i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 2 ( 2 0 1 7 ) 6 7 7 1 e6 7 8 6

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Selective membrane application for the industrial

one-step DME production process fed by CO2 rich
streams: Modeling and simulation

Marcello De Falco a,*, Mauro Capocelli a, Angelo Basile b

a
Unit of Process Engineering, Department of Engineering, Universita 

Campus Bio-Medico di Roma, via Alvaro del
Portillo 21, 00128, Rome, Italy
b
Institute on Membrane Technology of National Research Council (ITM-CNR), Via P. Bucci Cubo 17/C, c/o University
of Calabria, Rende, CS, 87036, Italy

article info abstract

Article history: The integration of a microporous zeolite membrane, highly selective to steam water in a
Received 10 October 2016 one-step DME synthesis reactor, is modeled and assessed. The membrane reactor perfor-
Received in revised form mance and the comparison with a conventional reactor, are studied mainly for a CO2-rich
17 January 2017 feedstock, i.e. derived from a biogas-derived syngas. The continuous removal of water from
Accepted 7 February 2017 the reaction environment reduces the inhibition effect of H2O on the CO2 hydrogenation
Available online 2 March 2017 and methanol dehydration reactions, thus allowing the achievement of high conversions,
DME yield and selectivity even at large CO2 composition in the inlet feedstock. If a CO2/CO
Keywords: ratio equal to 3 is imposed in the inlet stream, the DME yield reaches a value of 0.75 vs. 0.57
Membrane reactor in a conventional reactor operating at the same conditions, the XCOx and XCO2 are 0.75 and
Selective membrane 0.69, with an improvement of 15.4% and 30.2%, and the DME selectivity is close to 1.
One-step DME synthesis The membrane reactor behavior is assessed by a one-dimensional, non-isothermal
Hydrogen model. Fixing industrial scale parameters, the effect of the main operating conditions as
Reactor modeling temperature and pressure in the reactor environment, the Gas Hourly Space Velocity
(GHSV), the feedstock composition in terms of CO2/CO and H2/COx ratios, the pressure and
flow rate downstream to the selective membrane are analyzed and discussed.
The simulations confirm the improvement of the reactor performance, within large
ranges of operating conditions, derived from the integration of the selective membrane. On
this basis, membrane reactor for one-step DME synthesis process can be included in the
“CO2 valorization” framework since the greenhouse gas CO2 can be used as a reactant in an
industrial process and thus converted into a useful and marketable product.
© 2017 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

* Corresponding author.
E-mail address: m.defalco@unicampus.it (M. De Falco).
http://dx.doi.org/10.1016/j.ijhydene.2017.02.047
0360-3199/© 2017 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
6772 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 2 ( 2 0 1 7 ) 6 7 7 1 e6 7 8 6
Introduction
Dimetyl Ether (DME) is an organic compound mainly used as
aerosol propellant and as a reagent in the chemical industry for
the synthesis of widely applied products as the dimethyl sulfate
(a methylating agent), methyl acetate and light olefins [1,2].
Moreover, its handling characteristics similar to those of lique-
fied petroleum gas (LPG) as well as its excellent combustion
properties (cetane number ¼ 55e60) make the DME a promising
alternative fuel for the compression-ignition engines [3]. Feeding
an engine with a blend of diesel and DME with a content of
10e30% vol. leads to an enhancement of the cetane number, C/H
ratio and oxygen content with favorable effects on the combus-
tion characteristics and, consequently, with a reduction of smoke
(60% and more), NOx (15% approx.) and CO2 (20% approx.)
emissions, with a little penalty on CO and HC emissions [4].
This new and promising DME application has led to a
growing interest on DME industrial production: the projected
value of DME market is 9.7 bln USD by 2020, with a yearly
growth of 19.65% between 2015 and 2020 [5].
DME is traditionally produced by two methods [6,7]:
 The indirect method (two-steps configuration). It consists
in two steps: firstly, methanol is produced from a synthesis
gas (CO þ CO2 þ H2), generated from natural gas, coal or
biomasses; then, the methanol stream is de-hydrated
producing DME.
 The direct method (one-step configuration), where meth-
anol and DME production occurs simultaneously in a
reactor packed with a bi-functional catalyst as Cu-ZnO-
Al2O3/HZSM-5 [8] or physically mixed catalysts (Cu-ZnO-
Al2O3 for methanol synthesis and Cu-ZnO-HZSM-5 for
methanol dehydration).
For a large scale production, the direct method has to be
preferred considering the lower cost, compactness and higher
productivity [3].
The DME direct synthesis process is composed by the
following main reactions [9]:
CO2 hydrogenation: CO2 þ 3H2 4 CH3OH þ H2O
DHo ¼ 49.4 kJ/mol
CO hydrogenation: CO þ 2H2 4 CH3OH DHo ¼ 90.4 kJ/mol (2)
Water-gas shift: CO þ H2O 4 CO2 þ H2 DHo ¼ 41.0 kJ/mol (3)
Methanol dehydration: 2CH3OH 4 CH3OCH3 þ H2O
DHo ¼ 23.0 kJ/mol
Overall reaction: 3CO þ 3H2 4 CH3OCH3 þ CO2
DHo ¼ 258.3 kJ/mol
Reactions producing undesired by-products as C1eC10
paraffins, formaldehyde, formic acid and ethanol are
neglected. Among the 5 reactions, only 3 are independent: the
reactions scheme imposed in the following is composed by
CO2 hydrogenation (1), water-gas shift (3) and methanol
dehydration (4) reactions.
All reactions are exothermic and the process is thermo-
dynamically feasible at low temperature and high pressure.
Clearly, increasing the hydrogen content in the inlet stream
has a positive effect on reaction (1) conversion and, as a
consequence, on the DME production from reaction (4), while
it supports the reaction (3) towards the opposite direction
(reverse Water Gas Shift, r-WGS).
The one-step process is fed by a synthesis gas stream
composed by CO, CO2 and H2. The synthesis reactor can be
realized by three configurations:
-) a fixed bed reactor, where bi-functional catalyst particles
are packed in a adiabatic or isothermal tubular reactor [10];
-) a slurry reactor, where synthesis gas is dispersed as
bubbles in a solvent with suspended catalyst particles
[11e16];
-) a fluidized bed reactor, where catalyst particles are fluid-
ized by the reactant updraft stream [17].
From an industrial point of view, the fixed bed solution is
traditionally preferred thanks to the lower cost and easiness
in the reactor management.
The process performance is quantified by the CO2, COx and
H2 conversions (XCO2, XCOx, XH2), the DME yield (YDME) and the
DME selectivity (SDME), defined as follow:
Fin;CO2  Fout;CO2
XCO2 ¼ CO2 conversion (6)
Fin;CO2
Fin;CO þ Fin;CO2  Fout;CO  Fout;CO2
XCOx ¼ COx conversion (7)
Fin;CO þ Fin;CO2
Fin;H2  Fout;H2
XH2 ¼ H2 conversion (8)
Fin;H2
2Fout;CH3 OCH3
YDME ¼ DME yield (9)
Fin;CO þ Fin;CO2
2Fout;CH3 OCH3
SDME ¼ DME selectivity (10)
(1) 2Fout;CH3 OCH3 þ Fout;CH3 OH
where Fin,i and Fout,i are the inlet and outlet flow rates of i-
component, respectively.
Regardless of the reactor configuration, a thermodynamics
analysis of the global process [18] demonstrates that the in-
crease of CO2 content in the feedstock leads to a reduction of
DME yield (YDME, refer to eq. (9)): at 250  C, 50 bar and a ratio H2/
CO ¼ 2 in the inlet stream, the DME yield is 70% if no CO2 is fed to
the reactor, 37% if the CO2/CO ratio in the feedstock is equal to 1,
22% if it is equal to 2. This behavior has been experimentally
(4)
confirmed by Chen et al. [19], which has tested a bi-functional
Cu-ZnO-Al2O3/ZSM5 catalyst for the one-step DME synthesis
(5) process and obtained a strong negative influence of CO2 inlet
content on the DME production performance. The kinetics and
thermodynamics inhibition effect of CO2 on DME production is
also confirmed by many other scientific papers [20e24].
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 2 ( 2 0 1 7 ) 6 7 7 1 e6 7 8 6
The main reason of such a negative effect of CO2 on DME
yield is due to the WGS reaction (3): increasing the CO2 con-
centration leads to the promotion of the r-WGS causing a
H2O accumulation in the reaction environment with a
detrimental effect on the CO2 hydrogenation (1) and methanol
dehydration (4).
But, finding innovative configurations able to increase the
DME yield in the synthesis process fed by CO2-rich streams
would allow to include the one-step DME production process
in the context of “CO2 valorization technologies” [25], meaning
those technologies able to convert the greenhouse gas CO2
into useful and marketable products.
A promising solution is the integration of a H2O selective
membrane in the DME synthesis reactor, in a configuration
called membrane reactor [26e30]: removing the steam water
from the reaction environment allows the promotion of re-
actions (1) and (4) even if the r-WGS is supported by the high
CO2 content, thus leading to high CO2 conversion and high
DME yield and selectivity.
In the following, an analysis of the potential selective
membranes to be integrated in a DME synthesis membrane
reactor is reported and discussed and a proper membrane is
selected.
Hydrophilic membranes and membrane reactor
state-of-the-art
The hydrophilic membrane to be integrated has to have the
following properties:
-) stability at the DME production operating temperature and
pressure (200e300  C, 30e70 bar);
-) highly selective to water steam;
-) with high water steam permeability, leading to a high
permeated flux.
Conventionally, water selective membranes are applied in
the desalination processes, the dehydration of natural gas or
air and dehydration of organic compounds by pervaporation.
All these processes operate at low temperature (<150  C),
while, to be applied in the DME production process, the se-
lective membrane has to be able to operate at
temperatures > 200  C. But, the number of hydrophilic mem-
branes developed for such operating temperatures are
limited. High temperature hydrophilic membranes can be
classified in three different categories [31]:
 Microporous zeolite membranes, composed by a crystal-
line structure with a uniform pores distribution. They have
been largely tested [32e36] since zeolite-based membranes
show the best behavior in terms of H2O/H2 selectivity, H2O
permeability and thermal and mechanical stability at high
temperatures. Their hydrophilicity typically increases
decreasing the Si/Al ratio in the material lattice, even if at
low Si/Al ratio the membranes undergo a decay of stability
at low pH environment.
 Amorphous microporous membranes, which are charac-
terized by low permeability (<107 mol s1 m2 Pa1) and
6773
low H2O/H2 selectivity (<10) at temperatures > 200  C [37],
making them unsuitable for DME synthesis application.
 Polymeric membranes, which are characterized by a
degraded performance when the temperature increases
from 50 to 200  C (permeability equal to 4$107 mol
s1 m2 Pa1 at 50  C and to 4$108 mol s1 m2 Pa1 at 200  C;
H2O/H2 selectivity equal to 250 at 50  C and 18 at 200  C [38]).
Therefore, the only membranes suitable for integration in a
DME production reactor, operating at 200e300  C, are the
microporous zeolite ones. According to [31], which reviews the
H2O selective membranes for a similar application
(FischereTropsch synthesis with in situ H2O removal), zeolite
membranes can reach a H2O permeance within the range
107e106 mol s1 m2 Pa1 and a H2O/H2 selectivity > 10 at a
temperature of 250  C.
Some papers on membrane reactors application for DME
synthesis process are reported in the literature. Samimi et al.
[39] proposed a spherical packed bed membrane reactor for
methanol dehydration reaction (two-step configuration). The
integrated selective membrane is a hydroxy sodalite mem-
brane (H-SOD), a zeolite membrane with good thermal and
mechanical stability, 100% selectivity to water and maximum
H2O permeability ¼ 106 mol/(s m2 Pa) [40,41]. The simulation
study reports a methanol conversion improvement in respect
to a traditional reactor of 2.5% approximately. Iliuta et al. [42]
assessed the behavior of a membrane reactor for one-step
DME synthesis by a one-dimensional dynamic and
isothermal mathematical model, confirming the significant
increase of DME yield and selectivity if the selective mem-
brane H2O permeance is >107 mol s1 m2 Pa1. Marandpour
et al. [43] proposed a different DME direct production mem-
brane reactor, in which a Pd-based hydrogen selective mem-
brane is integrated in order to uniformly distribute the
reactant hydrogen inside the reactor, thus achieving im-
provements in DME production and CO-CO2 conversion. Sea
et al. [44] applied a alumina-silica membrane in a methanol
dehydration reactor, reaching a water/methanol selectivity
equal to 8.4, a water permeance of 107 mol s1 m2 Pa1 and a
CH3OH conversion of 82.5% versus 68% of a traditional reactor.
Volkov et al. [45] experimentally assessed the behavior of a F-
4SF (Nafion)/ceramic composite membrane integrated in un
fixed bed reactor for methanol dehydration, achieving a 100%
water selectivity and methanol conversion of 37% at the
operating conditions tested. Farsi and Jahanmiri [46] declare
that, from a modeling point of view, one-dimensional (fixed
tubular bed axial direction) and two-dimensional (both axial
and radial directions) models give similar simulation results
on membrane reactor behavior. Their study was focused on
the use of a alumina-silica composite membrane with a water
permeability of 1.14$107 mol s1 m2 Pa1 and a water/
methanol selectivity of 8.4 at 250  C for a fixed bed methanol
dehydration reactor (two-steps configuration): they obtained a
CH3OH conversion improvement from 81% (without selective
membrane) to 84% (with selective membrane).
From the study of the literature, it is clear how the selective
membrane integration leads to stronger reactor performance
improvement when it is applied in a one-step process.
In the following, a one-dimensional, non-isothermal
model for one-step DME production membrane reactor is
6774 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 2 ( 2 0 1 7 ) 6 7 7 1 e6 7 8 6
formulated with the scope to assess the reactor behavior
improvement if a CO2 rich stream is fed. The effect of the main
operating parameters as the Gas Hourly Space Velocity
(GHSV), the temperature and the pressure in the reactions
environment, the feedstock composition and the pressure and
flow-rate downstream to the selective membrane is assessed
and discussed imposing industrial operating conditions.
Then, a preliminary membrane reactor design is proposed and
compared with a traditional reactor.
Only Diban et al. [47,48] focused their efforts on the
assessment of the performance of a membrane reactor fed by
a CO2-rich stream and on the potentiality of DME one-step
production process as a “CO2 valorization” application. How-
ever, their works simulate a isothermal and isobaric lab-
scaled reactor, while it is well-known that the temperature
and pressure profiles strongly influence the membrane
reactor behavior, mainly for industrial applications [49,50].
Moreover, in this work the microporous zeolite selective
membrane permeability dependence on the temperature is
included, which also affects the final results as better
explained in the Results and comments paragraph. Finally, in
Ref. [48], only the effects on the reactor behavior of the sweep
gas molar flow-rate and of the recirculation factor of the
sweep gas stream leaving the membrane reactor are assessed,
while in this work also the other main process operating
conditions (gas velocity, temperature and pressure, feedstock
compositions) are simulated within wide ranges in order to
define a set of optimal operating parameters.
Process description
Fig. 1 illustrates a block diagram of the membrane reactor
based DME synthesis process, composed by:
 the membrane reactor, where the reactants are fed to the
reaction zone and a sweep gas to the permeation zone. The
sweep gas is a stream of CO2 (differently from Diban et al.
[47] and to Iliuta et al. [42], which impose a H2/COx (COx is
the sum of CO and CO2) mixture with the same ratio than in
the reactor feedstock), operating in a closed loop and which
Fig. 1 e Block scheme of the one-step DME production process with a membrane reactor and a CO2 closed loop as sweep gas
in the permeation zone.
allows an easy separation by condensation between the
sweep gas and the permeated water steam.
 the gas separation unit, where the incondensable compo-
nents (CO, CO2 and H2) are separated from the condensable
ones (methanol, DME and water);
 a first distillation step, where DME is separated from
methanol and H2O;
 a second distillation step, where the produced methanol is
recovered.
A sketch of the membrane reactor for the DME direct
synthesis is shown in Fig. 2. It is a tubular fixed bed reactor
composed by two co-axial tubes [49,50]:
 the internal tube is the H2O selective microporous zeolite
membrane, through which the steam permeates to the
inner section (Permeation Zone) where a sweep gas (CO2) is
sent to carry out the permeated flux;
 the external tube is a metallic tube in contact with a service
fluid (saturated water) able to remove the heat generated
by the exothermic reactions. During the heat removal, a
pressurized steam is generated. The annular zone between
the internal and external tubes is the Reaction Zone where
the catalyst particles are packed.
The use of CO2 as sweep gas depends on the membrane
selectivity: if a significant amount of hydrogen permeates
through the membrane, the sweep gas purification process is
much more difficult and expensive, since it would require a
H2/CO2 separation unit as well. This aspect is considered and
assessed in the process simulations reported in the next
paragraphs.
Concerning with the selective membrane to be integrated
in the reactor, as aforementioned the microporous zeolite
membranes are the best solution for applications at high
temperatures (>200  C) since they can achieve a H2O per-
meance within the range 107e106 mol s1 m2 Pa1 and a
H2O/H2 selectivity >10 at 250  C [31].
Among the zeolite membranes tested in the literature, the
most interesting for the DME synthesis operating temperature
range (200e300  C) are:
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 2 ( 2 0 1 7 ) 6 7 7 1 e6 7 8 6 6775

Fig. 2 e Membrane Reactor layout for DME production process.

 ZSM5/MFI membrane [51], a medium pore zeolite

(0.51  0.55 nm, 0.53  0.56 nm) with a water steam perme- dF_ H2

ability of 5$107 mol s1 m2 Pa1, 4$107 mol s1 m2 Pa1 ¼  rc ð1  εÞ$p R2e  R2i $ð3r1  r2 Þ  JH2 $2pRi (12)
dz
and 1.5$107 mol s1 m2 Pa1at 200  C, 250  C and 300  C,
respectively, and a corresponding H2O/H2 selectivity of 50, 30 dF_ CO

and 6. ¼  rc ð1  εÞ$p R2e  R2i $ðr2 Þ (13)
dz
 Mordenite (MOR) based membrane [52], a large pore zeolite
(0.65  0.70 nm, 0.26  0.57 nm) tested up to 255  C and with dF_ CO2

¼  rc ð1  εÞ$p R2e  R2i $ðr1  r2 Þ (14)
an average water permeability and water to hydrogen dz
selectivity of 3$107 mol s1 m2 Pa1 and 20, respectively,
within the range 200e250  C. dF_ CH3 OH

¼ rc ð1  εÞ$p R2e  R2i $ðr1  2r3 Þ (15)
dz
In the following, the ZSM5/MFI is selected for the integra-
tion in the DME production reactor. dF_ C2 H6 O

¼ rc ð1  εÞ$p R2e  R2i $ðr3 Þ (16)
A rigorous one-dimensional, non-isothermal mathemat- dz
ical model of the membrane reactor is formulated and where rc is the ratio of mass catalyst on the reaction volume
described. By the model, the chemical reactions conversion (catalyst density), r1, r2, r3 are the rates of the reactions (1), (3)
and the DME yield and selectivity are evaluated varying the and (4), respectively, Re and Ri are the external and internal
main process operating conditions. tubes radii and 3 is the void fraction in the catalyst bed. The
reaction rates for methanol synthesis, water gas-shift and
methanol dehydration on the bi-functional catalyst are
Mathematical modeling described by eqs. (17e19) [17], neglecting the absorption of
water and methanol:
The steady-state mass, energy and momentum balance
  
equations for the membrane fixed bed reactor are formulated PCO2 PH2 1  PCH3OH PW Keq1 PCO2 P3H2
assuming a 1-D plug-flow, meaning that the axial mass and r1 ¼ K1

3 (17)
1 þ KCO2 PCO2 þ KCO PCO þ √ KH2 PH2
heat dispersion are assumed negligible due to the high Gas
Hourly Space Velocity (GHSV, refer to eq. (32)) and to the
 
reactor length to diameter ratio always >25. The reactor PW  PCO2 PH2 Keq2 PCO
r2 ¼ K2

 (18)
(retentate compartment, reaction zone) is packed with bi- 1 þ KCO2 PCO2 þ KCO PCO þ √ KH2 PH2
functional catalytic particles of Cu-ZnO-Al2O3/HZSM-5. The
 2 
catalyst de-activation phenomena are neglected in this phase, PCH3OH PCH3OCH3
r3 ¼ K3  (19)
also because the water removal through the membrane allows PW Keq3
to reduce the de-activation effect on reactor performance. The
where Pj represents the partial pressures of the jth component
solidegas phases are described through pseudo-
(j ¼ H2O, H2, CO, CO2, CH3OH, DME) in the gaseous mixture
homogeneous modeling, by which the gas and solid inside
calculated according to the Dalton law, K1 , K2 and K3 are the
the reactor are considered as a one single phase. The mass
kinetic constants and Kj the Langmuir adsorption kinetic
balances of the six components for the fixed bed side are
constants of the respective compounds on the catalyst [53,54],
expressed by eqs. (11e16). The trans-membrane molar fluxes
calculated in function of the operating temperature according
for hydrogen and water are indicated as JH2 and JH2O.
to the Arrhenius' law. Coefficient for the calculation of kinetic
dF_ H2 O
 and adsorption constant are reported in a previous work of the
¼ rc ð1  εÞ$p R2e  R2i $ðr1  r2 þ r3 Þ  JH2 O $2pRi (11) authors [18]. The trans-membrane molar flux for hydrogen
dz
6776 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 2 ( 2 0 1 7 ) 6 7 7 1 e6 7 8 6

and water is proportional to the partial pressure difference kw is the wall conductivity, L the reactor length, D0 and Di the
across membrane and to the permeability according to: external and internal pipe diameter of the external tube and
  A0 and Ai the cross flow areas. The heat transfer coefficient
JH2 ¼ PermH2 pH2  pH2 (20)
between the gaseous phase and the tube wall hi is calculated
  through eq. (27) from Li-Finlayson [57]:
JH2 O ¼ PermH2 O pH2 O  pH2 O (21)
 1
lg Pr 3
where p and p are the partial pressure in the retentate and hi ¼ 0:17$ $ $Re0:79 (27)
dp 0:7
permeate sides, respectively, and PermH2 and PermH2O are the
permeabilities across the membrane of hydrogen and water where lg is the gas mixture conductivity, dp the catalyst par-
steam, respectively. The dependence of water and hydrogen ticle diameter, Re and Pr are the Reynolds and Prandtl
permeabilities on the temperature has been obtained inter- dimensionless numbers, respectively.
polating the experimental data for a ZSM5/MFI membrane The heat transfer coefficient in the shell side is expressed
reported in Ref. [51]. The selectivity of the membrane to the by eq. (28) [58]:
other components involved in the reactions (CO, CO2, meth-  0:4
P0
anol and DME) is neglected. h0 ¼ 7:96 ðT  Tv Þ3 (28)
Pa
In similarity, the conservation of species in the permeate
side (permeation zone) can be written as in eqs. (22e23) where where Po is the outside pressure (in the shell side) and Pa the
the spatial derivate for the other molar fluxes is equal to zero: atmospheric pressure.
The reactor modeling is completed with eq. (29), which
dF_ H2 O represents the momentum balance based on the character-
¼ ±JH2 O $2pRi (22)
dz istics of the mixture, the geometry of the reactor and the
catalytic bed in order to evaluate the pressure drop resulting
dF_ H2 from the Ergun equation for spherical particles [59]:
¼ ±JH2 $2pRi (23)
dz
where the sign ± depends on the co-current (þ) or counter- dP 150 m ð1  εÞ2 v 1:75 ð1  εÞr v2
¼ þ (29)
current () configuration of the reactant and sweeping dz ε dp
2 2 ε3 dp
streams fed to the reaction and permeation zones, respec-
The physical properties of the gaseous mixture (viscosity,
tively, according to the layout shown in Fig. 2.
the density, the specific heat and the thermal conductivity)
The cooling of the catalytic tubes takes place by means of
were calculated via the methods of Reid et al. [60] and are
natural circulation of boiling water between the steam drum
reported in Annex 1 - Physical properties. The set of ODEs
and the reactor. The exit stream is sent to the DME and
(11e16, 22e24, 29) are implemented in MatLab code and are
methanol purification sections and the system allows to
solved through the Runge-Kutta-Fehlberg method for the
exploit the enthalpy of exothermic reactions by producing
simulation of the fixed bed reactor defining the reactor
mediumehigh pressure steam also used for the feed pre-
configuration and the initial condition at z ¼ 0. In the next
treatment (e.g. steam reforming of natural gas).
section, the effects of the main reaction and permeation zones
The heat balance inside the reactor, neglecting the heat flux
operating conditions on the membrane reactor performance
from the reaction zone to the permeation zone, is written
are quantified and assessed.
through eq. (24) where and DHri is the heat of reaction and Hmix is
the enthalpy of the gas mixture that can be written in relation to
the temperature inside the reactor T as showed in eq. (25):
Results and comments
!
dHmix X
nr



¼  DHri ðTÞ ri $rc $ð1  εÞ$p$ R2e  R2i For the membrane reactor simulation, the operating condi-
dz i¼1
tions and properties of a conventional industrial DME fixed
 U ðT  Tv Þ$2pRe (24) bed reactor are imposed, as summarized in Table 1 [18].
Permeation zone operating conditions are defined by the
X
nc

 following parameters:
Hmix ¼ F_ j cpj $ T  Trif (25)
j¼1
P
h¼ (30)
The heat flux toward the shell is evaluated considering an P
overall heat transfer coefficient U and the temperature dif-
ference between the interior of the reactor at T and the Fsweep
SW ¼ (31)
external steam at Tv according to eq. (26) [55,56]: F
Another crucial operating parameter is the reactants
1 1 Ai lnðD0 =Di Þ Ai 1
¼ þ þ (26) mixture space velocity, called Gas Hourly Space Velocity
U hi 2pLkw A0 h 0
(GHSV, h1) and calculated as follow:
which introduces a rigorous calculation of the global coeffi-
3600$v 273
cient considering the dependence on the operating condi- GHSV ¼ $ $P (32)
L T
tions, through the evaluation of the physical quantities of the
where v is the superficial velocity of gas phase in fixed bed side
gaseous mixture, and on the geometry of the system, where
(m/s).
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 2 ( 2 0 1 7 ) 6 7 7 1 e6 7 8 6 6777

imposing a 30  C temperature difference between the inlet

Table 1 e Operation conditions and properties of
section of the reactor and the shell. Simulations are per-
conventional DME fixed bed reactor for the parametric
study. formed at two different CO2/CO ratio.
It is a worth assessment that:
Variable Value
Reactor diameter 0.038 m  membrane reactor performance is always better than
Bed length 1m
conventional reactor one. Thanks to the produced water
Catalyst density 1900 kg/m3
Void fraction of the bed 0.33
removal through the selective membrane, DME selectivity
Catalyst particle diameter 0.002 m is >0.92 over the whole range simulated versus a value of
Inlet gas temperature 473e573 K 0.82e0.89 for the conventional reactor.
Steam water temperature 443e543 K  operating temperature has a negative effect on both
Inlet pressure 50e70 bar membrane and conventional reactor, due to the reactions
CO2/CO 1e5
exothermicity.
H2/COx 1e3
 The benefits of membrane integration are reduced when
the temperature increases. The reason of this behavior is
In the following, a parametric study for the assessment of that the steam water permeability is lower at higher tem-
the main operating conditions effect on the DME yield/selec- perature as well as the H2O/H2 selectivity, as shown in Fig. 4
tivity and on the reactions conversions of the membrane (obtained interpolating the experimental data for a ZSM5/
reactor is reported. A comparison with a conventional DME MFI membrane reported in Ref. [51]), with a detrimental
synthesis reactor is assessed and discussed. A sweeping gas/ effect on membrane reactor performance.
reactants mixture co-current configuration is imposed in the  Selective membrane integration leads to a significant
membrane reactor (refer to Fig. 2). enhancement of COx and CO2 conversion over the whole
range simulated, even if such an enhancement is lower at
Effect of temperature higher temperatures.
 The increasing of CO2 composition in the inlet reactants
Fig. 3 shows the effect of the reactants mixture inlet temper- mixture leads to a reactors performance deterioration,
ature on YDME, SDME, XCOx and XCO2. The corresponding steam both for the membrane and for the conventional reactor. It
temperature in the cooling fluid side (Tv) is calculated always is a matter of fact that the performance of a conventional

Fig. 3 e Effect of the inlet reactor temperature on membrane (solid line) and conventional (dashed line) reactors performance
(reactor pressure ¼ 60 bar; GHSV ¼ 6.000 h¡1; H2/COx ¼ 3; h ¼ 0.06; Sw ¼ 2; saturated steam temperature ¼ inlet
temperature e 30 K).
6778 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 2 ( 2 0 1 7 ) 6 7 7 1 e6 7 8 6

reactor fed by a CO2 rich stream (CO2/CO ¼ 5) are always

unsatisfactory (YDME < 0.48, XCOx < 0.55) and the improve-
ments due to membrane installation are significant
(YDME ¼ 0.68 and XCOx ¼ 0.7 at T ¼ 473 K).
 CO2 conversion is slightly improved increasing the CO2
content in the inlet feedstock.

Effect of reactor pressure

The effect of the reaction pressure is illustrated in Fig. 5,

Fig. 4 e Steam water and hydrogen permeability vs.
membrane reactor operating temperature.
where the reactor performance indexes are calculated within
the range 50e70 bar (5e7$106 Pa). In the simulations, the
permeation zone pressure is fixed at 3.5 bar and the ratio h
varies from 0.05 to 0.07.
Globally, the pressure has a positive effect on both mem-
brane and conventional reactors performance for a thermo-
dynamics reason: in fact, the CO2 hydrogenation reaction (1) is
supported at high pressure, thus increasing the methanol
content and, consequently, promoting also the methanol
dehydration reaction (4). Only DME selectivity in the conven-
tional reactor is slightly reduced at higher pressures, since
higher pressures support the methanol production but not
influence the methanol dehydration and, consequently, the
DME synthesis.

Fig. 5 e Effect of the reactor pressure on membrane (solid line) and conventional (dashed line) reactors performance (inlet
temperature ¼ 523 K; GHSV ¼ 6.000 h¡1; H2/COx ¼ 3; permeation side pressure ¼ 3.5 bar; Sw ¼ 2; saturated steam
temperature ¼ 500 K).
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 2 ( 2 0 1 7 ) 6 7 7 1 e6 7 8 6 6779

Fig. 6 e Effect of the permeation and reaction zones pressure ratio h and of the sweeping gas and reaction inlet flow rate
ratio Sw on membrane reactor performance (inlet temperature ¼ 523 K; reaction pressure ¼ 60 bar; GHSV ¼ 6.000 h¡1;
H2/COx ¼ 3; CO2/CO ¼ 3; saturated steam temperature ¼ 500 K).

Fig. 7 e Effect of the GHSV on membrane (solid line) and conventional (dashed line) reactors performance (inlet
temperature ¼ 523 K; reaction pressure ¼ 60 bar; H2/COx ¼ 3; h ¼ 0.06; Sw ¼ 2; saturated steam temperature ¼ 500 K).
6780 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 2 ( 2 0 1 7 ) 6 7 7 1 e6 7 8 6
Membrane reactor behavior improvement is also due to the
increase of the pressure driving force across the membrane,
according to eq. (21).
The performance deterioration at larger CO2/CO ratio in
terms of DME yield/selectivity and of COx conversion is
confirmed, while the CO2 conversion is promoted if the CO2
composition in the inlet feedstock is higher.
Effect of permeation zone operating conditions
Fig. 6 reports the membrane reactor performance varying the
permeation zone to reaction zone pressure ratio h (fixing the
reaction zone pressure at 60 bar and changing the permeation
side pressure) and the sweeping gas to reactor inlet flow rate
ratio Sw.
It is clear that increasing the pressure difference between
the reaction and permeation zones, thus reducing the h ratio,
leads to a steep improvement of all the membrane reactor
performance indexes: fixing Sw at 2, the DME yield is 0.645 at a
permeation pressure of 3.6 bar and 0.605 at a permeation
pressure of 30 bar, the DME selectivity is reduced from 0.98 at
3.6 bar to 0.964 at 30 bar as well as the COx and CO2 conver-
sions (0.66 and 0.58 at 3.6 bar, 0.62 and 0.525 at 30 bar,
respectively). Such a behavior is due to the variation of pres-
sure driving force that modifies the water permeated flux, as
shown in eq. (21).
Also the ratio Sw has a positive effect on membrane reactor
performance, since increasing the sweeping gas flow rate al-
lows the reduction of the water partial pressure in the
permeate side and thus the increase of the water permeated
flux JH2O. However, this effect is negligible if the Sw ratio is >5,
since the absolute effect on water partial pressure in the
Fig. 8 e DME yield enhancement varying the inlet feedstock composition (inlet temperature ¼ 523 K; reaction
pressure ¼ 60 bar; GHSV ¼ 6.000 h¡1; h ¼ 0.06; Sw ¼ 4; saturated steam temperature ¼ 500 K).
permeation zone is less evident when the water dilution is
higher (larger sweeping gas flow).
Obviously, conventional reactor behavior is not influenced
by permeation zone pressure and sweeping gas flow rate.
Effect of the Gas Hourly Space Velocity
The GHSV effect on the membrane and traditional reactor in
depicted in Fig. 7. Increasing the gas velocity, thus reducing the
reactant mixture residence time, has an evident negative effect
on reactors performance, since the time for supporting the re-
actions is shorter. But, the effect is steeper for the membrane
reactor, because also the permeation phenomena are strongly
affected by the residence time: it is a worth noting that the in-
crease of gas velocity reduces the water permeation flux and the
membrane integration benefits are diminished in terms of DME
yield and carbon conversion when the GHSV is >60.000 h1. On
the other hand, when the GHSV is <10.000 h1, the benefits in
integrating the selective membrane are maximized.
Concerning with the DME selectivity, it has to be noticed
that its value is always high for the membrane reactor case
(>0.8) within the range assessed, meaning that the water
removal, and consequently the promotion of CH3OH dehy-
dration reaction (4), has always a strong positive effect on the
selectivity even at short reactants residence times.
Effect of inlet mixture composition
Figs. 8 and 9 report the DME yield and CO2 conversion
enhancement of membrane reactor in comparison with the
conventional reactor varying the inlet mixture composition
(CO2/CO and H2/COx), calculated as follow:
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 2 ( 2 0 1 7 ) 6 7 7 1 e6 7 8 6 6781

Fig. 9 e CO2 conversion enhancement varying the inlet feedstock composition (inlet temperature ¼ 523 K; reaction
pressure ¼ 60 bar; GHSV ¼ 6.000 h¡1; h ¼ 0.06; Sw ¼ 4; saturated steam temperature ¼ 500 K).

DYDME ¼ YDME;MR  YDME;CR (33)  the temperature has to be lower than 523 K, since its in-
crease has a negative effect on the exothermal reactions
DXCO2 ¼ XCO2 ;MR  XCO2 ;CR (34) and on the water steam permeation. On the other hand, a
too low value could be detrimental to the reactions
kinetics.
where YDME;MR and YDME;CR are the DME yield for the membrane
 Operating pressure has to be fixed as high as possible.
reactor and for the conventional reactor and XCO2 ;MR and XCO2 ;CR
 The h ratio has to be set as low as possible in relation to the
are the CO2 conversion inside the membrane reactor and the
materials and geometrical configuration of the MR, while
conventional reactor.
the value of Sw has to be large, thus reducing the water
It is clear how the performance improvement derived from
partial pressure in the permeation side and maximizing
the membrane installation is confirmed within the entire
the permeation flux, even if when the ratio is >5 its effect is
range of compositions simulated.
negligible.
Specifically, increasing the H2/COx ratio from 1 to 3 (stoi-
 Also GHSV has to be low, but, on the other hand, reducing
chiometric value) leads always to an increase of the DME yield
the gas velocity decreases the reactor productivity, leading
and CO2 conversion: while the membrane integration benefits
to the need of higher reaction volumes.
are close to zero when the H2/COx ratio is 1, the DME yield
enhancement is up to 0.24 and the DXCO2 is up to 0.31 when
A simulation of an optimized membrane reactor has been
the ratio is fixed at 3.
performed imposing the operating conditions listed in Table 2,
Concerning with the CO2 content in the inlet stream, while
where the optimal conditions obtained from the previous
the DYDME continuously improves increasing the CO2/CO ratio
simulations are summarized. Fig. 10 shows the molar fraction
(at H2/COx ¼ 2, its value is 0.06 and 0.14 at CO2/CO equal to 1
of reactants (top left) and products (top right) in the reaction
and equal to 5, respectively; at H2/COx ¼ 3, 0.15 and 0.23 at
side, the molar fraction of water and hydrogen in the
CO2/CO ¼ 1 and ¼ 5), the CO2 conversion enhancement im-
permeation side (down left) and the temperature profile inside
proves with the CO2 content at H2/COx < 2.5 and decreases at
H2/COx > 2.5: in fact, at H2/COx ¼ 2, DXCO2 is 0.12 and 0.14 when
CO2/CO is equal to 1 and equal to 5, respectively, while its
value, at H2/COx ¼ 3, is 0.31 at CO2/CO ¼ 1 and 0.23 at CO2/ Table 2 e Optimal operating conditions for membrane
reactor simulation.
CO ¼ 5.
GHSV [h1] 7.000
Membrane reactor preliminary design Tv [K] 470
Tin [K] 500
P [bar] 70
The previous simulations have allowed to understand the
h 0.05
effect of the main operating parameters on membrane reactor Sw 5
performance. To summarize, in order to maximize the DME H2/COx 3
yield and selectivity and the reactions conversion: CO2/CO 3
6782 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 2 ( 2 0 1 7 ) 6 7 7 1 e6 7 8 6

Fig. 10 e Molar fraction of reactants (top left) and of the products (top right) in the reaction zone, molar fraction of steam
water and hydrogen in the permeation zone (down left) and temperature profile along the membrane reactor (down right)
imposing the operating conditions summarized in Table 2.

the reactor (down right). Imposing a GHSV of 7.000 h1, the
reactions and the permeation flux tend to an equilibrium
since the molar fraction yDME in the reaction side reaches an
asymptotic value as well as the molar fractions yH2O and yH2 in
the permeation side. Concerning with the temperature, a hot
spot is generated in the first part of the reactor, when the re-
actions kinetics are faster; then the steam production in the
cooling fluid side removes the heat generated by the
exothermic reactions, lowering the temperature. Moreover, it
has to be noticed that the water fraction at the reactor outlet is
close to zero as well as the methanol fraction, confirming that
the methanol dehydration reaction (4) is strongly supported
thanks to the water removal from the reaction side.
Table 3 shows a comparison between the performance of
the membrane reactor and of a conventional reactor operating
at the same conditions: all the performance indexes are
strongly improved thanks to the membrane integration,
mainly the YDME (þ31.5%) and the CO2 conversion (þ30.2%).
Moreover, DME selectivity of the synthesis reactions in the
membrane reactor is close to 1.
It has to be noticed that the outlet stream from the
permeation zone has a 4% of hydrogen: it leads to the need of
adding a H2/CO2 separator in the sweeping CO2 closed loop,
shown in the process block diagram (Fig. 1). Alternatively, a
different process configuration can be implemented: a pure
CO2 stream is fed to the membrane reactor permeation side;
then, the outlet stream containing CO2, H2 (4.1%) and H2O (4%)
is sent to a condenser to separate water; the final flow rate
composed by CO2 and H2 is added to the syngas feedstock and
fed to the reaction zone. By this way, a pure CO2 stream is
exploited generating an added-value product as DME. Such a
configuration will be assessed in a next paper.

Table 3 e Membrane reactor and conventional reactor Conclusions

performance comparison.
Membrane Conventional Enhancement The application of a steam water selective membrane in a
reactor reactor one-step DME production process has been modeled and
YDME 0.75 0.57 þ31.5% simulated. Specifically, the use of a CO2-rich feedstock, i.e.
SDME 0.99 0.88 þ12.5% derived from the synthesis gas generated by a bio-gas stream,
XCOx 0.75 0.65 þ15.4% has been assessed. It is well-known that the CO2 presence in
XCO2 0.69 0.53 þ30.2% the DME synthesis reactor leads to a inhibition effect, due to
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 2 ( 2 0 1 7 ) 6 7 7 1 e6 7 8 6 6783

the promotion of the reverse WGS reaction causing a H2O kw wall thermal conductivity, W/(m K)
accumulation in the reaction environment with a detrimental Kj rate constant of the reaction j
effect on both the CO2 hydrogenation and methanol dehy- Ki adsorption equilibrium constant, Pa1
dration. It has been demonstrated that, integrating a micro- Keq equilibrium constant
porous zeolite membrane, highly selective to water and thus L reactor length, m
able to remove the produced steam from the reaction envi- LPG Liquefied Petroleum Gas
ronment, the DME production reactor performance is largely P reactor pressure in fixed bed side, Pa
improved in terms of carbon conversions, DME yield and P permeation zone pressure, Pa
selectivity: feeding the membrane reactor with a feedstock Po pressure in cooling fluid side, bar
characterized by a CO2/CO ratio of 3, the DME yield reaches a Pa atmospheric pressure, bar
value of 0.75 vs. 0.57 in the conventional reactor, the XCOx and Pj partial pressure of species j in fixed bed side, Pa
XCO2 are 0.75 and 0.69, with an improvement of 15.4% and pj partial pressure of species j in permeation side, Pa
30.2%, and the DME selectivity is close to 1. PermH2 hydrogen permeability through the selective
The improvement of the reactor performance due to the membrane, mol s1 m2 Pa1
selective membrane application has been confirmed within PermH2O steam water permeability through the selective
large ranges of operating conditions (temperature, pressure, membrane, mol s1 m2 Pa1
GHSV, feedstock composition, pressure driving force across Pr Prandtl number
the membrane and sweeping gas flow rate), with more evident ri rate of the reaction i, kmol/(kg$s)
benefits when the gas mixture velocity and operating tem- R idealgas constant
perature are low and the H2/COx ratio is high. Re external tube radius, m
Membrane reactor application in the DME synthesis process Ri internal tube radius, m
is a technology that can be included in the “CO2 valorization” Re Reynolds number
framework, meaning those technologies able to convert the SDME DME selectivity
greenhouse gas CO2 into useful and marketable products: a Sw sweeping gas to inlet total flow rate ratio
pure carbon dioxide stream can be used as sweeping gas in the T temperature, K
membrane reactor permeation side, collecting the permeated Tv steam temperature in cooling fluid side, K
water and hydrogen; then, after separating the steam by yi mole fraction of the component i
condensation, the CO2 þ H2 stream can be added to the syngas YDME DME yield
inlet in the membrane reactor feedstock, thus converting the YDME;MR DME yield for the membrane reactor
CO2 in a added-value product as DME. Such a process configu- YDME;CR DME yield for the conventional reactor
ration will be modeled and assessed in a future work, by which U overall heat transfer coefficient between pipe and
the overall DME synthesis plant, composed by the membrane shell, W/(m2 K)
reactor, the products purification units and potential reactants XCO2 conversion of CO2
recycling, will be simulated in Aspen environment. XCO2 ;MR CO2 conversion inside the membrane reactor
XCO2 ;CR CO2 conversion inside the conventional reactor
XCOx total conversion of CO and CO2
Nomenclature v superficial velocity of gas phase in fixed bed side, m/s
z axial coordinate, m
Ai inside area of the tube, m2
Ao outside area of the tube, m2 Greek letters
cp specific heat of the gaseous mixture at constant ε packed bed void fraction
pressure, J mol1 K1 h permeation side to reaction side pressures ratio
D0 tube outside diameter, m lg gas mixture conductivity, W/(m K)
Di tube inside diameter, m m gas phase dynamic viscosity, kg/(m s)
DME Dimetyl Ether r density of gas phase, kg/m3
dp particle diameter, m rc catalyst bed density, kg/m3
F total molar flow rate, kmol/s
Fin,i inlet molar flow rate of the component i, kmol/s
Fout,i outlet molar flow rate of the component i, kmol/s Annex 1. Physical properties
Fi molar flow rate of the component i, kmol/s
Fsweep sweeping gas flow rate in the permeation zone, The viscosity of the gas mixture is calculated according to the
kmol/s Wilke method as reported in Ref. [60]:
GHSV Gas Hourly Space Velocity, h1 X
n
mi
Hmix enthalphy of the gas mixture, kJ mmix ¼ Pn  . 
DHri heat of reaction, kJ/mol i¼1 j¼1 fij yj yi

hi heat transfer coefficient between the gas and the  . 1=2
 

2
wall, W/(m2 K) 1 þ mi mj Mj Mi
1=4

ho heat transfer coefficient outside of the tube, fij ¼ 
 1=2

W/(m2 K) 8 1 þ Mi Mj
k thermal conductivity, W/(m K)
6784 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 2 ( 2 0 1 7 ) 6 7 7 1 e6 7 8 6

 
mi Mj 1018:6 1098800
fij ¼ fj i lDME ¼ 0:059975*T0:2667 1þ þ
mj Mi T T2

Viscosity of components i are expressed by the following Density of the gaseous mixture is calculated though the
equations [61]: compressibility coefficient with PengeRobinson equation of
h state [60]:
mH2 O ¼ 103 $ 0:008115 þ 3:9343e5 ðT  273Þ


i Z3  ð1  BÞZ2 þ A  2B2  2B Z  AB  B3  B2 ¼ 0
9 2 12 3
 7:1973e ðT  273Þ þ 7:2056e ðT  273Þ
P$a P$b
h A¼ 2
;B ¼ ;
mCO ¼ 10 $ 0:016456 þ 5:0435e5 ðT  273Þ
3 ðRTÞ RT
i
 3:4705e8 ðT  273Þ2 þ 1:7166 e11 ðT  273Þ3 n X
X n
a¼ yi yj aij
h i¼1 j¼1

mCO2 ¼ 103 $ 0:0013799 þ 4:8847e5 ðT  273Þ

i X
n
 1:7863e8 ðT  273Þ2 þ 3:4755e12 ðT  273Þ3 aj ¼ yi aij
i¼1

h
mH2 ¼ 103 $ 0:0083337 þ 2:2:2e5 ðT  273Þ  1:1216e8 ðT  273Þ2  1=2

i aij ¼ a0i a0j 1  kij
þ 5:1704e12 ðT  273Þ3
a0j ¼ acj aj

mDME ¼ 2:68$107 $T0:3975 ð1 þ 534=TÞ 
 
acj ¼ 0:45724 RTcj Pcj
mMEOH ¼ 3:0663$107 T 0:69655 =1 þ 205=T
h 
 1=2 i2
The thermal conductivity is calculated according to the acj ¼ 1 þ mj 1  T Tcj
Wassiljewa equation as reported in Ref. [60]:
mj ¼ 0:384401 þ 1:522760u  0:213808u2 þ 0:034616u3
X
n
li
lmix ¼ Pn  .   0:001976u4
i¼1 j¼1 Aij yj yi

The coefficients Aij are expressed by the relation of Lind- X

n
b¼ yj bj
sayeBromley as reported in Refs. [60,62]: j¼1

.
1   

 3=4 T þ Si 2 2 T þ Sij RTcj
Aij ¼ 0:25 1 þ mi mj Mj Mi ; bj ¼ 0:077796
T þ Sj T þ Si Pcj
where the Sutherland constants Si e Sj of pure gases, function
of the boiling temperature in normal conditions Tbi, can be
calculated as follow: Component Tc [K] Pc [MPa] u
qffiffiffiffiffiffiffiffi H2O 647.096 22.06 0.3449
Si ¼ 1:5 Tbi ; Sii ¼ Si ; Sij ¼ Sji ; Sij ¼ Fs Si Sj H2 33.19 1.313 0.216
CO 132.92 3.5 0.0482
The thermal conductivities of pure components li CO2 304.21 7.383 0.2236
[W/(m K)] are calculated as follow: CH3OH 512.5 8.1 0.5658
CH3OCH3 400 5.37 0.2002
lH2 O ¼ 6:204*106 T1:3973


lH2 ¼ 0:002653$T0:7452 ð1 þ 12=TÞ Specific heat of the mixture cp [J/(mol K)]is calculated by the
following equations [61]:
 
57:13 501:92
lCO ¼ 0:00059882$ T0:6863 1þ þ 2
X
n
T T cpmix ¼ yi cpi
i¼1
 
964 1860000
lCO2 ¼ 3:69$T0:3838 1þ þ

T T2 cpH2O ¼ 4:18$ 8:22 þ 0:00015 T þ 1:34 106 T2 ;

lMeOH ¼ 5:7992*107 *T1:7862 cpH2 ¼ 4:18$ð6:62 þ 0:00081 TÞ;

 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 2 ( 2 0 1 7 ) 6 7 7 1 e6 7 8 6 6785

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