Chapter 8: Catalyst Materials and Properties

Awareness of catalysts and catalyst supports

Awareness of key properties of supports
Knowledge of the preparation and characterisation of zeolites
Knowledge of the use of zeolites in refinery operations
Chapter Summary
Introduction to common supports and zeolites. The reader should obtain
a good understanding of various zeolites and the importance of
selectivity. Also some common uses in the oil and gas industry will be
covered.
Catalytically Important Elements
Common Supports and Catalysts
Activated Alumina
Most common, varied acidity and SA
HSA = Gibbsite and boehmite prepn. by ppn. at varied pHs
Carbon
Prepared from natural sources by pyrolysis in inert gas,
such as CO
2
and/or steam:
Active carbon (T = 800 1500
o
C in active environment)
Graphitic (T up to 3000
o
C in inert environment)
Used in organic hydrogenations in fine chemical industry
Zeolites crown jewels of catalysis
Crystalline aluminosilicates with pores of molecular dimensions
Shape Selective Cracking Catalysts
What are Zeolites ?
Characteristics
Crystalline aluminosilicates
3D frameworks built up from SiO
4
4-
and AlO
4
5-
tetrahedra
Channels and cages of molecular size (defined by structure)
Cation exchange properties
Stability to heat and radiation
25% of Periodic table can be incorporated into structure
Surface area typically 400-500 m
2
g
-1
Large internal surface area (> 90%)
Faujasite or Zeolite Y
(12 T atoms = 0.74 nm)
ZSM-5 (10 T atoms = 0.55 x 0.51nm)
Mordenite
(12 T = 0.7 x 0.65 nm & 8 T =0.57 x 0.26 nm)
Linde A (8 T atoms = 0.41 nm)
Approximate effective diffusion coefficients of molecules in
porous solids (PB Weisz, 1973)
Breck DW., Zeolite Molecular sieves, J Wiley & Sons, NY (1974)
ZSM-5
(10 T atoms = 0.55 x 0.51nm)
Reactant Shape
Selectivity
n-BuOH dehydrated
using zeolite A
but not i-BuOH
Product Shape
Selectivity
Zeolites in Catalysis
Zeolites application in refinery context
Energy for process is balanced. The highly endothermic reaction is balanced
by the highly exothermic coke burn-off.
Flue Gas
Stack
Fractionating
Column
Reactor
Regenerator
FCCU
Note 1: changed product
distribution with increased
paraffins and aromatics
when using HY
Note 2: changed product
distribution reduced the no.
of barrels required to be
processed/day
Zeolites in a refinery (FCC)
Deactivation by Coking
ZSM-5
Deactivation / coking
Rapid due to coke deposition
Slower due to metals in feed deposition and sintering
More rapid due to pore blockage
Coke Deposition
Initial soft coke deposited (lower T)
H rich
Cycloparaffins, naphthenes, aromatics
Dehydrogenation follows hard coke deposited (higher T and longer
reaction times)
H deficient
polyaromatics
Coke deposition modifies pore size distribution
Decreased diffusion
Decreased activity
Coke deposition is reversed by oxidative regeneration
Coke formation heavily influenced by architecture of zeolite catalyst
What we covered today:
Awareness of catalysts
and catalyst supports
Learning Outcomes
Knowledge of the preparation
and characterisation of
zeolites
Awareness of key properties
of supports
Knowledge of the use of
zeolites in refinery operations