Article

pubs.acs.org/IECR

Improved Performance of a PBM Reactor for Simultaneous CO2

Capture and DME Synthesis
Nazely Diban,*, Ane M. Urtiaga, Inmaculada Ortiz, Javier Erena, Javier Bilbao,
and Andres T. Aguayo

Department of Chemical and Biomolecular Engineering, University of Cantabria, Av. de los Castros s/n, 39005 Santander, Spain
Department of Chemical Engineering, University of Basque Country, Apdo. 644, E-48080 Bilbao, Spain

ABSTRACT: The use of nonideal zeolite membranes for the in situ H2O removal in a packed-bed membrane reactor (PBMR)
during the synthesis of dimethyl ether (DME) allows the recovery of CO2 but unexpectedly reduces DME yield by 50% in
comparison to a packed-bed reactor (PBR) as previously reported [Diban et al. Chem. Eng. J. 2013, 234, 140]. Due to the
advantageous performance of PBMR, the present work aims to the theoretical analysis and optimization of the working
conditions and system conguration that enhance both DME yield and CO2 recovery. Here, the previously developed
mathematical model able to predict the mass transport rate of all the components present in the reactive system through zeolite
membranes has been modied and accounts for the sweep gas recirculation. The inuence of the sweep gas ow-rate in the range
0.061.80 molCOxh1 (laboratory scale) and sweep gas recirculation factor (0 < < 1) has been analyzed. Sweep gas ow-rates
>0.18 molCOxh1 favored CO2 conversion but only partial recirculation of the sweep gas promoted DME yields beyond those
obtained in a PBR due to the synergism between eective H2O removal and MeOH retention in the feed side. Although
energetically challenging, these results show promising prospects to apply the existing zeolite membranes for the chemical
transformation of CO2 into DME on a large scale.

1. INTRODUCTION
The concerns on the global warming are stressing the interest
of the scientic community for CO2 capture and sequestration13 and the chemical valorization of CO2 into the synthesis
of valuable products, e.g., formaldehyde, acetic acid, propylene,
methanol (MeOH), or hydrocarbons, have been explored in
the literature.47 The synthesis of dimethyl ether (DME) is a
catalytic process with promising prospects for CO2 valorization
on a large scale.6 In addition to being a propellant and coolant,
DME has a broad range of applications as an alternative clean
fuel for diesel engines, a source of H2 for fuel cells and a key
intermediate for producing automobile fuels and raw materials,
e.g., olens and BTX aromatics.810
The catalytic synthesis of DME is industrially performed in
two steps; in a rst packed-bed reactor (PBR), syngas is
transformed into MeOH using a metallic catalyst and in a
subsequent PBR, MeOH is converted into DME on an acidic
catalyst. The set of chemical reactions that take place is
described below.
In the rst PBR:
hydrogenation of CO

CO + 2H 2 CH3OH

water gas shift (WGS) reaction

hydrogenation of CO2

H 2O + CO H 2 + CO2

CO2 + 3H 2 CH3OH + H 2O

The use of a bifunctional catalyst with metallic and acidic

functions allows the synthesis of DME in a single step PBR
with the benet of switching the equilibrium of the synthesis of
MeOH (eq 1) toward the dehydration of MeOH into DME
(eq 5) and consequently increasing the conversion of CO and
CO2 even working at higher temperatures and lower
pressures.11 This bifunctional catalyst promotes cofeeding of
CO2 with the syngas.
The conversion of the reactions of CO2 hydrogenation (eq
3) and MeOH dehydration (eq 5) are limited by the presence
of H2O in the reaction site, as previously seen during the
synthesis of DME using feed mixtures of CO2+H2 and CO
+CO2+H2.1214 Hence, the in situ H2O removal from the
reaction site with a H2O permeable membrane would enhance
CO2 conversion and DME yield. This strategy has been
experimentally tested for the FischerTropsch (FT) reaction
with zeolite membranes (ZSM5, Mordenite (MOR) and
Silicalite-1 (SIL)), providing successful results in terms of
product yields (Espinoza et al., 1999 and 2000; Rohde et al.,
2005, 2006 and 2008; Schaub et al., 2008).1520 Iliuta et al.21
have theoretically explored the eciency of a packed-bed
membrane reactor (PBMR) conguration in the synthesis of
DME considering an ideal H2O selective membrane under
dierent permeance properties. Among the dierent membrane
materials tested in the literature,22 only zeolite membranes
would withstand the high demanding operating conditions
(225325 C, 1040 bar) required during DME synthesis.

(1)
(2)
(3)

formulation of C1C10 paraffins (HC) (nondesired byproducts)

nCO + (2n + 1)H 2 CnH 2n + 2 + nH 2O, (1 nc 10)

(4)
Received:
Revised:
Accepted:
Published:

In the second PBR:

dehydration of MeOH to DME

2CH3OH CH3OCH3 + H 2O

(5)
2014 American Chemical Society

19479

September 16, 2014

November 12, 2014
November 24, 2014
November 24, 2014
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Table 1. Characteristic Dimensions of the Membrane Reactor, Catalyst Properties and Operational Conditions in the Feed and
Sweep Gas Streams Employed in the Simulations and Mass Transport Properties of Zeolite (ZSM5, MOR and SIL) Membranes
(250300 C)a
parameter

value
6.13 103
10 103
13 103
100
0.015
0.5
2000
2.4 103
1/7
3/1
0.06

eective membrane area, Am (m )

internal membrane support diameter (m)
external membrane support diameter (m)
selective layer thickness (m)
eective length of the xed-bed (m)
voidage of the xed-bed ()
catalyst density (kg/m3)
catalyst mass (kg)
catalyst mass dilution ()
b
reactants ratio in the feed and sweep gas streams (H2/COx)c
b
F
COx molar ow rate in the feed stream, FCO
(molCOxh1)
x,0
d

COx molar ow rate in the sweep gas stream, FCOx,FSG (molCOxh1)

0.061.8

feed and sweep gas stream pressure, PF and PS (bar)

reactor temperature, T (C)
operation time (h)
H2O permeance, 7H2O(mols1m2Pa1)

40
275
30
6.8 108

H2O/comp. i selectivity

SH2O/H2

SH2O/COe

SH2O/CO2

SH2O/MeOH

SH2O/DMEf

SH2O/HC

real zeolite membrane

ideal zeolite membrane

49
0.5

19.6

17.7

2.8

43.2

57.3

a
Determination of H2, CO, CO2, H2O, DME and HC properties by Espinoza et al.15,16 in multicomponent mixtures and MeOH properties by Piera
et al.25 in binary H2O/MeOH mixtures. bValues at the entrance of the PBMR. These variables change with the position. cCOx refers to the total
amount of CO and CO2 being the CO/CO2 molar ratio of 50%. dInitial values of molar ow rate in the sweep stream at the entrance of the PBMR
S
FCOx,FSG = FCO
. eValues only available at 350 C. fValue of permselectivity of C8 hydrocarbons. It was considered to be similar to DME
x,=Tao,t=0
properties.

smallest molecules (H2 and H2O) over the rest of molecules

present in the system. This type of zeolite membrane was
already reported as hydroxy sodalite (H-SOD)19,24 but it
presented low hydrothermal stability and thus it was
inapplicable in the present system.
Meanwhile this ideal and stable zeolite membrane is
developed, further assessment of the system aroused the
following question: Could the DME yield be enhanced by using
an operational approach, that is, the operational variables and
the system conguration, with the hydrothermally stable zeolite
membranes currently available? The present work aims at going
deeper into the evaluation of the present PBMR process and
the knowledge of the inuence of the ow rate and
recirculation of the sweep gas stream on the process
performance. The hypotheses to be demonstrated is how
these working conditions would minimize the driving force of
the mass transport of the reactants and intermediate products
from the feed toward the sweep gas side. Additionally, this work
intends to evaluate future experimental research priorities based
on the application of theoretical modeling tools for the
development of an ecient PBMR aimed at the chemical
valorization of CO2 into DME.

Particularly, the zeolite membranes applied by Espinoza et

al.15,16 under FT conditions for in situ H2O removal were
ZSM5, MOR and SIL and showed improved reaction
performance. Therefore, we theoretically evaluated in a
previous study23 the potential application of these zeolite
membranes in a catalytic PBMR for DME synthesis with CO2
cofeeding using a bifunctional catalyst CuO-ZnO-Al2O3/Al2O3. Interestingly, we observed that the DME yield was
importantly reduced when introducing these zeolite membranes to remove H2O from the feed stream. This low DME
yield was caused by the low selectivity of the zeolite membranes
that allowed not only the permeation of H2O but also of
reactants and intermediate products, mainly the intermediate
MeOH that could not be further converted into DME.
According to these results, it seems that the selectivity of the
membrane had a strong inuence on the viability of using a
PBMR to capture CO2 and to eciently valorise it into DME
under the simulated conditions. These results led to the logical
conclusion that research eorts should be directed toward the
improvement of the membrane H2O selectivity and to reduce
the mass transport of MeOH through the membrane. This
would be a challenging defy for zeolite membrane researchers.
Attending to the selectivity of the zeolite membranes evaluated
by Diban et al.,23 it is clear that their hydrophilic characteristics
were determinant in the transport mechanism of the
components (MeOH selectivity was similar to that of H2O
and higher than the selectivity of smaller molecules such as H2,
CO and CO2, see also selectivity values in Table 1). The
synthesis of a zeolite membrane with ideal H2O selectivity over
MeOH selectivity would require that the mass transport of the
molecules through the membrane proceeds according to a
sieving mechanism, thus favoring the permeation of the

2. MATHEMATICAL MODEL MODIFICATIONS

2.1. PBMR Working at Variable Gas Velocities. A
mathematical model describing the mass transport through a
hydrophilic membrane of the components involved in the
catalytic synthesis of DME from a feed mixture of CO/CO2/H2
in a PBMR with in situ H2O removal was developed in our
previous work.23 Briey, the mass transport conservation
equations for component i along the PBMR, with the axial
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position expressed in terms of space time, , are (I) in the feed

side
F

FCOx ,0
dFiF( )
F
+ ji ( ) A m
+ ri( ) FCO
=0
x ,0
d
Wcat

i;
(6)

(II) in the permeate side

F

FCOx ,0
dFiS( )
ji ( ) A m
=0
d
Wcat

i;

(7)

And the mass transport ux of the component i through the

membrane can be expressed as
ji ( ) = 7i(piF ( ) piS ( ))

i;

(8)

There, the simulations were conducted considering the

dimensions of a laboratory scale PBR (Table 1) that had been
previously employed to determine experimentally the equilibrium thermodynamics and kinetics of the DME synthesis with
a bifunctional CuO-ZnO-Al2O3/-Al2O3 catalyst.26,27 It must be
noted that the CO2 hydrogenation in eq 3 (section 1) is linearly
dependent on eqs 1 and 2 and thus, it has not been included in
the mathematical modeling of the process thermodynamics and
kinetics. The former reaction conditions together with the
boundary conditions have been used in the present work (for
further details, please see Diban et al.23). The mathematical
model in Diban et al.23 considered that the feed and sweep gas
streams, circulating counter-currently through the PBMR,
owed with constant feed and sweep gas ow velocities and
under plug ow conditions, the stream pressures were xed at
the entrance of the PBMR and suered a pressure drop with
the axial position according to the consumption of reactants
and formation of products and mass transport through the
membrane. However, industrially the pressure of the gas
streams is usually xed at the PBR exit while the velocity of the
gas stream is widely aected within the PBR axial position, in
particular when there is an important change in the total
number of moles during the reaction progress. It must be noted
that considering the particle size (>150 m) and the applied
gas ow rate, the pressure drop along the reactor is negligible
and thus, constant pressure through the PBMR length can be
assumed for both the feed and sweep gas streams. This was
conrmed by simulations using COMSOL software. Therefore,
in the present work, the simulation conditions were adapted to
describe a PBR with variable fed gas ow rate by changing the
complementary equations in the mathematical model developed by Diban et al.23 as follows
Q F( ) =

FiF()
i

Q S( ) =

FiS()
i

RT
PF

RT
PS

Figure 1. Diagram of a PBMR system with partial sweep stream

recirculation.

partial condensation of H2O (separation unit), partial vent and

refreshment of the sweep stream (mixer unit) and the elements
required to restore the sweep gas temperature and pressure
conditions necessary in the catalytic PBMR (compressor and
heater). It must be noted that the unit for H2O and MeOH
removal has been simplied to allow only H2O condensation in
order to focus on the eect of the working conguration on the
PBMR performance.
For the simulations, the mathematical model reported in
section 2.1 was used. Additionally, the mathematical description
of condenser and mixer units has been incorporated. Regarding
the condenser, 95% of H2O condensation was considered
(none of the other components were condensed), and thus,
only 5% of H2O remains in the dry sweep stream, FSi,dry, to be
recirculated, which is mathematically described as follows
for H 2O: FHS 2O,dry = 0.05 FHS 2O, = 0

(11)

for the rest of the components: FiS,dry = FiS, = 0

t , i H2O

FHS 2O,dry,

(12)

FSi,dry

with
and
corresponding respectively to the H2O
and component i molar ow rates in the recycled sweep stream
coming from the partially dehydrated sweep gas stream. The
subscript = 0 indicates the axial position at the entrance of the
feed stream to the PBMR that is the position where the sweep
stream exits the PMBR.
The mass balance in the mixer unit (Figure 1) is

(9)

FiS,recirculated = FiS,dry + (1 ) Fi ,FSG

(10)

i, t

(13)

where is the recirculation factor of the sweep gas stream

dened as the fraction of the molar ow rate of the sweep gas
stream that is recycled to the PBMR to the total molar ow rate
of the sweep gas stream. took values ranging from 0 for no
recirculation to 1 for total recirculation. Fi,FSG is the molar ow
rate of each component i in the fresh sweep gas (FSG) stream.
The FSG stream was formed only by H2/CO/CO2 and at t = 0
FSi,recircualted = Fi,FSG. Attending to Figure 1, it can be seen that
S
FSi,recircualted = Fi,=tao
, which is the boundary condition for the

2.2. PBMR with Sweep Gas Recirculation. Figure 1

shows a ow diagram of the catalytic PBMR with in situ H2O
removal for DME synthesis with CO2 cofeeding where the
sweep gas could be recirculated to the PBMR at will. The feed
and sweep streams circulated counter-currently and the feed
stream owed in single-pass mode, similarly as in section 2.1.
For the recirculation of the sweep gas, additional elements were
included in the process diagram (Figure 1) to prevent H2O
accumulation in the sweep gas. Those elements aimed at the
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real zeolite membrane previously considered (see characteristics in Table1) was also conducted.
2.4. Denition of the Process Performance Parameters. To evaluate the eectiveness of the recirculation of the
sweep gas stream in the catalytic PBMR on the process
performance, the conversion of CO2 (XCO2) and the yields of
the main product DME (YDME), the intermediate MeOH and
the byproduct HC (YMeOH and YHC, respectively) were dened
similarly to Rhode et al.19 in eqs 15 and 16. This denition
accounted both for component losses to the permeate side
and/or cofeeding to the feed side.

sweep gas stream at the entrance of the catalytic PBMR and at

any time t (being =Tao also the exit position of the feed
stream). The boundary condition at the entrance of the
catalytic PBMR for the feed stream is
FiF, = 0 = FiF,0

i, t

(14)

The set of equations in this section (eqs 1114) were added

to the mathematical model equations described in section 2.1
and in Diban et al.23 and were implemented in the simulation
software Aspen Custom Modeler v2004.1 (Aspen Technology,
Inc., Cambridge, Massachusetts U.S.A.).
The characteristic dimensions of the PBMR and operational
conditions employed in the simulations are summarized in
Table 1. The total pressure of the sweep gas, PS, was the same
as in the feed side, PF, to keep partial pressures of reactants
(H2/CO/CO2) similar in the feed and sweep gas sides, thus
minimizing the driving force of the mass transport of the
reactants and the consequent reactant losses to the sweep gas
side. The operational conditions of temperature, pressure and
reactants molar ratio in the feed stream were selected in order
to give the highest DME yields in a PBR with the bifunctional
catalyst CuO-ZnO-Al2O3/-Al2O3 according to previous
results.26,27 The operational variables studied were (i) the
molar ow rate of the FSG stream in terms of COx (CO +
CO2) composition,FCOx,FSG, and (ii) the recirculation factor, ,
of the sweep gas stream leaving the PBMR.
2.3. Membrane Characteristics. As previously indicated,
in the present application zeolite membranes were selected
because they could withstand with the demanding experimental
conditions used in the catalytic PBMR in the present
application (temperature of 275 C and pressure 40 bar).
Particularly, the zeolite materials ZSM5, MOR and SIL were
tested by Espinoza et al.15,16 for in situ H2O removal in a
PBMR conguration for FT reactions that employed operational conditions very similar to those used in a catalytic PBR
for DME synthesis. The inuence of the mass transport
properties of these zeolite membranes on the process
performance of the present system was evaluated theoretically
in Diban et al.23 Due to the poor fabrication reproducibility of
the zeolite membranes,28 it was reported that these membranes
presented a wide range of values of H2O permeance, 7H2O, and
H2O/component i selectivity, SH2O/i. Diban et al.23observed
that the use of real zeolite membranes with low 7H2O and high
SH2O/i led to important CO2 conversions in systems operating
in once-through mode and constant feed and sweep gas
velocities despite the yield of DME was reduced almost 50% in
comparison to that attained in a PBR. Therefore, the zeolite
membranes with low 7H2O and high SH2O/i characteristics (see
values in Table 1) were selected in the present work to address
the inuence of the recirculation of the sweep gas stream on the
process performance. It must be noted that the permeance
value used in Table 1 for DME was actually for C 8
hydrocarbons,15,16 and thus, the results herein presented are
considered a rst approximation. Due to the higher DME
polarity, water solubility, etc. in comparison to those
parameters for octane (C8), it is expected that DME permeance
would be higher than octane permeance. Finally, the simulation
of the PBMR performance with an ideal zeolite membrane
allowing only H2 and H2O permeance (size exclusion
mechanism hypothesis) with the same H2O permeance as the

i =

Yi =

FiF| = 0 FiF| = Tao ji A m

FiF| = 0 Ftmb, i

(15)

nci FiF| = Tao + nci ji A m

F
|
Ftmb,COx
FCO
x =0

(16)

if Ftmb, i 0 (reactant loss)

0

being Ftmb, i =

(ji A m ) if Ftmb, i < 0 (reactant cofeeded)

and Ftmb,COx
0

if Ftmb,COx 0 (reactant loss)

=
((jCO + jCO )A m ) if Ftmb,COx < 0 (reactant cofeeded)

It must be remarked that the process suers a slow catalyst

deactivation and thus, the conversion of reactants and the
product yields change with the time on stream. Therefore, the
reactant conversions and the product yield were average values
after 30 h of time on stream.
The selectivity to the production of DME regarding the
production of the organic products has been dened as follows
DME =

YDME
Yi

i = DME, MeOH and HC

(17)

3. SIMULATION RESULTS AND DISCUSSION

3.1. Inuence of the Sweep Gas Streamow Rate. In
Figure 2, the inuence of the sweep gas ow rate, FCOx,FSG, in
the range 0.061.8 molCOxh1 under once-through mode
operation, on the process performance (XCO2, YDME, YMeOH and
YHC) is depicted. It can also be seen that FCOx,FSG had a high
inuence on the process performance in the range 0.060.60
molCOx h1, whereas above 0.60 molCOxh1, an asymptotic
trend is observed. This was in agreement with the observations
of Rhode et al.,17,18 which reported higher XCO2 when
increasing the sweep gas molar ow rate in the PBMR
conguration with in situ H2O removal for FT synthesis. At
FCOx,FSG = 0.06 molCOxh1, the values of XCO2 were negative,
similarly to those of a PBR. This result is againts the hypothesis
that the in situ removal of H2O from the feed side in a PBMR
would favor the chemical capture of CO2. To understand better
why a PBMR with FCOx,FSG of 0.06 molCOxh1 resulted in CO2
formation, a detailed analysis of the eect of the sweep gas ow
rates on the concentration proles of H2O and CO2 in the feed
and sweep streams owing through the PBMR is presented in
Figure 3.
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Figure 2. Inuence of the sweep gas ow rate in the PBMR on the

process performance (CO2 conversion and products yields (DME,
MeOH and HC)). Comparison between the PBMR (solid color lines)
and a PBR (black dotted lines).

Figure 3. Inuence of the sweep gas ow rate, FCOx,FSG (0.06 and 0.60
molh1), on the partial pressure of the H2O in the feed (solid color
lines) and sweep gas (dotted color lines) sides and of the CO2 in the
feed side with the position, , in the PBR (black line) and PBMR
(color lines) at the time on stream of 30 h.

Figure 3a depicts the change of H2O partial pressure in the

feed and sweep gas sides within PBMR position, , at sweep gas
ow rates of 0.06 and 0.60 molCOxh1. This plot shows that at
FCOx,FSG = 0.06 molCOxh1 the sweep gas stream is rapidly
saturated with H2O at the entrance of the PBMR ( = 40 gcath
molCOx1) and the partial pressure of H2O in the feed side,PHF 2O,
remains very similar to that in a PBR, indicating that H2O is not
eectively removed from the feed side. According to eq 2, the
high H2O pressure displaced the WGS reaction toward the
formation of CO2 and caused that the partial pressure of CO2
in the feed side, pFCO2, was always above 5 bar (the initial value
in the entrance of the PBMR) in Figure 3b. When FCOx,FSG
increased, the H2O partial pressure dierence between the feed
and sweep sides, that is the driving force of the H2O mass
transport through the membrane, also increased. Therefore,
FCOx,FSG values higher than 0.06 molCOxh1 reduced signicantly the presence of H2O in the feed stream. To keep PFCO2
below 5 bar in Figure 3b and thus to achieve positive XCO2, it
was found in Figure 3a that the maximum PHF 2O allowable in the
feed side is 0.58 bar.
Regarding the product yield, it is observed in Figure 2a,b that
YDME decreased when FCOx,FSG increased in the range 0.061.80
molCOxh1, contrary to YMeOH and YHC trends. Particularly, at
low FCOx,FSG, the partial pressure of MeOH in the feed side,

pFMeOH, rose up to about 1.3 bar and decreased as FCOx,FSG

increased, as illustrated in Figure 4. The higher the values of
pFMeOH, the higher is the dehydration of MeOH into DME in eq
5. As it can be seen in Figure 4, pFMeOHreaches the highest value

Figure 4. Inuence of the sweep gas ow rate, FCOx,FSG (0.06 and 0.60
molh1), on the partial pressure of the MeOH in the feed (solid lines)
and sweep gas (dotted lines) sides with the position in the PBMR, , at
the time on stream of 30 h.
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Figure 5. Inuence of the recirculation factor, , and sweep gas molar ow rate in terms of COx composition, FCOx,FSG (0.18 and 0.60 molh1), on
(a) the CO2 conversion (XCO2), (b) DME yield (YDME), (c) MeOH yield (YMeOH) and (d) HC yield (YHC). The feed gas molar ow rate FFCOx,0 was
0.06 molh1.

at FCOx,FSG = 0.06 molCOxh1 because the dierence between

the feed and sweep MeOH pressures is the lowest at this sweep
gas ow rate and increases when increasing FCOx,FSG, similar to
what happened to the H2O partial pressures in Figure 3a. The
low selectivity of the zeolite membrane to MeOH with
SH2O/MeOH values around 2 (see Table 1) caused a high
permeation of MeOH from the feed toward the sweep side. To
favor higher YMeOH values, MeOH should be retained in the
feed side as much as possible and consequently, low values of
FCOx,FSG would be recommended. However, at low FCOx,FSG,
XCO2 are very low or even negative. The solution to this low
XCO2 values comes from using FCOx,FSG > 0.06 molCOxh1. To
enhance DME yields by minimizing MeOH losses from the
feed side when using FCOx,FSG > 0.06 molCOxh1, the
recirculation of the sweep stream according to the system
explained in section 2.2 is evaluated in section 3.2.
3.2. Inuence of the Sweep Gas Stream Recirculation.
Figure 5 shows the eect of the molar ow rate of the FSG
stream in the mixer unit, FCOx,FSG, between 0.18 and 0.60
molCOxh1, and the recirculation factor, , between 0 and 1, on
the average XCO2, YDME, YMeOH and YHC values after 30 h of time
on stream. The increase of the sweep gas molar ow rate

allowed higher XCO2 values, as it was already observed in oncethrough mode operations, thus favoring the CO2 capture in the
process. Albeit XCO2 remains almost independent of at
FCOx,FSG = 0.18 molCOxh1, at FCOx,FSG, =0.60 molCOxh1, XCO2
decreased 27% when increasing from 0 to almost 1. The
eciency of the H2O removal at high FCOx,FSG is much more
pronounced than at low FCOx,FSG; therefore, the eect of the
recirculation of sweep gas may aect more signicantly the
XCO2 results at high FCOx,FSG, values.
YDME values in Figure 5b increased always at increasing
while YMeOH decreased (Figure 5c). By increasing , the MeOH
concentration in the sweep gas stream increased reducing the
driving force for the MeOH mass transfer across the membrane
as expected. MeOH was then retained in the feed stream and
could be transformed into DME. This eect is better illustrated
in Figure 6. In this gure, the values of pFMeOH and pSMeOH along
the position of the PBMR, , are depicted for dierent
recirculation factors, , for FCOx,FSG of 0.18 molCOxh1. It is
clearly observed that the increase in the values of from 0 up
to 0.975, leads to a noticeable increase in the values of pFMeOH
and pSMeOH in the PBMR. Furthermore, the driving force for the
mass transfer of MeOH, that is the dierence between the
F
S
values of pMeOH
and pMeOH
, is signicantly reduced by
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Figure 7. Results of the simulation of CO2 conversion DME yield and

DME selectivity under PBR and PBMR with a real zeolite membrane
(i) without recirculation ( = 0), (ii) with high recirculation factor (
= 0.9) and (iii) PBMR with an ideal zeolite membrane without
recirculation ( = 0), at a sweep gas molar ow rate FCOx,FSG = 0.18
molh1. The feed gas molar ow rate FFCOx,0 was 0.06 molh1.

Figure 6. Inuence of the recirculation factor, , on the partial

pressures of MeOH in the feed, pFMeOH (solid line), and sweep streams,
PSMeOH (dotted line), with the position in the PBMR, , at the time on
stream of 30 h. The FSG molar ow rate in terms of COx composition,
FCOx,FSG was 0.18 molh1 and the feed gas molar ow rate FFCOx,0 was
0.06 molh1. The entrance of the sweep gas stream was on = 40 gcat
hmolCOx1. The eect of on PFMeOH was evaluated in comparison to
the PBR.

3.9% in a PBR to 8.2% in a PBMR working at 0.18 molCOxh1.

This was attributed to the reduction of the H2O content in the
feed side. The H2O removal improved simultaneously the CO2
conversion and the HC formation. This was in agreement with
the ndings by Sierra et al.10 that observed that cofeeding H2O
in the feed stream at 0.2 H2O/syngas molar ratio led to lower
deactivation by coke deposition due to a lower HC formation
in comparison with systems without H2O cofeeding. Despite
the high values of YHC, the DME in a PBMR with sweep gas
recirculation are still comparable to those in a PBR. However,
as it was previously explained, a high formation of paran
byproducts has to be avoided because not only it deactivates
the catalyst but also adds diculty to the ecient separation of
the desired DME from the gas streams exiting the PBMR.
Therefore, paran formation must be reduced.
Finally, the performance of a PBMR working with an ideal
zeolite membrane at a FCOx,FSG = 0.18 molCOxh1 and in oncethrough mode operation, is presented in Figure 7. It can be
seen that the PBMR at high recirculation factors simulate the
conditions to approach the performance results to that of a
PBMR that uses an ideal zeolite membrane. The quest for the
ideal zeolite membrane for selective H2O removal seems very
unrealistic as the hydrophilic character of the zeolite
membranes applicable in the present system also favor the
MeOH permeance in addition to that of H2O. At the sight of
these results, it seems that PBMRs working with low sweep gas
molar ow rates (FCOx,FSG, of 0.18 molCOxh1) and reasonable
recirculation factors ( = 0.9) resulted in a compromise among
the results of XCO2, YDME and DME. Furthermore, these
conditions reduce the consumption of reactants in the sweep
gas stream, soften the recirculation settings and therefore
reduce the costs of this stage. However, a detailed evaluation of
the costs and technical feasibility of this conguration must be
further addressed.
In dierent simulations, independently of the operation
conditions (pressure, ow rate, recirculation and ideal/real
membrane selectivity) the values of YDME and YMeOH reached
asymptotic values of 30 and 10%, respectively (data not
shown). However, XCO2 could increase up to values >80% at the
cost of the raise of YHC. Further enhancements of the process
performance (high XCO2 and YDME values and low YMeOH and

increasing . The lower driving force reduced considerably the

permeation of MeOH from the feed phase toward the sweep
side at higher values of and it is negligible in the case of =
0.975. It is worthy to note that at = 0.975, pFMeOH in the
PBMR reaches values similar to those found in a PBR.
The formation of the undesired paran byproducts has to be
taken into account seriously during the analysis of the process
performance. Figure 5d shows the high inuence that the sweep
gas ow rate exerted on YHC. The change in FCOx,FSG, from 0.18
to 0.60 molCOxh1 at = 0.975, almost doubled the value of
YHC (from approximately 8 to 15%) but the YDME change was
less noticeable (from 27 to 31%). The formation of HCs
provokes deactivation of the catalyst by coke deposition on the
active sites of the metallic function,29 limits the formation of
MeOH and hinders the selective recovery of DME from the gas
stream. Therefore, the formation of HCs should be minimized.
In Figure 7, a comparison of the values of XCO2, YDME and
DME between a catalytic PBR and a PBMR conguration under
dierent working conditions is presented. As it has been
previously indicated in section 3.1, a PBR under the operational
conditions of reactants composition, pressure and temperature
employed in the present work does not allow the conversion of
CO2 into products; instead, CO2 was formed (see the negative
values of XCO2). The use of a PBMR conguration at FCOx,FSG =
0.18 molCOxh1 gave positive XCO2 values around 25%. At this
sweep ow rate, the YDME in a PBMR increased from almost
18% by working without recirculation of the sweep stream ( =
0) to 26% using a recirculation factor = 0.9 and were always
higher than in a PBR (16%). The improvement in the YDME
was caused, as it was previously explained, by the increase of the
MeOH concentration in the recycled sweep stream that
reduced the driving force of MeOH transfer from the feed
side to the sweep side of the PBMR. This benetted the
conversion of MeOH into DME and thus YMeOH dropped from
approximately 29 to 11% and the DME selectivity DME
increased from 33 to 55%, similar to the SDME in a PBR. It is
important to remark the high increase of YHC, which rose from
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Industrial & Engineering Chemistry Research

Article

Notes

YHC) will inescapably pass through the improvement of the

characteristics of the bifunctional CuO-ZnO-Al2O3/-Al2O3
catalyst employed in the present system.

The authors declare no competing nancial interest.

ACKNOWLEDGMENTS
Financial support by postdoctoral grant JCI-2011-10994 from
the Spanish Ministry of Science and Innovation and by projects
CTQ2008-00690, CTQ2010-19188 and ENE2010-15585 is
kindly acknowledged.

4. CONCLUSIONS
The present work aims at demonstrating the CO2 capture and
recovery in the DME synthesis performed in a packed bed
catalytic membrane reactor (PBMR) that incorporates a zeolite
membrane for in situ H2O removal. While in the traditional
packed bed reactor (PBR) CO2 was formed, the zeolite
membrane of the PBMR allowed in situ H2O removal from the
feed side and therefore the water gas shift (WGS) reaction was
displaced toward CO2 conversion. However, the low selectivity
of the zeolite membranes toward H2O permeation could cause
an important reduction of the DME yield in comparison to that
obtained in a PBR depending on the working conditions.
In this work, it is concluded that a wise conception of the
operational conditions such as the control of the sweep gas ow
rates and the recirculation of the sweep gas stream could
overcome the practical limitations on building an ecient
PBMR for CO2 transformation into DME, given the diculty
to produce a hydrophilic zeolite membrane with selective
characteristics similar to those of an ideal membrane and
hydrothermally stable. The PBMR conguration proposed in
the present work gives the following outstanding advantages
that make the PBMR conguration to surpass the PBR
performance: (1) Increases the conversion of CO2 up to 85%
when high sweep gas molar ow rates (FCOx,FSG > 0.60 molCOx
h1) are employed. (2) The recirculation of the sweep gas
stream reduces the loss of MeOH across the membrane toward
the sweep gas side due to a reduction of the MeOH driving
force, and thus the yield of DME obtained in the PBMR can
reach values around 30% at high recirculation factors. The
values of YDME in the PBMR were always higher than those
achieved in a PBR (16.3%) and similar DME (55%). (3) The
recirculation of the sweep gas stream allows for savings in the
consumption of reactants (H2/CO/CO2).
In summary, the strategic design of the operational mode in a
PBMR would favor the presence of the same components in
the feed and sweep gas side, leading to a minimization of the
driving force of the mass transport through the membrane and
thus, would allow a higher conversion of reactants (mainly H2
and CO2) and intermediate products (MeOH) toward the
aimed DME in the feed side of the PBMR.
A careful evaluation of the technical diculty of the
recirculation and the high costs associated with the energy of
cooling, heating and compressing the sweep gas stream must be
done. Anyway, although challenging, the quest for a stable and
H2O selective membrane still remains the preferable option.
Additionally, a yield of the byproduct parans (HCs) higher
than 4% is not acceptable in this system. The formation of HCs
promotes the catalyst deactivation by coke deposition and
hinders the MeOH formation. Attending to the results of the
simulations in the present work, further improvements of the
catalyst selectivity to reduce the formation of HCs becomes a
research priority to improve the process eciency and
therefore, this study is currently in progress.

NOMENCLATURE
Am = eective membrane area (m2)
F = molar ow rate (mol h1)
Ftmb = transmembrane ux in eqs 12 and 13 (mol m2 h1)
j = membrane partial ux dependent on time and space time
(module position) (mol m2 h1)
nc = number of carbon atoms in each component
p = partial pressure (bar)
P = total pressure (bar)
Q = volumetric total ow rate (m3 h1)
r = reaction rate (mol.h1.(g of catalyst)1)
R = ideal gas constant (bar m3 mol1 K1)
S = membrane permselectivity (dimensionless)
t = time (h)
T = temperature (K)

Greek Letters

= recirculation factor
DME = selectivity of the process to the formation of DME
= space time ((g of catalyst)hmolCOx1)
Y = products yield (%)
X = reactants conversion (%)

Other Symbols

7 = membrane permeance (units in the model, molbar1

m2h1; units in the text, molPa1m2s1)

Subscripts

CO = carbon monoxide
CO2 = carbon dioxide
COx = sum of CO and CO2 reactants
DME = dimethyl ether
dry = fraction of the sweep gas after partial H2O
condensation in Figure 1
FSG = fresh sweep gas (new sweep gas introduced in the
mixer unit in Figure 1)
HC = hydrocarbons (parans)
H2 = hydrogen
H2O = water
i = component (reactant or product)
MeOH = methanol
recirculated = stream leaving the mixer unit in Figure 1 that
enters the PBMR
Tao = feed stream exit position
0 = initial
Superscripts

F = feed side
S = sweep gas or permeate side

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AUTHOR INFORMATION

Corresponding Author

*N. Diban. E-mail: dibann@unican.es.

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