KNOW MORE ABOUT FCC CATALYSTS

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Introduction
Fluidized catalytic cracking
(FCC) technology was
commercialized in 1942.
One of the most important
conversion processes in all
modern refineries.
Converts heavier, lower
valued products from the
refining of crude oil to high
octane number gasoline
through the process of
catalytic cracking.
Schematic diagram of a typical FCC Unit
Source:www.Lummus.CBI.com
FCC Catalysts
Cracking requires the use of acid catalysts.
The earliest FCC catalysts were acid-leached clays
and artificial or natural silica-alumina catalysts.
Since the 1960s FCC catalysts are exclusively
based on Zeolites.
The first artificial zeolite was synthesized and
commercialized by Union Carbide Co. in 1954.
The first commercial zeolitic cracking catalyst was
developed by Mobil Oil Co.
Major Components of FCC Catalysts
Zeolites
Catalyst Matrix
Fillers and Binders
Zeolites
Zeolites are highly
crystalline, microporous
alumino-silicates with a
negatively charged
macromolecular inorganic
framework.
Pores accommodate a
variety of cations which are
easily exchanged by H
+
ions.
Characterized by uniformity
of lattice structure and pore
sizes (~ 8 A
o
), high specific
surface area available.
Various artificial zeolites
Typical Structure of a zeolite
Source: www.himfr.com
Zeolite Chemistry and Structure
♦ More than 150 artificial and 40 naturally occurring
varieties.
♦ The general chemical formula for zeolites is
Mex/z [(AlO2) x (SiO2) y]. nH2O.
♦ The basic building blocks are silica and alumina
tetrahedra.
♦ Both Bronsted and Lewis acid sites are present in the
structure,depending on temperature.
♦ The nomenclature of zeolites follows the convention set
by the Structure Commission of the International Zeolite
Association (IZA).
♦ Typical zeolites used as FCC catalysts are Zeolite X,
Zeolite Y, ZSM-5 and rare-earth exchanged zeolites.
Catalytic Activity of Zeolites
The catalytic activity of zeolites stems from the following
main facts:
Thermal stability- Zeolites are stable at even 650
0
C, so
they are suitable for FCC units. They also remain stable
over the numerous deactivation-regeneration cycles.
Acidity- The density of the acid sites can be controlled
by modifying the silica-to-alumina ratio.
Shape selectivity-Extreme regularity of pore structure
and usual pore sizes in zeolites enable shape selectivity
to be achieved.
Zeolite Synthesis
• Digestion of a mixture of
silica, alumina and caustic
soda is digested for 10
hours or more at prescribed
temperatures till the
appearance of crystallites
• Spray drying of slurry to
obtain zeolites
• Exchange of mobile Na
+
ions by rare earth elements
(Ce,La)
• Steam calcination of the
zeolite at a temperature of
~800
o
C
Source: Fluid catalytic Cracking Handbook,
Reza Sadeghbeigi, 2nd Edition
Flowsheet for the synthesis of Zeolites
Role of the Catalyst Matrix
• Matrix generally refers to that part of the catalyst other than
the zeolites.
• May or may not possess catalytic activity.
• Consist of amorphous silica-alumina gels or silica-magnesia
gels and acid treated clays like kaolinite and montmorrilonite.
• Performs various important functions like:
Catalyst support
Binding agent for micro-spheroidal catalyst particles
Diluting medium
Heat transfer medium
• Matrix activity helps in the pre-cracking of the heaviest
molecules in feedstock.
Major physical properties of FCC
catalysts
• Attrition Resistance
• Pore Size Distribution and Pore Volume
• Crystallinity
• High Surface Area
• Hydrothermal Stability
• Particle Size Distribution
The performance of the equilibrium FCC catalysts
under different conditions are evaluated from the
Microactivity test (MAT).
Typical XRD Pattern exhibited by a Zeolite
Source: Feng H et. al., Applied Clay Science 42 (2009) pg. 442
FCC Catalyst Composition and
Properties
• Effect of zeolites content
• Effect of rare earth exchanged zeolites
• Effect of various additives
CO Promoter
SO
x
Additive
ZSM-5
Metal Passivators
Computer generated image of the pore structure of ZSM-5
Source: www.3dchem.com
Correlation between zeolite unit cell size and structural Si/Al ratio
Source: Octane-enhancing, zeolitic FCC catalysts: scientific and technical aspects, pg 116
by Julius Scherzer
Effect of zeolite unit cell size on gas oil cracking selectivity
Source: Octane-enhancing, zeolitic FCC catalysts: scientific and technical aspects, pg 126
by Julius Scherzer
Catalyst Management in FCC Units
Involves the following aspects:
Minimizing catalyst losses by improving recovery
Replacement policy for spent catalyst
Ensuring proper catalyst circulation between reactor and regenerator
Stripping of hydrocarbons from the catalyst before regeneration
This is necessary because of the following reasons:
Regeneration is never 100% efficient
With time attrition of the catalyst particles takes place, leading to the
production of fines which are lost through the cyclones
Hydrocarbons have to be removed from the catalyst as far as possible
before the regeneration step by steam stripping so that coke formation
is minimized in subsequent cycles
Recent Developments in FCC Catalysts
• Modelling of FCC Catalyst Pore Structures
Pores in zeolites are of regular shape and size, hence
attempts are being made to obtain mathematical
descriptions of the pore structure.
Simple parallel bundle pore model for
supported zeolite
A 10 x 10 x 10 3-D stochastic pore network.
Source: R Mann, Catalysis Today 18 (1993) pg. 516 and 518
Recent Developments…..
• Special catalysts for short contact
time applications
Engelhard Corporation has developed and
commercialized the NapthaMax™catalyst which
enables catalytic cracking of even resids within 1
to 3 seconds.
The patented matrix technology is called
Distributed Matrix Structure (DMS). The zeolites
are highly dispersed over the matrix and hence
even the pre-cracking takes place on the zeolite
surfaces. This allows for better selectivity of the
catalyst and eliminates the need for a secondary
diffusion step to reach the active sites.
DMS Matrix
Conventional Zeolite
Source: Mc Lean J B and Stockwell D M, NaphthaMaxTM
Breakthrough FCC Catalyst Technology for Short Contact Time
Applications, NPRA 2001 Annual Meeting, New Orleans
Recent Developments…..
• Special Purpose FCC Catalysts
To maximize the production of specific hydrocarbons like the iso-olefins
through the use of proprietary catalyst formulations like IsoPlus™catalyst.
These hydrocarbons are required for production of MTBE or TAME for
reformulated gasoline.
The graphic shows the
relative Increase in the yield
of Iso-butylene with the use of
IsoPlus catalysts in FCC
Source: Mc Lean J B and Witoshkin
A, Isoolefins for Oxygenate
Production using IsoPlus™, NPRA
1993 Annual Meeting, Texas
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