CHPR5501: Advanced Reaction Engineering and Catalysis

Lecture 6-7: Heterogeneous Reaction Engineering

Winthrop Prof. Mike Johns

School of Mechanical and Chemical Engineering
University of Western Australia

Additional complicating factors Heterogeneous Reaction Systems

(i) Since more than one phase is present, the movement of material from phase to
phase is important. Thus the reaction rate equation must be adapted. It will probably
include mass transfer (e.g. diffusion) terms.
(ii) The contacting pattern of the different phases is important. Each phase can
present its own flow pattern (e.g. plug or well mixed) and the phase form
(discontinuous (e.g. droplets) or continuous) is also crucial.
What is rate limiting? (gas + Solid reaction)
Gas phase mass transfer (flux)
Qg =

1
=-kg(Cg-Cs)

Cg

reaction rate at surface (flux)

1
=-ks(Cs)

Qs =

Cs is unknown can eliminate from above

equations
Qs =
Cs =

Cs
Reaction Surface

C
+ g

Qs = =

1
1 1
+

Heterogeneous Non-Catalytic Reactions

A (fluid) + B (solid)

Initial
unreacted
particle

Solid liquid/gas Systems

fluid products

solid products
fluid + solid products

Partially
reacted
particle

Completely
reacted
particle

Final particle is hard,

firm, and unchanged in
size
Flaking ash or gaseous
products cause
shrinkage in size

Particle shrinks with time,

finally disappearing

Examples
(i) Solid does not appreciably change in size during reaction
a) Roasting (or oxidation) of sulphide ores to yield metal oxides. For example, in
the preparation of zinc oxide the sulphide ore is mined, crushed, separated by
flotation and then roasted to form hard white zinc oxide particles according to the
reaction
2ZnS(s) + 3O2(g) 2ZnO(s) + 2SO2(g)
Similarly, iron pyrites react as follows

4FeS2(s) + 11O2(g) 2Fe2O3(s) + 8SO2(g)

The nitrogenation of calcium carbide to produce calcium cyanamide:
CaC2(s) + N2(g) 2CaCN2(s) + C(amorphous)

Shrinking (Unreacted) Core Model no solid particle size change

ash

Low conversion

Unreacted core
time

High conversion

time

reaction
zone

Concentration of
solid reactant

Radial position

The above assumes an unreacted core alternative is a progressive conversion model

with no well-defined interface.

Representation of concentrations of reactants and products for the reaction

A(g) + bB(s)

rR(g) + sS(s)

For a particle of unchanging size:

Step1. Diffusion of gaseous reactant A through the film surrounding the particle
to the surface of the solid.
Step 2. Penetration and diffusion of A through the ash layer to the surface of the
unreacted core.
Step 3. Reaction of gaseous A with solid at the reaction surface.
Step 4. Diffusion of gaseous products R through the ash back to the exterior surface
of the solid.
Step 5. Diffusion of gaseous products R through the gas film back into the main body
of the fluid.
Note: Some steps may not exist. For example if no gaseous products are formed
Steps 4 and 5 will not be relevant.
Also the resistances of the different steps usually vary greatly from one another.
In such cases we can consider the step with the highest resistance to be
rate-controlling.

Step 1 or 5 controls
Diffusion of gas through the film surrounding the particle to/from the surface
of the solid.

Concentration of
gas phase reactant

rc radius of unreacted core

t time for complete reaction of particle

=1

Step 2 or 4 controls
Diffusion of gas through the Ash Layer control.

Concentration of
gas phase reactant

=13

+2

= 1 3(1 )2/3 +2 1

Step 3 controls
Chemical Reaction Controls

Concentration of
gas phase reactant

=1

= 1 (1 )1/3

For a Shrinking Particle

Step 2 and 4 are irrelevant as rate controlling steps no Ash layer
Step 3 (chemical reaction control) identical to non-shrinking particles
Step 1 or 5 controls Shrinking particle
R is now changing with time

=1

Concentration of
gas phase reactant

= 1 1

2/3

Assumes Stokes Law Regime

(diffusion only no flow affects)

All of the above assumes isothermal

conditions heats of reaction for fast reactions
can create temperature gradients in the particles
- These affect both reaction rates and diffusion coefficients

Plot of rc or R versus t

Plot of 1-XB versus t

rc / R
or
R/R0

1-XB

0
0

t/t

t/t

Contacting Patterns for Gas Solid Reactors

Fluid-Fluid Reactions
Example: Preparation of Sodium Amide
NH3(g) + Na(l) (250C) NaNH2(s) +0.5H2

The following factors are important:

(i) Overall Rate Expression: Generally both the mass transfer coefficient and the
chemical reaction rate are important
(ii) Equilibrium Solubility: This will limit movement between phases.
(iii) The Contacting Scheme: Counter-current schemes predominate, particularly
for gas-liquid systems.

Mass transfer resistance will exist in both the liquid and gas phases.

Contacting Patterns for GasLiquid (Fluid-Fluid) Reactors

The additional form of Heterogeneous Reaction Engineering is the use of Solid

Catalysts. These reduce the potential energy barrier over which the reactants must
pass to form products see diagram below

Whilst a catalyst will speed up a reaction, it never affects the end-point of the reaction
or the equilibrium this is determined by thermodynamics
Since the solid surface is responsible for catalytic activity, a large readily available
surface area and easily handled materials is desirable. By a variety of method, surface
areas of many 10s of meters per gram of (very porous) catalyst can be achieved.
A lot of catalysts are susceptible to poisoning. This is the chemisorption or physical
adsorption of materials on the catalytically active sites reducing their catalytic
effectiveness. A classic example is coke (carbon) laydown.
We will return to the topic of Catalysis towards the end of the course.