Membrane Separations

- Pressure-driven membrane processes:

P=

MF
0.11-0.3 MPa

UF
0.15-0.5 MPa

NF
0.5-1.5 MPa

Low molecular substances,

single charged ions
Mid-size organic substances,
multiple charged ions

High molecular substances, viruses

Bacteria, parasites, particles

RO
0.5-1.5 MPa

Membrane Separations

- Pressure-driven membrane processes:

Microfiltration (MF)

Ultrafiltration (UF)
Nanofiltration (NF)
Reverse Osmosis (RO)

Membrane Separations

Microfiltration (MF)
- First commercially developed (1930).
- Very popular and used (sharing with RO).
- Pore size between 0.05 and 10 m (0.45 m).
- Rejects particles between 0.2 and 10 m.
- Bacteria, fragmented cells or colloids.
- MW 300000.
- Driving force: pressure difference.
- Low operation pressure: 0.2 to 3.5 bar.
- Typical flux: > 200 L m-2 h-1.

Membrane Separations

Microfiltration (MF)
- Separation given by size exclusion mechanism.
- Flux: Hagen-Poiseuille or Kozeny-Carman.
- Hydrophobic membranes.
- Occurrence of adsorption
effects between the
membrane surface and the
rejected species.
- Important fouling and pore plugging.
- Dead-end filtration and cleaning.

Repels water
Absorbs oil
Fouls with free oils
Lower flux
Difficult to clean

Repels oils
Absorbs water
Not fouled by free oils
Higher flux
Easier to clean

Membrane Separations

Microfiltration (MF)
- Polymeric membranes made of a wide variety of
polymers or polymers blends:
PTFE, PVDF, PP, PS, CA, CN, CTA, PE, PC,
PEST, PI, Nylon ...
CA, CN o CTA are preferred due to their
hydrophilicity preventing fouling.
- Also ceramic, basically -Al2O3, because of
their easy cleaning, long lifetime and available
sterilisation

Membrane Separations

Microfiltration (MF)
- Applications:
Bioengineering, food industry, wastewater
treatment. Examples:
High organic loading water treatment.
Cutting oil emulsion treatment.
Juice, wine or beer clarification.
Fermentation product separation.
Recovering of precipitated metals.

Membrane Separations

Ultrafiltration (UF)
- Microporous membranes (?).
- Pore size between 1 and 50 nm.
- Rejects particles from 15 to 2000 .
- Polymers, proteins and colloids.
- Molecular weight from 5000 to 5106 Daltons*.
- Driving force: pressure difference.
- Moderate operating pressure: 1 to 10 bar.
- Typical flux: 5-200 L m-2 h-1.
* 1 Dalton 1.6610-24 g

Membrane Separations

Ultrafiltration (UF)
- Characteristic parameter: Molecular Weight Cut-Off
MWCO is the minimum MW the rejection being of
90%*.
Relation between MWCO and the pore size for UF
membranes.
Pore Diameter
MWCO (Daltons)

P

nm

1000000

0.1

100

1000

500000

0.02

20

200

100000

0.01

10

100

50000

0.04

40

10000

0.0025

2.5

25

5000

0.0015

1.5

15

* To design, the membrane MWCO must be taken about the half of lower MW species
to be retained.

Membrane Separations

Ultrafiltration (UF)
- Polymeric membranes made of a wide variety of
polymers or polymers blends:
CA, PS, PES, PAN, PVDF, PI
CA: low fouling, high flux.
PS: chemically stable.
PES: available sterilisation.
PI: solvent resistant, only tubular.
- Also ceramics, mainly made of and -Al2O3.
Easy cleaning, long lifetime and available
sterilisation.

Membrane Separations

Ultrafiltration (UF)
- Separation mostly given by size exclusion.
- In low pore size membrane, some solutiondiffusion phenomena are present (typical for
RO).
- Performance affected by pressure, temperature,
stirring, concentration and ionic environment.
- Significant fouling and pore plugging.
- Cross-flow filtration and cleaning.
- Any configuration.

Membrane Separations

Ultrafiltration (UF)
- Applications:
Food industry, wastewater treatment.
Also potentially useful paper pulping
or textile industry. Some Examples:
COD reduction in wastewater.
Treatment of cutting-oil emulsion.
Metal finishing water treatment.
Treatment of black-liquor from paper pulping.
Protein recovery from blood plasma.
Egg white concentration.
Serum recovery from milk.

Membrane Separations

Ultrafiltration (UF)
- Serum recovery from cheese production. The cheese production is a
biochemical process followed by precipitation (of the solid cheese). The
remaining solution contains, in addition to the water, the most part of the initial
lactose, proteins, vitamines and minerals.
Feed

Concentrate

UF

UF

UF

Permeate

Continuous UF process for recovering of lactoserum.

Membrane Separations

Nanofiltration (NF)
- Recent definition. Separation range between UF
and RO.
- Typical pore size 2 nm.
- Efficiently rejects, due to electrostatic interactions,
charged particles, mainly multivalent ions.
- Rejects non charged molecules (MW > 200 g/mol)
by molecular sieving.
- Driving force: pressure difference.
- Moderate Pressure: 15 bar.
- Typical flux: 20-80 L m-2 h-1.

Membrane Separations

Nanofiltration (NF)
- Polymeric membranes (CA, PA, PVA):
- Configuration of spiral-wound module.
- Applications: Water pretreatment, food industry,
recovery of metals.
Removal of coloured organic compounds and humic
acids (precursors of the trihalometanes).
Water softening (removal of multivalent ions).

- Still looking for applications. Potentially when

UF does not give sufficient rejection and RO is not
economical.

Membrane Separations

Nanofiltration (NF)
- In 1996 there were 150 plants all around the world
for drinking water by means of NF, with an overall
capacity of 600000 m3/day.
(compare with 3000000 m3/day capacity of plants
based on RO)
- For instance, it must be noted that NF is the
technology selected to obtain drinking water in
Florida (USA).

Membrane Separations

Reverse Osmosis (RO) [Hyperfiltration]

- Developed in the 50s.
- Very popular and used.
- Ions and low molecular weight species (MW < 200).
- Pore size < 1 nm.
- Water molecules freely pass (0.2 nm).
- Driving force: pressure difference.
- Operating pressure between 10-25 (brackish) and
40-80 bar (seawater).
- Average flux: 5-40 L m-2 h-1.

Membrane Separations

Reverse Osmosis (RO)

Membrane Separations

Reverse Osmosis (RO)

(1)

(2)

- Why does water cross the membrane ?

i = io (T )+ vi P + R T ln ( i ci )
(w1) = (w2)

v(w1) P (1) + R T ln a (w1) = v(w2) P ( 2) + R T ln a (w2)

membrane

v w P (1) P ( 2) = R T ln a (w2) R T ln a (w1)

=
Definition

R T
ln a w P =
vw

cR T

if csalts

Membrane Separations

Reverse Osmosis (RO)

Membrane Separations

Reverse Osmosis (RO)

- The water freely flows through the membrane
due to the pressure difference corrected by the .
J w = Q w = A (P )
Am
Jw: Solvent volume flux (m3/sm2)
Qw: Solvent volume flowrate (m3/s)
Am: Membrane area (m2)
A: Permeability (m3/sm2Pa)*
P: Hydraulic pressure difference (Pa)
: Osmotic pressure difference (Pa)
* A = AoKt Kc Ke

t: temperature; c: compaction; e: fouling

Membrane Separations

Reverse Osmosis (RO)

- Salt flux is due to both diffusion and convective
transport.
Js = J w Cp = B (Cm Cp ) + M J w Cm

J s B (Cm Cp )
Cp =
=
+ M Cm
J w A (P )

Js: Solute mass flux (mol/sm2)

Bi: Permeability (m/s)
Cm: Solute concentration on the membrane surface (mol/m3)
Cp: Solute concentration in the permeate (mol/m3)
M: Distribution constant (~ 0.005)

Membrane Separations

Reverse Osmosis (RO)

- Thus a relation between the local rejection,
Rl, and the permeate flux (or applied pressure)
can be found.
Cm Cp
Cp
Rl =
= 1
Cm
Cm
1 = 1 + B 1
R l (1 M ) (1 M ) J w
1 = 1 + B
1
R l (1 M ) (1 M ) A (P )

Membrane Separations

Reverse Osmosis (RO)

- Membranes mostly made of CA or PA.
- Configuration in spiral-wound or hollow fiber.
- Typical conversion between 10 and 30%.
- Flow limited by concentration polarisation.
- Rejection up to 99% (sometimes higher).
- Fouling problems and cleaning. Pretreatment.

Membrane Separations

Reverse Osmosis (RO)

- Concentration polarisation
boundary
layer

ln

cm

bulk

Jc
J cp

cp

dc
dx

D: Diffusion coeficient (m2/s)

/: boundary layer thickness (m)
k=D//: mass transfer coeficient (m/s)

cb cp

J
D

cm cp

J
= exp

cb cp
D

cb
D

cm cp

cm
=
cb

J
exp
k

J
R l + (1 R l ) exp
k

Membrane Separations

Reverse Osmosis (RO)

- Applications: Drinking water, food industry,
wastewater treatment. Examples:
Desalting of process water.
Desalination of brackish or seawater.
Production of ultrapure water for laboratories or
electronic industry.
Concentration wastewater in paper pulping.
Concentration of juices, milk or sugar solutions.
Concentration of coffee, te or soups.
Concentration of aminoacids (and other
pharmaceutical substances).

Membrane Separations

ED
5%

Reverse Osmosis (RO)

RO
35%
EVM
60%

- Seawater desalination:

30-40% market
Desalination technologies (1996)
Very competitive process
Module cascade in series and parallel
Comparison between the energetic cost for
seawater desalination.
Process

Energy (kWh/m3)

Multiple distillation

15.5

Reverse Osmosis
RO with energy recovery

9
6.5

Electrodialysis

12

Membrane Separations

Reverse Osmosis (RO)

Feed
UF
pretreatment
Permeate

1st pressure stage

: RO module

2nd pressure stage

Concentrate

Water production plant based on RO.