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Fischer-Tropsch Process

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The Fischer–Tropsch (FT) process is a collection of chemical reactions that

converts a mixture of carbon monoxide and hydrogen into liquid hydrocarbons.


The process was first developed by Franz Fischer and Hans Tropsch at the Kaiser-
Wilhelm-Institut für Kohlenforschung in Mülheim an der Ruhr, Germany, in 1925.
The FT process is an important reaction in both coal liquefaction and gas to liquids
technology for producing liquid hydrocarbons. In the usual implementation, carbon
monoxide and hydrogen, the feedstocks for FT, are produced from coal, natural gas,
or biomass in a process known as gasification.
The Fischer–Tropsch (FT) process then converts these gases into a synthetic
lubrication oil and synthetic fuel. The FT process has received intermittent attention
as a source of low-sulfur diesel fuel and to address the supply or cost of petroleum-
derived hydrocarbons.
a) Discuss production of synthetic liquid fuels and chemicals from coal via the
Fischer-Tropsch synthesis.
b) Classify the catalyst for Fischer-Tropsch process.
c) Discuss thermodynamics and kinetics of the Fischer-Tropsch synthesis
reactions

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a. PRODUCTION OF SYNTHETIC LIQUID FUELS AND
CHEMICALS FROM COAL VIA THE FISCHER-TROPSCH
SYNTHESIS:
The Fischer-Tropsch synthesis for producing liquid fuels and chemicals from coal
is carried out in two steps. First step is gasification of coal with steam and oxygen
and second is purification step to eliminate solids, sulfur compounds and most of
Carbon dioxide.
 PRODUCTION OF SYNTHESIS GAS:
The synthesis gas consists of mixture of hydrogen and carbon monoxide from
ratio 0.7H2:1CO to 2.5H2:1CO. At first the coke is heated by an air blow to heat
the bed and then steam is blown through the hot cokebed to produce hydrogen and
carbon monoxide.
C + O2 = CO2 ΔH = -94,555 cal (1500OK)
C + H2O = H2 + CO ΔH = +32,265 cal (1500OK)
The second reaction is an endothermic reaction. Due to cyclic nature of this
method, relatively low productive capacity and high cost of coke in relation to
coal, water gas generators are not considered as economical to manufacture
synthetic fuels.
Natural gas and Liquefied petroleum gas can be reformed with steam and CO2
over nickel catalyst at high temperature. Partial combustion of gaseous and liquid
hydrocarbons or solid fuels with 95-98% commercially pure oxygen and steam
can also produce synthesis gas. The partial combustion can be carried out at
pressure 400-450 psi.
Pressure gasification can be done with fie coal in suspension and I fluidized beds
or with lump coal in fixed beds.
CO2 + CO = 2CO ΔH = +39,460 cal (1500OK)
The pulverized coal is gasified with oxygen and steam and the gas leaves the
combustion zone at high temperature. Fresh coal is charged to the top of bed by
pressurized hopper and steam and oxygen are Fed to bottom of gasifier. Coking
occurs at top of bed producing by-product tar.

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 PURIFICATION OF SYNTHESIS GAS:
The raw synthesis gas is purified to remove solids like unburnt carbon and fine
ash. This is usually accomplished b water washing the gas in packed or spray
tower, cooling and cleaning the gas.
Hydrogen sulfide and organic sulfur can poison the catalyst and must be remove
to extremely law value. CO2 in high concentration is harmful to catalyst.
The two methods of purification are by Water or Rectisol scrubbing or by alkaline
wash such as monoethanolamine, diethanolamine or hot potassium carbonate
solution. The alkaline solutions can be regenerate by steam striping of spent
solution in regenerators. The other process is amine-scrubbing operation which
can also remove bonyl sulfide.
As the synthesis gas is under pressure I can also be scrubbed with water. Water
scrubbing usually depends upon physical solubility of CO2 and H2S in water
rather than upon chemical reaction. No steam heating is required in this process.
Cost for water washing are considerably higher than for alkaline-wash processes.
The Rectisol process is based on physical solubility of impurities in a methanol
solution at -40OC to -60OC. The small amount of methanol is thoroughly
regenerated by heating for final purification.

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Iron oxide infused on wood shavings effectively reduces the concentration of
hydrogen sulfide to trace amount acceptable for Fischer-Tropsch synthesis.

b. CATALYST FOR FISCHER-TROPSCH PROCESS:


In Fischer-Tropsch process commonly used catalysts are Nickel, Cobalt and iron
catalysts.
 Nickel catalyst are usually prepared by precipitation from a nitrate solution
with potassium carbonate in presence of thoria and kieselguhr in the
proportions 100Ni:18ThO3:100 kieselghur. The Nickel catalyst at low
pressure and 170-220OC form both liquid and gaseous products. The
Nickel catalyst at 300-350 OC and high pressure of 300-400 psi it only
produce methane.
 Cobalt catalysts are more preferred than nickel catalysts when greater
yields of liquid products are desired. The cobalt catalyst was used at
atmospheric pressure or at 7-10atm at 180-200OC. The standard German
Cobalt catalyst during World War II had a composition of
100Co:5ThO2:8MgO:200keiselguhr.
 Iron catalyst is more emphasized than Cobalt catalyst due to expenses and
scarcity of Cobalt. Iron catalyst can be prepared from magnetite (Fe3O4)
ore or from magnetite obtained by fusion of iron oxides, or by the
oxidation of metallic iron with steam. The iron catalyst used for Ammonia
synthesis performs quite well in Fischer-Tropsch synthesis. The addition
of potassium oxide in range of 0.1-0.5% are effective in increasing the
activity and change the selectivity of catalyst. Other promoters can also
add in iron catalyst but their effect is very less.
c. THERMODYNAMICS AND KINETICS OF THE FISCHER-

TROPSCH SYNTHESIS REACTIONS:


The reactions to produce paraffins and olefins by the Fischer-Tropsch synthesis
can be given as follows:
In the first set of reaction water is formed as a by-product.
(2n+1)H2 + nCO = CnH2n+2 + nH2O
2nH2 + nCO = CnH2n + nH2O

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In second set of reaction Carbon dioxide is formed as by-product.
(n+1)H2 +2nCO = CnH2n+2 + nCO2
nH2 + 2nCO = CnH2n + nCO2
The first two equations can be converted to corresponding equations in second set
by addition of water gas shift reaction.
CO + H2O= CO2 + H2
The formation of methane is an exothermic reaction. The 38-42 kcal heat energy
per carbon atom is liberated in the synthesis of paraffins when water is the
oxygenated product and 47-50 kcal heat energy liberate when carbon dioxide is
formed. The slightly less heat will liberate in the synthesis of olefins. The heat of
reaction amounts to about 70 Btu per cu ft of synthesis gas reacting or about 7000
Btu/lb of hydrocarbon produced. Standard state free energies are used to calculate
equilibrium constants.
-ΔFO = 2.303 RTlog10 k
Where R is gas constant and T is the absolute temperature in degrees Kelvin. ΔFO
Is highly negative up to 350OC and become less reactive with increasing
temperature. The favorable operating range is 250-350OC as indicated by the high
values of equilibrium constants. The limiting temperature range for favorable
equilibrium is 380-420OC at which the ΔFO for many hydrocarbons becomes zero.
KINETICS:
The kinetics of Fischer-Tropsch reaction has been studied on both iron and cobalt.
The synthesis of hydrocarbon on cobalt is different than iron. Only water is
obtained as oxygenated product with Cobalt while both Carbon dioxide and water
are obtained from iron catalyst. The rate of synthesis is independent of pressure
with cobalt while for iron it is linear with pressure up to 675 psi and
approximately proportional to partial pressure of carbon monoxide and hydrogen.
The Arrhenius plot against reciprocal of absolute temperature were almost linear.
The overall activation energy was 20.0-20.9 kcal/g mole.
𝐴
-log(1-x) = 𝑆 e – E/RT

The rate of reaction on fused or sintered iron increases with decreasing particle
size.

REFERENCE:
 Book: Unit Processes in Organic Synthesis by P.H. Groggins (9th Edition)

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