VGO Hydrocracking

7/30/2019 VGO Hydrocracking

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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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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


Content


CFHT / Mild Hydrocracking HyC-10TM



Conclusions


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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


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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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


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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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


Content


Mild Hydrocracking HyC-10TM



Conclusions


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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


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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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


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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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


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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Content


Mild Hydrocracking HyC-10TM



Conclusions


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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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


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


11/14


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


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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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)


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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Western European Catalyst Case

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


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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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

VGO Hydrocracking

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