Shell Global Solutions

The Fluidized Catalytic Cracking Process

65 years of inspiration for technology development
Mart Nieskens

Presentation to KIVI - NIRIA

October 4th 2007
 Shell Global Solutions 2

A 1990 presentation updated with a decade of developments

 Design
nt Im
ve me pl

em
ro

ent
Imp

ation
Subject of this
presentation

ion
R&

t
ra
e
Tro g/ Op
ubleshootin
Inspection Shell Global Solutions 3
 SIMPLIFIED REFINERY FLOW SCHEME

LPG HYDROSKIMMER
Naphtha Hydro LPG
Crude Crude Platformer Mogas
Treater
Distilling Hydro
Unit Kero/Gasoil Kero
Desulph. Gasoil
Unit
Long Residue (LR)
Fuel Oil

High Flashed
Distillate - Hydro
Vacuum Cat Cracker Desulph. Gasoil
Unit Unit
COMPLEX
Short Residue (SR)

Shell Global Solutions 4

Residue Upgrade
(>370 oC) in relation to
FCC process ability

Shell Global Solutions 5

 FLUID CAT. CRACKING UNIT (FCCU)

Pres., barg Temp., C

P
Flue gas
Reactor
2.0
T Light cycle oil

P 2.0 525
Heavy cycle oil
L
Steam
700
350
Riser Slurry
Fractionator oil

Flashed Distillate /
Air blower Long residue

Air

Shell Global Solutions 6

 2-stage cyclone systems
FCC Process 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

Regenerated catalyst flows to with regenerated catalyst in riser
bottom of liftpot-riser

Catalyst flow
controlled by
pressure-balance
and slide-valves
Shell Global Solutions 7
 FCC OPERATING Typ.
CONDITIONS Typical….
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 7.5
Air-rate, t/d 3750 FCC PRODUCT YIELDS Typical range
Regenerator temperature, °C 700
Dry gas 2-5
Coke burnt, t/d 250
LPG 8 - 18
Gasoline (C5 - 221 °C TBP) 40 - 55
LCO (221 - 370 °C TBP) 14 - 25
Design Feed rate varies from
1.500 to 20.000 t/d HCO + SO (370 + °C TBP) 6 - 15
Coke 4-8

Shell Global Solutions 8

 FCC CATALYSTS

Particle size ~ 70 micron

Particle density 1500 kg/m3

800 Real

600
ρ app

400

REQUIREMENTS: 200
• Activity, selectivity and stability Umb
Umf vg = ∆v [cm/s]
• Good fluidisation characteristics
0.01 0.1 1 10 100
• Carrier of heat from regenerator to riser
Shell Global Solutions 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

Shell Global Solutions 10

Shell Support to the FCC Customers

1990 2007
• SIPM Den Haag • Shell Global Solutions
- (Shell International Petroleum - Den Haag
Maatschappij) - Amsterdam
• Shell Oil Houston - Houston
• KSLA - Kuala Lumpur
- (Kon. Shell Lab. Amsterdam) - Bangalore

Shell Global Solutions is Shell’s technological consultancy group

for Up- & Downstream Facilities, with strong R&D capabilities.
Shell Global Solutions 11
 Shell Advised
Shell Global Fluid Catalytic Crackers
Solutions
Cat Cracking Services 1990 2007
• 30 units, being • 43 units, being
- Shell owned or - Shell Owned or
- alliances - Joint ventures, or

MONGSTAD - Third Party

BERRE HARBURG
DEER PARK PERNIS STANLOW REICHSTETT
SARNIA Miro
MARTINEZ Coryton PETIT COURONNE
MONTREAL EAST YOKKAICHI
NORCO RELIANCE
CONVENT SEIBU
PUGET SOUND TOA
PORT ARTHUR GEELONG
Tupras CLYDE

Petrotrin

ECOPETROL

CARDON BUENOS AIRES DURBAN PORT SRIRACHA SINGAPORE

DICKSON
 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)
Shell Global Solutions 13
Word-wide cat cracking capacity by Oil Company
Total FCC, KB/D Residue FCC, KB/D

ExxonMobil 1260 140

RD Shell 1080 510
Sinopec 740 170
Valero 730 50
BP 670 50
Petrobras 520 80
Total 430 75

World 16000 1750

Shell GS advise 1900 510
12 % 30%
Our challenge is to process residue
Residue FCC: > 25% residue content in a profitable and reliable way
Shell Global Solutions 14
 Development in Shell Cat Cracker Design till 1990

Gasoline + / fuel – Compact unit size

Zeolite catalyst Resid feed (CCR < 3) TSS build into Regen
The original…. 3
Big inventory , high C/O Riser Cracking no reactor; feedguns Innovative design
Stripper-baffles inside Cat.coolers; high High cap. Cat.cooler
Poorish cat., Much coke ShellT’s
Global Solutions 15

Lowish temp’s CCR<0.3 reactor. CCR < 1.5 Still single regen.vessel CCR < 7
Complete Combustion
Process and catalyst development have improved
the conversion and yields Late 1990’s:
• Alumina matrices for
Nickel passivation
• Metal traps for
Vanadium passivation
• Improved zeolite stability for
maximum conversion
• Improved catalyst porosity
for resid processing

2000’s : Additives
• ZSM-5 for
octane improvement
light olefins (C3=, C4=)

• SOx,, NOx, Gasoline Sulfur

Shell Global Solutions 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

Shell Global Solutions 17

The Geelong FCCU: World’s 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 spec’s only after tuning the
equipment elements
Shell Global Solutions 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)

Shell Global Solutions 19

 Port Dickson RFCC Unit (1999)
• Feed rate ~ 42,000 BPD;
• ConCarbon ~ 5.0 average, 6.2 max

Shell Global Solutions 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

Shell Global Solutions 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)

Shell Global Solutions 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
Shell Global Solutions 23
Shell High
Performance
Feed Nozzles

1. > 4 yrs reliable operation

2. Full riser coverage
3. Process benefits Yield Shifts (%wt on feed)
4. Low steam usage
Dry Gas - 0.3
LPG - 0.5
Gasoline (C5-176°C) + 0.7
LCO + 0.1
Coke Shell Global Solutions constant 24

Example of process benefits

 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

Shell Global Solutions 25

Again, result of large size experimentation in Amsterdam

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
Shell Global Solutions 26
 Minimising Coke Growth and Erosion in Cyclones

Coke growths on lee-side gas-outlet pipe

Erosion “holes-through” at inlet and bottom

1. Better design of cyclone top

2. Add Shell Bottom Internals
Shell Global Solutions 27

Phenomena studied in Dutch University and in Amsterdam

Shell FCC Cyclones System
1. Reliable Connections

2. Optimised I/O geometry

3. Internals to stop erosion

and increase efficiency

4. Reliable Diplegs
10-fold improvement in reliability
in last decade; steady since

Shell Global Solutions 28

Cyclone Service life exceeds 20 years

 Port Dickson RFCC – Unit Reliability
Port Dickson Mech. Availability, %
1999-2002 average 99.4
2002-2005 average 94.4
1999-2005 average 96.9
Solomon (2004) Asia-Pacific 94.6

Major issues and learning (2002 –2005) – T/A errors unrelated to design :
• 2003 :
- coking in the slurry recycle loop, due to 2002 T/A maintenance errors that
mayways of individual trays in main fractionation were left open
• 2004
- 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
Shell Global Solutions 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

Shell Global Solutions 30

 Shell Global Solutions

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) Hardware, R&R
2) Hardware, other Equipm ent
3) Coking
4) O ther Process Conditions
5) Hum an Error
6) Instrum entation and Safeguarding
7) Utilities
8) Scheduling/M argin
9) O utside FCC Com plex

Shell Global Solutions 32

Shell CCUs process high Resid feedstocks

2007:
CCR optimal at ~6 max.

Shell Global Solutions 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

Shell Global Solutions 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

Shell Global Solutions 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

Shell Global Solutions 36

Benefit from SHARC Applications

Results–of
Economic Benefit NORCO
Catalyst Catalyst
Selection Selection
Example
Before Base Catalyst SHARC Predictions After New Catalyst
May-Oct., 1999 New Catalyst Feb-Jul, 2000

Relative Margin $K/day - 14.2 16.7

Relative Feed Rate Change % 100.0 97.9 99.2
Catalyst Addition tons/day 9.1 5.9 6.4
CCR %wt 0.26 0.26 0.24
Basic Nitrogen ppm 192.3 192.3 228.4
C2&ltr (incl. H2S) %wt 4.39 4.51 4.60
C3= %wt 5.35 5.28 5.28
C4= %wt 6.34 6.24 6.44
Total LPG %wt 17.4 17.4 17.26
Naphtha (C5-221°C) %wt 45.44 46.95 46.93
LCO (221-355°C) %wt 15.86 15.19 15.96
HCO (355°C+) %wt 11.06 10.03 9.59
Coke %wt 5.85 5.92 5.66
221°C Conversion %wt 73.08 74.78 74.45
Riser temperature °C 533 539 535
FCC Naptha RON Clear 93.65 93.95 94.1
FCC Naptha MON Clear 81.53 82.03 82.2
E-Cat Activity (Grace) MAT 67.92 68.0
Shell Global Solutions 68.1 37

E-Cat Re2O3 (Grace) % 0.56 1.03 1.03

 Resid processing -
E-cat poisoning with Vanadium
Catalyst Vanadium resistance
• Some Shell advised resid units
operate in an excess of 7500 Improved catalyst Vanadium resistance
ppm Vanadium ! 63

• Vanadium = poison for E-cat 62

61
zeolite
E-cat activity
60
• SGSi pilot plant catalyst 59
58
selection procedure selects the 57
most Vanadium resistant 56 Catalyst A
catalysts for the SGSi advised 55 Catalyst B
54
CCUs 5500 6000 6500 7000 7500 8000
E-cat Vanadium, ppmw

Shell Global Solutions 38

 Resid processing -
E-cat poisoning with Nickel
Catalyst Nickel resistance
• Some Shell advised resid units
operate at very high E-cat Improved catalyst Nickel resistance
Nickel levels
0.40
• Nickel reacts hydrocarbons to
0.35
H2+coke

H2, wt%
• SGSi catalyst selection methods 0.30

test catalyst Nickel tolerance in 0.25

Catalyst B
realistic conditions in a pilot 0.20
Catalyst A
plant deactivation unit 0.15
4000 4500 5000 5500 6000
Ni+V/4, ppm

Shell Global Solutions 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)

Shell Global Solutions 40

Additives reduce CCU emissions - SOx

H2 S release

SOx absorption

Shell Global Solutions 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

100% 14.0
SOx reduction, %
80% 11.2
SOx reduction, %

R950 in INV, %
R950 in INV, %
60% 8.4
40% 5.6
20% 2.8
0% 0.0
-20% -2.8
Shell Global Solutions 42
Nov’06 Jan’07 May’07
 Effectiveness of Gasoline Sulfur reducing additive
- Target < 10 ppm Gasoline Sulfur achieved with feed HT and Additive

3.0%
Base
2.8%
Additive
2.6%
Gasoline Sulfur/Feed Sulfur (%)

2.4%

2.2%

2.0%

1.8% Additive reduced gasoline Sulfur

up to 40% at Constant Gasoline
1.6% Cut Point

1.4%

1.2%

1.0%
410 415 420 425 430 435 440 445 450 455 460
SIMDIST Gasoline T95 (°F)
Shell Global Solutions 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

Shell Global Solutions 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 gasoline- Technology is ongoing
fractions aiming at superior diesel / R&D in Shell Lab’s
propylene yields
Shell Global Solutions 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

Shell Global Solutions 46

Third Stage Separator System (TSS)
the reliable and cost-effective solution to reach lowest emissions

1. The Flue Gas Cleaning System

Shell Global Solutions 47

2. The Shell Third Stage Separator

 Evolution of Shell Third-Stage Separator

1960s-1980s
Expander
protection 1990s
Tightening Emission
Legislation 2005
Meeting <50 mg/m3
Shell Global Solutions 48
This is development……
Improving Clean Stack (and reducing SOx/NOx emission)
As we respect our neighbours, and
To keep our license to operate

Shell Global Solutions 49

Closing Remarks

• Shell Global Solutions is for CatCracking a unique entity to

provide 24 hr/day technological service to 12% of world’s FCC
users.
• For Residue-FCC’s 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 refiner’s need for wide flexibility on product-slate and feedstock

Shell Global Solutions 50