Fischer_Tropsch Process

Introduction
The FischerTropsch process (or FischerTropsch Synthesis or F-T) is an important
gas-to-liquids (GTL) technology and a set of chemical reactions that converts a
mixture of carbon monoxide gas and hydrogen gas into liquid hydrocarbons (fossil
fuels like gasoline or kerosene).The F-T process has received attention for many
different reasons, for example a way to produce low-sulfur diesel.
History
The original process was invented by Franz Fischer and Hans Tropsch. They were
working at the Kaiser Wilhelm Institute in the 1920s, when they invented the
original process. Ever since many changes have been made to improve the process.
The term "Fischer-Tropsch" now is used for many processes that are similar to the
original invention. Fischer and Tropsch submitted many patents. It was given to the
factories in Germany in 1936. Germany had an abundance of coal but very little
petroleum. The F-T process enables conversion of coal into gasoline, which is
important to gasoline based transport like cars, airplanes and trucks.
Being petroleum-poor but coal-rich, Germany used the FischerTropsch process
during World War II to produce ersatz (replacement) fuels. FischerTropsch
production accounted for an estimated 9% of German war production of fuels and
25% of the automobile fuel.
The Process Chemistry(Reactions and Products)
The FischerTropsch process involves many kinds of reactions, which lead to both
wanted and unwanted results. The desirable reactions create chemicals called
alkanes. Sometimes the gas methane (natural gas) is produced which is generally
undesirable. Sometimes different kinds of alcohol are produced in small amounts.
The FischerTropsch process involves a series of chemical reactions that produce a
variety of hydrocarbons, ideally having the formula (CnH(2n+2)). The more useful
reactions produce alkanes as follows:
(2n + 1) H2 + n CO CnH(2n+2) + n H2O
where n is typically 10-20. The formation of methane (n = 1) is unwanted. Most of
the alkanes produced tend to be straight-chain, suitable as diesel fuel. In addition to
alkane formation, competing reactions give small amounts of alkenes, as well as
alcohols and other oxygenated hydrocarbons.
The formation of paraffin is favored by high H2/CO ratios and catalysts with strong
hydrogenating abilities, the formation of olefins is favoured in syngas with low
H2/CO ratios and a catalyst with less strong hydrogenating abilities. Apart from
hydrocarbons, H2O is also a primary product from FTS. 15 The presence of water is

undesirable in FTS since it affects syngas conversion, hydrocarbon selectivity, FT

product distribution and the catalyst longevity due to its influence on the degree of
syngas adsorption on the catalyst, chain initiation, chain growth, methanation,
hydrogenation to paraffin and dehydrogenation to olefins.16 It is believed that a
high H2O concentration is one factor that leads to oxidation and deactivation of iron
carbides and therefore understanding H2O formation and desorption is important
for enhancing FTS activity.

Fischer-Tropsch catalysts
A catalyst is a chemical element you add to a process to make it go faster or speed
it up. Many different catalysts can be used for the FischerTropsch process. The
most common catalysts are the metals cobalt, iron, and ruthenium. These metals
are all transition metals. The metal nickel can also be used, but usually with
unwanted results. A nickel catalyst in the reaction usually produces a lot of
methane, which is undesirable.
Cobalt seems to be the most active catalyst (it has the biggest and fastest effect on
the process). When the input is a natural gas Cobalt catalysts are very good for the
Fischer-Tropsch process. Iron catalysts are better when the input gas is of lower
quality (less pure) such as coal or biomass.[2]
Most metals used for this process (like Cobalt, Nickel, and Ruthenium) remain in
their metal form when you add them to the process. However Iron catalysts behave
very differently. Often iron catalysts change form and chemical phase, like
converting into various oxides and carbides during the reaction. It is important to
control all of the iron reactions during the process, or else the process might not
work correctly.
Fischer-Tropsch catalysts are famous for being extremely sensitive to the addition of
sulfur. Even a tiny amount of sulfur can have an undesirable impact on the reaction.
Cobalt is more sensitive to sulfur than iron.
HTFT and LTFT[change | change source]
High-Temperature Fischer-Tropsch (or HTFT) is operated at temperatures of 330C350C. HTFT uses an iron-based catalyst. Sasol used HTFT in Coal-to-Liquid plants
(CTL). Low-Temperature Fischer-Tropsch (LTFT) is operated at lower temperatures
and uses a cobalt-based catalyst. Shell used LTFT in an integrated Gas-to-Liquid
(GTL) plant in Bintulu, Malaysia.[3]
Commercialization
The F-T process has been used by many large companies, however sometimes the
process is unpopular for many reasons. One such a reason is the high cost of
equipment to get F-T factories operational. High operational and maintenance costs
to keep the process problem free is another reason. Also, petroleum production cost
is highly unpredictable. Usually, the factories are only profitable when they have

access to "stranded gas". "Stranded gas" is what is referred to as sources of natural

gas very far from major cities that is too expensive to pump to these cities. If the
natural gas could be pumped to these cities and sold directly to consumers, it would
be much more profitable for these companies. Therefore several companies are
developing processes to enable practical exploitation of so-called stranded gas
reserves.
Research Developments
In 2009, chemists working for the U.S. Navy studied Fischer-Tropsch for making fuels
with hydrogen and electrolyzing seawater. This study produced mostly methane
gas, but the rest were short-chain hydrocarbons. Further refining of the
hydrocarbons produced could lead to making kerosene-based jet fuel.
The abundance of CO2 makes seawater look like a good different fuel source.
Scientists at the U.S. Naval Research Laboratory said that, "although the gas forms
only a small proportion of air around 0.04 per cent ocean water contains about
140 times that concentration".

Process efficiency
Using conventional FT technology the process ranges in carbon efficiency from 25 to
50 percent[38] and a thermal efficiency of about 50%[39] for CTL facilities idealised
at 60%[40] with GTL facilities at about 60%[39] efficiency idealised to 80%[40]
efficiency
Feed stocks Gasification
Other reactions relevant to F-T
To make the gases needed for the F-T process many steps are required. For
example, all chemicals entering the reactor must have all sulfur removed. For
factories that start out with methane and want to make a liquid hydrocarbon (like
kerosene), another important reaction is "steam reforming", which turns the
methane into CO (carbon monoxide) and H2 (hydrogen gas). This is the chemical
equation for how steam reforming works. Gasification refers to converting chemical
compounds into gas. Some F-T factories use coal, biomass or steam reforming.
Before these factories can start their F-T process, firstly, reactant gases entering a
FischerTropsch reactor must be desulfurized. Otherwise, sulfur-containing
impurities deactivate ("poison") the catalysts required for FischerTropsch reactions.
They must turn the solids into gases like CO, H2, and alkanes. This process is called
gasification. and the product is called synthesis gas ("Syngas").The gas collected
from coal gasification often has a CO/H2 ratio of ~0.7 instead of the best ratio of
~2. This ratio can be adjusted from 0.7 to 2.0 using the water-gas-shift-reaction.
Gasification is a dirty and expensive process. For FischerTropsch plants that use
methane as the feedstock, another important reaction is steam reforming, which
converts the methane into CO and H2:
H2O + CH4 CO + 3 H2

The reaction above describes one molecule of H2O (steam) plus one molecule of
CH4 (methane) converts into one molecule of CO(carbon monoxide) and three
molecules of H2 (hydrogen gas).
Coal-based FischerTropsch factories are factories that start out with coal, apply
gasification to the coal and then use the resulting gas for the Fischer-Tropsch
process. These factories can produce large volumes of CO2 in this way. One of the
main reasons for this approach is the large amounts of energy required for a coalbased gasification process.
In the BTL-FT process, biomass, such as woodchips and straw stalk, is firstly
converted into biomass-derived syngas (bio-syngas) by gasification. Then, a
cleaning process is applied to remove impurities from the bio-syngas to produce
clean bio-syngas which meets the FischerTropsch synthesis requirements. Cleaned
bio-syngas is then conducted into a FischerTropsch catalytic reactor to produce
green gasoline, diesel and other clean biofuels.
Biomass
Biomass is organic matter derived from living, or recently living organisms. Biomass
can be used as a source of energy and it most often refers to plants or plant-based
materials which are not used for food or feed, and are specifically called
lignocellulosic biomass