FCC Catalyst Design: Morphology, Physiology, Reaction Chemistry and Manufacturing

FCC Catalyst Design: Morphology, Physiology, Reaction Chemistry and Manufacturing

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

1. FCC Gatalyst Design
Morphology, Physiology, Reaction
Chemistry and Manufacturing

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2. GBH Enterprises Ltd.
= Introduction

= ECC 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

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3. FCC: POSITION IN REFINERY

Crude à Straight Run
——.,| Atmospheric | cts
Column

Atmospheric

Residue Vac. Gas Oil
|

y
Vacuum
Column

Vacuum

Residue HT Resid

y

Residue
Hydrotreater

FCC UNIT

+ Fuel Gas H2, C1, C2, C2=

C3's, C4's for LPG

C3= for dimersol / petrochem.
C3=, C4='s for cat. polym.
C3=, C4='s, i-C4 for alkylation
i-C4= for MTBE

> Gasoline C5 - 221°C

| Kerosene 150 - 250°C

200 - 350°C

> Cat. Heating Oil

> Diesel

In the FCC unit high mol. wt.
feeds
(VGO / Residue) are converted to
lighter, more valuable, products

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4. FGG Unit Operating Conditions : typical
Example

530°C
DISENGAGER

E 510°C
Stripping steam
735°C

REGENERATOR
720°C

Regenerator
flue gas

Feed 250°C

. 190°C
mm Fegpnerstor
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5. Catalyst Physical Properties

RETENTION / LOSSES
Mm - Attrition Resistance

FLUIDIZATION
- Particle Size Distribution
- Average Bulk Density

HEAT TRANSPORT
- Specific Heat Capacity

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6. GBH Enterprises Ltd.

FGG Gatalyst Components

{
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7. FCC Catalyst Components

Zeolite Y

Pseudo crystalline
Matrix Aluminas

| 70 ym (avg.)
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8. FCG Gatalyst Gomponents

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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9. Matrix

e Forms the continuum that holds together
the zeolite crystals

e Acid sites on active matrix component
catalyze cracking of feed molecules too
large to enter zeolite pores

e Matrix porosity facilitates diffusion of feed
molecules to zeolite

e Metals traps (e.g. for Vanadium or Nickel)
may be incorporated in the matrix

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10. a. GBH Enterprises Ltd.

The Zeolite

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11. a

Structure of Zeolite Y

Supercage

NE Va (a-cage)

~+7—— Sodalite cage
(B-cage)

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12. Zeolite Structure and Properties

= Zeolites are crystalline
microporous, alumino silicates

"Framework alumina (AlQ;) units
are associated with Acidic Active
Sites

= Cations within microporous
cages and channels (M"* = H*,
Las, Ces*, Ce4*)

= Hydrocarbon conversion
catalyzed at acid sites within
microporous channels

(Mn {(SiO,), (ALO) rrameworia Acid Site Activity and Acid Site
Density determine the Activity

o and Selectivity of the zeolite
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13. LC

Zeolite Acidity

= Bronsted acid
site,

IN yh ? je m Proton (H) donor
Si Al Si
Lewis acid site

O —— Al—— O Trivalent AI - hydride ion abstractor

o)
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14. LC

Bronsted Acid site

AR,

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15. 2 Routes for Zeolite Y
= Stabilization

= HREY

= RE ion-exchange calcine NH,* ion-exchange

= NaY EY , CREY NH¿CRE
= USY

= NH,* ion-exchange ultrastabilize RE** ion-exchange

=» NaY___, NH,Y USY REUSY

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16. > Sites (H*)

Ammonium Exchange
= Nat-Z + NH,~———— Nat + NH,+-Z

. calcine

= NH,*-Z u; H+-Z + NH;
2

Rare Earth Exchange

3Nat-Z + RE(H20)g?* 3Nat + RE(H,O),%*-[Z]5°

RE(H,0),*(Zy 2 DM RE(H,O) (OH): -H*-IZ]5

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17. Reaction Mechanism for Hydrothermal
. Dealumination and Stabilization of Y Zeolites

Framework NV Y
Dealumination Si
o 0
H20
Ss ou oa > =i—o0 OT si *AN(OH),
(Steam)
0
fl f Hydroxyl Nest
F k \ aN (defect site)
rework AY y
Stabilization 4 Si
Q
A H __ +Si02 a _
—SITo—H u = SF Si FO 5 o—si=
(Steam)
° 9
Hydroxyl Nest Jl
rn 1]
hi (defect site) MN

ii

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18. Unit-Gell Size and Si/Al ratio

= Numerous relationships given tn the literature

= Breck and Flanigen relationship widely used

= Ny / ucs = 115.2 [ a,- 24.191 ]
= and: Ns, / ucs = 192 - N,,/ ucs
=" thus: Si / Al Framework Ng / Nai

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19. Control of the equilibrium UGS

=

= UGS (A)

=» As-synthesized Nay 24.64 (54 Al/ uc)

= Ultra stabilized Y 24.54 (40 Al/ uc)

=» Steam deactivated US" 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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20. RE level, %
>
[=]

1
24.21 24.26 24.31 24.36 24.41
UCS (A)

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21. Zeolite Active Site Distribution

= + “ T =
Ye Ye A A
-? =
J ad « N m … > + \
x f \ N a Y y T
> \ "y x \
X A %
a ay A
NL
A
4
À
Equilibrium US-Y Zeolite Equilibrium CREY Zeolite
unit cell size 24.25 À unit cell size 24.38 À
Framework Si/Al = 27 Framework Si/AI = 7.8

> 7 Al atoms / unit cell 22 Al atoms / unit cell
|
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22. LC

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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23. Major Effects of Equilibrium
= Unit Gell Size

= Increasing Unit Cell Size :

e Increases Active Site Density
e Decreases Active Site Strength

= Hence, Increased Hydrogen Transfer vs. Cracking :

e Increased Gasoline Selectivity
« Lower Gasoline Octane Numbers (RONc and MONc)

e Decreased LPG (C, and C,) Selectivity
e Lower LPG Olefinicity

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24. Delta RON, Delta MON

3

Octane Response vs. Zeolite
Unit-Cell Size

n

2 r
Gasoline

o
d44%1M ‘PISIA SUIIOSE9 eyaq

24.24 24.28 24.32 24.36 24.40
Zeolite Unit Cell Size, À

Increasing rare earth

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25. dB

Relative Coke Selectivity of Zeolite Types

unit cell size range CREY
USY for minimum coke
24.28 - 24.34 A

REUSY

CSSN CSx

Relative Coke Selectivity

Equilibrium Unit Cell Size

=

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26. GBH Enterprises Ltd.

The Matrix

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27. Catalytically active surface

Less selective in cracking than zeolite

Variable acid site strength and pore structure

e Helps crack the bottoms to provide ‘feed’ for
the zeolite component

e Important for metals tolerance

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28. Matrix Design Gonsiderations

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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29. - Tuneable Matrix Alumina (TMA)

<>

Example Morphologies

Le bg),
AAO)

Li y
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30. Matrix Technology

n= 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 + Gros oP +++
Type 3 ++ +. ++ ++

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31. d (Pore Volume) / d log (Pore Diameter)

3

0.6

0.5

0.4

0.3

0.2

0.1

+ Catalyst A (steamed)
REUSY
High Matrix Activity

Catalyst B (steamed)
REUSY
Moderate Matrix Activity

10

100 1,000 10,000

Pore Diameter, (A)
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32. Highly Dispersed - Poor Ni Tolerance
Good Ni Support
High Ni dehydrogenation activity

Nickel Agglomeration
Chemical Reaction

Poor Ni Support
Low Ni dehydrogenation activity

Ni trapping matrix

Solid State Diffusion

Chemical Reaction Ni] u solid state Al
Strong Metal-Support Interaction diffusion
Low Ni dehydrogenation activity Al >; Al

a NiAI204
Al

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33. 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:
simproves 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

LAVOID EXCESS CATALYST SURFACE AREA - ONLY NEED
SURFACE AREA THAT CONTRIBUTES TO PRODUCING DESIRED
CONVERSION PRODUCTS

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34. -- Major Effects of Increased Z/M
E Ratio

Increasing Z/M :

_ Increases Selective Zeolite Cracking
_ Lower Coke and Fuel Gas (C,-) Yields
_ Increased Gasoline Selectivity

But,
- Lower LCO Selectivity
~ Increased Bottoms Selectivity

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35. Effect of Zeolite/Matrix Ratio on Product Selectivity's

MAT Reaction Conditions: 60 wt% conversion Feed: 0.919 g/ml, 11.5 Watson K

& 440 BE +
= 420 140 >
E 40.0 3
So dor
S 380 a
a pa 2
F 16.0

26.0 $
= 150 E
Sg 250 ;
© 140 8
E

24.0 130 7
in 8
3 18 ©
5 40 e
$ 14 8
E Oo
S 20 10 8

0 2 4
Amorphous | » Zeolite
Cracking Cracking

Zeolite / Matrix Surface Area Ratio of Steamed Catalyst
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36. GBH Enterprises Ltd.

ECC Additives

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37. GBH Enterprises Ltd.

ZSM-5 Additives

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38. ZSM-5 Additive Particle

MICROSTRUCTURE MESOSTRUCTURE

ga

Zeolite
ZSM-5

MACROSTRUCTURE

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39. an

Zeolite ZSM-5 Crystal Structure

ao

ZSM-5 framework structure ZSM-5 pore structure

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40. m ZSM-5 Shape Selectivity

Products

An

a
# à
Bp ue

“NN

„an
fie sow À
x

Reactants |

6
Je
p pq

| Non-reactants

Products

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41. 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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42. 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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43. Commercial Data: Unit Response
to 3 wt% Additive Addition

ZSM-5 Additive
Provided an Immediate
1.8 RON Gain

927

914

o
E
Le]
S
o
°
<£
o
$
a
o
ao
o
a
o
£
5
o
a
©

90

89 T Tr
-40 -30 -20 -10 0 10 20 30

: Days into ZSM-5 Usage
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44. 72 76
_ Conversion (wt%)

—* ECAT 521°C ECAT 543°C 4 ECAT 566°C
> 4% Additive 521°C. 2 4% Additive 543°C —@ 4% Additive 566°C.

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45. —* 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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46. ees
LC

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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47. GBH Enterprises Ltd.

Environmental Additives

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48. =), Sulfur Balance tn an FGG
o Unit

Light Gases, HS 20 - 60%

HN Gasoine 2- 10%
Feed Sulfur C F :
A u = 0)
Sulfides Light Cycle Oil 10-25%
Thiophenes A
Benzothiophenes Ce Heavy Cycle Oil 5-35%
Multi-ring Thiophenes

EF Goke 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

¡ gback end of the gasoline
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49. FLUE GAS
(with SOx )

REGENERATOR:

Formation of SOx
S(coke) + O,(g) = SO, (g)
SO» (9) + 20,(g) = SO; (g)

Formation of Metal Sulfate
SO, (g) + MeO(s) = MeSO, (s)
Regenerator
_ | Air

Catalytic SOx Reduction

7 = PRODUCTS
(with H,S )

STRIPPER:
Hydrolysis of Metal Sulfide

Mes (s) +H,0 (g) = MeO (s) + HS (g)

| Stripping Steam

RISER:

Reduction of Metal Sulfate

MeSO, (s) +4 H,(g) = MeS (s) + 4 H,0 (g)

MeSO, (s) + 4H, (g) = MeO (s) + HS (g) + 3 H,0 (g)

FEED
( with Sulfur )

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50. FEED SULFUR IN GASOLINE vs GASOLINE CUT POINT

9
8
+
6
5
4
3
2

€
2
£
3
3
8
Oo
£
5
2
S
Fl
an
3
3
2

205 210 215 220 225
Gasoline C.P. (°C)

—— W/O Additive E Comp X

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51. Addition of Pt
based Promoter

60% Reduction

oom

Addition of 0.5% XNOx
00 05 10 15 20
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52. f \_ GBH Enterprises Ltd.

Gatalyst Manufacturing

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53. = Synthesis of Zeolite Y

Al (SO4)s |

NaSiO, NaAlO,
| | u Seeds

ca. 100°C, 1-2 days
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54. ZEOLITE PLANT (Part 1)

Sodium
Silicate
Aluminium Sodium
Sulfate Aluminate
ML-Gel Seeds
yy
Water
RECI, /
(NH4)2SO4 due
CO Beitfilter CR.
Aluminium —_,
Sulfate iL © Bettfitter O
NH,-Y/
RE-Y Zeolite
Effluent
( ) Beltfilter X )
Effluent

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55. ZEOLITE PLANT (Part 2)

Bag Filter System

Dryer

NH¿Y/
RE-Y Zeolite

— Calciner

Hot Air CREY /
US-Y Zeolite

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56. FCC PLANT

Zeolite Water a
(e.9.. CREY/USY)

AAA | Spray

Drier
RECI,/
(NH,)SO, Water
——
Mixing Scrubbing System
>
© ___Bettfilter Oisusv o IR a
Calciner
— Clay
Water i
Effluent Auer
FCC
y CATALYST
WET END Mixing DRY END

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57. FU GBH Enterprises Ltd.

Reaction Chemistry

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58. Boiling Range Distribution of
OD FGG Feed and Products

a
8 3 9 9
à = FEED
N +
L
L
x
= PRODUCTS
Gas LPG Naphtha Slurry / Feedstock

Boiling Point, °C

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59. Alkylaromatic

Crackability (Conversion): Paraffinic > Naphthenic > Aromatic

j Coke-forming tendency (Heat Balance): Paraffinic < Naphthenic < Aromatic
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60. Principles of Gatalysis

Catalysts Lower Activation Energies
Ernermal of Forward & Backwards Reactions,
Increasing the Rates of Both

Ecatalytic

The Heat of Reaction is Unchanged

>
> by the Catalyst
=
i The Position of Thermodynamic
® Equilibrium is Unchanged by the
lo Es Catalyst
=
E, la Fa cecton Non-Equilibrium Distributions Occur
= Under Kinetic Controlled Conditions

Reaction Co-ordinate

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61. Thermal vs Catalytic Cracking
n-Hexadecane @ 500°C

a
Ss

Thermal Cracking
BH Catalytic Cracking

dires
ci C2 C3 C4 C5 C6

C7 C8 C9 C10 C11 C12 C13 C14

2
Ss

Moles Product / 100 Moles Cracked
a
g

o

Carbon Number

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62. sE

= Principle Reactions in FGG

Paraffins Cracking Paraffins + Olefins
= a
Olefins Cracking Light Olefins
Isomerisation Branched H Transfer Branched
Olefins Paraffins
H Transfer Raraffine
Cyclisation Dehydrogenation
Naphthenes Condensation Coke
Naphthenes en Olefins
Isomerisation
other Naphthenes i
Dehydrogenation . Dehydrogenation :
cyclo-Olefins Aromatics
Side-chain Crackin
Aromatics SEEN SIENNE. unsubstituted Aromatics + Olefins
Transalkylation
other Aromatics
Dehydrogenation Dehydrogenation Cok
. i oke
Condensation Boley rol pues Condensation

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63. f \_ GBH Enterprises Ltd.

p - Scission (cracking)
Reactions

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64. Reaction Mechanism

Gracking
A es.

Ht

Catalyst (Acid Site)

Protonation

Carbenium lon

B-scission

Olefin Product

Intermolecular

Rearrangemen

Deprotonation

Ht

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65. Thermal Reaction Mechanism

Free radical

formation

rr

-H=

H

H H H
HH HH 20
Secondary EN radical

homolytic fission
ce H B-seission NES sur
La D. fission (Cracking) C— E
c> — Te
=. 2 ey H oa
H H
pa u B-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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66. Summary of Gracking Reactions

Paraffin — _ Paraffin + Olefin
u 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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67. f \_ GBH Enterprises Ltd.

Hydrogen Transfer Reactions

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68. Hydrogen Transfer Reactions

olefin

+
a R-CH=CH-R’ - R-CH-CH-R’
Es protonation =
Ht
R-CH-CH,-R' Bean
4 i
|
oH - CH, hydrogen zen -CH,
ue x
HC CH-R” transfer H,C CH- R”
S 4 < 7.
CH, - CH, CH, - CH,
H
+ |
CH-CH CH=CH
7 S _H+ / N
H,C CH-R” H, C CH-R”
S 7 proton loss y 7
CH, - CH, CH, - CH,

olefin + naphthene paraffin + cyclo-olefin

olefin + cyclo-olefin paraffin + cyclo-diolefin
olefin + cyclo-diolefin paraffin + aromatic

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69. GBH Enterprises Ltd.

Heat Balance Considerations

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70. FCC Heat Balance Considerations

+. Most FCG process variables have an effect

on the heat balance - which, in turn, affects:
Conversion, Yields and Product: Qualities

e The FCC unit will always adjust itself to
remain in heat balance by burning enough
coke for the energy requirements

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71. - AH losses
ENERGY IS AH cracking
REQUIRED FOR ENERGY IS
HEATLOSSESTO = REQUIRED TO
ATMOSPHERE CRACK FEED

AH air AH vaporization
ENERGY IS ENERGY IS

¿ REQUIRED TO REQUIRED TO
HEAT AIR VAPORISE FEED
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72. o FCC Delta Coke Types

Occluded
Feed
Metals

Catalytic

ii

VGO Resid
- unstripped hydrocarbons 15% 14%
(product to regenerator)
high hydrogen content
__uncracked heavy feed 15% 28%
components e.g. asphaltenes,
Conradson carbon residue
= Formed via dehydrogenation 5% 28%
activity of contaminant metals
e.g. nickel, vanadium
> formed as a bi-product of 65% 30%

desired catalytic cracking

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73. Delta Coke

1.60

0.80

0.50
0.30
0.10

Feed Dependence of
Delta Goke

.
(Metals Coke) Increases

“feed Residue Coke
(Gonradson Carbon)
Increases

sOccluded Coke (Cat/ Oil
Coke) Same / Slight

Feed Residue Increase
Catalytic Coke Coke
Contaminant "Catalytic Coke
Coke (Conversion Coke)
Decreases

Occluded Coke

Decreasing Feed Quality —————>
Increasing: Density, ConCarbon, Metals, S, N.

Increasing Resid Content —————>
Increasing Ca/Cp ratio, Endpoint

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74. FCC Unit Conversion

Conversion Dependence on
Delta Goke

Constant Riser Outlet Temp.

Constant Coke Operation

Delta Coke, wt.%
Increasing Resid content

(Unit at Max. Blower Capacity)

Begenzi

Unit

Conversion
TI Cat/Oil

Ratio

—

Lower conversion by:

higher regen.
temperature

lower cat/ oil (lower
severity)

Lower effective activity
dueto:

coke blockage of pores
metals contamination

increased nitrogen
poisoning

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75. GBH Enterprises Ltd.

selecting the Right
Combination

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76. GBH Enterprises Ltd.

Gasoline Mode Operation

{
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77. FCC Optimization for Gasoline Production

Crude | atmospheric Sa -— Fuel Gas H2, C1, C2, C2=
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
| de i-C4= for MTBE
Vacuum > Gasoline C5 - 221°C
Column > Kerosene 150 - 250°C
——— Diesel 200 - 350°C
Vacuum Li, r ñ
Residue HT Resid FCC UNIT a AT ET
à À
Residue G li S I sf is f a
drenar asoline Selectivity is favored by:

high Zeolite / Matrix ratio (Z/M)
_ high Hydrogen Transfer (high ucs)

. _ high Catalyst Activity (Conversion)
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78. FCC Optimization for Gasoline Production

Crude | atmospheric ol —— Fuel Gas H2, C1, C2, C2=
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
ll a i-C4= for MTBE
Vacuum | Gasoline C5 - 221°C
Column > Kerosene 150 - 250°C
r > Diesel 200 - 350°C
Vacuum LL, : |
Residue HT Resid FCC UNIT a AT ET
=
Residue Gasoline Selectivity is f A
drenar asoline Selectivity is favored by:

high Catalyst / Oil ratio
moderate Riser Outlet Temperature

. high ECat Activity (MAT)
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79. GBH Enterprises Ltd.

Distillate Mode Operation

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80. FCC Optimization for Middle Distillates

Production
sua] Atmospheric Sp non + Fuel Gas H2, C1, C2, C2=
Solum C3's, C4's for LPG
C3= for dimersol / petrochem.
Atmospheric| — C3=, C4='s for cat. polym.
Residue Vac. Gas Oil || Gas Oil C3=, C4='s, i-C4 for alkylation
dl i-C4= for MTBE
Vacuum + Gasoline C5-221°C
Column [> Kerosene 150 - 250°C
\ rt Diesel 200 - 350°C
facuum = 1
Residue HT Resid FCC UNIT | ~~ Cat. Heating Oil
à À
Residue B aan Ma 7
Rydrotreater 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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81. FCC Optimization for Middle Distillates

Production
sua] Atmospheric Sp non + Fuel Gas H2, C1, C2, C2=
Solum C3's, C4's for LPG
C3= for dimersol / petrochem.
Atmospheric| — C3=, C4='s for cat. polym.
Residue Vac. Gas Oil || Gas Oil C3=, C4='s, i-C4 for alkylation
dl i-C4= for MTBE
Vacuum + Gasoline C5-221°C
Column [> Kerosene 150 - 250°C
\ rt Diesel 200 - 350°C
facuum = 1
Residue HT Resid FCC UNIT | ~~ Cat. Heating Oil
à À
Residue B aan Ma 7
Rydrotreater 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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82. GBH Enterprises Ltd.

Light Olefins Mode Operation

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83. FCC Optimization for Light Olefins Production

sua] Atmospheric Sp non + Fuel Gas H2, C1, C2, C2=
Lolumn C3's, C4's for LPG
C3= for dimersol / petrochem.
Atmospheric — C3=, C4='s for cat. polym.
Residue ‘Vac. Gas Oil | Gas Oil C3=, C4='s, i-C4 for alkylation
y i-C4= for MTBE
Vacuum + Gasoline C5 -221°C
Column > Kerosene 150 - 250°C
r > Diesel 200 - 350°C
Vacuum m M
Residue HT Resid FCC UNIT | ~~ Cat. Heating Oil
à À
Residue = = For: 7
arcos Light Olefin Selectivity is favored by:

ii

_ low Hydrogen Transfer (low ucs)
Use of ZSM-5 Zeolite containing additives
_ high Catalyst Activity (very high Conversion)

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84. FCC Optimization for Light Olefins Production

sua] Atmospheric Sp non + Fuel Gas H2, C1, C2, C2=
Lolumn C3's, C4's for LPG
C3= for dimersol / petrochem.
Atmospheric — C3=, C4='s for cat. polym.
Residue ‘Vac. Gas Oil | Gas Oil C3=, C4='s, i-C4 for alkylation
dl FA i-C4= for MTBE
Vacuum + Gasoline C5-221°C
Column > Kerosene 150 - 250°C
r > Diesel 200 - 350°C
Vacuum m M
Residue HT Resid FCC UNIT | ~~ Cat. Heating Oil
à À
Residue = = For: 7
arcos Light Olefin Selectivity is favored by:

ii

high Riser Outlet Temperature
high Catalyst / Oil ratio
high ECat Activity (MAT)

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85. GBH Enterprises Ltd.

Short Contact Time Operation

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86. FCC Optimization for Short Contact Time

Operations
sua] Atmospheric Sp non + Fuel Gas H2, C1, C2, C2=
Solum C3's, C4's for LPG
C3= for dimersol / petrochem.
Atmospheric| — C3=, C4='s for cat. polym.
Residue Vac. Gas Oil | Gas Oil C3=, C4='s, i-C4 for alkylation
dl i-C4= for MTBE
Vacuum F + Gasoline C5 - 221°C
Column > Kerosene 150 - 250°C
——— Diesel 200 - 350°C
Vacuum = 1
Residue HT Resid FCC UNIT Cat. Heating Ol
à À
Residue = ER 7
Rydrotreater Short Contact Time Operation is favored by:

ii

_ high Catalyst Activity
balanced Zeolite/Matrix ratio (Z/M)
_ high Hydrogen Transfer (high ucs)

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87. FCC Optimization for Short Contact Time

Operations
sua] Atmospheric Sp non + Fuel Gas H2, C1, C2, C2=
Solum C3's, C4's for LPG
C3= for dimersol / petrochem.
Atmospheric| — C3=, C4='s for cat. polym.
Residue ‘Vac. Gas Oil | Gas Oil C3=, C4='s, i-C4 for alkylation
y i-C4= for MTBE
Vacuum | Gasoline C5 - 221°C
Column > Kerosene 150 - 250°C
——— Diesel 200 - 350°C
Vacuum = 1
Residue HT Resid FCC UNIT Cat. Heating Ol
à À
Residue = ER 7
Rydrotreater Short Contact Time Operation is favored by:

ii

high Riser Outlet Temperature
high Catalyst / Oil ratio
high ECat Activity (MAT)

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88. f \_ GBH Enterprises Ltd.

Gasoline Olefins Reduction

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89. FCC Optimization for Gasoline Olefins

Reduction
crude >| Atmospheric a r > Fuel Gas H2, C1, C2, C2=
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 (a lees = =
Residue HT Resid FCC UNIT a AT ET
à À
Resid A r =
i ee 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)
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90. FCC Optimization for Gasoline Olefins

Reduction
crude >| Atmospheric a r > Fuel Gas H2, C1, C2, C2=
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 (a lees = =
Residue HT Resid FCC UNIT a AT ET
à À
Resid A r =
i ee Gasoline Olefins Reduction is favoured by:

high Catalyst / Oil ratio
low Riser Outlet Temperature

_ _ high ECat Activity
_ high Conversion
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91. VULCAN Catalyst Process

Technology Consultancy
Sales and Service

x GBH ENTERPRISES, LTD
O
EM |

Gerard B. Hawkins
Managing Director, C.E.O.

Skype: GBHEnterprises
Office: [phone]
Cell: [phone]