membranes

Article
Integration of Methane Steam Reforming and Water
Gas Shift Reaction in a Pd/Au/Pd-Based Catalytic
Membrane Reactor for Process Intensification
Bernardo Castro-Dominguez *, Ivan P. Mardilovich, Liang-Chih Ma, Rui Ma, Anthony G. Dixon,
Nikolaos K. Kazantzis and Yi Hua Ma
Center of Inorganic Membrane Studies, Department of Chemical Engineering, Worcester Polytechnic Institute,
100 Institute Road, Worcester, MA 01609, USA; ivanpm@wpi.edu (I.P.M.); lma@wpi.edu (L.-C.M.);
rma2@wpi.edu (R.M.); agdixon@wpi.edu (A.G.D.); nikolas@wpi.edu (N.K.K.); yhma@wpi.edu (Y.H.M.)
* Correspondence: bcastrodominguez@wpi.edu; Tel.: +1-508-8315666

Academic Editor: Peter Czermak

Received: 23 July 2016; Accepted: 9 September 2016; Published: 19 September 2016

Abstract: Palladium-based catalytic membrane reactors (CMRs) effectively remove H2 to induce

higher conversions in methane steam reforming (MSR) and water-gas-shift reactions (WGS). Within
such a context, this work evaluates the technical performance of a novel CMR, which utilizes two
catalysts in series, rather than one. In the process system under consideration, the first catalyst,
confined within the shell side of the reactor, reforms methane with water yielding H2 , CO and
CO2 . After reforming is completed, a second catalyst, positioned in series, reacts with CO and
water through the WGS reaction yielding pure H2 O, CO2 and H2 . A tubular composite asymmetric
Pd/Au/Pd membrane is situated throughout the reactor to continuously remove the produced
H2 and induce higher methane and CO conversions while yielding ultrapure H2 and compressed
CO2 ready for dehydration. Experimental results involving (i) a conventional packed bed reactor
packed (PBR) for MSR, (ii) a PBR with five layers of two catalysts in series and (iii) a CMR with
two layers of two catalysts in series are comparatively assessed and thoroughly characterized.
Furthermore, a comprehensive 2D computational fluid dynamics (CFD) model was developed to
explore further the features of the proposed configuration. The reaction was studied at different
process intensification-relevant conditions, such as space velocities, temperatures, pressures and
initial feed gas composition. Finally, it is demonstrated that the above CMR module, which was
operated for 600 h, displays quite high H2 permeance and purity, high CH4 conversion levels and
reduced CO yields.

Keywords: hydrogen production; catalytic membrane reactor; methane steam reforming;

water-gas-shift reaction; reaction coupling

1. Introduction
Methane steam reforming (MSR) is a well-established production method that currently generates
95% of hydrogen in the U.S. [1]. Conventionally, this reaction is carried out at high temperatures
(700–1000 ◦ C) and mild pressures (3–25 bar), which results in the production of CO and H2 with little
CO2 as a byproduct. Carbon monoxide is reacted downstream in two, high- and low-temperature,
water-gas-shift (WGS) reactors to further generate H2 and CO2 . Equations (1)–(3) [2] show both
chemical reactions where MSR is highly endothermic while WGS is exothermic. After the reaction,
the purification of H2 is traditionally carried out in a pressure swing adsorption (PSA) unit. Notice

Membranes 2016, 6, 44; doi:10.3390/membranes6030044 www.mdpi.com/journal/membranes

Membranes 2016, 6, 44 2 of 18

that in the conventional process, both MSR and WGS reactions are limited by their thermodynamic
equilibrium when carried out in customary packed bed reactors (PBRs).

MSR I CH4 + H2 O ↔ CO + 3H2 ∆H298K = 206 kJ/mol (1)

WGS CO + H2 O ↔ CO2 + H2 ∆H298K = −41 kJ/mol (2)

MSR II CH4 + 2H2 O ↔ CO2 + 4H2 ∆H298K = 165 kJ/mol (3)

The application of membrane technology is economically attractive since it helps to reduce the
number and size of equipment units needed, while simultaneously enhancing chemical conversions.
The higher efficiency of the so-called catalytic membrane reactors (CMRs) results from the constant
product removal from the reaction zone, through a selective membrane, altering the composition
of the system. This change in composition allows accomplishing higher conversions, and it is often
referred to as process intensification. Specifically, H2 -selective membranes can improve MSR and
WGS conversions while generating more hydrogen. Palladium-based membranes have been shown
to be the best candidates for implementation in these processes since they can isolate hydrogen from
gas mixtures in large quantities and at high purities while maintaining high stability and robustness.
Ma et al. [3,4] have demonstrated the performance of different pilot-scale Pd and Pd-alloy membranes
under industrial conditions. These membranes were capable of producing 1.16 kg/day of H2 with a
purity of 99.89% under actual coal-derived syngas at 450 ◦ C. Although a reduced H2 permeance was
displayed due to the presence of contaminants, the stability, robustness and physical integrity of the
membranes were successfully demonstrated.
In the case of CMR technology, the literature has shown membrane application up to a pilot-scale
magnitude [5], as shown in Table 1. Palladium membranes are capable of operating at temperatures
between 300 and 600 ◦ C, matching the temperatures of high-temperature WGS catalysts (310–450 ◦ C).
A low-temperature WGS unit is no longer needed, since high CO conversions can be achieved through
a single CMR unit. Furthermore, the effect of process intensification in MSR allows operating this
process at mild temperatures (Table 1) while maintaining high conversions, preventing coking and
reducing the CO yield. The experimental tests shown in the literature demonstrate the effect of process
intensification; nevertheless, the scale of operation is relevant for the industrial deployment of this
technology. Few pilot-scale tests have been published in this field, including the work presented by
Catalano et al. [6], where 5.6 m3 of H2 per day were produced through a WGS membrane reactor
at 440 ◦ C and 20 bar. Furthermore, Patrascu et al. [7] showed the performance of methane steam
reforming (MSR) in a large-scale CMR achieving a permeate flux of 1.6 NL/min at a temperature of
525 ◦ C and a pressure of 10 bar and utilizing a membrane with a surface area of 175 cm2 . Furthermore,
economically, CMR technology has shown success when integrated in power and hydrogen production
plants. Kazantzis et al. reported the specific market and regulatory conditions under which Pd-based
CMRs can be successfully integrated in the pertinent energy systems [8,9].
This work aims to implement the integration of one more processes into a single unit. Specifically,
the operation of a large-scale Pd-based CMR module is shown where both MSR and WGS reactions
are integrated in a single unit, in order to provide high CH4 yields with little or no CO. In the CMR,
the first catalyst (MSR) is confined on the shell side of the reactor, while the WGS catalyst is positioned
subsequently in series. A tubular Pd/Au/Pd membrane situated throughout the reactor continuously
removes the H2 to yield higher conversions. The higher shell pressure facilitates the acquisition of
clean pressurized CO2 and water, while ultrapure H2 is obtained in the permeate stream. Furthermore,
for comparison, the reaction is carried out in a conventional packed bed reactor for both configurations:
MSR and multistage MSR-WGS (five layers). Additionally, a two-dimensional computational fluid
dynamics (CFD) model was developed in order to further analyze the properties of this unit. Please
notice that the aim of this work is a proof-of-concept approach that explores the potential use of
catalysts packed in series and/or in parallel to enhance conventional processes.
Membranes 2016, 6, 44 3 of 18

Table 1. Palladium-based catalytic membrane reactors used for methane steam reforming (MSR) and
water gas shift (WGS) reactions.

Membrane Thickness Membrane Pressure Steam/Carbon Temperature

Reaction Reference
Type (µm) Area (cm2 ) (bar) Ratio (◦ C)
Pd/Ag 50 5.3 MSR 1.22 3–9 300–500 [10]
Pd/Ag/PSS * 10.3 10.7 MSR 1.36 3 400–550 [11]
Pd/PSS 20 60 MSR 9–20 3 400–500 [12]
Pd 4.5–22.5 6.3 MSR 1 3 500 [13]
Pd 4–5 175 MSR <10 2–4 525 [7]
Pd/Ag 200 46 MSR 1–4 2–5 300–400 [14]
Pd/Ag 1000 18.5 MSR 6–10 2.9 500 [15]
Pd–Ru/YSZ ** 5 13.28 MSR 35 3 580 [16]
Pd 20 25 WGS 3 1–5 400 [17]
Pd 1.4 21.5 WGS 2 3 350 [18]
Pd-Pd/Ag 7–10.3 50 WGS 1–12 1.1–2.6 350–450 [19]
Pd/Ag 25–40 15.7 WGS 1–4 7.4 200–300 [20]
Pd 10 200 WGS 7–20 2.5–3.5 420–440 [6]
Pd/Ag 2.2 6.8 WGS 26 5 400–450 [21]
Pd/Ag/alumina 4.5 17–35 WGS 2 NA 400 [22]
* PSS: porous stainless steel; ** YSZ: yttria-stabilized zirconia.

This work is structured as follows: Section 2 presents the methodological framework, as well as
an explicit description of the experimental procedure and CFD development. Section 3 encompasses
the results associated with the conventional reactors and the CMR’s performance characteristics along
with the pertinent simulation results accompanied by a thorough discussion related to the effect of
coupling two catalysts in one unit. Finally, some concluding remarks are offered in Section 4.

2. Methodology

2.1. Membrane Fabrication

A composite Pd/Au/Pd membrane was prepared on a 1.27-cm OD and 38.1-cm in length 316-L
porous stainless steel (PSS) support with media grade of 0.5 µm. The total permeable area of the
membrane was 152 cm2 . One end of the membrane was welded to a 316-L nonporous capped tube
while the other end was welded to a nonporous tube. The support showed an initial He flux of
200 L/min at a pressure difference of one bar. To synthesize the membrane, the support was first
covered with sol-gel and then calcined at 600 ◦ C for 12 h. After calcination, the supports were
graded following a previously-reported procedure with medium and fine pre-activated powder,
provided by Johnson Matthey (Royston, UK), based on a 2 wt % Pd-alumina catalyst without any
additional activation or treatment [23–25]. Notice that the grading procedure reduced the He leak
across the membrane by 3 orders of magnitude, as shown in Table 2. After grading, the surface of the
membrane was activated with SnCl2 -PdCl2 , and then, electroless plating was used to deposit a dense
Pd layer. A thin gold layer of 0.2 µm was deposited on top of the palladium surface via conventional
electroplating. Notice that gold has been shown to enhance the properties of Pd-based membranes,
such as permeance, stability and contaminant-recoverability [26], and therefore, was used in this
work. Finally, to provide active sides on this asymmetric membrane and further reduce the He leak
present, a pure Pd topmost layer was deposited. The thickness of the membrane was estimated by
gravimetric methods. The final composition and leak of the membrane was 6.9 Pd/0.2 Au/3.2 Pd
and <0.01 sccm/bar, respectively. The thicknesses and He leak at each step of the synthesis are shown
in Table 2.
Membranes 2016, 6, 44 4 of 18

Table 2. Characteristics of the membrane at different phases of the synthesis.

Membrane Synthesis Step Thickness/µm He Leak (sccm/bar) at 25 ◦ C

Initial support NA 197,360
Oxidation and calcination NA 91,830
Grading Pd(Al2 O3 ) 2.8 66
Membranes 2016, 6, 44 Pd layer 6.9 3 4 of 18
Au deposition 0.2 1.39
2.2. Reaction Tests and PdMembrane
layer (final)Characterization 3.17 NA

The H2 permeation tests and reactions were performed in the same WGS-CMR rig previously
2.2. Reaction Tests and Membrane Characterization
reported by Catalano et al. [6]. The composition of the feed was controlled by mass flow controllers
and premixed with steamtests
The H2 permeation generated in a preheater.
and reactions The wet in
were performed mixture
the samewasWGS-CMR
fed to the reactor, which
rig previously
contains the
reported membrane
by Catalano surrounded
et al. by the catalysts.
[6]. The composition of theThe
feedcatalysts used forbyMSR
was controlled massandflowWGS were a
controllers
nickel-based
and premixedcatalyst
with steam (HiFUEL R110,inAlfa-Aesar,
generated a preheater.Lancashire, UK) and
The wet mixture was anfed iron-chrome
to the reactor,catalyst
which
(HiFUEL the
contains W210, Alfa-Aesar),
membrane respectively;
surrounded by thethese catalysts
catalysts. Thewere crushed
catalysts usedandfor sieved
MSR and (16/+40
WGSmesh)were
abefore usage. The
nickel-based water(HiFUEL
catalyst of the retentate
R110, was condensed,
Alfa-Aesar, while theUK)
Lancashire, product
and an andiron-chrome
retentate flow rates
catalyst
were passed
(HiFUEL W210, through water absorbent
Alfa-Aesar), respectively; beds before
these the composition
catalysts were crushed wasand measured by massmesh)
sieved (16/+40 flow
meters usage.
before and a The gas water
chromatograph [6]. Three
of the retentate main experiments
was condensed, while the were conducted
product on the flow
and retentate CMR-rig,
rates
including:
were passed (i)through
MSR in watera conventional
absorbentpacked bed reactor
beds before (PBR); (ii)was
the composition multi-staged
measured (5 bylayers) MSR/WGS
mass flow meters
in a PBR;
and a gas and (iii) MSR/WGS
chromatograph [6].inThree
a CMR. mainIt isexperiments
important towere noteconducted
that no sweep gasCMR-rig,
on the was utilized in any
including:
of the
(i) MSR experiments presented
in a conventional in this
packed bedwork.
reactor (PBR); (ii) multi-staged (5 layers) MSR/WGS in a PBR;
For MSR/WGS
and (iii) the CMR reaction,in a CMR. a protective cage was
It is important to designed
note that innoorder
sweep to gas
prevent
was any potential
utilized damage
in any of the
of the membrane
experiments caused
presented by the
in this friction of the catalyst particles and the wall of the membrane, as
work.
previously
For thereported in the aliterature
CMR reaction, protective [22,27].
cage was Thedesigned
cage wasinmade
orderout of stainless
to prevent any steel grids,
potential and it
damage
consisted
of of two concentric
the membrane caused byconfines;
the frictionone ofsurrounded
the catalysttheparticles
membrane, andwhile the other
the wall of thewas used to
membrane,
hold
as the catalyst
previously in place,
reported in as
theshown in Figure
literature [22,27]. 1b.The
Notice
cagethat
wasthe surface
made out of
of the membrane
stainless was never
steel grids, and
inconsisted
it contact with the concentric
of two grid of theconfines;
cage. Theone catalyst section the
surrounded of the cage had while
membrane, a volume of 480was
the other cm3used
, andto it
was filled
hold with 120
the catalyst g of MSR
in place, catalyst
as shown and 1201b.
in Figure g of WGSthat
Notice catalyst for theofmembrane
the surface the membranereactor,
waswhile
neverthe in
PBR was
contact packed
with the gridin 5ofsections.
the cage.This membrane-catalyst
The catalyst section of thecage
cagesystem can be of
had a volume 480 cm3 ,inand
up-scaled order to
it was
develop
filled multi-tube
with 120 g of MSR CMRcatalyst
modules. and 120 g of WGS catalyst for the membrane reactor, while the PBR
was packed in 5 sections. This membrane-catalyst cage system can be up-scaled in order to develop
multi-tube CMR modules.

Figure 1.
Figure 1. Cage,
Cage,catalyst
catalystand
andmembrane
membrane configurations
configurations used
used in this
in this work:work: (a) assembled
(a) assembled protective
protective cage
cage without a membrane; (b) cross-sectional view of the cage and its schematic representation;
without a membrane; (b) cross-sectional view of the cage and its schematic representation; (c) different (c)
different components of the catalytic membrane reactor (CMR) module; (d) integrated cage-catalyst-
components of the catalytic membrane reactor (CMR) module; (d) integrated cage-catalyst-membrane
membrane

2.3. Mathematical Modeling Framework

A detailed modeling framework, helpful for the analysis of CMRs, has been used for the
interpretation of data [5], and accordingly, a 2D computational fluid dynamics (CFD) model was
Membranes 2016, 6, 44 5 of 18

2.3. Mathematical Modeling Framework

A detailed modeling framework, helpful for the analysis of CMRs, has been used for the
interpretation of data [5], and accordingly, a 2D computational fluid dynamics (CFD) model was
developed in COMSOL Multiphysics 4.3b (COMSOL, Inc., Burlington, VT, USA) in order to examine the
properties of the module and compare theoretical values with experimental results. A 2D configuration
Membranes 2016, 6, 44 5 of 18
of the model was chosen in order to include the non-ideal flow effects that occur in the reactor
due to the
against the axisymmetry of the reactors.
experimental values obtained The performance
in this work and, for of the
MSR, simulation
against thewas1Dcompared against
model presented
the experimental values obtained in this work and, for MSR, against the 1D
by Ayturk et al. [2], where a 99.4% accuracy was found when compared to other literature sources,model presented by
Ayturk et al. [2], where a 99.4% accuracy was found when compared to other
including conventional PBRs and CMRs. Figure 2 shows the configuration of the 2D model, where literature sources,
including
the conventional
MSR catalytic sectionPBRs and CMRs.
is located adjacentFigure 2 shows
to the the configuration
feed flow stream, followed of the
by 2Dthemodel, where
WGS section
the MSR catalytic section is located adjacent to the feed flow stream, followed
upstream; the membrane was specified to be at the bottom, taking advantage of the symmetrical by the WGS section
upstream; theofmembrane
configuration the reactorwas specified
module; to be at the
additionally, thebottom, takingmesh,
mathematical advantage of theinsymmetrical
displayed Figure 2, is
used to solve the momentum and continuity equations for the retentate side (EquationsFigure
configuration of the reactor module; additionally, the mathematical mesh, displayed in (4)–(6)) 2,
is used to solve the momentum and continuity equations for the
(COMSOL Multiphysics). The Darcy–Forchheimer law was applied in the present model retentate side (Equations (4)–(6))
(COMSOL Multiphysics).
accompanied by the followingThe Darcy–Forchheimer
assumptions: law was applied in the present model accompanied
by the following assumptions:
(1) Isothermal conditions;
(1) Steady
(2) state;conditions;
Isothermal
(3) Laminar flow;
(2) Steady state;
(3) Non-slip
(4) Laminar boundary
flow; condition for the fluid flow;
(5) Negligible effect of the
(4) Non-slip boundary condition protective cagefluid
for the on the flow pattern.
flow;
(5) Negligible effect of the protective cage on the flow pattern.

Figure 2. Configuration of the CMR simulation depicting the two catalyst sections, the location of the
membrane
Figure and the size and
2. Configuration geometry
of the of the used
CMR simulation mesh. the two catalyst sections, the location of the
depicting
membrane and the size and geometry of the used mesh.
The modified Navier–Stokes equation for a fixed bed porous medium is:
The modified Navier–Stokes equation for a fixed bed porous medium is:
   
ρ u µ 2u
ρ( u ·∇) u = ∇· − pI + μ (∇ u + (∇ u ) T
) −2u (∇· u ) I − (µk−1 + βF |u|)u + F (4)
(∇u (∇u)T) (∇ (μk −1
εp ((u ∙ ∇) ) = ∇ ∙ [−pI +
ε p ε p + − 3ε p ∙ u)I] − + βF |u|)u + F (4)
εp εp εp 3εp
where εp represents the system porosity and βF is the Forchheimer coefficient:
where εp represents the system porosity and βF is the Forchheimer coefficient:
∇·
∇ ∙ ((ρu) = 00
ρu) = (5)
(5)

∇· (−D
∇ ∙(− ∇ccii))+
Dii∇ +uu∙·∇
∇ccii =
=RRi i (6)
(6)
The reaction rates for MSR were specified as [2]:
3
k1 PCH4 PH2O − (PH2 PCO /K1 ) (7)
r1 = 2.5 × 2
PH2 DEN

k 2 PCO PH2O − (PH2 PCO2 /K 2 ) (8)

r2 = ×
PH2 DEN 2
Membranes 2016, 6, 44 6 of 18

The reaction rates for MSR were specified as [2]:

 
k1 PCH4 PH2O − P3H2 PCO /K1
r1 = 2.5 × (7)
PH2 DEN2

k2 P P − (PH2 PCO2 /K2 )

r2 = × CO H2O (8)
PH2 DEN2
 
2 4
k3 P CH4 PH2O − P H2 P CO /K 3
r3 = 3.5 × (9)
PH2 DEN2
where DEN is defined as:
KH2O PH2O
DEN = 1 + KCO PCO + KH2 PH2 + KCH4 PCH4 + (10)
PH2

Notice that r1 , r2 and r3 , correspond to the reactions specified in Equations (1)–(3), respectively.
Refer to the previous literature for the kinetic, adsorption and equilibrium constants [2]. Furthermore,
the reaction rate used for the WGS reactor model over Fe-Cr-based catalyst was specified as [28]:
 
−111
−0.36 −0.09 PH2 PCO2
r4 = 102.845 ·e Rg·T ·P1.0 P
CO CO2 H2 P · 1 − (11)
K PH2O PCO

where K is the equilibrium constant.

The reaction model is homogenous as the internal effectiveness factor was calculated to be 1.
The internal effectiveness factor is defined as the actual rate of reaction divided by the rate of reaction
that would occur if the entire internal surface of the catalytic particle would be exposed to the
external conditions.
Additionally, the flux across the membrane (Ni ) was based on Sieverts’ law as follows [2,29]:
q q 
Ni = PH2 PShell
H2 − PTube
H2 (12)

where PShell
H2 and PTube
H2 represent the hydrogen partial pressure at the retentate side and the permeate
side, respectively, and PH2 is the permeance of the membrane obtained experimentally. Furthermore,
the calculation of binary fluid diffusion coefficients (Dm ) was estimated according to standard
engineering procedures [30]:
s  
1 1 1
Dm = 0.0018583 T3 + (13)
MA MB Pσ2AB ϕD,AB

where Mi is the molecular weight of component i, P is the pressure of the system, σ2AB denotes the
parameters of the Lennard–Jones potential between molecules A and B and ϕD,AB represents the
collision integral for diffusion.
The longitudinal and transversal dispersion DL and DT are calculated using the equations
below [31]:
d·u
Pem = (14)
Dm
1/PeL = 1/ (τ·Pem ) + 1/2 (15)

1/PeT = 1/ (τ·Pem ) + 1/12 (16)

DL = u·d/PeL (17)

DT = u·d/PeT (18)
Membranes 2016, 6, 44 7 of 18

where Pem , PeL and PeT are the molecular Péclet number, the longitudinal Péclet number and
the transversal Péclet number, respectively; τ denotes tortuosity, and d represents the catalyst
particle diameter.
The conversion of methane was defined as [2]:

FCH4,feed − FCH4,ret
Xconversion = (19)
FCH4,feed

3. Results and Discussion

Membranes 2016, 6, 44 7 of 18
3.1. He Leak Tests and H2 Permeation Tests of the Membrane
After the
After the module
module waswas installed
installed in in the
the CMR
CMR rig,rig, the
thetemperature
temperature of of the
themembrane
membrane module
module waswas
increased from room temperature to 350 ◦°C under He gas at a rate
increased from room temperature to 350 C under He gas at a rate of 1 C/min and a pressure of of 1 ◦ °C/min and a pressure of
2 bar. At this temperature, a helium leak test showed an undetectable leak,
2 bar. At this temperature, a helium leak test showed an undetectable leak, and H2 was introduced and H 2 was introduced to

thethe
to module.
module. Hydrogen
Hydrogen permeance
permeancewas wasmeasured
measuredasasaafunction
functionof of time
time continuously
continuously everyevery 3030 ss as
as
shown in Figure 3. After 80 h, the temperature was increased to 450 ◦°C,
shown in Figure 3. After 80 h, the temperature was increased to 450 C, displaying a slight increase displaying a slight increase
in H
in H2 permeance.
permeance. The temperature was
The temperature was kept
kept for
for 160
160 h,h, and
and two
two helium
helium leak leak tests
tests were
were performed
performed
2
displaying undetectable He leak. Notice that on the first He leak test, steam
displaying undetectable He leak. Notice that on the first He leak test, steam was fed to the system was fed to the system
along with He for one hour to fully oxidize the WGS catalyst. The membrane
along with He for one hour to fully oxidize the WGS catalyst. The membrane showed a H2 permeance showed a H 2 permeance

of 70
of 70 and
and 8080Nm
Nm33··mm−−2·
2h
·h−·bar
·bar at0.5350
−1 1 −0.5− andand
at 350 450 450
°C, ◦respectively.
C, respectively.After 290 290
After h ofhcontinuous
of continuous testing, the
testing,
module temperature was increased to ~600 °C under
◦ a pure H 2 stream for 3 h to activate the MSR
the module temperature was increased to ~600 C under a pure H2 stream for 3 h to activate the
catalyst.
MSR NoticeNotice
catalyst. that after
thatactivation, the membrane
after activation, presented
the membrane a He leakaofHe
presented 0.4leak
sccm/bar
of 0.4at 450 °C. The
sccm/bar at
asymmetric
◦ Pd/Au/Pd membrane showed high H 2 flux and an ideal H2/He selectivity of over 4300
450 C. The asymmetric Pd/Au/Pd membrane showed high H2 flux and an ideal H2 /He selectivity
after
of over the4300
catalyst
afterwas
the activated.
catalyst was Even though itEven
activated. has been shown
though thatbeen
it has to improve
shown that the thermal
to improvestability
the
of the membranes,
thermal porous
stability of the Hastelloy
membranes, and Inconel
porous Hastelloy supports perform
and Inconel betterperform
supports than PSS at temperatures
better than PSS at
higher than 500
temperatures °C [32],
higher thanthe
500membrane
◦ C [32], theshowed
membrane a high thermal
showed stability.
a high thermal stability.

permeance, He
He leak tests at 350, 450 and activation ◦ C at different
Figure
Figure 3.3. Hydrogen permeance, activation at
at 585
585 °C at different
elapsed
elapsedtimes.
times.

Moreover, Gade
Moreover, Gade et et al.
al. [33]
[33]showed
showedthat
thatunannealed
unannealed Pd-Au
Pd-Au membranes
membranes require
require ~300
~300 hh under
under
typicaloperating
typical operating conditions
conditions to fully
to fully anneal
anneal in situ in
thesitu
Pd-Authesurface
Pd-Au surface
of the of theand
membrane membrane and
consequently
consequently reach a steady H flux. Nevertheless, as shown in Figure 3, after H
reach a steady H2 flux. Nevertheless, as shown in Figure 3, after H2 feed was introduced into the
2 2 feed was introduced
system 350 ◦ C,
into theatsystem atthe
350H °C, the across
2 flux H2 fluxthe
across the membrane
membrane reachedreached a steady
a steady statequickly.
state very very quickly. This
This effect
effect be
could could be theofresult
the result platingof Pd
plating Pdofon
on top thetop
Auof the Auwhich
surface, surface, which
added added
active sites active
for thesites for the
permeance
permeance
to occur. to occur.
Pure Pd membrane foils have shown a H2 permeance that follows the Arrhenius correlation, as
shown in Equation (20), where t is the thickness of the membrane in μm, 15,630 is the activation
energy in J/mol and 6322.7 is the pre-exponential factor in m3·μm·m−2·h−1·atm−0.5 [2]. Furthermore,
considering that the presented Pd/Au/Pd membrane has a Pd layer of 10.1 μm, the expected
permeance of its pure Pd foil analog is 47 Nm3·m−2·h−1·bar−0.5 at 450 °C. It is important to mention that
 Membranes 2016, 6, 44 8 of 18

15630
Membranes 2016, 6, 44 [6322.7 𝑒 − 𝑅𝑇 ]
(20)8 of 18
̅̅̅̅̅ ⁄
𝑃𝐻2 = 𝑡

Pure Pd membrane foils have shown a H2 permeance that follows the Arrhenius correlation,
as shown in Equation (20), where t is the thickness of the membrane in µm, 15,630 is the activation
energy3.2.
in MSR
J/mol in a Conventional Packed Bed Reactor: Single Catalyst 3
and 6322.7 is the pre-exponential factor in m ·µm·m−2 ·h−1 ·atm−0.5 [2]. Furthermore,
considering Methane
that thesteam reforming
presented was carriedmembrane
Pd/Au/Pd out in a conventional packed
has a Pd layer of bed
10.1reactor
µm, the(PBR) to
expected
experimentally
permeance of its puredemonstrate the effect
Pd foil analog is 47 of
Nm 3 ·m−2intensification
process ·h−1 ·bar−0.5 atand
450the◦ C.
presence of the secondary
It is important to mention
catalyst.
that the As mentioned
hydrogen before,
permeance of the
themajor advantage
presented of the CMR
Pd/Au/Pd compared is
membrane to asuperior
conventional
by aPBR is of
factor
the conversion enhancement of the equilibrium-limited MSR by removing in situ the produced H2.
1.7. This enhanced behavior of the membrane is due to the presence of gold, which as previously
Therefore, in order to study the performance of a PBR, a solid stainless steel pipe was placed instead
reported [3,34] can raise the permeance up to two-times higher due to an increase in diffusivity.
of the membrane in order to maintain identical geometric features of the CMR reactor. As shown in
Although the4,amount
Figure differentof goldvelocities,
space in the presented membrane
temperatures is 2%, whichratios
and steam-to-carbon is below
were the
usedoptimum 5% [35],
to investigate
the membrane displayed an excellent and stable
the performance of the PBR; all reaction conditions H flux.
2 were set to a total pressure of 2 bar, since higher
pressures did not show significant changesh in the reactioni performance. Notice that the catalyst
15630
loading was arranged in such a way that the6322.7 e− RT
operating GHSV was of 5000 h−1 as specified by the
provider of the catalyst. Furthermore, the=
PH2 experimental t results were graphically depicted along with (20)
the computational simulation outcomes as shown in Figure 4.
3.2. MSR inWe examine the performance
a Conventional of the PBR
Packed Bed Reactor: by analyzing
Single Catalyst its methane conversion at 500 °C and a
steam-to-carbon ratio of three. It is observed that even at small space velocities, methane conversion
Methane steam
is below its reforming
chemical was (shown
equilibrium carriedasout in a line
a dotted conventional
in Figure 4);packed bedis reactor
this effect caused by (PBR)
the to
experimentally
reduction ofdemonstrate
the contact time theofeffect
methaneof process
with theintensification and the
catalyst. Furthermore, thepresence of the secondary
effect of temperature on
catalyst.
the As mentioned
conversion before,isthe
of methane major
clear; advantage
it increased from of
40%thetoCMR compared
60% when to a conventional
the temperature PBR is
of the reactor
the conversion enhancement
was increased from 500 toof600 the°C.
equilibrium-limited
This is in agreementMSR with bythe removing
fact that MSR in situ
is anthe produced H2 .
endothermic
reaction,
Therefore, whichtois study
in order highlythefavored by high temperatures.
performance of a PBR, a solid stainless steel pipe was placed instead
Additionally,
of the membrane adding
in order steam hasidentical
to maintain a positivegeometric
effect on the reaction,ofdoubling
features the CMR thereactor.
conversion when in
As shown
the steam-to-carbon ratio is increased from 3 to 5. Furthermore, excess steam
Figure 4, different space velocities, temperatures and steam-to-carbon ratios were used to investigateis generally present in
the MSR process, since it not only increases conversion, but also prevents coke formation. It is
the performance of the PBR; all reaction conditions were set to a total pressure of 2 bar, since higher
important to mention that the results presented in this work are similar to the results reported in the
pressures did not show significant changes in the reaction performance. Notice that the catalyst
pertinent literature [2,36]. Additionally, the CFD simulation results, shown in Figure 4, match the
loading was arranged
experimental in such
data with a way that
an average errorthe operating
of 7.8%. GHSV was
The experiments of 5000
were h−out
carried
1 as specified by the
in a pilot-scale
provider of theand
module, catalyst. Furthermore,
therefore, these resultsthewere experimental
more susceptibleresults were graphically
to divergence depicted
from controlled along with
settings.
the computational simulation outcomes as shown in Figure 4.

Figure 4. Experimental and computer simulation methane conversions in a packed bed reactor (PBR)
Figure 4. Experimental and computer simulation methane conversions in a packed bed reactor (PBR)
as a function of different space velocities and conditions at a total pressure of 2 bar.
as a function of different space velocities and conditions at a total pressure of 2 bar.

3.3.examine
We MSR/WGS in performance
the a Conventional Packed
of theBed
PBRReactor: its methane conversion at 500 ◦ C and a
Dual Catalyst
by analyzing
steam-to-carbon ratio of three. It is observed that even at small space velocities, methane conversion
is below its chemical equilibrium (shown as a dotted line in Figure 4); this effect is caused by the
reduction of the contact time of methane with the catalyst. Furthermore, the effect of temperature on
the conversion of methane is clear; it increased from 40% to 60% when the temperature of the reactor
was increased from 500 to 600 ◦ C. This is in agreement with the fact that MSR is an endothermic
reaction, which is highly favored by high temperatures.
Membranes 2016, 6, 44 9 of 18

Additionally, adding steam has a positive effect on the reaction, doubling the conversion when
the steam-to-carbon ratio is increased from 3 to 5. Furthermore, excess steam is generally present in the
MSR process, since it not only increases conversion, but also prevents coke formation. It is important
to mention that the results presented in this work are similar to the results reported in the pertinent
literature [2,36]. Additionally, the CFD simulation results, shown in Figure 4, match the experimental
data with an average error of 7.8%. The experiments were carried out in a pilot-scale module, and
therefore, these results were more susceptible to divergence from controlled settings.

3.3. MSR/WGS in a Conventional Packed Bed Reactor: Dual Catalyst

The reforming
Membranes of methane and the water gas shift reactions were studied in a conventional
2016, 6, 44 9 ofpacked
18

bed reactor (PBR) to demonstrate the effect of the secondary catalyst and thus effectively demonstrate
The reforming of methane and the water gas shift reactions were studied in a conventional
the presence of a membrane. The reactor was packed in stages while a solid stainless steel pipe was used
packed bed reactor (PBR) to demonstrate the effect of the secondary catalyst and thus effectively
instead of a membrane in order to maintain the geometry of the module, as shown in Figure 5. The PBR
demonstrate the presence of a membrane. The reactor was packed in stages while a solid stainless
was packed inwas
steel pipe series
used with a fresh
instead Ni-based in
of a membrane reforming catalystthe
order to maintain and a Fe-Cr-based
geometry WGS as
of the module, catalyst
shown with
an overall proportion
in Figure 5. The PBR ofwas
20%packed
and 80% for reforming
in series with a freshand WGS,reforming
Ni-based respectively. Theand
catalyst configuration
a Fe-Cr-basedof the
catalysts
WGS within thewith
catalyst reactor, shown
an overall in Figureof5,20%
proportion wasandsplit80%
as MSR-WGS-MSR-WGS-MSR. The MSR-WGS
for reforming and WGS, respectively. The
configuration of the ◦
reactor was tested at 475 C since the Fe-Cr catalyst temperature limit is specified by the provider to
catalysts within the reactor, shown in Figure 5, was split as MSR-WGS-MSR-
500 ◦ C. After
be of WGS-MSR. The packing
MSR-WGS reactor
the module,was tested
steamatand475 He
°C since
werethe fedFe-Cr catalyst
to the systemtemperature
to oxidizelimit
theisWGS
specified
catalyst. by the provider
The catalyst emittedtoHbe of 500 °C. After packing the module, steam and He were fed to the
2 , and therefore, oxidation continued until H2 was not detectable by
system to oxidize the WGS catalyst. The catalyst emitted H2, and therefore, oxidation continued until
the GC [6]; this process took around 1 h. Afterwards, the temperature of the module was increased to
H2 was not detectable by the GC [6]; this process took around 1 h. Afterwards, the temperature of the
~600 ◦ C under pure H2 stream for 3 h to activate the MSR catalyst. After these procedures, the reaction
module was increased to ~600 °C under pure H2 stream for 3 h to activate the MSR catalyst. After
tests were carried out. Notice that a CFD simulation for this multistage packing configuration was
these procedures, the reaction tests were carried out. Notice that a CFD simulation for this multistage
performed
packing toconfiguration
further analyze was the PBR. to further analyze the PBR.
performed

Figure 5. Conceptual illustration of the catalyst distribution throughout the PBR reactor with the left
Figure 5. Conceptual illustration of the catalyst distribution throughout the PBR reactor with the left
side cut away to show the tube and the catalyst.
side cut away to show the tube and the catalyst.
The conversion of methane at 475 °C, 2 bar and a GHSV of 3500 h−1 was found to be 18%, as
shown
The in Figure 6;ofhowever,
conversion methaneit at 475 ◦ C,slightly
decreased as thea pressure
2 bar and GHSV of was3500 h−1 was
increased. It isfound
important
to beto 18%,
mention
as shown that the6;purpose
in Figure however, of adding the WGS
it decreased catalyst
slightly asisthe
to prevent
pressureor was
reduce the formation
increased. of CO in to
It is important
the module.
mention that theAs shown by
purpose of Figure
adding6,the
it can be observed
WGS catalystthat
is toalthough
preventinorsmall quantities,
reduce CO is present
the formation of CO in
in the product of the reaction. For both experiments and simulations, the amount of CO reduces as
the module. As shown by Figure 6, it can be observed that although in small quantities, CO is present
pressure increases; this indicates that the production of CO may be hindered by pressure or that the
in the product of the reaction. For both experiments and simulations, the amount of CO reduces as
activity of the WGS catalyst is favored at higher pressures (Equation (2)). Given the stoichiometry of
pressure increases; this indicates that the production of CO may be hindered by pressure or that the
MSR (Equations (1)–(3)), a reduction of methane conversion and simultaneously CO generation as
activity of the WGS
the pressure catalyst
of the reactorisincreases
favoredisatexpected;
higher pressures
at the same (Equation (2)). Given
time, as reported the stoichiometry
by Atwood et al. [37], of
MSR the(Equations (1)–(3)),
WGS reaction a reduction
intensifies of methane
at higher pressures.conversion
These two and simultaneously
mechanisms contributeCO to generation
obtaining as
the pressure
lower CO ofyields.
the reactor increases is expected; at the same time, as reported by Atwood et al. [37],
the WGS reaction intensifies at higher pressures. These two mechanisms contribute to obtaining lower
CO yields.
It is important to notice that in this dual-catalyst reactor, the WGS reaction occurs in the presence
of a significant amount of H2 , which limits its performance. Figure 7 shows that even though lower
theoretical CO is present in the dual-catalyst reactor, the experimental results of the pilot-scale bed
appeared to be hindered by the intrinsic error in the measurements. Nevertheless, through the
simulation, it is found that as the space velocity increases, the difference in CO production decreases
further for the dual-catalyst bed. This effect can be attributed to two factors: (i) the reduced presence of
 Figure 5. Conceptual illustration of the catalyst distribution throughout the PBR reactor with the left
side cut away to show the tube and the catalyst.

The conversion of methane at 475 °C, 2 bar and a GHSV of 3500 h−1 was found to be 18%, as
shown in Figure 6; however, it decreased slightly as the pressure was increased. It is important to
Membranes 2016, 6,that
mention 44 the purpose of adding the WGS catalyst is to prevent or reduce the formation of CO in 10 of 18
the module. As shown by Figure 6, it can be observed that although in small quantities, CO is present
in the product of the reaction. For both experiments and simulations, the amount of CO reduces as
H2 ; andpressure
(ii) lower concentrations
increases; of CO.
this indicates that The aforementioned
the production factors
of CO may are generated
be hindered dueor
by pressure tothat
reduced
the CH4
conversions.
activity of the WGS catalyst is favored at higher pressures (Equation (2)). Given the stoichiometry is
Additionally, a surface plot of CO concentration through the reactor module of shown
in Figure
MSR 8 to illustrate
(Equations the effect
(1)–(3)), of the water-gas-shift
a reduction catalyst.
of methane conversion At first, CO isCO
and simultaneously generated
generationonasthe first
the pressure
MSR catalyst of the reactor
bed section, increases
followed is expected;
by its at the by
consumption same
thetime,
WGS as reported
reaction by Atwood
zone. The et al. [37],
next MSR layer
inducesthetheWGS reaction intensifies
production of more CO,at higher
which pressures. These twoby
is later reduced mechanisms contribute
the following WGStosegment.
obtainingFinally,
lower CO yields.
the MSR catalyst at the end of the PBR increases the overall CO concentration inside the reactor.
Membranes 2016, 6, 44 10 of 18
Membranes 2016, 6, 44 10 of 18
Figure 6. Experimental and computational simulation of two catalysts in a PBR as a function of
Figure pressures
different 6. Experimental and of
at a GHSV computational simulationofof475
3500 h−1, a temperature two°Ccatalysts in a PBR as a ratio
and a steam-to-carbon function of
of five.
different pressures at a GHSV of 3500 h−1, a temperature of 475 °C and a steam-to-carbon ratio of five.
It is important to notice that in this dual-catalyst reactor, the WGS reaction occurs in the presence
It is important
of a significant amountto notice
of H2,that
whichin this dual-catalyst
limits reactor,Figure
its performance. the WGS reaction
7 shows occurs
that eveninthough
the presence
lower
of a significant amount of H 2, which limits its performance. Figure 7 shows that even though lower
theoretical CO is present in the dual-catalyst reactor, the experimental results of the pilot-scale bed
theoretical
appeared to CO
be is present by
hindered in the
thedual-catalyst
intrinsic errorreactor, themeasurements.
in the experimental results of the pilot-scale
Nevertheless, through bed
the
appeared to be hindered by the intrinsic error in the measurements. Nevertheless,
simulation, it is found that as the space velocity increases, the difference in CO production decreases through the
simulation,
further for theitdual-catalyst
is found that as theThis
bed. space velocity
effect increases,
can be theto
attributed difference in CO
two factors: (i) production
the reduceddecreases
presence
further for the dual-catalyst bed. This effect can be attributed to two factors: (i) the reduced presence
of H2; and (ii) lower concentrations of CO. The aforementioned factors are generated due to reduced
of H2; and (ii) lower concentrations of CO. The aforementioned factors are generated due to reduced
CH4 conversions. Additionally, a surface plot of CO concentration through the reactor module is
CH4 conversions. Additionally, a surface plot of CO concentration through the reactor module is
shown in Figure 8 to illustrate the effect of the water-gas-shift catalyst. At first, CO is generated on
shown in Figure 8 to illustrate the effect of the water-gas-shift catalyst. At first, CO is generated on
the first MSR catalyst bed section, followed by its consumption by the WGS reaction zone. The next
the first MSR catalyst bed section, followed by its consumption by the WGS reaction zone. The next
MSR layer induces the production of more CO, which is later reduced by the following WGS segment.
MSR layer induces the production of more CO, which is later reduced by the following WGS segment.
Finally, the MSR catalyst at the end of the PBR increases the overall CO concentration inside the
Finally, the MSR catalyst at the end of the PBR increases the overall CO concentration inside the
reactor.6. Experimental and computational simulation of two catalysts in a PBR as a function of different
Figure
reactor.
pressures at a GHSV of 3500 h−1 , a temperature of 475 ◦ C and a steam-to-carbon ratio of five.

Figure 7. Concentration
Figure 7.7.Concentration
Figure Concentration ofofof
CO
CO in
CO ininconventional
conventional PBRs
conventionalPBRs
PBRs containing
containing
containing a single
aa single
single MSRMSR catalyst
catalyst and a dual
and aa dual
and dual
MSR-WGS catalyst at aatat
pressure ofofof22bar, ◦ C and
MSR-WGS
MSR-WGS catalyst
catalyst a apressure
pressure bar,aatemperature
2bar, temperature ofof
temperatureof 475
475
475 °C
°C and a steam-to-carbon
and aa steam-to-carbon
steam-to-carbon ofratio
ratio of
ratio five. of five.
five.

Figure 8. CFD concentration profile of CO inside in a PBR containing MSR-WGS catalysts.

Figure 8. CFD concentrationprofile
profile of
Figure 8. CFD concentration of CO
COinside
insideinin
a PBR containing
a PBR MSR-WGS
containing catalysts.
MSR-WGS catalysts.
3.4.
3.4. MSR/WGSinina aCatalytic
MSR/WGS CatalyticMembrane
MembraneReactor
Reactor
Membranes 2016, 6, 44 11 of 18

3.4. MSR/WGS in a Catalytic Membrane Reactor

Membranes
The CMR 2016, 6, 44 packed with two layers of catalysts in series only (in contrast with
was 11 of 18 five
the
layers in the PBR) and with a membrane placed at the center of the reactor to remove in situ the
The CMR was packed with two layers of catalysts in series only (in contrast with the five layers
H2 generated by the reactions. The experimental CH4 conversion results are shown in Figure 9 for
in the PBR) and with a membrane placed at the center of the reactor to remove in situ the H2 generated
different
by thesteam-to-carbon ratios, a temperature
reactions. The experimental CH4 conversion 475 ◦ Care
of results and a pressure
shown in Figureof 5 bar.
9 for Notice
different steam-that, in
contrast
to-carbon ratios, a temperature of 475 °C and a pressure of 5 bar. Notice that, in contrast withCMR
with conventional PBRs, the pressure has a significant effect on the effectiveness of
technology. SincePBRs,
conventional the rate of removal
the pressure has of H2 is a function
a significant effect onof
theits partial pressure,
effectiveness of CMRhigher pressures
technology. Since will
ensurethea rate
betterof performance.
removal of H2 Furthermore,
is a function oftheits CMR
partialinpressure,
this reactor was
higher not tested
pressures willatensure
2 bar (as the PBR);
a better
performance.
because at such a Furthermore,
low pressurethe CMR in this
difference, it isreactor was to
expected notobserve
tested atreverse
2 bar (asflow
the PBR);
(frombecause at
the permeate
such a low pressure difference, it is expected to observe reverse flow (from
side to the reacting side) since H2 is pure on the permeate side. The highest conversion achieved the permeate side to the
was ofreacting
43.3%side)
at a since H2 is pure on the
steam-to-carbon permeate
ratio of fiveside.
andThe highest
a space conversion
velocity achieved
of 1172 h−1 . was of 43.3% at it is
Furthermore,
a steam-to-carbon ratio of five and a space velocity of 1172 h−1. Furthermore, it is found that as the
found that as the GHSV was increased, the conversion of methane decreased accordingly; this was
GHSV was increased, the conversion of methane decreased accordingly; this was caused by the
caused by the reduction of residence time in the reactor. In addition, the amount of water influenced
reduction of residence time in the reactor. In addition, the amount of water influenced the reaction
the reaction significantly;
significantly; a steam-to-carbon
a steam-to-carbon ratio of fiveratio of five
produced produced
about about
20% higher CH 20% higher CH4 conversion
4 conversion than a ratio
than aofratio
three.ofNotice
three.thatNotice
the Hthat the generated
2 purity H2 puritybygenerated by this
this Pd/Au/Pd Pd/Au/Pd
membrane membrane
was 99.94% was 99.94%
throughout a
throughout a testing
testing time of 350time of 350
h under h under
MSR/WGS MSR/WGS
conditions. The conditions. The best
best flux achieved flux
by the CMR achieved by the CMR
under optimum
underconditions
optimum was conditions
over 500 was over 500
NL/day. NL/day.
After After the experiments
the experiments were terminated,
were terminated, the surface the surface
of the
membrane did not show carbon deposition for the reason that the
of the membrane did not show carbon deposition for the reason that the protective cage separatedprotective cage separated
effectively
effectively the reaction
the reaction zonezone
fromfrom
thethe membrane.
membrane.

Figure 9. Experimental methane conversion of the dual catalyst CMR represented as scatter points and
Figure 9. Experimental methane conversion of the dual catalyst CMR represented as scatter points
the difference betweenbetween
CMR and PBR ◦ C.
and the difference CMR andatPBR
5 bar,
at 5atbar,
a temperature of 475
at a temperature of 475 °C.

The reactor
The reactor performance
performance indicatorfor
indicator forprocess
process intensification
intensification was
was quantitatively analyzed
quantitatively basedbased
analyzed
on the Δ-index previously reported by Ayturk et al. [2]. This index is represented in Equation (21) as
on the ∆-index previously reported by Ayturk et al. [2]. This index is represented in Equation (21)
the difference between the CH4 conversion achieved by the CMR and the one by PBR under similar
as the difference between the CH4 conversion achieved by the CMR and the one by PBR under
conditions.
similar conditions.
𝐶𝑀𝑅 𝑃𝐵𝑅
∆ =∆ 𝑋=𝐶𝐻4 X−CMR
𝑋𝐶𝐻4 PBR (21) (21)
CH4 − XCH4
It is important to mention that the PBR was not operated experimentally at 475 °C and 5 bar; ◦ C and 5 bar;
It is important
consequently, thetoCFD
mention that the
performance PBR was
outcome notconventional
of the operated experimentally
PBR was utilized atto475
estimate the
consequently,
Δ-index ofthe thisCFD
work.performance outcome of
The Δ-index represented inthe conventional
Figure 9 shows thatPBR
at allwas utilized
GHSV, to estimate
the conversion of the
∆-index of this
methane work. The
increases when ∆-index represented
sized against in Figure
a conventional 9 shows
reactor. that at allthe
Nevertheless, GHSV, the of
concept conversion
process of
methane increasesiswhen
intensification bettersized against
appreciated at alow
conventional reactor.
space velocities since Nevertheless, the concept
H2 has a better rate of removal ofand
process
the contactis
intensification time of the
better gases with the
appreciated catalysts
at low space increases.
velocities since H2 has a better rate of removal and
the contactFor the of
time simulation
the gasesresult,
withas expected,
the catalysts compared
increases.to a PBR, the constant removal of H2, shown
For the simulation result, as expected, compared to achanges
by the hydrogen concentration profiles in Figure 10, PBR, thetheconstant
composition of the
removal of Hretentate,
2 , shown by
allowing both reactions to proceed further. In Figure 10, it is possible to observe that as soon as the
the hydrogen concentration profiles in Figure 10, changes the composition of the retentate, allowing
 Membranes 2016, 6, 44 12 of 18

Membranes 2016, 6, 44 12 of 18
both reactions to proceed further. In Figure 10, it is possible to observe that as soon as the feed stream
feed
(onstream
the left)(on the
is in left) iswith
contact in contact withbed,
the catalyst the H catalyst bed, H2 is generated and increases as the
2 is generated and increases as the reaction proceeds;
reaction proceeds; this continues until the H 2 partial pressure in the retentate is high enough to
this continues until the H2 partial pressure in the retentate is high enough to provide the driving force
provide
for thethe driving force
membrane forremoving
to start the membrane to start
it. Notice thatremoving
even thoughit. Notice that even
the reaction thoughtothe
continues reaction
take place in
continues to take
the module, place in in
an increase theHmodule, an increase
concentration is no in H2 concentration
longer observed; thisiseffect
no longer
is observed;
caused by the this of
rate
2
effect is caused by the rate of removal overcoming the rate of reaction. Furthermore,
removal overcoming the rate of reaction. Furthermore, it is possible to observe, from top to bottom, it is possible to
observe, from top to bottom, a gradual reduction in H 2 concentration caused by the presence of the
a gradual reduction in H2 concentration caused by the presence of the membrane. This reduction in H2
membrane. This adjacent
concentration reductiontoin H2surface
the concentration adjacent tocauses
of the membrane the surface of the membrane
a H2 depleted boundarycauses a H2
layer formed
depleted
by low radial diffusion rates. This effect is often referred to as concentration polarization, and itas
boundary layer formed by low radial diffusion rates. This effect is often referred to can
concentration
significantlypolarization, and it can significantly
reduce the performance of the membrane reduce[38].
the performance of the membrane [38].

Figure
Figure 10.10. Concentration
Concentration profile
profile of2H
of H 2 inside
inside in aindual
a dual MSR-WGS
MSR-WGS catalytic
catalytic membrane
membrane reactor.
reactor.

ToTofurther
furthercharacterize
characterize thethe
performance
performance of of
thethemembrane
membrane reactor,
reactor,thethe
product
product of of
Damkohler
Damkohler andand
Péclet numbers (DaPe number) is utilized, since it provides the ratio of maximum
Péclet numbers (DaPe number) is utilized, since it provides the ratio of maximum reaction rate over reaction rate over
thethe
maximum
maximum permeation
permeation raterate
perper
volume
volume [39].[39].
In PBRs, the Damkohler
In PBRs, the Damkohler number (Da) exemplifies
number (Da) exemplifiesthe
performance of the reactors, since it shows the ratio of the reaction rate
the performance of the reactors, since it shows the ratio of the reaction rate over the convective over the convective mass
transport of the reactant;
mass transport while while
of the reactant; in membrane
in membrane technology, the Péclet
technology, the Pécletnumber
number shows shows thetherelative
relative
convection transport rate over the diffusive rate (permeation). Consequently,
convection transport rate over the diffusive rate (permeation). Consequently, the product DaPe dictates the product DaPe
dictates the overall
the overall effectiveness
effectiveness of the CMR;of theforCMR;
instance, for having
instance, having
a DaPe > 1 ameans
DaPethat
> 1the means that the
permeation rate
permeation
is low, andrate is low,
thus, the Hand
2
thus,
rate of the H
removal 2 rate of removal through the membrane is the limiting factor
through the membrane is the limiting factor of the reactor’s
of productivity.
the reactor’s productivity.
As reported As by reported
Battersbyby et Battersby
al. [39], the et al. [39],number
DaPe the DaPe cannumber can be as
be estimated estimated
shown in
as Equation
shown in Equation (22) where X equilib is the conversion achieved when the reaction is
(22) where Xequilib is the conversion achieved when the reaction is thermodynamically at
thermodynamically
equilibrium, and at equilibrium,
Xactual and Xactual displayed
is the conversion is the conversion
by the displayed
membraneby the membrane
reactor. Most of reactor.
the DaPe
Most of the DaPe numbers displayed by this CMR, shown in Table 3, are
numbers displayed by this CMR, shown in Table 3, are lower than one; this implies that the rate lower than one; this implies
that
of the rate of His2 high
H2 removal removal
enoughis high enoughthe
to change topseudo-equilibrium
change the pseudo-equilibriumstate favorably state favorably
to achieve to
higher
achieve higher conversions.
conversions. Notice that the Notice
termthat the term “pseudo-equilibrium”
“pseudo-equilibrium” is used to describeis usedthetosituation
describe wherethe
situation where the reaction product (H 2) is independently manipulated, by the use of a permeable
the reaction product (H2 ) is independently manipulated, by the use of a permeable membrane [39].
membrane
Furthermore,[39]. Table
Furthermore,
3 shows Table
that at3high
shows GHSV,that at thehigh
DaPe GHSV,
number theapproaches
DaPe number one,approaches
implying that one,the
implying
rate of reaction matches the maximum permeation equivalent. It is important to mention thatto
that the rate of reaction matches the maximum permeation equivalent. It is important it is
mention that itthat
considered is considered
the optimum that design
the optimum
of a CMR design of a CMR
should operateshould operate at aDaPe
at a theoretical theoretical
= 1. DaPe = 1.

Xequilib
𝑋𝑒𝑞𝑢𝑖𝑙𝑖𝑏
DaPe = (22)
𝐷𝑎𝑃𝑒 = Xactual (22)
𝑋𝑎𝑐𝑡𝑢𝑎𝑙

Table 3. The Damkohler and Péclet (DaPe) number of the dual catalyst CMR at different space
velocities at 5 bar and 475 °C.

GHSV (h−1) DaPe Number

1170 0.47
Membranes 2016, 6, 44 13 of 18

Table 3. The Damkohler and Péclet (DaPe) number of the dual catalyst CMR at different space velocities
at 5 bar and 475 ◦ C.

GHSV (h−1 ) DaPe Number

Membranes 2016, 6, 44 1170 0.47 13 of 18
1750 0.61
2270
1750 0.56
0.61
2810 0.61
2270 0.56
4680 0.77
2810
6250 0.61
1.07
4680 0.77
6250 1.07
The concentration of CO in the system was undetectable in this dual catalytic CMR. However,
The if
it is not clear concentration of CO in
this is the result ofthe
thesystem was undetectable
presence in this dual
of the secondary WGS catalytic
catalyst CMR. However,
or if it
it is caused by
is not clear if this is the result of the presence of the secondary WGS catalyst or
the presence of a H2 -permeable membrane, as previously reported [6,12,18,19]. For instance, Lin et al. if it is caused by the
presence of a H2-permeable membrane, as previously reported [6,12,18,19]. For instance, Lin et al.
described a reduction of CO yield from 50% down to <2% in a Pd-based CMR [12]. Therefore, to
described a reduction of CO yield from 50% down to <2% in a Pd-based CMR [12]. Therefore, to
observe the effect
observe of the
the effect of thesecondary
secondary catalyst,
catalyst, a a simulation
simulation of both
of both singlesingle
and dual and dual CMRs
catalyst catalyst
wasCMRs
was performed.
performed. In Figure 11a, it can be observed that the CO yield increases in both CMRs as theas the
In Figure 11a, it can be observed that the CO yield increases in both CMRs
temperature is increased
temperature andand
is increased the the
GHSVGHSV is is
reduced.
reduced.Nonetheless,
Nonetheless, the theeffect
effectofofthe
the secondary
secondary catalyst is
catalyst
also observed by reducing
is also observed the CO
by reducing the COyield, especially
yield, especiallyatat higher operating
higher operating temperatures.
temperatures. For instance,
For instance,
at the lowest
at the lowest GHSV GHSV and ◦650
and 650 °C, the
C, the COCO yield
yield at at
thethe retentateisisreduced
retentate reduced from
from 9%9% on onthe
theCMR
CMRwithwith one
one catalyst to 6.5% on the dual CMR, while at◦450 °C, it is reduced
catalyst to 6.5% on the dual CMR, while at 450 C, it is reduced from 0.2% down to <0.05%. from 0.2% down to <0.05%.

(a)

(b)
Figure 11. (a) CO yield and (b) H2 recovery for single and dual CMRs at 5 bar and a carbon-to-steam
Figure 11. (a) CO yield and (b) H2 recovery for single and dual CMRs at 5 bar and a carbon-to-steam
ratio of five.
ratio of five.
Membranes 2016, 6, 44 14 of 18

Membranes 2016, 6, 44 14 of 18
Additionally, Figure 11b shows the H2 recovery obtained by the CMRs at different space velocities
Additionally, In
and temperatures. Figure 11b shows
both CMRs, the H2increases
H2 recovery recoverywithobtained
higherby the CMRs and
temperatures at different space
reduced GHSV,
velocities and temperatures. In both CMRs, H recovery increases with higher
since these conditions are favorable for higher CH4 conversions. Additionally, it can clearly be seen
2 temperatures and
reduced
that GHSV, since
H2 recovery thesein
increases conditions are favorable
the dual CMR for higher
particularly as theCH 4 conversions.
temperature Additionally,
increases. it can
For instance,
clearly
the be seen of
operation that H2dual
the recovery
bed at 600 ◦ Cinisthe
increases dual CMR
expected particularly
to produce more as H
the
2 temperature
than the increases.
conventional
For instance,CMR.
single-stage the operation of the
Additionally, dualCO
lower bed at 600
yields °C is expected
intrinsically mean notto produce
only higher more H2Hgeneration
2 than the

conventional
and enriched single-stage
CO2 streamsCMR. at theAdditionally,
retentate, butlower
also CO yields intrinsically
the potential reductionmean of COnot only higher
poisoning H2
of the
generation and enriched CO streams at the retentate, but also the potential
membrane. Several studies have shown that severe reductions in H2 permeance occur in the presence
2 reduction of CO
poisoning
of CO mainly of the membrane.
caused Several studies
by the adsorption of CO have
on theshown that severe
Pd surface, reductions
hindering the activein H 2 permeance
sites available
occur
for H2intothe presence
adsorb [40]. of CO mainly
Reacting caused
CO with H2by thethe
O in adsorption of CO on
catalyst section the Pd
allows thesurface,
membrane hindering the
to be less
active sites available for H to adsorb [40]. Reacting CO with H O in the catalyst
exposed to CO reducing poisoning. Furthermore, the presence of the WGS can potentially decrease
2 2 section allows the
membrane
coking whento be less exposed
operating at lowtosteam-to-carbon
CO reducing poisoning.
ratios, asFurthermore,
carbon formationthe presence of the WGS can
is thermodynamically
potentially
favored decrease
by the cokingofwhen
dissociation CO [41].operating at low steam-to-carbon ratios, as carbon formation is
thermodynamically favored by the dissociation of CO [41].
2CO ↔ C + CO2 (23)
2CO ↔ C + CO2 (23)
The results obtained in the present work were compared against those shown in the literature literature
for methane steam reforming,
reforming, as shown
shown inin Figure
Figure 12a.
12a. The conversion of methane in traditional traditional
packed
packed bed
bedreactors
reactors(PBR)
(PBR)and membrane
and membranereactors (CMR)
reactors from from
(CMR) different literature
different sourcessources
literature was plotted
was
against
plotted different temperatures
against different as reported
temperatures by Gallucci
as reported by et al. [10],etand
Gallucci al. it[10],
is shown
and ittoisbe in agreement
shown to be in
with previously-reported
agreement values. Furthermore,
with previously-reported various COvarious
values. Furthermore, mole fractions
CO mole at fractions
the outletatofthe
theoutlet
reactor
of
were graphically
the reactor representedrepresented
were graphically as a functionasof different of
a function methane
different conversions, as shown inasFigure
methane conversions, shown 12b.
in
Figure
The 12b. The composition
composition of CO shownofexperimentally
CO shown experimentally
by this workby this work is lower
is significantly significantly lower
than those than
shown
those
in shown
other in other
sources, sources,
suggesting suggesting
that that the
the additional WGS additional
catalyst inWGSthe catalyst
CMR helped in theinCMR helpedthe
decreasing in
decreasing
residual CO.the residual CO.

(a)

Figure 12. Cont.

Membranes 2016, 6, 44 15 of 18
Membranes 2016, 6, 44 15 of 18

(b)
Figure
Figure 12.
12. Comparison
Comparison of
of the
the results
results presented
presented inin this
this work
work against
against those
those presented
presented in
in the
the literature
literature
for (a) methane conversion and (b) CO yield at 450–500 °C
◦ and 2–5 bar [10,42–44].
for (a) methane conversion and (b) CO yield at 450–500 C and 2–5 bar [10,42–44].

4. Conclusions
4. Conclusions
The
The concept
concept of
of catalyst
catalyst packing
packing in
in series
series was
was explored
explored through
through the development of
the development of aa catalytic
catalytic
membrane
membrane reactor
reactor (CMR)
(CMR) module
module utilizing
utilizing two
two catalysts
catalysts positioned
positioned inin series.
series. In
In the
the process
process system
system
under consideration, the methane steam reforming catalyst (MSR) is placed first to
under consideration, the methane steam reforming catalyst (MSR) is placed first to generate generate CO and
CO
H 2, followed by a water-gas-shift layer placed in series used to react CO, thus producing a higher H2
and H2 , followed by a water-gas-shift layer placed in series used to react CO, thus producing a
yield. In particular, a tubular Pd/Au/Pd membrane was synthesized, characterized and
higher H2 yield. In particular, a tubular Pd/Au/Pd membrane was synthesized, characterized and
accommodated throughout the reactor to remove the produced H2 in situ. The membrane was
accommodated throughout the reactor to remove the produced H2 in situ. The membrane was
surrounded by a protective catalyst cage in order to protect the surface of the membrane, which
surrounded by a protective catalyst cage in order to protect the surface of the membrane, which helped
helped in preventing carbon deposition on the surface of the membrane. The performance of this
in preventing carbon deposition on the surface of the membrane. The performance of this novel reactor
novel reactor was comparatively assessed against a conventional packed bed reactor (PBR) with no
was comparatively assessed against a conventional packed bed reactor (PBR) with no stages, as well
stages, as well as five-catalyst stages. In addition, a computational fluid dynamics (CFD) simulation
as five-catalyst stages. In addition, a computational fluid dynamics (CFD) simulation framework in
framework in 2D was developed to further analyze the characteristics of the CMR. The experimental
2D was developed to further analyze the characteristics of the CMR. The experimental results for
results for the conventional and CMR module are in agreement with the simulation-generated
the conventional and CMR module are in agreement with the simulation-generated performance
performance characterization ones. Moreover, the membrane used in this work displayed
characterization ones. Moreover, the membrane used in this work displayed experimental H2
experimental H2 permeances of3 70−and 80 Nm3·m−2·h−1·bar−0.5 at 350 and 450 °C, respectively. Notice
permeances of 70 and 80 Nm ·m 2 ·h−1 ·bar−0.5 at 350 and 450 ◦ C, respectively. Notice that this
that this configuration is reported for the first time in the pertinent literature and exhibited excellent
configuration is reported for the first time in the pertinent literature and exhibited excellent technical
technical performance. Indeed, it was demonstrated that excellent H2/He selectivity is attainable after
performance. Indeed, it was demonstrated that excellent H2 /He selectivity is attainable after catalyst
catalyst activation at 600 °C while producing H2 with a purity of >99.9% over 350 h of continuous
activation at 600 ◦ C while producing H2 with a purity of >99.9% over 350 h of continuous operation
operation under MSR/WGS conditions and 300 h under pure H2 testing conditions. The cumulative
under MSR/WGS conditions and 300 h under pure H2 testing conditions. The cumulative testing time
testing time of the membrane was 650 h or one month.
of the membrane was 650 h or one month.
The dual CMR was operated at a temperature of 475 °C, a pressure of 5 bar, steam-to-carbon
The dual CMR was operated at a temperature of 475 ◦ C, a pressure of 5 bar, steam-to-carbon
ratios of three and five and gas hourly space velocities between 1000 and 6000 h−−11. This dual CMR
ratios of three and five and gas hourly space velocities between 1000 and 6000 h . This dual CMR
showed higher methane conversion than the conventional reactor. Please notice that this effect, also
showed higher methane conversion than the conventional reactor. Please notice that this effect, also
known to be critically related to key process intensification objectives, was more noticeable at low
known to be critically related to key process intensification objectives, was more noticeable at low
space velocities. The CMR module had a DaPe number ranging between 0.5 and 1, demonstrating
space velocities. The CMR module had a DaPe number ranging between 0.5 and 1, demonstrating
the effective membrane performance at the specified conditions. Furthermore, the dual CMR module
the effective membrane performance at the specified conditions. Furthermore, the dual CMR module
showed a significant reduction in the CO content, which was shown to be the result of the subsequent
showed a significant reduction in the CO content, which was shown to be the result of the subsequent
“packing step” with the WGS catalyst introduced in the proposed module design.
“packing step” with the WGS catalyst introduced in the proposed module design.
Acknowledgment: The authors would like to thank Peter Czermak for the kind invitation to contribute to the
Special Issue “Membranes and Process Intensification” through the submission of the present manuscript. The
Membranes 2016, 6, 44 16 of 18

Acknowledgments: The authors would like to thank Peter Czermak for the kind invitation to contribute to
the Special Issue “Membranes and Process Intensification” through the submission of the present manuscript.
The authors are also indebted to the anonymous reviewers for their insightful remarks and helpful suggestions
that resulted in an improvement of the paper’s content. Financial support provided by the U.S. Department
of Energy through Grant No. DE-FE0004895 is gratefully acknowledged, as well. Finally, the authors would
like to thank Thomas Partington for the continuous technical support provided throughout the development of
this work.
Author Contributions: Bernardo Castro-Dominguez conceived of the experiments. Bernardo Castro-Dominguez
and Liang-Chih Ma designed and performed the experiments. Ivan P. Mardilovich synthesized the Pd/Au/Pd
membrane tubes for the experiments. Bernardo Castro-Dominguez, Liang-Chih Ma and Rui Ma designed and
developed the CFD modeling framework for the 2D simulation. Anthony Dixon provided insightful comments
and expertise in the CFD modeling framework. Nikolaos K. Kazantzis and Yi Hua Ma contributed to the thematic
content and organizational structure of the present research project. Yi Hua Ma provided expertise in membrane
technology. Bernardo Castro-Dominguez wrote the paper, while all authors analyzed the results and revised
the paper.
Conflicts of Interest: The authors declare no conflict of interest.

Nomenclature

$ Density of the gas mixture kg/m3

εp Porosity of the catalytic bed –
βF Forchheimer coefficient kg/m4
τ Tortuosity –
d Catalyst particle diameter m
Pi Partial pressure of component i in the reaction zone bar
Pem Péclet number –
Da Damkohler number –
ri Reaction rate kmol/kgcat /h
Ri Rate of generation and/or destruction of component i kmol/kgcat /h
ki Reaction rate constant varies
Ki Equilibrium constant varies
GHSV Gas hourly space velocity h−1
Ni Flux of component i mol/s
Rg Ideal gas constant J/K/mol
PH2 Hydrogen permeance of the membrane Nm3 ·m−2 ·h−1 ·bar−0.5
T Temperature K
∆ Delta index –
t Membrane’s thickness µm
u Velocity field m/s
F External body forces (gravity, electric, etc.) N
I Identity matrix –
X Conversion of methane –
D AB Binary diffusion coefficient between components A and B cm2 /s
MA Molecular weight of component A g/mol
ϕ D,AB Collision integral for diffusion Å
σAB Lennard–Jones potential between molecules A and B –

References
1. U.S. Office of Energy Efficiency & Renewable Energy. Available online: http://energy.gov/eere/fuelcells/
hydrogen-production-natural-gas-reforming (accessed on 1 March 2016).
2. Ayturk, M.E.; Kazantzis, N.K.; Ma, Y.H. Modeling and performance assessment of Pd- and Pd/Au-based
catalytic membrane reactors for hydrogen production. Energy Environ. Sci. 2009, 2, 430–438. [CrossRef]
Membranes 2016, 6, 44 17 of 18

3. Guazzone, F.; Catalano, J.; Mardilovich, I.P.; Kniep, J.; Pande, S.; Wu, T.; Lambrecht, R.C.; Datta, S.;
Kazantzis, N.K.; Ma, Y.H. Gas permeation field tests of composite Pd and Pd-Au membranes in actual coal
derived syngas atmosphere. Int. J. Hydrog. Energy 2012, 19, 14557–14568. [CrossRef]
4. Mardilovich, I.P.; Castro-Dominguez, B.; Kazantzis, N.K.; Wu, T.; Ma, Y.H. A comprehensive performance
assessment study of pilot-scale Pd and Pd/alloy membranes under extended coal-derived syngas atmosphere
testing. Int. J. Hydrog. Energy 2015, 40, 6107–6117. [CrossRef]
5. Dixon, A.G. Recent research in catalytic inorganic membrane reactors. Int. J. Chem. React. Eng. 2003, 1, 1–35.
[CrossRef]
6. Catalano, J.; Guazzone, F.; Mardilovich, I.P.; Kazantzis, N.K.; Ma, Y.H. Hydrogen production in a large scale
water-gas shift Pd-based catalytic membrane reactor. Ind. Eng. Chem. Res. 2013, 52, 1042–1055. [CrossRef]
7. Patrascu, M.; Sheintuch, M. On-site pure hydrogen production by methane steam reforming in high flux
membrane reactor: Experimental validation, model predictions and membrane inhibition. Chem. Eng. J.
2015, 262, 862–874. [CrossRef]
8. Koc, R.; Kazantzis, N.K.; Ma, Y.H. Membrane technology embedded into IGCC plants with CO2 capture: An
economic performance evaluation under uncertainty. Int. J. Greenh. Gas Control 2014, 26, 22–38. [CrossRef]
9. Ma, L.-C.; Castro-Dominguez, B.; Kazantzis, N.K.; Ma, Y.H. Integration of membrane technology into
hydrogen production plants with CO2 capture: An economic performance assessment study. Int. J. Greenh.
Gas Control 2015, 42, 424–438. [CrossRef]
10. Gallucci, F.; Paturzo, L.; Famà, A.; Basile, A. Experimental study of the methane steam reforming reaction in
a dense Pd/Ag membrane reactor. Ind. Eng. Chem. Res. 2004, 43, 928–933. [CrossRef]
11. Shu, J.; Grandjean, B.P.A.; Kaliaguine, S. Asymmetric Pd-Ag/stainless steel catalytic membranes for methane
steam reforming. Catal. Today 1995, 25, 327–332. [CrossRef]
12. Lin, Y.M.; Liu, S.L.; Chuang, C.H.; Chu, Y.T. Effect of incipient removal of hydrogen through palladium
membrane on the conversion of methane steam reforming: Experimental and modeling. Catal. Today 2003,
82, 127–139. [CrossRef]
13. Kikuchi, E.; Nemoto, Y.; Kajiwara, M.; Uemiya, S.; Kojima, T. Steam reforming of methane in membrane
reactors: Comparison of electroless-plating and CVD membranes and catalyst packing modes. Catal. Today
2000, 56, 75–81. [CrossRef]
14. Vásquez Castillo, J.M.; Sato, T.; Itoh, N. Effect of temperature and pressure on hydrogen production from
steam reforming of biogas with Pd-Ag membrane reactor. Int. J. Hydrog. Energy 2015, 40, 3582–3591.
[CrossRef]
15. Jorgensen, S.L.; Nielsen, P.E.H.; Lehrmann, P. Steam reforming of methane in a membrane reactor. Catal. Today
1995, 25, 303–307. [CrossRef]
16. Abu El Hawa, H.W.; Paglieri, S.N.; Morris, C.C.; Harale, A.; Way, J.D. Application of a Pd-Ru composite
membrane to hydrogen production in a high temperature membrane reactor. Sep. Purif. Technol. 2015, 147,
388–397. [CrossRef]
17. Uemiya, S.; Sato, N.; Ando, H.; Kikuchi, E. The water gas shift reaction assisted by a palladium membrane
reactor. Ind. Eng. Chem. Res. 1991, 30, 585–589. [CrossRef]
18. Bi, Y.; Xu, H.; Li, W.; Goldbach, A. Water-gas shift reaction in a Pd membrane reactor over Pt/Ce0.6 Zr0.4 O2
catalyst. Int. J. Hydrog. Energy 2009, 34, 2965–2971. [CrossRef]
19. Augustine, A.S.; Ma, Y.H.; Kazantzis, N.K. High pressure palladium membrane reactor for the high
temperature water-gas shift reaction. Int. J. Hydrog. Energy 2011, 36, 5350–5360. [CrossRef]
20. Mendes, D.; Chibante, V.; Zheng, J.-M.; Tosti, S.; Borgognoni, F.; Mendesa, A.; Madeira, L.M.
Enhancing the production of hydrogen via water-gas shift reaction using Pd-based membrane reactors.
Int. J. Hydrog. Energy 2010, 35, 12596–12608. [CrossRef]
21. Peters, T.A.; Stange, M.; Klette, H.; Bredesen, R. High pressure performance of thin Pd-23%Ag/stainless
steel composite membranes in water gas shift gas mixtures; influence of dilution, mass transfer and surface
effects on the hydrogen flux. J. Membr. Sci. 2008, 316, 119–127. [CrossRef]
22. Fernandez, E.; Helmi, A.; Coenen, K.; Melendez, J.; Viviente, J.L.; Tanaka, D.A.P.; van Sint Annaland, M.;
Gallucci, F. Development of thin Pd-Ag supported membranes for fluidized bed membrane reactors including
WGS related gases. Int. J. Hydrog. Energy 2015, 40, 3506–3519. [CrossRef]
23. Ma, Y.H.; Mardilovich, P.P.; She, Y. Hydrogen Gas-Extraction Module and Method Fabrication.
U.S. Patent 6,152,987, 28 November 2000.
Membranes 2016, 6, 44 18 of 18

24. Ma, Y.H.; Mardilovich, I.P.; Engwall, E.E. Composite Gas Separation Modules Having Intermediate Metal
Layer. U.S. Patent 7,175,694, 13 February 2007.
25. Ma, Y.H.; Guazzone, F. Method for Fabricating a Composite Has Separation Module. U.S. Patent 7,727,596,
1 July 2010.
26. Chen, C.-H.; Ma, Y.H. The effect of H2 S on the performance of Pd and Pd/Au composite membrane.
J. Membr. Sci. 2010, 362, 535–544. [CrossRef]
27. Brunetti, A.; Caravella, A.; Fernandez, E.; Pacheco Tanaka, D.A.; Gallucci, F.; Drioli, E.; Curcio, E.;
Viviente, J.L.; Barbieri, G. Syngas upgrading in a membrane reactor with thin Pd-alloy supported membrane.
Int. J. Hydrog. Energy 2015, 40, 10883–10893. [CrossRef]
28. Koc, R.; Kazantzis, N.K.; Ma, Y.H. A process dynamic modeling and control framework for performance
assessment of Pd/alloy-based membrane reactors used in hydrogen production. Int. J. Hydrog. Energy 2011,
36, 4934–4951. [CrossRef]
29. Ma, R.; Castro-Dominguez, B.; Mardilovich, I.P.; Dixon, A.G.; Ma, Y.H. Experimental and simulation
studies of the production of renewable hydrogen through ethanol steam reforming in a large-scale catalytic
membrane reactor. Chem. Eng. J. 2016, 303, 302–313. [CrossRef]
30. Bird, R.B.; Stewart, W.E.; Lightfoot, E.N. Transport Phenomena, 2nd ed.; John Wiley & Sons, Inc.: New York,
NY, USA, 2007.
31. Delgado, J.M.P.Q. A critical review of dispersion in packed beds. Heat Mass Transf. 2006, 42, 279–310.
[CrossRef]
32. Uemiya, S. State of the art of supported metal membranes for gas separation. Sep. Purif. Methods 1999, 28,
51–85. [CrossRef]
33. Gade, S.K.; Payzant, E.A.; Park, H.J.; Thoen, P.M.; Way, J.D. The effects of fabrication and annealing on the
structure and hydrogen permeation of Pd-Au binary alloy membranes. J. Membr. Sci. 2009, 340, 227–233.
[CrossRef]
34. McKinley, D.L.; Nitro, W.V. Method for Hydrogen Separation and Purification. U.S. Patent 3,247,648, 26
April 1966.
35. Gryaznov, V. Metal containing membranes for the production of ultrapure hydrogen and the recovery of
hydrogen isotopes. Sep. Purif. Methods 2000, 29, 171–187. [CrossRef]
36. Tong, J.; Matsumura, Y.; Suda, H.; Haraya, K. Experimental study of steam reforming of methane in a thin
(6 µM) Pd-based membrane reactor. Ind. Eng. Chem. Res. 2005, 44, 1454–1465. [CrossRef]
37. Atwood, K.; Arnold, M.R.; Appel, E.G. Water gas shift reaction: Effect of pressure on rate over an
iron-oxide-chromium oxide catalyst. Ind. Eng. Chem. 1950, 42, 1600–1602. [CrossRef]
38. Zhang, J.; Liu, D.; He, M.; Xua, H.; Li, W. Experimental and simulation studies on concentration polarization
in H2 enrichment by highly permeable and selective Pd membranes. J. Membr. Sci. 2006, 274, 83–91.
[CrossRef]
39. Battersby, S.; Teixeira, P.W.; Beltramini, J.; Duke, M.C.; Rudolph, V.; Diniz da Costa, J.C. An analysis of the
Peclet and Damkohler numbers for dehydrogenation reactions using molecular sieve silica (MSS) membrane
reactors. Catal. Today 2006, 116, 12–17. [CrossRef]
40. Li, A.; Liang, W.; Hughes, R. The effect of carbon monoxide and steam on the hydrogen permeability of a
Pd/stainless steel membrane. J. Membr. Sci. 2000, 165, 135–141. [CrossRef]
41. Rostrup-Nielsen, J.R.; Hansen, J.H.B. CO2 -reforming of methane over transition metals. J. Catal. 1993, 144,
38–49. [CrossRef]
42. Tong, J.; Matsumura, Y. Pure hydrogen production by methane steam reforming with hydrogen-permeable
membrane reactor. Catal. Today 2006, 111, 147–152. [CrossRef]
43. Chai, M.; Machida, M.; Eguchi, K.; Arai, H. Promotion of hydrogen permeation on metal-dispersed alumina
membranes and its application to a membrane reactor for methane steam reforming. Appl. Catal. A 1994,
110, 239–250. [CrossRef]
44. Madia, G.; Barbieri, G.; Drioli, E. Theoretical and experimental analysis of methane steam reforming in a
membrane reactor. Can. J. Chem. Eng. 1999, 77, 698–706. [CrossRef]

© 2016 by the authors; licensee MDPI, Basel, Switzerland. This article is an open access
article distributed under the terms and conditions of the Creative Commons Attribution
(CC-BY) license (http://creativecommons.org/licenses/by/4.0/).