ARTICLE IN PRESS

I N T E R N AT I O N A L J O U R N A L O F H Y D R O G E N E N E R G Y 33 (2008) 2105 – 2110

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The production of hydrogen through the uncatalyzed

partial oxidation of methane in an internal
combustion engine

Ghazi A. Karim, I. Wierzba

Department of Mechanical and Manufacturing Engineering, Schulich School of Engineering, University of Calgary, Calgary, Canada T2N1N4

art i cle info ab st rac t

Article history: The thermodynamic and kinetic limitations of the uncatalyzed partial oxidation of
Received 1 October 2007 methane for the production of synthesis gas, which is made up of mostly hydrogen and
Received in revised form carbon monoxide in a variety of proportions, are reviewed. It is suggested that such
15 January 2008 processes can be made to proceed successfully in a conventional internal combustion
Accepted 15 January 2008 engine when operated on excessively rich mixtures of methane and oxygenated air. This is
achieved while simultaneously producing power and regenerative exhaust gas heating.
Experimental results are described that show a dual fuel engine of the compression
Keywords:
ignition type with pilot liquid fuel injection can be operated on excessively rich mixtures of
Synthesis gas
methane and air supplemented with oxygen gas to produce hydrogen rich gas with high
Dual fuel engines
methane conversion rates. Similarly, a spark ignition engine was reported to be equally
Hydrogen production
capable of such production and performance. It is shown that there are viable prospects for
Power
the simultaneous production of synthesis gas in engines with efficient useful mechanical
power and exhaust gas regenerative heating.
& 2008 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights
reserved.

1. Introduction to achieve the wider application of hydrogen whether when

Much of the enormous quantities of hydrogen produced
globally are derived from fossil fuels as the raw materials,
especially natural gas. This is of special relevance to the
availability of hydrogen supplies for the petrochemical
industry, where hydrogen plays a dominant role in upgrading
of fuels and enhancing their quality as well as in the
production of a wide range of economically important
materials. Moreover, it has been demonstrated [1] that the
presence of some hydrogen in fuel mixtures can enhance very
significantly their performance in energy combustion systems
both whether for the production of power or thermal energy.
The economic production of hydrogen and its transport for
any application remain to be the key hurdles to be overcome
used as the primary fuel or when used as a supplement in a
variety of proportions to other fuels. A particular remaining
concern is the need to develop convenient and economic
approaches that can provide hydrogen, or gas mixtures
containing hydrogen on demand in a variety of supply rates
when needed. This, to our knowledge, has not been con-
veniently solved to date.
Much of the hydrogen used is normally produced from
fossil fuel resources particularly natural gas/methane via
their reforming with steam. These endothermic processes are
usually carried out in large capacity installations at high
temperatures and most often in the presence of suitable
catalysts. The production of hydrogen rich product gas
mixtures via such approaches promptly in relatively small

Corresponding author. Tel.: +1 403 220 5775; fax: +1 402 282 8406.
E-mail address: karim@enme.ucalgary.ca (G.A. Karim).
0360-3199/$ - see front matter & 2008 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.ijhydene.2008.01.051
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2106 I N T E R N AT I O N A L J O U R N A L O F H Y D R O G E N E N E R G Y 33 (2008) 2105 – 2110

units remains economically and operationally unattractive.

2.00
Moreover, hydrogen production from fossil fuel resources can 50 Atm

H2/CO Ratio in Products

be obtained also via partial oxidation processes where much
thermal energy is produced with some presence of complete 1.75 Carbon
1250 K
combustion products such as carbon dioxide and water
vapor as well as carbon monoxide with the hydrogen. Such 1.50 1500 K
partial oxidation approaches are attractive, particularly when
suitable catalysts are employed. To increase the relative 1700 K
1.25
yield of hydrogen in the products pure oxygen or highly
oxygenated air needs to be employed. However, such 2000 K
approaches represent increased cost and complexity. Of 1.00
course, throughout these partial oxidation processes em- 0.4 0.6 0.8 1.0 1.2 1.4
ployed for the production of hydrogen, much energy is Feed O2/CH4
produced simultaneously and may not be utilized easily and
Fig. 1 – Variation of the calculated hydrogen to carbon
effectively for the production of power [2,3]. There is a need to
monoxide molar ratio in the products at equilibrium with
develop means to produce hydrogen rich gas promptly on
feed oxygen to methane ratio, for four values of equilibrium
demand including in small supply rates. This is becoming
temperature at a pressure of 50 atm.
particularly necessary, not only to enhance the overall energy
utilization efficiency but also to reduce emissions including
greenhouse gases. 3.0
2000 K 50 Atm
The current contribution reviews the thermodynamic and 1700 K
kinetic factors that control the production of synthesis gas
2.5 1500 K
that is the product gas mixture made up of hydrogen and
(H2+CO)/CH4

carbon monoxide in various proportions and widely used as

the raw material for the production of quality fuels and 2.0 1250 K
chemicals. It is then suggested that the production of
hydrogen/synthesis gas mixtures from natural gas can be Carbon formation
produced locally where it is needed on demand virtually 1.5
instantaneously in conventional reciprocating engines while
simultaneously producing efficiently power. Such arrange-
1.0
ments can be made an integral part of regular engine 0.4 0.6 0.8 1.0 1.2 1.4
operation, particularly for stationary power production, so Feed O2/CH4
that the hydrogen containing products can be fed back to
represent a chemically active combustion enhancement Fig. 2 – Variation of the calculated relative molar production
with exhaust gas recirculation. The attractive features of of synthesis gas per mole of methane supplied with the feed
such approaches and the associated limitations will be oxygen to methane molar ratio for four values of
highlighted. equilibrium temperature at a pressure of 50 atm.

2. Thermodynamic considerations

Information about the production of hydrogen and synthesis
gas via the uncatalyzed partial oxidation of methane may be
obtained on the assumption that a state of chemical
equilibrium applies. Information derived this way has its
limitations since the oxidation processes are kinetically
controlled and accounting for the rate processes of the
system cannot be made. Nevertheless, some useful indica-
tions of the roles of the various influencing factors can be
obtained from the results of thermodynamic equilibrium
analysis [4].
The processes of the partial oxidation of methane have
been viewed to take place in two consecutive stages where
near complete combustion of part of the methane and much
of the oxygen is followed by a reforming stage when much of
the CO and H2 are produced. The equilibrium approach tends
to under-estimate the unconverted methane that will appear
in the products and the energy release following the
consumption of the bulk oxygen supplied. It can be seen in
Figs. 1 and 2 that the equivalence ratio of the feed is the
dominant controlling variable while the relatively high
temperature, though very important, tends in comparison to
have a lesser role. This is since the reaction rates and time are
extremely sensitive to temperature, yet they cannot be
accounted for by equilibrium considerations. But, in general,
increasing the mixture equivalence ratio well beyond the
stoichiometric value results in the increase of the relative
production of H2 and CO in comparison to those of H2O and
CO2 with product H2/CO ratio increasing almost linearly.
Higher temperatures increase the relative production of both
H2 and CO and reduce greatly the unconverted methane.
Thus, the production of synthesis gas per mole of methane or
oxygen in the feed can reach very high values at high
temperatures. However, the associated energy release per
unit of feed increases virtually linearly with equivalence ratio,
with temperature changes having a much lesser influence.
The effect of changes in pressure on the product composition
tends to be small in comparison to those of the equivalence
ratio and temperature [4].
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I N T E R N AT I O N A L J O U R N A L O F H Y D R O G E N E N E R G Y 33 (2008) 2105 – 2110 2107

102
3. Chemical kinetic considerations Equivalence Ratio = 3.0
2000 1800 Press. = 1.0 atm
The production of hydrogen through the uncatalyzed partial 100 1600

(CO+H2)/(CH4)0
oxidation of methane needs to be considered kinetically on
1400
non-equilibrium basis so as to obtain more realistic features
10-2
of the conversion process while accounting for the influence
of changes in residence time and space velocity. Only through 1200
suitable kinetic modeling that reliable guidelines can be made 10-4
to establish the product composition and the associated 1000
800
energy release rates. Prospects for speeding the conversion
10-6
process and enhancing the relative yield of hydrogen can
0 400 800 1200
then be evaluated. When sufficiently long time is allowed
Time (µs)
and/or appropriate catalysts provided, equilibrium based
product information may be relied on. Such a kinetic Fig. 4 – Variation of kinetically calculated relative molar yield
approach has become increasingly possible in recent years of synthesis gas per mole of methane supplied with time for
when the very many simultaneous possible elementary an equivalence ratio of 3.0 and at a range of constant values
reactions are identified and the corresponding chemical of reaction temperatures.
kinetic data becoming increasingly available. However, the
kinetic scheme for the oxidation reactions of rich metha-
ne–oxygen mixtures tend to be relatively more complex in 1.6
comparison to lean mixture oxidation since reactions invol- 2.0
ving a number of intermediate species containing C2 and C3 2.5
need to be included. Nevertheless, useful information about
1.2 3.0
details of the dynamic progress of the oxidation of methane
3.5
(CO+H2)/(CH4)0

to the production of hydrogen can be obtained, such as that

shown in Figs. 3–5.
Simulations that incorporate detailed chemical kinetics of 0.8 Temp. = 1600 K
the reactions involved show throughout the dominant role of Press. = 1.0 atm
reaction temperature in establishing the composition of the
products and the relative yield of hydrogen. At low reaction
0.4
temperatures the yield is much lower than that indicated
from equilibrium considerations [5,6]. The time needed to
approach near equilibrium values increases nearly logarith-
mically with the inverse of absolute temperature. Richer feed 0.0
mixtures which in principle can produce higher hydrogen 0 200 400 600
yield, require longer times. Time (µs)
Examination of the progress of the oxidation reaction
Fig. 5 – Variation of kinetically calculated relative molar
indicates that the hydrogen yield tends to be produced not
production of synthesis gas per mole of methane supplied
only from the conversion of the methane directly but also
variation with time for four different feed equivalence ratios
at a constant reaction temperature of 1600 K and
atmospheric pressure.

0.05
Temp. = 1600 K
Reaction Rate (mol/mm3.s)

0.04 2.0 Press. = 1.0 atms through the subsequent consumption of some H2O that has
2.5 been produced earlier on in the reaction sequence. This
0.03 would indicate that significantly long times associated with
3.0
low flow rates are needed to achieve high H2 yield. Moreover,
0.02
3.5 largely because of this, temperatures that are higher than
0.01 those corresponding to the final equilibrium temperature will
be encountered during the course of the reaction.
0.00

-0.01
0 200 400 600
4. Engine applications
Time (µs)
The reciprocating internal combustion engine, whether of the
Fig. 3 – Kinetically calculated reaction rate variation with spark ignition or compression ignition types can be viewed as
time for four different mixture equivalence ratios at a effective commonly available high temperature and pressure
temperature of 1000 K and atmospheric pressure. chemical reactors of widely different designs and sizes that
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2108 I N T E R N AT I O N A L J O U R N A L O F H Y D R O G E N E N E R G Y
can be operated without the need for the use of catalysts. It is
associated with very short residence times and responds
promptly to changes in the control variables. Much of the
products of the high temperature and pressure oxidation
processes in engines can be preserved to the final exhaust
stage through the quenching action of the rapid expansion of
the piston with the simultaneous production of power
accompanied by heat transfer. The hot exhaust gas can be
utilized to provide heating in co-generation systems. Accord-
ingly, in principle, conventional engines can be suitably
modified to operate on very rich mixtures of methane and
oxygen or oxygenated air to produce promptly on demand
hydrogen rich products and synthesis gas simultaneously
with power and heat extraction. This way a ‘‘triple’’-type co-
generation system is developed. However, such an approach
has its limitations and serious practical difficulties. The most
important of which is the fact that proper mixture quality
control while ensuring safe operation throughout is critical
and extremely demanding. The hydrogen produced will be in
association with other gaseous products.
There is evidence that low compression ratio and speed,
spark ignition engines of different manufacture and size were
employed with limited success in process type development
investigation with commercial aims to run on rich mixtures
of methane and oxygenated air and produce synthesis gas
and power [7–9]. No further work to our knowledge appears to
have been reported since then. Some of the main findings of
this early work were that engines can be run on rich mixtures
of methane and oxygenated air of up to 69% by volume O2 and
equivalence ratio of up to 2.5. The products appeared to be of
composition that approximates to the products of water–gas
shift reaction at an equilibrium temperature of 1400 1C. Care
was needed to maintain steady engine operation since any
operational disturbance produced erratic running with un-
acceptably high unconverted feed and very high intensity
knocking. There is a need to evaluate properly the operational
problems of this procedure and develop it further. This is to
be carried out, especially with the view of generating
hydrogen rich exhaust gases on board that can be fed as
additives to gas fueled engines, whether wholly or only to
some of the cylinders, to enhance their performance, when-
ever needed.
5. Synthesis gas production in a compression
ignition dual fuel engine
The dual fuel engine of the compression ignition type is a
modified form of diesel engines where a premixed gaseous
fuel–air mixture is admitted to the engine and then ignited by
the injection of a small quantity of diesel fuel in the usual way.
Such engines have many attractive operational features that
include high compression ratios, high efficiency, highly
energetic ignition source, operation on a wide range of
equivalence gas fuel–air ratios, low emissions and the capacity
to revert to normal diesel operation without interruption,
whenever needed [10]. Many of these distinct features are
conducive to operating a dual fuel type engine on very rich
mixtures of methane and oxygenated air while employing only
a relatively small supply of liquid diesel fuel for ignition. This is
33 (2008) 2105 – 2110
superior to the corresponding spark ignition engine with the
additional option of providing the hydrogen containing
products whenever needed, including on intermittent basis.
Of particular significance of the dual fuel engines features is
their having very high compression ratios in engines of robust
construction with a high energy external ignition source.
These attractive features were demonstrated by us to be
essentially valid, [11–13] through conversion of a direct
injection diesel engine of 115 mm bore, 152 mm stroke and a
compression ratio of 14.2:1 operating at 1000 rev/min. The dual
fuel mode engine needs a constant feed of a relatively small
mass of pilot diesel fuel injection ðFdiesel ¼ 0:08Þ. Much atten-
tion was given when feeding the methane-oxygenated air
mixtures to ensure safe operation and acceptable rates of
pressure rise, peak pressures and thermal engine loading
consistent with those normally encountered under conven-
tional operation. A summary of the main findings of our work
with this aspect of dual fuel operation is:
 Due to kinetic limitations, the operative equivalence ratio
of the intake charge needs to be maintained within a
narrow range that becomes narrower as the oxygen
concentration in the air is increased, Fig. 6. Intake
mixtures of equivalence ratios of up to 2.5 (i.e. molar
O2/CH4 of 0.80) and oxygen index values of up to 0.80
(i.e. O2/N2 of 4.0 by volume) could be employed.
 As shown in Figs. 7–9,Z very high levels of synthesis gas
production can be achieved up to 80% by volume in the dry
products when commercial methane of 90.7% purity
containing 6.3% CO2 by volume was used. No carbon or
higher hydrocarbon products were encountered under
steady operating conditions.
2.75
Ignition Failure Zone
Equivalence Ratio
2.25
Explosive Knocking Zone
1.75
Operating Range
1.25
0.2 0.4 0.6 0.8 1.0
O2/(O2+N2) (Feed Ratio by Vol.)
Fig. 6 – Experimentally determined variation of the stable
operating mixture range for the partial oxidation of
methane in a dual fuel engine with the overall feed
concentration of oxygen in the ‘‘air’’, bounded by zones of
ignition failure and onset of knock at 1000 rev/min,
unthrottled and at ambient intake temperature with 75 mg
of pilot diesel injection per working cycle (i.e. 0.227 kg/h).
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I N T E R N AT I O N A L J O U R N A L O F H Y D R O G E N E N E R G Y 33 (2008) 2105 – 2110 2109

100 1.6
Synthesis Gas in Dry Exhaust (%)

80

[H2/CO] Ratio in Products

1.2

60
0.8
0.227 kg/h, 1000 rev/min
40 15° BTDC

0.4
20

0 0.0
80 100 120 140 160 180 200 220 240 260 0.75 1.00 1.25 1.50 1.75 2.00 2.25 2.50
Equivalence Ratio Equivalence Ratio

Fig. 7 – Variation with the operating total equivalence ratio Fig. 9 – Variation of the ratio of the hydrogen to carbon
of the experimental production of synthesis gas in the dry monoxide ratio in the products with feed equivalence ratio;
exhaust of a dual fuel engine, at 1000 rev/min, unthrottled dual fuel engine operation at 1000 rev/min, unthrottled and
and at ambient intake temperature with 75 mg of pilot at ambient intake temperature and pressure with 75 mg of
diesel injection per working cycle (i.e. 0.227 kg/h). pilot diesel injection per working cycle (i.e. 0.227 kg/h).

70 60
% Hydrogen (Dry, Excluding N2, O2 and CH4)

0.227 kg/h, 1000 rev/min

60
Indicated Thermal Efficiency, %

50 15° BTDC
50
40
40
30
30
20
20
Based on Thermal Capacity
10
10 Based on Fuel
Based on Oxygen
0 0
0.8 1.0 1.2 1.4 1.6 1.8 2.0 2.2 0.75 1.00 1.25 1.50 1.75 2.00 2.25 2.50

O2/CH4 Feed Ratio

Equivalence Ratio

Fig. 10 – Variation of the indicated thermal efficiency

Fig. 8 – Variation with the oxygen to methane molar feed
calculated on the basis of the net heat release, fuel and
ratio, of the hydrogen volumetric concentration in the dry
oxygen energy with feed equivalence ratio; dual fuel engine
exhaust when excluding the nitrogen, oxygen and
operation at 1000 rev/min, unthrottled and at ambient
unconverted methane; dual fuel engine operation at
intake temperature and pressure with 75 mg of pilot diesel
1000 rev/min, unthrottled and at ambient intake
injection per working cycle (i.e. 0.227 kg/h).
temperature and pressure with 75 mg of pilot diesel
injection per working cycle (i.e. 0.227 kg/h).
tive of the amount of fuel employed while the efficiency on
fuel basis is that conventionally employing the heating
 The maximum power output of the engine when produ- value of all the fuel supplied.
cing synthesis gas was in excess of that produced when  The composition of the products is approximately con-
operating conventionally whether in the diesel or dual fuel sistent with that of the products of the water–gas shift
engine modes. The corresponding thermal efficiency reaction at an equilibrium temperature of 1700 K. However,
remains very high and its values were comparable with the exhaust gas composition reflects a trend where the
those obtained with the engine operating with diesel, as conversion of the reactants to final products is the
shown in Fig. 10. The efficiency when calculated on outcome of two stages where most of the oxygen is used
oxygen basis assumes that the oxygen releases the to oxidize part of the methane to be followed by a rate-
corresponding stoichiometric amount of energy irrespec- controlling reforming stage; when much of the hydrogen
 ARTICLE IN PRESS
2110 I N T E R N AT I O N A L J O U R N A L O F H Y D R O G E N E N E R G Y
and carbon monoxide are produced, higher engine speeds
tend to impede this latter stage.
 With the intake mixtures containing unusually high
concentrations of methane to be used in a conventional
engine of a fixed volumetric compression ratio, the
temperature at the end of compression will be reduced
substantially due to the effect of the increased mean
specific heat as compared to normal diesel operation on
air only. This feature unless remedied by suitable mea-
sures such as through increasing the compression ratio
and/or intake mixture preheating can undermine some-
what satisfactory engine operation, including limiting how
rich an equivalence ratio of the feed mixture can be
employed.
6. Concluding remarks
There is a good potential for producing gas mixtures contain-
ing hydrogen and synthesis gas through the partial oxidation
of methane with oxygenated air in specially fitted conven-
tional engines, especially those of the dual fuel compression
ignition type. This hydrogen production will be accompanied
simultaneously with efficiently produced power and with
good prospects of waste heat recovery from such operation.
However, further research and development efforts are
needed particularly in relation to when such products are
intended to be used as a fuel supplement in operating gas
fueled engines so as to enhance their performance. The
success of such applications will be dependent on the capital
expenditure needed, the cost and availability of the oxygen
33 (2008) 2105 – 2110
and methane and whether the potential benefits from such
applications will outweigh having to deal with multiple gas
and fuel supplies simultaneously and ensuring proper con-
trols for safe operation.
Acknowledgments
The contributions of Drs. G. Zhou, A. Hanafi and N.P.W. Moore,
the financial support of the Natural Science and Engineering
Research Council of Canada, NSERC and experimental facil-
ities at Imperial College-London are acknowledged.
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