Ind. Eng. Chem. Res.

2005, 44, 9191-9198 9191

Simulation and Thermodynamic Analysis of an Integrated Process

with a Two-Membrane Catalytic Partial Oxidation (CPO) Reactor
for Producing Pure Hydrogen
Wei Feng,† Peijun Ji,*,‡ Danxing Zheng,‡ Tianwei Tan,† and Jakob de Swaan Arons§
College of Life Science and Technology and College of Chemical Engineering, Beijing University of Chemical
Technology, Beijing, 100029, People’s Republic of China, and Physical Chemistry and Molecular
Thermodynamics, Delft University of Technology, Julianalaan 136, 2628 BL Delft, The Netherlands

Catalytic partial oxidation (CPO) is an important technology for producing hydrogen from
methane. A two-membrane CPO reactor, which has both an O2 membrane and a H2 membrane,
integrates various processing steps in a single reactor. It has many advantages, compared to a
conventional CPO reactor or a single-membrane reactor. The intent of this work is to simulate
and investigate the thermodynamic efficiency of the process with a two-membrane reactor to
produce pure hydrogen for application to fuel cells. The simulation of the two-membrane CPO
reactor is based on the kinetics of the reactions and the mechanisms of membrane permeation.
Other units of the process, which include a polymer electrolyte membrane (PEM) fuel cell, a
catalytic burner, compressors, and heat exchangers, have also been simulated. On the basis of
simulation results, the thermodynamic analysis of the process has been performed. The effect
of the inlet temperature of air, the inlet pressure, the flowing mode of the sweeping gas, and
the fraction of H2 recovered on the production rate of useful products (H2 and CO) of the two-
membrane CPO reactor, and on the thermodynamic efficiency of the integrated process, have
been discussed.

1. Introduction

Because of its potential application in the future,

hydrogen has been gaining more and more attention.
Catalytic partial oxidation (CPO) is one of the key
technologies for hydrogen production from natural
gas.1,2
In a conventional CPO process, air (together with
methane and steam) are fed into a conventional CPO
reactor, in which some of the methane is combusted to
provide the heat needed by the steam reforming reac-
tion. The produced hydrogen is mixed with other gases
such as N2 from the air, CO, CO2, steam, and uncon-
verted CH4. Some disadvantages of applying such a
hydrogen-rich gas mixture to a fuel cell are (i) the
hydrogen conversion in fuel cell is limited to 85% and
(ii) CO can damage a PEM fuel cell if the concentration
of CO is >40 ppm.3 Generally, two stages of water-gas-
shift (WGS) reactors and a selective oxidization reactor
are placed after the conventional CPO reactor, to
convert most of the CO into H2 and reduce the concen-
tration of CO. If a H2 membrane is applied to a CPO
reactor, pure hydrogen can be produced. The process
then can be simplified, and the thermodynamic ef-
ficiency of the process can be improved,4 because pure
H2 can be fully converted in the fuel cell.
The development of the O2 membrane5 also provides
the possibility to improve the conventional CPO process.
There are various advantages of an O2-membrane CPO
reactor, such as the elimination of N2 contamination in
* To whom correspondence should be addressed. Fax: 0086-
10-64416406. E-mail: jipj@mail.buct.edu.cn.
†
College of Life Science and Technology.
‡
College of Chemical Engineering.
§
Delft University of Technology.
10.1021/ie050741e CCC: $30.25 © 2005 American Chemical Society
Published on Web 11/01/2005
Figure 1. Scheme of a two-membrane catalytic partial oxidation
(CPO) reactor (the sweeping gas is in a co-current mode).
the product, and control of the supply of oxygen along
the reactor’s axial coordinate, mitigating the formation
of “hot spots” and eliminating NOx emission.
A two-membrane CPO reactor combines the charac-
teristics of an O2-membrane CPO reactor and a H2-
membrane CPO reactor. The scheme of a two-membrane
CPO reactor, which contains both an O2 membrane and
a H2 membrane, is shown in Figure 1. In the two-
membrane CPO reactor, O2 is transported across the
O2 membrane to the reaction side, where it reacts with
methane, which provides energy for the steam reforming
reaction. The syngas is formed through the steam
reforming reaction in the reaction side. The hydrogen
in the gas mixture permeates through a H2 membrane,
and the permeating H2 is then carried out by the
sweeping gas.
Minish et al.5 investigated a two-membrane CPO
system for its techno-economic feasibility. Based on
initial feasibility assessment, they determined that
there are no technical issues that will prevent the
development of the integrated two-membrane reactor.
Chen et al.6 simulated a novel circulating fast fluidized-
bed reactor with O2 and H2 membranes. By optimizing
the number of H2 membranes, the number of O2
membranes, the oxygen feed rate, and the steam-to-
carbon ratio, they determined that the hydrogen pro-
9192 Ind. Eng. Chem. Res., Vol. 44, No. 24, 2005
Table 1. Models for the Two-Membrane CPO Reactora
Reaction Side
gas-phase continuity equation
dFi/dz ) ar(1 - B)Fcpo s ∑k)1 (ηkυikRk) - aH2Ni + aO2Ni
NR H2
H2 H2 O2 O2
N4 ) NH2; Ni ) 0, i * 4; N6 ) NO2; Ni ) 0, i * 6
gas-phase energy equation
dTCPO 6
/dz ) 1/(∑i)1 FiCPI) [arFCPO NR
(1 - B)∑k)1 (-∆HkηkRK) -
r s
q1 - q2 - aH2NH2∆HH2 + aO2NO2∆HO2
q1 ) aH2km/δsp (TCPO - TCPO
nr ); q2 ) aO2km/δsp (Tr
CPO
- TCPO
r reaction, the kinetics of steam reforming to CO and CO2,
solid-phase equations for calculating the effectiveness factors
1/ξ2 d/dξ (De,iξ2 dps,i/dξ) ) 10-5 RT FCPOs rs2 ∑k)1
NR
(νi,kRs,k)
avDe,i/rs dps,i/dξ|ξ)1 ) 10 RT ∑k (ηkυikRk)
-5 NR
solid-phase boundary conditions
ξ ) 0, dps,i/dξ ) 0
gas-phase boundary conditions
z ) 0, Fi ) Fi|z)0, T ) Tin
Nonreaction Side
continuity equation
dGH2/dz ) aH2NH2 or dGO2/dz ) -aO2NO2
energy equation
CPO
dTnrH 2
/dz ) 1/∑jGjCpj[q1 + aH2NH2∆HH2];
CPO
dTnrO /dz ) 1/∑jGjCpj [q2 - aO2NO2∆HO2]
2
a The sweeping gas flows through the reactor in a co-current
mode.
ductivity in the novel reactor is ∼8 times higher than
that in typical industrial fixed-bed steam reformers.
The objective of this work is to conduct the thermo-
dynamic analysis for an integrated process that consists
of the following major units: a two-membrane CPO
reactor, a catalytic burner, compressors, heat exchang-
ers, and a fuel cell. For this purpose, the two-membrane
CPO reactor and other units are simulated to obtain
the production rate of H2 and the work output of the
integrated process under different operation conditions.
The simulation of the two-membrane reactor is based
on kinetic models and the permeation mechanisms of
membranes. Based on the simulation results, the ther-
modynamic analysis of the process has been performed.
2. Simulation
2.1. Two-Membrane Catalytic Partial Oxidation
(CPO) Reactor. For the simulation of a two-membrane
CPO reactor that has been provided with a Ni-Al2O3
catalyst, a one-dimensional steady-state heterogeneous
model is adopted. A uniform oxidation state of the
catalyst is assumed. The mechanism in the reaction and
nonreaction sides of the membrane is considered to be
of the plug-flow type. The influence of intraparticle
concentration gradients within the catalyst pellet is
taken into account by solving the solid-phase continuity
equation at each increment along the adiabatic fixed-
bed reactor coordinate. The gas-phase continuity, en-
ergy, and solid continuity equations in the reaction side,
as well as the continuity and energy equations in the
Table 2. Reaction Rate for the Reactions in the Two-Membrane CPO Reactor
reaction
number reaction
1 CH4 + 2O2 f CO2 + 2H2O
2 CH4 + H2O f CO + 3H2
3 CO + H2O f H2 + CO2
4 CH4 + 2H2O f CO2 + 4H2
a DEN ) 1 + KCOpCO + KH2pH2 + KCH4pCH4 + KH2OpH2O/pH2.
nonreaction side, are presented in Table 1, in which the
corresponding inlet and boundary conditions are also
listed. The energy equations in Table 1 take into
consideration the heat of reaction, the heat exchanged
O2
between the nonreaction zone and the reaction zone, and
the heat carried by the diffusing O2 or H2.
The decrease in pressure is not taken into consider-
ation. The simulation of a two-membrane CPO reactor
is based on the kinetics of the methane combustion
nr )
and the kinetics of the WGS reaction.7 The influence of
carbon deposition and that of the cracking of methane
on the catalyst activity were neglected. The rate equa-
tions, as well as the kinetic parameters applied in the
calculations of the reaction rate, are summarized in
Tables 2-4. In the reaction side, the subscript i repre-
sents a gas species (that is, CH4, H2O, CO, H2, CO2, O2,
or N2). In the solid-phase continuity equation, the
effective diffusivity of component i is related to the
molecular and Knudsen diffusivities. The effective dif-
fusivities are calculated according to the method in
the literature.8 The physical chemical properties Cip,9
equilibrium constants,10 and diffusivities11 are each
considered to be a function of temperature. The solid-
phase continuity equation in Table 1 is solved by
difference methods. The number of collocation points
defined is dependent on the effect on the final calcula-
tion results. Normally, 10 collocation points are defined.
The resulting difference equations are solved at each
increment of the axial reactor coordinate. In each
reactor increment, the intraparticle concentration gra-
dients of the previous step are used as the initial value
of the next step to solve the solid-phase continuity
equations; thus, rapid convergence is obtained.
2.2. Permeation Mechanism of the H2 Mem-
brane. The permeability of hydrogen through the H2-
permeable membrane is calculated according to eq 1:
h )]
Pm exp[- EA/(RT
NH2 )
δH2
high
( pH 2
- x xp low
H2 ) (1)
The apparent activation energy (EA) and pre-exponen-
tial factor (Pm) of the membrane are 29.73 kJ/mol and
7.71 × 10-4 mol m/(s m2 bar0.5), respectively.2
2.3. Permeation Mechanism of the O2 Mem-
brane. In the simulation, the composition of the per-
ovskite membrane for O2 permeation is La0.2Ba0.8Fe0.8-
Co0.2O3-δ. The permeability of oxygen through this
membrane is calculated from eq 2:
( )
high
h )]
A1 exp[- Ea/(RT pO 2
NO2 ) ln low (2)
δO2 pO2
The activation energy Ea and the pre-exponential factor
A1 are 63 kJ/mol and 7.34 × 10-7 mol/(m s K), respec-
kinetics of reactiona
R1 ) k1,axCH4xO2/(1 + KCH0 0
xCH4+KO xO2)2 + k1,bxCH4xO21/2/
4 2
0 0
(1 + KCH 4
x CH4+KO xO2)
2
R2 ) (k2/pH22.5)(pCH4pH2O - pH23pCO/Keq2)/DEN2
R3 ) (k3/pH2)(pCOpH2O - pH2pCO2/Keq3)/DEN2
R4 ) (k4/pH23.5)(pCH4pH2O2 - pH24pCO2/Keq4)/DEN2
 Ind. Eng. Chem. Res., Vol. 44, No. 24, 2005 9193

Table 3. Parameter Values for the Expression kk ) k0k H2 (the heat released by burning of H2 to steam at
LHV
exp[-Ea,k/(RT)] for the Reaction Rate Constant standard state, -241.83 kJ/mol) ∆HH 2
, as shown in
eq 5:15
reaction k0k [mol-1 kgcal-1 s-1] Ea,k [J/mol]
1 k1,a 3.14 × 10-4
1 k1,b 2.64 × 10-4 WFC
2 k2 1.17 × 1015 bar0.5 240.1 × 103 ηFC ) LHV
(5)
3 k3 5.43 × 105 bar-1 67.13 × 103 ηfFH2(-∆HH 2
)
4 k4 2.83 × 1014 bar0.5 243.9 × 103

Table 4. Parameters Values for the Expression Ki ) K0i In eq 5, FH2 and ηf represent the feeding rate of H2
exp[-∆Hads,i/(RT)] for the Adsorption Coefficients and the fraction of H2 converted in the fuel cell,
adsorption ∆Hads,i respectively. The work output of the fuel cell is calcu-
coefficient K0i [kJ/mol] lated by eq 6:
0
KCH 6.67 × 10-2 LHV
0
KO 2
4
4.34 × 10-5 WFC ) ηFCηfFH2(-∆HH 2
) (6)
KCH4 6.65 × 10-4 bar-1 -38.28
KCO 8.23 × 10-5 bar-1 -70.65 In this work, an ηf value of 100% is assumed for the
KH2 6.12 × 10-9 bar-1 -82.90 humidified pure H2.16,17
KH2O 1.77 × 105 88.68

tively. The oxygen permeation rate equation, and the
coefficients, have been obtained from the literature.12,13
2.4. Heat Exchanger. By solving the energy balance
equation, the heat exchangers are simulated; 20% of
heat loss in the units is assumed.
2.5. Compressor. The electric power used in the
compressor is calculated by assuming the compressor
exergy efficiency (ηcp) to be 50% (see eq 3).14
3. Simulation of the Two-Membrane CPO
Reactor
At a given methane conversion, the production rate
of useful products of a CPO reactor increases as the inlet
temperature of reactants increases.18,19 However, it is
difficult for industry to increase the temperature of
methane and steam above 800 K. Therefore, in this
work, the inlet temperature of methane and steam for
the two-membrane CPO reactors is set at 800 K.

( )
FtRT0 P In a two-membrane CPO reactor, H2 is transported
Wcp ) ln
ηcp P0
2.6. Catalytic Burner. A catalytic burner is used to
heat the reactants to the inlet temperature. The re-
maining H2, CO, CO2, N2, H2O, and CH4 in the exhaust
gas of the membrane reactor or the fuel cell are
introduced into the furnace. The temperature of the
after-combustion gas mixture leaving the furnace (Tend)
is calculated by solving eq 4:
∆Hheating 3 the temperature cools to the operation temperature of
ηburner
+ ∆H|TTfg0 + ∆H|TT0end + ∑ Fburner
l ∆Hcom
l )0
l)1
∆Hheating represents the heat required for heating the
reactants to the inlet temperature (Tin) of the two-
membrane CPO reactor. ηburner is the heating efficiency
of the catalytic burner. Fburner
l and ∆Hcom
l represent the
molar flow rate and the heat of combustion of the
combustible component l in the rejected fuel gas mixture
at T0, respectively. The combustible components in the
rejected fuel gas mixture include CH4, CO, and H2.
∆H|TT0end represents the heat required to elevate the
temperature of all after-combustion species (CO2, H2O,
and N2) from T0 to Tend. Tfg represents the temperature
of the fuel gas mixture before introducing it into the
burner. ∆H|TTfg0 is the heat released by the fuel gas
mixture when cooled from Tfg to T0. In this work, a 20%
heat loss in the furnace and heat exchangers is as-
sumed.
2.7. Polymer Electrolyte Membrane Fuel Cell
(PEMFC). The efficiency of fuel cell (ηFC) is usually
defined as the ratio of electrical power output WFC to
the rate of H2 converted and the lower heating value of
(3) to the permeate side of the H2 membrane, mainly driven
by the difference in the square root of the partial
pressure over the membrane. Using a sweeping gas,
lower H2 partial pressures at the permeate side of the
membrane can be achieved; thus, a higher fraction of
H2 recovered can be obtained. Normally, pure argon,
nitrogen, or steam is used as sweeping gas for H2
separation.6,20 In this work, the separated H2 is to be
fed into the PEM fuel cell, which requires pure H2 (or
humidified pure H2) to achieve 100% H2 conversion;
therefore, steam is chosen as the sweeping gas. After
the fuel cell, the separated H2 becomes humidified pure
H2; thus, the separated H2 can be fully converted to
(4) electricity in the fuel cell.16,17
Factors such as the inlet pressure, the inlet temper-
ature of air, the flowing mode of the sweeping gas, and
the fraction of H2 recovered will affect the production
rate of useful products (which include H2 and CO). In
the following sections, based on the simulation results,
the effects of these factors are discussed.
3.1. Definition of the Fraction of H2 Recovered.
Figure 2a shows the profile of the mole fraction of each
component in a two-membrane CPO reactor. The CH4
conversion rate is slow near the entrance of the reactor,
because of a gradually feeding of O2 through an O2
membrane. The removal of hydrogen through a H2
membrane drives the steam reforming reaction and the
WGS reaction toward a higher CH4 conversion and a
higher CO conversion; therefore, the mole fraction of
CO2 is much higher than that of CO. Because of the
continuous removal of hydrogen from the reactor, the
mole fraction of hydrogen does not change so much along
the reactor axial coordinate. In addition, the production
rate of separated H2 increases along the reactor length,
as shown in Figure 2b.
9194 Ind. Eng. Chem. Res., Vol. 44, No. 24, 2005
Figure 2. Plots of (a) molar fractions of the different species and
(b) the production rate of separated H2, each versus the dimen-
sionless axial coordinate of the two-membrane CPO reactor (at
Tin ) 800 K, Pin ) Pair )10 bar, and PH2 ) 1 bar; the inlet rates of
CH4 and H2O are 1.0 and 1.5 mol/s, respectively). The inlet rate
of O2 (the air) into the nonreaction side of the two-membrane
reactor is 0.35 mol/s, and the inlet rates of CH4, H2O, and O2 are
1.0, 1.5, and 0.35 mol/s, respectively. The H2 and O2-membrane
areas are 5 and 14 m2, respectively. Steam is the sweeping gas,
flowing at a rate of 5 mol/s.
The ratio of separated H2 to all the useful products is
defined as the fraction of H2 recovered (σ):
S are 1.0 and 1.5 mol/s, respectively.
FH 2
σ) S
(7)
FH + FRCO + FH
R
2 2
R
where FH 2
and FRCO are the flow rates of H2 and CO
S
remaining in the reaction region, respectively. FH 2
is
the flow rate of separated H2, and all the H2 and CO
produced are called the useful products in this work.
The fraction of H2 recovered is a very important
parameter, which is frequently used in the following
discussion, because the amount of H2 that is recovered
will have a great effect on the thermodynamic efficiency
of the integrated process.
3.2. Effect of the Inlet Temperature of Air on the
Useful Products. Figure 3 shows the temperature
profiles of the reaction gas mixture, the separated H2
together with the sweeping gas (steam), and the air
flowing along the reactor axial coordinate. The solid
lines and the dashed lines represent the results for the
inlet temperatures of air at temperatures of 800 and
1200 K, respectively.
From the temperature profiles, we know that, at the
inlet temperature of air (Tair ) 1200 K), the air provides
heat to the CPO reaction region. Because of the heat
from the air, the amount of CH4 required for combustion
is reduced and more methane can be converted to useful
Figure 3. Temperature profiles of air, the reaction gas mixture,
and the separated H2 of the two-membrane CPO reactor when Tair
) 800 and 1200 K. The CH4 conversion is 95%, and the fraction
of H2 recovered is 90%. Tin ) 800 K; Pin ) Pair ) 2 bar; PH2 ) 1
bar; and the inlet rates of CH4 and H2O are 1.0 and 1.5 mol/s,
respectively.
Figure 4. Production rate of useful products of the two-membrane
CPO reactor versus the fraction of H2 recovered at Tair ) 1200
and 800 K, respectively. The CH4 conversion is 95%. Tin ) 800 K;
Pin ) Pair ) 2 bar; PH2 ) 1 bar; and the inlet rates of CH4 and H2O
products. Therefore, the production rate of useful prod-
ucts increases as the inlet temperature of air Tair
increases, as shown in Figure 4.
3.3. Effect of the Fraction of H2 Recovered on
the Useful Products. If the type and thickness of the
H2 membrane is fixed, the fraction of H2 recovered (σ)
can be adjusted by changing the H2-membrane area
applied, the molar flow rate of the sweeping gas, and
the pressure at the permeate side or the reaction side.
In a conventional CPO reactor, the heat released by
the methane combustion reaction is used to provide heat
for the methane steam reforming reaction, increasing
the temperature of the gas mixture to achieve a given
methane conversion. In a two-membrane CPO reactor
with a H2 membrane, the steam reforming reaction is
not only driven by the methane combustion, but also
by the removal of H2 through a H2 membrane (the
removal of H2 changes the composition of the reaction
gas mixture and, thus, moves the gas mixture in the
reaction zone away from the equilibrium). Therefore, the
steam reforming reaction can achieve a given methane
conversion at a lower temperature, which requires the
combustion of less methane. Therefore, for a given
methane conversion and a given inlet condition, more
inlet methane can be converted to useful products; i.e.,

Figure 5. Production rate of useful products of the two-membrane
CPO reactor versus the inlet pressure. The CH4 conversion is 95%.
Tin ) 800 K; Tair ) 1200 K; Pin ) Pair; PH2 ) 1 bar; and the inlet
rates of CH4 and H2O are 1.0 and 1.5 mol/s, respectively.
Table 5. Effect of Pressure on the Required
H2-Membrane Areaa
pressure, P H2-membrane area
[bar] [m2]
9 2.28
16 1.59
a The production rate of separated H2 is 2.9 mol/s. Tin ) 800 K;
Tair ) 1200 K; PH2 ) 1 bar; the inlet rates of CH4 and H2O are 1.0
and 1.5 mol/s, respectively. Steam is the sweeping gas, at a flow
rate of 10 mol/s.
the production rate of useful products increases as σ
increases, as shown in Figures 4 and 5.
3.4. Effect of the Inlet Pressure on the Useful
Products. Figure 5 shows the effect of inlet pressure
on the production rate of useful products for the two-
membrane CPO reactor at different σ values. At higher
inlet pressure, less useful products are produced. How-
ever, at higher inlet pressure, the H2-membrane area
required by the two-membrane CPO reactor is reduced,
as shown in Table 5.
3.5. Effect of the Flowing Mode of Sweeping Gas.
For the two-membrane CPO reactor, the sweeping gas
of steam can be used to carry the separated H2 out,
either in a counter-current mode or in a co-current
mode. The reactor with a counter-current mode has been
modeled by a stepwise numerical procedure. It begins
with a fixed production rate of separated H2 for a
hypothetical flowing rate of sweeping gas at z ) 0 on
the permeate side. The outlet temperature of separated
H2 must be assumed. Repeating the calculation until
the convergence is achieved, the molar rate of separated
H2 is zero at the end of the reactor.
Figure 6 shows the comparison between counter-
current mode and co-current mode, in terms of the
amounts of steam required. Flowing in a counter-
current mode for the sweeping gas is better than in a
co-current model, because lesser amounts of steam are
needed.
4. Thermodynamic Analysis of the Integrated
Process
The thermodynamic efficiency (ηEx) is an important
parameter for a process.21,22 It reflects the fate of the
original work (Exinput) put into the process as fuel,
Ind. Eng. Chem. Res., Vol. 44, No. 24, 2005 9195
Figure 6. Effect of flowing mode on the amounts of steam (as
the sweeping gas) required at different inlet pressure. The fraction
of H2 recovered is 90%. The CH4 conversion is 95%. Tin ) 800 K;
Tair ) 1200 K; Pin ) Pair; PH2 ) 1 bar; the inlet rates of CH4 and
H2O are 1.0 and 1.5 mol/s, respectively.
electricity, or heat. The overall exergy efficiency ηEx for
the process is defined as given in eq 8:
Wnet
ηEx ) (8)
Exinput
where
Wnet ) WFC - Wcp (9)
The exergy input Exinput includes the exergy of methane
used as reactant in the two-membrane CPO reactor, the
exergy of the methane added as additional fuel in the
catalytic burner, and the exergy from some cooling
water. The net work output (Wnet) of each process is
equal to the work output of the fuel cell (WFC) minus
the work used in the compressors (Wcp), as expressed
in eq 9.
4.1. Exergy Flows of the Process. Figure 7 il-
lustrates the scheme of the integrated process with a
two-membrane CPO reactor, in which heat recovery and
heat integration have been taken into consideration,
using a catalytic burner and heat exchangers. Compres-
sors to compress the air are indicated, with the input
work needed. The energy of the fuel gas mixture rejected
from the two-membrane reactor is recovered by intro-
ducing the gas mixture into the catalytic burner, where
the combustion heat of the remaining fuel gas is utilized
to heat the reactants. Heat exchangers are used to
recover the heat from the hot streams used to make
steam as the sweeping gas, and they are used to heat
the air that is introduced into the reactor and the fuel
cell. Corresponding to the temperature of each stream,
the exergy flows have been indicated in the process
scheme.
4.2. Exergy Depletion of the Process. Based on
the exergy flows shown in Figure 7, the exergy balance
of the process has been obtained and is presented in
Figure 8, including the work lost in each step and the
fractions of work lost for some key steps. The results
show that the work loss of the process mainly occurs in
the fuel cell. Other contributors are in the sequence of
the catalytic burner, the two-membrane CPO reactor,
and the heat exchangers. Because of the work loss
9196 Ind. Eng. Chem. Res., Vol. 44, No. 24, 2005
Figure 7. Exergy flows in an integrated process. Pin ) 2 bar, and the CH4 conversion is 95%; the air inlet temperature is 1200 K. “HE”
denotes the heat exchanger.
Figure 8. Exergy balance of the process, corresponding to a
fraction of H2 recovered of σ ) 85%. The number, which is
expressed as a percentage, is the ratio of the work loss of some
key steps to the total work lost.
throughout the process, the overall exergy efficiency is
not higher than 40%.
4.3. Thermodynamic Efficiency of the Process.
In Figure 9, the effects of the flowing mode of sweeping
gas and the fraction of H2 recovered on the overall
exergy efficiency of the process are presented. The
sweeping gas flowing in a counter-current mode makes
the process have a higher thermodynamic efficiency
than in a co-current mode, because less steam is needed
in the counter-current mode. For a fraction of H2
recovered that is <80%, the flowing modes of the
sweeping gas have no effect on the overall exergy
efficiencies, because the remaining fuel gas in the
reactor is utilized and is sufficient to heat the reactants
and heat the water to generate steam. At a higher
fraction of H2 recovered, the process has a higher
thermodynamic efficiency, because more pure H2 is
Figure 9. Overall exergy efficiency (ηEx) versus the fraction of
H2 recovered (σ). Tair ) 1200 K, and the CH4 conversion is 95%.
Tin ) 800 K; Pin ) Pair ) 2 bar; and the inlet rates of CH4 and
H2O are 1.0 and 1.5 mol/s, respectively.
converted in the fuel cell. Figure 10 shows the effect of
the inlet pressure on the overall exergy efficiency. The
exergy efficiency decreases with the inlet pressure,
because of a lower production rate of useful products at
a higher inlet pressure. The temperature of the reaction
region increases as the inlet pressure increases. For a
given fraction of H2 recovered, there is a maximum inlet
pressure, which corresponds to the maximum temper-
ature in the reaction region that the H2 membrane can
tolerate.
5. Conclusions
Based on the simulation results and the thermody-
namic analysis, we can conclude that a higher inlet
temperature of air, the sweeping gas that follows in a
counter-current mode, a lower inlet pressure, and a
higher fraction of H2 recovered can make the two-

Figure 10. Overall exergy efficiency (ηEx) versus the inlet
pressure for different fractions of H2 recovered (σ); the CH4
conversion is 95%. Tin ) 800 K; Pin ) Pair; PH2 ) 1 bar; and the
inlet rates of CH4 and H2O are 1.0 and 1.5 mol/s, respectively.
For σ ) 75% and 80%, the results are independent of the flowing
mode.
membrane CPO reactor produce more useful products
and cause the process to have a higher thermodynamic
efficiency.
For industrial operation, the inlet pressure should be
chosen carefully. A lower inlet pressure is better, in
terms of producing more useful products and having a
higher thermodynamic efficiency. However, a lower
operation pressure leads to a larger area of the H2
membrane, which is still very expensive. By considering
the production rate of useful products, the thermody-
namic efficiency and the cost of H2 membrane together,
an appropriate inlet pressure can be determined.
List of Symbols
ar ) cross-sectional area of the reactor [m2]
aH2 ) H2 membrane area per unit reactor length [m2/m]
aO2 ) O2 membrane area per unit reactor length [m2/m]
av ) area of particle per unit mass of catalyst [m2/kg]
aw ) area of the wall between the reaction tube and the
parallel furnace of the reformer [m2/m]
A1 ) pre-exponential factor for the O2 membrane [J/mol]
Cip ) heat capacity of species i [J/(mol K)]
Cjp ) heat capacity of species j [J/(mol K)]
De,i ) effective diffusion coefficient of species i in the
catalyst pellet [m2/s]
Di(rpore) ) effective diffusivity of species i with a pore radius
rpore [m2/s]
Dki(rpore) ) Knudsen diffusivity of species i with a pore
radius rpore [m2/s]
Dmi ) molecular diffusivity of species i [m2/s]
h i ) average diffusivity of species i [m2/s]
D r2 ) tube outside radius [m]
EA ) apparent activation energy of the H2 membrane
[J/mol]
Ea ) activation energy [J/mol]
Ea,k ) activation energy of reaction k [J/mol]
ea ) activation energy [J/mol]
Ex ) exergy flow rate [J/s]
Fi ) molar flow rate of i [mol/s]
S Tfurnace ) temperature of the parallel furnace of a steam
FH 2
) production rate of separated H2 [mol/s]
R
FH 2
) molar flow rate of remaining H2 in the rejected fuel
gas from the H2-membrane reactor [mol/s]
FRCO ) molar flow rate of CO in the rejected fuel gas from
the H2-membrane reactor [mol/s]
Fburner
l ) molar flow rate of combustible component l in
the rejected fuel gas [mol/s]
Ft ) total molar flow rate [mol/s]
GH2 ) molar flow rate of H2 in the nonreaction side [mol/s]
Ind. Eng. Chem. Res., Vol. 44, No. 24, 2005 9197
Gj ) molar flow rate of component j in the nonreaction side
[mol/s]
GO2 ) molar flow rate of O2 in the nonreaction side [mol/s]
JO2 ) O2 permeation flux [cm3(STP)/(cm2 s)]
Keq ) equilibrium constant
Ki ) adsorption constant of species i
K0i ) pre-exponential factor for adsorption parameters
ke ) thermal conductivity of the catalyst bed [J/(m s K)]
kk ) reaction rate constant of reaction k
k0k ) pre-exponential factor for the reaction rate [mol/
(kgcal s)]
km ) averaged thermal conductivity of the membranes
[J/(m s K)]
ksp ) thermal conductivity of the membrane support layer
[J/(m s K)]
L ) reactor length [m]
NH2 ) H2 permeation rate through the H2 membrane [mol/
(m2 s)]
H2
Ni ) component i permeation rate through the H2
membrane [mol/(m2 s)]
NO i ) component i permeation rate through the O2 mem-
2
brane [mol/(m2 s)]
NO2 ) O2 permeation rate through the O2 membrane [mol/
(m2 s)]
NR ) number of reactions
ntube ) number of membrane tubes
Pair ) pressure of air of the two-membrane CPO reactor
[bar]
P° ) standard state pressure; P° ) 1 bar
Pm ) preexponential factor of the H2 membrane [mol m/(s
m2 bar0.5)]
P0 ) pressure of the environment; P0 ) 101.325 kPa
ps,i ) partial pressure of species i in a catalyst particle [bar]
pi ) partial pressure of species i in the gas phase [bar]
high
pH 2
) partial pressure of H2 in the reaction side [bar]
low
pH ) partial pressure of H2 in the nonreaction side [bar]
2
high
pO 2
) partial pressure of O2 in the nonreaction side [bar]
low
pO 2
) partial pressure of O2 in the reaction side [bar]
Pin ) inlet pressure of the two-membrane CPO reactor [bar]
q ) the heat flux between the reaction side and the
nonreaction side [J/(s m)]
R ) gas constant [J/(mol K)]
Rk ) rate of reaction k in the main stream of the
two-membrane CPO reactor, calculated with pi [mol/
(kgcat s)]
rs ) equivalent radius of the catalyst particle [m]
Rs,k ) rate of reaction k inside the catalyst particle,
calculated with ps,i [mol/(kgcat s)]
r1 ) tube inside radius [m]
r3 ) inner radius of the shell [m]
S(rpore) ) void volume fraction of a pore with radius rpore
T ) absolute temperature [K]
Tair ) inlet temperature of air of the two-membrane CPO
reactor [K]
Tfg ) temperature of the rejected fuel gas mixture [K]
reformer [K]
Tin ) inlet temperature of the two-membrane CPO reactor
[K]
Tnr ) temperature in the nonreaction side of the two-
membrane reactor [K]
Tr ) temperature in the reaction side of the membrane
reactors [K]
h ) average temperature of the membranes [K]
T
T0 ) temperature of the environment; T0 ) 298.15 K
9198 Ind. Eng. Chem. Res., Vol. 44, No. 24, 2005
Wcp ) work used for compression [J/s]
WFC ) work output of fuel cell [J/s]
Wlost ) work lost [J/s]
Wnet ) net work output [J/s]
xi ) molar fraction of species i
(XO2)12 ) fractional oxygen conversion
y ) thickness from central of catalyst bed to the membrane
wall [m]
z ) axial coordinate of the reactors [m]
Greek Letters
β ) β ) pCO2pH2/(pCOpH2OKeq)
B ) void fraction of packing
δO2 or δH2 ) thickness of the membrane layer [m]
s ) porosity of catalytic particle
δsp ) thickness of the support layer [m]
δw ) thickness of the wall between the reaction tube and
the parallel furnace of a steam reformer [m]
σ ) fraction of H2 recovered (on CO + H2 basis)
ηcp ) exergy efficiency of the compressor
ηf ) percentage of H2 converted in the fuel cell
ηFC ) efficiency of the fuel cell
ηburner ) efficiency of the catalytic burner
ηEx ) overall exergy efficiency
ηk ) effectiveness factor of reaction k
νik ) stoichiometric coefficient of component i of reaction k
µik ) chemical potential of component i of reaction k
Fs ) density of the catalyst [kg/m3]
τ ) tortuosity factor
ξ ) dimensionless pellet coordinate
ψ ) variable representing the effect of P and diffusion into
the catalytic slab
∆mixEx ) mixing exergy [J/s]
∆Hads,i ) standard adsorption enthalpy of component i [kJ/
mol]
∆HO2 ) heat transferred by permeating O2 from the
nonreaction side to the reaction side [J/mol]
∆HH2 ) heat transferred by permeating H2 from the
reaction side to the nonreaction side [J/mol]
∆Hheating ) heat required to heat the reactants [J/s]
LHV
∆HH 2
) H2 lower heat value [J/mol]
∆Hk ) heat of reaction k [J/mol]
∆Hcom
l ) combustion heat of component l [J/mol]
∆HTTfg0 ) heat of the rejected fuel gas from Tfg to T0 [J/s]
∆HTT0end ) heat of the combusted fuel gas mixture from T0
to Tend [J/s]
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Received for review June 21, 2005
Revised manuscript received August 24, 2005
Accepted September 29, 2005
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