Twenty-Seventh Symposium (International) on Combustion/The Combustion Institute, 1998/pp.

2283–2291

TWO-DIMENSIONAL MODELING OF PARTIAL OXIDATION OF METHANE

ON RHODIUM IN A SHORT CONTACT TIME REACTOR

OLAF DEUTSCHMANN and LANNY D. SCHMIDT

Dept. of Chemical Engineering and Materials Science
University of Minnesota
151 Amundson Hall
421 Washington Ave. SE
Minneapolis, MN 55455, USA

Partial oxidation of methane in monolithic catalysts at very short contact times has recently been shown
to offer a promising route to convert natural gas into syngas (CO, H2), which can subsequently be converted
to higher alkanes or methanol. Detailed models are needed to understand the complex interaction of
transport and kinetics occurring in these reactors. In this work, the partial oxidation of methane on rhodium
is studied numerically as an example of short contact time reactor modeling.
A tube wall catalytic reactor, which serves to model a single pore or channel of the monolithic catalyst,
is simulated. The simulation is carried out using a fully two-dimensional flowfield description, which is
coupled with a detailed surface reaction model. The catalyst is characterized by its temperature and cov-
erages of adsorbed species, which vary in the flow direction. The simulation offers a detailed description
of the complex interaction between mass and heat transfer as well as chemistry.
At the catalyst entrance, an extremely rapid variation of temperature, velocity, and transport coefficients
is found. The competition between complete and partial methane oxidation is explained using the calcu-
lated surface coverages whereby CO2 and H2O are formed in the entrance region of the catalytic reactor.
Methane conversion as well as H2 and CO selectivity are found to increase with increasing temperature.
Increasing reactor pressure reduces methane conversion, although the syngas selectivity decreases only
slightly.

Introduction CH4 ` 1/2 O2 → CO ` 2 H2

Catalytic combustion and conversion of methane,
the main component of natural gas, have recently
received extensive experimental and theoretical at-
tention because of their potential to reduce pollutant
emissions and synthesize useful chemicals. The cat-
alytic reactors used for these processes, such as foam
or extruded monoliths, wire gauzes, or sintered
spheres, have a complex interaction between the re-
active flow and reactions on the catalytic surface.
Therefore, the description of these heterogeneous
reactors requires a detailed description of the cou-
pling of the flowfield and the catalyst.
The direct partial oxidation of light alkanes in a
monolithic catalyst at very short contact times has
recently been shown to offer a promising route to
convert light alkanes to syngas, higher hydrocarbons,
and oxygenates [1–3]. Syngas formation from meth-
ane/oxygen mixtures on noble metal catalysts is char-
acterized by the competition between a complete
oxidation channel globally written as
CH4 ` 2 O2 → CO2 ` 2 H2O
DHR 4 1890 kJ/mol
and a partial oxidation channel written as
DHR 4 136 kJ/mol
Appropriate catalytic material and residence time
must be chosen to achieve high syngas (CO, H2) se-
lectivity. Rhodium-coated foam or extruded catalysts
with a residence time of approximately 1 ms were
found to be capable of producing this high syngas
selectivity (.90%) with a high methane conversion
(.90%) [1].
These processes, which can be run nearly autoth-
ermally and adiabatically, exhibit an extremely fast
variation of temperature, velocity, and transport co-
efficients of the reactive mixture near the catalyst
entrance. This variation causes strong disturbance of
the parabolic flowfield and two-dimensional effects
in heat and mass transfer. Furthermore, a significant
amount of the chemistry in this system takes place
in the entrance region of the catalyst.
In this paper, we study the partial oxidation of
methane in a tubular reactor with a rhodium cata-
lytic surface. The complex behavior at the catalyst
entrance region, the competition between complete
and partial oxidation, and the role of surface kinetics
are discussed. The dependence of conversion and

2283
2284 CATALYTIC COMBUSTION
selectivity on temperature and pressure is calcu-
lated, and the data are compared with experimental
results.
Numerical Model
The tube wall catalytic reactor, as shown in Fig. 1,
serves as a model of a single pore or channel in mon-
olithic catalysts. Typical pore diameter varies be-
tween 0.25 and 1 mm, and its length is typically 1
cm. In these small diameter channels the flowfield
is always laminar with a Reynolds number of ap-
proximately 20, which has the same order of mag-
nitude at the inlet and under reactor conditions. Ex-
perimental measurements indicate only small
temperature gradients over the catalyst for cases
simulated in this work, so the catalytic wall is as-
sumed to be isothermal. An adiabatic inert wall, 1
cm in length, is used in the model to simulate the
heat shields in front of and behind the catalytic sec-
tion.
Simulations of catalytic reactors often use a sim-
plified model of either the flowfield or chemistry.
This approach can be risky if there is a strong inter-
action between flow and chemistry as occurs in short
contact time reactors. Most previous studies have
assumed a plug flow tubular reactor model where
radial mass and heat transfer are included only
through effective mass or heat transfer coefficients,
which are often assumed to be constant over the
length of the reactor. The resulting initial value prob-
lem is easy to solve even for a system involving many
equations. This method was applied to study the
Fig. 1. Sketch of the tubular re-
actor model representing a single
pore of a monolithic catalyst (top),
axial velocity (middle), and tempera-
ture (bottom) profiles around cata-
lyst entrance. The axial position (z) is
zero at the catalyst entrance, axial
and radial (r) axes have the same
scale.
high-temperature surface chemistry of CH4 oxida-
tion on Pt and Rh [1]. However, the plug flow tu-
bular reactor model is not able to consider two-di-
mensional effects of the complex interaction
between mass and heat transport as well as chem-
istry. A more-sophisticated boundary layer model
was successfully applied to simulate catalytic oxida-
tion [4] over flat plates, although diffusion in flow
direction is still neglected (for a detailed discussion
see Ref. [5]) and this model is not capable of simu-
lating a more complex reactor geometry such as a
wire gauze reactor [3,6]. Because one motivation of
this work is to develop numerical tools that can be
easily applied to various reactor configurations, a
fully two-dimensional elliptic model is used based
on the commercial CFD code Fluent [7].
Only the use of a detailed surface reaction mech-
anism allows the explanation of characteristic fea-
tures of a catalytic reactor such as ignition or poi-
soning [8]. Therefore, we coupled Fluent to external
subroutines that model detailed surface chemistry.
Here, the state of the catalytic surface is described
by its temperature and its coverage with adsorbed
species, which vary in the flow direction. We have
developed subroutines to calculate the surface cov-
erages (Ui) and the surface mass fluxes (ṡiMi) at the
catalytic wall. On the catalytic wall, the boundary
condition for gas-phase species i becomes
r r r
ṡiMi 4 ( j i ` qYi u) n (i 4 1, . . . , Ng)
where ṡi is the creation or depletion rate by surface
r
reactions, Mi the molar mass, j i the diffusive flux, q
r
the density, Yi the mass fraction, u the Stefan veloc-
r
ity, n the unit vector normal to the surface, and Ng
the number of gas-phase species.
 PARTIAL OXIDATION OF METHANE
The chemistry is modeled by elementary reactions
on a molecular level. The chemical source term ṡi of
gas phase and surface species is given by
Ks Ng`Ns
ṡi 4 o
k41
mik kf k p
i41
[Xi ]m8ik
where Ks is the number of elementary surface re-
actions (including adsorption and desorption), mik
(right side minus left side of reaction equation) and
m8ik (left side of reaction equation) are stoichiometric
coefficients, kfk is the forward rate coefficients, Ns is
the number of species adsorbed, and [Xi] the con-
centration of species i. For adsorbed species, the
concentrations are given in mol/m2 and equal the
surface coverage Ui multiplied by the surface site
density C.
The temperature dependence of the rate coeffi-
cients is described by a modified Arrhenius expres-
sion:
Ns
1Eak
kfk 4 AkTbk exp 3 RT 4pU i41
l
ik exp
This expression takes an additional coverage depen-
dence into account. Here, the factor U l has to be
considered in connection to the factor [X]m in the
equation for ṡi.
We are interested in the steady-state solution,
hence the variation of the surface coverage Ui is
zero:
]Ui ṡ
4 i 40 (i 4 Ng ` 1, . . . , Ng ` Ns)
]t C As an example of the catalytic oxidation of meth-
In the external subroutines, this equation system is
solved to obtain surface coverages and surface mass
fluxes. Here, Fluent provides the concentration of
the gas-phase species and the temperature at each
computational cell with a catalytic wall as the bound-
ary. In the surface chemistry subroutines, coverages
and surface mass fluxes are calculated by an implicit
method, where gas-phase concentrations and tem-
perature are kept constant.
The tube wall catalytic reactor itself is described
by the two-dimensional conservation equations us-
ing cylindrical geometry. Detailed description of the
molecular transport are included in the equations,
and the transport coefficients depend on both com-
position and temperature. However, thermal diffu-
sion effects are ignored in these calculations.
For the simulation, a structured grid is used that
must be very fine around the catalyst entrance to
resolve the flowfield. The total number of grid points
varies between 103 and 104 depending on the reactor
diameter and external conditions such as tempera-
ture. The number of computational cells with sur-
face reaction boundaries varies between 30 and 100.
The numerical calculations were performed on a
Cray C916/12512. Typically, a CPU time of about 20
minutes is required to obtain a converged solution.
2285
Chemical Reaction System
In our simulations we use the surface reaction
scheme proposed by Hickman and Schmidt for the
high-temperature methane oxidation in a short con-
tact time reactor with a Rh-coated foam monolith
[1]. Table 1 shows the reaction mechanism with as-
sociated rate expressions. This scheme assumes dis-
sociative methane and oxygen adsorption, formation
of CO, CO2, H2, and H2O via OH, and desorption
of products. All reaction steps are reversible except
methane adsorption and CO2 desorption. It is as-
sumed that oxygen is adsorbed noncompetitively
with other species, whereas all other species are ad-
sorbed competitively. The site density (C) is assumed
to be 1.67 2 1015 mol/m2, which is 1015 atoms/cm2.
For more details such as reaction order, please refer
to the original work [1].
Only the conservation equations for stable species
CH4, O2, CO, H2, CO2, H2O, and N2 are considered
in the gas phase. Gas-phase reactions are assumed
e ik Ui
3 RT 4 to be negligible under given conditions of about 1
ms contact time and approximately 1200 K tem-
perature. The simulation of a homogeneous chemi-
cal reactor using a detailed gas-phase reaction mech-
anism that includes C1–C4 species [9] shows that
only for the high-pressure calculation (.10 bar, see
discussion below), gas-phase chemistry might have
some influence.
Results and Discussion
ane on rhodium in short contact time reactors, the
simulation of the following case is discussed: a meth-
ane/oxygen mixture (ratio: 1.8, 30% nitrogen dilu-
tion) flows at a uniform inlet velocity of 1 m/s and
at 298 K with a total pressure of 1.4 bar into a cylin-
drical tube 3 cm in length having a diameter of 0.5
mm (Fig. 1). The 1-cm-long inner catalytic wall in
the center of the tube has a constant temperature of
1123 K. The wall is adiabatic and inert in front of
and behind the catalytic section.
The catalyst entrance is characterized by an ex-
tremely fast variation of velocity, temperature, and
transport coefficients of the reactive mixture. In Fig.
1, the axial velocity and the temperature field around
the catalyst entrance are shown. The temperature
increases inward 1 mm, which corresponds to a
length of two tube diameters, to 1000 K. Simulations
using different tube diameters show an even smaller
entrance region of one tube diameter length for a
0.25-mm diameter, which corresponds to the fre-
quently used 80 ppi (pores per inch) monolith. The
entrance length was found to decrease approxi-
mately as D2 with tube diameter D. Furthermore,
the incoming gas is preheated immediately in front
of the catalyst by upstream thermal conductivity. We
note that radiation is not explicitly taken into account
2286 CATALYTIC COMBUSTION

TABLE 1
Surface reaction mechanism on rhodium (units: A [mol, cm, c], Ea [kJ/mol], s [1]) taken from Hickman and
Schmidt [1], to which the reader is referred for further details

Reaction A Ea s

CH4(g) → C ` 4H 1.9 • 1019 21.0

O2(g) → 2 O 0.01
H2(g) → 2H 0.16
CO(g) → CO 0.50
H2O(g) → H2O 0.16
2 O → O2(g) 3.0 • 1021 293.3
2 H → H2(g) 3.0 • 1021 75.4
CO → CO(g) 4.0 • 1013 132.4–44.4 • Uco
H2O → H2O(g) 1.0 • 1013 45.2
H `O → OH 4.2 • 1021 83.8
OH → O ` H 6.0 • 1021 21.0
H ` OH → H2O 1.8 • 1026 33.5
H2O → H ` OH 3.0 • 1023 155.0
OH ` OH → H2O ` O 2.4 • 1024 62.8
C ` O → CO 3.0 • 1022 62.8
CO → C ` O 6.0 • 1019 167.6
CO ` O → CO2(g) 6.0 • 1020 104.7

(g) 4 gas-phase species

because the large thermal conductivity of the mon-

Fig. 2. Mass fraction of methane (top) and oxygen (bot-
tom) as a function of position in the reactor. The axial po-
sition (z) is zero at the catalyst entrance, the catalytic wall
is at the radial position (r) of 0.25 mm.
olith results in an isothermal wall. The rapid increase
of the velocity from 1 m/s to greater than 10 m/s at
the catalyst entrance is not only a result of the den-
sity change due to the temperature increase but also
caused by the change of the composition, which
leads to almost two moles of products for each re-
actant under given conditions; methane oxidation
starts immediately at the catalyst entrance. In the
first noncatalytic section of the tubular reactor a par-
abolic flowfield is quickly established. This parabolic
flowfield is strongly disturbed at the catalyst en-
trance, and two maxima occur that can be seen from
the contour line at 4 m/s in Fig. 1. A few tube di-
ameters downstream the parabolic velocity field is
again established.
The rapid variation of the transport coefficients at
the catalyst entrance is caused by the temperature
increase and the composition change. The rise in
thermal conductivity, a factor of 10 between inlet
and reactor conditions, once again leads to an ac-
celeration of the gas temperature increase. Also, the
diffusion coefficients and the kinematic viscosity vary
approximately by a factor of 10 at the catalyst en-
trance. The variation of the transport coefficients
due to chemical reactions is caused mainly by the
formation of hydrogen. The hydrogen mole fraction
increases to 0.5 during the reaction.
Figures 2–4 show the mass fraction of the gas
phase species as a function of position in the reactor.
The catalytic part of the tubular reactor is between
 PARTIAL OXIDATION OF METHANE
Fig. 3. Mass fraction of the complete combustion prod-
ucts, CO2 (top) and H2O (bottom), as a function of position
in the reactor. The axial position (z) is zero at the catalyst
entrance, the catalytic wall is at the radial position (r) of
0.25 mm.
a 0- and 10-mm axial position and the radial position
is set to zero at the tube axis so that the catalytic wall
is at 0.25 mm. Methane oxidation starts directly at
the catalyst entrance where large radial and axial gra-
dients are formed. Oxygen is completely consumed
by catalytic reactions. However, there is still some
methane left at the catalyst exit, the methane con-
version being 95%.
The catalytic formation of hydrogen and carbon
monoxide as the desirable products and water and
carbon dioxide as the complete oxidation products
starts at the catalyst entrance. Here a competition
between the partial and the complete oxidation
paths occurs. In the beginning, the oxygen concen-
tration is large enough to quickly produce a signifi-
cant amount of CO2 and H2O, which leads to steep
radial concentration gradients of these species (Fig.
3). The desorbed water can again be readsorbed. In
contrast to H2O, the adsorption of CO2 molecules is
negligible due to the very low heat of adsorption for
CO2 on Rh. These kinetic differences and the larger
diffusion coefficient for water are responsible for the
higher peak of CO2 at the catalytic wall. After a 1-
mm catalyst length, the complete oxidation channels
practically extinguish, although there is still a con-
siderable amount of oxygen in the gas phase. Now
2287
Fig. 4. Mass fraction of the partial oxidation products,
CO (top) and H2 (bottom), as a function of position in the
reactor. The axial position (z) is zero at the catalyst en-
trance, the catalytic wall is at the radial position (r) of 0.25
mm.
oxygen is completely used for CO formation. The
activation energy for OH formation on rhodium is
higher than for CO formation, in contrast to plati-
num surfaces [1,8]. Therefore platinum can be used
for complete catalytic oxidation of methane, whereas
rhodium is preferred for partial oxidation, for syngas
formation. Furthermore, in the downstream direc-
tion an increasing number of carbon atoms on the
rhodium surface is available to consume oxygen.
This is illustrated in Fig. 5 where the surface cov-
erages are shown as a function of the axial position.
Here, it can be clearly seen that the oxygen coverage
decreases in the first part of the catalyst, so farther
downstream any adsorbed oxygen is consumed im-
mediately. In the first part of the catalyst, CO is the
major adsorbed species, which explains the forma-
tion of CO2 in this range. Here, the rate-limiting step
for water production is the OH formation. OH im-
mediately leads to water due to the high hydrogen
coverage. Therefore, the OH coverage is lower than
1016. At the catalyst entrance, the C coverage is still
low. The activation energy for CO2 formation is simi-
lar to that of OH formation. Both these factors lead
to water formation in the first part of the catalyst.
The increasing carbon coverage agrees with the ex-
perimentally indicated carbon surface coverage at
the catalyst exit.
2288 CATALYTIC COMBUSTION
Fig. 5. Surface coverage as a function of the axial posi-
tion in the reactor. The axial position is zero at the catalyst
entrance.
Fig. 6. H2 and CO selectivity as well as CH4 conversion
as a function of temperature. The symbols refer to an ex-
periment with a 65 ppi foam monolith [10].
Figure 4 shows the final high syngas selectivity,
where in this case the hydrogen selectivity is 93%
and the CO selectivity is 97%. The higher diffu-
sion coefficient of hydrogen compared with that of
carbon monoxide leads to the larger radial gradients
of CO.
At the catalyst entrance some backward diffusion
of the products occurs as indicated by the profiles in
Figs. 3 and 4. Because the processes at the catalyst
entrance are decisive for global selectivity and con-
version, a detailed description of these phenomena
is necessary, which can only be done using an elliptic
model.
The program was used to carry out parameter
studies such as the dependence of selectivity and
conversion on temperature, pressure, catalytic
material, pore diameter, and the methane/oxygen ra-
tio. The dependence on temperature and pressure
is discussed here in more detail.
Fig. 7. H2 (squares) and CO (triangles) selectivity as well
as CH4 conversion as a function of pressure. The symbols
refer to an experiment with a 80 ppi foam monolith [11].
The short contact time reactor allows the running
of the syngas formation on rhodium nearly autoth-
ermally and adiabatically if reactor insulation is used.
Only a small temperature gradient over the axial re-
actor position has been recorded [10]. Consequently,
the reactor temperature is determined by conver-
sion, selectivity, and heat loss. A higher reactor tem-
perature could be achieved by preheating the inlet
gases. We studied the influence of temperature vari-
ation on selectivity and conversion numerically by
varying the isothermal catalytic wall temperature.
Fig. 6 shows the increase of methane conversion and
syngas selectivity with increasing temperature. This
tendency agrees with the experimental observation
for preheated gases [1]. Furthermore, a comparison
with an experimental measurement on a 65 ppi Rh/
a-Al2O3 foam monolith is shown [10]. In this exper-
iment, the autothermal operating reactor tempera-
ture was 1073 K, which was determined experimen-
tally by a thermocouple. In spite of the fact that the
tubular reactor model is a simplification of a foam
monolith, the calculation and experimental data
agree quite well.
The industrial application of short contact time re-
actors depends on the possibility of running these
processes at higher pressures. In laboratory experi-
ments, measurements of the pressure dependence
are very limited due to safety and costs. In contrast,
the numerical simulation of higher pressure is rela-
tively straightforward. Therefore, a former experi-
mental study has been extended to higher pressures
by using the numerical code. In Fig. 7, the calculated
conversion and selectivity are shown and compared
with experimental data for the low pressure region.
In the experiment, a methane/oxygen ratio of 2 with
20% nitrogen diluent, a gas inlet velocity of 3.7 m/s,
and a Rh-coated 80 ppi foam monolith were used
[11]. These data are also used in a simulation
whereby a single pore of the 80 ppi catalyst is mod-
eled by a tube 0.25 mm in diameter. The adiabatic
 PARTIAL OXIDATION OF METHANE
reactor temperature, which is calculated from total
selectivity and conversion, is used as catalyst tem-
perature. Both the experimental and the calculated
data show the same qualitative behavior: decreasing
methane conversion and only slightly decreasing
syngas selectivity with increasing pressure. The
simulation shows that for higher pressures, the cat-
alyst is not long enough for complete conversion,
although the selectivities remain nearly constant.
The quantitative differences between experiment
and simulation can be caused by an oversimplified
model of the porous foam monolith, the uncertainty
in the experimental measurement, or the application
of a surface reaction mechanism that was established
using a one-dimensional model. Furthermore, ho-
mogeneous reactions might become significant at
higher pressures (.10 bar), which would result in
more CO2 and H2O.
Conclusions
A two-dimensional elliptic model based on the
CFD code Fluent has been coupled with external
subroutines that describe detailed surface chemistry.
We have applied this newly developed numerical
tool to simulate the partial oxidation of methane on
rhodium in a short contact time reactor. A 17-step
elementary surface reaction mechanism and a de-
tailed transport model have been used. The simu-
lation offers a detailed description of the complex
interaction between mass and heat transfer as well
as chemistry. At the catalyst entrance, an extremely
rapid variation of temperature, velocity, and trans-
port coefficients occurs. The competition between
complete and partial methane oxidation is explained
using the calculated surface coverages in which CO2
and H2O are formed in the entrance region of the
catalytic reactor. Methane conversion and syngas se-
lectivity increase with rising temperature. Increasing
reactor pressure reduces conversion, whereas the
syngas selectivity decreases only slightly.
In the cases studied in this paper, an isothermal
catalytic wall can be assumed, and gas-phase reac-
tions do not seem to influence the chemistry. How-
ever, the application of the computational tools to
some further chemical systems needs to involve
2289
models of both heat balances in the solid and de-
tailed chemistry in the gas phase. Future work will
address these problems.
Acknowledgment
We would like to thank Professor J. Warnatz for his con-
tinuous support in modeling of catalytic combustion. This
research is supported by using the computer facilities of
the Supercomputer Institute at University of Minnesota.
Financial support by the Department of Energy under
grant no. DE-FG02-88ER13878-A02 is acknowledged.
Olaf Deutschmann gratefully acknowledges a grant from
the DFG (Deutsche Forschungsgemeinschaft) for a one-
year stay at the University of Minnesota, Department of
Chemical Engineering and Materials Science.
REFERENCES
1. Hickman, D. A. and Schmidt, L. D., AIChE J.
39:1164–1177 (1993).
2. Huff, M. and Schmidt, L. D., AIChE J. 42:3484–3497
(1996).
3. Goetsch, D. A. and Schmidt, L. D., Science 271:1560–
1562 (1996).
4. Warnatz, J., Allendorf, M. D., Kee, R. J., and Coltrin,
M. E., Combust. Flame 96:393–406 (1994).
5. Karim, H., Pfefferle, L. D., Smooke, M. D., Markatou,
P., and Xu, Y., Combust. Sci. Technol. 119:107–130
(1996).
6. Iordanoglou, D. I. and Schmidt, L. D., J. Catalysis
176:503–512 (1998).
7. Fluent 4.4, copyright Fluent Inc., Lebanon, NH, 1997.
8. Deutschmann, O., Schmidt, R., Behrendt, F., and
Warnatz, J., in Twenty-Sixth Symposium (Interna-
tional) on Combustion, The Combustion Institute,
Pittsburgh, 1996, pp. 1747–1754.
9. Baulch, D. L., Cobos, C. J., Cox, R. A., Esser, C.,
Frank, P., Just, Th., Kerr, J. A., Pilling, M. J., Troe, J.,
Walker, R. W., and Warnatz, J., J. Phys. Chem. Ref.
Data 21:411–734 (1992).
10. Bodke, A. S. and Schmidt, L. D., J. Catalysis 179:138–
149 (1998).
11. Dietz III, A. G. and Schmidt, L. D., Catal. Lett. 33:15–
29 (1995).
2290 CATALYTIC COMBUSTION
COMMENTS
Laxminarayan L. Raja, Colorado School of Mines, USA.
The wall temperatures in your simulations are sufficiently
high that gas chemistry can play a role. Comment on the
accuracy of your solutions when you neglect this effect.
Author’s Reply. Indeed, the high temperature of more
that 1000 K may lead to significant gas-phase reactions,
even though the residence time of the mixture is only a
few milliseconds in the hot reactor. The comment also ad-
dresses an important point concerning a commercial ap-
plication of short contact time reactors. Here, the reactor
has to be operated at higher pressures of 20–30 bar that
will additionally increase the influence of gas-phase reac-
tions.
Therefore, we recently coupled the CFD code FLU-
ENT with a detailed gas-phase chemistry model [1]. In this
model, 164 gas-phase reactions among 22 chemical species
are used aside from the surface reaction mechanism. First,
results revealed that gas-phase chemistry is not significant
at all at atmospheric pressure. Hence, the solutions ob-
tained with only surface chemistry as in the present paper
are accurate at atmospheric pressure. However, at higher
pressure (over 10 bar), gas-phase reactions become more
and more important leading to an increase in CO2 and H2O
formation [1]. Here, the effect of gas-phase chemistry can-
not be neglected. Because of the interaction of gas phase
and surface chemistry, in particular, recombination of rad-
icals, the currently used surface reaction mechanism must
be improved by taking adsorption and desorption of inter-
mediates into account.
REFERENCE
1. Deutschmann, O. and Schmidt, L. D., “Partial Oxida-
tion of Methane in a Short Contact Time Reactor: Two-
Dimensional Modeling with Detailed Chemistry,”
AIChE J., in press.
● serve mass? Also, what are the discretizations and com-
I. A. B. Reid, British Petroleum, UK. In conventional
partial oxidation, the reaction takes place at higher tem-
perature and 30 bar. The mixture is kept at high tempera-
ture for several seconds to equilibrate the mixture. The
selectivity is similar to the SCTR at 1 bar. How can you
develop high-pressure SCTR to maintain high selectivity if
the gas-phase chemistry begins to dominate but tempera-
ture and residence time are too low to allow product equil-
ibration to CO and H2?
Author’s Reply. The increasing influence of gas-phase
chemistry on selectivity really seems to be one of the cru-
cial steps in the development of a high-pressure short con-
tact time reactor (SCTR). Recent simulations including
gas-phase chemistry actually show decreasing syngas selec-
tivity at increasing pressure [1 in comment]. However, the
impact of the catalytic surface on gas-phase intermediates
(recombination of radicals) has still to be revealed. If the
surface acts as a sink for these intermediates, what we ex-
pect, then catalytic monoliths with more channels per unit
(i.e., a smaller diameter of each channel) will help to sup-
press undesired gas-phase chemistry. However, the occur-
ring pressure drop has to be considered if thinner channels
are used. Generally, work still has to be done to solve the
problem described in the comment.
●
Paul Shardlow, University of Sydney, Australia. How
long does it take to solve for the temperature and species
profiles shown? Are there any problems in getting a solu-
tion?
Author’s Reply. The numerical calculations were per-
formed on a Cray C916/12512. Typically, a CPU time of
about 20 min is required to obtain a converged solution. If
detailed gas-phase chemistry is also added to the model, a
simulation takes several CPU hours.
Most of the time of this project was needed to develop
a numerical algorithm to achieved stable solutions. In par-
ticular, a pseudo-implicit method for the surface coverage
calculations and an under-relaxation procedure are used to
simulate the coupling of surface chemistry (very fast time
scales) and flow field. Now a new simulation, for example,
varying the chemical kinetics, is straightforward.
However, problems still occur in getting a converged so-
lution if gas-phase chemistry is also taken into account.
Work on this problem is in progress.
●
Dion Vlachos, University of Massachusetts, USA. Do you
use a Stefan velocity in the simulations, as implied in your
talk, as the mass average velocity should be zero to con-
putational times at different conditions?
Author’s Reply. The Stefan velocity is automatically cal-
culated in the CFD code used for the simulations. How-
ever, when the net mass flux at the surface is zero, the
Stefan velocity vanishes by definition, as you said. Because
steady-state solutions were calculated and there is no
growth or ablation on the surface in the presented simu-
lations, the Stefan velocity is always zero.
The discretization is based on a control volume finite-
difference method. The total number of grid points varies
between 101 and 104 depending on the reactor diameter
and external conditions such as temperature. The grid has
to be fine around the catalyst entrance where rapid varia-
tions of the variables occur.
Reference should be made to a previous comment con-
cerning computational times.
 PARTIAL OXIDATION OF METHANE 2291

● Author’s Reply. We agree that there are important con-

Bruce Gerhold, Phillips Petroleum, USA. The model im-
poses a fixed temperature for the catalyst wall. This tem-
perature can be critical in that it can determine whether
or not the flow ignites or blows through unreacted (both
solutions will be noted depending on gas-velocity). In re-
ality, the catalyst wall temperature results from local ther-
mal equilibrium between (1) catalyst wall heat conduction,
(2) radiation from downstream, (3) radiation to cooler areas
upstream, and (4) catalytic reaction. Can you provide es-
timates of these heat-transfer rates that support the as-
sumed catalyst wall temperatures?
siderations. Experiments show that the catalyst tempera-
ture varies by less than 1008 C until much higher flow rates
than those assumed in their calculations. We have included
wall temperature variations in more recent calculations,
and they confirm these assumptions. Radiation, while more
difficult to include, will make axial variations smaller. The
high flow rate situation and blowout possibilities need to
be examined in more detail.