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The kinetics of reactions involved in dehydrogenation of propane to propylene over PtSn/Al2 O3 catalyst was studied.
The simultaneous deactivation of individual dehydrogenation, hydrogenolysis and cracking sites was also studied.
A model was developed to obtain the transient conversion of propane, product selectivity and catalytic site activity.
The dehydrogenation reaction was considered as the main reaction governing propane and hydrogen concentrations
along the reactor. Catalytic test runs were performed in a xed-bed quartz reactor. The kinetic expressions developed for the main and side reactions were veried by integral and a combination of integraldifferential analysis of
reactor data, respectively, and the kinetic parameters were obtained. The deactivation of the active sites for the three
reactions was found to follow a rst-order independent decay law. The rate constants of deactivation were found to
decrease in the order of dehydrogenation, hydrogenolysis and cracking. Noncatalytic thermal cracking was found to
be comparable to the catalytic route resulting in a very low apparent deactivation rate constant for cracking reaction.
2011 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
Keywords: Propane dehydrogenation; PtSn catalysts; Cracking; Hydrogenolysis; Catalyst deactivation; Kinetics
1.
Introduction
Propylene is an important feedstock for producing a variety of petrochemicals such as polypropylene, acrolein and
acrylic acid. Due to ever-increasing demand and insufcient
supply by crackers, alternative production methods such
as propane dehydrogenation (PDH) has received attention
(Heinritz-Adrian et al., 2008):
C3 H8 C3 H6 + H2 ,
(1)
The reaction is highly endothermic and equilibriumlimited; therefore, higher temperatures and lower pressures
are necessary to achieve acceptable conversions. Unfortunately, these conditions favor side reactions and accelerate
catalyst deactivation as well.
In commercial practice both chromia (Arora, 2004; Miracca
and Piovesan, 1999; Weckhuysen and Schoonheydt, 1999) and
platinum (Bricker et al., 1990; Heinritz-Adrin et al., 2003;
Pujado and Vora, 1990) based catalysts have been employed
(2)
(3)
In commercial catalysts, Sn is used as promoter to suppress hydrogenolysis reaction through reduction of surface
Pt ensemble size by dividing Pt surface to smaller ensembles
Nomenclature
a
C
F
ki
kdi
Keq
ri
W
Xi
Xei
t
catalyst activity
concentration (mol/m3 )
feed rate (mol/h)
forward rate constant of reaction i
rate constant for catalyst deactivation in reaction i (h1 )
concentration equilibrium constant (mol/m3 )
rate of reaction i per mass of catalyst
(mol/(kg h))
weight of catalyst in the reactor (kg)
conversion of key reactant A in reaction i
equilibrium conversion of key reactant A in
reaction i
time-on-stream (h)
Greek symbols
2.
Experimental
2.1.
Materials
The propane, hydrogen and nitrogen feed gases were supplied by Roham Gas Co. with purity 99.5 wt.%, 99.99 wt.% and
99.99 wt.%, respectively. Commercial PtSn/-Al2 O3 catalyst
(Pt = 0.58 wt.%, Sn = 0.8 wt.% and surface area = 187 m2 /g) with
trade name DP-803, the characteristics of which is reported
elsewhere (Sahebdelfar and Tahriri Zangeneh, 2010), was supplied by Procatalyse company. Quartz powder with grain size
0.1 mm was used as catalyst diluent.
2.2.
(Barbier et al., 1980; Carvalho et al., 2001; Larese et al., 2000;
Takehira et al., 2004; Waku et al., 2003; Yu et al., 2007; Zhang
et al., 2006c, 2007).
Nevertheless, side reactions still occur to a rather appreciable extent on the catalysts, so that the selectivity of the UOP
Oleex process in dehydrogenation of propane and isobutane
is 90% and 92%, respectively (Bhasin et al., 2001).
Both cracking and hydrogenolysis reactions may occur by
single or multiple CC bond rupture according to the catalyst
formulation and operating conditions. However, a recent study
(Sahebdelfar and Tahriri Zangeneh, 2010) has shown that over
the catalyst and under reaction conditions employed in this
work, the former path is predominant. Consequently, reactions (2) and (3) can represent the side reactions.
It has been shown that side reactions result in signicant
inuence on the performance of commercial-sized dehydrogenation reactors (Sahebdelfar et al., 2011). Unfortunately, it
is difcult to study individual reactions independent of other
reactions. Hydrogenolysis occurs virtually on the same sites
as dehydrogenation. Cracking can occur separately, but under
conditions different from that of dehydrogenation reaction.
Another important difculty in commercial scale implementation of parafn dehydrogenation is rapid catalyst
deactivation due to coke formation (Moulijn et al., 2001). During the course of reaction, different sites deactivate at different
rates resulting in a change in activity and selectivity with
time-on-stream. The overall deactivation kinetics has been
1091
Set-up
2.3.
Experimental procedure
1092
Larsson et al. (1996) found that among several kinetic models tested for dehydrogenation of propane on PtSn/Al2 O3
catalysts, simple power-law model of this type resulted
in the best t. In fact most mechanistic kinetic models,
e.g. LongmuirHinshelwoodHougenWatson (LHHW) based
model of Padmavathi et al. (2005) with surface reaction as
rate-limiting step, approach to power law expressions at the
high-temperature, low-partial pressure (low surface coverage
(Scott Fogler, 1999)) prevalent in lower-parafn dehydrogenation practice.
To account for catalyst deactivation, the reaction rate can
be written in terms of site activity as:
(4)
r 1 = k1 a1
3.
3.1.
Kinetic expressions
r 1 = k1 CA k1 CB CH2 = k1
CB CH2
CA
Keq
(5)
where r1 is the rate of conversion of propane to propylene (reaction (1)) per catalyst weight, k1 and k1 are the
rate constants of forward and backward reactions, respectively, Keq is the equilibrium constant at reaction temperature,
C is the concentration, and, A and B, respectively, representing the key components, propane and propylene.
CB CH2
Keq
(6)
Most previous studies have shown that dehydrogenation reaction is rst-order in parafn concentration and negative half
to zeroth-order in hydrogen concentration (Resasco, 2003).
Therefore to incorporate the rst-order dependence on parafn concentration, hydrogen-inhibition effect, and chemical
equilibrium limitation, the following expression is assumed
to represent kinetics of the reaction:
CA
r 1 (t)
r 1 (t = 0)
(7)
Considering volume change of reaction, following necessary algebraic manipulations, one arrives at the following
expression for reaction rate in terms of propane conversion
(Moghimpour Bijani and Sahebdelfar, 2008):
r 1 =
k1 a1 CA0 (Xe1 X1 )( + X1 )
(1 + A X1 )
(8)
in which
=
(9)
(10)
1093
r 3 = k3 a3 C2A0
(1 X1 )
(1 + A X1 )
(1 + A X1 )
where kdi is the respective rate constant of deactivation. Integrating this equation yields a correlation for ai as a function
of time, t:
ln ai = kdi t
(14)
Reactor model
(15)
ln
ln
1
( A )
ln
( + Xe1 )
2
(1 + A Xe1 )
ln
( + Xe1 )
20
40
+ X
1,out
Xe1
2A X1,out
60
80
100
120
Conversion, %
Time-on-stream, h
(17)
(Xe1 X1 )( + X1 ) dX3
CA0 k3
=
exp((kd1 kd2 )t)
k1
(1 X1 )(H + X1 ) dX1
(18)
Eqs. (17) and (18) hold for any point along the reactor.
Rearranging, integrating with respect to Xi and then differentiating with respect to t, the following correlations are
obtained for cracking and hydrogenolysis reactions, respectively:
X X
e1
1,out
= kd1 t + ln(k1 )
20
30
10
(12)
(13)
40
(1 X1 )(H + X1 )
ln
50
dai
= kdi ai
dt
3.2.
60
(11)
70
= (kd1 kd2 )t + ln
= (kd1 kd3 )t + ln
k
2
k1
k C
3 A0
k1
(19)
(20)
(16)
4.
4.1.
Fig. 2 shows the overall conversion and conversion of individual reactions versus time-on-stream. The rst data points
showing the initial activity, characterized by large deviations, are never actually observed due to experimental
1094
Time-on-stream, h
y = 0.0439x + 2.4186
R = 0.9516
4
3.5
2
1.5
y = 0.063x - 0.2411
R = 0.9303
1
0.5
60
80
100
120
y = -0.0159x - 0.2855
R2 = 0.9543
-1
-1.5
-2
10
20
30
40
-2.5
Conversion to propylene, %
Modeling results
Fig. 4 shows a plot of Eq. (16) for a long-term run using experimental data with LHS showing the left-hand-side of that
equation. A favorable t is observed. The slope and intercept
give the deactivation and reaction rate constants for dehydrogenation reaction, respectively (Table 1).
In this way Eq. (16) provides a method to obtain timezero conversion to propylene i.e. an estimate of conversion in
the absence of deactivation effects which is useful for kinetic
study of the main reaction.
Unlike the integral method of analysis used in Fig. 4,
the plots of Eqs. (19) and (20) require a higher number and
ki
3
4.7 m /(kg h)
0.40 m3 /(kg h)
0.023 m6 /(mol kg h)
more accurate experimental data because of the appearance of time-derivative terms in these equations. To avoid
the uctuations encountered in numerical differentiation, it
has been proposed to t the data with an appropriate function and then differentiate the resulted interpolating function
(Levenspiel, 1999). The trends of time-data propose exponential functions as good candidates (Fig. 2) which in fact result
in fair ts. Figs. 5 and 6, respectively, show plots of Eqs. (19)
and (20) obtained by this approach after achieving convergence of deactivation rate constant difference terms by the
iterative procedure explained above, with LHS showing the
left-hand-side of these equations. Favorable ts are observed.
The resulted rate constants for side reactions are also given in
Table 1.
Table 1 reveals that the rate constants of side reactions
are more than one order of magnitude smaller than those
of the main reaction as required by a selective catalyst. Also,
the dehydrogenation sites deactivate more rapidly than those
of side reactions. This explains the observed drop of selectivity to propylene with time-on-stream. The seemingly smaller
deactivation rate constant in the case of cracking reaction can
be attributed to the simultaneous occurrence of non-catalytic
thermal cracking. The numerical values of rate and deactivation constants are also consistent with the experimental data
trends observed in Figs. 2 and 3.
The existence of a noncatalytic component in cracking
activity implies that higher orders of deactivation could give
Time-on-stream, h
0
20
40
60
80
100
0
-0.5
-1
-1.5
-2
-2.5
y = 0.01318x - 2.45327
R = 0.97686
-3
LHS of Eq. 19
1
2
3
40
-0.5
2.5
4.2.
20
LHS of Eq. 16
Conversion to by-products, %
4.5
-3.5
kdi
1
0.016 h
0.0027 h1
0.011 h1
-4
120
Time-on-stream, h
-2
20
40
60
80
100
120
-2.5
LHS of Eq. 20
-3
-3.5
-4
y = 0.0049x - 3.3575
R = 0.8367
-4.5
1095
-5
-5.5
-6
4.3.
Fig. 7 Correlation between experimental data and model predictions for total propane conversion and propane
conversions to species in operating conditions used.
1096
5.
Conclusions
Appendix.
Eq. (17) can be written as below:
(Xe1 X1 )( + X1 ) dX2
= k exp(At)
(1 X1 )(1 + A X1 ) dX1
(A1)
where
k=
k2
k1
(A2)
A = kd1 kd2
(A3)
(1 X1 )(1 + A X1 )
dX1
(Xe1 X1 )( + X1 )
(A4)
X1,out
X2,out = k exp(At)
0
(1 X1 )(1 + A X1 )
dX1
(Xe1 X1 )( + X1 )
(A5)
+ k exp(At)
t
X1,out
X1,out
(1 X1 )(1 + A X1 )
dX1
(Xe1 X1 )( + X1 )
(1 X1 )(1 + A X1 )
dX1
(Xe1 X1 )( + X1 )
(A6)
in which, the rst term on the right hand side is AX2,out (according to Eq. (A5)). In the second term, as differentiation is with
respect to t and the integral limits are functions of time, the
Leibnizs rule (Bird et al., 2002) must be applied. According to
this rule, for function F(x, t), where
b(t)
F(x, t) =
f (x, t)dx
(A7)
a(t)
f
db
da
dx + f (b, t)
f (a, t)
t
dt
dt
(A8)
Hence, the second term of the right hand side of Eq. (A6) is
k exp(At)
0
dX1 +
X1,out
(1 X1 )(1 + A X1 )
(Xe1 X1 )( + X1 )
(A9)
1097
ln
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= At + ln(k)
(A11)