Chemical Reaction Engineering: Sub-Session

ChemCon’04 Mumbai
The effect of vanadium oxide loading on the kinetic
parameters for the ODH of propane over well-characterized
V2O5/TiO2 catalysts
Debaprasad Shee, Rudra Pratap Singh and Goutam Deo*
*
Department of Chemical Engineering, Indian Institute of Technology Kanpur, Kanpur 208 016
Fax: +91-512-2590104; Tel: +91-512-2597881;
E-mail address: [email protected]

Abstract in mixed oxides and on supports for the ODH of

To understand the effect of vanadium oxide propane. The catalytic activity of these oxides
(vanadia) loading on titania supported vanadia depends on their surface structure, character of
catalysts several V2O5/TiO2 catalysts are chemical bond and the coordination unsaturation
prepared by the incipient wetness impregnation of the surface atom, etc. [1]. The effects on the
technique. The loadings varied from below kinetic parameters, however, are not well
monolayer to above monolayer coverages. The understood.
supported samples are characterized and these The present study deals with determining the
studies revealed that only surface molecularly effects of vanadium oxide loading on the kinetic
dispersed vanadia species are present on the TiO2 parameters for the ODH of propane. For this
support below monolayer coverage. Above purpose a series of well-characterized V2O5/TiO2
monolayer coverage bulk V2O5 and surface catalysts are considered. Kinetic analysis is
vanadia species are observed. The monolayer achieved by using power law model and a redox
coverage is ~11.0 V µmole/m2. Additionally, Mars-van Krevelen model. The parameters
some paramagnetic V+4 species are also detected. associated with this reaction model, namely the
The propane ODH reaction is carried out over pre exponential factors and activation energies,
the catalysts to observe the effect of loading on are estimated by optimization of an objective
the kinetic parameters. It is observed that function using Genetic Algorithm (GA).
propane conversion increased with vanadium
loading up to the monolayer coverage. The Experimental
kinetic-parameters are determined for the Catalyst Preparation
V2O5/TiO2 catalysts under net-reducing A series of supported V2O5/TiO2 catalysts were
conditions (C3H8:O2 ratios of 1:1, 2:1 and 3:1) prepared by the incipient wetness impregnation
using a power law and mechanistic (Mars van technique on a pretreated titania support
Krevelen) model. Comparison of the kinetic (Degussa, P-25). The precursor used was
parameters suggests that propane ODH reaction ammonium metavanadate (NH4VO3, 98%
follows first order dependency with respect to purity). Pretreatment of the support has been
propane partial pressure. However, the oxygen discussed elsewhere [2]. The pretreated support
partial pressure dependency is not necessarily and incipient volume of vanadium oxalate
zero order. Based on the kinetic-parameters the precursor solution were intimately mixed in
effect of contact time on conversion and propene order to prepare the catalyst with different
yield for the two catalysts are discussed. loading of vanadium oxide. The details
preparation method can be found elsewhere [2].
Keywords The V2O5/TiO2 catalysts of 2, 3 and 4 % V2O5
Propane ODH, vanadium, titania, kinetic- loading were prepared. These samples
parameters characterized, the details for which are also
available elsewhere [2].
Introduction Reaction setup
Vanadium oxide is a well-established catalyst The ODH of propane was carried out in a fixed
and has been widely used as an active component bed, down flow, tubular quartz reactor at
atmospheric pressure. The catalyst bed 1. Formation of propene (r1): The gas phase
containing a physical mixture of catalyst and the propane reacts with lattice oxygen to form gas
amount of quartz powder required to form a bed phase propene;
height of 1 cm was placed on quartz wool in the C 3 H 8 ( g ) + O( s ) → C 3 H 6 + H 2 O + *red (5)
reactor. The reactor tube was mounted vertically Where *red is a reduced site.
in a tubular furnace. The product gases were sent 2. Formation of CO from propene (r2): The gas
for online analysis to a gas chromatograph. For phase propene reacts with lattice oxygen to form
kinetic analysis different propane to oxygen gas phase CO:
ratios (1:1, 2:1 and 3:1) were used with a total
flow rate of 75ml/min. The effect of vanadium C 3 H 6 ( g ) + 6O( E ) → 3CO ( g ) + 3H 2 O + 6 *red
oxide loading was studied by varying the (6)
temperature between 613 and 673 K. Additional 3. Formation of CO2 from propene (r3): The gas
details can be found elsewhere [3]. phase propene reacts with lattice oxygen to form
Kinetic modeling and parameter estimation CO2 gas:
The differential material balance equation for C 3 H 6 ( g ) + 9O( s ) → 3CO2 ( g ) + 3H 2 O + 9 *red
each component, i, for a particular reaction can (7)
be written as 4. Re-oxidation (r4) : Finally, the catalyst is
∑
V0 xi |W −V0 xi |W + dW − nij r j dW = 0 I = 1...ν reoxidised by gas phase oxygen
(1) O2 + 2 *red → 2O( s ) (8)
Where, The reaction rate for the above four reactions,
V0 = volumetric flow rate of the feed (5)-(8) are expressed as
xi = mole fraction of the ith component. r1 = k1 PC3 H 8 (1 − β ) (9)
nij = stoichiometric coefficient of the ith
component for the jth reaction r2 = k 2 PC3 H 6 (1 − β ) (10)
Kj = kinetic parameters for the j th reaction r3 = k 3 PC3 H 6 (1 − β ) (11)
rj = rate of jth reaction and is a function of Kj or
rj r4 = k 4 PO2 β (12)
= fj(xi, Kj), Assuming that the rate of oxygen consumed in
ν = number of components the reactions r1, r2, and r3 is equal to the rate of
W = weight of the catalyst. oxygen replacement by the reaction r4, β can be
Simplification of Eqn. (1) results in expressed as
dxi 0.5k1 PC3 H 8 + 3.0k 2 PC3 H 6 + 4.5k 3 PC3 H 6
= ∑ nij r j /V0 (2) β=
dW j 0.5k1 PC3 H 8 + 3.0k 2 PC3 H 6 + 4.5k 3 PC3 H 6 + k 4 PO2
The details of kinetic modeling and parameter
(13)
estimation method are given elsewhere [3].
The rate constants, ki’s are expressed in the
Reaction Models
Arrhenius form as
Power Law model
Based on previous studies only one power law − Ei 1 1
k i = k i 0 exp[ ( − )] (14)
model, PL-1 was analyzed to determine the R T Tm
empirical reaction rates, which can further be Where,
used to develop mechanistic model [1]. The PL-1 ki0 = pre exponential factor,
model assumes that CO and CO2 are secondary Tm = mean temperature.
products and are formed from propene. The
general power law expression can be given as Results and Discussion
P P Characterization studies
ri = k i ( Cm ) ai ( Dm ) bi (4) The BET surface area of the titania support and
PC PD
V2O5/TiO2 samples were determined and
ki = rate constant for reaction i, where i = 1,2,..,4;
tabulated as in Table 1 along with Tmax and H/V
Pc and PD are partial pressure of reactant C and
atomic ratio from temperature programmed
D; PCm and PDm are mean partial pressures of C and reduction studies. It is observed that there is no
D; and ai and bi = partial pressure exponent of significant change in surface area, Tmax and H/V
the reactants for reaction i. ratio with increase in vanadia loading. Only one
Mars-van Krevelen ( MVK ) temperature maximum, Tmax was observed for all
According to MVK mechanism for ODH the sample studied. The H/V atomic ratios are
reactions the following four reactions are essentially constant and close to two. This value
considered, r1, r2, r3 and r4 [2, 4].
suggests that the surface V5+ oxide species are based on reaction studies reveals that the propane
reduced to V3+ oxide species by H2 reduction. conversion increases with temp as well as
From the TPR results, it was observed that vanadium oxide loading up to the monolayer
reduction behavior of the surface vanadium coverage. Contact time data shows that the
oxide species relatively independent of surface selectivity of primary product, propene (C3H6),
coverage till monolayer. decreased with increase in vanadium oxide
Table 1 loading. The selectivity of secondary products,
Surface are, Tmax and H/V atomic ratio of V2O5/TiO2 carbon oxides (COX), however increased with
samples vanadium oxide loading. It was also observed
that the propane activity determined at different
Sample Surface Tmax (K) H/V
temperature increased with vanadium oxide
atomic area (m2/g) ratio
loading up to monolayer coverage.
2% V2O5/TiO2 41 765 1.8 Based on the input output mole fraction the
3% V2O5/TiO2 41 783 1.8 kinetic parameters for PL-1 and MVK models
4% V2O5/TiO2 40 780 1.9 are determined. The parameters obtained for the
catalyst are compared to analyze the effect of
The Raman Spectra of 2-4% V2O5/TiO2 vanadia loading. Analysis of the parameter
samples were obtained under ambient conditions values reveals that the three pre-exponential
in the range 800-1000 cm-1 region. At less than factor, ki0, increases with increasing vanadium
4% vanadia loading two Raman bands were oxide loading for both models. Furthermore,
obtained. At low vanadium oxide loading bands power law model reveals that formation of
at ~940 cm-1 dominates and at high vanadium propene is first order with respect to propane
oxide loading bands at 990-1000 cm-1 dominates. partial-pressure; where as, propene formation
These bands are corresponds to metavanadate rate with respect to oxygen partial pressure is not
and decavanadate, respectively [5]. For 4% necessarily zero order. The pre-exponential
V2O5/TiO2 sample, a weak band at 994 cm-1 was factor usually corresponds to the number of
observed due to presence of V2O5 crystal. active sites or the activity per site. Consequently,
Consequently, the monolayer coverage is the number of active sites or the activity per site
achieved for this sample. The monolayer or both increases with increase in vanadium
coverage was calculated as ~11.0 V µmole/m2. oxide loading till monolayer.
Wachs and co workers [5-7] characterized the
6
V2O5/TiO2 catalysts using Raman spectroscopy
under both ambient and dehydrated conditions. 5 673 K PL-1
The Raman spectra under ambient condition for T= 643 K MVK
Propene Yield (%)

4
the catalysts in the present study are similar to 613K
the Raman spectra obtained by them. Hence the 3
dehydrated Raman spectra results in their study
can be used in the present study. It was 2

concluded that at low vanadium oxide loading 1

only monomeric tetrahedral species possessing
one V=O bond and three V-O-support bonds 0
0 100 200 300 400 500 600 700 800 900
exists and at high vanadium oxide loadings, in -3
W/F0 (Kg m s)
addition to monomeric oxide species, a
polymeric species also exists. Fig 1. Effect of contact time on predicted
The EPR spectra of all catalyst sample of propene Yield for 3% V2O5/TiO2 catalyst.
various loading were obtained at room C3H8:O2= 2:1.
temperature. All the spectra were centered at
3400 G. Then intensity of peaks increases with The kinetic parameter can also be used to obtain
vanadium oxide loading. The EPR spectra the optimum reactor operating conditions and for
suggest that minor amount of V+4 species are catalyst design. For a consecutive reaction
also present. mechanism, as in the Pl-1 and MVK models
Kinetic analysis chosen here, the propene yield depends on the
The 2 and 3% V2O5/TiO2 catalyst were chosen contact time and (k2+k3)/k1 value [8]. This is
for the propane ODH reaction. The propane shown in Fig 1 where the predicted propene
ODH reaction was carried out over these yield for the 3% V2O5/TiO2 catalyst is plotted
catalysts by varying the propane to oxygen ratio versus contact time for different (k2+k3)/k1
and the temperature. Comparison of the values values corresponding to different temperature. It
is observed that for PL-1 model an optimum increase in activity of catalyst. Using the kinetic
contact time is observed, whereas for MVK parameter the effect of contact time on propane
model oxygen is depleted before the propene conversion and propene yield was explained. For
yield reaches a maximum. Comparing the a consecutive reaction propene yield depends on
propene yield at a particular contact time for contact time and (k2+k3)/k1 value. The decrease
different (k2+k3)/k1 values suggests that the in (k2+k3)/k1 increases the propene yield. The
propene yield increases as the (k2+k3)/k1 numerical value of (k2+k3)/k1 decreases with
decreases or the reaction temperature increases. vanadium oxide loading. Thus, the vanadium
Additionally, for the PL-model the contact time oxide loading has a pronounced effect on the
where the propene yield is maximum also kinetic parameter for the ODH of propane.
increases with an increase in (k2+k3)/k1 value.
Similar trends are observed for first order Acknowledgements
consecutive reactions [8]. A change in the The authors are grateful to Prof. I.E. Wachs,
(k2+k3)/k1 can be achieved by changing the Lehigh University, for the Raman analysis. The
temperature or by changing the catalyst authors are also grateful for the partial financial
composition. support from ministry of human resource and
The effect of catalyst composition is shown Development (MHRD) for the present work.
in Fig 2, in which distinct optima is observed for
3% V2O5/TiO2 catalyst. For 2% V2O5/TiO2 References
catalyst, however, the plot becomes relatively [1] H.H. Kung, Adv. Catal. 40 (1994) 1.
flat after reaching maximum value due oxygen [2] K. Routray, K.R.S.K. Reddy, G. Deo, Appl.
depletion. The effect of contact time on Catal. A Gen. 265 (2004) 103.
conversion and selectivity show similar trend as [3] R.P. Singh, M.Tech Thesis, IIT Kanpur,
found experimentally [9]. 2004.
[4] D.C. Creaser, B. Anderson, R.R. Hudgins,
P.L silveston, Can. J. Chem. Eng. 78 (2000)
5 182.
[5] H.E. Eckert, I.E. Wachs, J. Phys Chem. 93
4 3% V 2O 5/TiO 2 (1989) 6796.
[6] G. Deo, I.E. Wachs, J. Phy. Chem. 95 (1991)
% Propene Yield

3 2% V 2O 5/TiO 2 5889.
[7] G. Deo, I.E. Wachs, J. Catal. 146 (1994) 323.
2 [8] H.S. Fogler, Elements of Chemical reaction
Engineering, Prentice-Hall of India Pvt. Ltd.,
1 3rd Edition, New Delhi, 2002.
[9] D. Shee, G. Deo, unpublished results.
0
0 300 600 900 1200 1500 1800
-3
W /Fo, Kg m s

Fig 2. Effect contact time on % predicted

propene Yield for 2 and 3% V2O5/TiO2. PL-1
Model, C3H8:O2= 2:1, at 643 K.

Conclusion
Several loadings of V2O5/TiO2 catalyst were
prepared by incipient wetness technique.
Characterization studies reveal that monolayer
coverage is achieved at 4% vanadium oxide
loading corresponding to ~11.0 V µmole/m2.
Some paramagnetic V+4 species were also
detected. The kinetic parameters were
successfully estimated for a power law and MVK
model by minimizing objective function using
genetic algorithm. It was observed that pre-
exponential factor; ki0 increases with increase in
vanadium oxide loading giving rise to an