International Conference on

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

Dr. Ujjwal Manna

CONFIDENTIAL

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

Disclaimer

Shell Global Solutions is a network of independent technology companies in the Shell Group.

In this document, the expressions “Shell” or “Shell Global Solutions” are sometimes used for convenience

where reference is made to these companies in general, or where no useful purpose is served by identifying

a particular company.

The information contained in this material is intended to be general in nature and must not be relied on as specific advice in

connection with any decisions you may make. Shell and Shell Global Solutions are not liable for any action you may take as a

result of you relying on such material or for any loss or damage suffered by you as a result of you taking this action.

Furthermore, these materials do not in any way constitute an offer to provide

specific services.

CONFIDENTIAL

Some services may not be available in certain countries or political subdivisions thereof.

Copyright ©2010 Shell Global Solutions International BV. All rights reserved. No part of this publication may be reproduced or

transmitted in any form or by any means, electronic or mechanical including by photocopy, recording or information storage

and retrieval system, without permission in writing from Shell Global Solutions International BV.

The information contained in this presentation is provided for general information purposes only. No representations or

warranties, express or implied, are made by Shell Global Solutions International B.V. or its affiliates concerning the applicability,

suitability, accuracy or completeness of the information contained herein and neither Shell Global Solutions International B.V.

nor its affiliates accept any responsibility whatsoever for the use of this information. Neither Shell Global Solutions International

B.V. nor any of its affiliates shall be liable in any way for any liability, loss, cost or damage incurred as a result of the receipt or

use of the information contained herein.

2

Long History of Innovation

Type II Technology Type I/II Technology

PLUS

Presulfurized Catalysts Oxidic/Easily Regenerated

CONFIDENTIAL

CENTERATM Is Key to Unlocking Unit PotentialAgenda

• Fundamental Understanding of CENTERATM

Advancements

• Broad application in hydroprocessing units

CONFIDENTIAL

• Case studies demonstrating CENTERATM Benefits

• CENTERATM makes it easier to move “Beyond ULSD”

CENTERATM Is Key to Unlocking Unit PotentialAgenda

• Fundamental Understanding of CENTERATM

Advancements

• Broad application in hydroprocessing units

CONFIDENTIAL

• Case studies demonstrating CENTERATM Benefits

• CENTERATM makes it easier to move “Beyond ULSD”

CENTERATM Catalyst TechnologyFundamental Story

Element of Technology DescriptionStrong 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

CONFIDENTIAL

Maximum Sulfidation Generates highest possible degree of 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 ParticlesContinuous Improvement Using Better Support

CONFIDENTIAL

Particle DiameterCENTINEL: 40 – 45 Å

CENTINEL GOLD: 30 – 35 ÅCENTERA: 25 – 35 Å

10 nm10 nm

NO / FTIRonly Ni

accessible

CENTERA

Ni

NO

Optimal Assembly of Active SitesPromoter Edge Decoration

CONFIDENTIAL

CENTINEL GOLD Mo

NO

First shell Mo-Scoordination number = 6

1.0

2.0 DN-3630DC-2618Bulk MoS2

1.0

2.0 DN-3630DC-2618Bulk MoS2

DN-3630DC-2618Bulk MoS2

Maximum SulfidationGenerates Fully Accessible Type II Active Phase

CONFIDENTIAL

0

R [Å]

2 4

-2.0

0.0

1.0

FT

-1.0

0

R [Å]

2 4

-2.0

0.0

1.0

FT

-1.0

Degree of sulfidation as in bulk MoS2

Enhanced Retention of ActivityKeeps Activity Following Activation, Upsets

25%RVA

Increase

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

360

355

CONFIDENTIAL

350

345

340

CENTERATM Is Key to Unlocking Unit PotentialAgenda

• Fundamental Understanding of CENTERATM

Advancements

• Broad application in hydroprocessing units

CONFIDENTIAL

• Case studies demonstrating CENTERATM Benefits

• CENTERATM makes it easier to move “Beyond ULSD”

Broad Application in Hydroprocessing UnitsImproved 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

CONFIDENTIAL

• 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 PTImproved HDS Becoming Critical for ULSG/ULSD Production

140

160

180

Rel

ativ

e V

olu

met

ric

Act

ivit

yHDS - FCC PT

HDN - FCC PT

CONFIDENTIAL

80

100

120

140

DC-200 DC-2118 Centinel

DC-2551 Ascent

DC-2650 CenteraR

elat

ive

Vo

lum

etri

c A

ctiv

ity

CENTERATM DN-3620 NiMo for HCPTRelieves HDN Constraints and Provides Big HDS Improvement

Outstanding Performance for LCO Hydrocracking

360

366

371

377

382fo

r 20

0 p

pm

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

CONFIDENTIAL

327

333

338

344

349

355

0 50 100 150 200 250 300 350 400 450 500 550 600 650 700

Catalyst Age, hrs

T R

eq'd

for

200 DN-3310

DN-3620

40%RVA

Increase

PLUSPLUS

CENTERATM DC-2618 CoMo for Low-Medium Pressure ULSDAdvantage Across the Board, Especially at Low Pressure

15

10

C

CONFIDENTIAL

5

0

20 barg 30 barg 40 barg 40 barg

CENTERATM DN-3630 NiMo for Medium-High Pressure ULSDSignificant 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

CONFIDENTIAL

350

345

340

CENTERATM Is Key to Unlocking Unit PotentialAgenda

• Fundamental Understanding of CENTERATM

Advancements

• Broad application in hydroprocessing units

CONFIDENTIAL

• Case studies demonstrating CENTERATM Benefits

• CENTERATM makes it easy to move “Beyond ULSD”

675

680

FOpportunity: Evaluate Tradeoffs of Activity and H2 Consumption• Both systems provided activity advantage over incumbent DN-3330 system• Sandwich CoMo/NiMo CENTERATM system showed H2 savings• CENTERATM DN-3630 system gave big activity benefit with some increase in H2 ConsumptionConclusion: Benefits of an all NiMo CENTERATM system allowed more cracked stock processing, which outweighed potential H2 savings

ULSD Testing of Heavy SR/LCO/LKGO BlendFeed: 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

CONFIDENTIAL

640

645

650

655

660

665

670

0 100 200 300 400 500 600 700 800 900 1,000 1,100 1,200 1,300

Temp

eratur

e Req

uired

for 8

ppm

Sulfu

r, °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 BenefitsOpportunity: ULSD Unit extremely activity constrained. Cycle life <<1 year.• Heavy feed and visbroken components add significant nitrogen, which inhibits HDS for high LHSV unit.• High SOR WABT puts unit in thermodynamically constrained region immediately.• Incorporating CENTERA NiMo significantly improves HDN, HDS. Dramatic reduction in SOR WABT.Conclusion: Benefits of adding NiMo CENTERATM opens up operaing window, and has potential to double cycle length.

ULSD Testing of Heavy SR/VB Blend

CONFIDENTIAL

12°C

ULSD Testing of Heavy SR/VB BlendFeed: 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 PotentialAgenda

• Fundamental Understanding of CENTERATM

Advancements

• Broad application in hydroprocessing units

CONFIDENTIAL

• Case studies demonstrating CENTERATM Benefits

• CENTERATM makes it easier to move “Beyond ULSD”

Diesel Hydrotreating Units Are Versatile AssetsCENTERATM Is The Key To Moving Beyond ULSD

CONFIDENTIAL

CONFIDENTIAL

Backup Slides

CENTERATM DC-2618 and DN-3630Features and Benefits

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

CONFIDENTIAL

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 ActivityInteraction with Alumina is Key Determinant

CONFIDENTIAL

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 TechnologyImprovement in Both Direct and Indirect HDS

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

50

60

70

80

90

100M

ole

fra

tcio

n %

CENTERA DN-3630 Hydrogenation HDSASCENT DN-3531 Hydrogenation HDSCENTERA DN-3630 Direct HDSASCENT DN-3531 Direct HDS

DBT hDBT

BP CHB BCH

CONFIDENTIAL

0

10

20

30

40

50

220 230 240 250 260

Temperature (C)

Mo

le f

ratc

ion

%

General ULSD Product Placement

Fee

d D

iffi

cult

y / S

ever

ity

CoMo vs NiMo

NiMo

CoNiMo

Or

CoMo - NiMo

Potential Stacking

Opportunities

CONFIDENTIAL

P = 600 psig P = 800 psigP = 400 psig P = 1300 psig

Fee

d D

iffi

cult

y / S

ever

ity

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 05 0S u m m e rS u m m e rW in te rW in te r W in te rW in te r

Catalytic DewaxingCommercially Proven Solutions

CONFIDENTIAL

-- 1 01 0

00

1 01 0

2 02 0

3 03 0

4 04 0

A u gA u g N o vN o v F e bF e b J u nJ u n S e pS e p D e cD e c M a rM a r

°° FF

c lo u d p o in t fe e dc lo u d p o in t fe e d

d e lta c lo u d p o in td e lta c lo u d p o in tc lo u d p o in t fe e dc lo u d p o in t fe e d

d e lta c lo u d p o in td e lta c lo u d p o in t