Membrane Separations

Microfiltration
Dan Libotean - Alessandro Patti
PhD students
Universitat Rovira i Virgili,
Tarragona, Catalunya
 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.

IDEAL
REAL MEMBRANE
Permeate Feed

Driving Force

Phase 2 Phase 1

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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
45
40
35
30
25
20
15
10
5
0
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
50

40

30

20

10

0
'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 UF NF RO
∆P= 10-300 kPa 50-500 kPa 0.5-1.5 MPa 0.5-1.5 MPa

Bacteria, parasites, Mid-size organic substances,

particles
HighLow
molecular
molecular
substances,
substances,
viruses
single charged ions
multiple 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

J – the solvent flux

  r P 2
P – pressure difference
J
8 x
x – thickness of membrane cylindrical pores
- tortuosity
 - viscosity
r – the pore radius
ε – surface porosity

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 Transport equations
2. Kozeny-Carman

 P 3
J
KS x
2
closely packed spheres

S – surface area per unit volume

K – Kozeny-Carman constant
(depends on the pore
geometry)

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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.

radiation source
membrane Track-etched 0.4 μm PC membrane

polymer film

etching bath
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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, Chemical phase inversion
a sudden drop in solution temperature causes 0.45 μm PVDF membrane
the polymer to precipitate. The solvent is
then washed out.
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 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
PTFE, teflon
Synthetic polymeric membranes: PVDF
PP
a) Hydrophobic PE
b) Hydrophilic
Cellulose esters
PC
Ceramic membranes PSf/PES
PI/PEI
Alumina, Al2O3 PA
Zirconia, ZrO2 PEEK
Titania, TiO2
Silicium Carbide, SiC
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 Materials used
1. Polymeric MF membranes

Stretching
Phase inversion

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:
1. Economy of manufacture 4. Minimum waste of energy

2. Membrane integrity against 5. Easy egress of

damage and leaks permeate

3. Sufficient mass transfer to keep 6. Permit the membrane

polarization in control to be cleaned

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 Modules: tubular
• 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 Diameter tubular membrane assembly
• Surface area/volume: low
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 Modules: hollow fiber
• 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 Hollow fiber module (inside-out)

• Cleaning: poor

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 Symmetric membranes

The cross section

shows a uniform
and regular structure

cross section surface

Symmetric ceramic membrane
(Al2O3)
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Asymmetric membranes
0.1/0.5 μm
Same material! 50/150 μm

Porous
Porousirregular
with toplayer
layer

The active layer is supported

over the porous layer.

Cross-section of
an asymmetric
PSf membrane.

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 Fouling and resistance
Fouling depends on: concentration, temperature
pH, molecular interactions

Resistances-in-series model to describe the flux decline:

J: flow
ΔP: pressure drop

flux, J
P η: viscosity
J Rm: membrane

 Rm  Rc  resistance
Rc: cake resistance
time, t

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 Fouling and resistance
gel layer porous
The build-up layer and the clogging membrane
of the pores are referred to as a
fouling layer.
R p : pore - blocking Rp
Ra : adsorption
Rm : membrane
Ra
Rg : gel layer formation Rm
Rcp : concentration polarizati on
Rm= Rm(t=0)+Ra+Rp; Rc=Rg+Rcp
Rtot=Rm+Rc
Rcp Rg
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 Methods to reduce fouling

Back-flushing
1. Pretreatment of the feed solution

2. Membrane properties
a.
a.
a.
a. Hydraulic
Heat
Reducing
Narrow cleaning
treatment
concentration
pore polarisation
size distribution
b.
b.
b. Mechanical
pH
a1.adjustament
Increasing
Hydrophilic cleaning
flux velocity
membranes
3. Module and process conditions c.c. Chemical
a2. Usingofcleaning
Addition complexing
low agents
flux membranes
d.
d.
b. Electric cleaning
Chlorination
Turbulence promoters
e. Adsorption onto active carbon
4. Cleaning f. Chemical clarification

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 Back-flushing
permeate

suspension
permeate

suspension
permeate
Restorable pressure
ΔP
J with back-flushing
Irreversible fouling
Restorable flux permeate
with back-flushing
Irreversible fouling
starting
starting pointspoints
t
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 Dead end and cross-flow
To reduce fouling two process modes exist:

1. Dead-end 2. Cross-flow

Feed Feed Retentate

Cake layer Permeate

Permeate

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 Available MF membranes
Pore size, μm Module Material Membrane area per module, m2 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

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 MF process applications
1. To replace four unit operations in the waste water
treatment process.

Waste COAG/
water MIX SED FILT
Pre FLOC MF
Filter Water
Disinfectants & Residual
Coagulants disinfectant

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 MF process applications
2. To eliminate organic matter using MF after a pre-treatment
with coagulants

Waste
water Pre MF
Filter Water
Coagulants

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 MF process applications
3. MF as pre-treatment for RO or NF

Water
RO
Waste
water Pre
MF
Filter

Water
NF

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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

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 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

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 Membrane Separations

Ultrafiltration & Nanofiltration

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
Membrane properties Membrane separation
properties

pore size rejection

pore size distribution separation factor
free volume enrichment factor
crystalinity

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 Membrane characterization
Membranes
 porous macropore f>50nm
mesopore 2nm<f<50nm
micropore f<2nm
 nonporous f = pore diameter

Process Driving force Membrane Pore Separation principle

Microfiltration pressure difference macropore filtration
(0.1 - 1 bar)
Ultrafiltration pressure difference mesopore filtration
(0.5 – 10 bar)
Nanofiltration pressure difference micropore filtration/
(5 – 20 bar) electrostatic interaction/
solution-diffusion

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 The characterization of porous
membranes
1. shape of the pore (pore geometry)

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 1. Pore geometries

J – the solvent flux

P – pressure difference
x – thickness of membrane
Hagen-Poiseuille equation
 - tortuosity
 - viscosity
ε  r ΔP2 r – the pore radius
J   – the surface porosity
8  η  τ Δx
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 1. Pore geometries

S – the internal surface area

K – Kozeny-Carman constant

Kozeny-Carman relationship

ε 3
ΔP
J 
K  η  S  1 - ε  Δx
2 2

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 1. Pore geometries
top layer thickness
0.1-1mm

sub layer thickness

50-150mm

The flux is inversely proportional commercial

to the thickness. 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
r – the pore radius
πr 2
ε  np  np – number of pores
Am Am – membrane area

Microfiltration membranes:   5-70%

Ultrafiltration membranes:   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 mm 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 (1Dalton1.66.10-24g)
average flux around 50-200 GFD (~ 80-340 l/m2.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 (Al2O3)
- zirconia (ZrO2)
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 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
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 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

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 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
The Donnan potential
RT a A RT a B
Ψ Don  Ψ -Ψ 
m
ln m  ln m
z A F a A z BF a B
Y - 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
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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 <1mm, sub layer ~50-150mm
asymmetric membranes (prepared by phase inversion techniques)
- cellulose esters
pH range 5-7, temperature < 30oC (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
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 Nanofiltration
Applications:

desalination of brackish and seawater to produce potable water

producing ultrapure water for the semiconductor industry

retention of bivalent ions such as Ca2+, CO32-

retention of micropollutants and microsolutes such as: herbicides,

insecticides, pesticides, dyes, sugar

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