Water Gas Shift Reaction: Rates and Composition Profiles

Consider the water gas shift reaction:

CO + H2O = CO2 + H2
( 1)

( 2)

( 3)

( 4)

This reaction occurs in a porous catalyst under the following conditions:

temperature and pressure
composition and partial
pressures of bulk gas

T := 672 K

p := 2.5 10

y1o := 0.10

p1o := y1o p

y2o := 0.60

p2o := y2o p

y3o := 0.08

p3o := y3o p

y4o := 0.22

p4o := y4o p

Under these conditions, the equilibrium pressure of CO is:

p1e := 1.398 10

The catalyst consists of cylinders with a height and diameter of:

H := 0.014

D := 0.014
:= 0.4

The catalyst has a porosity

You may regard the catalyst as a slab, with a thickness 2 given by:

volume :=
:=

4
volume

D H

area := D H + 2

= 2.333 10

area

the original catalyst with no hole

The rate of the reaction can be expressed in terms of the partial pressure of the limiting
reactant (CO):
75

r :=

p1e

( p1e p1 )

r = k1 ( p1e p1 )

or

k1 :=

75

mol ( CO )

p1e

m ( catalyst)

Diffusion into the slab is governed by:

dp1

= 1eff N1

dz

1eff := 8.163 10

A balance over a layer with thickness dz yields:

dz

( p1 = 1eff )

or (see Figure 22.13)

2

dZ

( P = K P)

K :=

k1 1eff

The solution to this equation is:

1

B :=
1+

(
exp (

)
K)

exp K

A := 1 B

A = 2.494 10
B=1

11

Q ( Z) := A exp Z K + B exp Z K

Here, only the second term is important. We plot this profile below
i := 0 .. 20

Zi :=

i
20

( )

Q Zi 0.5

0.5

Zi

We see that the driving force for the reaction is practically zero at Z = 0.4, or at one fifth of
the slab thickness.
The effectiveness factor of the catalyst is the ratio of the actual conversion to that when there
is no mass transfer resistance (and the driving force Q = 1 throughout the catalyst). It is given
by:

E :=

Q ( Z) dZ

E = 0.082

To calculate the flux through the catalyst surface, we need the pressure gradient at Z = 0:
Z := 0

p1' :=

p1o p1e d
Q ( Z)

dZ

N1 :=

1eff

p1'

N1 = 0.061

mol
2

m s

The effectiveness of the catalyst is not very good. You are to investigate what
happens if we use the same cylindrical catalyst, but now with a hole of one half of
the diameter along the axis (see Fig. 22.2).