Lecture # 3

Principles of Heterogeneous Catalysis

CHE633A, IIT Kanpur
 Course conduct and content
 A bit of history
o Metal, Type of metal and Surface area of metal
 Theories and postulates
 Important properties of heterogeneous catalysts
 Practical applications of catalysts
 Use of support
Supported catalysts are Essentially made up of Two Part
(Active component & Carrier or support)
 Most common catalysts used in the industry are metals and metal
oxides, such as: Pt, Pd, Rh, Ni, Co, Fe, V2O5, MoO3, and Cr2O3
 Active components are then dispersed on a carrier (support) such
as: Al2O3, SiO2, TiO2, zeolites, crystalline alumina-silicates, etc.
 Carriers are high surface area inorganic material containing a
complex pore structure on which the active component is dispersed
 Carrier/support was thought to provide only a higher dispersion of
the active component to maximize the catalytic surface area
 Recently, it has been shown to also play a critical role in controlling
the activity, selectivity and durability of the finished catalysts
Commonly used carriers in the industry are Al2O3, SiO2,
TiO2 and Zeolites
Al2O3 (alumina) is most commonly used as a support in industry
 it is of different types possessing varying surface areas, pore size
distribution, surface acidic properties and crystal structure
o these properties depend on its preparation, purity and thermal history
 The initial Al2O3 is produced by precipitation (ppt) either from acidic or
basic solutions of bauxite which results in different types of alumina
o bayerite (Al2O3.3H2O) formed when ppt from a solution at pH 11
o pseudo-boehmite (Al2O3.H2O) formed when ppt from a solution at pH 9
o acidic pH (pH ~6) the alumina formed is amorphous (no long range
order)
 Different transitional phases of Al2O3 are formed
depending on treatment
𝐵𝑜𝑒ℎ𝑚𝑖𝑡𝑒 500−850 850−1050 1050−1150 > 1150
 𝑔𝑎𝑚𝑚𝑎 𝛾 𝑑𝑒𝑙𝑡𝑎 𝛿 𝑡ℎ𝑒𝑡𝑎 𝜃 𝑎𝑙𝑝ℎ𝑎 (𝛼)
(𝑚𝑜𝑛𝑜ℎ𝑦𝑑𝑟𝑎𝑡𝑒)
𝐵𝑎𝑦𝑒𝑟𝑖𝑡𝑒 500−850 850−1050 > 1150
 𝑒𝑡𝑎 𝜂 𝑡ℎ𝑒𝑡𝑎 𝜃 𝑎𝑙𝑝ℎ𝑎 (𝛼)
(𝑡𝑟𝑖ℎ𝑦𝑑𝑟𝑎𝑡𝑒)
 Changes are irreversible with a loss of surface area and other properties (e.g., OH,
acidity)
 Collapse of surface area may also occlude the active sites within its pore structure
resulting in a loss of accessibility (catalyst deactivation)
 Presence of certain element(s) has an influence on the surface area changes at
high temperatures, e.g., small amounts of Na2O enhances sintering
o small amounts of La2O, CeO2, BaO and SiO2 stabilize the surface area reduces
the mobility of the Al and O ions
Precipitate is thoroughly washed to remove impurities
and then calcined
 if acidic solutions are neutralized with NaOH, the Na+ ions are
removed by washing
 Following ppt and washing the alumina is dried at 110oC to remove
excess water and other volatile species (NH3)
 Calcination at ~500oC forms the final surface area support
 Calcinations at different temperatures determines final crystal
structure → determines physical and chemical properties
H2O
OH OH
 Bronsted and Lewis acid sites are formed O
Al Al Al Al
depending on the level of dehydration
Silica, SiO2, is another commonly used support in the
chemical industry
 Especially useful towards sulfur bearing compounds (Al2O3 is very
reactive → deactivation)
 Sodium silicate is initially produced by dissolving silica sand in hot
caustic soda: 𝑆𝑖𝑂2 + 2𝑁𝑎𝑂𝐻 → 𝑁𝑎2 𝑆𝑖𝑂3 + 𝐻2 𝑂
 Alkaline solutions of silicate (pH >12) are neutralized with acid and
silicic acid is formed
𝑁𝑎2 𝑆𝑖𝑂3 + 𝐻2 𝑆𝑂4 → 𝐻2 𝑆𝑖𝑂3 + 𝑁𝑎2 𝑆𝑂4
 Silicic acid polymerizes forming a high surface area network with
interconnecting pores of varying sizes
𝐻2 𝑆𝑖𝑂3 + 𝐻2 𝑆𝑖𝑂3 → 𝐻𝑂 − 𝑆𝑖 𝑂 2 − 𝑂 − 𝑆𝑖 𝑂 2 − 𝑂𝐻 + 𝐻2 𝑂 → 𝑝𝑜𝑙𝑦𝑚𝑒𝑟
Chains of silica interact with each other initially forming
sols and then “hard” gels
 Time taken for sol formation and subsequent gelation (gel formation)
depends on pH, temperature and conc of sols

 Excess acid is used to form the silicate (pH~4) and the gel formation
time is avoided
o Na2SO4 is removed by washing and the gel is allowed to dry

 Similar to Al2O3 it is washed, dried and calcined → pore structure

 Surface areas ranging from 200 to 900 m2/g depending on above

factors
Importance of using SiO2 as a support

 No phase transition occurs and only sintering can occur at high T

o Robust carrier/support, which is used for reactions up to 700oC
 Silica is not inert and may influence reactions
o Reacts with water to form volatile hydrosilicates at high T → not used
for steam reforming or similar processes involving water
o If alkali or alkaline metal are present then corresponding silicates can
form, which are extremely mobile and can cause pore blockage
Titania, TiO2, as a support has specialized uses in partial
oxidation, SCR and for photocatalysis
 Made by the hydrolysis of TiOSO4 (sulfate route) or vapor phase
oxidation of TiCl4 (Chloride route)
o Sulfate route less used since large amounts of impure sulfuric acid
formed
 Essentially two types of crystal structures exist, anatase and rutile
o anatase is the more important form due to its higher surface area (~80
m2/g) and is thermally stable up to 500oC
o rutile structure has a low surface area (< 10 m2/g) and is formed at
~ 550oC
 Due to low temperatures required for anatase and rutile transformation
care taken, otherwise occlusion of active sites can occur
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
 Moderniate: 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