SPE 93580

GTL Update
G. Apanel, SRI Consulting

Copyright 2005, Society of Petroleum Engineers Inc.

This paper was prepared for presentation at the 14th SPE Middle East Oil & Gas Show and
Conference held in Bahrain International Exhibition Centre, Bahrain, 1215 March 2005.
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Abstract
Proven world natural gas reserves, which currently exceed
5,000 trillion cubic feet (TCF), have been growing at a faster
rate than proven oil reserves. These gas reserves currently
represent over 83% of the energy equivalence of proven oil
reserves, of which about 75% is considered to be the less
desirable heavy crude. In some remote locations, wellhead
costs of natural gas have been estimated to be below
$0.25/MMBtu, while the cost of reinjecting associated gas
from crude oil production as an alternative to flaring may
greatly exceed its value. About 3,000 TCF of such gas
reserves is considered to be stranded; i.e., accessible by
drilling but located too far from potential markets for
economical transportation to those markets.
The chemical conversion of methane to liquid fuels and
other higher value products or derivatives which may be more
cost effective to transport long distances from remote gas
sources has therefore attracted renewed interest. Even though
Fischer-Tropsch (FT) synthesis is a technically proven gas-toliquids (GTL) technology, the conversion of natural gas to
liquid fuels such as diesel and gasoline as opposed to higher
value chemical products such as chemical grade methanol has
only relatively recently been perceived to be a potentially
viable commercial proposition. Recent advances in FT
synthesis technologies, particularly with regard to natural gas
reforming and catalytic partial oxidation, coupled with
anticipated increased demand for clean diesel fuel appear to
be enhancing the economic viability of this route to GTL.
The focus of this paper is the prospective economics of
promising technologies for FT based GTL diesel production.
The scope of this paper includes a brief discussion of
potentially important new developments which could have a
significant impact on GTL process economics.

Introduction
Gas-to-liquids (GTL) technology generally entails the
chemical conversion of natural gas into readily transportable
liquids such as methanol or conventional petroleum refinery
type distillate fuels. More recently the term GTL has also been
more loosely applied to physical conversion processes such
as that for liquefied natural gas (LNG) as well as for chemical
conversion processes that produce products which may not be
in a liquid state under ambient conditions, such as
dimethylether (DME). In this paper, we focus on GTL
technologies based on the production of diesel fuel via
Fischer-Tropsch synthesis (FTS).
FTS generally involves the synthesis of hydrocarbons
and oxygenates from synthesis gas (syngas) consisting
primarily of a mixture of CO + H2. The types of hydrocarbons
produced can include olefins such as ethylene and propylene,
and an extremely wide range of saturated hydrocarbons
ranging from methane and ethane to long straight chain
paraffinic waxes. The oxygenated materials that are produced
consist primarily of alcohols such as methanol and ketones
such as acetone.
When configured to maximize the
production of paraffinic hydrocarbons, the resulting
intermediate product mix is often described as synthetic
crude oil (syncrude). Such syncrudes can be readily refined
into desirable distillate fuel fractions such as kerosene,
naphtha, and heating oil using conventional petroleum refining
techniques. The kerosene can be further refined or blended
into high quality diesel or jet fuel products while the naphtha
can be further refined into gasoline or used as a thermal
cracking feedstock for olefins production.
Catalysts for FTS were first developed in the early
1900s. Following the discovery by Sabatier and Senderens in
1902 that CO could be hydrogenated over Co, Fe, and Ni
catalysts to methane, BASF reported the production of liquids
over Co catalysts in 1913. Fischer and Tropsch later reported
production of hydrocarbons over alkalized iron in 1923. Much
of the early catalyst and process development continued in
Germany during the 1930s and 1940s. During World War II,
coal based FT production played an important role providing
the transportation fuel requirements of the German war effort
because of insufficient access to crude oil resources. This
production was discontinued when the war ended.
After the war, developments by Ruhrchemie and Lurgi of
Germany and by Kellogg Co. of the United States led to the

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SPE 93580

commissioning of the first commercial synfuels plant (Sasol I)

outside of Germany in Sasolburg, South Africa during 1955.
The Republic of South Africa had no option but to develop its
own synthetic fuels program from the low-cost coal
abundantly available because of political isolation and trade
sanctions being imposed against the country. The Sasol
program was expanded in the early 1980s with the
construction of two new coal-based units in Secunda (Sasol-II
and Sasol-III) for the production of various types of fuels and
chemicals.

Primary Process Steps in GTL Diesel Production

Four key process steps are generally required for FT
based GTL diesel production:

Sasols coal based synfuels program was therefore

initially motivated by political exigency and local feedstock
availability rather than economics. Commercial interest in
synfuels technologies began to develop elsewhere during the
1970s because of the rapid rise of crude oil prices. This
interest further intensified in early 1980s because of new
uncertainties over oil supplies from the Middle East and
further price increases. Interest waned again when oil supply
exceeded demand and oil prices fell. At that time, the
production economics of coal based synfuels were not found
to be favorable relative to crude oil products. Conventional FT
catalyst and process technologies available at the time were
faced with the following primary limitations, especially for
coal based feedstocks:

4. Fractionation of the distillates into the predominantly

diesel product, along with some byproduct kerosene,
naphtha, heating oil, and LPG type fuels.

High capital cost

Less than desirable thermal efficiency
Limited premium product selectivity
Inefficient
removal

reaction

1. Syngas generation with a minimum H2/CO ratio of

just over 2:1.
2. FT synthesis of paraffin rich hydrocarbon liquids.
3. Mild hydrocracking of the waxy paraffins to a diesel
rich middle distillates fraction.

A typical net product distribution appears to be roughly

in the following ranges for a thermally balanced plant where
internal process heat requirements are at least partially
satisfied by byproduct fuel utilization:
Diesel

35 - 45%

Kerosene

25 35%

Naphtha

20 30%

Heating Oil

0 - 5%

If a separate kerosene product fraction is not desired, it

may be blendable with the diesel product and thereby increase
the diesel product make proportionately. Figure 1 is a
simplified illustration of key steps in a general GTL
processing scheme.

heat

Catalyst deactivation, attrition,

and
inefficient
catalyst
recovery systems

CO2

CH4

LPG

Natural Gas
Natural

H 2O
Steam or Water

Step 1

Reforming

(Optionally) O2

More recently, the growing

Oxygen or Air
Heat
availability of massive natural gas
Catalyst
reserves, rising oil prices, increasing
environmental concerns, and gradual
improvements in FT and related process
technologies appear to be enhancing the economic prospects
of FT based GTL processes. Sasol continues to play an
important role in GTL technology development along with a
growing number of new technology developers.
Worldwide demand for diesel fuel is currently projected
to grow at a more rapid rate than that for gasoline while
maximum allowable sulfur levels and other specifications for
diesel are becoming particularly stringent. FT derived diesel
has been shown to exceed such specifications. These factors
currently appear to be stimulating interest in FT based GTL
diesel production based on recent project announcements, as
opposed to other FT based products.

CO and H2

Step 2

C5 C35

Step 3

C5 C19

Fischer-Tropsch

F-T Liquids

Hydrocracking

Diesel

Syngas

C19 C35
Resid

Heat
Catalyst

Heat
Catalyst
High Pressure

Figure1
General GTL Processing Scheme

Syngas Generation Technologies

Since most of the capital investment for a GTL plant is
associated with the syngas generation step, this has been an
area of intensive development by a number of licensers. Six
principal technologies for syngas production from natural gas
have been commercialized or are currently at an advanced
stage of development:
1. Steam methane reforming (SMR)
2. Autothermal reforming (ATR)
3. Non-catalytic partial oxidation (POX)
4. Catalytic partial oxidation (CPOX)

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SPE 93580

5. Heat exchange reforming (HER)

6. Compact reforming (CPR)
Steam Methane Reforming (SMR)
Steam methane reforming is currently a widely practiced
technology for hydrogen rich syngas production, used
primarily for smaller capacity methanol plants with production
capacities under 2500 t/d. It involves reacting steam with
methane over a Ni based catalyst via the following reaction
stoichiometry:
CH4 + H2O CO + 3H2, (+49.3 kcal/mol)

(1)

Typical operating temperatures and pressures for a

conventional SMR unit are 1600F (871C) and 300 psig at the
outlet. Because the reaction is strongly endothermic, a major
challenge and often the limiting factor in the design of a SMR
unit is providing sufficient heat into the reactor system to
maintain the required reaction temperatures. The reaction is
therefore typically conducted in an externally fired tubular
reactor resembling a large fuel fired furnace for conventional
reactor configurations. Aside from being extremely large
from the standpoint of physical dimensions, such units are
very costly from the standpoint of capital investment, steam
and fuel consumption. A substantial amount of excess steam
is required to prevent coking of the reactor tubes, typically
2.5:1 in terms of total molar steam to carbon ratio. Another
drawback of this technology is that the H2/CO ratio produced
(3:1) is much higher that the 2:1 ratio required for the
downstream FTS unit.
Autothermal Reforming (ATR)
During autothermal reforming, a mixture of steam,
methane, and oxygen is reacted adiabatically over a fixed bed
of Ni based catalyst in current commercial syngas
applications. In addition to the SMR reaction (1), a number of
other reactions also occur as typified by the following:
Oxidation
CH4 + 2O2 CO2 + 2H20, (-191.8 kcal/mol)

(2)

CH4 + 1/2O2 CO + 2H2, (-8.5 kcal/mol)

(3)

CO Shift
CO + H2O CO2 + H2, (-10 kcal/mol)

(4)

The heat requirement for the endothermic SMR reaction

(1) is provided by the exotherm generated by the oxidation
reactions (2 & 3). Excess hydrogen from the SMR reaction
(1) reacts with CO2 from oxidation reaction (2) to form
additional CO in accordance with the thermodynamic
equilibrium of the well-known CO shift reaction (4). These
reactions are believed to occur in essentially two sequences in

down flow mode within the confines of a refractory lined

pressure vessel containing the fixed catalyst bed. The
oxidation reactions occur immediately upon introduction into
the vessel through a burner nozzle in the vapor space above
the fixed catalyst bed. The SMR and CO shift reactions
apparently subsequently occur in the catalyst bed, resulting in
syngas exit temperatures from the ATR of approximately 1750
1922F (954 1050C).
Aside from being much smaller and requiring a much
lower investment than a SMR, an advantage of this approach
to syngas generation is that the H2/CO ratio is closer to the
desired level of about 2:1 for FT synthesis. Although excess
steam is also required to prevent soot formation, considerably
less is required than that for an SMR. Despite the additional
cost of a cryogenic oxygen plant or an air compressor for air
blown units, ATRs appear to be generally more economical
than conventional SMRs for large-scale FT diesel
applications.
Noncatalytic Partial Oxidation (POX)
For non-catalytic partial oxidation, also referred to as
gasification in most commercial installations, oxidation
reactions (2 & 3) generally appear to predominate to a greater
extent with generally less steam required than that for an ATR
to achieve a similar H2/CO ratio of 2:1. Higher reaction
temperatures of around 2372F (1300C) are generally
required to convert natural gas, thereby resulting in a possibly
higher oxygen requirement in some reactor configurations.
Shell appeared to favor this approach to syngas production in
their GTL process, at least for earlier variations of their
technology. The reactor typically consists of a refractory lined
open pressure vessel configuration. Some soot typically forms
in the POX effluent, which may require provision for soot
removal by downstream scrubbers prior to FT processing.
Catalytic Partial Oxidation (CPOX)
CPOX represents an interesting new approach to syngas
production, which has yet to be commercialized. Among the
potential advantages claimed in the literature for this
technology relative to ATR and POX units are a lower oxygen
consumption while requiring essentially no steam
consumption for operating temperatures under 1000C
(1832F). Because of the severe catalyst operating conditions
and the importance of suppressing soot formation with
minimal steam consumption, best results reported in the
available published literature appear to favor the use of
rhodium (Rh) based monolithic catalysts for such a service.
Aside from durability and resistance to coke formation, other
important catalyst selection considerations are cost, activity
and natural gas conversion. A drawback of rhodium is that on
a unit weight basis, it is among the most expensive of the
noble metal catalysts.

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SPE 93580

The potential advantages of CPOX for large-scale syngas

production have recently been the object of intensive
development by ConocoPhillips and other companies.

Fischer-Tropsch Synthesis Technology (FTS)

Three basic reactor configurations have been commercially
applied to FTS:

Heat Exchange Reforming (HER)

1. Tubular (also referred to as fixed bed)

Heat exchange reforming of natural gas generally

involves a promising two-stage approach to syngas production
which is currently undergoing advanced demonstration runs
but has not yet been commercialized. The first reforming
stage resembles a conventional heat exchanger in some
respects, in which SMR type conversion reactions occur in the
catalyst filled tube side of this reactor. The second stage
typically consists of a conventional ATR. The heat of reaction
required by the tube side SMR reaction is provided by the hot
effluent syngas from the ATR second stage. Among the
advantages claimed for this approach to natural gas reforming
are lower capital cost and higher thermal efficiency. Oxygen
consumption is claimed to be lower than that for a single stage
ATR while steam consumption is claimed to be lower than
that for a single stage SMR. One leading developers of this
technology, ICI, appears to be initially targeting Mega
methanol plant applications although they claim that it should
be equally applicable to GTL. Air Products has also been
developing HER technology.

2. Fluid bed (fixed and circulating)

Compact Reforming (CPR)

Compact reforming represents a novel mechanical design
approach to conventional SMR. Under development by BP, it
is currently undergoing extended test runs at their new 300 b/d
GTL demonstration facility in Alaska. Their reformer design
also appears to resemble a conventional shell and tube heat
exchanger, which is much more compact than the
conventional SMR furnace design configuration. The SMR
reactions occur tube side of this reactor, with the tubes filled
with conventional Ni based catalyst. Heat for the endothermic
SMR reactions is provided shell side, where the tubes are
heated by combustion of fuel and air mixture in a sea of
flames. Heat transfer is claimed to occur more efficiently in
what is described as a highly countercurrent device.
According to our review of the available patent literature, the
shell side combustion zone may also be under elevated
pressure. Such elevated pressure may also contribute to more
efficient convective heat transfer to the tubes. Relative to a
conventional SMR, considerably less catalyst is required while
the size of the unit is also considerably reduced hence the
term compact reforming coined by BP. The principal
advantages claimed for this approach compared to a
conventional SMR are a major reduction of capital cost along
with an improvement in thermal efficiency. The reduced
space requirements are claimed to make this reforming
technology more amenable to installation on barges or ocean
going plantships for the conversion of relatively small or
temporary sources of natural gas. A drawback of current state
of this technology is that a large number of parallel units
would be required for a world scale GTL plant.

3. Slurry phase (also referred to as a slurry bubble

column)
Because of the highly exothermic reactions involved in
FTS, a key factor in reactor design is the efficient removal of
reaction heat and maintaining reasonably uniform temperature
conditions. Among the factors influencing the choice of
reactor configuration are production scale and whether the
crude FT product is a gas or liquid phase under the reaction
conditions. Other factors are catalyst attrition resistance and
recovery as well as susceptibility to coking and the resulting
regeneration requirements. Since the commercial catalysts
used are extremely susceptible to sulfur poisoning, upstream
sulfur removal facilities or guard beds for the natural gas
feedstock or syngas intermediate are generally required. This
helps to assure an essentially sulfur free GTL product.
Depending on reaction conditions, the type of catalyst
used, and the reactor configuration, Fischer-Tropsch synthesis
can be used to produce alkanes, alkenes, or oxygenates such as
alcohols via the following generalized overall reaction
stoichiometry:
Low Temperature Fischer-Tropsch Synthesis
nCO + (2n+1)H2 CnH(2n+2) + nH2O

(5)

High Temperature Fischer-Tropsch Synthesis

nCO + 2nH2 CnH2n + nH2O

(6)

nCO + 2nH2 C(n-1)H(2n-1)CH2OH + (n-1)H2O

(7)

The production of middle distillates and diesel fuel via

FTS entail the synthesis of alkanes as a crude reaction product
as indicated by Reaction (5). Reaction temperatures of around
220-270C (428-518F) is generally required for this reaction
which is commonly referred to as Low Temperature FischerTropsch (LTFT) synthesis. A tubular or slurry phase reactor
configuration using a Co based catalyst is generally used.
The synthesis of olefins and oxygenates are favored by
higher temperatures of around 300-350C (572-662F) as
respectively indicated by Reactions (6) & (7). This is
therefore generally referred to as High Temperature FischerTropsch (HTFT) synthesis, and is commercially conducted
using an iron-based catalyst in a fluid bed reactor
configuration.
During FTS, intermediate products from all three of the
above reactions may form simultaneously to some extent

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SPE 93580

during the synthesis, regardless of whether it is LTFT or

HTFT.
Equilibrium calculations indicate that for the
simultaneous formation of methane, ethane, n-pentane and
propylene for example that methane formation is highly
favored over that of hydrocarbons with the higher molecular
weight. For this reason, the development of catalysts with
high selectivity for hydrocarbons other than methane has been
a major challenge for technology developers.
FTS Product Distribution
The hydrocarbon synthesis reactions involved in FTS
may be regarded as analogous to a polymerization reaction.
An essential characteristic of catalysts applied to FT diesel
production therefore is the ability to catalyze chain
propagation versus chain termination steps. The specific
selectivity for a particular hydrocarbon and the overall product
distribution may generally be described by a chain
polymerization kinetics model involving the stepwise addition
of one carbon to another on the growing chain. This model
has been ascribed to Anderson, Schultz, and Flory and is
commonly referred to as the Anderson-Schultz-Flory (ASF)
model. The ASF product distribution may be mathematically
represented by the following equation:
wn/n = (1 )2

(n 1)

(8)

where
n = number of carbon atoms in the hydrocarbon molecule
wn = weight fraction of product containing n carbon
atoms
= chain growth propagation probability
Higher values of generally correspond with increasingly
heavier hydrocarbon selectivity as desired for FT diesel
production, as determined by the choice of reaction conditions
and catalyst. Values of therefore increase with decreasing
reactor temperature as would be expected for LTFT. Since
values of also increase with decreasing H2/CO ratio and
increasing reactor pressure, such conditions would also tend to
favor FT diesel production relative to lighter hydrocarbon
product distributions
The following tabulation summarizes the FT crude
product weight fractions for two different values of chain
growth probability ():
Crude Product Cut

= 0.80

= 0.95

Carbon #

Wt%

Wt%

Gas

C1 C4

27.2

2.5

Naphtha

C1 C9

35.9

6.7

Diesel

C10 C19

30.1

18.5

Soft Wax

C20 C34

6.4

27.3

Hard Wax

C35+

0.4

45.0

Description

Hydrocracking Requirements for FT Diesel

Production
The indicated wax fractions in the crude product may be
converted to additional diesel via mild hydrocracking using
conventional technologies, such as that offered for license by
Chevron or UOP. The syngas generation unit must therefore
produce some excess hydrogen beyond FTS stoichiometric
requirements. Typical hydrocracking reactor conditions entail
temperatures of 320-400C (608-752F) and pressures of
1000-1500 psig.
FT Naphtha Conversion Options
The indicated naphtha fraction produced may be further
upgraded to gasoline via catalytic reforming. Alternatively, the
naphtha could be used as a steam cracker feedstock for olefins
production.
Summary of Principal GTL Technology Developers
Gas-to-liquids and related synfuel technology is an area of
intensive development activity by a number of companies.
Leading companies in this field include; Sasol Chemicals Ltd.
(South Africa), Shell International (Netherlands), Syntroleum
Corp. (United States), ExxonMobil (United States),
ConocoPhillips (United States), and BP (British Petroleum).
With the possible exception of Shell, all of the above
developers appear to be favoring the use of slurry phase FT
technology for diesel production. Shell appears to be favoring
tubular FT design configurations, at least for smaller scale
plants. Syntroleum GTL technology is based on air blown
reforming of natural gas, as opposed to pure oxygen.
ExxonMobil initially appeared to base their technology on an
innovative fluidized bed reactor for natural gas reforming, but
may more recently be favoring ATR based reforming. Aside
from their previously mentioned CPOX reforming technology,
ConocoPhillips has recently patented an innovative approach
to FT synthesis via reactive distillation. This could reduce
GTL costs by simplifying product recovery and improving
yields. BP has proposed the use of a low boiling solvent for
their slurry phase FT synthesis technology.
GTL Production Economics
SRI Consulting has evaluated the process design, capital
investment requirements, and cost of production economics
for a wide variety of GTL processes, including those under
development by the above technology developers. Preliminary
conceptual design schemes were developed on the basis of our
interpretation of nonproprietary information derived from the
public domain. Aspen simulation models were developed,
sized equipment lists compiled, and vendor quotes were
obtained in performing the assessment via our PEPCOST
program. Our economic assessments were based on a total
product production capacities of approximately 50,000 b/d,
which was extrapolated from base case design capacities of
approximately 12,000 b/d.

Source: Rentech

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SPE 93580

In this paper, we present our estimated cost of production

product values for three of the GTL design cases which we
have evaluated (References 1 & 2). These cases differ
primarily in terms of the type of reformer and FT synthesis
reactor technologies assumed for these key process steps. Case
1 is based on an ATR type reformer with a slurry phase FT
reactor. This case may be regarded as representative of the
current conventional state of the art for FT based diesel
production. Case 2 is based on our concept of a proposed
CPOX unit for the front end reforming but with a slurry phase
FT reactor. Case 3 is based on a similar ATR front end with
our concept of a proposed reactive distillation unit as derived
from the patent literature to conduct the FT synthesis. Case 2
and especially Case 3 should be regarded as speculative since
the CPOX and reactive distillation technologies assumed do
not yet appear to be commercially proven for FT based diesel
production.

Conclusion
FT diesel production from stranded natural gas currently
appears to be an economically attractive proposition if crude
oil prices remain above $35/b and if the natural gas feed is
available at a cost of $0.50/million Btu. The successful
commercialization of CPOX and reactive distillation
technologies could further enhance the economics of GTL.
Based on information available in the public domain, the
economic impact of CPOX and reactive distillation
technologies does not currently appear to be particularly
significant but would warrant further investigation and
development work in order to realize their full potential.
References
1.

Apanel, G.J., Gas-To-Liquids Update, PEP Report

247, Process Economics Program, Menlo Park,
California (December 2002)

2.

Apanel, G.J., Fischer-Tropsch Synthesis via Reactive

Distillation, PEP Review 2000-13, Process Economics
Program, Menlo Park, California (April 2003)

3.

Chang, T., Conoco Says Economies of Scale Key to

GTL Viability, Oil and Gas Journal, 98, 31 (2000),
46-47

4.

Parkinson, G., A New Era for Gas-To-Liquids

Technology, Chemical Engineering, V. 109, 7
(2002), 27-31

GTL Diesel Product Value Comparisons:

Case 1

Case 2

Case 3

Reformer Type

ATR

CPOX

ATR

FT Reactor type

Slurry

Slurry

35.4

33.3

Diesel Prod Val, $/b

Reactive Dist
34.0

Source: SRI Consulting (References 1 & 2)

The above product values are based on stranded
natural gas feedstock at a cost of $0.50/million Btu at an
assumed plant site at a remote location. These figures include
a 10% annual depreciation allowance with a 25% pretax return
on investment. Based on the above preliminary product value
calculations, FT diesel production should be profitable if
prevailing crude oil prices remain above $35/b. The use of
CPOX technology would represent the most economical case
as indicated by Case 2, reducing the diesel production cost by
about 6% on the basis of our estimates. The application of
reactive distillation technology to the FT step would also
improve economics relative to Case 1, but not to the extent as
for Case 2 on the basis of currently available information
about these technologies. While the estimated economic
impact of these technologies as summarized above do not
currently appear to be particularly significant, we believe that
the economic impact could be much more substantial if the
full potential of these technologies are ultimately realized. For
a design case incorporating both CPOX for reforming and
reactive distillation for FT synthesis, the cumulative reduction
in diesel production cost should be essentially additive,
thereby resulting in a maximum production cost reduction of
around 10% relative to Case 1.

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