The Shell GTL Process:

Towards a World Scale Project in Qatar:

the Pearl Project

Arend Hoek

Shell Global Solutions International, Amsterdam

DGMK-Conference Synthesis Gas Chemistry

October 4-6, 2006, Dresden
 Contents

Introduction

F-T catalysis

Hydroprocessing

Bintulu learning

Evolution

The Pearl project (Qatar)

Conclusions

2
 What is Gas To Liquids (GTL)?
Methane + Oxygen Hydrogen+ Carbon Fischer-Tropsch distillates+ Water
monoxid
e
Catalyst
Raw
Natural
Gas CH Syngas
Gas 4 Syngas Fischer Tropsch Products
Processing Manufacturing Synthesis Work-up
CO + 2H - CH -
2 2
O
2
LPG
Ethane Bintulu SMDS
GTL Naphtha
LPG
GTL Gas Oil
Condensate
n-Paraffins
Sulphur GTL Base
Oils

Conversion of natural gas to clean, high quality fuels

& products via the Fischer Tropsch process
3
 SGP Upscaling: Experience + Modelling

High quality Syngas:

Upscaling
based on H2/CO 1.8 mol/mol
design criteria CH4 slip < 0.5 vol % dry
used for 50 CO2 content ~ 2 vol % dry
years Carbon to CO ~94 vol %

Modelling tested against Bintulu

Sufficient reactant mixing time

Minimum temperature fluctuations

Upscaling
evaluated by near the refractory wall and no hot
fluid flow and spots
reaction
modelling Dimensioning to achieve long
refractory lifetime

Burner front design checked by

finite element stress analysis
4
 Technical challenges

Carbon efficiency
- selectivity of catalysts

Capex
- process intensity

Availability
- catalyst stability
- robustness

Materials
- resistance against corrosion, erosion,
metal dusting

A GTL plant is mainly a UTILITY complex

- efficient use of steam
5
 Advantages

All in house technology

No boundary issues between process

step

In house catalyst manufacturing

No secrecy issues

6
 Contents

Introduction

F-T catalysis

Hydroprocessing

Bintulu learning

Evolution

The Pearl project (Qatar)

Conclusions

7
 Fischer-Tropsch synthesis

Promoted Co catalyst

Fixed bed multi-tubular reactors

8
 Schulz - Flory FT Kinetics

= probability of chain growth

1
1- = probability of chain termination

CO
Probability

1
CH3 CH4 (1 )

1
C2H5 C2H6
(1 )
(1 ) n
Cn =

1 n-1
CnH2n+1 CnH2n+2 (1 )

9
 The Relevance of Catalyst Selectivity

%m
100
CWax
1-2 Fuel gas
80
C3-4 LPG Produce
wax
60
C5-12 Tops/Naphtha Crack
40
Gasoil back
20 C12-19 Wax
C 20 +
0
0.75 0.80 0.85 0.90 0.95
Probability of chain growth
Co (classic)
Fe (classic)
New catalysts
10
 Preferred process lay-out

Producing max. heavy wax (max. chain

growth probability leads to:

High efficiency (liquid yield)

High gas oil and base oil yield

High degree of isomerisation of gas oil

and base oil

11
 Fischer-Tropsch catalyst R&D

100
Liquid selectivity, %w

Bintulu
Design point
95 Bintulu DBN
Pearl GTL R&D cat.
design

2nd gen. Future

90 2nd gen. GTL?
Pearl GTL
1st gen. Bintulu

efficiency up

85

capex down

80
0 50 100 150 200 250 300 350

relative reactor productivity

12
 Shell FT: Heavy Paraffins Synthesis (HPS)
Configuration: Multi-tubular, water/steam cooled

Synthesis gas

Steam
Cooling
Light
Product Water

Heavy product
Performance:
Automated, fast catalyst loading, In situ catalyst regeneration
High productivity: 7,000 - 9,000 bbl/d per reactor
Liquid Selectivity (CO to liq.): >90%
Easy operation, including start-up, shut-down and transients
13
 Contents

Introduction

F-T catalysis

Hydroprocessing

Bintulu learning

Evolution

The Pearl project (Qatar)

Conclusions

14
 Hydroprocessing step

Dedicated catalyst and conditions

Hydrogenation of oxygenates and olefins

Hydrocracking/isomerisation of paraffins

Bifunctional catalyst: noble metal and acid

function

Low gas make, product flexibility

7.5 years in service

15
 TBP-GLC of hydroprocessing feed and prod.

100

90

80

70 total feed
recovery, %w

60 total product

50

40

30

20

10

0
0 100 200 300 400 500 600 700 800
atm.bp, C

16
 Screening of hydroconversion catalysts
70

60

catalyst 1
catalyst 2
50 catalyst 3
catalyst 4
catalyst 5
selectivity, %w

40

30

20

10

0
C1-C4 sel C5-150 sel 150-200 sel 200-370 sel

17
 Contents

Introduction

F-T catalysis

Hydroprocessing

Bintulu learning

Evolution

The Pearl project (Qatar)

Conclusions

18
 Shell MDS in Malaysia
SCOPE STRUCTURE
Conversion of 110 mmscf/d NG into Shell MDS (Malaysia) Sdn.
575 kt/a (14,700 b/d) of GTL Bhd.
products Shareholders: Shell,
Produces clean fuels and speciality Mitsubishi, Petronas,
products Sarawak State
Worldwide marketing
INVESTMENT
Initial capital investment
of US$850 million SABAH
2003 debottenecking
PENINSULAR investment of US$50
MALAYSIA
million

Kuala Lumpur Bintulu

Shell MDS Plant
Head Office SARAWAK

19
 SMDS - Bintulu - scheme

CH4 CO + 2H2 CH2 Solvents

Natural Syngas
Syngas Synthesis
Synthesis Hydrogenation
Hydrogenation
Gas manufacture
manufacture Waxes
SGP HPS
Middle
Hydrocracking
Hydrocracking
Distillates
O
O22 H2O Lube oil
HPC
ASU feedstock

100 MMSCF/d 14,700 bbl/d

20
 Shell MDS Plant in Bintulu
Malaysia LNG:
6 trains, total of 16.5 mln tpa

Bintulu SMDS:
One train of 14,700 b/d

21
 SMDS - Bintulu

Wax plant/
Specialties Waste water plant

ASU

HPC/HGU/
Distillation

Air coolers

HPS

Compressors

Boilers

HMU
SGP

22
 SMDS Bintulu story

SMDS research started 1973

Pilot plant 1983
SMDS-M project approved 1989
SMDS-M start-up 1993
ASU explosion: ingress of combustibles 1997
ex forest fires
Restart 2000
Debottlenecking 2003
1 year of operation without complex trip 2004

23
 Bintulu: Invaluable learning for Plant reliability

Plant Reliability (% on-

100 stream)
99 Huge challenges at start-up
98
97 You dont know what you
96 dont know
95
Has proven catalyst &
94
93
reactor systems,
procedures for start-up,
92
shut-down, regeneration,
91
emergencies and operability
90
of complex integrated
1994 1995 1996 1997 2001 2002 2003 2004
system
Air Separation Unit
Shell Gasification Process
FT Synthesis

24
 Continuous Improvement in S-MDS Bintulu Natural Gas Efficiency

energy consumed/ Overall 18% improvement in NG efficiency

tonne produced
(relative scale) Achieved by improved utilities integration

100
100
96
93
95

90 88
85 ~84
85

80

75
2001 2002 Pre-DBN Post- 2004 Proj. 2005
(2003) DBN **
steady state (2003)
(no statutory ** DBN = Debottlenecking
shutdown)

25
 GTL Products, yields and applications
GTL plant (Shell Bintulu)
Cracker complex
LPG
(0 5%)
GTL
Naphtha Plastic products
(30 40%) Shell V-Power:
GTL Gasoil Germany
(40 70%)
GTL Base
Oils
(0 30%)

Shell Pura: Thailand

Maximum value from GTL products is derived from an

understanding of the fully integrated value chain
Patent portfolio covering GTL products in high-value
Shell Helix Ultra: Global applications
26 Marketing GTL products for 10 years
 Launch of Shell-VW GTL Test : Berlin, 6th May 2003

Synthetic diesel based on SMDS Gasoil - Bintulu

27
 GTL Fuel can improve air quality in Mega Cities

Dieselisation will improve the CO2

emissions of the transport sector.
Reducing other diesel related
emissions will be a key enabler.
Options available
Reduced sulphur content in
Emission benefits* of Shell GTL fuel
diesel Growing importance of clean public transport
Based on trial result of 100% Shell GTL
Improved engine management Fuel in 25 Volkswagen Golfs without
any vehicle modifications, Berlin, 2003.
systems
Nitrogen Oxides - 6%
Exhaust after treatment Particulates (PM10) - 20%
(particle filter or chemical Hydrocarbon - 63%
CarbonMonoxides - 91%
treatment)
*Reference Fuel: Diesel < 10ppm sulphur
Introduction of GTL fuel Source: VW
28
 AndGTL Fuel is by no means slow
Shell worked with Audi to build the first diesel racing car
winning the Le Mans 24 hour race.
The Audi R-10 is fueled by a diesel containing GTL Fuel, based
on Shell V-Power technology.

Fuel and engine developments together deliver:

Exceptional Torque
Very low noise
Improved fuel
consumption

Audi R-10 during its maiden victory

at the 12 hours of Sebring
29
 with the Courtesy
of Volkswagen

30
 Contents

Introduction

F-T catalysis

Hydroprocessing

Bintulu learning

Evolution

The Pearl project (Qatar)

Conclusions

31
 Gas to Liquids coming of age
compare: LNG

Train capacity Mtpa

Existing 8
GTL Plant Costs Proposed 7

Specific cost, a.u.

Construction 6
Bintulu (12,500 bpd) 5
4
3
2
Specific Capex, a.u.

1
Economies 0
1960 1970 1980 1990 2000 2010
of Scale
Start-up Year
Two trains
(140,000 bpd) Brown Field
2nd generation
catalyst Expansion

3rd generation
catalyst

32 1990 2000 2010 2020

 Contents

Introduction

F-T catalysis

Hydroprocessing

Bintulu learning

Evolution

The Pearl project (Qatar)

Conclusions

33
 Qatar Shell GTL Project Overview

Fully integrated project Two wellhead

NORTH FIELD platforms

Development Production
Two multiphase
Sharing Agreement (DPSA), pipelines
100% Shell
Two onshore phases
Ethane
~1,600 MMscf/d well head gas Gas Treating
Propane
C2/LPG Extr.
Butane
Cond.Process.
Ras Laffan Condens.
140,000 b/d GTL products Sulphur Recov. Sulphur
GTL Naphtha
Doha Utilities Gasoil
Two phases, start-up phase 1: Storage
n-Paraffins
BaseOils
General Fac.
2009/2010 Water

34
 Tangible Progress in Qatar
Seismic
800 km2 3 D seismics completed in 2003
Providing info for appraisal drilling and for
subsurface modelling of allocated area

Appraisal Well Drilling

First well spud on 14th February and completed
31st August 2004
Second well spud on 4th September and
completed 19th December 2004

Geotechnical Site Investigations

First phase completed Dec.03 April 04

35
 Pearl GTL Project Progress Continues
2002: Statement of Intent

2003: Heads of Agreement (HOA)

2004: Development Production Sharing Agreement (DPSA)

2005: Front End Engineering Design (FEED) completed

Permit to Construct granted
Project Management Contractor (PMC) appointed
All EPC contracts tendered
FT synthesis reactors ordered
Development drilling contract awarded

2006: Submission of Final Development Plan

F-T catalyst production started
Final project approvals
Award EPC contracts
Start site activities
Intense procurement activities

36
 Tangible Progress: FEED and Contracting Activities
Offshore Front-End-Engineering-Design (FEED):
Conducted in Shell offices, Aberdeen during
March 2004 to February 2005
Onshore FEED:
Conducted by JGC, primarily in the London
offices of MW Kellogg (joint venture of JGC &
KBR), during March 2004 May 2005
Close to 500,000 man-hours

Investment Decision
July 2006

EPC Contracting:
Multiple contractor strategy
Several bids awarded (Sep. 2006)
37
 SMDS capacity build-up configuration
Modular sections
Configuration for 70,000 bpd

ASUs SGPs HPS reactors

Common
Utilities

Work-up
incl HPC

Storage &
Single train
Loading

Work-up
incl HPC General
Facilities
Single train

Additional modules to build to capacity of 140,000 bbl/d

38
 Pearl project (Qatar Shell GTL)

Watertreating Gas Processing GTL Process

Utilities

ASUs
Storage

39
 Onshore construction dimensions

er s 144
et 0m
0m e te r
161 Type Quantity s
Equipment 2,300 items
Equipment 100,000 tons

Piping 50,000
tons
Structural steel 30,000 tons
Concrete 200,000 m3
Cables 1,800 km
Insulation 700,000 m2
Control loops 3,500
40
 Pearl will break many records
The world's largest capacity to produce premium quality base oils.

The worlds largest producer of GTL based normal paraffin and will be
the worlds lowest cost normal paraffins producer.
The largest single train Hydrocracker in Shell and the worlds largest
Hydrocracking capacity in one location.
The worlds largest ASU in terms of high purity Oxygen and the worlds
largest overall Oxygen production on one location.
The worlds largest ever catalyst supply contract.

The worlds largest system for full recovery of industrial process water,
achieving 'zero-liquid discharge.
One of the worlds largest and most advanced Fieldbus instrumentation
and control systems.
One of the worlds most advanced multipurpose, multi plant dynamic
process simulators.
The largest steam generation capacity of any hydrocarbon processing
plant in the world (or indeed ... in the Petroleum Industry).
41
 GTL Challenges: From Reservoir to Market
LPG
Naphtha

Gasoil

LDF
Baseoils
Upstream: GTL R&D: Project Commercial etc:
Seismics Surface sciences Implementation: Economics
Geology Adv. analytical tools Process technology Financing
Petrophysics FT catalyst Utilities technology Legal
Reservoir development Offsites technology Taxation
engineering Reactor engineering C, M, E, I Authority
Production CFD modelling engineering engineer.
technology Syngas Process control Marketing
Well engineering development Rotating equipment Trading
Well testing Hydro conversion QA/QC Shipping
Offshore structures Bench scale testing HSE management Accounting
Pipelines Pilot plant testing Materials&Corrosion HR management
Materials&Corrosion IP protection Project engineering IT management
Operations Process modelling Logistics Traning&Devel.
Value engineering Risk
.. excellence over huge span Contracting&Procur. management
Commissioning& SU Project
of skills integration
42 Operations
 Contents

Introduction

F-T catalysis

Hydroprocessing

Bintulu learning

Evolution

The Pearl project (Qatar)

Conclusions

43
Why Gas to Liquids?
Energy security Strategic diversification of energy
supply
Biomass and Coal to Liquids
Environment Trend towards cleaner fuels
Economic development Remote gas reserves
commercialisation
Most cost effective alternative fuel
Strategic diversification of gas market
GTL Fuel has unique properties:

-Virtually free of sulphur and

aromatics

-High cetane number

44
 Shell GTL Development
Integrated world scale Qatar project based on proven technology
A platform for exciting new industry based on unique new products

World-scale plant:
Bintulu Malaysia Shell Qatar GTL
14 700 b/d 140 000 b/d
Pilot plant 1993 2009
1983
Laboratory
1973

Long lead times & entry hurdles characterise GTL

development
45
 The end

Thank you for your attention

46
 Back-up slides

47
 GTL as Alternative to LNG

Fixed Chain
600 LNG Plant Shipping ~ 3500 nm Regasification
MMSCF/D ~ 4 mtpa 3 x 130,000 m3

600 MMSCF/D SMDS Unconstrained Market

75,000 bbl/day
Product carriers- Distribution/
spot/term Blending

48
 GTL Appeals to Gas Resource Holders

LNG GTL product slate

150 mln tpa 2,000 mln tpa

8%
i r tu ally
V
s tr icted
u n re

0.6%

15 tcf gas
over project life

Growth of GTL is not market constrained and complementary to pipelines and

LNG

49
 Cold flow properties of Shell GTL fuel (340C endpoint)
0

-5
Cloud
CFPP

-10
CP or CFPP, C

-15
changing
process conditions

-20

-25

-30
78 79 80 81 82 83 84 85 86 87
Cetane number

50
 POTENTIAL TO MEET REGULATIONS

0.08 1.2
M.Benz
0.07 VWBora
1 CitroenXantia
0.06
Euro III limit
0.8
PM g/km

CO g/km
0.05 Euro III limit
0.04 0.6
0.03
0.4 Euro IV limit
0.02 Euro IV limit
M.Benz
M.Benz

0.01
VW Bora
VWBora 0.2
oenXantia
CitroenXantia
Citr

0 0
0 20 40 60 80 100 0 20 40 60 80 100
Shell GTL fuel content % Shell GTL fuel content %

51
 Gas grows faster than oil

mln boed Gas growth driven

by:
120
Oil & Gas demand

z CCGT* economics
100 and power
Oil liberalisation
80 z Customer
preference for clean
60 Gas fuel
z Kyoto and CO2
40 constraints

20 Gas for Power

Generation
0
1990 2000 2010 2020 *CCGT = Combined cycle gas
turbine

52
 Gas Utilisation

2000 million scf/d

Pipeline LNG 1000

500
GtL Quantity
200

100

50
Electricity
20
Chemicals
10
Distance 1000 2000 3000 4000 5000 km
53
Continuous operation of Bintulu complex without unplanned shutdown

450 430

400

350
Days between complex shutdown

300
270

250

200
157
141
150
114

100 79 85
71
56

50 15

0
1993 1994 1995 1996 1997 1998 1999 2000 2001 2002 2003 2004

54
 LNG & GTL in comparison

Targetting different markets

LNG: Dedicated shipping and receiving terminals

Long term contracts
Power generation and gas markets
GtL: Viable for smaller gas reserves
Potential to substitute for oil imports
High quality, ultra clean fuel applications

55
 Life Cycle Analysis GHG Emissions
Industry LCA studies show the GHG emissions of a
Greenhouse Gases
GTL system to be comparable to a complex refinery (CO2 equivalents)
system
100%
Efforts are focused on GTL process
efficiency through R&D programs,
targeting up to 20% efficiency
improvements
Advanced GTL engines are being
developed, sponsored by
governments, and targeting up to
10% efficiency improvements

The GTL system also has: 0

GTL GTL
significant lower impact on air REFINERY GTL System -
System -
acidification and smog formation Use of products Potential Potential
Transport to users (Process
lower emissions of particulate matter Production of products (Engine
Extraction of feedstock Efficiency) Efficiency)
less hazardous waste production
56
 Emissions Performance Volkswagen Test

0,3
Grenzwerte EU IV Diesel < 10ppm S
NOx= - 6,4% Part. = - 26% Shell GTL
Emissionswerte [g/km]

0,2

HC = - 63% CO = - 91%
0,1
EU IV

0
NOx Partikel10 HC CO

Berlin Fleet test 2003 - VW Golf with Shell GTL

57 Fuel
 Key Processes: Shell Proprietary Technology
Simplified
.. GTL
proven in Process Overview
Bintulu

Natural
Gas Steam Hydrogen Manuf.
Methane Unit (HMU) H2
Reformer
Natural (SMR)
Heavy Heavy
Gas Shell Paraffins Paraffins Synthetic LPG
Gasification Synthesi Conversion Crude Distiller Naptha
Process s (HPS) (HPC) (SCD) Gasoil
(SGP)
O2 Lube Base Lube
Light Oils Units Base
Air Air (BO) Oils
Detergent Normal
Separation Feedstock unit Paraffins
Unit (ASU) (LDF)

Utilities

Off-sites & Common Facilities

58