Ind. Eng. Chem. Res.

2002, 41, 5619-5626 5619

Kinetic Modeling of Dehydrogenation of Isobutane on Chromia/

Alumina Catalyst
Sanna M. K. Airaksinen,* M. Elina Harlin,† and A. Outi I. Krause
Helsinki University of Technology, Department of Chemical Technology, P.O. Box 6100,
FIN-02015 HUT, Finland

The kinetics of isobutane dehydrogenation was studied on a chromia/alumina catalyst developed

for fluidized-bed operation. The dehydrogenation activity measurements were carried out in a
laboratory-scale plug-flow reactor at 520-580 °C under atmospheric pressure. Several kinetic
models were derived from different mechanisms, and the suitability of the models in describing
the rate of the dehydrogenation reaction was tested. The results of the kinetic modeling suggested
that the rate-determining step is isobutane adsorption, possibly on a pair of chromium and oxygen
ions. A satisfactory description of the reaction rate depended on inclusion of the isobutene and
hydrogen adsorption parameters in the mathematical model. The activation energy of the
dehydrogenation reaction was estimated to be 133-142 kJ/mol.

Introduction in crystalline chromia. On alumina-supported catalysts,

Light alkenes, such as propene and butenes, are
important intermediates in the manufacture of polymers
and chemicals. The most selective way to produce these
short-chain alkenes is the direct catalytic dehydroge-
nation of the corresponding alkanes. Industrial dehy-
drogenation processes use chromia- or platinum-based
catalysts generally supported on alumina and promoted
with alkali metals.1 The structure and activity of
chromia catalysts have been studied extensively in an
attempt to understand better how the properties of
supported chromia influence the dehydrogenation
activity.2-10 However, an understanding of the system
also requires information about the reaction mechanism.
The kinetics and mechanism of alkane dehydrogena-
tion on chromia/alumina catalysts have been explored
in various publications.11-19 However, the findings of
these studies have not always been in agreement. Not
only different mechanisms but also different rate-
determining steps and, thus, different kinetic models
have been proposed. The rate-determining step in the
dehydrogenation of isobutane has been suggested to
involve alkane adsorption,15,16 whereas in the dehydro-
genation of propane and n-butane, it has been proposed
to involve the surface reaction of the adsorbed alkyl
group.11,12,18,19 Furthermore, results of tracer studies
with 13C-labeled isobutane and deuterium on chromia
gel20 and with deutero-propane on chromia/alumina17
suggest a mechanism with the surface reaction as the
slow step.
The dehydrogenation activity of chromia catalysts is
most often attributed to coordinatively unsaturated Cr3+
ions.3-10 Varying with the sample properties and treat-
ment conditions, three types of Cr3+ have been observed:
2,3,5,6 (i) redox Cr3+ formed in the reduction of Cr5+ and
redox Cr3+ is the most abundant species at low chro-
mium contents, and its amount stabilizes to about 2-3
atoms of Cr/nm2 (2-3 wt % chromium, depending on
the support surface area) for total chromium contents
above 5 atoms of Cr/nm2 (4-8 wt %).5,6,8 The amount of
amorphous chromia increases with the total chromium
content, and crystalline chromia is mainly observed, by
X-ray diffraction, above about 8-10 atoms of Cr/nm2 (6-
16 wt %).5,6,8 It has been suggested that both redox and
nonredox Cr3+ are active in dehydrogenation,5,6 whereas
crystalline chromia is less active.6
In addition to the Cr3+ ions, surface oxygen ions might
also participate in the reaction.3,9,10,21,22
Dehydrogenation might involve a stage where the
alkane adsorbs and dissociates, in one or two steps, onto
a pair of chromium and oxygen ions to give an alkyl
group bonded to surface chromium and a hydrogen atom
bonded to surface oxygen,3,21,22 as schematized in eq 1
Cr-O + R-H f R‚ ‚ ‚Cr-O‚ ‚ ‚H (1)
In kinetic modeling studies, the active site of the
catalyst has generally been described as a single ion.
However, if both the chromium and oxygen ions take
part in the reaction, as has been suggested, the active
site should be described as a Cr-O pair.
In this work, the dehydrogenation of isobutane on a
chromia/alumina catalyst was studied to clarify the
reaction kinetics of alkane dehydrogenation. Kinetic
models were derived on the basis of different mecha-
nisms and rate-determining steps, and the suitabilities
of the models in describing the measured dehydroge-
nation activities were tested.

Cr6+ present on oxidized samples, (ii) nonredox Cr3+ in Experimental Section

an amorphous chromia phase that is present in both
reduced and oxidized samples, and (iii) the Cr3+ present Materials. The chromia/alumina catalyst used in the
study was a sample developed for fluidized-bed opera-
* To whom correspondence should be addressed. E-mail tion. The chromium content of the catalyst was 12 wt
address: airaksinen@polte.hut.fi. Fax: +358-9-451 2622. %, and the average particle size was 96 µm. The gases
† Current address: Fortum Oil and Gas Oy, P. O. Box 310, were supplied by Aga, and their purities were N2,
FIN-06101 Porvoo, Finland. 99.999%; air, 99.5%; H2, 99.999%; i-C4H10, 99.95%; and
10.1021/ie020371j CCC: $22.00 © 2002 American Chemical Society
Published on Web 10/17/2002
5620 Ind. Eng. Chem. Res., Vol. 41, No. 23, 2002
Table 1. Reaction Conditions Applied in the Kinetic
Activity Measurements
feed composition
amount of WHSV T i-C4H10/H2/N2
series catalyst (g) (h-1) (°C) (mol:mol:mol)
1 0.1 15, 30 520-580 1:0:1, 3:0:7
2 0.2 7.5, 15, 30 520-580 1:0:1
3 0.1 15, 30 520-580 1:1:1, 1:1/2:1, 1:1/4:1
Ar, 99.999%. Nitrogen and argon were purified with
Oxisorb (Messer-Griesheim).
Dehydrogenation Equipment and Analytical
Methods. The dehydrogenation activities were mea-
sured in a continuous-flow fixed-bed microreactor. The
catalyst sample (0.1 or 0.2 g) was loaded between two
layers of silicon carbide into a quartz-glass reactor with
a 7-mm inside diameter. The catalyst bed length was 3
or 6 mm for 0.1- or 0.2-g loading, respectively. The
reaction temperature was monitored with a thermo-
couple in the catalyst bed, and the flow rates of gases
were regulated with mass flow controllers.
The reaction products were analyzed on-line with a
Gasmet Fourier transform infrared (FTIR) gas analyzer
(Temet Instruments Ltd.) equipped with a Peltier-cooled
mercury-cadmium telluride detector and with an HP
6890 gas chromatograph (GC) equipped with an HP
PLOT/Al2O3 “M” column and a flame ionization detector.
The FTIR spectra were recorded in the wavenumber
range 4000-850 cm-1 with a resolution of 8 cm-1 and
a scanning rate of 10 scans/s. The analysis cuvette (9
cm3) was maintained at constant temperature (175 °C)
and pressure (1.03 bar). The spectra were measured
every 3 s during the first 2 min on stream, every 5 s
during the next 2 min, and every 30 or 60 s thereafter.
The compounds analyzed by FTIR spectroscopy were
methane, ethane, ethene, propane, propene, n-butane,
isobutane, 1-butene, cis-2-butene, trans-2-butene, 1,3-
butadiene, isobutene, benzene, toluene, carbon monox-
ide, carbon dioxide, and water. The composition of the
product stream was calculated by the classical least-
squares multicomponent analysis method using an
analysis program (Calcmet, Temet Instruments Ltd.)
with calibration spectra for the measured compounds.
The method for analyzing light hydrocarbons by FTIR
spectroscopy has been described in detail elsewhere.23
Activity Measurements. Three series of activity
measurements were carried out at atmospheric pressure
(1.03 bar) under different reaction conditions. As de-
scribed in Table 1, the catalyst loading, reaction tem-
perature, isobutane weight hourly space velocity (WHSV),
and molar ratios of isobutane to hydrogen and to
nitrogen in the feed were varied in the experiments.
Each series consisted of about 50 (pre)reduction-
dehydrogenation-regeneration cycles with the same
catalyst load. During the first 15-20 cycles, the catalyst
activity stabilized to a constant level. Then, the kinetic
measurements were started. The stability of the catalyst
activity was verified regularly with standard experi-
ments. The stabilization and standard dehydrogenation
stages were carried out at 580 °C and a WHSV value of
15 h-1. The isobutane feed was diluted with nitrogen,
the molar ratio of isobutane to nitrogen being 1:1. No
hydrogen was added to the feed. Some experiments were
performed with argon instead of nitrogen as the inert
gas.
The catalyst was reduced either (i) with hydrogen
before the dehydrogenation stage or (ii) with isobutane
during the first few minutes on the isobutane stream.
The hydrogen prereduction was done at 590 °C with
10% H2/N2 and a reduction time of 15 min. The reduc-
tion products were analyzed by FTIR spectroscopy. The
influence of hydrogen prereduction on the catalyst
activity and product distribution was studied in cycles
1-12: cycles 1-6 and 12 did not include a prereduction
stage, whereas cycles 7-11 did. The kinetic measure-
ments were done with the prereduced catalyst com-
mencing at about cycle 16. During the dehydrogenation
stage, the isobutane feed was continued for 11 or 15 min.
The reaction products were monitored by FTIR spec-
troscopy for the first 6 min on stream, a GC sample was
taken after 8 or 10 min, and the FTIR analysis was then
continued. The catalyst was regenerated after the
dehydrogenation stage with 2% O2/N2 for 2 min, with
5% O2/N2 for 2 min, and with 10% O2/N2 for 30 min.
The amounts of the regeneration products, carbon
oxides and water, were determined by FTIR spectros-
copy. The amount of coke deposited on the catalyst
during dehydrogenation was calculated from the mea-
sured amounts of carbon oxides.
Thermal reactions in the system were investigated
by replacing the catalyst with silicon carbide but
otherwise implementing the dehydrogenation procedure
as usual. Internal mass transfer was considered with
the Weisz-Prater criterion, and external mass transfer
by conducting dehydrogenation experiments with two
catalyst loadings at the same reaction temperature and
WHSV value.
Calculation of Conversions and Selectivities.
The conversions of isobutane and the product selectivi-
ties determined from the FTIR results were calculated
on the basis of the measured amounts of carbon-
containing compounds. The molar amount of carbon in
the feed was assumed to be equal to the molar amount
of carbon in the product; the amount of coke deposited
on the catalyst during dehydrogenation was ignored.
The amount of isobutane fed CA,in was thus
∑C1 × 4 + ∑C2 × 4 + ∑C3 × 4 + ∑C4 +
1 2 3
CA,in )
6 7
C6 × + C7 × (2)
4 4
The accuracy of this calculation was verified by calcu-
lating the mass balance of carbon in the reactor sys-
tem: the calculated inlet isobutane concentration CA,in
was compared with the measured inlet concentration.
The conversion of isobutane X was calculated as
CA,in - CA,out
X ) 100% × (3)
CA,in
The selectivity Si to product i was calculated as
Ci
Si ) 100% × (4)
CA,in - CA,out
The yield of product i was calculated by multiplying the
conversion of isobutane X by the selectivity Si to product
i. The conversions and selectivities determined from the
GC results were calculated on a molar basis.
Kinetic Models. Several kinetic models were tested
to describe the rate of dehydrogenation; the equations
are presented in Table 2. Model 1 is a power-law model
that includes both the forward and the reverse reaction
rates. Models 2-8 were derived from possible dehydro-
 Ind. Eng. Chem. Res., Vol. 41, No. 23, 2002 5621

Table 2. Kinetic Models Tested for the Dehydrogenation Data

model rate equation model rate equation

1 (
k pA -
pEpH2
K ) 7
(
k′ pA -
pEpH2
K )
1/2
(III-b) [1 + KApA + K′pEpH2 + (KH2pH2)1/2]2

2
(
k′ pA -
K
pEpH2
) 8
(
k′ pA -
K
pEpH2
)
(I-a) 1 + KEH2pEpH2 + KEpE + KH2pH2 (IV-a) 1 + KEH2pEpH2 + KH2pH2

3
(
k′ pA -
K
pEpH2
) 9
(
k′ pA -
K
pEpH2
)
(I-b) (1 + KApA + KEpE + KH2pH2)2 (IV-b) 1 + KApA + KH2pH2

4 K (
k′ pA -
pEpH2
) 10
(
k′ pA -
K
pEpH2
)
(II-a) [1 + K′pEpH2 + KEpE + (K′′′pH2)1/2 + KH2pH2]2
1/2 1 + KEH2pEpH2 + KEpE

(
k′ pA -
pEpH2
K ) (
k′ pA -
K
pEpH2
)
[ ]
5 11
(II-b) pA 2 1 + KEpE + KH2pH2
(K′′′pH2)1/2 1 + K′′ 1/2 + KEpE + (K′′′pH2)1/2 + KH2pH2
pH2

6
(
k′ pA -
K
pEpH2
) 12
(
k′ pA -
K
pEpH2
)
(III-a) 1 + KEH2pEpH2 + K′pEpH21/2 + (KH2pH2)1/2 (1 + KH2pH2)(1 + KApA + KEpE)

genation mechanisms with use of the general principles
of the Langmuir-Hinshelwood approach.27 These mod-
els will be referred to in the form “model I-a”, where
the Roman numeral indicates the mechanism and the
letter (a or b) the reaction rate-determining step (RDS),
with the letter a referring to the adsorption of isobutane
and b to the surface reaction. Models with isobutene or
hydrogen desorption as the slow step were tested in
some calculations, but these models described the
activity results poorly. Moreover, it has been concluded
from tracer experiments that the desorptions of isobutene
and hydrogen are in equilibrium.20 Desorption models
were, therefore, not considered more closely. Mecha-
nisms I and II are presented in eqs 5a-d and 6a-e,
respectively.
Mechanism I
i-C4H10(g) + S T i-C4H10‚ ‚ ‚S
rate of isobutane dehydrogenation on unsupported
chromia gel.
Mechanisms I and II imply that the hydrocarbon and
hydrogen species occupy the same type of active surface
site S, for example, chromium. Mechanisms III and IV,
however, assume that (i) the active site requires both a
chromium and an oxygen ion, as has been suggested;3,21,22
(ii) some steps occur on the same Cr-O pair, with the
use of both the chromium and the oxygen ion; and (iii)
it is not necessary in the model derivation to write
separate site balances for the chromium and oxygen
ions. In mechanism III, proposed by Carrà et al.12 for
n-butane dehydrogenation on chromia/alumina, the
alkane adsorbs dissociatively on a Cr-O pair (step 7a).
In the surface reaction, the adsorbed alkyl group reacts
with a neighboring Cr-O pair (step 7b), and finally, the
alkene and the hydrogen desorb from the surface (steps
(5a) 7c and d).

i-C4H10‚ ‚ ‚S + S T i-C4H8‚ ‚ ‚S + H2‚ ‚ ‚S (5b) Mechanism III

i-C4H8‚ ‚ ‚S T i-C4H8(g) + S (5c) i-C4H10(g) + Cr-O T i-C4H9‚ ‚ ‚Cr-O‚ ‚ ‚H (7a)

H2‚ ‚ ‚S T H2(g) + S (5d) i-C4H9‚ ‚ ‚Cr-O‚ ‚ ‚H + Cr-O T

i-C4H8‚ ‚ ‚Cr-O‚ ‚ ‚H + H‚ ‚ ‚Cr-O (7b)
Mechanism II
i-C4H10(g) + 2S T i-C4H9‚ ‚ ‚S + H‚ ‚ ‚S (6a) i-C4H8‚ ‚ ‚Cr-O‚ ‚ ‚H T i-C4H8(g) + Cr-O‚ ‚ ‚H (7c)

i-C4H9‚ ‚ ‚S + S T i-C4H8‚ ‚ ‚S + H‚ ‚ ‚S (6b) Cr-O‚ ‚ ‚H + H‚ ‚ ‚Cr-O T H2(g) + 2 Cr-O (7d)

i-C4H8‚ ‚ ‚S T i-C4H8(g) + S (6c) In the reaction equations, the notation i-C4H9‚ ‚ ‚Cr-
2H‚ ‚ ‚S T H2‚ ‚ ‚S + S (6d) O‚ ‚ ‚H, for example, means that the alkyl group and
the hydrogen atom are adsorbed on the Cr-O pair.
H2‚ ‚ ‚S T H2(g) + S (6e) Mechanism III can be simplified to mechanism IV,
suggested by Burwell et al.,22 by assuming that the
Kao et al.20 used mechanism II with a surface reaction dehydrogenation reaction takes place on a single Cr-O
(step 6b) as the rate-determining step to describe the pair. Recently, Weckhuysen and Schoonheydt3 proposed
5622 Ind. Eng. Chem. Res., Vol. 41, No. 23, 2002
a similar mechanism for dehydrogenation. Although
they described the adsorption of the alkane and the
dissociation to an alkyl group and a hydrogen atom as
two separate steps, their mechanism leads to a math-
ematical expression similar to that obtained with mech-
anism IV.
Mechanism IV
i-C4H10(g) + Cr-O T i-C4H9‚ ‚ ‚Cr-O‚ ‚ ‚H (8a)
i-C4H9‚ ‚ ‚Cr-O‚ ‚ ‚H T
i-C4H8(g) + H‚ ‚ ‚Cr-O‚ ‚ ‚H (8b)
H‚ ‚ ‚Cr-O‚ ‚ ‚H T H2(g) + Cr-O (8c)
In mechanism IV, step 8a is the adsorption of isobu-
tane, and step 8b the surface reaction. Mechanisms III
and IV both include the formation of Cr-H and O-H
bonds, in agreement with the results of FTIR studies
by Busca,24 who detected Cr-H and O-H species on
unsupported chromia during hydrogen adsorption at
room temperature. The main difference between the two
mechanisms is the surface reaction: mechanism III
requires two chromium ions and mechanism IV only one
ion. De Rossi and co-workers8-10 suggested the active
site to consist of one Cr3+ ion, with neighboring oxygen
ion(s) involved in the reaction. This might support a
mechanism with one chromium ion. However, Cavani
et al.6 proposed amorphous chromia to be the most
active species, which might support a mechanism
involving multiple chromium ions or else a mechanism
involving one chromium ion but with the activity of the
single ion higher in an environment with several
chromium ions nearby.
In addition, three other models presented in earlier
studies were tested: models 10 and 11 (Table 2), with
adsorption as the RDS, proposed by Zwahlen and
Agnew15 and Happel et al.,16 respectively, for the
dehydrogenation of isobutane on chromia/alumina, and
model 12, with surface reaction on two different types
of sites as the RDS, proposed by Suzuki and Kaneko19
for the dehydrogenation of propane on a potassium-
modified chromia/alumina catalyst.
Parameter Estimation. The parameters of the
kinetic equations were estimated from the results of 59
dehydrogenation stages carried out with a hydrogen-
prereduced catalyst. The amounts of isobutane, isobutene,
hydrogen, and nitrogen were used in the estimation. The
molar amounts of isobutane and isobutene were deter-
mined from the results of FTIR analyses after 5 min on
the isobutane stream, and the amount of hydrogen was
assumed to equal that of isobutene. The data set did
not include the results of the stabilization or the
standard dehydrogenation stages so that the effects of
deactivation and the overemphasis of certain reaction
conditions could be ruled out. The parameters were
estimated with the Kinfit program25 by minimizing the
sum of squares of the residuals (SSR) between the
measured and calculated compositions of the product
stream. The kinetic model was combined with an
integral plug-flow reactor model, and the minimization
was performed by the Levenberg-Marquardt method.
The temperature dependence of the reaction rate
constant was described with an Arrhenius equation that
was rewritten as
k ) Ameane-zE (9)
where Amean is A0e-E/RTmean and z is 1/R(1/T - 1/Tmean).
The temperature 550 °C was used as Tmean. The rep-
arametrization was done to reduce the correlation
between the parameters. During preliminary modeling,
the adsorption/desorption equilibrium constants were
described with an equation similar to eq 9. However,
this resulted in poor identifiability of the models.
Therefore, the adsorption equilibrium constants were
assumed to be temperature-independent. Consequently,
the parameters are not real adsorption equilibrium
constants but represent mean values in the temperature
range studied (520-580 °C). The equilibrium constant
of the dehydrogenation reaction was calculated from the
thermodynamic data in the Flowbat program26
122 kJ/mol
K ) 2.1 × 107 exp - ( RT )
bar (10)
Results and Discussion
General Remarks. Mass Balance of Carbon. The
mass balance of carbon in the reactor system was
calculated from the molar amounts of hydrocarbons
measured by FTIR spectroscopy during dehydrogena-
tion. The mass balance was generally 97-99%. Coke
deposition on the catalyst during dehydrogenation was
low, and the effect of coke on the total mass balance
was less than 1%.
Thermal Reactions. The thermal reactions were stud-
ied by replacing the catalyst with an equal amount of
silicon carbide. Without the catalyst, the yield of
isobutene was 0-3.7% in the studied temperature range
of 520-580 °C, with the highest yields being obtained
at high temperatures and low feed rates.
Mass Transfer. The effect of external mass transfer
was studied in dehydrogenation experiments done at
580 °C with a WHSV value of 15 h-1 with use of two
different catalyst loadings (0.1 and 0.2 g). The isobutane
conversion was 31% with both loadings, and the selec-
tivities to isobutene were 93 and 96% with 0.1 and 0.2
g, respectively. The similar results indicated that ex-
ternal mass-transfer limitations were negligible.27 In-
ternal mass transfer was considered with the Weisz-
Prater criterion. The calculated value was about 10-7
in magnitude (,1), which implied that internal mass-
transfer effects were not significant.
Effect of Nitrogen Dilution. Noda et al.18 accounted
for nitrogen adsorption onto the catalyst surface in their
kinetic investigation of n-butane dehydrogenation on
chromia/alumina. Even though nitrogen was not ex-
pected to interact with the oxide catalyst,28 the adsorp-
tion effect of nitrogen was investigated in the present
study by doing some experiments with argon instead of
nitrogen dilution. The experiments were carried out
with a 0.2-g catalyst loading at 580 °C and a WHSV
value of 15 h-1. The conversion of isobutane and the
selectivity to isobutene were 30 and 95%, respectively,
for both nitrogen and argon dilution. Thus, the nitrogen
adsorption parameter was not included in the kinetic
equations.
Activity in the Dehydrogenation of Isobutane. To
determine whether to perform the kinetic measure-
ments with a hydrogen-prereduced or a nonprereduced
catalyst, the effect of the reducing medium on the
product distribution was studied in the first 12 cycles
of the series. A typical product distribution for the
nonprereduced catalyst is shown in Figure 1. During
the first few minutes on stream, carbon oxides and
water were formed in the reduction of Cr6+ and Cr5+ to

Figure 1. Product distribution with a nonprereduced catalyst.
Figure 2. Yield of isobutene at 10 min on the isobutane stream
in the stabilization and standard dehydrogenation stages for the
first series, as measured by GC. (Reaction conditions: 580 °C, 0.1
g, 15 h-1, and 50% i-C4H10/N2.)
Cr3+ with isobutane, and water was formed in the
prereduction with hydrogen. With the isobutane reduc-
tion, the amount of dehydrogenation products stabilized
only after the formation of carbon oxides terminated,
whereas with hydrogen prereduction, no carbon oxides
or water were formed during the dehydrogenation stage.
The kinetic experiments were, therefore, carried out
with a prereduced catalyst. The most significant side
reaction in all dehydrogenations was the cracking of C4
hydrocarbons to C1-C3 hydrocarbons, mostly methane
and propene. In addition, a low concentration (<1%) of
C4 hydrocarbons other than isobutane and isobutene
was detected.
The experimental data consisted of dehydrogenation
activities measured in three series. Figure 2 shows, as
an example for the first series, the yield of isobutene at
10 min on the isobutane stream for the first 16 dehy-
drogenation stages and for the standard stages. Figure
3 presents a typical example of the catalyst activity with
time on the isobutane stream after hydrogen prereduc-
tion. During the initial 16 cycles, the catalyst activity
decreased, most likely as a result of structural changes
on the catalyst5 and possibly also accumulation of
unburned coke on the surface. After the deactivation
period, the catalyst activity stabilized as a function both
of the number of cycles and of the time on the isobutane
stream. With the stabilized catalyst, the conversion of
isobutane and the selectivity to isobutene were 31 ( 1
Ind. Eng. Chem. Res., Vol. 41, No. 23, 2002 5623
Figure 3. Activity of the catalyst as a function of time on stream
after hydrogen prereduction. (Reaction conditions: 580 °C, 0.2 g,
15 h-1, and 50% i-C4H10/N2.)
Figure 4. Results of selected kinetic activity measurements.
(Reaction conditions: 520-580 °C, 0.1 g, 15 or 30 h-1, and 50%
i-C4H10/N2.)
and 93 ( 1%, respectively, in the standard dehydroge-
nation stages of the first series. The results were similar
for the second and third series. In the kinetic activity
measurements, the conversion was 3.6-34%, and the
selectivity to isobutene was 90-99%, depending on the
reaction conditions. Figure 4 shows the conversion of
isobutane at different temperatures with a catalyst
loading of 0.1 g and WHSV values of 15 and 30 h-1
without hydrogen in the feed. At 550 °C, the thermo-
dynamic equilibrium conversion is about 61% with the
isobutane feed diluted with nitrogen at a molar ratio of
1:1.29
Addition of hydrogen to the isobutane feed decreased
the conversion and the selectivity. The main reason for
the lower selectivity was that the cracking reaction of
C4 hydrocarbons was mainly a thermal reaction. Thus,
hydrogen affected only the yield of isobutene and not
the yield of cracking products. The additional hydrogen
in the gas phase might have decreased the conversion
by slowing the desorption of hydrogen from the surface,
thereby decreasing the number of vacant surface sites.
The effect might also have been purely kinetic: the
reaction rate decreased because of the increased hydro-
gen partial pressure. In any case, the results suggest
that the hydrogen partial pressure is required in the
kinetic model.
The effect of the reducing medium on the yield of
isobutene can be seen from Figure 2 (cycles 1-12). The
5624 Ind. Eng. Chem. Res., Vol. 41, No. 23, 2002

Table 3. Results of the Parameter Estimation for the Kinetic Models

model parameter valuea model parameter valuea model parameter valuea
1 Ameanb 0.0313 ( 0.0003 5 (II-b) Ameanb 0.0160 ( 0.0139 9 (IV-b) Ameanb 0.0371 ( 0.0008
E (kJ/mol) 99 ( 5 E (kJ/mol) 147 ( 6 E (kJ/mol) 115 ( 4
SSR 218 K′′ (bar-1/2) 0.33 ( 0.09 KA (bar-1) 1 × 10-8 c
2 (I-a) Ameanb 0.0507 ( 0.0028 KE (bar-1) 4.02 ( 1.10 KH2 (bar-1) 2.75 ( 0.36
E (kJ/mol) 141 ( 3 K′′′ (bar-1) 0.33 ( 0.37 SSR 89
KEH2 (bar-2) 9.72 ( 12.89 KH2 (bar-1) 6 × 10-6 c 10 Ameanb 0.0383 ( 0.0010
KE (bar-1) 7.33 ( 2.03 SSR 85 E (kJ/mol) 133 ( 5
KH2 (bar-1) 3.87 ( 0.62 6 (III-a) Ameanb 0.0596 ( 0.0037 KEH2 (bar-2) 58.00 ( 8.09
SSR 27 E (kJ/mol) 141 ( 3 KE (bar-1) 6 × 10-8 c
3 (I-b) Ameanb 0.0540 ( 0.0046 KEH2 (bar-2) 8 × 10-6 c SSR 66
E (kJ/mol) 139 ( 3 K′ (bar-3/2) 22.90 ( 7.25 11 Ameanb 0.0524 ( 0.0021
KA (bar-1) 0.14 ( 0.10 KH2 (bar-1) 7.56 ( 2.19 E (kJ/mol) 142 ( 3
KE (bar-1) 3.14 ( 0.32 SSR 24 KE (bar-1) 8.76 ( 1.09
KH2 (bar-1) 1.56 ( 0.13 7 (III-b) Ameanb 0.0599 ( 0.0052 KH2 (bar-1) 4.28 ( 0.38
SSR 28 E (kJ/mol) 140 ( 3 SSR 27
4 (II-a) Ameanb 0.0581 ( 0.0035 KA (bar-1) 0.15 ( 0.10 12 Ameanb 0.0557 ( 0.0049
E (kJ/mol) 141 ( 3 K′ (bar-3/2) 7.56 ( 0.82 E (kJ/mol) 140 ( 3
K′ (bar-3/2) 2.69 ( 2.39 KH2 (bar-1) 0.93 ( 0.17 KH2 (bar-1) 3.55 ( 0.27
KE (bar-1) 1.70 ( 0.92 SSR 24 KA (bar-1) 0.35 ( 0.23
K′′′ (bar-1) 1.11 ( 0.25 8 (IV-a) Ameanb 0.0414 ( 0.0008 KE (bar-1) 6.37 ( 0.81
KH2 (bar-1) 1 × 10-6 c E (kJ/mol) 137 ( 4 SSR 27
SSR 24 KEH2 (bar-2) 51.17 ( 6.26
KH2 (bar-1) 1.95 ( 0.25
SSR 33
a ( 95% confidence limit. b Units of mol/(kgcat s bar). c 95% confidence limit very large.

conversion of isobutane was lower after prereduction of
the catalyst with hydrogen than after its reduction with
the isobutane feed; the selectivity to isobutene was the
same. The observation that hydrogen prereduction
lowers the alkane conversion on chromia/alumina is in
accordance with the results of Hakuli30 and Gorriz et
al.31 but contrary to those of De Rossi et al.9 In general,
the reduction of the chromia phase liberates water in
hydrogen prereduction and carbon oxides and water in
isobutane reduction according to eqs 11 and 12, respec-
tively
H2 + O2- f H2O + 2e-
i-C4H10 + (4x + 5)O2- f
4COx + 5H2O + (8x + 10)e- (12)
In the present study, the amount of water detected
by FTIR spectroscopy during hydrogen prereduction and
isobutane reduction was lower than anticipated from
the amount of carbon oxides released in the hydrocarbon
they might have lowered the activity by changing the
dispersion of the chromia phase.32 Hydrogen addition
to the feed, in turn, might have decreased the reaction
rate purely through the influence of the increased
partial pressure on the catalyst surface.
Kinetic Modeling. Comparison of the Models. The
12 models presented in Table 2 were tested for the
measured dehydrogenation data, and the results of the
parameter estimation are presented at Table 3. The sum
of squares of the residuals (SSR) was significantly
higher with the power-law model (SSR 218) than with
the models assuming some adsorption effect (SSR 24-
(11) 89). Thus, the least accurate model was the power-law
equation. Models II-b, IV-b, and 10 were also rejected,
as their SSRs were in the range 66-89.
The lowest SSR value of 24 was obtained with models
II-a, III-a, and III-b. For model III-a, which assumed
adsorption as the RDS, the value of the isobutane
adsorption term KEH2pEpH2 was near 0. Thus, the model
could be simplified to eq 13 by omitting this term from
the model. The parameter values were not significantly
changed from those presented in Table 3.

reduction. Some water must have remained on the
catalyst, as proposed by Hakuli et al.4 and De Rossi et
al.9,10 The water remaining on the catalyst, in the form
of OH/H groups for example, has been suggested to
modify the active sites,30 possibly by influencing their
coordinative unsaturation. Moreover, De Rossi et al.10
observed that addition of water to the alkane feed
decreased the dehydrogenation activity of chromia/
zirconia catalysts. They suggested that the water ad-
sorbed on the surface and saturated a fraction of the
active sites. Here, saturation of some of the active sites
might explain the lower activity measured after hydro-
gen prereduction compared to that measured after
hydrocarbon reduction. It is questionable, however,
whether the lower activity observed after hydrogen
prereduction and the lower activity we observed upon
hydrogen addition to the feed were due to the same
cause, for example, the decrease in the number of vacant
surface sites. The oxygen-containing species formed in
the prereduction might have had an additional effect:
in addition to influencing the coordinative unsaturation,
( )
pEpH2
k′ pA -
K
-r′A ) 1/2
(13)
1 + K′pEpH2 + (KH2pH2)1/2
The additional parameters and the squared denomi-
nators in models II-a and III-b compared to eq 13 did
not decrease the SSR. The similar descriptions of the
three models can be explained by the estimation results,
as the values for the reaction rate constant factors Amean
and E are similar for the three models (Table 3).
Therefore, the values of the denominators should also
be similar, indicating that the parameter values were
determined so that they compensated for the modifica-
tions in the form of the equation. Thus, the three models
can be expressed with the simplest of them, eq 13.
Although the best modeling results were obtained
with eq 13, models I-a, I-b, IV-a, 11, and 12 (Table 2)
were also satisfactory (SSR 27-33). These five models
derive from quite similar mechanisms with adsorption

Figure 5. Correlation between weight fractions in the product
stream estimated with model 11 and eq 13 and the measured
weight fractions.
on one site, S or Cr-O, and desorption of alkene and
hydrogen also from single sites. When comparing the
form and the parameter estimation results of the
equations that adequately described the reaction, cer-
tain generalizations can be made. First, the adsorption
term of isobutane was either poorly determined, or its
value was near zero. Thus, it could be omitted from the
equations without increasing the SSR or changing the
values of the other parameters significantly. Second,
both the isobutene and hydrogen adsorption terms were
required in the equations for a satisfactory description
of the reaction rate. The effect of hydrogen was also clear
from the activity results: addition of hydrogen to the
feed lowered the conversion. In addition, the results of
model II-a (Table 3) indicated that the hydrogen atom
combination and desorption could be treated as a single
step. Third, squaring the denominator, corresponding
to an RDS with two similar active sites, only adjusted
the parameter values but did not decrease the SSR. The
simplest model studied to incorporate only the isobutene
and hydrogen adsorption terms was model 11, with
adsorption as the RDS, suggested earlier by Happel et
al.16 Figure 5 shows the weight fractions of isobutane,
isobutene, and hydrogen in the outlet stream as esti-
mated with eq 13 and model 11 versus the measured
weight fractions. Both equations can be used to describe
the isobutane dehydrogenation reaction with good ac-
curacy.
The finding that the isobutane adsorption term was
not required in the equations for a satisfactory descrip-
tion of the reaction rate supports a model with adsorp-
tion of isobutane as the slow step; the two proposed
models, eq 13 and model 11, both assume this RDS. In
addition, the results suggest that the adsorption re-
quires only one site because squaring the denominator
did not improve the description. This agrees with the
idea that the adsorption can occur dissociatively on the
suggested3,21,22 active site, a Cr-O pair. If the surface
reaction of the adsorbed species to the adsorbed alkene
were the slow step, the amount of adsorbed isobutane
or adsorbed i-C4H9- would be significant and, thus,
necessary in the equation. Our speculation for the rate-
determining step is in accordance with models suggested
by Zwahlen and Agnew15 and Happel et al.16 for isobu-
tane dehydrogenation on chromia/alumina but contrary
to the proposal of Kao et al.20 that the surface reaction
of the adsorbed alkyl group is the RDS in isobutane
dehydrogenation on chromia gel. Dissociative adsorption
Ind. Eng. Chem. Res., Vol. 41, No. 23, 2002 5625
of the alkane has been suggested to determine the rate
of isobutane dehydrogenation on supported Pt/Sn cata-
lysts33 and the molecular adsorption of the alkane the
rate of propane dehydrogenation on silicalite-supported
zinc oxide.34
The activation energy of the reaction rate-determining
step was estimated to be 133-142 and 115-147 kJ/mol
with models assuming, respectively, adsorption and
surface reaction as the RDS. Lower values than these
have been estimated before for isobutane dehydrogena-
tion on chromia/alumina with models assuming alkane
adsorption as the RDS: Zwahlen and Agnew15 esti-
mated a value of 112 kJ/mol with model 10 and Happel
et al.16 a value of 73 kJ/mol with model 11. Both models
10 and 11 are simplified forms of model I-a (Table 2),
with model 10 leaving out the KH2pH2 term of model I-a
and model 11 the KEH2pEpH2 term. Zwahlen and Agnew
modeled dehydrogenation and deactivation of the cata-
lyst simultaneously, which increased the number of
parameters to be fitted and might have reduced the
accuracy of the estimates. In addition, the values for
the reaction equilibrium constants were different in the
earlier studies from the values used in our study. These
differences might explain the higher values obtained
here for the activation energy.
Comparison of the Mechanisms. The modeling results
support mechanisms I and IIIsboth assuming adsorp-
tion on single site and surface reaction on dual sitess
approximately equally. Mechanism II, with adsorption
on dual sites, seems less probable as the results suggest
that the adsorption might require only one site. The
weakness of mechanism I, however, is the unlikely
abstraction of the hydrogen molecule from the alkane
in a single step; the weakness of mechanisms II and III
is that they require three and two similar active sites.
Mechanism IV, suggested by Weckhuysen and
Schoonheydt3 and by Burwell et al.,22 would seem to be
the most realistic on the basis of the conclusions of De
Rossi et al.8-10 that the reaction requires only one
chromium ion. However, our modeling results do not
support mechanism IV as strongly as the other mech-
anisms. It might be beneficial to treat the chromium
and oxygen ions as separate SCr and SO sites in the
model derivation rather than as a Cr-O pair. However,
if the adsorption/dissociation of alkane is the slow step
in the reaction, the other steps are more difficult to
elucidate with kinetic modeling of reaction rate data.
Isotopic tracer studies might also prove helpful in
deciding among the different mechanisms, and such an
approach is under study.
Conclusions
The kinetics of isobutane dehydrogenation was stud-
ied on a chromia/alumina catalyst developed for fluid-
ized-bed operation. The catalyst used was active and
selective in isobutane dehydrogenation. The activity was
lower after prereduction of the catalyst with hydrogen
than after reduction with the isobutane feed. The lower
activity might have been caused by the modification of
the active sitesspresumably coordinatively unsaturated
Cr-O pairssby the water formed during prereduction
and subsequently retained on the catalyst. The results
of the kinetic modeling suggest that the rate-determin-
ing step is isobutane adsorption, possibly with dissocia-
tion on a Cr-O pair. The isobutene and hydrogen
adsorption parameters were required in the kinetic
equation for a satisfactory description of the reaction
5626 Ind. Eng. Chem. Res., Vol. 41, No. 23, 2002
rate by the model. A value of 133-142 kJ/mol was
calculated for the reaction activation energy.
Acknowledgment
Financial support from the Academy of Finland is
gratefully acknowledged. We thank Ms. Jaana Kanervo
and Dr. Juha Linnekoski for valuable discussions and
help with the modeling.
Nomenclature
A0 ) preexponential factor, mol/(kgcat s bar)
Cn ) molar amount of compound containing n carbon
atoms, including hydrocarbons and carbon oxides
E ) activation energy, J/mol
k′ ) (apparent) rate constant, mol/(kgcat s bar)
K ) reaction equilibrium constant, bar
Ki ) adsorption equilibrium constant of component i, bar-1
KEH2, K′, K′′, K′′′ ) combined equilibrium constants
pi ) partial pressure of component i, bar
ri′ ) reaction rate of component i, mol/(kgcat s)
R ) 8.314 J/(mol K)
RDS ) rate-determining step
SSR ) sum of squares of the residuals
S ) adsorption site on the catalyst
Si ) selectivity to component i
T ) temperature, K or °C
X ) conversion of isobutane
Subscripts
A ) isobutane
E ) isobutene
A,in ) isobutane in the feed
A,out ) isobutane in the product stream
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Received for review May 20, 2002
Revised manuscript received September 11, 2002
Accepted September 13, 2002
IE020371J