Fcccatalystdesignmorphphysiooptimization 150107212315 Conversion Gate01

FCC Catalyst Design
Morphology, Physiology, Reaction

Chemistry and Manufacturing
By:
Gerard B. Hawkins
Managing Director, CEO
 Introduction
 FCC Catalyst Components

 - the Zeolite
 - the Matrix
 - Additives ( ZSM-5, other )
 Catalyst Manufacturing
 Reaction Chemistry
 - b scission (cracking)
 - hydrogen transfer
 - heat balance considerations
 Selecting the Right Combination

FCC: POSITION IN REFINERY
Crude Straight Run Fuel Gas H2, C1, C2, C2=

Atmospheric
Products
Column
C3's, C4's for LPG
C3= for dimersol / petrochem.
Atmospheric C3=, C4='s for cat. polym.
Residue Vac. Gas Oil C3=, C4='s, i-C4 for alkylation
i-C4= for MTBE
Vacuum Gasoline C5 - 221°C
Column Kerosene 150 - 250°C
Diesel 200 - 350°C
Vacuum
FCC UNIT Cat. Heating Oil
Residue HT Resid
Residue
In the FCC unit high mol. wt.
Hydrotreater
feeds
(VGO / Residue) are converted to
lighter, more valuable, products
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FCC Unit Operating Conditions : Typical
Example
Prod uc ts

Reg enera tor 530°C
flue g a s
DISENGAGER
510°C
Strip p ing stea m
735°C
REGENERATOR
RISER
720°C
Feed 250°C
190°C
Reg enera tor
Air
Catalyst Physical Properties
RETENTION / LOSSES
- Attrition Resistance
FLUIDIZATION
- Particle Size Distribution
- Average Bulk Density
HEAT TRANSPORT
- Specific Heat Capacity
FCC Catalyst Components
7 µm
Binder
Zeolite Y
Clay
Pores
Pseudo crystalline
Matrix Aluminas
70 µm (avg.)
Zeolite
 Primary catalytic component for selective cracking
 Can be substantially modified to alter its activity,

selectivity and effect on product quality
 Generally rare-earth exchanged or ultrastable Y

zeolites
 More than 10,000 times more active than amorphous

catalysts used before the introduction of zeolite Y
Role of the FCC Catalyst Matrix
Matrix
 Forms the continuum that holds together
the zeolite crystals
 Acid sites on active matrix component

catalyze cracking of feed molecules too
large to enter zeolite pores
 Matrix porosity facilitates diffusion of feed

molecules to zeolite
 Metals traps (e.g. for Vanadium or Nickel)

may be incorporated in the matrix
The Zeolite
Structure of Zeolite Y
Supercage
(α-cage)
Sodalite cage
(β-cage)
Zeolite Structure and Properties
Zeolites are crystalline
microporous, alumino silicates
Framework alumina (AlO2)- units
are associated with Acidic Active
Sites
Cations within microporous
cages and channels (Mn+ = H+,
La3+, Ce3+, Ce4+)
Hydrocarbon conversion
catalyzed at acid sites within
microporous channels
(Mn+)z/n {(SiO2)y (AlO2)-z} framework Acid Site Activity and Acid Site
Density determine the Activity
and Selectivity of the zeolite
Zeolite Acidity
 Brönsted acid
site H
O O
Proton (H) donor
Si Al Si
Lewis acid site

O Al O Trivalent Al - hydride ion abstractor
O
Brönsted Acid Site
H+
O-
O
Si Al
O
O O
O O
Routes for Zeolite Y
Stabilization
 HREY
 RE ion-exchange calcine NH4+ ion-exchange

 NaY REY CREY NH4CRE
 USY
 NH4+ ion-exchange ultrastabilize RE3+ ion-exchange

 NaY NH4Y USY REUSY

Ion Exchange to Generate Acid
Sites (H+)
Ammonium Exchange
 Na+-Z- + NH4+ Na+ + NH4+-Z-

calcine
 NH4+-Z- H+-Z- + NH3
↑
Rare Earth
 Exchange
3Na+-Z- + RE(H2O)63+ 3Na+ + RE(H2O)63+-[Z]3-

hydrolysis
RE(H2O)63+-[Z]3- RE(H2O)5(OH)2+ -H+-[Z]3-
Reaction Mechanism for Hydrothermal
Dealumination and Stabilization of Y Zeolites
Framework
Si
Dealumination Si
O
O
+H2O
H +Al(OH)3
Si O Al O Si Si O H H O Si
(Steam) H
O
O
Si Hydroxyl Nest
Si
(defect site)
Framework
Si
Stabilization Si
O
O
H +SiO2
Si O H H O Si Si O Si O Si
H (Steam)
O
O
Hydroxyl Nest
Si
Si (defect site)
Unit-Cell Size and Si/Al ratio
 Numerous relationships given in the literature
 Breck and Flanigen relationship widely used
 NAl / ucs = 115.2 [ ao - 24.191 ]
 and: NSi / ucs = 192 - NAl / ucs
 thus: Si / Alframework = NSi / NAl
Control of the equilibrium UCS
 UCS (Å)
 As-synthesized NaY 24.64 (54 Al / uc)

 Ultra stabilized Y 24.54 (40 Al / uc)
 Steam deactivated USY 24.21-24.30*(2-13 Al /uc)
 *Depends on rare-earth level

 - (the higher the RE, the higher the UCS)
RE level vs UCS (Å)
100
90
80
70
RE level, %
60
50
40
30
20
10
0
24.21 24.26 24.31 24.36 24.41
UCS (Å)
Zeolite Active Site Distribution
Equilibrium US-Y Zeolite Equilibrium CREY Zeolite

unit cell size 24.25 Å unit cell size 24.38 Å
Framework Si/Al = 27 Framework Si/Al = 7.8
7 Al atoms / unit cell 22 Al atoms / unit cell
Dealumination
 Effect of Si / Al ratio on Zeolite
Properties
 High Al Low Al
high zeolite unit cell size low
low thermal stability high
low hydrothermal stability high
high intrinsic cracking activity low

high hydrogen transfer activity low
Major Effects of Equilibrium
Unit Cell Size
 Increasing Unit Cell Size :
 Increases Active Site Density

 Decreases Active Site Strength
 Hence, Increased Hydrogen Transfer vs. Cracking :
 Increased Gasoline Selectivity

 Lower Gasoline Octane Numbers (RONc and MONc)
 Decreased LPG (C3 and C4) Selectivity

 Lower LPG Olefinicity
Octane Response vs. Zeolite
Unit-Cell Size
Delta Gasoline Yield, Wt%FF

3
Delta RON, Delta MON
RON
2
Gasoline
MON 1
1
0
0
24.24 24.28 24.32 24.36 24.40
Zeolite Unit Cell Size, Å

Increasing rare earth
Relative Coke Selectivity of Zeolite Types
Relative Coke Selectivity
unit cell size range CREY

USY for minimum coke
24.28 - 24.34 Å
REUSY
CSSN CSX
Equilibrium Unit Cell Size
The Matrix
Selective Active Matrices
 Catalytically active surface
 Less selective in cracking than zeolite
 Variable acid site strength and pore structure
 Helps crack the bottoms to provide ‘feed’ for
the zeolite component
 Important for metals tolerance
Matrix Design Considerations
Matrix Requirements
 Crack bottoms with minimum coke and gas penalty

 Provide resistance to Nickel, Vanadium and Nitrogen
 Controlled porosity eliminates heavy feed diffusion limitations
 The appropriate Matrix type depends upon feed characteristics

(e.g. aromaticity, Concarbon, metals, nitrogen, etc.)
 Optimize Zeolite / Matrix ratio for low coke and gas as well as
low SA/K number
Tuneable Matrix Alumina (TMA)
Example Morphologies
Matrix Technology
 Optimal matrix system is selected depending on the
main operating objectives / constraints as below
Matrix Bottoms Coke/Gas Vanadium Nickel

System Cracking Selectivity Tolerance Tolerance
Type 1 +++ + +++ +
Type 2 + +++ + +++
Type 3 ++ ++ ++ ++
0.6
d (Pore Volume) / d log (Pore Diameter)
Catalyst A (steamed)
0.5 REUSY
High Matrix Activity
0.4
Catalyst B (steamed)
REUSY
0.3 Moderate Matrix Activity
0.2
0.1
0
10 100 1,000 10,000
Pore Diameter, (Å)

Nickel Tolerance - Matrix Consideration
Ni Ni
Highly Dispersed - Poor Ni Tolerance Ni
Ni Ni Ni
Ni
Ni Ni
Ni
Good Ni Support Ni Ni
Ni Ni
High Ni dehydrogenation activity Ni
Nickel Agglomeration
Chemical Reaction Ni Ni Ni Ni
Ni Ni
Ni Ni Ni
Poor Ni Support Ni
Low Ni dehydrogenation activity Å 100
Ni trapping matrix
Solid State Diffusion

Chemical Reaction Ni
Al
solid state Al
Strong Metal-Support Interaction

Al diffusion
Low Ni dehydrogenation activity Al
NiAl2O4
Al
SA/K Number
Total ECat Surface Area Total ECat Surface Area
SA/K number = =
Kinetic Conversion MAT Conv. / (100 - MAT Conv.)
 Lower SA/K number:
 improves catalyst strip ability (decreasing occluded coke)
provides a poorer support for contaminant metals

(decreasing contaminant coke)
Both the above contribute to improved coke and gas

selectivity
AVOID EXCESS CATALYST SURFACE AREA - ONLY NEED


SURFACE AREA THAT CONTRIBUTES TO PRODUCING DESIRED

CONVERSION PRODUCTS
Major Effects of Increased Z/M
Ratio
Increasing Z/M :
 Increases Selective Zeolite Cracking

 Lower Coke and Fuel Gas (C2-) Yields
 Increased Gasoline Selectivity
But,
 Lower LCO Selectivity
 Increased Bottoms Selectivity
Effect of Zeolite/Matrix Ratio on Product Selectivity's
MAT Reaction Conditions: 60 wt% conversion Feed: 0.919 g/ml, 11.5 Watson K
15.0
Gasoline, wt%
44.0
C3 + C4, wt%
42.0 14.0
40.0
13.0
38.0
12.0
16.0
LCO, wt%
HCO, wt%
26.0
15.0
25.0
14.0
24.0
13.0
Dry Gas, wt%

Coke, wt%
1.8
4.0
1.4
2.0 1.0
0 2 4
Amorphous Zeolite
Cracking Cracking
Zeolite / Matrix Surface Area Ratio of Steamed Catalyst

FCC Additives
ZSM-5 Additives
ZSM-5 Additive Particle
MICROSTRUCTURE MESOSTRUCTURE
Filler
Zeolite
ZSM-5
Binder
7 µm
MACROSTRUCTURE
75 µm
Zeolite ZSM-5 Crystal Structure
ZSM-5 framework structure ZSM-5 pore structure
ZSM-5 Shape Selectivity
Products
fast
slow
Reactants Non-reactants
Products
Selective Conversion of Low
Octane Species
The relative cracking for various hydrocarbons are:
Hydrocarbon Type Rel. rate Rel. octane

Straight chain paraffins & olefins Fast Low
Moderately branched paraffins & olefins Moderate Moderate
Highly branched paraffins & olefins Slow High
Naphthenes Slow Low
Aromatic side-chains Slow High
Cracking Mechanism
ZSM-5 Additive Technology
Hydrogen Transfer
Low active site density of ZSM-5 (relative to H-Y) results
in low hydrogen transfer activity thus products have a
high degree of olefinicity
Isomerization
Isomerization of lower to higher branching is favored
due to the relative stabilities of carbo-cation
intermediates (tertiary > secondary > primary)
Commercial Data: Unit Response
to 3 wt% Additive Addition
95
ZSM-5 Additive
94
Gasoline Research Octane
Provided an Immediate
1.8 RON Gain
93
92
91
90
89
-40 -30 -20 -10 0 10 20 30
Days into ZSM-5 Usage
DCR Testing of ZSM-5 Additive:
Propylene Yield
12
10
C3= (wt%)
2
64 68 72 76 80 84
Conversion (wt%)
ECAT 521°C ECAT 543°C ECAT 566°C

4% Additive 521°C 4% Additive 543°C 4% Additive 566°C
DCR Testing of ZSM-5 Additive: Alky
Feed Yield
17
Total C4= + iC4 (wt%)
15
13
11
7
64 68 72 76 80 84
Conversion (wt%)
ECAT 521°C ECAT 543°C ECAT 566°C
4% Additive 521°C 4% Additive 543°C 4% Additive 566°C
Yield and Octane Shifts With ZSM-5 Additives
 Low octane gasoline components are converted

to LPG olefins
 Gasoline composition changes:

decreased paraffins and olefins in "octane-dip" range
increased light iso-paraffins
increased light olefins
increased aromatics (via concentration)
 Gasoline RONc and MONc increased
 No change in coke, dry gas, or bottoms yield
Environmental Additives
Sulfur Balance in an FCC
Unit
Light Gases, H2S 20 - 60%
F Gasoline 2 - 10%
Feed Sulfur C Light Cycle Oil 10 - 25 %
Sulfides
Thiophenes
Benzothiophenes
C Heavy Cycle Oil 5 - 35 %
Multi-ring Thiophenes
Coke, SOx 2 - 30 %
• FCC gasoline typically contributes >90% of the total gasoline pool

sulfur
• Up to 50% of FCC gasoline sulfur is usually concentrated in the
back end of the gasoline
Catalytic SOx Reduction
PRODUCTS

( with H2S )
FLUE GAS
( with SOx )
STRIPPER:
Hydrolysis of Metal Sulfide
REGENERATOR:
Formation of SOx MeS (s) + H2O (g) = MeO (s) + H2S (g)
S (coke) + O2 (g) = SO2 (g)
Stripping Steam
SO2 (g) + ½ O2 (g) = SO3 (g)
RISER:
Formation of Metal Sulfate Reduction of Metal Sulfate
SO3 (g) + MeO (s) = MeSO4 (s) MeSO4 (s) + 4 H2 (g) = MeS (s) + 4 H2O (g)
MeSO4 (s) + 4 H2 (g) = MeO (s) + H2S (g) + 3 H2O (g)
Regenerator
FEED
Air
( with Sulfur )
Comp X Allowed Refinery C to
Reduce Sulfur by ca. 20-25%
FEED SULFUR IN GASOLINE vs GASOLINE CUT POINT
8
Feed Sulphur in Gasoline (%)
1
180 185 190 195 200 205 210 215 220 225 230
Gasoline C.P. (ºC)
W/O Additive Comp X
NOx Emissions: XNOx vs. Pt. Promoter
500
Addition of Pt
based Promoter
400
300
NO (ppm)
60% Reduction
200
100
Addition of 0.5% XNOx

0
-1.5 -1.0 -0.5 0.0 0.5 1.0 1.5 2.0
Hours www.gbhenterprises.com
Catalyst Manufacturing
Synthesis of Zeolite Y
NaSiO3 NaAlO2
Al2(SO4)3 Seeds
ca. 100°C, 1-2 days

Sodium ZEOLITE PLANT (Part 1)
Silicate
Aluminium Sodium
Sulfate Aluminate
ML-Gel Seeds
Water
RECl3 /
(NH4)2SO4
Beltfilter Water
Na-Y Zeolite
Aluminium
Sulfate Beltfilter
NH4-Y /
RE-Y Zeolite
Effluent
Beltfilter
Effluent
ZEOLITE PLANT (Part 2)
Bag Filter System
Dryer
NH4-Y /
Calciner
RE-Y Zeolite
Hot Air CREY /

US-Y Zeolite
FCC PLANT
Hot
Zeolite Water
Air
(e.g.. CREY/USY)
Spray
Drier
RECl3 /
(NH4)2SO4 Water
Mixing Scrubbing System
Beltfilter LS-USY
Calciner
Clay
Water Binder
Effluent
FCC
CATALYST
WET END Mixing DRY END
Reaction Chemistry
Boiling Range Distribution of
FCC Feed and Products

C2
C4
221°C
400°C
FEED
Wt% FF
PRODUCTS
Gas LPG Naphtha LCO Slurry / Feedstock
Boiling Point, °C
Hydrocarbon Types
CHAIN STRUCTURES RING STRUCTURES
H H
H H H H H H H H H
R H
R R
R
H H H H H H H
H H H H H H H H H
H H
H H
Paraffin Naphthene
H H H H
H H H H H
R R
R R H H H
H H H H
H H H H H H H
H
Olefin Alkylaromatic
Crackability (Conversion): Paraffinic > Naphthenic > Aromatic
Coke-forming tendency (Heat Balance): Paraffinic < Naphthenic < Aromatic
Principles of Catalysis
Catalysts Lower Activation Energies

EThermal of Forward & Backwards Reactions,
Increasing the Rates of Both
ECatalytic
The Heat of Reaction is Unchanged
Free Energy
by the Catalyst
The Position of Thermodynamic

Equilibrium is Unchanged by the
EB Catalyst
EA ∆ Hreaction Non-Equilibrium Distributions Occur

Under Kinetic Controlled Conditions
Reaction Co-ordinate
Thermal vs Catalytic Cracking
n-Hexadecane @ 500°C
150
Moles Product / 100 Moles Cracked
Thermal Cracking
Catalytic Cracking
100
50
C1 C2 C3 C4 C5 C6 C7 C8 C9 C10 C11 C12 C13 C14
Carbon Number
Principle Reactions in FCC
Paraffins Cracking Paraffins + Olefins

Olefins Cracking Light Olefins
Isomerisation Branched H Transfer Branched
Olefins Paraffins
H Transfer
Paraffins
Cyclisation Dehydrogenation
Naphthenes Coke
Condensation
Cracking
Naphthenes Olefins
Isomerisation
other Naphthenes
Dehydrogenation Dehydrogenation
cyclo-Olefins Aromatics
Side-chain Cracking
Aromatics unsubstituted Aromatics + Olefins
Transalkylation
other Aromatics
Dehydrogenation Dehydrogenation
poly-Aromatics Coke
Condensation Condensation
β - Scission (cracking)
Reactions
Cracking Reaction Mechanism
Si Al Si
O O - O
H
+ Catalyst (Acid Site)
H H
H H H H H H H
Protonation
R R R + R
H H H H H H
H H H H H H H H H H
Carbenium Ion
H H H
H H H H H H
R + R ß-scission R R
+ H
H H H H H H
H H H H H H H H H H
Olefin Product
H H
R Intermolecular H H
+
Rearrangemen H
H H R +
H H H H t H
H H
H H
H H
H Deprotonation H H
R + H
H R
H H H
H H - H
H H
H+
Thermal Reaction Mechanism
H H H H H
Free radical H H H H H
formation
R H R H
H
H H
H
H H H H
H
-H . H
H H
H
H H . H
H
Secondary Free radical

hom olytic fission
hom olytic fission
ß-scission
C H
hom olytic fission (Cracking) C C
C C
H H H H H H
R
. H R
.
H
H H H H H H
H H H H H H H H
ß-scission
New free Ethylene (cracking) Primary Free alpha- Olefin
radical radical Product
Thermal cracking gives high yields of methane,

alpha-olefins and ethylene, no increased branching
Summary of Cracking Reactions
Paraffin Paraffin + Olefin
 Naphthene Olefin
Alkylaromatic Alkylaromatic + Olefin
Olefin Olefin + Olefin
Relative Cracking Rates:

Olefin > Naphthene = Alkylaromatic > Paraffin
Olefins most readily form carbocations
Aromatic side-chains readily undergo cracking

reactions, however, aromatic rings do not crack
Hydrogen Transfer Reactions
Hydrogen Transfer Reactions
olefin +
 R - CH = CH - R’ R - CH - CH - R’
protonation H
H
+
+ R - CH - CH2 - R’
R - CH - CH2 - R’
H H
+
CH - CH2 hydrogen CH - CH2
H2 C CH - R” transfer H2 C CH - R”
CH2 - CH2 CH2 - CH2
H
+
CH - CH CH = CH
- H+
H2 C CH - R” H2 C CH - R”
proton loss
CH2 - CH2 CH2 - CH2
olefin + naphthene paraffin + cyclo-olefin

olefin + cyclo-olefin paraffin + cyclo-diolefin
olefin + cyclo-diolefin paraffin + aromatic
Heat Balance Considerations
FCC Heat Balance Considerations
 Most FCC process variables have an effect

on the heat balance - which, in turn, affects:
Conversion, Yields and Product Qualities
 The FCC unit will always adjust itself to

remain in heat balance by burning enough
coke for the energy requirements
Heat Demands are Satisfied by
Burning Coke
 ∆H losses
ENERGY IS
∆H cracking
REQUIRED FOR ENERGY IS
HEAT LOSSES TO REQUIRED TO
ATMOSPHERE CRACK FEED
∆H air ∆H vaporization
ENERGY IS ENERGY IS
REQUIRED TO REQUIRED TO
HEAT AIR VAPORISE FEED
FCC Delta Coke Types
VGO Resid
Occluded  unstripped hydrocarbons 15% 14%
(product to regenerator)
high hydrogen content
Feed  uncracked heavy feed 15% 28%

components e.g. asphaltenes,
Conradson carbon residue
Metals  Formed via dehydrogenation 5% 28%

activity of contaminant metals
e.g. nickel, vanadium
Catalytic  formed as a bi-product of 65% 30%

desired catalytic cracking
Feed Dependence of
Delta Coke
Contaminant Coke
1.60 (Metals Coke) Increases
Feed Residue Coke

(Conradson Carbon)
Increases
Delta Coke
Occluded Coke (Cat/Oil

0.80 Coke) Same / Slight
Feed Residue Increase
Catalytic Coke Coke
0.50 Contaminant Catalytic Coke
Coke (Conversion Coke)
0.30 Decreases
0.10 Occluded Coke
Decreasing Feed Quality

Increasing: Density, ConCarbon, Metals, S, N.
Increasing Resid Content

Increasing Ca/Cp ratio, Endpoint
Conversion Dependence on
Delta Coke
Constant Riser Outlet Temp.
Constant Coke Operation  Lower conversion by :
(Unit at Max. Blower Capacity)
 higher regen.
temperature
Regen T
FCC Unit Conversion
 lower cat/oil (lower

severity)
Unit  Lower effective activity

Conversion due to :
Cat/Oil  coke blockage of pores

Ratio
 metals contamination
Delta Coke, wt.%
 increased nitrogen
Increasing Resid content poisoning
Selecting the Right
Combination
Gasoline Mode Operation
FCC Optimization for Gasoline Production

Atmospheric
Products
Column
C3's, C4's for LPG
i-C4= for MTBE
Diesel 200 - 350°C
Vacuum
Residue HT Resid
Residue
Hydrotreater
Gasoline Selectivity is favored by:
 high Zeolite / Matrix ratio (Z/M)
 high Hydrogen Transfer (high ucs)
 high Catalyst Activity (Conversion)
FCC Optimization for Gasoline Production

Atmospheric
Products
Column
C3's, C4's for LPG
i-C4= for MTBE
Diesel 200 - 350°C
Vacuum
Residue HT Resid
Residue
Hydrotreater
Gasoline Selectivity is favored by:
 high Catalyst / Oil ratio
 moderate Riser Outlet Temperature
 high ECat Activity (MAT)
Distillate Mode Operation
FCC Optimization for Middle Distillates
Production
Atmospheric
Products
Column
C3's, C4's for LPG
Atmospheric
C3=, C4='s for cat. polym.
i-C4= for MTBE
Diesel 200 - 350°C
Vacuum
Residue HT Resid
Residue
Hydrotreater
Middle Distillate Selectivity is favored by:
 high Matrix Activity (lower Z/M)
 low Catalyst Activity (low Conversion)
FCC Optimization for Middle Distillates
Production
Atmospheric
Products
Column
C3's, C4's for LPG
Atmospheric
i-C4= for MTBE
Diesel 200 - 350°C
Vacuum
Residue HT Resid
Residue
Hydrotreater
Middle Distillate Selectivity is favored by:
 low Catalyst / Oil ratio
 low Riser Outlet Temperature
 low ECat Activity (MAT)
 use of Recycle (HCO/Slurry)
Light Olefins Mode Operation
FCC Optimization for Light Olefins Production

Atmospheric
Products
Column
C3's, C4's for LPG
Atmospheric
i-C4= for MTBE
Diesel 200 - 350°C
Vacuum
Residue HT Resid
Residue
Hydrotreater
Light Olefin Selectivity is favored by:
 low Hydrogen Transfer (low ucs)
 use of ZSM-5 Zeolite containing additives
 high Catalyst Activity (very high Conversion)
FCC Optimization for Light Olefins Production

Atmospheric
Products
Column
C3's, C4's for LPG
Atmospheric
i-C4= for MTBE
Diesel 200 - 350°C
Vacuum
Residue HT Resid
Residue
Hydrotreater
Light Olefin Selectivity is favored by:
 high Riser Outlet Temperature
Short Contact Time Operation
FCC Optimization for Short Contact Time
Operations
Atmospheric
Products
Column
C3's, C4's for LPG
Atmospheric
i-C4= for MTBE
Diesel 200 - 350°C
Vacuum
Residue HT Resid
Residue
Hydrotreater
Short Contact Time Operation is favored by:
 high Catalyst Activity
 balanced Zeolite/Matrix ratio (Z/M)
FCC Optimization for Short Contact Time
Operations
Atmospheric
Products
Column
C3's, C4's for LPG
Atmospheric
i-C4= for MTBE
Diesel 200 - 350°C
Vacuum
Residue HT Resid
Residue
Hydrotreater
Short Contact Time Operation is favored by:
 high Riser Outlet Temperature
Gasoline Olefins Reduction
FCC Optimization for Gasoline Olefins
Reduction
Atmospheric
Products
Column
C3's, C4's for LPG
i-C4= for MTBE
Diesel 200 - 350°C
Vacuum
Residue HT Resid
Residue
Hydrotreater
Gasoline Olefins Reduction is favored by:
 high Zeolite / Matrix ratio (Z/M)
 moderate Matrix Activity (SAM-700)
 high Metals Tolerance (e.g. Ni and V)
FCC Optimization for Gasoline Olefins
Reduction
Atmospheric
Products
Column
C3's, C4's for LPG
i-C4= for MTBE
Diesel 200 - 350°C
Vacuum
Residue HT Resid
Residue
Hydrotreater
Gasoline Olefins Reduction is favoured by:
 low Riser Outlet Temperature
 high ECat Activity
 high Conversion
Questions ?

Fcccatalystdesignmorphphysiooptimization 150107212315 Conversion Gate01

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FCC Catalyst Design

Morphology, Physiology, Reaction

 FCC Catalyst Components

 Selecting the Right Combination

Crude Straight Run Fuel Gas H2, C1, C2, C2=

 Primary catalytic component for selective cracking

 Can be substantially modified to alter its activity,

 Generally rare-earth exchanged or ultrastable Y

 More than 10,000 times more active than amorphous

 Acid sites on active matrix component

 Matrix porosity facilitates diffusion of feed

 Metals traps (e.g. for Vanadium or Nickel)

Lewis acid site

 RE ion-exchange calcine NH4+ ion-exchange

 NH4+ ion-exchange ultrastabilize RE3+ ion-exchange

3Na+-Z- + RE(H2O)63+ 3Na+ + RE(H2O)63+-[Z]3-

 Breck and Flanigen relationship widely used

 NAl / ucs = 115.2 [ ao - 24.191 ]

 and: NSi / ucs = 192 - NAl / ucs

 thus: Si / Alframework = NSi / NAl

 As-synthesized NaY 24.64 (54 Al / uc)

 *Depends on rare-earth level

Equilibrium US-Y Zeolite Equilibrium CREY Zeolite

high intrinsic cracking activity low

 Increases Active Site Density

 Hence, Increased Hydrogen Transfer vs. Cracking :

 Increased Gasoline Selectivity

 Decreased LPG (C3 and C4) Selectivity

Delta Gasoline Yield, Wt%FF

24.24 24.28 24.32 24.36 24.40

Zeolite Unit Cell Size, Å

unit cell size range CREY

Equilibrium Unit Cell Size

 Crack bottoms with minimum coke and gas penalty

 The appropriate Matrix type depends upon feed characteristics

Matrix Bottoms Coke/Gas Vanadium Nickel

Type 1 +++ + +++ +

Type 2 + +++ + +++

Pore Diameter, (Å)

Low Ni dehydrogenation activity Å 100

Solid State Diffusion

Strong Metal-Support Interaction

 Lower SA/K number:

 improves catalyst strip ability (decreasing occluded coke)

provides a poorer support for contaminant metals

Both the above contribute to improved coke and gas

AVOID EXCESS CATALYST SURFACE AREA - ONLY NEED

SURFACE AREA THAT CONTRIBUTES TO PRODUCING DESIRED

 Increases Selective Zeolite Cracking

Dry Gas, wt%

Zeolite / Matrix Surface Area Ratio of Steamed Catalyst

ZSM-5 framework structure ZSM-5 pore structure

Hydrocarbon Type Rel. rate Rel. octane

Highly branched paraffins & olefins Slow High

Naphthenes Slow Low

Aromatic side-chains Slow High

ECAT 521°C ECAT 543°C ECAT 566°C

 Low octane gasoline components are converted

 Gasoline composition changes:

 Gasoline RONc and MONc increased

 No change in coke, dry gas, or bottoms yield

• FCC gasoline typically contributes >90% of the total gasoline pool