Advances in Hydroprocessing Catalysts

Laxmi Narasimhan

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

CONFIDENTIAL

Laxmi Narasimhan

General Manager

Centre for Novel Catalytic Materials

Shell Technology Centre

Shell India Marketing pvt Limited, Bangalore

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CONFIDENTIAL

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2

Agenda

� About Shell Technology Centre, Bangalore

� New Directions in Hydroprocessing R&D

� Hydrocracking

� Beyond ULSD

� Case study

� Heavy Oil upgradation

CONFIDENTIAL 3

� Heavy Oil upgradation

Refining

Naptha HT

Upstream & Renewables

GTL

CRI/Criterion Inc. Family

Chemicals

Ethylene Oxide

Three Business Units

CONFIDENTIAL

Naptha HTDistillate HTHydrocrackingFCC PretreatLubesResid UpgradingTail GasClean Fuel Projects

GTLAcid & Heavy CrudeH2 / MembranesRenewable Fuels & Chemicals

Ethylene OxideSelective HydrogenationEnvironmental

5

Impact

Upstream

Core

Technologies Maturation

Co-

Drivers

National Oil

Companies

Major Resource

Technology Engine

CONFIDENTIAL

Downstream

Alternative

Energy

Systems

DevelopDiscover Demonstrate Deploy

First

Emerging

Buy Build

Co-Create

Major Resource

Holders

Governments

Customers

New Horizons

6

Enhancing R&D effectiveness by deploying High throughput tools

Parallel catalyst preparation unit

Parallel pelletizing, crushing and sieving tools

CONFIDENTIAL7

Conditions:

1. Tmax = 800 °C

2. Pressure = 1-12 bar

3. MS analyzer

Conditions:

1. Tmax = 500 °C

2. Pressure = 1-100 bar

3. Online GC

4. S/N analyzer

16 barrel unit for hydroprocessing 16 barrel unit for flue gas applications

THE FOUR Cs APPROACH Customizing catalysts for hydrotreating

feed

R-1

R-2

R-3

Chemistry (HDN/HDS)

Composition (feed blend)

CONFIDENTIAL 13 April 2012 8

R-3

R-4

R-5

R-6

Composition (feed blend)

Conditions (Unit operation & limitations)

Catalyst (Activity, stability, shape & selectivity)

Product

State-of-the Art Technology HCU Catalysts

Hydrogenation function

Metals

Hydrogenation function

Metals

DD--VUSY compared to VUSYVUSY compared to VUSY VUSYVUSY DD--VUSYVUSY

More active Y zeolites

Same intrinsic VUSY type selectivity

Gives

Higher binder content

Extra room for hydrogenating metals

Room to add extra functionality

How utilized

CONFIDENTIAL

Step out function

Hydrocracking function

D-VUSY

?

Hydrocracking function

VUSY

BinderBinder

How utilized

Zeolites with content & activity/selectivity optimized to catalysts type

Morphology to maximize access of feed molecules

Metals balanced to binder surface for premium products

Third function to enhance other chemistries

- Aromatics saturation

- Cold Flow property improvement

Selectivity enhancements

Zeolyst Hydrocracking Portfolio

Z-503

Z-513

Z-603

Z-623

Z-673

Z-2513

Z-2623

Z-2723

Z-FX10

Mid

Dis

till

ate

Se

lec

tivit

yDiesel Mid Distillate Mid Distillate/Naphtha Naphtha

Similar Surface Area

CONFIDENTIAL

Z-673

Z-723

Z-733

Z-803

Z-753

Z-3723

Z-3733

Z-853Z-863

Z-FX10

Z-NP10

Mid

Dis

till

ate

Se

lec

tivit

y

Activity

Classic State-of-the-art New step-out portfolio

Similar Surface Area

200 – 230m2/g

Moving zeolite manufacturing into the 21st century

Direct feedback

from R&D to

manufacturing.

“Nano-scale”

engineered

CONFIDENTIAL

engineered

materials are

feasible at

industrial-scale

productions.

“Nano-scale” engineered materials produced at industrial scale.

Beyond ULSD: Motivation (1)

� Refinery Business Drivers -- Evolution:

� Increased Heavy/Sour Crude Processing

� Increased Bottoms Conversion

� Increased Distillates Production/Product Quality

(Higher Cetane, Lower Aromatics Content, etc.)

CONFIDENTIAL

1212

� ULSD Unit Flexibility: Capture Changing Opportunities

Typical Feed Effects – Final Boiling Point/Endpoint

16000

18000

20000

22000

24000

26000

28000

30000

32000

34000

S (

wp

pm

)

800

900

1000

1100

1200

1300

1400

1500

1600

1700

N (

wp

pm

)

Total S (wppm)

Total N (wppm)

°F °C

300 149

350 177

400 204

450 232

500 260

Significant S & Dramatic N Increases with Increasing Incremental Boiling Range.

CONFIDENTIAL 13

0

2000

4000

6000

8000

10000

12000

14000

16000

30

23

16

33

13

45

36

13

76

39

04

05

41

94

35

45

04

64

47

84

93

50

95

23

53

85

52

56

75

83

59

76

12

62

66

40

65

76

71

68

57

00

71

47

30

74

57

59

77

47

88

80

4

Boiling Fraction Midpoint (oF)

S (

wp

pm

)

0

100

200

300

400

500

600

700

800

N (

wp

pm

)

500 260

550 288

600 316

650 343

700 371

750 399

800 427

Range.

0.5

0.6

0.7

0.8

0.9

1.0

1.1

ANTHRACENE

PHENANATHRENE

FLUORENE

ACRIDINE

CARBAZOLEDB

T H

DS

RA

TE

Moderate Pressure Hydrotreater Conditions &

NiMo/Al2O3 Catalyst

Feed Effects: Hydrotreating Catalyst Inhibition

CONFIDENTIAL 14

0.0

0.1

0.2

0.3

0.4

0.5

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

RELATIVE INHIBITOR MOLAR CONCENTRATION

CARBAZOLE

INIT

IAL

4,6

-DM

-DB

T H

DS

RA

TE

Organic N: Strongest Inhibitor

Increasing Feed N Increases Catalyst Inhibition.

Reference: T. Koltai, et.al., Applied Catalysis A: General, (2002) 231, P- 253

� Solutions: Rapid Implementation / Immediate Economic Payback

� Commercially Proven – Low Risk

� Multiple Technologies Available

� Optimal Solution – Refinery/Unit Specific

Beyond ULSD: Motivation (3)

CONFIDENTIAL 15

Drivers:• “Clean” Product• Hydrogenation Environment

Catalyst Technology High Performance Catalysts: Enhance Feed/Product Quality Flexibility

� High Performance Catalysts:

� Reduce HT Catalyst Requirements

� Make Reactor Volume Available – Speciality Catalysts

� Enable Additional Upgrading Reactions Possible

CONFIDENTIAL

1616

Current or Design ULSD

FutureEnhanced Diesel

Operation

UpgradingChemistry

Isomerization

Selective Hydrocracking in ULSD Operations: (SRO and MHC)

� Fills ULSD/Hydrocracking Performance Gap

� Cheaper H2: Improves Economic Viability

� Operating Flexibility: Maximize Product Margin

� Technology Drivers

ULSDULSG

CONFIDENTIAL 17

LCN+

HCN

LCO

LVGO ULSDLVGO

ULSD EAS DAS HC

LCO

FCCU

ULSD

Beyond ULSD Technologies

ULSG

SRO

ULSG

MHC

Introduction/Background

• Pilot Plant Study – Grass Roots ULSD Unit Project

�ULSD Test

�ULSD/MHC Test

ULSD/MHC Operation: Gasoline/Distillate Flexibility

CONFIDENTIAL18

�ULSD/MHC Test

• Unit Design Objectives

�Gasoline/Distillate Flexibility

�Cetane Improvement

Feed Blend, Process Conditions, & Catalyst Systems Tested

ULSD Process Conditions

LHSV (hr-1) 1.0

ppH2 (psia) 75

H2/Oil (SCFB) 420

WABT (oF) 340

ULSD/MHC Operation: Gasoline/Distillate Flexibility

Feed Blend (Vol%)

SRD 55

LCGO 23

LCO 11

CN 11

CONFIDENTIAL19

Catalyst DN-3110

ULSD/MHC Process Conditions

LHSV (hr-1) 0.9

ppH2 (psia) 75

H2/Oil (SCFB) 710

WABT (oF) 340 - 350

Catalyst NiMo/HC (85/15 –Vol/Vol)

CN 11

Substantial Cracked Stocks

Catalyst Volumes Adjusted to Provide Equal HDS Activity

Z-503

Z-513

Z-603

Z-623

Z-673

Z-2513

Z-2623

Z-2723

Z-FX10

Mid

Dis

till

ate

Se

lec

tivit

y

Classic

ULSD/MHC Operation: Gasoline/Distillate Flexibility

Hydrocracking Catalyst Portfolio

CONFIDENTIAL

Z-723

Z-733Z-803

Z-753

Z-3723Z-3733

Z-863Z-853

Mid

Dis

till

ate

Se

lec

tivit

y

Activity

Classic

State-Of-The-Art

+ cold flow

Step out

Diesel Diesel/Jet Jet/Naphtha

ULSD

Feed TLP Diesel Naphtha

193°C+ 193°C-

Density @ 15 C (g/cc) 0.8664 0.8423 0.8536 0.7720

Sulfur (wppm) 7800 7 7 4

Nitrogen (wppm) 275 <1 <1 <1

SFC Aromatics (wt%)

Mono- 30.0 ----- 21.2 15.9

Di- 10.6 ----- 2.0 0.1

Tri- 1.1 ----- 0.2 0.0

WABT = 340oC

ULSD/MHC Operation: G/D Flexibility - ULSD Operation

ULSD Operation Product Quality: Significant Cetane Upgrade with Minimal Distillate Yield Loss

CONFIDENTIAL21

Tetra+ 0.7 ----- 0.8 0.1

Total 42.4 ----- 24.2 16.1

Hydrogen Consumption (Nl/l) 116

Cetane Index (D-4737-A) 36.8 43.8 45.1 -----

D-86 Distillation, (°C)

IBP 62 121 212 92

5 vol% 127 158 227 110

50% 262 251 260 146

95% 324 319 329 183

FBP 332 329 332 191

Incremental 82-193°C (vol%) 0 1.1 ----- -----

ULSD/MHC

Feed TLP Diesel Naphtha TLP Diesel Naphtha

193oC+ 193

oC- 193

oC+ 193

oC-

Density @ 15 C (g/cc) 0.8664 0.8286 0.8420 0.7840 0.8217 0.8375 0.7782

Sulfur (wppm) 7800 2 3 <1 2 2 <1

Nitrogen (wppm) 275 <1 <1 <1 <1 <1 <1

SFC Aromatics (wt%)

Mono- 30.0 ----- 10.9 16.7 ----- 12.6 16.1

Di- 10.6 ----- 0.7 0.1 ----- 0.8 0.1

Tri- 1.1 ----- 0.1 0.0 ----- 0.1 0.0

WABT = 340oC WABT = 350

oC

ULSD/MHC Operation: Gasoline/Distillate Flexibility ULSD/MHC Product Quality: Extensive Cetane Upgrade

ULSD/MHC Yields: Significant Naphtha Production & T-95 Shift

CONFIDENTIAL22

Tri- 1.1 ----- 0.1 0.0 ----- 0.1 0.0

Tetra+ 0.7 ----- 0.1 0.0 ----- 0.2 0.0

Total 42.4 ----- 11.8 16.8 ----- 13.7 16.2

Hydrogen Consumption (Nl/l) 150 155

Cetane Index (D-4737-A) 36.8 46.2 49.1 ----- 46.8 49.4 -----

D-86 Distillation (°C)

IBP 62 109 203 92 107 198 72

5 vol% 127 142 231 113 134 224 111

50% 262 243 257 149 234 252 143

95% 324 312 324 188 308 317 182

FBP 332 321 326 193 321 324 189

Incremental 82-193oC (vol%) 0 9.6 ----- ----- 16.3 ----- -----

Enhanced Aromatic Saturation (EAS) � Extension of Aromatic Saturation Technology

� (Base Metal) Catalyst

� Higher Aromatic Saturation (ASAT) Levels

� Process

� Uniform Product Quality: SOR/EOR

� Liquid Quench – Temperature Management / Compressor Design

EAS DAS

CONFIDENTIAL

2323

EAS DAS

Enhanced Aromatic Saturation (EAS) Case Study

� Issue

� Increase ULSD Product Volumes

� Maximize LCO ���� Diesel Pool (SOR/EOR - Throughout Cycle)

� CI Loss SOR ���� EOR: 1-2 CI Numbers

� Throughput Reduction: 1-2 kB/D

� Solution

� Revamp Moderate Pressure DHT

� Base Metal Catalyst

CONFIDENTIAL

� Base Metal Catalyst

� Minor Process Modifications

� Treat Maximum LCO

� Value to Customer

� €3M/YR

(Increased

Diesel Yield)

24

Property Feed Product Delta or Conv Feed Origin LCO/Hydrotreated - 55/45 (Vol Basis) (Feed-Prod or %) Density (kg/m3) 922.9 872.6 50.3 Cetane Index ASTM D-4737-A 28.0 37.9 9.9 UV Aromatics (wt%) PNA 24.31 0.92 96% Total 36.16 15.37 57%

Distillation D-2887 (oC) wt% 10 209 196 13 50 275 257 18 90 344 330 14 95 358 351 8

ULSD/EAS Operations at MOR Conditions*

* Max Reactor Temperatures ~ 375 oC

Diesel Catalytic Dewaxing (DCDW)

� ENABLER: shape-selective zeolites

� Meet seasonal cold flow properties

� Reduce additives

� Increase diesel endpoint / volume

� Minimise kero blending

⇒ Economic Drivers – Cold Flow Improvement /

Diesel Yield Preservation

Single Stage Dewaxing

CONFIDENTIAL

� Minimise kero blending

(jet value high in places)

Paraffin Isomerization:

(Many Possible Isomers)No H2 Consumption &

Very Low ∆HRXN

Two-Stage Dewaxing

25

Selective Paraffin Hydrocracking:

+ H2

+

(Many Possible Cracking Products)

H2 Consumption & ∆HRXN

� Issue

� Upgrade a range of low quality diesel streams (LCO, LVGO)

� Multiple upgrading objectives and two different operating modes

� Do all upgrading in a single unit

Feed Blend, wt% ULSD

Mode

Upgrading Mode

Feed Information

Case Study: Multiple Upgrading Options

CONFIDENTIAL

Mode Mode

LCO 80 60

SRGO1 20 20

SRGO2 20

Density , kg/m3 875.3 862.0

Sulphur, wppm 1813 1412

Total nitrogen, wppm 1181 682

Solidification point, °C 0.7 1.5

Cetane number 30.5 35.6

26

ULSD Mode Upgraded Mode

Case Study 2 –Multiple Upgrading Options

� Solution

� Combine dewaxing

catalyst for seasonal cold

flow improvement of LVGO

components with a mild

hydrocracking catalyst to

upgrade LCO to meet both jet

HydrotreatingMode

Upgrading Mode

Yields, wt%

Gas 1.8 3.0

Naphtha 1.4 4.0

Jet Fuel 23.2

CONFIDENTIAL

upgrade LCO to meet both jet

smoke point and diesel

cetane specifications

� Value to Customer

� Single unit design

� Minimise capital investment (P ~ 90 barg, LHSV = 1.5 hr-1)

Diesel 98.3 72.0

Kero Properties

Density, kg/m3 816.3 816.8

Smoke Point, mm 12.4 21.3

Diesel Properties

Density, kg/m3 844.4 832.1

Sulphur, wppm <10 <10

Solidification point, °C 0 -9

Cetane number 35.6 47.8

27

Heavy Oil conversion

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Conclusions

� Hydroprocessing Catalysts play key role in future of Refining Industry

� Major directions

� Selective Hydrocracking pushing limits of selectivity (better pre-

treat and specially engineered Zeolite combinations)

� Low Hydrogen consumption

CONFIDENTIAL

� Beyond ULSD – HT/MHC combination for jet & diesel

� Enhanced Aromatic saturation

� LCO upgradation

�Heavy Oil upgradation

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