Use of Fischer-Tropsch to Convert

Gas Coal or Biomass to Crudes

Section 1

FISCHER-TROPSCH SYNTHESIS
History Fischer-Tropsch Synthesis
• In 1923, Two German scientists Franz Fischer and Hans
Tropsch discovered synthesis gas could be converted into
heavier hydrocarbons suitable as synthetic fuels
• The Germans used Fischer-Tropsch (F-T) technology
during World War II to produce 4.5 Million Barrels of
Synthetic oil from coal to fuel the German Army
• In 1955 Sasol-I was built by the South African Govt. to
product synthetic oil from coal
• Expanded by building Sasol-II and Sasol-III in the
1980s
• Current capacity is approximately 160 KB/D of synthetic oil
• Coal based Fischer-Tropsch is proven
Technology operated successfully in South Africa
for over 50 years
History of Gas-to- Liquids
• The South African Govt. built a 12.5 Kb/D plant
based on natural gas feed (GTL) at Mossel Bay
SA in 1991
• Shell built a 12.5 KB/D GTL plant using natural
gas at Bintulu Malaysia in 1993
• Qatar Petroleum and Sasol built a 35 KB/D GTL
plant at Ras Laffan Qatar that started up in 2007.
• To date GTL and CTL been technical successes
with questionable economic viability.
• Enormous investment cost is difficult to justify
even with very low feed costs
History Fischer-Tropsch Synthesis (cont.)
• More recently there has been interest in using
operate a large plantBiomass, vegetation or wood
chips as feed to F-T gasifier feed.
• Small demonstration plants (<100 BPD) have been built but
to date no commercial size plants have been built.
• BTL is very difficult to justify because of the high
investment cost and difficulty continuously gathering
enough feedstock to operate a large plant.
Fischer-Tropsch Chemistry

• Similar to many other Polymer reactions:

• Monomer formation: CO + 2H2 => CH2 + H2O
• Polymerization CH2 + CnH2n => Cn+1 H2n+2
• Termination CnH2n + H2 => CnH2n+2
• The distribution of N-Paraffin products is
determined by the relative probability of
polymerization instead of termination dfined as a
Fischer-Tropsch Product Distribution

• Mechanism is similar to many other Polymer

reactions:
• Monomer formation: CO + 2H2 => CH2 + H2O
• Polymerization CH2 + CnH2n => Cn+1 H2n+2
• Termination CnH2n + H2 => CnH2n+2
• The distribution of N-Paraffin products is
determined by the probability that the chain
continues to polymerize instead of terminating
this probability is defined as a
Fischer-Tropsch Product Distribution
• Mechanism is similar to many other Polymer
reactions:
• Monomer formation: CO + 2H2 => CH2- + H2O
• Polymerization CH2-+ CnH2n- => Cn+1 H2n+2-
• Termination CnH2n- + H2 => CnH2n+2
• The distribution of N-Paraffin products is
determined by the probability that the chain
continues to polymerize instead of terminating
this probability is defined as a
• For commercial catalyst a varies between 0.5
and 0.95
 Fischer-Tropsch Product Distribution
• Described mathematically by the Anderson-
Schulz-Flory Distribution
• PredictsWeight fraction by carbon no:
– Wn = (1- a )2 a n-1
Fischer-Tropsch Product Qualities
• Product quality depends on catalyst
• Cobalt based catatyst primarily produces N-paraffins
• Iron based catalyst produces more Oxygenates (primarily
alcohols) and Olefins as byproducts.
• Lower temperature and higher activity catalyst tend to
produce heavier products (higher a )
• Exceptionally high quality Diesel (80+CN) and Jet product
• Naphtha Octane is low but may have high value as
petrochemical feedstock
• Heavy Wax is excellent FCCU or Lubes plant feed
• Often mildly hydrocracked to form diesel
• Plants that produce large amounts of light olefins will
oligomerize C3/C4 olefins to produce addition diesel.
Fischer Tropsch Process Summary
• Fischer –Tropsch (F-T) is a mature technology
that has been successfully operated commercially
for over 50 years.
• The F-T process using synthesis gas ( a
combination of Co and H2 ) as a building block to
produce high quality synthetic crudes.
• F-T feedstock is extremely flexible because any
Hydrocarbon can be converting into synthesis
gas via partial oxidation or steam reforming
reactions
• F-T products are a broad range of Hydrocarbons
that required additional processing to maximize
value.
Section 2

XTL PROCESS CONFIGURATIONS

Fischer-Tropsch Process Configurations
• Three Step Process
• Syngas Generation
• F-T Synthesis
• Product Upgrading
• Overall configuration is very similar for gas,coal or
biomass feeds.
• Syngas generation section must have a gasifier for solid feeds
and solids handling facilities for feed and ash.
• Conventional Steam Reforming followed by Secondary
Reforming is typical for Natural gas feeds
• F-T reaction and upgrading is the same independent of feed
source – Mild Hydrocracking to maximize diesel is the most
common upgrading method.
 Typical GTL Process Flow

Removed CO2 Naphtha

Air Light Product

O2 HDS
Air Separation
CO2 Kero
removal
F-T
Liquid Diesel
Vacuum Flash
F-T Reaction F-T Gas distillation
Feed
Gas loop
Secondary
Reformer Syn
Gas Liquid Product
Steam Separation

PSA: H2 removal for

Primary Wax
Hydroprocessing
Reformer hydrocracking Wax Recycle

Main Process Flows

Recycles

Air and O2

Steam
PROPRIETARY INFORMATION 14
Hydrogen
 Typical CTL/BTL Process Flow

Removed CO2 Naphtha

Air Light Product

O2 HDS
Air Separation
CO2 Kero
removal
F-T
Liquid Diesel
Vacuum Flash
Feed F-T Reaction F-T Gas distillation
Coal/Biomass loop
Gasifier Syn
Gas Liquid Product
Steam Separation

PSA: H2 removal for

Autothermal Wax
Hydroprocessing
Reformer hydrocracking Wax Recycle

Main Process Flows

Recycles

Air and O2

Steam
PROPRIETARY INFORMATION 15
Hydrogen
 Syngas Generation Targets
• Cobalt Catalyst – Only CO and H2 react
– All CO2 separated (component splitter)
– CO2 recycle to Secondary controlled with “Adjust”
to maintain desired H2 / CO ratio (approx 2.1)
• Iron Catalyst- CO2 also reacts
– Water has shift also occurs CO2 + H2  C0 + H2O
– Amount removed controlled using Adjust to give
Syngas with desired Riblett Ratio (1.0-1.05)
• Riblett Ratio = H2 / (2*CO + 3*CO2)
– Some CO2 is removed for Riblett ratio control

PROPRIETARY INFORMATION 16
 F-T “Gas Loop” Considerations
• Syngas conversion at F-T reactors is typically 60-
80% per pass
– Product is flashed and flash gas is recyled
– Unconverted Synthesis gas is recycled along with C4-
produced in the in the F-T reactor.
– Small purge to syngas generation to prevent C1-C4
build up in recycle ”gas loop”.

PROPRIETARY INFORMATION 17
 F-T “Gas Loop” Considerations
• Syngas conversion at F-T reactors is typically 60-
80% per pass
– Product is flashed and flash gas is recyled
– Unconverted Synthesis gas is recycled along with C4-
produced in the in the F-T reactor.
– Small purge to syngas generation to prevent C1-C4
build up in recycle ”gas loop”.

PROPRIETARY INFORMATION 18
 Integrating F-T Into an existing Refinery
• Petroleum coke is gasified to produce Syn Gas
– A portion could be used for H2 production or power
generation
– Remaining Syngas goes to a F-T reactor to produce
additional high quality refinery products.
– Heavy F-T wax is excellent quality FCCU or HCU feed

PROPRIETARY INFORMATION 19
Integration of CTL into an existing Refinery
Low Btu
Gas to
Pet Coke
Refinery

Sweet
Sour Syngas
Syngas F-T
Sep
Gasifier Scrubber Slurry
Drum
Reactor
Char and Slag

Purge gas Naphtha

H2
HCU Diesel
Fractionator

+ F-T Liquid to
Separator Wax
FCC Feed HT
Fractionator
Drum
Hydrocracked Wax + Lighter
Section 3

SYNGAS GENERATION AND

PRODUCT UPGRADING
Syngas Generation Process Options
• Catalytic Reforming of Natural gas in a Steam Methane
Reformer.
• Partial Oxidation of Coal/Biomass or Natural Gas
• Catyaytic Secondary Reforming or “Autothermal
Reforming” of Natural gas and/or Primary Reforming
effluent over a fixed bed at 950-1000C
• Gasification of Coal or Biomass typically at 1000-1300 C.
• Gasification is considerably less reliable than reforming (80-
85% vs 99%)
• Requires spare
• CO2 Removal and operating conditions adjusted to achieve
H2/CO ratio or Riblett ratio target
 Typical CTL/BTL Process Flow

Removed CO2 Naphtha

Air Light Product

O2 HDS
Air Separation
CO2 Kero
removal
F-T
Liquid Diesel
Vacuum Flash
Feed F-T Reaction F-T Gas distillation
Coal/Biomass loop
Gasifier Syn
Gas Liquid Product
Steam Separation

PSA: H2 removal for

Autothermal Wax
Hydroprocessing
Reformer hydrocracking Wax Recycle

Main Process Flows

Recycles

Air and O2

Steam
PROPRIETARY INFORMATION 23
Hydrogen
Steam Methane Reforming Furnace
Gasification Reactor
Syngas Generation Chemistry
• Partial Oxidation Reactions (O2 limited):
• CxHy + ½ x O2 => x CO + ½ y H2
• CO + ½ O2 => CO2
• H2 + ½ O2 => H2O
• Reforming: CH4+ H2O  3H2+ CO
• Equilibrium limited:
Kref = P2(CO)(H2)3 /((CH4)(H20))
• Water gas Shift: CO + H2O  H2 + CO2
Kshift = (CO2)(H2)/((CO)(H20)
 Typical CTL/BTL Process Flow

Removed CO2 Naphtha

Air Light Product

O2 HDS
Air Separation
CO2 Kero
removal
F-T
Liquid Diesel
Vacuum Flash
Feed F-T Reaction F-T Gas distillation
Coal/Biomass loop
Gasifier Syn
Gas Liquid Product
Steam Separation

PSA: H2 removal for

Autothermal Wax
Hydroprocessing
Reformer hydrocracking Wax Recycle

Main Process Flows

Recycles

Air and O2

Steam
PROPRIETARY INFORMATION 27
Hydrogen
Product Upgrading Options
• Fractionation to recover Naphtha, Jet and Diesel
Products:
• Diesel and Jet is extremely high quality
• Gasoline Octane is low
• Naphtha Specialty chemical value may be higher
with expensive recovery options like Molex.
• F-T wax (heavier than diesel cut) can be converted
to high quality diesel in low severity Hydro-
Isom/Hydrocracking reactor
• May be more valuable as specialty wax or
lubricants but market Is limited
Summary
• Fischer-Tropsh is a commercially proven technology that
can be used to convert any Hydrocarbon into a high
value synthetic crude.
• It is a three step process:
• Syngas generation
• F-T Synthesis
• Product Upgrading
• The Diesel and Jet product is extremely high quality
• Investment cost is extremely high.
• Economics are more attractive than they have been in
the past because of low natural gas prices and high
crude oil values.
Backup Material
Gasification Reactor
Gasification Reactor

Oxygen
Coal
Water
Gasification Reactor
Gasification Reactor