Kinetics and Parameter

estimation

Carlos Omar Castillo Araiza.

October 11th,18th and 25th, 2013.
Contents

n  Catalysis and Kinetics

n  Parameter Estimation
n  Trends in Kinetics
 How much do we know about
catalysis??

6000 BC 1835
Jöns Jacob Berzelius
Fermentation systematic work in catalysis
 Research in Catalysis
n  A multi-discipline approach:
n  Reaction kinetics and mechanism
n  Reaction paths, intermediate formation & action, interpretation of results obtained
under various conditions, generalising reaction types & schemes, predict catalyst
performance…

n  Catalyst development

n  Material synthesis, structure properties, catalyst stability, compatibility…

n  Analysis techniques

n  Detection limits in terms of dimension of time & size and under extreme conditions
(T, P) and accuracy of measurements, microscopic techniques, sample preparation
techniques…
 Research in Catalysis

n  Reaction modelling

n  Elementary reactions and rates, quantum mechanics/chemistry, physical
chemistry

n  Reactor modelling

n  Mathematical interpretation and representation, the numerical method,
micro-kinetics, structure and efficiency of heat and mass transfer in
relation to reactor design …

n  Catalytic process

n  Heat and mass transfers, energy balance and efficiency of process …
What is a Catalyst?
A Potential Diagram Energy.
 Note:::

n  It is important to remember that the use of catalyst DOES

NOT vary ΔG & Keq values of the reaction concerned, it
merely change the PACE of the process.
n  Whether a reaction can proceed or not and to what
extent a reaction can proceed is solely determined by
the reaction thermodynamics, which is governed by the
values of ΔG & Keq, NOT by the presence of catalysts.
n  In another word, the reaction thermodynamics provide
the driving force for a rxn; the presence of catalysts
changes the way how driving force acts on that process.
 Example:

e.g CH4(g) + CO2(g) = 2CO(g) + 2H2(g) ΔG°373=151 kJ/mol (100 °C)

ΔG°973 =-16 kJ/mol (700 °C)
n  At 100°C, ΔG°373=151 kJ/mol > 0.
There is no thermodynamic driving force, the reaction won t proceed
with or without a catalyst
n  At 700°C, ΔG°373= -16 kJ/mol < 0.
The thermodynamic driving force is there. However, simply putting CH4
and CO2 together in a reactor does not mean they will react. Without a
proper catalyst heating the mixture in reactor results no conversion of
CH4 and CO2 at all. When Pt/ZrO2 or Ni/Al2O3 is present in the reactor at
the same temperature, equilibrium conversion can be achieved (<100%).
 Types of Catalysts & Catalytic
Reactions
n  Classification based on the catalyst physical state, a catalyst can
be:
n  gas,
n  liquid,
n  solid
n  Classification based on the substances from which a catalyst is
made:
n  Inorganic (gases, metals, metal oxides, inorganic acids, bases
etc.)
n  Organic (organic acids, enzymes etc.)
 Types of Catalysts & Catalytic
Reactions
n  Classification based on the ways catalysts work:
n  Homogeneous - both catalyst and all reactants/products are in
the same phase (gas or liquid)
n  Heterogeneous - reaction system involves multi-phase
(catalysts + reactants/products)

n  Classification based on the catalysts action:

n  Acid-base catalysts; Enzymatic; Photocatalysis;
Electrocatalysis, etc.
 Solid Catalysts
n  Catalyst composition:
n  Active phase
n  Where the reaction occurs (mostly metal/metal oxide)

n  Promoter
n  Textual promoter (e.g. Al - Fe for NH3 production)

n  Electric or Structural modifier

n  Poison resistant promoters

n  Support / carrier Catalyst

n  Increase mechanical strength

Support

n  Increase surface area (98% surface area is supplied within the

porous structure)
n  may or may not be catalytically active
 General requirements for a good
catalyst:

n  Activity - being able to promote the rate of desired

reactions.
n  Selective - being to promote only the rate of desired
reaction and also retard the undesired reactions.

Note: The selectivity is sometime considered to be

more important than the activity and sometime it is
more difficult to achieve.
 General requirements for a good
catalyst
n  Stability - a good catalyst should resist to
deactivation, caused by
n  the presence of impurities in feed (e.g. lead in petrol poison
TWC.
n  thermal deterioration, volatility and hydrolysis of active
components.
n  attrition due to mechanical movement or pressure shock.

n  A solid catalyst should have reasonably large surface

area needed for reaction (active sites). This is usually
achieved by making the solid into a porous structure.
 Solids and Solid Surface

n  Defects and dislocation on surface crystalline structure

n  A perfect crystal can be made in a controlled way
n  Surface defects
Terrace Step
n  terrace
n  step
n  Kink
n  vacancy
n  Dislocation
n  screw dislocation

n  Defects and dislocation can be desirable for certain catalytic reactions as
these may provide the required surface geometry for molecules to be
adsorbed, beside the fact that these sites are generally highly energised.
 What about the reactor??
n  A catalytic reaction can be operated in a batch manner
n  Reactants and catalysts are loaded together in
reactor and catalytic reactions (homo- or
heterogeneous) take place in pre-determined
temperature and pressure for a desired time /
desired conversion.
n  Type of reactor is usually simple, basic
requirements
n  Withstand required temperature & pressure
n  Some stirring to encourage mass and heat transfers
n  Provide sufficient heating or cooling
 Catalytic Reaction
Processes

n  Catalytic reactions are commonly operated in

a continuous manner
n  Reactants, which are usually in gas or liquid
phase, are fed to reactor in steady rate (e.g. mol/h,
kg/h, m3/h)
n  Usually a target conversion is set for the reaction,
based on this target
n  required quantities of catalyst is added
n  required heating or cooling is provided
n  required reactor dimension and characteristics are
designed accordingly.
Catalytic Reaction Processes
n  Reactants in continuous operation are mostly in
gas phase or liquid phase
n  easy transportation
n  The heat & mass transfer rates in gas phase is much
faster than those in liquid
n  Catalysts are pre-loaded, when using a solid
catalyst, or fed together with reactants when
catalyst & reactants are in the same phase and pre-
mixed
n  It is common to use solid catalyst because of its easiness to separate
catalyst from unreacted reactants and products
Note: In a chemical process separation usually accounts for ~80% of
cost.
Kinetics :
Kinetics :
Kinetics :
Kinetics :
Kinetics :
Kinetics :
 Kinetics in industry:
www.eurokin.com

Kinectis Transport Phenomena

+
Kinetics

Inquiry: 24 European Companies.

Kinetics
n  Elementary
reaction is
such a
reaction in
which one or
more of the
species react
directly to
form
products.
Adsorption-Reaction-
Desorption.
 Adsorption on Solid Surface
n  Adsorption is a process in which molecules from gas (or liquid) phase land on,
interact with and attach to solid surfaces.
n  The reverse process of adsorption, i.e. the process in which adsorbed molecules
escape from solid surfaces, is called Desorption.
n  Molecules can attach to surfaces in two different ways because of the different
forces involved. These are Physisorption (Physical adsorption) & Chemisorption
(Chemical adsorption)

Physisorption Chemisorption
force van de Waal chemical bond
number of adsorbed layers multi only one layer
adsorption heat low (10-40 kJ/mol) high ( > 40 kJ/mol)
selectivity low high
temperature to occur low high
 Adsorption On Solid Surface
Adsorbent and adsorbate
n  Adsorbent (also called substrate) - The solid that provides surface for adsorption
n  high surface area with proper pore structure and size distribution is essential
n  good mechanical strength and thermal stability are necessary
n  Adsorbate - The gas or liquid substances which are to be adsorbed on solid
Surface coverage, θ

The solid surface may be completely or partially covered by adsorbed

molecules (i).

define θ i= fraction of adsorption sites occupied

fraction of adsorption sites available
θi = 0~1
 Adsorption On Solid Surface
Adsorption heat:

n  Adsorption is usually exothermic (in special cases dissociated

adsorption can be endothermic)

n  The heat of chemisorption is in the same order of magnitude of

reaction heat but:

The heat of physisorption is in the same order of magnitude of

condensation heat.
31
 The Langmuir adsorption isotherm

n  Basic assumptions

n  surface uniform (ΔHads does not vary with coverage)
n  monolayer adsorption, and
n  no interaction between adsorbed molecules and adsorbed
molecules immobile
n  The Langmuir adsorption isotherm
n  The Langmuir adsorption isotherm
n  The Langmuir adsorption isotherm
 Note: Adsorption On Solid Surface. Ideal or not
ideal??.
Five types of adsorption isotherms are found
over all solids……..

I n  Type I is found for porous materials with small pores e.g. charcoal.
It is clearly Langmuir monolayer type, but the other 4 are not

II
n  Type II for non-porous materials
amount adsorbed

III n  Type III porous materials with cohesive force between adsorbate
molecules greater than the adhesive force between adsorbate
molecules and adsorbent
IV
n  Type IV staged adsorption (first monolayer then build up of
additional
layers)
V

n  Type V porous materials with cohesive force between adsorbate

1.0
molecules and adsorbent being greater than that between
relative pres. P/P0
adsorbate molecules
Adsorption On Solid Surface
n  Other adsorption isotherms for chemisorption:

Many other isotherms are proposed in order to explain the observations

n  The Temkin (or Slygin-Frumkin) isotherm
n  Assuming the adsorption enthalpy ΔH decreases linearly with surface
coverage

ΔH of ads
1 [b1eQs /RT P RT $ 1+b1CA '
1 Langmuir
!i = " !i dS = " dS = ln & i )
Temkin
0 0 (1+b eQs /RT P
1 i % 1+b C
1 A exp ( # RT ) (
θi

n  The Freundlich isotherm

n  assuming logarithmic change of adsorption enthalpy DH with surface
coverage

"! N % [b e i i
$
1
Q/RT
CA / (1+ b1eQ/RT CA )]#aeQ/Q0 dQ ΔH of ads
!= =i 0 Langmuir
i
" N i
%0
$
aeQ/Q0 dQ Freundlich
i
θi
 gas phase
n  The long journey for reactant molecules to reactant molecule

1. travel within gas phase 1 gas phase

2. cross gas-liquid phase boundary
2
3. travel within liquid phase/stagnant layer
3 liquid
4. cross liquid-solid phase boundary 45 phase /
stagnant
5. reach outer surface of solid layer
6. diffuse within pore 6
7. arrive at reaction site porous pore
solid
8. be adsorbed on the site and activated
9. react with other reactant molecules, either
being adsorbed on the same/neighbour 78 9
sites or approaching from surface above
 History of catalysis

Hougen-Watson

Langmuir-Hinschelwood

Michaelis-Menten

1910 s 1940 s 1990 s

ki is extracted from fitting particular kinetic equations

Parameter estimation
Modern history of catalysis
Dumesic-Rudd
Froment

1910 s 1940 s 1990 s

ki is either calculated or measured

 What is microkinetics about?
Microkinetic analysis (MK)

examination of catalytic reactions in terms of elementary

chemical reactions that occur on the catalytic surface and
their relation with each other and with the surface during a
catalytic cycle.

It means that the subject of investigation is not the overall

reaction but each particular elementary reaction.

J. A. Dumesic et al., Ind. Eng. Chem. Res. 1987, 26 (1399)

What is microkinetics about?
What is microkinetics about?
What is microkinetics about?
What is microkinetics about?
What is microkinetics about?
Compare of micro and
conventional models
Micro Conventional
Limited to the
Detail Very complex terminal species and
r.d.s.
Trends, what s going Accurate information
Information on on the surface the selectivity,
temperature profile
Interval of Narrow, determined
application Wide by experimental
conditions
Application Catalyst and process Reactor and process
design design
Kinetic variables in MK
Kinetic variables in MK
n  Preexponential factor
n  Transition State theory
n  Collision theory
n  Activation energy
n  Unity Bond Index – Quadratic Exponential
Potential (UBI-QEP)
n  DFT

n  Energy barrier

n  UBI-QEP
Transition state theory

K‡ k
A + B ↔ AB‡ → C + D
when C and D emerge, the reaction has to go
through the lowest energy barrier (represented
by the transition state)
The relation between concentration of reactants
and molecules in transition state is given by
equilibrium constant

‡ aAB ⎛ ΔG 0‡ ⎞ ⎛ ΔS 0‡ ⎞ ⎛ ΔH 0‡ ⎞
K= = exp ⎜ − ⎟ = exp ⎜ ⎟ exp ⎜ − ⎟
a A aB ⎝ k BT ⎠ ⎝ kB ⎠ ⎝ k BT ⎠
Transition state theory
Transition state theory
Transition state theory
Transition state theory
Transition state theory
Transition state theory
 UBI-QEP
n  allows us to enumerate
n  adsorption heats (atomic, di-, polyatomic molecules)
n  activation energy of the reaction
n  more phenomenological than empirical approach
n  usually good accuracy (≈ 1-3 kcal/mol)
n  the theory is based on the assumptions that there is
a two-center interaction between the surface metal
atom and adatom

E. Shustorovich et al., Surf. Sci. Rep. 1998, 31 (1)

UBI-QEP
n  all relevant equation and their derivation is available
in the literature
n  there are some information which one has to know
n  geometry of adsorption
n  total bond energy in gas phase of each adsorbed compound
n  the number of bonds between catalyst and admolecule
Activation barriers
n  Algorithm based on UBI-QEP
n  Dissociation (AB –> A + B)
⎛ QQ ⎞
ΔE * = 1 ⎜ DAB + A B + QAB − QA − QB ⎟
2 QA + QB
⎝ ⎠

n  Recombination (A + B -> AB)

1 ⎛ QAQB ⎞
ΔE = ⎜ DA + DBC − DAB − DC +
*
+ QA + QBC − QAB − QC ⎟
2 QA + QB
⎝ ⎠
n  Disproportionation (AB + C -> A + BC)
QAQB
ΔE = *

QA + QB
Activation barriers
Activation barriers
 Composition of MK model
Overall reactions 2 Independent reactions
A+B ↔ AB 12 Species
5 gaseous A, B, AB, C, AC2 G
A+2C ↔ AC2 7 surface *, A*, B*, C*, AC*, AB*, AC2* Sur

Elementary reactions 12 Equations

A + * ↔ A* (G-1) reactor equations
depends whether reactor is CSTR or
B + * ↔ B*
plug flow
C + * ↔ C* (Sur-1) Steady state
A* + B* ↔ C* + * dΘ/dt=0
A* + C* ↔ AC* + * 1 mass conversion
AC* + C* ↔ AC2* + * Σyi=1
AB* ↔ AB + * 1 site conversion
AC2* ↔ AC2 + * ΣΘi=1
 MK model - example

rCO* = 3r1-r5-2r11
r* = -3r1-r2+2r3+r4+r5+r6
+r7+r8-2r9-2r10+2r11
rH2O* = 2r2-2r9
rCO2* = 2r3-2r11
rCH3OH* = -r4+r8
rH* = -r5-r6-r7-r8+2r9+2r10
rHCO* = r5-r6
rH2CO* = r6-r7
rH3CO* = r7-r8
rOH* = 2r9-2r10
rO* = 2r10-2r11
3 CO + 2 H2O = 2 CO2 + CH3OH
 Examples
CO
H2
CO2
H2O
a) T = 623K
ptot = 2,1 MPa
H2/CO = 3
b)  T = 573K
ptot = 1,1 MPa
H2/CO = 3
c) T = 553K
ptot = 2,1 MPa
H2/CO = 3
d) T = 523K
ptot = 2,1 MPa
H2/CO = 3

G. Lozano-Blanco et al., Ind. Eng. Chem. Res. 2008, 47 (5879)

 MK Today
n  microkinetics seems to be quite handy
tool for the catalyst design
n  its background is still rather
undetermined and there are many
interpretation of MK models
n  it has to be combined with experiments
to prove results coming out of it
TRENDS IN KINETICS!!
Literature
J. A. Dumesic, The Microkinetics of Heterogeneous Catalysis ,
ACS, Washington, 1993
R. D. Cortright, Advances in Catalysis, 2001, 46 (161)
E. Shustorovich et al., Surf. Sci. Rep. 1998, 31 (1)
J. A. Dumesic et al., Ind. Eng. Chem. Res. 1987, 26 (1399)