Structure-Reactivity Relationship for Titania

Supported Vanadium-Phosphorous-Oxide
Catalysts: ODH of Propane

Rudra Pratap Singh

Roll No.- Y210240

Department of Chemical Engineering

Indian Institute of Technology
Kanpur, 208 016
 OUTLINE
• Introduction
• Catalyst Preparation
• Characterization
 BET
 XRD
 EPR Studies
 TPR Studies

• ODH Reaction Studies

 Reproducibility
 Contact Time Effects
 Modeling Data

• Kinetic Parameter Estimation

 Objective Function
 Kinetic Models
 Predicted Concentrations

• Conclusion
ODH as an Alternative Route for Alkene
Formation
Conversion of Alkane to Alkene:
Dehydrogenation & ODH

 ODH Reaction Is
• Thermodynamically Stable
• Irreversible
• Exothermic

• But due to side reactions, selectivity of Alkene decreases

• Reaction is susceptible to Explosion
Supported V-P-O system is Active and
Selective for ODH of Propane

V2O5 Catalyst V2O5/TiO2 Catalyst

( +5, +4, +3) [V2O5/TiO2 > V2O5/ZrO2
> V2O5/Al2O3 > V2O5/MgO]

VPO Catalyst
[VOPO4, (VO)2P2O7] VPO/TiO2
Catalyst
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
 Incipient Wetness Impregnation Method
for Catalysts Preparation
Oxalic acid
solution
• Dried overnight at RT in a dessicator
Support • Dried for 12 Hrs at 383 K
(TiO2) • Calcined for 12 Hrs at 723 K

Precalculated amount of Heat treatment similar to

precursor in the solution Mixing the pretreatment of support

Precursors Final Catalyst

• Vanadium : Ammonium-meta-vanadate
• Phosphorous : Diammonium hydrogen phosphate
Nomenclature and Composition of Samples

Nomenclature Wt % of Wt % of V: P Molar
V2O5 in P2O5 in Ratio
catalyst catalyst
TiO2 0.0 0.0 -

3VTi 3.0 0.0 -

2V1PTi 3.0 1.2 2:1

1V1PTi 2.9 2.3 1:1

1V2PTi 2.9 4.5 1:2

1.2PTi 0.0 1.2 -

4.6PTi 0.0 4.6 -

Characterization
 No significant change of
Surface Area and XRD Patterns
• The surface area values are between 41 to 47 m2/g
• Peaks observed only due to the TiO2 support for
supported samples
• No peak of crystalline V2O5 is observed in the
supported samples
• Bulk V2O5 is present in unsupported 2V1P whereas
unsupported 1V1P and 1V2P does not show bulk V2O5
• It appears that the support is not significantly affected
during the preparation of the catalysts.
 EPR Reveals the Presence of V4+ Species
3VTi • V4+ species is present as
2V1PTi VO2+(hexa-coordinated)
1V1PTi
hydrated species in 3VTi
1V2PTi
• The formation of a
Intensity (a.u.)

VO(H2O)2+-O-P takes
place in 2V1PTi and
1V1PTi materials
• Something different is
formed over 1V2PTi
• No peak is present in the
spectrum of 1.2PTi and
4.6PTi
2400 2800 3200 3600 4000 4400
[G]
 TPR Shows the Reducibility of
Modified Catalysts
3VTi 2V1PTi 1V1PTi 1V2PTi
• Single peak detected
except for 1V2PTi
• Surface reduction rate
TCD Signal(a.u.)

varies as,
3VTi > 2V1PTi >
1V1PTi > 1V2PTi
• No peak detected for
1.2PTi and 4.6PTi

500 600 700 800 900 1000 1100

Temperature (K)
Reducibility of catalyst decreases with
the phosphorous content

Catalyst Tmax (K) H/V Ratio

3VTi 715 2.0

2V1PTi 750 1.6

1V1PTi 750 1.4

1V2PTi 778, 862 1.3

Different Vanadium Sites observed on TiO2 Support

New species V+5

V+4
Bulk V2O5 * * * * * *
* * ** * * * * New species
V+4 * * * * ** * * * V+5
* ** * * * * * **
TiO2 Support

• Bulk V2O5 – absent as detected by XRD analysis

• V+5 – observed by the TPR profiles for each catalyst
• V+4 – observed by the EPR spectra and TPR profiles
• New species – observed by EPR & TPR profiles for 1V2PTi
ODH Reaction Studies
 Reactor setup for Propane ODH

Pressure gauge
(1 atm) T
C Temp. Sensor (613-673 K)

Mass flow
Furnace
Controllers
Reactor (0.03-0.20 g)
(Propane: O2= 1:1; 2:1 10 port valve
and 3:1) To analysis
(Flow rate: 20-120 ml/min) GC (C3H8, C3H6, CO and
CO2)
 Generalized Reaction Scheme
CO
r5 • Reaction 1: Primary product C3H6
r2
• Reaction 2 & 3: Secondary product
r1 r6
C3H6 CO and CO2
C3H8
r3 • Reaction 4 & 5: Primary product
r4 CO2 and CO

CO2 • Reaction 6: Tertiary CO2

 Reaction Data is Reproducible
2 • Reaction Conditions:
3VTi C3H6
 Propane : O2 = 1:1

 Wt. of catalyst = 0.05g

Yield (%)

1
CO  Total flow Rate =
75ml/min

CO2
 Temp. = 653 -713 K (I)
 Temp. = 713 -653 K (II)

0
650 663 676 689 702 715
Temperature (K)
 Conversion Increases with Contact Time
3VTi 2V1PTi 1V1PTi 1V2PTi
5
• C3H8:O2 = 2:1
Propane Conversion (%)

4
• Temperature = 643 K
3
• Conversion Follows
the order:
2 3VTi > 2V1PTi >
1V1PTi > 1V2PTi
1

0
0 40 80 -1 120 160
Contact Time (kg lit s)
 Conversion and Selectivity are inversely
related
3VTi 2V1PTi 1V1PTi 1V2PTi
95
• Selectivity Shows the
inverse behavior
Propene Selectivity (%)

as,1V2PTi > 1V1PTI >

85 2V1PTi > 3VTi

• Curve of 2V1PTi and

1V1PTi are almost
75
parallel

• Reaction conditions are

65 same
0.5 1.5 2.5 3.5
Propane Conversion (%)
Reaction Studies: 3VTi; Weight of the catalyst = 0.03 g;
Reaction Yield (%) C-
C3H8/O2
Temp. Effect Effect balance
ratio
(K) C3H6 CO2 CO (Cout/Cin)

0.60 0.03 0.07 1:1 0.998

613 0.55 0.02 0.05 2:1 0.998

0.51 0.02 0.04 3:1 0.999

0.97 0.06 0.12 1:1 0.988

0.86 0.06 0.10 2:1 0.993

633
0.79 0.05 0.08 3:1 0.996

1.42 0.12 0.23 1:1 0.994

653 1.31 0.10 0.19 2:1 0.999

1.20 0.09 0.16 3:1 0.966

1.99 0.21 0.41 1:1 0.917

673 1.92 0.22 0.38 2:1 0.979

1.75 0.19 0.33 3:1 0.951

Kinetic Parameter Estimation
 Methodology used for the Kinetic-
Parameter Estimation

Optimization
Modeling Data Objective Function Technique
(Reaction Studies) (Determinant Criterion)
(GA)

Standard Error Kinetic-parameters Kinetic Models

Calculation (ki0, Ei, ai and bi) (PL and MVK)
Determinant Criteria is the ideal Objective
Function for the Optimization
For multiple response systems

Objective function = min |Zhk|

n
Where Zhk   ( y hu  g hu )( y ku  g ku ),
u 1
h and k = 1,..v

Responses are: mole fractions of C3H8, C3H6,

CO and CO2.
u = no. of experiments v = no. of responses
yhu and ghu = experiment and predicted mole
fraction of hth component in uth experiment
 Methodology used in Parameter
Estimation is good
1

3VTi
0.8
Predicted Concentrations

2V1PTi
1V1PTi
1V2PTi
0.6

0.4

0.2
PL-1 Model
0
0 0.2 0.4 0.6 0.8 1
Actual Concentrations
PL-1 Model:-12 parameter PL-2 Model:-12 Parameter
CO CO
r5
r3

r1 r1
C3H8 C3H6 C3H8 C3H6

r2 r4

CO2 CO2
ri = ki pA ai pBbi Where, i = 1, 2, 3, 4, 5
A = C3H8 and C3H6 ( for PL-1 model)
A = C3H8 ( for PL-2 model)

B = O2 ( for PL-1 and PL-2 model)

ki=ko*e- (Ei/R(1/T– 1/Tm))

PL-1 Model is Better than the PL-2 Model
Determinant Determinant
Catalyst Value for PL-1 Value for PL-2
Model Model

3VTi 2.41E-30 4.00E-30

2V1PTi 6.25E-30 6.88E-30

1V1PTi 2.48E-29 2.48E-29

1V2PTi 2.16E-31 2.16E-31

PL-1 Model: Calculated at P mC3H8 =0.2958 atm, PmO2=0.148 atm,
Tm =643.16 K
Catalyst
Parameter Units Conclusion
(3VTi) (2V1PTi) (1V1PTi) (1V2PTi)

k10 9.51 6.51 2.80 0.97

ml STP min-1
(g cat)-1 atm-
Values are

(ai+bi)
k20 1.04 0.44 0.17 0.04 decreasing (3VTi
to 1V2PTi)
k30 0.99 0.50 0.18 0.04
Constant (within
E1 80 85 83 69 error range)
except 1V2PTi
kJ mol-1

E2 64 80 95 55 Increasing except
1V2PTi
E3 52 58 79 37

a1 1 1 1 1 First Order

b1 0.49 0.68 0.65 0 Half Order

Dimensionless

a2 0.82 0.70 0.52 0.62 Can’t Say

b2 0 0 0 0 Zero Order

a3 1 1 0.72 1 First Order

b3 0 0.55 0.24 0.93 Can’t Say

PmC3H6 atm 0.0033 0.0033 0.0035 0.0028

Mars-van Krevelen Model: 8 Parameter Model
• Mechanism:
C3H8 (g) + O (s) C3H6 (g) + 3H2O + *red

C3H6 (g) + 6O (s) 3CO (g) + 3H2O + 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- )
r3 = k3 pC3H6 (1- )
r4 = k4 pO2  0.5k1 PC3H8  3.0k 2 PC3H 6  4.5k 3 PC3H 6

ki=ko*e- (Ei/R(1/T– 1/Tm)) 0.5k1 PC3H8  3.0k 2 PC3H 6  4.5k 3 PC3H 6  k 4 PO2
 MVK-1 Model: Tm =643.16 K
Catalyst
Parameter Units Conclusion
(3VTi) (2V1PTi) (1V1PTi) (1V2PTi)

k10 34 29 14 4
(0.28) (0.30) (0.22) (0.18)
ml STP min-1 (g cat)-1 atm-1
k20 357 204 92 18
(3) (21) (2) (1) Values are
decreasing
(3VTi to
k30 328 196 84 17 1V2PTi)
(3) (2) (1) (1)

k40 874 150 52 28

(61) (5) (2) (4)

E1 81 79 70 69
(1) (1) (1) (2)

E2 51 51 44 30 Values are
-1
(1) (1) (2) (3) similar (within
kJ mol the error
range) except
E3 45 52 44 33 for 1V2PTi
(1) (1) (1) (3)

E4 154 123 137 83

(5) (3) (3) (9)
 Pre-exponential factors decreases with
the Phosphorous-modification
1.2

k10
1
k20
k30
0.8
(Ki0) normalised

k40
k10
0.6
k20
1 - 3VTi k30
0.4
2 - 2V1PTi
0.2 3 - 1V1PTi
4 - 1V2PTi
0
1 2 3 4
Catalyst
• Relative decrease is different for each catalyst
• Number of active sites or activity per site decrease with an
increase in P-content
 Degree of Reduction (β) increases with
Propane Conversion
1
• At low conversions
2V1PTi
0.9 (<5%) the degree of
1V1PTi
1V2PTi
reduction is same for
0.8 3VTi each catalyst
β value

0.7 • At high conversions

(>5%) β follows the
0.6 trend
3VTi > 2V1PTi >
0.5 1V1PTi > 1V2PTi

0.4
0 3 6 9 12 15 18
Propane Conversion (%)
Predicted Propene Yield vs. Contact Time
6 (k 2+k 3)/k 1= 1.12, T= 673 K
PL-1
5 MVK-1
Propene Yield (%)

(k 2+k 3)/k 1= 1.14, T= 643 K

4
(k 2+k 3)/k 1= 1.18, T= 613 K

1
3VTi
0
0 300 600 900
W/F 0 (Kg m-3s)
Predicted Propene Yield vs. Propane Conv.
18

PL-1
Propene Yield (%)

15
MVK-1
12 1V2PTi, (k 2+k 3)/k 1= 0.08

9
1V1PTi, (k 2+k 3)/k 1= 0.23
6
2V1PTi, (k 2+k 3)/k 1= 0.53
3 3VTi, (k 2+k 3)/k 1= 1.14

0
0 5 10 15 20 25 30
Propane Conversion (%)
 Conclusion
• No significant change of BET surface area and XRD pattern
was observed.

• Paramagnetic V+4 species are present and increases with the

phosphorous content as suggested by EPR spectra

• TPR profile reveals the presence of V+5 and V+4 species and new
species is observed for 1V2PTi catalyst

• The propane ODH reaction reveals that the conversion and

selectivity are inversely related

• Kinetic parameters are successfully calculated and are close

correspond with the experimental and characterization results.

• PL-1 model describes the reaction data better than the PL-2
model
Conclusions (Contd…..)
• Observed decrease in propane conversion with the
phosphorous content is due to the decrease in the pre-
exponential factors

• The increase in propene yield at iso-conversion with an

increase in temperature and phosphorous modification
is related to the decrease in the (k2+k3)/k1 ratio.

• The decrease in (k2+k3)/k1 ratio with phosphorous addition is

primarily due to the dissimilar decrease of pre-exponential
factors.

• Mechanistic MVK-1 model appears to be better suited to

explain the variations in conversion and propene yields.

• Propane ODH reaction studies reveal that phosphorous

poisons the catalyst sites but the relative poisoning is
different for the different catalysts.
Thank You
Structure of V2O5
Structure of Bulk V2O5
TiO2 Rutile Surface