FCC Catalyst Design: Morphology, Physiology, Reaction Chemistry and Manufacturing
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Transcript of FCC Catalyst Design: Morphology, Physiology, Reaction Chemistry and Manufacturing
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
In the FCC unit high mol. wt. feeds
(VGO / Residue) are converted to lighter, more valuable, products
C3=, C4='s for cat. polym. C3= for dimersol / petrochem. C3's, C4's for LPG
C3=, C4='s, i-C4 for alkylation i-C4= for MTBE
Fuel Gas H2, C1, C2, C2=
Gasoline C5 - 221°C
Kerosene 150 - 250°C
Cat. Heating Oil
Diesel 200 - 350°C
FCC UNIT
Crude Atmospheric Column
Straight Run Products
Atmospheric Residue Vac. Gas Oil
Vacuum Residue
Vacuum Column
Residue Hydrotreater
HT Resid
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FCC Unit Operating Conditions : Typical Example
DISENGAGER
RISER REGENERATOR
190°C
735°C
720°C
Feed
Stripping steam
Produc ts
Regenerator flue gas
Regenerator Air
530°C
510°C
250°C
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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
70 µm (avg.)
7 µm
Pseudo crystalline Matrix Aluminas
Pores
Clay
Binder Zeolite Y
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FCC Catalyst Components
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
Zeolite
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Role of the FCC Catalyst 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
Matrix
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The Zeolite
Structure of Zeolite Y
Sodalite cage (β-cage)
Supercage (α-cage)
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(Mn+)z/n {(SiO2)y (AlO2)-z} framework
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
Acid Site Activity and Acid Site Density determine the Activity and Selectivity of the zeolite
Zeolite Structure and Properties
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Zeolite Acidity Brönsted acid
site
Al
Lewis acid site
O O
O
Al Si Si
O O
H
Proton (H) donor
Trivalent Al - hydride ion abstractor
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Brönsted Acid Site
O-
O O
O
H+ O
O O
Si Al
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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+)
Na+-Z- + NH4+ Na+ + NH4
+-Z- NH4
+-Z- H+-Z- + NH3 ↑
calcine
3Na+-Z- + RE(H2O)63+ 3Na+ + RE(H2O)6
3+-[Z]3-
RE(H2O)63+-[Z]3- RE(H2O)5(OH)2+ -H+-[Z]3-
hydrolysis
Ammonium Exchange
Rare Earth Exchange
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Reaction Mechanism for Hydrothermal Dealumination and Stabilization of Y Zeolites
Framework Dealumination
Framework Stabilization
Al O Si O Si
O
Si
O
Si
O Si O Si
O
Si
O
Si
H H H H
+H2O
(Steam) +Al(OH)3
O Si O Si
O
Si
O
Si
H H H H
Hydroxyl Nest
(defect site)
Si O Si O Si
O
Si
O
Si
+SiO2
(Steam)
Hydroxyl Nest
(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)
0 10 20 30 40 50 60 70 80 90
100
24.21 24.26 24.31 24.36 24.41
UCS (Å)
RE
leve
l, %
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Zeolite Active Site Distribution
Equilibrium US-Y Zeolite unit cell size 24.25 Å Framework Si/Al = 27 7 Al atoms / unit cell
Equilibrium CREY Zeolite unit cell size 24.38 Å Framework Si/Al = 7.8 22 Al atoms / unit cell
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Dealumination Effect of Si / Al ratio on Zeolite
Properties
High Al Low Al
zeolite unit cell size thermal stability
hydrothermal stability
intrinsic cracking activity hydrogen transfer activity
low high high
low low
high low low
high high
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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
Gasoline
MON
RON
0
1
2
3
0
1
2
24.24 24.28 24.32 24.36 24.40
Zeolite Unit Cell Size, Å
Del
ta R
ON
, Del
ta M
ON
D
elta Gasoline Yield, W
t%FF
Increasing rare earth
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Relative Coke Selectivity of Zeolite Types
Equilibrium Unit Cell Size
Rel
ativ
e C
oke
Sele
ctiv
ity
REUSY
CREY unit cell size range for minimum coke 24.28 - 24.34 Å
USY
CSSN CSX
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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
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
Matrix Requirements
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Example Morphologies
Tuneable Matrix Alumina (TMA)
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Matrix Technology
Matrix System Type 1 Type 2 Type 3
Bottoms Cracking
+++
+
++
Coke/Gas Selectivity
+
+++
++
Vanadium Tolerance
+++
+
++
Nickel Tolerance
+
+++
++
Optimal matrix system is selected depending on the main operating objectives / constraints as below
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d (P
ore
Volu
me)
/ d
log
(Por
e D
iam
eter
)
0
0.1
0.2
0.3
0.4
0.5
0.6
10 100 1,000 10,000
Catalyst A (steamed) REUSY High Matrix Activity
Catalyst B (steamed) REUSY Moderate Matrix Activity
Pore Diameter, (Å) www.gbhenterprises.com
Ni Ni
Ni
Ni
Ni
Ni
Ni Ni
Ni
Ni
Ni Ni Ni
Ni Ni
Highly Dispersed - Poor Ni Tolerance Good Ni Support High Ni dehydrogenation activity
Nickel Tolerance - Matrix Consideration
Ni Ni Ni Ni Ni
Ni
Ni Ni Ni Ni
Nickel Agglomeration Chemical Reaction Poor Ni Support Low Ni dehydrogenation activity Å 100
Ni Al
Al
Al
Al
Al
NiAl2O4
Solid State Diffusion Chemical Reaction Strong Metal-Support Interaction Low Ni dehydrogenation activity
Ni trapping matrix
solid state
diffusion
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SA/K Number
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
SA/K number = Total ECat Surface Area Kinetic Conversion
= Total ECat Surface Area MAT Conv. / (100 - MAT Conv.)
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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
Zeolite / Matrix Surface Area Ratio of Steamed Catalyst
Amorphous Cracking
Zeolite Cracking
LCO
, wt%
C
oke,
wt%
0 2 4
2.0
4.0
24.0
25.0
26.0
38.0
40.0
42.0
44.0 G
asol
ine,
wt%
Dry
Gas
, wt%
H
CO
, wt%
C
3 +
C4,
wt%
1.0
1.4
1.8
16.0
15.0
14.0
13.0
15.0
14.0
13.0
12.0
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FCC Additives
ZSM-5 Additives
ZSM-5 Additive Particle
MICROSTRUCTURE MESOSTRUCTURE
MACROSTRUCTURE
75 µm
Zeolite ZSM-5
7 µm
Binder
Filler
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ZSM-5 framework structure ZSM-5 pore structure
Zeolite ZSM-5 Crystal Structure
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ZSM-5 Shape Selectivity
slow
Products
Products
Reactants
fast
Non-reactants
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Selective Conversion of Low Octane Species
The relative cracking for various hydrocarbons are:
Rel. rate Rel. octane Hydrocarbon Type
Straight chain paraffins & olefins
Moderately branched paraffins & olefins
Highly branched paraffins & olefins
Naphthenes
Aromatic side-chains
Fast
Moderate
Slow
Slow
Slow
Low
Moderate
High
Low
High
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ZSM-5 Additive Technology Cracking Mechanism
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
89
90
91
92
93
94
95
-40 -30 -20 -10 0 10 20 30
Days into ZSM-5 Usage
Gas
olin
e R
esea
rch
Oct
ane
ZSM-5 Additive Provided an Immediate
1.8 RON Gain
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2
4
6
8
10
12
64 68 72 76 80 84
Conversion (wt%)
C3=
(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: Propylene Yield
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7
9
11
13
15
17
64 68 72 76 80 84
Conversion (wt%)
Tot
al C
4= +
iC4
(wt%
) DCR Testing of ZSM-5 Additive: Alky
Feed Yield
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)
No change in coke, dry gas, or bottoms yield
Gasoline RONc and MONc increased
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Environmental Additives
Sulfur Balance in an FCC Unit
F
C
C
Feed Sulfur Sulfides Thiophenes Benzothiophenes Multi-ring Thiophenes
Light Gases, H2S 20 - 60%
Gasoline 2 - 10%
Light Cycle Oil 10 - 25 %
Heavy Cycle Oil 5 - 35 %
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 )
MeSO4 (s) + 4 H2 (g) = MeS (s) + 4 H2O (g)
RISER: Reduction of Metal Sulfate
MeSO4 (s) + 4 H2 (g) = MeO (s) + H2S (g) + 3 H2O (g)
Stripping Steam
STRIPPER: Hydrolysis of Metal Sulfide MeS (s) + H2O (g) = MeO (s) + H2S (g)
FEED ( with Sulfur )
FLUE GAS ( with SOx )
Regenerator Air
REGENERATOR: Formation of SOx S (coke) + O2 (g) = SO2 (g)
SO2 (g) + ½ O2 (g) = SO3 (g)
Formation of Metal Sulfate SO3 (g) + MeO (s) = MeSO4 (s)
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FEED SULFUR IN GASOLINE vs GASOLINE CUT POINT
1
2
3
4
5
6
7
8
9
180 185 190 195 200 205 210 215 220 225 230 Gasoline C.P. (ºC)
Feed
Sul
phur
in G
asol
ine
(%)
W/O Additive Comp X
Comp X Allowed Refinery C to Reduce Sulfur by ca. 20-25%
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NOx Emissions: XNOx vs. Pt. Promoter
0
100
200
300
400
500
-1.5 -1.0 -0.5 0.0 0.5 1.0 1.5 2.0
NO
(ppm
)
Hours
Addition of 0.5% XNOx
Addition of Pt based Promoter
60% Reduction
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Catalyst Manufacturing
Synthesis of Zeolite Y
NaSiO3 NaAlO2
Al2(SO4)3 Seeds
ca. 100°C, 1-2 days www.gbhenterprises.com
Sulfate Aluminate
Silicate Aluminium
Sodium
Sodium
Seeds ML-Gel
Sulfate
Beltfilter
Effluent
Aluminium
Water
Beltfilter Na-Y Zeolite
ZEOLITE PLANT (Part 1)
RE-Y Zeolite
(NH4)2SO4
RECl3 /
Water
Beltfilter
Effluent
NH4-Y /
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Bag Filter System
Calciner
US-Y Zeolite CREY /
ZEOLITE PLANT (Part 2)
RE-Y Zeolite
NH4-Y /
Hot Air
Dryer
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Binder Water Clay
Mixing
Water
Calciner
CATALYST FCC
FCC PLANT
Water
Beltfilter LS-USY
(NH4)2SO4
Effluent
RECl3 /
WET END
Spray Drier
Hot Air
Scrubbing System
DRY END
Zeolite (e.g.. CREY/USY)
Mixing
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Reaction Chemistry
Boiling Range Distribution of FCC Feed and Products
Wt%
FF
Boiling Point, °C
Gas LPG Naphtha LCO Slurry /
FEED
Feedstock 40
0°C
221°
C
C4
C2
PRODUCTS
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Hydrocarbon Types CHAIN STRUCTURES
Paraffin
H H H H
H H H H
R R
H H H H H H
RING STRUCTURES
Olefin
H H H
H H H H
R R
H H H H H
Naphthene
H
H H
H R
H H H
H H
H H
R
H H
H H H
H
H
Alkylaromatic H
H H
H H
H H H H
R R
H H
H
Crackability (Conversion): Paraffinic > Naphthenic > Aromatic
Coke-forming tendency (Heat Balance): Paraffinic < Naphthenic < Aromatic
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Principles of Catalysis
Catalysts Lower Activation Energies of Forward & Backwards Reactions, Increasing the Rates of Both The Heat of Reaction is Unchanged by the Catalyst The Position of Thermodynamic Equilibrium is Unchanged by the Catalyst Non-Equilibrium Distributions Occur Under Kinetic Controlled Conditions
Free
Ene
rgy
Reaction Co-ordinate
ECatalytic
∆ Hreaction
EThermal
EB
EA
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0
50
100
150
Thermal vs Catalytic Cracking n-Hexadecane @ 500°C
Mol
es P
rodu
ct /
100
Mol
es C
rack
ed
Carbon Number
C1 C2 C3 C4 C5 C6 C7 C8 C9 C10 C11 C12 C13 C14
Catalytic Cracking
Thermal Cracking
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Principle Reactions in FCC
Olefins Cracking Light Olefins
Isomerisation other Naphthenes
Naphthenes Cracking Olefins
Transalkylation other Aromatics
Aromatics Side-chain Cracking
unsubstituted Aromatics + Olefins
Dehydrogenation poly-Aromatics
Dehydrogenation Coke
Condensation Condensation
Dehydrogenation cyclo-Olefins
Dehydrogenation Aromatics
Cracking Paraffins + Olefins Paraffins
H Transfer Paraffins
Condensation Cyclisation
Naphthenes Dehydrogenation
Coke
Olefins Paraffins Isomerisation H Transfer Branched Branched
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β - Scission (cracking) Reactions
Cracking Reaction Mechanism
H+
Si O
Al O
Si O -
Catalyst (Acid Site)
H H H H
H H H H
R R
H H H H
Carbenium Ion H
H H H
H H H
R R
H H H H
+
H H
Protonation
H H H H
H H H
R R
H H H H
+ H H
ß-scission
Olefin Product
H H
H H
R
H H H H
+
H H
H
R H
H
H H
H H
R
H H H H
+
H H
H
H H
R H
H
+ H
Intermolecular Rearrangement
H H
H
H H
R H
H
+ H
H H
H H
R H
H
H
Deprotonation
-
H+ www.gbhenterprises.com
Thermal Reaction Mechanism
Thermal cracking gives high yields of methane, alpha-olefins and ethylene, no increased branching
H H
H H H
H H H H H
H R
H H H H
Free radical formation
- H . Secondary Free radical
H H H H
H H
R
H H H
H H H
H
H .
ß-scission (Cracking)
Primary Free radical
. H H
H H
H H
R
H H
alpha- Olefin Product
H
H H
H
H H
ß-scission (cracking) Ethylene
H
H
H H
New free radical
H H
H
R
H
.
homolytic fission
C H homolytic fission
C C homolytic fission
C C
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Summary of Cracking Reactions
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
Alkylaromatic Alkylaromatic + Olefin
Naphthene Olefin
Paraffin Paraffin + Olefin
Olefin Olefin + Olefin
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Hydrogen Transfer Reactions
olefin + naphthene paraffin + cyclo-olefin
Hydrogen Transfer Reactions
olefin + cyclo-olefin paraffin + cyclo-diolefin olefin + cyclo-diolefin paraffin + aromatic
H
CH - CH2
CH2 - CH2 CH - R” H2 C
R - CH - CH2 - R’ +
H+ R - CH = CH - R’
olefin protonation
R - CH - CH - R’ H
+
hydrogen transfer
H
R - CH - CH2 - R’
CH - CH2
CH2 - CH2 CH - R” H2 C
+
H
CH - CH
CH2 - CH2 CH - R” H2 C
+ CH = CH
CH2 - CH2 CH - R” H2 C - H+
proton loss
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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 air
ENERGY IS REQUIRED TO
HEAT AIR
∆H cracking
ENERGY IS REQUIRED TO CRACK FEED
∆H vaporization
ENERGY IS REQUIRED TO
VAPORISE FEED
∆H losses
ENERGY IS REQUIRED FOR
HEAT LOSSES TO ATMOSPHERE
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FCC Delta Coke Types
Occluded Feed Metals Catalytic
unstripped hydrocarbons (product to regenerator) high hydrogen content uncracked heavy feed components e.g. asphaltenes, Conradson carbon residue Formed via dehydrogenation activity of contaminant metals e.g. nickel, vanadium formed as a bi-product of desired catalytic cracking
15%
15%
5%
65%
VGO 14%
28%
28%
30%
Resid
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Feed Dependence of Delta Coke
Contaminant Coke (Metals Coke) Increases
Feed Residue Coke (Conradson Carbon) Increases
Occluded Coke (Cat/Oil Coke) Same / Slight Increase
Catalytic Coke (Conversion Coke) Decreases
Contaminant Coke
Feed Residue Coke
Occluded Coke 0.10
0.30
0.50
0.80
1.60
Del
ta C
oke
Catalytic 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
Lower conversion by :
higher regen. temperature
lower cat/oil (lower severity)
Lower effective activity due to :
coke blockage of pores
metals contamination
increased nitrogen poisoning
FCC
Uni
t Con
vers
ion Regen T
Cat/Oil Ratio
Unit Conversion
Delta Coke, wt.%
Increasing Resid content
Constant Riser Outlet Temp. Constant Coke Operation (Unit at Max. Blower Capacity)
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Selecting the Right Combination
Gasoline Mode Operation
FCC Optimization for Gasoline Production
high Zeolite / Matrix ratio (Z/M) high Hydrogen Transfer (high ucs) high Catalyst Activity (Conversion)
C3=, C4='s for cat. polym. C3= for dimersol / petrochem. C3's, C4's for LPG
C3=, C4='s, i-C4 for alkylation i-C4= for MTBE
Fuel Gas H2, C1, C2, C2=
Gasoline C5 - 221°C Kerosene 150 - 250°C
Cat. Heating Oil
Diesel 200 - 350°C
FCC UNIT
Crude Atmospheric Column
Straight Run Products
Atmospheric Residue Vac. Gas Oil
Vacuum Residue
Vacuum Column
Residue Hydrotreater
HT Resid
Gasoline Selectivity is favored by:
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FCC Optimization for Gasoline Production
high Catalyst / Oil ratio moderate Riser Outlet Temperature high ECat Activity (MAT)
C3=, C4='s for cat. polym. C3= for dimersol / petrochem. C3's, C4's for LPG
C3=, C4='s, i-C4 for alkylation i-C4= for MTBE
Fuel Gas H2, C1, C2, C2=
Gasoline C5 - 221°C Kerosene 150 - 250°C
Cat. Heating Oil
Diesel 200 - 350°C
FCC UNIT
Crude Atmospheric Column
Straight Run Products
Atmospheric Residue Vac. Gas Oil
Vacuum Residue
Vacuum Column
Residue Hydrotreater
HT Resid
Gasoline Selectivity is favored by:
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Distillate Mode Operation
FCC Optimization for Middle Distillates
Production
high Matrix Activity (lower Z/M) high Hydrogen Transfer (high ucs) low Catalyst Activity (low Conversion)
C3=, C4='s for cat. polym. C3= for dimersol / petrochem. C3's, C4's for LPG
C3=, C4='s, i-C4 for alkylation i-C4= for MTBE
Fuel Gas H2, C1, C2, C2=
Gasoline C5 - 221°C
Kerosene 150 - 250°C
Cat. Heating Oil
Diesel 200 - 350°C
FCC UNIT
Crude Atmospheric Column
Straight Run Products
Atmospheric Residue Vac. Gas Oil
Vacuum Residue
Vacuum Column
Residue Hydrotreater
HT Resid
Middle Distillate Selectivity is favored by:
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FCC Optimization for Middle Distillates
Production
low Catalyst / Oil ratio low Riser Outlet Temperature low ECat Activity (MAT) use of Recycle (HCO/Slurry)
C3=, C4='s for cat. polym. C3= for dimersol / petrochem. C3's, C4's for LPG
C3=, C4='s, i-C4 for alkylation i-C4= for MTBE
Fuel Gas H2, C1, C2, C2=
Gasoline C5 - 221°C
Kerosene 150 - 250°C
Cat. Heating Oil
Diesel 200 - 350°C
FCC UNIT
Crude Atmospheric Column
Straight Run Products
Atmospheric Residue Vac. Gas Oil
Vacuum Residue
Vacuum Column
Residue Hydrotreater
HT Resid
Middle Distillate Selectivity is favored by:
www.gbhenterprises.com
Light Olefins Mode Operation
FCC Optimization for Light Olefins Production
low Hydrogen Transfer (low ucs) use of ZSM-5 Zeolite containing additives high Catalyst Activity (very high Conversion)
C3=, C4='s for cat. polym. C3= for dimersol / petrochem. C3's, C4's for LPG
C3=, C4='s, i-C4 for alkylation i-C4= for MTBE
Fuel Gas H2, C1, C2, C2=
Gasoline C5 - 221°C
Kerosene 150 - 250°C
Cat. Heating Oil
Diesel 200 - 350°C
FCC UNIT
Crude Atmospheric Column
Straight Run Products
Atmospheric Residue Vac. Gas Oil
Vacuum Residue
Vacuum Column
Residue Hydrotreater
HT Resid
Light Olefin Selectivity is favored by:
www.gbhenterprises.com
FCC Optimization for Light Olefins Production
high Riser Outlet Temperature high Catalyst / Oil ratio high ECat Activity (MAT)
C3=, C4='s for cat. polym. C3= for dimersol / petrochem. C3's, C4's for LPG
C3=, C4='s, i-C4 for alkylation i-C4= for MTBE
Fuel Gas H2, C1, C2, C2=
Gasoline C5 - 221°C
Kerosene 150 - 250°C
Cat. Heating Oil
Diesel 200 - 350°C
FCC UNIT
Crude Atmospheric Column
Straight Run Products
Atmospheric Residue Vac. Gas Oil
Vacuum Residue
Vacuum Column
Residue Hydrotreater
HT Resid
Light Olefin Selectivity is favored by:
www.gbhenterprises.com
Short Contact Time Operation
FCC Optimization for Short Contact Time
Operations
high Catalyst Activity balanced Zeolite/Matrix ratio (Z/M) high Hydrogen Transfer (high ucs)
C3=, C4='s for cat. polym. C3= for dimersol / petrochem. C3's, C4's for LPG
C3=, C4='s, i-C4 for alkylation i-C4= for MTBE
Fuel Gas H2, C1, C2, C2=
Gasoline C5 - 221°C Kerosene 150 - 250°C
Cat. Heating Oil
Diesel 200 - 350°C
FCC UNIT
Crude Atmospheric Column
Straight Run Products
Atmospheric Residue Vac. Gas Oil
Vacuum Residue
Vacuum Column
Residue Hydrotreater
HT Resid
Short Contact Time Operation is favored by:
www.gbhenterprises.com
FCC Optimization for Short Contact Time
Operations
high Riser Outlet Temperature high Catalyst / Oil ratio high ECat Activity (MAT)
C3=, C4='s for cat. polym. C3= for dimersol / petrochem. C3's, C4's for LPG
C3=, C4='s, i-C4 for alkylation i-C4= for MTBE
Fuel Gas H2, C1, C2, C2=
Gasoline C5 - 221°C Kerosene 150 - 250°C
Cat. Heating Oil
Diesel 200 - 350°C
FCC UNIT
Crude Atmospheric Column
Straight Run Products
Atmospheric Residue Vac. Gas Oil
Vacuum Residue
Vacuum Column
Residue Hydrotreater
HT Resid
Short Contact Time Operation is favored by:
www.gbhenterprises.com
Gasoline Olefins Reduction
FCC Optimization for Gasoline Olefins
Reduction
high Zeolite / Matrix ratio (Z/M) high Hydrogen Transfer (high ucs) moderate Matrix Activity (SAM-700) high Metals Tolerance (e.g. Ni and V)
C3=, C4='s for cat. polym. C3= for dimersol / petrochem. C3's, C4's for LPG
C3=, C4='s, i-C4 for alkylation i-C4= for MTBE
Fuel Gas H2, C1, C2, C2=
Gasoline C5 - 221°C Kerosene 150 - 250°C
Cat. Heating Oil
Diesel 200 - 350°C
FCC UNIT
Crude Atmospheric Column
Straight Run Products
Atmospheric Residue Vac. Gas Oil
Vacuum Residue
Vacuum Column
Residue Hydrotreater
HT Resid
Gasoline Olefins Reduction is favored by:
www.gbhenterprises.com
FCC Optimization for Gasoline Olefins
Reduction
high Catalyst / Oil ratio low Riser Outlet Temperature high ECat Activity high Conversion
C3=, C4='s for cat. polym. C3= for dimersol / petrochem. C3's, C4's for LPG
C3=, C4='s, i-C4 for alkylation i-C4= for MTBE
Fuel Gas H2, C1, C2, C2=
Gasoline C5 - 221°C Kerosene 150 - 250°C
Cat. Heating Oil
Diesel 200 - 350°C
FCC UNIT
Crude Atmospheric Column
Straight Run Products
Atmospheric Residue Vac. Gas Oil
Vacuum Residue
Vacuum Column
Residue Hydrotreater
HT Resid
Gasoline Olefins Reduction is favoured by:
www.gbhenterprises.com
Questions ?