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Membrane Separations

Microfiltration
Dan Libotean - Alessandro Patti
PhD students
Universitat Rovira i Virgili,
Tarragona, Catalunya
MF - UF - NF 2
Definition of a membrane
A membrane can be defined as a barrier (not necessarily solid)
that separates two phases as a selective wall to the mass transfer,
making the separation of the components in a mixture possible.

I
D
E
A
L

M
E
M
B
R
A
N
E

Permeate
Feed
Driving Force

R
E
A
L


M
E
M
B
R
A
N
E

Phase 1 Phase 2
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The growing use of MF
1. More attention paid to environmental problems linked to
drinking and non-drinking water

2. Increased demand for water (using currently available
sources more effectively)

3. Market power
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Membranes market in W. Europe
0
5
10
15
20
25
30
35
40
45
MF Dialysis UF RO Other
% of total 1997 consumption in Western Europe
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Demand in U.S.A., 2001
MF has been used more and more
to eliminate particles and micro
organisms in untreated water,
leading to a lower consumption
of disinfectant and to a lower
concentration of SPD (sub-
products of disinfections).

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Cumulative capacity of MF
0
10
20
30
40
50
'86-'88 '89-'90 '91-'92 '93-'94 '95-'96
Number of plants
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Driving Forces
A driving force can make the mass transfer through the membrane possible;
usually, the driving force can be a pressure difference (P), a concentration
difference (c), an electrical potential difference (E).
Membranes can be classified according their driving forces:
P

c

T

E

Microfiltration

Pervaporation

Thermo-osmosis

Electrodialysis

Ultrafiltration

Gas separation

Membrane distillation

Electro-osmosis

Nanofiltration

Vapour permeation



Membrane electrolysis

Reverse osmosis

Dialysis





Piezodialysis

Diffusion dialysis





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Pressure driven processes
MF
10-300 kPa
RO
0.5-1.5 MPa
NF
0.5-1.5 MPa
UF
50-500 kPa P=
Bacteria, parasites, particles
High molecular substances, viruses
Mid-size organic substances,
multiple charged ions
Low molecular substances, single charged ions
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Pore size of MF membranes
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Pores and pore geometries
Porous MF membranes consist of polymeric matrix in which pores
are present.
The existence of different pore geometries implies that different
mathematical models have been developed to describe transport
phenomena.
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Transport equations
The Hagen-Poiseuille and the Kozeny-Carman equations can be applied to
demonstrate the flow of water through membranes. The use of these equations
depends on the shapes and sizes of the pores.
1. Hagen-Poiseuille
x
P r
J
A
A
=
qt
c
8
2
cylindrical pores
J the solvent flux
AP pressure difference
Ax thickness of membrane
t tortuosity
q viscosity
r the pore radius
surface porosity
MF - UF - NF 12
Transport equations
2. Kozeny-Carman
x
P
S K
J
A
A
=
2
3
q
c
S surface area per unit volume
K Kozeny-Carman constant
(depends on the pore
geometry)
closely packed spheres
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How to prepare MF membranes
1. Stretching

Semycristalline polymers (PTFE, PE, PP)
if stretched perpendicular to the axis of
crystallite orientation, may fracture in such a
way as to make reproducible microchannels.
The porosity of these membranes is very high,
and values up to 90% can be obtained.

Stretched PTFE membrane
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How to prepare MF membranes
2. Track-etching

These membranes are now made by exposing
a thin polymer film to a collimated bearn of
radiation strong enough to break chemical
bonds in the polymer chains. The film is then
etched in a bath which selectively attacks the
damaged polymer.
Track-etched 0.4 m PC membrane
radiation source
polymer film
etching bath
membrane
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How to prepare MF membranes
3. Phase inversion (PI)

Chemical PI involves preparing a
concentrated solution of a polymer in a
solvent. The solution is spread into a thin
film, then precipitated through the slow
addition of a nonsolvent, usually water,
sometimes from the vapour phase.
In thermal PI a solution of polymer in poor
solvent is prepared at high temperatures.
After being transformed into its final shape,
a sudden drop in solution temperature causes
the polymer to precipitate. The solvent is
then washed out.
Chemical phase inversion
0.45 m PVDF membrane
MF - UF - NF 16
How to prepare MF membranes
4. Sintering

This method involves compressing a powder consisting of particles of
a given size and sintering at high temperatures.
The required temperature depends on the material used.

HEAT
pore
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Materials used
Synthetic polymeric membranes:

a) Hydrophobic
b) Hydrophilic
Ceramic membranes
PTFE, teflon
PVDF
PP
PE

Cellulose esters
PC
PSf/PES
PI/PEI
PA
PEEK
Alumina, Al
2
O
3

Zirconia, ZrO
2

Titania, TiO
2

Silicium Carbide, SiC
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Materials used
1. Polymeric MF membranes
Phase inversion
Stretching
Track-etching
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Materials used
2. Ceramic MF membranes
Anodec, anodic oxidation (surface) US Filter, sintering (cross section, upper part)
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Modules
A module is the simplest membrane element that can be used in
practice.
Module design must deal with the following issues:
2. Membrane integrity against
damage and leaks
3. Sufficient mass transfer to keep
polarization in control
4. Minimum waste of energy
5. Easy egress of
permeate
6. Permit the membrane
to be cleaned
1. Economy of manufacture
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Modules: tubular
Diameter tubular membrane assembly
Membranes diameter: >0.5 mm

Active layer: inside the tube

Flux velocity: high (up to 5 m/s)

Tube: reinforced with fiberglass
or stainless steel

Number of tubes: 4-18

Flux: one or more channels

Cleaning: easy

Surface area/volume: low
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Modules: hollow fiber
Hollow fiber module (inside-out)
Fibers: 300 5000 per module

Fibers diameter: <0.5 mm

Flux velocity: low (up to 2.5 m/s)

Feed: inside-out or outside-in

Surface area/volume: high

Pressure drop: low (up to 1 bar)

Maintenance: hard

Cleaning: poor
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Symmetric membranes
Symmetric ceramic membrane
(Al
2
O
3
)
surface
cross section
The cross section
shows a uniform
and regular structure
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Asymmetric membranes
Cross-section of
an asymmetric
PSf membrane.
Porous irregular layer
The active layer is supported
over the porous layer.
50/150 m
Porous with toplayer
Same material!
0.1/0.5 m
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Fouling and resistance
Fouling depends on: concentration, temperature
pH, molecular interactions
( )
c m
R R
P
J
+
A
=
q
Resistances-in-series model to describe the flux decline:
J: flow
P: pressure drop
: viscosity
R
m
: membrane
resistance
R
c
: cake resistance
time, t
f
l
u
x
,

J
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Fouling and resistance
m
a
p
R
R
R
g cp
R R
porous
membrane
gel layer
The build-up layer and the clogging
of the pores are referred to as a
fouling layer.
on polarizati ion concentrat R
f ormation layer gel R
membrane R
adsorption R
blocking pore R
cp
g
m
a
p
:
:
:
:
:
R
m
= R
m
(t=0)+R
a
+R
p
; R
c
=R
g
+R
cp
R
tot
=R
m
+R
c

MF - UF - NF 27
Methods to reduce fouling
1. Pretreatment of the feed solution
2. Membrane properties
3. Module and process conditions
4. Cleaning
a. Reducing concentration polarisation
a1. Increasing flux velocity
a2. Using low flux membranes
b. Turbulence promoters
a. Narrow pore size distribution
b. Hydrophilic membranes
a. Heat treatment
b. pH adjustament
c. Addition of complexing agents
d. Chlorination
e. Adsorption onto active carbon
f. Chemical clarification
a. Hydraulic cleaning
b. Mechanical cleaning
c. Chemical cleaning
d. Electric cleaning
Back-flushing
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Back-flushing
suspension
permeate
permeate
suspension
permeate
permeate
J
t
Restorable flux
with back-flushing
Irreversible fouling
starting points
P
t
Restorable pressure
with back-flushing
Irreversible fouling
starting points
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Dead end and cross-flow
To reduce fouling two process modes exist:
Feed
Permeate
Permeate
Feed Retentate
1. Dead-end 2. Cross-flow
Cake layer
MF - UF - NF 30
Available MF membranes
Pore size, m Module Material Membrane area per module, m
2
Producer
2, 3, 5 T C 0.02 7.1 US Filters
1.4 T C 0.005 7.4 US Filters
1 T C 0.09 10.0 CTI TechSep
0.45 T C 0.13 11.5 Ceramen
0.45 FH PSf 0.01 3.7 AG Technology
0.2 T C 0.02 7.1 US Filters
0.2 FH PP 2.0 Akzo
0.2 FH PP/PF 10.8 15 Memtec
0.1 T C 0.02 7.1 US Filters
0.1 FH PSf 0.01 3.7 AG Technology
MF - UF - NF 31
MF process applications
1. To replace four unit operations in the waste water
treatment process.
COAG/
FLOC
SED MIX
FILT
Disinfectants &
Coagulants
Waste
water
Water
Residual
disinfectant
MF
Pre
Filter
MF - UF - NF 32
MF process applications
2. To eliminate organic matter using MF after a pre-treatment
with coagulants
Water
Waste
water
Coagulants
MF
Pre
Filter
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MF process applications
Waste
water
3. MF as pre-treatment for RO or NF
Water
MF
Pre
Filter
RO
NF
Water
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Retentate: how will it be used?
1. Sent to a treatment plant
2. Discharged into a body of water
3. Sent to a storage facility
4. For ground applications
5. Recycled back to water source

MF - UF - NF 35
Some industrial applications
1. Waste-water treatment
2. Clarification of fruit juice, wine and beer
3. Ultrapure water in the semiconductor industry
4. Metal recovery as colloidal oxides or hydroxides
5. Cold sterilization of beverages and pharmaceuticals
6. Medical applications: transfusion filter set, purification of
surgical water
7. Continuous fermentation
8. Purification of condensed water at nuclear plants
9. Separation of oil-water emulsions

Membrane Separations
Ultrafiltration & Nanofiltration
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Membrane separation
SPECIES RANGE OF DIMENSIONS (NM)
Yeasts and fungi 1000-10000
Bacteria 300-10000
Oil emulsions 100-10000
Colloidal solids 100-1000
Viruses 30-300
Proteins, polysaccharides 2-10
Enzymes 2-5
Common antibiotics 0.6-1.2
Organic molecules 0.3-0.8
Inorganic ions 0.2-0.4
Water 0.2
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Membrane separation
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Membrane separation
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Membrane characterization
pore size
pore size distribution
free volume
crystalinity
Membrane properties Membrane separation
properties
rejection
separation factor
enrichment factor

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Membrane characterization
Membranes
porous

nonporous



Process Driving force Membrane Pore Separation principle
Microfiltration pressure difference
(0.1 - 1 bar)
macropore filtration
Ultrafiltration pressure difference
(0.5 10 bar)
mesopore filtration
Nanofiltration pressure difference
(5 20 bar)
micropore filtration/
electrostatic interaction/
solution-diffusion
macropore |>50nm
mesopore 2nm<|<50nm
micropore |<2nm
| = pore diameter
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The characterization of porous
membranes
1. shape of the pore (pore geometry)
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1. Pore geometries
x
P
8
r
J
2

=
Hagen-Poiseuille equation
J the solvent flux
AP pressure difference
Ax thickness of membrane
t tortuosity
q viscosity
r the pore radius
c the surface porosity
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1. Pore geometries
( )
x
P
1 S K

J
2
2
3


=
Kozeny-Carman relationship
S the internal surface area
K Kozeny-Carman constant
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1. Pore geometries
top layer thickness
0.1-1m
sub layer thickness
50-150m
The flux is inversely proportional
to the thickness.
commercial
interest
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The characterization of porous
membranes
2. pore size distribution
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The characterization of porous
membranes
3. surface porosity
m
2
p
A
r
n

=
r the pore radius
n
p
number of pores
A
m
membrane area
Microfiltration membranes: c ~ 5-70%
Ultrafiltration membranes: c ~ 0.1-1%
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The characterization of porous
membranes
Characterization methods:
structure-related parameters
(pore size, pore size distribution, top layer thickness,
surface porosity)
permeation-related parameters
(actual separation parameters using solutes that are more or
less retained by the membranes - cut-off measurements
*
)
* cut-off is defined as the molecular weight which is 90% rejected by the membrane

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The characterization of porous
membranes
Characterization methods
Microfiltration Ultrafiltration
scanning electron microscopy gas adsorption-desorption
bubble-point method thermoporometry
mercury intrusion porometry permporometry
permeation measurements liquid displacement
rejection measurement
transmission electron microscopy
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Ultrafiltration
... separation of one component of a solution from another component by
means of pressure and flow exerted on a semipermeable membrane, with
membrane pore sizes ranging from 0.05 m to 1nm.

is used begining with years 30
the operating pressure 0.1-5 bar
typically used to retain macromolecules and colloids
the lower limit are solutes with molecular weights of a few thousands
Daltons (1Dalton1.66
.
10
-24
g)
average flux around 50-200 GFD (~ 80-340 l/m
2.
h), at an operating
pressure of 50 psig (~ 3,5bar)
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Ultrafiltration
Membranes used:
polymeric
- polysulfone/poly(ether sulfone)/sulfonated polysulfone
- poly(vinylidene fluoride)
- polyacrilonitrile
- cellulosics
- polyimide/poly(ether imide)
- aliphatic polyamides
- polyetheretherketone
ceramic
- alumina (Al
2
O
3
)
- zirconia (ZrO
2
)

MF - UF - NF 52
Ultrafiltration
Process performance do not depend only to the intrinsic
membrane properties, but also to the occurence of
different phenomena:

concentration polarization
fouling
adsorption
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Concentration polarization
The concentration of removed species is higher near the
membrane surface than it is in the bulk of the stream.
Result:
a boundary layer of substantially high concentration
permeate of inferior quality
Resolution:
high fluid velocities are maintaned along the membrane
surface
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Fouling
Build-up of impurities in the membrane that can keep it
from functioning properly.
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Ultrafiltration
Crossflow Mode
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Ultrafiltration
Dead End Mode
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Cleaning
Cleaning in Backwash mode
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Cleaning
Cleaning in Forward Flush mode
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Adsorption
The main factor enhancing this phenomenon is hydrophobic
interaction between the surface of the membrane and substance
molecules.
Hydrophobic groups are more prone to adsorbtion than
hydrophilic groups
Hydrophobic Hydrophilic
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Adsorption
The number of molecules adsorbed on the surface, can be
reduced by modifying hydrophobic membrane surface to
hydrophylic membrane surface.





It is also easy to clean a hydrophilic membrane.
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Ultrafiltration
Applications:
food and dairy industry (the concentration of milk and cheese making, the
recovery of whey proteins, the recovery of potato starch and proteins, the
concentration of egg products, the clarification of fruit juices and alcoholic
beverages)
pharmaceutical industry (enzymes, antibiotics, pyrogens)
textile industry
chemical industry
metallurgy (oil-water emulsions, electropaint recovery)
paper industry
leather industry
sub layers in composite mebranes for nanofiltration, reverse osmosis, gas
separation or prevaporation
MF - UF - NF 62
Ultrafiltration
Factors affecting the performance:
flow across the membrane surface
high flow velocity high permeate rate
operating pressure
due to increased fouling and compaction, pressures
rarely exceed 100 psig (1 psig=0.068948 bar)
operating temperature
high temperature high permeate rate

MF - UF - NF 63
Nanofiltration
...used when low molecular weight solutes as inorganic salts or small organic
molecules (glucose, sucrose) have to be separated.

pore size < 2 nm
the operating pressure 10-20 bar
material directly influences the separation
nanofiltration membranes are considered intermediate between porous
and nonporous membranes
most of the nanofiltration membranes are charged
two models for the separation mechanism
1. permeation through a micropore
2. the solution-diffusion into the membrane matrix
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1. The permeation mechanism
...is explained in terms of charge and/or size effects.

uncharged solutes sieving
charged components Donnan exclusion mechanism

m
B
B
B
m
A
A
A
m
Don
a
a
ln
F z
RT
a
a
ln
F z
RT
= = =
+ - the electrical potential z - the valence
R - the gas constant F - the Faraday constant
T - the temperature a - the activity of the solutes
m refers to the membrane phase, while A and B are the components in the
solution
The Donnan potential
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2. The solution-diffusion mechanism
membrane behaves as a nonporous diffusion barrier

each component dissolves in the membrane in accordance
with an equilibrium distribution law

each component diffuses through the membrane by a
diffusion mechanism in response to the concentration and
pressure differences


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Nanofiltration
Membranes for which the Donnan exclusion
seems to play an important role
negatively charged membrane pozitively charged membrane
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Nanofiltration
Membranes for which the diffusion seems to play
an important role
nonporous membrane
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Nanofiltration
Membranes used:
asymmetric structure: top layer <1m, sub layer ~50-150m
asymmetric membranes (prepared by phase inversion techniques)
- cellulose esters
pH range 5-7, temperature < 30
o
C (for avoiding the hydrolysis
of the polymer)
- polyamides
- polybenzimidazoles, polybenzimidazolones, polyamidehydrazide, polyimides
composite membranes
- first stage is preparing the porous sub layer
- placing a thin dense layer on the top of the sub layer: dip coating, in-situ
polymerization, interfacial polymerization, plasma polymerization

MF - UF - NF 69
Nanofiltration
Applications:

desalination of brackish and seawater to produce potable water

producing ultrapure water for the semiconductor industry

retention of bivalent ions such as Ca
2+
, CO
3
2-

retention of micropollutants and microsolutes such as: herbicides,
insecticides, pesticides, dyes, sugar