Professional Documents
Culture Documents
Refining
Catalyst
Development
Processes
INDIANOIL
Dr. S K Ray
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Contents
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Refining
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Weak
refinery
margins
Refinery
operations
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Deteriorating
Crude
quality
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Interplay between
Feedstock-hardware-catalyst-process control
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FCC
Reforming
Hydroprocessing
(HT, HC)
Isomer.
Alkylation
MTBE
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Merox,
Claus
etc.,
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ENVIRONMENT
33%
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CHEMICALS
27%
REFINING
40%
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HC
9%
FCC
50%
ISO.ALKY
6%
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REF.
6%
HT
29%
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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
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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
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: 15
~ 26
~ 42
10
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FCC Process
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490-550 OC
650-680 OC
Rx
Rg
Riser
Feed
11
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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
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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
0.5-1;
20-45%
600 m2/g
Amorphous
matrix
Alumina 1 ,
Sol =0.01
30250m2/g
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C
C
C
C
C
C
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FCC (Acid)
n-decane
C
C
C
C
n-hexane
C
C
C
C
n-butene
15
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Reactions in FCC
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H+
0
0
Si
Al0
Si
0
Si
0
Al0
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Si
0
-H2O
0
0
Si
0
Al-
Si+
0
0
Si
Al
0
Si
0
RParaffins
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Paraffins + Olefins
Cracking
LPG Olefins
Cyclization
Naphthenes
Isomerization Branched Olefins
H Transfer
Paraffins
Cracking
Olefins
Cyclization
Condensation
Dehydrogenation
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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
Alkylation
Dehydrogenation
Condensation
Coke
18
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FCC Catalyst
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Catalyst Components
Zeolite
Matrix
Binder
Filler
FCC Catalyst preparation
Non-Wash route
Wash route
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Structure of Zeolite
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Super
cage
Hexagonal
Prisms
Sodalite
cage
20
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Zeolite
Preparation:
Na Silicate Na Aluminate Al2(SO4)3
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NaOH
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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
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Ammonium Exchange:
Na+ - Z- + NH4+
NH4+ - Z-
Calcination
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Na+ + NH4+ - Z-
H+ - Z- + NH3
RE(H2O)n3+ - [Z]3-
Hydrolysis
23
- 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:
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- Si
O
+SiO2
- Si O H H O Si
H
- Si
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- Si
O
- Si O Si O Si - +
[Steam, T]
- Si
2H2O
25
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Zeolite properties
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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
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USY
Low
Low
Low
High
Low
27
Matrix
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Physical functions
Binder
Diffusivity
Diluting medium
Sodium sink
Heat transfer
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Matrix
Active
Medium active
Inactive
28
FCC Catalyst
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Manufacturing:
Gel
compo
nents
Seed
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(NH4)2SO4
H2O wash
NH4 NaY
NaY
Calciner
Filter
NaY Crystallization
FCC Catalyst
29
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FCC Catalyst
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30
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RFCC Catalysts
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RFCC Catalyst
Zeolite
RE-HSY
RE, HY
Matrix
(active)
Additives
31
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RECENT ADVANCES
IN CATALYST
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ROLE OF ADDITIVES
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Improved Operation
Flexibility
Why
Additive ??
Quick
Response
Easy to Add /
Withdraw
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FCC Additives
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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
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ZSM-5 additive
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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
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37
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ZSM - 5 Additive
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38
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39
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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
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H2 make
Nickel
High
Vanadium
Moderate
Moderate
High
42
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Nickel
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Vanadium
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44
Ni passivators
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Ni passivating agents are antimony, bismuth and rare earth
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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
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Vanadium Passivators
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Metal traps
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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.
47
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Feed sulfur
F
C
C
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(20 - 60%)
Gasoline
(2 - 10%)
(5 - 35%)
Coke, SOx
(2 - 30%)
48
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Grace
AKZO
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BCA Additive
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HYDROPROCESSING OPTIONS
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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
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HYDROPROCESSING CATALYSTS
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Hydrotreating
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Butane
CH
HC
CH
H2
Metal
C
H2S
S
CH Pyridine
HC
CH
HC
CH
H2
Pentane
Metal
Ammonia
NH3
N
52
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Where HT is used?
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53
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Selectivity
Chemically induced:
Controlled acidity,
Support Architecture induced: Zeolite and
support pore geometry
55
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PORE ARCHITECTURE OF
TYPICAL HP CATALYSTS
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-Pore volume
----------------- pore diameter
HDS catalyst
Unimodel
HDM Catalyst
Bimodel
HDM Catalyst
Pore size in A
56
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Hydrocracking
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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
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Al2O3
Al2O3-halogen
SiO2-Al2O3
Zeolite
Increasing hydrogenation
activity
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Raw material
Methods of preparation
Scale-up feasibility
Cost-effectiveness
59
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ALKYLATION
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Catalytic reforming
.Chemical process to convert
petroleum refinery naphthas,
typically having low octane ratings,
into high-octane liquid products
62
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Basics
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Overall effect
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By-products
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CATALYTIC REFORMING
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More
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FEED
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Catalytic Reforming
n-decane
C
C
Reforming
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C
C
(metal +acid)
CH3
C
toluene
HC
CH
HC
H2
CH
C
H
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Reforming Catalysts
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Sulfur tolerant
Low coke generation
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Catalyst Mechanism
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Catalyst Manufacture
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Stock
RON
MON
Butane
95
92
Iso-pentane
92
89
94
85
99
88
Heavy reformate
113
102
FCC gasoline
91
80
Alkylate
95
92
Isomerate
85
82
MTBE
115
99
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20
10
10
C5 C6 C7 C8 C9 C1
Aromatic
Paraffin
Paraffin
Naphthene
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C5 C6 C7 C8 C9 C10
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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
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Catalyst Changeover
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77
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78
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Indian Scenario
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81
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82
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Indmax (Process)
Indalin (Process)
Lotus 24 (FCC catalyst)
IMAX additive (Additive)
83
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Expertise Developed
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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
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Process
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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
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INDALIN
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US Patent awarded
Patent no. 6153089 dated Nov 28, 2000
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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
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FCC Catalyst
Lotus -24
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90
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Conclusion
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91