Drioli

PROGRESSES IN CATALYTIC
MEMBRANE REACTORS
Enrico Drioli, Enrica Fontananova
Institute on Membrane Technology (ITM-CNR), c/o University of Calabria, Via

P. Bucci, 17/C, 87030, Rende (CS), Italy
Department of Chemical Engineering and Materials, University of Calabria, Via
P. Bucci, Rende (CS), Italy.
Tel.: +39 0984 492039; Fax: +39 0984402103;
E-mail:e.drioli@itm.cnr.it; e.drioli@unical.it
Web site: www.itm.cnr.it
II WORKSHOP NAZIONALE AICIng - Messina, 12-14 Settembre 2007

Catalysis: one of chemistry’s most important and
powerful technologies
Sustainable Chemistry Strategic Research Agenda 2005 (www.suschem.org)
The concept of sustainable growth calls for

additional and substantial developments in
catalysis
Main characteristics of an “ideal catalyst”:
- low costs,
- high selectivity,
- high stability under reaction conditions,
- non-toxicity,
- “green properties” first of all recoverability (possibility to
reuse more times the same catalyst).
Most of these requirements can be addressed by the

heterogenization of the catalyst using appropriate support
materials.
Among the different heterogenization strategies, the entrapping of

catalysts in membranes,
membranes or in general the use of a catalyst
confined in a catalytic membrane reactor (CMR), offers new
possibility for the design of new catalytic processes.
Catalytic membranes reactors (CMRs) are
integrated systems that combine chemical
conversions with a physical separation
process guided by a membrane
General advantages of an integrated membrane

processes:
 synergic effects
 simplicity
possibility of advanced levels of
automatization
E. Drioli, M. Romano, Industrial Engineering Chemical Research, 40 (2001) 1277-1300
E. Drioli, E. Fontananova, Chemical Engineering Research & Design 82 (A12) (2004) 1557-1562

Membrane technologies and process intensification
strategy: a road to sustainability
Production Costs
Remote control Energy consumption
Process Waste generation
Design and Scale-Up
Intensification
Process Flexibility Equipment size

a
b
Scanning electron microscopy (SEM) images of the cross

section of a flat sheet (a) and of a hollow fiber (b) membrane
prepared from a modified polyetheretherketone known as
PEEK-WC

Common membrane processes combined with reactions
Mode of Species
Process Driving Force Species Passed
transport Retained
Suspended solids,
Microfiltration Pressure difference Size esclusion Solvent (water) and
fine particulars, some
(MF) 100-500 kPa convection dissolved solutes
colloids
Size esclusion Solvent (water) and
Ultrafiltration Pressure difference Macrosolutes and
convection low molecular weight
(UF) 100-800 kPa colloids
solutes (<1000 Da)
Solvent (water), low
Nanofiltration Pressure difference Size esclusion Molecular weight
molecular weight
Solution diffusion compounds >200 Da
(NF) 0.3-3 MPa solutes, monovalent
Donnan exclusion multivalent ions
ions
Membrane Based Chemical potential Compounds soluble Compounds non
Solvent Extration or concentration Diffusion partition in the extraction soluble in the
(MBSX) difference solvent extraction solvent
Gas molecules having Gas molecules having
Gas Separation Pressure difference low molecular weight high molecular
Solution diffusion
(GS) 0.1-10 MPa or high solubility- weight or low
diffusivity solubility-diffusivity
Chemical potential
Pervaporation High permeable Less permeable solute
or concentration Solution diffusion
(PV) solute or solvents or solvents
II WORKSHOP NAZIONALE AICIng -difference
Messina, 12-14 Settembre 2007
Filtration spectrum of some pressure driven membrane operations

Membrane contactors
Among separation techniques involving membranes,
membrane contactors (MC) are expected to play a
decisive role for the design of alternative production
systems appropriate for sustainable growth.
The basic idea is to use a solid, microporous,
hydrophobic polymeric matrix in order to create an
interface for mass transfer and/or reaction between two
phases: large exchange area and independent fluid-
dynamic allow a perfectly and easily controlled operation.
CONCENTRATE STRIPPING Accurel PP membrane

MEMBRANE CONTACTORS

Membrane contactors

The combination of advanced molecular separation and chemical
conversion, realized in a CMR, is expected to offer viable
solutions to the main drawback of the homogeneous catalysis: the
catalyst recycling.
In addition, the membrane can actively take part in the reactive

processes by controlling the concentration profiles thanks to the
possibility to have membrane with well defined properties
(materials & structure)
The selective transport properties of the membranes can be used

to shift the equilibrium conversion, to selectively remove products
and by-products from the reaction mixture, to selectively supply
the reagents.

Sketch of some different CMRs
S. Miachon,J.-A. Dalmon, Topics in Catalysis,29 (2004) 59-65
Extractor: The membrane is used to Distributor: The membrane controls Contactor:

remove a reaction product from the the introduction of one of the Membrane is used
reaction zone. reactants in the reaction zone. to facilitate the
contact between
Advantages: Advantages: reactants and
Increase reaction yields in equilibrium Reactants concentration is kept at a catalyst.
limited reactions; low level in the entire reaction zone
improving the selectivity towards a increasing selectivity of reactions Advantages:
primary product in consecutive (e.g. selective oxidations) and/or Improvements in
reactions via its selective extraction reducing the possible dangerous activity and
through the membrane. interations (e.g. flammable mixtures) selectivity

Role of the membrane:
Inert
Catalytically active
Nature of the membrane:
Organic
Nature of the catalyst:
Inorganic
Organic
Metallic
Inorganic
Biological
CMR set-up to evaluate the performance of the CMR:
flat sheet membrane reactor;

batch experiments for a
fast but incomplete
screening
(no evaluation of the
membrane selective
transport)
tubular membrane reactor;

I.F.J. Vankelecom, Chem. Rev. 102 (2002) 3779-3810
Membrane functions in a CMR
• retaining and recycling of the catalyst (retention in

the reactor of fine particles, enzymes and homogeneous
catalysts or heterogenization of catalyst in the membrane)
The heterogenization of catalysts in membrane is

particularly suitable for catalyst design at the atomic
and molecular level !

Example 1:
1 coupling of photocatalysis and membrane
processes in water purification
4-nitrophenol mineralization
2 C6H5NO2 + 15 O2 → 12 CO2 + 2 HNO3 + 4 H2O
Scheme of a membrane photoreactor with TiO2

immobilized in a PSF membrane (catalytically Scheme of a membrane photoreactor
active membrane) system with TiO2 particles suspended
R. Molinari et al. Journal of Membrane Science 206
confined by means of a UF or NF
(2002) 399–415 membrane (inert membrane)
• selective removal of products from the reaction
mixture to prevent consecutive reactions or to
circumvent the limitation by the equilibrium
(dehydrogenations, esterifications, etc.);
• selective supply of reactants to reduce the number
of process steps required (e.g. integrated oxygen
separation for partial oxidation) or to influence the
selectivity of the reaction (provide reactants in selective
form, influence on the concentration profile).
The separation function often results in

enhanced selectivity and/or yield !
Example 2: improved selectivity in consecutive reactions by
extration of a primary product (i-octene - C8) in a zeolite membrane
reactor (ZMR) respect to a a conventional fixed bed reactor (FBR)
Liquid-phase oligomerization of i-butene
2 C4H8 → C8H16
E. Piera et al. Catalysis Today 67 (2001) 127–138

Example 3: increase of the reaction yield respect to a
conventional reactor by selective removal of the product (H2)
Isobutane (iC4) dehydrogenation in an extractor-type CMR
C4H10 → C4H8 + H2
A: MFI zeolite A: Pd
membrane membrane
L. van Dyk et al. Catal. Today 82 (2003) 167

A: MFI-zeolite membrane growth on a tubular alumina host material;
B: Pd membrane electroless deposited on the same tubular support.
(1) experimental data; (2) modelling; (3) thermodynamic equilibrium in a

conventional reactor.
Example 4: dense mixed-oxide membranes used for partial
oxidations of methane
CH4 + ½ O2 → CO + 2 H2
V.V. Kharton et al. Catalysis Letters 99 (2005) 249-255

SrFe0.7Al0.3O3-d (SFA) –perovskite like oxide- exhibits substantial
catalytic activity towards partial oxidation of methane
It has been proposed that the oxygen species diffusing through the membrane
generate at its surface very active and selective oxygen entities that give
higher yields that molecular oxygen.
Perovskite
Perovskite-structured oxides
can be used as solid electrolytes
for oxygen separation.
Both oxygen ions and electronic

defects are transported in an
internal circuit in the membrane
material.
Perovskite membranes are

interesting systems not only for
their possible applications (e.g.,
fuel cells, oxygen generators,
oxidation catalysts) but also for The migration ion within the perovskite
the fundamental fascination of lattice takes place along the edge of the
fast oxygen transport in solid BO6 octahedron into neighbouring
state ionic. vacancy.
M. Saiful Islam, Solid State Ionics 154–155 (2002) 75–
85

SEM photographs of an asymmetric membrane of perovskite-type oxide
(La0.6Sr0.4Co0.2Fe0.8O3-δ) and temperature-dependence oxygen permeation
flux of the asymmetric membrane and a sintered membrane disc
W. Jin et al. Journal of Membrane Science 185 (2001) 237–243

Use of a mixed oxygen ion–
electronic conductor for oxygen
separation with direct reforming
of methane, followed by the use
of a mixed protonic–electronic
conductor for hydrogen
extraction
The products are thus pure

hydrogen and synthesis gas with
reduced hydrogen content, the
latter suitable for example,
Fisher–Tropsch synthesis of
methanol.
T.Norby/SolidStateIonics125(1999)1–11
•In some cases, the membrane defines the reaction

volume e.g. by providing a contacting zone for two
immiscible phases (phase transfer catalysis)
Exclusion of polluting solvents and reducing the

environmental impact of the process

Example 5: Cyclohexane oxidation by tertiary-butyl hydroperoxide
at room temperature using FePcY-Zeozymes occluded in a PDMS
O OH
O2
+
Separating the two immiscible

reactant phases the membrane:
eliminates the need for a solvent
Incorporation of iron phthalocyanine (FePc) actively controls the concentration

complex in the supercages of zeoliteY and of the reactants near the active sites
subsequent incorporation of these zeolite crystals in
I.F.J. Vankelecom et al.J. of Catalysis
the PDMS-membrane. 163 (1996) 457–464
Further advantages of the CMRs:
An integrated process involves lower investment costs
Membrane separations often have the advantage of operating at

much lower temperatures, especially when compared with thermal
processes such as reactive distillation. They might thus provide a
solution for the limited thermal stability of either catalyst or
products. Furthermore, the membrane separation processes is not
restricted to volatile components.
Under specific conditions, the heat dissipated in an exothermic

reaction can be used in an endothermic reaction, taking place at the
opposite side of the membrane, like, e.g., in
hydrogenation/dehydrogenation.
The downstream processing of the products can be substantially

facilitated when they are removed from the reaction mixture by
means of a membrane.
III.F.J. Vankelecom,
WORKSHOP Chem.
NAZIONALE AICIng Rev.12-14
- Messina, 102 (2002)
Settembre 3779-3810
2007
CMRs have been investigated for a broad variety of
reactions, however there is still a large discrepancy
between the many investigations on CMRs in
academic and a few industrial applications.
An industrial example is the consortium of BP/Amoco,

Praxair, Statoil, SASOL, and Phillips Petroleum working on
solid oxide membrane reactor based synthesis gas
production.
The main problem is the development of reliable and

financially competitive membranes.

Typical limitations in CMRs:
 Manufacturing cost of the membranes and modules
 Limited membrane life time
 Considerable technical complexity of the process

which renders modeling and prediction more difficult

The understanding of properties, behavior and
synthesis of materials is fundamental in order to
exploit the potential use of novel highly complex
composite systems, molecules and new multi-
functional materials derived from them.
Computational strategies, theoretical,

simulation and modelling are key tools to be
considered in CMRs

ORGANIC OR
INORGANIC MEMBRANES ?

I norganic m em branes
Advantages Disadvantages
Resistance to aggressive High capital costs

environments Brittleness
High thermal stability Generally low permeability of the
Resistance to high pressure highly selective (dense) membranes
at medium temperatures
Difficult membrane-to-module
sealing at high temperatures

CMRs for high temperature applications
Due to the generally severe conditions of

heterogeneous catalysis, most CMR applications
use inorganic membranes which can be dense
or porous, inert or catalytically active.

Palladium membranes for selectivity improvement in
dehydrogenation and hydrogenation reactions:
only hydrogen could permeate through the Pd membrane with a 100%
selectivity
Pd-Rh
The mechanism involves a alloy
series of steps: layer
1) adsorption
2) dissociation
3) ionization Support
4) diffusion
5) reassociation
6) desorption
http://www.stillwaterpalladium.com/hydrogen.html V.M. Gryaznov, Petroleum Chemistry 35 (1995) 181-188
To reduce the Pd consumption is possible to produced dense palladium

alloy layers (Pd-Ag, Pd-Rh, etc.) on thermostable porous support

Combination of the dehydrogenation on one surface of the Pd-
based catalytic membrane and hydrogenation by the diffused
hydrogen on the other surface
V. Gryaznov, Catalysis Today 51 (1999) 391±395

Other examples of inorganic membrane reactors
E. Drioli et al. Clean Products and Processes 2 (2000) 179–186

Typical examples of inorganic membrane reactors
II WORKSHOP NAZIONALE AICIngE. Drioli12-14

- Messina, et al. Clean
Settembre Products
2007 and Processes 2 (2000) 179–186
Polymeric membranes are usually used
when the reaction temperatures are lower, i.e.
in the field of fine chemicals or when
biocatalysts are present

Advantages of polymeric membranes
• A much wider choice of polymeric membranes is

available as compared with metallic or ceramic
membranes, and the costs are generally lower.
• The technology to manufacture polymeric

membranes is much better developed than the
one for inorganic and metallic membranes.
• The relatively low operating temperature of

polymeric catalytic membranes are also
associated with less stringent demands for the
materials needed in the module construction.

Although polymeric membranes are generally
less resistant to high temperature and
aggressive chemicals than inorganic or metallic
membranes, many polymeric materials as
amorphous perfluoro polymers (Hyflon)
resistant under rather harsh conditions, are
available.
Moreover, many reactions of relevant interest in

fine chemical synthesis or in the water treatment
take place under mild conditions .

Basic principles of the heterogenization of catalysts in
polymeric membranes
Major issues in the polymer selection:
good affinity for the catalyst in order to avoid catalyst leaching and
to have a good adhesion between polymer and catalyst with
dispersion of the same
mechanical, thermal, and chemical stability under reaction

conditions
good transport properties for the reagents and products

For a porous membrane, the choice of polymer is of less importance
for transport properties in comparison with dense membranes, as
permeation does not take place through the polymer matrix but
through the membrane pores. However the membrane material is
relevant for the stability and surface properties, such as wettability
and fouling.
Depending on the pore and molecule size, molecules are

transported through porous membranes via viscous flow, Knudsen
flow, molecular diffusion, surface diffusion, capillary condensation,
or molecular sieving.
Transport through dense membranes follows the solution-diffusion

model, according to which a molecule first sorbs in the polymer
before it diffuses through it and finally desorbs again.

Transport mechanism through porous membranes
Viscous flow
Knudsen flow
Surface diffusion
Capillar condensation

In viscous flow 1
J∝
ε r ∆ P Hagen-
2
η
J= Poiseuille
8η τ ∆ x equation
r pores radius
η viscosity
τ tortuosity
ε surface porosity ε = n π r / A p
2
n p number of the pores

A m membrane area

In Knudsen flow 1
J∝
M
π nr D ∆ p 2 W
J= k
RTτ l
D k Knudsen diffusion coefficient
8 RT
D = 0.66r
πM
k
T temperature
M molecular weight
w
n number of the pores

Transport mechanism through dense membranes
Solution-diffusion
Permeability ( P ) = So lub ility ( S ) x Diffusivity ( D)

Also interface phenomena have to be considered!

The performance of liquid phase pressure driven membrane
operation is particularly influenced by concentration
polarisation phenomena
dc
Jc + D = Jc
dx
p
Eric M. Vrijenhoek, Seungkwan Hong, Menachem Elimelech; Journal of Membrane Science 188 (2001) 115–128.
J. Mueller, R. H. Davis, Journal of Membrane Science 116 (1996) 47-60.

Fouling is another phenomenon that can
considerably change the system
performance during a membrane process,
Membrane fouling is the deposition of

retained particles, colloids, emulsions,
suspensions, macromolecules, salts, etc.
on or in the membrane.

Main techniques used in order to control
concentration polarization phenomena and
subsequent fouling:
 turbulence promoters
 corrugated membrane surfaces
 pulsatile flow
 vortex generation
 two-phase flow (solid/liquid and gas/liquid two
phase flow)

Membranes and biotechnological tools can be used for
improving traditional production systems.
Typical examples of application include:
new and improved foodstuffs, in which the desired

nutrients are not lost during thermal treatment;
novel pharmaceutical products with well-defined

enantiomeric compositions;
wastewater treatment wherein pollution by traditional

processes is a problem.

Biocatalytic membranes reactors
Recirculated (external) Integrated MBR

MBR
Biocatalyst Biocatalyst Biocatalyst Biocatalyst Biocatalyst
continuously flushed segregated within entrapped within gelified on bound to
along membrane membrane module membrane pores membrane membrane
Support binding Cross-linking
Physical Ionic Covalent

Adsorption binding Binding
Biocatalyst immobilized using different methods
Giorno, L., Drioli, E., Trends in Biotechnology, 2000, 18, 339-348
The immobilization of enzymes and microbial cell in artificial

membranes it is a well accepted technique that reproduces in many
aspects the natural operating conditions in living systems.
Thermophylic microbial cells (Caldariella acidophila or
Sulfolobus solfataricus) have been successful immobilized,
without loss of activity, in cellulose acetate artificial
membranes, since in the early eighties
M. De Rosa, A. Gambacorta, E. Esposito, E. Drioli, S. Gaeta, Thermophylic microbial

cells immobilized in cellulose acetate membranes, Biochimie 62 (1980) 517-522.

The possibility of using phase inversion technique for
preparing artificial polymeric membranes entrapping free
enzyme or whole cells containing the desired enzyme has
been limited by the requirement to avoid non-aqueous
solvents in the casting solution and thermal treatment
which typically denature the enzyme.
On the contrary, thermophilic microorganism showing high

resistance to acid, organic solvents, classical denaturating
agents (e.g. urea, guanidine, etc) and temperature up to
100°C, offer interesting opportunity for the immobilization
of biological catalysts in polymeric artificial membranes.

Submerged membrane bioreactors (SMBRs) are today
considered as a BAT (Best Available Technology)
Permeate
In the submerged MBR the driving force is achieved by
pressurizing the bioreactor or creating negative
pressure on the permeate side.
A diffuser is usually placed directly beneath the

membrane module to facilitate scouring of the filtration Reactor Membrane unit
surface. Aeration and mixing are also achieved by the

Feed
same unit.
Cleaning of the membrane is usually achieved Gas Diffuser

principally by bubbling, but also by permeate back-
pulsing and occasional by chemical backwashing.
SMBRs have been successfully applied in wastewater

treatment providing an effective alternative to
conventional processes such as activated sludge
The reduction in energy consumption associated with

the recirculation cost and the low transmembrane
pressures required make SMBRs well suited to
relatively large-scale applications.
Classic Sewage Treatment process
Primary Secondary treament Tertiary

treatment (Activated Sludge Process) treament
Effluent Primary Anoxic/ Secondary

sedimentation Aerobic clarifier
Disinfection
(sedimentation)
Replaced by a Submerged Membrane Bioreactor
Micro- Ultra-filtration
operation combined with
biomass treatment
Effluent Primary Anoxic/ Secondary Disinfection
sedimentation Aerobic clarifier
(sedimentation)
The membrane bioreactor (MBR)

combines biological treatment with
membrane separation. The treated
water is separated from the purifying
bacteria (active sludge) by a process
of membrane filtration rather than in
a settling tank as in conventional
systems. Only the treated effluent
passes through the membrane. It is
then pumped out. The sludge is
recovered and dewatered.
Improved performance:
The biomass contained in an MBR is
far more concentrated, varied and
lasting than in a conventional
system. These properties enhance
treatment efficiency.
http://www.sustainability.renault.com/s/s4i.htm
Wastewater treatment by Submerged
membrane bioreactor
 Final effluent quality
suitable for reuse
 Small footprint < 50% of
a conventional plant
 Easy to control, can be
monitored remotely
 Less sludge production,
generally 40% less
Schematic representation of external MBR
In the early 1990s, MBR installations were
mostly constructed in external configuration, in
which case the membrane modules are outside
the bioreactor and biomass is recirculated
through a filtration loop. This limited wider
application in treatment of municipal
wastewater. After the mid 1990s, with the
development of submerged MBR system, MBR
applications in municipal wastewater extended
widely.
Schematic representation of SMBR The concept of immersed

membranes was conceived in the
late 1980s/early 1990s by
independent teams in Japan and
Canada. In Japan, University of
Tokyo professors Aya and
Yamamoto, conducted laboratory
experiments with fine hollow fibers
immersed in an activated sludge
reactor. They published their results
in the late 1980s in a Japanese
journal.
External modules
Immersed modules
Example of effluents requirements
and achievable value by SMBR
Paramenter Regulation limit SMBR design
(mg/L) value (mg/L)
COD 125 125
BOD 25 25
TSS 35 5
TN - 10
TP - 10
Data from a Zenon plant in Brescia (Italy) for

treatment of sewage water
Representative costs for life cycle for
the Zenon MBR System
15%
8% Chemicals
40%
Membrane
Energy
Equipment
37%
MBR for wastewater treatment in
Porto Marghera: the largest
membrane bioreator unit in the
world!
Eni and Ondeo Industrial

Solutions have designed
and built the MBR
wastewater treatment unit
in order to extract
remaining pollutants in
tertiary water prior to
disposal into the Venetian
Lagoon.
UF section of the MBR plant in Porto Marghera (VE)
The ultrafiltration unit, containing submerged PVDF hollow fibers
membranes (ZeeWeed® by Zenon), is designed to treat 1600 m3/h of
wastewater with a COD/h of 445 kg.
There are two interconnected UF

lines.
Each line contains 4 unit composed
by 9 ZeeWeed® modules.
Total membrane area: 100.000 m2
Suspended matter of the treated

water <1mg/L: respect of the
regulations dealing with
wastewater disposal in the
Venetian Lagoon. Scheme of the UF unit containing 9
ZeeWeed® modules

Heterogenization of
polyoxometalates in polymeric
membranes for oxidation reactions

Catalytic oxidation reactions are nowadays widely in
different fields:
 Hydrocarbons transformation (petrolchemical industry)
 Selective oxidation of organic substrates (fine chemical synthesis)
Degradation of organic pollutants (wastewater treatment)
Membrane technology could offer interesting possibilities in

catalytic oxidations:
The use of non-covalent supports that bring together catalysts and
substrates in a suitable nano-environment may be particularly
advantageous
Heterogenization of polyoxometalates (active in
photo-oxidation reactions and operating in water with
O2) in polymeric membranes
Catalyst on the surface
Catalyst entrapped in
of plasma modified
the membrane
membranes
Ar/NH3 plasma
Phase inversion
F F
F
C C
F i
+ W10 PVDF-W10
PVDF-
PVDF
PVDF
PVDF-NH2
PVDF-NH2-W12 W12 aq.

W10 = TBA4 W10O32 W12 = H3PW12O40
Van der Waals interactions Ionic interactions catalyst-

catalyst-polymer! polymer!
M. Bonchio, M. Carraro, G. Scorrano, E. Fontananova and E. Drioli, Advanced Synthesis & Catalysis, 2003, 345, 1119-1126.
E. Fontananova et al. Heterogenization of polyoxometalates on the surface of plasma modified polymeric membranes (In preparation).
Catalyst entrapped in the membrane
676.79
61 2.91
762.20
600.95
Characteristic bands of
TBA4W10O32
949.25 747.38
1 453.1 8
PVDF (blank)
Wave
1 333.45
Group
51 0.32
482.1 3
1 429.89
number
Vibration
301 9.05
1 41 1 .42 1 202.95 1 073.28 880.49
(cm-1)
2979.25 839.79
W-Oc-W
599.1 3
%T
PVDF-W10 (25.0 wt%) 595 streching
1 483.44
1 453.43
1 334.38
476.07
509.49
803 W-Ob-W streching
2878.40
2967.76 1 072.82 957.84 958 W=O streching
W10 (in KBr) 1 670.92
1 637.28
1 403.93 1 283.94 1 1 71 .65
1 347.1 1
1 249.1 0 1 1 06.47
882.35
840.21
803.70
501 .26
1 1 52.53 1 027.1 2
CH2 (TBA
1 065.89 583.88
1 380.90
sym.
2870
994.29
3467.79
group) streching
2935.00 1 483.1 4
958.88
2873.1 8
2961 .07
890.80
4 0 0 0 .0 3600 3200 2800 2400 2000 1800 1600 1400 1200 1000 800 600 4 5 0 .0
cm- 1
 The catalyst structure is preserved within the polymeric

membrane

Phenol photodegradation by porous PVDF-W10 catalytic
membranes in a CMR
OH TMP=0 bar
1
TMP=0.5 bar
0.9 TMP=1 bar
0.8 TMP=1.5 bar

CO2 + H2O
Ct / C0
0.7
0.6
PVDF-W10 (14.3 wt%); 0.88 micromoles 0.5

1 PVDF-W10 (25.0 wt%); 1.73 micromoles
PVDF-W10 (33.3 wt%); 2.83 micromoles 0.4
0.9 0 50 100 150 200 250 300
0.8 Time (min)
Ct/C 0
0.7
0.6
Ct is the phenol concentration at the time t
0.5 C0 is the initial concentration
0.4
0 100 200 300
Time (min)
Effect of the catalyst loading (CL)and TMP on phenol degradation:

maximum efficiency was reached with CL= 25.0 wt% and TMP=1 bar
E. Fontananova, L. Donato, E. Drioli, M. Bonchio, M. Carraro, G. Scorrano, Heterogeneous Photo-Oxidation Performed By Polymeric Catalytic Membranes, 7th International
Conference on Catalysis in Membrane Reactors (ICCMR7) 11-14 Sept. 2005, Cetraro (CS) – Italy
E. Fontananova, E. Drioli, L. Donato, M. Bonchio, M. Carraro, G. Scorrano, Heterogeneous photooxidation of phenol by catalytic membranes, 7th World Congress
IIon
WORKSHOP NAZIONALE
Recovery, Recycling AICIng - Messina,
and Re-integration 12-14
(R’05), SettembreSeptember
Beijing·China, 2007 25 - 29, 2005
PHENOL DEGRADATION (%)
TIME (min) W10 (homogeneous) PVDF-W10 (25.0 wt%)
150 36.2 36.0

300 49.5 52.0
Phenol mineralization (TOC loss %)
TIME (min) W10 (homogeneous) PVDF-W10 (25.0 wt%)
150 24.7 36.0

300 34.0 48.8
The % of phenol degradation is similar in both homogeneous and

heterogeneous reactions
An higher % of phenol mineralization is observed with the catalytic
membrane
Catalytic membranes can be recycled without loss of activity in successive
catalytic runs

Catalyst on the surface of plasma modified membranes
XPS analyses of native and modified PVDF membrane by plasma technique
Substrate C% O% W4f% P2p% F% N% O/C N/C W/C F/C

PVDF 54,2 1,9 - - 43,8 / 0,04 - - 0,80
PVDF-NH2 57,6 4,7 - - 28,1 9,4 0,08 0,16 - 0,48
PVDF-NH2-W12 53,1 18,3 3,5 0,4 19,3 5,1 0,34 - 0,07 0,36
N% value is a measure of the efficiency of the grafting of N-groups.

This value diminishes from 9,4 for PVDF-NH2 to 5,1 for PVDF-NH2-W12, due
to the linking with the catalyst that partially quench the nitrogen groups.
W-based catalysts binding can be monitored by the XPS W%.
The W4f peak in the XPS spectra

of the catalytic membrane shows
two major components and this
behaviour is typical of tungsten
oxides
Catalyst on the surface of plasma modified membranes
Phenol photodegradation by PVDF-NH2-W12

0
-0.1 Process k (min-1) R2
-0.2 W12 0.00110 0.99
-0.3
PVDF-NH2-W12
0.00199 0.97
ln (n/n0)
-0.4 (TMP=0)
-0.5 PVDF-NH2-W12
PVDF-NH2-W12 (TMP=1 bar) 0.00313 0.98
-0.6 (TMP=1 bar)
-0.7 PVDF-NH2-W12 (TMP=0 bar)
-0.8 W12
-0.9
0 50 100 150 200 250
Time (min)
First order plot for the photocatalytic degradation of phenol in homogeneous W12 and heterogeneous PVDF-NH2-W12
reactions (n0 are the initial moles of phenol and nt the moles at the time t)
Catalytic activity is dependent on the transmembrane pressure

(concentration and contact time catalyst-substrate)
 Heterogeneous photodegradation is faster than homogeneous due to
high affinity polymer-substrate and optimal dispersion of the catalyst on
membrane surface
 The catalytic membranes are stable and recyclable
E. Fontananova, L. Donato, E. Drioli, L. Lopez, P. Favia, R. d’Agostino, Chemistry of Materials 18 (2006) 1561-1568
L. C. Lopez, M. G. Buonomenna, E. Fontananova, G. Iacoviello, E. Drioli, R. d’Agostino, P. Favia, Advanced Functional Materials 16 (2006), 1417–1424
IIL.C.
WORKSHOP NAZIONALE
Lopez, M.G. Buonomenna,AICIng - Messina, 12-14
E. Fontananova, Settembre
E. Drioli, 2007
P. Favia, R. d’Agostino, PLASMA PROCESSES & POLYMERS, 4 (2007) 326–333
New hydrophobic polymer for catalyst heterogenization:
Hyflon
Copolymers of tetrafluoroethylene (TFE) and 2,2,4trifluoro, 5trifluorometoxy 1,3 dioxide (TTD)
Perfluoro polymer
F F
Tg (AD60x) =110°C
F F Tg (AD80X)=135°C
O O
WCA=108° ±1
O F F F Thermal decomposition
temperature >400°C
CF3 n m
TTD TFE Highly transparent to light from
deep UV to near infrared
V. Arcella, P. Colaianna, P. Maccone, A. Sanguineti, A. Gordano, G.
Clarizia, E. Drioli, Journal of Membrane Science 163 (1999) 203–209.
High O2 solubility 0.33 cm3/(cm3bar)
V. Arcella, A. Gordano, P. Maccone, E. Drioli, Patent US Patent
deposited 24/05/2000, N°. 09/576,992
n = 0.85 for Hyflon AD80X and 0.6 for Hyflon AD60X,
respectively and m=1-n

(nBu4N)4W10O32 (TBAW10) heterogenised in Hyflon
Cross section Surface
Catalyst
aggregates
Poor dispersion of the catalyst!!!

Low affinity polymer-catalyst!!!
Possible solution: exchange of the counterion of W10 with a
fluorinated one (PFA) H C 3
H3C
CF2 CF2
F2C CH3
F2C
CF2 CF2
H3C CF2 F2C F2C CF2
F2C
F2C CF2 CF2 CF2 F2C CF2
F2C
F2C CF2 F2C CF2 CH3
CF2 CF2 F2C F2C CF2
F2C CF CF2 F2F2C CF
2 2
F2 F C CF2
2 F
C 2 C
H3C C C C F2 F2
N+
C
F2 F C C N+
2 F2 CH3 4- H3C
CH3 H3C
F2
N + N+
F
F2
C F2C CF2 F2 F
F2 C2 C C C C C2
C C C F2 F2 C
H3C F2 F2
F2C
F2C F2 C CH3
F2C CF2 F2C CF2 F2
F2C
F2C CF2 CF2 CF2 F2C CF2
F2C CF2 F2C
F2C
H3C F C
CF2 CF2 F2C CF2
2
CF2 F2C F2C CH
F2C CF2 3
CH3 F2C
CH3
PFA-W10
M. Carraro,
II WORKSHOP M. Gardan,
NAZIONALE G. Scorrano,
AICIng - Messina, E. Drioli,
12-14 Settembre E.
2007 Fontananova and M. Bonchio, Chem Comm. 43 (2006) 4533–4535
Membrane preparation by phase inversion
induced by solvent evaporation
Sol 1: PFA-W10 in Esafluoropropanol Mixing Sol 2: Sol 1 = 14.2 -8.5 (g/g):
(6.8 wt%)
→ homogeneous solution
Sol 2: Hyflon in Galden

(2.4 wt%)
Solvent
evaporation
Hy-PFAW10 dense membranes

Membrane Loading PFA-W10 (wt % ) Thickness (µm)
1 16.7 8±2
2 16.7 44±5
3 19.9 50±11
4 25.0 12±2
5 26.3 94±23
6 25.0 18±3
PFAW10 heterogenised in Hyflon (#2)
Cross section Surface
Good dispersion of the catalyst!!!

DR-UV spectra of the Hy-PFAW10 membrane
W10 in water (10-4 M)
W10 in membrane
CT band
characteristic of the
W10
The catalyst hetrogenized in membrane presents the CT band at 324 nm

Hyflon-PFA-W10 membranes were tested for the oxidation of
ethylbenzene
OOH OH O
4-
W10O32
+
λ > 345 nm, pO2=1 atm
T= 20°C 1 2 3
O2
Batch experiments for a

fast but incomplete
Membrane
Solution under screening of the catlytic
membranes
magnetic stirrer
hν

Ethylbenzene photooxidation by different catalytic
membranes
1300
1200 Hy-PFAW10
1100
1000
900
800
TON
700
600
500 Hy-TBAW10
400
300
200
100
0 PDVF-TBAW10
0 1 2 3 4
time (h)
Reaction conditions: ethylbenzene, 1.1 ml; pO2 1 atm; λ>345 nm; T=25°
Hy-PFAW10 50 µm, 0.18 µmol. Hy-TBAW10 76 µm, 0.2 mmol. PVDF-TBAW10 185 mm, 0.32
 Higher efficiency with the fluorinated W10 in Hyflon membranes
M. Carraro,
NAZIONALE AICIngG. Scorrano,
- Messina, E.Settembre
12-14 Drioli, E.2007
Fontananova and M. Bonchio, Chem Comm. 43 (2006) 4533–4535
Oxidation of ethylbenzene
Catalyst Solvent Cat. Products, mM TON

µmol (% 1:2:3)
a
TBAW10 CH3CN 0.20 64 351
(36: 32:32)
a
PFAW10 HFP 0.18 95 581
(56: 23:21)
PVDF-TBAW10 neat 0.32 23 78
(45: 23:32)
Hy-TBAW10 neat 0.20 81 443
(14: 66:20)
Hy-PFAW10 neat 0.18 196 1198
(25: 41:34)
1: peroxide, 2: alcohol , 3: keton. Reaction conditions: ethylbenzene, 1.1 ml; pO2,1 atm; l>345 nm;
T=25°C; 4 h irradiation time. Turnover number calculated as products (mol)/catalyst (mol). a pseudo-
neat conditions by addition of 20 µl of solvent
 Higher selectivity for the alchool with Hyflon membranes,

in particular with Hyflon-PFA-W10
M. Carraro,
NAZIONALE AICIngG. Scorrano,
- Messina, E.Settembre
12-14 Drioli, E.2007
Fontananova and M. Bonchio, Chem Comm. Chem Comm. 43 (2006) 4533–4535
W w − Wd
SW % = ⋅ 100
Wd
W w and W d are the weight of swollen and dry
membrane at 30±1°C
LogP is the logarithm of the partition coefficient

between n-octanol and water
The more hydrophobic polymeric material, i.e. Hyflon, has a higher affinity towards the
more hydrophobic (higher LogP value) liquid: ethylbenzene. On the contrary it has a low
affinity for the more hydrophilic liquid: 2-phenylethanol. These data can contribute to
explain the high reactivity of the catalyst heterogenized in Hyflon membranes (high
affinity for the reagent) and the high selectivity (low affinity for the product of interest,
i.e. the alcohol, which limits the possibility of over-oxidation of the same).
The better performance of the catalytic Hyflon membranes can depend also from
electronic effect of the perfluorinated polymer (electron attractor) on the catalyst
Moreover it is also well known that fluorinated environment can promote oxidation
reactions
Morphological analyses of Hyflon membrane containing the TBA-W10
clearly revealed the presence of catalyst aggregates
On the other hand, the use of a fluorinated cations linked to the

decatungstate anion (PFA-W10) improves the affinity between catalyst and
polymer and the catalyst can be thoroughly dispersed in the membrane.
Batch experiments of ethylbenzene (neat) oxidation were carried out with

Hyflon-PFA-W10 membranes. These systems showed super catalytic
performance (higher turnover number and better selectivity) compared to
homogeneous catalyst
Future work will be aimed in order to improve the membrane preparation

method and testing these new and promising catalytic membranes in a real
CMR operating with flow through both for neat oxidations of organic
compounds

Enzyme Membrane Reactors (EMR)
for Enantiomeric Production

Production of optically pure (S)-naproxen
Naproxen ((S)-2-(6-Methoxy-2-naphthyl) propionic acid) is an important

member of the family of 2-aryl propionic acid derivatives, which is widely
used as nonsteroidal anti-inflammatory drug.
(S)-naproxen is 28 times more active than the (R)-naproxen
Lipase from Candida rugosa preferentially hydrolyses (S)-naproxen ester
Reaction scheme
lipase
COOH
COOCH3 + COOCH3
CH3O H2O CH3O CH3O
(R,S)-naproxen methyl ester (S)-naproxen (R)-naproxen methyl ester

Emulsion&Enzyme
Loaded Membrane
Reactor
L ip a s e in o r g a n ic / w a t e r p h a s e
Lipase
H2 O
II WORKSHOP NAZIONALE AICIng - Messina, 12-14 Settembre 2007 Membrane

2.00E-01
1.60E-01
1.20E-01 S-Naproxen
R-Naproxen
mmol
8.00E-02
4.00E-02
0.00E+00
0 50 100 150 200 250
Time (h)
Behavior of S- and R-isomer as a function of time in
emulsion and enzyme immobilised in a two separate
phase enzyme-emulsion membrane reactor
4.E-02 1.0
Production µ(mol)
0.8
3.E-02
0.6
ee (-)
2.E-02
0.4
1.E-02
0.2
0.E+00 0.0
0 100 200 300
Time (h)
(
S)-
naproxen (
R)-
naproxen ee
Behaviour of stability and selectivity as a function of time for

experiments in semi-continuous mode (20% organic dispersed
phase, enzyme mainly present within the membrane pores).
 The production and selectivity of the enzyme-loaded
membrane reactor were affected by:
• the membrane cut-off, which affects the membrane
loading capacity;
• the amount of enzyme immobilized;
• the immobilization site, which affected O/W interface.
 Very small microemulsion were prepared by

membrane Emulsifier using UF membrane.
 O/W interface problem was overcome in E-EMR,

where native enantioselectivity was observed as
reaction occurred at the organic/water interface
Membrane technology in
petrochemical industry

Catalytic membrane reactors (CMRs): new opportunities
in the petrochemical field
Air Coke
Pure H 2
A OEA MF for Water Water
Byi Membrane Treatment MR FOR CO
r
Operation (coke removal) CLEAN-UP
GAS
COMPRESSION
H2
to
flares Membrane C4+
Feedstock CRACKING MCs for GS DISTILLATION
HOT SECTION Acid Gas
FURNACES Diution H2 CH4
Steam Removal RECOVERY
Acid gas
C2+ C3+
Condensed stream
MRs FOR Membrane GS Membrane GS

MCs for Water
ETHYLENE ETHYLENE/ PROPYLENE/
Purification
PRODUCTION ETHANE PROPANE
C3H6
C2H4
Ethane/Propane recycle
Reference plant:
800,000 t/a ethylene; ethylene yield = 31%; propylene yield = 18%; H2 yield = 1% (weight basis)
energy consumption = 30 GJ/t ethylene
P. Bernardo, A. Criscuoli, G. Clarizia, G. Barbieri, E. Drioli G. Fleres and M. Picciotti, Clean Technologies and Environmental Policy, (2003) , 6 (2004) 78–95.

Ethylene by catalytic processes
Cracking processes: energy and capital intensive.
Highly endothermic reactions, complex furnaces, coking.
Catalytic processes: reduced energy consumption

Ethane oxidative dehydrogenation (EOD)
Promising new way to produce ethylene
C2H6 + 1 / 2 Ο 2 → C2H 4 + Η 2 Ο
• Exothermic and not equilibrium limited
• Coking limited by O2; no need for steam
• Long-term stable operation
Significantly less investment expected!

Ethane oxidative dehydrogenation (EOD) with O2
controlled addition in a CMR
C2 H 6 + 1 / 2 Ο 2 → C2H 4 + Η 2 Ο
Air side
O2 separation from air
½ O2 + 2 e → O- 2-
Oxygen conducting membranes*: oxygen selective

O2- e- Catalytic membrane transport at high T (>700 °C)
C2H6 + O2- → C2H4 + H2O + 2 e-

Activated oxygen provided
Reaction side to the ethane side
*
Akin and Lin, J Membr Sci 209 (2002) 457.
• Improved safety (O2 and C2H6 separated)

• Better heat management
• Air can be fed to the MR
• Intensified
II WORKSHOP process
NAZIONALE AICIng (large
- Messina, 12-14 amounts
Settembre 2007 of inert N excluded)
Ethylene by EOD: Exergetic analysis
Conversion Selectivity
93 TR1 [TR1 Monolith reactor (Pt-Cu on MgO)] DOW:

88 Bharadwaj et al., US Patent No. 6,566,573 (2003).
80 80
75 74 70
63 TR2
[TR2 (Perovskite catalyst)] Donsì et al., J Catal 209
(2002) 51.
MR1
[MR1 (catalytic membrane)] Akin and Lin, J Membr
Sci 209 (2002) 457.
MR2
[MR2 (Perovskite catalytic membrane)] Rebeilleau et
al., Catal Today 104 (2005) 131
C efficiency , %
Exergy losses, kJ/mol ethylene 82
984
890 60
56
53
708
621
524
TR 1 TR 2 MR1 MR2
mol C C 2 H 4
TR1 TR1+GS TR2 MR1 MR2 C Efficiency = ⋅ 100
mol C C 2 H 6
P. Bernardo, G. Barbieri, E. Drioli,, An exergetic analysis of membrane unit operations integrated in the Ethylene Production cycle,
IICHERD
WORKSHOP
(2006), NAZIONALE
accepted. AICIng - Messina, 12-14 Settembre 2007
Reaction Metrics: Ethylene production by Ethane oxy-
dehydrogenation
CH +O →CH +HO kg INTOT
2 6 2 2
Mass Intensity =
4 2
kg Ethylene
Mass Intensity , kg IN/kg ethylene
8 ,6
8 ,2
5 ,8 Molar Intensi ty , m ol IN/m ol ethylene

11,5
2 ,9
7,9
5,5
4,3
TR 1 TR 2 MR1 MR2
TR 1 TR 2 MR1 MR2

dehydrogenation
Considering the air required to produce the O2 for
the reactor
Mass Intensity , kg IN/kg ethylene

8 ,6
8 ,2
8,2
5,5
TR 1 TR 2 MR1 MR2

dehydrogenation
C2H6 + O2 → C2H4 + H2O
mol CC 2 H 4
C Efficiency = ⋅ 100
mol CC 2 H 6
Formed
2 FC2H4
= ⋅ 100
Feed
2 FC2H6 C efficiency , %
= YC 2 H 6 82
60
56
Reaction Yield 53
TR 1 TR 2 MR1 MR2
Membrane technology in H2
production

Integrated Membrane Plant for H2 production by Water
Gas Shift Reaction
CO + H2O = CO2 + H2 ∆H0298 = - 41 kJ/mol
Steam Retentate
Pd
ra ne -A
H2
lloy
Reforming mb
Feed HDS ca
Me Me
mb
ra n
Sili e
WGS-MR
Fuel
Support
Retentate
Catalyst
Sweep SS-Shell Permeate

Membrane
Feed
WGSR in Silica MR
1
MR CO Conversion, -
MR @ 4 bar
TREC
SiO2 selective layer 1 µm; dpore <1 nm
MR @ 6 bar
Allumina intermediate layer 5 µm;

0.8
TR @ 1 bar
MR @ 3 bar
0.6
50
Before
reaction Before 200 250 300 350
reaction
Temperature, °C
Selectivity , -
After
25 After
reaction
reaction
The catalytic membrane reactor
overcomes the traditional
H2/CO H2/CO2 reactor equilibrium conversion
0 (TREC)
200 250 200 250 300
Temperature, °C
Brunetti A., Barbieri G., Drioli E., Lee K.-H., Sea B., Lee D.-W., “WGS Reaction in Membrane Reactor Using a Porous Stainless Steel Supported Silica
Membrane”. Chemical Engineering and Processing 46 (2007) 119–126

Integrated Membrane systems in
energy production
H2 H2 H2 H2
CO2 CO2 CO2 (low) CH4(low)
CO CO (low) CO (low)
H2O H2O CO -SELECTIVE H2O
HYDROCARBON 2
REFORMER WATER GAS METHANATOR FUEL CELL
MEMBRANE
SHIFTER
SEPARATOR
CO2
From U.S. Patent 6,579,331, ExxonMobil property
Membranes have a central role both in hydrogen

production (CMRs) and purification (GS) and in the
fuel cells as proton exchange membrane (PEM)!

Process intensification by miniaturization
Micro-reactors have demonstrated their clear advantages in catalysis

and micro-reaction engineering is rapidly developing
Advantages:
reduction of length scale
decreasing of heat and mass transfer distances decrease
realization of specific interfaces for multiphase flow
 smaller reagent volumes and correspondingly lower costs
Properties Micro-reactor Conventional reactor
internal volume 1-10 µl >> 1 ml
specific surface 10000 m2/m3 100 m2/m3
phase boundary surfaces for 5000 – 50000 m2/m3 100 m2/m3
liquid/ liquid mixtures
flows laminar character turbulent
Micro-membranes fabricated using standard
MEMS microfabrication processes enable new
applications because of their small size, fast thermal
response times and high efficiency

Pd-based micro-membranes for the Water Gas
Shift Reaction in a miniature fuel
processor for micro fuel cells
Schematic of the integrated microreactor

Karnik et al.Journal of microelectromechanical systems, 12 (2003) 93-100
An innovative potential application of membrane
technology in catalysis and in catalytic
membrane reactors, might be the possibility to
produce catalytic crystals with a well defined
size, size distribution and shape, by membrane
crystallization
Lysozyme Trypsin
Di Profio, G. Curcio, E. Drioli E. Membrane crystallization of lysozyme: kinetic aspects. Journal of Crystal Growth 2003; 257: 359-369.
Di Profio, G. Curcio, E. Drioli E. Trypsin crystallization by membrane-based techniques. Journal of Structural Biology 2005; 150: 41–49.

Driving force: vapour pressure difference
p ( c, T ) = p ( T ) a ( c, T )
0
temperature difference concentration difference
thermal membrane crystallization osmotic membrane crystallization
supersaturated solution
nucleation and crystal growth

The presence of the polymeric membrane
increases the probability of nucleation with
respect to other locations in the system
(heterogeneous nucleation)
Lysozyme crystals grown on PP microporous hydrophobic membrane

G. Di Profio, E. Curcio, E. Drioli, Journal of Crystal Growth, 257 (2003) 359-369

The value of the activation barrier is a crucial parameter to be controlled!
Polymeric materials can be used to promote and modulate the nucleation
process that often represents the limiting step in macromolecular
crystallization (Curcio, E. Fontananova, G. Di Profio, E. Drioli, Journal of Physical Chemistry B.; 110(25) (2006) 12438-12445)
1
PP
Hyflon
1 3 1 
∆G = ∆G  2 − 4 cos α + 4 cos α 
het hom 3
0.8
PDMS
(-)
0.6 PVDF(KF2800)
hom
PVDF(KF2800)-LiCl-2,5%
∆G /∆G
h et
PVDF(KF2800)-PVP-2,5%
0.4
PVDF(Kynar460)
PVDF(Kynar460)-PVP-2,5
0.2
0
0 50 100 150 200
contact a ngle (°)
Reduction in the free energy of the nucleation barrier due to heterogeneous nucleation as a function of the
lysozime solution (40 mg/mL; 2% wt NaCl) contact angle with some polymeric surface

Glycine polymorphs selection in membrane crystallization
γ - Polymorph α - Polymorph γ - Polymorph
Glycine dissolved in pure water: pH 6.1

2 4 6 8 1
0
1
2
pH
Static system Dynamic system

J/(mL/h) Polymorph v/µm⋅sec-1 Polymorph
6,9 x 10-3 γ 349,6 γ
13,8 x 10-3 γ 539,9 γ
18,4 x 10-3 α 709,1 α
20,7 x 10-3 α 899,9 α
23,0 x 10-3 α 989,9 α
27,9 x 10-3 α 1349,8 α
34,5 x 10-3 α 1845,5 α
G. Di Profio, S. Tucci, E. Curcio, E. Drioli, Cystal Growth & Design, in press

Selective polymorphs crystallization by controlling the rate of
achievement of supersaturation
Solvent Vapor
Low flow rate
Stripping Solution
Glycine Solution
Solvent Vapor
γ-Polymorph
Solvent Vapor
High flow rate

Solvent Vapor
α-Polymorph
The control of the rate for the achievement of supersaturation allows to switching
from a kinetically to a thermodynamically controlled nucleation stage thus
triggering the production of either a stable or metastable form .
G. Di Profio, S. Tucci, E. Curcio, E. Drioli, Cystal Growth & Design, in press

Conclusions
 Membrane technology has led to significant

innovations in processes and products over the last few
decades offering new opportunities in the design,
rationalization and optimization of innovative productions
in the frame of the process intensification strategy.
Catalytic membrane reactors are an interesting example

of integrated system in which molecular separation and
chemical conversions are combined in one step.
The heterogenization of catalysts in membrane is

particularly suitable for catalyst design at the atomic
and molecular level.

CMRs have been successfully applied in small scale
operations and can really to be considered as an
emerging technology.
However, for a large scale application, more research,
mainly related to optimization of membranes and modules
manufacturing and reactors design, is required.
A better valuation of this technology can be obtained by

introducing new appropriate metrics in the overall process
analysis

8th International Conference on Catalysis in Membrane
Reactors (ICCMR8 ), December 18-21, 2007
Kolkata, India
ICCMR8
The aim of the ICCMR8 conference is to provide a common platform for scientific
exchanges in the field of catalysis in membrane reactors. The ICCMR8 will resume the
tradition of cross-disciplinary and international cooperation set by the previous
conferences held in Lyon (1994), Moscow (1996), Copenhagen (1998), Zaragoza (2000),
Dalian (2002), Lahnstein (2004) and Cetraro (2005).
The conference will focus on futuristic technologies for clean

energy and green environment.
The technical programme of the conference will include invited
plenary and keynote lectures and contributed papers for oral and
poster presentations on all aspects of membrane reactors.

8th International Conference on Catalysis in Membrane
Reactors (ICCMR8 ), December 18-21, 2007
Kolkata, India
Conference Secretariat Conference Co-Chairman
Central Glass & Ceramic Research Prof. Enrico Drioli
Institute Director, National Research Council
(Council of Scientific & Industrial Institute on Membrane Technology
Research) (ITM-CNR), Italy
196, Raja S. C. Mullick Road Phone: +39-984 492039
PO – Jadavpur University Fax: +39-984 402103
Kolkata – 700 032, India Email : e.drioli@itm.cnr.it,
Phone : (0091) 33 24733469/96 e.drioli@unical.it
Extn. 3393
DID Line : (0091) 33 Conference Coordinator
24838079/8089 Dr. Sibdas Bandyopadhyay
FAX: (0091) 33 24730957 Deputy Director & Head
E-mail : iccmr8@cgcri.res.in Ceramic Membrane Division
Central Glass & Ceramic Research
Conference Chairman Institute
Dr. H. S. Maiti Kolkata-700 032, India
Director, Central Glass & Ceramic Phone: +91-33-24839248
Research Institute Fax : +91-33-24730957
Kolkata-700 032, India Email : sibdas@cgcri.res.in
Phone: +91-33-24735829
Fax : +91-33-24730957
Email : director@cgcri.res.in

Drioli

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PROGRESSES IN CATALYTIC

Enrico Drioli, Enrica Fontananova

Institute on Membrane Technology (ITM-CNR), c/o University of Calabria, Via

II WORKSHOP NAZIONALE AICIng - Messina, 12-14 Settembre 2007

Sustainable Chemistry Strategic Research Agenda 2005 (www.suschem.org)

The concept of sustainable growth calls for

Most of these requirements can be addressed by the

Among the different heterogenization strategies, the entrapping of

General advantages of an integrated membrane

II WORKSHOP NAZIONALE AICIng - Messina, 12-14 Settembre 2007

II WORKSHOP NAZIONALE AICIng - Messina, 12-14 Settembre 2007

Scanning electron microscopy (SEM) images of the cross

II WORKSHOP NAZIONALE AICIng - Messina, 12-14 Settembre 2007

II WORKSHOP NAZIONALE AICIng - Messina, 12-14 Settembre 2007

CONCENTRATE STRIPPING Accurel PP membrane

II WORKSHOP NAZIONALE AICIng - Messina, 12-14 Settembre 2007

II WORKSHOP NAZIONALE AICIng - Messina, 12-14 Settembre 2007

II WORKSHOP NAZIONALE AICIng - Messina, 12-14 Settembre 2007

In addition, the membrane can actively take part in the reactive

The selective transport properties of the membranes can be used

II WORKSHOP NAZIONALE AICIng - Messina, 12-14 Settembre 2007

S. Miachon,J.-A. Dalmon, Topics in Catalysis,29 (2004) 59-65

Extractor: The membrane is used to Distributor: The membrane controls Contactor:

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flat sheet membrane reactor;

tubular membrane reactor;

• retaining and recycling of the catalyst (retention in

The heterogenization of catalysts in membrane is

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Scheme of a membrane photoreactor with TiO2

The separation function often results in

E. Piera et al. Catalysis Today 67 (2001) 127–138

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L. van Dyk et al. Catal. Today 82 (2003) 167

(1) experimental data; (2) modelling; (3) thermodynamic equilibrium in a

V.V. Kharton et al. Catalysis Letters 99 (2005) 249-255

Both oxygen ions and electronic

Perovskite membranes are

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The products are thus pure

•In some cases, the membrane defines the reaction

Exclusion of polluting solvents and reducing the

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Separating the two immiscible

eliminates the need for a solvent

Incorporation of iron phthalocyanine (FePc) actively controls the concentration

Membrane separations often have the advantage of operating at

Under specific conditions, the heat dissipated in an exothermic

The downstream processing of the products can be substantially

An industrial example is the consortium of BP/Amoco,

The main problem is the development of reliable and

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 Manufacturing cost of the membranes and modules

 Limited membrane life time

 Considerable technical complexity of the process

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Computational strategies, theoretical,

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Resistance to aggressive High capital costs

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Due to the generally severe conditions of

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