VGO Hydrocracking

Latest Improvements in Hydrocr Hyd rocrack acking ing Tech Technol nologie ogies s Jérôme Bonnardot

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Content

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Axens Axens’’ Hydro Hydroco conve nversi rsion on Offer Offer

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CFHT / Mild Mild Hydrocr Hydrocracki acking ng – HyC-10 HyC-10TM

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High Convers Conversion ion Hydrocr Hydrocracki acking ng – HyKTM

•

New Generation Generation of Hydrocracking Hydrocracking Catalysts

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Conclusions

ARTC Refining and and Petrochemicals Petrochemicals - Kuala Lumpur Lumpur - 10-12 March March 2009

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1

Conversion Mapping g n i p p o T

Crude Oil

CFHT* MHC** HyC-10

. VGO t s i D . c a V

s o n FCC i s t t a y r s i ga l u t f a n C t o C s s e t s HyK c e a LCO o L P r

Hyvahl H-OilRC ® HDHPLUS

LPG Naphtha Jet / Kero

R2R Diesel

VR

Fuel-Oil Solvahl HCGO

DAO

H-OilDC

Pitch

HySCOP ARTC Refining and Petrochemicals - Kuala Lumpur - 10-12 March 2009

Syncrude * CFHT = Cat Feed HydroTreating; **MHC = Mild Hydrocracking

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Content

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Axens’ Hydroconversion Offer

•

CFHT / Mild Hydrocracking – HyC-10TM

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High Conversion Hydrocracking – HyKTM

•

New Generation of Hydrocracking Catalysts

•

Conclusions

ARTC Refining and Petrochemicals - Kuala Lumpur - 10-12 March 2009

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HyC-10TM Configuration Fuel gas, Naphtha

MHC section

• Processes cracked

VGO

H2

Off spec Diesel

Polishing section

LCO LCGO Heavy SRGO

Low S FCC feed ULSD (10 ppm S)

GO + LCO, LCGO in the polishing reactor and produce ULSD

• Saves 2 compressors • Minimizes CAPEX/OPEX

• 2 units in operation and 1 under design

Produces low Sulphur FCC Feed + ULSD simultaneously 5


HyC-10TM Commercial Experience MOH: Corinth Refinery Start-up: Nov 2005 Feedstocks: MHC: SRVGO+ aro extract Polishing: GO ex MHC + LCO + SRGO + VB naphtha Products: FCC Feed: S < 600 wtppm Diesel: S < 10 wtppm & CI > 51 Total Conversion: 30 wt% ARTC Refining and Petrochemicals - Kuala Lumpur - 10-12 March 2009

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3

HR 568 CoMoNi For CFHT Application Effluent Sulfur Content, wt ppm

Breakthrough Catalyst

1800 1600

Straight run VGO Same operating conditions

HR 448

1400 1200

HR 548

6 references (in 5 months) obtained after pilot tests

1000 800 600 400 200 0

HR 568 10 °C

5 °C

More Active in HDA Same HDN Activity

Reactor Temperature, °C


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Revamp of VGO Pretreat to MHC Unit

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2 Catalytic solutions : • Alumina Type catalyst only (NiMo, NiCoMo) • Low Conversion Activity • Small Conversion boost Required

• HDT + ASA Type Catalyst (HR 548 + HDK 776) • Good Selectivity toward MD • No dedicated SIL system required • Good Tolerance to Nitrogen • Better Activity than Alumina type


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HR 548 + HDK 776 For Mild Hydrocracking Application Higher conversion is possible through a dual catalyst system with NiMo on Alumina and NiW on ASA 50

NiMo / Alumina HR 548 HDS HDN NiW / ASA HDK 776 HDA HCK

) % t w ( n o i s r e v n o C t e N

HR 548 + HDK776 40

5 15 % %

30

20

HR 548 10

HR 448

0

Reactor Temperature (°C)

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Content

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•

Mild Hydrocracking – HyC-10TM

•


•


•

Conclusions


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5

Axens HP Hydrocracker Flexible Process H2 Conventional crude VGO Special crude VGO

Euro V Diesel, Jet A1 + High VI Lube Oil Bases and/or SC Feed

Coker VGO Visbreaker VGO

FLEXIBLE PROCESS

DAO Furfural extracts Paraffins LCO HCO

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Single Stage Once-Through SSOT Western Europe Reference - 2006 −

SSOT Scheme, 50 000 BPSD (Construction Phase) FG / LPG

85 wt. % Conversion

Naphtha Isom / CCR

Feed

HDT

HyK

LVGO HVGO HCGO 25%

SEP

F R A C

Kerosene Jet A1

Diesel Euro V

• High UCO value • Lowest CAPEX

UCO

• Nine awards since 2005

Group III Lube Oil Production


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6

Single Stage Once-Through SSOT South America Reference - 2007 −

•

For feed with high nitrogen content up to over 5000 ppm (Marlim Crude)

•

SSOT Scheme, 54 000 BPSD (FEED Phase) 85 wt. % Conversion on Marlim crude FG / LPG

H2S + NH3

Light Naphtha Steam Cracking

Feed LVGO HDT1 HVGO HCGO 18%

SEP1

HDT2

HyK

F R A C

SEP2

Integrated Reaction Section

Heavy Naphtha CCR + Aromatics

Medium Distillate Steam Cracking

• Dedicated for very heavy VGO Feeds • High product values

UCO Petrochemical FCC

• One award since 2007

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Single Stage with Recycle SSREC Middle East Reference - 2007 −

SSREC Scheme, 38 000 BPSD (FEED Phase) FG / LPG

97 wt. % Conversion

Naphtha Pool / CCR

Feed

HDT

HyK

SEP

VGO HCGO 16%

F R A C

Kerosene Jet A1

Diesel Euro V

• Higher MD yield

liquid recycle

Bleed

• Higher product quality • Two awards since 2007 ARTC Refining and Petrochemicals - Kuala Lumpur - 10-12 March 2009

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Two Stage with Recycle TSREC African Reference - 2006 −

TSREC Scheme, 66 000 BPSD (FEED Phase) FG / LPG

98 wt. % Conversion

Naphtha

Feed

HDT

HyK

CCR / Isom

F R A C

SEP

HVGO HCGO 22%

Kerosene Jet A1

Diesel Euro V

• Highest MD yield Bleed

HyK

• High diesel incentive • One award since 2006

2nd Stage 15


Hydrocracking Licensing Geographical Breakdown

22 5 6

CIS

Europe

16

North America Asia - Pacific

12

Middle East - Africa 8

Central & South America 32% 9%

World Total: 71 Licenses Cumulative Capacity: ~ 2,935,000 bpsd

Between 2005 and 2008 13 References in HCK 15 References in MHC / CFHT ARTC Refining and Petrochemicals - Kuala Lumpur - 10-12 March 2009

7% 12%

23% 17% as of December 2008

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8

Content

•


•

Mild Hydrocracking – HyC-10TM

•


•


•

Conclusions


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Latest in Hydrocracking Catalysts

•

500 Series - Hydrotreating •

•

700 Series - Hydrocracking •

•

HyKTM application (Pretreating section)

HyKTM applications (Cracking section)

More than 40 commercial references

• Apply also for CFHT & HyC-10 TM application


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9

HyKTM Catalysts Arrangement

HF 858 NiMo / Alumina HRK 558 NiMo / Alumina

HYK 742 NiMo / Zeolite

HDK 776 NiW / ASA

HR 516 CoMo / Alumina

HDM HDS HDN HDA HCK

Optimum Cycle Length Optimum Middle Distillates Yields Optimum Product Quality (VI and naphtha S content) 19


Latest in Hydrocracking Catalysts Middle Distillate Selectivity

•

500 Series - Hydrotreating • MHC, HyKTM applications (Pretreating section)

HR 548 • New 700 Series - Hydrocracking • MHC, HyKTM applications (Cracking section) HRK 558

Alumina

HDK 776 Very High Middle Distillate

HYC 652 High Middle Distillate

HYK 742 HYC 642 High Conversion

Conversion Activity

More than 40 commercial references for MHC & HyKTM applications ARTC Refining and Petrochemicals - Kuala Lumpur - 10-12 March 2009

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10

HYK 700 Series Optimizing Acidic Support Properties

Tuned porosity

Optimized shaping

Tuned acidity -20

0

20

Al1 -Al3

Al2-Al3

40

60

Al1-Al1 80 80

60

Al2 -Al1 40

3800 20

0

3750

3700

3650

3600

3550

3500

3450

3400

Wavenumbers(cm-1)

-20

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ARTC Refining and Petrochemicals - Kuala Lumpur - 10-12 March 2009 (ppm)

Towards Molecular Scale Understanding of Catalyst Arrangement Comprehensive Feedstock characterization AL crude VGO (370-566 C)

Heavy fraction from SAR

°

5 - r i n g s 4 - r i n g s

HDT inhibitor identification

Tetraaromatics +

3 - r i n g s

N-species heavy aromatics

Triaromatics Diaromatics Monoaromatics Saturates nC44

nC50

increasing b.p.

increasing b.p.

Kinetics modelling

1,4 1,2

Extended PIONA

) w / w % ( t n e t n o C

1,0 N-paraffins Iso-paraffins

0,8

Mono-naphthens 0,6

Monoaromatics Diaromatics

0,4

Triaromatics 0,2 0,0 14

1 5

1 6

1 7

1 8

1 9

2 0

2 1

2 2

23

24

25

26

27

28

2 9

3 0

3 1

3 2

3 3

3 4

3 5

3 6

37

38

39

40

41

42

43

44

45

46

47

48

49

5 0

5 1

Atom carbon number


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Comprehensive Reaction Progress Three-Dimensional Gas Chromatography HRK HRK 558 558 Feedstock

HDK HDK 776 776

Pretreating section

HYK HYK 742 Hydrocracking section

n- pa r af fi n s

n+iso par af fi ns

iso-par af fi ns

nC48

nC41

nC22

nC22

nC22

nC41

1 -r i n g 2 - ri n g

N a p ht he n a ro m s a t ic s

3 - ri n g

n a p h te n e s

> 3- r i ng

Arabian Light VGO (370-566°C)

Unconverted Product (370+ °C) HDN, HDA activity tuning Pretreating / Hydrocracking balance

Unconverted Product (370+ °C) Cracking balance Hydrogenation / Acidity tuning • MD selectivity • UCO VI optimization 23


HYK 742 High Activity & Middle Distillate Selectivity •

HYK 742 catalyst characteristics • New optimized acidity & porosity zeolite • New high surface area alumina gel • Higher Mo content & dispersion

) % . 100 t w ( - 90 C ° 0 7 3 80 n i n o 70 i s r e v n 60 o C

5 to 8°C moreactive active 8°C more than previous generation than previous generation HYK742

HYC642

50 Reactor Temperature


•

Key features • Controlled acidity • Distance between acid and metal sites • Higher metal availability

Same Middle Distillate Selectivity y t i v i t c e l e S e t a l l i t s i D e l d d i M

HYC642

HYK742

°

Conversion in 370 C- (wt.%) 24

12

Western European Catalyst Case

• • •

7200 tons/day Conversion 80-85 % Started-up end 2006 25


HyKTM Catalysts Arrangement Previous Loading

Actual Loading

ACT 077

ACT 069 / ACT 077

HMC 945/ HMC 841

HMC 868

HR 448

HRK 558

HYC 642

HDK 776

HR 406

HYK 742 HR 516


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13

Hydrocracking Technology Conclusions •

HyC-10TM state of the art technology for CFHT / MHC • Combined production of low sulphur FCC feed and ULSD

•

HyKTM state of the art technology for Hydrocracking • Key route to produce high yields of high quality diesel & jet fuels • Optimized process configuration for meeting requested conversion and selectivity • Use EquiFlowTM internals (distributor, quench devices)

•

New generation of Combined Catalyst System generates higher returns for refiner • Performing Analytical tool linked with kinetic modeling permit to fine tuned catalytic system


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Latest Improvements in Hydrocracking Technology

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VGO Hydrocracking

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