Latest Improvements in Hydrocracking Technologies

Jrme Bonnardot

Content

Axens Hydroconversion Offer CFHT / Mild Hydrocracking HyC-10TM High Conversion Hydrocracking HyKTM New Generation of Hydrocracking Catalysts Conclusions

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

Conversion Mapping
Topping

Vac. Dist.

Crude Oil

VGO

CFHT* MHC** HyC-10

s on FCC ai rstts y au igl nft Ca to C tes ss HyK La LCOoce r P

LPG Naphtha Jet / Kero Diesel Fuel-Oil

Hyvahl H-OilRC HDHPLUS

VR

R2R

Solvahl
HCGO Pitch

DAO

H-OilDC Syncrude
* CFHT = Cat Feed HydroTreating; **MHC = Mild Hydrocracking
3

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

Content

Axens Hydroconversion Offer CFHT / Mild Hydrocracking HyC-10TM High Conversion Hydrocracking HyKTM New Generation of Hydrocracking Catalysts Conclusions

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

HyC-10TM Configuration
MHC section
Fuel gas, Naphtha

Processes cracked
GO + LCO, LCGO in the polishing reactor and produce ULSD Saves 2 compressors Minimizes CAPEX/OPEX 2 units in operation and 1 under design

VGO

Off spec Diesel

H2

Polishing section

LCO LCGO Heavy SRGO

Low S FCC feed ULSD (10 ppm S)

Produces low Sulphur FCC Feed + ULSD simultaneously

ARTC Refining and Petrochemicals - Kuala Lumpur - 10-12 March 2009 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 6

HR 568 CoMoNi For CFHT Application

Effluent Sulfur Content, wt ppm
1800 1600 1400 1200 1000 800 600 400 200 0

Breakthrough Catalyst Straight run VGO Same operating conditions 6 references (in 5 months) obtained after pilot tests

HR 448 HR 548 HR 568 10 C More Active in HDA Same HDN Activity

5 C

Reactor Temperature, C
7

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

Revamp of VGO Pretreat to MHC Unit

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

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

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

Net Conversion (wt%)

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

HR 548 + HDK776
40

30 20

5% 15 %
HR 548 HR 448

10

Reactor Temperature (C)

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

Content

Axens Hydroconversion Offer Mild Hydrocracking HyC-10TM High Conversion Hydrocracking HyKTM New Generation of Hydrocracking Catalysts Conclusions

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

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Axens HP Hydrocracker Flexible Process

H2
Conventional crude VGO Special crude VGO Coker VGO Visbreaker VGO DAO Furfural extracts Paraffins LCO HCO
ARTC Refining and Petrochemicals - Kuala Lumpur - 10-12 March 2009 11

FLEXIBLE PROCESS

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

Single Stage Once-Through SSOT Western Europe Reference - 2006

SSOT Scheme, 50 000 BPSD (Construction Phase) 85 wt. % Conversion FG / LPG Naphtha
Isom / CCR

Feed
LVGO HVGO HCGO 25%

HDT

HyK

SEP

F R A C

Kerosene
Jet A1

Diesel
Euro V

High UCO value Lowest CAPEX Nine awards since 2005 UCO
Group III Lube Oil Production

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

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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
H2S + NH3 FG / LPG

Light Naphtha

Feed
LVGO HDT1 HVGO HCGO 18%
SEP1

HDT2

HyK

SEP2

Integrated Reaction Section

F R A C

Steam Cracking

Heavy Naphtha
CCR + Aromatics

Medium Distillate
Steam Cracking

Dedicated for very heavy VGO Feeds High product values One award since 2007
ARTC Refining and Petrochemicals - Kuala Lumpur - 10-12 March 2009

UCO
Petrochemical FCC

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Single Stage with Recycle SSREC Middle East Reference - 2007

SSREC Scheme, 38 000 BPSD (FEED Phase) 97 wt. % Conversion FG / LPG Naphtha
Pool / CCR

Feed
VGO HCGO 16%

HDT

HyK

SEP

F R A C

Kerosene
Jet A1

Diesel
Euro V

Higher MD yield Higher product quality Two awards since 2007

liquid recycle

Bleed

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) 98 wt. % Conversion FG / LPG Naphtha Feed
HVGO HCGO 22% CCR / Isom

HDT

HyK

SEP

F R A C

Kerosene
Jet A1

Diesel
Euro V

Highest MD yield High diesel incentive One award since 2006

HyK

Bleed

2nd Stage
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ARTC Refining and Petrochemicals - Kuala Lumpur - 10-12 March 2009

Hydrocracking Licensing Geographical Breakdown

22 5 6

Europe
12

CIS

16

North America Asia - Pacific

Middle East - Africa

Central & South America

32% 9%

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

7% 12% 23% 17%

as of December 2008

Between 2005 and 2008 13 References in HCK 15 References in MHC / CFHT

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

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Content

Axens Hydroconversion Offer Mild Hydrocracking HyC-10TM High Conversion Hydrocracking HyKTM New Generation of Hydrocracking Catalysts Conclusions

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

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Latest in Hydrocracking Catalysts

500 Series - Hydrotreating

HyKTM application (Pretreating section)

700 Series - Hydrocracking

HyKTM applications (Cracking section)

More than 40 commercial references

Apply also for CFHT & HyC-10TM application

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

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HyKTM Catalysts Arrangement

HF 858 NiMo / Alumina HRK 558 NiMo / Alumina HDK 776 NiW / ASA HDM HDS HDN HDA HCK HYK 742 NiMo / Zeolite HR 516 CoMo / Alumina

Optimum Cycle Length Optimum Middle Distillates Yields Optimum Product Quality (VI and naphtha S content)
ARTC Refining and Petrochemicals - Kuala Lumpur - 10-12 March 2009 19

Latest in Hydrocracking Catalysts

Middle Distillate Selectivity

HR 548 HRK 558

500 Series - Hydrotreating MHC, HyKTM applications (Pretreating section) New 700 Series - Hydrocracking MHC, HyKTM applications (Cracking section)

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 20

10

HYK 700 Series Optimizing Acidic Support Properties

Tuned porosity

Tuned acidity
-20

Optimized shaping

20

Al1-Al3

Al2-Al3

40

60

Al1-Al1
80 80 60

Al2-Al1
40 20 0 -20

3800

3750

3700

3650 3600 3550 Wavenumbers (cm-1)

3500

3450

3400

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

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Towards Molecular Scale Understanding of Catalyst Arrangement

Comprehensive Feedstock characterization AL crude VGO (370-566C) Heavy fraction from SAR
5- r 4- r
Tetraaromatics +

ing s

ing s

3- r
Triaromatics Diaromatics Monoaromatics Saturates nC44 nC50

HDT inhibitor identification N-species heavy aromatics

ing s

increasing b.p.
1,4 1,2

increasing b.p.

Kinetics modelling
N-paraff ins Iso-paraffins Mono-naphthens Monoaromatics Diaromatics Triaromatics

Content (% w ) /w

1,0 0,8 0,6 0,4 0,2 0,0 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47

Extended PIONA

48

49

50

51

Atom carbon number

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

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Comprehensive Reaction Progress Three-Dimensional Gas Chromatography

HRK 558 HRK 558
Feedstock
n+iso paraffins

HDK 776 HDK 776

HYK 742 HYK 742

Hydrocracking section
iso-paraffins

Pretreating section
n-paraff ins

nC48 nC22
1-rin g 2-rin g 3-rin g >3-r ing

nC41

nC22 nC41
arom Nap hth ens atic s
nap hten es

nC22

Arabian Light VGO (370-566C)

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

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 5 to C more active 8 8C more active than previous generation than previousgeneration
Conversion in 370C- (wt.%)

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

Same Middle Distillate Selectivity

Middle Distillate Selectivity

100 90 80 70 60 50

HYK742

HYC642

HYC642

HYK742

Reactor Temperature

Conversion in 370C- (wt.%)

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

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Western European Catalyst Case

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

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

HyKTM Catalysts Arrangement

Previous Loading
ACT 077 HMC 945/ HMC 841 HR 448 HYC 642 HR 406

Actual Loading
ACT 069 / ACT 077 HMC 868 HRK 558 HDK 776 HYK 742 HR 516

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

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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

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

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Latest Improvements in Hydrocracking Technology

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