TOPIC 3: COAL AS RAW MATERIAL
• The Production of Synthesis Gas (from Coal, Steam
Reforming).
• The Fischer-Tropsch Process.
► See also Reppe Chemistry (Topic 2)
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SYNTHESIS (SYN) GAS FROM COAL
► Synthesis gas is a mixture of carbon monoxide and hydrogen for use
in chemical manufacture.
► It may be produced from coal using the water gas process.
Here water steam is reacted with white-hot coal in the following reaction:
C + H2O → CO + H2 DH = + 130 kJ mol-1
► The reaction is endothermic. In order to supply the required energy to
enable the water gas process, air is blown into the furnace causing the
following two exothermic reactions:
C + O2 → CO2 DH = - 406 kJ mol-1
2 C + O2 → CO DH = - 246 kJ mol-1
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THE SHIFT REACTION
The control of the CO/H2 ratio is important for the manifold use of
synthesis gas.
This is accomplished by regulating the steam input of water and the
following reaction, which is also known as the shift reaction:
CO + H2O → CO2 + H2 DH = - 42 kJ mol-1
The corresponding equillibrium constant has a value of K ca. 1 at 830 ºC.
The reaction is exotherm and therefore it is necessary to work at low T.
Catalysts help to accelerate the formation of the equillibrium:
► High temperature conversion (350-380 ºC; 3-4 vol% CO residue):
Fe/Cr- or Cr/Mo-containing catalysts
► Low temperature conversion (200-250 ºC; < 0.3 vol% CO residue):
Cu/Zn-containing catalysts
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PROPOSED MECHANISM OF THE SHIFT REACTION
Formation of a metal-
carbonyl complex Hieber’s base reaction:
nucleophilic addition of
water to the carbonyl C
Decarboxylation and
formation of a metal
hydride
Reductive elimination
Protonation, formation
of H2
of a dihydrido-metal
complex
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SYN GAS FROM NATURAL GAS OR PETROLEUM
This process is called steam reforming.
In the case of methane a mixture with steam is passed over a nickel
catalyst.
CH4 + H2O → CO + 3 H2 DH = + 205 kJ mol-1
Disadvantages:
The process is endothermic and requires high temperatures.
Sulfur sources in the raw material are likely to poison the catalyst system.
However, the process is nowadays preferred.
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POST-TREATMENT OF SYN GAS
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POSSIBILITIES OF SYN GAS: JUST MIX IT! – A FIRST LOOK
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PRO’s AND CONTRA’s OF SYN GAS
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USE OF SYN GAS
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THE FISCHER-TROPSCH PROCESS
The Fischer-Tropsch Process is the
hydrogenation of carbon monoxide with
hetereogeneous catalyst systems (transition
metals; Fe, Co, Ni, Ru) to yield saturated and
unsaturated hydrocarbons (mainly linear).
Fischer Tropsch Minor products: alcohols, aldehydes, ketones,
organic acids
n CO + 2n H2 -(-CH2-)n + n H2O DH = -158.5 kJ mol-1
Side reactions: CO + 3 H2 CH4 + H2O
(methanization – extreme
case of Fischer-Tropsch)
2 CO C + CO2 (Boudouard reaction,
C deposit on catalyst) 11
SOME HISTORICAL REMARKS
1902: Sabatier and Senderens, first hydrocarbon synthesis (methane)
from synthesis gas using Ni and Co as catalysts at 300 ºC
from 1925: Fischer and Tropsch (Institute for Coal Research in
Mühlheim/Ruhr, Germany), conversion of synthesis gas to higher
hydrocarbons (olefines, parafins) and oxygen-containing compounds with
Fe-, Co-, and Ni-containing catalysts at atmospheric pressure and
temperatures of 160-300 ºC
1936: Ruhrchemie AG/Oberhausen, Germany, first technical realization of
a Fischer-Tropsch process (modified Co-catalyst, normal and medium
pressure conditions)
1944: Climax of fuel production with Fischer-Tropsch chemistry (coal as
raw material for synthesis gas production); stop of production after the end
of World War II
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SOME HISTORICAL REMARKS
since 1955: SASOL/South Africa, large scale production of gasoline,
diesel, waxes, olefines and oxygen-containing compounds based on
coal, use of Fe-catalysts; capacity: ca. 6.000.000 t/year
since 1992: Petro SA/South Africa, gasoline by Fischer-Tropsch
synthesis based on natural gas; capacity: ca. 1.500.000 t/year
since 1993: Bintulu/Malaysia, diesel, kerosine on basis of natural gas
and Fischer-Tropsch chemistry on Co-catalysts (Shell Middle Distillate
Process, SMDS); capacity: 390.000 t/year
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MECHANISM FISCHER-TROPSCH SYNTHESIS
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CARBENE MECHANISM
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HYDROXYCARBENE MECHANISM
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CO-INSERTION MECHANISM
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KINETIC DESCRIPTION
Molar fraction of total products, Mn
a – probability of chain growth
(independent on chain length n) 18
KINETIC DESCRIPTION
lg a
Relationship comes from investigations
about ideal polymerizations (Schulz-
Flory kinetics)!
Growth probabilities of 0.7 to 0.9 are possible in technical processes
(depends on reaction temperature and catalyst).
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PRODUCT FORMATION
Linear hydrocarbons and olefines
parafins (ca. 20 %)
1-olefines (ca. 80%)
Main products of the Fischer-Tropsch synthesis.
Parafins: associative desorption under addition of H
Olefines: dissociative desorption under a-CH-cleavage
Olefines can readsorb and be hydrogenated to parafins in follow-up reactions.
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PRODUCT FORMATION
Hydrocarbons with ramifications
up to ca. 15 mass%
(only mono-methyl ramifications)
Mechanisms are less clear.
A) Secondary reintegration of an olefine.
B) Reaction of methyl species with alkylidene intermediates.
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PRODUCT FORMATION
Oxygen-containing compounds
alcohol
aldehyde
< 10 mass%
Mechanisms less clear.
a) Insertion of surface-adsorbed CO.
b) Addition of a surface OH group.
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CATALYST SYSTEMS
► Fe, Co, Ni, Ru (actualmente only Fe and Co)
► Ni can form easily Ni(CO)4
► Ru is very expensive
► Technical catalysts are often modified:
Supports (SiO2, Al2O3, TiO2)
Structural promoters (MgO, ZrO2, ThO2…)
Reduction promoters (Cu, Pt, Ru)
Chemical promoters (K in case of Fe catalysts)
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INTERRELATIONSHIP BETWEEN REACTION PARAMETERS
T p pH2 pCO pH2O K
Methane + - + - - -
selectivity
Chain length - + - + + +
Olefine selectivity ~ ~ - + + +
Alcohol selectivity - + +
Ramifications + - ~ ~ ~ -
Catalyst activity + + + ~ ~ -
- -
Carbon formation + ~ -
+: positive influence
-: negative influence
~: indifferent
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TECHNICAL IMPLEMENTATION
A technical Fischer-Tropsch
process consists in three steps:
► Generation and purification
of synthesis gas
► Fischer-Tropsch synthesis
► Fractionation following boiling
point and functionality
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TECHNICAL IMPLEMENTATION
The process is performed at pressures between 20 and 40 bar.
Depending on the temperature low- and high-temperature processes
are distinguished:
► Low temperature process (210-250 ºC): long chains (high a);
production of diesel and wax (middle distillate).
► High temperature process (320-350 ºC): short chains; gasoline
production; olefines and alcohols as important basis chemicals.
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