Ultra low Sulfur HSD production - CENTERA TM Catalysts Are Key To - - PowerPoint PPT Presentation

International Conference on

Ultra low Sulfur HSD production - CENTERATM Catalysts Are Key To unlock potential of Hydrotreaters

• International Conference on

‘Refining Challenges- Way forward’ April 16-17, 2012 Organised by Petrofed, New Delhi, India

Disclaimer

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Long History of Innovation

Type II Technology Type I/II Technology

• Presulfurized Catalysts Oxidic/Easily Regenerated

CENTERATM Is Key to Unlocking Unit Potential Agenda

• Fundamental Understanding of CENTERATM

Advancements

• Broad application in hydroprocessing units
• Case studies demonstrating CENTERATM Benefits
• CENTERATM makes it easier to move “Beyond ULSD”

CENTERATM Is Key to Unlocking Unit Potential Agenda

• Fundamental Understanding of CENTERATM

Advancements

• Broad application in hydroprocessing units
• Case studies demonstrating CENTERATM Benefits
• CENTERATM makes it easier to move “Beyond ULSD”

• Element of Technology

Description

Strong Legacy Builds on Innovations from CENTINEL GOLD and ASCENT technologies Better Dispersion Utilizes improved support technology for better dispersion of active metals Maximum Sulfidation Generates highest possible degree

• Maximum Sulfidation

Generates highest possible degree

• f sulfidation to form ideal Type II

active phases Optimal Assembly of Active Sites (Nanotechnology) Results in optimal decoration/configuration of promoter metals on MoS2 and higher performance with better metals Enhanced Retention of Activity Allows sites to be locked in place

Better Dispersion of MoS2 Particles

Continuous Improvement Using Better Support

• Particle Diameter

CENTINEL: 40 – 45 Å CENTINEL GOLD: 30 – 35 Å CENTERA: 25 – 35 Å

NO / FTIR

• nly Ni

accessible

CENTERA

Ni

NO

Optimal Assembly of Active Sites

Promoter Edge Decoration

• CENTINEL GOLD

Mo

NO

First shell Mo-S coordination number = 6

1.0 2.0

DN-3630 DC-2618 Bulk MoS2

1.0 2.0

DN-3630 DC-2618 Bulk MoS2 DN-3630 DC-2618 Bulk MoS2

Maximum Sulfidation

Generates Fully Accessible Type II Active Phase

• R [Å]

2 4

• 2.0

0.0 1.0

FT

• 1.0

R [Å]

2 4

• 2.0

0.0 1.0

FT

• 1.0

Degree of sulfidation as in bulk MoS2

Enhanced Retention of Activity

Keeps Activity Following Activation, Upsets

25% RVA Increase

Difficult (50%) Cracked Stock Blend: ~70 barg Operation

360 355

• 350

345 340

CENTERATM Is Key to Unlocking Unit Potential

Agenda

• Fundamental Understanding of CENTERATM

Advancements

• Broad application in hydroprocessing units
• Case studies demonstrating CENTERATM Benefits
• CENTERATM makes it easier to move “Beyond ULSD”

Broad Application in Hydroprocessing Units

Improved Performance in Many Areas

• Applied across wide range of pressures (20-200 barg)
• Improved HDN
• Drives higher HDS in ULSD service
• Enhances aromatic saturation and conversion in higher

pressure applications like FCC PT and HCPT

• Improved HDS
• Important in FCC PT, HC and ULSD applications to

maximize production of low sulfur gasoline and diesel across an entire cycle

• Improved stability
• Enhanced retention of initial activity
• Significantly lower SOR temperatures lead to lower

deactivation rates

CENTERATM DC-2650 CoMo for FCC PT

Improved HDS Becoming Critical for ULSG/ULSD Production

140 160 180

ric Activity

HDS - FCC PT HDN - FCC PT

• 80

100 120 140

DC-200 DC-2118 Centinel DC-2551 Ascent DC-2650 Centera

Relative Volumetric

CENTERATM DN-3620 NiMo for HCPT

Relieves HDN Constraints and Provides Big HDS Improvement Outstanding Performance for LCO Hydrocracking

360 366 371 377 382

00 ppm S DN-3310

11 ° C or 40%

HCPT Testing of 100% LCO Feed

P = 78 bar; LHSV = 1.4; TGR = 1265 Nm3/m3 Feed: S = 3.05 wt%; N = 726 ppm

• 327

333 338 344 349 355

50 100 150 200 250 300 350 400 450 500 550 600 650 700

Catalyst Age, hrs

T Req'd for 200 DN-3310 DN-3620

40% RVA Increase

• CENTERATM DC-2618 CoMo for Low-Medium Pressure ULSD

Advantage Across the Board, Especially at Low Pressure

15 10 C

• 5

20 barg 30 barg 40 barg 40 barg

CENTERATM DN-3630 NiMo for Medium-High Pressure ULSD

Significant HDS Advantage Driven By Improved HDN

ULSD Testing of Heavy Arab Med SRGO Feed

P = 60 barg; LHSV = 1.0 hr-1; TGR = 200 Nm3/m3 Feed: S = 1.67 wt%; N = 185 ppm

360 355

• 350

345 340

CENTERATM Is Key to Unlocking Unit Potential

Agenda

• Fundamental Understanding of CENTERATM

Advancements

• Broad application in hydroprocessing units
• Case studies demonstrating CENTERATM Benefits
• CENTERATM makes it easy to move “Beyond ULSD”

675 680

F

!

• "#$%&&&'
• () ( !
• $%&*&'##( !

! " ULSD Testing of Heavy SR/LCO/LKGO Blend

Feed: S = 1.1 wt%; N = 950 ppm P = 42 barg; LHSV < 1.0 hr-1; TGR = 400 Nm3/m3

Case Study #1:

Evaluate CENTERATM vs CENTINEL GOLD Systems

CENTERATM Catalysts Provide Significant Performance Benefits

360

• 640

645 650 655 660 665 670 100 200 300 400 500 600 700 800 900 1,000 1,100 1,200 1,300

Temperature Required for 8 ppm Sulfur, °F Catalyst Age, hours

CENTINEL GOLD DN-3330 CENTERA Stack/Sandwich CENTERA DN-3630

16℉ ℉ ℉ ℉

355 350 345 340

9 C

Case Study #2:

Evaluate CENTERATM vs ASCENT Systems

CENTERATM Catalysts Provide Significant Performance Benefits

+,$+-.//0.

• #1 2(# $, 3.
• 4".
• 5 $2 $.$4".

# $ ULSD Testing of Heavy SR/VB Blend

• 12

° C

ULSD Testing of Heavy SR/VB Blend

Feed: S = 0.3 wt%; N = 170 ppm P = 400 barg; LHSV > 1.5 hr-1; TGR ~ 80 Nm3/m3 360 370 365 355

CENTERATM Is Key to Unlocking Unit Potential

Agenda

• Fundamental Understanding of CENTERATM

Advancements

• Broad application in hydroprocessing units
• Case studies demonstrating CENTERATM Benefits
• CENTERATM makes it easier to move “Beyond ULSD”

$ +3

2 3%+$0%!

• Backup Slides

2 4-5/6!4757.

!0

ULSD Feature Customer Benefit

Maximum HDS Performance

• DC-2618 - Highest Activity CoMo at

Low-Med P (5-20° F, 3-12° C) vs DC-

• 2533. Comparable to CENTINEL

GOLD DC-2318 at Med-High P.

• DN-3630 - Highest Activity

Conventional NiMo in Market (8-13° F, 5-8° C) more active than DN-3330.

• Longer runs
• Process heavier/harder feeds
• Enable diesel upgrading for non-sulfur

properties (e.g. cetane, cold flow)

• Enables use of more regen catalyst usage.

Enhanced Retention of Activity Higher SOR activity. Less hyperactivity during first month of operations. Top Performance CoMo and NiMo for Provides ability to manage both activity and H

• Top Performance CoMo and NiMo for

customized application Provides ability to manage both activity and H2

• consumption. Enables stacking and sandwiching

combinations. Handling and Loading Flexibility No special packaging required. Loading of reactor easily handled in air environment Normal sulfiding procedures No long holds at intermediate temperatures required for some Type II activations Robust during startup Extended gas phase heatup (12-hr at 150° C) possible before liquid is introduced. Permits leak testing and reactor wall heating to satisfy temper embrittlement requirements. Regenerable by ENCORE Best multi-cycle economics

MoS2 - Type I

• mainly single layers
• incomplete sulfidation
• Al-O-Mo bonding still present
• poor accessibility of active sites
• less active than Type II

Particle Morphology Affects Activity

Interaction with Alumina is Key Determinant

• MoS2 – Type II
• stacked particles
• fully sulfided
• no Al-O-Mo bonding
• high accessibility of active sites
• high hydrogenation activity
• more active than Type I

CENTERATM Catalyst Technology

Improvement in Both Direct and Indirect HDS

Comparison of DBT HDS Pathways for CENTERA and ASCENT NiMo Catalysts CENTERA Shows Improvement in Both Reaction Routes

50 60 70 80 90 100 ratcion % CENTERA DN-3630 Hydrogenation HDS ASCENT DN-3531 Hydrogenation HDS CENTERA DN-3630 Direct HDS ASCENT DN-3531 Direct HDS

DBT hDBT BP CHB BCH

• 10

20 30 40 50 220 230 240 250 260 Temperature (C) Mole fra

General ULSD Product Placement

iculty / Severity CoMo vs NiMo

NiMo CoNiMo Or CoMo - NiMo Potential Stacking Opportunities

• P = 600 psig

P = 800 psig P = 400 psig P = 1300 psig

Feed Difficu

Hydrogenation Environment / H2 Consumption CoMo CoMo - NiMo Combinations Opportunities

North American Example

Drop-in catalyst for short-term solution Revamp implemented later with full ULSD solution High activity catalyst plus dewaxing used to increase feed by 12% Same dewaxing catalyst used for both cycles (even some regen)

5 0 5 0

S u m m e r S u m m e r W in te r W in te r W in te r W in te r

Catalytic Dewaxing

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• 1 0

1 0 1 0 1 0 2 0 2 0 3 0 3 0 4 0 4 0 A u g A u g N o v N o v F e b F e b J u n J u n S e p S e p D e c D e c M a r M a r

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