HG

chemengineering
Membrane and
Membrane Reactors
Operations in
Chemical Engineering
Edited by
Adolfo Iulianelli
Printed Edition of the Special Issue Published in ChemEngineering
www.mdpi.com/journal/chemengineering
Membrane and Membrane Reactors
Operations in Chemical Engineering
Membrane and Membrane Reactors
Operations in Chemical Engineering
Special Issue Editor

Adolfo Iulianelli
MDPI • Basel • Beijing • Wuhan • Barcelona • Belgrade

Adolfo Iulianelli
University of Calabria
Italy
Editorial Office
MDPI
St. Alban-Anlage 66
4052 Basel, Switzerland
This is a reprint of articles from the Special Issue published online in the open access journal
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ChemEngineering/special issues/Membrane Reactors Operations).
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Contents
About the Special Issue Editor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . vii
Preface to ”Membrane and Membrane Reactors Operations in Chemical Engineering” . . . . ix
Parisa Biniaz, Niloofar Torabi Ardekani, Mohammad Amin Makarem and

Mohammad Reza Rahimpour
Water and Wastewater Treatment Systems by Novel Integrated Membrane Distillation (MD)
Reprinted from: ChemEngineering 2019, 3, 8, doi:10.3390/chemengineering3010008 . . . . . . . . 1
René Ruby-Figueroa, Monica Nardi, Giovanni Sindona, Carmela Conidi and

Alfredo Cassano
A Multivariate Statistical Analyses of Membrane Performance in the Clarification of Citrus
Press Liquor
Marina Holgado and David Alique

Preliminary Equipment Design for On-Board Hydrogen Production by Steam Reforming in
Palladium Membrane Reactors
Tiziana Marino, Alberto Figoli, Antonio Molino, Pietro Argurio and Raffaele Molinari
Hydrogen and Oxygen Evolution in a Membrane Photoreactor Using Suspended Nanosized
Au/TiO2 and Au/CeO2
Kay Marcel Dyrda, Vincent Wilke, Katja Haas-Santo and Roland Dittmeyer
Experimental Investigation of the Gas/Liquid Phase Separation Using a Membrane-Based
Micro Contactor
Barbara Morico, Annarita Salladini, Emma Palo and Gaetano Iaquaniello

Solar Energy Assisted Membrane Reactor for Hydrogen Production
Alessio Caravella, Adele Brunetti, Monia Grandinetti and Giuseppe Barbieri

Dry Reforming of Methane in a Pd-Ag Membrane Reactor: Thermodynamic and Experimental
Analysis
Shabnam Majidi Salehi, Rosangela Santagada, Stefania Depietra, Enrica Fontananova,

Efrem Curcio and Gianluca Di Profio
Ionic Liquid Hydrogel Composite Membranes (IL-HCMs)
v
About the Special Issue Editor
Adolfo Iulianelli (Ph.D.) holds a degree in Chemical Engineering (2002) from the University of
Calabria (Italy), where he also obtained his PhD in Chemical and Materials Engineering in 2006.
Nowadays, he is a Researcher at the Institute on Membrane Technology of the Italian National
Research Council (CNR-ITM). He is author or co-author of more than 170 scientific contributions
in the form of international peer-reviewed articles in ISI journals (h-index = 29, Scopus database),
patents, proceedings of national and international conferences, as well as more than 30 peer-reviewed
book chapters. Furthermore, he is Reviewer of more than 30 international ISI journals and has been
the Invited and Keynote Speaker of several international conferences and training schools, amongst
others. Furthermore, A.I. has been a member of the Organizing and Scientific Committee of several
international conferences.
A.I. is the Editor of various scientific and international books about hydrogen, membrane
technology, and renewable sources, and is Associate Editor of the International Journal of Membrane
Science & Technology, Sectional Editor of Journal of New Developments in Chemistry—Green Chemistry,
Sectional Editor of Current Alternative Energy, member of the editorial board of several scientific
journals, and serving as Guest Editor for International Journal of Hydrogen Energy, Membranes, and
ChemEngineering.
A.I is qualified as Associate Professor with expertise in 1) Chemical Industrial Process and
Plants, 2) Systems, Methodologies & Technologies of Chemical and Process Engineering, and
3) Fundamentals of Chemistry Technologies.
His research interests include membrane reactors, fuel cells, gas separation, hydrogen
production from reforming reactions of renewable sources exploitation, and green chemistry.
vii
Preface to ”Membrane and Membrane Reactors
Operations in Chemical Engineering”
In the last four decades, membrane technology has largely contributed to the valorization
of process intensification strategy in several strategic engineering sectors, demonstrating the high
potentialities of membrane operations as an alternative approach to conventional processes.
In the field of chemical engineering, high process efficiency and easy operation, high product
selectivity and permeability, elevated compatibility in integrated membrane systems, energy saving
and environmentally friendly processes, and membrane and membrane reactor operations represent
a well-established scientific and industrial reality, as also reported in the various works collected in
this Special Issue.
In this Special Issue, Rahimpour and co-authors (Water and Wastewater Treatment Systems
by Novel Integrated Membrane Distillation (MD)) have reviewed the recent state-of-the-art and
sophisticated advances in membrane distillation technology for wastewater treatment. Di Profio
and co-authors (Ionic Liquid Hydrogel Composite Membranes (IL-HCMs)) presented a novel
experimental route for the preparation of hydrogel composite membranes for utilization as membrane
contactors in desalination applications.
Dittmeyer and co-authors (Experimental Investigation of the Gas/Liquid Phase Separation
Using a Membrane-Based Micro Contactor) investigated the gas/liquid phase separation of CO2 from
a water–methanol solution at the anode side of a micro direct methanol fuel cell using hydrophobic
polytetrafluoroethylene as a membrane microcontactor. Cassano and co-authors (A Multivariate
Statistical Analyses of Membrane Performance in the Clarification of Citrus Press Liquor) performed
statistical analysis on the experimental behaviors of polyvinylidene fluoride membranes applied in
the clarification of citrus press liquor.
Marino et al. (Hydrogen and Oxygen Evolution in a Membrane Photoreactor Using Suspended
Nanosized Au/TiO2 and Au/CeO2 ) proposed a method for one-step hydrogen and oxygen
separation through a photocatalytic membrane reactor using a modified Nafion membrane. Through
experiments, Morico et al. (Solar Energy-Assisted Membrane Reactor for Hydrogen Production)
studied a pilot-scale membrane reformer coupled with solar-assisted molten salt-heating to generate
hydrogen, also proposing an economic analysis of its industrial feasibility at reduced environmental
impact.
Caravella et al. (Dry Reforming of Methane in a Pd–Ag Membrane Reactor: Thermodynamic and
Experimental Analysis) performed an experimental campaign on the CO2 reforming of methane in a
catalytic Pd-based membrane reactor, including a detailed thermodynamic analysis, demonstrating
the benefits of this membrane-integrated reaction process while making the production of syngas
more efficient and with additional environmental advantages. To conclude, Holgado and Alique
(Preliminary Equipment Design for On-Board Hydrogen Production by Steam Reforming in
Palladium Membrane Reactors) presented the design of an on-board hydrogen production Pd-based
membrane reactor integrated to a PEM fuel cell, demonstrating the feasibility of a one-step process
for vehicle applications.
Last but not least, the Editor of this Special Issue would like to thank all the authors for their
excellent work and acknowledge their contribution to the success of this project.
Adolfo Iulianelli
ix
chemengineering
Review
Water and Wastewater Treatment Systems by Novel
Integrated Membrane Distillation (MD)
Parisa Biniaz, Niloofar Torabi Ardekani, Mohammad Amin Makarem and
Mohammad Reza Rahimpour *
Department of Chemical Engineering, Shiraz University, Shiraz 71345, Iran; [email protected] (P.B.);
[email protected] (N.T.A.); [email protected] (M.A.M.)
* Correspondence: [email protected]; Tel.: +98-917-713-9296
Received: 30 September 2018; Accepted: 7 January 2019; Published: 15 January 2019
Abstract: The scarcity of freshwater has been recognized as one of the main challenges people
must overcome in the 21st century. The adoption of an environmentally friendly, cost-effective,
and energy-efficient membrane distillation (MD) process can mitigate the pollution caused by
industrial and domestic wastes. MD is a thermally driven process based on vapor–liquid equilibrium,
in which the separation process takes place throughout a microporous hydrophobic membrane.
The present paper offers a comprehensive review of the state-of-the-art MD technology covering
the MD applications in wastewater treatment. In addition, the important and sophisticated recent
advances in MD technology from the perspectives of membrane characteristics and preparation,
membrane configurations, membrane wetting, fouling, and renewable heat sources have been
presented and discussed.
Keywords: membrane distillation; wastewater treatment; membrane configuration; fouling renewable

heat sources
1. Introduction
Freshwater scarcity and the excessive consumption of water have been regarded as serious
challenges over past decades. Several contributing factors such as an increasing population,
improving living standards, agricultural sector growth, and industrialization have threatened a
further reduction in the water level and given rise to this crisis [1]. Based on the type of industry,
a vast amount of wastewater containing salinity and organic compounds such as arsenic, fluoride,
cadmium, chromium, mercury, manganese, lead, etc., have been produced. Discharging these
contaminant elements above their effluent standard has exerted catastrophic effects on aquatic and
terrestrial habitats and human health [2]. To address this issue, several treatment technologies
have been investigated by scientists such as reverse osmosis, disinfection, granular filtration,
gravity separation, coagulation-flocculation, air stripping and aeration ion exchange, adsorption,
and membrane filtration [3]. Among all the conventional techniques under study, the membrane
process has become highly popular due to the potential benefits associated with the technology.
Generally, in a membrane, some particular substances are selectively allowed to pass through
while others are retained (retentate phase) [4]. The permeating compounds pass through the membrane
based on a driving force such as a pressure gradient, concentration gradient, temperature gradient,
or electrical gradient [5,6]. This phenomenon emerges from membrane module characterization
(pore size, pore shape), membrane surface characteristics (porosity, charge/hydrophobicity) and
membrane configuration (geometry, dimensions) [7]. To put it another way, membrane separation
processes applied in wastewater treatment are categorized as the isothermal and non-isothermal
process. The former includes concentration-driven membrane processes (pervaporation and membrane
extraction), pressure-driven membrane processes (microfiltration, ultrafiltration, nanofiltration,
ChemEngineering 2019, 3, 8 1 www.mdpi.com/journal/chemengineering

ChemEngineering 2019, 3, 8
and reverse osmosis) and electrically driven membrane processes (electrodialysis, electrophoresis)
while the latter is a thermally driven membrane process named membrane distillation (MD) [8–10].
According to the literature, among all the membrane processes, MD has been perfectly able to treat
water with an extremely high level of salinity [11,12] and hazardous contaminants [13]. In this context,
extensive research has been conducted by scientists and researchers all over the world over recent
years. Drioli et al. [14] investigated the current and prospective role of membrane engineering in
attaining the objectives of a process intensification strategy to improve the efficiency and sustainability
of novel membrane processes including MD.
The present study assesses the evolution of membrane distillation in wastewater treatments.
The work investigates the characteristics, material, module, and different configurations of MD applied
in water treatment as well as covering the fouling and wetting phenomena. Furthermore, the benefits
and limitations of MD processes, economic analysis, and future research directions of interest have
been pointed out. While various review papers focusing on MD technology have been conducted
by researchers, most of them provide a full membrane perspective, without being highly focused on
the novel MD membrane designs and process configurations. In this critical review, the authors aim
to review the recent advances in MD technology in terms of low-grade or renewable heat sources,
such as waste heat from industrial processes which reduce transmembrane heat loss and increase
the proportion of heat recovered from the permeate stream. Moreover, nontraditional anti-fouling
processes and recently developed membranes prepared from surface modifications of polymers and
nanomaterials such as plasma surface modification and electrospinning are investigated thoroughly.
2. Membrane Distillation
2.1. History of MD Process

Membrane distillation was patented in 1963 [15] and Findley published the first MD paper in 1967
in the “Industrial & Engineering Chemistry Process Design Development” journal [16]. Nonetheless,
the MD process did not attract considerable interest until the early 1980s when more efficient module
membranes such as Gore-Tex became accessible [17]. The term MD originates from the significant
similarity between the MD method and typical distillation process since both of them operate based
on the liquid/vapor equilibrium. Moreover, in both processes feed stream is heated by the energy
source to obtain the necessary potential heat of vaporization [18]. Being a practical and effective
wastewater treatment, MD has been the topic of worldwide investigation by many researchers and
scientists. Besides, the interest in MD processes has rapidly grown over the recent years. Table 1 gives
up-to-date and interesting information concerning the application of MD in wastewater treatment
based on several patents published from 2016 to 2018.
2
Table 1. List of published patents in the application of membrane distillation (MD) in wastewater treatment (2016 to 2018).
Patent Highlights
The present invention relates to a zero-discharging treatment device for desulfurization wastewater
Desulfurization waste water zero-discharging treatment technology
that consists of a nanofiltration system, calcium removal sedimentation pool set, a heavy metal and
for coal-fired power plants
magnesium removal pool set, an evaporating crystallizer, and a membrane distillation system.
Publication number: CN105712557A
Crystal salt gained from evaporating crystallization can be entirely recycled, and treatment and
Publication date: 2016-06-29
operating cost are extremely reduced.
A membrane distillation system that is used for concentration of

The utility model reveals the MD system that is applied for the handling of the concentration of
desulfurization waste water
desulfurized wastewater, with this considered to have some benefits such as a simple structure, safe
Publication number: CN204981458U
operation, and a smaller area.
Salt-containing wastewater treatment system The present utility model includes a salt-containing wastewater treatment system that contains an
Publication number: CN205133326U electrodialysis device for receiving and handling salted wastewater, which is connected to the
Publication date: 2016-04-06 MD system.
Process and system for produced water treatment This invention relates to a system and process for produced water treatment. A heat exchanger,
Publication number: US20170096356A1 a vacuum tank, an adsorption-desorption, and MD crystallization process are in this process
Publication date: 2017-04-06 combination. The efficiency related to costs of maintenance and energy consumption is considered.
Modularly installed energy-saving membrane distillation The present invention represents a modularly installed energy-saving MD wastewater treatment
3
wastewater treatment device and method device which consists of a post-treatment and primary treatment module. The proposed device
Publication number: CN106865663A assembles easily and has suitable energy-saving effects for the treatment of different types
Publication date: 2017-06-20 of sewage.
Energy -saving membrane distillation effluent treatment plant of The utility model relates to an energy-saving MD sewage treatment plant of modularization
modularization installation installation and consists of post-processing and primary treatment modules. The applied used
Publication number: CN206635064U equipment in the device is energy conserving, convenient, and effective for all types of effluent
Publication date: 2017-11-14 treatment.
The present utility model reveals a highly concentrated organic wastewater treatment system that
High -concentration organic wastewater treatment system consists of a liquid bath of raw material, anaerobic biological treatment device, and a positive
Publication number: CN206318843U osmotic membrane. Highly concentrated organic wastewater from a bioreactor is handled in the
Publication date: 2017-07-11 combined MD system. This system proposes greater recovery of the pure water rate and reduces the
concentration of organic matters.
Multi-stage submerged membrane distillation water treatment
apparatus and a resource recovery method This investigation related to a submerging multi-stage membrane distillation water
Publication number: US20170313610A1 treatment device.
Table 1. Cont.
Wastewater treatment system This utility model shows a wastewater treatment system that consists of an MD unit connected to
Publication number: CN207243660U magnetism loaded flocculation unit. This proposed wastewater treatment system has some benefits
Publication date: 2018-04-17 like simple equipment, efficient sewage treatment, and a lower energy consumption.
Concentrated decrement device of vacuum membrane distillation
This invention concerns a zero-discharging wastewater treatment device, which is particularly
wastewater that frequently flows backwards
related to a vacuum membrane distillation (VDM). MD has some effective benefits, for instance,
Publication number: CN207734625U
it enhances the service life, and shows great abilities to treat wastewater with high salinity.
Slot-type solar sea water desalination device based on membrane The invention reveals a slot-type solar seawater desalination device integrated with membrane
distillation distillation. The required heat energy of the process is supplied from solar energy emitted by a
Publication number: CN107720863A slot-type condenser mirror, in which solar energy is reflected and condensed onto an arc heat
Publication date: 2018-02-23 collection tube.
Porous membrane for membrane distillation, and method for
A membrane distillation device, with a hydrophobic porous hollow fiber membrane, and a
operating membrane distillation module
condenser for condensing water vapor is invented for water treatment. The membrane has an
Publication number: WO2018174279A1
average pore diameter of 0.01–1 μm.
Hollow fiber membrane module for direct contact membrane The invention is a desalination system by direct contact membrane distillation integrated with a
distillation-based desalinization cylindrical cross-flow module comprising high-flux composite hydrophobic hollow fiber
4
Publication number: WO2018195534A1 membranes. A model is developed and directed to the system and shows the observed water vapor
Publication date: 2018-10-25 production rates for various feed brine temperatures at different feed brine flow rates.
A membrane distillation technique and method for treating
The invention shows a seed film distillation procedure and technology for processing radioactive
radioactive waste water systems
waste including (pretreatment, preheating, membrane separation, condensation process) by
Publication number: CN108597636A
accumulating the wastewater
Multistage immersion type membrane distillation water treatment
apparatus and a resource recovery method using the same number This invention provides a multistage immersion-type membrane distillation water treatment system
of oil resources and a viable resource recovery technique applying the same number of oil resources which can
Publication number: KR101870350B1 substantially reduce the heat energy.
2.2. Definition of MD
MD is a thermally driven treatment process in which the thermal gradient is generated across a
microporous hydrophobic membrane [19]. Simultaneously, the process can be operated by low-grade
heat and/or waste including solar energy [20], geothermal energy [21], wind, tidal, and nuclear
energy, or low-temperature industrial streams [22]. It should be noted that the process is driven by
the vapor pressure difference between the permeable hydrophobic membrane pores. In other words,
volatile vapor molecules are allowed to pass through the MD while non-volatile compounds are
retained on the retentate stream. The permeated volatile vapors are then collected or condensed by
various techniques. Finally, completely pure products that are theoretically 100% free from solid,
harmful substances and non-volatile contaminants are produced [23]. Figure 1 illustrates a schematic
diagram of the MD process.
As the graph reveals, volatile vapor molecules in the hot feed which are vaporized at the
liquid/vapor interface are able to pass through the pores of the membrane. The liquid feed, on the
other hand, is prevented from transporting through the membrane pores. This phenomenon is mainly
because of the hydrophobic nature of the MD membrane and its surface tension. Therefore, it is
important to note that the dry pores must not be wetted by the liquid feed which is directly in contact
with the hydrophobic membrane [24–26].
Figure 1. Schematic diagram of the MD process [10].
2.3. Limitation and Benefits of MD Process

In comparison with other conventional membrane separation systems, MD separation process
brings tremendous benefits such as having low operating temperatures, being cost-effective by
applying waste heat and renewable energy sources, being able to treat wastewater with a high level of
purity, and being less likely to suffer from membrane fouling [18,27,28]. Therefore, these remarkable
features make MD an attractive method for wastewater treatment, seawater desalination, and so
many other industrial applications including environmental purification, in the food industry [29],
in medicine [30,31], and in the production of acids, etc. However, employing MD in industry is limited
by some significant challenges like the risk of total or partial membrane wetting [32] or not being
commercially available on a large scale [33]. Regarding previous studies, the choosing of suitable
membranes and the energy efficiency are the two main factors that must be taken into account when
applying the MD process [18,23]. Table 2 presents a detailed overview of the positive and negative
aspects of the MD process.
5
Table 2. A comprehensive overview of the positive and negative points of the MD process.
Advantages Disadvantages Reference

Low operating temperature (the process Lower permeate flux compared to other
liquid is not essentially heated up to the commercialized separation processes, such [9,19,33–35]
boiling temperatures) as RO.
Lower hydrostatic pressure required
compare to pressure-driven membrane
[9,19,33]
separation processes such as reverse
osmosis (RO).
High rejection (99–100%) for High susceptibility of permeate flux to
macromolecules, non-volatile compounds temperature and concentration polarization
[19,36,37]
(colloids, salts), and inorganic ions. In fact, effects, partial or total pore wetting, and
100% separation happens, theoretically. membrane scaling and fouling.
Lower requirements on the mechanical
[18,33]
properties of the membrane.
Larger pore size and less chemical
High heat loss (by conduction) and energy
interaction between process solution and [33,36]
consumption
membrane lead to less fouling.
Alternative low-grade energy sources like
waste heat, solar energy, and geometrical Pore wetting risk [8,38]
heat can be utilized.
The possibility to combine with some other Unclear economic and energy costs for
separation processes in order to build an different MD applications and
[8,33]
integrated separating system, like an RO configurations, just when waste heat is
unit or ultrafiltration available MD becomes cost competitive.
An efficient method to eliminate heavy
[33]
metals and organic from wastewater.
The lack of commercially available MD
It is an effective and safe process to remove modulus manufactured for large-scale
[33,39]
radioactive waste. applications and high-performance
membrane.
MD is able to work with a saturated
solution or high solute concentration in a [33]
liquid stream
Fewer vapor spaces needed in comparison
with common distillation process so MD Having less producers of MD technology [8,33]
can be used at a smaller scale.
Reduced sensibility to concentration
[8,33,38]
polarization.
High concentration polarization or osmotic
pressure does not limit performance.
Having low cost and less sophisticated
Limitations of MD permeate flux, due to a
installation and construction (because of
further mass transfer resistance caused by [18,33]
lower operating temperature and pressure),
trapped air through the membrane
leads to a full level of automation.
Being less sensitive to membrane pollution
or concentration polarization and without a [8,33,36]
pretreatment stage.
6
2.4. Membrane Characteristics

Hydrophobicity is the fundamental necessity for an MD membranes process. Therefore,
the membranes must be fabricated with original or modified hydrophobic polymers with low surface
energies. Moreover, the membrane applied in the MD should have a low resistance to mass transfer
and low thermal conductivity to prevent heat loss across the membrane. In addition, the membrane
should have good thermal stability in high temperatures, and good chemical resistance to acids and
bases. High permeability is another significant feature that a membrane should possess in order to
be applied in the MD process. To satisfy this feature, the membrane surface layer must be as thin
as possible so that the vapors are allowed to pass through the membrane in a short period of time.
Another notable characteristic of a membrane is a high liquid entry pressure (LEP). LEP is regarded as
the minimum hydrostatic pressure in an MD system that prevents the liquid solutions from penetrating
into the membrane pores. A sufficiently high LEP can be achieved by applying a membrane material
with high hydrophobicity and a small maximum pore. In addition, the surface porosity and pore size
of the membrane must be as large as possible [18,40].
2.5. Membrane Materials and Modules

The most popular micro-porous hydrophobic membranes are commercially fabricated with
polypropylene (PP), polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyethylene (PE),
inorganic materials, and carbon nanotubes (CNTs) available in plate and frame, hollow fiber, tubular,
spiral wound, and flat sheet modules. Currently, PTFE with unique features such as high hydrophobicity
and strong resistance against severe operating conditions has dominated the commercial and laboratory
applications of MD [23,41,42]. Figure 2 makes a comparison between different membrane modules
with their positive and negative points [9]. Table 3 provides information about the characteristics of
commercial membranes commonly applied in the MD process.
Figure 2. Advantage and disadvantages of membrane modules.
7
Table 3. Commercial membranes applied in MD (membrane thickness, δ; porosity, ε; liquid entry

pressure of water, LEPw).
Membrane Trade
Material Manufacturer δ (μm) ε (%) LEPW (kPa) Reference
Name
TF200 PTFE */PP ** Gelman 178 80 282
TF450 PTFE/PP Gelman 178 80 138 [8,18,43]
TF1000 PTFE/PP Gelman 178 80 48
PT20 PTFE/PP Gore 64 ± 5 90 ± 1 3.68 ± 0.01 [8]
PT45 PTFE/PP Gore 77 ± 8 89 ± 4 2.88 ± 0.01
TS1.0 PTFE/PP Osmonics Corp. 175 70 -
TS22 PTFE/PP Osmonics Corp. 175 70 - [18]
TS45 PTFE/PP Osmonics Corp. 175 70 -
Taflen PTFE/PP Gelman 60 50 -
FGLP PTFE/PE Millipore 130 70 280
FHLP PTFE/PE *** Millipore 175 85 124
GVHP PVDF **** Millipore 110 75 204
PV22 PVDF Millipore 126 ± 7 62 ± 2 2.29 ± 0.03 [8,44]
PV45 PVDF Millipore 116 ± 9 66 ± 2 1.10 ± 0.04
HVHP (Durapore) PVDF Millipore 140 75 105
GVSP PVDF Millipore 108 80 - [18]
Gore PTFE Gore 64 90 368
Gore PTFE Gore 77 89 288
Teknokrama PTFE Teknokrama - 80 -
G-4.0-6-7 PTFE GoreTex Sep GmbH 100 80 463
Sartorious PTFE Sartorious 70 70 -
MD080CO2N PP Enka Microdyn 650 70 -
MD020TP2N PP Enka Microdyn 1550 70 - [8,18]
Accurel® PP Enka A.G. 400 74 -
Celgard X-20 PP Hoechst Celanese Co 25 35 -
Accurel® S6/2 PP AkzoNobel 450 70 1.4
Enka PP Sartorious 100 75 -
Enka PP Sartorious 140 75 - [18]
3MA PP 3M Corporation 91 66 -
3MB PP 3M Corporation 81 76 -
3MC PP 3M Corporation 76 79 -
3MD PP 3M Corporation 86 80 -
3ME PP 3M Corporation 79 85 -
Membrana PP Membrana, Germany 91 - -
PP22 PP Osmonics Corp. 150 70 -
Metricel PP Gelman 90 55 -
Celgard 2400 PP Hoechst Celanese Co. 25 38 -
Celgard 2500 PP Hoechst Celanese Co. 28 45 -
EHF270FA-16 PE Mitsubishi 55 70 -
* Polytetrafluoroethylene; ** Polypropylene; *** polyethylene; **** Polyvinylidene fluoride.
3. Conventional MD Configurations
A MD process can be categorized into four basic configurations, which plays a fundamental
role in separation efficiency and processing cost. Figure 3 shows a schematic diagram of various
conventional configurations including direct contact membrane distillation (DCMD), air gap membrane
distillation (AGMD), sweeping gas membrane distillation (SGMD), and vacuum membrane distillation
(VMD) [40,45–47].
8
Figure 3. Schematic diagram of conventional membrane configurations (a) direct contact membrane
distillation (DCMD); (b) sweeping gas membrane distillation (SGMD); (c) air gap membrane distillation
(AGMD); (d) vacuum membrane distillation (VMD).
3.1. Direct Contact Membrane Distillation (DCMD)

DCMD is the simplest MD configuration, in which a liquid phase (feed) with high temperature
is in direct contact with the hot side of the membrane surface, and a cold aqueous phase is in direct
contact with the permeate side. Therefore, volatile compounds evaporate at the hot liquid/vapor
interface at the feed side. Having been passed through the membrane pores, the vapor phase will
be condensed in the cold liquid/vapor interface at the permeate side. It is notable that the vapor
pressure difference is induced by the temperature difference across the membrane and the hydrophobic
nature of the membrane prevents the feed from penetrating through the membrane. Despite its
simplicity, the conduction heat loss associated with this process is higher than in other configurations.
Membrane modules in DCMD could be shell-and-tube or plate-and-frame employed under cross-flow
or longitudinal flow [38,48–52].
3.2. Air Gap Membrane Distillation (AGMD)

In this configuration, the evaporator channel is similar to that in DCMD. However, an air gap,
which is the controlling factor for the heat and mass transfers, is interposed among the membrane
and the cooled surface. The evaporated volatile compounds pass through the membranes and the
air gap and then condense onto the cold surface. A significant point about this configuration is that
the condensation surface separates the permeate (distillate) from the cold liquid (coolant). Therefore,
the cold liquid can be other liquid like cold feed water. The AGMD configuration has the highest
energy efficiency among the other configurations and the applied membrane could be both flat sheet
and hollow fiber. Furthermore, the used condensation surface is usually a thin dense polymer or metal
9
film [53–59]. Nonetheless, when it comes to popularity, the AGMD process lags behind DCMD and
VMD processes because of its complicated module design [60]. Kalla et al. [60] comprehensively
reviewed the most recent developments in the AGMD process. Based on their investigation,
material gap membrane distillation, double stage AGMD unit, conductive gap membrane distillation,
superhydrophobic condenser surface, multi-stage and multi-effect membrane distillation, modified air
gap membrane distillation, tangent and rotational turbulent inlet flow, and vacuum assisted air gap
membrane distillation process are recent advancements in AGMD process. Woldemariam et al. [61]
presented an exergetic analyzing (exergy evaluations are necessary tools for analyzing the performance
of separation systems, including those featuring MD.) of AGMD systems at a laboratory and pilot
scale. The energy efficiency results indicated that the materials of the condensation plate play a crucial
role in optimizing the performance of MD systems such as heat transfer across modules. Stainless steel
and polypropylene were considered as the appropriate materials in this regard.
3.3. Sweeping Gas Membrane Distillation (SGMD)

In SGMD, which is also known as air stripping membrane distillation, an inert gas (stripping
gas) is applied at the permeate side of the membrane as a carrier to sweep the vapor or collect
vapor molecules from the membrane surface. Similar to AGMD, a gas barrier decreases the heat
loss and significantly increases mass transfer making SGMD a process with promising future
perspectives [62,63]. Nonetheless, SGMD generates a small volume of permeate vapors while
needing large volumes of sweep gas and external condensers, consequently incurring extra expenses.
Therefore, the process has received little attention in comparison with other MD configurations such
as DCMD [19,64]. Applying metallic hollow fibers or a coating membrane with polydimethylsiloxane
could significantly enhance the water vapor permeate flux up to 40% in sweep gas membrane
distillation [65]. Moore et al. [66] developed a non-steady process model to simulate an SGMD
system integrated with solar thermal and photovoltaic power for the desalination of drinking water.
The economic analysis indicated that the optimized proposed technology for cost recovery over
a 20-year service life is 84.7 $/m3 , which is more than alternative sources water costs. Therefore,
future work on SGMD is necessary to make this system economically competitive.
3.4. Vacuum Membrane Distillation (VMD)

In the VMD configuration, a vacuum is created by a pump at the permeate side of the membrane
module. Then, an external condenser is used as for AGMD if the permeate stream is the product.
In addition, the vapor pressure difference is formed by continuous removal of the vapor permeate from
the vacuum chamber. To form the driving force, the created vacuum must be less than the saturation
pressure of volatile compounds in the aqueous feed. For the VMD configuration, the conduction
heat loss is negligible and membrane wetting is avoidable [9,18,67–69]. Table 4 makes a comparison
between different conventional MD configurations and represents the merits and demerits of each
conventional process.
Table 4. The merits and demerits of conventional MD configurations.
Method of Treatment Advantages Disadvantages Reference

Not suitable for removing
non-volatile organics and
Simplest operation
dissolved gasses (water must be
DCMD Least required equipment [33,38,48]
permeating flux)
Simplest MD configuration
Highest heat loss by conduction
among other configurations
High flexibility in MD configuration
Creation of additional resistance
Less conductive heat loss
to mass transfer
AGMD Less tendency to fouling [8,9,55]
Hard module designing
High flux
Minimum obtained output ratio
Without wetting on the permeate side
10
Table 4. Cont.
A suitable configuration for removing Large condenser needed due to

contaminant (volatile component and the small volume of permeate
SGMD dissolved gasses) diffuses in a large sweep gas [8,9,33,70,71]
Without wetting from the permeate side volume
Lower thermal polarization Low flux
Pore wetting risk
Negligible conductive heat loss
Higher fouling
VMD High flux [8,9,33]
Vacuum pump and external
Suitable for aroma compounds recovery
condenser
4. New MD Configurations
Several novel configurations with low energy consumption and improved permeation flux have
been developed by scientists and researchers. A brief review of newly proposed MD configurations is
now presented.
4.1. Thermostatic Sweeping Gas Membrane Distillation (TSGMD)

The AGMD and SGMD processes can be combined in a process named thermostatic sweeping
gas membrane distillation (TSGMD). As Figure 4 clearly illustrates, the inert gas is passed through
the gap between the condensation surface and the membrane. Part of the vapor is condensed on
the condensation surface (AGMD) and the remainder is condensed over the external condenser
(SGMD) [18,72]. This phenomenon basically takes place to minimize the temperature of the
sweeping gas, which increases significantly along the membrane module length. In other words,
the presence of the condensation surface in the permeate side decreases the temperature of the
sweeping gas, which leads to an enhancement in the driving force and the wastewater treatment
performance [33,47]. Condensate production in the TSGMD can be increased by enhancing the
membrane area, recycling cool air back to the membrane module, and decreasing the airflow across
the cooling fins.
Figure 4. Schematic diagram of thermostatic sweeping gas membrane distillation (TSGMD) [73].
Tan et al. [74] developed a novel SGMD system coupled with a thermoelectric heat pump
(TSGMD) to improve the energy efficiency of the water treatment system. The results indicated that
applying a T-SGMD system is capable to double the condensate production per unit energy consumed.
Furthermore, condensate production in the proposed system can be increased by enhancing the
membrane area, recycling cool air back to the membrane module, and decreasing the airflow across
the cooling fins. Cool air recycle could affect the condensate flux without a serious loss of cooling
in comparison with other tested factors during the operation of the T-SGMD. More importantly,
the TSGMD system was able to increase the condensate produced per unit energy without a significant
loss in the cooling capacity per unit energy input. This process can be simulated by using a
11
multicomponent Stefan–Maxwell mathematical model. Based on the model analysis, Rivier et al. [62]
concluded that since the selectivity of TSGMD is far from unity and can be manipulated by changing
operational conditions, this process is suitable for separating azeotropes. Furthermore, the thermal
conductivity of the sweeping gas in TSGMD is four-fold lower than that of the membrane, and a
small mass transfer resistance exists in the cold chamber due to the gaseous bulk. In one study,
the formic acid-water azeotropic mixture was separated by this module [75]. Both experimental and
modeling results suggested that TSGMD can considerably shift selectivity with respect to vapor-liquid
equilibrium (VLE) data, and the system can be successfully used for the separation processes.
4.2. Multi-Effect Membrane Distillation (MEMD)

This configuration is an AGMD module with an internal heat recovery system based on the
concepts of multi-effect, which is suitable for seawater desalination. The cold feed is placed under
the condensation surface as a coolant to condense the permeated vapor compounds as well as to
absorb heat. The pre-heated feed solution is heated once again before entering the feed channel [19,76].
Figure 5 shows a schematic diagram of the MEMD process. The source of heating for this system
should be between 50 to 100 ◦ C and the utilized membrane is usually micro-porous PTFE. It is reported
that the module has very low specific energy consumption (between 56 to 100 kWh/m3 ) [77].
Figure 5. Schematic diagram of the multi-effect membrane distillation (MEMD) [19].
4.3. Vacuum Multi-Effect Membrane Distillation (V-MEMD)

VMEMD shares a similar concept with the multi-effect membrane distillation (MEMD) except for
the vacuum enhancement. The system includes a heater, multiple evaporation–condensation stages,
and an external condenser. Consequently, the distillate is created in both condensation surfaces and
inside the external condenser. In addition, the vacuum condition is developed at the air gap between
membrane and condensation surfaces to eliminate the excess air/vapor from the process. In this
context, memsys is a state of the art technology and relatively new configuration based on vacuum
multi-effect membrane distillation. This highly efficient technology consists of a novel internal heat
recycling concept that results in a significant reduction in energy consumption [19,69,78–80]. Figure 6
shows a schematic diagram of the V-MEMD system. The performance of this type of membrane is
affected by changing heating conditions, cooling, and feed. The main factors for its optimization and
scale-up are the number of stages and the size of each stage. In an experimental study, Zhao et al. [80]
found that heating and cooling temperatures are the most important factors affecting the module
flux and efficiency. By comparing this module with common technologies, one can conclude that
it can provide better heat and mass transfer rates [81]. Furthermore, Mohamed et al. [82] reported
that flow rates are also important factors affecting the module performance. They suggested that the
system performance can be improved more by performing the following tips: separating distillate and
brine tanks, utilizing magnetic or float flow meters, using a separate pump for heating recirculation,
and improving the heat isolation or recovering the heat loss in the brine stream.
12
Figure 6. Schematic diagram of vacuum multi-effect membrane distillation (V-MEMD) [19].
4.4. Material-Gap Membrane Distillation (MGMD)

Since AGMD has shown the lowest permeation flux among all configurations, a new and efficient
configuration named material gap membrane distillation (MGMD) was developed and designed by
researchers to compensate for the weakness of AGMD. In this membrane module, the air gap is filled
with either nonconductive materials such as porous support, sand, and sponge (polyurethane) or
conductive materials such as the metal mesh. Therefore, the vapor compound flux increases up to
200–800% [83–86]. Figure 7 shows a schematic diagram of the MGMD system.
Figure 7. Schematic diagram of material gap membrane distillation (MGMD) [83].
To simulate large-scale module conditions, it is essential to perform the experiments at

low-temperature gradients across the membrane. This is because at this condition, the heat recovery is
maximized and the water vapor flux would be at a minimum [81].
4.5. Permeate-Gap Membrane Distillation (PGMD)

The combination of DCMD configuration and AGMD module is regarded as permeate-gap
membrane distillation (PGMD) or liquid-gap membrane distillation (LGMD). In this configuration,
the additional compartment between the membrane and the condensation surface is filled with
13
a static cold liquid solution or with permeate. It is also notable that applying PGMD leads to a
higher-surface-related permeate output in comparison with AGMD. This is mainly because, in AGMD,
the diffusion resistance of the air layer acts as an obstacle in the process. However, PGMD has greater
heat loss than AGMD [83]. Figure 8 shows a schematic diagram of the PGMD system. Winter et al. [85]
proposed PGMD with internal heat recovery that was achieved by separating the distillate and
coolant. As a result, any liquids such as the feed water can be utilized as the coolant. Therefore,
one can place PGMD between AGMD and DCMD to lower the sensible heat transfer to the permeate,
but at the cost of greater heat loss. By accepting the superior performance of PGMD over AGMD,
Swaminathan et al. [84] reported that the countercurrent flow of the pure water in the gap to the
cold stream results in the highest energy efficiency, and increasing the gap conductivity enhances the
permeate production.
Figure 8. Schematic diagram of permeate-gap membrane distillation (PGMD) [86].
5. Application of MD
Generally, MD has been applied in various areas including desalination, the chemical industry,
the food industry, the textile industry, pharmaceutical, and biomedical industries and the nuclear
industry. Table 5 provides more information about each application.
Table 5. The application of the MD process in different industries.
Area Application MD Configuration Reference

Removing volatile organic compounds from water VMD
Acid concentrating DCMD
Chemical industry [33,87–89]
Crystallization SGMD
Azeotropic mixtures separation AGMD
VMD
DCMD
Desalination Producing pure water from brackish water [33,34,90,91]
SGMD
AGMD
Juice concentrating VMD
Food industry (Juice
Processing of milk DCMD [33,92–95]
and Dairy)
Temperature sensitive materials AGMD
14
Table 5. Cont.
Dye removal VMD

Textile industry [33,96–98]
Wastewater treatment DCMD
Removing sodium sulfate, organic and inorganic
Pulp and paper compounds, adsorbable organic halogens (AOX), color,
DCMD [99–101]
industry phenolic compounds, and chemical oxygen demand (COD)
from wastewater
Pharmaceutical and Wastewater treatment
DCMD [30,33,102,103]
biomedical industries Water removing from protein and blood solutions
Producing pure water
DCMD
Nuclear industry Wastewater treatment [31,33,104,105]
VMD
Radioactive solutions concentrating
Reusing mining effluents
Gold mining Removing hazardous metals and ions such as sulfate from DCMD [106]
mining effluents
Bioethanol production
Recovery of ethanol from scrubber-water AGMD [107]
plants
The Application of MD in Water and Wastewater Treatment

MD technology has been extensively used in the purification of wastewater produced from
various industries, in order to recover valuable compounds or make wastewater less dangerous to the
environment. However, in comparison with other membrane processes, MD is more difficult to apply
on an industrial scale because of some serious economic and engineering problems.
When it comes to desalination, many various types of technologies are available including
thermal- and membrane-based desalination processes. The thermal-based group comprises
processes such as multistage flash distillation (MSF); multi-effect distillation (MED); and, single- or
multiple-effect evaporation (SEE/MEE) systems, which can be coupled to mechanical or thermal vapor
compression (MVC/TVC). Membrane technologies include reverse osmosis (RO), forward osmosis
(FO), electrodialysis (ED), and membrane distillation (MD). Onishi et al. comprehensively reviewed
the main advantages and disadvantages of each process [108].
RO has been considered as the most economical and the least energy intensive technology for
large-scale seawater desalination, followed by MED and MSF [23,109,110]. However, the unique
characteristics of MD have made this process an excellent option with high efficiency. For instance, MD,
in particular, DCMD, has enormous potential in the desalination of highly saline wastewaters where
MD fluxes can remain comparatively high, much higher than those for RO. Moreover, in small-scale
applications where the quality of water is not suitable for currently established technologies such
as RO-based processes, MD is an effective alternative. This process could also be co-located with
industrial facilities and power generation systems to take advantage of the waste heat and low-cost
thermal energy to produce high-quality water. In addition, MD is a potential treatment candidate
for combining with other separation techniques such as RO, ED, crystallization, and bioreactors
to enhance water recovery and decrease the amount of concentrate requiring disposal. Therefore,
MD has a practical application in water treatment with zero (or near zero) liquid discharge and can
be more economical than other established thermal processes in zero-liquid discharge applications.
The permeate with extremely high quality in the MD process compared to RO permeate can also
offer considerable benefits particularly when purified water is required as boiler feed [19,23,111].
In mining industries, the process combining ultrafiltration (UF) and reverse osmosis (RO) is widely
applied for wastewater treatment, in which 80% of COD, more than 95% chroma and almost all the
ferrous irons and bacteria can reject significantly. Nonetheless, the brine discharge and the water
recovery ratio (limited to around 30% to 60%) of the RO process remain serious issues in this regard.
Therefore, MD could be proposed to address these problems by enhancing the water recovery ratio
and recovering minerals [8,112,113].
Lokare et al. [114] investigated the synergies and potential of DCMD for wastewater treatment
produced during gas extraction from unconventional (shale) reservoirs in Pennsylvania (PA).
15
An exhaust stream from Natural Gas Compressor Station (NG CS) was used as the waste heat source
for DCMD operation providing a feasible option to treat high salinity generated water. They developed
an ASPEN Plus simulation of DCMD using fundamental heat and mass transfer equations and the
literature correlations to optimize the design and operation of large-scale saline water desalination
and estimated the energy requirements of the process. The minimum temperature gradient of 10 ◦ C
between the permeate-side and feed stream was used to achieve the optimum membrane area when
several membrane modules are provided in series. According to obtained results, the amount of
available waste heat of NG CS regardless of the produced water salinity is much higher than the
amount of waste heat needed to concentrate produced water in PA to 30% salinity. Moreover, the results
indicated that DCMD is able to concentrate all the produced water in PA utilizing NG CS waste heat.
Nonetheless, the economic probability of the process must be assessed to determine major cost drivers
and barriers. Ali et al. [115] evaluated the integration of a microfiltration and membrane distillation
process for water treatment and minerals recovery from produced water. The results indicated that
the integrated process offers the opportunity of converting generated water into salt and freshwater
highly efficiently and also minimizes the issue of waste disposal. Nonetheless, to make the system
commercially available, better arrangements for separating crystals of various salts should be made.
Boukhriss et al. [116] simulated and experimentally studied an AGMD membrane distillation pilot for
the desalination of brackish water and seawater with zero liquid discharged. The theoretical model
was generated using Matlab and verified utilizing pilot-scale experimental data. Their investigation
showed that the AGMD configuration is capable of producing desalinated water with zero liquid
discharged even at a low hot-fluid supply temperature of 25 ◦ C, which makes the system feasible to
be coupled with low-temperature heat sources such as a solar collector. Baghbanzadeh et al. [117]
investigated a zero thermal energy input membrane distillation (ZTIMD) process which was also
a zero-waste system. The required thermal driving force for the process was provided by using
the warm seawater of the surface as the feed and the cold water at the bottom of the sea as the
coolant. The innovative concept of their invention revolutionized the seawater desalination industry.
This is mainly because ZTIMD was revealed to be economically more efficient than current seawater
desalination processes by simulations based on a single-pass DCMD system. In other words, under the
optimum conditions, the proposed ZTIMD process could provide pure water with a cost of $0.28/m3
at the particular energy consumption of 0.45 kW h/m3 , which is notably lower than that of the
main current seawater desalination methods such as RO ($0.45–2.00/m3 ). A novel water desalination
method which couples thermal membrane distillation (TMD) with reverse osmosis (RO) was developed
by Huang et al. [118]. They proposed a water–energy integration process with the strong nexus
of water and energy. Furthermore, a dual-objective model was formulated to analyze the system
thermodynamically and optimize the process under the objective function of minimizing fuel and
freshwater consumption. The sensitivity analysis of the heat-to-power demand ratio revealed that
the RO-TMD coupling water desalination process is superior to traditional single RO at a high
heat-to-power demand ratio in terms of minimizing freshwater and fuel consumption. In the proposed
novel water–energy integration system, the fuel and freshwater consumptions were reduced by 1.7%
and 21.0%, respectively, compared with those of the conventional system.
A comprehensive summary of more MD applications in wastewater treatment on a
laboratory-scale is presented in Table 6. Although the number of research papers published in
the MD application in wastewater treatment has increased significantly over the past few years,
tremendous effort should be taken to design and fabricate novel membrane modules to permit
a successful industrial application of this separation technique. It is worth mentioning that,
various excellent membrane modules have become available in the market recently. Therefore, in the
near future, a MD process with industrial applications may become increasingly available.
16
Table 6. Summary of MD applications in wastewater treatment.
Feed Membrane Configuration Membrane Material Contaminant Removal Efficiency (%) Scale Reference
Radioactive wastewater (SrCl2) VMD PP Sr2+ Over 99.60 laboratory-scale [104]
Metal solution Poly(vinylidenefluoride)-titanium
(salts of Co (II), Zn (II), Cu (II), Ni VMD tetraisopropoxide Heavy metals Total removal laboratory-scale [119]
(II), Cd (II) and Pb (II)) PVDF-TTIP
Distilled water and crude oil VMD PVDF Total Organic Carbon (TOC) 93.4–97 laboratory-scale [120]
Polyphenols 99.6
Olive Mill WasteWater (OMWW) DCMD & VMD PP laboratory-scale [121]
TOC 89 and 99.6
Colour
95.3
Total Dissolved Solids(TDS)
Industrial textile wastewater DCMD PVDF-Cloisite 15A nanocomposite 93.7 laboratory-scale [122]
Chemical Oxygen
90.8
Demand(COD)
PVDF modified by ethylene glycol
Synthetic dye solution DCMD RB5 99.86 laboratory-scale [98]
(EG)
Highly saline radioactive Nuclides (Co(II), Sr(II), Cs(I))
DCMD PP >99.97% laboratory-scale [123]
wastewater and boron (B)
Osmotic membrane
Synthetic wastewater and PTFE active layer and a PP
bioreactor (OMBR)—(DCMD) 30 trace organic contaminants >90% laboratory-scale [37]
Seawater supporting layer
hybrid system
17
Geothermal water AGMD PP, PTFE and PVDF Boron 99.5% laboratory-scale [21]
High salinity hydraulic
Combined Electrocoagulation Ethylene chlorotrifluoroethylene Turbidity, Total suspended 96%, 91% and 61%,
fracturing produced water laboratory-scale [124]
(EC) and DCMD (ECTFE) solids (TSS) and TOC respectively
(HFPW)
DCMD combined with
Industrial dyeing wastewater physicochemical and PTFE and PVDF COD and color removal 96% and 100% respectively laboratory-scale [49]
biological treatment
PVDF modified with silica
Oil and gas emulsified
Saline oily wastewater DCMD nanoparticles and Polystyrene (PS) Highly desirable laboratory-scale [125]
wastewater
microspheres
PVDF membrane was coated by
Mining wastewater VMD Hyflon AD materials (Hyflon Mining waste Highly efficient laboratory-scale [126]
AD40L, Hyflon AD40H)
Bentazon herbicide solutions VMD PTFE Bentazon Very effective laboratory-scale [127]
Fermentation wastewater DCMD PP COD, TOC 95% laboratory-scale [128]
6. Fouling Phenomenon in MD Process

The term “fouling” has been regarded as a complex phenomenon which is an inevitable part
of each membrane process and adversely affects membrane performance. Generally, fouling is the
precipitation and accumulation of various foulants such as particles and dissolved components on the
external surface or inside the membrane as pore blocking. Figure 9 clearly illustrates external surface
fouling and internal fouling pore blocking.
Figure 9. Schematic diagram of surface fouling (external) and pore blocking (internal) [35].
A fouling layer puts on extra thermal and hydraulic resistance to the process and decreases the
temperature difference across the membrane, which means a sharp reduction in the driving force.
Consequently, the permeate flux decreases drastically. If fouling does not address this properly,
it will contribute to membrane damage, early membrane replacement or even shutdown of the
operation [35]. The main fouling phenomena commonly occur during water and wastewater treatment
and are categorized based on the foulant type as organic, inorganic (scaling), biological, and particle
fouling. When suspended solids and metal hydroxide in source water accumulate on the membrane
surface and inside the membrane pores, forming a cake layer, the phenomenon is known as particle
fouling. Scaling is regarded as the precipitation of inorganic salts presented in source water such
as calcium carbonate, calcium sulfate, silicate, NaCl, calcium phosphate, BaSO4 , SrSO4 , ferric oxide,
iron oxide, aluminum oxide, inside the membrane pores, which leads to bulk, pore plugging/clogging,
and membrane crystallization. Furthermore, the adsorption of natural organic matter (NOM) such
as HA, fulvic acid, protein, polysaccharides, and polyacrylic polymers on the membrane has been
considered as organic fouling which contributes to gel formation of the macromolecular compounds
and membrane wetting. As well as that, when various aquatic organisms such as fungi, sludge, algae,
yeast, and micro-organisms in source water form a biofilm on the membrane, the fouling is named
biofouling [35,129]. Nevertheless, mostly, a combination of several types of fouling mechanisms
occurs in actual MD processing, as opposed to a single fouling mechanism which makes the problem
more complicated to address. It is worth mentioning that membrane fouling is expected to be
less devastating in MD, due to the absence of hydraulic pressure in such processes compared to
pressure-driven membrane processes. Nonetheless, the continuing presence of the membrane in the
highly concentrated feed solution to meet the pure liquid discharge makes the MD process vulnerable
to membrane fouling.
18
Bush et al. [130] compared the performance and fouling behavior of MD and nanofiltration
(NF) processes applying silica-saturated water from 225 mg/L to 600 mg/L SiO2 to illustrate the
potential differences in the silica scaling behavior and its impacts on MD performance compared to a
pressure-driven membrane process. The results showed that salt rejection during MD was >99.8% for
all solutions tested and was unaffected by scaling, while rejection during NF was between 78–90% and
tended to decrease after scaling. NaOH solution at pH > 11 was used to clean the fouled membranes
for both processes, which was extremely effective at the restoring water flux but unable to remove
the silica scale layer completely. Tow et al. [131] analyzed the fouling and scaling behavior of RO,
forward osmosis (FO), and DCMD using a single membrane module under the same hydrodynamic
conditions (flux and cross-flow velocity). During fouling experiments, calcium sulfate was used as a
model inorganic foulant and alginate was utilized as a model organic foulant. Based on their results,
FO showed the greatest scaling resistance while MD tolerated organic fouling much better than FO and
RO. Although FO and MD each indicated a higher resistance to one type of foulant, neither process
outperformed RO in the resistance to complex fouling including organic and inorganic fouling.
Typically, the characteristics of foulants (concentration, molecular size, solubility, diffusivity,
hydrophobicity, charge), water (solution chemistry, pH, ionic strength, presence of organic/inorganic
matters), and membrane (hydrophobicity, surface roughness, pore size, surface charge,
surface functional groups), as well as operational conditions (flux, solution temperature, flow velocity),
can significantly affect the fouling formation phenomenon [61,132]. In this regard, various approaches
are employed by researchers in order to detect and prevent membrane fouling summarized in
Table 7. Shan et al. developed a versatile approach for designing an amphiphobic membrane
surface [133]. During this method, a biomimetic system was investigated to design an amphiphobic
surface with a unique structure and controllable wettability. A commercial PVDF was modified
via superhydrophobic nanocoating using polydopamine (PDA) followed by the fluorination of
1H,1H,2H,2H-perfluorodecanethiol. The proposed amphiphobic membrane indicated excellent
superhydrophobicity with a water contact angle of 167.6◦ + 0.27◦ as well as remarkable chemical
and thermal stability under severe conditions. Another striking feature about this membrane was its
outstanding anti-fouling capability with higher flux and great salt rejection in the long-term DCMD
process, which exhibits promising potentials for industrial applications.
19
Table 7. Summary of detection and prevention methods for membrane fouling.
Detection Method(s) Prevention Process(es) Reference
• Permeate flux decline

• Scanning electron microscopy (SEM)
• Energy dispersive X-ray spectroscopy (EDS) to evaluate the
elemental composition of a fouled layer
• X-ray powder diffraction (XRD) to analyze and evaluate the

crystalline nature of inorganic, organic, polymers, metals, or
composite materials • Membrane flushing (membrane cleaning by regular deionized
• Atomic force microscopy (AFM) is applied to characterize the (DI) water)
surface of the membrane • Ultrasonic irradiation technique
• SEM–EDS/TEM (transmission electron microscopy)–EDS • Chemical cleaning of membrane by acids, alkalis, metal
• Atomic absorption spectroscopy (AAS) analysis to determine chelating agents, surfactants, enzymes, and oxidizing agents (2
the fouling composition using the absorption of optical h water, with 0.1 M NaOH or 2–5 wt.% HCl solutions or 0.029
radiation (i.e., light) by free atoms in the gaseous state M Na2 EDTA and 0.058 M NaOH or citric acid followed by
• Contact angle (CA) (the angle between the liquid drop and the NaOH or by HCl)
horizontal surface, an angle below 90◦ shows hydrophilic • Pretreatment (coagulation, multimedia filtration, sonication,
behaviour, while an angle above 90◦ shows hydrophobicity) deep-bed filtration, pH changes boiling/thermal water
softening, chlorination, degasification,)
20
• Membrane autopsy [35,61,128,129,132,134–150]
• Fourier transform infrared (FTIR) to obtain the infrared (IR) • Gas bubbling
spectra of the sample for evaluating and identifying the • Increasing the feed flow rate
chemical bonds and molecular structure of organic molecules • Temperature and flow reversal
and analyzing of organic and inorganic functional groups on • Using anti-fouling membranes (such as membrane surface
the membrane surface modification by applying different superhydrophobic coatings
• Attenuated total reflectance-fourier transform infrared such as sodium alginate hydrogel, TiO2 nanoparticles, a
spectroscopy (ATR-FTIR) to analyze organic and mixture of polydimethylsiloxane (PDMS) and hydrophobic
inorganic fouling SiO2 nanoparticles)
• Gel permeation chromatography or gel filtration • Using antiscalants (chemical additives) such as condensed
chromatography (HPSEC) or using flow field-flow polyphosphates, organophosphonates, and polyelectrolytes
fractionation FlFFF to determine the size or molecular weight
distribution of organic matters
• Liquid-chromatogram organic carbon detection (LC-OCD)
• Zeta potential (to determine the electrokinetic phenomena of
membranes and evaluate the possible interaction between the
foulants and membrane surface)
Table 7. Cont.
• Tensile strength
• Direct visualization
• EXSOD (ex-situ scale observation detector) for real-time
crystal monitoring of membranes
• Autopsy
• Optical laser sensor method for investigation of the deposit

thickness on a membrane
• Ultrasonic time-domain reflectometry (UTDR) to observe and
evaluate the deposition of combined organic and colloidal
fouling on the membrane surface as well as providing physical
characteristics of the media where the waves travel and also
providing the real-time measurement of the location of
an interface
• Inductively coupled plasma mass spectrometry (ICP-MS) to
determine the concentration (ppm, ppb) of metal and
non-metal elements in a fouling layer
• Streak-plate method to determine the number
of microorganisms
21
• A confocal laser scanning microscopy (CLSM) technique is
applied to obtain high-resolution optical images with depth
selectivity and also to visualize and quantify biofilms in-situ in
combination with a fluorescent probe.
• Infrared thermography (IRT) technique is applied to measure
the surface temperature and its distribution figure out whether
a foulant is metallic or non-metallic in nature
• Excitation Emission-Matrix Fluorescence Spectroscopy (EEM)
to detect proteins, acid and other organic materials present in
fouled membranes
7. Wetting Phenomenon in MD Process

In the wetting phenomenon, water enters the pores of the membrane and fills them by breaking
the surface tension presenting between liquid and vapor on the surface of the membrane [151].
As previously described, mass transfer through the membrane pores only takes place in the vapor
phase, from a hot feed solution. Therefore, the liquid feed must not be allowed to penetrate partially
or entirely through the dry membrane pores. As Figure 10 clearly illustrates, the degree of membrane
wettability may vary according to the area wetted by the liquid. The water might be present only
in the external surface layers of membrane pores, or a fraction of pores inside the membrane with
the largest diameters might be wetted, or all the pores inside the membrane might be filled by water.
To address this issue, various approaches have been developed [152–156]. Extra liquid entry pressure
and membrane fouling are two principal causes of membrane wetting. Kim et al. [157] fundamentally
investigated the MD process integrated with crystallization in order to prevent inorganic scaling
induced by multivalent ions such as barium and calcium in shale-gas-produced water treatment.
By utilizing the proposed system, scalant loading was decreased significantly and membrane wetting
was mitigated dramatically. Therefore, the total recovery of the process was increased up to 62.5%.
Furthermore, experimental results indicated that the pretreatment process for oil and grease before MD
application is mandatory for enhancing the stability of water production and sustaining the integrity
of permeate water quality.
A comprehensive review of wetting mechanisms, wetting causes, and wetting detection methods
was carried out by the authors of [156]. Jacob et al. [26] developed a novel method to visualize and
evaluate wetting in the MD system based on the detection of dissolved tracer intrusion, which is
capable of detecting all pore wetting mechanisms at different locations on a membrane. The function
of the developed method was based on the ex-situ detection of a tracer (salt) intrusion by SEM-EDX,
after the performance of the VMD applying a saline solution. Guillen-Burrieza et al. [158] investigated
the effects of the MD operation variables on membrane wetting. They concluded that the wetting
time and rate are significantly reduced by the parameters enhancing flux. Damtie et al. [159]
suggested a new methodology to treat highly polluted industrial wastewater and analyzed the wetting
tendency of different membranes. They studied the performance of the most popular commercially
available hydrophobic membranes including polytetrafluoroethylene (PTFE), polypropylene (PP),
and polyvinylidene fluoride (PVDF). The investigation confirmed that the type of membrane material
and membrane pore size greatly influence the process efficiency. Moreover, the relationship between
the membrane surface wettability and MD performance is affected by the composition of feed water
during the water treatment [160].
Eykens et al. [161] explored an alternative for the traditional hydrophobic membrane
materials through the deposition of a hydrophobic coating using vacuum plasma on a commercial
hydrophilic membrane with a microporous structure to prevent membrane wetting at high salinity.
The required hydrophobicity (>100◦ ) was obtained and membrane wetting was prevented effectively.
Chen et al. [162] developed a ZnO nanostructure on alumina hollow fiber membranes with a uniform
pore size of 197 nm and a thin wall of 200 μm to enhance the wetting resistance during the DCMD
process with a low surface tension feed. The contact angle of the omniphobic hollow fiber (HF)
membrane for a 90% v/v ethanol/water mixture was as high as 138.1◦ . The SEM, EDX, and AFM
analyses showed that the omniphobic alumina hollow fiber membranes not only showed extraordinary
wetting resistance for desalinating low surface tension wastewaters but also showed a great potential
for industrial applications because of the simplicity of scaling-up.
22
Figure 10. Schematic diagram of membrane wettability stages: (a) non-wetted, (b) surface wetted,
(c) partial wetted, and (d) fully wetted [35].
8. Novel Approaches to MD Technology

Polymeric porous membranes are traditionally fabricated by conventional methods, most of
which contribute to relatively low porosity. Recently, various novel membrane production techniques
that have a high porosity above 80% and interconnected open pore structures with a high surface
roughness are applied to enhance the membrane performance and provide high flux in MD [163].
Figure 11 illustrates a detailed classification of traditional and novel membrane production methods.
Eykens et al. [163] offered a comprehensive definition of each technique and provided advantages and
disadvantages of each method in their review paper.
Figure 11. Schematic diagram of various methods for membrane production applied in MD
technology [163].
23
Woo et al. [164] investigated the development and performance of an omniphobic PVDF
membrane which was successfully fabricated by electrospinning and modified by tetrafluoromethane
(CF4 ) plasma treatment for water brine treatment with an AGMD system. They studied the effects of
various durations of plasma treatment on the characteristics of the nanofiber membrane. The optimum
obtained results (treatment duration: 15 min; liquid entry pressure: 187 kPa; flux: 15.28 L/(m2 ·h);
salt rejection ~100%) demonstrated that the formation of new CF2 -CF2 and CF3 bonds after plasma
treatment without considerably altering the morphology and physical properties could resist the
wetting phenomenon by reducing membrane surface energy and providing omniphobic property
for low surface tension liquids such as methanol, mineral oil, and ethylene glycol. Therefore,
the proposed omniphobic membrane has great potential to treat water containing high salinity
and organic contaminants. An et al. [165] fabricate an amphiphobic PVDF-co-HFP electrospun
nanofibrous membrane with excellent anti-wetting properties for the MD process. They applied
1H,1H,2H,2H-perfluorodecyltriethoxysilane (FAS) to fluorinate PVDF-co-HFP fibers followed by a
crosslinking process to form a network upon dealcoholization under thermal treatment. Based on their
results, the FAS-coated PVDF-co-HFP nanofibrous membranes show excellent stable amphiphobicity
with high contact angles of 127◦ against water and oil even on challenging and critical conditions such
as long-term operation, presenting sodium dodecyl sulfate surfactant in the saline feed, or boiling
water and strong base and acid etchings. Boo and Elimelech [166] provided a self-heating membrane
for MD via CNT Joule heating which enhances the desalination efficiency of high-salinity brines.
This novel technology increases the thermal driving force by increasing the temperature of the saline
feed stream without the need for external heat. Joule heating that is also known as ohmic heating or
resistive heating is the process in which thermal energy is produced by the resistance of a conductor to
electron flow. In general, in self-heating membranes, a thin conductive composite layer is formed via
a sequential spray coating of CNTs and Polyvinyl alcohol (PVA) on a hydrophobic porous substrate
(polytetrafluoroethylene).
More importantly, applying novel renewable energy-driven systems in water treatment has
dramatically increased with the aim of energy conservation. Figure 12 illustrates using different
renewable energy sources including solar energy, waste heat, and geothermal energy as well as
applying a membrane distillation crystallization (MDC) method via the precipitation of crystal salts
under supersaturation conditions in a crystallizer. A detailed explanation of each method could be
found in the following references [64,167]. Furthermore, MD systems with water recycling and heat
regeneration could significantly enhance water recovery and thermal efficiency and, consequently,
are capable to meet the actual demand [168]. Long et al. [169] investigated a DCMD system integrated
with low-temperature waste heat for water treatment. They developed a modified model characterizing
the heat and mass transfer in the DCMD, which was validated by excellent agreement with the
experimental data. Based on their study, gain output ration (GOR) and mass recovery rate are two
major factors to evaluate the performance of a DCMD system with heat recovery. Lee et al. studied the
effects of two different types of seawater-coolant feed (backward feed (BF) and parallel feed (PF))
arrangements in a waste-heat-driven multistage vacuum membrane distillation with regard to the
improvement of system performance [170]. Based on their investigations, the proposed system with the
BF arrangement is more efficient and economical for freshwater production than the PF arrangement at
a smaller number of module stages in terms of the specific thermal energy consumption. Furthermore,
they comprehensively analyzed different BF arrangement scenarios and found the optimal number to
be a 24-stage VMD desalination system in terms of energy efficiency and cost.
24
ȱ
Figure 12. Schematic diagram of various renewable energy-driven MD systems.
9. Economic Analysis of MD Process

Energy-efficient water treatment and desalination processes play a crucial role in enhancing
freshwater supplies without imposing considerable strain on scarce resources. By applying low-grade
or waste heat, membrane distillation (MD) has shown great potential to augment sustainable water.
Nonetheless, economic analyses are essential for the viability of the MD process since a huge amount of
energy is used for the water evaporation in order to separate water from non-volatile contaminants and
pumping [33]. Furthermore, it should be noted that an energy-efficient MD system effectively applies
the thermal gradient for vapor transfer in comparison with conductive heat loss, which is measured
by the membrane thermal efficiency of the membrane. In addition, the latent heat of condensation is
productively reused in an economical MD system [90]. Recently, the authors of [171] critically examined
the crucial factors affecting the energy efficiency of MD processes and explained how future membrane
design and process development could considerably boost MD efficiency. They demonstrated that the
size of the system can significantly influence the performance of the process. Moreover, they found
that enhancing the porosity of the membrane and optimizing its thickness can dramatically increase
the MD efficiency. In addition, the configuration of the process plays a leading role in maximizing the
latent heat recovery. More importantly, the novelty of membrane materials and surface modification
are essential for increasing membrane robustness. Swaminathan et al. [172] comprehensively analyzed
a single-stage MD system in terms of the energy efficiency (indicate as a gained output ratio or GOR)
and vapor flux for the desalination of feed streams up to a high feed salinity. The system was designed
to determine the thickness of the membrane with an optimal cost as well as the size of the system as a
function of the ratio of specific costs of heat energy and module area. Based on the obtained results,
in the small systems with low salinity, GOR increases and flux decreases with a rise in the membrane
area. Furthermore, for the solutions with high salinity, it is essential to determine a critical system size
beyond which GOR begins to decrease.
25
Based on the performance of the MD, the total capital cost of the system, optimum flow conditions,
and MD configurations, and the cost of the MD system production may vary from 0.26 to 130 $/m3 .
Furthermore, the total energy consumption of the process could change from 1 to 9000 kWh/m3
based on the type and size of the system, operating conditions, sources of the provided energy,
recovery approaches, and the estimated cost of the procedures. Additionally, by applying waste heat,
the production cost of a 30,000 m3 /d (capacity plant) MD desalination plant could be reduced from 2.2
to 0.66 $/m3 [173,174].
A comprehensive cost evaluation of a 111 MWe solar power tower (SPT) plant integrated with the
DCMD system was investigated by Soomro and [114,175]. The average freshwater production by the
proposed MD system was evaluated up to 40,759 L/day with a cost of $0.392/m3 . The authors of [176]
evaluated the economic feasibility of MD for wastewater treatment by performing a techno-economic
assessment (TEA) for a hypothetical 0.5 million gallons per day (MGD) direct contact MD (DCMD)
which concentrates produced water from 10% (100,000 mg/L) TDS to 30% salinity. Sensitivity analysis
showed that the TDS level of the feed and the price of thermal energy significantly affect the total
cost of treating produced water. Furthermore, they revealed that utilizing a source of waste heat
could considerably decrease the total cost from $5.70/m3f eed to $0.74/m3f eed . Hitsov et al. [177]
demonstrated a graphical user interface tool which could design a comprehensive MD system,
comprising all of the supporting equipment and capable to estimate the price of the obtained distillate
for different distillation configurations at various production scales and concentration factors. They also
investigated several case studies that varied from 2 to 1000 m3 of distillate per day, with a final brine
salinity up to 20 wt.% and feed temperature up to 80 ◦ C, and demonstrated the optimal system design
for each case. The cost of distillation varied from 25 €/m3 (the smallest scale) to 2.1 €/m3 for the
largest scale. Soomro and Kim [178] published an economic evaluation of integrating a 50 MWe
parabolic-trough (PT) plant with the DCMD system for freshwater production. The economic analysis
illustrated that the proposed system could be a sustainable and economical process producing up to
14.33 m3 of freshwater per day at a price of $0.64/m3 .
According to a technical economic study conducted by the authors of [106], the capital expenditure
(or capital expenses) (CAPEX) and operational expenditure (or operational expenses) (OPEX ) of DCMD
applied in gold mining effluent treatment (for a membrane lifespan of 1–5 years) are estimated to be
US$ 305,483.85 and 0.13 to 0.27 US$/m3 , respectively, while the amounts are US$ 575,490.30 and 2.00
to 2.10 US$/m3 for the NF process. This is mainly because the required energy for NF is almost 40
times greater than that for DCMD, due to the need for cooling the feed in the NF process. Moreover,
98% of the thermal energy consumption in DCMD is reduced by applying the residual heat of the
effluent. The CAPEX was measured as explained by Hitsov et al., considering a membrane area of
24 m2 per module and the capital cost (Ccap) was calculated per cubic meter of effluent (Ccap/m3 ),
as explained in great detail by Reis et al. [106]. Woldemariam et al. [107] evaluated the CAPEX and
OPEX of an industrial-scale district heat-driven MD process for the recovery of ethanol from scrubber
water. The economy of the distillation system was obtained from the case studied plant including
production rate, the amount of steam used, and other costs such as capital investment. Results of
the techno-economic investigation indicated that MD could be a competitive technology for ethanol
recovery when the system is supplied by low-grade heat such as waste heat or district heating network.
10. Future Trends and Conclusions

MD is a thermally driven treatment process, which has been perfectly able to treat water
containing an extremely high level of salinity and hazardous contaminants. More importantly,
MD has the possibility to integrate with other separation processes and renewable energy sources.
Nonetheless, few studies were performed on a large scale and with long-term MD application since
several challenges such as high energy consumption, fouling, scaling, and pore wetting have limited
its commercial application. Therefore, it is essential to fabricate novel membranes with specific
characteristics such as low resistance to mass transfer, low thermal conductivity, high thermal stability,
26
high chemical resistance, or a membrane with surface modifications to improve MD performance and
characteristics in order to minimize fouling and wetting phenomena and energy consumption, as well
as enhancing the permeate flux quality and quantity. Moreover, the development of MD application
in wastewater treatment needs to handle more organic and biological fouling, in combination with
inorganic scaling. This makes the fouling study more complicated; therefore, more insight into the
mechanisms of mixed fouling should be given careful and special attention in the future.
Generally, MD process can be categorized into four basic configurations including direct
contact membrane distillation (DCMD), air gap membrane distillation (AGMD), sweeping gas
membrane distillation (SGMD), and vacuum membrane distillation (VMD). Additionally, various novel
configurations with low energy consumption and improved permeation flux such as TSGMD, MEMD,
V-MEMD, MGMD, and PGMD have been proposed recently. Polypropylene (PP), polyvinylidene
fluoride (PVDF), polytetrafluoroethylene (PTFE), polyethylene (PE), inorganic materials, and carbon
nanotubes (CNTs) are the most popular micro-porous membranes commercially fabricated in the
form of plate and frame, hollow fiber, tubular, spiral wound, and flat sheet. However, different novel
techniques such as electrospinning and surface modification have been employed recently to produce
a membrane with a high porosity of above 80% and enhance the membrane performance by providing
high flux.
Author Contributions: The manuscript was written by P.B. and reviewed by all authors. All authors have given
approval to the final version of the manuscript.
Funding: This research received no external funding.
Conflicts of Interest: The authors declare no conflict of interest.
Abbreviations and Symbols

AGMD Air Gap Membrane Distillation
COD Chemical Oxygen Demand
CN Cellulose Nitrate
CNT Carbon Nanotube
DCMD Direct Contact Membrane Distillation
ECTFE Poly (ethene-co-chlorotrifluoroethene)
ED Electrodialysis
FEP poly (vinylidene fluoride-co-chlorotrifluoroethylene)
FO Forward Osmosis
FS Flat sheet
HF Hollow fiber
LEPW Liquid Entry Pressure of Water
LGMD Liquid-Gap membrane distillation
MD Membrane Distillation
MEE Multiple-Effect Evaporation
MED Multiple-Effect Distillation
MGMD Material-Gap Membrane Distillation
MSF Multi-Stage Flash
NF Nanofiltration
NOM Natural Organic Matter
PES Polyethersulfone
PET Poly(ethylene terephthalate)
PGMD Permeate-Gap Membrane Distillation
PP Polypropylene
PS Polysulfone
PPESK Poly(phthalazinone ether sulfone ketone)
PTFE Polytetrafluoroethylene
27
PVA Polyvinyl alcohol

PVDF Polyvinylidene fluoride
PVDF-co-CTFE Pol (vinylidene fluoride-co-chlorotrifluoroethylene(
PVDF-co-HFP Poly(vinylidene fluoride-co-hexafluoropropylene)
PVDF-co-TFE Poly(vinylidene fluoride-cotetrafluoroethylene)
RC Regenerated cellulose
RO Reverse Osmosis
SGMD Sweeping Gas Membrane Distillation
SEE Single-Effect Evaporation
TDS Total Dissolved Solids
TOC Total Organic Carbon
TSGMD Thermostatic Sweeping Gas Membrane Distillation
TSS Total suspended solids
VMD Vacuum Membrane Distillation
V-MEMD Vacuum Multi-Effect Membrane Distillation
ZTIMD Zero Thermal Input Membrane Distillation
δ Thickness
ε Porosity
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© 2019 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access
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36
chemengineering
Article
A Multivariate Statistical Analyses of Membrane
Performance in the Clarification of Citrus
Press Liquor
René Ruby-Figueroa 1 , Monica Nardi 2 , Giovanni Sindona 2 , Carmela Conidi 3 and
Alfredo Cassano 3, *
1 Programa Institucional de Fomento a la Investigación, Desarrollo e Innovación, Universidad Tecnológica
Metropolitana, Ignacio Valdivieso 2409 P.O. Box 8940577 San Joaquín, Santiago, Chile; [email protected]
2 Department of Chemistry, University of Calabria, via P. Bucci, 12/C, I-87030 Rende (CS), Italy;
[email protected] (M.N.); [email protected] (G.S.)
3 Institute on Membrane Technology, ITM-CNR, c/o University of Calabria, via P. Bucci, 17/C,
I-87030 Rende (CS), Italy; [email protected]
* Correspondence: [email protected]; Tel.: +39-0984-492067; Fax: +39-0984-402103
Received: 19 October 2018; Accepted: 10 January 2019; Published: 17 January 2019
Abstract: The orange press liquor is a by-product of the orange juice production containing
bioactive compounds recognized for their beneficial implications in human health. The recovery
of these compounds offers new opportunities for the formulation of products of interest in food,
pharmaceutical and cosmetic industry. The clarification of orange press liquor by microfiltration
(MF) and/or ultrafiltration (UF) processes is a valid approach to remove macromolecules, colloidal
particles, and suspended solids from sugars and bioactive compounds. In this work the clarification
of orange press liquor was studied by using three flat-sheet polymeric membranes: a MF membrane
with a pore size of 0.2 μm and two UF membranes with nominal molecular weight cut-off (MWCO) of
150 and 200 kDa, respectively. The membrane performance, in terms of permeate flux and membrane
rejection towards hesperidin and sugars, was studied according to a multivariate analyses approach.
In particular, characteristics influencing the performance of the investigated membranes, such as
molecular weight cut-off (MWCO), contact angle, membrane thickness, pore size distribution, as well
as operating conditions, including temperature, and operating time, were analysed through the partial
least square regression (PLSR). The multivariate method revealed crucial information on variables
which are relevant to maximize the permeate flux and to minimize the rejection of hesperidin and
sugars in the clarification of orange press liquor.
Keywords: microfiltration (MF); ultrafiltration (UF); orange press liquor; clarification; multivariate
analysis
1. Introduction
Oranges contribute significantly to the bulk of world’s citrus fruit production accounting for more
than 50% of the global citrus production. During the marketing year 2015/2016, the global orange
production amounted to about 47.06 million metric tons, with Brazil producing 24% of the world total
followed by China and India [1].
Although the juice is the main product derived from orange, various by-products are produced
during the manufacturing process. The produced wastes consist mainly in wet peels and whole
rejected fruits containing 82% of water [2].
Most of the waste residue from commercial juice extractors is shredded, limed, cured, and pressed
into press liquors and press cakes which are then processed independently. Press liquors are semisolid

wastes containing soluble sugars (sucrose, glucose, and fructose), insoluble carbohydrates, fiber,
organic acids, essential oils, flavonoids, and carotenoids [3]. These residues have a considerable amount
of organic matter leading to environmental and health problems due to water runoff and uncontrolled
fermentation. At the same time, orange peels and pulp contain several bioactive compounds, such
as flavonoids and phenolic acids, recognized for their beneficial implications in human health due to
their antioxidant activity and free radical scavenging ability [4].
Recent research and development efforts have aimed at converting the potential of wastes
into profitable products creating new segments of production and offsetting the disposal costs [5].
Indeed, polyphenolic compounds are used as raw materials in the production of dietary supplements
and functional foods, as colouring and flavouring agents in food industries as well as in health
and pharmaceutical industries due to their antibacterial, antiviral, anti-inflammatory, antiallergic,
and vasodilatory action [6].
Conventional extraction techniques to recover polyphenolic compounds from agro-food waste
matrixes usually rely on solid-liquid extraction (SLE) based on the use of volatile organic compounds,
such as ethanol, methanol, or acetone solutions as extractants [7]. However, the use of solvents is
characterized by serious problems for both consumers and environment due to their toxicity, high
volatility, and non-renewable properties.
The growing interest in the biological activity of phenolic compounds has intensified research
efforts to develop novel and sustainable procedures for their extraction, separation, and purification in
an efficient and environmentally friendly manner without affecting their stability.
Membrane technologies have received great attention in the last years for the recovery of
antioxidants from agricultural by-products due to their advantages over conventional methodologies
which include mild operating conditions, low energy requirement, no additives, separation efficiency,
and easy scale-up [8]. In particular, microfiltration (MF), ultrafiltration (UF), nanofiltration (NF),
and reverse osmosis (RO) have been largely investigated, also in sequential design, for the recovery of
phenolic compounds from a wide variety of agricultural products and by-products including olive
mill wastewaters [9], artichoke wastewaters [10], wine by-products [11], and citrus by-products [12].
An interesting approach to recover and concentrate valuable compounds from orange press liquor
is based on the sequential use of membrane operations including ultrafiltration (UF), nanofiltration
(NF), and osmotic distillation (OD) [13]. As in the clarification of fruit juices, MF and UF processes
allow to remove high molecular weight compounds like cellulose, hemicellulose, cell debris, pectins,
and microorganisms from the raw press liquor overcoming typical drawbacks of conventional methods
of clarification which include enzymatic treatment (depectinization), cooling, flocculation (gelatin,
silica sol, bentonite and diatomaceous earth), decantation, centrifugation, and filtration [14].
These processes separate the flow from the press liquor into a permeate having a total soluble
solids content and an acidity level similar to that of the press liquor and a retentate containing
suspended solids such as proteins and fibers and high molecular weight carbohydrates, such as
cloud pectins.
It is generally recognized that the performance of MF and UF membranes in term of productivity
and selectivity is affected by different factors such as membrane characteristics (e.g., pore size, pore size
distribution, and contact angle) [15], as well as by operating and fluid-dynamic conditions, including
transmembrane pressure, temperature, and feed flowrate [16].
These parameters have to be carefully selected and optimized in order to control concentration
polarization and membrane fouling phenomena due to the accumulation of rejected solutes on the
membrane surface or within membrane pores.
Generally, the analysis of membrane performance is carried out by using the “one-factor-at-a-time”
approach in which each parameter is studied independently of each other. However, it is crucial to
take into account the multivariate nature of membrane processes in which the correlation between
the variables is usually non-linear, and several factors affect the filtration phenomena simultaneously.
38
Earlier studies on membrane filtration have shown that the utilization of multivariate analysis extends
the information obtained from univariate analysis [17].
In previous studies, the response surface methodology (RSM) approach has been employed to
investigate the interaction of different operating conditions, such as transmembrane pressure (TMP),
temperature and feed flowrate on permeate flux [18] and the recovery of antioxidant compounds [19]
in the clarification of orange press liquor by UF hollow fibre membranes.
Experimental data of permeate flux and fouling index, obtained in optimized operating conditions,
resulted in a good agreement with the predicted values of the regression model. The optimized
operating conditions to maximize permeate fluxes and the recovery of antioxidant compounds as well
as to minimize fouling index were identified.
The present work aimed at investigating the effect of membrane characteristics such as membrane
thickness, pore size distribution, contact angle as well as operating conditions, such as temperature
and operating time, on the performance of three different flat-sheet MF and UF membranes in terms of
permeate flux and rejection of hesperidin and sugars (glucose, fructose, and sucrose) in the treatment
of orange press liquor. To accomplish that, the partial least squares regression (PLSR) was used as a
multivariate tool, to correlate the membrane characteristics (grouped in an X matrix) with membrane
performance (grouped in a Y matrix).
2. Theory
Partial least squares regression (PLSR), in its simplest form, can be defined as a statistical method
for relating two data matrix, X and Y, to each other by a linear multivariate model [20–23]. The PLSR
applications have been reported in three principal areas: quantitative structure-activity relationship
(QSAR) modeling, multivariate calibration, and process monitoring and optimization [23].
As a historical note, PLSR or just named PLS approach was originated around 1975 by Herman
Wold for the modeling of complex data [23]. PLS can be defined as a multivariate linear regression
methodology, based on the decomposition of the data into a set of orthogonal components or latent
variables (LVs) [23–26]. It is recognized as a robust method with a robust statistical basis able to
analyze data with noisy, collinear, numerous variables and even missing data-points in both the input
(X matrix) and output (Y matrix) data sets. An essential aspect of this technique is that the output
data structure guides the decomposition of the input data in a way that the respective orthogonal
components explain as much as possible of the covariance between the input and output [27].
As mentioned above, PLS links the input and the output matrices with “new” variables that are
estimated as a linear combination of the original variables or their rotation. The following equation
gives these new variables called X-scores and denoted by ta (a = 1, 2, . . . A):
tia = ∑ Wka∗ Xik ; (T = XW∗ ) (1)

k
where W is the weight matrix that relates the X-scores with each variable of X. On the other hand,
the input matrix X can be obtained from the linear combination between the X-scores T and the loading
P in order to minimize the X-residuals E:
Xik = ∑ tia pak + eik ; (X = TP + E) (2)

a
Then, the output matrix Y can be obtained by means of the following equation:
Yim = ∑ cma tia + fim ; (Y = TC’ + F) (3)

a
where C is the weight matrix that relates the X-scores with each variable of Y, meanwhile fim represents
the deviation between the observed and modeled responses, and comprises the elements of the
Y-residuals matrix, F.
39
Finally, the multivariate regression model can be obtained combining Equations (1) and (3):
∗
Yim ∑ cma ∑ wka xik + f im = ∑ bmk xik + fim ; (Y = XW∗ C’ + F = XB + F) (4)
a k k
The PLS regression coefficients, bmk (B) can be written as:
∗
bmk = ∑ cma wka ; ( B = W ∗ C’ ) (5)
a
The line obtained by linear regression of that swarm of data points, in the direction of maximum
variance, is the first latent variable or just factor. In other words, it captures the main trend in the data
set. Then, another linear regression is performed in the second direction of maximum variance, but
keeping in mind that this direction should be orthogonal to the first. This corresponds to the second
factor. The remaining factors are obtained accordingly [27].
3. Materials and Methods
3.1. Feed Solution

Citrus press liquor was supplied by Gioia Succhi Srl (Rosarno, Reggio Calabria, Italy). Liquors
were left overnight at room temperature to let the majority of the cloud particles settle out. Partially
clear liquor was recovered by filtration with a nylon cloth. The physico-chemical characteristics of the
resulting liquor are reported in Table 1.
Table 1. Physico-chemical characteristics of orange press liquor.
Hesperidin (mg/L) 159.60 ± 14.42

Glucose (mg/mL) 14.69 ± 0.19
Fructose (mg/mL) 20.48 ± 0.11
Sucrose (mg/mL) 2.11 ± 0.13
Total soluble solids (g/100 g) 8.6 ± 0.1
Solid content, after lyophilisation (g/100 mL) 4.94 ± 0.04
Density (kg/L) 1.02835 ± 0.0005
pH 3.58 ± 0.03
15 ◦ C 1.60 ± 0.02
Viscosity (cp) 25 ◦ C 1.45 ± 0.01
35 ◦ C 1.31 ± 0.03
3.2. MF-UF Equipment and Procedures

MF and UF experiments were performed by using a laboratory bench plant (Figure 1) equipped
with a stainless steel cell suitable to contain a flat-sheet membrane with a diameter of 47.2 mm.
Experimental runs were performed by using three polyvinylidenfluoride (PVDF) flat-sheet membranes
supplied by Microdyn-Nadir GmbH (Wiesbaden, Germany). Properties of selected membranes are
reported in Table 2. Experimental runs were performed according to the total recycle (TR) configuration
in which both permeate and retentate streams were continuously recycled back to the feed tank. This
configuration ensured a steady-state in the volume and composition of the feed. In order to evaluate the
effect of feed concentration on the membrane performance, experiments were also performed according
to the batch concentration (BC) configuration in which the permeate stream was continuously removed.
In both configurations operating conditions such as transmembrane pressure (TMP), temperature
and feed flowrate were fixed at 1 bar, 26.0 ± 1.0 ◦ C and 185 L/h, respectively. Each run was stopped
after 180 min of operation. Experimental runs were performed in triplicate. Permeate flux data were
expressed as average value ± SD.
40
Figure 1. Schematic diagram of the experimental set-up: (1) feed tank; (2) feed pump; (3,5) pressure
gauges; (4) flat-sheet cell; (6) digital balance; (7) retentate valve; (8) permeate tank; and (9) thermometer.
Table 2. Characteristics of selected membranes.
Membrane Type MV020T UV150T FMU6R2

Membrane process MF UF UF
Membrane configuration flat-sheet flat-sheet flat-sheet
Membrane material PVDF PVDF PVDF
pH range 2–11 2–11 2–11
Processing temperature (◦ C) 5–95 5–95 5–95
Thickness (mm) 0.188 ± 0.005 b 0.212 ± 0.004 b 0.190 ± 0.003 b
MWCO (kDa) - 150 a 200 a
Pore size (μm) 0.2 a - -
Maximum pore size distribution (frequency, %) 93.21 b 79.77 b 40.47 b
Diameter at maximum pore size distribution (μm) 0.488 ± 0.048 b 0.195 ± 0.019 b 0.212 ± 0.021 b
MWCO, molecular weight cut-off; PVDF, polyvinylidenfluoride (PVDF). a data from the manufacturer; b
experimental data.
The permeate flux (J) was determined by weighing the amount of permeate with a digital balance
and calculated according to the following equation:
Wp
J= (6)
t· A p
where Wp is the permeate weight collected during the time interval t and Ap is the membrane surface area
of permeation. The mass of permeate collected was measured with an accuracy of ± 0.1 g every 5 min.
3.3. Determination of Sugars

The quantitative determination of glucose, fructose and sucrose was carried out by an HPLC
system (Agilent Technologies, Palo Alto, CA, USA) equipped with a Luna reverse phase C18 column
(5 μ, 100 Å, 250 × 4.6 mm i.d. from Phenomenex (Torrance, CA, USA), an isocratic pump (model series
1100) and a refractive index detector (Series 200a).
Isocratic elution was used at a flow rate of 1 mL/min with two solvents: Solvent A, water/acetic
acid (0.1% v/v), 80%, and Solvent B, methanol, 20%.
For each reference sugar, a set of calibration standards using stock and working reference standard
solutions were prepared. Glucose, fructose, and sucrose were purchased from Sigma-Aldrich (Milan,
Italy). Sugar standards were dried at 60 ◦ C in a vacuum oven overnight and dissolved in 50% methanol
(injection solvent). The resultant solutions were filtered using a syringe filter and injected into HPLC.
41
The injection volume was 20 μL. The peak areas in the chromatograms were plotted against
calibration curves obtained from standard solutions (external standard method), in a concentration
range of 0.5–2 mg/mL for each compound. Results were expressed as mean ± SD of three
independent determinations.
3.4. Determination of Hesperidin

The quantitative determination of hesperidin was carried out by an HPLC system (Shimadzu
LC-20AB, Kyoto, Japan) equipped with a binary pump, autosampler and a UV/vis detector (SPD-20A),
monitored at 284 nm and 360 nm. Samples were centrifuged before injection. The column used
was a Discovery C18 (25 cm × 4.6 mm, 5 μm from Supelco, Bellefonte, PA, USA). The mobile phase
consisted of two solvents: Solvent A, water/phosphoric acid (0.1% v/v) and Solvent B, acetonitrile.
Phenolic compounds were eluted under the following conditions: 1 mL/min flow rate and ambient
temperature; gradient conditions from 0% to 5% B in 0.01 min, from 5% to 10% B in 19.9 min, from
10% to 20% B in 20 min, from 20% to 25% B in 20 min, from 25% to 35% B in 20 min, from 35%
to 60% B in 15 min, from 60% to 5% B in 3 min, followed by washing and reconditioning of the
column. The identification of hesperidin was obtained comparing the retention time by using authentic
standard. Hesperidin was from Sigma-Aldrich (Milan, Italy). Results were expressed as mean ± SD of
three independent determinations.
3.5. Pore size and Pore Size Distribution Measurement

Membranes pore size and pore size distribution were determined by using a PMI Capillary Flow
porometer (Porous Materials Inc., Ithaca, NY, USA) according to the bubble point method [28,29].
A porewick solution (surface tension 16 dynes/cm) was used as a wetting liquid. Fully wetted samples
were sealed in the cell and measurements were carried out by the wet up/dry down method using the
software Capwin (Porous Materials Inc., USA). Data were processed and exported as an Excel file by
the software Caprep (Porous Materials Inc., USA).
3.6. Thickness and Contact Angle Measurement

The thickness of each membrane was determined by a multiple-point measurement, using a
digital micrometre Mahr 40E (Mahr GmbH, Esslingen, Germany). Contact angle measurement were
carried out by using the sessile drop method with a CAM 200 contact angle meter (KSV instrument LTD,
Helsinki, Finland). The droplets were deposited on the membrane surface by using a micro-syringe
with automatic dispenser, while the images were captured by a digital camera allowing apparent static
contact angles to be measured at different time. An average of 20 readings was obtained for each
specimen and the respective mean value was calculated.
3.7. Data Analysis
3.7.1. Pre-Processing
Data were initially organized into dataset X-matrix (n × k) which is composed of 114 observations
and five factors or predictors such as membrane thickness, diameter at maximum pore size distribution,
contact angle, operating time, and temperature. On the other hand, Y-matrix (n × m), also called
response, was composed of 114 observations and five responses: permeate flux and rejection towards
hesperidin, glucose, fructose, and sucrose.
In any analytical application, data are usually processed before using PLSR. In this work, in which
factors and responses are discrete variables, data were pre-processed in order to obtain the maximum
information from the dataset. In general, pre-processing is but a minor modification of the dataset,
with the aim of minimizing the impact from extraneous noise and also putting each variable both on
an equal level with an equal scaling allowing to participate equally in the data modeling process [30].
Results of projection methods, such as PLSR, depend on the scaling of the data. With an appropriate
42
scaling, one can focus the model on more important Y-variables, and use the experience to increase
the weights of more informative X-variables [23,31]. In our case, the absence of knowledge about the
relative importance of the variables and the fact that the factors and responses are in different units
have forced to probe different techniques such as normalize and moving average.
3.7.2. Number PLSR Components or Factors and Model Validation

In any empirical modeling, it is essential to determine the real complexity of the model.
Considering numerous and correlated X-variables, a substantial risk exists for “over-fitting” that
means a well-fitting model with little predictive power [23]. Cross-validation (CV) is a practical
and reliable way to test the predictive significance [20,32–34]. Basically, in CV the data are divided
into groups followed by the development of parallel models that are evaluated with the differences
between observed and predicted Y-values. In the evaluation, the observations are kept out of the
developed model while the response values (Y) are predicted and compared with the observed values.
The procedure is repeated several times until every observation has been kept out. The sum of squares
of these differences is computed and collected from all the parallel models to form the predictive
residual sum of squares (PRESS), which estimates the predictive ability of the model [23]. The ability
of the model can be summarized using the R2 of the calibration and validation set, the root mean
square error of calibration and validation (RMSE), the standard error of calibration and validation
(SE is similar to RMSE except it is corrected for the bias) and the bias which is the mean value over all
points that either lie systematically above (or below) the regression line (a value close to zero indicate
a random distribution of point about the regression line).
All the statistical computations were performed using Unscrambler 10.4.1 software (CAMO AS,
Oslo, Norway).
4. Results and Discussion
4.1. Membrane Characteristics

Measurements performed to characterize the selected membranes are shown in Table 2.
The membranes used in this study, made of PVDF, are basically hydrophilic membranes with contact
angle values lower than 90◦ . The FMU6R2 membrane showed the most hydrophilic surface, followed
by UV150T and MV020T membranes. Thickness measurements showed no significant differences
between the membranes studied. The main differences between the selected membranes are related
with the pore size. The measurements carried out to evaluate the maximum pore size for each
membrane showed differences with the data reported by the manufactures. In addition, significant
differences related to the maximum pore size distribution were found. In particular, the FMU6R2
membrane showed the minimum frequency (40%); this means that only 40% of the membrane surface
has a pore size of 0.2 μm, and the rest of surface could present higher or lower values. On the other
hand, MV020T and UV150T membranes showed higher frequency of distribution: therefore, these
membranes are more homogeneous in their pore size distributions. These factors will be strongly
related with the type of fouling produced and, therefore, with the membrane performance in terms of
permeate flux and rejection towards hesperidin and sugars.
4.2. Time Evolution of Permeate Flux

Figure 2 shows the time evolution of permeate flux under the TR configuration. For all selected
membranes the permeate flux reduces constantly due to concentration polarization and fouling
phenomena until to reach a uniform rate known as steady-state. In particular, the MV020T membrane
and the FMU6R2 membrane showed a quite similar flux decay (35.6 and 31.6%, respectively); for the
UV150T membrane the flux decay was of about 41.4%. These effects could be attributed to the type of
fouling produced during the treatment of the orange press liquor. As expected, the MF membrane,
with larger pore size, exhibited highest permeate flux values in comparison with UF membranes.
43

)085
897

097

-SNJP K

2SHUDWLQJWLPHPLQ
Figure 2. Time course of permeate flux for selected membranes under total recycle configuration.
Operating conditions: TMP, 1 bar; temperature, 26.0 ± 1.0 ◦ C; feed flowrate, 185 L/h.
In the BC configuration the permeate stream is continuously removed from the system, while the
retentate stream is recycled back to the feed reservoir leading to an increase of the feed concentration
during the filtration process. The increased feed concentration results in a more severe concentration
polarization and, consequently, in a more pronounced flux decline in comparison with the TC
configuration (Figure 3). In these conditions the MF membrane with larger pores showed the maximum
flux decay (51.4%), followed by FMU6R2 and UV150T membranes with flux decay values of 38.4%
and 36.1%, respectively.

)085

897
097

-SNJP K

2SHUDWLQJWLPHPLQ
Figure 3. Time course of permeate flux for selected membranes under batch concentration configuration.
Operating conditions: TMP, 1 bar; temperature, 26.0 ± 2.0 ◦ C; and feed flowrate, 185 L/h.
4.3. Data Analyses

The data were pre-processed by using several normalization tools and moving average. Table 3
shows the results obtained for the PLSR models, all of them with four components of factors.
The pre-processing of area normalization, followed by moving average, was the once which obtained
the highest values of R2 for the calibration and validation, as well as the minimum values of RSME, SE,
and bias for all the responses studied. This PLSR model with four factors can explain the 95.64% of the
total variance. Even though, there are differences in the capacity of prediction of the PLSR model for
each response variable in all the cases the prediction was higher than 91% (R2 ), as shown in Table 3.
44
Table 3. Comparison of various pre-processing methods for the PLSR modeling. Pre-processing:
A: Normalize (area normalization) and moving average; B: Normalize (unit vector normalization) and
moving average; C: Normalize (mean normalization) and moving average (Cal: Calibration data set;
Val: Validation data set).
Pre-Processing
Response Parameters None A B C
Cal Val Cal Val Cal Val Cal Val
Slope 0.596 0.576 0.966 0.959 0.978 0.973 0.966 0.959
R2 0.596 0.564 0.966 0.962 0.978 0.975 0.966 0.962
Permeate
RMSE (C,P) 4.339 4.521 0.003 0.003 0.007 0.008 0.031 0.033
flux
SE (C,P) 4.358 4.541 0.003 0.003 0.007 0.008 0.031 0.033
Bias 0 −0.001 0 −7.4 × 10−5 0 −7.9 × 10−5 0 −3.4 × 10−4
Slope 0.864 0.859 0.963 0.957 0.962 0.961 0.963 0.956
R2 0.864 0.852 0.963 0.958 0.962 0.959 0.963 0.958
Hesperidin RMSE (C,P) 3.906 4.076 0.003 0.004 0.011 0.011 0.035 0.038
SE (C,P) 3.923 4.094 0.003 0.004 0.011 0.011 0.036 0.038
Bias 0 −0.032 0 −7.1 × 10−5 0 4.9 × 10−5 0 −4.4 × 10−4
Slope 0.280 0.257 0.925 0.921 0.899 0.899 0.925 0.921
R2 0.280 0.245 0.925 0.917 0.899 0.894 0.925 0.919
Glucose RMSE (C,P) 7.554 7.853 0.005 0.005 0.018 0.019 0.051 0.054
SE (C,P) 7.587 7.887 0.005 0.005 0.018 0.019 0.051 0.054
Bias 0 −0.057 0 −8.9 × 10−5 0 1.3 × 10−4 0 −0.0006
Slope 0.309 0.286 0.978 0.981 0.675 0.676 0.978 0.981
R2 0.309 0.274 0.978 0.975 0.675 0.641 0.978 0.975
Fructose RMSE (C,P) 7.133 7.413 0.003 0.003 0.037 0.039 0.031 0.033
SE (C,P) 7.164 7.445 0.003 0.003 0.038 0.039 0.031 0.033
Bias 0 −0.060 0 7.4 × 10−5 0 0.0006 0 3.4 × 10−4
Slope 0.052 0.022 0.951 0.9546 0.636 0.637 0.951 0.954
R2 0.052 0.001 0.951 0.943 0.636 0.595 0.951 0.946
Sucrose RMSE (C,P) 18.465 19.074 0.005 0.006 0.044 0.047 0.053 0.057
SE (C,P) 18.547 19.159 0.005 0.006 0.044 0.047 0.053 0.057
Bias 0 −0.051 0 1.1 × 10−4 0 0.0008 0 0.0006
Figure 4 shows the analysis of the presence of outliers which were carried out by the use of
Hotelling T2 statistic, a multivariate generalization of the student t-test [35]. In this figure, several
points can be appreciated in the regions 1, 2, and 3. They represent samples similar to the majority of
the calibration population, samples which fit the model but are extreme in properties and samples
which differ from the average model population, respectively. On the other hand, samples which are
different and extreme, those considered as outliers are placed in the region 4. Thus, none of the data
was removed for the PLSR modelling.
Figure 4. Influence plot with Hotelling’s T2 statistic.
45
The PLSR scores-plot shown in Figure 4 was used to evaluate the relationship between the
samples. Factors 1 and 2, including 100% of the X-matrix data and explaining the 83% of the
variability in the Y-matrix, demonstrate that there are differences in the membranes studied and can be
grouped according to the tested membrane; this means that each membrane is characterized by specific
parameters which discriminate it from each other leading to a specific performance. In particular,
the FMU6R2 membrane showed similarities, and it is grouped clearly as a cluster, as well as UV150T
membrane placed in the negative sector of factor 2 (Figure 5a). The MV020T membrane has not
grouped, and it is placed in the positive and negative part of factor 2. On the other hand, regarding the
type of process, the score-plot (Figure 5b) showed a grouping between the TR and BC configuration.
Figure 5. PLS Score plot for the two principal factors. (a) Measurements griped by membrane studied,
and (b) measurements by type of processing.
This group is not clearly observed for the FMU6R2 membrane placed in the origin of factor 2:
for this membrane TRC and BC are not grouped. These results highlight the differences not only
between the membrane characteristics but also between the type of configuration in which the principal
difference is related to the increase of feed concentration which produces a variance in the type of
fouling and, consequently, in the membrane performance.
The correlation among all membrane characteristics and operating conditions with the responses
variables used to evaluate the membrane performance is illustrated in Figure 6. In this figure
differences in the influence of membrane characteristics and operating conditions on the permeate
flux and rejection of hesperidin and sugars can be appreciated. In particular, operating time and
thickness play a significant role (they are far away from the responses) on the permeate flux and
46
rejections: this means that higher values of thickness and operating time produce a lower value of
permeate flux and rejection towards hesperidin and sugars. In this regard, it is well known that an
increase in membrane thickness produces an additional resistance to the mass transfer across the
membrane. Thus membranes with lower values of membrane thickness are preferred. On the other
hand, higher operating times are related to a progressive membrane fouling leading to an increasing
of membrane resistance. The decrease in the membrane rejection is related to the concentration
polarization phenomena which produces an increase in the particle concentration at the membrane
surface where the difference in the chemical potential produces a diffusion of hesperidin and sugars
with a decreasing of membrane rejection.
Figure 6. PLS loading plot for the two principal factors.
The loading-plot also shows the positive correlation between temperature, contact angle, and pore
size distribution with permeate flux and rejection of hesperidin since they are located in the positive
quadrant of factors 1 and 2. Even though these variables have presented less importance in the
model, their influences in the responses should not be neglected. According to the film model [36],
an increase in temperature enhances permeate flux due to an increase of the mass-transfer coefficient.
An increasing in MWCO produces an increase in the rejection towards hesperidin due to the type of
fouling produced. In particular, in membranes with larger pores, such as MF membranes, a complete
pore blocking or a partial pore blocking is the dominant fouling mechanism which produces a decrease
in the pore size and a consequent increase in the rejection as is shown in Figure 7. The physical
blockage of the pores also produces a more significant flux decline in comparison with membranes
having tight pores. Similar results were obtained by Lin et al. [37] which evaluated the effects of
dissolved organic matter retention and membrane pore size on membrane fouling and flux decline.
By referring to the sugars rejection, it is appreciated in factor 2 of the loading-plot that glucose,
fructose, and sucrose are negatively related to pore size, contact angle, and temperature. According
to results obtained by Jiraratananon and Chanachai [38] in the clarification of passion fruit juice
by UF membranes, the operating temperature enhances the back diffusion of solutes into the bulk
solution reducing the thickness of the concentration polarization layer. Fructose, glucose, and sucrose
rejections showed a similar behavior because are closer in the negative quadrant of factors 1 and 2 in
the loading plot.
47

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)UXFWRVH

6XFURVH
5HMHFWLRQ

097 89 3085
Figure 7. Rejections of sugars and hesperidin for selected membranes under batch concentration
configuration. Operating conditions: TMP, 1 bar; temperature, 26.0 ± 1.0 ◦ C; and feed flowrate, 185 L/h.
The PLSR model built after data pre-treatment including four factors is suitable to predict the
response variables by correlation of membrane characteristics and operating conditions. Table 3 shows
that the model fits well the experimental data with R2 values of 96.2, 95.8, 91.7, 97.5, and 94.3 for
permeate flux, hesperidin, glucose, fructose, and sucrose rejection, respectively. The obtained model
can be used to predict the permeate flux, as well as hesperidin and sugars rejections, by using input
data such as contact angle, membrane thickness, pore size distribution, as well as operating conditions,
such as temperature and process time. The model is consistent with the knowledge obtained in early
studies and supplies new information concerning membrane filtration in citrus juice processing.
5. Conclusions
Orange press liquor was clarified by using three flat-sheet MF and UF polymeric membranes in
both total recycle and batch concentration configuration. A multivariate analyses approach was used
to study the relationship between membrane characteristics and operating conditions and membrane
performance in terms of permeate flux and membrane rejection towards hesperidin and sugars (glucose,
fructose, and sucrose). In particular, the partial least squares regression (PLSR) model was used in
order to predict the response variables by using input data such as contact angle, membrane thickness,
pore size distribution as well as operating conditions, such as temperature and process time.
The model well fitted the experimental data with R2 values of 96.2, 95.8, 91.7, 97.5, and 94.3 for
permeate flux, hesperidin, glucose, fructose, and sucrose rejection, respectively. Therefore, the capacity
of prediction of response variables resulted higher than 91.7%.
The obtained results indicated that the multivariate method appears as an efficient tool in the
examination of experimental results and reveals crucial information on which variables are relevant to
maximize the permeate flux and to minimize the rejection of hesperidin and sugars in the clarification
of orange press liquor, so maximizing the productivity of the process and the recovery of target
compounds in the permeate stream.
Author Contributions: Conceptualization: A.C. and R.R.-F.; methodology: A.C., C.C., R.R.-F. and G.S.; software:
R.R.-F.; analytical measurements: M.N.; data elaboration: R.R.-F.; writing—original draft preparation: A.C. and
R.R.-F.; supervision: A.C.
Acknowledgments: The authors wish to thank Silvia Simone from ITM-CNR for her valuable contribution in the
characterization of flat-sheet membranes used in the present work.
48
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50
chemengineering
Article
Preliminary Equipment Design for On-Board
Hydrogen Production by Steam Reforming in
Palladium Membrane Reactors
Marina Holgado and David Alique *
Department of Chemical, Energy and Mechanical Technology, Rey Juan Carlos University, C/Tulipán s/n,
28933 Móstoles, Spain; [email protected]
* Correspondence: [email protected]; Tel.: +34-914887603; Fax: +34-914887068
Abstract: Hydrogen, as an energy carrier, can take the main role in the transition to a new energy
model based on renewable sources. However, its application in the transport sector is limited by its
difficult storage and the lack of infrastructure for its distribution. On-board H2 production is proposed
as a possible solution to these problems, especially in the case of considering renewable feedstocks
such as bio-ethanol or bio-methane. This work addresses a first approach for analyzing the viability
of these alternatives by using Pd-membrane reactors in polymer electrolyte membrane fuel cell
(PEM-FC) vehicles. It has been demonstrated that the use of Pd-based membrane reactors enhances
hydrogen productivity and provides enough pure hydrogen to feed the PEM-FC requirements in one
single step. Both alternatives seem to be feasible, although the methane-based on-board hydrogen
production offers some additional advantages. For this case, it is possible to generate 1.82 kmol h−1
of pure H2 to feed the PEM-FC while minimizing the CO2 emissions to 71 g CO2 /100 km. This value
would be under the future emissions limits proposed by the European Union (EU) for year 2020.
In this case, the operating conditions of the on-board reformer are T = 650 ◦ C, Pret = 10 bar and
H2 O/CH4 = 2.25, requiring 1 kg of catalyst load and a membrane area of 1.76 m2 .
Keywords: hydrogen; on-board; steam reforming; ethanol; methane; membrane reactor;

palladium; modeling
1. Introduction
The current energy model, mainly based on fossil fuels, presents two main drawbacks (i) limitation
of reservoirs, which are getting scarcer and, consequently, increasing the price; and (ii) generation of
CO2 emissions during their combustion, definitively contributing to global warming [1]. Under this
situation, especially critical in big cities, it is clear there is a need for a new and sustainable energy
model, based on renewable energies, capable of facing the increasing energy demand associated
with the exponential growth of the global population and, simultaneously helping the reduction of
pollutant emissions [2]. This modification of the energy model will not be immediate nor focused on
a unique energy source, so a progressive transition in the short-middle term is necessary to achieve
a completely stable and safe energy grid while fossil fuels gradually cease [3]. Most perspectives
establish hydrogen as the key for this transition due to its high performance and absence of CO2
emissions during its combustion. It is considered a clean energy carrier because it allows both storage
of diverse primary energy sources, renewable ones in an ideal situation, and transformation into
different forms of energy, i.e., electrical energy in fuel cells [1]. In this manner, a hydrogen-based
energy model could combine at the same time traditional fossil fuels with other renewable sources,
while minimizing the environmental impact [4]. However, the lack of highly efficient storage devices
and distribution infrastructures is slowing down its real penetration into the system, especially

with regard to the transport sector [5,6]. Development of on-board hydrogen production systems
would be a great solution to overcome these limitations, generating the H2 just inside the vehicle
from other compounds and, thus, minimizing its difficult storage and transport [7]. However, this
application needs to be carefully addressed, especially in terms of dimensions and weight of the
on-board H2 production unit due to the space restrictions in an average vehicle and optimization
of power requirements. Considering the reduction of CO2 emissions as one of the main reasons
to use hydrogen in transport, renewable sources need to be pursued for its production, preferably
being also easily stored and distributed [8]. Bio-ethanol [9] and bio-methane [10] could accomplish
reasonably these requirements. However, it is important to note that the purity of these compounds
could affect the associated H2 production process and storage requirements. In fact, bio-ethanol is
usually accompanied by a significant amount of water, while bio-methane could be together with
20%–40% carbon dioxide. Both alternatives have been widely studied due to the use of mature
techniques, i.e., steam-reforming [11–14], although only few of them address on-board production for
their future application to the transport sector [15]. Among them, only some laboratory-scaled works
or modeling studies using small fuel cells of 1–5 kW can be found [15], producing hydrogen via steam
reforming, although it is really rare to find the combination of dimensioning the production unit with
the polymer electrolyte membrane fuel cells (PEM-FC) requirements in real conditions required for
most of typical vehicles (in terms of power and available space). Therefore, the viability of this strategy
to power bigger fuel cells, as most of prototypes demand, needs to be properly addressed. Moreover,
requirements of H2 purity are especially important as the PEM-FC (widely proposed for H2 -vehicles)
can be easily poisoned with trace amounts of CO [16], and available space inside a typical vehicle for a
purification unit is very limited.
In this context, the use of membrane reactors, which combine both chemical reaction and
separation steps in a single device, appears as a very attractive alternative for efficient process
intensification [17,18]. Selective permeation of hydrogen through an adequate membrane shifts
the equilibrium, enhancing the chemical reaction and, thus, improving both conversion and global
efficiency while a high-purity product is simultaneously obtained in the permeate side [4,17,18].
Over recent years, multiple experimental and modeling works with membrane reactors can be found
in the literature for diverse processes, mainly steam reforming [19], auto-thermal reforming [20],
and water gas shift [21]. Most of them present a multi-tubular structure in which the catalyst is placed
as a fixed-bed [22] or fluidized-bed [23,24] and the tubes are made of H2 -selective material, usually Pd
or Pd-based alloys with high perm-selectivity and good thermal resistance [25]. However, the study of
these systems for direct H2 production on-board is still scarce [15].
In this context, the present work analyzes the use of membrane reactors for ultra-pure H2
production on-board, capable to power a typical PEM-FC, feeding directly previously purified
bio-ethanol or bio-methane in the vehicle. The most convenient operating conditions were studied
through modeling to enhance the H2 production, maximizing the permeation rate and, thus,
the chemical reaction displacement, while assuring both thermal and mechanical stability. The reactor
design (catalyst load and membrane area) was performed while taking into account main limitations
of available space in vehicles. Finally, some considerations about energy integration, economy,
and environmental impact were also addressed.
2. Experimental Details
2.1. Process Design for Hydrogen Production On-Board

The process design was focused on the hydrogen requirements of the considered fuel cell, in this
case a PEM-FC type. According to the Technology Road Map published for fuel cells and H2
transition [26], the recommended power energy for utility vehicles goes from 80 to 120 kW with
higher heating value efficiencies (HHV) up to 60% (ratio between fuel cell power and high heating
value of the gases fed to the anode). Considering the minimum value of this range (80 kW) and typical
52
efficiencies, the on-board production system would need to supply around 1.70 kmol·h−1 of pure H2 ,
which was taken as the target value for this work.
Figure 1 presents a block diagram for the entire process designed in the present work. Two main
deposits contain the main reactants of the process: fuel (ethanol or methane from previous
bio-production processes) and water. Here, it is important to note that a previous purification and
conditioning of fuels were considered, feeding the vehicle with pure compounds for easier comparison
between both alternatives. Inside the vehicle, the reactants are pre-treated to reach the operating
conditions prior to entering the membrane reactor. Basically, this pre-treatment consists of pumping
and heating the reactants (vaporizing in case of liquids) until reaching the operating conditions.
Then, H2 is produced in the membrane reactor unit (R-1), being simultaneously separated through
a palladium membrane to feed the fuel cell (low-temperature polymer electrolyte membrane fuel
cell, LT-PEMFC). The H2 flux needs to be cooled and stabilized in a buffer to enlarge the PEM-FC
life cycle. The retentate coming from R-1 is fed to a combustor, where the non-converted reactants
(bio-ethanol or bio-methane), CO, and non-permeated H2 are burnt to provide the required energy for
both pre-treatment units and R-1. Water is separated from CO2 by condensation and then returned to
the intake deposit.
Figure 1. Block diagram for H2 -production on-board.
2.2. Membrane Reactor Modeling

The entire process for H2 -production on-board, the membrane reactor was modeled in
Aspen-Plus® v.10, selecting the SR-POLAR method as the thermodynamic model for the calculations.
However, the software does not have a specific block to simulate membrane reactors, in which both
the chemical reaction and the product separation are carried out simultaneously. To overcome this
problem, the multi-tubular membrane reactor R-1 designed for this work was simulated by successive
modules emulating both chemical reaction and H2 separation. Thus, R-1 is divided into a limited
number of units formed by a chemical reactor (RPLUG) and a consecutive separator to perform the real
membrane reformer. This scheme is usually adopted as a good solution for simulating accurately the
ideal shift effect of the membrane in a membrane reactor when only considering the thermodynamic
equilibrium [27,28]. In this work, besides the equilibrium displacement, the kinetics of the possible
chemical reactions were also considered as detailed in the following section. Figure 2 shows a simplified
diagram of the block scheme used to simulate the membrane reactor in Aspen-Plus® v.10.
53
Figure 2. Membrane reactor simulation by finite elements (micro-reactor + micro-separator).
The H2 permeation through the membrane for each separator unit was calculated following
Sievert’s Law [29].
0,5 0,5
FH2 = kH2 × A × PH 2 ,ret
− PH 2 ,perm
(1)
where FH2 represents the hydrogen permeate flow in mol/s, kH2 the H2 permeance, A is the permeation
area, PH2 ,ret and PH2 ,perm the hydrogen partial pressure in retentate and permeate sides, respectively.
For this study, a general permeance of kH2 = 2.43 × 10−3 mol·m−2 ·s−1 ·Pa−0.5 was considered, taking
as reference the DOE (Department of Energy of United States of America) technical targets for dense
metallic membranes, in which 300 scfh/ft−2 hydrogen flow-rate is recommended when operating
under 150 and 50 psia hydrogen partial pressure in retentate and permeate sides, respectively [30].
The permeate side was maintained at ambient pressure (1 bar) without applying any gas carrier,
while the partial pressure of hydrogen in the retentate side was calculated by multiplying the operating
pressure of the reactor and the hydrogen fraction present in the products that leave the previous reactor
unit. This assumption is very realistic if considering a low pressure drop inside the reactor due to its
considered length and the common control of pressure with back-regulators. The membrane area used
in the Sievert’s Law for each separator unit will be the total membrane area considered in the study
divided by the number of separator units that emulate the membrane reactor. Once the permeated
hydrogen has been calculated, the split fraction is obtained by dividing this value by the total hydrogen
that has entered this separator unit. No sweep gas was considered in the permeate stream in order to
obtain ultra-pure hydrogen that feeds the fuel cell and, consequently, powers the vehicle.
2.3. Chemical Reactions and Kinetics

As it was previously mentioned, not only the chemical equilibrium was considered but the
kinetics for diverse possible reactions inside the membrane reactors were also taken into account
for the modeling. Chemical reactions considered in the present work were collected from diverse
experiments from literature and the most relevant ones can be summarized as follows:
Ethanol decomposition : C2 H5 OH → CO + CH4 + H2 (2)
Ethanol steam reforming : C2 H5 OH + H2 O → CO2 + CH4 + 2H2 (3)
Methane steam reforming (i) : CH4 + 2H2 O ↔ CO2 + 4H2 (4)
Methane steam reforming (ii) : CH4 + H2 O ↔ CO + 3H2 (5)
Water gas shift : CO + H2 O ↔ CO2 + H2 (6)
Reverse water gas shift : CO2 + H2 ↔ CO + H2 O (7)
Based on previous publications from Llera et al. [31] and Hou et al. [32] for ethanol and methane
steam reforming, respectively, Langmuir-Hinshelwood (LHHW) kinetics have been implemented
in this work for modeling all described possible chemical reactions. LHHW equations involve each
adsorption, reaction, and desorption steps carried out during the chemical reaction, thus providing
more precise results than a Power Law model. All details about the kinetics expressions used in
54
Aspen-Plus® v.10 are included in Appendix A. Both reactor dimensions and, therefore, the residence
time, vary during the modeling for the optimization of the membrane area in the present study.
3.1. Preliminary Membrane Reactor Design: Modeling and Main Operating Conditions
An adequate membrane reactor design involves the selection of specific catalysts for principal
chemical reactions, catalyst load, membrane characteristics, device dimensioning (including the
required permeation area), and main operating conditions. As it was previously stated, proper catalysts
for each alternative addressed in the present work, as well as the associate kinetics parameters,
were taken from literature [31,32]. Thus, the present section is focused on modeling the membrane
reactor and analyzing the main operating conditions. The adopted strategy for modeling the membrane
reactor is based on dividing the equipment in a limited number of consecutive RPLUG reactor and
separator blocks. Thus, the first task was to determine the optimal number of units for simulating the
shift effect of the reaction thanks to the simultaneous H2 permeation through the membrane. This study
was carried out with some preliminary operating conditions, including a total catalyst load of 35 kg
and a maximum possible membrane area (2.42 m2 ) that fits in the available space inside the vehicle.
This area was divided into equal parts for each considered number of simulation units. Depicted
in Figure 3, we found both the permeate flux and the total amount of H2 generated from ethanol
(Figure 3a) or methane (Figure 3b) in the membrane reactor for an increasing number of simulation
units (reactor-separator). In general, H2 production increases as a greater number of simulation units
is considered due to the shift effect on the thermodynamic equilibrium; while a contrary effect can be
observed on permeate flux, due to the H2 depletion along the axial dimension of the reactor. For both
ethanol and methane intakes, H2 production seems to stabilize after 10 simulation units, so this value
was selected to continue the study and analyze in detail the best operating conditions.
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with: (a) ethanol (feed = 10 kmol/h, T = 600 ◦ C, P = 10 bar, H2 O/feed = 2) and (b) methane
(feed = 10 kmol/h, T = 600 ◦ C, P = 10 bar, H2 O/feed = 2). Legend: continuous line = total generated
H2 and dashed line = permeated H2 .
After determining the suitable number of simulation units for the membrane reactor, the influence
of temperature, H2 O/feed ratio and pressure were addressed as the main operating parameters for
both ethanol and methane feeding the membrane reactor (Figure 4). For these studies, 35 kg catalyst
load and 2.42 m2 of membrane area were maintained, keeping in mind that they were provisional
values to be optimized afterwards.
The temperature optimization was first studied maintaining a pressure of 10 bar and the steam
to feed ratio at four and three in the case of reforming ethanol or methane, respectively. As it can
be observed in Figure 4a, an increasing temperature favors the hydrocarbons transformation into
hydrogen. The main ethanol decomposition (Equation (2)) and steam reforming (Equations (3)–(5))
are endothermic reactions so they will be thermodynamically improved by increasing temperature.
55
Additionally, both reaction kinetics and hydrogen permeance through the membrane are also increased
with temperature, following an Arrhenius-type dependence, so the shift effect of the membrane
reactor is also boosted and, consequently, the hydrogen production rate. Thus, it can be stated
that, in general, higher temperatures improve the hydrogen production. However, temperature is
limited by the thermal stability of the H2 -selective membrane. Pd-based membranes are prepared
onto supporting materials and experimentally they are used in the typical range of 400–550 ◦ C to
prevent possible damages on the composite structure, although it is expected to resist slightly higher
temperatures [33,34]. In this manner, it is also possible to find several works in which these membranes
operate at temperatures up to 650 ◦ C with satisfactory results in terms of mechanical stability [35–38].
Under this perspective, and considering that temperatures above 650 ◦ C do not increase the hydrogen
productivity remarkably, this value was selected as the most appropriate operating temperature to
perform the process when feeding both ethanol and methane.
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W;ďĂƌͿ W;ďĂƌͿ
Figure 4. Influence of main operating conditions for the membrane reactor when feeding ethanol or
methane: (a) temperature, (b) steam to feed hydrocarbon ratio and (c) total retentate pressure. Legend:
continuous line = total generated H2 and dashed line = permeated H2 .
Steam to feed hydrocarbon ratio in the membrane reactor was the next operating condition
analyzed in this work (Figure 4b). For this study, the reactor temperature was maintained at 650 ◦ C,
considering the optimum value obtained in the previous study, and the reactor pressure at a preliminary
value of 10 bar. As it can be extracted from the results, total hydrogen production is enhanced
by increasing values of steam content in the feed. In general, the presence of water promotes all
chemical reactions in which it acts as reactant, shifting the thermodynamic equilibrium towards
56
further hydrogen production, according to Le Châtelier’s principle. However, large quantities of water
dilute the generated hydrogen, reducing its partial pressure in the retentate side and, in consequence,
the driving force of the permeation process. Thus, the thermodynamic equilibrium shift due to the H2
extraction through the membrane is limited. These opposite effects can explain the results collated in
Figure 4b. First, the permeate flow-rate increases as steam to feed hydrocarbon ratio increases, as the
chemical reaction improvement is more important than the hydrogen dilution effect. A maximum
value around the ratio 2–3 is reached for the permeate flow-rate, the dilution effect becoming greater
than the chemical reaction improvement from this point. This effect is caused by a drastic hydrogen
partial pressure decrease in the retentate side, also affecting the pure hydrogen recovery. Considering
this behavior and the energy requirements for heating the entire feed stream to the membrane reactor
(including both hydrocarbon and steam), values of 3.00 and 2.25 were selected for steam-to-ethanol
and steam-to-methane ratio, respectively.
Finally, the operating pressure in the membrane reactor was also evaluated, taking the optimal
values obtained in previous studies for the temperature and steam to feed ratio. The modeling
performance at these conditions is shown in Figure 4c. In general, an increase in both total produced
H2 and permeate H2 can be observed as the pressure increases in the retentate side, being able to
extract almost all the H2 generated in the membrane reactor as a pure gas in the permeate side at
pressures higher than 10 bar. This separation is slightly easier in the case of feeding methane instead of
ethanol due to the relationship between membrane area (kept constant) and the total H2 generated.
A pressure increase clearly makes the H2 separation through the membrane easier due to the associated
improvement of the permeation driving force. The higher the H2 permeation, the greater the shift effect
on the thermodynamic equilibrium for chemical reactions R1 to R4, therefore enhancing the global
productivity. However, in the case of ethanol steam reforming, previous studies found a decrease of
H2 yield in a traditional fixed-bed reactor due to the production of methane, which cannot be easily
converted into hydrogen at high pressures as the reaction is shifted towards the reactants, accordingly
to Le Châtelier’s principle [39]. Of course, this negative effect on the H2 production is clear in the
case of directly feeding methane to the process. However, as it can be extracted from the modeling
results, this negative effect on the thermodynamics seems to be compensated by the continuous
hydrogen removal through the membrane, obtaining a steady increase in hydrogen production as the
pressure rises in the studied range. Considering other aspects related to the mechanical stability of
the membrane, a total pressure of 10 bar for the retentate side was selected as the most appropriate
operating condition to be used in the membrane reactor, both for ethanol and methane intakes.
The stability of H2 -selective membranes at this operating pressure was demonstrated in previous
works at lab scale, avoiding cracks generation or delamination of the selective film [36,40].
3.2. Reactor Design Optimization

After analyzing the main operating parameters for the membrane reactor, the equipment design
was optimized in terms of catalyst load, required permeation area, possible energy integration,
and some preliminary economic considerations, aiming to produce 1.70 kmol·h−1 of pure H2 to
power the considered 80 kW PEM-FC for the vehicle.
The maximum size considered for the membrane reactor is based on the available space under
the rear seats of a standard vehicle, where it will be placed. In order to maximize the compactness of
the reformer and maximize the permeation area, a multi-tubular reactor configuration was adopted.
In this reactor, a triangular distribution of membranes with 1.25 in of inter-tubular space to ensure
good heat transfer was considered, thus being possible to accommodate a maximum of 38 tubes of
80 cm in length. This reached a maximum membrane area of 2.42 m2 .
Theoretically, the amount of catalyst affects the space velocity inside the reactor, the hydrocarbon
conversion and, consequently, the amount of produced hydrogen. Figure 5 collates the results obtained
for different catalyst loads when feeding the membrane reactor with ethanol (Figure 5a) and methane
(Figure 5b). A stable H2 production rate is reached for a catalyst load of 5 kg and 1 kg when feeding
57
the reactor with ethanol and methane, respectively. The facility to reach a stable value with a smaller
amount of catalyst in the second case can be explained by the kinetic parameters. The pre-exponential
factors for the kinetic expression of methane steam reforming (Equation (4)) are higher by several
orders of magnitude than the corresponding ones for ethanol steam reforming (Equation (3)). It means
that higher conversions can be achieved with a smaller catalyst load. In the case of feeding the
membrane reactor with ethanol, almost complete conversions (around 99.99%) were achieved for
catalyst loads greater than 5 kg, while this value was maintained around 40% in the case of using 1 kg
of catalyst.
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ϭ͘Ϯϱ ϭ͘Ϯϱ
ϭ͘ϬϬ ϭ͘ϬϬ
Ϭ͘ϳϱ Ϭ͘ϳϱ
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Ϭ ϱ ϭϬ ϭϱ ϮϬ Ϯϱ ϯϬ Ϭ ϭ Ϯ ϯ ϰ ϱ
ĂƚĂůǇƐƚůŽĂĚ;ŬŐͿ ĂƚĂůǇƐƚůŽĂĚ;ŬŐͿ
Figure 5. Influence of catalyst load when feeding: (a) ethanol and (b) methane. Legend: continuous
line = total generated H2 and dashed line = permeated H2 .
Then, several combinations of catalyst load, membrane area and reactant feed were tested aiming
to achieve the production target of 1.70 kmol·h−1 of pure H2 . With these simulations we can see
that, despite hydrogen production being maintained as very stable for increasing catalyst loads,
the associated decrease of space velocity improves the hydrogen recovery, as it is possible to save part
of the initially considered membrane area. In this manner, it could be possible to maintain similar
hydrogen production, saving 20% of membrane area by doubling the catalyst load from 5 kg to 10 kg.
However, by doubling again the catalyst load from 10 kg to 20 kg this effect would only save another
3% of the membrane area. Thus, 10 kg was chosen as the optimum catalyst load for the ethanol steam
reformer. This effect is negligible in the case of considering a methane feed.
The optimal combination was found to be 1.87 m2 membrane area, 10 kg of catalyst load,
and 0.37 kmol h−1 feed for the ethanol steam reforming and 1.76 m2 , 1 kg of catalyst and 0.54 kmol·h−1
when feeding methane. As it was previously described, these membrane areas were achieved by
considering the use of a multi-tubular membrane reactor. The recent trends in membrane preparation
used for hydrogen production processes have been directed to synthesize composite membranes in
which a thin layer of palladium or a palladium-based alloy is deposited onto a porous supporting
material [34]. Selecting standard dimensions for these supports, i.e., outside diameter of 1.0 in and
total length around 24 in, the membrane reactor design will require 28 membranes, ensuring a good fit
to the available space under the rear seats in any utility vehicle.
The energy requirements for the proposed model, including the reactants pre-treatment and
the heat of reaction requirements, can be achieved by combusting the retentate gases from the
membrane reactor. Thus, both ethanol/methane intake and membrane area were optimized to
reach an autonomous process in terms of energy, while the desired pure-H2 to feed the PEM-FC was
maintained. The transitory state until achieving this situation was not taken into account in the present
study. Before the reactor reaches the optimum operating temperature to act as an autonomous system,
ethanol or methane would need to be fed directly to the combustor, providing the necessary energy for
the initial process conditioning. Thus, the total fuel consumption would be slightly higher than that
indicated in this work.
58
On analyzing the convenience of using a membrane reactor for the on-board H2 generation
instead of a traditional reaction system, clear benefits can be found. In this manner, a 75% rise in
H2 production is achieved by using a membrane reactor for the on-board hydrogen production from
ethanol compared to that obtained in a conventional reactor operating under the same conditions
(T = 650 ◦ C, Pret = 10 bar, H2 O/C2 H5 OH = 3 and mcat = 10 kg). Thus, the H2 flow-rate is increased from
1.06 kmol h−1 to 1.85 kmol·h−1 due to the total conversion of the ethanol being reached, whereas it
was maintained below 95% in a conventional reactor. In the case of feeding the system with methane,
a similar behavior can be found, although in this case the increase was greater. Hydrogen productivity
and methane conversion were increased from 0.9 kmol·h−1 to 1.82 kmol·h−1 and from 42.8% to 84.9%,
respectively, operating under the same conditions for both conventional and membrane reactors
(T = 650 ◦ C, Pret = 10 bar, H2 O/CH4 = 2.25 and mcat = 1 kg). All these parameters are summarized
in Table 1. The results also imply additional benefits in both weight and space savings due to the
intensification of the process reached with the membrane reactor.
Table 1. Optimization results for the membrane reactor design.
Amembrane Catalyst Pretentate N H2, out Net Energy

Feed HC Nin (kmol h−1 ) T (◦ C) H2 O/HC XHC (%)
(m2 ) Load (kg) (bar) (kmol h−1 ) Balance (kW)
C2 H5 OH 0.37 1.87 10 650 10.0 3.00 1.85 100 −3.13
CH4 0.54 1.76 1 650 10.0 2.25 1.82 84.9 −2.99
Finally, a preliminary approach to main economic and environmental aspects was also included
to analyze roughly the viability of on-board H2 production via membrane reactors for powering
vehicles. First commercial hydrogen vehicles on the market have an autonomy of around 500–650 km
with a pressurized hydrogen tank of 5 kg [41,42]. Considering conservative criteria, a preliminary
consumption of 1 kg H2 /100 km for general PEM-FC vehicles is estimated. If hydrogen on-board
generation is assumed, there is no need to store it, thus solving one of the main drawbacks for
commercially introducing hydrogen vehicles in the near future. Considering a regular deposit of 55 L
for liquid fuels (i.e., ethanol coming from bio-routes), and simulated results of this work, 8.5 kg of
hydrogen could be generated, giving an autonomy for the car of around 850 km. On the other hand,
considering a 15 kg deposit for the methane alternative (value used in current natural gas-powered
vehicles in the market), 5.8 kg of hydrogen could be produced, making it possible to cover around
580 km. The membrane would be one of the most expensive elements in the process; estimating
its cost from economic targets proposed by the US Department of Energy for ensuring commercial
viability of this technology, assuming a cost of 500 US $/ft2 , it would mean, around 1520 € m2 with
the current exchange rate [30]. In this context, the cost for the membranes of the on-board reformers
would be around 2650–2800 € in the case of considering feeding the vehicle with bio-methane or
bio-ethanol, respectively. This cost can be easily absorbed by both manufacturers and customers,
especially considering that CO2 emissions can be significantly reduced. The European Commission
indicates that CO2 emissions need to be maintained below 95 g·km−1 for year 2020 [43]. Under this
perspective, the studied process feeding with bio-ethanol presents potential CO2 emissions of around
97 g CO2 /100 km, slightly higher than the limit proposed by the UE. However, feeding the system
with methane, this value could be reduced to 71 g CO2 /100 km due to its higher H/C ratio. Here, it is
important to remember that previous purification processes for bio-ethanol and bio-methane feedstock
have been considered, feeding the vehicle with the pure compounds to avoid a reduction of the useful
volume of the vehicle tank. Both of them represent good results, noticeably reducing current values for
latest gasoline and diesel vehicles, with CO2 emission levels of 123 and 119 g CO2 /100 km, respectively.
4. Conclusions
This work addressed a first approach for analyzing the viability of H2 on-board production by
membrane reactors in PEM-FC vehicles via mathematical modelling with Aspen-Plus® v.10. Despite
further experimental studies needing to be performed, some interesting insights can be extracted
59
for alternative hydrogen production from bio-ethanol or bio-methane. Firstly, it was demonstrated
that the use of membrane reactors enhances the hydrogen productivity and provides enough pure
hydrogen to feed the PEM-FC requirements in one single step. Operating conditions for both
alternatives were optimized, studying the effect of temperature, pressure, steam/hydrocarbon ratio,
and catalyst load for each case. The methane-based on-board hydrogen production seems to be
the best alternative, generating 1.82 kmol·h−1 of pure H2 for feeding the PEM-FC and minimizing
the CO2 emissions up to 71 g CO2 /100 km, ensuring the future limitation proposed by the UE for
year 2020 is achieved. This alternative ensures an autonomy of around 580 km for the H2 -vehicle
assuming a typical methane deposit of similar capacity to the gas-feed commercially available vehicles.
For this alternative, the on-board reformer operates at T = 650 ◦ C, Pret = 10 bar, and H2 O/CH4 = 2.25,
requiring 1 kg of catalyst load and a membrane area of 1.76 m2 . However, the alternative achieved
from bio-ethanol can also be considered for the future, reaching similar results (1.87 kmol·h−1 of pure
H2 at comparable operating conditions) and ensuring a more realistic production from renewable
routes in the required terms.
Author Contributions: D.A. and M.H. conceived and designed the experiments; M.H. performed the experiments;
D.A. and M.H. analyzed the data; no reagents nor materials were necessary for this study; M.H. wrote the paper
with revision of D.A.
Funding: This research received no external funding apart the facilities of Rey Juan Carlos University for
studying Chemical Engineering and the collaboration scholarship for M.H. in the Department of Chemical, Energy,
and Mechanical Technology of the above-mentioned university.
Acknowledgments: The authors of this work are hugely grateful for the support achieved from Rey Juan Carlos
University (Spain). M. Holgado especially acknowledges the collaboration scholarship of 8 months in the
Department of Chemical, Energy, and Mechanical Technology of the above-mentioned university. Additionally,
we also thanks prof. José Antonio Calles for his advises in preliminary works of this research.
Appendix A
The LHHW kinetics expressions considered in the present work for the ethanol steam reforming
are summarized as follows:
−1 −1/2
k R1 y E yCH y
4 H2
r R1 = 2
(A1)
DEN
−1 −1
k R2 y E yH2 O yCH y
4 H2
r R2 = (A2)
DEN 2
−5/2
k R3 y2H2 O yCH4 yH (1 − β R3 )
r R3 = 2
(A3)
DEN 3
k R6 yCO2 y1/2
H2 (1 − β R6 )
r R6 = (A4)
DEN 2
−1/2 −1 −1 −1/2
DEN = 1 + KEt y Et + KEt y Et yH2
+ K Ac y Et yH2
+ KCHO y Et yCH y
4 H2
−1/2 −1 −3/2
+KCH3 yCH4 yH + K y y
CH2 CH4 H2 + + K y y
CH CH4 H2
2
−1/2 (A5)
+KH2 O yH2 O + KOH yH2 O yH 2
+ KCH4 yCH4 + KCO yCO
+KCO2 yCO2 + KH y1/2 H2 + KH2 yH2
where β is the ratio between the product of each component fraction to the stoichiometric coefficient
and the equilibrium constant of the considered reaction:
y4H2 yCO2
β R3 = eq (A6)
K R3 yCH4 y2H2 O
60
yH2 O yCO
β R6 = eq (A7)
K R6 yCO2 yH2
At the same time, the equilibrium constant can be defined as the ratio between the kinetics
constants for both direct and reverse reactions, obtaining:

−5 k R−3 y4H yCO2
k R3 y2H2 O yCH4 yH22 1 − 2
k R3 yCH4 y2H
−5/2
k R3 y2H2 O yCH4 yH k R−3 yCO2 y3/2
2O H2
r R3 = = 2
− (A8)
DEN 3 DEN 3 DEN 3

k R−6 yH O yCO
k R6 yCO2 y1/2
H 1− k y 2 y
2
=
R6 CO2 H2
r R6 DEN 2 (A9)
−1/2
k R6 yCO2 y1/2 k R−6 yCO yH2 O yH
= DEN 2
H2
− DEN 2
2
In the case of feeding methane, LHHW kinetics expressions can be described as follows:
4

PCH4 PH2 O PCO2 PH
k3 1,75 1− K P3
2 2
PCH4 PH 2O
PH
r3 = 2
(A10)
DEN 2
0,5 3

PCH4 PH PCO PH
k4 1,25
2O
1 − K
2
P P
CH4 H2 O
PH P4
r4 = 2
(A11)
DEN 2
0,5 P P
PCO PH O
1−
2 CO2 H2
k5 0,5 K P5 PCO PH2 O
PH
r5 = 2
(A12)
DEN 2
0,5 −1
DEN = 1 + KCO PCO + KH PH + KH2 O PH2 O PH2
(A13)
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63
chemengineering
Article
Hydrogen and Oxygen Evolution in a Membrane
Photoreactor Using Suspended Nanosized Au/TiO2
and Au/CeO2
Tiziana Marino 1, *, Alberto Figoli 1 , Antonio Molino 2 , Pietro Argurio 3 and
Raffaele Molinari 3, *
1 Institute on Membrane Technology (ITM), National Research Council of Italy (CNR), Via P. Bucci Cubo 17C,
I-87036 Rende (CS), Italy; a.fi[email protected]
2 Research Centre of Portici, Italian National Agency for New Technologies, Energy and Sustainable Economic
Development (ENEA), Piazzale Enrico Fermi 1, Portici, 80055 Napoli, Italy; [email protected]
3 Department of Environmental and Chemical Engineering, University of Calabria, Via P. Bucci, 44/A,
I-87036 Rende (CS), Italy; [email protected]
* Correspondence: [email protected] (T.M.); [email protected] (R.M.)
Abstract: Photocatalysis combined with membrane technology could offer an enormous potential for
power generation in a renewable and sustainable way. Herein, we describe the one-step hydrogen
and oxygen evolution through a photocatalytic membrane reactor. Experimental tests were carried
out by means of a two-compartment cell in which a modified Nafion membrane separated the
oxygen and hydrogen evolution semi-cells, while iron ions permeating through the membrane
acted as a redox mediator. Nanosized Au/TiO2 and Au/CeO2 were employed as suspended
photocatalysts for hydrogen and oxygen generation, respectively. The influence of initial Fe3+
ion concentration, ranging from 5 to 20 mM, was investigated, and the best results in terms of
hydrogen and oxygen evolution were registered by working with 5 mM Fe3+ . The positive effect of
gold on the overall water splitting was confirmed by comparing the photocatalytic results obtained
with the modified/unmodified titania and ceria. Au-loading played a key role for controlling the
photocatalytic activity, and the optimal percentage for hydrogen and oxygen generation was 0.25 wt%.
Under irradiation with visible light, hydrogen and oxygen were produced in stoichiometric amounts.
The crucial role of the couple Fe3+ /Fe2+ and of the membrane on the performance of the overall
photocatalytic system was found.
Keywords: water splitting; Z-scheme; photocatalysis; photocatalytic membrane reactor
1. Introduction
Photocatalytic water splitting to generate hydrogen from solar light is a process that can play
an important role for the future development of clean and renewable energies alternative to fossil
fuels [1–8]. The combination of photocatalysis, which allows converting solar energy into chemical
energy, and membrane-based operations could offer the possibility to achieve one-step hydrogen
generation from water splitting at ambient temperature without needing further energy inputs.
Hydrogen attracted increasing interest as a valid candidate for fossil-fuel substitution, enough to
give rise to create the so-called “hydrogen economy” in 1970 [9–12].
From a thermodynamic point of view, hydrogen oxidation can offer three times the energy per
gram in comparison to fossil fuels as gasoline. Moreover, hydrogen oxidation leads to the formation of
water, making it a zero-emission fuel. Hydrogen also finds applications in the chemical industry as a
reagent in fine-chemical synthesis [12].

Since Fujishima and Honda discovered photocatalytic water splitting by means of TiO2 electrodes
in 1972 [13], noticeable works were carried out in order to investigate photocatalytic-based hydrogen
generation from water via both photocatalysis and photoelectrochemistry [14]. Particular attention was
paid to semiconductor oxides, due to their simple preparation through calcination and their stability
toward oxygen generation [15–19]. The water-splitting pathway involves a series of radical reactions
initiated by light-driven photocatalyst activation, as deeply described in the literature [3].
Among the well-known semiconductors, nanosized TiO2 is attracting more and more interest,
due to its unique properties of physico-chemical stability and inertness, low cost, biocompatibility,
durability, long-term photo-stability, and potent oxidative power under ultraviolet (UV)-light
irradiation [20–22]. Despite its numerous advantages, the use of TiO2 still presents a limitation,
i.e., only UV light, representing ~4% of total solar energy, can be absorbed by titania nanoparticles.
Therefore, extending TiO2 light absorption to the visible fraction represents a challenging target
for photocatalysis applications. Various techniques, such as noble-metal and non-metal doping,
dye sensitization, and coupling with carbon materials were adopted in order to modify the electronic
band of titania [23].
In a previous work, we reported that gold nanoparticles supported on titania (Au/TiO2 )
represent a suitable photocatalyst for the generation of hydrogen with visible light using methanol
and ethylenediaminetetraacetic acid (EDTA) as sacrificial electron donors [14]. A remarkable
overall efficiency of approximately 5% measured at 560 nm was determined [14]. In this system,
gold nanoparticles act as a durable and stable photosensitizer, absorbing visible light and injecting
electrons in the conduction band of the TiO2 . Using 0.25 wt% gold loading on titania and methanol as
a sacrificial agent, ~98 μmol of hydrogen was obtained (catalyst content 2 g/L) after 4 h of irradiation
with visible light [14].
Also, we showed that ceria of small average particle size can behave as a semiconductor with
a remarkably high efficiency for the photocatalytic generation of oxygen from water using Ag+ or
Ce3+ as a sacrificial electron acceptor [24]. The best performing CeO2 sample was that prepared
using a biopolymer “alginate” as a templating agent to synthesize about 5 nm of average particle size
with a Brunauer-Emmett-Teller (BET) surface area of 93 m2 ·g−1 [24]. Also, in this case, visible-light
photocatalytic activity was implemented by depositing gold nanoparticles on CeO2 (Au/CeO2 ),
which allowed achieving ~50 μmol of oxygen when the aqueous suspension containing 0.25 wt% gold
deposited on CeO2 was irradiated for 4 h with visible light in the presence of AgNO3 as a sacrificial
agent [24].
Considering the above precedents and the visible-light photocatalytic activity for independent
hydrogen and oxygen generation using Au/TiO2 or Au/CeO2 , respectively, in the presence of an
appropriate sacrificial agent, it occurs that these two photocatalysts could also work in a system to
perform the simultaneous generation of hydrogen and oxygen in the absence of sacrificial agents
using a Z-scheme [25–28]. In this Z-scheme methodology, hydrogen and oxygen are generated
photocatalytically in different cells that are irradiated and separated by a membrane [5,29–34].
An electrolyte is used to ensure the electroneutrality in each cell and to allow charge transfer from one
compartment to the other.
Li et al. [5] reported concomitant hydrogen generation and phenol degradation in a photocatalytic
twin reactor under simulated solar light. In the proposed system, Pt/STO:Rh was used as a
photocatalyst for hydrogen evolution, while WO3 was chosen for phenol oxidation. A Nafion
membrane separated the two compartments of the cell. Fe3+ /Fe2+ pairs were used for electron
transfer. The obtained data evidenced a hydrogen generation rate of 1.90 μmol·g−1 ·h−1 . Moreover,
by employing a phenol initial concentration of 200 μmol·L−1 , hydrogen yield reached a value of
11.37 μmol·g−1 after 6 h of irradiation, corresponding to an increase of 20% compared to that of
pure water splitting. Fujihara et al. [35] studied water splitting in a two-compartment cell using
Pt/TiO2 -anatase as a catalyst for hydrogen generation suspended in a Br2 /Br− aqueous solution and
Pt/TiO2 -rutile for simultaneous oxygen evolution in an Fe3+ /Fe2+ redox couple solution. Yu et al. [33]
65
also reported the experimentation of a twin reactor for the synchronized formation of hydrogen,
through the photocatalytic activity of BiVO4 , and oxygen using Pt/SrTiO3 :Rh. A Nafion membrane
was inserted in the two-side system to assure the separate generation of the two gases. Similarly to the
above mentioned works, the Fe3+ /Fe2+ redox couple was also selected in this case as a redox mediator.
Hydrogen and oxygen in a stoichiometric ratio (2:1) were obtained, with a maximum hydrogen
formation rate of 0.65 μmol·g−1 ·h−1 . Lo et al. [31] investigated the water-splitting process for the
one-step H2 and O2 generation by means of a membrane twin reactor under visible-light irradiation.
Pt/SrTiO3 :Rh and WO3 were designated as hydrogen- and oxygen-evolution semiconductors,
respectively. The formation of the two gases reflected their stoichiometric ratio, with an average
hydrogen evolution rate equal to 1.59 μmol·g−1 ·h−1 .
Nafion represents a valid choice as a membrane material, since it is characterized by outstanding
chemical and physical resistance [36] and an affinity for iron species. Ramirez et al. [37] investigated
the uptake characteristics of different cations (Fe3+ , Cu2+ , and Ni2+ ) by Nafion 117, which is commonly
used as a separator for different chemical processes. The membrane exhibits its affinity in the order
Fe3+ ≥ Ni2+ ≥ Cu2+ , similar to that reported in a previous study [38]. In another study [39], it was
reported that a Nafion/Fe membrane was resistant to the attack of the highly oxidative radical •OH
(E◦ •OH/–OH = 1.90 eV vs. normal hydrogen electrode (NHE)) and did not allow leaching of the
Fe exchanged on the sulfonic groups within the 3000-h testing period. Kiwi et al. [40] demonstrated
that iron compounds supported on a Nafion membrane gave good results in a photo-Fenton water
treatment process, where the Fe ions were fixed and remained active in H2 O2 decomposition.
In the present work, we studied the overall photocatalytic water splitting using Au nanoparticles
as a sensitizer of TiO2 and CeO2 semiconductors irradiated with visible light in combination, a Nafion
film as a membrane separating two cells, and ferric sulfate as the electrolyte. Diffusion tests on the
iron-modified Nafion membrane were performed to determine its ability to allow diffusion of iron
species. The influence on system performance of initial Fe3+ concentration and of Au loading on the
O2 and H2 evolution photocatalysts was determined. Finally, the photocatalytic activity of the pairs
(Au/TiO2 and Au/CeO2 ) for the photocatalytic water splitting through a Z-scheme under visible light
was demonstrated.

TiO2 (particle size: 20 nm; rutile/anatase: 85:15, 99.9%) was a commercial P25 sample supplied by
Degussa. CeO2 was prepared starting from an aqueous solution of alginate that was flocculated with
cerium nitrate followed by calcination as previously reported [24]. Gold nanoparticles were deposited
on TiO2 and CeO2 via the deposition–precipitation method starting from AuHCl4 and maintaining
pH = 10 as described in Reference [14]. TEM images were recorded with a Jeol 200 Cx microscope
operating at 200 kV.
2.1. Photocataytic Tests

The photocatalytic membrane reactors (PMRs) experimented in the present work for simultaneous
generation of hydrogen and oxygen from water splitting mimic the Z-scheme mechanism used by
plants for natural photosynthesis. The Z-scheme (Figure 1a) basically includes two photocatalysts:
(i) the oxygen evolution photocatalyst (Au/CeO2 in this study) leading to O2 formation via water
oxidation, and (ii) the hydrogen evolution photocatalyst (Au/TiO2 in this study) which promotes H2
formation via water reduction. The aqueous suspensions containing the two photocatalysts need to
be separated by a membrane able to transports electrons via a redox couple (Fe3+ /Fe2+ in this study)
acting as an electron redox mediator.
The experimental set-up (Figure 1b) consisted of a two-compartment Pyrex cell, each with a
volume of 50 mL, separated by a Nafion modified membrane with an exposed membrane surface
area of 3.14 cm2 . Each compartment, containing 60 mg of photocatalyst suspended in 30 mL of
Milli-Q water (corresponding to 2 g·L−1 photocatalyst concentration), was irradiated with a 125-W
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medium-pressure mercury lamp (DLU, HDLM E27) equipped with a Pyrex glass jacket which allows
maintaining the system at a temperature of 20 ◦ C. The suspensions were purged with argon flow for
at least 30 min before irradiation in order to remove dissolved air. For polychromatic visible-light
irradiation, an Fe2 (SO4 )3 solution (3% w/v), circulated into the Pyrex glass jacket of the lamp, was used
as a cut-off filter (λ > 400 nm). Hydrogen and oxygen generation was determined by injecting 0.1 mL
of each Pyrex cell headspace gas in a gas chromatograph (GC; Agilent 7890A) equipped with a thermal
conductivity detector. The GC determination was carried out by operating in isothermal conditions
(50 ◦ C), with a capillary column (CP-PoraPLOT Q, molecular sieve, 530 μm inner diameter, 15 m
length) and argon as a carrier gas.
(a)
(b)
Figure 1. (a) Diagram of the Z-scheme overall water splitting using Au/CeO2 as a photocatalyst for
oxygen generation, Au/TiO2 for hydrogen generation, and Fe3+ /Fe2+ as a redox couple. (b) Conceptual
scheme of the set-up used for photocatalytic experiments.
67
2.2. Membrane Modification

The Nafion 117 membrane (Aldrich, thickness of 178 μm) was modified using the procedure
described herein before its use. In the first step, the membrane was boiled in a 1 M HNO3 solution for
2 h to remove any contaminant; then, it was washed with Milli-Q water, immersed in a 1 M NaOH
solution, and subsequently in a 1 M H2 SO4 solution for 4 h, each for conditioning the membrane [41].
Finally, the Nafion membrane was immersed in a 0.5 M Fe2 (SO4 )3 solution for 24 h to change its
functional groups (H+ ) with Fe3+ ions.
2.3. Iron Spectrophotometric Determination

Spectrophotometric analyses were performed using 1,10-phenanthroline (Fluka, Aquanal Plus
kit) and potassium thiocyanate (Aldrich), for total iron (λ = 510 nm) and ferric ion (λ = 477 nm)
determinations, respectively. Ferrous iron ion concentration present in solution was calculated by the
difference between total and ferric iron concentration.
3.1. Diffusion Test

The iron-containing modified Nafion membrane was tested to determine its ability to allow
diffusion of iron species. Similar concentrations of Fe2+ and Fe3+ as that utilized in the photocatalytic
experiments were used in one compartment and, then, the presence of corresponding iron species over
time was determined in the other compartment. The corresponding profiles of iron species diffusing
through the membrane are provided in Figure 2.
Figure 2. Fe2+ () and Fe3+ () transport over time through the Nafion membrane in the compartment
cell with no initial salt.
It was observed that, while Fe3+ diffusion could be fitted by a straight line, i.e., the concentration
of Fe3+ in the chamber without it grew linearly over time, similar experiments with Fe2+ salt
clearly revealed two regimes. These results might be explained considering that, in the first regime,
ion exchange of Fe3+ and Fe2+ occurred in the Nafion membrane concomitantly to the diffusion. In the
second regime, the Nafion membrane behaved essentially as a Fe2+ exchanger.
The iron content in the membrane before and after its use was estimated by SEM energy dispersive
X-ray spectroscopy (EDX) analysis. The results showed an iron weight loading of ~1.3% and this value
did not change after using the membrane (Figure 3).
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Figure 3. SEM picture of Nafion membrane used for the photocatalytic test (A) and energy-dispersive
X-ray spectroscopy (EDX) analysis of ferric ion-modified membrane (B).
Figure 4 reports TEM pictures of the Au/TiO2 and Au/CeO2 photocatalysts. The average
particle size of photocatalyst nanoparticles, determined by considering a statistically relevant number
of particles in the TEM images of the samples, resulted in 2.7 and 5.0 nm for Au/TiO2 and
Au/CeO2 , respectively.
Figure 4. TEM images of Au/TiO2 (A) and Au/CeO2 (B).
3.2. Photocatalytic Tests

For the irradiation of the suspensions, a 125-W medium-pressure mercury lamp was used.
This lamp exhibited emission peaks at a discrete wavelength, mostly in the visible region (total
irradiation 2133 mW/m2 with 61% in the visible range). The inset of Figure 5 shows the emission
peaks in the spectrum of the lamp used.
Preliminary photocatalytic tests were carried out evidencing the crucial role of the couple
Fe3+ /Fe2+ on both hydrogen and oxygen generation. Indeed, by starting the working of the
cell with Fe2+ ions in the cell containing Au/TiO2 and Fe3+ ions in the cell containing Au/CeO2 ,
oxygen generation in both cells was observed during the first 30 min. We suggest that the reason
why oxygen was generated in Au/TiO2 cell instead of the expected hydrogen was because Fe3+ was
formed by Fe2+ oxidation, in the presence of oxygen by air, during the preparation of the work-up
cell. Analysis of the Fe3+ concentration in the Au/TiO2 cell confirmed that about 22% of Fe2+ ions
were oxidized to Fe3+ during this stage. The formed Fe3+ quenched the generation of hydrogen and
promoted the formation of oxygen, owing to the preferential reduction of Fe3+ by photogenerated
electrons with respect to the photoreduction of water. As a consequence, during the first 30 min,
oxygen generation (instead of hydrogen) was observed into the Au/TiO2 cell before changing to
continuous hydrogen generation.
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On the basis of these preliminary results, to avoid the presence of Fe3+ ions in the Au/TiO2 cell,
the iron ions were initially added to the system only in the form of Fe3+ at different concentrations,
as reported in Table 1, in the cell containing Au/CeO2 , while, in the Au/TiO2 cell, the initial iron
concentration was zero. Figure 5 shows the temporal evolution of hydrogen in the Au (0.25 wt%)/TiO2
cell and oxygen in the Au (0.25 wt%)/CeO2 cell when 5 mM Fe3+ was added in the Au/CeO2 cell.
Operating under these conditions, the reaction started on Au/CeO2 with oxygen evolution via water
oxidation coupled with the reduction of Fe3+ to Fe2+ . The so-produced Fe2+ ions permeated across
the Nafion modified membrane starting hydrogen evolution in the Au/TiO2 compartment. As a
consequence, during this early stage of the reaction (approximately 5 min), the ratio H2 :O2 was
about 1:1 (see Figure 5) and evidenced that H2 generation was promoted by Fe2+ which permeated
through the membrane. After this initial stage, two regimes can be observed: a first one, until 60 min,
and a second one, from 60 to 300 min. This trend can be explained considering that, in Figure 2,
a similar trend with the same two regimes can be observed for Fe2+ permeation through the membrane.
It could be deduced that Fe2+ ion diffusion during the first regime was faster than that during the
second regime (0.043 vs. 0.022 μmolFe 2+ min−1 ) and this behavior affected the photocatalytic reaction.
Indeed, the Fe2+ ions produced in the Au/CeO2 cell permeated across the membrane and promoted
a generation of hydrogen in the Au/TiO2 cell. After 300 min, a very low hydrogen production was
detected, probably because of the negligible permeation of Fe2+ ions across the membrane (see Figure 2)
which blocked the Z-scheme mechanism. However, it should be observed that both photocatalysts
efficiently worked during these two regimes (slopes of 1.25 μmolH2 ·min−1 during the first regime and
0.41 μmolH2 ·min−1 during the second regime), promoting the simultaneous generation of hydrogen
and oxygen in a stoichiometric amount in the Au/TiO2 and Au/CeO2 cells, respectively, and that
blocking was only caused by Fe2+ ion permeation through the membrane.
Figure 5. Hydrogen production () using Au (0.25 wt%)/TiO2 and oxygen production () using Au
(0.25 wt%)/CeO2 compared with hydrogen production ( ) using TiO2 and oxygen production () using
CeO2 only (initial Fe3+ concentration was 5 mM in the Au/CeO2 cell and initial Fe2+ concentration
was zero in the Au/TiO2 cell).
The initial concentration of Fe3+ ions in the Au/CeO2 cell varied in the range from 2 to 50 mM,
and it was found that 5 mM gave the best photocatalytic performance with the highest initial reaction
rate (Table 1).
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Table 1. Photocatalytic activity (initial reaction rate, r0 , evolved hydrogen and oxygen at 7 h) of the
series of ferric aqueous solutions (initial Fe3+ concentration, C0 ) under study, using Au (0.25 wt%)/TiO2
and Au (0.25 wt%)/CeO2 for hydrogen and oxygen generation, respectively.
C0 Fe3+ Evolved H2,7h Evolved O2,7h H2 r0 × 102 O2 r0 × 102

(mM) (μmol) (μmol) (μmol·min−1 ) (μmol·min−1 )
2 56.2 28.1 34.2 20.7
5 166.1 75.6 114.0 53.4
10 86.2 43.0 96.3 32.5
20 43.2 24.2 34.8 21.1
50 25.5 16.3 33.4 23.5
Au/CeO2 was selective for oxygen generation as it was found to be unable to generate hydrogen.
The reason for this behavior might be related to the energy of the electrons in the conduction band of
Au/CeO2 , which was not sufficient for water reduction (see Figure 1). In contrast, these electrons were
able to reduce Fe3+ to Fe2+ .
The influence of gold on the photocatalytic performance of the Z-scheme overall water splitting
by TiO2 and CeO2 was determined by comparing the photocatalytic activity of the gold-containing
semiconductors in comparison with the same semiconductors without gold (Figure 5).
As expected, despite the irradiation source used not permitting exclusively visible-light emission,
a positive effect of the presence of gold was observed.
The gold loading plays an important role in the photocatalytic efficiency of the system.
To demonstrate this point, we performed some photocatalytic tests with equal gold loading on titania
and ceria varying from 0.25 to 1.0 wt%. By measuring the initial rate of hydrogen generation, it was
concluded that the optimum gold loading under these conditions was the lowest (0.25 wt%) (Table 2).
Table 2. Photocatalytic activity (initial reaction rate, r0 , evolved hydrogen and oxygen at 7 h) of the
series of gold-containing samples under study, using a 5 mM ferric solution and TiO2 and CeO2 as
photocatalysts for hydrogen and oxygen generation, respectively.
Au Loading Evolved H2,7h Evolved O2,7h H2 r0 × 102 O2 r0 × 102

(wt%) (μmol) (μmol) (μmol·min−1 ) (μmol·min−1 )
0.25 166.1 75.6 114.0 53.4
0.6 152.0 61.3 112.1 70.8
1.0 71.0 25.1 67.0 32.2
Au content in the aqueous reacting environment after the reaction was below the detection limit
(0.1 ppm).
In a precedent work it was also observed that Au loading is a key parameter controlling the
photocatalytic activity of Au/TiO2 and that an optimal Au percentage exists. Since the presence
of Au nanoparticles is detrimental for the efficiency of TiO2 photocatalysis under UV irradiation,
but enhances the photocatalytic efficiency for visible-light irradiation, the observed beneficial effect
of Au might be explained considering that, by operating under our conditions, visible light gave the
largest contribution to the total photocatalytic water splitting. In view of the above data, we propose
the water-splitting mechanism shown in Figure 6.
Upon light absorption (mostly visible), electrons (in the conduction band) and holes (in the
valence band) were generated in Au/CeO2 . It was found that electrons in Au/CeO2 were inefficient to
generate hydrogen and, therefore, they were captured by Fe3+ , forming Fe2+ ions that diffused through
the Nafion membrane to the Au/TiO2 cell. The holes located on Au of the Au/CeO2 photocatalyst had
sufficient oxidation power to generate oxygen via water oxidation as previously proven [42]. In the
Au/TiO2 cell, similar charge separation as in the Au/CeO2 cell would occur upon photon absorption;
however, in this case, the reduction potential of the TiO2 conduction band had enough energy to form
71
hydrogen via water reduction. The holes on Au were, in this case, quenched by oxidation of Fe2+
diffusing through the Nafion membrane from the Au/CeO2 cell.
Figure 6. Elementary steps occurring in the photocatalytic reaction upon irradiation of a

gold-containing photocatalyst sample under ultraviolet (UV) irradiation: (1) photon absorption;
(2) electron migration from Au to semiconductor conduction band; (3) electron quenching by P;
(4) Q oxidation by H+ mediated by Au.
To demonstrate the photocatalytic activity of the pair Au/TiO2 and Au/CeO2 for the overall
water splitting through a Z-scheme under visible light, analogous photocatalytic experiments were
performed by filtering light to almost completely remove the irradiation wavelength below 400 nm
(Figure 7). Under these conditions, the irradiance decreased from 2133 mW·m−2 to 570 mW·m−2 .
In Figure 7, the two regimes previously observed in Figure 5 were not present. This can be ascribed to
the lower irradiance (3.6 times lower for the visible light compared to UV irradiation), which decreased
the H2 /O2 generation rate (slopes of 0.08 μmolH2 ·min−1 and 0.04 μmolO2 ·min−1 ), thus requiring a
lower Fe2+ ion diffusion rate.
Figure 7. Hydrogen production () using Au (0.25 wt%)/TiO2 and oxygen production () using Au
(0.25 wt%)/CeO2 , under visible-light irradiation (initial Fe3+ concentration was 5 mM in the Au/CeO2
cell and initial Fe2+ concentration was zero in the Au/TiO2 cell).
Also under these conditions, hydrogen and oxygen generation was observed in stoichiometric
amounts in the Au/TiO2 and Au/CeO2 cells, respectively (Table 3).
72
Table 3. Photocatalytic activity (initial reaction rate, r0 , evolved hydrogen and oxygen at 7 h) of the Au
(0.25 wt%)/TiO2 and Au (0.25 wt%)/CeO2 samples using a 5 mM ferric solution for hydrogen and
oxygen generation, respectively, under visible-light irradiation.
Au Loading Evolved H2,7h Evolved O2,7h H2 r0 × 102 O2 r0 × 102

(wt%) (μmol) (μmol) (μmol·min−1 ) (μmol·min−1 )
0.25 30.36 14.89 11.0 4.2
4. Conclusions
In the present article, we combined the high activity of Au/TiO2 to photocatalytically generate
hydrogen with the high activity of Au/CeO2 to promote oxygen evolution from water. Thus,
overall water splitting was obtained by operating through a Z-scheme using a Nafion membrane and
Fe3+ /Fe2+ as an electrolyte.
The obtained results showed the following:
— The employed photocatalysts promoted simultaneous hydrogen and oxygen generation;

— The optimal content of ferric ions in the Au/CeO2 compartment was 5 mM;
— Gold operated as a photosensitizer allowing photocatalytic hydrogen and oxygen formation
under visible light;
— A gold loading of 0.25 wt% led to the best results in terms of hydrogen and oxygen evolution
(166.1 and 75.6 μmol, respectively, after 7 h of UV-visible-light irradiation);
— Hydrogen and oxygen were produced in stoichiometric amounts, i.e., 30.36 and 14.89 μmol,
respectively, after 7 h of irradiation with visible light;
— The decrease in permeation rate of iron ions through the Nafion membrane affected the
photocatalytic performance, slowing the generation rates of both hydrogen and oxygen.
Author Contributions: T.M. and R.M. conceived and designed the experiments; T.M. performed the experiments;
T.M., R.M., P.A. and A.M. analyzed the data; R.M. and P.A. contributed reagents/materials/analysis tools; T.M.,
R.M., P.A., A.M., A.F. wrote the paper.
Conflicts of Interest: The authors declare no conflicts of interest.
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75
chemengineering
Article
Experimental Investigation of the Gas/Liquid Phase
Separation Using a Membrane-Based Micro Contactor
Kay Marcel Dyrda *, Vincent Wilke, Katja Haas-Santo and Roland Dittmeyer
Karlsruhe Institute of Technology, Institute for Micro Process Engineering,
76344 Eggenstein-Leopoldshafen, Germany; [email protected] (V.W.);
[email protected] (K.H.-S.); [email protected] (R.D.)
* Correspondence: [email protected]; Tel.: +49-721-608-23430
Received: 28 September 2018; Accepted: 6 November 2018; Published: 14 November 2018
Abstract: The gas/liquid phase separation of CO2 from a water-methanol solution at the anode side
of a μDirect-Methanol-Fuel-Cell (μDMFC) plays a key role in the overall performance of fuel cells.
This point is of particular importance if the μDMFC is based on a “Lab-on-a-Chip” design with
transient working behaviour, as well as with a recycling and a recovery system for unused fuel. By
integrating a membrane-based micro contactor downstream into the μDMFC, the efficient removal of
CO2 from a water-methanol solution is possible. In this work, a systematic study of the separation
process regarding gas permeability with and without two-phase flow is presented. By considering
the μDMFC working behaviour, an improvement of the overall separation performance is pursued.
In general, the gas/liquid phase separation is achieved by (1) using a combination of the pressure
gradient as a driving force, and (2) capillary forces in the pores of the membrane acting as a transport
barrier depending on the nature of it (hydrophilic/hydrophobic). Additionally, the separation
efficiency, pressure gradient, orientation, liquid loss, and active membrane area for different feed inlet
temperatures and methanol concentrations are investigated to obtain an insight into the separation
process at transient working conditions of the μDMFC.
Keywords: gas/liquid separation; micro direct methanol fuel cell (μDMFC); porous membranes;
micro channel; two-phase flow; micro contactor; separator
1. Introduction
In recent years, the operating time and the miniaturisation of portable electronic devices such as
smartphones, laptops, and many others devices has become a field of high importance. Unfortunately,
due to the low energy capacity of conventional electrochemical accumulators e.g., lithium ion batteries,
this kind of energy supply or recharging systems (power banks) are no longer appropriate for long
operating times. To overcome short operating times, many possibilities are currently being investigated
to replace lithium ion battery-based energy supplies or recharging systems [1–3]. Small-sized
membrane-based fuel cell systems with a highly specific energy density are among the most promising
candidates to overcome short operating times. Using a micro direct methanol fuel cell (μDMFC) based
on a lab-on-a-chip (LOC) design, integrated fuel supply for methanol, and a separation system, the
operating time can be extended significantly without increasing the weight or volume of the portable
device disproportionately. In addition, the μDMFC can be refuelled instantly with methanol, which is
an easily storable, convenient liquid fuel with an energy density of 4.42 kWh/dm3 [1–5].
During the operation of the μDMFC, methanol from the liquid water-methanol mixture is oxidised
to gaseous carbon dioxide while at the cathode side, oxygen from gaseous air is reduced to liquid
water. Subsequently, two-phase flows are formed by the produced carbon dioxide and water at both
-anode and cathode- side. This occurring two-phase flow, on the one hand, decreases the accessibility of

methanol and oxygen to the catalyst layer on the respective electrode area inside the μDMFC, leading,
on the other hand, to a channel blocking phenomena in one or more channels during operation. In
both cases, the two-phase flow causes a reduction of the overall fuel cell performance. Therefore,
to ensure the permanent operation of a μDMFC in recirculation mode and to improve the fuel cell
performance stability, produced carbon dioxide as waste product or byproduct must be removed
continuously from the anodic loop. Furthermore, the water must be efficiently recovered from the
cathodic loop and fed into the anodic loop to compensate the water losses during μDMFC operation
and CO2 separation [6–8].
In conventionally-operated DMFCs, the occurring two-phase flow is passively separated in small
vessels due to the difference in density and the use of gravity [4]. For μDMFCs based on LOC design,
the separation of a two-phase flow is significantly more complex. Only flat separation systems to realise
a compact and portable design can be considered. By combining membrane- and micro-engineering
-technology, an orientation-independent removal and recovery of carbon dioxide and water from the
two-phase flow is possible [9–12]. This can be achieved by using a porous membrane-based micro
contactor installed downstream of the μDMFC with additional integration on the bipolar plates to
achieve a compact and flat LOC design including a recycling system. Different design approaches and
investigations for several microcontactors are summarised in Table 1.
Table 1. Examples of previous works on the gas/liquid separation in microstructured devices using
polymeric membranes or inorganic microsieves as a separation layer.
Investigator Research Topic Membrane Material Fluids Mode

Meng et al. [9] Distributed Breather Microsieve Silicon CO2 (g)/H2 O (l) P
Lee et al. [10] Micro Bubble Separator Microsieve Silicon CO2 (g)/H2 O (l) P
Amon et al. [11] Micro-electro-mechanical based μDMFC Microsieve Silicon CO2 /H2 O + CH3 OH (l) P
Alexander et al. [12] Micro-breather (heat sink) Microsieve Silicon H2 O (g)/H2 O (l) P
Kraus et al. [13] Orientation indipendent microseparator Membrane PTFE CO2 (g)/H2 O (l) A
Meng et al. [14–16] Membrane based micro separator in a μDMFC Membrane PTFE|PP CO2 (g)/H2 O + CH3 OH (l) A
Xu et al. [17] Active gas/liquid phase separation Membrane ACP N2 (g)/H2 O (l) A
David et al. [18] Micro heat exchanger and microgas separator Membrane PTFE Air (g)/H2 O (l) A
Fazeli et al. [19] Differential pressure on the gas/liquid separation Membrane PTFE CO2 (g)/H2 O + CH3 OH (l) A
PTFE: Polytetrafluoroethylene; PP: Polypropylene; ACP: Acrylic Copolymer; P: Passive; A: Active.
All of the studies summarised in Table 1 describe different membrane-based micro contactors for
the gas/liquid phase separation, studying different types of membranes and parameters. Nevertheless,
these studies fail to systematically investigate the gas permeability and influence of diffusion fluxes at
single and two-phase flow conditions, the separation efficiency regarding the gas permeability, and
the active membrane area during the gas/liquid separation process. In this work, a membrane-based
micro contactor for the gas/liquid phase separation with its corresponding systematic study of the gas
permeability, influence of the diffusion fluxes, and separation performance at single and two-phase
flow conditions, is presented for four different membranes.
2. Theoretical Background
To provide a solid background on the separation process in a porous membrane-based micro
contactor, capillary forces and mass transfer concepts—i.e., fundamentals of passive or active
gas/liquid phase separation—will be introduced.
2.1. Capillary Pressure

The capillary pressure (capillary forces), which has been known since 1830, can be mathematically
described by the Young-Laplace equation for ideal circular pores Equation (1) and rectangular/square
micro channels Equation (2). Detailed information about the capillary force can be found in the
supplementary information.
Circular Pore
4 · σlg · cos(ϕ)
pcap = (1)
dh
77
Rectangular/Square Micro Channel

cos(ϕt ) cos(ϕb ) cos(ϕl ) cos(ϕr )
pcap = σlg · + + + (2)
h h w w
where σlg represents the surface tension, ϕ the contact angle, and dh the characteristic diameter
(hydraulic or circular) of the pores of the polymer based membrane. Using Equation (1), the capillary
pressure can be calculated indicating the maximum water entry pressure of a porous membrane. For
an ideal circular pore diameter of 500 nm and a water contact angle of 100◦ (σH2 O = 0.072 N/m), a
capillary pressure, or in a broader sense, a capillary force of −1 bar (N/m) acting against the pore
wetting should be applied. The negative value of the calculated capillary pressure indicates the acting
direction of the force.
Figure 1 shows the capillary pressure calculated by Equation (2) for four different micro channel
configurations and pores (round capillary) depending on a scaling factor s dividing the starting values
width and/or height of the channel geometry.
Figure 1. Capillary Pressure pcap for water at 20 ◦ C, σH2 O = 0.07275 N/m, dependent on channel
geometry, surface properties, and material combination. Rectangular I (wall contact angle: 60◦ , width:
1 mm, height: 0.5 mm) without a hydrophobic membrane on the top of the micro channel. Rectangular
II (wall contact angle: 60◦ , width: 1 mm, height: 0.5 mm) with hydrophobic membrane made of PTFE
(contact angle: 120◦ [20]) on the top of the micro channel. Round Capillary I (wall contact angle: 60◦ ,
diameter: 1 mm). Round Capillary II (wall contact angle: 60◦ , diameter: 0.5 mm).
In Figure 1, it is clearly visible that homogenous wetted micro channels with a width of 1 mm
and a height of 0.5 mm always have the highest positive capillary pressure with an increasing
scaling factor. Heterogeneous wetted micro channels, as they can occur in a membrane-based micro
contactor (see Figure 2), instead have the lowest positive capillary pressure due to the high influence
of the hydrophobic membrane. To utilise the capillary pressure as a driving force for the passive
gas/liquid phase separation, the size of the channel plays a major role and must be taken into account
if passively-operated gas/liquid separation is the main objective.
78

Figure 2. Cross and longitudinal section of the separation process.
However, to ensure the portability of portable energy systems or applications, the gas/liquid
phase separation must be independent of orientation, which can be ensured by the capillary forces
in the micro channels. In macroscopic channels, gravitational forces have a considerable influence
on the behaviour of the two-phase flow (TPF), since buoyancy forces exceed the capillary forces. The
influence of capillary forces increases with decreasing channel diameter, as shown in Figure 1. To
quantify the ratio of capillary and gravitational forces, the Confinement number (Co) is calculated
by Equation (3). The Eötvös number (Eo), related to the Confinement number, can be calculated by
Equation (4).
1
σlg
Co = (3)
dh g · ρ − ρ
l g
1
Eö = (4)
8 · Co2
where dh represents the hydraulic diameter, g the gravitational acceleration, ρl the liquid density, and ρg
the gas density. For a rectangular or square channel, the hydraulic diameter can be calculated using the
cross-section area A and wetted perimeter Uw , as shown in Figure 1, by using the following equation:
4·A
dh = (5)
Uw
According to Huh et al. [21], Serizawa et al. [22], Suo et al. [23] and Brauner et al. [24], the capillary
forces become predominant over the buoyancy forces if Co ≥ 3.3 or Eö < 0.01. Using the data for a
micro channel with a height of 0.5 mm and a width of 1.0 mm with water + air at 20 ◦ C, a Confinement
number of Co ≈ 4 and an Etövös Number of Eö ≈ 0.0075 are obtained. In both cases, the capillary
forces are predominant over the gravitational forces, and an orientation-independent separation can
be assumed.
2.2. Mass Transfer

The working principle of the separation process is illustrated in Figure 2, showing the cross
sectional (left side) and longitudinal section (right side) views of the feed and permeate channel. As can
be observed, the combination of heterogeneous channel walls and hydrophobic porous membranes
leads to a spatial separation behaviour of the two-phase due to the capillary forces.
In addition, it can be seen that the gas phase directly contacts the porous membrane, and
is then pushed through. The driving force of the gas separation is the transmembrane pressure
difference ΔpTM :
ΔpTM = pg,feed − pg,sweep (6)
Furthermore, as shown in Figure 1, the capillary pressure on a gas bubble in a rectangular

microchannel with a hydrophobic membrane at a reduction factor of 1 (Figure 1) is about 1 mbar. For
the effective separation of typical amounts of gas over a small membrane area, higher pressures are
necessary. Therefore, the capillary pressure is considered negligible and the pressure in the gas and
liquid phases of the feed channel can be assumed to be equal, as shown in Equation (7).
79
pg,feed = pl,feed (7)
In the longitudinal section of the micro contactor (Figure 2), an overview of the different mass
transfer processes is given. Gaseous species are transported by convection as well as diffusion.
2.2.1. Convective Mass Transfer

The predominant mass transport through the gas covered area of the membrane is the pressure
driven convective flow. Depending on the thermodynamic state of the system, the feed gas is saturated
by the liquid species through evaporation, which is subsequently also separated from the liquid
stream convectively.
In the 19th century, Henry Darcy described the laminar convectional flow through porous media
empirically. His mathematical correlation is today known as the Darcy’s law. As assumed by this law,
the amount of the transferred fluid is directly proportional to the pressure difference across the porous
structure, as described by Equation (8) [17,18]:
. κ · A · ΔpTM
V= (8)
η· l
.
where V represent the volume flow rate of a fluid through a porous structure, κ the permeability of the
porous structure, A the available separation area which is usually completely covered by the separable
fluid, ΔpTM the transmembrane pressure difference across the porous structure, η the viscosity of the
fluid, and l the thickness of the separation layer.
The available or active membrane area during the separation process of a two-phase flow is
defined by the percentage of the overall allocable membrane area where the separable gas flow is
concentrated, and only thereby available for the separation process. For determination of the active
membrane area, Equation (9) can be used.
κTPF
Aactive = Amem · (9)
κg
where Aactive represent the active membrane area, Amem the maximum available membrane area in
the separation unit, κTPF the measured gas permeability with two-phase flow, and κg the measured
gas permeability with single-phase flow.
2.2.2. Diffusive Mass Transfer

In tight porous media, the interaction between the diffusing molecules and the channel walls
becomes more relevant at a Knudsen number of Kn > 0.01. If the Knudsen number exceeds this value,
the diffusion regime turns to a Knudsen diffusion regime in which collisions with walls occur more
often than collisions among molecules. In general, the Knudsen number is defined as:
λ
Kn = (10)
dp
with
4 · kB · T
λ= (11)
π · σ2coll · p
where λ is the free mean path length of the molecule, dP is the pore diameter, kB is the Boltzmann
constant, σcoll is the collision diameter of the molecule, and T and p are the temperature and pressure
respectively. At Kn > 2, only Knudsen diffusion is occurring. The Knudsen diffusion coefficient is
given by [25]:
1 2 · kB · T
DKn = · dp · (12)
3 mmol
80
where mmol is the molecular mass. In contrast, at Kn < 0.01, free molecular diffusion can be assumed.
In that case, the diffusion coefficient DAB,mol of substance A in substance B can be calculated using
Fuller’s equation with sufficient accuracy [26].

0.001 · T1.75 · MA + MB
1 1
DAB,mol = 2 (13)
p · 3 (vA + vB )
where T is the temperature, M is the molar mass, p the pressure, and v is the molecular diffusion
volume. To describe the diffusive mass transfer processes in the porous membrane-based micro
contactor, the gas covered and liquid covered areas of the membrane can be studied separately. At
the gas liquid interface, i.e., the area above the liquid covered area of the membrane, liquid species
evaporate and are thereupon transported diffusively through the membrane. Also, feed gas and
evaporated liquid is diffusively transported through the gas-covered area of the membrane into the
permeate channel if no convective flux is occurring.
On the other hand, the sweep gas diffuses via the membrane into the feed channel, but is then
transported back by the convection flow. It is important to mention that the overall diffusion through
the gas-covered membrane area is strongly affected by the convection flow. To approximate the rate of
diffusion of transport through the membrane in the deployed micro contactor without convection flow
or liquid feed, a simple calculation based on Fick’s law [25] e.g., for the sweep gas (synthetic air), can
be used: .
Vair,diff = Ap · Δyair · βmem (14)
.
where Vair, diff is the diffusion flux of air through the membrane, Ap is the cumulative surface area of
the pores, Δyair is the gradient of the molar fraction of air through the membrane, and βmem is the
mass transfer coefficient in the membrane. Normally, the examined membranes are built with a backer
material. In this case, a combined mass transfer coefficient can be calculated as follows:
1
βmem = (15)
1
βair,CO2 ,backer + 1
βair,CO2 ,active
with
Dair,CO2 ,i
βair,CO2 ,i = (16)
li
where βair,CO2 ,i is the mass transfer coefficient in the respective layer i, li is the thickness of the
respective layer i, and Dair,CO2 ,i is the diffusion coefficient of air in CO2 in the respective layer i.
2.2.3. Dissolving of Feed Gas

At the gas-liquid interface in the feed stream, gas is dissolved into the liquid. Small channel
dimensions generate a high surface to volume ratio, and the diffusion process is enhanced by the small
distances. Saturation of the liquid stream with feed gas can therefore be assumed. In the case of carbon
dioxide as the feed gas and water as the feed liquid, the maximum solubility of CO2 can be determined
approximately using an equation developed by R. Weiss [27]:

100 T mol
kCO2 = exp X1 + X2 · + X3 ln · (17)
T 100 L · atm
with
1 1
X1 = −58.9031; X2 = 90.5069 ; X3 = 22.294 (18)
K ln 1
K
81
where kCO2 is the solubility coefficient of CO2 calculated applying constants X1 , X2 , and X3 and system
temperature T, and p is the pressure in the system.
In addition, as shown by Schüler et al. [28] the solubility of CO2 in a water-methanol mixture
up to 2 mol/L at room temperature is approximately 20% (f(T) = 1.2) higher, at 40 ◦ C nearly
constant (f(T) = 1.0), and at 60 ◦ C significantly below 70% (f(T) = 0.3) than in pure water. The
.
maximal-dissolved volume flux of CO2 VCO2 ,sol can therefore be calculated.
. .
VCO2 ,sol = f(T) · Vl · kCO2 (T) · p · Vm,CO2 (19)
.
where Vl is the volume flux of liquid, f(T) is the solubility multiplier needed for aqueous methanol
solutions, and Vm,CO2 is the molar volume of the CO2 gas.
2.2.4. Separation Performance

For the characterisation of the separation efficiency, the separation performance (SP ) is commonly
used as an evaluation criterion. .
ni,perm
SP,i = . (20)
ni,feed,in
For a given maximum separable feed gas amount calculated by Darcy’s law, the SP,i value is equal
to 1, as long as the feed gas inlet volume flow is lower than the maximum separable feed gas amount.
If the feed gas inlet volume flow is higher than the highest separable feed gas amount, the SP,i curve
shows theoretically a regressive profile, as illustrated in Figure 3.
Figure 3. Theoretical SP,i trend according to a maximum separable gas feed amount of 78.3 mL/min,
156.7 mL/min, and 235.0 mL/min calculated by Darcy’s law with κ = 7.8 · 10−15 m, A = 114.5 mm,
ΔpTM = 50 mbar, 100 mbar, and 150 mbar, η = 17.1 μ Pa s, and l = 200 μm.
2.2.5. Mass Balance

For the characterisation of the separation performance, as well as the measurement of the loss of
water/methanol by evaporation, gas saturation and diffusion through the membrane in this work,
the composition of the gas from the sweep side outlet of the micro contactor was determined by
Fourier-transform infrared spectral analysis (FTIR). The sweep gas (spectrally-inactive synthetic air)
was used as a dilution and reference medium. Because of the lack of any chemical reaction, the amount
82
of material is constant and the mass balance of the membrane based micro contactor, as illustrated in
Figure 4, can be formulated as:
. . . .
nfeed,in + nsweep,in = nretentate,out + nsweep,out (21)
. .
where nfeed,in is the feed flux of liquid (aqueous methanol solution) and gas (CO2 ), nsweep,in is the flux
.
of sweep gas (synthetic air), nretentate,out is the flux of gas and or liquid leaving the feed channel and
.
nsweep,out is the cumulative flux of sweep gas and permeate leaving the sweep channel.

Figure 4. Mass balance model of the separation process.
The cumulative flux of sweep gas and permeate can be calculated using Equation (22)
. . .
nsweep,out = nsweep,in + nperm (22)
if the separation performance SP is

SP = 1 (23)
or
SP < 1 and ΔpTM ≥ ΔpTM,crit (24)
It should be noted, that Equation (21) is only valid when no sweep gas is lost through the feed
outlet. If the gas separation is complete (SP,i = 1), only liquid is leaving the feed channel. At a state of
incomplete gas separation, sweep gas can be transported diffusely across the membrane into the feed
channel and leave the feed side outlet. In this case, as shown in Section 4.2, a critical transmembrane
pressure difference is sufficient to prevent significant sweep gas loss. When these conditions are met,
the amount of separated gaseous substances i can be calculated with Equation (25).
. .
ni,perm = Yi,sweep,out · nsweep,in (25)
where Yi,sweep,out is the loading of species i in the gas stream leaving the sweep gas channel.
Equation (25) can also be written as:
. yi,sweep,out .
ni,perm = · nsweep,in (26)
1 − ∑ yi,sweep,out
with .
ni,perm
yi,sweep,out = . (27)
nsweep,out
where yi,sweep,out is the molar fraction of species i in the gas stream leaving the sweep gas channel
measured by calibrated Fourier-transform infrared spectral analysis.
3. Materials and Methods (Experimental)
3.1. Micro Contactor

The experimental investigation of the gas permeability, diffusion, and active-pressure-driven
gas/liquid phase separation was performed using the membrane-based micro contactor shown in
Figure 5.
83

Figure 5. Exploded-view of the membrane based micro contactor with integrated T-junction for
two-phase flow generation.
The main components of the membrane-based micro contactor are the bottom plate, the top plate,
the milli/micro channel structure, the integrated T-Mixer, the sealing, and the membrane. Both plates
have one straight milli/micro channel with a width of 1.7 mm, a height of 0.5 mm, and a length
of 67.35 mm. The overall available membrane area for the separation process is 114.5 mm2 . For a
visual observation of the gas/liquid phase separation, the membrane-based micro contactor is made of
PMMA, with a contact angle of 60◦ according to the literature [29].
Two inlets for the feed, i.e., gas and liquid, and one outlet for the retentate are integrated into the
top plate. The bottom plate possesses only one inlet and outlet for the sweep gas. In addition, the
permeate leaves the micro contactor via the sweep gas outlet. If no sweep gas is used, the inlet of the
bottom plate can instead be used as an outlet for the permeate. To generate a two-phase flow, gas and
liquid are mixed by a T-junction with a milli/micro channel depth of 0.5 mm, width of 1 mm, and
length of 20 mm.
3.2. Porous Membranes

Based on theoretical considerations (Equations (1) and (2)), only hydrophobic membranes for
gas/liquid phase separation were chosen as a separation membrane in a micro contactor. Due to the
high gas permeability and low pressure loss of porous membranes, the required membrane area for the
separation task can be customised to the available pressure gradient, which is the driving force for the
gas/liquid phase separation process. Hereby, a compact μDMFC with LOC design and well-defined
dimensions for the separation system can be realised.
In this article, four commercial-available porous hydrophobic membranes from two different
suppliers (Clarcor Industrial Air and Pall Corporation, Overland Park, KS, USA) were compared.
All membranes were built with a two-layer structure including the functional membrane layer and
stabilising support layer.
As shown in Table 2, different functional layers and different supporting materials were taken
into account for the experimental study. Water entry pressure ranges between 1 to 4.5 bar, as measured
by the supplier, which are high and safe enough for use as a separation layer in a μDMFC with LOC
design. Furthermore, all membranes are supposed to be temperature resistant in the working range of
84
a μDMFC. Images of the membrane surfaces with a scanning electron microscope (SEM) can be found
in Section 4 “Results”.
Table 2. Data summary of the polymer based porous hydrophobic membranes. Data extracted from
the data sheet provided by Clarcor Air for Aspire® QP955 and Aspire® QL217 and by Pall for Supor®
200PR and Versapor® . Contact angle of water determined by contact angle measurements at lab
conditions against air with a measuring accuracy of ±2.5◦ .
Hydrophobic Functional Layer Water Entry

Support Material Thick-Ness Pore Size Contact Angle
Membranes Material Pressure
®
Aspire QP955 [30] PTFE Polyester 200 μm 100 nm 120◦ ≥4.5 bar
Aspire® QL217 [31] PTFE Polypropylen 200 μm 200 nm 120◦ ≥1.0 bar
Supor® 200PR [32] Polyethersulfon Polyester 170 μm 200 nm 138◦ ≥1.38 bar
Versapor® 200PR [33] Acrylic Copolymer Nylon 230 μm 200 nm 120◦ ≥1.79 bar
3.3. Experimental Setup
3.3.1. Equipment
In Figure 6, a sketch of the experimental setup is shown. It can be divided into fluid dosing –
1 ,
4
micro contactor ,
5 pressure regulation ,6 and analysis –7 .
8
Figure 6. Scheme of the experimental setup.
To ensure fluctuation-free liquid admission, the methanol and water vessels 1 were pressurised
by a controlled influx of nitrogen. The liquid flow was regulated with mini CORI-FLOWTM s, utilising
Coriolis force as a measurement principle, whereas gas flows were regulated with an EL-FLOW®
thermal mass flow controller (MFC). Both regulation units were manufactured by Bronkhorst
High-Tech B.V. The specifications of the employed mini CORI-FLOWTM s and MFCs can be found in
the supplementary information.
In addition, the liquids were merged in a micro mixer (Part No. 1446-A-9.0) which was designed
and manufactured by the Institute of Micro Process Engineering (IMVT, Eggenstein-Leopoldshafen,
Germany) . 3 Two identically-manufactured cross-flow micro heat exchangers (Part No. 1469-A-1.2
85
and Part No. 1343-K-1.2), also designed by IMVT, were used to regulate the temperature of
the liquid and gas . 4 As a thermostating fluid, water was heated and pumped through the
micro heat exchangers by a PROLINE P12 thermostat (Lauda Dr. R. Wobser GmbH & Co. KG,
Lauda-Königshofen, Germany). Data sheets of the micro mixer and micro heat exchanger can be found
in the supplementary information.
Feed gas, sweep gas, and liquid then entered the micro contactor module 5 where the separation
process took place. At a state of incomplete separation, a two-phase flow streamed out at the outlet of
the top plate. For pressure control of the single and two-phase flow, a pressure buffer was integrated
.
6 The temperature of permeate and sweep gas leaving the micro contactor 7 were held at a constant
80 ◦ C by a double jacket heat exchanger . 7 Hereby, the condensation of evaporated liquid species
was prevented. Subsequently, the permeate/sweep gas mixture was spectrally analysed in a Fourier
transform infrared spectrometer (FTIR) Vector 22 MIR 8 (Bruker® Corporation, Billerica, MA, USA)
equipped with a 17 mL gas cell with optical windows made from zinc selenide. The multicomponent
calibration (CO2 , water, and methanol) of the gas analysis was carried out using the software OPUS
.
6.5. With a backward calculation using Equation (26), a constant nsweep,in and yi,sweep,out from the
spectral analysis, the amount of the permeate was determined. For the sweep gas loss experiments or
measurements of the retentate, an additional bubble flow meter Definer 220 (Mesa Labs, Lakewood,
CO, USA) was used.
The experimental data acquisition and process automation as well as control was done using
LabManager® /LabVision® 2.11 (Hitec Zang GmbH, Herzogenrath, Germany) on a standard PC operated
with Windows® 7. Verification of the methanol concentration in the water-methanol mixture produced
inline at the experimental setup was done using density-based measurements pycnometer at 20 ◦ C
(BRAND GMBH & CO KG, Wertheim, Germany). Water contact angle measurements were done manually
with an optical contact angle measurement system OCA5 (DataPhysics Instruments GmbH, Filderstadt,
Germany). Surface images of the unused and used porous membrane were taken with a JSM-6300
(tungsten cathode) scanning electron microscope (JOEL GmbH Germany, Freising, Germany).
3.3.2. Chemicals
All chemicals were used as bought. Methanol was bought from Merck in p.A. grade. Water was
purified with a Milli-Q Reference by Merck® Millipore (serial number F5PA67202D). The electrical
resistance of the purified water was measured to be 18.2 MΩ cm. All gases were purchased from Air
Liquid in grad N4.5 (separation experiments).
3.4. Operation Conditions

Generally, experiments were performed at a temperature of 20 ◦ C ± 2 ◦ C and a relative humidity
of 65% ± 4%. Experiments on separation performance and liquid loss by diffusion and evaporation
were measured at feed entry temperatures of 40 ◦ C and 60 ◦ C.
For the orientation tests, a feed entry temperature of 40 ◦ C was chosen. For the determination of
the methanol loss, the methanol concentration cCH3 OH of the water-methanol mixture was set to 1 and
2 mol/L, i.e., the usual fuel concentration in an active μDMFC system. For all other experiments, the
methanol concentration was generally set to 1 mol/L to study the influence it had on the separation
process and membrane material resistance.
3.4.1. Gas Permeability

The gas permeability was measured with a dead-end method for all porous membranes. With
this method, the incoming gas volume flow can only leave the membrane micro contactor across the
porous membrane. For the determination of the gas permeability, the pressure drop for different gas
.
volumetric flows up to Vg,feed = 1000 NmL/min was detected. Furthermore, the gas permeability and
the sweep gas loss for ΔpTM = 50, 75, and 100 mbar was checked in detail with an open-end method
86
.
with a constant feed gas volumetric flow Vg,feed = 500 NmL/min and different sweep gas volumetric
.
flows up to Vg,sweep = 200 NmL/min in the permeate channel.
3.4.2. Separation Efficiency

The separation efficiency or performance was evaluated by the following three different criteria:
• Separation performance
• Liquid loss by evaporation and diffusion
• Orientation independence
All experimental parameters for each evaluation criteria are summarised in Table 3.
Table 3. Summary of the experimental parameter for each evaluation criteria.

. . .
Evaluation Criteria cCH3 OH [ mol
l ]
mL
Vl,feed,in [ min ] Vg,feed,in [ NmL
min ] Vg,sweep [ NmL
min ]
ϑ [◦ C] ΔpTM [mbar]
Separation Performance 1 5 50 . . . 400 200 20, 40, 60 100
Liquid Loss 0, 1, 2 5 50 . . . 400 200 20, 40, 60 100
Orientation
1 5 200, 350 200 40 100
Independence
For all porous membranes and evaluation criteria, the transmembrane pressure ΔpTM was set to
. .
100 mbar and the liquid volume flow Vl,feed,in to 5 mL/min. The feed gas volume flow Vg,feed,in was
varied between 50 NmL/min and 400 NmL/min. Additionally, the gas permeability was investigated
at separations factors below SP,i < 1, indicating the maximum gas permeability of the porous
membrane under two-phase flow conditions. Furthermore, the temperature was varied and the
methanol concentration cCH3 OH of the water-methanol was set to 1 mol/L.
For the diffusive liquid loss at single phase flow, the Aspire® QL217 membrane was used as an
example to detect the real liquid loss by diffusion of water and methanol at room temperature for
different methanol concentrations and sweep gas volume flows.
The determination of the orientation independent gas/liquid phase separation with the porous
membrane-based micro contactor was checked for four different orientations. The orientation was
clockwise radially rotated by 90◦ , 180◦ , and 270◦ with respect to gravity. With these test scenarios, all
occurring critical orientations were tested.
3.4.3. Active Membrane Area

Considering the two-phase flow, the membrane area was not completely used during the
separation process, especially at full separation. If SP,i < 1, a two-phase flow would be still present
at the feed outlet. The determination of the active membrane area or participating membrane area
during the separation process was done for the Aspire® QL 217 membrane at room temperature with
different methanol concentrations. To quantify the active membrane area, the permeability values for
single phase and two-phase flow were experimentally determined and afterwards compared. The
sweep gas was set to 100 NmL/min.
4. Results
4.1. Gas Permeability

As shown in Figure 7, the transmembrane pressure rose with an increasing feed gas volume flux
at room temperature for all membranes.
87

.
Figure 7. Transmembrane pressure at different VCO2 for all membranes at ϑ = 20 ◦ C and calculated
average permeabilities for all membranes at ϑ = 20 ◦ C.
Gas permeability κ values shown in Table 4 were calculated by rearranging Equation (8). The
total membrane thickness (active membrane layer + supporting material) was used for the calculation
of the permeability.
Table 4. Gas permeability values for single phase conditions.
Membrane Gas Permeability κi [10−15 m2 ] at 20 ◦ C

Aspire® QL217 9.3
Aspire® QP955 14.0
Versapor® 200PR 10.3
Supor® 200PR 7.9
The highest gas permeability was detected for the membrane Aspire® QL217. The Versapor®
200PR membrane showed the lowest gas permeability, due to the increased thickness of the active
membrane layer compared to the other membranes. The relatively low gas permeability of the
membrane Aspire® QP955 was caused by the smaller pores (100 nm) compared to the other membranes
(200 nm).
4.2. Diffusion
The gas diffusion process from the sweep gas channel into the feed gas channel and vice versa
played a significant role at low pressure gradients and low convective flux rates. This can be seen
by the exemplary calculated diffusion values for a 10 μm thick active membrane layer with a pore
diameter of 200 nm supported by a porous backer material with a thickness of 190 μm. The Knudsen
number for air in the active microporous membrane layer is calculated to be Kn = 0.34 with a mean
path length λair = 68 nm at 1 bar and 298.15 K [34]. Thus, in this case, the diffusion mechanism is a
mixture of Knudsen and free molecular diffusion.
However, as a simplification, only pure Knudsen diffusion in the active membrane layer

Dair,CO2 ,active = Dair,Kn is assumed to be equal to the highest possible mass transfer coefficient.
The Knudsen diffusion value is Dair,Kn = 27.6 mm2 /s, whereas the free diffusion value is
88
Dair,CO2 ,mol = 47.5 mm2 /s. In the real case, it is evident that the diffusion value of the active membrane
Dair,CO2 ,active lies in between Dair,Kn and Dair,CO2 ,mol .
In direct comparison, the transport coefficient in the membrane layer βair,CO2 ,active = 2.76 m/s
is over 10 times higher than the transport coefficient βair,CO2 ,backer = 0.25 m/s in the thick backer
material. It is clear that the backer material limits the mass transfer by diffusion. Due to this, a uniform
and free molecular diffusion through the membrane can be assumed, and the Knudsen diffusion can
be neglected.
With an average concentration gradient of Δy = 0.5, considering a pore area of Ap = Amem 0.5 ≈
50 mm, the diffusive volume flux of sweep gas (air) is Vair,diff ≈ 350 NmL/min. Additionally, an
equimolar flow of CO2 can be supposed to be transported diffusively in the opposite direction.
It is important to note that this is only a rough estimation. Many aspects, including the diffusive
mass transport within feed and sweep channel and exact membrane characteristics such as tortuosity,
porosity, and pore length, are not considered. Nevertheless, it can be assumed that the polymer
membranes used is this article, just like those considered in the model membrane, have a very low
mass transfer resistance.
In addition, the sweep gas loss by diffusion was detected at different sweep gas fluxes and
transmembrane pressure gradients, as shown in Figure 8. A clear correlation between low pressure
gradients and high concentration gradient-driven sweep gas loss by diffusion was observed.

Figure 8. Measured sweep gas loss through a Aspire® QL217 membrane for different sweep gas flows
.
at ϑ = 20◦ C and Vgas,feed,in = 500 NmL/min.
At a pressure gradient of 100 mbar, these losses became insignificant. Diffusive transport of the
feed gas also inevitably followed this behaviour. It can be concluded that diffusive mass transfer
phenomena will be irrelevant at pressure gradients higher or equal to ΔpTM,crit = 100 mbar.
4.3. Separation Efficiency

The effectiveness of a separation process was assessed by the separation performance, liquid loss,
and orientation independence. A detailed overview of the results and a discussion are provided below.
89
4.3.1. Separation Performance

In principle, the porous membrane-based micro contactor can be installed downstream of the
μDMFC system to achieve a flat, compact, and portable LOC design. By doing so, an open or closed
breather can be realised. In the case of the open breather, the membrane is visible from the outside,
and directly separates the CO2 into the environment, whereas the closed breather has an additional
channel for flushing by a sweep gas. However, in both cases, isothermal operating conditions cannot
be assumed due to the transient operating mode of the portable μDMFC.
In all experiments where the separation efficiency was investigated at increased fluid inlet
temperatures and without isothermal micro contactor operating conditions, liquid condensation
under single- and two-phase conditions at the membrane support, i.e., the sweep gas channel, was
observed. First, the liquid species evaporated at the membrane side into the gas phase. Thereafter,
the vapour was transported by diffusion or convection through the active and supporting layer of
the membrane. Subsequently, the vapour condensed at the membrane support due to the lower
temperature within the sweep gas channel as shown in Figure 9.
2" 1K2"

*22" )22"

Figure 9. Degree of condensation of the evaporated and diffusively transported liquid species at
40 ◦ C within the sweep gas channel on the supporting material, observed for different operating
times. Illustrated pictures are for following operating times 0 s, 150 s, 300 s, and 600 s using
. . .
Vl,feed,in = 5 mL/min, Vg,feed,in = 0 NmL/min, and Vg,sweep,in = 0 NmL/min.
As a consequence, the pores of the porous membrane got blocked and the separation performance
decreased rapidly after 10 min. To reduce the diffusive flux (part of the liquid loss of water and
methanol) and to avoid the condensation, a micro heat exchanger installed downstream after the
μDMFC should be taken into account for the μDMFC with LOC design.
Another possibility for avoiding condensation is an increased sweep gas flow up to 200 NmL/min.
Hereby, an increased liquid loss of water and methanol by liquid species diffusion during the
experiments without condensation was observed (see Section 4.3.2.). Moreover, the constantly supplied
sweep gas (synthetic air) was used as reference and dilution to detect inline the real separated CO2
amount by FTIR measurements. The experimental results for ϑinlet = 20 ◦ C, 40 ◦ C, and 60 ◦ C are
shown in Figure 10.
All porous membranes showed complete separation behaviour (SP ≥ 1 or SP = const.) for CO2
gas feed volume flows between 100–150 NmL/min. A decrease of SP was observed at CO2 feed gas
volume flows above 100–150 NmL/min. In both cases, a dependence on the inlet temperature ϑinlet was
noticed due to the liquid evaporation increasing the amount of gas to be separated, as well as decreasing
surface tension and viscosity of the water-methanol mixture. Nevertheless, the curve characteristics
for all porous membranes were almost identical, except for the maximum separation amount.
90

.
Figure 10. Comparison of the separation performance SP,CO2 for different Vg,feed,in at ϑinlet = 20 ◦ C,
.
40 ◦ C, and 60 ◦ C (Vl,feed,in = 5 mL/min, ΔpTM = 100 mbar, and cCH3 OH = 1 mol/L.
The turning point of SP indicated the maximum separable amount of CO2 at any given
transmembrane pressure as described by Darcy’s law. From this point, a characteristic regressive curve
was detected, agreeing with the theory.
At room temperature, the SP values for a complete separation were observed to be slightly
below 1, whereas at 60 ◦ C, the SP values were slightly above 1. In both cases, the gas solution and
dissolution processes of CO2 into the water-methanol mixture during the separation were responsible
for this phenomenon.
Moreover, only the porous membrane Supor® 200PR showed a dramatic decrease in
SP at ϑinlet = 60 ◦ C. After decreasing the temperature back to ϑinlet = 40 ◦ C, nearly the same SP
values were detected. It is assumed that a reversible temperature and methanol-induced change in the
porous membrane took place, leading to reduced gas permeability. Several repetitions with increasing
and decreasing inlet temperatures showed the same behaviour.
After the experiments, the membrane surfaces of all used membranes were investigated by SEM
and compared with the unused ones, as shown in Figure 11. For the PTFE-based membranes Aspire®
91
QP955 and Aspire® QP217, no significant changes on the membrane surface could be observed. The
Supor® 200PR membrane instead showed an irreversible closing effect of the pores by chemical
or thermal bonding of the membrane material (red squares). In the case of the porous membrane
Versapor® 200PR, an increase in surface porosity by visually larger pore diameter was noticed.

Figure 11. Images of the membrane surface by scanning electron microscopy after usage as separation
layer for all experimental investigations.
During short term tests using Supor® 200PR and Versapor® 200PR membranes, the detected
changes of the surface structure did not affect the separation performance. Nevertheless, it was
concluded that the acrylic copolymer-based membrane (Versapor 200PR) was degraded at the
top of the surface by the water-methanol mixture. For the observed surface behaviour of the
polyethersulfon-based membrane (Supor® 200PR), additional investigations are needed.
The comparison of the gas permeability under single and two-phase flow conditions in Table 5
showed that the gas permeability of the pure gas (Section 4.1) was significantly higher than with
two-phase flow conditions. It is assumed that this result is in general due to the not fully utilised
membrane area during the separation process.
Table 5. Comparison of the gas permeability under single and two-phase flow conditions.
κi [10−15 m2 ] at 20 ◦ C Ai [mm2 ]
Membrane κTPF
κg κTPF κg Aactive
Aspire® QP955 9.3 7.2 0.77 88.7
Aspire® QL217 14.0 10.6 0.76 86.7
Supor® 200PR 10.3 9.0 0.87 100.0
Versapor® 200PR 9.1 7.7 0.85 96.9
92
However, the liquid part of the two-phase flow partially reduced the active membrane area at slug,
transient, and corner flow state. In general, the membrane was covered by the liquid slugs at slug flow
conditions, whereas at under liquid corner flow conditions, i.e., at high feed gas volumetric flows, only
the edges were covered by the liquid. In addition, a proportion of the pores can be physically blocked
by the liquid. A detailed investigation of the utilised membrane area can be found in Section 4.3
“Active Membrane Area”.
For all CO2 gas feed volume flows, the Aspire® QL217 from CLARCOR Industrial Air, followed
by the Supor 200PR from Pall delivered the best separation performance and gas permeability values
for 20 ◦ C and 40 ◦ C.
4.3.2. Liquid Loss of Water/Methanol

Knowledge about liquid loss of water and methanol by evaporation and diffusion in a porous
membrane-based micro contactor operating as a closed or open breather for a μDMFC with LOC
design is an important evaluation criterion. Through a multi-variant calibration, all species in the
sweep gas outlet leaving the micro contactor could be determined. Thus, the real amount of liquid loss
during the separation process was measurable.
In order to exclude condensation in the sweep gas channel and piping, a higher sweep gas volume
flow was set. Hereby, the proportion of liquid loss by diffusion was higher than at lower sweep gas
volume flows, as shown in Figure 12, for a porous membrane-based micro contactor without TPF.

Figure 12. Diffusive liquid loss for water and methanol under single phase flow conditions (liquid)
of the porous membrane depending on the sweep gas volume flow for Aspire® QL217 at 20 ◦ C and
.
Vl,feed,in = 5 mL/min.
Furthermore, the liquid loss of water was larger than the liquid loss of methanol. For the liquid loss
of methanol, a proportional behaviour to the methanol concentration was observed. Simultaneously,
increased liquid loss of water was detected due to a higher vapour pressure of the water-methanol
mixture. In addition, a slight contribution to the liquid loss by a decreasing surface tension and
viscosity is assumed.
In direct comparison, the liquid loss by diffusion was significantly higher than the liquid loss
through feed gas saturation by evaporation. Furthermore, it can be clearly seen in Figures 13 and 14
that the liquid loss of water and methanol increased with rising temperatures and feed gas volume
93
flows. Additionally, the impact of increasing volume flows was lower than the increasing temperatures
on the liquid loss of water and methanol.

Figure 13. Overall liquid loss for water and for all porous membrane under two-phase flow conditions
◦ ◦ 60 ◦ C) and feed gas volume flows
different feed inlet temperatures (ϑinlet = 20 C, 40 C, and
for
. .
Vl,feed,in = 5 min
mL
and Vg,feed,in = 50 NmL
min , 100
NmL
min , and 150 NmL
min .

Figure 14. Overall liquid loss for methanol and for all porous membrane under two-phase flow
conditions
for different feed inlet temperatures (ϑinlet = 20 ◦ C, 40 ◦ C, and ◦
60 C) and feed gas volume
. .
flows Vl,feed,in = 5 min
mL
and Vg,feed,in = 50 NmL
min , 100
NmL
min , and 150 NmL
min .
The Aspire® QP955 and Supor® 200PR had the lowest liquid loss for water and methanol over
the whole tested range compared to the other porous membranes. In the case of the Aspire® QP955
membrane, the smaller pore diameter (dp = 100 nm) was probably responsible for this behaviour,
whereas for the Supor® 200PR, the surface structure of the membrane was responsible. The highest
liquid losses of water and methanol were detected for the Aspire® QL217 und Versapor® 200PR.
94
Based on the presented results, it can be concluded that the liquid loss due to the diffusion was
the largest in a closed breather with additional sweep gas. The liquid loss in a closed or open breather
without sweep gas is mainly caused by gas saturation through evaporation.
4.3.3. Orientation Independence

The portability of a porous membrane-based micro contactor for the gas/liquid phase separation
depends primarily on the orientation independent working principle. Theoretically, as mentioned in
Section 2 “Theoretical Background”, a calculated Confinement number of Co = 3.5 and the Etövos
number of Eo = 0.1 should be sufficient for an orientation-independent gas/liquid phase separation.
For the calculation of Co and Eo, a micro channel filled with water + air, a height of 0.5 mm, and a
width of 1.7 mm was assumed.
Nevertheless, different orientations, as shown in Figure 15, were tested for all membranes at
complete separation state (SP = 1 or SP = const.) and incomplete separation state (SP < 1) were
tested, to confirm the orientation independent gas/liquid phase separation. As an example, the result
for the Aspire® QL217 is shown in Figure 15. With a feed gas volume flow rate of 200 NmL/min and
350 NmL/min, a SP ≤ 1 and SP ≤ 0.6 was detected, respectively.

.
Figure 15. Orientation independence tests for Aspire® QL217 (Vl,feed,in = 5 mL/min, ϑinlet = 40 ◦ C,
ΔpTM = 100 mbar, and cCH3 OH = 1 mol/L).
The orientations had only a minimal influence on the separation performance—less than 3%—for
a feed gas volume flow rate of 200 NmL/min. For a feed gas volume flow rate of 350 NmL/min, an
influence of less than 5% was observed. Identical results were also obtained for the other membranes.
Based on the results shown above, an orientation independent separation performance can be assumed.
4.4. Active Membrane Area

When two-phase flow is present in the feed channel of the micro contactor module, a fraction of
the overall available membrane is covered with liquid, and can therefore not be used for gas separation.
Only the gas-covered part of the membrane, defined as active membrane area, contributes to the
separation process. The active membrane area, calculated using Equation (9) and κg from Table 4,
grows with increasing feed gas flux.
95
In Figure 16, this phenomenon is shown for the membrane Aspire® QL217 and for different feed
liquid methanol concentrations. At a state of complete gas separation (SP = 1 or SP = const.), the
active membrane area increased linearly with increasing flow rate of the feed gas. When the feed gas
flux exceeded the separation capability of the membrane (SP < 1), the calculated values for the active
membrane area shows exponentially-decreasing behaviour.
Figure 16. Active membrane area (calculated with Equation (9)) of membrane QL 217 at ϑ = 20 ◦ C,
. .
ΔpTM = 100 mbar, Vliq,feed,in = 5 mL/min, and Vgas, sweep, in = 10 mL/min for different methanol
.
concentrations and different Vgas,feed,in (left image). Development of the transmembrane pressure
.
gradient with increasing Vgas,feed,in (right image).
In addition, an increased feed gas flux led to a higher pressure gradient, and subsequently, to a
higher gas permeation flux. At the same time, the gas/liquid ratio in the feed channel and the mean
velocity increased. Through this, the residence time of the liquid on the membrane was reduced by
pushing the liquid out of the feed channel more rapidly, resulting in a decreased membrane area
blocked by liquid.
The high discontinuity of the measurement results at 200–300 NmL/min was caused by the
instability of the separation at the point where the separation first became incomplete and insignificant
amounts of gas could leave the feed channel outlet. At this point, pressure increased abruptly because
of the additional pressure loss caused by the gas pushing the liquid in the line out, leaving the feed
channel. This effect was dynamic, and pressure fluctuation could also be high at this point. The
separation stabilised when more feed gas was used.
The concentration of methanol in the feed liquid flow—in the range of 0–2 mol/L—had no direct
influence on the available membrane area or the active membrane area during the separation process.
5. Conclusions
In general, the applicability of porous membranes as a separation layer under μDMFC working
conditions (physically and chemically) was confirmed. Due to the high capillary pressure in the small
pores, the permeation of liquid was prevented, while gas could be transported via the pores of the
membrane across the membrane by applying a pressure gradient. In addition, the diffusion flow via
these membranes is substantial, and should not be neglected if the separation exceeds the capability of
the available membrane area and a high sweep gas flux is used.
In the investigated separation module, the pressure in the gas bubble or phase, which is strongly
dependent on the channel size, was negligible compared to the pressure gradient required for an
96
efficient gas separation process. Furthermore, the capillary pressure was always overlain by the
pressure drop caused by the active transport of fluids through the narrow channel. Through this
observation, it can be concluded that the gas separation solely driven by the capillary pressure in the
gas phase located in the channel cannot be realised in a compact and active driven μDMFC.
To increase the capillary pressure in the gas bubble or gas phase, the channel size has to be reduced
by an order of 10–20. However, by reducing the channel size, the pressure drop due to the smaller
channel would increase dramatically. A parallel arrangement of smaller channels instead of a single
channel could be helpful to normalise the pressure drop again, but the distributions of two-phase
into the smaller channels is not homogenous enough and less controllable. As a result, uncontrollable
short-circuit flows of unseparated gas can occur.
Furthermore, the gas separation was found to follow Darcy’s law describing the separated gas
amount as proportional to the pressure gradient over the membrane. To obtain complete phase
separation under some of the investigated conditions, it was observed that for an effective gas
separation, a transmembrane pressure of at least 100 mbar was necessary. In addition, it is known
that the low bubble pressure, i.e., the capillary pressure of the gas phase or bubble within the micro
channel, amounts to a single digit mbar value, so that the driving force has to be a sufficiently high
transmembrane pressure. With an area of 114.5 mm2 , all membranes were capable of separating at
least 100 NmL/min CO2 under μDMFC working conditions using a pressure gradient of 100 mbar.
This is sufficient for a typical 20 W DMFC producing 93 NmL/min CO2 gas at a considered efficiency
of 41% [35].
The diffusion of the liquid species and the amount of sweep gas also affected the diffusion of feed
gas into the sweep channel and vice versa. The diffusion process was also dependent on the convective
gas flow through the membrane, and thereby, was dependent on the applied pressure gradient. At
high pressure gradients, diffusion rates of feed and sweep gas were found to be insignificant. It was
observed that the convective flux is predominant at an empirically-determined, critical transmembrane
pressure gradient ΔpTM,crit of 100 mbar, suppressing the diffusion flow of the sweep gas completely.
Finally, alternatives to polymer-based membranes should be investigated to overcome negative
properties such as swelling or chemical resistance against methanol. At present, metallic microsieves
coated with hydrophobic layers are considered as a potential substitute, and are being studied at the
Institute of Micro Process Engineering. With respect to the separation system and its integration in a
μDMFC, further research is still required. Different channel geometries and channel coatings could
provide a better liquid/gas distribution during the separation, and could increase the active membrane
area for the gas separation. Finally, using a prototype μDMFC to create the two-phase-flow feed stream
to accurately replicate the conditions that would be expected in a complete integrated system, could
improve the separation process under transient working conditions.
Supplementary Materials: The following are available online at http://www.mdpi.com/2305-7084/2/4/55/s1.

Author Contributions: Conceptualisation, K.M.D.; methodology, K.M.D.; formal analysis, K.M.D. and V.W.;
investigation, V.W. and K.M.D.; resources, KIT; data curation, V.W. and K.M.D., writing—original draft
preparation, K.M.D.; writing—review and editing, K.H.-S.; visualisation, K.M. and V.W.; supervision, R.D.;
project administration, K.M.D. and K.H.-S.; funding acquisition, K.H.-S. and R.D.
Funding: This work was funded and supported by the BMWi and AiF through IGF-Project 18741 N.
Acknowledgments: The authors acknowledge support of this work by staff of the Institute for Micro Process
Engineering at Karlsruhe Institute of Technology. We also thank “Clarcor Industrial Air” and “Pall Corporation”
for the graciously provided porous membranes.
97
Nomenclature
Latin Symbols
A area (m2 )
Co confinement number (-)
d diameter (m)
D diffusion coefficient (m2 s−1 )
dh hydraulic dimeter (m)
Eö Eötvös number (-)
f multiplication factor (-)
g standard gravity (9.981 kg m s−2 )
h height (m)
H mean curvature (m−1 )
k curvature of sphere (m−1 )
kCO2 solubility coefficient (mol L−1 atm−1 )
K Parameter (-)
kb Boltzmann constant (1.38 10−23 J K−1 )
Kn Knudsen number (-)
l thickness (m)
m mass (kg)
M molar mass (kg mol−1 )
.
n molar flux (mol s−1 )
p pressure (Pa)
r radius (m)
R radius of channel geometry (m)
Sp separation performance (-)
T temperature (K)
U perimeter (m)
V volume (m3 )
.
V volume flux (m3 s−1 )
Vm molar volume (m3 mol−1 )
v diffusion volume (-)
w width (-)
x/y molar fraction (-)
X solubility constant (-)
Y molar loading (-)
Subscripts
active active
air air
backer backer material
cap capillary
coll. collision
crit critical
CH3 OH methanol
CO2 carbon dioxide
diff diffusive
feed feed
gas gas
H2 O water
in in
inlet inlet
Kn Knudsen
98
liq liquid
lg liquid-gas-interface
mem membrane
mol molecular
nw non-wetted
out out
p pores
perm permeate
sg solid-gas-interface
sl solid-liquid-interface
sol dissolved
sweep sweep
tm trans membrane
TPF two-phase-flow
w wetted
t,b,l,r top, bottom, left, right
Greek symbols
β mass transfer coefficient (m s−1 )
η dynamic viscosity (Pa s)
ϑ temperature (◦ C)
κ permeability (m2 )
λ mean free path length (m)
ρ density (kg m−3 )
σ surface tension (N m−1 )
σcoll collision diameter (m)
ϕ contact angle (◦ )
Δ gradient (-)
ω mass fraction (-)
Abbreviations
μDMFC micro-direct methanol fuel cell
DIK Deutsches Institut für Kautschuktechnologie
FTIR Fourier-transform infrared
IMVT Institute for Micro Process Engineering
KIT Karlsruhe Institute of Technology
LOC lab on a chip
PMMA polymethylmethacrylate
PP polypropylene
PTFE polytetrafluoroethylene
SEM scanning electron microscope
SP separation performance
TPF two-phase flow
ZBT Zentrum für Brennstoffzellentechnik
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101
chemengineering
Article
Solar Energy Assisted Membrane Reactor for
Hydrogen Production
Barbara Morico 1 , Annarita Salladini 1 , Emma Palo 2 and Gaetano Iaquaniello 2, *
1 Processi Innovativi srl, Via di Vannina 88, 00156 Rome, Italy; [email protected] (B.M.);
[email protected] (A.S.)
2 KT—Kinetics Technology S.p.A., Viale Castello della Magliana 27, 00148 Rome, Italy; [email protected]
* Correspondence: [email protected]; Tel.: +39-06-60216231
Received: 9 November 2018; Accepted: 2 January 2019; Published: 15 January 2019
Abstract: Pd-based membrane reactors are strongly recognized as an effective way to boost H2 yield
and natural gas (NG) conversion at low temperatures, compared to conventional steam reforming
plants for hydrogen production, thereby representing a potential solution to reduce the energy penalty
of such a process, while keeping the lower CO2 emissions. On the other hand, the exploitation of
solar energy coupled with a membrane steam reformer can further reduce the environmental impact
of these systems. On this basis, the paper deals with the design activities and experimentation carried
out at a pilot level in an integrated prototype where structured catalysts and Pd-based membranes are
arranged together and thermally supported by solar-heated molten salts for steam reforming reaction
Keywords: membrane reactor; Pd-based membrane; hydrogen; steam reforming; solar energy
1. Introduction
Pd-based membrane reactors are strongly recognized as an effective way to boost H2 yield and
natural gas (NG) conversion at low temperatures, compared to conventional steam reforming plants
for hydrogen production [1–5].
Indeed, the NG steam reforming (CH4 + H2 O = CO + 3H2 ) is an endothermic reaction
(ΔH0 298K = 206 kJ/mol) and is limited by chemical equilibrium. This means that operation at high
temperatures (850–900 ◦ C) are required to reach significant hydrogen yields. In order to supply
the reaction heat duty, a stream of NG is typically burned in the steam reforming furnace, thereby
determining a reduction of the overall process efficiency as well as an increase in CO2 emissions.
Under such a scenario, the coupling of the steam reforming unit with a Pd-based hydrogen-selective
membrane can provide for the following benefits: (i) enhancement of hydrogen yield and process
efficiency at low temperatures, since the continuous selective removal of hydrogen from reaction
environment allows maintaining the gas mixture composition far from equilibrium one; (ii) replacement
of the high-temperature flue gases used in the furnace with a cleaner energy source or with waste heat
available from another process; (iii) use of cheaper steel alloys for the fabrication of the reforming tube
instead of the expensive materials currently used to withstand the high operating temperatures of
conventional steam reforming plants.
KT—Kinetics Technology has gained an impressive experience over the last 15 years in the design
and operation of innovative pilot plants, membrane reformers-based, for the production of pure
hydrogen [6–11]. In particular, a pilot unit of 20 Nm3 /h of pure hydrogen has been designed and
tested for more than 3000 h in a relevant industrial environment with NG supplied from the town grid,
with a basic configuration characterized by sequential steps of reaction and membrane separation,
in order to achieve the overcoming of thermodynamic equilibrium, while maintaining at the same time
slightly decoupled operating conditions for a reformer and a membrane module, thereby avoiding a
great deal of thermal stress for Pd-based membranes. The former proposed configuration, even not

totally in line with the process intensification concept, represents a more simplified membrane reactor
concept, where the membrane reactor in principle does not suffer from engineering design challenges
and accordingly might boost the industrial acceptance of the novel technology in the first phases of
transition to it.
Over the last few years, with the aim to further reduce the CO2 emissions, typical of the highly
energy-intensive processes of the hydrocarbon industry, attention has been focused by the Company
on the application of solar energy as a renewable energy source, with the possibility to exploit it with
molten salts having the role of heating medium and energy vector. The integration between the solar
plant and industrial processes is widely studied all over the world [12–15]. For instance, Concentrating
Solar Power (CSP) offers an attractive option to power industrial-scale desalination plants requiring
thermal and electrical energy. Integration of CSP with multi-effect distillation (MED) and Reverse
Osmosis (RO) seems to be cheaper than photovoltaic (PV) systems [16]. Another potential application
of solar energy is to power chemical processes when a high thermal duty is required: this is the case
for endothermic reactions, which are a very promising opportunity for the production and storage of
usable energy, and mitigation of CO2 emissions.
Therefore, the aim of this paper is to report the experimental activities performed by the
KT—Kinetics Technology-controlled company Processi Innovativi in the framework of the EU Project
CoMETHy (Compact Multifuel Energy To Hydrogen conversion) in this field, studying the coupling of
an integrated membrane reformer with solar-assisted molten salts heating, with the operation of a pilot
unit specifically designed to this aim. The main feature of such a reactor is the complete integration of
catalyst and membranes in only one vessel according to the process intensification concepts [17].
An economic analysis has been also carried out, in order to check the industrial feasibility of the
option to provide for a competitive novel technology at reduced environmental impact.
2. Experimental: Pilot Plant Description

The pilot plant was designed for a capacity of 3 Nm3 /h of pure hydrogen. The facility is available
at ENEA Casaccia premises, and the process scheme of the pilot unit is reported in Figure 1.
Figure 1. Solar energy-assisted membrane pilot plant process scheme.
The plant architecture is based on a first prereformer stage (R-01) placed upstream to an integrated
membrane reactor (R-02). Methane is supplied by pressurized gas cylinders. A process steam and
a sweep steam for membranes are produced with a dedicated electrical boiler. Reaction heat to R-01
and R-02 is supplied through a molten salts mixture fed to R-02 at a maximum inlet temperature of
550 ◦ C and further routed to the R-01.
103
Molten salts are countercurrently flowing through the two reactors, entering first R-02 at the
desired temperature and flow rate. Molten salts are stored in a tank and pumped at the desired flow
rate through an electrical heater, where the desired temperature is applied before being sent to the
chemical test section. Due to the relatively low thermal duty of the reactors, the molten salts return
temperature from the test section was just about 10 ◦ C lower than the molten salts supply temperature.
For this reason, in order to maintain a temperature lower than 500 ◦ C inside the molten salts tank,
a fraction of the heat from the back stream was recovered by heating the molten salts stream from the
tank, and finally the temperature was further reduced by means of an air cooler.
In the prereformer stage of R-01, a partial methane conversion occurs, and accordingly the
produced syngas mixed with unconverted methane routed to R-02 contains a certain amount of
hydrogen, allowing membrane in R-02 to be active just at the inlet of reactor.
R-01 was designed in a shell and tube configuration where molten salts mixture flows in the shell
side supplying reaction heat, and catalysts are installed inside tubes (Figure 2).
Figure 2. Catalyst arrangement in R-01 reactor.
R-02 was also designed in a shell and tube configuration (Figure 3).
(a) (b)
Figure 3. R-02 reactor. (a) overall reactor; (b) reactor installation.
The main difference with the R-01 reactor is that in particular in R-02, catalysts and membranes
are arranged according to a tube-in-tube configuration with catalysts in the annular section around the
membrane tube (Figure 4). The latter is equipped with an inner tube to allow for sweep gas flow on
the permeate side.
104
Figure 4. R-02 reactor membrane arrangement.
Ten Pd-based membrane tubes are installed in R-02, with a permeate stream collected from R-02
and cooled down in order to easily separate sweep gas as condensate.
The installed membranes were provided by ECN (Energy Research Centre of the Netherlands)
and they had an outside diameter of 14 mm and a length of 80 cm for an overall area of about 0.35 m2 .
The main characteristics of the membranes are reported in Table 1.
Table 1. Main characteristics of membranes installed in R-02.
Membr. Thick. Permeance,

Membr.
Membrane Supplier Support Selective Selective Geometry Production Method Nm3/(hm2bar0.5)
Area, m2
Layer Layer, m at 400–450 ◦ C
Electroless
M (R-02) ECN Al2 O3 Pd 3–6 0.35 Tubular 10–15
Deposition
A bifunctional catalyst, nickel-noble metals-based, deposited on silicon carbide foam, is installed

in both R-01 and R-02 reactors separately, shaped in the form of cylinder for R-01 (Figure 2) and annular
cylinder for R-02 wrapped around the membrane tube (Figure 5).
Figure 5. R-02 reactor catalyst arrangement.
The catalysts were prepared at the ProCeed Lab of the University of Salerno. To improve
membrane separation efficiency, a superheated steam is used as a sweep gas in a countercurrent
configuration. Reactors R-01/R-02 and piping in contact with molten salts are electrical traced, in order
to assure, during the start-up and shut down procedures, temperature above the salts freezing point.
105
The main operating conditions of the catalytic tests carried out with the integrated membrane
reactor are reported in Table 2.
Table 2. Main operating conditions for the integrated membrane reactor.
Description Value
Flow rate
CH4 inlet pre-reforming reactor R-01, kg/h 0.3–1.5
H2 O inlet pre-reforming reactor R-01, kg/h 4.5–6.0
H2 O Sweep gas, kg/h 0–2.0
Molten salts, kg/h 1250–1650
Pressure
P feed side, barg 9.8–9.5
P permeate side, barg 0.4
Temperature
T range molten salts, ◦ C 450–550
For the calculation of heat and material balances of the pilot plant, each of these units was
modeled with Aspen Plus 9.0 as a standard process simulator. For the integrated membrane reactor
simulation, ASPEN Plus 9.0 was combined with the kinetic equations reported by Xu and Froment [18]
and membrane permeation derived on Pd membranes coming from the same supplier and tested by
the authors in the framework of previous experimental activities.

Different parameters were considered for the performance evaluation of the integrated system,
such as the molten salts temperature, sweep steam flow rate and steam-to-carbon ratio. The effects of
molten salts temperature on the methane conversion and the permeate H2 flow rate at an operating
pressure of 8.5 barg are reported in Figure 6.
Figure 6. Effects of molten salts temperature on the methane conversion and the permeate H2 flow rate.
It can be observed that by increasing the molten salts temperature, the methane conversion
increases since the endothermic reforming reaction is promoted at high temperatures, with CH4
conversion increasing from around 30% at 450 ◦ C to around 60% at 540 ◦ C. Obviously, the same trend
can be observed for the flow rate of hydrogen permeating through the Pd membranes. At 540 ◦ C,
a permeate hydrogen flow rate of around 3.5 Nm3 /h of hydrogen can be observed. It is also of interest
the low CO concentration can be detected on the permeate side. Such values in consequence of the low
106
level in the retentate side are in order of 12 ppmv (dry basis) at 450 ◦ C and about 50 ppmv (dry basis)
at 540 ◦ C. The increase of CO concentration on the permeate side is in line with the occurrence of water
gas shift more promoted at lower temperatures, thereby reducing the CO content on the retentate side
and accordingly the CO detected on the permeate side. In terms of permeate purity, all tests accounted
for an average H2 content higher than 99.8% mol (dry basis).
The effects of the sweep gas flow rate on the methane conversion and the permeate H2 flow
rate are reported in Figure 7 for two operating temperatures, 544 ◦ C and 500 ◦ C, respectively, at an
operating pressure of 8.5 barg.
Figure 7. Effects of sweep gas flow rate on the methane conversion and the permeate H2 flow rate.
For both operating temperatures, an increase in methane conversion and accordingly in the
permeate H2 flow rate can be observed with increasing of the sweep gas flow rate, since a higher value
for the latter parameter enables a higher driving force across the membrane. However, it is important
to observe that the strongest effect can be checked when the sweep gas flow rate is increased up to
1 kg/h. At higher flow rates, the impact is more negligible. At about 1 kg/h of sweep gas flow rate,
the hydrogen recovery is around 70% at 544 ◦ C. A productivity of H2 of 1.5 Nm3 /h can be obtained,
even in absence of sweep gas on the permeate side.
The effects of steam-to-carbon ratio on methane conversion and H2 recovery are reported in
Figure 8, at the three operating temperatures of 500 ◦ C, 530 ◦ C, 544 ◦ C and an operating pressure of
8.5 barg. The sweep gas flow rate was kept constant at 2 kg/h.
An increase in methane conversion can be observed with increasing of the steam-to-carbon ratio
in the feed. The effect is more pronounced at low temperatures. At the highest steam-to-carbon ratio
investigated of 16 (on weight basis), a methane conversion of 99% can be detected at 544 ◦ C. In terms
of hydrogen recovery, in this condition, it is possible to achieve a recovery of more than 90%.
The performance comparison of the integrated membrane system with the thermodynamic
equilibrium without a membrane is reported in Figure 9, at a feed pressure of 8.5 barg and
a steam-to-carbon ratio of 4 (on weight basis).
107
(a) (b)
Figure 8. Effects of steam-to-carbon ratio on methane conversion (a) and H2 recovery (b).
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Figure 9. Methane conversion with an integrated membrane reactor and without a membrane.
An overall feed conversion of 58% can be achieved at 543 ◦ C, doubling the conversion that can be
achieved in a conventional reformer at the same temperature.
The system performance was also investigated in time-on-stream tests, in order to check its
potential feasibility at industrial conditions. The results in terms of the methane conversion and the
permeate hydrogen concentration are reported in Figure 10.
The system performance is very stable for more than 100 h of continuous operation and
no macroscopical signs of reactor performance loss have been evidenced over the experimental
operation period, despite handling of catalysts and membranes and the several switches of operative
conditions. The achieved results confirm the potentiality of the solution for application at industrial
conditions; even if this concept is further assessed, it would be important to check the behavior of
the membrane-catalyst coupling for at least 1000 h of continuous operation. Indeed, this order of
magnitude of stability time is usually required for the catalyst at an accepted industrial level. In this
way, if the stability of the membrane and that of catalyst are aligned to such order of magnitude,
this allows to avoid too many frequent shut down operations of the plant for any procedure of
maintenance or replacement of key components.
108
(a)
(b)
Figure 10. Methane conversion (a) and permeate H2 concentration (b) in time-on-stream tests.
4. Economic Analysis
In order to make a preliminary economic analysis about the potentiality of the solar energy
coupling with membrane reactors at an industrial capacity of 5000 Nm3 /h of hydrogen, for the sake of
simplicity, it was assumed to operate with a six-step membrane reactor in an open architecture, where
reactions stages are followed by membrane stages.
A process arrangement has been studied in order to realize a high-energy-efficiency process
coupled with a low hydrogen production cost and CO2 removal, based on the work proposed by
Atsonios et al. [19]. The process scheme considered with CO2 capture in pre-combustion is reported in
Figure 11. The main units are represented by: (i) the multistep membrane steam reformer, (ii) product
compression, (iii) power island. Each of these units was modeled with a standard process simulator.
The rate of hydrogen removed with a Pd/Ag membrane is described by the Hydrogen Recovery
Factor (HRF), which is strongly correlated with the total installed membrane area, the pressure at
the permeate side, and that at the retentate side. The pressure at the feed side was set to be equal to
9.2 barg, and meanwhile, the permeate side was kept at 0.7 barg. A low-pressure steam extracted from
109
the steam cycle was used as a sweep gas to reduce hydrogen partial pressure. A sweeping steam was
added in order to have an equimolar mixture of hydrogen and steam on the permeate side. The HRF
(Hydrogen Recovery Factor) was kept constant in our simulation and equal to 90% (overall).
Figure 11. Process scheme for membrane steam reforming solar energy assisted with export
power production.
The solar field was designed for heat molten salts with a temperature up to 550 ◦ C. Molten salts
are fed to a steam reforming section composed by a pre-reformer and a six-step membrane Steam
Reforming reactor. The outlet temperature of molten salts exiting the reaction section is 490 ◦ C, so they
can be used to produce the process steam required for the steam reforming reaction and the sweeping
steam to be used at the membrane separation stage: additional steam is produced and used to generate
power in a steam turbine.
Excess power is then exported. Molten salts are then forwarded to the solar field at a temperature
of 290 ◦ C. The NG is mixed with steam and sent to the reaction section; the produced hydrogen is
recovered by membranes and then compressed to a pressure of 20 barg. The retentate is cooled down
to generate steam (heat recovery) and then, after a CO2 removal stage through a conventional amine
unit, compressed and recirculated to the SR section. In this way, such a scheme achieves the complete
conversion of NG in H2 and CO2 . The total duty provided by the solar field is 16.7 MMkcal/h, much
larger than what is required by the reforming section. The specific export of power was calculated in
0.4 kWh/Nm3 of produced hydrogen for an overall production of 2 MWh. The membrane area was
estimated at 976 m2 . In the calculation, a 5 μm thick larger of Pd/Ag23 wt% with a permeability of
30 Nm3 /h m2 bar0.5 and H2 /CO minimum selectivity of 200 was assumed [6].
The cost of production (COP) per Nm3 of H2 produced was calculated by adding the capital
expenditure (CAPEX) and the operating expenditure (OPEX) costs. No benefit was taken for CO2
reduction emission. In addition, it is assumed that SR reactor is powered with a molten salts flow
heated with solar energy for 5000 h/year, and in the remaining period of time, 3400 h/year, molten
salts are heated through a process heater where NG is fired. Parameters used for economic analysis
are reported in Table 3.
Table 4 reports, together with operating conditions, the relevant COP for the innovative scheme
compared with a conventional steam reformer scheme, where reaction duty is provided by purge
110
gas from pressure swing adsorption (PSA) and additional fuel gas. The plant architecture is that it
provides the steam required by the reboiler of the CO2 recovery unit.
Table 3. Key economic parameters for the economic evaluation.
Description Values
NG cost, €/kg 0.22
Electricity cost, €/kWh 0.075
Annual depreciation factor 10
N◦ of hours powered by sun 5000
Table 4. Cost of production (COP) of H2 for the conventional scheme and molten salts-based
steam reforming.
Description Conventional SR Molten Salts-Based SR

H2 production, Nm3 /h 5000 5000 5000
N of hours 8400 5000 3400
Feed + Fuel, ton/h 1.6 0.98 2.57
Reformer duty, MMkcal/h 5.0 3.9 3.9
Solar field duty, MMkcal/h - 16.7 -
H2 compression at 20 barg, kWh/Nm3 H2 - Included Included
CO2 recovery, ton/h 2.55 2.55 2.55
OPEX, €/Nm3 H2 (calculated) 0.077 0.045 0.115
CAPEX, M€ 12.5 22.5 22.5
Export of power, kWh/Nm3 H2 - 0.4 0.4
Depreciation rate per year, M€ 1.25 2.3 2.3
Depreciation rate, M€/Nm3 H2 0.030 0.054 0.054
Total production costs, €/Nm3 H2 0.106 0.068 0.138
Total average production cost, €/Nm3 H2 0.106 0.097
Total production cost comparison 100 91
It is quite evident that the innovative scheme is interesting and that the membrane assisted H2
production powered by solar energy, and coupled with CO2 removal may already compete with
conventional steam reforming if electricity price is high enough.
In this regard, by increasing the electricity price, the difference in COP between the conventional
scheme and the molten salts-based SR is higher at a higher electricity price. Anyway, as shown
in Figure 12, the two configurations become equivalent at an electricity price much lower than
current values.
Figure 12. Influence of COP vs. electricity cost.
111
It is also important to note that in conventional technology, about 70% of the production costs are
related to the variable costs. The situation is quite different for the innovative scheme, where more
than 55% of COP is related to the CAPEX and then only 45% is related to OPEX. Such a difference
implies that, if accelerated depreciation is applied, production costs of a scheme will be more affected
than for the conventional SR technology. In particular, it is calculated that the break-even point is
reached at a depreciation factor of 7; with a depreciation factor of 12, the difference becomes even more
important, reaching almost 15%.
5. Conclusions
The performance of a compact membrane reactor for steam reforming coupled with solar energy
has been evaluated at a pilot level. The membrane reactor has been designed to integrate structured
catalysts and Pd-based membranes with an overall thermal sustainment provided by solar heated
molten salts. The design activities show that the engineering of a membrane reactor involves the
proper optimization and arrangement of catalyst volume and membrane area. The experimentation
carried out clearly indicates that the developed system is able to guarantee a high-purity hydrogen
stream, keeping low feed consumption. In addition, a preliminary economic analysis, aiming at
evaluating the benefits from the integration between solar energy and membrane steam reforming in
open architecture, shows that the solution is a promising approach to minimizing the energy penalty,
the hydrogen production cost and CO2 emitted per ton of product. Experimental time-on-stream
tests with longer duration than the reported ones in this paper would further be helpful to definitely
consider this scheme potentially applicable at an industrial level.
It is also worth mentioning that a proper design of a thermal storage as well as that of a back-up
system could allow managing properly fluctuation of solar energy in order to assure continuous
operation for the hydrogen plant.
6. Patents
Iaquaniello, G., Salladini, A., Morico, B. Method and system for the production of hydrogen. US
Patent US9493350B2, 15 November 2016 (priority date 16 March 2012).
Author Contributions: All authors contributed to writing and correcting the paper.
Funding: The research leading to these results has received funding from the European Union’s Seventh
Framework Programme (FP7/2007-2013) for the Fuel Cells and Hydrogen Joint Technology Initiative under
grant agreement number 279075 for CoMETHy project.
Conflicts of Interest: The authors declare no conflicts of interest.
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113
chemengineering
Article
Dry Reforming of Methane in a Pd-Ag Membrane
Reactor: Thermodynamic and Experimental Analysis
Alessio Caravella 1,2 , Adele Brunetti 1, * , Monia Grandinetti 1,2 and Giuseppe Barbieri 1
1 Institute on Membrane Technology, National Research Council (ITM-CNR), Via P. Bucci, Cubo 17C,
87036 Rende (CS), Italy; [email protected] (A.C.); [email protected] (M.G.);
[email protected] (G.B.)
2 Department of Environmental and Chemical Engineering (DIATIC), University of Calabria, Via P. Bucci,
Cubo 44A, 87036 Rende (CS), Italy
* Correspondence: [email protected]; Tel.: +39-0984-492012; Fax: +39-0984-402103
Received: 13 September 2018; Accepted: 9 October 2018; Published: 10 October 2018
Abstract: The present work is a study of CO2 Reforming of Methane (DRM) carried out in a catalytic
Pd-based membrane reactor. A detailed thermodynamic analysis is carried out, calculating the
chemical equilibrium parameters in two different cases: (a) DRM along with the Reverse Water Gas
Shift (RWGS) reaction and (b) DRM along with both RWGS and the Boudouard Reaction (BR). The
performance of membrane reactor is then experimentally analyzed in terms of methane conversion,
hydrogen recovery and H2 /CO reaction selectivity by varying feed pressure and CO2 /CH4 feed
molar ratio and 500 ◦ C and GHSV = 100 h−1 . Among the obtained results, a CH4 conversion of about
26% and a H2 recovery of 47% are achieved at low feed pressures, exceeding the traditional reactor
equilibrium conversion. This effect can be attributed to the favorable thermodynamics coupled
to the hydrogen permeation through the membrane. This study further demonstrates the general
effectiveness of membrane-integrated reaction processes, which makes the production of syngas
more efficient and performing, providing important environmental benefits.
Keywords: membrane engineering; hydrogen production; CO2 conversion
1. Introduction
In the last decade, the energy demand has been growing by 1.2% a year and fossil fuels
still maintain a production share of ca. 75%. However, the ever-stricter problems connected to a
sustainable growth and to a lower environmental impact lead to the conclusion that the time of easy oil
consumption is finished. Nowadays, the necessity to release energy production from oil and natural
gas as primary energy sources is becoming more and more pressing [1–3]. Indeed, more in general,
diversifying such sources in order to assure supply, and in the meantime increase effort dedicated
to the reduction of environmental problems, has led to the development of alternative technologies
designed to enhance both the efficiency and environmental acceptability of energy production, storage
and use, in particular for power generation [4]. Among these technologies, the exploitation of light
hydrocarbons is surely the main realistic energy source, since they allow both power generation and
environmentally-friendly fuel production [5,6].
Actually, converting CO2 into valuable hydrocarbons seems to be one of the most recent advances
in CCU (Carbon Capture and Utilization), being one of the best solutions to both global warming
and energy lacking problems. Several technologies have recently been explored and are reported in
literature for CO2 conversion [7]. These technologies are based on hydrogenation, electrochemical,
thermochemical or biocatalytic processes, and photocatalytic reduction. Among these, photocatalytic
conversion is growing faster in the development not only of more active catalysts but also in the
design of innovative process units [8,9]. In addition, biochemical and bio-mimetic approaches are

also reaching interesting results although they are still to be applied at large scale. [10,11]. A very
active research area is the development of an “artificial leaf” [12] that collects energy in a similar
way as a natural one [13,14], combining water oxidation and CO reduction to produce liquid fuels
by artificial photosynthesis; however, the development of this technology is also far from real scale,
owing to limitations on solar energy-to-chemical conversion efficiency, costs, robustness and of easy
construction [13].
Dry reforming of methane (DRM) is a reaction that has led significant interest owing to the
possibility to convert greenhouse gases, CO2 and CH4 to produce valuable products. The resulting
synthesis gas has, in fact, a CO/H2 ratio close to 2, which is more appropriate for forming hydrocarbons
by Fischer-Tropsch synthesis and for carbonylation and hydroformylation reactions [15]. Moreover,
natural gas and biogas from fields having high carbon dioxide content can be directly used for reaction,
avoiding separation and purification stages. Although the undoubted benefits, DRM development on
large scale is still limited owing to the usual rapid deactivation of catalysts due to coke formation and
the occurrence of side reactions, which decrease the yield of syngas [16–19].
◦
CH4 +CO2 ↔ 2CO + 2H2 , ΔH 298K = 247 kJ/mol (1)
◦
CO2 +H2 ↔ CO + H2 O, ΔH 298K = 41.4 kJ/mol (2)
◦
2CO ↔ CO2 + C, ΔH 298K = −172.4 kJ/mol (3)
A common overbearing problem is the reverse water-gas shift (RWGS) associated with dry
reforming, which consumes the hydrogen produced by the reaction to form water. This is much more
evident at high pressure, because the reaction (2) is favoured with respect to reaction (1) owing to the
much higher reactivity of H2 over CH4 [20].
Membrane reactors (MRs) are a promising solution to overcome these limitations, combining the
reaction and H2 separation by means of a selective membrane. The presence of a hydrogen-selective
membrane allows the removal of hydrogen from reaction side with a contemporary recovery a
hydrogen rich/pure stream [21] and the shifting of the reaction toward further conversion. In addition,
as the permeation is a pressure driven process, the negative effect of reaction pressure, which favors
RWGS, is counterbalanced by the promotion of hydrogen removal from reaction volume. In addition,
MR operates below 600 ◦ C, thus, below the temperature range at which coke deposition readily
occurs [22]. In most cases, the MRs used for DRM are constituted by a selective membrane—usually
Pd-based—having only the separating function, whereas the catalyst is packed in the annulus between
the membrane and reactor shell [23–29].
As it is well known, Ni-based is the most used commercial catalyst for DRM. However, it suffers
from severe loss of catalytic activity mainly due to the coke formation. Industrial steam reformers are
fed with steam-to-carbon ratios close to 3 to suppress the coking, resulting in less efficient operation.
To enable operation with lower steam-to-carbon ratios, new catalysts need to be developed that are
simultaneously highly active, resistant to coking, and low cost. Such catalysts can be based on novel
materials based on platinum group metals (Ru, Rh, Pt, Pd, etc.) [30,31]. Very recently, Simak and
Leshkov [32] demonstrated the advantages obtained by using a 0.15 wt % Ru/-Al2 O3 catalyst in
methane steam reforming coupled with a Pd-Ag membrane (5 micrometer thick). This MR, operated
at 650 ◦ C and 8 bar of feed pressure, showed high catalytic activity with a methane conversion higher
than 50% and hydrogen yield of about 70%. At the same time, the MR showed stable performance
over a total of 400 h on stream, including operation with low steam-to-carbon ratios of 1 and 2, and
combined dry-steam reforming. On the basis of these positive results, we decided to carry out DRM in
a Pd-Ag MR at 500 ◦ C in the presence of a 0.5 wt % Ru/Al2 O3 catalyst. As also observed by Simak and
Leshkov [32], conversions achievable are quite low (<50%) owing to RWGS and the coke formation.
This latter can affect not only the catalyst activity but also the membrane stability. For this purpose, we
decided to use a Pd-Ag commercial membrane (100 micron thick), which exhibits high chemical and
mechanical resistance, good permeability and infinite H2 selectivity [21], circumventing the various
115
issues that usually could affect ultrathin membranes. The coupling of the selective hydrogen removal
offered by the membrane with the stability of an Ru-based catalyst could provide interesting insight in
DRM reaction development.
CH4 conversion, hydrogen recovery and reaction selectivity were analyzed as a function of feed
pressure and CO2 /CH4 feed molar ratio. In addition, the experimental analysis was coupled with a
detailed thermodynamic study of DRM reaction, calculating the chemical equilibrium parameters in
two different cases: (a) DRM along with the Reverse Water Gas Shift (RWGS) reaction, and (b) DRM
along with both RWGS and the Boudouard Reaction.

The experiments were carried out in a tube in tube MR (Figure 1) where the outer tube is a
stainless-steel shell, whereas the inner tube is the Pd-alloy self-supported membrane, blind on one
end. The catalytic bed was 0.5% Ru/Al2 O3 commercial catalytic pellets, packed in the annulus and
the permeated stream is recovered in the core of the membrane (permeate side). The sealing between
the membrane and the reactor shell was obtained with a graphite O-ring via compression. Both the
membrane and MR characteristics are summarized in Table 1.
Figure 1. Membrane reactor scheme.
Table 1. Membrane reactor characteristics.
Membrane Pd-Ag Commercial (Goodfellow) Self-Supported

Thickness 100 micrometers
Superficial Area 3 cm2
Outer Diameter 1 mm
Length 93 mm
Catalyst Weight 8.5 g
The laboratory plant assembled to perform the present investigation is sketched in Figure 2.
The reactor was placed inside an electric furnace to keep the desired temperature. The gas mixture
was fed into the module by two mass flow controllers (Brooks Instrument 5850S, Hatfield, PA, USA).
The outlet streams were fed to two bubble soap flow meters in order to measure the gas flow rates and,
thus, to evaluate the permeating flux. A pressure gauge with a backpressure controller was placed on
the retentate stream to keep and measure the feed pressure; whereas permeate pressure was regulated
by a vacuum pump. The retentate and permeate streams compositions were analyzed by means of a
gas chromatograph (Agilent 7890N, Santa Clara, CA, USA) with two parallel analytical lines. Each
line was equipped with two columns: An HP-Plot-5A (to separate permanent gases such as H2 , N2
and CO) and an HP-Poraplot-Q (for other species) allowing the retentate and permeate streams to be
analyzed at the same time. The temperature was measured by using a thermocouple positioned in the
middle of the reactor shell (inside the catalyst bed). After assembly, the membrane reactor was charged
under nitrogen pressure at 8 bar on the feed side, closing the retentate. No pressure falls were detected
after one hour, confirming the absence of leakages. The same procedure was repeated at 500 ◦ C, before
starting reaction measurements. Before reaction experiments, the membrane was assembled in the
module without packing the catalyst and permeation measurements were carried out with H2 single
gases at different temperatures and pressures. For this purpose, the feed-side absolute pressure was set
116
at 4, 6 and 8 bar, whilst the permeation-side pressure was fixed at atmospheric pressure during each
series of permeation measurements. Afterwards, a CO2 :CH4 stream was fed for reaction experiments
at 500 ◦ C, analyzing, in particular, the effects of the feed molar ratio, and the feed and permeate
pressures. A summary of the operating conditions are reported in Table 2.
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Figure 2. Sketch of the lab-scale plant for permeation and reaction experiments.
Table 2. Operating conditions for experimental measurements.
Permeation 400, 450, 500

Temperature, ◦ C
Reaction 500
Feed 1–8
Pressure, bar
Permeate 0.02; 1
CO2 /CH4 Feed Molar Ratio 1, 1.5
GHSV, h−1 100
Generally, as also done in the present work, the H2 permeating flux through Pd-alloy membranes
can be described by Sieverts’ law (Equation (4)) when the diffusion through the metal bulk is the
rate-determining step. Under these conditions, the hydrogen permeating flux is considered a linear
function of the permeation driving force, which is given by the difference of the square root of the H2
partial pressure on both membrane sides. This assumption has been done since, as it can be seen in the
next section, the permeating flux is fully linear with the square root of the H2 partial pressure on both
membrane sides.

H2 permeating f lux = PermeanceH0 2 e− E/R T Reaction
PH 2
Side − Permeate
PH2
Side , mol·m−2 ·s−1 (4)
As for the reactor performance, CH4 conversion in both TR and MR was calculated using
Equation (5) including CH4 present in the feed and retentate streams. In particular, the conversion was
117
calculated as the average value between the CH4 fed to the MR and that detected in the retentate. Each
value of conversion reports an error bar taking into account the carbon balance. It was calculated for
each measurement and it is comprised in the range −8.7% to 5%.
CH4Feed − CH4Retentate
CH4 conversion = , − (5)
CH4Feed
The recovery capability of the MR was quantified in terms of H2 recovery (Equation (6)), which is
defined as the H2 fraction permeated through the membrane with respect to all of the H2 present in
both outlets of MR.
Permeate
FH
H2 Recovery = 2
Permeate + FRetentate
, − (6)
FH2 H2
Catalyst is periodically regenerated with a diluted stream of 10% H2 in argon after each set of
reaction experiments. The reverse methane decomposition is an exothermic reaction favoured at low
temperatures. If coke is present, it would react with hydrogen to produce methane. Based on this
fact, it is possible to calculate the coke reacted from the methane produced. For this purpose, the
retentate stream was analyzed by gas chromatography, measuring at the same time the outlet flow
rate by bubble flow meter. From such methanation tests, the total coke content in the catalyst after the
reaction experiment was calculated from the amount of CH4 formed and crosschecked with carbon
balance calculations. Each measurement was repeated three times, alternated by methanation, for a
total experimental campaign that lasted about 500 h. The measurements are reproducible, confirming
a good stability of catalyst for the whole period of experiments.
3.1. Thermodynamic Analysis

The understanding of the thermodynamic behavior of DRM for syngas and hydrogen production
is important to determine the most favorable reaction conditions. The theoretical background of
thermodynamic analysis is reported in Appendix A. The thermodynamic equilibrium of DRM along
with some side-reactions is evaluated by minimization of the total Gibbs free energy, which is carried
out in the MATLAB® environment (see Appendix A for calculation details). As mentioned above, the
independent reactions considered are the following: The DRM, RWGS and Boudouard reaction. More
specifically, the analysis of the Boudouard reaction is important because coke is formed by it. To the
best of our knowledge, there are no references in the open literature about equilibrium calculation in
the co-presence of coke.
3.1.1. Calculation Validation

To verify the accuracy of the calculated values, the equilibrium of DRM and reverse WGS reaction
was preliminarily studied comparing the obtained results with some present in the literature in terms
of CH4 conversion and equilibrium constant. As shown in Figure 3 (equilibrium conversion) and in
Table 3 (equilibrium constant), the results from both MATLAB code and literature data agree very well.
118
Figure 3. CH4 conversion at equilibrium: (Left side) as a function of pressure, CO2 /CH4 feed molar
ratio of 1, temperature of 650 ◦ C ( ) and 600 ◦ C (), compared with experimental data (Lee (2003) [33]);
(right side) as a function of temperature, CO2 /CH4 feed molar ratio of 1.5, pressure of 1 bar (),
compared with experimental data (Chein et al. (2015) [34]).
Table 3. Equilibrium constant for dry reforming of methane (DRM) and reverse water gas shift (RWGS)
reactions calculated at a temperature of 600 ◦ C and 650 ◦ C and compared with experimental data of
Lee (2003) [33].
Equilibrium Constant Keq

DRM RWGS
Lee (2003) [33] MATLAB code Lee (2003) [33] MATLAB code
600 ◦ C 0.19 0.20 0.37 0.40
650 ◦ C 1.31 1.38 0.48 0.53
3.1.2. Equilibrium Calculation: DRM and RWGS

After ensuring the MATLAB method correctness, both CO2 /CH4 feed molar ratio and pressure
effect were evaluated on the methane equilibrium conversion. Figure 4 shows the CH4 equilibrium
conversion as a function of temperature and varying CO2 /CH4 feed molar ratio for 1 bar (left side)
and 10 bar (right side). At a pressure value sets, CH4 conversion increases with CO2 /CH4 feed molar
ratio and with temperature. The DRM reaction is endothermic, and is favored at high temperature.
Figure 5 shows the CH4 equilibrium conversion as a function of temperature and varying pressure for
CO2 /CH4 feed molar ratio of 1 (left side) and 2 (right side). As pressure increases, CH4 conversion
decreases. The DRM reaction occurs with the increase in molar number and is unfavorable at high
pressures. The pressure negative effect is due to the reaction thermodynamics, according to the
Le Chatelier-Braun principle. In particular, methane conversion approaches limiting values as the
pressure increases.
119
Figure 4. CH4 equilibrium conversion at 1 bar (left side) and 10 bar (right side) as a function of
temperature, varying CO2 /CH4 feed molar ratio from 1 to 2.
Figure 5. CH4 equilibrium conversion at CO2 /CH4 feed molar ratio of 1 (left side) and 2 (right side)
as a function of temperature, varying the pressure from 1 to 10 bar.
3.1.3. Equilibrium Calculation: DRM, Reverse WGS and Boudouard Reactions

Carbon formation is one of the basic phenomena when hydrocarbon species are involved in
chemical reactions. It is therefore interesting to examine its effect on the reaction. Figure 6 shows the
equilibrium constants variation of the reactions involved as a function of temperature. For a strong
endothermic reaction, DRM equilibrium constant increases dramatically with increasing reaction
temperature. Thus, high conversion is favored at high temperatures. The equilibrium constants of
the moderate endothermic reactions, the reverse WGS reaction, also increase with temperature. The
carbon deposition by Boudouard reaction is exothermic and thermodynamically unfavorable at high
temperatures. Therefore, high reaction temperatures are more favorable to increasing the equilibrium
conversion of the DRM reaction than that of the side reactions. The equilibrium results for the case
with carbon formation for DRM process as a function of temperature are showed in Figure 7 at pressure
of 1 bar (left side) and 10 bar (right side) by varying CO2 /CH4 feed molar ratio, and in Figure 8 at
CO2 /CH4 feed molar ratio of 1 (left side) and 2 (right side) by varying pressure. At a relatively low
temperature, the equilibrium constant of the Boudouard reaction is much higher than the unity and,
thus, the formation of coke and CO2 is favoured. This causes an enhanced conversion of methane due
to a major presence of CO2 , whose consumption by RWGS is not sufficient to overcome the effect of the
Boudouard reaction. At a moderately higher temperature, however, the influence of the Boudouard
reaction is modest and, at the same time, that of RWGS increases. This causes a higher consumption of
120
CO2 , which tends to push the equilibrium of DRM towards the reactants leading to a slightly lower
CH4 conversion. On the other hand, at a higher temperature the DRM is favoured over both RWGS
and Boudouard reactions, causing a boost in the CH4 conversion. The overall result of these different
tendencies is the presence of minima in the trends shown in Figures 7 and 8, which are justly caused
by considering the effect of the Boudouard reaction.
Figure 6. Equilibrium constant as a function of temperature for DRM ( ŷ)), reverse WGS ( ŷ)) and
Boudouard ( ŷ)) reactions.
Figure 7. CH4 equilibrium conversion at 1 bar (left side) and 10 bar (right side) as a function of
temperature at different CO2 /CH4 feed molar ratio taking into account carbon formation.
121
,ϰŽŶǀĞƌƐŝŽŶ͕Ͳ
Figure 8. CH4 equilibrium conversion at CO2 /CH4 feed molar ratio of 1 (left side) and 2 (right side)
as a function of temperature at different pressures taking into account carbon formation.
Furthermore, carbon formation is more important as both pressure and CO2 /CH4 feed molar
ratio increase.
Figure 9 shows the CH4 equilibrium conversion as a function of pressure at temperature of
500 ◦ C and a CO2 /CH4 feed molar ratio of 1 for both cases previous described. In an ideal situation
the optimum condition in which it operates is between the two equilibrium curves, i.e., lower than
methane conversion which takes into account coke formation, and greater than methane conversion
that does not take into account coke formation.
Figure 9. CH4 equilibrium conversion at CO2 /CH4 feed molar ratio of 1 and temperature of 500 ◦ C as
a function of pressure.
3.2. Permeation Measurements

Figure 10 shows the hydrogen permeating flux as a function of the Sieverts permeation driving
force at different values of temperature. As expected, hydrogen flux increases linearly with increasing
driving force, indicating an ideal membrane behavior (i.e., permeation completely controlled by
internal diffusion and hydrogen concentration in the metal lattice close to the infinite dilution).
122
H2 permeating Flux, mmol m-2 s-1
Figure 10. Hydrogen flux as a function of Sieverts’ driving force at different temperatures.
This situation is confirmed by the Arrhenius-type plot of the hydrogen permeance, which
shows a linear trend indicating an ideal permeance (and, thus, permeability, Figure 11). Table 4
summarizes the values of apparent activation energy, pre-exponential and hydrogen permeance at the
temperatures considered.
H2 permeating Flux, mmol m-2 s-1
π π
π
π = π 0 exp (-E/RT)
π 0 = 455 mmol m-2 s-1 Pa -0.5
E = 4942 J mol-1
Figure 11. Arrhenius plot of hydrogen permeance.
Table 4. Apparent activation energy, pre-exponential factor and hydrogen permeance values.
Apparent Activation Energy, E J·mol−1 4942

Permeance Pre-Exponential Factor mol·m−2 ·s−1 ·Pa−0.5 455
400 ◦ C 190
Hydrogen Permeance,
mol·m−2 ·s−1 ·Pa−0.5 450 ◦ C 196
500 ◦ C 211
It must be noticed that the reaction experiments lasted ca. 500 h—alternating reaction with
regeneration by methanation—and no drop of separating properties of the membrane, measured
before and after reaction, was observed during this time.
123
3.3. Reaction Measurements

Before performing the DRM reaction measurements in MR, the catalyst activation was carried out
in the presence of gas mixture having a molar concentration 90:10 = H2 :N2 at 400 ◦ C and atmospheric
pressure for two hours. The values of CH4 and CO2 feed flow rates were calculated and set by fixing
CO2 /CH4 feed molar ratio, GHSV (space velocity), temperature and feed pressure. Figure 12 (left axis)
shows the CH4 conversion as a function of the feed pressure at GHSV of 100 h−1 , temperature of 500 ◦ C
and CO2 /CH4 feed molar ratio of 1.5. The error bars indicate the carbon balance. The experimental
conversion values obtained in the MR were compared with the equilibrium conversion obtained in
the traditional reactor. In particular, the experimental CH4 conversion was found to decrease with
increasing feed pressure according to Le Chatelier-Braun principle since there is a net increase in
the number of moles. It is noticeable that at sufficiently low feed pressures (1 bar in the specific
case), the experimental conversions in the MR were higher than equilibrium conversion of a TR since
the removal of the H2 product shifts the equilibrium to the right. The permeation supplies such a
significant contribution to overcoming the equilibrium performance. The higher feed pressure hinders
the conversion since the reaction occurs with an increase in molar number, thus the hydrogen partial
pressure on the feed side is lower and, similarly, its permeation.
,ǇĚƌŽŐĞŶZĞĐŽǀĞƌǇ͕й
,ϰŽŶǀĞƌƐŝŽŶ͕й
Figure 12. CH4 conversion ( ) and H2 recovery () as a function of feed pressures at CO2 /CH4 feed
molar ratio = 1.5, permeate pressure = 0.02 bar. Equilibrium conversion values in a traditional reactor
(dashed line).
These data were obtained considering a permeate pressure of 0.02 bar. We decided to operate
under vacuum for increasing the permeation rate. CH4 conversion obtained at the permeate pressure
of 1 bar is less than that of the equilibrium. With a low hydrogen permeate pressure value it is, thus,
possible to significantly exceed the thermodynamic limit of the traditional reactor, reaching conversion
significantly higher.
A higher methane conversion means a higher methane amount that reacts for producing hydrogen.
For this reason, the hydrogen recovery follows the same trend as that of conversion (Figure 12,
right axis). At a feed pressure of 1 bar and 0.02 bar of vacuum on the permeate, about 47% of hydrogen
is recovered as a pure stream in the permeate. A higher feed pressure means a lower CH4 conversion,
and, thus, less hydrogen produced and that can be recovered. However, it has to be pointed out that,
even in the worse conditions (i.e., 8 bar), around 15% of hydrogen is recovered.
124
Another reaction measurement was carried out at stoichiometric feed molar ratio under the
same operating conditions as the just-analyzed ones (Figure 13). Additionally, in this case, the
CH4 conversion decreases with pressure (Figure 13, left axis). At low pressures, the experimental
conversions in the MR are higher than equilibrium conversions since the removal of H2 product
shifts the equilibrium to the right. However, at the high pressure, the conversion in the MR is lower
than the equilibrium one. This is a non-favourable condition because, despite using an MR, the H2
permeation through the membrane cannot compensate the feed pressure negative effect induced by
thermodynamics. Therefore, the reactor behavior is similar to that of a TR. Figure 13 (right axis) shows
the effect of feed pressure on the H2 recovery. Although conversion is low, a hydrogen recovery
of about 20% was found. This could mean that, despite the small amount of methane converted,
a sufficiently large amount of hydrogen is produced by reaction to permeate through the membrane.
In an MR, a high feed pressure involves an increase of hydrogen permeation driving force, favouring a
higher hydrogen removal from the reaction side towards the permeate side with a consequently higher
hydrogen recovery. The opposite trend between methane conversion and hydrogen recovery can be
justified by the combination of the negative effect induced by thermodynamics and the positive effect
induced by permeation.
Figure 13. CH4 conversion ( ) and H2 recovery () as a function of feed pressures at CO2 /CH4 feed
molar ratio = 1, permeate pressure = 0.02 bar. Equilibrium conversion values in a traditional reactor
(dashed line).
Figure 14 shows H2 /CO reaction selectivity as a function of the feed pressure for different feed
molar ratio. As feed pressure increases, H2 /CO reaction selectivity decreases. It is less than 100%
for all feed pressure range considered, that is, the CO amount produced is greater than that of H2 .
This could mean that, operating at CO2 /CH4 feed molar ratio of 1.5, H2 product reacts with CO2 fed
(in excess) to produce CO and H2 O by reverse WGS side reaction.
125
ϭϬϬ
ϳϱ
ϱϬ
Ϯϱ
Ϭ
Ϭ ϭ Ϯ ϴ
&ĞĞĚWƌĞƐƐƵƌĞ͕ďĂƌ
Figure 14. H2 /CO reaction selectivity as a function of feed pressures at CO2 /CH4 feed
molar ratio = 1–1.5, permeate pressure = 0.02 bar.
4. Conclusions
This work consists of an analysis of dry reforming of methane in a catalytic Pd-based membrane
reactor. A 0.5 wt % Ru/Al2 O3 catalyst was packed in the annulus between the shell and a Pd-Ag
commercial membrane and the performance of the MR were analyzed as a function of feed pressure
and feed molar ratio. The whole experimental period lasted about 500 h and any significant change
in membrane permeation properties was observed during this time. Moreover, the catalyst was
stable for the whole reaction period (alternated by a periodic regeneration with a diluted stream of
10% H2 in argon), with no drops of its activity. Coke formation was continuously monitored, and
carbon balance was below ±10%. The higher conversion was achieved at low feed pressures owing
to the favourable thermodynamics, reaching a higher value than the equilibrium one obtainable in a
traditional reactor thanks to the hydrogen permeation through membrane. At 500 ◦ C, MR showed
good performance in terms of both CH4 conversion and hydrogen recovery (CH4 conversion = 26%
and H2 recovery = 46% @ 100 h−1 , 1 bar, 0.02 bar on permeate side) exceeding the traditional reactor
equilibrium conversion. Comparing the results, it can be deduced that at a CO2 /CH4 feed molar ratio
of 1.5 there is a higher methane conversion but a lower H2 recovery and H2 /CO reaction selectivity
with respect to the stoichiometric feed molar ratio. This could indicate that both the reverse WGS and
Boudouard reactions occur along with DRM, meaning that part of the H2 produced is consumed to
make water as a by-product, and part of CO produced is consumed to produce coke. So far, the main
limitation to DRM industrialization remains as coke formation. The development of new catalysts with
high and stable activity, is thus highly recommended. Membrane engineering with MR technology
can play a fundamental role in the integration of the units and processes and, at the same time, in the
definition of the knowledge necessary to drive the process by maximizing the gains both in terms of
efficiency, productivity and plant size reduction.
Author Contributions: Conceptualization, A.B., G.B. and A.C.; Methodology, A.C.; Software, A.C.; Validation,
M.G.; Formal Analysis, M.G. and A.C.; Investigation, M.G. and A.C. Resources, G.B. and A.C.; D.C., A.C.;
Writing—Original Draft Preparation, A.C. and A.B.; Writing—Review & Editing, A.B. and A.C.; Supervision, A.B.,
A.C., G.B.
126
Appendix A
Appendix A.1 Calculation Approach for Thermodynamic Equilibrium

The following sub-sections report the details of the calculation approach used to evaluate
the equilibrium trend of DRM in the presence of the following side-reactions: The RWGS and
Boudouard reaction.
The total Gibbs free energy of a single-phase only for a gas or a solid system can be respectively
represented by Equations (A1) and (A2):
g

N ◦g N fi
∑ ni Gi + RT ∑ ni ln
tg
G(T,P) = ◦g (A1)
i =1 i =1 fi

N
◦s
N f is
G(tsT,P) = ∑ ni Gi + RT ∑ ni ln ◦
fi s
(A2)
i =1 i =1
Hence, the total Gibbs free energy of a two-phase system is written as Equation (A3):
g

N ◦g N fi N
◦s
N f is
G(t T,P) = ∑ ni Gi + RT ∑ ni ln ◦g + ∑ ni Gi + RT ∑ ni ln ◦
fi s
(A3)
i =1 i =1 fi i =1 i =1
◦g ◦ ◦g
The standard state is defined as the pure ideal gas state at 1 atm, f i = P = 1 atm and Gi equals
to zero for each element in its standard state. The solid phase is assumed as a pure solid carbon and
its reference state is at atmospheric pressure and 25 ◦ C. The partial fugacity is written as shown in
Equation (A4):
◦
f is = f i s (A4)
The total Gibbs free energy of the system is expressed in Equation (A5) by the summation over
N species:
N N
◦ f
G t = ∑ ni Gi + RT ∑ ni ln ◦i + ns Gs (A5)
i =1 i =1 fi
◦
where Gi is the Gibbs free energy of species i under standard conditions, R is the universal molar gas
◦
constant, fi and fi are fugacity of species i at standard and operating conditions, respectively, ni is the
number of moles of species i, and T is the temperature. If carbon is formed in the overall reactions, ns
represents the number of solid carbon molecules, while Gs is the Gibbs free energy of solid carbon at
the operating conditions.
To reach equilibrium, Gibbs energy is minimized with respect to reaction degree ξ for which there
are constraints to be respected (Equation (A6)). The necessary condition to have a minimum of Gt is
reported in Equation (A7).
t (ξ )
min GT,P
ξ 1 ,ξ 2 ,ξ 3
s.t. 0 ≤ ξ 1 ≤ 1 (A6)
0 ≤ ξ2 ≤ 1
0 ≤ ξ3 ≤ 1
dG t
=0 (A7)
dξ
The vector of the reaction degrees ξ is written between the species involved in a reaction by a
mass balance between both the initial and generic condition (Equation (A8)). As the number species in
the system, more variables are necessary. In particular, many reactions degree as reactions are in the
127
system. A reaction constrains the moles number variation of each species through the stoichiometry.
Moles number must be positive.
NR
Ni = Ni0 + ∑ υij ξ j (A8)
j =1
where Ni0 is moles number of the specie i at reaction inlet (=0), υij is stoichiometric coefficient of specie
i in the reaction j and NR is number of independent reactions.
Appendix A.2 Equilibrium Calculation: Numerical Procedure

The thermodynamic equilibrium condition of a reaction system is calculated using the Gibbs
free energy minimization method, at both constant P and T and with given initial composition. This
method is based on the principle that the total Gibbs energy of system has its minimum value at
chemical equilibrium. Furthermore, it requires the formalization of the reactions and the identification
of all the species, beyond the reactants, which may be present at equilibrium.
The reactions used must be linearly independent, that is the stoichiometric matrix rank ν (whose
elements νij correspond to the stoichiometric coefficient of species i in the reaction j) must be equal to
the independent reactions number (Equation (A9)). The latter variable is obtained by Equation (A10).
Rank(ν) = Number o f Indipendent Reaction (A9)
Number o f Indipendent Reaction = C − Rank ( A) (A10)
where C is a species number and A is an atom/species matrix.

The independent reactions systems considered in this paper work, for dry reforming of methane
process, are: DRM (Equation (1)), reverse WGS (Equation (2)) and Boudouard (Equation (3)) reactions.
MATLAB was used in the equilibrium problem resolution. In particular, fmincon (MATLAB solver)
attempts to find a constrained minimum of a scalar function of several variables starting at an initial
estimate. This is generally referred to as constrained nonlinear optimization. During the process
of optimization, the equilibrium condition is evaluated by varying the temperature (600:5:1073 K),
pressure (1:1:10 bar) and molar feed ratio CO2 /CH4 (1:0.5:2) value, whereas catalyst, reaction kinetics,
and the transport process are not considered.
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chemengineering
Article
Ionic Liquid Hydrogel Composite
Membranes (IL-HCMs)
Shabnam Majidi Salehi 1,2 , Rosangela Santagada 1 , Stefania Depietra 1 , Enrica Fontananova 1 ,
Efrem Curcio 2 and Gianluca Di Profio 1, *
1 National Research Council of Italy (CNR), Institute on Membrane Technology (ITM), Via P. Bucci c/o
Università della Calabria Cubo 17/C, 87036 Rende (CS), Italy; [email protected] (S.M.S.);
[email protected] (R.S.); [email protected] (S.D.); [email protected] (E.F.)
2 University of Calabria (UNICAL), Department of Environmental and Chemical Engineering (DIATIC),
Via P. Bucci Cubo 45/C, 87036 Rende (CS), Italy; [email protected]
* Correspondence: g.diprofi[email protected]; Tel.: +39 0984 492010; Fax: +39-0984-402103
Received: 19 February 2019; Accepted: 26 April 2019; Published: 5 May 2019
Abstract: In this work, novel hydrogel composites membranes comprising [2-(Methacryloyloxy)ethyl]

dimethyl-(3-sulfopropyl)ammonium hydroxide as monomer, N,N-methylene bisacrylamide as
cross-linker, and 1-butyl-3-methylimidazolium hexafluorophosphate as ionic liquid additive, have
been developed. Ionic liquid hydrogel composite membranes (IL-HCMs) were tested for membrane
contactors applications, aiming to reduce surface hydrophobicity of the polypropylene support,
to reduce wetting tendency due to interaction with hydrophobic foulants, while affecting salts rejection
in desalination operation, because of the entrapment of ILs inside the porous mesh-like structure of
the gel layer. Transmembrane flux comparable to the sole polypropylene support was observed for IL
content > 1 wt.%. Furthermore, all IL membranes presented a larger rejection to sodium chloride than
the PP support or the composites without ionic liquid inside. Although the overall transmembrane
flux of IL-HCMs developed in this work is comparable with that of state of the art MD membranes,
this study demonstrated that the strong hydrophilic hydrogel layer, with C.A. < 50◦ for IL content
larger than 1 wt.%, serves as a stabilization coating, by providing the new media between the feed
and the hydrophobic membrane surface, thus potentially controlling the diffusion of hydrophobic
foulant molecules. This would result in a decrease in the membrane wetting and fouling aptitude.
Keywords: advanced separations; desalination; hydrogel composite membranes; ionic liquids

membranes; membrane distillation
1. Introduction
Hydrogels are soft materials consisting of a mesh-like structure with polymer chains physically
or chemically cross-linked and water molecules filling the interstitial spaces [1,2]. Due to their
permeable net-like consistence, hydrogels can exert separation functions based on molecular size
exclusion [3]. Since the mesh size can be modulated by adapting the swelling state in response to
externally applied stimuli, like temperature, pH, ionic strength, interaction with specific molecules,
electric or magnetic field, transport of specific solution components through hydrogels can be controlled
by a stimuli-responsive behavior [4–14].
Because of their unique features as separative media, hydrogels are facing notable implications
in the field of membrane processes [15]. The combination of a hydrogel layer with a porous support
provides favorable synergisms, resulting in composite materials with totally new separation functions
with respect to the bulk hydrogel or the substrate, while affording improved mechanical stability of the
supported soft gel phase.

Recently, we have developed several hydrogel composite membranes, containing a hydrophobic

support and a hydrophilic surface layer, whose main application is in the field of membrane contactors.
Hydrogel composite membranes (HCMs) have been developed: (1) for membrane distillation (MD) [16],
with enhanced salt rejection under Donnan exclusion effect generated by the polyelectrolyte nature
of the gel phase, (2) as protein crystallization environment [17,18], to produce crystals at lower
supersaturation and of larger size compared to conventional crystallization methods, (3) as biomimetic
mineralization platform [19], for the synthesis of calcium carbonate structures displaying multi-scale
and hierarchical architecture, and (4) as antibacterial food package materials [20], due to the effect of
enzyme crystals included in the hydrogel layer.
In this study, ionic liquid hydrogel composite membranes (IL-HCMs) have been prepared
by layering a [2-(Methacryloyloxy)ethyl]dimethyl-(3-sulfopropyl)ammonium hydroxide hydrogel,
cross-linked with N,N-methylene bisacrylamide in the presence of 1-butyl-3-methylimidazolium
hexafluorophosphate as ionic liquid (IL) additive, and tested for MD applications. The main purpose
of this work was the development of a suitable membrane functionalization strategy, that would be
effective in reducing the hydrophobic interaction of the polymeric surface with potential foulants,
thanks to the presence of the more hydrophilic hydrogel layer, while enforcing salts rejection due to
the contribution of the ILs entrapped in the porous structure of the gel layer.
In fact, membrane fouling is particularly concerning when intrinsically hydrophobic membrane
materials are used to treat feed solutions containing an abundance of organic components, due to their
strong hydrophobic interactions with the polymeric surface [21–23]. This is particularly detrimental
in MD applications, where severe fouling of the hydrophobic membrane is the starting point of
pore wetting. In such cases, extensive feed pre-treatment is requested to remove the hydrophobic
contaminants ahead the membrane process, with significant increases of treatment costs. Therefore,
membrane surface modification is the most common method to improve membrane anti-fouling
and anti-wetting properties in MD. For instance, shifting membrane surface hydrophobicity toward
super hydrophobicity allows to generate an air gap between the liquid and the surface that helps to
increase the admissible pore size prior to pore wetting occurrence, thus ensuring higher mass flux and
membrane stability [24,25]. On the other hand, changing the membrane surface from hydrophobic to
more hydrophilic behavior, imparts robust resistance to fouling [26–28], thanks to the formation of a
hydration shell which renders the membrane surface less susceptible to interaction with the hydrophobic
contaminants [29–32]. Such kind of membrane functionalization strategy is potentially suitable for
membrane contactors applications, such as membrane distillation and membrane crystallization,
since the hydrophilic layer protects membrane’s surface from low-surface-tension components, thus
preventing feed solutions from penetrating into the pores [33,34].
While the development of membranes with (super) hydrophilic skin layer has allowed the
applications of MD to desalinate more challenging feed waters [22,35], little studies have been proposed
so far on the development of hydrogel-functionalized membranes for membrane contactors. In a
previous study, a thin layer of agarose hydrogel was positioned on the surface of a Teflon membrane,
providing good anti-wetting behavior in the presence of surfactant in MD desalination [36]. In another
study [37], composite membranes including poly(diallyldimethylammonium chloride)/poly acrylic acid
semi-interpenetrating hydrogel on a polyvinylidene fluoride support, showed long-term robustness
with 3 wt.% NaCl solution containing cationic, ionic and non-ionic surfactants in direct contact MD
experiments. Here, we show that, in addition to potentially improved membrane resistance to wetting
due to the protective hydrophilic hydrogel layer, larger rejection to sodium chloride than the PP
membrane can be generated under the effect of ionic liquid entrapped in the polyelectrolyte layer, with
the resulting increase in charge density in the gel network that rejects ions at the solution/hydrogel
interface by the Donnan exclusion potential.
132
2. Experimental Section
2.1. Materials
Polypropylene (PP) flat membranes (Accurel PP 2E HF, nominal pore size 0.2 μm) were purchased
from Membrana GmbH (Germany). [2-(Methacryloyloxy)ethyl]dimethyl-(3-sulfopropyl)ammonium
hydroxide (monomer, SPE, cod. 537284), N,N-methylene bisacrylamide (cross-linker, MBA, cod. 146062),
2-hydroxy-2-methyl propiophenone (photoinitiator, cod. 1001451059), and 1-Butyl-3-methylimidazolium
hexafluoro phosphate (ionic liquid, IL, cod. 18122) (Figure 1) were from Sigma-Aldrich (Italy). Sodium
chloride (NaCl, cod. 131659.1211) was from Panreac (Italy). Methanol (CH3 OH, HPLC grade, cod.
20844.320) was from VWR (Italy). All chemicals were used without any further purification. Milli-Q
water was used for all solutions and as condensing fluid in MD tests.
1-Butyl-3-methylimidazolium hexafluorophosphate (IL)
[2-(Methacryloyloxy)ethyl]dimethyl-(3-sulfopropyl) ammonium hydroxide (SPE)
N,N'-Methylenebisacrylamide (MBA)
Figure 1. Structural formula of hydrogel components used in this work.
2.2. Preparation of Hydrogel Composite Membranes

Polypropylene membranes, used as support for hydrogel composites, were conditioned by soaking
in methanol for 24 h at room temperature and then dried with tissue paper immediately before use.
The monomer SPE was dissolved in water by magnetic stirring (50 rpm) at 50 ◦ C. The cross-linker MBA
was then added to the monomer solution under stirring until complete dissolution. Subsequently,
the photoinitiator was added to the solution together with the proper amount of IL additives (see
Table 1). The solutions were then left to stir for 1 h at room temperature. The pre-polymer solutions
were then cast onto the conditioned PP substrate by a micrometric film applicator (Elcometer 3570)
at a selected thickness of the liquid film (100, 350, or 600 μm). Photo-initiated graft polymerization
was then performed under the UV/Vis irradiation lamp (GR.E, 500 W) in a vented exposition chamber
(Helios Italquartz, Italy), for 20 min. Composite membranes without IL were also prepared as reference
samples. After that, composite membranes were washed and stored in water at room temperature for
characterization and MD tests.
133
Table 1. Hydrogel composite membrane sample codes, compositions of the pre-polymerization solution
and thickness of the casted film layer.
Membrane Monomer Crosslinker Photoinitiator H2 O IL Casting

Sample Code (wt.%) (wt.%) (wt.%) (wt.%) (wt.%) Thickness (μm)
SPE-100 10.0 1.0 0.3 88.7 0 100
SPE-IL1%-100 10.0 1.0 0.3 88.6 0.1 100
SPE-IL5%-100 10.0 1.0 0.3 88.2 0.5 100
SPE-IL10%-100 10.0 1.0 0.3 87.7 1.0 100
SPE-IL15%-100 10.0 1.0 0.3 87.2 1.5 100
SPE-350 10.0 1.0 0.3 88.7 0 350
SPE-IL1%-350 10.0 1.0 0.3 88.7 0.1 350
SPE-IL5%-350 10.0 1.0 0.3 88.6 0.5 350
SPE-IL10%-350 10.0 1.0 0.3 88.2 1.0 350
SPE-IL15%-350 10.0 1.0 0.3 87.7 1.5 350
SPE-600 10.0 1.0 0.3 88.7 0 600
SPE-IL1%-600 10.0 1.0 0.3 88.7 0.1 600
SPE-IL5%-600 10.0 1.0 0.3 88.6 0.5 600
SPE-IL10%-600 10.0 1.0 0.3 88.2 1.0 600
SPE-IL15%-600 10.0 1.0 0.3 87.7 1.5 600
2.3. Membrane Morphology Examination

Morphological analyses of membranes top and cross section were performed by a Quanta 200 F
FEI Philips scanning electron microscope (SEM). Samples were attached with carbon conductive tape
to steal stubs and sputtered with chromium. The accelerating voltage was 12.0–15.0 kV under high
vacuum. Samples were cryo-fractured with liquid nitrogen prior to examine membrane cross-section.
2.4. Water Contact Angle

Static contact angle was measured by a goniometer (Nordtest, Italy) at ambient temperature.
A 5 μL drop of water was put onto the membrane sample by a micro-syringe and measurements were
carried out by setting the tangents on both visible edges of the droplet. The average value of five
measurements at different detection positions for each sample is reported in Table 2.
2.5. Chemical Surface Analysis

Surface chemical analysis of HCMs was carried out by Fourier transform infrared spectroscopy
(Nicolet iS10 FT-IR spectrometer, Thermo Scientific, USA). Spectra were recorded in the range of
650–4000 cm−1 using an ATR (attenuated total reflectance) device, with a resolution of 1 cm−1 , and
averaged over 30 scans.
2.6. Direct Contact Membrane Distillation Experiments

Figure 2 shows the direct contact membrane distillation (DCMD) equipment used in this work.
Technical details are reported elsewhere [16]. The starting feed and condensing water volumes were
3 L each. The temperature of the feed and the distillate was 60 ◦ C and 20 ◦ C, respectively. Co-current
solutions circulation flow rate was 12 L·h−1 . Active membrane was 3.5 × 10−3 m2 . Tests were performed
with pure water or NaCl solution (1 g·L−1 ) as feed. Each test lasted 6 h.
134
Figure 2. Membrane distillation plant used in direct contact configuration.
NaCl rejection was calculated by using Equation (1) by measuring the electrical conductivity
(Jenway, Bibby Scientific, UK) of the distillate. Salt rejection R is defined as:

C
R = 1 − distillate × 100 (1)
C f eed
where Cfeed and Cdistillate are NaCl concentrations in the feed and in the distillate, respectively. R is
quantified by mass balance after properly considering the electrical conductivity of the overall distillate
with the time and the transmembrane flux under opportune calibration. Transmembrane flux J was
taken as the average value detected under steady conditions (normally occurring during the last three
hours of the test) and it is calculated as:
M
J= (2)
Δt · A
with M the mass of liquid passed through the membrane in the time interval Δt, and A the effective
membrane area.

Figure 3 shows an SEM cross-section image of an SPE-MBA ionic liquid hydrogel composite
membrane (IL 10 wt.%) prepared by casting the pre-polymerization solution at 100-μm thickness. It is
evident the homogeneous hydrogel layer, typically around 20 ± 5 μm thick, was well linked to the
PP support. For the same pre-polymerization solution composition, changing the casing thickness
of solution layer (100, 350, or 600 μm) resulted in different width of the final hydrogel layer upon
polymerization under UV irradiation. Normally, 350 and 600 μm-thick liquid layers load on the
support lead to hydrogel layers of 80 ± 20 μm and 150 ± 30 μm, respectively, after polymerization.
No significant effect of the amount of IL on the final hydrogel layer thickness was observed during
membrane preparation (variation less than 10%). In the case of IL > 10 wt.%, pre-polymerization
solution presented some persistent phase separation upon mixing of the components.
135
Figure 3. Typical scanning electron microscope (SEM) cross-section image of an SPE-MBA ionic liquid
(IL 10 wt.%) hydrogel composite membrane (HCM) prepared by casting the pre-polymerization solution
at 100-μm thickness.
Figure 4 displays ATR-FTIR spectra of IL-HCMs prepared with an increasing amount of IL.
The growth of the peak around 840 cm−1 , assigned to the asymmetric stretching of the PF6 ion and
bending of the imidazolium ring [38,39], with rising amounts of IL in the pre-polymerization solution
can be observed. The strong electrostatic interactions between IL and SPE components provide
stability of the hydrogel phase against the possible release of the IL from the composite membrane.
The cationic part of the imidazolium group of the IL (Figure 1) interacts well with the sulfonic group
of the SPE, while the ammonium part of SPE has an affinity for the hexafluorophosphate ion, thus
keeping electroneutrality of the system.
136
(a)
(b)
Figure 4. (a) ATR-FTIR spectra of ionic liquid hydrogel composite membranes (IL-HCMs) prepared
with an increasing amount of IL (see Table 1): (A) SPE, (B) SPE-IL1%, (C) SPE-IL5%, (D) SPE-IL10%,
(E) SPE-IL15%. (b) Schematic illustrating the effect of interaction between the fixed polyelectrolyte
charges and mobile ionic liquid charges. White region denotes the hydrogel mesh structure with
polymer chains and cross-linking points, blue spaces represent voids. The polymer mesh structure
drawn here does not necessarily represent the effective system. The size of the ions relative to the mesh
size is not drawn to scale.
137
Table 2 reports the water contact angles for IL-HCMs prepared at 350-μm thickness of the casting
solution. As observed, the strong hydrophobic nature of the polypropylene support (138◦ ) turns into
hydrophilic (C.A. ~68◦ ) with the functional hydrogel layered on the PP surface, while it becomes even
more hydrophilic (C.A. < 50◦ ) when introducing IL > 1 wt.% in the hydrogel layer.
Table 2. Water contact angles for IL-HCMs prepared at 350-μm film solution with different amounts
of IL.
Membrane Sample Code Water Contact Angle (◦ )

PP support 138.0 ± 1.0
SPE-350 67.9 ± 3.4
SPE-IL1%-350 61.1 ± 0.9
SPE-IL5%-350 45.6 ± 1.9
SPE-IL10%-350 44.5 ± 2.0
SPE-IL15%-350 40.8 ± 1.0
Composite membranes were tested for membrane distillation application by using the experimental
equipment of Figure 2 with pure water or NaCl solution at 1 g·L−1 as feed. Figure 5 displays observed
transmembrane fluxes J and salt rejections R performances. Despite the change of the nature of the
membrane layer facing the feed from strongly hydrophobic to hydrophilic, all composite membranes
demonstrated salt rejection > 99% over 6 h operation, indicating no occurrence of wetting, thus making
them suitable for MD applications.
20 100.0
18 99.8
Transmembrane flux, J (kg h m )
-2
16 99.6
-1
14 99.4
NaCl Rejection, R (%)
12 99.2
10 99.0
8 98.8
6 98.6
Transmembrane Flux NaCl Rejection
4 Polypropylene Polypropylene 98.4
SPE-IL-600 SPE-IL-600
SPE-IL-350 SPE-IL-350
2 SPE-IL-100 SPE-IL-100 98.2
SPE SPE
0 98.0
00
00
50
50
00
00
2O
00
00
50
50
00
00
l
aC
10
35
60
-1
-1
-3
-3
-6
-6
-1
-1
-3
-3
-6
-6
-H
-N
E-
E-
E-
%
%
1%
1%
5%
1%
5%
PP
PP
SP
SP
SP
10
15
10
15
10
15
5
IL
IL
IL
IL
IL
IL
IL
IL
IL
IL
IL
IL
E-
E-
E-
E-
E-
E-
E-
E-
E-
E-
E-
E-
SP
SP
SP
SP
SP
SP
SP
SP
SP
SP
SP
SP
Membrane Sample
Figure 5. Observed transmembrane fluxes J and NaCl rejections R for tested membranes. Horizontal
line is a guide for readers and refers to the rejection of NaCl salt of unfunctionalized PP support.
The first two bars of Figure 5 display the flux observed for the PP support alone with pure water
(PP-H2 O) and with the saline solution (PP-NaCl) as feed, respectively. As noted, the slight decline
in transmembrane flux (around to 7%) for NaCl feed solution compared to pure water, is due to the
reduction of water vapour pressure under the effect of the dissolved salt, that decreases the driving
138
force Δp (the vapour pressure gradient evaluated at the membrane surfaces) for mass-transfer in
MD [40]. The observed rejection of NaCl for PP membrane support is 99.7%.
The consistent reduction of J is observed in Figure 5 for the membrane SPE-100, dropping by
almost 30% (from 12.8 Kg·h−1 ·m−2 for pristine PP to 9.4 Kg·h−1 ·m−2 ), when the hydrogel phase is
layered on the surface of the PP support in the resulting HCM. This can be explained by the additional
resistance to mass transfer, compared to untreated PP membranes, generated by the presence of the
hydrogel. In the case of HCMs prepared by casting the pre-polymerization solution at 350 μm (SPE-350)
and 600 μm (SPE-600), J was observed to scale almost linearly with the thickness of the casted solution.
At 600 μm thickness, the reduction in J is almost 40% compared to the transmembrane flux registered
for PP alone, dropping to 7.7 Kg·h−1 ·m−2 .
When including IL at 1 wt.% in the casting solution (SPE-IL1%-100), the transmembrane flux of
the hydrogel-coated membrane is almost completely recovered (only 3% less) with respect to the PP,
while it grows regularly up to 13.8 Kg·h−1 ·m−2 (i.e., larger than for the sole PP support) by increasing
the amount of IL up to 10 wt.% (SPE-IL10%-100). In the latter case, rejection of NaCl reaches 99.99%.
Compared to a previous study, where transmembrane flux reduced by 71% when an agarose
hydrogel layer was attached on the surface of a Teflon membrane [36], we found that including
the IL additive in the hydrogel layer of HCMs allows almost complete salt rejection without
affecting productivity.
The similar increasing trend of J is observed for HCMs prepared at 350 and 600 μm of casting
solution, although the beneficial contribution of the IL to J at lower content (1 wt.%) is less effective
than in the former case. Interestingly, increasing the amount of ionic liquid in the pre-polymerization
solution, salt rejection increases regularly for all samples. For all the IL-HCMs, NaCl rejection overruns
the observed value for the pristine PP support. Regardless of the gel layer thickness, the increase of
ILs > 10 wt.% is associated with a slight decrease of both transmembrane flux and salt rejection. This
behavior, in combination with the visual observation of liquid-liquid phase separation occurring in
the pre-polymerization solution for the largest amount of ILs (15 wt.%), indicates that this solution
composition is unsuitable for the preparation of IL-HCMs.
The singular response of IL-HCMs in MD testing, depending on the gel layer composition, is due
to the synergistic interaction of the hydrogel phase and the ionic liquid dispersed in the mesh-like
structure. According to experiments, it is clear that the presence of mobile ionic species in the
polyelectrolyte gel network is responsible for the increased NaCl rejection. Figure 5, in fact, reveals
that salt rejection for composite membranes without IL is always lower than that observed for the PP
support. In the case of NaCl as a feed solution, polarized groups existing in the gel network affect
mobile ions distribution at the hydrogel/feed interface by interacting with Na+ cations and Cl− anions.
The overall flux of ions (both Na+ and Cl− ) from the bulk solution to the hydrogel phase is sustained
by the diffusive transport under concentration gradient, which is also affected by the osmotic pressure
generated by the attraction of water molecules by the strongly hydrophilic gel phase. In the absence
of IL, the enhanced mobile charges density in the hydrogel network is responsible for the lower salt
rejection. On the other hand, the increase of salt rejection observed for the membranes doped with IL
can be rationalized considering the electrostatic repulsion (Donnan effect [41–43]) of either cationic
or anionic species with charged moieties IL. Obviously, the mechanism of the Donnan exclusion in
the case of ILs is more complex than simpler charged species, because of their unique molecular
structure, polarity, and charge distribution [44]. SPE contains quaternary amminic and sulphonic
groups (Figure 1) that may interact strongly with both cation and anion part of the IL. It is possible to
speculate that the hydrophilic micro-channels formed by the interactions between the polyelectrolyte
gel network and the IL (Figure 4) exert higher resistance to the transport of ionic species: Na+ cations
are rejected by the imidazolium component of the IL and Cl− anions are rejected by the phosphate
ion. At the same time, the resistance to the water transport is reduced with respect to a hydrogel layer
without IL, thanks to the well-interconnected network of hydrogen bonds formed between the two
components (IL and polyelectrolyte).
139
4. Conclusions
In this work, ionic liquid hydrogel composite membranes were successfully prepared
and tested for membrane contactors applications. Namely, [2-(Methacryloyloxy)ethyl]dimethyl-
(3-sulfopropyl)ammonium hydroxide hydrogel, cross-linked with N,N-methylene bisacrylamide, and
containing 1-butyl-3-methylimidazolium hexafluorophosphate as ionic liquid additive, have been
demonstrated suitable for membrane distillation applications. Overall, water transport through
IL-HCMs is not negatively affected by the presence of the hydrogel when the IL is included in the gel
network. Complete recovery, and even improvement, of the transmembrane flux, compared to the
sole hydrophobic support, was observed for IL content > 1 wt.%. Furthermore, all IL membranes
presented a larger rejection of sodium chloride than the PP membrane or the composite without ionic
liquid inside. This is due to the effect of the ionic liquid entrapped inside the polyelectrolyte layer
with the resulting increase in charge density in the gel network that rejects ions at the feed/hydrogel
interface under the effect of the Donnan exclusion potential. This effect brings salt rejection as high as
99.99% for composite membranes containing IL up to 10 wt.%. Increasing further the amount of IL
induces phase separation in the pre-polymerization solution, thus making this composition unsuitable
for IL-HCMs preparation.
Although the overall transmembrane flux of IL-HCMs developed in this work is comparable with
that of state-of-the-art MD membranes, this study demonstrated that a hydrophobic macroporous
membrane could be functionalized by a hydrogel layer comprising IL. The strong hydrophilic hydrogel,
in addition to the increased transmembrane flux and salt rejection, serves as a stabilization layer, by
providing the new media between the feed and the hydrophobic membrane surface, thus potentially
controlling the diffusion of hydrophobic foulant molecules. This would result in a decrease in the
membrane wetting and fouling aptitude.
Author Contributions: Conceptualization, G.D.P.; methodology, G.D.P., E.F., E.C.; investigation, S.M.S., R.S., and
S.D.; data curation, S.M.S., R.S., and S.D.; writing-original draft preparation, G.D.P.; writing-review and editing,
G.D.P., E.F., and E.C.; supervision, G.D.P., E.F.; funding acquisition, G.D.P., E.C.
Funding: The Education, Audiovisual and Culture Executive Agency (EACEA) for the financial support of
the doctoral research fellowship of S. M. S. through the programme Erasmus Mundus Doctorate in Membrane
Engineering—EUDIME (FPA 2011-0014).
Acknowledgments: Authors wish to thank The Education, Audiovisual and Culture Executive Agency (EACEA)
for the financial support to the doctoral research fellowship of S. M. S. through the programme Erasmus Mundus
Doctorate in Membrane Engineering—EUDIME (FPA 2011-0014).
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ISBN 978-3-03921-022-0 (Pbk)

About the Special Issue Editor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . vii

Preface to ”Membrane and Membrane Reactors Operations in Chemical Engineering” . . . . ix

Parisa Biniaz, Niloofar Torabi Ardekani, Mohammad Amin Makarem and

René Ruby-Figueroa, Monica Nardi, Giovanni Sindona, Carmela Conidi and

Marina Holgado and David Alique

Barbara Morico, Annarita Salladini, Emma Palo and Gaetano Iaquaniello

Alessio Caravella, Adele Brunetti, Monia Grandinetti and Giuseppe Barbieri

Shabnam Majidi Salehi, Rosangela Santagada, Stefania Depietra, Enrica Fontananova,

Received: 30 September 2018; Accepted: 7 January 2019; Published: 15 January 2019

Keywords: membrane distillation; wastewater treatment; membrane configuration; fouling renewable

ChemEngineering 2019, 3, 8 1 www.mdpi.com/journal/chemengineering

2.1. History of MD Process

A membrane distillation system that is used for concentration of

Figure 1. Schematic diagram of the MD process [10].

2.3. Limitation and Beneﬁts of MD Process

Advantages Disadvantages Reference

2.4. Membrane Characteristics

2.5. Membrane Materials and Modules

Figure 2. Advantage and disadvantages of membrane modules.

Table 3. Commercial membranes applied in MD (membrane thickness, δ; porosity, ε; liquid entry

3.1. Direct Contact Membrane Distillation (DCMD)

3.2. Air Gap Membrane Distillation (AGMD)

3.3. Sweeping Gas Membrane Distillation (SGMD)

3.4. Vacuum Membrane Distillation (VMD)

Table 4. The merits and demerits of conventional MD conﬁgurations.

Method of Treatment Advantages Disadvantages Reference

A suitable conﬁguration for removing Large condenser needed due to

4.1. Thermostatic Sweeping Gas Membrane Distillation (TSGMD)

4.2. Multi-Effect Membrane Distillation (MEMD)

Figure 5. Schematic diagram of the multi-effect membrane distillation (MEMD) [19].

4.3. Vacuum Multi-Effect Membrane Distillation (V-MEMD)

Figure 6. Schematic diagram of vacuum multi-effect membrane distillation (V-MEMD) [19].

4.4. Material-Gap Membrane Distillation (MGMD)

Figure 7. Schematic diagram of material gap membrane distillation (MGMD) [83].

To simulate large-scale module conditions, it is essential to perform the experiments at

4.5. Permeate-Gap Membrane Distillation (PGMD)

Figure 8. Schematic diagram of permeate-gap membrane distillation (PGMD) [86].

Table 5. The application of the MD process in different industries.

Area Application MD Conﬁguration Reference

Dye removal VMD

The Application of MD in Water and Wastewater Treatment

6. Fouling Phenomenon in MD Process

Detection Method(s) Prevention Process(es) Reference

• Permeate ﬂux decline

• X-ray powder diffraction (XRD) to analyze and evaluate the

• Optical laser sensor method for investigation of the deposit

7. Wetting Phenomenon in MD Process

8. Novel Approaches to MD Technology

9. Economic Analysis of MD Process

10. Future Trends and Conclusions

Abbreviations and Symbols

PVA Polyvinyl alcohol

Received: 19 October 2018; Accepted: 10 January 2019; Published: 17 January 2019

ChemEngineering 2019, 3, 10 37 www.mdpi.com/journal/chemengineering

tia = ∑ Wka∗ Xik ; (T = XW∗ ) (1)

Xik = ∑ tia pak + eik ; (X = TP + E) (2)

Yim = ∑ cma tia + fim ; (Y = TC’ + F) (3)

The PLS regression coefﬁcients, bmk (B) can be written as:

3. Materials and Methods

3.1. Feed Solution

Table 1. Physico-chemical characteristics of orange press liquor.

Hesperidin (mg/L) 159.60 ± 14.42

3.2. MF-UF Equipment and Procedures

Table 2. Characteristics of selected membranes.

Membrane Type MV020T UV150T FMU6R2

3.3. Determination of Sugars

3.4. Determination of Hesperidin

3.5. Pore size and Pore Size Distribution Measurement

3.6. Thickness and Contact Angle Measurement

3.7. Data Analysis

3.7.2. Number PLSR Components or Factors and Model Validation

4. Results and Discussion

Xik = ∑ tia pak + eik ; (X = TP + E) (2)