The Shell GTL Process - DGMK

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

Raw Natural Gas

Gas Processing

CH 4

O

Hydrogen+ Carbon Fischer-Tropsch distillates+ Water monoxid e Catalyst

Syngas Manufacturing

Syngas CO + 2H 2

Fischer Tropsch Synthesis

- CH 2

Products Work-up

2

Bintulu SMDS

Ethane LPG

LPG GTL Naphtha GTL Gas Oil

Condensate Sulphur

GTL Base Oils Conversion of natural gas to clean, high quality fuels & products via the Fischer Tropsch process

3

n-Paraffins

SGP Upscaling: Experience + Modelling Upscaling based on design criteria used for 50 years

• High quality Syngas: H2/CO 1.8 mol/mol CH4 slip < 0.5 vol % dry CO2 content ~ 2 vol % dry Carbon to CO ~94 vol %

• Modelling tested against Bintulu • Sufficient reactant mixing time Upscaling evaluated by fluid flow and reaction modelling

• Minimum temperature fluctuations near the refractory wall and no hot spots • 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


7

Fischer-Tropsch synthesis

Promoted Co catalyst Fixed bed multi-tubular reactors

8

Schulz - Flory FT Kinetics α 1−α 1-

= probability of chain growth

= probability of chain termination

CO Probability

CH3

1−α

CH4

(1 − α)

α C2H5

1−α

C2H6

α (1 − α)

α

Cn =

α CnH2n+1 9

(1 − α)

1−α

n-1

CnH2n+2

α (1 − α)

α

α

n

The Relevance of Catalyst Selectivity

%m 100 80

CWax 1-2 C3-4

Fuel gas

Produce wax

LPG

60

C5-12

Tops/Naphtha

40

Gasoil

20

Wax

C12-19

C 20 +

0 0.75

0.80

0.85 Co (classic)

0.90

0.95

Probability of chain growth

Fe (classic) New catalysts 10

Crack back

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

Liquid selectivity, %w

100

95

Bintulu DBN

Bintulu design

90 1st gen.

Design point Pearl GTL

R&D cat.

Future GTL?

2nd gen. Pearl GTL

2nd gen. Bintulu

efficiency up 85

capex down 80 0

50

100

150

200

250

relative reactor productivity 12

300

350

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


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

recovery, %w

80 70

total feed

60

total product

50 40 30 20 10 0 0

100

200

300

400 atm.bp, °C

16

500

600

700

800

Screening of hydroconversion catalysts 70

60 catalyst 1 catalyst 2 catalyst 3 catalyst 4 catalyst 5

selectivity, %w

50

40

30

20

10

0 C1-C4 sel

17

C5-150 sel

150-200 sel

200-370 sel


18

Shell MDS in Malaysia STRUCTURE

SCOPE Conversion of 110 mmscf/d NG into 575 kt/a (14,700 b/d) of GTL products Produces clean fuels and speciality products

Shell MDS (Malaysia) Sdn. Bhd. Shareholders: Shell, Mitsubishi, Petronas, Sarawak State

Worldwide marketing

PENINSULAR MALAYSIA

INVESTMENT Initial capital investment of US$850 million 2003 debottenecking investment of US$50 million

Kuala Lumpur Head Office 19

SABAH

Bintulu Shell MDS Plant SARAWAK

SMDS - Bintulu - scheme

CH4

Natural Gas

– CH2 –

CO + 2H2

Syngas Syngas manufacture manufacture

SGP

Synthesis Synthesis

Solvents

Hydrogenation Hydrogenation

HPS Hydrocracking Hydrocracking

O O22 ASU 100 MMSCF/d

20

H2O

HPC

Waxes Middle Distillates Lube oil feedstock 14,700 bbl/d

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 (% onstream) 100 Huge challenges at start-up

99 98

“You don’t know what you

97

don’t know”

96 95

Has proven catalyst &

94 93 92 91 90 1994 1995 1996 1997 2001 2002 2003 2004 Air Separation Unit Shell Gasification Process FT Synthesis

24

reactor systems, procedures for start-up, shut-down, regeneration, emergencies and operability of complex integrated system

Continuous Improvement in S-MDS Bintulu Natural Gas Efficiency

Overall 18% improvement in NG efficiency

energy consumed/ tonne produced (relative scale)

100

Achieved by improved utilities integration

100 96 93

95 90

88 85

~84

85 80 75 2001

2002

Pre-DBN (2003) steady state (no statutory shutdown)

25

PostDBN ** (2003)

2004

Proj. 2005

** DBN = Debottlenecking

GTL Products, yields and applications GTL plant (Shell Bintulu)

LPG (0 – 5%) GTL Naphtha (30 – 40%) GTL Gasoil (40 – 70%)

Cracker complex

Plastic products Shell V-Power: Germany

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 26

applications 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 diesel Improved engine management systems Exhaust after treatment (particle filter or chemical treatment) Introduction of GTL fuel 28

Emission benefits* of Shell GTL fuel Growing importance of clean public transport Based on trial result of 100% Shell GTL Fuel in 25 Volkswagen Golfs without any vehicle modifications, Berlin, 2003.

Nitrogen Oxides Particulates (PM10) Hydrocarbon CarbonMonoxides

- 6% - 20% - 63% - 91%

*Reference Fuel: Diesel < 10ppm sulphur Source: VW

And…………GTL 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


31

Gas to Liquids coming of age

Specific Capex, a.u.

Bintulu (12,500 bpd)

Specific cost, a.u.

GTL Plant Costs

Economies of Scale

8 7 6 5 4 3 2 1 0 1960 1970 1980 1990 2000 2010 Start-up Year

Existing Proposed Construction

Two trains 2nd generation catalyst

(140,000 bpd)

Brown Field Expansion

3rd generation catalyst

32

1990

2000

2010

2020

Train capacity Mtpa

compare: LNG


33

Qatar Shell GTL Project Overview Fully integrated project

Two wellhead platforms

NORTH FIELD

Development Production Sharing Agreement (DPSA), 100% Shell

Two multiphase pipelines Two onshore phases

~1,600 MMscf/d well head gas 140,000 b/d GTL products Two phases, start-up phase 1: 2009/2010

34

Ras Laffan Doha

Gas Treating C2/LPG Extr. Cond.Process. Sulphur Recov. GTL Utilities Storage General Fac.

Ethane Propane Butane Condens. Sulphur Naphtha Gasoil n-Paraffins BaseOils Water

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

35

First phase completed Dec.’03 – April ’04

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 Configuration for 70,000 bpd

Modular sections ASUs

SGPs

HPS reactors Common Utilities Work-up incl HPC

Single train

Work-up incl HPC

Single train Additional modules to build to capacity of 140,000 bbl/d 38

Storage & Loading

General Facilities

Pearl project (Qatar Shell GTL) Watertreating Gas Processing GTL Process Utilities

ASUs Storage 39

Onshore construction dimensions

161

s r e t e 0m

0m e te r

Type

Quantity

Equipment

2,300 items

Equipment

100,000 tons

Piping tons

50,000

Structural steel

30,000 tons

Concrete

200,000 m3

Cables Insulation Control loops 40

144

1,800 km 700,000 m2 3,500

s

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 41

plant in the world (or indeed ... in the Petroleum Industry).

GTL Challenges: ‘From Reservoir to Market’ LPG Naphtha Gasoil LDF Baseoils

Upstream: • • • • • • • • • • •

GTL R&D:

Seismics • Geology • Petrophysics • Reservoir • engineering Production • technology • Well engineering Well testing • Offshore structures • Pipelines • Materials&Corrosion • Operations •

Surface sciences Adv. analytical tools FT catalyst development Reactor engineering CFD modelling Syngas development Hydro conversion Bench scale testing Pilot plant testing IP protection Process modelling

.. excellence over huge span of skills 42

Project Implementation: • • • • • • • • • • • • • • •

Process technology Utilities technology Offsites technology C, M, E, I engineering Process control Rotating equipment QA/QC HSE management Materials&Corrosion Project engineering Logistics Value engineering Contracting&Procur. Commissioning& SU Operations

Commercial etc: • • • • • • • • • • • • • •

Economics Financing Legal Taxation Authority engineer. Marketing Trading Shipping Accounting HR management IT management Traning&Devel. Risk management Project integration


43

Why Gas to Liquids? → Strategic diversification of energy

Energy security supply

→ Biomass and Coal to Liquids Environment

→ Trend towards cleaner fuels

Economic development commercialisation

→ Remote gas reserves

→ 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

Pilot plant 1983

Bintulu Malaysia 14 700 b/d 1993

World-scale plant: Shell Qatar GTL 140 000 b/d 2009

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 MMSCF/D

LNG Plant ~ 4 mtpa

600 MMSCF/D

SMDS

75,000 bbl/day

Shipping ~ 3500 nm 3 x 130,000 m3

Regasification

Unconstrained Market Product carriersspot/term

48

Distribution/ Blending

GTL Appeals to Gas Resource Holders LNG 150 mln tpa

GTL product slate 2,000 mln tpa

8%

ally u t r i V icted r t s 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 (340°C endpoint) 0

-5 Cloud

CP or CFPP, °C

CFPP

-10

-15 changing process conditions

-20

-25

-30 78

50

79

80

81

82 83 Cetane number

84

85

86

87

POTENTIAL TO MEET REGULATIONS 0.08

1.2 M.Benz

0.07 Euro III limit CO g/km

PM g/km

0.06 0.05 0.04 0.03 M.Benz M.Benz VW Bora VWBora CitroenXantia Citr oenXantia

0.01

Euro III limit

0.6 Euro IV limit

Euro IV limit 0.2

0

51

0.8

0.4

0.02

0

VWBora CitroenXantia

1

20

40 60 80 Shell GTL fuel content %

100

0 0

20

40 60 80 Shell GTL fuel content %

100

Gas grows faster than oil Gas growth driven by:

mln boed Oil & Gas demand

120

z

100 Oil

80 60

Gas

40 20

Gas for Power Generation

0 1990 52

CCGT* economics and power liberalisation z Customer preference for clean fuel z Kyoto and CO2 constraints

2000

2010

2020

*CCGT = Combined cycle gas turbine

Gas Utilisation

2000 million scf/d

LNG

Pipeline

1000 500

GtL

200 100 50

Electricity Chemicals Distance 1000 53

2000

3000

4000

20

10 5000 km

Quantity

Continuous operation of Bintulu complex without unplanned shutdown

450

430

Days between complex shutdown

400 350 300

270

250 200 157 141

150

114

100

85

79

71

56

50

15

0 1993

54

1994

1995

1996

1997

1998

1999

2000

2001

2002

2003

2004

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 GTL system to be comparable to a complex refinery system

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: –

56

Greenhouse Gases (CO2 equivalents)

100%

significant lower impact on air acidification and smog formation

–

lower emissions of particulate matter

–

less hazardous waste production

0

GTL REFINERY

GTL

Use of products Transport to users Production of products Extraction of feedstock

System Potential

GTL System Potential

(Process (Engine Efficiency) Efficiency)

Emissions Performance – Volkswagen Test 0,3

Diesel < 10ppm S

Emissionswerte [g/km]

Grenzwerte EU IV ΔNOx= - 6,4%

ΔPart. = - 26%

Shell GTL

0,2

ΔHC = - 63%

ΔCO = - 91%

0,1

EU IV 0

NOx

57

Partikel·10

HC

Berlin Fleet test 2003 - VW Golf with Shell GTL Fuel

CO

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

Natural Gas

Natural Gas

Air

Steam Methane Reformer (SMR) Shell Gasification Process (SGP) O2 Air Separation Unit (ASU)

Hydrogen Manuf. Unit (HMU)

Heavy Paraffins Synthesi s (HPS)

H2

Heavy Paraffins Conversion (HPC)

Light Detergent Feedstock unit (LDF)

Utilities Off-sites & Common Facilities 58

Synthetic Crude Distiller (SCD)

Lube Base Oils Units (BO)

LPG Naptha Gasoil Lube Base Oils Normal Paraffins

The Shell GTL Process - DGMK

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