vgo hydrocracking
TRANSCRIPT
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1
Latest Improvements in
Hydrocracking Technologies
Jrme Bonnardot
2ARTC 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
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3ARTC Refining and Petrochemicals - Kuala Lumpur - 10-12 March 2009
LCO
Conversion Mapping
Crude
Oil
Naphtha
Jet / Kero
Diesel
Fuel-Oil
FCCCFHT*
MHC**
HyC-10
HyK
Solvahl H-OilDC
R2R
LPG
DAO
VR
VGO
Hyvahl
H-OilRCHDHPLUS
PitchHCGO
HySCOPSyncrude
Topp
ing
Vac.Dist.
* CFHT = Cat Feed HydroTreating;
**MHC = Mild Hydrocracking
Proc
essC
onfig
uratio
ns
Lates
tCata
lysts
4ARTC 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
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5ARTC Refining and Petrochemicals - Kuala Lumpur - 10-12 March 2009
LCO
LCGO
Heavy SRGO
Processes crackedGO + LCO, LCGO
in the polishing
reactor and
produce ULSD
Saves 2compressors
MinimizesCAPEX/OPEX
2 units in operation
and 1 under design
Produces low Sulphur FCC Feed + ULSD simultaneously
VGO
H2
Low S
FCC feed
Off specDiesel
Polishingsection
Fuel gas,
NaphthaMHCsection
ULSD (10 ppm S)
HyC-10TM Configuration
6ARTC Refining and Petrochemicals - Kuala Lumpur - 10-12 March 2009
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%
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7ARTC Refining and Petrochemicals - Kuala Lumpur - 10-12 March 2009
0
200
400
600
800
1000
1200
1400
1600
1800
Reactor Temperature, C
Effluent Sulfur Content, wt ppm
5 C
HR 548
HR 568
HR 448
10 C
HR 568 CoMoNiFor CFHT Application
Breakthrough Catalyst
Straight run VGO
Same operating conditions
6 references (in 5 months)
obtained after pilot tests
More Active in HDA
Same HDN Activity
8ARTC 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
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9ARTC Refining and Petrochemicals - Kuala Lumpur - 10-12 March 2009
HDSHDN
HDA
HCK
NiW / ASA
HDK 776
NiMo / Alumina
HR 548
Higher conversion is possible through a dual
catalyst system with NiMo on Alumina and NiW on ASA
HR 548 + HDK 776For Mild Hydrocracking Application
5 %
HR 448
0
10
20
30
40
Reactor Temperature (C)
NetConversion(wt%)
HR 548 + HDK776
HR 548
15 %
50
10ARTC 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
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11ARTC Refining and Petrochemicals - Kuala Lumpur - 10-12 March 2009
Axens HP HydrocrackerFlexible Process
H2
DAO
Furfural extracts
Paraffins
Coker VGO
Visbreaker VGO
LCO
HCO
Special crude
VGO
Conventional
crude VGO
FLEXIBLE PROCESS
Euro V
Diesel,
Jet A1
+
High VI
Lube Oil
Bases
and/or SC
Feed
12ARTC Refining and Petrochemicals - Kuala Lumpur - 10-12 March 2009
SEP
FG / LPG
NaphthaIsom / CCR
KeroseneJet A1
DieselEuro V
UCOGroup III Lube
Oil Production
FeedLVGO
HVGO
HCGO 25%
F
R
A
C
HDT HyK
SSOT Scheme, 50 000 BPSD (Construction Phase)
High UCO value
Lowest CAPEX
Nine awards since 2005
85 wt. % Conversion
Single Stage Once-Through SSOTWestern Europe Reference - 2006
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13ARTC Refining and Petrochemicals - Kuala Lumpur - 10-12 March 2009
FG / LPG
UCOPetrochemical FCC
For feed with high nitrogen content up to over 5000 ppm(Marlim Crude)
SSOT Scheme, 54 000 BPSD (FEED Phase)
SEP2
Light NaphthaSteam Cracking
Medium DistillateSteam Cracking
FeedLVGO
HVGO
HCGO 18%
F
R
A
C
HDT2 HyK
Dedicated for very heavy VGO Feeds High product values
One award since 2007
85 wt. % Conversion on Marlim crude
SEP1HDT1
H2S + NH3
Heavy NaphthaCCR + Aromatics
Single Stage Once-Through SSOTSouth America Reference - 2007
Integrated Reaction Section
14ARTC Refining and Petrochemicals - Kuala Lumpur - 10-12 March 2009
SEP
FG / LPG
NaphthaPool / CCR
DieselEuro V
Bleedliquid recycle
HDT HyK
Higher MD yield
Higher product quality
Two awards since 2007
F
R
A
C
FeedVGO
HCGO 16%
KeroseneJet A1
SSREC Scheme, 38 000 BPSD (FEED Phase)
97 wt. % Conversion
Single Stage with Recycle SSRECMiddle East Reference - 2007
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15ARTC Refining and Petrochemicals - Kuala Lumpur - 10-12 March 2009
SEP
FG / LPG
NaphthaCCR / Isom
KeroseneJet A1
DieselEuro V
Bleed
HDT HyK
HyK
2nd Stage
Highest MD yield
High diesel incentive
One award since 2006
F
R
A
C
Feed
HVGO
HCGO 22%
TSREC Scheme, 66 000 BPSD (FEED Phase)
98 wt. % Conversion
Two Stage with Recycle TSRECAfrican Reference - 2006
16ARTC Refining and Petrochemicals - Kuala Lumpur - 10-12 March 2009
Between 2005 and 2008
13 References in HCK
15 References in MHC / CFHT
Hydrocracking LicensingGeographical Breakdown
6
22
8
12
16
World Total: 71 Licenses
Cumulative Capacity: ~ 2,935,000 bpsd
North America
Europe
Central & South America
Middle East - Africa
Asia - Pacific
23%
32%
7%
9%
17%
12%
as of December 2008
5
CIS
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17ARTC 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
18ARTC Refining and Petrochemicals - Kuala Lumpur - 10-12 March 2009
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-10TMapplication
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19ARTC Refining and Petrochemicals - Kuala Lumpur - 10-12 March 2009
Optimum Cycle Length
Optimum Middle Distillates Yields
Optimum Product Quality (VI and naphtha S content)
HYK 742 NiMo / ZeoliteHRK 558 NiMo / Alumina
HDK 776 NiW / ASA
HDS
HDN
HDA
HCK
HR 516 CoMo / Alumina
HF 858 NiMo / Alumina
HDM
HyKTM Catalysts Arrangement
20ARTC Refining and Petrochemicals - Kuala Lumpur - 10-12 March 2009
Conversion Activity
Middle Distillate
Selectivity
Latest in Hydrocracking Catalysts
Alumina
Very High Middle
Distillate
High Middle
Distillate
High
Conversion
HR 548HRK 558
HDK 776
HYC 652
HYK 742HYC 642
500 Series - Hydrotreating MHC, HyKTM applications (Pretreating section)
New 700 Series - Hydrocracking MHC, HyKTM applications (Cracking section)
More than 40 commercial references for
MHC & HyKTM applications
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21ARTC Refining and Petrochemicals - Kuala Lumpur - 10-12 March 2009
HYK 700 SeriesOptimizing Acidic Support Properties
34503500355036003650370037503800
Wavenumbers(cm-1)
3400
Tuned porosity
Tuned acidity
(ppm)
-20020406080
-20
0
20
40
60
80
Al2-Al1Al1-Al1
Al1-Al3 Al2-Al3
Optimized shaping
22ARTC Refining and Petrochemicals - Kuala Lumpur - 10-12 March 2009
AL crude VGO (370-566C) Heavy fraction from SAR
increasingb.p.
3-rings
4-rings
5-rings
HDT inhibitor
identification
N-species
heavy aromatics
nC50nC
44
Tetraaromatics +
Triaromatics
Diaromatics
Monoaromatics
Saturates
nC50nC
44
Tetraaromatics +
Triaromatics
Diaromatics
Monoaromatics
Saturates
Extended
PIONA
increasing b.p.
0,0
0,2
0,4
0,6
0,8
1,0
1,2
1,4
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
Content(%w/w)
N-paraffins
Iso-paraffins
Mono-naphthens
Monoaromatics
Diaromatics
Triaromatics
Kinetics modelling
Comprehensive Feedstock characterization
Towards Molecular Scale Understandingof Catalyst Arrangement
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23ARTC Refining and Petrochemicals - Kuala Lumpur - 10-12 March 2009
Feedstock
nC22
nC48
1-ring2-ring
3-ring
>3-ring
n+isoparaffins
HRK 558HRK 558 HDK 776HDK 776
Pretreating section
HDN, HDA activity tuning
Pretreating / Hydrocrackingbalance
HYK 742HYK 742
nC22nC41
iso-paraffins
naphtenes
Cracking balance
Hydrogenation / Aciditytuning MD selectivity UCO VI optimization
nC22nC41
aromatics
n-paraffins
Naphthens
Comprehensive Reaction ProgressThree-Dimensional Gas Chromatography
Hydrocracking section
Arabian Light VGO
(370-566C)
Unconverted Product
(370+ C)
Unconverted Product
(370+ C)
24ARTC Refining and Petrochemicals - Kuala Lumpur - 10-12 March 2009
HYK 742 catalyst characteristics New optimized acidity & porosity
zeolite
New high surface area alumina gel
HigherMo content & dispersion
Key features Controlled acidity
Distance between acid and metalsites
Highermetal availability
50
60
70
80
90
100
Reactor Temperature
Conversionin
370C-(wt.%)
HYC642
HYK742
88C more activeC more active
than previous generationthan previous generation
50
60
70
80
90
100
Reactor Temperature
Conversionin
370C-(wt.%)
HYC642
HYK742
88C more activeC more active
than previous generationthan previous generation
Conversion in 370C- (wt.%)
Middle
Distillate
Selectivity
HYC642
HYK742
SameSame MiddleMiddle DistillateDistillate SelectivitySelectivity
Conversion in 370C- (wt.%)
Middle
Distillate
Selectivity
HYC642
HYK742
SameSame MiddleMiddle DistillateDistillate SelectivitySelectivity5 to 8C more active
than previous generation
HYK 742High Activity & Middle Distillate Selectivity
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25ARTC Refining and Petrochemicals - Kuala Lumpur - 10-12 March 2009
Western European Catalyst Case
7200 tons/day Conversion 80-85 % Started-up end 2006
26ARTC Refining and Petrochemicals - Kuala Lumpur - 10-12 March 2009
ACT 069 / ACT 077
HR 448
HYC 642
HMC 945/ HMC 841
HyKTM Catalysts Arrangement
HR 406
ACT 077
HMC 868
HRK 558
HDK 776
HYK 742
HR 516
Previous Loading Actual Loading
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27ARTC Refining and Petrochemicals - Kuala Lumpur - 10-12 March 2009
Hydrocracking TechnologyConclusions
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 ofCombined Catalyst System generateshigher returns for refiner
Performing Analytical tool linked with kinetic modeling permit tofine tuned catalytic system
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Latest Improvements in
Hydrocracking Technology