Lecture 7

Catalysts and Catalytic Reactors

Catalytic reactor models: Fixed Bed reactors

CATALYSTS
Most processes use a catalyst
Catalysts increase the rate of reaction but are unchanged in quantity
and chemical composition at the end of the reaction.
Catalysts for multiple reactions: the catalyst may have different effects
on the rates of the different reactions
Catalysts need to be developed that increase the rate of the desired
reactions relative to the undesired reactions

The choice of catalyst is very important

but still largely empirical.

 The catalytic process can be

Homogenous
Heterogenous
Biochemical

(i) Homogeneous Catalyst

The reactions proceeds entirely in the vapour or liquid phase
The catalyst may modify the reaction mechanism by participation in the
reaction but is regenerated in a subsequent step. The catalyst is then free
to promote further reaction
E.g. Production of acetic anhydride
CH3COOH
acetic acid

CH2=C=O
ketene

Catalyst : triethyl phosphate

+ H2O

water

(ii) Heterogeneous Catalyst

The catalyst is in a different phase from the reacting species
Solid catalyst
Bulk catalytic materials : the gross composition does not change significantly
through the material, such as platinum wire mesh
Supported catalysts : the active catalytic material is dispersed over the surface
of a porous solid
- most often, the heterogeneous catalyst is a solid

Catalytic gas-phase reactions : important to many bulk chemical

processes and most petroleum refinery processes
The effective area of the catalyst is critically important
Industrial catalysts are usually supported on porous materials
much larger area per unit of reactor volume

Heterogeneous Gas-Solid Reaction Rate

The reaction rate of catalysed reactions is more complex than that
of uncatalysed ones.
The overall rate of a heterogeneous gas-solid reaction is made up
of a series of physical steps as well as the chemical reaction.
Mass transfer of reactant from the bulk gas phase to the external solid surface
Diffusion from the solid surface to the internal active sites
Adsorption on solid surface
Activation of the adsorbed reactants
Chemical reaction
Desorption of products
Internal diffusion of products to the external solid surface
Mass transfer to the bulk gas phase

all these steps are rate processes and are temperature dependent
rate controlling step : the step that is slower than the others

Effectiveness Factor
Effectiveness factor = the ratio of the observed rate to that which would be

obtained if the whole of the internal surface of the pellet

were available to the reagents at the same concentrations
as they have at the external surface

The optimal performance of the catlayst is obtained by locating the

Dirac Delta catalyst distrubtion so as to maximize the reaction rate by
taking advantage of both temperature and concentration gradients
within the pellet.
Location of Dirac Delta Function to be optimsed.
In practice, step function is used for Dirac Delta Function
Less than 5 % of the
characteristic dimension
of the pellet

(a) Dirac delta function.

(b) Step function.

(Morbidelli, Gavriilidis and Varma (2001) Catalyst Design: Optimal Distribution

of Catalyst in Pellets, Reactors and Membranes, Cambridge University Press).

Solid-catalysed reactions
Usually, multiple reactions
The gross flow pattern of fluid through reactor should be
considered
For parallel reactions
Maintaining the appropriate high or low concentration and temperature levels
of reactants at the catalyst surface
- Encourage the desired reaction
- Discourage the byproduct reaction

For series reactions

Avoiding the mixing of fluids of different compositions

Local non-homogeneity of catalyst

Lowered reactant concentration or change in temperature within the catalyst
pellets
The concentration and temperature in the interior of catalyst pellets may differ from the
main body of the gas
Different product distribution from that for homogenous system

Two extremes for local non-homogeneity

Surface reaction controls

concentrations of reactant
within the pellets

concentrations of reactant in
the main gas stream

The gross flow pattern of fluid through the reactor would be considered
Diffusion controls
concentrations of reactant
at the catalyst surface

Lowered reactant concentration

favours the reaction of lower order

concentrations of reactant in
the main gas stream
When the desired reaction is of lower order,
operating under conditions of diffusion control
increases selectivity

Selectivity for solid catalysed reactions

Optimum selectivity given by Dirac Delta Function
Step function can be used in practice
Need to optimize the location of the step function within the
catalyst pellet
(Morbidelli, Gavriilidis and Varma, (2001) Catalyst Design: Optimal Distribution of
Catalyst in Pellets, Reactors and Membranes, Cambridge University Press)

Practical difficulties in producing catalyst pellets with precise

location of catalyst step function
Deterioration of catalyst performance with time needs to be
considered

Temperature Control
Adiabatic operation leads to the simplest and cheapest reactor
design
Temperature control is required for
- Unacceptable temperature rise for exothermic reactions
- Unacceptable temperature fall for endothermic reactions

Temperature control for adiabatic operation

Cold shot or hot shot : the injection of cold or hot fresh feed directly into the
reactor
- Temperature control by direct contact heat transfer
- Concentration control of feed material to adjust the rate of reaction

Indirect heat transfer with the reactor: indirect heating or cooling

- Heat transfer takes place inside the reactor or
- Material is taken outside of the reactor to a heat transfer device and returned to the
reactor.

Example of Temperature Control (I)

Temperature control for adiabatic operation (continued)
Heat carrier : An inert material can be introduced with the reactor feed
- to increase the feed CP (mass flowrate multiplied by specific heat capacity)
- to reduce the temperature rise or fall for reactions
When possible, the existing process fluids should be used as heat carriers
Product or byproduct recycling as a mean of temperature control should not have
a detrimental effect on the selectivity of the reaction.

Catalyst profiles
- Change of the distribution of active material in the catalyst bed or
- Use a different catalyst in different parts of the reactor or
- Use a mixture of catalyst and inert solid to dilute the catalyst
Easy to control the rate of reaction in different parts of the bed

Example of Temperature Control (II)

Exothermic reaction with non-uniform catalyst performance
Reaction
proceeds

Reaction
proceeds

Low
concentration

REACTANTS

Catalyst
arrangement
with gradient

Cooling
medium

High
concentration

Catalyst

Cooling
Medium
PRODUCTS

Better temperature
control

Heat release
from the reaction

Tubular Reactor

Cooling duty
Feed
concentration
Reactor inlet

Reactor outlet

Example of Temperature Control (III)

Production of methanol
CO

2H2

CO 2

H2

: Exothermic reaction

CH3OH

CO + H 2O : Endothermic reaction

Tubular reactor

Cold shot reactor

30OC

Gas inlet temp

water temp

REACTANTS

REACTANTS

STEAM
CATALYST
BOILED
FEEDWATER

CATALYST

PRODUCTS

PRODUCTS
O

4 C
230

250

270

Temperature profile is relatively smooth

230

250

270

Significant temperature fluctuations

Accidental catalyst overheating and
shortening of catalyst life

Quenching of Reactor Effluent

The reactor effluent may need to be cooled rapidly, or quenched, by
Indirect heat transfer : conventional heat transfer equipment
Direct heat transfer : mixing with another fluid
e.g. Cooling of gaseous products mixed with a liquid.
The cooling is accomplished by mixing with a liquid that evaporates.

Reasons to use quenching with direct heat transfer

The reaction is very rapid and must be stopped quickly to prevent excessive byproduct formation.
The reactor product cooling would cause excessive fouling in a conventional exchanger.
Special materials-of-construction or an expensive mechanical design is required because the
reactor products are so hot or corrosive.

The liquid used for the direct heat transfer should be easy to separate from the
reactor product.
Use of extraneous materials for the direct quenching may be used.
But it should not
Create additional separation problems
Degrade the specifications of product purity
Cause additional environmental problems

Choosing Heat Transfer in the Reactor

Yes
Yes

Is Adiabatic
Operation
Acceptable ?

Yes

Is High
Temperature
or High Flux
Required ?
No

No

Is Indirect
Heat Transfer
Feasible ?
No

Heat
Carrier

Heat
Carrier

Catalyst Degradation
Catalytic degradation can cause a loss of performance
Physical loss
- Homogenous catalysts : generally important
- Heterogenous catalysts : particularly for catalytic fluidized bed reactors
Attrition of the particles causes the catalyst particles to be broken down

Surface deposits
- The formation of deposits on the surface of solid catalysts introduces a physical barrier to the reacting
species.
- Most often, the deposits are insoluble or non-volatile.
e.g. Coke formation (carbon deposits) in hydrocarbon reactions
suppression by adjustment of feed composition or regeneration by air oxidation at elevated temperatures

Sintering : molecular re-arrangement below the melting point

- Sintering causes a reduction in the effective surface area of catalyst.
- Sintering results from high temperature reaction / poor heat transfer / poor mixing of reactants / catalyst
regeneration at high temperature

Poisoning
- Usually impurities in the raw materials or products of corrosion chemically react with or form strong
chemical bonds with the catalyst

Chemical change
- some catalysts can slowly change chemically with a consequent reduction in activity

Effects of Catalyst Degradation

Catalyst degradation is important for :
the choice of catalyst
reactor conditions
reactor configuration

Deterioration in catalyst performance lowers the rate of reaction.

Increasing the temperature of reactor gradually can be used to compensate for
the deterioration in performance.
High temperature can decrease selectivity considerably and often accelerate the catalyst
degradation.

The reactor configuration must make a provision if degradation is rapid.

Use standby capacity
or
Removal of catalyst from the bed on a continuous basis

The lost or degraded catalyst implies cost and environmental impacts.

Types of catalytic reactors: Fixed-bed reactors

Major part of catalytic processes carried out in fixed-bed reactors
With the exception of catalytic cracking of gas-oil
Carried out in fluidised beds

Typical fixed bed industrial processes include:

Chemical
industry

Petrochemical
Industry

Petroleum refining

Steam reforming

Ethylene oxide

Catalytic reforming

CO conversion

Ethylene
dichloride

isomerization

Synthesis:

Vinyl acetate

polymerization

Sulfuric Acid

butadiene

hydrodesulfurisation

Methanol

Maleic anhydride

hydrocracking

Oxo

cyclohexane

ammonia

styrene
hydrodealkylation

Technical innovations
Fixed-bed reactors are large capacity units
To address high market demands
Made possible by progress in both technical and fundamental areas
Introduction of better materials of construction
E.g. centrifugal cast 25% Cr 20% Ni steel tubes to increase operating Ts and
throughput

Better design of reactor internals to improve the rate of uniformity of heat

removal
By molten salts

Better design techniques allowing construction of multi-bar reactors with

approx 20,000 tubes of large diametre.
Modification of auxiliary equipment increase the capacity of established
processes such as ammonia synthesis
Centrifugal compressors

Flow pattern modifications

Use of radial flow reactors to reduce pressure drop and enhance recycle capacity
of compressor

Use combinations of small catalyst particles to enhance heat transfer and of

large catalyst particles to limit pressure drop
Design of improved control scheme
Development of new catalysts and modifications of existing ones
Formulation of stable low P methanol synthesis catalyst
Introduction of low T CO shift catalyst

Availability of more reliable kinetic data and physicochemical data

Advanced experimental design techniques
Improved methods in data analysis

Improved reactor models

Fixed-bed reactor models

Principles of general models
Models of variable complexity
Required degree of sophistication depends on specific process
Kinetic reaction scheme
Sensitivity to perturbing operating conditions

Both macroscale and microscale issues

Microscale deal with catalyst particles and sites
Macroscale mainly determined by hydrodynamics
Plug flow enough or more accurate?

Model classification in two big categories:

Pseudohomogeneous models:
Do not expliciltly account for the presence of catalyst

Heterogeneous models:
Separate conservation equations for fluid and catalyst

Models can be 1-D or 2-D

2-D models account for variations in radial dimension

Mixing in axial directions to account for non-ideal flow conditions

can be included

1-D pseudo-homogeneous model

Concentration and T gradients only occur in axial
direction
Overall transport mechanism: plug flow
Conservation equations:
S.S. and single rxn in tube:
d (u s C A )
= rA B
dz
dT
U
u s g cP
= HrA B 4 (T Tr )
dz
dt

g us
dp
t = f
dz
dp

I.Cs: at z=0, CA=CA0, T=T0, pt=pt0

dp is the equivalent particle diameter, us the superficial
velocity, g the gas density, U the overall heat transfer
coefficient, dt the internal tube diameter, Tr the ambient T, B
the catalyst bulk density and f the friction factor

1-D pseudo-homogeneous model (cont d)

Heat transfer coefficient

Overall heat transfer coefficient

1 1 d Ab 1 Ab
= +
+
U ai Am au Au

ai=heat transfer coefficient on the bed side (kJ/m2soC)

au= heat transfer coefficient, transfer medum side (kJ/
m2soC)
Ab= heat exchanging surface, bed side (m2)
= heat conductivity of the wall (kJ/m-hroC)
Au= heat exchanging surface, heat transfer medium
side (m2)
Am= log mean of Ab and Au (m2)

1-D pseudo-homogeneous model (cont d)

Pressure drop
Pressure drop equation for flow through packed beds:
Ergun 1952
Bed of connecting parallel channels with hydraulic radius Rh= /v
= void fraction
v= surface solid per m3 bed

Equivalent particle diameter, dp, diameter of sphere with the same

surface area per unit volume as actual particle, Sv = v / (1- )

So dp=6 (1- ) / v
Ergun proposed:
f =

b(1 )
+ a +
Re

=1.75 and b=150

3
Handley and Heggs (1968) derived: =1.24 and b=368
Hicks (1970) found that Erguns equation is limited to Re / (1- ) < 500
Handley and Heggs equation to 1000 < Re / (1- ) < 5000

1-D pseudo-homogeneous model

with axial mixing
Mixing in the axial direction
Due to turbulence and presence of packing
Accounted by superimposing an effective
transport mechanism
On overall transport by plug flow

Flux due to this mechanism analogous to

Ficks law for mass transfer, Fouriers law for
heat transfer
Proportionality constants effective diffusivities,
conductivities
They implicitly contain the effect of the velocity
profile

1-D pseudo-homogeneous model

with axial mixing (cont d)
Steady-state mass balance for component A:
d 2C A
dC A
Dea

u
rA B = 0
s
2
dz
dz

Energy equation:

d 2T
dT
U
ea 2 us g cP
+ ( H )rA B 4 (T Tr ) = 0
dz
dz
dt

The b.c. s used in general are:

dC A
for z = 0
dz
dT
g u s c p (T0 T ) = ea
for z = 0
dz
dC A dT
=
=0
for z = L
dz
dz

u s (C A0 C A ) = Dea

1-D pseudo-homogeneous model

with axial mixing (cont d)
Two-point boundary value problem
Effect of axial dispersion for heat and mass on
conversion
Negligible when bed depth > 50 particle diameters
More accurately, for monotonically decreasing rate:
Axial dispersion negligible when:

rA0 B d p
u s C0

<< Pema

(H )rA0 B d p
(T0 Tw )u s g c p

<< Peha

Addition of axial mixing leads to the possibility of steady

state multiplicity for adiabatic case

2-D pseudo-homogeneous model

1-D models neglect resistance to heat and mass transfer
in radial direction
Predict uniform temperatures, conversions in cross-section
Problem for rxns with high heat effects

2-D model here uses effective transport concept

In r-direction
Effective diffusivity non-isotropic
Radial component different from axial component
Based on flow characteristics

Effective conductivity e decreases strongly near the wall

Can consider e constant away from wall and introduce new
coefficient for heat transfer near the wall

dT
aw (TR TW ) = er

dr w

2-D pseudo-homogeneous model (cont d)

Mass balance for single component A
d 2C A 1 dC A
dC A
( Der ) s ( 2 +
) us
rA B = 0
dr
r dr
dz

Energy balance
B.C.s

d 2T 1 dT
dT
us g cP
er 2 +
+ ( H )rA B = 0
r dr
dz
dr
C A = C A0
T = T0

at z = 0, 0 r R
at z = 0, 0 r R

dC
=0
at r = 0, and 0 r = R, z
dr
dT
=0
at r = 0, z
dr
aw
dT
=
(TR TW )
at r = R, z
dr
er

Note that (Der)s=Der and er based on superficial flow velocity

1-D heterogeneous model

accounts for interfacial gradients
Very rapid rxns with high heat effects
Need to distinguish between conditions in the fluid and
on catalyst surface
Even inside catalyst

Can have 1-D or 2-D models

Steady state mass and energy balances for single rxn:
For fluid: us dC A = k g av (C Css )
dz
dT
U
u s g cP
= h f av (Tss T ) 4 (T Tr )
dz
dt

For solid:

B rA = k g av (C Css )
(H ) B rA = h f av (Tss T )

1-D heterogeneous model

accounts for interfacial gradients (cont d)
B.C s: at z=0, C=C0 and T=T0

kg=mass transfer coefficient from gas to solid interface

v=external particle surface area per unit volume
hf=heat transfer coefficient for film surrounding particle

Most likely interfacial gradient to occur is

temperature gradient
Compared to the corresponding pseudohomogeneous 1-D model

Fluid/solid intrerface can lead to multiplicity of steady

states
Heat produced in the catalyst: sigmoidal curve
Heat removed by the fluid through the film: straight line
3 steady states arise from their intersections

1-D Heterogeneous model accounting for

interfacial and intraparticle gradients
When resistance to mass and heat transfer inside particle
is important
Rate or rxn not uniform throughout particle
Equations describing concentration and temperature gradients
inside particle are needed
Steady state mass and energy balances for single rxn become:
Fluid: u s dC A = k g av (C Css )
dz
dT
U
u s g cP
= h f av (Tss T ) 4 (T Tr )
dz
dt
Solid: D d
e
2
d

2 dC s

s rA (Cs , Ts ) = 0
d

e d 2 dTs

+ s (H )rA (Cs , Ts ) = 0
2 d d

1-D Heterogeneous model accounting for

interfacial and intraparticle gradients
(cont d)
B.Cs: C=C0 T=T0 at z=0
dC s dTs
=
=0
d
d

at = 0

k g (Css C ) = De
h f (Tss T ) = e

dC s
d

dTs
d

at =
at =

dp
2

dp
2

A single particle is considered not whole solid

The shape of particle also determines values for De and e
Set ODEs describing intra-particle gradients need to be integrated at
each computational node of the fluid
Computationally tedious

Even with strongly exothermic rxns particle practically isothermal

Main resistance inside the pellet to mass transfer

1-D Heterogeneous model accounting for

interfacial and intra-particle gradients
Effectiveness factor
When gradients occur inside particle use effectiveness factor

Multiplies rxn rates at particle surface conditions
To account for rate actually experienced when conditions inside
particle are different

System then becomes:

Fluid:

dC A
us
= k g av (C Css )
dz
dT
U
s
u s g cP
= h f av (Ts T ) 4 (T Tr )
dz
dt
Solid:
B rA (Cs , Ts ) = k g av (C Css )

(H ) B rA (Cs , Ts ) = h f av (Tss T )
Effectiveness factor depends on Thiele modulus f and needs to be
computed at each computational node