Applied Energy 130 (2014) 350–356

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Applied Energy
journal homepage: www.elsevier.com/locate/apenergy

Combustion of propane with Pt and Rh catalysts in a meso-scale heat

recirculating combustor
Teresa A. Wierzbicki a,b, Ivan C. Lee b, Ashwani K. Gupta a,⇑
a
Department of Mechanical Engineering, University of Maryland, 2181 Martin Hall, Campus Dr., College Park, MD 20742, USA
b
Sensors and Electron Devices Directorate, U.S. Army Research Laboratory, 2800 Powder Mill Rd., Adelphi, MD 20783, USA

h i g h l i g h t s

 Compared extinction limits of catalytic and non-catalytic combustor operation.

 Analyzed catalytic conversion, product selectivity/yield, and activation energy.
 Results used to predict the catalytic combustor performance with liquid fuel.
 Catalysts offered enhanced stable operation of combustor than without catalyst.
 Rh is more suitable for liquid fuel due to higher fuel conversion and output energy.

a r t i c l e i n f o a b s t r a c t

Article history: The results obtained from the combustion behavior of propane over platinum and rhodium catalysts in a
Received 9 February 2014 meso-scale heat recirculating combustor are presented. The extinction limits, conversion, product selec-
Received in revised form 21 April 2014 tivity/yield, and activation energy using the two catalysts were compared in an effort to predict their per-
Accepted 31 May 2014
formance using a liquid fuel. The extinction limits were also compared to those of non-catalytic
Available online 17 June 2014
combustion in the same combustor. The results showed that the use of a catalyst greatly expanded the
range of stable operating conditions, in terms of both extinction limits and flow rates supported. The
Keywords:
Rh catalyst was found to exhibit a higher propane conversion rate, reaching a maximum of 90.4% at stoi-
Catalytic combustion
Heat-recirculating combustor
chiometric conditions (as compared to only 61.4% offered by the Pt catalyst under lean conditions), but
Meso-scale combustion the Pt catalyst had superior CO2 selectivity for most of the examined conditions, indicating more of the
Propane oxidation heat released being used for product formation as opposed to being lost to the environment. However,
Combustion behavior despite having a higher rate of heat loss, the combustion with the Rh catalyst produced an overall higher
amount of enthalpy than the Pt due to its superior fuel conversion. The Pt catalyst also had a significantly
smaller activation energy (13.8 kJ/mol) than the Rh catalyst (74.7 kJ/mol), except at equivalence ratios
richer than U = 1.75 (corresponding to catalyst temperatures below 500 °C), where it abruptly changed
to 211.4 kJ/mol, signifying a transition from diffusion-limited reactions to kinetically limited reactions
at this point. The results reveal that Rh would be a more suitable catalyst for use in liquid-fueled
meso-scale combustors, as fuel conversion has been found to be a limiting factor for combustion stability
in these systems, and as its higher output energy allows for greater flexibility of use.
Ó 2014 Elsevier Ltd. All rights reserved.

1. Introduction
Much interest in meso-scale combustion systems has been gar-
nered of late due to the benefits they offer in terms of local power
production, micro thrust, and micro propulsion generation. Hydro-
carbon fuels have much higher specific energies than batteries,
⇑ Corresponding author. Tel.: +1 301 405 5276.
E-mail addresses: twierz@umd.edu, teresa.wierzbicki.civ@mail.mil
(T.A. Wierzbicki), ivan.c.lee2.civ@mail.mil (I.C. Lee), akgupta@umd.edu (A.K. Gupta).
implying that even devices with very low thermal-to-electric effi-
ciencies can yield higher electrical outputs than batteries, and thus
offer significant performance improvements in portable electronic
devices, i.e. longer lifetime and reduced weight [1]. Liquid hydro-
carbons are ideal for use in these devices, as they are very
energy-dense and can be easily stored. Several studies have dem-
onstrated the successful coupling of meso-scale combustion sys-
tems with thermoelectric/thermophotovoltaic devices to produce
electric power [2–6]. However, there are some problems inherent
to meso-scale combustion systems. When the system is scaled

http://dx.doi.org/10.1016/j.apenergy.2014.05.069
0306-2619/Ó 2014 Elsevier Ltd. All rights reserved.
 T.A. Wierzbicki et al. / Applied Energy 130 (2014) 350–356
Nomenclature
A0 pre-exponential factor
C/O carbon to oxygen ratio
Ea activation energy
k reaction rate constant
[k] concentration of species k
NC,k total moles of carbon in species k
NC,out total moles of carbon in combustion products
r reaction rate
down, the heat loss to heat generation (or surface area to volume)
ratio increases, which can induce flame quenching as the system
size is reduced. A prevalent technique to diminish this effect is to
utilize a heat recirculating, swiss roll-style combustor, which
allows heat to be transferred from the products to the reactants,
thus permitting stable combustion in channels with a characteris-
tic dimension smaller than the flame quenching distance. The pre-
heating of reactants also broadens the range of stable operating
conditions by extending the lean flammability limits of the fuel
used [7]. Much research has been done to investigate the effects
of geometry, scaling, operating conditions, and combustor material
on the extinction limits and thermal performance of meso- and
micro-scale swiss roll combustors [8–14]. By varying the geometry
and inlet conditions (i.e. equivalence ratio and Reynolds number),
meso-scale swiss roll combustors can be tailored to suit a wide
range of both power generation and thrust applications [15,16].
Shirsat and Gupta [9] studied this concept in the context of thrust
generation for such applications as nanosatellites, power genera-
tion, and small robotics, and reported that the optimal geometry
for flame maintenance while minimizing heat loss and maximizing
exhaust enthalpy was a single-turn combustor design.
Another intrinsic difficulty in meso- and micro-combustion
systems is the very short residence time within the combustion
chamber. At such short residence times, complete combustion
of heavier hydrocarbons, especially in blended fuels, may not
always occur, resulting in significant soot formation and flame
instabilities [15]. A possible solution to this problem is to utilize
a catalyst in the system. Catalysts have been shown to help
stabilize liquid fuel combustion at short residence times, even
for petroleum-based jet fuels [17–19]. The high surface area to
volume ratio that is characteristic of small-scale systems is also
ideal for use with a catalyst, as increased surface area favors cat-
alytic combustion by providing more sites upon which the fuel
and oxidizer can adsorb. The addition of a catalyst has been
shown in many studies to widen the range of stable operating
conditions, lower the overall reactor temperatures, and increase
the hydrocarbon oxidation rates [20–22]. Spadaccini et al. [23]
found that the addition of a porous platinum catalyst to their
microscale gas turbine allowed for an increase in operable mass
flow rates through the system, leading to an 8.5-fold increase in
power density over the maximum achieved for a non-catalytic
system of similar geometry. Catalysts also play a key role in ther-
mal management—lower overall temperatures result in smaller
temperature gradients throughout the system, reducing the risk
of thermal stresses. Also, since chemical reactions theoretically
only occur on catalyst surfaces, the heat source location is fixed,
unlike in homogenous combustion, where the flame location
may change depending on operating conditions [8]. Due to this
enhanced stability and improved thermal management,
integration of catalytic micro- and meso-scale combustors with
such energy-harnessing devices as thermoelectrics/thermophoto-
voltaics and steam reformers is conjectured to be much simpler
than the corresponding non-catalytic burners [24].
351
R universal gas constant
t time
T temperature
V_ k volumetric flow rate of species k
mk stoichiometric coefficient of species k
U equivalence ratio
The current study examines the impact of adding a porous foam
catalyst to a single-turn swiss roll combustor burning a mixture of
propane and air. Two different catalysts, rhodium and platinum,
were investigated. The objective of this study is to analyze the role
of Rh and Pt catalysts in terms of extinction limits (particularly
how these limits compare to those of non-catalytic combustion
in the same reactor), conversion, selectivity, and activation energy.
Total oxidation of propane is used as a probe reaction in this study,
since oxidation reactions are essential to maximizing stability and
efficiency while minimizing emissions in power generation and
thrust production applications [25]. The results will help guide in
determining as to which catalyst would be most suitable for imple-
mentation in a similar combustor using liquid fuels.
2. Experimental
2.1. Combustor and catalyst
A single turn heat recirculating combustor similar to that uti-
lized by Shirsat and Gupta [9] and Wierzbicki et al. [15] was used.
The fuel and the oxidizer were introduced to the combustion
chamber partially premixed, with the fuel injected downstream
from the oxidizer to prevent any flashback into the inlet reactant
tubing. A step entrance to the combustion chamber was created
to generate a vortical flow structure and local recirculation zone
within the chamber, recirculating both heat and active species
from the products to the reactants. The aerodynamics of this flow
structure allowed for flame stabilization to occur in homogenous
gas-phase combustion, a concept used by Shirsat and Gupta [9].
The combustor was fabricated from a 1.5 in (3.8 cm) square
monolith alumina silicate block using conventional micro machin-
ing tools. The material has a thermal conductivity of 1.98 W/m K in
its green state, and has a low porosity relative to other more ther-
mally insulating materials, such as zirconium phosphate, which
has a thermal conductivity of 0.8 W/m K [11]. Porosity is an impor-
tant factor to consider, due to the possibility of altering the ratio of
fuel to oxidizer within the combustion chamber via reactants dif-
fusing into the reactor itself. Additionally, the low thermal conduc-
tivity of the material ensures large temperature gradients through
the channel walls, enabling favorable heat transfer rates from
products to reactants, as well as reduced heat loss from the com-
bustion chamber to the surroundings, thus increasing the resis-
tance to thermal quenching [12]. After machining, the combustor
was heat treated for 45 min at 1050 °C at a ramp rate of 2 °C per
minute. This process increased the hardness and strength of the
alumina silicate, thus lessening the possibility of the material
cracking due to thermal stresses.
The catalysts were fabricated using an incipient wetness
impregnation technique. Solutions of Rh(NO3)3 and Pt(NO3)4 were
deposited onto yttria-stabilized zirconia (YSZ) felts with a porosity
of 95% and thermal conductivity of approximately 0.09 W/m K.
This extremely low thermal conductivity allowed for very steep
352 T.A. Wierzbicki et al. / Applied Energy 130 (2014) 350–356
Fig. 1. Schematic of experimental facility.
temperature gradients between the front and back faces of the cat-
alyst. The felt was then calcinated at 700 °C for 16 h before inser-
tion into the combustor.
2.2. Experimental facility and procedure
Fig. 1 shows a schematic diagram of the experimental facility.
The experimental facility was designed to allow for efficient data
acquisition on the extinction limits, thermal performance, and fuel
conversion under both the heterogeneous (catalytic) and homoge-
neous (non-catalytic) operating conditions. Three thermal conduc-
tivity mass flow controllers were used to regulate the flow rates of
oxygen, argon, and propane in the combustor. A mixture of 21% O2
and 79% Ar, simulating air, was used as an oxidizer. K-type thermo-
couples were used to monitor the inlet air temperature, mixture
pre-heat temperature, product gas temperature (at the exit of the
combustion chamber), and exhaust gas temperature. In addition,
for the catalytic combustion experiments, the temperatures at
the front and back faces of the catalysts were also monitored. Care-
ful insertion of the thermocouples ensured that the tips did not
protrude too far into the channels and disturb the flow. For the het-
erogeneous combustion experiments, the catalyst was placed
directly into the combustion chamber, and blank YSZ felt was
placed in the inlet channel to serve as a heat shield. To initiate
Fig. 2. Photograph of (a) catalytic combustor and (b) non-catalytic combustor.
combustion, propane and air were allowed to flow though the
combustor and the system was heated until the propane autoignit-
ed on the catalyst. For the homogenous combustion experiments, a
high voltage spark generator was used to ignite the fuel/air mix-
ture via ignition electrodes located in the combustion chamber.
Fig. 2 shows photographs of the heterogeneous and homogeneous
combustors. The product gases from the combustor were then fed
into a micro-gas chromatograph and a mass spectrometer for com-
position analysis.
The extinction limits were determined by stabilizing a flame
within the combustion chamber and varying the flow rates of oxy-
gen, argon, and propane until the reaction could no longer be sup-
ported. To determine the effect of equivalence ratio on the
combustion behavior, propane flow rate was held constant, and
the flow rates of oxygen and argon were varied. For each operating
condition examined, the system was allowed to reach steady state,
as indicated by constant temperatures and product concentrations.
The two primary parameters observed were propane conversion
(to determine the effectiveness of the two catalysts) and CO2/CO
selectivity, to determine the completeness of combustion. A kinetic
analysis was also performed to determine the activation energy of
each catalyst.
3. Results and discussion
3.1. Extinction limits
The measured extinction limits of the catalytic and non-cata-
lytic combustors are shown in Fig. 3a and b, respectively. These
limits were defined as the points at which combustion was no
longer sustainable. This occurred when the flame was either blown
Fig. 3. Extinction limits for (a) catalytic combustors and (b) non-catalytic
combustor.
 T.A. Wierzbicki et al. / Applied Energy 130 (2014) 350–356 353

out (at the lean limits) or extinguished (at the rich limits) in the
homogeneous experiments, and when the catalyst underwent a
steep, steady drop in temperature in the heterogeneous experi-
ments. In this study, the equivalence ratio, U, is defined as the
actual carbon to oxygen (C/O) ratio divided by the stoichiometric
C/O ratio:

ðC=OÞactual
U¼ ð1Þ
ðC=OÞstoich
The catalysts were both able to sustain very lean combustion,
down to an equivalence ratio of U = 0.593 for the Rh catalyst and
U = 0.322 for Pt. The ability of the Pt catalyst to support such sig-
nificantly leaner combustion than the Rh catalyst is likely due to
Fig. 4. Propane conversion percentage in catalytic combustors.
its lower activation energy (13.8 kJ/mol for Pt vs. 74.7 kJ/mol for
Rh). This will be further discussed in Section 3.3. No absolute rich
limits were found for either catalyst, even at equivalence ratios in exception of equivalence ratios below 0.8, the Rh catalyst delivered
excess of U = 15, which is consistent with previously reported a significantly higher conversion than Pt, especially under fuel rich
studies on catalytic microcombustion with propane and air [8]. conditions, reaching a maximum of 90.4% at U = 1.0. However,
However, for super-rich combustion (U > 3) the fuel conversion under lean conditions, the conversion was found to have a very
was extremely low and the exhaust gas temperature was low, indi- steep decline. It is conjectured that this is due to the shorter con-
cating that the combustor could not be used for any practical pur- tact times at the higher flow rates that accompany lean combus-
poses at these conditions. Fig. 3a shows the lean blowout limits for tion, which result in insufficient time for complete conversion of
the Rh and Pt catalytic combustors. While the results obtained fuel. This implies that at these conditions mass transfer limitations
revealed that there is a relationship between total flow rate and for the combustion reaction on Rh may exist, as the higher flow
blowout limit for the Rh catalyst (higher flow rates can sustain rates may prevent the reactants from diffusing from the bulk flow
lower equivalence ratios), the same did not appear to be true for to the catalyst surface. With the Pt catalyst, the conversion
the Pt catalyst; for all flow rates studied the blowout limit was increased as equivalence ratio decreased, reaching a maximum of
approximately constant. This difference in trends is likely due to 61.4% at U = 0.66, the leanest condition studied and thus the point
the activation energies of the catalysts. As less fuel is added to at which the most O2 was available to oxidize the propane.
the system (i.e. less input thermal energy), the overall temperature The selectivities of CO2 and CO were investigated to evaluate
decreases due to the lower heat release from the chemical reac- the completeness of combustion, as this is a good representative
tions. At low total flow rates, very low fuel flow rates must be used measure of catalyst performance. In addition to the experimental
in order to achieve lean combustion. The Pt catalyst was able to data, thermodynamic equilibrium product gas compositions were
sustain combustion at these low temperatures due to its relatively found using CHEMKIN software, and the equilibrium CO2 and CO
low activation energy. However, due to its higher activation
energy, the Rh required a higher catalyst temperature to propagate
the combustion reactions, and at low fuel flow rates the heat
release was insufficient to sustain these higher temperatures.
The non-catalytic combustor was found to have a much smaller
operating range, as shown in Fig. 3b. Although it could sustain
combustion down to a minimum equivalence ratio of 0.425, it
could not support combustion at total flow rates above approxi-
mately 950 SCCM (cm3/min). This is consistent with previous stud-
ies, which showed that the use of a porous foam catalyst increases
the maximum flow rate supportable by the combustor [23]. Addi-
tionally, for all flow rates examined, the non-catalytic combustor
had relatively low rich extinction limits, reaching a maximum at
an equivalence ratio of only 1.75.

3.2. Exhaust gas analysis

The fuel conversion, CO2/CO selectivity, and CO2/CO yield were

calculated using:

V_ C3 H8 ;in  V_ C3 H8 ;out
%Conv ersion ¼  100% ð2Þ
V_ C H ;in
3 8

NCout;k
Selectiv ity of species k ¼  100% ð3Þ
NCout
Yield of species k ¼ Conv ersion  Selectiv ity ð4Þ

where V_ C3 H8 represents the volumetric flow rate of propane, and

N Cout represents the total moles of carbon present in the combustion
products.
Fig. 4 shows the total propane conversion under heterogeneous
conditions using the Rh and Pt catalysts. It is clear that, with the Fig. 5. Product selectivity in catalytic combustors for (a) CO2 and (b) CO.
354 T.A. Wierzbicki et al. / Applied Energy 130 (2014) 350–356

selectivities calculated from these values. As seen in Fig. 5, the Pt

catalyst had a considerably larger CO2 selectivity (and Rh a consid-
erably larger CO selectivity) for all the conditions examined, with
the exception of U < 0.8, where there was adequate excess O2 pres-
ent to completely oxidize the fuel. As CO2 has a higher enthalpy of
formation than CO, a higher CO2 selectivity is indicative of a higher
percentage of enthalpy being directed into forming products, and
thus is not lost to the environment. The general trend for both cat-
alysts is the highest CO2 selectivities under lean conditions,
decreasing to a minimum between 1.75 < U < 2, and then increas-
ing again beyond this point. It is expected that the selectivities
would be highest at lean operating conditions, as there is excess
oxygen available to form CO2, but the reason for the increase above
U = 2 is not as obvious. It is conjectured that this may be due to the
longer contact times occurring with richer conditions that allow
more time for the reaction to overcome the lack of excess oxygen.
This requires substantiation and further examination.
The equilibrium calculations did not take into account the cat-
alytic effect on product selectivity, as evidenced by the discrepan-
cies between the two data sets. As seen in Fig. 6a, the CO2 and CO
selectivities from the Rh mimic the equilibrium trend fairly well up
until U = 2, where the experimental trend diverges from the
model, with the equilibrium calculations under-predicting the CO
(and over-predicting the CO2). This over-production of CO is fairly
typical behavior of Rh, as it has been found that, at operating tem-
peratures similar to those in this study, Rh does not catalyze the
water gas shift (WGS) reaction (Eq. (5)) very well [26].
H2 O þ CO ! H2 þ CO2 ð5Þ

Fig. 7. Product yield in catalytic combustors for (a) CO2, (b) CO, and (c) H2.

The experimental data from the Pt catalyst, on the other hand,

Fig. 6. Experimental (closed symbols) and equilibrium (open symbols) CO2 and CO
selectivities for (a) Rh catalyst and (b) Pt catalyst.
although exhibiting a similar trend, does not mimic the shape of
the equilibrium curve. As shown in Fig. 6b, lean of U = 1, the CO
selectivity is under-predicted and the CO2 selectivity over-pre-
dicted, and the opposite is true under fuel-rich conditions.
Despite having a significantly lower CO2 selectivity, due to the
superior conversion rates of the Rh catalyst, it had a slightly higher
CO2 yield than the Pt at all examined conditions, as seen in Fig. 7a.
This indicates that, in spite of having a higher rate of heat loss to
the environment, there is an overall higher enthalpy in the exhaust
from the Rh catalyst, which is reflected in the slightly higher tem-
peratures recorded for virtually every operating condition exam-
ined. This was further validated by calculating the enthalpy in
the exhaust for both catalysts (see Fig. 8). A higher amount of
enthalpy present in the exhaust implies greater potential for use
in both thrust production and power generation applications. The
Rh catalyst also had significantly higher CO and H2 yields than
the Pt (Fig. 7b and c), which suggests that a meso-scale combustion
system with an Rh catalyst could be further optimized to produce
 T.A. Wierzbicki et al. / Applied Energy 130 (2014) 350–356
Fig. 8. Exhaust enthalpy in catalytic combustors.
syngas, for such applications as fuel cells. Additionally, at the con-
dition of maximum conversion (90% at U = 1), the Rh system
paired with a low-temperature thermoelectric device can achieve
a power density up to 70% higher than a lithium ion battery of
equivalent mass.
The data obtained here suggests that, in terms of conversion,
selectivity, and yield, Rh is a more suitable choice than Pt for a
meso-scale combustor. Conversion is particularly important when
utilizing liquid fuels in a combustor of this scale, as the residence
time is often not sufficient to fully combust the heavier
hydrocarbons.
3.3. Kinetic analysis
The rate constant governing steady-state combustion was cal-
culated using:
1 d½C3 H8 
r¼  ð6Þ
vC H
3 8
dt
r ¼ k  ½C3 H8 v C3 H8  ½O2 v O2
where v C3 H8 and v O2 represent the stoichiometric coefficients of
C3H8 and O2, respectively. As argon was a non-reacting species in
these experiments, and since its concentration was very large com-
pared to those of propane and oxygen, its contribution to the overall
reaction rate was neglected. For non-stoichiometric mixtures of
propane and air, the equivalence ratio, U, was used for v C3 H8 . The
results were then plotted in an Arrhenius plot (Eq. (8)), shown in
Fig. 9, and linear regression was used to determine the activation
energies required for steady-state combustion.
Ea
k ¼ A0 eRT
As presented in the extinction limit analysis in Section 3.1, the
activation energy of the Rh catalyst was relatively high (74.7 kJ/
mol) and the Pt catalyst relatively low (13.8 kJ/mol) for most of
the conditions examined. However, as seen in Fig. 9b, the slope
of the Arrhenius plot for Pt changes drastically at low temperatures
(T < 500 °C), which corresponds to higher equivalence ratios
(U P 1.75). For these low temperatures, the activation energy
was calculated to be 211.4 kJ/mol. This drastic change signifies a
transition from mass diffusion-limited reactions at lower equiva-
lence ratios to chemical kinetics-limited reactions at higher equiv-
alence ratios. It has been postulated that this transition with
respect to equivalence ratio is due to the adsorption of O(s) onto
the Pt surface, since at low temperatures O(s) desorption from
the catalyst surface is slow, thus reducing the catalytic activity
[27]. Additionally, at low temperatures, the high O(s) surface cov-
355
Fig. 9. Arrhenius plots for (a) Rh catalyst and (b) Pt catalyst.
erage inhibits C3H8 adsorption to the catalyst surface; however, at
fuel-rich conditions, the excess C3H8 is able to prevent complete
O(s) surface coverage [8,22]. Thus, for these low-temperature,
fuel-rich conditions, there is more competitive adsorption on the
Pt surface between the C3H8 and the O2, leading to kinetically lim-
ited reactions. Furthermore, the calculated value of 211.4 kJ/mol is
ð7Þ in excellent agreement with the activation energy of O(s) desorp-
tion from Pt at low temperatures (213.0 kJ/mol) provided in an
established mechanism [28], further supporting that, at these con-
ditions, the rates of the reactions occurring on the Pt surface are
controlled by the chemical kinetics.
However, for most operating conditions studied, the activation
energy of the Pt catalyst was significantly lower than that of the
Rh, indicating greater ease of ignition (i.e. less input energy) for
the system with Pt catalyst. Based on the value of the Rh catalyst
activation energy one can conjecture that the reactions occurring
in the Rh combustor are chemical kinetics-limited. However, the
steep drop in propane conversion at equivalence ratios lean of stoi-
ð8Þ chiometry suggests a possible influence of mass transfer limita-
tions. A closer examination of Fig. 9a reveals that it is not
entirely clear from the data whether the reactions are entirely
kinetics-limited, or if it is a combination of kinetic and diffusion
limitations. A future study analyzing a much wider range of oper-
ating conditions may strive to address this question thus gaining
further insights into the complex phenomena.
4. Conclusions
A meso-scale, heat recirculating combustor was utilized to
examine the gas phase and catalytic combustion behavior of pro-
pane. Rh and Pt catalysts were used. The results showed that the
addition of a catalyst to the system greatly increased the stability
limits, and completely eliminated the rich extinction limit up to
the regions examined. The Pt catalyst was able to support signifi-
356 T.A. Wierzbicki et al. / Applied Energy 130 (2014) 350–356
cantly leaner combustion than the Rh catalyst at all the flow rates
examined. The two catalysts were further compared to determine
their effectiveness, combustion behavior, and activation energies.
The results showed that, although having a considerably higher
propane conversion rate for virtually all the equivalence ratios
examined, the Rh catalyst had an overall poorer CO2 selectivity
than Pt, indicating a higher rate of heat loss to the environment.
However, due to its superior conversion, the CO2 yield from the
Rh was higher than from the Pt, indicating higher overall output
enthalpy. The calculated activation energies for each catalyst
(74.7 kJ/mol for Rh and 13.8 kJ/mol for Pt) suggested that the com-
bustion reactions on Rh were largely controlled by chemical reac-
tion kinetics and on the Pt by diffusion limitations. However, at
high equivalence ratios (U P 1.75), there is an abrupt change in
the reaction kinetics on the Pt catalyst, likely due to the low-tem-
perature competitive adsorption between C3H8 and O2 on the Pt
surface, which signifies a transition to kinetically limited combus-
tion. The results revealed that higher conversion and CO2 yield
with the Rh catalyst make it a better choice for use of this system
with a liquid fuel. This is in spite of the higher activation energy of
the Rh; conversion is a more important parameter than activation
energy to consider for these applications, as the residence time in a
meso-scale combustor is often too short to fully combust the heavy
hydrocarbons, and the energy required to vaporize the fuel is
higher than that needed for catalytic ignition.
Acknowledgments
Research support provided to Teresa Wierzbicki by the U.S.
Army Research Laboratory is gratefully acknowledged. Thanks
are also due to Dr. Vivek Shirsat for all his help and support in var-
ious stages of this research and in the design and development of
heat recirculating micro-combustors.
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