate, a function of the partial pressures and temperature which reduces to a constant for a
given experiment in the thermobalance. Several expressions were tried for cpc (Froment and Bischoff, 1961).
Ind. Eng. Chem., Process Des. Dev., Vol. 15, No. 2, 1976

293

the results of Depauw and Froment (1975) obtained with a

completely different system. An explanation based upon a
pore blocking mechanism has been attempted (Dumez and
Froment, to be published). The parameter a was found to
be identical for coking from either butene or butadiene and
independent of the operating variables, as can be seen from
the partial correlation coefficients between a and T,p ~ ,
p ~ and
, p ~ respectively,
,
shown in Table IV. This table
also contains the calculated t values for the zero hypothesis
for the partial correlation coefficients. The t values do not
exceed the tabulated value of 2.03 for the 95% probability
level.
The determination of the complete rate equation for
coke deposition required the simultaneous treatment of all
experiments, so that p ~ p , ~p , ~and
, T were varied. The
exponential deactivation function was substituted into the
rate equation for coking. After integration of the latter the
parameters were determined by minimization of

+ model t 2
o model e 2

t 2 calc

115

120

125

Figure 1. Arrhenius diagram of

130

bl

k"O.

Several rate equations, either empirical or based on the

Hougen-Watson concept, were tested. The best global fit
was obtained with the following equation.

with

kCeo = Aceo exp(-EcB/RT)

(12)

kcDo = A o o exp(-EcD/RT)
and KCH independent of temperature. The integrated
equation used in the objective function (10) was

Figure 2. C, vs. t measured on the thermobalance.

Again the frequency factors Aceo and ACD' were modified

as follows

ACB' = ACB" exp(EcB/RTm)

pc = exp(-aC,)
p.2 = 1 -

ac,

ACD' = ACD" exp(EcD/RT,)

p, = (1- aC,)2
47, =
$0,

1/(1 CYC,)

= 1/(1 CYC,)2

Note that the deactivation function is expressed in terms of

the carbon content of the catalyst, not in terms of time as
has been done frequently; indeed, time is not the true variable into eq 7 and integration with respect to time yields
respectively

(9)

to facilitate the parameter estimation.

The parameter values and their approximate standard
deviation are given in Table V. An example of the fit obtained with this equation is shown in Figure 2.
The frequency factors Aceo and ACDO are easily calculated from (14)

Ace0 = 1.559 X lo8

A

~ = 5.108
~ O x 105

Since the order with respect to butene, ~ C B and

,
to butadiene, ncD, is smaller than 1, it has been attempted to derive
an adequate mathematical model based on the LangmuirHinshelwood or Hougen-Watson concept.
The formation of what is called cokes proceeds over a sequence of steps involving addition and/or dehydrogenation.
Let the rate-determining step in this sequence be represented by
IlBL

IlDL

a and rCo were determined by fitting of the experimental

data by means of a least-squares criterion.
For the majority of the 50 experiments pc = exp(-aC,)
turned out to give the best fit. This, by the way, agrees with
Ind. Eng. Chem., Process Des. Dev., Vol. 15,No. 2, 1976

+ (nBB)L

for coking from butene, and by

294

(14)

+ (nDD)L

IhBL

ZhDL

for coking from butadiene. Z ~ B Land Z~DLare adsorbed

lower intermediates in equilibrium with butene and butadiene and I h B L and I h D L higher intermediates. For pure
addition ne and n D would be unity, for pure dehydrogena-

Table IV. Test of Partial Correlation Coefficients between

CY and the Independent Variables
p Value

t Value

-0.1612
0.98

+0.3042
1.92

-0.0627
0.38

-0.0530
0.32

Table VI Values of the parameters of the

Langmuir-Hinshelwood Model

__

Parameter

Value

Approx.
std dev

CY

39.67
0.6049
30873
0.970
148.66
18117
1.767

1.724
0.0694
1300
0.051
18.77
7 84
0.034

AcB"(T,

ACD
Approx.

Value
45.53
0.2917
32800
0.743
1.3168
21042
0.853
1.695

822.8 K )

n C B o,

Table V. Kinetic Parameters for Coking

Parameter

=
ECB

std dev

ECD
nCD

1.08

0.0209
7 58
0.029

0.1158
501
0.023
0.076

n B

+1

nCD = n D

+1

nCB

KB,K H ,and K D have already been estimated (section 11.2).

,
n C B , AcDO, E C D ,ncD, and CY were
The values of A c B ~ ECB,
tion zero, whereas if both mechanisms would be involved in
the rate-determining step ne and n D would be between
zero and one.
Neglecting possible reverse reactions the rate of coking
may be written

rc = k c B ' C r l B r , C i n p B ) I , -k

kcD'CIlnL CinoD)L

(15)

The unmeasurable concentration of adsorbed species can

be eliminated by accounting for the equilibria between butene and butadiene and the lower intermediates, so that
(15) becomes

From (16) the concentration of free active sites C I may

~ be
eliminated in favor of bulk partial pressures by means of a
balance on the total number of active sites. When the concentrations of the adsorbed lower intermediates are neglected with respect to the concentrations of adsorbed butene, butadiene, and hydrogen, CL is given by
CL =

C t L - CSL
1 + KBPB+ K n P H

+ KDPD

(17)

with C t L the total number of active sites and CSL the number of sites covered by coke. The coking rate becomes

k C H ' K I i e L PBnB+'

f kCD'KIiDL pDnDtl

(18)
(1 + K B P R+ K H P H+ I ~ D P D ) ~

A deactivation function for the coking may now be defined

by

T h e problem with this function is that it contains the inaccessible concentration of adsorbed higher intermediate.
There is no way out, here, except to resort to the empirical
relation between coke and the deactivation derived from
the experiments, qc = exp(-pCc). When this expression is
substituted into (181, the resulting equation can be integrated with respect to time, since the partial pressures and
temperature remain constant in the thermobalance experiments, to give

where

estimated by nonlinear regression and are given in Table

VI [AcBO and ACB' were also modified according to (14)].
From the values of n c B and ncD, it can be concluded that
the rate-determining step for coking from butene would be
dehydrogenation step

I~BL L

+H 2 L

Z~BL

T h e activation energy E C B agrees remarkably well with

that found for dehydrogenation of butene. The rate-determining step for coking from butadiene would be

IlDL

+ (0.75g)L

IhDL

i.e. would mainly consist of addition. The value for ECD

seems to support this conclusion.
The accuracy of the Langmuir-Hinshelwood model (18)
is lower than that of model ( l l ) , however. This is believed
t o result, partly a t least, from the lower mathematical flexibility of eq 18 as compared to (11). In addition, the Langmuir-Hinshelwood model is probably oversimplified. On
the other hand and apart from kinetics, the approach
seems to lead to some interesting conclusions as to the
mechanisms of coking.

IV. Effect of Coke on the Rate of Dehydrogenation

The deactivation function for the dehydrogenation was
also determined by means of the thermobalance, in the
same way as done by Tackeuchi et al. (1966) and by Ozawa
and Bischoff (1968), i.e., by measuring simultaneously the
coke content and the composition of the exit gases as functions of time. T o eliminate the effect of bypassing, the conversions were all referred to the one first measured. It was
checked that the ratio of the amounts of gas flowing
through and around the basket remained constant and was
not affected by the coke deposition: in a regeneration experiment the burning rate, determined from the weight loss
measured by means of the balance, completely agreed with
that calculated from the amount of CO and COS in the exit
gases, for the whole duration of the experiment.
Figure 3 shows the relation between r H / r H n =
and the
coke content, easily derived from the measurements r H / r H o
= p~ vs. time and coke content vs. time. Although there is a
certain spread on the data, no systematic trend with respect to the temperature or the partial pressures could be
detected. The temperature ranged from 520 to 616 "C; the
butene pressure from 0.036 to 0.16 atm.
Again, the best fit was obtained with an exponential
function: VH = exp(-nC,). A value of 42.12 was calculated
for a. The agreement with the value found for the deactivaInd. Eng. Chem., Process Des. Dev., Vol. 15, No. 2, 1976

295

.O1

.02

04

.03

.05

.06

eration without prior investigation of the effect of the particle size on the rate of the overall process consisting of reaction and internal transport.
The effect of transport phenomena inside the particle is
generally expressed by means of the effectiveness factor,
which has been related to the geometry of the catalyst, the
effective diffusivity and the rate parameters of the reaction
in a closed form only for single reactions and simple kinetics. Bischoff (1967) has proposed the use of a generalized
modulus which allows handling any reaction rate equation
along the lines developed for simple kinetics, but the method requires the reaction rate to be expressed as a function
of the concentration of one component only. In the case
studied here the amounts of butene and butadiene involved
in coking reactions were too important to be neglected with
respect to those involved in the main reaction. Therefore,
three continuity equations had to be taken into account for
the gaseous components. The equations may be written, for
quasi-steady state conditions, negligible external transport
resistance and isothermal particles

Figure 3. Activity of t h e catalyst for dehydrogenation vs. coke

content.

(23)

tion parameter for the two coking reactions is remarkable.

I t may be concluded that the main reaction and the coking
reactions occur on the same sites.
The set of rate equations may now be written
1.826 X loTexp(-29236/RT)

p~ - -

+ 1 8 7 2 7 +~ ~3.593pH + 3 8 . 0 2 8 ~ ~ ) ' exp(-42.12CJ

1.5588 x 10' e X p ( - 3 2 8 6 0 / R T ) p ~ O .+~ 5.108
~ ~ X lo5 e x p ( - 2 1 0 4 2 / R T ) p ~ ~ . ~ ' ~
rc =
exp(-45.53Cc)
(1 + 1.695 6)'
rH

(1

V. Experiments in a n I n t e g r a l R e a c t o r
The equations derived from experiments in differential
reactors were tested by a few experiments carried out in an
integral reactor. In this reactor the catalyst bed was divided into five sections, separated by metal gauze, to enable
unloading the catalyst in well defined sections a t the end of
a run. The temperature was measured in each section by
means of thermocouples. The exit gas compositions were
measured as a function of time. The temperature varied
during an experiment, because of deactivation of the catalyst. The catalyst particle size was the same as that used in
the differential reactor.
The experimental results were compared with those obtained by numerical integration of the continuity equations
for the different species, containing the rate equations
(21)-(22). The temperature variations were also accounted
for through (21)-(22).
Figures 4 and 5 show the results for a typical run (PB =
0.22 atm, T = 595 "C). The agreement between calculated
and experimental results is excellent. I t is worthwhile noticing that there is hardly any coke profile. There are two
reasons for this: coke is formed from both butene and butadiene, and hydrogen, a reaction product, inhibits the coke
formation.
VI. Influence of Catalyst P a r t i c l e Size
The rate equations (21)-(22) were determined with catalyst particles small enough to eliminate resistances to internal transport. With experiments a t low temperatures, the
diameter was 0.7 mm, a t higher temperatures 0.4 mm. Industrially the particle size is generally around 4 mm, to
limit the pressure drop through the bed. Consequently, the
results given above cannot be extrapolated to industrial op296

Ind. Eng. Chem., Process Des. Dev., Vol. 15,No. 2, 1976

(21)
(22)

with boundary conditions

r = Re;

CB,k = CB; CH,k = CH; CD,k = CD

(24)

is expressed in kmollkg of cat. h, rCB and rCD in kg coke/

kg of cat. h. Therefore, the conversion factors $CB and $CD
are required. They are expressed in kg of coke per kg of butene or butadiene involved in the coking and thus account
for the loss of hydrogen associated with the coke formation.
DB, DH, and DD are the effective diffusivities for butene,
hydrogen, and butadiene and are related to the molecular
and the Knudsen diffusivities. For butene, e.g.
rH

The molecular diffusivities were calculated from a weighted average of the binary diffusion resistances. The binary
diffusion coefficients were estimated from the formula of
Fuller et al. (Reid and Sherwood, 1958).
The calculation Of DB,k, DH,k, and DD,k requires information about the pore size. The catalyst studied had a bimodal pore size distribution. Further, via electron microscopy,
it was found that the catalyst consisted of crystallites of
about 5 p separated by voids of about 1 p. Consequently,
the maximum length of the micropores with average diameter 70 A cannot exceed 5 p. I t is easily calculated that this
is too short to develop any significant concentration gradients. Therefore, only the macropores with a pore volume of
0.155 cm3/g and with average pore diameter of 10000 A
were considered in the evaluation of the Knudsen diffusivitY.

Table VII. Experimental and Calculated Effectiveness

Factors with r = 5

R,, mm

p e , atm

T, "C

77
(exptl)

77
77
(calcd) (Bischoff)

2.3
2.3
2.3
2.3
0.6
0.35

0.2165
0.2159
0.2181
0.2492
0.2184
0.2038

500
550
550
599
580
595

0.334
0.187
0.199
0.140
0.521
0.808

0.346
0.229
0.229
0.135
0.493
0.621

rrp

~~

CalC

0.426
0.282
0.282
0.185
0.610
0.723

given particle size, by the true chemical rate calculated

from (21). Except for 0.35 mm the agreement is excellent.
T h e last column of this table contains the values obtained
by means of the generalized modulus defined by Bischoff.
However, t o do so, the coking reactions had to be neglected
t o be able to express the reaction rate as a function of the
concentration of one component only. The diffusivities
were supposed t o remain constant in the whole particle.
T h e generalized modulus is calculated by means of the following formula

10

20

30

40

50

I (mm)

Figure 4. Butadiene yield vs. time in the integral reactor.

Ct

03-

.02

01 -

secllon

Figure 5 . Coke profile in the integral reactor.

T h e effective diffusivities were allowed to vary with the
composition inside the particle. The only unknown parameter left in the continuity equations is the tortuosity factor,
T . This factor was determined from a comparison between
the experimental rates a t zero coke content, measured in a
differential reactor, and the surface fluxes. The latter were
calculated, using Fick's law, and for a given T , from the concentration profiles obtained by numerical integration of eq
23. A value of 5 for T led to the best fit of the experimental
data. This is the generally accepted value for the tortuosity
factor in catalysts of the type used in this work.
The calculated value for the effectiveness factor for dehydrogenation was obtained by dividing the calculated hydrogen flux a t the particle surface by the true chemical reaction rate. Table VI1 compares these values with those obtained by dividing the experimental rate corresponding to a

with L , the length of the pores and p the partial pressure

of the component considered. The effectiveness factor is
then evaluated from the graph given by Bischoff (1967). As
can be seen from Table VII, t h e effectiveness factors determined in this way are higher than the values obtained
through integration of the continuity equations. However,
Bischoff showed the integral to be exact for plates only.
When applied to spheres, the effectiveness factor may be
overestimated, as pointed out by Aris (1957): the maximum
deviation is observed around rj = 0.60 and amounts to 0.09.
T h e values obtained here are also about 10% higher than
t h e calculated ones.
T h e Bischoff approach does not provide the concentration profiles inside the particles so that the coking of the
catalyst cannot be predicted. T h e advantage of the method
lies in the simplicity of the calculations as compared to the
integration of the continuity equations.
Figure 6 illustrates the partial pressure profiles inside
the particle for zero deactivation and the coke profile after
0.25 h. The full lines correspond to the results obtained by
numerical integration using a Runge-Kutta-Gill routine.
T h e circles represent the partial pressures calculated by
the collocation method (Villadsen, 1970), applied with constant effective diffusivities. Values based on the gas phase
composition were used. The agreement is perfect and all in
favor of the collocation method, which is much faster from
the computational standpoint. The coke profile inside the
particle is relatively flat and very similar to that measured
in the integral reactor (Figure 5). If coke were formed from
butene only a decreasing profile from the surface to the
center of the particle would be observed; if coke would originate from butadiene only, the profile would be ascending
(Froment and Bischoff, 1961; Masamune and Smith, 1966).
The combination of both mechanisms and the inhibiting
effect of hydrogen, whose concentration is maximum a t the
center, leads to the actual profile. The optimization of the
process, which will be discussed in a later section, required
a large number of numerical integrations of the reactor
model, including the set of equations ( 2 3 ) . The integration
of this set in each node of the grid selected for the fluid
field equations was the time consuming step in the reactor
simulation, even when collocation was resorted to. A drastic simplification was required here, aiming a t eliminating
the set of equations (23) by relating in an algebraic way the
observed reaction rate to the conditions in the bulk of the
Ind. Eng. Chem., Process Des. Dev., Vol. 1 5 , No. 2 , 1976

297

Table VIII. Characteristics of an Industrial Reactor for

Butene Dehydrogenation
Length
Cross section

Catalyst and inert diameter

Catalyst bulk density
Inert bulk density
Catalyst geometrical
surface area
Inert surface area

.10

Inlet total pressure

Inlet butene pressure
Molar flowrate
Feed temperature
Initial bed temperature

!5

0.8 m
1 m'
0.0046 m
400 kg of cat./m3 of diluted
reactor
900 kg of cat./m3 of diluted
reactor
274 mz/m3of diluted
reactor
411 m*/m3of diluted
reactor
0.25 ata
0.25 ata
1 5 kmol/m* cross section h
600 "C
600 " C

1.25

+ I = ;25

rlR,

Figure 6. Dehydrogenation rates, partial pressure, and coke profiles inside the catalyst particles.

fluid. T o do so, the effective reaction rate was calculated,

for various temperatures and partial pressures in the bulk
gas phase, as the surface flux derived from the profiles obtained by integration of the set (23). This effective rate was
then plotted vs. the true reaction rate corresponding with
the gas phase conditions selected. A unique curve was obtained, with very little spread (Dumez and Froment, to be
published) and which could be expressed as
rE = -0.0034

+ dO.O0685(r~+ 0.0067)

(27)

For large values of rH and thus for small values of 7, the effective rate becomes proportional to
When both sides
of (27) are divided by rH, the resulting equation behaves
asymptotically like the relation between 7 and the Thiele
modulus 4 for first-order irreversible reactions. Note that
this simplification is only possible either in the absence of
coke inside the particle or with uniform coke deposition.
The butene and butadiene profiles in the reactor calculated in the way outlined above were in complete agreement with those obtained by the rigorous approach described in the next section.

6.

VII. Simulation of an Industrial Reactor

Industrially the dehydrogenation is carried out around
600 "C in adiabatic reactors and under reduced pressure.
The bed is diluted with inert particles which provide a heat
reservoir that reduces to a certain extent the effect of endothermicity of the reactor. Due to catalyst deactivation
the run length is generally limited to about 15 min, after
which regeneration is necessary. Before the regeneration is
started the reactor has to be purged. The heat given off
during the regeneration restores the original temperature
level in the reactor. After purging the reactor, butene may
be fed again and a new cycle starts. The characteristics of a
typical reactor and the operating conditions are given in
Table VIII.
The continuity and energy equations are as follows.
Fluid phase:
298

Ind. Eng. Chem., Process Des. Dev., Vol. 15, No. 2, 1976

where Ct = CB + CH + CD.
Nonsteady-state terms were considered here. However,
since the interstitial flow velocity is 4 m/sec and the bed
length is only 0.8 m the second terms in the left-hand sides
of the equations can be neglected.
The product (uSC,) is kept under the differential in
these equations to account for the important change in
number of moles in the gas phase owing to the dehydrogenation and t o a certain extent to the coking. The righthand side in (31) expresses the amount of heat exchanged
between the gas and the solid particles, catalytic and inert.
Solid phase:

T h e second term in the right-hand side of (32) and (33) expresses the amount of heat exchanged between the catalyst
and the inert particles, by conduction and radiation. Inside
the catalyst particles

-++-2-a2CD,k 2aCDk
t
aCD,k - - PK (rH

ar2

r ar

DD at

DD

-)rCD
~CCDMD

(36)
(37)

Again the nonsteady-state tcrms in (34), (35), and (36) can

be neglected. Notice further that no energy equation is
written for the catalyst particle, for the reasons already
mentioned. The boundary conditions are

8 70

r=O

860.
~

The particle equations were solved by means of collocation,

the continuity equations for the fluid phase by means of a
Runge-Kutta-Merson routine, and the energy equations in
a semianalytical manner. T h e heat transfer coefficients
were calculated from the j H correlation (Handley and
Heggs, 1968). The results of one rigorous computation are
shown in Figures 7, 8, and 9. In Figure 7 the temperature is
seen to drop rapidly under the initial value, due to the endothermic nature of the reaction. A temperature wave travels rapidly through the reactor as the reaction gradually extends to increasing depths. In the presence of coking no
true steady state is reached, however; the temperature profile is slowly translated upward, because of the decrease in
reaction rate due to the catalyst deactivation. The corresponding coke profiles are shown in Figure 8. The profile is
decreasing, mainly because of the higher temperature a t
the inlet and of the inhibition of the coke formation due to
the hydrogen near the outlet. Figure 9 illustrates the butadiene flow rate a t the outlet as a function of time. The
rapid initial decrease corresponds t o the initial temperature drop.
Beyond this initial period, the decrease in production is
much slower. The catalyst is deactivated by the coke deposition, but as the dehydrogenation rate is lowered the bed
temperature slowly rises, thus favoring again the butadiene
production.

VIII. Process Optimization

As mentioned already in section VI, the large number of
simulations involved in the optimization of the process necessitated the simplification of the system of equations
28-37 into the set (28-33), (37), and (27). This eliminated
the integration of the particle equations in each node of the
grid used in the integration of the fluid field equations.
Further, to permit the simulation of nonisobaric situations
arising with high flow rates, the Leva pressure drop equation was added to the model (Leva, 1959).
Various aspects of the process were optimized: the conversion and selectivity, by the choice of reactor bed depth,
flow rate and operating pressure; the dilution with inert
material and the optimal on stream time (Dumez, 1975).
Only the last aspect will be dealt with here.
The adiabatic reactor considered here has a bed depth of
0.80 m, a cross-sectional area of 1 m2, and contains 800 kg
of catalyst, undiluted. The initial catalyst temperature was
taken to be uniform and equal to the inlet temperature. In
industrial operation the initial temperature is not entirely
uniform after regeneration and evacuation. I t follows from
Figure 7, however, that the temperature profile is completely translated through the bed after 5 min so that the
following calculations and results are believed to be sufficiently representative, certainly for the longer dehydrogenation periods of the order of 45 min. The butadiene yield,
averaged over one complete cycle (including dehydrogenation, purge, regeneration and evacuation) is given by the
following formula

850-

i
I

1
840-

I
830 0

~~

OM

040

*
060

zlm)

Figure 7. Temperature profiles in the reactor.

tf

+ t,

The yield, I , is maximized by the optimal choice of the on

stream time tf. But t , is a complex function of t f , through
the coke content of the catalyst. The following expression
was chosen for t ,

t, = t,

+ t , + A@,

(39)

with t , the purge time and t , the evacuation time, both

equal to 2 min in industrial operation.
The linear relation between the regeneration time and
the average coke content of the catalyst is a reasonable approximation of the true relation: the rate of oxidation of
coke is proportional to the coke content and decreases as
the regeneration proceeds, but this is nearly compensated
by the temperature rise of the bed. A value of 0.05 h/% coke
was chosen for A.
In Figure 10, the yield I and the average coke content are
plotted vs. t,, the total cycle time for a reactor operating a t
600 "C, with inlet pressure of 0.30 ata and inlet flowrate of
20.4 kmol/m* h butene. I has a maximum for t , = 1.1 h.
The corresponding average coke content of the catalyst
amounts to 3.7%. This is much more than the content required to reheat the catalyst bed to the inlet gas temperature.
T o avoid excessive temperatures in the reactor after regeneration, the inlet temperature of the regeneration gas
would probably have to be monitored, for instance by admixing cold gas to the preheated stream. In industrial operation the dehydrogenation period is interrupted when the
amount of coke deposited is sufficient to provide, during
the regeneration, the heat compensating the heat lost during the on stream period (Hydrocarbon Process., 1971;
Hornaday et al., 1961; Thomas, 1970); 1.5 to 2% coke suffices for this purpose. According to Figure 10 the cycle time
is then 0.4 h, which is clearly suboptimal, not only for the
butadiene yield, but also for the selectivity. Indeed, after
Ind. Eng. Chem., Process Des. Dev., Vol. 15, No. 2, 1976

299

! \

1.015

1:OIO

0.01 1.005

t :0.025

*
0.2

0.6

0.4

0.8

Z(m)

Figure 8. Coke profiles in the reactor.

t (hr)

Figure 9. Outlet butadiene flowrate as a function of time.

0.1 h of dehydrogenation, the cumulative selectivity is only

0.776, after 0.3 h it amounts to 0.813, and after 0.9 h (the
value of tf corresponding to the optimum) to 0.855.

Acknowledgment

F. Dumez is grateful to the Belgian Nationaal Fonds

voor Wetenschappelijk Onderzoek for a grant over the period 1972-1974. This paper was presented a t the Sixtyeighth Annual Meeting of the American Institute of Chemical Engineers held in Los Angeles, Calif., Nov 16-20, 1975.
Nomenclature
= external surface of inert material, m2/m3
= external surface of catalyst, m2/m3
U ; k = contact surface between inert and catalyst, m*/m3
ci = specific heat of inert material, kcal/kg OC
ck = specific heat of catalyst, kcal/kg C
cpg = specific heat of gas, kcal/kmol C
hi = heat transfer coefficient of gas-inert, kcal/m* C h
ai
Uk

I
2

)
tC

Figure 10. Optimal cycle time.

300

Ind. Eng. Chem., Process Des. Dev., Vol. 15, No. 2, 1976

h k = heat transfer coefficient of gas-catalyst,

"c

kcal/m2
h
h,k = heat transfer coefficient inert-catalyst, kcal/m2 "C
h
kcBo = initial rate constant for coking from component B,
kg/kg of cat. h
~ H O= initial rate constant for dehydrogenation, kmol/kg
of cat. h
P B = partial pressure of component B, atm
r H o = initial reaction rate for dehydrogenation, kmol/kg
of cat. h
r H = reaction rate for dehydrogenation, kmol/kg of cat. h
rco = initial reaction rate for coking, kg/kg of cat. h
r c = reaction rate for coking, kg/kg of cat. h
T E = effective reaction rate, kmol/kg of cat. h
t = time, h
t , = evacuation time, h
t f = on-stream time, h
f'; = purge time, h
t , = regeneration time, h
t , = cycle time, h
u = superficial flow velocity, m/h
u = dilution catalyst bed
X D = conversion of butene into butadiene
z = reactor coordinate, m
AHO = frequency factor dehydrogenation, kmol/kg of cat.
h atm
Ac0 = frequency factor coking, kg/kg of cat. h
CB = concentration of component in the gas phase, kmol/
m3
CB,k = concentration in catalyst pores, kmol/m3
C, = coke content of the catalyst, kg of coke/kg of cat.
C t ~
= total concentration of active sites, kmol/kg of cat.
CL = concentration of free active sites, kmol/kg of cat.
CBL = concentration of sites covered with B, kmol/kg of
cat.
CSL = concentration of deactivated sites, kmol/kg of cat.
D B = effective diffusitivity of B, m2/h
D B ,=
~ molar diffusivity of B, m2/h
D g k = Knudsen diffusivity of B, m2/h
E H = activation energy for dehydrogenation, kcal/kmol
Ecg = activation energy for coking from B, kcal/kmol
F D = outlet butadiene flowrate, kmol/m2 h
(-AH) = heat of reaction, kcal/kmol
I = objective function, butadiene production averaged
over cycle time, kmol/h
K = equilibrium constant for dehydrogenation, atm
K , = equilibrium constant for reaction step i
L , = length of pores, m
M I = molecular weight of component I, kg/kmol
R = gas constant, kcal/kmol K
R e = equivalent radius of catalyst particle, m

SH =

mol of butadiene produced per mol of butene converted, averaged over on-stream time
T = gas temperature, "C
T k = temperature catalyst particle, "C
Ti = temperature inert particle, "C
T B = generalized modulus according to Bischoff
a = deactivation parameter, kg of cat./kg of coke
t k = pore volume of catalyst, m3/kg of cat.
t = void fraction in reactor
7 = effectiveness factor
p k = specific weight of catalyst, kg/m3
pi = specific weight of inert material, kg/m3
'T = tortuosity factor on the pores
(PH = deactivation function for dehydrogenation
(pc = deactivation function for coking

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Received for reuiew J u n e 30, 1975

Accepted October 28,1975

Ind. Eng. Chem., Process Des. Dev., Vol. 15, No. 2, 1976

301