Gas to Liquids (GTL)

(Gas to Synthetic Fuels)

Technology and Economics

Widodo W Purwanto
Dijan Supramono
 Outline
 What is GTL

 GTL Process

 Syngas Production

 Key Technical Issues

 FT synthesis

 Product Upgrading

 GTL Economics

 Product Quality & Market

 GTL Projects

 Future of GTL
 Future fuel supply

CTL/

Notes:
1. CG and H2 as gas fuel feeds to fuel cell
2. CTL = coal to liquids
3. Biomass as raw material to make biofuels Source:APEC
 Natural gas conversions

Pipeline
Liquefied natural gas (LNG)

Compressed natural gas (CNG)

SUPPLY MARKETS
Gas to Solids (GTS)
Gas to Liquids (GTL)

Gas to Chemicals (GTC)

Gas to Wire (GTW)

Physical conversion : pipeline, CNG, LNG, GTS (gas to solid)

Chemical conversion : GTL, CTL, GTW

 What is gas hydrates
(Gas to solid)?
o Gas hydrates are crystalline substances
composed of water and gas in which a solid
water-lattice accommodates gas molecules in a
cagelike structure (clathrate)
water
o Types of gas hydrates methane

1. Natural gas hydrates

2. Synthetic gas hydrates
Synthetic Natural gas hydrate (NGH) system from pellet production to
the NGH utilization in gas turbine power plant
What is Gas to
Liquids (GTL)?
 What is Gas to Liquids?
Professor Franz Fischer .. and
Dr Hans Tropsch were
inventors of a process to
create liquid hydrocarbons
from carbon monoxide gas
and hydrogen using metal
catalyst

Gas-to-Liquid (GTL) fuels may be produced from natural gas using a

Fischer- Tropsch chemical reaction process. The liquids produced include
diesel, naphtha, and chemical feedstocks. GTL diesel can be used as neat or
blended with today’s diesel fuel in existing diesel engines. These fuels provide
an opportunity to reduce dependence on petroleum-based fuels and reduce
tailpipe emissions. GTL fuel has virtually no sulfur, aromatics, or toxics. It
can be blended with non-complying diesel fuel to make the fuel cleaner so it
will comply with new diesel fuel standards.
Fischer-Tropsch Diesel
 Why need synthetic fuels?

 To substitute to petroleum fuels

 Can be manufactured using infrastructure of
petroleum-based fuels
 As ultra-clean fuels: near-zero sulfur and
aromatic, high cetane number
but
Need chemical conversions
Diesel quality regulation

Source: Sasol
GTL Process
Petroleum to liquids (fossil fuels)
for comparison
 Feedstock of liquids (synthetic
fuels and chemicals)
H/C 0.1 2 4 0.1

Feed to FT
process
H2/CO= 2

Source: Sasol, modified

 Indirect process conversion to synthetic
fuels + chemicals (through syngas)
Synthetic fuels
Biomassa
sis
Gasification the
Feed + O2 + H2O S yn
H2/CO FT DME
s
S y nthesi
Coal DME
Syngas MeOH Synthesis MeOH
(H2+CO)
SMR (CH4+H2O)
Fue

ll
lC

l Ce
ells

MT
POX (CH4+O2)

Fue
IGC
Gas

O
C
CO2R (CH4+CO2) NH
3 Electricity
Sy
nt
Combined Reforming he Olefins
si
s
NH3
 Direct process conversion to
synthetic fuels + chemicals
Pyrolisis
Synthetic fuels
Coal (liquid/gas)
Hydrogenation
Ethylene
g
lin
Heat Combustion
Co
up
e
ativ
id Methanol
Ox
i da tion Formaldehyde
r ti al Ox
P a
CH4
Methane C
onversion
Aromatics
Me
tha
ne
cr a
cki
ng
Hydrogen
nanocarbon
 GTL Flow Diagram (through POX)
H2S, CO2, H2O Electricity

CH4 H2,CO
Natural
Gas Desulphurizer Syngas Cogeneration
Unit Production Unit Unit

O2 H2,CO Tail
Air Gas
Air Separation Polybed PSA
Unit Unit H2
Light
H2/CO=2 Ends

N2 FT Synthesis Upgrading
Unit Unit
Catalyst
Separation Naphtha,
Syncrude Diesel
Syngas Production
 Synthetic gas (syngas) reactions
• Steam Reforming of Methane (SRM)
CH4 + H2O  CO + 3 H2 205.9 kJ/mole (H >> 0)
• Partial Oxidation (POX)

CH4 + ½ O2  CO + 2 H2 -35.9 kJ/mole (H < 0)

• CO2 Reforming (CO2R or DRM)

CH4 + CO2  2CO + 2 H2 247.1 kJ/mole (H >> 0)

. Water gas shift reaction (side-reaction of SRM)
CO + H2O  CO2 + H2 -41.2 kJ/mole
. Carbon deposition (side-reactions of DRM)
2 CO  C(solid) + CO2 - 171.5 kJ/mole (dis-proportionate Boudouard)
CO + H2  C(solid) + H2O - 131.3 kJ/mole
Syngas quality is ratio of H2/CO
 Production of synthesis gas
(syngas)
 Production of synthesis gas (“syngas”) mostly occurs using
either partial oxidation or steam reforming.
 Partial oxidation: CH4 + 1/2 O2  CO + 2 H2 (exothermic)
 Steam reforming: CH4 + H2O  CO + 3 H2 (endothermic)
 Other possible reactions:
• CO + H2O  CO2 + H2 (water gas shift reaction)
• CH4 + CO2  2 CO + 2 H2
 CO2 reforming in general is avoided due to its tendency to form
carbon deposit (see carbon deposition reactions). This
reforming is applied for certain purposes such as for CO 2
capture, DME manufacturing (requires H2/CO = 1).
 Partial Oxidation Synthesis Gas
Production
 CH4 + 1/2 O2  CO + 2 H2
 Combustion chamber at high temperature (1200 -1500°C)
and high pressure (up to 7 MPa); no catalyst. Carbon
efficiency 90% (Eilers et al, 1990).
 Main competing reaction: decomposition of methane to
carbon black (due to high temperature, non-catalytic nature
of the chemistry)
 Three process sections:
 Burner section where combustion occurs (with pure
oxygen to avoid presence of nitrogen—nitrogen is
desirable only when making ammonia)
 Heat recovery section
 Carbon black removal section: first by water scrubbing,
then extraction by naphtha
 Steam Reforming Synthesis Gas
Production
 CH4 + H2O  CO + 3 H2
 Carried out in the presence of catalyst—usually nickel dispersed on
alumina support
 Operating conditions: 850-940°C, 3 MPa
 Due to water gas shift reaction, more H2 is produced, which can be
used in hydrocracking. Excess CO2 is absorbed in amine scrubber.
 Uses tubular, packed reactors with heat recovery using hot flue
gases for feed preheating or for steam production in a waste heat
boilers
 New process combines steam reforming with partial oxidation
resulting in autothermic reforming (ATR) where gases from partial
oxidation burner are mixed with steam and sent to the steam
reformer
Key Technical Issues
Carbon and thermal energy
efficiencies

Source: Foster Wheeler

 Carbon and thermal energy
efficiencies
Fuel Losses (CO2)
23 Btu
23 Carbon

GAS FEED HC Product

100 Btu GTL plant 60 Btu
100 Carbon 77 Carbon

Water Make
EE: 60% 17 Btu
CE: 77% 0 Carbon

Source: Foster Wheeler

 Carbon and energy efficiencies

AC AD = acetic acid; integrated: power generated due to process excess

heat; stand alone: power generated independent of process excess heat
 Poly-generation
(fuels, chemicals & power)
• Syngas production technologies: H2/CO, Energy
• - SMR (steam reforming): H /CO >2, H >> 0
2
• - CO2R (CO or DR (dry) reforming): H /CO < 2, H >> 0
2 2
• - POX (partial oxidation): H /CO ~ 2, H < 0
2
• - Combined (SMR+POX=ATR (auto reforming)) H /CO ~ 2, H >0
2
• FT synthesis depends on: H2/CO ratio of feed, catalyst types,
temperature
• Excess of light ends & steam (FT: H < 0) are consumed by power
plant
• Excess of H2 for product upgrading of FT and manufacturing
chemicals as co-products
Poly-generation (fuels, chemicals
& power)

Source: Foster Wheeler

Fischer Tropsch (FT) Synthesis
 FT Reactions
Main Reactions
Paraffin : (2n+1) H2 + n CO  CnH2n+2 + n H2O (exothermic)
Olefin : 2n H2 + n CO  CnH2n + n H2O (exothermic)
Alcohols : 2n H2 + n CO  CnH2n+2O + (n-1)H2O (exothermic)
H2/CO ratio dictates reactions towards carbon chain length
Side Reactions
Water gas shift : H2O + CO  CO2 + H2 (exothermic)
Dis-proportionate Boudouard : CO + CO  CO2 + C (exothermic)
Surface carbonaceous material : (x+(y/2)) H2 + x CO  CxHy + x H2O
Oxidation-reduction of catalyst : y H2O + x M  MxOy + y H2
y CO2 + x M  MxOy + y CO
Methanation : CO + 3 H2  CH4 + H2O (exothermic)
 Main reactions compete with methanation (reverse of
steam reforming) which is even more exothermic:
 CO + 3 H  CH + H O
2 4 2
 To promote F-T over methanation, reaction is run at low
temperatures and high pressure: 220-350°C; pressure: 2-
3 MPa (case of diesel manufacture)
 FT synthesis requires high pressure. Thus, the exit flow
pressure of partial oxidation and autothermal reforming
are more suitable to this requirement.
 Because of the nature of the FT catalyst, syngas should
be purified from sulphur and sulphur compounds. In
practice, zinc oxide beds are used to remove traces of
sulphur.
 Reaction Performances
Conversion: reactant converted/initial reactant

Product Selectivity for certain carbon chain n was formulated

by Anderson–Flory–Schulz kinetics

log (Wn/n) = n log  + log [(1-)2/]

With chain growth probability  , carbon number n, mass

fraction Wn.

 = 0.8 premium/gasoline
 > 0.9 diesel
diesel carbon chain is longer than gasoline carbon chain
Typical products of FT which depend on catalyst, temp, pressure,
reactor type . Main product is gasoline.
 Parameter Impacts
Nilai  tinggi, produk mengarah diesel
Katalis. Nilai  yang tinggi diperoleh dari:
Pemilihan logam : Co > Ru > Fe
Penyangga : TiO2 > Al2O3 > SiO2
Promotor : K2O, V2O5, ZrO2, Cr2O3 menaikkan 
Konsentrasi logam : loading lebih tinggi, nilai  naik
Ukuran partikel : ukuran lebih kecil, nilai  naik
Kondisi Proses.
Rasio H2/CO : rasio H2/CO naik, nilai  naik
Suhu (T) : suhu naik, nilai  turun
Tekanan (P) : tekanan naik, nilai  naik
Reaktor : Kontrol suhu
Fixed bed : suhu rendah, nilai  tinggi
hot spot menurunkan nilai 
Fluidized bed : suhu tinggi, nilai  rendah
Slurry : suhu rendah, nilai  tinggi
 Catalyst comparison
Fe Co

Pembuatan Presipitasi Presipitasi

Penyangga - TiO2, Al2O3,SiO2, MgO
Daya tahan Rendah Tinggi
Rasio H2/CO
0.7 – 2 2
umpan syngas
Fasa aktif Fe  Fe3C  Fe5C2 Co
Selektifitas Lebih bersifat olefinik Lebih bersifat parafinik
Produk  rendah  lebih tinggi
Produk samping CO2 > H2O >
Lebar tergantung kondisi Terbatas (tanpa water gas
Fleksibilitas (dengan water gas shift shift reactor) karena CO
reaction) karena CO tinggi rendah
Umur Pendek (orde minggu) Panjang (orde tahun)
Regenerasi Tidak/Jarang Ya
Harga Murah Mahal (supply limited)
 Typical FT Reactors
Gas phase in liquid phase in
heat exchange heat exchange

Fixed Bed Circulating Bed Slurry Bed

 FT Reactor Characteristics
Fixed Bed Circulating Bed Slurry Bed

Limited heat transfer Good heat transfer Uniform heat transfer

Low operating High operating Low operating
temperature,  high temperature,  low temperature,  high
Simple design, Circulated solid Slurry catalyst,
stationary solid catalyst, replaceable replaceable during the
catalyst during process process
Problems of hot spot Problem of large Problem of wax/catalyst
and pressure drop dimension separation

Product: heavy Product: light fraction Product: heavy fraction

fraction (diesel) (naphta, gasoline) (diesel)

1,500 – 5,000 bpd 1,600 – 6,500 bpd 10,000 – 17,000 bpd

 Sasol FT reactor types

High temp Advanced

(350oC), low  Synthol
Synthol
Gasoline &
olefins

Low temp
Arge Slurry
(250oC), high  (fixed
Waxes & Diesel bed)

Conventional technology Advanced technology

Source: Sasol
FT reactor capacity

Source: Sasol
 Slurry phase Diesel reactor –
Oryx, Qatar
Commercially proven
Designed, developed, operated and
licensed by Sasol 2500 bbl/day unit
operated since 1993 using high
efficiency catalyst

Currently designed for integration

with the scale of 17000 bbl/day

Source: Sasol
Slurry phase Diesel reactor –
Oryx, Qatar

Oryx GTL

Source: Sasol
Typical flow regime of slurry phase
reactor (in terms of proportion of
slurry, small and large bubbles)

Source: Krishna
Product Upgrading
Upgrading process (for wax production
followed by wax hydrocracking)
Tail Gas

Syngas
REAKTOR
Water FISCHER Steam
(cooler) TROPSCH

Gas

Wax/Slurry
Katalis
H2 Naphta
SEPARASI UNIT SEPARASI
KATALIS HYDRO - PRODUK
& WAX PROCESSING
Diesel

Wax
Upgrading Process
GTL Economics
Range of capital investment costs
for synthetic fuel plant
(1000 US$ per barrel/day (BPD) of capacity)

Source: EIA, DOE

 Capex vs Capacity
100
CAPEX (1000 US$/BPD)
80

60

40

20

0
0 20 40 60 80 100 120
Kapasitas Plant GTL (1000 BPD)

Sasol Other Trendline

Estimated production cost

Source: IFP
 Cost breakdown (25 years service
life)
2%

22% Capex
52%
Gas Price
$0.5/MMBtu
~ $4.5/bbl Opex
Capex
~ $9.0/bbl
Opex Feed Costs
~ $4.5/bbl

Other Costs
24%
 $18/bbl

Source: Foster Wheeler

Indicative capital cost breakdown

20%
30% Syngas Production
F-T Synthesis
Product Work-up
Other Process units
15%
Utilities
Offsites
10% 15%
10%

Source: Foster Wheeler

Cost of products

Source: Foster Wheeler

Product quality and market
FT Diesel properties

Source: Morita, 2001

FT Diesel emission test

Source: Sasol
GTL projects
ORYX progress work at site

Source: Foster Wheeler

 Technology developers

• Syngas Technology Licensors ( Haldor Topsoe,

Lurgi, others)

• FT Synthesis Oil Companies & Licensors (Sasol, Shell,

Syntroleum, Rentech)

• Product Upgrade Refinery Licensors (UOP,CHEVRON)

• Oxygen Package Vendors (Air Products, BOC)

• Integration Engineering Contractors (Foster

Wheeler, Technip, )

Source: Foster Wheeler

Technology providers - syngas
Technology Provider Process Name Provider Category
Foster Wheeler SMR Contractor
KTI/Technip SMR Technology Company
Kellogg (Ammonia) SMR Contractor
bp/Kvaerner SMR Oil Major
Linde SMR Technology Company
Kruppe Udhe SMR / UCAR (ATR) Contractor
ZAK ATR Technology Company
Syntroleum ATR Technology Company
Haldor Topsøe ATR & SMR Technology Company
ExxonMobil ATR / Fluid Bed Oil Major
JMC- One Synergy GHR Other
Shell POX Oil Major
ChevronTexaco POX Oil Major
Conoco POX Oil Minor
Lurgi POX, ATR & SMR Technology Company
OTM Alliance Ceramic Membrane Industry Alliance
ITM Alliance Ceramic Membrane Industry Alliance
BOC Ceramic Membrane Other
Synergy Corporation Plasma (GlidArc) Technology Company

Source: Foster Wheeler

 Future of GTL

 To monetize stranded gas

 To substitute petroleum based fuels

 To produce ultra-clean fuels

 To secure fuel supply

 The longest standing plant is at Mossel Bay in South
Africa, operated by PetroSA since 1987 (it is assume this
is another legacy of apartheid sanctions) which has a
36kbd output capacity.
 In 1993, Shell began operating a small plant in Bintalu,
Malaysia, and increased its capacity in 2005 (from
12.5kbd to 14.6kbd).
 Most recently, Sasol and Qatar Petroleum brought on
stream the Oryx plant in Qatar. This had a difficult start
up, but is now apparently operating at the designed
34kbd capacity.
 In early 2007, Exxon Mobil and Qatar petroleum
announced the cancellation of the proposed 154000 b/d
Palm GTL project, citing severe cost escalation as the
main reason. It was originally scheduled to cost about $7
billion, but reports suggested that costs may have risen
to around as high as $18 billion.
 Sonatrach of Algeria has deferred bids on its planned
65000 b/d Tinhert GTL plant from 2006 until later in 2007
 In the light of these developments over the past year or
so, it now seems likely that the prospects of a significant
contribution from GTL products could be later and
smaller than has been envisaged in recent years.
 A University of Houston chemical engineering professor,
Michael J. Economides, in 2005 found that GTL can
compete with crude oil in the transportation-fuels market
as long as oil prices are high and natural gas prices low .
GTL can be more attractive at very low gas prices, he
found.
 "Availability of large volumes of low-priced natural gas
feedstock is critical to the economics of GTL plants,"
Economides concluded.
Appendices
Integrated GTL - Scenario 1
(ATR-FT-UREA-POWER)
Integrated GTL - Scenario 2
(SMR-FT-UREA-POWER)
 Integrated GTL - Scenario 3
(ATR-FT-DME-POWER)

Nat.Gas
Integrated GTL - Scenario 4
(SDR-FT-ACETIC ACID- POWER)
 Integrated GTL - Scenario 5
(DR-FT-ACETIC ACID-POWER)

Nat.Gas
CO2