Combustion and Flame 159 (2012) 16441651

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Combustion and Flame

j o u r n a l h o m e p a g e : w w w . e l s e v i e r . c o m / l o c a t e / c o m b u s t fl a m e

Effects of catalyst segmentation with cavities on combustion enhancement

of blended fuels in a micro channel q
Yueh-Heng Li a,b,, Guan-Bang Chen a, Fang-Hsien Wu b, Tsarng-Sheng Cheng c, Yei-Chin Chao b,
a

Research Center for Energy Technology and Strategy, National Cheng Kung University, Tainan 701, Taiwan, ROC
Department of Aeronautics and Astronautics, National Cheng Kung University, Tainan 701, Taiwan, ROC
c
Department of Mechanical Engineering, Chung Hua University, Hsinchu 300, Taiwan, ROC
b

a r t i c l e

i n f o

Article history:
Received 11 July 2011
Received in revised form 31 October 2011
Accepted 25 November 2011
Available online 28 December 2011
Keywords:
Numerical simulation
Catalytic combustion
Catalyst segmentation
Cavity
Micro-reactor
Syngas

a b s t r a c t
A novel design concept for combustion enhancement of H2/CO, CH4/CO, and H2/CH4 blended fuels in a
micro channel using combined effects of catalyst segmentation and cavities is proposed. The enhancement and combustion characteristics are evaluated by numerical simulation with detailed heterogeneous
and homogeneous chemistries. Effects of unsegmented and segmented catalysts with and without cavities are examined and discussed in terms of different multi-fuel mixtures. In general, it is found that the
chemical process of conventional catalytic combustion is a competition for fuel, oxygen, and radicals
between heterogeneous and homogeneous reactions. On the other hand, the purpose of using catalyst
segmentation and cavities in a micro-reactor is to integrate advantages of heterogeneous and homogeneous reactions, to enhance fuel conversion, and to promote complete combustion in a short distance.
In the proposed catalyst conguration, the heterogeneous reaction in a prior catalyst segment produces
chemical radicals and catalytically induced exothermicity, and the homogeneous reaction can be subsequently ignited and anchored in the following cavity. H and OH radicals from both hydrogen and methane may obviously change the chemical pathway of CO oxidation. Full multi-fuel conversion and
complete combustion can thus be achieved in a short distance. The existence of cavities appreciably
extends the stable operational range of the micro-reactor for a wide range of inlet ow velocities. Moreover, cavities in a small-scale system can further stabilize the ame, and serve as a heat source to enhance
the reaction. These features allow the proposed catalyst conguration to apply to various small-scale
power, heat generation and propulsion systems.
2011 The Combustion Institute. Published by Elsevier Inc. All rights reserved.

1. Introduction
Hydrocarbon-fueled micro-reactors have received increasing
attention for electrical power generation in portable electronics
due to their superior energy density (45 KJ/g) compared to that
of state-of-the-art lithium batteries (1.2 KJ/g) [1]. The conversion
of the chemical energy of fuels into electricity in a micro-scale
device without moving parts can be achieved using fuel cells,

q
This paper is submitted for publication in Combustion and Flame. Materials in
this manuscript have neither been published in nor submitted to a journal
previously, nor will it be submitted to another journal during the review process of
Combustion and Flame.
Corresponding authors. Addresses: Research Center for Energy Technology and
Strategy, National Cheng Kung University, No. 1, Ta-Hsueh Rd., Tainan 701, Taiwan,
ROC. Fax: +886 6 2095913 (Y.-H. Li), Department of Aeronautics & Astronautics,
National Cheng Kung University, No. 1, Ta-Hsueh Rd., Tainan 701, Taiwan, ROC. Fax:
+886 6 2389940 (Y.-C. Chao).
E-mail addresses: yuehheng.li@gmail.com (Y.-H. Li), ycchao@mail.ncku.edu.tw
(Y.-C. Chao).

photovoltaics [2,3], and thermoelectrics [4]. A major threshold in

practical micro-reactors (with characteristic dimensions <1 mm)
is their enhanced heat loss and combustion instability. Homogeneous ames are typically quenched when conned in spaces with
dimensions below their quenching distances [5].
The increased surface-to-volume ratio of micro-reactors leads
to thermal and radical quenching of reactions. Catalytic microcombustor exhibits wider stability than homogeneous micro-combustor [6,7]. The catalytic layer deposited on the reactor walls may
sustain chemical reactions at lower temperatures and in the presence of higher heat losses, thus reducing the impact of thermal
quenching. However, complicated heterogeneoushomogeneous
interactions can be observed in catalytic micro-reactors. Wellknow aspects of these interactions include the promotion of gasphase reactions due to catalytically induced exothermicity and
the inhibition of gaseous reactions caused by the competition of
fuels and oxidizers of the catalyst bed versus gas phase reactions.
The competition between heterogeneous and homogeneous reactions often leads to incomplete combustion and a narrowing of
the stable operating range. Nevertheless, some strategies have thus

0010-2180/$ - see front matter 2011 The Combustion Institute. Published by Elsevier Inc. All rights reserved.
doi:10.1016/j.combustame.2011.11.017

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Y.-H. Li et al. / Combustion and Flame 159 (2012) 16441651

been proposed for micro-reactors, such as heat recuperation [8,9]

and utilizing quench-resistant fuels [10], etc.
Undoubtedly, a proper combustor conguration [1113] and a
well designed catalyst bed [14,15] can improve the reaction and
reduce heat and radical loss. Federici et al. [8] demonstrated that
the thermal properties of reactor materials play a vital role in
the overall thermal stability of micro-reactors. The reactor walls
not only contribute to heat loss through conduction, but they are
often responsible for the majority of heat transfer from upstream,
which is necessary to preheat the feed to ignition temperature. In
other words, a properly maintained high wall temperature in
localized space can extend the gas reaction and mitigate radical
quenching. Li et al. [11] and Benedette et al. [13] reported that a
hybrid micro-combustor consisting of alternating catalytic and
non-catalytic segment have been designed to operate under high
velocities to overcome the blow-out regions or to selectively promote homogeneous combustion to improve the overall conversion
in the system.
Recently, most research activities in the eld of catalytic combustion for energy production has emphasized on the use of
methane, mainly for its nature of clean fuel, widely available
world-wise. Nonetheless, methane is inherently the most stable,
difcult-to-oxidize hydrocarbon with outstanding characteristics
that its catalytic ignition occurs at relatively high temperature
even on the most active and expensive PdO-based catalysts.
Some strategies were proposed to overcome the shortcoming,
such as preheating the fuelair gas, adding hydrogen in methane-fuel and proposing new catalyst layout to improve heteroand homo-geneous reaction in a conned space. In our previous
[16], we proposed a conguration of catalyst segmentation with
cavity to accelerate the methane conversion in a microreactor.
The details in the correlation between heterogeneous and homogeneous reaction in different catalyst layouts are briey addressed in the following section. Furthermore, Westbrook and
Dryer [17] identied heterogeneoushomogeneous radical coupling in methane combustion over platinum tubes. The gasphase combustion of methane can be roughly described by a
two-step process, the incomplete oxidation of CH4 to CO and
the main heat-releasing oxidation of CO to CO2. However, carbon
monoxide is certainly active on the platinum surface due to its
high sticking coefcient (0.85 on Pt). By depriving CO from the
gas-phase, the catalyst inhibits the homogeneous reaction of
CO. Accordingly, mixing methane with CO and H2, such as composition of the syngas and gasied biomass [18], might be
advantageous due to the higher reactivity of such compounds
which could facilitate star-up [19] and/or stabilize the catalytic
reaction without the need of further pre-heating or piloting
[20]. When burning multi-fuels of carbon monoxide and hydrogen, blending with hydrocarbon in a catalytic micro-reactor will
exhibit complicated heterogeneous and homogeneous reactions
due to their different diffusive and catalytic characteristics. Nevertheless, the interplay of kinetics and transport of CH4/CO/H2
multi-fuel reactions in catalytic micro-reactors have rarely been
studied.
The utilization of micro-combustor requires high power design
depending on purpose, which can be obtained by increasing the inlet mass ow rate and thus gas velocity. On the contrary, to reach
high conversions, the residence time should be relatively high
which means that low inlet gas velocities are needed to prevent
blow-out. As a result, a trade-off in the choice of inlet gas velocities
has to be reached. Traditionally, the stable operating range of a
micro-reactor is restricted to low inlet velocities (less than 1 m/s)
[710]. To extend the operation range and to study the interplay
of H2/CO/CH4 multi-fuel reactions in a catalytic micro-reactor a
novel catalyst bed design that uses catalyst segmentation with
cavities is proposed in the present study.

2. Numerical model and chemical mechanism

In this work, a commercial code, CFD-ACE [21], was modied
and incorporated with detailed gas-phase and surface reaction
mechanisms in CHEMKIN format to simulate the ow and reaction
characteristics inside a micro channel. For simplicity, the microreactor was modeled as a two-dimensional system in the numerical simulation, with a gap width (L) of 1 mm between the two
parallel plates. In practical applications, a micro-reactor with a
large aspect ratio can be fabricated using MEMS technology. The
governing equations consist of two-dimensional NavierStokes
equations, mass and energy conservation equations, and a species
equation for each chemical species. Figure 1 shows a schematic of
the catalytic micro channel modeled in this work. Simulations
were performed on half of the channel due to symmetry. The reactor was 3 cm in length and had a wall thickness of 0.2 mm. Cavities
were used to increase the residence time and to enhance the
homogeneous reaction. The catalyst segments were coated with
platinum. A total catalyst length of 1 cm was used for segments
of various lengths in the comparisons. The cavity width was
1 mm and the cavity depth was 0.2 mm.
For boundary conditions, the stoichiometric fuelair mixture
was specied at the inlet. Three multi-fuel compositions were
studied: 50%H2 + 50%CO, 50%CH4 + 50%CO, and 50%CH4 + 50%H2.
The inlet temperature for the fuel/air mixture was 300 K. A uniform velocity prole of 10 m/s was specied at the inlet. A laminar
ow eld was used for all cases. The thermal boundary condition at
the wall was the heat lost to the ambient air at 300 K. The exterior
heat loss was due to heat convection by air, described as:

q00 hT w  300

1
2

where h is the heat transfer coefcient (20 W/m /K in this study)

and Tw is the wall temperature. At the exit, the pressure was specied as a constant ambient pressure of 101 kPa and an extrapolation
scheme was used for species and temperature.
Non-uniform meshes were used with more grids distributed in
the reaction region to provide sufcient grid resolution in the computational domain. Grid independence was examined and a nonuniform mesh with a distribution of 211  65 grid points in the axial and transverse directions was used. The simulation converged
when the residuals of all governing equations approached steady
states with residuals smaller than 104.
For gas properties and transport coefcients, the mixture density was calculated using the ideal gas law and the mixture viscosity, specic heat, and thermal conductivity were calculated from a
mass average of species properties. Detailed gas-phase and
catalytic surface reaction mechanisms were applied. The reaction
rate was represented by the modied Arrhenius expression. A
modied Arrhenius expression can be introduced by expressing
k(T) = BTa Exp(Ea/RT), where B is a constant, Ea is the activation
energy of the reaction (J/mole) and a is temperature exponent.
The GRI-Mech 3.0 mechanism was used for gas phase reactions;
it comprises 53 species and 325 reaction steps. The surface reaction mechanism was compiled primarily from that proposed by
Deutschmann et al. [22]. These reaction mechanisms have been
used in previous studies and comparisons with experimental results were satisfactory [23,24]. For methane fuel, eleven surface

Fig. 1. Schematic of computational domain.

Y.-H. Li et al. / Combustion and Flame 159 (2012) 16441651

species (C(s), CH(s), CH2(s), CH3(s), CO(s), CO2(s), H(s), H2O(s), O(s),
OH(s), PT(s)) describe the coverage of the surface with adsorbed
species. PT(s) denotes free surface sites available for adsorption.

3. Results and discussion

3.1. Effects of catalyst conguration
An investigation of methane combustion in a catalyst channel
was conducted rst since methane is typically weak in hetero-/
homo-geneous coupling and requires a long catalyst length for
complete conversion over platinum [25,26]. In our previous paper
[16], three kinds of micro-reactor design were implemented to improve the methane conversion: the catalytic system with a single
catalyst sector, system with catalyst segmentation, and system
with catalyst segmentation and cavities. The OH radical is one of
signicant radicals in the hydrocarbon oxidation, and the existence
of OH radical is generally indicated the reaction zone and high
temperature regions. Consequently, OH mass fraction is usually
used to delineate the gas reaction in a catalyst combustion
[22,25]. Figure 2 shows the computed results of methane and OH
mass fraction contours for various catalyst congurations for the
entire section. The equivalence ratio of these cases is 0.6 and the
inlet velocity is 10 m/s. This velocity substantially exceeds the
ame speed of methane; homogeneous combustion cannot be
sustained in a micro-reactor with non-catalytic walls under this
condition. However, the catalyst on the wall evidently extends
the blowout limit of methane. Numerical results indicate that the
homogeneous combustion exists in the centerline for all cases.
The corresponding ame anchoring positions, as shown by the high
OH concentration regions, are apparently distinct. In the single
catalyst case, fuel is consumed partially by the heterogeneous reaction in the vicinity of the catalyst and the other is consumed by the

homogeneous reaction in the centerline region. The catalytic surface supplies heat, intermediate species, bare active sites or others,
and sustains the gas reaction in this region.
For the multi-segment catalyst case, homogeneous combustion
is sustained in spaces between adjacent catalyst segments, where
the mixture inherits prior catalytically induced exothermicity
and intermediate species. High ow velocity moves the ame
anchoring downstream of the second catalyst segment. Methane
depletion occurs within the rst two catalysts, and surface chemistry dominates the local reaction in this region. Subsequently, a
large number of radicals congregated on the non-catalyst wall,
where homogeneous chemistry dominates the local reaction, as
shown in Fig. 2b. For the case of multi-segment catalyst with
cavities, methane attains complete conversion in a short distance,
and the ame anchoring moves upstream, as shown in Fig. 2c. The
existence of cavities can provide the low velocity zone to stabilize
the gas reaction, so that the methane oxidation can be accelerated
by assisting homogeneous and heterogeneous reaction. The performance of integrated catalyst segmentation with interlacing
cavities is superior to that of the single catalyst, especially in
high-velocity ows.

0.9

Y (mm)

1646

0.0E+00

-0.9
CH4:

0.0000 0.0113 0.0225 0.0338

OH:

0.0E+00 2.0E-03 4.0E-03 6.0E-03

CH4
0.0338

0.2

0.4

0.6

0.8

0.9

0.9

OH
8.0E-03

Y (mm)

Y (mm)

OH
6.0E-03

-0.9

1.0E-04

CH4
0.0338

(a)

Y (mm)

0.9
-0.9

0.0000

0.2

0.4

0.6

0.8

0
0.9

OH
6.0E-03

-0.9

Y (mm)

(b)

Y (mm)

0.9

0.0E+00

0
CH4
0.0338

-0.9

0.5

1.5

2.5

Axial distance (cm)

(c)
Fig. 2. Color-coded contours of methane and OH mass fraction for various catalyst
congurations: (a) without segmentation and cavity, (b) with 2 mm  5 segmentation, and (c) with 2 mm  5 segmentation and cavities.

-0.9

0.2

0.4

0.6

0.8

Axial distance (cm)

Fig. 3. Velocity magnitude and CO mass fraction contours superposed on colorcoded OH and CH4 mass fraction for the rst 1.0 cm section of various catalyst
congurations: (a) without segmentation and cavity, (b) with 2 mm  5 segmentation, and (c) with 2 mm  5 segmentation and cavities.

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Y.-H. Li et al. / Combustion and Flame 159 (2012) 16441651

3.2. Issues of fuel composition

Generally, gasied biomass, syngas and industrial residual gas
[27,28] contain various amount of hydrogen, carbon monoxide
and light hydrocarbons. However, these fuels, such as H2, CO and

For interpretation of color in Figs. 112, the reader is referred to the web version
of this article.

CH4, have distinct physical and chemical characteristics in heteroand homogeneous reactions. In order to investigate the interplay of
these fuels over platinum catalyst, binary fuels among H2, CO and
CH4 were addressed and compared for the hetero- and homogeneous reactions of three catalyst congurations in the stoichiometric condition. The composition ratio of binary fuel is considered as
5050% mixture and its corresponding inlet velocity is xed at
10 m/s for all cases.
3.2.1. Hydrogen and carbon monoxide mixture
Hydrogen and carbon monoxide have relatively high sticking
coefcients to platinum catalyst. However, hydrogen has an inherently large mass diffusivity compared to that of carbon monoxide,
so hydrogen rst reaches the catalyst bed and triggers the heterogeneous reaction. Figure 4 shows the computed contours of fuel
and the intermediate species mass fractions for stoichiometric
mixtures of an inlet velocity of 10 m/s for micro channels with conguration of single catalyst, catalyst segmentation and catalyst
segmentation with cavities. For the single catalyst conguration,
hydrogen inherently triggers heterogeneous reaction on the catalyst section, approximately reaches complete conversion and then
successively induces the gas reaction behind the catalyst. The gas
reaction mainly performs the fuel conversion of carbon monoxide,
so that the carbon monoxide conversion in a 30-mm micro-channel is about 83%. Nevertheless, in the cases of a multi-segment catalyst with and without cavities no signicant difference between
the two catalyst congurations was observed. Similarly, the gas
reaction was anchored in the inert walls or cavities between adjacent catalyst segments. The hydrogen and carbon monoxide conversion for both congurations can reach to 97% and 90%,
respectively, which is denitely higher than that in a single catalyst
case. In order to understand the interaction between hetero- and
homo-geneous reactions in a single catalyst case, Fig. 5 shows
the ratio of surface mass fraction to mean bulk mass fraction along

Y (mm)

0.9

H2

0.012
0.009
0.006
0.003
0.000

-0.9

0.162
0.108
0.054
0.000

CO

0.5

1.5

2.5

(a)
Y (mm)

0.9

H2

0.012
0.009
0.006
0.003
0.000

-0.9

0.162
0.108
0.054
0.000

CO

0.5

1.5

2.5

(b)
0.9

Y (mm)

In order to further explore the hetero- and homo-geneous interaction in various catalyst congurations, Fig. 3 shows signicant
specie and radical distributions along the rst 1.0 cm section of
the micro channel. The computed velocity magnitude, CO, CH4
and OH mass fractions expressed in iso-velocity, iso-concentration
and color1 codes of methane catalytic combustion in the microchannel with a single 10-mm-long catalyst was displayed in
Fig. 3a. The result shows that methane is depleted in the catalyst
bed via the heterogeneous reaction, and the following homogeneous reaction, which anchors in the boundary layer, is sequentially induced. The OH radicals are congregated in the centerline
of the channel, whereas the radicals near the catalyst bed are subject to absorption by the catalyst bed due to the high sticking coefcient of OH radicals. It leads to deprive the homogeneous reaction
of OH radicals. This phenomenon is related to specie quenching,
namely the competition of hetero- and homogeneous reactions.
Besides, the contour of the CO mass fraction in Fig. 3a demonstrates the formation of carbon monoxide behind the homogeneous reaction, and it occurs by incomplete combustion. Figure
3b shows methane catalytic combustion in the micro channel with
catalyst segmentation (ve segments of the 2-mm catalyst). It displays that the heterogeneous reaction occurs in rst two catalyst
segments, and the majority of methane conversion is achieved in
rst two catalyst segments. The OH mass fraction distribution denotes the location of the gas reaction in the centerline of the channel. The space between adjacent catalyst segments provides a
proper dwelling place for sustaining a homogeneous reaction with
sufcient intermediate species and catalytically induced exothermicity from upstream. It appears that ames are anchored on these
spaces, and the ame behavior is similar to the results of Benedettos work [13]. The increase of the CO mass fraction in Fig. 3b reveals incomplete combustion of the homogeneous reaction in high
velocity conditions, and the decrease of the CO mass fraction after
the following catalyst segments is caused by its high sticking coefcients on Pt surface. The catalyst segmentation effectively integrates the hetero- and homogeneous reactions to accomplish
complete methane conversion in a short length in a micro-reactor.
However, the ames which stabilize on the spaces are prone to be
affected by gas velocity.
High inlet velocity may reduce the residence time and defer
the onset of homogeneous ignition downstream. In order to
enhance ame stabilization in the micro-reactor, localized cavities
on the channel wall are proposed. The function of cavities is to provide a low-velocity zone to stabilize the homogeneous reaction.
Figure 3c shows that the gas velocity magnitude inside the cavity
is relatively low compared to that in the main stream; that is, cavities can stabilize the homogeneous reaction by providing a lowvelocity asylum. The CO mass fraction distribution illustrates the
reaction of the fuel mixture in a prior catalyst segment, and the
congregation of OH radicals in the cavities represents the ame
anchoring. The distance for complete methane depletion is reduced
and the ame anchoring location moves upstream compared to
that shown in Fig. 3a and b. As to the effects of inlet velocity, segment catalyst layout and cavity dimension, the further discussions
of methane combustion in a micro-scale catalytic channel are presented in the previous paper [26].

H2
0.012
0.009
0.006
0.003
0.000

CO

-0.9

0.5

1.5

2.5

0.162
0.108
0.054
0.000

Axial distance (cm)

(c)
Fig. 4. Computed contours of H2, CO (color coded), OH and CO2 mass fraction with
an equivalence ratio of 1.0 and an inlet velocity of 10 m/s for (a) single catalyst, (b)
multi-segment catalyst and (c) multi-segment catalyst with cavities.

Y.-H. Li et al. / Combustion and Flame 159 (2012) 16441651

100
95%

90

CO mass fraction
H2 mass fraction

80

Ys /Yb (%)

70
60
50
Heterogeneous
reaction

40
30

Homogeneous
reaction

20
10
Catalyst section

0
0

0.2

0.4

5%

0.6

0.8

1.2

1.4

1.6

1.8

Axial distance (cm)

Fig. 5. Ratio of surface mass fraction to mean bulk mass fraction of reactant along
the single catalyst micro-channel.

the channel. In general, the heterogeneous reaction can be considered as kinetically controlled, for which the surface concentration
is greater than 95% of the bulk concentration, and as mass transfer
controlled, for which the surface concentration is less than 5% of
the bulk. Within the 10 mm-long catalyst bed, hydrogen is completely consumed, but carbon monoxide has no signicant reaction. It appears that hydrogen tends to induce heterogeneous
reaction over the Pt catalyst, but the length of catalyst section is
not enough to develop into mass-transfer-control region. Heterogeneous reaction of carbon monoxide is barely observable and it
belongs to kinetic-control region in the catalyst section. However,
induced homogeneous reaction behind the catalyst prompts further acceleration of hydrogen/carbon monoxide chemical reactions. It turns out that carbon monoxide conversion dominantly
counts on homogeneous reaction, while hydrogen conversion
equally relies on heterogeneous and homogeneous reactions. Consequently, the fuel conversion efciency in single catalyst microchannel would be strongly related to fuel concentration, fuel ow
rate, fuel composition and catalyst length.
Figure 6 shows the fuel mass fraction distribution along the axial direction close to the inner wall for three different catalyst congurations. For multi-segment catalyst without and with cavities,
hydrogen tends to lightoff early on the catalyst surface, providing
catalytically induced exothermicity and signicant amounts of

0.014
H2

CO

mass fraction
Single catalyst case
Segment catalyst case
Segment catalyst with cavities case

0.01

3.2.2. Methane and carbon monoxide mixture

Methane and carbon monoxide have similar Lewis numbers, but
CO has a high sticking coefcient to platinum. Nevertheless, the
maximum laminar burning velocity increases with increasing CO
content in the CH4-air mixture, and fuelair mixture leans toward
fuel-rich side [29]. For example, laminar burning velocity of
50%CH4 + 50%CO fuel mixture in stoichiometric condition increases
by 30% than that of pure methane. In the single catalyst case, the
CH4/CO mixture cannot stabilize in high ow velocity. However, a
multi-segment catalyst sustains the gas reaction in the micro channel. Figure 8 shows that methane becomes depleted in the rst two
catalyst segments. However, incomplete combustion yields a high
concentration of CO species. The upstream heterogeneous reaction
provides chemical radicals and exothermicity, and the homogeneous reaction speeds up the dissociation of fuel species. However,
the very short residence time leads to a high carbon monoxide concentration in the exhaust gas. Subsequently, the following sequentially-segmented catalyst helps deplete carbon monoxide in the
residual combustible mixture until a complete conversion. For the
case with cavities, it shows that the gas reaction moves upstream

0.18

120

0.16

110
100

0.14
0.12

0.008

0.1

0.006

0.08
0.06

0.004

CO mass fraction

H2 mass fraction

0.012

chemical radicals to support the downstream hetero-/homogeneous reaction of carbon monoxide. It shows the effects to move
the carbon monoxide reactions upstream. Some bumps in fuel concentration distributions appear in non-catalyst section, where fuel
has no heterogeneous consumption but concentration accumulates
due to diffusion from mean stream. The Lewis number of hydrogen
is about 0.346, which is much smaller than that of CO (1.376). This
means that hydrogen is responsible for initializing surface reaction
and stabilizing the gas reaction in high ow velocity due to its high
mass diffusivity, and carbon monoxide is charged for main heat release in homogeneous reaction due to the fact that most hydrogen
is consumed in catalyst section.
In general, syngas and gasied biomass have varying amounts
of fuel compositions on hydrogen and carbon monoxide. In order
to investigate the fuel properties issues in the multi-segment catalyst with cavities system, Fig. 7 shows the fuel mass fraction distributions along the axial direction close to the inner wall for cases
of various fuel compositions, 30%H2 + 70%CO, 50%H2 + 50%CO and
70%H2 + 30%CO, respectively. Results show no signicant difference among these conditions, and have certainly high fuel conversions. Proper hydrogen amount in fuel mixture benets to prompt
the hetero- and homogeneous reactions of carbon monoxide in the
micro channel.

0.04
0.002

0.02

H2

CO

mass fraction
30%H2+70%CO

90

50%H2+50%CO

80

Ys/Yb (%)

1648

70%H2+30%CO

70
60
50
40
30
20
10

0
0

0.5

1.5

2.5

Axial distance (cm)

Fig. 6. Fuel (50%H2 and 50%CO) mass fractions for single catalyst, multi-segment
catalyst and multi-segment catalyst with cavities.

0
0

0.5

1.5

Axial distance (cm)

Fig. 7. Fuels (H2 and CO) mass fractions for various fuel compositions in a multisegment catalyst with cavities within the rst 2 cm from the entrance.

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Y.-H. Li et al. / Combustion and Flame 159 (2012) 16441651

0.12

0.9

Y (mm)

CH4
0.041
0.033

0.1

0.025
0.016
0.008

0.08

0.5

1.5

2.5

Mass fraction

0.000

-0.9

(a)
0.9

0.06

0.04

Y (mm)

CO
0.110
0.092
0.073
0.055
0.037
0.018
0.000

-0.9

0.5

1.5

2.5

Segment catalyst with cavities

Segment catalyst without

0.02

(b)

0.5

1.5

1.5

Axial distance (mm)

0.9
0.007

Segment catalyst with cavities

Segment catalyst without

0.005
0

0.5

1.5

2.5

Axial distance (cm)

(c)
Fig. 8. Computed contours of (a) CH4, (b) CO, and (c) OH mass fractions with an
equivalence ratio of 1.0 and an inlet velocity of 10 m/s for multi-segment catalyst
(top) and multi-segment catalyst with cavities (bottom).

and anchors in the rst cavity. Furthermore, a shorter distance is required for a relatively high conversion.
Figure 9 shows the fuel and radical mass fraction distributions
in the rst 2 mm from the entrance. In the rst 1 mm, methane becomes depleted in the catalyst segment, yielding CO and CH3 species. In the next 1 mm, the OH distribution in the cavity implies a
gas reaction, so CH4 and CH3 are further depleted in this region. A
high ow velocity postpones the onset of the gas reaction in the
multi-segment catalyst case, and the increase of the methane mass
fraction along the axial distance in the gure is due to mass diffusion from the main stream. Although methane may also yields carbon monoxide if incompletely reacted, OH and H radicals from the
gas reaction may promote CO depletion. The fast chemical reaction
of CO + OH ? CO2 + H for the gas reaction is more active than the
dry CO oxidation reaction of CO + O2 ? CO2 for the surface reaction. In other words, the CO surface reaction dominates in the rst
catalyst segment, providing exothermicity to pre-react methane.
Methane releases H and OH radicals to assist CO conversion in
the following gas reaction.
3.2.3. Hydrogen and methane
For hydrogen and methane mixture, there is no obvious gas
reaction in the single and multi-segment catalyst micro-reactors
under the stoichiometric and inlet velocity of 10 m/s conditions ,
but gas reaction can be stabilized in the micro-reactor for the case
with cavities. Comparing with the CH4/CO results above, the
hydrogen in CH4/H2 mixture has a similar volumetric energy density (12.7 MJ/m3) with that of CO (11.6 MJ/m3), but hydrogen has
higher mass diffusivity. Therefore, most hydrogen is consumed in
the upstream section of the catalyst. It turns out that catalytically
induced exothermicity from hydrogen in the single and multi-segment catalyst cases is unable to ignite the gas reaction of methane
due to low energy density and high heat loss. Hydrogen concentration in CH4/H2 mixture plays an essential role in successfully

Mass fraction

-0.9

0.006

0.004

0.003

0.002

0.001

0.5

Axial distance (mm)

Fig. 9. (a) Fuel (50%CH4 and 50%CO) and (b) radical mass fraction for multi-segment
catalyst and multi-segment catalyst with cavities within the rst 2 mm from the
entrance.

110
100
90
80
70

Ys /Yb (%)

Y (mm)

OH
8.0E-03
6.0E-03
4.0E-03
2.0E-03
0.0E+00

H2

CH4

mass fraction
20%CH4+80%H2

60

30%CH4+70%H2

50

50%CH4+50%H2

40
30
20
10
0
0

0.2

0.4

0.6

0.8

1.2

1.4

1.6

1.8

Axial distance (cm)

Fig. 10. Fuel (H2 and CH4) mass fractions for various fuel compositions in a multisegment catalyst within the rst 2 cm from the entrance.

triggering of hetero- and homogeneous reactions in a micro channel. Figure 10 shows fuels mass fractions for various hydrogen

Y.-H. Li et al. / Combustion and Flame 159 (2012) 16441651

H2

Y (mm)

0.9

0.005
0.004
0.003
0.001
0.000

-0.9

CH4

CO

0.5

1.5

0.044
0.033
0.022
0.011
0.000

2.5

3
OH

0.9

Y (mm)

8.0E-03
6.0E-03
4.0E-03
2.0E-03
0.0E+00

-0.9

0.5

1.5

2.5

5.0E-04
4.0E-04
3.0E-04
2.0E-04
1.0E-04
0.0E+00

Axial distance (cm)

Fig. 12. Computed contours of (a) fuel and (b) radical mass fraction with an
equivalence ratio of 1.0 and an inlet velocity of 10 m/s for multi-segment catalyst
with cavities.

1800

0.05
Temperature
CH4
H2(x10)

1700

0.04

1600

0.03

1500

0.02

1400

0.01

Mass fraction

volumetric concentrations in CH4/H2 mixture in a multi-segment

catalyst case. For the case of 50%H2 + 50%CH4 there is almost no
chemical reaction of methane, but hydrogen has obvious fuel consumption along the channel. Once hydrogen volumetric concentration in CH4/H2 mixture increases to 70%, methane is consumed
periodically on the catalytic surface very slowly in the downstream
region of the catalyst segments, but no signicant gas reaction can
be found. When hydrogen is increased to 80 vol.% in CH4/H2 mixture, the surface reaction of hydrogen can successfully ignite the
gas reaction of methane and has complete conversion of methane.
The minimum hydrogen volumetric concentration in CH4/H2 mixture for complete methane conversion in this specic condition is
71 vol.%.
In addition, the thermal conductivity of wall material in the micro channel is another essential parameter to affect hetero- and
homogeneous reactions. Figure 11 shows that fuel mass fraction
for three kinds of wall materials in the multi-segment catalyst case,
silicon (124 W/m/K), platinum (69.1 W/m/K) and cordierite
(3.3 W/m/K), respectively. These materials are feasible and practically applied in MEMS systems. Results show that high thermal
conductivity materials, such as silicon, signicantly enhance chemical reactions of methane and hydrogen. It means that high thermal
conductivity can deliver thermal heat from catalyst section to noncatalyst section for stabilizing gas reaction and even heat up the
downstream catalyst segments for accelerating sequential surface
reaction.
In principal, cavities decelerate the ow in localized spaces and
accumulate radicals from upstream. Figure 12 shows the fuel and
radical mass fractions for the multi-segment catalyst with cavities.
Reactions in the cavity stabilize the main gas reaction in the channel. As shown by the mass fraction distributions in Fig. 13a, methane is consumed in two stages within 2 mm from the entrance. The
rst stage, within the rst 1 mm, is dominated by the heterogeneous reaction of the catalyst, while the second stage, in the next
1 mm, is responsible for the gas reaction anchoring in the cavity.
A sharp temperature rise and OH radical congregation imply a
gas reaction in the cavity, as shown in Fig. 13b. The amount of
hydrogen decreases in the catalyst section, and then abruptly rises
in the cavity section after the dissociation of methane. The CO mass
fraction has a broadband distribution in two sections. Accordingly,
the incomplete combustion of methane leads to a high CO
concentration.

Temperature (K)

1650

1300
0

0.5

1.5

Axial distance (mm)

0.06

0.05

0.04

Mass fraction

110
100
90
80

0.02

0.01

70

Ys /Yb (%)

CO
CH3
OH

0.03

H2

CH4

mass fraction
Silicom (124 W/m/K)
Platinum ( 69.1W/m/K)
Cordierite ( 3.3W/m/K)

60
50

-0.01

40

0.5

1.5

Axial distance (mm)

30

Fig. 13. (a) Temperature, fuel (50%CH4 and 50%H2), and (b) radical mass fraction for
multi-segment catalyst and multi-segment catalyst with cavities within the rst
2 mm from the entrance.

20
10
0
0

0.2

0.4

0.6

0.8

1.2

1.4

1.6

1.8

Axial distance (cm)

Fig. 11. Fuel (50%CH4 and 50%H2) mass fractions for various wall materials in a
multi-segment catalyst within the rst 2 cm from the entrance.

The high wall temperature in the high ow velocity case is the

key to sustaining a gas reaction in the micro-reactor. In view of the
low volumetric energy density but high mass diffusivity of hydrogen, diminishing heat loss and providing a stable heat source on

Y.-H. Li et al. / Combustion and Flame 159 (2012) 16441651

the wall are important factors for high chemical conversion. Consequently, the hydrogen volumetric concentration in the CH4/H2
mixture and wall properties is an important design parameter.
4. Conclusion
The effects of catalyst segmentation and cavities on H2/CO/CH4
multi-fuel combustion enhancement in a micro-reactor were
investigated using numerical simulation with detailed heterogeneous and homogeneous mechanisms of methane, carbon monoxide, and hydrogen. Three catalyst congurations were considered
to improve the hetero- homo-geneous reactions in the micro channel. Results reveal that the heterogeneous reaction in the prior catalyst segment can produce active chemical radicals and
catalytically induced exothermicity; a homogeneous reaction is
subsequently induced and anchored in the following cavity. The
CO/H2 mixture can be sustained in high ow velocity for all three
catalyst congurations due to the high sticking coefcients of CO
and H2. This allows CO/H2 to lightoff on the catalyst segment.
The CO/CH4 mixture can be stabilized in high ow velocity in a micro channel with a multi-segment catalyst and with a catalyst with
cavities. In the upstream catalyst segment, incomplete combustion
of methane yields carbon monoxide, and the following catalyst
segments can then completely consume the yielded carbon monoxide due to the preferred CO catalytic reaction of a high sticking
coefcient on the platinum surface. Furthermore, OH and H radicals from methane enhance the CO gas reaction by switching the
chemical reaction pathway of CO. For the CH4/H2 mixture, only
the case with catalyst segmentation and cavities can stabilize the
gas reaction with high inlet ow velocities. Cavities can collect radicals and hot gases from upstream and provide low velocity zone to
sustain and anchor gas reactions for high inlet ow velocity mixtures even though hydrogen provides low volumetric energy density. These processes of multi-fuel catalytic combustion are
associated with the mutual assisting coupling between the heterogeneous and homogeneous reactions, instead of the competition
found in the conventional catalyst reactor. A complete methane
conversion and combustion can thus be accomplished in a short
distance, allowing the system to be further scaled down. The cavities appreciably extend the stable operation range of the multifuel micro-reactor for a wide range of inlet ow velocities. These
features allow the proposed catalyst conguration to be applied
to various small-scale power and heat generation systems.

1651

Acknowledgments
The computer time and the numerical packages provided by the
National Center for High-Performance Computing, Taiwan (NCHCTaiwan), are sincerely acknowledged.
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