Shell Global Solutions The Fluidized Catalytic Cracking Process 65 years of inspiration for technology development Mart
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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
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A 1990 presentation updated with a decade of developments
Im pl
Imp
ation ent
ro
em
ve
t n e m
Design
R&
ion
Subject of this presentation
ra t
D Tro / g ubleshootin Inspection
e Op
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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) Shell Global Solutions
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Residue Upgrade (>370 oC) in relation to FCC process ability
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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 Shell Global Solutions
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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
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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
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FCC CATALYSTS
Particle size ~ 70 micron Particle density 1500 kg/m3 800 600
Real
ρ
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
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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
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Shell Support to the FCC Customers 1990 • SIPM Den Haag -
• •
(Shell International Petroleum Maatschappij)
Shell Oil Houston KSLA -
(Kon. Shell Lab. Amsterdam)
2007 • Shell Global Solutions -
Den Haag Amsterdam Houston Kuala Lumpur Bangalore
Shell Global Solutions is Shell’s technological consultancy group for Up- & Downstream Facilities, with strong R&D capabilities. Shell Global Solutions
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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) Shell Global Solutions
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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 Shell Global Solutions
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Development in Shell Cat Cracker Design till 1990
The original…. Big inventory , high C/O Poorish cat., Much coke Lowish temp’s CCR 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 (C5-176°C)
+ 0.7
LCO
+ 0.1
Coke
Shell Global Solutions
constant
Example of process benefits
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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
Again, result of large size experimentation in Amsterdam
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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
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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 Shell Global Solutions
Phenomena studied in Dutch University and in Amsterdam
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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
Shell Global Solutions
Cyclone Service life exceeds 20 years
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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 Shell Global Solutions
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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
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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) 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
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Shell CCUs process high Resid feedstocks
2007: CCR optimal at ~6 max.
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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
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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
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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
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Benefit from SHARC Applications
Economic Benefit Catalyst Selection Example Results–of NORCO Catalyst Selection Before Base Catalyst May-Oct., 1999 Relative Margin Relative Feed Rate Change Catalyst Addition CCR Basic Nitrogen C2<r (incl. H2S) C3= C4= Total LPG Naphtha (C5-221°C) LCO (221-355°C) HCO (355°C+) Coke 221°C 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 Shell Global Solutions 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
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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
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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
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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)
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Additives reduce CCU emissions - SOx
H2 S release
SOx absorption
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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 Nov’06
Jan’07
Shell Global Solutions
May’07
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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) Shell Global Solutions
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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
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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 Lab’s Shell Global Solutions
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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
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Third Stage Separator System (TSS) the reliable and cost-effective solution to reach lowest emissions
1. The Flue Gas Cleaning System Shell Global Solutions
2. The Shell Third Stage Separator
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Evolution of Shell Third-Stage Separator
1960s-1980s Expander protection
1990s Tightening Emission Legislation
2005 Meeting