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The Role of GTL Technology as an Option to Exploit

Natural Gas Resources
Hussein K. Abdel-Aal and Maha Abdel-Kreem

*National Research Center, Cairo, EGYPT

email: [email protected]

**Higher Technical Institute, Tenth of Ramadan

email: [email protected]

Abstract

High amounts of Global sources of remote natural reserves gas are identified along with
the main objective to allow energy contained in to be moved economically to the
market. The current options that are adopted to export natural gas are basically two:-

1. To liquefy the gas and ship it as LNG (Liquefied Natural Gas)

2. To convert it to bulk petrochemicals in particular methanol or ammonia and
other down-stream products.

The last approach represents relatively small usage of the gas with limited markets.
Chemical conversion before transportation of natural gas to liquid (GTL), using Fisher-
Tropsch process offers an attractive alternative to unlock remote sources of natural gas.
It is reported to be most promising on the basis of its current level of development and
its potential future improvements.

The two main components of Fisher-Tropsch process are carefully examined: synthesis
gas generation and its subsequent conversion to clean petroleum fuel. Different
methods of producing synthesis gas are described. These include: steam reforming, non
catalytic partial oxidation (NCPO), auto thermal reforming (ATR) and combined
reforming. Chemical reactions underlying the Fisher-Tropsch process are presented with
trends of developments in the GTL technology.

Commercial applications of GTL technology worldwide are cited, especially in some

Arab countries. The positive impact of GTL on the environment is emphasized because
of two reasons:1st the clean-burning properties of the produced diesel fuels, 2 nd
converting natural gas to liquid allows oil producers to utilize the natural gas that would
otherwise be flared and pollute the atmosphere

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Introduction

New technology is being developed and applied to convert natural gas to liquids,
known as GTL. The key influences on the competitiveness of the GTL approach are the
following factors:-

1. Cost of capital investment 2. Operating costs of the plant

3. Cost of feed stock 4. Anticipated scale of production and the ability to achieve high
utilization rates in production.

GTL not only adds value by utilizing remote natural gas, but capable of producing
superior products that can be sold or blended into refinery products.GTL, however is not
competitive against conventional oil production unless the gas has a low opportunity
value and not readily transported. The difficulty of moving remote natural gas to the
market in a profitable way can be comprehended if we know that many important gas
fields are very far from the main international market. The following are some specific
examples:

• Sakhalin area (Russia) is about 3,000 km from Tokyo (Japan)

• Bonny area (Nigeria) is about 8,000 km from Rotterdam (The Netherlands)

• Abu Dhabi fields ( U.A.R.) are about 11,000 km from both Rotterdam and Tokyo

• In addition, large gas reserves exist in Qatar, Iran, Saudi Arabia, Canada and
Alaska.

The world’s proven gas reserves are estimated at a value of 6000 trillion cubic feet (tcf);
while the potential reserve is reported to be around 13,000 tcf. Only a small fraction of
the world marketed production of natural gas is internationally traded today. Of the
proven and potential gas reserve, up to 80 % are too far from large markets to be
transported by pipeline. Some remote gas reserves are shipped as LNG (Liquefied
Natural Gas) using cryogenic liquefaction which requires expensive insulated and
pressurized vessels. Other option is to convert natural gas into chemical products such
as methanol which is exported using conventional tankers.

A different kind of technology for converting hydrocarbon gases to liquids, called gas-
to-liquid (GTL) is on the verge of changing the exploitation of remote reserves of natural
gas in the world. Many large oil and gas companies are developing expertise in this
new field. A few already have commercially operating plants and many have initiated
pilot projects.

In summary, the conversion of remote natural gas reserves to liquid products to be

shipped by tankers is illustrated in Figure 1.

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GTL Technology

The primary objective of GTL technology is to convert natural gas into clean petroleum
products. In principle, there are two broad technologies to convert natural gas to
liquids:-

a) Syncrude- the direct approach to convert natural gas into what is known as
“syncrude” :

The direct conversion of natural gas (typically from 85 to 90 % methane), eliminates

the cost of producing synthesis gas as intermediate step, but it involves high activation
energy and is difficult to control .Several direct conversion processes have been
launched, but none have been commercialized; being economically unattractive.

b) Synthesis gas (syngas): the indirect conversion of natural gas to liquids

Instead of carrying a heavy load in one trip, divide it and make two trips. .In principle,
the process of converting natural gas into clean petroleum liquids involves basically two
steps:-

1st Generation of synthesis gas

2nd Conversion of synthesis gas to petroleum fuels via Fisher-Tropsch (F-T) synthesis

Converting gases to liquid, in its general term, i.e. GTL, could imply the following two
options:-

First- GTL products obtained from hydrocarbons recovered from natural gas- this
may involve the production of high octane gasoline fuels by alkylation and
polymerization processes. In addition, the application of fuel-cells using methane
as a feed stock produces energy plus water as products.

Second- GTL products obtained from natural gas as a feed stock, as shown in
Figure 2.This may involve producing synthesis gas ( referred to as “syngas” which
is a mixture of H2 & CO) from sulfur-free feed using one of the following four well-
established processes:-

1. Steam reforming (SR)

2. Non catalytic partial oxidation (NCP)
3. Auto-thermal reforming (ATR)
4. Combined or two-step reforming (TSR)

When handling sour natural gas (gas containing sulfur compounds), the non-
catalytic partial oxidation process (NCPO) is recommended for the production of
syngas, along with sulfuric acid as presented in Figure 3.

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GTL Technology Using Fisher-Tropsch Process

The discovery of Fisher Tropsch chemistry dates back to the 1920s .Its development has
been for strategic rather than economic reasons as in Germany during World War II and
in South Africa during the apartheid era.

During the last years, there has been a renewed interest to use Fischer-Tropsch
technology to convert natural gas to liquid (GTL). The following are some of the factors
that motivated this new trend:-

1. The discovery of huge reserves of natural gas, mostly remote or stranded

reserves; and the need to mobilize it to the international market.
2. Environmental restrictions against flaring associated gas.
3. Developments in the technology of the process along with improvements in the
cost-effectiveness of converting the gas to liquid.
The conversion process, in general, encompasses the following three basic
stages:-

 Generation of syngas
 Conversion of syngas to petroleum products
 Hydro-processing to upgrade the produced products into finished ones

These stages are schematically illustrated in Figure 4.

1-Generation of Synthesis gas

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a) Steam reforming

The first stage is the reaction between the hydrocarbons; exemplified with
methane and steam:-

CH4 + H2O  CO + 3H 2 …(1) followed by

CO + H2O  CO2 + H2

The total overall reaction may be represented by

CH4 + 2H2O CO2 + 4H2

Inspection of equation (1) shows that the reaction conditions should be as

follows:- Pressure is adverse, since two molecules of reactant give four molecules
of product. Excess steam will tend to push equilibrium in favor of CO. The
reaction is highly exothermic and equilibrium moves favorably with rise of
temperature. In practice, the theoretical equilibrium is approached by the using
catalysts. The most common is nickel promoted with magnesia or alumina,
mounted on an inert support. Steam reforming may be considered to generate
syngas under the following conditions:- A relatively small GTL plant (capacity is
below 10, 0000 bbl/day). Additional hydrogen could be used to produce
methanol or/ and ammonia as co-product .The source of natural gas has a high
CO2 content. Water is available at a low cost.

b) Non-catalytic partial oxidation (NCPO)

The non- catalytic partial combustion of methane produces syngas with H2/CO
ratio < 2, which is close to the optimum needed by Fisher-Tropsch process .This
low ratio results from the very little steam that is used in the process. Due to the
absence of catalysts, the reformer operates at an exit temperature of 1400
degree C. This high temperature along with absence of catalysts could lead to:-
1-The formation of soot 2- Higher oxygen consumption

c) Auto-thermal reforming (ATR)

Unlike NCPO, auto thermal reforming uses a catalyst for reforming in the
presence of steam and oxygen. Due to the milder operating conditions (exit
temperature about 1000 degree C) and the use of steam (S/C ratio about 1.3),
the synges is soot free. However, at this S/C ratio, syngas produced will have a
H2/C ratio about 2.5, higher than what is needed by Fisher-Tropsch

d) Combined reforming or two-step reformer (TSR)

Combining a steam reformer and an auto thermal reformer will bring in better
energy utilization than can be achieved with either one. Although less expensive

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than steam reforming on its own, this type of reforming is more expensive than
auto thermal reforming. The choice between combined reforming on one hand
and auto thermal reforming, on the other side will depend on the cost of natural
gas.

2. Conversion of Synthesis Gas to Petroleum Products

The conversion of syngas to liquid hydrocarbons is a chain-growth chemical
reaction of carbon mono-oxide and hydrogen on the surface of a heterogeneous
catalyst. To state differently, the reaction could be described as the catalytic
condensation of carbon monoxide and hydrogen to give high molecular weight
hydrocarbons with the elimination of water. The main reaction is represented by:-

(2n+1) H2 + n CO  H -(CH2)n- + nH2O (g)

The “carbon number” of hydrocarbons produced by F-T reaction always has a wide
range. “n” ranges from 1 to an upper limit of 50, 70 or even 100. The hydrocarbons
obtained are mixtures of paraffin and olefins. They include LPG, Naphta, Diesel, Heavy
Gas oil(Wax).

The ratio depends on two parameters:1.The reaction conditions inside the reactor( T &
P) 2.The ratio of carbon mono-oxide to hydrogen in the syngas.

Carbon dioxide formation represents wastage of the valuable carbon monoxide. It can
be avoided by suitable choice of catalyst. On the other hand, methane formation
could be minimized by careful choice of reaction conditions. The two vital factors for
the successful operation of the Fisher-Tropsch process are: 1-Accurate control of
temperature 2-Provision of an active and long-lived catalyst.

3.Hydro-Processing

This is the final step in shaping up the final products. The wax and the hydrocarbon
condensate produced by the Fisher-Tropsch process is predominantly linear paraffin
with a small fraction of olefins and oxygenates. By using hydrogen, the main chemical
reactions taking place in hydro-processing are:-

1- Hydrogenation of the olefins and oxygenates

2- The hydro cracking of the wax to naphtha and diesel

Hydro processing can be done at relatively mild conditions. In the design of

hydrocracker, a balance must be found between the per-pass conversion, diesel
selectivity and diesel properties. The higher the per pass conversion, on one hand, the
smaller the cracker will be due to less recycle of material back to the cracker. This will
be however, at the expense of the diesel selectivity, since over-cracking of the liquid to
gases will occur.

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Trends in the development of GTL technology and commercial applications

A survey of the existing GTL plants is given first, to indicate the most recent trends
taking place in synthesis gas production and the corresponding F-T process :-

Name of comp.& Locat. Need of O2 Syngas Ref. FT Syngas Cat. capacity (bbl/day)

JOGMEC/Japan No Tubular Slurry bed (Co) 7 (pilot unit

Sasol /South Africa Yes ATR Slurry bed (Co) 17,000 (2 units)

Shell/ Malaysia Yes NCPO Fixed bed (Co) 3,000 (4 units)

ExxonMobil/USA Yes ATR Slurry bed (Co) 200

(demonstration)

Conoco/USA Yes CPO Slurry bed (Co) 400

(demonstration)

BP/USA Yes Compact reformer Slurry bed (Co) 300

(demonstration)

ATR: Auto-thermal reformer, NCPO: non-catalytic partial oxidation, CPO: catalytic partial oxidation

Today, South Africa is the world’s leading producer of liquid fuel from natural gas (GTL
Technology).Sasol is a synfuel technology supplier established to provide petroleum
products in coal-rich, but oil-poor South Africa. The firm has built a series of Fisher-
Tropsch coal-to-oil plants. It has developed the world’s largest synthetic fuel project, the
Mossgas complex at Mossel Bay in South Africa that was commissioned in 1993.

The following is a list of some major companies with estimated capacities of existing
and potential GTL plants that they undertake in different parts of the world:-

Shell Iran 75,000

Sasol Iran 110,000

NNPC Nigeria 30,400

Shell Malaysia 12,500

Syntroleum Peru 40,000

Shell-OPC Qatar 75,000

ExxonMobil-OPC Qatar 100,000

Sasol-OPC Qatar 34,000

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PetroSA South Africa 30,000

ANGTL USA 50,000

POVSA Venezuela 15,000

Total Production 980,000

(bbl/day)

Conclusions and Recommendations

1. Fisher-Tropsch technology plays a key role in the GTL conversion process. It offers an
effective means to use untapped natural gas resources and a diversification of fuel
resources by ensuring substitutes for crude oil. GTL not only add value, but capable of
producing products that could be sold or blended into refinery stock as superior
products with clean-burning properties. Diesel fuels produced by the process have an
energy density comparable to conventional diesel, but with higher cetane number. This
should be considered the most significant advantage of GTL process.

2. GTL process needs low-cost natural gas as a feed stock; less than $1.0 per million Btu
to compete with traditional diesel fuels. Some sources of remote natural gas called
“stranded gas”, that are not otherwise economically available will be ideally suited for
this process. Examples are: Alaska and Qatar. GTL in operation today, converts 10,000
cubic feet (286 cubic meters) of natural gas into slightly more than one barrel of liquid
(synthetic fuel).

3. While the cost of producing GTL fuel has been declining as a result of using better
catalysts, scale up and plant design, the transport and distribution costs are slightly
higher compared to refinery-produced fuels. Research and development is focused on
reducing costs further. Examples are cited for Co catalysts as follows: Increasing the
catalyst life by making it more resistant to irreversible sulfur poisoning. Changing the
selectivity dependency on the H2/CO ratio to such an extent that high diesel yields can
be obtained at H2/CO ratios similar to the usage ratio.

4. Converting natural gas to liquid fuel benefits the environment in producing clean
fuels, Fisher-Tropsch process manufactures diesel with zero sulfur. In addition, GTL
encourages oil producers to utilize the associated gas produced in the oil fields and not
to be flared.

5. Associated natural gas could be converted to petroleum fuels and blended with
heavy crude oils. This will upgrade the quality of the crude and cut, at the same time,
the expenses incurred in collecting and transporting the associated gas.

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6. The composition of the HC feed stock sets the preferred conversion routes for the
production of liquid transportation fuels- eg: Gasoline or Middle Distillate Fuels
(kerosine/gas oil):when the C/H ratio of feed stocks and products are well matched; as
with the case: coal aromatic gasoline, and with natural gas middle distillates, then
a relatively high theoretical efficiency is possible. If the C/H ratio of the feed/products
differs substantially, rejection of C or Hydrogen- as the case may be – is inevitable and
lower conversion efficiencies are the result. This is schematically illustrated in Figure 5.

References
1- Abdel-Aal, H.K. and M. A. Shalabi (1996), “Non Catalytic Oxidation of Sour
Natural Gas versus Catalytic Steam Reforming of Sweet Natural Gas”, Ind
.Eng. Chem. Res., Volume 35, number 5, Pages 1785-1787
2- Abdel-Aal, H. K. et al (1999)“Simulation of the Direct Production of
Synthesis Gas from Sour Natural Gas by None Catalytic Partial Oxidation
(NCPO): Thermodynamics and Stoichiometry, Volume 38, Number 3, Pages
1069-1074

3- Bartholomew, C.H. (1991), “Recent Developments in Fischer-Tropsch Catalysis”,

New Trends in CO Activation, Ed. L. Guczi, Elsevier Publishing Company

4- Bradner, T. (2002), “BP to produce its first barrels of GTL by April,” Alaska Oil %&
Gas Reporter(March 6.

5- Ennique Iglesia et al(1995)”F-T synthesis on Fe-based catalyst”www.fisher-

tropsch.org/DOE/DOE_reports/40308

6- Singleton, A. H. (1997), “Advances Make Gas -to-Liquids Process Competitive for

Remote Locations”,Oil & Gas J journal, August 4.

7- Thackeray, F.(2003). “GTL in 2007”, Petroleum Review, January, Pages, 10-19.

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