Catalysis and macrokinetics Outline

Catalyst: definition, effect on activity and selectivity, classification (homogeneous, heterogeneous, bio-catalysis) Heterogeneous catalysis: introduction steps, macrokinetics rate determining step (regimes) mass transport by convection diffusion (Ficks law) external diffusion internal diffusion simultaneous internal and external diffusion
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Catalysis
Importance: approximately 85-90% of the products of chemical industry are made in catalytic processes. Definition: catalysis is a process in which the rate of a reaction is enhanced by a relatively small amount of a different substance (catalyst) that does not undergo any permanent change itself.

How catalysts act ?

A catalyst accelerates a chemical reaction by forming bonds with the reactants, allowing them to form the products, which detach from the catalyst, and leave it unaltered. A
separation

catalyst bonding

P
catalyst reaction

A
catalyst

Thus, the catalytic reaction is a cyclic event in which the catalyst participates and is recovered, in its original form, at the 3 end of the cycle.

Catalysis and activity

1. The catalyst offers an alternative path for the reaction, which is energetically more favorable (higher reaction rate implies lower reactor capacity).
A potential energy P (elementary reaction)
thermal reaction

E c< E t

Et
catalytic reaction

A Ec
catalyst bonding

H react.

P
catalyst

A
catalyst

P
reaction catalyst

separation
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reaction coordinate

2. The catalysts change the kinetics, not the thermodynamics. 3. The catalysts accelerate both the forward and the reverse reaction to the same extent.

There are also cases in which the combination of catalyst with reactant or product is not successful: Bond with the reactant too weak Bond with the reactant (or product) too strong (catalyst poisoning)

Catalysis and selectivity

In the presence of multiple reactions (consecutive and parallel reactions), a catalyst can accelerate selectively one reaction, thus increasing the process selectivity. Higher selectivity implies reduction of the separation costs and waste of reactants.

Types of catalysis
Homogeneous catalysis:

reactants and catalyst are in the same phase (liquid or gas)

Heterogeneous catalysis:

reactants and catalyst are in different phases Catalyst: solid, liquid Reactant: liquid, gas
Biocatalysis:

enzymes are natural catalysts composed primarily of proteins (many aminoacids coupled by peptide bonds). Enzymes are the most efficient catalysts: highly active (1081011-fold rate increase) and extremely selective. They work under mild conditions of temperature and pH.
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Properties of catalysts
Properties Homogeneous catalyst varying high mild limited difficult Heterogeneous catalyst varying low drastic high easy

Activity Selectivity Reaction conditions Variety of application Catalyst separation

Heterogeneous catalysts
Heterogeneous catalysts are solid materials which can be single or mixture of substances. Often, the active component is supported on another, generally inert substance, called support. As the reaction occurs on the surface, in general it is important to have high surface area per unit of weight. High surface area can be obtained by using porous materials. The catalytic activity is associated to localized points of the surface, called active centers. The decrease of the catalyst activity with the time is referred to as catalyst deactivation and it can be associated to various phenomena (fouling, sintering, poisoning etc.).

Heterogeneous catalyst can have different shapes (powder, granules, gauzes, pellets, extrudate, rings etc.) and different dimensions depending on the reactor type.

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Steps in a heterogeneously-catalyzed reactions

Heterogeneous catalytic reactions take place on the catalyst surface . As the reactant have to be transported from the bulk fluid to the solid/fluid interface, the overall reaction includes also physical transport processes, beside chemical steps.

Seven different steps : 1. External diffusion: transfer of the reactants from the fluid phase surrounding the catalyst particle (bulk fluid phase) to the external surface of the catalyst 2. Internal diffusion: transport of the reactants from the external surface of the particle through the pores to the active sites on the interior surface 3. Adsorption of the reactant on the active site 4. Surface reaction 5. Desorption of the product from the active site. 6. Internal counter-diffusion: transport of the product through the pores to the external surface 7. External counter-diffusion: transport of the product from the external 11 surface to the bulk fluid phase

Steps in a heterogeneously-catalyzed reactions

Steps 3,4,5 are purely chemical phenomena:

microkinetics
The transfer steps 1 and 7 depend upon the flowdynamics of the system. The transport steps 2 and 5 are present only with porous catalysts and 12 depend on the geometry of catalyst particles.

macrokinetics

Step 1,2,6,7 are strictly physical steps (transport phenomena)

Rate determing step

Steps 1 and 7 (external diff.) are in series with steps 3-5 (chemical steps): the external transfer occurs separately from the chemical reaction. Steps 2 and 6 (internal diff.) occur simultaneously with the chemical reaction.

As the heterogeneously catalyzed reaction involves sequential steps, at steady state the rate of these steps must be the same. If the rate constant of one of these steps is markedly smaller than the other, the overall rate is determined by this step, which is called the rate determining step. The reaction is said to be under the regime corresponding to the rate determining step.

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Regimes
Kinetic regime: rds = chemical reaction (synonym: chemical regime) External diffusion regime: rds = external diffusion (synonyms: film diffusion, external mass transfer limitation) Internal diffusion regime: rds = internal diffusion (synonyms: pore diffusion, internal mass transfer limitation).

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Convective and diffusive transport

Convection = transport by bulk motion of the fluid

initial condition

Diffusion = transport due to gradients

(concentration gradients if the transported property is the mass, temperature gradients if the transported property is the thermal energy)

As the time passes

mixing occurs 15

Mass transport by diffusion: the Ficks law

The diffusive mass transport transfer can be described by the Ficks law:

J = D

dC dx

mol m2 s

is the mass flux, i.e. the moles transported per unit of time and per unit of surface perpendicular to the diffusive movement C is the concentration of the diffusing substance, D is the diffusion coefficient.

The negative sign indicates that the diffusion occurs in the opposite direction of the concentration gradient.
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External diffusion: film model

If the supply of reactant from the bulk fluid to the external surface of the catalyst is slower than the rate of the surface chemical reaction, the reactant concentration on the catalyst surface Cs will be lower than that in the bulk fluid phase Cb. conc

solid film

fluid bulk Cb
existing conc. profile conc. profile according the film model

Cs
0

distance x

from the interface

Film model:

Existence of a stagnant layer (film), of thickness , surrounding the external surface of the catalyst, where is located the concentration gradient. 17 In the bulk fluid phase the concentration is constant.

External diffusion: Ficks law

The rate of mass transfer is expressed by the Ficks law:

By integration:

J dx = D dC
0 Cs

Cb

J =

(Cb C s )

mol m2 s

= thickness of the external film

As the determination of the thickness of the external film is difficult, normally is included in the constant giving the mass transfer coefficient

J = (C b C s )

mol m2 s

At steady state, the rate r of mass transfer must be equal to the rate of the surface reaction, expressed per unit external surface area:

r = a (Cb Cs ) = kCsn
a = catalyst external surface per unit of catalyst volume
NB. k is the kinetic constant referred to the unit of volume catalyst
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External diffusion: 1st order reaction

For 1st order reaction (n=1):

r = a (Cb Cs ) = kCs

By expressing the unknown surface concentration Cs in function of the known bulk concentration Cb:

r=

1 1 1 + k a

Cb

Only the known bulk concentration Cb appears. At the denominator there is the sum of resistances for sequential processes: 1/k = chemical resistance 1/ = external mass transfer resistance
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External diffusion: limit cases

r= 1 1 1 + k a Cb

for 1st order reaction:

conc
solid fluid film bulk

k << a

r = kC b

1 2 3 4 0

Cb

No limitation by film diffusion (kinetic regime) No gradient concentration

k >> a

r = a Cb

Strong limitation by film diffusion (external diffusion regime) steep gradient concentration

1. No limitation by film diffusion 2.,3 film diffusion and reaction 4. maximum limitation by film diff.

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External diffusion: external effectiveness factor e

The degree of the external diffusion limitation is given by the external effectiveness factor:

robs observed reaction rate = e = kCbn reaction rate at bulk fluid conditions
If the supply of reactant from the bulk fluid to the external surface of the catalyst will be not sufficiently fast to keep place with the potential intrinsic rate of the chemical reaction, the concentration of the reactant on the catalyst surface will be lower than that in the bulk fluid phase. For positive reaction orders, the observed reaction rate is lower than that corresponding to the bulk concentration (e <1)
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Internal diffusion
For most catalysts the fraction of active sites located at the external surface can be neglected. The reactant have to be transported through the pores to reach the active sites. The driving force for this transport (internal diffusion) is the concentration gradient inside the catalyst particle due to the chemical reaction. The resistance for this transport originates from collisions of the molecules, either with each other or with the pore walls.

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Internal diffusion
The diffusive mass transport inside the catalyst particle can be formally described by the Ficks law: dC mol J = De m2 s dx

x = perpendicular distance from the center of the particle

De = effective diffusion coefficient (instead of D). De takes into account that: 1. 2. (the diffusion does not occur in all the particle volume but only through the pores)

p = porosity of the catalyst particle (characteristic values: 0,2<p<0,7) =tortuosity of the pores (characteristic values: 3<<7)

(the pores neither are straight nor have the same cross-section: they have irregular structure) 3. the resistance towards transport originates from collision of the molecules either which each other (Dm = molecular diffusivity) or with the pore walls (Dk= Knudsen diffusivity)

De =

1 1 + Dm Dk

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Internal diffusion: internal effectiveness factor i

A degree of the internal diffusion limitation is given by

robs observed reaction rate = i = reaction rate at external surface conditions kC sn

If the diffusion of the reactant from the external surface inside the particle is not fast enough to compensate for its disappearance by reaction, a decreasing concentration profile is established in the particle. For positive reaction orders, this leads to lower reaction rates at positions away from the external surface and, hence, to a lower reaction rate when averaged over the complete particle volume (i <1).
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Thiele modulus
It is possible to demonstrate that the internal effectiveness i depends on a dimensionless number , called Thiele modulus
rate of chem. reac. without pore diff.

=1
small ( < 0.3)

= 3/
large ( > 3)

Vp Ap

kCs DeCs

kinetic Vp regime

Ap

kCtransition s DeCs

Int. diff. regime

maximum rate of pore diff.

Small : reaction rate is small; reaction limits the overall rate (kinetic regime) Large : diffusion rate is small: internal diff. the overall rate (int. diff. regime)
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Simultaneous external and internal diffusion

At steady state, the rate of external mass transfer must be equal to the rate of the surface reaction with internal diffusion.

rdiff ex = a (Cb Cs )

mol m3 s

a = catalyst external surface per unit of catalyst volume

rreact .+int.diff . = i k C s
At steady state: By substitution:

mol m3 s

(for 1st order reaction)

robs = rdiff ex = rreact .+int.diff .

robs

k Cb = i i k 1+ a

general formula (for 1st order reaction from this formula all the limited cases can be obtained)
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rds: surface reaction

robs

i k Cb = i k 1+ a

general formula (for 1st order reaction)

1. At low reaction temperatures, the rate constant is small relative to the mass transfer coeffient Additionally, the Thiele modulus is small (since k is small relative to De) and thus is unity. In this case the surface reaction is controlling and the concentration profile across the film and inside the pore is flat. The activation energy derived from the reaction rate correspond to the true activation energy of the chemical reaction without mass transport limitations

r = kCb

Eapp = Eatt
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ln k = k0 exp( Eatt / RT )

rds: internal pore diffusion

robs =

i k Cb i k 1+ a

general formula (for 1st order reaction)

1. At intermediate reaction temperatures, the combination of pore diffusion and surface reaction is slowest: pore diffusion is controlling and there is a concentration gradient inside the pore. The activation energy derived from the observed reaction rate constant corresponds to approximately the half of the true activation energy

r = i kCb

kCb

Ap Vp

Ap DeCs kCb = kCs Vp

De k Cb = k app Cb

Eapp = 0.5 Eatt

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rds: external pore diffusion

robs =

i k Cb i k 1+ a

general formula (for 1st order reaction)

1. At high reaction temperatures, external diffusion is controlling and there is a concentration gradient across the film. The activation energy derived from the observed reaction rate constant is generally below 5kJ/mol

r = aCb
Eapp 5 10kJ / mol

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Arrhenius diagram
ln k
Eeff = 5 kJ/mol Eeff = 0,5*Ea

Filmdiffussion/ Stoffbergang

Eeff =Ea Porendiffusion

Kinetisches Gebiet/ kein Transporteinfluss

1/T
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Books
Van Santen, van Leeuwen, Moulijn, Averill Catalysis: An Integrated Approach Second, revised and enlarged edition (NIOK, 1999) http://www.ltc1.uni-erlangen.de/htdocs/e/index.htm Chapter IV . Chemical reaction and processes of transport Macrokinetics. Octave Levenspiel Chemical Reaction Engineering, third edition, Wiley (1999).

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Vocabulary
Active centre Active component Activity Adsorption Biocatalysis Chemical regime Convection Deactivation Desorption Diffusion Effective diffusion coefficient Effectiveness External mass transport regime Gradient Heat and mass transport processes Heterogeneous catalysis Homogeneous catalysis Internal diffusion Knudsen diffusion Macrokinetics Mass transfer Mass transfer coefficient Microkinetics Molecular diffusion Porosity Porosity factor Porous material Rate determining step Regime Selectivity Stagnant layer Support Surface area Surface reaction Thiele Modulus Tortuosity Aktives Zentrum Aktiver Bestanteil Aktivitt Adsorption Biokatalyse Chemisches Regime Konvektion Deaktivierung Desorption Diffusion effektiver Diffusionkoeffizient Wirkungsgrad Stoffbergang zum Korn (uere Diffusion, Filmdiffusion, Grenzfilmdiffusion) Gradient Stoff- und Wrmetransport Heterogene Katalyse Homogene Katalyse Innerer Stofftransport, Porendiffusion Knudsen-Diffusion Makrokinetik Stofftransport Massentransferkoeffizient Mikrokinetik Molelulare Diffusion Porositt Porosittsfaktor Porses Materiall Geschwindigkeitsbestimmender Schritt Regime Selectivitt laminare Schicht Trger Oberflche Oberflchenreaktion Thiele-Modul Labyrinthfaktor

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