Ucalgary 2003 Younis Lubna Basheer 536517

UNIVERSITY OF CALGARY
Numerical and Experimental Studies of Catalytic Combustion
in aPacked Bed Reactor
by
LUBNA BASHEER YOUNIS
A DISSERTATION
SUBMITTED TO THE FACULTY OF GRADUATE STUDIES
IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE
DEGREE OF DOCTOR OF PHILOSOPHY
DEPARTMENT OF MECHANICAL AND MANUFACTURING ENGINEERING
CALGARY, ALBERTA
NOVEMBER, 2003
- © LUBNA BASHEER YOUNIS 2003

UNIVERSITY OF CALGARY
FACULTY OF GRADUATE STUDIES
The undersigned certify that they have read, and recommend to the Faculty of Graduate
Studies for acceptance, a thesis entitled "Numerical and Experimental Studies of
Catalytic Combustion in aPacked Bed Reactor" submitted by Lubna Younis in partial
fulfillment of the requirements of the degree of Doctor of Philosophy.
Supervisor, Dr. I. Wierzba

Department of Mechanical and
Manufacturing Engineering
Dr. G A. Karim
Department of Mechanical and
Manufacturing Engineering
Department of Chemical and

Petroleum Engineering
Dr. A. Jeje
Department of Chemical and
Peleum..Egineering
External Examiner, Dr. M. D. Checkè

Department of Mechanical Engineering
University of Alberta
November 28th 2003

Date
11
ABSTRACT
A one-dimensional, non-equillibrium mathematical model of the catalytic combustion in
apacked bed reactor was developed. The model includes heat conduction, convective and
radiative heat transfer, axial diffusion, and accounts for both homogeneous (gas-phase)
and heterogeneous (surface) reactions of the Arrhenius type. The unsteady state equations
of conservation of mass, chemical species, and energy with appropriate boundary and
initial conditions were solved using afinite-difference procedure. Numerical simulation
was conducted with mainly lean premixed preheated methane-air mixtures over platinum
and abinary mixture of C0304/Cr2O3 catalysts for arange of equivalence ratios, approach
velocities, and inlet temperatures for three different cases: (i) inert bed (gas-phase), (ii)
heterogeneous reaction only, and (iii) both heterogeneous and homogeneous reactions.
The effects of the bed porosity, solid thermal conductivity, and bed length on methane
conversion were also studied. It was found that the solid thermal conductivity has a
strong influence on methane conversion when both homogeneous and heterogeneous
reactions were included. The results also showed that the bed length affected the methane
oxidation significantly especially when the bed porosity was greater than 0.45.
The catalytic combustion of other gaseous-fuels (ethane, propane, carbon monoxide, and
hydrogen) over platinum and binary mixture of C0304/Cr2O3 catalysts was also examined
numerically. The results show that the conversion of these fuels exhibits similar behavior;
i.e. the conversion of the fuel increased with an increase in the inlet temperature and
equivalenáe ratio, and a decrease in the approach velocity. It was also found that the
complete conversion of hydrogen took place at much lower inlet temperatures than those
required for the complete conversion of other fuels. The obtained results are consistent
with the reactivity of theses fuels as well as with the observed experimental trends.
Experimental studies for model validation were also conducted for the catalytic oxidation
of lean methane-air mixtures within the packed bed reactor. The model developed
together with the corresponding experimental data was used to establish the kinetic data
for global surface reaction (the activation energy and the pre-exponential factor), over
platinum and C0304/Cr2O3 catalysts for the fuels employed within the packed bed
reactor.
111
ACKNOWLEDGMENTS
The author wishes to express her sincere gratitude to her supervisor, Dr. I. Wierzba for
her valuable advice, support and guidance during the course of thi research and thesis
writing.
The author also would like to extend her thanks to Dr. G. A. Karim, Dr. D. Checkel, Dr.
S. A. (Raj) Mehta, and Dr. A. Jeje for serving on her exam committee and providing
valuable suggestions in conjunction with this study. Dr. Karim's continuous support and
encouragement throughout the duration of this investigation is highly appreciated.
Thanks should also go to Dr. A. A. Mohamad for his invaluable and endless advises and
guidance regarding the model development part of this research.
Thanks should go to the technical staff of the Department of the Mechanical and
Manufacturing Engineering machine shops, especially to R. Apperal, G. East, B.
Ferguson, A. Moehrle, R. Mosher, and B. Sanders for their assistance in instrumentation

and apparatus preparation and modifications.'
Sincere thanks go to J. McNeely, for his prompt response to any assistance required by
the author for the apparatus and instrumentations repair and preparation with
considerable effort. The author also acknowledges N. Vogt for providing technical staff
promptly when they are needed.
The author would like to thank her office-colleague H. Li for his constructive comments
and discussion during the progress of this work. Thanks should also go to her lab-
colleagues Q. Wang and C. Veer.
The cooperation of the secretarial staff in the Department of the Mechanical and
Manufacturing Engineering is also acknowledged.
Special thanks are attributed to the author's family for their continuous encouragement,
devotion and moral support throughout the duration of this study.
Finally, the financial assistance of the University of Calgary and National Science and
Engineering Research Council of Canada (NSERC) is greatly acknowledged.
iv
DEDICATION
To my beloved parents
who taught me that knowledge is the
key to success
To my daughters, Shand and Danya,
my son, Mustafa, and
my wonderful husband Majeed

TABLE OF CONTENTS
PAGE
ABSTRACT
ACKNOWLEDGMENTS S iv
DEDICATION
TABLE OF CONTENTS Vi
LIST OF TABLES X
LIST OF FIGURES Xi
LIST OF SYMBOLS xxii
CHAPTER 1: INTRODUCTION 1
1.1 Background .. 1
1.2 Objectives of the Study .12
1.3 Thesis Organization 13
CHAPTER 2: LITERATURE REVIEW 14

2.1 Introduction 14
2.2 Experimental Work 14
2.2.1 Fundamental Studies . 15
2.2.2 Applications .17
2.2.3 Non-Noble Metal Catalysts .19
2.2.4 Catalytic Oxidation of Some Common Gaseous Fuels 20
2.3 Theoretical and Computational Studies 27
2.3.1 Bulk Diffusion 28
2.3.2 Intraparticle Diffusion 28
2.3.3 Coupled Heterogeneous and Homogeneous Reactions . .29
2.3.4 Transport Mechanisms 33
vi
2.4 Summary = 35
CHAPTER 3: ANALYSIS AND MATHEMATICAL MODELING 37

3.1 Introduction .37
3.2 Description of the Physical Model 38
3.3 Description of the Mathematical model 39
3.3.1 Governing Equations ... 39
3.3.2 Kinetic Modeling .44
3.3.3 Initial Conditions ..45
3.3.4 Boundary Conditions 45
3.4 Numerical Model 46
3.4.1 Method of Solution . .46
3.4.2 Computer Code Development .46
3.5 Preliminary Results of Numerical Simulation of Methane 49
3.5.1 Inert Bed 52
3.5.2 Heterogeneous Reactions 55
3.5.3 Coupled Homogeneous-Heterogeneous Reactions 58
3.5.4 Effect of Bed Porosity .60
3.5.5 Effect of Bed Length 64
3.5.6 Effect of Thermal Conductivity of the Bed of Solids •75
CHAPTER 4: EXPERIMENTAL APPARATUS AND PROCEDURE 79

4.1 Motivation 79
4.2 Experimental Apparatus .80
4.2.1 Catalytic Reactor .83
4.2.2 Compressed Air and Main Heater Assembly .86
4.2.3 The Choked Nozzle Meter System .. 86
4.2.4 Fuel Injection System ..88
4.2.5 Exhaust Gas Analysis System 88
vi'
4.2.6 Instrumentation and Measurements 92
4.3 Experimental Procedure .93 -
4.4 Pellet Materials for the Packed Bed Reactor 95
4.5 Apparatus Limitations and Operational Parameters .96
CHAPTER 5: EXPERHV[ENTAL RESULTS 98
5.1 Introduction 98
5.2 Inert Packed Bed 99
5.3 Catalytic Packed Bed .. 101
5.3.1 Effect of Catalyst Aging 101
5.3.2 Combustion of Methane over Aged Platinum Catalyst 107
54 Oxidation of Methane over Binary (C0304/Cr2O3) Catalyst .111
5.5 Summary ...116
CHAPTER 6: NUMERICAL SIMULATION OF METHANE
COMBUSTION IN A PACKED BED REACTOR 117

6.1 Introduction . .117
6.2 Determination of Kinetic Data for Surface Reactions 117
6.2.1 Platinum Catalyst 117
6.2.2 C0304/Cr2O3 Catalyst 122

6.3 Results of Model Prediction 125
6.3.1 Methane Oxidation within the Inert Bed 125
6.3.2 Methane Oxidation within the Heterogeneous Bed 127
6.4 Summary 128

I
CHAPTER 7: OXIDATION OF OTHER GASEOUS FUELS
IN A PACKED BED REACTOR 130
7.1 Introduction 130
viii
7.2 Ethane Combustion 134
7.3 Propane Combustion 139
7.4 Carbon Monoxide Combustion .144
7.5 Hydrogen Combustion .148
CHAPTER 8: COMPARISON OF MODEL PREDICTION WITH
THE EXPERIMENTAL DATA 155
8.1 Introduction 155
8.2 Determination of Kinetic Data for Surface Reactions of Common

Gaseous Fuels .155
8.3 Summary ..162
CHAPTER 9: CONCLUSIONS AND RECOMMENDATIONS 166
9.1 Summary and Conclusions 166,

9.2 Recommendations for Further Work .169
REFERENCES 170
Appendix A: Thermophysical Properties 188
A.1 Gas Specific Heats 188
A.2 Diffusion Coefficient 189
A.3 Gas Thermal Conductivity 191
Appendix B: Choked Nozzles Calibration .......................................192
Appendix C: Thermocouple Correction 195
Appendix D: Pressure Drop .............................. 196
Appendix E: Gas Analysis ......... ............................... .198
Appendix F: Program Listing.............................. ... 199
ix
LIST OF TABLES
TABLE PAGE
Table 3.1 Values of operating parameters employed in the numerical
calculations 49
Table 4.1 Comparison between the measured methane using the gas
chromatograph and the gas analyzer for 4= 0.35 at different
inlet temperatures 90
Table 7.1 Kinetic parameters for gas-phase reactions 132
Table 7.2 Kinetic parameters for surface reactions 133
Table 8.1 Kinetic data for platinum and C0304/Cr2O3 catalysts within the
packed bed reactor for all the fuels employed in this study 161
Table A. 1 Gas specific heat correlation constants 188
Table A.2 Gas specific heat correlation (Eq. A.2) constant 189
Table A.3 Lennard-Jones parameters for species employed in the

calculation 191
LIST OF FIGURES
FIGURE PAGE
Figure 1.1 Classification of catalysts (Hagen, 1999) . .3
Figure 1.2 Reactions of synthesis gas (Hagen, 1999) 5
Figure 1.3 Mechanisms of catalyst deactivation (M =metal) (Hagen, 1999) 8
Figure 3.1 Schematic diagram of the physical model 38
Figure 3.2 Control volumes and mesh generation .47
Figure 3.3 Flow chart of the numerical model 48
Figure 3.4 Comparison between predicted methane conversion using the
kinetic data of Westbrook (1981) and experimental data for
methane conversion from Depiak and Wierzba (1999); u = 1.0
m/s, 4= 0.35, k = 1.0 W/m.K, inert bed 52
Figure 3.5 Comparison between calculated and experimental results of
methane conversion; u = 1.0 m/s, 4= 0.35, ks 1.0 W/m.K,
inert bed 53
Figure 3.6 Calculated methane conversion as a function of inlet
temperature at different equivalence ratios; u= 1.0 m/s, k = 1.0
W/m.K, inert bed, (*) Depiak and Wierzba (1999) 54
temperature at different approach velocities; 4= 0.35, k = 1.0

W/m.K, inert bed 54
temperature for various equivalence ratios; u= 1.0 m/s, lc = 1.0
W/m.K, Pt catalyst . 56
Figure 3.9 Calculated methane conversion along the bed; = 0.71, u= 1.0
m/s, Tin = 1200 K, Pt catalyst 56
xi
temperature for different approach velocities; 4) = 0.35, k = 1.0
W/m.K, Pt catalyst 57
temperature at different equivalence ratios; u= 1.0 m/s, k = 1.0
temperature for different approach velocities; 4) = 0.35, k = 1.0
temperatur&for various bed porosities; 4) = 0.35, u= 1.0 mIs, k5
= 1.0 W/(m.K),L50 mm 61
Figure 3.14 Calculated methane conversion as afunction of bed porosity for
different inlet temperatures; 4) = 0.35, u = 1.0m/s, k = 1.0
W/m.K,L50mm 61
Figure 3.15 Effect of bed porosity on methane mass fraction along the
packed bed for 4) = 0.35, u= 1.0 m/s, k1.0 W/m.K, and T1
750 K; homogeneous-heterogeneous model 63
Figure 3.16 Temperature distribution for the gas (solid line) and the solid
(broken line) for various bed porosities with 4) = 0.35, u = 1.0
m/s, k3 = 1.0 W/m.K and Tin = 750 K; homogeneous-
heterogeneous model 63
temperature for different bed lengths; c= 0.50, 4) 0.35, u 1.0
m/s, k3= 1.0 W/ m.K; Pt catalyst 65
Figure 3.18 Calculated methane conversion as afunction of bed length for
different inlet temperatures; u= 1.0 mIs, 4) = 0.35, c= 0.2, k
1.0 W/m.K; Pt catalyst 65
xli
Figure 3.19 Calculated methane conversion as a fqnction of inlet
temperature fOr different porosities; L = 75 mm, 4) = 0.35, u=
1.0 m/s, k = 1.0 W/ m.K; pt catalyst 66
temperature different bed porosities; L = 100 mm, 4) = 0.35, u=
1.0 m/s, ks= 1.0 W/ m.K; Pt batalyst 66
Figure 3.21 Methane mass fraction along the packed bed at various inlet
temperatures for a= 0.2 (thick line) and a=0.9 (thin line;
0.35, u=1.0 m/s; heterogeneous reaction, Pt catalyst 68
Figure 3.22 Calculated metliane conversion as afunction of bed porosity for
different bed lengths; u = 1.0 m/s, 4) 0.35, Ti,, = 1100 K, k =
1.0 WIm.k; Pt catalyst 68
Figure 3.23 Bed Solid temperature at the outlet as afunction of porosity for
various inlet temperatures; u 1.0 m/s, 4) = 0.35, L = 75 mm, k
= 1.0 W/m.K; Pt catalyst 69
Figure 3.24 Temperature distribution along the bed for different bed lengths;
(a) L = 25 mm, (b) L = 50 mm, (c) L = 100 mm, 4) = 0.35, u=
1.0 m/s, a = 0.4, 750 K; homogeneous-heterogeneous
model, Pt catalyst 71
Figure3 .25 Temperature distribution for the gas (solid line) and the solid
(broken line) along the packed bed for various inlet temperature;
4) = 0.35, u= 1.0 mIs, k = 1.0 W/m.K, a 0.45, L = 100 mm;
homogeneous-heterogeneous model, Pt catalyst 73
(broken line) for various bed porosities with 4) = 0.35, u = 1.0
m/s, ks = 1.0 W/m.K, Tin = 800K, L = loomm; homogeneous-
heterogeneous model, Pt catalyst 73
(broken line) for various bed porosities with 4) 0.35, u = 1.0
xl"
m/s, k = 1.0 W/m.K, Ti
ff = 800 K, L = 50 mm; homogeneous-
heterogeneous model, Pt catalyst 74
Figure 3.28 Calculated methane conversion, as a function of inlet
- , temperature for various solid thermal conductivities; 4) = 0.35, u
1.0 m/s, L = 50 mm, s= 0.4; Pt catalyst 76 -
Figure 3.29 Methane mass fraction along the bed , at various inlet
temperatures for different solid thermal conductivities, 4) = 0.35,
u= 1.0 m/s; heterogeneous reaction, Pt catalyst 76
Figure 3.30 Methane mass fraction along the packed bed for different values
of thermal conductivities of the solid bed; 4) = 0.35, u= 1.0 m/s,
s= 0.4, Tffi = 750 K; homogeneous-heterogeneous reactions, Pt
catalyst 78
(broken line) phases along the bed ,for different solid thermal
conductivities; 4) =0.35, u = 1.0 m/s, c = 0.4, Ti

ff = 750 K;
homogeneous-heterogeneous reactions, Pt catalyst 78
Figure 4.1 Schematic diagram of the experimental apparatus 81
Figure 4.2 A photographicview of the experimental apparatus ' 82
Figure 4.3 Cross-section view of the reactor 84
Figure 4.4 A photographic view of the' experimental packed bed 85
Figure 4.5 A photographic view of the choked nozzle nieters assembly 87
Figure 4.6 Exhaust gas sampling system with gas chromatograph 91
Figure 5.1 Comparison between experimental and numerical methane
conversion within the inert bed for 4) = 0.35, u= 1.0 m/s 100
Figure 5.2 Exhaust concentrations of CH4,CO2 and CO as a function of
inlet temperature within the inert bed for 4) = 0.35, u = 1.0
m/s 100
xiv
Figure 5.3 Effect of deactivation of fresh platinum catalyst on methane
conversion, = 0.35, u= 1.0 m/s 102
Figure 5.4 Exhaust concentrations of CH4 and CO 2 as afunction of inlet
temperature; fresh platinum catalyst, 0.35, u= 1.0 m/s 102
Figure 5.5 Exhaust gas temperature and methane conversion as afunction
of inlet temperature; fresh platinum catalyst, 4) = 0.35, u = 1.0
M/ -s 105
Figure 5.6 Comparison of methane conversion over fresh and aged
platinum catalyst, 4) = 0.35, u= 1.0 m/s 105
Figure 5.7 Exhaust gas temperature and methane conversion as afunction
of inlet temperature; fresh (5.0 h) platinum catalyst, 4) = 0.35, u
1.0 m/s 106
Figure 5.8 Methane conversion as a function of inlet temperature for
different equivalence ratios, u= 1.0 m/s; aged Pt catalyst 108
Figure 5.9 Methane conversion versus equivalence ratio at different inlet
temperatures, u= 1.0 m/s; aged Pt catalyst 108
Figure 5.10 Methane conversion as a function of inlet temperature at
different approach velocities with 4) = 0.35; aged Pt catalyst 110
Figure 5.11 Effect of approach velocity on methane conversion at different
inlet temperature with 4) = 0.35; aged Pt catalyst 110
Figure 5.12 Methane conversion as a function of inlet temperature within
the Co 3O4ICr2O3 catalytic bed, 4) = 0.35 and u= 1.0 m/s 112
Figure 5.13 Exhaust concentrations of CH4,CO and CO 2 as afunction of
inlet temperature; C0304/Cr2O3 catalyst, u = 1.0 m/s and 4) =
0.35 112
Figure 5.14 Methane conversion as a function of inlet temperature for
different equivalence ratios; C0304/Cr2O3 catalyst, u= 1.0 m/s 113
xv
Figure 5.15 Exhaust concentration of CO as afunction of inlet temperature
for different equivalence ratios; Q0304/Cr2O3 catalyst, u = 1.0
m/s 113
Figure 5.16 Comparison between Pt and C0304/Cr2O3 catalysts for Methane
conversion at different inlet temperatures, u= 1.0 m/s, 4) = 0.35 115
Figure 5.17 Exhaust concentration of CH4 and CO 2 as a function of inlet
temperature; Pt and C0304/Cr2O3 catalysts, u= 1.0 m/s, 4) = 0.35 115
Figure 6.1 Experimental data and predicted methane conversion as a
function of inlet temperature for various pre-exponential factors
and activation energies; platinum catalyst, u= 1.0 mIs, 4) = 0.35 120
Figure 6.2 Experimental and calculated methane conversion as afunction
of inlet temperature, platinum catalyst, u= 1.0 m/s, 4) = 0.35, E
= 46.0 k.T/mol for T1≥ 750 K, E= 42.0 kJ/mol for Tm< 750 K,
A3=1.03x10 3 kmol/m2.K 121

of inlet temperature for two equivalence ratios, platinum

'
catalyst, u= 1.0 m/s 121

of inlet temperature for two approach velocities, platinum

.
catalyst, 4) = 0.35 122
of inlet temperature, C0304/Cr2O3 catalyst, u = 1.0 m/s, 4) =
0.35, E = 42.8 kJ/mol for 775 K, E = 46.3 kJ/mol for Tin
> 775 K, A = 2.2 x i0 kmol/ m2.K 123

Figure 6.6 Experimental and numerical methane conversion as afunction
of the inlet temperature for two equivalence ratios, C0304/Cr2O3
catalyst, u= 1.0 m/s 124
xvi
of inlet temperature for two approach velocities, C0304/Cr2O3
catalyst, 4) = 0.35 124
temperature for various bed porosities within the inert bed, 4) =
0.35,u= 1.0 m/s, k = 1.0W! m.K, L = 50 mm 126
temperature for different bed lengths; s 0.4, 4) = 0.35, u= 1.0
mls,k5= 1.OW/m.K 126
temperature for various solid thermal conductivities; 4) = 0.35, u
1.0mls,L=50 mm, c=0.4 127
temperature for various bed porosities; 4) = 0.35, u= 1.0 m/s, k
= 1.0 Wlm.K, L = 50 mm; Pt catalyst 128
temperature for different bed lengths; s= 0.5, 4) = 0.35, u= 1.0
m/s, k = ,I .0 W/ m.K; Pt catalyst 129
temperature for various solid thermal conductivities; 4) = 0.35, u
= 1.0mls,L=50 mm, c=0.4;Ptcatalyst 129
Figure 7.1 Calculated fuel conversion as a function of inlet temperature
within an inert (* symbol) and catalytic packed beds, 4) = 0.35, u
1.0 m/s 135
Figure 7.2 Calculated ethane conversion as afunction of inlet temperature
within an inert bed for different equivalence ratios, u = 1.0 m/s,
k1.0W/m.K,L=50mm 135
xvii
for different equivalence ratios, u= 1.0 m/s, k = 1.0 W/m.K, L
= 50 mm; Pt catalyst 137
Figure 7.4 Calculated emperature distribution for the gas (solid line) and
the solid (broken line) along the bed for various equivalence
ratios of ethane, u= 1.0 m/s; Pt catalyst 137
within the catalytic (thin lines) and inert (*, thick lines) beds for
different approach velocities, 4=0.35 138
Figure 7.6 Calculated propane conversion as a function of inlet
temperature within the inert bed at different equivalence ratios,
u=1.0mIs,k1.0WIm.K,L=50min 140
temperature at different equivalence ratios, u= 1.0 m/s, k = 1.0
WIm.K, L = 50 mm; Pt catalyst 140
Figure 7.8 Calculated temperature distribution for the gas (solid line) and
the solid (broken line) along the bed for various equivalence
ratios of propane, u= 1.0 m/s; Pt catalyst 142
temperature within the catalytic (thin lines) and inert (*, thick
lines) beds for different approach velocities, = 0.35 142
Figure 7.10 Calculated fuel conversion as a function of inlet temperature
within catalytic (thick lines) and inert (*, thin lines) beds, 4 =
0.35, u= 1.0 mIs 143
Figure 7.11 Calculated carbon monoxide oxidation as a function of inlet
temperature within the inert bed for various equivalence ratios,
u1.0m/s 145
Figure 7.12 Calculated carbon monoxide oxidation as a function of inlet
temperature for various equivalence ratios, u = 1.0 m/s; Pt
catalyst 145
xviii
(broken line) along the catalytic bed for various equivalence
ratios of carbon monoxide; u= 1.0 m/s; Pt catalyst 146
Figure 7.14 Effect of approach velocity on calculated, carbon monoxide
conversion as a function of inlet temperature within the inert
bed, 4)= 0.35 147
Figure 7.15 Effect of approach velocity on calculated carbon monoxide
conversion as a function of inlet temperature, 4) = 0.35; Pt
catalyst 147
Figure 7.16 Calculated hydrogen conversion as a function of inlet
temperature at different equivalence ratios within the inert bed,
u=1.0m/s.... 149
temperature at different equivalence ratios, u = 1.0 m/s; Pt
catalyst 149
Figure 7.18 Comparison between calculated hydrogen conversion within the
catalytic and inert beds (*; thick lines) versus inlet temperatures
for various ëquivalénce ratios, u= 1.0 m/s 151
Figure 7.19 Calculated temp'eràture distribution for the gas (solid line) and
the solid (broken line) ,along the bed for various equivalence
ratios of hydrogen; u= 1.0 m/s; Pt catalyst 151
Figure 7.20 Calculated temperature distribution for the gas (solid line) and
the solid (broken line) for CH4,C2H, C3H, CO, and H2 along
the bed, 4) = 0.35, u= 1.0 m/s; Pt catalyst 152
temperature within the inert bed for different approach
velocities, 4) = 0.10 . 152
xix
temperature within the inert bed for different approach
velocities, = 0.35 . 153
temperature for different approach velocities, = 0.35; Pt
catalyst 154
Figure 7.24 Comparison between calculated hydrogen conversion within the
catalytic and inert beds (*; thick lines) versus inlet temperature
for various approach velocities, = 0.35 154
Figure 8.1 Calculated and experimental propane conversion as a function
of inlet temperature within platinum bed, 4i = 0.35, u= 1.0 m/s 156
Figure 8.2 Calculated and experimental propane conversion as afunction
of inlet temperature within C0304/Cr2O3 bed, 4i = 0.35, u= 1.0
rn/s 156
Figure 8.3 Calculated and experimental carbon monoxide conversion as a
function of inlet temperature within platinum bed, = 0.35, u=
1.0 mIs 158
Figure 8.4 Calculated and experimental carbon monoxide conversion as a
function of inlet temperature within C0304/Cr2O3 bed, 4= 0.35,
u=1.0m/s 158
Figure 8.5 Calculated and experimental hydrogen conversion as afunction
of inlet temperature within platinum bed, = 0.35, u= 1.0 mIs 160
Figure 8.6 Calculated and experimental hydrogen conversion as afunction
of inlet temperature within C0304/Cr2O3 bed, = 0.35, u= 1.0
rn/s 160
Figure 8.7 Comparison of calculated propane conversion as afunction of
inlet temperature within platinum bed, 4 = 0.35, u= 1.0 m/s 164
xx
Figure 8.8 Comparison of calculated carbon monoxide conversion as a
function of inlet temperature within platinum bed, 4) = 0.35, u=
1.0rnls 164
Figure 8.9 Comparison of calculated hydrogen conversion as afunction of
inlet temperature within platinum bed, 4) = 0.35, u= 1.0 m/s 165
Figure B. 1 Calibration curves for 0.09mm diameter nozzle 192
Figure B.2 Calibration curves for 0.20 mm diameter nozzle 193
Figure C. 1 Temperature distribution 'across the reactor,Tin 41 °C ' 195
Figure D. 1 Pressure drop across the packed bed reactor as afunction of the
flow rate at Tin=20 °C and P = 88.1 kPa 196
Figure D.2 Pressure drop across the packed bed reactor as afunction of the
approach velocity at Tin,

= 20 °C and P = 88.1 kPa 197
xxi
LIST OF SYMBOLS
Symbols Descripton
A pre-exponential factor (kmollm3.$)
a catalyst activity
catalyst spepific surface area (m2/m)
C concentration
Cp g specific heat of the mixture at constant pressure (J/kg.K)
specific heat of pellets (J/kg.K)
D Diffusion coefficient (m2/s)
d pellet diameter (mm)
E activation energy (kJ/mol)
Hk specific enthalpy of species k(J/kg)
h heat transfer coefficient (W/m2.K)
hv volumetric heat transfer coefficient (W/m3 .K)
k thermal conductivity (W/m.K)
effective thermal conductivity (W/m.K)
L length of the bed(mm)
MW molecular weight (kg/kmol)
MW molecular weight of the mixture (kglkmol)
Nu Nusselt number
P pressure (kPa)
Pr Prandtl number
Re
Reynolds number
Ru universal gas constant (kJ/kmol.K) -
SP surface area of apellet (mm2)
T temperature (K)
t time (s)
Q volume flow rate (rn3/h)
u approach velocity (m/s)
V volume (m)
V 3
volume of apellet (mm)
-
V3 space velocity (m3/(m3.h))
X axial coordinate (m)
Y mass fraction
Greek symbols
/3 extinction coefficient (1/m)

e porosity
equivalence ratio
viscosity (kg/m.$)
V
kinematic viscosity (m2/s)
molar consumption rate per unit volume for gas phase reactions
(kmol/m 3 s)
molar cons
umption rate per unit area of the catalyst for surface
reactions (kmol/m2.$)
mixture density (kg/m3)
Stefan-Boltzman constant (W/m2.K4)
Subscripts
CH 4 methane
cony conversion
eff effective
f fuel
g gas
in inlet, initial
k species
o oxidant
0 2 oxygen
out outlet
p pellet
s solid, surface
Superscripts
h gas-phase
m, n constants(Eq.' 2.11)
I
s catalytic surface
xxiv
1
CHAPTER 1
INTRODUCTION
The present experimental and numerical work is intended to address the catalytic
combustion in apacked bed reactor. The developed mathematical model is based on one
dimensional flow, heat and mass transfer with global reaction, which is adequate enough
to produce dependable results for design purposes. Moreover, alab scale experimental set
up is constructed with necessary measuring instrumentations. The experiments were
conducted for two reasons; to validate the developed model and to assist in establishing
the kinetic data for global surface reaction over platinum and C0304/Cr2O3 catalysts for
the gaseous fuels employed within the packed bed reactor. Also, the model is used to
investigate the effects of controlling parameters, such as inlet temperature, inlet velocity,
bed porosity and bed thermal conductivity on the characteristics of the homogenous and
heterogamous combustion. The model provided areasonable study of the characteristics
of the catalytic reactor.
The following paragraphs provide abackground to the physics and mechanisms of the
catalytic process, which is essential in developing the mathematical model. It also
introduces terminologies used in the catalytic literature. Finally, the objectives of the
present work and outlines of the thesis are introduced.
1.1 Background
Most industrial syntheses and nearly all biological reactions require catalysts.
Furthermore, catalysis is the most important technology in environmental protection, i. e.,

2
the reduction of emissions. A well-known example is the catalytic converter for
automobiles. The term "catalysis" was introduced as early as 1836 by Berzelius and a
definition that is still valid today that of Ostwald (1985): "a catalyst accelerates a
chemical reaction without affecting the position of the equilibrium". While it was
formerly assumed that the catalyst remained unchanged in the course of the reaction, it is
now known that the catalyst is involved in chemical bonding with the reactants during the
catalytic process. Thus, catalysis is acyclic process: the reactants are bound to one form
of the catalyst, and the products are released from another, regenerating the initial state.
In theory, an ideal catalyst would not need replenishing, but this is not the case in
practice. Owing to competing reactions, the catalyst undergoes chemical and physical
changes, and its activity decreases (catalyst deactivation). Thus catalysts must be
regenerated or eventually replaced.
Apart from accelerating reactions, catalysts have another important property: they
can influence the selectivity of chemical reactions. This means that completely different
products can be obtained from a given starting material by using different catalyst
materials. Industrially, this targeted reaction control is even more important than the
catalytic activity (Hagen, 1999).
Catalysts can be in gaseous, liquid, or solid state. Most industrial catalysts are
liquids or solids. Nuhierous organic intermediate products required for the production of
plastics, synthetic fibers, pharmaceuticals, dyes, crop-protection agents, resins, and
pigments, can only be produced by catalytic processes. Most of the processes involved in
crude oil processing and petrochemistry, such as purification, refining, and chemical
transformations, require catalysts. Environmental protection measures such as automobile
exhaust control and purification of off-gases from power stations and industrial plants
would be much less effective without catalysts.
Catalysts can be classified, according to various criteria such as structure,
composition, area of application or state of aggregation. Figure 1.1 represents the
classification of catalysts according to the state of aggregation in which they act.

3
Catalysts
Homogeneous Heterogeneous Heterogeneous

catalysts homogeneous catalysts
catalysts
[i ncl
.biocatalysts
Acid/base (enzymes)] Bulk
catalysts catalysts
Transition Supported
metal catalysts
compounds
Fig. 1.1 Classification of catalysts (Hagen, 1999).
Heterogeneous catalysis takes place between different phases. Generally the
catalyst is a solid, and the reactants are gases or liquids. In supported catalysts, the
catalytically active substance is applied to asupport material that has alarge surface area
and is usually porous (Hagen, 1999).
The suitability of a catalyst for an industrial process depends mainly on the
following three properties: (1) Activity, (2) Selectivity, and (3) Stability.
The activity of a catalyst is a measure of how fast one or more reactions
proceed in the presence of the catalyst. Activity can be defined in terms of
kinetics. Mostly, the activity of the catalyst is determined by measuring the
reaction rates in the temperature and concentration ranges that will be present
in the reactor. However in practice, the activity of the catalyst e.g., for catalyst
screening, determination of process parameters, optimization of catalyst
production conditions, and deactivation studies, is measured by one of the
following activity measures:

4
o Conversion under constant reaction conditions
o Space velocity for agiven, constant conversion 0
o Space-time yield
o Temperature required for agiven conversion.
• The selectivity of acatalyst of areaction is the ability of the catalyst to give
the desired product, out of all possible products, e.g. the percentage of the
starting material (reactant) that is converted to the desired product. The
selectivity is of great importance in industrial catalysis, as demonstrated by
the example of synthesis gas chemistry, in which, depending on the catalyst
used, completely different reaction products may be obtained (Fig. 1.2).
• The stability (deactivation behavior) of a catalyst refers to its chemical,
thermal, and mechanical stability. This determines its operational lifetime in
industrial reactors. Catalyst stability is influenced by numerous factors,
including its decomposition, coking, and poisoning. Catalyst deactivation can
be estimated by measuring the activity or selectivity as a function of time.
Catalysts that lose activity during processes can often be regenerated before
they ultimately have to be replaced. The total catalyst lifetime is of crucial
importance for the economics of aprocess. The mechanisms involved in the
deactivation and regeneration of catalytic surfaces will be reviewed next in
order to better understand the concept involved in such processes.
Generally, it is difficult to choose which of the above functions (properties) is the
most important because the demands made on the catalyst are different for each process
or application.
5
Ni CH+HO
o Methanization
Cu/Cr/Zn oxide 11 CH, OH Methanol synthesis

CO/H2
Fe, Co CnH n+m + H20 Fischer-Tropsch
Synthesis
Rh cluster CH2-CH2
Glycol
'oH OH
Fig. 1.2 Reactions of synthesis gas (Hagen, 1999).
• Catalyst Deactivation
Catalysts have only alimited lifetime. Some lose their activity after afew minutes, others
last for more than ten years. The maintenance of catalyst activity for as long as possible is
of major economic importance in industry. Catalyst deactivation, also known as aging, is
expressed by the decrease with time in the catalyst activity defined as the ratio of the
reaction rate at agiven time to the reaction rate at the time (t = 0) and is presented as
follows:
)(t = 0)
where, ais the catalyst activity, t is the time and w is the reaction rate of -
the catalyst
under the same condition. Not only does the decreasing catalyst activity lead to aloss of
productivity, it is. also often accompanied by a lowering of the catalyst selectivity.
Therefore, in industrial processes great efforts are made to avoid catalyst deactivation or
to regenerate deactivated catalyst.

6
A decline in activity during the process can be the result of various physical and chemical
factors. The four most common causes of catalyst deactivation are:
1. Poisoning of the catalyst. Typical poisons are H2S, Pb, Hg, S. and P.
2. Blocking of the active sites by deposits on the catalyst surface and change of the
pore structure (e.g., coking).
3. Sintering due to over heating of the catalyst leading to aloss of active surface
area.
4. Loss of the catalyst (e.g. through, formation of volatile metal carbonyls with CO).
These processes are described below and are shown schematically in Fig. 1.3 (Hagen,
1999).
o Catalyst Poisoning
Catalyst poisoning is a chemical effect. Catalyst poisons form strong adsorptive
bonds with the catalyst surface, blocking active centers, Therefore, even very small
quantities of the catalyst poisons can influence the adsorption of reactants on the
catalyst. The term catalyst poison is usually applied to foreign materials in the
reaction system.
o Deposits on the catalyst surface
The blocking of catalyst pores by polymeric components, especially coke, is another
widely encountered cause of catalyst deactivation. In many reactions of
hydrocarbons, side reactions lead to formation of polymers. If these are deposited
near the pore opening, catalyst activity and selectivity can be influenced due to
impaired mass transport into and out of the pores. At high temperatures (above
200 °C) these polymers are dehydrogenated to carbons, aprocess known as coking.
Catalysts with acidic or hydrogenating/dehydrogenating properties (e.g. metal,
oxides, and sulfides catalysts in catalytic reforming) are especially susceptible to
coking. The extent of coke formation depends directly on the acidity of the catalyst.
.7
o Thermal processes and sintering
Sintering is defined as the loss of active surface area by the agglomeration of small
crystallites into larger ones in the case of supported metal catalysts, or the collapse of
pore structure and loss of internal surface area in the case of the supports or various
unsupported (normally oxide) catalysts. Sintering is athermally activated process and
is physical rather than chemical in nature. The transformation of 7-.A1203 into a-
A1203 with its lower surface area is one example of sintering of the support due to
phase transformation. The rate of sintering increases with increasing tempeiature,

decreasing crystallite size, and increasing contact between the crystallite particles.
Phase changes due to overheating can limit the catalyst activity or lead to catalyst-
substrate interactions. However, achange in selectivity can also occur, especially in
the case of structure-sensitive .reactions.
o Catalyst losses via the gas phase.
High reaction temperatures in catalytic processes cafi lead to the loss of active
components by evaporation via processes such as volatilization. This does not only,
occur with compounds that are known to. be volatile (e.g., P205 in H3PO 4,silica
gel/activated carbon), it also occurs when metals react to give volatile oxides,
chlorides, or carbonyls (Hagen, 1999).

8
Fig. 1.3 Mechanisms of catalyst deactivation (M = metal) (Hagen, 1999).
In general, acatalyst must be chemically stable under actual operating conditions
(over a wide range of temperatures, air/fuel ratios, flow rates etc.) and resistant to
poisoning. Catalysts must also pose no potential danger to the environment (such as the
emission of finely dispersed particles of metals or their toxic derivatives) (Prasad et al.,
1984).
Environmental pollution and air quality are certainly a worldwide concern.
Combustion devices and processes contribute very, significantly to pollution through
exhaust emissions (CO, NO,,, unburned hydrocarbons and particulates, SO2, etc)
promoting the formation of smog, and acid rain and contributing to the greenhouse effect,
9
which has been liable for a general rise in global temperature and increased weather
variations (Prather, and Logan, 1994). These pollutants can cause asignificant hazard to
human and animal health as well as agricultural and economical impact. Seinfeld (1986)
indicated four principal effects of air pollution in the troposphere: (1) altered properties
of the atmosphere 'and precipitation; (2) harm to vegetation; (3) soiling and deterioration
of materials; and (4) potential increase in morbidity and mortality -in humans. The public
has an increased awareness of the necessity for controlling emissions for preserving our
planet. Governments around the world, especially those of advanced industrial nations,
are responding with increased regulations for emission control from mobile and
stationary sources. Ambient air quality standards were legislated and were put in force in
the early 1970s in Canada, U.S.A., Europe and Japan. Amendments to these later on have
generally imposed more strict standards and have brought more and more sources of air
borne pollutants under scrutiny (Koshland, 1996). In fact, the 90s has being called the
"decade of the environment". A concept known as "polluter pays principle", (PPP), has
been established in Canada, U.S.A., Japan, Europe and other countries (Nakajima, 1991;
Heck and Farrauto, 1994).
There are two approaches to consider in reducing undesirable emissions. They
are: to treat the pollutant being emitted or, better still, not to produce the pollutant at all!
Often the former is more realistic because there is no easy and economically acceptable
approach which avoids producing the pollutant with present day technology.
Catalysts in emission control processes have to be adaptable to the conditions of
the effluent gas to be treated. It is difficult to employ pre-treatment devices for the
removal of catalyst poison and dust, because they make the processes complicated and
costly.
One approach used to enhance the reactivity of fuels and to decrease emissions is the use
of catalytic combustion. Catalytic combustion enables the oxidizing of fuels very
efficiently under lean conditions (i.e. below the lean flammablity limit for fuel-air
mixtures) minimizing the emissions of unburned hydrocarbons (LJHC) and CO. This
takes place at relatively low temperatures and results in decreased formation of NO,,.
10
Therefore, catalytic combustion offers aclear opportunity to provide solutions to many

environmental issues.
The drive to lower pollutant emissions from combustion processes has led not
only to increased research in catalytic combustion but also to increased research in
alternative sources of energy and fuels such as natural gas, hydrogen, CO, gasified
biomass, etc.. Natural gas, which mainly consists of methane, has received increased
attention as an alternative fuel for internal combustion engines, commercial vehicles, gas
turbines, industrial furnaces and boilers because of its environmental advantages.
However, methane tends not to react relatively easily with air, especially, at low
.
temperatures. The presence of catalysts can permits the oxidation of methane at lower
temperatures and with faster rates than in their absence. ,Because a great amount of
natural gas, is utilized in many practical energy conversion systems, a better
understanding of, its catalytic oxidation will benefit combustion systems employing
natural gas by achieving more effective fuel utilization, reducing pollutant emissions,
improving the production of synthesis gas and reducing safety hazards.
Cars and stationary combustion facilities such as power plants and industrial
boilers are identified as amajor source of emissions of HC, CO, SO 2 particulates and
NO, to the atmosphere. Nitrogen oxides are formed in practical combustion systems by
high temperature oxidation of atmospheric nitrogen and nitrogen bound in the fuel.
Catalytic oxidation at low temperatures is awell et.blished technique to limit NO
production (Cybulski, and Moulijn, 1998). The cost of the catalyst, which in most cases
contains noble metals, and its susceptibility to aging or damage caused by thermal stress,
sintering and poisoning, have so far slowed down the widespread use of catalytic
combustion. Despite this, increasingly severe regulations on combustion emissions have
motivated research oriented toward the development of cheaper, regenerative and durable
catalytic materials. Thus, many new catalysts have been discovered and we may expect
more to be 'discovered. The development of catalysts which can withstand high
combustion temperature and which are inexpensive is an important area of research

(Zwinkels et al., 1993; Bozo et al., 1999).
11
In many of the applications mentioned earlier, the questions that often remain to be
answered are:
1. How much catalyst is needed in order to achieve the required stability of catalyst,
desired emissions, and desired heat transfer characteristics?
2. Is the catalyst only needed to ignite the mixture and does it then remain unused?
3. If it remains active in the higher temperature range, what is its role and in which
part of the reactor it is needed?
The following chapters attempt to answer some of these questions;

12
1.2 Objectives of the Study
The present research is related to catalytic oxidation of gaseous fuel-air mixtures in a
packed bed reactor. This study was initiated and designed to determine the kinetic data
(activation energy and the pre-exponential factor) for catalytic oxidation of common
gaseous fuels over non-noble metals (binary mixtures of cobalt and chromium oxides) as
well as platinum catalysts. Therefore, amathematical model and experimental program
were developed to investigate the performance of these catalysts in the oxidation of lean
premixed common gaseous fuel-air mixtures in apacked bed reactor.
The specific tasks of the present research are as follows:
1. To develop atheoretical model for the catalytic oxidation of fuel-air mixtures in
apacked bed reactor.
2. To investigate experimentally the effectiveness of platinum as well as anon-
noble binary mixture ,of cobalt and chromium oxides as catalysts in the
oxidation of lean homogeneous mixtures of gaseous fuel and air at atmospheric
pressure and different operational conditions in apacked bed reactor.
3. To validate the theoretical model against the experimental data obtained in this
investigation as well as against other published data.
4. To obtain the kinetic data for abinary mixture of cobalt and chromium oxides
• catalyst as well splatinum in apacked bed reactor.
5. To investigate the effect of bed porosity s, length of the. bed L, and solid thermal
conductivity kon the conversion of methane in apacked bed reactor.

13
1.3 Thesis Organization
The outline of the remaining chapters of the dissertation is as follows:
- Chapter 2: Covers the literature review.
- Chapter 3: Covers the physical and mathematical descriptions of the problem
under consideration and the detailed steps used to develop the mathematical
model. It also presents preliminary results and discussions of the model's
prediction of the oxidation of methane in air and compares the model's prediôtion
with any available corresponding experimental data. -
- Chapter 4: Desctibes the experimental apparatus and procedure used throughout
the course of this study.
- Chapter 5: Presents the experimental results for methane in air within the inert
and catalytic (platinum or binary mixture of cobalt and chromium oxides) packed
bed reactors.
- Chapter 6: Presents the kinetic data obtained for methane oxidation in air within
the inert and catalytic (platinum or binary mixture of cobalt and chromiuth
oxides) packed bed reactor.
- Chapter 7: Considers the catalytic oxidation of other commOn gaseous fuels (i.e.
ethane, propane, carbon monoxide, and hydrogen) in air.
- Chapter 8: Covers comparison of model prediction with the experimental data of
common gaseous fuels (i.e., propane, carbon monoxide, and hydrogen) in air in
order to determine the surface kinetic data for these fuels within the platinum or
the binary mixture of cobalt and chromium oxides catalysts.
- Chapter 9: Summarizes the relevant conclusions drawn from the study and
suggests some recommendations for possible future work.

14
CHAPTER 2
LITERATURE REVIEW
2.1 Introduction
Catalytic combustion has been vigorously explored as an effective route to energy
conversion in view of its capability to oxidize different fuels with high efficiency at
relatively low temperatures and under lean conditions, thus simultaneously preventing the
formation of NOx and minimizing the emissions of unburned hydrocarbons (UHC) and
CO. Extensive research on catalytic combustion has been conducted experimentally and
theoretically. A review of some relevant research is presented below.
2.2 Experimental Work
Experiments have been carried out on catalytic combustion for over 160 years.
Interestingly, the first use of catalysis was to promote combustion. Davy discovered in
1840 that platinum wires could induce combustion of flammable mixtures. The resulting
reactions appeared to take place on the surface of the wire, "without flame" and with the
high radiative fluxes associated with the solid surface emittance rather than the low
emittance characteristic of gaseous combustion products (Kesselring 1986). Davy's
observations led to the development of numerous radiative heater devices and, thus, the
first practical use of catalysis (Kendall et al., 1992). This discovery stimulated numerous
experiments throughout the late 19th century which demonstrated that various materials
could catalyze heterogeneous combustion.

15
2.2.1 Fundamental Studies
Some of the studies and investigations which might be termed "fundamental studies of
heterogeneous catalysis in combustion" have attempted to: identify specific.
heterogeneous reactions, quantify reaction kinetics for these reactions, define the
mechanisms by which the solid surface promotes or accelerates oxidation reactions and
identify catalyst properties leading to high activity.
Hiam et al, (1968) obtained aformula for the oxidation of propane-air mixtures
over platinum catalyst. Trimm and Lam (1980) studied the oxidation of methane over
platinum supported on porous and non-porous alumina fibres. They observed permanent
catalyst deactivation due to sintering of platinum or alumina; the latter effect was
accelerated in the presence of steam. Fresh and aged catalysts were characterized in their
investigation. Trimm and Lam also proposed global rate expressions for the oxidation of
methane for two temperature regimes, below and abpve 813 K. They suggested that the
formation of intermediates may affect the reaction selectivity from one in which oxygen
adsorption is predominant to one in which methane adsorption is most important. Otto
(1989) investigated methane oxidation over platinum/7-alumina. Oxidation was found to
be structure sensitive; this was reflected in the change in the apparent activation energy.
They reported that methane oxidation kinetics were consistent with the existence of at
least two different platinum entities, termed dispersed and particulate platinum oxide,
which were characterized by differences in particle size and oxidation state. Otto
concluded that the reaction kinetics of methane oxidation depend strongly on the
pretreatment of the platinum samples since oxidation tends to disperse platinum while
reduction can cause sintering. Song et al. (1991) studied the ignition and extinction of
lean methane or propane in air on platinum foil in stagnation-point flow. They developed
an irreversible one-step reaction rate expression able to show that the heterogeneous
reaction dominates the system behavior at the lower temperature while both
homogeneous and heterogeneous reactions play important roles in the higher temperature
range. It was also predicted that the homogeneous ignition temperature was higher with
the surface reaction than without the surface reaction. This is because the homogeneous-
16
heterogeneous reactions expand the stabilized operating regions with high reaction rates
compared with either the heterogeneous or the homogeneous reaction alone.
Voltz et al. (1973) determined the rate constants and activation energies of carbon
monoxide and propylene oxidation on apelleted platinum-alumina catalyst with synthetic
gas mixtures (i.e. ablend, of pure CO, C3H8,02, NO, CO 2,and N2)between 477 and 644
K to simulate a real ,engine's exhaust conditions. The relative importance of catalyst
density and heat capacity, catalyst activity, initial bed temperature, inlet exhaust gas
composition and temperature, and converter location were studied and it was found that
they could change depending on the converter systems and test procedure (Kuo et al.,
1980). It was found also that the exhaust gas flow rate, heat loss from the converter,
oxygen concentration in excess of 2.0%, and gas channeling in the catalyst bed were of
minor importance. Kuo et al. estimated the kinetic parameters of the global reaction of
CO and HC from their experimental and theoretical investigations of the operational
catalytic converter and later used them in modeling the oxidation of CO.
Pfefferle et al. (1989a) investigated the effect of catalytic activity on gas ph ase
ignition in an ethane-air boundary layer by measuring OH concentration profiles over

heated platinum and quartz surfaces. They found that platinum catalytic influence on gas
phase ignition depends strongly on the fuel-air ratio. Depletion of fuel near the catalytic
surface by mass transfer-limited oxidation reactions can account for the catalyst
inhibiting effect. Also, their results indicated that catalytic surface-induced production of
active intermediates can promote gas phase ignition and offset the effect of reactant
depletion near the surface. Pfefferle et al. (1989b) showed that aplatinum catalyst acts to
promote the formation of oxygen atoms in the region adjacent to the surface. They
concluded that such effect was most apparent at lean equivalence ratios (4 <0.30 for
ethane). It was also reported that at higher equivalence ratios the ignition of ethane in air
at atmospheric pressure was inhibited by the platinum surface because of fuel depletion at
the surface due to the mass transfer-limited catalytic oxidation reaction. However, at low
pressures ranging from 5.3 to 18.7 kPa, ethane ignition was promoted by catalytic
reaction at all equivalence ratios studied (Griffin et al., 1992). Furthermore, it was shown
that N2O substitution for 02 strongly inhibited the gaseous ignition of ethane, hydrogen,
17
and acetylene over platinum surfaces, and suppressed the preignition level of OH radical
concentrations to avalue below their detection limits. Pitchai and Klier (1986) reported
that formaldehyde is an important combustion intermediate in both gas-phase and
catalytic-surface combustion. They suggested that the apparent formation of OH radicals

could result from formaldehyde production on the surface and its subsequent oxidation in
the boundary layer.
2.2.2 Applications
•Some studies reported in the literature as applied research could be called "reduction to
practice", these include attempts to construct and employ practical devices exploiting
heterogeneous combustion. In fact, there are many devices under development employing
catalytic combustion, such as domestic water heaters (Seonhi, and Scholten, 1997;
Ragaini et al., 1999), cookers (Scholten et al., 1999), and space and process heaters (Cho
et al., 1999; Kang et al., 1999); some of them are already on the market. Moreover, gas
turbines with catalytic combustors are currently in the final stages of testing for durability
such as in the U.S. Kang, 1999; Beebe et al., 1999; Smith et al., 1999) and Japan
(Tochihara and Ozawa, 1999).
Unlike radiant catalytic heaters, adiabatic catalytic oxidation systems have been
developed relatively recently, within the list 40 years. With the ability to burn very low
concentrations of combustibles at low temperatures in the presence of comparably low
concentrations of oxygen (outside of the homogeneous flammable limits), catalytic fume
abatement reactors, automotive catalytic converters, and nitric acid plant tail gas reactors
have found widespread use. In fact, such applications to date present one of the largest
single markets for catalysts. A major advantage of these devices is their ability to burn
fuels with negligible NO formation. Catalytic reactors have also been used to destroy
preexisting NO (three-way automotive catalytic reactors are one example).
Will and Bennett (1992) studied the effect of flow maldistributions on emission
control in automotive converter canisters for inlet velocities from 1to 15 m/s and catalyst
18
specific space velocities ranging from 11.1 to 22.2 (us) at ambient pressure. Their results
show anoticeable effect of the velocity on the emission conversion. P'attas, et al. (1994)
used aCFR engine to measure NO and matched it to the predicted results of their model
in order to obtain the kinetic data for NO reduction. The formation and destruction of
NO in acatalytic combustor of methane was studied by Agarwal et al. (1994) using a
series of Lai..Sr-
.Sr,, (La is Lanthanum; Sr is Strontium where both are catalyst
promoters) catalysts. The emission of NO was less than 3.0 ppm under lean combustion
conditions (3.8% CH4 in air) at temperatures as high as 1000°C. They attributed the low
NO emission during the lean catalytic combustion to the low temperature. Li and Li
(1995) studied three-way reactions to remove CO, BC, and NO,,. They showed that the
three-way performance depended not only on thç reaction of CO and HC with 02, but
also on the number and strength of NO adsorption sites. They concluded that the three-
way noble metal catalysts reactions for the removal of CO, UHC, and NO Were
controlled by internal diffusion at high space velocity of 44.4 (its). However, with non-
noble metal catalysts (La, Ce, Cu, Co, Mn, and Fe) there are 'internal diffusion controls at
space velocities less than 11.1 (its) and kinetic control at above there space velocity.
Moreover, Li and Li (1996) used rare earth (RE)-transition metal oxides for
simultaneously removing three major pollutants, CO, BC, and NO in automotive
emissions. They also showed that acatalyst of RE-transition metal with the following
composition RE(3%), Ni(2%), Co(3%), Mn(1%) has awider "Three-Way Window" than
acatalyst with acomposition of RE(3%)with Cu(4%) and Mn(2%) or Fe(2%). Schlegel
et al. (1996) investigated experimentally as well as numerically the NO emissions from

both catalytic and non-catalytic, lean premixed combustion of methane at atmospheric
pressure. This study reported that the higher the catalytic conversion of methane was, the
lower the NO emissions were. The NO level in catalytic combustor was significantly
lower than those of non-catalytic combustor. Corma et al. (1998) studied NO reduction
with propane using copper or cobalt on metal exchange zeolites. It was reported that this
catalyst has agood stability.

19
2.2.3 Non-Noble Metal Catalysts
Non-noble metal catalysts have gained agreat deal of interest in catalytic combustion
research as alternatives to very costly noble metal catalysts. Jones (1997) tested different
transition metal oxides (MoO 3,Cr2O3,Co3O4,Fe2O3,Y203,CeO 2,m-ZrO2,and MgO) in
the combustion of propane-air mixtures and showed that their light-off temperature
values were comparable with that of platinum catalyst. The temperature at which a
catalyst begins to operate is called the light-off temperature where the combustion
process changes from kinetically controlled regime (corresponding to 10% conversion
of the fuel) to mass transfer controlled regime (corresponding to —90% conversion of the
fuel) (Cybulski, and Moulijn, 1994). It was reported in the literature that metal oxides of
cobalt and chromium and their mixture'

shave showed high activity for the oxidation of
light hydrocarbons (Prasad et al., 1980; Depiak, 2003). The main advantage of metal
oxide catalysts over noble metal catalysts is the lower cost and high thermal stability over
arange of temperatures, which are typical for catalytic combustors (Sokolovskii, 1990;
Zwinkels et al., 1993). Also, interest in the catalytic combustion of alternative fuels such
as heavy distillates, low Btu gas and synthetic fuels directed investigations into the
oxidation of fuel-bound nitrogen (fuel-N) in acatalytic combustor (Prasad et al., 1981).
Under lean conditions, catalytic combustors using noble metal catalysts produce very
high levels of fuel-N conversion to NO (50 - 90%). It is evident from aliterature survey
that the formation of nitrogen oxides from fuel-bound nitrogen may be suppressed by
using metal oxide catalysts (Ismagilov and Kerzhentsev, 1990). Prasad et al. reported
1981) that transition metal oxide (C0304/Cr2O3) catalysts yield very low levels of fuel-N
conversion (10 - 20%), in the lean fuel range of operation (4 = 0.4). Non-noble catalysts
(such as MoO3,Cr2O3,Co 3O4,Co/ZSM-5, CuZSM-5, LaMnO 3,V205,NiO, CuO, and

C0304/Cr2O3) were efficient in the oxidation of very lean methane-air mixtures
(Blazowski and Walsh, 1975; Quinlan et al., 1986; Cybulski and Moulijn, 1994; Li and
Li, 1996; Depiak and Wierzba, 1999; Cerri et al., 2000), and have shown enhanced
activity for CO oxidation, and NO reduction (Bharadwaj and Schmidt, 1994; Adelman et
al., 1996; Desai et al., 1999). These investigations focused on methane oxidation over
20
various non-noble metals catalysts. There is aneed to examine further the effectiveness
of such catalysts in relation to their applications to the combustion of natural gas, carbon
monoxide, hydrogen, etc. in order to obtain kinetic coefficients for these fuels over non-
noble metal catalysts.
2.2.4 Catalytic Oxidation of Some Common Gaseous Fuels
The ability of catalysts to oxidize various fuels to products of combustion has been
studied extensively. High combustion efficiency results in both minimum fuel

consumption and low pollutant emissions of CO through the complete oxidation of the
fuel to CO 2 and 1120. However, catalytic combustion efficiency depends on flow
conditions of the premixed reactants such as stoichiometry, pressure, inlet temperature
and velocity as well as catalyst configuration (monolithic structure, fibre burners, ceramic
cylinders, and pellet beds, etc.) and activity. The parametric study of Prasad et al. (1981)
on the performance characteristics of binary transition metal oxides (Co304,Cr203)
supported on alumina pellets using lean propane-air mixtures showed that the conversion
efficiency at the exit was very sensitive to small changes in the inlet conditions. During
the experiment they measured CO, UHC, and CO 2 at the exit from the reactor and
calculated the combustion efficiency on the basis of carbon balance. It was found that the
combustor performance was more sensitive to temperature than it was to the inlet
velocity or the equivalence ratio; a 1.0 percent change in the inlet temperature could
cause a50% change in overall propane conversion.
CH4 Oxidation: Cullis and Willatt (1983) found that the conversion of methane was
lower over aplatinum catalyst than over apalladium catalyst. They also showed that the
conversion efficiency -of methane over platinum or palladium could be affected by the
catalyst supports materials. Oh et al. (1991) conducted aset of experiments to show the
activity of agroup of noble metal catalysts (Rh, Pd, and Pt) in methane oxidation with or
without cerium (Ce) additives. They reported that the complete methane oxidation
activity ranking was Pd > Rh > Pt in the absence of Ce and was Rh> Pd Pt in the
21
presence of Ce. However, under reducing conditions in the absence of Ce, methane
oxidation activity decreased in the order Pd > Rh > Pt, with the tendency to form CO
decreasing in the order Rh > Pd > Pt. The activity of the catalyst depends on the fuel type
too as illustrated by Depiak and Wierzba (2003). The oxidation of several fuels such as
CR4,C2R4, C3H8,
CO, and H2 over platinum as well as over binary C0304/Cr2O3 catalysts
was studied. It was shown that aplatinum catalyst was superior to aC0304/Cr2O3 catalyst
for all the fuels employed in their study. Moreover, the conversion efficiency of the fuel
based, on the bed temperature on both catalysts (i.e. platinum or C0304/Cr2O3), decreased
in the order H2 > C2H4 > CO > C3H8 > CR4 (with H2 is the most reactive fuel).. The
conversion efficiency,
of the fuel is defined as the ratio between the initial and exit fuel
concentration to that of the initial concentration of the fuel.
The activity of acatalyst is also subject to variation with time as high combustion
temperatures physically change the catalyst materials. Cullis and Willatt (1983) reported
that prolonged exposure of the precious metals to oxygen at the temperature of 823 K
caused structural changes in palladium catalyst, although this did not occur with
platinum. The different behavior of palladium and platinum catalysts was attributed to the
difference in the ability of these precious metals to adsorb oxygen prior to reaction. They
also found that the catalytic activity for methane oxidation was independent of the size of
palladium particles dispersed on ?-aluminum oxide support. Hicks et al. (1990)
investigated the effect of palladium particle size on its atal,rtic activity in methane
oxidation at 260 to 370 °C. They showed that the catalytic activity of palladium depends
on its particle size. Their results suggested that the methane oxidation activity of the
dispersed PdO was significantly lower than that of the small palladium crystallites. It was
also shown that the catalytic activity of platinum depends on the distribution of the
dispersed metal and crystalline phases.
C2116 Oxidation: The influence of the addition of asecond fuel on the performance of a
given catalyst was investigated by L. D. Pfefferle et al.(1989a, 1989b and 1992). They
found that addition of small amount of ethane to amethane-air mixture allowed easier
22
ignition and flame propagation through aflat plate boundary layer system with platinum
as the catalyst.
ff8 Oxidation: The effect of the addition of propane on the ignition-extinction behavior
of methane in air over platinum foils in stagnation flow at atmospheric pressure has been
studied by Song et ál. (1990) and Balakrishna et al. (1994). Propane is the lightest
straight-chain hydrocarbon whose homogeneous oxidation kinetics appears to be typical
of higher molecular weight hydrocarbons (Glassman, 1980; Hautman et al., 1981). It was
observed that the combined mixture of methane-propane in air with sufficiently high
propane contents ignited at much lower temperature and power input than in the case of a
methane-air mixture. Moreover, coking was observed for fuel rich mixtures in cases in
which methane and propane were the fuel. An early investigation of Wampler et al.
(1976) was concerned with evaluating emission indexes and combustion efficiencies of
propane-air mixtures at inlet temperatures of 700-730 K as afunction of C3H8/air ratios
by volume on a platinum coated monolith. The maximum combustion efficiency
(99.99%) was achieved at C3H8/air = 0.0152 (4 = 0.24) with inlet temperature of 719 K
and the emission indexes, (g pollutant/kg fuel), of NO., and CO were 0.042, and 0.222,
respectively. The differences between platinum itself and very dilute platinum-in-gold
alloys on the dehydrogenation of propane to propene have been investigated by Biloen et
al. (1977). They found that propane dehydrogenation over platinum and over the alloys
occur via the same mechanism which includes the conversion of propyl radicals to ii-
bonded propene, using two adsorption sites located on one platinum atom, one of which
carried a hydrogen atom. Bruno et al. (1983) studied propane conversion at inlet
temperatures of 650 to 800 K, 110 kPa .pressure, velocities of 10 to 40 m/s, and
equivalence ratios of 0.19 to 0.32 with ahoneycomb platinum catalyst with 7-alumina
washcoat. It was found that the propane is mainly converted to CO 2 and H20 at the
surface. They also concluded that under the above conditions; gas-phase reactions tend to
become rapidly more important as temperature and equivalence ratio are increased and as
flow velocity decreased. Also, the surface propane conversion rate was much faster than
the rate of propane diffusion to the surface, resulting in adiffusion-controlled oxidation.

23
The oxidation of propane in air over transitional metal oxide catalysts was investigated
by Prasad et al. (1980) as mentioned earlier. The activities of oxides of Cr, Mn, Mg, Co,
and Fe in single or in -binary mixtures were tested for combustion of C3H8/air in an
adiabatic tubular reactor at various inlet temperatures (563-728 K) and equivalence ratios
(0.07-0.66). They found that the binary mixture of cobalt oxide and chromium oxide were
the .most effective in propane oxidation among the catalysts examined. Moreover, it was
concluded that the complete conversion of propane over C0304/Cr2O3 catalyst started at
an equivalence ratio of 0.196, an inlet velocity of 2.6 m/s, and an inlet temperature of 58Q
K; the NO emission in for these conditions was 0.03 g/kg fuel and was dependent
solely on the value of the exit temperaiure.
CO Oxidation: Carbon monoxide has its share of attention in research in the field of
catalytic combustion not only because of being part of emission products but also as an
important commodity in petrochemical industry. In fact, the oxidation of carbon
monoxide on platinum is one of the oldest known catalytic reactions and one of the most
thoroughly studied, yet it continues to pose difficulties and challenges to both

experimentalists and theoreticians, mostly due to the frequent observations of hysteresis,
associated with steady-state multiplicity, and self-sustained oscillations in the reaction. In
fact, there is no generally accepted theoretical explanation at hand, even though alarge
number of studies have addressed the subject. These studies were summarized by Razon
and Schmitz (1986). It is suggested that such hysteresis is due to the interaction between
reaction processes on the surface and transport processes between the surface and the gas
phase producing unstable phenomena (i.e., steady-state multiplicity and oscillations). Gas
phase impurities can produce spurious behavior. However, gas phase impurities were
dismissed as being the sole cause of this behavior after great care had been taken to
eliminate impurities from the system. This leads to the conclusion that the unstable
phenomenon must also be related to processes that occur on the surface (catalyst
morphology), of which the kinetic mechanism is the most important factor.
As early as 1959, Khitrin and Solovyeva investigated the role of surface reactions
in the combustion of carbon monoxide to obtain kinetic data inside narrow platinum and
24
copper tubes at temperatures ranging from 500 to 1400 °C. The global rate expression
obtained for small carbon monoxide concentrations was independent of oxygen
concentration. The mechanism of dry carbon monoxide oxidation over precious metals
was reported by Dwyer (1972). Employing platinum gauze as a catalyst and. using C
tracer measurements, the stoichiometric number of the carbon monoxide oxidation
reaction was measured. It was concluded that the reaction scheme and most probable
mechanism over platinum surface is: -
02 at the surface) (2.2)
CO + °(adsorbed at the surface) > CO 2 (2.3)
The investigation of carbon monoxide oxidation from synthetic gas mixtures on a

pelleted platinum-alumina catalyst at atmospheric pressure and in atemperature range of
200-370 °C was studied by Voltz et al. (1973) in order to establish arate expression fpi
CO (with 10% H20 on a wet basis) oxidation. A complex kinetic equation was
formulated with rate constants and activation energies. They reported that the rates of
oxidation were increased with increasing oxygen concentration and were inhibited by
carbon monoxide, propylene, and nitric oxide. Aging of pelleted-alumina and platinum
monolithic catalysts was also addressed in their investigation. However, this study was
intended for automotive emission control systems as was the work of Kuo et al. (1980). A
much simpler rate expression form was proposed by the later study of humid carbon
monoxide on platinum-alumina pellets. It was reported by Kuo et al. that lowering the
catalyst density or heat capacity by 25% enabled the inlet gas to warm up alarger portion
of the catalyst, and therefore increased the CO and HC conversion during warm-up.
Boehman et al. (1992) obtained an overall reaction rate for carbon monoxide oxidation
for temperatures from 180 to 300 °C and CO concentrations from 0.1 to 4.0%. The rate
expression was based on the dual-site Langmuir-Hinshelwood mechanism with empirical
modifications to account for the effect of high CeO 2 content over platinum. Langmuir-
Hinsheiwood mechanism is based on the assumption that both reactants are adsorbed
25
without dissociation at different free sites on the catalyst surface. This is then followed by
the actual surface reaction between neighboring chemisorbed molecules' to give the
product adsorbed on the surface. In the final step the product is desorbed away from the
surface. Dekker et al. (1994) studied the oxidation of dry car12on monoxide over an
alumina supported copper-chromium oxide catalysts for automotive pollution control
using the step response method. It was found that the catalyst goes through an
oxidation/reduction cycle when the gas feed composition is changed between oxidizing
and reducing. In the oxidation cycle, the catalyst temperature was raised to 773 K in an
oxygen stream for half an hour followed by cooling to room temperature. While in the
reducing cycle, ahelium gas stream was used. Also, the activity of the catalyst is higher
than the steady-state activity after the gas composition has changed from reducing to
oxidizing. It was also shown that 27.0% of the surface was covered with CO and CO 2 in a
reducing reaction mixture and 18.0% in an oxidizing reaction mixture. Other
investigations dealt with different issues indirectly involving carbon monoxide such as
the catalytic combustion of alow heating value fuel (biomass). Magnus and Jaras, (1997)
noticed-an improved oxidation of methane over LaMAl 11 O19 (La is acatalyst promoter;
M = Cu, Mn, Ni, Co, Al) catalysts by the presence of CO (with 10-12% H2O) and H2.
112 Oxidation: Catalytic oxidation of hydrogen has also been the subject of many
investigations. Hydrogen has many attractive features. Apart from being an excellent fuel
itself,it is needed increasingly for the upgrading of fossil fuels, the production of
alternative fuels, such as methanol, and awide range of other products. It is used in fuel
cells and is an important raw material in the petrochemical industry. Boudart et al. (1977)
studied the effect of pressure on reactions between hydrogen and oxygen on platinum
foils supported on silica gel in mixtures with an excess of oxygen. They found that
catalytic' activity was much less at high pressure than that at low pressure. Mori et al.
(1977) showed that the oxidation of hydrogen (2-7 mol %) at high pressure can be
improved by employing high temperatures up to 1100 K, so as not to produce nitrogen
oxide for hydrogen-air. Hanson and Boudart (1978) investigated the effect of platinum
dispersion and particle size on the reaction between H2 and 02 over Pt/SiO 2 catalysts at
26
temperatures between 273 and 373 K. Their results show that mixtures with an excess of
hydrogen reveal that the catalyst with the highest dispersion was seven times more active
at 273 K than was the catalyst of lowest dispersion. Whereas the reaction was first order
in oxygen and zero order in hydrogen. In the mixtures with an excess of oxygen, the
catalytic activity was independent of particle size, and the reaction was first order in
hydrogen and zero order in oxygen. Schefer et al. (1980) studied interactions between the
gas-phase combustion of hydrogen-air mixtures and surface reactions over aplatinum flat
plate in high-temperature combustion. The results obtained for arange of equivalence
ratios from. 0.05 to 0.30 and platesurface temperatures from 470 to 1300 K showed a
significant surface heat release for all mixtures at plate temperatures as low as 470 K. The
investigation of Schefer et al. was continued by Brown et al. (1983). It was devoted to
developing acatalytic combustion system in which the surface kinetics of various fuel-air
mixtures could be studied. Moreover, the system was intended to enable the study of the
high temperature surface oxidation rate for lean H2/air mixtures on aplatinum catalyst
over arange of surface temperatures from 450 to 1070 K and equivalence ratios from
0.05 to 0.20. They found that in the laminar boundary layer of aheated catalytic plate the
surface reaction rapidly became diffusion limited downstream of the plate leading edge.
This enabled them to obtain the surface reaction kinetics under such conditions where
surface reaction rates were significantly influenced by transport effects. The production
of hydrogen from direct oxidation of methane to synthesis gas over aNi/Al2O3 catalyst at
low temperatures was the subject of research by Choudhary et al. (1993, 1998). Their
results reveal that the performance of the reduced catalyst (reduction by H2 at 500 °C)
was better. It was also concluded that the partial oxidation of methane over Ni/A1203
under nonequilibrium conditions using high space velocity of 138.8 (its) results in a
much higher selectivity and productivity of CO and H2 than that obtained at the
equilibrium, with achange in the reaction path.

27
2.3 Theoretical and Computational Studies
Many mathematical models of catalytic reactors have been recently developed in order to
study their behavior and improve their performance. The performance of a catalytic
combustor is dependent upon operational conditions of the combustor i.e. the flow,
temperature, and composition of the mixture, the combustor design, and the properties of
the catalyst used. To find the optimal combinations of these factors by building and
testing actual catalytic combustors (reactors) would require avery elaborate ,and costly
experimental program. A desirable alternative is to develop and use apredictive model of
the combustor so that various combinations can be screened to determine which should
be built and tested.
The mechanisms of fuel conversion in catalytic combustion are very complex
phenomena. These to be' accounted for in catalytic combustion modeling include
heterogeneous and homogeneous chemical reactions, energy, mass and momentum
transfer by convection and diffusion in the gas phase as well as at the gas-solid interface.
These phenomena are strongly interactive and nonlinear because of the thermal effects
associated with the chemical reactions. Considering the strong nonlinearity associated
with temperature effects, the numerical solution of the governing equations is quite
difficult and requires the making of anumber of approximations. However, there are
successful attempts to model the transport, phenomena and chemical reaction
mathematically (Corma et al., 1998). The subject of mathematical modeling of catalytic

combustors is well reviewed by different authors. The most recent review is published by
Groppi et al (1999). They concluded that mathematical models represent apowerful tool
for the design, analysis and operation of catalytic combustors for gas turbines. The
complex physical and chemical phenomena affecting the behavior of a catalytic
combustor are numerous and the identification of reasonable approximation levels is
crucial. Computational studies reported in the literature present theories and analyses
which attempt to mathematically investigate the following:'

28
2.3.1 Bulk Diffusion
The diffusion of premixed hydrogen-air mixture over ahot platinum and non-catalytic
(quartz) surface (flat plate) has been, modeled by Markatou et al. (1991). They have
shown that the production of OH radicals during the surface reaction enhanced the
combustion of lean mixtures. Also, the thermal and mass boundary layers of hydroxyl
radical concentration became thinner for hydrogen combustion at = 0.10 and aplate
temperature of 1170 K. Markatou et al. attributed the thinner thermal and mass boundary
layers in the case of catalytic walls to the depletion of the fuel due to the surface reaction.
Their findings agree with the mass boundary layer thicknesses observed experimentally
for catalytic combustion of CH4IC2H4/air and H2 combustion under other conditions.
Goraiski and Schmidt (1999) have modeled the effect of catalyst pore size, fuel
concentrations, temperatures and pressures on the tubular plug-flow reactor exhaust
compositions in the high-temperature (T = 1473 K) combustion of methane on platinum.
They pointed out that the homogeneous chemical reaction is significantly inhibited by the
heterogeneous reactions. This inhibition is aresult of the adsorption of radical species
from the gas phase at the surface of the catalysts, which prevents initiation of gas-phase
free-radical chain reactions. The resuls of Goraiski and Schmidt (1999) showed that at
high temperatures and pressures the adsorption of the radical species 0, H, and OH on
the surface ihhibits the homogeneous chemical reaction enough that negligible amounts
of NO and CO are formed.
2.3.2 Intraparticle Diffusion
Mathematical models have also been developed to investigate the effects of an
intraparticle difftisional resistance (diffusion within the catalyst pores) on the ignition
performances of acatalyst. Trimm and Lam (1980) numerically studied the oxidation of
methane over platinum supported on porous and non-porous alumina fiber. The kinetics
of the reactions have been evaluated at temperatures above and below 815 K, where a
change in the apparent activation energy was found to occur. It was pointed out that pore
29
diffusion should be significant between 950 and 1000 K from their calculation of the
effectiveness factors (defined as the ratio of the rate of reaction when diffusion is
important at high temperatures to the rate of reaction when constant concentration
prevails throughout the catalyst at low temperatures). Nakhjavan et al. (1995) have
investigated the effect of catalyst surface area on monolith' combustor performances by
using a1-D model which accounts for heterogeneous and homogeneous reactions and for
axial heat conduction in the solid phase. Their analysis was applied to laminar flow
conditions and the results indicated that the porosity of the bed has an effect on the
ignition of the catalytic combustor. It was shown that larger catalyst surface areas will
benefit catalytic ignition especially during start-up. The results of Nakhjavan et al. also
show that the effect of porosity is more important in the transient state than in the steady
state. Moreover, the effect of porosity in their simulation was found to depend on the type
of fuel used for the combustion (i.e. slow oxidizing fuel such as methane, fast oxidizing
fuel such as propane',and extremely fast oxidizing fuel such as hydrogen). Groppi et al.
(1999) investigated the role of surface area on steady-state ignition performance of the
segmented catalyst section of ahybrid combustor. They developed a 1-D mathematical
model of a single monolith channel fueled by natural gas. The reaction-diffusion
phenomena within the catalyst poreswere accounted for by calculation of the catalyst
effectiveness factor based on the Thiele modulus .(defined as the ratio between the
intrinsic reaction. rate to the effective diffusivity of the limiting reactant or product), using
the analytical solution for first-order kinetics and for isothermal catalysts. Their
simulation results showed that a minimum level of catalyst specific surface area is
required to achieve best performance of th6 combustor.
2.3.3 Coupled Heterogeneous and Homogeneous Reactions
A number of theoretical and experimental studies have been conducted to acquirea better
understanding of the interaction between homogeneous and heterogeneous reactions. The
significant effect of this interaction demonstrates the importance of considering

30
homogeneous-heterogeneous reactions on various configurations such as the flat plate
boundary layer, the stagnation-point flow, and monolithic reactor.
Schefer and co-workers (1980, 1982, and 1983) conducted fundamental studies to
understand the role of catalytic activity at the boundary layer. They were among the first
to investigate the relation between catalyzed heterogeneous reactions at the wall and
homogeneous reactions in the adjacent boundary layer. The results of their simulation
showed that aplatinum wall acted as asource of free radicals only near the plate leading
edge. Further downstream, it appeared to be asink for free radicals, unlike quartz which
does not promotes fecombination of OH radicals, at the given conditions of 1 = 0.1 at
1170 K. The roles of heat and mass transfer and their effect on the combustion process
were also investigated. Their results indicate the existence of an initial region near the
plate leading edge in which the radical concentration increases with little associated heat
release, and adownstream region where heat release due to gas-phase combustion results
in a significant increase in thermal boundary layer thickness. The main difference
between Markatuo et al. (1991) study and of Cattolica and Schefer (1982) is that the later
did not observe the thinner thermal and mass boundary layers due to the surface
combustion of hydrogen. Treviflo (1981) and Treviflo and Peters (1 985) also used a
boundary layer model to establish criteria for gas-phase ignition in catalytic systems with
external heat loss. They assumed amass-transfer-limited surface fuel oxidation and one-
step homogeneous reaction. Markatou et al. (1993) used detailed gas-phase reaction in
their boundary layer model for the combustion of methane-air mixtures over heated
catalytic and non-catalytic surfaces maintained at constant temperature. They found
computationally that 0, H, or OH radicals can significantly accelerate the induction
period for ignition of light hydrocarbon mixtures in air. Their results illustrate the
sensitivity of the predicted methane flame propagation on the surface boundary
conditions used, which is more pronounced than for ahydrogen flame studied earlier..
The interaction between the heterogeneous and homogeneous reactions was also
investigated in different flow configurations (stagnation point flow). A computational
study of.the combustion of mixtures of hydrogen and air (4 from 0.15 to 0.3) impinging
on aplatinum plate at an elevated temperature of 1173 K was presented by Ikeda et al.

31
(1993). It was shown that, at relatively low surface temperatures and low concentrations
of hydi'ogen, heterogeneous reactions dominate while at higher temperatures and higher
concentrations homogeneous reactions tend to do so. However, their model was not
validated experimentally. Vlachos and co-workers (1993, 1995, and 1996) computed the
ignition and extinction of the homogeneous combustion of lean H2 in air from room
temperature up to 1500 K with stagnation point flow and detailed chemistry numerically.
They concluded from their studies that H atoms are, the most important in shifting both
ignition and extinction points away from the surface, especially near a heated wall at
sufficiently large equivalence ratios (about 12% H2). The HO 2 radical is the next most
important in ignition, but the least important in extinction. Moreover, the presence of
H20 in the initial mixture results in aslightly enhanced combustion of 112. Machos et al.
also pointed out that ignition and extinction can be influenced by heat transfer, especially
at low pressures. At high pressures flame instabilities are mainly driven by reaction heat
generation and are strongly affected by the enhanced third body efficiency of 1120 in the
reaction H + 02 + M --> HO2 + M. A more rigorous multi-component model of the
catalytic ignition of CH4, CO, and 112 oxidation on platinum and palladium at
atmospheric pressure was studied by Deutschmann et al. (1996) for two simple
configurations. The simulation includes detailed reaction mechanisms for the gas-phase
and the surface. A quantitative agreement between measured and, calculated ignition
temperatures was obtained. It has been shown that the ignition temperature of CH4
decreases with increasing CH4/0 2 ratio up to an equivalence ratio of 0.9.
For monolithic tubes geometry in high temperature catalytic processes, the
behavior of reactors in which homogeneous and heterogeneous reactions occur
simultaneously is modeled and investigated by Harrison and Ernst (1978). A steady-state
model of heat and mass transfer for the combustion of four mole percent dry carbon
monoxide in an adiabatic laminar tubular flow reactor was considered. However, axial
heat conduction and diffusion were not included. Three reaction models were
investigated: homogeneous phase reactions only, heterogeneous reactions only, and
combined heterogeneous and homogeneous reactions. Comparison of results from these
three models demonstrates that it is necessary, to include both homogeneous and

32
heterogeneous reactions when modeling adiabatic high temperature "catalytic converters"
because at temperatures between '650 and 1150 K homogeneous reactions ,begin to

contribute significantly to the intermediate pool of radicals. However, they concluded
that for design purposes, for sufficiently high inlet temperatures (i.e. near the upper end
of this range, which is close to 1150K), acatalyst may be necessary only near the reactor
inlet to light-off the homogeneous reaction. Bensalem and Ernst (1982) modified the
previous model (l'aminar flow) and applied it to atwo-chamber, reactor (laminar and
turbulent flow) of the same length in order to improve its performance at high
temperature. The first chamber was asmall diameter,

channel with acatalytic wall which
was' mainly controlled by amass transfer surface reation. The chamber was not coated
with catalyst and had alarger diameter. In this terminal portion of the reactor, the bulk
gas temperature was high enough to support the homogeneous combustion of the fuel.
Bensalem and Ernst showed that this particular deign minimizes considerably the
pressure drop without altering the overall conversion at relatively ahigh temperature and
turbulent flow. Such atwo-chamber reactor might be used when there is an interest in
minimizing the pressure-drop (e.g. combustors, stack clean-up reactors). Their results
also confirmed the earlier results of Harrison and Ernst indicating that both the
homogeneous and heterogeneous reactions are important at the intermediate range of
'temperatures from about 650 to 1100 K. T'ien (1981) developed atransient model to
investigate the behavior of catalytic monolith combustors including both heterogeneous
and homogeneous reactions in fuel-lean operation. He used aone-dimensional model that
allowed for temperature transients in the thin monolith wall and aquasi-steady-state gas
thermal balance. T'ien's results also indicate that higher combustor temperatures and
adiabatic flame temperatures shorten the response time to a change in the upstream
conditions. Alin et al. (1986) developed a one-dimensional transient model similar to
T'ien's model, which accounted for the effect of thermal conductivity in the wall. They
confirmed that cold start-up was astrong function of the monolith's thermal inertia, its
material and configuration. Metallic monoliths were found to respond much more quickly
to changes in operating conditions when compared with ceramic monoliths. Higher inlet
temperatures and operating pressures, and lower gas velocities were shown to result in
33
faster response times. Performance of reactors of square channel geometry was better
than that of triangular or sinusoidal geometry because of the better heat and mass
characteristics of the square channel geometry.
2.3.4 Transport Mechanisms
Chen et al. (1988) developed athree-dimensional model to analyze the transient response
of an axisymmetric ceramic monolith car converter during its warm-up and engine
misfiring. Their model simulates the thermal and conversioh characteristics of anon-
adiabatic monolithic converter operating under flow maldistribution conditions. Their
model accounts for convective heat and mass transport, gas-solid heat and mass transfer,
heat conduction, chemical reactions and their attendant heat release, and heat loss to the
surroundings. The results of their simulations indicated that variation in the exhaust flow
rate had aminor effect on conversion efficiency during warm-up. However, the noble
metal loading and the flow distribution of the exhaust gas were shown to have astrong
influence on the solid temperature profile during the converter warm-up. Flow
maldistribution and radiant heat loss were identified as the major sources for the
temperature gradient. The predicted temperature profiles provided abasis for the analysis
of thermal stresses and fatigue in the monolith converter assembly.
Groppi et al. (1995, 1997, 1999) have reported that 1-D models for avarious
channel geometry (triangular) lead to predictions of gas exit temperatures for asingle
segmented monolith in CH4-fueled catalytic combustors that are in fair agreement with
those of more rigorous 2-D and 3-D models. This conclusion is obtained under the
assumption that light-off occurs immediately downstream of the catalyst inlet.
Bond et al. (1996) developed a numerical model of the catalytic combustion
process based on CHEMKIN code (Coltrin et al., 1991) for detailed gas-phase and
surface kinetics. The effect of equivalence ratio (ranging from 0.11 to 0.44) and inlet
velocity (from 5.5 to 10.0 m/s) at atmospheric pressure were considered. The predictions
of the numerical model of combustion of natural-gas over platinum supported on ceramic

34
honeycomb monoliths were in fair agreement with

' the experimental data at temperatures
below 900 K. However, at higher temperatures the predicted fuel conversion was two
orders lower than the measured data. NO emissions were shown below 1ppm and CO
was observed at the ppm level.
The application of catalysts in radiant burners was considered by Rumminger et
al. (1999). Simulations were performed to investigate the effect of platinum catalyst
loading, location of the catalyst layer, and its thickness on the performance of burners
with single and bi-layered porous media. It was shown that only athin layer of catalyst
placed at the downstream edge of the porous medium was required for efficiency
improvements. The model predictions were compared with experimental data obtained on
catalytic radiant burners.
The effects of operating conditions on combustion efficiency and pollutant
formation were reported by Moallemi et al. (1999). The numerical and experimental
investigations were carried out using palladium and platinum based catalytic monoliths
for methane combustion (for heating purposes). The model for a well-stirred reactor
included detailed homogeneous/heterogeneous chemical kinetics for methane-air
mixtures of equivalence ratios ranged from 0.3 to 06 and space'velocities between 400
and 1209 (1/mm). Dupont et al. (2000) extended the above model to investigate the effect
of the catalyst (Pt and, Pd) loading, flow rates ranging from 40 I/min to 94 1/mm, and
monolith length. It was found that apalladium catalyst provided alarger range of stable
operation than platinum ones for equivalence ratio ranging from 0.44 to 0.80. Their
results showed that the pollutant emissions (i.e., CO, NO,,, and UHC) were "near zero"
•
for the operating conditions employed in their investigation. The catalyst role was proved
not only necessary to enable the ignition of fuel mixtures below flammability limits, but
also to ensure the complete oxidation of the fuel' to CO 2 via surface reactions in the
steady state. Also areduction of 70% in the original length (of 50 mm) of the monolith
was found possible.
Accordingly, in view of the key role that mathematical modeling can play in
future developments of catalytic combustor technology, joint efforts from experimental

and theoretical work groups devoted to model validation are strongly recommended.
35
In general, the above mentioned models were developed for specific applications
and cannot be applied directly to other conditions. In addition some of these models were
not validated experimentally. Recently, amodel of atransient plug-flow reactor which
includes bed heat conduc'tion, radiative heat transfer, axial diffusion, and convective heat
transfer between the solid and gas in addition to the homogeneous and heterogeneous
reactions was pr
oposed by Younis and Wierzba (2002, 2004) and is the subject of the
present thesis. The effect of operating conditions such as inlet temperatures, approach
velocities, and equivalence ratios on methane conversion efficiency were investigated:
2.4 Summary
Catalytic combustion is employed in a wide range of applications to utilize various

gaseous fuels efficiently a:nd suppress exhaust emissions without major increase in the
cost. A substantial research effort has resulted in some interesting options for materials
utilized in catalytic combustion. Especially, the incorporation of non-noble metal
catalysts on high thermal resistance alumina support seems to provide an opportunity to
circumvent loss of surface area and catalytic activity even at high temperatures. Several
single and complex transition metal oxides such as cobalt and chromium oxides have
ben shown to have high oxidation activity, approaching the noble metals. However, it
appears to be difficult to combine the two toughest demands for combustion catalysts,
namely, sufficient low temperature activity and high-temperature stability. Even though
positive results have been achieved, attention should be focused on metal oxides catalysts
because of the advantages they offer such as lower cost and potentially higher maximum
operating temperatures. The catalytic combustion within packed bed reactors is not we ll
pursued specially for non-noble metal catalysts, most probably due to its high pressure
drop even though, packed bed reactors have a wide application in the .petrochemical
industry. Furthermore, there is alack of kinetic data for non-noble, metal oxide catalyst
which is important for modeling purposes. Therefore, modeling and experimental
research are necessary to generate realistic models to improve the reactor design and
36
operation. Moreover, the combined heterogeneous and homogeneous reactions are
important, especially for high temperature combustion and in some cases for ignition.'
The present study attempts to develop a mathematical model for the catalytic
combustion in apacked bed reactor and thus to obtain kinetic data for abinary mixture of
cobalt and chromium oxides catalyst. The developed model incorporating the kinetic data
obtained during this investigation should allow more time and cost efficient parametric
study of such catalyst.

37
CHAPTER 3
ANALYSIS AND MATHEMATICAL MODELING
3.1 Introduction
The development of the present model followed the philosophy of constructing a
catalytic packed bed reactor mathematical model which includes only the essential
parameters of the reactor. These parameters were determined by beginning with asimple
model that contained only the major transport processes and physical and chemical
parameters and then comparing the performance of the model with values measured in an
experimental catalytic reactor. When any significant discrepancy arose, the model was
refined by including more details (e.g., the model initially assumed constant gas
properties, then the model was refined for these properties to be afunction of the local
temperature), but without including any parameters that are arbitrarily adjusted to
improve the model predictions.
Accordingly, in the present investigation, amathematical model was proposed for

the oxidation of lean fuel-air mixtures within inert and catalytic packed bed reactors. The
transient model developed includes heat and mass transfer (i.e. axial heat conduction in
the gas and solid phases, radiative heat transfer, axial diffusion, and convective heat
transfer between the solid and gas) as well as both homogeneous and heterogeneous
reactions. The developed model is general in applicability and can be applied to any
gaseous fuel and catalyst but the calculations are mainly made for methane with platinum
as the catalyst. The present model is used to obtain kinetic data for other fuels over non-
noble metal catalysts such as the binary mixtures of cobalt and chromium oxides within
the packed bed reactor.

38
Thus, in this chapter, a detail description of the steps and efforts employed in
developing the mathematical model including homogeneous reactions will be addressed.
In order to validate the mathematical model, an experimental program was conducted in

parallel. The mathematical analysis starts with the physical description of the system
under consideration.
3.2 Description of the Physical Model.
A premixed, preheated homogenous fuel-air mixture enters into acylindrical packed bed
reactor (catalytic or non-catalytic), initially at auniform temperature. The temperature of
the packed pellets and the fuel-air mixture changes with time and distance due to heat
transfer and chemical reaction processes. The schematic diagram of the physical model
under consideration is shown in Fig. 3.1.
Fig. 3.1 Schematic diagram of the physical model.

39
The transport processes taking place in the packed bed reactor are very complex, as they
involve several modes of heat transfer, as well as homogenous and heterogeneous
chemical reactions. When the preheated fuel-air mixture flows through the reactor bed
the heat transfer processes involve convective heat transfer between the gaseous mixture
and pellets, axial heat conduction in the pellets as well as heat radiation. Radiative heat
transfer in the porous bed is an extremely complex process. It can take place between the
solid pellets themselves, between the solid pellets and gases, as well as between the
pellets, gases and the walls. Although, radiative heat transfer is not very significant at low
temperatures, it can b'ecome a dominant mechanism of heat transfer at elevated
temperatures. The most significant mode of radiation is the radiation in the solid pellets.
Therefore, the radiative heat transfer in only the solid pellets is accounted for in the
model prediction. Since the gas temperature is intimately coupled to the solid via internal
convection, it also exhibits transient behavior until steady state is reached. Moreover,
heat conduction takes place in the solid, in both directions from the location in the packed
bed where chemical reactions commence, as that location will be heated first. The heat
transfer modes mentioned above take place simultaneously in addition to the
homogeneous and heterogeneous chemical reactions. Some of these heat transfer modes
such as radial heat conduction and radiative transfer in the gas need not to be accounted
for in the present one-dimensional analysis, due to the numerical. complexity involved in
solving the resulting nonlinear partial differential equations.
3.3 Description of the Mathematical problem
3.3.1 Governing Equations
Governing equations for ageneral packed bed reactor are presented here for the oxidation
of fuel-air mixtures within atransient system. In the system described, the following
assumptions were made:
1. The velocity of the flow is uniform, i.e., plug flow.
2. The reactor is operated adiabatically.

40
3. The gas and solid are not in local thermal equilibrium, i.e., separate energy
equations are employed for these two phases.
4. Gaseous radiation is negligible compared to the pellet radiation.
5. Radiative heat transfer in the packed bed was modeled using the concept of so-
called effective thermal conductivity (Eq. 3.4) of the pellets which is considered
to be afunction of their temperature.
6. The density, the specific heat and the thermal conductivity of the gases are
considered to be variable and are evaluated for the instantaneous local

temperature and mixture composition.
7. The thermal properties such as the density, thermal conductivity, specific heat,
and porosity of the pellets are uniform and constant.
It should be noted that the thermal conductivity of the solid (pellets) is not the same as
the effective conductivity of the material. The effective conductivity constitutes the
pellet's solid thermal conductivity and flow conditions (i.e., the porosity of the bed) as
well as the radiation effect.
The resulting laminar, axisymmetric, unsteady, one-dimensional (plug flow) conservation
equations of mass, energy and species for the transport phenomena can be written as:
Continuity
7(P g s) + ax (P g "i) 0 (3.1)
where, p is the density of gaseous mixture, tis the time, xis the axial distance along the
reactor, uis the axial velocity, 6 is the porosity, and subscript 'g' refers to gas.
Energy equation for the gaseous phase:

41
a a a aT
—(pc sT)+—(p usc T)
at g pg g ax g pg g 8x g ax
(3.2)
-(1--s)h -1'3- ethHkAiflf
In the above equation, T is the local temperature, kg is the gas thermal conductivity and
c, is the constant pressure specific heat of the mixture, k is the volumetric heat transfer
h
coefficient per unit volume, Hk is the specific enthalpy of species k, (Dk is the molar
production rate per unit volume of species k due to homogenous reaction in the pore,
MJ4 is the molecular weight of species k, where subscript 's' refers to solid and, 'k'
refers to species k (i.e., the fuel or the oxidant). The gas property data are listed in
Appendix A.
The first term of the left-hand side of equation (3.2) represents the storage of
energy in the gas per unit volume. The second term accounts for the energy advected by
the gas per unit volume. The first term of the right-hand side of the equation (3.2)
accounts for heat conduction in the gas phase per unit volume. The second term
represents internal gas/solid convection per unit volume. The third term represents the
amount of energy released in the as per unit volume due to homogeneous reactions.
Energy equation for solid phase (pellets):
a = H15)keff) + (1—e)h(2--I)
ax ax
(3.3)
+ (1—e)th HkMWk acat
where cs is the specific heat of the solid, Wk is the molar consumption 'rate per unit area
of species kdue to catalytic reaction (to be discussed in the next section), and acat is the
catalyst specific surface area. -

42
The left-hand side of equation (3.3) represents the storage of energy in the solid per unit
volume. The right-hand side first term accounts for heat conduction per unit volume. The
second terñi represents internal heat convection between the gas and pellets per unit
volume. The third term stands for the amount of energy released. at the surface per unit
volume due to heterogeneous reaction.
In equation (3 .3), 'kW is the effective thermal conductivity of the pellets calculated using
aRosseland diffusion approximation as follows (Modest, 1993):
keff = k + 16a7 or keff = f(T) (3.4)

38
where o is the Stefan-Boltzmann constant, 5.67 x1 W/(m2.K4), and 0is the extinction
coefficient.
The volumetric heat transfer coefficient h equation (3.2 and 3.3) between the gaseous
mixture and pellets is calculated as:
hV (3.5)
where S, and V, are the surface area and volume of apellet correspondingly, h is the
convective heat transfer coefficient calculated as follows (Wakao and Kaguei, 1982) for
gaseous laminar flow:
hd 0. 6
Nu ,
= - 2.0 + 1.1Pr Re (3.6).
kg
In the above equation, Nu, is the averaged Nusselt number, d, is the pellet diameter, Pr,
is the Prandtl number, and Re p ,is the Reynolds number.

43
where
/1 Cpg
Pr = (3.7)
kg
where p is the viscosity of the mixture.
and
ud
Re = —a (3.8)
Vg
where v9 is the kinematic viscosity.
Chemical species balance:
o a a
.(pg eY)
j + — Co euYk) = ,. — )
—(pg .- D l + a'd)MWk (3.9)
ax g OX Ox
where Yk is the mass fraction of species k, Dk is the mixture diffusion coefficient of

species k.
In equation (3.9) the first term of the right-hand, side represents the molecular diffusion
of the species kper unit volume in the mixture. The second term stands for the generation
of the species kdue to homogeneous chemical reaction per unit volume. The first term of
the left-hand side of the equation (3.9) represents the rate of gain of mass of species kper
unit volume in the gas mixture. The second terms accounts for the mass flow of species k
out due to advection by bulk flow per unit volume.
The gaseous mixture is treated as an ideal gas at constant atmospheric' pressure.
Therefore, the mixture density is calculated from:
pMW
1
09 (3.10)
R Tg
44
In equation (3. 10), p is the pressure, MW is the mean molecular weight of the mixture
and R is the universal gas constant.
3.3.2 Kinetic Modeling
• Gas Phase (Homogeneous Reactions)Kinetic Modeling
The energy released due to gas-phase reactions is calculated by employing an
irreversible one-step overall homogeneous reaction of the Arrhenius type as
follows:
h = Ag Cm C exp [j Eg (3.11)
where Ag is the pre-exponential factor for homogeneous reaction. Cf and C0 are
molar concentrations of the fuel and oxygen respectively. Eg is the activation
energy for, the gas-phase reaction. m, and n are the exponents of the molar
concentration of the fuel and oxygen.
• Catalytic Surface (Heterogeneous Reactions) Kinetic Modeling
The surface reaction rates over the catalytic pellets are modeled as an irreversible,
one-step reaction rates using the empirical expressions proposed by Soiig et al.
(1991) and Markatou et al. (1993):
A Cf C' 5
ex[
ES
R J (3.12)
45
where A is apre-exponential factor for the heterogeneous reaction, Cf and CO
are molar concentrations of the fuel and oxygen respectively, E8 is the activation
energy for the heterogeneous reaction.
This form of the rate epression is consistent with all experimental results cited
under conditions relevant to this study (high oxygen concentration). This would be
consistent with aLangmuir-Hinshelwood type reaction mechanism assuming low
overall surface coverage and dissociative adsorption of oxygen.
The molar concentration of the species, Ck, is related to their mass fraction, Yk,
by:
Ck =P g Yk /MWk (3.13)
3.3.3 Initial conditions:
The gaseous mixture is assumed initially to be at uniform initial temperature and mixture
composition:
At t=O and O≤x≤L
U= Ujn, Tg= Tin, Yi = 0 (3.14)
3.3.4 Boundary Conditions:
For the system described in section (3.2), the following boundary conditions are
considered:
atx=0 uu; Tg Ts Tin; Yk.= Ykin (3.15)
at x= L au =0; -=0 g=
(3.16)
ax' 5x ax
46
3.4 Numerical Model
3.4.1 Method of Solution
The SIMPLE algorithm for solving the equations is discussed in detail by Patankar
(1980). The methodology used to solve equations (3.1, 3.2, 3.3, and 3.9) with the
associated boundary conditions is based on the implicit, control volume, finite-difference
technique. The unsteady finite-difference form of the energy equations is obtained for
each node location, by integrating equations (3.2) and (3.3) over space in the x-direction
and over time. These algebraic equations are then solved using aline-by-line iterative
method. Due to the nonlinearity, the gas and the solid temperatures are underrelaxed. The
underrelaxation of temperatures helps to prevent the solution from diverging. .The time
dependence is handled by stepping in time using fully Euler method and retaining a
converged solution at each time step. The grid used in the finite-difference scheme
establishes the positions of the nodes; the control volume boundaries are shown in Pig.
3.2, where the dashed vertical lines are the control volume boundaries. The spacing
between the boundaries is the control volume thickness. The solid dotted lines denote the
node position. There are atotal of M nodes in the porous bed of length L. The number of
nodes used to generate the results is 101 nodes in a50'mm bed length.
3.4.2 'Computer Code Development
A 'step-by-step approach was pursued in developing a computer code to simulate the

flow; heat and mass transfer in the packed bed reactor. Each stage of the program was
tested carefully and evaluated. A summary of the steps followed in the process of
.developing the computer code is listed below:
1. The energy equations for the fluid and the solid were solved. The sensitivity of the
program with respect to volumetric heat transfer coefficient was tested by setting the
initial temperature of the fluid and solid at different values. The solution converged
47
to the same temperature for the fluid and solid after acertain period of time. The
period to reach equilibrium was dependent on the velocity.
2. All the above steps were applied first for constant thermophysical properties of the
fluid and the solid. Then variable .propèrties were implemented in the computer -
program.
(
3. The species conservation equation was added with a global irreversible one-step
reaction (Arrhneius type).
4. The global one-step heterogeneous reaction was added to the solid energy equation
and was implemented in the numerical code.
A flow chart of the numerical code is shown in Fig. 3.3.
Fig. 3.2 Control volumes and mesh generation.

48
(
Start
Input data
(Tj, uj, and )
I Calculate
1 thermophysical
properties of the gas
Set boundary and

initial conditions
S.
Solve energy
equations for gas
and solid phases
I
I
Solve species
equation
Update the
solution
If the time
> max. time
Yes
Output
Fig. 3.3 Flow chart of the numerical model.

49
3.5 Preliminary Results of Numerical Simulation of Methane
The conversion of afuel in lean fuel-air mixtures depends on various parameters, such as
inlet temperature, equivalence ratio, 4) (defined as the actual fuel/air ratio divided by the
stoichiometric fuel/air ratio), approach velocity, and u(defined as the average velocity of
the flow in the conduit without packed pellets). The effects of these parameters on the
extent of conversion of afuel were investigated numerically using the above model for
the range of operating conditions summarized in Table 3.1.
Table 3.1 Values of operating parameters employed in the numerical calculations.
Length of reactor (mm) 50.0; 75.0; 100.0
Type of packed pellets 0.5% Pt on y-Al2O3; y-A1203
Apparent average density of the packed bed, Ps (kg/m3) 100.0
Thermal conductivity of the packed bed, k5(W/m.K) 1.0-4.0
Specific heat of the packed bed, CPs (J/kg.K) 837.0
Porosity, s 0.2 - 0.9
Inlet temperature, Tin (K) 293 - 1300
Approach veloèity, u(m/s) 1.0 - 3.0 -
Equivalence ratio, 4) 0.05 - 0.50
Fuel CR4;C2H6;C3118;CO; H2
The fuel conversion was calculated as:
% fuel cony = 4fue1 100 = fuel, fuel out 100

(3.17)
-
fiiel 1 fuel,
Moreover, the effects of bed porosity, solid thermal conductivity, bed length, and fuel
type were also investigated.

50
Methane was employed as the primary fuel in the present study. The influences of the
numerous parameters identified above on the conversion rate of the methane were
studied. Three different types of calculations were conducted with methane as afuel. In
the first case only gas-phase (homogeneous) chemistry was considered as in the case of
an inert packed bed reactor. In the second case only heterogeneous (surface) reactions
were taken into account, as in the case of very low inlet temperatures. In the third case
both homogeneous (gas-phase) and heterogeneous (surface) reactions were considered, as
in the case of oxidation at higher temperatures.
The homogeneous (gas-phase) reaction rates for methane oxidation over the inert
pellets were modeled using an irreversible one-step reaction rate (Eq. (3.11)) in the
general form:
Eg
= Ag C 4C ex[ RTgJ (3.18)
It is readily acknowledged that this formulation for the reaction rate is in adequate to
represent its variation during the course of the oxidation process and sufficiently detailed
reaction kinetics need to be employed. However, for the overall modelling being pursued
here with the objective of obtaining a parametric study, this assumed form was
considered to be adequate for the purpose. The values of the pre-exponential factor "Ag"
and the activation energy "E.g"in the above equation (Eq. (3.18)) were first chosen on the
basis of the values available in the literature for methane-air mixtures in premixed flame
and were: A. = 7.90 x 1010 kmol/m3.s, and Eg = 202.60 kJ/mol (Westbrook, 1981). These
data have been used by other researchers and in some cases the value for power of the
fuel and oxidant concentration as well as the pre-exponential factor have been changed to
fit the conditions under.consideration. For example, Hautman et al. (1981) started with •
the above equation (Eq. 3.18) and developed amultiple step kinetic for the oxidation of
hydrocarbons within flow reactors and shock tubes. They developed rate expressions
which encompass an equivalence ratio range 0.12 to 2. 0, atemperature range from 960 to
51
1540 K, and apressure range 1to 9atm. Duterque et al. (198 1) altered the above reaction
to apply it intheir well-stirred reactor for the combustion of light hydrobarbon in air for
equivalence ratios from 0.65 to 1.2 and temperatures from 1450 to 1960 K. However,
Coffee (1985) used Westbrook's rate expression to obtain kinetic rate expressions and
data for stoichiometric and rich methane-air mixtures at atmospheric pressure. A wide
range of other formulation and corresponding data also can be found in the literature with
various degrees of agreement with experimental observations. Figure 3.4 shows methane
conversion as afunction of the inlet temperature for the equivalence ratios of 4) = 0.35
and u= 1.0 m/s using the kinetic data of Westbrook (1981). It can be seen that such data
cannot predict the experimental data of Depiak and Wierzba (1999) for methane
conversion in a packed bed reactor within reasonable accuracy. Therefore, kinetic

coefficients were obtained by matching the model prediction with the experimental data
of Depiak and Wierzba within the packed bed reactor. These acquired values which were
used throughout this investigation are: A. = 6.6 x 1010 kmollm3.s, Eg= 180.0 kJ/mol.
The heterogeneous (surface) reaction rates for methane over catalytic pellets were
modeled as an irreversible one-step reaction rate using the equation suggested by Song et
al., 1991:
CO AS CcH4 CexP[
Ts
] (3.19)
where the ',alues of the parameters A3 1.03 x i0 kmollm2.s, and E3= 86.0 kJ/mol were
chosen from (Trimm, and Lam, 1980 for V > 813 K) for methane-air mixtures with
platinum as the catalyst (i.e., platinum supported on porous alumina fibre). These
coefficients were used at the early stages of this research to investigate the behavior of
the packed bed reactor under different operating conditions. These results will be
discussed in this chapter. However, when using the above mentioned kinetic data in the
model could not predict to areasonable accuracy the experimental data of the packed bed
reactor. Therefore, new kinetic data were derived for the packed bed reactor in the
following chapters.
52
100 -
— Experimental (Depiak and Wierzba, 1999),

80 -. - Calculated (Westbrook kinetic data) ,
- 1
60
I
40 - I
I I
I
-
20 - I
A
AW
goo 900 1000 1100 1200

Inlet Temperature (K)
Fig 3.4 Comparison between predicted methane conversion using the kinetic data of
Westbrook (1981) and experimental data for methane conversion from Depiak and.
Wierzba (1999); u= 1.0 rn/s, 4) = 0.35, k3= 1.0 W/m.K, inert bed.
3.5.1 Inert Bed
The effect of the inlet gas temperature on methane conversion in areactor with an inert
bed due to gas-phase reactions is shown in Fig. 3.5 for the equivalence ratio (4)) of 0.35
and an approach velocity of u= 1.0 m/s (calculated at reference-unheated conditions) It
can be seen that below 900 K there is no significant conversion of methane. Rapid
chemical reaction occurs at an inlet temperature of -j 1080 K. It can also be seen that the
predicted results are in fair agreement with the corresponding experimental data of
Depiak and Wierzba (1999) for the '

same operating conditions. However, the predicted
conversion of methane at lo w
' temperatures is somewhat less than that obtained
experimentally.
As the equivalence ratio of these lean mixtures increases the conversion ofthe methane is
completed at lower temperatures, as shown in Fig. 3.6. The complete conversion of

53
methane in the mixture with an equivalence ratio of 0.50 takes place at an inlet
temperature of 860 K, while a temperature of 1200 K is needed for the complete
conversion of methane in the mixture with an equivalence ratio of 0.15.
The effect of approach velocity is shown in Fig. 3.7 for amixture with of 0.35. An
increase in the approach velocity causes a significant decrease in the conversion rate,
which was expected due to adecrease in the residence time. For example, at the inlet
temperature of 1088 K, the methane conversion was 100.0%, 12.2%, and 6.1% at the
approach velocities of 1.0, 2.0, and 3.0 m/s respectively.
100 A
- - - - Calculated (present work)

80 - A Experimental (Depiak and Wiex2ba)
.9 60
40
20
A AAA ±A A #
goo 900 1000 1100 1200
Fig. 3.5 Comparison between calculated and experimental results of methane conversion;
u= 1.0 m/s, = 0.35, ks= 1.0 W/m.K, inert bed.

54
100
----0.15 I
80— - --0.2
1 i
II
0.35
II
0.4
0.5
I
'-,
60 -
A 0.35,Exp.
.-
-
ii
40
ts
20— 1/
- I I
.0
I I
00 ' 700 800 900 1000 ' 100 1200
Met Temperature (K)
Fig. 3.6 Calculated methane conversion as afunction of inlet temperature at different
equivalence ratios; u = 1.0 m/s, k = 1.0 W/m.K, inert bed, (*) Depiak and Wierzba
(1999).
100
u1.0m/s
80 u=2.0 m/s
u3.Om/s
c40
20
-
- -
•__7 I I
900 1000 1100 1200

approach velocities; 4) = 0.35, k = 1.0 W/m.K, inert bed.

55
3.5.2 Heterogeneous Reactions
In order to examine the combustion processes under the idealized artificial condition of
the combustion process is assumed to be controlled by the surface reaction only (purely
heterogeneous reactions) in this case. It can be seen (Fig. 3.8) that, as in the first case of
homogeneous reactions (inert bed), methane conversion increases with an increase in the
inlet temperature. The temperature at which complete conversion of methane occurs is
higher than the corresponding temperature found for the case of solely gas-phase
reactions. This is areflection of the values for activation energy and the pre-exponential
factor (A = 1.03 x 10"5 kmol/m2.s, and Es = 86.0 kJ/mol; (Trimm and Lam, 1980))
chosen with platinum as catalyst and methane as the fuel that were obtained for a
different reactor configuration (see page 118 for the sensitivity of methane conversion
due to changes in the pre-exponential factor and activation energy).
It can also be seen that the increase in the equivalence ratio from 0.20 to 0.50 has
little effect on methane conversion. At the inlet temperature of 1075 K, a maximum
difference of 4.83% was obtained for methane conversion as the equivalence ratio
increased from k= 0.35 to 4= 0.50 at the light-off regime. The light-of regime
corresponded to inlet temperature ranges from 1050 to 1125 K. The most noticeable
conversion difference occurred within this regime, otherwise, it was negligible. Since,
there is no data available in the literature for methane conversion along the packed bed
for = 0.35, the range of equivalence ratio was extended to 4 0.71 in order to compare
the simulated methane conversion with the predicted data of Goralski and Schmidt (1999)
in aplug flow reactor. The conversion of methane as afunction of the axial position in
the reactor at = 0.71, u= 1.0 m/s and T = 1200 K is shown in Fig 3.9. Methane begins
to react immediately upon entering the catalytic bed and continues to react along the bed.
Goralski and Schmidt surface reactions 'are modeled with detailed kinetics using an
elementary 19-step mechanism for combustion of methane on platinum. The results are in
reasonable agreements. However, methane conversion obtained from the present
investigation is higher than that of Goralski and Schmidt taking into consideration that
the predicted methane conversion from the present study is calculated using one-step
irreversible surface reactions.

56
100
80
• 60
0
40
20
900 1000 1100 1200 1300

Inlet Tem perature (K)
Fig. 3.8 Calculated methane conversion as a function of inlet temperature for various
equivalence ratios; u= 1.0 m/s, k = 1.0 W/m.K, Pt catalyst.
100
80
"p
0
.-
20
00 0.01 0.02 0.03 0.04 0.05

Distance along the bed (m)
Fig. 3.9 Calculated methane conversion along the bed; 1i = 0.71, u= 1.0 m/s, Ti. = 1200
K, Pt catalyst.
57
The effect of the approach velocity on methane conversion is presented in Fig. 3.10 for 4
= 0.35. As in the case of inert beds the conversion of methane decreases with an increase
in the velocity. The maximum decrease in the conversion of-methane with an increase in
velocity is obtained in the light-off regime of the catalyst i.e. within the temperature
range from 1000 to 1200 K. At higher approach velocities, ahigher inlet temperature is
required to obtain the same conversion of methane (e.g., for a 50% conversion of
methane, the inlet temperatures were 1100, 1150, 1175 K at the approach velocities of
1.0, 2.0, and 3.0 m/s respectively.
100
80
• 60
rj 40
20
900 1000 1100 1200 1300

Fig. 3.10 Calculated methane conversion as afunction of inlet temperature for different
approach velocities; 0.3.5, k3= 1.0 W/m.K,Pt catalyst.

58
3.5.3 Coupled Homogeneous-Heterogeneous Reactions
In an actual catalytic bed both homogeneous and heterogeneous reactions are taking
place. Therefore, it is important to include both these reactions in the model using the
kinetic data for the gas-phase reactions of Ag = 6.6 x 1010 kmo11m3.s, Eg = 180.0 kJ/mol
and for the surface reactions A = 1.03 x i0 kmol/m2.s, and E = 86.0 kJ/mol.
The effect of the inlet temperature and mixture equivalence ratio on methane
conversion in the catalytic bed is shown in Fig. 3.11. As the equivalence ratio of the
mixture is increased, the conversion of the methane is completed at a much lower
temperatute. At temperatures lower than the light-off temperature fuel conversion is

negligible and once the light-off temperature is reached, the conversion rises rapidly. It
can be seen (Fig. 3.11) that the light-off temperature increases with decreasing
equivalence ratio. For example, the light-off temperature for avery lean mixture of j =
0.15 is -4000 K while that for the somewhat richer mixture of = 0.35 is -'740 K.
The effect of the approach velocity on methane conversion within the catalytic
bed is shown in Fig. 3.12. Similarly to the previous two cases (with the inert or
heterogeneous reaction only beds), methane conversion decreases with the increase in the
flow velocity (i.e. as the residence time decreases). For instance, at the velocity of 1.0
m/s, complete methane conversion occurs at an inlet temperature of - 750 K, while at
velocities of 2.0 and 3.0 m/s it occurs at much higher inlet temperatures of— 895 and 987
K respectively. In contrast to the case of heterogeneous reaction only (Fig. 3.10), it can
be seen that this effect of the approach velocity is less profound as the value of the
velocity increases. The same trend was observed experimentally by Depiak and Wierzba
(1999) for different catalysts such as cobalt oxides, chromium oxides and their binary
mixtures. The effect of approach velocity for equivalence ratio of 4= 0.1 on fuel
conversion is given in page 150.
It appears that the gas-phase reactions occurring alongside surface reactions in the packed
bed enhance the methane oxidation rate and allow it to occur at much lower inlet
temperatures than those achieved by the heterogeneous or homogeneous reactions alone.

59
800 900 1000 1100 1200

equivalence ratios; u= 1.0mJs,k = 1.0. W/m.K, Pt catalyst.
100 I
80
.2 60
0
40
U=1.0 mIs
20
u2.Om/s.
u3.Om/s
OS —_J I,
700 800 900 1000 1100
approach velocities; = 0.35, k5= 1.0 W/m.K, Pt catalyst.

60
3.5.4 Effect of Bed Porosity
The porosity of the bed, defined as the ratio of the volume of the void (i.e. gas volume) to
the total volume of the bed, depends on the solid particles size and the method of their
packing in the reactor. For example,. in conventional packed beds, such as distillation and
adsorption columns, the particles are of a relatively large size, typically 1-2 in. in
diameter (Cybulski and Moulijn, 1998). In catalytic beds, however, much smaller
particles are used, with typical diameters between I.and 3mm, and the porosity is much
lower, typically around 0.4. Enlargement of the catalyst particles will lead to apoor
utilization of the catalyst particles. Smaller pore sizes Swill result in higher catalyst
surface-area-to-volume ratios and will increase the relative rate of heterogeneou
reactions, whereas larger pores will tend to allow relatively more gas-phase reactions.
The large particle size also implies that apoor use is made of the reactor space, which is a
significant cost factor. For the same reason, a very loose packing with a very high
porosity will be unacceptable in such aprocess.
The effect of the bed porosity for the same geometrical shape of particles on
methane conversion due to heterogeneous reaction only within a bed 50 mm long is
shown in Figs. 3.13 and 3.14. Methane conversion at the exit of the bed decreases as the
bed porosity increases at the same temperature. Generally, such atrend can be expected
since an increase in the porosity means a smaller catalytic surface area. The largest
differences in methane conversion occur within the inlet temperature range of 1000-1150
K (Fig. 3.14), corresponding to the light off regime. Methane conversion at an inlet
temperature of 1100 K is about 27% higher for bed porosity of 0.20 than that for the bed
porosity of 0.45. For the higher porosity of 0.50 only negligible amounts (-1.0%) of
,methane conversion were ,obtained.

61
100
9.
1 Heterogeneous reaction only

80
S =0.30
8 - 0.35
. 60
4,)
20
=O5O
- 0
700 800 900
-9 .
1000 1100
_f:::.:L — —
1200
_.
1300
Fig. 3.13 Calculated methane conversion as afunction of inlet temperature for various
bed porosities; 4) = 0.35, u= 1.0 m/s, k = 1.0 W/(m.K), L = 50 mm.
100
Heterogeneous reaction only .
80 - - - - - T•m=1000 K
- T1=1050K
Tm=1100K
- T=1150K
. 60
4,)
C
40
20
I I I
00
0.1 0.2 0.3 0.4 05
Porosity
Fig. 3.14 Calculated methane conversion as afunction of bed porosity for different inlet
temperatures; 4) = 0.35, u= 1.0 m/s, k = 1.0 WIm.K, L = 50 mm.

62
The performance of the catalytic reactor model was different when both the
homogeneous and heterogeneous reactions were accounted for. It can bee seen (Fig. 3.15)
that even at the relatively low temperature of 750 K complete methane conversion could
be obtained within abed 50 iiim long for arange of the bed porosities (c = 0.20 - 0.40).
Moreover, with an increase in the bed porosity from 0.20 to 0.35, complete conversion
took place at an earlier location within the reactor. However, further increase in the bed
porosity to 0.40 resulted in the full consumption of methane at alocation farther from the
inlet to the reactor. And in the case of the porosity of 0.45 there was no methane
conversion at all within abed 50 mm long. Such abehavior is most probably due to the
following competing factors. An increase in the bed porosity results in an increase in the
bed temperture (Fig. 3.16) due to the reduced bed solid mass and its heat capacity. This
enhances the oxidation reaction. Moreover, the increase in the porosity results in a
decrease in the local velocity and an increase in the residence time within the bed. On the
other hand, the increase in the porosity decreases the catalytic surface area which is
essential in promoting the methane oxidation at such alow temperature (750 K). For the
bed porosity of 0.40 the later factor is probably dominant, which results in shifting the
oxidation reactions to alater (downstream) location within the bed. And it appears that
for the bed porosity of 0.45 the catalytic surface area is not enough to initiate the
oxidation process.
It is also worth to mention that the maximum value in the gas temperatures (peak)
for the mixture of = 0.35 are generated by the thermal energy released by methane. This
maximum value in the gas temperature diminishes as the mixture reaches the equilibrium
state due to heat exchange between the gas and solid phases by convection. Also, it is
worth emphasizing that the maximum gas temperature for the methane-air mixture is
below 1700 K. Thus, a rule-of-thumb, the thermal NO mechanism is usually

unimportant at temperatures below 1800 K.
63
0.02
0.0175
0.015
0.0125
0.01
. 0.0075
0.005
0.0025
0 •..__I I I I I a I
0 0.01 0.02 0.03 0.04 0.05
Distance Along the Bed (m)
Fig. 3.15 Effect of bed porosity on methane mass fraction along the packed bed for
=O.35, u=1.O m/s, k=l.O W/m.K, and T= 750 K; homogeneous-heterogeneous model.
1700
1600
1500
1400
N
c=0.20 =O.3O
N
s=O.35
1300
I e=O.40
1200 I
I
1100 I
I
1000 1
/
/
900 /
/ 0.45
800
700
0 0.01 0.02 0.03 0.04 0.05
Fig. 3.16 Temperature distribution for the gas (solid line) and the solid (broken line) for
various bed porosities with 4i = 0.35, u = 1.0 m/s, ks = 1.0 Wlm.K and Tin = 750 K;
homogeneous-heterogeneous model.
64
3.5.5 Effect of Bed Length
It is expected that the bed length would influence fuel conversion. The effect of the bed
length on the methane conversion due to surface reactions only is shown in Fig. 3.17 for a
bed porosity of 0.5. It can be seen, that although no methane conversion was obtained
within a shorter bed of 50 mm long, the complete conversion of the methane was
obtained for abed of increased length (75 and 100 mm). Increasing the bed length while
other parameters kept constant increases the surface area of the catalyst as well as the
residence time, i.e. more time is available for the completion of the oxidation reactions.
The maximum methane conversion is obtained for bed porosity of c= 0.2, therefore, the
effect of the length of the bed at different inlet temperatures and bed porosity of 0.2 is
illustrated in Fig. 3.18. The maximum increase in the conversion of methane as the bed
length increased is at the inlet temperature of 1050 K which corresponds to the start of
the light-off regime of the catalyst. For example at this temperature, the increase in
methane conversion is 35.7 % with an increase in the bed length from 50 to 100 mm.
However, this increase in the methane conversion decreases to avalue of 17.2 % with an
increase in the bed length from 50 to 75mm. It can be seen also that increasing the inlet
temperature further diminishes the effect of the bed length (e.g., at the inlet temperature
of 1200 K). At such relatively high temperatures this behavior is expected because the
mass diffusion processes are controlling the combustion process. The results suggest that
the increase in the catalytic surface area as well as the heat capacity of the longer beds do,
not have a significant influence on methane conversion; such behavior is in agreement
with the reactor performance at the mass diffusion regime.
The effect of the length of the bed on methane conversion can also be seen in Figs. 3.19'
and 3.20 for different bed porosities. Comparison of the results (Figs. 3.13, 3.19 and
3.20) shows that at the same inlet temperatures and for the same porosity the methane
conversion values are significantly higher for the longer bed of 100 mm than those for the
shorter bed of 50 mm as expected. For instance, at the inlet temperatures of 1100 K for
the bed porbsity of 0.2 and bed lengths of 50 and 100 mm, methane conversion was
66.9% and 93.6% respectively. Moreover, for the longer bed of 100 mm complete
methane conversion can be achieved even with-a very high value of bed porosity of 0.9.
65
100
Heterogeneous reaction only
80
L=75min
100 mm
. 60
40
20
L=50mm
0-r - - ,-I J - - - l_I - - I_I -- + -,-
700 800 900 1000 1100 1200 1300

bed lengths; c= 0.50, 0.35, u= 1.0 m/s, k5= 1.0 W/ m.K; Pt catalyst.
100
80
g
• 60
qu
C
40
20
1000 K
0
50 75 100
Length of Bed (nun)
Fig. 3.18 Calculated methane conversion as a function of bed length for different inlet
temperatures; u= 1.0 m/s, 4= 0.35, s= 0.2, k 1.0 W/m.K; Pt catalyst.

66
100
80
• 60
0
40
20
700 800 900 1000 1100 1200 1300

bed porosities; L= 75 mm, 4= 0.35, u= 1.0 m/s, k = 1.0W! m.K; Pt catalyst.
800 900 1000 1100 1200 1300

bed porosities; L = 100 mm, 4= 0.35, u= 1.0 m/s, k = 1.0 W/ n.K; Pt catalyst.
67
It can also be seen (Fig. 3.21), that at the relatively high inlet temperature of 1300 K the
effect of porosity is rather small and that complete oxidation of methane is achieved
already at ashort distance from the inlet to the reactor for both porosities. However, at
the lower inlet temperatures, the effect of the porosity becomes significant. Few factdrs
contribute to the observed trends. As the catalytic surface area is increased so the surface
reactions increased, which is important to the heating of the solid. Expectedly, the
exothermic catalytic surface reaction will increase the solid temperature and this increase
in temperature will enhance methane conversion. Moreover, for the longer bed, its heat
capacity is larger which also facilitates an increase in the temperature of the bed. The
difference in methane mass fraction at the inlet temperature of 1100 K, is greater than at
1000 or 1200 K for bed porosity of 0.2 aiid 0.9 due to the high difference of methane
conversion at the inlet temperature of 1100 K.
Figure 3.22 illustrates the effect of both the bed length and bed porosity on
methane conversion at the inlet temperature of 1100 K. The highest methane conversion
is obtained for the bed length of 100 mm followed by the bed length of 75 mm for all
porosities employed in this investigation ranging from 0.2 to 0.9. For the bedlength of 50
mm, methane conversion is negligible for the bed porosity of s≥ 0.5 for the reasons
mentioned earlier. The results suggest that for abed length of 50 mm with bed porosities
of s≥0.5, the catalytic surface area has the key role in methane oxidation which seems as
if it is not large enough to initiate the oxidation of methane.
The temperature of the solid at the exit of the bed versus the bed porosity for
different inlet temperatures with abed length of 75 mm is presented in Fig. 3.23. It can be
seen from Fig. 3.23 that the solid temperature exceeds the inlet temperaure due to
exothermic reaction at the catalytic surface. This increase in the solid temperature is
always beneficial in enhancing the methane conversion. The smaller the bed porosity is
the higher the difference between the inlet and the solid temperature The maximum
effect occurs for inlet temperatures ranging from 1050 to 1100 K. (i.e., the light-off
regime where most of the methane conversion takes place) with the bed porosities of s<
0.5 where more than 57% of methane has been reacted.

68
0.02
t ..
0.0175 L
I .. .
I
0.015 + ..
a ••
0.0125 ..
Th •\*
0.01
:tt
-
•\
. 0.0075
T )
0.005 : --- ---- 1000
1100
- — 1300
0.0025 : -.-.- 1000

----.- 1100 ••_••_.._.._..
- - 1300 ,
I I
0 0 0.02 0.04 0.06 0.08 01

Fig. 3.21 Methane mass fraction along the bed for various inlet temperatures for c= 0.2
(thick line) and a= 0.9 (thin line; *), k = 0.35, u = 1.0 m/s; heterogeneous reaction, Pt
catalyst.
100

..-
80
.5
"p . .5 -
. 60
S ..
C
cj 40
Tin = 1100 K
20 L =100nun
L=75mm
L=50mm
0 I I I
00 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 10
Bed Porosity
Fig. 3.22 Calculated methane conversion as afunction of bed porosity for different bed
lengths; u=1.0 m/s, = 0.35; Ti,, = 1100 K, ks= 1.0 W/m.k; Pt catalyst.
69
1400
T in Heterogeneous reaction only
1300K
1200 K
1150K
1100K
1075 K
1050 K
_ . .-. - .-.
- . _ -
- 1000K - --------
I IIIIIIIII1Ii 11 I1111I1111I
I I IIIIIIIIIIIII i
00 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 10

Bed Porosity
Fig. 3.23 Bed solid temperature at the bed outlet as afunction of porosity for various inlet
temperatures; u= 1.0 m/s, 4) = 0.35, L = 75 mm, k = 1.0 W/m.K; Pt catalyst.
Furthermore, Fig. 3.23 shows that the solid temperature decreases as the bed porosity
increases due to the corresponding decrease in the catalytic surface area per volume.
Therefore, alower catalytic surface reaction rate will lead to lower solid temperatures and
lower methane conversion as a consequence. At much higher temperatures (i.e. Tin ≥
1175 K), methane conversion reaches 90 - 97% for bed porosities ranging from 0.2 - 0.9.
Therefore the heat release due to the surface reaction is much smaller than at the lower
inlet temperature. Thus, the increase in the solid temperature at the exit is very small.
70
In the case of coupled heterogeneous-homogeneous reactions, the effect of bed length is
less profound, as can be seen in Fig. 3.24 for = 0.35, u= 1.0 m/s at the inlet temperature
of Tir,= 750 K and for various bed lengths. Methane conversion for the bed porosity of s
= 0.40 is not enhanced by increasing the bed length from 50 to 100 mm. The location of
the complete oxidation of methane occurs at the same distance into the bed for both bed
length of 50 and 100 mm as shown in Fig. 3.24 (b) and (c). However, no methane
conversion for the shorter bed of 25 mm long was obtained (Fig. 3.27 (a)) at such low
temperature (750 K). It appears that the bed length is not enough to induce the oxidation
processes in the bed due to the smaller catalytic surface area and shorter residence time.
The effect of inlet temperatures on methane conversion for the longer bed of 100 mm is
illustrated in Fig. 3.25 in the gas and solid phases temperature distribution along the bed
for abed porosity of è= 0.45. No methane conversion is obtained at the inlet temperature
of 750 K. However, at the higher inlet temperature of 760 K, complete conversion of
methane is obtained at the exit of the bed. Increasing the inlet temperature further
allowed the complete conversion to take Olace at an earlier location into the reactor (e.g.,
methane oxidation completed at the 9mm for the inlet temperature of 800 K). The results'
suggest, that although the longer bed has larger catalytic surface area and longer residence
time, it is still not enough to initiate methane oxidation at the inlet temperature of 750 K.
Expectedly as the inlet temperature increases, the role of the gas-phase reactions
increases too and so does the conversion of methane.
71
1800
1600
(a)
1400
1200
E- 1000 Gas
- - - - Solid
800
I,I I II,, I-
0 0.005 0.01 0.015 0.02 0.025
1800
1600 (b)
1400
1200
E
E
- 1000
Gas
- - - - solid
800
I I I r I I I
0.01 0.02 . 0.03 0.04 0.05

1800
1600
(c)
1400
1200
B
E
- 1000
Gas
Solid
800
0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09 01

Fig. 3.24 Temperature distribution along the bed for different bed lengths; (a) L = 25
mm, (b) L 50 mm, (c) L = 100 mm, = 0.35, u = 1.0 m/s, F, = 0.4, T= 750K;
homogeneous-heterogeneous model, Pt catalyst.

72
The influence of both the bed length and bed porosity on methane conversion is presented
in Figs. 3.26 and 3.27 at the inlet temperature of Tin = 800 K for bed lengths of L = 100
and 50 mm respectively and for various bed porosities. The complete conversion of
methane is obtained for the bed porosities of s= 0.40, 0.45, 0.50, and 0.53 for L = 100
mm. A negligible amount of methane (i.e., less than 1.0%) is converted for bed porosities
of ≥ 0.55 as it can be seen from Fig. 3.27. Furthermore, the results suggest that the
optimum value of the bed porosity at this temperature (T m = 800 K) is the bed porosity of
= 0.40. Although the location of the complete oxidation of methane is negligible
between the bed porosities of 8 = 0.40 and 0.45, the temperature of the exhaust gas is
lower for the bed of s= 0.40. For the bed length of L = 50 mm (Fig. 3.27), the value of
the maximum porosity is c= 0.50 for the complete conversion of methane to take place.
As mentioned earlier for shorter beds the catalytic surface area is smaller and less
residence time is available for the fuel to oxidize.
The performance of the coupled heterogeneous-homogeneous reactions is different than
the case of the heterogeneous reaction only. It appears more likely in this case (eyen at
such moderate temperatures) that assuming the presence of gas-phase reactions occurring
alongside surface reactions in the bed, will offer a more effectively predictive and
sensitive model.-
73
1800
1600
a 1400
I
1200
1000
800
I I
0.00 0.02 0.04 0.06 0.08
Fig. 3.25 Temperature distribution for the gas (solid line) and the solid (broken line)
along the packed bed for various inlet temperature; 4 = 0.35, u = 1.0 m/s, k8 = 1.0
W/m.K, s= 0.45, L = 100 mm; homogeneous-heterogeneous model, Pt catalyst.
1800
1600
a 1400
I 1200
ENO
1000
74
1800
1600 /
Tm =800K
1400
&= 0.45
1200 /
/
= 0.50
/
1000 /
I
0.52
800
I II I I I I 1I I , I
0.00 0.01, 0.02 0.03 . 0.04 0.05
Fig. 3.27 Temperature distribution for the gas (solid line) and the solid (broken line) for
various bed porosities with 0.3 5, u= 1.0 m/s, k = 1.0W/m.K, Ti,= 800 K, L = 50
mm; homogeneous-heterogeneous model, Pt catalyst.

75
3.5.6 Effect of Thermal Conductivity of the Bed of Solids
Calculations show (Fig. 3.28) that an increase in the solid thermal conductivity of the bed
from 0.5 W/(m.K) to 4.0 W/(m.K) has no effect on methane conversion within abed of
50 mm long when only heterogeneous reaction is considered.
The methane mass fraction along the bed is plotted in Fig. 3.29 for the above
values of thermal conductivity at various inlet temperatures. The. effect of solid thermal
conductivity is negligible at the kinetic control regime of the catalyst where the methane
conversion is about 10% or less at the inlet temperature of Tj 1000 K. However, as the
inlet temperature increases and reaches into the light-off regime the effect of solid
thermal conductivity is more apparent on the mass fraction along the bed (i.e. at Tin =
1100 K). The increase in the inlet temperature further reduces the effect of solid thermal
conductivity on the mass fraction of methane along the bed. This corresponds to the
range of temperature between Ti,, = 1200 to 1250 K where most of the methane is already
consumed. It can be seen from Fig. 3.29 at an inlet temperature of Tin = 1100 K, that the
higher the conversion of the methane along the bed the more profound the effect of
thermal conductivity. At higher inlet temperatures (1200 and 1250 K), the influence of
the thermal conductivity is larger at the beginning of the bed where most of the methane
is oxidized. This effect diminishes as the methane conversion reaches completion along
the bed.
76
100
80 k0.5W/mK
k: = 1.0 W/mK
k =2.0 W/mK
. 60 k5 =3.OW/mK
k=4.0W/mK
(40
20
I I I I I i I r I
00 800 '900 1000 1100 1200 1300

solid thermal conductivities; 4) = 0.35, u = 1.0 m/s, L = 50 mm, a= 0.4; Pt catalyst.
0.02
0.0175
0.015
0
•' 0.0125
z 0.01
k1=0.5 W/mK
.0.0075
k8= 1.OW/niK
kg=20W/niK
0.005 k4.0W/mK
0.0025
0
0.01 0.02 0.03 0.04 0.05
Fig. 3.29 Methane mass fraction along the bed at various inlet temperatures for different
solid thermal conductivities, 4) = 0.35, u = 1.0 m/s; heterogeneous reaction, Pt catalyst.'

77
The effect of the thermal conductivity when the coupled homogeneous-heterogeneous
reactions are considered in the model is shown Fig. 3.30. It can be seen that the value of
the thermal conductivity affected the location of complete methane conversion within the
bed. The higher the value of ksis, the shorter the distance needed to complete the methane
conversion. Figure 3.31 represents the temperature profiles for the gas and solid for the
above cases. It can be seen that an increase in the solid thermal conductivity will increase
the solid temperature significantly at the inlet part of the bed due to enhanced heat
conduction in the bed, and this will accelerate the oxidation process. Thus, the full
consumption of methane will take place at an earlier location within the catalytic reactor.
Also, it can be seen that higher values of thermal conductivity result in lower, exhaust gas
temperatures due to increased heat dissipation rates. It was also found that there will be
no conversion of methane for a solid thermal conductivity below avalue of k = 1.0
W/m.K. This is in agreement with the results of Groppi et al. (1999). This is the case
where heat conduction is negligible such as for ceramic material. However, for all values
of k = 1.0 - 4.0 W/m.K, complete conversion was achieved within abed 50 mm long at
Tin =750K.
78
0.020
0.018
to
0.015
M 0.013
0.010
0.008
0.005
0.003
0.01 0.02 0.03 0.04 0.05

Fig. 3.30 Methane mass. fraction along the packed bed for different values of thermal
conductivities of the solid bed; = 0.35, u= 1.0 m/s, e= 0.4, T= 750 K; homogeneous-
heterogeneous reactions, Pt catalyst.
1600
1400
1200
1000
800
0.01 0.02 0.03 0.04 0.05

phases along the bed for different solid thermal conductivities; 0.35, u = 1.0 m/s,
s=0.4, T1 =750 K; homogeneous-heterogeneous reactions, Pt catalyst.

79
CHAPTER 4
EXPERIMENTAL APPARATUS AND PROCEDURE
4.1 Motivation
The approach of the present study has been to examine catalytically supported
combustion in awell characterized system in which most of the important physical and
chemical processes found in larger-scale catalytic combustors are present. The geometry
chosen is apacked bed reactor. Studies of catalytic combustion reported to date tend to,
stress either experimental or theoretical aspects, and few make the comparison between
theoretical and' experimental results necessary to understand the essence of surface
combustion (Mori et al., 1977; Groppi, 1999). The parallel development of anumerical
modeling program was necessary for the analysis of the experimental results obtained in
this study.
One of the objectives of this study was to obtain experimental data on fuel
conversion at different operational conditions (inlet temperature, equivalence ratio, and
approach velocity) and compare the data with the corresponding numerically predicted
data to determine the reaction rate constant and activation energy for aone-step surface
reaction. Moreover, the effectiveness of the catalyst for complete combustion of lean
fuel-air mixtures at relatively low temperatures 'and atmospheric pressure was to be

determined experimentally.
80
4.2 Experimental Apparatus
The apparatus required for this investigation had already been designed and was
operational (Mehta, 1990; Khalil, 1993; Depiak, 2003). However, some modifications
(and repairs) were made to meet the objectives of the present investigation. A schematic
diagram of the experimental apparatus is shown in Figure 4.1. The apparatus consists
mainly of a catalytic packed bed reactor, a compressed air supply and main heater
assembly capable of providing a wide range of air velocity and temperature, and
instrumentation (choked nozzle flow meters, thermocouples, gas analyzers for exhaust
gas diagnosis, etc.). A photographic view of the apparatus layout is shown in Fig. 4.2
which displays the above mentioned main components of the set-up. The main parts of
the apparatus are made of stainless steel (#316L) for durability as well as to withstand
continuous operation at high temperature.

2
Gas Cylinder Fuel Injector
4r T
r Thermocouple Read-out
System Exhaust Gas
Cooling System
1
I Main Heater
Catalytic Reactor
2
Temp. Controller Flame Trap
Auxiliary Heater
Gas Analyzers
( Holding,
Dryer
Tank
Legend
1. Thermocouples
2. Chocked nozzles flow meters
Compressor
Fig. 4.1 Schematic diagram of the experimental apparatus.

Fig. 4.2 A photographic view of the experimental apparatus.
83
4.2.1 Catalytic Reactor
The reactor is aquartz tube which has a28 mm inside diameter and is 300 mm long.
Figure 4.3 shows a' cross-section view of the reactor. An external electrical ceramic
radiant heater has been installed to provide a'100 mm long section of uniform
temperature (± 3 °C) along the reactor. This auxiliary heater is connected to adjustable
powerstats to obtain the desired uniform temperature. Within this section there is a50
mm long catalytic bed made of 3.2 mm diameter 7-alumina base pellets held in place by
two 25.4 mm long honeycomb monoliths (ceramic cordirite-Celcor; manufactured by
Corning Glass) as illustrated in Fig.4.4. An opening in the center of the honeycomb
monolith piece at the end of the packed pellet is made in order to slide in and out asheath
thermocouple measuring the exhaust gas temperature.
A high temperature heating tape (Omega series FGS high temperature heating tape of 627
Watts and 25.5 x 152.4 mm) was wrapped around the pipe system (including aflame trap
and fuel injector) connecting the main heater with the reactor to minimize the heat loss.
Also, aspecial insulation that can withstand high temperature was wrapped around the
piping system. The reactor can be seen in Figs. 4.2 - 4.4.

Radiant Heater
/
1
r Heating Tape / Packed Bed

/ / /
/ / I Insulation
/
/
4,
z. ••
Exhaust gas
/ sampling
/
probe
/
/
/
t
i i/I
1 / 1
/
_ Honeycomb
I
Monolith
• NN N \\
1/
Thermocouples V
Fig. 4.3 Cross-section view of the reactor.

Fig. 4.4 A photographic view of the experimental packed bed.
86
4.2.2 Compressed Air and Main Heater Assembly
Compressed air is supplied to the apparatus from the laboratory compressed air line. This
line is connected to an air filter to remove any moisture or oil residue in the air at the inlet
to the apparatus. A pressure regulator is installed after the air filter to regulate the air
supply into the choked nozzle assembly. This pressure regulator is able to provide
compressed air with maximum pressure of 100 psi. The compressed air at 'the required
mass flow rate is passed through achoked nozzle flow meter to determine the air flow
rate into the main heater. The main heater assembly consists of six 1.5 kW ceramic
heating elements made of Ni-Cr wire. These elements are mounted in astainless steel
rectangular box with gas inlet and outlet ports. They are controlled with aprogrammable
microprocessor-assisted temperature controller system. The main heater is connected to
high voltage power supply of 208 V. The details of the main heater assembly can be seen
elsewhere (Mehta, 1990). A maximum temperature of 625 °C was set in order to ensure a
longer running life for the heater's elements. The main heater assembly was controlled by
aPD temperature controller with aprogrammed microprocessor which maintained the
desired air temperature value for each running condition with accuracy of ± 0.2% of
reading. Temperature was measured by aK tye thermocouple placed at the exit of the
heater and connected to the temperature controller. This assembly is capable of supplying
air over awide range of temperatures (293 - 898 K).
4.2.3 The Choked Nozzle Meter System
Flow rates of the fuel and air entering the reactor were metered by apre-calibrated set of
choked nozzles. Figure 4.5 shows aphotographic view of the control panel of the choked
nozzle metering system used throughout the course of this study. A wet test meter and/or
orifice plates were used for calibration of the chocked nozzles depending on the flow
rate. Typical calibration figures are shown in Appendix B.

87
Fig. 4.5 A photographic view of the choked nozzle meters assembly.

88
4.2.4 Fuel Injection System
The system for fuel injection was designed to achieve ahomogeneous fuel-air mixture at
the inlet to the reactor. The radial-jet fuel injector has an inner chamber of 12.7 mm
diameter. The chamber contained 12 radially drilled holes of 0.4 mm diameter each, and
equally spaced around the inner periphery of the injector. The injector was positioned
approximately 500 mm upstream from the reactor. The fuel-air mixing was further
enhanced by the presence of aflame trap positioned downstream of the injector.
4.2.5 Exhaust Gas Analysis System
Gas samples were drawn during experiments using awater cooled 1/16-in (1.58-mm)
inside diameter stainless steel probe placed at the center line of the reactor at its end (Fig.
4.3). Use of the water cooled probe allowed the experimentor:
1. to quench the reactions within the gas sample quickly so that further chemical
reactions were halted (i.e. freezing the reactions),
2. to condense the water vapor in the exhaust gas,
3. to cool down the exhaust gas before it entered the gas analyzers. The exhaust
gas enters the probe at atemperature of up to 1400 K (this temperature depends
on the inlet mixture's temperature; equivalence ratio of the mixture and
percentage of the converted fuel), but enters the gas analyzers at atemperature
around 300 K.
Provision was made to process a gas sample using either gas analyzers or a gas
chromatograph. A valve was installed upstream of the probe connected to two
polypropylene tubing lines of 6-mm outside diameter. One line is connected to aset of
gas analyzers while the second line is connect to agas chromatograph for gas analysis.
The exhaust gas samples were withdrawn from the reactor with the aid of a sampling
system which includes asuction pump, awater trap, apenna drier, apressure regulator,
and a flow meter. In the present investigation the sample was delivered to the gas
analyzers at aflow rate and pressure of 800 ml/min and 112 kPa respectively. Species
89
concentrations in the exhaust gas were measured using Beckman gas analyzers (Model
864): an infra-red analyzer for hydrocarbons such as CH4 (0.05% accuracy), and infra-red
analyzers for CO and CO 2 (0.01% and 0.06% accuracy correspondingly). A magneto-
penu'matic analyzer (Model 755) was used to measure 02 concentration (0.1% accuracy).
The gas analysis system is shown in Fig. 4.2. A multi-channel data acquisition system
was connected to the gas analyzers to monitor the concentration of each constituent of the
exhaust gas.
Samples could also be analyzed using a3800 Varian gas chromatograph (GC) as
illustrated in Fig. 4.6. The sampling system in this case includes asuction pump, purge
line, and asample container that can hold up to six liters of sampled exhaust gas. This
sampling system is connected directly to the GC. The GC analysis was performed using
two columns in series. A flame ionized detector (FJD-GC) was employed to detect the
hydrocarbons such as CH4,C2H6, and C3H8. A thermal conductivity detector (TCD-GC)
was also used for detecting CO, CO 2,02, and N2 in the exhaust gas. The feed sample.
flow rates as well as the calibration gas flow rates into the GC were set at 100.0 ml/min.
The gas chromatograph was calibrated using standards for all the species listed above
except H20. From the preliminary test, the total time required for full analysis of the
sample, including a10-minute stabilizing period and 2-minute of retention period for the
FIDD column, as well as a 15-minute stabilizing period and a11-minute retention period
for TCD column, was 37 minutes. However, the total time required for full sample
analysis using the set of analyzers was only 4-5 minutes. Table 4.1 shows the value of
met
hane measured using the two apparati mentioned above for = 0.35 at different inlet
temperatures. The maximum difference in the value of measured methane between the
reading of the gas chromatograph and the gas analyzer was 0.71 % of reading. Thus it
was mostly the gas analyzers which were used throughout this investigation for
consistency and efficiency.
90
Table 4.1 Comparison between the measured methane using the gas chromatograph and
the gas analyzer for 4= 0.35 at different inlet temperatures.
Measured Methane
Measured Methane
Inlet Temperature using the Gas Difference
using the GC
(K) Analyzer (%)
(/o)
(%)
292 3.49 3.5 0.29
459 . . 3.5 0.0
524 3.46 . 3.45 0.29
573 3.44 3.44 0.0
651 3.41 3.40 0.0
726 3.33 3.35 0.60
773 3.19 3.18 0.31
798 2.91 2.90 0.34
869 2.78 2.8 ' 0.71

Fig. 4.6 Exhaust gas sampling probe with gas chromatograph.
92
4.2.6 Instrumentation and Measurements
• Temperature Measurement
The temperatures of the fuel-air mixture at the inlet, the outlet, and within the reactor
were measured by aset of Inconel 600 sheathed K-type (chromel-alumel, i.e., Ni-
Cr/Ni-Al) thermocouples with 1/16-in OD.
Thermocouples were also used to monitor the temperature of the air at the exit from
the main heater and the temperature of the wall at the inlet to the reactor. In order to
measure the gas temperature at the exit from the reactor, axial thermocouple was
placed through the honeycomb monolith as shown in Fig. 4.3. Two other
thermocouples were used for monitoring the wall temperature of the reactor catalytic
bed. The loëations of the above thermocouples are shown in Figs. 4.1 and 4.3.
The thermocouples were connected to athermocouple readout through aconnector
block which can accommodate six independent thermocouples. The temperature
distribution in the radial direction at the outlet from the reactor was measured during
the preliminary tests using atransverse thermocouple. This distribution is shown in

Appendix C Fig. C.1).
Measured temperatures can be different than actual gas temperatures due to heat
losses via conduction in the wires, radiation from the wires, and conduction and
convection from the gas to the wires. This analysis for the thermocouple correction is
shown in Appendix C. However, temperature values f'or, the experimental data
represent uncorrected measured values. The accuracy in the thermocouples
measurements for K-type is 2.2 °C or 0.75% of the reading whilst, an uncertainty of±
0.5% of the measured values is expected in the thermocouples readout.
• Pressure Measurement
The pressure drop in the packed bed reactor was measured using differential pressure
transducer. The pressure taps were mounted at the inlet and outlet of the 300 mm long
reactor. Figures D. 1and .D.2 (Appendix D) show the pressure drop along the packed
93
bed reactor which varied from 0.08 to 0.54 kPa ±0.5 Pa for the flow rates of 0.03 and
4.8 m3/h respectively. Such small pressure drops mean that the reactor effectively
operated under atmospheric pressure (the local atmospheric pressure is 89 kPa).
4.3 Experimental Procedure
The apparatus was regularly checked for leaks before taking measurements. The steps
required to prepare the experimental apparatus (i.e. calibration of equipments, check for
leaks, etc.) before acquiring each set of data were:
1. Opening of the fuel cylinder (i.e., standard calibration gases, fuel and nitrogen)
valves and setting the pressure gages to the desired pressure.
2. Calibration of all the gas analyzers; starting with the oxygen analyzer followed by
carbon dioxide; carbon monoxide and methane analyzers.
3. Calibration of the GC was checked once aweek only, in cases when the GC was
used.
4. Switching-on all the equipment and instrumentation being used (see section 4.2 of
this chapter).
5. Switching-on the water supply for the exhaust gas sampling probe.
6. Opening the valve to the gas analyzers or to GC.
7. Tuning the choked nozzle valve to the required pressure; calculated for adesired air
flow rate.
8. Setting amethane flow rate to the required value by adjusting the choked nozzle
pressure corresponding to the desired value of the fuel-air mixture equivalence

ratio.
9. Opening the valve for methane injection allowing it to flow through the reactor.
10. Analyzing the gas sample at room temperature. This step is used to ensure the
• required mixture equivalence ratio was obtained properly. Also, it is amethod for
eliminating the possibility of leaks throughout the system.

94
11. If the required equivalence ratio was obtained correctly, the methane injector valve
will be switched-off.
12. An extra precaution was employed throughout the experimental part of this
research. In cases of compressed air shut off due to compressor failure or leaks etc.,
a standby nitrogen cylinder was connected to the apparatus. The, compressed
nitrogen supplies aflow through the reactor which will cool,the main heater and the
catalytic bed as well to prevent damage to either part.
The following procedural steps were followed in obtaining the experimental data in the
order in which they appear.
1. Setting the main heater controller to the required air temperature.
2. Switching-on the main heater. The time needed to reach desired steady state
temperature depends on values of the air velocity and temperature. In those cases
when high inlet gas temperature experiments were conducted special attention was
paid to setting the required main heater temperature. A rate of 50 °C per five
minutes was adopted in raising the main heater temperature in order to prolong the
life of the elements of the main heater and to avoid more frequent repairs.
3. Switching-on the power of the auxiliary radiant and tape heaters and adjusting their
powerstats to the desirable temperature.
4. Recording the temperatures from all the thermocouples.
5. Opening the valve of the methane injector once the steady state temperature was
reached (usually, it took five to 15 minutes to reach asteady state temperature for
values between 400 and 900 K) and recording the temperature at the inlet and exit of
the reactor.
6. Analyzing exhaust gas sample withdrawn from the reactor after 30 seconds of the
methane injection. This time corresponds to the response -of the first gas analyzer
(i.e. 02 analyzer).
7. Recording the readings of all the analyzers as well as the thermocouples after a
steady conversion of methane is reached (usually , to 5minutes).
8. Switching-off the methane injection valve.

95
9. Resetting the main heater controller to ahigher inlet air temperature for the next run'.
10. Repeating steps 3to 8.
After covering the required range of inlet temperatures within the capability of the
apparatus, the following shut-off procedure was adopted:
1. Switching-off the power to the radiant and tape heaters.
2. Reducing the main heater set' temperature 50 °C per five minutes while only air is
flowing through the reactor until atemperature of 100 °C was reached. This measure
was adopted to help to prolong the life of the elements used in the main heater
assembly.
3. Switching-off the power to the main heater and allowing the cooling process of the
reactor.' -
4. Closing the upstream valve of the gas sample probe.
5. Shutting-off the water supply to the cooling sampling probe.
6.. Closing the methane cylinder valve as well as the standby nitrogen cylinder value.
7. Switching-off all other instrumentation.
4.4 Pellet Materials for the Packed Bed Reactor
Non-catalytic and catalytic pellets were employed in the reactor. For a non-atalytic
packed bed (inert packed bed) Gamma alumina oxide' (y-'A1203) pellets manufactured by
Johnson Mattey Inc. with aspecific surface area of about 300 m2/g were used (Alfa Aesar
catalog, A Johnson Matthey Company, 2001-02).
For catalytic bedpellets, two different catalysts were used, namely platinum and anon-
noble metal oxide catalyst (a binary mixture of cobalt oxide and chromium oxide,
Co 3O4JCr2O3,3.13 ratio by mass). These catalysts were deposited on the same gamma-
alumina oxide ('y-A1 203)pellets as the non-catalytic pellets. The loading of the platinum
catalyst, "manufactured by Johnson Mattey Inc., was 0.5% Pt by weight with aspecific
surface area of about 90 m2/g, while the loading of C0 304/Cr2O3 catalyst, made in house
(Depiak, 2003), was 5.33% by weight. ,

96
A set of preliminary tests was conducted to measure the apparent density and the porosity
of the packed beds. The average apparent density which includes the effect of the bed
porosity was found to be 100.0 kg/m3,the porosity of the bed was measured by the
investigator on the basis of several trials as being between 0.38 and 0.42 depend on the
packing of the pellets. These values were consistent with the values cited in the literature
for packed beds (Cybuiski, and Moulijn, 1998).
Experiments were conducted with methane as the primary fuel in this study which was
supplied from high pressure cylinders. Methane of high purity grade of 99.9% by volume
(<0.2% nitrogen balance) was used.
4.5 Apparatus Limitations and Operational Parameters
A series of preliminary tests were conducted which assisted in establishing operating
ranges and apparatus capabilities. The operating range of the apparatus was set by these
preliminar
ytests.
Experiments were conducted with lean methane-air mixtures of different equivalence

ratios (0.2 - 0.6) at different inlet temperatures up to 920 K and different approach
velocities up to 3.0 m/s, calculated at the reference temperature of 293 K and an
atmospheric pressure of 88 kPa.
It is customary in chemical industries to use the parameter "space velocity" instead of an

approach velocity. The space velocity "V5" is defined as the ratio of the volume flow rate
of the mixture "Q" (m3/h)to the volume of the reactor "V" (m) (Eq. (4.1)).
M /(rn 3h)) (4.1)
The value of the space velocity used in the present investigation based on the above
definition is between 54,000 and 216,000 (m3/(m3h)) corresponding to the approach
velocities between 0.75 and'3.0 m/s respectively.

97
The maximum inlet temperature ( 1040 K) for the inert packed bed was higher than the
above limited temperature value of 920 K. The maximum inlet temperature (1040 K) was
used at the early stage of this study and alarge number of difficulties and problems were
encountered. Thus, a decision was made to limit the operating inlet temperature to a
lower and safer operational value of 920 K.
Another limitation was discovered during the experiments. The temperature inside the
reactor could not exceed 1300. °C. Beyond such atemperature, the quartz could start to
soften and deform (melting point of quartz 1600 °C (1873 K). Thus, the temperature
inside the reactor was monitored and kept below 1200 °C for all the experiments
conducted in this investigation.

98
CHAPTER 5
EXPERIMENTAL RESULTS'
5.1 Introduction
The effect of various operational parameters, such as inlet temperature, equivalence ratio,
and approach velocity was investigated experimentally using the apparatus described in
Chapter 4. Three different beds were employed: inert (y-A1203 pellets); and two catalytic
('y-A1203 with 0.5% Pt and C0304/Cr2O3 (3.13 ratio by mass) with 5.33% loading by
weight). The majority of the experiments were conducted using the platinum catalytic
bed. The data obtainea were used to validate the mathematical Imodel and to obtain
kinetic data (activation energy and pre-exponential factor) for the surface reaction on Pt
and C0304/Cr2O3 catalysts.
The concentrations of the measured species in the exhaust gas were based on the
dry volumetdc percentage. They were corr

ected to account for the moisture (1120) that is
removed from the exhaust prior to analysis. This correction yields so-called wet
concentration. All the experimental data presented for species conversion were expressed
on wet basis: The exhaust gas correction is discussed in detail in Appendix E.
The value of the conversion of methane was calculated as:
CH 4 LCH 4 CH4,,,, - CH4,0.

(5.1)
where, CH4,
in represents the inlet concentration of methane in the mixture and CH4, 0 t
represents the corrected measured methane concentration at the exit of the reactor.
99
5.2 Inert Packed Bed
The experimental data obtained during the present work as well as the experimental data
of Depiak and Wierzba (1999) have been used to find the kinetic data for the numerical
simulation of the gas-phase reactions within the inert packed bed. The same kinetic data
for the gas-phase reactions have also been used in the numerical simulation within 'the
catalytic beds.
The results of the methane oxidation in air at equivalence ratio 4 = 0.35 and approach
velocity u = 1.0 m/s are shown in Fig. 5.1 for the inert bed. It can be seen that the
noticeable conversion within the inert bed starts at arelatively high temperature 800 K.
The conversion increases slowly up to atemperature of 1078 K when rapid conversion
(ignition) takes place. For comparison the predicted results (using the model described)
and experimental data of Depiak and Wierzba (1999) were also ihown in Fig. 5.1. It can
be seen that they were in afair agreement, especially at temperatures greater than 1000
K. However, the predicted conversion of methane at low temperatures is somewhat.
smaller than that obtained experimentally.
The exhaust gas concentrations of CH4,CO 2,and CO within the inert bed over the entire
inlet temperature range for the above condition of 4= 0.35, u= 1.0 m/s are plotted in Fig.
5.2. There is anoticeable CO concentration detected in the exhaust at the middle inlet
temperature range. The maximum measured concentration of CO is obtained at an inlet
temperature of- 1020 K. Beyond this temperature (1020 K), the methane concentration
becomes significantly low due to higher reaction rates and consequently the CO
concentration begins to fall producing essentially a zero concentration at the inlet
temperature of 1060 K and above.

100
100
90
Inert Bed
80
—A Experimental data (present work)
— — — — Calculated data (present work)
' 70
—a Experimental data Depiak & Wierzba (1999)
• 60
50
40
30
(-)
20
10
fi
200 400 600 800 1000 1200
Temperature (K)
Fig. 5.1 Comparison between experimental and calculated methane conversion within the
inert bed for 4 = 0.35, u= 1.0 m/s.
4 0.4
3.5 0.35
0.25
Inert Bed
0.2
—n---- CH
—e--- Co,
.A Co 0.15
6 0.5 0.05
0 400 600 I 800 ioo' 0

Temperature (K)
Fig. 5.2 Exhaust concentrations of CH4,CO 2 and CO as afunction of inlet temperature
within the inert bed for = 0.35, u= 1.0 m/s.

101
5.3 Catalytic Packed Bed
5.3.1 Effect of Catalyst Aging
The results of methane combustion obtained with fresh platinum catalyst are presented in
Figs. 5.3 and 5.4 with 4 = 0.35 and u = 1.0 m/s. It can be seen that at temperatures
between 673 and 723 K, the conversion of methane over the fresh catalyst dropped
sharply and is consistent with CO 2 concentration. Such behavior could be attributed to the
following factors:
1. Initially anti-oxidant s
ealant (LPS Anti-Seize) was used between the flanges as
well as on the screws connecting the reactor to the apparatus. This sealant
contains lead and zinc, the vapors of which can poison the platinum catalyst
(Hagen, 1999; Cybulski, and Moulijn, 1998). At higher temperatures the vapors
of the sealant could have been deposited on the external surface of the catalytic
pellets and have block access to their interior. Thus, the deactivation of the
catalyst could have occurred by pore blockage. This conclusion was drawn after a
sudden stop and resumption of the conversion with inlet temperature between 673
and 723 K. Since with an increase in the inlet temperature above 700 K the
conversion of methane also increased as shown in Fig. 5.4. This is probably due
to evaporation of the sealant and the consequent regeneration of the catalyst.
Moreover, the lead poisoning is reversed athigher temperatures (T> 1000 K) due
to the decomposing and volatilization of the lead compounds (Kesselring et al.
1979). It can be seen in Fig. 5.5 that the temperature at the exit from the reactor
reached - 1275 K. The reactor was dismantled and cleaned of the sealant. Another
set of experimental data was obtained after reassembling the reactor with the same
fresh catalyst which had been used for five hours only.
102
50
40 - ----- Fresh Pt Catalyst -
0"
© 30
C_) 20
10
I I 1 9 1 I
00 400 500 600 700 800
Fig. 5.3 Effect of deactivation of fresh platinum catalyst 'on methane conversion, k =
0.35, u= 1.0 m/s.
4.0
(3.5
0 •'
1- 1
0 3.0
2.5
Pt Catalyst
2.0
: —a--- CH Concentration
—4----- CO, Concentration
1.0
0.5
0 0 cJ
bo
- -
400 500 600 700 800 900 100

Fig. 5.4 Exhaust concentrations of CH4 and CO 2 as afunction of inlet temperature; fresh
platinum catalyst, 1= 0.35, u= 1.0 m/s.

103
2. Sintering of platinum catalyst caused by thermal stress. It can be seen (Fig 5.5)
that at the inlet temperature of 673K, 40% of methane was oxidized and the
exhaust gas temperature reached 1275 K.
It had been reported in the literature (Prasad, 1984) that platinum sinters
rapidly at temperatures of 500 - 900 °C (i.e., 773 - 1173 K). It was also found.
that platinum at temperature above 585 °C will form large metallic crystállites.
This change in crystallite size is known as the agglomeration of platinum. The
formation of large crystallites of platinum results in much reduced activity (Lee,
and Ruckenstein, 1983; Ruckeiistein, and Dadyburjor, 1983; Butt, and Petersen,
1988; Hagen, 1999; Cybuiski, and Moulijn, 1998).
A change in the color of the catalytic pellets was observed after
conducting experiments for more than 130 hours. The color of the fresh catalytic
pellets changed from metallic medium/dark gray to alighter gray after using them
for 19 hours and to avery light gray (almost white) after 131.5 hours. Other
researchers have also observed similar changes -in catalys

t color and the
corresponding activity of their catalysts (Bharadwaj, and. Schmidt, 1994;
Torniainen et al., 1994). They explained that the changes in color of the catalyst
are due to sintering of the platinum metal into largei particles with smaller
surface-to-volume ratios, and to the exposure of Al2O3.Large crystals of platinum
metal (- 100 j.tm) were observed on their used catalysts. .
3. A series of phase changes of the catalyst support, y-A1203,occur when it is heated
to highertemperatures. y-Al2O3 with a specific high surface area of about 300
m2/g can be transformed into cc-A1203 with its specific surface area of less than 10
m2/g. Such transformation takes place at temperatures around 1173 K. Sintering
thus results in pore closure and aburying of active catalytic sites in the alumina
support (Prasad, 1984; Richardson, 1989; Cybulski, and Moulijn, 1994 and 1998.-
Hagen, 1999; Alfa Aesar catalog, 2001-02).

104
A significant change in the performance between the fresh catalyst used for 5.0 h and
used catalyst for 131.5 h(aged) was also observed (se Fig. 5.6). At temperatures below
750 K, the highest conversion obtained was over the'catalyst which was 5.0 h old. At
these temperatures the difference in methane conversion over the catalysts aged for 19.5
and 131.5 hwas very small.
The exhaust as temperatures were measured at the exit of the packed bed with the 5.0 h
platinum catalyst with u = 1.0 m/s and 4 = 0.35. They are plotted against the inlet
temperatures in Fig. 5.7 together with the corresponding values of the conversion of
methane. The increasein the exit gas temperature is linear and slow for inlet temperatures
below 625 K. The exhaust gas temperatures at the inlet temperature above 625 K (which
correspond to the start of the light-off iegime) increase significantly due to asubstantial
increas
e in the rate of methane oxidation. A corresponding increase in exhaust
temperature was observed. For example at inlet temperature of 748 K the exhaust
temperature was 1350 K. This value is in afair agreement with the value of 1364 K
obtained by Bond et al. (1996) for 38% of methane conversion. The corresponding
calculated adiabatic flame temperature (for 40% of converted methane) is 1429 K which
is rather in good agreement taking into consideration that the measured temperature was
not corrected for the heat loss. However, the error in the thermocouple measurements due
to radiation and convection is calculated (Appendix C) and the r

esults are shown in Fig.
5.7. The repeatability in the experimental methane conversion is also shown in Fig. 5.7
with amaximum error of 4.8%.
105
1400 100
1200
80 '
1000 0
60
800
0
0
40
600
20
400
200 1 0, I I I I I I I I o
400 500 600 700 . 800
Fig. 5.5 Exhaust gas temperature and methane conversion as a function of inlet
temperature; fresh platinum catalyst, 41 = 0.35, u= 1.0 m/s.
100
Pt Catalyst
80
• Fresh catalyst (5.0 h)
—4k----- Aged catalyst 19.5 h
---- Aged catalyst l3l.5h
260
20
I t I I I In I I II II I I I I I
400 500 600 700 800 900 1000

Fig. 5.6 Comparison of methane conversion over fresh and aged platinum catalyst 41 =
0.35, u= 1.0 m/s.

106
1400 100
Pt Catalyst
1200 Temperature
a
- 80
conversion
1000 0
- 60
800
- 40
600
20
400
200
400 500 600 700 800 0
Fig. 5.7 Exhaust gas temperature and methane conversion as a function of inlet
temperature; fresh (5.0 h) platinum catalyst, = 0.35, u= 1.0 mi's.

107
5.3.2 Combustion of Methane over Aged Platinum Catalyst
Aging of the platinum catalyst affected the conversion of the fuel drastically. Therefore,
aged catalysts were used to obtain trends on the effects of inlet temperature, equivalence
ratio, and approach velocity independent of the current activity of the catalyst. All the
results below were obtained, with the aged catalyst. Experiments were performed over the
range of equivalence ratios from 0.2 to 0.6 with approach velocities varied from 0:75 to
3.0 m/s. Howevef, -some experiments were carried with fresh platinum catalyst for
comparison purposes.
It can be seen from'

Fig. 5.8 that.noticeable methane conversion starts at much lower inlet
±emperatures (500 K) than in the case of the inert bed. It was also illustrated that methane
conversion increases with increasing inlet temperatures. Generally, at low temperatures,
conversion is controlled by reaction kinetics ("kinetic limitation") at the catalytic surface

(Bond, et al., 1996; Pfefflerle and Pfefflerle, 1987), while at higher temperatures, surface
reactions are fast compared to the rate of mass diffusion to the surface ("diffusion
limitation"). Between these two regimes exists an unstable operating region, where the
methane conversion depends very strongly on the inlet temperature. For temperatures
above 800K this sudden increase in conversions is observed for equivalence ratios of
>0.35.
The effect of equivalence ratio on methane conversion for the approach velocity of u
1.0 m/s,is illustrated in Figs. 5.8 and 5.9. An increase in the methane equivalence ratio
increased the conversion of methane for the entire inlet temperature range employed. At
temperatures below 500 K methane oxidation for all equivalence ratios is negligible and
at relatively low temperature about 650 K, the fractional conversion is approximately
independent of the equivalence ratio. Methane conversion -

is much higher in the mixture
with the equivalence ratio of c,f = 0.6 at temperatures above 700 K probably due to the
fact that such ejuivalence ratio is within the flammability range of methane. The
conversion improves significantly with increasing inlet temperature (Fig. 5.9).

108
300 400. 500 600 700 800 900 1000

Fig. 5.8 Methane conversion as afunction of inlet temperature for different equivalence
ratios, u= 1.0 m/s; aged Pt catalyst.
100
Pt Catalyst
80
----- 1573K
-,--- T=698K
—a---- T,=74SK
—4-- T823K
• 60 ' 1848K
41
40
20
0.2 0.4- 0.6 08

Equivalence Ratio
Fig. 5.9 Methane conversion versus equivalence ratio'at different inlet temperatures, u=
1.0 m/s; aged Pt catalyst.

109
As expected, the strong effect 'of inlet temperature is apparent throughout the entire range
of equivalence ratios tested. For instance, the conversion increases from 12.9% to 36.4%
as the equivalence ratio increases from 0.20 to 0.60, respectively at an inlet temperature
of 823 K. A similar trend, i.e. the increase in methane conversion with an increase in the
equivalence ratio over platinum catalysts supported on ceramic honeycomb monoliths
was also reported by Bond et al. (1996). However, their measured methane conversions at
850 K inlet gas temperature are higher than those obtained in this investigation, 13.5%
and 38% for equivalence ratios of 0.18 and 0.30, respectively. It appears that at higher
temperatures the performance improved for all equivalence ratios although above 850 °C
(i.e. 1123 K) the platinum catalyst exhibited achange in characteristics due to thermal
stress; in addition to the phase change of the catalyst support. It is worth mentioning that
the experiment with the equivalence ratio of 0.35 was conducted first. It was followed by
experiments with the equivalence ratios of 0.20, 0.50, and. 0.60. As pointed out, the
results suggest that aging of the platinum catalyst may influence the conversion curves
for higher equivalence ratios as discussed in the previous section.
. Experiments were also performed to determine the effect of approach velocity on the
reactor performance. The velocity was calculated based on the reference temperature of
•293 K and the atmospheric pressure of 88 kPa. Approach velocities were varied from
0.75 to 3.0 m/s for the mixture equivalehce ratio of = 0.35. The results are shown in
Figs 5.10 and 5.11. The expected decrease in methane conversion was observed at higher
velocities. It can be seen that as the approach velocity decreases, the light-off position is
progressively shifted to lower inlet temperatures. At higher inlet 'temperatures the effect
of velocities is somewhat more pronounced, e.g. at the hilet temperatures of 823 atid 598
K, the methane conversion decreased from 28.2% to 13.7% and from 5.9% to 0.0%
correspondingly, when the velocity increased from 1.0 to 3.0 m/s. Higher approach
velocities correspond to reduced residence time (contact time between the catalysts and
the fuel). This trend has also been observed experimentally and numerically by other
researchers (Dupont et al., 2000; Moallemi et al., 1999). -

110
50
Pt Catalyst
40
—A---- uO.75m/s
X u1.Om/s
— y u2.Om/s
•— u- 2.5m/s
• 30 • u3.Om/s
C20
10
400 500 600 700 800 900 1000

Fig. 5.10 Methane conversion as afunction of inlet temperature at different approach
velocities with = 0.35; aged Pt catalyst.
50
Pt Catalyst
40
—a--- T=598K
A T698K
T,=748K
T=823K
30 -.---
I
c320
10
%0 0.5 1.0.. 1.5 2.0 2.5 3.0 35

Approach Velocity (m/sec)
Fig. 5.11 Effect of approach velocity on methane conversion at different inlet
temperature with = 0.35; aged Pt catalyst.

111
5.4 Oxidation of Methane over Binary (Co 3O4ICr2O3)Catalyst
The performance of C0 304/Cr2O3 (3.13 ratio by mass) within the reactor in methane
oxidation was investigated and was compared to those of Depiak (2003) in Fig. 5.12 at
various inlet temperatures for 4, = 0.35 and u= 1.0 m/s. In Depiak's work the conversion
of methane plotted against measured temperatures which were taken at the middle of the
reactor. Therefore, these measured temperatures were adjusted based on his temperature
distribution along the bed to reflect the inlet temperatures corresponding to this work and
compared to the values of the present investigation. Moreover, they exhibited high
temperature stability over a range of temperatures, which are typical for catalytic
combustors. The corresponding exhaust concentrations of CH4,CO, and CO 2 with
C0304/Cr2O3 catalyst at the above mentioned operational conditions are shown in Fig.
5.13. At low temperatures, the oxidation was relatively small' However, the oxidation of
methane at the inlet temperature of 750 K was increased significantly. At the inlet
temperatures above 600 K a noticeable amount of CO was measured. With further
increase in the temperature value the CO concentration in exhaust gases increased
significantly. At an inlet temperature of 880 K, the detected CO concentration was
0.095%.
The effect of equivalence ratio on methane conversion with the C0304/Cr2O3 catalyst is
illustrated in Fig. 5.14 at different inlet temperatures. The trends observed are similar to
those for Pt catalyst i.e. as the equivalence ratio increased so does, the conversion of
methane. It was also found that the concentration of CO increased with an increase in
equivalence ratio, especially in the region of light-off temperatures, for example from
0.063% for 4, = 0.35 to 0.165% for 4, = 0.50 at inlet temperature of 798 K as shown in
Fig. 5.15.
112
500 600 700 800 900 1000

Fig. 5.12 Methane conversion as afunction of inlet temperature within the C0304/Cr2O3
catalytic bed, = 0.35 and u= 1.0 m/s.
4.0 0.40
0.35
Co 3O4ICr2O3 Catalyst
—4---- CH4
CO'
• co
- 0.05
300 400 500 600 700 800 900 i00%-oo

Fig. 5.13 Exhaust concentrations of CH4,CO and CO 2 as afunction of inlet temperature;
C0304/Cr2O3 catalyst, u= 1.0 m/s and 4i = 0.35.

113
400 500 600 700 800 900 1000

Inlet Tempemtwie (K)
Fig. 5.14 Methane conversion as afunction of inlet temperature for different equivalence
ratios; Co 3O4JCr2O3 catalyst, u= 1.0 m/s.
0.20
C0 304/Cr2O3 Catalyst
0.15
• 0.35
0.50
C
.,
0.10
0.05
0.00
P & I
300 400 500 610 700 800 900 1000
Fig. 5.15 Exhaust concentration of CO as afunction of inlet temperature for different
equivalence ratios; C0304/Cr2O3 catalyst, u= 1.0 rn/s.

114
Furthermore, the performance of C0 304/Cr2O3catalyst (aged for 17.0 h) was compared to
that of the platinum catalysts (fresh and aged) as shown in Fig. 5.16. In fact, platinum and
palladium are the most commonly used catalysts in catalytic combustion applications for
their high specific activity in comparison to base metal oxides. However, practical
limitations such as high volatility and limited supply restrict their use. Therefore, finding
alternative catalysts of base metal oxides is of great importance. Metal oxide catalysts
typically have lower catalytic activity and higher light-off temperatures than noble metal
catalysts. This is demonstrated in Fig. 5.16, in which the performance of afresh (5.0 h)
platinum catalyst is much better than that of Co 3O4JCr2O3.The light-off temperature for a
binary catalyst of cobalt and chromium oxides is around 750 K while avalue of 610 K
was identified for fresh (5.0 h) platinum catalyst. At an inlet temperature of 723 K, the
difference in the conversion of methane between these two catalysts is very large about
78.57%. However, Co3O/Cr2O3 catalysts were more stable at high temperatures. Als
o,
Fig. 5.16 illustrates clearly that the effect of the catalyst aging on methane conversion for
platinum catalyst in comparison to C0 304/Cr2O3 catalyst, which is more thermally stable
at high temperature. It has been shown in the literature (Prasad et al., 1981) that the
C0304/Cr2O3 catalysts have been tested for up to 400 h of operation at maximum

temperatures of up to 1373 K without significant deactivation. Furthermore, Depiak
(2003) has shown insignificant effect of aging for 50 hof the C0 304/Cr2O3 (0.33 ratio by
mass) catalysts exposed to the .temperatures of 800 K and above on methane conversion
for 4
= 0.35 and u= 1.0 m/s. It can be seen that the fresh (5.0 h) Pt catalyst and one aged
for 19.5 hperform much better than C0 304/Cr2O3 catalysts. However platinum catalysts
are not able to sustain their activity over longer exposures to high temperature. Thus,
C0 304/Cr2O3 catalysts showed better performance in methane conversion than Pt ones
aged for 131.5 h. Both catalysts show similar performance before the light-off
temperatures were reached. The exhaust concentration of CH4 and CO 2 for fresh (5.0 h)
Pt catalyst was compared with that of C0 304/Cr2O3 catalysts in Fig. 5.17 under the same
conditions of tfi = 0.35 and u = 1.0 m/s. At all temperatures no CO was detected in the
exhaust with Pt catalyst. Both catalysts exhibited similar behavior with shifted curves
toward the higher temperature region for C0304/Cr2O3 catalysts.

115
100
• Fresh Pt catalyst (5.0 h)

80
—'v'---- Aged Pt catalyst 19.5 h
-4----- Aged Pt catalyst 131.5 h
0'
—*----- Co,04/Cr,O, catalyst
• 60
Q 40
20
0 ej
400 500 600 700 800 900 1000
Fig. 5.16 Comparison between Pt and C0304/Cr2O3 catalysts for methane conversion at
different inlet temperatures, u= 1.0 m/s, 4) = 0.35.
4.0
3.5
CH4 (Pt catalyst, 5.0 h)

• CO 2 (Pt catalyst, 5.0 h)
o CH 4 (Co,O/Cr,O, catalyst)
o CO 2 (Co,O 4ICr2O, catalyst)
400 500 600 700 800 900 1000

Fig. 5.17 Exhaust concentration of CI- 4 and CO 2 as afunction of inlet temperature; Pt
and Co 3O4JCr2O3 catalysts, u= 1.0 m/s, 4) = 0.35.

116
5.5 Summary
The effects of inlet temperature, equivalence ratio, and approach velocity on methane
conversion over inert and catalytic beds were investigated experimentally. It is found that
there is aneed for higher inlet temperature (Tj> 1078 K) to initiate methane conversion
over the inert bed, while relatively low temperature (T m > 620 K) is needed for methane
conversion by utilizing catalytic bed. In general, the conversion of methane increased
with increasing the inlet temperature and equivalence ratio or decreasing the approach
velocity. It was also found that platinum catalyst exhibited aging within five hours of
usage, which affect the conversion of methane drastically.
The main objective of this experimental work is to establish kinetic data for methane
conversion within the packed bed reactor needed for the mathematical modeling, which is
the topic of the next Chapter.

117
CHAPTER 6
NUMERICAL SIMULATION OF METHANE COMBUSTION IN A
PACKED BED REACTOR
6.1 Introduction
The model developed for the present investigation includes two overall reaction rates,
one .forthe catalytic reaction occurring at the surface and the other for ahomogeneous
reaction within the gas-phase. The rate expressions for asingle-step overall irreversible
homogeneous reaction (Eqs. (3.11) and (3.18)) and for asurface reaction (Eqs. (3.12) and
(3.19)) of the Arrhenius type were used. This research intended to investigate whether
such simplified rate expressions obtained from the literature can predict satisfactorily
some of the experimentally observed trends of such complex systems. It also intended to
derive from experimental observations kinetic data for methane oxidation in the packed
bed reactor. The effect of some of the operating parameters on the methane conversion
within the packed bed addressed in the preliminary results is reconsidered in this Chapter
using the kinetic data obtained from the present work.
6.2 Determination of Kinetic Data for Surface Reactions
6.2.1 Platinum Catalyst
Results of the numerical simulation obtained with kinetic data chosen from the literature
for similar conditions, specifically, Trimm and Lam (1980), Song et al. (1991) and
Markatou et al. (1993) do not match well our experimental results as was mentioned
118
earlier (Fig. 3.14). Therefore, the pre-exponential factor and the activation energy of the
surface reaction were obtained from the experimental data under the conditions in the
packed bed reactor, using the following procedure:
1. Substituting equation (3.12) for the surface reaction rate (i.e. heterogeneous reaction
rate) in the energy equation of the solid (pellets) in rder to include the surface
reaction effect on methane conversion within the catalytic bed.
2. Choosing as a first approximation a value for the activation energy and pre-
exponential factor for the surface reaction from the literature. Trimm and Lam
(1980) give two values of (E, = 86 kJ/mol. and B8 = 46 kJ/mol with As = 1.03x10 5
kmoll(m2.K)) for methane-air mixtures with platinum as the catalyst.
3. Calculating the methane conversion curve as afunction of the inlet temperature.

4. Comparing the predicted methane conversion curve with the experiment.
5. If the calculated and measured methane conversion curves in step (3 and 4) were far
apart, the value' of the pre-exponential factor was changed, while the value of the
activation energy was held fixed. The value of the pre-exponential factor was varied
until the model reasonably predicts the methane conversion. This procedure was
done only for one set of data (4 = 0.35, u 1.0 m/s).
6. Changing the value of the activation energy in order to reach even better matching
between the experimental and predicted methane conversion curves as afunction of

the inlet temperature.
7. Repeating steps (3) and (4) every time the activation energy value was changed until
a good agreement was reached between the two mentioned curves of methane
conversion.
8. The final values of the pre-exponential factor and activation energy with the best
match between one set of experimental data and predicted methane conversion will
be the adopted value of the kinetic data for the platinum catalyst within the packed
bed reactor.
119
Figure 6.1 shows the methane conversion curves corresponding to different chosen values
of the activation energy and the pre-exponential factor used to determine the kinetic data
for methane-air mixture of 4= 0.35 and at u= 1.0 m/s over the fresh platinum catalyst.
Furthermore, Fig. 6.2 shows the experimental data and thQ predicted methane conversion
obtained by using values of the pre-exponential factor and the activation energy obtained
from the present investigation for two temperature regimes. The resulting activation
energy of the surface reaction was found to be 46.0 ± 1.0 kJ/mol over the. temperature
range 750 - 925 K. Moreover, the obtained kinetics of methane oxidation shows achange
in the activation energy at temperatures below 750 K. The value of the activation energy
of 42.0 ± 0.8 kJ/mol at temperatures < 750 K was found to better match the experimental
results. The pre-exponential value was found to be 1.03 x 10 -3 kmol/(m2.

s) for the entire
range of temperature. The predicted results for methane conversion at different
temperatures using the above mentioned values of activation energy and pre-exponential
factor showed good agreement with the experimental data obtained during this
investigation as well as with data of Depiak and Wierzba (1999).
The conversion of the methane at = 0.50 using the pre-exponential factor and
surface activation energy obtained during this investigation was plotted in Fig. 6.3 with u
= 1.0 m/s. The oxidation of methane was enhanced by increasing the concentration of the
methane at the inlet.
The increase in the approach velocity from 1.0 to 3.0 m/s showed areasonable
agreement with the experimental data of Depiak (2003) using the above mentioned
kinetic data as illustrated in Fig. 6.4.

120
100 .-.--
/
I.
/
80 -
I /
I
60—,
I I
I I /
40-
/
20- I
I
A AA /
0 A' I It IttI Ii
400 600 800 1000 1200
A Experimental data (present work)

Experimental data (Depiak & Wierzba, 1999)
- E5 86 kJ/kmol; A5 1.03x10 5
E=46 kJ/kmol; A5=1.03x10 5
E3=46 kJ/kmol; A2.Ox1O5
E=46 kJ/kmol; A1.O3x1O 2
Fig. 6.1 Experimental data and predicted methane conversion as a function of inlet
temperature for-various pre-

exponential factors and activation energies; platinum catalyst,
u= 1.0m/s,=0.35.
121
100
Pt catalt
ys I ,
-
- A Experimental data (present work)

80 -- - - - Calculated data (present work)
- Experimental data (Depiak & Wierzba, 1999) I
0••
• 60
(540
20
0
200 400 600 800 1000
Fig. 6.2 Experimental and calculated methane conversion as a function of inlet
temperature, platinum catalyst, u= 1.0 m/s, 4) = 0.35, E8=46.0 kJ/mol for Tj≥ 750 K, E5
= 42.0 kJ/rnol for Tm< 750 K, A5=1.03x10 3 kmol/m2.K.
100
Pt catalyst /
A Experimental data (present work, 0.35) /

80 Calculated data (present work, 0.35) 1
j
- - - -
Experimental data (Depiak & Wierzba, 0.35)

- . - - - Calculated data (present work; 0.50) . /
/
. 60
-
. /
- !'
-
20 - I]
I'
0
200 400 600 800
temperature for two equivalence ratios, platinum catalyst, u= 1.0 m/s.

122
100
Pt catalyst
- - - -. Calculated data-
(present work)
80 - Experimental data (Depiak& Wierzba, 1999)
,0
- - - - Calculated data (present work)
0'•' 49 Experimental data (Depiak & Wierzba, 1999)
60
40
U = 1.0 rn/s ,
I.
I
U 3.0 rn/s
20
'tj.
0
0 200 4(J 600 800 1000
Inlet temperature (K)
temperature for two approach velocities, platinum catalyst, 4) = 0.35.
6.2.2 C0304/Cr2O3 Catalyst
The same sequence of steps in obtaining the kinetic data has been carried out for methane
conversion over the C0304/Cr2O3 catalyst at u = 1.0 m/s and 4) = 0.35. The agreement
between the experimental methane conversion data and the computed results is shown in
Fig. 6.5. The values of the activation energy and the pre-exponential factor for a
heterogeneous reaction were estimated to be 46.3 ± 0.3 kJ/mol and 2.2x10 3 kmol/(m2.$)
respectively for temperatures greater than 775 K. These have afair agreement with the
experimental data. However, at temperatures less than or equal 775 K, the activation
energy was 42.8 ± 0.8 kJ/mol.
Figure 6.6 illustrates the improved conversion with increasing the equivalence
ratio as a function of inlet temperatures using the kinetic data obtained through this
investigation. For instance, starting from methane conversion of 64.9% at 4) = 0.35,

1.23
methane conversion increased with increasing 4), attaining avalue of 85.11% at 4) = 0.50.
The predicted methane conversion is in reasonable agreement with the experimental, data
for 4) = 0.50. However at temperatures above 800 K, the predicted methane conversion is
as much as 20% higher than the measurements. These observations suggest adeficiency
in the surface chemistry mechanism, which may require a more detailed reaction
mechanism.
The same tendency as that in the case of platinum catalyst toward the dependence
of methane conversion on the approach velocity is observed for the C0304/Cr2O3 catalyst
(Fig. 6.7).
100
80 Experimental data (present work)
- - - Calculated data (present work)
Experimental data (Depiak & Wierzba, 1999) .../
/
.2 60
34o
16
20
in
400 600 800 1000

temperature, C0304/Cr2O3 catalyst, u= 1.0 m/s, 4) = 0.35, B5= 42.8 kJ/mol for ≤ 775
K, B5= 46.3 Id/mo! for Tin > 775 K, A = 2.2 x i0 kmoll m2.K.
124
100
Co 3O/CiO3 Catalyst
80
-
- - - • - - Experimental
Calculated data
data
(present
(present
work;4) 4)=
work;=0.35)
0.35) /
•
Experimental data (Depiak & Wierzba;4) =0.35)!

/
,
Calcu l
ate ddata (
present work;(j) =0.50)
/
- - . - - -
.9 60 - i Experimental data (present work; 4) =0.50)
40 -
20 -
a
,
200 400 600 800 1000

temperature for two equivalence ratios, C0304/Cr2O3 catalyst, u= 1.0 m/s.
100
/
I Co 3O4ICr2O3 Catalyst /
/
80
-, Experimental data (present work) /
- - - Calculated data (presentwork)
I
- l Experimental data (Depiak & Wietzba) /
Calculated data (present work) /
I
'A
40 00 u3.0m/s
u= 1.0 m/s
20
ii till I
400 600 800 1000 1200
temperature for two approach velocities, C0304/Cr2O3 catalyst, = 0.35.

125
6.3 Results of Model Prediction
In Chapter 3 the effects of the parameters that. influence methane conversion were
presented using kinetic data from the open literature. In this section the effect of some of
these parameters are presented using kinetic data obtained during the present
investigation for homogeneous and surface reactions.
6.3.1 Methane Oxidation within the Inert Bed
Effect of bed porosity. The effect of bed porosity on the methane conversion as afunction
of the inlet temperature is shown in Fig. 6.8. The decrease in the surface area by
increasing the bed porosity decreases the conversion of methane within the inert bed. The
effect of bed porosity is more pronounced between a= 0.2 and a= 0.4 than between a=
0.4 and a= 0.9,
Effect of bed length. The variation of methane conversion with inlet temperature, for
different bed lengths, may be seen in Fig. 6.9. Th6 curves of the conversion of methane
shifted to the left as aresult of increasing the residence time. The inlet temperatures
corresponding to the complete conversion of methane for bed lengths of 50,75, and 100
mm are 1088, 1050, and 1040 K, respectively.
Effect of solid thermal conductivity. Increasing the solid thermal conductivity enhanced
the conversion of methane and allowed complete conversion to take place at alower inlet
temperature (Fig. 6.10). This is due to increased heat conduction to the upstream region
of the bed.
126
100
Inert Bed
80
---"-6=0.4
8 - 0.
5
c40
20
I I
0 .
400 600 800 1000 1200

Fig. 6.8 Calculated methane conversion as afunction of inlet temperature for various bed
porosities within the inert bed, = 0.35, u= 1.0 m/s, k = 1.0 W/ m.K, L = 50 mm.
100
Inert Bed
80
- - - - L=50nun
L75nun
LI00mm
• 60
0
40
20
I I
0
400 600 800 1000 1200
Fig. 69 Calculated methane conversion as afunction of inlet temperature for different
bed lengths; s= 0.4, k= 0.35, u 1.0 m/s, k

= = 1.0 W/ m.K.
127
100
80
= Inert Bed
- - - - k = 0.5 W/(m.K)
k1.0W/(m.K)
- - - - - = 2.0 W/(m.K)
•9 60
40
20
I I
0
400 600 800 1000 1200
Inlet Temperature (IC)
solid thermal conductivities; 4= 0.35, u= 1.0 m/s, L= 50 mm, a= 0.4.
6.3.2 Methane Oxidation within the Heterogeneous Bed
Effect of bed porosity. The effect of bed porosities on methane conversion at the exit of
the reactor is shown in Fig. 6.11. The complete conversion of methane was obtained over
the entire range of bed porosities employed (a 0.2 to 0.9) for abed length of L = 50
mm. Increasing the bed porosities results in smaller catalytic surface area which yields
smaller conversion of methane. Thus, light-off temperature was increased significantly as
the bed porosity is increased. The light-off temperatures for bed porosities of a= 0.2, 0.4,
0.5, and 0.9 are 720, 870, 910, and 1000K, respectively.
Effect of bed length. The effect of bed length on the conversion of methane is illustrated
in Fig. 6.12 for abed porosity of a= 0.5. The complete conversion of methane is obtained
for the three bed lengths employed. Over the entire temperature range, the highest
conversion of methane is attained within the bed of 100mm long. This is due to the
increase of the catalytic surface area as well as the residence time for the longer bed.
128
Effect of solid thermal conductivity. The effect of solid thermal conductivity on the
conversion of methane for 1= 0.35, u= 1.0 rn/s within aheterogeneous bed is shown in
Fig. 6.13. As indicated earlier, the effect of thermal conductivity is negligible especially
for methane conversion of above 75%. The increase in the thermal conductivity increased
the conversion of methane in particular at the light-off regime. This trend is due to the
increased surface reactions and increased thermal dissipation at the solid.
6.4 Summary
The predicted performance of the catalytic reactor using the measured kinetic coefficients
of the present investigation revealed similar dependence on equivalence ratio, velocity,
bed porosity, bed length and solid thermal conductivity as when using the kinetic
coefficients obtained from the literature (Chapter 3). However, using the kinetic
coefficients obtained during the present investigation shifted methane conversion curves
toward lower inlet temperatures.
•100
- . • - - -•
Heterogeneous reaction only .
0 80 ------8=0.2 1
q
80.4 /
-----8=0.5 /
•- 60 ! I /
I.
40
- ! /
V.
I ,
20
I , /
-
I / /
I I I I
0 1(111!! i I I
400 600 800 1000 1200

bed porosities; 4) = 0.35, u= 1.0 m/s, k = 1.0 W/(m.K), L = 50 mm; Pt catalyst.

129
100
..- 80
•- 60
40
20
0
400 600 800 1000 1200
Inlet Temperature(K)
bed lengths; F, = 0. 5, k= 0.35, u= 1.0 m/s, k = 1.0 W/ m. K; Pt catalyst.
100
eaction only
Heterogeneous r
80 1ç0.5W/(m.K)
= 1.0 W/(m.K)
- - - - 1ç2.OW/(m.K) 1
•
60
I
40 k.=4.0 i m.K))/d
20
900 800 900 1000 1100 1200

solid thermal conductivities; = 0.35, u= 1.0 m/s, L = 50 mm, a= 0.4; Pt catalyst.

130
CHAPTER 7
OXIDATION OF OTHER GASEOUS FUELS IN A PACKED BED
REACTOR
7.1 Introduction
One of the important considerations in the selection of acatalyst is its ability to operate
on specific fuels. As mentioned earlier in the literature survey, several investigations have
shown variations in performance with fuel type for aparticular catalyst. For example,
higher molecular weight hydrocarbons such as propane can be burnt over awider range
of conditions than natural gas, and low calorific value gases may be even easier to
oxidize (Kesslering, 1986). The performance of acatalytic combustor is determined by a
large number of operational and physical conditions. Performance can be quantified by
measurements of combustion efficiency, emissions and fuel applicability.
In this chapter, the results of calculations of the oxidation of other common
gaseous fuels such as ethane, propane; carbon monoxide and hydrogen within apacked
bed reactor using the developed model are described. The results of the model predictions
are compared to the available experimental data (Depiak, 2003) obtained under the same
conditions for platinum and abinary mixture of C0304/Cr2O3 catalysts in order to obtain
the kinetic data for these fuels in the packed bed reactor.
The homogeneous (gas-phase) and heterogeneous (surface) reaction rates for the
fuel over the catalytic pellets were modeled as an irreversible one-step reaction rates as
discussed earlier in Chapter (3). They are listed below:

131
h = Ag c;Co" exp [ Eg
RTg1
C
o = AsCf C0. 5 expf --j (7.2)
The kinetic parameters for surface (As, E) and gas-phase (Ag,Ed reactions as well as
power coefficients in and nwere obtained from the literature for lean fuel-air mixtures
with platinum as acatalyst. They are listed in Tables 7.1 and 7.2. Other alternatives of
kinetic data could have been chosen, however these data were chosen because the range
of equivalence ratios and temperatures they correspond to are within the same range of
the present study. The kinetic data adopted from the literature are used in the parametric
study of the fuels oxidation in the packed bed reactor.

Table 7.1 Kinetic parameters for gas-phase reactions.
Mixture Conditions Ag Eg
Fuel m n Reference
(i.e., Flow Type, , Ti,,) (kmol/m3.$) (kJ/mol)
Premixed Present work (matching

CH4 0.2 1.30 6.6 x 10 10 180.0
0.15 <4 <0.50 experimental and predicted data)
Laminar flame model

C2H6 0.1 1.65 6.19 x10 9 125.0 Westbrook and Dryer, 1981
•O.5<<1.9
Laminar flame model; 0.5 < < 1.9

Westbrook and Dryer, 1981
C3H8 Shock tube; 0.12<<2.0 0.1 1.65 4.836x 10 9 125.0
Hautman et al., 1981
Ti
n
Sobolev, 1957
CO 820 <T1 < 2400 1.0 0.0 1.07 x i07 107.1
Aleksandrov and Azatyan, 1973
Premixed
H2 . 1.0 1.0 5.155 x 10 9 125.3 Mon et al., 1977
Tm<1000 •
Table 7.2 Kinetic parameters for surface reactions.
Temperature Range A E
Fuel Reactor Type Reference
(K) (kmollm2 .$) (kJ/mol)
CI- 4 723 <Tin < 853 platinum on alumina fibre 1.03 x i0 86.0 Trimm, and Lam, 1980
C2H6 435 <T1,

1< 770 platinum filament 4.237 x i0 68.85 Haim et al., 1968
435 <T m < 770 platinum filament; Haim et al., 1968;

C3H8 3.478x10 3 70.85
298 <T1 < 1223 platinum foil Song et al., 1991
CO 535 <Tm <760 Platinum catalytic converter 2.2 x10 3 23.56 Kuo et al., 1980
273 <Tm <450 platinum wire; 10.30 Boreskov, 1954;

H2 5.4x104
450 <Tm < 1073 platinum coated flat plate 16.05 Brown et al., 1983
134
7.2 Ethane Combustion
Natural gas composition varies significantly from one source to another. The methane
content of natural gas varies from 70% to 95%, the ethane content varies from 3% to 18%
with higher hydrocarbons, hydrogen, nitrogen and carbon dioxide making up the balance
(Griffin et al., 1989). Since methane is much less reactive than ethane the combustion
characteristics of natural gas depend on the amounts of minor constituents present.
Variations in the composition of natural gas can affect the performance of combustion
devices and may substantially increase -the emissions. It has also been shown by Pfefferle
et al. (1989a and 1989b), that the use of catalytic combustion reduced the dependence of
the system on the natural gas composition. Moreover, it has been shown that the addition
of asmall amount of ethane (less than 20% of the total fuel) to apredominantly methane
fuel enhanced significantly the OH radical production in the gas-phase allowing easier
ignition and flame propagation in their burner (Griffin et al., 1989). The catalytic
oxidation of premixed ethane in air within a packed bed reactor is discussed in this
section. The kinetic data used to obtain the predicted results are listed in Tables 7.1 and
7.2.
The conversion of ethane at different inlet temperatures is shown in Fig. 7.1. For
comparison, the conversion of methane is also shown. It can be seen that the noticeable
conversion within the inert bed starts at the inlet temperature of about 800 K for ethane
and 900 K for methane. The temperatures at which ignition of the fuel takes place are
855 and 1078 K for ethane and methane respectively, which is consistent with the fuels
reactivity. The ignition temperature of the fuel is defined as the temperature beyond
which a considerable amount of the fuel (10% and higher) is oxidized. As expected,
within the catalytic bed, the ignition and complete conversion take place at much lower
temperatures than within the inert bed, i.e. at 628 K for ethane and 745 K for methane.
- The conversion curves of ethane-air mixtures with different equivalence ratios'
and u1.0 m/s are shown in Fig. 7.2 for the inert bed. An increase in the equivalence ratio
towards stoichiometric value enhances the oxidation very significantly as would be
expected.
135
100
Catalytic Bekl CH
80
CH4
Fuel Conversion (%
C2
C2H6
60
40
Inert Bed
20
0 L
600 700 800 900 1000 1100

Fig. 7.1 Calculated fuel conversion as afunction of inlet temperature within an inert (*
symbol) and catalytic packed beds, 4= 0.35 and u= 1.0 m/s.
100
Inert Bed
80
0:15
0.24
.2' 60 0.35
0.50
,. c540
Q .
cJ
20
700 800 900 1000 . 1100

Fig. 7.2 Calculated ethane conversion as a function of inlet temperature within. an inert
bed for different equivalence ratios, u= 1.0 m/s, k5= 1.0 W/m.K, L = 50 mm.
136
For instance, the inlet temperature corresponding to 10% conversion of ethane decreases
from 995 to 677 K when the mixture equivalence ratio increases from 0.15 to 0.50.
Furthermore, aconsiderable decrease in the slope of the conversion curves i noticeable
when the mixture became very lean.
The equivalence ratio also has a similar effect on ethane oxidation within a
catalytic .bed (Fig. 7.3). However, the conversion of ethane starts at much lower inlet
temperatures than in case of the inert bed for the same conditions. For example, the
conversion of 100% ethane in mixtures of equivalence ratio of 0.50, 0.35, 0.24, and 0.15
is obtained at inlet temperatures of 470, 629, 760, and 845 K, respectively.
The gas and solid temperatures along the bed for these equivalence ratios at the
inlet temperature corresponding to the complete oxidation of ethane at the exit of the
reactor are plotted in Fig. 7.4. As the equivalence ratio of the mixtures decreases from
0.50 to 0.15 the exhaust temperature was reduced from 1711 to 1226 K respectively.
Moreover, the maximum gas temperatures corresponding to 84.4% ethane conversion
were decreased from 1816 to 1200 for = 0.50 and 0.15 respectively. It is also worth
emphasiing that the maximum value in the gas temperatures for mixtures of 4= 0.50,
0.35 and 0.24 are generated by the thermal energy released by ethane. This maximum
value in the gas temperatures diminishes as the mixture reaches the equilibrium state due
to heat exchange between the gas and solid phases by convection. Furthermore, the
maximum difference in the temperature between the gas and solid diminishes as
decreaes from 0.50 to 0.24. The thermal energy released for 4, = 0.15 was very small.
Thus, there was no peak value observed in the gas temperature under such conditions. It
appears that the thermal energy released by the mixture is reduced significantly with
decreasing the equivalence ratio in the mixture. This is rather expected. It is also noted
that the maximum temperature along the reactor is shifted from the left to the right as 4,
increases from 0.15 to 0.50 as shown in Fig. 7.4. This trend is expected because for the
mixture of 4, = 0.15 the inlet temperature is relatively high in comparison to the mixture
of 4, = 0.50; therefore, oxidation of ethane starts at an earlier location in the bed and
continues to increase gradually due to the low energy release from the fuel.
137
100
Catalytic Bed
80
. 60
0
Q40
QY
/ 4)
0.15
20- ' ! 0.24
1 0.35
- ! •.' -. 0.50
I ...... .
_______. . .
I I I
500 600 700 800 900 1000

Fig. 7.3 Calculated ethane conversion as a function of inlet temperature for different
equivalence ratios, u= 1.0 m/s, k = 1.0 W/m.K, L = 50 mm; Pt catalyst.
Fig. 7.4 Calculated temperature distribution for the gas (solid line) and the solid (broken
1800
Catalytic Bed 4=0.50
1600
1400
1200
1000
800
0.01 0.02 0.03 0.04 0.0

line) along the bed for various equivalence ratios of ethane, u= 1.0 m/s; Pt catalyst.
138
The effect of the flow velocity is shown in Fig. 7.5. It can be seen that an increase in the
flow velocity reduces the residence time and that this requires an increase in the inlet
temperature for the complete conversion of the fuel within the bed. The catalytic bed
improves ethane conversion significantly and allows it to take place at much lower inlet
temperatures. For example, the complete conversion of ethane for u= 3.0 m/s is obtained
at the inlet temperature of 850 K within the catalytic bed while the corresponding
temperature in the case of the inert bed was - 1080 K.
100 T
- Catalytic Bed
80 - i---.— u'1.O&s *
- u2.Om/s I
! u =3 .
0 m 1s
- i—.—.— u1.Om/s I
o 60 u2.Om/s I
I
-
- ! 3.
0 m/s
• :'
1
I
I
0
L) 40 -.
- I I
ii
20-. /
Inert Bed I
o il
600 700 800 900 1000
'I
1100
Fig. 7.5 Calculated ethane conversion as a function of inlet temperature within the
catalytic (thick lines) and inert (*, thin lines) beds for different approach velocities,
=0.35.
139
7.3 Propane Combustion
Catalytic oxidation of homogeneous mixtures of propane-air within the catalytic and inert
packed bed reactors are discussed in this section. The kinetic data used to obttain the
results of predictions for the heterogeneous and gas-phase reactions are listed in Tables
7.1 and 7.2.
The results of the calculations of the oxidation of homogeneous propane-air mixture
within the inert bed are shown in Fig. 7.6 at u= 1.0 m/s for various equivalence ratios.
-The trends observed are similar to those for other fuels (i.e., methane and ethane). As the
equivalence ratio of these lean mixtures increases the conversion of the propane is
completed at lower temperatures. For example, the complete conversion of propane in the
mixture with equivalence ratio of 0.50 took place at the inlet temperature of 767 K while
the temperature of 1150 K was needed for the complete conversion of propane in the
mixture with the equivalence ratio of 0.15. The conversion of propane was very fast with
an increase in the inlet temperature for the mixture of 4= 0.50 as it reaches conditions
corresponding to its lean flammability limit in air.
In the catalytic bed, propane is oxidized completely at amuch lower inlet temperature.
-
than in case of the inert bed for the same conditions. Moreover, the effects of the inlet
temperature and mixture equivalence ratio are also significant for the mixtures passing
through the catalytic bed (Fig. 7.7). An-increase in the equivalence ratio lowers the inlet
temperature at which complete oxidation of C3H8 occurs. For example, the complete
- conversion of the propane in mixtures with equivalence ratios of 0.15 and 0.50 is
obtained at the inlet temperatures of 900 and 540 K respectively. A similar trend was
observed by Bruno et al. (1983) experimentally and numerically for propane in a
platinum monolithic reactor for arange of equivalence ratios from 0.19 to 0.32.
140
100
InertBed
80 4)
0.15
0.24
- - - - - 0.35
. 60
c40
20
I I , I I , I p
900 800 900 1000 1100 1200

Fig. 7.6 Calculated propane conversion as afunction of inlet temperature within the inert
bed at different equivalence ratios, u= 1m/s, k = 1.0 W/m.K, L = 50 mm.
100
Catalytic Bed i
4):
-------0.15 I
0.24
0.35
- ---0.50
20
400 500 600 700 800 900 1000

Fig. 7.7 Calculated propane conversion as a function of inlet temperature at different
equivalence ratios, u= 1m/s, k = 1.0 W/m.K, L = 50 mm; Pt catalyst.

141
The calculated gas and solid temperatures distribution curves along the packed bed for
the complete oxidation of propane-air mixtures of equivalence ratios ranging from 0.50 to
0.15 are shown in Fig. 7.8. The trends of these curves demonstrated similar behavior to
those of ethane. However, two differences from ethane are observed in these curves.
First, the difference between the gas temperatures and solid temperatures in the region
corresponding to the peak in the gas temperature is smaller for propane-air mixtures than
for ethane-air mixtures for 4) = 0.50, 0.35, and 0.24. Second, for propane-air mixture the
temperatures of the gas and solid are higher than for ethane-air mixtures at all the
equivalence ratios examined. These higher temperatures are attributable to the higher
inlet tempethtures for complete oxidation in the case of propane-air mixtures. Such
behavior is consistent with the fuel reactivity.
Figure 7.9 shows the results of the oxidation of lean propane-air mixtures in inert and
catalytic packed beds at different approach velocities and 4) =0.35. Propane conversion
exhibits adependence on the approach velocity similar to that of the ethane-air mixture
with either bed. An increase in the approach velocity increased the inlet temperature for
the complete conversion of propane within the catalytic and inert beds (Fig. 7.9).
Figure 7.10 represents the conversion of methane, ethane and propane within the catalytic
and inert beds as afunction of the inlet temperatures for the flow condition of 4) = 0.35
and u = 1.0 m/s. Methane's complete conversion takes place at much higher inlet
temperatures than those required for the complete conversion of ethane or propane within
either an .inert or catalytic bed. This is consistent with the fuel reactivity which is higher
for ethane and lower for methane.
For instance for a fuel-air mixture of 4) = 0.35 within the inert bed, the complete
conversion of ethane is obtained at about -860 K while it requires inlet temperatures of

about -940 and 1088 K to achieve the full conversion of propane" and methane
,
respectively. This is expected due to the lower reactivity of methane in air compared with
that of ethane or propane. It should be also noted, that when the mixture is passing
142
91400
L
I
I
Ll 1200
1000
800
0 0.01 0.02 0.03 0.04 0.0

line) along the bed for various equivalence ratios of propane, u= 1.0 m/s; Pt catalyst.
100
80
. 60
C_) 40
20
700 800 900 1000 1100 1200

Fig. 7.9 Calculated propane conversion as a function of inlet temperature within the
catalytic (thick lines) and inert (*, thin lines) beds for different approach velocities,
=0.35.
143
through the inert bed, the effect of the mixture equivalence ratio is stronger for the
ethane-air and propane-air mixtures, than for the methane-air mixtures. Since only gas-
phase reactions are considered, the fuel r

eactivity mostly influences the conversion.
In the case of the catalytic bed, the corresponding temperatures for complete fuel
conversion are much lower as mentioned above (i.e. 628 Kfor ethane, 696 K for propane
and 745 K for methane). It can also be seen that in this case (catalytic bed) areverse trend
is observed, i.e. the effect of the mixture equivalence ratio is significantly stronger for the
methane-air mixtures than the ethane-air or propane-air mixtures. Such behavior is in
agreement with the experimental data of Griffin et al. (1992) for equivalence ratios
ranging from 0.03 to 0.5 and plate temperatures up to 1405 K. They found experimentally
that at atmospheric pressure, the platinum surface enhanced methane combustion to a
greater extent than that of ethane. It appears that the surface production of radicals
becomes more important to the ignition of methane.
100
CH4 *
C2H6 !
C3H8 1
80
CH4
I----- C2H.
C3H8
.9 60
40
20
)
600 700 800 900 1000 1100

Fig. 7.10 Calculated fuel conversion as afunction of inlet temperature within catalytic
(thick lines) and inert (*, thin lines) beds, = 0.35 and u= 1.0 m/s.
144
7.4 Carbon Monoxide Combustion
The oxidation of humid CO over platinum catalysts has been studied for many years, but
the conclusions regarding the mechanisms and rate equations are somewhat conflicting.
Tables 7.1 and 7.2 show the pre-exponential factor and the activation energy used to
obtain the predicted results in this section for catalytic and inert beds at atmospheric
pressure. The obtaining of asimple rate equation an aim of this investigation is of much
importance.
Figure 7.11 shows the results of the conversion within the inert bed for carbon
monoxide-air mixtures passing through the reactor as afunction of inlet temperatures
with u= 1.0 m/s and different equivalence ratios. An increase in the mixture equivalence
ratio significantly improved the firel conversion and allowed complete conversion at
much lower temperatures. For very lean mixtures of = 0.20 and 0.15 and at
temperatures below 1060 K, the effect of equivalence ratio appears negligible.
However, carbon monoxide conversion exhibited different behavior within the

catalytic bed than in the inert bed in its dependence on the equivalence ratio and inlet
temperatures. As illustrated in Fig. 7.12, the effect of the equivalence ratio is more
apparent at low temperatures. Whilst, the effect of the equivalence ratio diminishes as the
oxidation of the fuel reaches completion (i.e. exceeds 95%) carbon monoxide conversion
and for inlet temperatures of more than 800 K.
For the maximum conversion (- 97.5 %) of the carbon monoxide at the exit of the
50 mm long bed, the gas and solid temperature distributions for each of these equivalence
ratios is plotted in Fig. 7.13 along the catalytic bed. Similarly to the other fuels, the
increase in the equivalence, ratio increases the exhaust temperature and shifts the curves
toward the exit of the reactor. Since the energy release per unit volume of the carbon
monoxide mixtures is smaller than that for the hydrocarbon fuel, the peak in the gas
temperature distribution is not observed. The difference in the inlet temperature for all the
equivalence ratios tested is within 50 K. For instance, the inlet temperatures at = 0.35
and 0.15 are 800 and 850 K.

145
100
1
Inert Bed
80
-- - - - 0.15 II
- - -. - 0.20
0.35
60
.-
40 I ,
I,
C
U I,
20 '7 .
0
700 .800 900 1000 1100 1200 1300
Inlet Temperaturre (K)
Fig. 7.11 Calculated carbon monoxide oxidation as afunction of inlet temperature within
the inert bed for various equivalence ratios, u= 1.0 m/s.
CO Conversion (%)
400 500 . 600 700 800

Fig. 7.12 Calculated carbon monoxide oxidation as afunction of inlet temperattire for
various equivalence ratios, u= 1.0 m/s; Pt catalyst.

146
The effect of the approach velocity on the conversion of carbon monoxide within the
inert bed is similar to that of the other fuels as shown in Fig. 7.14 with stronger effects
between the velocities of u= 1.0 and 2.0 m/s.
A similar trend is observed for the dependence of carbon monoxide conversion on
approach velocities within the catalytic bed (see Fig. 7.15). The effect of the velocity is
stronger as the conversion reaches 80 % and above.
1800
1700
1600
1500
1400
1300
1200
1100
1000
900
800
0 0.01 0.02 0.03 0.04 0.05
along the bed for various equivalence ratios of carbon monoxide; u= 1.0 m/s; Pt catalyst
147
100
80
•o 60
.-
C
U
20
• 00 900 1000 1100. 1200 1300

Inlet Temperatune (K)
Fig. 7.14 Effect of approach velocity on calculated carbon monoxide conversion as a
function of inlet temperature within the inert bed, = 0.35.
100
80
CO Conveision (%)
60
40
20
600 800 1000 1200 1400

Fig. 7.15 Effect of approach velocity on calculated carbon monoxide conversion as a
function of inlet temperature, 4 = 0.35; Pt catalyst.

148
7.5 Hydrogen Combustion
The effect of the equivalence ratio on the conversion of hydrogen is presented in Fig.
7.16 within the inert bed with u= 1.0 m/s. Unlike the other fuels, methane, ethane, and
propane, the slopes of the hydrogen conversion curves are less steep even for the
equivalence ratio of 0.35. As the mixture become leaner, the slope of these conversion
curves becomes smaller. However, all the fuels employed in this investigation exhibited
similar behavior in their dependence on the mixture equivalence ratio. That is, the higher
the value of the fuel concentration, the higher is the rate of conversion of these fuels as
expected based onEqs. (7.1) and (7.2).
Hydrogen oxidation in the catalytic packed bed is presented in Fig. 7.17 for
various equivalence ratios and u= 1.0 m/s. A considerable amount of hydrogen ('-.25 %)
was oxidized already at room temperature 293 K for the mixture of 4i 0.35 with the
complete oxidation of hydrogen obtained at the inlet temperature of 420 K. A comparison
between the performance of the catalytic and inert beds is presented in Fig. 7.18 for
hydrogen-air mixtures of different equivalence ratios and u 1.0 m/s. The following
conclusions can be drawn from Fig. 7.18:
• The complete conversion of hydrogen within the catalytic bed was obtained at a
much lower temperature than that within the inert bed.
• The effect of the equivalence ratio on the hydrogen conversion within the inert
bed becomes significant at inlet temperatures above 760 K. When ignition started
at temperatures 770 and 800 K for the mixtures of equivalence ratios of 0.35
and 0.05 respectively, the reaction rate is very fast for 4= 0.35 and much slower
for the very lean mixture of 4= 0.05.
• The effect of the equivalence ratio on hydrogen conversion within the catalytic
bed is much stronger than that within the inert bed. Pfefferle and Pfefferle (1987)
have experimentally observed similar behavior for hydrogen mixtures of
equivalence ratio less than 0.3. They have explained that such promotion is due to
the very efficient ability of platinum to dissociate molecular oxygen.

149
100
,
,
Inert Bed
/
80 l) /
0.05
0.10 /
- - - - 0.15
- - - - - 0.35
60
40
/
20
700 800 900 1000

Fig. 7.16 Calculated hydrogen conversion as afhnction of inlet temperature at different
equivalence ratios within the inert bed, u= 1.0 m/s.
100
/
80
/
-
/
/
60
I
I
/
40
I
/ Catalytic Bed
/
0.05
20
/ 0.10
I 0.15
I 0 i
300 400 500 600 700 800 900

Fig. 7.17 Calculated hydrogen conversion as afunction of inlet temperature at different
equivalence ratios, u= 1.0 m/s; Pt catalyst.

150
The temperature distribution along the catalytic bed for the complete conversion of
hydrogen in air is shown in Fig. 7.19 for various equivalence ratios and u= 1.0 m/s. The
temperature increases as the equivalence ratio increases which is rather expected.
Moreover, several differences were observed between hydrogen mixtures and the other
fuels considered in this investigation. A gradual increase in the temperature of the gas
and solid along the bed is observed. Furthermore, there is no peak in the gas temperature
curve after ignition observed for hydrogen. This can be attributed to the fact that the
energy release by hydrogen, on avolume basis of the mixture, is smaller. The influence
of ahot catalytic surface on the ignition of gas-phase combustion in fuel/air mixtures has
been shown to be a strong function of mixture stoichiometry (Pfefferle and Pfefferle,
1987). Besides, Schefer and Robben (1980) found that for ethane, propane and hydrogen
ignition the catalytic inhibition effect becomes lower as the mixtures were made leaner.
Figure 7.20 shows the temperature distribution of the solid and gas for all the fuels (i.e.
CH4,C2H6,C3H8,CO, and H2)employed in this investigation within the catalytic bed at 4

= 0.35 and u = 1.0 m/s. The complete conversion of the fuel is achieved at the lowest
inlet temperature of 420 K for the hydrogen-air mixture. Furthermore, the lowest exhaust
gas temperature is obtained for hydrogen fuel because it has the lowest inlet temperature
required for the complete conversion. This is consistent with its high reactivity. Also, it is
worth to mention that the maximum gas temperature for the fuels employed in the present
investigation is below 1700 K and hence thermal NO emission is insignificant.
The dependence of hydrogen conversion on the approach velocity within the inert bed is
similar to the other fuels. Figures 7.21 and 7.22 illustrate this dependence for two
different equivalence ratios of hydrogen-air mixture ( = 0.10 and 0.35). The lean
flammability limit for hydrogen in air is of = 0.15 at 400 °C for horizontal gas phase
propagation (Zabetakis, 1965). Thus, the mixture with an equivalence ratio of 0.35 is
within the flammable region while the mixture of k 0.10 is outside.

151
100
-
I.
-.—.,
,. II
80 - 'I Catalytic Bed / I

- I
I !
Inert Bed
40 0.05
:!
0.10
0.15
I/I 0.35
20 I
/1 0.05 •
0.10
I 0.15 •
/ 0.35
0
400 600 800 1000
Fig. 7.18 Comparison between calculated hydrogen conversion within the catalytic and
inert beds (*; thin lines) versus inlet temperature for various equivalence ratios, u=1.0
m/s.
1200
1100
800
700
600
500
I I i
400 o 0.01 0.02 0.03 0.04 0.0

line) along the bed for various equivalence ratios of hydrogen; u= 1.0 m/s; Pt catalyst.
152
1800
Catalytic Bed
1600
g 1400
1200
Fi000
800
600
400 o
0.01 0.02 0.03 0.04 0.05
line) for CH4,C2H6,C3H8, CO, and H2 along the bed, = 0.35, u= 1.0 m/s; Pt catalyst.
100
/
IneitBed
/
80 ------u1.Om/s I
u2.Om/s I
....... u=3.Om/s /
ç 40
20
/
/
700 800 900 1000

Fig. 7.21 Calculated hydrogen conversion as afunction of inlet temperature within the
inert bed for different approach velocities, = 0.10.

153
It is clear from Figs. 7.21 and 7.22 that for both mixtures the effect of the approach
velocity on hydrogen conversion is more significant at higher inlet temperatures.
Complete conversion of hydrogen at u = 1.0 m/s is achieved at the inlet temperatures of
820 K and 980 K for 4) = 0.35 and 0.10 respectively. Inlet temperatures of 875 K and
1050 K are needed to obtain the complete conversion of hydrogen at u= 2.0 m/s. For the
complete conversion of hydrogen with velocities of 1.0 and 2.0 m/s, an inlet temperature
difference of 55 K and 130 Kis obtained for the mixtures 4) 0.35 and 0. 10, respectively.
The effect of approach velocity on hydrogen conversion within the catalytic bed
(Fig. 7.23) is more pronounced than that within the inert, bed (Fig. 7.22). Figure 7.24
shows a comparison of hydrogen conversion between the catalytic and inert beds for
various approach vekocities at 4) = 0.35. The effect of the velocity within the catalytic bed
is significant especially for hydrogen conversion less than 40%. Moreover, it is
noticeable that at the velocity of 3.0 m/s within the catalytic bed a much higher inlet
temperature is required to achieve the complete conversion of hydrogen than when the
velocity is 1.0 rn/s.
Inert Bed
I
- - - - u1.OmJs
u2.Om/s
u3.Om/s
I
I
I
I
/
I
I
50 700 750 800 850 900

Fig. 7.22 Calculated hydrogen conversion as afunction of inlet temperature within the
inert bed for different approach velocities, 4) 0.35.

154
100
80
c 40
20
0
300 400 500 600 700 800
Fig. 7.23 Calculated hydrogen conversion as afunction of inlet temperature for different
approach velocities, 4) = 0.35; Pt catalyst.
100 ,
Ij
Ii
I I
80
i Catalytic Bed/
i I
Ii
I
60
I I
I I I I
I.
- I i/
1 I
I
I
(
I
40
I. InertBed
, I! - - - - u1.Om/s
uQ.Om/s
u3.Om/s
20 u1.0m1s
I u-2.0 m/s'
- / 1
• u=3.0 m/s *
I 1 !IIII I II I- 111 I I I I
0 300 400 500 600 700 800 900 1000 1100
Fig. 7.24 Comparison between calculated hydrogen conversion within the catalytic and
inert beds (*; thin lines) versus inlet temperature for various approach velocities, 4) =
0.35.
155
CHAPTER 8
COMPARISON OF MODEL PREDICTION WITH THE
EXPERIMENTAL DATA
8.1 Introduction
One of the aims of this investigation is to estimate more accurately the rate expression for
catalytic oxidation within apacked bed reactor. Based on experimental data obtained by
Depiak (2003) with two different catalysts, the kinetic data (i.e. the activation energy and
the pre-exponential factor) for the overall rate expression within the packed bed reactors
were determined using the same procedure discussed in section 6.2 of Chapter 6. The
gas-phase kinetic coefficients for C3H8, CO, and H2 are from the literature and are listed
in Table 7.1.
8.2 Determination of Kinetic Data for Surface Reactions of Common
Gaseous Fuels
Propane-air mixture: Fig. 8.1 shows the experimental and predicted results of propane
conversion within the platinum bed of 4= 0.35 and u= 1.0 m/s: For the platinum packed
bed, the corresponding value of the activation energy is 27.7 ± 1.1 kJ/mol and the pre-
exponential factor is 1.70 x10 -3 kmoll(rn2.

s).
However for the Co 3O4ICr2O3 packed bed these values, as can be seen in Fig. 8.2, are:
Activation energy (Es)of 25.10 ± 1.9 kJ/mol at inlet temperatures 700 K;
Activation energy (Es) of 29.87 ±0.9 k3/mol at inlet temperatures > 700 K;
with the pre-exponential factor (As)of 1.70 x i0 kmoll(m2.$).

156
100 • ..41- -
80
0
I
/
/
/
/
I
/
/
Pt Catalyst
20
- - - Calculated Data (present work)
• Experimental Data (Depiak, 2003)
400 500 600

I 700 800 900 1000
Fig. 8.1 Calculated and experimental propane conversion as a function of inlet
temperature within platinum bed, t1 = 0.35, u= 1.0 m/s.
100
80
° 60
$ 1
0
ç..) 40
C0 30./Cr2O3 catalyst
20 1'
- - - - Calculated Data (present work)
• Experimental Data (Depiak, 2003)
04 o8 I I I I I I
500 600 700 800
+I
900 1000
Fig. 8.2 Calculated and experimental propane conversion as a function of inlet
temperature within C0304/Cr2O3 bed, 1= 0.35, u = 1.0 m/s.

157
Carbon monoxide-atmospheric air mixture: for the temperature range tested there seem
to be two activation energies for the surface reaction of carbon monoxide over aplatinum
catalyst. The following activation energies provided and an adequate representation of the
experimental data of Depiak (2003), as can be seen in Fig. 8.3.
Activation energy (Es) of 25.56 ± 1.7 kJ/rnol at inlet temperatures < 650 K;
Activation energy (E s)of 20.56 ±2.0 kJ/mol at inle

ttemperatures> 650 K.
Thd pre-exponential factor (As) for the above activation energies is 2.2 x 10-3 kmol/(m2.$).
Furthermore, the Co 3O4ICr2O3 catalyst yields an activation energy (Es) of 27.0 ±
1.0 kJ/mol at inlet temperatures 650 K and avalue for E of 23.0 ± 1.3 kJ/mol at inlet
temperatures> 650 K. The pre-exponential factor for the ço3O4JCr2O3 packed bed is 2.4
x i0 kmoll(m2.$) (Fig. 8.4).

158
100
80
CO Conversion (%)
I,
60
/
/
/
40
/
Pt Catalyst
/
/
20
- - - Calculated Data (Present work)
Experimental Data (Depiak, 2003)
0
400 500 600 700 800 900
Inlet Tem perature (K)
Fig. 8.3 Calculated and experimental carbon monoxide conversion as afunction of inlet
temperature within platinum bed, 4) = 0.35, u = 1.0 m/s.
100
80 /
Co 3O4ICiO3 Catalyst
20
- - - - Calculated Data (Present work)
I I
500 600 700 800 900
Fig. 8.4 Calculated and experimental carbon monoxide conversion as afunction of inlet
temperature within C0304/Cr2O3 bed, 4) = 0.35, u= 1.0 m/s.

159
Hydrogen-air mixture: kinetic data for hydrogen within the platinum packed bed is also
obtained as shown in Fig. 8.5. At inlet temperature 350 K, the activation energy (E) is
10.0 ± 0.5 kJ/mol. An activation energy is 9.4 ± 0.6 kJ/mol at inlet temperature >350 K.
The pre-exponential factor for this mixture is 5.4 x 10-5 kmoL'(m2.$). The activation
energy determined in this investigation is close to the value reported by Boreskov (1954),
10 kJ/mol, for his high activity platinum wire in excess of oxygen. Moreover, Hanson
and Boudart (1978) reported avalue for the activation energy of 7.5 kJ/mol in their study
of hydrogen conversion to water (H20) over platinum supported on silica at temperatures
from 273 to 373 K at atmospheric pressure. Furthermore, avalue of 16.1 kJ/mol was
reported by Brown et al. (1983): Their reaction is in the temperature range from 450to
1074K and equivalence ratios from 0.05 to 0.20 for hydrogen on aplatinum catalyst
within the laminar heated boundary layer. Also, an earlier study of Gidaspow and
Ellington (1964) noted arather abrupt change in the mechanism at temperatures near 450
K. This change was expressed as a decrease in activation energies for temperatures
greater than 450 K.
Applying the same strategy to hydrogen oxidation over the C0304/Cr2O3 catalyst
will yield an activation energy of 10.3 ± 1.0 kJ/mol (Fig. 8.6).
The kinetic data for the common gaseous fuels in air mixtures employed in this
investigation over the platinum and C0304/Cr2O3 catalysts are summarized in Table 8.1.
160
100
80 -
40-
20-
r Pt catalyst
0 Experimental Data (Depiak, 2003)

- - - Calculated Data (present work)
9oo 300 400 , 500 600 700

Fig. 8.5 Calculated. and experimental hydrogen conversion as a function of inlet
temperature within platinum bed, 4) = 0.35, u= 1.0 m/s.
,100
a/
60
40
20
- - - - Calculated Data (present work)
I I
00 300 400 500 600 700
Inlet Ternpemtun (K)
Fig. 8.6 Calculated and experimental hydrogen ,conversion as a function of inlet
temperature within C0304/Cr2O3 bed, 4) = 0.35, u= 1.0 m/s.

Table 8.1 Kinetic data for platinum and C0304/Cr2O3 catalysts within the packed bed reactor for all the fuels employed in this
study.
Platinum Catalyst C0 3 0 4 /Cr 2 O 3 catalyst Temperature Range

Fuel Type
(To
A (kmoLf(m2.K)) E (kJfmol) A (kmol/(m2.K)) E (kJ/mol)
42.0 42.8 775.0

CH4 1.03 x iO 3 2.2x1c13
46.0 46.3 >775.0
25.1 700.0
C3H8 1.70 x iO 3 27.7 1.7x i0
29.8 >700.0
25.56 27.0 650.0

CO 2.2x10 3 2.4x iO
20.56 23.0 > 650:0
10.0 350.0
H2 5.4x i0 5.4x iO 10.3
9.4 >350.0
162
8.3 Summary
A comparison between the. predicted results using the kinetic data obtained during the
present investigation with the predicted results using the kinetic data from the literature is
presented in Figs. 8.7 to 8.9 when platinum is the catalyst.
Propane-air mixture: the kinetic data used for the parametric study of propane reaction
mechanism in section 7.3 when compared to the kinetic data reported in the present study
as shown in Fig. 8.7 for 4= 0.35 and u= 1.0 m/s show significant differences. It appears
that the value of the activation energy of 27.7 ± 1.1 kJ/mol is far apart from that reported
by Song et al. of 70.85 kJ/mol for lean propane-air mixtures -over aplatinum flat plate.
Such large discrepancy in the values of the activation energy may be due to the different
reactor geometry which can have alarge influence on the values of the activation energy
as was indicated in the literature review. In addition, the effective activation energy is
dependent on the nature of the platinum surface (i.e., dispersed or particulate platinum)
which is not clearly stated in the various experimental results. The extent of fuel
conversion results is structure-sensitive to the platinum surfaces as shown by Otto (1989).
However, aan activation energy of 29.69 kJ/mol was

' reported by Kuo et al. (1980) for
fast oxidizing hydrocarbon group which includes prOpane over platinum catalytic
converter (packed spherical particles). This value of the 'activation energy, is only ,6.7 %
higher than the value obtained in the present investigation. In any case, it is ,to b
remembered that the concept of assuming that the multi-reactions on the catalytic,, surface
can be represented by asingle overall reaction step is highly approximate and c'an lead to
substantial differences in the values of the results.
Carbon monoxide-atmospheric air mixture: acomparison is presented (Fig. 8.8) of the
predicted carbon monoxide conversion using the kinetic data obtained here with the
predicted results from the literature (Table 7.2) over a platinum catalyst. Activation
energies of 25.56 ± 1.7 kl/mol and 20.56 ±2.0 kJ/mol for temperatures above and below
650 K, respectively are obtained which compare to that of 23.56 kJ/mol of Kuo et al.
163
(1980). The calculated carbon monoxide conversion when using the kinetic data of Kuo
et al. is over-predicted for the temperature range between 450 to 650 K, while
temperatures higher than 650 K, is under predicted. Such behavior is also mainly due to
the use of single activation energy over the entire range of temperature (i.e., 450 - 850 K)
while more than one activation energy is needed. Thus, atwo temperature regime (above
and below 650 K) for the activation energy is employed to better fit the experimental
data. The two regime approach is for example also consistent with the data of Song et al.
(1990). At low temperature regime, the difference in the activation energy between the
values of the present study and that of Kuo et al. is 13.0%, and at the higher temperature
regime is 8.0%.
Hydrogen-air mixture: the activation energy obtained during the present investigation is
10.0 ± 0.5 kJ/mol for temperatures 350 K and 9.4 ± 0.6 kl/mol for temperatures> 350
K. There are many low values of the activation energy which is consistent with the highly
reactive behavior of hydrogen. Calculated hydrogen conversion is compared to that of
Boreskov (1954) in Fig. 8.9 and show adeviation in the activation energy value from his
values of 2.9% for low temperature regime and 6.0% for the high temperature regime.
It can be concluded that using single activation energy for awide range of temperature
may lead to significant error in the fuel conversion. Therefore, it is recommended the use
of at least two or may be more than two activation energies for the entire range of
temperature required to achieve the complete conversion of the fuel.

164
100
Pt Catalyst
= - - - - Calculated Data (present work)
Calculated Data (Kinetic data of Haim et al.)
- Experimental Data (Depiak, 2003) I
I
.2 60 I
41
I
o
0 /
40 /
e. I
/
20
100
80
/
o 60
/
/
/
C I.
0 Pt Catalyst
/
20 Calculated Data (Kinetic data, present work)
Calculated Data (Kinetic data; Kuo et al.)
I I I
400 500 600 700 800 90
Fig. 8.8 Comparison of calculated carbon monoxide conversion as afunction of inlet
temperature within platinum bed, 4= 0.35, u= 1.0 m/s.

165
60
540
Pt catalyst
- - - - - Calculated Data (KInetic data; present work)

Calculated Data (Kinetic data of Boreskov)
5 Experimental Data (Dcpiak, 2003)
II I I III I I II I i I
300 400 500 600 700
Fig. 8.9 Comparison of calculated hydrogen conversion as afunction of inlet temperature
within platinum bed, 4= 0.35, u = 1.0 m/s.

166
CHAPTER 9
CONCLUSIONS AND RECOMMENDATIONS
9.1 Summary and Conclusions
The oxidation of lean fuel-air mixtures within a packed bed .reactor was investigated
experimentally and numerically. An unsteady plug-flow mathematical model of fuel
conversion in lean premixed and preheated fuel-air mixtures in apacked bed reactor with
inert or platinum catalyst deposited on y-alumina pellets was developed. The governing
conservation equations of mass, chemical species, and energy for both the gas and the
solid and the corresponding boundary conditions were solved using afinite-difference
procedure. The reaction rates, for the gas-phase (homogeneous) and catalytic surface
(heterogeneous) of the Arrhenius type modeled as single-step reactions, were
incorporated to determine the conversion of fuel as afunction of inlet temperatures. The
model allows for considering the role of individual homogeneous and heterogeneous
reactions as well as coupled homogeneous-heterogeneous reactions in the fuel oxidation.
Even though, the model was based on aone-step reaction, it was adequate enough to
predict the features of the catalytic packed bed reactor. The predicted results obtained
were compared with experimental values. Accordingly, aparametric investigation was
performed. Also, effects of changes in the bed porosity, solid thermal conductivity, and
bed length on the conversion of lean methane-air mixtures were investigated.
Experiments were performed on two types of packed beds: inert and catalytic.
The fuel conversion was obtained for each catalytic bed tested namely platinum and a
binary mixture of cobalt and chromium oxides. The range of the operational parameters
covered in the experiments was between approach velocities of 0.75 to 3.0 m/s,
equivalence ratios of 0.2 to 0.6, and inlet temperatures of 293 to 1300 K. The kinetic data
for the oxidation of methane, propane, carbon monoxide, and hydrogen within the packed
167
bed reactor were obtained for platinum and the binary mixture of cobalt and chromium
oxide catalysts.
The major conclusions of this study for all the fuels employed within the inert and
catalytic packed beds are listed below:
, The complete conversion of the fuel, as expected, increased with increasing
inlet temperatures and equivalence ratios or decreasing approach velocities
regardless of fuel type.
• The conversion of the fuel is most sensitive to inlet temperature among the
three inlet parameters (Ti,,,f, and u). It was found that, aone percent change in
inlet temperature can cause asignificant change in overall conversion.
. Fuel conversion within catalytic beds takes place at much lower temperatures
than it does in inert beds for the same equivalence ratio and approach velocity
for all the fuels considered in this investigation.
• For only the heterogeneous reaction case, methane oxidation improved with the
decrease in the bed porosity and or increase in the bed length.
• The effect of solid thermal conductivity (k = 1.0 - 4.0 W/m.K) on methane
conversion was negligible for the only heterogeneous reaction case.
• For the coupled homogeneous-heterogeneous reactions case, an increase in the
bed porosity enhanced methane oxidation and allowed complete conversion to
take place at an earlier location in the reactor.
• A bed length of L = 50 mm was sufficient for completing the oxidation of

methane for a bed porosity of 0.4 or less when the coupled homogeneous-
heterogeneous reaction was considered for k 0.35

= and u= 1.0 m/s.
• An increase in the thermal conductivity of the solid improved the oxidation
process and allowed complete conversion to take place at an earlier location
within the reactor for the case of coupled homogeneous-heterogeneous reaction.
• It is important to consider the coupled homogeneous-heterogeneous reactions
when modeling the fuel oxidation within the packed bed reactor.
168
• The activation energies and pre-exponential factors were obtained for all the
fuel-air mixtures oxidized over the platinum and C0304/Cr2O3 catalysts in this
investigation. The values of these kinetic data are summarized in Table 7.3.
• Methane oxidation exhibited similar behavior with the metal oxides and
platinum catalysts. Increases in the equivalence ratio as well as in the inlet
temperatures or decreases in mixture approach velocity improved methane
conversion. The effect of equivalence ratio was more significant at intermediate

temperatures.
• For the platinum catalyst asubstantial decrease in the methane conversion was
associated with ageing. A fresh platinum catalyst exhibited higher reactivity
than aC0304/Cr2O3 catalyst in methane conversion. However, aC0304/Cr2O3
catalyst showed better performance in methane conversion than an aged
platinum one.
• No carbon monoxide was detected in the exhaust gas under any operating
conditions employed for the platinum catalyst. A noticeable increase in the
carbon monoxide concentration in the exhaust gas was observed with an
increase in the inlet temperatures and equivalence ratio for the C0304/Cr2O3
catalyst.
• The C0304/Cr2O3 catalyst exhibited higher thermal stability than the platinum
catalyst.
The developed mathematical model is sufficient for design purposes. The model was
used to provide a parametric investigation for fuel conversion within the packed bed
reactor such as inlet temperature, equivalence ratio, approach velocity, bed porosity, solid
thermal conductivity, and bed length. The developed model has proven successfully its
capability to provide the parametric study for the catalytic and the inert packed beds.
Accordingly, the costly and lengthy experimental verification can be reduced or
minimized.
169
9.2 Recommendations for Further Work
Several recommendations can be made for future work on catalytic oxidation of fuels
within packed bed reactors:
• To improve the modeling of the oxidation of fuel and air mixtures, it is
recommended that a detailed chemical kinetics for homogeneous reactions
should be included especially at low temperature to investigate the effect of
gas-phase radical formation on surface reactions.
• It is beneficial to include detailed surface chemistry in the modeling of catalytic
combustion in spite of the fact that it is very complicated and still at the early
stages of development. It can qualitatively account for the characteristic
behavior of the reactor and lead to further improvement in the combustion

processes.
• The model developed should be extended to consider the oxidation of lean
binary fuel mixtures in air.
• The model should be modified to include rich equivalence ratios for methane's
partial oxidation to produce hydrogen as apart of synthesis gas. This avenue, of
hydrogen production could be very beneficial.
• Obtaining experimental data on the effect of bed porosity for the oxidation of
lean fuel-air mixtures for the purposs of model validation. This could be done
by using different pellet diameters and/or different shapes to cover wider ranges
of porosity and topology of porous materials.
• A ceramic bed reactor capable of withstanding higher operating temperatures

than with quartz needs to be developed and employed.
170
REFERENCES
Adelman, B. J., Beutel, T., Lei, G.-D., and Sachtler, W. M. H., "Mechanistic Cause of
Hydrocarbon Specificity over Cu/ZSM-5 and Co/ZSM-5 Catalysts in the Selective
Catalytic Reduction of NO N", J. Catal., Vol. 158, pp. 327-335 (1996).
Agarwal, S. K., Jang, B. W.-L., Oukaci, R., Riley, A., and Marcelin, G., "NO Control by
Catalytic Combustion of Natural Gas", American Chemical Society chp. 18,.pp. 224-232
(1994).
Ahn, T., Pinczewski, W. V., and Trimm, D. L., "Transient Performance of Catalytic
Combustors for Gas Turbine Applications", Chem. Eng. Sci., Vol. 41(1), pp. 55-64
(1986).
Aleksandrov, E. N., and Azatyan, V. V., "Oxidation of Carbon Monoxide", Dokl. Akad.
Nauk. SSSR, Vol. 210, No. 6, pp. 1358-1361 (1973).
Alfa Aesar catalog, A Johnson Matthey Company, Ward Hill, Ma 01835-8099 'USA
(2001-02).
Anderson, S. J., Friedman, M. A., Krill, W. V., Kesselring, J. P., "Development of a
Small-Scale Catalytic Gas Turbine Combustor", Trans. ASME, Vol. 24, pp. 52-57
(1982).
Balakrishna, A., Schmidt, L. D., and Aris, R., "Pt-Catalyzed Combustion of CH4-C3H8
Mixtures", Chem. Eng. Sci., Vol. 49(1), pp. 11-18 (1994).'

171
Beebe, K, Cairns, K, and Pareek, V., "Development of Catalytic Combustion Technology
for Single-Digit Emission Industrial Gas Turbines", 4th International Workshop on
Catalytic Combustion, San Diego, 14-16 April (1999).
Bensalem, 0., and Ernst, W. R., "Mathematical Modeling of Homogeneous-
Heterogeneous Reactions in Monolithic Catalysts", Combust. Sci. Technol., Vol. 29, pp.
1-13 (1982).
Bharadwaj, S. S., and Schmidt, L. D., "Synthesis Gas Formation by Catalytic Oxidation
of Methane in Fluidized Bed Reactors", J. Catal., 146, pp. 11-21(1994).
Biloen, P., Dautzenberg, F. M., and Sachtler, W. M. H., "Catalytic Dehydrogenation of
Propane to Propene over Platinum and Platinum-Gold Alloys", J. ôatal., Vol. 50, pp. 77-
86(1977).
•Blazowski, W. S., and, Walsh, D. E., "Catalytic Combustion: an Important Consideration
for Future Applications", Combust. Sci. and Technol., Vol. 10, pp. 233-241 (1975).
Boehman, A. L., Niksa, S., and Moffat, R. 5., "Catalytié Oxidation of Carbon Monoxide
in aLarge Scale Planar Isothermal Passage", SAE 922332, pp. 119-128 (1992).
Bond, T. C., Noguchi, R. A., Chou, C.-P., Mongia, R. K., Chen, J.-Y., and Dibble, R. W.,
"Catalytic Oxidation of Natural Gas over Supported Platinum: Flow Reactor Experiments
and Detailed Numerical Modeling", Twenty-Sixth Symposium (International) on
Combustion/The combustion Institute, pp. 1771-1778 (1996).
Boreskov, G. K., J. Chim. Phys., Vol. 51, pp. 759 (1954).

172
Boudart, M., Collins, D. M., Hanson, F. V., and Spicer, W. E., "Reactions between H2
and 02 on Pt at Low and High Pressures: A Comparison", J. Vac. Sci. Technol., Vol.
14(1), pp. 441-443 (1977).
Bozo, C., Guilhaume, N., Garbowski, E., and Primet, M., "Combustion of Methane on
CeO 2-ZrO 2 Based Catalysts", 4th International Workshop on Catalytic Combustion, San
Diego, 14-16 April (1999).
Bradley, D., and Matthews, K. J., "Meauremënts .of High Gas Temperatures with Fine
Wire Thermocouples", J. Mech. Eng. Sci., Vol. 10(4), pp. 299-305 (1968).
Brown, N. J., Schefer, R. W., and Robben, F., "High-Temperature Oxidation of H2 on a
Platinum Catalyst", Combust. Flame, Vol. 51, pp. 263-277 (1983)
Bruno, C., Walsh, P.M., Santavicca, D.A., Sinha, N., Yaw, Y., and Bracco, F. V.,
"Catalytic combustion of propane/air mixtures on platinum", Combust. Sci. Technol.,
Vol. 31, pp. 43-73 (1983).
Bui, P.-A., Vaichos, D. G., and Westmoreland, P. R., "Homogeneous Ignition of
Hydrogen-Air Mixtures Over Platinum", Twenty-Sixth Symposium (International) on
Combustion/The Combustion Institute, pp. 1763-1770 (1996).
Butt, J. B. and Petersen, E. E., Activation, deactivation, and poisoning of catalysts,
Acadimic Press, Inc. (1988).
Cern, I., Saracco, G., and Specchia, V., "Methane Combustion over Low-Emission
Catalytic Foam Burners", Catal. Today, Vol. 60, pp. 21-32 (2000).
173
Chen, D. K. S., Bissett, E. J., Oh, S. H., and Ostrom, D. L. V., "A Three-dimensional
Model for The Analysis of Transient Thermal and Conversion Characteristics of
Monolithic Catalytic Converters", SAE paper 880282, pp. 1-13 (1988).
Cho, W., Back, Y.-S., Oh, Y., Lee, Y., Park, D., and Pang, H., "Development of the
Catalytic Burner of Natural Gas for a Textile Pad Dryer and aPrototype Boiler", 4th
International Workshop on Catalytic Combustion, San Diego, 14-16 April (1999).
Choudhary, V. R., Rajput, A. M., and Mamman, A. S., "NiO-Alkaline Earth Oxide
Catalysts for Oxidative Methane-to-Syngas Conversion: Influence of Alkaline Earth
Oxide on the Surface Properties and Temperature-Programmed Reduction/Reaction by
H2 and Methane", J. Catal., Vol. 178, pp. 576-585 (1998).
Choudhary, V. R., Rajput, A. M., and Prabhakar, B., "Nonequilibrium Oxidation of
Methane to CO and H2 with High Selectivity and Productivity over Ni/A1203 at Low
Temperatures", J. Catal:, Vol. 139, pp. 326-328 (1993).
Coffee, T. P., "On Simplified Reaction Mchanisms by Oxidation of Hydrocarbon Fuels
in Flames by C. K. Weestbrook and F. T. Dryer", Combust. Sci. Technol., Vol. 43, pp.
333-339 (1985).
Coltrin, M. E., Kee, R. J., and Rupley, F. M., "Surface Chemkin: A General Formalism
and Software for Analyzing Heterogeneous Chemical Kinetics at a Gas-Surface
Interface", Int. J. of Chem. Kinet., Vol. 3, pp. 1111-1128 (1991).
Corma, A., Palomares, A. E., and Fornes, V., "A Comparative Study on the Activity of
Metal Exchange MCM22 Zeolite in the Selective Catalytic Reduction of NOR", Res.
Chem. Intermed., Vol. 24, pp. 613-623 (1998).

174
Cullis, C. F., and Willatt, B. M., "Oxidation of Methane over Supported Precious Metal
Catalysts", J. Catal., Vol. 83 pp. 267-285 (1983).
Cybulski, A., and Moulijn, J. A., "Monoliths in Heterogeneous Catalysis", Catal. Rev.-
Sci. Eng., Vol. 35 (2), pp. 179-270 (1994).
Cybulski, A., and Moulijn, J., Structured Catalytsts and Reactors, Marcel Dekker (1998).
Dalla Betta, R. A., "Field Testing and Commercialisation of XONON Catalytic
Combustion Technology in Gas Turbines", 4tli International Workshop on Catalytic
Combustion, San Diego, 14-16 April (1999).
Davy, H., "Some New Experiments and Observations on the Combustion of Gaseous
Mixtures", in The Collected Works of Sir Humphery Davy (J. Davy, ed.), Vol. 6, Smith,
Elder and Co., Cornhill, London (1840).
Dekker, F. H. M., Dekker, M. C., Bliek, A., Kapteijn, F., and Moulijn, J. M., "A
Transient Kinetic Study of Carbon Monoxide Oxidation over Copper-Based Catalysts for
Automotive Pollution Control", Catal. Today, Vol. 20, pp. 409-422 (1994).
Depiak, A. M., "Catalytic Oxidation of Heated Lean Homogeneous Gaseous Fuel-Air
Streams" Ph D. Thesis, Department of Mechanical and Manufacturing Engineering, The
University of Calgary, Calgary, Alberta (2003).
Depiak, A. M., and Wierzba, I., "An Experimental Investigation of Oxidation of
Common Gaseous Fuels over Cobalt Oxide /Chromium Oxide Catalyst in aPacked-Bed
Reactor", ASME-Energy Sources Technology Conference & Exhibition, ETCE99-6709,
pp. 1-5 (1999).

175
Depiak, A. M., and Wierzba, I., "The Catalytic Oxidation of Heated Lean
Homogeneously Premixed Gaseous-Fuel Air Streams", J. Chem. Eng., Vol. 91, pp. 287-
295 (2003).
Desai, Amit .
J., Kovaichuk, Vladimir I., Lombardo, Eduardo A., and d'Itri, Julie L.,
"CoZSM-5: Why This Catalyst Selectively Reduces NO with Methane", J. Catal., Vol.
184, pp. 396-405 (1999).
Deutschmann, 0. D., and Schmidt, L. D., "Two-Dimensional Model of Partial Oxidation

of Methane on Rhodium in aShort Contact Time Reactor", Twenty-Seventh Symposium
(International) on Combustion/The Combustion Institute, pp. 2283-2291 (1998).
Deutschmann, 0., Schmidt, R., Behrendt, F., and Warnatz, J., "Numerical Modeling of
Catalytic Ignition", Twenty-Sixth Symposium (International) on Combustion/The
Combustion Institute, pp. 1747-1754 (1996).
Dupont, V., Moallemi, F., Williams, A. and Zhang, S.-H., "Combustion of Methane in
Catalytic Honeycomb Monolith Burner", mt. J. Engy Res., pp. 1-21 (2000).
Duterque, J., Borghi, R., and Tichtinsky, H., "Study of Quasi-Global Schemes for
Hydrocarbon Combustion", Cdmbust. Sci. Technol., Vol. 26, pp. 1-15 (1981).
Dwyer, F. G., "Catalysis for Control of Automotive Emissions", Catal-Rev., Vol 6, No.
2, pp. 261-291 (1972).
Gidaspow, D., and Ellington, R. T., A.I.Ch.E.J., Vol. 10, pp. 107 (1964).
Glassman, I., "The homogeneous oxidation kinetics of hydrocarbons: concisely and with
application", Dept. of mech. and Aerosp. Engin. Rep. 1446, Princeton Univ., Princeton,
N.J. (1980).
176
Goralski, C. T., and Schmidt, L. D., "Modeling Heterogeneous and Homogenous
reactions in the High-Temperature Catalytic Combustion of Methane", Chem. Eng. Sci.,
Vol. 54, pp. 579 1-5807 (1999).
Griffin, T. A., Calabrese, M., Pfefferle, L, D., Sappey, A., Copeland, R., and Crosley, D.
R., "The Influence of Catalytic Activity on the Ignition of Boundary Layer Flows. Part
III: Hydroxyl Radical Measurements in Low-Pressure Boundary Layer Flows", Combust.
Flame, Vol. 90, pp. 11-33 (1992)
Griffin, T. A., 'Pfefferle, L. D., Dyer, M. J., and Crosley, D. R., "The Ignition of
Methane/Ethane Boundary Layer Flows by Heated Catalytic Surfaces", Combust. Sci.
Technol., Vol. 65, pp. 19-37 (1989).
Groppi, G., Belloli, A., Tronconi, E. and Forzatti, P., "Comparison of Lumped and
Distri1uted models of Monolith Catalysts in Hybrid Combustors for Gas Turbines",
Chem.Eng. Sci., Vol. 50, pp. 2705-2715 (1995).
Groppi, G., and Tronconi, E., "Theoretical Analysis of Mass and Heat Transfer in
Monolith Catalysts with Triangular Channels", Chem. Eng. Sci., Vol. 52, No. 20, pp.
3521-3526 (1997).
Groppi, G., Tronconi, E. and Forzatti; P., "Mathematical Models of Catalytic
Combustors", Catal. Rev.-Sci. Eng., Vol 41(2), pp. 227-245 (1999)..
Hagen, J., Industrial Catalysis A Practical Approach, WILEY-VCH (1999).
Hanson, F. V., and Boudart, M., "The Reaction Between H2 and 02 over Supported
Platinum Catalysts", J. Catal, Vol. 53, pp. 56-67 (1978).

177
Harrison, B. K., and Ernst, "Catalytic Combustion in Cylindrical Channels: A
Homogeneous-Heterogeneous Model", Combust. Sci. Technol., Vol. 19, pp. 31-38
(1978).
Hautman, D. J., Dryer, F.L., Schug, K.P., and Glassman, I., "A multiple-step overall
kinetic mechanism for the oxidation of hydrocarbons", Combust. Sci. Technol., Vol. 25,
pp. 219-235 (1981).
Hayes, R. E., Kolaczkowski, S. T., and Thomas, W. J., "Finite-Element Model for a
Catalytic Monolith Reactor", Comp. Chem. Eng., Vol. 16, pp. 645-657 (1992).
Heywood, J. B., Internal Combustion Engine Fundamentals, McGraw-Hill, New York
(1988).
Hiam, L., Wise, H., and Chaikin, S., "Catalytic Oxidation of Hydrocarbons on Platinum",
J. Catal, Vol. 9, pp. 272-276 (1968).
Heck, R. M., and Farrauto, R. J., "Catalysis for Environmental Control", Special
Publication of the Royal Society of Chemistry, Chemically Modified Surfaces, Vol. 139,
pp. 12b-139 (1994).
Hicks, R. F., Qi, H., Young, M. L., and Lee, R. G., "Structure Sensitivity of Methane
Oxidation over Platinum and Palladium", J. Catal., Vol. 122, pp. 280-294 (1990).
Ikeda, H., Libby, P. A., and Williams, F. A., "Catalytic Combustion of Hydrogen-Air
Mixtur
es in Stagnation Flows", Combust. Flame, Vol. 93, pp. 138-148 (1993).
Ismagilov, Z. R., and Kerihentsev, M. A., "Catalytic Fuel Combustion - A Way of
Reducing Emission of Nitrogen Oxides", Rev.-Sci. Eng., Vol. 32(1 & 2), pp. 51-103
(1990).
178
Jones, R. L., "Surface and Coatings Effects in Catalytic Combustion in Internal
Combustion Engine", Surface and Coatings Technology 94-95, pp. 118-122 (1997).
Kang, S.-K., Jeong, N.-J., Rye, 1.-S., and Beak, Y.-S., "Combustion Control
Technologies of Catalytic Burner Applying to Reduction-Induced Furnace", 4th
Karim, G. A., and Klat, S. R., "The Measurement of the Mass Flow Rate of Different
Gases Using a Choked Nozzle", Journal of Laboratory Practice, Vol. 15, pp. 184-186
(1966).
Kendall, R. M., DesJardin, S. T., and Sullivan, J. D., Basic Research on Radiant Burners,
Gas Research Institute Report number 92/0181. Alzeta Corporation Report number 92-
7027-171 (1992).
Kesselring, J. P., Advanced Combustion Methods, Academic Press Inc. (London), (1986).
Kesselring, J. P., Krill, W. V., Atkins, H. L., Kendall, R. M., Kelley, and Kelley, J. T.,
"Design Criteria for Stationary Source Catalytic Combustion Systems", EPA-600/7-79-
181, August (1979).
Khalil, E. B. F., "Heat and Mass Transfer within Granular Beds" M.Sc. Thesis,
Department of Mechanical Engineering, The University of Calgary, Calgary, Alberta
(1993).
Khitrin, L. N., and Solovyeva, L. S., "Homogeneous-Heterogeneous Combustion of
Carbon' Monoxide in Narrow Tubes (Channels)", Seventh Symposium (International) on
Combustion, The Combustion Institute, Butterworth's Scientific Publication, London, pp.
532-538 (1959).
179
Koshland, C. P., "Impacts and Control of Air Toxics from Combustion", Twenty-Sixth
Symposium (International) on Combustion, The Combustion Institute, Pittsburgh; PA,
pp. 2049-2065 (1996).
Kuo, I. C. W., Morgan, C. R., and Lassen; H. G., "Mathematical Modeling of CO and
HC Catalytic Converter Systems", SAE Trans., Vol. 80, pp. 1098-1125 (1980).
Lee, H. H., and Ruckenstein, B., "Catalyst Sintering and Reactor Design", Catal. Rev.-
Sci. Eng., Vol. 25, pp. 475 (1983).
Li, S.-Y., and Li, B.-L., "Kinetic Characteristics of Catalytic Reactions of CO, HC and
NO on Different Three-Way Catalysts", React. Kinet. Catal. Lett., Vol. 56, pp. 283-289
(1995).
Li, S.-Y., and Li, B.-L., "Study on Non-Noble Metal Catalysts for Automotive Emissiion
Control" React. Kinet. Lett. Vol. 57, No. 1, pp. 183-190 (1996).
Magnus, E., and Jaras, S. G., "Catalytic Combustion of Low-Heating Value Fuel-Gases:
Ignition of CO, H2,and CH4,Symposium on Catalytic Combustion Presented Before the
Division of Petroleum Chemistry, Inc., 213 th National Meeting, American Chemical
Society, San Francisco, CA, April 13-17, pp. 146-150 (1997).
Markatou, P., Pfefferle, L. D., and Sinooke, M. D:, "A Computational Study of Methane-
Air Combustion over Heated. Catalytic and Non-Catalytic Surfaces", Combust. Flame,
Vol. 93, pp. 185-201 (1993).
Markatou, P., Pfefferle, L. D., and Smooke, M. D., "The Influence of Surface Chemistry
on the Development of Minor Species Profiles in the Premixed Boundary Layer
Combustion of an 112 /Air Mixture", Combust. Sci. Technol., Vol. 79, pp. 247-268
(1991).
180
Mehta, S. A., "An Examination of the Combustion and Transport Processes Within
Fractured Oil Sands Beds", Ph D. Thesis, Department of Mechanical Engineering, The
University of Calgary, Calgary, Alberta (1990).
Modest, M. F., Radiative Heat Transfer, McGraw-Hill, New York (1993).
Moallemi, F., Batley, G., Dupont, V., .Foster, T.J., Pourkashanian, M., and Williams, A.,
"Chemical Modelling and Measurements of the Catalytic Combustion of CH4Iair
Mixtures on Platinum and Palladium Catalysts", Catal. Today, Vol. 47, pp. 235-244
(1999).
Mori, Y., Miyauchi, T., and Hirano, M., "Catalytic Combustion of Premixed Hydrogen-
Air", Combust. Flame, .Vol. 30, pp. 193-205 (1977).
Nakajiina, F., "Air Pollution Control vith Catalysis", Catal. Today, Vol. 10, pp. 1-20
(1991).
Nàkhjava, A., Bjornbom, P., Zwinkels, M. F. M., and Jaras, S. G., "Numerical Analysis
of the Transient Performance of High-Temperature Monolith Catalytic Combustions:
Effect of Catalyst Porosity", Chem. Eng. Sci., Vol. 50(14), pp. 2255-2262 (1995).
Oh, S. H., and Cavendish, J. C., "Transients of Monolithic Catalytic Converters:
Response to a Step Change in Freestream Temperature as Related to Controlling
Automobile Eimission", I
nd. Eng. Chem., Prod. Res. Dev., Vol. 21, pp. 29 (1982).
Oh, S. H., Mitchell, P. J., and .Siewert, R. M., "Methane Oxidation over Alumina-
supported Noble Metal Catalysts with and without Cerium Additives", J. Catal., Vol. 132,
pp. 287-301 (1991).

181
Otto, K., "Methane Oxidation over Pt on 'y-Alumina: Kinetics and Structure Sensitivity",
Langmuir, Vol. 5, pp. 1364-1369 (1989).
Patankar, S. V., Numerical Heat Transfer and Fluid Flow, Hemisphere, Washington
(1980).
Pattas, K. N., Stamatelos, A. M., Pistikopoulos, P. K., Koltsakis, G. C., Konstandinidis,
P. A., Volpi, E., and Leveroni, E., "Transient Modeling of 3-Way Catalytic Converters",
SAE 940934, pp. 289302 (1994).
Pfefferle, L. D., and Pfefferle, W. C., "Catalysis in Combustion", Catal. Rev.- Sci. Eng.,
Vol. 29(2&3), pp. 219-267 (1987).
Pfefferle, L. D., Griffin, T. A, Dyer, M. J., and Crosley, D. R., "The Influence of
Catalytic Activity on the Gas Phase Ignition of Boundary Layer Flows Part II: Oxygen
Atom Measurements", Combust. Flame, Vol. 76, pp. 339-349 (1989).
Pfefferle, L. D., Griffin, T. A., Winter, M., Crosley, D. R., and Dyer "The Influence of
Catalytic Activity on the Ignition of Boundary Layer Flows Part I: Hydroxyl Radical
Measurements", Combust. Flame, Vol. 76, pp. 325-338 (1989).
Pfefferle, W. C., "Catalytically Supported Thermal Combustion", Belgian Pat. 814,752, 8
November (1974); and U.S. Pat. 3,928,961, 30 December (1975) (orig. filing 1971).
Pitchai, R., and Klier, K., "Partial Oxidation of Methane", Catal. Rev.-Sci. Eng., Vol. 28,
No. 1, pp. 13-88 (1986).
Prasad, R., Kennedy, L. A., and Ruckenstein, E., "Catalytic Combustion of Propane
Using Transitional Metal Oxides", Combust. Sci. and Technol., Vol. 22, pp. 271-280
(1980).
182
Prasad, R,, Kennedy, L. A., and Ruckenstein, E., "Oxidation of Fuel Bound Nitrogen in a
Transitional Metal Oxides Catalytic Combustor", Combust. Sci. and Technol., Vol. 27,
pp. 45-56 (1981).
Prasad, R., Tsia, H. L., Kennedy, L. A., and Ruckenstein, E., "Effect of Inlet Parameters
and Bed Length on the Operating Characteristics of aCatalytic Combustor", Combust.
Sci. and Technol., Vol. 25, pp. 71-84 (1981).
Prasad, R., Tsia, H. L., Kennedy, L. A., and Ruckenstein, E., "Occurance of Multiple
Steady States in the Catalytic Combustion of Propane", Combust. Sci. and Technol., Vol.
26, pp. 51-64 (1981).
Prasad, R., Kennedy, L. A., and Ruckenstein, E., "Catalytic Combustion", Catal. Rev.-
Sci. Eng., 26, pp. 1-58 (1984).
Prather, M. J., and Logan, J. A., "Combustion's Impact on the Global Atmosphere", -
Twenty-Fifth Symposium (International) on Combustion, The Combustion Institute,
Pittsburgh, PA, pp. 1513-1527 (1994).
Ragaini, V., Vitali, S., and Luzzato, D., "Development of a Catalytic Burner and
Evaluation of Its Performances in Comparison with Other Not Catalysed Burners", 4th
Razon, L. F., and Schmitz, R. A., "Intrinsically Unstable Behavior during the Oxidation
of Carbon Monoxide on Platinuth", Catal. Rev.-Sci. Eng., Vol. 28, No. 1, pp. 89-164
(1986).
Reid, R. C., Prausnitz, J. M., and Poling, B. E., The Properties of Gases and Liquids, 4th
Ed., McGraw-Hill, New York (1987).

183
Richardson, J. T., Principles of Catalyst Development, Plenum Press, New York, pp. 104-
106(1989).
Ruckenstein, E., and Dadyburjor, D. B., "Sintering and Redispersion of Supported Metal
Catalysts" Catal. Rev.-Sci. Eng., Vol. 1, pp. 251 (1983).
Rumminger, M. D., Hamlin, R. D., Dibble, R. W., "Numerical Analysis of aCatalytic

Radiant Burner: Effect of Catalyst on Radiant Efficiency and Operability", Catal. Today,
Vol. 47, pp. 253-262 (1999).
Schefer, R. W., "Catalyzed Combustion of H2/Air Mixtures in aFlat Plate Boundary
Layer: IL Numerical Model", Combust. Flame, Vol. 45, pp. 171-190 (1982).
Schefer, R. W., and Robben, and Cheng, R. K., "Catalyzed Combustion of H2/Air
Mixtures in aFlat-Plate Boundary Layer: I. Experimental Results", Combust. Flame. Vol.
38. pp. 51-63 (1980).
Schlegel, A., Benz, P. Griffin, T., Weisenstein, and Bockhorn, H., "Catalytic
Stabilization of Lean Premixed Combustion: Method for Improving NO x Emission",
Combust. Flame, Vol. 105, pp. 332-340 (1996).
Scholten, A., Van Yperen, R., and Emmerzaal, I. J., "A Zero NO Catalytic Ceramic
Natural Gas Cooker", 4th International Workshop on Catalytic Combustion, San Diego,
14-16 April (1999).
Seinfeld, J. H., Atmospheric Chemistry and Physics ofAir Pollution, John Wiely & Sons,
New York, 1986.

184
Seonhi, R., and Scholten, A., "Comparison of Catalytic and Catalytically Stabilised
Domestic Natural Gas Burners", 20th World Gas Conference Proceedings, Copenhagen,
(1997).
Smith, L., Karim, H, Castaldi, Etemad, S., and Pfefferle,W., "Catalytic Combustion f6r
Ultra Low Emission Ground Power Application", 4th International Workshop on
Catalytic Combustion, San Diego, 14-16 April (1999).
Sobolev, G. K., "High-Temperature Oxidation and Burning of Carbon Monoxide", Sixth
Symposium (International) on Combustion, Reinhold, New York, paper No. 57, pp. 386
(1957).
Sokolovskii, V. D., "Principles of Oxidative Catalysis on Solid Oxides", Catal. Rev.-Sci.
Eng., Vol. 32(1 & 2), pp. 1-49 (1990).
Song, X., W i
lliams, W. R., Schmidt, L. D., and Ails, R., "Bifurcation Behavior in
Homogeneous-Heterogeneous Combustion: II. Computations for Stagnation-Point Flow,
Combust. Flame, Vol. 84, pp. 292-311 (1991).
Song, X., Williams, W. R., Schmidt, L. D., and Aris, R., "Ignition and extinction of
homogeneous-heterogeneous combustion: CH4 and C3H8 oxidation on PT", Twenty-
Third Symposium (International) on Combustion, The Combustion Institute, pp. 1129-
1137(1990).
T'ien, J. S., "Transient Catalytic Combustor Model", Combust. Sci. and Technol.; Vol.
26, pp. 65-75 (1981).
Tochihara, Y., and Ozawa, Y., "Improvement of Catalyst Using Catalytic Combustor for
aGas Turbine", 4th International Workshop on Catalytic Combustion, San Diego, 14-16
April (1999.). .
185
Torniainen, P. M., Chu, X., and Schmidt, L. D., "Comparison of Monolith-Supported
Metals for the Direct Oxidation of Methane to Syngas", J catal., Vol. 146, pp. 1-10
(1994).
Treviflo, C., "Catalytic Flat Plate Boundary Layer Ignition", Combust Flame, Vol. 26, pp.
245-251 (1981).
Treviflo, C:,. and .Peters, N., "Gas Phase Boundary Layer Ignition on aCatalytic Flat Plate
with Heat Loss", Combust. Flame, Vol. 61, pp. 39-49 (1985).
Trimm, D. L., and Lam, C.-W., "The Combustion of Methane on Platinum-Alumina
Fiber Catalysts-I Kinetics and Mechanism", Chem. Eng. Sci., Vol. 35, pp. 1405-1413
(1980).
Twigg, M. V., Catalyst HandbooK, Manson Publishing Ltd., London (1996).
Twigg, M. V., and Wilkins, A. I 1, "Autocatalysts-Past, Present, and Future" in
Structured Catalysts and Reactors, Marcel Dekker, Inc., chapter 4, pp. 91-120 (1998).
Quinlan, M., Wise, H., and McCarty, J., "Basic Research on Natural Gas Combustion
Phenomena-Catalytic Combustion";, GRI Annual Report, pp. 1-59 (1986).
Vaichos, D. G., "The Interplay of Transport, Kinetics, and Thermal Interactions in the
Stability of Premixed Hydrogen IAir Flames Near Surfaces", Combust. Flame, Vol. 103,
pp. 59-75 (1995).
Valchos, D. G., Schmidt, L. D., and Aris, R., "Ignition and Extinction of Flames Near
Surfaces: Combustion of H2 in Air", Combust. Flame, Vol. 95, pp. 313-335 (1993).
186
Voltz, S. E., Morgan, C. R., Liedermañ, D., and Jacob, S. M., "Kinetic Study of Carbon
Monoxide and Propylene Oxidation on Platinum Catalysts", I

nd. Eng. Chem. Prod. Res.
Develop., Vol. 12(4), pp. 294-301 (1973).
Wakao, N., and Kaguei, S., Heat and Mass Transfer in Packed Beds, Gordon and Breach
Science Publishers (1982).
Wampler, F. B., Clark, D. W., and Gaines, F. A., "Catalytic Combustion of C3H8 on Pt
Coated Monolith", Combust, Sci. Technol.., Vol. 14, pp. 25-31 (1976).
Wanicer, R., Raupenstrauch, H., and Staudinger, G., "A fully Distributed Model for the
Simulation of aCatalytic Combustor", ,Chem. Eng. Sci., Vol. 55, pp. 4709-4718 (2000).
Wark, K. Jr., Thermodynamics, McGraw-Hill, New York (1988).
Westbook, C. K., "Simplified Reaction Mechanisms for the Oxidation of Hydrocarbon
Fuels in Flames", Combust. Sci. Technol., Vol. 27, pp. 31-43 (1981).
Will, N. S., and Bennett, C. J., "Flow Maldistributions in Automotive Converter
Canisters and their Effect on Emission Control", SAE 922339, pp. 18.3-210 (1992).
Younis, L. B., and Wierzba, "Numerical Analysis of Methane-Air Oxidation within
Catalytic and Non-Catalytic Packed Bed Reactors", The Combustion Institute Canadian
Section, Spring Technical Meeting, Windsor, Ontario, pp. 45.1-45.7 (2002).
Younis, L. B., and Wierzba, I., "A Numerical Investigation of Catalytic Oxidation of
Very Lean Methane-Air Mixtures within aPacked Bed Reactor", to be published in J.
Porous Media, Vol. 2(2004).

187
Zabetakis, M. G., "Flammability Characteristics of Combustible Gases and Vapors", U.S.
Bureau of Mines, Bulletin 627, Pittsburgh, Pennsylvania, (1965).
Zwinkels, M. F. M., Jaras, S. G., Govind Menon, P., and Griffin, T. A., "Catalytic
Materials for High-Temperature Combustion", Catal. Rev.-Sci. Eng., Vol. 35(3), pp.319-
358 (1993).
188
Appendix A
Thermophysical Properties
The specific heat at constant pressure of the gas mixture Cp g and the transport properties:
the mass diffusion coefficient Dk, and thermal conductivity of the gas mixture kg in the
calculation are listed in the following sections. Properties for each component are
calculated as afunction of the local temperature.
Ad Gas Specific Heats
The specific heat at constant pressure (heat capacity) for the pure components considered
in the modeling is determined from the following formula (Heywood, 1988):
Cp g (kJ/kmol.K) = 4.184 (ai + a2 0+ a3 92 + a4 0 3 + a50 -

2) (A. 1)
where 0 T (K) /1000 and ai, a2, a3, a4,and as are constants (curve fit coefficients)'
specific to the gas as listed in Table A. 1.
Table A.1 Gas specific heat correlation constants,
component a1 a2 a3 -
a
4 a5
CH4 -0.29149 26.327 -10.610 1.5656 0.16573
C3R8 -1.4867 74.339 -39.065 8.0543 0.01219
For air and other ideal gases the specific heat at constant pressure in (J/kmol.K) is
obtained from the following correlation (Wark, 1988):

189
Cpg
= a+bT+cT 2 +dT 3 +eT 4 (A.2)
R
The constants a, b, c, d, and ear listed in Table A.2 and T is in (K).
Table A.2 Gas specific heat correlation q. A.2) constant.
Component a bx10 3 cx 10 6 dx 10 9 fexlO'2 1

CO 3.710 -1.619 3.692 -2.032 0.240
H2 3.057 2.677 -5.810 5.521 -1.812
02 3.626 -1.878 7.055 -6.764 2.156
Air 3.653 -1.337 3.294 -1.913 0.2763
A.2 Diffusion Coefficient
The binary diffusion coefficients are calculated based on the Chapman-Enskog
theoretical description of the binary mixtures of gases at low to moderate pressures. In
this theory, the binary diffusion coefficient for the species pair A and B is
DAB 3 (42rkB T/MW)

2 fD (A.3)
16 (F/RU T)
-
AB 2D
where kB is the Boltzmann constant, T (K) is the absolute temperature, F (Pa) is the
pressure, Ru is the universal gas constant, and fD is atheoretical correction factor whose
190
value is sufficiently close to unity to be assumed the same. The remaining terms are
defined below: -
MWAB = 2{(1/M) + (1/MWB)f' (A.4)
where MJVA and MWB are the molecular weights of species A and B, respectively;
cYAB = (0 A + (A.5)
where qA7 and o are the hard-sphere collision diameters of species A and B,
respectively, values of species employed in the model prediction are shown in Table D.3.
The collision integral, 92 D, is a dimensionless quantity calculated using the following
expression:
A C E G
nD = * + * + * + * (A.6)
(2' ) exp(DT ) exp(FT) exp(HT )
where
A = 1.06036, B = 0.15610,
C=0.19300, D=0.47635,
E=1.03587, F=1.52996,
G= 1.76474, H=3.89411,
and where the dimensionless temperature f is defined by
= kB T/e = kB T/(SA SB )112 (A.7)
Values of the characteristic Lennard-Jones energy, Si, are also tabulated in Table A.3
(Reid et al., 1987).

191
Table A.3 Lennard-Jones parameters for species employed in the calculation.

o
Species a(A) e/1GB (K)
Air 3.711 78.6
CH4 3.758 148.6
CO 3.690 91.7
C2R 4.443 215.7
C3H8 5.118 237.1
112 2.827 59.7
02 3.467 106.7
Substituting numerical values for the constants in Eq D.3 results in
0.0266 T1/2
(A.8)
= FWWA112 OAB ≤ D
with the following associated units: D[=] m2/s, T[=] K, P [=] Pa, and o[=] A.
A.3 Gas Thermal Conductivity
The pure gas component thermal conductivity is determined from the following formula
(Oh and Cavendish, 1982):
kg = 2.269x10 Tg
°832 (A.9)
where Tg is in (K), and k

g is in (W/cm.K)
192
Appendix B
Choked Nozzles Calibration
The fuel (methane) and air were metered by the choked flow nozzle system connected to
the experimental set-up. These nozzles were calibrated with awet test meter using air as
the working fluid. These results were then converted to yield flow rates for methane
using the equation suggested by Karim and Klat (1966):
mair Cair IkIlVair pair

(B.1)
-
MWCH4 CH4
mcu 4
where m is the mass flow rate, C is the coefficient of discharge, MW is the molecular
weight.
Calibration of all choked nozzles was conducted while they were mounted on the panel
where they were eventually used. The calibration curves for air and methane with their
corresponding equations are shown in Fig. B.1, B.2, B.3, B.4 and B.5.
4,00E-02
3.50E-02
3.COEO2
2.50E-02
2.COE-02
1.50E-02
1.E-02
5.COE-03
O.00E+0O
0 5 10 15 20 25 30 35 40 4
pi-r° 5(kpaIK°5 )
Fig. B.1 Calibration curves for 0.09 mm diameter nozzle.
193
0.25
0.2 y= 0.0053x + 0.0061
E
0
>
0.05
0
0 5 10 15 20 25 30 35 40 45
pir ° (kPa/K ° )
0.6
0.5
0.4
a
0
0.3
I..
0
E 0.2
0
>
0.1
0
0 5 10 15 20 25 30 35 40 45
PIT (kPa/K °)

194
1.4
1.2
E
0.8
0
I-
o9
.6
0
E
0.4
0.2
0
5 15 20 25 30 35 40 45
PIT °5 (kPa/K °)
6.00E+00
5.00E+00
y 0.2183x - 0.3662,' -
I19i
C.,
E 4.00E+00
0
CV
3.00+0O
2.00E+00
l.00E+00.
0.E+00
0 5 10 15 20 25 30
PIT °5 (kPa/K °5 )

195
Appendix C
Thermocouple Correction
The error in the, thermocouple measurements due to radiation and convection was
calculated using the following formula (Bradley and Mathews, 1

,968):
0.
Tcorrec/
ed = Tuncorrecte d +
(C.1)
h
where 0. is Stefan Boltzmann constant, s is the emissivity, and his the convection heat
transfer coefficient.
The temperature distribution' at the inlet across the reactor was measured using a
thermocouple sheathed-with 600 Inconel as shown in Fig. C.1. This thermocouple was,
first calibrated with adigital calibration thermometer.
25
20
15
E
>-
10
0
0 5 10 1 15 20 25 30 35 40 45 50
Temperature (
°C)
Fig. C.1 Temperature distribution across the reactor, Ti,, = 41 °C.

196
Appendix D
Pressure Drop
The pressure drop within the packed bed was measured using differential pressure
transducer. Figure D. 1shows the pressure drop as afunction of the flow rates while Fig
D.2 illustrate the pressure drop across the bed as afunction of the approach velocities. 1
0.6
0.5 4
0.1
0
00 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 50
Flow rate (m 3lh)

Fig. Di. Pressure drop across the packed bed reactor as afunction
of the flow rate at Tm= 20 °c and P = 88.1 kPa.
197
0.6
0.5
0.4
a.
0.
0
0.3
U
U)
U)
U
0.2
0.1
*
0
00 0.6 1.0 1.5 2.0 25
Aproach Velocity (mis)
Fig. D.2 Pressure drop across the packed bed reactor as afunction
of the approach velocity at Tin = 20 °C and P= 88.1 kPa.

198
Appendix E
Gas Analysis
The concentration of major species such as CH4,CO, CO2,and 02 in the exhaust gas was
measured and recorded continuously using Beckman gas analyzers. The measured
concentrations of the species were based on adry volumetric percentage. Assuming that
there is no carbon monoxide (CO) formed which was confirmed experimentally. The
overall combustion equation can be written as:
xCH4 + (1-x) (0.2102 + 0. 79N2) - aCH4 - bCO2 + dH20 + e02
+ 0. 79('l-x) N2 (E.1)
where xrepresent the initial concentration of methane in the mixture while a, b, d, and e
represent the corrected concentrations of CH4,CO 2,H20 and 02, respectively in the
exhaust gas. The corrected concentrations of the mentioned species were calculated on
the basis of elemental mass balance as follows:
a (E.2)
(E.3)
= (O.79+O.2l)r m
[(1—rn)]
1
where k, 1and m represent the measured concentrations (dry basis) of CH4,CO 2 and 02,
respectively.
All the experimental data presented for species conversion were the corrected ones
obtained from equations (E.2 - E.4). The comparison of the "dry" and "wet" conversion
over the range of 0to 50% methane conversion, for methane-air mixture of equivalence
ratio 0.35, shows amaximum of 1.8%difference. In all cases with the platinum bed, CO
concentrations were below 1ppm, which is the detection limit of the CO gas analyzer.
Appendix F
Program Listing
1cpsl(4),porl(4),sigel(4),pdl(4),wol(4)
c ANONEQTJILIBRIUM MATHEMATICAL MODEL PROGRAM OF A dimension amda(11),eta(11),sige(11),pd(11),amu(11)
PACKED-BED REACTOR dimension condt(11),convt(I1),unst(11),radt(11)
c BYL.B.YOUNIS C
c THE MECHANICAL AND MANUFACTURING ENGINEERING, ENTRY GRID
UNIVERSITY C
OF CALGARY, CANADA. sumro0.
o SEP. 2001 iter=0.
CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCC00000C00000CCCCCCCCCCCC nts=1
SUBROUTINE USER C Uniform grid
xu(2)=0.
logical lsolve,lstop dxxllfloat(11-2)
parameter(11 10 1) do 1i=3,11
common f(ll,6),rho(11),gam(11),con(11),aip(11),aim(11), 1xu(i)xu(i-1)+dx
1ap(11),x(11),xu(11),xdif(11),xcv(11),xcvs(L1),fo(11,6), return
2u(ll),xcvi(11),xcvip(11) C
common fr(ll),fxm(11),pt(11),qt(11) ENTRY START
commonhindx/nfnfinax,12,13,ist,iter,1astre1ax(5), C
ltime,dt,xl,lsolve(5),ntimes(5) ntsltmax/dt
common/cntlllstop,ntsl,nts nco0
commonIcoe'flow,diffacof isw=1
c do2i1,11
tf(i)tin
dimension hf(11),tf(11),ts(ll),ym(11),rhof(11),rhos(11),yf(11), ts(i)tin
1yper(ll) ym(i)fu11n
equivalence (f(1, 1),tf(1)),(f(1,2),ts(1)),(f(l,3),ym(1)), wfu(i)=0.
1(f(1,4),hf(1)) dqdx(i)=0.
real tkf(11),tks(ll),qrp(11),qrm(11),qrt(11),dqdx(11) 2 continue
real cpf(ll),cps(11),por(ll),hv(11),wfti(11) do 5i1,ll
real difc(ll),xo2(11),sr(11),wfuo(11),wo(ll),wsu(11),wsuo(11) do5n'l,6
dimension xly(4),xloc(4),nle(4),ñlb(4),rhosl(4),tksl(4), 5 fo(i,n)f(i,n)
C 22 continue
c print of input data--------- Cl 111111 Ill-H-Ill II
print ,' do i=2,12
print *,hl Multi-Layer xsp0.0
print fsp=0.
return if(x02(i).gt.0.0) xsp(rhof(i)*x02(i)/32.0)**0.5
C if(ym(i).gt.0.0) fsp=(rhof(i)*ym(i)/16.0)
ENTRY DENSE temps—ts(i)
C wsusprecat*xsp*fsp*exp(engsI(83 14.0*temps+1.0e20))
do 10 i1,11 wsu(i)1.0*((2.25/1.0)*wSus)
1) rho(i)=por(i)*rhof(i)*cpf(i)
if(nfeq. end do
if(nf.eq.2) rho(i)=(L_por(i))*rhos(i)*cps(i)
if(nfeq.3) rho(i)rhof(i) return
10 continue
return ENTRY OUTPUT
C
ENTRY BOUND if(iter.ne.0) return
C if(nts.ge.ntsl) go to 310
do 12 1=1,11 printcprintc4dt
u(i)un1et if(printc.lt.timepr) return
xo2(i)=xo2instmr*(fu1inym(i)) printc=0
12 continue 310 print *,hflme&,time
fmass=u(1)*rhof(1) print 316
heats=fmass*fulin*hfg 316 format(lx,'x', l0x,'ts', 10x,tf, 14x,'qrt', lOx,

heatsf=heats/flamt 1'qr+', lOx,'qr-', l0x,'Ym')
tf(1)=(u(1)*cpf(1)*rhof(1)*tgin+tkf(1)*tf(2)/xdif(2))/ do 315 i=1,11
1(u(1)*cpf(1)*rhof(1)itkf(1)/xdif(2)) print 317,x(i),ts(i),tf(i),qrt(i),qrp(i),qrrn(i),ym(i)
lf(11)=tf(12) 315 continue
ts(11)=ts(12) 317 format(lx,f6.4,2x,fl0.3,2x,flo.3,2x,f12.3,
ym(1)fulin 12x,fl2.3,2x,f12.3,2x,f12.3,2x,elO.3)
ym(11)ym(12) if(nts.lt.ntsl) return
hf(1)=hfin pel=u(1)*rhof(1)*cpf(1)*xdif(2)/tkf(1)
hf(11)=hf(12) aac=amaxl(0.0,(1.-0. 1*abs(pel))**5)
do 22 i=1,11 smkl=tkf(1)*aac*(tf(2)_tf(1))/xdif(2)
re=pd(i)*u(1)*rhof(1)/amu(i) enfl=u(1)*rhof(1)*cpf(1)*tgin
pr=(amu(i)*cpf(i)/tkf(i))**0.3333 enfo=u(1)*rhof(1)*cpf(11)*tf(11) -
hv(i)=6.0*tkf(i)*(2.0+1. 1*pr*re**0.6)/(pd(i)*pd(i)) ensi=tks(1)*(ts(2)_ts(1))/xdif(2)

enso=tks(11)*(ts(12)_ts(11))/xdif(11) 415 continue
qrad=(1.rfao)*qrm(1)+ endif
1(1._rfal)*qrp(11) do 412 i=2,12
1 emi*stf*por(1)*tgin**4emo*stf*por(11)*tamo**4 412 con(i)=con(i)+por(i)*wftlo(i)*hfg
heattO. go to 450
do 318 i=2,12 420 do 422 i=nfb,nfe
318 heatt'=heatf+w.fij(i)*hfg*xcv(i) 422 con(i)=con(i)+heatsf
if(time.gt.thin) heats=heatf 450 continue
balance=heats-I-enfl-enfo-enso-ensi-qrad rresi=rhof(i)*u(1)*cpf(i)*tkf(i)/(tkf(1)+rhof(i)*u(i)*cpf(1)
balance--balance/heats 1*xdjf(2))
lstop=.true. con(2)=con(2)+rresi*tginlxcv(2)
return ap(2)=ap(2)-rresilxcv(2)
C gam(11)=0.
ENTRY GAMSOR ,gam(i)=0.
C c---Solid matrix
c 1gas temperature 500 if(nfne.2) go to 600
c 2solid matrix temperature do 510 i=2,12
c 3mass fraction of the products ap(i)=_(1._por(i))*hv(i)
do i=2,12 con(i)(i._por(i))*hv(i)*tf(i)
xJflJ(j)=(ff*((ym(j)*rhof(j)/16O)**O2 c radiation effect
1*(x02(j)*rhof(j)/320)**]3)* radtt= 16. *slf*ts(i)*ts(i)*ts(i)/(3.*sige(i))
1exp(-eng/(83 14.0*tf(i)+1.0e_20))) gam(i)=gam(i)+(1._por(i))*radtt
end do 510 continue
do 401 i1,11 c---- set inlet boundary condition
gam(i)=por(i)*tkf(i) gam(i)=0.
if(nf.eq.2) gam(i)=(1._por(i))*tks(i) gam(li)=0.
if(nfeq.3) gam(i)=difc(i)*rhof(i) c for catalytic reaction
401 continue if(iter.eq. (last-i)) then
if(nfne.1) go to 500 do i2,12
do 410 1=2,12 wsuo(i)wsu(i)
con(i)(1._por(i))*hv(i)*ts(i) end do
ap(i)=_(1._por(i))*hv(i) end if
410 continue do i=2,12
if(time.lt.tnin) go to 420 con(i)con(i)+(1.0_por(i))*wsuo(i)*hfg
if(iter.eq. (last-i)) then end do
do 415 i=2,12 C
wfuo(i)=wfu(i) 600 if(nfne.3) go to 700
do 610 i=2,12 difc(i)1.00e-5
con(i)0.5*wfil(i) amu(i)=(1.40 le_6*t['(i)** 1.5)1(108.5 1+tf(i))
ap(i)_1.5*wfu(i)/(ym(i)+1.e_10) 800 continue
610 continue rhof(1)883251(rair*tin)
gam(11)=0. do 810 j1,nl
700 continue do 810 i=nlb(j),nle(j)
return por(i)=porl(j)
C rhos(i)=rhosl(j)
ENTRY PROP tks(i)=tksl(j)
C cps(i)=cpsl(j)
c----av =Surface area per unit volume pd(i)=0.0032/pdl(j)
c---- ii = Heat transfer coefficient sige(i)=sigel(j)
c---- hfg = Heat content of the fuel wo(i)=wol(j)
c 5xe7 J/Kg 810 continue
c---- p01= porosity C
if(nts.le. 1) then return
stf=5.67e-8
print *,'exafr',exafr C
fulin=16./(16.+(1.+exair)*274.56)
x02in64.*(1.+exair)/(16.+274.56*(1.+exair)) c******************************************************
c precat is pref'actor for catalyst and engs is activation energy for solid c=======Subroutine Layer to calculate the beginning and ending
c precat1.03e-5 node of each layer
engs=0.86e8 ENTRY LAYER
precatl.03e-3 sum0.
engs=0.46e8 do 900 j=1,nl
stmr4. sumsum+xly(j)
engl.8e8 xloc(j)sum
ff6.6e10 900 continue
runi=83 14.0 suni10.
hfg=5.00e7 do 915 j=1,nl
rair=run1128.97 do 910 i=2,12
endif sumlsuml+xcv(i)
do 800 i=1,11. if(suml.ge.xloc(j)) go to 920
c Density of air as function of P and T. 910 continue
rhof(i)=88325.0I(rair*tf(i)) 920 nle(j)=i
cpf(i)=1160. nlb(j+1)i+1
tkf(i)=(2.645 le-3 *tf(i)** 1.51(230.68+tf(i))) 915 continue
nle(nl)=11 read(3,*)unlet
nlb(1)=1 read(3,*)
C Calculated pre-set flame position read(3,*)exair
sunîfb=0. read(3,*)
sumfe=0. read(3,*)tin,tgin,tami,tamo
do 925 1=2,12 read(3,*)
sumfb=sumfb+xcv(2) read(3,*)hi,ho
if(sumfb.ge.floc) go to 930 read(3,*)
925 continue read(3,*)emi,emo
930 nfb=i c read(3,*)
do 935 i=2,12 c read(3,*) yJ
sumfe=sumfe+xcv(2) read(3,*)
if(sumfe.ge.(floc+fth)) go to 940 read(3,*) ni
935 continue read(3,*)
940 nfe=i read(3,*)(xly(i),11,nl)
flamt=0. sum0.0
do 941 intb,nfe dok=1,nl
941 flamt=flamt+xcv(i) sumsuni+xly(k)
print *,'Number of Layers=',nl end do
print *,'xloc. of each layer',(xloc(j)j=l,nl) xlsum
print *,'Beg inning node of each 1ayer'(nlb(j),j=1,nl) read(3,*)
print *,'End node of each 1ayer',(nle(j),jl,nl) read(3,*)(porl(i),i1,nl)
print *,'flame location',floc read(3,*)
print ,flame thickness',fth
* ' read(3,*)(rhosl(i),i1,nl)
print *,'Beginning node of flãme',nfb read(3,*)
print *,'End node of flame',nfe read(3,*)(tksl(i),i1,nl)
print *,f1ajne',f1amt read(3,*)
return read(3,*)(cpsl(i),i 1,nl)
C INPUT DATA read(3,*)
ENTRY INPUT read(3,*)(pdl(i),i1,nl)
read(3,*) read(3,*)
read(3,*)dt,tmax read(3,*)floc,fth
read(3,*) read(3,*)
read(3,*)timepr read(3,*)
read(3,*). read(3,*)(sigel(i),i=1,nl)
read(3,*)tnin return
read(3,*)
C OUTPUT
REPORT write(4,*)'
ENTRY REPORT
open(4,file='outp') write(4,*)I! SELECTED OUTPUT PARAMETERS II'
write(4,*)
write(4, * )' OUTPUT REPORT----------- write(4,*)'
write(4,*)'
write(4,*)hINPUT DATA' write(4,*)
write(4, *)'Flow rate of fuel and air (m3/s)
' balance=balance* 100.
write(4,*)volf,volair write(4,*)'Energy imbalance =',balance,' %'
write(4,*)'Cross sectional area of the duct (m2)' heatsheats*area
write(4,*)area heatb=heats*3 .413
write(4,*)hlnifial, gas inlet,and outlet ambient temperatures (K)' write(4,*)'Heat released by combustion=',heats,'W',heatb,'Btu/hr'
write(4,*)tin,,tgin,tarno exair=exair* 100
write(4,*)'Heat transfer coeff. at the inlet and outlet (W/m2 K)' write(4,*)'Excess air ',exair,' %'
write(4,*)hi,ho write(4,*)
write(4,*)'Emissivity of matrix at inlet and outlet surfaces' write(4,*)' AT THE OUTLET
write(4,*)emi,emo
write(4, *)'Total thiclaiess of the poous layers (rn)' C Plotting Files
write(4,*) xl open(17,file='xtgas')
write(4,*)'Number of layers' open(8,file='xtsol')
write(4,*) n1 open(9,f11e'xqrnet')
write(4,*)'Thickness of each layer (m)' open(10,fi1e'xfuel')
write(4,*)(xly(i),i=1,nl) open(11,fi1e'x02')
write(4,*)'Porosity of each layer' open(33,fi1e'xwfus')
rite(4,*)(porl(i),i1,nl) open(36,fi1e'xwsus')
write(4,*)'Density of solid matrix of each layer (kg/m3)' open(37,file='perfuel')
write(4,*)(rhosl(i),i=1,nl) do 1100 i1,ll
write(4, * )'Thermal conductivity of matrix of each layer (W/mK)' write(17,*)x(i),tf(i)
write(4,*)(tksl(i),i= 1,nl) write(8,*)x(i),ts(i)
wr.ite(4,*)'Specffic heat of each layer' write(9,*)x(i),qrt(i)
write(4,*)(cpsl(i),i=1,nl) write(10,*)x(i),ym(i)
write(4, *)'Number of pores per inch to each layer (PPI)' write(11,*)x(i),x02(i)
write(4,*)((i),i=1,nl) write(33,*)x(i),wfu(i)
write(4,*)'RADIATION PROPERTIES' write(36,*)x(i),wsu(i)
write(4,*)'Extinction coefficient of each layer (1/rn)' yper(i)((fulin_yln(i))ffulin)* 100.
write(4,*)(sigel(i),i=1,nl) write(37,*)x(i),yper(i)
1100 continue tkefw=2.*tks(i)*tks(i_1)/(tks(i)+tks(i_1))
return tkefe2.*tks(i)*tks(i+1)/(tks(i)+tks(i+1))
c condte=tkefe*(ts(i+1)ts(i))/xdif(i+1)
C Subroutine to calculate energy term contributions condtw=tkef'w*(ts(i)ts(i_1))/xdif(i)
entry TERM condt(i)(condte-condtw)/xcv(i)
if(iter.ne. last-i) return
advt=advt+dt convt(i)hv(i)*(tf(i)_ts(i))
if(advt.lt.50.) return unst(i)rhos(i)*cps(i)*(ts(i)_fo(i,2))/dt
advt=0. radt(i)dqdx(i)/xcv(i)
1200 continue
write(7,*) 'time=,time do 1220 i=2,12,2
write(7, 1202) 1220 write(7, 123 0)x(i),unst(i),condt(i),convt(i),radt(i)
1202 format(6x,'x',9x,'storge',9x,'conduction1,7x,'convection',6; 1230 forniat(fl0.5,4e16.5)
1'radiation') return
do 1200 i2,12 end

Ucalgary 2003 Younis Lubna Basheer 536517

Uploaded by

Document Information

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Ucalgary 2003 Younis Lubna Basheer 536517

Uploaded by

Copyright:

Available Formats

UNIVERSITY OF CALGARY

Numerical and Experimental Studies of Catalytic Combustion

in aPacked Bed Reactor

LUBNA BASHEER YOUNIS

SUBMITTED TO THE FACULTY OF GRADUATE STUDIES

IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE

DEGREE OF DOCTOR OF PHILOSOPHY

DEPARTMENT OF MECHANICAL AND MANUFACTURING ENGINEERING

- © LUBNA BASHEER YOUNIS 2003

FACULTY OF GRADUATE STUDIES

Studies for acceptance, a thesis entitled "Numerical and Experimental Studies of

Catalytic Combustion in aPacked Bed Reactor" submitted by Lubna Younis in partial

fulfillment of the requirements of the degree of Doctor of Philosophy.

Supervisor, Dr. I. Wierzba

Department of Chemical and

External Examiner, Dr. M. D. Checkè

November 28th 2003

A one-dimensional, non-equillibrium mathematical model of the catalytic combustion in

initial conditions were solved using afinite-difference procedure. Numerical simulation

strong influence on methane conversion when both homogeneous and heterogeneous

encouragement throughout the duration of this investigation is highly appreciated.

guidance regarding the model development part of this research.

Manufacturing Engineering machine shops, especially to R. Apperal, G. East, B.

Ferguson, A. Moehrle, R. Mosher, and B. Sanders for their assistance in instrumentation

promptly when they are needed.

colleagues Q. Wang and C. Veer.

devotion and moral support throughout the duration of this study.

Engineering Research Council of Canada (NSERC) is greatly acknowledged.

who taught me that knowledge is the

To my daughters, Shand and Danya,

my son, Mustafa, and

my wonderful husband Majeed

LIST OF SYMBOLS xxii

1.2 Objectives of the Study .12

1.3 Thesis Organization 13

CHAPTER 2: LITERATURE REVIEW 14

2.2 Experimental Work 14

2.2.1 Fundamental Studies . 15

2.2.2 Applications .17

2.2.3 Non-Noble Metal Catalysts .19

2.2.4 Catalytic Oxidation of Some Common Gaseous Fuels 20

2.3 Theoretical and Computational Studies 27

2.3.1 Bulk Diffusion 28

2.3.2 Intraparticle Diffusion 28

2.3.3 Coupled Heterogeneous and Homogeneous Reactions . .29

2.3.4 Transport Mechanisms 33

CHAPTER 3: ANALYSIS AND MATHEMATICAL MODELING 37

3.2 Description of the Physical Model 38

3.3 Description of the Mathematical model 39

3.3.1 Governing Equations ... 39

3.3.2 Kinetic Modeling .44

3.3.3 Initial Conditions ..45

3.3.4 Boundary Conditions 45

3.4 Numerical Model 46

3.4.1 Method of Solution . .46

3.4.2 Computer Code Development .46

3.5 Preliminary Results of Numerical Simulation of Methane 49

3.5.1 Inert Bed 52

3.5.2 Heterogeneous Reactions 55

3.5.3 Coupled Homogeneous-Heterogeneous Reactions 58

3.5.4 Effect of Bed Porosity .60

3.5.5 Effect of Bed Length 64

3.5.6 Effect of Thermal Conductivity of the Bed of Solids •75

CHAPTER 4: EXPERIMENTAL APPARATUS AND PROCEDURE 79