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Steam reforming of methane and methanol in simulated macro & micro-scale

membrane reactors: Selective separation of hydrogen for optimum
conversion

Article in Journal of Natural Gas Science and Engineering · May 2014

DOI: 10.1016/j.jngse.2014.03.008

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 Journal of Natural Gas Science and Engineering 18 (2014) 286e295

Contents lists available at ScienceDirect

Journal of Natural Gas Science and Engineering

journal homepage: www.elsevier.com/locate/jngse

Steam reforming of methane and methanol in simulated macro &

micro-scale membrane reactors: Selective separation of hydrogen for
optimum conversion
Anubhav Pratap Singh a, Siddhartha Singh a, Somenath Ganguly a, *, Anand V. Patwardhan b
a
Department of Chemical Engineering, Indian Institute of Technology, Kharagpur 721302, India
b
Department of Chemical Engineering, Institute of Chemical Technology, Mumbai, India

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

Article history: Various configurations of membrane reactor for steam reforming of methane and methanol are studied
Received 24 December 2013 here using mathematical model. Micro-scale membrane reactor is conceptualized as a channel with one
Received in revised form wall coated with catalyst material, and the other wall permeating hydrogen through a layer of palladium.
10 March 2014
The membrane layer helps in removal of hydrogen from the reaction site, thereby shifting the equilib-
Accepted 11 March 2014
Available online 3 April 2014
rium conversion. In comparison with macro-scale model, the membrane micro-reactor required a shorter
residence time to achieve the same level of conversion. This is primarily because of better removal of
hydrogen, and is true even when the dispersed catalyst density remained same in both macro and micro
Keywords:
Membrane
models. Any perturbation in the rate constants of sub-reactions that could be arising from catalyst site
Reactor rearrangements in the micro-fabricated layer does not significantly affect the conversion. Effects of the
Steam thickness of the membrane and operating temperature on the conversion are discussed. The pressure
Reforming drop along the length of the channel arising from friction, reaction stoichiometry, and permeation of
Model product component was estimated. The ratio of membrane area to the catalytic surface area in the
Micro-channel channel as a function of distance from the inlet end should be such that the conversion is maximized.
Macro This is observed that with selective placement of membrane and catalyst, a methane conversion of more
Methane
than 95% can be achieved by considering only 40% of the wall, covered with membrane.
Methanol
Ó 2014 Elsevier B.V. All rights reserved.

1. Introduction steam reforming of methane is known for production of synthesis

Over the last few years, large numbers of electronic devices,
such as computers, cellular phones have become portable with the
miniaturization of electronic components. Improved performance
of these electronic devices requires supply of power from a source
that has sufficient power density and life-time. At smaller size, the
electrochemical devices are more competitive because of their
simplicity. They also promise higher energy densities, as scaling is
no longer a function of volume. Typically, the fuel cells rely on
production of hydrogen at the point of application. Catalytic steam
reforming of methane is a method to generate hydrogen for this
purpose. Fuel processors utilizing steam reforming of hydrocarbons
are actively being developed for small and micro-scale portable
hydrogen generators (Roychoudhary et al., 2005). In addition,
* Corresponding author. Tel.: þ91 3222 283956; fax: þ91 3222 282700.
E-mail address: snganguly@che.iitkgp.ernet.in (S. Ganguly).
gas (H2 and CO), a feedstock for important raw materials.
Micro-reactor offers many advantages, e.g., improvements in
energy efficiency, reaction speed, safety, reliability, scalability, on-
site and on-demand production, better control, and possibly bet-
ter yield and selectivity compared to those of conventional reactors.
The use of micro-reactor in steam reforming potentially minimizes
the temperature gradient, and ensures higher average temperature
and process efficiency. The diffusion paths in catalytic coatings of
the microchannels are small (Karakaya et al., 2009) so that heat and
mass transport resistances can be neglected. In addition, small
channel dimensions and presence of adiabatic conditions allow
gradients in the radial direction to be neglected.
In order to release Hydrogen from hydrocarbons, chemical re-
actions are needed to break hydrogen bonds from these com-
pounds and release hydrogen, which has to be then recovered from
the multi-component gas stream. However, the proton exchange
membrane fuel cells require the purity of hydrogen, such that the
CO concentration is less than 50 ppm to avoid poisoning of the
anode catalyst (Choudhary et al., 2003). The control of individual

http://dx.doi.org/10.1016/j.jngse.2014.03.008
1875-5100/Ó 2014 Elsevier B.V. All rights reserved.
 A.P. Singh et al. / Journal of Natural Gas Science and Engineering 18 (2014) 286e295 287

sub-reactions, e.g., steam reforming, wateregas shift, and prefer-

ential oxidation (Amphlett et al., 1981; Zalc and Loffler, 2002) can
help in achieving the purity levels for fuel cell application, though
may not be feasible for small scale usage. The use of a H2 permeable
membrane reactor offers the potential for a compact unit in
combining both the reaction and separation in a single unit
(Holladay et al., 2005). Membrane reactors permit simultaneous
reaction and separation, and thereby enhance the conversion in
thermodynamically limited reactions by the removal of one or
more of the product species as they are generated. Further, the
traces of CO and other gases can be completely eliminated from the
hydrogen stream by the use of palladium membranes that are
highly selective towards hydrogen. Theoretical models are widely Fig. 1. Schematics of macro-scale reactor.
used to study the performance of membrane reactor for steam
reforming of methane or methanol (Gallucci et al., 2004; Ohmori
et al., 2005; Annaland et al., 2006; Caravella et al., 2008; Falco,
2008; Rui et al., 2008; Harale et al., 2010; Teixeira et al., 2010;
Dehkordi et al., 2011).
Development of microstructured membrane reactor has been
pursued very recently by a few research groups. Al2O3 hollow fibers
with internal coating of catalyst and external coating of palladium
(García-García et al., 2010), silicon substrate (Mejdell et al., 2009)
are some of the examples. Use of porous stainless steel multi-
channel plate and a stainless steel housing to accomplish Knoeve-
nagel condensation reaction has been reported (Lai et al., 2003).
The multichannel assembly was coated internally with ZSM-5 for
selective separation, and Cs-exchanged NaX faujasite zeolite for
catalytic action. Each channel has one wall coated with catalytic
material and other wall allows separation of water through hy-
drophilic ZSM-5 membrane. The arrangement displayed supra-
equilibrium conversion and better purity of product compared to
the performance of packed bed membrane reactor.
Therefore, the importance of micro-scale membrane reactor has Fig. 2. Schematics of micro-scale reactor.
been widely appreciated. However, the dynamics of the reaction
and permeation processes, and their interplay at micro-scale have
not been looked into. Any scope for optimization arising from this
pressure is assumed constant. From the mass balance over a dif-
interplay has not been explored. In this article, a mathematical
ferential length of the reactor a set of ODE-s were developed in the
model of a micro-channel membrane reactor is described. Steam
Appendix. The values of parameters are listed in Table 1. The
reforming of methane and methanol are considered here. Partial
equations were solved using Matlab.
pressures of reactants and products at various axial positions of the
The membrane is assumed 100% selective to hydrogen. Dense
channel are simulated. The conversion as function of residence time
palladium membrane on alpha Al2O3 support is known for very
is compared for macro and micro models. The dispersed catalyst
high selectivity to hydrogen (Shen et al., 2003). Permeation occurs
density is considered same in both cases. The effect of membrane
through dissociative adsorption and re-combinative desorption at
thickness and operating temperature on conversion is presented.
the surface, as well as diffusion in accordance with Sievert’s Law.
Further, it is realized that for the purpose of shifting the equilib-
rium, the separation of hydrogen may not be required for the entire
length of the reactor. Accordingly, an arrangement is made to
optimize the use of membrane area along the length of the reactor. Table 1
Also, the sensitivity of the conversion to perturbations in reaction Values of operating parameters.
rate constants that might have arisen because of rearrangements of Parameter Methane Methanol
catalyst sites in fabricated microstructure is evaluated. The pressure
For macro-scale reactor
gradient along the length of the channel is computed accounting Inner radius (in m) 0.1016 0.1016
the friction, the stoichiometry of reaction and permeation of the Membrane radius (in m) 0.0203 0.0203
product component through channel wall. Length (in m) 10 10
Catalyst coating density (in g cat/cm3) 2355.2 2355.2
For micro-scale reactor
2. Conceptual model Width (in cm) 1 1
Height (in mm) 100 100
Figs. 1 and 2 describe the physical model of tubular membrane Length (in m) 0.1 0.1
reactor and the micro-channel with catalyst-coated wall. Plug flow Catalyst coating density (in g cat/cm3) 7 7
For both type of reactors
of gas (Kandlikar et al., 2002; Bahrami et al., 2006) at steady state is
Feed flux of methane/methanol (mol/m2 s) 1000 1000
considered under isothermal condition. The kinetic model, used in Temperature (in  C) 700 700
this study is adapted from the work of Xu and Froment (1989), for Pressure (in atm) 29 5
methane steam reforming and of Nair and Harold (2006), and Methane:steam/methanol:steam 1:2 1:2
Lattner and Harold (2007), for methanol steam reforming. The Membrane thickness, d (in mm) 3 3
Permeate side partial pressure (in atm) 1 1
models are described in detail in the Appendix. Permeate side
288 A.P. Singh et al. / Journal of Natural Gas Science and Engineering 18 (2014) 286e295

simulations were repeated with varied length of membrane unit

   n n

JP ðH2 Þ ¼ ðb=dÞexp  EaH2 RT * Ppermeate  Pretentate (1) and cut-off concentration of hydrogen.

The heterogeneous reaction occurs at the catalyst surface on the 3. Results and discussion
floor of the micro-channel. Concentrations of the components are
assumed uniform over the entire cross-section of the channel. In Steam reforming of methane and methanol in a conventional
case of macro reactor, a dispersed catalyst density is defined as the plug flow reactor are simulated as base case. The flow rates of
weight of catalyst per unit total volume of the reactor. For the different species present in the system are plotted as a function of
purpose of comparison, the thickness of the catalyst layer in micro- the length of the reactor in Fig. 3. The flow rates were made
channel reactor is selected such that the dispersed catalyst density dimensionless with reference to the inlet feed flow rate. The
remains same in both macro and micro models. hydrogen concentration did not increase beyond a distance of 5 m
For macro-scale reactor, the pressure is assumed constant over from the inlet face in case of methane, and 1 m in case of methanol.
the entire length of the reactor. In case of micro-reactor, such Further reaction is not favored thermodynamically. In a conven-
assumption may not be valid. Kandlikar et al. (2002), have plotted tional reactor, at 700  C, the maximum conversion of methane
the pressure drop as a function of hydraulic diameter. The logelog achievable is less than 25%, and same for Methanol is less than 18%
plot for water and air in a square channel under fully developed for a 10 m reactor length. The utile length of the reactor (length
laminar condition shows an exponential increase in pressure after which the conversion does not increase appreciably) for
gradient with decrease in the channel dimensions. In the present methane steam reforming was 5 m and 1 m for methanol steam
article, the pressure gradient in a micro-channel is accounted as reforming. This was due to the buildup of hydrogen after the utile
sum of two terms. The first one is due to the frictional forces and the length, which inhibited the progress of reaction, by shifting the
second term accounts for the change in the number of moles. equilibrium in reverse direction. This thermodynamic constraint
    can however be overcome by the membrane reactor.
dp dp dp 2*14:23*L*mmix *Q X dfi =dz Fig. 4 reproduces the previous plots for membrane reactor. The
¼ þ ¼  þ P
dz dz f dz J Dh2 *AC *ð101325Þ fi Hydrogen concentration in the channel is smaller, and the con-
(2) version is enhanced. The removal of product form the reacting
system ensures that the reaction moves in the forward direction,
The frictional pressure drop in rectangular cross-section is and helps overcoming the thermodynamic constraints of the sys-
estimated using the following expressions (Bahrami et al., 2006) tem. Also, unlike the concentration of reactant species in conven-
tional reactor, the species in membrane reactor continued to
f Re ¼ 14:23 (3) decrease beyond the distances of 5 m and 1 m for methane and
methanol. The entire length of the reactor becomes utile for con-
DP 2fG2 version of the reactant in the membrane reactor.
¼  (4) The methane and methanol conversion as function of distance
L rD
from the inlet face are compared for the two types of reactors in
where, G ¼ mass flow rate Dh ¼ hydraulic diameter; Re ¼ Reynold’s Fig. 5. The membrane reactor shows a significant improvement
number; f ¼ friction fanning factor; mmix ¼ mixture viscosity, and
Ac ¼ Area of cross-section. The mixture viscosity is calculated using
ChapmaneEnskog Theory.
The pressure drop term due to change in number of moles (re-
action) is evaluated using ideal gas laws, as:
 
vP RT dn P d X  d X  X dxi
¼ ¼ ni ¼ P xi ¼ P
vz n V dz n dz dz dz
X dfi =dz
¼ P
fi
(5)
Therefore, Equation (2) is considered in addition to the ODEs in
the appendix concerning mass balance to account for the pressure
drop in the micro-channel.
Proportioning of the membrane activity and the catalyst activity
inside the micro-channel for maximum conversion is accomplished
as per the following scheme. The complete coverage of catalyst was
considered for one of the two major walls of the rectangular
channel. On the other wall, a membrane of unit length (10% of the
overall length of the channel) was applied only after the hydrogen
buildup was more than a threshold value. On application of the
membrane action, the hydrogen diffused out of the channel, and
the concentration got reduced. Beyond the stretch of the mem-
brane, the hydrogen concentration started rising again. Another
stretch of membrane of unit length is applied for the second time,
where the hydrogen concentration reached the cut-off value. This
process was repeated every time the threshold concentration of
hydrogen is reached. The stretches, where membrane action was Fig. 3. Concentration of reactants and products at various axial positions of the con-
absent, catalyst was introduced to enable quick conversion. The ventional plug flow reactor.
 A.P. Singh et al. / Journal of Natural Gas Science and Engineering 18 (2014) 286e295
Fig. 4. Concentration of reactants and products at various axial positions of the
membrane reactor.
over the conventional reactor when all the parameters remain
unchanged. It is observed that the conversion of methane and
methanol, which stopped increasing for a conventional reactor af-
ter the utile length, continues to increase for a membrane reactor.
The conversion increases from 25% to 40% for methane steam
reforming and from 18% to 34% for methanol steam reforming. A
reactor length of 10 m is considered for both types of reactors.
Fig. 5. Conversion along the length of the simple and membrane reactor.
289
Fig. 6. Conversion at various operating temperatures for membrane reactor and con-
ventional plug flow reactor.
Fig. 6 compares the effects of temperature on conventional and
membrane reactors. The temperature of the isothermal reactors
was varied from 600  C to 1000  C both methane and methanol
steam reforming. The same reaction kinetics, discussed in
Appendix was used for the entire range of temperature. Higher
temperature generally enhanced the conversion in both types of
reactors. At the highest limit of temperature, the conversion in
conventional reactor and membrane reactor is almost the same.
Fig. 7 describes the conversion of methane and methanol for
various thickness of membrane. The membrane thickness was
varied from 0.5 mm to 10 mm. A thinner membrane facilitates higher
flux of hydrogen according to the Sievert’s Law (Equation (1)), and
thereby reduces the thermodynamic constraint and enhances the
conversion. However the membrane thickness cannot be decreased
below a certain limit due to difficulties in pinhole-free fabrication.
The species, other than hydrogen, permeate by Knudsen diffu-
sion through the pinholes. The diffusivity in such case is given by
the following equation.
1=2
2 8RT
D ¼ a (6)
3 pMi
Pinhole diameters of 2 nm occupying 90% of the membrane face
was considered to evaluate the concentration of other species, in
Fig. 7. Effect of membrane thickness on conversion of methane and methanol.
290 A.P. Singh et al. / Journal of Natural Gas Science and Engineering 18 (2014) 286e295

0.08 1

Methanol
Carbon Dioxide Concentration in Permeate

0.07
0.8
Methane
0.06 Methane
0.6 Methanol

Conversion
0.05

0.04 0.4

0.03
0.2
0.02

0
0.01 0 100 200 300 400 500 600
Residence Time in seconds
0
0 1 2 3 4 5 6 7 8 9 10 Fig. 11. Conversion in membrane reactor as a function of residence time.
Membrane Thickness, in micrometer

Fig. 8. CO concentration in permeate as function of membrane thickness.

It is observed that the concentration of the other species in the
permeate decrease with increase in the membrane thickness. Fig. 8
1 describes the concentration of CO in the permeate stream. Due to
this, the purity of hydrogen collected decreased with increase in the
0.9
membrane thickness.
Hydrogen mole fraction in permeate

Fig. 9 describes hydrogen mole fraction on the permeate side for

methanol the two reactants. It is observed that the hydrogen mole fraction in
0.8 methane
permeate fell lower than 0.9, for membrane thickness less than
3 mm. The purity of hydrogen is a major concern, because the
0.7
permeated hydrogen can be used for other operations. Hence, if the
membrane thickness is less than 3 mm, there shall difficulty in
0.6 fabrication and also loss of quality of hydrogen extracted. Hence, a

0.5

0.4

0 1 2 3 4 5 6 7 8 9 10
Membrane thickness in micrometer

Fig. 9. Hydrogen selectivity as function of membrane thickness.

the permeate. It was achieved by considering the additional terms

in the flux equation for each species. The modified ODEs were
solved using Matlab routine.

3.5

3
Methane
Methane or Methanol Flow Rate

2.5
Methanol
Component Flowrate /

1.5

0.5

0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Distance from inlet
Fig. 12. Concentration of reactants and products at various axial positions of the mi-
Fig. 10. Rate of hydrogen permeation at various axial positions of the channel. cro-scale membrane reactor.
 A.P. Singh et al. / Journal of Natural Gas Science and Engineering 18 (2014) 286e295 291

0.9

0.8
Methanol
0.7 Methane

0.6
Conversion
0.5

0.4

0.3

0.2

0.1

0
0 50 100 150 200 250 300 350 400 450 500
Residence Time, in s

Fig. 13. Conversion in micro-channel as a function of residence time.

thickness of 3 mm is proposed to be the optimum thickness for
membrane reactor.
The rate of hydrogen permeation at various axial positions of the
channel is plotted in Fig. 10. The flow rate of hydrogen has been
made dimensionless using the methane or methanol flow rate at
the inlet. For all subsequent calculations, the membrane thickness
of 3 mm, and the pinholes of pore size 100 mm occupying 90% of the
membrane face are considered.
To summarize the benefits of membrane reactor, a conversion of
more than 80% could be achieved here by increasing the residence
time (Fig. 11). The maximum conversion in a conventional reactor is
not even one-third of this level at the temperature considered here
(Fig. 5). In conventional reactor the final conversion is achieved
within a length of 1e5 m. However, the length of the membrane
reactor that can provide the residence time required for the level of
conversion in Fig. 11 is about 60e80 m. This implies that there is
scope to make the conversion enhancement process in the con-
ventional reactor more efficient by focusing on better management
of hydrogen removal. Also, the buildup of hydrogen near the inlet
end of the membrane reactor is mostly uncontrolled. A larger
membrane surface area around this region of the reactor would
have enhanced the conversion significantly.
With the above understanding of the macro-scale performance,
the results for micro-scale membrane reactor are visited next.
Fig. 12 describes the concentration of various components along
the length of the channel. The most noticeable difference from the
trend in macro-scale reactor (Fig. 3) is the absence of hydrogen
buildup. That is, Fig. 12 suggests better removal of hydrogen from
the reaction site due to greater provision of membrane area per
unit mass flux of the feed. Fig. 13 describes the conversion in
micro-scale reactor as a function of residence time. In comparison
with the similar plot for macro-scale unit (Fig. 11), the conversion
is achieved at a shorter residence time. For a residence time of
100 s, the fractional conversion of methane and methanol are 0.64
and 0.32 respectively for macro-scale unit. The corresponding
values for micro-scale unit are 0.82 and 0.55. This is because the
membrane area-coverage has increased substantially in the micro-
model.

5.05
Methanol Pressure Drop
5
Pressure, in atm

4.95

4.9

4.85

0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1

29.005

29 Methane pressure drop

28.995
Pressure, in atm

28.99
28.985
28.98

28.975
28.97
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1

Dimensionless length

Fig. 14. Pressure drop along the length of the micro-channel.

292 A.P. Singh et al. / Journal of Natural Gas Science and Engineering 18 (2014) 286e295

Fig. 15. Sensitivity of conversion vs. residence time plots to reaction rate constants. A. Methane B. Methanol.

Fig. 14 describes the pressure drop along the length of the
micro-channel for the operating conditions in Table 1. For small
length of the reactor, and high value of pressure at the inlet, the
pressure gradient does not have much effect on the conversion.
Also, this is noted that the overall reaction is the cumulative
effect of different sub-reactions, involving individual rate constants.
Rather, the pieces of membrane length unit are placed at specific
axial positions of the reactor. The algorithm, discussed before de-
cides the axial positions for the membrane unit such that the
conversion is maximized. In Fig. 16, the cut-off value was taken as
1
Component Flowrate/Methane Flowrate

The conversion in the micro-reactor can be sensitive to the 0.9

perturbation in the rate constants. As part of this investigation a
sensitivity analysis was conducted to evaluate how the plot for 0.8

conversion as function of residence time gets affected because of 0.7

perturbations in the rate constants. When one rate parameter was
varied, all other parameters were held constant. Fig. 15 describes 0.6 Methane without optimization
the conversion as a function of residence time when the rate con- H2 without optimization
0.5
Methane with optimization
stants k1, k2, and k3 were varied. The rate-expressions are described
0.4 H2 with optimization
in the Appendix, and listed in Table 3. Fig. 15 indicates that the
perturbation in rate constant for wateregas shift reaction has 0.3
negligible effect on the final conversion. The perturbation in rate
0.2
constants involving decomposition and reforming affects the final
conversion to some extent. The perturbation is considered positive 0.1
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
by 100% when the rate constant was doubled, and negative by 100%
Distance from inlet
when the same was halved.
Fig. 16 reproduces Fig. 12 with the exception that the membrane Fig. 16. Concentration of methane and hydrogen at various axial positions of the mi-
does not extend continuously over the entire length of the reactor. cro-scale reactor with optimum use of membrane lengths.
 A.P. Singh et al. / Journal of Natural Gas Science and Engineering 18 (2014) 286e295 293

Table 2
Results for optimization.

Length of one No. of such Starting position for methane Conversion achieved Starting position for methanol Conversion achieved Membrane amount
stretch of membranes for methane for methanol total (% of length)
membrane used

0.20 3 0.043, 0.2521, 0.4788 96.13% 0.0291, 0.2429, 0.4757 89.32% 60%
0.10 4 0.0973, 0.2021, 0.3232, 0.5398 93.58% 0.0382, 0.2453, 0.3498, 0.4983 83.22% 40%

0.4 times the normalized flow rate. The unit fixed length of mem- 4. Conclusion
brane as one-fifth of the overall length was considered. The con-
centration of hydrogen in the reactor started rising above the cut- Use of membrane in tandem with a catalyst enhances the con-
off value of 0.4 at the normalized axial length of 0.0616. From this version for methane and methanol steam reforming for both macro
position to further downstream, the membrane unit is placed. As a and micro-scale model by removing the hydrogen from the reac-
result, the dimensionless flow rate of hydrogen decreased for a tion site. For these reactions, the conversion is found to increase
length up to 0.2616 on normalized length scale. Beyond this point, significantly with the increase in operating temperature. The level
the membrane action was non-existent for a stretch, where of conversion in a plug flow reactor matches that of a membrane
hydrogen started building up again. The placement of another reactor at a significantly high operating temperature. Smaller
membrane unit was repeated when the cut-off value was reached membrane thickness enhances the flux of hydrogen. However, with
for the second time. Finally in this case, two membrane units were reduced thickness of the membrane, it becomes difficult to avoid
used covering 40% of the wall area. In earlier situation (as per the pinholes, through which the feed components can escape non-
schematic of Fig. 2) entire wall area was used as membrane. With selectively by Knudsen diffusion.
reduced membrane coverage, the conversion achieved was 92.30%. Micro-scale membrane reactor provides the same level of con-
The simulations with selective placement of membrane were version at a smaller residence time. Hence, better removal of
repeated using different sets of unit length of the membrane, and hydrogen from the catalyst site is possible in the micro-scale unit.
the cut-off values of hydrogen concentration. The results for all the The conversion vs. residence time plot for both methane and
sets of values are presented in Table 2. methanol reforming in the micro-reactor are found sensitive to the
perturbations in the rate constants of decomposition and reform-
ing, arising due to rearrangement in the catalyst sites during the
fabrication of microstructure. The perturbation in rate constant for
wateregas shift reaction does not affect the final conversion. The
Table 3 use of membrane has been optimized through an algorithm in this
Model parameters. article. By locating membrane pieces at pre-designed positions
Rate constant or Pre-exponential Units Ea (kJ/mol) along the length of the channel, same conversion could be achieved
equilibrium constant factor with only 40% of original membrane coverage.
k1 4.22Eþ15 mol atm0.5/g h 240.1
k2 1.96Eþ06 mol/g h 57.12
k3 1.02Eþ15 mol atm0.5/g h 243.9 Appendix
KCH4 6.65E-04 atm1 38.28
KH2 O 1.77Eþ05 88.68
KH2 6.12E-09 atm1 82.9 Kinetic model e methane steam reforming
KCO 8.23E-05 atm1 70.65
K1 7.85Eþ12 atm1 220.2 The kinetic model for the reaction on a Ni/MgAl2O4 catalyst is
K2 1.41E-02 37.32
2 based on Langmuir Hinshelwood reaction mechanisms. The details
K3 1.11Eþ15 atm 182.4
of the kinetic model are as given below (Xu and Froment, 1989).
DSi kN
i DHi Ea
(J mol1 K1) (m2 s1 mol1) (kJ mol1) (kJ mol1)
CH4 þ H2O / CO þ 3H2
kR 7.4Eþ14 102.8
KCH3 Oð1Þ ðbar0:5 Þ 41.8 20
CO þ H2O / CO2 þ 3H2
KOH(1)(bar0.5) 44.5 20
KH2 ð1aÞ ðbar0:5 Þ 100.8 50
KHCOOð1Þ ðbar1:5 Þ 179.2 100 CH4 þ 2H2O / CO2 þ 4H2
kD (m2 s1 mol1) 3.8Eþ20 170.0
KCH3 Oð2Þ ðbar0:5 Þ 30 20 The rate expressions for the three reactions are
KOHð2Þ ðbar0:5 Þ 30 20
KH2 ð2aÞ ðbar0:5 Þ 46.2 50
PH3 PCO
kW (m2 s1 mol1) 5.9Eþ13 87.6 k1
PCH4 PH2 O  2
PH2:5 K1
Other parameters Value Units R1 ¼ 2
(7)
2
DEN2
KR 1.145 atm
Kw 149.9 atm0
h i
KD 76.25 atm2 k2 PH PCO
CTS1a 1.5E-5 mol m2 PH2 PCO PH2 O  2K2 2
CTS2a 1.5E-5 mol m2
R2 ¼ (8)
DEN2
CTS1 7.5E-6 mol m2
CTS2 7.5E-6 mol m2
Sc 5Eþ4 m2/kg k3 PH4 PCO2
2
PCH4 PH  2
b 2.89E-01 m3/(m h atm0.5) PH2:5 2O K3
EaH2 12.54 kJ mol1 R3 ¼ 2
(9)
DEN2
294 A.P. Singh et al. / Journal of Natural Gas Science and Engineering 18 (2014) 286e295

Where dfH2 r *Ac *L

¼ cat 0 *ð3R1 þ R2 þ 4R3 Þ
dZ FCH4
   
0
FH 0
FH sw*2pRm *L b EaH2 (20)
DEN ¼ 1 þ 2O
þ 2
þ KCH4 PCH4 þ KCO PCO þ KH2 PH2  0
* exp
0
FCH 0
FCH FCH d RT
4 4  4

n n
KH2 O PH2 O * PH  PH
þ (10) 2; permeate 2; retentate
PH2
The rate of appearance and disappearance of different species J
(species) can be given as follows:
Kinetic model e methanol steam reforming
JðCO2 Þ ¼ R2 þ R3 (11)
The details of the kinetic model for methanol steam reforming
JðCOÞ ¼ R1  R2 (12) are given below (Peppley et al., 1999; Nair and Harold, 2006;
Lattner and Harold, 2007)
JðH2 OÞ ¼ ðR1 þ R2 þ 2R3 Þ (13)
CH3 OH þ H2 O/CO2 þ 3H2 ðsteam reforming RÞ

JðCH4 Þ ¼ ðR1 þ R3 Þ (14)

CH3 OH/CO þ 2H2 ðmethanol decomposition DÞ
JðH2 Þ ¼ 3R1 þ R2 þ 4R3 (15)
The mass balance across a differential length of the reactor gives
CO þ H2 O/CO2 þ H2 ðwater gas shift WÞ
dfCO2 r *Ac *L
¼ cat 0 *ðR1 þ R3 Þ (16) The rate expressions for the three reactions are:
dZ FCH4

 .   
1=2 3 P T CT S
kR KCH3 Oð1Þ PM PH2 1  PH CO2
KR P M Pw CS1 S1A C
RR ¼ h  .   . 2   . ih i (21)
1=2 1=2 1=2 1=2 1=2
1 þ KCH3 Oð1Þ PM PH2 þ KHCOOð1Þ PCO2 PH2 þ KOHð1Þ PW PH2 1 þ KH2 ð1aÞ PH2

 .   T 2
1=2

kW KOHð1Þ PCO PW PH2 1  PH2 PCO2 KW PCO Pw CS1 SC
RW ¼ h  .   .   . i2 (22)
1=2 1=2 1=2
1 þ KCH3 Oð1Þ PM PH2 þ KHCOOð1Þ PCO2 PH2 þ KOHð1Þ PW PH2

  . 
1=2 2 P T CT S
kD KCH3 Oð2Þ PM PH2 1  PH 2 CO2
KD PM CS2 S2A C
RD ¼ h  .   . ih i (23)
1=2 1=2 1=2 1=2
1 þ KCH3 Oð2Þ PM PH2 þ KOHð2Þ PW PH2 1 þ KH2 ð2aÞ PH2

dfCO r *Ac *L
¼ cat 0 *ðR1  R2 Þ (17)
dZ FCH4 The values of the various parameters are given in Table 3.

dfH2 O r *Ac *L
¼  cat 0 *ðR1 þ R2 þ 2R3 Þ (18)
dZ FCH 4 ki ¼ kN
i expðEai =RTÞ (24)

 
dfCH4 r *Ac *L DSi DHi
¼  cat 0 *ðR1 þ R3 Þ (19) Ki ¼ exp  (25)
dZ FCH R RT
4
 A.P. Singh et al. / Journal of Natural Gas Science and Engineering 18 (2014) 286e295 295

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 0
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FCH d RT Nomenclature
 4

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 PH 2; retentate Ac: Retentate side cross-sectional area, m2
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D: Diffusivity, m2/s
Dh: Hydraulic diameter, m
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