You are on page 1of 91

R&D

Refining
Catalyst
Development
Processes

INDIANOIL

Dr. S K Ray

Indian Oil Corporation Limited,


R&D Centre,
Faridabad

R&D

Contents

INDIANOIL

Refining Process & Catalysts

Fluid Cracking Catalyst (FCC)


FCC additives
Reforming Catalyst
Hydroprocessing and other Catalysts
R & D & Commercialization Status in India
Conclusion

R&D

Refining

INDIANOIL

Process to produce useful fuels from crude oil


Separation, Conversion, Treatment & Blending

Primary processes- fractionation


Secondary Processes- conversion processes
improve the product quality
upgrade heavier ends to lighter products
Predominantly catalytic processes

R&D

Weak
refinery
margins

Product pattern shift

Refinery
operations

INDIANOIL

Deteriorating
Crude
quality

Refinery emission control


(NOx and Sox)
4

R&D

More profit in a refinery unit?

INDIANOIL

Interplay between
Feedstock-hardware-catalyst-process control

Today, refiners have less control on


feedstock
Hardware change -an expensive proposition
Look for catalyst option

R&D

REFINERY CATALYTIC PROCESSES

FCC

Reforming

Hydroprocessing
(HT, HC)

Isomer.
Alkylation
MTBE

INDIANOIL

Merox,
Claus
etc.,

R&D

World Wide Catalyst Market

ENVIRONMENT
33%

INDIANOIL

CHEMICALS
27%

REFINING
40%

R&D

REFINING CATALYST MARKET


($1.5 billion/year)

HC
9%

FCC
50%
ISO.ALKY
6%

INDIANOIL

REF.
6%
HT
29%

R&D

Trends in Catalysis

Relative complexity

Liquid acids
Non-selectivity
Hazardous
Capital, Energy
intensive

Brute
force
Olden days

Zeolites
High selectivity
Min. by-products
Knowledge base

INDIANOIL

Scalpel

.
Knife Enzymes or catalyst
mimic enzymes
Hammer
Very high selectivity
Clean process
Highly Knowledge
based
Inorganic catalysts
Improved selectivity
By-products concerns
Last 50 Years

Present

Future

R&D

FCC SCENARIO IN INDIA

FCC Units in Operation

INDIANOIL

: 15

Total FCC Capacity


MMTPA

~ 26

Future FCC Capacity


MMTPA

~ 42

10

R&D

FCC Process

INDIANOIL

490-550 OC
650-680 OC

Rx

Rg
Riser

Feed
11

R&D

FCC: Some Interesting Facts

INDIANOIL

Nearly 20% of crude is being processed at FCC


Larger FCC units holds about 400 Tonnes of catalyst
Four major manufactures (Grace Davision, Engelhard,
Akzo Nobel, CCIC) supply 1400 tons of catalyst daily
to process 12 million barrels per day (600 MMT/day)
400 FCC units in world
12

R&D

GROWTH OF CATALYSTS IN FCC

INDIANOIL

Sox additive
CO promoter
Y zeolite
based
catalysts
High alumina
catalyst

1915

Nickel passivation
(Bi)

BCA,,
Resid
FCC
Octane
additive
USY
zeolite

Nickel passivation
(Sb)
First commercial FCC, natural clay
First catalytic cracking AlCl3
1940 1950 1960 1970 1980 1990 2000
13

Cross section of FCC catalyst particle

INDIAN OIL

Zeolite
binder

Filler Clay
1

Catalyst Pore
volume: 0.2-0.5 cc/g

Zeolite pores
6.5-13. 5A

5-55%

Interparticle void
clay
Matrix pores
10-200A

10-40 m2/g
1 micron

Other elements (Sodium, Rare earth, metals


such as Vanadium, Nickel etc.)

0.5-1;
20-45%
600 m2/g
Amorphous
matrix
Alumina 1 ,
Sol =0.01

30250m2/g

R&D

Fluid Catalytic Cracking


C
C

C
C

C
C

C
C

INDIANOIL

FCC (Acid)

n-decane
C
C

C
C

n-hexane

C
C

C
C

n-butene
15

R&D

Reactions in FCC

INDIANOIL

Paraffins are cracked to give olefins and smaller paraffins


Olefins are cracked to give smaller olefins
Napthenes (cycloparaffins) are cracked to olefins,

Alkyl aromatics lose their side chains

Isomerisation of olefins to iso-olefins


H-transfer reactions
16

Acidity of solid catalysts


0

H+
0

0
Si

Bronsted Acid sites


H+
0
0
0

Al0

Si
0

Si
0

Al0

INDIAN OIL

Si
0

-H2O
0

0
Si

0
Al-

Si+
0

0
Si

Al
0

Si
0

Lewis acid sites

Main reactions in FCC Catalysis

RParaffins
&D

Paraffins + Olefins
Cracking
LPG Olefins
Cyclization
Naphthenes
Isomerization Branched Olefins
H Transfer
Paraffins
Cracking

Olefins

Cyclization
Condensation
Dehydrogenation

INDIANOIL

H Transfer

Branched Paraffins

Coke

Cracking

Naphthenes

Olefins
Dehydrogenation
Dehydrogenation
Cyclo-Olefins
Isomerization
Naphthenes with different rings
Side chain cracking
Trans alkylation

Aromatics

Dehydrogenation
Condensation

Aromatics

Unsubstituted aromatics + Olefins


Different alkylaromatics
Polyaromatics

Alkylation
Dehydrogenation
Condensation

Coke
18

R&D

FCC Catalyst

INDIANOIL

Catalyst Components
Zeolite
Matrix
Binder
Filler
FCC Catalyst preparation

Non-Wash route

Wash route
19

R&D

Structure of Zeolite
INDIANOIL

Super
cage

Hexagonal
Prisms
Sodalite
cage

20

R&D

Zeolite

Preparation:
Na Silicate Na Aluminate Al2(SO4)3

INDIANOIL

NaOH

Na Aluminosilicate gel NaY Seeds


Crystallization
NaY Slurry
Filtration
DM water washing
NaY zeolite
21

R&D

Further treatments of NaY zeolite


INDIANOIL

Ion Exchange
RE Exchange
Preparation methods of High-Silica Y zeolites
Thermal and hydrothermal modification
Chemical modification
Combination of hydrothermal and chemical
modification

22

Ion Exchange

R&D

Ammonium Exchange:
Na+ - Z- + NH4+

NH4+ - Z-

Calcination

INDIANOIL

Na+ + NH4+ - Z-

H+ - Z- + NH3

Rare Earth Exchange:


3Na+ - Z- + RE(H2O)n3+

RE(H2O)n3+ - [Z]3-

3Na+ + RE(H2O)n3+ - [Z]3-

RE(H2O)n-1 (OH)2+- H+- [Z]3-

Hydrolysis

23

R & D Thermal and hydrothermal modification


INDIANOIL
Framework Dealumination:

- Si - Si

O
O

+H2O

- Si O - Al- H+ - O Si
- Si O H H O Si - +

[ Steam,T]
H

O
- Si

- Si
Al(OH)3 24

Framework Stabilization:
R&D

- Si
O

+SiO2

- Si O H H O Si
H

- Si

INDIANOIL

- Si
O

- Si O Si O Si - +
[Steam, T]

- Si
2H2O
25

R&D

Zeolite properties

INDIANOIL
Unit cell size:
It is an elementary building block of the zeolite crystal.
It is a measure of aluminium sites or the total potential
acidity.
NSi + NAl = 192

Al/Unit cell = 111.52 (UCS 24.191) developed by


Breck and Flannigan
UCS (oA)
Al/Unit cell
NaY (As synthesized) 24.64 24.67
54
USY
24.50 24.54
40
Equilibrated USY
24.25 24.30
2 - 13
26

R&D

Rare earth level:


Rare earth elements serve as a bridge to stabilize
aluminium atoms in the zeolite structure.
Rare earth exchanged
zeolite
High
UCS
High
Zeolite activity
High
Gasoline selectivity
Low
RON
High
Hydrogen transfer

INDIANOIL

USY
Low
Low
Low
High
Low
27

Matrix

R&D

Physical functions
Binder
Diffusivity
Diluting medium
Sodium sink
Heat transfer

INDIANOIL

Matrix

Active

Medium active

Inactive
28

FCC Catalyst

R&D

Manufacturing:

Gel
compo
nents

Seed

INDIANOIL

(NH4)2SO4
H2O wash
NH4 NaY

NaY

Calciner

Filter
NaY Crystallization

NaY Ion exchange


Clay
Alumina source
Silica source

FCC Catalyst

Mixing of Zeolite with matrix components

29

R&D

FCC Catalyst

INDIANOIL

30

R&D

RFCC Catalysts

Characteristics of Resid FCC Catalysts


Low coke and dry gas selectivities
High thermal and hydrothermal stability
Resistance to deactivation by metals
Resistance to nitrogen poisoning
Ability to crack selectively heavy hydrocarbons

INDIANOIL

RFCC Catalyst

Zeolite
RE-HSY
RE, HY

Matrix
(active)

Additives

31

R&D

RECENT ADVANCES
IN CATALYST

Catalyst with High Nickel Tolerance and


Vanadium Traps
Improved coke Selectivity
High Matrix Catalyst
Accessibility
Regenerability
Strippability

INDIANOIL

R&D

Properties of High-Silica Y Zeolites


INDIANOIL

Framework Si/Al ratio


Thermal and hydrothermal stability
Ionic exchange capacity
Unit cell size
XRD, Si-MasNMR {[Si(0Al)]}
Total acidity
Acid strength
Catalytic site density
Hydrogen transfer activity
33

R&D

ROLE OF ADDITIVES

INDIANOIL

To Meet Specific Objectives


Significant Economic
Benefits

Improved Operation
Flexibility

Why
Additive ??
Quick
Response

Easy to Add /
Withdraw

R&D

FCC Additives

INDIANOIL

To Improve Performance
Reduction of Sulphur
(SOX) 30-40% S from FCC

CO Emmission control
(CO)

Additive
Bottom Reduction
(BCA)

Metal Passivator
ZSM-5 additive

35

R&D

ZSM-5 additive

INDIANOIL

Octane boosting
Increase in C3 and C4 olefins and LPG
maximization
Preference for higher butylene yield
Initially ZSM-5 cracks paraffins and
olefins. As cycle time increases, olefin
isomerisation dominates while gasoline
loss and octane improvement is minimum
36

R&D

Structure of ZSM-5 zeolite


INDIANOIL

37

R&D

ZSM - 5 Additive

INDIANOIL

38

R&D
INDIANOIL

39
39

R&D

Mechanism for Catalytic reduction of SO x


INDIANOIL
emissions

Regenerator:
Formation of SOx: 1. S in coke + O2
SO2(>90%)+SO3(<10%)
Oxidation of SO2: 2. SO2+(1/2)O2
SO3
Formation of metal Sulfate: 3. MO+SO 3
MSO4
Reactor:
Reduction of metal sulfate:
4. MSO4 + 4H2
MS+4H2O
5. MSO4 + 4H2
MO+H2S+3H2O
Stripper:
Hydrolysis of metal sulfate:
6. MS + H2O
MO+H2S

40

R&D

Metal Passivators and Metal Traps

Metals contain in resid fluids:


Nickel
Vanadium
Iron
Copper
Process:
Demetallization
Passivation

INDIANOIL

Reactions between metal contaminant and passivator


Preferential sorption or reaction with metal contaminants
41

R&D

Nickel and Vanadium


INDIANOIL

H2 make

Nickel
High

(4 times more than V)


Coke make
High
Reducing Conversion
Medium

Vanadium
Moderate
Moderate
High

The relative activity of contaminant metals to degrade


catalyst surface area
Ni < Fe < Na << V

42

R&D

Nickel

Ni on equilibrium catalyst exists as Ni+2 and Ni+3. INDIANOIL


In the regenerator Ni presented on the catalyst
converted to Nickel Oxide.
At FCC reactor conditions Ni acts as a dehydrogenation
and dehydrocyclization catalyst.
It is catalytically active in the regenerator producing high
concentrations of CO2.
Ni is more active whenever there is an interaction
between Ni and alumina.
After depositing on the catalyst it is immobilized.
Ni reacts with alumina to form NiAl2O4.
Ni reacts with silica to form NiSiO3.
43

R&D

Vanadium
INDIANOIL

At regenerator conditions, Vanadium on equilibrium


catalyst exists as V+5.
In the regenerator V presented on the catalyst
converted Vanadium pentoxide (V2O5).
Under regenerator conditions V2O5 is mobile because it
melts at regenerator conditions.
In the presence of steam V2O5 is converted to Vanadic
acid (H3VO4).

44

Ni passivators

R&D
Ni passivating agents are antimony, bismuth and rare earth
INDIANOIL
compounds (Ce, La, etc).
Antimony:
This is a first commercially used additive.
Ni-Sb alloys formed.
(i) Antimony will block Ni active sites.
(ii) Alternation of electronic and chemisorption properties.
(iii) The amount of antimony available to passivate nickel will be
determined by the equilibrium between antimony and nickel.
Draw back: Antimony effects on CO combustion promoters.

45

R&D

Vanadium Passivators
INDIANOIL

Vanadium passivating agents are Tin, Titanium,


Zirconium and rare earth compounds.
Other than the above stated passivating agents there
are other passivating agents are also reported. They
are germanium, gallium, indium, tellurium,
aluminium, barium, zinc, boron, phosphorous,
tungsten, tantalum, lithium and cadmium.

46

R&D

Metal traps

INDIANOIL
Metal traps are added to the FCC Catalyst as separate
particle or incorporated directly into the catalyst
particle.
These metal traps react with incoming metals like
nickel and vanadium and form an inert compounds.

Why rare earths?

47

R&D

DISTRIBUTION OF FCC FEED SULFUR

Feed sulfur

F
C
C

INDIANOIL

Fuel gas, H2S

(20 - 60%)

Gasoline

(2 - 10%)

Total Cycle Oil (10 - 25%)


Clarified Oil

(5 - 35%)

Coke, SOx

(2 - 30%)

48

R&D

Catalyst/Additives for Sulphur Control

Grace

GSR Technology for sulphur reduction 15-25%


Sulphur reduction is achieved mainly from front end
For Gasoline

AKZO

Resolve FCC catalyst selective matrix activity

INDIANOIL

15-30% Sulphur reduction


Optimized access
For Gasoline

BCA Additive

20-30% achieved pesovskite /Spinel


Alumina Matrix
Sulphur capture by Matrix

No Catalyst yet for Diesel


49

R&D

HYDROPROCESSING OPTIONS

INDIANOIL

RESIDUE
+570 C
GAS OIL
NAPHTHA
DIESEL

FUEL OIL

H
Y
D
R
O
P
R
O
C
E
S
S
I
N
G

H-CRACKING
H-ADDITION,
HDS,HDN,HDM
DEEP DE-SULF,
Ar. SATURATION
HDS, CETANE
IMPROVEMENT
DESULFURISATION

50

R&D

HYDROPROCESSING CATALYSTS

INDIANOIL

SUPPORTED METAL CATALYST


ALMOST INERT SUPPORT

SUPPORTED METAL CATALYSTS


ACTIVE SUPPORT
51

R&D

Hydrotreating

INDIANOIL

(HDS, HDN, HDM)


Thiophene
HC

Butane

CH

HC

CH

H2

Metal
C

H2S

S
CH Pyridine
HC

CH

HC

CH

H2

Pentane

Metal

Ammonia

NH3

N
52

R&D

Where HT is used?

INDIANOIL

Reformer feeds are hydrotreated to remove S to


<1ppm. (naphtha treating)
FCC feeds are pretreated
to remove S and N
increase H/C ratio for improved cracking

Hydrocracking feeds are hydrotreated to remove N


Diesel hydrotreating to remove S
Gasoline hydrotreatment to reduce S& olefins

Co-Mo/Ni-Mo Catalyst on Alumina

53

R&D

CATALYT COMPONENTS FOR


HYDROPROCESSING

INDIANOIL

METALS OF GROUP VI-A WITH METALS OF


GROUP - VIII A AS PROMOTER
- W / Mo PROMOTERS Ni / Co
NOBLE METALS
- Pt, Pd
SUPPORTS
- Alumina
- Silica Alumina
- Zeolites
NON NOBLE METAL CATALYSTS ARE ACTIVE IN
SULFIDED FORM
54

R&D

Catalyst variations for


hydroprocessing

INDIANOIL

Selectivity

Chemically induced:
Controlled acidity,
Support Architecture induced: Zeolite and
support pore geometry

55

R&D

PORE ARCHITECTURE OF
TYPICAL HP CATALYSTS

INDIANOIL

-Pore volume
----------------- pore diameter

HDS catalyst
Unimodel
HDM Catalyst

Bimodel
HDM Catalyst

Pore size in A

56

R&D

Hydrocracking

INDIANOIL

Hydrocracking
C
C

C
C

C
C

C
C

+ H2 (metal +acid)

n-decane
C
C

C
C

n-hexane

C
C

C
C

n-butane
57

R&D

Hydro Processing Catalysts

INDIANOIL

Al2O3
Al2O3-halogen
SiO2-Al2O3
Zeolite

Increasing hydrogenation
activity

Increasing cracking activity

Cracking Function Hydrogenation Function


[Acid]
[Metal]
Co-Mo
(HDS)
Ni-Mo
(HDN)
Ni-W (HC)
Pt (Pd)
(HYN)
58

R&D

Design of Hydroprocessing Catalyst

INDIANOIL

Choice of support and support characteristics


Choice of metal components
cost, availability, S tolerance

Raw material
Methods of preparation
Scale-up feasibility
Cost-effectiveness

59

R&D

ALKYLATION

INDIANOIL

Process to transform C4 hydrocarbons to value


added alkylates
Industrially following acids are used, HF, H 2SO4,
AlCl3, BF3
World production of alkylates: 67 MMTPA
Existing technology suffers from two drawbacks
high catalyst consumption
toxic effluent
hazardous chemicals

Challenge is to develop new environment friendly


catalyst.

60

R&D

SEARCH FOR NEW SOLID ACID


CATALYSTS

INDIANOIL

Broad variety of solid catalysts capable for


alkylation
medium and large pore zeolite
Zeolite beta
Chlorinated Alumina
Heteropoly acids
Sulphated Zirconia

61

R&D
INDIANOIL

Catalytic reforming
.Chemical process to convert
petroleum refinery naphthas,
typically having low octane ratings,
into high-octane liquid products
62

R&D

Basics

INDIANOIL

Pprocess re-arranges or re-structures the hydrocarbon


molecules in the naphtha feedstocks
Breakes some of the molecules into smaller molecules

63

R&D
Overall effect

INDIANOIL

Product reformate contains hydrocarbons with more


complex molecular shapes having higher octane values
than the hydrocarbons in the naphtha feedstock

64

R&D

By-products

INDIANOIL

The process separates hydrogen atoms from the


hydrocarbon molecules and produces very significant
amounts of byproduct hydrogen gas for use in a
number of the other processes involved in a modern
petroleum refinery.
Other byproducts are small amounts of methane, ethane

65

R&D

CATALYTIC REFORMING

INDIANOIL

A major conversion process in petroleum refining and petrochemical industries


Process converts straight run naphtha (C6-C10, Straight chain paraffins
and napthenes) to gasoline components of high antiknock quality
Manufacture of Hydrogen and LPG as bye-products
The octane of reformate is provided mainly by aromatics having 6 to 10 carbon atoms
and light isoparaffins
Alkanes and cycloalkanes are selectively converted to aromatic
hydrocarbons
Transforms low octane naphtha to high octane reformate
66

R&D

More
INDIANOIL

Reaction temperature 700-800 oK,


pressure 70-450 psi
Reaction is carried out in hydrogen
atmosphere even though the hydrogen is
one of the product
Reforming is primarily endothermic.
67

R&D

FEED

INDIANOIL

Straight run naphtha is most common


choice
Naphtha from thermal & catalytic
crackers can also be used

68

R&D

Catalytic Reforming
n-decane
C
C

Reforming

INDIANOIL

C
C

(metal +acid)

CH3
C
toluene

HC

CH

HC

H2

CH
C
H

69

R&D

Reforming Catalysts

INDIANOIL

First recognized dual function catalyst


Cracking/hydrogenation/dehydrogenetaion
Isomerisation

Sulfur tolerant
Low coke generation

70

R&D

Catalyst Mechanism

INDIANOIL

Platinum or rhenium on a silica or silica-alumina support base


Some contain both platinum
and rhenium
Fresh catalyst is chlorided (chlorinated) prior to use
The noble metals are considered to be catalytic sites for
the dehydrogenation reactions and the chlorinated
alumina provides the acid sites needed for isomerization, cyclization and
hydrocracking reactions.
The LIFE of the catalyst is reduced over time during operation by
carbonaceous coke deposition and chloride loss
Catalyst can be periodically regenerated or restored by in situ
high temperature oxidation of the coke followed by chlorination.
Normally, the catalyst can be regenerated perhaps 3 or 4 times before it must be
returned to the manufacturer for reclamation of the valuable platinum and/or rhenium
content
71

R&D

Catalyst Manufacture

INDIANOIL

Acidic Support(Alumina from Aluminium chloride)


Spray drying of aluminum hydroxide solution to
produce alumina
Removal of excess chloride by slurrying
Spray dried or extrudates formed
Impregnation of metals, e.g PtCl3
drying

72

R&D

RON & MON OF VARIOUS MOTOR


INDIANOIL
FUEL STOCKS

Stock

RON

MON

Butane

95

92

Iso-pentane

92

89

Medium pressure reformate

94

85

Low pressure reformate

99

88

Heavy reformate

113

102

FCC gasoline

91

80

Alkylate

95

92

Isomerate

85

82

MTBE

115

99
73

R&D

Typical Feed Composition


20

20

10

10

C5 C6 C7 C8 C9 C1

Aromatic

0 0.2 1.2 3.5 4.3 0.9

Paraffin

0.2 3.3 6.1 9.8 3.9 3.6

Naphthene 0.3 5.8 14 14 17 11


Aromatic

Paraffin

Naphthene

INDIANOIL

C5 C6 C7 C8 C9 C10

Naphthene 0 2.3 5.8 8.27 5.95 0.63


Aromatic 0 0.41 3.18 6.8 3.08 0
Paraffin

0 5.49 16.83 21.38 17.26 2.59

Naphthene Aromatic Paraffin

74

R&D

CATALYTIC REFORMERS IN INDIAINDIANOIL


S. Refinery
No

Capacity
MMTPA

Type of
process

Duty

Catalyst
by

BPCL

0.33

SR

Benzene Procatalyse

BRPL

0.11

SR

Xylenes

Procatalyse

CPCL

0.09

SR

Octane

IPCL-IIP

IOCL, Barauni

0.3

SR

Octane

Procatalyse

IOCL, Digboi

0.09

SR

Octane

Procatalyse

IOCL, Haldia

0.196

SR

Octane

Procatalyse

IOCL,
Mathura

0.5

CCR

Octane

Procatalyse

IOCL, Painpat

0.5

CCR

Octane

Procatalyse

Contd75

R&D
INDIANOIL

R & D & Commercialization Status


in India

76

R&D

Catalyst Changeover

INDIANOIL

FCC Daily charge for replenishment,


reactor- regenerator cycle
Hydrocracking- total charge,
regeneration every 2-3 yrs
Reforming- total charge, regeneration
every 3 or more yrs

77

R&D

Wide Range of Catalysts

INDIANOIL

All units do not use same catalyst


Requirement of each unit are different
Custom catalyst- need of the day

78

R&D

Catalyst & Additive Sourcing


Needs Consideration

INDIANOIL

India is totally dependant of overseas supply

R & D have acquired many patents for catalyst


& additive formulations as well as
manufacturing process

Since Large amount of catalyst is required for a


plant trial, decent size manufacturing facility is
to be created at first.
79

R&D

Indian Scenario

INDIANOIL

Most of the refining catalysts are imported


Catalyst consumption is increasing
No major manufacturing facilities in the
country
Research and development confined to
isolated pockets
Urgent need to bridge gaps in scale-up and
commercial activities
80

R&D

Catalyst Research-Indian Scenario

INDIANOIL

Excellent Knowledge base


Laboratory stage developments
Large gap between laboratory to plant

81

R&D

Gaps to be bridged for catalyst


breakthrough

INDIANOIL

Rigorous evaluation under simulated


conditions in association with user
Manufacturing Facility-to solve problems of
catalyst manufacture
scale-up

Willingness to take risk by refineries

82

R&D

Catalyst based new refining


processes in India

INDIANOIL

Indmax (Process)
Indalin (Process)
Lotus 24 (FCC catalyst)
IMAX additive (Additive)

83

R&D

Expertise Developed

INDIANOIL

Catalyst formulations
* IOCAT-65
* Synergy-21: conventional route FCC
* LOTUS series non-wash route and uses Advanced
zeolite
LOTUS-24 LC
LOTUS-24

Additive formulations
* CO-promoter
* ZSM-5 additive

Zeolites
* IOZ-33 (high crystallite size)

84

R&D

The Indmax Process

INDIANOIL

Circulating fluidized bed


Heavier molecules crack to intermediate range
compounds on Active Matrix and USY zeolite
catalyst
Intermediate range compounds further crack to
LPG range on USY & Pentasil Zeolite catalyst
Coupled with very high severity operation
leading to Ultimate Catalytic Cracking
85

R&D

Olefin yield comparison of


Indmax with FCC & DCC

Process

INDIANOIL

FCC DCC* Indmax

Yield, wt%
Ethylene

--

5.1

3.1

Propylene

3.6

17.4

23.2

Isobutylene

1.2

4.8

10.0

Total butylene

--

11.0

18.9

* Thai Petrochemical Ind. Public Co.Ltd., Thailand

86

R&D

INDALIN

INDIANOIL

Indian Oils Aromatic and Light Olefin Technology


Upgradation of Naphtha / Gas oil to LPG and
Aromatics rich Gasoline
Selective production of LPG and aromatic rich (low
benzene) gasoline
No feed pretreatment is necessary
Can handle gas oil range feed stocks

US Patent awarded
Patent no. 6153089 dated Nov 28, 2000

R&D
INDIANOIL

INDALIN
Indalin is more flexible in terms of feed &
catalyst
Higher yields of olefinic LPG & aromatic
rich (low benzene) gasoline
Relatively simple configuration & operation

Indalin is better choice for upgradation


of low value naphtha / gas oil

R&D

FCC Catalyst
Lotus -24

INDIANOIL

IOC Developed indigenous FCC catalyst


formulation suitable for Indian FCC units
Catalyst performance better than imported
catalysts
US patent awarded
Successfully scaled up in a commercial
plant
Refinery trial is on
89

R&D

Gaps to be bridged for catalyst


breakthrough

INDIANOIL

Rigorous evaluation under simulated


conditions in association with user
Manufacturing Facility-to solve problems of
catalyst manufacture
scale-up

Willingness to take risk by refineries

90

R&D

Conclusion

INDIANOIL

Reefing Catalysts- critical input to refineries


Proper selection of catalyst is vital for
profitability
Sustained research input required to develop
formulations suitable for Indian Refineries
Custom catalyst-need of the refiners

91