PRINCIPLES OF CATALYSIS

Part 1c: Diffusion

Steps in the Catalytic Reaction

A schematic diagram of a tubular packed bed with catalyst pellets is shown below:

Packed catalyst bed

Catalyst pellet

Catalyst pellet surface

Pores

The overall rate of reaction is equal to the slowest step in the mechanism (Step 1-7):

Physical kinetics Chemical kinetics (rate of adsorption, rate of desorption, rate of chemical reaction)

Steps in the Catalytic Reaction

STEPS IN A CATALYTIC REACTION (Table Form)
1.

2.

3.

4.
5. 6.

7.

Mass transfer of the reactant(s) or External Diffusion In from the bulk fluid to the external surface of the catalyst pellet. Diffusion of the reactant or Internal Diffusion In from the pore mouth through the catalyst pores to the immediate vicinity of the internal catalytic surface. Adsorption of reactant A onto the catalyst surface. Reaction on the surface of the catalyst (e.g.,A B) Desorption of product B from the catalyst surface Diffusion of the products or Internal Diffusion Out from the interior of the pellet to the pore mouth at the external surface. Mass transfer of the products or External Diffusion Out from the external pellet surface to the bulk fluid.

Steps in Catalytic Reaction

1. 2. 3. 4. 5. 6. 7. Diffusion of the reactant(s) (e.g., species A) from the bulk fluid to the external surface of the catalyst pellet Diffusion of the reactant from the pore mouth through the cat. pores to the immediate vicinity of the internal catalytic surface Adsorption of reactant onto the catalyst surface Reaction on the surface of the catalyst (e.g., A B) Desorption of the product Diffusion of the products from the interior of the pellet to the pore mouth at the external surface Diffusion of the products from the external pellet surface to the bulk fluid
A B A 1 7
External diffusion Internal diffusion

B A

2 6 2

3
4

Catalytic surface

Steps in the Catalytic Reaction

Steps

in the catalytic reaction can be divided into two categories:

Diffusion steps (1, 2, 6, and 7 in table in the next slide) Reaction steps (3, 4, and 5)

The

overall process can be broken down into sequence of individual steps.

Types of Adsorption
Types of Adsorption Characteristic

Physical adsorption Unselective, low energy of adsorption. Extent of adsorption related to boiling point of (physisorption) gas, not nature of solid surface. No breaking of bonds in molecules and negligible changes in bond energies. Selective, strongly dependent on both gas and Associative solid surface. chemical Higher energies of adsorption than those of adsorption physisorption. (chemisorption) Bonds in the adsorbed molecules are changed in strength but not broken, i.e. molecules adsorbed whole molecular fragments Selective, strongly dependent on both gas and Dissociative solid surface. chemical Higher energies of adsorption than those of adsorption physisorption. (chemisorption) Bonds are in the adsorbed molecules are broken, i.e. molecules adsorbed as two or more molecular fragments

Types of Adsorption (contd)

C-O C-O
Molecule approaches surface Physical adsorption

O C C O C
Associative chemisorption

Dissociative chemisorption

Reaction and adsorption

Increasing interaction with metal surface

Representation of adsorption, and possible subsequent reaction of CO on various solid surfaces

Example: CO adsorption on Al2O3 ,Bu ,Ni Associative Chemisorption: CO + 3H2

CO + H2
Cu

CH4 +H2O CH3OH

Dissociative Chemisorption: CO

Ni

C+O

Reaction Steps

Example:
The decomposition of cumene to form benzene and propylene. C6H5CH(CH3)2 C6H6 + C3H6

Reaction Steps (Adsorption)

STEP 3 The catalytic mechanism extends beyond the surface to involve physical diffusion to & inside the particle leading to the following: Adsorption on the surface: kads

Chemisorption

Results from chemical bonds between the molecule (adsorbatereactant/product) and the solid surface (adsorbent-catalyst) Very specific because receptive sites for chemisorption must exist Comes from Van der Waals forces & physical in origin Weaker than chemisorption & not specific

Physical adsorption

Adsorption on the catalyst surface: rate of adsorption = rateattachment ratedetachment = kadsf(reactant,products)

kads = adsorption equilibrium constant

Reaction Steps (Surface Reaction)

VARIOUS TYPES OF KINETIC MODELS

Single site
AS BS

Dual site (Langmuir-Hinshelwood kinetics):

1.

AS+BS
A B

CS+DS
C D

1.

A S + B S
B A

CS+DS
C D

Eley Rideal
A S + B(g)
B A

C S + D(g)
C D

Mechanistic Transformation at The Surface of Catalyst

R(g) + OL P + OL

and

+ O2
OL = Lattice oxygen

Steps in the Catalytic Reaction (4)

The catalytic mechanism extends beyond the surface to involve physical diffusion to & inside the particle leading to the following: (cont.) SURFACE REACTION: ks

Single

site (A S
B

B S)

Reaction Step 5 (Desorption)

The catalytic mechanism extends beyond the surface to involve physical diffusion to & inside the particle leading to the following: (cont.) Desorption of product/s BS B+S
B B

Rate

of desorption = -rate of adsorption

Diffusion Steps (1 & 7) (External)

The catalytic mechanism extends beyond the surface to involve physical diffusion to & inside the particle leading to the following: External Diffusion of Molecule A:

k ext.diff. = kg Sext.

Motion of A through the fluid outside the particle is governed by external or bulk diffusion or mass transfer diffusion Decreasing particle diameter/size, density & viscosity result in an increase in the external diffusion rate

Diffusion Step (External)

Ficks

first law of diffusion:

J A - cDAB y A J A molar diffusive flux of species A c total concentrat ion D AB diffusivity of A in B y A mole fraction of A

In

term of molar flux of species A:

WA J A y A (WA WB ) WA molar flux of A WB molar flux of B

Diffusion Steps 6 & 7 (External)

1.

Types of molar flux Equimolar Counterdiffusion WA - WB -D ABCA

A A B B

2.

Dilute concentration When the mole fraction of the diffusing solute and the bulk motion in the direction of the diffusion are small. Then,

WA J A -D ABCA

Diffusion Steps 6 & 7 (External)

3.

Types of molar flux Diffusion Through a Stagnant Gas The diffusion of a solute A through a stagnant gas B often occurs in systems in which two phases are present. If gas B is stagnant, there is no net flux of B with respect to a fixed coordinate: that is, WB = 0 then,

WA -cD ABy A y A WA
4.

Forced Convection
WA BAZ C A Vz BAZ bulk flow

AC

CA

JAZ JAx

Vz Terminal velocity A c Crossectional area C A Concentration of A

Diffusion Steps 2 & 6 (Internal)

Overview

of the internal diffusion

External diffusion

External diffusion

Internal diffusion

Porous catalyst pellet

External surface

Diffusion Step (Internal)

The catalytic mechanism extends beyond the surface to involve physical diffusion to & inside the particle leading to the following: (cont) Internal Pore Diffusion: k int.diff. = ks Sint.h

Second step in the mechanism is diffusion into the pores leading to the reacting surface sites Resistance to this diffusion is through collisions either with other molecules (bulk diffusion) or with the walls of the pore (Knudsen Diffusion) Rates of pore diffusion-controlled reactions can be increased by decreasing the particle radius or increasing the diffusivity (by increasing the pore radius)

External Diffusion
Diffusion of the reactants and products between the bulk fluid and the external surface of the catalyst. An essential condition for successful kinetic measurements is to ensure that the reaction is free of mass transfer limitations (external and internal diffusion) Detecting a limitation in External Diffusion
v 2v

3v

4v

5v

conversion

F1 G1

F2 G2

F3 G3

F4 G4

conversion

No limitation by external diffusion

F G

5F 5G

No limitation from external diffusion

Limitation by external diffusion Limitation by external diffusion

(a)

(b)

Two diagnostic tests to indicate if a reaction is limited by external diffusion (a) if the flow rate is increased proportionately to the catalyst volume, so that the space velocity is constant as the mass flow increases; a constant conversion indicates no limitation by external diffusion. (b) if plots conversion versus contact time for two markedly different catalyst volumes are compared, superimposable curves indicate no limitation by external diffusion

Internal Diffusion
Diffusion of the reactants or products from the external pellet surface (pore mouth) to the interior of the pellet
Detecting a limitation in Internal Diffusion
dp
dp/2 dp/3 dp/4

conversion

F G

F G

F G

F G

Limited by internal diffusion

Chemical kinetic control

dp

Experiment to find out whether reaction kinetics or internal diffusion limits a conversion. Maintain constant all operating variables (volumetric gas flow, space velocity, contact time, reaction temperature, inlet gas composition, and catalyst volume) as the particle sizes of the catalyst are progressively varied, as dp, dp/2, dp/3, and dp/4. Then plot conversion against particle size; and if the conversion varies, internal diffusion is limiting, whereas a constant conversion indicates limitations of reaction kinetics only

Phenomena of Diffusion
- Reaction takes place only on the catalyst and not in the fluid surrounding it - The fluid velocity in the vicinity of the spherical pellet will very with position around the sphere
CAs CAb

The flow of gas

Catalyst pellet Boundary layer

As illustrated, the change in concentration of A from CAb to CAs takes place in a very narrow fluid layer next to the surface of the sphere

- At low velocities the mass transfer boundary layer thickness is large and diffusion limits the reaction -As the velocity past the sphere is increased, the boundary layer thickness decreases and the mass transfer across the boundary layer no longer limits the rate of reaction - Reaction-limiting conditions can be achieved by using very small particles, but the smaller particle size, the greater the pressure drops in a packed bed.

Rate-controlling
When heterogeneous reactions are carried out at steady state, the rates of each of the three reaction steps in series (adsorption, surface reaction, and desorption) are equal to one another. However, one particular step in the series is usually found to be rate-limiting or rate-controlling.
6

Adsorption-limited reaction
initial rate

0.4

0.35

Surface-reaction-limited

5
0.3

initial rate

0.25

0.2

0 . 15

0.1

1
0.05

0 0 1 2 3 4 5 6

0 0.09 2.09 4.09 6.09 8.09 10 . 0 9 12 . 0 9

initial concentration of reactant

initial concentration of reactant

3.5

Desorption-limited reaction

initial rate

2.5

1. 5

0.5

0 0 1 2 3 4 5 6

initial concentration of reactant

1.8 Steps in catalytic reaction The catalytic mechanism extends beyond the surface to involve physical difusion to and inside the particle Sequence of stages through the gas phase reaction by a heterogeneous catalyst
1. 2. 3. Transport of reactants through the gas phase to the exterior of the catalyst pellet Transport of reactants through the pore system of the catalyst pellet toa catalytically-active site Adsorption of reactants at the catalytically-active site

4.
5. 6. 7.

Chemical reactions between reactants at the catalytically-active site (frequently several steps)
Desorption of products from the catalytically-active site Transport of products through the catalyst pore system from the catalytically-active site to the exterior of the catalyst pellet Transport of products into gas phase from the exterior of the catalyst pellet

1 External diffusion K ext. diff = Kg S ext

4 Surface reaction Ks + 5 Desorption of B 6. Internal diffusion of B 7. External diffusion of B

2 Internal diffusion K int. diff = Ks S int

A A

3 Adsorption K ads

Ko = Kg S ext

Ks S int

+
ads

Ks S int

External Diffusion
Example For NRE = 1000 Mass transfer factor = 0.57 X (1000) -0.41 = 0.03 When does NRE become small, < 50 NRE = 2R . G liner mass velocity for NRE = 10 Mass transfer factor = 0.84 (10) -0.51 = 0.25

Increase particle size, Increase linear mass velocity To circumvent this in the LAB 1. Make catalyst chips 2. Feed + diluent (ballast) How to check for external diffusion - Vary catalyst bed volume NRE NRE

DETECTING A LIMITATION IN EXTERNAL DIFFUSION

Test 1
V 2V 3V 4V

G = mass flow of reacting gas, vary = constant catalyst pellet-diameter ( const. int. diffusion)
F1 2F1 2G1 3F1 3G1 4F1 4G1

G1

Conversion

Limitaton by external diffusion

No limitation from external diffusion

Fo Flow rate

IF FLOW RATE IS INCREASED PROPORTIONATELY TO THE CATALYST OLUME, SO THAT SPACE VELOCITY IS CONSTANT (LHSV = FO ) AS THE MASS FLOW INCREASES, THEN G CONSTANT CONVERSION = NO LIMITATION

1.8.2 Internal Pore Diffusion

The second step in reaction mechanism is diffusion ino the catalyst pores leading to the reacting surface sites. Resistance to this diffusion is through collisions either with 1. Other molecules (bulk diffusion), DB or 2. The walls of the pore (Knudsen diffusion) DK DB=T 3/2/PT Bulk Diffusion, DB DK = T 1/2 TP Knudsen Diffusion, DK Where T = temperature PT = total pressure TP = radius of the pore Eqn 6 Eqn 7

Usually DB and DK are combined Dave = DB DK DB + DK

Eqn 8

And corrected for particle porosity, and tortuosiity of the pores Eeff = Dave Eqn 9

Porosity is measurable but is difficult to characterize. As an approximation = 1/0 Eqn 1 Is useful. If not known, sufficient accuracy is achieved by the approximation that = 0.5. thus it is good enough to assume Deff = (0.25) D ave Eqn 11 For simple nth order irreversible reactions models for diffusion-reaction lead to the relationship