Chapter 32

NATURAL GAS AS FEEDSTOCK

Jacques C. Védrine
Laboratoire de Physico-Chimie des Surfaces, ENSCP, 11, rue P. & M. Curie, F- 75005 Paris,
France

Abstract: Natural gas is a very cheap and abundant raw material but its main
components, methane, ethane and propane, are rather chemically inactive
compounds, which makes their upgrading to more valuable products quite
difficult. Moreover the natural resources are often quite far from consumers,
which makes their commercialisation even more difficult. However, in the last
thirty years, natural gas has seen its importance growing tremendously due to
the increase in price of oil and its expected and inexorable shortage in a more
or less far future.
The actual challenge is then to use natural gas as an important feedstock and
to transform it to more valuable compounds. There are two ways:
1 - The industrially applied processes based on partial oxidation to syngas
(CO+H2) and its further transformation to synfuel or methanol;
2 - All chemical transformation to other compounds such as direct partial
oxidation to methanol or formaldehyde, or direct conversion to aromatics or a
variety of hydrocarbons, etc.
In this paper we are considering the actual state of the art in industrial
processes and summarising all ideas expressed during a workshop held at a
NATO-ASI in July 2003 in Vilamura, Portugal, as possibilities for the future.

Key words: Natural Gas, Feedstock, challenges, running processes, new reactions of
methane and new products

403

E.G. Derouane et al. (eds.), Sustainable Strategies for the Upgrading of Natural Gas:
Fundamentals, Challenges, and Opportunities, 403–412.
© 2005 Springer. Printed in the Netherlands.
404 Jacques C. Védrine

1. INTRODUCTION

Natural gas as feedstock is a real challenge since it involves all

bottlenecks met in conversion of light alkanes. Depending on the source of
natural gas, it contains various and non negligible amounts of methane
(major), ethane, propane and other alkanes and its price depends mainly on
its geographical location, since its resources are rarely located in areas with
high population. Therefore, natural gas price reflects it. For chemical
industries the main application, at present, consists in partial oxidation to
syngas (CO+H2).
Such syngas technology dates from the beginning of the last century,
with deployment of the so-called Haber-Bosch process in 1917, developed
in Germany. The process comprises endothermic reaction of steam reacting
with coke producing hydrogen according to [1] followed by the slightly
exothermic water gas shift reaction WGSR [2]and Boudouard reaction [3]:

C + H2O ĺ CO + H2 (1)
CO + H2O ' CO2 + H2 'H = -41 kJ mol-1 (2)
2CO ' C + CO2 'H = -172 kJ mol-1 (3)

The gas obtained is rich in hydrogen and was used in the Haber process
for ammonia production by adding nitrogen and in the Fischer-Tropsch
process for the conversion of coal to liquid fuels.
The concept of activating methane via analogous reactions of steam
reforming was investigated in Germany at about the same time. In the 1950s
it appeared that naphta could be steam reformed economically to provide a
cheap source of hydrogen. Many plants were then constructed, when
methane sources were too remote or not easily available. In the past 25
years, natural gas was increasingly available as the main feedstock for steam
reforming. Two applications of syngas are becoming of increasing
importance:

x Manufacture of liquid fuel from remote or marginal natural gas resources

(Fisher-Tropsch route being major);
x Generation of hydrogen for fuel cells

The sources of natural gas remaining in 2003 amount to ca. 180 trillions
m3, corresponding to 70 years of production at 2001 level [1]. The Middle
East has the greatest remaining resources with 40%, followed by former
Soviet Union. Production equaled 3 trillions m3 per year in 2000 with 92%
sold and the 8% remaining being re-injected or flared. At present the largest
producer is North America (33%), followed by Middle East (26%), Western
Natural Gas as Feedstock 405

Europe, andformer Soviet Union (11.5%), Africa (11.2%), Asia & Oceania
(8.9%), etc. “fire ice”-methane hydrates on ocean bottoms may be estimated
as 8,000 trillions cubic metres.
The conversion of natural gas to methanol via CO+H2 or to synfuel is the
most widely practiced actual route to added value. The first step is the
conversion of natural gas to syngas, which in turn is converted to synfuel,
with 65% of cost associated with the production of syngas. Several routes to
syngas are possible and different processes giving different CO/H2 ratio
values, as schematized in the reactions given below in part 2. Syngas does
represent the best route for hydrogen (as source for NH3, etc.), H2-CO
(methanol, for MTO, MTP, MTG processes), for H2-CO (FT products,
waxes, lubricants, etc.). The MTO (methanol to olefines, mainly ethylene
and propylene) process has recently overcome the exploratory phase with
two technologies, the methanol to olefines by Hydro/UOP on SAPO-34
zeolitic material and the methanol to propylene on proprietary zeolite
catalyst by Lurgi/Statoil. The old MTG process from Mobil on ZSM-5
zeolite was only developed industrially in New Zealand and produces
currently mainly methanol. The production of hydrogen in syngas process
will be increasingly important, for instance for solid oxide fuel cell (SOFC)
or for all hydrotreating catalytic reactions. The objective in fuel cell is to
convert methane or hydrogen or other fuel directly to electricity as expressed
by the Nernst equation (E0 = n'G0), i.e. ideal efficiency is expressed by
'G0/'H0 for the overall combustion reaction.

2. PROCESSES OF INDUSTRIAL APPLICATIONS

The choice of the syngas technology is dictated by the need for high
conversion, the requirements for syngas composition and the scale of
operation. Lets us consider several of these reactions:

2.1 Steam reforming:

CH4 + H2O ' CO + 3H2 'H = +206 kJ mol-1 (4)

CnHm + nH2O ' nCO + (n+m/2)H2 'H = +1175 kJ mol-1for nC7H16 (5)
CO + H2O ' CO2 + H2 'H = -41 kJ mol-1 (2)
406 Jacques C. Védrine

2.2 CO2 “Dry” Reforming:

CH4 + CO2 ' 2CO + 2H2 'H = +247 kJ mol-1 (6)

2.3 Catalytic partial oxidation (CPO):

CH4 + ½O2 ĺ CO + 2H2 'H = -36 kJ mol-1 (7)

2.4 Autothermal reforming (ATR)

CH4 + 3/2O2 ' CO + 2H2O 'H = -519 kJ mol-1 (8)

CH4 + H2O ' CO + 3H2 'H = +206 kJ mol-1 (4)
CO + H2O ' CO2 + H2 (WGSR) 'H = -41 kJ mol-1 (2)
CH4 + ½ O2 ' CO+ 2H2 'H = -36 kJ mol-1 (7)

2.5 Total Oxidation

CH4 + 2O2 ĺ CO2 + 2H2O 'H = -802 kJ mol-1 (9)

Steam and CO2 reforming reactions are strongly endothermic and, hence,
the manufacture of syngas requires a high temperature to achieve high
methane conversion. The overall heat of reaction becomes negative, which
implies that heat should be supplied to the system. Note that dry reforming is
not yet practiced industrially, although its CO/H2 ratio is more suitable for
FT reaction process than steam reforming reaction. It was studied in the 50s
on Ni catalyst by M. Prettre et al. [2].
Classic Fischer-Tropsch (FT) reaction on Co or Fe based catalysts
converts syngas to synfuel, i.e to mixtures of hydrocarbons, particularly
waxes. The main products are n-paraffins for more than 90% together with
olefines and alcohols. The molecular weight distribution follows the
Schultz-Flory model.
Methane is firstly converted to syngas, which may then be processed to
give alcohols and hydrocarbons [3-8]:
Natural Gas as Feedstock 407

CH4 + H2O ' CO + 3H2 'H = +206 kJ mol-1 (4)

CH4 + CO2 ' 2CO + 2H2 'H = +247 kJ mol-1 (6)
CH4 + ½ O2 ' CO + 2H2 'H = -36 kJ mol-1 (7)
CO + 2H2 ' CH3OH (10)
nCO + (2n+1)H2 ' CnH2n+2 + nH2O (11)

The production of methanol is an important industrial reaction with high

yield on Cu/ZnO-Al2O3 type-catalysts as in the process developed by ICI
long time ago. The production of synfuel via the Fisher-Tropsch process [7]
is economically less attractive and is used in only few places. However, the
expected ineluctable shortage of crude oil has led to serious consideration of
wider applications of methane sources.

3. PROCESSES NOT YET INDUSTRIALLY APPLICABLE

The obvious attraction of the direct processing of natural gas to obtain

more valuable products has led to the study of oxidation (oxidative coupling
in the 70s), NO catalysed oxidation and direct oxidation to formaldehyde or
methanol on MoO3/SiO2 catalyst, of reactions with halides or sulfates and of
pyrolysis based reactions. Only high temperature pyrolysis has been
exploited industrially, the other processes based on these reactions were
more or less abandoned for economical reasons. Many studies were
performed in the 70s by industry and 80s in academia of oxidative coupling
of methane at high temperature (>650oC) on basic complex oxides (e.g.
MgO, doped with rare earth-based oxides [9]) with formation of
ethane/ethylene. This tentative failed for economical reasons, as a 20%
maximum yield in C2 hydrocarbons was reached.
It therefore appears that alternative routes to syngas for C1 utilisation
remains a major challenge. This implies:

x New reactions for commodities, fine chemicals and functional chemicals;

x Revisiting our concept and ideas about energy, electricity, re-injection
and flaring issues;
x Implication on sustainable strategy (CO2, environment, etc.);
x Financial aspects, costs and profits;
x Careful analysis of 'T parameter, which is an important parameter of the
analysis, as described by J Rostrup-Nielsen in his paper [1]. It
corresponds to the price of product minus that of the feedstock minus
investment minus profit minus process running and minus energy spent;
x Great efforts in improving reactors efficiency by new chemical
engineering studies and processes should be emphasised. The use of
408 Jacques C. Védrine

membranes as gas distributors or removal of products or water may be of

importance for the future, if diffusivity problems are solved physically
(flow rates rapid enough to avoid huge reactors, resistance to membrane
deterioration during reactions, etc.) andeconomically speaking.

The most obvious idea to think about any possibility is to look at

methane dissociation or insertion of elements such as oxygen, according to
the following schemes:

3.1 CH4 decomposition:

CH4 ĺ C + 2H2, [12], 'H = + 75 kJ mol-1), 'S > 0, T > T* = 'H0/'S0

3.2 Direct oxygen insertion (oxidation)

One may then think about the following reactions:

x CH4 + ½ O2 ĺ CH3OH on H2SO4 (oleum)

x CH4 + O. ĺ CH3OH
x CH4 thermal decomposition on Ni or Ni alloy into H2 and carbon tubes
as pioneered by R.T. Baker from Exxon in the 70s;
x Photochemical dissociation of dioxygen into reactive O. (TiO2 solar)

Recent possibilities have been proposed as alternatives

x Oxidative coupling, which consists of converting methane to CH3o
radicals in the presence of oxygen and a basic doped oxide catalyst [9] at
ca. 700oC, see supra. The CH3o radicals couple to form ethane , which
thermally dehydrogenates to ethane under reaction conditions, according
to:

2CH4 + [(1+x)/2]O2 ĺ xCH2=CH2 + (1-x)CH3-CH3 + (1+x)H2O (12)

The process developed by ARCO could provide 16% yield at 20%

conversion and 80% selectivity, but was not economically attractive and
then abandoned;
x Oxidative esterification by two major routes, one to CH3Cl and the
other one to CH3OSO3H. The first route consists in converting
methane with O2 and HCl over oxychlorination catalyst with an yield
of 30%, much higher than the 2% for direct oxidation. For the second
route the methyl group can be protected to further oxidation by an
Natural Gas as Feedstock 409

electronegative group, such as HSO4-. Methane is then oxidised to

methylbisulfate with 80% yield per pass, using SO3 as oxidant
according to:

CH4 + H2SO4 + SO3 ĺ CH3-OSO3H + H2O + SO2

In a second step, methylbisulfate is hydrolysed to methanol and, then,

SO2 is oxidised to SO3. Note that traces of water are to be avoided, since
SO3 gives then H2SO4, which imposes drastic dried conditions, while
corrosive sulfuric acid limits application.
x Direct partial oxidation of methane to methanol at high pressure or
formaldehyde at low pressure. Many catalysts have been proposed,
but the reactions can occur, even without any catalyst. The yield
rarely exceeds 2% and is then not economically attractive;
x Non oxidative routes. Several routes have been proposed to convert
methane to olefines or aromatics without the use of oxidants:
x High temperature thermal pyrolysis to methane and ethyne [10]
x High temperature methane aromatisation, mainly to benzene and
naphthalene, at high temperature (>700 oC) using Mo/ZSM-5 catalyst
[11, 12] and assigned to MoC2 formed in ZSM-5 material during pre-
activation or reaction.
x Low temperature methane coupling via surface carbides [13].
x These processes necessitate swing-type reactors and are highly energy
consuming, at least for the first two, which limits their applicability.
x A rather recent and surprising finding is the observation that methane
can react with other reactants such as CnHm giving products, as given in
the following examples:
x Method for production of aromatics from methane, called
“Bicyclar” process such as CH4 + n[C2-C4] ĺ aromatics + 6H2, e.g.
CH4 + 2 C3H8 ĺ C6H5CH3 + 6H2 T* = 600oC on Zn, Ga/ZSM-5
catalyst with CH4/[C2-C4] >4. This process corresponds to a Russian
patent assigned to the Boreskov Institute of Catalysis, Novosibirsk,
RU [14];
x Method for production of components for motor fuels, called “Bi-
reforming” process, such as CH4 + C5 giving benzene + 4H2 at
T* ~ 725oC on Pt/Al2O3 catalyst. E.g. [C1-C4] + Cn giving bilateral
chain benzenes + 4H2. This process corresponds to a Russian patent
assigned to the Boreskov Institute of Catalysis, Novosibirsk, RU [15].
CH4 + CnH2n ļ Cn+1H2(n+1)+2, at T<T*
nCH4 + CnH2n+2 ļ 2CnH2m+2.
Another challenge, obviously not limited to natural gas is to deal with
sustainability, which is a major concern of this NATO, Advanced Study
410 Jacques C. Védrine

Institute. Let us ask some questions and make suggestions, although not
often realistic, but which express our present abnormal human
behaviour.
x What is sustainability? Certainly we cannot meet sustainability with
everything nor do- with the exception of photocatalysis. Obviously
we need better selectivity resulting in less consumption/loss for the
same effect;
x What we should be doing is to minimise problems, energy
consumption and raw material consumption by using catalysis,
which is a key technology;
x Why not to limit American cars to 2L engines, increase the
price of fuel significantly and plant trees, extensively!
x We should focus on:
x Increased selectivity;
x Avoidance of obvious problems, such as halides or sulfates;
x Regard sustainability as a real objective, not a word
associated with a successful grant application;
x Accept that people will not readily change their way of life,
but work to make it more sustainable;
x How can we avoid natural gas, which is flared in the NG
fields, and succeed in its transformation in liquid or
commodities fuel? ;
x How natural gas from biomass can be exploitable ?;
x How to exploit oil fields and natural resources at best, i.e.
with limited loss: including heavy oils, tar sands, oil shale? ;
x CO2 minimisation and heat thermal pollution remain a major
issue and any progress is hardly expected and should be
looked for in research plans. This is the next “hot topic”, after
the sulfur and VOCs issues have been solved in a satisfactory
manner;
x Development of renewable fuels against fossil fuels;
x Move to 100% selectivity in carbon to products
transformation;
x Sustainability measured by financial, environmental and
social impacts;
x Syngas to further conversion, as the process is not at
maximum efficiency.

4. CONCLUSIONS
Necessity for natural gas as a feedstock has become increasingly
important and economic policy has changed in the five last years and
Natural Gas as Feedstock 411

remains a great challenge for the future, due to the increase in price of oil
and its expected and inexorable shortage in a more or less far future. At the
present time, the main industrial process in operation consists in methane
partial oxidation to syngas, followed by its transformation to methanol or
synfuel. Two applications of syngas are becoming of increasing importance:

x Manufacture of liquid fuel from remote or marginal natural gas resources

(Fisher-Tropsch route being major);
x Generation of hydrogen for fuel cells.

Reforming for fuel cell hydrogen has been proposed as an alternative,

comprising generally a mix of partial oxidation of methane, autothermal
reforming and compact reforming.
Alternative routes have been proposed, particularly for direct conversion
of methane and are still not commercially interesting. Therefore, a large
place remains for further researches in the field, which should absolutely
associate catalyst makers, chemical engineering and economics. Some trends
have been proposed to activate directly methane by reactant as oxygen,
chlorine, oleum, and, even, other hydrocarbons (e.g., bicyclar or bi-
reforming processes).

5. REFERENCES
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fundamentals, challenges and opportunities”, E.G. Derouane et al. (ed.), Kluwer
Academic Press, Dordrecht, 2004, this book;
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[12] Y. Xu, L. Wang, M. Xie and X. Gou, Catal. Lett., 30 (1995) 135;
[13] E. Mielezarski, S. Monteverdi, S. Amariglio and H. Amariglio, Appl. Catal. A: Gen.,
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[14] Russian patent, assigned to the Boreskov Institute of Catalysis, Novosibirsk, RU,
No.2188225, issued on 27.08.2002;
412 Jacques C. Védrine

[15] Russian patent, assigned to the Boreskov Institute of Catalysis, Novosibirsk, RU,
No.2144942, issued 10.01.2000.