1.

Catalytic Reactions
2. Catalytic Reactors
3. Porous catalysts
4. Transport and reaction
5. Mass transfer coefficient
6. External mass transfer
7. Pore diffusion
8. Langmuir-Hinshelwood kinetics
9. Designing catalytic reactors

CPE 624 Advanced Chemical

Reaction Engineering
 What is catalyst?
◦ To enhance the reaction rate
◦ Does not consumed in the reaction
 How does the catalyst functioning?
◦ Providing lower energy barrier
 Two categories of catalyst
1) Porous 2) Non-porous
 Homogeneous catalysis
◦ Catalyst in solution with min one reactant
◦ Re-use the catalyst after separation
◦ Catalyst in the same phase as the reactants
◦ Ex : industrial Oxo process : manufacturing isobutyl-
aldehyde
 Heterogeneous catalysis
◦ Involves more that one phase
◦ Catalyst in solid form, products/reactants in liquid or
gaseous
 Ex : Benzene production, hydrodesulfurization
◦ More economical, catalyst kept inside the reactor
◦ Reaction occurs at /very near the fluid-solid interface
◦ Other forms are gas-liquid (mass transfer limited) and gas-
liquid-solid system

CPE 624 Advanced Chemical

Reaction Engineering
1. Transport steps of reactants & products
2. Many industrial reactors : kinetics of
individual reaction unknown

3. Essential in any multiphase reactor – Why?

CPE 624 Advanced Chemical

Reaction Engineering
1. Porous catalysts

1. Monolithic catalyst
2. Supported/Unsupported catalysts

CPE 624 Advanced Chemical

Reaction Engineering
 Catalyst that has a large area resulting from pores
 Typical silica-alumina cracking catalyst
◦ Pores volume of 0.6cm3/g
◦ Average pore radius of 4 nm
◦ Surface area 300m2/g
 Raney nickel used in hydrogenation of vegetable and
animal oils
 Molecular sieves-Small pores to avoid large molecules
from entering
◦ derived from certain clays and zeolites
 Totally synthetic ie crystalline aluminosilicates
 Selective catalyst- pores to control residence time of
various molecules

CPE 624
Advanced Chemical Reaction Engineering
 Process with major considerations in pressure drop
and heat removal
◦ ie platinum gauze reactor used in the ammonia oxidation
portion of nitric acid manufacture
◦ catalytic converters used to oxidize pollutants
 Porous (honeycomb) or nonporous (wire gauze)

CPE 624
Advanced Chemical Reaction Engineering
 Support- particles of an active material
dispersed over a less active substance
 The active material is frequently a pure metal
or metal alloy
 Promoters – active ingredients to increase
catalyst activity

CPE 624 Advanced Chemical

Reaction Engineering
1. Packed bed reactor (PBR)
2. Slurry reactor
3. Fluidized bed reactor
4. Riser reactor

CPE 624 Advanced Chemical

Reaction Engineering
 Typical tank/tube filled with catalyst pellets
 Fluid flow & void space
 PBR/multitube/single tube
 Fluid in PBR flows from one end to another
end (no mixing)

CPE 624 Advanced Chemical

Reaction Engineering
 dC j
u  v j r (Single reaction)
dz
dC j
u   vij ri (Multiple reactions)
dz i

VR  V fluid  VCatalyst
V fluid  VR
V Catalyst  (1   )V R
CPE 624 Advanced Chemical
Reaction Engineering
 Fluid and catalyst are stirred
 Fluid is a liquid (catalyst must be small)
 The catalyst in powder/pellets form
 Moving fluid is frequently well mixed hence
equal to a CSTR :
C Ao  C A  r
 Residence time :
V fluid VR
 
 
CPE 624 Advanced Chemical
Reaction Engineering
 Fluid and catalyst are stirred
 Fluid is gas (catalyst must be very small)
 The catalyst in powder/pellets form
 Moving fluid is frequently well mixed hence
equal to a CSTR :
C Ao  C A  r
 Residence time :
V fluid VR
 
 
CPE 624 Advanced Chemical
Reaction Engineering
 High velocity in the reactor
 Solids entrained in the flowing fluid and move
with nearly same fluid velocity
 Catalyst is carried with the reactants,
separated and returned to the reactor
 Completely mixed, hence no mixing and
behave to a PBR :
dC A
u  r
dz

CPE 624 Advanced Chemical

Reaction Engineering
 Assumption for heterogeneous reactions:
◦ No reaction in the fluid phase
◦ All reaction occurs on the catalyst surface

Table 7-1 : Homogeneous & Surface reaction rates

Rate Significance Units
Homogeneous/ moles/vol.time
r Pseudohomogeneous rate
r " Rate per catalyst area moles/area.time
Rate per weight of catalyst moles/weight.time
r '

CPE 624 Advanced Chemical

Reaction Engineering
- determination of equivalent homogeneous rate for
heterogeneous reaction

 area  surface area of catalyst

r  r" vol.of reactor
 volume 

CPE 624 Advanced Chemical

Reaction Engineering
Example :
PBR filled with pellets with surface area Sgc per unit/pellet
volume

 area  V catalyst
   Sg c  S g  c (1   )
 volume  V fluid

Surface
area/weight of
(1   )
catalyst Fraction occupied
Density of by the catalyst
catalyst pellet

CPE 624 Advanced Chemical

Reaction Engineering
 Homogeneous:
vol .of reactor V
  
inlet volumetric f / rate o

 Heterogeneous:
V fluid  V R

V R
  
 o

CPE 624 Advanced Chemical

Reaction Engineering