Lecture # 4

Principles of Heterogeneous Catalysis

CHE633A, IIT Kanpur
 Course conduct and content
 A bit of history
 Theories and postulates
 Important properties of heterogeneous catalysts
 Applications of catalysts
 Use of support
 Different types of support
 Preparation of Al2O3, SiO2, TiO2
Support
Zeolites are crystalline silica-alumina material
 Formed by hydrothermal treatment of co-gels of silica and alumina
in an autoclave at ~10 atm and temperatures between 90 to 180oC,
in the presence of OH (-ve) ions, organic template and a seed crystal
 Various crystalline structures have been made using different Si/Al
ratios forming different pore geometries and sizes
 Al2O3 and SiO2 are bound together as 4 co-ordinated units
o each Al and Si cation is bonded to four oxygen O O
o each O-2 is bonded to either Si+4 or Al+3 Al+3 Al+3 Si+4 Al+3

 An extra Na+ or H+ must be present for charge neutrality

o this extra cation gives rise to an exchangeable cation site
o when H+ is present the sites are acidic
Zeolites act as molecular sieves
 Pore structures can be maintained between 3 and 8 Ao, which is the
range of small reactant molecules
 Modernite: Si/Al ratio is ~ 5 and it has 2 non-intersecting pores
o Main pore has 12 oxygens in an elliptical shaped aperture: ~6.7*7 Ao
o Minor pore has 8 oxygen with: ~2.9 * 5.7 Ao
 Larger molecules are prevented from entering the zeolite
(molecular sieves)
 Proposed that the framework AlO-H+ or AlO-M+ are the active sites
for catalytic reactions
Other supports used for heterogeneously catalyzed
reactions
 Silica-Alumina, Zirconia (ZrO2), and Carbon are also used as
supports for a variety of applications
 Silica-Alumina is used cracking catalysts or as acidic supports
 Zirconia support is used in Methanol synthesis
 Carbon is used as a catalyst support for a number of very specific
organic reactions in the Fine Chemicals Industry
Catalysts Preparation is Difficult to Generalize
 It is important to understand how industrial catalysts are made
o Critical preparation details are maintained as trade secrets, e.g.,
activation and conditioning (protect proprietary nature)
 Patents are made by suppliers for various preparation procedures
o no guarantee what is disclosed in patent literature is what is
practiced
o this is essential for each supplier to maintain an advantage over
competitors’ products
 Consequently, only general commonly used procedures are
mentioned
Forming of the support material
 Before the active material is deposited on the support/carrier the
support undergoes pretreatment
o Support is extruded or pelletized to give a strong matrix on which the
active phase is placed
 Extrudates are formed from paste of the support and this paste is
extruded in different shapes and cut into various sizes
o Extrudates are dried, fired/calcined at temps to provide the required
strength
 Pellets are made from dry powder of the support mixed with
“lubricants” such as graphite and then put into a pelletizing machine
o Pellets are also dried (if necessary) and calcined to impart the final
strength
Preformed supports are often used to carry the active
material
 Active material introduced onto the support by
o Impregnation
o Deposition-precipitation
 In both cases a solution of the active material (precursor) is made
and introduced into the pores of the preformed supports
 Finally, the support containing the active material is dried and
calcined
 Additional steps may also be carried out to maintain the proprietary
nature of the catalyst, such as reduction and passivation
 Impregnation is usually employed in the industry for
practical (ease) and economic (cheap) reasons
 Impregnation allows:
o Use of pre-shaped or structured supports
o Use commercially available supports, which is an advantage since
supports with optimal properties can be selected
 Type of interaction between support surface and ion of active
material in solution depends on:
o Ion-exchange with the acidic hydrogen ions or surface hydroxyl groups
o Electrostatics
o More of a physical nature when the ions exceed the surface
concentration of hydroxyl (-OH) groups OH OH OH
S S S

S is Al or Si or Ti or Zr, etc
Type of impregnation depends on the volume of solution
and volume of the pores
 Dry impregnation is when volume of solution containing the ions is
less than or equal to the volume of the pores
o Method of interaction depends more on retaining the ions inside
the pores rather than on a specific interaction
o Weight of the added component is easily controlled

 Wet impregnation is when the solution containing the ions is more

than the pore volume, specific interactions occur, e.g., ion exchange
o Distribution of added component is more uniform
o If concentration of component is low than deposition may occur
only at the “mouth” of the pore → egg-shell catalyst
o Multiple impregnation required for uniform distribution
Processes that occur during Impregnation
 For dry impregnation the following processes occur:
o Transport of the precursor containing solution within the pore system
of the support
o Uptake of the solute (precursor) by the pore wall
 For wet impregnation the transport of the solute to the outer surface
is also required
 Depending on the process conditions different profiles of the active
phase over the support is obtained
The drying process after impregnation is an important
step
 Very quick drying might result in solution being driven out of the
pores and the solute depositing on the exterior surface
o Adherence of the solute would be weak and “dusting” might occur,
which would result in accumulation of dust downstream of the reactor
 If calcination is required, then products of decomposition of
precursor salt and solvent needs to be removed by flushing
 If catalyst is to be reduced, then reduction is carried out by
gradually increasing the temperature in a reduced environment