9th “FCC Workshop for Refinery Engineers”

Indian Oil Corporation Ltd, R&D Centre, 25th – 28th Nov, 2013

FCC Catalyst & Additives 
FCC Catalyst & Additives
Roles & Recent Developments
November 26, 2013

Alex C Pulikottil
(pulikottilac@indianoil.in)
 This presentation is only for the attendees of 9th Workshop on “FCC for Refinery 
Engineers” held at R&D Centre Indian Oil Corporation Ltd Faridabad during November
Engineers”  held at R&D Centre, Indian Oil Corporation Ltd., Faridabad during November 
25‐28, 2013. Neither the whole nor any part of this may be reproduced or distributed in 
any form or by any means without the prior written consent of Indian Oil Corporation
any form or by any means without the prior written consent of Indian Oil Corporation 
Limited, R&D Centre, Faridabad.

2
 FCC PROCESS
•Major secondary refining process
•Circulating fluid bed reactor
•Conversion of heavier fractions to lighter fuel products
Products
Feed Dry gas (H2,
(H2 C1C1, C2)
Vacuum gas oil (VGO) LPG (C3, C4)
Hydro-treated VGO Light cracked naphtha
H d
Hydro-cracker
k b bottom
tt (LCN) (C5-150 °C) C)
Coker gas oil (CGO) Heavy cracked naphtha
De-asphalted oil (DAO) (HCN) (150 – 220 °C)
Reduced crude oil (RCO) Light cycle oil (LCO)
Vacuum residue (VR) (220 – 370 °C)
Clarified oil (CLO) or
Decant oil (DO)
( )

Low value feed into value added products

 Typical reaction in FCC 
Feed stock
Reaction Products obtained
component
Paraffins Cracking Lower paraffin olefins
Cracking Lower Olefins
Cyclization Naphthenes
Olefin Isomerization Branched hydrocarbons
Ht
H-transfer
f P
Paraffins
ffi
Condensation Coke
Cracking olefins
Naphthenes Dehydrogenation Cyclo olefins, Aromatic
Isomerisation p
Naphthenes
Side chain cracking Unsubsituted aromatics
Aromatics transalkylation Alkyl aromatics
dehydrogenation polyaromatics
 FCC PROCESS (Contd)
Effects of Feed Properties
• High CCR ‐ Affects coke yield‐ unit heat balance
• Large quantity of high boiling fractions ‐ Product yield and quality
• High level metal contaminants like Ni, V, Fe, Na etc‐ Undesired side reactions, 
catalyst deactivation
catalyst deactivation

Catalyst Systems
• Multi‐Functional/Component catalyst systems
• Metal Trapping/passivation
• Selective bottoms upgrading
pg g
• High stability
• Additives for selectivity control
• Problem of particulate and gaseous emission

Combination of operating conditions, catalyst & additives choice can be adjusted

to suit feed and product slates
 Increasing Complexities in  FCC Catalyst

Sox additive

Nickel passivation (Bi)
p ( ) BCA,, Resid 
CO promoter FCC

Y zeolite 
based
based  Octane
Octane 
catalysts additive
Re‐Y USY zeolite
High alumina
catalyst
y
Nickel passivation (Sb)

First commercial FCC,  natural clay
First catalytic cracking AlCl3
1915 1940 1950 1960 1970 1980 1990 2000
 FCC CATALYST COMPOSITION

CLAY
Zeolites
Y‐ zeolite, ZSM‐5, β‐ zeolite ZEOLITE
Re‐EARTHS

Amorphous matrix 
Silica, silica‐alumina, alumina MATRIX

Fillers
Clays (Kaolin, halloysite, Pillared clay)
Clays  (Kaolin halloysite Pillared clay)

Other elements like rare earth metals

S
Spray dried
d i d in
i to
t microspheres:
i h (PSD 10-120
(PSD- 10 120 μm, about
b t 50% pore volume)
l )
 Features required for FCC Catalysts 

Attrition Resistance
Particle Size Distribution
Bulk Density

Pore Volume and Pore Size Distribution

Thermal and Hydrothermal Stability
S f
Surface A
Area
Crystallinity of active zeolite
Acid strength distribution
 FCC Catalysts – Constituent

Active component
Matrix
A i
Active I
Inert
Zeolite Synthetic Natural

Clay
SiO2,Al2O3 & SiO2-Al
Al2O3 Modified Clay

FCC catalysts Binder

 Characteristics of zeolites

Super cage(8-9 A)

Na56[(AlO2)56(SiO2)136].250H2O
NSi + NAl = 192

Y‐ zeolite (Large Pore Zeolite‐ Cage like structure)

Zeolites X & Y:   7.4 Å

Mordenite:  6.5 x 7.0 Å
Beta:  ~ 7.0 Å
Å
ZSM‐5 (Medium Pore Zeolite‐ Channel system
ZSM‐5:  ~ 5.5 Å 
10
 Properties of zeolites that influence FCC catalysts

ACIDITY bridged hydroxyl

• Nature
• Bronsted acidity

• Lewis acidity
L i idit

• Number of Bronsted
N b fB d acid sites
id i
• Frame work SiO2 / Al2O3 ratio
• Reflected in the Unit Cell Size (UCS) of 
( )
zeolite

• Strength of Bronsted acid sites
• Frame work SiO2 / Al2O3 ratio
• Type of zeolite
Type of zeolite
 Properties of zeolites that influence FCC catalysts
((contd..))
CRYSTAL CHARACTERISTRICS Y zeolite crystallize in a cubic form
•Crystallinity Total frame Al + Si
Total frame Al  Si= 192
192

•Crystallite size Al/Unit cell    = 111.52 (UCS – 24.191)

y g
•Smaller crystal size higher conversion Si (Atoms/Unit Cell) = 192 - Al(Atoms/Unit Cell)
•Lower stability

Unit Cell Size (UCS)
•Unit Cell Size (UCS)
•Smallest repetitive unit of a crystal

1 UCS = 4 Complete cage; 6 half cage ; 8,1/8 cage
Typical effect of UCS on product yiels
 Properties of zeolites that influence FCC catalysts
(contd..)

STABILITY
• Ultra stabilization
• Hydrothermal
d h l
• Chemical

•Rare earth exchange
•Impacts  catalyst stability
Slows steam deactivation 
•Increase metal tolerance

PORE ARCHITECTURE
Microporous
Mesoporosity

Microporous

Pore modification alter selectivity
 Typical FCC Catalysts – Preparation 

Alumina

Clay
Alumina/Clay Slurry

Zeolite Mixing

Zeolite /Alumina/Clay Slurry

Silica Mixing

Zeolite /Clay/SiO2-Al2O3 Slurry

Spray Drying

FCC Catalyst

14
 Role and Properties of Matrix

Influences physical properties of catalyst

Influences physical properties of catalyst
• Facilitates formation of size and shape 
• Can act as binder of zeolites
bi d f li in the microspheres
i h i h
• Acts as diffusion medium for feedstocks and products
• Facilitates  heat transfer from regenerator
• Prevents structural damage to active zeolite
Prevents structural damage to active zeolite
• Can act as sink for sodium ions and other contaminants
 Role and Properties of Matrix
Amorphous  silica containing matrices
• Silica hydrosol generally employed as the precursor
• Pore size tailoring to control diffusion characteristics

Active alumina containing matrices
• Pseudo boehmite generally employed as the precursor
• Catalytic activity due to acidic alumina
• Can serve as metal trap and for reduction of SOx emission
Can serve as metal trap and for reduction of SO
• Improves attrition resistance

Amorphous silica‐alumina containing matrices

Amorphous silica‐alumina containing matrices
• Active matrix system due to acidity
•Catalytic property influenced by composition
• Pore size tailoring to control diffusion characteristics

Matrices with modified clay
•Thermally and/or chemically modified clay as active matrix
•Good hydrothermal stability and possibility for porosity modification
 Binders used in FCC Catalyst

Binders imparts the required attrition resistance for the microspheres

Typical binder types employed in commercial catalyst
• Silica sol
Silica sol

•Peptized alumina

• Aluminum chlorhydrol

•Aluminum phosphate systems

•In situ binding
 Design of FCC Catalyst

C
Small UCS
A
Lowest coke make
Best bottom cracking Moderate gasoline make
Highest C3 + C4 Moderate octane
ne Increase

Highest Octane
Highest Octane
RE Content Increased

Highest Octane‐Bbl
Octan

D
B
Highest gasoline make
Good bottom cracking Lowest octane
Lower C3 + C4 Lowest C3+ C4
Highest Coke Make Lowest Bottom cracking

Large UCS 1 2 3 4
Lower Higher
Z/M Activity Ratio
Z/M Z/M
Matrix Activity Increase
Coke Make Increase
 Lotus‐24 : Robust Catalyst for FCC/RFCC

 Tailored zeolite composition and rare earth distribution
p

 Designed matrix for bottoms up gradation
Designed matrix for bottoms up gradation

 Increased octane barrel
I d b l

 High attrition index

19
 Performance of IOCL Lotus series FCC catalyst

CATALYST Commercial Catalyst Lotus‐24

Yield, wt% 
ld

LPG Base + 0.67

Gasoline Base + 2.5
TCO Base ‐ 3.2
CLO B
Base ‐ 0.11
0 11
Operating condition
Feed T’put
Feed T put, m3/hr
m3/hr 150
Reactor top temp 3900C
Dense bed temp
Dense bed temp 6530C
Cat cir rate, TPH 907

20
 FCC Additives

Meeting specific
objectives
Types of Additives
Significant • ZSM-5
economic benefit
• Bottom Cracking
Improved operation • SOx Additive
Additive
fl ibilit
flexibility • V-Trap
• CO-promoter
Easy to add/
withdraw • GSR
• Ni Passivator

Quick Response
 Application of FCC Additives

Additive Applications

ZSM-5 Increases gasoline octane & C3/C4 olefins yields

CO promoter
t E h
Enhances CO b
burning
i g iin regenerator
g t dense
d bed
b d

BCA • Upgrades bottom of the feed

• Increases the LCO yield

SOx additive Reduces SOx in regenerator flue gas

Ni & V Reduces detrimental effects of metals on

Passivators product yields & catalyst health

GSR Additive Reduces sulfur in gasoline product

 ZSM-5 Additives for Propylene Production

 Reduce heavy gasoline olefins (C6+) and increase light olefins (C5-)

 More effective than increasing riser temperature for maximizing LPG

olefins in FCC

 Temperature increase of 45 °C  4 wt % of the ZSM-5 additive

 ZSM-5: Increases RON and MON

Ind. Eng. chem. Res., 38 (10)1999,3849

ZSM-5 -commercially used zeolite in FCC units other than faujasite

 Phosphorus Stabilization of ZSM-5

Relative rate constant k n-C6 for n-hexane cracking at 811 K

ZSM-5 100
ZSM-5 steamed * 1
ZSM-5 doped with 1 wt % Phosphorus 80
ZSM-5 steamed * doped with 1 wt % 6
Phosphorus

*- Steaming : 5 h, 1033 K ,100 % steam, atm. pressure

 Retard aluminum from ZSM-5 framework –MAS NMR

 Phosphorus reduces initial acidity of ZSM
ZSM-5
5, after steaming
results in the larger fraction of acidity

F
Formation
ti off Aluminophosphate
Al i h h t stabilizes
t bili ZSM-5
ZSM 5

MMM 35-36 (2000) 245- 252

 Interaction of P with Bronstead acid sites

 Optimum for a P/Al molar ratio of around 0.5–0.7

05 07
 Phosphorus : Acidity and activity alters significantly.

J. Catal 237 (2006) 267–277

 Propylene Production Pathway in FCC

C3= ×
1 Paraffins
3 &
Aromatics

Gasoil 2 Gasoline
range Olefin ×
1 & 2 : Catalytic Cracking by FCC base catalyst
3 : Catalytic cracking by ZSM-5 additive
 Undesired products (paraffin's) by hydrogen transfer of FCC
catalyst
 Challenges in ZSM-5 additives

Hydrogen transfer properties of the

feed
F
Feedd naphthenes
hth saturates
t t th
the
Gasoline range olefins
before cracking by ZSM-5

Ind.Eng.Chem.Res ,38 (10),1999, Page 3859

 Challenges in ZSM-5 additives

Effect of UCS on Propylene

Conversion 70 wt %
ZSM-5 wt.% additive 4

UCS 24.20 24.30

Propylene enhancement 33 wt. % 15 wt. %

Effect of Rare earth on FCC Cat

 Higher acid site density with high

UCS enhances hydrogen transfer of
Y-zeolite.
 IOCL ZSM-5 additives

IOCL Developed ZSM-5 additive formulations with

proprietary composition

Commercial Products : i-MAX series


 i-MAX Premium : Low ZSM-5 content

 i-MAX
i MAX Supreme
S : M di
Medium ZSM-5
ZSM 5 content
t t

 i-MAX Ultra : High ZSM-5 content

 Enhanced propylene yield & Gasoline octane number

 Lower undesired heavy end hydrocarbon yield
 Suitable attrition index and other physical properties
 Characteristics of IOCL ZSM-5 additives

Properties Premium Supreme Ultra

 Case Study 1

Effect of different ZSM-5 additive Influence of ZSM-5

by varying zeolite content additive concentration
12
40

ene in LPG (wt %)

wt %

10
30
Prropylene w

6
20
4

10

Propyle
2

0
0
Base A B C 1 2
ZSM-5 addtive concentration(wt %)
Different ZSM
ZSM-5
5 addtives

ROT:511 Deg C, ZSM-5 additive : 15 wt %, ROT:534 Deg C, ZSM-5 additive : 2-

Ni:3500 ppm, V:6500 ppm, Feed : Resid 4 wt % Feed : VGO
 Case study – Plant Prediction

FCC Base + 2 wt % FCC base + Imax

Olefin max supreme -2 wt %

Dry Gas 3.19 2.92

LPG 22 5
22.5 22 99
22.99
Gasoline 36.19 37.08
Heavy
y Naphtha
p 9.3 9.32
Light cycle oil 14.18 13.36
Total cycle oil 23.48 22.68
CLO 10.24 10.09
Coke 4.4 4.24
Conversion wt % (216 75 6
75.6 76 5
76.5

Propylene 5.85 7.12

Feed rate: 215 M3/hr, ROT: 525 Deg C, Cat/Oil 6.0

Superior performance than commercially available products
 Metal Passivator :  IndVi

Additive approach: Adsorption approach:
black particles  zoned catalyst
represent metal passivator

Designed for simultaneous Ni and V passivation

33
 Feed Properties and Operating Conditions for IndVi

Density at 15 o C (gm/ml) 0.9387

o
% Vol., Distillation C
IBP 318
10 353
50 458
FBP -

Sulfur, wt% 3.5

CCR, wt% 3.7
Basic N2, ppm 990
Vanadium, ppm 15
Nickel, ppm 9
Operating condition
Feed T’put, m3/hr 99
Cat cir rate, TPH 474
Riser top temp, 0C 510
Regen dense beds RG1/RG2, 0C 676/730 34
 Effect of IndVi on Activity & Selectivity

80
Base case-1 (RFCC catalyst+ 5wt% ZSM-5 additive)
68.11 69.52
70 Base case-1+ 5 wt% IndVi additive

60
Predicted yield at equal coke level

50
Wt%
Yields, W

40

29.07 28.14
30

22.61 23 35
23.35
19.09
20 17.43

9.73 10.78
9.28
10 7 11
7.11 7 11
7.11 7 08
7.08
4.77 4.53

0
Dry gas LPG Gasoline HN LCO CLO Coke 216- conv
Product Distribution

35
 Effect of IndVi on Activity & Selectivity

Predicted yield with increased thro’put. 110 m3/hr
ROT= 505 0C
70
65.43
Base case-2 (Catalyst similar to case 1, change in ROT, feed t’put) 64
Base case-2 + 5 wt% IndVi additive
60

50

40
Yields, Wt%

30 28.75 27 88
27.88
Y

24.05 24.8

20
15.93
14 32
14.32
11.96
9.67 10.73
9.77
10 7.00 6.87
4.26 4.02

0
Dry gas LPG Gasoline HN LCO CLO Coke 216- conv
Product Distribution
 EDAX of Metal  Passivator
Catalyst  and   Passivator
additive
Blue speck 
indicate passivator

V Ni

37
Recent trends in FCC catalyst technology
 Scientific innovations in FCC catalyst development

• More active binding materials/ matrix

• Improved catalyst assembly technology and control of pore 
architecture

• Better understanding of reaction kinetics

• Improved regeneration kinetics and control over regeneration

• Improved zeolite accessibility

• Improvement in catalyst activity testing methodology 
 Improvements in Fluid Catalytic Cracking

Year Avg. barrels / 
g / Max concarbon  Avg. conversion 
g
pound catalyst treated for VGO
1950 20
2.0 ‐1%
1% 62%

1975 40
4.0 2 5%
2.5% 73%

2000 67
6.7 7 5%
7.5% 79%

Substantial improvement in catalyst stability and activity

(Source:  Albemarle)
 Diesel selective FCC catalyst

Philosophy of working of FCC catalyst

Macropores
Mesopores Micropores
Resid/ Gasoline
Gas oil
VGO

Catalyst design factors
Catalyst design factors
Low zeolite/matrix surface area ratio
Coke/gas selectivity of matrix
Hydrothermal stability of matrix
y y
Mesoporous matrix components 
Better accessibility of reactants
 Innovations in FCC catalyst technology

FCC catalyst particles with staged reaction zones

FCC catalyst particles with staged reaction zones

Different catalytic properties for each stage
y p p g

Manufacturing process allows combination of two or more FCC 
catalyst functionalities in single catalyst particle

Staging approach allows processing heavier feedstock or 
Staging approach allows processing heavier feedstock or
achieving desired product yields  

Multi‐Stage Reaction (MSRC) technology platform introduced by 
BASF
 BASF Prox‐SMZ catalyst technology

Macroporous matrix with in‐situ generated 
zeolites on the walls in a single step
g p

Proximal stable matrix and zeolite (Prox‐
SMZ)
BASF FCC catalyst platform
Intimate contacting of matrix and zeolite reduces 
coke
High accessibility for reactants
Hydrothermally stable matrix
HDXtra for VGO and Stamina for resid FCC
Increase of diesel selectivity by 4‐6%

IIncreased 
d
matrix stability

Increased bottom 
Upgradability to diesel
 Diesel selective FCC catalyst

Albemarle FCC catalyst technology‐ AMBER MD
 Low zeolite/matrix ratio
 Albemarle Developed Matrix (ADM) and Zeolite
(ADZ)
 High accessibility for heavy feed molecules
 Product selectivity for mid‐distillate 
 High metal tolerance and lower pore blockage Accessibility Index vs.  LCO yield 

GRACE’s MIDAS technology
Moderate zeolite/matrix ratio
Moderate zeolite/matrix ratio
Porosity in mesoporous region 100‐600 A
 ZSM‐5 additive for propylene

To be avoided

Production of olefin in FCC

To avoid hydrogen transfer
To avoid hydrogen transfer
Reduce Y‐zeolite in main catalyst & rare earth content ‐affects conversion &
stability
 Increase ZSM‐5 additive content ‐excess of additive cause dilution & reduce
Increase ZSM‐5 additive content ‐excess of additive cause dilution & reduce
conversion
Compensate with Y‐zeolite??‐facilitate hydrogen transfer

ZSM-5 would be of most beneficial, when used in small amounts

 Modification of ZSM‐5 vs. Propylene

Light olefins yield on naphtha cracking (Fixed bed 
reaction))

Appl. Catal A : Gen. 398(2011)

Modification of ZSM-5 improves propylene selectivity

 New zeolitic materials vs.propylene

Comparative MAT data at constant conversion (75%)

Light olefins yield

Fuel 90(2011)

Improved materials for enhancing propylene yield

 Grace’s ProtAgon FCC catalyst

 Primary cracking of the FCC main catalyst and

shape selective cracking function of ZSM5
additive are combined.
Grace’s ProtAgon technology

Product selectivity from gasoline range olefin cracking

Grace’s ProtAgon plus technology

High acid strength along with good shape selectivity in the catalyst will
lead to higher propylene selectivity.
 FCC catalysts for propylene

BASF’s Petrochemical FCC catalyst

 Uses conventional FCC catalyst system (Y zeolite main catalyst + ZSM‐5 
additive) along with another additive
 New additive is based on beta‐zeolite
 Patent claims that zeolite
Patent claims that zeolite beta has good catalytic activity for the 
beta has good catalytic activity for the
enhancement of light olefins
 Processing of bottom‐of–the‐barrel

sulfur

API gravity

Hart Energy (2010)

 Declining crude oil quality
 Heavy crude oils are cheaper
Heavy crude oils are cheaper
Innovative technologies are needed for 
processing heavier fractions
Rive molecular highway technology for RFCC

 Rive zeolite technology invented 
at MIT in 2000 & Grace as
at MIT in 2000 & Grace as 
commercial partner
 RFCC catalyst commercialization 
from 2011
 Bottoms upgrading & coke 
selectivity
 Improved gasoline yield 
JGCC RFCC Catalyst design

Increasing mesopores in the 
zeolite leads to effective cracking
 Conclusions

 FCC process is still evolving and a versatile tool for refiners

 Catalyst is the heart of the technology and plays a key role in process
optimization and furthers process innovation

 Optimal design of cracking catalyst for desired requirement involves

fundamental understanding of reaction sequences and its interplay with
catalyst properties

 New catalytic materials development and superior catalyst assembly

technology key for developing further high active and selective catalyst
systems

53
Thank You