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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
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Catalyst Physical Properties

RETENTION / LOSSES
- Attrition Resistance

FLUIDIZATION
- Particle Size Distribution
- Average Bulk Density

HEAT TRANSPORT
- Specific Heat Capacity

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FCC Catalyst Components
FCC Catalyst Components
7 µm

Binder
Zeolite Y
Clay

Pores

Pseudo crystalline
Matrix Aluminas

70 µm (avg.)

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FCC Catalyst Components
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

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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

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The Zeolite
Structure of Zeolite Y

Supercage
(α-cage)

Sodalite cage
(β-cage)

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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

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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
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Brönsted Acid Site

H+
O-
O

Si Al
O
O O
O O

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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


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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-

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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)

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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

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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)

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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)

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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

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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

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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

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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

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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

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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

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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

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Tuneable Matrix Alumina (TMA)
Example Morphologies

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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 ++ ++ ++ ++

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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)


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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

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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

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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

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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


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FCC Additives
ZSM-5 Additives
ZSM-5 Additive Particle

MICROSTRUCTURE MESOSTRUCTURE

Filler
Zeolite
ZSM-5
Binder

7 µm

MACROSTRUCTURE

75 µm

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Zeolite ZSM-5 Crystal Structure

ZSM-5 framework structure ZSM-5 pore structure

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ZSM-5 Shape Selectivity

Products

fast

slow

Reactants Non-reactants

Products

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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

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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)

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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

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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

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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

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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

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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

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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 )

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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

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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
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Catalyst Manufacturing
Synthesis of Zeolite Y

NaSiO3 NaAlO2
Al2(SO4)3 Seeds

ca. 100°C, 1-2 days


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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

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ZEOLITE PLANT (Part 2)

Bag Filter System

Dryer

NH4-Y /
Calciner
RE-Y Zeolite

Hot Air CREY /


US-Y Zeolite

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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

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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

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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

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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

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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

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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
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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+

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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

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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

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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

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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

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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
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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

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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

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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

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Selecting the Right
Combination
Gasoline Mode Operation
FCC Optimization for Gasoline Production

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
Hydrotreater
Gasoline Selectivity is favored by:
 high Zeolite / Matrix ratio (Z/M)
 high Hydrogen Transfer (high ucs)
 high Catalyst Activity (Conversion)

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FCC Optimization for Gasoline Production

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
Hydrotreater
Gasoline Selectivity is favored by:
 high Catalyst / Oil ratio
 moderate Riser Outlet Temperature
 high ECat Activity (MAT)

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Distillate Mode Operation
FCC Optimization for Middle Distillates

Production
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
Hydrotreater
Middle Distillate Selectivity is favored by:
 high Matrix Activity (lower Z/M)
 high Hydrogen Transfer (high ucs)
 low Catalyst Activity (low Conversion)

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FCC Optimization for Middle Distillates

Production
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
Hydrotreater
Middle Distillate Selectivity is favored by:
 low Catalyst / Oil ratio
 low Riser Outlet Temperature
 low ECat Activity (MAT)
 use of Recycle (HCO/Slurry)
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Light Olefins Mode Operation
FCC Optimization for Light Olefins Production

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
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)

www.gbhenterprises.com
FCC Optimization for Light Olefins Production

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
Hydrotreater
Light Olefin Selectivity is favored by:
 high Riser Outlet Temperature
 high Catalyst / Oil ratio
 high ECat Activity (MAT)

www.gbhenterprises.com
Short Contact Time Operation
FCC Optimization for Short Contact Time

Operations
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
Hydrotreater
Short Contact Time Operation is favored by:
 high Catalyst Activity
 balanced Zeolite/Matrix ratio (Z/M)
 high Hydrogen Transfer (high ucs)

www.gbhenterprises.com
FCC Optimization for Short Contact Time

Operations
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
Hydrotreater
Short Contact Time Operation is favored by:
 high Riser Outlet Temperature
 high Catalyst / Oil ratio
 high ECat Activity (MAT)

www.gbhenterprises.com
Gasoline Olefins Reduction
FCC Optimization for Gasoline Olefins

Reduction
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
Hydrotreater
Gasoline Olefins Reduction is favored by:
 high Zeolite / Matrix ratio (Z/M)
 high Hydrogen Transfer (high ucs)
 moderate Matrix Activity (SAM-700)
 high Metals Tolerance (e.g. Ni and V)
www.gbhenterprises.com
FCC Optimization for Gasoline Olefins

Reduction
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
Hydrotreater
Gasoline Olefins Reduction is favoured by:
 high Catalyst / Oil ratio
 low Riser Outlet Temperature
 high ECat Activity
 high Conversion
www.gbhenterprises.com
Questions ?

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