9314 Ind. Eng. Chem. Res.

2008, 47, 9314–9320

Propane Dehydrogenation over Pt-Sn-K/γ-Al2O3 Catalyst in a Two-Zone

Fluidized Bed Reactor
M. Pilar Lobera, Carlos Téllez, Javier Herguido,* and Miguel Menéndez
Aragon Institute for Engineering Research (I3A), UniVersity of Zaragoza, 50009 Zaragoza, Spain

A two-zone fluidized bed reactor (TZFBR) is employed for propane dehydrogenation over a Pt-Sn-K/γ-
Al2O3 catalyst. This type of reactor constitutes an alternative to the use of two separate reactors with solid
circulation between them or of a single reactor with periodic operation and allows continuous operation with
in situ catalyst regeneration. The effect of the main TZFBR operating variables is studied and the reactor
performance compared with results obtained in other works using Pt-Sn based catalysts, showing that a
steady state is reached with similar selectivity to that reported in the literature for other reactors which suffer
the problem of catalyst deactivation.

1. Introduction Fluidized bed reactors where separate oxidation and reduction

The increasing consumption of propylene derivates has
heavily increased propylene demand during recent years. It is
expected that to cover future propylene demand, other processes
will have to be developed (dehydrogenation, oxidative dehy-
drogenation, metathesis, or use of membrane reactors) in add-
ition to traditional petrochemical or refinery processes (steam
cracking, fluid catalytic cracking), since it is forecast that the
propylene market will grow faster than the ethylene market.1
The dehydrogenation of light paraffins comprises several
technologies: Oleflex (UOP), STAR (Phillips Petroleum), Cato-
fin (Houndry, United Catalysts Inc., ABB Lummus Crest),
Linde-BASF, and FBD (Snamprogetti-Yarsintez). The catalysts
used are either promoted Pt supported on various carriers
(alumina and Group II spinels are preferred) or variously doped
chromia-aluminas. Although these processes and their respective
catalysts are highly optimized, they all suffer from the common
disadvantage that their olefin yields are thermodynamically
limited. Propane dehydrogenation is an equilibrium limited and
highly endothermic reaction (∆HR298K ) 120 kJ mol-1) and
hence requires an external supply of heat which is expensive.2
Therefore one of the most important problems to be solved in
the development of a suitable reactor for an industrial dehy-
drogenation process is how to supply the huge quantity of heat
needed by the reaction at temperatures well above 500 °C,
maintaining in the meantime a careful control of temperature
to minimize the formation of byproduct (cracking) and maximize
the yield to the desired product.3
In addition, coke is rapidly formed at high temperatures, and
as a consequence of the catalyst deactivation, its regeneration
is necessary. The most usual option for catalyst regeneration is
the combustion of the coke deposits by mixtures of oxygen and
inert diluent. Apart from some of above-cited technologies (e.g.,
UOP or FBD), regeneration is very often carried out off-line,
either in a separate reactor or in the same reactor, after purging
the flammable hydrocarbon gases. In any case, the downtime
for regeneration represents a significant economic penalty, and
this provides the incentive for processes where the catalyst is
continuously regenerated.
The great majority of industrial processes operate cyclically
with fixed bed reactors where propane is cofed with hydrogen
to decrease coke formation. Overall, propene selectivity of
85-90% is reached.
* Corresponding author.
10.1021/ie800848c CCC: $40.75  2008 American Chemical Society
Published on Web 11/04/2008
zones are present in the same vessel have been developed in
our laboratory and used for various different processes during
the past decade. The advantages of the two-zone fluidized bed
reactor have been proven in a variety of reactions belonging to
two different groups: (a) catalytic oxidations where the catalyst
acts as an oxygen carrier,4 allowing the reaction with a low
oxygen concentration in the gas phase, and (b) dehydrogenation
processes, where the catalyst becomes deactivated by coking
in the reaction zone and is regenerated at the oxidizing zone.5,6
A review of the use of these reactors has previously been
published.7
The objective of this research is to employ as a reactor a
single vessel that can be operated in steady state. To achieve
this objective, we have developed different types of fluidized
bed reactors with separate oxidation and reduction zones. One
of these is called the two-zone fluidized bed reactor. This
consists of a fluidized bed where oxygen is fed to the lower
part of the reactor, mixed with an inert gas, and the hydrocarbon
(or in general the compound to be oxidized) is fed in at an
intermediate point of the bed. Thus two zones are created in
the reactor: in the lower zone the catalyst is reoxidized (re-
generated) by gas phase oxygen, a process that causes the gas
stream to become depleted in oxygen. In the upper zone, the
chemical reaction takes place, and the catalyst is deactivated.
Reaction products, unconverted reactants, and inert diluent exit
together at the top of the bed. The good circulation of the solid,
characteristic of fluidized beds, provides transport of solid
between both zones, and as a result stationary state is reached.7
In reactions like propane dehydrogenation, two of the most
important problems are the fast deactivation of the catalyst by
coking and the quantity of heat required by the reaction. The
TZFBR may be employed to implement continuous catalyst
regeneration in the reactor, and the quantity of heat necessary
for the reaction can be supplied in part by the sensible heat
stored in the catalyst bed in the regeneration zone. Furthermore,
the use of a fluidized bed reactor provides a good control of
temperature, which helps to minimize the formation of byprod-
uct (cracking) and maximize the yield to propene. To better
understand the reaction, a previous kinetic model for the propane
dehydrogenation, the coke formation, and the effect of coke on
catalyst deactivation has been developed under transient condi-
tions.8
 Ind. Eng. Chem. Res., Vol. 47, No. 23, 2008 9315
Table 1. Range of Operating Conditions
variable range studied units
T 480-540 °C
ur1 2.8-5.0
propane molar fraction 0.5
oxygen molar fraction 0.0-0.2
bed length (H) 8-14 cm
bed length (HFC3H8 - ha)/ha 0.3-2.0
Wr/FC3H8 38-205 s kg mol-1

tube equipped with a quartz distributor plate (for the Ar/O2

Figure 1. Scheme of the two-zone fluidized bed reactor (TZFBR).
In this work, propane dehydrogenation over Pt-Sn-K/γ-
Al2O3 has been studied under a variety of operating conditions
in laboratory scale, using a two-zone fluidized bed reactor
(TZFBR). In addition, we present a comparison with results in
the literature and the results obtained in a previous work6 with
commercial Cr2O3/Al2O3 catalysts in TZFBR for propane
dehydrogenation.
2. Experimental Section
mixture). A movable axial quartz probe was used to introduce
the propane at different reactor heights (ha). All the streams
were mass flow controlled (Brooks).
A second movable quartz probe located near the reactor axis
was used to take gas samples at different bed heights (h). The
mobile sampling probe was connected to an online gas chro-
matograph (Agilent 3000 µ-CG), which was used to determine
the profile concentration of the different species throughout the
reactor. The reaction products were also analyzed by gas
chromatography. Carbon balances were always better than (3%.
Besides propene, cracked products were formed (ethane, eth-
ylene, and methane). Propane conversion, propene selectivity,
and propene yield were defined as follows:
ni
∑ 3 [F ] i out - [FC3H8]out
i
XC3H8 ) × 100 (1)
ni
∑ [F ]
3 i out
i

2.1. Catalyst Preparation. The Pt-Sn-K/γ-Al2O3 catalyst ni

was prepared by incipient wet impregnation in accordance with [F ]
3 i out
the procedure9 described in the literature but with variations in Si ) × 100 (2)
ni
composition: lower weight percentages of Pt, Sn, and K were ∑ [F ] - [FC3H8]out
3 i out
used to obtain a more easily stabilizable catalyst. The nominal i

composition of the catalysts corroborated by ICP measurements XC3H8SC3H6

was 0.05, 0.14, and 0.10 wt % of Pt, Sn, and K, respectively.
Commercial γ-Al2O3 support (Puralox Sasol Germany GmbH)
with particle size 160-250 µm and BET surface area 153 m2
g-1 was used, with distilled water as solvent. Details of the
catalyst preparation have been given elsewhere.8 After calcina-
tion a 144 m2 g-1 solid catalyst was obtained.
Before the study, the catalyst was pretreated with six cycles
of reduction-reaction-regeneration in a fluidized bed reactor
to obtain an aged and stable catalyst.10,11 In each cycle the
catalyst was (a) reduced in situ in a H2:He ) 1:2 flow during
2 h at 550 °C; (b) reacted in C3H8:Ar ) 1:1 during 30 min at
500 °C; and (c) regenerated in O2:He ) 1:20 during 1 h
at 500 °C.
Finally, the catalyst was ground and sieved to a particle size
of 160-250 µm. This size fraction had a minimum fluidization
velocity (umf) of 0.96 cm3 (STP) cm-2 s-1, obtained with He
at 500 °C. Before each reaction test the catalyst was regenerated
in O2:He ) 1:20 during 2 h at 500 °C and was then reduced in
situ in a H2:He ) 1:2 flow during 2 h at 550 °C. The aged and
stable catalyst, after 150 h of reaction, has a BET surface area
of 138 m2 g-1 and a pore volume of 0.45 cm3 g-1.
2.2. Catalytic Tests. Figure 1 shows a scheme of the two-
zone fluidized bed reactor (TZFBR) used in this work, whose
main characteristics have been described previously.7 The
reactor was placed inside an electrical furnace. The tempera-
ture was measured by a thermocouple while a PID controller
maintained temperature variations within (0.5 °C of the set
point. The reactor was a 30 mm i.d. and 300 mm long quartz
YC3H6 ) (3)
100
where i includes all the components with carbon atoms in the
exit gas stream, ni is the number of carbon atoms of component
i, and Fi is its molar flow.
To obtain a profile of the coke content in the catalyst along
the fluidized bed, the following experimental procedure was
carried out: once steady state was reached, the flow of gas
was suddenly stopped and then a small flow of inert gas (Ar)
was fed, insufficient to fluidize the catalyst, and the reactor was
cooled. Then samples of the catalyst at several axial positions
were taken with a movable quartz probe. The coke content in
the catalyst samples was analyzed in a Mettler-Toledo TGA/
SDTA 851e thermobalance. Also BET surface area tests were
made for these coked samples.
The main reactor-related variables studied were the bed
temperature (T), the relative gas velocity (ur ) u/umf), the amount
of oxygen fed to the reactor as a percentage of the total feed
flow in the bottom of the reactor, and the relative height of the
regeneration and reacting zones. Table 1 shows the reference
values used in this study for these variables.
3. Results and Discussion
3.1. Reactor Stability. Several experiments were performed
to verify that it was possible to reach steady state in the TZFBR,
since continuous work would represent a significant improve-
ment in the propane dehydrogenation.
9316 Ind. Eng. Chem. Res., Vol. 47, No. 23, 2008
Figure 2. Evolution of propene yield with time. T ) 500 °C, Wr/FC3H80 )
90 s kg/mol, 50% C3H8, ha/H ) 0.5, 5% O2 (TZFBR).
Figure 3. Effect of temperature upon propane conversion, propene
selectivity, and product cracking selectivity. Wr/FC3H8 ) 55 s kg/mol, 50%
C3H8, ha/H ) 0.5, ur1 ) 4, and 10% O2.
The stability of the reactor operation was verified by analyz-
ing the exit stream for an extended period of time. Figure 2
shows the evolution of the propene yield as a function of time
for the TZFBR with 5% of oxygen with respect to the total
flow fed and for a conventional fluidized bed reactor (FBR)
without oxygen being fed. While the propene yield decreased
strongly with time in a FBR due to deactivation by coke
deposition, a constant propene yield, approximately 13%, was
reached in the TZFBR, after an initial transient behavior for a
short period of around 15 min. This is due to the stabilization
of the coke content of the catalyst along the reactor for a given
set of experimental conditions. This means that constant exit
flow rates are achieved after an equilibrium is reached between
coke formation in the reacting zone (ha < h < H) and coke
burning in the regeneration zone (0 < h < ha). Therefore CO
and CO2 (COx) appear as products of coke burning in the
regeneration zone but always in very low concentrations (e.g.,
with 5% oxygen in the feed the COx yield is lower than 1%).
In the following sections, all the results reported for the TZFBR
correspond to those obtained after 2 h on stream and thus
correspond to the steady state.
3.2. Effect of Temperature. Figure 3 shows the effect of
temperature upon the propane conversion, propene selectivity,
and selectivity to cracking products. These experiments were
performed keeping the remaining operation variables constant:
ratio between the height of the reaction and the regeneration
zones, (H - ha)/ha, relative gas velocity, ur, catalyst mass, and
flow rates of propane, argon, and oxygen. It may be seen that
at low temperatures (480-500 °C) the propane conversion to
propene and to cracking products increases, as may be expected
Figure 4. Coke concentration along the catalyst bed for different temper-
atures. Operating conditions same as Figure 3.
since both are endothermic reactions, and therefore their
equilibrium conversion increases with the temperature. However,
the propane conversion decreases for temperatures higher than
500 °C, which can be explained from the kinetic model on coke
formation previously developed:8 since the coke formation rate
increases with temperature, the catalyst will be more deactivated
at higher temperatures (i.e., the equilibrium between coke
formation and coke combustion in the TZFBR will be reached
at higher coke content). Cracking is favored over propane
dehydrogenation at high temperatures,8 and as a con-
sequence the propene selectivity decreases. It can be observed
that the maximum of propane conversion and of propene
selectivity are at the same temperature, 500 °C.
The coke content in the catalyst along the bed is shown in
Figure 4 for two different temperatures. The amount of coke
increases along the bed, more quickly in the regeneration
zone than in the reaction zone. Furthermore, the coke content
in the catalyst increases with the reaction temperature. This
has also been observed by several authors.11-14 As would
be expected, the temperature is a very important variable
controlling the coke formation,12 and the large formation of
coke at high temperature explains the surprising decrease of
propane conversion at temperatures higher than 500 °C
(Figure 3). The average surface area obtained for these coked
catalysts is around 120 m2 g-1.
3.3. Influence of Oxygen Flow Rate. The combustion of
coke formed during propane dehydrogenation takes place in
the regeneration zone. Therefore, the amount of oxygen fed
will be a main variable in the operation of a TZFBR. Some
experiments were carried out with a constant input of
propane, while the percentage of oxygen fed to the bottom
of the reactor was varied to keep a constant relative gas
velocity in the regeneration zone (ur2). The remaining
operation parameters were maintained constant: the relation
between the heights of the reaction and the regeneration
zones, (H - ha)/ha, catalyst mass, and reaction temperature.
Figure 5 shows the selectivity to propene versus propane
conversion for experiments performed with different percent-
ages of oxygen in the reactor feed. It can be seen that while
propane conversion increases with the percentage of oxygen
in the reactor feed, the propene selectivity decreases. In all
cases, the steady state is reached, so the coke formation rate
and the catalyst regeneration rate are equal. The coke content
in the catalyst along the bed decreases with the amount of
oxygen fed into the reactor, as shown in Figure 6. These
results can be explained by the fact that as more oxygen is
fed, more coke is burned and the activity of the catalyst is
higher in the dehydrogenation zone. Furthermore, most of

Figure 5. Propene selectivity vs propane conversion for experiments
performed with different O2 flows fed into the reactor and different relative
gas velocityies in the reaction zone, ur1. T ) 500 °C, WT ) 60 g, 50%
C3H8, and ha/H ) 0.5.
Figure 6. Coke concentration along the catalyst bed for two different O2
flows fed into the reactor, operating conditions are the same as Figure 5.
For the 5% O2 run, the profile of oxygen along the bed is shown.
the oxygen fed is consumed in the lower reactor zone where
the regeneration of the catalyst takes place (Figure 6).
Moreover, the propene selectivity decreases because of the
increased formation of COx. It is also possible that if there
is more oxygen than the amount necessary to burn the coke
formed in the reaction zone, some oxygen will reach the up-
per zone of the reactor and new oxidation reactions could
take place. As Pt/Al 2O 3 catalyst is able to promote
combustion,15,16 the hydrocarbon will react with the remain-
ing oxygen to produce COx.
As discussed before, dehydrogenation of propane and
cracking are both very endothermic reactions, so it is ne-
cessary to bring energy to the system. The burning of coke
formed during the propane dehydrogenation brings part of
this energy. A Hysys Plant simulator has been used to
calculate the heat involved in the process for two tests with
different percentages of oxygen fed into the reactor (2.5 and
5% O2), while maintaining the rest of the operating condi-
tions: T ) 500 °C, Wr/FC3H8 ) 90 s kg mol-1, 50% C3H8,
and ha/H ) 0.5. Taking into account the experimentally
obtained yields to the main reaction products, the net heat
produced in the experiment with 5% O2 is 4940 kJ (kmol
C3H8)-1 while with 2.5% O2 it is just 344 kJ (kmol C3H8)-1;
that is, in these cases the combustion of coke brings more
energy than that necessary to carry out the dehydrogenation
reaction. This could avoid having to use an expensive
Ind. Eng. Chem. Res., Vol. 47, No. 23, 2008 9317
Figure 7. Influence of relation between length of the reacting and the
regenerating zones using the same amount of catalyst in the bed. T ) 500
°C, WT ) 60 g, 50% C3H8, H ) 14 cm, and ur1) 2.8.
multitubular reactor to provide the reaction heat, as is
currently used in some industrial processes.
3.4. Effect of the Ratio between the Heights of the
Reaction and the Regeneration Zones. The ratio between the
heights of the reaction and regeneration zones, (H - ha)/ha,
has two effects on the operation of the TZFBR. An increase
in this ratio involves a higher Wr/F ratio in the reaction zone
and a smaller size of the regeneration zone.
Figure 7 shows the propene yield for the same catalyst
weight in the reactor (WT) but for different propane feeding
points (ha), that is, for the same total bed length (H) but
different ratios between the height of the reaction and re-
generation zones (different Wr/F ratios). The flows of oxygen,
propane, and argon fed to the reactor were the same in all
cases. This procedure was repeated with different percentages
of oxygen fed to the bottom of reactor. For 5% of oxygen,
it can be seen that the propene yield increases with (H -
ha)/ha, but for higher values of (H - ha)/ha, the propene yield
decreases. So an optimum propene yield was found when
(H - ha)/ha ) 1; that is, the reaction zone and the
regeneration zone had the same size. Furthermore, stable
operation was not achieved when (H - ha)/ha was higher
than 2 (the height of the regeneration zone was not sufficient
to compensate for the catalyst coking in the reaction zone).
However, when these experiments were carried out with a
larger oxygen flow rate (10% of oxygen), the optimum
propene yield was found at higher values of (H - ha)/ha.
Moreover, when the height of the regeneration zone decreases
(higher values of (H - ha)/ha), the coke content in the catalyst
along the bed increases (Figure 8), as may be expected from
the previous reasoning.
These results can be explained with the help of a previous
kinetic study8 since a higher coke content, as was found in the
experiments with a larger reaction zone, has a greater effect on
the dehydrogenation reaction than on the cracking. Therefore,
more catalyst in contact with the propane feed increases the
propane conversion (approaching the equilibrium value) but
decreases the propene selectivity, and for higher values of
(H - ha)/ha the propene yield decreases, due probably to the
higher amount of coke formed per unit of time and the smaller
size of the regeneration zone.
3.5. Influence of Relative Gas Velocity (ur). Figure 5 shows,
besides the effect of percentage of oxygen in the feed, the
propene selectivity versus propane conversion for experiments
performed with a constant oxygen percentage (5%) and different
relative gas velocities, ur. It can be seen that both propane
conversion and propene selectivity decrease with relative gas
9318 Ind. Eng. Chem. Res., Vol. 47, No. 23, 2008
Figure 8. Coke concentration along the catalyst bed for different ratios of
length of the reacting zone/length of the regenerating zone. T ) 500 °C,
WT ) 60 g, 50% C3H8, H ) 14 cm, and ur1 ) 2.8.
Figure 9. Variation of the propane (full symbols) and oxygen (open
symbols) concentration profiles along the reactor for different values of
ur1. Other operation conditions are the same as Figure 8.
velocity, but propane conversion is more sensitive than propene
selectivity to an increase in ur. The decrease in propane con-
version is easily explained since a larger ur implies a shorter
space time and greater bypass of gas in the bubbles. The ex-
planation for the decrease in selectivity is related with the
decrease in conversion: since the percentage of oxygen in the
feed is constant and is fully consumed, the yield to COx also
remains quite constant, and with a lower propane conversion
this implies a higher selectivity to COx and lower selectivity to
propene.
A second phenomenum that appears in a fluidized bed with
sufficiently high gas velocity (typically ur > 3-5) is the
backmixing of gas.17 In a fluidized bed backmixing of the
gas takes place through a mechanism that is related with
the mixing of solids. Thus, solid material forming the bubble
wake is transported upward with the bubbles; the same solid
flow, but in the downward direction, exists in the emulsion
phase that surrounds the bubbles. If the velocity of the solid
moving downward is higher than the relative gas-solid
velocity in the emulsion phase (which is roughly the
minimum fluidization velocity), then the solid in the emulsion
phase draws gas downward, and the undesired gas backmix-
ing is produced.7 As shown in Figure 9, a clear separation
between the reaction and the regeneration zones can be
obtained if the operating conditions are chosen carefully. It
can be seen that at h < ha the oxygen concentration drops
rapidly as a consequence of the combustion of carbonaceous
deposit on the catalyst. Moreover, at ur ) 2.8 all of the
Figure 10. Comparison between flammability region of propane-oxy-
gen-nitrogen at 500 °C and operating zone in TZFBR, and the operation
conditions are the same as in Figure 9.
Figure 11. Selectivity vs (conversion/equilibrium conversion) for TZFBR
runs and comparison with results from the literature. Diverse operating
conditions.
oxygen fed at the bottom of the bed (h ) 0) is consumed
before reaching the propane inlet (h ) ha), and with an
increase of relative gas velocity, propane was detected below
the hydrocarbon inlet point (h < ha). This effect can also
explain the decrease in selectivity and conversion when the
relative gas velocity increases, because the presence of
propane with oxygen in the regeneration zone can produce
COx due to oxidation of the hydrocarbon while at the same
time reducing coke combustion.
Figure 10 represents the gas composition at different points
inside the TZFBR, for several operating conditions, according
to the values obtained in this study together with the flam-
mability diagram for propane-oxygen-nitrogen mixtures at 500
°C. The flammability region has been taken from the work by
Zabetakis.18 This plot shows the operating zone in the TZFBR
is outside the actual flammability region at the operation
temperature. The diagram is therefore useful to illustrate the
ability of the TZFBR to attain a safe operation.
3.6. Comparison with Results in the Literature. Figure
11 summarizes the catalytic results obtained with the
Pt-Sn-K/γ-Al2O3 catalyst synthesized in this work and
commercial Cr2O3/Al2O36 catalysts used in a TZFBR for
propane dehydrogenation. Some of the best results for Pt-Sn
based catalysts extracted from a survey of the literature are
also shown. To compare the results regardless of the operating

conditions, the results were standardized with the equilibrium
conversion in each case, because the graph includes experi-
mental results from authors that have worked with significant
amounts of hydrogen or inert gas in the feed. Therefore,
Figure 11 shows propene selectivity versus conversion/
equilibrium conversion (at operating conditions). Salmones
et al.19 used a Pt-Sn/MgAl2O4 catalyst in a fixed bed reactor,
co-feeding propane and H2. Assaburmrungrat et al.20 used
several modified Pt/Al2O3 catalysts in a microreactor with a
mixture of 3% propane in nitrogen. Results presented by
Hullmann et al.21 correspond to a platinum silicon nitride
catalyst in a tubular fixed bed reactor, co-feeding propane
and H2. Jabloski et al.22 tested a PtGa/Al2O3 catalyst in a
quartz fixed-bed reactor with high dilution of propane. In
these works, the catalyst was deactivated by coke in spite of
the dilution with inert gas or H2, which in industrial ope-
rations would make necessary its regeneration in another
stage. Moreover, these results show lower ratios of conver-
sion/(equilibrium conversion) in conventional reactors than
in the TZFBR. The selectivity to propene for a given
normalized conversion (which corresponds to much lower
actual propane conversion values in the experiments from
the literature) is similar to that of the TZFBR. The lower
propene selectivity in the TZFBR is due to the formation of
COx, as a product of coke burning in the regeneration zone.
The TZFBR allows in situ regeneration of the catalyst, with
the reaction and regeneration taking place in the same vessel,
so that it can work in continuous mode. Furthermore, the
trend observed in this figure is that the TZFBR results
obtained with both catalysts (synthesized Pt-Sn-K/γ-Al2O3
and commercial Cr2O3/Al2O3) are fairly similar.
4. Conclusions
The main conclusion of this work is that a stable operation
can be achieved for propane dehydrogenation over a Pt-Sn-K/
γ-Al2O3 catalyst in a two-zone fluidized bed reactor, which
can work in continuous mode. The operating variables (bed
temperature, relative gas velocity, oxygen fed into the reactor,
and relative height of the regenerating and reacting zones)
have an important role in the reactor performance, because
when the rates of coke formation (in the reaction zone) and
coke burning (in the regeneration zone) are equal, stable
operation is achieved.
Furthermore, the TZFBR has other advantages over conven-
tional reactors:
(a) In many of the available commercial processes for
dehydrogenation of olefins, hydrogen is fed to reduce coke
formation; however, in a TZFBR no hydrogen is needed.
(b) The coke formed in the reaction zone becomes an
important source of the energy necessary for the dehydrogena-
tion reaction.
(c) Reaction and catalyst regeneration take place in the same
vessel.
(d) Oxygen and hydrocarbons are fed at different points of
the reactor avoiding the formation of a flammable mixture.
Acknowledgment
The authors thank DGI (Spain) for financial support for the
project CTQ2004-01721/PPQ.
Nomenclature
TZFBR ) two-zone fluidized bed reactor
∆HR ) reaction enthalpy [kJ mol-1]
Ind. Eng. Chem. Res., Vol. 47, No. 23, 2008 9319
u0 ) gas velocity [cm3 (STP) cm-2 s-1]
umf ) minimum fluidization velocity [cm3 (STP) cm-2 s-1]
ur ) relative gas velocity [u0/umf]
ur1 ) relative gas velocity in reaction zone [u0 reaction zone/umf]
ur2 ) relative gas velocity in regeneration zone [u0 regeneration zone/
umf]
XC3H8 ) propane conversion [-]
SC3H8 ) propene selectivity [-]
YC3H8 ) propene yield [-]
FC3H8 ) molar flow of propane [mmol min-1]
Fi ) molar flow of a compound i [mmol min-1]
ni ) number of carbon atoms of product i
Wr ) mass of catalyst in reaction zone [g]
WT ) mass of catalyst in reaction zone [g]
QT ) total flow rate [cm3 (STP) min-1]
T ) reaction temperature [K]
t ) time [min]
h ) bed height [cm]
ha ) propane feed point [cm]
H ) total bed length [cm]
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ReceiVed for reView May 27, 2008
ReVised manuscript receiVed September 15, 2008
Accepted September 28, 2008
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