Chap 03 Masters

Catalytic Reaction Kinetics
Reactor design equation - Packed bed

Molar flow i
Why Catalytic Reaction Kinetics ?

Derivation rate expressions
Simplifications
Rate determining step
Initial reaction rate
Limiting cases
Temperature dependency
Pressure dependency
Examples
stoichiometric coefficient i
dFi
= i rW
dW
rate expression
bed coordinate
catalyst effectiveness
Dimension of rate?
Catalysis Engineering - Kinetics
Rate expression
Rate expression Gas phase reaction
How much detail ?

Catalyst
A+B
A+B
C+D
[intermediates]
A+B+*
C+D
AB*
*+C+D
etc.
conditions
forward rate
overall rate expression?
chance to success
r = f ( pi ,T , k, K eq , catalyst .....)
rate constant(s)
backward
r = k + c A cB k cC2
thermodynamics
amount of A chance to meet B
Role of catalyst?
Concentrating reactants
adsorption/complexation
Providing alternative reaction path
catalyst selectivity
other activation energy barrier
But:
other components adsorb, too
block active sites
fixed number of active sites
Rate vs. pressure/concentration ?
affect rate
rate
mol/s.gcat
rate constant
affect rate
pressure / kPa
affect rate
fixed number of active sites

mono & bimolecular reactions
other form rate expression expected

Kinetics
Rate expression Catalysed reaction

forward rate
chance to success
backward
r = k + c Aads s B k cCads sC
amount of A adsorbed
chance of adjacent B adsorbed
Rate expressions in principle crucial for
design
process start-up and control
process development and improvement
selection reaction model
Often used in catalysis
r = k pin p mj
power rate models
models based on elementary processes
sNT k 2K A K B2 pA pB2 / K eq
r =
(1 + K A p A + K B pB )2
Note:
cgas and cads differ
ratios components differ
extrapolation more reliable

intellectually process better understood
Simple example: reversible reaction

A
B
monomolecular
e.g. isomerization
A*
Rate expression follows from rate equation
r = r1 r1 = k1 p A NT * k 1 NT A
Elementary processes
A
Elementary processes
r = r2 r 2 = k 2 NT A k 2 NT B
r = r3 r 3 = k 3 NT B k 3 p B NT *
B*
Eliminate unknown surface occupancies

Langmuir adsorption
Elementary processes contd.
Quasi-equilibrium / rate determining step

Algebraic eqs.
1= * +A +B
Site balance:
(3.5)
d A
=0
dt
d B
=0
dt
Steady state assumption:

(3.6-7)
r2
r-2
rate determining
r3
r-3
Rate expression:
(3.9)
quasi-equilibrium
r =
r1
r-1
NT k1k2k 3 ( pA pB / K eq )
(.....) + (......) p A + (......) pB
with :
K eq = K 1K 2K 3
Microkinetics
Michaelis-Menten
r = r2 - r-2
Rate expression, contd.
Rate expression - r.d.s.

Substitution:
Rate determining step:
r = r2 r2 = k 2 NT K1pA * k 2 NT pB * / K 3
r = r2 r2 = k 2 NT A k 2 NT B
r = k 2 NT K1 * { p A k 2 p B / k 2 K1K3 }
Eliminate unknown occupancies
k1 p A NT * = k 1 NT A
r1 = r 1
So:
A = K1p A *
B =
p
Keq = K1K 2 K3 = B
p A eq
where:
Quasi-equilibrium:
with: K1 =
k1
k 1
pB
*
K3
Unknown still *
Surface occupancies
Rate expression, contd.

Site balance:
1 = * + A + B = * {1 + K1p A + p B / K3 }
Empty sites
1
* =
(1 + K1p A + p B / K3 )
Occupied by A
Finally:
r=
k 2 NT K1 p A pB / Keq
(1 + K1p A + p B / K3 )
* =
(1 + K1p A + p B / K3 )
K1p A
A =
(1 + K1p A + p B / K3 )
B =
(1 + K1p A + p B / K3 )
}
Occupied by B
p B / K3
1
= KB
K3
Thermodynamics
Other steps rate determining
Equilibrium constant
Adsorption r.d.s
r=
k1 NT pA pB / Keq
RT ln K eq = G (T ) = H (T ) T S
1 + (1 + 1 / K2 )p B / K3
k 2 NT K1 p A pB / Keq
(1 + K1p A + p B / K3 )
= i Gfo,i (T )
Adsorption constant
Desorption r.d.s.
r=
k 3 NT K1K2 p A p B / Keq
1 + (1 + K 2 )K1p A
ln K A =
Rule of thumb:Generally surface reaction r.d.s.

S o H o
R
RT
atm-1
Langmuir adsorption
1.0
A =
K A pA
1 + K A pA
0.8
100
KA /bar -1
10
0.6
A =
0.2
0.1
0
0
K 1p A
(1+ K p + K p )
1
1.0
0.4
0.2
0.4
Adsorption enthalpy,<0
(J/mol)
Multicomponent adsorption / inhibition
Uniform surface (no heterogeneity)

Discrete number of sites
No interaction between adsorbed species
A*
Adsorption entropy, <0

(J/mol K)
Data sources: Handbooks, API,JANAF

Chemsage, HSC
Langmuir adsorption
A+*
Reaction enthalpy
Surface reaction r.d.s.

r=
Reaction entropy
0.6
pA /bar
0.8
Inhibitors
1.0
Langmuir adsorption model
Dissociative adsorption
Generally used
although nonlinear, mathematically simple
simple physical interpretation
rather broadly applicable
multicomponent adsorption
non-uniform surfaces
H2 + 2*
2H*
(K p )
+
1 (K p )
0.5
compensation effect
very weak and strong sites do not contribute much
to the rate
H =
H2
H2
for microporous media (activated carbons) often

not satisfactory
H2
0.5
H2
Two adjacent sites needed
Dual site reaction :

A+B
C
Initial rate expressions

Forward rates
Product terms negligible
Adsorption
r = k ' p0A
Surface
k 'p0A
r=
1+ KA p0 A
Desorption
r = k'
A + *
A*
B + *
B*
A* + B*
C* + *
C + *
T1
T1
T1
T2
r0
T2
T3
pA
T3
pA
C*
(r.d.s.)
T2
r =
T3
pA
See tutorial
k 3 sNT K1K 2{p A pB pC / K eq }
{1 + K1pA + K 2 pB + pC / K 4 }2
More than one reactant
Dual site reaction, contd.
e.g. hydrogenation, oxidation
One-site models
r = r3 r 3 = s NT {k 3 A B k 3 C * }
r = kNT AB =
dual site reaction
r = kNT s A B =
Two-site models
Number of neighbouring sites (here: 6)
kNT K A K AB pA pB
1 + K A p A (1 + K AB pB )
single site reaction
kNT s K A p A K B pB
(1 + K A p A + K B pB )2
r = kNT s A B =
different sites
kNT s K A p A K B pB
(1 + K A pA ) (1 + K B pB )
Number of sites conditions dependent

NT 0 (K A pA )
12
NT =
{1+ (K
A pA )
12
optimal surface concentrations

optimal adsorption strengths
What about observed:
reaction order
activation energy ?
Langmuir-Hinshelwood/Hougen-Watson models
(LHHW)
Determination:
For: A+B
includes NT, k(rds)
r =
pApB-pCpD/Keq
slope = -Eaobs/R
slope = order ni
C+D
ln r
ln r
( kinetic factor ) ( drivin g fo rce )

( a dsorp tio n te rm ) n
molecular: KApA
dissociative: (KApA)0.5
= 0, 1, 2...
number species in
and before r.d.s.
ni =
ln pi
1/T
ln r
ln pi
E aobs = RT 2
LHHW models ?
r =
ln r
T
k 2 NT K A p A
(1 + K A p A + K B p B )
Reaction order - Activation energy

rate expression
Reaction order
r =
Limiting cases - forward rates

k 2 NT K A p A
(1 + K A p A + K B p B )
1. Strong adsorption A
nA = 1 A
r = k 2 NT
nB = B
Activation energy
r =
k 2 NT K A p A
(1 + K A p A + K B pB )
A*#
E aobs = Ea 2 + (1 A ) H A B H B
E aobs = E a 2
Ea2
depend strongly on occupancy!

vary during reaction
A*
limiting cases?
B*
k 2 NT K A p A
r =
(1 + K A p A + K B p B )
r = k 2 NT K A pA
r =
A*#
A(g) + *
Ea2
obs
a
k 2 NT K A p A
K B pB
A*#
B+*+A
= E a 2 + H A H B
A*
A*
B* + A
k 2 NT K A p A
(1 + K A p A + K B p B )
3. Strong adsorption B
2. Weak adsorption
E aobs = E a 2 + H A
r =
Ea2
Cracking of n-alkanes over ZSM-5
n-Alkanes cracking
J. Wei I&EC Res.33(1994)2467
Energy diagram
r0 = k2 K A p A
E aobs = E a 2 + H A
Initial state
200
Ea2
100
kJ/mol
0
-100
-200
0
Transition state
A+*
negative!?
Ea,obs
Eaobs
Hads
Ea2
HA
B*,C*
10
15
20
A*
Adsorbed state
Carbon number
Observed temperature behaviour
Catalytic reaction kinetics, summary

Langmuir adsorption
T higher
coverage lower
Highest Ea most favoured
Change in r.d.s.
uniform sites, no interaction adsorbed species,

finite number of sites, multicomponent
adsorption r.d.s.
Rate expression derivation
desorption r.d.s.
LHHW models
inhibition, variable reaction order, activation
energy
1/T
mechanism
kinetics
r
pl e
ln robs
series of elementary steps

steady state assumption, site balance
quasi-equilibrium / rate determining step(s)
initial rates (model selection)
sim
Composition oil fractions
Hydrodesulphurization kinetics
Sie, AIChE-J 42(1996)3498
Vacuum gasoil
Sulphur compounds
Example HDS vacuum gasoil
2.2
2.0
1/S-1/S 0 (1/wt.%)
Apparent second order behaviour

H2S inhibits strongly
Gasoil
CoMo-alumina
trickle flow
L=0.2-0.4 m
1.8
1.6
1.4
Thioethers
R
R
S S
1.2
Thiophene
Benzthiophene
1.0
0.8
0.6
0.4
2.0
concentration
0.2
0.0
1.5
0.0
conversion
1.0
0.1
0.2
0.3
0.4
0.5
0.6
Dibenzthiophene
1/LHSV (h)
10
15
20
25
30
Simulated distillation b.p.
0.5
0.0
0.0
0.2
0.4
0.6
0.8
fast decrease followed

by slow decrease
1.0
bed length
R
complex mixtures
different reactivities
lumping
Simulated profiles - HDS reactivity lumping

Three lump model: first order reactions
Simulated model data:

2nd order
k=10 m3/mol.s
c0=2 mol/m3
Kinetic coupling between catalytic cycles

Bifunctional catalysis: Reforming
2.0
sum
concentration
Three lump model:

1st orders
k1=36.1 s-1
c01=1.23
k2=16.0 s-1
c02=0.59
-1
k3=7.5 s
c03=0.18
Substituted
dibenzthiophene
Isomerization n-pentane: n-C5 -> i-C5
1.5
1
1.0
Pt-function:
0.5
n-C5 -> n-C5=

surface diffusion
Acid function:
low concentration
close proximity
n-C5= -> i-C5=

surface diffusion
Pt-function:
0.0
0.0
0.2
0.4
0.6
0.8
i-C5= -> i-C5
1.0
bed length
Three lump model adequate

Inhibition through LHHW models
Coupled catalytic cycles on different sites
Which groups lumped?
model studies
See tutorial
Initial rates - CO hydrogenation over Rh

Van Santen et al.
Kinetic model
1.
2.
CO + * CO*
CO* + * C* + O*
(r.d.s.)
800
Initial rate
r0 = sNT k 2 CO *
r0 =
Rate
600
400
200
sk2 NT KCO pCO
{ 1 + KCO pCO }2
0.2 O
cc
up
0.4
a
0.6ncy
(
0.8-)
600
550
500
450
1.0
400
Tem
(K
ture
pera
Catalysed N2O decomposition over oxides
N2O decomposition over Mn2O3

Vannice et al. J.Catal. 1996
Winter, Cimino
Rate expressions:
2 N2O
r = k obs p N 2O
r = k obs
Kinetic model
pN 2O
( pO )
strong O2 inhibition
0.5
k obs p N 2O
1 + ( pO 2 K 3 )
0.5
moderate inhibition
N2O*
N2 + O*
2* + O2
Rate expression
Also: orders 0.5-1

water inhibition
r =
k 2 NT K 1 p N 2O
(1+ K p
1 N 2O
= Explain / derive =
N2O + *
N2O*
2 O*
1.
2.
3.
r =
2N2 + O2
1st order
+ ( pO 2 K 3 )
0.5
Vannice et al. 1996
Vannice et al. 1995

Kinetic model
order N2O ~0.78
Oxygen inhibition
Values
0.4
r / 10-6 mol.s -1.g-1
0.3
638 K
623 K
608 K
598 K
0.1
0.0
0.0
2.0
4.0
6.0
Rate expression
r =
E a2 = 130 kJ / mol
648 K
0.2
H1 = 29 kJ/mol
S1 = 38 J/mol K
pN2O = 10 kPa
Eaobs = 96 kJ/mol
N2O + * N2O*
N2O*
N2 + O*
2 O*
2* + O2
1.
2.
3.
k 2 NT K 1 pN 2O
(1 + K p
1 N 2O
0 .5
H3 = 92 kJ/mol
S3 = 109 J/mol K
8.0
10.0
p O2 / kPa
= Thermodynamically consistent =
= Explain =
Initial rates - linear transformation
Ethanol dehydrogenation
Ethanol dehydrogenation
Franckaerts &Froment
Cu-Co cat.
C2H5OH
Full expression
CH3CHO + H2
Initial rate
Model:
1.
2.
3.
4.
A+*
A* + *
R*
S*
A*
R* + S*
R+*
S+*
(r.d.s.)
r =
r0 =
k 2 s NT K A
{p
p R p S / K eq
{ 1 + K A p A + K R p R + K S p S }2
k K A pA
{ 1 + K A p A }2
After rearrangement
pA
=
r0
1
k KA
KA
k KA
pA
linear form: y = a + b x
= Derive rate expression =
+ ( pO 2 K 3 )
linear least squares fit

trends, positive parameters
Kinetic studies
Differential reactor:
plug flow, low conversion
CSTR
dx i
= i r
d W Fi o
Take care catalyst

effectiveness = 1 !
r =
xi
i (W Fi o )
Integral reactor
Model selection
Mechanistic information
Initial rate measurements
Fit data on rate expressions (non-linear least squares)
Best model:
low SSR (sum of squares of residuals)
no trending in residuals
parameters significant
parameters obey thermodynamics
linearization
Rate equation
= model selection =
= rate parameters =
Data fitting - Parameter estimation

Linear least squares - straightforward
Nonlinear least squares methods:
Simplex / Powell etc. (iterative)
Levenberg-Marquardt (gradient)
O. F. = Min ( x obs x calc )
Model selection
Divergence rival models

Experimental design (sequential)
model 1
2
model 2
rate
with: x calc = f (.... k , K j ...)

to be estimated
experimental range
= initial parameters values needed =

po
N2O decomposition over ZSM-5 (Co,Cu,Fe)

Kapteijn et al. 11th ICC,1996
2 N2O
2N2 + O2
Kinetic model
1.
2.
N2O + * N2 + O*
N2O + O* N2 + O2 + *
Rate expression
r=
k1 NT p N 2O
k2 )
(1 + k1
no oxygen inhibition
N2O decomposition over ZSM-5 (Co,Cu,Fe)
Effect of CO on N2O decomposition
Kapteijn et al. 11th ICC,1996

1.0
1.0
0.8
Oxygen inhibition model

1.
2.
3.
N2O + *
N2O + O*
O2 + *
N2 + O*
N2 + O2 + *
*O2
Rate expression
r=
k1 NT pN 2O
k 2 + K3 pO 2 )
(1 + k1
X(N 2O)
833 K
0.6
CO2 + *
CO + *
CO* (Cu+)
793 K
Cu-ZSM-5
Fe-ZSM-5
0.4
0.8
CO + O*
Co-ZSM-5
0.2
X(N2O)
743 K
733 K
Fe-ZSM-5 (673 K)
0.4
0.2
Co-ZSM-5 (693 K)
688
0.0
0.0
773 K
0.0
0
Cu-ZSM-5 (673 K)
0.6
0.5
10
1.0
molar CO/N 2O ratio
p(O2 ) / kPa
CO removes oxygen from surface

so enhances step 2, oxygen removal
now observed: rate of step 1
increase: ~2, >3, >100
r1 = k1 NT pN2O
1.5
2.0
Effect of CO on N2O decomposition
Apparent activation energies N2O decomposition

CO/ N2O = 2
rate without CO
r =
rate with CO
Apparent activation energies (kJ/mol)
k 1NT pN 2O
(1 + k1 k 2 )
r = k1 NT pN 2O
ratio = 1 + k1/k2
So k1/k2 = :
1
Co
>2
Cu
>100 Fe
and: O * =
O* =
only N2O
k1 k 2
1+ k1 k2
0.7
>0.9
>0.99
CO/N2O=2
Co
110
115
Cu
138
187
Fe
165
78
Co,
Fe
r = k 1 NT pN 2O
Cu
r=
E aobs = E a 1
Eaobs = E a1 + HCO
k1 NT pN 2O
k N p
1 T N 2O
k2 + KCO pCO )
KCO pCO
(1 + k1
Apparent activation energies N2O decomposition
Kinetic coupling between catalytic cycles

adsorption effect on selectivity
CO/ N2O = 0
Hydrogenation:
Apparent activation energies (kJ/mol)
only N2O
CO/N2O=2
Co
110
115
Cu
138
187
Fe
165
78
butyne and butene compete for the same sites

but:
K1 >> K2
resulting high selectivity for butene (desired) possible
even when k2 > k1
since:
Co,
Cu
k N p
r = 1 T N 2O
(1 + k1 k2 )
Fe
r = k 2 NT pN 2O
butyne -> butene -> butane

A1
A2
A3
E aobs = m ix( E a 1, E a 2 )
S1,2 =
k1K 1
k 2K 2
Meyer and Burwell (JACS 85(1963)2877) mol%:

2-butyne
22.0
cis-2-butene
77.2
trans-2-butene
0.7
1-butene
0.0
butane
0.1
E aobs = E a 2

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Catalytic Reaction Kinetics

Reactor design equation - Packed bed

Why Catalytic Reaction Kinetics ?

Catalysis Engineering - Kinetics

Catalysis Engineering - Kinetics

Rate expression Gas phase reaction

How much detail ?

overall rate expression?

amount of A chance to meet B

Rate vs. pressure/concentration ?

fixed number of active sites

other form rate expression expected

Catalysis Engineering - Kinetics

Rate expression Catalysed reaction

Rate expressions in principle crucial for

Often used in catalysis

extrapolation more reliable

Catalysis Engineering - Kinetics

Simple example: reversible reaction

Rate expression follows from rate equation

Eliminate unknown surface occupancies

Catalysis Engineering - Kinetics

Elementary processes contd.

Quasi-equilibrium / rate determining step

Steady state assumption:

Catalysis Engineering - Kinetics

Rate expression, contd.

Rate expression - r.d.s.

Rate determining step:

Eliminate unknown occupancies

Catalysis Engineering - Kinetics

Catalysis Engineering - Kinetics

Rate expression, contd.

Catalysis Engineering - Kinetics

Catalysis Engineering - Kinetics

Other steps rate determining

Rule of thumb:Generally surface reaction r.d.s.

Catalysis Engineering - Kinetics

Multicomponent adsorption / inhibition

Uniform surface (no heterogeneity)

Adsorption entropy, <0

Data sources: Handbooks, API,JANAF

Catalysis Engineering - Kinetics

Surface reaction r.d.s.

Catalysis Engineering - Kinetics

Langmuir adsorption model

for microporous media (activated carbons) often

Catalysis Engineering - Kinetics

Two adjacent sites needed

Catalysis Engineering - Kinetics

Dual site reaction :

Initial rate expressions

Catalysis Engineering - Kinetics

Catalysis Engineering - Kinetics

k 3 sNT K1K 2{p A pB pC / K eq }

More than one reactant

Dual site reaction, contd.

e.g. hydrogenation, oxidation

dual site reaction

Number of neighbouring sites (here: 6)

single site reaction

Number of sites conditions dependent

Catalysis Engineering - Kinetics

optimal surface concentrations