School of Chemical and Materials Engineering

(SCME)

CHE-211 – Assignment 2

Name: Hamzah Kamran

Class: CHE15A
CMS ID: 424447
Submitted to: Dr. Asadullah Khan
THE FISCHER-TROPSCH PROCESS

The Fischer–Tropsch process (FT) is a series of chemical reactions that transform a mixture
of carbon monoxide and hydrogen, termed syngas, into liquid hydrocarbons. This process
holds significance in both coal liquefaction and gas to liquids technology for the production
of liquid hydrocarbons. Normally, carbon monoxide and hydrogen, the raw materials for FT,
are generated from coal, natural gas, or biomass through a method called gasification.
Subsequently, these gases are converted into synthetic lubrication oil and synthetic fuel. The
technique has garnered attention as a means to obtain low-sulfur diesel fuel and address
challenges related to the supply or cost of petroleum-derived hydrocarbons. Initially
developed by Franz Fischer and Hans Tropsch at the Kaiser Wilhelm Institute for Coal
Research in Mülheim an der Ruhr, Germany, in 1925, the process has since undergone
significant advancements.

History
The FT process garnered attention as a method utilized by Nazi Germany to manufacture
liquid hydrocarbons. Initially developed by Franz Fischer and Hans Tropsch at the Kaiser-
Wilhelm-Institut for Chemistry in 1926, they secured several patents for their innovations. It
was later put into commercial operation by Brabag in Germany in 1936. Given Germany's
scarcity of petroleum but abundance of coal, the process was utilized during World War II to
produce alternative fuels. FT production contributed to an estimated 9% of German wartime
fuel production and 25% of automobile fuel. Numerous enhancements have been made to the
process since its inception by Fischer and Tropsch.
In the United States, under the Synthetic Liquid Fuels Act, the Bureau of Mines employed
seven Operation Paperclip scientists specialized in synthetic fuel in a Fischer–Tropsch
facility in Louisiana, Missouri in 1946.
In Britain, Alfred August Aicher secured multiple patents for advancements to the process
during the 1930s and 1940s. His company, Synthetic Oils Ltd., was involved in this work.
During the 1930s and 1940s, Arthur Imhausen developed and put into practice an industrial
method for producing edible fats from these synthetic oils via oxidation. These products were
fractionally distilled, and the edible fats were derived from the C9-C16 fraction, which were
then reacted with glycerol synthesized from propylene. "Coal butter" margarine, derived from
synthetic oils, was discovered to be both nutritious and palatable, supplementing diets with
up to 700 calories per day. The process required a minimum of 60 kg of coal per kg of
synthetic butter.

Chemical Reactions
The Fischer–Tropsch process involves a sequence of chemical reactions that yield various
hydrocarbons, ideally conforming to the formula (CnH2n+2). Predominantly, the reactions yield
alkanes, exemplified by the equation:
(2n + 1)H2 + nCO → CnH2n+2 + nH2O
where n usually ranges between 10 and 20. Undesirably, methane (n = 1) can also form. The
majority of produced alkanes are linear, suitable for diesel fuel. Alongside alkane production,
secondary reactions yield minor quantities of alkenes, alcohols, and other oxygenated
hydrocarbons. The process is highly exothermic with a standard reaction enthalpy (ΔH) of
−165 kJ/mol CO combined.
The conversion of a H2 and CO mixture into aliphatic products involves several intermediate
compounds and is a multi-step reaction. The growth of the hydrocarbon chain can be
conceptualized as a repetitive process wherein hydrogen atoms are added to carbon and
oxygen, splitting the C–O bond, and forming new C–C bonds. For the generation of one –
CH2– group from CO + 2H2 → (CH2) + H2O, multiple reactions are necessary:
• Adsorption of CO
• Cleavage of the C–O bond
• Adsorption of 2H2
• Transfer of 2H to oxygen to produce H2O
• Desorption of H2O
• Transfer of 2H to carbon to produce CH2
The conversion of CO to alkanes involves hydrogenation, hydrogenolysis of C–O bonds, and
C–C bond formation. These reactions are presumed to commence with the formation of metal
carbonyls on the surface. Potential intermediates include various C1 fragments like formyl
(CHO), hydroxycarbene (HCOH), hydroxymethyl (CH2OH), methyl (CH3), methylene (CH2),
methylidyne (CH), and hydroxymethylidyne (COH). Crucial to liquid fuel production are
reactions forming C–C bonds, such as migratory insertion.
Incorporation of isotopically labelled alcohol into the feed stream demonstrates C–O bond
scission. Using 14C-labeled ethylene and propene over cobalt catalysts leads to their
integration into the growing chain. Chain growth reactions thus involve both 'olefin insertion'
and 'CO-insertion'.
An illustrative reaction equation is:
8CO + 17H2 → C8H18 + 8H2O

Feedstocks
Fischer–Tropsch plants linked to biomass, coal, or similar solid feedstocks (carbon sources)
initially undergo a conversion process where the solid fuel is transformed into gases, known
as gasification. This process yields gases such as CO, H2, and alkanes. Syngas, acquired
through biomass/coal gasification, is a mixture of hydrogen and carbon monoxide, with the
H2:CO ratio adjusted using the water-gas shift reaction. Coal-based FT plants generate
varying levels of CO2, contingent on the energy source utilized in the gasification process.
However, the majority of coal-based facilities rely on the feed coal to meet all energy
demands of the process.
Carbon monoxide necessary for FT catalysis is obtained from hydrocarbons. In gas-to-liquids
(GTL) technology, hydrocarbons typically consist of low molecular weight materials often
considered waste or subject to flaring. Stranded gas offers a comparatively economical
resource. For GTL to be economically feasible, gas prices must remain relatively lower than
oil.
Several reactions are essential for acquiring the gaseous reactants necessary for FT catalysis.
Initially, incoming reactant gases must undergo desulfurization to prevent sulfur-containing
impurities from poisoning the catalysts vital for FT reactions.
Adjusting the H2:CO ratio involves several reactions, with the water-gas shift reaction being
paramount. This reaction serves as a hydrogen source at the expense of carbon monoxide:
H2O + CO → H2 + CO2
In FT plants utilizing methane as the feedstock, another significant reaction is dry reforming,
converting methane into CO and H2:
CH4 + CO2 → 2CO + 2H2

Catalysts, Promoters, and Supports

Four metals are recognized as catalysts for the Fischer–Tropsch process: iron, cobalt, nickel,
and ruthenium. Due to the FT process's tendency to convert cost-effective starting materials
into intricate mixtures necessitating further refinement, catalysts typically feature economical
metals, notably iron and cobalt. Nickel, while effective, tends to generate excessive methane
and is therefore not employed.
Typically, heterogeneous catalysts are prepared via precipitation from iron nitrate solutions,
allowing for the deposition of metal salt onto the catalyst support. These treated materials are
activated into catalysts through heating under CO, H2, or in the presence of the feedstock to
be treated. Given the multifaceted nature of the FT process, characterizing the catalytically
active species proves challenging. Iron catalysts, for instance, may exhibit multiple phases
that play diverse roles in the reaction, including various oxides, carbides, and metal
polymorphs. Managing these constituents is pertinent to controlling product distributions.
In addition to iron and cobalt, nickel and ruthenium demonstrate activity in converting CO/H 2
mixtures into hydrocarbons. Ruthenium, albeit costly, boasts superior activity among FT
catalysts, operating at lower temperatures and yielding higher molecular weight
hydrocarbons. Ruthenium catalysts consist solely of the metal, simplifying mechanistic
analysis, yet their high cost limits industrial application.
Cobalt catalysts exhibit heightened activity for FT synthesis when utilizing natural gas as the
feedstock, obviating the need for the water-gas shift reaction due to natural gas's high
hydrogen to carbon ratio. Cobalt-based catalysts also exhibit greater sensitivity compared to
iron counterparts.
Practically, catalyst selection varies based on operational parameters. High-temperature FT
processes typically employ iron-based catalysts, while low-temperature FT processes opt for
either iron- or cobalt-based catalysts.
Catalysts comprise three key components: the active metal (usually Fe or Co), promoters, and
the catalyst support. Promoters, such as potassium and copper, enhance catalyst performance
and are typically added as salts. The choice of promoters depends on the primary metal; for
instance, iron catalysts benefit from alkali promotion, while cobalt catalysts do not. Catalysts
are supported on high-surface-area materials like silica, alumina, or zeolites.

The Production Process

Generally, the synthesis of fuels through the FT process comprises of the following steps:
 1. Feedstock Gasification
Feedstocks such as coal, natural gas, or biomass undergo gasification, typically at
temperatures between 700°C to 1000°C and pressures of 20 to 30 bar.

C + H2O ⟶ CO + H2

This reaction produces syngas.

2. Water-Gas Shift Reaction

Syngas enters the water-gas shift reactor, where water vapor reacts with carbon
monoxide to produce additional hydrogen and carbon dioxide.

CO + H2O ⟶ H2 + CO2
This reaction helps adjust the ratio of hydrogen to carbon monoxide (optimizing it for
the subsequent Fischer-Tropsch synthesis). It typically occurs at temperatures between
200°C to 400°C, facilitated by catalysts such as iron oxide or copper-zinc.

3. Fischer-Tropsch Synthesis
Adjusted syngas enters the Fischer-Tropsch reactor, where it undergoes catalytic
reactions to produce liquid hydrocarbons, primarily long-chain alkanes.

(2n + 1)H2 + nCO ⟶ CnH2n+2 + nH2O

This reaction involves the hydrogenation of carbon monoxide and the subsequent
polymerization of hydrocarbons over metal catalysts, typically iron or cobalt. It
occurs at temperatures ranging from 150°C to 300°C and pressures of one to several
tens of atmospheres.

4. Product Refinement
The resulting hydrocarbons from the Fischer-Tropsch synthesis undergo further
refining processes to remove impurities and adjust their properties as per desired fuel
specifications.
Controlling reaction conditions and catalyst properties is essential to favor the production of
desired hydrocarbons, particularly straight-chain alkanes suitable for use as fuels.
Types of Reactors Used
1. Multi-tubular fixed bed reactor
2. Entrained flow reactor
3. Slurry reactor
4. Fluidised bed and circulating catalyst reactor
Process Flow Diagram

SYNTHESIS GAS PRODUCTION FROM COAL AND BIOMASS

In industrial chemistry, coal gasification refers to the method of generating syngas, a mixture
primarily composed of carbon monoxide (CO) and hydrogen (H2), using coal along with
water, air, and/or oxygen. Presently, large-scale coal gasification facilities are predominantly
employed for electricity generation purposes or for the production of chemical feedstocks.
The hydrogen derived from coal gasification serves various functions, including the
production of ammonia or the enhancement of fossil fuels. Alternatively, the syngas derived
from coal can be further processed to yield transportation fuels such as gasoline and diesel.
Moreover, it can be converted into methanol, which can be transformed into gasoline through
subsequent processes.
In the context of bioenergy, "biomass" refers to material derived from organisms that were
recently living but are now dead. This definition of biomass may vary, encompassing solely
plant matter, a combination of plants and algae, or that of plants and animals. However, plants
are the predominant source of biomass used for bioenergy purposes. Bioenergy is categorized
as a renewable energy source, and it holds promise in aiding efforts to mitigate climate
change.
History
The origins of coal gasification to produce syngas trace back to the early 19th century,
marked by pioneering experiments conducted by scientists like William Murdoch and
William Murdock. These early endeavors laid the groundwork for practical applications, with
Murdoch's demonstration of illuminating his home with coal gas in 1792 serving as a notable
milestone. However, it wasn't until the mid-19th century that coal gasification gained
significant commercial traction. Cities such as London, Manchester, and Paris established
gasworks that utilized coal as the primary feedstock to produce coal gas. This gas found
widespread use in street lighting, heating, and cooking, marking the initial rise of coal gas as
a vital energy source.
Throughout the late 19th and early 20th centuries, coal gasification witnessed notable
technological advancements. Innovations in gas retorts and purification methods enhanced
the efficiency and reliability of coal gas production. These advancements spurred the growth
of the coal gas industry, enabling it to meet the increasing demand for synthetic fuels. The
onset of World War I and World War II further propelled coal gasification, as petroleum
shortages necessitated the development of alternative fuel sources. During these periods,
gasification technologies were refined to produce synthetic fuels, contributing to energy
security efforts.
However, the mid to late 20th century saw a decline in coal gasification with the discovery of
abundant natural gas reserves and the widespread adoption of petroleum-based fuels. Despite
its historical significance, coal gasification faced challenges from competing energy sources.
Nevertheless, concerns over energy security, environmental pollution, and greenhouse gas
emissions have reignited interest in coal gasification in recent decades. Modern
advancements in gasification technologies aim to produce syngas not only for traditional
applications but also for the production of chemicals, fertilizers, and synthetic fuels.

The Production Processes

The industrial production processes of synthesis gas from coal and biomass share
fundamental steps, although there are some variations due to differences in raw materials and
properties.
Synthesis Gas Production from Coal
1. Coal Preparation
Coal undergoes preparation, including crushing and sizing, to optimize its reactivity
and facilitate subsequent processing.
2. Coal Gasification
In the gasification stage, coal reacts with steam and/or oxygen at high temperatures
(700°C to 1000°C) to produce syngas.

C + O2 ⟶ CO2 (partial oxidation)

C + H2O ⟶ CO + H2 (steam reforming)

 3. Syngas Cooling and Cleaning
The hot syngas is cooled to remove excess heat and undergoes cleaning to eliminate
impurities like sulfur compounds and particulates.

4. Water-Gas Shift Reaction

The cooled syngas undergoes the water-gas shift reaction, where CO reacts with
steam to form CO2 and H2.

CO + H2O ⟶ H2 + CO2

5. Gas Separation and Compression

The shifted syngas is separated to isolate specific components such as hydrogen and
carbon monoxide, which are then compressed to the desired pressure for downstream
processes.

6. Product Refinement and Utilization

The separated syngas components can be further refined for specific industrial needs
or utilized directly in processes like ammonia production or Fischer-Tropsch synthesis
for fuels and chemicals.

Synthesis Gas Production from Biomass

1. Biomass Preparation
Biomass, such as wood chips or agricultural residues, undergoes preparation
involving drying and grinding to enhance reactivity.

2. Biomass Gasification
Biomass is gasified with steam, oxygen, or a combination of both at high
temperatures to produce syngas.

C + O2 ⟶ CO2, C + H2O ⟶ CO + H2 (similar to coal gasification)

3. Syngas Cooling and Cleaning

The hot syngas is cooled and cleaned to remove impurities such as tar, sulfur
compounds, and particulates.

4. Water-Gas Shift Reaction

The cooled syngas undergoes the water-gas shift reaction to adjust the hydrogen to
carbon monoxide ratio.

CO + H2O ⟶ H2 + CO2

5. Gas Separation and Compression

The shifted syngas is separated into its components and compressed for further
processing.
 6. Product Refinement and Utilization
The separated syngas components are refined or utilized directly in various industrial
applications, similar to the process for coal-derived syngas.

Commercialization
As per the Gasification and Syngas Technologies Council, a trade association, there are
currently 272 operational gasification plants worldwide with 686 gasifiers, with an additional
74 plants, with 238 gasifiers, under construction. The majority of these plants use coal as
their primary feedstock.
As of 2017, substantial expansion within the coal gasification industry was primarily
observed in China. Local governments and energy enterprises in China actively promote this
industry to stimulate employment opportunities and create a market for coal. Typically, these
plants are situated in remote regions abundant in coal resources.

Process Flow Diagram

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