CHEMCON - 2004 - Research Paper

The effect of vanadium oxide loading on the kinetic
parameters for the ODH of propane over well-

characterized V2O5/TiO2 catalysts.
Reaction Engineering and Catalysis
Debaprasad Shee, R.P. Singh and G. Deo
Department of Chemical Engineering

Indian Institute of Technology Kanpur
Kanpur, 208 016, INDIA
Catalytic ODH- An efficient way of obtaining
high value products from abundant, low-
Ethane value feedstock High
Propane Value
Butane Olefins
Catalytic Ethylene
Possible Feedstock ODH Propylene
(Low Temp.) Butylenes
Polymers
Detergents
Adhesives
Paints
Various Supported V2O5/TiO2 samples
Prepared and Characterized
 Supported V2O5/TiO2 catalyst were prepared by

the incipient wet-ness impregnation technique
 Characterized for Surface area and by Raman, XRD,
EPR and TPR studies
 No significant change in surface area was observed.
(Surface area: 40-41 m2/g)
 Only one temp maximum was observed in TPR profile
of all the supported samples. Also H/V ratio: 1.8-1.9
 EPR studies reveal presence of some V+4
paramagnetic species
Raman Spectroscopy Detects Surface Species and
Monolayer Coverage
 At low Vanadium oxide
x% V2O5/TiO2
(ambient spectra) loading bands at ~940 cm-1
dominates.
4%  At high vanadium oxide
loading bands at 990-1000 cm-1
Intensity (a.u.)
3%
dominates.
 For 4% V2O5/TiO2 sample, a
2% weak band at 994 cm-1 was
observed due to presence of
1% V2O5 crystal.
 Monolayer coverage
achieved for 4% V2O5/TiO2
1200 1000 800 sample
-1
Raman Shift (cm )
Surface Vanadia Species are Present on Supported
Vanadium Oxide Catalysts
O O
O
Polyvanadate
V V
O O
O
O O
V
O O Wachs and Co-workers
O
Monovanadate V2O5 crystals
Oxide Support
Under dehydrated conditions:

• at low vanadium oxide loading only monomeric tetrahedral species
possessing one V=O bond and three V-O-support bonds exists
• at high vanadium oxide loadings a polymeric species possessing
V-O-V bond also exists
Several Pathways are Possible When
Propane Reacts
CO CO
Most suitable mechanism
C3H8 C3H6 C3H8 C3H6
CO2 CO2
C3H8:O2 = 1:1 to 3:1
Temp = 340 oC to 400 oC
Catalyst = x% V2O5/TiO2
• The reactor operated under isothermal, steady state condition

• The gas phase reactions are negligible
• The catalyst activity remains constant.
Kinetic Modeling of ODH Leads to
Non-Linear Optimization Problem
• Differential material balance for, ith, component
dx i
  n ijrj / v 0
dw j
i  1.......v
Where, rj = fj(yi, Kj ) Power law model chosen
• Nonlinear mass balance equations are solved by using

fourth order Runge-Kutta equation
w
x i   ( n ijrj / v 0 )dw w = weight of the catalyst
0 j
Kinetic Parameters Estimation
Minimization of an objective function is required to obtained the best

value of the parameters.
For multi-response system = min |Zhk|
n
Where Z hk   ( y hu  g hu )( y ku  g ku ) , h and k = 1,..v

u 1
Responses are: mole fractions of C3H8, C3H6, CO and CO2.

n = no. of experiments v = no. of responses
yhu and ghu = experiment and predicted mole fraction of hth component in uth
experiment
Genetic Algorithm is Used for Optimization

Power Law Model:-12 parameter
CO
r2 Primary Product: Propene,C3H6
Secondary products: CO and CO2
r1
C3H8 C3H6
r3 General Power law expression
PC ai PD bi
CO2 ri  k i ( m ) ( m ) i =1,2…
PC PD
Where ki = rate constant for reaction i,

PC and PD are partial pressure of reactant C and D
PCm and PDm are mean partial pressures of C and D
ai and bi = partial pressure exponent of the reactants
for reaction i
Mars-van Krevelen (MVK) model: 8 parameter
Mechanism:
C3H8 (g) + O (s) C3H6 (g) + 3H2O + *red
C3H6 (g) + 6O (s) 3CO (g) + 3H 2O + 6*red
C3H6 (g) + 9O (s) 3CO2 (g) + 3H2O + 9*red
O2 + 2*red 2O (s)
Reaction Rate Expressions

r1 = k1 pC3H8 (1-)
r2 = k2 pC3H6 (1- )
0.5k1 PC3H8  3.0k 2 PC3H 6  4.5k 3 PC3H 6

r3 = k3 pC3H6 (1- ) 0.5k1 PC3H8  3.0k 2 PC3H 6  4.5k 3 PC3H 6  k 4 PO2
r4 = k4 pO2 
 = degree of reduction of catalyst
ki=ko*e- (Ei/R(1/T– 1/Tm))
Kinetic Parameters Reveal Changes for
Different Vanadia Coverage
1% V2O5/TiO2 2% V2O5/TiO2 3% V2O5/TiO2
k10 1.48 5.42 9.51 • Pre-exponential factor increases

E1 89 86 80 with increase in V2O5 loading
• Activation energy for ODH reaction
C3H8 C3H6 is relatively independent of loading
k20 0.42 1.01 1.04 • Propane ODH reaction follows first
E2 51 64 64 order dependency with respect to
propane partial pressure
C3H6 CO
• oxygen partial pressure dependency
k30 0.37 0.87 0.99 is not necessarily of zero order
E3 39 54 52
C3H6 CO2 Model: Power Law
a1 1.0 1.0 1.0 Ei: kJ mol-1
b1 0 0 0.49 ki0= ml STP min-1(g cat)-1
Vanadia Loading Affects Propene Yield and
Ratio of Rate Constant
5
5
% propene yield
4 3VTi
k1/(k2+k3)
4
3 2VTi
3
2
1VTi
1 2
0 1
0 2 4 6 8 10 1 2 3
% Propane conversion % V2O5 loading

• Increasing the loading increases k1/(k2+k3) ratio at
a particular temperature
C3H8:O2 = 2:1 • With increase in k1/(k2+k3) ratio the propene yield
Temp = 643 K
increases
Propene Yield Increases with Increase in Reaction
Temperature
8 8 5
7 4.5
3VTi 4
6 6
3.5
% Propene yield
k1/(k2+k3)
5 3
k1/(k2+k3)
4 2VTi 4 2.5
3 2
1.5
2
2 1VTi 1
1 0.5
0 0
0
575 625 675 575 625 675
Reaction Temp ,K Reaction Temp, K
• with increase in reaction temp k1/(k2+k3) ratio increases

• with increase in reaction temp propene yield increases
Propene yield and Propane conversion
increases with increase in contact time
5 16
% Propane conversion
14 C3H8:O2 = 2:1 3VTi
4 3VTi Temp = 643 K
12
2VTi
% Propene yield
3 10 2VTi
8
2
1VTi 6
1 4
2 1VTi
0 0
0 200 400 600 0 200 400 600
Contact time, Kg m-3 s Contact time, Kg m-3 S
• Propene yield increases with increase in contact time.

• Propane conversion also increases with increase in contact time
Conclusions
• Characterization studies reveal that monolayer coverage is

achieved at 4% vanadium oxide loading corresponding to
~11.0 V mmole/m2.
• Some paramagnetic V+4 species were also detected.
• pre-exponential factor; ki0 increases with increase in
vanadium oxide loading
• For a consecutive reaction propene yield depends on contact
time and k1/(k2+k3) value.
• The numerical value of k1/(k2+k3) increases with vanadium
oxide loading and reaction temperature.
Conclusions
• The increase in k1/(k2+k3) ratio increases the propene yield.
• Propene yield increases with increase in contact time.
• Propane conversion also increases with increase in contact
time.
Acknowledgment
• Ministry of Human Resources and Development (INDIA)
Acknowledgments
• Ministry of Human Resources and Development (INDIA)

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The effect of vanadium oxide loading on the kinetic

parameters for the ODH of propane over well-

Reaction Engineering and Catalysis

Debaprasad Shee, R.P. Singh and G. Deo

Department of Chemical Engineering

 Supported V2O5/TiO2 catalyst were prepared by

Under dehydrated conditions:

• The reactor operated under isothermal, steady state condition

Where, rj = fj(yi, Kj ) Power law model chosen

• Nonlinear mass balance equations are solved by using

Minimization of an objective function is required to obtained the best

Where Z hk   ( y hu  g hu )( y ku  g ku ) , h and k = 1,..v

Responses are: mole fractions of C3H8, C3H6, CO and CO2.

Genetic Algorithm is Used for Optimization

Where ki = rate constant for reaction i,

C3H6 (g) + 6O (s) 3CO (g) + 3H 2O + 6*red

C3H6 (g) + 9O (s) 3CO2 (g) + 3H2O + 9*red

Reaction Rate Expressions

k10 1.48 5.42 9.51 • Pre-exponential factor increases

% Propane conversion % V2O5 loading

• with increase in reaction temp k1/(k2+k3) ratio increases

• Propene yield increases with increase in contact time.

• Characterization studies reveal that monolayer coverage is

• Ministry of Human Resources and Development (INDIA)

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