Journal of Membrane Science 380 (2011) 1–8

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Journal of Membrane Science

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Perspective

Membrane engineering in process intensification—An overview

Enrico Drioli a,b,c,1 , Andrzej I. Stankiewicz d,2 , Francesca Macedonio a,b,∗
a
Department of Chemical Engineering and Materials, University of Calabria, Via P. Bucci Cubo 42/A, 87030 Arcavacata di Rende (CS), Italy
b
National Research Council – Institute on Membrane Technology, ITM-CNR, c/o University of Calabria, Via P. Bucci Cubo 17/C, 87030 Arcavacata di Rende (CS), Italy
c
Hanyang University, WCU Energy Engineering Department, Room 917 9th Floor FTC Bldg., 17 Haengdang-dong, Seongdong-gu, Seoul 133-791 South Korea
d
Process & Energy Department, Delft University of Technology, Leeghwaterstraat 44, 2628 CA Delft, The Netherlands

a r t i c l e i n f o a b s t r a c t

Article history: One of the crucial challenges currently facing the world is “to support sustainable industrial growth”. A
Received 15 December 2010 possible solution is offered by process intensification (PI), a design approach offering concrete benefits in
Received in revised form 24 June 2011 manufacturing and processing, substantially shrinking equipment size, boosting plant efficiency, saving
Accepted 25 June 2011
energy, reducing capital costs, increasing safety, minimizing environmental impact and maximizing the
Available online 8 July 2011
raw materials exploitation.
Membrane processes address the goals of PI because they have the potential to replace conventional
Keywords:
energy-intensive techniques, to accomplish the selective and efficient transport of specific components,
Membrane engineering
Process intensification
and to improve the performance of reactive processes. On a number of occasions, commercial conven-
tional separation processes in industry were converted to membrane separation processes with significant
reductions in cost, energy, and environmental impact.
This paper discusses how membrane engineering contributes to realization of the principles of process
intensification. An overview of current developments in the field of membrane operations and their
place in the intensification of chemical manufacturing and processing is presented. Several cases of
successfully commercialized technologies are discussed in detail. Finally, the opportunity to integrate
conventional membrane units with innovative membrane systems or into existing industrial processes
is also emphasized.
© 2011 Elsevier B.V. All rights reserved.

1. Introduction – process intensification: its strategy
motivations, methodology and objectives
The driving forces of the current world are globalization, sus-
tainability, partnership, innovation, discovery and development.
However, nowadays, the way to satisfy the increasing demand for
progress, improvement, raw materials, energy and products under
the constraints imposed by the concept of sustainable development
is a complex problem. A possible solution is offered by process inten-
sification (PI), a strategy that increases the competitiveness of the
process industries by making industrial processes more efficient,
faster and more environmentally friendly.
The aim of process intensification is to bring drastic improve-
ments in manufacturing and processing, substantially decreasing
∗ Corresponding author at: Department of Chemical Engineering and Materials,
University of Calabria, Via P. Bucci Cubo 42/A, 87030 Arcavacata di Rende (CS), Italy.
Tel.: +39 0984 492014; fax: +39 0984 402103.
E-mail addresses: e.drioli@itm.cnr.it (E. Drioli), A.I.Stankiewicz@tudelft.nl
(A.I. Stankiewicz), macedonio@unical.it (F. Macedonio).
1
Tel.: +39 0984 492039; fax: +39 0984 402103.
2
Tel.: +31 15 2786678; fax: +31 15 2786975.
equipment size and energy consumption, increasing plant effi-
ciency, reducing capital costs, increasing safety, minimizing waste
production and reducing environmental impact. Sustainability and
competitiveness are essential objectives for the process industry,
and the accelerated implementation of process intensification will
help to achieve a sustainable and economically strong process
industry. The potential benefits of process intensification for the
process industry are significant in terms of energy savings, reduc-
tion of CO2 emissions and enhanced cost competitiveness. They will
significantly impact each sector of the process industry in one way
or another.
Process intensification has been considered for more than two
decennia as a kind of technological “toolbox” containing some
spectacular examples of process improvement. In 2009 the first
attempt to define the fundamentals of process intensification was
undertaken by Van Gerven and Stankiewicz [1] and four generic
principles/objectives of PI have been defined [1].
This paper will try to answer the question of how membrane
engineering could and should contribute to the realization of the
process intensification strategy. It will discuss the relevancy and
ways of realization of the generic PI-principles in membrane engi-
neering, moving across all the relevant time and length scales, from
molecules up to the processing unit or even plant level.

0376-7388/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.memsci.2011.06.043
2 E. Drioli et al. / Journal of Membrane Science 380 (2011) 1–8
2. Application areas of membrane engineering for the
realization of process intensification strategy
Thirty-five years ago, when Colin Ramshaw and his co-workers
propounded the concept of process intensification, PI was defined
as a “reduction in plant size by at least a factor 100” (which was
quite a challenging number). In those days, in fact, the challenge
was seeking ways to improve process performance and reduce
capital cost. In the twenty-first century the focus has shifted to
sustainability of processes and products while competitiveness has
become the key objective. It is necessary to promote innovative,
low-cost, non-polluting, defect-free and safe industrial production
processes including avant-garde cycles whose design could support
the reduction of pollutant emissions and a more rational use of nat-
ural resources. Acting according to process intensification strategy
means pointing towards technologies and processes that are com-
pact and that reduce energy consumption, material use, and waste
production. For a long time process intensification has been applied
in only a few niche areas. Currently, it can offer a methodology
to suit many chemical and related industries, from petroleum to
pharmaceutical, agricultural, food, health, environmental, textile,
electronics and so on.
Membrane engineering has already provided interesting solu-
tions to some of the major problems of our modern industrialized
society. Membrane processes meet the requirements of PI because
they have the potential to replace conventional energy-intensive
techniques, to accomplish the selective and efficient transport of
specific components, and to improve the performance of reac-
tive processes. Membrane techniques are essential to a wide
range of applications including the production of potable water,
energy generation, tissue repair, pharmaceutical production, food
packaging and the separations needed for the manufacture of
chemicals, electronics and a range of other products [2]. At the
heart of every membrane process there is an interface clearly
materialized by a nano-structured/functionalised thin barrier. It
controls the exchange between two phases not only by exter-
nal forces and under the effect of fluid properties, but also
through the intrinsic characteristics of the membrane material
itself.
Membrane technology has already gained a huge importance in
the last two decades and now is competing with other separation
technologies in terms of energy efficiency, high separation capac-
ity, selective separation and capital investments. On a number of
occasions, commercial conventional separation processes in indus-
try were converted to membrane separation processes. This is what
happened, for example, in water desalination. In this field, con-
ventional thermal technologies have been gradually replaced with
Reverse Osmosis (RO) [3].
Membrane engineering has a much wider spectrum of poten-
tial applications as unit operations in process engineering than
in other technological areas. Membrane operations can be used
to conduct molecular separations (microfiltration, ultrafiltration,
reverse osmosis, etc.), chemical transformations (membrane reac-
tors, catalytic membranes, membrane bioreactors, etc.), and mass
and energy transfer between different phases (membrane con-
tactor, membrane distillation, membrane crystallizer, membrane
emulsifiers, membrane strippers, membrane scrubbers, etc.). The
availability of very thin interfaces (membranes) between differ-
ent phases for energy and mass transfer represents an important
opportunity for the optimization of a wide range of chemical and
biochemical operations.
In the following sections, a vision on the current developments
in the field of membrane operations and their place in the intensifi-
cation of chemical manufacturing and processing will be presented.
Several cases of successfully commercialized technologies will be
discussed in more detail.
2.1. Desalination
Seawater desalination through membrane technology, and in
particular through reverse osmosis, represents one of the unique
successes of membrane technology and it is probably one of the
clearest examples today of how the principles of process intensifi-
cation can be achieved.
Reverse osmosis desalination plants are currently the leader in
the desalination market, with RO installations representing 60% of
the total number of worldwide plants, whereas thermal processes
representing just 34.8% [4]. The widespread use of RO for desalina-
tion is due to its lower energy consumption, higher recovery factor
and lower cost with respect to conventional thermal plants.
Reverse osmosis allows one to desalinate waters through a
more energy efficient technology, with less CO2 discharge from
the energy consumed and less highly concentrated brine to be
disposed of as waste. The latter represents one of the biggest prob-
lems in desalination and the primary limitation to widespread
application of RO for inland brackish water desalination. There-
fore, the objectives of process intensification, consisting in “the
development of novel apparatuses and techniques that, compared to
those commonly used today, are expected to bring dramatic improve-
ments in manufacturing and processing, substantially decreasing
equipment-size/production-capacity ratio, energy consumption, or
waste production, and ultimately resulting in cheaper, sustainable
technologies”, as described by Stankiewicz and Moulijn [5] more
than 10 years ago, are better reached through membrane than
thermal processes.
Actually, further sustainable and efficient desalination pro-
cesses can be achieved in the future through integrated membrane
systems. Key characteristics of membrane operations are, in fact,
their great flexibility, operational simplicity and mutual compati-
bility for integration. These distinctive features offer the possibility
of combining different membrane technologies for minimizing the
limits of the single membrane units and for increasing the effi-
ciency of the overall system. Let’s see, for example, what happens
when membrane processes are used for RO pre- and post-treatment
instead of conventional technologies.
2.1.1. RO pre-treatment
Feed water to RO systems needs pretreatment to remove inor-
ganic and organic membrane foulants. Conventional pretreatment
uses rotating screens, chemical additives, chemical precipitation
and flocculation, followed by sand and cartridge filtration. The
process is complex and has a high operating cost. There is a
growing trend to replace all of these equipments with microfiltra-
tion/ultrafiltration. These membrane pre-treatment processes can
handle a large variation in raw water quality and still produce water
for the RO unit that is of better quality than water produced by the
conventional technology [6–9]. Membrane pretreatment systems
are also more compact and have lower operating costs than the
conventional processes. A comparison of the two technologies is
given in Table 1.
Proof of the benefits in the adoption of membrane over con-
ventional pre-treatment is their recent proliferation. CH2M Hill’s
Rob Huehmer has identified 94 such SWRO installations that are
in operation or have been contracted through April 2010. A break-
down of the market share based on installed capacities for MF/UF
membrane suppliers is shown in Fig. 1.
Currently, the possibility of making use of a membrane biore-
actor (MBR) as RO pre-treatment is also being investigated (as in
“MEDINA” research project, http://medina.unical.it). Usually MBR
is employed in wastewater treatment and reuse. In a MBR, low-
pressure membrane filtration (MF or UF) is used to separate effluent
from activated sludge. Since the membrane is an absolute bar-
rier for bacteria and, in the case of UF also for viruses, MBR
 E. Drioli et al. / Journal of Membrane Science 380 (2011) 1–8
Table 1
Comparison of conventional and MF/UF pre-treatment.
Item
Foot print
Energy requirements of pre-treatment
Chemical cost
RO capital cost
RO operating costs
RO energy requirements
RO membrane replacement
Modified from: Vedavyasan [9].
process provides disinfected effluents of high quality, especially
suitable for reuse and recycling of wastewater. Moreover, it could
also be of great interest in the removal of a variety of anthro-
pogenic organic pollutants and fouling agents that are increasingly
present in sea/brackish-water. MBR systems typically operate using
a submerged membrane module, with bundles of freely suspended
hollow fiber membranes with flow from outside-to-in. This inter-
esting new module design can be extended to a large variety
of other membrane operations in a very wide range of possible
applications including immersed membrane distillation, immersed
membrane reactors, immersed nanofiltration, immersed electro-
dialysis, etc.
Further improvements to RO pre-treatment that fall within
the domain of process intensification can be achieved through
the utilization of nanofiltration (NF) for the removal of turbidity,
microorganisms, hardness and most multivalent ions. This reduces
the osmotic pressure of the RO feed so that the system can be oper-
ated at higher recovery factors. In fact, according to [10,11], the
recovery factor of a coupled NF + RO seawater desalination system
is 10–12% higher than that of an SWRO plant based on conventional
pre-treatment.
2.1.2. RO post-treatment
One of the main problems related to seawater desalination
plants is that of brine disposal. At present the majority of desali-
nation facilities discharge their concentrated waste streams into
surface waters or oceans. However, this disposal method may dam-
age the environment unless safe and scrupulous measures are
Fig. 1. MF/UF membrane suppliers for SWRO pre-treatment:
installed/contracted capacity.
Source: Water Desalination Report, Volume 46, Number 26, 12 July 2010.
3
Conventional pre-treatment MF/UF pre-treatment
Larger footprint than MF/UF Significantly smaller
footprint
Less than MF/UF as it could be gravity flow Higher than conventional
High due to coagulant, disinfection, de-chlorination Low due to the low
and process chemicals needed chemical use
Higher than MF/UF since RO operates at lower flux Higher flux is possible
resulting in lower capital
cost than conventional
pre-treatment
Higher costs than MF/UF due to the high fouling Lower RO operating costs
potential of RO feed water (high fouling causes high due to less fouling
operating pressure, cleaning and chemical use) potential
Higher costs than MF/UF due to the high fouling that Lower
causes high operating pressure
High due to the high fouling Low
adopted to mitigate and control the impact of the discharged brine.
An interesting solution is once again offered by Membrane Engi-
neering and, in particular, by the use of novel and avant-garde
Membrane Contactor operations, such as direct contact membrane
distillation (DCMD) and membrane crystallization (MCr). DCMD
and MCr are two variants of the membrane distillation (MD) con-
cept, both of which operate at relatively low temperatures.
Membrane distillation is being investigated worldwide and it is
one of the best known methods for process-intensification [4]. The
technique is widely considered as an alternative to reverse osmo-
sis and evaporation. Membrane distillation employs hydrophobic
membranes for the separation of aqueous solutions. In an MD oper-
ation, an aqueous feed solution is brought into contact with one side
(feed or retentate side) of a hydrophobic microporous membrane.
The hydrophobic nature of the membrane prevents penetration of
the aqueous solution into the pores. Therefore, only volatile com-
ponents of the feed can be transported through the membrane in
the MD process. The temperature difference is the driving force for
the process which has seven basic advantages:
1. 100% rejection of ions, macromolecules, colloids, cells, and other
non-volatile components;
2. lower operating temperatures than in conventional evaporation
or distillation because it is not necessary to heat the pro-
cess liquids above their boiling temperatures. This enables the
processing of temperature-sensitive materials. Moreover, low-
grade waste and/or alternative energy sources can be coupled
with MD systems for a cost and energy efficient liquid separation
system.
3. Less membrane fouling owing to the use of larger pore size mem-
branes compared to RO and UF and to the fact that liquid cannot
enter the pores.
4. Lower operating pressure across the membrane than in the pres-
sure driven processes, which translates to lower equipment costs
and increased process safety.
5. Robust membranes since, in MD, they act merely as a support for
a vapor–liquid interface. Consequently, MD membranes can be
fabricated from almost any chemically resistant polymers with
intrinsic hydrophobic properties. This characteristic increases
membrane life.
6. MD permeate flux is only slightly affected by the salt concen-
tration of the feed water, and thus, unlike other membrane
processes, productivity and performance remain roughly the
same for high salt concentration feed-waters.
% of
7. By using hollow-fiber membrane modules, large mass-transfer
areas can be created, resulting in compact equipment.
4 E. Drioli et al. / Journal of Membrane Science 380 (2011) 1–8
As single units membrane contactors might also be more effi-
cient than corresponding traditional unit operations. However,
their coupling with other membrane operations is expected to pro-
vide even greater improvements in the efficiency of the overall
process.
Membrane contactors in water treatment systems can be used
for: (1) the reduction of the amount of oxygen or carbon dioxide
dissolved in the streams, (2) the removal of dangerous compo-
nents from polluted waters, (3) the diminution of the brine disposal
problem:
1. Oxygen and carbon dioxide present in seawater affect the per-
formance and the material life of desalination plants. Removal
of these gases is usually done by stripping in a packed column,
with the final water pH adjusted by means of caustic soda. This
operation is difficult to fine control owing to the very low dosing
rates, and it is not well accepted by end users who are uncom-
fortable using chemically treated waters. Membrane contactors
working on RO permeate and/or feed can provide the desired
control of oxygen and carbon dioxide content, thus avoiding the
need for chemicals. Moreover, membrane contactors can be also
applied for bubble-free water ozonation.
2. A second important and potential membrane contactor appli-
cation is for water purification when pollutants are non-volatile
components. An example can be found in [12], where DCMD has
been used for boron and arsenic removal from water.
3. Owing to the fact that DCMD/MCr operations are not limited
by concentration polarization phenomena, they can be used to
treat the concentrate streams of membrane desalination plants.
In particular, NF and/or RO retentate streams can be treated with
DCMD/MCr to recover water and salts, thus increasing the over-
all recovery factor of the desalination plant, reducing the volume
of the concentrated streams that need to be discharged, and,
in the case of MCr, recovering the dissolved salts in the form
of high-quality crystals. In some previous papers [13,14] it was
shown that recovery factors as high as 92.8% can be achieved in
integrated membrane-based seawater desalination plants with
MCr units working both on NF and on RO retentate streams.
Moreover, an integrated RO + Wind Aided Intensified Evapora-
tion + MCr brackish water desalination system has been used to
reduce the discharged brine to less than 0.75–0.27% of the raw
water fed to the system [15]. Therefore, DCMD/MCr cannot only
reduce the environmental problems related to brine disposal,
but can also increase the technical feasibility of inland brackish
water RO with the ions contained in the concentrated streams
recovered for agricultural, domestic or industrial use.
4. Details related to the characterization of the salts produced
through MCr operation in the treatment of NF/RO retentate
streams as well as the analysis of the stability and control of
MCr process can be found in [14,16].
Integrated membrane systems offer, therefore, new opportu-
nities in the design, rationalization and optimization of water
desalination cycles. They are emerging as essential tools for achiev-
ing “zero-liquid-discharge”, “total raw materials utilization” and “low
energy consumption” consistent with the process intensification
strategy.
2.2. Membrane-based reactive separations
Also the use of membranes in reacting systems provides a
combination of diverse functions that can lead to significant
improvements in the process performance. Those improvements
include, among other things, better yields/selectivities (e.g. via
equilibrium shift), better energy management, more compact
design, extension of catalyst lifetime, etc. Sirkar [17] gives an inter-
esting overview of various functions that a membrane may play in a
chemical reactor. Those functions are schematically shown in Fig. 2
and summarized in Table 2.
A nice example of combining catalytic and membrane functions
on the nano-scale can be found in Nishiyama et al. [18]. Coating
of the catalytic nanoparticles with membrane layers (e.g. carbon
molecular sieves or silicate-1) allowed the realization of a con-
trolled and selective feed to the active sites or a controlled product
removal.
Large-scale application areas of catalytic membrane reactors
include dehydrogenation, steam reforming, water-gas shift, and
selective oxidation reactions. Membrane price, robustness and low
fluxes still present barriers that hinder large-scale commercializa-
tion. An excellent review of the potential applications of catalytic
membrane reactors can be found in the monograph by Sanchez
Marcano and Tsotsis [19].
On the other hand, membranes are frequently employed in com-
bination with a bioreactor, for instance, to remove products in situ
in enzymatic processes (details in Section 2.2.1).
2.2.1. Membrane bioreactor
Integrating the properties of membranes with that of a biological
catalyst (such as cells or enzymes) is the basis of an important new
technology called a membrane bioreactor (MBR). The membrane
layer is especially useful for immobilizing whole cells (bacteria,
yeast, mammalian, plant cells) or bioactive molecules (enzymes)
to produce a wide variety of chemicals and substances [20]. The
catalytic action of the biocatalysts is extremely efficient and selec-
tive compared to conventional chemical catalysts. They can provide
higher reaction rates, milder reaction conditions and greater stere-
ospecificity [21]. The use of biocatalysts in combination with a
membrane enables bio-transformations to be integrated into con-
tinuous production lines. These systems work in time-invariant
conditions at steady state, providing better control of reaction con-
ditions with an increase in lifetime, productivity and economic
viability of the process. In addition, the separation, purification,
and concentration of the product can occur in a single integrated
unit operation. Thanks to the biocatalyst and membrane selectiv-
ity the mass intensity can be very high, with minimal by-product
formation, while producing high value co-products [21].
Membrane bioreactors were introduced over 30 years ago and
have established themselves as an alternative configuration for
traditional bioreactors. They seem particularly suited to carry out
complex enzymatic/microbial reactions and/or to separate, in situ,
the product in order to increase the reaction efficiency. Membrane
bioreactors can be used in a wide variety of applications and they
have been recommended or applied for the production of foods,
plant metabolites, amino acids, antibiotics, anti-inflammatories,
anticancer drugs, vitamins, proteins, optically pure enantiomers,
isomers, fine chemicals, biofuels and for wastewater treatment.
2.3. Membrane-based hybrid separations
Hybrid separations integrate two or more different separation
methods in a single operation, taking advantage of the synergies
between the processes. A membrane can actually be coupled with
any other type of separation and such combinations are briefly
reviewed below.
2.3.1. Membrane distillation
Membrane distillation presents a promising separation method
primarily applicable in environmental technologies. Currently, the
most important application area for membrane distillation is the
earlier described water desalination technology. Fig. 3 shows an
example of the water desalination processes developed by the
Japanese Water Re-Use Promotion Center, in co-operation with
 E. Drioli et al. / Journal of Membrane Science 380 (2011) 1–8 5

MEMBRANE
Product Selectively Removed
A+B C+D
B+D E D+F G
(Undesirable)
F
Purity Reactant A from Species F
Before Addition

Reactant B Reactant A

Distribute Reactant A
in a Controlled Fashion

Phase Interface Immobilized in

a Contactor
Non-Dispersive Contacting
on the Membrane

Immobilize Catalyst
in the Membrane

Membrane is the Catalyst

Retain Catalyst
in Reactor Membrane is the Reactor

Electrode Solid Electrolyte Membrane

Supports Electrodes,
Conducts Ions, and Reactions on Surface

Heat Transfer

Immobilized Liquid
Medium
Reactor Sweep, One Reactant
(Pure or a Mixture)

MEMBRANE

Fig. 2. Membrane functions in chemical reactor systems (after Sirkar [17]).

Table 2
Examples of membrane functions in chemical reactor systems (after Sirkar [17]).

Function Examples

1. Separation of products from the reaction mixture
2. Separation of a reactant from a mixed stream for introduction into
the reactor
3. Controlled addition of one reactant or two reactants
4. Non-dispersive phase contacting, with reaction at the phase
interface or in the bulk phases
5. Segregation of a catalyst (and cofactor) in a reactor
6. Immobilization of a catalyst in (or on) a membrane
7. Membrane is the catalyst
8. Membrane is the reactor
9. Solid-electrolyte membrane supports the electrodes, conducts ions,
and achieves the reactions on its surface
10. Transfer of heat
11. Immobilizing the liquid reaction medium
In situ product removal from enzymatic reactor via a nanofiltration or ultrafiltration
membrane
Removal of selected enantiomer via a liquid membrane
Removal of water in esterification reactions via a pervaporation membrane
Hydrogen removal in catalytic dehydrogenation reactions
Separation of oxygen from air for oxidizing methane to syngas
Separation of hydrogen from dehydrogenation reaction to oxidize it with oxygen on
permeate side
Separation of organic priority pollutants from wastewater for biological purification
Controlled oxygen addition in partial oxidation reactions (to increase selectivity)
Controlled air introduction in oxidative dehydrogenations
Emulsion-free enzymatic splitting of fats
Bubble-free oxygen/ozone supply in wastewater treatment via hollow-fiber
membranes
Segregation of enzymes with respect to molecular weight on ultrafiltration
membranes
Immobilization of enzymes or cells on polymeric membranes
Immobilization of metals (Pd, Pt) on ceramic membranes
Cation-exchange membranes for esterification reactions
Palladium membranes for hydrogenation/dehydrogenation reactions
Reactions in flow-through membrane systems (“pore flow through reactors”)
Solid electrolyte membranes as H+ and O2− conductors in fuel cells
Membranes coupling endo- and exothermic reaction zones (e.g.
hydrogenation–dehydrogenation)
Supported liquid membranes (SLM) for homogeneous catalytic processes
6 E. Drioli et al. / Journal of Membrane Science 380 (2011) 1–8
Fig. 3. Water desalination processes developed by the Japanese Water Re-Use Promotion Center, in co-operation with Takenaka Corporation and Organo Corporation.
Takenaka Corporation and Organo Corporation. This process uses
solar energy and can therefore be installed at locations without an
electricity supply [22].
Also membrane-based distillation technologies for fractionation
of non-water-based systems have been developed. An example
is MEMFRAC technology developed at the TNO institute in Hol-
land, which offers high energy efficiency in compact equipment
for vapor–liquid separations. Additional advantages of the technol-
ogy include: lack of entrainment, flooding, foaming or channeling
(owing to indirect gas-liquid contact), independent gas/liquid con-
trol and the possibility of modular plant design.
2.3.2. Integrated distillation-pervaporation/vapor permeation
systems
On the other hand, a membrane can be coupled with a
conventional distillation column, resulting in a hybrid mem-
brane/distillation process [23,24]. The combination of membrane
processes like pervaporation and vapor permeation with distil-
lation offers several advantages including reduction of energy
consumption, improvement of product quality and avoidance of
entrainers, making this technology especially suitable for close-
boiling or azeotropic mixtures [25]. Most industrial applications
have focused on the dehydration of solvents. Roza and Maus [26]
report possible significant energy savings of up to 50% compared
to extractive and pressure swing distillation; it leads also to lower
operating and investment costs. Fontalvo [27] showed that total
cost reductions of up to 60% are possible using a hybrid membrane-
distillation process for acetonitrile dehydration.
A further step is the integration of membrane separation and
reactive distillation (RD) which results in a highly intensified pro-
cess unit. An industrially applied process for the production of fatty
acids was presented by von Scala [28]. The authors claim that the
process can provide energy savings of up to 50%.
2.3.3. Membrane absorption/stripping
In membrane absorption a gaseous component is selectively
transported via a membrane and dissolved in the absorb-
ing liquid. It is also possible to carry out a membrane-based
absorption–desorption process with liquids on both sides of the
membrane [29], or a membrane stripping process in which selected
components are removed from the liquid phase through the mem-
brane by a stripping gas [30].
Membrane absorption, often seen in biological systems (e.g.
lungs or intestines), found its first applications in the medical sec-
tor in artificial heart–lung machines. One of the most important
industrial application areas of membrane absorption is the capture
of CO2 from flue gas. An example here is a membrane absorption-
based technology for the removal of CO2 from turbine exhaust gases
in offshore applications developed by Kvaerner [31]. The process
offers a very significant reduction in the weight and size of equip-
ment (70–75% and 65%, respectively) – a particular advantage for
offshore technology.
2.3.4. Membrane chromatography (adsorptive membranes)
Membrane chromatography is a separation technique applied
in the downstream processing of proteins [32–36]. Traditionally,
most chromatographic purification steps in protein processing use
columns packed with bead-shaped particles. The main feature and
advantage of membrane chromatography is the absence of pore
diffusion, which is the main transport resistance in traditional
chromatography. Dissolved molecules are carried directly to the
adsorptive sites in the membranes by the convective flow, which
can significantly increase the throughput of the process. Membrane
chromatography presents a process-intensive option for protein
A, G or L affinity chromatography, as well as for metal affinity,
ion-exchange, hydrophobic interaction and reversed-phase chro-
matography.
2.3.5. Membrane extraction
In membrane extraction the treated solution and the extrac-
tant/solvent are separated from each other by means of a solid or
liquid membrane [37–41]. The technique is primarily applied in
three areas: wastewater treatment (e.g. removal of pollutants or
recovery of trace components), in biotechnology (e.g. removal of
products from fermentation broths or separation of enantiomers)
and in analytical chemistry (e.g. on-line monitoring of pollutant
concentrations in wastewater).
2.3.6. Membrane crystallization
Membrane processes and crystallization have been also coupled
in the form of a membrane crystallizer (MCr) [11,42]. Membrane
Crystallization, which is an extension of the membrane distillation
concept, uses evaporative mass transfer of volatile solvents through
microporous hydrophobic membranes in order to concentrate feed
 E. Drioli et al. / Journal of Membrane Science 380 (2011) 1–8
solutions above their saturation limit, inducing supersaturation to
produce an environment where crystals may nucleate and grow.
For pressure lower than the entry limit, the hydrophobicity of the
membrane hinders the passage of liquid solutions through the
membrane. A liquid/vapor interface is present on both sides of each
pore with the gradient in chemical potential between these two
interfaces providing the driving force for the overall process. One
of the main characteristics of MCr is that the membrane not only
provides a support for the solvent evaporation but also induces
heterogeneous nucleation. The lowering of the barrier for nucle-
ation due to heterogeneous activation [11] is confirmed by the small
induction time for the appearance of crystals compared with other
crystallization techniques [43]. The possibility of growing crystals
using smaller quantities is an additional advantage of the process,
especially in proteomics [43].
Another main feature of MCr compared to conventional crys-
tallizers is the large number of extraction pores where solvent is
removed in the vapour phase. This improves the homogeneity of the
mother liquor providing crystals with good structural properties
and narrow size distribution.
Other advantages of MCr compared to conventional crystalliz-
ers include the increase in crystal growth rate and the possibility
of producing solid materials of high quality and controlled proper-
ties (as specific polymorphs) by controlling the rate of variation of
supersaturation. In fact, it is well known that the rate of variation
of the supersaturation affects the width of the metastable zone,
which influences the properties of the crystalline product (such as
size, size distribution and shape).
Owing to its intrinsic characteristics, the membrane crystal-
lizer may be an answer to the ever-growing market demand for
specialty high-value-added products, allowing control of crystal
shape and size, enhancing crystal growth kinetics, and achieving
selective crystallization of specific polymorphs. Potential appli-
cations include crystallization of proteins or the recovery of
crystalline materials from the brine in seawater desalination (as
earlier stated in Section 2.1.2). Membrane crystallization is also a
promising new technology for manufacturing pharmaceuticals [43]
and agro-chemical compounds (specific polymorphs preparation,
enantiomeric crystals, etc.).
3. Conclusions
Since the beginning of the 21st century, electronics, computer
science, medicine, chemistry and the related process industries
(from oil to pharmaceutical, agro and food, environment, textile,
building materials, cosmetics, etc.) have been continuously evolv-
ing, thanks to increasing and unprecedented market demands and
to emerging constraints from the public over environmental and
safety issues. The development of innovative processes that follow
the process intensification principles for a sustainable industrial
development is critical to the production of products with non-
polluting, defect-free and safe industrial processes.
Membrane science and technology offer new options for the
design, rationalization and optimization of innovative production
cycles. Membrane operations show a higher efficiency than con-
ventional separation and reaction unit operations. There are also
some interesting opportunities to integrate membrane operations
into existing industrial processes to achieve the benefits of PI.
Membrane engineering plays a dominant role in water desalina-
tion (currently dominated by Reverse Osmosis), in municipal water
treatments (with immersed membrane bioreactors), in agro-food
and petrochemical industries, in biotechnological processes and
regenerative medicine, and in the field of gaseous mixture sep-
arations (where membrane engineering represents an attractive
alternative to distillation). Natural gas dehumidification, separa-
tion of air components, separation and recovery of CO2 from biogas
7
and natural gas and of H2 from refinery industrial gases are some
other examples in which membrane technology is already applied
at the industrial scale. Moreover, oxygen-enriched air produced
by membranes has been used in various fields. A membrane reac-
tor might be ideally used to carry out hydrogenation reactions for
chemical production using CO2 recovered from exhaust gases by
membrane separation.
The design and development of innovative membrane-based
integrated processes continues to increase, providing critical sup-
port for the future development of sustainable industrial growth.
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