2088 Ind. Eng. Chem. Res.

1992,31,2088-2093

Isobutane Dehydrogenation Kinetics Determination in a Modified Berty

Gradientless Reactor
Andreas G. Zwahlen and John B. Agnew*
Department of Chemical Engineering, The University of Adelaide, S.A. 5001, Australia

A standard Berty gradientless reactor, designed to operate at temperatures up to 350 "C and pressures
between 3 and 35 bar, has been successfully modified for operation up to 600 "C and at atmospheric
pressure without appreciable interparticle transport resistance. The reactor is used to establish the
kinetics of the catalytic dehydrogenation of isobutane at 530-570 "C and 1 bar, using a concen-
tration-control system to decouple the effects of concentration and activity on reaction rate. A
single-site LHHW model is found to provide a good fit to initial rate data. Catalyst deactivation
data are also presented for dehydrogenation and coking reactions.

Introduction
The catalytic dehydrogenationof isobutane to isobutene
is an industrial reaction of considerable importance, e.g.,
for the production of methyl methacrylate, butylphenols,
tert-butylmercaptans, and particularly methyl tert-butyl
ether (MTBE) for use as a gasoline octane enhancer. The
reaction is endothermic and proceeds at an appreciable
rate with high product yield in the temperature range
500-600 "C and at low pressure (ca.1 bar). Rapid catalyst
deactivation occurs as temperature is increased above 550
"C.
Although a large number of investigations of the dehy-
drogenation of n-butane and n-butene have been reported
since the early work of Dodd and Watson (1945),few pa-
pers have been published on isobutane dehydrogenation.
Happel et al. (1973),using a Houdry catalyst (20% chro-
mia) in a continuous-flowreactor in the temperature range
377-490 "C,found that the best fit to their data was given
by an eight-parameter Langmuir-Hinshelwood-Hougen-
Watson (LHHW) model with a single rate-controlling step,
viz., the chemisorption of isobutane. Masson et al. (1979)
used a catalyst of 7.5% chromia on alumina in a flow
reactor at 533-596 "C to determine a four-parameter in-
itial-rate correlation without consideration of deactivation.
The experimental determination of intrinsic and deac-
tivation kinetics at temperatures above 500 "C and at low
pressure is a difficult problem. Well-mixed internal-recycle
("gradientless") reactors have become increasingly pre-
ferred for solid-catalyzedgas reaction studies because of
their favorable features, viz., high conversion levels, iso-
thermality, and constant gas composition. However,
available reactors are generally limited to lower-tempera-
ture and higher-pressure conditions than apply for iso-
butane dehydrogenation.
This paper is concerned with (a) the development of an
appropriate experimental system for studying the kinetics
of high-temperature, low-pressure, solid-catalyzed gas re-
actions and (b) use of the system to establish intrinsic and
deactivation kinetic relations for isobutane dehydrogena-
tion on commercial Hmhaw chromia-on-aluminacatalyst.
Reactor Development
In a general review paper, Bennett et al. (1972)high-
lighted the suitability of internal recycle rectors for tran-
sient kinetics experiments. Weekman (1974)pointed out
the advantages, disadvantages, and limitations of the
commonly employed types of laboratory reactors, with the
stirred, contained-solids reactor receiving high marks.
Berty (1984),in a later paper, emphasized the particular
features of internal recycle rectors for testing catalysts and
for kinetic studies. Reaction in such a system involves no
significant interparticle concentration or temperature
263i-2oaa$o3.00/0 0 1992 American Chemical Society
oaaa-5aa5/92/
gradient over the bed. "Intrinsic" kinetic data can thus
be obtained, free of external heat and mass-transfer lim-
itations, coke gradients, etc., which would normally be
encountered in fixed-bed systems.
Rapid catalyst deactivation poses an additional problem.
When the rate of change of catalyst activity is concen-
tration-dependent, analysis of experimental results be-
comes extremely difficult. Levenspiel (1972)proposed the
use of a well-mixed flow reactor with regulated feed rate
to ensure constant concentration in the reactor in order
to decouple activity and concentration effects on reaction
rate. In complex reaction systems, adjusting the flow rate
does not necessarily ensure constant composition. How-
ever, in many cases the influence of the main reaction is
so great as to overshadow the side reactions. Only a few
studies have been reported which use this technique
(Petersen and Pacheco, 1984;Christoph and Beams, 1985;
Broucek et al., 1986).
Internal-Recycle Reactor. As no commercially
available recycle reactor for operation above 500 "C and
at low pressure was known to the authors, it was decided
to modify a Berty reactor (designed for temperatures up
to 350 "C and pressures up to 35 bar) supplied by Design
Technology Inc. of Pittsburgh, PA. Berty (1984)recom-
mended a lower pressure limit of 3 bar for his reactor
because of the difficulty of maintaining adequate mass
velocities at lower pressure and correspondingly low gas
densities.
The measured internal gas flow rate produced by ita
turbine was determined to be insufficient for gradientless
operation at 1 bar and 600 "C. To increase the gas flow
rate, two modifications were made.
(i) The air motor, designed for a maximum shaft speed
of 2500 rpm, was replaced by a direct-flanged three-phase
motor (0.55kW) driven by a variable speed control device
(Parajust F) to permit an increase in maximum shaft speed
to 4500 rpm. This resulted in a 3.5-fold increase in the
pressure head generated (see Figure 1).
(ii) The original eight-blade single-stage turbine was
replaced with a specially designed three-stage turbine (see
Figure 2). The first stage radial turbine was designed with
enlarged vanes positioned at an angle of 45"; the flow
guiding channel was machined in such a way as to reduce
internal drag. Two axial stages with eight vanes at 45"
were added. Three sets of static vanes (eight blades at
-45") were placed at the exit of each stage. In order to
reduce the internal back-flow (which became more im-
portant as the pressure produced by the turbine was in-
creased), a complex labyrinth seal was incorporated into
the system.
Turbine and drive shafts were carefully statically bal-
anced to increase the life of the carbon bearings to an

50 -
Modified 1 -Stage Turbine
0 1000 2000 3000 4000
Turbine Speed (rpm)
Figure 1. Pressure head generated by turbines.
I 0
,,,;' i ,$','
M M
Figure 2. Three-stage turbine arrangement.
acceptable level. The outer magnet was axially adjusted
to keep the drive shaft and turbine assembly floating.
Bronze impregnated carbon (MY3D Morganite) was used
as bearing material in order to remove excess heat from
the ehaft/bearing system. The whole drive assembly was
additionally cooled by a constant flow of compressed air.
These modifications enabled the generated pressure
head to be increased by a factor of 10 (at 4500 rpm) over
the original turbine (at 2500 rpm) (Figure 1).
In order to minimize the effects of homogeneous and
surface reaction at elevated temperature, provision was
made for increasing the catalyst/reactor surface ratio,
without increasing the catalyst bed depth (and hence
pressure drop). This was achieved by enlarging the cata-
lyst bed diameter from 50 to 60 mm, resulting in a 40%
increase in catalyst volume at constant bed height.
Tracer studies at turbine shaft speeds of 2000 and 3000
rpm indicated that perfect mixing could be assumed. A
step change from argon to nitrogen was introduced at the
feed inlet, and the exit gas composition was monitored by
an on-line mass spectrometer (see Gas Analysis in the
Experimental Section). Semilog plots of fractional con-
centration versus time are shown in Figure 3 for different
gas flow r a t e and turbine shaft speeds. The corresponding
theoretical lines for perfect mixing, based on an estimated
reactor void volume of 0.66 L, showed excellent fit.
Ind. Eng. Chem. Res., Vol. 31, No. 9, 1992 2089
5000
0 2000 4000 0 10 20
Turbine Speed (rprn) Gas Velocity (rnis)
Figure 4. Typical relationships between superficial gas velocity,
pressure drop and turbine shaft speed (W = 70 9).
Heating System. The original 600-W top-band heating
system was not powerful enough to maintain the higher
temperature levels and was replaced. An annular stainless
steel ring was tightly fitted around the outside of the top
part of the reactor, accommodating eight equally spaced
heat cartridges (Super Watt Cartridge, 3/8 in. X 1.5 in., 160
W, by Helios), to give a total power rate of 1280 W. The
bottom heating arrangement was also modified, and more
suitable high-temperature cartridges were installed (Red
Hotrods, 0.25 in., by Helios). Additional insulation was
installed.
Temperature control to within f0.5 O C was achieved
with the top heater under Variac-adjustable steady load
and the bottom heater controlled by a microprocessor-
based Eurotherm 818 controller (self-adaptive tuning al-
gorithm) driving a Eurocube Thyristor Unit 424 solid-state
contactor. With this system, the temperature difference
across the catalyst bed could be kept to 1 "C.
Internal Flow Rate. An indirect method was used
(Berty, 1984). The catalyst basket (plus catalyst) was first
placed into a specially designed flow device in which the
flow rate was measured by a rotameter and the pressure
drop was measured by a highly sensitive differential ma-
nometer (Askania,fO.l mm of water). Measurements were
then made in the reactor of the pressure drop over the
catalyst bed as a function of shaft speed and bed height
under normal operating conditions. Plots of pressure drop
versus shaft speed at various temperatures with a set
amount of catalyst were obtained; these were then used
in conjunction with plots of presaure drop versus superficial
gas velocity to give the required overall relationship.
Typical plots are shown in Figure 4.
Experimental Section
Gas Analysis. A Hewlett-Packard Model 5830A gas
chromatograph was used for accurate analysis. The col-
2090 Ind. Eng. Chem. Res., Vol. 31, No. 9,1992
Table I. Prowrties of Harshaw Catalyst C r 0211 T 5/32
surface area, m2g-l 50
pore volume, cm3 g-' 0.29
external surface area, cm2 g-' 7.61
average bed density, g cm-3 1.2
pellet density, g 1.99
pellet porosity 0.58
shape cylindrical
diameter, cm 0.40
length, cm 0.40
umn used was VZ-10 60/80,3 m in length to give good
separation of hydrogen and methane. A thermal con-
ductivity detector was employed, with nitrogen as the
carrier gas. The sample time was 14 min. For dynamic
gas analysis, a VG Micromass 6 mass spectrometer was
used. Details of the gas sample inlet system are given by
Zwahlen (1989).
Readout and Control System. "his consisted of a data
logger, PC, and appropriate software. The amplified
analog electron multiplier output signal (0-10 V) was
converted into a digital signal and transferred to the PC.
Concurrently the PC sent, via the data logger, an analog
signal (0-10 V) to the programmed power supply where
it was converted to a 0-5-V signal which was applied to
the acceleration plates of the ion source. The sample-line
pressure gauge output signal (0-5 V) was digitized and
transferred to the PC, from which a signal was sent via the
logger to the reactor inlet mass flow meter/controller
(Brooks Instruments B.V. Model 5800 TR) to adjust the
set point. Two reactor thermocoupleswere also connected
with the logger and PC.
PC Software. Specific software was developed for mass
spectrometer calibration,reactor control, and monitoring.
The mass spectrometer was calibrated by introducing
pure gases and noting their relative peak heights at certain
m/e ratios. Software was written to solve the relevant set
of simultaneous equations to determine component sen-
sitivities and cracking pattern coefficients of pure com-
ponent gases periodically and also to determine partial
pressures of components in reaction gas mixtures.
Concentration control was effected by set-point ad-
justment of the isobutane flow controller via a serial-
line-driven D/A converter. The set point was determined
using a proportional-integral-derivative(PID) control al-
gorithm. The control variable was the ratio of concen-
trations of isobutene and isobutane in the reactor. (This
ratio was used, rather than a single partial pressure, be-
cause of the inability of the mass spectrometer to deter-
mine hydrogen partial pressure). Software was also written
for the monitoring, recording, and displaying of particular
operating conditions.
Materials. The isobutane used was instrument grade
(99.9%) supplied by Matheson Gases Inc. through CIG
Ltd.,Adelaide. The catalyst used was CT0211 T 5/32
chromia-alumina catalyst (Cr20318%; ZrOz0.25%; A1203
82% (w/w)) from Harshaw Chemie BV Holland, supplied
through Brown and Dureau Ltd.,Adelaide. The physical
properties are summarized in Table I.
Procedure. A weighed quantity of dried catalyst (20-50
g) was placed in the catalyst basket, and the reactor was
closed up. The reactor was purged with nitrogen, the
heating system was activated, and the turbine motor was
initially set to 500 rpm. When the temperature had
reached 300 "C, nitrogen flow was replaced with hydrogen
for 2 h to reduce and activate the catalyst. The turbine
speed was gradually increased as the temperature was
raised to the required operating level. The computer
control system was initialized, and the mass spectrometer
and GC systems were set in operation.
0.15
1
0.6
.
0.7 0.8 0.9 1
P A bar1
Figure 5. Homogeneous rate of reaction of isobutane (mol/h).
Isobutane flow was initiated via the PC. GC analysis
of the exit stream was performed at 14-min intervals as
a check on the mass spectrometer. Exit flow was checked
every 10 min using a soapbubble meter. At the end of the
run, isobutane flow was replaced with nitrogen and the
heaters were turned off. Runs were also carried out
without catalyst at 530,550, and 570 "C to establish the
extent of surface and homogeneous reactions. For the
purpose of this study, these were lumped together; their
combined effect will subsequently be referred to as
'homogeneous reaction".
Results
For constant feed flow rate, the exit stream concen-
trations change with time as the catalyst deactivates. A
dynamic mass balance for pure isobutane (A) feed yields
For slow deactivation, the accumulation term can be ne-
glected. The rate of coke formation is obtained from an
overall dynamic mass balance:
For constant exit composition the feed flow rate is con-
trolled to keep the exit stream compositions constant so
that reduction of the feed flow counteracts the loss of
catalyst activity and during the whole run the catalyst is
exposed to the same gas composition. Hence
The rate of coke formation is again given by eq 2. It should
be noted that the heterogeneous rates are expressed as
moles per hour per gram of catalyst and homogeneous rates
as moles per hour in the above equations.
Homogeneous Kinetics. Figure 5 shows rate of reac-
tion of isobutane against partial pressure at three tem-
peratures, in the absence of catalyst. From the limited
data, the apparent activation energy for homogeneous
reaction was estimated to be about 275 kJ/mol.
Heterogeneous Kinetics. At three temperatures, viz.,
530,550, and 570 "C, and over a range of concentrations
to establish reaction rate data, 27 runs were carried out.
Corrections were made for a homogeneous reaction rate
which was significantlylower than the heterogeneous rate;
expressed on a similar basis, heterogeneous rates were
 Ind. Eng. Chem. Res., Vol. 31, No. 9, 1992 2091

Table 11. Kinetic Models for the Initial Reaction Rate

no. of
model -rA params catalytic step/remarks
I 4 power law
I1 10 A + S Y AS, adsorption on single site
A + S * AS, hydrogen term neglected
I11
IV
V
VI
VI1
10
8
10
8
8 - -
AS + S * ES + HS, surface reaction on dual sites
AS + S ES + H, surface reaction, on single site
ES E + S, HS * H + S, desorption
ES E + S, desorption
VI11 8 adsorption of A
IX 4 two rate-determining steps, adsorption and surface reaction
2 power law (irreversible)
7 power law

0.02 Table 111. Deactivation Models

h model deactivation function,

+ A +i A , +
Table IV. Deactivation Model Parameter Estimation
0.01
model m, x IO4 m2 m, x IO-" m, x2 x 103
D1 1.6 150 1.34
D2 1.2 148 1.28
D3 2.2 154 2.0 128 1.19

4
tL O
0 40 80 120
Time [nun] 3. 0.75

Figure 6. Catalyzed rate of reaction of isobutane and gaa partial &

pressures against time at T 5 550 "C (run 187). A
0.5-
generally at least 1 order of magnitude greater than ho- V
C
mogeneous rates. Initial reaction rates were obtained by a
extrapolation to zero time. Plots of partial pressures and 8 0.25-
reaction r a t a for a typical run (187)are shown in Figure
6. An exponential decay function was found to give an
excellent fit to the rate data: 0
0 20 40 60 80 100 120 140 160
-rA = (-rA)ht exp(-bt) (4) Time (min.)
For run 187 the correlation coefficient was 0.988. For Figure 7. Coke content of catalyst against time.
23 runs, the correlation coefficient was greater than 0.9;
the lowest value was 0.71 (run 189). therefore be theoretically related to coke deposition which
A set of 11 kinetic models was examined for their can in turn be related to the concentration of hydrocarbon
suitability in fitting the experimental initial rate data (27 species in the gas phase (Froment and Bischoff, 1961,
points). These are listed in Table 11. Model X,the sim- 1962). Three models were examined (see Table 111).
plest, was used by Otake et al. (1965)for n-butane dehy-
drogenation. Models 11-VI11 are LHHW-type models
based on various assumptions for the reaction A R +
S. Model VIII, proposed by Happel et al. (1973)for iso-
- Model D1 was concentration-independent; in model D2,
the first-order concentration dependencies on isobutane
and isobutene were assumed to be equal; and model D3
assumed unequal dependencies. Parameter estimation
butane dehydrogenation, assumes that chemisorption of yielded the values shown in Table IV.
isobutane is the rate-controlling step. Model IX was de- Limited measurements were also made of coke depos-
rived by Maeeon et al. (1979)to model the initial reaction ition. The 5 experiments were conducted at identical
rate of isobutane dehydrogenation. conditions, viz., T = 550 O C , PA = 0.62,p E = 0.184,and
Model parameters were determined using established pH= 0.184. In each case, 20 g of fresh catalyst was used;
nonlinear least-squares algorithms (Simplex and Mar- the reactor was run under identical Conditions for different
quardt). Details are given by Zwahlen (1989). times (viz., 30,60,90,120, and 150 min). The catalyst was
Deactivation Kinetics. Catalyst activity is defined as removed and the carbon was burned off in a muffle furnace
@(T,C,t)= r(T,C,t)/r(T,C,O) (5) to determine coke content. A plot of coke content against
time is shown in Figure 7,with a curve of best fit shown.
The dependencies of activity on temperature, concen- Activity functions for dehydrogenation and coking reac-
tration, and time must be determined. The experimental tions were determined as a function of coke concentration
activity decay observed earlier is in agreement with the (mass fraction):
Herington-Rideal first-order decay reported for dehy-
drogenation of paraffins on chromia-alumina catalyst. @A = 1- 68Cc (6)
Deactivation is assumed to occur primarily by coke de-
position from hydrocarbon cracking reactions. Activity can = exp(-148Cc) (7)
2092 Ind. Eng. Chem. Res., Vol. 31,No. 9,1992
- 1
t A i E I ference between the models is apparent, with generally
i / :
0 0.04 0.08
-rA experimental
Figure 8. Predicted versus experimental reaction rates for three
models (mol/(h E)).
Discussion
Modified Reactor. The modified Berty reactor per-
formed well under the severe temperature conditions.
Impeller shaft speed was kept to 2600 rpm, which was
sufficient for minimizing the interparticle diffusional re-
sistances and at the same time for minimizing bearing
wear. However, the heating system and the reactor closing
mechanism showed substantial wear and should be re-
constructed using better high-temperature-resistant ma-
terials. The modified turbine/catalyst-bed configuration
in this design would provide a very versatile laboratory
reactor for a range of reactions.
Concentration Control. Automatic manipulation of
the gas feed rate was effective in maintaining the con-
centrations of reacting species at constant values during
the runs despite fairly rapid catalyst deactivation (see
Figure 6).
Transport Limitations. Runs were carried out at
identical reaction conditions but with two different shaft
speeds, e.g., 1500 and 2700 rpm. An additional run was
carried out with catalyst pellets split in half. Reaction rate
profiles were virtually identical, indicating the absence of
significant interphase and intraparticle diffusional re-
sistances. This was confirmed by theoretical calculations
of temperature difference between bulk gas and catalyst
external surface (approximately 1 K); the estimated iso-
butane concentration difference was also small (0.01 bar),
and the Weisz-Prater modulus (ca. 0.5) was in the non-
limiting region (Satterfield and Sherwood, 19631,allowing
for the expected error in estimating effective diffusivity.
Catalyst Regeneration. The same batch of catalyst
was used in three consecutive experiments at identical
conditions, with intermediate regeneration in a furnace
with oxygen-enriched air. No significant loss of activity
was detected, although this would most likely not have
been the case had a greater number of regenerations been
carried out.
Model Fit. All initial-rate models except IX and X
fitted the data reasonably well, based on a minimum-
sum-of-squares criterion (including experimental error).
The model with the smallest residual sum of squares (x2)
was taken to be the best. All of the hyperbolic models had
values of x2 around 4 X lo4 and a standard deviation of
around 14%. The power-law models I and XI had higher
standard deviations, viz., 23 and 1970,respectively, while
the simple power-law models M and X had standard de-
viations of 36%. The best fit was obtained with LHHW
model 111,which was based on the assumption of adsorp-
Table V. Final Kinetic Model
- P@H/K)@A/(~
-rA = k ( p ~ + KE@@H + K@E) (mol(h E))
-(d@A/dt) = + ~$E)@A
where
k = 8.9 X 106 exp(-112/RT)
K = 1.4 X lo6 exp(-117/RT)
KEH 1.2 X 10' exp(-79/RT)
KE = 2.5 X lo6 exp(-87/RT)
kl = 2.2 x 10e exp(-154/RT)
k2 = 2.0 X 10s exp(-128/RT)
tion of isobutane on a single site (model II),neglecting the
denominator hydrogen term. Predicted versus measured
rates are shown in Figure 8 for models 1-111. Little dif-
good fit to all data over the range of experimental rates
covered. Model VI11 of Happel et al. (1973)also gave a
reasonable fit with a standard deviation of 14.4% (cf.
12.7% reported by Happel). The other isobutane-dehy-
drogenation model M due to Maason et al. (1979) was not
suitable (standard deviation 35% 1. Dual-site surface-re-
action model IV,which was found suitable by Dumez and
Froment (1976)for 1-butene dehydrogenation, was also
found to be suitable for isobutane dehydrogenation.
Deactivation models incorporating concentration de-
pendency showed improved fit to the data. This is con-
sistent with the assumption that coke formation depends
on the concentrations of both isobutane and isobutene.
Model D3,which amumes unequal dependencies, gave the
best fit to the data.
Final Model. The complete model, incorporating
catalyst activity function and the full set of parameter
values, is shown in Table V. Parameter estimation was
based on 243 data points. Standard deviation was esti-
mated as 14.7%.
Conclusions
(1) The standard Berty reactor was successfully modified
for gradientless operation at temperatures up to 600 OC
and at pressures close to atmospheric. This represents a
substantial extension to the recommended 350 OC maxi-
mum temperature and 3 bar minimum pressure limits.
(2)Concentration control, by manipulation of the gas
feed rate, was found to be an effective way to decouple the
effects of concentration and activity on reaction rate under
fairly rapidly deactivating conditions.
(3)A LHHW model based on adsorption of isobutane
on a single site was found to give the best fit to experi-
mental isobutane dehydrogenation data.
(4)A firsborder deactivation model with concentration
dependency provided the best fit to experimental data.
Acknowledgment
A grant from the Australian Research Grants Committee
and support from Amt fiir Ausbildungsbeitriige, Basel,
Switzerland, for A.G.Z., are gratefully acknowledged.
Nomenclature
a = constant
b = parameter defined in eq 4
C = concentration (mol/L, g/g)
E = activation energy (kJ/mol)
F = molar flow rate (mol/h)
k = reaction rate constant
K = equilibrium constant
m = deactivation model parameter
M = molecular weight
p = partial pressure (bar)
r = reaction rate (mol/(h g), mol/h or g/g)
R = gas constant
 I n d . Eng. Chem. Res. 1992,31,2093-2103 2093

T = temperature (Kor "C) Wasserstoff zu Methan. Chem. Eng. Technol. 1985,57,775-778.

t = time Dodd, R. H.; Watson, K. M. Process Design of Catalytic Reactors-
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u = volumetric flow rate (L/h) Chicago Meeting, Dec 16-19, 1945; AIChE: New York, 1945.
Dumez, F. J.; Froment, G. F. Dehydrogenation of 1-Butene into
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Froment, G. F.; Bischoff, K. B. Non-steady-state behaviour of fixed
@ = catalyst activity bed catalytic reactors due to catalyst fouling. Chem. Eng. Sci.
x2 = s u m of squares of deviations 1961,16,189-201.
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A = isobutane Chem. Eng. Sci. 1962,17,105-114.
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Triigerkatalysator fcU die Hydrierung von Restkohlenmonox in Accepted June 16, 1992

Kinetics of Vacuum Gas Oil Cracking on a Zeolitic Catalyst

Jo F. Coopmans, Pieter Mars, and Rokus L. de Groot*
Physical Chemistry Department, Corporate Research, Akzo Research Laboratories Arnhem, P.O. Box 9300,
6800 SB Arnhem, the Netherlands

Pulse experiments on the cracking of gas oil as a function of the reaction time and the oil partial
vapor pressure are described. The catalyst activity decay is shown to be negligible in the pulse
conditions. However, the shape of the pulse is important since the oil conversion turns out to be
higher a t lower oil pressures. A kinetic expression is given on the basis of a Langmuir equation,
in which the adsorption of the products dominates. Therefore, cracking is slowed down by the
presence of heavier aromatics, including those formed from the naphthenes in the feed by hydro-
gen-transfer reactions. The kinetics have been extended to account for the composition of the feed.
In this form it is pmible to correlate the conversions of 16 feed charges of very different composition
as obtained in a flow reador by Nace and co-workers. The second-order kinetics so frequently used
in this field can be regarded as an approximation of the equations derived in this work.

1. Introduction sometimes fmt-order kinetics (hribas et al., 1987;Corma

The kinetics of the cracking of hydrocarbons has been
formulated in different ways. The cracking of pure hy-
drocarbons has been described with a first-order kinetic
equation (Voge, 1958;Nace, 1969) or using a Langmuir
type of equation (Pansing, 1965;Abbot and Wojciechowski,
1987). All authors using flow reactors are confronted with
the deterioration of the catalyst by coke formation. Hence,
they are forced to combine the search for an accurate
description of the cracking rate with an investigation into
the influence of catalyst deactivation. For instance, the
conclusion of Abbot and Wojciechowski (1987)that the
olefins retard the cracking process is not necessarily true,
since this interpretation can be considered equivalent to
the supposition that the catalyst activity remaining after
fouling is inversely proportional to the oil conversion. For
the cracking of hydrocarbon mixtures, e.g. oil fractions,
0888-5885/92/2631-2093$03.00/00 1992 American Chemical Society
et al., 1984) but more often second-order relations can be
found in the literature (Weekman, 1968;Nace et al., 1971;
Voltz et al., 1971;Gross et al., 1974). The occurrence of
second-order kinetics with respect to the time of reaction
was argued by Blanding (1953)to be caused by the ex-
pansion of the gas stream by the reaction products. Voge
(1958)developed a kinetic expression based on this as-
sumption. He also elaborates on the kinetics on the basis
of the Langmuir adsorption of reactants and products and
advocates the expression
-[ln (1 - XI]- a l X = ka,(w/F)
the coefficients a being complicated functions of the ad-
sorption coefficients and the partial pressures. This
equation has rarely been used in the literature, and more
often the second-order kinetics in time has been applied.