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Heterogeneous Catalysis –

Basic principles, catalyst synthesis and


characterisation, and industrial applications

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

CATALYST SYNTHESIS AND CHARACTERISATION


6. Catalyst synthesis ................................................................................... 137
6.1 Precipitation/crystallization/condensation .......................................... 139
6.1.1 Basic principles in precipitation and crystallization ................. 139
6.1.1.1 Rate of nucleation ...................................................... 142
6.1.1.2 Rate of crystal growth ................................................ 143
6.1.1.3 Rate of agglomeration ................................................ 144
6.1.2 Synthesis of support materials ............................................... 144
6.1.2.1 Alumina ...................................................................... 145
6.1.2.2 Silica .......................................................................... 147
6.1.2.3 Titania ........................................................................ 148
6.1.3 Co-precipitation ..................................................................... 148
6.1.4 Crystallization: synthesis of molecular sieves and zeolites .... 149
6.2 Deposition ......................................................................................... 159
6.2.1 Support material in contact with a solution ............................. 159
6.2.1.1 Strong electro-static adsorption .................................. 162
6.2.1.2 Grafting/ligand exchange ........................................... 162
6.2.1.3 Precipitation-deposition .............................................. 162
6.2.1.4 Impregnation .............................................................. 163
6.2.1.5 Structured catalyst particles ....................................... 163
6.3 Solid state reactions .......................................................................... 164
6.3.1 Fused catalysts...................................................................... 164
6.3.2 Skeletal catalysts ................................................................... 165
6.4 Drying ............................................................................................... 165
6.5 Calcination ........................................................................................ 166
6.6 Catalyst shaping................................................................................ 167
6.7 Catalyst activation ............................................................................. 169
7. Acid Catalysis ......................................................................................... 174
7.1 Acid strength ..................................................................................... 174
7.2 Heterogeneous acids ....................................................................... 176
7.3 Zeolites ............................................................................................. 177
7.3.1 Zeolite synthesis .................................................................... 181
7.3.1.1 Crystallization process of zeolite formation ................ 182
7.4 Mechanism of acid catalysed reactions ............................................. 189
7.5 Industrially acid catalysed reactions
7.5.1 Catalytic cracking
7.5.2 Olefin oligomerisation
7.5.3 Alkylation
8 Metal Catalysis ....................................................................................... 194
List of symbols
a external area of catalyst particle per unit
mass m2/g
a.u. arbitrary units
c ratio of adsorption constant on uncovered
surface relative to adsorption constant on
surface covered with adsorbent
cp specific heat at constant pressure J/(mol K))
d diameter m
eq equilibrium
f forward
h heat transfer coefficient J/(K m2 s)
k rate constant (units to match the rate of reaction)
kL mass transfer coefficient m/s
m mass kg
n number of moles, reaction order
p pressure atm, Pa
r rate of reaction mol/(s.kg)
r radius m
t thickness of physisorbed layer Å
u linear velocity m/s
x,y mol fraction
z bed or pore length m

A pre-exponential factor in rate expressions


C concentration mol/m3
D diffusion coefficient cm2/s
Ea activation energy J/mol
F molar flow rate mol/s
G Gibbs free energy kJ
G molar Gibbs free energy kJ/mol
H molar enthalpy kJ/mol
J molar flux mol/(m2.s)
K equilibrium constant
L length m
M molar weight g/mol
N number
R ideal gas constant 8.314 J/(mol K)
R radius of catalyst particle m
S molar entropy J/(mol K)
S selectivity (amount of material formed
relative to amount of reactant converted)
SR selectivity ratio (amount of material P
Formed relative to amount of S formed)
SA surface area m2/kg
T temperature K
V volume m3
V molar volume m3/mol
X number of atoms at the surface per unit
surface area nm-2

 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