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1.1. History of GTL

In 1902 Paul Sabatier and Jean Sanderens discovered a way of converting
Carbon Monoxide (CO) and Hydrogen (H2) to Methanol (CH3OH). Franz Fischer
and Hans Tropsch developed this synthesis to mainly oxygenated products and
hydrocarbons in 1923 using alkalized iron as a catalyst.
In 1925 the two German scientists further developed
this reaction by converting the mixture of (CO) and (H2)
which is called Synthesis Gas or "Syngas" in a
laboratory to oxygenated products and liquid
hydrocarbons using Cobalt and Nickel catalysts at
atmospheric pressures. They also found (which became latter as an assumption)
that low pressures produced mainly hydrocarbons while high pressures produced
oxygenates. In 1930 the Fischer – Tropsch reaction to make chemicals
commercialized and became a process known as (F-T) process.
The produced raw hydrocarbons can be refined and upgraded to different fuels like
gasoline, diesel, and other products. In the mid 1930s a number of Fischer-Tropsch
plants were constructed, and by 1938 over 590,000 tons of oil and gasoline were
being produced annually in Germany from synthesis gas manufactured from coal.
During 1930s plants were also constructed in Japan, Britain, and France. During
World War II Germany operated nine F-T plants that produced 12,000 bbl/d of
fuel. Those plants that were not destroyed during the war were shut down
subsequently as cheap petroleum crude and natural gas became available.
One country which has continued to pursue the development of indirect coal
liquefaction by Fischer-Tropsch process is South Africa. In the following years
many companies like Mobile, Sasol, Shell, Rentech, ConocoPillips, Syntroleum,
and BP, have started technology developments of the Fischer-Tropsch process

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either in response to oil crises, or due to high crude oil price. The main purpose of
these developments is to make any industrial plant use this technology to become
commercially successful.
Fischer-Tropsch Synthesis (F-T) converts synthesis gas (CO and H2) which can be
made from coal, natural gas, petroleum residues, biomass, and any carbonaceous
materials to long chain hydrocarbons. If liquid petroleum-like fuel, lubricant, or
wax is required, then the Fischer- Tropsch process is the right process which can
be applied. This is an alternative route to obtain fuels and chemicals rather than the
current dominant petroleum resources. Fischer-Tropsch synthesis now is becoming
competitive to petroleum due to its improved catalysts and processes.
Currently, Gas to Liquids (GTL) is the major focus on the (F-T); however, coal to
oil is still a vital solution for countries with abundant coal resources. Chemically
the (GTL) in Fischer-Tropsch process is a series of catalyzed chemical reactions in
which carbon monoxide and hydrogen are converted into liquid hydrocarbons of
various forms. Typical catalysts used are based on iron and cobalt. The principal
purpose of this process as mentioned above is to produce a synthetic petroleum
substitute.

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1.2. Background
Natural gas is recognized as one of the cleanest and most abundant fossil fuels.
With the growing global market for natural gas, it is important to identify effective
methods for deploying the vital resource worldwide.
In many cases, there is an economic incentive to ship the gas in liquid form which
occupies much less volume than the gaseous form. In this regards two main
approaches have been adopted: liquefaction leading to liquefied natural gas (LNG)
and chemical conversion to convert gas to liquid (GTL). The key concept of a GTL
process is to chemically convert the gas to longer-chain hydrocarbons that will
typically be in the range of liquid transportation fuels. A leading GTL technology
is the Fischer Tropsch (F-T) process. It is beneficial to compare the key features of
GTL and LNG. Table 1.1 lists, the main points of comparison between GTL and
LNG, where BSCFD is set as billion standard cubic feet per day, BPD is barrels
per day, MMTPA is million tones per year, bbl is barrels, CAPEX is capital
expenditures. Carbon efficiency is defined as (carbon molecules in the final
products)/ (carbon molecules in natural gas feed), and energy efficiency is set as
(low heating value of liquid final products)/ (low heating value of natural gas), as
indicated in that report. They produce quite different products for markets. The
products of GTL range from gasoline and jet fuel to middle distillates.
Different from LNG, middle distillates are the most popular products from GTL,
and can be utilized as the feedstock to produce ethylene and propylene.
Considering the cost for the process, GTL process will be prospective if the crude
oil obtained diesel has a price higher than some limit.
SO, Gas-to-liquid (GTL) process involves the chemical conversion of natural gas
(or other gas sources) into synthetic crude that can be upgraded and separated into

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different useful hydrocarbon fractions including liquid transportation fuels. A
leading GTL technology is the Fischer Tropsch process.

There are environmental advantages for using F-T based GTL technologies. These
include low content of sulfur compounds and NOx, coupled with the benefit of less
aromatics left reducing the toxicity and the particulate matter generated when
combustion. Focus also goes to the ability to diversify further to higher valued
chemical products other than fuels, with a higher cetane number (70-80) allowing a
superior performance for engine design. it tackles the problem of transportation of
natural gas, and the products could be blended with refinery stock as superior
diesel as an alternative way.

Fig 1.1. Comparison between GTL and LNG

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1.3. Environmental advantages

The primary environmental advantages for GTL compared to refineries are

illustrated in Fig. 1.2

Fig 1.2. Environmental advantages of GTL processes compared to normal diesel

(GTL emission reduction % based on normal diesel)

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1.4. Basic Process Steps

The GTL process is mainly comprised of three steps shown in Fig. 1.2. These are
steam reforming of natural gas to produce syngas (CO and H2), followed by F-T
reaction, and finally upgrading of the products to cracking and hydro-processing
units for the synthesis liquid hydrocarbons to yield products that meet the market
specifications.

Fig. 1.3 main parts of GTL process

The GTL process in Fig.1 has 3 main steps (i) production of synthesis gas
(syngas), (ii) Fischer-Tropsch (FT) reactor and (iii) upgrading units. In the syngas
unit, a mixture of hydrogen and carbon monoxide is produced and is sent to the
Fischer-Tropsch (FT) reactor for converting to liquid fuels. The syngas and FT
units make up almost 70% of total investment cost of the plant. In our work, our
focus is on these two units.

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1.5. Process description

1.5.1Feed data:
Natural gas feed is assumed at the following conditions:
Flow rate: 8195 kmol/hr, Pressure: 25 bar, Temperature: 40 °C
Composition: CH4 (95.5%), C2H6 (3%), C3H8 (0.5%), nC4H10 (0.4%),
N2 (0.6%)
H2O = 6025 kmol/hr ,,, O2 = 6149.32 kmol/hr

In GTL processes, there are different routes for syngas production from natural
gas, including Auto Thermal Reforming (ATR), steam reforming, partial oxidation
of methane and CO2 reforming. ATR is a combination of steam reforming and
oxidation of methane. It is claimed to be the best route for syngas production and
has been selected for this study.
To avoid the potential problem that the ATR works as a steam cracker, producing
olefins from higher hydrocarbons in the feed.
1.5.2. Pre-Reformer
The temperature is 350-550°C and all higher hydrocarbons are converted
according to the following reactions:
Complete conversion reactions (endothermic, so energy is needed):

C2H6+ 2H2O→5H2+ 2CO ΔH = +350 (1)

C3H8+ 3H2O→7H2+ 3CO ΔH = +500 (2)

C4H10+ 4H2O→9H2+ 4CO ΔH = +650 (3)

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Equilibrium reactions:

CO+ 3H2→ CH4+ H2O ΔH = -210 (4)

CO+ H2O→ CO2+ H2 ΔH = -41 (5)

In our case, natural gas and water are preheated to 455°C and fed to the performer.
In spite of the exothermic equilibrium reactions the overall reactions are
endothermic and the outlet temperature is about 416°C.

1.5.3 ATR

The pre-reformer outlet stream is heated in a fired heater to 675 °C before entering
the authothermal reformer (ATR). Oxygen is preheated to 200 °C and is also fed to
the ATR. The ATR is the main reactor in producing the synthesis gas and the
following three main reactions take place:
CH4+ 1.5O2→ CO+ 2H2O ΔH = -520 (6)

CH4+ H2O→ CO+ 3H2 ΔH = +210 (7)

CO+ H2O→ CO2+ H2 ΔH = -41 (8)

Because of the large heat generated by combustion in reaction (6) the net reactions
are exothermic, and the outlet temperature of the ATR is about 1000 ºC. and
pressure at 18 bar.
A high-pressure CO2 capturing process with MDEA as an absorbent is used to
remove most of the CO2 from the syngas.

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A mixture of hydrogen and carbon monoxide is the main product of ATR and a
ratio of around 2-2.3 is desired to have maximum conversion to liquid fuels in
the subsequent FT reactor.

1.5.4 FT reactor

The syngas is sent to the FT reactor. The FT synthesis with cobalt catalyst
produces mostly n-alkanes and 1-alkenes.The main reaction is
nCO + 2nH2 → (-CH2-)n + nH2O
The product distribution of the hydrocarbons “(–CH2-)n” are assumed to follow
an Anderson-Schulz-Flory (ASF) distribution to methane, alkanes and alkenes,
which can be expressed as:

The pressure is maintained at 30 bar and temperature is set to be between 200-

240°C

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1.6. Synthesis Gas Preparation

The feedstock reacts with steam and oxygen to produce hydrogen, carbon
monoxide and carbon dioxide. The technologies for producing syngas from natural
gas involve: partial oxidation “POX”, catalytic steam methane reforming “SMR”,
two-step reforming, autothermal reforming ATR, and heat exchange reforming.
The choice of the reactor is determined by balancing between the characteristics of
each one. SMR doesn’t require oxygen and high temperature, but it produces much
higher hydrogen to CO ratio than needed. POX could allow absence of catalyst and
thus lower CO2 content, but it requires oxygen and high operating temperature
causing soot formation that’s hard to handle. ATR, known as endothermic syngas
reforming reactions automatically happening by virtue of the internal heat brought
in by oxidation of a portion of the feed hydrocarbons, has the most favorable
H2/CO ratio, but it needs oxygen to proceed and has limited commercial
experience. Heat exchange for reforming can use compact equipment and
introduces flexibility to application, but in some cases it must be coupled with
other syngas producing techniques to achieve the job. Oxygenblown reforming has
received more attention over air-blown reforming in the low air compression
power demands, high thermal efficiency, the ability to recycle F-T tail gas, and the
smaller downstream equipment sizes mission. Also, ATR shows up in many
commercial processes due to the ability to handle large scale scenarios.
The H2/CO ratio is subject to adjustment by controlling some factors including the
flowrate of CO2 and use of steam. While recycling CO2, and removing H2 will
decrease ratio, increasing steam would yield opposite effect.

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1.7. Different type of Fischer-Tropsch reactor

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1.8. Product Upgrading
Separation is typically the way to tackle the products with many phases. Pressure
requirements should be met to facilitate the atmospheric storage. First light gases
are separated. Oxygenated compounds are usually removed from the liquid for the
ease of later processing. Then, through fractionation and extractive distillation
olefins could be removed from the straight liquid products. They are either
oligomerised, alkylated or hydroformylated to produce desired products or blended
with other liquid products for the mixing use. The other products are generally
converted into naphtha and diesel by the means of hydrogenation step and
fractionated. The naphtha can be further processed to gasoline. For LTFT
processes with cobalt catalyst only hydroprocessing and separation are employed
since the olefin content is low.
Usually, the produced diesel is blended with special chemicals to enhance stability.
At the same time, other methods may be used to improve properties such as
lubricity.
Chemical conversion is one method involving hydro-isomerisation, in which
straight chain hydrocarbons are changed to branched ones for improving cold flow
properties.

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While long chain hydrocarbons have two ways to go. One is hydrocracked to
further provide naphtha. Alternative one is hydroprocessed to high quality
lubricant base oils.
To get further cuts or fractions, vacuum or short path distillation is used to produce
special demanded wax or products.
In light of the increasing demand for diesel for transportation and industrial uses,
producing diesel mainly from GTL process is a good choice, especially this diesel
is very low in sulfur content. Thus, wax could be cracked with certain selectivity to
diesel with the help of special catalysts, and produced naphtha is another resort to
get diesel through various processes.
The plant scale generally depends on whether the latter processes are justified.
Although the LPG with C3 to C4 parrafins takes little place in the whole products,
it shouldn’t be looked down for the significant higher prices. It is recovered
directly from the vapor product of the F-T reactor. They can be further produced to
plastics or cracked to olefins.
Small fractions of oxygenates are dissolved in the reaction water and by distillation
from the bulk water they can be processed to a variety of chemical ranges.

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