E. van Steen
2014
Table of Content
BASIC PRINCIPLES
1. Introduction ................................................................................................. 1
1.1 Historical development of catalytic processing ...................................... 2
1.2 Basic rules in catalysis .......................................................................... 4
1.3 Thermodynamic limitations .................................................................... 9
2. Heterogeneous catalysts........................................................................... 14
2.1 Porosity ............................................................................................... 14
2.1.1 Mercury porosimetry ................................................................ 16
2.1.2 Capillary condensation ............................................................ 18
2.1.3 Classification of porous systems .............................................. 21
2.2 Surfaces .............................................................................................. 22
2.2.1 Dispersion ............................................................................... 24
2.3 Adsorption on Surfaces ....................................................................... 25
2.3.1 Measuring adsorption on surface ............................................. 26
2.3.1.1 Static volumetric method ............................................ 26
2.3.1.2 Dynamic flow method ................................................. 27
2.3.1.3 Gravimetric method .................................................... 28
2.3.2 Heat of adsorption ................................................................... 28
2.3.3 Modelling chemisorption .......................................................... 30
2.3.3.1 Langmuir isotherm ...................................................... 30
2.3.3.2 Temkin isotherm ......................................................... 33
2.3.3.3 Freundlich isotherm .................................................... 35
2.3.3.4 DFT-derived adsorption isotherms .............................. 36
2.3.3.5 Multi-component adsorption........................................ 37
2.3.4 Physisorption ........................................................................... 38
2.3.4.1 Classification of physisorption isotherms .................... 38
2.3.4.2 Hysteresis in physisorption isotherms ........................ 39
2.3.4.3 BET-isotherm.............................................................. 40
2.3.4.4 Alternative models describing physisorption ............... 43
2.3.5 Interpretation of N2-adsorption isotherms ................................. 43
2.3.5.1 Determination of BET-surface area ............................ 44
2.3.5.2 Pore size distribution – BJH method .......................... 46
3. Kinetics of heterogeneously catalysed reactions ....................................... 49
3.1 Intrinsic kinetics of heterogeneously catalyst reactions........................ 50
3.1.1 Langmuir-Hinshelwood approach ............................................ 51
3.1.2 Steady-state approach............................................................. 54
3.1.3 Principle of rate determining step............................................. 55
3.1.4 Micro-kinetic modelling ............................................................ 61
3.1.4.1 Modelling an elementary surface reaction step ............ 62
3.1.4.2 Adsorption and desorption processes .......................... 66
3.1.4.3 Building a micro-kinetic model ...................................... 67
3.2 Internal mass and heat transfer limitations – pore diffusion ................. 72
3.2.1 Concentration gradient in catalyst pores .................................. 73
3.2.1.1 Concentration gradient in a catalyst particle ................. 76
3.2.2 Pressure gradient in a catalyst particle .................................... 78
3.2.3 Temperature profile in a catalyst particle ................................. 81
3.2.4 Effect of mass and heat transfer limitations on activity ............. 83
3.2.4.1 Isothermal reaction A P in a spherical catalyst pellet 84
3.2.4.2 Isothermal reaction A s P in a porous catalyst pellet 86
3.2.4.3 Non-isothermal reactions in a spherical catalyst pellet . 87
3.2.5
Effect of internal mass and heat transfer limitations on selectivity
................................................................................................ 89
3.2.5.1 Parallel reactions of a common reactant ...................... 89
3.2.5.2 Parallel reactions of two reactants................................ 90
3.2.5.3 Consecutive reactions: A P S ............................... 91
3.2.6 Elimination of internal mass and heat transfer limitations ......... 93
3.3 External mass and heat transfer limitations ......................................... 94
3.3.1 Mass transfer through the boundary layer................................ 94
3.3.2 Heat transfer through the boundary layer................................. 95
4. Catalyst deactivation ................................................................................. 98
4.1 Inherent catalyst deactivation .............................................................. 99
4.1.1 Volatilization ............................................................................ 99
4.1.2 Sintering ................................................................................ 101
4.1.3 Creep of support .................................................................... 103
4.1.4 Phase transformation of the catalytically active phase ........... 105
4.1.5 Coking ................................................................................... 107
4.2 Operational catalyst deactivation ....................................................... 111
4.2.1 Fouling .................................................................................. 111
4.2.2 Catalyst poisoning ................................................................. 112
4.2.3 Mechanical failure of catalysts ............................................... 115
4.3 Catalyst regeneration ........................................................................ 115
4.4 Consequences of catalyst deactivation for activity/selectivity ............ 116
5. Catalyst testing ....................................................................................... 124
5.1 General definitions ............................................................................ 124
5.2 Ideal reactors .................................................................................... 126
5.2.1 Batch reactors ....................................................................... 127
5.2.2 Packed bed reactors .............................................................. 129
5.2.3 Continuous stirred tank reactors (CSTR) ............................... 132
5.3 Catalyst comparison .......................................................................... 123
Prater number
surface energy/tension J/m2
Arrhenius number
porosity
integration variable
Thiele module
effectiveness factor
density kg/m3
viscosity Pa s
diffusion volume
mean area per molecule
surface coverage
tortuosity
dimensionless length
stoichiometric coefficient
contact angle
dimensionless concentration
Sub-/superscripts
ads adsorbed
Av Avogadro
cr crystal
eq equilibrium
i compound i
p pressure
p pore
r reverse
pa particle
rxn reaction
vap vapour
IG ideal gas
G gas/vapour
L liquid