TABLE OF CONTENTS

Overview and History of Synfuels .................................................................................................. 1

Synthetic Gas Production ................................................................................................................ 3

Fischer-Tropsch Reaction ............................................................................................................... 4

Sasol Reactor Technology .............................................................................................................. 6

4.1

Step 1: Natural Gas Reforming ............................................................................................... 6

4.2

Step 2: Sasols Proprietary Conversion Process ..................................................................... 6

4.3

Step 3: Product Separation and Upgrade ................................................................................ 6

GTL and CTL Technology ............................................................................................................. 7

5.1

GTL Technology ..................................................................................................................... 7

5.2

CTL Technology ..................................................................................................................... 8

OCM Technology ......................................................................................................................... 10

References ..................................................................................................................................... 12

LIST OF TABLES
Table 1 - Reactions depecting the reactions for different functional groups of the Fischer-Tropsch
process .................................................................................................................................................... 4

LIST OF FIGURES
Figure 1 - Syngas production scheme ..................................................................................................... 3
Figure 2 - Illustration of Fischer-Tropsch process .................................................................................. 5
Figure 3 - GTL process used at Sasol ..................................................................................................... 6
Figure 4 - Illustaration of gas-to-liquid process ...................................................................................... 7
Figure 5 - Direct coal conversion of coal-to-liquids process .................................................................. 8
Figure 6 - Indirect coal conversion of coal-to-liquid process ................................................................. 9
Figure 7 - Illustration for the proposed Siluria OCM process .............................................................. 11
Figure 8 - Illustration for the OCmol OCM process ............................................................................. 11

1 OVERVIEW AND HISTORY OF SYNFUELS

Fossil fuelscoal, petroleum (oil), and natural gas are concentrated organic compounds found in
the Earths crust. They are created from the remains of plants and animals that lived millions of years
ago in the form of concentrated biomass. Prior to petroleum fractions, coal was the leading source of
fuel. With the advent of the gasoline and diesel oil engines, as well as the industrial revolution, the
demand for fuel had increased as well as the need for a fuel to offer a high source of energy. However,
many countries which do not have crude oil reservoirs had to develop alternate methods to produce fuel.
This need for an alternate fuel led to the development of synthetic fuels (Fossil Fuels, 2015).
Germany, having no petroleum reservoirs, had no problems prior to the twentieth century as Germany
possessed abundant coal reserves. Coal provided for commercial and home heating; it also fulfilled the
needs of industry and the military, particularly the navy. In the opening decade of the twentieth century,
Germanys fuel requirements began to change. Two reasons were especially important. First, Germany
became increasingly dependent on gasoline and diesel oil engines. The appearance of automobiles,
trucks, and then airplanes demanded a plentiful supply of gasoline. Moreover, oceangoing ships
increasingly used diesel oil rather than coal as their energy source. Second, Germanys continuing
industrialization and urbanization led to the replacement of coal with smokeless liquid fuels that not
only had a higher energy content but were cleaner burning and easier to handle (Lesch, 2000).
Petroleum was clearly the fuel of the future, and to insure that Germany would never lack a plentiful
supply, German scientists and engineers invented and developed two processes that enabled them to
synthesize petroleum from their countrys abundant coal supplies and to establish the worlds first
technologically successful synthetic liquid fuel industry.
Friedrich Bergius began the German drive for energy independence with his invention and early
development of high-pressure coal hydrogenation or liquefaction. Bergius results had been published
as a patent 1913, which lead to the industrialization of the process and was assisted by Karl
Goldschmidt. The process is known as the Bergius process and is the direct method for the production
of liquefied fuel from coal. Production began in 1919. A decade after Bergius began his work Franz
Fischer and Hans Tropsch invented a second process for the synthesis of liquid fuel from coal. This is
known as the Fischer-Tropsch (FT) process and is the indirect method for the production of liquefied
fuel from coal. Several breakthroughs contributed to the success of coal hydrogenation, the most
significant of which were the sulphur resistant catalysts and the two stage liquid-vapor phase
hydrogenation that Matthias Pier developed in 1920. For the FT synthesis, the cobalt catalysts that
Fischer and his co-workers prepared in the 1920-30 were crucial to its success (Stranges, 2001).
Another direct method is the Kohleoel process, which was also developed in Germany. In this process
coal is mixed with a recycle solvent and iron catalyst, which is then preheated and pressurized followed
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by adding hydrogen. The process takes place within a tubular reactor at a temperature and pressure of
470 C and 300 bar, respectively. This process was also explored by SASOL in South Africa.
Solvent refined coal processes were implemented as pilot plants in the United States. Hydrogenation
processes, patented in 1976, involved mixing dried, pulverised coal with roughly 1% molybdenum
catalyst at high temperatures and pressures to produce Naphtha, a synthetic crude product. The 1980s
saw Japanese companies develop the NEDOL process (Lesch, 2000).

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2 SYNTHETIC GAS PRODUCTION

Synthesis gas or briefly, syngas, is a mixture of carbon monoxide (CO), carbon dioxide (CO2) and
hydrogen (H2). Syngas can be produced from many sources, including natural gas, coal, biomass, or
virtually any hydrocarbon feedstock, by reaction with oxygen or steam. Syngas is a crucial intermediate
resource for production of hydrogen, ammonia, methanol, and synthetic hydrocarbon fuels
(Syngaschem, 2012).
Depending on the feedstock either gasification or steam reforming is undertaken. For coal and biomass
feedstock gasification is typically used. Gasification is achieved by reacting the feedstock at high
temperatures, typically above 700 C, without combustion, with a controlled amount of oxygen and/or
steam. In a gasification reactor the feedstock is transformed into a syngas, a mixture of H2, CO and CO2,
which opens up to making a variety of downstream energy carriers. The carbon in the coal combines
with oxygen in the water to create carbon monoxide, while the leftover hydrogen atoms create hydrogen
gas. The syngas could be used as a fuel at this stage or further processing can develop diesel and
kerosene (Blesl & Bruchof, 2010).
For a natural gas feedstock, typically steam reforming in used. The formation of syngas is strongly
endothermic and requires high temperatures. Steam reforming of natural gas proceeds in tubular
reactors that are heated externally. The natural gas, mainly methane (CH4) and steam react at high
temperatures (700 1100 C), in the presence of the nickel catalyst forming CO and H2. The process
uses a nickel catalyst on a special support that is resistant against the harsh process conditions.
Additional hydrogen can be recovered by a lower-temperature gas-shift reaction with the carbon
monoxide produced. The following two reactions summarize the process:
CH4 +H2 O CO+3H2

(1)

CO+H2 O CO2 +H2 O

(2)

Reaction (1) is highly endothermic and reaction (2) is moderately exothermic. Figure (1) summarizes a
typical syngas production scheme.

Figure 1 - Syngas production scheme

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3 FISCHER-TROPSCH REACTION
The Fischer-Tropsch Synthesis converts syngas into hydrocarbons which form the basis for gasoline,
diesel, jet fuel, and chemicals such as olefins and waxes. It forms the heart of the Gas-to-Liquids (GTL)
and Coal-to-Liquids (CTL) plants in South Africa, Qatar, Malaysia and China. The product distribution
is broader than liquids hydrocarbons alone, and includes methane and alkanes, CnH2n+2 (with n from 1
100), alkenes or olefins (CnH2n; n 2), and to a lesser extent oxygenated products such as alcohols.
Catalysts for the Fischer-Tropsch Synthesis are either based on cobalt or the much cheaper iron. In fact,
the iron-based catalyst is an iron carbide under reaction conditions, whereas cobalt works in the metallic
state (Syngaschem, 2012).
The synthetic gas produced from gasification is passed through reactors maintained at high temperatures
and pressures over a catalyst which speeds up the reaction of the gases together to form products useful
in daily life. Iron is the preferred catalyst to use in the Fischer-Tropsch process as it is not susceptible
to catalyst poisoning. Amongst the many products from the reaction chamber, the most useful are the
long chained alkanes consisting of hydrogen and carbon atoms. The lightest fuel is methane, having the
smallest chain, while longer heavier chains are responsible for products such as gasoline and kerosene.
Paraffins and waxes are derived from the much larger alkane chains. The medium chains are most
favoured and therefore, the reaction conditions are controlled to produce these intermediate chains.
Finally, the products are separated, cleaned and may be processed further to increase yields of desirable
products (Fischer-Tropsch Process, 2014).
The feedstock to FT are either coal, natural gas or biomass. The overall reaction equations are
depicted below:
Table 1 - Reactions depecting the reactions for different functional groups of the Fischer-Tropsch process

FISCHER-TROPSCH FUNCTIONAL GROUP REACTIONS

Alkanes

nCO+(2n+1)H2 Cn H2n+2 +nH2 O

(3)

Alkenes

nCO+(2n)H2 Cn H2n +nH2 O

(4)

Alcohol

nCO+(2n)H2 Cn H2n+1 +(n-1)H2 O

(5)

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The reactions are exothermic and dealing with the heat is an important issue in the reactor design.
Reaction conditions include temperatures of 200 350 C and pressures of 20 - 50 bar. The FT process
conditions are chosen such that the formation of hydrocarbon liquid fuels having higher molecular
weight is maximized. The process also involves some other side reactions of which the water-gas-shift
reaction is dominant.
CO+H2 O H2 +CO2

(6)

The most commonly used reactors for Fischer-Tropsch Synthesis is the fixed bed reactor, the fluidised
bed reactor and the slurry reactor. These vessels are favoured due to their excellent heat transfer
characteristics, resulting in stable reactor conditions. No diffusion limitations and possibility of
continuous refreshment of catalyst particles (Boerrigter & Van der Drift, 2004). The slurry reactor is
used to carry out the reaction at the lower temperatures between 220 - 250 C. The reactor uses lower
temperature for the production of heavier components (greater than C20), forming the basis of wax and
paraffins production for FT synthesis. The fluidized bed reactor is used for high temperature FT
synthesis between 320 350 C. This type forms the basis of petroleum chemicals due to the production
for lighter components of between C1 C20.

Figure 2 - Illustration of Fischer-Tropsch process

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4 SASOL REACTOR TECHNOLOGY

SASOL, South Africa uses a Gas to liquid (GTL) technology for the production of synthetic fuels. GTL
technology converts natural gas into high quality liquid petroleum product which includes naphtha and
diesel. Raw natural gas is purified in a hydrogenation reactor and a washing system. The purified feed
gas is then pre-treated by saturation with process waster and preheating (SASOL LTD., 2010). Once
pre-treated, the GTL conversion process consists of three main steps:

4.1 STEP 1: NATURAL GAS REFORMING

Synthetic gas for the GTL process can be produced through various technologies that require mostly
steam and air or oxygen. During this process, hydrogen atoms are stripped from hydrocarbon molecules
present in the natural gas and the carbon atoms are used to react with oxygen (which is introduced as
steam, air or a pure gas) to produce carbon monoxide molecules. Synthetic gas, which consists of
hydrogen, carbon monoxide and carbon dioxide, is the resulting product of this step in the production
process (SASOL LTD., 2010).

4.2 STEP 2: SASOLS PROPRIETARY CONVERSION PROCESS

The purified synthetic gas produced by step 1 is sent to a slurry phase synthetic reactor, and depending
on the temperature, pressure and type of catalyst used, either light synfuels or waxy synfuels are
produced. Hydrogen and carbon monoxide yield linear hydrocarbons, oxygenated hydrocarbons and
reaction water through a catalytic chemical process under heat and pressure with the aid of a catalyst
(either cobalt or iron based). The liquefied synthesis reactor is then employed and the products from
this reactor are cooled successively in a product recovery plant until most components become liquefied
(SASOL LTD., 2010).

4.3 STEP 3: PRODUCT SEPARATION AND UPGRADE

Liquid products are separated in the final upgrading unity which makes use of mild hydrocracking to
convert higher molecular weight waxes and lubes into everyday products such as naphtha, diesel and
liquefied petroleum gas. The resulting diesel is clear and burns more easily compared to conventional
fuels as the diesel has been purified of sulphur and other impurities before the synthesis of the liquid
fuel (SASOL LTD., 2010).

Figure 3 - GTL process used at Sasol

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5 GTL AND CTL TECHNOLOGY

5.1 GTL TECHNOLOGY

The gas-to-liquids (GTL) process involves two main operations: the conversion of natural gas into a
mixture of carbon monoxide and hydrogen, which is syngas, via processes such as steam methane
reforming (SMR) or autothermal reforming (ATR), followed by the Fischer-Tropsch (FT) process to
convert the syngas into paraffinic hydrocarbons. The products of the FT process can be blended with
naturally occurring crude oil to provide an economic route to market, or upgraded to produce a wide
range of high quality finished products including ultra-clean diesel, kerosene (jet fuel), naphtha, bases
for synthetic lubricants and waxes. Products of the FT process offer significantly better performance
than their petroleum-based equivalents (Gas-to-liquids, 2015).

Figure 4 - Illustaration of gas-to-liquid process

Natural gas is one of the most abundant energy sources available globally. The conversion of natural
gas is liquid fuels attracts wider markets due to easier handling and transportation. With the expected
rise in demand for diesel fuels, GTL technology provides an additional option to provide cleaner, more
environmentally fuels to meet global demands (Gas-to-Liquids, 2013).

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5.2 CTL TECHNOLOGY

The technology used for the conversion of Coal to Liquids (CTL) is referred to as coal liquefaction as
it allows for the transformation of coal into an alternative oil or fuel source. Clean petroleum and diesel,
synthetic waxes, lubricants, chemical feedstocks and alternative liquid fuels such as methanol are the
resulting products achieved from the process. CTL is particularly suited for countries that have large
coal reserves and currently depend on oil imports (Coal to Liquids, 2013).Two methods are currently
used for CTL technology:

1. Direct Liquefaction: coal is dissolved in a solvent at a high temperature and pressure. This
process is highly efficient, however, the liquid products require further refining to achieve high
grade fuel characteristics.

2. Indirect Liquefaction: this method calls for the gasification of coal to form a syngas. The syngas
is then condensed over a catalyst in a process like that of the FisherTropsch, to produce high
quality and clean products (Coal to Liquids, 2013).

Figure 5 - Direct coal conversion of coal-to-liquids process

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Figure 6 - Indirect coal conversion of coal-to-liquid process

Advantages of CTL process:

Coal is affordable and there is an abundant supply globally. This would prevent the drilling of
crude reservoirs and eliminate the import of oil.

Fuels derived from coal are sulphur free and low in nitrogen oxides.

Uses of coal liquids include transport, cooking, power generation and industrial application.

CTL process provides ultra clean cooking fuels hence the coal liquid fuels reduce the health
risks of indoor air pollution. (Coal to Liquids, 2013).

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6 OCM TECHNOLOGY
The oxidative coupling of methane (OCM) is a type of chemical reaction discovered in the 1980s for
the direct conversion of natural gas, primarily consisting of metharne, into value-added chemicals.
Methane, being the predominant component of natural gas, provides the perfect example of attractive
feedstock as a result of its enormous supply, low cost and global availability. Oxidative Coupling of
Methane (OCM) technology refers to the coupling of methane to form valuable products such as ethane,
ethylene and other such C2 hydrocarbons. The principle product of OCM is ethylene, the worlds largest
commodity chemical and the chemical industry's fundamental building block. While converting
methane to ethylene would offer enormous economic benefits, it is a major scientific challenge. The
use of ethylene in industry is limited for use in higher-value commodity processes and chemicals due
to its high cost. Enabling the production of ethylene will result in the deduction of the costs associated
with ethylene derived chemicals and liquid fuels. The steam cracking route to ethylene is the most used
in present times. Ethylene production by steam cracking consumes large amounts of energy, uses
valuable oil fractions, such as naphtha and is the largest contributor to Greenhouse gas emissions in the
chemical industry. The OCM reaction takes place at high temperatures of between 600 and 800 C, but
produces low C2 yields which is the main reason that it has not yet been commercialized despite its
potentially high profitability (Tullo, 2014).

Over Catalyst (Oxides)

CH4 +O2

C2 Products (C2 H6 and C2 H4 )

(7)

More specifically, the oxidative coupling of methane to ethylene is:

2CH4 +O2 C2 H4 +2H2 O

(8)

The reaction is exothermic. The ethane subsequently undergoes dehydrogenation to form ethylene.
Hundreds of catalysts have been tested, and several promising candidates were extensively studied.
Researchers were unable to achieve the required chemoselectivity for economic operation. Instead of
producing ethylene, the majority of methane was non-selectively oxidized to carbon dioxide .

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Extensive research and funding has been generated for the development of the OCM process. Figures
(7) and (8) illustrates two processes displaying the advancement in the OCM process.

Figure 7 - Illustration for the proposed Siluria OCM process

Figure 8 - Illustration for the OCmol OCM process

Figure (7) is the process proposed by Siluria. Siluria are the leading researchers in OCM. Figure (8)
shows the OCmol proposed OCM method which includes oligoerization.

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7 REFERENCES
Blesl, M., & Bruchof, D. (2010, May 2). Syngas Production from Coal . Retrieved from Energy
Technology Systems Analysis Program: http://www.iea-etsap.org/web/e-techds/pdf/s01coal%20gasification-gs-gct.pdf
Coal to Liquids. (2013). Retrieved 04 30, 2014, from World Coal Association:
http://www.worldcoal.org/coal/uses-of-coal/coal-to-liquids/
Fischer-Tropsch Process. (2014). Retrieved May 05, 2014, from Hub Pages:
http://flyingvet.hubpages.com/hub/Fischer-Tropsch-process
Gas-to-Liquids. (2013, June). Retrieved April 30, 2014, from Chevron: Human Energy:
http://www.chevron.com/deliveringenergy/gastoliquids/
Gas-to-liquids. (2015, February 18). Retrieved from Velocys:
http://www.velocys.com/our_products_applications_gtl.php
Lesch, J. E. (2000). The German Chemical Industry in th eTwentieth century. Dordrecht: Kluwer
Academic publishers.
SASOL LTD. (2010). GTL Technology. Alberta.
Syngaschem. (2012, February 15). Synthesis Gas Chemistry and Synthetic Fuels. Retrieved from
Syngaschem: http://www.syngaschem.com/syngaschem
Tullo, A. H. (2014, July 7). Silurias Oxidative Coupling Nears Reality. Retrieved from C&EN:
http://cen.acs.org/articles/92/i27/Silurias-Oxidative-Coupling-NearsReality.html?h=567597735

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