2670 Znd. Eng. Chem. Res.

1992,31,2670-2674

Propane Dehydrogenation and Coke Formation on Chromia-Alumina

Catalysts: Effect of Reductive Pretreatments
Osvaldo F. Gorriz,+Vicente Cortes Corberin? and Jose L. G. Fierro*?*
Znstituto de Znvestigaciones en Tecnologia Quimica, ZNTEQUZ, Casilla Correo 290,5700 San Luis, Argentina,
and Znstituto de Catdlisis y Petroleoquimica, CSZC, Campus UAM Cantoblanco, 28049 Madrid, Spain

Propane dehydrogenation and coke formation over a series of alumina-supported chromia catalysts
with different chromia contents were examined. X-ray photoelectron spectroscopy (XPS)showed
that the calcined catalysts displayed Cr(VI) and Cr(III) in proportions which depended on the overall
chromia content. Cr(VI) appeared to be reduced in the initial stagea of the dehydrogenationreaction,
for which important changes in the selectivity to propene and in the coking rate were noted. These
changes were mainly related to the hydrocarbon combustion by the oxygen released from Cr203and
to the suppression of the strong acid sites by coking. Coke formation on CO-prereduced catalysta
was fast and could be related to the level and stability of the conversion to propene. Both activity
and selectivity of the catalysts were determined by the dispersion of Cr and by the effect of Cr content
on the porous structure of the catalysts.

Introduction Table I. Catalyst Samples Characterirticr

Dehydrogenation of light alkanes has a great industrial
importance because it represents an alternative for ob-
taining alkenes for polymerization and other organic
syntheses from low cost saturatad hydrocarbon feedstocks.
Supported chromia catalysts have been used for many
decades in alkane dehydrogenation (Kearby, 1955). As
dehydrogenation thermodynamicsrequires high temper-
atures, usually above 800 K, for acceptable alkene yields
to be obtained, highly stable carriers are of prime impor-
tance. Alumina is widely used since it is a refractory, high
surface area oxide; however, it presents the difficulty of
catalyzing side reactions, i.e., coking and cracking, leading
to catalyst deactivation.
Within this frame, there is a controversy in the literature
on the influence of carbon deposita during dehydrogenation
over chromiaalumina catalysta. While some authora argue
on the existence of a correlation between catalyst deac-
tivation and the amount of coke deposited (Noda et al.,
1974; Toei et al., 1975; Dumez and Froment, 1976), some
others claim that this correlation is not so clear (Heine-
mann, 1951; Shendrik et al., 1965; Boutry et al., 1967). In
previous studies, Gorriz et al. (1989) have reported that
the catalytic behavior of chromia-alumina catalysts pre-
pared by impregnation show an initial period during which
propene yield remains essentially unchanged, and then
deactivation occurs. In this initial step of reaction, whose
duration depends on the chromia content and the reaction
conditions, several authors have found an activity maxi-
mum, which was attributed to redox effects of the chro-
mium oxide phase produced in the course of the reaction
(Shendrik et al., 1965; Boutry et al., 1967; Gorriz et al.,
1989). A recent report (Gorriz et al., 1992) indicated that
the initial activity of the catalysts can be related to the
amount of Cr(VI) present in the catalyst before the reac-
tion, while the conversion stability before deactivation is
related to the dispersion of the chromium oxide phase.
Also, the pronounced deactivation of the catalysts after
this stability period has been attributed by some authors
to the formation of Cr(I1) (Marcilly and Delmon, 1972),
which almost coincides with the deposition of a limited
amount of coke that could modify the surface texture of
the catalyst.
Accordingly, the present work was undertaken with the
aim of analyzing the behavior of the catalysts in the ab-
+ INTEQUI.
* CSIC.
0888-5885/92/2631-2670$03.00/0@ 1992 American Chemical Society
% %
~ r z 0 3
4
(mZ/g) 9
(cm /g) cr209 (=$a) 5
(cm /g)
0 145 0.38 9.0 126 0.32
1.5 137 0.38 12.0 109 0.30
3.0 138 0.37 15.0 96 0.28
6.0 140 0.35
sence of redox changes to correlate this behavior only to
the coke formation. To reach this goal, the behaviors of
oxidized and reduced catalysts for propane dehydrogena-
tion were compared to observe the effect of oxidized
chromium on the activity and coke formation. Also the
catalysta reduction, the coke formation from propane and
propene, and the effect of this coke on the catalyst texture
were studied.
Experimental Section
Catalyst Preparation and Textural Analysis. Cat-
alyst samples were prepared by impregnating a commercial
y-alumina ALCOA F110, previously heated at 773 K in air
for 7 h (specific surface area 150 m2/g, pore volume 0.38
cm3/g, and average pore radius 2 nm) with an aqueous
solution of chromic acid, according to the pore filling
method. The samples were then dried at 383 K for 7 h
and calcined at 773 K for 30 h. The samples will be re-
ferred to hereafter as CA-x, where x denotes the chromia
content of the sample, expressed as the weight percent of
Cr203.
Textural analysis of catalyst samples was done by means
of adsorption-desorption of nitrogen at 77 K, using an
Accu Sorb 2100 E equipment (Micromeritics). Chemical
composition, specific surface areas, and pore volumes of
the prepared samples are shown in Table I.
X-ray Photoelectron Spectroscopy. X-ray photo-
electron (XP)spectra of powdered catalysta were acquired
by using a Leybold LHS 10 spectrometer, equipped with
a magnesium anode (Mg Ka = 1253.6 eV) operated at 12
kV and 10 mA and hemispherical electron analyzer. Each
spectral region of photoelectrons of interest was scanned
a number of times in order to obtain good signal-bnoise
ratios. The residual pressure inside the analysis chamber
was kept at values below 7.5 X lo4 Torr. C Is, Al2p, and
Cr 2p signals were recorded for each catalyst. All binding
energies (BE) were referred to the adventitious C 1s line
at 284.6 eV.
Microgravimetry. Catalyst reduction by CO and ex-
tent of coke deposition on the reduced samples were con-

585 580 575
BE (eV)
Figure 1. Cr 2 ~ 3core
, ~ level spectra of fresh catalysts: (a) CA-1.5;
(b) CA-3.0; (c) CA-6.0; (d) CA-9.0; (e) CA-12.0; (f) CA-15.0.
ducted by microgravimetryon a Cahn 2000 microbalance,
operated with a sensitivity of 1pg for the reduction ex-
periments and 10 pg for the coke deposition studies. In
these experiments, samples were charged in the microba-
lance and heated at a rate of 4 K/min up to the reduction
temperature in He flow. Reduction was made with a 42
mol % mixture of CO in He, at a total flow of 36 cm3/min,
until constant weight was attained. After catalyst reduc-
tion, the system was purged to remove CO, and the study
of the coke formation was started by feeding a gaseous
mixture of 35 mol % of the hydrocarbon (propane or
propene, according to the experimental program) in He
at a total flow of 44 cm3(STP)/min.
Catalytic Activity Tests. The activity of the catalyst
samples for the dehydrogenation of propane was tested in
a stainless steel, fixed-bed tubular reactor, at 873 K and
atmospheric pressure, using a catalyst charge of 2 g and
a gaseous mixture of 50 mol % propane in nitrogen at a
total flow of 1cm3(STP)/s as a feed. The fed gases were
carefully dried by passing them through a column filled
with silica gel and molecular sieve and preheated before
being introduced into the reactor. Prior to the run, the
catalyst was heated up to the reaction temperature in
flowing nitrogen. Reactant and effluent reaction products
were analyzed by GC by using an activated alumina packed
column and a flame ionization detector (FID). Propene
and, in some cases, carbon oxides were the only volatile
products detected. Conversion and selectivity to propene,
expressed as mole percent, were calculated as the ratio of
moles of converted propane to the moles of fed propane
and the ratio of moles of formed propene to the moles of
converted propane, respectively.
Ind. Eng. Chem. Res., Vol. 31, No. 12, 1992 2671
I I I
5 10 1s
wt % Cr,O,
Figure 2. Dependence of the Cr 2p/M 2p XPS intensity ratio on
the chromium content of the Catalysts.
I
0 6 10 16 20 26
Time (min)
Figure 3. Influence of chromia content in the reduction of catalpta
*,
by C O 0 , CA-1.5; +, CA-3.0; CA-6.0; O , CA-9.0; X, CA-12.0; 0 ,
CA-15.0.
Remults and Discussion
Surface Characterization by XPS. The oxidation
state of chromium and the chromia exposure at the sup-
port surface as a function of chromia contents were studied
by XPS. Figure 1 shows the most intense Cr 2pSl2peak
of catalysts with variable chromium contents. As can be
seen, the Cr 2P3l2 profile is quite complicatedand markedly
depends on chromia content. For the lowest Cr contents
only a peak at BE ca.580.0 eV was o b s e ~ dhowever,
, two
other peaks, of almost the same intensity, at ca. 580.0 and
578.1 eV were clearly distinguished for the highest Cr
contents. For intermediate chromia contents the peak at
580.0 eV also dominated, but a shoulder placed in the low
BE side at ca. 578.1 eV can be discerned. From the BE
values and in agreement with literature findings (Hard-
castle and Wachs, 1988; Wachs and Hardcastle, 1988), it
can be inferred that Cr(V1) species appear on catalyst
surfaces for every explored composition, while Cr(II1)
species become stable only at higher chromia contents.
The relative exposure of the chromium oxide on the
support surface was calculated by comparing the intensity
of signals corresponding to the Cr 2p and Al 2p peaks.
Figure 2 shows the dependence of IcrJIAIwith chromia
content. This relation was almost linear on low chromia
contents (below 6 mol %). Further increases in the
chr~miacontenta produced a lower increase of this relation,
indicating a poorer surface exposure of chromia.
Reduction Pretreatments. Figure 3 shows the weight
losses of different catalyst samples produced by CO re-
duction at 873 K as a function of the time of reaction. The
maximum extent of reduction was the highest for the
catalyst with the lowest chromia content (CA-1.51, and it
decreased as the chromia content increased. Table I1 is
a compilation of the values of the extent of reduction (Am),
initial reduction rate ( r J , and the reduction degree (a),
2672 Ind. Eng. Chem. Res., Vol. 31, No. 12,1992

Table 11. Reduction of Catalysts by CO at 873 K Table 111. Coke Formation on Chromia-Alumina Catalysts
ri [lo‘ g/(g of Am(expt) [1@ at 873 K
% CrzOa catalyst-min)] g/(g catalyst)] a ri 110s g/(mT of max coke loading (109
1.5 5.52 2.35 0.497 catalyst).min] g/m2 of catalyst)a
3.0 4.02 1.82 0.175 ICrzOs propane propene propane propene
6.0 5.03 2.08 0.109 0 2.0 12.3 2.13 (309)
9.0 3.06 1.09 0.038 1.5 11.0 48.5 0.80 (110) 2.12 (290)
12.0 3.34 1.26 0.033 3.0 14.0 63 0.75 (104) 2.12 (293)
15.0 4.82 1.09 0.021 6.0 32.1 76 0.73 (102) 2.01 (281)
9.0 32.9 99 0.83 (105) 2.13 (268)
12.0 41.3 105 0.78 (85) 2.25 (245)
I c 1 15.0 48.0 120 0.84 (81) 2.05 (197)
0 a Values in parentheses are expressed in mg/(g of catalyst).

1eo

* . * .

0
0 40 SO
Time (min)
120
1 ,
;n 40

Figure 4. Coke deposition from propane onto catalysts prereduced

by CO: 0 , CA-0.0; +,
CA-1.5; *,
CA-3.0; 0,CA-6.0; X, CA-9.0; 0 ,
CA-12.0; A, CA-15.0. 0
0 100 200 300
Coke (mg/g cat)
I I
Figure 6. Influence of coke deposition in the surface areas of cat-
300 1 alyst~. , +,
CA-3.0 coked by propene; CA-15.0 coked from propene;
*,CA-x (0 Iz 5 6.0) coked from propane; 0,CA-z (12.0 Iz I15.0)
coked from propane.

1 R

0 60 100 160 200

Time ( m i n )
Figure 5. Coke deposition from propene onto catalysts prereduced
by CO: 0 , CA-0.O; +, CA-1.5; *,
CA-3.0; X,CA-15.0.
expressed as the ratio of the experimental weight loss to
the theoretical value expected for the reduction of all the
chromium present from Cr(VI) to Cr(lII). Observed weight
losses in samples with the lower chromia contents were
almost double those with the higher chromia contents.
The calculated a values were in good agreement with the
tendency observed by XPS.
Coke Formation on Prereduced Catalysts. The ki-
netic curves of coke formation on chromia-alumina cata-
lysts for a feed of propane and propene are displayed in
Figurea 4 and 5, respectively. From these curves, the initial
rate of coke formation has been calculated from the slope
of the curves at zero time. Moreover, the extent of coke
formation was taken from the “equilibrium”values mea-
sured at very long reaction times. Both parameters are
compiled in Table 111. The initial rate of coke formation
as well as the total amount of deposited coke for both
propane and propene varied depending on the chromia
content of the catalysts.
In general, as the chromia content increased, the initial
rate of coke formation increased, but conversely the extant
of coke deposited per unit mass of catalyst decreased.
However, when the final coke loadings were referred to the
specific surface area of the catalysts, there was an almost
constant value irrespective of chromium oxide content of
the catalysts. Table 111 also evidences that initial rates
of coke formation were much higher for propene than for
0 2 4 s 8 10 12
Pore Radius (nm)
Figure 7. Influence of coke deposition in the pore distribution of
catalysts 0 , CA-3.0 with 5 (mg of coke)/(g of catalyst); 0 , CA-3.0
with 39.3 (mg of coke)/(g of catalyst); 0,CA-15.0 with 5 (mg of
coke)/(g of catalyst);4 CA-15.0 with 30 (mg of coke)/(g of catalyst).
propane. This can be interpreted assuming that the alkene
or surface species originating from it are the precursors
of coke, as suggested by K h i g and T6Gnyi in their study
of ethane dehydrogenation on u118upported CqO3 (K6nig
and TBGnyi, 1976a,b). Note also that the initial coking
rate with propene on the bare support surface (0% Cr203)
was 1order of magnitude higher than with propane, and
of the same order as compared with those observed in the
lower chromia content catalyst samples (CA-1.5 and CA-
3.0) with propene. Although one should expect that initial
rates should be determined by the conversion level of
propane to propene, it is clear also that the chromia con-
tent plays a role, as a variation can be observed even when
the propene concentration is kept constant in the feed,
especially on the lower chromium contents samples.
The participation of the alumina carrier (0% Cr2O3) to
coking rates and extant of coke formation is not s u r p r i s i i .
This arises in the acid sites present on its surface which
induced a faster dehydrogenation for the propene than for
propane. To avoid this side reaction, poisoning of the acid
sites of alumina, very often with potassium, was a common
 Ind. Eng. Chem. Res., Vol. 31, No. 12, 1992 2673

* X'
* *
X .
361 *' x
x *
x Ik'*'

-20' I
0 S 10 16 20
Time (min)
Figure 9. Influence of pretreatments in the evolution of coke for-
mation from propene onto CA-15.0 0,unreduced, 0, prereduced by
co.
60 1 I100

t I .-

0
I/--------
0 60 100 160
0
200
Time-on-Stream (min)
Figure 10. Influence of chromia content in the catalytic propane
dehydrogenation over chromia-alumina catalpts prereduced by C O
0, CA-1.5; 0, CA-3.0; 0 , CA-6.0; A, CA-15.0. Full symbols con-
version. Open symbols: Selectivity.

The oxidation state of chromium also affected the se-

lectivity of the samples. So, the initial selectivity of the
unreduced sample was much lower than that of the re-
duced ones, but it recovered quickly to similar levels with
time on stream. Selectivity to propene increased with time
on stream in all cases. In the unreduced sample this be-
havior was due to the initial formation of oxygenated
compounds, produced in the reduction of Cr(V1) by the
hydrocarbon, which disappeared as the reduction to Cr(lII)
was completed. In reduced samples it implied suppression
of the strong acidic centers by the quick deposition of coke
in the initial stages of the reaction. This result excludes
participation of Cr(V1) in dehydrogenation of propane.
Several authors claim that the active site in alkane dehy-
drogenation is Cr(II) (Ashmawy,1980, Lug0 and Lunsford,
1985), while others propose that Cr(II1) sites are active
(Marcilly and Delmon, 1972; Kiinig and TgGnyi, 1976a,b).
The combined use of XPS, microgravimetric reduction,
and activity data obtained in this study lead us to conclude
that in the CrzO3/Al2O3catalysts the dehydrogenation
activity is related to Cr(II1).
The influence of oxidation state of chromium on coke
formation has also been examined. Microgravimetric
studies of coke deposition on one unreduced CA-15.0
sample and its CO-prereduced homologue showed that
coke formed immediately when contacting propene with
the reduced sample, but this formation was not observed
on the unreduced sample until a certain time had elapsed
(Figure9). In this time lapse,comparable to that observed
in the reduction experiments with CO, a clear inhibition
of coke formation was observed. After this initial period,
the rate of coke formation attained values similar to those
observed for the prereduced sample.
In general, the catalytic behavior of samples prereduced
by CO was found to depend on the chromia content
2674 Ind. Eng. Chem. Res., Vol. 31, No. 12, 1992
(Figure 10). The initial conversion increased with in-
creasing chromia content up to a 6 w t %. A further in-
crease of chromia content was accompanied by a much
lower increase of the initial conversion. From a comparison
of these data with those of XPS in Figure 2, it is clear that
a parallelism exists between the initial propane conversion
and the intensity ratio Icr/IAI.
Finally, the increase of conversion with increasing
chromia content can also explain the results of coke for-
mation from propane. The increase of initial rates of coke
formation with chromia content, in the region in which the
XPS intensity ratio ICr/IAIprogressively increased, can be
interpreted as due to the increase of exposed Cr(II1) sites
responsible for the reaction. Upon the addition of larger
chromia amounts, the number of exposed sites does not
increase and hence the activity remains constant. This
direct relationship between initial coke formation rate and
propane conversion is clear evidence of the participation
of the olefinic product in the formation of coke.
Conclusions
Chromium in the oxidized state affected both catalytic
activity and coke formation in the initial stages of the
reaction time, while the reduction of the catalysts was
produced. In these first stages substantial changes in the
selectivity to olefiic product as well as an important in-
hibition of coke formation were observed.
The changes of selectivity noted in the unreduced cat-
alysts came from the transformation of the hydrocarbon
into oxygenated products, mainly COz and water, and
suppression of strong acid centers by coke deposition.
Catalyst samplea prereduced by CO showed only selectivity
changes determined by the suppression of acid sites.
Coke formation onto prereduced catalysts was imme-
diate and was related to the level and stability of the
conversion to the olefinic product. Activity and stability
of the catalysts studied here were determined by the Cr
dispersion and by the effect of the chromia content on the
porous structure of the catalyst, respectively.
The catalytic stability of catalysts with high chromia
content was lower because the chromia content affected
the surface texture. The fact that the chromia content
affected the porous structure was evidenced by the pro-
gressive decrease of both BET area and pore volume with
increasing Cr content (cf. Table I). The final coke loading
was related to the total surface area of the catalysta. Fresh
catalysts having the higher micropore volume and the
higher surface areas acquired, after the first coking, a
porous structure close to that of catalysts with the higher
chromia content, and from this moment the rates of coking
for the fresh and partially coked catalyst with similar
textural properties were essentially the same.
Acknowledgment
"his work was developed thanksto a cooperative project
in the frame of the CONICET-CSICScientific Cooperation
Program.
Nomenclature
dV/dR = pore size distribution
I,,/I*, = ratio of intensity of XPS signals corresponding to
the Cr 2p and AI 2p peaks, undimensional
Am = extent of reduction expressed aa experimental weight
loss during reducing treatments, g/ (g of catalyst)
ri = initial rate of reduction, g/(g of catalyst-min)
S, = specific surface area, m2/g
V, = specific pore volume, cm3/g
cy = reduction degree, expressed as ratio of the experimental
weight loss to the theoretical value expected for the re-
duction of all the chromium present from Cr(VI) to Cr(III),
undimensional
Registry No. ALCOA F110, 1344-28-1;propene, 115-07-1;
chromia, 1308-38-9;propane, 74-98-6.
Literature Cited
Ashmawy, F. M. Surface composition and catalytic activity of chro-
mia-alumina catalysts. J. Chem. SOC.,Faraday Trans. 1 1980,76,
2096.
Boutry, P.;Montarnal, R.; Blejean, C. Influence of the reaction
medium on the dehydrogenation activity of chromium oxide.
Determination of the nature of catalytic surface sites. Bull. SOC.
Chim. Fr. 1967,10,3690.
de R m i , S.;Ferrati, G.;Fremiotti, S.; Cimino, A.; Indovina, V.
Propane dehydrogenation on chromia/zirconia catalysts. Appl.
Catal. 1992,81,113.
Dumez, F. J.; Froment, G. F. Dehydrogenation of 1-butene into
butadiene. Kinetics, catalyst cooking and reactor design. Ind.
Eng. Chem. Process Des. Dev. 1976,15,291.
Gorriz, 0.F.;Arrua, L. A.; Cadus, L. E.; Rivarola, J. B. P. Catalytic
dehydrogenation of propane to propylene. Lat. Am. Appl. Res.
1989,19,31.
Gorriz,0. F.; Cadus, L. E.; Rivarola, J. B. P. Catalytic dehydroge-
nation of propane: Deactivation by coke. To be published, 1992.
Hardcastle, F. D.; Wachs, I. E. Raman spectroscopy of chromium
oxide supported on Al2O3, Ti02 and Si02: A comparative study.
J. Mol. Catal. 1988,46,173-186.
Heinemann, H. Dehydrogenation of methylcyclopentadiene over
chromia-alumina catalysts. Ind. Eng. Chem. 1951,43,2098.
Hino, M.;Arata, K. Dehydrogenation of hexane to benzene over
zirconia-supported chromia. J. Chem. SOC.,Chem. Commun.
1987,1355.
Kearby, K. K. Catalytic dehydrogenation. In Catalysis; Emmett, P.
H., Ed.; Reinhold: New York, 1955;Vol. 3,p 453.
Kanig, P.; TBtBnyi, P. Kinetics of ethane dehydrogenation of a-
chromium(II1) oxide catalysts. I. The rate determining step.
Acta Chim. Acad. Sci. Hung. 1976a,89,123.
Kanig, P.; TBtBnyi, P. Kinetics of ethane dehydrogenation of a-
chromium(III) oxide catalysts. II. The rate equation. Acta Chim.
Acad. Sci. Hung. 1976b,89,137.
Lugo, H. J.; Lunsford, J. H. The dehydrogenation of ethane over
chromium catalysts. J. Catal. 1985,91,155.
Marcilly, Ch.; Delmon, B. The activity of true Crz03-A1203solid
solutions in dehydrogenation. J. Catal. 1972,24,336.
Noda, H.; Tone, S.; Otake, T. Kinetics of isopentane dehydrogena-
tion on a chromia-aluminacatalyst with catalyst fouling. J. Chem.
Eng. Jpn. 1974, 7,110.
Shendrik, M. M.; Boreskov, G.K.; Kirilyuk, L. V. Variation of the
activity of chromia-alumina Catalysts in the process of dehydro-
genation of butane (in Russian). Kinet. i Katal. 1965,6, 313.
Tanabe, K. Surface and catalytic properties of zirconia. Mater.
Chem. Phys. 1985,13,347.
Toei, R.; Nakanishi, K.; Yamada, K.; Okazaki, M. Catalytic fouling
in the dehydrogenation of butane over chromia-aluminacatalysts.
J. Chem. Eng. Jpn. 1975,8,131.
Wachs, I. E.; Hardcastle, F. D. b a n spectroscopy of supportad
metal oxides on Al2O3, TiOp and SiOz: A comparative study.
Proceedings of the International Congress on Catalysis 9th,
Calgary, 1988;Chemistry Institute of Canada: Calgary, 1988, Vol.
3,p 1449-1466.
Received for review June 1, 1992
Accepted September 25, 1992