1588 Ind. Eng. Chem. Res.

2003, 42, 1588-1597

Evolution of Processes for Synthesis Gas Production: Recent

Developments in an Old Technology
Sebastián C. Reyes,* John H. Sinfelt,† and Jennifer S. Feeley

Corporate Strategic Research, ExxonMobil Research and Engineering Company,

1545 Route 22 East, Annandale, New Jersey 08801

The manufacture of gas mixtures of carbon monoxide and hydrogen has been a vitally important
part of chemical technology for about a century. Originally, such mixtures were obtained by the
reaction of steam with incandescent coke and were known as “water gas”. Used first as a fuel,
water gas soon attracted attention as a source of hydrogen and carbon monoxide for the
production of chemicals, at which time it gradually became known as synthesis gas. Eventually,
steam reforming processes, in which steam is reacted with natural gas (methane) or a petroleum
naphtha over a nickel catalyst, found wide application for the production of synthesis gas. A
modified version of steam reforming known as autothermal reforming, which is a combination
of partial oxidation near the reactor inlet with conventional steam reforming further along the
reactor, improves the overall reactor efficiency and increases the flexibility of the process.
Noncatalytic partial oxidation processes using oxygen instead of steam also found wide
application for synthesis gas manufacture, with the special feature that they could utilize low-
value feedstocks such as heavy petroleum residua. In recent years, catalytic partial oxidation
employing very short reaction times (milliseconds) at high temperatures (850-1000 °C) is
providing still another approach to synthesis gas manufacture, as Professor Lanny Schmidt
and his students have shown in their pioneering exploratory research in this area. (See, for
example, Hickman and Schmidt Science 1993, 259, 343.) Here, we consider some crucial issues
in catalytic partial oxidation and report some new data with a bearing on these issues. Nearly
complete conversion of methane, with close to 100% selectivity to H2 and CO, can be obtained
with a Rh monolith under well-controlled conditions. Experiments on the catalytic partial
oxidation of n-hexane conducted with added steam give much higher yields of H2 than can be
obtained in experiments without steam, a result of much interest in obtaining hydrogen-rich
streams for fuel cell applications.

Introduction At 1000 °C, there is a negligible formation of carbon

The production of gas mixtures rich in carbon mon-
oxide and hydrogen has been important industrially for
a long time, roughly from about 1900 to the present. In
an early method of obtaining such mixtures, a bed of
hot coke was exposed alternately to blasts of air and
steam.1 During the period of exposure to air, the burning
of some of the coke heated the bed to a temperature in
the vicinity of 1000 °C. After the air blast, the blast with
steam brought about the overall reaction
C + H2O ) CO + H2 (1)
The use of steam in this step led to the early use of the
term “water gas” in referring to the mixture of carbon
monoxide and hydrogen formed. The reaction is endo-
thermic (∆H°298 ) +31 kcal for graphitic carbon),2 in
contrast to the highly exothermic reaction of carbon with
oxygen that occurred during the air blast. The rise in
temperature of the bed in the exothermic combustion
step provided the heat for the subsequent endothermic
reaction of the steam with coke.
* Corresponding author. Phone: (908) 730-2533. E-mail:
sebastian.c.reyes@exxonmobil.com.
†
Senior Scientific Advisor Emeritus.
10.1021/ie0206913 CCC: $25.00 © 2003 American Chemical Society
Published on Web 01/09/2003
dioxide attributable to the overall reaction
C + 2H2O ) CO2 + 2H2 (2)
If equilibrium is assumed for both reactions 1 and 2,
thermodynamic calculations of the composition of the
gas mixture show that carbon dioxide and water are
present in only trace amounts at 1000 °C, consistent
with observations in the early water gas generators.
Reaction 2, like reaction 1, is endothermic, but the heat
of reaction is smaller (∆H°298 ) +21 kcal for graphitic
carbon). We note that the equation for reaction 2 is a
simple combination of the equation for reaction 1 and
the equation for the so-called “water gas shift” reaction
3 of CO with H2O3
CO + H2O ) CO2 + H2 (3)
which is exothermic (∆H°298 ) -10 kcal).
Because of their high heating values, water gas
mixtures rich in carbon monoxide and hydrogen were
originally of interest as fuels. Later, they attracted
interest as sources of either H2 or CO, or of appropriate
mixtures of the two, for the synthesis of various
chemicals. A very important early example was the
recovery of hydrogen from water gas for use in the
catalytic synthesis of ammonia4 from elemental nitrogen

and hydrogen
N2 + 3H2 ) 2NH3 (4)
In this particular example, the nitrogen for the reaction
could be obtained from the same operation as was used
to generate the water gas mixture, because the gas
issuing from the reactor during the air blast contained
mostly nitrogen and carbon monoxide, the oxygen
having been completely consumed. The combination of
products formed during the alternate air and steam
blasts of the coke thus consisted largely of a mixture of
N2, CO, and H2, with some CO2. The concentration of
CO in this mixture was then decreased to a very low
level by exploitation of the water gas shift reaction. The
equilibrium for this reaction was displaced in the
direction of increased concentrations of CO2 and H2 by
addition of excess H2O vapor to the mixture, coupled
with cooling of the mixture to a temperature of about
500 °C. A satisfactory rate of reaction was obtained by
contact of the mixture with an iron oxide catalyst. The
concentration of CO was decreased to a level of about
1%, and the remaining CO, which is a severe poison for
the metallic iron catalyst used in ammonia synthesis,
was then removed by contacting the gas mixture with
an ammoniacal solution of a cuprous salt.4-6 Prior to
removal of the CO in this manner, CO2 was removed
by contact with water under elevated pressure in an
absorption tower. A later development for the removal
of the last trace amounts of CO was its reaction with
hydrogen to form methane over a nickel catalyst,7 as
the methane is not a poison for the ammonia synthesis
catalyst.
An early example where both the hydrogen and the
carbon monoxide from a water gas mixture were used
in the production of an important chemical is the
catalytic synthesis of methanol8
2H2 + CO ) CH3OH (5)
using a mixture of zinc oxide and chromia as a catalyst.
As in the case of ammonia synthesis, the reaction is
exothermic and is conducted at high pressures for
thermodynamic reasons.
Other examples of important processes using both H2
and CO as reactants include the Fischer-Tropsch
process for the production of hydrocarbons for fuels and
lubricating oil base stocks as well as oxygenated hydro-
carbons for chemicals,9,10 the “oxo” synthesis for the
production of aldehydes in particular (hydroformyla-
tion),11 and the direct catalytic synthesis of higher
alcohols using modified methanol synthesis catalysts.12
Because of the wide use of mixtures of H2 and CO for
the synthesis of chemicals, it became common practice
to refer to such mixtures as “synthesis gas” (or “syn-
gas”).13,14
Steam Reforming
In the 1920s and 1930s, the use of natural gas
(methane) rather than incandescent coke in the produc-
tion of synthesis gas began to attract attention.14,15 The
overall reaction between methane and steam
CH4 + H2O ) CO + 3H2 (6)
is highly endothermic (∆H°298 ) +49 kcal). A catalyst,
commonly containing nickel as the active component,
Ind. Eng. Chem. Res., Vol. 42, No. 8, 2003 1589
Figure 1. Water-gas shift and methane steam reforming equi-
librium constants.
is used, and the process has come to be known as steam
reforming. The process is typically operated with excess
steam (H2O/CH4 mole ratio ) 2:1-4:1) at temperatures
above about 800 °C. The composition of the product gas
generally approaches that expected at equilibrium very
closely. Both reactions 3 and 6 are important in deter-
mining the equilibrium composition. Figure 1 shows
plots of the equilibrium constants as a function of
temperature for these two important reactions. At a
given reactor pressure and mole ratio of H2O to CH4 in
the inlet gas stream to the reactor, the amount of carbon
monoxide increases with increasing temperature, whereas
the amounts of carbon dioxide and methane decrease.
If the reactor pressure is increased, the amounts of
methane and water increase substantially.
Steam reforming was first applied commercially by
the Standard Oil Company of New Jersey (now Exxon-
Mobil) in 1930 at Baton Rouge, LA.16 In the 1950s and
1960s, interest began to develop in the use of light
petroleum naphthas as feedstocks, particularly the
highly paraffinic Middle East naphthas that were less
desirable feedstocks for the production of aromatic
hydrocarbons by another type of process known as
catalytic reforming. The use of the same name, reform-
ing, for the two very different kinds of processes can
understandably be a source of confusion, but it should
be clearly understood that they have no connection to
one another. The catalytic reforming process is not
operated with steam as a reactant or diluent. It is
utilized for producing high-octane-number aromatic
hydrocarbons for gasoline with the aid of so-called
“bifunctional” precious metal catalysts.17-19
The steam reforming of light petroleum naphthas was
originally of particular interest in regions of the world
where natural gas was not readily available. Although
steam reforming is used primarily for the production of
hydrogen and carbon monoxide mixtures, a lower-
temperature version of the process employing naphtha
feedstocks attracted attention for the production of
methane for so-called “town gas” for residential use.
European cities were places where town gas manufac-
ture was especially important. Dent and associates at
the British Gas Council did considerable work in this
area in the late 1950s.15 Highly active and stable nickel
catalysts for application in town gas production were
developed in the laboratories of the Exxon Research and
Engineering Company in the 1960s.20-24 The use of
these catalysts for hydrogen production from naphthas
was also considered.25,26
1590 Ind. Eng. Chem. Res., Vol. 42, No. 8, 2003
In steam reforming for town gas production, elevated
pressures (30-40 atm) are employed and operating
temperatures (400-450 °C) are much lower than those
used for the production of synthesis gas. The molar
ratios of steam to hydrocarbon are typically in the range
of 8:1-12:1. The high ratios are important for limiting
the formation of deactivating carbonaceous residues on
the catalyst. If we consider n-hexane to be representa-
tive of the hydrocarbons in a light petroleum naphtha,
we can think of the overall steam reforming process for
producing methane as one that involves two major
parts. The first part is the decomposition of the reactant
hydrocarbon and the formation of CO and H2 as primary
products. We represent this step by the overall reaction
C6H14 + 6H2O ) 6CO + 13H2 (7)
which is highly endothermic (∆H°298 ) +228 kcal).2 The
second part of the process consists of reaction 3 and the
reverse of reaction 6, both of which are exothermic. As
already mentioned, reactions 3 and 6 are close to being
equilibrated in steam reforming operations, and the
catalysts used in such operations have sometimes been
called equilibration catalysts.27 Increasing the pressure
and decreasing the temperature of the operation drive
reaction 6 to the left, as desired for town gas applica-
tions.
Steam reforming catalysts were early candidates for
application in catalytic converters for decreasing the
emissions of harmful pollutants in exhaust gases from
automobiles.27 The chemistry in steam reforming is very
versatile and important for many applications. Although
steam reforming of petroleum naphthas declined in
importance after huge quantities of natural gas were
discovered in the North Sea area in the late 1960s, there
has been a strong renewed interest in recent years in
naphtha steam reforming for the production of hydrogen
for fuel cells in connection with applications in electric-
powered automobiles.28,29
Autothermal Reforming and Partial Oxidation
From its very inception, steam reforming has been
an important process, continually exhibiting advances
in catalysts and in various engineering features of the
reformers. One of these advances, autothermal reform-
ing, was introduced by Haldor Topsøe in the late
1950s.30,31 It is a combination of partial oxidation and
steam reforming, involving the introduction of both
oxygen (or enriched air) and steam into a reforming
reactor. The partial oxidation occurs in an inlet zone of
the reactor, providing heat for the steam reforming
reaction occurring in a second zone of the vessel that is
packed with catalyst. Consequently, there is no need to
supply heat to the reactor over and above the amount
provided in the preheating of the reactants. This
advance in steam reforming technology improves the
overall reactor efficiency and increases the flexibility of
the process. The ratio of molecules of oxygen gas to
atoms of carbon in the hydrocarbon reactants (O2/C) is
typically about 0.5-0.6, well below that required for
complete combustion. The partial oxidation part of the
process in the case of n-hexane as a feedstock is
illustrated by the reaction
C6H14 + 3O2 ) 6CO + 7H2 (8)
if the selectivity to CO and H2 were 100%. In practice,
of course, there is also some formation of CO2 and H2O.
Reaction 8 is very exothermic (∆H°298 ) -118 kcal),
contrasting markedly with the endothermicity of the
steam reforming reaction of n-hexane, i.e., reaction 7.
In the steam reforming section of an autothermal
reformer, reactions 3 and 6 are equilibrated as in a
conventional steam reformer, so that product composi-
tions can be controlled by altering operations in a
manner dictated by thermodynamic considerations. It
is interesting that the basic idea of using an exothermic
reaction to supply heat for an endothermic reaction is
reminiscent of the alternate air and steam blasts in the
old water gas generators.
Another kind of process for the production of synthesis
gas was also developed and commercialized in the 1940s
by the Texaco32 and Shell33 Oil Companies. It is of
particular interest for the gasification of low-quality
feedstocks, such as petroleum residua and even coal or
coke. Reaction with oxygen occurs in a refractory-lined
vessel. There is commonly no addition of steam, and the
reactor is not packed with a catalyst. Indeed, the
operation is not conducive to the use of conventional
catalysts. Oxygen rather than air is used to enable the
reactors to reach temperatures high enough (about 1400
°C) to circumvent the problems with carbon formation.
An O2/C ratio of about 0.7 is required for this purpose.
As in the case of autothermal reforming, the design of
the burners used in the process is a crucial issue. The
reactors, which are commonly called gasifiers or thermal
POX (partial oxidation) units, operate at pressures as
high as 70 atm in the general range of temperature from
1200 to 1600 °C. The H2/CO ratios in the products are
generally lower than about 2, and it might be necessary
to make adjustments in the ratio by additional process-
ing depending on the ultimate application of the syn-
thesis gas. The technology is versatile and has been very
widely employed since the initial applications. A very
recent report indicates that several hundred gasifiers
are in operation today.34
Catalytic Partial Oxidation
In recent years, the catalytic partial oxidation of
hydrocarbons utilizing precious metals supported on
porous ceramic monoliths has been the subject of much
research. Professor Lanny Schmidt of the University of
Minnesota has been a pioneer in this area.35-41 Other
investigators are also now active in the field.42-46
Reaction times are very short (milliseconds), reminis-
cent of the old and widely used Ostwald process for the
oxidation of ammonia on platinum or platinum-alloy
gauzes in the commercial manufacture of nitric acid (ref
1, pp 597-598, and ref 13, pp 72-73). The monolith
form of catalyst also resembles the kind of structural
support used in catalytic converters for pollution control
in automobile exhaust systems. In the case of methane
oxidation, the desired reaction is
CH4 + 0.5O2 ) CO + 2H2 (9)
which yields H2 and CO in a molar ratio of 2:1. Such a
ratio is ideal for the reactant stream in methanol or
Fischer-Tropsch synthesis. The direct partial oxidation
of methane, in contrast to conventional steam reforming
via reaction 6, is mildly exothermic (∆H°298 ) -8.5
kcal). Consequently, after the reactants are preheated
to a desired inlet temperature, there is no need for
additional input of heat through the reactor walls or

through provision for a separate inlet section of the
reactor in which exothermic combustion reactions are
conducted to provide heat for a downstream endother-
mic process such as reaction 6. Moreover, the direct
catalytic partial oxidation reaction is much faster than
the corresponding catalytic steam reforming reaction,
by roughly 2 orders of magnitude.35-41 With an inlet
reactant mixture of CH4 and O2 in a 2:1 molar ratio,
thermodynamics indicates essentially complete methane
conversion (>99%) to a 2:1 mixture of H2 and CO at
temperatures above about 850 °C. However, the forma-
tion of H2 and CO as primary products does not proceed
without any competition from the complete oxidation
reaction to H2O and CO2. The competing reaction delays
the attainment of the final equilibrium, with the result
that some of the methane is still present in the product
gases. The amount of unconverted methane is especially
sensitive to the nature of the catalyst and the temper-
ature to which the inlet reactant stream is preheated.
Experiments have shown that the amount of uncon-
verted methane decreases, and the selectivity to H2 and
CO increases, when rhodium is used in place of plati-
num in the monolith. Similar positive effects are ob-
served when the reactants are preheated to suitably
high temperatures prior to their entrance into the
reactor. The advantage of rhodium over platinum is
attributed to a lower tendency of surface H atoms to be
oxidized to surface hydroxyl radicals leading to the
formation of water.47,48 As a result, desorption of the H
atoms as H2 molecules becomes the favored process on
rhodium.
Work on catalytic partial oxidation employing mono-
lith catalysts and very short reaction times at high
temperatures is still in an exploratory stage, and
prospects for industrial applications are not yet clear.
However, there is much excitement in the area. In the
next section of this paper, we present further discussion
of important issues and report some new data with a
bearing on these issues.
Recent Results Concerning Key Issues in
Catalytic Partial Oxidation
In this section, we discuss some recent data on the
catalytic partial oxidation of hydrocarbons using mono-
lith catalysts. We focus on two examples that illustrate
well some of the key factors influencing the product
yields in high-temperature, short-contact-time reactors.
In the first example, we examine the conversion of
methane to synthesis gas. By making use of thermody-
namic equilibrium calculations, we first identify condi-
tions that favor high yields of H2 and CO with a molar
ratio of 2. These mixtures are, of course, of great interest
in the production of Fischer-Tropsch liquids and in the
synthesis of methanol. In the second example, we study
the generation of synthesis gas mixtures from n-hexane.
This example is representative of an important class of
reactions in which higher hydrocarbons are reacted with
air and steam to produce a synthesis gas with a high
hydrogen content. The use of steam as a co-reactant is
beneficial for a number of reasons. It converts some of
the carbon monoxide to carbon dioxide and additional
hydrogen via the water gas shift reaction, it lowers the
oxygen requirement (thereby decreasing the amount of
nitrogen fed to the reactor), and it mitigates carbon
formation on the catalyst surface. The generation of
synthesis gas mixtures from higher hydrocarbons is now
attracting considerable attention because, upon further
Ind. Eng. Chem. Res., Vol. 42, No. 8, 2003 1591
Figure 2. Equilibrium mole fractions of products for an inlet
methane and oxygen mixture having an O2/C molar ratio of 0.5.
Calculations with pure oxygen at a total pressure of 1 atm.
processing, a hydrogen-rich stream suitable for fuel cell
applications can be produced. The processing usually
entails additional water gas shift stages (with water
addition) that drive the concentration of CO to very low
levels, complemented by a final purification stage in
which CO is substantially removed to levels that no
longer interfere with the reactions on low-temperature
fuel cell electrodes.
The purpose of these two examples is to show that
product compositions close to those at equilibrium can
be obtained in very short reaction times, provided that
suitable catalysts and conditions are used. The catalysts
must be very active and very selective. In the transfor-
mation of methane to synthesis gas, for example, the
disproportionate formation of H2O and CO2 through
reactions in the gas phase or on the catalyst surface
must be avoided because such reactions inevitably delay
the attainment of equilibrium that dominantly favors
H2 and CO as final products. In addition to the require-
ments of high catalyst activity and selectivity, another
important requirement is a suitably high reaction
temperature, which is paramount for achieving high
yields of H2 and CO.
In the partial oxidation of methane to synthesis gas,
we would ideally like the transformation to proceed to
completion via a direct path represented by the overall
reaction 9. As shown by the results of thermodynamic
calculations in Figure 2, H2 and CO are virtually the
only products at equilibrium at very high temperatures.
The equilibrium mole fractions in Figure 2 were calcu-
lated for an inlet reactant mixture of CH4 and O2 in a
2:1 molar ratio at atmospheric pressure. These mole
fractions are shown as a function of temperature over
the range 400-1000 °C. Consistent with expectations,
the oxygen in the inlet reactant mixture is completely
depleted. We emphasize the following points regarding
the calculated mole fractions in Figure 2. First, the
equilibria for both reactions 3 and 6 are completely
taken into account. Second, equilibria involving carbon
are not included in the calculations; i.e., equilibrium was
not established for reactions such as 1 or 2, or for
reactions 10 and 11 shown below
CH4 ) C + 2H2 (10)
2CO ) C + CO2 (11)
The justification for not including carbon is simply a
1592 Ind. Eng. Chem. Res., Vol. 42, No. 8, 2003
Figure 3. Adiabatic outlet temperature as a function of inlet
preheat temperature. Calculations are for an inlet methane-
oxygen mixture having an O2/C molar ratio of 0.5 with either pure
oxygen or air at a total pressure of 1 atm.
consequence of experience in catalytic partial oxidation
and steam reforming operations, indicating that a
steady state is approached in which the rate of forma-
tion of carbon is negligible compared to the rate of
formation of the desired reaction products. The product
compositions in such operations approach very closely
the equilibrium compositions calculated without inclu-
sion of carbon.
As can be seen in Figure 2, as temperature increases,
the conversion of methane increases, and the amounts
of CO2 and H2O decrease. Such trends simply reflect
the tendency of reaction 6 to convert CH4 and H2O and
of reaction 3 in the reverse direction to consume CO2
as temperature increases. Although the highest yields
of H2 and CO are realized at the highest temperatures,
the matter of attaining such temperatures in a suitable
manner requires some discussion.
According to Figure 2, temperatures approaching
1000 °C are required to achieve essentially complete
conversion to H2 and CO. Reaching this temperature
level requires some provision for heat input because the
desired overall reaction 9 is only mildly exothermic and
therefore generates insufficient heat for the purpose. In
Figure 3, the adiabatic outlet temperature is plotted as
a function of the inlet preheat temperature for an inlet
feed mixture having a CH4/O2 molar ratio of 2:1 with
the use of pure oxygen in one case and air in the other.
As the preheat temperature is increased from 300 to
600 °C, the outlet temperature increases from 805 to
920 °C for pure oxygen and from 710 to 820 °C for air.
These calculated temperatures are a reflection of the
lower amounts of H2O and CO2 present at equilibrium
at higher temperatures and also of the diluting effect
of nitrogen in the case of air. Thus, even in the ideal
situation of an adiabatic operation, the results of Figure
3 indicate that high preheat temperatures are needed
to bring the reaction temperature to a level of 1000 °C.
These results also provide a reason for the use of pure
oxygen instead of air.
The previous discussion clearly illustrates the impor-
tance of reaching a sufficiently high reaction tempera-
ture. In our experience, the reactor outlet temperature
is the critical parameter limiting the yields of H2 and
CO from methane in laboratory experiments. However,
there are several kinds of problems that contribute to
undesirably low temperatures in such experiments.
First, there is the difficulty of avoiding heat losses from
Figure 4. Schematic depiction of experimental monolith catalyst
system employed in the present study.
small reactors. Laboratory studies typically employ
cylindrical monoliths with diameters smaller than about
1 in. Second, there is the difficulty of premixing methane
and oxygen rapidly and completely at high temperatures
while avoiding gas-phase ignition. The complete oxida-
tion products formed as a result of such ignition totally
undermine the purpose of the experiment by eliminating
the direct conversion of CH4 to H2 and CO in the
subsequent action of the catalyst, thereby delaying the
approach to the desired product equilibrium. Conse-
quently, preheat temperatures in laboratory experi-
ments have typically been lower than about 450 °C in
previously reported studies. Also, if experiments are
carried out with air instead of pure oxygen, as shown
in Figure 3, the adiabatic temperature rise is substan-
tially lower because of the added heat capacity of the
nitrogen.
In the present work, we have addressed the issue of
reactor heat losses by employing a well-insulated quartz
reactor within a three-zone furnace. We have also been
able to preheat the reactants to high temperatures
without ignition problems, and we have used pure
oxygen instead of air. Figure 4 shows a schematic
representation of the reactor used in our experiments.
It corresponds to a standard setup in which the active
monolith is sandwiched between two heat shields to
preserve adiabaticity. The reactants are mixed and
heated to about 150 °C prior to their entrance into the
inlet zone of the reactor. Within the inlet zone of the
reactor prior to contact with the catalyst, they are
further preheated to the desired temperature by a
controlled input of heat in the top section of the furnace.
The temperature in each of the three zones within the
furnace is independently controlled.
For a rhodium catalyst supported on an alumina foam
monolith, Figure 5 shows the methane conversion and
selectivities to H2 and CO as a function of the preheat
temperature. The preheat temperature is measured by
the thermocouple located upstream of the front radia-
tion shield. Figure 5 shows that very high yields of H2
and CO can be obtained at atmospheric pressure using
CH4 and pure oxygen with a CH4/O2 molar ratio of 2:1

Figure 5. Experimental CH4 conversion and H2 and CO selectivi-
ties as a function of preheat temperature. Experiments carried
out with an inlet methane and oxygen mixture having an O2/C
molar ratio of 0.5. Pure oxygen, atmospheric pressure, GHSV )
144 000 h-1.
Figure 6. Experimental outlet temperature as a function of
preheat temperature. Experiments carried out with an inlet
methane and oxygen mixture having an O2/C molar ratio of 0.5.
Pure oxygen, atmospheric pressure, GHSV ) 144 000 h-1.
and a high gas hourly space velocity (GHSV ) 144 000
h-1). The GHSV is measured at standard conditions of
pressure and temperature and is based on total mono-
lith volume. Accounting for molar expansion and tem-
perature rise we calculate that the contact time in these
experiments is in the vicinity of 10 ms. The measured
reactor outlet temperatures are given in Figure 6. The
experimental results presented in Figures 5 and 6 are
very consistent with the calculated values given in
Figures 2 and 3. The conversion of methane increases
as the reactor outlet temperature in the experiment
increases. At a preheat temperature of 600 °C, the
selectivities to H2 and CO are about 98 and 99%,
respectively. The corresponding amounts of H2O and
CO2 are very small but consistent with the values
expected from equilibrium calculations. Because of the
very high conversion of methane, yields of H2 and CO
greater than about 95% are obtained. To our knowledge,
this level of performance has not been reported earlier.
Our experiments with methane and oxygen therefore
demonstrate that very high yields of H2 and CO can be
obtained at atmospheric pressure with foam monoliths
using metallic rhodium as the active catalyst. One of
the key remaining challenges in this area is the attain-
ment of high yields at high pressures. This is necessary
Ind. Eng. Chem. Res., Vol. 42, No. 8, 2003 1593
Figure 7. Equilibrium mole fractions of products for an inlet
n-hexane and air mixture having an O2/C molar ratio of 0.5 at a
total pressure of 1 atm.
because the processes that utilize synthesis gas operate
at high pressures. High pressures complicate the situ-
ation significantly. Because of the increase in the
number of moles of species occurring in the production
of synthesis gas from methane and other hydrocarbons,
operations at higher pressure require higher tempera-
tures to maintain yields of H2 and CO at a given level,
as follows from Le Châtelier’s principle. Higher tem-
peratures, in turn, increase the potential for nonselec-
tive gas-phase reactions either during the mixing and
preheating of the reactants or during the time in the
reactor. Clearly, overcoming these difficulties requires
the design of very specialized mixers that avoid gas-
phase ignition prior to entrance of the reactants into
the catalyst zone and the development of very effective
catalysts that permit the desired surface-catalyzed
reactions to proceed more rapidly than the competing
gas-phase reactions. The potential commercial applica-
tion of this technology hinges heavily on these issues.
We now turn to the example of the partial oxidation
of n-hexane with air and steam to produce a synthesis
gas rich in hydrogen. The analysis of this example has
some similarities to that of the previous example on
methane partial oxidation, but there are also some
important differences. To understand better some of the
features of this example, it is instructive to examine first
the simpler situation where n-hexane and air are
reacted without steam in a typical partial oxidation
situation. Figure 7 shows the equilibrium mole fractions
of products as a function of temperature for an inlet feed
mixture having a C6H14/O2 molar ratio of 1:3 (i.e., O2/C
) 0.5) at a total pressure of 1 atm. This molar ratio
corresponds to that of the reactants in the overall partial
oxidation reaction 8. As in Figure 2, equilibria involving
carbon are not included in the thermodynamic calcula-
tions. One of the first observations that can be made is
that n-hexane is completely reacted to synthesis gas
throughout the temperature range of interest for this
type of reaction. The only hydrocarbon present in the
equilibrium mixture is methane (below 800 °C), and this
is a general feature in the partial oxidation of other
hydrocarbon types as well. Thus, some of the conclusions
drawn here for the reactions of n-hexane, air, and steam
in monolith catalysts are applicable to the reactions of
hydrocarbons in general. The nitrogen mole fraction is
explicitly included in Figure 7 to remind us of nitrogen’s
role in lowering the adiabatic temperature rise and in
1594 Ind. Eng. Chem. Res., Vol. 42, No. 8, 2003
Figure 8. Equilibrium mole fractions of products for an inlet
n-hexane, air, and steam mixture having an O2/C molar ratio of
0.5 and a H2O/C molar ratio of 1 at a total pressure of 1 atm.
lowering the partial pressures of the desired synthesis-
gas components.
As in the previous example on methane, H2 and CO
are the main products of the reactions of n-hexane with
air at temperatures greater than about 800 °C. How-
ever, in the ideal situation described by reaction 8, the
H2/CO molar ratio approaches a value of only 7/6 as a
result of the lower H/C ratio in n-hexane compared to
that in methane. The purpose of steam addition is
therefore to exploit the water gas shift reaction 3 to
produce additional hydrogen and carbon dioxide. Ther-
modynamic calculations can be used to determine how
much steam should be added as a reactant for that
purpose. Although the water gas shift reaction is
exothermic, and thus not favored at high temperatures,
increasing the steam partial pressure can increase the
amount of CO transformed by the reaction. The steam
that does not react, however, limits the reaction tem-
perature by taking up some of the heat released by the
oxidation reactions. These competing effects ultimately
give rise to an optimal amount of steam that properly
balances the extent of water gas shift conversion with
the resulting reaction temperature. Figure 8 shows
equilibrium mole fractions of products as a function of
temperature for a typical situation in which steam is
added to the reactant mixture. These compositions were
calculated for an inlet mixture having a C6H14/O2 mole
ratio of 1:3 (i.e., O2/C)0.5) and a C6H14/H2O mole ratio
of 1:6 (i.e., H2O/C)1) at a total pressure of 1 atm.
Contrasting the results in Figure 7 with those of Figure
8, one can clearly see the role of steam in producing
additional H2 and CO2. The hydrogen mole fraction goes
through a broad maximum when the temperature level
reaches about 700 °C. This maximum in hydrogen
occurs in the same temperature region where methane
is no longer an equilibrium product. Thus, when steam
is added to the reactant mixture, high yields of synthesis
gas with a H2/CO molar ratio greater than about 2 can
be obtained at a temperature of about 700 °C. Steam
also helps reduce the amount of methane present at
equilibrium. The drawback of this operation is that the
mixture now contains CO2 and unreacted H2O, and
depending on its ultimate use, some additional process-
ing might be necessary. In the specific case of fuel cell
applications, the final amounts of CO2 and H2O become
even larger as a result of the lower-temperature water-
gas shift steps (with water addition) that are used to
increase the H2 content further. Fortunately, the fuel
Figure 9. Adiabatic outlet temperature as a function of preheat
temperature for an inlet n-hexane, air, and steam mixture with
various O2/C and H2O/C molar ratios at a total pressure of 1 atm.
cell is largely unaffected by the presence of the N2, H2O,
and CO2 that end up with the desired H2-rich stream.
The critical issue with the fuel cell is the removal of
CO, which is a poison for the catalyst surface in the
anode.
With regard to the control of the reaction temperature
for optimal yields in these systems, there are some
compensating effects that require discussion. They
relate to reaction exothermicity and the requirements
of air and steam. The key issues are illustrated in Figure
9 where the adiabatic outlet temperature is plotted as
a function of the inlet preheat temperature. This figure
shows results for three cases in which the O2/C and
H2O/C ratios are varied within typical values. When an
inlet mixture having an O2/C molar ratio of 0.5 and a
H2O/C molar ratio of 1 is used, the adiabatic outlet
temperatures exceed 800 °C even at preheat tempera-
tures as low as 300 °C. This simply reflects the high
exothermicity of the overall partial oxidation reaction
8, which is supplemented by additional heat release
from the mildly exothermic water gas shift reaction.
Because the results of Figure 8 suggest that tempera-
tures in the neighborhood of 700 °C are needed for
maximum yields of H2, one can consider lowering the
amount of air or increasing the amount of steam.
Lowering the air decreases the amount of nitrogen in
the products, and additional steam increases the amount
of hydrogen. Figure 9 shows that lowering the amount
of air to decrease the O2/C molar ratio from 0.5 to 0.44
still leads to high enough reaction temperatures for
optimum H2 yields. The simultaneous decrease of air
to decrease the O2/C molar ratio from 0.5 to 0.44 and
increase of steam from a H2O/C molar ratio of 1 to 2
decreases the temperature to levels that could become
suboptimal at the lower preheat temperatures. It is
emphasized that these trends are strictly valid under
the ideal situation of adiabatic operation. In practice,
any heat losses will tend to increase the amount of
methane to the point where hydrogen yields might be
compromised. It is advisable to aim for reaction tem-
peratures slightly above the optimal values set by the
theoretical analysis, especially when using small labo-
ratory reactors where heat losses are a problem. Be-
cause of the broad maximum in hydrogen content of the
product as a function of temperature (see Figure 8), the
potential yield deficit arising from decreased water-
gas shift conversion at higher temperatures is small.
This is consistent with the mild temperature depen-

Figure 10. Experimental methane conversion and H2 and CO
selectivities obtained in n-hexane experiments with air and steam
at atmospheric pressure (upper field). Experimental values of O2/
C, H2O/C, and preheat temperatures used in n-hexane experiments
with air and steam at atmospheric pressure (lower field).
dence of the equilibrium constant for the water gas shift
reaction (see Figure 1).
On the basis of these considerations, we carried out
numerous experiments to study the reactions of n-
hexane with air and steam in monolith catalysts con-
taining rhodium as the active component. The reactor
setup was the same as that used in the methane partial
oxidation experiments. As shown in the lower field of
Figure 10, these experiments included systematic varia-
tions in the O2/C (0.4-0.54) and H2O/C (0-2.4) molar
ratios, as well as in the preheat temperature (644-858
°C). A set of conditions (O2/C ) 0.44, H2O/C ) 1, T )
700 °C, and GHSV ) 68 000 h-1) that was repeated
several times during the sequence of experiments
confirmed that the catalyst maintained activity with
time on stream. The upper field of Figure 10 sum-
marizes the trends in the selectivities to H2, CO, CO2,
and CH4 for each of the conditions given in the lower
field of the figure. For convenience, the hydrogen
selectivity is defined as the amount of hydrogen in the
products divided by the amount of hydrogen in the
n-hexane reactant. A hydrogen selectivity in excess of
100% is therefore a measure of how much of the
hydrogen in the steam is converted via the water gas
shift reaction. In cases in which no steam is added as a
reactant (i.e., under standard partial oxidation condi-
tions), the hydrogen selectivity drops below 100% be-
cause some water is actually formed in the process (see
Figure 7). One can also see that the amount of methane
is generally small and consistent with the expected
dependence on reaction temperature and on the amount
of steam present in the reaction mixture. There is a very
close correspondence between the pattern of variation
of H2 selectivity in the upper field of Figure 10 and the
pattern of changing H2O/C ratio in the lower field.
Ind. Eng. Chem. Res., Vol. 42, No. 8, 2003 1595
Overall, the results of Figure 10 clearly demonstrate
that hydrogen yields obtained in n-hexane partial
oxidation with monolith catalysts containing rhodium
as the active component improve substantially when
water is added to the feed stream, as a result of the
exploitation of the water gas shift reaction. Because of
the dilution effect of both nitrogen and steam in the feed
stream, gas-phase ignition is less of an issue than in
operations without steam addition.
Concluding Remarks
The production of synthesis gas mixtures very rich
in carbon monoxide and hydrogen is aided by high
temperatures. This has been clear since the earliest
industrial operations employing water gas generators
for the reactions of steam and air with red-hot coke. It
is a consequence of thermodynamics. Thus, a mixture
of steam and methane in a 1:1 molar ratio will yield an
equilibrium mixture of hydrogen and carbon monoxide
in a 3:1 molar ratio at 1000 °C, with only trace amounts
of carbon dioxide, water, and methane being present.
Similarly, a mixture of methane and oxygen in a molar
ratio of 2:1 will yield a 2:1 equilibrium mixture of
hydrogen and carbon monoxide at the same tempera-
ture. With a starting mixture of steam and methane,
the high endothermicity of the steam-methane reaction
requires that provision be made for the addition of heat
well beyond the amount of preheat needed initially to
bring the reactants to the desired temperature. Achiev-
ing this in the most efficient manner has been a key
issue in the improvement of steam reforming operations
over the years. With oxygen and methane as the
starting mixture, the exothermicity of a methane-
oxygen reaction removes this issue, the only consider-
ation being the extent of reactant preheat required to
supplement the heat released by the reaction in raising
the temperature of the gas mixture to the desired level.
The mechanism of the catalytic partial oxidation of
methane to hydrogen and carbon monoxide at high
temperatures is a matter of much interest.35-46 Consider
the reaction of a mixture of methane and oxygen with
a 2:1 molar ratio over a catalyst containing a precious
metal (e.g., rhodium) as the active component. At
temperatures much lower than those used in the
production of synthesis gas, say in the range of 150-
200 °C, rhodium and other group VIII precious metals
are very active oxidation catalysts, but only complete
oxidation products (CO2 and H2O) are observed. What
is happening at much higher temperatures with the
monolith catalysts? One might simply argue that CO2
and H2O are still the initial reaction products, but that
unconverted methane then enters into reaction with
these products via the same chemistry that occurs in
steam reforming, with the final product composition
being governed by the equilibria for the water gas shift
and methanation reactions. However, the reaction oc-
curring in the monoliths is observed to be much faster
(by roughly 2 orders of magnitude) than the steam-
reforming reaction on nickel catalysts, possibly implying
that it takes a different course. Professor Lanny Schmidt
and his students have concluded from their extensive
work in this area that carbon monoxide and hydrogen
are formed as primary reaction products.35-41 The rate
of formation of these products relative to the rate of
formation of complete oxidation products is therefore
much higher than it is at low temperatures. The term
direct partial oxidation is thus used in referring to this
phenomenon.
1596 Ind. Eng. Chem. Res., Vol. 42, No. 8, 2003
In a simple idealized situation, the selectivity of the
catalyst for the direct partial oxidation reaction would
be so high that conversion of the methane would proceed
completely to hydrogen and carbon monoxide without
any significant occurrence of other reactions. The extent
to which this simple situation is approached in a given
case has not been clearly established. Although very
high selectivities to H2 and CO have been obtained with
nearly complete conversion of methane, the absence of
extensive data at low to moderate conversion levels
precludes one from drawing firm conclusions about the
possible contributions of other reactions as the rapid
conversion of the methane proceeds. The possibility of
complete oxidation products contributing significantly
to the ultimate formation of H2 and CO is not readily
dismissed. However, regardless of the present state of
understanding of this matter, the approach of using
monolith catalysts and millisecond reaction times at
high temperatures has been a major development in the
catalytic partial oxidation of hydrocarbons.
As demonstrated by results reported in this paper,
at a methane conversion close to 97%, selectivities to
H2 and CO of 98-99% have been obtained with a
rhodium monolith catalyst at atmospheric pressure.
This has been achieved by careful attention to experi-
mental details such as preheating the reactants to a
suitably high temperature to ensure that the temper-
ature reached in the reactor is high enough for es-
sentially complete conversion of the methane to hydro-
gen and carbon monoxide. The minimization of reactor
heat losses from the small laboratory reactors used in
obtaining the results, coupled with still other experi-
mental measures pointed out in the discussion of the
results, has been crucial for obtaining methane oxida-
tion data under well-controlled conditions.
In recent years, there has been much interest in
obtaining hydrogen from hydrocarbons in the gasoline
boiling range for application in fuel cells for powering
automobiles. In addition to the results reported in this
paper, some results of Schmidt in this regard have been
reported recently.49,50 This approach would have the
advantage of exploiting the existing infrastructure for
dispensing gasoline to the consumer. For an “on-board”
application in an automobile, high-temperature catalytic
partial oxidation could find application here. A variation
of the latter in which steam is added along with air to
the hydrocarbon fuel stream admitted to the reactor
provides a way to increase substantially the amount of
hydrogen obtained in such an operation. The added
water is clearly the source of the increased amount of
hydrogen, as the total production of hydrogen is much
higher than what can be obtained from the hydrocarbon
fuel alone. This has been demonstrated very clearly by
the results presented in this paper. The participation
of the added water in the overall process is similar to
that already mentioned in connection with a possible
role of complete oxidation products in secondary reac-
tions occurring in the basic version of the process
operated without the addition of water. Thus, we see
advantages again for utilizing both air and steam in a
reactor for the production of synthesis gas. This is a
theme that has surfaced repeatedly in a number of
processes that differ in detail but depend in an impor-
tant way on the use of both of these common reagents.
The theme goes all the way back to the water gas
generators used in the early 1900s.
In closing this discussion of synthesis gas production,
we emphasize the decisive role that it has played in
chemical technology for the past century and that it
appears destined to play in major technological innova-
tions envisioned for the future. The new results pre-
sented in this paper provide a flavor for the kind of
research currently done in connection with exciting new
applications of old “water gas” chemistry.
Acknowledgment
The authors thank Mrs. Carol Bordok and Mr. Bruce
A. DeRites for the generation of the experimental data
on methane and n-hexane partial oxidation, respec-
tively, presented in this paper. Many thanks also go to
Dr. Paul J. Berlowitz for helpful discussions and guid-
ance in the n-hexane study, which is part of a broader
set of activities in the production of hydrogen-rich
streams from hydrocarbons for fuel cell applications.
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Received for review September 9, 2002
Accepted October 29, 2002
IE0206913