Beruflich Dokumente
Kultur Dokumente
UKZN
April 2013
Sasol Technology R&D, P.O. Box 1, Sasolburg, 1947, South Africa
Fischer-Tropsch Technology
Dr Franz Fischer
Dr Ing Hans Tropsch
Catalytic Process for the Production of
Long Chain Hydrocarbon Paraffins
from
Carbon Monoxide and Hydrogen
22 July 1925
Types of FT technology
Can be divided in to three types:
CTL Coal to Liquids
GTL Gas to Liquids
Sasol
Mozambique
Botswana
Namibia
Pretoria
Johannesburg
Sasolburg
Secunda
Richards Bay
Durban
South
Africa
Refineries
Cape
Town
Mossel Bay
Port Elizabeth
Synfuels Plants
Qatar GTL
Qatar Petroleum/Sasol
34 000 bpd
Qatar GTL
Qatar Petroleum/Shell
Nigeria
Sasol Chevron 34 000 bpd
Malaysia GTL
Running
Shell
12 500 bpd
Construction
15 600 bpd
47 000 bpd
Gasification
Synthesis gas
Coal
or
Biomass
Product
upgrading
Product upgrading
Synthesis gas
LPG
Gasoline
Kerosene
Diesel
Chemicals
Current
LPG
Naphtha
Diesel
Natural gas
Reforming
Copyright reserved 2010, Sasol Technology R&D
Future
Kerosene
Base oils
Syngas production
Crude oil
Fuel Products
Consumer
Coal
Components
Commercial
Co-products
Exploration
& production
FT process
Chemicals
Products
Natural gas
Markets
Components Processes Products
3rd party
producer
Coal, crude oil and natural gas sold to open market
Copyright reserved 2010, Sasol Technology R&D
Wholesale
Feedstocks
LPG
BASE OILS
GASOLINE
NAPHTHA
ALCOHOLS
REACTION
WATER
ACIDS
DIESEL
REFINING
& FUELS
JET FUEL
WAXES
FUEL OIL
Raw materials:
Coal
Crude Oil
Natural gas
NITRO
(Ammonia,
nitric acid,
fertilisers,
explosives)
CARBOTAR
PHENOLICS
& CRESYLICS
KETONES
OLEFINS/
AROMATICS
PARAFFINS
Syngas
Generation:
Reforming
HT Gasification
LT Gasification
Fischer Tropsch:
LT-FT (Co)
LT-FT (Fe)
HT-FT (Fe)
OXYGENATES
LABs
MONOMERS
POLYMERS
POWER, WATER,
CO2 UTILISATION
METHANOL/
DME
OLEFINS
REDUCTION GAS;
HYDROGEN
CO-MONOMERS
LABs
TRANSPORT FUELS,
FUEL CELLS
D
E
R
I
V
A
T
I
V
E
S
DET ALCOHOLS
ALCOHOLS
SYNGAS TO
CHEMICALS
OLEFINS
AROMATICS
ALCOHOLS
SOLVENT
BLENDS
INTEGRATED FT COMPLEXES
10
ALCOHOLS
BASE OILS
LPG
NAPHTHA
GASOLIN
RE
WATER
KETONES
ACIDS
REFINING
& FUELS
JET FUEL
WAXES
FUEL OIL
Raw materials:
Coal
Crude Oil
Natural gas
OLEFINS/
PARAFFINS
Syngas
Generation:
Reforming
HT Gasification
Fischer Tropsch:
LT-FT (Co)
LT-FT (Fe)
HT-FT (Fe)
OXYGENATES
LABs
MONOMERS
POLYMERS
NITRO
(Ammonia,
nitric acid,
fertilisers,
explosives)
CARBOTAR
PHENOLICS
& CRESYLICS
OLEFINS
METHANOL/
DME
COLABs
DET ALCOHOLS
D
E
R
I
V
A
T
I
V
E
S
ALCOHOLS
AROMATICS
CHEMICALS
ALCOHOS
SOLVENT
BLENDS
11
Structure of coal
Natural Gas
Natural gas is a gas consisting primarily of methane
Also contains other hydrocarbons ethane, propane, butane and
pentanes
It is found associated with other fossil fuels, in coal beds, as methane
clathrates, and is created by methanogenic organisms in marshes,
bogs, and landfills
It is an important fuel source, a major feedstock for fertilizers, and a
potent greenhouse gas
Environmental
Produces about half the amount of CO2 compared to coal
Sulphur compounds and NOx less than coal
BASE OILS
LPG
NAPHTHA
GASOLIN
RE
WATER
KETONES
ACIDS
REFINING
& FUELS
JET FUEL
WAXES
FUEL OIL
Raw materials:
Coal
Crude Oil
Natural gas
OLEFINS/
PARAFFINS
Syngas
Syngas
generation:
Generation:
Reforming
Gasification
HT Gasification
Reforming
Fischer Tropsch:
LT-FT (Co)
LT-FT (Fe)
HT-FT (Fe)
OXYGENATES
LABs
MONOMERS
POLYMERS
NITRO
(Ammonia,
nitric acid,
fertilisers,
explosives)
CARBOTAR
PHENOLICS
& CRESYLICS
OLEFINS
METHANOL/
DME
COLABs
D
E
R
I
V
A
T
I
V
E
S
DET ALCOHOLS
ALCOHOLS
AROMATICS
CHEMICALS
ALCOHOS
SOLVENT
BLENDS
16
Gasification
Gasification is a process that converts carbonaceous materials,
such as coal, or biomass, into carbon monoxide and hydrogen by
reacting the raw material at high temperatures with a controlled
amount of oxygen and/or steam
The resulting gas mixture is called synthesis gas or syngas
C + 1/2 O2
CO
C + O2
CO2
C + H 2O
CO + H2
Gasifiers
Four types of gasifier are currently available for commercial use:
counter-current fixed bed, co-current fixed bed, fluidized bed and
entrained flow
ZnO
400 800 oC
1000 1200 oC
21
LPG
NAPHTHA
GASOLIN
RE
WATER
ALCOHOLS
KETONES
ACIDS
REFINING
& FUELS
JET FUEL
WAXES
FUEL OIL
Raw materials:
Coal
Crude Oil
Natural gas
OLEFINS/
PARAFFINS
Syngas
Generation:
Reforming
HT Gasification
Fischer
Tropsch:
Fischer
Tropsch:
LT-FT (Co)
LTFT (Co)
LT-FT (Fe)
LTFT (Fe)
HT-FT
(Fe)
HTFT
(Fe)
OXYGENATES
LABs
MONOMERS
POLYMERS
NITRO
(Ammonia,
nitric acid,
fertilisers,
explosives)
CARBOTAR
PHENOLICS
& CRESYLICS
OLEFINS
METHANOL/
DME
COLABs
D
E
R
I
V
A
T
I
V
E
S
DET ALCOHOLS
ALCOHOLS
AROMATICS
CHEMICALS
ALCOHOS
SOLVENT
BLENDS
22
CO hydrogenation reaction
CO + 2H2 C1* + H2O (Exothermic)
Polymerisation reaction
C1-C1-C1-C1-C1* + C1* C1-C1-C1-C1-C1-C1*
Cn* + C1* Cn+1*
CH4
CO
O2
C3H5OH
H2
CH3COOH
2H2
CO
C2H6
CO
CH3
Fe
Fe Fe Fe
C2H4
C2H3
Fe
Fe
Fe
C2H4
0.20
0.04
Mass fraction
0.03
LTFT (cobalt slurry phase, 220C)
0.10
0.02
LTFT (iron slurry phase, 240C)
0.05
0.01
0.00
0
0
10
15
20
25
Carbon number
30
35
40
45
Fe-FT Technology
Two types of FT processes
High Temperature Fischer-Tropsch (HT FeFT)
Low Temperature Fischer-Tropsch (LT FeFT)
HT FeFT
Produces lighter components (C1 to C20)
Produces oxygenates in highest quantities
Basis for petrol and chemicals
Fluidised bed reactor
LT FeFT
Produces heavier components (>C20)
Produces oxygenates in lower quantities, wax is major product
Basis for wax and paraffins
Slurry Reactor
CH4
C2-4 olefins
C2-4 paraffins
Gasoline
Distillate
Oils and waxes
Oxygenates
Low
Temperature
220 - 2500C
High
Temperature
330 3500C
Alpha ~ 0.95
4
4
4
18
19
48
3
Alpha ~ 0.7
7
24
6
36
12
9
6
HT-FeFT
Reactors CFB and SAS
Operation of SAS
Products formed
U- Bend
Gas outlet
Cyclones
Cooling coils
Slide
valve
Gas inlet
Riser
Cyclones
Catalyst Bed
Cooling coils
Gas in
Operation of SAS
10m reactors (diameter)
Gas enters from the bottom not pure syngas
Syngas and carbon dioxide WGS reaction
CO + H2O
CO2 + H2
nCO + 2nH 2 C n H 2 n + nH 2 O
nCO + (2n 1) H 2 C n H 2 n O + (n 1) H 2 O
nCO + 2nH 2 C n H 2 ( n +1) O + ( n 1) H 2 O
nCO + ( 2n 2) H 2 C n H 2 n O2 + ( n 2) H 2 O
(for paraffins)
(for olefins)
(for carbonyls)
(for alcohols)
(for acids)
200-240oC
Precipitated Iron-based catalyst
5m diameter
100 kt pa (2500 bbl/d)
More isothermal
Lower dP across catalyst bed
Online catalyst replacement possible
Products mainly wax and paraffins
35
Copyright reserved 2009, Sasol Technology R&D
Selectivity of FT-processes
50
40
LTFT
HTFT
30
20
10
0
CH4
C2-C4 Olef
C2-C4
Paraf
Gasoline
Mid Dist
Wax
Oxyg
Sam Mahomed
CHEMICALS FROM FT
LPG
BASE OILS
GASOLINE
NAPHTHA
ALCOHOLS
REACTION
WATER
ACIDS
DIESEL
REFINING
& FUELS
JET FUEL
WAXES
FUEL OIL
Raw materials:
Coal
Crude Oil
Natural gas
NITRO
(Ammonia,
nitric acid,
fertilisers,
explosives)
CARBOTAR
PHENOLICS
& CRESYLICS
KETONES
OLEFINS/
AROMATICS
PARAFFINS
Syngas
Generation:
Reforming
HT Gasification
LT Gasification
Fischer Tropsch:
LT-FT (Co)
LT-FT (Fe)
HT-FT (Fe)
OXYGENATES
LABs
MONOMERS
POLYMERS
POWER, WATER,
CO2 UTILISATION
METHANOL/
DME
OLEFINS
REDUCTION GAS;
HYDROGEN
CO-MONOMERS
LABs
TRANSPORT FUELS,
FUEL CELLS
D
E
R
I
V
A
T
I
V
E
S
DET ALCOHOLS
ALCOHOLS
SYNGAS TO
CHEMICALS
OLEFINS
AROMATICS
ALCOHOLS
SOLVENT
BLENDS
INTEGRATED FT COMPLEXES
38
reaction water
Primary
separation
Carbonyl
recovery
acetone
MEK
methanol
aldehydes
Alcohol
recovery
Acid
recovery
95% ethanol*
HPE
99.9% ethanol
i-propylol
EA
ethyl acetate
n-propylol*
NPA
n-propanol
i-butylol
sabutol
acetic acid
propionic acid
alcohols
-H2
OH
(A)
+H2
-H2
OH
O
-E tOH
(B)
(C)
+H2
O
O
(D)
(340C)
Acetic acid
0.84
Propionic acid
0.19
Butyric acid
0.11
Acetaldehyde
0.5
Propionaldehyde
0.1
0.5
Acetone
4.0
23
MEK
0.3
Methanol
24
0.5
Ethanol
45
40
n-Propanol
13
12
i-Propanol
N-Butanol
S-Butanol
i-Butanol
Ref: Fischer-Tropsch Technology, Studies in Surface Science & Catalysis 152, Authors: AP Steynberg; ME
Dry
41
Olefins
Extractive distillation
Olefins that are extracted hexene, octene and pentene
Ethylene and propylene gas product
Octene also synthesised via 1-heptene
Hydroformylation to produce octanal
R1
CO/H2
catalyst
R1
Hydrogenated to octanol
R1
catalyst
H2
OH
R1
Dehydrated to 1-octene
R1
OH
catalyst
R1
H2O
Fuels - Refining
Temp (C)
<30C
30-90C
90-180C
180-230C
230-350C
350-500C
500+C
Some terms
LPG = liquefied petroleum gas
Petrol = gasoline (naphtha = raw petrol)
Distillate = Precursor to diesel
Kerosene = jet fuel or commercial paraffin
Coke = carbon
Upgrading
Converting molecules into more valuable products
Fuel specs
Addressing product quality issues
Chemicals
Extracting or forming chemicals
Environmental
ENVIRONMENTAL
Aqueous Effluents
Saline Waters
Water Utilisation
Gaseous Emissions
H2S = 89 000 t/a
GHG emissions
= 73.1 million t/a
Solid Wastes
Hazardous = 270 000 t/a
Non-Hazardous = 1 126 000 t/a
Water use
= 161 billion l/a
Aqueous Effluents
Data from Sasol Sustainability Report - 2007
Copyright 2009, Sasol Technology R&D, All rights reserved
42 billion litres/a
Pollutant
Projects
Solid Waste
Water
Water Re-use
Salt/Ash
Management
H2S emission
reduction
Black products
remediation
Improved Fuel
quality e.g.
remove metallic
additives
Blowdown upgrade
Air
Pollutants
Dry Cooling
Anaerobic vs.
Aerobic digestion
Waste Re-use
e.g. Bricks,
Cement
Boiler
Technology
e.g. CFB
GHG
Energy
Efficiency
Carbon Capture
and Sequestration
Non-fossil fuel
based energy
sources
Air pollutants
SOx, NOx, Particulate Matter (PM), Heavy metals
Sulphur in coal ends up as H2S or in ash from gasification
Carbon footprint
Inherent process inefficiencies
Thermodynamic constraints
Utility generation
Transportation
67.8%
Transportation
72.8%
Improve efficiency
Demand side
Supply side
Copyright 2009, Sasol Technology R&D, All rights reserved
Sequester
Direct capture
Natural sinks
Decarbonisation
Renewables
Nuclear
Lower C:H ratio
Alternative Energy
Options
Nuclear
Solar
Hydroelectricity
Biomass
Alternative Energy
Options
Wind
Geothermal
Tidal
Cleaner Technology
Ash Utilisation
Ash Bricks; Cement manufacture
Geopolymers; Road sub-base; Raw feed for cement clinkers
Sasolburg ash used in manufacture of bricks