The Fluidized Catalytic Cracking Process 65 years of ... - kivi niria

Shell Global Solutions 

The Fluidized Catalytic Cracking Process 

65 years of inspiration for technology development 

Mart Nieskens 

Presentation to KIVI - NIRIA 

October 4 th 2007


2 

A 1990 presentation updated with a decade of developments

3 

Implementation 

Operation 


Troubleshooting/ 

Inspection 

Design 

Subject of this 

presentation 

Improvement 

R&D

SIMPLIFIED REFINERY FLOW SCHEME 

LPG 

HYDROSKIMMER 

Crude 

Crude 

Distilling 

Unit 

Naphtha 

Kero/Gasoil 

Hydro 

Treater 

Long Residue (LR) 

Platformer 

Hydro 

Desulph. 

Unit 

LPG 

Mogas 

Kero 

Gasoil 

Fuel Oil 

High 

Vacuum 

Unit 

Flashed 

Distillate 

Short Residue (SR) 

- 

Cat Cracker 

Hydro 

Desulph. 

Unit 

Gasoil 

COMPLEX 


4

Residue Upgrade 

(>370 o C) in relation to 

FCC process ability 


5

FLUID CAT. CRACKING UNIT (FCCU) 

Pres., barg Temp., C 

Flue gas 

Reactor 

P 

2.0 

T 

L 

P 

2.0 

525 

Light cycle oil 

Heavy cycle oil 

700 

Riser 

Steam 

350 

Fractionator 

Slurry 

oil 

Air blower 

Flashed Distillate / 

Long residue 

Air 


6

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 

Regenerated catalyst flows to 

bottom of liftpot-riser 

Fresh Feed & Recycles contacted 

with regenerated catalyst in riser 

Catalyst flow 

controlled by 

pressure-balance 

and slide-valves 


7

Feedrate, t/d 

Feed temperature, °C 

Riser temperature, °C 

Catalyst Circulation Rate (CCR), t/min 

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

Air-rate, t/d 

FCC OPERATING 

CONDITIONS 

Regenerator temperature, °C 

Coke burnt, t/d 

Design Feed rate varies from 

1.500 to 20.000 t/d 

Typ. 

5000 

250 

525 

25 

7.5 

3750 

700 

250 

FCC PRODUCT YIELDS 

Dry gas 

LPG 

Gasoline (C5 - 221 °C TBP) 

LCO (221 - 370 °C TBP) 

HCO + SO (370 + °C TBP) 

Coke 

Typical…. 

Typical range 

2 - 5 

8 - 18 

40 - 55 

14 - 25 

6 - 15 

4 - 8 


8

FCC CATALYSTS 

Particle size ~ 70 micron 

Particle density 1500 kg/m 3 

800 

Real 

600 

ρ app 

REQUIREMENTS: 

• Activity, selectivity and stability 

• Good fluidisation characteristics 

• Carrier of heat from regenerator to riser 

400 

200 

U mb 

U mf v g = ∆v [cm/s] 

0.01 0.1 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 

• 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. 


11

DEER PARK 

MARTINEZ 

NORCO 

CONVENT 

PUGET SOUND 

PORT ARTHUR 

Shell Global Advised Solutions Fluid Catalytic Crackers 

Cat Cracking Services 

SARNIA 

MONTREAL EAST 

PERNIS 

STANLOW 

Coryton 

1990 

• 30 units, being 

- Shell owned or 

- alliances 

MONGSTAD 

BERRE 

REICHSTETT 

PETIT COURONNE 

Tupras 

2007 

• 43 units, being 

- Shell Owned or 

- Joint ventures, or 

- Third Party 

HARBURG 

Miro 

RELIANCE 

YOKKAICHI 

SEIBU 

TOA 

GEELONG 

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) 

3 rd 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 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% 

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 temp’s CCR

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 5 for 

octane improvement 

light olefins (C3 = , C4 = ) 

• SO x, 

, NO x, 

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: 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 


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. > 4 yrs reliable operation 

2. Full riser coverage 

3. Process benefits 

4. Low steam usage 

Yield Shifts 


(%wt on feed) 

Dry Gas - 0.3 

LPG - 0.5 

Gasoline (C5-176 

176°C) 

+ 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. Better design of cyclone top 

2. 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 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 


29

FCC “Performance Pyramid” 

Shell Global Solutions experience in all 

areas of the FCC performance pyramid: 

1. Reliable design 

2. Unit operation (incl. SU & SD) 

3. Feed characterization 

4. Catalyst selection 

Catalyst 

Feed 

Operation 

Design 


30


Mechanical availability of Shell GS Cat Crackers 

1% = $ 60 mln per year

Causes of Unscheduled Downtime 

Downtime Days / Events (in %) per category 

1) Hardware, R&R 

2) Hardware, other Equipment 

3) Coking 

4) Other Process Conditions 

5) Human Error 

6) Instrumentation and Safeguarding 

7) Utilities 

8) Scheduling/Margin 

9) Outside FCC Complex 


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 Results – of Catalyst NORCO Selection Catalyst Example Selection 

Before Base Catalyst 

May-Oct., 1999 

SHARC Predictions 

New Catalyst 

After 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. H 2 S) %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 

E-Cat Re2O3 (Grace) % 0.56 1.03 1.03 

37

Resid processing - 

E-cat poisoning with Vanadium 

• Some Shell advised resid units 

operate in an excess of 7500 

ppm Vanadium ! 

• Vanadium = poison for E-cat 

zeolite 

• SGSi pilot plant catalyst 

selection procedure selects the 

most Vanadium resistant 

catalysts for the SGSi advised 

CCUs 

E-cat activity 

Improved catalyst Vanadium resistance 

63 

62 

61 

60 

59 

58 

57 

56 

55 

54 

Catalyst Vanadium resistance 

Catalyst A 

Catalyst B 

5500 6000 6500 7000 7500 8000 

E-cat Vanadium, ppmw 


38

Resid processing - 

E-cat poisoning with Nickel 

• Some Shell advised resid units 

operate at very high E-cat 

Nickel levels 

• Nickel reacts hydrocarbons to 

H2+coke 

• SGSi catalyst selection methods 

test catalyst Nickel tolerance in 

realistic conditions in a pilot 

plant deactivation unit 

H2, wt% 

Catalyst Nickel resistance 

0.40 

0.35 

0.30 

0.25 

0.20 

0.15 

Improved catalyst Nickel resistance 

Catalyst B 

Catalyst A 

4000 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 - SO x 

H2 S release 

SOx absorption 


41

Additives for CCU emissions – SO x and NO x 

SGSi gives support for SO x and NO x additive selection and monitoring 

Example: SO x 

additive trial at Reichstett – up to 85% SO x 

reduction 

SOx reduction, % 

100% 

80% 

60% 

40% 

20% 

0% 

SOx reduction, % 

R950 in INV, % 

14.0 

11.2 

8.4 

5.6 

2.8 

0.0 

R950 in INV, % 

-20% 

-2.8 

Nov’06 Jan’07 


May’07 

42

Effectiveness of Gasoline Sulfur reducing additive 

- Target < 10 ppm Gasoline Sulfur achieved with feed HT and Additive 

Gasoline Sulfur/Feed Sulfur (%) 

3.0% 

2.8% 

2.6% 

2.4% 

2.2% 

2.0% 

1.8% 

1.6% 

1.4% 

1.2% 

Additive reduced gasoline Sulfur 

up to 40% at Constant Gasoline 

Cut Point 

Base 

Additive 

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: 

New Enabler: 

- “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 

- 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 


45

Catalyst Circulation Enhancement Technology 

Additions to Standpipe 

inlet 

• Unrivalled, recent concept 

• Ensures standpipe-stability 

• Enables much enhanced 

circulation rate 

(15-50% 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

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 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 


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The Fluidized Catalytic Cracking Process 65 years of ... - kivi niria

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