membrane

Dr.rer.nat. Heru Susanto

PRESSURE DRIVEN MEMBRANE

PROCESS

1. Concentrate
2. Purify a dilute (aqueous or non aqueous)

1. Stucture membrane
2. Pore size
3. Pore size distribution

PORE SIZE

MICROFILTRATION
Is the membrane process which most closely resembles conventional coarse
filtration.
Pore size:

Suitable for retaining suspensions and emulsions

The Darcys Law :

J A P

Where the permeability constant A contains structural factors

such as the porosity and pore size (pore size distribution)

For laminar convective flows through a porous systems :

r 2 P
J
8 x

Where r is the pore radius, x is the membrane thickness,

is he dynamic viscosity and
is the tortuosity factor ehich
is unity in the case of cylindrical pores.

May be prepared from organic materials (polymers) and inorganic (ceramics,

metals, glasses)
Various techniques can be employed :
1. Sintering

2. Streching

3. Track - etching

4. Phase inversion

Frequently, inorganic membranes are used instead of polymeric membranes

because of their outstanding chemical and thermal resistances.

Process

Porosity

Pore size distribution

Sintering

Low / medium

Narrow / wide

Stretching

Medium / high

Narrow / wide

Track-etching

Low

Narrow

Phase inversion

High

Narrow / wide

These various techniques allow to prepare microfiltration membranes from virtually all
kinds of materials of which polymers and ceramics are the most important.
HYDROPHOBIC POLYMERIC MEMBRANES

HYDROPHILIC POLYMERIC MEMBRANES

CERAMIC MEMBRANES

Polytetrafluoroethylene (PTFE)
Poly(vinylidene fluoride) (PVDF)
Polyproylene (PP)
Polyethylene (PE)

Cellulase esters
Polycarbonate (PC)
Polysulfone / poly(ether sulfone)
(PS/PES)
Aliphatic polyamide (PA)
Polyetheretherketone (PEEK)

Alumina (Al2O3)
Zirconia (ZrO2)
Titania (TiO2)
Silicium carbide (SiC)

FLUX
DECLINE
NEED
NEED

DEAD END FILTRATION

The feed flow is perpendicular to the membrane

surface, so that the retained particles accumulate
and form a type of a cake layer at the membrane
surface. The thickness of the cake increases with
filtration times and consequently the permeation rate
decreases with increasing cake layer thickness

CROSS FLOW FILTRATION

The feed flow is along the membrane surface, so that

part of the retained solutes accumulate

1. Cold sterilisation of beverages and pharmaceutical

2. Cell harvesting
3. Clarification of fruit juice, wine and beer
4. Ultrapure water in the semiconductor industry
5. Metal recovery as colloidal oxides or hydroxides
6. Waste-water treatment
7. Continuous fermentation
8. Separation of oil-water emulsions
9. Dehydration of latices

Membranes :

(a)Symmetric porous

Thickness :

10 150 um

Pore sizes :

0,05 10 um

Driving force :

Pressure (< 2 bar)

Separation principles :

Sieving mechanism

Membrane material :

Polymeric, and ceramic

Main application :

Analytical applications
Sterilisation (food, pharmaceutical)
Ultrapure water (semiconductor)

ULTRAFILTRATION
Is a membrane process whose nature lies between nanofiltration and
microfiltration
Pore size:
UF is typically used to retain macromolecules and colloids from a solution. UF and
MF can oth be consider as porous membrane where rejection is determined by the
size and shape of the solutes relatives to the pore size in he membrane and where
the transport of solvent is directly proportional to the applied pressure.
In fact both UF and MF involve similar membrane processes based on the same
separation principle. However, an important difference is that UF membrane have
an asymmetric structure with a much denser top layer (small pore size and lower
surface porosity) and consequently a much higher hydrodynamic resistance.

Most of UF membrane used commercially these day are

prepared from :
POLYMERIC MEMBRANES

Polytetrafluoroethylene (PTFE)
Poly(vinylidene fluoride) (PVDF)
Polyacrylonitrile
Polyimide
Polyetheretherketone
Aliphatic polyamides
Cellulosics

INORGANIC (CERAMIC)

Alumina (Al2O3)
Zirconia (ZrO2)

1 FOOD AND DAIRY INDUSTRY

Recovery of whey proteins

Recovery of potato starch and proteins
Concentration of egg product
Clarification of fruit juices and alcoholic
beverages

2 PHARMACEUTICAL INDUSTRY
3 METALLURGY
4 CHEMICAL INDUSTRY
5 TEXTILE INDUSTRY
6 LEATHER INDUSTRY
7 PAPER INDUSTRY

Membranes :

Asymmetric porous

Thickness :

150 um (or monolithic for some ceramics)

Pore sizes :

1 100 nm

Driving force :

Pressure (1-10 bar)

Separation principles :

Sieving mechanism

Membrane material :

Polymeric (PS, Polyacrilonitrile)

Ceramic (zirconium oxide, aluminium oxide)

Main application :

Dairy (milk, whey, cheese making)

Food (potato starch and protein)
Metallurgy (oil-water emulsion, electropaint recovery)
Textile (indigo)
Pharmaceutical (enzymes, antibiotics, pyrogens)
Automotive (electropaint)
Water treatment

REVERSE OSMOSIS AND

NANOFILTRATION
RO and NF are used when low molecular weight solutes such as inorganic salts or small
organic mocules such as glucose, and sucrose have to be separated from solvent.

The membrane is permeable to

the solvent (water) but not to the
solute (salt). In order to allow
water to pass through the
membrane, the applied pressure
must be higher than the osmotic
pressure.
Membrane
Complete barrier to dissolved
salt

Salt solution
Pure water

The pressure used in reverse osmosis range from 20 100 bar and ini nanofiltration
from about 10 20 bar, which much higher than those used in ultrafitration
Both process are considered as one process since the basic principles are the same.
NF membranes are the same as RO membranes only the network structure is more
open.
Comparison of retention characteristic between nanofiltration (NF) and reverswe
osmosis (RO) are listened :
Solute

RO

NF

Monovalent ions (Na, K, Cl, NO3)

>98%

<50%

Bivalent ions (Ca, Mg, SO4, CO3)

>99%

>90%

Bacteria and virusses

>99%

<99%

Microsolutes (Mw >100)

>90%

>50%

Microsolutes (Mw < 100)

0-99%

0-50%

The flux is approximately inversely proportional

to the membrane thickness and for this reason
most reverse osmosis membranes have an
asymmetric structure with a thin dense toplayer
(thickness 1um) supported by a porous
sublayer (thickness 50 150 um), the resistance
towards transport being determined mainly by
distinguished: (i) integral asymmetric
membranes, and (ii) composite membranes.

Both toplayer and sublayer consists of the same material. These membrane are
prepare by phase inversion technique. The polymeric material from which the
membrane it to be prepared is soluble in a solvent or a solvent mixture.

An important class of
asymmetric
membranes are :

cellulose esters. This materials are very suitable for

desalination because of their high permeability towards
water in combination with a (very) low solubility towards
salt.

Aromatic pides. These material also show high

selectivities towards salts but their water flux is somewhat
lower.

Polybenzimidazoles, polybenzimidazolones,
polyamidedehydrazide, and polyimides

The second type of structure frequently used in RO while most of the NF membrane are
in fact composite membrane.
In such membranes the top layer and sublayer are composed of different polymeric
materials so that each layer can be optimised separately.
The first stage is the are preparation of the porous sublayer. Important criteria forthis
sublayer are surface porosity and pore size distribution and asymmetric ultrafiltration
membranes are often used. Different methods have been employed for placing a thin
dense layer on top of this sublayer :
dip coating
In-situ polymerisation
Interfacial polymerisation
Plasma polymerisation

RO

purification water, desalination of brackish and seawater to produce potable water

Production of ultrapure water for the semiconductor industry
Concentration step particularly in the food industry ( concentration of fruit juice)
Galvanis industry (concentration of waste stream)
Dairy industry (concentration of milk to prior cheese manufacture)

NF
When a high retention is required for NaCl with high feed concentrations reverse
osmosis reverse osmosis is the preferred process. In other cases with much
lower concentrations, divalent ions and micro solutes with molecular weight
nanofiltration is the preferred process. Since the water permeability is (much)
higher in nanofiltration the capital cost for a certain application will be lower.

Membranes :

Composite

Thickness :

Sublayer : 150 um
Toplayer : 1 um

Pore sizes :

< 2 nm

Driving force :

Pressure (10 25 bar)

Separation principles :

Solution diffusion

Membrane material :

Polyamide (interfacial polymerisation)

Main application :

Desalination of brackish and seawater

Removal of micropllutents
Water softening
Wastewater treatment
Retention of dyes (textile industry)

Membranes :

Asymmetric or composite

Thickness :

Sublayer : 100 um
Toplayer : 1 um

Pore sizes :

< 2 nm

Driving force :

Pressure : brackish water (15 25 bar)

seawater (40 80 bar)

Separation principles :

Solution-diffusion

Membrane material :

Cellulose triacetate, aromatic polyamide, polyamide

and poly(ether urea) (interfacial polymerisation)

Main application :

Desalination of brackish and seawater

Production of ultrapure water (electronic industry)
Concentration of food juice and sugars (food
industry) and the concentration of milk dairy
industry)

Microfiltration

Ultrafiltration

Nanofiltration / reverse
osmosis

Separation of particles

Separation of
macromolecules (bacteris,
yeasts)

Separation of low MW solute

(salt, glucose, lactose,
micropollutent)

Osmotic pressure negligible

Osmotic pressure negligible

Osmotic pressure high

(1-25 bar)

Applied pressure low (< 2bar) Applied pressure low (1-10

bar)

Applied pressure high (10-60

bar)

Symmetric structure
Assymetric structure

Asymmetric structure

Asymmetric structure

Thickness of separating layer: Thickness of actual

Symmetric structure :
separating layer : 0,1-1,0 um
10-150 um
Assymetric structure :1 um

Thickness of actual
separating layer : 0,1 1 um

Separation based on particle

size

Separation based on
differences in solubility and
diffusivity

Separation based on particle

size