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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
CH2=C=O
ketene
+ H2O
water
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
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
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
concentrations of reactant in
the main gas stream
When the desired reaction is of lower order,
operating under conditions of diffusion control
increases selectivity
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
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
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
2H2
CO 2
H2
: Exothermic reaction
CH3OH
CO + H 2O : Endothermic reaction
Tubular reactor
30OC
REACTANTS
REACTANTS
STEAM
CATALYST
BOILED
FEEDWATER
CATALYST
PRODUCTS
PRODUCTS
O
4 C
230
250
270
230
250
270
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
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
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
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
Heterogeneous models:
Separate conservation equations for fluid and catalyst
g us
dp
t = f
dz
dp
b(1 )
+ a +
Re
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
u s (C A0 C A ) = Dea
rA0 B d p
u s C0
<< Pema
(H )rA0 B d p
(T0 Tw )u s g c p
<< Peha
dT
aw (TR TW ) = er
dr w
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
For solid:
B rA = k g av (C Css )
(H ) B rA = h f av (Tss T )
2 dC s
s rA (Cs , Ts ) = 0
d
e d 2 dTs
+ s (H )rA (Cs , Ts ) = 0
2 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
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