Article

pubs.acs.org/IECR

Kinetic Modeling of Propane Oxidative Dehydrogenation over VOx/γ-

Al2O3 Catalysts in the Chemical Reactor Engineering Center Riser
Reactor Simulator
S. Al-Ghamdi,†,‡ J. Moreira,† and H. de Lasa*,†
†
Chemical Reactor Engineering Centre, University of Western Ontario, London, Ontario, Canada
‡
Research & Development Center, Saudi Aramco Oil Company, Dhahran, Saudi Arabia
*
S Supporting Information

ABSTRACT: This study reports kinetic modeling of propane oxidative dehydrogenation (ODH) employing a new VOx/γ-
Al2O3 catalyst especially designed for propane ODH with a controlled acidity. This catalyst is prepared with different vanadium
loadings (5−10 wt %). Kinetic experiments are carried out under an oxygen-free atmosphere in the Chemical Reactor
Engineering Center fluidized bed riser simulator at 475−550 °C and atmospheric pressure. Successive-injection propane ODH
experiments (without catalyst regeneration) over partially reduced catalysts show good propane conversions (11.73%-15.11%)
and promising propylene selectivity (67.65−85.89%). Regarding propylene selectivity, it increases while that for COx decreases as
the catalyst degree of reduction augments with the consecutive propane injections. This suggests that a controlled degree of
catalyst reduction is needed for high propylene selectivity. Under such oxygen-free conditions, the lattice oxygen of the catalyst is
consumed via the ODH reaction. On the basis of the data obtained, a kinetic model is proposed. In this model, reaction rates are
related to the degree of catalyst reduction using an exponential decay function. The kinetic and decay model parameters are
estimated using nonlinear regression analysis. Activation energies and Arrhenius pre-exponential constants are calculated with
their respective confidence intervals. The proposed parallel-series kinetic model satisfactorily predicts the ODH reaction of
propane under the selected reaction conditions.

1. INTRODUCTION studies have been based on experiments involving cofeeding of

With the increasing worldwide demand for light olefins, the
conversion of light paraffins, ethane, propane, and butane, to
their corresponding olefins is a topic of current commercial
interest.1−20 Light olefins, such as ethylene and propylene are
important raw materials for the synthesis of polymers and
various petrochemical products. Oxidative dehydrogenation
(ODH) of light paraffins has been the most investigated route
for olefin production, overcoming many limitations of the
current olefin production processes, namely, high energy
requirements, coke formation, and thermodynamic con-
straints.21−27 However, the low selectivity toward the desired
olefin products is the main problem of light paraffin ODH
process preventing it from an industrial application.2,28−32
Light paraffin oxidative dehydrogenation involves a complex
reaction network. This reaction network involves competitive
reactions taking place simultaneously. In such system, oxygen
supply plays an important role. This is the case as the reaction
rates for both olefin production and reactants/products
combustion are strongly influenced by oxygen concentration.
Thus, optimized oxygen concentration is required in order to
maximize selectivity toward the desired olefin products.
Kinetic studies for short chain alkane (ethane, propane, and
butane) ODH have been the subject of a significant number of
papers in the open literature.14,16,30,33−57 These contributions
use different kinetic models such as the Langmuir−Hinshel-
wood, the Eley−Rideal, or the Mars van Krevelen models. It is
important to mention that the proposed kinetic models in these
hydrocarbon species and molecular oxygen to the reaction unit.
However, only a few studies among the above-mentioned
research have considered propane ODH in the absence of gas
phase oxygen, and only a few of them reported data on kinetic
investigations.45,50,52,58−65 In all these studies, the proposed
kinetic models involved hydrocarbon molecules reacting with
the lattice oxygen of the supported metal oxides, giving olefins
and H2O. The reduced metal oxides are reoxidized by gas phase
molecular oxygen to regenerate the active metal oxides and
replenish the lattice oxygen.
Moreover, there is limited information that deals with light
olefins ODH in dense fluidized beds, risers, or downers
reactors. These studies are being confined mainly to butane
ODH.35,66−68 There is also the motivation of using fluidized-
bed reactors in light paraffins ODH. This is due to their
controlled isothermal conditions, uniform residence time
distributions, and the absence of mass transfer limitations.
Hence, one can circumvent with these units, the potential issues
with nonisothermal conditions in fixed-bed catalytic reactors.
Moreover, fluidized reactors with periodic catalyst reoxida-
tion offer the means that enables the transport of the reduced
catalyst from the oxidative dehydrogenation reaction unit to the
Special Issue: Alirio Rodrigues Festschrift
Received: December 1, 2013
Revised: January 29, 2014
Accepted: February 3, 2014

© XXXX American Chemical Society A dx.doi.org/10.1021/ie404064j | Ind. Eng. Chem. Res. XXXX, XXX, XXX−XXX
Industrial & Engineering Chemistry Research
reoxidation unit. Thus, the operation of twin reactors, one for
the ODH reaction and one for catalyst regeneration appears to
be a requirement for the implementation of this technology at
an industrial scale. In this regard, ethane ODH over VOx/γ-
Al2O3 has been successfully tested in the Chemical Reactor
Engineering Center (CREC) riser simulator in the absence of
molecular gas oxygen. Promising ethane conversions and
ethylene selectivities have already been published.69,70 Thus,
it is in our interest and given the significant prospects for
industrial applications to extend our research and explore
propane ODH in the CREC riser simulator over VOx/γ-Al2O3
catalysts in an oxygen-free atmosphere.
Given the above-described facts, the goal of this paper is to
establish propane ODH kinetics over a new VOx/γ-Al2O3
fludizable catalyst for propane ODH in the absence of gas
phase oxygen. To accomplish this, a kinetic model in which
reaction rates are related to the degree of catalyst reduction
using an exponential decay function is proposed. It is our
understanding that such propane ODH kinetics in the absence
of molecular oxygen gas together with a very selective
vanadium-based catalyst and the demonstration of its perform-
ance in a fluidized bed laboratory reactor has not been reported
before.
2. EXPERIMENTAL SECTION
2.1. Catalyst Preparation and Characterization. The
VOx/γ-Al2O3 catalysts used in this investigation were prepared
by wet saturation-impregnation of a commercial porous γ-Al2O3
support with (SASOL, Catalox SCCa 5/200), with an aqueous
solution of NH4VO3 (Sigma Aldrich, 99%) and oxalic acid
(Sigma Aldrich, 99%) in a 1:2 weight ratio and at a pH of ∼2.
The prepared samples were characterized by BET surface area,
temperature programmed reduction (TPR), X-ray diffraction
(XRD), and NH3 temperature programmed oxidation (NH3-
TPD), O2 pulse chemisorption, and laser Raman spectroscopy
(LRS). A detailed description of the catalyst preparation and
characterization techniques used are given in a recent
publication by Al-Ghamdi et al.71 For the sake of avoiding
already reported information, the specifics on the preparation
and characterization techniques will not be given in the present
manuscript.
2.2. Propane ODH Reaction Studies. The catalytic
propane oxidative dehydrogenation experiments over various
supported vanadium oxide catalysts were established at the
CREC using the riser simulator. The CREC riser simulator is a
bench-scale mini-fluidized bed reactor, invented by de Lasa.72
This unit is specially designed for catalyst evaluation and kinetic
studies under fluidized bed (riser/downer) reactor conditions.
Details of the CREC riser simulator as well as the experimental
procedure and setup have already been reported elsewhere by
Al-Ghamdi et al.70
Thermal and catalytic experiments of propane ODH were
carried out at four temperatures (475, 500, 525, and 550 °C),
one catalyst loading (0.76 g) and four contact times (5, 10, 15,
and 20 s). All catalytic runs were repeated at three times to
ensure reproducibility of the experimental results. The carbon
mass balance closures, which considered all carbon-containing
products such as CO, CO2, CH4, ethylene, ethane, propylene,
propane, and carbon deposited over the catalyst were in the ± 7
% range. For each catalyst, 10 sequential propane injections
were used at a particular temperature and contact time.. On the
basis of the inlet and outlet concentrations, the conversion,
selectivity, and yield were calculated.
B dx.doi.org/10.1021/ie404064j | Ind. Eng. Chem. Res. XXXX, XXX, XXX−XXX
Article
3. KINETIC MODELING
Propane ODH involves a network of consecutive and parallel
reactions, namely, the ODH of propane, the undesired
combustion of propane feed, and the secondary combustion
of propylene product. These reactions can be described
stochiometrically as
1
C3H8 + O2 → C3H6 + H 2O
2 (1)
1
C3H8 + (3x + 4)O2 → 3COx + 4H 2O
2 (2)
1
C3H6 + (3x + 3)O2 → 3COx + 3H 2O
2 (3)
with the latter two reactions 2 and 3 being the limiting ones for
propylene selectivity and yield during propane ODH.
On the basis of the observed dependence between propane
conversion and product selectivities for propane ODH, a
parallel-series “triangular” reaction network is proposed in this
study as described in Figure 1.
Figure 1. Proposed reaction network for propane ODH over VOx/γ-
Al2O3 catalysts in a CREC riser simulator.
The proposed reaction network assumes that propane feed
reacts with lattice oxygen promoting two parallel reactions. One
of the possible reactions is the formation of the desired
propylene product via ODH, with a rate constant k1.
Alternatively, propane can be competitively converted forming
combustion products (COx), with a rate constant k2. Finally,
the formed propylene may also follow a secondary reaction step
leading to the formation of combustion products (COx), with
rate constant k3.
3.1. Kinetic Model Development. Regarding kinetic
model development and in cases such as the one of the
present study, in which propane ODH is carried out in the
absence of gas phase oxygen, it can be postulated that oxygen
from the catalyst lattice is consumed via propane ODH
reactions only. Under such conditions, the catalyst oxygen
content has to be included in the kinetic model. Moreover, an
allowance must be made for the catalyst’s time on stream or
catalyst history in order to achieve a kinetic model capable of
describing all transient observations during the course of the
ODH reaction.
To accomplish this, the catalyst oxygen content can be
expressed using a time dependent degree of oxidation (%
oxidation). This time-dependent degree of oxidation can be
defined as the ratio of oxygen content left after the ODH
reaction over the original oxygen content of the catalyst before
the ODH run. The catalyst degree of oxidation is expected to
decrease during the ODH reaction cycle. This is especially true,
Industrial & Engineering Chemistry Research Article

as in the present study, if one does not allow catalyst C3H8 − [S2 ](s) + (4 + 3x)[S1O](s)
reoxidation, or replenishment of the lattice oxygen by gas-phase k2
molecular oxygen in between ODH reaction cycles. → 3COx (g) + 4H 2O(g) + (4 + 3x)[S1R ](s)
A possible approach to kinetic modeling based on the
+ [S2 ](s) (8)
available lattice oxygen during oxygen-free ODH reactions is
the use of an exponential decay function based on converted
propane. This type of activity decay function is similar to the (v) Formation of COx from propene (r3) via further reaction
one initially proposed by de Lasa and Al-Khattaf73 for FCC of adsorbed propene with lattice oxygen in an oxidized
catalytic activity decay, Hossain et al.74 for ethylbenzene site [S1O]:
dehydrogenation to styrene, and recently by Al-Ghamdi et al75
for ethane ODH reaction, and it can be written as follows: C3H6 − [S2 ](s) + (3 + 3x)[S1O](s)
→ 3COx (g) + 3H 2O(g) + (3 + 3x)[S1R ](s)
ϕ = exp[−λ(XC3H8)] (4)
+ [S2 ](s) (9)
where ϕ is the catalyst’s degree of oxidation, λ is a constant, and
X is the propane conversion. The main advantage of this (vi) Reoxidation of the reduced metallic center by molecular
function is that it accounts for the effects of reaction conditions oxygen:
(temperature, concentration, and contact time) on the catalyst
extent of oxidation. O2 (g) + 2[S1R ](s) → [S1O](s) + [S1O](s) (10)
Furthermore, the choice of the kinetic model for propane On the basis of a MVK mechanism, the rate equations
ODH is of paramount importance. With this in mind, a Mars corresponding to each surface reaction in the above steps, (i.e.,
van Krevelen (MVK) mechanism is considered in the present r1, r2, and r3) are expressed as follows:
study. This model is generally accepted for oxidative
dehydrogenation reactions over vanadia catalysts involving r1 = k1θC3H8(1 − β) (11)
VOx lattice oxygen species. On the basis of a MVK mechanism
established in the context of two catalyst sites for propane r2 = k 2θC3H8(1 − β) (12)
ODH, the catalyst is reduced by the reaction of the adsorbed
propane with catalyst lattice oxygen to produce propylene r3 = k 3θC3H6(1 − β) (13)
molecules and carbon oxides. Moreover, the adsorbed
propylene product on the catalyst surface can further react where ri is the reaction rate (mol/g·sec), ki is the reaction rate
with lattice oxygen producing carbon oxides. Gas phase oxygen constant (mol/g·sec), θi is the surface coverage of adsorbed
can be intermittently introduced following several propane species “i”, with β + γ = 1, in which β represents the reduced
injections to replenish the lattice oxygen by reoxidation of the vanadium sites and γ = 1 − β represents the oxidized vanadium
catalyst. sites (site 1 type), and θC3H8 + θC3H6 + θv = 1 describes the
As a result, the following six-step mechanism is proposed as alumina based sites (site 2 type).
shown below, with [S1O] representing lattice oxygen in an Thus, and as a result, the surface coverage θi is given by
oxidized site-1, [S1R] denoting a surface oxygen vacancy in a
K C3H8CC3H8
reduced site-1, and [S2] representing alumina-based sites θC3H8 =
(i) Propane adsorption on a site type-2 [S2] on the catalyst (1 + K C3H8CC3H8 + K C3H6CC3H6) (14)
surface:
K C3H6CC3H6
K C3H8 θC3H6 =
C3H8(g) + [S2 ](s) ←⎯⎯→ C3H8 − [S2 ](s) (5) (1 + K C3H8CC3H8 + K C3H6CC3H6) (15)

where Ki is the adsorption constant (cm3/mol) of species “i”

(ii) Formation of propylene (r1) via the surface reaction of
and Ci is the concentration (mol/cm3) of species “i”. Moreover,
adsorbed propane with lattice oxygen in an oxidized site given the proposed decay model for the catalyst’s degree of
[S1O] via H-abstraction: oxidation (ϕ) in eq 4, β can be related to ϕ as
C3H8 − [S2 ](s) + 2[S1O](s) (1 − β) = φ (16)
k1
→ C3H6 − [S2 ](s) + H 2O(g) + [S1O](s) A substitution of eqs 14 to 16 into eqs. 11 to 13 gives the
following rate equations based on the proposed reaction
+ [S1R ](s) (6) network in Figure 1:
k1K C3H8CC3H8
(iii) Desorption of adsorbed propylene from a reduced site: r1 = exp[−λ(XC3H8)]
K C3H6
(1 + K C3H8CC3H8 + K C3H6CC3H6)
C3H6 − [S2 ](s) ←⎯⎯→ C3H8(g) + [S2](s) (7) (17)

k 2K C3H8CC3H8
(iv) Formation of COx from propane (r2) via the reaction of r2 = exp[−λ(XC3H8)]
adsorbed propane with lattice oxygen in an oxidized site (1 + K C3H8CC3H8 + K C3H6CC3H6)
[S1O]: (18)

C dx.doi.org/10.1021/ie404064j | Ind. Eng. Chem. Res. XXXX, XXX, XXX−XXX

Industrial & Engineering Chemistry Research Article

k 3K C3H6CC3H6 dyi Wc ⎛ MWi VR ⎞

r3 = exp[−λ(XC3H8)] = ⎜ ⎟ri
(1 + K C3H8CC3H8 + K C3H6CC3H6) dt VR ⎝ Whc ⎠ (25)
(19)
This equation is appropriate under the conditions of the
One can notice in eqs 17,18, and 19 that the rate of reaction is present study given that (a) the CREC riser simulator is a
related to the adsorption constants, the catalyst extent of bench-scale isothermal well-mixed batch reactor unit with a
oxidation, and the intrinsic kinetic parameters. high fluid gas recirculation and mixing times in the 20−30 ms
Furthermore, using these rate equations, one can establish scale77 and (b) the catalyst particles operate freely from
the overall rate of consumption and/or formation of chemical intraparticle diffusional transport controls. The second
species. This can be accomplished on the basis of the algebraic condition is met given the small size of catalyst particles (90
addition of reaction rates consistent with the reaction network μm) and the porous structure of the fludizable alumina used.
given in Figure 1. On the basis of this, the following rate By establishing one equation such as eq 25 for each
equations could be established for each chemical species component, one can obtain a set of differential equations to
involved in the propane ODH reaction network: represent the propane ODH network. This set of ordinary
differential equations is obtained by substituting the rate
Rate of Propane Consumption: equation of each component given in eqs 20 to 22 into eq 25
and considering that
rC3H8 = −(r1 + r2) yC H Whc
3 8
−(k1 + k 2)K C3H8CC3H8 CC3H8 =
= exp[−λ(XC3H8)] MWC3H8VR (26)
(1 + K C3H8CC3H8 + K C3H6CC3H6)
and
(20)
yC H Whc
Rate of propylene formation: CC3H6 = 3 6

MWC3H6VR (27)
rC3H6 = r1 − r3
One can obtain
(k1)K C3H8CC3H8 − (k 3)K C3H6CC3H6
= exp[−λ(XC3H8)]
(1 + K C3H8CC3H8 + K C3H6CC3H6) for propane:
(21)
dyC H −Wc ⎛ MWC3H8 VR ⎞
Rate of COx formation: 3 8
= ⎜ ⎟
dt VR ⎝ Whc ⎠
rCOx = r2 + r3 (k1 + k 2)αK C3H8yC H
3 8
(k 2)K C3H8CC3H8 + (k 3)K C3H6CC3H6 ×
= exp[−λ(XC3H8)] (1 + αK C3H8yC H + βK C3H6yC H )
3 8 3 6
(1 + K C3H8CC3H8 + K C3H6CC3H6)
(22)
× exp[−λ(XC3H8)] (28)
3.2. Kinetic Modeling in the CREC Riser Simulator. for propylene:
Kinetic modeling in the CREC riser simulator requires species
balances. Such species balance equations can be established on
dyC H Wc ⎛ MWC3H6VR ⎞
3 6
= ⎜ ⎟
the basis of a well mixed isothermal batch-scale reactor.76,77 dt VR ⎝ Whc ⎠
Thus, the following CREC riser simulator equation can be
considered: k1αK C3H8yC H − k 3βK C3H6yC H
3 8 3 6
×
VR dCi (1 + αK C3H8yC H + βK C3H6yC H )
3 8 3 6
ri =
Wc dt (23) × exp[−λ(XC3H8)] (29)
where VR is the volume of riser simulator (cm3), Wc is the
for COx:
weight of the catalyst (g), Ci is the concentration of species “i”
(mol/cm3), and t is the time (seconds). dyCO Wc ⎛ MWCOxVR ⎞
The concentration of any species (Ci) is related to its weight
x
= ⎜ ⎟
fraction (yi) as dt VR ⎝ Whc ⎠
k 2αK C3H8yC H + k 3βK C3H6yC H
yW
i hc 3 8 3 6
Ci = ×
MWi VR (24) (1 + αK C3H8yC H + βK C3H6yC H )
3 8 3 6

where Whc is the total mass of hydrocarbons injected into the × exp[−λ(XC3H8)] (30)
riser simulator (g), MWi is the molecular weight of ith
component (g/mol), and VR is the riser simulator volume where α = (Whc)/(MWC3H8VR) and β = (Whc)/(MWC3H6VR)
(cm3). The system of ODE given in eqs 28 to 30 can be solved with
After replacing eq 24 into eq 23 and after the required a carefully selected set of initial conditions. This allows
algebraic steps, the CREC riser simulator design equation is describing the mass fraction changes of various chemical
obtained in terms of weight fractions chemical species: species (e.g., propane, propylene, and COx) with reaction time.
D dx.doi.org/10.1021/ie404064j | Ind. Eng. Chem. Res. XXXX, XXX, XXX−XXX
Industrial & Engineering Chemistry Research Article

Table 1. Characteristics of Alumina Support and Supported Vanadia Catalyst

V contenta SBET (m2/ H2 uptake (cm3 % surface density NH3 uptake (cm3 Lewis/Brønsted % dispersionc
sample (wt %) g) STP/g) reductionb (V/nm2) STP/g) ratio (O/V)
γ-Al2O3 0 203.52 0.54 16.26
(activated)
5% V/γ-Al2O3 5 188.64 0.45 81.28 3.1 10.94 1.8 63.26
7% V/γ-Al2O3 7 179.27 0.46 83.06 4.6 11.50 4.2 59.81
10% V/γ-Al2O3 10 153.37 0.39 99.18 7.7 13.02 5.1 43.25
a
V content, in wt % was determined by ICP. bBased on V2O5 + 2H2 → V2O3 + 2H2O. cDispersion = fraction of vanadium atoms at the surface,
assuming Oads/Vsurf = 1

Furthermore, to obtain the intrinsic kinetic parameters
(activation energies (Ei) and pre-exponential factors (kio)),
the temperature dependence of each (ki) parameter in eqs 28 to
30 can be represented using the Arrhenius’ equation as follows:
⎡ −E ⎛ 1 1 ⎞⎤
ki = kio exp⎢ i ⎜ − ⎟⎥
⎢⎣ R ⎝ T Tm ⎠⎥⎦ (31)
where koi is the pre-exponential factor (mol/g·sec) expressing
ODH vanadium oxidize catalyst reactivity at reaction time zero
and T = Tm, Ei is the activation energy (kJ/mol), R is the
universal gas constant, and Tm is the average temperature (K).
To reduce the cross-correlation between the pre-exponential
factors koi and the activation energies Ei, the ki constants were
reparameterized, as shown in eq 31. This was accomplished by
centering the reaction temperature at an average value of Tm =
512.5 °C. This temperature corresponds to the average reaction
temperatures used in the present study as recommended by
Hossain and de Lasa.78
In the same way and on the basis of adsorption
thermodynamics, one can relate the adsorption constant Ki
with the reaction temperature T, as
⎡ −ΔH ⎛ 1
1 ⎞⎤
K i = K io exp⎢ i
⎜ − ⎟⎥
⎢⎣ R ⎝ T Tm ⎠⎥⎦ (32)
where −ΔHi is the heat of adsorption (kJ/mol) and is the koi
pre-exponential factor (cm3/mol). The substitution of eq 32
and eq 33 into eqs 29 to 31 gives a new set of ordinary
differential equations with the intrinsic kinetic parameters (koi ,
Ei, Koi and −ΔHi) to be estimated.
4. RESULTS AND DISCUSSION
4.1. Catalyst Characterization. Catalyst characterization
results are summarized in Table 1. Additional information
regarding catalyst characterization can be found in our recent
publication by Al-Ghamdi et al.71 BET surface area analysis of
the prepared VOx/γ-Al2O3 catalysts showed a moderate
decrease in the total surface area of the catalyst upon vanadium
loading on the calcined γ-Al2O3 support. This decrease of the
surface area was due to the plugging of some of the support
pores by vanadium species.
H2-TPR showed that all VOx/γ-Al2O3 catalysts exhibited a
single low temperature reduction peak at around 450 °C which
was due to the reduction of isolated and two-dimensional
structures of surface vanadia. Moreover, the reducibility (%
reduction) of the surface VOx species increased with surface
VOx surface density in the submonolayer region.
O2-chemisorption and Raman spectroscopy demonstrated
that the structure and dispersion of the VOx surface species
depend on their surface density. The surface vanadia species
becomes more polymerized with increasing vanadium loading.
E dx.doi.org/10.1021/ie404064j | Ind. Eng. Chem. Res. XXXX, XXX, XXX−XXX
NH3-TPD and pyridine FTIR analysis showed that both the
number and nature of the acid sites change with vanadium
loading. The surface vanadia species (VOx) cover the exposed
alumina surface Lewis acid sites, resulting in lower acidity than
that of the bare support. Moreover, the number of surface
Brønsted acid sites increased with increasing surface VOx. This
indicated that polymeric surface VOx species possess more
Brønsted acid character than the isolated surface VOx species.
X-ray diffraction (XRD) demonstrated the absence of V2O5
bulk surface species and the high dispersion of VOx on the
support surface. No evidence of AlV3O9 was detected in any of
the samples suggesting that the reaction between VOx and
Al2O3 is negligible during the treatment at 600 °C.
Moreover, XRD analysis on spent catalysts after 10
consecutive ODH propane injections and at the most severe
reaction conditions showed no diffraction patterns. This result
was assigned to the structural changes other than those
occurring in the bare γ-Al2O3 support. This can also be viewed
as an indication of the high catalyst stability under the reaction
conditions.
4.2. Propane ODH in CREC Riser Simulator. Table 2
reports propane conversion and product selectivities for the
successive-injection propane ODH experiments over the
various VOx/γ-Al2O3 catalysts at various contact times and
different temperatures. One should also notice that the only
identifiable carbon-containing products other than propylene
were CO, CO2, CH4, C2H6, and C2H4.
On the basis of the product distribution results shown in
Table 2, the variation of product selectivities with propane
conversion is shown in Figure 2, for the various VOx/γ-Al2O3
catalysts. It is apparent from Figure 2 that the propene
selectivity is inversely related to the conversion for each
catalyst.
The decrease in propylene selectivity with a corresponding
increase in COx selectivities shows that propylene is the
primary reaction product of the propane ODH while COx is the
secondary product of the consecutive oxidation of propane feed
and propylene product. On the basis of these results, a parallel-
series “triangular” reaction network with “direct alkane
combustion” together with “alkene formation” and later “alkene
combustion” could be proposed for propane ODH as given in
Figure 1. Further discussion about the reaction network is given
in the Kinetic Modeling section.
Figure 3 reports the various gas species conversions/
selectivities as a function of a propane injection for two sets
of propane ODH experiments over the various VOx/γ-Al2O3
catalysts. Figure 3a,b describes successive-propane injections
during ODH runs. The catalyst is not regenerated in between
propane injections (pulses). It can be observed in Figure 3a
that the conversion of propane is highest after the first injection
for all catalysts, and then decreases with the increasing number
of propane injections.
Industrial & Engineering Chemistry Research Article

Table 2. Conversion and Product Distribution Results for Sequential-Injections Propane ODH Experiments over Various VOx/
γ-Al2O3 Catalystsa
selectivity (%)
o
catalyst time (s) T ( C) XC3H8 (%) C3H6 COx CH4 C2H6 C2H4 C3H6 yield (%)
5% VOx/γ-Al2O3 5 475 2.35 70.89 86.49 2.76 0.24 0.70 1.63
500 3.08 73.37 86.26 4.73 0.60 1.30 2.18
525 3.83 75.44 88.01 6.14 1.51 2.26 2.85
550 4.08 76.38 89.66 6.30 1.54 3.78 3.13
7% VOx/γ-Al2O3 475 3.24 60.73 35.81 2.57 0.25 0.64 1.62
500 3.74 64.75 29.00 4.45 0.65 1.16 2.14
525 4.60 65.29 24.36 6.31 1.76 2.28 2.63
550 5.06 66.20 20.01 7.12 2.43 4.24 3.18
10% VOx/γ-Al2O3 475 3.73 55.12 41.52 2.48 0.27 0.61 1.48
500 4.22 57.24 36.74 4.27 0.71 1.04 2.01
525 5.26 58.79 30.29 6.60 2.06 2.26 2.47
550 6.16 60.64 23.79 7.83 3.18 4.56 3.49
5% VOx/γ-Al2O3 10 475 3.29 76.86 89.88 2.97 0.27 0.67 2.50
500 4.59 77.53 89.96 4.20 0.69 1.06 3.46
525 6.32 79.92 91.09 5.67 2.10 2.03 5.03
550 6.08 81.24 91.86 5.49 2.20 2.76 4.98
7% VOx/γ-Al2O3 475 4.18 67.20 29.30 2.61 0.30 0.59 2.59
500 5.60 68.94 24.78 4.29 0.89 1.11 3.53
525 6.55 70.60 19.46 5.79 2.20 1.94 4.34
550 8.41 71.49 15.64 6.60 2.98 3.30 5.90
10% VOx/γ-Al2O3 475 4.67 61.99 34.59 2.49 0.33 0.59 2.57
500 6.27 63.43 30.05 4.44 1.03 1.06 3.42
525 7.24 64.75 25.05 6.04 2.28 1.88 4.10
550 10.50 66.18 18.79 7.51 3.68 3.84 6.64
5% VOx/γ-Al2O3 15 475 4.19 80.35 91.53 2.97 0.29 0.67 3.35
500 5.77 81.89 91.89 4.98 0.94 1.12 4.71
525 7.99 83.28 92.90 5.58 2.60 1.99 6.67
550 9.12 84.52 93.88 5.05 3.30 2.44 7.73
7% VOx/γ-Al2O3 475 5.14 67.68 28.76 2.64 0.32 0.61 3.29
500 6.89 71.58 22.00 4.37 1.01 1.03 4.69
525 9.77 71.98 19.11 5.00 2.31 1.61 6.78
550 11.21 74.46 11.67 6.73 3.92 3.22 8.36
10% VOx/γ-Al2O3 475 5.90 61.67 34.82 2.60 0.34 0.57 3.32
500 7.68 64.64 29.27 4.13 1.03 0.92 4.52
525 10.79 65.78 25.89 4.85 2.07 1.41 6.56
550 12.93 66.81 16.13 8.53 4.75 3.78 8.53
5% VOx/γ-Al2O3 20 475 5.38 84.42 94.45 2.94 0.31 0.61 4.53
500 7.32 84.70 95.22 4.15 0.89 0.96 6.21
525 8.88 85.79 95.52 4.84 2.30 1.75 7.64
550 11.73 85.94 96.90 5.41 3.62 1.55 10.11
7% VOx/γ-Al2O3 475 6.42 71.20 25.19 2.73 0.34 0.55 4.36
500 8.11 73.09 21.03 4.02 0.99 0.87 5.82
525 11.88 73.79 17.51 4.78 2.40 1.51 8.45
550 13.36 75.34 10.43 7.21 4.44 2.58 10.06
10% VOx/γ-Al2O3 475 7.16 64.13 32.45 2.53 0.36 0.53 4.24
500 9.14 65.73 28.66 3.72 1.07 0.82 5.70
525 13.41 67.29 23.58 5.21 2.48 1.43 8.32
550 15.05 67.77 15.01 8.72 4.99 3.51 10.16
a
Reported values are the average of 10 consecutive C3H8 injections.

As no molecular oxygen is fed with the injection, the catalyst that the decrease of propane conversion over VOx/γ-Al2O3
is believed to supply all the oxygen for the ODH reaction. catalysts mainly resulted from the consumption of the reactive
Following the first injection, propane conversion declined lattice oxygen species present on the catalyst with propane
drastically from 58.9, 76.5, and 81.9 to 12.5, 14.4 and 16.4%. injections. Moreover, it can be seen for all catalysts that the first
Following this, there was a further gradual decrease to 11.5, injection also has very low propylene selectivity and high COx
12.4, and 13.6% with subsequent propane injections over the selectivity.
5%VOx/γ-Al2O3, 7%VOx/γ-Al2O3, and 10%VOx/γ-Al2O3 cata- Fully oxidized VOx/γ-Al2O3 catalysts are considered non-
lysts samples, respectively. Therefore, it is plausible to suggest selective for the ODH reaction as seen from the results
F dx.doi.org/10.1021/ie404064j | Ind. Eng. Chem. Res. XXXX, XXX, XXX−XXX
Industrial & Engineering Chemistry Research
Figure 2. Propylene selectivities (filled symbols) and COx selectivities (empty symbols) as a function of C3H8 conversion (C3H8 injected = 10 mL,
contact time = 20 s, catalyst loaded = 0.76 g). Error bars correspond to standard deviation of three trials (data reported for 10 consecutive pulses
without catalyst regeneration between the injections).
obtained at the first injection. When the catalyst is in a fully
oxidized state, there is a higher population of nonselective
surface oxygen species which is more likely to promote the
deep oxidation of hydrocarbons to carbon oxides. These
nonselective oxygen species could be formed due to either the
loosely bound lattice oxygen or the adsorbed oxygen from the
regeneration step which could have remained on the VOx/γ-
Al2O3 catalyst surface.
However, it can be noticed in Figure 3b that following the
first propane injection, the selectivities for propylene increase
with propane injections showing stable values at around 92%,
82.2%, and 76.1% over the 5%VOx/γ-Al2O3, 7%VOx/γ-Al2O3
and 10%VOx/γ-Al2O3 catalysts samples, respectively. On the
other hand, selectivities for COx decrease with propane
injections and this seems to indicate that a certain degree of
catalyst reduction is required in order to obtain good propylene
selectivity. In this regard, a selective catalyst surface would be
obtained only after the adsorbed oxygen had been consumed by
the first propane injection. This is evident from the subsequent
propane injections where the selectivity to propylene increases
with the number of propane injections while that for
combustion products (COx) decreases.
G dx.doi.org/10.1021/ie404064j | Ind. Eng. Chem. Res. XXXX, XXX, XXX−XXX
Article
These findings demonstrate that in consecutive ODH
reactions without catalyst regeneration in between (oxygen-
free environment), propane can be converted selectively to
propylene. This occurs due to the lattice oxygen involvement in
the ODH reaction mechanism. One can also notice that
following the first ethane injection (first pulse), the catalyst
tested displays a stable performance in terms of ethane
conversion and ethylene selectivity even after 10 successive
reduction runs.
On the other hand, Figure 3c,d reports a second set of
experiments involving repeated ODH reaction-regeneration
cycles at 550 °C over the various VOx/ γ-Al2O3 catalysts.
Catalyst regeneration was conducted by flowing air at 550 °C
over the catalyst after each propane injection (pulse). Results
show that propane conversion and product selectivities
(equivalent to a per-pass conversion and selectivity in a
continuous riser/downer unit) remain stable during the
different runs. It can be observed in Figure 3c,d that propane
conversion remains at the 60, 73.2, and 80.1% values over the
5%VOx/γ-Al2O3, 7%VOx/γ-Al2O3, and 10%VOx/γ-Al2O3 cata-
lysts samples, respectively. On the other hand, very low
propylene selectivities in the 2.1, 0.93, and 0.57% levels are
observed over the 5%VOx/γ-Al2O3, 7%VOx/γ-Al2O3, and 10%
Industrial & Engineering Chemistry Research Article

Figure 3. Propane conversion, propylene, and COx selectivities over various VOx/γ-Al2O3 catalysts in the CREC riser simulator. (T = 550 °C, C3H8
injected = 10 mL, reaction time = 20 s, catalyst loaded = 0.76g): (a,b) consecutive ODH runs without catalyst reoxidation in between propane
pulses; (c,d) consecutive ODH runs with catalyst reoxidation in between propane pulses. Error bars correspond to standard deviation of three trials.

Table 3. Intrinsic Kinetic Parameters for the Proposed Kinetic Model. Kinetic Parameters Are Reported with Their 95%
Confidence Interval over Various VOx/γ-Al2O3 catalysts
5% VOx/γ-Al2O3 7% VOx/γ-Al2O3 10% VOx/γ-Al2O3
parameter value 95% CI value 95% CI value 95% CI
ko1a 3.17 x10−3 ±3.89 × 10−5 4.82 x10−3 ±1.00 x10−4 6.34 x10−3 ±2.68 x10−4
ko2 9.28 x10−4 ±1.52 x10−5 3.04 x10−3 ±6.76 x10−5 5.91 x10−3 ±2.30 x10−4
ko3 8.52 x10−5 ±6.78 x10−4 2.97 x10−4 ±1.67 x10−3 6.33 x10−4 ±3.06 x10−3
KoC3H8b 76.72 ±0.93 51.14 ±1.01 38.34 ±1.45
KoC3H6 29.95 ±3.65 28.58 ±5.37 26.12 ±7.82
E1c 124.92 ±1.33 115.08 ±0.99 109.42 ±2.52
E2 52.81 ±1.71 51.07 ±1.42 45.58 ±2.34
E3 52.54 ±8.99 52.73 ±10.94 53.75 ±17.55
−ΔHC3H8c 68.18 ±1.41 50.47 ±1.14 40.32 ±2.18
−ΔHC3H6 54.59 ±8.22 56.86 ±10.80 41.60 ±12.34
σd 2.15 × 10−4 2.65 × 10−4 3.90 × 10−4
λe 0.01−0.053 0.017−0.056 0.015−0.047
m 960 960 960
DOF 950 950 950
a
mol gcat−1 s−1. bcm3/mol. ckJ/mol. dσ = (∑(Xexperimental − Xestimated)2/(m − p))1/2, where m is the number of data points, p is the number of model
parameters, and DOF is the degree of freedom. eDeactivation constant (λ) calculated by independent fitting of experimental data.

VOx/γ-Al2O3 catalysts samples, respectively. In addition, COx γ-Al2O3, 7%VOx/ γ-Al2O3, and 10%VOx/γ-Al2O3 catalysts
selectivities remain stable at 88, 90, and 93% over the 5%VOx/ samples, respectively.
H dx.doi.org/10.1021/ie404064j | Ind. Eng. Chem. Res. XXXX, XXX, XXX−XXX
Industrial & Engineering Chemistry Research Article

Figure 4. Energy diagram for the ODH reaction: (a) propane ODH reaction forming propylene, (b) propane oxidation forming COx, (c) propylene
oxidation forming COx.

Table 4. Standard heat of Reaction for Propane and
Propylene Combustion
reaction ΔHorxn (kJ/mol)
1 reported in Figure 3a,b.
C3H8 + O2 → C3H6 + H 2O −117.6
2 4.3. Kinetic Parameters Estimation. The postulated rate
7 expressions in eqs 28 to eq 30 are nonlinear with respect to
C3H8 + O2 → 3CO + 4H 2O −1195.1
2 their parameters. This is due to the fact that the parameters
C3H8 + 5O2 → 3CO2 + 4H 2O −2043.9
C3H6 + 3O2 → 3CO + 3H 2O −1077.5
9
C3H6 +
2
O2 → 3CO2 + 3H 2O −1926.4
Regarding propylene and COx selectivities during repeated
ODH reaction−regeneration cycles, they are in clear contrast
with the ones reported in Figure 3a,b for consecutive propane
ODH runs. They show that the formation of the CO and CO2
is promoted by gas phase oxygen introduced for the catalysts
regeneration. These low propylene selectivities and higher COx
selectivities obtained at any given propane conversion during
the repeated cycles of single injection ODH experiments can be
related to both the amount and type of surface oxygen species
available on the fresh catalyst surface. Excess amounts of surface
oxygen as well as the existence of nonselective oxygen species
on the fresh catalyst surfaces are believed to favor the
conversion of propane and the produced propylene into
combustion products.
In view of the above, it can be concluded that fully oxidized
(fresh) VOx/γ-Al2O3 catalysts are active but not selective for
propane ODH reactions. This fact can be attributed to the
excess (nonstoichiometric) amount of oxygen species on the
catalysts surface. These species could be either loosely bound
lattice oxygen or weakly adsorbed oxygen species produced
from gas-phase O2 during pretreatment and the catalyst
regeneration. Both types of oxygen species may be involved
in the total oxidation of propane and propylene product.
Thus, one can conclude that the performance of the various
VOx/γ-Al2O3 catalysts of the present study is affected
considerably by both ODH operation conditions and catalyst
regeneration. It appears that consecutive reaction injections
(pulses) are a preferred mode of operation for ODH. As a
result, ODH catalyst regeneration shall only be allowed once
this series of consecutive reaction cycles are completed.
One can, for instance, envision that this is equivalent to
operating a twin circulating fluidized reactor process (reactor−
regenerator), where the following occurs: (a) most of the
catalyst stream leaving the reactor is returned to the ODH unit
I dx.doi.org/10.1021/ie404064j | Ind. Eng. Chem. Res. XXXX, XXX, XXX−XXX
directly; (b) only a small fraction of the catalyst stream is
directed toward the regenerator. This operational strategy can
allow the functioning of industrial scale ODH processes with
high propylene selectivities, under conditions close to the ones
appear both in the numerator and in the denominator of the
rate expressions such as in the case of the adsorption constant
(Ki). Therefore, the estimation of the 10 parameters (ko1, ko2, ko3,
E1, E2, E3, KoC3H8, KoC3H6, −ΔHC3H8 and −ΔHC3H6) was developed
using nonlinear least-squares regression. The MATLAB routine
“LSQCURVEFIT” was used for the regression analysis. The
numerical integration of the system of ODE given in eqs 29 to
31 and the determination of the 95% confidence intervals for
each estimated parameter were performed using the MATLAB
functions “ode113”; and “nlparci”, respectively.
Experimental data at different reaction temperatures were
used to evaluate reaction rate parameters. Moreover, an
Arrhenius type of temperature-dependence function was used
to express the specific rate constants. This was done by taking
into account the temperature dependence of the experimental
data as shown in eq 32.
Moreover, the deactivation constant “λ” given in eq 4 was
obtained through an independent fitting of the propane
conversion data for every run (e.g., using the propane
conversions obtained for injection 4 at 5 s, 10 s, 15 s, and 20
s). The ‘λ” parameter was calculated via nonlinear regression.
Regression coefficients were, in all cases, in excess of 0.98. The
obtained values of the deactivation constant “λ” were used as
inputs in the proposed kinetic model along with all the mass
fractions of the reactants/products. This approach was valuable
to eliminate the high cross-correlation observed between λ and
the other kinetic parameters
The optimization criteria considered was established having
the following bounds for the model parameters: (a) rate
constants and activation energies for each reaction must be
positive, (b) heats of adsorption (ΔHi) must be negative. On
this basis, a minimum sum of squares of errors was calculated:
N
SSR = ∑ (xi ,exp − xi ,pred)2
i=1 (33)
where xi,exp and xi, pred are the mass fraction of component i
obtained experimentally and predicted by the kinetic model,
respectively.
Industrial & Engineering Chemistry Research
Figure 5. Comparison between experimental data and model predictions () over a 5% VOx/γ-Al2O3 catalyst sample: (a) T = 475 °C; (b) T = 500
°C; (c) T = 525 °C; (d) T = 550 °C. (Data points are reported for the average of 2nd to 10th injections.)
Furthermore, discrimination between possible models was
based on (i) correlation coefficients (R2), (ii) lower SSR (sum
of the squares of the residuals) criteria, (iii) lower cross-
correlation coefficient (γi), and (iv) smaller individual
confidence intervals for the model parameters.
The values of the 10 estimated parameters along with their
corresponding 95% confidence intervals (CI) are reported in
Table 3 for the different VOx/γ-Al2O3 catalysts. It can be
noticed that all the estimated parameters display a reduced and
acceptable 95% C.I. Moreover, the ability of establishing the 10
model parameters is consistent with the high DOF (degree of
freedom) in this analysis with 960 experimental data points for
each catalyst sample considering three trials for each run.
One can also observe that all 10 parameters in Table 3 were
calculated with reduced spans. In addition, several kinetic
parameter trends regarding the effect of vanadium loading on
the catalytic activity can be observed in Table 3. One can notice
that the pre-exponential factors (ko1, ko2, and ko3) augment as the
vanadium loading is increased.
In view of these findings, one can consider correlating
changes in the ko1, ko2, and ko3 values with the different vanadia
structures present at specific vanadium loadings, though other
factors may also be involved. In this respect, one can also notice
that the increase in ko1 is in agreement with the experimental
results. Specific initial rates of propane ODH were found to
J dx.doi.org/10.1021/ie404064j | Ind. Eng. Chem. Res. XXXX, XXX, XXX−XXX
Article
increase with VOx surface density. This suggests that
polyvanadate surface species, which are more dominant at
higher VOx surface densities, are more active than mono-
vanadate species.
Similarly, the increase in the ko2 and ko3 pre-exponential factors
with vanadium loading is also in agreement with the
experimental results. It was also found that COx formation
rates increase with VOx surface density. This can be attributed
to the excess surface oxygen species available at higher loadings.
This is also consistent with the decreasing propylene selectivity
with VOx surface density as more COx are formed.
Regarding the relative magnitude of the activation energies
obtained as reported in Table 3, it can be noticed that COx
formation activation energies (E2 and E3) are consistently
smaller than E1. On the basis of this observation, one could
argue that the obtained values are consistent with the energy
diagrams given in Figure 4. One can observe in these diagrams,
the major difference of the heats of reaction: the COx heat of
reaction being much larger than the C3H6 heat of formation via
ODH. Thus, on this basis, one can also envision the propane
ODH reaction forming propylene with activation energy larger
than the ones for the reactions leading to COx as reported in
Table 4. These facts may contribute to explaining the limited
ODH propylene selectivity at higher temperatures.
Industrial & Engineering Chemistry Research Article

Figure 6. Comparison between experimental data and model predictions () over a 7% VOx/γ-Al2O3 catalyst sample: (a) T = 475 °C; (b) T = 500
°C; (c) T = 525 °C; (d) T = 550 °C. (Data points are reported for the average of 2nd to 10th injections.)

In addition, further insights into the validity of the proposed
kinetic model and the estimated kinetic parameters could be
obtained. This can be done by comparing the model
predictions for products and reactant mass fractions with
experimental data. This was, in fact, done for all the catalysts of
this study as reported in Figures 5−7. It can be noted that,
within the limits of experimental error, the model predictions
compare very well with the experimental data. Thus, this
comparison validates the adequacy of the proposed reaction
model.
Moreover, it can also be inferred from the parity plots
reported in Figures 5−7 for model predictions, as compared to
the experimental data, that the data is not clustered in
horizontal or vertical lines. Horizontal bands may be the result
of changes in the observed conversion caused by an
independent variable which is not included in the kinetic
model. On the other hand, vertical lines are an indication of the
kinetic model overparameterization.79,80
The adequacy of the estimated parameters was checked by
analyzing their dependence on each other through the cross-
correlation matrix as shown in Table 5. It can be observed, that
in most cases, cross-correlation coefficients are below 0.90 with
only three of them surpassing the 0.9 value. Hence, it can be
concluded that the kinetic model as proposed is not
overparameterized and that the defined parameters can be
K dx.doi.org/10.1021/ie404064j | Ind. Eng. Chem. Res. XXXX, XXX, XXX−XXX
related to physicochemical properties of the catalysts under
study.
On the basis discussed above, it can be concluded that the set
of adsorption and kinetic parameters established as well as the
kinetic model developed are adequate to predict propane ODH
reaction rates in the CREC riser simulator in the range of the
operating conditions studied.
It is important to review the values of the activation energies
obtained in the present study and to compare them with values
already reported in the technical literature. Table 6 reports the
activation energies for propane ODH on various supported
VOx catalysts. Although the reported values for the three
propane ODH catalysts of this study are consistently within the
same range, there is some discrepancy between these energies
of activation (± 20 kJ/mol) when compared with other values
published in the technical literature. This discrepancy can be
attributed to the dissimilarity in experimental systems,
operating conditions, proposed ODH kinetic model, and
catalysts studied.
It should be stressed, however, that the values of activation
energies for the propane ODH of this study are close to the
ones reported by Rao and Deo, 200446 using VOx/γ-Al2O3
catalysts with similar vanadium loadings. For instance, for the
propane ODH step, Rao and Deo, 2004 reported activation
energies for propylene formation of 113.6, 100, and 98 kJ/mol
Industrial & Engineering Chemistry Research Article

Figure 7. Comparison between experimental data and model predictions () over a 10% VOx/γ-Al2O3 catalyst sample: (a) T = 475 °C; (b) T =
500 °C; (c) T = 525 °C; (d) T = 550 °C. (Data points are reported for the average of 2nd to 10th injections.)

for catalysts with vanadium loadings of 7.5, 10, and 12.5 wt %,
respectively. The values of activation energies observed in this
study for the same step were 124.9, 115.1, and 82 KJ/mol for 5,
7, and 10 wt % catalysts, respectively.
However, in the case of COx formation, the reported values
by Rao and Deo, 200446 differ by ±20 kJ/mol from those
obtained in the context of the present study. This discrepancy
between activation energies of COx formation can be attributed
to both the different reaction considered by Rao and Deo,
2004, where oxygen is being cofed with propane, and the
different reaction network paths involved. Rao and Deo, 2004,
assumed that CO and CO2 are formed from propylene instead
of following the the parallel-series “triangular” reaction network
of the present study. This proposed “triangular” reaction
network of the present study is reinforced by the fact that COx
species are observed even at very low propane conversions.
Thus, a direct COx formation step from propane is required.
As a result, on the basis of the experimental evidence
gathered and on the adequacy of the parallel-series “triangular”
kinetic model proposed, the following can be considered as
reported in Figure 1: (i) There is an alkene formation step, (ii)
there is a competitive direct alkane combustion step, and (iii)
once alkene is formed, there is further alkene combustion.
In summary, the catalytic runs of the present study together
with the phenomenologically based kinetic model developed
L dx.doi.org/10.1021/ie404064j | Ind. Eng. Chem. Res. XXXX, XXX, XXX−XXX
support an ODH process using twin circulating fluidized beds
with (a) an ODH reactor with oxygen being supplied from the
catalyst lattice only and (b) a reoxidation reactor where the
catalyst lattice oxygen is replenished. It is anticipated that in this
type of ODH process, only a 1/23 fraction of the catalyst in the
reactor outlet stream is going to be treated per pass in the
reoxidation reactor. This is estimated considering up to 23
injections are required in the CREC riser simulator until
oxygen is fully depleted from the VOx/γ-Al2O3 catalysts.71 The
rest or most of the catalyst in the ODH reactor outlet stream is
going to be partially cooled and recycled back directly to the
reactor input stream. It is expected that such a twin and
integrated ODH fluidized bed process will yield higher olefin
selectivities as reported in the present study.
5. CONCLUSIONS
The following key points can be considered as the main
conclusions of this study:
1. Propane was converted to propylene via ODH reaction
over VOx/γ-Al2O3 catalysts utilizing the lattice oxygen of
the catalysts. Good propane conversion (11.73%−
15.11%) and promising propylene selectivity (67.65−
85.89%) were achieved in successive-injection propane
ODH experiments (without catalyst regeneration) in the
CREC riser simulator at 475−550 °C.
Industrial & Engineering Chemistry Research Article

Table 5. Cross-Correlation Coefficients for the Kinetic Model Optimized Parameters over Various VOx/ γ-Al2O3 Catalyst
Samples
ko1 ko2 ko3 KoC3H8 KoC3H6 E1 E2 E3 −ΔHC3H8 −ΔHC3H6
(a) 5% VOx/γ-Al2O3 Catalyst Sample
ko1 1.000
ko2 0.657 1.000
ko3 0.150 −0.617 1.000
KoC3H8 −0.975 −0.803 0.061 1.000
KoC3H6 0.031 0.027 −0.019 −0.036 1.000
E1 −0.064 0.039 −0.112 0.027 0.099 1.000
E2 −0.127 0.232 −0.434 0.029 0.082 0.871 1.000
E3 0.009 0.020 −0.020 −0.016 −0.029 0.101 0.080 1.000
−ΔHC3H8 0.064 −0.028 0.103 −0.032 −0.101 −0.994 −0.888 −0.098 1.000
−ΔHC3H6 0.049 −0.047 0.119 −0.018 −0.497 −0.285 −0.291 −0.328 0.291 1.000
(b) 7% VOx/γ-Al2O3 Catalyst Sample
ko1 1.000
ko2 0.696 1.000
ko3 0.344 −0.405 1.000
KoC3H8 −0.949 −0.881 −0.051 1.000
KoC3H6 −0.062 −0.093 0.014 0.083 1.000
E1 −0.521 −0.330 −0.169 0.449 0.096 1.000
E2 −0.670 −0.255 −0.507 0.535 0.063 0.705 1.000
E3 −0.043 0.016 −0.067 0.024 −0.103 −0.032 −0.019 1.000
−ΔHC3H8 0.625 0.474 0.143 −0.588 −0.104 −0.928 −0.823 0.039 1.000
−ΔHC3H6 0.129 0.121 0.017 −0.136 −0.477 −0.066 −0.076 −0.329 0.086 1.000
(c) 10% VOx/γ-Al2O3 Catalyst Sample
ko1 1.000
ko2 0.838 1.000
ko3 0.381 −0.159 1.000
KoC3H8 −0.965 −0.949 −0.143 1.000
KoC3H6 −0.122 −0.118 −0.070 0.127 1.000
E1 0.696 0.588 0.290 −0.678 −0.096 1.000
E2 0.591 0.644 −0.044 −0.639 −0.074 0.834 1.000
E3 0.091 0.090 0.032 −0.094 −0.503 0.046 0.017 1.000
−ΔHC3H8 −0.648 −0.516 −0.293 0.612 0.083 −0.961 −0.892 −0.030 1.000
−ΔHC3H6 0.002 −0.023 0.060 0.008 −0.382 0.040 0.002 −0.196 −0.033 1.000

Table 6. Reported Activation Energies for Main Products Formation in Ethane ODH
activation energy of formation (kJ/mol)
catalyst C3H6 carbon oxides reference
5% VOx/γ-Al2O3 124.9 (COx) 52.8a (COx) 52.53b (present study)
7% VOx/γ-Al2O3 115.1 (COx) 51.1a (COx) 52.7b (present study)
10% VOx/γ-Al2O3 109.5 (COx) 45.6a (COx) 53.7b (present study)
10% VOx/γ-Al2O3 82 (CO) 35b (CO2) 52.2b 81
2.1%VOx/γ-Al2O3 113.6 (CO2) 87.5b 82
7.5% V/γ-Al2O3 100 (CO) 50b (CO2) 46b 46
10% V/γ-Al2O3 98 (CO) 55b (CO2) 49b 46
12.5% V/γ-Al2O3 92 (CO) 83b (CO2) 75b 46
24%V/MgO 114 (CO) 72a (CO) 101b (CO2) 42a (CO2) 92b 43
0.6%VOx/SiO2 147 (CO2) 96b 82
a
Formation from C3H8. bFormation from C3H6.

2. The selectivity for propylene increased and that for COx
decreased as the degree of reduction of the catalyst
increased with propane injections. This shows that a
controlled degree of catalyst reduction is needed in order
to obtain higher propylene selectivity. Under such
oxygen-free conditions, the oxygen from the catalyst
lattice is consumed by ODH reactions.
3. A parallel-series “triangular” reaction network was
proposed for propane ODH over VOx/γ-Al2O3 catalysts
where there is a propylene formation step, a competitive

M dx.doi.org/10.1021/ie404064j | Ind. Eng. Chem. Res. XXXX, XXX, XXX−XXX

Industrial & Engineering Chemistry Research
direct propane combustion step, and propylene
combustion step.
4. This heterogeneous kinetic model based on a Marsvan
Krevelen mechanism, allowed us to describe the effect of
vanadia loading on propane ODH reaction over VOx/γ-
Al2O3 catalysts. The proposed kinetic model accounts for
all reactants (propane) and products (propylene and
COx). On this basis, rate equations are developed
including both reactant adsorption and catalytic reaction
on the catalyst surface.
5. The change in degree of oxidation of the catalyst during
oxygen-free ODH reactions was effectively modeled and
included in the rate equations by using a decay function
based on reactant conversion. The proposed kinetic
model was established with a DOF of 950. This model
satisfactorily predicts the ODH reaction of propane
under the selected reaction conditions over the various
VOx/γ-Al2O3 catalysts with different vanadium loadings.
6. The determined kinetic parameters included the pre-
exponential factor, koi , the adsorption constant, Koi , the
activation energies, Ei, for the propene formation,
propane oxidation, and propene oxidation and desorp-
tion energies, −ΔHi.
7. The intrinsic kinetic parameters were estimated using a
nonlinear least-squares fit regression. The calculated
kinetic parameters were able to predict the observed
outlet mass fractions of all carbon containing compounds
and were found to vary with vanadia loading.
8. The calculated pre-exponential factors (ko1, ko2, and ko3)
increased as the vanadium loading was augmented. In
addition, the activation energies for COx formation (E2
and E3) were consistently smaller than the one for
propylene formation (E1).
■
ASSOCIATED CONTENT
* Supporting Information
S TCD = thermal conductivity detector
Experimental results of propane ODH in the CREC riser
simulator using the various VOx/γ-Al2O3 catalyst samples for
10 consecutive propane injections (pulse) without catalyst
regeneration between injections; “λ” deactivations constants
obtained via numerical regression for every propane injection
and data at 5 s, 10 s, 15 s, and 20 s. This material is available
free of charge via the Internet at http://pubs.acs.org.
■
AUTHOR INFORMATION
Corresponding Author
*Tel: +1-519-661-2144. Fax: +1-519-850-2931. E-mail:
hdelasa@eng.uwo.ca.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
The authors wish to acknowledge the National Sciences and
Engineering Research Council of Canada (NSERC) for their
financial support of this research and the Saudi Arabian Oil
Company (Saudi ARAMCO), Saudi Arabia, for the scholarship
awarded for the development of this Ph.D. research at the
University of Western Ontario.
■
NOTATIONS
ri = Rate of reaction i (mol/g.s)
VOx = vanadium oxide surface species
N dx.doi.org/10.1021/ie404064j | Ind. Eng. Chem. Res. XXXX, XXX, XXX−XXX
Article
XC3H8 = propane conversion, (%)
Si = selectivity of component i (%)
Yi = yield of product i
SBET = Brunauer−Emmet−Teller specific surface area (cm2/
g)
Nopropane = Initial moles of propane, (mols)
Wcat = weight of catalyst, (g)
Ei = activation energy of desorption, (kJ/mol)
−ΔHi = heat of adsorption, (kJ/mol)
koi = pre-exponential factor (mol gcat−1 s−1)
Kd = adsorption constant (cm3/mol)
Tm = centering temperature (K)
R = the universal gas constant
s = surface-adsorbed species
g = gas phase species
Greek Symbols
β = degree of reduction of catalysts, (%)
θdes = surface coverage of adsorbed species
ν = stoichiometric number
λ = catalyst deactivation constant established via numerical
for every injection in the consecutive injection series using
propane conversion at 5 s, 10 s, 15 s, and 20 s
ϕ = degree of oxidation of the catalyst (% oxidation)
σ = standard deviation
Abbreviations
ODH = oxidative dehydrogenation
MW = molecular weight
CREC = Chemical Reactor Engineering Center
XRD = X-ray diffraction
TPR = Temperature-programmed reduction
TPO = temperature-programmed oxidation
TPD = temperature-programmed desorption
LRS = laser Raman spectroscopy
XPS = X-ray photoelectron spectroscopy
FID = flame ionization detector
AOS = average oxidation state
■ REFERENCES
(1) Blasco, T.; López-Nieto, J. M. Oxidative Dehydrogenation of
Short Chain Alkanes on Supported Vanadium Oxide Catalysts. Appl.
Catal. A Gen. 1997, 157, 117.
(2) Mamedov, E. A.; Corberan, V. C. Oxidative Dehydrogenation of
Lower Alkanes on Vanadium Oxide-Based Catalysts. The Present State
of the Art and Outlooks. Appl. Catal. A Gen. 1995, 127, 1.
(3) Baerns, M.; Buyevskaya, O.; Mulla, S. A. R. A Comparative Study
on Non-Catalytic and Catalytic Oxidative Dehydrogenation of Ethane
to Ethylene. Appl. Catal. A Gen. 2002, 226, 73.
(4) Shen, Z.; Liu, J.; Xu, H.; Yue, Y.; Hua, W.; Shen, W.
Dehydrogenation of Ethane to Ethylene over a Highly Efficient
Ga2O3/HZSM-5 Catalyst in the Presence of CO2. Appl. Catal. A Gen.
2009, 356, 148.
(5) Č apek, L.; Bulánek, R.; Adam, J.; Smoláková, L.; Sheng-Yang, H.;
Č ičmanec, P. Oxidative Dehydrogenation of Ethane over Vanadium-
Based Hexagonal Mesoporous Silica Catalysts. Catal. Today 2009, 141,
282.
(6) Shi, X.; Ji, S.; Wang, K. Oxidative Dehydrogenation of Ethane to
Ethylene with Carbon Dioxide over Cr−Ce/SBA-15 Catalysts. Catal.
Lett. 2008, 125, 331.
(7) Č apek, L.; Adam, J.; Grygar, T.; Bulánek, R.; Vradman, L.;
Košová-Kučerová, G.; Č ičmanec, P.; Knotek, P. Oxidative Dehydro-
genation of Ethane over Vanadium Supported on Mesoporous
Materials of M41S Family. Appl. Catal. A Gen. 2008, 342, 99.
(8) Klose, F.; Wolff, T.; Lorenz, H.; Seidelmorgenstern, A.;
Suchorski, Y.; Piorkowska, M.; Weiss, H. Active Species on Γ-
Industrial & Engineering Chemistry Research
Alumina-Supported Vanadia Catalysts: Nature and Reducibility. J.
Catal. 2007, 247, 176.
(9) Danica, B.; Desislava, A.; Mirko, P.; Stefan, H. An Experimental
Study of the Partial Oxidation of Ethane to Ethylene in a Shallow
Fluidized Bed Reactor. J. Serbian Chem. Soc. 2007, 72, 183.
(10) Haddad, N.; Bordes Richard, E.; Hilaire, L.; Barama, A.
Oxidative Dehydrogenation of Ethane to Ethene on Alumina-
Supported Molybdenum-Based Catalysts Modified by Vanadium and
Phosphorus. Catal. Today 2007, 126, 256.
(11) Karamullaoglu, G.; Dogu, T. Oxidative Dehydrogenation of
Ethane over Chromium-Vanadium Mixed Oxide and Chromium
Oxide Catalysts. Ind. Eng. Chem. Res. 2007, 46, 7079.
(12) Tope, B.; Zhu, Y.; Lercher, J. A. Oxidative Dehydrogenation of
Ethane over Dy2O3/MgO Supported LiCl Containing Eutectic
Chloride Catalysts. Catal. Today 2007, 123, 113.
(13) Cavani, F.; Ballarini, N.; Cericola, A. Oxidative Dehydrogen-
ation of Ethane and Propane: How far from Commercial
Implementation? Catal. Today 2007, 127, 113.
(14) Lemonidou, A. A.; Heracleous, E. Reaction Pathways of Ethane
Oxidative and Non-Oxidative Dehydrogenation on Γ-Al2O3 Studied
by Temperature-Programmed Reaction (TP-Reaction). Catal. Today
2006, 112, 23.
(15) Solsona, B.; Dejoz, A.; Garcia, T.; Concepcion, P.; López-Nieto,
J. M.; Vazquez, M.; Navarro, M. T. Molybdenum−Vanadium
Supported on Mesoporous Alumina Catalysts for the Oxidative
Dehydrogenation of Ethane. Catal. Today 2006, 117, 228.
(16) Heracleous, E.; Lemonidou, A. A. Ni−Nb−O Mixed Oxides as
Highly Active and Selective Catalysts for Ethene Production via
Ethane Oxidative Dehydrogenation. Part II: Mechanistic Aspects and
Kinetic Modeling. J. Catal. 2006, 237, 175.
(17) Heracleous, E.; Lemonidou, A. A. Ni−Nb−O Mixed Oxides as
Highly Active and Selective Catalysts for Ethene Production via
Ethane Oxidative Dehydrogenation. Part I: Characterization and
Catalytic Performance. J. Catal. 2006, 237, 162.
(18) Botella, P.; Dejoz, A.; López-Nieto, J. M.; Concepcion, P.;
Vazquez, M. Selective Oxidative Dehydrogenation of Ethane over
MoVSbO Mixed Oxide Catalysts. Appl. Catal. A Gen. 2006, 298, 16.
(19) Nakagawa, K.; Miyake, T.; Konishi, T.; Suzuki, T. Oxidative
Dehydrogenation of Ethane to Ethylene over NiO Loaded on High
Surface Area MgO. J. Mol. Catal. A Chem. 2006, 260, 144.
(20) López-Nieto, J. M.; Botella, P.; García-González, E.; Dejoz, A.;
Vazquez, M.; González-Calbet, J. Selective Oxidative Dehydrogenation
of Ethane on MoVTeNbO Mixed Metal Oxide Catalysts. J. Catal.
2004, 225, 428.
(21) Anon, R. New Propylene Production Technologies Hold Great
Promise. Oil Gas J. 2004, 102, 50.
(22) Bhasin, M. Is True Ethane Oxydehydrogenation Feasible? Top.
Catal. 2003, 23, 145.
(23) Resasco, D.; Haller, G. Catalytic Dehydrogenation of Lower
Alkanes. Catal. R. Soc. Chem. 1994, 11.
(24) Chan, K. Y. G.; Inal, F.; Senkan, S. Suppression of Coke
Formation in the Steam Cracking of Alkanes: Ethane and Propane.
Ind. Eng. Chem. Res. 1998, 37, 901.
(25) Dharia, D.; Letzsch, W.; Kim, H.; McCue, D.; Chapin, L.
Increase Light Olefins Production. Hydrocarb. Process. 2004, 83, 61.
(26) Ren, T.; Patel, M.; Blok, K. Olefins from Conventional and
Heavy Feedstocks: Energy Use in Steam Cracking and Alternative
Processes. Energy 2006, 31, 425.
(27) Farrauto, R. J.; Bartholomew, C. H. Fundamentals of Industrial
Catalytic Processes; 1st ed.; Chapman & Hall: London, 1997.
(28) Chen, K.; Xie, S.; Bell, A. T.; Iglesia, E. Alkali Effects on
Molybdenum Oxide Catalysts for the Oxidative Dehydrogenation of
Propane. J. Catal. 2000, 195, 244.
(29) Kung, H. Oxidative Dehydrogenation of Light (C2 to C4)
Alkanes. Adv. Catal. 1994, 40, 1.
(30) Chen, K.; Khodakov, A.; Yang, J.; Bell, A. T.; Iglesia, E. Isotopic
Tracer and Kinetic Studies of Oxidative Dehydrogenation Pathways on
Vanadium Oxide Catalysts. J. Catal. 1999, 333, 325.
O dx.doi.org/10.1021/ie404064j | Ind. Eng. Chem. Res. XXXX, XXX, XXX−XXX
Article
(31) Bell, A. T.; Khodakov, A.; Olthof, B.; Iglesia, E. Structure and
Catalytic Properties of Supported Vanadium Oxides: Support Effects
on Oxidative Dehydrogenation Reactions. J. Catal. 1999, 181, 205.
(32) Chen, K.; Xie, S.; Bell, A. T.; Iglesia, E. Structure and Properties
of Oxidative Dehydrogenation Catalysts Based on MoO3/Al2O3. J.
Catal. 2001, 198, 232.
(33) Grabowski, R.; Sloczynski, J. Kinetics of Oxidative Dehydrogen-
ation of Propane and Ethane on VOx/SiO2 Pure and with Potassium
Additive. Chem. Eng. Process. 2005, 44, 1082.
(34) Grabowski, R. Kinetics of Oxidative Dehydrogenation of C2-C3
Alkanes on Oxide Catalysts. Catal. Rev. 2006, 48, 199.
(35) Lemonidou, A. A. Oxidative Dehydrogenation of C4 Hydro-
carbons over VMgO Catalyst  Kinetic Investigations. Appl. Catal. A
Gen. 2001, 216, 277.
(36) Machli, M.; Boudouris, C.; Gaab, S.; Find, J.; Lemonidou, A. A.;
Lercher, J. A. Kinetic Modelling of the Gas Phase Ethane and Propane
Oxidative Dehydrogenation. Catal. Today 2006, 112, 53.
(37) Klose, F.; Joshi, M.; Hamel, C.; Seidelmorgenstern, A. Selective
Oxidation of Ethane over a VOx/γ-Al2O3 CatalystInvestigation of
the Reaction Network. Appl. Catal. A Gen. 2004, 260, 101.
(38) Rahman, F.; Loughlin, K. F.; Al-Saleh, M. A.; Saeed, M. R.;
Tukur, N. M.; Hossain, M. M.; Karim, K.; Mamedov, E. A. Kinetics
and Mechanism of Partial Oxidation of Ethane to Ethylene and Acetic
Acid over MoV Type Catalysts. Appl. Catal. A Gen. 2010, 375, 17.
(39) Chen, K.; Iglesia, E.; Bell, A. T. Isotopic Tracer Studies of
Reaction Pathways for Propane Oxidative Dehydrogenation on
Molybdenum Oxide Catalysts. J. Phys. Chem. B 2001, 105, 646.
(40) Bell, A. T.; Iglesia, E.; Argyle, M. D.; Chen, K. Ethane Oxidative
Dehydrogenation Pathways on Vanadium Oxide Catalysts. J. Phys.
Chem. B 2002, 106, 5421.
(41) Bell, A. T.; Dinse, A.; Schomäcker, R. The Role of Lattice
Oxygen in the Oxidative Dehydrogenation of Ethane on Alumina-
Supported Vanadium Oxide. Phys. Chem. Chem. Phys. 2009, 11, 6119.
(42) Lemonidou, A. A.; Heracleous, E.; Lercher, J. A. Mechanistic
Features of the Ethane Oxidative Dehydrogenation by in Situ FTIR
Spectroscopy over a MoO3/Al2O3 Catalyst. Appl. Catal. A Gen. 2004,
264, 73.
(43) Ramos, R.; Pinal, M. P.; Menendez, M.; Santamaria, J. Patience,
G. S. Oxidative Dehydrogenation of Propane to Propene, 1: Kinetic
Study on V/MgO. Can. J. Chem. Eng. 2001, 79, 891.
(44) Creaser, D.; Andersson, B. Oxidative Dehydrogenation of
Propane over V-Mg-O: Kinetic Investigation by Nonlinear Regression
Analysis. Appl. Catal. A Gen. 1996, 141, 131.
(45) Creaser, D.; Andersson, B.; Hudgins, R. R.; Silverston, P. L.
Transient Kinetic Analysis of the Oxidative Dehydrogenation of
Propane. J. Catal. 1999, 182, 264.
(46) Rao, T. V. M; Deo, G. Kinetic Parameter Analysis for Propane
ODH: V2O5/Al2O3 and MoO3/Al2O3 Catalysts. AIChE J. 2007, 53,
1538.
(47) Chen, K.; Iglesia, E.; Bell, A. T. Kinetic Isotopic Effects in
Oxidative Dehydrogenation of Propane on Vanadium Oxide Catalysts.
J. Catal. 2000, 192, 197.
(48) Creaser, D.; Andersson, B. Oxidative Dehydrogenation of
Propane over V-Mg-O: Kinetic Investigation by Nonlinear Regression
Analysis. Appl. Catal. A Gen. 1996, 141, 131.
(49) Dinse, A.; Khennache, S.; Frank, B.; Hess, C.; Herbert, R.;
Wrabetz, S.; Schlögl, R.; Schomäcker, R. Oxidative Dehydrogenation
of Propane on Silica (SBA-15) Supported Vanadia Catalysts: A Kinetic
Investigation. J. Mol. Catal. A Chem. 2009, 307, 43.
(50) Balcaen, V.; Sack, I.; Olea, M.; Marin, G. B. Transient Kinetic
Modeling of the Oxidative Dehydrogenation of Propane over a
Vanadia-Based Catalyst in the Absence of O2. Appl. Catal. A Gen.
2009, 371, 31.
(51) Bottino, A.; Capannelli, G.; Comite, A.; Storace, S.; Felice, R. D.
Kinetic Investigations on the Oxidehydrogenation of Propane over
Vanadium Supported on Γ-Al2O3. Chem. Eng. J. 2003, 94, 11.
(52) Grabowski, R.; Pietrzyk, S.; Słoczy, J.; Genser, F.; Wcisło, K.;
Swierkosz, B. G.-. Kinetics of the Propane Oxidative Dehydrogenation
Industrial & Engineering Chemistry Research Article

on Vanadia/Titania Catalysts from Steady-State and Transient (74) Hossain, M. M.; Atanda, L.; Al-Yassir, N.; Al-Khattaf, S. Kinetics
Experiments. Appl. Catal. A Gen. 2002, 232, 277. Modeling of Ethylbenzene Dehydrogenation to Styrene over a
(53) Leveles, L. Oxidative Conversion of Propane over Lithium- Mesoporous Alumina Supported Iron Catalyst. Chem. Eng. J. 2012,
Promoted Magnesia Catalyst I. Kinetics and Mechanism. J. Catal. 207−208, 308.
2003, 218, 296. (75) Al-Ghamdi, S. A.; Volpe, M.; Hossain, M. M.; de Lasa, H. I.
(54) Kumar, C. P.; Gaab, S.; Müller, T. E.; Lercher, J. A. Oxidative VOx/c-Al2O3 Catalyst for Oxidative Dehydrogenation of Ethane to
Dehydrogenation of Light Alkanes on Supported Molten Alkali Metal Ethylene: Desorption Kinetics and Catalytic Activity. Appl. Catal. A
Chloride Catalysts. Top. Catal. 2008, 50, 156. Gen. 2013, 450, 120.
(55) Al-Zahrani, S. M.; Abasaeed, A. E.; Putra, M. Kinetics of (76) Ginsburg, J.; de Lasa, H. I. Catalytic Gasification of Biomass in
Oxidehydrogenation of Propane over Alumina-Supported Sr−V−Mo CREC Fluidized Riser Simulator. Int. J. Chem. React. Eng. 2005, 3, A38.
Catalysts. Catal. Commun. 2012, 26, 98. (77) Pekediz, A.; Kraemer, D. W.; Chabot, J.; de Lasa, H. I. Mixing
(56) Late, L.; Blekkan, E. A. Kinetics of the Oxidative Dehydrogen- Patterns in a Novel Riser Simulator. Appl. Sci. 1992, 133.
ation of Propane over a VMgO Catalyst. J. Nat. Gas Chem. 2002, 11, (78) Hossain, M. M.; de Lasa, H. I. Reduction and Oxidation Kinetics
33. of Co−Ni/Al2O3 Oxygen Carrier Involved in a Chemical-Looping
(57) Gascón, J.; Valenciano, R.; Téllez, C.; Herguido, J.; Menendez, Combustion Cycles. Chem. Eng. Sci. 2010, 65, 98.
M. A Generalized Kinetic Model for the Partial Oxidation of N-Butane (79) Jarosch, K.; El Solh, T.; de Lasa, H. I. Modelling the Catalytic
to Maleic Anhydride under Aerobic and Anaerobic Conditions. Chem. Steam Reforming of Methane: Discrimination between Kinetic
Eng. Sci. 2006, 61, 6385. Expressions Using Sequentially Designed Experiments. Chem. Eng.
(58) López-Nieto, J. M.; Soler, J.; Concepcion, P.; Herguido, J.; Sci. 2002, 57, 3439.
(80) Moreira, J.; Serrano, B.; Ortiz, A.; de Lasa, H. I. A Unified
Menendez, M.; Santamaria, J. Oxidative Dehydrogenation of Alkanes
Kinetic Model for Phenol Photocatalytic Degradation over TiO2
over V-Based Catalysts: Influence of Redox Properties on Catalytic
Photocatalysts. Chem. Eng. Sci. 2012, 78, 186.
Performance. J. Catal. 1999, 332, 324.
(81) Routray, K.; Reddy, K. R. S.; Deo, G. Oxidative Dehydrogen-
(59) Sadykov, V. A.; Pavlova, S.; Saputina, N.; Zolotarskii, I.;
ation of Propane on V2O5/Al2O3 and V2O5/TiO2 Catalysts:
Pakhomov, N.; Moroz, E.; Kuzmin, V.; Kalinkin, A. Oxidative Understanding the Effect of Support by Parameter Estimation. Appl.
Dehydrogenation of Propane over Monoliths at Short Contact Catal. A Gen. 2004, 265, 103.
Times. Catal. Today 2000, 61, 93. (82) Dinse, A.; Frank, B.; Hess, C.; Habel, D.; Schomäcker, R.
(60) Leveles, L. Oxidative Conversion of Propane over Lithium- Oxidative Dehydrogenation of Propane over Low-Loaded Vanadia
Promoted Magnesia Catalyst II. Active Site Characterization and Catalysts: Impact of the Support Material on Kinetics and Selectivity. J.
Hydrocarbon Activation. J. Catal. 2003, 218, 307. Mol. Catal. A Chem. 2008, 289, 28.
(61) Zhao, R.; Wang, J.; Dong, Q.; Liu, J. Selective Oxidation of
Propane by Lattice Oxygen of Vanadium−Phosphorous Oxide in a
Pulse Reactor. J. Nat. Gas Chem. 2005, 14, 88.
(62) Fukudome, K.; Ikenaga, N.; Miyake, T.; Suzuki, T. Oxidative
Dehydrogenation of Propane Using Lattice Oxygen of Vanadium
Oxides on Silica. Catal. Sci. Technol. 2011, 1, 987.
(63) Yoon, Y. S.; Ueda, W.; Moro-oka, Y. Oxidative Dehydrogen-
ation of Propane over Magnesium Molybdate Catalysts. Catal. Lett.
1995, 35, 57.
(64) Creaser, D.; Andersson, B.; Hudgins, R. R.; Silverston, P. L.
Transient Study of Oxidative Dehydrogenation of Propane. Appl.
Catal. A Gen. 1999, 187, 147.
(65) Stern, D. L.; Grasselli, R. K. Propane Oxydehydrogenation over
Molybdate-Based Catalysts. J. Catal. 1997, 167, 550.
(66) Rubio, O.; Herguido, J.; Menendez, M. Oxidative Dehydrogen-
ation of N-Butane on V/MgO Catalysts-Kinetic Study in Anaerobic
Conditions. Chem. Eng. Sci. 2003, 58, 4619.
(67) Soler, J.; López-Nieto, J. M.; Herguido, J.; Menendez, M.;
Santamaria, J. Oxidative Dehydrogenation of N-Butane in a Two-Zone
Fluidized-Bed Reactor. Ind. Eng. Chem. Res. 1999, 38, 90.
(68) Rubio, O.; Herguido, J.; Menendez, M. Oxidative Dehydrogen-
ation of Butane in an Interconnected Fluidized-Bed Reactor. AIChE J.
2004, 50, 1510.
(69) Al-Ghamdi, S. A.; Hossain, M. M.; Lasa, H. I. De. Kinetic
Modeling of Ethane Oxidative Dehydrogenation over VOX/Al2O3
Catalyst in a Fluidized-Bed Riser Simulator. Ind. Eng. Chem. Res.
2013, 52, 5235−5244.
(70) Al-Ghamdi, S. A.; Volpe, M.; Hossain, M. M.; de Lasa, H. I.
VOx/c-Al2O3 Catalyst for Oxidative Dehydrogenation of Ethane to
Ethylene: Desorption Kinetics and Catalytic Activity. Appl. Catal. A
Gen. 2013, 450, 120.
(71) Al-Ghamdi, S. A.; de Lasa, H. I. Propane Oxidative
Dehydrogenation over a VOx/Al2O3 Catalyst: Characterization and
Catalytic Performance. Fuel 2013, submitted.
(72) De Lasa, H. I. Canadian Patent 1,284,017, (1991). USA Pat.
5,102,628, 1992.
(73) De Lasa, H. I.; Al-Khattaf, S. Catalytic Cracking of Cumene in a
Riser Simulator: A Catalyst Activity Decay Model. Ind. Eng. Chem. Res.
2001, 5398.

P dx.doi.org/10.1021/ie404064j | Ind. Eng. Chem. Res. XXXX, XXX, XXX−XXX