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
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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
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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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11
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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