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0d

Journal of Membrane Science 339 (2009) 160–170

Contents lists available at ScienceDirect

Journal of Membrane Science

journa l homepage: www.e lsev ier .com/ locate /memsci

ydrogen production by methanol steam reforming in a membrane reactor:alladium vs carbon molecular sieve membranes

andra Sá a, Hugo Silva a, José M. Sousa a,b, Adélio Mendes a,∗

LEPAE-Departamento de Engenharia Química, Faculdade de Engenharia, Universidade do Porto, Rua Dr. Roberto Frias, s/n 4200-465 Porto, PortugalDepartamento de Química, Universidade de Trás-os-Montes e Alto Douro, Apartado 202, 5001-911 Vila-Real Codex, Portugal

r t i c l e i n f o

rticle history:eceived 17 February 2009eceived in revised form 13 April 2009ccepted 24 April 2009vailable online 3 May 2009

a b s t r a c t

In this study, the production of hydrogen by methanol steam reforming in a membrane reactor (MR) wassimulated using a one-dimensional mathematical model. The model assumes axially dispersed plug-flow with pressure drop for the retentate side, and plug-flow behaviour with no axial dispersion andno pressure drop for the permeate side. The finite volume method was used for space discretization,

eywords:ydrogenethanol steam reforming

arbon molecular sieve membranesalladium membranes

being the dependent variables determined with high-resolution schemes. Two types of membranes weresimulated, namely a carbon molecular sieve membrane (CMS) and a palladium membrane (Pd). Thesimulation results showed that the CMS membrane reactor presents higher hydrogen recoveries, whilethe Pd membrane reactor has the advantage of producing a pure hydrogen stream. It was also studied amembrane reactor with two membrane sections, one made of CMS and the other made of palladium. Thisnew configuration revealed some advantages compared to the reactor equipped with either membrane

ed th

odelling type, and namely it show

. Introduction

Nowadays, worldwide environmental concerns are triggeringhe search for clean energy sources. Lowering the emissions of gaseshat contributes to the greenhouse effect and global warming ismperative, and fuel cells are providing an attractive solution to thisroblem. Presenting only heat and water as emissions, hydrogen

uel cells are an important source of clean electrical power [1–4]. Toenerate power, polymer electrolyte membrane fuel cells (PEMFC)equire hydrogen as fuel. However, direct use of hydrogen in theEMFC presents distribution and storage problems caused by its

ow energy density per normal volume. Hydrogen production initu from hydrocarbon fuels comes as a possible solution to thisroblem [5–7]. Methanol presents several advantages compared tother fuels, namely: is liquid at atmospheric conditions, has highydrogen to carbon ratio, and its reforming temperature is relatively

ow (200–300 ◦C) [8–10]. In what concerns methanol supply, it cane produced from a variety of sources, including natural gas, coalnd biomass. Alternatively to steam reforming, methanol can be fed

irectly to a fuel cell (DMFC—direct methanol fuel cell) in order toenerate power. However, compared to the PEMFC, these devicesresent lower efficiency, lower power density and higher catalystsage, which results in higher costs [11]. Taken all into concern,

∗ Corresponding author. Tel.: +351 22 508 1695; fax: +351 22 508 1449.E-mail address: mendes@fe.up.pt (A. Mendes).

376-7388/$ – see front matter © 2009 Elsevier B.V. All rights reserved.oi:10.1016/j.memsci.2009.04.045

e highest hydrogen recovery.© 2009 Elsevier B.V. All rights reserved.

methanol steam reforming is seen as a reliable source of hydrogenfor fuel cell applications.

According to the literature [12,13], three chemical reactionscan be considered in the methanol steam reforming process: themethanol steam reforming itself (SR, Eq. (1)), the main reaction,and the side reactions methanol decomposition (MD, Eq. (2)) andwater gas shift (WGS, Eq. (3)):

CH3OH + H2O � CO2 + 3H2 �H = 49.7 kJ mol−1 (1)

CH3OH � CO + 2H2 �H = 92.0 kJ mol−1 (2)

CO + H2O � CO2 + H2 �H = 41.2 kJ mol−1 (3)

Besides the non-reacted methanol and water, the reaction prod-ucts are hydrogen (desired product), carbon dioxide and carbonmonoxide. To feed a fuel cell, the hydrogen stream needs purifica-tion, mainly because carbon monoxide poisons the anodic catalystof the fuel cell and its concentration must be lower than 10 ppm[14]. This could be done in several ways, namely using a permse-lective membrane. Combining in the same device both operations,reaction and separation, membrane reactors present several advan-tages towards conventional reactors. Besides reducing the numberof process units, a MR could also achieve conversions higher than

the ones obtained in a conventional reactor at the same operatingconditions. Gallucci et al. [15], for example, showed how methanolconversion, hydrogen production and hydrogen selectivity can beenhanced by using a membrane reactor over the values obtainedin a traditional reactor. Matzakos et al. [16] also used a membrane

rane S

rcdg

rimssfastpt[sah

septapmrmlt

tmlCimbtdmwrcgr1

2

Ipttm

S. Sá et al. / Journal of Memb

eactor for hydrogen production, and presented an integrated pro-ess with a steam reformer and a fuel cell. In their work, the authorsescribe an overall process-flow diagram, showing that an inte-rated system is viable.

The choice of the membrane kind to use in a membraneeactor must consider both cost and performance. Several stud-es have been published concerning the use of palladium based

embrane reactors [9,17–20]. Palladium membranes are highlyelective to hydrogen and allow the production of a pure H2tream, at least theoretically. However, these membranes suf-er from hydrogen-embrittlement cracking during thermal cyclingnd readily evidence surface contamination by sulphur-containingpecies [21]. Moreover, they are expensive, so a cheaper solu-ion is strongly needed. Although these membranes are onlyermeable to hydrogen, they have limited applications due toheir low permeability compared to porous inorganic membranes22,23]. As a possible alternative, CMS membranes are less expen-ive and present higher permeabilities than Pd membranes. As

drawback, they are brittle and present lower selectivities toydrogen.

The use of carbon molecular sieve membranes in methanolteam reforming reactors has not been extensively studied. Zhangt al. [10], for example, presented an experimental study com-aring a traditional reactor with a CMS membrane reactor forhis reaction. They concluded that higher methanol conversionnd lower carbon monoxide yield were achieved, enhancing theotential of these membranes. Harale et al. [24] studied a CMSembrane reactor for another application: the water gas shift

eaction. The membranes presented very high hydrogen per-eation fluxes, reinforcing the idea that higher flow rates and

ower membrane areas can be used with such membrane reac-ors.

These promising results justify the need of a detailed study ofhe potential advantages of CMS membranes over the palladium

embranes. In this thought line, the present work aims to ana-yze and compare the advantages and disadvantages of both Pd andMS membrane reactors to conduct the methanol steam reform-

ng. Its main objective is to analyze in which conditions each of theembranes perform better than the other and how can both mem-

ranes be integrated simultaneously in the same reactor in ordero get a synergy. To perform such study, it was developed a one-imensional comprehensive mathematical model of a packed-bedembrane reactor. A set of simulation results are then providedhich illustrate some key points about the use of this membrane

eactor, namely the methanol conversion, carbon monoxide con-entration in the hydrogen rich stream and hydrogen recovery. Theoal is to maximize the methanol conversion and the hydrogenecovery, keeping the CO concentration at the permeate side below0 ppm.

. Development of the membrane reactor model

Fig. 1 shows the scheme of the simulated membrane reactor.t consists of a tubular membrane with surface area AM, housing a

acked-bed of catalyst in the inner side and a permeate chamber onhe outer side. A gas phase stream of methanol and water is fed tohe reaction side, producing hydrogen, carbon dioxide and carbon

onoxide. At the permeate side, water vapour is used as sweep gas.

Fig. 1. Scheme of the simulated membrane reactor.

cience 339 (2009) 160–170 161

Two types of membranes are considered in this work: a palladiummembrane and a carbon molecular sieve membrane.

The mathematical model proposed comprises the steady-statemass balance equations for the reaction and permeation sides, aswell as the respective boundary conditions. This model consid-ers isothermal conditions and ideal gas behaviour. The retentateis assumed to follow an axially dispersed plug-flow pattern, withpressure drop described by the Ergun equation [25] and filledwith a methanol steam reforming catalyst with an uniform cross-sectional void fraction. The permeate is assumed to be plug-flowwith no axial dispersion, with no pressure drop and flowing inco-current.

2.1. Retentate (reaction) side

Partial mass balance

− ddz

(uRpRi )−Dax

ddz

(PR d

dz

(PR

i

PR

))− 2�rM

εAR�TNi+

mcat

εVR�TRi = 0

(4)

Total mass balance

− ddz

(uRPR) − 2�rM

εAR�T

∑i

Ni + mcat

εVR�T�catRi = 0 (5)

Pressure drop

− dPR

dz= 150

�uR

d2p

(1 − ε)2 + 74

�gas(uR)2

dP

1 − ε

ε(6)

Boundary conditionsThe partial mass balance is a second order differential equation,

thus, two boundary conditions are needed [26]. When the pres-sure drop cannot be considered negligible, it must be imposed oneboundary condition in z = 0 and other in z = 1, as follows:

z = 0 : εDaxddz

(pR

i

PR

)= uR

pRi

− pR,ini

PRand uR = uR,in (7)

z = 1 :ddz

(pR

i

PR

)= 0 and PR = PR,out (8)

where the superscript R stands for retentate side, i refers to the ithcomponent, z is axial coordinate, u is the interstitial velocity, p isthe partial pressure, P is the total pressure, Dax is the effective axialdispersion coefficient, rM is the internal radius of the membrane,AR is the cross-sectional area of the retentate chamber, VR is thevolume of the retentate chamber, ε is the void fraction of the cat-alyst bed, � is the gas constant, T is the absolute temperature, N isthe flux through the membrane, and mcat is the mass of catalyst,dP is the catalyst particle diameter, � is the gas viscosity and �gas

is the gas density. R is the rate of consumption or formation of theindividual species, which is given by:

Ri =∑

j

�ijrj (9)

where rj is the reaction rate of reaction j (described below) and �ijis the stoichiometric coefficient for species i in the reaction j, takennegative for reactants, positive for reaction products, and null for

the components that do not take part in the reaction.Kinetic model

The reaction rate expressions used in this model are the onesdeveloped by Peppley et al. [13]. It is assumed that the reactionoccurs only at the catalyst surface, and that there is no mass trans-

1 rane S

H2O)C

/p1/H2

COpH

H2O/p

aSA

1/2H2

)

2

2

at

N

wdfiia

2

tti(

−

−

−

advantage of using this high-resolution scheme is that it is bounded,which means that no unphysical oscillation occurs during the com-

62 S. Sá et al. / Journal of Memb

fer resistance between the bulk gas and the catalyst surface.

rSR =kSRK∗

CH3OH(1) (pCH3OH/p1/2H2

)(1 − p3H2

pCO2 /KeSRpCH3OHp

(1 + K∗CH3OH(1) (pCH3OH/p1/2

H2) + K∗

HCOO(1) pCO2 p1/2H2

+ K∗OH(1) (pH2O

rWGS =kWGSK∗

OH(1) (pCOpH2O/p1/2H2

)(1 − pH2 pCO2 /KeWGSp

((1 + K∗CH3OH(1) (pCH3OH/p1/2

H2) + K∗

HCOO(1) pCO2 p1/2H2

+ K∗OH(1) (p

rMD =kMDK∗

CH3OH(2) (pCH3OH/p1/2H2

)(1 − p2H2

pCO/KeMDpCH3OH)CT

S2CTS2

(1 + K∗CH3OH(2) (pCH3OH/p1/2

H2) + K∗

OH(2) (pH2O/p1/2H2

))(1 + K1/2

H(2a) p

where kj and Kej

are the reaction rate and equilibrium constants forreaction j, respectively; Ki is the adsorption coefficient for surfacespecies i, CT

S1 and CTS2 are the total catalyst surface concentration

of sites 1 and 2, respectively, CTS1a and CT

S2a are the total catalystsurface concentration of sites 1a and 2a, respectively, and SA is thesurface area of the catalyst.

.2. Permeate side

Partial mass balance

ddz

(uPpPi ) − 2�rM

AP�TNi = 0 (13)

Total mass balance

PP duP

dz− 2�rM

AP�T

∑i

Ni = 0 (14)

Boundary conditions

z = 0 : pPi = pP,in and uP = uP,in (15)

where superscript P stands for permeate side and AP is the cross-sectional area of the permeate chamber

.3. Membrane permeation equation

The mass transfer of each component through the membrane isssumed to be described by its local driving force and a global massransfer coefficient, according to the following equation:

i(z) = Li{(pRi (z))

n − (pPi (z))

n} (16)

here L is a permeance coefficient and n is 1/2 for the palla-ium membrane (Sievert’s law) and 1 for the CMS membrane. Thelm transport resistance supposed at the interface gas/membrane

s considered negligible and the permeability coefficients aressumed constant.

.4. Dimensionless equations

The model variables were made dimensionless with respecto the retentate feed (uR,in), to hydrogen (LH2 and MH2 ) and tohe reactor length, . Changing for dimensionless variables andntroducing suitable dimensionless parameters, Eqs. (4)–(8) and13)–(16) become as follows:

ddx

(uR∗pR∗

i ) + 1Pe

ddx

(PR∗ d

dx

(pR∗

i

PR∗

))− T∗N∗

i + DaT∗R∗i = 0

(17)

∑ ∑

ddx

(uR∗PR∗

) − T∗

i

N∗i + DaT∗

i

R∗i = 0 (18)

dPR∗

dx= ˛�uR∗ + ˇ

�∗gas

T∗ |uR∗ |uR∗(19)

cience 339 (2009) 160–170

TS1CT

S1aSA

2))(1 + K1/2

H(1a) p1/2H2

)(10)

2O)CT2

S1 SA

1/2H2

))(1 + K1/2

H(1a) p1/2H2

))2

(11)

(12)

x = 0 :1Pe

ddx

(pR∗

i

PR∗

)= uR,in∗ pR∗

i− pR,in∗

i

PR∗ and uR∗ = uR,in∗(20)

x = 1 :d

dx

(pR∗

i

PR∗

)= 0 and PR∗ = PR,out∗ (21)

ddx

(uP∗pP∗

i ) − �T∗N∗i = 0 (22)

PP∗ duP∗

dx− �T∗

∑i

N∗i = 0 (23)

x = 0 : pP∗i = pP,in∗

and uP∗ = uP,in∗(24)

N∗i (x) = L∗

i [(pR∗i (x))

n − (pP∗i (x))

n] (25)

where ˛ = 150(1 − ε)2uref/ε2d2pPref, ˇ = 1.75(1 − ε)Mrefu

2ref/

εdp�Tref, p∗i

= Pi/Pref, P* = Pi/Pref, u* = u/uref, R∗i

= Ri/kSR,refCTS1CT

S1aSA,L∗

i= Li/Lref, x = z/, Da = mcat�TrefkSR,refC

TS1CT

S1aSA/εurefARPref,

� = εAR/AP, = AM�TrefPn−1ref Lref/εurefA

R, Pe = uref/Dax, Mref is thereference molar mass, Lref is the reference permeance coefficient ofthe membrane, x is the dimensionless axial coordinate of the reac-tor, Pe is the Peclet number for mass transfer, Da is the Damköllernumber, is the contact time (ratio between permeate flow ofreference component when fed pure for null permeate pressureand the total molar feed flow), kSR,ref is the rate constant for thesteam reforming reaction at the reference temperature, Pref is thereference pressure (set to 100 kPa), Tref is the reference pressure(set to 298 K), uref is the reference velocity, AM is the permeationarea of the membrane and is the reactor’s length.

2.5. Numerical solution strategy

To simulate the steam reforming membrane reactor, it is nec-essary to solve Eqs. (17)–(19), (22) and (23) with the respectiveboundary conditions.

In order to overcome numerical instability problems, it was usedthe same strategy adopted already [27] for solving the equations:a time derivative term was added to their right-hand side, trans-forming this problem into a pseudo-transient one. The resultantpartial differential equations were spatially discretized using thefinite volumes method [28], being the partial pressure of compo-nent i determined with high-resolution schemes (WACEB) [29]. The

puted solution. The time advancement was accomplished by LSODA[30], a numerical package developed at the Lawrence LivermoreNational Laboratory. The solution was considered to be in steadystate when the time derivative of each dependent variable and foreach of the spatial coordinate was smaller than a pre-defined value.

S. Sá et al. / Journal of Membrane Science 339 (2009) 160–170 163

Fi

3

ttemacwmBF

bistsagTtwipp

Table 1Parameters for the simulation.

Da ∈ [0.01–100] ∈ [1–4]PR,out ∈ [100–300] kPa PP ∈ [1–80] kPaT (K) ∈ [473–573] S/C (H2O/CH3OH) ∈ [1–4]Lref(Pd) = 1.57 × 10−7 kmol m−2 s−1 kPa−0.5 Lref(CMS) = 3.53 × 10−7

kmol m−2 s−1 kPa−1

LPd∗ = 1 LCMS∗ = 1

ig. 2. Experimental and simulated data for the: (A) CMS membrane reactor (exper-mental data from [10]); (B) Pd membrane reactor (experimental data from [31]).

. Discussion

In order to compare the performance of the membrane reac-ors equipped with Pd and CMS membranes, a systematic study onhe effect of the most important operating variables and param-ters was made. Such comparison focused on the analysis of theethanol conversion, H2/CO reaction selectivity, CO concentration

t the permeate side and hydrogen recovery. Ideally, methanolonversion and hydrogen recovery should be as high as possible,hile the CO concentration should be below 10 ppm. The developedathematical model was validated using the experimental data by

asile et al. [31] and by Zhang et al. [10]. As it can be realized fromig. 2, the model agrees well with the experimental data.

The sweep gas used was water vapour and the sweep ratio (ratioetween the inlet permeate velocity and the inlet retentate veloc-

ty) was set to 1 [32]. Compared to nitrogen, the advantage of usingteam as sweep gas is mainly related to the simplicity of its separa-ion from the hydrogen stream by condensation. Moreover, recenttudies from Yu et al. [24,33] reported higher hydrogen productionnd recovery when compared to the use of nitrogen as a sweepas. The operating parameters for the simulation are presented inable 1. The steam to carbon ratio was varied from 1 to 4 according

o what is commonly used in the literature [34]. The temperatureas in the range of 473–573 K [32] and the reaction pressure var-

ed from 1 to 3 bar [18]. In order to obtain high driving forces, theermeate pressure was varied from 0.01 to 0.8 bar. The hydrogenermeance was taken from Harale et al. [24] for the CMS membrane,

H2 H2

LCMS∗H2O = 0.313 LCMS∗

CH3OH = 0.001

LCMS∗CO2

= 0.080 LCMS∗CO = 0.015

and from Basile et al. [35] for the Pd membrane. The permeance datawere used to estimate the contact time values, using feed flow ratesand membrane areas commonly used in the literature [10,34]. TheDa number interval was estimated using the kinetic data from Pep-pley et al. [13] and the commonly used catalyst mass and feed flowrates [10,34].

3.1. Methanol conversion

Palladium and palladium–silver membranes are used in mem-brane reactors to separate hydrogen from a gas mixture. Due totheir unique characteristics of being permeable only to this gas, theyallow the formation of a pure hydrogen stream that can be used tofeed fuel cells. However, due to their relatively low permeability, thereactor must operate with high membrane areas, to recover mostof the hydrogen produced. In order to obtain the desirable recover-ies of hydrogen at a lower membrane area, CMS membranes can beused instead. These membranes present relatively high permeabil-ities, but they have the drawback to be permeable to other species,resulting in a not pure hydrogen permeate stream.

The permeation behaviour of the two membranes can have asignificant effect in the membrane reactor performance. To evaluatesuch influence, it was simulated the methanol conversion (XCH3OH,Eq. (26)) as a function of the Damköller number and temperature,for both CMS and Pd membrane reactors—Fig. 3.

XCH3OH =FR,in∗

CH3OH − FR,in∗CH3OH − FP,in∗

CH3OH

FR,in∗CH3OH

(26)

where Fi is the dimensionless flow rate: F∗i

= p∗iu∗/T∗.

The methanol conversion pattern achieved in both membranereactors is very similar, which could indicate that the permeationbehaviour of the two membranes has no effect in the reactor’s per-formance in what concerns the consumption of methanol. In Fig. 4it can be seen the methanol conversion of both reactors as a func-tion of the Damköller number for a given temperature; it is nowclear that both reactors perform very closely.

Although the differences between the conversions achieved byboth MR are almost unnoticeable, it is important to know what aretheir causes and in which conditions are they more or less impor-tant. The methanol steam reforming and secondary reactions (MDand WGS), are equilibrium limited reactions. For of these reactions,the conversion is determined by the reaction rate and by the con-centration of reactants (which should be as high as possible) andthe concentration of products (which should be maintained as lowas possible). In opposite to what occurs in the Pd-MR, water per-meates through the CMS membrane, diminishing its concentrationat the reaction side. At low to medium Damköller numbers, thishas a negligible impact, because the needs of water for the reac-

tion are relatively low. Conversely, at medium to high Damköllernumbers, the reaction is faster, consuming more water. The per-meation of this species through the membrane should deplete itfrom the reaction side faster than for the non-permeable membrane(consumption only by reaction), thus decreasing the conversion.

164 S. Sá et al. / Journal of Membrane Science 339 (2009) 160–170

F er fora

Hetpfltsr

raSmitdots

at

FmP

ig. 3. Methanol conversion as a function of the temperature and Damköller numbnd PP∗ = 0.1.

owever, the simulated results show a different pattern. This appar-nt contradiction is related to the change in the residence time ofhe reaction mixture in the reaction zone. More specifically, theermeation of all species in the CMS-MR lowers the total retentateow rate, increasing the residence time of the reaction mixture,hus enhancing methanol conversion. Corroborating what has beenaid, Fig. 5 shows the difference between the gas velocities at theetentate side for both membrane reactors.

To improve methanol conversion, the permeate pressure can beeduced in order to increase the driving force for hydrogen perme-tion. The removal of hydrogen from the reaction side shifts theR and the MD reactions toward the products, resulting in higherethanol conversion. However, it should be taken into account that

n a CMS-MR the water flux through the membrane can occur fromhe retentate to the permeate side or vice versa, according to theriving force. To determine if the reaction conversion is positivelyr negatively affected by water permeation from the permeate to

he retentate side, the influence of the total permeate pressure wastudied—Fig. 6(A).

It is clear from Fig. 6 that for an intermediate relative perme-te pressure region, the CMS-MR presents better performance thanhe Pd-MR, concerning methanol conversion. In fact, the permeate

ig. 4. Methanol conversion as a function of the Damköller number for a palladiumembrane reactor and a CMS membrane reactor S/C = 1.5, T = 473 K, = 2, PR,out∗ = 1,

P∗ = 0.1.

: (A) CMS membrane reactor. (B) Pd membrane reactor. S/C = 1.5, = 2, PR,out∗ = 1

pressure in the CMS-MR does not need to be as low as the one inthe Pd-MR to achieve the same conversion. For the same reason,the sweep gas flow rate does not have to be as high as the onein the Pd-MR. Outside this region, Pd-MR presents higher conver-sions. When a CMS membrane is used, the effect of water depletionby permeation must be considered, in opposite to what happensin a Pd membrane. At very low relative permeate pressures, belowPP∗ ≈ 0.02 in the present case, water is depleted in the reactionside due to its high permeation rate (high driving force), lower-ing subsequently the methanol conversion relatively to the oneachieved by the Pd-MR. Above PP∗ ≈ 0.02, the conversion of theCMS-MR becomes higher than the one achieved by the Pd-MR. AsPP∗

increases, the loss of water by permeation decreases also, beingno longer depleted from the reaction side. Additionally, the per-meation of water from the retentate side increases the residencetime of the reaction mixture, as discussed before, enhancing themethanol conversion. Finally, above PP∗ ≈ 0.44, the water partial

pressure at the retentate side is lower than the one at the per-meate side, which causes a permeation flux from the permeate tothe retentate side. This is shown in Fig. 6(B) where the water par-tial pressure difference between retentate and permeate is givenalong the reactor’s length. The water inlet from the permeate side

Fig. 5. Relative gas velocity at the retentate side along the reactor’s length pressurefor a palladium membrane reactor and a CMS membrane reactor. S/C = 1.5, T = 473 K, = 2, Da = 40, PR,out∗ = 1, PP∗ = 0.1.

S. Sá et al. / Journal of Membrane Science 339 (2009) 160–170 165

Fig. 6. (A) Methanol conversion as a function of the total relative permeate pressurefor a palladium membrane reactor and a CMS membrane reactor. (B) Differenceb

s

imHursmt

ab(Fhpp

i0C

�

wi

etween the water partial pressure at the reaction side (pR∗H2O) and the permeate

ide (pP∗H2O) along the reactor’s length. S/C = 1.5, T = 473 K, 2, Da = 40 and PR,out∗ = 1.

ncreases its concentration at the reaction side, subsequently aug-enting the total retentate flow rate. Although the increase of the2O/CH3OH ratio promotes the reaction to move toward the prod-cts, thus increasing the conversion, the increase of the total flowate in the reaction zone decreases the amount of methanol con-umed due to a decrease in the residence time. Therefore, the CMSembrane reactor is penalized relatively to the Pd membrane reac-

or for this region of permeate pressures.It is also important to analyse how the hydrogen driving force is

ffected by the pressure. The driving force for CMS and the Pd mem-ranes is not the same: when Pd is used, the Sievert’s law is appliedn = 0.5 in Eq. (25)); on the other hand, when CMS is used n = 1.ig. 7 shows the difference between the CMS-MR and the Pd-MRydrogen driving force, (�DF, Eq. (27)) as a function of the hydrogenartial pressure at the permeate side, for various hydrogen retentateressures. For pR∗

H2> 1, the hydrogen driving force in the CMS-MR

s always higher than in the Pd-MR. On the other hand, for pR∗H2

<

.25 the driving force in the Pd-MR is always higher than in theMS-MR.

0.5 0.5

DF = (pR

H2− pP

H2) − ((pR

H2) − (pP

H2) ) (27)

According to Fig. 7, the CMS-MR presents a higher driving forcehen the amount of hydrogen at the retentate side is higher, which

ndicates that CMS membranes are more adequate to recover higher

Fig. 7. Difference between the CMS-MR and the Pd-MR hydrogen driving force, as afunction of the hydrogen partial pressure ate the permeate side, for various hydrogenretentate pressures.

hydrogen amounts and Pd membranes are more suitable for lowerhydrogen concentrations.

3.2. H2/CO selectivity

Besides the conversion of methanol, it is important to analyse thereaction selectivity towards the desired product—hydrogen. For thisreason, the SR reaction should be favoured relatively to the MD reac-tion, in order to reduce the formation of CO. The amount of hydrogenproduced relatively to the amount of CO can be characterized by theH2/CO selectivity [36], given by Eq. (28):

SH2/CO =FR,out∗

H2+ FP,out∗

H2

FR,out∗CO + FP,out∗

CO

(28)

The influence of the Damköller number and the contact time inthe H2/CO selectivity is presented in Fig. 8. It is important to clar-ify that the contact time represents the ratio between a referencepermeation flow and the feed flow. Knowing that the permeance ofthe reference component (hydrogen) for CMS and Pd membranesis very different, the permeation flux is also different. As so, for agiven feed flow rate, both membranes can present the same con-tact time value as long as the product LrefAM is the same for both ofthem.

As it can be seen in Fig. 8, the H2/CO selectivity increaseswith the Da number until a maximum value is reached. After-wards, for high Da numbers, H2/CO selectivity decreases. Whenthe reaction rates are relatively low, Da = [0.01–1], the consump-tion of the reactants is also low, thus the water partial pressure atthe retentate side is high. As the Da number increases, this excessof steam shifts the SR and the WGS reactions towards the prod-ucts, producing hydrogen and consuming carbon monoxide, thusincreasing the selectivity. At high Da numbers, the reaction ratesare also high and the gas mixture composition at the reaction sideis altered due to the high methanol conversion. In particular, theconcentration of water diminishes and the concentration of carbondioxide increases. This combination shifts the reverse water gasshift (RWGS) reaction towards the products, consuming hydrogen,producing carbon monoxide and decreasing the reaction selectivity.

The influence of the contact time on the membrane reactor per-formance, on the other hand, is dependent of the membrane type.The higher the value of the higher is the fraction of the feedflow that permeates, that is, the stage cut. Concerning the Pd-MR,an increase in the contact time value results in higher hydrogen

166 S. Sá et al. / Journal of Membrane Science 339 (2009) 160–170

F or: (AP

porsofhStRsro

cvhlpttwTt

FbP

ig. 8. H2/CO selectivity as a function of contact time and the Damköller number fP∗ = 0.1.

ermeation flux compared to the total feed flow rate. The removalf hydrogen from the retentate side shifts the SR and the WGSeactions towards the products, producing more hydrogen and con-uming carbon monoxide. Conversely, in the CMS-MR, an increasef the contact time value results in higher relative permeation fluxesor all species. The permeation of hydrogen and carbon dioxideas a positive influence in the H2/CO selectivity, promoting theR and the WGS reaction to move towards the products. However,he permeation of water has the opposite effect: it promotes theWGS reaction, more carbon monoxide is produced, and the H2/COelectivity decreases. In addition, less water is available for the SReaction and less hydrogen is produced. This effect overrides thethers and the H2/CO selectivity decreases.

Comparing the performance of both membranes in what con-erns the H2/CO selectivity, the CMS-MR presents slightly higheralues at low to medium Da numbers, while the Pd-MR showsigher values at medium to high Da numbers—Fig. 9. Due to the

ower retentate flow rate of the CMS-MR, mostly due to the waterermeation, the extent of all reactions is higher at first. However,

he low concentration of water at high Da numbers will promotehe RWGS reaction over the others. In the Pd membrane reactor,ater does not permeate, so the RWGS is not so highly enhanced.

herefore, its concentration at the reaction side is then kept higherhan in the CMS-MR, resulting in higher H2/CO selectivity.

ig. 9. H2/CO selectivity as a function of Damköller number for a palladium mem-rane reactor and a CMS membrane reactor. S/C = 1.5, T = 473 K, = 2, PR,out∗ = 1,P∗ = 0.1.

) CMS membrane reactor; (B) Pd membrane reactor. S/C = 1.5, T = 473 K, PR,out∗ = 1,

3.3. Hydrogen recovery

The amount of hydrogen that is recovered at the permeate sideis an important factor to evaluate the performance of the reactor.Fig. 10 shows the influence of the contact time and the Damköllernumber in the hydrogen recovery, which is defined by (29):

RecH2 =FP∗

H2

FP∗H2

+ FR∗H2

(29)

As it can be seen, the pattern for both membrane reactors issomehow complex. An increase of the Damköller number has twodifferent effects, depending on the contact time value. Specifically,at low , the membrane reactor operates at low stage cut andthe relative hydrogen permeation flux is, therefore, low. With anincrease of the Da number, the amount of hydrogen produced ishigher, but due to low relative permeation flux, the hydrogen recov-ery at the permeate side decreases. This effect is more pronouncedin the Pd-MR than in the CMS-MR because the permeation of waterin the CMS-MR causes a decrease of its partial pressure and, subse-quently, an increase of the hydrogen partial pressure. On the otherhand, higher indicates a higher stage cut, meaning a higher per-meation flux relative to the retentate flow rate. When the hydrogengeneration increases due to the Da number, its partial pressure atthe retentate side also increases. Consequently, the hydrogen driv-ing force is higher and its recovery enhanced.

In what concerns the effect of the contact time, the major dif-ference in the performance of these membrane reactors occurs atlow Damköller numbers. While increasing in the Pd-MR seemsto have almost no effect, in the CMS-MR it strongly enhances thehydrogen recovery. According to what was discussed before, whenthe amount of hydrogen produced is low (low Da numbers) thePd-MR presents a higher driving force than the CMS-MR. Confirm-ing what has been said, Fig. 10 shows higher hydrogen recovery forthe Pd-MR than the CMS-MR at low Da and low . However, forlow Da and high , the membrane reactors perform very differ-ently. Beginning with the analysis on the Pd-MR, low Da numbersresult in low hydrogen production rate, thus low driving force. Inthis case, where hydrogen is the only permeating species, a changein the contact time has very little effect on the recovery. In fact, the

increase of the hydrogen recovery would only be noticeable at veryhigh contact time values. On the other hand, all species permeatein the CMS-MR; although the amount of hydrogen in the reactionside is low, its partial pressure increases with the permeation ofthe other species, mainly water, towards the permeate side. In fact,

S. Sá et al. / Journal of Membrane Science 339 (2009) 160–170 167

F er forP

th

3

aoasp

ratt

a

0pctsiaCtid

tFclaTst

alcft

products, producing carbon dioxide and hydrogen and consumingcarbon monoxide.

Fig. 13 shows the influence of both temperature and steam tocarbon ratio on the carbon monoxide concentration at the perme-

ig. 10. Hydrogen recovery as a function of contact time and the Damköller numbR,out∗ = 1, PP∗ = 0.1.

he decrease of water partial pressure leads to an increase of theydrogen partial pressure, resulting in a higher driving force.

.4. Carbon monoxide permeation

As mentioned before, carbon membranes, unlike Pd membranes,re permeable to carbon monoxide, a poison to the anode catalystf the fuel cells. In order to feed the permeate stream directly toPEMFC, the amount of CO must be lower than 10 ppm [14]. As

o, the effect of the various parameters on the amount of CO thatermeates through the membrane is of great importance.

Several authors have shown the advantages of increasing theeaction pressure in order to improve methanol conversion, as wells the hydrogen recovery, in a Pd-MR [18,34]. Indeed, an increase ofhe reaction pressure enhances the hydrogen driving force, shiftinghe reaction equilibrium towards the products. On the other hand,

ccording to the Le Chatelier principle, in reactions where∑

i

�i >

as steam reforming and methanol decomposition, the increase ofressure shifts the equilibrium towards the reactants and methanolonversion decreases. Fig. 11 shows the influence of the contactime and the total pressure in the conversion of methanol. It can beeen that the conversion in the Pd-MR is positively affected by thencrease of the pressure due to the higher hydrogen driving forcend by the increase of due to the higher stage cut. However, theMS-MR does not reveal the same behaviour. As there are two wayso consume water, namely, permeation and chemical reaction, theres a value of at which the methanol conversion starts to decreaseue to the depletion of water.

Despite the decrease in methanol conversion shown in Fig. 11,he hydrogen recovery was not penalized by water depletion. In fact,ig. 12(A) shows a small increase of the hydrogen recovery when theonversion starts to decrease. As the amount of hydrogen producedowers, its recovery rises, so the increase of pressure seems to havepositive effect in the CMS-MR. However, this is not entirely true.he CO permeation also increases with the pressure, inhibiting thetream to be fed directly to the PEMFC—Fig. 12(B). As so, unlike Pd,hese membranes are better suited for working at low pressures.

Carbon monoxide is formed by the endothermic reactions MD

nd RWGS. Thus, the extent of these reactions can be reduced byowering the reaction temperature. The increase of the steam toarbon feed ratio is another way of reducing the carbon monoxideormation. The excess of steam will promote the SR reaction towardhe products and less amount of methanol is decomposed to carbon

: (A) CMS membrane reactor. (B) Pd membrane reactor. S/C = 1.5, T = 473 K, Da = 40,

monoxide. In the same way, the WGS reaction is shifted toward the

Fig. 11. Methanol conversion as a function of contact time, at various retentate pres-sures, for: (A) CMS membrane reactor. (B) Pd membrane reactor. S/C = 1.5, T = 473 K,Da = 40 and PP∗ = 0.1.

168 S. Sá et al. / Journal of Membrane Science 339 (2009) 160–170

Fig. 12. (A) Hydrogen recovery as a function of contact time, at various retentatepressures for a CMS membrane reactor. (B) Permeate CO concentration as a functionof contact time, at various retentate pressures for a CMS membrane reactor. S/C = 1.5,T = 473 K, Da = 40 and PP∗ = 0.1.

Fig. 13. Carbon monoxide concentration at the permeate side as a function of thetemperature and the H2O/CH3OH feed ratio for a CMS membrane reactor. Da = 40, = 2, PR,out∗ = 1 and PP∗ = 0.1.

Fig. 14. Scheme of the simulated CMS/Pd membrane reactor.

ate side. Although the amount of CO decreases with higher steam tocarbon ratios and lower reaction temperatures, it is still remainingabove 10 ppm and, thus, too high to be fed into a PEMFC. Lower con-tact time values could be used to decrease the CO content, but thiswould also decrease the hydrogen recovery. In order to overcomethis difficulty, a new membrane reactor configuration was studiedas described in the next section.

3.5. Combination of Pd and CMS membranes

As discussed above, each membrane has some advantage overthe other. As so, an improved system would result from combin-ing in the same reactor a high permeation flux while keeping theCO at the permeation side at low concentrations. In order to findsuch a system, a new reactor configuration is proposed and simu-lated, combining a Pd membrane and a CMS membrane, as shownin Fig. 14.

The present simulated reactor comprises two membranes. Firstthe CMS membrane, less selective and less expensive with a higherpermeation flux; afterwards, the highly selective Pd membranewith lower permeation flux. A preliminary study was made in orderto determine the most adequate ratio of the CMS/Pd membranelength. It was concluded that the value of 1.2 was the most suitablefor a large range of the studied operating parameters, keeping theCO concentration at the permeate side bellow 10 ppm and a highhydrogen recovery.

The major disadvantage of the CMS membrane is the COpermeation. As shown in Fig. 15, the combination of the mem-branes overcomes this problem, allowing to produce a permeatestream with an amount of carbon monoxide under 10 ppm. Placingthe Pd membrane after the CMS membrane, avoids the perme-ation of CO where its partial pressure is higher—the end of thereformer.

Concerning the hydrogen permeation flux, Fig. 16 shows that thisnew reactor configuration allows a higher recovery of the hydrogenformed. As discussed before, the permeation of water lowers its par-tial pressure at the reaction side and increases the hydrogen partial

Fig. 15. Carbon monoxide concentration in the permeate side as a function of theDamköller number for a CMS/Pd membrane reactor. T = 473 K, = 2, PR,out∗ = 1 andPP∗ = 0.1.

S. Sá et al. / Journal of Membrane Science 339 (2009) 160–170 169

Fr

pfl

Dbpfa

4

shts

ssasTbiiChtpmi

tbtkItp

A

3p

Nomenclature

A area (m2)CT

S1 total catalyst surface concentration of site 1(mol m−2)

CTS1a total catalyst surface concentration of site 1a

(mol m−2)dp catalyst diameter (m)Da Damköller numberDax axial dispersion coefficient (m2 s−1)Fi dimensionless molar flow rate of species iki rate constant for reaction i (m2 s−1 mol−1)Ke

jequilibrium constant for reaction j

Ki adsorption coefficient for surface species ikSR,ref rate constant for the steam reforming reaction

(m2 s−1 mol−1) reactor’s length (m)Li permeance coefficient of species i

(kmol m−2 s−1 kPa−n)mcat mass of catalyst (kg)Mref reference molar mass (kg mol−1)Ni flux of the component i through the membrane

(mol s−1 m−2)Pe Peclet number for mass transferpi partial pressure of component i (kPa)Pref reference pressure (kPa)P total pressure (kPa)� gas constant (kPa m3 mol−1 K−1)rj rate of reaction j (mol s−1 m−2)rR radius of the reactor (m)Ri rate of consumption or formation of species i

(mol s−1 kg cat−1)SA surface area of the catalyst (m2 kg−1)T absolute temperature (K)u interstitial velocity (m s−1)uref reference velocity (m s−1)x relative length of the reactorz length of the reactor (m)

Greek lettersε void fraction of the catalyst bed contact time� gas viscosity (kg m−1 s−1)� dimensionless time variable� gas density (kg m−3)�cat catalyst density (kg cat m−3)�ij stoichiometric coefficient for species i in the reac-

tion j

SuperscriptsM membraneP permeateR retentate

SubscriptsMD methanol decompositionRWGS reverse water gas shift

ig. 16. Hydrogen recovery as a function of contact time for a CMS/Pd membraneeactor. S/C = 1.5, T = 473 K, Da = 40, PR,out∗ = 1 and PP∗ = 0.1.

ressure. The hydrogen driving force is higher and its permeationux is increased.

In comparison to the CMS-MR, the hydrogen recovery at lowamköller numbers is higher due to the presence of the Pd mem-rane at the end of the reactor. As discussed before, when theroduction of hydrogen is low, the Pd-MR shows a higher driving

orce compared to the CMS-MR. In this way, the hydrogen perme-tion flux increases and the hydrogen recovery is enhanced.

. Conclusions

Two types of membranes were studied to work in a methanolteam reforming membrane reactor. CMS membranes presentigher permeabilities, higher hydrogen recovery, and lower selec-ivities. Pd membranes are more expensive but exhibit much higherelectivity towards hydrogen.

This study was focused on the analysis of the methanol conver-ion, H2/CO reaction selectivity, CO concentration at the permeateide and hydrogen recovery. The effect of several parameters wasnalysed. More specifically, it was concluded that methanol conver-ion is enhanced by the Da number and the reaction temperature.he H2/CO reaction selectivity increases with for the Pd-MRut has the opposite effect for the CMS-MR. Hydrogen recovery

ncreases with and Da numbers for both MR, although the effects almost unnoticeable for the Pd-MR and for low Da numbers. TheMS-MR presents higher hydrogen recovery than the Pd-MR at highydrogen concentrations, and the Pd-MR proved to be more advan-ageous for lower hydrogen production rates. Finally, the Pd-MRerformance is enhanced by high retentate pressures and low per-eate pressures, while the CMS-MR performance is enhanced for

ntermediate values.A combined CMS + Pd membrane reactor was studied in order

o explore the advantages of both membrane systems. The com-ination of these membranes revealed some advantages towardshe CMS-MR; specifically, higher hydrogen recovery is achieved,eeping the CO concentration at the permeate side below 10 ppm.n comparison to the Pd-MR, this membrane combination allowshe use of smaller membranes and higher feed flow rates, withoutrejudice of the membrane reactor performance.

cknowledgments

The work of Sandra Sá was supported by FCT, grant SFRH/BD/0385/2006. The research was also supported by funds from FCTrojects PTDC/EQU-EQU/71617/2006 and POCI/ENR/59323/2004.

SR steam reformingWGS water gas shift

References

[1] G. Cacciola, V. Antonucci, S. Freni, Technology up date and new strategies onfuel cells, J. Power Sources 100 (2001) 67–79.

1 rane S

[

[

[

[

[

[

[

[

[

[

[

[

[

[

[

[[

[

[

[

[

[

[

[

70 S. Sá et al. / Journal of Memb

[2] J.M. King, M.J. O’Day, Applying fuel cell experience to sustainable power prod-ucts, J. Power Sources 86 (2000) 16–22.

[3] D. Ramirez, L.F. Beites, F. Blazquez, J.C. Ballesteros, Distributed generationsystem with PEM fuel cell for electrical power quality improvement, Int. J.Hydrogen Energy 33 (2008) 4433–4443.

[4] C. Stone, A.E. Morrison, From curiosity to “power to change the world”, SolidState Ionics 152–153 (2002) 1–13.

[5] A.S. Damle, Hydrogen production by reforming of liquid hydrocarbons n amembrane reactor for portable power generation–model simulations, J. PowerSources 180 (2008) 516–529.

[6] D.G. Löffler, K. Taylor, D. Mason, A light hydrocarbon fuel processor producinghigh-purity hydrogen, J. Power Sources 117 (2003) 84–91.

[7] T.L. Reitz, S. Ahmed, M. Krumpelt, R. Kumar, H.H. Kung, Characterization ofCuOrZnO under oxidizing conditions for the oxidative methanol reformingreaction, J. Mol. Catal. A: Chem. 162 (2000) 275–285.

[8] J.C. Telotte, J. Kern, S. Palanki, Miniaturized methanol reformer for fuel cellpowered mobile applications, Int. J. Chem. Reactor Eng. 6 (2008).

[9] A. Basile, A. Parmaliana, S. Tosti, A. Iulianelli, F. Gallucci, C. Espro, J. Spooren,Hydrogen production by methanol steam reforming carried out in membranereactor on Cu/Zn/Mg-based catalyst, Catal. Today 137 (2008) 17–22.

10] X. Zhang, H. Hu, Y. Zhu, S. Zhu, Methanol steam reforming to hydrogen in acarbon membrane reactor system, Ind. Eng. Chem. Res. 45 (2006) 7997–8001.

11] D.R. Palo, R.A. Dagle, J.D. Holladay, Methanol steam reforming for hydrogenproduction, Chem. Rev. 107 (2007) 3992–4021.

12] B.A. Peppley, J.C. Amphlett, L.M. Kearns, R.F. Mann, Methanol steam reformingon Cu/ZnO/Al2O3. Part 1: the reaction network, Appl. Catal., A 179 (1999) 21–29.

13] B.A. Peppley, J.C. Amphlett, L.M. Kearns, R.F. Mann, Methanol steam reformingon Cu/ZnO/Al2O3 catalysts. Part 2. A comprehensive kinetic model, Appl. Catal.,A 179 (1999) 31–49.

14] H.P. Dhar, L.G. Christner, A.K. Kush, Nature of CO adsorption during H2 oxidationin relation to modeling for CO poisoning of a fuel cell anode, J. Electrochem. Soc.134 (1987) 3021–3026.

15] F. Gallucci, L. Paturzo, A. Basile, Hydrogen recovery from methanol steamreforming in a dense membrane reactor: simulation study, Ind. Eng. Chem. Res.43 (2004) 2420–2432.

16] A.N. Matzakos, S.L. Wellington, T. Mikus, J.M. Ward, Integrated flamelessdistributed combustion/steam reforming membrane reactor for hydrogen pro-duction and use thereof in zero emissions hybrid power system, US patent6,821,501 (2004).

17] C.-H. Fu, J.C.S. Wu, Mathematical simulation of hydrogen production viamethanol steam reforming using double-jacketed membrane reactor, Int. J.Hydrogen Energy 32 (2007) 4830–4839.

18] A. Iulianelli, T. Longo, A. Basile, Methanol steam reforming in a dense Pd–Agmembrane reactor: the pressure and WHSV effects on CO-free H2 production,J. Membr. Sci. 323 (2008) 235–240.

[

[

[

cience 339 (2009) 160–170

19] F. Gallucci, A. Basile, S. Tosti, A. Iulianelli, E. Drioli, Methanol and ethanolsteam reforming in membrane reactors: an experimental study, Int. J. HydrogenEnergy 32 (2007) 1201–1210.

20] B.K.R. Nair, M.P. Harold, Hydrogen generation in a Pd membrane fuel proces-sor: productivity effects during methanol steam reforming, Chem. Eng. Sci. 61(2006) 6616–6636.

21] L. Shao, B.T. Low, T.-S. Chung, A.R. Greenberg, Polymeric membranes for thehydrogen economy: contemporary approaches and prospects for the future, J.Membr. Sci. 327 (2009) 18–31.

22] A.F. Ismail, L.I.B. David, A review on the latest development of carbon mem-branes for gas separation, J. Membr. Sci. 193 (2001) 1–18.

23] G.A. Sznejer, I. Efremenko, M. Sheintuch, Carbon membranes for high temper-ature gas separations: experiment and theory, AIChE J. 50 (2004).

24] A. Harale, H.T. Hwang, P.K.T. Liu, M. Sahimi, T.T. Tsotsis, Experimental studies of ahybrid adsorbent-membrane reactor (HAMR) system for hydrogen production,Chem. Eng. Sci. 62 (2007) 4126–4137.

25] S. Ergun, Fluid flow through packed columns, Chem. Eng. Prog. 48 (1952) 89–94.26] P.V. Danckwerts, Continuous flows systems—distribution of residence times,

Chem. Eng. Sci. 2 (1953) 1.27] J.M. Sousa, A. Mendes, Simulation study of a dense polymeric catalytic mem-

brane reactor with plug–flow pattern, Chem. Eng. J. 95 (2003) 67–81.28] P. Cruz, J.C. Santos, F.D. Magalhães, A. Mendes, Simulation of separation pro-

cesses using finite volume method, Comput. Chem. Eng. 30 (2005) 83–98.29] B. Song, G.R. Liu, K.Y. Lam, R.S. Amano, On a higher-order bounded discretization

scheme, Int. J. Num. Methods Fluids 32 (2000) 881–897.30] L. Petzold, Automatic selection of methods for solving stiff and nonstiff sys-

tems of ordinary differential equations, Siam. J. Sci. Stat. Comput. 4 (1983)136–148.

31] A. Basile, G.F. Tereschenko, N.V. Orekhova, M.M. Ermilova, F. Gallucci, A.Iulianelli, An experimental investigation on methanol steam reforming withoxygen addition in a flat Pd–Ag membrane reactor, Int. J. Hydrogen Energy 31(2006) 1615–1622.

32] F. Gallucci, A. Basile, Pd–Ag membrane reactor for steam reforming reac-tions: a comparison between different fuels, Int. J. Hydrogen Energy 33 (2008)1671–1687.

33] W. Yu, T. Ohmori, S. Kataoka, T. Yamamoto, A. Endo, M. Nakaiwa, N. Itoh, Acomparative simulation study of methane steam reforming in a porous ceramicmembrane reactor using nitrogen and steam as sweep gases, Int. J. HydrogenEnergy 33 (2008) 685–692.

34] F. Gallucci, A. Basile, Co-current and counter-current modes for methanol steamreforming membrane reactor, Int. J. Hydrogen Energy 31 (2006) 2243–2249.

35] A. Basile, F. Gallucci, L. Paturzo, A dense Pd/Ag membrane reactor for methanolsteam reforming: experimental study, Catal. Today 104 (2005) 244–250.

36] H.S. Fogler, Elements of Chemical Reaction Engineering, fourth ed., PrenticeHall, Upper Saddle River, NJ, 2005.