1.

1
Catalytic
reactions

1.4
Porous
Catalyst

1.7
External
Mass
Transfer

1.2
Catalytic
reactors
1.5
Transport
and
Reaction

1.3
Surface and
Enzyme
Reaction Rates
1.6
Mass
Transfer
Coefficient

1.8
Pore
Diffusion
1.8-1.10
Langmuir-Hinshelwood
Kinetic Mechanism

CPE624: ADVANCED CHEMICAL REACTION ENGINEERING

Gradients in the
reactor

Length scales in the

reactor

TRANSPORT AND
REACTION

Transport
Steps

CPE624: ADVANCED CHEMICAL REACTION ENGINEERING

When a catalytic reaction occurs on the surfaces within a

catalyst pellet in a packed bed, there are inevitably
concentration gradients around and within the pellet.

Need to consider several length scales in attempting to

describe catalytic reactors.
The reactor is on the order of 1 meter diameter and length,
the pellet is typically 1 cm diameter, the pores within the
pellet are 0.1 mm (10-4 m) or smaller in diameter, and
catalyst particles might be 100 , or lo-6 m in diameter, and
the reactant molecule might be 3 or l0-10 m in diameter.

CPE624: ADVANCED CHEMICAL REACTION ENGINEERING

Catalyst particle Catalyst pore Pellet Reactor

We are interested in the position.........
Reactor: in the bed z or height of the bed L.
Pellet : in the position x in the pellet with radius R
Pore : distance x down the pore diameter dpore
Walls of the pore : reactions on the catalyst particle
diameter dparticle

CPE624: ADVANCED CHEMICAL REACTION ENGINEERING

CPE624: ADVANCED CHEMICAL REACTION ENGINEERING

Small gradient dCj/dz down the reactor from inlet to exit.

Then, gradient in Cj around the
catalyst pellet.
Finally, there is the gradient within
the porous catalyst pellet and
around the catalytic reaction site
within the pellet.
CAb = concentration of reactant
A in bulk fluid

CAs = concentration of reactant

A at external catalyst
surface
CAx = concentration of reactant
A within the pellet
CPE624: ADVANCED CHEMICAL REACTION ENGINEERING

Consider first the unimolecular reaction

which occurs on a catalyst surface.....

Surface reaction rate coefficient as k,

using units of k (length/time) to satisfy
the dimensions of r (moles/area time)
and CAS (moles/volume).

The steps that must be involved in a

catalytic reaction on a surface are shown
in Figure 7-8

CPE624: ADVANCED CHEMICAL REACTION ENGINEERING

STEPS INVOLVED ARE:

Reactant Ab in the bulk
of the flowing fluid must
migrate
through
a
boundary layer over the
pellet at the external
surface of the pellet.
It must then migrate
down pores within the
pellet to find surface
sites where it adsorbs
and reacts to form B,
which then reverses the process to wind up in the flowing fluid,
where it is carried out of the reactor
CPE624: ADVANCED CHEMICAL REACTION ENGINEERING

The structures and concentration profiles of reactant near and

in a catalyst particle might look as illustrated in Figure 7-9.
For the reactant to migrate into the particle, there must be a
concentration difference between the flowing bulk fluid CAb, the
concentration at the external surface CAs, and the concentration
within the pellet CA(x).

We
write
the
concentration within the
pellet as CA(x), indicating
that it is a function of
position x, which will be
different
for
different
geometries, as we will
consider later

CPE624: ADVANCED CHEMICAL REACTION ENGINEERING

Steps in Heterogeneous Catalytic Reaction........

1. External mass transfer (diffusion) of the reactants (e.g.,
species A) from the bulk fluid to the external surface of the
catalyst pellet
Low/High velocities of fluid flow
Mass transfer resistance
Rate of reaction, rA = k(CAbkCAs)
2. Pore diffusion of the reactant from the pore mouth through
the catalyst pores to the immediate vicinity of the internal
catalytic surface.

Transport from the pore mouth catalyst to the internal

catalytic surface
Reactant A diffuses into the interior of the catalyst pellet
Large or small pellet will determine the diffusion time hence
the reaction rate
CPE624: ADVANCED CHEMICAL REACTION ENGINEERING

Steps in Heterogeneous Catalytic Reaction........

3. Adsorption of reactant A onto the active site of catalyst
surface
4. Reaction on the surface of the catalyst (A B)

conversion of A into product

5. Desorption of the products (e.g., B) from the surface.
Note : LangmuirHinshelwood Kinetics Mechanism
6. Pore diffusion of the products from the interior of the pellet
to the pore mouth at the external surface
7. External mass transfer of the products from the external
pellet surface to the bulk fluid
CPE624: ADVANCED CHEMICAL REACTION ENGINEERING

Steps in Heterogeneous Catalytic Reaction........

CPE624: ADVANCED CHEMICAL REACTION ENGINEERING

Mass transfer correlations for gases....

If there is a concentration difference of A between two
locations 1 and 2, then

JA = kmA (CA1 CA2)

JA is the mass transfer flux, [mol/s.m2]

km is the mass transfer coefficient, [mol/(sm2)/(mol/m3), or m/s]

CA1-CA2, concentration difference [mol/m3].
k mA

JA
(C A1 C A2 )

CPE624: ADVANCED CHEMICAL REACTION ENGINEERING

Mass transfer coefficient can be defined through the

Sherwood number:
[convective mass transfer rate]
Shl =

[diffusive mass transfer rate]

Shl

k mAl
DA

l is length and DA is the diffusion coefficient of A

Then kmA can be defined:

k mA

Shl D A

CPE624: ADVANCED CHEMICAL REACTION ENGINEERING

Sherwood numbers for several geometries:

1. Flow over a flat plate
2. Flow over a sphere
3. Flow through a tube
4. Flow over a cylinder
5. Tube banks and packed spheres
6. Heat transfer

CPE624: ADVANCED CHEMICAL REACTION ENGINEERING

1. Flow over a flat plate

For flow over a flat plate of length L.......
Flow is laminar if ReL < 105,

ShL 0.66 Re L Sc
1

Flow is turbulent if ReL > 105,

ShL 0.036 Re Sc
0.8
L

CPE624: ADVANCED CHEMICAL REACTION ENGINEERING

1. Flow over a flat plate

The Reynolds number is
is the velocity
v is the kinematic viscosity

Schmidt SC number

DA the diffusivity of

species A, both of which

have units of length2/time.

For gases, SC =1

CPE624: ADVANCED CHEMICAL REACTION ENGINEERING

2. Flow over a sphere

Important geometry in catalyst spheres, liquid drops, gas
bubbles, and small solid particles

The characteristic length is the sphere diameter D

ShD 2.0 0.4 Re D 0.06 Re D3 Sc 0.4

1

In the limit of slow flow over a sphere ShD = 2.0, and

this corresponds to diffusion to or from a sphere
surrounded by a stagnant fluid.

CPE624: ADVANCED CHEMICAL REACTION ENGINEERING

3. Flow through a tube

the characteristic length is the tube diameter D
Flow is laminar if ReD < 2100,

8
ShD
3
Flow is turbulent if ReD > 2100,

ShD

0.023 Re0D.8

Sc

CPE624: ADVANCED CHEMICAL REACTION ENGINEERING

4. Flow over a cylinder

The transition from laminar to turbulence depends on
position around the cylinder
Flow is laminar if ReD < 4,

CPE624: ADVANCED CHEMICAL REACTION ENGINEERING