FCC Catalyst - FCC Refinery Training Network

12/21/2019 FCC Catalyst | FCC Refinery Training Network
FCCU FREQUENTLY A…
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FCC Catalyst
COMPONENTS OF FCC CATALYST
Slide Valves • ZEOLITE - Primary Catalytic Component for selective cracking.

• MATRIX - Forms the continuum that holds together the Zeolite crystals.
Main Column Bot… 1 • FILLER - A clay incorporated into the catalyst to dilute its activity.
• BINDER - Serves as a glue to hold the Zeolite, Matrix and Filler
together.
Dos and Don’ts o… 1
NORMAL OPERATION …
Wet Gas Compressor - …
Wet Gas Compre… 1
FCC Operating V… 1
FCC Catalyst
FCC feed characteristic…
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ZEOLITE STRUCTURE :
• Zeolite - Primary ingredient for selective cracking
• Wide range of activity, selectivity, product quality
• Diffusion limited with heavy components
• Zeolite, or more properly, acid site, is the key ingredient of the FCC
catalyst. Zeolite Structure
• Zeolite is sometimes called molecular sieve. It has a well-defined lattice
structure.
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FCC Catalyst
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Fig - Its basic building blocks are silica and alumina tetrahedral (pyramids).
Each tetrahedron consists of a silicon or aluminum atom at the center of the
tetrahedron, with oxygen atoms at the four corners
Sodalite Cages and hexagonal prisms enclose a so called Super cage. 1 unit
cell has 8 super cages
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Zeolite lattices have a network of very small pores. The pore diameter of
nearly all of today's FCC zeolite is approximately 8.0 angstroms (°A). These
small openings, with an internal surface area of roughly 600 square meters
per gram, do not readily admit hydrocarbon molecules that have molecular
diameter greater than 8.0°A to 10°A
ZEOLITE CHEMISTRY - A typical zeolite consists of silicon and aluminum

NORMAL OPERATION … atoms that are tetrahedrally joined by four oxygen atoms. The acid sites are
both the Bronsted and Lewis types. The Bronsted acid sites can be further
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enhance their strengths. The zeolite activity comes from these acid sites.
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FEATURES Sidebar Snapshot- The
OF ZEOLITES Timeslide
zeolites with applications to FCC are Type X,
FCC Common Problems… Type Y, and ZSM-5. Both X and Y zeolites have essentially the same
crystalline structure. The X zeolite has a lower silica-alumina ratio than the Y
zeolite. The X zeolite also has a lower thermal and hydrothermal stability than
the Y zeolite. Some of the earlier FCC zeolite catalysts contained X zeolite;
however, virtually all of today's catalysts contain Y zeolite or variations
Slide Valves thereof.
1 Type Y zeolite is the primary catalytic ingredient. It provides high activity, high
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gasoline selectivity and enhanced coke selectivity. Adjusting Y zeolite silica-
alumina ratio influences
– Gasoline selectivity and octane
– Coke selectivity
NORMAL OPERATION … – Olefin selectivity zeolite
– hydrothermal stability
Manufacturing factors affecting zeolite stability are Fresh zeolite Si/Al ratio
and Degree of rare earth exchange. Zeolites are diffusion limited by large high
molecular weight hydrocarbons. However, Meso pores formed in zeolite of
Wet Gas Compre… 1 hydrothermally manufactured USY increase its ability to crack larger
molecules.
Matrix - The term matrix refers to the catalyst binder, components of the
catalyst other than zeolite and the term active matrix means the component of
FCC Catalyst
the catalyst other than zeolite having the catalytic activity. Alumina is the
source for an active matrix. Most active matrices used in FCC catalysts are
FCC feed characteristic… amorphous.
Physical Attributes of Matrix: It provides particle size and shape for

fluidization, determines attrition characteristics and density, determines
accessibility to cracking sites via a proper pore structure.
Chemical Attributes of Matrix: It may be inert, may be active to help up
gradation of bottoms to LCO, may provide other functions like metal
passivation, can enhance coke and gas formation
Filler and Binder - The filler is a clay incorporated into the catalyst to dilute its
activity. Kaoline [Al2(OH)2, Si2O5] is the most common clay used in the FCC
catalyst.
PERFORMANCE FEATURES OF FCC CATALYST
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CATALYST PROPERTIES
1. Activity –
FCC Catalyst
I. MAT or ACE - Significance: Measure of ability of Catalyst to crack into
useful products.Final outcome of the manufacturing technique and
FCC feed characteristic… physio-chemical properties of the catalyst.
Conversion = (100-LCO-Slurry),wt%
II. Hydrogen Factor (HF) :
Hydrogen Factor = ( H2 yield in FG )

0.12
Operating effects of increased HF --- factor increases due to increase in

contaminant metals resulted in H2 to CH4 ratio increases, wet gas compressor
MW decreases and discharge pressure drops, ROT or severity reduction
required, may limit unit with WGC operations
Recommended response – Flush metals with Fresh cat or good quality E-
cat, reduce contaminant metals, passivate with antimony, add macro-porous
alumina (ADM60) to formulations
III. Coke Factor (CF) –
Coke Factor = (Coke Yield) { 100-Conv }

{ Conv }
NORMAL OPERATION … Relative measure term of delta coke in unit or coke production in test
CF is a function of: Catalyst formulation, Ecat equivalent Ni content, Important

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Operating effects of increased CF – Coke factor increases due to increase in
FCC Common Problems… contaminant metals resulted in delta coke increases, main air blower (MAB)
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requirement Snapshot
increases, Timeslide
assuming constant CRC, ROT or severity reduction
FCC Common Problems… required, may limit MAB air or regenerator temperature increase
Recommended response - Flush metals with Fresh cat or good quality E-cat,
reduce contaminant metals, passivate with antimony, add macro-porous
alumina (ADM60) to formulations
Slide Valves 2. Physical properties - SA, PSA, ABD, F prop
1 Surface Area (SA), M2/g - The reported surface area is the combined surface
Main Column Bot…
area of zeolite and matrix. In zeolite manufacturing, the measurement of the
zeolite surface area is one of the procedures used by catalyst suppliers to
control quality. The surface area is commonly determined by the amount of
nitrogen adsorbed by the catalyst.
NORMAL OPERATION … The surface area correlates fairly well with the fresh catalyst activity. Upon
request, catalyst suppliers can also report the zeolite surface area. This data
is useful in that it is proportional to the zeolite content of the catalyst.
Operating effects of increasing SA - Catalyst selectivity improves, equilibrium
FST increases, delta coke increases, regenerator temperature increases, Cat-
Wet Gas Compre… 1 to-Oil decreases, conversion increase less than the FST increase
FCC Catalyst
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Particle Size Distribution (PSD) - The PSD is an indicator of the fluidization
properties of the catalyst, In general, fluidization improves as the fraction of
Wet Gas Compre… 1 the 0-40 micron particles is increased; however, a higher percentage of 0-40
micron particles will also result in greater catalyst losses.
FCC Operating V… 1 The fluidization characteristics of an FCC catalyst largely depend on the unit's
mechanical configuration. The percentage of less than 40 microns in the
circulating inventory is a function of cyclone efficiency
FCC Catalyst
Particle Size Analysis (PSA) - Why important? : Maximize catalyst circulation

FCC feed characteristic… rate, Monitor catalyst fluidization characteristics, Monitor cyclone efficiency
and monitor circulating inventory attrition. PSA is Calculated from PSD
Apparent Bulk Density (ABD) - The ABD is determined by measuring the mass
of a known volume of catalyst, settled freely under its own weight. The ABD is
important for circulation and cyclone efficiency, higher ABD would improve
the separating efficiency of cyclones.
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F prop - F Prop provides a simple tool to monitor the fluidization
NORMAL OPERATION … characteristics of the FCC. Empirical observation defines the minimum F Prop
for smooth fluidization
Wet Gas Compre… 1
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3. Chemical properties - Al2O3, RE, Ni, V, Na, C, Pt, P2O5, Fe, Sb, Sn
Alumina Oxide (Al2O3) - Usually constant in most units. Total alumina

including alumina in Zeolite framework depends on the starting raw materials,
can be used to monitor catalyst change outs, alumina is the source of active
Matrix, analyzed by XRF technique
Operating effects of increasing Al2O3: Adds Lewis acid sites, Cracks resid
and gas oils into primarily LCO & gasoline, Increases delta coke, Increases
LPG & gasoline olefinicity, shifts hydrogen from bottoms to LCO, reduces
slurry density
Rare earth (RE) – Usually constant in most units, Indicates zeolite stability
attribute, needs to be optimized as per unit specific objectives, can be used to
catalyst monitor change outs, Analyzed by XRF technique,
Operating effects of increasing REO: Saturates LPG & gasoline olefins,
reduces octane, reduces dry gas & LPG, Increases gasoline, increases delta
coke
Rare earth improves the catalyst activity and hydrothermal stability. Catalysts
can have a wide range of rare earth levels depending on the refiner's
NORMAL OPERATION … objectives. Rare earth (RE) elements serve as a "bridge“ to stabilize the Al
atoms in the zeolite structure. RE prevent the aluminum atoms from
separating from the zeolite lattice when the catalyst is exposed to high
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FCC Common Problems… Nickel - Nickel is introduced with the feed. Nickel deposits on catalyst surface
Classic Flipcard Magazine Mosaic
- NickelSidebar Snapshotcatalyst
slightly reduces Timeslide
activity via pore blockage, no direct zeolite
FCC Common Problems… destruction
It Promotes dehydrogenation reactions (extracts hydrogen forming unstable
olefins, polymerization to heavy hydrocarbons & coke). Increase in Nickel in
catalyst increases delta coke (increases regenerator temperatures, decreases
cat-to-oil & conversion reduces liquid yield)
Slide Valves Increase in Nickel in catalyst Increases H2 yield (reduces wet gas molecular
weight, limits discharge pressure (centrifugal), lower pressure implies less
1 capacity) hence resulting in reduced ROT or conversion
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Nickel activity - Fresh Ni most active, approximately 1/3 of Ni will promote

dehydrogenation reactions, chloride in feed will reactivate aged nickel.
Monitoring of dehydrogenation reactions due to Nickel as H2 to CH4 ratio
NORMAL OPERATION … increases, H2 yield increases in fuel gas production.
Nickel Passivation using Antimony - Passivates about 70% of the Ni, antimony
blocks Ni surface from hydrocarbons, effective at > 1000 ppm on equlibrium
catalyst, optimum antimony/nickel ratio is 0.2-0.6, depends on Ni level and
make-up rate, excess antimony rejected in slurry
Wet Gas Compre… 1
Caution on Nickel Passivation - High antimony levels found in deposits in
slurry exchangers – carcinogenic, cuts platinum promoter activity by 1/3-1/2
Vanadium (V) - Migrates to zeolite which results in zeolite destruction, reduces
catalyst activity, reduces some hydrogen & coke production (about 1/4 of Ni
FCC Catalyst
effect), reduces conversion & liquid yields
Vanadium Passivation using Sn - Tin passivates about 50% of vanadium's
FCC feed characteristic… effects on hydrogen & coke, Tin passivates about 30% of vanadium's effects
on conversion & gasoline yield, apply very carefully, tin is a catalyst poison at
high concentrations, limited effectiveness. Vanadium traps can be used as
other options for Vanadium passivation.
Sodium (Na) Content - The sodium on the catalyst originates either from
zeolite during its manufacture or from the FCC feedstock. It is important for
the fresh zeolite to contain very low amounts of sodium. Sodium decreases
the hydrothermal stability of the zeolite.

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NORMAL OPERATION … [https://1.bp.blogspot.com/-

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4. Advanced analyses - AAI, UCS

Wet Gas Compre… 1
Unit Cell Size - The UCS is a measure of aluminum sites or the total
FCC Operating V… 1 potential acidity per unit cell. The negatively-charged aluminum atoms
are sources of active sites in the zeolite. A freshly manufactured zeolite
has a relatively high UCS in the range of 24,50°A to 24.75°A. The thermal
FCC Catalyst
and hydrothermal environment of the regenerator extracts alumina from
the zeolite structure and, therefore, reduces its UCS
TYPICAL EQUILIBRIUM CATALYST ANALYSIS
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FCCU FREQUENTLY A… Posted 28th November 2016 by Let's Understand FCC

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12/21/2019 FCC Catalyst | FCC Refinery Training Network

Slide Valves • ZEOLITE - Primary Catalytic Component for selective cracking.

Wet Gas Compressor - …

Wet Gas Compre… 1

FCC feed characteristic…

FCC Common Problems…

FCC Common Problems…

Main Column Bot… 1

Dos and Don’ts o… 1

Wet Gas Compressor - …

Wet Gas Compre… 1

FCC feed characteristic…

ZEOLITE CHEMISTRY - A typical zeolite consists of silicon and aluminum

Physical Attributes of Matrix: It provides particle size and shape for

PERFORMANCE FEATURES OF FCC CATALYST

FCC Common Problems…

Main Column Bot… 1

Dos and Don’ts o… 1

Wet Gas Compre… 1

II. Hydrogen Factor (HF) :

Hydrogen Factor = ( H2 yield in FG )

Operating effects of increased HF --- factor increases due to increase in

III. Coke Factor (CF) –

Coke Factor = (Coke Yield) { 100-Conv }

CF is a function of: Catalyst formulation, Ecat equivalent Ni content, Important

Slide Valves 2. Physical properties - SA, PSA, ABD, F prop

FCC feed characteristic…

FCC Common Problems…

FCC Common Problems…

Main Column Bot… 1

Dos and Don’ts o… 1

Wet Gas Compressor - …

Particle Size Analysis (PSA) - Why important? : Maximize catalyst circulation

FCC Common Problems…

Main Column Bot… 1

Wet Gas Compressor - …

Wet Gas Compre… 1

FCC Operating V… 1 [https://3.bp.blogspot.com/-

FCC feed characteristic…

Alumina Oxide (Al2O3) - Usually constant in most units. Total alumina

Nickel activity - Fresh Ni most active, approximately 1/3 of Ni will promote

FCC Common Problems…

FCC Common Problems…

Main Column Bot… 1

Dos and Don’ts o… 1

NORMAL OPERATION … [https://1.bp.blogspot.com/-

4. Advanced analyses - AAI, UCS

FCCU FREQUENTLY A… Posted 28th November 2016 by Let's Understand FCC

FCC Common Problems…

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FCC feed characteristic…

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