Shell Residue Fluidized Catalytic Cracking Process

Shell Global Solutions
The Fluidized Catalytic Cracking Process

65 years of inspiration for technology development
Mart Nieskens
Presentation to KIVI - NIRIA

October 4th 2007
A 1990 presentation updated with a decade of developments
Im
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Design
R&
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Subject of this
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Inspection
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SIMPLIFIED REFINERY FLOW SCHEME

HYDROSKIMMER
LPG
Naphtha
Crude
Crude
Distilling
Unit
Hydro
Treater
Platformer
Hydro
Desulph.
Unit
Kero/Gasoil
Long Residue (LR)
High
Vacuum
Unit
Flashed
Distillate
LPG
Mogas
Kero
Gasoil
Fuel Oil
Cat Cracker
Hydro
Desulph.
Unit
Gasoil
COMPLEX
Short Residue (SR)

Residue Upgrade
(>370 oC) in relation to
FCC process ability
FLUID CAT. CRACKING UNIT (FCCU)

Temp., C
Pres., barg
P
Flue gas
Reactor
2.0
T
P
Light cycle oil
525
2.0
Heavy cycle oil
L
700
Steam
Riser
350
Fractionator
Air blower
Slurry
oil
Flashed Distillate /
Long residue
Air
FCC Process
2-stage cyclone systems

keep catalyst inside unit
Hydrocarbon/steam vapour to
Main Fractionator & work-up
Inter & Intra-stitial hydrocarbons

stripped from catalyst using steam
Spent catalyst flows to regenerator and
reactivated by burning off coke
Catalyst gradually deactivated by

formation of coke on surface
Fresh Feed & Recycles contacted

with regenerated catalyst in riser
Regenerated catalyst flows to

bottom of liftpot-riser
Catalyst flow
controlled by
pressure-balance
and slide-valves
FCC OPERATING
CONDITIONS
Typ.
Feedrate, t/d
5000
Feed temperature, C
250
Riser temperature, C
525
Catalyst Circulation Rate (CCR), t/min
25
Catalyst to Oil (C/O) ratio, t/t

Air-rate, t/d
7.5
3750
Regenerator temperature, C
700
Coke burnt, t/d
250
Design Feed rate varies from

1.500 to 20.000 t/d
Typical.
FCC PRODUCT YIELDS
Typical range
Dry gas
LPG
Gasoline
LCO
2-5
8 - 18
(C5 - 221 C TBP)
(221 - 370 C TBP)
HCO + SO (370 +
C TBP)
Coke
40 - 55
14 - 25
6 - 15
4-8
FCC CATALYSTS
Particle size ~ 70 micron

Particle density 1500 kg/m3
800
600
Real
app
400
REQUIREMENTS:
Activity, selectivity and stability
Good fluidisation characteristics
200
Carrier of heat from regenerator to riser
Umb
Umf
0.01
0.1
vg = v [cm/s]
1
10
100
9
Fluid. Cat. Circulation Unit (FCCU)

Purposes
Circulates Catalyst from A to B and back
Does so unattended, smoothly and reliably
Gives good P build-up at any rate
Elements
gas and catalyst quality
flow-phenomena, (non)-fluidisation
Separations : particles from gas; stripping; burning
Slide Valve: control / safety
10
Shell Support to the FCC Customers

1990
SIPM Den Haag
-
(Shell International Petroleum

Maatschappij)
Shell Oil Houston

KSLA
-
(Kon. Shell Lab. Amsterdam)
2007
-
Den Haag
Amsterdam
Houston
Kuala Lumpur
Bangalore
Shell Global Solutions is Shells technological consultancy group

for Up- & Downstream Facilities, with strong R&D capabilities.
11
Shell Global
Solutions
Shell
Advised
Fluid Catalytic Crackers
Cat Cracking Services
1990
2007
30 units, being
- Shell owned or
- alliances
MONGSTAD
DEER PARK
MARTINEZ
NORCO
CONVENT
PUGET SOUND
PORT ARTHUR
SARNIA
MONTREAL EAST
PERNIS
STANLOW
Coryton
BERRE
REICHSTETT
PETIT COURONNE
43 units, being
- Shell Owned or
- Joint ventures, or
- Third Party
HARBURG
Miro
RELIANCE
YOKKAICHI
SEIBU
TOA
GEELONG
CLYDE
Tupras
Petrotrin
ECOPETROL
CARDON
BUENOS AIRES
DURBAN
PORT
DICKSON
SRIRACHA
SINGAPORE
FCC Business Size

World = 16 million bbl/d
(46% in USA)
Bigger than hydrocracking, coking and thermocracking capacities

altogether
Shell = 1.0
MM bbl/d
(> 53 MM tons/a in 23 FCC units:
6/2 US/Canada; 7/2 AsiaP/South; 6 EUR)
3rd party customers: 0.9 MM bbl/d

(47 MM t/a)
11 Kb/d to 200 Kb/d FCC units
Margin:
@ 40 USD/t FCC > $ 2 bln/a
@ 120 USD/t FCC > $ 6 bln/a (2006)
13
Word-wide cat cracking capacity by Oil Company

Total FCC, KB/D Residue FCC, KB/D
ExxonMobil
RD Shell
Sinopec
Valero
BP
Petrobras
Total
World
Shell GS advise
1260
1080
740
730
670
520
430
140
510
170
50
50
80
75
16000
1900
12 %
1750
510
30%
Residue FCC: > 25% residue content
Our challenge is to process residue

in a profitable and reliable way
14
Development in Shell Cat Cracker Design till 1990
The original.
Big inventory , high C/O
Poorish cat., Much coke
Lowish temps CCR<0.3
Zeolite catalyst
Riser Cracking
Stripper-baffles inside
reactor. CCR < 1.5
Complete Combustion
Compact unit size

Gasoline + / fuel
TSS build into Regen
Resid feed (CCR < 3)
3
Innovative design
no reactor; feedguns
High cap. Cat.cooler
Cat.coolers; high
15
ShellTs
Global Solutions
CCR
<
7
Still single regen.vessel
Process and catalyst development have improved

the conversion and yields
Late 1990s:
Alumina matrices for

Nickel passivation
Metal traps for
Vanadium passivation
Improved zeolite stability for
maximum conversion
Improved catalyst porosity
for resid processing
2000s :
Additives
ZSM-5 for
octane improvement
light olefins (C3=, C4=)
SOx,, NOx, Gasoline Sulfur

16
This is development
Improving Product Yields (while increasing residue in feed)
For a 5000 t/d unit, any 1 % conversion
increase equates a gain of 1 million Euro
per year gross margin
In 2000s
Dry Gas Down
LPG + Gasoline + LCO
further optimized
All with more difficult
feedstock
17
The Geelong FCCU: Worlds most compact RFCCU
Fine Spray Feed Nozzles

Riser reaching reactor top
Compact Reactor Separation
Compact Stripper Packing
Catalyst Spreader in Regen.
Deleting one stage of
cyclones in regenerator
Low Energy
Unit performed reliably and
to specs only after tuning the
equipment elements
18
The path towards the current Shell Design RFCCU

Started from the innovative design in Geelong RFCCU
Reliability Revamp options brought into the Singapore RFCCU
New standard set with the Port Dickson RFCCU (Malaysia)
19
Port Dickson RFCC Unit (1999)

Feed rate ~ 42,000 BPD;
ConCarbon ~ 5.0 average, 6.2 max
20
Port Dickson RFCC Project Execution and Operation

14 million man-hours without a lost time incident
Project execution: on time, 10% under budget
Total installed cost: $370 million (1999)
Flawless Start-up:
set new FCC/RFCC record of on spec products 48 hours after
feed in (old record 72 hours)
Best grassroots RFCC:

set new record of on stream factor of 99.4% for the first run
(1999 2002). The 3-year run-length is mandated
21
Port Dickson RFCC Unit Operation and Performance

Unit objective Max. gasoline and propylene
Crude - 52.5 %w Oman and 47.5 %w Bach Ho
Feed - LR API 23.9, ~ 5.0 concarbon
Catalyst CCIC ~ 7 ton/day, 2% ZSM-5,

Ni ~4700 ppm, V ~ 4000 ppm
Unit yields
70 wt% conversion (4.8% dry gas, 17.2 % LPG, 50.7 % gasoline),
11.3 wt % LCO,
8.6 % HCO/Slurry, 7. 4 % coke
0.05 to 0.1 wt% ash in slurry (by-pass hydroclone)

Partial burn regenerator with COB
Cat loss from flue gas < 0.5 ton/day (< 50mg/nM3)
22
Shell High Performance Feed Nozzles

Feed Nozzle Configuration
Side View of Nozzle Arrangement
D ~ 1.5 m
Full size tested in Amsterdam

Proven reliability in severe conditions
23
Shell High
Performance
Feed Nozzles
1.
2.
3.
4.
> 4 yrs reliable operation

Full riser coverage
Process benefits
Low steam usage
Yield Shifts
(%wt on feed)
Dry Gas
- 0.3
LPG
- 0.5
Gasoline (C5-176C)
+ 0.7
LCO
+ 0.1
Coke
constant
Example of process benefits
24
Reactor Riser Internals
Shell proprietary riser internals prevent

the natural segregation of catalyst from
vapour
Benefits:
Reliable; does not erode away
Gasoline yield > + 0.5 %wof
No extra pressure-drop
Minimized coking
Again, result of large size experimentation in Amsterdam
25
Adding Reliable Internals for Improved Stripping
Packing enhances the hydrocarbon recovery from catalyst

surface by counter flow of steam up and catalyst down.
Closely structured packing has questionable reliability due to
plugging, particularly for RFCC operation
PentaFlow Packing is an improved design balancing high
performance, high reliability and easy maintenance
26
Minimising Coke Growth and Erosion in Cyclones
Coke growths on lee-side gas-outlet pipe

Erosion holes-through at inlet and bottom
1.
2.
Better design of cyclone top

Add Shell Bottom Internals
Phenomena studied in Dutch University and in Amsterdam
27
Shell FCC Cyclones System

1. Reliable Connections
2. Optimised I/O geometry
3. Internals to stop erosion

and increase efficiency
10-fold improvement in reliability

in last decade; steady since
4. Reliable Diplegs
Cyclone Service life exceeds 20 years
28
Port Dickson RFCC Unit Reliability

Port Dickson Mech. Availability, %
1999-2002 average
2002-2005 average
1999-2005 average
Solomon (2004) Asia-Pacific
99.4
94.4
96.9
94.6
Major issues and learning (2002 2005) T/A errors unrelated to design :
2003 :
-
2004
-
coking in the slurry recycle loop, due to 2002 T/A maintenance errors that
mayways of individual trays in main fractionation were left open
crack in regenerator overhead line due to an error in 2002 T/A that a repair was
not carried out resolved by adding an expansion joint
2005
nationwide power failure

29
FCC Performance Pyramid

Shell Global Solutions experience in all
areas of the FCC performance pyramid:
Catalyst
1.
Reliable design
2.
Unit operation (incl. SU & SD)
3.
Feed characterization
4.
Catalyst selection
Feed
Operation
Design
30
Mechanical availability of Shell GS Cat Crackers

1% = $ 60 mln per year
Causes of Unscheduled Downtime

Dow ntim e Days / Events (in %) per category
1)
2)
3)
4)
5)
6)
7)
8)
9)
Hardware, R&R
Hardware, other Equipm ent
Coking
O ther Process Conditions
Hum an Error
Instrum entation and Safeguarding
Utilities
Scheduling/M argin
O utside FCC Com plex
32
Shell CCUs process high Resid feedstocks
2007:
CCR optimal at ~6 max.
33
Catalyst Selection
Objective: catalyst cost reduction + margin
optimisation
Testing properly aged catalysts in our pilot
plant, using actual feedstock and process
conditions tailored to your operation
Translating pilot plant results to your
commercial unit using the Shell FCC
Process Model (SHARC)
Ranking according to value added
Independence from catalyst producers
Unique pilot plant capabilities
34
Catalyst Selection (continued)
Triggers for catalyst selection

Change
in Refinery objectives (i.e. to make more octane,

more propylene, lower gasoline olefins, etc.)
Major FCC unit revamp (i.e. close coupled cyclones, etc.)
Change of feedstock to unit
Availability of new catalyst technology
5-6 locations per year
Benefits: ~$ 1.5 mln/yr per location

35
SHARC Shell FCC Process Model

Proprietary heat-balanced FCC
process model developed by Shell
Yield predictions are validated
against commercial test run data.
Integrated with FCC on-line
optimization system and refinery
planning and scheduling tools.
Users of SHARC have seen their

FCC profitability improve by an
annual margin increase of say
USD 2-3 million
36
Benefit from SHARC Applications
Economic Benefit
Catalyst
Selection
Example
Resultsof
NORCO
Catalyst
Selection
Before Base Catalyst
May-Oct., 1999
Relative Margin
Relative Feed Rate Change
Catalyst Addition
CCR
Basic Nitrogen
C2&ltr (incl. H2S)
C3=
C4=
Total LPG
Naphtha (C5-221C)
LCO (221-355C)
HCO (355C+)
Coke
221C Conversion
Riser temperature
FCC Naptha RON Clear
FCC Naptha MON Clear
E-Cat Activity (Grace)
E-Cat Re2O3 (Grace)
$K/day
%
tons/day
%wt
ppm
%wt
%wt
%wt
%wt
%wt
%wt
%wt
%wt
%wt
C
MAT
%
100.0
9.1
0.26
192.3
4.39
5.35
6.34
17.4
45.44
15.86
11.06
5.85
73.08
533
93.65
81.53
67.92
0.56
SHARC Predictions
New Catalyst
After New Catalyst

Feb-Jul, 2000
14.2
97.9
5.9
0.26
192.3
4.51
5.28
6.24
17.4
46.95
15.19
10.03
5.92
74.78
539
93.95
82.03
68.0
1.03
16.7
99.2
6.4
0.24
228.4
4.60
5.28
6.44
17.26
46.93
15.96
9.59
5.66
74.45
535
94.1
82.2
68.1
1.03
37
Resid processing E-cat poisoning with Vanadium

Catalyst Vanadium resistance
Some Shell advised resid units

operate in an excess of 7500
ppm Vanadium !
SGSi pilot plant catalyst

selection procedure selects the
most Vanadium resistant
catalysts for the SGSi advised
CCUs
63
62
E-cat activity
Vanadium = poison for E-cat

zeolite
Improved catalyst Vanadium resistance
61
60
59
58
57
56
Catalyst A
55
Catalyst B
54
5500
6000
6500
7000
7500
8000
E-cat Vanadium, ppmw
38
Resid processing E-cat poisoning with Nickel

Catalyst Nickel resistance
Some Shell advised resid units

operate at very high E-cat
Nickel levels
Improved catalyst Nickel resistance

0.40
Nickel reacts hydrocarbons to

H2+coke
H2, wt%
SGSi catalyst selection methods

test catalyst Nickel tolerance in
realistic conditions in a pilot
plant deactivation unit
0.35
0.30
0.25
0.20
0.15
4000
Catalyst B
Catalyst A
4500
5000
5500
6000
Ni+V/4, ppm
39
Additives to adjust product slate or quality

ZSM-5 and gasoline-S reducers
SGSi has pilot plant facilities to carry out dedicated pilot
plant evaluations for ZSM-5 and Gasoline Sulfur
reduction additives
Several SGSi advised units use these additives
continuously (ZSM-5)
40
Additives reduce CCU emissions - SOx
H2 S release
SOx absorption
41
Additives for CCU emissions SOx and NOx

SGSi gives support for SOx and NOx additive selection and monitoring
Example: SOx additive trial at Reichstett up to 85% SOx reduction
14.0
SOx reduction, %
80%
11.2
R950 in INV, %
60%
8.4
40%
5.6
20%
2.8
0%
0.0
-20%
R950 in INV, %
SOx reduction, %
100%
-2.8
Nov06
Jan07
May07
42
Effectiveness of Gasoline Sulfur reducing additive

- Target < 10 ppm Gasoline Sulfur achieved with feed HT and Additive
3.0%
Base
2.8%
Gasoline Sulfur/Feed Sulfur (%)
Additive
2.6%
2.4%
2.2%
2.0%
1.8%
Additive reduced gasoline Sulfur

up to 40% at Constant Gasoline
Cut Point
1.6%
1.4%
1.2%
1.0%
410
415
420
425
430
435
440
445
450
455
460
SIMDIST Gasoline T95 (F)

43
Latest Shell Developments Examples
Process Design Modifications towards maximized

flexibility in products like Diesel / Propylene
Catalyst Circulation Enhancement for increased

capacity
Flue Gas Cleaning towards very low stack

emissions
44
Process Design Modifications towards maximized

flexibility in products like Diesel / Propylene
Enablers:
-
In conventional FCCU tuning of operating conditions, like:

- cat-to-oil ratio
- Riser temperature
- Sharpened design of feedguns, riser-internals, post-riser
contact time
- Catalyst formulation and activity
- Tuning of ZSM-5 catalyst-additive for propylene
New Enabler:
-
Equipment addition to conventional

FCCU to cleverly re-inject gasolinefractions aiming at superior diesel /
propylene yields
Technology is ongoing
R&D in Shell Labs
45
Catalyst Circulation Enhancement Technology

Additions to Standpipe
inlet
Unrivalled, recent concept

Ensures standpipe-stability
Enables much enhanced
circulation rate
(15-50% increase)
Even with poor E-Cat
10 designs, 5 installed
46
Third Stage Separator System (TSS)

the reliable and cost-effective solution to reach lowest emissions
1. The Flue Gas Cleaning System

2. The Shell Third Stage Separator
47
Evolution of Shell Third-Stage Separator
1960s-1980s
Expander
protection
1990s
Tightening Emission
Legislation
2005
Meeting <50 mg/m3
48
This is development
Improving Clean Stack (and reducing SOx/NOx emission)
As we respect our neighbours, and
To keep our license to operate
49
Closing Remarks
Shell Global Solutions is for CatCracking a unique entity to

provide 24 hr/day technological service to 12% of worlds FCC
users.
For Residue-FCCs where reliability is most at stake, the leading
position is even stronger.
Despite increased heaviness and impurities in feed (S, N etc) Cat
Cracking remains a worldwide leading conversion technology
Main challenges for the RFCC process are:
-
Reliability of operation
Quality of products and of environment
Meeting refiners need for wide flexibility on product-slate and feedstock
50

Shell Residue Fluidized Catalytic Cracking Process

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Shell Global Solutions

The Fluidized Catalytic Cracking Process

Presentation to KIVI - NIRIA

Shell Global Solutions

A 1990 presentation updated with a decade of developments

Shell Global Solutions

SIMPLIFIED REFINERY FLOW SCHEME

Long Residue (LR)

Short Residue (SR)

Shell Global Solutions

FLUID CAT. CRACKING UNIT (FCCU)

Light cycle oil

Heavy cycle oil

2-stage cyclone systems

Inter & Intra-stitial hydrocarbons

Catalyst gradually deactivated by

Fresh Feed & Recycles contacted

Regenerated catalyst flows to

Shell Global Solutions

Catalyst Circulation Rate (CCR), t/min

Catalyst to Oil (C/O) ratio, t/t

Coke burnt, t/d

Design Feed rate varies from

FCC PRODUCT YIELDS

Shell Global Solutions

Particle size ~ 70 micron

Activity, selectivity and stability

Good fluidisation characteristics

Carrier of heat from regenerator to riser

Shell Global Solutions

Fluid. Cat. Circulation Unit (FCCU)

Shell Support to the FCC Customers

(Shell International Petroleum

Shell Oil Houston

(Kon. Shell Lab. Amsterdam)

Shell Global Solutions is Shells technological consultancy group

FCC Business Size

Bigger than hydrocracking, coking and thermocracking capacities

3rd party customers: 0.9 MM bbl/d

Word-wide cat cracking capacity by Oil Company

Residue FCC: > 25% residue content

Our challenge is to process residue

Development in Shell Cat Cracker Design till 1990

Compact unit size

Process and catalyst development have improved

Alumina matrices for

SOx,, NOx, Gasoline Sulfur

The Geelong FCCU: Worlds most compact RFCCU

Fine Spray Feed Nozzles

The path towards the current Shell Design RFCCU

Shell Global Solutions

Port Dickson RFCC Unit (1999)

Shell Global Solutions

Port Dickson RFCC Project Execution and Operation

Best grassroots RFCC:

Shell Global Solutions

Port Dickson RFCC Unit Operation and Performance

Crude - 52.5 %w Oman and 47.5 %w Bach Ho

Feed - LR API 23.9, ~ 5.0 concarbon

Catalyst CCIC ~ 7 ton/day, 2% ZSM-5,

8.6 % HCO/Slurry, 7. 4 % coke

0.05 to 0.1 wt% ash in slurry (by-pass hydroclone)

Shell High Performance Feed Nozzles

Side View of Nozzle Arrangement