Energy & Fuels 2006, 20, 463-472 463

Performance Enhancement of Steam Methane Reforming Using

Tubular Packed-Bed Microreactors and Dilution by Adsorbent

R. Rajasree, V. Ravi Kumar,* and B. Dattatraya Kulkarni

Chemical Engineering and Process DeVelopment DiVision, National Chemical Laboratory,

Pune, 411 008, India

ReceiVed July 8, 2005. ReVised Manuscript ReceiVed December 21, 2005

For an endothermic reaction such as steam methane reforming (SMR), temperature gradients in the packed
bed can play a significant role in process performance. A reactor design strategy that considers the combination
of tubular packed-bed microreactor (TPBM) operation and catalyst dilution by adsorbent is proposed for
enhancement of the SMR process. Simulation studies have been performed with the proposed strategy to
quantitatively study the effect of heat transfer limitation and process performance in terms of methane conversion
and hydrogen purity. This is carried out using a dynamic 2D pseudohomogeneous model incorporating kinetic
and reactor/reaction mechanisms describing the process. The results of these studies show that the temperature
gradient in TPBM is better controlled with less catalyst loading in comparison with traditionally used larger
diameter reactors. It is seen that improved heat transfer characteristics of the TPBM combined with the effects
of catalyst dilution and adsorption complement each other, and enhanced performance in terms of methane
conversion and hydrogen purity is observed. The findings based on this study give an insight into the performance
improvement of the SMR process and show that cost reduction and process miniaturization of fuel processors
for fuel cell applications are possible.

1. Introduction controlled directly by bypassing cold feed around main feed

The key issue regarding the widespread commercialization
of fuel cells is the ability to reduce cost and reactor dimensions
to acceptable levels for both stationary and transport applica-
tions. The fuel processor that produces H2-rich streams from
hydrocarbon-based feedstock is a major component whose
design and operation play an important role in achieving overall
system efficiency. In fuel processing, research has a long way
to go in the development of cost-effective strategies and its
overall optimization.1-10
Traditionally, these processes have been carried out in fixed
bed reactors packed with catalysts where both exothermic and
endothermic reactions occur together. Controlling the reactor
temperature is very crucial for optimum reactor performance,
and a number of methods have been studied for this aim.11-24
For an exothermic reversible reaction, the temperature may be
* Corresponding author. Phone: (91) 20-25902161. Fax: (91) 20-2589
3041. E-mail: v.ravikumar@ncl.res.in.
(1) Park, G. G.; Seo, D. J.; Park, S. H.; Yoon, Y. G.; Kim, C. S.; Yoon,
W. L. Chem. Eng. Technol. 2004, 101, 87-92.
(2) Ouyang, X.; Besser, R. S. J. Power Sources 2005, 141, 39-46.
(3) Lee, S. H.; Han, J.; Lee, K. W. J. Power Sources 2002, 109, 394-
402.
(4) Shah, K.; Ouyang, X.; Besser, R. S. Chem. Eng. Technol. 2005, 28,
303-313.
(5) Tonkovich, A. Y.; Zilka, J. L.; LaMont, M. J.; Wang, Y.; Wegeng,
R. S. Chem. Eng. Sci. 1999, 54, 2947-2957.
(6) Srinivas, S.; Dhingra, A.; Im, H.; Gulari, E. Appl. Catal., A 2004,
274, 285-293.
(7) Choi, Y.; Stenger, H. G. J. Power Sources 2003, 124, 432-439.
(8) Avcı, A. K.; Trimm, D. L.; Önsan, Z. I. Chem. Eng. J. 2002, 90,
77-87.
(9) Avcı, A. K.; Trimm, D. L.; Önsan, Z. I. Appl. Catal., A 2001, 216,
243-256.
(10) Ji, P.; Feng, W.; van der Hooi, H. J.; de Swaan Arnos, J. Ind. Eng.
Chem. Res. 2004, 43, 2005-2016.
preheater and distributing it along the length of the reactor.12,13
Another method is cold stream injection that cools the bulk
reacting fluid.16 The above operations require an optimal policy
in rate of addition of cold feed such that the reaction rate is
maximized with respect to variation of the mass flow rate at
each point of the reactor. Tailoring catalyst characteristics such
as nonuniform catalysts and catalyst size can be applied to
control the reaction rate.20 Novel reactor designs, for example,
multibed, multitubular reactor,21 and packed-bed membrane
reactor22 strategies have also been employed, and further
improvements in the design and analysis of these strategies are
(11) Lee, K.; Aris, R. Ind. Eng. Chem. Process Des. DeV. 1963, 2, 300-
306.
(12) Dyson, D. C.; Horn, F. J. M. J. Optim. Theory Appl. 1967, 1, 40-
52.
(13) Dyson, D. C.; Graves, J. R. Chem. Eng. Sci. 1968, 23, 435-446.
(14) Caldwell, A. D.; Calderbank, P. H. Brit. Chem. Eng. 1969, 14,
1199-1201.
(15) Sadhukan, P.; Petersen, E. E. AIChE J. 1976, 22, 808-810.
(16) Burghardt, A.; Patzek, T. Chem. Eng. J. 1978, 16, 153-164.
(17) Danziger, D.; Popovic, D.; Schulz-Ekloff, G. Can. J. Chem. Eng.
1983, 61, 126-128.
(18) Quina, M. M. J.; Ferreria, R. M. Q. Ind. Eng. Chem. Res. 1999, 38,
4615-4623.
(19) Quina, M. M. J.; Ferreria, R. M. Q. Chem. Eng. Sci. 2000, 55, 3885-
3897.
(20) Hwang, S.; Linke, P.; Smith, R. Chem. Eng. Sci. 2004, 59, 4245-
4260.
(21) Papageorgiou, J. N.; Froment, G. F. Chem. Eng. Sci. 1996, 51,
2091-2098.
(22) Pena, M. A.; Carr, D. M.; Yeung, K. L.; Varma, A. Chem. Eng.
Sci. 1998, 53, 3821-3834.
(23) Xiu, G. H.; Li, P.; Rodrigues, A. E. Chem. Eng. Sci. 2003, 58, 3425-
3437.
(24) Xiu, G. H.; Li, P.; Rodrigues, A. E. Chem. Eng. Res. Des. 2004, 82
(A2), 192-202.

10.1021/ef050205z CCC: $33.50 © 2006 American Chemical Society

Published on Web 02/03/2006
464 Energy & Fuels, Vol. 20, No. 2, 2006
required. Recently, a new generalized strategy using the principle
of temperature-induced equilibrium shift by controlling the
subsection wall temperature has been developed by Xiu et al.23,24
This strategy is an efficient way for controlling the temperature
along the reactor. However, other subsection-controlling pa-
rameters such as number of subsections, the subsection packing
ratio of adsorbent and catalyst, and temperature in each
subsection need to be well-optimized.
The heat transfer rates in the packed-bed reactor are known
to depend weakly on internal field intraparticle temperature
gradients in comparison with external field interparticle gradi-
ents.25 The external field interparticle temperature gradients can
be minimized by decreasing the reactor diameter, by diluting
the solids, or by diluting the reactant. Due to volume constraints,
reactant dilution may not be feasible in commercial reformers.
Therefore, it has been suggested that controlling external field
interparticle heat transfer in a packed-bed reactor by decreasing
the reactor diameter and by solids dilution may prove to be
advantageous.26,27
Tubular packed-bed reactors with small diameters have the
advantage of providing higher surface-to-volume ratios. This
results in decreasing mass transport and heat transport resistances
and makes them attractive for achieving efficient thermal and
mass transfer rates. Karim et al.27 applied this concept for
methanol steam reforming on a commercial CuO/ZnO/Al2O3
catalyst and showed its potential in the area of fuel processing
for fuel cell applications. Their study points out that there exist
heat transfer limitations in the bed and that the majority of
activity measurements that have been reported for methanol
steam reforming could be influenced by temperature gradients
within the reactor.
Catalyst dilution by solids increases the wall area to catalyst
volume for heat transfer. It establishes specific temperature
profiles (both in the radial and axial directions) in the packed-
bed reactor and thereby improves the isothermicity while
simultaneously suppressing other effects that adversely affect
performance (e.g., nature of axial dispersion, channeling loss).
The strategy of dilution by solids has been studied to improve
packed-bed reactor performance and is now being increasingly
applied.17-19,28-31 The cost of catalyst forms a major component
in reactor operation, and dilution can help in this aspect. In
addition to packed-bed catalytic reactors, catalyst dilution by
solids has been applied to fluidized-bed reactors32,33 and trickle-
bed reactors.34,35 Care should be taken, however, to prevent
bypass of flow inside a reactor while employing the dilution
strategy.29-31 Catalyst dilution studies reported in the literature
use inert solid-catalyst mixtures. In the present study, we
assume that the catalyst is diluted with an adsorbent that acts
(25) Kirillov, V. A.; Kuzin, N. A.; Mescheryakov, V. D.; Droboshevich,
V. I. Chem. Eng. Sci. 2001, 56, 381-386.
(26) Mears, D. E. J. Catal. 1971, 20, 127-131.
(27) Karim, A.; Bravo, J.; Datye, A. Appl. Catal., A 2005, 282, 101-
109.
(28) Taniewski, M.; Lacjowicz, A.; Skutil, K.; Czechowicz, D.; Ferreria,
R. M. Q. Chem. Eng. Sci. 1996, 55, 4271-4278.
(29) Hwang, S.; Smith, R. Chem. Eng. Sci. 2004, 59, 4229-4243.
(30) Berger, R. J.; Pérez-Ramı́rez, J.; Kapteijn, F.; Moulijn, J. A. Chem.
Eng. J. 2002, 90, 173-183.
(31) van den Bleek, C. M.; van der Wiele, K.; van de Berg, P. J. Chem.
Eng. Sci. 1969, 24, 681-694.
(32) Irani, R. K.; Kulkarni, B. D.; Doraiswamy, L. K. Ind. Eng. Chem.
Process. Des. DeV. 1979, 18, 648-655.
(33) Irani, R. K.; Kulkarni, B. D.; Doraiswamy, L. K.; Hussain, S. Z.
Ind. Eng. Chem. Process Des. DeV. 1982, 21, 192-195.
(34) Van Klinken, J.; Van Dongen, R. H. Chem. Eng. Sci. 1980, 35,
59-66.
(35) Al-Dahnan, M. H.; Dudukovic, M. P. AIChE J. 1996, 42, 2594-
2606.
Rajasree et al.
not only as a diluent for the catalyst but also at the same time
as an adsorbent for CO2. Steam methane reforming (SMR)
reactions are equilibrium-controlled, and selective removal of
CO2 from the reaction zone increases methane conversion
according to Le Chatelier’s principle. Hydrotalcite adsorbent,
which selectively removes CO2 from the reaction zone and is
stable under wet gas and high temperature, is particularly known
to be suitable for the SMR process.36,37
Temperature gradients in SMR in a packed bed can adversely
affect process performance, and this article focuses on the use
of tubular packed-bed microreactors (TPBM) and employs a
catalyst dilution strategy for performance enhancement of SMR
for controlling the temperature gradient in the bed. As discussed
above, these two aspects of reactor design (viz., microreactor
operation and catalyst dilution by solids) have generally been
studied separately. In the present work, we consider a strategy
where the above two features can take place simultaneously.
For the above objective, we have studied the SMR process
performance in TPBM for diluted and undiluted conditions using
a dynamic 2D pseudohomogeneous model. The model incor-
porates mass and energy balances with nonlinear adsorption
isotherm together with a linear-driving force (LDF) model for
adsorption rate and this is coupled with the SMR reactions. The
results of simulation are presented and discussed in detail in
section 3 and show the improvement in SMR performance
pertaining to effects of varying reactor diameter, extent of
catalyst dilution by adsorbent, and solids packing density.
2. 2D Mathematical Model for the SMR Process
The key chemical reactions of the SMR process are given
by:
CH4 + H2O S CO + 3H2, ∆H298 ) 206.2 kJ/mol (1)
CH4 + 2H2O S CO2 + 4H2, ∆H298 ) 164.9 kJ/mol (2)
CO + H2O S CO2 + H2, ∆H298 ) -41.1 kJ/mol (3)
The mathematical model used to describe the SMR reactor
with adsorbent dilution is a dynamic 2D pseudohomogeneous
model that considers the nonisothermal, nonadiabatic, and
nonisobaric nature of operation. The model assumptions used
are:
1. Axial dispersed plug flow prevails in the bed.
2. Mass dispersion in the axial direction is considered.
3. Mass dispersion in the radial direction is assumed to be
negligible.
4. The system is nonisothermal. Thermal dispersion in both
axial and radial directions is considered.
5. The reaction kinetic model employed is that proposed by
Xu and Froment.38 This kinetic model has been shown to be
useful to study the SMR process.39-41
6. Volumetric change of flow due to adsorption and reaction
is taken into account in the overall material balance.
7. The gas is assumed to be an ideal gas.
8. The adsorbent and catalyst particles are the same size and
spherical in shape.
(36) Zou, Y.; Mata, V.; Rodrigues, A. E. Ind. Eng. Chem. Res. 2001,
40, 204-209.
(37) Ding, Y.; Alpay, E. Chem. Eng. Sci. 2000, 55, 3461-3474.
(38) Xu, J.; Froment, G. F. AIChE J. 1989, 35, 88-96.
(39) Ding, Y.; Alpay, E. Chem. Eng. Sci. 2000, 55, 3929-3940.
(40) Xiu, G. H.; Soarse, J. L.; Rodrigues, A. E. AIChE J. 2002, 48, 2817-
2832.
(41) Xiu, G. H.; Li, P.; Rodrigues, A. E. Chem. Eng. J. 2003, 95, 83-
93.
Performance Enhancement of SMR Energy & Fuels, Vol. 20, No. 2, 2006 465

9. The pressure distribution in the packed bed adsorptive ∂T ∂T

reactor is described by the Ergun equation.42 [tCCvg + (Fad + Fcat)Cps] + CCpgu -

( )
10. The effect of changing bed voidage with variation ∂t ∂z
n ∂qji n III

∑ ∑ ∑υijηjRj∆HRj )
of reactor-to-particle diameter ratio43 on methane conver-
sion, hydrogen purity, and in the Ergun equation has been
Fad -∆Hadi - Fcat
∂t

( ) ( )
i)1 i)1 j)I
considered.
11. The gas phase and the catalyst/adsorbent particles are ∂ ∂T 1 ∂ ∂T
kz + krr (8)
assumed to be in local mass/thermal equilibrium at all times. ∂z ∂z r ∂r ∂r
12. Five chemical species are considered, viz., CH4, H2O,
CO, H2, and CO2. Because the effective axial and radial thermal conductivities
13. The nonlinear Langmuir model is used to describe the do not vary by orders of magnitude, we choose for purpose of
multicomponent adsorption equilibrium isotherm for CO2. simulation studies kr ) kz and use an estimated value obtained
14. The LDF model is used for the adsorption rate mecha- from the correlation given by Yagi et al.45 For the simulation
nism. In the present study, hydrotalcite37 is used as adsorbent of the undiluted bed, the adsorbent parameters (mi, bi, kfi,
for CO2 and the Langmuir isotherm model, and the LDF rate ∆Hadi,Fad) are zero-valued.
model was found to give an adequate description of CO2 6. Initial conditions:
adsorption and desorption behavior. The initial conditions (at t ) 0) used in the present study are
15. The catalyst is assumed to be uniform and small in size, as follows:
so that the effectiveness factor is considered to be unity and is
PH2
the same for all reactions.
T ) Tf, qji ) 0, PH2 ) Pf, CH2 ) , Pi ) 0,
16. External field interparticle heat transfer effects (both RTf
radial and axial temperature gradients in the framework of Ci ) 0 (i ) CH4, H2O, CO, CO2) (9)
packed-bed reactor taken as a whole) in the reactor are
considered. where Tf and Pf are feed gas temperature and pressure,
17. There is complete mixing of the adsorbent and catalyst respectively.
particles with negligible catalyst deactivation. 7. Boundary conditions:
18. The feed stream and column wall are maintained at the The following boundary conditions are used in the simulations
same constant temperature. (i) Reactor inlet (z ) 0, 0 e r e R0)
For the above assumptions, the governing equations with
initial and boundary conditions are summarized below.
1. The overall mass balance equation: -bDL ( )
∂Ci
∂z
) uf(Cfi - Ci) (10a)

∂C
t +
∂(uC)
+ Fad ∑
n ∂qji n III
- Fcat∑∑υijηjRj ) 0 (4)
-kz(∂T∂z ) ) u CC f pg(Tf - T) (10b)
∂t ∂z i)1 ∂t i)1 j)I u ) u f, P ) P f (10c)
2. The component mass balance for component i in the gas (ii) Reactor outlet (z ) L, 0 e r e R0)
phase:
∂Ci ∂T

( )
) 0, )0 (10d)
∂Ci ∂(uCi) ∂qji III
∂ ∂Ci ∂z ∂z
t + + Fad - Fcat ∑ υijηjRj ) b DL (5)
∂u ∂P
∂t ∂z ∂t j)I ∂z ∂z ) 0, )0 (10e)
∂z ∂z
where DL is the axial dispersion coefficient and is evaluated by (iii) At the center of reactor (r ) 0, z g 0)
the correlation given by Edwards and Richardson.44
3. Mass transfer rates: ∂Ci ∂T
) 0, )0 (10f)
∂r ∂r
∂qji
) kfi(q/i - qji) (6) ∂u ∂P
∂t ) 0, )0 (10g)
∂r ∂r
where kfi is the LDF mass transfer coefficient and may be (iv) At the reactor wall (r ) R0, z g 0)
evaluated by the correlation reported by Ding and Alpay.37
4. Adsorption equilibrium: ∂Ci
)0 (10h)
∂r
mibiPi
q/i ) (7) -kr
∂T
) hw(Tw - T) (10i)
n ∂r
1+ ∑ bjPj
∂u ∂P
j)1 ) 0, )0 (10j)
∂r ∂r
5. The energy balance for the bed-volume element: where Tw is the wall temperature (assumed to be equal to Tf for
purposes of simulation) and hw is the wall heat transfer
(42) Ergun, S. Chem. Eng. Sci. 1952, 48, 89-94.
(43) de Klerk, A. AIChE J. 2003, 49, 2022-2029. coefficient.
(44) Edwards, M. H.; Richardson, J. F. Chem. Eng. Sci. 1968, 23, 109-
123. (45) Yagi, S.; Kunii, D.; Wakao, N. AIChE J. 1960, 6, 543-546.
466 Energy & Fuels, Vol. 20, No. 2, 2006 Rajasree et al.

Table 1. Parameter Values Used in the Simulations

parameter value
bco2 a diluted bed: 2.36 × 10-4 Pa-1; undiluted bed: 0
dpb 5 × 10-4 m
Cpga 42 J/mol K
Cpsa 850 J/kg K
∆HadCO2a diluted bed: -17000 J/mol; undiluted bed: 0
mco2a diluted bed: 0.65 mol/kg; undiluted bed: 0
Pfc 445.7 kPa
hwb 71 J/m2‚K
ufc 0.008 m/s
Tfc 773 K
H2O/CH4b 6
bb 0.48
pb 0.24
tb 0.64
µa 2.87 × 10-5 Pa-s
Fadb diluted bed: 498 kg/m3, undiluted bed: 0
Fcatb 249 kg/m3
ηb 1.0
a Data from refs 37 and 39. b Data from ref 40. c Present study.
Figure 2. Radial temperature profiles at z ) 0.03 m (where
the temperature is the highest) for a 6-mm-diameter reactor at
different feed temperatures. Values of other parameters are given in
Table 1.

Figure 1. Axial temperature profiles at the center (r ) 0.0) for a 6-mm-

diameter reactor at different feed temperatures. Values of other
parameters are given in Table 1.
Figure 3. Effect of steady-state SMR performance as a function
de Klerk43 has reported a model that obtains a good of reactor diameter. Values of other parameters are given in Table
description of the influence of column-to-particle diameter ratio 1.
(D/dp) on the average bed voidage (b). This model is valid for
a first principles approach. It involves both reaction and
equally sized spheres and for D/dp > 2. In the present study,
adsorptive separations occurring simultaneously. The adsorption
we consider D/dp ) 4-50 with catalyst and adsorbent of
equilibrium isotherm is nonlinear, and the values of its constants
uniform spherical particles of the same diameter. The above
depend on temperature and pressure. Also, the above equations
model may therefore be used in the present study for calculating
are highly coupled and nonlinear, and this can even cause steep
the bed voidage with D/dp and is given by
axial composition gradients in the reactor depending on

(
b ) i + 0.35 exp -0.39
D
dp ) (11)
where i is defined as the average bed voidage of an infinite
diameter column. de Klerk43 showed that the effect of D/dp on
b is more pronounced for small values of D/dp (<4) and the
bed voidage becomes constant at higher values of D/dp (>15).
In the present study, the value of average voidage for the infinite
diameter column is assumed to be the situation when D/dp )
5040 (i.e., i ) 0.48). The average bed voidage b can then be
calculated by using eq 11. The effect of change of bed voidage
with D/dp has therefore been incorporated in the SMR model
formulation.
3. Results and Discussion
It may be noted that the model considered is sufficiently
rigorous for analysis of SMR system behavior and is based on
parameter values and operating conditions.
Equations 4-8 with initial and boundary conditions (eqs
9 and 10) are numerically solved by a finite differ-
ence formulation, and the solutions obtained predict the SMR
process performance for undiluted and diluted bed conditions.
For simulation purposes the finite difference formula-
tion employed a sufficient number of grid points along
the reactor length and radius so that numerically stable and
accurate solutions that describe the system dynamics in time
are obtained.
The overall mass balance equation (eq 6) and Ergun equa-
tion42 are solved to obtain the velocity and pressure profiles in
the reactor along with eqs 5 and 8 for the effluent mole fractions
and reactor temperature profiles. The process performance is
then quantitatively compared by studying the conversion of
methane XCH4 and hydrogen purity yH2(dry basis) defined as,
respectively,40
Performance Enhancement of SMR Energy & Fuels, Vol. 20, No. 2, 2006 467

Feed of CH4 (mol/s) - Effluent of CH4 (mol/s) state temperature profiles were obtained by solving the dynamic
XCH4 ) model for a sufficiently long time. The steady-state axial
Feed of CH4 (mol/s)
temperature profiles at the center (at r ) 0.0 m) and the radial

[ ( )( ) ]
RTf uPyCH4 temperature profiles where the temperature is the highest at z
) 1- (12) ) 0.03 m are plotted in Figures 1 and 2, respectively. For
ufPfyCH4 feed
RT outlet
varying Tf, Figure 1 shows that steep axial temperature gradients
exist that move further downstream for higher Tf. With increase
y H2
in Tf, higher values of conversion of methane (XCH4) are possible.
yH2(dry basis) ) (13)
1 - yH2O In turn, this leads to higher heat removal rates by reaction, and
consequently, steeper temperature gradients are observed near
Temperature Gradients in a Tubular Packed-Bed Mi- the reactor inlet. Figure 2, however, shows that even for a 6-mm-
croreactor. To check whether the SMR performance is affected diameter reactor radial temperature gradients can exist due to
by the existence of temperature gradients, simulation studies interparticle heat transfer, and this becomes more dominant at
for a 6-mm diameter packed-bed reactor for varying feed higher Tf. Mears26 developed a criterion to assess the presence
temperature (Tf) was first carried out. The catalyst loading (Wc) of radial heat transfer resistance by evaluating R0/RP. According
was kept constant at 6.45 g. The values of other parameters to the criterion, if R0/RP > 100 then the resistance may be
used in the simulation studies are listed in Table 1. The steady neglected. In our study, R0/RP ) 12, and the results obtained in

Figure 4. Temperature profiles: (a) d ) 2 mm and (b) d ) 15 mm. Values of other parameters are given in Table 1.
468 Energy & Fuels, Vol. 20, No. 2, 2006
Figure 5. Velocity profiles: (a) d ) 2 mm and (b) d ) 15 mm. Values of other parameters are given in Table 1.
Figures 1 and 2 showing the presence of heat transfer limitations
are supported by the Mears criterion. The above results suggest
that the SMR reactor diameter is an important parameter that
affects external field interparticle heat transport mechanisms.
We therefore studied the effects of decreasing reactor diameter
on performance, and the results obtained are discussed next.
SMR Process Performance in Tubular Packed-Bed Mi-
croreactors. Studies are carried out by reducing the reactor
diameter (d) systematically from 25 mm to 2 mm, keeping
a catalyst loading of 6.45 g. The reaction was assumed to be
carried out at Tf ) 773 K. The other parameter values are chosen
as given in Table 1. The steady-state process performance
in terms of methane conversion (XCH4) and H2 purity (yH2)
is plotted in Figure 3. As seen, there is a significant improve-
ment in the process performance with decrease in d. For
decreasing d, the reactor length L needs to be altered to main-
tain constant catalyst loading. To assess the results, the needed
reactor length with decreasing reactor diameter is also shown
in Figure 3. For a catalyst loading of 6.45 g, the methane
Rajasree et al.
conversion increases from 20 to 100% upon reducing d
from 25 to 2.8 mm. A reactor with d ) 2.8 mm with the
corresponding length can therefore be designed for full
methane conversion. It is seen that, even at lower d, process
miniaturization by appropriate design and integration is feasi-
ble for the calculated values of reactor length and chosen
diameter.
Figure 4 compares the axial and radial temperature profiles
plotted for reactors having d ) 2 mm and (Figure 4a) and 15
mm (Figure 4b). It is clearly seen that the temperature gradients
are controlled for d ) 2 mm when compared to d ) 15 mm,
especially in the radial direction. It has been reported that the
advantages resulting from isothermality by reducing the reactor
diameter are significantly higher than the effects of channeling
for R0/RP ratios as low as even 4.26,31 In the present study, for
a 2-mm-diameter reactor where isothermality is approached, R0/
RP ratio is 4. This suggests that choosing an appropriate tubular
microreactor diameter is possible with negligible channeling
effects.
Performance Enhancement of SMR
Figure 6. Pressure profiles: (a) d ) 2 mm and (b) d ) 15 mm. Values of other parameters are given in Table 1.
We also studied the effects of velocity change and pres-
sure drop due to adsorption and reaction in the reactor. The
nature of the velocity profiles obtained is illustrated in Fig-
ure 5 for d ) 2 mm (Figure 5a) and d ) 15 mm (Figure 5b).
The results indicate that, for the similar superficial veloci-
ties, smaller-diameter reactors can provide good radial flow
features in the extended reaction zone. Hence, it may now
be possible to control the hydrodynamics and thereby the
reaction behavior in the reaction zone. Likewise, the pres-
sure drop for the lower d ) 2 mm reactor is in the range of
2-3 kPa, does not seems to be significant. It may also be
seen in Figure 6 that the magnitudes and nature of pres-
sure profiles for both d ) 2 mm and d ) 15 mm reactors
are not considerably different. This is again advantageous from
design considerations as the effects of pressure drop may
not be important for the SMR process taking place in a
TPBM.
Energy & Fuels, Vol. 20, No. 2, 2006 469
The dynamics of the SMR process in time at the exit of the
reactor is illustrated in Figure 7a,b in terms of XCH4 and yH2 for
d ) 2, 4, 10, and 25 mm. It is observed from Figure 7a,b that
the transient period is longer as the reactor diameter becomes
smaller from 25-mm to 4-mm reactors. For a 2-mm-diameter
reactor, 100% conversion at the reactor outlet is seen throughout
the operation of the process. This suggests that, for a TPBM
with lower diameter, a lower Wc and therefore of shorter length
would suffice for achieving complete conversion. Our calcula-
tion showed that a 2-mm-diameter reactor and length corre-
sponding to a Wc of 5.5 g yield 100% conversion. Hence,
operating with TPBM will help in running the SMR process at
low Wc than conventionally employed larger-diameter reactors
for the same performance parameters.
Effect of Adsorbent Dilution on the SMR Process. Simula-
tion for effects of catalyst dilution is carried out by assuming
hydrotalcite as the diluent that also acts as adsorbent for CO2
470 Energy & Fuels, Vol. 20, No. 2, 2006 Rajasree et al.

Figure 7. Transient profiles of SMR performance as a function of reactor diameter at the exit: (a) Methane conversion (XCH4) and (b) hydrogen
purity (yH2). Values of other parameters are given in Table 1.

Figure 8. Effect of adsorbent dilution on SMR performance as a function of reactor diameter. Constant bulk packing density of (a) methane
conversion (XCH4) and (b) hydrogen purity (yH2). Solid line: undiluted reactor. Dashed line: diluted reactor. Values of other parameters are given
in Table 1.

in the reaction zone. The equilibrium and kinetic constants for
hydrotalcite adsorbent have been taken from Ding and Al-
pay.37,39 The effects of adsorbent dilution are investigated in
two ways: (1) by comparing the performance of dynamics of
diluted and undiluted TPBM of varying diameters having a fixed
catalyst loading (Wc) and (2) by studying the effects of dilution
as a function of adsorbent loading (Wa) in a TPBM for varying
bulk packing density Fb with constant catalyst loading.
Microreactor Dynamics with Dilution. In carrying out the
studies, we assume Wc ) 6.25 g and Wa ) 12.5 g for the diluted
bed. The bulk packing density Fb(Fb ) Fcat + Fad) is assumed
to be 747 kg/m3. The process performance in time at the outlet
of the diluted beds in terms of XCH4 and yH2 is presented,
respectively, in Figure 8a,b for varying d. The performance of
the undiluted beds for the same catalyst loading, Wc ) 6.25 g
(with Wa ) 0.0 g) and Fb(Fb ) Fcat) equal to 249 kg/m3, are
also given in Figure 8a,b for comparison. The solid lines are
for the undiluted systems, while the dashed lines are for the
diluted reactors. It is clearly seen that for smaller-diameter
reactors (e.g., Figure 8a, 4-mm curve) the effects of dilution
are much more pronounced than those for the larger-diameter
reactor (e.g., Figure 8a, 25-mm curve). Interestingly, for smaller-
diameter tubular microreactors (e.g., Figure 8a, 4-mm curve)
the time taken to reach the steady state is far greater than the
larger-diameter reactor (e.g., Figure 8a, 25 mm). This implies
that higher conversions are possible for longer time duration
for the diluted bed when compared to the undiluted bed. The
radial temperature drop due to the endothermic nature of SMR
Performance Enhancement of SMR
Figure 9. Effect of adsorbent dilution on SMR performance for a
3-mm-diameter reactor: Varying bulk packing density. Values of other
parameters are given in Table 1.
is more uniform in smaller-diameter reactors with dilution as
seen in Figure 4. The average temperature during the initial
transient regime (i.e., before the system reaches the steady state)-
in the smaller-diameter reactor is lower when compared to the
larger-diameter reactor. Adsorption is favored at lower temper-
ature, and this enhances the performance of adsorbent and
thereby decreases the CO2 concentration in the reaction zone.
This decreases the bulk-phase CO2 concentration, while increas-
ing the temperature due to the exothermic nature of adsorption.
These effects are favorable for steam reforming reactions given
by eqs 1 and 2 and allow an optimal balance between reaction
and adsorption. Saturation of adsorbent by adsorbate occurs in
the case of catalyst dilution by adsorbent, and regeneration of
adsorbent is necessary. This is usually carried out by cyclic
operations such as pressure swing adsorption (PSA), temperature
swing adsorption (TSA), or a combination of the above.46-50
The longer transient time observed in the case of smaller TPBM
permits longer cycle time for the cyclic operation of the
adsorption-enhanced SMR process. This is an added advantage
in terms of operating costs.
Effects of Dilution for Varying Bulk Packing Density with
Constant Catalyst Loading. To get insights into the effects of
increasing Wa, we carried out studies by increasing the adsorbent
loading but with a constant Wc ) 6.25 g. For this, the bulk
packing density needs to be altered to keep constant Wc. We
now define a dilution ratio parameter, B, as
Vad
B) (14)
(Vad + Vc)
analogous to dilution with inert solids,26 where Vad is the volume
of adsorbent and Vc is the volume of catalyst.
The steady-state performance for 3-mm-diameter TPBM is
shown in Figure 9 for varying dilution ratio B. It is evident
from Figure 9 that there is an influence of dilution effect for B
> 0.25, and this enhances with increase in B with complete
(46) Rajasree, R.; Moharir, A. S. Comput. Chem. Eng. 2000, 24, 2493-
2505.
(47) Ruthven, D. M. Principles of Adsorption and Adsorption Processes;
Wiley & Sons: New York, 1984.
(48) Ruthven, D. M.; Farooq, S.; Knaebel, K. S. Pressure Swing
Adsorption; VCH Publishers: New York, 1994.
(49) Yang, R. T. Gas Separation by Adsorption Processes; Butter-
worths: Boston, 1987.
(50) Tien, C. Adsorption Calculations and Modeling; Butterworth:
Boston, 1994.
Energy & Fuels, Vol. 20, No. 2, 2006 471
conversion of methane observed for B ) 0.8. However, a longer
reactor length is now required for accommodating the increased
Wa (also shown in Figure 9). The proper choice of B and reactor
diameter can therefore help in choosing a reactor of optimal
length.
In summary, the results obtained on studying the SMR
reaction in TPBM show reduction in thermal gradients in the
reactor. This makes control of the temperature the key operating
parameter for the endothermic SMR reaction and thereby
enhances the process performance in terms of methane conver-
sion and hydrogen purity. The advantage of lower average
temperature for smaller-diameter columns during the initial
transient regime is shown to bring about further enhancement
in SMR process performance for the case of dilution by
adsorbent as adsorption is inherently exothermic in nature. The
results obtained also indicate that the effects of pressure drop
due to the use of TPBM may be controlled for the SMR reaction.
The known advantages of using (a) tubular packed-bed mi-
croreactors and (b) catalyst dilution in reactor operation (as
discussed in the Introduction) have been amalgamated in this
study to show how their combined presence can simultaneously
improve SMR reactor performance.
4. Conclusions
Studies with a dynamic 2D pseudohomogeneous process
model have shown that TPBM and catalyst dilution by adsorbent
enhance the SMR process. Decreasing the reactor diameter
significantly increases the SMR process performance, and
complete conversion of methane is attainable. Also, for the same
process performance, TPBM allows running the SMR process
at a catalyst loading lower than that of larger-diameter reactors.
Analyzing dilution of catalyst by adsorbent material in TPBM
while maintaining constant bulk packing density enhances the
SMR performance in the adsorption-enhanced reaction zone.
This enhancement increases further with decreasing reactor
diameter and also permits longer cycle time for the cyclic
operation of the adsorption-enhanced SMR process. It therefore
offers an added advantage in terms of operating costs. Adsorbent
dilution by varying bulk packing density also has a very
significant effect on SMR process performance. This study
suggests that, by simultaneous optimization of reactor diameter
and adsorbent loading, reduction in process costs and improving
the SMR performance may be possible.
It may be noted that for tubular packed-bed microreactors,
the effects of higher pressure drop (although it may be controlled
for the SMR reaction as seen in the present study), potential
blockage, reactor packing, productivity, effects of nonuniform
flow field due to voidage effects at low particle diameters,
internal field intraparticle gradients, and so forth need to be
analyzed in detail. The development of more sophisticated
models involving flow in disordered packed beds and relating
both microscopic and macroscopic properties using networked
models are likely to lead to more detailed information.51 The
basic trends in the simulation results obtained here from first
principles modeling of tubular packed-bed microreactors with
adsorbent dilution for the SMR reaction are encouraging, and
this strategy needs to be validated by carrying out detailed
experiments.
Acknowledgment. R.R. acknowledges the Council of Scientific
and Industrial Research (CSIR), New Delhi, for financial support.
(51) Thompson, K. E.; Fogler, S. AIChE J. 1997, 43, 1377-1389.
472 Energy & Fuels, Vol. 20, No. 2, 2006 Rajasree et al.

Nomenclature Rp ) Radius of the particle, m

t ) Time, s
B ) Dilution ratio T ) Temperature in bulk gas phase, K
bi ) Langmuir model constant for component i, Pa-1 Tf ) Feed gas temperature, K
C ) Total molar concentration in the bulk phase, mol/m3 Tw ) Wall temperature, K
Cfi ) Molar concentration of component i in the feed, mol/m3 u ) Superficial velocity, m/s
Ci ) Molar concentration of component i, mol/m3 uf ) Initial superficial velocity, m/s
Cpg ) Gas-phase heat capacity, J/mol‚K Vad ) Volume of adsorbent, m3
Cps ) Solid-phase heat capacity, J/kg‚K Vc ) Volume of catalyst, m3
Cvg ) Gas-phase heat capacity at constant volume, J/mol‚K Wa ) Adsorbent loading, kg
d ) Reactor diameter Wc ) Catalyst loading, kg
dp ) Particle diameter z ) Axial coordinate in the reactor, m
D ) Diameter of the reactor, m
DL ) Axial dispersion coefficient, m2/s Greek Letters
hw ) Wall heat transfer coefficient J/m2‚s‚K b ) Bed voidage, dimensionless
kfi ) LDF mass-transfer coefficient of component i, s-1 i ) Average bed voidage of an infinite diameter column
kr ) Effective radial thermal conductivity, J/m‚s‚K P ) Particle porosity, dimensionless
kz ) Effective axial thermal conductivity, J/m‚s‚K t ) Total bed porosity, dimensionless
L ) Reactor length, m ηi ) Catalyst effectiveness factor, dimensionless
mi ) Langmuir constant for component i, mol/kg Fad ) Mass of adsorbent per bed volume, kg/m3
P ) Local total pressure, kPa Fb ) Bulk packing density of the adsorbent and catalyst, kg/m3
Pf ) Feed pressure, kPa Fcat ) Mass of catalyst per bed volume, kg/m3
Pi ) Partial pressure of gas-phase component i, kPa µ ) Viscosity of fluid, kg/m‚s
q* ) Equilibrium solid-phase concentration, mol/kg υij ) Stoichiometric coefficient of component i in reaction j,
qji ) Solid-phase concentration for component i (averaged over an dimensionless
adsorbent particle), mol/kg -∆Hadi ) Adsorption heat of component i, J/mol
r ) Radial coordinate in the reactor, m ∆HRi ) Reaction heat of reaction i, J/mol
R ) Universal gas constant, J/mol‚K
R0 ) Inner radius of the reactor, m EF050205Z