Gas to Liquid Fuels Technology (GTL)

Valrie Sage
CSIRO Petroleum Resources Gas Processing and Conversion
WA:ERA Gas Technologies Breakfast Seminar 19.02.2009

The Alternative Route to Oil

Alternative Feedstock Natural Gas Coal Biomass Products

GTL

XTL CTL
BTL

Transport Fuels Chemicals

CSIRO GTL - WA:ERA Gas Technologies Breakfast Seminar - 19.02.2009

XTL Processes

GTL

Natural Gas

Reformer

Syngas

FT Products

Products upgrade

Oxygenates

Air

BTL

Bio ma s

Air Separation Unit

Fischer-Tropsch Reactor
Paraffin

Gasification
al Co

Syngas

Syncrude

Hydrocracker

Diesel Naphtha Lubricants

CTL
Sequestrated CO2

Syngas = CO and H2
CSIRO GTL - WA:ERA Gas Technologies Breakfast Seminar - 19.02.2009

Well to Wheel GHG Emissions (syn-diesel)

From ASFE Position Paper: Emissions from Synthetic Fuels, Alliance for Synthetic Fuels in Europe (ASFE), January 2007 (http://www.synthetic-fuels.org/documents/20070221124435_ASFE%20Position%20Paper%20on%20Emissions.pdf)
CSIRO GTL - WA:ERA Gas Technologies Breakfast Seminar - 19.02.2009

Which Feedstock ?
Biomass
+ Lower emissions - Not enough supply (~5% of needs) - Food vs. fuels issues

Coal
+ Large reserves - Capital cost ~60% more than GTL - Processing more expensive - Higher emissions

Gas
+ Abundant reserves, especially in WA + Use of stranded, associated, and off-shore gas resources - Emissions similar to conventional diesel
CSIRO GTL - WA:ERA Gas Technologies Breakfast Seminar - 19.02.2009

Gas Reserves in Australia

CSIRO GTL - WA:ERA Gas Technologies Breakfast Seminar - 19.02.2009

Is GTL the answer?

Other alternatives to transform natural gas Liquefied Natural Gas (LNG)
Deep refrigeration Special ships for transport Large investments for liquefaction and regasification terminals Security issues

Compressed Natural Gas (CNG)

Pressurisation Special ships for transport Less expensive than LNG Competitive only for small distance and volume

In both cases, the receiving end product is still gas

CSIRO GTL - WA:ERA Gas Technologies Breakfast Seminar - 19.02.2009

Benefit of GLT
Security of supply
Available in increasing volumes Alternative supply locations (e.g. stranded)

Environmental performance local emissions

Cleaner products (middle distillates) GTL Fuels
Lower emissions (NOx, HC, CO, SOx) Higher cetane number (75-80)

CSIRO GTL - WA:ERA Gas Technologies Breakfast Seminar - 19.02.2009

Benefit of GLT (cont)

Compatibility
Can be used in existing engines and refuelling infrastructure

Cost effectiveness
Existing infrastructure

Diversification
Stranded and associated gas reserves use BTL

CSIRO GTL - WA:ERA Gas Technologies Breakfast Seminar - 19.02.2009

GTL Around the World

Existing large scale commercial GTL - FT process plants
Shell (Malaysia)
Natural gas as feedstock low-sulphur diesel fuels products Multitubular fixed-bed reactor Co based catalysts 15,000 bbl/day

Sasol (South Africa)

Coal and natural gas as feedstock Variety of synthetic petroleum products Synthol reactors (fluidized bed): > 120,000 bbl/day Slurry bubble reactor: 2,500 bbl/day

Sasol/Chevron (Oryx, Qatar)

Natural gas feedstock Variety of synthetic petroleum products Slurry bubble reactor 34,000 bbl/day

PetroSA
Circulating fluid bed reactor 14,000 bbl/day/reactor (3 reactors)

CSIRO GTL - WA:ERA Gas Technologies Breakfast Seminar - 19.02.2009

Oryx GTL Plant (Qatar)

Reformer Oxygen Plant

FT Reactor

Capacity: 34,000 b/d of liquids

- 70 % of diesel - 26 % of naphtha - 4 % of LPG
(100,000 b/day by 2009) (130,000 b/day by 2010)

Oryx GTL plant at Qatar, Being Operated from July, 2006

1 mile2 surface
CSIRO GTL - WA:ERA Gas Technologies Breakfast Seminar - 19.02.2009

GTL Plants
Large plants
Oxygen generation unit Reformer Fischer-Tropsch reactor Post-treatment unit

High capital investment and operating cost

CSIRO GTL - WA:ERA Gas Technologies Breakfast Seminar - 19.02.2009

GTL Challenges and Opportunities

Reduce costs (capital and operational) Minimise emissions
CO2 Sequestration

Reduce plant footprint

Plant usable for small operations
Associated gas (on or off-shore) Stranded gas reserves (on or off-shore)

CSIRO GTL - WA:ERA Gas Technologies Breakfast Seminar - 19.02.2009

Syngas Production
Steam reforming Dry reforming Partial oxidation Combustion Water gas shift Thermal pyrolysis
CH4 + H2O CO + 3H2 CH4 + O2 CO + 2H2 H2O + CO CO2 + H2 2CH4 C2H4 + 2H2 H0=206 kJ/mol H0=-36 kJ/mol H0=-41 kJ/mol H0=202 kJ/mol

CH4 + CO2 2CO + 2H2 H0=247 kJ/mol CH4 + 2O2 CO2 + 2H2O H0=-802 kJ/mol

Combined exo- end endothermic reaction

Autothermal reforming: partial oxidation + steam reforming Oxypyrolysis: partial oxidation + thermal pyrolysis

CSIRO GTL - WA:ERA Gas Technologies Breakfast Seminar - 19.02.2009

Synfuel Production
Fischer-Tropsch synthesis
n CO + 2n H2 -(CH2)n + H2O

Conditions
Optimum H2:CO = 2:1 Transition metal-based catalyst Fe, Co, Ni, or Ru High temperature (> 300 C, Fe catalysts) Low temperature (~ 200 C, Co catalysts) Pressure > 2 MPa

CSIRO GTL - WA:ERA Gas Technologies Breakfast Seminar - 19.02.2009

Fischer-Tropsch Synthesis (cont)

Refining step necessary
CnH2n+2 Fuels, lubricants, etc.

Large range of products:

Naphtha, diesel, paraffin, oxygenates (inc. alcohols)

FT Product distribution as a function of chaingrowth probability

Extracted from http://www.fischer-tropsch.org/primary_documents/presentations/acs2001_chicago/chic_slide05.htm CSIRO GTL - WA:ERA Gas Technologies Breakfast Seminar - 19.02.2009

Fischer-Tropsch Synthesis Challenges

Highly exothermic reaction
Need efficient heat removal

Solid separation
Wax formation - Removal from the reactor system

Side reactions
Water gas shift (CO + H2O CO2 + H2) Steam reforming (CH4 + 2 H2O CO + 3 H2) Dry reforming (CH4 + 2 CO2 2 CO + 2 H2)

Large range of product

Poor selectivity

CSIRO GTL - WA:ERA Gas Technologies Breakfast Seminar - 19.02.2009

Future of Fischer-Tropsch Process

Catalysis design
Co based catalysts more resistant than Fe based catalyst Ru based supported slurry catalysts

Reactor design
Shift from fixed-bed reactor to slurry phase process
Improved heat removal efficient mixing

Gas recycling Reduced plant footprint Reduced capital cost

Process optimisation
Reaction conditions Use of additives
CSIRO GTL - WA:ERA Gas Technologies Breakfast Seminar - 19.02.2009

In Summary, Why GTL?

Security of supply Valorisation of stranded and off-shore gas reserves Use of existing infrastructure Develop a cost effective production of synthetic fuels Build capability Diversification
FT applicable to gas, coal, and biomass

CSIRO GTL - WA:ERA Gas Technologies Breakfast Seminar - 19.02.2009

CSIRO Petroleum Resources Dr Valrie Sage Research Scientist Gas Processing and Conversion Group Phone: 08 6436 8836 Email: valerie.sage@csiro.au Web: www.dpr.csiro.au

Thank you
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