Membrane Processes and Renewable Energies

Renewable and Sustainable Energy Reviews 43 (2015) 1343–1398
Contents lists available at ScienceDirect
Renewable and Sustainable Energy Reviews

journal homepage: www.elsevier.com/locate/rser
Membrane processes and renewable energies

M.G. Buonomenna a,n, J. Bae b
a
Ordine dei Chimici della Campania—Via A. Tari, 22, 80138 Napoli, Italy
b
Department of Applied Chemistry, Dongduk Women’s University, Seoul 136-714, Republic of Korea
art ic l e i nf o a b s t r a c t
Article history: In this work, an overview of the interconnections between membrane technology and renewable energy
Received 19 November 2013 sources (biomass, salinity gradient power, wind, solar) is given.
Received in revised form Regarding biomass, membrane processes such as membrane reactors and bio-reactors, membrane
19 November 2014
contactors, membrane distillation in the logic of process intensification strategy may be opportunely
Accepted 25 November 2014
integrated in the production processes of green fuels. Their advantages such as reduction of the
Available online 5 January 2015
separation load and stage number, improved yields and selectivities compared to conventional processes
Keywords: imply low direct energy consumption, lower footprint area occupied by the processes plants. Moreover,
Biomass the possibility of integration these advanced membrane processes with other traditional membrane
Membrane reactors
operations such as microfiltration (MF), ultrafiltration (UF), nanofiltration (NF), reverse osmosis (RO),
Membrane gas separation
pervaporation (PV) allows the reduction of indirect energy consumption through the recycling and reuse
Membrane contactors
Salinity gradient power of raw materials and secondary materials minimizing the formation of wastes.
Reverse electrodialysis (RED) Both Pressure Retarded Osmosis (PRO) and Reversed Electro Dialysis (RED), the only two technol-
Sustainable desalination ogies for which salinity gradient power-based demonstration projects are running, use membranes. In
this article, key points and challenges to be faced for both PRO and RED are reported.
On the other side, membrane desalination plants, are more often considered excellent locations to
install wind and solar power generators. Most advanced research in the field is focused on solar assisted
membrane distillation (MD). In the logic of fully "sustainable desalination", highly innovative technol-
ogies such as Microbial desalination cells (MDCs) could be integrated as pre-treatment stage in
membrane desalination plants in remote, arid regions.
& 2014 Elsevier Ltd. All rights reserved.
Contents
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1344
2. Renewable energy sources (RES) exploitation and the active role of membrane processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1347
2.1. Biomass: Energy carriers and membrane processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1347
2.1.1. Hydrogen from biomass thermo-chemical conversions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1350
2.1.2. Biological production of energy carriers and their upgrading . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1361
2.1.3. Biobutanol production . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1374
2.2. Salinity gradient power: Pressure retarded osmosis or reverse electrodialysis? . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1376
2.2.1. Pressure retarded osmosis (PRO): Design for the optimal membrane . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1378
2.2.2. Reverse electrodialysis: Novel compartment and cell design . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1379
3. Renewable energy for membrane desalination . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1381
3.1. Large/medium scale RO plants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1382
3.2. Solar assisted small scale/demonstrative plants. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1384
3.2.1. PV assisted RO . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1384
3.2.2. Solar assisted MD. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1386
3.3. Microbial desalination cells: A high innovative desalination technology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1387
4. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1389
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1390
n
Corresponding author.
E-mail address: [email protected] (M.G. Buonomenna).
http://dx.doi.org/10.1016/j.rser.2014.11.091
1364-0321/& 2014 Elsevier Ltd. All rights reserved.
1344 M.G. Buonomenna, J. Bae / Renewable and Sustainable Energy Reviews 43 (2015) 1343–1398
1. Introduction industry due to hydrofracking, enabling firms to extract natural

gas from unconventional reserves such as vast deposits of shale
In the recent declaration by the United Nations of 2014 to 2024 [3]. Extensive shale gas deposits are found around the world:
as the Decade of Sustainable Energy for All, it’s emphasized that North and South America, Russia, China, Australia, North Africa,
“improving energy efficiency, increasing the share of renewable Europe, but, so far, the shale gas boom is largely confined to the US
energy, and cleaner and energy-efficient technologies are important [3]. The International Energy Administration (IEA) has estimated
for sustainable development” [1]. The crucial role played by renew- that Europe could hold trillions of recoverable cubic metres of
able energy sources (RES) for the “Sustainable development” item is shale gas across several Member States [4]. In Europe there are
underscored by the choice of the title “Promotion of new and currently no commercial drilling operations. Exploration is cur-
renewable sources of energy” as its sub-item [1]. In the declaration, rently taking place in the UK, Poland, Germany, Romania, Denmark
it’s recognized “that the current share of new and renewable and Hungary [4]. However, this new approach to fossil fuels
sources of energy in the global energy supply is still low owing exploitation is not less, if more, problematic from environmental
to, among other factors, high costs and lack of access to appropriate and economic point of views than that of conventional hydro-
technologies, and calls for action to achieve economic viability of carbons: hydrofracking is a consumptive use of water and some of
new and renewable sources of energy through enhanced research the chemical additives and the vast quantities of water used have
….” [1]. The primary role of RES has been emphasized also in raised environmental concerns [5]; the disposal of that water deep
another document adopted by the European Commission (EU), i.e. underground has been linked to an uptick in small to moderate
“Energy Roadmap 2050” [2]. The EU is committed to reducing earthquakes [6]; it is unknown how long the US gas boom, or
greenhouse gas emissions (GHG) by 2050 to 80–95% below 1990 when if started in other countries, will continue: wells drilled into
levels in the global context of necessary reductions by developed discontinuous shale rock formations peak in their production after
countries as a group. the first year and then decline rapidly; the formations are not
The various scenarios explored in the Energy Roadmap 2050 sufficiently permeable to allow free flow of the hydrocarbons
are towards decarbonization of the energy system. Among them, through naturally existing pore spaces and only artificially induced
strong support measures for RES leading to their high share both fractures provide access to fluids [7]. As known, RES are also called
in final energy consumption (30% by 2030 and 75% in 2050) and in alternative energy because are energy sources that have no
electricity consumption reaching 97% (Fig. 1). undesired consequences on the contrary to the conventional and
Indeed, Europe has been working towards legally binding uncoventional fossil fuels or nuclear energy. Alternative energies
renewable energy 2020 targets instituted by the EU 20-20-20 (i.e. Biomass Energy, Wind Energy, Solar Energy, Geothermal
package since 2009. The RES Directive of 2009 sets a highly Energy, Hydroelectric Energy) sources are renewable and are
challenging and ambitious target, i.e. that 20% of energy consumed thought to be “free” energy sources. Renewable energies will play
in the EU by 2020 will be produced by RES, with mandatory a key role in the transition to a truly sustainable energy sector,
targets for individual Members States. The RES Directive reserves with access to sustainable energy for all. Today’s renewable power
to Member States the flexibility and the scope to place differing generation technologies are increasingly cost-competitive and are
emphases on different renewable technologies according to now the most economic option for off-grid electrification in most
national priorities. A number of Member States see significant areas, and in locations with good resources, the best option for
economic advantages in increasing the proportion of energy centralized grid supply and extension.
generated by RES. Moreover, encouraging renewable energy by Renewable power generation technologies now account for
way of targets and related support schemes has encouraged around half of all new power generation capacity additions world-
technological development and resulted in significant cost reduc- wide. In 2011, the additions included 41 GW of new wind power
tions for renewable energy technology. capacity, 28 GW of solar photovoltaic (PV), 25 GW of hydropower,
The necessity to a rapid transition to a renewable energy future 6 GW of biomass, 0.5 GW of concentrated solar power (CSP) and
is urgent also in the context of the current revolution of the energy 0.1 GW of geothermal power [8]. There are other sources of
Fig. 1. EU Decarbonisation scenarios—2030 and 2050 range of fuel shared in primary energy consumption compared to 2005 outcome (in %) [2].
M.G. Buonomenna, J. Bae / Renewable and Sustainable Energy Reviews 43 (2015) 1343–1398 1345
sustainable energy including, but not limited to, tidal power, ocean are wide and very site-specific. As a result, there is no single “best”
wave power, and ocean thermal energy conversion [9]. The renewable power generation technology. It is also important to
salinity-gradient energy, also called blue energy, is available note that distributed renewable technologies, such as rooftop solar
worldwide where fresh water streams flow into the sea. The PV and small wind, can provide new capacity without the need for
global energy output from estuaries is estimated at 2.6 TW [9] additional transmission and distribution investment and therefore
which represents approximately 20% of the present worldwide cannot be directly compared to large utility-scale renewable
energy demand. The 2012 data on renewable power generation solutions.
costs by the International Renewable Energy Agency (IRENA) How is it possible to increase the competitiveness of renewable
indicate that the levelized cost of electricity (LCOE) is declining energies? One possible answer to this question is in the Process
for wind, solar PV, CSP and some biomass technologies, while intensification (PI) approach by membrane processes.
hydropower produced at good sites is still the cheapest way to Membrane processes can introduce considerable PI in the
generate electricity [10]. The LCOE of a given technology is the extraction of energy from renewable sources. PI consists of the
ratio of lifetime costs to lifetime electricity generation, both of development of novel apparatuses and techniques that, compared
which are discounted back to a common year using a discount rate to those commonly used today, are expected to bring dramatic
that reflects the average cost of capital. These technologies, improvements in manufacturing and processing, substantially
excluding hydropower, have high learning rates. The rapid deploy- decreasing equipment-size/production-capacity ratio, energy con-
ment of renewables, working in combination with the high sumption, waste production, and ultimately resulting in cheaper,
learning rates for some technologies, has produced a circle that sustainable technologies [11]. In a shorter form, any chemical
leads to significant cost declines and promotes the renewable engineering development that leads to a substantially smaller,
revolution. cleaner, and more energy efficient technology represent PI [11]. PI
The declining costs of renewable power generation technolo- occurs through two area: process-intensifying equipment, such as
gies have made renewables the default option for off-grid elec- novel reactors, and intensive mixing, heat-transfer and mass-
trification. Solar PV, biomass and wind are highly modular transfer devices; and/or process-intensifying methods, such as
solutions to the challenge of extending electricity access to remote new or hybrid separations, integration of reaction and separation,
locations, and thus help meet economic and social development heat exchange, or phase transition (in so-called multifunctional
goals. Renewable technologies can be significantly cheaper than reactors), techniques using alternative energy sources and new
diesel-fired generation, particularly in remote areas with poor or process-control methods (like intentional unsteady-state opera-
even non-existent infrastructure where transport costs can tion) (Fig. 3) [11].
increase the cost of diesel by 10% to 100%. Fig. 2 shows the cost- In the European Roadmap for PI[12], the potential benefits of PI
effectiveness of today’s renewable technologies. The cost ranges that are recommended for the acceleration of its implementation in
Fig. 2. The levelized cost of renewable power generation technologies. Note: Cost of capital is 10%. The bands reflect ranges of typical investment costs (excluding
transmission and distribution) and capacity factors. PT¼ parabolic trough; ST¼solar tower; BFB/CFB ¼bubbling fluidized bed/circulating fluidized bed, AD ¼ anaerobic
digester, CHP ¼combined heat and power[10].
Fig. 3. Process Intensification and its components [11].

the process industry have been identified. The PI Roadmap has been important technologies for the upgrading of hydrogen and alternative
developed for different sectors such as Petrochemicals, bulk che- energy vectors. In addition to these well-known membrane opera-
micals (PETCHEM), Specialty chemicals, pharmaceuticals (FINE- tions, technologies such as reverse electrodialysis and pressure
PHARM), food ingredients (INFOOD), consumer food (CONFOOD), retarded osmosis, discovered in the ’70s contemporary to traditional
demonstrating that the benefits of PI can be significant in terms of membrane operations such as reverse osmosis and dug up in recent
cost competitiveness, energy savings and sustainability. Several years for recovering the osmotic energy (also called salinity gradient
programs exist in Europe to advance PI across industries, such as power) of a system and convert it into a more exploitable form, allow
the Action Plan Process Intensification (APPI). In the recent Research sustainable power generation from sea or brackish water.
Agenda published as part of the Delft Skyline Debates, the devel- On the other side, for the current trend of reducing greenhouse
opment of the industrial system in the year 2050 has been well gases emissions, always more frequently, membrane operations
defined. In many strategic sectors such as water, energy, food, such as reverse osmosis desalination are powered by means of RES
health, etc. the necessary transformations will take place consis- (wind, solar energies) (Scheme 1b), especially in areas far away
tently with the PI principles [13]. An in-depth understanding of from the electricity grid, favored by the reduction of costs of solar
these principles places membrane technology and membrane energy compared to diesel generation [20]. Membrane distillation
engineering in a crucial role for the implementation of this strategy is a promising new corner to the desalination processes which can
[14]. With their intrinsic characteristics of efficiency and operational be coupled to low-grade and renewable sources as wind and solar
simplicity, high selectivity and permeability for the transport of energy.
specific components, compatibility between different membrane Membrane processes coupled to RES have been discussed by
operations in integrated systems, low energetic requirement, good different authors addressing separately to specific issues:
stability under operating conditions and environment compatibility, Bakonyi et al. gave an overview on the operational conditions
easy control and scale-up, and large operational flexibility, mem- affecting the performance of non-porous, polymeric and ionic-
brane operations represent an interesting answer for the rationa- liquid based gas separation membranes in biohydrogen purifica-
lization of chemical productions [15,16]. One of the significant and tion [21] and more specifically, they analyzed the possibility of
recognized benefits of membrane operations is their low direct using polymeric gas separation membranes [22]; Makaruk et al.
energy consumption because of the absence of phase transforma- [23] and Basu [24] et al. reviewed biomethane purification via
tions. The second, but not less important feature, is the possibility membrane-based technologies; Cicek et al. [25] and Visvanathan
for reducing indirect energy consumption through the recycling and and Abeynayaka [26] illustrated enhanced biomethane production
reuse of raw and secondary materials minimizing the formation of via membrane bioreactors; Logan and Elimelech [27], Ramon et al.
wastes [15]. In addition, the utilization of membrane operations as [28] and Post et al. [29] discussed membrane-based processes (e.g.
hybrid systems, in combination with other conventional techniques pressure retarded osmosis, reverse electrodialysis) for sustainable
or integrated with different membrane operations is considered as a power generation using water; Qtaishat and Banat [30], Subramani
way for more rationale applications [17–19]. et al. [31], Li et al. [32] reviewed solar assisted sea water
In the last decade, the increasing number of researches on the membrane desalination.
application of membrane technology in the field of renewable energies In this study, for the first time in literature, a complete and
indicates the interest from the scientific community towards the topic. updated overview of the interconnections existing between mem-
The combination membrane technology/RES is a reality in several brane processes and renewable energies on the basis of recent
research fields such as biogas production, desalination, salinity gra- literature (last five years) is given.
dient power (Scheme 1). Relevant researches in the field of RES In particular, the article consists of two sections. The first one
exploitation have aimed at increasing productivity, yield of the covers the discussion of the active role played by membrane
processes, and decreasing their cost. Cost-effectiveness of RES exploi- processes in the production and/or upgrading of energy carriers
tation such as hydrogen production from biomass, biomethane from renewable energy sources. Particular attention has been
upgrading, and biobutanol separation gain advantages from the devoted to membrane operations used: (i) to assist biogas (both
integration with membrane processes (Scheme 1a). Membrane bior- biohydrogen and biomethane) and liquid biofuel generation (bio-
eactors, membrane gas separation, membrane contactors represent butanol) and upgrading, (ii) to recover salinity gradient power.
enhanced production/upgrading
Hydrogen
from biomass gasification Membrane Gas Separation
Biohydrogen
Membrane Contactors
Membrane
Salinity Gradient
Biomethane Bioreactors
Energy
Pervaporation
Solar Energy Pressure Retarded

Reverse Osmosis
Bioethanol Osmosis
Wind Energy Biobutanol Membrane

Reverse electrodyalisis
distillation
Power
Scheme 1. Interconnections between renewable energy sources and membrane operations.

The second section is focused on the growing role of renewable many functionalities which make biomass very reactive. In depen-
energies to power membrane desalination plants, discussed on the dence on the operating conditions, the gasification can make a
basis of plants sizes. The integration of membrane processes with stream containing mainly CH4 or syngas, which is comprised
BES (bioelectrochemical systems) such as Microbial Electrolysis predominantly of H2 and CO, together with various impurities
Cells (MECs), Microbial Reverse-Electrodialysis Cells (MRCs), including H2S, NH3 and high molecular weights compounds
Microbial Desalination cells (MDCs) has been highlighted. known as tars [35]. Maximization of H2 content requires cleaning
The analysis of both the active and passive role of membrane of its contaminants that include in addition to the compounds
operations relative to RES is aimed to give to a broad audience of reported above also others byproducts (the exact composition
readers, also not experts in the field, a clear picture of the depending on the operating conditions). The most straightforward
potentialities of the combination “membranes/RES”. biomass-to-hydrogen route seems to be gasification coupled with
water gas shift (WGS) reaction (Fig. 4). In WGS reaction cleaned
syngas is processed with steam to convert the CO into additional
2. Renewable energy sources (RES) exploitation and the active H2 and CO2 in order to produce pure H2 after CO2 is removed.
role of membrane processes When biomass (and coal, in the case of co-feeding biomass along
with coal) gasification and H2 generation are combined with
2.1. Biomass: Energy carriers and membrane processes electricity production via a turbine or a fuel cell, the process is
known as the integrated gas combined (power generation) cycle
Biomass resources are the organic matters in which the solar (IGCC).
energy is stored via chemical bonds, i.e. algae, trees, crop, and It is important to emphasize that both major components of
animal manure [33]. Among all the renewable sources of energy, IGCC, i.e. the gasification process system and the combined cycle
biomass is the only renewable feedstock that can be converted power block, are associated with mature tested technologies and
into energy and chemical products. Biomass usage as a source of have been broadly utilized in the petrochemical, chemical proces-
energy presents several advantages: (i) biomass has a low sulfur sing industries as well as for power generation (electricity produc-
content; (ii) the combustion of biomass produces less ash than tion from natural gas). Their integration has been demonstrated in
coal combustion and the produced ash can be used as a soil only a few facilities around the world, such as the two plants of
additive on farms, etc.; (iii) it is an effective use of waste products Wabash and Tampa Electric in US and the two European plants of
that reduces the significant problem of waste disposal, particularly Willem Alexander in Buggenum (The Netherlands) and ELCOGAS
in municipal areas; (iv) biomass usage could be a way to prevent (Puertollano, Spain), representing a recent technology option for
more carbon dioxide emissions in the atmosphere as it does not the commercial production of electricity [36].
increase the atmospheric carbon dioxide level. Beér [37] emphasized how the power generation efficiency is
A distinction can be made between the uses of dry biomass important also for longer term solutions of reducing CO2 emission
(such as wood) and wet biomass sources (such as organic fraction such as carbon capture and sequestration (CCS). On the basis of
of domestic waste, agro-industrial wastes and slurries, and Beér analysis, IGCC with CCS results to have cost advantage over
wastewater). other power generation systems with CCS such as pulverized coal
Dry biomass is used preferentially for thermo-chemical conver- combustion in supercritical steam boiler (PC/SC) due partly to the
sions, i.e. direct combustion, co-firing, gasification, pyrolysis, lower cost of CO2 removal and also because in IGCC the CO2 is
supercritical water gasification. available at high pressure and little or no additional capital
CO2 neutral hydrogen production (biomass derived hydrogen expenditure and energy will be required for its compression and
can be classified as carbon neutral because the CO2 released during liquefaction in preparation for sequestration.
hydrogen production is consumed by further biomass generation) Biomass offers during IGCC greater potential for CO2 emissions
can be achieved by both biomass gasification and pyrolysis of bio- reductions than coal. State-of-the-art gasifiers amenable to co-
oils (Fig. 4). As with coal, gasification remains today the main feeding biomass along with coal are available [38,39]. Co-feeding
method for H2 production from biomass [34]. of the biomass along with coal appears to be a strategy for
Biomass gasification is conducted at a much lower temperature building large scale IGCCs, capable of producing clean fuels such
(700–800 1C), than that of coal gasification due to the presence of as H2 by further processing decarbonized syngas [39,40].
Fig. 4. Production of hydrogen from biomass via gasification and pyrolysis (adapted from Tanksale et al. [134].
1348
Table 1
Some membrane processes for biomass conversion and upgrading.
Membrane processes Biomass conversion process Advantages (A)/challenges (C) Refs.
Pressure driven membrane operations: microfiltration Thermochemical conversions: upgrading of the aqueous phase A: No phase changes; No chemical additives; Simplicity in operation; [51–60]
(MF), ultrafiltration (UF), nanofiltration (NF), reverse of pyrolysis bio-oils Modularity; Easy control and scale-up; Compatibility between different
osmosis (RO)/membrane bio-reactors (MBRs) Biological conversions: pre-treatment, post-treatment and membrane operations in integrated systems; Low energy consumption
treatment of biomass by coupling UF/MF separations with C: Membrane fouling and durability
biological processes in membrane bio-reactors (MBRs)
Pervaporation (PV) Thermochemical conversions: upgrading of the aqueous phase A: Lower thermal damage of the products; Lower energy consumption [61]
of pyrolysis bio-oils compared to traditional separation processes
Biological conversions: upgrading of liquid fuels, volatile fatty C: Membrane reliability in harsh environments; high cost of membrane
M.G. Buonomenna, J. Bae / Renewable and Sustainable Energy Reviews 43 (2015) 1343–1398
acids (VFAs) coming from fermentation processes production and module fabrication; integrated systems with traditional
separation processes such as distillation in a pervaporation-distillation hybrid
process represents the most popular configuration for biofuel separation
Forward osmosis (FO) Thermochemical conversions: dewatering of the pyrolysis bio- A: Energy-friendly process; since the retentate of the FO process is the target [62–65]
oils aqueous phase product, there is a great flexibility for choosing an appropriate draw solute, and no
Biological conversions: dewatering of liquid fuels separation is required for the diluted draw solution
C: Optimized FO membranes and suitable draw solutes are needed to realize
processes for practical application
Membrane contactors (MCs) Biological conversions: upgrading of biogas; upgrading of volatile A: low energy consumption; [66–69]
fatty acids (VFAs) coming from fermentation processes; removal of the limitation on the flow rate ratio of the two phases as long as
upgrading of appropriate pressure conditions are maintained and break-through pressure
biomass hydrolysates; pre-treatment of fermentation broths difference between the phases is avoided; a much enhanced surface area per
unit equipment volume leading to highly compact devices when hollow fiber
membranes are used; modular equipment for easy scale up or scale down;
nondispersive operation eliminating foaming and weeping in gas–liquid
systems; prevention of emulsification in liquid–liquid systems; elimination of
the need for coalescence in liquid–liquid contacting processes
C: Optimized membrane contactor technology for large-scale practical
applications is not yet available due to three critical key points:
i) The development of novel microporous membranes with excellent
antiwetting, chemical and thermal resistances
ii) The utilization of new effective absorbents with low cost for regeneration and
excellent compatibility to the membrane used
iii) The development of novel membrane modules that can enhance mass
transfer in both the gas and liquid phases
Gas permeation separation (GS)/membrane reactors Thermochemical conversions: A: Ion transport membrane (ITM) as ASU technology compared to conventional [21,23,34,41–
(MRs) Gasification—(i) purification of O2 in the ASU cryogenic separation reduces both the power consumption and capital costs 46,70–76]
(ii) Steam or autothermal reforming, water gas shift in engineering Steam or autothermal reforming, followed by water gas shift in MRs:
systems in which both the reaction and separation of hydrogen are – Improvements of yields and selectivities due to equilibrium shift effect
carried out in the same device (MRs) – Reduced downstream separation costs because separation is integrated
Fast pyrolysis-steam or autothermal reforming, water gas shift in – Large reduction in process units such as heat exchangers
engineering systems in which both the reaction and separation of – Reduction of the reformer operating temperature
hydrogen are carried out in the same device (MRs). – Easier recyclability due to the reduction of components and materials in the
reactor
Upgrading of biogases (H2, CH4) coming from fermentative processes:

Biological conversions: upgrading of biogases (H2, CH4) coming – Low energetic requirement
from fermentative processes – Safety and simplicity of operation
– Easy maintenance
– Operation without hazardous chemicals
– Compatibility between different membrane operations in integrated systems
– If the upgraded biogas is to be supplied to the gas grid under pressure, the gas
permeation technology should gain advantage over upgrading technologies
Membranes can be integrated into IGCC in a variety of ways

[34], and clearly they are most effective (as shown in the Section
2.1.1) when applied to concentrated high pressure streams due to
greater driving forces for separation. Their use for both hydrogen
separation and CCS has been studied by several authors [40–46]
catalysts for SMR and ATR, because at these conditions the catalysts are much
much lower temperatures than in conventional catalytic reformers represents

– The main advantages of , namely MRsoperation at much lower temperatures
development of novel catalysts with a high activity and a good selectivity at

that operate at atmospheric pressure since it uses the compression for both
and in Section 2.1.1.1 of this paper it has been revised on the basis
membrane durability;– High product recovery can be obtained in multi-stage

– Sulfur poisoning and other impurities could damage the membranes and
– Biogas pre-treatment is necessary to avoid membrane damage and .extend

of recent literature.
and lower steam-to-carbon ratio, pose great challenges for conventional
Pyrolysis of biomass involves the thermal decomposition of the

steam or autothermal reforming, followed by water gas shift in MRs
Upgrading of biogases (H2, CH4) coming from fermentative processes

less active and more prone to catalyze carbon formation. Thus the
biomass in the absence of air or oxygen. It occurs at around 500 1C.

With severe pyrolysis conditions, more gases (CO, H2, CO2 and
CH4) are produced. The remaining bio-oil after condensation can
then be treated further to produce additional H2 [47]. Alterna-
tively, all the bio-oil can be treated in an autothermal or steam
reformer to produce H2 (see Fig. 4). In particular, autothermal
reforming (ATR) is an attractive alternative to steam reforming of
bio-oils [48]: it’s a combination of steam reforming and partial
oxidation of the hydrocarbons to produce CO, CO2 and H2.
Wet biomass and residues are less suitable for thermochemical
conversions because transport and drying require a considerable
upgrading and grid injection
amount of energy, which leads to a limited or even negative effect

a crucial aspect in the topic
on the overall CO2 reduction. The available amount of wet biomass

reduce their durability
and residues is considerable, so that their use as feedstock for

membrane configuration
renewable energy production is certainly worthwhile [49]. Biolo-

gical conversion processes (fermentative hydrogen production,
photo-fermentation, biological water gas shift reactions) are par-
ticularly useful for this application because they are catalyzed by
the microorganisms in the aqueous environments at low tem-
perature and pressure. Furthermore, these techniques are well
C:
suited for decentralized energy production in small-scale installa-

tions where biomass or wastes are available, thus avoiding energy
expenditure and costs for transport. The general expectation is
that biotechnological processes will play a substantial role in the
production of energy vectors and liquid biofuels such as bioetha-
nol and ABE (Acetone–Butanol–Ethanol) [49,50].
In Table 1 an overview of the most relevant membrane
processes coupled to biomass conversion and reviewed in this
section is given. Particular attention has been devoted to hydrogen
production both from dry biomass via gasification and fast
pyrolysis (Section 2.1.1) and wet biomass via biological routes
(Section 2.1.2).
Hydrogen is not a primary energy source like coal and gas. It is
an energy carrier (or vector) and as such makes it possible to
transmit a given quantity of energy from the place of production to
the place of consumption. Currently, it is produced predominately
using existing energy systems based on different conventional
primary energy carriers and sources. In the longer term, RES will
become the most important source for the production of
hydrogen.
Regenerative hydrogen, and fossil-based energy conversion
systems with capture, and safe storage (sequestration) of CO2
emissions, are almost completely carbon-free energy pathways. A
crucial role for the hydrogen energy is played by fuel cells. As
described in Sections 2.1.1 and 2.1.2.3, (devoted to hydrogen from
biomass gasification and biohydrogen), respectively, the fuel cells
unit is always present.
In fact, hydrogen, used in association with fuel cells, which are
very efficient energy conversion devices, could replace the con-
ventional duo formed by hydrocarbons/combustion systems with
consequent benefits such as decreased pollution, sharply reduced
GHG emissions and increased energy independence of oil con-
suming countries. The wide range of options for sources, con-
verters and applications, shown in Fig. 5, although not exhaustive,
illustrates the flexibility of hydrogen and fuel cell energy systems
[77].
Fuel cells convert fuel and air directly to electricity, heat and
water in an electrochemical process. A fuel cell consists of two
electrodes sandwiched around an electrolyte. Oxygen passes over paper. At the interface between the porous electrode and the
one electrode and hydrogen over the other, generating electricity, polymer membrane there is a layer with catalyst particles, typi-
water and heat. cally platinum supported on carbon. A schematic of PEMFC is
Unlike other electrochemical devices such as batteries, a fuel shown in Fig. 6.
cell does not run down or require recharging. It produces energy An extended treatise on PEMFCs may be found in [79,80].
in the form of electricity and heat as long as fuel is supplied. PEMFCs are particularly attractive for low (less than 1 kW) to
Unlike conventional engines, they do not burn the fuel and run intermediate power levels (up to 50 kW) and for applications that
pistons or shafts and so have fewer efficiency losses, low emissions require rapid start-up and quick response to load changes.
and no moving parts. Their advantages are: (i) high efficiency; (ii) Decentralized production of electricity with or without heating
zero emissions when using hydrogen and very low emissions for single or multiple family housing or industrial parks (small and
when using other fuels; (iii) low vibration and noise; (iv) a high medium sized enterprises, light industry, etc.) represents a sig-
ratio of electricity to heat compared to conventional combined nificant outlet given the excellent energy efficiency of the fuel cell
heat and power plants [77]. Different fuel cell systems operate at used. As shown in Fig. 7a, the applications of fuel cells (i.e.
different temperature levels from room temperature up to 1000 1C stationary, transportation and portable) indicate an increase pri-
and some can use fuels other than hydrogen such as natural gas or marily in the stationary market, attributable to residential units
methanol. Table 2 lists the different types of fuel cells. The main [81]. In fact, there is steady increase in Megawatts shipped for
difference among them is the type of materials used in the fuel cell most of the period, but a slight decline between 2010 and 2011,
stack to generate the chemical reaction needed to make electricity. primarily in the stationary market (Fig. 7b): residential units
Their modular nature means fuel cells can be used over a broad typically produce a few kilowatts of power each, a small fraction
range of applications from small portable electronic devices to of the output of large stationary units.
large stationary applications as well as for transport.
T. Grubb of General Electric (GE) developed the first Proton
Exchange Membrane Fuel Cell (PEMFC) in 1954 [79]. Launched in 2.1.1. Hydrogen from biomass thermo-chemical conversions
the early 1990s by the Canadian company Ballard, which provided 2.1.1.1. Gasification
to reduce the membrane costs, PEMFCs use a proton conductive 2.1.1.1.1. Membrane gas separation. The most straightforward
polymer membrane as the electrolyte to convert hydrogen into biomass-to-hydrogen route seems to be gasification coupled with
electrical energy [79]. the water gas shift reaction. As mentioned above, when biomass
At the heart of a PEMFC is a polymer membrane that has gasification and H2 generation are combined with electricity
specific characteristics: it is impermeable to gases and conducts production, the process is known as IGCC. Employing biomass as
protons. The membrane, which acts as the electrolyte, is squeezed a feedstock has the advantage of being carbon neutral or even
between the two porous, electrically conductive electrodes. These carbon negative if carbon is captured and sequestered (CCS).
electrodes are typically made out of carbon cloth or carbon fiber
Fig. 5. Hydrogen: primary energy sources, energy converters and applications [77]. Fig. 6. Basic design of PEMFC [78].
Table 2
Types of fuel cells.
Type Electrolyte Operating temperature (1C) Commercial applications
Proton exchange membrane (PEMFC) Solid polymer, proton conducting electrolyte 50–90 Transportation, stationary, portable power
Direct methanol Solid polymer, proton conducting electrolyte 40–100 Portable power, transportation, stationary
Solide oxide Yttria stabilized zirconia 800–1000 Transportation, stationary, portable power
Phosphoric acid Phosphoric acid 190–210 Stationary
Molten carbonate 630–650 Stationary
Fig. 7. Fuel cells systems (a) and megawatts (MWs) (b) of fuel cells shipped by application, World markets (2008–2011) [81].
Fig. 8. Generic flow diagram for separation of H2 and CO2 in IGCC–CCS applications.
However, gasification of pure biomass for application in IGCC (ASU) (Fig. 8, left) plays a key role in improving the efficiency,
has either failed due to some technical difficulties or been availability, and operability of an oxygen-fed IGCC power plant
removed from the commercial power sector due to not being [88]. However, the conventional ASU technology which uses
economically competitive [82–85]. Therefore, it is more economic- cryogenic separation has a significant parasitic power consump-
ally attractive and less technically challenging to co-gasify biomass tion as much as 15% of the IGCC gross power output [89]. Highly
(more specifically biomass wastes) with coal [86,87]. The addition selective membranes to separate O2 from hot compressed air
of different amounts of biomass as feedstock reduces carbon (800–900 1C) can overcome the drawback of cryogenic separation
footprint as well as the SOx and NOx emissions. by increasing power efficiency [39].
In Fig. 8 a simplified process flow diagram for hydrogen or In the late 1980s Air Products identified a class of perovskite
energy production via IGCC integrated with membrane gas ceramic materials with high flux and separation selectivity for
separation is given. oxygen ions. These materials have become the basis for a novel
Biomass (and coal in case of biomass co-feeding) gasified with class of air separation technologies, referred to as ion transport
O2 after clean-up is passed through a water–gas shift bed to membranes (ITMs). These membranes separate oxygen from air at
maximize H2 and CO2 production. This stream is fed to a hydrogen high temperature in an electrochemically driven process. The
purification unit: the purified hydrogen can be fed to a hydrogen oxygen in air is ionized on the surface of the ceramic and diffuses
turbine for power production or can be used for fuel cell or through the membrane as oxygen ions, driven by an oxygen
industrial uses. activity (partial pressure) gradient to form oxygen molecules on
Membrane gas separation can be used in the two separation the other side. In addition, these materials conduct electrons as
units schematized in Fig. 8, i.e. in the air separation unit (ASU) and well as ions, meaning that no external source of electrical power is
to purify the hydrogen from the water–gas shift reaction. required. The air separation system that results from the use of
In high temperature gasifiers, the gasifier efficiency increases ITMs produces a hot, pure oxygen stream and a hot, pressurized,
and the size of downstream equipment is reduced when oxygen, oxygen-depleted stream from which significant amounts of energy
instead of air, is used in the gasifier [87]. The air separation unit can be extracted.
Thermodynamic and process economic analyses indicate that In the membrane unit of Fig. 8 a hydrogen-selective membrane
the ITM Oxygen process produces oxygen at a significantly lower is used, but also CO2-selective membranes appropriately selected
cost than conventional cryogenic processes [90]. The high selec- could improve the economics of CO2 capture from an IGCC process
tivity to oxygen separation afforded by the membrane and its [35–37]. Actually, hydrogen-selective membranes offer several
rapid oxygen flux result in compact membrane devices with little advantages compared to CO2-selective membranes: they could
pressure drop, resulting in 430% reduction in the cost of oxygen. operate at elevated temperature immediately downstream of the
A block diagram of this concept as implemented in an IGCC facility shift reactor, eliminating the costs of a cooling step; the CO2 in the
is shown in Fig. 9 [91]. In this diagram, the ITM Oxygen system retentate remains nearly at gasifier pressure of 20–40 bar, which
operates fully integrated with the main gas turbine of the IGCC reduces the power needed for the compression to pipeline
plant. A pressurized air stream is extracted from a gas turbine and pressure; sweep gas, for example excess N2 from the ASU, may
fed to the ITM unit after passing through a direct combustor to be applied differently than the case of CO2-selective membranes
raise the feed temperature to 800–900 1C; oxygen-depleted off- where it would diminish the CO2 purity; also the sweep gas will
gas from the membrane unit, at substantially the same pressure as act as a diluent in the gas turbine combustor with favorable effect
the feed air, is reinserted into the combustion turbine for conver- on low NOx emissions.
sion of its thermal and hydraulic energy to shaft work. The The current leading technologies for CO2 capture from shifted
compressed air not extracted from the gas turbine goes directly syngas in an IGCC system are physical absorption processes, such
to the combustion turbine (not shown). By contrast, if the air is fed as Selexol™ or Rectisols [93].
to a cryogenic ASU instead of the ITM Oxygen unit, the heat in the In Table 3 a comparison between these technologies and
air stream would be rejected and much of the pressure energy membrane processes is given.
would be expended during the oxygen extraction. The absorption systems consume large amounts of energy in
As schematized in Fig. 8, the syngas after cleaning, is shifted the absorber-stripper operation. Membrane processes, in the
with steam to produce more hydrogen via water gas shift reaction specific case Membrane Gas separation and Membrane Reactors
(WGS): (entries 2 and 3, respectively, in Table 3) offer an interesting
alternative approach for hydrogen purification and CO2 capture in
CO þ H2 O⇄CO2 þ H2 ð1Þ IGCC power plants.
Both H2-selective membranes and CO2-selective membranes
and treated to remove CO2 via a membrane separation unit prior have been explored (Table 3, entry 2) by a number of authors to
to combustion to avoid emission of this greenhouse gas. The WGS separate IGCC CO2/H2 mixtures [41,43–46].
reaction is exothermic, its equilibrium conversion favored by low Highly selective inorganic hydrogen-permeable membranes
temperatures. In the traditional system, two reactors in series are based on palladium, palladium alloys, ceramics, zeolites (Table 3,
typically used to overcome both equilibrium and kinetic limita- entry 2) are mandatory for high purity hydrogen, although some
tions and to increase conversion [92]: one known as the high- drawbacks such as high costs, embrittlement by hydrogen, sensi-
temperature shift (HTS) reactor, operates at high temperatures tivity to sulfur compounds, constituted the driving force for
(370 1C) using Fe/Cr based catalyst; the other, known as the low further studies in the field, as discussed later.
temperature shift (LTS), operates at lower temperatures (200 1C) For IGCC power applications where high purity hydrogen is not
using a Cu/Zn based catalyst. required for combustion turbine fuel, polymeric membranes offer
Ultimately the syngas is sent to a combustion turbine and the the advantage of cheap production on a large scale compared to
waste heat from gasification and syngas combustion are used to more selective ceramic or metallic proton conducting membranes.
power steam turbines. They can easily be manufactured as hollow fibers or thin sheets
Fig. 9. Block diagram of an ITM oxygen unit in an IGCC facility [91].

Table 3
H2 coproduction in IGCC with CCS via coal and biomass mixture: comparison of state-of-art CO2 capture technology with membrane processes.
Entry Technology Main characteristics Advantages Disadvantages References
1 Physical absorption Use of a physical solvent No-fouling and inherently no-foaming Rectisol is an acid gas which uses a methanol solvent therefore due to the required [93]
(e.g. Selexol, Rectisol) Loading directly proportional to Low vapor pressure and therefore low refrigeration to cool the methanol, Rectisol can be quite expensive
partial pressure solvent loss Large and complex absorption systems, which consume large amounts of energy in
Operating conditions No formation of heat stable salts the absorber-stripper operation. Capturing and sequestering 90% of the CO2 using
Temperatures: 313 K (Selexol), 213- At high pressure, physical solvents might Selexol will result in about a 30% increase in the levelized cost of the electricity
263 k (Rectisol) be a better choice than chemical solvents (LCOE).
Pressures:
430 atm (Selexol)
30–80 atm (Rectisol)
2 Membrane gas 1) H2 permeable membranes Compactness and modularity High membrane selectivity are required to be competitive with commercial [42–46]
separation Inorganic membranes: Placement at more than one location to technologies
Pd and Pd alloys, ceramics, carbons, separate H2 from CO2 and other gas H2 permeable membranes: H2/CO2 selectivity 4 50 [44]
zeolites components
Operating conditions Simplicity of operation
150–550 1C (silica-based) Easy scale-up
600–900 1C (doped rare-earth oxides) Low plant cost compared to Selexol CO2 permeable membranes: CO2/H2 selectivity 460 [44]
320–450 1C (Pd) Estimated LCOE increase lower than Selexol
150–550 1C (carbon molecular
sieves)
150–450 1C (zeolites)
Polymeric membranes:
Polyetherimide, ethyl cellulose ,
polyimide, polysulfone,
polyethersulfone,
polybenzilimidazole (PBI)
Operating conditions
o 200 1C (commercial polymers)
o 400 1C (PBI)
2) CO2 permeable membranes
Poly(amide-6-b-ethylene oxide)
(Pebaxs)
Pebaxs/polyethylene glycol blend
Poly(ethylene glycol) diacrylate
Crosslinked PEG copolymer
Polyvinylamine (PVAm)
PVAm/PVA blend
Operating conditions
Low temperatures: 25 10 1C
3 Membrane reactors Pd based membranes microporous Higher conversion in a single-stage reactor Pd membranes: [98–101] (Pd
(water gas shift silica microprous zeolites Reduction of the amount of Sensitivity to syngas impurities, particularly H2S with reduction of membranes);
membrane reactors) CMS membranes superstoichiometric steam, needed in permeability and surface scale of Pd sulfides; Limited availability
Operating conditions: 300 1C conventional WGS reactor of the metal [102–104]
High purity H2 with reduced need for Silica membranes: low hydrothermal stability (microporous
downstream hydrogen purification. When silica);
ultra-high purity hydrogen is required [105,106]
(e.g. for PEM fuel cells), Pd membranes (zeolite
show good potential for use membranes);
[107–109]
(CMS
membranes)
1353
exhibiting high area to volume ratios [41]. The disadvantage lies in separation [14,97]. Both these approaches have been discussed
the limited thermal stability (up to 200 1C, except polybenzilimi- briefly in the following paragraphs.
dazole which is stable up to 400 1C, Table 3 entry 2) and the low 2.1.1.1.2. Hybrid membrane processes. Two studies are discussed
selectivity [41,94]. in this paragraph: the first by Merkel et al. at MTR [43] and the
Franz and Scherer [44] compared the performance of CO2 and second carried out at General Electric by Ku et al. [46].
H2 selective polymeric membranes for CO2 separation in IGCC Merkel et al. [43] proposed different membrane processes
processes: as a prerequisite to be competitive with CO2 technol- designs based both on H2-selective and CO2-selective membranes:
ogies like Selexol or Rectisol it has been postulated that efficiency compared to Selexol, current membrane designs use less energy
losses below 10% points must be achieved for separation degrees and cost significantly less. The authors emphasized how a H2-
above 85% and purities above 95%. These pre-defined goals selective membrane is preferred over a CO2-selective membrane
for purity and separation degree resulted in a relation between for the advantages reported above. However, if only currently
membrane selectivity and power plant efficiency. In particular, available membranes (with a modest selectivity) are used, a design
the analysis by Franz and Scherer [44] revealed that the selectiv- using both H2-selective and CO2-selective membranes integrated
ities of current polymeric membranes [94] (neither CO2 selective with cryogenic condensation (Fig. 10) offers significant advantages
nor H2 selective membranes) are not sufficient to reach the goals over a membrane-only approach.
defined. The design reported in Fig. 10 makes use of N2 available from
Membranes with hard-to-achieve selectivities and permeances the on-site ASU as a sweep gas to reduce the energy cost of
are required to bring the process into the economically feasible recompressing permeated hydrogen going to combustion turbine.
range: (i) for CO2 -selective membranes CO2/H2 selectivities have The nitrogen sweep concept, which can be used with a hydrogen-
to rise above 150 which is tenfold the selectivity of state of the art selective membrane to treat syngas while maintaining both the
(15.5) polymeric membranes [95]. With membrane cascade con- CO2-enriched residue and hydrogen-enriched permeate streams at
cept the selectivity can be reduced to 60; (ii) for hydrogen- elevated pressure, is not new: it has been proposed for inorganic
selective membranes selectivities in the order of 50 (state of the membrane reactors (as reported below) and discussed by Ciferno
art 5.9) are needed to achieve efficiency losses below 10% point at and Marano [41], as mentioned above.
separation degrees of 85%. More in detail of Fig.10, the hot shifted syngas is passed
Actually, as observed on the basis of techno-economic evalua- through a hydrogen-permeable membrane. N2 from the ASU unit
tion of systems also with highly selective CO2 permeable mem- is circulated countercurrently to the feed gas on the permeate side.
branes [44,95] the major efficiency loss does not arise from the The retentate stream is heat exchanged and then cooled in a
separation process itself, but from the shift reaction of CO to CO2. fractionating condenser to capture liquid CO2. The role of the CO2-
The shift accounts for an efficiency drop of approximately 4.3% selective membrane is that of treating the overhead gas of the CO2
points which is a specific drawback of ICGG when used for CO2 condenser producing a retentate stream containing inert gases and
separation [44]. H2 that can be burned. In this design, the CO2 liquefaction can be
The approaches explored to reduce as soon as possible the conducted at higher temperatures (i.e. less refrigeration power is
efficiency loss, required to make membrane gas separation inte- used) than the design without CO2-permeable membrane unit to
grated in a ICGG plant competitive compared to traditional the front of the condenser. Overall, the integration of membrane
separation processes, are mainly two, both broadly used in many units with cryogenic condensation reduces the membrane require-
industrial membrane applications in the logic of PI, mentioned in ments necessary to achieve the separation targets (90% CO2
Section 1. capture and 99% H2 recovery). In addition, minor syngas compo-
The first one consists of using membrane gas separation in nents such as CH4, CO, that have fuel value, thanks the cryogenic
conjunction with other separation techniques (hybrid membrane step downstream of the hydrogen-selective membrane may be
processes) to take advantages of the benefits of each technology recovered from the CO2-enriched retentate stream and sent with
[96]; the second approach is of integrating the membrane intrinsic H2 to the combustion turbine.
separation function with that of reaction into one unit by using Ku et al. [46] proposed a design (Fig. 11) with a one stage H2-
membrane reactors (entry 3, Table 2), realizing a so-called reactive permeable membrane and a catalytic oxider which combusts the
Fig. 10. A membrane process that uses both H2 and CO2 selective membranes [43].
unpermeated H2, along with unshifted CO, CH4 and other compo- Pd membranes have some drawbacks: they are more expensive
nents with fuel value, i.e. the fuel components from the syngas feed than other inorganic membranes; H2O and CO block dissociation
retained in the retentate, so-called fuel slip. One of the primary sites on the membrane surface and reduce hydrogen recovery,
performance metrics of power plants is thermal efficiency,but it is especially at temperatures below 350 1C [110].
difficult for membrane technologies to economically recover all of Common syngas impurities (e.g. H2S) are known to adversely
the fuel components in the syngas (i.e. unrecovered H2, CO, and affect the Pd membrane characteristics, even at very low concen-
CH4). In the design proposed by Ku et al. [46] the shifted syngas is tration levels.
sent to a high temperature H2-permeable membrane module. The The technical challenges associated with Pd membranes
H2 permeate is blended with a compressed N2 stream from the ASU induced to investigate other types of high-temperature mem-
and sent to a gas turbine without further compression for electricity branes, such as microporous silica and CMS membranes. Silica
generation. The retentate stream is cooled, cleaned of H2S and other membranes have proven effective for the WGS-MR application,
contaminants, and fed through a catalytic combustor to generate but they are known to be sensitive to high-temperature and
steam from the unrecovered H2, and other fuel components such as pressure steam.
CO and CH4. In this way, the thermal efficiency of the power plant is Carbon molecular sieve membranes have proven equally effec-
improved by using the produced steam to generate electricity in a tive for the WGS-MR application, in addition to being stable in the
steam turbine or for heat integration. The catalytic oxidizer has the presence of steam in the WGS Environment [111].
same role of the cryogenic step in the design proposed by Merkel They have also proven to be stable for more than a month
et al. [43], discussed above: since no known membrane materials under the WGS reactive environment using a feed with high levels
exhibit significantly higher transport rates for CO and CH4 over CO2, of H2S, with no apparent change in the membrane permeation
downstream operations on the retentate stream of H2-permeable characteristics indicative of the good stability of the membranes in
membranes are needed to recover the energy from CO, CH4 and the presence of the impurities [111].
unrecovered H2 [46]. However, in addition to H2S, NH3, organic vapors and tars are to
2.1.1.1.3. Membrane reactors. In the designs illustrated above be considered in WGSMR processing of biomass-derived syngas.
(see Figs. 8–11) the function of the membrane units is that of Studies by Tsotsis and co-workers to evaluate the stability of
purifying the shifted syngas to obtain a H2 rich stream for CMSM in the presence of simulated biomass-derived syngas
combustion turbine fuel, where high-purity hydrogen is not containing realistic amounts of naphatlene, as a model tar and
required. toluene as a model organic vapor, showed stable performance as
However, if the hydrogen produced from biomass is clean and long as the temperature stayed above 250 1C [34]. These results
of high purity, a PEMFC can be integrated directly with the were also validated with real coal-derived and/or biomass-derived
biomass gasification process. syngas by using a pilot-scale CMSM module containing 86 mem-
A membrane reactor that combines the WGS reaction with branes [74].
hydrogen separation into a single unit (WGSMR) (Fig. 12) thus In a recent study, the same research group summarized the
eliminating the need for the two separate WGS reactors and for a efforts for hydrogen production from coal and biomass using
distinct purification section simplifies and improves significantly membrane-based reactive separations, in particular by using
in terms of conversion and H2 purity the process. CMSM [112]. The novelty of the WGSMR discussed by these
In a WGSMR either the membrane surface itself has to be authors is that it uses impurity-resistant CMS membranes and a
catalytically active or the feed channel has to be filled with
catalytically active material. By continuously removing H2 from
the product side of the WGS reaction, the equilibrium of the
reaction (1) can be shifted to the products, i.e. H2 and CO2,
ultimately resulting in higher conversions in a single-stage reactor.
In addition, MRs also eliminate the need for excess steam for the
reaction, which is needed in conventional WGS reactor without H2
removal, and minimize the need for downstream H2 purification.
In Table 3 (entry 3) a list of membranes used in WGSMR is given.
Most studies utilize high temperature membranes including dense
Pd [98–101], microporous silica [102–104], zeolite [105,106] and
CMS membranes (CMSM) [107–109]. Pd membranes when used in
WGSMR deliver high CO conversions and high-purity H2. However, Fig. 12. Water gas shift membrane reactor (WGSMR).
Fig. 11. System layout for IGCC system with membrane-based CO2 capture [46].
Co/Mo/Al2O3 catalyst, both of which show high tolerance for H2S High hydrogen production efficiency: according to the authors
and NH3, the main impurities in the syngas produced from coal more than 40% higher than the conventional biomass gasifica-
and biomass. By means of this approach, termed the “one box” tion systems in terms of hydrogen production.
process, not only the H2 purification step, but also the use of a Low cost: reduction of biomass feed and its handling cost for
separate syngas pre-treatment are avoided compared to the the same quantity of hydrogen produced; reduction/elimina-
conventional dual bed WGS (Fig. 13A and B). tion downstream processing steps.
With a view to considerably reducing the cost of H2 production Low emissions: minimum combustion products released to atmo-
by biomass gasification, a specific membrane reactor design has sphere.
been proposed and investigated by Doong et al. [113] in the Project High purity: No additional hydrogen separation/purifica-
PD-070 entitled “One Step Biomass Gas Reforming-Shift Separa- tion (PSA)
tion Membrane Reactor” coordinated by the Gas Technology
Institute (GTI) and recently completed (June 2013) in the frame-
work of Hydrogen Program for the development of hydrogen H2
technologies to establish the “long-term viability of hydrogen as H 2 permselective membrane
an energy carrier for transportation and stationary power” [114].
Retentate gas
In this new gasification concept, a H2 permselective membrane is Feedstock
incorporated into the freeboard region of a bubbling fluidized bed
Freeboard
reactor in order to extract directly hydrogen from the syngas region
(Fig. 14). The membrane module consists of a gas conditioning/
cleaning reactor, a booster compressor, and a water gas shift
reactor to enhance the hydrogen generation from the producer
gas followed by the selective membrane.
In Fig. 13 C a scheme of H2 production by biomass gasification
based on membrane gasification reactor is given. v
Separating off H2 directly in the gasification reactor (where 50–
60% of the total H2 is produced) allows to maximize H2 production
Steam/O2
by shifting the WGS equilibrium displacement (Eq. (1)) as that of or
steam reforming reaction. Moreover, the WGS reaction carried out Air
in a membrane reactor at high temperature induces an increasing
membrane extraction efficiency.
In summary, the advantages of the proposed hydrogen mem-
Ash
brane gasifier concept over conventional gasification technologies
are: Fig. 14. Scheme of membrane gasification reactor [113].
biomass
Gasifier
oxygen Gas clean-up HT-WGS LT-WGS PSA H2
steam
Contaminants
, Optional Pd membrane
CO2 separator to deliver
highpurity H2 for fuel
cells
biomass CMS/WGS
Gasifier Membrane Pd
oxygen H2
Reactor Warm gas Membrane
steam cleanup
Syngas containing impurities
typically present in biomass-
derived syngas(H2 S, NH3 )
High T resistant
membrane H2
biomass
Gasifier
oxygen
Gas
steam cleaning
CO2 removal l CO2
Power generation
Fig. 13. H2 production by biomass gasification based on (A) conventional gasifier, (B) WGSMR, with an optional Pd membrane separation stage for high purity H2 for fuel
cells, [112], (C) membrane gasifier reactor [113].
Highly efficient generation of electricity when combined with a the biomass gasification, i.e. temperatures above 700 1C and
fuel cell. pressures above 20 atm. In addition to the optimization of Pd–Cu
alloy membranes with respect to sulfur resistance and other non-
On the basis of GTI’s study, hydrogen membrane gasifier concept sulfur contaminants, other high temperature, sulfur poisoning
can potentially improve the hydrogen production efficiency by resistant, hydrogen selective membranes such as high-
more than 40% based on thermodynamic analysis, thereby reducing temperature ceramics and multiphase membranes such as cermet
the costs of the feedstock and the gasification unit for the same membranes (composite membranes composed of hydrogen-
quantity of hydrogen produced. The syngas generated from biomass transporting metal embedded in a thermodynamically stable,
gasification is usually converted to power and heat via IGCC for proton-conducting, ceramic matrix) could be tested and employed
larger plants or Reciprocating Internal Combustion Engine (RICE) in the membrane gasification reactor (Table 4).
for smaller units. Combination of gasification processes with
advanced technologies such as fuel cells may produce electricity 2.1.1.2. Fast pyrolysis. Pyrolysis corresponds to the thermal
without pollution. One scenario for the fuel cells to operate with transformation of biomass under inert atmosphere. Three phases
biomass as the energy source is to use directly the hydrogen are produced: gases, liquids (tars, condensable vapors, etc.) and
produced from the proposed membrane gasifier to generate elec- solids (char) (Scheme 2). Their fractions depend on the operating
tricity (Fig. 15). The operating temperature of PEMFCs is typically conditions. For example, at low temperatures or small heating
low and, as a result, common impurities found in conventional rates, char production is enhanced (carbonization) and therefore
hydrogen production for example CO, can be adsorbed and poison in these conditions this process is not attractive for producing
the catalysts used. Therefore, high-purity hydrogen is required for hydrogen. In the early 1990s fast pyrolysis technology was
the operation of such systems. The hydrogen produced from the developed on a commercial scale: fast heating rates, higher
proposed membrane gasifier concept can meet this stringent temperatures and short residence times (of the order of a few
requirement because the membrane materials identified for its seconds) can produce high yields of either liquids (so-called
application are 100% selective to hydrogen. bio-oils) or gases (CO, H2, CO2 and light hydrocarbons) [129].
In membrane gasification reactor the research and selection of In particular, as the temperature increases from 500 to 750 1C, the
resistant and efficient membranes is a major challenge. char and bio-oils yields decrease while the yield of the gaseous, in
Pure Pd membranes with their infinite selectivity along with particular of H2 as a percentage of the total gases evolved,
high hydrogen permeability are not resistant to such poisons as CO increases. Recently, Uddin et al. [130] emphasized the influence
and H2S which are typical components of producer gas from of biomass characteristics and compositions, moisture content,
gasification process. Incorporation of another metal into Pd may particle size, heating rate, temperature, reactor system, and carrier
improve chemical stability. Considerable work has been done with gases and catalysts on the production of H2, CO,CO2, and CH4,
Pd–Cu membranes because Cu is not as costly a material as Ag and generated by the pyrolysis process. The composition of the non-
Pd–Cu alloys do not show embrittlement [115–119]. Promising condensable gases varies widely depending on the properties of
membranes are those based on Pd–Cu alloy, which has been the biomass and moisture content, which play key roles on the
assessed over a wide range of temperatures (to 900 1C) and mole fraction of H2 in the final products.
pressures (to 35 atm) for its hydrogen permeability [120]. The Reforming non condensable gas into H2 via a shift reaction is
alloys containing 53%, 60% and 80% of Pd by weight have demon- significant in increasing the total hydrogen formation in the
strated negligible decreases in flux in the presence of 1000 ppm presence of catalysts.
H2S [120]. A possible explanation of the higher resistance to sulfur As for gasification, also for pyrolysis in comparison to
poisoning of Pd–Cu alloys is found in the recent work of Ozdogan conventional configuration in which the thermo-chemical pro-
et al. [121]. Therefore, Pd–Cu membranes were identified as cess is combined with catalytic steam reforming (or auto-
preferred candidate materials for hydrogen separation application thermal reforming), WGS and downstream separation units,
in the membrane gasification reactor [113] under the conditions of the use of membrane reactors can bring various potential
H2 CO, H , CO , CH
PEM
Fuel cell
biomass Biomass Volatiles (Tar) Secondary Tar (bio-oils)

Gasifier
oxygen
steam power
Char/Coke
Fig. 15. Membrane gasifier integrated with PEMFC [113]. Scheme 2. Biomass pyrolysis products.
Table 4
High temperature resistant , hydrogen permselective membranes.
Membrane type Membrane material T (1C) Permeability H2 [10 13 (mol/m/m2/s/Pa)] Refs.
Ceramic–metal composite (cermet)a Ni–Ba(Zr0.1Ce0.7Y0.2)O3 δ 900 8.7 [122]

Ceramic–metal composite Pd–Ce0 8Gd0.2O2 δ 900 540 [123]
Ceramic–metal composite Pd-YSZ (Pd/Y stabilized ZrO2) 900 330 [124]
Ceramic–metal composite Pd–CaZr0 9Y0.1O3 d 900 390 [125]
Dense ceramic membranes La5.5WO11.25 δ 4700 – [126]
Dense ceramic membranes La0.99Ca0.01NbO4 1000 0.22 [127]
Dense ceramic membranes La5.5WO12 δ 900 – [128]
Dense ceramic membranes BaCe0.2Zr0.7Yb0.08Ni0.02O3 δ 600–900 – [128]
a
Composite membranes composed of metals embedded in proton-conducting ceramic matrix.
advantages such as reduced capital costs, due to the reduction Membrane operations such as nanofiltration (NF), reverse
in size of the process unit, improved yields and selectivity due osmosis (RO), forward osmosis (FO) have been investigated for
to the equilibrium shift effect (as discussed above for gasifica- treatment of the aqueous fraction of bio-oils for dewatering [62],
tion) and reduction downstream separation costs, due to the removal and recovery of acids [51], separation of sugars [52]. For
integration of separation. each case study, the main characteristics (membrane materials,
Fig. 16A reports a scheme of the conventional route for H2 types) and advantages of membrane operations compared to
production from biomass pyrolysis, whereas Fig. 16B shows the conventional treatments are summarized in Table 5.
integration with MRs. The presence of MRs for steam reforming In various studies related to biomass pyrolysis [136–139],
and WGS reduces the three reaction stages plus a PSA unit in only hydrogen production occurs in two stages: fast pyrolysis of
two reactors able to produce pure hydrogen. Least but not last, in biomass to generate bio-oils and catalytic steam reforming of
both MRs the conversion is enhanced, as discussed above for bio-oils to hydrogen and carbon dioxide. There are concepts to
gasification and illustrated in Fig. 12. Therefore, the overall process produce hydrogen from either the whole bio-oils or from only the
yield is maximized. residual fractions after co-products have been separated. Consid-
As mentioned above, fast pyrolysis produces bio-oils with yields ering for example lignocellulosic biomass, the cheapest and most
as high as 70–80% based on the starting biomass weight [131]. The abundant form of plant biomass for the production of bio-fuels,
production of bio-oils is one of the advantages of fats pyrolysis which includes trees, grasses, energy crops and agricultural
compared to gasification: bio-oils represent an intermediate energy wastes, its hydrogen content is only 6–6.5 wt% compared to almost
carrier, that can be stored and transported economically, so that the 25 wt% in natural gas. Therefore, only an integrated process, in
upstream biomass conversion via pyrolysis and the downstream which biomass is partly used to produce more valuable materials
processing of bio-oils can be carried out at different locations, times or chemicals, while the residual fractions are utilized for the
and scales. generation of hydrogen, can be economically viable in today’s
Depending on its source, bio-oils typically contain water (about energy market [134,138,140]. This process concept can be
20–30 wt%) and organics (about 70 wt%) such as acids, ketones, improved significantly in terms of yield enhancement, reduction
aldehydes, sugars, alcohols, esters, furans, furfurals, and some char of energy load, by means of integration of membrane operations
particles micron sized [132,133]. such as NF, RO (Table 5) and MRs as shown in Fig. 17, which
Due to their insolubility in petroleum derived fuels, corrosive- represents an integration of Fig. 16B.
ness, phase instability, high viscosity, and high char content, bio- Biomass is fed into pyrolysis reactor which produces char,
oils are not currently considered fuels themselves [134]. Upgrading organic vapors and gases in different ratio depending on the
is necessary to meet fuel specifications and demands. operative conditions as mentioned above. CO-free H2 by means
Bio-oils can be separated into an aqueous phase and a heavier of MRs can be produced both from the gas coming out the
organic phase upon addition of water. The aqueous fraction of bio- condenser via catalytic steam reforming and WGS MRs (Fig. 17,
oils contains sugars, organic acids, hydroxyacetone, hydroxyace- top) and from either the whole bio-oil (path a) or from only the
taldehyde, furfural, and small amounts of guaiacols that may be aqueous soluble fractions after co-products have been separated
further upgraded to produce not only hydrogen, but also alkanes, (path a0 ). The water insoluble compounds (pyrolytic lignins,
aromatics, or olefins [135]. monophenols) can be treated to produce chemicals [138,140].
Low Temp High Temp

H2 PSA
WGS 200°C WGS 370°C
Cyclone Catalytic Steam

Condenser Reformer
separator
Biomass H2, CO, 750-850°C
Pyrolysis CO2, CH4
reactor
Bio-oils
Char/Carbon
H2 WGS
300°C

Condenser Reformer
separator
Biomass H2, CO, 500°C
Pyrolysis CO2, CH4
reactor
Bio-oils
Char/Carbon
Fig. 16. Scheme of (A) conventional and (B) innovative, integrated by membrane reactors, biomass pyrolysis plants for hydrogen production.
Table 5
Upgrading of pyrolysis oil by membrane technology.
Case study Process targets Traditional Membrane Membranes Status of Advantages (A)/challenges (C) Refs.
technology operations (membrane membrane
materials) technology
application
Removal of char Removal of char particles 41 μm and o 10 μm from bio-oils – MF Membraloxs TI-70 Lab scale A: Easy removal of char particles 41 μm from bio-oil [149]
particles down to a target of 0.01 wt% for improving the applicability of (alumina C: Membrane fouling with cake formation requires a
bio-oil as fuel membrane tube) detailed investigation in terms of operative conditions able
to reduce it , e.g. the cross-flow velocity and the
concentration of char particles present in the feed stream
Removal and Recovery Organic acids separation: reduction of corrosion problems Ion exchange NF, RO GE Osmonics Desal Lab scale A: Selective, easy removal of organic acids, which can be [51]
of organic acids in down-stream processing equipment Extraction DK (aromatic recovered in the permeate streams without use of
Organic acids recovery: realization of an integrated Vacuum polyamide) Koch stoichiometric reagents
process economically viable: biomass is partly used to evaporation MPF 34
produce more valuable bio-products, while the residual Distillation GE Osmonics RO C: Irreversible damage of the membranes due to the
fractions are utilized for the generation of hydrogen AG (aromatic interactions of phenolics compounds with membrane
polyamide) materials. different, resistant polymer formulation and/or a
GE Osmonics RO pre-treatment step to remove phenolics are required to
CE (cellulose realize a practical membrane process
acetate)
Concentration of the Concentration of the hydrolyzed aqueous fraction solution Vacuum RO Alfa Laval-RO90 Lab scale A: Fast, easy concentration of monosugars in the retentate [52]
monosugars in the before and after the solvent separation to remove phenolic evaporation (thin film stream
hydrolyzed aqueous lignin fragments composite C: Membrane fouling due to the presence of phenolic
fraction membrane on compounds, which decreases the efficiency of the process.
polyester support) Therefore, a pre-treatment step (i.e. solvent extraction)
before membrane treatment is necessary for the success of
the process
Separation of organic Removal of phenols and furfural by aqueous phase and Distillation PV Silicone rubber Lab scale A: Efficient separation of phenols and furfural from aqueous [61]
compounds from subsequent concentration Evaporation RO membrane (PV) phase by means of PV
biomass pyrolysis- polyamide
derived aqueous nmembrane. (RO)
solution
Dewatering of Removal of water without valuable components dissolved Liquid–liquid FO using Cellulose triacetate Lab scale A: FO process is a promising process for removing water from [62]
pyrolysis oil from the aqueous phase of the pyrolysis oil sedimentation NaCl and membrane the pyrolysis oil aqueous phase
aqueous phase process MgCl2 draw (developed by C: Appropriate draw solutions and membranes should be
Ceramic solutions Hydration investigated for practical application, i.e. reasonable
Microfiltration Technologies fluxeswith minimal or negligible reverse solute flux
Innovations)
1359
H WGS
300°C

Condenser Reformer
separator
Biomass H , CO, 500°C
Pyrolysis CO , CH
reactor
Char/Carbon Bio-oils
water
Phenolic Phenolic Separation

resins intermediates
Water soluble
a) compounds
Concentrated
NF, RO
Aqueous fraction of bio-oil
Corrosive organic
a)’ compounds
WGS Steam Reformer
H
or Autohermal
Reformer
Biodiesel
glycerin/lipids Trap grease Processed food
Transesterification Food processing
Plants & animal fats
Fig. 17. Biomass pyrolysis to hydrogen: process concept via innovative plant integrated by membrane reactors (adapted from [138]).
The aqueous soluble organics, after NF, RO treatments to remove staged reactor concept has been introduced: by lowering the
organic acids, in order to reduce bio-oil corrosiveness, or to temperature of the fluidized bed from 850 1C to 432–500 1C, its
concentrate sugars (see Table 5), can be further reformed to function is changed from a gasifier to an evaporator, and in this
produce H2 via steam reforming or autothermal reforming (ATR) way vaporized pyrolysis oil compounds (instead of a fuel gas), can
and WGS (path a0 of Fig. 17). more readily convert in the subsequent catalyst bed for traditional
Steam reforming of bio-oil is still in an early stage of develop- reforming at temperatures 4750 1C. This approach assures
ment and far from industrial application mainly due the short extended high activity of the catalyst, but with reduced hydrogen
lifetime of the catalysts [141] and the very high steam to carbon yields.
ratio used to avoid coke deposition, which increases the energy A MR concept applied to bio-oil steam reforming followed by
demand of the plant. First studies on steam reforming chemistry of WGS could: (i) increase the overall efficiency of the process due to
biomass pyrolysis-derived liquids, i.e. bio-oil, are by Chornet and integration and intensification; (ii) reduce the reformer operating
co-workers [138,142], who initially focused their research on the temperature ( o700 1C); produce hydrogen, with very high purity
catalyst development for processing only the aqueous carbohy- (CO-free) without need of additional expensive gas separation
drate derived bio-oil fraction [143]. They also identified the step; (iii) reduce in process units such as heat exchangers. From
shortcomings of the traditional fixed-bed steam reforming process our best knowledge, no research articles on membrane steam
used for natural gas or naphtha in the application to bio-oil: the reforming of pyrolysis bio-oil are reported in literature. Only
steam reforming reaction competes with the gas-phase thermal membrane steam reforming of acetic acid, chosen as intermediate
decomposition reaction of bio-oil resulting in coke formation that liquid bio-fuel model, has been investigated at relatively low
can plug the reactor and deactivate the catalysts. Rioche et al. [144] temperature of 400 1C with H2 yield and CO-free H2 recovery
investigated catalytic steam reforming of whole bio-oil produced around 50% and 70%, respectively [75,76]. A Ni-based commercial
by fast pyrolysis of beech wood that includes the oligomeric lignin catalyst (packed in the lumen side of the membrane reactor) was
derived material. With fixed-beds of ceria-zirconia supported used. However, the state-of-the-art in catalytic reforming for the
noble metal catalysts (Pt, Rh) they obtained hydrogen yields production of hydrogen mainly concerns the high temperature
between 50 and 60% of the stoichiometric potential and the range ( 900 1C) and commercial catalysts such as Ni-based
carbon-to-gas conversion of 90% during a 9-h operation. Czernik catalysts have been designed to face most constraints of the
et al. [139] obtained the highest yields of H2 (80% of the stoichio- process at these conditions. The main advantages of MRs, namely
metric potential) by steam reforming whole bio-oil in a fluidized operation at much lower temperatures and lower steam-to-carbon
bed of nickel catalyst (in all tests the process temperature was ratio, pose great challenges for conventional catalysts such as Ni-
850 1C). However, this yield decreased in longer duration catalytic based catalysts for steam reforming because at these conditions
tests due to catalyst deactivation for both incomplete carbon to gas the catalysts are much less active. Thus, MRs integrated in steam
conversion, which resulted in carbon deposits, and presence of reforming process require the development of novel catalysts by
inorganic impurities in the bio-oil. To overcome these drawbacks, exploring the catalytic behavior of new metal nanoparticles and
Van Rossum et al. [145,146] focused their attention on the reactor new supports, with a high activity and a good selectivity at much
type more than on the catalyst: a disadvantage of a fluidized bed lower temperatures than in conventional catalytic reformers. This
reactor is that it operates at a single high temperature, and both concept may be extended also to ATR, an attractive alternative to
evaporation and the endothermic reforming take place in a single steam reforming to produce hydrogen from bio-oil [147,148]. ATR
vessel, which requires a very high single heat duty. Therefore, a is a combination of steam reforming (endothermic) and partial
oxidation (exothermic) to produce CO, CO2 and H2. ATR has many
[156,157,158,159]
advantages compared to steam reforming especially for small scale
[156,158,159]
[157,158,159]
distributed production of hydrogen from bio-oil. Among them,
[164–166]
Not available, but assumed higher than Not available, but assumed higher than [161–163]
[158,159]
[157,159]
(i) the heat generated from the partial oxidation of bio-oil can be
provided to the endothermic steam reforming; (ii) the water
Ref.
produced as by-product in the oxidations can be used during
steam reforming, reducing in this manner the external water and
energy required for producing excess steam.
1.9% (theoretical limit 68% [160])

H2 synthesis rate (mmol H2/L/h) [155] Conversion efficiency [155,156]
2.1.2. Biological production of energy carriers and their upgrading
2.1.2.1. Some general considerations. The important advantage of
biological processes over thermo-chemical methods is represented
by the mild operations conditions. Methane production through
individual stages
anaerobic digestion of wastewater and residues (including sewage
sludge, manure and the organic fraction of municipal waste) is
60–80%b
already broadly applied [150].
0.5–2%a
Section 2.1.2.2 of this article is devoted to discuss the combina-
78c
–
–
tion of methane, produced by biological methods, with membrane
processes. In particular, the integration with membrane bioreac-
tors to enhance biomethane production (Section 2.1.2.2.1) and its
purification via membrane gas separation (Section 2.1.2.2.2) are
discussed.
Section 2.1.2.3 is focused on hydrogen produced by biological
processes (bio-hydrogen). The potential of bio-hydrogen is recog-
nized worldwide. The Netherlands is very active in the research on
individual stages
the application of bacteria for H2 production from biomass, similar
as Sweden, Hungary, Turkey and the UK. Also in Asia, Canada, and
especially in the US, biological H2 production is seen as one of the
Overall energy efficiency including the applied voltage and energy in the substrate. It does not include hydrogen purification.
0.355
options for renewable H2 production on the longer term, as
0.07
0.16
121
5.8
96
presented in the US document ‘National Hydrogen Energy Road-
map’ [151]. The progress in research on hydrogenase enzymes and
Fermentative bacteria, Photosynthetic bacteria
Fermentative bacteria followed by anoxygenic

basic physiological parameters of hydrogen producing bacteria
forms the basis for continuation and expanding the developments
in Europe following the approach of The Netherlands [152,153].
In the anaerobic digestion (Fig. 15), hydrogen is an intermedi-
ary product that is, however, not available because it is rapidly
taken up and converted into methane by methane-producing
Purple bacteria, microalgae
Microalgae, Cyanobacteria
microorganisms.
Microorganisms used
Fermentative bacteria
phototrophic bacteria
Several processes are currently under development for the

production of bio-hydrogen, ranging from biomass fermentations
to photo-biological processes. In Table 6 an overview of the
Microalgae
biological hydrogen production processes, that are being explored

in fundamental and applied research, is given. The production of Maximum theoretical yield of 4 moles H2 per mole glucose catabolized.
hydrogen from a dark fermentation metabolism, which has favor-
able operational costs and high yield compared to the other
technologies (Table 6), blocking the methanogenesis in the anaero-
Stage II (photo-fermentation):
C6H12O6 þ 6H2O-12H2 þ 6CO2
bic pathway, is one of the key issues, due to the conversion of

Stage I (dark fermentation):
CH3COOH þ2H2Oþ light-4

CH3COOH þ2H2Oþ light-
C6H12O6 þ 2H2O-4H2 þ 2
12H2Oþlight-12H2 þ O2
hydrogen to methane in this step (see Fig. 18) Another important

Biological hydrogen production processes, modified from [154].
2H2Oþlight-2H2 þO2
issue in the production of hydrogen, from anaerobic fermentation,

CO þ H2O-CO2 þ H2
General reactions
is the type of fermentation, as discussed in Section 2.1.2.3.

CH3COOH þ2 CO2
2H þ þ2e -H2
Biological production of hydrogen is an exciting area of tech-

4H2 þ2CO2
nology development that offers potential production of usable

H2 þ2CO2
hydrogen from a variety of renewable resources. But, there are

some questions. Can biohydrogen production systems be devel-
oped at a practical and commercial scale? And more specifically,
Microbial aided electrolysis
Can biohydrogen production systems be integrated with hydrogen

Water gas shift reaction
fuel cell technologies to generate electricity at a practical scale

Light conversion efficiency.
Hybrid (or multi-stage)
Indirect Biophotolysis
(“stand-alone system”)?
Direct Biophotolysis
Photo-fermentation
Dark fermentation
Both bio-methane and bio-hydrogen production methods are

inherently extensive processes i.e. requiring relatively large pro-
cells (MEC)
cess volumes. Furthermore, the feedstock (wet biomass or bio-

Entry Process
system
waste) cannot be easily transported over large distances. Based on

these two characteristics, relatively small-scale production sys-
tems are located where bio-wastes or other biomass sources
Table 6
should be available. This leads to two possible configurations for

b
a
c
1
2
3
4
5
6
the ‘production to end-use chain’. Either the gas is used directly at

Complex organic compounds the point of production or the gas is supplied to an existing grid for
Carbohydrates, proteins, fats use at another location. The first type of system is indicated as
“stand-alone system” and the second as “grid-connected produc-
Hydrolytic bacteria Hydrolysis tion systems”. Levin et al. [159] answered to the second question
(reported above) by calculating the size of bio-hydrogen systems
Simple organic compounds
that would be required to power PEMFCs of various sizes. The
Sugar, amino acids, fatty acids
advantages of membrane processes over conventional processes
Acidogenic bacteria Acidogenesis such as reduced capital cost, lower energy consumption, lower
installation costs due to their modular design and simplified
Organic acids and operation would make them very suitable for “stand-alone sys-
alcohols
Acetogenesis tem”. In this context, there is the issue of bio-hydrogen production
Acetogenic bacteria and upgrading assisted by membrane processes, discussed in
Section 2.1.2.3.
Acetic acid and
H2, CO 2 2.1.2.2. Biomethane. In recent years, interests in anaerobic
acetate
biological treatment have increased because of merits such as
lower energy consumption, low sludge production, and biogas
Methanogenic bacteria Methanogenesis
generation.
CH4 , CO2 In 1984, the first centralized biogas plant was established in
Denmark. This plant, like most of its successors, was equipped with
combined heat and power production facilities, as heat was
Fig. 18. Anaerobic decomposition process for the production of biogas.
supplied to a nearby village and electricity was sold to the
electricity grid. The main purpose of this and other early centralized
plants was energy production. It later emerged that centralized
biogas plants make a significant contribution for solving a number
of environmental problems in the fields of agriculture, waste
recycling, and greenhouse gas reduction. In recognition of these
advantages, the Danish government has supported the develop-
ment in different ways: appropriate legislative framework, various
research and development programs, investment grants, and other
subsidies.
Anaerobic processes have been widely and effectively used in
the solid waste treatment (e.g. landfill) and in the wastewater
sector for sludge treatment. Biogas is generated under mesophi-
lic (20–40 1C) or thermophilic (up to 60 1C) temperatures, con-
sisting of methane (CH4) and carbon-dioxide (CO2) along with
some trace gases such as water vapor, hydrogen sulphide (H2S),
nitrogen, hydrogen and oxygen. The composition of biogas varies
depending upon the origin of the anaerobic digestion process.
Landfill gas typically has methane concentration around 50%.
Advanced waste treatment technologies can produce biogas with
55–75% methane, which can be increased to 80–90% methane
using in-situ gas purification techniques (see next paragraphs).
Biogas is the end product of anaerobic decomposition process,
which can be divided into four distinct phases (hydrolysis,
Fig. 19. AnMBR with membrane unit external to reactor [168]. acidogenesis, acetogenesis, and methanogenesis) (Fig. 18).
Fig. 20. Submerged bioreactor with membrane unit external to reactor [173].
During each phase, various microorganisms and enzymes work a longer SRT would benefit methanogenesis (Fig. 18) and lead to
symbiotically. more biogas generation [177].
2.1.2.2.1. Biomethane generation. Anaerobic biological process A recent study by Lin et al. [178] demonstrated the technical
assisted by membranes could provide excellent suspended solids and economic feasibility of SAnMBR treating municipal waste-
removal and improved biomass retention for wastewater treat- water, providing that the membrane performance was signifi-
ment. This combination improves the biological treatment process cantly improved or membrane price significantly decreased. In
while allows the recovery of energy through biogas. Anaerobic particular, a laboratory-scale SAnMBR (Fig. 22a) was operated for
membrane bioreactor (AnMBR) as the case of WGSMR, (discussed 106 days for municipal secondary wastewater treatment. The
above in Section 2.1.1 Hydrogen from biomass thermo-chemical results of laboratory-scale experiment were used to full-scale
conversions) is a classic example of PI, i.e. “development in the SAnMBR design. The study revealed that the SAnMBR for munici-
process equipment or method that contributes to dramatic pal secondary wastewater treatment was technically feasible in
improvements in manufacturing and processing, resulting in a terms of COD removal, sludge production and biogas yield. Cost
cheaper and more sustainable technology” [11]. In particular, the analysis of the full-scale SAnMBR system (Fig. 22b) showed that
difficulty in retaining slow-growth anaerobic microorganisms with membrane costs and gas scouring energy accounted for the largest
short hydraulic retention time (HRT) [167] could be resolved by fraction of total life cycle capital costs and operational costs,
using AnMBR: the membrane can retain biomass effectively, respectively. The operational costs can be totally offset by benefits
producing a solids-free effluent and prevent unintended sludge from biogas recovery.
wasting. Low-pressure membrane filtration, either UF or MF is Anaerobic wastewater treatment is especially suitable for high
used to separate effluent from activated sludge. Most of AnMBRs strength wastewaters and could operate in higher loading rates.
studied employ a membrane externally connected to the reactor Furthermore, with the advantages of biomass retention,
(Fig. 19) [168]. While external AnMBRs show the advantages listed
above, they still have several drawbacks.
High hydraulic shear force associated with external configura-
tion involves an important source of energy consumption, and also
disrupts anaerobic bio-solids, favoring small particle sizes, which
significantly increase membrane fouling. In addition, the high
shear stress has been observed to harm the biological activity of
anaerobic biomass [169]. Considering these drawbacks, together
with the positive experiences gained from the successful applica-
tion of aerobic submerged MBR (SMBR) for wastewater treatment
(Fig. 20), submerged anaerobic membrane bioreactor (SAnMBR),
which is believed to be able to overcome the drawbacks men-
tioned above, has recently attracted more interests [170–172].
In SAnMBR, the membrane is submerged directly in the
bioreactor (Fig. 21a) or in a separate tank (Fig. 21b) and filtration
takes place by applying vacuum to the inside of the membrane. To
reduce cake formation on the membranes in SAnMBR, the pro-
duced biogas is recirculated and used instead of air bubbling in
aerobic submerged MBRs [174–176].
SAnMBR could achieve excellent treatment performance in
terms of COD removal and biogas production for treating low
strength synthetic wastewater in long-term operation.
A longer SRT (solid retention time) operation achieved a better
treatment performance. Biomass concentration and biogas pro-
duction rate were affected significantly by both SRT and HRT. With
a shorter HRT, biomass concentration was higher, which conse-
quently resulted in higher methane production. On the other hand, Fig. 22. (a) laboratory-scale and (b) full-scale SAnMBR [178].
a b
Biogas Biogas
permeate retentate
permeate
Gas sparging
Feed Feed
Biomass waste Biomass waste
Fig. 21. Two possible configurations of AnMBRs.

Table 7
Selected characteristics of AnMBRs for wastewater treatment.
Wastewater T (1C) HRT (h) Flux (L/m2/h) CODfeed (kg/m3) Efficiency (%) Membrane type/configuration Ref.
Pretreated alcohol distillery 55 250 – 40 490 1. Polypropylene [188]

2. Zirkonia skinned inorganic
External MF-cross flow
Food wastewater 37 42 – 15 90 Polyethersulfone UF [189]
External cross flow
Acetate and ethanol based synthetic wastewater 33 24 4.7 1-5.9 80 Polysulfone, pore size 0.2 μm [190]
Submerged
Synthetic wastewater 55 6 16–23 5 – Polysulfone, pore size 0.2 μm [191]
Gas-sparged submerged
Cheese Whey 37 24 – 70 98.5 Ceramic membrane [179]
External MF cross flow
Synthetic wastewater 55 – 7 – – Submerged [192]
Sucrose, meat extract based synthetic wastewater – 6 9 4 98 Polyethylene, pore size 0.4 μm [180]
Submerged
Synthetic wastewater 30 – 15 10–11 – Tubular MF [193]
External
Thermo-mechanical pulping whitewater 37 – 4.8-9.1 – 90 Submerged [176]
Table 8
Comparison among different techniques for biogas upgrading (modified from Ref. [194]).
Technique Cost price Maximum Maximum Advantages Disadvantages

upgraded achievable yield achievable purity
biogas % %
Chemical 0.28 90 98 Almost complete H2S removal Removal of one component

absorption in column
Regenaration step expensive
High pressure 0.15 94 98 High purity, good yield H2S damages equipment
water Simple technique, no special chemicals or High water quantity required, even
scrubbing equipment required with the regenerative process
Pressure swing 0.26 91 98 497% CH4 enrichment Additional complex H2S removal
adsorption Low power demand step needed
Adsorption of N2 and O2
Membrane 0.22 78 89.5 Easy process Relatively low CH4 yield

separation Easy control and scale-up Membrane cost expensive
Large operational flexibility
Low energy requirements
Small footprint due to high packing densities of
membranes in the membrane modules
Product gas already at natural gas grid pressure.
anaerobic membrane bioreactors are able to operate at higher Studies on AnMBR conducted with low to medium strength
loadings conditions. In addition, considering the excellent bio- wastewater have generally achieved more than 90% removal
mass retention by membranes, the application of thermophilic efficiencies. Most of them have used biogas bubbling as a fouling
conditions and particulate wastewater conditions, it is expected reduction strategy and achieved successful performances [180,181].
that AnMBR performances would be successful. A summary of Methane yield is an important parameter which reflects the
performances of selected studies on AnMBR is listed in Table 7. performances of the anaerobic wastewater treatment systems. As
Most of the studies were based on synthetic wastewaters at the the research on AnMBR is still under development, the issue of
initial stage due to the easiness in process control. The feed biogas yield optimization has not gained much attention. However, a
solutions used in these studies were: volatile fatty acids (VFA), couple of studies, which reported the methane yields, indicate
sucrose, glucose, simulated domestic wastewater, and simulated around 0.27–0.36 m3 CH4/kg CODR [182–184], in the range of yields
high salinity wastewaters. Among these studies, almost all have of other high rate anaerobic reactors, but the effluent quality is not
achieved removal efficiencies higher than 90%. The use of indus- good in terms of suspended solids removal. An extensive treatise of
trial or other types of high strength real wastewater was also anaerobic membrane bioreactors is far beyond the scope of this
studied and very good removal efficiencies as well have been paper and further reading of the recent reviews [185–187] on the
observed. For example, Saddoud et al. [179] studied cheese whey subject is recommended.
effluents with COD in the range of 12–80 kg/m3 and COD loading 2.1.2.2.2. Biomethane upgrading. In a controlled reaction system,
of 3–20 kg COD/m3/d. Interestingly, the study was able to achieve the gaseous mixture produced in anaerobic digestion of biological
98.5% of COD removal efficiency. resources and most interestingly of biological waste can contain up
to 70% of biohydrogen and biomethane that can be used after

purification. Purified biogas enriched in H2 could be used as a feed
to fuel cell. Similarly, CH4 could be used for domestic applications,
automobile fuel and power generation. Carbon dioxide and trace
gases such as water vapor and H2S must be removed before the
biogas use because water vapor may cause corrosion when com-
bined with H2S on metal surfaces and reduce the heating value.
When distributing the biogas using pipelines, oil and gas pipeline
standards may become applicable. Producing pipeline quality gas
requires the use of advanced technologies such as chemical absorp-
tion, high pressure water scrubbing, cryogenic separation, pressure Fig. 23. The process equipment for a membrane-based upgrading process [197].
swing adsorption and membrane separation. Each technique has its

advantage depending on the goal. Both high pressure water scrub-
bing and membrane separation are easy to operate and no membranes, i.e. high-temperature separations and separations of
chemicals are needed. In Table 8 an overview of the main variables aggressive media [209]. Polymeric membranes dominate traditional
to be evaluated for their comparison is given [194]. gas separations because they are (i) much cheaper than inorganic
Detailed information on conventional upgrading equipment is membranes, (ii) easily fabricated into commercially viable hollow
available in Refs. [195,196]. Scholtz et al. [197] compared the fibers or flat sheets that can be processed into hollow fiber or spiral
various conventional upgrading processes in terms of electrical wound modules, (iii) in advanced stage of development, (iv) stable
and thermal energy demand as well as specific upgrading costs. at high pressures, and (v) easily scalable. Polymeric membranes
Gas permeation membranes have been applied to natural gas exhibit inverse permeability/selectivity behavior (‘upper bound
treatment [198–204]. trade-off’ curve plotted between selectivity and permeability of
Biogas upgrading deals primarily with the separation of CO2 gases) [210,211].
and CH4. Actually, the same task is performed for upgrading Mixed matrix membranes (MMMs) formed by dispersing
natural gas. Therefore, research results published on natural gas inorganic filler in a polymer matrix offer a viable approach
upgrading with membranes can be applied to biogas upgrading. towards combining the low cost and processability of polymeric
However, the process conditions in natural gas treatment and membranes with the high selectivity and permeability of inorganic
biogas upgrading are different. The natural gas is under pressure membranes [212–233].
when it leaves the natural gas field whereas in biogas upgrading, Several molecular sieving materials such as zeolites, carbon
the raw gas has to be compressed to the pipeline pressure. molecular sieves (CMS), carbon nanotubes (CNTs), metal–organic
Basically, two entirely different membrane processes can be frameworks (MOFs) and covalent organic frameworks (COFs) are
applied for the separation of CO2 and CH4: membrane gas separa- used as filler to prepare MMMs. The aim was to achieve better
tion (permeation)and membrane contactors. The first one is permeability and/or selectivity and to overcome the limitations of
already mature and frequently applied [197]. the ‘upper bound trade-off line’ that exist for solution diffusion
The potential of membrane gas separation for biogas upgrading type transport in pure polymeric membranes [210,211].
was noticed more than thirty years ago. Schell and Houston In Table 9 a list of membrane materials suitable for biogas
reported on a process for biogas treatment that used commercial upgrading, i.e. dealing primarily with the separation of CO2 and
cellulose acetate spiral-wound membranes [205]. Harasek et al. CH4 is given.
[206] and Makaruk et al. [207] have reported on a membrane gas In contrast to polymeric membranes which are commercially
permeation plant for biogas upgrading and grid supply of 100 m3 available, MMMs have not reached this stage yet, but their
stp/h of natural gas substitute. Recently, Makaruk et al. [23,208] performance is promising for development on large scale.
discussed and simulated by using numerical modeling membrane
configurations for biogas upgrading. The work proposes basic
concepts for the integration of membrane biogas upgrading into 2.1.2.3. Biohydrogen. Various authors reviewed biological hydrogen
biogas plants while taking into account the permeate utilization production processes [155,156,158,234] both traditional routes such as
and the heating requirements of biogas plants. biophotolysis, indirect biophotolysis, photofermentation, and dark
In Fig. 23 a simplified scheme for gas permeation membrane fermentation and new technologies such as aqueous phase
for biogas separation is given [197]. The membrane-based separa- reforming (APR) and Microbial electrolysis cells [155]. Dark fermenta-
tion plant is mainly designed to remove CO2 from the CH4 bulk. tion continues to be one of the leading technology for biohydrogen
The membranes used are CO2 permeable and therefore separates production with 2–4 orders of magnitude higher hydrogen production
CH4 by retaining it (retentate current is CH4 enriched). In this way, rates than photo-fermentation and biophotolysis systems (Table 6).
the product gas is already at natural gas grid pressure. The raw gas Direct biophotolysis can produce gas of high H2 purity (up to 99.5%)
leaving the fermenter is pressurized up to the grid pressure by a but cannot produce hydrogen at competitive rates to dark
multistage compressor using interstage cooling. Subsequently, the fermentation and photofermentation. Photo-fermentation systems
gas temperature is controlled in a heat exchanger to protect the show H2 production rates values intermediate between those ones
gas permeation membrane from high temperatures. The permeate of dark fermentation and direct biophotolysis (Table 6).
stream is fed to an exhaust gas treatment unit which captures the In dark fermentations, hydrogen is produced by anaerobic
components not to be fed to the environment. A desulfurization bacteria grown in the dark on carbohydrate-rich substrates and its
step of the retentate stream is included. production depends on the type of substrate as shown in Fig. 24.
Single stage gas permeation processes is not enough to produce Fermentation reactions can be operated at mesophilic (25–40 1C),
a high CH4 purity and simultaneously obtain a high CH4 recovery. thermophilic (40–65 1C), extreme thermophilic (65–80 1C), or
Hence, multi stage concepts are mandatory. Two-stage systems are hyperthermophilic (80 1C) temperatures. In dark-fermentation pro-
common. cesses, a mixed biogas containing primarily H2 and CO2, which may
In the past decade, intense research efforts have been made in also contain lesser amounts of methane (CH4), CO, and/or hydrogen
the development and improvement of inorganic membranes for use sulfide (H2S), is produced. Bacteria known to produce hydrogen
in separations that are difficult to achieve by conventional polymer include species of Enterobacter, Bacillus, and Clostridium.
Table 9 CO2
Membrane materials intended for CO2/CH4 separation.
Entry Membrane materials CO2 α (CO2/ Development Ref.

(Barrer) CH4) stage CO2 + H2 CO2+ H2
1 PI 10.7 42.8 Commercial [15] H2
2 CA 6.3 30 Commercial [15]
3 PSf 5.6 22.4 Commercial [15]
4 PC 4.2 32.5 Commercial [15] Carbohydrates
5 Matrimid/ZIF-8 8.8 81 Research [216] Waste water Organic Acids
6 PES/MWCNTs 6.79 250 Research [222] LIGHT
7 PI/MWCNTs 37.31 16.5 Research [220] Organic Acids
8 Perfluoropolymer/ 102 32 Research [219]
SAPO-34
9 6FDA-DAM/ZIF-90 720a 37a Research [229] Dark fermentation Photo- fermentation
Fig. 25. Hybrid biohydrogen production.
PI: polyimide; CA: cellulose acetate; PSf: polysulfone; PC: polycarbonate; PES:
polyethersulfone; MWCNTs: multi-walled carbon nanotubes; ZIF-8: zeolitic imida-
zolate framework-8; SAPO-34: silicoaluminophosphate with topology CHA; 6FDA- The overall substrate conversion efficiencies for hybrid sys-
DAM: polyimide; ZIF-90: zeolitic imidazolate framework-90.
tems (combined dark and photo-fermentation) look promising
a
Mixed-gas permeation properties with a 1:1 CO2/CH4 mixture.
and the production rates for this hybrid systems could theore-
tically be at least as productive as the most productive dark
fermentation system [158,237–243]. The two steps hybrid dark-
photofermentation is not the only possible strategy to increase
energy conversion efficiency. A three-stage process comprising
dark fermentation, photofermentation, and methanogenesis
(Fig. 26) showed a total energy yield of hydrogen and methane
higher than those through the two-stage (dark fermentation
and methanogenesis) and single-stage (methanogenesis) meth-
ods, respectively [244,245].
However, current hydrogen biological production technologies
are not at commercial scale compared to other technologies such as
steam reforming, partial oxidation of hydrocarbons, biomass gasi-
fication, alkaline electrolyzer [155] In order to favor the production
of H2 via biological routes at commercial scale, a decentralized
strategy has been recommended in the US DOE Hydrogen Initiative
from the National Academy of Engineering [247] with: on-site
production for hydrogen fueling stations for fuel-cell vehicles or
on site fermentors with direct links to fuel cells for home-based
Fig. 24. Biogas production (60% of H2 and 40% of CO2) in reactors using different
substrates [235]. energy, which can reduce the costs associated with transport and
storage of the elusive small size molecule.
In order to assess the potential application of the various
Glucose, isomers of hexoses, or polymers in the form of starch biohydrogen production technologies listed in Table 6 (i.e. direct
or cellulose, yield different amounts of H2 per mole of glucose, biophotolysis, indirect biophotolysis, photo-fermentations, and
depending on the fermentation pathway and end-product(s). dark-fermentation) Levin et al. [159] have calculated the size of
When acetic acid is the end-product, a theoretical maximum of bioreactors that would be required to supply sufficient H2 to
4 mol H2 per mol of glucose is obtained: PEMFCs to generate enough electricity to meet the energy
demands of a typical house located in the Pacific Northwest of
C6H12O6 þ2H2O-2CH3COO þ4H2 þ2CO2 (2)
North America (British Columbia, Canada). The choice of a PEMFC
When butyrate is the end-product, a theoretical maximum of by Levin et al. [159] is based on the idea that biohydrogen systems
2 mol H2 per mol of glucose is obtained: might be used as a best mean of delivering small and distributed
power systems to communities. PEMFC utilizes hydrogen protons
C6H12O6 þ2H2O-CH3CH2CH2COO þ2H2 þ2CO2 (3) (H þ ) as the mobile ion, operate in the 50–100 1C range, requires
pure H2 and is extremely sensitive to the presence of CO. Of all the
Thus, the highest theoretical yields of H2 are associated with fuel cell systems available, PEMFC systems are especially suitable
acetate as the fermentation end-product. In practice, however, for mobile and transportation applications, and PEMFC engines
high H2 yields are associated with a mixture of acetate and have been demonstrated successfully in both cars and buses. Small
butyrate fermentation products, and low H2 yields are associated PEMFCs, in the 1–10 kW range, are also under commercial devel-
with propionate and reduced end-products (alcohols, lactic acid). opment as small stationary power units to provide electricity to
Clostridium pasteurianum, C. butyricum, and C. beijerinkii are high homes and small businesses. If a bio-hydrogen production system
H2 producers, while C. Propionicum is a poor H2 producer [236]. can deliver enough H2 to power a PEMFC for 24 h on a continuous
In photofermentation organic compounds, like acetic acid, are basis, and the fuel cell system can produce enough electricity to
converted into H2 and CO2 with sunlight by bacteria. This process supply the electrical demand year round, the bio-hydrogen system
takes place under anaerobic conditions and can be combined with could have a truly useful and potentially commercial application.
dark hydrogen fermentation in a hybrid or multistage system The analysis carried out by Levin et al. [159] indicated that
(Table 6): in dark hydrogen fermentation acetic acid is one of the some dark-fermentation systems and the CO–water shift reaction
end products, which is completely converted into hydrogen and CO2 of R. gelatinosus appear promising, whilst photosynthesis-based
in the second stage of photofermentation (Fig. 25). systems do not produce H2 at rates that are sufficient to meet the
Pretreatment
c
H2, H2
Dark fermentation
CO2
Supernatant
(mainly acetate, butyrate and ammonium)
CO2
Solids residues
Pretreatment
c H 2, H2
Photofermentation
CO2
CH4, CO2
CO2 CO2
c
Methanogenesis
CH4
Fig. 26. Three stages hybrid process integrated with membrane gas separation.
Fig. 27. Metabolic pathways in fermentative hydrogen evolution [267].
Table 10
Sizes of bioreactors required to power PEMFCs of different output [159].
BioH2 system H2 synthesis rate (mmol H2 (L h)) Ref. Size of bioreactor required to powera
1.0 kW FC(l) 1.5 kW FC(l) 2.5 kW FC(l) 5.0 kW FC(l)
Direct photolysis 0.07 [248] 3.41 105 5.12 105 8.56 105 1.71 106
Indirect photolysis 0.355 [249] 6.73 104 1.01 105 1.69 105 3.37 105
Photo-fermentation 0.16 [250,251] 1.49 105 2.24 105 3.74 105 7.58 105
CO-oxidation by R. gelatinosus 96.0 [252] 2.49 102 3.74 102 6.24 102 1.25 103
Dark-fermentations
Mesophilic, pure strainb 21.0 [253] 1.14 103 1.71 103 2.85 103 5.70 103
Mesophilic, undefinedc 64.5 [254] 3.71 102 5.57 102 9.29 102 1.86 103
Mesophilic, undefined 121.0 [255] 1.98 102 2.97 102 4.95 102 9.89 102
Thermophilic, undefined 8.2 [256] 2.91 103 4.38 103 7.31 103 1.46 104
Extreme thermophilic, undefinedd 8.4 [257,258] 2.85 103 4.28 103 7.13 103 1.43 104
a
Approximate volumes. Calculated volumes were rounded up to nearest whole value.
b
Clostridium species #2.
c
A consortium of unknown microorganisms cultured from a natural substrate and selected by the bioreactor culture conditions.
d
Caldicellulosiruptor saccharolyticus.
goal of providing enough H2 to power even a 1 kW PEMFC on a biomethane in Section 2.1.2.2, can assist fermentative biohydrogen
continuous basis. technology with multiple roles. For example, as for biomethane
Bioreactors of reasonable size would be sufficient to power the AnMBRs with their ability to efficiently retain active biomass
5.0 kW fuel cell using undefined consortia of mesophilic bacteria, within the fermenter, enhanced stability and reliable operation,
enriched for Clostridium species. A bioreactor of 495 L would improve biohydrogen generation as confirmed by various authors
provide enough H2 to power a 2.5 kW PEMFC, while a bioreactor of [259–264]. Compared to conventional reactors, a significantly
approximately 1000 L would provide sufficient H2 to power a higher concentration of active, hydrogen producing biomass can
5.0 kW PEMFC (Table 10). be ensured leading to a definite increment in hydrogen turnover
Fuel cells in general and PEMFCs, in particular, provide the rate as observed for biomethane. However, in the present paper,
most efficient conversion device for converting hydrogen into particular attention, has been devoted to the active role played by gas
electricity, a winning couple to realize sustainable energy. More- separation (gas permeation membranes and membrane contactors)
over, membrane-based processes, as described above for and microbial electrolysis cells (MECs) (Table 6, entry 7)) in the
Fig. 28. Gas separation membrane bioreactor (GSMBR) [21].
production of biohydrogen due to their specific characteristics. Therefore, an efficient gas separation step will contribute to
Regarding MECs, it's important to emphasize that different config- significant increases in H2 production. Recently, Bakonyi et al. [21]
urations, as described below, are possible, with or without the use of gave a comprehensive overview on the applications of non-porous,
a polymer electrolyte membrane (PEM) and therefore, in general, polymeric, and ionic liquid supported membranes for bio-
MECs cannot be defined as a membrane process, even though, recent hydrogen recovery and discussed the integrated bio-hydrogen
studies showed that the presence of an adequate membrane limits production and purification concept using gas separation mem-
the methanogenesis drawback favoring hydrogen as final product gas branes. It is another type of membrane bioreactors, where gas
[265,266]. separation membranes are built-in (Fig. 28) instead of their water
2.1.2.3.1. Membrane gas separation. In dark fermentation the filtration counterparts. Such an apparatus can be called as Gas
continuous removal of hydrogen from the fermentation bath by Separation Membrane Bioreactor, abbreviated as GSMBR.
means of membrane gas separation represents an efficient GSMBR possesses two benefits. First, bioH2 could be diluted
strategy to increase the bio-hydrogen production (Fig. 26). In and higher activity of the hydrogen producing microbial popula-
Fig. 27, common metabolic routes that can occur during fer- tion is expected due to its reduced partial pressure. Hydrogen
mentative hydrogen production are reported. As can be see, purification can simultaneously be performed, and H2 can be used
hydrogen is derived from pyruvate, which is formed during the in the PEMFC if the purification degree is high. In literature, few
breakdown of glucose. The pyruvate is then catalyzed by studies dealing with the integration of biohydrogen generation
pyruvate ferredoxin (flavodoxin) oxidor eductase (PFOR), under and gas membrane separation are reported. Separation of biohy-
anoxic conditions, to produce acetylCoA and reduced ferredoxin drogen does not require high temperature conditions, thus less
(Fd(red)); ATP can be obtained from the former, while H2 is thermostable (and cheaper) polymer-based membranes over
derived from Fd(red) via the hydrogenase [267,268]. The by- expensive inorganic materials (e.g. palladium) may be suitable.
products of the fermentation include ethanol, propanoic and In GSMBR the membrane acts as a selective gas extractor which
lactic acids; these substances represent hydrogen that has not increases H2 production and also, if an efficient separation mem-
been released as gas. In the case where pyruvate breakdown is brane is used, a H2 purification unit is no longer necessary
catalyzed by pyruvate formate lyase (PFL), production of acet- resulting in PI.
ylCoA is simultaneous with formate generation (not shown). In Two entirely different membrane gas separation processes can
general, strict anaerobic bacteria produce hydrogen through the be applied to the separation of H2 and CO2: gas permeation
oxidation of Fd(red) [268]. membrane and membrane contactors.
To maximize the yield of H2, the metabolism of the bacterium Gas permeation membranes Regarding the gas permeation
must be directed away from alcohols (ethanol, butanol) and membranes, a list of commercial polymers suitable for bio-
reduced acids (lactate) towards volatile fatty acids (VFA). The hydrogen separation, i.e. dealing primarily with the separation of
partial pressure of H2 (pH2) is an extremely important factor for H2 and CO2 is given in Table 11. The H2-selective membranes are
continuous H2 synthesis. Hydrogen synthesis pathways are sensi- made of so-called glassy polymers sieving molecules based on size
tive to H2 concentrations and are subject to end-product inhibi- and permeating preferentially hydrogen rather than the other
tion. As H2 concentrations increase, H2 synthesis decreases and larger and less motile chemical substances e.g. CO2.
metabolic pathways shift to production of more reduced sub- Most of membranes for H2-separation was made of commercial
strates such as lactate, ethanol, acetone, butanol, or alanine. The polymers which have originally been engineered for other pur-
concentration of CO2 also affects the rate of synthesis and final poses e.g. natural gas upgrading/sweetening [270].
yield of H2. Cells synthesize succinate and formate using CO2, On the other hand, a large number of high performance, tailor-
pyruvate, and reduced nicotinamide adenine dinucleotide (NADH) made polymers have been developed for H2-selective membranes
via the hexose monophosphate pathway [268,269]. This pathway but presently most of them are still at research level [213,246].
competes with reactions in which H2 is synthesized by NADH- As research experiences with the membranes for gas separa-
dependent hydrogenases (which oxidize NADH to NAD þ ). Efficient tion under real hydrogen fermentation conditions are poor, more
removal of CO2 from the fermentation system would reduce research and tests are essential with complex, H2-containing
competition for NADH and thus result in increased H2 synthesis. gaseous mixtures in order to reveal what kind of system and
operational conditions (e.g. separation temperature and pressure, is due to the elimination or by-passing of limitations of conven-
gas pretreatment to remove or control humidity, etc.) could be the tional chemical engineering equipment, whereas, MRs illustrate a
most feasible for the enrichment of H2 in an integrated process, type of development consisting of a combination of two functions
where biohydrogen formation and purification can take place (i.e. reaction and separation) in one device leading to smaller/
simultaneously. compact equipment for the same production goal.
Membrane contactors Membrane contactors are membrane In Fig. 29 the membrane contactor system developed at TIPS for
systems used to contact two phases in order to promote the mass the purification of gas mixtures of biological origin [274,275]
transfer between them. In membrane contactors, the membrane is shown.
does not act as a selective barrier, but the separation is based on The main advantage of this gas cleaning system which has been
the principles of phase equilibrium. An extended review of designed for decentralized bio-hydrogen production is its low
membrane contactors may be found elsewhere [273]. Membrane energy consumption. Rhodobacter capsulatus was used for lactate
contactors are interesting and suitable options for the purification or low organic decomposition to H2-containing gas mixture and
of bio-hydrogen from CO2 [274–276]. Gas–liquid membrane con- Thermohydrogenium kirishi was used for H2 production from
tactor (GLMC) is a device where mass exchange between gas and glucose. The simplest case of active membrane system is without
liquid phases takes place through a membrane. The principle of compressor: it combines in one block the membrane and absorp-
the gas mixture separation in GLMC is similar to traditional tion methods in the recirculating mode with moving liquid carrier.
absorption separation technique: gas mixture enters from one In this way low-energy consumption active membranes systems
side of GLMC while liquid absorbent enters from the other side, provide high purity H2.
some components of gas mixture are absorbed by liquid absorbent This active membrane system consists of absorption (mem-
whereas other components are almost insoluble in liquid. The brane absorber) and desorption (membrane desorber) membrane
main difference of GLMC is the presence of a membrane which contactors operating in a circular mode (Fig. 29). In membrane
separates gas and liquid phases and forms a geometry of gas– absorber, the feed gas mixture blows over the polymeric mem-
liquid interface. GLMC has the advantages both of absorption (such brane: the permeable component is going through the membrane,
as high selectivity and wide list of known absorbents) and of while the non-permeable one goes to output as a retentate. The
membrane separations (such as determined and constant area of component of the gas mixture, which is permeable through the
mass exchange and high specific area) [277] and represents polymer membrane and soluble in liquid (CO2 in this case), moves
another example of PI. However, differently from PI by MRs with it into the membrane desorber for the reverse degassing
mentioned above, such as WGSMR (Section 2.1.1), MBRs and process through the other polymeric membrane.
GSMBR , GLMC specifically, and membrane contactors (membrane Different silicon-containing polymers such as polytrimethylsi-
absorbers) more in general, represent another type of develop- lylpropyne (PTMSP), polyvinyltrimethylsilane (PVTMS) and poly-
ment which qualifies as PI: dramatic improvements in processing dimethylsiloxane (PDMS) were proposed as materials for the
membranes used in the membrane contactor system. The best
results were achieved using PVTMS membranes with a dense layer
Table 11 of 0.2 μm. The flowing liquid is based on water solutions of
Polymers intended for H2/CO2 separation. monoethanolamine or carbonates of alkaline metals (Li2CO3,
Na2CO3 and K2CO3) in various concentrations (1–3 M) containing
Entry Membrane materials H2 permeability (Barrer) α (H2/CO2) Ref. propylenecarbonate used as liquid absorbent. It was shown that
1 EC 87 3.28 [270]
the best liquid carrier with balanced properties is water solution of
2 PEI 7.8 5.91 [270] K2CO3. In Fig. 30, the results for the selective removal of CO2
3 PPO 113 1.49 [270] indicated that the active membrane system based on PVTMS as
4 PSf 14 2.50 [270] membrane and K2CO3 as carrier is appropriate not only for
5 PMP 125 1.48 [270]
hydrogen but also for CH4 and O2 containing mixtures.
6 PI (Matrimid) 28.1 2.63 [270]
7 PES 8.96 2.65 [271] The authors of these studies suggested that the active mem-
8 PBI 11.2 16 [233] brane system proposed might be successfully used for the separa-
9 PVDF 2.4 2.0 [272] tion of CO2/H2 mixtures as well as of CO2/O2 CO2/CH4 of microbial
10 PMMA 2.4 4.0 [272] origin. In Fig. 31, the integration of the active membrane system
EC: Ethyl cellulose; PEI: Polyetherimide; PPO: Polyphenyleneoxide; PSf: Polysul-
with aerobic and anaerobic bioreactors proposed by Teplyakov
fone; PMP: Polymethylpentene; PI: Polyimide; PES: Polyethersulfone; PS: Poly- et al. [275] is reported.
styrene; PVDF: Poly(vinylidenefluoride); PMMA: Poly(methylmethacrylate); The advantages offered by the active membrane system concept in
PBI: Polybenzimidazole. terms of minimum energy demand compared to conventional gas
purification systems in the specific application of bio-hydrogen
upgrading were recognized in the framework of Hyvolution project,
acronym for Non-thermal production of pure hydrogen from biomass
[278]. In this integrated project recently completed, funded by the
European Union in the Sixth Framework Programme and Sustainable
Energy Systems, different issues such as pretreatment of biomass,
thermophilic fermentation, photofermentation, gas upgrading, logis-
tics, system integration and societal integration were addressed.
Hydrogen is produced in a two-step fermentation process using
thermophilic and photofermentative bacteria, consecutively (see
above, hybrid (or staged system) dark fermentation/photo fermenta-
tion, Table 6). The goal of the work package Gas upgrading, was the
purification and assessment of the gas, produced in the bioreactors.
The aim was to produce hydrogen of constant quality. Therefore, the
objectives were the development of an appropriate gas upgrading
Fig. 29. Membrane contactor for biohydrogen production [274]. system and its coupling to the bioreactors developed in the other work
packages. The most important boundary condition for this system is containing 30% to 40% CO2 the results strongly favor the membrane
the minimum energy demand needed to keep the overall process separation, especially in terms of energy demand. K2CO3 promoted by
efficiency high. Among conventional gas upgrading options, Vacuum piperazine has been selected for the CO2 absorption in the active
Swing Adsorption (VSA) has been selected based on the assumption membrane system for the Hyvolution process since it has a low energy
that the gas mixture produced in the bioreactors will contain no more demand and a higher theoretical capacity than monoethanolamine
than 33% of CO2. The technological applicability of VSA in the bio- [278,279] and a considerably higher reactivity than K2CO3 alone
hydrogen process has been demonstrated and evaluated by connect- [278,280]. Application of the same set up for desorption of CO2
ing a test device to the photobioreactor. Two zeolites (13X and 5A) was unsuccessful at 60 1C. The modification of several process para-
have been selected as adsorbing substances. The trade-off study on the meters such as temperature, liquid flow rate and sweep/stripping
conventional gas upgrading systems has shown energy losses of rate failed to release the CO2 when loading was at typical amounts
around 20% when applying a hydrogen-rich stream contaminated by of 0–50% (mmol CO2/mL solution). Therefore, the membrane c
30% of CO2 to the VSA. When comparing gas upgrading of mixtures ontactor was replaced by a bubble column which allowed a regenera-
tion of the absorbent to less than 0.3% CO2 at 80 1C and a liquid
velocity of 0.4 cm/s. The cassette-type membrane contactor module
itself and its manufacture have been optimized continually. The
current estimation of the requested size for the membrane when
applied in a 60 kg/h H2 production plant (2 MW thermal power) is
10,000 m2 equal to 12.5 m3 [278]. The technologies developed as a
result of the research in this Project will be commercialized after 2015.
This will be in time to facilitate the transition to mass hydrogen
markets, since the European Commission has set an objective of 20%
substitution by bio-fuels in the road transport sector in 2020.
2.1.2.3.2. Microbial electrolysis cells (MECs). As reported above
in Eqs. (2) and (3), respectively, the maximum hydrogen production
from fermentation, assuming only acetate or butyrate is produced
Fig. 30. Selective removal of CO2 by means of active membrane system based on from glucose, is of 4 mol H2/mol glucose and 2 mol H2/mol glucose,
PVTMS for different gas pairs [274]. respectively. The greatest hydrogen yield theoretically possible using
microorganisms (without an external source of energy) is therefore
4 mol H2/mol glucose based on production of acetic acid. Higher yields
can be achieved using photobiological process integrated as in hybrid
process (combined dark fermentation and photofermentation,
Table 6), supplemental light, or using pure enzymes. In the Hyvolution
project cited above [278], with a hybrid two steps fermentation, the
overall efficiency was 53% and increased to 64% if a genetically
modified mutant was used for the photofermentation. However, the
cost analysis for hydrogen production indicated that over 80% of the
total cost is needed for the photofermentation. In particular, the final
cost of hydrogen amounts to € 55–60/kg H2 using tubular photobior-
eactors. However, replacement by panel photobioreactors with a
8.5 times higher illuminated area per unit ground space increases
the cost to € 385–390/kg H2. Moreover, of all the different types of
biomass available for making hydrogen, only materials rich in carbo-
hydrates are suitable fermentation substrates. This fact merits some
Fig. 31. Integration of the active membrane system with aerobic and anaerobic attention for a global bioenergy production in the context of sustain-
bioreactors [275]. able development, i.e. based on the three pillars of the economy,
H2
Power supply
e- e- H2
CO2 CO2
Anaerobic Anaerobic
Power Supply
H + CO2 H2
H+ CO2 + H 2
Substrate
H+
Bacteria
Anode Cathode Anode Cathode
ion exchange membrane

Fig. 32. Schematization of two MEC configurations: (a) two-chamber and (b) single-chamber membrane-less integrated with an external membrane gas separation unit.
society and environment. Acosta-Michlik et al. [281] discussed the efficiencies of these four volatile acids ranged from 67 to 90%.
complexity of the bioenergy structure: it not only provides opportu- Therefore, MEC can theoretically produce 12 mol H2/mol glucose
nities to generate multiple benefits apart from energy generation, but compared to the maximum 4 mol H2/mol glucose, produced in
also causes conflict with many interests due to all those inter-linkages conventional fermentation process.
[282]. In particular, the recent undesirable experiences on food The variety of fuel sources and high hydrogen yield make MEC
availability and accessibility (e.g. [283–285]), forest degradation (e.g. process a promising approach for economically viable biohydrogen
[286–288]), and social conflicts (e.g. [289–291]) attest complex production, particularly from biomass with low or negative
relationships, which early policies promoting bioenergy have over- economic value, such as wastewater, biowaste and agriculture
looked. In this complex framework, the great impact of MECs lies. In residue. A typical MEC is a dual-chamber system consisting of an
2005, one patent [292] and one article [293] by two independent anodic and a cathodic chamber separated by an ion exchange
research groups reported that bacteria could be used to make membrane (Fig. 32a): CO2 is collected in the anode chamber
hydrogen gas in an electrolysis-type process based on microbial fuel headspace and H2 in the cathode headspace. However, single-
cells (MFCs). In a MFC, bacteria, growing on the surface of the anode, chamber membrane-less architecture was developed [164,298–
oxidize any form of biodegradable organic matter generating CO2, 300]. In particular, Call and Logan [164] developed a membrane-
electrons and protons [294]. The electrons flow from the anode less MEC with a graphite fiber brush anode to provide a high
through an electrical circuit to the cathode where they are consumed surface area for the bacteria, and a cathode placed in close
in the reduction of oxygen. When oxygen is present at the cathode, proximity to the anode (schematized in Fig. 32b). The system
current can be produced, but without oxygen, current generation is design improved current densities, resulting in a maximum
not spontaneous: the reduction reaction of H þ ions to H2 at the hydrogen production rate of 3.12 m3 H2/m3/d at an applied voltage
cathode has a lower redox potential than the anode; an additional of 0.8 V over a fed-batch cycle time of 12 h with cathodic hydrogen
voltage must be applied in order to the reaction proceeds. By applying recoveries ranged from 78% to 96% at applied voltages of 0.3–0.8 V.
a voltage 40.2 V between the anode and the cathode, much lower However, in addition to methane production due to methanogen-
than the theoretical value of 1.2 V required for water electrolysis, esis (1.3% average), carbon dioxide was typically present in the
hydrogen gas is produced at the cathode through the reduction of product gas at 7–8% as a result of the single chamber design,
protons. The process was defined electrohydrogenesis or microbial compared to o0.5% in MEC reactors using membranes. In fact in
electrolysis to emphasize that in MEC there is an electrically driven the single chamber design both CO2 and H2 are collected in the
hydrogen evolution process that is distinct from fermentation. The same headspace making necessary a step of gas purification,
presence of oxygen can inhibit the growth of obligate anaerobic which could be realized as reported above in Section 2.1.2.3.1 via
microorganisms. Therefore MECs differently from MFCs operate under membrane gas permeation or membrane contactor (Fig. 32b).
completely anaerobic conditions. MEC is an electrolysis reactor that With the single cell membrane less architecture high CEs (Cou-
produces hydrogen (Table 6), while a MFC is a fuel cell that produces lombic efficiencies) and hydrogen recoveries can be obtained with
electricity [295]. an apparent reduction of equipment costs due to the membrane
MECs have two main advantages over other biological hydro- absence (the purification costs of the gas produced should be
gen production processes (Table 6). First, fermentative hydrogen taken in account), but further work is needed to investigate the
production requires carbohydrate-rich substrates while in MECs long-term stability of the system to avoid methane generation, as
various organic matters can be used as substrate, including confirmed by the results reported by Cusick et al. [266]. These
cellulose, glucose, glycerol, acetic acid, sewage sludge and varied authors reported the results of a pilot-scale continuous flow MEC
wastewaters [293,166,296]. Second, non-fermentable substrates fed winery wastewater where no membrane partitioning was
(e.g. acetate, butyrate), which are byproducts of dark fermentation used. Although the target product was hydrogen gas, the majority
due to thermodynamical limitations, can be completely oxidized, of the gas produced (86 7 6%) by volume was converted to
resulting in high H2 yields [293,296]. In fact, under standard methane: the absence of the compartmentalization contributed
biological conditions (T ¼25 1C, P ¼1 bar, pH ¼7) the Gibbs free to the hydrogen diffusion into the anode zone where methano-
energy of reaction (ΔGr) for acetate oxidation to hydrogen is [297]: genesis occurred. Further, the efficiency of MEC in the membrane-
less configuration on actual wastewaters that may contain high
CH3COO þ4 H2O-2HCO3 þ H þ þ4H2 (ΔGr ¼ þ 104.6 kJ/mol) (4)
concentrations of hydrogen-consuming microorganisms also
This reaction has a positive ΔGr and therefore additional needs further evaluation.
energy has to be added in order to overcome this thermodynamic In Table 12 advantages/disadvantages for dual chamber with
limit for hydrogen evolution and the added voltage supplied by membrane MEC architecture are reported. It is important to empha-
the power supply provides this extra energy input for a MEC. size that different configurations are possible for MEC and in Table 13
Experiments have shown that the microbial electrolysis reactions the main important aspects derived from recent case-studies are
typically start to occur at applied voltages above 0.2 V, which summarized [265,266,306]. In particular, systems with two liquid
corresponds to an energy requirement of 0.43 kW h/m3 H2 (at chamber (schematized in Fig. 32a) [265,301–309]; one liquid cham-
100% cathodic hydrogen recovery). The energy efficiency ranged ber and one gas chamber [303,304]; continuous-flow MEC with one
from 681 to 243% when evaluated in terms of only the voltage liquid chamber and one gas chamber [299]; single-chamber MEC
addition (0.2–0.8 V) as a result of energy contributed by bacterial cube-type with graphite brush anode and carbon cloth cathode
oxidation of the acetate. In comparison, hydrogen produced by (schematized in Fig. 32b) [164]; bottle MEC with carbon cloth anode
water electrolysis can never exceed 100%, and it typically has and cathode [310]; bottle-type MECs with graphite rod electrodes
efficiencies of 50–70% [296]. [311]; tube-type MEC with carbon cloth anode and cathode sepa-
Direct high-yield hydrogen gas production was demonstrated rated by cloth [312] are described in literature. Logan et al. [296]
by using glucose, several volatile acids (acetic, butyric, lactic, comprehensively reviewed MEC technology. Recent advances on
propionic, and valeric), and cellulose at maximum stoichiometric MECs designs and performances may be found in two recent reviews
yields of 54–91% and overall energy efficiencies of 64–82% [166]. In [313,314].
particular, the predominant acids produced by glucose fermenta- The membrane function in MEC is different from that in
tion (i.e. acetic, butyric, lactic, propionic, and valeric) were suc- MFC: in MFC it prevents the explosive mixtures of oxygen and
cessfully used to generate hydrogen gas in the electrohydrogenic hydrogen gases evolved from the electrodes; in MEC the
process at energy recoveries of 66–82%. Stoichiometric conversion membrane is needed for practical and not safety reasons
Table 12
Advantages/Disadvantages of two chamber MEC with membrane.
Advantages Disadvantages
Avoided contamination of H2 with CO2 without necessity of an Potential loss caused by the membrane resistance, thereby decreasing the current density and
upgrading step hydrogen production rate compared to membrane-less architecture
Reduced problems of H2 utilization by bacteria (methanogenesis) Increased cost of the system due to the presence of a membrane
compared to single cell membrane-less system Simplified reactor architecture
Table 13
Characteristics and performance of MECs in some studies.
System Membrane type Total reactor liquid Applied Overall H2 H2 production rate, Q Energy input Ref.
configuration volume (L) voltage Yield, (%) (m3/m3/day) (kW h/m3)
Two chambers AEM (AMI-7001; Membranes 0.04 0.6 88 1.1 1.3 [166]
International, NJ, USA)
Two chambers CEM (Fumasep_ FKE, FuMa-Tech – 1 – 0.4 – [325]
GmbH, Germany)
Two chambers AEM (Fumasep FAA, FuMa-Tech GmbH, – 1 – 2.1 – [325]
Germany)
Two chambers CEM (CMI 7000, Membranes – 0.85 – 0.2 – [306]
International, NJ, USA)
Two chambers CEM (Nafion 117) 0.03 0.45 61 0.37 1.0 [293]
Single chamber Membrane free 0.03 0.8 93 3.12 1.7 [164]
Single chamber Membrane free 0.3 0.6 64 0.69 1.4 [298]
Single chamber AEM/CEM 3.3 1 23 0.3 2.2 [329]
because of a lack of oxygen evolution. In MEC, the membrane 4H2 þ CO2 ¼ CH4 þ 2H2O (6)
not only reduces the crossover of fuels and bacteria from the
Wang et al. [319] showed that the origin of the methane
anode to the cathode, but also helps to maintain the purity of
recovered in MECs is primarily associated to the hydrogen gas
the hydrogen gas evolved at the cathode limiting its diffusion
consumption and not to acetoclastic methanogenesis, explaining
into the anode solution where it can be lost to bacterial
the reason for which in many tests using mixed culture inocula in
oxidation (methanogenesis).
small- and larger-scale MECs with single chamber designs, there
Methane production occurs during hydrogen gas generation in
was very little net hydrogen production [320–322,266]. The
MECs, particularly when single chamber systems, which do not
authors indicated that in order to produce and recover a high
keep gases, generated at the cathode, separated from the anode,
purity hydrogen gas in larger MECs, two chamber configurations
are used. Methane production cannot be prevented in single
had to be used. In fact, for the single chamber architecture,
chamber MECs unless inhibitors are used [315], or two chamber
methane generation is difficult to control in mixed culture MECs
systems are used. It is important to emphasize that rather than
that produce high concentrations of hydrogen gas. By keeping
avoid methane production, it has been suggested that membrane
cycle times short, and using higher applied voltages (0.6 V), it is
less MECs might be a viable polishing step for the treatment of the
possible to reduce methane gas concentrations (o 4%) but not
effluent of anaerobic digesters as methane was produced under
eliminate methanogenesis in MECs [319].
low organic loading conditions and at room temperature, forming
Established that two-chamber configuration reduces the pro-
a viable method of bioenergy production primarily due to
blem of methanogenesis, further studies were focused to over-
methane from hydrogen gas [316,317]. In this perspective, MECs
come the drawback of internal resistance associated with the
specifically designed for producing methane via electromethano-
presence of a membrane. More in details, early studies [324,325]
genesis (different from electrohydrogenesis or microbial electro-
reported in literature to reduce the overpotential, were focused on
lysis MEC where an electrically driven hydrogen evolution process
the membrane type, while recently the analysis of the effect of
occurs) provides an additional route for biofuel production accom-
catholyte solutions with high conductivity resulted to greatly
panied with carbon dioxide capture, without the need for precious
reduce the problem of the internal resistance [313,265,326].
metal catalysts. In the electromethanogenesis, microorganisms
A pH drop in the anode chamber and a contemporary pH
(methanogens) are used on the cathode (methanogenic bio-
increase in the cathodic compartment occurred due to the faster
cathode) where direct electron transfer to methanogens occurs:
charge transfer rates of cations other than proton across the cation
methane gas is produced from carbon dioxide and electrical
exchange membrane (CEM) because Na þ , K þ , NH4þ Ca2 þ in
current at rates much greater than those possible via hydrogen
wastewaters are typically present at concentrations 10 times
gas evolution from a noncatalyzed electrode [318].
higher than the protons. This phenomenon results in a loss of
However, in conventional MECs designed for hydrogen produc-
voltage consistent with the Nerst Equation that limits the hydro-
tion (i.e. without using a methanogenic biocathode) indesired
gen evolution reaction. Based on the Nernst equation and typical
methane production can occur from two routes in the presence
solution conditions, each unit of pH increase in the cathodic
of acetate, carbon dioxide and hydrogen gas [319]. The first
compartment could increase overpotential by 59 mV [323].
pathway is by acetoclastic methanogenesis (the main route of
Otherwise, a reduced pH at the anode limits bacterial growth.
methane generation in anaerobic digestion), while the second is
Low pH cannot be used at the anode because exoelectrogenic
from hydrogenotrophic methanogenesis:
bacteria require near-neutral pH conditions. By using an anion
C2H4O2-CH4 þCO2 (5) exchange membrane (AEM), proton conduction was enhanced by
protons being carried by chemical buffers, such as phosphate and Jeremiasse et al. [326] who used a 0.1MKCl solution (no buffer) in a
bicarbonate alkalinity, across the membrane [325]. This result was two chamber MEC with a Ni foam cathode: the catholyte increased
confirmed by the same research group exploring the performance to a pH ¼12 but the hydrogen production rates were higher than
of an AEM at different applied voltages. While ionic imbalances are those obtained in a neutral pH buffered system.
detrimental to the general operation of MECs, the movement of More recently, Nam and Logan [265] reported the tests results
ions across the membrane during current generation provides a with different salt concentration in the cathode chamber in order
method for altering water chemistry in a manner that can be to better identify the effect of catholyte conditions on hydrogen
useful for achieving water desalination as shown for microbial production in MECs, and improve gas production rates. In parti-
desalination cells (MDCs) in Section 3 of this article (Section 3.3), cular, the anode pH was examined in conjunction to different
focused on desalination powered by renewable energy sources. cathode salt concentrations to better optimize the performance of
Rozendal et al. [324] studied four types of ion exchange the two chamber MEC for hydrogen gas production. A low anode
membranes: (i) a CEM, (ii) an AEM, (iii) a bipolar membrane pH is well known to inhibit current generation [327,328].
(BPM), and (iv) a charge mosaic membrane (CMM). With respect Cathodic hydrogen recoveries (rcat) remained high (490%) in
to the electrochemical performance of the four biocatalyzed most tests where the final anolyte pHs were above 6.0. These
electrolysis configurations, the ion exchange membranes are rated values are all high, compared to those in single chamber MECs,
in the order AEM 4CEM 4CMM 4BPM. However, with respect to where hydrogen recoveries are much lower due to the conversion
the transport numbers for protons and/or hydroxyl ions (tH/OH) of most of the hydrogen to methane [310,320,329].
and the ability to prevent pH increase in the cathode chamber, 2.1.2.3.3. Production of biohydrogen, without electrical grid
the ion exchange membranes are rated in the order energy. Reducing electricity supply is a key issue for the successful
BPM 4AEM 4CMM 4CEM. Sleutels et al. [325] further studied application of MECs. MECs can be integrated both with reverse
the different performance of AEM and CEM by comparing two electrodialysis via microbial reverse-electrodialysis electrolysis
analysis methods for bio-electrochemical systems, based on poten- cells (MRECs) and MFC in a dual bioelectrochemical system (BES)
tial losses and partial system resistances. The study reconfirmed (Scheme 3) avoiding in both cases the need of electrical grid
the large difference in performance between the AEM configura- energy.
tion (2.1 m3 H2 m3/d) and CEM configuration (0.4 m3 H2 m3/d) at In particular, MRECs powered by salinity gradient energy (see
1 V. This better performance was caused mainly by the much Section 2.2) offer interesting perspectives for large scale realiza-
lower internal resistance of AEM compared to CEM. This lower tion of a fully green MEC technology. In 2011 Kim and Logan
internal resistance could be attributed to the lower transport published, for the first time in literature, that H2 can be produced
resistance of ions through the AEM compared to the CEM caused in a single process by capturing the salinity driven energy along
by the properties of both membranes. with organic matter degradation using exoelectrogenic bacteria
Regarding the option of using a catholyte with a high con- [330]. In other words the authors integrated RED (reverse electro-
ductivity, Nam and Logan reported that the use of a solution dialysis) with MEC [330,331]. Reverse electrodialysis (RED) is one
66 mM NaCl with a conductivity of 7.3 mS/cm, greatly reduces the of the most studied membrane process for converting salinity
catholyte solution resistance of a dual chamber MEC equipped differences between seawater and river water into electrical
with an AEM [308]. Hydrogen production in a two chamber power. More details and recent results on RED to capture salinity
system without pH control was superior to that of MEC with a gradient energy are reported in Section 2.2 of this article. In a RED
phosphate buffer, despite the increase of the pH in the non- system, seawater and river water are pumped between the
buffered catholyte to a pH ¼11 [308]. This effect was confirmed by membranes in a stack that can contain 20 or more membrane
MFC RED
>0.2volts
CO2 Power
e- Source e- H2
H+
H+
H+
H+
MEC
Scheme 3. Electricity sources (a, MFC and b, RED) alternative to electrical grid energy to power MECs.
pairs ( 0.1 to 0.2 V per membrane pair) to generate sufficient systems to boost MFC voltages through the use of charge-pumps
potential to split water. However, the results reported by Kim and [338,339], diodes [340], DC/DC converters [341], batteries [342].
Logan [330,331] indicated that a RED stack of only 5 membrane Hatzell et al. [343] examined capacitor based circuit as a method
pairs between the electrodes, incorporated in an MEC synergisti- to efficiently transfer energy and boost applied voltages from MFCs
cally increases the performance of the integrated system com- to MECs. In this approach, multiple MFCs are used to charge
pared to the individual systems. A small RED stack by itself cannot capacitors in parallel, and then the charged capacitors are dis-
produce current. However, in the integrated system proposed by charged in series, improving voltage production and hydrogen
Kim and Logan [330], the exoelectrogens on the anode produce energy recoveries. In particular, the use of the capacitor charging
current and create a favorable reaction, and thus substantially system increased energy recoveries from 9 to 13%, and H2
reduce the electrode overpotential. The added salinity driven production rates increased from 0.31 to 0.72 m3/m3-day, com-
energy, provided by using only a small number of RED cell pairs, pared to coupled systems without capacitors. The circuit efficiency
eliminates the need for an external power source for MEC (Fig. 33). (the ratio of the energy that was discharged to the MEC to the
H2 production is achieved by two driving forces: a thermodyna- energy provided to the capacitor from the MFCs) was 90%.
mically favorable oxidation of organic matter by exoelectrogens on
the anode; and the energy derived from the salinity gradient
between seawater and river water. Moreover, the MREC is effective 2.1.3. Biobutanol production
in organic matter removal, which can lead to effective wastewater To conclude the section of this article on biomass-based
treatment. No electrical grid energy is needed, and therefore both renewable energy sources, in this section some membrane pro-
H2 production and wastewater treatment would be carbon neutral cesses able to enhance the production liquid biofuels are proposed.
as the organic matter is fixed and not derived from fossilized Biobutanol has been selected as case study among biodiesel,
carbon. biomethanol, bioethanol etc. Biodiesel, considered as a possible
One limitation of MREC for H2 production is that this process substitute of conventional diesel fuel, usually consists of fatty acid
requires sources of organic matter and seawater in close proximity methyl/ethyl esters, obtained from triglycerides by transesterifica-
making the process useful only in coastal and not inland regions tion with methanol/ethanol, respectively [344,345]. Alcohols,
[332]. Nam et al. [332] investigated the effectiveness of ammo- mainly ethanol and to a much lesser extent methanol, are
nium bicarbonate for providing a regenerable high salinity solu- considered as alternative fuels for internal combustion engines
tion to produce hydrogen gas without any external power source [346,347]. Ethanol is a biomass-based renewable fuel that can be
in MRECs. Ammonium bicarbonate salts, which can be regenerated produced by alcoholic fermentation of sugar from vegetable
using low-temperature waste heat, can also produce sufficient materials, such as corn, sugar cane, sugar beets, barley, sweet
voltage for H2 generation in MREC. To maximize the performance sorghum, and agricultural residues [348,349]. Methanol is mainly
of the system with NH4HCO3, different salinity ratios, salt con- produced from coal or petrol based fuels. Therefore, ethanol is
centrations, and flow directions (co- or countercurrent) of solu- superior to methanol due to its renewability and is widely used as
tions in the RED stack were examined [332]. an additive or alternative fuel in many countries, such as the US,
The use of MFCs to directly power MECs (Scheme 3) has been Brazil, China, etc. However, ethanol is corrosive to the existing
proposed in several studies [333–337]. As reported above, MFCs pipelines through general corrosion (dry and wet corrosion). A
use bacteria to generate electricity from the oxidation of organic very competitive biofuel for use in engines is butanol. Biobutanol
matter and the reduction of oxygen. Coupled together, the dual demonstrated various significant properties over bioethanol (com-
BES has the advantage of removing organics from wastewater mercialized biofuel) such as high calorific value, low freezing
while generating H2, without consuming any electrical grid point, high hydrophobicity, low heat of vaporization, no need of
energy. However, the performance of these systems has been modification in exiting car engines, less corrosive, no blending
limited by low voltages produced when the two systems were limit (can be used up to 100%). Like ethanol, butanol is a biomass-
directly connected. Several approaches have been used to increase based renewable fuel that can be produced by alcoholic fermenta-
voltage production. One approach is to use power management tion of the biomass feedstocks [350]. However, economic feasi-
bility of biobutanol fermentation is limited by its low productivity
[351]. Production of industrial butanol and acetone, via ABE
(acetone, butanol, ethanol) fermentation, one of the oldest known
industrial fermentations, started in 1912–1916 [352]. Fig. 34 shows
a scheme of the production pathway through ABE [353].
In the acidogenic phase, acetic and butyric acids, carbon dioxide
and hydrogen are produced from sugars, followed by the solvento-
genic phase where acids are converted into acetone, butanol and
ethanol, typically in the ratio of 3:6:1. Since the 1950s, ABE
fermentation declined continuously mainly because the price of
petrochemicals dropped below that of starch and sugar substrates
such as corn and molasses, and almost all butanol was produced
via petrochemical routes, so it is called petro-butanol. Therefore,
during this stage, butanol production from fossil fuel became more
popular than that from ABE fermentation. The chemical pathway
for n-butanol production from propylene [354] is shown in Fig. 35.
One of the most critical problems in ABE fermentation is solvent
toxicity. Clostridial cellular metabolism is inhibited in the presence
of 20 g/L or more of butanol [355]. This limits the concentration of
carbon substrate that can be used for fermentation resulting in
low final butanol concentration and productivity. A butanol
Fig. 33. Schematic of microbial reverse-electrodialysis electrolysis cells (modified recovery step after or continuously as in situ removal during the
from [330]). fermentation is necessary. Valuable improvements of butanol
production concern metabolic engineering of Clostridium acetobu- Membrane technology may enhance both the fermentation
tylicum; enhanced fermentation process and butanol recovery process and butanol recovery allowing its in-situ/online removal
technology; application of cheap substrates for butanol fermenta- in an economic and energy efficient way. In fact, the dilute
tion. Membrane cell recycle reactor is another option to improve product mixture and high boiling point of butanol (118 1C) make
fermentation productivity: a membrane (usually hollow fiber not convenient the solvent recovery by using traditional energy-
ultrafiltration membranes) allows the aqueous product solution intensive and costly processes such as distillation. Integration of
to pass while retaining the cells. The reactor feed and product Pervaporation (PV) [357–361] or supported liquid membranes
removal are continuous and a constant volume is maintained in (SLMs) [358] with a fermentation unit for in situ product
the reactor [356]. recovery is possible, enabling an increased yield and productivity
(Fig. 36).
Several PV studies, with the membrane unit not in line in
continuous mode operation with the fermentor, have been done
by using both model ABE–water solutions and fermentation broths
in order to test the operational feasibility of the process in terms of
membrane separation factors [362–369]. PV is a membrane
permeation process where the feed liquids contact the membrane
on one side and the permeate is removed as vapor (Fig. 37). The
process involves three steps (solution-diffusion mechanism):
(i) selective sorption of the species into the membrane on the
feed side; (ii) selective diffusion through the membrane; (iii)
desorption into a vapor phase on the permeate side.
The efficiency of the separation may be expressed by using the
separation factor (β):

X A =X B
β¼ permeate ð7Þ
X A =X B retentate
where X is the mole fraction, A represents the preferentially

transported component (butanol) and B stands for water.
In traditional distillation, the separation is controlled by vapor–
Fig. 34. Fermentation pathway of butanol by C. acetobutylicum [353]. liquid equilibrium (the difference of boiling point of the species to
be separated is crucial); in PV the differences in solubility and
diffusivity of the species in the membrane are the driving force of
the process. Separation is determined by physico-chemical affinity
between membrane material and permeant. Therefore, an accu-
rate selection of the membrane material is at the basis of success-
ful separation via PV. In particular, from an economic point of
view, PV is advantageous for small plants compared to distillation.
For large feed volume, the use of hybrid distillation/pervaporation
and the research of new membranes to improve membrane
selectivity are mandatory to make PV more competitive than
traditional distillation.
PV separations have found applications for several categories of
mixtures which can be classified as follow [370]:
a) Water/organic mixtures, for:

– dehydration, water being the minor component to be
extracted;
– removal of organic compounds diluted in water; in this case,
the aim is to recover the organic compounds by selective
transfer through the membrane; in this category, the
separation of alcohols from water is very attractive.
Obviously these two cases require membranes endowed
with very different properties, having respectively reverse
Fig. 35. Chemical pathway for n-buatnol production [354]. selectivities.
Fig. 36. Integrated fermentation with membrane operations (SLM, PV) for the production of biobutanol.
b) Organic/organic mixtures, with some typical cases: Other membrane materials include polyetherblockamide
– polar/non polar mixtures, like azeotropes; a particular type (PEBA), polytetrafluoroethylene (PTFE), poly(1-trimethylsilyl-1-
is protic/non protic mixtures which are certainly the easiest propyne) (PTMSP). Both commercial and laboratory scale MMMs
to be treated (e.g. alcohol-ether); based on PDMS and silicalite-1 are widely used for butanol
– mixtures of low - or non - polar mixtures, isomers (e.g. separation (Table 15). The presence of the hydrophobic zeolite,
xylenes, C8 isomers or closely boiling components, benzene/ which acts as molecular sieve, enhances the transport of butanol
cyclohexane mixtures). compared to water (separation factors higher than pure PDMS),
but reduces the flux as observed in different studies [371,372].
Corresponding to these typical PV cases, four basic kinds of PV Further, composite membranes have been recently used for
membranes can be identified (Table 14). Various hydrophobic n-butanol recovery [368,373,374]. Composite membranes are
polymer membranes have been used for the recovery of butanol composed of two or more layers with an active layer, which acts
(Table 15). Polydimethylsiloxane (PDMS) membranes have been as permeselective layer. The support layer should have both a high
widely used in n-butanol recovery because of their highly hydro- porosity (in order to no limit the mass transfer of permeating
phobic properties and good chemical, mechanical and thermal compounds) and a good mechanical stiffness to protect the
stability. selective layer.
2.2. Salinity gradient power: Pressure retarded osmosis or reverse

electrodialysis?
In 1974, R.S. Norman published in Science journal a paper

entitled “Water Salination: A Source of Energy” in which it was
envisaged that techniques available for desalination could be used
to generate power from salinity gradients when operated in the
reversed mode [380]. Several approaches to recover “osmotic
Fig. 37. Scheme of PV separation [370]. energy” (i.e. salinity gradient power) of a system and convert it
Table 14
Classification of membranes for PV [370].
Membrane type Characteristics
Hydrophilic polymeric Prepared usually from crosslinked polar polymers, i.e. PVA or alginate derivatives, to limit the swelling in aqueous feeds and so to promote
membranes the permselectivity of water versus alcohol or organic solvents
Hydrophilic inorganic Based on amorphous silica or NaA zeolite materials having a very narrow pore size distribution to induce size sieving effect favoring water
membranes permeation
Organophilic polymeric Two categories should be clearly distinguished: the first one corresponds to membranes used for the recovery of organic compounds, low
membranes concentrated VOCs, either from vapor or liquid mixtures; polydimethylsiloxane membranes have been widely studied for these
applications;
the second one concerns the separation of organic-organic mixtures; in that case, there is no universal membrane and the polymer
structure must be carefully designed and tailored to reach the best trade-off coping with the industrial target
Hydrophobic inorganic Prepared from MFI zeolites having highly selective organophilic adsorption properties
membranes
Table 15
PV membranes for butanol separation and their separation factors.
Membrane Feed solution (pure butanol or ABE solutions conc.) Temperature (1C) Separation factor Ref.
(β)
PTMSP Butanol (0.02 wt%) 37 46.3 [375]

Silicalite-filled Butanol (o 0.5 wt%) 65 41.5 [372]
PEBA Butanol (0.03–0.4 wt%) 40 19–24a [376]
Silicalite-filled PDMS (GFT 1070) Butanol (1 wt%) 40 36.3 [371]
PDMS (GFT 1060) Butanol (1 wt%) 40 26.8 [371]
PDMS Butanol (1 wt%) 50 34 [377]
PDMS tri-layer composite membrane Butanol (2 wt%) 37 32 [373]
PTFE Butanol (0.3–3.0 v/v%) 39 3–9 [369]
Perv.2200 (Sulzer Co.) Butanol (0.6–5 wt%) 33 2–14 [378]
PDMS–PAN (selective layer of PDMS on a support layer of PAN) Butanol (3.5 wt%) 42 22 [374]
Silicalite-filled PDMS ABE-solutions (1.5–2.0 wt%) 70 93 [364]
PEBA2533 ABE-solutions (1.91 wt%) 23 13.2 [365]
PDMS/ceramic composite ABE-solutions (1.1 wt%) 37 15.1 [368]
PTFE ABE-solutions (0.3–3.0 v/v%) 39 10–15 [369]
Silicalite-filled PDMS ABE-solutionsb 78 97 [379]
PDMS ABE-solutionsc 78 44 [379]
PTMSP ABE-solutions 37 7.4 [375]
PEBA: Poly(ether block amide) ; PDMS: poly(dimethyl siloxane); PAN: polyacrilonitrile; PTMSP: poly[-1-(trimethylsilyl)-1-propyne]; PP: propylene; PTFE: polytetra-
fluoroethylene.
a
The range of values is due to the study of the effects of feed concentration, temperature, and membrane thickness on the separation performance.
b
Fermentation broth: 12 g/L BuOH 6.1 g/L Ac2O, 0.51 g/L EtOH, 0.33 g/L HAc, 0.11 g/L HBu.
c
Fermentation broth: 9.1 g/L BuOH, 2.25 g/L Ac2O, 0.25 g/L EtOH, 1.0 g/L HAc, 1.0 g/L HBu.
Fig. 38. Schematization of pressure retarded osmosis (PRO) [389].
into a more exploitable form are being developed, but the most
promising are pressure-retarded osmosis (PRO) [380,381] and
reverse electrodialysis (RED) [382,383].
PRO uses the flow of water through the membranes to produce
pressurized water that generates electricity. The idea of exploiting
the energy from mixing fresh water and sea water with PRO was
first developed by Prof. Sidney Loeb in the early 1970s. The
estimated energy cost of osmotic power is comparable and
competitive with the other new renewable energy sources, such
as wave, tidal and offshore wind being in the range of 50–100
€/MW h [384].
In PRO process, at the basis of the water flow, there’s the
concentration difference between two water sources: one with a
high salinity (generally seawater) and another more dilute fresh-
water source (river, brackish, or waste water). The two types of
water are placed in adjacent chambers separated by a semi-
permeable membrane (Fig. 38). Due to the resulting concentration
gradient, water diffuses across the membrane from the freshwater
chamber to the seawater chamber. The buildup of water volume in
the more concentrated region creates pressure that spins a
turbine, generating electricity. Meanwhile, a second channel
recycles the freshwater by returning it to its original chamber.
The major challenges in realizing successful PRO process lies in
designing an appropriate semi-permeable fouling resistant mem- Fig. 39. Schematization of reverse electrodialysis (RED) [389].
brane. These aspects are described in the next paragraph.
RED uses membranes for ion – but not water – transport, and
the electrical current generated is captured directly from the flow (as discussed in Section 3). Regarding the technological benefits, the
of ions (Fig. 39). RED system is set up with alternating salt water use of sea or brackish water (instead of fresh water) as diluate
and fresh water channels separated by ion-exchange membranes. allows reducing the electrical resistance of the diluate compartment
Each salt water channel lies between two fresh water channels, and increasing the achievable output power [388].
bounded by an anion-exchange membrane on one side and a To optimize RED power density, researchers are working to
cation-exchange membrane on the other. As salt water and fresh redesign spacers, structures that provide mechanical support
water mix, anions and cations diffuse in opposite directions between membranes. Conventional spacers interfere with ion
toward two electrodes on either end of RED apparatus. Electrodes transport, but newly-developed conductive spacers are permeable
receive the ions and convert this energy into an electrical current to ion flow. Some aspects related to this issue are discussed below,
carried by a connecting wire. Research has revealed that the in Section 2.2.2. A major challenge to implementing widespread
maximum amount of energy that RED can theoretically produce RED systems is the cost of the ion-exchange membranes, but
depends on the salinity, or salt concentration, of the water source. researchers predict that prices will go down as global demand
Whereas typical seawater can produce just under 1 kW-h of energy, increases. Post et al. [390] developed a method which allows for a
highly concentrated salt water sources like the Dead Sea can comparison of the potential performances of both PRO and RED at
generate over 14 times that amount. Current research projects not equal conditions, with respect to power density and energy
only on RED, but also on PRO investigate salinity gradients gener- recovery. Based on the model calculations obtained by these
ated by the mixing of seawater (instead of fresh water) and very authors, each technique has its own field of application. In
concentrated brines also from RO desalination plant [385] in particular, PRO seems to be more attractive for power generation
integrated cycles [386]. In fact the production of energy from using concentrated saline brines because of the higher power
salinity gradients generated by ultra-concentrated brines and sea- density combined with higher energy recovery; RED is appropriate
water offers both technological benefits for RED [387,388] process for power generation using seawater and river water. However, the
and new potentials for the exploitation of brines (Fig. 40) [386] analysis of Post et al. has been recently revised by Ramon et al.
type tested in PRO was represented by conventional thin film

Desalination Fresh water composite (TFC)-RO membranes, which exhibited high salt rejec-
unit tion and satisfied the chemical stability and mechanical strength
requirements. However, TFC-RO membranes yield very poor
Brine permeate water fluxes in forward osmosis (FO). When water
diffuses across the support layer, the draw solution on the
permeate side is diluted substantially, while the back diffusion
Saltworks Food & Industrial grade NaCl draws solutes through the support layer and works to compensate
the diluted draw solutes (Fig. 41). The compensation process is
severely hindered by the tortuous, dense and thick support
Saturated exhausted (necessary to withstand large hydraulic pressures) of TFC-RO
Brine membranes. As a result, the competition between the dilution
and back diffusion equilibrates at a transverse draw solute con-
Minerals
Recovery centration profile, resulting in an internal concentration polariza-
RED
(e.g. Mg2+, Ca2+) Sat. Brine tion (ICP) problem.
ICP adversely affects the performance of all asymmetric mem-
branes in FO, with the effects being exacerbated for TFC-RO
membranes due to their thick and dense porous support. The
porous support layer acts as a diffusive boundary layer, which
Raw materials Energy severely reduces the osmotic pressure difference across the active
(e.g. Mg(OH)2 or MgCl2) layer [396]. Therefore, the fabrication of an ideal membrane for
Fig. 40. Integrated cycle for reuse and exploitation of brines as a non-conventional PRO relies on eliminating the ICP in the support layers. Both
source of minerals and energy, adapted from [386]. experiments and modeling suggested that the additional resis-
tance to mass transfer of the diffusive boundary layer is propor-
tional to the support layer thickness and tortuosity, and inversely
[391]. PRO, on the basis of their calculations has a better potential proportional to the support layer porosity [397].
for use as a mean for harvesting salinity-gradient energy, no Therefore, the ideal support layers for FO membranes to
matter what salinity gradient is used as the energy source, in enhance performance would be very thin, highly porous, and
contrast with the conclusions drawn by Post et al. [390]. In provide a direct path from the draw solution to the active surface
particular, Ramon et al. [391] reported that current state-of-the of the membrane.
art, optimum power density achievable for PRO for the sea-river Yip et al. [398] provided basic criteria for the design of
water is 2.3 W/m2 compared to 1.3 W/m2 for RED. With projected customized PRO membranes by establishing the influence of
improvements, the gap should increase to 7.7 W/m2 vs. 3.4 W/m2 membrane characteristics on PRO performance. The membranes
for sea-river water pair, while if RO brine is used, the correspond- used in the work are hand-made TFC, consisting of a polysulfone
ing values become 21.2 W/m2 and 5.2 W/m2 [391]. support layer and a polyamide active layer. Post-treatment was
Statkraft, which recently has announced it will discontinue its carried out to produce different batches of TFC-PRO membranes,
effort to develop osmotic power technology [392], pioneered the characterized by different active layer transport properties. The
field of Osmotic Power by developing knowledge and experience post treatment consisted in exposing the polyamide active layer to
in the PRO technology, and later by opening in 2009 a prototype chlorine, which has previously demonstrated increased water
facility in Tofte, Norway [393]. Processes, membranes and other permeability and decreased selectivity (or salt rejection) of the
elements have been tested in the facility, which represented a membrane [399–401]. In practice, three batches of membranes
meeting place for manufacturers and utilities. In a recent state-of- were tested: the first batch of membranes was not subjected to
the-art review, Achilli and Childress [394] gave an interesting any post-treatment and was designated “LP” for its relatively
excursus of PRO development, from the pioneering days in the lower water and salt permeabilities; the second and third batches
middle of the 20th century to the first experimental installation. were immersed in solutions of increased concentration of sodium
The authors emphasized how the Norway installation in Tofte has hypochlorite and were designated as “MP” for its medium water
evoked several specialized and main-stream press news articles.
Even though the research on membranes suitable for PRO pro-
duced interesting results, several technical hurdles regarding the
Support layer
Active layer
overall hydraulics still must be considered and need to be Salt back
overcome. diffusion
JW
2.2.1. Pressure retarded osmosis (PRO): Design for the optimal Cd

membrane
The first membrane elements used by Statkraft were asym- Draw
Feed Solution
metric cellulose acetate (CA) membranes achieving a power Solution (permeate
density of 0.5 W/m2 [395]. This power density is an order of
Side)
magnitude lower than the power density of 5 W/m2 required for
Ci =Cd x e-Jw S/D
this specific installation to be commercially interesting. Since then,
C
the research on suitable membranes for PRO has been focused to
obtain membranes compatible with the selected draw solution,
capable to reject dissolved solutes, produce high permeate water
fluxes, and withstand the mechanical stresses generated by the
operating conditions. After the first exploration of cellulose acetate
and triacetate asymmetric membranes, the second membrane Fig. 41. Concentration polarization in a TFC RO membrane used in PRO.
and salt permeabilities and “HP” for its high water and salt the fabricated membranes is essential to take advantage of more
permeabilities, respectively. permeable but less selective active layers. The membranes are able
The performance of the three batches was evaluated in PRO to tolerate greater increases in water permeability than mem-
configuration using a synthetic seawater draw solution paired with branes with a larger S value (e.g. commercial RO membranes)
river or brackish water feed solutions. In Fig. 42, the characteristic because the low S enables fast diffusion to keep the solution
membrane parameters, i.e. intrinsic water permeability (A); solute within the support sufficiently mixed, thereby mitigating the
permeability coefficient (B); and support layer structural parameter detrimental effect of reverse salt permeation. On the basis of the
(S) of the different membranes are displayed above the water flux analysis on the role played by permeability, selectivity and
plots as bar graphs. The support layer structural parameter S is structure factor, Ramon et al. [391] reported that the efforts aimed
determined solely by the microstructure of the support membrane at reducing the structure factor are less important if they are not
and is defined as S¼ tsτ/ε, where ts is the support thickness, τ is the accompanied by increasing water permeability even at the
tortuosity, and ε is the porosity. The three characteristic properties expense of salt rejection. In the context defined above, several
were used by Yip et al. [398] to extrapolate the water flux and recent papers by different research groups are focused on the
power density as a function of applied hydraulic pressure (Fig. 42, fabrication of high performance membranes for PRO [402–412].
below). The solid and dashed lines show the calculated power
densities for river water and brackish water feed solutions, respec- 2.2.2. Reverse electrodialysis: Novel compartment and cell design
tively. A horizontal dashed line, corresponding to a power density Post et al. [413] showed that it is possible to generate energy
W of 5 W/m2, was included as a visual guide in the plots of power from sea and river water with RED at a price comparable with that
density. of wind energy. They executed their calculations based on the
Despite the water peameability of HP#1 (A), its maximum assumption of a power density of 2 W/m2 and an energy recovery
power density achievable (Wpeak) was significantly lower than the of 70% (equivalent to a river water yield of 1.1 MJ/m3). However,
less permeable MP#1. This observation can be attributed to the existing values with real membranes and real spacers are much
substantially higher solute permeability (B) of HP#1, which leads lower and it is obvious that the current design and membranes
to more reverse salt permeation. The adverse effect of reverse salt should be improved for use in economical operated RED stacks.
permeation coupled with ICP is severely amplified, overwhelming As reported above, RED is an electro-chemical process which
the benefit of higher water permeability. Therefore, the resulting converts the ionic flux directly into electric current on the contrary
water flux and power density are markedly reduced. of PRO, which requires an additional hydro-turbine process step
In order to maximize PRO performance, the membrane active after the osmosis membrane unit. As with PRO, concentration
layer should have a high water permeability and a low solute polarization is inherently present for RED in a purely diffusive
permeability. Yip et al. [398] emphasized how the low S value of form, since convection due to osmosis is very weak and results in a
Fig. 42. Top: membrane characteristic properties, i.e. intrinsic water permeability (A); solute permeability coefficient (B); and support layer structural parameter (S). Bottom:
extrapolated water flux and power density as a function of applied hydraulic pressure [398].
decreased electrochemical potential gradient across the mem-

brane. However, losses from co-ion transport and electro-
osmosis are significant at low current densities. The article by
Veerman et al. [414] with an impressive title “Electrical Power
from Sea and River Water by Reverse Electrodialysis: A First Step
from the Laboratory to a Real Power Plant” represented a turning
point in the optimization of RED process for real applications. As
schematized above, in Fig. 39, a number of alternately stacked CEM
and AEM are separated by spacers. These spacers are open
structures that are necessary for structural stability of the stack
and the promotion of turbulence within the compartments. The
spacer filled compartments are fed alternately with seawater and
river water. The cations diffuse from sea to river water compart-
ments through the CEMs and the anions through the AEMs in the
opposite direction. The ion current in the stack is converted to an
electron current at the electrodes by redox reactions. In the article
by Veerman et al. [414] the performance of small laboratory stacks
(10 10 cm2) with that of an up-scaled 25 75 cm2 stack was
compared. With this larger stack, the authors explored some
crucial aspects for a real implementation at large scale, such as
residence time, flow direction (co or counter-current), flow velo-
city, and segmentation of electrodes (various current densities as a
function of the position in the stack). In particular, it was Fig. 43. Power density as function of residence time for different RED systems
determined that segmented electrodes increased total power out- [414].
put. The lower the stack residence time and thus the lower the
concentration difference between flow inlet and outlet, the less
the influence of electrode segmentation on total power output. the flow path length (L), which should be very short. However, it is
Fig. 43 compares data of experiments with different process difficult to incorporate very short values of L within the concept of
parameters for two membrane types (Fumasep and Qianqiu), classical plate-and-frame stacks or for spiral wound modules as
two stack sizes (small and large), three flow directions (cross-, designed for normal electrodialysis. Therefore, new compartment
co-, and counter-current), and two cell numbers (25 and 50). and cell design are necessary, specific for RED. Brauns [417]
The main conclusion from Fig. 43 is that the residence time is proposed the use of corrugated membranes in a RED stack to
the key parameter governing the power density. A power density avoid the use of spacers.
of 0.93 W/m2 was achieved by using a 50-cell RED stack, the Veerman and co-workers [416] suggested the concept of fractal
highest power density achieved from a sea-river water salinity- spacers. In Fig. 44 a complete RED cell with a profiled AEM
gradient source [415]. (serving as seawater compartment) and a profiled CEM (serving
Normally, spacers are used between the membranes. They are as river water compartment) is shown. The reactor channels are
used for mechanical stability of the stack and may furthermore short, spacerless, and have a low hydrodynamic resistance. In this
promote mixing within the compartments, thereby reducing the context, membranes optimized for RED should be used. Recently,
thickness of the diffusion layers. Güler et al. [418] characterized the bulk membrane properties of
Veerman et al. [414] also reported that further increase of both commercially available membranes and tailor made mem-
power density and energy efficiency can be obtained with a more branes (i.e. made of sulfonated polyetheretherketone (SPEEK) as a
open spacer, which may be beneficial for RED in two ways: less cation-exchanging material and polyepichlorohydrin (PECH) as an
shielding and lower pressure drop. Less shielding decreases the anion-exchanging material) and correlated these to experimental
electrical resistance of the cell. For further scaling-up the RED RED performance data. The highest power density was obtained
process, Veerman et al. [416] elaborated a model which describes with tailor made membranes because of their significantly
the RED process and forecasts the power density and efficiency. In reduced membrane resistance. In particular, depending on the
particular, aim of the model is the optimization of spacer thick- properties and especially membrane thickness, application of
nesses and flow rates. membranes based on PECH in RED resulted in a high power
The performance of four cell configurations was determined by density of 1.27 W/m2, which exceeds the power output obtained
using the models: (i) without spacers and with ideal membranes; with the commercially available AMX membranes and confirms
(ii) with real spacers and with ideal membranes; (iii) without the potential for the design of ion-exchange membranes for a
spacers and with real membranes; (iv) with real spacers and with viable blue energy process [419]. The same authors [418] devel-
real membranes. oped a model based on multiple linear regression for gross power
An ideal membrane does not have an electrical resistance, density. The results set the directions towards tailoring ion
osmosis and co-ion transport. The real membranes used by Veer- exchange membranes for RED applications and show that low
man et al. [416] are the Qianqiu homogeneous membranes. For resistance membranes should be developed, whereas further
spacerless cells, there is supposed to exist a laminar flow between increase of the permselectivity only has a limited effect. Generally,
the membranes. The real spacers are those studied in the paper by membrane resistances are determined at an external salt concen-
the same authors [414]. By comparing the results of the four cell tration of 0.5 M NaCl and a temperature of 25 1C. A recent research
configurations, the main conclusions carried out by Veerman et al. [420] indicated that the actual membrane resistance in practical
[416] concern the membranes, spacers and the flow path length. In applications such as in RED stack where the membrane is placed
particular, the authors found that: (i) improvements of the between solutions of different concentrations, may be an order of
membranes (minimal electrical resistance) have more effect on magnitude higher than that specified in standard resistance
power density and efficiency than improvements of the spacer characterization measurements with 0.5 M solutions at both sides
(minimal hydrodynamic resistance); (ii) the crucial parameter is of the membranes. In this context, Galama et al. [421] reported
natural freshwater ecosystems [424]. In the last decade, there

has been a rapid growth in the installation of seawater desalina-
tion facilities in order to augment water supply in water-deficient
countries [425,426]. In 2016, the global water production by
desalination is projected to exceed 38 billion m3 per year, twice
the rate of global water production by desalination in 2008 [426].
Reverse osmosis (RO) is currently the fastest growing technique
for treating different types of water. For the GCC (Gulf Cooperation
Council) region, thermal desalination (Multi effect distillation
(MED)/Multi-stage flash (MSF)) is and will continue as the leading
technology because energy is still not an urgent issue for these
regions. MED has a greater potential as an evaporation technique,
while vapor compression may be suitable for resort areas or small
sites. Processes for extracting salt such as electro-dialysis (ED), ion
exchange (IE) and capacitive deionization (CDI) are normally used
in brackish water desalination but not for seawater desalination.
Other techniques have been proven to be inefficient such as the
freezing technique, solar stills and many others [427]. Among all
the desalination processes mentioned, RO, MSF and MED account
for about 94% of the global desalination capacity as shown in
Fig. 46 [428].
In particular, the large scale seawater RO (SWRO) plants,
constructed in the framework of the Spanish [423] and Israel
[429] hydrological plans defined in the last decade, have con-
firmed the leading role of the pressure-driven membrane technol-
ogy over other mature technologies.
However, regarding the energy crisis the world is facing, the
Fig. 44. A RED cell with fractal profiled membranes [416]. question of how much energy is needed to make water is
constantly arising. Some environmentalists, decision makers, and
experimental results on the resistance of ion exchange membranes even scientists, consider energy consumption in desalination to be
having different salinities at both sides. These experimental data very high and are seeking new ways of reducing it, which often
were used for a model, to estimate the cation exchange membrane involves increasing capital investment [427]. On the other side,
resistance, even when using different salt concentrations at either leading scientists emphasized that confusion on this issue exists
side of the membrane, improving the previous modeling results today, and even the best researchers are making common mis-
[416] and furthermore provides insight in how to influence the takes in this respect. In particular, Semiat compares the energy
membrane resistance for practical application. consumption for desalination to that utilized in other common
Finally, before to conclude this overview on the technical household usages, putting the problem in its right perspective
improvements needed to make RED competitive with other [427]. Some conclusions of his analyses are that: (i) the lowest
processes used to extract renewable energies, Capacitive Reverse energy consumption is achieved by RO desalination integrated
Electrodialysis (CRED) merits to be mentioned. CRED is a newly with energy recovery devices; (ii) distillation techniques consume
proposed technology to generate electricity from mixing of salt more energy; (iii) the energy consumption of RO desalination is
water and fresh water (salinity gradient energy) by using a not very high especially compared to other daily consumptions.
membrane pile as in RED and capacitive electrodes [422]. In Regarding the environmental issues related to water produced
RED, redox reactions occurring at the electrodes convert the ionic via desalination schematized in Fig. 45, i.e. one major concern is
charge transport into electrical charge transport to generate the potential environmental impacts caused by extensive brine
power. Major limitations of such a redox system are the strong discharge and the environmental degradation related to hypersa-
negative environmental impact and the occurrence of possible linity. It is estimated that 2 m3 is generated as reject brine for
side reactions, both being highly undesired side effects for a every 1 m3 of desalinated water. Brine disposal is a real environ-
sustainable technology. CRED is considered to be a stable, safe, mental problem that should be considered and studied when
clean and high performance technology to obtain energy from installing a desalination plant. Indeed, even if the production costs
mixing of salt water and fresh water. In CRED, capacitive electro- have decreased in the last decade, those related to the disposal of
des composed of activated carbon on a support of Ti/Pt mesh are the brine have shown only limited reduction in the relative costs.
used to store ions and their charge. The performance of stacks
with capacitive electrodes is close to or even better than similar
stacks with conventional electrode systems [422].
IN OUT
ENERGY GHC
3. Renewable energy for membrane desalination
Water, energy and environmental issues are closely related. Desalination

Fresh water
This interconnection in the specific case of desalination is sche-
matized in Fig. 45. SEAWATER
The only methods to increase water supply beyond what is
Brine
available from the hydrological cycle are desalination and water
reuse. Of these, seawater desalination offers a seemingly unlim-
ited, steady supply of high-quality water, without impairing Fig. 45. Desalination process “metabolism” [423].
In most cases, the easiest way to get rid of the important brine In particular, many arid regions in Australia [434,435], Medi-
flow (70 to 55% of intake flow) is to discharge it in the sea via a terranean [436,437], and Middle East countries [438] have a great
brine outfall pipe. Brine concentration has a much higher density potential to cover their water needs with autonomous and stand-
than seawater and therefore tends to fall on the sea floor near the alone desalination systems powered by renewable energy units at
brine outfall outlet (plume effect), creating a very salty layer which competitive cost. During the last decade, a lot of research has been
can have negative impacts on the flora, the marine life and any done in the field of applicability and reliability of desalination
related human activities. Sustainability is currently a main focus of methods using renewable energy sources [432,439,440]. Further-
high-level political discussions in the world, as it involves envir- more, the results of different research programs [436,441] show
onmental pollution and global warming. Today, the challenge is to that the implementation of such desalination schemes can con-
consider the brine, instead of a harmful by-product, as a valuable tribute successfully to the water shortage problems.
source for several compounds to be involved in diverse industrial When several alternative renewable energy sources-
processes [430,431]. As traditional approaches in mining are cost desalination combinations are applicable in a specific case, the
intensive or inapplicable in abandoned and remote regions, choice of the most prominent combination should be based on
research needs to be focused on non-traditional sources such as three criteria: (i) commercial maturity of technology; (ii) avail-
brines coming from desalination plants [431]. ability of local support; (iii) simplicity of operation and main-
Reuse and exploitation of brines as a non-conventional source tenance of the system. Since desalination plants are usually
of minerals and energy by RED, as mentioned in the previous located on the coast of arid sunny regions, the contribution of
paragraph (see Fig. 40), have been investigated in an integrated wind and solar energy becomes an evident partner of the water
cycle where the brines from the desalination unit could provide production industry. However, the main problem that seems to
significant amounts of Mg2 þ , resulting in a very promising source appear at the interface of both technologies is that renewable
of this element as an alternative to traditional mining, whilst the energy production systems – such as wind turbines or photo-
Ca2 þ ,Mg2 þ free brine could be perfectly suitable for feeding the voltaic panels – are subject to natural intermittent and variable
salinity gradient power—RED unit [386]. intensities, whereas desalination processes are designed for con-
An additional concern related to desalination plants is the tinuous steady-state operation [427,442]. In Table 16 a list of the
production of greenhouse gases associated with the required most applicable renewable energy sources-desalination combina-
power generation. In particular, the reduction of CO2 “greenhouse” tions according to the size of desalination plants is given.
gas originated from the use of fossil fuel has led to the goal of Below, in Section 3.1 different examples of membrane desali-
supplying desalination energy from renewable energy sources nation via RO coupled to renewable energies in recent large/
[432,433]. In this context, very often, water treatment plants are medium scale plants are reported. Photovoltaic (PV) powered
viewed as excellent potential locations to install wind and solar systems, almost commercially available in small scale and com-
power generators, while biogas combustion in combined heat and pacts plants, are discussed in the Section 3.2 (“Small scale,
power engines can potentially be exploited at certain sites. demonstrative plants”). This paragraph reports also on membrane
distillation (MD) solar assisted systems, which are still at labora-
tory scale, nevertheless intense research in last decade was carried
out. Finally, the last paragraph (Section 3.3) is devoted to labora-
tory scale, under development studies, such as microbial desalina-
tion cells (MDCs).
3.1. Large/medium scale RO plants
Different largest urban centers in Australia have water storage

volumes less than 50% of their capacities. This is due to an
expansion in total urban water demand, in large part due to
population growth, combined with reduced inflows to storages
Fig. 46. Total worldwide installed desalination capacities by technology, 2010 due to the ongoing drought in many parts of Australia [444].
[428]. Desalination has been proposed for a number of urban centers as a
Table 16
Possible combinations renewable energy sources/desalination (adapted from [443]).
Feed water Plant size Small (1–50 m3/d) Medium (50–250 m3/d) Large ( 4250 m3/d)
n n n
Brackish water Conventional Energy/RO, ED
n
Solar distillation
n
PV/RO
n
PV/ED
n n
Wind/RO
n n
Wind/ED
n n n
Sea water Conventional Energy/RO, ED, MSF, VC, MED
n
Solar distillation
n
PV/RO
n
PV/ED
n n
Wind/RO
n n
Wind/ED
n n
Wind/VC
n n
Solar Thermal/MED
n
Solar thermal/MSF
n n
Geothermal/MED
n
Geothermal/MSF
supplement to existing infrastructure. Large-scale desalination in Melbourne, Australia [447]. The pressure exchangers recover the
does, however, raise a different set of sustainability issues than residual pressure of brines (25 bar), which is transferred to the
those associated with established urban water systems. In parti- feed flow of seawater with an efficiency rate of 95%. In order to
cular, a number of State governments have therefore proposed minimize the environmental footprint, an innovative system of
methods by which they plan to address the greenhouse implica- brine dispersion has been set up, which favors its dispersion and
tions of any desalination plants they build. Sydney and Perth are dilution in the aquatic environment. The plant incorporates double
two of the largest urban areas in Australia and are the locations of pass membranes to achieve a salinity below 200 mg/I and a
important desalination plants, designed to address the critical bromide content below 0.1 mg/I [447]. The PSDP became the first
energy and environmental issues related to large desalination largest plant to have its power consumption offset with renewable
plants. energy generation to address the important challenges of the
During the ceremony for the 2011 Global Water Awards in publicly demanded energy efficiency and limited greenhouse gas
Berlin, the Sydney’s Desalination Plant, one of the largest Reverse emissions.
Osmosis plants in the world, has been named “Desalination Plant Another example of medium scale RO desalination plant
of the Year”. The Sydney’s Desalination Plant began providing powered by renewable energies is the Adelaide Desalination Plant
drinking water in January 2010 and currently has an average which commenced construction in 2009 as part of the Govern-
capacity of 250,000 m3/day [445]. In the Sydney’s Desalination ment of South Australia’s Water For Good plan to secure water
Plant every kilowatt-hour of energy used is fully offset by renew- supplies for all South Australians and reduce the States reliance on
able energy sourced from a purpose-built wind farm at Bungen- the River Murray. The Adelaide Desalination Plant has been
dore in New South Wales. The yearly generation capacity of the supplying water to the Adelaide water network since October
wind farm is greater than the yearly energy use at the desalination 2011 and has been operating at a full capacity of 100 GL per year
plant. Sydney’s desalination plant can supply up to 15% of Sydney’s since the end of 2012. It is powered by 100% accredited renewable
current water needs. The plant can be quickly upgraded to twice green energy sources within South Australia [448,449]. The plant’s
its size if necessary, providing up to 30% of Sydney's water needs. buildings have been designed to maximize natural light during the
The Perth desalination plant (PSDP) of 143,000 m3/day was day and PV cells have been placed on the reverse osmosis
built at Kwinana, 25 km south of Perth in Western Australia [446]. buildings for localized power generation. Each reverse osmosis
The facility includes seawater intake, pre-treatment structures, building has an approximately 100 kW solar cell array providing a
reverse osmosis desalination units and pumping and reminerali- site capacity of approximately 200 kW at peak sun hours. Energy
zation units (Fig. 47). The facility started operating at the begin- recovery devices are installed to reduce energy consumption in
ning of October 2006. At the time of commissioning, the Perth the plant. In addition, two turbine generators in the outfall tunnel
Seawater Desalination Plant was the largest SWRO plant operating take advantage of the plant elevation 50 m above sea level. This
in the southern hemisphere and the largest single source of water mini-hydroelectric system is capable of producing 1290 kW of
for the city of Perth, supplying approximately 17% of the city’s renewable electricity which is fed back into the plant, reducing
needs. The energy consumed by the plant is supplied by a 50 MW energy consumption by approximately 2.5%.
wind farm. The plant uses innovative technology, which provides Thames Gateway (Beckton, UK) is a 150,000 m3/d four stages
energy savings of 15–20%. The most energy intensive part of the RO plant in Beckton, East London, drawing tidal brackish water
plant, which accounts for 50% of total operational costs, is water from the Thames Estuary. Thames Water’s determination to
pressurization to 80 bar before RO [447]. To reduce the power protect the environment and ensure sustainability is at the heart
consumed and greenhouse gases emitted by the RO process, of the Beckton project: the company secured special permission to
Energy Recovery Inc’s PX Pressure Exchanger technology withdraw water during the ebb tide when the river is at its lowest
(Fig. 47) was implemented into the process design in the largest salinity, in order to reduce the plant’s energy consumption [450].
installation of these devices at that time. The company, tasked Ultrafiltration provides a barrier against viruses and other patho-
with design of PSDP, Degrémont, has validated the selection of the gens that integrity can be automatically tested. Thames Gateway
PX devices by using them in subsequent projects such as, the desalination plant was opened in June 2010 and can supply
200,000 m3/d Barcelona Plant and the 411,000 m3/d SWRO facility enough water for 1 million people. The project obtains its entire
Fig. 47. Perth seawater desalination plant at Kwinana [447].

power requirement from renewable energy generated onsite from desalination technologies driven by renewable energies for the
biofuels to supply the estimated 6.3 MW annually. Ultimately, the provision of potable water to remote and isolated communities
objective is to use wind power to meet as much of the energy where the electric grid and the proper infrastructure are lacking.
requirement as possible. Beside the PV technology, RO plants have a modular construction
The above examples of desalination plants are powered by and can be well coupled to a solar photovoltaic. Stand-alone PV
wind or (in the case of Thames Gateway) also by biofuels, but the systems are used in areas that are not easily accessible to
exploration and investigation of new renewable energy sources electricity. Typically a stand-alone PV-powered RO system consists
continues rapidly. CETO is a wave-energy technology that converts of a module, batteries and a charge controller. For example, Herold
ocean swells into renewable power and desalinated freshwater. It and Neskakis [461] illustrated a small PV-driven RO desalination
has been developed by Carnegie Wave Energy Limited, an Aus- plant on the island of Gran Canaria with an average daily drinking
tralian ASX-listed inventor and owner of the patented device. The water production of 0.8–3 m3/d. The plant was supplied by a
company Perth-based Carnegie Wave Energy signed a co- stand-alone 4.8 kWp PV system with an additional battery storage
operation agreement with the WA-based Water Corporation of 60 kW h. At the time of the work, the installation constituted
(which built the first large-scale, mainland desalination plant in the smallest PV supplied seawater desalination plant currently in
Australia at Kwinana in 2006) to support a pilot desalination operation. Starting from this prototype, the feasibility of small PV-
project to be built alongside the Perth Wave energy demonstration RO systems (1–5 m3/d) was investigated. The energy supply of the
project that is now being built near the Garden Island naval base RO plant was realized by a stand-alone photovoltaic generator. To
near Perth [451]. The desalination pilot plant will integrate off-the- achieve a greater flexibility of RO plant operation and adaptation
shelf RO desalination technology with the infrastructure of the to the renewable energy supply, different refined operation
adjoining wave energy project. Combining energy and fresh water strategies have been developed (Static regulation, Flexible regula-
has long been touted as a key differentiation for the CETO tion, Dynamic regulation), depending on the battery charge
technology. The 2 MW demonstration project off Garden Island condition.
will be the first in the world to deploy multiple wave energy Bouguecha et al. [462] compared three different solar assisted
machines. It will feature the CETO technology, that comprises desalination technologies, i.e. solar multiple effects distillation, RO
submerged buoys, 11 m in diameter, that are tethered to pumps driven by photovoltaic panels, and MD using a geothermal
which deliver pressurized water onshore via an underwater pipe. resource. The technological design of the prototype has three
There, the water is used to drive hydroelectric turbines, generating compartments: pre-treatment, desalination and post treatment.
zero-emission electricity, or it can be used to supply a RO The batteries allow operation at constant flow and pressure. They
desalination plant, replacing or reducing the reliance on green- are sized to stabilize the power supply to the RO unit on a daily
house gas-emitting, electrically driven pumps [451]. basis, as well as to account for fluctuations in solar energy and
water demand.
PV-powered RO systems without batteries have also been the
3.2. Solar assisted small scale/demonstrative plants
subject of significant research [463–467]. There has been a lot of
debate over the years about the suitability of batteries as energy
The viability of combined solar power and desalination plants has
storage in PV-RO systems. Many authors and membrane manu-
been investigated for regions such as Mediterranean. The vast solar
facturers often propose batteries in order to address the problem
energy resources of the South can be activated by international
of variable operating conditions (pressure and flow) that follow
renewable energy alliances and allow for a smooth transition of the
solar fluctuations. On the other hand, others argue that lead-acid
present electricity schemes to a sustainable power system based on
batteries (accumulators) which have been used until now in PV-
renewable energy sources [452]. Desalination using solar energy can
RO systems are very troublesome and associate them with various
be classified as thermal and electrochemical processes. Solar collec-
problems such as increase environmental risk in case of spillage
tors can be used to provide heat (solar thermal) or electrical energy
(because of accidents or improper disposal in remote areas where
(solar photovoltaic). The most popular combination of photovoltaic
recycling is limited), worse performance and faster degradation at
(PV) cells is with RO. The feasibility of PV-powered RO (PVRO) for
higher temperatures, a fact which is relevant, since most potential
desalination at remote sites is a proven combination. Different from
sites for PV-RO applicability do experience high temperatures.
PVRO plants, solar-thermal RO desalination plants are still far from
With increasing operating temperature, the charge efficiency
commercialization. Membrane distillation (MD) is a non-isothermal
decreases, eventually reducing the number of battery lifecycles.
separation process consisting of the combination of water evapora-
Thomson [466–468] proposed the design, construction and testing
tion and vapor condensation in an integrated membrane process. MD
of PV-RO desalination system, which doesn’t require batteries,
is an excellent example of process intensification, representing as for
since the rate of production of freshwater varies throughout the
membrane reactors the type of development which consists of a
day according to the available solar power. Initial testing of the
combination of two processes leading to smaller/compact devices for
system with the solar resource available in UK provided freshwater
the same production goal.
at approximately 1.5 m3/day. Nearer to the equator and with a PV
MD requires low temperature heat and electricity. In this respect,
array of only 2.4 kWp, a software model of the system predicts
solar collectors and PV are mature technologies which could be
production of over 3 m3/day throughout the year. The system is
coupled to MD process. MD, differently from RO, can tolerate fluctua-
shown in Fig. 48.
ting and intermittent operating conditions as well as it requires low
The interest for PV-RO battery-less has been confirmed in
grade thermal energy [453]. Extended reviews of solar assisted sea
recent years by the analysis of Schies et al. [469] from the
water desalination may be found elsewhere [432,440,453–456]. In
impressive title “Operating control strategies and dimensioning
the following paragraphs, only solar assisted membrane desalination
of photovoltaic powered reverse osmosis desalination plants with-
plants, in particular RO and MD are discussed.
out batteries”. High requirements for the operating control stra-
tegies must be satisfied. A PV-RO system has been modeled in the
3.2.1. PV assisted RO Dymola simulation environment. This system minimizes the
PV is considered a proper solution for small RO desalination specific energy consumption (SEC) and accordingly distributes
application in sunny areas [457–459]. More than 10 years ago, the incoming PV power to the different pumps in the PV-RO
Houcine et al. [460] pointed out the importance of small-scale system. The operating control strategy also accounts for the
Fig. 48. PV-powered RO without battery [466].
requirements stipulated by the membrane producer. To obtain the the desalination plant site, then the solar system alone becomes
required amount of permeate every day of the year, a tool has been the only solution, even though the cost of the produced water is
developed especially for dimensioning the PV generator for the higher (US$2.859/m3). Usually the cost of electricity produced
PV-RO system under the local boundary conditions. However, in from a solar system in remote areas is lower than the cost of
the absence of batteries, the power from a PV system varies with electricity produced from a diesel generator. But due to the 24-h
solar radiation; if one wants to make the best use of this variable continuous nature of the RO plant, the system needs a large
power, the RO unit should work on variable power, which is number of batteries, which results in a higher net present cost of
contrary to the normal operation of this unit. This lowers the the PV system and a higher cost of electricity. This leads to a higher
efficiency of the RO unit and challenges the system balance. cost of permeate water produced from the RO system. The analysis
Therefore, it is also common practice to connect PV systems to emphasizes that the location of the desalination plant (remote
the local electricity grid, in area where it is available. During the area or not; with/without national grid) has a strong influence on
day, the energy generated from the PV system is used directly the economic feasibility of a desalination system among different
whilst power is utilized from the electricity grid at night. Thus the systems possible. This conclusion is confirmed by other authors.
grid acts as an energy storage system [454]. However, for small Bilton et al. [471] in their paper entitled “Photovoltaic reverse
systems used in remote areas, where the electricity grid is very far osmosis-Feasibility and a pathway to develop technology” illu-
from the plant and expensive to extend, diesel generators could be strated a research program focused on improving the feasibility of
used in these areas and constitute a lower capital cost; but fuel, PV-RO systems. All the results reviewed by the authors show that
transportation, and generator maintenance costs make their the economic feasibility is a strong function of location.
operations costly compared to renewable energy systems. Al- Before to conclude this paragraph, it should be mentioned the
Karaghouli and Kazmerski [470] analyzed the performance and importance of the research focused on photovoltaic active materi-
economics of a medium-capacity (2000 m3/day) RO/PV desalina- als to improve PV power, as strategy to make PV-RO competitive.
tion plant proposed to be installed in Umm Qasr city, south of It’s recent the news which reports on the building of world's
Basra, Iraq. The objective of the study was to determine cost- largest solar-powered desalination plant in the city of Al-Khafji
effective and feasible energy options to produce the required [472]. The plant will use a new kind of concentrated PV technology
amount of water using the SWRO plant. The types of energy and new RO membranes, which King Abdulaziz City for Science
options under consideration included national grid power, and a and Technology (KACST) developed with IBM. When completed
hybrid of PV system and diesel generator. The analysis shows that (original completion foreseen for the end of 2012), the plant will
the water production cost is the lowest (US$1.024/m3) when produce 30,000 cm3 of desalinated water per day to meet the
electricity is supplied from the national grid. When the desalina- needs of 100,000 people. In a concentrated PV system, lenses or
tion plant is far from the grid and there is a need to extend the mirrors focus sunlight on ultra-efficient solar cells that convert the
transmission line or when the desalination plant is installed in a light into electricity. The idea is to cut costs by using fewer
remote area, then the cost of the grid electricity is much higher. semiconductor solar cell materials. But multiplying the sun's
For this situation, the use of the electricity produced from renew- power by hundreds of times creates a lot of heat. IBM's solution
able energy systems will be the best choice. For this case, using a is to use a highly conducting liquid metal – an indium gallium
system comprising PV arrays, batteries, and diesel generator as alloy – on the underside of silicon computer chips to ferry heat
auxiliary is the best choice and the cost of the fresh water away. Using this liquid metal, the researchers have been able to
produced is US$1.957/m3. The cost of permeate water produced concentrate 2300 times the sun’s power onto a one-square-
from using only AC generator is higher (US$2.199/m3) in addition centimeter solar device. That is three times higher than what’s
to the difficulties of transporting fuel to the site and problems of possible with current concentrator systems. For the RO unit, IBM
greenhouse gas emission. When it is difficult to transport fuel to has worked with researchers at the University of Texas at Austin to
develop a robust membrane that makes RO more energy-efficient. improvements in MD as well as the application characteristics
Desalination is done today with polyamide membranes that get required for commercial deployment. Compared to conventional
clogged with oil and organisms in seawater. The chlorine used to separation processes, MD, due to its mass and heat transfer
pretreat seawater also breaks down the membranes over time. The mechanisms, can be operated at low temperatures than the
new polymer membrane contains hexafluoro alcohols, a material traditional distillation and lower operating hydrostatic pressures
used by IBM to pattern copper circuits on computer chips. At high than the pressure driven operations with high productivity, less
pH, the fluorine groups become charged and protect the mem- demanding membrane mechanical properties and high rejection
brane from chlorine and clogging. As a result, water flows through factor achieved for solutions containing non-volatile solutes such
it 25% to 50% faster than through currently used RO membranes. as salts in the case of desalination. MD has been widely studied for
The new membranes remove 99.5% of the salt in seawater, a desalination purposes at bench scale and experiments at pilot
rejection comparable with that of conventional polyamide mem- scale have also shown promising results [475,476]. In particular,
branes. The Al-Khafji desalination plant is the first of three steps in water flux in MD are only slightly sensitive to the feed salinity
a solar-energy program launched by KACST to reduce desalination [474,477] making MD particularly suited to desalinate high salinity
costs. The second step will be a 300,000-cm3 facility and the third sources without substantial productivity reduction. Almost com-
phase will involve several more solar-power desalination plants at plete salt rejection has consistently been reported in the literature,
various locations. even for very high salinity feeds [478,479].
It should be clarified that MD has not been yet commercialized
for large scale desalination plant in spite of its attractive features.
3.2.2. Solar assisted MD MD has the disadvantage compared to MED and MSF of additional
In MD differently from other isothermal membrane processes resistance to mass transport by the membrane with consequent
such as pressure driven membrane operations (ultrafltration, lower flux and some technical problems such as the membrane
microfiltration, nanofiltration, reverse osmosis), both thermal wetting. However, intense research to overcome these drawbacks
energy and mechanical energy are required. MD is a thermally by developing new membranes for MD is in progress [480–483].
driven process in which a hydrophobic microporous membrane MD desalination requires both thermal energy to drive the phase-
acts as a physical barrier separating, in the specific case of change process and the electricity required to drive the membrane
desalination application, seawater on one side of the membrane process. In Fig. 50 schematization of solar assisted MD is shown:
(hot) and condensing vapor on the other side (cold). The hydro- low grade heat from solar collectors or a solar pond and electricity
phobic membrane prevents seawater from passing through the from a PV system or the power grid could be used. A summary of
membrane pores and only allows the generated vapor transfer to some pilot and commercial solar-powered MD plants is given in
the other side. There are four kinds of configurations depending on Table 17. For all the plants listed in Table 17, the aim was that of
the method by which the vapor is recovered once it has migrated developing environmentally friendly improved-cost desalination
through the membrane: direct contact membrane distillation technology based on solar MD in order to supply fresh water in
(DCMD); air gap membrane distillation (AGMD); sweeping gas arid and semi-arid regions. Medesol project, for example, evalu-
membrane distillation (SGMD); vacuum membrane distillation ated the technical feasibility of producing potable water from
(VMD) (Fig. 49). seawater by integrating several membrane distillation modules
Camacho et al. [473] and Alkhudhiri et al. [474] reviewed recent (Multi-step Membrane Distillation System) to develop systems for
advances in MD on module configurations, applications and a capacity ranging from 0.5 to 50 m3/day [485]. Fraunhofer ISE
economics, identifying areas that may lead to technological developed solar thermally driven compact desalination systems
Feed Sweep gas out

Feed
Permeate
Product
Membrane
Membrane
Feed Sweep gas

Feed Permeate
DCMD SGMD
Feed Cooling fluid

Feed
Vacuum
Air gap
Membrane Membrane
Product
Condensing plate
Feed Feed
Cooling fluid
Product
VMD AGMD
Fig. 49. Membrane distillation (MD) configurations.

Fig. 50. Schematic of solar assisted MD [440].
based on spiral wound MD for capacities between 100 and 500 L/ development. The disadvantages of additional resistance to mass
day and larger systems of up to 10 m3/day. Eight pilot plants were transport by the membrane compared to MSF and MED can be
installed in five different countries, i.e. Grand Canaria, Egypt, compensated by creating larger area for heat and mass transfer. In
Jordan, Germany, and Italy [489]. The compact system in Italy addition, MD could be used integrated with RO for high recovery
was powered by a hybrid system using solar energy and waste or highly concentrated salt water treatment, that RO could not
heat from diesel engines [490]. handle and which normally require high energy consumption.
The approach of using solar assisted MD is not only diffuse in Operating in a proper way, pure water by seawater desalination
Mediterranean and Arabic countries, but also experimented in Asia using an integrated membrane system can be produced with a
and Australia. The Japanese Water Re-use promotion center higher recovery factor compared to a RO unit alone. On the basis of
(WRPC) in co-operation with Takenaka Corporation (a construc- simulation and experiments at bench-scale, VMD has proved to be
tion company) and Organo Corporation (a water-processing equip- very interesting when integrated in a seawater treatment line as a
ment manufacturer), has developed and demonstrated a complementary process to SWRO [493].
desalination system which uses MD process provided with heat
and electricity generated solely by solar energy (Fig. 51). 3.3. Microbial desalination cells: A high innovative desalination
All the electricity required in the plant is supplied by a PV technology
power generation system made up of 46 single crystalline silicon
modules each 0.45 m wide and 1.0 m long, producing a total of In Section 2.1.2.3.2 of this article, MECs, i.e. bioelectrochemical
2.3 kW. A variable voltage and frequency inverter connected to the systems that use bacteria to create renewable energy in the form
photovoltaic system automatically starts up the desalination of hydrogen (and methane) have been mentioned. Differently from
system according to the amount of solar radiation available and MECs, biolectrochemical systems such as Microbial desalination
runs the pumps by controlling the output of the photovoltaic cells (MDCs), use bacteria to create renewable energy in the form
system [491]. National Centre of Excellence in Desalination in of electricity (such as MFCs) to power desalination through ionic
Australia (NCEDA) is a partnership with University of Technology exchange membranes. The recent discovery of MDC [494] has
Sydney, the WA Department of Housing, Memsys, Parsons Brinck- drawn great attention as the exponential increase of research
erhoff, IFTS (France) and Singapore Membrane Technology Centre articles in the field demonstrates because it provides a promising
in an innovative project based on solar powered VMD to secure approach for sustainable wastewater treatment and low cost
water supplies in desert communities characterized by abundant desalination [495–508]. Water desalination can be accomplished
hypersaline groundwater. A four stage VMD pilot plant, supplied without external electrical energy input or high water pressure by
by Memsys, will produce up to one kilolitre (kL) of distilled water using a source of organic matter as fuel to desalinate water. A MDC
per day from hypersaline ground water. Successful operation will was obtained by the modification of a MFC (see Section 2.1.2.3.2 of
lead to construction of a large plant of around 20 kL per day. Power this article), by placing two ion exchange membranes between the
and heat will be initially supplied by diesel but replaced with a anode and cathode, creating a middle chamber for water desalina-
combination of PV and sunlight concentrated by a parabolic tion [495] (Fig. 52).
reflector, supplied by a US company, Cogenra [492]. An anion exchange membrane (AEM) was placed adjacent to the
As for MD energy consumption and cost, there are some anode, and a cation exchange membrane (CEM) was positioned next
disagreements among the researchers. Some believe that MD is to the cathode. When current was produced by bacteria on the
unfavorable when compared to evaporative not membrane-based anode, ionic species in the middle chamber were transferred into the
processes such as MED and MSF from an energy utilization point two electrode chambers, desalinating the water in the middle
of view because of the additional resistance to mass transport and chamber. More in details, the AEM prevents protons and other
reduced thermal efficiency (due to heat conductivity losses) positively charged ions from leaving the anode chamber, so charge
offered by the membrane; while other scientists claim that MD is balanced by anions (Cl ) moving from the central desalination
consumption is comparable to that of MSF plants but the pumping chamber into the anode chamber. Protons are depleted in the
power is less [440]. Overall, solar assisted MD is still under cathode chamber when they combine with electrons and oxygen
Table 17
Some pilot and commercial solar assisted MD plants.
Acronym technology MD Configuration Capacity Thermal energy consumption Electricity consumption Stage Ref
Scarab AGMD 1–2 m3/day 5–12 kW h/m3 0.6–1.5 kW h/m3 Commercialized [484]
Medesol AGMD 0.5–50 m3/day 810 kW h/m3 – Pilot plant [485]
Memstill AGMD 80–50 m3/day 22–90 kW h/m3 – Pilot plant [486]
Memsys VMD 1 m3/day 175–350 kW h/m3 0.75–1.75 kW h/m3 Commercialized [487]
Smades Spiral wound MD 0.6–0.8 m3/day 200–300 kW h/m3 – Pilot plant [488]
Fig. 51. Water desalination plant based on membrane process using solar energy, developed by the Japanese water re-use promotion center, in co-operation with Takenaka
Corporation and Organo Corporation [491].
produce higher cathode potentials than oxygen which may have

aided the overall extent of desalination [495]. The reduction in
the water salinity over a single cycle was up to a 63%, lower than
e- the system with ferricyanide. While this extent of desalination
e-
accomplished is relatively large, and no external source of
Aerobic electrical was needed, it was insufficient to treat the water to
Anaerobic Desalination
cell levels needed for drinking water. Therefore, Mehanna et al. [495]
O2 suggested that the most useful application for a MDC with an air
H+ CO2 cathode may be as a pre-treatment method of saline water for RO
Cl- processing (Scheme 4).
The energy needed for RO decreases with a reduction in the
salinity of the treated water, and thus the reduction of the con-
ductivity of the saline water by 50% or more would greatly benefit
Substrate Na+ energy consumption in the RO process [495]. Also Brastad and He
H2O [505] proposed to use MDC as pre-treatment step in membrane
Bacteria
desalination processes, and specifically in alternative to lime soft-
Anode AEM CEM Cathode ening. Lime softening adds lime to hard water to precipitate calcium
Fig. 52. Three-chamber MDC used for desalination.
ions as calcium carbonate and magnesium ions as magnesium
hydroxide [506]. Lime softening is also recognized by the U.S.
Environmental Protection Agency (EPA) as the best applied technique
to form water, with charge balanced by cations (Na þ ) passing from for arsenic, barium, beryllium, chromium, copper, fluoride, lead,
the desalination chamber through the CEM into the cathode chamber mercury, cadmium, nickel, and radionuclides [505].
(Fig. 52). As a consequence of these two charge-transfer processes, MDC represents an environmentally friendly, cost-effective,
NaCl in the middle desalination chamber is removed and the water is and low energy consuming process, without the drawbacks of
desalinated. Proof-of-concept experiments for this approach using lime softening such as the production of a high-volume lime
MDC was demonstrated using water at different initial salt concen- sludge stream, and the required use of chemicals such as quick
trations (5, 20, and 35 g/L) with acetate used as substrate for the lime, coagulants (iron or aluminum based), soda ash, and acids for
bacteria and a ferricyanide catholyte [494]. The MDC produced a adjusting the pH. The encouraging results reported by Brastad and
maximum of 2 W/m2 (31 W/m3) while at the same time removing He [505] demonstrated the potentiality of MDCs as interesting
about 90% of the salt in a single desalination cycle. In a subsequent solution for the water softening market using only a source of
research article [495], the same research group reported the perfor- biodegradable organic matter and bacteria. An extensive treatise of
mance of a MDC where desalination was sustained using oxygen at all the aspects concerning MDC is far beyond the scope of this
the cathode (air cathode) rather than ferricyanide. Chemical cath- review and further reading of some recent reviews on the subject
olytes such as ferricyanide are not sustainable, but they generally is recommended [507–509].
Feed water consumption, well fits a decentralized bio-hydrogen produc-

with >50% of Permeate
RO
tion approach, characterized by reduced costs associated with
salinity
MDC transport and storage of the elusive small hydrogen molecule.
reduction
A membrane operation such as Reverse Electrodialysis (RED)
integrated with microbial electrolysis cell (MEC) in microbial
Brine
reverse-electrodialysis electrolysis cell (MREC) represents
another excellent example of PI. H2 production in MRECs is
achieved by two driving forces: a thermodynamically favorable
Scheme 4. MDC as pretreatment step for RO.
oxidation of organic matter by exoelectrogens on the anode of
MEC; and the energy derived from the salinity gradient
4. Conclusions between seawater and river water, extracted with RED.
Salinity gradient power is another important renewable energy
In the examples given in this article two types of interconnec- source, created from the difference in salt concentration
tions between membrane processes and renewable energy sources between two fluids, commonly fresh and salt water, e.g. when
have been reviewed: i) membrane processes with active roles in a river flows into the sea. The two technologies for which
the “extraction” of renewable energy (i.e. hydrogen from biomass demonstration projects are running are both membrane-based,
gasification, biomethane/biohydrogen generation and upgrading, i.e. PRO and RED. The salinity gradient difference is the driving
biobutanol production and recovery, salinity gradient power); force in transporting water (in PRO) or ions (RED). In the case of
ii) membrane technologies for water desalination such as mem- PRO freshwater flows through the semipermeable membrane,
brane distillation powered by renewable energies. In most of them increasing the pressure within the seawater chamber; the
the key features of process intensification approach i.e. improve- augmented flow of the pressurized stream then passes through
ments in processing, substantially decreasing equipment-size/ a hydroelectric turbine which extracts the power. In RED, the
production-capacity ratio, energy consumption, waste production, ions transport, generated from the salinity gradient difference
provide real opportunities for optimizing conventional processes. results in an electric potential, which is then converted to
electricity.
In thermochemical biomass conversions such as gasification In both PRO and RED, several technological challenges, includ-
and fast pyrolysis the use of unconventional technologies such ing quality of the membranes, technology to produce large
as MRs for steam reforming and water gas shift: reduces capital amounts of durable and affordable membranes, bio-fouling,
and downstream separation costs (the four reaction stages plus development of the modules containing membranes, pre-
a PSA unit of the conventional biomass gasification are reduced treatment of water are to be addressed.
in only two reactors able to produce hydrogen, CO free); Regarding the membranes, it is estimated that they account for
improves yields and selectivities (extraction of hydrogen via up to 80% of total process capital costs because currently
membrane gas permeation from the product side of WGS shifts available membranes for salinity gradient power are 2-3 times
the equilibrium of the reaction to the product side, i.e. more expensive than commercially available membranes.
H2 þCO2). However, the integration of membrane technology Therefore, the current research trend in the field is addressed
in steam reforming or promising autothermal reforming to find membranes that are efficient and robust enough to
requires the development of novel catalysts and membranes boost production.
with high performance at much lower temperatures than in Excluding recent large and medium scale RO desalination
conventional catalytic reformers and ideal separation condi- plants where the objective is to use wind power to meet as
tions, respectively. In fact, regarding the membranes, metallic much of the energy requirement as possible, much effort in the
membranes not only are relatively expensive, but are first of all research on membrane desalination powered by renewable
sensitive to sulfur contained in the syngas; dense ceramic energies concerns solar assisted MD for small, in most cases
membranes require high syngas temperatures ( 4900 1C) for remote, arid, delocalized regions, in the logic of “Sustainable
ion conduction, requiring an additional step of hot syngas Energy for all”. MD requires low temperature heat and elec-
clean-up. Promising results were obtained with carbon mole- tricity. MD, in fact, differently from RO, can tolerate fluctuating
cular sieves membranes, which revealed exceptionally stable and intermittent operating conditions as well as it requires low
membrane performance in the presence of raw coal and grade thermal energy. In this respect, solar collectors and PV
biomass gasifier off-gas with no pre-treatment prior to mem- are mature technologies which showed their successful inte-
brane exposure to syngas [74]. gration with MD process in various pilot plants. However, in the
On the other side, dense ceramic and cermet membranes techno-economic analyses of MD, compared to conventional
which are operational at high temperatures (4700 1C) are thermal desalination processes such as MED and MSF, a crucial
necessary if used in the intensified gasification concept of role is played by the membrane, with its resistance to mass
membrane gasification reactor [113], where a high temperature transport and reduced thermal efficiency, due to heat conduc-
H2 permselective membrane is incorporated into the gasifica- tivity losses. Therefore, the enhancement of membrane perfor-
tion reactor and separates off H2 directly during the gasification mances by developing novel membrane architecture is of great
stage, maximizing its production by shifting the water gas shift importance for MD in general and solar assisted MD, in
equilibrium displacement as well as that of steam reforming, particular.
reducing the five stages (four reaction stages plus a PSA unit) in Least, but not last, Microbial desalination cells (MDCs) repre-
only one reactor able to produce pure hydrogen. sent another example of “sustainable desalination” strictly
In biological biomass conversion such as fermentation, various related to “Sustainable Energy for all”: the energy source for
studies on the application of AnMBRs with their characteristics desalination, which occurs by driving ion transport through
of efficient retention of active biomass within the fermenter, ion-exchange membranes, is the electrical potential that exoe-
enhanced stability and reliable operation, demonstrated an lectrogenic microorganisms produce from the degradation of
enhancement of biogas production. Regarding its upgrading, organic matter. MDCs, which are new technologies that are just
the use of membrane gas separation, in particular of membrane beginning to be developed and therefore have several chal-
absorbers (another example of PI) with their low energy lenges to be faced, may have multiple applications and uses,
and different types of systems may be developed depending on [28] Ramon GZ, Feinberg BJ, Hoek EMV. Membrane-based production of salinity-
the intended use of both the desalinated product water, and the gradient power. Energy Environ Sci 2011;4:4423–34.
[29] Post JW, Veerman J, Hamelers HVM, Euverink GJW, Metz SJ, Nymeijer K,
wastewater. When high desalinated water is the target, the best et al. Salinity gradient power: evaluation of pressure-retarded osmosis and
use of MDCs will be as RO pre-treatment step; if desalinated reverse electrodialysis. J Membr Sci 2007;288:218–30.
water produced by MDCs is used for irrigation or more [30] Qtaishat MR, Banat F. Desalination by solar powered membrane distillation
systems. Desalination 2013;308:186–97.
conventional grey water applications, then partial desalination [31] Subramani A, Badruzzaman M, Oppenheimer J, Jacangelo JG. Energy mini-
of a brackish water might be acceptable. mization strategies and renewable energy utilization for desalination: a
review. Water Res 2011;45:1907–20.
[32] Li C, Goswami Y, Stefanakos E. Solar assisted sea water desalination: a
review. Renewable Sustainable Energy Rev 2013;19:136–63.
[33] Bridgewater AV. Principles and practice of biomass fast pyrolysis processes
References for liquids. J Anal Appl Pyrolysis 1999;51:3–22. 〈http://www.navigantre
search.com/newsroom/global-investment-in-biomass-power-generation-
[1] 〈http://www.se4all.org/wp-content/uploads/2013/10/GA-resolutio will-total-104-billion-through-2021〉.
n-A-67-215-SE4ALL-DECADE.pdf〉; 2014 (viewed on 26 October 2014). [34] Abdollahi M, Yu J, Hwang HT, Liu PKT, Ciora R, Sahimi M, et al. Process
[2] 〈http://ec.europa.eu/energy/energy2020/roadmap/doc/com_2011_8852_en. intensification in hydrogen production from biomass-derived syngas. Ind
pdf〉; 2013 (viewed on 23 October 2013). Eng Chem Res 2010;49:10986–93.
[3] Malakoff D. The gas surge. Science 2014;6191:1464–5. [35] Bridgwater AV. Renewable fuels and chemicals by thermal processing of
[4] 〈http://shalegas-europe.eu/shale-gas-explained/shale-gas-and-europe/〉; biomass. Chem Eng J 2003;91:87–102.
2014 (viewed on 30 October 2014). [36] Koc R, Kazantzi NK, Ma YH. Membrane technology embedded into IGCC
[5] Vidic RD. Impact of shale gas development on regional water quality. Science plants with CO2 capture: an economic performance evaluation under
2013;340:12350091–9; uncertainty. Int J Greenhouse Gas Control 2014;26:22–38.
Robinson P. Fracking fluid data found wanting. Chem World 2014;11(10):10; [37] Beér J. High efficiency electric power generation; the environmental role.
Bowley E. Concerns over reclaimed fracking fluid. Chem World 2014;11 Prog Energy Combust Sci 2007;33:107–34.
(10):25. [38] Siemens Fuel Gasification Technology. Siemens energy sector; 2008. 〈http://
[6] Ellsworth WL. Injection-induced Earthquakes. Science 2013;341:12259421–7. www.energy.siemens.com.cn/CN/downloadCenter/Documents/E_F_fuel_gasi
[7] McNutt M. Bridge or Crutch? Science 2013;342:909. fier_en.pdf〉 [accessed 22.08.14].
[8] IRENA costing papers (〈www.irena.org/publications〉) and REN21’s “renew- [39] Chen Q, Rao A, Samuelsen S. H2 coproduction in IGCC with CCS via coal and
ables 2012 global status report”. biomass mixture using advanced technologies. Appl Energy 2014;118:258–70.
[9] Wick GL, Schmitt WR. Prospects for renewable energy from sea. Mar Technol [40] Cormos CC. Hydrogen and power co-generation based on coal and biomass/
Soc J 1977;11:16–21. solid wastes co-gasification with carbon capture and storage. Int J Hydrogen
[10] International Renewable Energy Agency (IRENA), Renewable power genera- Energy 2012;37:5637–48.
tion costs in 2012: an Overview. Abu Dhabi, United Arab Emirates; 2013. [41] Marano JJ, Ciferino JP. Integration of gas separation membranes with IGCC
(〈www.irena.org/Publications〉). identifying the right membrane for the right job. Energy Proc 2009;1:361–8.
[11] Stankiewicz AI, Moulijn JA. Process intensification: transforming chemical [42] Lin H, He Z, Sun Z, Vu J, Ng A, Mohammed M, et al. CO2-selective membranes
engineering. (January). Chem Eng Prog 2000:22–34. for hydrogen production and CO2 capture—Part I: Membrane development. J
[12] 〈http://www.efce.info/index.php?id=111785&site=efce&lang=en〉 European Membr Sci 2014;457:149–61.
roadmap. [43] Merkel TC, Zhou M, Baker RW. Carbon dioxide capture with membranes at
[13] 〈http://www.ispt.eu/media/DSD_Research_Agenda.pdf〉; 2013 (viewed on 23 an IGCC power plant. J Membr Sci 2012;389:441–50.
October 2013). [44] Franz J, Scherer V. An evaluation of CO2 and H2 selective polymeric membranes
[14] Charpentier JC. Modern chemical engineering in the framework of globaliza- for CO2 separation in IGCC processes. J Membr Sci 2010;359:173–83.
tion, sustainability and technical innovation. Ind Eng Chem Res 2007;46: [45] Franz J, Maas P, Scherer V. Economic evaluation of pre-combustion CO2-
3465–3485. capture in IGCC power plants by porous ceramic membranes. Appl Energy
[15] Drioli E, Romano M. Progress and new perspectives on integrated membrane 2014;130:532l542.
operations for sustainable industrial growth. Ind Eng Chem Res 40, 2001, [46] Ku AY, Kulkarni P, Shisler R, Wei W. Membrane performance requirements
1277-1300; for carbon dioxide capture using hydrogen-selective membranes in inte-
Nunes SP, Peinemann KV. Membrane Technology in the Chemical Industry. grated gasification combined cycle (IGCC) power plants. J Membr Sci
Weinheim: Wiley-VCH; 2001. 2011;367:233–9.
[16] Buonomenna MG. Membrane processes for a sustainable industrial growth. [47] Trane R, Dahl S, Skjøth-Rasmussen MS, Jensen AD. Catalytic steam reforming
RSC Adv 2013;3:5694–740. of bio-oil. Int J Hydrogen Energy 2012;37:6447–72;
[17] Shen J, Huang J, Ruan H, Wang J, Van der Bruggen B. Techno-economic Tanksale A, Beltramini JN, Lu GM. A review of catalytic hydrogen produc-
analysis of resource recovery of glyphosate liquor by membrane technology. tion processes from biomass. Renewable Sustainable Energy Rev 2010;14:
Desalination 2014;342:118–25. 166–182.
[18] Lubsungneon J, Srisuno S, Rodtong S, Boontawan A. Nanofiltration coupled [48] Czernik S, French R. Distributed production of hydrogen by auto-thermal
with vapor permeation-assisted esterification as an effective purification reforming of fast pyrolysis bio-oil. Int J Hydrogen Energy 2014;39:744–50.
step for fermentation-derived succinic acid. J Membr Sci 2014;459:132–42. [49] Kosaric N, Velikonja J. Liquid and gaseous fuels from biotechnology:
[19] Ang WL, Mohammad AW, Hilal N, Leo CP. A review on the applicability of challenge and opportunities. FEMS Microbiol Rev 1995;16:111–42.
integrated/hybrid membrane processes in water treatment and desalination [50] Claassen PAM, van Lier JB, Lopez Contreras AM, van Niel EWJ, Sijtsma L,
plants. Desalination 2014. http://dx.doi.org/10.1016/j.desal.2014.03.008; Stams AJM, et al. Utilisation of biomass for the supply of energy carriers.
Buonomenna MG. Hybrid membrane processes in desalination systems. in: Appl Microbiol Biotechnol 1999;52:741–55.
Recent developments in separation research, editor. Pandalai, SG, Transworld [51] Teella A, Huber GW, Ford DM. Separation of acetic acid from the aqueous
Research Network. Trivandrum, India. 2012, ISBN: 978-81-7895-574-2. fraction of fast pyrolysis bio-oils using nanofiltration and reverse osmosis
[20] 〈https://www.irena.org/menu/index.aspx? membranes. J Membr Sci 2011;378:495–502.
mnu=Subcat&PriMenuID=36&CatID=141&SubcatID=277〉. [52] Hassan EB, Abou-Yousef H, Steele P. Increasing the efficiency of fast pyrolysis
[21] Bakonyi P, Nemestóthy N, Bélafi-Bakó K. Biohydrogen purification by process through sugar yield maximization and separation from aqueous
membranes: an overview on the operational conditions affecting the fraction bio-oil. Fuel Process Technol 2013;110:65–72.
performance of non-porous, polymeric and ionic liquid based gas separation [53] Pinto PCR, Mota IF, Loureiro JM, Rodrigues AE. Membrane performance and
membranes. Int J Hydrogen Energy 2013;38:9673–87. application of ultrafiltration and nanofiltration to ethanol/water extract of
[22] Bakonyi P, Kumar G, Nemestóthy N, Lin CY, Bélafi-Bakó K. Biohydrogen Eucalyptus bark. Sep Purif Technol 2014;132:234–43.
purification using a commercial polyimide membrane module: studying the [54] Wang C, Li Q, Tang H, Yan D, Zhou W, Xing J, et al. Membrane fouling
effects of some process variables. Int J Hydrogen Energy 2013;38:15092–9. mechanism in ultrafiltration of succinic acid fermentation broth. Bioresour
[23] Makaruk A, Miltner M, Harasek M. Membrane biogas upgrading processes Technol 2012;116:366–71.
for the production of natural gas substitute. Sep Purif Technol 2010;74: [55] Toledano A, García A, Mondragon I, Labidi J. Lignin separation and fractiona-
83–92. tion by ultrafiltration. Sep Purif Technol 2010;71:38–43.
[24] Basu S, Khan AL, Cano-Odena A, Liu C, Vankelecom IFJ. Membrane-based [56] Krawczyk H, Arkell A, Jönsson A-S. Membrane performance during ultra-
technologies for biogas separations. Chem Soc Rev 2010;39:750–68. filtration of a high-viscosity solution containing hemicelluloses from wheat
[25] Cicek N, Winnen H, Suidan MT, Wrenn BE1, Urbain V, Manem J. Effectiveness bran. Sep Purif Technol 2011;83:144–50.
of the membrane bioreactor in the biodegradation of high molecular weight [57] Qi B, Luo J, Chen G, Chen X, Wan Y. Application of ultrafiltration and
compounds. Water Res 1998;32:1553–63. nanofiltration for recycling cellulase and concentrating glucose from enzy-
[26] Visvanathan C, Abeynayaka A. Developments and future potentials of matic hydrolyzate of steam exploded wheat straw. Bioresour Technol
anaerobic membrane bioreactors (AnMBRs). Membr Water Treat 2012;3: 2012;104:466–72.
1–23. [58] Dalmau M, Monclús H, Gabarrón S, Rodriguez-Roda I, Comas J. Towards
[27] Logan BE, Elimelech M. Membrane-based processes for sustainable power integrated operation of membrane bioreactors: effects of aeration on
generation using water. Nature 2012;488:313–9. biological and filtration performance. Bioresour Technol 2014;171:103–12.
[59] Wallace JM, Safferman SI. Anaerobic membrane bioreactors and the influ- cycle (IGCC) power plant with CO2 capture. Fuel Process Technol
ence of space velocity and biomass concentration on methane production for 2011;92:1685–95.
liquid dairy manure. Biomass Bioenergy 2014;66:15–143. [89] Repasky JM, Foster EP, Armstrong PA, Stein VE, Anderson LL. ITM oxygen
[60] Wang Z, Ma J, Tang CY, Kimura K, Wang Q, Han X. Membrane cleaning in development for advanced oxygen supply. (October 12). San Francisco, CA,
membrane bioreactors: a review. J Membr Sci 2014;468:276–307. USA: Gasification Technologies Council; 2011.
[61] Sagehashi Masaki, Nomura Tsuyoshi, Shishido Hiromu, Sakoda Akiyoshi. [90] Mak A, Foster TEP, Armstrong PA, Repasky JM, Stein VE. ITM oxygen
Separation of phenols and furfural by pervaporation and reverse osmosis technology for clean energy applications. In: 2013 30th Annual international
membranes from biomass—superheated steam pyrolysis-derived aqueous Pittsburgh coal conference 2013, PCC; 2013. 1, p. 270–300.
solution. Bioresour Technol 2007;98:2018–26. [91] Repasky JM, Anderson LL, Stein VE, Armstrong PA, Foster EP. ITM Oxygen
[62] Kaombe DD, Hägg M-B. Forward osmosis for the dewatering of pyrolysis oil technology: scale-up toward clean energy applications. In: 2012 International
aqueous phase. Sep Purif Technol 2014;138:92–7. Pittsburgh coal conference 2012. Pittsburgh, PA., USA; October 15–18, 2012.
[63] Buckwalter P, Embaye T, Gormly S, Trent JD. Dewatering microalgae by [92] Aznar MP, Caballero MA, Corella J, Molina G, Toledo JM. Hydrogen produc-
forward osmosis. Desalination 2013;312:19–22. tion by biomass gasification with steam-O2 mixtures followed by a catalytic
[64] Gerardo ML, Oatley-Radcliffe DL, Lovitt RW. Integration of membrane steam reformer and a CO-shift system. Energy Fuels 2006;20:1305–9.
technology in microalgae biorefineries. J Membr Sci 2014;464:86–99. [93] Kohl AL, Nielson R. Gas purification. 5th ed.. Houston, TX: Gulf Publishing;
[65] Zhao S, Zou L, Tang CY, Mulcahy D. Recent developments in forward osmosis: 1997.
opportunities and challenges. J Membr Sci 2012;396:1–21. [94] Shao L, Low BT, Chung TS, Greenberg AR. Polymeric membranes for the
[66] Modigell M, Schumacher M, Teplyakov VV, Zenkevich VB. A membrane hydrogen economy: contemporary approaches and prospects for the future.
contactor for efficient CO2 removal in biohydrogen production. Desalination J. Membr. Sci 2009;327:18279.
2008;224:186–90. [95] Grainger D, Hagg M. Techno-economic evaluation of a PVAm CO2-selective
[67] Grzenia DL, Schell DJ, Ranil Wickramasinghe S. Membrane extraction for membrane in an IGCC power plant with CO2 capture. Fuel 2008;87:14–24.
removal of acetic acid from biomass hydrolysates. J Membr Sci 2008;322: [96] Baker RW. Membrane technology and applications. 2nd ed.. Chichester,
189–195. England: John Wiley & Sons Ltd.; 2004.
[68] Praveen P, Loh K-C. Simultaneous extraction and biodegradation of phenol in [97] Stankiewicz AI. Reactive separations for process intensification: an industrial
a hollow fiber supported liquid membrane bioreactor. J Membr Sci perspective. Chem Eng Process 2003;42:137–44.
2013;430:242–51. [98] Iyoha O, Enick R, Killmeyer R, Howard B, Morreale B, Ciocco M. Wall-
[69] Singhania RR, Patel AK, Christophe G, Fontanille P, Larroche C. Biological catalyzed water–gas shift reaction in multi-tubular Pd and 80 wt% Pd 20 wt
upgrading of volatile fatty acids, key intermediates for the valorization of % Cu membrane reactors at 1173 K. J Membr Sci 2007;298:14–23.
biowaste through dark anaerobic fermentation. Bioresour Technol [99] Bi Y, Xu H, Li W, Goldbach A. Water–gas shift reaction in a Pd-membrane
2013;145:166–74. reactor over Pt/Ce0.6Zr0.4O2 catalyst. Int J Hydrogen Energy 2009;34:2965–71.
[70] Chen Q, Rao A, Samuelsen S. H2 coproduction in IGCC with CCS via coal and [100] Mendes D, Chibante V, Zheng IM, Tosti S, Borgognoni F, Mendes A, et al.
biomass mixture using advanced technologies. Appl Energy 2014;118: Enhancing the production of hydrogen via water–gas shift reaction using Pd-
258–270. based membrane reactors. Int J Hydrogen Energy 2010;35:12596–608.
[71] Armstrong PA, Foster EP, Gunardson HH, ITM oxygen for gasification. In: SPE/ [101] Lewis AE, Kershner DC, Paglieri SN, Slepicka MJ, Way JD. Pd–Pt/YSZ
PS-CIM/CHOA international thermal operations and heavy oil symposium. composite membranes for hydrogen separation from synthetic water–gas
Society of Petroleum Engineers: Calgary, AB, Canada; 2005. shift streams. J Membr Sci 2013;437:257–64.
[72] He X, Hägg M-B. Membranes for environmentally friendly energy processes. [102] Battersby S, Duke MC, Liu S, Rudolph V, Diniz da Costa JC. Metal-doped silica
Membranes 2012;2:706–26. membrane reactor: operational effects of reaction and permeation for the
[73] Yu J, Tan M, Liu PKT, Sahimi M, Tsotsis TT. Hydrogen production from water gas shift reaction. J Membr Sci 2008;316:46–52.
biomass-derived syngas using a membrane reactor based process. Ind Eng [103] Battersby S, Smart S, Ladewig B, Liu S, Duke MC, Rudolph V, et al.
Chem Res 2014;53:819–27. Hydrothermal stability of cobalt silica membranes in a water gas shift
[74] Parsley D, Ciora Jr RJ, Flowers DL, Laukaitaus J, Chen A, Liu PKT, et al. Field membrane reactor. Sep Purif Technol 2009;66:299–305.
evaluation of CMS membranes for the separation and purification of [104] Smart S, Beltramini J, Diniz da Costa JC, Katikaneni SP, Pham T. Microporous
hydrogen from coal and biomass derived syngas. J Membr Sci silica membranes: fundamentals and applications in membrane reactors for
2014;450:81–92. hydrogen separation. In: Basile A, editor. Handbook of membrane reactors.
[75] Basile A, Gallucci F, Iulianelli A, Borgognoni F, Tosti S. Acetic acid steam Woodhead Publishing; 2013. p. 337–69.
reforming in a Pd–Ag membrane reactor: the effect of the catalytic bed [105] Kim SJ, Xu Z, Reddy GK, Smirbiotis P, Dong JH. Effect of pressure on high-
pattern. J Membr Sci 2008;311:46–52. temperature water gas shift reaction in microporous zeolite membrane
[76] Iulianelli A, Longo T, Basile A. CO-free hydrogen production by steam reactor. Ind Eng Chem Res 2012;51:1364–75.
reforming of acetic acid carried out in a Pd–Ag membrane reactor: the effect [106] Zhang Y, Wu Z, Hong Z, Gu X, Xu N. Hydrogen-selective zeolite membrane
of co-current and counter-current mode. Int J Hydrogen Energy 2008;33: reactor for low temperature water gas shift reaction. Chem Eng J
4091–4096. 2012;197:314–21.
[77] Hydrogen energy and fuel cells – a vision of our future – European [107] Sá S, Silva H, Sousa JM, Mendes A. Hydrogen production by methanol steam
Commission-Directorate General for Research; 2003. reforming in a membrane reactor: palladium vs. carbon molecular sieve
[78] 〈http://media-3.web.britannica.com/eb-media/64/97264-004-127AEA3B.gif〉. membranes. J Membr Sci. 2009;339:160–70.
[79] Behling NH. Fuel cells: current technology challenges and future research [108] Harale A, Hwang HT, Liu PKT, Sahim M, Tsotsis TT. Experimental studies of a
needs. Amsterdam: Elsevier; 2013. hybrid adsorbent-membrane reactor (HAMR) system for hydrogen produc-
[80] Barbir F. PEM fuel cells: theory and practice. New York, NY: Elsevier tion. Chem Eng Sci 2007;62:4126–37.
Academic Press; 2005. [109] Harale A, Hwang HT, Liu PKT, Sahimi M, Tsotsis TT. Design aspects of the
[81] 2011 Fuel cell technologies market report, U.S. Department of Energy, Energy cyclic hybrid adsorbent-membrane reactor (HAMR) system for hydrogen
Efficiency & Renewable Energy; July 2012. production. Chem Eng Sci 2010;65:427–35.
[82] Long HA, Wang TA. System performance and economic analysis of IGCC with [110] Li H, Goldbach A, Li WZ, Xu HY. PdC formation in ultrathin Pd membranes
supercritical steam bottom cycle supplied with varying blends of coal and during separation of H2/CO mixtures. J Membr Sci 2007;299:130–7.
biomass feedstock . In: Proceedings of ASME 2011 international mechanical [111] Abdollahi M, Yu J, Liu PKT, Ciora R, Sahimi M, Tsotsis TT. Hydrogen production
engineering congress and exposition, 2011. Denver, CO, USA; November 11- from coal using a membrane reactor based process. J Membr Sci
17, 2011. 2010;363:160–9.
[83] Wang T, Long HA. Performance and economic analysis of biomass/coal co- [112] Liu PKT, Sahimi M, Tsotsis TT. Process intensification in hydrogen production
gasification IGCC systems with supercritical steam bottom cycle, Part 1— from coal and biomass via the use of membrane-based reactive separations.
Post-Combustion CCS. In: Proceedings of ASME 2012 international mechan- Curr Opin Chem Eng 2012;1:1–10.
ical engineering congress and exposition, 2012. Houston, TX, USA; November [113] 〈http://www.hydrogen.energy.gov/pdfs/review12/pd070_roberts_2012_o.pdf〉;
9–15, 2012. Lau F, Doong S-J. Hydrogen production process from carbonaceous materials
[84] Wang T, Long HA. Performance and Economic analysis of biomass/coal co- using membrane gasifier. US Patent US 20050039400 A1, 24; February 2005.
gasification IGCC systems with supercritical steam bottom cycle, Part 2—Pre- [114] 〈http://www.hydrogen.energy.gov/delivery.html〉.
Combustion CCS. In: Proceedings of ASME 2012 international mechanical [115] Kulprathipanja A, Alptekin O, Falconer JL, Way JD. Pd and Pd–Cu membranes:
engineering congress and exposition, 2012. Houston, TX, USA; November 9– inhibition of H2 permeation by H2S. J Membr Sci 2005;254:49–62.
15, 2012. [116] Miller JB, Morreale BD, Gellman AJ. The effect of adsorbed sulfur on surface
[85] Long HA, Wang T. Case Studies for biomass/coal co-gasification in IGCC segregation in a polycrystalline Pd 70 Cu 30 alloy. Surf Sci 2008;602:1819–25.
applications. In: Proceedings of ASME Turbo Expo 2011. Vancouver, Canada; [117] McKinley DL, Nitro WV. Method for hydrogen separation and purification, U.
June 6–10, 2011. S. Patent no. 3,439,474; 1969.
[86] Long HA, Wang T. Case studies for various IGCC parameters using blended coal/ [118] Edlund D, Newbold D, Frost C, Chester B. Composite hydrogen separation
biomass with supercritical steam bottom cycles. In: Proceedings of 29th element and module. U.S. Patent no.5,646,626; 1996.
international Pittsburgh coal conference. Pittsburgh, USA; October 15–18, 2012. [119] Edlund DJ. Composite hydrogen separation element and module EP Patent
[87] Capehart BL, editor. Encyclopedia of energy engineering and technology. 783919; 1997.
Boca Raton, FL: CRC Press; 2007. p. 2–3. [120] Howard BH, Killmeyer RP, Rothenberger KS, Cugini AV, Morreale BD, Enick
[88] Jones D, Bhattacharyya D, Turton R, Zitney SE. Optimal design and integra- RM, et al. Hydrogen permeance of palladium–copper alloy membranes over
tion of an air separation unit (ASU) for an integrated gasification combined a wide range of temperatures and pressures. J Membr Sci 2004;241:207–18.
[121] Ozdogan E, Wilcox J. Investigation of H2 and H2S adsorption on niobium- and [154] Benemann J. Hydrogen biotechnology: progress and prospects. Feature
copper-doped palladium surfaces. J Phys Chem B 2010;114:12851–8. Hydrogen Biotechnol 1996;14:1101–3.
[122] Zhu Z, Sun W, Yan L, Liu W, Liu W. Synthesis and hydrogen permeation of Ni– [155] Holladay JD, Hu J, King DL, Wang Y. An overview of hydrogen production
Ba(Zr0.1Ce0.7Y0.2)O3 δ metal–ceramic asymmetric membranes. Int J Hydro- technologies. Catal Today 2009;139:244–60.
gen Energy 2011;36:6337–42. [156] Chaubey R, Sahu S, James OO, Maity S. A review on development of industrial
[123] Jeon S-Y, Choi M-B, Park C-N, Wachsman ED, Song S-J. High sulfur tolerance processes and emerging techniques for production of hydrogen from renew-
dual-functional cermet hydrogen separation membranes. J Membr Sci able and sustainable sources. Renewable Sustainable Energy Rev 2013;23:
2011;382:323–7. 443–446.
[124] Balachandran U, Lee TH, Chen L, Song SJ, Picciolo JJ, Dorris SE. Hydrogen [157] Saxena RC, Adhikari DK, Goyal HB. Biomass-based energy fuel through
separation by dense cermet membranes. Fuel 2006;85:150–5. biochemical routes: a review. Renewable Sustainable Energy Rev 2009;13:
[125] Jeon S-Y, Lima D-K, Choi M-B, Wachsman ED, Song S-J. Hydrogen separation 167–178.
by Pd–CaZr0.9Y0.1O3 δ cermet composite membranes. Sep Purif Technol [158] Brentner LB, Peccia J, Zimmerman JB. Challenges in developing biohydrogen
2011;79:337–41. as a sustainable energy source: implications for a research agenda. Environ
[126] Escolástico S, Solís C, Scherb T, Schumacher G, Serra JM. Hydrogen separation Sci Technol 2010;44:2243–54.
in La5.5WO11.25 δ membranes. J Membr Sci 2013;444:276–84. [159] Levin DB, Pitt L, Love M. Biohydrogen production: prospects and limitations
[127] Haugsrud R, Norby T. High-temperature proton conductivity in acceptor- to practical application. Int J Hydrogen Energy 2004;29:173–85.
doped LaNbO4. Solid State Ionics 2006;177:1129–35. [160] U.S. Department of Energy Hydrogen. Fuel cells and infrastructure technol-
[128] van Holt D, Forster E, Ivanova ME, Meulenberg WA, Müller M, Baumann S, ogies program, multi-year research. Development and Demonstration Plan,
et al. Ceramic materials for H2 transport membranes applicable for gas U.S. Department of Energy; 2007.
separation under coal-gasification-related conditions. J Eur Ceram Soc [161] Su H, Cheng J, Zhou J, Song W, Cen K. Combination of dark and photo-
2014;34:2381–9. fermentation to enhance hydrogen production and energy conversion
[129] Klass DL. Biomass for renewable energy, fuels, and chemicals. San Diego: efficiency. Int J Hydrogen Energy 2009;34(21):8846–53.
Academic Press; 1998. [162] Su H, Cheng J, Zhou J, Song W, Cen K. Improving hydrogen production from
[130] Uddin MdN, Wan Daud WMA, Abbas HF. Potential hydrogen and non- cassava starch by combination of dark and photofermentation. Int J Hydrogen
condensable gases production from biomass pyrolysis: insights into the Energy 2009;34(4):1780–6.
process variables. Renewable Sustainable Energy Rev 2013;27:204–24. [163] Yokoi H, Mori S, Hirose J, Hayashi S, Takasaki Y. H2 production from starch by
[131] Bridgwater AV, Peacocke GVC. Fast pyrolysis processes for biomass. Renew- mixed culture of Clostridium butyricum and Rhodobacter sp M-19. Biotechnol
able Sustainable Energy Rev 1999;4:1–73. Lett 1998;20:895–9.
[132] Bridgwater AV, Meier D, Radlein D. An overview of fast pyrolysis of biomass. [164] Call D, Logan BE. Hydrogen production in a single chamber microbial electrolysis
Org Geochem 1999;30:1479 (chem.). cell (MEC) lacking a membrane. Environ Sci Technol 2008;42:3401–6.
[133] Lu Q, Li WZ, Zhu XF. Overview of fuel properties of biomass fast pyrolysis oils. [165] Ditzig J, Liu H, Logan BE. Production of hydrogen from domestic wastewater
Energy Convers Manage 2009;50:1376 (Con). using a bioelectrochemically assisted microbial reactor (BEAMR). Int J
[134] Tanksale A, Beltramini JN, Lu GM. A review of catalytic hydrogen production Hydrogen Energy 2007;32:2296–304.
processes from biomass. Renewable Sustainable Energy Rev 2010;14:166–82. [166] Cheng S, Logan BE. Sustainable and efficient biohydrogen production via
[135] Vispute TP, Huber GW. Production of hydrogen, alkanes and polyols by electrohydrogenesis. PNAS 2007;104:18871–3.
aqueous phase processing of wood-derived pyrolysis oils. Green Chem [167] Haandel AC, Lettinga G, editors. Anaerobic sewage treatment: a practical
2009;11:1433–45. guide for regions with a hot climate. Chichester, New York: J. Wiley; 1994.
[136] Wang D, Czernik S, Montane D, Mann M, Chornet E. Biomass to hydrogen via [168] Choo K-H, Lee C-H. Hydrodynamic behavior of anaerobic biosolids during
pyrolysis and catalytic steam reforming of the pyrolysis oil and its fractions. crossflow filtration in the membrane anaerobic bioreactor. Water Res
Ind Eng Chem Res 1997;36:1507–18. 1998;32(11):3387–97.
[137] Wang D, Czernik S, Chornet E. Production of hydrogen from biomass [169] Kim JS, Lee CH, Chang IS. Effect of pump shear on the performance of a
by catalytic steam reforming of fast pyrolysis oils. Energy Fuels crossflow membrane bioreactor. Water Res 2001;35(9):2137–44.
1998;12:19–24. [170] Huang Z, Ong SL, Ng HY. Submerged anaerobic membrane bioreactor for low-
[138] Czernik S, French R, Feik C, Chornet E. Hydrogen by catalytic steam reforming strength wastewater treatment: effect of HRT and SRT on treatment perfor-
of liquid byproducts from biomass thermoconversion processes. Ind Eng mance and membrane fouling. Water Res 2011;45:705–13.
Chem Res 2002;41:4209–15. [171] Lin H, Liao B-Q, Chen J, Gao W, Wang L, Wang F, et al. New insights into
[139] Czernik S, Evans R, French R. Hydrogen from biomass-production by steam membrane fouling in a submerged anaerobic membrane bioreactor based on
reforming of biomass pyrolysis oil. Catal Today 2007;129:265–8. characterization of cake sludge and bulk sludge. Bioresour Technol
[140] Wang S, Wang Y, Cai Q, Wang X, Jin H, Luo Z. Multi-step separation of 2011;102:2373–9.
monophenols and pyrolytic lignins from the water-insoluble phase of bio-oil. [172] Lin HJ, Xie K, Mahendran B, Bagley DM, Leung KT, Liss SN, et al. Factors
Sep Purif Technol 2014;122:248–55. affecting sludge cake formation in a submerged anaerobic membrane
[141] Trane R, Dahl S, Skjøth-Rasmussen MS, Jensen AD. Catalytic steam reforming bioreactor. J Membr Sci 2010;361:126–34.
of bio-oil. Int J Hydrogen Energy 2012;37:6447–72. [173] 〈http://www.triqua.eu/Triqua/fs3_site.nsf/htmlViewDocuments/
[142] Wang D, Czernik S, Montane´ D, Mann M, Chornet E. Biomass to hydrogen via C679E5A29C032314C12573D00043C20E〉.
fast pyrolysis and catalytic steam reforming of the pyrolysis oil or its [174] Dagnew M, Parker W, Seto P. Anaerobic membrane bioreactors for treating
fractions. Ind Eng Chem Res 1997;36:1507–18. waste activated sludge: short term membrane fouling characterization and
[143] Garcia L, French R, Czernik S, Chornet E. Catalytic steam reforming of bio-oils control tests. J Membr Sci 2012;421–422:103–10.
for the production of hydrogen: effects of catalyst composition. Appl Catal, A: [175] Lin HJ, Gao WJ, Leung KT, Liao BQ, Lin HJ. Characteristics of different fractions
Gen 2000;201:225–39. of microbial flocs and their role in membrane fouling. Water Sci Technol
[144] Rioche C, Kulkarni S, Meunier F, Breen J, Burch R. Steam reforming of model 2011;63(2):262–9.
compounds and fast pyrolysis bio-oil on supported noble metal catalysts. [176] Gao WJ, Qu X, Leung KT, Liao BQ. Influence of temperature and temperature
Appl Catal, B: Environ 2005;61:130–9. shock on sludge properties, cake layer structure, and membrane fouling in a
[145] van Rossum G, Kersten SRA, van Swaaij WPM. Catalytic and noncatalytic submerged anaerobic membrane bioreactor. J Membr Sci 2012;421–
gasification of pyrolysis oil. Ind Eng Chem Res 2007;46:3959–67. 422:131–44.
[146] van Rossum G, Kersten SRA, van Swaaij WPM. Staged catalytic gasification/ [177] Meng F, Shi B, Yang F, Zhang H. New insights into membrane fouling in
steam reforming of pyrolysis oil. Ind Eng Chem Res 2009;48:5857–66. submerged membrane bioreactor based on rheology and hydrodynamics
[147] Vagia EC, Lemonidou AA. Thermodynamic analysis of hydrogen production concepts. J Membr Sci 2007;302:87–94.
via autothermal steam reforming of selected components of aqueous bio-oil [178] Lin H, Chen J, Wang F, Ding L, Hong H. Feasibility evaluation of submerged
fraction. Int J Hydrogen Energy 2008;33:2489–500. anaerobic membrane bioreactor for municipal secondary wastewater treat-
[148] Czernik S, French R. Distributed production of hydrogen by auto-thermal ment. Desalination 2011;280:120–6.
reforming of fast pyrolysis bio-oil. Int J Hydrogen Energy 2014;39:744–50. [179] Saddoud A, Hassairi I, Sayadi S. Anaerobic membrane reactor with phase
[149] Javaid A, Ryan T, Berg G, Pan X, Vispute T, Bhatia SR, et al. Removal of char separation for the treatment of cheese whey. Bioresour Technol 2007;98
particles from fast pyrolysis bio-oil by microfiltration. J Membr Sci (11):2102–8.
2010;363:120–7. [180] Stuckey DC, Trzcinski AP. Continuous treatment of the organic fraction of
[150] Reith JH, Wijffels, Barten H, editors. Biomethane & biohydrogen. Status and municipal solid waste in an anaerobic two-stage membrane process with
perspectives of biological methane and hydrogen production. The Nether- liquid recycle. Water Res 2009;43(9):2449–62.
lands: Dutch Biological Hydrogen Foundation, c/o Energy research Centre of [181] Jeison D, van Lier JB. Feasibility of thermophilic anaerobic submerged
The Netherlands ECN, Unit Biomass; 2003. membrane bioreactors (AnSMBR) for wastewater treatment. Desalination
[151] 〈http://www1.eere.energy.gov/hydrogenandfuelcells/pdfs/national_h2_road 2007;231:227–35.
map.pdf〉. [182] Lin HJ, Gao WJ, Leung KT, Liao BQ. Characteristics of different fractions of
[152] Verhaart MR, Bielen AA, van der Oost J, Stams AJ, Kengen SW. Hydrogen microbial flocs and their role in membrane fouling. Water Sci Technol
production by hyperthermophilic and extremely thermophilic bacteria and 2011;63:262–9.
archaea: mechanisms for reductant disposal. Environ Technol 2010;1(8- [183] Wijekoon KC, Visvanathan C, Abeynayaka A. Effect of organic loading rate on
9):993–1003. VFA production, organic matter removal and microbial activity of a two-stage
[153] 〈http://www.biohydrogen.nl/publicitem.m?key=stairway2h2&pgid=22373& thermophilic anaerobic membrane bioreactor. Bioresour Technol 2011;102:
trail=/stairway2h2/22373〉. 5353–5360.
[184] Fakhru'l-Razi A. Ultrafiltration membrane separation for anaerobic waste- In: Buonomenna MG, Golemme G, editors. Sharjah, U.A.E.: Bentham Science
water treatment. Water Sci Technol 1994;30:321–7. Publishers; 2012.
[185] Skouteris G, Hermosilla D, López P, Negro C, Blanco A. Anaerobic membrane [216] Zornoza B, Tellez C, Coronas J, Gascon J, Kapteijn F. Metal organic framework
bioreactors for wastewater treatment: a review. Chem Eng J 2012;198– based mixed matrix membranes: an increasingly important field of research
199:138–48. with a large application potential. Microporous Mesoporous Mater
[186] Smith AL, Stadler LB, Love NG, Skerlos SJ, Raskin L. Perspectives on anaerobic 2013;166:67–78.
membrane bioreactor treatment of domestic wastewater: a critical review. [217] Mason CR, Buonomenna MG, Golemme G, Budd PM, Galiano F, Figoli A, et al.
Bioresour Technol 2012;122:149–59. New organophilic mixed matrix membranes derived from a polymer of
[187] Lin H, Peng W, Zhang M, Chen J, Hong H, Zhang Y. A review on anaerobic intrinsic microporosity and silicalite-1. Polymer 2013;54(9):2222–30.
membrane bioreactors: applications, membrane fouling and future perspec- [218] Ordoñez MJC, Balkus KJ, Ferraris JP, Musselman IHJ. Molecular sieving
tives. Desalination 2013;314:169–88. realized with ZIF-8/Matrimids mixed-matrix membranes. J Membr Sci
[188] Kang JI, Yoon SH, Lee CH. Comparison of the filtration characteristics of 2010;361:28–37.
organic and inorganic membranes in a membrane-coupled anaerobic bior- [219] Golemme G, Buonomenna MG, Bruno A, Manes R. Method for preparing
eactor. Water Res 2002;36(7):1803–13. hydrophobic fluorinated mixed matrix membranes, said membranes, and
[189] He Y, Xu P, Li C, Zhang B. High-concentration food wastewater treatment by separation methods using said membranes. EP2668995 A1, 04 December 2013.
an anaerobic membrane bioreactor. Water Res 2005;39:4110–8. [220] Aroon MA, Ismail AF, Montazer-Rahmati MM, Matsuura T. Effect of chitosan
[190] Vallero MVG, Lettinga G, Lens PNL. High rate sulfate reduction in a as a functionalization agent on the performance and separation properties of
submerged anaerobic membrane bioreactor (SAMBaR) at high salinity. J polyimide/multi-walled carbon nanotubes mixed matrix flat sheet mem-
Membr Sci 2005;253:217–32. branes. J Membr Sci 2010;364:309–17.
[191] Jeison D, van Lier JB. Cake layer formation in anaerobic submerged mem- [221] Buonomenna MG, Golemme G, Tone CM, De Santo MP, Ciuchi F, Perrotta E.
brane bioreactors (AnSMBR) for wastewater treatment. J Membr Sci Amine-functionalized SBA-15 in poly(styrene-b-butadiene-b-styrene) (SBS)
2006;284:227–36. yields permeable and selective nanostructured membranes for gas separa-
[192] Jeison D, van Lier JB. Anaerobic wastewater treatment and membrane tion. J Mater Chem A 2013;1(38):11853–66.
filtration: a one night stand or a sustainable relationship? Water Sci Technol [222] Ismail AF, Rahim NH, Mustafa A, Matsuura T, Ng BC, Abdullah Sand
2008;57(2):527–32. Hashemifard SA. Gas separation performance of polyethersulfone/multi-
[193] Jeison D, Kremer B, van Lier JB. Application of membrane enhanced biomass walled carbon nanotubes mixed matrix membranes. Sep Purif Technol
retention to the anaerobic treatment of acidified wastewaters under extreme 2011;80:20–31.
saline conditions. Sep Purif Technol 2009;64(2):198–205. [223] Sorribas S, Zornoza B, Téllez C, Coronas J. Mixed matrix membranes
[194] de Hullu J, Maassen J, van Meel P, Shazad S, Vaessen J. IFP project-biogas comprising silica-(ZIF-8) core–shell spheres with ordered meso–micropor-
upgrading. (June). Technische Universiteit Eindhoven University of Technology; osity for natural- and bio-gas upgrading. J Membr Sci 2014;452:184–92.
2008. [224] Gorgojo P, Sieffert D, Staudt C,s, Tellez C, Coronas J. Exfoliated zeolite Nu-6
[195] Evaluation of upgrading techniques for biogas. Report SGC 142. Swedish Gas (2) as filler for 6FDA-based copolyimide mixed matrix membranes. J Membr
Center; November 2003. Sci 2012;411–412:146–52.
[196] Ryckebosch E, Drouillon M, Vervaeren H. Techniques for transformation of [225] Rubio C, Zornoza B, Gorgojo P, Tellez C, Coronas J. Separation of H2 and CO2
biogas to biomethane. Biomass Bioenergy 2011;35(5):1633–45. containing mixtures with mixed matrix membranes based on layered
[197] Scholz M, Melin T, Wessling M. Transforming biogas into biomethane materials. Curr Org Chem 2014;18:2351–63.
using membrane technology. Renewable Sustainable Energy Rev 2013;17: [226] Burmann P, Zornoza B, Téllez C, Coronas J. Mixed matrix membranes
199–212. comprising MOFs and porous silicate fillers prepared via spin coating for
[198] Baker R, Lokhandwala K. Natural gas processing with membranes: an gas separation. Chem Eng Sci 2014;107:66–75.
overview. Ind Eng Chem Res 2008;47(7):2109–21. [227] Thompson JA, Vaughn JT, Brunelli NA, Koros WJ, Jones CW, Nair S. Mixed-
[199] Scholes CA, Stevens GW, Kentish SE. Membrane gas separation applications linker zeolitic imidazolate framework mixed-matrix membranes for aggres-
in natural gas processing. Fuel 2012;96:15–28. sive CO2 separation from natural gas. Microporous Mesoporous Mater
[200] Lokhandwala K, Pinnau I, He Z, Amo K, DaCosta A, Wijmans J. Membrane 2014;192:43–51.
separation of nitrogen from natural gas: a case study from membrane [228] Zhang C, Dai Y, Johnson JR, Karvan O, Koros WJ. High performance ZIF-8/
synthesis to commercial deployment. J Membr Sci 2010;346(2):270–9. 6FDA-DAM mixed matrix membrane for propylene/propane separations. J
[201] Chinn D, Okeowo S, Euhus J, Husain S. Process for upgrading natural gas with Membr Sci 2012;389:34–42.
improved management of CO2. US Patent application 12/361, 961; 2009. [229] Bae T-H, Lee JS, Qiu W, Koros WJ, Jones CW, Nair S. A high-performance gas-
[202] Bhide BD, Stern SA. Membrane processes for the removal of acid gases from separation membrane containing submicrometer-sized metal–organic fra-
natural gas. II. Effects of operating conditions, economic parameters, and mework crystals. Angew Chem Int Ed Engl 2010;49:9863–6.
membrane properties. J Membr Sci 1993;81(3):239–52. [230] Zhang C, Zhang K, Xu L, Labreche Y, Kraftschik B, Koros WJ. Highly scalable
[203] Datta AK, Sen PK. Optimization of membrane unit for removing carbon ZIF-based mixed-matrix hollow fiber membranes for advanced hydrocarbon
dioxide from natural gas. J Membr Sci 2006;283:291–300. separations. AIChE J 2014;60:2625–35.
[204] Yeo ZY, Chew TL, Zhu PW, Mohamed AR, Chai SP. Conventional processes and [231] Noble RD. Perspectives on mixed matrix membranes. J Membr Sci
membrane technology for carbon dioxide removal from natural gas: a 2011;378:393–7.
review. J Nat Gas Chem 2012;21(3):282–98. [232] Ploegmakers J, Japip S, Nijmeijer K. Mixed matrix membranes containing
[205] Schell WJ, Houston CD. Use of membranes for biogas treatment. Energy Prog MOFs for ethylene/ethane separation Part A: Membrane preparation and
1983;3:96–100. characterization. J Membr Sci 2013;428:445–53.
[206] Harasek M, Makaruk A, Miltner M, Schlager R. Membrane separation process [233] Jorgensen BS, Young JS, Espinoza BF. Cross-linked polybenzimidazole mem-
for biogas upgrading. In: Proceedings of 15th European biomass conference brane for gas separation. US 6946015 B2; 2005.
& exhibition; 2007. [234] Kothari R, Singh DP, Tyagi VV, Tyagi SK. Fermentative hydrogen production—
[207] Makaruk A, Harasek M, Miltner M. Biogasaufbereitung und Netzeinspeisung. an alternative clean energy source. Renewable Sustainable Energy Rev
In: Beitrage zu Abfallwirtschaft, 6. Fachtagung-Anaerobe biologische Abfall- 2012;16:2337–46.
behandlung, Neue Tendenzen in der Biogastechnologie; Dresden 23–24, [235] Logan BE, Oh S-E, Kim IS, Van Ginkel S. Biological hydrogen production
September, 2008. measured in batch anaerobic respirometers. Environ Sci Technol
[208] Makaruk A, Miltner M, Harasek M. Biogas desulfurization and biogas 2002;36:2530–5.
upgrading using a hybrid membrane system—modeling study. Water Sci [236] Hawkes FR, Dinsdale R, Hawkes DL, Hussy I. Sustainable fermentative
Technol 2013;67(2):326–32. biohydrogen: challenges for process optimization. Int J Hydrogen Energy
[209] Meinema HA, Dirrix RWJ, Brinkman HW, Terpstra RA, Jekerle J, Kösters PH. 2002;27:1339–47.
Ceramic membranes for gas separation—recent developments and state of [237] Özgür E, Peksel B. Biohydrogen production from barley straw hydrolysate
the art. Interceram 2005;54:86–91. through sequential dark and photofermentation. J Cleaner Prod
[210] Robeson LM. Correlation of separation factor versus permeability for poly- 2013;52:14–20.
meric membranes. J Membr Sci 1991;62:165–85. [238] Chen CY, Yang MH, Yeh KLS, Liu CH, Chang JS. Biohydrogen production using
[211] Robeson LM. The upper bound revisited. J Membr Sci 2008;320:390–400. sequential two-stage dark and photofermentation processes. Int J Hydrogen
[212] Widjojo N, Li Y, Jiang L, Chung TS. Recent progress and challenges on mixed Energy 2008;33(18):4755–62.
matrix membranes in both material and configuration aspects for gas [239] Su H, Cheng J, Zhou J, Song W, Cen K. Combination of dark and photo-
separation in advanced materials for membrane preparation. In: Buono- fermentation to enhance hydrogen production and energy conversion
menna MG, Golemme G, editors. Sharjah, U.A.E.: Bentham Science Publish- efficiency. Int J Hydrogen Energy 2009;34(21):8846–53.
ers; 2012. [240] Su H, Cheng J, Zhou J, Song W, Cen K. Hydrogen production from water
[213] Buonomenna MG, Yave W, Golemme G. Some approaches for high performance hyacinth through dark and photofermentation. Int J Hydrogen Energy
polymer based membranes for gas separation: block copolymers, carbon 2010;35(17):8929–37.
molecular sieves and mixed matrix membranes. RSC Adv 2012;2:10745–73. [241] Su H, Cheng J, Zhou J, Song W, Cen K. Improving hydrogen production from
[214] Golemme G, Bruno A, Manes R, Muoio D. Preparation and properties of cassava starch by combination of dark and photofermentation. Int J Hydrogen
superglassy polymers—zeolite mixed matrix membranes. Desalination 2006; Energy 2009;34(4):1780–6.
200; 440–442. [242] Cheng J, Su H, Zhou J, Song W, Cen K. Microwave-assisted alkali pretreatment
[215] Ferraris JP, Musselman IH, Balkus KJJR. Mixed matrix membranes based on of rices traw to promote enzymatic hydrolysis and hydrogen production in
metal–organic frameworks in advanced materials for membrane preparation. dark-and photo-fermentation. Int J Hydrogen Energy 2011;36(3):2093–101.
[243] Cheng J, Su H, Zhou J, Song W, Cen K. Hydrogen production by mixed bacteria [273] Sirkar K. Membrane contactors. In: Li NN, Fane AG, Winston Ho WS,
through dark and photofermentation. Int J Hydrogen Energy 2011;36 Matsuura T, editors. Advanced membrane technology and applications.
(1):450–7. Hoboken, New Jersey: John Wiley & Sons, Inc.; 2008. p. 687–702.
[244] Xia A, Cheng J, Lin R, Lu H, Zhou J, et al. Comparison in dark hydrogen [274] Modigell M, Schumacher M, Zenkevich VB, Teplyakov VV. A membrane
fermentation followed by photo hydrogen fermentation and methanogenesis contactor for efficient CO2 removal in biohydrogen production. Desalination
between protein and carbohydrate compositions in Nannochloropsis oceanica 2008;224:186–90.
biomass. Bioresour Technol 2013;138:204–13. [275] Teplyakov VV, Gassanovaa LG, Sostinaa EG, Slepovab EV, Modigell M,
[245] Xia A, Cheng J, Ding L, Lin R, Huang R, Zhou J, et al. Improvement of the Netrusov AI. Lab-scale bioreactor integrated with active membrane system
energy conversion efficiency of Chlorella pyrenoidosa biomass by a three- for hydrogen production: experience and prospects. Int J Hydrogen Energy
stage process comprising dark fermentation, photofermentation, and metha- 2002;27:1149–55.
nogenesis. Bioresour Technol 2013;146:436–43. [276] Beggel F, Nowik IJ, Modigell M, Shalygin MG, Teplyakov VV, Zenkevitch VB. A
[246] Shao L, Low BT, Chung T-S, Greenberg AR. Polymeric membranes for the novel gas purification system for biologically produced gases. J Cleaner Prod
hydrogen economy: Contemporary approaches and prospects for the future. 2010;18:S43–50.
J Membr Sci 2009; 327; 18–31. [277] Teplyakov VV, Khotimskii VS, Yakovlev AV, Shalygin MG, Gasanova LG,
[247] Meyer PE, Winebrake JJ. Modeling technology diffusion of complementary Zen'Kevich VB, et al. Membrane systems for the recovery of energy carriers
goods: the case of hydrogen vehicles and refueling infrastructure. Technova- from products of organic waste recycling. Catal Ind 2011;3:62–9.
tion 2009;29:77–91. [278] 〈http://www.biohydrogen.nl/hyvolution/31852/7/0/20〉.
[248] Francou N, Vignais PM. Hydrogen production by Rhodopseudomomonas [279] Cullinane JT, Rochelle GT. Carbon dioxide absorption with aqueous potassium
capsulate cells entrapped in carrageenan beads. Biotechnol Lett carbonate promoted by piperazine. Chem Eng Sci 2004;59:3619–30.
1984;6:639–44. [280] Cullinane JT, Rochelle GT. Thermodynamics of aqueous potassium carbonate,
[249] Taguchi F, Mizukami N, Hasegawa K, Saito-Taki T. Microbila conversion of piperazine, and carbon dioxide. Fluid Phase Equilib 2005;227:197–213.
arabinose and xylose to hydrogen by a newly isolated Clostridium sp. No. 2. [281] Acosta-Michlik L, Lucht W, Bondeau A, Beringer T. Integrated assessment of
Can J Microbiol 1994;40:228–33. sustainability trade-offs and pathways for global bioenergy production:
[250] Melis T. Green alga production: process, challenges and prospects. Int J framing a novel hybrid approach. Renewable Sustainable Energy Rev
Hydrogen Energy 2002;27:1217–28. 2011;15:2791–809.
[251] Polle JEW, Kanakagiri S, Jin E, Masuda T, Melis A. Truncated chlorophyll [282] Faaij AP. Bio-energy in Europe: changing technology choices. Energy Policy
antenna size of the photosystems—a practical method to improve microalgal 2006;34:322–42.
productivity and hydrogen production in mass culture. Int J Hydrogen Energy [283] Naylor RL, Liska AJ, Burke MB, Falcon WP, Gaskell JC, Rozelle SD, et al. The
2002;27:1257–64. ripple effect: biofuels, food security and the environment. Environment
[252] Zhu H, Ueda S, Asada Y, Miyake J. Hydrogen production as a novel process of 2007;49:30–43.
wastewater treatment-studies on tofu wastewater with entrapped R. sphae- [284] von Braun J, Vargas RH, Pandya-Lorch R, editors. The poorest and hungry.
toides and mutagenesis. Int J Hydrogen Energy 2002;27:1349–58. assessments, analyses, and actions. An IFPRI 2020 Book. Washington, DC:
[253] Ueno Y, Otauka S, Morimoto M. Hydrogen production from industrial International Food Policy Research Institute; 2009.
wastewater by anaerobic microflora in chemostat culture. J Ferment Bioeng [285] Lustig N. Thought for food: the challenges of coping with soaring food prices.
1996;82:194–7. Working paper number 155, Center for Global Development, Washington;
[254] Jouanneau Y, Lebecque S, Vignais PM. Ammonia and light effect on nitro- 2008.
genase activity in nitrogen-limited continuous cultures of Rhodopseudomo- [286] Brühl CA, Eltz T. Fuelling the biodiversity crisis: species loss of ground-
nas capsulate: role of glutamate synthetase. Arch Microbiol 1984;119:326–31. dwelling forest ants in oil palm plantations in Sabah, Malaysia (Borneo).
[255] Moran M, Shapiro H. Fundamentals of engineering thermodynamics. 3rd ed.. Biodivers Conserv 2010;19:519–29.
New York, NY: Wiley; 1996. [287] Ceccon E, Miramontes O. Reversing deforestation? Bioenergy and society in
[256] Lindblad P, Christensson K, Lindberg P, Federov A, Pinto F, Tsygankov A. two Brazilian models Ecol Econ 2008;67:311–7.
Photoproduction of H2 by wildtype Anabaena PCC 1720 and a hydrogen [288] Butler RA, Laurance WF. Is oil palm the next emerging threat to the Amazon?
uptake deficient mutant: from laboratory to outdoor culture. Int J Hydrogen Trop Conserv Sci 2009;2:1–10.
Energy 2002;27:1271–81. [289] Jumbe CB, Msiska FB, Madjera M. Biofuels development in sub-Saharan
[257] Ko I-B, Noike T. Use of blue optical filters for suppression of growth of algae Africa: are the policies conducive? Energy Policy 2009;37:4980–6.
in hydrogen producing non-axenic cultures of Rhodobacter sphaeroides RV. [290] Hall J, Matos S, Severino L, Beltrao N. Brazilian biofuels and social exclusion:
Int J Hydrogen Energy 2002;27:129–302. established and concentrated ethanol versus emerging and dispersed bio-
[258] Kondo T, Arawaka M, Wakayama T, Miyake J. Hydrogen production by diesel. J Cleaner Prod 2009;17:S77e.
combining two types of photosynthetic bacteria with different characteris- [291] Ariza-Montobbio P, Lele S. Jatropha plantations for biodiesel in TamilNadu, India:
tics. Int J Hydrogen Energy 2002;27:1303–8. viability, livelihood trade-offs, and latent conflict. Ecol Econ 2010;70:189–95.
[259] Singhania RR, Christophe G, Perchet G, Troquet J, Larroche C. Immersed [292] Rozendal RA, Buisman CJN. Process for producing hydrogen. Patent
membrane bioreactors: an overview with special emphasis on anaerobic WO2005005981; 2005.
bioprocesses. Bioresour Technol 2012;122:1712 (o). [293] Liu H, Grot S, Logan BE. Electrochemically assisted microbial production of
[260] Lee D-Y, Li Y-Y, Oh Y-K, Kim M-S, Noike T. Effect of iron concentration on hydrogen from acetate. Environ Sci Technol 2005;39:4317–20.
continuous H2 production using membrane bioreactor. Int J Hydrogen [294] Logan BE, Aelterman P, Hamelers B, Rozendal R, Schrö der U, Keller J, et al.
Energy 2009;34:1244–52. Microbial fuel cells: methodology and technology. Environ Sci Technol
[261] Lee D-Y, Li Y-Y, Noike T, Cha G-C. Behavior of extracellular polymers and bio- 2006;40:5181–92.
fouling during hydrogen fermentation with a membrane bioreactor. J Membr [295] Logan BE. Microbial fuel cells. Hoboken, NJ: John Wiley & Sons, Inc.; 2008.
Sci 2008;322:13–8. [296] Logan B, Call D, Cheng S, Hamelers HVM, THJA Sleutels, Jeremiasse AW, et al.
[262] Lee DY, Li Y-Y, Noike T. Continuous H2 production by anaerobic mixed Microbial electrolysis cells for high yield hydrogen gas production from
microflora in membrane bioreactor. Bioresour Technol 2009;100:690–5. organic matter. Environ Sci Technol 2008;42:8630–40.
[263] Jung K-W, Kim D-H, Kim S-H, Shin H-S. Bioreactor design for continuous dark [297] Thauer RK, Jungermann K, Decker K. Energy conservation in chemotrophic
fermentative hydrogen production. Bioresour Technol 2011;102:8612–20. anaerobic bacteria. Bacteriol Rev 1977;41:100–80.
[264] Lee D-Y, Li, Noike T. Influence of solids retention time on continuous H2 [298] Hu H, Fan Y, Liu H. Hydrogen production using single chamber membrane-
production using membrane bioreactor. Int J Hydrogen Energy 2010;35:52–60. free microbial electrolysis cells. Water Res 2008;42:4172–8.
[265] Nam J-Y, Logan BE. Optimization of catholyte concentration and anolyte pHs [299] Tartakovsky B, Manuel MF, Wang H, Guiot SR. High rate membrane-less
in two chamber microbial electrolysis cells. Int J Hydrogen Energy microbial electrolysis cell for continuous hydrogen production. Int J Hydro-
2012;37:18622–8. gen Energy 2009;34(2):672–7.
[266] Cusick RD, Bryan B, Parker DS, Merrill MD, Mehanna M, Kiely PD, et al. [300] Call D, Logan BE. A method for high throughput bioelectrochemical research
Performance of a pilot-scale continuous flow microbial electrolysis cell fed based on small scale microbial electrolysis cells. Biosens Bioelectron
winery wastewater. Appl Microbiol Biotechnol 2011;89:2053–63. 2011;26:4526–31.
[267] Ren N, Li J, Li B, Wang Y, Liu S. Biohydrogen production from molasses by [301] Liu H, Grot S, Logan BE. Electrochemically assisted production of hydrogen
anaerobic fermentation with a pilot-scale bioreactor system. Int J Hydrogen from acetate. Environ Sci Technol 2005;39:4317–20.
Energy 2006;31:2147–57. [303] Jeremiasse AW, Hamelers HVM, Buisman CJN. Microbial electrolysis cell with
[268] Hallenbeck PC, Benemann JR. Biological hydrogen production: fundamentals a microbial biocathodes. Bioelectrochemistry 2010;78:39–43.
and limiting processes. Int. J Hydrogen Energy 2002;27:1185–93. [304] Rozendal RA, Jeremiasse AW, Hamelers HVM, Buisman CJN. Hydrogen produc-
[269] Das D, Nejat VT. Hydrogen production by biological processes: a survey of tion with a microbial biocathode. Environ Sci Technol 2008;42:629–34.
literature. Int J Hydrogen Energy 2001;26:13–28. [306] Kyazze G, Popov A, Dinsdale R, Esteves S, Hawkes F, Premier G, et al.
[270] Abetz V, Brinkmann T, Dijkstra M, Ebert K, Fritsch D, Ohlrogge K. Develop- Influence of catholyte pH and temperature on hydrogen production from
ments in membrane research: from material via process design to industrial acetate using a two chamber concentric tubular microbial electrolysis cell.
application. Adv Eng Mater 2006;8:328–58. Int J Hydrogen Energy 2010;35:7716–22.
[271] Li Y, Chung TS. Highly selective sulfonated polyethersulfone (SPES)-based [308] Nam J-Y, Logan BE. Enhanced hydrogen generation using a saline catholyte in
membranes with transition metal counterions for hydrogen recovery and a two chamber microbial electrolysis cell. Int J Hydrogen Energy
natural gas separation. J Membr Sci 2008;308:128–35. 2011;36:15105–10.
[272] Orme CJ, Stone ML, Benson MT, Peterson ES. Testing of polymer membranes for [310] Hu H, Fan Y, Liu H. Hydrogen production using single-chamber membrane-
the selective permeability of hydrogen. Sep Sci Technol 2003;38:3225–38. free microbial electrolysis cells. Water Res 2008;42:4172–8.
[311] Lee HS, Torres CI, Parameswaran P, Rittmann BE. Fate of H2 in an upflow [343] Hatzell MC, Kim Y, Logan BE. Powering microbial electrolysis cells by
single-chamber microbial electrolysis cell using a metal-catalyst-free cath- capacitor circuits charged using microbial fuel cell. J Power Sources
ode. Environ Sci Technol 2009;43:7971–6. 2013;229:198–202.
[312] Hu H, Fan Y, Liu H. Hydrogen production in single chamber tubular microbial [344] Murugesan A, Umarani C, Subramanian R, Nedunchezhian N. Bio-diesel as an
electrolysis cells using non-precious metal catalysts (NiMo, NiW). Int J alternative fuel for diesel engines—a review. Renewable Sustainable Energy
Hydrogen Energy 2009;34:8535–42. Rev 2009;13:653–62.
[313] Liu H, Hu H, Chignell J, Fan Y. Microbial electrolysis: novel technology for [345] Murugesan A, Umarani C, Chinnusamy TR, Krishnan M, Subramanian R,
hydrogen production from biomass. Biofuels 2010;1(1):129–42. Neduzchezhain N. Production and analysis of bio-diesel from non-edible oils
[314] Zhou M, Wang H, Hassett DJ, Gu T. Recent advances in microbial fuel cells —a review. Renewable Sustainable Energy Rev 2009;13:825–34.
(MFCs)and microbial electrolysis cells (MECs) for wastewater treatment, [346] Weber C, Farwick A, Benisch F, Brat D, Dietz H, Subtil T. Trends and
bioenergy and bioproducts. J Chem Technol Biotechnol 2013;88:508–18. challenges in the microbial production of lignocellulosic bioalcohol fuels.
[315] Chae K-J, Choi M-J, Kim K-Y, Ajayi FF, Chang I-S, Kim IS. Selective inhibition of Appl Microbiol Biotechnol 2010;87:1303–15.
methanogens for the improvement of biohydrogen production in microbial [347] Luo L, van der Voet E, Huppes G. An energy analysis of ethanol from cellulosic
electrolysis cells. Int J Hydrogen Energy 2010;35:13379–86. feedstock–corn stover. Renewable Sustainable Energy Rev 2009;13:2003–11.
[316] Clauwaert P, Toledo R, Ha D, Crab R, Verstraete W, Hu H, et al. Combining [348] Ezeji T, Qureshi N, Blaschek HP. Production of acetone–butanol–ethanol
biocatalyzed electrolysis with anaerobic digestion. Water Sci Technol (ABE) in a continuous flow bioreactor using degermed corn and Clostridium
2008;57:575–9. beijerinckii. Process Biochem 2007;42:34–9.
[317] Clauwaert P, Verstraete W. Methanogenesis in membraneless microbial [349] Hansen AC, Kyritsis DC, Lee CF. Characteristics of biofuels and renewable fuel
electrolysis cells. Appl Microbiol Biotechnol 2009;82:829–36. standards. In: Vertes AA, Blaschek HP, Yukawa H, Qureshi N, editors. Biomass
[318] Cheng S, Xing D, Call DF, Logan BE. Direct biological conversion of electrical to biofuels—strategies for global industries. New York, NY: John Wiley; 2009.
current into methane by electromethanogenesis. Environ Sci Technol [350] Togbe C, Dayma G, Mze-Ahmed A, Dagaut P. Experimental and modeling
2009;43:3953–8. study of the kinetics of oxidation of simple biodiesel-biobutanol surrogates:
[319] Wang A, Liu W, Cheng S, Xing D, Zhoud J, Logan BE. Source of methane and methyl octanoate-butanol mixtures. Energy Fuels 2010;24:3906–16.
methods to control its formation in single chamber microbial electrolysis [351] Kumar M, Gayen K. Biobutanol: the future biofuel. In: Baskar C, Baskar S, Dhillon
cells. Int J Hydrogen Energy 2009;34:3653–8. RS, editors. Biomass conversion. Verlag Berlin Heidelberg: Springer; 2012.
[320] Nam J-Y, Tokash JC, Logan BE. Comparison of microbial electrolysis cells [352] Weizmann C. British Patent 1912; p. 4845.
operated with added voltage or by setting the anode potential. Int J [353] Durre P. Fermentative butanol production: bulk chemical and biofuel. Ann
Hydrogen Energy 2011;36:10550–6. NY Acad Sci 2008;1125:353–62.
[323] Zhuang L, Zhou S, Li Y, Yuan Y. Enhanced performance of air-cathode two- [354] 〈https://www.biofuelsdatabase.org/wiki/index.php5/N-Butanol〉 Pathway.
chamber microbial fuel cells with high-pH anode and low-pH cathode. [355] Woods DR. The genetic engineering of microbial solvent production. Trends
Bioresour Technol 2010;101:3514–9. Biotechnol 1995;13:259–64.
[324] Rozendal RA, THJA Sleutels, Hamelers HVM, Buisman CJN. Effect of the type [356] Pierrot P, Fick M, Engasser JM. Continuous acetone–butanol fermentation
of ion exchange membrane on performance, ion transport, and pH in with high productivity by cell ultrafiltration and recycling. Biotechnol Lett
biocatalyzed electrolysis of wastewater. Water Sci Technol 2008;57:1757–62. 1986;8:253–6.
[325] Sleutels THJA, Hamelers HVM, Rozendal RA, Buisman CJN. Ion transport [357] Izák P, Schwarz K, Ruth W, Bahl H, Kragl U. Increased productivity of
resistance in microbial electrolysis cells with anion and cation exchange Clostridium acetobutylicum fermentation of acetone, butanol, and ethanol
membranes. Int J Hydrogen Energy 2009;34:3612–20. by pervaporation through supported ionic liquid membrane. Appl Microbiol
[326] Jeremiasse AW, Hamelers HVM, Saakes M, Buisman CJN. Ni foam cathode Biotechnol 2008;78:597–602.
enables high volumetric H2 production in a microbial electrolysis cell. Int J [358] Ezeji TC, Qureshi N, Blaschek HP. Butanol fermentation research: upstream
Hydrogen Energy 2010;35:12716–23. and downstream manipulations. Chem Rec 2004;4:305–14.
[327] Yuan Y, Zhao B, Zhou S, Zhong S, Zhuang L. Electrocatalytic activity of anodic [359] Qureshi N, Blaschek HP. Production of acetone butanol ethanol (ABE) by a
biofilm responses to pH changes in microbial fuel cells. Bioresour Technol hyper-producing mutant strain of Clostridium beijerinckii BA101 and recovery
2011;102:6887–91. by pervaporation. Biotechnol Prog 1999;15:594–602.
[328] He Z, Huang Y, Manohar AK, Mansfeld F. Effect of electrolyte pH on the rate [360] Qureshi N, Meagher MM, Huang J, Hutkins RW. Acetone butanol ethanol
of the anodic and cathodic reactions in an air-cathode microbial fuel cell. (ABE) recovery by pervaporation using silicalite–silicone composite mem-
Bioelectrochemistry 2008;74:78–82. brane from fed-batch reactor of Clostridium acetobutylicum. J Membr Sci
[329] Rozendal RA, Hamelers HVM, Molenkamp RJ, Buisman CJN. Performance of 2001;187:93–102.
single chamber biocatalyzed electrolysis with different types of ion exchange [361] Iza´k P, Schwarz K, Ruth W, Bahl H, Kragl U. Increased productivity of
membranes. Water Res 2007;41:1984–94. Clostridium acetobutylicum fermentation of acetone, butanol, and ethanol by
[330] Kim Y, Logan BE. Hydrogen production from inexhaustible supplies of fresh pervaporation through supported ionic liquid membrane. Appl Microbiol
and salt water using microbial reverse-electrodialysis electrolysis cells. PNAS Biotechnol 2008;78:597–602.
2011;27:16176–81. [362] Qureshi N, Meagher MM, Hutkins RW. Recovery of butanol from model
[331] Kim Y, Logan BE. Microbial reverse electrodialysis cells for synergistically. solutions and fermentation broth using a silicalite/silicone membrane. J
[332] Nam J-Y, Cusick RD, Kim Y, Logan BE. Hydrogen generation in microbial Membr Sci 1999;158:115–25.
reverse-electrodialysis electrolysis cells using a heat-regenerated salt solu- [363] Niemisto ̈ J, Kujawski W, Keiski RL. Pervaporation performance of composite
tion. Environ Sci Technol 2012;46:5240–6. poly(dimethyl siloxane) membrane for butanol recovery from model solu-
[333] Sun M, Sheng GP, Zhang L, Xia C-R, Mu ZX, Liu XW, et al. An MEC-MFC- tions. J Membr Sci 2013;434:55–64.
coupled system for biohydrogen production from acetate. Environ Sci [364] Huang J, Meagher MM. Pervaporative recovery of n-butanol from aqueous
Technol 2008;42:8095–100. solutions and ABE fermentation broth using thin-film silicalite-filled silicone
[334] Sun M, Sheng GP, Mu ZX, Liu XW, Chen YZ, Wang HL, et al. Manipulating the composite membranes. J Membr Sci 2001;192:231–42.
hydrogen production from acetate in a microbial electrolysis cell–microbial [365] Liu F, Liu L, Feng X. Separation of acetone–butanol–ethanol (ABE) from dilute
fuel cell-coupled system. J Power Sources 2009;191:338–43. aqueous solutions by pervaporation. Sep Purif Technol 2005;42:273–82.
[335] Wang A, Sun D, Cao G, Wang H, Ren N, Wu WM, et al. Integrated hydrogen [366] Thongsukmak A, Sirkar KK. Pervaporation membranes highly selective for
production process from cellulose by combining dark fermentation, micro- solvents present in fermentation broths. J Membr Sci 2007;302:45–58.
bial fuel cells, and a microbial electrolysis cell. Bioresour Technol [367] Zhou H, Su Y, Chen X, Wan Y. Separation of acetone, butanol and ethanol
2011;102:4137–43. (ABE) from dilute aqueous solutions by silicalite-1/PDMS hybrid pervapora-
[336] Zhao H, Zhang Y, Zhao B, Chang Y, Li Z. Electrochemical reduction of carbon tion membranes. Sep Purif Technol 2011;79:375–84.
dioxide in an MFC–MEC system with a layer-by-layer self-assembly carbon [368] Liu G, Wang W, Wu H, Dong X, Jiang M, Jin W. Pervaporation performance of
nanotube/cobalt phthalocyanine modified electrode. Environ Sci Technol PDMS/ceramic composite membrane in acetone butanol ethanol (ABE)
2012;46:5198–204. fermentation–PV coupled process. J Membr Sci 2011;373:121–9.
[337] Zhang Y, Angelidaki I. Innovative self-powered submersible microbial elec- [369] Vrana DL, Meagher MM, Hutkins RW, Duffield B. Pervaporation of model
trolysis cell (SMEC) for biohydrogen production from anaerobic reactors. acetone–butanol–ethanol fermentation product solutions using Polytetra-
Water Res 2012;46:2727–36. fluoroethylene membranes. Sep Sci Technol 1993;28:2167–78.
[338] Dewan A, Donovan C, Heo D, Beyenal H. Evaluating the performance of [370] Roizard D, Favre E. Trends in design and preparation of polymeric mem-
microbial fuel cells powering electronic devices. J Power Sources branes for pervaporation in advanced materials for membrane preparation.
2010;195:90–6. In: Buonomenna MG, Golemme G, editors. Sharjah, U.A.E.: Bentham Science
[339] Wang H, Park JD, Ren Z. Active energy harvesting from microbial fuel cells at Publishers; 2012.
the maximum power point without using resistors. Environ Sci Technol [371] Jonquieres A, Fane AJ. Filled and unfilled composite GFT PDMS membranes
2012;46:5247–52. for the recovery of butanols from dilute aqueous solutions: influence of
[340] Park JD, Ren Z. High efficiency energy harvesting from microbial fuel cells alcohol polarity. J Membr Sci 1997;125:245–55.
using a synchronous boost converter. J Power Sources 2012;208:322–7. [372] Fouad EA, Feng X. Pervaporative separation of n-butanol from dilute aqueous
[341] Donovan C, Dewan A, Peng H, Heo D, Beyenal H. Power management system solutions using silicalite-filled poly(dimethyl siloxane) membranes. J Membr
for a 2.5 W remote sensor powered by a sediment microbial fuel cell. J Power Sci 2009;339:120–5.
Sources 2011;196:1171–7. [373] Li SY, Srivastava R, Parnas RS. Separation of 1-butanol by pervaporation
[342] Zhang B, He Z. Energy production, use and saving in a bioelectrochemical using a novel tri-layer PDMS composite membrane. J Membr Sci 2010;363:
desalination system. RSC Adv 2012;2:10673–9. 287–294.
[374] Niemistö J, Kujawski W, Keiski RL. Pervaporation performance of composite [404] Lay WCL, Zhang J, Tang C, Wang R, Liu Y, Fane AG. Factors affecting flux
poly(dimethyl siloxane) membrane for butanol recovery from model solu- performance of forward osmosis systems. J Membr Sci 2012;394–
tions. J Membr Sci 2013;434:55–64. 395:151–68.
[375] Fadeev AG, Meagher MM, Kelley SS, Volkov VV. Fouling of poly[-1-(tri- [405] Sukitpaneenit P, Chung TS. High performance thin-film composite forward
methylsilyl)-1-propyne] membranes in pervaporative recovery of butanol osmosis hollow fiber membranes with macrovoid-free and highly porous
from aqueous solutions and ABE fermentation broth. J Membr Sci structure for sustainable water production. Environ Sci Technol 2012;46:
2000;173:133–44. 7358–65.
[376] Elsayed A, Fouad XF. Use of pervaporation to separate butanol from dilute [406] Yip NY, Elimelech M. Performance limiting effects in power generation from
aqueous solutions: effects of operating conditions and concentration polar- salinity gradients by pressure retarded osmosis. Environ Sci Technol
ization. J Membr Sci 2008;323:428–35. 2011;45:10273–82.
[377] Hickey PJ, Juricic FP, Slater CS. The effect of process parameters on the [407] Alsvik IL, Zodrow KR, Elimelech M, Hägg MB. Polyamide formation on a
pervaporation of alcohols through organophilic membranes. Sep Sci Technol cellulose triacetate support for osmotic membranes: effect of linking mole-
1992;27:843–61. cules on membrane performance. Desalination 2013;312:2–9.
[378] El-Zanati E, Abdel-Hakim E, El-Ardi O, Fahmy M. Modeling and simulation of [408] Setiawan L, Rong Wang R, Tan S, Shi L, Fane AG. Fabrication of poly(amide-
butanol separation from aqueous solutions using pervaporation. J Membr Sci imide)-polyethersulfone dual layer hollow fiber membranes applied in
2006;280:278–83. forward osmosis by combined polyelectrolyte cross-linking and depositions.
[379] Qureshi N, Meagher MM, Huang J, Hutkins RW. Acetone butanol ethanol Desalination 2013;312:99–106.
(ABE) recovery by pervaporation using silicalite–silicone composite mem- [409] Sivertsen E, Holt T, Thelin W, Brekke G. Pressure retarded osmosis efficiency
brane from fed-batch reactor of Clostridium acetobutylicum. J Membr Sci for different hollow fibre membrane module flow configurations. Desalina-
2001;187:93–102. tion 2013;312:107–23.
[380] Norman RS. Water salination: a source of energy science. Science 1974; 186; [410] Song XX, Liu ZY, Sun DD. Nano gives the answer: breaking the bottleneck of
350–352; internal concentration polarization with a nanofiber composite forward
Chung TS, Li X, Ong RC, Ge Q, Wang H, Han G. Emerging forward osmosis osmosis membrane for a high water production rate. Adv Mater 2011;23
(FO) technologies and challenges ahead for clean water and clean energy (29):3256–60.
applications. Curr Opin Chem Eng 2012;1:246–57. [411] Tiraferri A, Yip NY, Phillip WA, Schiffman JD, Elimelech M. Relating perfor-
[381] Chou S, Wang R, Shi L, She Q, Tang C, Fane AG. Thin-film composite hollow mance of thin-film composite forward osmosis membranes to support layer
fiber membranes for pressure retarded osmosis (PRO) process with high formation and structure. J Membr Sci 2011;367:340–52.
power density. J Membr Sci 2012;389:25–33. [412] Yip NY, Tiraferri A, Phillip WA, Schiffman JD, Elimelech M. High performance
[382] Post JW, Hamelers HVM, Buisman CJN. Energy recovery from controlled thin-film composite forward osmosis membrane. Environ Sci Technol
mixing salt and fresh water with a reverse electrodialysis system. Environ Sci 2010;44(10):3812–8.
Technol 2008;42:5785–90. [413] Post JW, Goeting CH, Valk J, Goinga S, Veerman J, Hamelers HVM, et al.
[383] Veerman J, Saakes M, Metz SJ, Harmsen GJ. Electrical power from sea and Towards implementation of reverse electrodialysis for power generation
river water by reverse electrodialysis: a first step from the laboratory to a from salinity gradients. Desalin Water Treat 2010;16:18210.
real power plant. Environ Sci Technol 2010;44:9207–12. [414] Veerman J, Saakes M, Metz SJ, Harmsen GJ. Electrical power from sea and
[384] Stein ES. Osmotic power—a new, renewable energy source. Desalin Water river water by reverse electrodialysis: a first step from the laboratory to a real
Treat 2010;15:271–8. power plant. Environ Sci Technol 2010;44:9207–12.
[385] 〈http://salinitygradientpower.eu/wp-content/uploads/2011/08/Report-Barce [415] Veerman J, Saakes M, Metz SJ, Harmsen GJ. Reverse electrodialysis: perfor-
lona-2012.pdf〉; 2014 (viewed on 29 October 2014). mance of a stack with 50 cells on the mixing of sea and river water. J Membr
[386] Cippolina A. Integrated cycle for the production of fresh water, minerals and Sci 2009;327:136–44.
energy. Workshop water and power: challenges and solutions. Brussels, [416] Veerman J, Saakes M, Metz SJ, Harmsen GJ. Reverse electrodialysis: a
Belgium; 19–20 November 2012. validated process model for design and optimization. Chem Eng J
[387] Tedesco M, Cipollina A, Tamburini A, Micale G, Helsen J, Papapetrou M. REA 2011;166:256–68.
power: use of desalination brine for power production through reverse [417] Brauns E. Salinity gradient power by reverse electrodialysis: effect of model
electrodialysis. Desalin Water Treat, 2014 10.1080/19443994.2014.934102. parameters on electrical power output. Desalination 2009;237:378–91.
[388] Tedesco M, Cipollina A, Tamburini A, van Baak W, Micale G. Modelling the [418] Güler E, Elizen R, Vermaas DA, Saakes M, Nijmeijer K. Performance-
Reverse ElectroDialysis process with seawater and concentrated brines. determining membrane properties in reverse electrodialysis. J Membr Sci
Desalin Water Treat 2012;49:404–24. 2013;446:266–76.
[389] Elimelech M. Membrane-based technologies for sustainable production of [419] Guler E, Zhang Y, Saakes M, Nijmeijer K. Tailor-made anion-exchange
power in water–energy nexus symposium. Exhibition Center, Tel-Aviv; membranes for salinity gradient power generation using reverse electro-
January 29, 2013. dialysis. ChemSusChem 2012;5:2262–70.
[390] Post JW, Veerman J, Hamelers HVM, Euverink GJW, Metz SJ, Nymeijer K, et al. [420] Geise GM, Curtis AJ, Hatzell MC, Hickner MA, Logan BE. Salt concentration
J Membr Sci 2007;288:218–30. differences alter membrane resistance in reverse electrodialysis stacks.
[391] Ramon GZ, Feinberg BJ, Hoek EMV. Membrane-based production of salinity- Environ Sci Technol Lett 2014;1:36–9.
gradient power. Energy Environ Sci 2011;4:4423–34. [421] Galama AH, Vermaas DA, Veerman J, Saakes M, Rijnaarts HHM, Post JW, et al.
[392] 〈http://www.statkraft.com/media/news/News-archive/2013/Statkraft-halt Membrane resistance: the effect of salinity gradients over a cation exchange
s-osmotic-power-investments/〉; 2014 (viewed on 02 November 2014). membrane. J Membr Sci 2014;467:279–91.
[393] Statkraft Press Centre, Crown princess of Norway to open the world’s first [422] Vermaas DA, Bajracharya S, Bastos Sales B, Saakes M, Hamelers B, Nijmeijer K.
osmotic power plant; 2009. 〈http://www.statkraft.com/presscentre/press-re Clean energy generation using capacitive electrodes in reverse electrodia-
leases/crownprincess- mette-marit-to-open-the-worlds-first-osmotic-po lysis. Energy Environ Sci 2013;6:643–51.
wer-plant.aspx〉. [423] Meerganz von Medeazza GL. ‘‘Direct’’ and socially-induced environmental
[394] Achilli A, Childress AE. Pressure retarded osmosis: from the vision of Sidney impacts of desalination. Desalination 2005;185:57–70.
Loeb to the first prototype installation—review. Desalination 2010;261:205–11. [424] Elimelech M, Phillip WA. The future of seawater desalination: energy,
[395] Skilhagen SE, Dugstad JE, Aaberg RJ. Osmotic power — power production technology,and the environment. Science 2011;333:712–7.
based on the osmotic pressure difference between waters with varying salt [425] Service RF. Desalination freshens up. Science 2006;313:1088–90.
gradients. Desalination 2008;220:476–82. [426] Schiermeier Q. Water: purification with a pinch of salt. Nature 2008;452:
[396] McCutcheon JR, Elimelech M. Influence of concentrative and dilutive internal 260–261.
concentration polarizationonflux behavior in forward osmosis. J Membr Sci [427] Semiat R. Energy issues in desalination processes. Environ Sci Technol
2006;284(1–2):237–47. 2008;42:8193–201.
[397] McCutcheon JR, Elimelech M. Modeling water flux in forward osmosis: [428] The IDA desalination yearbook 2011–2012. Water desalination report.
implications for improved membrane design. AIChE J 2007;53(7):1736–44. [429] Dreizin Y, Tenne A, Hoffman D. Integrating large scale seawater desalination
[398] Yip NY, Tiraferri A, Phillip WA, Schiffman JD, Hoover LA, Chang Kim Y, et al. plants within Israel’s water supply system. Desalination 2008;220:132–49.
Environ Sci Technol 2011;45:4360–9. [430] Turek M, Mitko K, Chorążewska M, Dydo P. Use of the desalination brines in
[399] Glater J, Zachariah MR, Mccray SB, Mccutchan JW. Reverse-osmosis mem- the saturation of membrane electrolysis feed. Desalin Water Treat 2013;51:
brane sensitivity to ozone and halogen disinfectants. Desalination 1983;48 2749–2754.
(1):1–16. [431] De Vito C, Mignardi S, Ferrini V, Martin RF. Reject brines from desalination as
[400] Kwon YN, Leckie JO. Hypochlorite degradation of crosslinked polyamide possible sources for environmental technologies. Prof. Robert Y Ning editor,
membranes—II. Changes in hydrogen bonding behavior and performance. J ISBN: 978-953-307-624-9, InTech; 2011. Available from: 〈http://www.inte
Membr Sci 2006;282:456–64. chopen.com/books/expanding-issues-in-desalination/reject-brines-from-de
[401] Jons SD, Stutts KJ, Ferritto MS, Mickols WE. Treatment of composite salination-aspossible-sources-for-environmental-technologies〉.
polyamide membrane to improve performance. Patent 5876602; 1999. [432] Charcosset C. A review of membrane processes and renewable energies for
[402] Chou S, Wang R, Fane AG. Robust and high performance hollow fiber desalination. Desalination 2009;245:214–31.
membranes for energy harvesting from salinity gradients by pressure [433] Gude VG, Nirmalakhandan N, Deng S. Renewable and sustainable approaches
retarded osmosis. J Membr Sci 2013;448:44–54. for desalination. Renewable Sustainable Energy Rev 2010;14:2641–54.
[403] Chou S, Wang R, Shi L, She Q, Tang C, Fane AG. Thin-film composite hollow [434] De Munari A, Capao DPS, Richards BS, Schaefer AI. Application of solar-
fiber membranes for pressure retarded osmosis (PRO) process with high powered desalination in a remote town in South Australia. Desalination
power density. J Membr Sci 2012;389:25–33. 2009;248(1–3):72–82.
[435] Richards LA, Richards BS, Schaefer AI. Renewable energy powered membrane [468] Thomson M, Infield D. A photovoltaic-powered seawater reverse-osmosis
systems: inorganic contaminant removal from Australian groundwaters. system without batteries. Desalination 2003;153:1–8.
Membr Water Treat 2011;2(4):239–50. [469] Schies A, Went J, Heidtmann C, Eisele M, Kroemke F, Schmoch H, et al.
[436] Papapetrou M, Epp C, Tzen E. Autonomous desalination units based on Operating control strategies and dimensioning of photovoltaic powered
renewable energy systems—a review of representative installations world- reverse osmosis desalination plants without batteries. Desalin Water Treat
wide. L Rizzuti et al. editors. Solar desalination for the 21st century; 2007. 2010;21:131–7.
p. 343–353. [470] Al-Karaghouli A, Kazmerski L. Economic and technical analysis of a reverse-
[437] Trieb F, Nitsch J, Kronshage S, Schillings C, Brischke LA, Knies G, et al. osmosis water desalination plant using DEEP-3.2 software. J Environ Sci Eng,
Combined solar power and desalination plants for the Mediterranean region A 2012;1(3A):318–31.
—sustainable energy supply using large-scale solar thermal power plants. [471] Bilton Amy M, Kelley Leah C, Steven Dubowsky. Photovoltaic reverse osmosis
Desalination 2003;153:39–46. —feasibility and a pathway to develop technology. Desalin Water Treat
[438] Jeridi Bachellerie I. Renewable energy in the GCC countries. Resources, 2011;31:24–34.
poetential, prospects. 2012. Gulf Research Center; 2012. [472] 〈http://www.constructionweekonline.com/article-23968-saudi-solar-power
[439] Eltawil MA, Zhengming Z, Yuan L. Renewable energy powered desalination ed-desal-plant-ready-by-year-end/#.UoJ-fyfr7Kc〉;2013 (viewed on 12
systems: technologies and economics-state of the art. Twelfth international November 2013).
water technology conference, IWTC12 2008. Alexandria, Egypt; 2008. [473] Camacho LM, Dumée L, Zhang J, Li J-d, Mikel Duke M, Gomez J, et al.
[440] Li C, Goswami Y, Stefanakos E. Solar assisted sea water desalination: a Advances in membrane distillation for water desalination and purification
review. Renewable Sustainable Energy Rev 2013;19:136–63. applications. Water 2013;5:94–196.
[441] Papapetrou M, Wieghaus M, Biercamp C. Roadmap for the development of [474] Alkhudhiri A, Darwish N, Hilal N. Membrane distillation: a comprehensive
desalination powered by renewable energy; 2010 Prodes Project. 〈www. review. Desalination 2012;287:2–18.
prodes-project.org〉. [475] Jansen AE, Hanemaaijer JH, van Medevoort J, Dotremont C, van Sonsbeek E.
[442] Richards BS, Capao DPS, Schaefer AI. Renewable energy powered membrane Memstill_ membrane distillation—a future desalination technology. In:
technology. 2. The effect of energy fluctuations on performance of a photovoltaic Proceedings of the international conference on advances in science and
hybrid membrane system. Environ Sci Technol 2008;42(12):4563–9. engineering for brackish water and seawater desalination. , ECI. Cetraro,
[443] Missirlis K, Manoli E, Arambatzis G, Assimacopoulos D. The design of a Italy; May 8-12, 2010. p. 82-84.
desalination plant powered by renewable energies. Fifth international water [476] Koschikowski J, Wieghaus M, Rommel M. Solar thermal driven desalination
technology conference, IWTC2000. Alexandria, Egypt; 3–5 March 2000. plants based on membrane distillation. Desalination 2003;156:295–304.
[444] Knights D, MacGill I, Passey R. The sustainability of desalination plants in [477] Khayet M, Matsuura T. Membrane distillation: principles and applications.
Australia: is renewable energy the answer? OzWater conference. Sydney; 5th Oxford: Elsevier; 2011.
March 2007. [478] Singh D, Sirkar KK. Desalination of brine and produced water by direct
[445] 〈http://sydneydesal.com.au/〉. contact membrane distillation at high temperatures and pressures. J Membr
[446] 〈http://www.watercorporation.com.au/water-supply-and-services/solution Sci 2012;389:380–8.
s-to-perths-water-supply/desalination/perth-seawater-desalination-plant〉. [479] Alkhudhiri A, Darwish N, Hilal N. Produced water treatment: application of
[447] 〈http://www.degremont.com/en/activities/references/references/?reference air gap membrane distillation. Desalination 2013;309:46–51.
_id=49〉. [480] Susanto H. Towards practical implementations of membrane distillation.
[448] 〈http://www.macdow.com.au/news/adelaide-desalination-plant-fully- Chem Eng Process 2011;50:139–50.
operational〉. [481] Francis L, Ghaffour N, Alsaadi AA, Amy GL. Material gap membrane distilla-
[449] 〈http://www.acciona.com/news/acciona-to-double-the-capacity-of-the-ade tion: a new design for water vapor flux enhancement. J Membr Sci
laide-%28australia%29-desalination-plant-〉. 2013;448:240–7.
[450] 〈http://waterprojectsonline.com/case_studies/2010/Thames_Beckton_2010.pdf〉. [482] Zuo G, Wang R. Novel membrane surface modification to enhance anti-oil
[451] 〈http://reneweconomy.com.au/2013/ fouling property for membrane distillation application. J Membr Sci
carnegie-to-develop-first-wave-powered-desalination-plant-81863〉. 2013;447:26–35.
[452] Schillings C, Trieb F, Czisch G, Knies G, Nitsch J, Brischke LA, et al. Combined [483] Dumée LF, Gray S, Duke M, Sears K, Schütz J, Finn N. The role of membrane
solar power and desalination plants for the Mediterranean region—sustain- surface energy on direct contact membrane distillation performance. Desa-
able energy supply using large-scale solar thermal power plants. Desalina- lination 2013;323:22–30.
tion 2002;153:39–46. [484] 〈http://www.usbr.gov/research/AWT/reportpdfs/report081.pdf〉; 2013 (viewed
[453] Qtaishat MR, Banat F. Desalination by solar powered membrane distillation on 12 November 2013).
systems. Desalination 2013;308:186–97. [485] 〈http://www.psa.es/webeng/projects/medesol/overview.php〉; 2013 (viewed
[454] Subramani A, Badruzzaman M, Oppenheimer J, Jacangelo JC. Energy mini- on 12 November 2013).
mization strategies and renewable energy utilization for desalination: a [486] 〈http://www.pub.gov.sg/research/Key_Projects/Pages/Membrane3.aspx〉;
review. Water Res 2011;45:1907–20. 2013 (viewed on 12 November 2013).
[455] Qiblawey HM, Banat F. Solar thermal desalination technologies. Desalination [487] 〈http://www.memsys.eu/technology.html〉; 2013 (viewed on 12 November 2013).
2008;220:633–44. [488] Banat F, Jwaied N. Autonomous membrane distillation pilot plant unit driven
[456] Ali MT, Fath HES, Armstrong PR. A comprehensive techno-economical review by solar energy: experiences and lessons learned. Int J Sustainable Water
of indirect solar desalination. Renewable Sustainable Energy Rev 2011;15: Environ Syst 2010;1:21–4.
4187–4199. [489] Koschikowski J, Wieghaus M, Rommel M, Ortin VS, Peñate Suarez B,
[457] Qiblawey H, Banat F, Al-Nasser Q. Performance of reverse osmosis pilot Betancort Rodríguez JR. Experimental investigations on solar driven stand-
plant powered by photovoltaic in Jordan. Renewable Energy 2011;36: alone membrane distillation systems for remote areas. Desalination 2009;248:
3452–60. 125–131.
[458] Bilton AM, Wiesman R, Arif AFM, Zubair SM, Dubowsky S. On the feasibility [490] Cipollina A, di Sparti MG, Tamburini A, Micale G. Development of a
of community-scale photovoltaic-powered reverse osmosis desalination membrane distillation module for solar energy seawater desalination. Chem
systems for remote locations. Renewable Energy 2011;36:3246–56. Eng Res Des 2012;90:2101–21.
[459] Abdallah S, Abu-Hilal M, Mohsen MS. Performance of a photovoltaic powered [491] 〈http://m.konetic.or.kr/tech/view4.asp?unique_num=8787〉; 2013 (viewed
reverse osmosis system under local climatic conditions. Desalination on 12 November 2013).
2005;183:95–104. [492] 〈http://desalination.edu.au/2013/07/solar-desal-hybrid-trialled-in-remote-t
[460] Houcine I, Benjema F, Chahbani MH, Maalej M. Renewable energy sources for juntjuntjara/#.UoSbYifr7Kd〉; 2013 (viewed on 12 November 2013).
water desalting in Tunisia. Desalination 1999;125:123–32. [493] Mericq JP, Laborie S, Cabassud C. Vacuum membrane distillation of seawater
[461] Herold D, Neskakis A. A small PV-driven reverse osmosis desalination plant reverse osmosis brines. Water Res 2010;44:5260–73.
on the island of Gran Canaria. Desalination 2001;137:285–92. [494] Cao X, Huang X, Liang P, Xiao K, Zhou Y, Zhang X, et al. A new method for
[462] Bouguecha S, Hamrouni B, Dhahbi M. Small scale desalination pilots powered water desalination using microbial desalination cells. Environ Sci Technol
by renewable energy sources: case studies. Desalination 2005;183:151–65. 2009;43:7148–52.
[463] Riffel DB, Carvalho PCM. Small-scale photovoltaic-powered reverse osmosis [495] Mehanna M, Saito T, Jingling Y, Hickner MA, Cao X, Huang X, et al. Using
plant without batteries: design and simulation. Desalination 2009;250: microbial desalination cells to reduce water salinity prior to reverse osmosis.
42–53. Energy Environ Sci 2010;3(8):1114–20.
[464] Al-Karaghouli A. and Kazmerski L.L. Economic analysis of a brackish water [496] Jacobson KS, Drew D, He Z. Efficient salt removal in a continuously operated
photovoltaic-operated (BWRO-PV) desalination system. World renewable upflow microbial desalination cell with an air cathode. Bioresour Technol
energy congress XI. Abu Dhabi, United Arab Emirates; September 25–30, 2011;102:376–80.
2010. [497] Chen X, Xia X, Liang P, Cao X, Sun H, Huang X. Stacked microbial desalination
[465] Cheah SF. Photovoltaic reverse osmosis desalination system. Littleton, CO, cells to enhance water desalination efficiency. Environ Sci Technol
USA: ITN Energy Systems, Inc.; 2004. 2011;45:2465–70.
[466] Thomson M, Miranda M, Gwillim J, Rowbootom A, Draisey I. Batteryless [498] Mehanna M, Kiely PD, Call DF, Logan BE. A microbial electrodialysis cell for
photovoltaic reverse osmosis desalination system. DTI Sustainable Energy simultaneous water desalination and hydrogen gas production. Environ Sci
Programmes; 2001, Crown. Technol 2010;44(24):9578–83.
[467] Thomson M, Infield D. Laboratory demonstration of a photovoltaic-powered [499] Luo H, Jenkins PE, Ren Z. Concurrent desalination and hydrogen generation
seawater reverse-osmosis system without batteries. Desalination 2005;183: using microbial electrolysis and desalination cells. Environ Sci Technol
105–111. 2011;45(1):340–4.
[500] Ping Q, Cohen B, Dosoretz C, He Z. Long-terminvestigation of fouling of [505] Brastad KS, He Z. Water softening using microbial desalination cell technol-
cation and anion exchange membranes in microbial desalination cells. ogy. Desalination 2013;309:32–7.
Desalination 2013;325:48–55. [506] Bergman RA. Membrane softening versus lime softening in Florida: a cost
[501] Davis RJ, Kim Y, Logan BE. Increasing desalination by mitigating anolyte ph comparison update. Desalination 1995;102:11–24.
imbalance using catholyte effluent addition in a multi-anode bench scale [507] Zhang B, He Z. Energy production, use and saving in a bioelectrochemical
microbial desalination cell. ACS Sustainable Chem Eng 2013;1:1200–6. desalination system. RSC Adv 2012;2(28):10673–9.
[502] Chen X, Liang P, Wei Z, Zhang X, Huang X. Sustainable water desalination and [508] Kim Y, Logan BE. Simultaneous removal of organic matter and salt ions from
electricity generation in a separator coupled stacked microbial desalination saline wastewater in bioelectrochemical systems. Desalination 2013;308:
cell with buffer free electrolyte circulation. Bioresour Technol 2012;119: 115–121.
88–93. [509] Kim Y, Logan BE. Microbial desalination cells for energy production and
[503] Morel A, Zuo K, Xia X, Wei J, Luo X, Liang P, et al. Microbial desalination cells desalination. Desalination 2013;308:122–30.
packed with ion-exchange resin to enhance water desalination rate. Bior-
esour Technol 2012;118:243–8.
[504] Qu Y, Feng Y, Liu J, He W, Shi X, Yang Q, et al. Salt removal using multiple
microbial desalination cells under continuous flow conditions. Desalination
2013;317:17–22.

Membrane Processes and Renewable Energies

Uploaded by

Copyright:

Available Formats

Membrane Processes and Renewable Energies

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Membrane Processes and Renewable Energies

Uploaded by

Copyright:

Available Formats

Renewable and Sustainable Energy Reviews 43 (2015) 1343–1398

Contents lists available at ScienceDirect

Renewable and Sustainable Energy Reviews

Membrane processes and renewable energies

1. Introduction industry due to hydrofracking, enabling ﬁrms to extract natural

Fig. 3. Process Intensiﬁcation and its components [11].

Solar Energy Pressure Retarded

Wind Energy Biobutanol Membrane

Scheme 1. Interconnections between renewable energy sources and membrane operations.

Membrane processes Biomass conversion process Advantages (A)/challenges (C) Refs.

Upgrading of biogases (H2, CH4) coming from fermentative processes:

Membranes can be integrated into IGCC in a variety of ways

much lower temperatures than in conventional catalytic reformers represents

development of novel catalysts with a high activity and a good selectivity at

membrane durability;– High product recovery can be obtained in multi-stage

– Biogas pre-treatment is necessary to avoid membrane damage and .extend

Pyrolysis of biomass involves the thermal decomposition of the

Upgrading of biogases (H2, CH4) coming from fermentative processes

biomass in the absence of air or oxygen. It occurs at around 500 1C.

amount of energy, which leads to a limited or even negative effect

on the overall CO2 reduction. The available amount of wet biomass

and residues is considerable, so that their use as feedstock for

renewable energy production is certainly worthwhile [49]. Biolo-

suited for decentralized energy production in small-scale installa-

Type Electrolyte Operating temperature (1C) Commercial applications

Fig. 9. Block diagram of an ITM oxygen unit in an IGCC facility [91].

Entry Technology Main characteristics Advantages Disadvantages References

biomass Biomass Volatiles (Tar) Secondary Tar (bio-oils)

Membrane type Membrane material T (1C) Permeability H2 [10 13 (mol/m/m2/s/Pa)] Refs.

Ceramic–metal composite (cermet)a Ni–Ba(Zr0.1Ce0.7Y0.2)O3 δ 900 8.7 [122]

Low Temp High Temp

Cyclone Catalytic Steam

Cyclone Catalytic Steam

Cyclone Catalytic Steam

Phenolic Phenolic Separation

Transesterification Food processing

Plants & animal fats

1.9% (theoretical limit 68% [160])

Fermentative bacteria, Photosynthetic bacteria

Fermentative bacteria followed by anoxygenic

Several processes are currently under development for the

biological hydrogen production processes, that are being explored

bic pathway, is one of the key issues, due to the conversion of

CH3COOH þ2H2Oþ light-4

hydrogen to methane in this step (see Fig. 18) Another important

issue in the production of hydrogen, from anaerobic fermentation,

is the type of fermentation, as discussed in Section 2.1.2.3.

Biological production of hydrogen is an exciting area of tech-

nology development that offers potential production of usable

hydrogen from a variety of renewable resources. But, there are

Can biohydrogen production systems be integrated with hydrogen

fuel cell technologies to generate electricity at a practical scale

Both bio-methane and bio-hydrogen production methods are

cess volumes. Furthermore, the feedstock (wet biomass or bio-

waste) cannot be easily transported over large distances. Based on

should be available. This leads to two possible conﬁgurations for

the ‘production to end-use chain’. Either the gas is used directly at

Fig. 21. Two possible conﬁgurations of AnMBRs.

Pretreated alcohol distillery 55 250 – 40 490 1. Polypropylene [188]